AU2015258134B2

AU2015258134B2 - Preparations having an outer gel phase and an inner particulate phase comprising stabilized oxidation-and/or UV-sensitive active ingredients

Info

Publication number: AU2015258134B2
Application number: AU2015258134A
Authority: AU
Inventors: Dana BOELKE; Sven Fey; Janne MOEBIUS
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2014-05-06
Filing date: 2015-02-05
Publication date: 2020-01-16
Anticipated expiration: 2035-02-05
Also published as: AU2015258134A1; WO2015169455A1; EP3139897A1; BR112016025462A2

Abstract

The invention relates to cosmetic preparations, comprising an outer flowable gel-type phase on an aqueous basis, which is provided with a transmission for light of the wavelength 700 nm from the range of 30 to 100%, and/or which has a viscosity selected from the interval of 1000 to 10000 mPas at a temperature of 25°C and a shear rate of about 10, preferably of 3000 to 9000 at a temperature of 25°C and a shear rate of about 10, in particular preferably of 5000 to 8000 at a temperature of 25°C and a shear rate of about 10, and which, optionally, contains conventional water-soluble or dispersible auxiliary agents and or additives; an inner solid particulate phase, which comprises substantially spherical particles, whose average diameter is selected from the range of 0.1 to 10 mm, preferably 2 to 7.5 mm. The particulate phase comprises a polymer matrix that is substantially insoluble in water, one or more substances selected from the group of ubiquinones and/or plastoquinones, one or more light-filter substances, which is selected, or are selected, from the group of metal oxide pigments, optionally one or more light-filter substances, which is, or which are, selected from the group of the conventional cosmetic light-protective filter substances.

Description

Preparations having an outer gel phase and an inner particulate phase containing stabilized oxidation and/or uv-sensitive active agents

The present invention relates to preparations having an outer gel phase and an inner particulate phase which contains stabilized, oxidation and/or UV-sensitive active agents.

The present invention relates to cosmetic and/or dermatological preparations containing active agents for the care and protection of the skin, especially sensitive and dry skin, as well as most especially, and most of all, skin which is aged or aging as the result of intrinsic and/or extrinsic factors, as well as for the support of the skin's natural lipid metabolism, and the use of such active agents and combinations of such active agents in the field of cosmetic and dermatological skincare.

Cosmetic skin care should be understood primarily to mean that the natural function of the skin as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the loss of endogenous substances (e.g. water, natural fats, electrolytes) is strengthened or restored.

If this function becomes impaired, the result can be increased resorption of toxic or allergenic 0 substances, or attack by microorganisms, leading to toxic or allergic skin reactions.

Another aim of skincare is to compensate for the fat and water loss from the skin caused by daily washing. This is particularly important if the natural ability to regenerate is inadequate. Furthermore, skincare products should protect against environmental influences, in particular 25 against sun and wind, and delay skin aging. Chronological skin aging is caused, for example, by endogenous, genetically determined factors. By way of example, in the epidermis and dermis, the following structural damage and functional disorders, which can also fall under the term senile xerosis, occur with increasing age:

a) dryness, roughness and formation of dryness wrinkles,

b) itching and

c) reduced refatting by sebaceous glands (e.g. after washing).

Exogenous factors, such as UV light and chemical noxae, can have a cumulative effect and, 35 for example, accelerate and/or supplement the endogenous aging processes. By way of example, in the epidermis and dermis, the following structural damage and functional

2015258134 12 Dec 2019 disorders can occur in the skin, to a greater degree and with greater damage than in the case of chronological aging, and in particular as a result of exogenous factors:

d) visible vascular dilations (telangiectasias, cuperosis);

e) flaccidity and formation of wrinkles;

f) local hyperpigmentation, hypopigmentation, and abnormal pigmentation (e.g. age spots) and

g) increased susceptibility to mechanical stress (e.g. cracking).

The present invention particularly relates to products for the care of naturally aged skin, as well as for the treatment of damage caused by photoaging, in particular the phenomena listed under a) to g).

Products for the care of aged skin are known per se. They contain, for example, retinoids (vitamin A acid and/or derivatives thereof) and/or vitamin A and/or its derivatives. Their efficacy for combatting structural damage is, however, limited. Moreover, there are considerable difficulties in product development regarding stabilizing the active agents sufficiently against oxidative decomposition. The use of products containing vitamin A acid also often leads to severe erythematous skin irritations. Retinoids can therefore be employed 0 only in low concentrations.

In particular, the present invention relates to cosmetic preparations having effective protection against harmful oxidation processes in the skin, but also for the protection of cosmetic preparations themselves and/or for the protection of the constituents of cosmetic 25 preparations against harmful oxidation processes. The present invention further relates to antioxidants, preferably those which are used in skin-care cosmetics or dermatological preparations. In particular, the invention also relates to cosmetic and dermatological preparations containing such antioxidants. In a preferred embodiment, the present invention relates to cosmetic and dermatological preparations for the prophylaxis and treatment of 30 cosmetic or dermatological changes in the skin such as skin aging - in particular skin aging caused by oxidative processes.

In addition, the present invention relates to active agents and preparations, containing such active agents, for the cosmetic and dermatological treatment or prophylaxis of erythematous, 35 inflammatory, allergic or autoimmune-reactive symptoms, in particular dermatoses.

2015258134 12 Dec 2019

The present invention relates in a further advantageous embodiment to active agent combinations and preparations which serve the purpose of prophylaxis and treatment of photosensitive skin, in particular of photodermatoses.

The damaging effect of the ultraviolet part of solar radiation on the skin is generally known. While rays with a wavelength of less than 290 nm (the UVC region) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB range, cause erythema, a simple sunburn or even more-or-less severe burns.

The relatively narrow range around 308 nm is considered the maximum for the erythema activity of sunlight.

Numerous compounds are known for protection against UVB radiation, specifically derivatives of 3-benzylidenecamphor, of 4-aminobenzoic acid, of cinnamic acid, of salicylic 5 acid, of benzophenone and also of 2-phenylbenzimidazole.

For the range between about 320 nm and about 400 nm, the so-called UVA region, it is important to have filter substances available, since rays thereof can cause reactions in cases of photosensitive skin. It has been shown that UVA radiation leads to damage of the elastic 0 and collagenous fibers of connective tissue, which causes the skin to age prematurely, and that it can be seen as a cause of numerous phototoxic and photoallergic reactions. The damaging effect of UVB radiation can be intensified by UVA radiation.

Certain derivatives of dibenzoylmethane are therefore used for protection against rays in the 25 UVA range, wherein the photostability thereof (Int. J. Cosm. Science 10, 53 (1988)) is not sufficient.

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products influence the skin's metabolism.

Such photochemical reaction products are predominantly free-radical compounds - for example hydroxyl radicals. Undefined free-radical photoproducts which are formed in the skin itself can also result in uncontrolled secondary reactions due to their high reactivity. However, singlet oxygen, a non-radical excited state of the oxygen molecule, can also arise 35 as a result of UV irradiation, as can short-lived epoxides and many other species. Singlet oxygen, for example, is distinguished from the triplet oxygen normally present (the free3

2015258134 12 Dec 2019 radical ground state) by increased reactivity. However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

Furthermore, UV radiation is ionizing radiation. There is therefore the risk of ionic species also arising upon UV exposure, and then being able in turn to oxidatively interrupt biochemical processes.

To prevent these reactions, additional antioxidants and/or free-radical scavengers can be incorporated into the cosmetic and/or dermatological preparations.

The use of vitamin E, a substance with known antioxidative action in sunscreen preparations, has already been suggested, although here as well the effect achieved falls far short of expectations.

The object of the invention was therefore also that of creating cosmetic, dermatological and pharmaceutical active agents and preparations, as well as photoprotective preparations, which serve the purpose of prophylaxis and treatment of photosensitive skin, in particular photodermatoses, preferably PLD.

Other names for polymorphous light dermatosis are PLD, PLE, Mallorca acne and a variety of other names, as described in the literature (for example: A. Voelckel et al, Zentralblatt Haut und Geschlechtskrankheiten (1989) 156, p.2).

Erythematous skin symptoms also occur as accompanying symptoms in certain skin diseases or irregularities. By way of example, the typical skin rash is often red to a greater or lesser degree in the symptoms of acne.

Antioxidants are mainly used as substances which protect against the deterioration of preparations containing them. Nevertheless, it is known that undesired oxidation processes can also occur in human and animal skin. Such processes play an essential role in skin aging.

The article Skin Diseases Associated with Oxidative Injury in Oxidative Stress in Dermatology, p.323 ff. (Marcel Decker Inc., New York, Basel, Hong Kong, Publisher: Jurgen 35 Fuchs, Frankfurt, and Lester Packer, Berkeley, California) discusses oxidative skin damage and its proximate causes.

2015258134 12 Dec 2019

Antioxidants and/or free-radical scavengers can also be incorporated into cosmetic or dermatological preparations for the purpose of preventing such reactions.

A number of antioxidants and free radical scavengers are known. As such, the use of vitamin E, a substance with known antioxidative action in sunscreen preparations, has already been suggested in US patents 4,144,325 and 4,248,861, along with numerous other documents, although here as well the effect achieved falls far short of expectations.

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

The object of the present invention was therefore that of finding ways to avoid the disadvantages of the prior art. In particular, the effect of remedying the damage associated with endogenous, chronological and exogenous skin aging, and the prophylaxis, should be long-term, sustainable and without the risk of side effects.

Overcoming these shortcomings was the object of the present invention.

It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

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

Coenzyme Q-10 is characterized by the following structural formula

2015258134 12 Dec 2019

In the Japanese unexamined patent publication 58,180,410, the suitability of coenzyme Q-10 is described for cosmetics. It is believed to activate skin cell metabolism and suppress oxidation. Coenzyme Q10 accordingly has an important role in the prevention of skin damage caused by UV rays and the prevention of skin aging. In people of 20 to 40 years of age, skin roughness is improved by supplying the skin with moisture.

According to the invention, the quinones can be advantageously selected from among the group of biological quinones. Bioquinones are prenylated quinones which occur in the animal 0 and plant kingdom, where they perform biochemical functions. Particularly preferred are ubiquinones and plastoquinones.

According to the invention, the hydroquinones can advantageously be selected from among the group of the reduced forms of the corresponding bioquinones - i.e. particularly preferably 5 the ubiquinols and plastoquinols.

Ubiquinones represent the most widespread, and therefore best-studied, bioquinones.

Ubiquinones are characterized, according to the number of isoprene units linked in the side chain, as Q-1, Q-2, Q-3, etc., or, according to the number of carbon atoms, as U-5, U-10, U0 15 etc. They occur preferentially with particular chain lengths for example, in some microorganisms and yeasts, where n = 6. In most mammals, including humans, Q-10 is the most common.

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

Plastoquinones have the general structural formula:

They can be isolated from chloroplasts and play a role as redox substrates in photosynthesis 6

2015258134 12 Dec 2019 for cyclic and non-cyclic electron transport, wherein they transition reversibly into the corresponding hydroquinones (plastoquinol). Plastoquinones differ in the number n of isoprene moieties and are characterized accordingly for example as PQ-9 (n = 9). Furthermore, there exist other plastoquinones with different substituents on the quinone ring.

A drawback of the prior art is that ubiquinones and plastoquinones disintegrate in an oxidative environment, as well as under UV radiation, and thus lose their effectiveness.

An object of the present invention was therefore to increase the stability of oxidation and/or

UV-sensitive active agents, and to create stable preparations containing oxidation-sensitive and/or UV-sensitive active agents, wherein the effectiveness thereof is maintained over a long period.

Fluids can be distinguished with regard to their rheological properties by their flow and deformation behavior. Ideal, elastic bodies undergo elastic deformation caused by external forces, and the deformation spontaneously and completely reverses upon removal of the external force. The shape of ideal, viscous bodies is changed irreversibly by external forces. The increasing deformation is termed flow. Most fluids are neither ideally elastic nor ideally viscous; rather, they exhibit both viscous and elastic properties and are therefore referred to 0 as viscoelastic substances.

In the majority of viscoelastic solutions, dispersed particles or gas bubbles will always sink or rise, respectively. They have a finite structural relaxation time. This means that the networks in these systems respond to a deformation with a corresponding shear stress. However, this 25 relaxes over a finite time to zero, such that the entire solution is again in a stable resting state without stress. This also means that these solutions have a defined zero shear viscosity, and thus achieve a constant viscosity value at low shear rates.

In contrast to these systems, there are also those in which dispersed particles or gas bubbles 30 do not sediment out. It is noticeable that these systems only flow above a characteristic value. This value is called the liquid limit. Closer inspection of the rheological properties of these systems reveals that the storage modulus in the entire frequency range is independent of the oscillation frequency, and always significantly greater than the loss modulus.

In contrast, the magnitude of the complex viscosity does not reach a constant value even at the smallest frequencies, but rather continues to increase.

2015258134 12 Dec 2019

Carbopol gels contain acrylic acid polymers which can be linear or cross-linked and which bear a high number of carboxyl groups. In dissolved form, these structures bind water. The neutralization of the carboxyl groups leads to an expansion, and hence swelling, of the polymer chains, due to the electrostatic repulsion. In this state, the Carbopol gels reach their typical rheological properties, such as the increase in the viscosity of the cosmetic preparation and/or formation of a liquid limit.

The effect of the formation of a liquid limit is thus based on the electrostatic repulsion of the 0 carboxyl groups. Additional electrolytes shield these charges. As a result, the networks collapse, the liquid limit collapses and particles or gas bubbles can no longer be kept in suspension.

According to a first aspect the invention provides a cosmetic preparation, comprising

- an outer, flowable, gelatinous, water-based phase

- which allows the transmission of light of the wavelength 700 nm in the range of at least 30 %, and/or

- which has a viscosity selected from the range of 1,000 to 10,000 mPas at a temperature of 25 °C and a shear rate of about 10s'¹, and

- an inner, solid, particulate phase which

- comprises spherical particles with an average diameter selected from the range of 0.1 to 10 mm and wherein the particulate phase comprises

- a polymer matrix which is insoluble in water,

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

- one or more light filter substances which is/are selected from among the group of metal oxide pigments.

It was surprising and unforeseeable for a person skilled in the art that - and the solution of the problems according to the invention is based on the fact that - cosmetic preparations comprising:

- an outer, flowable, gelatinous, water-based phase

- which allows the transmission of light of the wavelength 700 nm in the range of

30 to 100%, and/or

2015258134 12 Dec 2019

- which has a viscosity selected from the range of 1,000 to 10,000 mPas at a temperature of 25 °C and a shear rate of about 10, preferably from 3000 to 9000 at a temperature of 25 °C and a shear rate of about 10, and particularly preferably of 5000 to 8000 at a temperature of 25 °C and a shear rate of about

10, and

- which can optionally contain conventional, water-soluble or dispersible auxiliaries and/or additives,

- an inner, solid, particulate phase which

- comprises substantially spherical particles with an average diameter 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 polymer matrix which is substantially insoluble in water,

- one or more light filter substances which is/are selected from among the group of metal oxide pigments,

- optionally one or more light filter substances which is/are selected from among the group of conventional cosmetic photoprotective filter substances, remedy the deficiencies of the prior art.

The preparations of the invention are entirely satisfactory preparations in every respect, and are not restricted to a limited choice of raw materials. Accordingly, they are particularly 25 suitable to serve as a basis for formulations having diverse applications. The preparations according to the invention exhibit very good sensory and cosmetic properties, such as extensibility on the skin or the ability to be absorbed into the skin, and are further distinguished by very good photoprotection effectiveness coupled with excellent skincare data.

According to the invention, advantageous preparations can be obtained by the outer, flowable, gelatinous, water-based phase containing of one or more hydrocolloids.

Hydrocolloid is the technical abbreviation for the more correct term, hydrophilic colloid. 35 Hydrocolloids are macromolecules which have a largely linear structure and intermolecular forces of interaction which permit secondary and primary valence bonds between the

2015258134 12 Dec 2019 individual molecules, and thus the formation of a reticular structure. They are partially watersoluble natural or synthetic polymers which form gels or viscous solutions in aqueous systems. They increase the viscosity of the water by either binding water molecules (hydration) or else by absorbing and enveloping water into their interwoven macromolecules, 5 while at the same time restricting the mobility of the water. Such water-soluble polymers represent a large group of chemically very different natural and synthetic polymers whose common feature is their solubility in water or aqueous media. The prerequisite for this is that these polymers have a sufficient number of hydrophilic groups for solubility in water, and are not too greatly crosslinked. The hydrophilic groups can be nonionic, anionic or cationic in 0 nature, for example as follows:

+

—COO	M⁺	—nr₂ I
—so₃-	M ⁺	(CH₂)_n
—po\|	m²⁺	so₃'
+
—nh₃	X'	+
+		—nr₂
—nr₂h	X'	I
+		(CH₂)_n
—nr₃+	X’	I COO'
—PR₃	X’

—NH₂ —NH—R —OH —SH —ΟΙ —N— —COOH

O

II — NH—c—NH₂

NH

II — NH—c—NH₂

O’ +/ —CH=N

X

O

The group of cosmetically and dermatologically relevant hydrocolloids can be divided as follows into:

. organic, natural compounds, such as, for example, agar-agar, carrageenan, tragacanth, gum arable, alginates, pectins, polyoses, guar gum, carob bean gum, starches, dextrins, gelatins, casein;

. organic, modified natural substances, such as, for example, carboxymethylcellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose and the like;

. organic, completely synthetic compounds such as, for example, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides;

. inorganic compounds, such as, for example, polysilicic acids, clay minerals such as montmorillonite, zeolites, silicas.

2015258134 12 Dec 2019

According to the invention, preferred hydrocolloids are, for example, methylcelluloses, which is the name for the methyl ethers of cellulose. They are characterized by the following structural formula:

Structural formula II wherein R can be a hydrogen or a methyl group.

Particularly advantageous for the purposes of the present invention are the mixed cellulose 0 ethers, likewise generally referred to as methylcelluloses, which in addition to a predominant content of methyl groups also contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. Particular preference is given to (hydroxypropyl-) methylcelluloses - by way of example those available under the trade name Methocel E4M from Dow Chemical Comp.

According to the invention, sodium carboxymethylcellulose is also advantageous, along with the sodium salt of the glycolic ether of the cellulose, for which R in structural formula I is hydrogen and/or CH2COONa. Particular preference is given to sodium carboxymethylcellulose, available under the trade name Natrosol Plus 330 CS from Aquaion, and also known as cellulose gum.

Particularly preferred according to the present invention is xanthan (CAS-No.1 1 138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide which is generally formed by fermentation from corn sugar and is isolated as the potassium salt. It is produced by Xanthomonas campestris and several other species under aerobic conditions, with a molecular weight of 2x10^{5 6} to 24x10⁶. Xanthan is formed from a chain with β-1,4-bonded glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthan is the name for the first microbial, anionic heteropolysaccharide. It is produced by Xanthomonas campestris and some other species under aerobic conditions, with a molecular weight of 2x10⁶ to 15x10⁶. Xanthan is formed from a chain with β-1,4-bonded glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The

2015258134 12 Dec 2019 number of pyruvate units determines the viscosity of the xanthan. Xanthan is produced in two-day batch cultures with a yield of 70 - 90% based on carbohydrate used. Yields of 25 30 g/L are achieved. The batch is worked up by killing the culture by precipitation with, for example, 2-propanol. Xanthan is subsequently dried and ground.

A particularly advantageous gel former for the purposes of the present invention is, furthermore, carrageenan, a gel-forming extract similar in structure to agar, from red algaes present in the North Atlantic and classified among the florideaes (Chondrus crispus and Gigartina stellata).

Often, the name carrageen is used for the dried algae product and carrageenan for the extract thereof. 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 to 800,000 and a sulfate content of about 25%. Carrageenan, which is very readily soluble in warm water, forms a thixotropic gel upon cooling, even if the water content is 95-98%. The strength of the gel is the result of the double helix structure of the carrageenan. There are three main components of carrageenan: the gel-forming κ fraction consists of D-galactose-4-sulfate and 3,6-anhydro-a-D-galactose, which has alternating glycoside bonds in the 1,3 and Impositions (agar, in contrast, contains 3,6-anhydro-a-L-galactose). The non-gelling λ fraction is 0 composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6disulfate moieties, and is highly soluble in cold water. The ι-carrageenan from D-galactose-4sulfate at the 1,3 position and 3,6-anhydro-a-D-galactose-2-sulfate at the 1,4 position is both water soluble and gel-forming. Further carrageen types are likewise referred to with Greek letters: α, β, γ, μ, v, ξ, π, ω, χ. The type of cations present (K+, NH4+, Na+, Mg2+, Ca2+) 25 also influences the solubility of the carrageenans.

Polyacrylates are also advantageous gelators to use for the purposes of the present invention. Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those selected from the group of carbomers or Carbopols 30 (Carbopol® is actually a registered trademark of the BF Goodrich Company). In particular, the acrylate-alkyl acrylate copolymer(s) which are advantageous according to the invention is/are characterized by the following structure:

2015258134 12 Dec 2019

CH₃ —CH₂—CH—

C=O

OH ch₂—c c=o

Ck R' ^J y

In the above, R’ is a long-chain alkyl moiety and x and y are numbers which symbolize the respective stoichiometric proportion of each of the comonomers.

According to the invention, particular preference is given to acrylate copolymers and/or acrylate alkylacrylate copolymers which are available under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984 from the BF Goodrich Company.

Furthermore, particularly advantageous are copolymers of C10-30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or esters thereof which are crosslinked with an allyl ether of sucrose or an allyl ether of pentaerythritol.

Particularly advantageous are compounds carrying the INCI name acrylates/C10-30 alkyl acrylate crosspolymer. Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from the BF Goodrich Company.

Further particularly advantageous are ammonium acryloyldimethyltaurate/vinylpyrrolidone copolymers, in particular those having the empirical formula [C7H16N2SO4L [CeHgNOJm, corresponding to a statistical structure as follows:

2015258134 12 Dec 2019

Preferred species for the purposes of the present invention are archived in the Chemical Abstracts under the registry numbers 58374-69-9, 13162-05-5 and 88-12-0, and available under the trade name Aristoflex® AVC from Clariant GmbH.

The advantageous total amount of one or more hydrocolloids in the finished cosmetic or dermatological preparations according to the invention is in the range of 0.005 to 5 wt.%, preferably between 0.1 and 2.0 wt.%, and in particular between 0.25 and 0.75 wt.%, in each case based on the total weight of the outer, flowable, gelatinous, water-based phase.

The polymer matrix, which represents as it were the backbone of the particulate phase, can be selected from among the group of conventional cosmetically or dermatologically tolerated, substantially water-insoluble polymeric substances by way of example selected from among the group of the following substances: algin, carrageenan, agar, gellan gum, chitosan.

Particular advantageous is a matrix of alginates, preferably sodium alginates, as are also used in DE 44 24 998 A1.

Metal oxide pigments which are preferred according to the invention are, in particular, oxides of titanium (T1O2), zinc (ZnO), iron (e.g. Fe2O3), zirconium (ZrC>2), silicon (S1O2), manganese (e.g. MnO), aluminum (AI2O3) cerium (e.g. Ce2O3), mixed oxides of the corresponding metals and mixtures of such oxides, and the sulfate of barium (BaSCU).

It is particularly advantageous to use oxides of titanium (T1O2) as metal oxide pigments which are particularly preferred according to the invention.

The pigments can also be advantageously used for the purposes of the present invention in the form of commercially available oily or aqueous predispersions. Dispersants and/or solubilizers can advantageously be added to these predispersions.

According to the invention, the pigments can advantageously be surface-treated (coated), wherein a hydrophilic, amphiphilic or hydrophobic character should be formed or retained, by way of example. This surface treatment can consist of equipping the pigments according to methods known per se with a thin hydrophilic and/or hydrophobic inorganic and/or organic layer. The various surface coatings can for the purposes of the present invention also contain 35 water.

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Inorganic surface coatings for the purposes of the present invention can consist of aluminum oxide (AI2O3), aluminum hydroxide AI(OH)3 or aluminum oxide (also: alumina, CAS no. 133384-2), sodium hexametaphosphat (NaPCfije, sodium metaphosphate (NaPCfijn, silicon dioxide (S1O2) (also: silica CAS no. 7631 -86-9) or iron oxide (Fe2O3). These inorganic surface coatings can occur alone, in combination, and/or in combination with organic coating materials.

Organic surface coatings for the purposes of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination, and/or in combination with inorganic coating materials.

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

2015258134 12 Dec 2019

Trade name	Coating	Manufacture r
Z-Cote HP1	2% Dimethicone	BASF
Z-Cote	/	BASF
ZnO NDM	5% Dimethicone	H&R
ZnO Neutral	/	H & R
MZ 505 M	5% Methicone	Tayca Corp.

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

Trade name	Coating	Manufacturer
MT-100TV	aluminum hydroxide/stearic acid	Tayca Corporation
MT-100Z	aluminum hydroxide/stearic acid	Tayca Corporation
Eusolex T-2000	Alumina/Simethicone	Merck KgaA
Titanium dioxide T805 (Uvinul TiO₂)	Octyltrimethylsilane	Degussa
Tioveil AQ 10PG	Alumina/Silica	Solaveil/Uniquema

A310 Tudor Aspen Kronos 1171 Kingfisher Colours Ltd.

Kronos Worldwide, Inc.

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

Other advantageous UV filter substances for the purposes of the present invention are sulfonated, water-soluble UV filters - by way of example:

• phenylene-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic acid and its salts, particularly the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS no. 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP from Haarmann & Reimer;

2015258134 12 Dec 2019 • salts of 2-phenyl benzimidazole-5-sulfonic acid, such as its sodium, potassium or its triethanolammonium salt, and the sulfonic acid itself with the INCI name Phenylbenzimidazole sulfonic acid (CAS. No. 27503-81-7) which is available for example under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann & Reimer;

• 1,4-di(2-oxo-10-sulpho-3-bornylidenemethyl)benzene (also: 3,3'( 1,4phenylendimethylene)-bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-ylmethane sulfonic acid) and its salts (particularly the corresponding 10-sulfatocompounds, especially the corresponding sodium, potassium or triethanolammonium salt), also known as benzene-

1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid). Benzene-1,4-di(2-oxo-3bornylidenemethyl-10-sulfonic acid) has the INCI name terephthalidene dicamphor sulfonic acid (CAS no. 90457-82-2) and is, for example, available under the trade name Mexoryl SX from 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-3bornylidenemethyl)sulfonic acid, and salts thereof.

Advantageous UV filter substances for the purposes of the present invention are also socalled broadband filters i.e., filter substances which absorb both UV-A and UV-B radiation. 0

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, by way of example • 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6(4-methoxyphenyl)-1,3,5-triazine (INCI: methylene bis-benzotriazolmethylbutylphenol), which is available from CIBA-

Chemikalien GmbH under the trade name Tinosorb® S;

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

• 4,4',4-(1,3,5-triazine-2,4,6-triyltriimino)-tris-benzoic acid-tris(2-ethylhexylester), also: 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: octyl triazone), marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

An advantageous broadband filter for the purposes of the present invention is also 2,2'methylene-bis(6(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol) (INCI: bisoctyltriazole), which is available under the trade name Tinosorb® M from CIBA35 Chemikalien GmbH.

2015258134 12 Dec 2019

An advantageous broadband filter for the purposes of the present invention is also 2-(2Hbenzotriazole-2-yl)-4-methyl-6[2-methyl-3-[1,3,3,3-tetramethyl-1[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol (CAS no. 155633-54-8) with the INCI name drometrizole trisiloxane.

The further UV filter substances can be oil-soluble. Advantageous oil-soluble filter substances are, by way of example:

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

4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid-(2ethylhexyl)ester, 4-(dimethylamino)benzoic acid amylester;

derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and UV filters bonded to polymers.

A further photoprotective filter substance to be used advantageously according to the invention is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene), which is available under the name Uvinul® N 539 from BASF.

Particularly advantageous preparations for the purposes of the present invention contain, in addition to the filter substance(s), preferably also 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-(4methoxyphenyl)-1,3,5-triazine, each either alone or in any combination with each other.

The list of said UV filters which can be used for the purposes of the present invention is naturally not intended to be exhaustive.

The particulate phase advantageously contains a total amount of the substances which absorb UV radiation in the UV-A and/or UV-B-range of, by way of example, 0.1 wt.% to 30 wt.%, preferably 0.5 to 20 wt.%, in particular 1.0 to 15.0 wt.%, each based on the total weight of the particulate phase.

It is possible and optionally advantageous according to the invention, although not obligatory, 35 to equip not only the particulate phase but also the outer, flowable, gel-based phase with UV

2015258134 12 Dec 2019 filter substances, as long as the requirements for turbidity are met. Typically, water-soluble UV filter substances are used in the outer gel phase.

Where water-soluble UV filter substances will be used in the outer gel phase, the same contains a total amount of substances which absorb UV radiation in the UV-A and/or UV-Brange of 0.1 wt.% to 30 wt.%, preferably 0.5 to 20 wt.%, more preferably 1.0 to 15.0 wt.%, each based on the total weight of the outer gel phase.

To produce the particles which constitute the inner, solid, particulate phase, a method which 0 is known from DE 44 24 998 A1 can be used advantageously. In this method, the composition constituting the particulate phase, and optionally a composition from which the particulate phase will develop, and which is preferably in a flowable form, is formed into a liquid jet directed into the environment which has the curing effect, and the portions are formed by the liquid jet being divided before the curing environment into defined portions, 5 such that the portions continue to move substantially in the direction of the liquid jet.

This method can currently be designed in such a manner that a liquid jet is initially formed from the composition which composes the particulate phase, or optionally a composition from which the particulate phase will develop, by the liquid particles moving in the direction of the 0 environment which produces the curing effect. After formation of the liquid jet, the same is mechanically divided into defined portions, wherein the accordingly formed portions continue to move in the direction determined by the liquid jet. The division of the liquid jet is thus carried out by periodically removing liquid from the liquid jet, thereby forming the defined portions. The length of these portions can be kept so short that during the remaining movement up to the environment which produces the curing effect, in particular the surface of a curing medium, an at least approximately spherical shape is formed due to the surface tension of the liquid medium, such that spherical particles are formed.

For liquid media which have a certain viscosity, it is advantageous if the liquid medium is forced through the nozzle to form the liquid jet. This is usually done by applying an overpressure in the reservoir and/or in the line to the liquid jet nozzle.

In many applications there is a need to equip the preferably spherical particles with a coating. This coating can optionally be cured in the same environment. It is possible according to the 35 present invention to coat the portions of the liquid medium prior to curing by generating at

2015258134 12 Dec 2019 least one liquid cross-jet with a liquid which is suitable for coating, wherein the portions pass through the same.

The liquid cross-jet can be expediently designed as a flat jet, such that the possible passage 5 area is enlarged for the portions.

A modification of the method can involve the nozzle arrangement being configured to form at least one liquid jet, and a movable dividing device being arranged below the nozzle arrangement for the at least one liquid jet.

The dividing device in this case can be partly positioned directly at the outlet of the nozzle arrangement. Preferably, the moving dividing device can be driven with rotation, and is equipped with elements which interrupt the liquid jet. The rotating drive of the dividing device enables a particularly simple construction of the device according to the invention.

In one advantageous embodiment, the elements which interrupt the liquid jet can be radiallyoriented radiant elements which are implemented as wires, plastic threads, or the like. The elements can be designed without inherent shape stability, only obtaining their radial orientation upon the rotation of the first dividing device. In another embodiment, a rotating 0 disk can be used which has passage openings arranged tightly next to each other on a radius for the liquid jet. The struts between the passage openings in this case form the elements which interrupt the liquid jet.

The dividing device is advantageously surrounded by a cylindrical housing which is open at 25 least in the area of the liquid jet, and which has a capturing recess to capture liquid which runs off the housing wall. In this manner, the liquid conveyed outward radially by the elements interrupting the liquid jet can be captured and directed back to the associated reservoir. The capturing recess is preferably formed by a circumferential groove which is configured with a drain.

To form a coating of the particles as mentioned above, the device can have a cross nozzle arranged downstream of the dividing device with respect to the liquid jet, oriented at an angle to the liquid jet and connected to a reservoir for a liquid which is suitable for coating. The cross nozzle in this case can embody a flat jet nozzle.

2015258134 12 Dec 2019

In an exemplary embodiment, a liquid jet of a cell emulsion in a sodium alginate solution can exit the nozzle, and the cross jet can be formed by a cell-free sodium alginate solution, while a CaCI? solution fills the capturing container 5 as the curing medium.

Upon passage through the cross jet which is preferably designed as a flat beam, the liquid portions which contain the cells are coated with the cell-free alginate solution for 3 min. and then crosslinked immediately so that a migration of cells from the core into the coating layer cannot occur - since the Ca ions are able to diffuse much faster into the alginate droplets than the cells can move.

It is possible to equip a conventional cosmetic container with a preparation according to the invention in such a manner that the inner particulate phase approaches the densest possible packing of spheres (space-filling, cubic close packing of spheres: about 74%), the interstitia of which are filled by the outer, aqueous, gel phase.

Therefore, the volume ratio of the inner particulate phase to the outer, aqueous gel is preferably in the range of about 20% : 80% to 74% : 26%, particularly preferably 30% : 70% to 65% : 35%, and particularly preferably from 40% : 60% to 60% : 40%.

Preparations according to the invention can be packaged in a visually attractive and advantageous manner and in this further aspect, also inventively per se in a container (B),

- which has a tubular body (K),

- the wall (Wk) of which allows the transmission of visible light of 25% to about

100%,

- wherein a dispensing head (SK) is attached to the upper end thereof,

- which is bounded on the bottom by a movable trailing piston (SCH).

The dispensing head (SK) can particularly advantageously have

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

- a base unit (BO) which lies on the tubular body (K), having an opening (Ο) to the tubular body, and

- a flexible, inner, substantially cylindrical, molded hollow body (H) with bellows-like walls (Wh), wherein the elements of the dispenser head are designed in such a manner that

2015258134 12 Dec 2019

- the hollow body (H) has openings (Oo), (Ou) on each of the two ends (So), (Su),

- the hollow body (H) lies with its lower end face (SU) on the base unit (BO), and wherein the opening (0) thereof and the lower opening (OU) of the hollow body (H) are positioned one above the other, in such a manner that, when

- the actuating element (BE) compresses the inner hollow body (H) in the direction of its longitudinal axis as a result of external pressure,

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

- when the external pressure ceases, the return force of the flexible inner hollow body (H) suctions substance out of the tubular body (K) and into the flexible inner hollow body (H).

Fig. 1 shows an inventively advantageous container (B),

- which has a tubular body (K),

- wherein a dispensing head (SK) is attached to the upper end thereof,

- which is bounded on the bottom by a movable trailing piston (SCH), and

- which has a dispenser head (SK), wherein in Fig. 1a, the container (B) is illustrated as separated into the body (K) and the dispenser head (SK) (in this case configured with an additional closure cap which is not indicated).

Fig. 1a shows a dispenser head (SK),

- which has an outer actuating element (BE) with a dispensing opening (SPO) which is closed off by a check valve (RV),

- a base unit (BO) which lies on the tubular body (K), having an opening (0) to the tubular body, and

- a flexible, inner, substantially cylindrical, molded hollow body (H) with bellows-like walls (Wh).

Fig. 1 b shows a perspective view of an embodiment of the flexible, inner, substantially cylindrical, molded hollow body (H),

- with bellows-like walls (Wh),

- wherein the lower end face (Su) and the opening (Ou) thereof are visible.

2015258134 12 Dec 2019

Fig. 1c shows the outline of one embodiment of the flexible, inner, substantially cylindrical, molded hollow body (H),

- with bellows-like walls (Wh), wherein the elements of the dispenser head are designed in such a manner that

- the hollow body (H) has openings (Oo), (Ou) on each of the two ends (So), (Su), and wherein the hollow body (H) is designed in such a manner that the lower opening (OU) on the lower end (SU) comprises a device (V) which divides the substance stream from the interior of the tubular body (K) into the hollow body into a plurality of partial streams.

Fig. 1d shows a device (V), which is included for the purpose of dividing the substance stream from the interior of the tubular body (K) (not shown here) into the hollow body (H) (not shown here) into three partial streams by means of three passage openings (Du).

In the preparations according to the invention the ubiquinone(s) and/or plastoquinone(s) are optimally protected against oxidation and the harmful effects of UV radiation.

When the preparations are applied to a surface, the inventive preparations are rubbed into a homogeneous emulsion which absorbs quickly into the skin and is visually and sensually very appealing.

It is particularly surprising that, when a dispenser is used, the shear forces at the dispenser output are adequate to transform the originally into separate compartments (that is, the outer gel phase and the inner particulate phase) into an optically homogeneous entity.

The cosmetic and dermatological preparations according to the invention can comprise cosmetic excipients such as are customarily used in such preparations - by way of example preservatives, preservation aids, bactericides, perfumes, substances for preventing foaming, dyestuffs, pigments which have a coloring action, thickeners, moisturizing and/or humectant substances, fillers which improve the skin feel, fats, oils, waxes, or other customary constituents of a cosmetic or dermatological preparation 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 donors (such as, for example, DMDM hydantoin, which is available, for example, under the trade name Glydant™ from the Lonza company), iodopropylbutyl carbamates (e.g. sold under the trade names Glycacil-L, Glycacil -S available from the Lonza

2015258134 12 Dec 2019 company, and/or Dekaben LMB from Jan Dekker), parabens (that is, p-hydroxy benzoic acid alkyl esters such as methyl, ethyl, propyl and/or butylparaben), phenoxyethanol, ethanol, benzoic acid and the like. Typically, the preservative system according to the invention further advantageously comprises preservation aids such as octoxyglycerol, glycine soya etc.

Particularly advantageous preparations are also obtained when antioxidants are used as additives or active agents. According to the invention, the preparations advantageously comprise one or more antioxidants. Favorable, but nevertheless optional, antioxidants can include all antioxidants which are suitable or customary for cosmetic and/or dermatological 0 applications.

Particularly advantageous for the purposes of the present invention is the use of watersoluble antioxidants, such as vitamins - by way of example ascorbic acid and derivatives thereof, as well as D-biotin, natural and/or synthetic isoflavonoids, alpha-glucosylrutin, 5 panthenol, aloe vera, honokiol, magnolol.

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

It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic or dermatological active agents, wherein preferred active agents are antioxidants which can protect the skin against oxidative stress.

Advantageous further active agents are natural active agents and/or derivatives thereof such as phytoene, carnitine, carnosine, creatine, N-acetyl-hydroxyproline, taurine and/or betaalanine.

The outer, aqueous gel phase of the preparations according to the invention can advantageously contain conventional cosmetic excipients such as alcohols, in particular those of low carbon number, preferably ethanol and/or isopropanol, diols or polyols of low carbon number, and ethers thereof, preferably propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethylether or -monobutylether, propylene glycol monomethyl-, monoethylor monobutylether, diethylene glycol monomethylor monoethylether, and analogous products, polymers, foam stabilizers, electrolytes, and especially one or more thickeners, which can advantageously be selected from among the group silica, aluminum

2015258134 12 Dec 2019 silicates, polysaccharides or derivatives thereof, for example hyaluronic acid, xanthan gum, hydroxypropyl methylcellulose, particularly advantageously from among the group of polyacrylates, preferably a polyacrylate from among the group of Carbopols, for example Carbopol grades 980, 981, 1382, 2984, 5984, either individually or in combination.

Moisturizers can also preferably be used.

Moisturizers are substances or mixtures of substances which impart to cosmetic or dermatological preparations the property of reducing moisture loss by the horny layer (also called transepidermal water loss (TEWL)) and/or positively influencing the hydration of the 0 horny layer following application or distribution on the skin surface.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and/or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccharide gum-1, glycine soja, ethylhexyloxyglycerin, pyrrolidone and urea.

Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of polysaccharides which are water-soluble and/or water-swellable, and/or can gel with the aid of water. Particularly advantageous are, byway of example, hyaluronic acid, chitosan and/or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registry number 178463-23-5, and is available, by way of example, under the name of fucogel® 1000 0 from SOLABIA S.A.

The cosmetic or dermatological preparations according to the invention can also advantageously, but not necessarily, comprise fillers which further improve, for example, the sensory and cosmetic properties of the formulations and bring about or enhance a velvety or 25 silky feel on the skin, for example. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum and/or sodium starch octenyl succinate and the like), pigments which have neither primarily UV filter effect nor a coloring effect (for example, boron nitride, etc.) and/or Aerosile® (CAS no. 7631-86-9).

The following examples illustrate the present invention without limiting it. The numerical values in the examples are percentages by weight, based on the total weight of the preparations.

m CN

Examples, inner particulate phase:

Variants

LU

LO T^-

0.2

0.3

CM T^-

CO

CM

CM T^-

0.4

0.6

0.5

CM

ad 100

Q

LO T^-

0.13

CM

co

CM T^-

co

0.8

0.6

0.5

CM

ad 100

O

LO T^-

0.25

0.5

LO

LO T^-

1

0.5

o

0.6

0.5

CM

ad 100

LO T^-

o

LO T^-

LO

T^-

0.49

0.6

0.5

CM

ad 100

<

LO T^-

0.19

2.50

10.00

0.25

8.00

1.00

0.60

0.50

2.00

ad 100

INCI

Algin

Ubiquinone

Cl 77891

Cyclomethicone (BRB CM 56; BRB International)

Cyclomethicone + Dimethiconol (Xiameter PMX 1501 Fluid; Dow Corning)

Sodium stearyl glutamate (Eumulgin SG; BASF Personal Care and Nutrition)

Polyglyceryl-3 methylglucose distearate (Tego Care 450; Evonik Industries)

Polymethylsilsesquioxane (Gransil PSQ; Grant Industries)

Fragrance

Phenoxyethanol

1,2-hexanediol

Methylpropanediol

Water

The ingredients of the recipe of Examples A to E are prepared as in the experimental example in DE 44 24 998, column 5, and formed into essentially spherical particles with a diameter of approximately 6 mm.

2015258134 12 Dec 2019

Variants	co	0.07	0.02	0.4	0.8	22	ir>	1.63		0.6	0.5	CN	1	1	1	1.63	ir>	ad 100
	0.04	0.01	0.2	0.5	LO		90' l·	0.8	0.6	0.5	CN	1	1	1	o		ad 100
to	0.07	0.02	0.4	0.8	22	LO	1.63		0.6	0.5	CN	1	1	2.5	1	LO	ad 100
	0.04	0.01	0.2	0.5	LO		90' l·	0.8	0.6	0.5	CN	1	1	CN	1		ad 100
	0.07	0.02	0.4	0.8	22	LO	1.63		0.6	0.5	CN	1	1.63	1	1	LO	ad 100
co	0.04	0.01	0.2	0.5	LO		GO' l·	0.8	0.6	0.5	CN	1	o	1	1		ad 100
CN	0.07	0.02	0.4	0.8	22	LO	1.63		0.6	0.5	CN	2.33	1	1	1	LO	ad 100
	0.04	0.01	0.2	0.5	LO		GO' l·	0.8	0.6	0.5	CN	1.28	1	1	1		ad 100
Example, outer aqueous gel:	INCI	Creatine	Creatinine	Sodium hyaluronate	PEG-40 hydrated castor bean oil (Eumulgin CO 40; BASF Personal Care and Nutrition)	Glycerine	1,2-propanediol	Sodium citrate (Tri-sodiumcitrate-5,5-hydrate A.R. No. 10⁶431; Merck)	Sodium hydroxide 45%	Phenoxyethanol	1,2-hexanediol	Methylpropanediol	Acrylic acid/VP crosspolymer (Ultrathix P-100; Ashland Specialty Ingredients)	Acrylates/C 10-30 alkylacrylate crosspolymer	Ammonium acryloyldimethyltaurate/VP copolymer (Aristoflex AVC; Clariant)	Carbomer (Carbopol 980 or Carbopol 981; Lubrizol Advanced Materials)	Lubrajel Oil Free; Ashland Specialty Ingredients	Water

CN

2015258134 12 Dec 2019

The recipe ingredients in Examples 1-8 are stirred into a mixture at 25 °C until clear gels have formed.

Particles and gels were combined in various volume ratios with each other, as in the following examples. The first value indicates the particulate phase, and the second value 5 indicates the gel phase.


	1	2	3	4	5	6	7	8
A	25 : 75	30 : 70	50 : 50	40 : 60	25 : 75	40 : 60	40 : 60	50 : 50

B	30 : 70	40 : 60	25 : 75	30 : 70	40 : 60	35 : 65	35 : 65	25 : 75

C	50 : 50	40 : 60	40 : 60	50 : 50	35 : 65	25 : 75	50 : 50	40 : 60

D	40 : 60	35 : 65	35 : 65	35 : 65	30 : 70	40 : 60	30 : 70	50 : 50

E	25 : 75	35 : 65	50 : 50	35 : 65	40 : 60	35 : 65	40 : 60	35 : 65

In charges of 40 ml, the preparations A1-E8 were filled into containers as described in Figure 1a to Figure 1d.

Claims

Claims

1. A cosmetic preparation, comprising

- an outer, flowable, gelatinous, water-based phase

5 - which allows the transmission of light of the wavelength 700 nm in the range of at least 30 %, and/or

- which has a viscosity selected from the range of 1,000 to 10,000 mPas at a temperature of 25 °C and a shear rate of about 10s'¹, and

0 - an inner, solid, particulate phase which

- comprises spherical particles with an average diameter selected from the range of 0.1 to 10 mm and wherein the particulate phase comprises

- a polymer matrix which is insoluble in water,

- one or more substances selected from among the group of

5 ubiquinones and/or plastoquinones,

- one or more light filter substances which is/are selected from among the group of metal oxide pigments.
2. A cosmetic preparation according to claim 1 wherein the outer, flowable, gelatinous

0 water-based phase has a selected from 3000 to 9000mPas at a temperature of 25 °C and a shear rate of about 10s'¹.
3. A cosmetic preparation according to claim 1 wherein the outer, flowable, gelatinous water-based phase has a viscosity selected rom which has a viscosity selected from

25 5000 to 8000mPas at a temperature of 25 °C and a shear rate of about 10s'¹.
4. A cosmetic preparation according to any one of claims 1 to 3 wherein the inner, solid, particulate phase comprises spherical particles with an average diameter selected from the range of 2 to 7.5 mm.
5. A cosmetic preparation according to any one of claims 1 to 4, wherein that the outer flowable gelatinous water-based phase is characterized by a content of one or more hydrocolloids which is/are selected from among the group of celluloses/methyl celluloses, polyacrylates.

2015258134 12 Dec 2019
6. A cosmetic preparation according to any one of claims 1 to 4 wherein the outer flowable gelatinous water-based phase is charcterized by a content of one or more hydrocolloids which is/are selected from among the group containing carrageenan, xanthan, acrylate/C 10-30 alkyl acrylate crosspolymers, and

5 ammoniumacryloyldimethyltaurate/vinylpyrrolidone copolymers, carbomers, acrylic acid/VP crosspolymers.
7. A cosmetic preparation according to claim 5 or 6, wherein the total amount of one or more hydrocolloids is less than 1.5 wt.% with respect to the total weight of the

0 preparation.
8. A cosmetic preparation according to claim 5 or 6, wherein the total amount of one or more hydrocolloids is between 0.1 and 1.0 wt.% with respect to the total weight of the preparation.
9. A cosmetic preparation according to any one of the previous claims, wherein the polymer matrix of the inner particulate phase is selected from among the group of the following polymer matrices: algin/alginate, carrageenan, agar, gellan gum, chitosan.

0
10. A cosmetic preparation according to one of the previous claims, wherein the metal oxide pigment(s) is/are selected from among the group of oxides of titanium (TIO₂), zinc (ZnO), iron (e.g. Fe₂O3), zirconium (ZrO₂), silicon (SiO₂), manganese (e.g. MnO), aluminum (AI2O3), cerium (e.g. Ce₂O3), mixed oxides of the corresponding metals, and mixtures of such oxides, as well as the sulfate of barium (BaSCU).
11. A cosmetic preparation according to claim 10, wherein the one or more metal oxide pigments is/are selected from among the group of oxides of titanium (TIO₂).
12. A cosmetic preparation according to any one of the preceding claims, wherein

30 ubiquinone 10 (coenzyme Q10) is selected as the ubiquinone.
13. A cosmetic preparation according to any one of the preceding claims, wherein ubiquinone is present in the reduced form (ubiquinol).

35
14. A cosmetic preparation according to any one of the previous claims, wherein the inner solid particulate hase further comprises a photoprotective filter substance or

2015258134 12 Dec 2019 substances selected from among the group of octylmethoxycinnamates, octocrylene, Tinosorb M, Tinosorb S, Mexoryl XL, benzophenone-3, benzophenone-4.
15. A cosmetic preparation according to any one of the previous claims, wherein the

5 volume ratio of the inner particulate phase to the outer, aqueous gel is in the range from about 20%: 80% to 74%: 26%.
16. A cosmetic preparation according to any one of the previous claims, wherein the volume ratio of the inner particulate phase to the outer, aqueous gel is in the range

0 from about 30%: 70% to 65%: 35%.
17. A cosmetic preparation according to any one of the previous claims, wherein the volume ratio of the inner particulate phase to the outer, aqueous gel is in the range from about 40%: 60% to 60%: 40%.