WO2008119448A1 - Cosmetic preparation having hydrophobically modified polysaccharides and water-soluble uv filters - Google Patents

Abstract

A cosmetic preparation comprising water-soluble UV filters and non-ionic, water-soluble, hydrophobically modified hydroxyethyl cellulose (HEC), characterized by linking it with at least one short-chained hydrophobic group having (3 to 8) carbon atoms, particularly preferably having (3 to 5) carbon atoms, and at least one long-chained hydrophobic group having (9 to 24) carbon atoms.

Description

 Beiersdorf Aktiengesellschaft Hamburg

description

Cosmetic preparation with hydrophobically modified polysaccharides and water-soluble UV filters

The present invention relates to a cosmetic preparation with hydrophobically modified polysaccharides and water-soluble UV filters.

Polymeric compounds, for example polyacrylates or polysaccharides, have been used for many years as "thickeners" for increasing the viscosity, in particular of aqueous foods, cosmetic preparations, building materials, etc. One particular class of polymeric thickeners is the polysaccharides, which, on the basis of their properties mostly of natural origin, both biologically acceptable (ie non-toxic, biodegradable, etc.) both when consumed and non-culinary applications Examples of such polysaccharides include compounds from the group of gums (for example gum arabic, locust bean gum, tragacanth, karaya , Guar gum, pectin, gellan gum, carrageenan, agar, algine, chondrus, xanthan gum), hyaluronic acid, chitin, chitosan, chondroitin sulfates, starch and starch derivatives, and cellulose and cellulose derivatives.

A particular challenge is the thickening of cosmetic preparations. Cosmetic preparations are sometimes highly complex mixtures (for example aqueous gels or emulsions) from a wide variety of chemical compounds. A thickener for cosmetic preparations must therefore have a high compatibility with a variety of substances. Despite the (apparently) wide range of polymeric thickening agents, it has been a major problem for a person skilled in the art to date to find a suitable compound for a cosmetic preparation. to find custody. In particular, the temperature stability, storage stability, tolerance to other ingredients and the cosmetic performance are difficult for a person skilled in the formulation of a cosmetic preparation. If the preparation should have a slightly viscous viscosity, according to the prior art relatively large amounts of thickening agent have to be added to the preparation, whereby it leaves an unpleasantly greasy-sticky impression when applied to the skin, which is unacceptable to the user. A further problem area in the thickening of cosmetic preparations is the incorporation of salt-like compounds (electrolytes), whose incorporation into thickened formulations regularly leads to precipitations and phase separations.

An emulsion is a mixture of two or more immiscible liquids, one of which is in droplet form in the other. In the classical emulsion, the oil may either be dispersed in the water (oil-in-water or o / w emulsion) or the water may be dispersed in the oil (water-in-oil, w / o or inverse emulsion). This terminology is important because the emulsion characteristically takes on the properties of the external phase, a key factor in the emulsion formulation and design. For example, an oil-in-water emulsion may be diluted with water or dried by evaporation, leaving the other ingredients as a film. The water-in-oil emulsion, on the other hand, can not be dried.

Emulsions are used in a variety of fields such as textiles, leather and metal treatments, foods, cosmetics, pharmaceuticals and paints, agrochemicals, polymerization, cleaning and polishing, and ore and petroleum extraction.

Emulsions are inherently unstable systems and the risk of deterioration during storage is greater than for a non-emulsified product. Although emulsion technology seems to be based on simple interfacial principles, it is highly complex, especially when considering dynamic and static conditions.

The most obvious and typically most significant emulsions properties are the following: easy thinnability, viscosity, color and Stability. For a particular type of emulsifier, these properties depend on (1) the continuous phase properties, (2) the external to internal phase ratio, (3) emulsion particle size, (4) the continuous phase to particle ratio (including ionic charges) and (5) the properties of the discontinuous phase. For a given emulsion, the properties depend on which liquid forms the external phase, ie, whether the emulsion is o / w or w / o. The resulting emulsion is determined by the emulsifier (type and amount), the ratio of ingredients and the order of addition of ingredients during mixing.

The dispersibility (solubility) of the emulsion is determined by the continuous phase. Thus, if the continuous phase is water-soluble, the emulsion can be diluted with water. Conversely, if the continuous phase is oil-soluble, the emulsion can be diluted with oil.

Emulsions can be thin or thick fluids or fluids, pastes or gels and can exhibit thixotropy or dilatancy. The viscosity is influenced by (1) the characteristics of the external phase, including the additives, (2) the volume ratio of the two phases, and (3) the particle size. Note that the type of emulsion is not considered to be a major influence on viscosity despite the common belief that o / w emulsions are thinner than w / o. This is true only in so far as the commonly used oils are more viscous than water. The viscosity of an emulsion is essentially the viscosity of the external phase, as long as it accounts for more than half of the total volume. As the proportion of the internal phase increases, the viscosity of the emulsion increases to the point where the emulsion is no longer liquid. When the volume of the internal phase exceeds the volume of the external phase, the emulsion particles are densely packed and the apparent viscosity is partly structural viscosity.

The addition of thickeners or gelling agents that are compatible with the emulsifier can increase the viscosity of the continuous phase. Many thickeners, such as carboxymethylcellulose (CMC), methylcellulose (MC), and plant gums or clays, can often be added with little or no change in the basic emulsifier. If the thickening agent or gelling agent on its own Surfactant, the overall balance of the emulsifier probably requires a readjustment. The emulsion viscosity can often be reduced by increasing the proportion of the continuous phase, usually water. The addition of polar solvents, such as alcohol or acetone, which can reduce the viscosity, usually caused a marked reduction in emulsion stability. Presumably, since the emulsifier is more soluble in the polar solvent, it is extracted from the interface, which is subsequently weakened. Thickening or dilution of the dispersed phase usually has little or no effect on the total viscosity. With normally liquid o / w polymer emulsions, viscosity differences can be obtained by varying the nature of the adsorbed water structure around each particle by means of a change in surfactant or electrolyte concentration.

Another problem is the stable incorporation of water-soluble and ionic compounds, which by their polarity essentially have a destabilizing effect on the emulsion or preparation. Neutralized crosslinked polyacrylic acids are most commonly used as thickeners. It is known that the ionic compounds are incompatible with polyacrylic acid thickeners. As a rule, the ionic compounds break the emulsions.

Prior to the present invention, there was a need in the personal care industry for a product which could emulsify cosmetic oil-in-water lotions or water-in-oil creams without the need for heat, and which would preserve the emulsion by preventing phase separation and degradation Could stabilize creaming.

An emulsion is stable as long as the particles of the internal phase do not coalesce. The stability of an emulsion depends on: (1) the particle size; (2) the difference in the density of the two phases; (3) the viscosity of the continuous phase and the completed emulsion; (4) the charges on the particles; (5) nature, effectiveness and amount of emulsifier used; and (6) storage conditions, including temperature variation, agitation and vibration, as well as dilution or evaporation during storage or use. The stability of an emulsion is influenced by almost all factors involved in its formulation and preparation. For formulas containing fairly large amounts of emulsifier, stability is predominantly a function of the type and concentration of the emulsifier. Emulsifiers can be classified as ionic or nonionic depending on their behavior. An ionic emulsifier is composed of an organic lipophilic group (L) and a hydrophilic group (H). Hydrophilic-lipophilic balance (HLB) is often used to characterize emulsifiers and related surfactant materials. The ionic types can be further classified into anionic and cationic, depending on the nature of the ion-active group. The lipophilic portion of the molecule is usually considered to be the surface active portion.

Nonionic emulsifiers are completely covalent and show no obvious

Tendency to ionization. They can therefore be combined with other nonionic surfactants and also with either anionic or cationic agents. The nonionic emulsifiers are also less susceptible to the action of electrolytes than the anionic surfactants. The solubility of an emulsifier is of utmost importance in the preparation of emulsifiable concentrates.

Emulsifiers, which are surfactants, reduce the surface and interfacial tensions and increase the tendency of their solution to spread.

Oil-in-water emulsifiers provide emulsions in which the continuous phase is hydrophilic; therefore, such emulsions are generally dispersible in water and conduct electricity. The surfactants capable of producing such an emulsion typically have an HLB of greater than 6.0 (preferably 7) with the hydrophilic portion of their molecules predominating. (Between HLB 5 and 7, many surfactants function as either w / o or o / w emulsifiers, depending on how they are used.)

Two important parameters of the emulsion are droplet size and long-term storage stability over a certain temperature range. Small droplets (ie, less than 5 microns) are desired so that emulsions have a high degree of opacity and are easier to stabilize. The long-term storage stability correlates with rheological parameters, such as yield stress and elasticity. Ultimately, formulated lotions need to have an acceptable feel with consumers. A conventional procedure for the provision of emulsification and stabilization in cosmetic oil-in-water lotions is via a three-dimensional surfactant network, which forms on heating of waxy surfactant solutions to more than 65 ⁰ C. The network is an association of a large excess of surfactant molecules (that is, 5 - 10 wt .-%) and shows a limited temperature stability (less than 40 - 45 ⁰ C). To enhance the stabilizing attributes of the surfactant network, physical gellants, such as Carbopol® crosslinked polyacrylates, are typically added. This combined procedure (excess surfactant and physical gel) achieves both emulsification and long-term storage stability. The disadvantages of these cosmetic lotions are the heat required for emulsification and the high concentration of surfactant that can cause skin irritation. A material which can provide both room temperature emulsifying properties and stabilizing properties at a low usage level is desirable.

Polymeric emulsifiers are hydrophilic polymers that are hydrophobically modified by the introduction of an alkyl chain. Their chemical structure makes them act as oil-in-water emulsifiers (and as stabilizers). Hydrophobically modified crosslinked polyacrylic acid copolymers (eg Carbopol ETD 2020) are used as primary emulsifiers in the cosmetics industry. However, because of their anionic character, they can not be formulated in electrolyte-containing emulsions because electrolytes "break" the emulsion and liquefy it.

Another approach to overcoming the instability problem of the oil-in-water emulsions is to greatly increase the level of emulsifier in these emulsions. However, emulsifiers, when used in large quantities, are known to be irritating to certain skin types. Moreover, the resulting creams are often compact and heavy or stiff.

Stabilization of emulsions against flocculation and / or coalescence required the presence of an energy barrier between the droplets to prevent close approximation (the van der Waals attraction being strong). Two general mechanisms can be used to create such a high (repulsive) energy barrier. Electrostatic stabilization

It is based on the formation of an electric double layer. When two droplets approach a separation distance at which the bilayers begin to lobule, a strong repulsion occurs, provided the surface or zeta potential is sufficiently high and the electrolyte concentration and valence of the ions are low.

Steric stabilization - It is based on the adsorption of the surfactant or polymers at the oil / water interface with the hydrophobic (alkyl) group directed to the oil phase (or dissolved therein) and the hydrophilic chain formed in the aqueous phase remains. When two droplets approach each other at a separation distance such that the adsorbed layers begin to overlap, repulsion occurs as a result of two mechanisms: o unfavorable mixing of the polymer layers when under good solvent conditions (osmotic effects); and o Reduction of configuration entropy with significant overlap

(entropy effects).

U.S. Patent No. 4,904,772 discloses the use of water-soluble cellulose ether having at least two hydrophobic moieties of from 6 to 20 carbon atoms wherein one of the hydrophobic moieties has a carbon chain length longer by at least two carbon atoms than the other hydrophobic residues. This patent discloses that this cellulose ether can be used in paints, as stabilizers in emulsion polymerization, as protective colloids in suspension polymerization, as thickening agents in cosmetics and shampoos, and as flocculants in mineral processing.

U.S. Patent No. 6,166,078 discloses the use of cetyl-modified hydroxyethyl cellulose (Polysurf 67) in stable gel compositions containing a dispersed oil and large amounts of electrolytes. The disadvantages of these electrolyte-containing emulsions are the limited short-term storage stability at elevated temperatures. and the limited long-term storage stability of emulsions without the presence of electrolytes at elevated temperatures.

It was therefore the object of the present invention to eliminate the disadvantages of the prior art, and to develop a new, more suitable for cosmetic preparations with water-soluble UV filters thickener.

The object is surprisingly achieved by a cosmetic preparation comprising water-soluble UV filters and a nonionic, water-soluble, hydrophobically modified polysaccharide characterized by linking with at least one short-chain hydrophobic group having 3 to 7, particularly preferably 3 to 5 carbon atoms and at least one long-chain hydrophobic group 8 to 24 carbon atoms

This invention also seeks to provide a skin care and / or sunscreen cosmetic product which comprises the above emulsion and at least one active body care ingredient or contains electrolytes.

It has surprisingly been found that a mixed hydrophobic polysaccharide could function both as an emulsifier and as a stabilizer in skin care products. This mixed hydrophobic polysaccharide functionally replaces a portion of the surfactant in cosmetic emulsions, creams and lotions at significantly lower levels of use.

EMULSIONS

According to this invention, emulsions with this mixed hydrophobic polysaccharide have small droplets (ie less than 5 μm) and rheological properties that surprisingly do not change with temperature. Thus, the emulsion stability is maintained to 50 ⁰ C. The small droplets are desirable so that emulsions have a high degree of opacity and are easier to stabilize. The

Long-term storage stability correlates with theological parameters, such as yield stress and elasticity. This attribute of temperature stability is typical of structured surfactant or polymer solutions which "melt" with increasing temperature and cause loss of emulsion stability at elevated temperatures. Find it the skin-leave cosmetic products of the present invention are useful in a variety of applications where a structure over a wide temperature range is required. Nevertheless, formulated lotions ultimately have an acceptable consumer feel.

In accordance with this invention, emulsions may be oil-in-water or water-in-oil, designating the continuous and discontinuous or internal phases. In general, O / W emulsions conduct electricity, are dilutable with water, feel more like water, dry quickly (lose water), can be washed off (from the skin, etc.), are more corrosive and exhibit the watery properties of the skin continuous phase. On the other hand, w / o emulsions conduct electricity poorly, if at all, can be diluted with oil or solvents, feel more like oil, are resistant to drying or water loss, although they easily lose a volatile solvent, are difficult to wash off, are less corrosive - rosic or corrosive and generally show, depending on the oil phase, the properties of the continuous oil phase.

The particle size of a liquid emulsion is related to the manufacturing process, the energy input, the viscosity difference between the phases and the type, and the amount of surfactant used. With regard to the formation of a small particle size, emulsions can be classified into formulas having a low emulsifier content which require only a moderate amount of mechanical power. The energy supply is an important variable. The particle size generally decreases with high agitation, a small difference in viscosity between the two phases and the use of a larger amount of the appropriate surfactant. In this invention, less surfactant is used or needed than usual because the mixed hydrophobic polysaccharide functions both as an emulsifier and as a stabilizer. Thus, fewer components are needed to form the emulsion with the result that less energy is needed to form the small particle size emulsion.

In an emulsion, the larger the particle, the greater the tendency to coalesce and further increase the particle size. Thus, fine particles promote stable emulsions. In this invention, coalescence is enhanced by the use of This mixed hydrophobic gum slows down, providing a protective colloid effect.

POLYSACCHARIDES

According to this invention, the polysaccharide polymer for the backbone of the hydrophobically modified polymer is cellulose ether. Examples of cellulose ethers are hydroxyethylcellulose (HEC) and methylhydroxyethylcellulose (MHEC).

Cellulose ethers are widely used polysaccharides for applications such as thickeners in personal care products. The size and amount of hydrophobe primarily determine the water solubility and rheological properties of these polymers. For example, a hydroxyethyl cellulose derivative having a long alkyl chain hydrophobicity (i.e., a chain length of 12 or greater) exhibits very high aqueous viscosity at a much lower alkyl content than its shorter alkyl chain (i.e., less than 8 carbon atoms) containing counterparts. However, similar polymers with long alkyl chains become water insoluble at a lower degree of alkyl substitution. This insolubility severely restricts their usefulness in situations where a higher level of hydrophobicity is best suited to achieve the desired performance characteristics, such as improved color development and paint spray resistance.

According to the present invention, the polysaccharide polymers have associative, hydrophilic and hydrophobic properties. The term "associative" when applied to the thickening agent means a water-soluble polymer, the hydrophobic one

Contains groups whose attractive force to one another in the aqueous phase and latex and pigment particles in the dispersed phase both thicken the paint and regulate the rheology of the paint. The term "hydrophilic" means water-loving or attracted to water. The term "hydrophobic" means water repellent or rejected by water. Therefore, the different properties in the molecule of the present invention provide a complex environment that requires balancing the components of the molecule for optimal properties. This compensation itself lends itself to numerous possibilities for changes in the properties. According to this invention, the short-chain hydrophobic group contains 3 to 5 carbon atoms. Examples of such units are propyl, butyl and pentyl radicals, the long-chain hydrophobic group containing 8 to 24 carbon atoms. Examples of such units are octyl, hexadecyl and decyldodecyl. Two or more of the following performance characteristics can be attained simultaneously by regulating the amount of short chain alkylhydrophobe, long chain alkylhydrophobe, and hydroxyethyl modification method present in the molecule, as well as the molecular weight of the polymers.

The polymers of this invention can be prepared directly from cellulose. First, chemical cotton is added to a mixture of an inert organic diluent and alkali metal hydroxide. Thereafter, ethylene oxide or other substituent is added to the resulting alkali cellulose, and after the reaction is completed, the product is treated with nitric acid. To this reaction mixture are added the alkyl glycidyl ethers and optionally a second addition of ethylene oxide. After completion of the reaction, the product is neutralized, filtered, washed with aqueous inert diluents and dried.

In particular, the preferred procedure for preparing a polymer using alkyl bromides involves the alkylation of cellulose in a mixture of t-butyl alcohol, isopropyl alcohol, acetone, water and sodium hydroxide in a nitrogen atmosphere for a time sufficient to allow the alkali to the cellulose to distribute. Thereafter, ethylene oxide is added to the alkali cellulose slurry, followed by heating at 70 ° C for one hour. The resulting slurry is partially neutralized and additional ethylene oxide is added to the reaction mixture. Then, the resulting reaction mixture is heated for 90 minutes at 90-95 ⁰ C. Alkali and alkyl bromides (two different alkyl bromides, one having 3-5 carbon atoms and the other having 8-24 carbon atoms) are added, followed by heating the reaction mixture at 115 ° C for 2 hours and neutralizing the reaction mixture. The reaction mixture is washed and then the resulting polymer is purified.

Another method of making the polymer of the present invention is to start from a commercial intermediate. In short, the modifications can be carried out by slurrying a polymer such as hydroxyethyl cellulose in an inert organic diluent such as a lower aliphatic alcohol, ketone or hydrocarbon, and adding a solution of alkali metal hydroxide to the resulting slurry at low temperature. When the ether is thoroughly wetted and swollen by the alkali, the alkyl glycidyl ether is added and the reaction is continued with stirring and heating to completion. Residual alkali is then neutralized and the product is recovered, washed with inert diluents and dried.

According to the present invention, the polysaccharide polymers for the backbone of the hydrophobically modified polymer have a weight average molecular weight (Mw) generally lower limit of 50 kDa, preferably 100 kDa, more preferably 300 kDa and most preferably 800 kDa. The upper limit of the molecular weight (Mw) is generally 3000 kDa, preferably 1500 kDa, more preferably 1200 kDa (1 kDa = 1000 Da = 1000 g / mol).

The backbone has at least one short chain hydrophobic group composed of C3-C7, preferably C3-C5, and more preferably C4. The backbone has at least one long-chain hydrophobic group made up of C8-C24, preferably C14-C22, more preferably C14-C18, and most preferably C16.

The content of short-chain hydrophobic groups is at least 0.5% by weight, preferably between 3.0 and 4.0% by weight.

The content of long-chain hydrophobic groups is at least 0.2 wt .-%, preferably between 0.5 and 0.8 wt .-%.

Preferred polysaccharides are modified hydroxyethycelluloses (HEC) linked to 3.0 to 4.0% by weight of butyl groups and 0.5 to 0.8% by weight of palmityl groups through ether linkages.

A preferred polymer according to the invention has a weight-average molecular weight (Mw) of 1000 kDa, the backbone comprising 3.36% by weight of short-chain hydrophobic has a group which is n-butyl, and 0.65% by weight long-chain hydrophobic group which is hexadecyl.

BODY CARE PRODUCTS

According to the present invention, skin-leave products are defined as any formulation used to protect or treat or improve the appearance of the skin of a human. The composition left on the skin normally comprises: 1) a vehicle system which normally comprises a thickener and solvent; and 2) an active ingredient.

According to the present invention, the solvent used in the vehicle system should be compatible with the other components in the present composition. Examples of the solvents used in the present invention are water, water-lower alkanol mixtures and polyhydric alcohol having 3 to 6 carbon atoms and having 2 to 6 hydroxyl groups. Preferred solvents are water, propylene glycol, water-glycerol, sorbitol-water and water-ethanol. The solvent (in the case of use) in the present invention is present in the composition in a proportion of 0.1 to 99% by weight of the composition.

Surprisingly solved the object is further characterized by a preparation already described characterized in that the polysaccharide has a molecular weight of 300 kDa to 3000 kDa. Furthermore, it is preferred according to the invention if the water-soluble UV filter from the group compounds phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium , Potassium or triethanolammonium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt, salts of 2-phenylbenzimidazole-5-sulfonic acid, such as their sodium, potassium or their triethanolammonium salt and the sulfonic acid itself, 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 and the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt and sulfonic acid derivatives of the 3 Benzylidencamphers, such as. B. 4- (2-oxo-3-bionylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts becomes. It is further preferred if it is an emulsion with droplet sizes less than 5 microns. It is particularly preferred if their viscosity in the temperature range from 10 to 50 ^° C. is essentially independent of temperature and differs by at most 30% in the temperature range indicated. It is very particularly preferred if the viscosity of the preparation is 100 to 20 000 mPas. It is exceptionally preferred if the preparation contains an O / W emulsifier.

The viscosity according to the invention was measured with a Haake ViscoTester 02 viscometer. This type of viscometer consists of a rotating cylinder and a stationary measuring cup. The device uses the rotational resistance force of the formulation to determine the viscosity of the sample. Speed (rpm) = 62.5. Viscosity after 30 s. determine. (Measuring temperature = RT)

Cosmetic preparations according to the invention can be present in various forms. So they can e.g. a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the water-in-oil type in water (W / O / W), a gel, a solid stick, an ointment, a foam or even an aerosol.

In this case, it is preferred according to the invention if the cosmetic preparation is in the form of an emulsion and particularly preferred if the preparation is in the form of an O / W emulsion.

In the case of the cosmetic preparations according to the invention, methods of preparation or uses, it is preferred according to the invention if salt-like UV light protection filters are contained.

Preparations according to the invention which are particularly preferred according to the invention, processes for their preparation or uses which are characterized in that the water-soluble UV light protection filters are selected from the group of the compounds phenylene-1,4-bis- (2-benzimidazyl) -3,3'- 5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt, salts of 2-phenylbenzimidazole 5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself, 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene (also: S.S. -O-phenylenedimethylene-bis-1H-dimethyl-oxo-bicyclo-β-i-hept-1-ylmethane sulfonic acid) and its salts, and the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, in particular its sodium salt.

According to preferred additional ionic active substances are selected from Crea- tin and folic acid.

Emulsions of the invention are advantageous and contain e.g. Fats, oils, waxes and other fats, as well as water and an emulsifier as commonly used for such type of formulation.

The lipid phase can advantageously be selected from the following substance group: mineral oils, mineral waxes

Oils such as triglycerides of capric or caprylic acid, further natural oils such as e.g. Castor oil, macadamia, avocado or jojoba oil, dialkyl ethers such as e.g. Di-n-octyl ethers and dialkyl carbonates such as di-n-octyl carbonate fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;

benzoates;

Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from caprylic / capric triglycerides, dicaprylyl carbonate, mineral oil, C12-15 alkyl benzoates, cocoglycerides, octyldodecanol, butylenes glycol dicaprylates / dicaprate, dicaprylyl ether, hydrogenated Polyisobutenes, cetearyl isononanoate, isodecyl neopentanoate, squalane and C13-16 isoparaffin Advantageously, the oil phase may further comprise a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.

It is advantageous to use cyclomethicone (octamethylcyclotetrasiloxane) and dimethicone as the silicone oil to be used according to the invention. However, other silicone oils are also advantageous for the purposes of the present invention, for example hexamethylcylotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), phenyltrimethicones.

The preparations according to the invention may furthermore advantageously comprise one or more substances from the following group of siloxane elastomers, for example in order to increase the water resistance and / or the sun protection factor of the products:

(a) siloxane elastomers which contain the units R ₂ SiO and RSiO _{1 5} and / or R ₃ SiO ₀ , ₅ and / or SiO ₂ , where the individual radicals R are each independently hydrogen, C _1-24 -alkyl ( such as methyl, ethyl, propyl) or aryl (such as phenyl or ToIyI), alkenyl (such as vinyl) and the weight ratio of the units R ₂ SiO to RSiO _{1p5 is selected} from the range of 1: 1 to 30: 1;

(b) Siloxane elastomers which are insoluble and swellable in silicone oil obtainable by the addition reaction of an organopolysiloxane (1) containing silicon-bonded hydrogen with an organopolysiloxane (2) containing unsaturated aliphatic groups, the proportions used being such be such that the amount of hydrogen of the organopolysiloxane (1) or the unsaturated aliphatic groups of the organopolysiloxane (2)

In the range of 1 to 20 mol%, if the organopolysiloxane is not cyclic and

In the range of 1 to 50 mol%, when the organopolysiloxane is cyclic.

Advantageously in the context of the present invention, the siloxane elastomer (s) are in the form of spherical powders or in the form of gels. Advantageously present in the form of spherical powder siloxane elastomers are those with the INCI name dimethicone / vinyl Dimeticone Crosspolymer, for example, that available from Dow Corning under the trade names Dow Corning 9506 Powder available.

According to the invention, the preparation according to the invention advantageously contains one or more film formers. Film formers for the purposes of the present invention are substances of different composition, which are characterized by the following property: If a film former is dissolved in water or other suitable solvents and the solution is then applied to the skin, it forms a film after the solvent has evaporated which essentially has a protective function.

It is particularly advantageous to use the film formers from the group of polymers based on polyvinylpyrrolidone (PVP).

zu wählen. Besonders bevorzugt sind Copolymere des Polyvinylpyrrolidons, beispielsweise das PVP Hexadecen Copolymer und das PVP Eicosen Copolymer, welche unter den Handelsbezeichnungen Antaron V216 und Antaron V220 bei der GAF Chemicals Cooperation erhältlich sind.

to choose. Particularly preferred are copolymers of polyvinylpyrrolidone, for example the PVP hexadecene copolymer and the PVP eicosene copolymer, which are available under the trade names Antaron V216 and Antaron V220 in the GAF Chemicals Cooperation.

Also advantageous are other polymeric film formers, such as sodium polystyrene sulfonate, sold under the tradename Flexan 130 at National Starch and Chemical Corp. and / or polyisobutene, available from Rewo under the tradename Rewopal PIB1000. Further suitable polymers are, for example, polyacrylamides (Seppigel 305), polyvinyl alcohols, PVP, PVP / VA copolymers, polyglycols. Also advantageous is the use of hydrogenated castor oil dimerdilinoleate (CAS 646054-62-8, INCI Hydrogenated Castor OiI Dimer Dilinoleate), which can be purchased from Kokyu Alcohol Kogyo under the name Risocast DA-H or PPG-3 Benzylethermyristat ( CAS 403517-45-3), which is under the trade Crodamol STS can be purchased from Croda Chemicals and Dermacryl 79 (acrylate / octylacrylamide copolymer) from National Starch.

If appropriate, the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore low C-number alcohols, eg Ethanol, isopropanol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, glycerol. In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient.

Emulsions of the invention are advantageous and contain e.g. the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as it is usually used for such a type of formulation.

On the one hand, it is advantageous according to the invention if the preparation is in the form of a GYW emulsion. In this case, it is particularly preferred according to the invention if the preparation comprises one or more O / W emulsifiers selected from the group of the compounds glyceryl stearate citrate, glyceryl stearate (self-emulsifying), stearic acid, stearate salts, polyglyceryl-3-methylglycose distearate, ceteareth-20, PEG Contains -40 stearate, PEG-100 stearate, sodium stearoyl glutamate and sodium cetearyl sulfate.

On the other hand, it is advantageous according to the invention if the preparation is in the form of a W / O emulsion. In this case, it is particularly preferred according to the invention if the preparation contains one or more W / O emulsifiers selected from the group of the compounds polyglyceryl-2-dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, cetyl dimethicone copolyol, polyglyceryl-3 diisostearate.

Gels according to the invention usually contain low C number alcohols, e.g. Ethanol, isopropanol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, glycerol and water.

The cosmetic preparations according to the invention may contain cosmetic adjuvants such as are conventionally used in such preparations, for example preservatives, bactericides, perfumes, substances for preventing foaming, colorants. Fe, pigments which have a coloring effect, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other customary constituents of a cosmetic or dermatological formulation, such as alcohols, polyols, polymers, foam stabilizers, Electrolytes, organic solvents or silicone derivatives.

In particular, active ingredient combinations used according to the invention can also be combined with other antioxidants and / or radical scavengers.

Such antioxidants in the context of the present invention are advantageously chosen from:

Peptides such as D, L-camosine, D-carnosine, L-camosine and their derivatives (eg anserine), (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, Malic acid), EDTA, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives (in particular ubiquinone Q10), vitamin C and derivatives (eg ascorbyl palmitate, Na ascorbyl phosphate) , Tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), plant polyphenols with a log P of 1-3, α-glycosylrutin, butylhydroxytoluene,, creatine / creatinine, licocalcone, Flavonoids / isoflavonoids (from soy), grape seed oil, urea, dicarboxylic acid.

Particularly advantageous for the purposes of the present invention, water-soluble antioxidants can be used, such as vitamins, eg. As ascorbic acid and its derivatives.

Preferred antioxidants are also vitamin E (α-tocopherol) and its derivatives as well as vitamin A (retinol) and its derivatives.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1-10 wt .-%, based on the total weight of Preparation. Preparations according to the invention may advantageously comprise further UV light protection filters, the total amount of the filter substances being, for example, 0.1% by weight to 30% by weight, preferably 0.5% to 10% by weight, in particular 1% to 6.0% by weight %, based on the total weight of the preparations, in order to provide cosmetic preparations which protect the hair or the skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for hair.

Advantageously, preparations according to the invention may contain further UV light protection filters, the total amount of filter substances being e.g. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1, 0 to 6.0 wt .-%, based on the total weight of the preparations to cosmetic preparations for To provide the hair or the skin against the entire range of ultraviolet radiation. They can also serve as a sunscreen for hair.

If the preparations according to the invention contain UVB filter substances, they may be oil-soluble or water-soluble. Advantageously oil-soluble UVB filters according to the invention are, for example:

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 cinnamic acid, preferably 4-methoxycinnamate (2-ethylhexyl) ester, 4-

methoxycinnamate; Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate,

Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-

Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzalmalonate,

Esters of 2-cyano-3,3-diphenylacrylic acid, preferably ethylhexyl-2-cyano-3,3-diphenylacrylate. The list of said UVB filters which can be used in combination with the active compound combinations according to the invention should of course not be limiting.

It may also be advantageous to use UVA filters that are commonly included in cosmetic preparations. These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- (4 '-isopropylphenyl) propane-1,3-dione.

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

und unter dem Uvinul A Plus bei der Fa. BASF erhältlich ist.

and Uvinul A Plus is available from BASF.

Also advantageous according to the invention is 2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine with the CAS No. 288254-16-0, which is available from 3V Sigma under the trade name Uvasorb® K2A.

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives such. B. dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade designation UVASORB HEB from Sigma 3V; and 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-r-hexyloxy)] - 1, 3,5-triazine (INCI: Octyl Triazone), which is marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

Advantageous broadband filter according to the present invention is further the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1] [(trimethylsilyl) oxy] disiloxa- nyl] propyl] -phenol (CAS No .: 155633-54-8) with the INCI name drometrizole trisiloxanes.

Further advantageous UV filters are derived from the group of triazines, e.g. the 2,4-bis- [4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (trade name Tinosorb® S) and the Group of triazoles, such as the 2,2'-methylenebis [6-2H-benzotriazol-2yl] -4- (1,1,3,3-tetramethylbutyl) phenol) (trade name Tinosorb® M).

The amounts used for the UVB combination can be used.

It is also according to the invention if, in addition, inorganic pigments are contained. Such 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 ).

Zinc oxide particles which are suitable according to the invention and predispersions of zinc oxide particles are obtainable from the following companies under the following commercial names:

Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available from the following companies under the following trade names:

Furthermore, according to the invention, organic UV filter pigments, in particular the particulate organic sunscreen filters 2, 4, 6-tris (biphenyl) -1, 3, 5-triazine and / or 2,4,6-tris (terphenyl) -1, may advantageously be used. 3,5-triazine can be used advantageously.

Furthermore, the preparations according to the invention may also advantageously contain repellents for protection against mosquitoes, ticks and spiders and the like. Advantageous z. B. N, N-diethyl-3-methylbenzamide (trade name: Meta-delphene, "DEET"), di- methyl phthalate (trade name: Palatinol M, DMP) ₁ 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester and in particular 3- (Nn-butyl-N-acetylamino) -propionic acid ethyl ester (available commercially from Merck under the trade name Insekt Repellent® 3535. The repellents can be used both individually and in combination.

Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or spreading on the skin surface, to reduce the moisture release of the homschicht (also called trans-epidermal water loss (TEWL)) and / or hydration to positively influence the Homschicht.

Advantageous humectants (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, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Moisturizers can also be used as anti-wrinkle active substances to protect against skin changes, as they are known, for example. B. occur during skin aging, can be used.

It is advantageous for the purposes of the present invention if the preparation according to the invention comprises one or more humectants in a total concentration of 0.1 to 20 % By weight and preferably in a total concentration of 0.5 to 10% by weight, based in each case on the total weight of the preparation.

The cosmetic preparations according to the invention may furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or 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 mainly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ^® (CAS no. 7631-86-9).

These cosmetic or dermatological preparations may also be aerosols with the auxiliaries normally used for them.

The compositions according to the invention optionally contain additives customary in cosmetics, for example perfumes, dyes, deodorants, antimicrobials, moisturizing agents, complexing and sequestering agents, pearlescing agents, effect substances, plant extracts, vitamins, active ingredients and the like.

It is preferred according to the invention to add complexing agents to the cosmetic preparations according to the invention.

The complexing agent (s) can advantageously be selected from the group of the customary compounds, preference being given to at least one substance selected from the group consisting of tartaric acid and its anions, citric acid and its anions, aminopolycarboxylic acids and their anions (such as, for example, ethylenediaminetetraacetic acid (EDTA) and Anions, nitrilotriacetic acid (NTA) and their anions, hydroxyethylenediamine triacetic acid (HOEDTA) and its anions, diethylenetaminopentaacetic acid (DPTA) and their anions, trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) and their anions) and tetrasodium iminodisuccinate (IDS).

The complexing agent (s) according to the invention are advantageously present in cosmetic or dermatological preparations, preferably to 0.01% by weight to 10% by weight, preferably to 0.05 wt .-% to 5 wt .-%, particularly preferably from 0.1 to 2.0 wt .-%, based on the total weight of the preparations.

For use, the cosmetic preparations according to the invention are applied to the skin in a sufficient amount in the manner customary for cosmetics.

The preparations according to the invention are used in particular in skin or face creams, skin or face lotions and day or night creams or lotions.

The use in sunscreens according to the invention is particularly preferred.

Advantageous in the context of the present invention are preparations for the care of the skin: they can serve the cosmetic sunscreen, as well as make-up product in decorative cosmetics.

Example formulations for cosmetic preparations according to the invention

Preferred C4 / C16-mixed hydrophobic hydroxyethylcellulose (polysaccharide skeleton, Mw = 1000 kDa) according to the invention:

O/W-Emulsionen

O / W emulsions

¹ Dry FIo PC, National Starch

² Cleargum CO 01, Roquette

³ Tapioca Pure, National Starch O / W emulsions

⁴ Carbopol 980, Noveon

⁵ Dry FIo-PC, National Staren

⁶ Cleargum CO 01, Roquette

⁷ Tapioca Pure, National Starch O / W emulsions

¹ Carbopol 981, Noveon

Dry FIo-PC, National Starch

¹⁰ Cleargum CO 01, Roquette

¹¹ Tapioca Pure, National Starch

¹² corn PO4 PH "B", Dr. Hauser O / W emulsions

13 Carpobol 1382, Noveon

14

Dry FIo-PC, National Starch

15 Cleargum CO 01, Roquette

16 Tapioca Pure, National Starch O / W emulsions

17 Pemulen TR-2, Noveon

18 Dry FIo-PC, National Starch

19 Cleargum CO 01, Roquette

20 Tapioca Pure, National Starch

Claims

claims 1. Cosmetic preparation containing water-soluble UV filters and a nonionic, water-soluble, hydrophobically modified hydroxyethycellulose (HEC) characterized by linking with at least one short-chain hydrophobic group having 3 to 8 carbon atoms, more preferably having 3 to 5 carbon atoms and at least one long-chain hydrophobic group 9 to 24 carbon atoms. 2. Preparation according to claim 1, characterized in that the hydroxyethycellulose (HEC) with 3.0 to 4.0% by weight of n-butyl groups and 0.5 to 0.8 wt.% Palmi- tylgruppen is linked by ether bonds. 3. Preparation according to one of the preceding claims characterized marked net that the polysaccharide before modification has a weight average molecular weight of 0.3 to 3 MDa, particularly preferably 0.8 to 1.2 MDa. 4. Preparation according to one of the preceding claims, characterized in that the water-soluble UV filter from the group compounds 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, salts of 2-phenylbenzimidazole 5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself, 1,4-di (2-oxo-10-sulfo-3-bomylidene-methyl) -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 and the corresponding 10-sulfato compounds , in particular the corresponding sodium, potassium or triethanolammonium salt and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, in particular its sodium salt. 5. Preparation according to one of the preceding claims, characterized in that it is an emulsion with droplet sizes less than 5 microns. 6. Preparation according to one of the preceding claims, characterized in that its viscosity in the temperature range of 10 to 50 ⁰ C is substantially independent of temperature and in the specified temperature interval at most differs by 30%. 7. Preparation according to one of the preceding claims, characterized in that its viscosity is 100 to 20,000 mPas. 8. Preparation according to one of the preceding claims, characterized in that it contains an O / W emulsifier.