Microcapsules-vi

FIELD OF THE INVENTION

[0001] The invention is in the field of encapsulation of active ingredients and relates to novel microcapsules, to a process for their preparation, and to their use in the field of cosmetics, pharmacy and food additives.

PRIOR ART

[0002] The term “microcapsule” is to be understood as meaning spherical aggregates with a diameter in the range from about 0.1 to about 5 mm which comprise at least one solid or liquid core which is surrounded by at least one continuous shell. More precisely, they are finely disperse liquid or solid phases surrounded by film-forming polymers, during the preparation of which the polymers, following emulsification and coacervation or interfacial polymerization, are deposited onto the material to be enclosed. In another process, liquid active ingredients are taken up in a matrix (“microsponge”) which, as microparticles, may additionally be coated with film-forming polymers. The microscopically small capsules, also called nanocapsules, can be dried like powders. As well as single-core microcapsules, multicore aggregates, also called microspheres, are also known which contain two or more cores distributed in the continuous shell material. Single- or multicore microcapsules can additionally be surrounded by an additional second, third etc. shell. The shell can consist of natural, semisynthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid and its salts, e.g. sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolyzates, sucrose and waxes. Semisynthetic shell materials are, inter alia, chemically modified celluloses, in particular cellulose esters and ethers, e.g. cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and starch derivatives, in particular starch ethers and esters. Synthetic shell materials are, for example, polymers, such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

[0003] Examples of microcapsules of the prior art are the following commercial products (the shell material is in each case given in brackets): Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapseln (alginic acid, agar agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropyl-methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids).

[0004] In this connection, reference may be made to the German patent application DE 19712978 A1 (Henkel), which discloses chitosan microspheres which are obtained by mixing chitosans or chitosan derivatives with oil bodies and introducing these mixtures into surfactant solutions which have been made alkaline. German patent application DE 19756452 A1 (Henkel) also discloses the use of chitosan as encapsulation material for tocopherol.

[0005] The active ingredients are usually released from the microcapsules during application of the preparations comprising them by destruction of the shell as a result of mechanical, thermal, chemical or enzymatic action. In this connection, it is disadvantageous that the microcapsules only permit controlled release of the active ingredients from their insides to an inadequate degree, if at all, and the capsules have inadequate stability in the presence of surfactants, especially anionic surfactants. The object of the present invention was therefore to overcome these disadvantages.

DESCRIPTION OF THE INVENTION

[0006] The invention provides microcapsules with average diameters in the range from 0.1 to 5 mm which are obtainable by

[0007] (a) processing aqueous active ingredient preparations with oil bodies in the presence of emulsifiers to give O/W emulsions,

[0008] (b) treating the resulting emulsions with aqueous solutions of anionic polymers,

[0009] (c) bringing the resulting matrix into contact with aqueous chitosan solutions and

[0010] (d) separating off the resulting encapsulation products from the aqueous phase.

[0011] The novel microcapsules are formed here by coacervation between the anionic polymers and the cationic chitosans which takes place at the lipophilic interfaces of the O/W emulsion droplets. In this way, it is also possible to encapsulate those substances for which this is usually very difficult. In addition, the microcapsules are characterized by significantly improved surfactant stability.

[0012] The invention further provides a process for the preparation of microcapsules with average diameters in the range from 0.1 to 5 mm in which

[0013] (a) aqueous active ingredient preparations are processed with oil bodies in the presence of emulsifiers to give O/W emulsions,

[0014] (b) the resulting emulsions are treated with aqueous solutions of anionic polymers,

[0015] (c) the resulting matrix is brought into contact with aqueous chitosan solutions and

[0016] (d) the resulting encapsulation products are separated off from the aqueous phase.

[0017] Active Ingredients

[0018] The choice of active ingredients to be encapsulated is unimportant per se. They should be water- or oil-soluble substances which may be chosen, for example, from the group of fats and waxes, pearlescent waxes, lecithins, phospholipids, biogenic active ingredients, UV light protection factors, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, insect repellents, self-tanning agents, tyrosine inhibitors, perfume oils, dyes and the like.

[0019] Typical examples of fats and waxes are glycerides, i.e. solid or liquid vegetable or animal products which consist essentially of mixed glycerol esters of higher fatty acids, suitable waxes are, inter alia, natural waxes, such as, for example, candellila wax, carnauba wax, japan wax, espartograss wax, cork wax, guaruma wax, ricegerm oil wax, sugarcane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial grease, cerasin, ozokerite (earth wax), petrolatum, paraffin waxes, microcrystalline waxes; chemically modified waxes (hard waxes), such as, for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes, and synthetic waxes, such as, for example, polyalkylene waxes and polyethylene glycol waxes. In addition to the fats, suitable additives are also fat-like substances, such as lecithins and phospholipids. The term lecithins is understood by the person skilled in the art as being those glycerophospholipids which form from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are thus often also referred to in the specialist field as phosphatidylcholines (PC). Examples of natural lecithins which may be mentioned are cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipids usually means mono- and, preferably, diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally considered to be fats. In addition, sphingosines and sphingolipids are also suitable.

[0020] Examples of suitable pearlescent waxes are: alkylene glycol esters, specifically ethylene glycol distearate; fatty acid alkanolamides, specifically coconut fatty acid diethanolamide; partial glycerides, specifically stearic acid monoglyceride; esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, specifically long-chain esters of tartaric acid; fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which have a total of at least 24 carbon atoms, specifically laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and/or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

[0021] UV light protection factors is to be understood as meaning, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and give off the absorbed energy again in the form of longer-wave radiation, e.g. heat. UVB filters may be oil-soluble or water-soluble. Examples of oil-soluble substances are: 3-benzylidenecamphor or 3-benzylidenenorcamphor and derivatives thereof, e.g. 3-(4-methylbenzylidene)-camphor, as described in EP 0693471 Bi; 4-amino-benzoic acid derivatives, preferably 2-ethylhexyl 4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)-benzoate and amyl 4-(dimethylamino)benzoate; esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methyl-benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably di-2-ethyl-hexyl 4-methoxybenzmalonate; triazine derivatives, such as, for example, 2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and Octyl Triazone, as described in EP 0818450 A1 or dioctylbutamido-triazone (Uvasorb® HEB); propane-1,3-diones, such as, for example, 1-(4-tert-butylphenyl)-3-(4′methoxy-phenyl)propane-1,3-dione; ketotricyclo(5.2.1.0)decane derivatives, as described in EP 0694521 B1.

[0022] Suitable water-soluble substances are: 2-phenyl-benzimidazole-5-sulfonic acid and the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof; sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; sulfonic acid derivatives of 3-benzylidenecamphor, such as, for example, 4-(2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl—5-(2-oxo-3-bornylidene)sulfonic acid and salts thereof.

[0023] Suitable typical UV-A filters are, in particular, derivatives of benzoylmethane, such as, for example, 1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione, 4-tert-butyl-4′-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione, and enamine compounds, as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g. 4-tert-butyl-4′-methoxy-dibenzoylmethane (Parsol® 1789) and 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene) in combination with esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate and/or propyl 4-methoxycinnamate and/or isoamyl 4-methoxycinnamate. Those combinations with water-soluble filters, such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof, are advantageously combined.

[0024] In addition to said soluble substances, insoluble light protection pigments, namely finely disperse metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and also oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. Salts which may be used are silicates (talc), barium sulfate or zinc stearate. The oxides and salts are used in the form of the pigments for skincare and skin-protective emulsions and decorative cosmetics. The particles here should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal shape or a shape deviating in some other way from the spherical form. The pigments can also be surface-treated, i.e. hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides, such as, for example, titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents here are primarily silicones and, specifically in this case, trialkoxyoctylsilanes or simethicones. In sunscreens, preference is given to using micropigments or nanopigments. Preference is given to using micronized zinc oxide. Further suitable UV light protection filters are given in the review by P. Finkel in SÖFW-Journal 122, 543 (1996) and Parf.Kosm. 3, 11 (1999).

[0025] As well as the two abovementioned groups of primary light protection substances, it is also possible to encapsulate secondary light protection agents of the antioxidant type; these interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples thereof are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propyl-thiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof), and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g. pmol to μmol/kg), and also (metal) chelating agents (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, 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), and coniferyl benzoate of benzoin resin, rutic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, zinc and derivatives thereof (e.g. ZnO, ZnSO4) selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active ingredients which are suitable according to the invention.

[0026] Biogenic active ingredients are to be understood, for example, as meaning tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and fragmentation products thereof, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

[0027] Suitable antimicrobial agents are, in principle, all substances effective against Gram-positive bacteria, such as, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea, 2,4,4′-trichloro-2′-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethyl-phenol, 2,2′-methylenebis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chloro-phenol, 3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, oil of cloves, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid N-alkylamides, such as, for example, n-octylsalicylamide or n-decylsalicylamide.

[0028] Suitable enzyme inhibitors are, for example, esterase inhibitors. These are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and, in particular, triethyl citrate (Hydagen CAT). The substances inhibit enzyme activity, thereby reducing the formation of odor. Other substances which are suitable esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, such as, for example, glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and esters thereof, such as, for example, citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

[0029] Suitable odor absorbers are substances which are able to absorb and largely retain odor-forming compounds. They lower the partial pressure of the individual components, thus also reducing their rate of diffusion. It is important that in this process perfumes must remain unimpaired. Odor absorbers are not effective against bacteria. They comprise, for example, as main constituent, a complex zinc salt of ricinoleic acid or specific, largely odor-neutral fragrances which are known to the person skilled in the art as “fixatives”, such as, for example, extracts of labdanum or styrax or certain abietic acid derivatives. The odor masking agents are fragrances or perfume oils, which, in addition to their function as odor masking agents, give the deodorants their respective fragrance note. Perfume oils which may be mentioned are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts from flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches, and resins and balsams. Also suitable are animal raw materials, such as, for example, civet and castoreum. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, and the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the ionones and methyl cedryl ketone, the alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linaool, phenylethyl alcohol and terpineol, and the hydrocarbons include mainly the terpenes and balsams. Preference is, however, given to using mixtures of different fragrances which together produce a pleasing fragrance note. Essential oils of relatively low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavandin oil. Preference is given to using bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur, iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat alone or in mixtures.

[0030] Suitable astringent antiperspirant active ingredients are primarily salts of aluminum, zirconium or of zinc. Such suitable antihydrotic active ingredients are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and complex compounds thereof, e.g. with 1,2-propylene glycol, aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complex compounds thereof, e.g. with amino acids, such as glycine.

[0031] Suitable antidandruff active agents are Piroctone Olamine (1-hydroxy-4-methyl-6-(2,4,4-trimythyl-pentyl)-2-(1H)-pyridone monoethanolamine salt), Baypival® (climbazole), Ketoconazol®, (4-acetyl-1-{4-[2-(2,4-dichlorophenyl) r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}piperazine, ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monoleate, sulfur ricinol polyethoxylate, sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid monoethanolamide-sulfosuccinate Na salt, Lamepon® UD (protein-undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione/dipyrithione magnesium sulfate.

[0032] Suitable insect repellants are N,N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionate. A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosine inhibitors, which prevent the formation of melanin and are used in depigmentation agents, are, for example, arbutin, ferulic acid, kojic acid, coumaric acid and ascorbic acid (vitamin C).

[0033] Perfume oils which can be encapsulated and which may be mentioned are: mixtures of natural and synthetic fragrances. Natural fragrances are extracts from flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, cumin, juniper), fruit peels (bergamot, lemon, orange), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine wood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf-pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Also suitable are animal raw materials, such as, for example, civet and castoreum. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl-methylphenyl glycinate, allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the ionones, α-isomethylionone and methyl cedryl ketone, the alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, and the hydrocarbons include predominantly the terpenes and balsams. Preference is, however, given to using mixtures of different fragrances which together produce a pleasing fragrance note. Essential oils of relatively low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to using bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat alone or in mixtures.

[0034] Finally, dyes which can be used are the substances which are approved and suitable for cosmetic purposes, as are listed, for example, in the publication “Kosmetische Färbemittel” [Cosmetics Colorants] from the Farbstoffkommission der Deutschen Forschungsgemeinschaft [Dyes Commission of the German Research Council], Verlag Chemie, Weinheim, 1984, pp. 81-106.

[0035] All said active ingredients are used, based on the microcapsules, usually in concentrations of from 0.001 to 10% by weight, preferably 0.5 to 5% by weight and in particular 1 to 2% by weight.

[0036] Oil Bodies

[0037] Suitable oil bodies, which form constituents of the O/W emulsions, are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18-C38-alkylhydroxy carboxylic acids with linear or branched C6-C22-fatty alcohols (cf. DE 19756377 A1), in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades etc.) and/or aliphatic or naphthenic hydrocarbons, such as, for example, such as squalane, squalene or dialkylcyclohexanes. The amount of oil bodies may be 10 to 30% by weight and preferably 15 to 30% by weight, based on the microcapsules.

[0038] Emulsifiers

[0039] Suitable emulsifiers are, in principle, anionic, cationic or ampholytic surfactants. However, preference is given to using nonionogenic surfactants, which may be chosen, for example, from at least one of the following groups.

[0040] Addition products of from 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, onto fatty acids having 12 to 22 carbon atoms, onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, and alkylamines having 8 to 22 carbon atoms in the alkyl radical;

[0041] Alkyl and/or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alk(en)yl radical and ethoxylated analogs thereof;

[0042] Addition products of from 1 to 15 mol of ethylene oxide onto castor oil and/or hydrogenated castor oil;

[0043] Addition products of from 15 to 60 mol of ethylene oxide onto castor oil and/or hydrogenated caster oil;

[0044] Partial esters of glycerol and/or sorbitan with unsaturated, linear or saturated, branched fatty acids having 12 to 22 carbon atoms and/or hydroxy-carboxylic acids having 3 to 18 carbon atoms, and adducts thereof with 1 to 30 mol of ethylene oxide;

[0045] Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside), and polyglucosides (e.g. cellulose) with saturated and/or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and/or hydroxycarboxylic acids having 3 to 18 carbon atoms, and adducts thereof with 1 to 30 mol of ethylene oxide;

[0046] Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols as in German patent DE 1165574 and/or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerol or polyglycerol,

[0047] Mono-, di- and trialkyl phosphates, and mono-, di-and/or tri-PEG alkyl phosphates and salts thereof;

[0048] Wool wax alcohols;

[0049] Polysiloxane-polyalkyl-polyether copolymers and corresponding derivatives;

[0050] Block copolymers, e.g. polyethylene glycol-30 dipolyhydroxystearate;

[0051] Polymer emulsifiers, e.g. Pemulen grades (TR-1, TR-2) from Goodrich;

[0052] Polyalkylene glycols and

[0053] Glycerol carbonate.

[0054] The addition products of ethylene oxide and/or of propylene oxide onto fatty alcohols, fatty acids, alkylphenols or onto castor oil are known commercially available products. These are homolog mixtures whose average degree of alkoxylation corresponds to the ratio of the quantitative amounts of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C12/18-fatty acid mono- and diesters of addition products of ethylene oxide onto glycerol are known from German patent DE 2024051 as refatting agents for cosmetic preparations.

[0055] Alkyl and/or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are prepared, in particular, by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides, in which a cyclic sugar radical is glycosidically bonded to the fatty alcohol, and also oligomeric glycosides having a degree of oligomerization of up to, preferably, about 8, are suitable. The degree of oligomerization here is a statistical average value which is based on a homolog distribution customary for such technical-grade products.

[0056] Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid moglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, malic acid diglyceride, and the technical-grade mixtures thereof which may also comprise small amounts of triglyceride as a minor product of the preparation process. Likewise suitable are addition products of 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide onto said partial glycerides.

[0057] Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate, and technical-grade mixtures thereof. Likewise suitable are addition products of from 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide onto said sorbitan esters.

[0058] Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3 diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (Polyglycerol Caprate T2010/90), polyglyceryl-3 cetyl ether (Chimexane® NL), polyglyceryl-3 distearate (Cremophor® GS 32) and polyglyceryl polyricinoleate (Admul® WOL 1403), polyglyceryl dimerate isostearate, and mixtures thereof. Examples of other suitable polyesters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.

[0059] The concentration of the emulsifiers may be 1 to 10% by weight and preferably 2 to 8% by weight, based on the microcapsules.

[0060] Anionic Polymers

[0061] Suitable anionic polymers are, in addition to anionic polysaccharides, such as, for example, carboxymethylcellulose, or poly(meth)acrylic acids and derivatives thereof, such as, for example, salts and esters, preferably salts of alginic acid. Alginic acid is a mixture of carboxyl-group-containing polysaccharides having the following idealized monomer building block:

[0062] The average molecular weight of the alginic acids or of the alginates is in the range from 150 000 to 250 000. In this connection, the salts of alginic acid are to be understood as meaning both their complete and also their partial neutralization products, in particular the alkali metal salts and, of these, preferably sodium alginate (“algin”), and the ammonium and alkaline earth metal salts. Particular preference is given to mixed alginates, such as, for example, sodium/magnesium or sodium/calcium alginates. In an alternative embodiment of the invention, however, anionic chitosan derivatives are also suitable for this purpose, such as, for example, carboxylation and especially succinylation products, as are described, for example, in German patent specification DE 3713099 C2 (L'Oréal), and the German patent application DE 19604180 A1 (Henkel). The amount of anionic polymers used is usually 0.01 to 1% by weight, preferably 0.05 to 0.1% by weight, based on the microcapsules.

[0063] Chitosans

[0064] Chitosans are biopolymers and belong to the group of hydrocolloids. With the anionic polymers, they form membranes. When considered chemically, they are partially deacetylated chitins of varying molecular weight which contain the following—idealized—monomer building block:

[0065] In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair care and body care compositions and also pharmaceutical preparations (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, p. 231-232). Reviews on this topic have also been published, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and E. Onsoyen et al. in Seifen-Öle-Fette-Wachse 117, 633 (1991). The chitosans are prepared starting from chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large amounts. In this connection, the chitin is usually, in a process which was described for the first time by Hackmann et al., deproteinated by the addition of bases, demineralized by the addition of mineral acids and, finally, deacetylated by the addition of strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Corresponding processes are known, for example, from Makromol. Chem. 177, 3589 (1976) or the French patent application FR 2701266 A. Preference is given to using those grades disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) and which have an average molecular weight of from 10 000 to 500 000 or 800 000 to 1 200 000 daltons and/or have a viscosity in accordance with Brookfield (1% strength in glycolic acid) of less than 5 000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight. For reasons of better solubility in water, the chitosans are usually used in the form of their salts, preferably as glycolates. The amount of chitosans used is preferably in the range from 0.01 to 1% by weight, preferably 0.05 to 0.1% by weight, based on the microcapsules.

[0066] Preparation of the Microcapsules

[0067] To prepare the microcapsules according to the invention, an O/W emulsion is firstly prepared which, in addition to the oil body, water and the active ingredient, comprises an effective amount of emulsifier. To prepare the matrix, an appropriate amount of an aqueous anionic polymer solution is added to this preparation with vigorous stirring. The membrane is formed by adding the chitosan solution. The entire operation preferably takes place in the weakly acidic range at pH=3 to 4. If necessary, the pH is adjusted by adding mineral acid. Following membrane formation, the pH is raised to 5 to 6, for example by adding triethanolamine or another base. This results in an increase in the viscosity, which can be aided further by adding further thickeners, such as, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and Tyloses, carboxymethylcellulose and hydroxyethylcellulose, higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyacrylamides and the like. Finally, the microcapsules are separated off from the aqueous phase by, for example, decantation, filtration or centrifugation.

[0068] Industrial Applicability

[0069] The invention further relates to the use of the microcapsules according to the invention for the preparation of cosmetic and/or pharmaceutical preparations, such as, for example, hair shampoos, hair lotions, foam baths, shower preparations, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fatty compositions, stick preparations, powders or ointments. These may in turn again comprise active ingredients, oil bodies and emulsifiers in nonencapsulated form, as has already been described at the beginning; another list is therefore not necessary.

[0070] The preparations may be food additives, for example additives for athlete food and the like. The microcapsules may be present in these compositions in amounts of from 1 to 50% by weight, preferably 5 to 15% by weight.

EXAMPLES

Example 1

[0071] In a stirred apparatus, 0.5 g of

[0072] preservative (Phenonip®) were dissolved in 50 g of a 2% strength by weight aqueous preparation of carboxymethylcellulose, and the mixture was adjusted to pH=3.5. Then, with vigorous stirring, a mixture consisting of 10 g of a 10% strength by weight solution of retinol in soybean oil (Retinol® S20, BASF) and 0.5 g of sorbitan monostearate+20EO (Eumulgin® SMS 20, Cognis Deutschland GmbH) was added with vigorous stirring. Then, with continued stirring, an amount of a 1% strength by weight solution of chitosan in glycolic acid (Hydagen® CMF Cognis Deutschland GmbH) was added such that a chitosan concentration of 0.075% by weight, based on the preparation, was established. Finally, the pH was raised to 5.5 by adding triethanolamine, and the resulting microcapsules were decanted.

Example 2

[0073] In a stirred apparatus, 0.5 g of preservative (Phenonip®) were dissolved in 50 g of a 2% strength by weight aqueous preparation of polyacrylic acid (Pemulen® TR-2), and a pH of 3 was established. Then, with vigorous stirring, a mixture consisting of 10 g of a 10% strength by weight solution of retinol in soybean oil (Retinol® S20, BASF) and 0.5 g of sorbitan monolaurate+15EO (Eumulgin® SML 15, Cognis Deutschland GmbH) was added. Then, with continued stirring, an amount of a 1% strength by weight solution of chitosan in glycolic acid (Hydagen® CMF Cognis Deutschland GmbH) was added such that a chitosan concentration of 0.01% by weight, based on the preparation, was established. Finally, the pH was raised to 5.5 by adding triethanolamine, and the resulting microcapsules were decanted.

Example 3

[0074] In a stirred apparatus, 0.5 g of preservative (Phenonip®) were dissolved in 50 g of a 2% strength by weight aqueous preparation of polyacrylic acid (Pemulen® TR-2), and a pH of 3 was established. Then, with vigorous stirring, a mixture consisting of 5 g of a solution of tocopherol in mineral oil and 0.5 g of coco glucosides (Plantacare APG 1200, Cognis Deutschland GmbH) was added. Then, with continued stirring, an amount of a 1% strength by weight solution of chitosan in glycolic acid (Hydagen® CMF Cognis Deutschland GmbH) was added such that a chitosan concentration of 0.01% by weight, based on the preparation, was established. Finally, the pH was raised to 5.5 by adding triethanolamine, and the resulting microcapsules were decanted.

[0075] Table 1 gives a number of formulation examples.

1TABLE 1Cosmetic preparations (water, preservative ad 100% by weight)Composition (INCI)12345678910Texapon ® NSO——————38.0 38.0 25.0 —Sodium Laureth SulfateTexapon ® SB 3————————10.0 —Disodium Laureth SulfosuccinatePlantacare ® 818——————7.07.06.0—Coco GlucosidesPlantacare ® PS 10—————————16.0 Sodium Laureth Sulfate (and) Coco GlucosidesDehyton ® PK 45————————10.0 —Cocamidopropyl BetaineDehyquart ® A2.02.02.02.04.04.0————Cetrimonium ChlorideDehyquart L ® 801.21.21.21.20.60.6————Dicocoylmethylethoxymonium Methosulfate (and)Propylene Glycol)Eumulgin ® B20.80.8—0.8—1.0————Ceteareth-20Eumulgin ® VL 75——0.8—0.8—————Lauryl Glucoside (and) Polyglyceryl-2-Polyhydroxy-stearate (and) GlycerolLanette ® O2.52.52.52.53.02.5————Cetearyl AlcoholCutina ® GMS0.50.50.50.50.51.0————Glyceryl StearateCetiol ® HE1.0———————1.0PEG-7 Glyceryl CocoateCetiol ® PGL—1.0——1.0—————Hexyldecanol (and) Hexyldecyl LaurateCetiol ® V———1.0——————Decyl OleateEutanol ® G——1.0——1.0————OctyldodecanolNutrilan ® Keratin W———2.0——————Hydrolyzed KeratinLamesoft ® LMG——————3.02.04.0—Glyceryl Laurate (and) Potassium CocoylHydrolyzed CollagenEuperlan ® PK 3000 AM———————3.05.05.0Glycol Distearate (and) Laureth-4 (and) Cocamido-propyl BetaineGenerol ® 122 N————1.01.0————Soya SterolTocopherol Microcapsules as in example 31.01.01.01.01.01.01.01.01.01.0Hydagen ® CMF1.01.01.01.01.01.01.01.01.01.0ChitosanHighcareen ® GS——0.10.1——————Beta GlucanArlypon ® F——————3.03.01.0—Laureth-2Sodium Chloride———————1.5—1.5Composition (INCI)11121314151617181920Texapon ® NSO20.0 20.0 12.4 —25.0 11.0 ————Sodium Laureth SulfateTexapon ® K14 S————————11.0 23.0 Sodium Myreth SulfateTexapon ® SB 3—————7.0————Disodium Laureth SulfosuccinatePlantacare ® 8185.05.04.0—————6.04.0Coco GlucosidesPlantacare ® 2000————5.04.0————Decyl GlucosidePlantacare ® PS 10———40.0 ——16.0 17.0 ——Sodium Laureth Sulfate (and) Coco GlucosidesDehyton ® PK 4520.0 20.0 ——8.0————7.0Cocamidopropyl BetaineEumulgin ® B1————1.0—————Ceteareth-12Eumulgin ® B2———1.0——————Ceteareth-20Lameform ® TGI———4.0——————Polyglyceryl-3 IsostearateDehymuls ® PGPH——1.0———————Polyglyceryl-2 DipolyhydroxystearateMonomuls ® 90-L 12————————1.01.0Glyceryl LaurateCetiol ® HE—0.2————————PEG-7 Glyceryl CocoateEutanol ® G———3.0——————OctyldodecanolNutrilan ® Keratin W————————2.02.0Hydrolyzed KeratinNutralin ® I1.0————2.0—2.0——Hydrolyzed CollagenLamesoft ® LMG————————1.0—Glyceryl Laurate (and) Potassium CocoylHydrolyzed CollagenLamesoft ® 156—————————5.0Hydrogenated Tallow Gyceride (and)Potassium Cocoyl Hydrolyzed CollagenGluadin ® WK1.01.54.01.03.01.02.02.02.0—Sodium Cocoyl Hydrolyzed Wheat ProteinEuperlan ® PK 3000 AM5.03.04.0————3.03.0—Glycol Distearate (and) Laureth-4 (and)Cocamidopropyl BetaineArlypon ® F2.61.6—1.01.5—————Laureth-2Tocopherol Microcapsules as in example 31.01.01.01.01.01.01.01.01.01.0Hydagen ® CMF1.01.01.01.01.01.01.01.01.01.0ChitosanSodium Chloride—————1.62.02.2—3.0Glycerol (86% strength by weight)—5.0—————1.03.0—Composition (INCI)21222324252627282930Texapon ® NSO—30.0 30.0 —25.0 —————Sodium Laureth SulfatePlantacare ® 818—10.0 ——20.0 —————Coco GlucosidesPlantacare ® PS 1022.0 —5.022.0 ——————Sodium Laureth Sulfate and Coco GlucosidesDehyton ® PK 4515.0 10.0 15.0 15.0 20.0 —————Cocamidopropyl BetaineEmulgade ® SE—————5.05.04.0——Glyceryl Sterate (and) Ceteareth 12/20 (and)Cetearyl Alcohol (and) Cetyl PalmitateEumulgin ® B1———————1.0——Ceteareth-12Lameform ® TGI————————4.0—Polyglyceryl-3 IsostearateDehymuls ® PGPH—————————4.0Polyglyceryl-2 DipolyhydroxystearateMonomuls ® 90-O 18————————2.0—Glyceryl OleateCetiol ® HE2.0——2.05.0————2.0PEG-7 Glyceryl CocoateCetiol ® OE————————5.06.0Dicaprylyl EtherCetiol ® PGL———————3.010.0 9.0Hexyldecanol (and) Hexyldecyl LaurateCetiol ® SN—————3.03.0———Cetearyl IsononanoateCetiol ® V—————3.03.0———Decyl OleateMyritol ® 318———————3.05.05.0Coco Caprylate CaprateBees wax————————7.05.0Nutrilan ® Elastin E20—————2.0————Hydrolyzed ElastinNutrilan ® I-50————2.0—2.0———Hydrolyzed CollagenGluadin ® AGP0.50.50.5————0.5——Hydrolyzed Wheat GlutenGluadin ® WK2.02.02.02.05.0———0.50.5Sodium Cocoyl Hydrolyzed Wheat ProteinEuperlan ® PK 3000 AM5.0——5.0——————Glycol Distearate (and) Laureth-4 (and) Cocamido-propyl BetaineArlypon ® F——————————Laureth-2Retinol Microcapsules as in example 11.01.01.01.01.01.01.01.01.01.0Hydagen ® CMF1.01.01.01.01.01.01.01.01.01.0ChitosanMagnesium Sulfate Hepta Hydrate————————1.01.0Glycerol (86% strength by weight)—————3.03.05.05.03.0Composition (INCI)31323334353637383940Dehymuls ® PGPH4.03.0—5.0——————Polyglyceryl-2 DipolyhydroxystearateLameform ® TGI2.01.0————————Polyglyceryl-3 DiisostearateEmulgade ® PL 68/50————4.0———3.0—Cetearyl Glucoside (and) Cetearyl AlcoholEumulgin ® B2———————2.0——Ceteareth-20Tegocare ® PS——3.0———4.0———Polyglyceryl-3 Methylglucose DistearateEumulgin VL 75—————3.5——2.5—Polyglyceryl-2 Dipolyhydroxystearate (and)Lauryl Glucoside (and) GlycerolBees wax3.02.05.02.0——————Cutina ® GMS—————2.04.0——4.0Glyceryl StearateLanette ® O——2.0—2.04.02.04.04.01.0Cetearyl AlcoholAntaron ® V 216—————3.0———2.0PVP/Hexadecene CopolymerMyritol ® 8185.0—10.0 —8.06.06.0—5.05.0CocoglyceridesFinsolv ® TN—6.0—2.0——3.0——2.0C12/15 Alkyl BenzoateCetiol ® J 6007.04.03.05.04.03.03.0—5.04.0Oleyl ErucateCetiol ® OE3.0—6.08.06.05.04.03.04.06.0Dicaprylyl EtherMineral Oil—4.0—4.0—2.0—1.0——Cetiol ® PGL—7.03.07.04.0———1.0—Hexadecanol (and) Hexyldecyl LaurateBisabolol1.21.21.21.21.21.21.21.21.21.2Retinol Microcapsules as in example 11.01.01.01.01.01.01.01.01.01.0Hydagen ® CMF1.01.01.01.01.01.01.01.01.01.0ChitosanCopherol ® F 13000.51.01.02.01.01.01.02.00.52.0Tocopherol/Tocopheyl AcetateNeo Heliopan ® Hydro3.0——3.0——2.0—2.0—Sodium Phenylbenzimidazole SulfonateNeo Heliopan ® 303—5.0———4.05.0——10.0 OctocryleneNeo Heliopan ® BB1.5——2.01.5———2.0—Benzophenone-3Neo heliopan ® E 10005.0—4.0—2.02.04.010.0 ——Isoamyl p-MethoxycinnanateNeo Heliopan ® AV4.0—4.03.02.03.04.0—10.0 2.0Octyl MethoxycinnamateUnivul ® T 1502.04.03.01.01.01.04.03.03.03.0Octyl TriazoneZinc Oxide—6.06.0—4.0————5.0Titanium Dioxide———————5.0——Glycerol (86% strength by weight)5.05.05.05.05.05.05.05.05.05.0(1-4) Hair rinse, (5-6) Hair cure, (7-8) Shower preparation, (9) Shower gel, (10) Washing lotion (11-14) Shower preparation “Two-in-One), (15-20) Shampoo (21-25) Foam bath, (26) Soft cream, (27, 28) Moisturizing emulsion, (29, 30) Night cream (31) W/O sunscreen cream, (32-34) W/O sunscreen lotion, (35, 38, 40) O/W sunscreen lotion

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