EP1478325A1

EP1478325A1 - Biphasic sunscreen preparation comprising a w/o emulsion

Info

Publication number: EP1478325A1
Application number: EP03704616A
Authority: EP
Inventors: Jens Schulz; Anja Göppel; Simone Budow
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2002-02-19
Filing date: 2003-02-14
Publication date: 2004-11-24
Also published as: WO2003070202A1; DE10206796A1

Abstract

Biphasic cosmetic and/or dermatological sunscreen preparation comprising a) a W/O emulsion, b) a lipophilic or aqueous phase, c) at least one W/O emulsifier and d) at least one organic and/or inorganic UV filter, characterised in that at least one phase is not transparent or translucent.

Description

Beiersdorf Aktiengesellschaft Hamburg

Two-phase sunscreen preparations with W / O emulsion

The present invention relates to two-phase cosmetic and / or dermatological sunscreen preparations, one phase of which contains a W / O emulsion and the other phase of which contains a lipophilic or aqueous phase, with at least one phase which is not transparent and / or translucent, and the use thereof.

The trend away from the paleness towards "healthy, sporty brown skin" has been going on for years. In order to achieve this, people expose their skin to the sun's radiation, since this causes pigment formation in the sense of melanin formation. The ultraviolet radiation of sunlight has however, it also has a damaging effect on the skin In addition to the acute damage (sunburn), long-term damage such as an increased risk of developing skin cancer occurs with excessive exposure to light from the UVB range (wavelength: 280-320 nm) UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue, which leads to numerous phototoxic and photoallergic reactions and results in premature skin aging.

To protect the skin, a number of light protection filter substances have therefore been developed that can be used in cosmetic preparations. These UVA and UVB filters are summarized in most industrialized countries in the form of positive lists such as Appendix 7 of the Cosmetics Regulation.

In order to be able to estimate the effectiveness of the sun protection filters for the skin, Schulze introduced the sun protection factor (SPF or LF) and sun protection factor (SF) in the 1950s. It is defined as follows:

M ^ ED protected skin

LSF = MED = Er themschwellendose (English minimum er themal

MED unprotected skin can) The UV light protection filters approved for cosmetic applications also include compounds of the basic structure of triazine:

Another class of UV light protection filters is derived from benzimidazole sulfonic acids:

A third class of advantageous light protection filters is based on the structural element of benzotriazole:

Sun protection preparations are usually offered in the form of emulsions. However, these homogeneous preparations are increasingly perceived by consumers as monotonous and boring. However, the possibilities for making these formulations more visually attractive are limited. Increasingly, consumers are tired of the flood of ready-to-use finished products and are inspired by the desire to prepare the cosmetic formulations themselves in order to do "something good" afterwards. In order to meet this new drive of consumers, two-phase cosmetic preparations are increasingly being offered which the customer can convert to a homogeneous emulsion by simply shaking and then apply to allow mix "before each use, the homogeneous emulsion, however, must in a timely re-segregate. Only then _^ can complied with the playfulness of consumers and the joy be guaranteed to the application. Finally, allow two-phase products completely new optical design possibilities.

Unfortunately, according to the current state of the art, only transparent two-phase cosmetic sunscreen preparations based on a lipophilic and an aqueous phase are to be formulated. However, these have the disadvantage that they usually separate out too quickly after homogenization by shaking. In addition, it has not hitherto been possible to use pigmentary organic and / or inorganic UV filters in these preparations in order to achieve high sun protection factors in this way. Last but not least, due to their appearance, these products do not evoke the association of care and UV protection, which are usually associated with white-colored preparations with a creamy consistency.

It was therefore the object of the present invention to eliminate the shortcomings of the prior art and to develop two-phase cosmetic and / or dermatological sun protection preparations with high UV protection based on which at least one phase is not transparent.

Surprisingly, the object is achieved by two-phase cosmetic and / or dermatological sun protection preparations containing a) a W / O emulsion, b) a lipophilic or aqueous phase, c) at least one W / O emulsifier, d) at least one organic and / or inorganic UV filter substance, characterized in that at least one phase is not transparent and / or translucent.

According to the invention, W / O stands for water-in-oil emulsion or emulsifier.

Two-phase cosmetic and / or dermatological sun protection preparation in the sense of the present invention means that the W / O emulsion and the lipophilic or aqueous phase are separately layered on top of each other. The W / O emulsion is regarded as one phase in this consideration, although it is of course known to the person skilled in the art that W / O emulsions are in themselves formed from two phases homogenized with one another. The W / O emulsion is long-term stable. This means that it will last for an extended period of time. (Months, years) there is no segregation or phase separation. The peculiarity of the present invention, which is to be expressed with the term two-phase, is that the W / O emulsion and the lipophilic or aqueous phase, which is present separately as the second phase, are present in layers separated from one another. These two phases or layers can be, for example, through. Briefly emulate the shaking to a homogeneous emulsion, which is not stable in the long term, but rather segregate over a period of minutes, hours or days into a layered W / O emulsion and lipophilic or aqueous phase.

It is advantageous according to the invention if the amount of the lipophilic or aqueous phase is 5 to 95% by volume, in particular 10 to 90% by volume, based on the total volume of the formulation.

The sun protection preparations according to the invention are characterized in that they contain one or more W / O emulsifiers in a concentration of 0.1 to 3% by weight.

With the aid of the emulsifier concentration, the separation rate of the preparation according to the invention which has been homogenized by shaking can be precisely adjusted.

According to the invention, the W / O emulsifier (s) can be selected from the group of silicone emulsifiers. Advantageously from the group of alkyl methicon copolyols and / or alkyl dimethicone copolyols, in particular from the group of compounds which are characterized by the following chemical structure: in which X and Y are selected independently of one another from the group H (hydrogen) and the branched and unbranched alkyl groups, acyl groups and alkoxy groups having 1 to 24 carbon atoms, p represents a number from 0 to 200, q represents a number from 1 to 40, and r represents a number from 1 to 100.

An example of silicone emulsifiers to be used particularly advantageously for the purposes of the present invention are dimethicone copolyols, which are available from Th.Goldschmidt AG under the trade names ABIL® B 8842, ABIL® B 8843, ABIL® B 8847, ABIL® B 8851, ABIL® B 8852, ABIL® B 8863, ABIL® B 8873 and ABIL® B 88183.

Another example of surface-active substances to be used particularly advantageously for the purposes of the present invention is cetyl dimethicone copolyol, which is sold by the company Th.Goldschmidt AG under the trade name ABIL® EM 90.

Another example of surface-active substances to be used particularly advantageously for the purposes of the present invention is the cyclomethicone dimethicone copolyol, which is sold by the company Th.Goldschmidt AG under the trade name ABIL® EM 97.

Furthermore, the emulsifier lauryl methicone copolyol, which is sold under the trademark Dow Corning® 5200 Formulation Aid by the company Dow Corning Ltd., has proven to be particularly advantageous. is available.

Another advantageous silicone emulsifier is 'octyl dimethicone ethoxy glucoside' from Wacker. Furthermore, the W / O emulsifier (s) according to the invention can preferably be selected from the following group:

Sorbita stearate, sorbitan oleate, lecithin, glyceryl alcoholate, lanolin, ozokerite, hydrogenated castor oil, glyceryl isostearate, polyglyceryl 3-oleate, wool wax acid mixtures, wool wax alcohol mixtures, pentaerythrithyl isostearate, polyglyceryl 3-diisostearate

Methylglu ^{'cosedioleat,} PEG-7 hydrogenated castor oil, polyglyceryl-4 isostearate, hexyl laurate, acrylate / C _{10 degrees.} _30- alkyl acrylate cross-polymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-4-dipolyhydroxystearate, PEG-30-dipolyhydroxy-stearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-3-polyglyceryl-glyceryl-3-polyglyceryl-glyceryl-3-polyglyceryl-glyceryl-3-polyglyceryl-3-diol dioleate.

The following combinations of lipophilic components and emulsifiers are advantageous, among others: ^' Sorbitan oleate in a mixture with hydrogenated castor oil, beeswax (Cera alba) and stearic acid, sodium dihydroxycetyl phosphate in a mixture with isopropylhydroxycetyl ether, methylglucose dioleate in a mixture with hydroxystearate and beeswax, mineral with petrolatum, ozokerite, glyceryl oleate and lanolin alcohol, petrolatum in a mixture with ozokerite, hydrogenated castor oil, glyceryl isostearate and polyglyceryl 3-oleate, sorbitan oleate in a mixture with PEG-2 hydrogenated castor oil, ozokerite and hydrogenated castor oil, sorbitan isostearate 2 in a mixture with hydrogenated castor oil.

According to the invention, cetyldimethicone copolyol, glyceryl isostearate, polyglyceryl-2-dipolyhydroxystearate and / or PEG-30 dipolyhydroxystearate are particularly advantageously used as W / O emulsifiers.

Embodiments of the invention which are advantageous according to the invention can also contain additional O / W emulsifiers (oil-in-water emulsifiers) as coemulsifiers. According to the invention, the O / W emulsifier (s) are preferably selected from the following group:

Ceteareth-20, trilaureth-4 phosphate, cetyl phosphate, cetearyl sulfate, PEG-40 stearate, PEG-100 stearate, Polysorbate-60 and / or Polysorbate-65. Glyceryl stearate citrate, cetearyl sulfate, ethoxylated fatty acids (PEG-40 stearate, PEG-100 stearate) and / or phosphate emulsifiers (for example cetyl phosphate) are used as O / W emulsifiers which are particularly advantageous according to the invention - as coemulsifiers.

It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not to protect against sunlight, but which nevertheless contain other UV protection substances. So z. B. in day care products or make-up products usually incorporated UV-A or UV-B filter substances. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage.

Accordingly, the preparations in the sense of the present invention preferably contain at least one UV-A, UV-B and / or broadband filter substance and / or at least one inorganic pigment reflecting and / or absorbing UV light. The formulations may, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances, which may be present in the water and / or the oil phase.

According to the invention are all embodiments in which the UV protective substances are exclusively in one of the two phases or in both phases of the preparations according to the invention.

The preparations according to the invention can also advantageously be in the form of so-called oil-free cosmetic or dermatological preparations which contain a water phase and at least one UV filter substance which is liquid at room temperature as a further phase.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-dipheny! Acrylate (INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate ( 2-ethylhexylsalicylate, octylsalicylate, INCI: ethylhexyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: ethylhexyl methoxycinnamate) and 4-methoxyentyl acetate (4-methoxyentyl acetate) - methoxycinnamate, INCI: Isoamyl p-methoxycinnamate) and polymeric UV filters such as the (3- (4- (2,2-bis-ethoxycarbonylviny!) - phenoxy) propenyl) - methylsiloxane / dimethylsiloxane copolymer, which is available, for example, from Hoffmann-La Röche is available under the trade name Parsol SLX.

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (TiO), zinc (ZnO), iron (e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (e.g. MnO), aluminum (AI ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals as well as mixtures of such oxides and the sulfate of barium (BaSO ₄ ) ,

For the purposes of the present invention, the pigments can also advantageously be used in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.

According to the invention, the pigments can advantageously be surface-treated ("coated"), for example, a hydrophilic, amphiphilic or hydrophobic character should be formed or retained. This surface treatment can consist in the pigments being treated in a manner known per se with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer The various surface coatings can 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 (Al ₂ O), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , Sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), barium sulfate (BaSO) or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings can occur 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: 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 suitable according to the invention are available under the following trade names from the companies listed:

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

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

Advantageous further UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. B .:

Phenyien-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, in particular 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 Disodium Phenyl Dibenzimidazole Tetrasulfonate (CAS No .: 180898-37-7), which is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP;

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

• 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene)) bis- (7,7-dimethyl-2- oxo-bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also known as benzene-1, 4-di (2-oxo-3-bomylidene-methyl-10-sulfonic acid) Benzene-1,4-di (2-oxo-3-bomylidene-methyl-10-sulfonic acid) has the INCI name Terephthalic Dicampher Sulfonic Acid ( CAS.-No .: 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;

• Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bomylidene-methyl) benzoisulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and salts thereof. Hydroxybenzophenone derivatives, such as e.g. 2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester, which is available, for example, from BASF under the trade name Uvinul® A Plus.

• benzoxazole derivatives, such as e.g. the 2,4-bis- [5-1 (dimethylpropyl) benzossazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine (CAS no .: 288254-16-0), which is available, for example, from 3V Sigma.

Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B. • 2,4-bis - {[4- (2-Ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH;

• Diethylhexylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), 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-ethylhexyl), also: 2,4,6-tris [anilino - (p-carbo-2 ^, -ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: Ethylhexyl 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 the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ), CAS No .:

103597-45-1, which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is available under the trade name Mexoryl® XL from Chimex ,

The other UV filter substances can be oil-soluble or water-soluble.

Advantageous oil-soluble UV-B and / or broadband filter substances in the sense of the present invention are e.g. B .:

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

^■ 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester; ^■ Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone

^■ as well as UV filters bound to polymers. 3- (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethyisiloxane copolymer which is available, for example, from Hoffmann La Röche under the trade name Parsol® SLX.

Particularly advantageous preparations within the meaning of the present invention, which are distinguished by a high or very high UV-A and / or UV-B protection, preferably also contain further UV-A and in addition to the filter substance (s) according to the invention / or broadband filter, in particular dibenzoylmethane derivatives [for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane], phenylene-1, 4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine and / or the 2,4-bis- [5- 1 (dimethylpropyl) benzossazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1, 3,5-triazines, each individually or in any combination with one another.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The UV light protection filters advantageous according to the invention are preferably used in a concentration of 0.1 to 30% by weight, in particular in a concentration of 0.5 to 15% by weight, based on the total weight of the formulation.

The sunscreen preparations advantageous according to the invention contain, as organic filters, asymmetrically substituted triazines, bisimidazylates and / or benzotriazoles.

According to the invention, the cosmetic and / or dermatological light protection formulations can be composed as usual and serve the cosmetic and / or dermatological light protection, furthermore for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics. The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliary substances, as are usually used in such preparations, e.g. B. preservatives, preservation aids, complexing agents, bactericides, perfumes, substances to prevent or increase foaming, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, Waxes or other common components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

An additional level of antioxidants is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L- Carnosine and its derivatives (e.g. Anserin), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thio dipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta- ion sulfones, penta- xa-, heptathionesulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), -hydroxy acids (e.g. citric acid, lactic acid, malic acid) , Humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, -Glycosylrutin, Ferulasäure,. Furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO) selenium and its derivatives (e.g. selenium methylene derivatives, e.g. stilbene and its derivatives) , Trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 10% by weight, particularly preferably 0.05 to 7% by weight, in particular 0.1 to 5% by weight, based on the Total weight of the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 5% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant (s), it is advantageous to use their respective concentrations in the range from 0.001 to 5% by weight, based on the total weight of the formulation. to choose.

In addition, selected recipes according to the invention are suitable, which e.g. B. known anti-wrinkle agents such as flavone glycosides (especially σ-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as z. B. occur with skin aging (e.g. wrinkles and fine lines). They are also advantageous against the appearance of dry or rough skin.

If σ-glycosylrutin is the antioxidant, it is advantageous to choose their respective concentrations from the range from 0.001 to 5% by weight, based on the total weight of the formulation. An aqueous phase present as a second, independent water phase or the water phase of the W / O emulsion of the preparations according to the invention can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols low C number and their ethers, preferably propylene glycol, glycerol, butylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, polymers, foam stabilizers, in particular, and electrolytes one or more thickeners, which one or which can advantageously be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles [from Bf. Goodrich], for example carbopoles of types 980, 981, 1382, 2984, 5984, ETD 2020, ETD 2050, Ultrez 10, each individually or in combination.

The preparations according to the invention can also advantageously contain self-tanning substances, such as, for example, dihydroxyacteon and / or melanin derivatives in concentrations of 1% by weight to 10% by weight, based on the total weight of the preparation.

The preparations according to the invention can also advantageously contain repellents for protection against mosquitoes, ticks and spiders and the like. Are advantageous for. B. N, N-diethyl-3-methylbenzamide (trade name: Meta-delphene, "DEET"), dimethyl phthalate (trade name: Palatinol M, DMP) and in particular 3- (Nn-butyl-N-acetylamino) - ethyl propionate (available under the trade name Insekt Repellent® 3535 from Merck) The repellents can be used both individually and in combination.

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also known as trans-epidermal water loss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively. Advantageous moisturizers for the purposes of the present invention are, for example, glycerin, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidone carboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. is available under the name Fucogel®1000 from the company SOLABIA SA. Moisturizers can also advantageously be used as anti-wrinkle active ingredients for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as those described for. B. occur in skin aging, are used.

The cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like), pigments which have neither mainly UV filter nor coloring effects (such as e.g. B. boron nitride etc.) and / or Aerosile ^® (CAS No. 7631-86-9).

A second lipophilic phase, which is present as an independent oil phase, or the oil phase of the W / O emulsion of the formulations according to the invention is advantageously selected from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, specifically the triglycerol esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as. B. cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like. According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax and other insect waxes, and berry wax, shea butter and / or lanolin (wool wax).

For the purposes of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such

Ester oils can then advantageously be selected from the group octyl palmitate, octyl co-coat, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate,

Isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, ri-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethyl hexylateyl, ethyl stylate, 2-ethyl hexyl laurate, 2-ethyl hexyl laurate, 2-ethyl hexyl laurate Oleylerucat, Erucyloleat, Erucylerucat, Tridecyistearat, Tridecyltrimellitat, as well as synthetic, semi-synthetic and natural mixtures of such esters, such as. B. Jojoba oil.

Furthermore, the oil phases can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates. B. Dicaprylyl ether (Cetiol OE) and / or Dicaprylyl carbonate, for example that available under the trade name Cetiol CC from Cognis.

It is further preferred pentylglykoldiheptanoat the one or more oil components from the group consisting of isoeicosane, neopentyl, propylene glycol dicaprylate / dicaprate, caprylic / capric / Diglyceryl- succinate, butylene glycol dicaprylate / dicaprate, C _12-13 alkyl lactate, di-C _12-13 -Alkyltartrat , Triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tri-caprylin, dimethylisosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C _12-15 alkyl benzoate or consists entirely of this. Advantageous oil components are also e.g. B. butyl octyl salicylate (for example that available under the Hallbrite BHB trade name from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethyl hexyl naphthalate (Hallbrite TQ or Corapan TQ from H&R).

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.

Furthermore, the oil phases can also advantageously also contain nonpolar oils, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane. Among the polyolefins, polydecenes are the preferred substances.

The oil phases can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups) are saturated). The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights. Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, from Th. Goldschmidt under the trade names Abil 10 to 10,000. Phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also referred to as cyclomethicones, are also advantageous, amino-modified silicones (INCI: amodimethicone and silicone wax). B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available from Th. Goldschmidt as different types of abil wax. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

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

(a) Siloxane elastomers which contain the units R ₂ SiO and RSiO ^ and / or R ₃ SiO _0.5 and / or SiO ₂ , the individual radicals R each independently of one another being hydrogen, C _1-24 -alkyl (such as for example methyl, ethyl, propyl) or aryl (such as phenyl or tolyl), alkenyl (such as vinyl) and the weight ratio of the units R ₂ SiO to RSiO _{1ι5 is selected} from the range from 1: 1 to 30: 1;

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

• is in the range from 1 to 20 mol% if the organopolysiloxane is not cyclic and

• is in the range of 1 to 50 mol% when the organopolysiloxane is cyclic. For the purposes of the present invention, the siloxane elastomer or elastomers are advantageously in the form of spherical powders or in the form of gels.

Advantageous siloxane elastomers in the form of spherical powder according to the invention are those with the INCI name Dimethicone / Vinyl Dimethicone Crosspolymer, for example that available from DOW CORNING under the trade names DOW CORNING 9506 Powder.

It is particularly preferred if the siloxane elastomer is used in combination with oils from hydrocarbons of animal and / or vegetable origin, synthetic oils, synthetic esters, synthetic ethers or mixtures thereof.

It is very particularly preferred if the siloxane elastomer is used in combination with unbranched silicone oils which are liquid or pasty at room temperature or cyclic silicone oils or mixtures thereof. Organopolysiloxane elastomers with the INCI name Dimethicone / Polysilicone-11 are particularly advantageous, especially the Gransil types GCM, GCM-5, DMG-6, CSE Gel, PM-Gel, LTX, ININ available from Grant Industries Inc. Gel, AM-18 gel and / or DMCM-5.

It is very exceptionally preferred if the siloxane elastomer is used in the form of a gel composed of siloxane elastomer and a lipid phase, the content of the siloxane elastomer in the gel being 1 to 80% by weight, preferably 0.1 to 60% by weight , each based on the total weight of the gel.

For the purposes of the present invention, it is advantageous for the total amount of the siloxane elastomers (active content) to be in the range from 0.01 to 10% by weight, advantageously from 0.1 to 5% by weight, based in each case on the total weight of the formulation, to choose.

The cosmetic and dermatological preparations according to the invention can contain dyes and / or color pigments, in particular if they are in the form of decorative cosmetics. According to the invention, the individual phases of the preparation can advantageously be colored differently. Embodiments of the invention in which only one of the two phases is colored are also advantageous according to the invention. The dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In in most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (for example Fe ₂ O ₃ , Fe ₃ O, FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

, If there are formulations of the invention in the form of products which are applied on the face, it is favorable as a dye, one or more substandard ^■ zen to select from the following group: 2,4-dihydroxyazobenzene, 1- (2'-chloro- 4'-nitro-T-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1,2'-azonaphthalene-1 '-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid , Aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthyl-azo) -2-naphthol-3,6-disulfonic acid, 1 - (4-Sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1 - (4-sulfophenyl) -5-hydroxy-pyrazolon-3 -carbonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluor orescein, S '^'. δ'.θ'-tetrachlor ^^. S ^ -tetrabromo-fluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigo disulfonic acid , red and black iron oxide (CIN: 77491 (red) and 77499 (black)), iron oxide hydrate (CIN: 77492), manganese ammonium diphosphate and titanium dioxide.

Also advantageous are oil-soluble natural dyes, such as. B. paprika extracts, ß-carotene or cochineal.

Formulations containing pearlescent pigments are also advantageous for the purposes of the present invention. The types of pearlescent pigments listed below are particularly preferred:

1. Natural pearlescent pigments, such as. B.

■ "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and

■ "mother-of-pearl" (ground mussel shells)

2. Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI) 3. Layer-substrate pigments: e.g. B. mica / metal oxide

Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. B. the gloss pigment listed under CIN 77163.

The following pearlescent pigment types based on mica / metal oxide are also advantageous:

Z are particularly preferred. B. the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.

The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Are advantageous for. B. with TiO ₂ and Fe ₂ O ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles. It can also be advantageous to do without a substrate such as mica. Iron pearlescent pigments which are produced without the use of mica are particularly preferred. Such pigments are e.g. B. available under the trade name Sicopearl Kupfer 1000 from BASF.

Also particularly advantageous are effect pigments, which are available from Flora Tech under the trade name Metasomes Standard / Glitter in various colors (yello, red, green, blue). The glitter particles are present in mixtures with various auxiliaries and dyes (such as, for example, the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

The dyes and pigments can be present either individually or in combination, and can be mutually coated, different color effects generally being produced by different coating thicknesses. The total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 to 15 wt .-%, in particular from 1.0 to 10 wt .-%, each based on the total weight of the preparations.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ™), iodopropyl butyl carbamate (for example those under the trade names Glycacil-L , Glycacil-S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate, such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, Benzoic acid and the like. According to the invention, the preservation system usually also advantageously comprises preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.

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

It is also advantageous according to the invention to store the preparation according to the invention in clear and / or translucent packaging containers.

The viscosities of the preparations according to the invention are advantageously between aqueous thin (0-700 mPas) up to a flowable consistency (700-4000 mPas). The very low viscosity preparations could be used in containers with pump systems as a spray or as a fluid.

In the two-phase preparation according to the invention, the choice of which phase floats on the other can be determined in a simple manner which is obvious to the person skilled in the art. As is generally known, the layer sequence of the individual phases depends on their density. This can be adjusted almost arbitrarily by varying the concentration of individual components of the respective phases. Furthermore, the person skilled in the art is of course aware that the demixing speed of the two phases, after the preparation has been homogenized by shaking, can also be set in a targeted manner by selecting the density of the individual phases, the principle that the demixing speed increases with the difference in density of the two phases , Since the compositions of both phases can be varied according to the invention, the layer sequence and the separation rate can also be varied according to the invention.

The preparations according to the invention can advantageously be used according to the invention as a cream or lotion. Their use in the form of a spray, e.g. of a pump spray advantageous according to the invention, the preparations advantageously also being able to be foamed.

In addition, the use of W / O emulsifiers to adjust the phase separation speed of homogenized sunscreen preparations and the use of preparations according to the invention as sunscreen after they have been homogenized by shaking are in accordance with the invention. The preparations according to the invention are particularly preferably stored and presented in transparent or translucent packaging.

In principle, two processes are suitable for the preparations according to the invention for their preparation.

Procedure 1:

Step 1:

Production of a W / O emulsion by a process common to the person skilled in the art. 2nd step:

Production of an aqueous or lipophilic phase by, if necessary, heating to up to 90 ° C. in order to dissolve less soluble substances.

3rd step:

Mixing of the W / O emulsion produced in step 1 with the aqueous or lipophilic phase prepared in step 2. The mixing can be done by simple stirring up to a strong homogenization. For this purpose, the W / O emulsion is placed in a sufficiently large container and then the aqueous - or the lipophilic phase is added with stirring. The rate of segregation can be influenced by the strength of the stirring or homogenization. In contrast to a low energy input (simple stirring), the complete separation of the two phases is slowed down by a high energy input. It is advisable to ensure a sufficiently good homogenization before filling into the final containers. Or alternatively both phases are filled one after the other (layered) into the final containers. With this type of filling, usually the volumes of the individual phases can be set even more precisely.

In this process, the phase-volume ratios of the W / O emulsion to the aqueous or lipophilic phase can be set in a ratio of 1: 3 to 3: 1 for the 2-phase product.

Procedure 2:

In this method, the two-phase system is made according to a method known to the person skilled in the art

Process for producing a W / O emulsion. After manufacturing begins the aqueous or lipophilic phase separates within 1 second to 1 hour.

In contrast to method 1, the phase-volume ratio is determined for this production before the production of the W / O emulsion. That For a 2-phase system consisting of a W / O emulsion and a lipophilic phase which is to be produced using this method, the total oil phase concentration can be between 10 and 95% by weight, in particular between 15 and 90% by weight. For a 2-phase system consisting of a W / O emulsion and an aqueous phase which is to be produced by this process, the total water phase concentration can be between 10 and 95% by weight, in particular between 15 and 90% by weight. For the filling of two-phase systems, which have been produced using process 2, a particularly good homogenization before filling or, on the other hand, filling with stirring is suitable. With both filling variants, it must be ensured that a constant phase volume ratio is maintained.

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

Examples:

1. 2-phase systems produced by method 1 with a W / O emulsion and a lipophilic phase.

The respective phases (a) and (b) can be mixed with one another in phase-to-volume ratios of 3: 1 to 1: 3. The separation speed until the phases are clearly separated is between 1 minute and 1 hour.

The 2-phase systems produced in this way can be used as very low-viscosity sprays or also as low-viscosity / free-flowing lotions / fluids.

2. 2-phase systems produced by process 1 with a W / O emulsion and an aqueous phase.

3. 2-phase systems produced by method 2 with a W / O emulsion and an aqueous phase.

The 2-phase systems produced in this way - using method 2 - can be used as very low-viscosity sprays or also as low-viscosity / free-flowing lotions / fluids.

4. 2-phase systems produced by method 2 with a W / O emulsion and a lipophilic phase.

Claims

claims

1. Two-phase cosmetic and / or dermatological sun protection preparations containing a) a W / O emulsion, b) a lipophilic or aqueous phase, c) at least one W / O emulsifier, d) at least one organic and / or inorganic UV filter, characterized in that at least one phase is not transparent and / or translucent.

2. Sun protection preparations according to claim 1, characterized in that they contain a lipophilic or aqueous phase in an amount of 5 to 95 vol .-%, in particular 0 to 90 vol .-%, based on the total volume of the formulation.

3. Sun protection preparations according to claim 1 or 2, characterized in that they contain one or more W / O emulsifiers in a concentration of 0.1 to 3% by weight.

4. Sunscreen preparations according to claims 1 to 3, characterized in that cetyldimethicone copolyol, glyceryl isostearate, polyglyceryl-2-dipolyhydroxystearate and / or PEG-30 dipolyhydroxystearate are used as W / O emulsifiers.

5. Sun protection preparations according to claim 1 to 4, characterized in that asymmetrically substituted triazines, bisimidazylates, benzotriazoles and / or UV filters which are liquid at room temperature are used as the organic UV filters.

6. Sun protection preparations according to claim 1 to 5, characterized in that titanium dioxide and / or zinc oxide is used as the inorganic pigmentary UV filter.

7. Sun protection preparations according to claim 1 to 6, characterized in that they are stored in clear and / or translucent packaging containers and are used from these.

8. A method for producing sunscreen preparations according to one of the preceding claims, characterized in that the W / O emulsion and the lipophilic or aqueous phase are first prepared in separate vessels and then combined.

9. Use of W / O emulsifiers according to one of the preceding claims for adjusting the phase separation speed of homogenized sunscreen preparations according to one of claims 1 to 7.

10. Use of sunscreen preparations according to one of the preceding claims as a sunscreen after it has been homogenized by shaking.