ES2834960T3 - Cosmetic product - Google Patents

Abstract

Cosmetic products, which comprise a container (B), - which has a tube-shaped body (K), - whose wall (Wk) has a transmission for visible light of 25 - approximately 100%, - on whose upper end it is placed a dispensing head (SK), - which is delimited underneath by a movable drag plunger (SCH), a cosmetic preparation inside the container (B), comprising: - an external, flowable gel-like phase and water-based - exhibiting a transmission for 700 nm wavelength light in the range of 30 to 100% and / or - exhibiting a selected viscosity in the range of 1,000 - 10,000 mPas at a temperature of 25 ° C and a shear rate of about 10, preferably 3000-9000 at a temperature of 25 ° C and a shear rate of about 10, particularly preferably 5000-8000 at a temperature of 25 ° C and a shear rate of approximately 10, and - q which optionally contains common adjuvants and / or additives, soluble in water or which can be dispersed in water, - an internal solid particulate phase, which - essentially comprises particles in the shape of a sphere, the average diameter of which is selected from the range of 0.1 to 10 mm, preferably from 2 to 7.5 mm, - wherein the ratio by volume of internal particulate phase to external aqueous gel is selected from the range of approximately 20%: 80% to 74%: 26%, particularly preferably from 30%: 70% to 65% relative to 35%, particularly preferably 40% relative to 60% to 60%: 40%, - and the arrangement of sphere-shaped particles, which form the internal fixed particulate phase , enriched in a packing of spheres as compact as possible, which is defined so that the filling of the space of a more compact packing of spheres in a cubic way of this type amounts to approximately 74%, whose cavities are filled lenan by means of the external aqueous gel phase, and where in the dispensing head (SK) it comprises - an external actuating element (BE) with a dispensing opening (SPO), which is closed by means of a check valve (RV), - a base unit (BO) resting on the tube-shaped body (K) with an opening (O) towards the tube-shaped body, as well as - a flexible, internal hollow body (H) and essentially shaped from cylindrical with bellows-like walls (Wh), the elements of the dispensing head being configured such that - the hollow body (H) has openings (Oo) at each of the two front ends (So), (Su) , (Ou), - the hollow body (H) rests with the lower front end (Su) on the base unit (BO), and its opening (O) and the lower opening (Ou) of the hollow body (H ) one on top of the other, so that when - the actuating element (BE) compresses the internal hollow body (H) towards its axis by external pressure longitudinal. - the substance inside the hollow body (H) is transported through the check valve (RV) and the dispensing head (SK) out of the container (B), and - when the external pressure is reduced, the Return force of the internal flexible hollow body (H) sucks substance from the tube-shaped body (K) into the internal flexible hollow body (H).

Description

DESCRIPTION

Cosmetic product

The present invention relates to stabilized active principles sensitive to oxidation or UV as well as to cosmetic and dermatological formulations with stabilized active principles sensitive to oxidation or UV.

The present invention relates to preparations with an external gel phase and an internal particulate phase, containing stabilized active ingredients sensitive to oxidation and / or UV. The present invention relates to cosmetic or dermatological preparations containing active principles for the care and protection of the skin, in particular of sensitive skin and dry skin, as well as very especially in priority of aged skin. or that ages due to intrinsic and / or extrinsic factors as well as to support the skin's own lipid metabolism as well as the use of such active principles and combinations of such active principles in the field of cosmetic and dermatological skin care.

By cosmetic skin care, it must be understood first of all that the natural function of the skin as a barrier against environmental influences (for example dirt, chemicals, microorganisms) and against the loss of substances inherent to the body (for example water , natural fats, electrolytes) is strengthened or restored.

If this function is destroyed, it may lead to enhanced reabsorption of toxic or allergenic substances or attack by microorganisms, resulting in toxic or allergic skin reactions.

The goal of skin care is also to compensate for the loss of oil and water from the skin caused by daily washing. This is precisely important when the capacity for natural regeneration is not sufficient. Furthermore, skincare products must protect against environmental influences, in particular against the sun and wind, and must delay skin aging.

Chronological skin aging is caused, for example, by endogenous, genetically determined factors. In the epidermis and dermis, the following structural damage and functional disorders occur, for example, in a manner conditioned by aging, which can also be found under the term "senile xerosis":

a) dryness, roughness and formation of small dry wrinkles,

b) itching and

c) reduced re-greasing by the sebaceous glands (for example after washing).

Exogenous factors, such as UV light and harmful chemical influences, can be cumulatively effective and for example accelerate or complement endogenous aging processes. In the epidermis and dermis, the following structural damage and functional disorders in the skin are produced in particular by exogenous factors, for example, which exceed the extent and quality of damage in the case of chronological aging:

d) visible vascular dilatations (teleangiectasias, couperose);

e) sagging and wrinkling;

f) hyperpigmentation, local hypopigmentation and lack of local pigmentation (for example age spots) and

g) increased propensity against mechanical stress (eg cracks).

The present invention relates in particular to products for the care of naturally aged skin, as well as for the treatment of damage resulting from photoaging, in particular of the phenomena described in a) to g).

Products for the care of aging skin are known per se. These contain, for example, retinoids (vitamin A and / or its derivatives) or vitamin A and / or its derivatives. Its action on structural damage is, however, peripherally limited. In addition, there are considerable difficulties in product development in stabilizing the active principles sufficiently against oxidative decomposition. The use of products containing vitamin A acid also frequently causes severe erythematous skin irritations. Retinoids can therefore be used only in low concentrations.

In particular, the present invention relates to cosmetic preparations with effective protection against harmful oxidation processes on the skin, however also for the protection of the cosmetic preparations themselves or for the protection of the constituent parts of cosmetic preparations against processes. of harmful oxidation.

The present invention further relates to antioxidants, preferably those used in cosmetic or dermatological skin care preparations. In particular, the invention also relates to preparations cosmetic and dermatological, which contain such antioxidants. In a preferred embodiment, the present invention relates to cosmetic and dermatological preparations for the prophylaxis and treatment of cosmetic or dermatological skin modifications, such as for example skin aging, in particular skin aging caused by oxidative processes.

Furthermore, the present invention relates to active principles and preparations, containing such active principles, for the cosmetic and dermatological treatment or prophylaxis of erythematous, inflammatory, allergic or autoimmune reactive phenomena, in particular dermatoses.

The present invention relates in another advantageous embodiment to combinations of active principles and preparations which are used for the prophylaxis and treatment of photosensitive skin, in particular photodermatosis. The damaging action of the ultraviolet part of solar radiation on the skin is generally known. While rays with a wavelength that is less than 290 nm (the so-called UVC region) are absorbed by the ozone layer in the earth's atmosphere, they originate the rays in the range between 290 nm and 320 nm, the so-called UVB region. , an erythema, a simple sunburn or even more or less severe burns.

As a maximum for erythema activity in sunlight the narrowest range around 308 nm is indicated. For protection against UVB radiation, numerous compounds are known, in the case of which are derivatives of 3-benzylidenecamphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone as well as 2- phenylbenzimidazole.

Also for the range between about 320 nm and about 400 nm, of the so-called UVA region, it is important to have filter substances available, since their rays can provoke reactions in case of photosensitive skin. It has been found that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which can prematurely age the skin, and to be seen as the origin of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be reinforced by UVA radiation.

For the protection against rays of the UVA region certain derivatives of dibenzoylmethane are therefore used, the photostability of which (Int. J. Cosm. Science 10, 53 (1988)), is not sufficiently provided.

However, UV radiation can also lead to photochemical reactions, whereby the photochemical reaction products enter the metabolism of the skin.

In particular, these photochemical reaction products of radical compounds, for example hydroxy radicals, are concerned. Also undefined radical photoproducts, which are produced on the skin itself, can show uncontrolled secondary reactions due to their high reactivity. However also singlet oxygen, a non-radical excited state of the oxygen molecule, can be produced during UV radiation, also short-lived epoxides and many others. Singlet oxygen for example is characterized by increased reactivity compared to the normally encountered triplet oxygen (radical basic state). However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

Furthermore, UV radiation belongs to ionizing radiation. Therefore, there is the risk that ionic species are also produced during UV exposure, which in turn are capable of being introduced oxidatively into biochemical processes.

To prevent these reactions, additional antioxidants and / or radical scavengers can be added to cosmetic or dermatological formulations.

It has already been proposed to use vitamin E, a substance with known antioxidant action in light protection formulations, however also in this case the action achieved has lagged behind what was expected. The aim of the invention was therefore also to create active principles and cosmetic, dermatological and pharmaceutical preparations as well as light protection formulations, which are used for the prophylaxis and treatment of photosensitive skin, in particular photodermatoses, preferably PLD.

Other names for polymorphic photodermatosis are PLD, PLE, acne de Mallorca and a number of other names, as indicated in the literature (for example A. Voelckel et al, Zentralblatt Haut- und Geschlechtskrankheiten (1989), 156, p. 2).

Erythematous skin phenomena also occur as concomitant phenomena in certain diseases or skin irregularities. For example, the typical skin rash in the appearance of acne is regularly reddened more or less intensely.

Antioxidants are mainly used as protective substances against the deterioration of the preparations that contain them. However, it is known that unwanted oxidation processes can also occur in human and animal skin. Such processes play an essential role in skin aging.

In the article "Skin Diseases Associated with Oxidative Injury" in "Oxidative Stress in Dermatology", p. 323 et seq. (Marcel Decker Inc., New York, Basel, Hong Kong, editors: Jürgen Fuchs, Frankfurt, and Lester Packer, Berkeley / California), oxidative skin damage and its more detailed causes are mentioned.

Also for the purpose of preventing such reactions, additional antioxidants and / or radical scavengers can be added to cosmetic or dermatological formulations.

Specifically, some antioxidants and radical scavengers are known. Thus, it has already been proposed in US patents 4,144,325 and 4,248,861 as well as in numerous other documents to use vitamin E, a substance with known antioxidant action in light protection formulations, however also in this case the action achieved It has lagged far behind what was expected.

The aim of the present invention was therefore to find ways that avoid the drawbacks of the state of the art. In particular, the action to eliminate the damage associated with endogenous, chronological and exogenous skin aging and prophylaxis must be long-lasting, persistent and without the risk of side effects.

The aim of the present invention was to remedy these drawbacks.

Furthermore, cosmetic preparations with coenzyme Q-10 are known from DE-A-33 09 850, which are suitable for the treatment of skin diseases, for the prophylaxis of dystrophic and dysmetabolic conditions of the skin and for their application in cases from chemical and physical respiratory damage or in case of delayed respiration associated with age and use.

Coenzyme Q-10 is characterized by the following structural formula

The suitability of Coenzyme Q-10 for cosmetic products has been described in Japanese Application Publication 58,180,410. This must activate the metabolism of skin cells and suppress oxidation. Coenzyme Q10 has an important role in preventing UV damage to the skin and preventing skin aging. In the case of 20 to 40 years of age, the roughness of the skin is improved, providing the skin with moisture.

According to the invention quinones can advantageously be selected from the group of bioquinones. Bioquinones are preylated quinones, which are produced in the animal and plant kingdoms and perform biochemical functions there. In particular ubiquinones and plastoquinones are preferred.

According to the invention, the hydroquinones can advantageously be selected from the group of the reduced forms of the corresponding bioquinones, that is to say especially preferably the ubiquinols and plastoquinols.

Ubiquinones represent the most widespread bioquinones and thus the best subjected to study. Ubiquinones are designated depending on the number of the isoprene units linked in the side chain as Q-1, Q-2, Q-3 etc. or according to the number of C atoms like U-5, U-10, U-15 etc. These occur preferably with certain chain lengths, for example in some microorganisms and yeasts with n = 6. Q-10 predominates in most mammals including humans.

Ubiquinones serve organisms as electron transmitters in the respiratory chain. They are found in the mitochondria where they allow cyclic oxidation and reduction of substrates of the citric acid cycle.

Plastoquinones have the general structural formula

These can be isolated from chloroplasts and play a role as redox substrates in photosynthesis in cyclic and non-cyclic electron transport, converting these reversibly into the corresponding hydroquinones (plastoquinol). Plastoquinones differ in the number n of isoprene residues and are designated accordingly, for example PQ-9 (n = 9). In addition, there are other plastoquinones with different substituents on the quinone ring.

A disadvantage of the state of the art consists in that ubiquinones and plastoquinones rapidly decompose in an oxidative medium, however also with UV radiation, and thus lose their activity.

An objective of the present invention was therefore to increase the stability of active principles sensitive to oxidation or sensitive to UV as well as to create stable preparations with active principles sensitive to oxidation or sensitive to UV, whose activity remains for a period of time. length.

Liquids can be differentiated with respect to their rheological properties by their flow and deformation behavior. Ideally elastic bodies undergo an elastic deformation by external forces, which with the withdrawal of the action of the external force produces a spontaneous, complete setback of the deformation. Ideally viscous bodies are irreversibly modified by external forces in their shape. Increasing strain is referred to as flowability. Most liquids are neither ideally viscous nor ideally elastic, but exhibit both viscous and elastic properties and are therefore referred to as viscoelastic substances.

In most viscoelastic solutions, dispersed particles or gas vesicles always settle or enlarge. These have a final structural relaxation time. This means that the networks in these systems react to a strain with a corresponding shear stress. However, this relaxes in a final time with respect to the zero value, so that the whole solution is again in a stable state of rest without tension. This further means that these solutions have a defined zero viscosity and consequently achieve a constant value of the viscosity at low shear rates.

In contrast to these systems, however, there are also those in which the dispersed particles or gas vesicles do not settle. It is obvious that these systems flow in the first place above a characteristic value. This value is called the flow limit. With more detailed observation of the rheological properties of these systems it becomes apparent that the full frequency range storage modulus is independent of the oscillation frequency and is always essentially larger than the loss modulus.

On the contrary, the value of the complex viscosity does not reach a constant value even at the lowest frequencies, but increases further.

Carbopol gels contain acrylic acid polymers, which can be linearly structured or cross-linked and carry a high number of carboxyl groups. In dissolved form, these structures bind water. The neutralization of the carboxyl groups, due to their electrostatic repulsion, leads to an extension and thus swelling of the polymer chains. In this state, carbopol gels achieve their typical rheological properties, such as, for example, increasing the viscosity of the cosmetic preparation and / or the formation of a flow limit.

The effect of the formation of a flow limit is therefore based on the electrostatic repulsion of the carboxyl groups. Additional electrolytes shield these charges. Through this, the networks collapse, breaking the flow limit, and the gas particles or vesicles can no longer be kept in suspension.

It was surprisingly and could not be foreseen by the expert, and in this is found the solution for the purposes according to the invention with foundation, that cosmetic products, comprising a container (B),

- having a tube-shaped body (K),

- whose wall (Wk) a transmission for visible light of 25 - approximately 100%,

- on the upper end of which a dispensing head (SK) is placed,

- which is delimited below a mobile drive piston (SCH), a cosmetic preparation inside the container (B), comprising:

- a water-based external flowable gel-like phase

- having a transmission for light with a wavelength of 700 nm in the range of 30% to 100% and / or

- having a viscosity selected from the range of 1000 - 10000 mPas at a temperature of 25 ° C and a shear rate of approx. 10, preferably 3000-9000 at a temperature of 25 ° C and a shear rate of approx. 10, in particular preferably 5000-8000 at a temperature of 25 ° C and a shear rate of approx. 10, and

- possibly containing common adjuvants and or additives, soluble in water or which can be dispersed in water,

- an internal solid particulate phase, which

- it comprises essentially sphere-shaped particles, the average diameter of which is selected from the range 0.1 to 10 mm, preferably 2 to 7.5 mm,

- wherein the volume ratio of internal particulate phase to external aqueous gel is selected from the range of approximately 20%: 80% to 74%: 26%, especially preferably 30%: 70% to 65% with with respect to 35%, in particular preferably 40% with respect to 60% to 60%: 40%, - and where the sphere-shaped particles reach a packing of spheres as compact as possible, (filling of the packing space of more compact spheres in a cubic way: approximately 74%), whose cavities are filled by the external aqueous gel phase.

- and where the dispensing head (SK) comprises

- an external actuating element (BE) with a dispensing opening (SPO), which is closed by means of a check valve (RV),

- a base unit (BO) resting on the tube-shaped body (K) with an opening (O) towards the tube-shaped body, as well as

- an internal flexible hollow body (H), essentially cylindrical with bellows-like walls (Wh),

the elements of the dispensing head being configured so that

- the hollow body (H) has at the two front ends (So), (Su) in each case openings (Oo), (Ou), - the hollow body (H) rests with the lower front end (Su) on the base unit (BO), and its opening (O) and the lower opening (Ou) of the hollow body (H) being one above the other,

so when

- the actuating element (BE) compresses the internal hollow body (H) towards its longitudinal axis by external pressure,

- the substance inside the hollow body (H) is transported through the check valve (RV) and the dispensing head (SK) out of the container (B), and

- by reducing the external pressure, the return force of the internal flexible hollow body (H) sucks substance from the tube-shaped body (K) into the internal flexible hollow body (H),

they remedy the drawbacks of the state of the art.

A particularly preferred embodiment of the present invention relates to cosmetic products, which comprise

a container,

- having a tube-shaped body,

- whose wall has a visible light transmission of 25 - approximately 100%,

- on the upper end of which a dispensing head is placed,

- which is delimited below a movable towing piston,

a cosmetic preparation inside the container, comprising:

- a water-based external flowable gel-like phase

- having a turbidity in the range from 0 to 500, preferably from 0.00001 to 100, particularly preferably from 0.01 to 10

- possibly containing common adjuvants and or additives, soluble in water or which can be dispersed in water,

- an internal solid particulate phase, which

- it comprises essentially sphere-shaped particles, the average diameter of which is selected from the range of 0.1 to 10 mm, preferably 2 to 7.5 mm, and wherein the particulate phase comprises

- a polymeric matrix, which is essentially insoluble in water,

- one or more substances selected from the group of ubiquinones and / or plastoquinones

- one or more light filter substances, selected or selected from the group of metal oxide pigments,

- optionally one or more light filter substances, which is or are selected from the group of customary cosmetic light protection filter substances

- wherein the volume ratio of internal particulate phase to external aqueous gel is selected from the range of approximately 20%: 80% to 74%: 26%, especially preferably 30%: 70% to 65% with relative to 35%, in particular preferably 40% relative to 60% to 60%: 40%.

The cosmetic products according to the invention represent highly satisfactory products in all respects, which are not limited to a limited selection of raw materials.

Correspondingly, they are very particularly suitable for serving as a basis for preparation forms with multiple purposes.

Advantageous preparations according to the invention can be obtained, the external flowable gel-like phase of the aqueous base having a content of one or more hydrocolloids.

“Hydrocolloid” is the technological abbreviated designation for the more correct designation itself “hydrophilic colloid.” Hydrocolloids are macromolecules that have a largely linear configuration and have intermolecular interaction forces, which allow secondary and major valence bonds between the individual molecules and thus the formation of a network-like structure. These are natural or synthetic polymers partially soluble in water, which in aqueous systems form gels or viscous solutions. These raise the viscosity of water, binding these or water molecules (hydration) or nevertheless absorbing and enveloping water in its interwoven macromolecules, limiting these at the same time the mobility of water. Such water-soluble polymers represent a large group of chemically very different natural and synthetic polymers, whose common characteristic is its solubility in water or aqueous media Precondition for this is that these polymers have a sufficient number of hydrophilic groups for solubility in water and are not too strongly crosslinked. Hydrophilic groups can be nonionic, anionic or cationic in nature, for example as follows:

The group of the cosmetically and dermatologically relevant hydrocolloids can be divided as follows into: • natural organic compounds, such as for example agar-agar, carrageenan, gum tragacanth, acacia, alginates, pectins, polysos, guar flour, carob bean flour, starch, dextrin, gelatin, casein, • natural organic substances , modified, such as for example carboxymethylcellulose and other cellulose ethers, hydroxyethyl- and -propylcellulose and the like,

• fully synthetic organic compounds, such as, for example, polyacryl and polymethacryl compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides,

• inorganic compounds, such as for example poly (silicic acids), clay minerals such as montmorillonites, zeolites, silicic acids.

Preferred hydrocolloids according to the invention are, for example, methyl celluloses, which are designated as the methyl ethers of cellulose. They are characterized by the following structural formula of

structural formula I

where R can represent a hydrogen or a methyl group.

In particular, advantageous for the purposes of the present invention are mixed cellulose ethers, also generally referred to as methylcelluloses, which in addition to a dominant content of methyl groups also contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. Especially preferred are (hydroxypropyl) methylcelluloses, for example obtainable under the trade designation Methocel E4M by Dow Chemical Comp.

Sodium carboxymethylcellulose, the sodium salt of the glycolic acid ester of cellulose, for which R in structural form I can represent hydrogen and / or CH ² -COONa, is also advantageous according to the invention. Sodium carboxymethyl cellulose available under the trade name Natrosol Plus 330 CS by Aqualon, also referred to as cellulose gum, is especially preferred.

Particularly preferred for the purposes of the present invention is furthermore xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide, which is generally formed by fermentation of corn sugar and isolated as a potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 * 106 to 24x106. Xanthan gum is formed from a chain with glucose linked by (3-1,4 (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthan gum is the name of the first microbial anionic heteropolysaccharide. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 106. Xanthan gum is formed from a chain with glucose linked by p-1,4 ( cellulose) with side chains. The subgroup structure consists of glucose, mannose, glucuronic acid, acetate, and pyruvate. The number of pyruvate units determines the viscosity of xanthan gum. Xanthan gum is produced in batch cultures of two days with a yield of 70-90%, with respect to the carbohydrate used. In this respect yields of 25-30 g / l are achieved. The processing is carried out after destruction of the culture by means of pr ecipitation with for example 2-Propanol. The xanthan gum is then dried and ground.

A particularly advantageous gelling agent in the sense of the present invention is also carrageenan, an agar-like structured gel-forming extract of North Atlantic red algae belonging to the florideas ( Chondrus crispus and Gigartina stellata).

The name carrageenan is often used for the dried seaweed product and carrageenan for its extract. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with a molecular weight range of 100,000-800,000 and a sulfate content of approx. 25%. Carrageenan, which is very easily soluble in hot water; on cooling, a thixotropic gel forms, even when the water content is 95-98%. The strength of the gel is caused by the double helix structure of the carrageenan. In the case of carrageenan, three main constituent parts are distinguished: the gel-forming fraction k is made up of D-galactose-4-sulfate and 3,6-anhydro-aD-galactose, which are alternately glycosidically linked in position 1, 3 and 1,4 (agar correspondingly contains 3,6-anhydro-αL-galactose). Non-gelling fraction A is composed of 1,3-linked glycosidic-linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan which is made up of 1,3-linked D-galactose-4-sulfate and 1,4-linked 3,6-anhydro-aD-galactose-2-sulfate is both water soluble and gel-forming. Other types of carrageenan are also designated by Greek letters: a, p, y, v, n, rn, %. Also the type of existing cations (K +, NH4 +, Na +, Mg2 +, Ca2 +) influences the solubility of carrageenans.

Polyacrylates are gel formers which will also be used to advantage in the sense of the present invention. Advantageous polyacrylates according to the invention are acrylate-alkyl acrylate copolymers, in particular those which are selected from the group of so-called carbomers or carbopoles (Carbopol® is actually a registered trademark of B. F. Goodrich Company). In particular, the advantageous acrylate-alkyl acrylate copolymer (s) according to the invention are characterized by the following structure:

In this R 'represent a long chain alkyl residue and x and y numbers symbolize the respective stoichiometric ratio of the respective comonomers.

Acrylate copolymers and / or acrylate-alkyl acrylate copolymers, which are available under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984 by B. F. Goodrich Company, are particularly preferred according to the invention.

In addition, copolymers of C ^10-30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are cross-linked with an allyl ether of sucrose or an allyl ether of pentaerythritol, are particularly advantageous.

Compounds bearing the INCI designation "C10-30 alkyl acrylate / acrylate crosspolymers" are particularly advantageous. In particular, those obtainable under the trade names Pemulen TR1 and Pemulen TR2 by B. F. Goodrich Company are advantageous.

Furthermore, the copolymers of ammonium acryloyldimethyltaurates / vinylpyrrolidone are particularly advantageous, in particular those having the molecular formula [C7Hi6N2SO4] n [C6HgNO] m, which corresponds to a statistical structure as follows

The preferred species in the sense of the present invention are registered in the Chemical Abstracts under the registration numbers 58374-69-9, 13162-05-5 and 88-12-0 and can be obtained under the trade name Aristoflex®AVC from the company Clariant GmbH.

The total amount of one or more hydrocolloids is selected in the cosmetic or dermatological preparations prepared according to the invention advantageously from the range 0.005% to 5% by weight, preferably between 0.1% and 2.0% by weight, in particular between 0.25% and 0.75% by weight, in each case relative to the total weight of the aqueous-based external flowable gel-like phase.

The polymeric matrix, which represents in a certain way the basic structure of the particulate phase, can be selected from the group of the usual, cosmetically or dermatologically innocuous polymeric substances, essentially insoluble in water, for example selected from the group of the following substances: algin, carrageenan, agar, gellan gum, chitosan.

A matrix of alginates, preferably sodium alginates, such as are also used in DE 4424998 A1, is particularly advantageous.

Preferred metal oxide pigments according to the invention are in particular oxides of titanium (TO ² ), of zinc (ZnO), of iron (for example Fe2O3), of zirconium (ZrO ² ), of silicon (SO ² ) , of manganese (for example MnO), of aluminum (Al2O3), of cerium (for example Ce2O3), mixed oxides of the corresponding metals as well as mixtures of such oxides as well as barium sulfate (BaSO4).

It is very particularly advantageous to use titanium oxides (TO ² ) as especially preferred metal oxide pigments according to the invention.

The pigments can be used advantageously for the purposes of the present invention also in the form of oily or aqueous pre-dispersions which are commercially available. Dispersion aids and / or solubilization mediators can advantageously be added to these pre-dispersions.

The pigments may be surface-treated ("coated") advantageously according to the invention, for example having to form or retain a hydrophilic, amphiphilic or hydrophobic character. This surface treatment may consist in that the pigments are provided according to known methods in yes of an inorganic and / or organic hydrophilic and / or hydrophobic thin layer The various surface coatings may also contain water for the purposes of the present invention.

Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (AhO3), aluminum hydroxide Al (OH) 3, or hydrated aluminum oxide (also: alumina, CAS No .: 1333- 84-2), sodium hexametaphosphate (NaPO ³ ) ⁶ , sodium metaphosphate (NaPO ³ ) n, silicon dioxide (SO ² ) (also: silica, CAS #: 7631-86-9), or oxide iron (Fe2O3). These inorganic surface coatings can be produced alone, in combination and / or in combination with organic coating materials. Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicones), methylpolysiloxane (methicones), simethicones (a mixture of dimethylpolysiloxane with an average chain length of ² O ⁰ to 350 dimethylsiloxane units and silica gel), or alginic acid. These organic surface coatings can be produced alone, in combination and / or in combination with inorganic coating materials.

Suitable zinc oxide particles according to the invention and zinc oxide particle pre-dispersions can be obtained under the following trade names by the companies mentioned:

Suitable titanium dioxide particles and pre-dispersions of titanium dioxide particles can be obtained under the following trade names by the companies mentioned:

A310 Tudor Aspen - Kingfisher Colors Ltd.

Kronos 1171 - Kronos Worldwide, Inc.

Advantageous UV filter substances according to the invention are for example dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is marketed by DSM under the trademark Parsol® 1789 and by Merck under the trade name Eusolex® 9020.

Other advantageous UV filter substances within the meaning of the present invention are water-soluble, sulphonated UV filters, such as, for example

• 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 bis salt -Phenylene-1,4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid sodium with the INCI designation bisimidazilate (CAS No: 180898-37-7), obtainable for example under the trade name Neo Heliopan AP by Haarmann &Reimer;

• 2-phenylbenzimidazole-5-sulfonic acid salts such as its sodium, potassium or triethanolammonium salt, as well as sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81 7), which can be obtained for example under the trade name Eusolex 232 by Merck or with Neo Heliopan Hydro by Haarmann &Reimer;

• 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) -benzene (also: 3,3 '- (1,4-phenylenedimethylene) -bis- (7,7-dimethyl-2-oxobicyclo acid - [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfate compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1 acid, 4-di (2-oxo-3-bornylidenemethyl-10-sulfonic) Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name terephthalidene dialcamphor sulfonic acid (n. CAS #: 90457-82-2) and can be obtained for example under the trade name Mexoryl SX by the company Chimex;

• sulfonic acid derivatives of 3-benzylidenecamphor, such as for example 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their salts.

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 radiation and also UV-B radiation.

Advantageous broadband filters or UV-B filter substances are for example triazine derivatives, such as for example

• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (IN-CI: methylene bisbenzotriazolemethylbutylphenol) , available under the trade name Tinosorb® S from CIBA-Chemikalien GmbH;

• dioctylbutylamidotriazone (INCI: diethylhexylbutamidotriazone), available under the trade name UVASORB HEB from Sigma 3V;

• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-tris-benzoate of tris (2-ethylhexyl), also: 2,4,6-tris- [anilino - (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

An advantageous broadband filter in the sense of the present invention is also 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl ) -phenol) (INCI: bisoctyltriazole), available under the trade name Tinosorb® M from CIBA-Chemikalien GmbH.

An advantageous broadband filter in the sense of the present invention is furthermore 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3- Tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl] -phenol (CAS No: 155633-54-8) under the INCI name drometrizol trisiloxane.

Additional UV filter substances can be oil soluble. Advantageous oil-soluble filter substances are for example:

■ 3-benzylidenecamphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidenecamphor;

■ 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) -benzoate, amyl 4- (dimethylamino) benzoate;

■ benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone

■ as well as polymer-bonded UV filters.

Another light-protective filter substance to be used advantageously according to the invention is ethylhexyl-2-cyano-3,3-diphenyl acrylate (octocrylene), which is available from BASF under the name Uvinul® N 539.

Especially preferred preparations for the purposes of the present invention contain, in addition to the filter substance (s) according to the invention, preferably further UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [for example 4- (tert-butyl) -4'-methoxydibenzoylmethane] and / or 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1 , 3,5-triazine, in each case individually or in combinations discretionary with each other.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should logically be non-limiting.

Advantageously, the particulate phase contains substances that absorb UV radiation in the UV-A and / or UV-B region, in a total amount of, for example, 0.1% by weight to 30% by weight, preferably 0.5%. 20% by weight, in particular 1.0% to 15.0% by weight, in each case relative to the total weight of the particulate phase.

It is possible and according to the invention possibly advantageous, although not necessarily, to provide a content of UV filter substances not only the particulate phase but also the external flowable gel-based phase, provided that the requirements of the turbidity. As a rule, water-soluble UV filter substances are used in the outer gel phase.

When water-soluble UV filter substances are to be used in the external gel phase, this contains the substances that absorb UV radiation in the UV-A and / or UV-B region, in a total amount of for example 0.1% by weight to 30% by weight, preferably from 0.5% to 20% by weight, in particular from 1.0% to 15.0% by weight, in each case relative to the total weight of the external gel phase.

To prepare the particles constituting the internal solid particulate phase, a process known from DE 4424998 A1 can be advantageously used. In this process, the composition, which is made up of the particulate phase, or optionally a composition, from which the particulate phase must develop, and which is preferably in a flowable form, is molded to obtain a directed liquid jet. to the setting causing environment and portion formation occurs because the liquid jet splits ahead of the setting causing environment into defined sections so that the sections are subsequently moved essentially in the direction of the liquid jet.

This process can currently be developed so that from the composition, from which the particulate phase is constituted, or optionally a composition, from which the particulate phase is to be developed, a jet of liquid is first formed, in the liquid particles move towards the environment causing hardening. After the formation of the jet of liquid, it is mechanically divided into defined sections, the sections thus formed subsequently moving in the direction predetermined by the jet of liquid. The division of the liquid jet is therefore carried out by periodically separating the liquid from the liquid jet, so that the defined sections are formed. The length of these sections can in this case be kept briefly so that during the remaining movement towards the environment causing hardening, in particular the surface of a hardening medium, a form of at least approximate sphere, so that sphere-shaped particles are produced.

In the case of fluid media having a certain viscosity, it is convenient when the fluid medium is pressed by the nozzle to form the liquid jet. This is usually done by applying an overpressure in the storage container or in the line to the liquid jet nozzle.

In many application cases there is a need to coat the particulate material preferably in the shape of a sphere. This coating can optionally be cured in the same environment, it being possible according to the present invention to already coat the sections formed of the fluid medium before curing, generating at least a transverse jet of liquid with a suitable liquid for the coating, through which the formed sections pass.

In this case, the transverse liquid jet can advantageously be designed as a flat jet, so that the possible passage area for the sections is increased.

A modification of the method can consist in that the nozzle arrangement is adjusted for the formation of at least one liquid jet and a movable partial device for the at least one liquid jet is arranged below the nozzle arrangement. .

The part device is in this case positioned directly at the outlet of the nozzle arrangement.

Preferably, the movable part device can be rotatably driven and is provided with elements that cut off the jet of liquid. By means of the rotary drive of the partial device, a particularly simple structure of the device according to the invention can be achieved.

The elements that cut the jet of liquid can in an advantageous embodiment be radially oriented jet-shaped elements, which are made of wires, plastic threads or the like. In this case, the elements can be designed without their own dimensional stability and can maintain their radial orientation only during rotation of the partial device.

In another embodiment, a rotary disk with passage openings arranged next to each other in a compact manner with respect to a radius for the liquid jet can be used. The webs between the through openings form the elements that cut through the jet of liquid.

Conveniently, the partial device is surrounded by a cylindrical housing, open at least in the area of the liquid jet, which has a collecting cavity for collecting liquid that runs off on the housing wall. In this way the liquid thrown radially outward by the elements that cut the liquid jet is collected and can be fed back to the corresponding storage container. The collecting cavity is preferably formed by means of a surrounding groove, which is provided with a sump.

For the formation of the aforementioned coating of the particles, the device can have a transverse nozzle arranged with respect to the liquid jet downstream of the partial device, directed at an angle to the liquid jet, which is connected to a storage container for a liquid. suitable for wrapping. The transverse nozzle can represent a flat jet nozzle in this regard.

In an exemplary embodiment, a liquid jet of an emulsion of cells in a sodium alginate solution may exit the nozzle, and the transverse jet may consist of a cell-free sodium alginate solution, whereas A CaCh solution is found in the collecting container 5 as a curing medium.

During the passage through the transverse jet preferably formed as a flat jet, the cell-containing liquid sections are enveloped for 3 min with the cell-free alginate solution and then immediately crosslinked, so that no migration of the cells from the cell occurs. the nucleus into the envelope layer, since the Ca ions diffuse essentially faster in the alginate droplets than cells can move.

Figure 2 represents a container that represents a typical dispenser with a drag plunger, in which the interior of the container is filled with a particulate phase, which is surrounded (not represented in this case) by an external aqueous gel phase.

In the preparation according to the invention, the ubiquinone (s) and / or plastoquinones are best protected against oxidation and the damaging influence of UV radiation.

When the preparations are applied to a surface, the preparations according to the invention can be spread by rubbing to give a homogeneous emulsion, which quickly penetrates the skin and is optically as well as haptically very attractive.

It is especially surprising that when a dispenser is used, the shear forces at the dispenser outlet are already sufficient to transform the unit originally in separate compartments (ie the outer gel phase and the inner particulate phase) into an optically homogeneous unit.

In particular it is advantageous when the inner hollow body (H) is configured so that the lower opening (Ou) around the lower front end (Su) comprises a device (V), which cuts off the flow of substance from inside the body at tube shape (K) into the hollow body in various partial flows. In the simplest case, a device of this type consists of a plate with at least two through openings (Du). These can be arranged radially in a particularly advantageous manner.

Figure 1 shows an advantageous container (B) according to the invention,

- having a tube-shaped body (K),

- on the upper end of which a dispensing head (SK) is placed,

- which is delimited below a movable drag piston (SCH), and

- a dispensing head (SK),

the container (B) in the body (K) and the dispensing head (SK) (in this case provided with an additional closing cap, not designated in more detail) being represented separately in FIG. 1a.

Figure 1a shows a dispensing head (SK),

- comprising an external actuating element (BE) with a dispensing opening (SPO), which is closed by means of a check valve (RV),

- a base unit (BO) resting on the tube-shaped body (K) with an opening (O) towards the tube-shaped body, as well as

- an internal, flexible hollow body (H), essentially cylindrically shaped with bellows-like walls (Wh).

Figure 1b shows a perspective view of an embodiment of the internal, flexible hollow body (H), essentially shaped cylindrically

- with bellows-like walls (Wh),

- the lower front end (Su) and its opening (Ou) being visible.

Figure 1c shows the elevation of an embodiment of the internal, flexible hollow body (H), shaped essentially cylindrically

- with bellows-like walls (Wh),

the elements of the dispensing head being configured so that

- the hollow body (H) at the two front ends (So), (Su) each have openings (Oo), (Ou),

and the hollow body (H) being configured such that the lower opening (Ou) around the lower front end (Su) comprises a device (V), which cuts off the flow of substance from inside the tube-shaped body (K ) into the hollow body in several partial flows.

Figure 1d shows a device (V), which is provided so that the flow of substance from inside the tube-shaped body (K) (in this case not shown) must be cut off into the hollow body (H) ( in this case not shown) by means of three through openings (Du) in three partial flows.

The cosmetic and dermatological preparations according to the invention may contain cosmetic adjuvants, as are commonly used in such preparations, for example preservatives, preservatives, bactericides, perfume, substances to prevent foaming, colorants, pigments, that have a coloring action, thickening agents, humectants and / or that maintain humidity, fillers that improve the sensation on the skin, fats, oils, waxes or other common constituent parts of a cosmetic or dermatological 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-separating agents (such as, for example, DMDM hydantoin, which can be obtained, for example, under the trade name Glydant ™ by Lonza), iodopropyl butylcarbamates (for example They can be obtained under the trade names Glycacil-L, Glycacil-S by Lonza and / or Dekaben LMB ex Jan Dekker), parabens (i.e. alkyl p-hydroxybenzoates, such as methyl-, ethyl-, propyl- and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid, and the like. The preservative system according to the invention usually comprises, further advantageously, also preservative assisting agents, such as, for example, octoxyglycerin, Glycine soy etc.

Especially advantageous preparations are also obtained when antioxidants are used as additive or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. As favorable antioxidants, however, which are nevertheless to be used optionally, all antioxidants suitable or customary for cosmetic and / or dermatological applications can be used.

Water-soluble antioxidants, such as, for example, vitamins, for example ascorbic acid and its derivatives as well as D-biotin, natural and / or synthetic isoflavones, alpha-glucosylrutin, panthenol, are particularly advantageous in the sense of the present invention. aloe vera, honokiol, magnolol.

The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001% to 30% by weight, particularly preferably 0.05% to 20% by weight, in particular 0.1% 10% by weight, relative to the total weight of the preparation.

It is particularly advantageous when the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, the preferred active ingredients being antioxidants, which can protect the skin against oxidative wear.

Other advantageous active ingredients are natural active ingredients and / or their derivatives, such as, for example, phytoene, carnitine, carnosine, creatine, N-acetyl-hydroxyproline, taurine and / or p-alanine.

The external aqueous gel phase of the preparations according to the invention may advantageously contain customary cosmetic adjuvants, such as, for example, alcohols, in particular those with a low C number, preferably ethanol and / or isopropanol, diols or polyols with a low C number. C as well as their ethers, preferably 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, polymers, as well as foam stabilizers in particular one, electrolytes or various thickening agents, which can be or can be selected advantageously from the group of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of carbopols mentioned, for example carbopols of the types 980, 981, 1382, 2984, 5984, in each case of individually or in combination. Moisturizing agents can also preferably be used.

Moisturizing agents are substances or mixtures of substances that confer on cosmetic or dermatological preparations the property of reducing, after application or distribution on the skin surface, the emission of moisture from the horny layer (also called water loss transdermal, transepidermal water joss (TEWL)) and / or positively influence the hydration of the horny layer.

Advantageous moisturizing agents in the sense of the present invention are, for example, glycerin, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, Gum-1 biosaccharide, Glycine Soja, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizing agents from the group of polysaccharides that are water-soluble and / or can swell in water and / or can be gelled with the aid of water. In particular, advantageous are, for example, hyaluronic acid, chitosan and / or a polysaccharide rich in fucose, which is deposited with Chemical Abstracts under the registration number 178463-23-5 and can be obtained, for example, under the name Fucogel®1000 from the company SOLABIA SA.

The cosmetic or dermatological preparations according to the invention may also advantageously, but not necessarily, contain fillers that further improve, for example, the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky skin sensation. Advantageous fillers in the sense 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 mainly have no filter action. UV or coloring action (such as for example boron nitride etc.) and / or Aerosile® (No. Ca s 7631-86-9).

The following examples will illustrate the present invention without limiting it. The numerical values in the examples mean percentages by weight, with respect to the total weight of the respective preparations.

Examples of internal particulate phases:

The formulation constituent parts of Examples A to E are processed analogously to the test example in d E 4424998, column 5, and shaped to give approximately spherical particles of diameter approximately 6 mm.

The formulation constituent parts of Examples 1-8 are mixed together at 25 ° C, until clear gels have formed.

Particles and gels were combined with each other in different volume ratios, as mentioned in the following combined examples. The first value reproduces the particulate phase, the second value the gel phase

In each case 40 ml of the preparations A1-E8 are introduced, each one separately, into containers, as described in the figures Fig. 1a to Fig. 1d.

Claims (8)

1. Cosmetic products, which include a container (B), - having a tube-shaped body (K), - whose wall (Wk) has a transmission for visible light of 25 - approximately 100%, - on the upper end of which a dispensing head (SK) is placed, - which is delimited underneath by a movable drag piston (SCH), a cosmetic preparation inside the container (B), comprising: - an external, water-based, flowable gel-like phase - having a transmission for light with a wavelength of 700 nm in the range of 30 to 100% and / or - having a viscosity selected from the range of 1000 - 10000 mPas at a temperature of 25 ° C and a shear rate of approximately 10, preferably 3000 - 9000 at a temperature of 25 ° C and a shear rate of approximately 10, in particular preferably 5000 -8000 at a temperature of 25 ° C and a shear rate of about 10, Y - possibly containing common adjuvants and or additives, soluble in water or which can be dispersed in water, - an internal solid particulate phase, which - it comprises essentially sphere-shaped particles, the average diameter of which is selected from the range 0.1 to 10 mm, preferably 2 to 7.5 mm, - wherein the volume ratio of internal particulate phase to external aqueous gel is selected from the range of approximately 20%: 80% to 74%: 26%, especially preferably 30%: 70% to 65% with with respect to 35%, in particular preferably 40% with respect to 60% to 60%: 40%, - and the arrangement of particles in the form of a sphere, which form the internal fixed particulate phase, enriched in a packing of spheres as much as possible. possible compact, which is defined so that the space filling of such a more cubically compact packing of spheres amounts to about 74%, the cavities of which are filled by the external aqueous gel phase, and wherein the dispensing head (SK) comprises - an external actuating element (BE) with a dispensing opening (SPO), which is closed by means of a check valve (RV), - a base unit (BO) resting on the tube-shaped body (K) with an opening (O) towards the tube-shaped body, as well as - a flexible hollow body, internal (H) and essentially cylindrical with bellows-like walls (Wh), the elements of the dispensing head being configured so that - the hollow body (H) has at each of the two front ends (So), (Su) openings (Oo), (Ou), - the hollow body (H) rests with the lower front end (Su) on the base unit (BO), and its opening (O) and the lower opening (Ou) of the hollow body (H) being one above the other, so when - the actuating element (BE) compresses by external pressure the internal hollow body (H) towards its longitudinal axis. - the substance inside the hollow body (H) is transported through the check valve (RV) and the dispensing head (SK) out of the container (B), and - as the external pressure is reduced, the return force of the internal flexible hollow body (H) sucks substance from the tube-shaped body (K) towards the internal flexible hollow body (H). Products according to claim 1, in which the inner hollow body (H) is configured so that its lower opening (Ou) around the lower front end (Su) comprises a device (V), which cuts off the flow of substance from the inside of the tube-shaped body (K) towards the inside of the hollow body in several partial flows. Products according to one of the preceding claims, characterized in that the external gel phase is characterized by a content of one or more hydrocolloids, which is or are selected from the group of celluloses / methylcelluloses, polyacrylates and particularly preferably of the Carrageenan group, of the xanthan gum, "C10-30 alkyl acrylate / acrylate crosspolymer" and ammonium acryloyldimethyltaurate / vinylpyrrolidone copolymers. Products according to one of the preceding claims, characterized in that the total amount of one or more hydrocolloids is advantageously selected to be less than 1.5% by weight, preferably between 0.1 and 1.0% by weight, with respect to the total weight of the preparations. Products according to one of the preceding claims, characterized in that the polymeric matrix of the internal particulate phase is selected from the group of algin, carrageenan, agar, gellan gum, chitosan as well as alginates, in particular sodium alginate. 6. Products according to one of the preceding claims, characterized in that the metal oxide pigment (s) is or are selected from the group of oxides of titanium (TO ² ), zinc (ZnO), iron (for example Fe2O3), zirconium (ZrO ² ), silicon (SO ² ), manganese (for example MnO), aluminum (AhO3), cerium (for example Ce2O3), mixed oxides of the corresponding metals as well as mixtures of such oxides as well as barium sulfate ( BaSO4). Products according to one of the preceding claims, characterized in that ubiquinone 10 (coenzyme Q10) is selected as ubiquinone. Products according to one of the preceding claims, characterized in that the light protection filter substance or substances in the particulate phase is or are selected from the group of octyl methoxycinnamate, octocrylene, Tinosorb M, Tinosorb S, Mexoryl XL, benzophenone-3, benzophenone-4.