US20100278882A1 - Use of protein microbeads in cosmetics - Google Patents

Use of protein microbeads in cosmetics Download PDF

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US20100278882A1
US20100278882A1 US12/161,352 US16135207A US2010278882A1 US 20100278882 A1 US20100278882 A1 US 20100278882A1 US 16135207 A US16135207 A US 16135207A US 2010278882 A1 US2010278882 A1 US 2010278882A1
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protein
acid
microbead
microbeads
phase
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Burghard Liebmann
Marcus Fehr
Arne Ptock
Thomas Scheibel
Daniel Hümmerich
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1629—Organic macromolecular compounds
    • A61K9/1658—Proteins, e.g. albumin, gelatin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/671—Vitamin A; Derivatives thereof, e.g. ester of vitamin A acid, ester of retinol, retinol, retinal
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

Definitions

  • the present invention relates to the use of protein microbeads in cosmetics, in particular in skin cosmetics.
  • EP 1110534 describes a cosmetic product of ultrafine crystalline silk powder which is produced by treating silk under alkaline conditions at a temperature above 100° C. and subsequent mechanical comminution.
  • the present invention relates, in a first embodiment, to the use of protein microbeads in cosmetics.
  • Protein microbeads consist of polypeptides which are constructed from amino acids, in particular from the 20 naturally occurring amino acids.
  • the amino acids can also be modified, for example acetylated, glycosylated, farnesylated.
  • the protein microbeads have a globular structure with an average particle diameter of from 0.1 to 100 ⁇ m, in particular from 0.5 to 20 ⁇ m, preferably from 1 to 5 ⁇ m and particularly preferably from 2 to 4 ⁇ m.
  • Protein microbeads can preferably be produced by the method described below:
  • Solvents which can be used are, for example, aqueous salt solutions.
  • aqueous salt solutions In particular, highly concentrated salt solutions with a concentration greater than 2 molar, in particular greater than 4 molar and particularly preferably greater than 5 molar, whose ions have more marked chaotropic properties than sodium ions and chloride ions are suitable.
  • a salt solution is 6 M guanidinium thiocyanate or 9 M lithium bromide.
  • organic solvents can be used for dissolving the proteins.
  • fluorinated alcohols or cyclic hydrocarbons are suitable. Examples thereof are hexafluoroisopropanol and cyclohexane.
  • the protein microbeads can be produced in the described solvents. Alternatively, this solvent can be replaced by a further solvent, e.g. low-concentration salt solutions (c ⁇ 0.5 M) through dialysis or dilution.
  • the end concentration of the dissolved protein should be between 0.1-100 mg/ml.
  • the temperature at which the method is carried out is usually 0-80° C., preferably 5-50° C. and particularly preferably 10-40° C.
  • aqueous solutions When using aqueous solutions, these may also be admixed with a buffer, preferably in the pH range 4-10, particularly preferably 5 to 9, very particularly preferably 6 to 8.5.
  • a buffer preferably in the pH range 4-10, particularly preferably 5 to 9, very particularly preferably 6 to 8.5.
  • phase separation is induced.
  • emulsified protein-rich droplets adopt a round shape.
  • the average diameter of the protein microbeads can be adjusted to values between 0.1 ⁇ m and 100 ⁇ m.
  • additive all substances can be used which, on the one hand, are miscible with the first solvent and, on the other hand, induce the formation of a protein-rich phase. If the microbead formation is carried out in organic solvents, then organic substances suitable for this purpose are those which have a lower polarity than the solvent, e.g. toluene. In aqueous solutions, salts may be used as additive whose ions have more marked cosmotropic properties than sodium ions and chloride ions (e.g. ammonium sulfate; potassium phosphate). The end concentration of the additive should be between 1% and 50% by weight, based on the protein solution, depending on the type of additive.
  • the protein-rich droplets are fixed by curing, with retention of the round shape.
  • the fixing is based here on the formation of strong intermolecular interactions.
  • the type of interactions may be noncovalent, e.g. through the formation of intermolecular ⁇ -pleated sheet crystals, or covalent, e.g. through chemical crosslinking.
  • the curing can take place through the additive and/or through the addition of a further suitable substance.
  • the curing takes place at temperatures between 0 and 80° C., preferably between 5 and 60° C.
  • This further substance may be a chemical crosslinker.
  • a chemical crosslinker is understood here as meaning a molecule in which at least two chemically reactive groups are joined together via a linker. Examples thereof are sulfhydryl-reactive groups (e.g. maleimides, pydridyldisulfides, ⁇ -haloacetyls, vinylsulfones, sulfatoalkylsulfones (preferably sulfatoethylsulfones)), amine-reactive groups (e.g.
  • carboxy-reactive groups e.g. amines etc.
  • hydroxyl-reactive groups e.g. isocyanates etc.
  • unselective groups e.g. aryl azides etc.
  • photoactivatable groups e.g. perfluorophenyl azide etc.
  • the stabilized microbeads are washed with a suitable further solvent, e.g. water, and then dried by methods known to the person skilled in the art, e.g. by lyophilization or spray-drying.
  • a suitable further solvent e.g. water
  • the success of bead formation is checked with the help of scanning electron microscopy.
  • Suitable proteins for producing protein microbeads are proteins which are present in predominantly intrinsically unfolded form in aqueous solution. This state can be calculated, for example, by an algorithm on which the program IUpred is based (http://iupred.enzim.hu/index.html; The Pairwise Energy Content Estimated from Amino Acid Composition Discriminates between Folded and Intrinsically Unstructured Proteins; Zsuzsanna Dosztányi, Veronika Csizmók, Péter Tompa and István Simon; J. Mol. Biol. (2005) 347, 827-839). A predominantly intrinsically unfolded state is assumed if a value of >0.5 is calculated for more than 50% of the amino acid radicals according to this algorithm (prediction type: long disorder).
  • Suitable proteins for producing protein microbeads are silk proteins. These are understood below as meaning those proteins which comprise highly repetitive amino acid sequences and are stored in the animal in a liquid form and during their secretion fibers are produced by shearing or spinning. (Craig, C. L. (1997) Evolution of arthropod silks. Annu. Rev. Entomol. 42: 231-67).
  • Particularly suitable proteins for producing protein microbeads are spider silk proteins which can be isolated in their original form from spiders.
  • Preferred silk proteins are ADF3 and ADF4 from the “Major Ampullate” gland of Araneus diadematus (Guerette et al., Science 272, 5258:112-5 (1996)).
  • suitable proteins for producing protein microbeads are natural or synthetic proteins which are derived from natural silk proteins and which have been produced using genetic engineering methods heterologously in prokaryotic or eukaryotic expression systems.
  • prokaryotic expression organisms are Escherichia coli, Bacillus subtilis, Bacillus megaterium, Corynebacterium glutamicum etc.
  • Nonlimiting examples of eukaryotic expression organisms are yeasts, such as Saccharomyces cerevisiae, Pichia pastoris etc., filamentous fungi, such as Aspergillus niger, Aspergillus oryzae, Aspergillus nidulans, Trichoderma reesei, Acremonium chrysogenum etc., mammal cells, such as Hela cells, COS cells, CHO cells etc., insect cells, such as Sf9 cells, MEL cells etc.
  • synthetic proteins which are based on repeat units of natural silk proteins.
  • synthetic repetitive silk protein sequences these can additionally comprise one or more natural nonrepetitive silk protein sequences (Winkler and Kaplan, J Biotechnol 74:85-93 (2000)).
  • synthetic silk proteins for producing protein microbeads, preference is given to synthetic spider silk proteins which are based on repeat units of natural spider silk proteins. Besides the synthetic repetitive spider silk protein sequences, these can additionally comprise one or more natural nonrepetitive spider silk protein sequences.
  • the so-called C16-protein is preferably to be specified (Huemmerich et al. Biochemistry, 43(42):13604-13612 (2004)).
  • This protein has the polypeptide sequence shown in SEQ ID NO: 1.
  • “functional equivalents” are understood in particular as meaning also mutants which have an amino acid other than that specifically given in at least one sequence position of the abovementioned amino acid sequences but nevertheless have one of the abovementioned biological properties. “Functional equivalents” thus comprise the mutants obtainable by one or more amino acid additions, substitutions, deletions and/or inversions, where the specified changes can arise in any sequence position provided they lead to a mutant with the profile of properties according to the invention. Functional equivalence is in particular also present if the reactivity patterns between mutant and unchanged polypeptide are in qualitative agreement. “Functional equivalents” in the above sense are also “precursors” of the described polypeptides, and “functional derivatives” and “salts” of the polypeptides.
  • precursors are natural or synthetic precursors of the polypeptides with or without the desired biological activity.
  • salts is understood as meaning either salts of carboxyl groups or acid addition salts of amino groups of the protein molecules according to the invention.
  • Salts of carboxyl groups can be produced in a manner known per se and comprise inorganic salts, such as, for example, sodium, calcium, ammonium, iron and zinc salts, and also salts with organic bases, such as, for example amines, such as triethanolamine, arginine, lysine, piperidine and the like.
  • Acid addition salts such as, for example, salts with mineral acids, such as hydrochloric acid or sulfuric acid and salts with organic acids, such as acetic acid and oxalic acid, are likewise provided by the invention.
  • “Functional derivatives” of polypeptides according to the invention can likewise be produced on functional amino acid side groups or on their N- or C-terminal end using known techniques.
  • Such derivatives comprise, for example, aliphatic esters of carboxylic acid groups, amides of carboxylic acid groups, obtainable by reaction with ammonia or with a primary or secondary amine; N-acyl derivatives of free amino groups, prepared by reaction with acyl groups; or O-acyl derivatives of free hydroxy groups, prepared by reaction with acyl groups.
  • the invention further provides protein microbeads which consist of couplings of a protein (i) and an effector molecule (ii). All of the proteins already specified above are suitable as protein (i).
  • the protein (i) can either itself already be present as protein microbead and then be coupled with an effector molecule (ii), or else the protein (i) is not in the form of a protein microbead and is coupled with the effector molecule (ii) and only then is the coupled molecule converted to a protein microbead or the coupling takes place during phase separation.
  • Effector molecules (ii) are understood below as meaning molecules which have, a certain predictable effect. These may either be protein-like molecules, such as enzymes, or non-proteinogenic molecules, such as dyes, photoprotective agents, vitamins, provitamins, antioxidants and fatty acids, conditioners or compounds comprising metal ions.
  • effector molecules oxidases, peroxidases, proteases, glucanases, mutanase, tyrosinases, laccases, metal-binding enzymes, lactoperoxidase, lysozyme, amyloglycosidase, glucose oxidase, super oxide dismutase, photolyase, T4 endonuclease, katalase, thioredoxin, thioredoxin reductase.
  • effector molecules antimicrobial peptides, hydrophobins, collagen, proteins binding carotenoid, proteins binding heavy metals, proteins binding odorants, proteins binding cellulose, proteins binding starch, proteins binding keratin.
  • Highly suitable protein-like effector molecules (ii) are also hydrolyzates of proteins of vegetable and animal sources, for example hydrolyzates of proteins of marine origin.
  • carotenoids are preferred.
  • carotenoids are understood as meaning the following compounds and their esterified or glycosylated derivatives: ⁇ -carotene, lycopene, lutein, astaxanthin, zeaxanthin, cryptoxanthin, citranaxanthin, canthaxanthin, bixin, ⁇ -Apo-4-carotenal, ⁇ -Apo-8-carotenal, ⁇ -Apo-8-carotenoic esters, neurosporene, echinenone, adonirubin, violaxanthin, torulene, torularhodin, individually or as a mixture.
  • Preferably used carotenoids are ⁇ -carotene, lycopene, lutein, astaxanthin, zeaxanthin, citranaxanthin and canthaxanthin.
  • Further preferred effector molecules (ii) are UV photoprotective filters. These are understood as meaning organic substances which are able to absorb ultraviolet rays and release the absorbed energy again in the form of long-wave radiation, e.g. heat.
  • the organic substances may be oil-soluble or water-soluble.
  • Oil-soluble UV-B filters which may be used are, for example, the following substances: 3-benzylidenecamphor and derivatives thereof, e.g. 3-(4-methylbenzylidene)camphor;
  • 4-aminobenzoic 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, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene);
  • esters of salicylic acid preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylate;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone;
  • esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate
  • triazine derivatives such as, for example, 2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine (octyltriazone) and dioctylbutamidotriazone (Uvasorb® HEB);
  • propane-1,3-diones such as, for example, 1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,
  • Suitable water-soluble substances are:
  • sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzo-phenone-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.
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene).
  • derivatives of benzophenone in particular 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and the use of propane-1,3-diones, such as, for example, 1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione is preferred.
  • Suitable typical UV-A filters are:
  • benzoylmethane such as, for example, 1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione, 4-tert-butyl-4′-methoxydibenzoylmethane or 1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione;
  • benzophenones such as, for example, N,N-diethylaminohydroxybenzoyl n-hexylbenzoate.
  • UV-A and UV-B filters can of course also be used in mixtures.
  • Suitable UV filter substances are given in the table below.
  • secondary photoprotective agents of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin.
  • Typical examples thereof are superoxide dismutase, catalase, tocopherols (vitamin E), coenzyme Q10, ubiquinanes, quinones and ascorbic acid (vitamin C).
  • a further group are antiirritants which have an antiinflammatory effect on skin damaged by UV light.
  • antiirritants which have an antiinflammatory effect on skin damaged by UV light.
  • Such substances are, for example, bisabolol, phytol and phytantriol.
  • Effector molecules (ii) according to the invention are also inorganic pigments which stop UV rays. Preference is given to pigments based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water and chosen from the group of oxides of zinc (ZnO), titanium (TiO 2 ), iron (e.g. Fe 2 O 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese (e.g. MnO), aluminum (Al 2 O 3 ), cerium (e.g. Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides.
  • the inorganic pigments can be present here in coated form, i.e. are treated superficially.
  • This surface treatment can consist, for example, in providing the pigments with a thin hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
  • effector molecules (ii) are vitamins, in particular vitamin A and esters thereof.
  • retinoids are understood as meaning vitamin A alcohol (retinol) and its derivatives, such as vitamin A aldehyde (retinal), vitamin A acid (retinoic acid) and vitamin A ester (e.g. retinyl acetate, retinyl propionate and retinyl palmitate).
  • retinoic acid here comprises both all-trans retinoic acid and also 13-cis-retinoic acid.
  • the terms retinol and retinal preferably comprise the all-trans compounds.
  • a preferred retinoid used for the suspensions according to the invention is all-trans-retinol, referred to below as retinol.
  • Further preferred effector molecules (ii) are vitamins, provitamins and vitamin precursors from the groups A, C, E and F, in particular 3,4-didehydroretinol, ⁇ -carotene (provitamin of vitamin A), ascorbic acid (vitamin C), and the palmitic esters, glucosides or phosphates of ascorbic acid, tocopherols, in particular ⁇ -tocopherol, and its esters, e.g. the acetate, the nicotinate, the phosphate and the succinate; also vitamin F, which is understood as meaning essential fatty acids, particularly linoleic acid, linolenic acid and arachidonic acid.
  • vitamins, provitamins and vitamin precursors from the groups A, C, E and F in particular 3,4-didehydroretinol, ⁇ -carotene (provitamin of vitamin A), ascorbic acid (vitamin C), and the palmitic esters, glucosides or phosphate
  • vitamins, provitamins or vitamin precursors of the vitamin B group or derivatives thereof and the derivatives of 2-furanone to be used with preference according to the invention include, inter alia:
  • Vitamin B 1 trivial name thiamine, chemical name 3-[(4′-amino-2′-methyl-5′-pyrimidinyl)-methyl]-5-(2-hydroxyethyl)-4-methylthiazolium chloride.
  • Vitamin B 2 trivial name riboflavin, chemical name 7,8-dimethyl-10-(1-D-ribityl)-benzo[g]pteridine-2,4(3H,10H)-dione.
  • riboflavin occurs, for example, in whey, other riboflavin derivatives can be isolated from bacteria and yeasts.
  • a stereoisomer of riboflavin which is likewise suitable according to the invention is lyxoflavin, which can be isolated from fish meal or liver and bears a D-arabityl radical instead of the D-ribityl radical.
  • Vitamin B 3 The compounds nicotinic acid and nicotinamide (niacinamide) often bear this name. According to the invention, preference is given to nicotinamide.
  • Vitamin Bs pantothenic acid and panthenol. Preference is given to using panthenol.
  • Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol, and cationically derivatized panthenols.
  • derivatives of 2-furanone can also be used in addition to pantothenic acid or panthenol.
  • Particularly preferred derivatives are the also commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone with the trivial name pantolactone (Merck), 4-hydroxymethyl- ⁇ -butyrolactone (Merck), 3,3-dimethyl-2-hydroxy- ⁇ -butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck), with all stereoisomers being expressly included.
  • effector molecule compounds advantageously impart moisturizing and skin-calming properties to the protein microbeads (i) according to the invention.
  • Vitamin B 6 which is not understood here as meaning a uniform substance, but the derivatives of 5-hydroxymethyl-2-methylpyridin-3-ol known under the trivial names pyridoxin, pyridoxamine and pyridoxal.
  • Vitamin B 7 also referred to as vitamin H or “skin vitamin”.
  • Biotin is (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]imidazole-4-valeric acid.
  • Panthenol, pantolactone, nicotinamide and biotin are very particularly preferred according to the invention.
  • suitable derivatives salts, esters, sugars, nucleotides, nucleosides, peptides and lipids
  • suitable derivatives can be used as effector molecules.
  • lipophilic, oil-soluble antioxidants from this group preference is given to tocopherol and derivatives thereof, gallic esters, flavonoids and carotenoids and also butylhydroxytoluene/anisole.
  • Preferred water-soluble antioxidants are amino acids, e.g. tyrosine and cysteine and derivatives thereof, and tannins, in particular those of vegetable origin.
  • peroxide decomposers i.e. compounds which are able to decompose peroxides, particularly preferably lipid peroxides.
  • organic substances such as, for example, pyridine-2-thiol-3-carboxylic acid, 2-methoxypyrimidinolcarboxylic acids, 2-methoxypyridinecarboxylic acids, 2-dimethylaminopyrimidinolcarboxylic acids, 2-dimethylaminopyridinecarboxylic acids.
  • Triterpenes in particular triterpenoic acids, such as ursolic acid, rosmaric acid, betulinic acid, boswellic acid and bryonolic acid.
  • a further preferred effector molecule (ii) is lipoic acid and suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids).
  • Further preferred effector molecules (ii) are fatty acids, in particular saturated fatty acids which carry an alkyl branch, particularly preferably branched elcosanoic acids, such as 18-methyleicosanoic acid.
  • effector molecules (ii) are dyes, for example food dyes, semi-permanent dyes, reactive or oxidation dyes.
  • oxidation dyes it is preferred to link a component as effector molecule (ii) with the protein microbeads (i) and then to couple oxidatively with the second dye component at the site of action, i.e. following application to skin.
  • oxidation dyes it is also preferred to carry out the coupling of the dye components before the linkage with the protein microbeads (i).
  • the reactive dyes can also preferably be linked as a component as effector molecule (ii) with the protein microbeads (I) and then be applied to the skin.
  • those dyes which are linked as effector molecule (ii) with the protein microbeads (i) can be used in decorative cosmetics by application to skin.
  • Suitable dyes are all customary hair dyes for the molecules according to the invention. Suitable dyes are known to the person skilled in the art from cosmetics handbooks, for example Schrader, Klan and Phuren der Kosmetika [Fundamentals and formulations of cosmetics], Hithig Verlag, Heidelberg, 1989, ISBN 3-7785-1491-1.
  • Particularly advantageous dyes are those specified in the list below.
  • the Colour Index Numbers (CIN) are given in the Rowe Colour Index, 3rd edition, Society of Dyers and Colourists, Bradford, England, 1971.
  • Food dyes can also be highly suitable as dyes.
  • the effector molecules (ii) are joined to protein (i).
  • the bond between (i) and (ii) can either be a covalent bond, or be based on ionic or van der Waals' interactions or hydrophobic interactions or hydrogen bridge bonds or adsorption.
  • Each type of coupling, covalent or noncovalent, of effector molecule (ii) to protein (i) forming the microbead can take place in the dissolved state before phase separation. After the coupling, the formation of microbeads described in Example 1 takes place by phase separation.
  • a coupling of the effector molecule (ii) can also take place onto the protein microbead (i) already produced by phase separation, or during the phase separation process.
  • the effector molecule is incorporated into the protein microbeads (i) or bonded to their surface.
  • effector molecules (ii) non-covalently to the microbead-forming protein (i) are dissolved in the same solvent to give a common phase.
  • both components can be brought directly into solution by a solvent or a solvent mixture.
  • the effector molecule (ii) can firstly be dissolved in a solvent other than the microbead-forming protein (i) and then be mixed with the protein solution (i), again giving a common phase.
  • the predissolution of the effector molecule (ii) is especially of advantage if the effector molecule (ii) and the microbead-forming protein (i) can not be dissolved in the same solvent, such as, for example, in the case of aqueous protein solutions (i) and hydrophobic effector molecules (ii).
  • suitable, water-miscible solvents are alcohols, such as methanol, ethanol and isopropanol, fluorinated alcohols, such as hexafluoroisopropanol and trifluoroethanol, alkanones, such as acetone, and also sulfoxides, such as, for example, dimethyl sulfoxide or formamides such as dimethylformamide.
  • microbead-forming protein (i) can be dissolved in fluorinated alcohols, such as, for example, hexafluoroisopropanol or trifluoroethanol, and the protein solution can then be mixed with effector molecules (ii) in organic solvents.
  • fluorinated alcohols such as, for example, hexafluoroisopropanol or trifluoroethanol
  • Suitable solvents which can, for example, be mixed well with hexafluoroisopropanol are, inter glia, alcohols, such as methanol, ethanol and isopropanol, alkanones, such as acetone, sulfoxides, such as, for example, dimethyl sulfoxide, formamides, such as dimethylformamide, haloalkanes, such as methylene chloride, and also further organic solvents, such as tetrahydrofuran.
  • the noncovalent binding of the effector molecule (ii) to the microbead-forming protein (i) takes place during the assembly of the protein (i) to microbeads, where the assembly can take place as described in Example 1 through induced phase separation into a solid protein phase and a solvent phase.
  • the average diameter of the protein microbeads can be adjusted to values between 0.1 ⁇ m and 100 ⁇ m.
  • the morphology of the microbeads (i) should be determined by light and electron microscopic methods.
  • the binding of the effector molecule can be based on hydrophobic interactions, hydrogen bridges, ionic interaction and van der Waals' interactions or a mixture of these intermolecular forces.
  • the effector molecule can be bound to the surface of the protein microbeads (i), be incorporated into the protein microbeads (i), or be associated with the protein microbeads (i) in both ways.
  • the binding of the effector molecule to the protein microbeads (i) can be determined through the depletion of the assembly stock of soluble effector molecules (ii).
  • concentration of the effector molecules (ii) can be measured by a quantitative analysis of the effector molecule properties.
  • the binding of colored effector molecules (ii) can be analyzed, for example, by photometric methods.
  • the coloring of the protein microbeads (i) or the decoloring of the assembly stock are determined by measuring the absorption of the colored effector molecule.
  • a covalent linking of the effector molecule (ii) to the protein microbeads (i) can take place as described in Example 6. This can take place, for example, via the side chains of the polypeptide sequence of the microbead-forming protein (i), in particular via amino functions or hydroxy functions or carboxylate functions or thiol functions. Preference is given to a linking via the amino functions of one or more lysine radicals, via the carboxylate functions of one or more glutamate or aspartate radicals, one or more thiol groups of cysteine radicals or via the N-terminal or C-terminal function of the microbead-forming polypeptide (i).
  • amino acids with suitable functions e.g. cysteines, lysines, aspartates, glutamates
  • suitable functions e.g. cysteines, lysines, aspartates, glutamates
  • amino acids of the microbead-forming polypeptide sequence (i) can be substituted by such amino acid functions.
  • the linking of the effector molecules (ii) with the microbead-forming protein (i) can either take place directly, i.e. as a covalent linking of two chemical functions already present in (i) and (ii), for example an amino function of (i) is linked with a carboxylate function of (ii) to give the acid amide.
  • the linking can, however, also take place via a so-called linker, i.e. an at least bifunctional molecule which enters into a bond with (i) with one function and is linked to (ii) with one or more other functions.
  • effector molecule (ii) likewise consists of a polypeptide sequence
  • the linking of (i) and (ii) can take place as a so-called fusion protein, i.e. a general polypeptide sequence which consists of the two part sequences (i) and (ii).
  • spacer elements for example polypeptide sequences which have a potential cleavage site for a protease, lipase, esterase, phosphatase, hydrolase, or oligo- or polypeptide sequences which permit simple purification of the fusion protein, for example so-called His tags, i.e. oligohistidine radicals.
  • the spacer elements can be composed of alkyl chains, ethylene glycol and polyethylene glycols.
  • linker and/or spacer elements which have a potential cleavage site for a protease, lipase, esterase, phosphatase, hydrolase, i.e. are enzymatically cleavable.
  • linkers and spacers which are thermocleavable, photocleavable.
  • linkers and spacers which are thermocleavable, photocleavable.
  • Corresponding chemical structures are known to the person skilled in the art and are integrated between the molecule parts (i) and (ii).
  • the linking in the case of a non-protein-like effector molecule with the protein microbeads (i) takes place preferably through functionalizable radicals (side groups, C or N terminus) on the microbead-forming polypeptide (i), which enter into a covalent bond with a chemical function of the effector molecule.
  • a further preferred linking of the protein microbeads (i) with an effector molecule (ii) is the use of a tailored linker.
  • a linker has two or more so-called anchor groups with which it can link the microbead-forming polypeptide sequence (i) and one or more effector molecules (ii).
  • an anchor group for (i) may be a thiol function by means of which the linker can enter into a disulfide bond with a cysteine radical of the microbead-forming polypeptide (i).
  • An anchor group for (ii) can, for example, be a carboxyl function by means of which the linker can enter into an ester bond with a hydroxyl function of the effector molecule (ii).
  • the linker used is governed by the functionality to be coupled.
  • molecules which couple to microbead-forming polypeptides e.g. maleimides, pydridyldisulfides, ⁇ -haloacetyls, vinylsulfones, sulfatoalkylsulfones (preferably sulfatoethylsulfones) and to effector molecules (ii) by means of
  • a direct coupling between effector molecules and the protein microbeads (i) can be carried out, for example, by means of carbodiimides, glutardialdehyde, the abovementioned or other crosslinkers known to the person skilled in the art.
  • effector molecules (ii) coupled to protein microbeads (i) covalently or noncovalently may be active in their bonded form.
  • the effector molecules (ii) coupled to protein microbeads (i) can, however, also be released from the protein microbeads (i) or from their surface.
  • covalently coupled effector molecules (ii) from the protein microbeads (i) can take place through cleavage of specifically introduced cleavable spacers or coupling linkers, which may, for example, be thermocleavable, photocleavable or enzymatically cleavable, but also through proteolytic degradation (e.g. by proteases) as described in Example 5 or through dissolution of the protein microbeads (i) or through mechanical destruction of the protein microbeads (i).
  • cleavable spacers or coupling linkers which may, for example, be thermocleavable, photocleavable or enzymatically cleavable, but also through proteolytic degradation (e.g. by proteases) as described in Example 5 or through dissolution of the protein microbeads (i) or through mechanical destruction of the protein microbeads (i).
  • noncovalently coupled effector molecules (ii) from the protein microbeads (i) can take place through desorption in suitable solvents, through degradation of the microbeads (i) by proteases or through dissolution of the protein microbeads (i) or through mechanical destruction of the protein microbeads (i).
  • suitable solvents for the desorption are all solvents or solvent mixtures in which the effector molecule (ii) can dissolve.
  • Solvents which can dissolve the protein microbeads (i) are, for example, fluorinated alcohols, such as trifluoroethanol and hexafluoroisopropanol and also solutions of chaotropic salts, such as, for example, urea, guanidinium hydrochloride and guanidinium thiocyanate.
  • fluorinated alcohols such as trifluoroethanol and hexafluoroisopropanol
  • chaotropic salts such as, for example, urea, guanidinium hydrochloride and guanidinium thiocyanate.
  • Suitable proteases can be added as technical proteases to a suspension of protein microbeads (i) in a targeted way or occur naturally at the desired site of action of the effector molecules (ii), such as, for example, skin proteases or proteases released by microorganisms.
  • the rate and kinetics of the release of the effector molecules (ii) can be controlled through the charge density with effector molecules (ii) and the average size of the microbeads (i).
  • the protein microbeads (i) are formulated with customary further active ingredients and auxiliaries used in cosmetics.
  • the protein microbeads (i) according to the invention are used for skin cosmetics. They permit a high concentration and long action time of skincare or skin-protecting effector substances.
  • auxiliaries and additives for producing hair cosmetic, nail cosmetic or skin cosmetic preparations are known to the person skilled in the art and can be found in cosmetics handbooks, for example Schrader, Klan and Phuren der Kosmetika [Fundamentals and formulations of cosmetics], Weghig Verlag, Heidelberg, 1989, ISBN 3-7785-1491-1.
  • the cosmetic compositions according to the invention may be skin cosmetic, nail cosmetic, hair cosmetic, dermatological, hygiene or pharmaceutical compositions.
  • compositions according to the invention are in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • compositions according to the invention can additionally comprise cosmetically and/or dermatologically active ingredients, and auxiliaries.
  • the cosmetic compositions according to the invention comprise at least one protein microbead, and at least one constituent different therefrom which is chosen from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, photoprotective agents, bleaches, gel formers, care agents, colorants, tinting agents, tanning agents, dyes, pigments, consistency regulators, humectants, refatting agents, collagen, protein hydrolyzates, lipids, antioxidants, antifoams, antistats, emollients and softeners.
  • the protein microbeads (i) can also be present in the cosmetic preparations in encapsulated form.
  • the antioxidants are chosen from the group consisting of 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. ⁇ -carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g.
  • amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazoles e.g. urocanic acid
  • peptides such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine)
  • carotenoids e.g.
  • thiols e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters thereof
  • salts thereof dilauryl thin-dipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g.
  • buthionine sulfoximines in very low tolerated doses (e.g. pmol to ⁇ mol/kg), also (metal) chelating agents (e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), ⁇ -hydroxy acids (e.g.
  • citric acid citric acid, lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA and derivatives thereof
  • unsaturated fatty acids and derivatives thereof e.g. ⁇ -linolenic acid, linoleic acid, oleic acid
  • folic acid and derivatives thereof ubiquinone and ubiquinol and derivatives thereof
  • vitamin C and derivatives thereof e.g. sodium ascorbate, ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate
  • tocopherol and derivatives e.g.
  • vitamin E acetate, tocotrienol
  • vitamin A and derivatives vitamin A palmitate
  • coniferyl benzoate of benzoin resin rutinic acid and derivatives thereof, ⁇ -glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO 4 ), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide).
  • benzoin resin rutinic acid and derivatives thereof, ⁇ -glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxy
  • peroxide decomposers i.e. compounds which are able to decompose peroxides, particularly preferably lipid peroxides.
  • organic substances such as, for example, pyridine-2-thiol-3-carboxylic acid, 2-methoxypyrimidinolcarboxylic acids, 2-methoxypyridinecarboxylic acids, 2-dimethylaminopyrimidinolcarboxylic acids, 2-dimethylaminopyridinecarboxylic acids.
  • Customary thickeners in such formulations are crosslinked polyacrylic acids and derivatives thereof, polysaccharides and derivatives thereof, such as xanthan gum, agar-agar, alginates or tyloses, cellulose derivatives, e.g. carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone. Preference is given to using nonionic thickeners.
  • Suitable cosmetically and/or dermocosmetically active ingredients are, for example, coloring active ingredients, skin and hair pigmentation agents, tinting agents, tanning agents, bleaches, keratin-hardening substances, antimicrobial active ingredients, photofilter active ingredients, repellent active ingredients, hyperemic substances, keratolytically and keratoplastically effective substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, antioxidative active ingredients and/or active ingredients which act as free-radical scavengers, skin moisturizing or humectant substances, refatting active ingredients, antierythematous or antiallergic active ingredients, branched fatty acids, such as 18-methyleicosanoic acid, and mixtures thereof.
  • Artificially skin-tanning active ingredients which are suitable for tanning the skin without natural or artificial irradiation with UV rays are, for example, dihydroxyacetone, alloxan and walnut shell extract.
  • Suitable keratin-hardening substances are usually active ingredients, as are also used in antiperspirants, such as, for example, potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
  • Antimicrobial active ingredients are used to destroy microorganisms or to inhibit their growth and thus serve both as preservative and as deodorizing substance which reduces the formation or the intensity of body odor.
  • These include, for example, customary preservatives known to the person skilled in the art, such as p-hydroxy-benzoic esters, imidazolidinylurea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
  • deodorizing substances are, for example, zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citrate, chlorhexidine etc.
  • Suitable preservatives which are listed below with their E number, are to be used advantageously according to the invention.
  • preservatives or preservative auxiliaries customary in cosmetics dibromodicyanobutane (2-bromo-2-bromomethyl-glutarodinitrile), 3-iodo-2-propynyl butylcarbamate, 2-bromo-2-nitropropane-1,3-diol, imidazolidinylurea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, formaldehyde cleavers.
  • phenyl hydroxyalkyl ethers in particular the compound known under the name phenoxyethanol on account of its bactericidal and fungicidal effects on a number of microorganisms.
  • antimicrobial agents are likewise suitable for being incorporated into the preparations according to the invention.
  • Advantageous substances are, for example, 2,4,4′-trichloro-2′-hydroxydiphenyl ether (irgasan), 1,6-di(4-chlorophenylbiguanido)-hexane (chiorhexidine), 3,4,4′-trichlorocarbanilide, quaternary ammonium compounds, oil of cloves, mint oil, thyme oil, triethyl citrate, farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), and the active ingredients or active ingredient combinations described in the patent laid-open specifications DE-37 40 186, DE-39 38 140, DE-42 04 321, DE-42 29 707, DE-43 09 372, DE-44 11 664, DE-195 41 967, DE-195 43 695, DE-195 43 696, DE-195 47 160, DE-196 02 108, DE-196 02 110
  • Suitable photofilter active ingredients are substances which absorb UV rays in the UV-B and/or UV-A region.
  • Suitable UV filters are, for example, 2,4,6-triaryl-1,3,5-triazines in which the aryl groups can each carry at least one substituent which is preferably chosen from hydroxy, alkoxy, specifically methoxy, alkoxycarbonyl, specifically methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • substituent is preferably chosen from hydroxy, alkoxy, specifically methoxy, alkoxycarbonyl, specifically methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • p-aminobenzoic esters cinnamic esters, benzophenones, camphor derivatives, and pigments which stop UV rays, such as titanium dioxide, talc and zinc oxide.
  • Suitable UV filter substances are any UV-A and UV-B filter substances. Examples to be mentioned are:
  • the cosmetic and dermatological preparations according to the invention can advantageously also comprise inorganic pigments which stop UV rays and are based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, chosen from the group of oxides of zinc (ZnO), titanium (TiO 2 ), iron (e.g. Fe 2 O 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese (e.g. MnO), aluminum (Al 2 O 3 ), cerium (e.g. Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides.
  • inorganic pigments which stop UV rays and are based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, chosen from the group of oxides of zinc (ZnO), titanium (TiO 2 ), iron (e.g. Fe 2 O 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese
  • the inorganic pigments can be present here in coated form, i.e. are treated superficially.
  • This surface treatment can consist, for example, in providing the pigments with a thin hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
  • Suitable repellent active ingredients are compounds which are able to repel or drive away certain animals, in particular insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide etc.
  • Suitable hyperemic substances which stimulate the flow of blood through the skin, are e.g. essential oils, such as dwarf pine extract, lavender extract, rosemary extract, juniperberry extract, horse chestnut extract, birch leaf extract, hayflower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc.
  • Suitable keratolytic and keratoplastic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.
  • Suitable antidandruff active ingredients are, for example, sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc.
  • Suitable antiphlogistics, which counteract skin irritations are, for example, allantoin, bisabolol, dragosantol, camomile extract, panthenol, etc.
  • compositions according to the invention can comprise, as cosmetic and/or pharmaceutical active ingredient (also, if appropriate, as auxiliary), at least one cosmetically or pharmaceutically acceptable polymer.
  • cosmetic and/or pharmaceutical active ingredient also, if appropriate, as auxiliary
  • at least one cosmetically or pharmaceutically acceptable polymer include, quite generally, cationic, amphoteric and neutral polymers.
  • Suitable polymers are, for example, cationic polymers with the INCI name Polyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazolium salts (Luviquat FC, Luviquat HM, Luviquat MS, Luviquat&commat, Care), copolymers of N-vinyl-pyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat PQ 11), copolymers of N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts (Luviquat E Hold), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7) and chitosan.
  • Polyquaternium e.g. copolymers of vinylpyrrolidone/N-viny
  • Suitable cationic (quaternized) polymers are also Merquat (polymer based on dimethyldiallylammonium chloride), Gafquat (quaternary polymers which are formed by reacting polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and plant-based cationic polymers, e.g. guar polymers, such as the Jaguar grades from Rhodia.
  • polystyrene resin examples include polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate, poly-siloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and salts thereof, polyvinylamines and salts thereof, cellulose derivatives, polyaspartic acid salts and derivatives.
  • neutral polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate, poly-siloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and salts thereof, polyvinylamines and salts thereof, cellulose derivatives, polyaspartic acid salts and derivatives.
  • Luviflex 0 Swing partially hydrolyzed copolymer
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, e.g. Luviskol 0 Plus (BASF), or polyvinyl-pyrrolidone and copolymers thereof, in particular with vinyl esters, such as vinyl acetate, e.g. Luviskol 0 VA 37 (BASF), polyamides, e.g. based on itaconic acid and aliphatic diamines, as are described, for example, in DE-A-43 33 238.
  • polyvinylcaprolactam e.g. Luviskol 0 Plus (BASF)
  • vinyl esters such as vinyl acetate, e.g. Luviskol 0 VA 37 (BASF)
  • BASF Luviskol 0 VA 37
  • polyamides e.g. based on itaconic acid and aliphatic diamines, as are described, for example, in DE-A-43 33 238.
  • Suitable polymers are also amphoteric or zwitterionic polymers, such as the octylacryl-amide/methyl methacrylate/tert-butylaminoethyl methacrylate-hydroxypropyl methacrylate copolymers obtainable under the names Amphomer (National Starch), and zwitterionic polymers, as are disclosed, for example, in the German patent applications DE39 29 973, DE 21 50 557, DE28 17 369 and DE 3708 451. Acrylamido-propyltrimethylammonium chloride/acrylic acid or methacrylic acid copolymers and alkali metal and ammonium salts thereof are preferred zwitterionic polymers.
  • zwitterionic polymers are methacroylethylbetaine/methacrylate copolymers, which are commercially available under the name Amersette (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N,N-dimethylamino-ethyl methacrylate and acrylic acid (Jordapon (D)).
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, e.g. polyether siloxanes, such as Tegopren 0 (Goldschmidt) or Besi&commat (Wacker).
  • polyether siloxanes such as Tegopren 0 (Goldschmidt) or Besi&commat (Wacker).
  • the formulation base of cosmetic compositions according to the invention preferably comprises cosmetically and/or pharmaceutically acceptable auxiliaries.
  • Pharmaceutically acceptable auxiliaries are the auxiliaries which are known for use in the field of pharmacy, food technology and related fields, in particular the auxiliaries listed in the relevant pharmacopeia (e.g. DAB Ph. Eur. BP NF), and other auxiliaries whose properties do not preclude a physiological application.
  • Suitable auxiliaries may be: glidants, wetting agents, emulsifying and suspending agents, preservatives, antioxidants, antiirritatives, chelating agents, emulsion stabilizers, film formers, gel formers, odor masking agents, resins, hydrocolloids, solvents, solubility promoters, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, refatting and superfatting agents, ointment, cream or oil base substances, silicone derivatives, stabilizers, sterilizing agents, propellants, drying agents, opacifiers, thickeners, waxes, softeners, white oil.
  • the active ingredients can be mixed or diluted with a suitable auxiliary (excipient).
  • Excipients may be solid, semisolid or liquid materials which can serve as vehicles, carriers or medium for the active ingredient.
  • the admixing of further auxiliaries takes place, if desired, in the manner known to the person skilled in the art.
  • the polymers and dispersions are suitable as auxiliaries in pharmacy, preferably as or in (a) coating composition(s) or binder(s) for solid drug forms. They can also be used in creams and as tablet coatings and tablet binders.
  • compositions according to the invention are a skin cleansing composition.
  • Preferred skin cleansing compositions are soaps of liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes, exfoliating soaps, moisture wipes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels, foam baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • transparent soaps such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes, exfoliating soaps, moisture wipes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels, foam baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • compositions according to the invention are cosmetic compositions for the care and protection of the skin and hair, nailcare compositions or preparations for decorative cosmetics.
  • Suitable skin cosmetic compositions are, for example, face tonics, face masks, deodorants and other cosmetic lotions.
  • Compositions for use in decorative cosmetics include, for example, concealing sticks, stage make-up, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, blushers, powders and eyebrow pencils.
  • the dermatological compositions according to the invention can be used in nose strips for pore cleansing, in antiacne compositions, repellents, shaving compositions, aftershave and preshave care compositions, aftersun care compositions, hair removal compositions, hair colorants, intimate care compositions, footcare compositions, and in baby care.
  • the skincare compositions according to the invention are, in particular, W/O or O/W skin creams, day creams and night creams, eye creams, face creams, antiwrinkle creams, sunscreen creams, moisturizing creams, bleaching creams, self-tanning creams, vitamin creams, skin lotions, care lotions and moisturizing lotions.
  • the protein microbeads (i) can, inter alia, contribute to the moisturization and conditioning of the skin and to an improvement in the feel of the skin.
  • the protein microbeads (i) can also act as thickeners in the formulations.
  • Skin cosmetic and dermatological compositions preferably comprise at least one protein microbead (i) in an amount of from about 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the composition.
  • Particularly photoprotective compositions based on the protein microbeads (i) have the property of increasing the residence time of the UV-absorbing ingredients compared to customary auxiliaries such as polyvinylpyrrolidone.
  • compositions according to the invention can be applied in a form suitable for skincare, such as, for example, as cream, foam, gel, stick, mousse, milk, spray (pump spray or propellant-containing spray) or lotion.
  • a form suitable for skincare such as, for example, as cream, foam, gel, stick, mousse, milk, spray (pump spray or propellant-containing spray) or lotion.
  • the skin cosmetic preparations can also comprise further active ingredients and auxiliaries customary in skin cosmetics, as described above.
  • these include, preferably, emulsifiers, preservatives, perfume oils, cosmetic active ingredients, such as phytantriol, vitamin A, E and C, retinol, bisabolol, panthenol, photoprotective agents, bleaches, colorants, tinting agents, tanning agents, collagen, enzymes, protein hydrolyzates, stabilizers, pH regulators, dyes, salts, thickeners, gel formers, consistency regulators, silicones, humectants, refatting agents and/or further customary additives.
  • emulsifiers such as phytantriol, vitamin A, E and C, retinol, bisabolol, panthenol, photoprotective agents, bleaches, colorants, tinting agents, tanning agents, collagen, enzymes, protein hydrolyzates, stabilizers, pH regulators, dyes, salts, thickeners,
  • Preferred oil and fat components of the skin cosmetic and dermatological compositions are the abovementioned mineral and synthetic oils, such as, for example, paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such as, for example, sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as, for example, triglycerides of C6-C30 fatty acids, wax esters, such as, for example, jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.
  • mineral and synthetic oils such as, for example, paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms
  • animal and vegetable oils such as, for example, sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes
  • fatty acids such as, for example, triglycerides of C6-C30
  • the protein microbeads (i) according to the invention can also be mixed with conventional polymers if specific properties are to be established.
  • the skin cosmetic and dermatological preparations can additionally also comprise conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • the cosmetic or dermocosmetic preparations are produced by customary methods known to the person skilled in the art.
  • the cosmetic and dermocosmetic compositions are present in the form of emulsions, in particular as water-in-oil (W/O) or oil-in-water (O/W) emulsions.
  • W/O water-in-oil
  • O/W oil-in-water
  • Emulsifier-free formulations such as hydrodispersions, hydrogels or a Pickering emulsion are also advantageous embodiments.
  • Emulsions are produced by known methods. Besides at least one protein microbead (i), the emulsions usually comprise customary constituents, such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • customary constituents such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • a suitable emulsion in the form of a W/O emulsion generally comprises an aqueous phase which is emulsified in an oil or fatty phase using a suitable emulsifier system.
  • a polyelectrolyte complex can be used for the provision of the aqueous phase.
  • Preferred fatty components which may be present in the fatty phase of the emulsions are: hydrocarbon oils, such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophyllum oil, lanolin and derivatives thereof, castor oil, sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil, mineral oils whose distillation start-point under atmospheric pressure is at about 250° C. and whose distillation end-point is at 410° C., such as, for example, Vaseline oil, esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g.
  • the fatty phase can also comprise silicone oils which are soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • silicone oils which are soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes can also be used, such as, for example, carnauba wax, candelilia wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • an emulsion according to the invention may be in the form of an O/W emulsion.
  • Such an emulsion usually comprises an oil phase, emulsifiers which stabilize the oil phase in the water phase, and an aqueous phase, which is usually present in thickened form.
  • Suitable emulsifiers are preferably O/W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides.
  • compositions according to the invention are a shower gel, a shampoo formulation or a bathing preparation.
  • Such formulations comprise at least one protein microbead (i) and usually anionic surfactants as base surfactants and amphoteric and/or nonionic surfactants as cosurfactants.
  • suitable active ingredients and/or auxiliaries are generally chosen from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, and thickeners/gel formers, skin conditioning agents and humectants.
  • formulations advantageously comprise 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropyl-betaines, alkylsulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or -propionates, alkyl amphodiacetates or -dipropionates.
  • cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and/or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 mol per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan ether esters are suitable.
  • washing, shower and bath preparations can comprise customary cationic surfactants, such as, for example, quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • customary cationic surfactants such as, for example, quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • shower gel/shampoo formulations can comprise thickeners, such as, for example, sodium chloride, PEG-55, propylene glycol oleate, PEG-120 methylglucose dioleate and others, and also preservatives, further active ingredients and auxiliaries and water.
  • thickeners such as, for example, sodium chloride, PEG-55, propylene glycol oleate, PEG-120 methylglucose dioleate and others, and also preservatives, further active ingredients and auxiliaries and water.
  • compositions according to the invention are a hair-treatment composition.
  • Hair-treatment compositions according to the invention preferably comprise at least one protein microbead (i) in an amount in the range from about 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.
  • the hair treatment compositions according to the invention are in the form of a setting foam, hair mousse, hair gel, shampoo, hair spray, hair foam, end fluid, neutralizer for permanent waves, hair colorant and bleach or hot-oil treatment.
  • the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax.
  • Hair sprays include here both aerosol sprays and also pump sprays without propellant gas.
  • Hair foams include both aerosol foams and also pump foams without propellant gas.
  • Hair sprays and hair foams preferably include predominantly or exclusively water-soluble or water-dispersible components.
  • the compounds used in the hair sprays and hair foams according to the invention are dispersible in water, they can be applied in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm.
  • the solids contents of these preparations are here usually in a range from about 0.5 to 20% by weight.
  • These microdispersions do not usually require emulsifiers or surfactants for their stabilization.
  • the hair cosmetic formulations according to the invention comprise, in a preferred embodiment, a) 0.01 to 30% by weight of at least one protein microbead (i), b) 20 to 99.95% by weight of water and/or alcohol, c) 0 to 50% by weight of at least one propellant gas, d) 0 to 5% by weight of at least one emulsifier, e) 0 to 3% by weight of at least one thickener, and up to 25% by weight of further constituents.
  • Alcohol is understood as meaning all alcohols customary in cosmetics, e.g. ethanol, isopropanol, n-propanol.
  • compositions customary in cosmetics, for example propellants, antifoams, interface-active compounds, i.e. surfactants, emulsifiers, foam formers and solubilizers.
  • interface-active compounds i.e. surfactants, emulsifiers, foam formers and solubilizers.
  • the interface-active compounds used may be anionic, cationic, amphoteric or neutral.
  • customary constituents may also be, for example, preservatives, perfume oils, opacifiers, active ingredients, UV filters, care substances, such as panthenol, collagen, vitamins, protein hydrolyzates, alpha- and beta-hydroxycarboxylic acids, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, salts, humectants, refatting agents, complexing agents and further customary additives.
  • styling and conditioner polymers known in cosmetics which can be used in combination with the protein microbeads (i) according to the invention if quite specific properties are to be established.
  • Suitable conventional hair cosmetics polymers are, for example, the above-mentioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is made here.
  • the preparations can additionally also comprise conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds, such as amodimethicones (CTFA).
  • the polymers according to the invention are particularly suitable as setting compositions in hair styling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (as aerosol foams and pump foams without propellant gas).
  • spray preparations comprise a) 0.01 to 30% by weight of at least one protein microbead (i), b) 20 to 99.9% by weight of water and/or alcohol, c) to 70% by weight of at least one propellant, d) 0 to 20% by weight of further constituents.
  • Propellants are the propellants customarily used for hair sprays or aerosol foams. Preference is given to mixtures of propane/butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air.
  • a formulation preferred according to the invention for aerosol hair foams comprises a) 0.01 to 30% by weight of at least one protein microbead (i), b) 55 to 99.8% by weight of water and/or alcohol, c) 5 to 20% by weight of a propellant, d) 0.1 to 5% by weight of an emulsifier, e) 0 to 10% by weight of further constituents.
  • Emulsifiers which can be used are all emulsifiers customarily used in hair foams. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
  • nonionic emulsifiers are laureths, e.g. laureth-4; ceteths, e.g. ceteth-1, polyethylene glycol cetyl ether, ceteareths, e.g. ceteareth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkyl polyglycosides.
  • cationic emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimonium chloride, cetyltrimonium bromide, cocotrimonium methyl sulfate, Quaternium-1 to x (INCI).
  • Anionic emulsifiers can be chosen, for example, from the group of alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • a preparation suitable according to the invention for styling gels can, for example, have the following composition: a) 0.01 to 30% by weight of at least one protein microbead (1), b) 80 to 99.85% by weight of water and/or alcohol, c) 0 to 3% by weight, preferably 0.05 to 2% by weight, of a gel former, d) 0 to 20% by weight of further constituents.
  • the use of gel formers may be advantageous in order to establish specific rheological or other application-related properties of the gels.
  • Gel formers which can be used are all gel formers customary in cosmetics. These include slightly crosslinked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g.
  • ICI Paraffinum Liquidum
  • PPG-1 trideceth-6 acrylamidopropyltrimonium chlor
  • the protein microbeads (i) according to the invention can be used as conditioners in cosmetic preparations.
  • a preparation comprising the protein microbeads (i) according to the invention can preferably be used in shampoo formulations as setting and/or conditioning compositions.
  • Preferred shampoo formulations comprise a) 0.01 to 30% by weight of at least one protein microbead (i), b) 25 to 94.95% by weight of water, c) 5 to 50% by weight of surfactants, c) 0 to 5% by weight of a further conditioning agent, d) 0 to 10% by weight of further cosmetic constituents.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropyl-betaines, alkylsulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or -propionates, alkyl amphodiacetates or -dipropionates.
  • cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and/or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 mol per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkyl polyglycosides or sorbitan ether esters are suitable.
  • the shampoo formulations can comprise customary cationic surfactants, such as, for example, quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • customary conditioning agents can be used in combination with the protein microbeads (i).
  • cationic polymers with the INCI name Polyquaternium, in particular copolymers of vinylpyrrolidone/N-vinylimidazolium salts (Luviquat FC, Luviquat&commat, HM, Luviquat MS, Luviquat Care), copolymers of N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat D PQ 11), copolymers of N-vinylcaprolactam/N-vinylpyrrolidone/N-vinyl-imidazolium salts (Luviquat D Hold), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).
  • protein hydrolyzates can be used, and also conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • Further suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds, such as amodimethicones (CTFA).
  • CTFA dimethicone copolyols
  • amino-functional silicone compounds such as amodimethicones
  • cationic guar derivatives such as Guar Hydroxypropyltrimonium Chloride (INCI) can be used.
  • aqueous C16 solution is prepared.
  • lyophilized C16 is dissolved in 6 M guanidinium thiocyanate (GdmSCN) with an end concentration of 0.1-10 mg/ml.
  • GdmSCN guanidinium thiocyanate
  • the GdmSCN is then removed by dialysis against 5 mM potassium phosphate pH 8.0.
  • ⁇ -pleated-sheet-rich C16-microbeads The formation of ⁇ -pleated-sheet-rich C16-microbeads is induced at room temperature by rapidly adding 500 mM potassium phosphate pH 8.0 or 800 mM ammonium sulfate (end concentration) to the protein solution, followed by brief mixing (e.g. swirling the reaction vessel).
  • the mean particle diameter is dependent on the protein concentration used and can be varied between 0.5 ⁇ m and 15 ⁇ m.
  • the particles are then washed with water and lyophilized. The success of the microbead formation is checked using scanning electron microscopy.
  • the thermal stability of C16-microbeads was determined using the “Thermogravimetric Analyser TGA 7” apparatus from Perkin-Elmer. Here, aluminum sample pans with a volume of 40 ⁇ l were used. The flushing gas used for the balance was 4 I/h of nitrogen, and the flushing gas used for the sample space was 1.6 I/h of nitrogen or air (in each case following measurement). The sample was heated from 30 to 500° C. at a heating rate of 5 K/min. During the measurement, the sample weight and the oven temperature were recorded. FIG. 1 shows the course of the C16-microbead sample weight as a function of the temperature. It can be clearly seen that the majority of the analyzed C16-microbeads is stable up to temperatures of at least 250° C. Only then is a significant loss in mass seen, the reason for this being the decomposition of the sample.
  • C16-Microbeads can absorb and release water from the air and thus serve as moisture-regulating substance in cosmetic applications.
  • 0.4 g-0.5 g of C16-microbeads which have been stored beforehand at ⁇ 20° C., were dried for 16 h under reduced pressure.
  • the microbeads lost 12% of their weight (based on the dry weight).
  • Subsequent storage at room temperature and 100% atmospheric humidity led to a slow weight increase of 25% over the course of 19 days (see FIG. 2 ). Drying again under reduced pressure achieved the original dry weight again.
  • the canthaxanthin was removed quantitatively from the solution, as could be shown by determining the absorbance in the supernatant after centrifuging off the C16-microbeads ( FIG. 3 ).
  • the centrifuged-off C16-microbeads appeared clearly pink-violet in color.
  • the charged C16-microbeads were analyzed by means of electron microscopy. In the electron micrograph, the charged C16-microbeads do not differ from the uncharged control which was prepared under the same conditions, as a result of which it becomes evident that the C16-microbeads and the canthaxanthin form a common solid phase ( FIG. 4 ).
  • the charged microbeads were washed with 5 mM potassium phosphate (pH 8.0), 5 mM potassium phosphate (pH 8.0)+5% DMSO and pure DMSO.
  • the C16-microbeads were incubated with 1 ml of each of the solutions for about 1 min. Centrifugation was then carried out and the canthaxanthin content in the supernatant was measured by determining the absorbance.
  • the release can also take place by degrading the C16-microbeads.
  • solvents such as, for example, DMSO
  • the release can also take place by degrading the C16-microbeads.
  • 150 ⁇ l of C16 in 5 mM potassium phosphate (pH 8.0) were mixed with 150 ⁇ l of a saturated solution of canthaxanthin in DMSO.
  • 700 ⁇ l of a 1 M potassium phosphate solution (pH 8.0) were then added in order to induce the formation of the C16-microbeads.
  • the supernatants were removed and the C16-microbeads charged with canthaxanthin were taken up in 1 ml of a 5 mM potassium phosphate solution (pH 8.0).
  • the canthaxanthin content in the supernatants was determined photometrically by reference to the canthaxanthin absorbance (supernatant after C16 precipitation). Whereas as in the control without C16, the total canthaxanthin remained in the supernatant, the canthaxanthin in the two batches with C16 was bound quantitatively by the C16-microbeads ( FIG. 7 ).
  • the coupling of ethylenediamine to the activated C16 carboxyl groups was carried out by adding 500 mM ethylenediamine and incubating the batch for two hours at room temperature. The batch was then dialyzed against 5 mM potassium phosphate pH 8.0.
  • fluorescein isothiocyanate was bound to the free amino group of the ethylenediamine coupled to C16 ( FIG. 8 ).
  • the following stock solutions were used:
  • the FITC stock solution was prepared in each case shortly prior to use.
  • the FITC coupling was carried out according to the following protocol:
  • Dermocosmetic preparations according to the invention comprising the C16-microbeads prepared according to Example 1 or C16-microbead-canthaxanthin produced according to Example 4 are described below.
  • Preparation Heat phases A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Stir phase C into the combined phases A and B and homogenize again. Cool with stirring to about 40° C., add phase D, adjust the pH to about 6.5 with phase E, homogenize and cool to room temperature with stirring.
  • the formulation is prepared without protective gas. Bottling must take place in oxygen-impermeable packagings, e.g. aluminum tubes.
  • Preparation Heat phases A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Incorporate phase C into the combined phases A and B and homogenize. Cool to about 40° C. with stirring. Add phase D, adjust the pH to about 6.5 with phase E and homogenize. Cool to room temperature with stirring.
  • Perfume Oil D 3.0 Polyquaternium-44 0.5 Cocotrimonium Methosulfate 0.5 Ceteareth-25 2.0 Panthenol, Propylene Glycol 4.0 Propylene Glycol 0.1 Disodium EDTA 1.0 C16-Microbead 60.7 Aqua dem. Al 5%: A 10.0 Cetearyl Ethylhexanoate 10.0 Caprylic/Capric Triglyceride 1.5 Cyclopentasiloxane, Cyclohexasilosane 2.0 PEG-40 Hydrogenated Castor Oil B 3.5 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer C 1.0 Tocopheryl Acetate 0.2 Bisabolol q.s.
  • Dissolve phase A Stir phase B into phase A, incorporate phase C into the combined phases A and B.
  • Dissolve phase D stir into the combined phases A, B and C and homogenize. After-stir for 15 min.
  • Preparation Mix the components of phase A. Dissolve phase B, incorporate into phase A and homogenize.
  • Preparation Mix the Components of Phase A. Stir Phase B into Phase A with homogenization. Neutralize with phase C and homogenize again.
  • Preparation Heat the components of phase A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Heat phase C to about 80° C. and stir into the combined phases A and B with homogenization. Cool to about 40° C. with stirring, add phase D and homogenize again.
  • D 1.0 Tocopheryl Acetate 0.2 Bisabolol q.s. Perfume Oil q.s. Preservative Al 5%: A 3.5 Ceteareth-6, Stearyl Alcohol 1.5 Ceteareth-25 7.5 Ethylhexyl Methoxycinnamate 2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate 2.0 Cyclopentasiloxane, Cyclohexasiloxane 0.5 Bees Wax 3.0 Cetearyl Alcohol 10.0 Caprylic/Capric Triglyceride B 5.0 Titanium Dioxide, Silica, Methicone, Alumina C 3.0 Glycerin 0.2 Disodium EDTA 0.3 Xanthan Gum 1.0 Decyl Glucoside 2.0 Panthenol, Propylene Glycol 5.0 C16-Microbead 52.3 Aqua dem. D 1.0 Tocopheryl Acetate 0.2 Bisabolol q.s. Perfume Oil q.s. Preserv
  • Preservative C 1.0 Bisabolol 1.0 Tocopheryl Acetate D 5.0 Witch Hazel Extract Al 5%: A 2.0 Ceteareth-6, Stearyl Alcohol 2.0 Ceteareth-25 5.0 Cetearyl Ethylhexanoate 4.0 Cetyl Alcohol 4.0 Glyceryl Stearate 5.0 Mineral Oil 0.2 Menthol 0.5 Camphor B 65.3 Aqua dem. 5.0 C16-Microbead-Canthaxanthin q.s. Preservative C 1.0 Bisabolol 1.0 Tocopheryl Acetate D 5.0 Witch Hazel Extract
  • Preparation Heat the components of phases A and B separately from one another to about 80° C. Stir phase B into phase A with homogenization. Cool to about 40° C. with stirring, add phases C and D and briefly after-homogenize. Cool to room temperature with stirring.
  • Preparation Heat phases A and B separately from one another to about 85° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phase C and briefly homogenize again. Cool to room temperature with stirring.
  • Preparation Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
  • Preparation Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
  • Preparation Mix the components of phase A. Dissolve the components of phase B to give a clear solution, then stir phase B into phase A. Adjust the pH to 6-7, bottle with phase C.
  • Preparation Mix the components of phase A. Add the components of phase B one after the other and dissolve. Dissolve phase C in the mixture with A and B, then adjust the pH to 6-7. Bottle with phase D.
  • Preparation Mix the components of phase A. Add the components of phase B one after the other and dissolve. Dissolve phase C in the mixture with A and B, then adjust the pH to 6-7. Bottle with phase D.
  • phase A Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
  • phase A Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
  • phase A Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
  • Preparation Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
  • Citric Acid Al 5% A 30.0 Sodium Laureth Sulfate 6.0 Sodium Cocoamphoacetate 6.0 Cocamidopropyl Betaine 3.0 Sodium Laureth Sulfate, Glycol Distearate, Cocamide MEA, Laureth-10 5.0 C16-Microbead 7.7 Polyquaternium-44 2.0 Amodimethicone q.s. Perfume Oil q.s. Preservative 1.0 Sodium Chloride 39.3 Aqua dem. B q.s. Citric Acid
  • Preparation Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
  • Preparation Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
  • Preparation Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
  • Preparation Weigh in the components of phase A and dissolve. Adjust the pH to 6-7. Add phase B and heat to about 50° C. Cool to room temperature with stirring.
  • Citric Acid Al 5% A 2.0 Ceteareth-25 2.0 Ceteareth-6, Stearyl Alcohol 3.0 Cetearyl Ethylhexanoate 1.0 Dimethicone 4.0 Cetearyl Alcohol 3.0 Glyceryl Stearate SE 5.0 Mineral Oil 4.0 Simmondsia Chinensis (Jojoba) Seed Oil 3.0 Mineral Oil, Lanolin Alcohol B 5.0 Propylene Glycol 5.0 C16-Microbead 1.0 Panthenol 0.5 Magnesium Aluminum Silicate q.s Preservative 61.5 Aqua dem. C q.s. Perfume Oil D q.s. Citric Acid
  • Preparation Heat phases A and B separately to about 80° C. Briefly prehomogenize phase B, then stir phase B into phase A and homogenize again. Cool to about 40° C., add phase C and homogenize well again. Adjust the pH to 6-7 with citric acid.
  • Perfume Oil Al 5% A 6.0 PEG-7 Hydrogenated Castor Oil 10.0 Cetearyl Ethylhexanoate 5.0 Isopropyl Myristate 7.0 Mineral Oil 0.5 Shea Butter ( Butyrospermum Parkii ) 0.5 Aluminum Stearate 0.5 Magnesium Stearate 0.2 Bisabolol 0.7 Quaternium-18-Hectorite B 5.0 Dipropylene Glycol 0.7 Magnesium Sulfate 5.0 C16-Microbead q.s. Preservative 58.9 Aqua dem. C q.s. Perfume Oil
  • Preparation Heat phases A and B separately to about 80° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phase C and homogenize again. Allow to cool to room temperature with stirring.
  • Titanium Dioxide 1.1 Iron Oxides Al 5% A 2.0 Ceteareth-6, Stearyl Alcohol 2.0 Ceteareth-25 6.0 Glyceryl Stearate 1.0 Cetyl Alcohol 8.0 Mineral Oil 7.0 Cetearyl Ethylhexanoate 0.2 Dimethicone B 3.0 Propylene Glycol 1.0 Panthenol 5.0 C16-Microbead-Canthaxanthin q.s. Preservative 57.9 Aqua dem. C 0.1 Bisabolol q.s. Perfume Oil D 5.7 C.I. 77 891, Titanium Dioxide 1.1 Iron Oxides
  • Preparation Heat phases A and B separately to about 80° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phases C and D and thoroughly homogenize again. Allow to cool to room temperature with stirring.
  • Dermocosmetic preparations according to the invention comprising the C16-microbead prepared according to Examples 1, or C16-microbead-canthaxanthin prepared according to Example 4.
  • the following data are parts by weight of an aqueous solution.
  • ad 100 ad 100 ad 100 Adjust pH to 6.0 Clear conditioner shampoo Polyquaternium-10 0.50 0.50 0.50 Sodium Laureth Sulfate 9.00 8.50 9.50 C16-Microbead 5.0 0.1 3.0 Uvinul M ® 40 1.00 1.50 0.50 0.20 0.20 0.80 Preservative, Perfume Oil, Thickener q.s. q.s. q.s. Aqua dem.
  • ad 100 ad 100 ad 100 Adjust pH to 6.0 Clear conditioner shampoo with volume effect Sodium Laureth Sulfate 10.00 10.50 11.00 Uvinul ® MC 80 2.00 1.50 2.30 C16-Microbead 10.0 0.1 0.5 Cocamidopropyl Betaine 2.50 2.60 2.20 Disodium EDTA 0.01 0.10 0.01 Preservative, Perfume Oil, Thickener q.s. q.s. q.s. Aqua dem. ad 100 ad 100 Adjust pH to 6.0
  • cosmetic sunscreen preparations comprising a combination of at least one inorganic pigment, preferably zinc oxide and/or titanium dioxide and organic UV-A and UV-B filters.
  • the content of C16-microbead prepared according to Example 1 or C16-microbead-canthaxanthin prepared according to Example 4 refers to 100% active ingredient.
  • the active ingredients according to the invention can be used either in pure form or in the form of an aqueous solution. In the case of the aqueous solution, the content of water dem. in the particular formulation must be adjusted.
  • Neoheliopan AP Disodium Phenyl Dibenzimidazole Tetrasulfonate 0.20 Edeta BD Disodium EDTA 5.00 1,2-Propylene Glycol Care Propylene Glycol D 1.00 Vitamin E Acetate Tocopheryl Acetate q.s.
  • Preservative 26 A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol 2.00 Cremophor A 25 Ceteareth-25 3.00 Syncrowax HRC Tribehenin 2.00 Lanette O Cetearyl Alcohol 2.00 Luvitol EHO Cetearyl Ethylhexanoate 7.00 Uvinul N 539 T Octocrylene 1.00 Ganex V-220 VP/Eicosene Copolymer 7.00 Isopropyl palmitate Isopropyl Palmitate B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina Hydrate, Methicone/Dimethicone Copolymer C 0.50 Keltrol Xanthan Gum 1% C16-Microbead-Canthaxanthin 0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl Taurate Copolymer, Squalane, Polysorbate 60 64.60 Water dem.
  • Bisabolol 1.84 Vitamin E Acetate Tocopheryl Acetate 0.42 D,L-Alpha-Tocopherol Tocopherol 2% C16-Microbead-Canthaxanthin 39.38 Castor oil Castor (Ricinus Communis) Oil A 6.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil 2.00 Elfacos ST 9 PEG-45/Dodecyl Glycol Copolymer 3.00 Isopropyl myristate Isopropyl Myristate 8.00 Jojoba oil Simmondsia Chinensis (Jojoba) Seed Oil 4.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate 2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate 1.00 Abil 350 Dimethicone B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone 3.00 T-Lite SF Titanium Di
  • Bisabolol A 25.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane 20.00 Dow Corning 245 Fluid Cyclopentasiloxane 8.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate 4.00 Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone 7.00 T-Lite SF Titanium Dioxide, Alumina Hydrate, Dimethicone/Methicone Copolymer B 17.00 Ethanol 95% Alcohol 10.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone 4.50 Water dem. Aqua dem.
  • a 4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2 Dipolyhydroxystearate, Glycerin 2.00 Lanette O Cetearyl Alcohol 12.00 Myritol 331 Cocoglycerides 8.00 Finsolv TN C12-15 Alkyl Benzoate 8.00 Cetiol B Dibutyl Adipate B 6.00 T-Lite SF Titanium Dioxide, Alumina Hydrate, Dimethicone/Methicone Copolymer 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone C 3.00 Glycerin 87% Glycerin 0.10 Edeta BD Disodium EDTA 1.50 Veegum Ultra Magnesium Aluminum Silicate 1.50 Lanette E Sodium Cetearyl Sulfate 2% C16-Microbead 0.30 Keltrol Xanthan Gum 45.10 Water dem.
  • Preservative A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate 5.00 Uvinul N 539 T Octocrylene 3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol 2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate 1.00 Fitoderm Squalane 0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil 0.50 Cremophor PS 20 Polysorbate 20 2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone 0.03 Sicomet Blue P 77 007 C.I.
  • Bisabolol 1.84 Vitamin E Acetate Tocopheryl Acetate 1.0% C16-Microbead 0.42 D,L-Alpha-Tocopherol Tocopherol 40.38 Castor oil Castor (Ricinus Communis) Oil A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16 Dimethicone, Caprylic/Capric Triglyceride 3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil 0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil 2.00 Mexoryl XL Drometrizole Trisiloxane 10.00 Witconol APM PPG-3 Myristyl Ether 1.00 Uvinul T 150 Ethylhexyl Triazone 1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane 5.00 Uvinul N 539 T Octocrylene B 3.00 T-Lite SF-S Titanium Dioxide, Silica

Abstract

Use of protein microbeads in cosmetics

Description

  • The present invention relates to the use of protein microbeads in cosmetics, in particular in skin cosmetics.
    • PRIOR ART
  • EP 1110534 describes a cosmetic product of ultrafine crystalline silk powder which is produced by treating silk under alkaline conditions at a temperature above 100° C. and subsequent mechanical comminution.
    • DESCRIPTION OF THE INVENTION
  • The present invention relates, in a first embodiment, to the use of protein microbeads in cosmetics.
    • Protein Microbeads (i)
  • Protein microbeads consist of polypeptides which are constructed from amino acids, in particular from the 20 naturally occurring amino acids. The amino acids can also be modified, for example acetylated, glycosylated, farnesylated.
  • In addition, the protein microbeads have a globular structure with an average particle diameter of from 0.1 to 100 μm, in particular from 0.5 to 20 μm, preferably from 1 to 5 μm and particularly preferably from 2 to 4 μm.
  • Protein microbeads can preferably be produced by the method described below:
  • The protein is dissolved in a first solvent. Solvents which can be used are, for example, aqueous salt solutions. In particular, highly concentrated salt solutions with a concentration greater than 2 molar, in particular greater than 4 molar and particularly preferably greater than 5 molar, whose ions have more marked chaotropic properties than sodium ions and chloride ions are suitable. One example of such a salt solution is 6 M guanidinium thiocyanate or 9 M lithium bromide. Furthermore, organic solvents can be used for dissolving the proteins. In particular, fluorinated alcohols or cyclic hydrocarbons are suitable. Examples thereof are hexafluoroisopropanol and cyclohexane. The protein microbeads can be produced in the described solvents. Alternatively, this solvent can be replaced by a further solvent, e.g. low-concentration salt solutions (c<0.5 M) through dialysis or dilution. The end concentration of the dissolved protein should be between 0.1-100 mg/ml. The temperature at which the method is carried out is usually 0-80° C., preferably 5-50° C. and particularly preferably 10-40° C.
  • When using aqueous solutions, these may also be admixed with a buffer, preferably in the pH range 4-10, particularly preferably 5 to 9, very particularly preferably 6 to 8.5. By adding an additive, phase separation is induced. This produces a protein-rich phase emulsified in the mixture as solvent and additive. On account of surface effects, emulsified protein-rich droplets adopt a round shape. Through the choice of solvent, of additive and of protein concentration, the average diameter of the protein microbeads can be adjusted to values between 0.1 μm and 100 μm.
  • As additive, all substances can be used which, on the one hand, are miscible with the first solvent and, on the other hand, induce the formation of a protein-rich phase. If the microbead formation is carried out in organic solvents, then organic substances suitable for this purpose are those which have a lower polarity than the solvent, e.g. toluene. In aqueous solutions, salts may be used as additive whose ions have more marked cosmotropic properties than sodium ions and chloride ions (e.g. ammonium sulfate; potassium phosphate). The end concentration of the additive should be between 1% and 50% by weight, based on the protein solution, depending on the type of additive.
  • The protein-rich droplets are fixed by curing, with retention of the round shape. The fixing is based here on the formation of strong intermolecular interactions. The type of interactions may be noncovalent, e.g. through the formation of intermolecular β-pleated sheet crystals, or covalent, e.g. through chemical crosslinking. The curing can take place through the additive and/or through the addition of a further suitable substance. The curing takes place at temperatures between 0 and 80° C., preferably between 5 and 60° C.
  • This further substance may be a chemical crosslinker. A chemical crosslinker is understood here as meaning a molecule in which at least two chemically reactive groups are joined together via a linker. Examples thereof are sulfhydryl-reactive groups (e.g. maleimides, pydridyldisulfides, α-haloacetyls, vinylsulfones, sulfatoalkylsulfones (preferably sulfatoethylsulfones)), amine-reactive groups (e.g. succinimidyl esters, carbodiimides, hydroxymethylphosphine, imido esters, PFP esters, aldehydes, isothiocyanates etc.), carboxy-reactive groups (e.g. amines etc.), hydroxyl-reactive groups (e.g. isocyanates etc.), unselective groups (e.g. aryl azides etc.) and photoactivatable groups (e.g. perfluorophenyl azide etc.). These reactive groups can form covalent linkages with amine, thiol, carboxyl or hydroxyl groups present in proteins.
  • The stabilized microbeads are washed with a suitable further solvent, e.g. water, and then dried by methods known to the person skilled in the art, e.g. by lyophilization or spray-drying. The success of bead formation is checked with the help of scanning electron microscopy.
  • Suitable proteins for producing protein microbeads are proteins which are present in predominantly intrinsically unfolded form in aqueous solution. This state can be calculated, for example, by an algorithm on which the program IUpred is based (http://iupred.enzim.hu/index.html; The Pairwise Energy Content Estimated from Amino Acid Composition Discriminates between Folded and Intrinsically Unstructured Proteins; Zsuzsanna Dosztányi, Veronika Csizmók, Péter Tompa and István Simon; J. Mol. Biol. (2005) 347, 827-839). A predominantly intrinsically unfolded state is assumed if a value of >0.5 is calculated for more than 50% of the amino acid radicals according to this algorithm (prediction type: long disorder).
  • Suitable proteins for producing protein microbeads are silk proteins. These are understood below as meaning those proteins which comprise highly repetitive amino acid sequences and are stored in the animal in a liquid form and during their secretion fibers are produced by shearing or spinning. (Craig, C. L. (1997) Evolution of arthropod silks. Annu. Rev. Entomol. 42: 231-67).
  • Particularly suitable proteins for producing protein microbeads are spider silk proteins which can be isolated in their original form from spiders.
  • Very particularly suitable proteins are silk proteins which could be isolated from the “Major Ampullate” gland of spiders.
  • Preferred silk proteins are ADF3 and ADF4 from the “Major Ampullate” gland of Araneus diadematus (Guerette et al., Science 272, 5258:112-5 (1996)).
  • Likewise suitable proteins for producing protein microbeads are natural or synthetic proteins which are derived from natural silk proteins and which have been produced using genetic engineering methods heterologously in prokaryotic or eukaryotic expression systems. Nonlimiting examples of prokaryotic expression organisms are Escherichia coli, Bacillus subtilis, Bacillus megaterium, Corynebacterium glutamicum etc. Nonlimiting examples of eukaryotic expression organisms are yeasts, such as Saccharomyces cerevisiae, Pichia pastoris etc., filamentous fungi, such as Aspergillus niger, Aspergillus oryzae, Aspergillus nidulans, Trichoderma reesei, Acremonium chrysogenum etc., mammal cells, such as Hela cells, COS cells, CHO cells etc., insect cells, such as Sf9 cells, MEL cells etc.
  • Of particular preference for producing protein microbeads are synthetic proteins which are based on repeat units of natural silk proteins. Besides the synthetic repetitive silk protein sequences, these can additionally comprise one or more natural nonrepetitive silk protein sequences (Winkler and Kaplan, J Biotechnol 74:85-93 (2000)).
  • Among the synthetic silk proteins, for producing protein microbeads, preference is given to synthetic spider silk proteins which are based on repeat units of natural spider silk proteins. Besides the synthetic repetitive spider silk protein sequences, these can additionally comprise one or more natural nonrepetitive spider silk protein sequences.
  • Among the synthetic spider silk proteins, the so-called C16-protein is preferably to be specified (Huemmerich et al. Biochemistry, 43(42):13604-13612 (2004)). This protein has the polypeptide sequence shown in SEQ ID NO: 1.
  • Besides the polypeptide sequence shown in SEQ ID NO:1, functional equivalents, functional derivatives and salts of this sequence in particular are also preferred.
  • According to the invention, “functional equivalents” are understood in particular as meaning also mutants which have an amino acid other than that specifically given in at least one sequence position of the abovementioned amino acid sequences but nevertheless have one of the abovementioned biological properties. “Functional equivalents” thus comprise the mutants obtainable by one or more amino acid additions, substitutions, deletions and/or inversions, where the specified changes can arise in any sequence position provided they lead to a mutant with the profile of properties according to the invention. Functional equivalence is in particular also present if the reactivity patterns between mutant and unchanged polypeptide are in qualitative agreement. “Functional equivalents” in the above sense are also “precursors” of the described polypeptides, and “functional derivatives” and “salts” of the polypeptides.
  • Here, “precursors” are natural or synthetic precursors of the polypeptides with or without the desired biological activity.
  • Examples of suitable amino acid substitutions are given in the table below:
  • Original radical Examples of substitution
    Ala Ser
    Arg Lys
    Asn Gln; His
    Asp Glu
    Cys Ser
    Gln Asn
    Glu Asp
    Gly Pro
    His Asn; Gln
    Ile Leu; Val
    Leu Ile; Val
    Lys Arg; Gln; Glu
    Met Leu; Ile
    Phe Met; Leu; Tyr
    Ser Thr
    Thr Ser
    Trp Tyr
    Tyr Trp; Phe
    Val Ile; Leu
  • The expression “salts” is understood as meaning either salts of carboxyl groups or acid addition salts of amino groups of the protein molecules according to the invention. Salts of carboxyl groups can be produced in a manner known per se and comprise inorganic salts, such as, for example, sodium, calcium, ammonium, iron and zinc salts, and also salts with organic bases, such as, for example amines, such as triethanolamine, arginine, lysine, piperidine and the like. Acid addition salts, such as, for example, salts with mineral acids, such as hydrochloric acid or sulfuric acid and salts with organic acids, such as acetic acid and oxalic acid, are likewise provided by the invention.
  • “Functional derivatives” of polypeptides according to the invention can likewise be produced on functional amino acid side groups or on their N- or C-terminal end using known techniques. Such derivatives comprise, for example, aliphatic esters of carboxylic acid groups, amides of carboxylic acid groups, obtainable by reaction with ammonia or with a primary or secondary amine; N-acyl derivatives of free amino groups, prepared by reaction with acyl groups; or O-acyl derivatives of free hydroxy groups, prepared by reaction with acyl groups.
  • The invention further provides protein microbeads which consist of couplings of a protein (i) and an effector molecule (ii). All of the proteins already specified above are suitable as protein (i). The protein (i) can either itself already be present as protein microbead and then be coupled with an effector molecule (ii), or else the protein (i) is not in the form of a protein microbead and is coupled with the effector molecule (ii) and only then is the coupled molecule converted to a protein microbead or the coupling takes place during phase separation.
    • Effector Molecules (ii)
  • Effector molecules (ii) are understood below as meaning molecules which have, a certain predictable effect. These may either be protein-like molecules, such as enzymes, or non-proteinogenic molecules, such as dyes, photoprotective agents, vitamins, provitamins, antioxidants and fatty acids, conditioners or compounds comprising metal ions.
  • Among the protein-like effector molecules, enzymes and antibodies are preferred. Among the enzymes, the following are preferred as effector molecules (ii): oxidases, peroxidases, proteases, glucanases, mutanase, tyrosinases, laccases, metal-binding enzymes, lactoperoxidase, lysozyme, amyloglycosidase, glucose oxidase, super oxide dismutase, photolyase, T4 endonuclease, katalase, thioredoxin, thioredoxin reductase. For the protein-like, but not enzymatic effector molecules, the following are preferred as effector molecules (ii): antimicrobial peptides, hydrophobins, collagen, proteins binding carotenoid, proteins binding heavy metals, proteins binding odorants, proteins binding cellulose, proteins binding starch, proteins binding keratin.
  • Highly suitable protein-like effector molecules (ii) are also hydrolyzates of proteins of vegetable and animal sources, for example hydrolyzates of proteins of marine origin.
  • Among the non-protein-like effector molecules (ii), carotenoids are preferred. According to the invention, carotenoids are understood as meaning the following compounds and their esterified or glycosylated derivatives: β-carotene, lycopene, lutein, astaxanthin, zeaxanthin, cryptoxanthin, citranaxanthin, canthaxanthin, bixin, β-Apo-4-carotenal, β-Apo-8-carotenal, β-Apo-8-carotenoic esters, neurosporene, echinenone, adonirubin, violaxanthin, torulene, torularhodin, individually or as a mixture. Preferably used carotenoids are β-carotene, lycopene, lutein, astaxanthin, zeaxanthin, citranaxanthin and canthaxanthin.
  • Further preferred effector molecules (ii) are UV photoprotective filters. These are understood as meaning organic substances which are able to absorb ultraviolet rays and release the absorbed energy again in the form of long-wave radiation, e.g. heat. The organic substances may be oil-soluble or water-soluble.
  • Oil-soluble UV-B filters which may be used are, for example, the following substances: 3-benzylidenecamphor and derivatives thereof, e.g. 3-(4-methylbenzylidene)camphor;
  • 4-aminobenzoic 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, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene);
  • esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylate;
  • derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone;
  • esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
  • triazine derivatives, such as, for example, 2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine (octyltriazone) and dioctylbutamidotriazone (Uvasorb® HEB);
  • propane-1,3-diones, such as, for example, 1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,
  • Suitable water-soluble substances are:
  • 2-phenylbenzimidazole-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-methoxybenzo-phenone-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.
  • Particular preference is given to the use of esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene).
  • Furthermore, the use of derivatives of benzophenone, in particular 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and the use of propane-1,3-diones, such as, for example, 1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione is preferred.
  • Suitable typical UV-A filters are:
  • derivatives of benzoylmethane, such as, for example, 1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione, 4-tert-butyl-4′-methoxydibenzoylmethane or 1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione;
  • aminohydroxy-substituted derivatives of benzophenones, such as, for example, N,N-diethylaminohydroxybenzoyl n-hexylbenzoate.
  • The UV-A and UV-B filters can of course also be used in mixtures.
  • Suitable UV filter substances are given in the table below.
  • CAS No.
    No. Substance (=acid)
    1 4-Aminobenzoic acid 150-13-0
    2 3-(4′-Trimethylammonium)benzylidenebornan-2-one methyl 52793-97-2
    sulfate
    3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9
    (homosalate)
    4 2-Hydroxy-4-methoxybenzophenone 131-57-7
    (oxybenzone)
    5 2-Phenylbenzimidazole-5-sulfonic acid and its potassium, 27503-81-7
    sodium and triethanolamine salts
    6 3,3′-(1,4-Phenylenedimethine)bis(7,7-dimethyl- 90457-82-2
    2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its
    salts
    7 Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9
    8 2-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3
    9 2-Ethylhexyl salicylate 118-60-5
    10 2-Isoamyl 4-methoxycinnamate 71617-10-2
    11 2-Ethylhexyl 4-methoxycinnamate 5466-77-3
    12 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6
    (sulisobenzone) and the sodium salt
    13 3-(4′-Sulfobenzylidene)bornan-2-one and salts 58030-58-6
    14 3-Benzylidenebornan-2-one 16087-24-8
    15 1-(4′-Isopropylphenyl)-3-phenylpropane-1,3-dione 63260-25-9
    16 4-Isopropylbenzyl salicylate 94134-93-7
    17 3-Imidazol-4-ylacrylic acid and its ethyl ester 104-98-3
    18 Ethyl 2-cyano-3,3-diphenylacrylate 5232-99-5
    19 2′-Ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4
    20 Menthyl o-aminobenzoate or: 134-09-8
    5-methyl-2-(1-methylethyl)-2-aminobenzoate
    21 Glyceryl p-aminobenzoate or: 136-44-7
    1-glyceryl 4-aminobenzoate
    22 2,2′-Dihydroxy-4-methoxybenzophenone (dioxybenzone) 131-53-3
    23 2-Hydroxy-4-methoxy-4-methyl-benzophenone 1641-17-4
    (mexenone)
    24 Triethanolamine salicylate 2174-16-5
    25 Dimethoxyphenylglyoxalic acid or: 4732-70-1
    3,4-dimethoxyphenylglyoxal acidic sodium
    26 3-(4′-Sulfobenzylidene)bornan-2-one and its salts 56039-58-8
    27 4-tert-Butyl-4′-methoxydibenzoylmethane 70356-09-1
    28 2,2′,4,4′-Tetrahydroxybenzophenone 131-55-5
    29 2,2′-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3,- 103597-45-1
    tetramethylbutyl)phenol]
    30 2,2′-(1,4-Phenylene)bis-1H-benzimidazole-4,6- 180898-37-7
    disulfonic acid, Na salt
    31 2,4-bis[4-(2-Ethylhexyloxy)-2-hydroxy]phenyl- 187393-00-6
    6-(4-methoxyphenyl)-(1,3,5)-triazine
    32 3-(4-Methylbenzylidene)camphor 36861-47-9
    33 Polyethoxyethyl 4-bis(polyethoxy)paraaminobenzoate 113010-52-9
    34 2,4-Dihydroxybenzophenone 131-56-6
    35 2,2′-Dihydroxy-4,4′-dimethoxybenzophenone-5,5′- 3121-60-6
    disodium sulfonate
    36 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester 302776-68-7
    37 2-(2H-Benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- 155633-54-8
    tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol
    38 1,1-[(2,2′-Dimethylpropoxy)carbonyl]-4,4-diphenyl-1,3-butadiene 363602-15-7
  • Besides the two abovementioned groups of primary photoprotective substances, it is also possible to use secondary photoprotective agents of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples thereof are superoxide dismutase, catalase, tocopherols (vitamin E), coenzyme Q10, ubiquinanes, quinones and ascorbic acid (vitamin C).
  • A further group are antiirritants which have an antiinflammatory effect on skin damaged by UV light. Such substances are, for example, bisabolol, phytol and phytantriol.
  • Effector molecules (ii) according to the invention are also inorganic pigments which stop UV rays. Preference is given to pigments based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water and chosen from the group of oxides of zinc (ZnO), titanium (TiO2), iron (e.g. Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminum (Al2O3), cerium (e.g. Ce2O3), mixed oxides of the corresponding metals and mixtures of such oxides.
  • The inorganic pigments can be present here in coated form, i.e. are treated superficially. This surface treatment can consist, for example, in providing the pigments with a thin hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
  • Further preferred effector molecules (ii) are vitamins, in particular vitamin A and esters thereof.
  • For the purposes of the present invention, retinoids are understood as meaning vitamin A alcohol (retinol) and its derivatives, such as vitamin A aldehyde (retinal), vitamin A acid (retinoic acid) and vitamin A ester (e.g. retinyl acetate, retinyl propionate and retinyl palmitate). The term retinoic acid here comprises both all-trans retinoic acid and also 13-cis-retinoic acid. The terms retinol and retinal preferably comprise the all-trans compounds. A preferred retinoid used for the suspensions according to the invention is all-trans-retinol, referred to below as retinol.
  • Further preferred effector molecules (ii) are vitamins, provitamins and vitamin precursors from the groups A, C, E and F, in particular 3,4-didehydroretinol, β-carotene (provitamin of vitamin A), ascorbic acid (vitamin C), and the palmitic esters, glucosides or phosphates of ascorbic acid, tocopherols, in particular α-tocopherol, and its esters, e.g. the acetate, the nicotinate, the phosphate and the succinate; also vitamin F, which is understood as meaning essential fatty acids, particularly linoleic acid, linolenic acid and arachidonic acid.
  • The vitamins, provitamins or vitamin precursors of the vitamin B group or derivatives thereof and the derivatives of 2-furanone to be used with preference according to the invention include, inter alia:
  • Vitamin B1, trivial name thiamine, chemical name 3-[(4′-amino-2′-methyl-5′-pyrimidinyl)-methyl]-5-(2-hydroxyethyl)-4-methylthiazolium chloride.
  • Vitamin B2, trivial name riboflavin, chemical name 7,8-dimethyl-10-(1-D-ribityl)-benzo[g]pteridine-2,4(3H,10H)-dione. In free form, riboflavin occurs, for example, in whey, other riboflavin derivatives can be isolated from bacteria and yeasts. A stereoisomer of riboflavin which is likewise suitable according to the invention is lyxoflavin, which can be isolated from fish meal or liver and bears a D-arabityl radical instead of the D-ribityl radical.
  • Vitamin B3. The compounds nicotinic acid and nicotinamide (niacinamide) often bear this name. According to the invention, preference is given to nicotinamide.
  • Vitamin Bs (pantothenic acid and panthenol). Preference is given to using panthenol. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol, and cationically derivatized panthenols. In a further preferred embodiment of the invention, derivatives of 2-furanone can also be used in addition to pantothenic acid or panthenol. Particularly preferred derivatives are the also commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone with the trivial name pantolactone (Merck), 4-hydroxymethyl-γ-butyrolactone (Merck), 3,3-dimethyl-2-hydroxy-γ-butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck), with all stereoisomers being expressly included.
  • These effector molecule compounds advantageously impart moisturizing and skin-calming properties to the protein microbeads (i) according to the invention.
  • Vitamin B6, which is not understood here as meaning a uniform substance, but the derivatives of 5-hydroxymethyl-2-methylpyridin-3-ol known under the trivial names pyridoxin, pyridoxamine and pyridoxal.
  • Vitamin B7 (biotin), also referred to as vitamin H or “skin vitamin”. Biotin is (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]imidazole-4-valeric acid.
  • Panthenol, pantolactone, nicotinamide and biotin are very particularly preferred according to the invention.
  • According to the invention, suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids) of the specified compounds can be used as effector molecules. As lipophilic, oil-soluble antioxidants from this group, preference is given to tocopherol and derivatives thereof, gallic esters, flavonoids and carotenoids and also butylhydroxytoluene/anisole. Preferred water-soluble antioxidants are amino acids, e.g. tyrosine and cysteine and derivatives thereof, and tannins, in particular those of vegetable origin.
  • Furthermore, preference is given to so-called peroxide decomposers, i.e. compounds which are able to decompose peroxides, particularly preferably lipid peroxides. These are understood as meaning organic substances, such as, for example, pyridine-2-thiol-3-carboxylic acid, 2-methoxypyrimidinolcarboxylic acids, 2-methoxypyridinecarboxylic acids, 2-dimethylaminopyrimidinolcarboxylic acids, 2-dimethylaminopyridinecarboxylic acids.
  • Triterpenes, in particular triterpenoic acids, such as ursolic acid, rosmaric acid, betulinic acid, boswellic acid and bryonolic acid.
  • A further preferred effector molecule (ii) is lipoic acid and suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids).
  • Further preferred effector molecules (ii) are fatty acids, in particular saturated fatty acids which carry an alkyl branch, particularly preferably branched elcosanoic acids, such as 18-methyleicosanoic acid.
  • Further preferred effector molecules (ii) are dyes, for example food dyes, semi-permanent dyes, reactive or oxidation dyes. In the case of the oxidation dyes, it is preferred to link a component as effector molecule (ii) with the protein microbeads (i) and then to couple oxidatively with the second dye component at the site of action, i.e. following application to skin. In the case of oxidation dyes it is also preferred to carry out the coupling of the dye components before the linkage with the protein microbeads (i).
  • The reactive dyes can also preferably be linked as a component as effector molecule (ii) with the protein microbeads (I) and then be applied to the skin. In addition, those dyes which are linked as effector molecule (ii) with the protein microbeads (i) can be used in decorative cosmetics by application to skin.
  • Suitable dyes are all customary hair dyes for the molecules according to the invention. Suitable dyes are known to the person skilled in the art from cosmetics handbooks, for example Schrader, Grundlagen and Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics], Hithig Verlag, Heidelberg, 1989, ISBN 3-7785-1491-1.
  • Particularly advantageous dyes are those specified in the list below. The Colour Index Numbers (CIN) are given in the Rowe Colour Index, 3rd edition, Society of Dyers and Colourists, Bradford, England, 1971.
  • Chemical or other name CIN Color
    Pigment Green 10006 green
    Acid Green 1 10020 green
    2,4-Dinitrohydroxynaphthalene-7-sulfonic acid 10316 yellow
    Pigment Yellow 1 11680 yellow
    Pigment Yellow 3 11710 yellow
    Pigment Orange 1 11725 orange
    2,4-Dihydroxyazobenzene 11920 orange
    Solvent Red 3 12010 red
    1-(2′-Chloro-4′-nitro-1′-phenylazo)-2-hydroxynaphthalene 12085 red
    Pigment Red 3 12120 red
    Ceres Red; Sudan Red; Fett Red G 12150 red
    Pigment Red 112 12370 red
    Pigment Red 7 12420 red
    Pigment Brown 1 12480 brown
    4-(2′-Methoxy-5′-sulfodiethylamido-1′-phenylazo)-3-hydroxy- 12490 red
    5″-chloro-2″,4″-dimethoxy-2-naphthanilide
    Disperse Yellow 16 12700 yellow
    1-(4-Sulfo-1-phenylazo)-4-aminobenzene-5-sulfonic acid 13015 yellow
    2,4-Dihydroxyazobenzene-4′-sulfonic acid 14270 orange
    2-(2,4-Dimethylphenylazo-5-sulfonic acid)-1-hydroxy- 14700 red
    naphthalene-4-sulfonic acid
    2-(4-Sulfo-1-naphthylazo)-1-naphthol-4-sulfonic acid 14720 red
    2-(6-Sulfo-2,4-xylylazo)-1-naphthol-5-sulfonic acid 14815 red
    1-(4′-Sulfophenylazo)-2-hydroxynaphthalene 15510 orange
    1-(2-Sulfo-4-chloro-5-carboxy-1-phenylazo)-2-hydroxy- 15525 red
    naphthalene
    1-(3-Methylphenylazo-4-sulfo)-2-hydroxynaphthalene 15580 red
    1-(4′,(8′)-Sulfonaphthylazo)-2-hydroxynaphthalene 15620 red
    2-Hydroxy-1,2′-azonaphthalene-1′-sulfonic acid 15630 red
    3-Hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red
    1-(2-Sulfo-4-methyl-1-phenylazo)-2-naphthylcarboxylic acid 15850 red
    1-(2-Sulfo-4-methyl-5-chloro-1-phenylazo)-2-hydroxy- 15865 red
    naphthalene-3-carboxylic acid
    1-(2-Sulfo-1-naphthylazo)-2-hydroxynaphthalene-3-carboxylic 15880 red
    acid
    1-(3-Sulfo-1-phenylazo)-2-naphthol-6-sulfonic acid 15980 orange
    1-(4-Sulfo-1-phenylazo)-2-naphthol-6-sulfonic acid 15985 yellow
    Allura Red 16035 red
    1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6-disulfonic acid 16185 red
    Acid Orange 10 16230 orange
    1-(4-Sulfo-1-naphthylazo)-2-naphthol-6,8-disulfonic acid 16255 red
    1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6,8-trisulfonic acid 16290 red
    8-Amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red
    Acid Red 1 18050 red
    Acid Red 155 18130 red
    Acid Yellow 121 18690 yellow
    Acid Red 180 18736 red
    Acid Yellow 11 18820 yellow
    Acid Yellow 17 18965 yellow
    4-(4-Sulfo-1-phenylazo)-1-(4-sulfophenyl)-5-hydroxypyrazolone- 19140 yellow
    3-carboxylic acid
    Pigment Yellow 16 20040 yellow
    2,6-(4′-Sulfo-2″,4″-dimethyl)bis(phenylazo)-1,3-dihydroxy- 20170 orange
    benzene
    Acid Black 1 20470 black
    Pigment Yellow 13 21100 yellow
    Pigment Yellow 83 21108 yellow
    Solvent Yellow 21230 yellow
    Acid Red 163 24790 red
    Acid Red 73 27290 red
    2-[4′-(4″-Sulfo-1″-phenylazo)-7′-sulfo-1′-naphthylazo]-1-hydroxy- 27755 black
    7-aminonaphthalene-3,6-di-sulfonic acid
    4′-[(4″-Sulfo-1″-phenylazo)-7′-sulfo-1′-naphthylazo]-1-hydroxy- 28440 black
    8-acetylaminonaphthalene-3,5-disulfonic acid
    Direct Orange 34, 39, 44, 46, 60 40215 orange
    Food Yellow 40800 orange
    trans-β-Apo-8′-Carotenaldehyde (C30) 40820 orange
    trans-Apo-8′-Carotenic acid(C30)-ethyl ester 40825 orange
    Canthaxanthin 40850 orange
    Acid Blue 1 42045 blue
    2,4-Disulfo-5-hydroxy-4′-4″-bis(dimethylamino)triphenylcarbinol 42051 blue
    4-[(-4-N-Ethyl-p-sulfobenzylamino)phenyl-(4-hydroxy- 42053 green
    2-sulfophenyl)(methylene)-1-(N-ethyl-N-p-sulfobenzyl)-
    2,5-cyclohexadienimine]
    Acid Blue 7 42080 blue
    (N-Ethyl-p-sulfobenzylamino)phenyl-(2-sulfophenyl)methylene- 42090 blue
    (N-ethyl-N-p-sulfobenzyl)-□2,5-cyclohexadienimine
    Acid Green 9 42100 green
    Diethyldisulfobenzyldi-4-amino-2-chloro-di-2-methyl- 42170 green
    fuchsonimmonium
    Basic Violet 14 42510 violet
    Basic Violet 2 42520 violet
    2′-Methyl-4′-(N-ethyl-N-m-sulfobenzyl)amino- 42735 blue
    4″-(N-diethyl)amino-2-methyl-N-ethyl-N-m-sulfobenzyl-
    fuchsonimmonium
    4′-(N-Dimethyl)amino-4″-(N-phenyl)aminonaphtho-N-dimethyl- 44045 blue
    fuchsonimmonium
    2-Hydroxy-3,6-disulfo-4,4′-bis-dimethylaminonaphtho- 44090 green
    fuchsonimmonium
    Acid Red 52 45100 red
    3-(2′-Methylphenylamino)-6-(2′-methyl-4′-sulfophenylamino)- 45190 violet
    9-(2″-carboxyphenyl)xanthenium salt
    Acid Red 50 45220 red
    Phenyl-2-oxyfluorone-2-carboxylic acid 45350 yellow
    4,5-Dibromofluorescein 45370 orange
    2,4,5,7-Tetrabromofluorescein 45380 red
    Solvent Dye 45396 orange
    Acid Red 98 45405 red
    3′,4′,5′,6′-Tetrachloro-2,4,5,7-tetrabromofluorescein 45410 red
    4,5-Diiodofluorescein 45425 red
    2,4,5,7-Tetraiodofluorescein 45430 red
    Quinophthalone 47000 yellow
    Quinophthalonedisulfonic acid 47005 yellow
    Acid Violet 50 50325 violet
    Acid Black 2 50420 black
    Pigment Violet 23 51319 violet
    1,2-Dioxyanthraquinone, calcium-aluminum complex 58000 red
    3-Oxypyrene-5,8,10-sulfonic acid 59040 green
    1-Hydroxy-4-N-phenylaminoanthraquinone 60724 violet
    1-Hydroxy-4-(4′-methylphenylamino)anthraquinone 60725 violet
    Acid Violet 23 60730 violet
    1,4-Di(4′-methylphenylamino)anthraquinone 61565 green
    1,4-Bis(o-sulfo-p-toluidino)anthraquinone 61570 green
    Acid Blue 80 61585 blue
    Acid Blue 62 62045 blue
    N,N′-Dihydro-1,2,1′,2′-anthraquinonazine 69800 blue
    Vat Blue 6; Pigment Blue 64 69825 blue
    Vat Orange 7 71105 orange
    Indigo 73000 blue
    Indigo-disulfonic acid 73015 blue
    4,4′-Dimethyl-6,6′-dichlorothioindigo 73360 red
    5,5′-Dichloro-7,7′-dimethylthioindigo 73385 violet
    Quinacridone Violet 19 73900 violet
    Pigment Red 122 73915 red
    Pigment Blue 16 74100 blue
    Phthalocyanine 74160 blue
    Direct Blue 86 74180 blue
    Chlorinated phthalocyanines 74260 green
    Natural Yellow 6,19; Natural Red 1 75100 yellow
    Bixin, Norbixin 75120 orange
    Lycopene 75125 yellow
    trans-alpha-, beta- or gamma-Carotene 75130 orange
    Keto and/or hydroxyl derivatives of carotene 75135 yellow
    Guanine or pearlizing agent 75170 white
    1,7-Bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione 75300 yellow
    Complex salt (Na, Al, Ca) of carminic acid 75470 red
    Chlorophyll a and b; copper compounds of the chlorophylls and 75810 green
    chlorophyllins
    Aluminum 77000 white
    Clay earth hydrate 77002 white
    Hydrous aluminum silicates 77004 white
    Ultramarine 77007 blue
    Pigment Red 101 and 102 77015 red
    Barium sulfate 77120 white
    Bismuth oxychloride and its mixtures with mica 77163 white
    Calcium carbonate 77220 white
    Calcium sulfate 77231 white
    Carbon 77266 black
    Pigment Black 9 77267 black
    Carbo medicinalis vegetabilis 77268 black
    Chromium oxide 77288 green
    Chromium oxide, hydrous 77289 green
    Pigment Blue 28, Pigment Green 14 77346 green
    Pigment Metal 2 77400 brown
    Gold 77480 brown
    Iron oxides and hydroxides 77489 orange
    Iron oxide 77491 red
    Iron oxide hydrate 77492 yellow
    Iron oxide 77499 black
    Mixtures of iron(II) and iron(III) hexacyanoferrate 77510 blue
    Pigment White 18 77713 white
    Manganese ammonium diphosphate 77742 violet
    Manganese phosphate; Mn3(PO4)2 □ 7 H2O 77745 red
    Silver 77820 white
    Titanium dioxide and its mixtures with mica 77891 white
    Zinc oxide 77947 white
    6,7-Dimethyl-9-(1′-D-ribityl)isoalloxazine, lactoflavin yellow
    Sugar coloring brown
    Capsanthin, capsorubin orange
    Betanin red
    Benzopyrylium salts, anthocyans red
    Aluminum, zinc, magnesium and calcium stearate white
    Bromothymol blue blue
    Bromo cresol green green
    Acid Red 195 red
  • Food dyes can also be highly suitable as dyes.
    • Linking (Coupling) of the Effector Molecules (ii) to the Protein (i)
  • The effector molecules (ii) are joined to protein (i). The bond between (i) and (ii) can either be a covalent bond, or be based on ionic or van der Waals' interactions or hydrophobic interactions or hydrogen bridge bonds or adsorption.
  • Each type of coupling, covalent or noncovalent, of effector molecule (ii) to protein (i) forming the microbead can take place in the dissolved state before phase separation. After the coupling, the formation of microbeads described in Example 1 takes place by phase separation.
  • Alternatively, a coupling of the effector molecule (ii) can also take place onto the protein microbead (i) already produced by phase separation, or during the phase separation process.
  • Preference is given to a noncovalent coupling of the effector molecule (ii) onto protein (i) forming the microbead. This can be based either on ionic or van der Weals' interactions or hydrophobic interactions or hydrogen bridge bonds. Here, during the phase separation, as described in Ex. 4, the effector molecule is incorporated into the protein microbeads (i) or bonded to their surface.
  • In order to bind effector molecules (ii) non-covalently to the microbead-forming protein (i), the effector molecule (ii) and the protein (i) are dissolved in the same solvent to give a common phase. For this, both components can be brought directly into solution by a solvent or a solvent mixture. Alternatively, the effector molecule (ii) can firstly be dissolved in a solvent other than the microbead-forming protein (i) and then be mixed with the protein solution (i), again giving a common phase. The predissolution of the effector molecule (ii) is especially of advantage if the effector molecule (ii) and the microbead-forming protein (i) can not be dissolved in the same solvent, such as, for example, in the case of aqueous protein solutions (i) and hydrophobic effector molecules (ii). Examples of suitable, water-miscible solvents are alcohols, such as methanol, ethanol and isopropanol, fluorinated alcohols, such as hexafluoroisopropanol and trifluoroethanol, alkanones, such as acetone, and also sulfoxides, such as, for example, dimethyl sulfoxide or formamides such as dimethylformamide. Alternatively, the microbead-forming protein (i) can be dissolved in fluorinated alcohols, such as, for example, hexafluoroisopropanol or trifluoroethanol, and the protein solution can then be mixed with effector molecules (ii) in organic solvents. Suitable solvents which can, for example, be mixed well with hexafluoroisopropanol are, inter glia, alcohols, such as methanol, ethanol and isopropanol, alkanones, such as acetone, sulfoxides, such as, for example, dimethyl sulfoxide, formamides, such as dimethylformamide, haloalkanes, such as methylene chloride, and also further organic solvents, such as tetrahydrofuran.
  • The noncovalent binding of the effector molecule (ii) to the microbead-forming protein (i) takes place during the assembly of the protein (i) to microbeads, where the assembly can take place as described in Example 1 through induced phase separation into a solid protein phase and a solvent phase. Through the choice of solvent and protein concentration, the average diameter of the protein microbeads can be adjusted to values between 0.1 μm and 100 μm. After the assembly reaction, the morphology of the microbeads (i) should be determined by light and electron microscopic methods.
  • The binding of the effector molecule can be based on hydrophobic interactions, hydrogen bridges, ionic interaction and van der Waals' interactions or a mixture of these intermolecular forces. Here, the effector molecule can be bound to the surface of the protein microbeads (i), be incorporated into the protein microbeads (i), or be associated with the protein microbeads (i) in both ways.
  • The binding of the effector molecule to the protein microbeads (i) can be determined through the depletion of the assembly stock of soluble effector molecules (ii). The concentration of the effector molecules (ii) can be measured by a quantitative analysis of the effector molecule properties. For example, the binding of colored effector molecules (ii) can be analyzed, for example, by photometric methods. For this, for example, the coloring of the protein microbeads (i) or the decoloring of the assembly stock are determined by measuring the absorption of the colored effector molecule. Through these methods it is also possible to calculate the charge density of the protein microbeads (i) (effector molecules per protein) and the charge efficiency (% bonded effector molecules).
  • Alternatively to the noncovalent coupling, a covalent linking of the effector molecule (ii) to the protein microbeads (i) can take place as described in Example 6. This can take place, for example, via the side chains of the polypeptide sequence of the microbead-forming protein (i), in particular via amino functions or hydroxy functions or carboxylate functions or thiol functions. Preference is given to a linking via the amino functions of one or more lysine radicals, via the carboxylate functions of one or more glutamate or aspartate radicals, one or more thiol groups of cysteine radicals or via the N-terminal or C-terminal function of the microbead-forming polypeptide (i). Apart from the amino acid functions occurring in the microbead-forming polypeptide sequence (i), amino acids with suitable functions (e.g. cysteines, lysines, aspartates, glutamates) can also be attached to the sequence or be inserted into the sequence, or amino acids of the microbead-forming polypeptide sequence (i) can be substituted by such amino acid functions.
  • The linking of the effector molecules (ii) with the microbead-forming protein (i) can either take place directly, i.e. as a covalent linking of two chemical functions already present in (i) and (ii), for example an amino function of (i) is linked with a carboxylate function of (ii) to give the acid amide. The linking can, however, also take place via a so-called linker, i.e. an at least bifunctional molecule which enters into a bond with (i) with one function and is linked to (ii) with one or more other functions.
  • If the effector molecule (ii) likewise consists of a polypeptide sequence, the linking of (i) and (ii) can take place as a so-called fusion protein, i.e. a general polypeptide sequence which consists of the two part sequences (i) and (ii).
  • It is also possible for so-called spacer elements to be incorporated between (i) and (ii), for example polypeptide sequences which have a potential cleavage site for a protease, lipase, esterase, phosphatase, hydrolase, or oligo- or polypeptide sequences which permit simple purification of the fusion protein, for example so-called His tags, i.e. oligohistidine radicals.
  • In addition, the spacer elements can be composed of alkyl chains, ethylene glycol and polyethylene glycols.
  • Particular preference is given to linker and/or spacer elements which have a potential cleavage site for a protease, lipase, esterase, phosphatase, hydrolase, i.e. are enzymatically cleavable.
  • Examples of enzymatically cleavable linkers which can be used in the case of the molecules according to the invention are specified, for example, in WO 98/01406, to the entire content of which reference is hereby expressly made.
  • Particular preference is given to linkers and spacers which are thermocleavable, photocleavable. Corresponding chemical structures are known to the person skilled in the art and are integrated between the molecule parts (i) and (ii).
  • The linking in the case of a non-protein-like effector molecule with the protein microbeads (i) takes place preferably through functionalizable radicals (side groups, C or N terminus) on the microbead-forming polypeptide (i), which enter into a covalent bond with a chemical function of the effector molecule.
  • Preference here is given to the binding linkage via an amino, thiol or hydroxy function of the microbead-forming polypeptide (i), which can enter into a corresponding amide, thioester or ester bond, for example with a carboxyl function of the effector molecule (ii), if appropriate following activation.
  • A further preferred linking of the protein microbeads (i) with an effector molecule (ii) is the use of a tailored linker. Such a linker has two or more so-called anchor groups with which it can link the microbead-forming polypeptide sequence (i) and one or more effector molecules (ii). For example, an anchor group for (i) may be a thiol function by means of which the linker can enter into a disulfide bond with a cysteine radical of the microbead-forming polypeptide (i). An anchor group for (ii) can, for example, be a carboxyl function by means of which the linker can enter into an ester bond with a hydroxyl function of the effector molecule (ii).
  • The use of such tailored linkers permits the precise matching of the linking to the desired effector molecule. Furthermore, it is thereby possible to link a plurality of effector molecules with a microbead-forming polypeptide sequence (i) in a defined way.
  • The linker used is governed by the functionality to be coupled. Of suitability are, for example, molecules which couple to microbead-forming polypeptides (i) by means of sulfhydryl-reactive groups, e.g. maleimides, pydridyldisulfides, α-haloacetyls, vinylsulfones, sulfatoalkylsulfones (preferably sulfatoethylsulfones) and to effector molecules (ii) by means of
      • sulfhydryl-reactive groups (e.g. maleimides, pydridyldisulfides, α-haloacetyls, vinylsulfones, sulfatoalkylsulfones (preferably sulfatoethylsulfones)
      • amine-reactive groups (e.g. succinimidyl esters, carbodiimides, hydroxy-methylphosphine, imido esters, PFP esters, aldehyde, isothiocyanate etc.)
      • sugars and oxidized sugar-reactive groups (e.g. hydrazides etc.)
      • carboxy-reactive groups (e.g. amines etc.)
      • hydroxyl-reactive groups (e.g. isocyanates etc.)
      • thymine-reactive groups (e.g. psoralene etc.)
      • unselective groups (e.g. aryl azides etc.)
      • photoactivatable groups (e.g. perfluorophenyl azide etc.)
      • metal-complexing groups (e.g. EDTA, hexahis, ferritin)
      • antibodies and fragments (e.g. single-chain antibodies, F(ab) fragments of antibodies, catalytic antibodies).
  • Alternatively, a direct coupling between effector molecules and the protein microbeads (i) can be carried out, for example, by means of carbodiimides, glutardialdehyde, the abovementioned or other crosslinkers known to the person skilled in the art.
  • The effector molecules (ii) coupled to protein microbeads (i) covalently or noncovalently may be active in their bonded form. Alternatively, the effector molecules (ii) coupled to protein microbeads (i) can, however, also be released from the protein microbeads (i) or from their surface.
  • The release of covalently coupled effector molecules (ii) from the protein microbeads (i) can take place through cleavage of specifically introduced cleavable spacers or coupling linkers, which may, for example, be thermocleavable, photocleavable or enzymatically cleavable, but also through proteolytic degradation (e.g. by proteases) as described in Example 5 or through dissolution of the protein microbeads (i) or through mechanical destruction of the protein microbeads (i).
  • The release of noncovalently coupled effector molecules (ii) from the protein microbeads (i) can take place through desorption in suitable solvents, through degradation of the microbeads (i) by proteases or through dissolution of the protein microbeads (i) or through mechanical destruction of the protein microbeads (i). Suitable solvents for the desorption are all solvents or solvent mixtures in which the effector molecule (ii) can dissolve. Solvents which can dissolve the protein microbeads (i) are, for example, fluorinated alcohols, such as trifluoroethanol and hexafluoroisopropanol and also solutions of chaotropic salts, such as, for example, urea, guanidinium hydrochloride and guanidinium thiocyanate.
  • Suitable proteases can be added as technical proteases to a suspension of protein microbeads (i) in a targeted way or occur naturally at the desired site of action of the effector molecules (ii), such as, for example, skin proteases or proteases released by microorganisms.
  • The rate and kinetics of the release of the effector molecules (ii) can be controlled through the charge density with effector molecules (ii) and the average size of the microbeads (i).
  • For the use according to the invention in cosmetics, the protein microbeads (i) are formulated with customary further active ingredients and auxiliaries used in cosmetics.
  • Preferably, the protein microbeads (i) according to the invention are used for skin cosmetics. They permit a high concentration and long action time of skincare or skin-protecting effector substances.
  • Suitable auxiliaries and additives for producing hair cosmetic, nail cosmetic or skin cosmetic preparations are known to the person skilled in the art and can be found in cosmetics handbooks, for example Schrader, Grundlagen and Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics], Hüthig Verlag, Heidelberg, 1989, ISBN 3-7785-1491-1.
  • The cosmetic compositions according to the invention may be skin cosmetic, nail cosmetic, hair cosmetic, dermatological, hygiene or pharmaceutical compositions.
  • Preferably, the compositions according to the invention are in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • The cosmetically or pharmaceutically active compositions according to the invention can additionally comprise cosmetically and/or dermatologically active ingredients, and auxiliaries.
  • Preferably, the cosmetic compositions according to the invention comprise at least one protein microbead, and at least one constituent different therefrom which is chosen from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, photoprotective agents, bleaches, gel formers, care agents, colorants, tinting agents, tanning agents, dyes, pigments, consistency regulators, humectants, refatting agents, collagen, protein hydrolyzates, lipids, antioxidants, antifoams, antistats, emollients and softeners. The protein microbeads (i) can also be present in the cosmetic preparations in encapsulated form.
  • Advantageously, the antioxidants are chosen from the group consisting of 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. 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 thin-dipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximines, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g. pmol to μmol/kg), 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 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 thereof (e.g. sodium ascorbate, ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherol and derivatives (e.g. vitamin E acetate, tocotrienol), vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutinic 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, 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).
  • Also advantageous are so-called peroxide decomposers, i.e. compounds which are able to decompose peroxides, particularly preferably lipid peroxides. These are understood as meaning organic substances, such as, for example, pyridine-2-thiol-3-carboxylic acid, 2-methoxypyrimidinolcarboxylic acids, 2-methoxypyridinecarboxylic acids, 2-dimethylaminopyrimidinolcarboxylic acids, 2-dimethylaminopyridinecarboxylic acids.
  • Customary thickeners in such formulations are crosslinked polyacrylic acids and derivatives thereof, polysaccharides and derivatives thereof, such as xanthan gum, agar-agar, alginates or tyloses, cellulose derivatives, e.g. carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone. Preference is given to using nonionic thickeners.
  • Suitable cosmetically and/or dermocosmetically active ingredients are, for example, coloring active ingredients, skin and hair pigmentation agents, tinting agents, tanning agents, bleaches, keratin-hardening substances, antimicrobial active ingredients, photofilter active ingredients, repellent active ingredients, hyperemic substances, keratolytically and keratoplastically effective substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, antioxidative active ingredients and/or active ingredients which act as free-radical scavengers, skin moisturizing or humectant substances, refatting active ingredients, antierythematous or antiallergic active ingredients, branched fatty acids, such as 18-methyleicosanoic acid, and mixtures thereof.
  • Artificially skin-tanning active ingredients which are suitable for tanning the skin without natural or artificial irradiation with UV rays are, for example, dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are usually active ingredients, as are also used in antiperspirants, such as, for example, potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
  • Antimicrobial active ingredients are used to destroy microorganisms or to inhibit their growth and thus serve both as preservative and as deodorizing substance which reduces the formation or the intensity of body odor. These include, for example, customary preservatives known to the person skilled in the art, such as p-hydroxy-benzoic esters, imidazolidinylurea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for example, zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citrate, chlorhexidine etc.
  • Suitable preservatives, which are listed below with their E number, are to be used advantageously according to the invention.
  •
    E 200 Sorbic acid
    E 201 Sodium sorbate
    E 202 Potassium sorbate
    E 203 Calcium sorbate
    E 210 Benzoic acid
    E 211 Sodium benzoate
    E 212 Potassium benzoate
    E 213 Calcium benzoate
    E 214 Ethyl p-hydroxybenzoate
    E 215 Ethyl p-hydroxybenzoate Na salt
    E 216 n-Propyl p-hydroxybenzoate
    E 217 n-Propyl p-hydroxybenzoate Na salt
    E 218 Methyl p-hydroxybenzoate
    E 219 Methyl p-hydroxybenzoate Na salt
    E
    220 Sulfur dioxide
    E 221 Sodium sulfite
    E 222 Sodium hydrogensulfite
    E 223 Sodium disulfite
    E 224 Potassium disulfite
    E 226 Calcium sulfite
    E 227 Calcium hydrogensulfite
    E 228 Potassium hydrogensulfite
    E
    230 Biphenyl (diphenyl)
    E 231 Orthophenylphenol
    E 232 Sodium orthophenylphenoxide
    E 233 Thiabendazole
    E 235 Natamycin
    E 236 Formic acid
    E 237 Sodium formate
    E 238 Calcium formate
    E 239 Hexamethylenetetramine
    E 249 Potassium nitrite
    E 250 Sodium nitrite
    E 251 Sodium nitrate
    E 252 Potassium nitrate
    E 280 Propionic acid
    E 281 Sodium propionate
    E 282 Calcium propionate
    E 283 Potassium propionate
    E 290 Carbon dioxide
  • Also suitable according to the invention are preservatives or preservative auxiliaries customary in cosmetics dibromodicyanobutane (2-bromo-2-bromomethyl-glutarodinitrile), 3-iodo-2-propynyl butylcarbamate, 2-bromo-2-nitropropane-1,3-diol, imidazolidinylurea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, formaldehyde cleavers.
  • Also suitable as preservatives are phenyl hydroxyalkyl ethers, in particular the compound known under the name phenoxyethanol on account of its bactericidal and fungicidal effects on a number of microorganisms.
  • Other antimicrobial agents are likewise suitable for being incorporated into the preparations according to the invention. Advantageous substances are, for example, 2,4,4′-trichloro-2′-hydroxydiphenyl ether (irgasan), 1,6-di(4-chlorophenylbiguanido)-hexane (chiorhexidine), 3,4,4′-trichlorocarbanilide, quaternary ammonium compounds, oil of cloves, mint oil, thyme oil, triethyl citrate, farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), and the active ingredients or active ingredient combinations described in the patent laid-open specifications DE-37 40 186, DE-39 38 140, DE-42 04 321, DE-42 29 707, DE-43 09 372, DE-44 11 664, DE-195 41 967, DE-195 43 695, DE-195 43 696, DE-195 47 160, DE-196 02 108, DE-196 02 110, DE-196 02 111, DE-196 31 003, DE-196 31 004 and DE-196 34 019 and the patent specifications DE-42 29 737, DE-42 37 081, DE-43 24 219, DE-44 29 467, DE-44 23 410 and DE-195 16 705. Sodium hydrogencarbonate is also to be used advantageously. Antimicrobial polypeptides can also likewise be used.
  • Suitable photofilter active ingredients are substances which absorb UV rays in the UV-B and/or UV-A region. Suitable UV filters are, for example, 2,4,6-triaryl-1,3,5-triazines in which the aryl groups can each carry at least one substituent which is preferably chosen from hydroxy, alkoxy, specifically methoxy, alkoxycarbonyl, specifically methoxycarbonyl and ethoxycarbonyl and mixtures thereof. Also suitable are p-aminobenzoic esters, cinnamic esters, benzophenones, camphor derivatives, and pigments which stop UV rays, such as titanium dioxide, talc and zinc oxide.
  • Suitable UV filter substances are any UV-A and UV-B filter substances. Examples to be mentioned are:
  • CAS No.
    No. Substance (=acid)
    1 4-Aminobenzoic acid 150-13-0
    2 3-(4′-Trimethylammonium)benzylidenebornan-2-one methyl 52793-97-2
    sulfate
    3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9
    (homosalate)
    4 2-Hydroxy-4-methoxybenzophenone 131-57-7
    (oxybenzone)
    5 2-Phenylbenzimidazole-5-sulfonic acid and its potassium, 27503-81-7
    sodium and triethanolamine salts
    6 3,3′-(1,4-Phenylenedimethine)bis(7,7-dimethyl- 90457-82-2
    2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its
    salts
    7 Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9
    8 2-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3
    9 2-Ethylhexyl salicylate 118-60-5
    10 2-Isoamyl 4-methoxycinnamate 71617-10-2
    11 2-Ethylhexyl 4-methoxycinnamate 5466-77-3
    12 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6
    (sulisobenzone) and the sodium salt
    13 3-(4′-Sulfobenzylidene)bornan-2-one and salts 58030-58-6
    14 3-Benzylidenebornan-2-one 16087-24-8
    15 1-(4′-Isopropylphenyl)-3-phenylpropane-1,3-dione 63260-25-9
    16 4-Isopropylbenzyl salicylate 94134-93-7
    17 3-Imidazol-4-ylacrylic acid and its ethyl ester 104-98-3
    18 Ethyl 2-cyano-3,3-diphenylacrylate 5232-99-5
    19 2′-Ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4
    20 Menthyl o-aminobenzoate or: 134-09-8
    5-methyl 2-(1-methylethyl)-2-aminobenzoate
    21 Glyceryl p-aminobenzoate or: 1-glyceryl 4-aminobenzoate 136-44-7
    22 2,2′-Dihydroxy-4-methoxybenzophenone (dioxybenzone) 131-53-3
    23 2-Hydroxy-4-methoxy-4-methylbenzophenone 1641-17-4
    (mexenone)
    24 Triethanolamine salicylate 2174-16-5
    25 Dimethoxyphenylglyoxalic acid or: 4732-70-1
    3,4-dimethoxyphenylglyoxal acidic sodium
    26 3-(4′-Sulfobenzylidene)bornan-2-one and its salts 56039-58-8
    27 4-tert-Butyl-4′-methoxydibenzoylmethane 70356-09-1
    28 2,2′,4,4′-Tetrahydroxybenzophenone 131-55-5
    29 2,2′-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3,-tetra- 103597-45-1
    methylbutyl)phenol]
    30 2,2′-(1,4-Phenylene)bis-1H-benzimidazole- 180898-37-7
    4,6-disulfonic acid, Na salt
    31 2,4-bis[4-(2-Ethylhexyloxy)-2-hydroxy]phenyl- 187393-00-6
    6-(4-methoxyphenyl)-(1,3,5)-triazine
    32 3-(4-Methylbenzylidene)camphor 36861-47-9
    33 Polyethoxyethyl 4-bis(polyethoxy)paraaminobenzoate 113010-52-9
    34 2,4-Dihydroxybenzophenone 131-56-6
    35 2,2′-Dihydroxy-4,4′-dimethoxybenzophenone- 3121-60-6
    5,5′-disodium sulfonate
    36 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl], hexyl ester 302776-68-7
    37 2-(2H-Benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetra- 155633-54-8
    methyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol
    38 1,1-[(2,2′-Dimethylpropoxy)carbonyl]-4,4-diphenyl-1,3-butadiene 363602-15-7
  • The cosmetic and dermatological preparations according to the invention can advantageously also comprise inorganic pigments which stop UV rays and are based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, chosen from the group of oxides of zinc (ZnO), titanium (TiO2), iron (e.g. Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminum (Al2O3), cerium (e.g. Ce2O3), mixed oxides of the corresponding metals and mixtures of such oxides.
  • The inorganic pigments can be present here in coated form, i.e. are treated superficially. This surface treatment can consist, for example, in providing the pigments with a thin hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
  • Suitable repellent active ingredients are compounds which are able to repel or drive away certain animals, in particular insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide etc. Suitable hyperemic substances, which stimulate the flow of blood through the skin, are e.g. essential oils, such as dwarf pine extract, lavender extract, rosemary extract, juniperberry extract, horse chestnut extract, birch leaf extract, hayflower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable antidandruff active ingredients are, for example, sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics, which counteract skin irritations, are, for example, allantoin, bisabolol, dragosantol, camomile extract, panthenol, etc.
  • The cosmetic compositions according to the invention can comprise, as cosmetic and/or pharmaceutical active ingredient (also, if appropriate, as auxiliary), at least one cosmetically or pharmaceutically acceptable polymer. These include, quite generally, cationic, amphoteric and neutral polymers.
  • Suitable polymers are, for example, cationic polymers with the INCI name Polyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazolium salts (Luviquat FC, Luviquat HM, Luviquat MS, Luviquat&commat, Care), copolymers of N-vinyl-pyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat PQ 11), copolymers of N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts (Luviquat E Hold), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7) and chitosan.
  • Suitable cationic (quaternized) polymers are also Merquat (polymer based on dimethyldiallylammonium chloride), Gafquat (quaternary polymers which are formed by reacting polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and plant-based cationic polymers, e.g. guar polymers, such as the Jaguar grades from Rhodia.
  • Further suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate, poly-siloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and salts thereof, polyvinylamines and salts thereof, cellulose derivatives, polyaspartic acid salts and derivatives. These include, for example, Luviflex 0 Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, BASF).
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, e.g. Luviskol 0 Plus (BASF), or polyvinyl-pyrrolidone and copolymers thereof, in particular with vinyl esters, such as vinyl acetate, e.g. Luviskol 0 VA 37 (BASF), polyamides, e.g. based on itaconic acid and aliphatic diamines, as are described, for example, in DE-A-43 33 238.
  • Suitable polymers are also amphoteric or zwitterionic polymers, such as the octylacryl-amide/methyl methacrylate/tert-butylaminoethyl methacrylate-hydroxypropyl methacrylate copolymers obtainable under the names Amphomer (National Starch), and zwitterionic polymers, as are disclosed, for example, in the German patent applications DE39 29 973, DE 21 50 557, DE28 17 369 and DE 3708 451. Acrylamido-propyltrimethylammonium chloride/acrylic acid or methacrylic acid copolymers and alkali metal and ammonium salts thereof are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine/methacrylate copolymers, which are commercially available under the name Amersette (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N,N-dimethylamino-ethyl methacrylate and acrylic acid (Jordapon (D)).
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, e.g. polyether siloxanes, such as Tegopren 0 (Goldschmidt) or Besi&commat (Wacker).
  • The formulation base of cosmetic compositions according to the invention preferably comprises cosmetically and/or pharmaceutically acceptable auxiliaries. Pharmaceutically acceptable auxiliaries are the auxiliaries which are known for use in the field of pharmacy, food technology and related fields, in particular the auxiliaries listed in the relevant pharmacopeia (e.g. DAB Ph. Eur. BP NF), and other auxiliaries whose properties do not preclude a physiological application.
  • Suitable auxiliaries may be: glidants, wetting agents, emulsifying and suspending agents, preservatives, antioxidants, antiirritatives, chelating agents, emulsion stabilizers, film formers, gel formers, odor masking agents, resins, hydrocolloids, solvents, solubility promoters, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, refatting and superfatting agents, ointment, cream or oil base substances, silicone derivatives, stabilizers, sterilizing agents, propellants, drying agents, opacifiers, thickeners, waxes, softeners, white oil. An embodiment in this regard is based on specialist knowledge, as shown, for example, in Fiedler, H. P. Lexikon der Hilfsstoffe für Pharmazie, Kosmetik and angrenzende Gebiete [Lexicon of auxiliaries for pharmacy, cosmetics and related fields], 4th edition, Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
  • To produce the dermocosmetic compositions according to the invention, the active ingredients can be mixed or diluted with a suitable auxiliary (excipient). Excipients may be solid, semisolid or liquid materials which can serve as vehicles, carriers or medium for the active ingredient. The admixing of further auxiliaries takes place, if desired, in the manner known to the person skilled in the art. In addition, the polymers and dispersions are suitable as auxiliaries in pharmacy, preferably as or in (a) coating composition(s) or binder(s) for solid drug forms. They can also be used in creams and as tablet coatings and tablet binders.
  • According to a preferred embodiment, the compositions according to the invention are a skin cleansing composition.
  • Preferred skin cleansing compositions are soaps of liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes, exfoliating soaps, moisture wipes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels, foam baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • According to a further preferred embodiment, the compositions according to the invention are cosmetic compositions for the care and protection of the skin and hair, nailcare compositions or preparations for decorative cosmetics.
  • Suitable skin cosmetic compositions are, for example, face tonics, face masks, deodorants and other cosmetic lotions. Compositions for use in decorative cosmetics include, for example, concealing sticks, stage make-up, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, blushers, powders and eyebrow pencils.
  • Furthermore, the dermatological compositions according to the invention can be used in nose strips for pore cleansing, in antiacne compositions, repellents, shaving compositions, aftershave and preshave care compositions, aftersun care compositions, hair removal compositions, hair colorants, intimate care compositions, footcare compositions, and in baby care.
  • The skincare compositions according to the invention are, in particular, W/O or O/W skin creams, day creams and night creams, eye creams, face creams, antiwrinkle creams, sunscreen creams, moisturizing creams, bleaching creams, self-tanning creams, vitamin creams, skin lotions, care lotions and moisturizing lotions.
  • Skin cosmetic and dermatological compositions based on the protein microbeads described above display advantageous effects. The protein microbeads (i) can, inter alia, contribute to the moisturization and conditioning of the skin and to an improvement in the feel of the skin. The protein microbeads (i) can also act as thickeners in the formulations. By adding the protein microbeads (i) according to the invention it is possible, in certain formulations, to achieve a considerable improvement in skin compatibility.
  • Skin cosmetic and dermatological compositions preferably comprise at least one protein microbead (i) in an amount of from about 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the composition.
  • Particularly photoprotective compositions based on the protein microbeads (i) have the property of increasing the residence time of the UV-absorbing ingredients compared to customary auxiliaries such as polyvinylpyrrolidone.
  • Depending on the field of use, the compositions according to the invention can be applied in a form suitable for skincare, such as, for example, as cream, foam, gel, stick, mousse, milk, spray (pump spray or propellant-containing spray) or lotion.
  • Besides the protein microbeads (i) and suitable carriers, the skin cosmetic preparations can also comprise further active ingredients and auxiliaries customary in skin cosmetics, as described above. These include, preferably, emulsifiers, preservatives, perfume oils, cosmetic active ingredients, such as phytantriol, vitamin A, E and C, retinol, bisabolol, panthenol, photoprotective agents, bleaches, colorants, tinting agents, tanning agents, collagen, enzymes, protein hydrolyzates, stabilizers, pH regulators, dyes, salts, thickeners, gel formers, consistency regulators, silicones, humectants, refatting agents and/or further customary additives.
  • Preferred oil and fat components of the skin cosmetic and dermatological compositions are the abovementioned mineral and synthetic oils, such as, for example, paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such as, for example, sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as, for example, triglycerides of C6-C30 fatty acids, wax esters, such as, for example, jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.
  • The protein microbeads (i) according to the invention can also be mixed with conventional polymers if specific properties are to be established.
  • To establish certain properties, such as, for example, improving the feel to the touch, the spreading behavior, the water resistance and/or the binding of active ingredients and auxiliaries such as pigments, the skin cosmetic and dermatological preparations can additionally also comprise conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • The cosmetic or dermocosmetic preparations are produced by customary methods known to the person skilled in the art.
  • Preferably, the cosmetic and dermocosmetic compositions are present in the form of emulsions, in particular as water-in-oil (W/O) or oil-in-water (O/W) emulsions.
  • However, it is also possible to choose other types of formulation, for example gels, oils, oleogels, multiple emulsions, for example in the form of W/O/W or O/W/O emulsions, anhydrous ointments or ointment bases, etc. Emulsifier-free formulations, such as hydrodispersions, hydrogels or a Pickering emulsion are also advantageous embodiments.
  • Emulsions are produced by known methods. Besides at least one protein microbead (i), the emulsions usually comprise customary constituents, such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water. The choice of additives specific to the type of emulsion and the production of suitable emulsions is described, for example, in Schrader, Grundlagen and Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics], Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, third part, to which reference is hereby expressly made.
  • A suitable emulsion in the form of a W/O emulsion, e.g. for a skin cream etc., generally comprises an aqueous phase which is emulsified in an oil or fatty phase using a suitable emulsifier system. A polyelectrolyte complex can be used for the provision of the aqueous phase.
  • Preferred fatty components which may be present in the fatty phase of the emulsions are: hydrocarbon oils, such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophyllum oil, lanolin and derivatives thereof, castor oil, sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil, mineral oils whose distillation start-point under atmospheric pressure is at about 250° C. and whose distillation end-point is at 410° C., such as, for example, Vaseline oil, esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl or isopropyl palmitate, octanoic or decanoic acid triglycerides and cetyl ricinoleate.
  • The fatty phase can also comprise silicone oils which are soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • Besides the protein microbeads (i), waxes can also be used, such as, for example, carnauba wax, candelilia wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • In addition, an emulsion according to the invention may be in the form of an O/W emulsion. Such an emulsion usually comprises an oil phase, emulsifiers which stabilize the oil phase in the water phase, and an aqueous phase, which is usually present in thickened form. Suitable emulsifiers are preferably O/W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides.
  • According to a further preferred embodiment, the compositions according to the invention are a shower gel, a shampoo formulation or a bathing preparation.
  • Such formulations comprise at least one protein microbead (i) and usually anionic surfactants as base surfactants and amphoteric and/or nonionic surfactants as cosurfactants. Further suitable active ingredients and/or auxiliaries are generally chosen from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, and thickeners/gel formers, skin conditioning agents and humectants.
  • These formulations advantageously comprise 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
  • In the washing, shower and bath preparations, all of the anionic, neutral, amphoteric or cationic surfactants customarily used in body-cleansing compositions can be used.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • These include, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropyl-betaines, alkylsulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or -propionates, alkyl amphodiacetates or -dipropionates.
  • For example, cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and/or propylene oxide. The amount of alkylene oxide is about 6 to 60 mol per mole of alcohol. In addition, alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan ether esters are suitable.
  • Furthermore, the washing, shower and bath preparations can comprise customary cationic surfactants, such as, for example, quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • In addition, the shower gel/shampoo formulations can comprise thickeners, such as, for example, sodium chloride, PEG-55, propylene glycol oleate, PEG-120 methylglucose dioleate and others, and also preservatives, further active ingredients and auxiliaries and water.
  • According to a further preferred embodiment, the compositions according to the invention are a hair-treatment composition.
  • Hair-treatment compositions according to the invention preferably comprise at least one protein microbead (i) in an amount in the range from about 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.
  • Preferably, the hair treatment compositions according to the invention are in the form of a setting foam, hair mousse, hair gel, shampoo, hair spray, hair foam, end fluid, neutralizer for permanent waves, hair colorant and bleach or hot-oil treatment. Depending on the field of use, the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax. Hair sprays include here both aerosol sprays and also pump sprays without propellant gas. Hair foams include both aerosol foams and also pump foams without propellant gas. Hair sprays and hair foams preferably include predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are dispersible in water, they can be applied in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm. The solids contents of these preparations are here usually in a range from about 0.5 to 20% by weight. These microdispersions do not usually require emulsifiers or surfactants for their stabilization.
  • The hair cosmetic formulations according to the invention comprise, in a preferred embodiment, a) 0.01 to 30% by weight of at least one protein microbead (i), b) 20 to 99.95% by weight of water and/or alcohol, c) 0 to 50% by weight of at least one propellant gas, d) 0 to 5% by weight of at least one emulsifier, e) 0 to 3% by weight of at least one thickener, and up to 25% by weight of further constituents.
  • Alcohol is understood as meaning all alcohols customary in cosmetics, e.g. ethanol, isopropanol, n-propanol.
  • Further constituents are to be understood as meaning the additives customary in cosmetics, for example propellants, antifoams, interface-active compounds, i.e. surfactants, emulsifiers, foam formers and solubilizers. The interface-active compounds used may be anionic, cationic, amphoteric or neutral. Further customary constituents may also be, for example, preservatives, perfume oils, opacifiers, active ingredients, UV filters, care substances, such as panthenol, collagen, vitamins, protein hydrolyzates, alpha- and beta-hydroxycarboxylic acids, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, salts, humectants, refatting agents, complexing agents and further customary additives.
  • Also included here are all styling and conditioner polymers known in cosmetics which can be used in combination with the protein microbeads (i) according to the invention if quite specific properties are to be established.
  • Suitable conventional hair cosmetics polymers are, for example, the above-mentioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is made here.
  • To establish certain properties, the preparations can additionally also comprise conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds, such as amodimethicones (CTFA).
  • The polymers according to the invention are particularly suitable as setting compositions in hair styling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (as aerosol foams and pump foams without propellant gas).
  • In a preferred embodiment, spray preparations comprise a) 0.01 to 30% by weight of at least one protein microbead (i), b) 20 to 99.9% by weight of water and/or alcohol, c) to 70% by weight of at least one propellant, d) 0 to 20% by weight of further constituents.
  • Propellants are the propellants customarily used for hair sprays or aerosol foams. Preference is given to mixtures of propane/butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air.
  • A formulation preferred according to the invention for aerosol hair foams comprises a) 0.01 to 30% by weight of at least one protein microbead (i), b) 55 to 99.8% by weight of water and/or alcohol, c) 5 to 20% by weight of a propellant, d) 0.1 to 5% by weight of an emulsifier, e) 0 to 10% by weight of further constituents.
  • Emulsifiers which can be used are all emulsifiers customarily used in hair foams. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
  • Examples of nonionic emulsifiers (INCI nomenclature) are laureths, e.g. laureth-4; ceteths, e.g. ceteth-1, polyethylene glycol cetyl ether, ceteareths, e.g. ceteareth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkyl polyglycosides.
  • Examples of cationic emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimonium chloride, cetyltrimonium bromide, cocotrimonium methyl sulfate, Quaternium-1 to x (INCI).
  • Anionic emulsifiers can be chosen, for example, from the group of alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • A preparation suitable according to the invention for styling gels can, for example, have the following composition: a) 0.01 to 30% by weight of at least one protein microbead (1), b) 80 to 99.85% by weight of water and/or alcohol, c) 0 to 3% by weight, preferably 0.05 to 2% by weight, of a gel former, d) 0 to 20% by weight of further constituents. The use of gel formers may be advantageous in order to establish specific rheological or other application-related properties of the gels. Gel formers which can be used are all gel formers customary in cosmetics. These include slightly crosslinked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g. hydroxypropylcellulose, hydroxyethylcellulose, cationically modified celluloses, polysaccharides, e.g. xanthan gum, caprylic/capric triglyceride, sodium acrylate copolymers, polyquaternium-32 (and) Paraffinum Liquidum (INCI), sodium acrylate copolymers (and) paraffinum liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride/acrylamide copolymers, steareth-10 allyl ether, acrylate copolymers, polyquaternium-37 (and) paraffinum liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and) propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium-7, polyquaternium-44.
  • The protein microbeads (i) according to the invention can be used as conditioners in cosmetic preparations.
  • A preparation comprising the protein microbeads (i) according to the invention can preferably be used in shampoo formulations as setting and/or conditioning compositions. Preferred shampoo formulations comprise a) 0.01 to 30% by weight of at least one protein microbead (i), b) 25 to 94.95% by weight of water, c) 5 to 50% by weight of surfactants, c) 0 to 5% by weight of a further conditioning agent, d) 0 to 10% by weight of further cosmetic constituents.
  • In the shampoo formulations, all of the anionic, neutral, amphoteric or cationic surfactants customarily used in shampoos can be used.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • Of suitability are, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropyl-betaines, alkylsulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or -propionates, alkyl amphodiacetates or -dipropionates.
  • For example, cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and/or propylene oxide. The amount of alkylene oxide is about 6 to 60 mol per mole of alcohol. In addition, alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkyl polyglycosides or sorbitan ether esters are suitable.
  • Furthermore, the shampoo formulations can comprise customary cationic surfactants, such as, for example, quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • In the shampoo formulations, in order to achieve certain effects, customary conditioning agents can be used in combination with the protein microbeads (i).
  • These include, for example, the abovementioned cationic polymers with the INCI name Polyquaternium, in particular copolymers of vinylpyrrolidone/N-vinylimidazolium salts (Luviquat FC, Luviquat&commat, HM, Luviquat MS, Luviquat Care), copolymers of N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat D PQ 11), copolymers of N-vinylcaprolactam/N-vinylpyrrolidone/N-vinyl-imidazolium salts (Luviquat D Hold), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). In addition, protein hydrolyzates can be used, and also conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins. Further suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds, such as amodimethicones (CTFA). In addition, cationic guar derivatives, such as Guar Hydroxypropyltrimonium Chloride (INCI) can be used.
    • EXPERIMENTAL SECTION Example 1 Method of Producing Spherical Protein Microbeads from the Silk Protein C16 in Solution
  • An aqueous C16 solution is prepared. For this, lyophilized C16 is dissolved in 6 M guanidinium thiocyanate (GdmSCN) with an end concentration of 0.1-10 mg/ml. The GdmSCN is then removed by dialysis against 5 mM potassium phosphate pH 8.0.
  • The formation of β-pleated-sheet-rich C16-microbeads is induced at room temperature by rapidly adding 500 mM potassium phosphate pH 8.0 or 800 mM ammonium sulfate (end concentration) to the protein solution, followed by brief mixing (e.g. swirling the reaction vessel). The mean particle diameter is dependent on the protein concentration used and can be varied between 0.5 μm and 15 μm. The particles are then washed with water and lyophilized. The success of the microbead formation is checked using scanning electron microscopy.
    • Example 2 Determination of the Thermal Stability of C16-Microbeads by Thermogravimetric Analysis (TGA)
  • The thermal stability of C16-microbeads was determined using the “Thermogravimetric Analyser TGA 7” apparatus from Perkin-Elmer. Here, aluminum sample pans with a volume of 40 μl were used. The flushing gas used for the balance was 4 I/h of nitrogen, and the flushing gas used for the sample space was 1.6 I/h of nitrogen or air (in each case following measurement). The sample was heated from 30 to 500° C. at a heating rate of 5 K/min. During the measurement, the sample weight and the oven temperature were recorded. FIG. 1 shows the course of the C16-microbead sample weight as a function of the temperature. It can be clearly seen that the majority of the analyzed C16-microbeads is stable up to temperatures of at least 250° C. Only then is a significant loss in mass seen, the reason for this being the decomposition of the sample.
    • Example 3 Water Absorption of C16-Microbeads
  • C16-Microbeads can absorb and release water from the air and thus serve as moisture-regulating substance in cosmetic applications. In order to demonstrate this, 0.4 g-0.5 g of C16-microbeads, which have been stored beforehand at −20° C., were dried for 16 h under reduced pressure. As a result of this treatment, the microbeads lost 12% of their weight (based on the dry weight). Subsequent storage at room temperature and 100% atmospheric humidity led to a slow weight increase of 25% over the course of 19 days (see FIG. 2). Drying again under reduced pressure achieved the original dry weight again.
    • Example 4 Formulation of Canthaxanthin
  • In order to show that the C16-microbeads are suitable as carriers and formulation auxiliaries for effector molecules, canthaxanthin was bound as example to C16-microbeads.
  • For this, 500 μl of a solution of 20 mg/ml of C16 in 5 mM potassium phosphate (pH 8.0) were mixed with 50 μl of a solution of 2 mg/ml of canthaxanthin in DMSO after the insoluble microcrystals have been removed by centrifugation. Subsequently, the formation of C16-microbeads was induced by adding 500 μl of a 1 M potassium phosphate solution (pH 8.0).
  • During the formation of the C16-microbeads, the canthaxanthin was removed quantitatively from the solution, as could be shown by determining the absorbance in the supernatant after centrifuging off the C16-microbeads (FIG. 3). The centrifuged-off C16-microbeads appeared clearly pink-violet in color. Following the lyophilization, the charged C16-microbeads were analyzed by means of electron microscopy. In the electron micrograph, the charged C16-microbeads do not differ from the uncharged control which was prepared under the same conditions, as a result of which it becomes evident that the C16-microbeads and the canthaxanthin form a common solid phase (FIG. 4).
  • In order to test how strong the bonding of the canthaxanthin to the C16-microbeads was, the charged microbeads were washed with 5 mM potassium phosphate (pH 8.0), 5 mM potassium phosphate (pH 8.0)+5% DMSO and pure DMSO. For this, the C16-microbeads were incubated with 1 ml of each of the solutions for about 1 min. Centrifugation was then carried out and the canthaxanthin content in the supernatant was measured by determining the absorbance. Whereas washing without and with only 5% DMSO was not able to bring any canthaxanthin into solution, single washing with pure DMSO resulted in the majority of the bound canthaxanthin being brought into solution (FIG. 5). The canthaxanthin can thus no longer be washed out by the conditions under which it has been bound to the microbeads (5% DMSO), which indicates a firm association to the microbeads.
  • As control, 500 μl of a solution of 5 mM potassium phosphate (pH 8.0) were mixed with 50 μl of the canthaxanthin solution in DMSO. In the absence of C16, the solution remained clear even after adding 500 μl of a 1 M potassium phosphate solution (pH 8.0). The canthaxanthin was not able, under the conditions of assembly, to form a solid phase on its own.
  • In order to test whether the canthaxanthin is essentially adsorbed to the surface of the C16-microbeads or whether the canthaxanthin has also been incorporated into the C16-microbeads, 500 μl of a solution of 5 mM potassium phosphate (pH 8.0) were mixed with 50 μl of the canthaxanthin solution in DMSO and then 10 mg of uncharged, white C16-microbeads were added. 500 μl of the 1 M potassium phosphate solution (pH 8.0) were then added to the suspension. After centrifuging off the C16-microbeads, the majority of the canthaxanthin used was found in the supernatant, only a small part was bound to the microbeads (FIG. 3), which was also evident from the slightly violet coloration of the C16-microbeads. Again, by washing with 1 ml of a solution of 5% DMSO in 5 mM potassium phosphate (pH 8.0), it was tested how strong the association of the canthaxanthin to the C16-microbeads is. In contrast to the C16-microbeads which were formed in the presence of canthaxanthin, the total bound canthaxanthin could now be washed out (FIG. 6), which suggests a significantly weaker association of canthaxanthin to already existing C16-microbeads. Overall, the binding of the canthaxanthin to the C16-microbeads which were formed in the presence of canthaxanthin differs from the absorption to already existing C16-microbeads, which indicates inclusion of the canthaxanthin into the microbeads during assembly.
    • Example 5 Release of Canthaxanthin from C16-Microbeads
  • Besides washing out canthaxanthin using solvents such as, for example, DMSO (FIG. 5), the release can also take place by degrading the C16-microbeads. In order to show the degradation of the C16-microbeads by proteases, in a total of two batches (FIG. 7, a and b), in each case 150 μl of C16 in 5 mM potassium phosphate (pH 8.0) were mixed with 150 μl of a saturated solution of canthaxanthin in DMSO. 700 μl of a 1 M potassium phosphate solution (pH 8.0) were then added in order to induce the formation of the C16-microbeads. As control, 150 μl of a solution of 5 mM potassium phosphate (pH 8.0) were mixed with 150 μl of a saturated solution of canthaxanthin in DMSO and 700 μl of a 1 M potassium phosphate solution (pH 8.0) (control without C16). All batches were incubated for 1.5 hours at RT and then centrifuged. While in the case of the batches with C16, orange-violet colored microbeads have formed, no precipitation was observed in the case of the control.
  • The supernatants were removed and the C16-microbeads charged with canthaxanthin were taken up in 1 ml of a 5 mM potassium phosphate solution (pH 8.0). The canthaxanthin content in the supernatants was determined photometrically by reference to the canthaxanthin absorbance (supernatant after C16 precipitation). Whereas as in the control without C16, the total canthaxanthin remained in the supernatant, the canthaxanthin in the two batches with C16 was bound quantitatively by the C16-microbeads (FIG. 7).
  • In order to degrade the microbeads, 3 U of Proteinase K (Roche) were added next to the C16-microbeads from batch (a) and incubated together with the control without protease (batch b) at 37° C. At the end of incubation, centrifugation was carried out and the supernatants were measured photometrically. Whereas in the case of the control without protease (batch b), no canthaxanthin could be measured in the supernatant, in the batch with protease (a), canthaxanthin was released quantitatively from the C16-microbeads. Overall, through the experiment it becomes clear that canthaxanthin can be released through proteolytic degradation of the microbeads.
    • Example 6 Incorporation of Fluorescein into C16-Microparticles by Covalent Bonding
  • The fact that effector molecules can be bonded covalently to C16 and then incorporated into microbeads was shown using fluorescein as an example. Firstly, an aqueous C16 solution was prepared. For this, lyophilized C16 was dissolved in 6 M guanidinium thiocyanate (GdmSCN) with an end concentration of 10 mg/ml. The GdmSCN was then removed by dialysis against 5 mM potassium phosphate pH 8.0. The carboxyl groups of the C16 were activated in order then to react with ethylenediamine to form an amide (FIG. 8). For this, the following stock solutions were used:
      • 10 mg/ml of C16 5 mM potassium phosphate pH 8.0
      • 250 mM 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, hydrochloride (EDC) in water
      • 250 mM N-hydroxysulfosuccinimide, sodium salt (NHS) in water
      • 500 mM 2-morpholinoethanesulfonic acid (MES) pH 5.0
      • 2 M ethylenediamine in water
  • The stock solutions of EDC and NHS were each prepared shortly prior to use.
  • For the activation of the C16 carboxyl groups, the following batch was incubated for 15 min at room temperature:
      • 5 mg/ml C16
      • 100 mM MES pH 5.0
      • 25 mM EDC
      • 5 mM NHS
  • The coupling of ethylenediamine to the activated C16 carboxyl groups was carried out by adding 500 mM ethylenediamine and incubating the batch for two hours at room temperature. The batch was then dialyzed against 5 mM potassium phosphate pH 8.0.
  • In a second step, fluorescein isothiocyanate was bound to the free amino group of the ethylenediamine coupled to C16 (FIG. 8). For this, the following stock solutions were used:
      • ethylenediamine-modified C16 in 5 mM potassium phosphate pH 8.0
      • 1 M sodium carbonate pH 9.0
      • 10 mg/ml of fluorescein isothiocyanate (FITC) in dimethyl sulfoxide (DMSO)
      • 1 M potassium phosphate pH 8.0
  • The FITC stock solution was prepared in each case shortly prior to use.
  • The FITC coupling was carried out according to the following protocol:
      • addition of 100 mM sodium carbonate pH 9.0 and 1 mg/ml of FITC to the C16 solution
      • incubation for 1 h at room temperature (in the dark)
      • precipitation of the C16 with 660 mM potassium phosphate
      • incubation for 1 h at room temperature (in the dark)
      • centrifugation at 10000×g for 10 min at room temperature
      • 3× washing of the pellet with 5 mM potassium phosphate pH 8.0
      • dissolution of the pellet in 6 M guanidinium thiocyanate (end concentration of the protein: 5 mg/ml)
      • dialysis against 5 mM potassium phosphate pH 8.0 (in the dark)
      • precipitation with 500 mM potassium phosphate pH 8.0
      • 3× washing of the pellet with water
      • resuspension in water
      • freezing in liquid nitrogen
      • lyophilization (in the dark)
  • The precipitation of the soluble RTC-labeled C16 with potassium phosphate produces, as in the case of untreated C16-protein, round microbeads although, in contrast to untreated C16-microbeads, these exhibit significant fluorescence (FIG. 9).
  • The efficiency of the coupling of fluorescein onto C16 was determined photometrically. For this, a 5 mg/ml suspension of the lyophilized modified C16 protein was digested proteolytically (100 mM tris(hydroxymethyl)aminomethane (Tris) pH 8.0; 0.1% sodium dodecylsulfate (SDS); 50 μg/ml of Proteinase K (Roche); incubation for 1 h at 37° C.). The concentration of the fluorescein in the digested solution was calculated using the molar absorbance coefficient ε494nm=77000 cm−1M−1. The coupling efficiency could be calculated from the calculated fluorescein concentration and the known used amount of protein.
  • In this way, in the C16-microbeads, an average coupling of 12.8 fluorescein molecules onto a C16 molecule was established. As control, a sample was treated according to the same protocol, replacing the EDC and NHS during the activation with water. The coupling efficiency of this sample was less than one fluorescein molecule per C16 molecule. It can be concluded from this that the binding of the fluorescein to C16 follows the mechanism postulated in FIG. 8 and is not based on nonspecific binding effects.
  • Dermocosmetic preparations according to the invention comprising the C16-microbeads prepared according to Example 1 or C16-microbead-canthaxanthin produced according to Example 4 are described below.
    • Example 7 Use of C16-Microbead in an Emulsion for Daycare—O/W Type
  • % Ingredient (INCI)
    Al 1%:
    A 1.7 Ceteareth-6, Stearyl Alcohol
    0.7 Ceteareth-25
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 PEG-14 Dimethicone
    3.6 Cetearyl Alcohol
    6.0 Ethylhexyl Methoxycinnamate
    2.0 Dibutyl Adipate
    B 5.0 Glycerin
    0.2 Disodium EDTA
    1.0 Panthenol
    1.0 C16-Microbead
    q.s. Preservative
    67.8  Aqua dem.
    C 4.0 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    D 0.2 Sodium Ascorbyl Phosphate
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
    1.0 Caprylic/Capric Triglyceride, Sodium Ascorbate, Tocopherol,
    Retinol
    E q.s. Sodium Hydroxide
    Al
    5%:
    A 1.7 Ceteareth-6, Stearyl Alcohol
    0.7 Ceteareth-25
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 PEG-14 Dimethicone
    3.6 Cetearyl Alcohol
    6.0 Ethylhexyl Methoxycinnamate
    2.0 Dibutyl Adipate
    B 5.0 Glycerin
    0.2 Disodium EDTA
    1.0 Panthenol
    5.0 C16-Microbead
    q.s. Preservative
    63.8  Aqua dem.
    C 4.0 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    D 0.2 Sodium Ascorbyl Phosphate
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
    1.0 Caprylic/Capric Triglyceride, Sodium Ascorbate, Tocopherol,
    Retinol
    E q.s. Sodium Hydroxide
  • Preparation: Heat phases A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Stir phase C into the combined phases A and B and homogenize again. Cool with stirring to about 40° C., add phase D, adjust the pH to about 6.5 with phase E, homogenize and cool to room temperature with stirring.
  • Note: The formulation is prepared without protective gas. Bottling must take place in oxygen-impermeable packagings, e.g. aluminum tubes.
    • Example 8 Use of C16-Microbead in a Protective Daycream—O/W Type
  • % Ingredient (INCI)
    Al 1%:
    A 1.7 Ceteareth-6, Stearyl Alcohol
    0.7 Ceteareth-25
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 PEG-14 Dimethicone
    3.6 Cetearyl Alcohol
    6.0 Ethylhexyl Methoxycinnamate
    2.0 Dibutyl Adipate
    B 5.0 Glycerin
    0.2 Disodium EDTA
    1.0 Panthenol
    1.0 C16-Microbead
    q.s. Preservative
    68.6  Aqua dem.
    C 4.0 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    D 1.0 Sodium Ascorbyl Phosphate
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
    E q.s. Sodium Hydroxide
    Al
    5%:
    A 1.7 Ceteareth-6, Stearyl Alcohol
    0.7 Ceteareth-25
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 PEG-14 Dimethicone
    3.6 Cetearyl Alcohol
    6.0 Ethylhexyl Methoxycinnamate
    2.0 Dibutyl Adipate
    B 5.0 Glycerin
    0.2 Disodium EDTA
    1.0 Panthenol
    5.0 C16-Microbead
    q.s. Preservative
    64.6  Aqua dem.
    C 4.0 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    D 1.0 Sodium Ascorbyl Phosphate
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
    E q.s. Sodium Hydroxide
  • Preparation: Heat phases A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Incorporate phase C into the combined phases A and B and homogenize. Cool to about 40° C. with stirring. Add phase D, adjust the pH to about 6.5 with phase E and homogenize. Cool to room temperature with stirring.
    • Example 9 Use of C16-Microbead in a Face Cleansing Lotion—O/W Type
  • % Ingredient (INCI)
    AL 1%:
    A 10.0 Cetearyl Ethylhexanoate
    10.0 Caprylic/Capric Triglyceride
    1.5 Cyclopentasiloxane, Cyclohexasilosane
    2.0 PEG-40 Hydrogenated Castor Oil
    B 3.5 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    C 1.0 Tocopheryl Acetate
    0.2 Bisabolol
    q.s. Preservative
    q.s. Perfume Oil
    D 3.0 Polyquaternium-44
    0.5 Cocotrimonium Methosulfate
    0.5 Ceteareth-25
    2.0 Panthenol, Propylene Glycol
    4.0 Propylene Glycol
    0.1 Disodium EDTA
    1.0 C16-Microbead
    60.7 Aqua dem.
    Al 5%:
    A 10.0 Cetearyl Ethylhexanoate
    10.0 Caprylic/Capric Triglyceride
    1.5 Cyclopentasiloxane, Cyclohexasilosane
    2.0 PEG-40 Hydrogenated Castor Oil
    B 3.5 Caprylic/Capric Triglyceride, Sodium Acrylates Copolymer
    C 1.0 Tocopheryl Acetate
    0.2 Bisabolol
    q.s. Preservative
    q.s. Perfume Oil
    D 3.0 Polyquaternium-44
    0.5 Cocotrimonium Methosulfate
    0.5 Ceteareth-25
    2.0 Panthenol, Propylene Glycol
    4.0 Propylene Glycol
    0.1 Disodium EDTA
    5.0 C16-Microbead
    56.7 Aqua dem.
  • Preparation: Dissolve phase A. Stir phase B into phase A, incorporate phase C into the combined phases A and B. Dissolve phase D, stir into the combined phases A, B and C and homogenize. After-stir for 15 min.
    • Example 10 Use of C16-Microbead-Canthaxanthin in a Daily Care Body Spray
  • % Ingredient (INCI)
    Al 1%:
    A 3.0 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    1.0 Polyquaternium-44
    3.0 Propylene Glycol
    2.0 Panthenol, Propylene Glycol
    1.0 Cyclopentasiloxane, Cyclohexasiloxane
    10.0 Octyldodecanol
    0.5 PVP
    10.0 Caprylic/Capric Triglyceride
    3.0 C12-15 Alkyl Benzoate
    3.0 Glycerin
    1.0 Tocopheryl Acetate
    0.3 Bisabolol
    1.0 C16-Microbead-Canthaxanthin
    59.2 Alcohol
    Al
    5%:
    A 3.0 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    1.0 Polyquaternium-44
    3.0 Propylene Glycol
    2.0 Panthenol, Propylene Glycol
    1.0 Cyclopentasiloxane, Cyclohexasiloxane
    10.0 Octyldodecanol
    0.5 PVP
    10.0 Caprylic/Capric Triglyceride
    3.0 C12-15 Alkyl Benzoate
    3.0 Glycerin
    1.0 Tocopheryl Acetate
    0.3 Bisabolol
    5.0 C16-Microbead-Canthaxanthin
    55.2 Alcohol
  • Preparation: Weigh in the components of phase A and dissolve to give a clear solution.
    • Example 11 Use of C16-Microbead in a Skincare Gel
  • % Ingredient (INCI)
    Al 1%:
    A 3.6 PEG-40 Hydrogenated Castor Oil
    15.0 Alcohol
    0.1 Bisabolol
    0.5 Tocopheryl Acetate
    q.s. Perfume Oil
    B 3.0 Panthenol
    0.6 Carbomer
    1.0 C16-Microbead
    75.4 Aqua dem.
    C 0.8 Triethanolamine
    Al
    5%:
    A 3.6 PEG-40 Hydrogenated Castor Oil
    15.0 Alcohol
    0.1 Bisabolol
    0.5 Tocopheryl Acetate
    q.s. Perfume Oil
    B 3.0 Panthenol
    0.6 Carbomer
    5.0 C16-Microbead
    71.4 Aqua dem.
    C 0.8 Triethanolamine
  • Preparation: Dissolve phase A to give a clear solution. Allow phase B to swell and neutralize with phase C. Stir phase A into the homogenized phase B and homogenize.
    • Example 12 Use of C16-Microbead-Canthaxanthin in an Aftershave Lotion
  • % Ingredient (INCI)
    Al 1%:
    A 10.0 Cetearyl Ethylhexanoate
    5.0 Tocopheryl Acetate
    1.0 Bisabolol
    0.1 Perfume Oil
    0.3 Acrylates/C10-30 Alkyl Acrylate Crosspolymer
    B 15.0 Alcohol
    1.0 Panthenol
    3.0 Glycerin
    1.0 C16-Microbead-Canthaxanthin
    0.1 Triethanolamine
    63.5 Aqua dem.
    Al 5%:
    A 10.0 Cetearyl Ethylhexanoate
    5.0 Tocopheryl Acetate
    1.0 Bisabolol
    0.1 Perfume Oil
    0.3 Acrylates/C10-30 Alkyl Acrylate Crosspolymer
    B 15.0 Alcohol
    1.0 Panthenol
    3.0 Glycerin
    5.0 C16-Microbead-Canthaxanthin
    0.1 Triethanolamine
    59.5 Aqua dem.
  • Preparation: Mix the components of phase A. Dissolve phase B, incorporate into phase A and homogenize.
    • Example 13 Use of C16-Microbead in an Aftersun Lotion
  • % Ingredient (INCI)
    Al 1%:
    A 0.4 Acrylates/C10-30 Alkyl Acrylate Crosspolymer
    15.0 Cetearyl Ethylhexanoate
    0.2 Bisabolol
    1.0 Tocopheryl Acetate
    q.s. Perfume Oil
    B 1.0 Panthenol
    15.0 Alcohol
    3.0 Glycerin
    1.0 C16-Microbead
    63.2 Aqua dem.
    C 0.2 Triethanolamine
    Al
    5%:
    A 0.4 Acrylates/C10-30 Alkyl Acrylate Crosspolymer
    15.0 Cetearyl Ethylhexanoate
    0.2 Bisabolol
    1.0 Tocopheryl Acetate
    q.s. Perfume Oil
    B 1.0 Panthenol
    15.0 Alcohol
    3.0 Glycerin
    5.0 C16-Microbead
    59.2 Aqua dem.
    C 0.2 Triethanolamine
  • Preparation: Mix the Components of Phase A. Stir Phase B into Phase A with homogenization. Neutralize with phase C and homogenize again.
    • Example 14 Use of C16-Microbead-Canthaxanthin in a Sunscreen Lotion
  • % Ingredient (INCI)
    Al 1%:
    A 4.5 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    3.0 Octocrylene
    2.5 Di-C12-13 Alkyl Malate
    0.5 Tocopheryl Acetate
    4.0 Polyglyceryl-3 Methyl Glucose Distearate
    B 3.5 Cetearyl Isononanoate
    1.0 VP/Eicosene Copolymer
    5.0 Isohexadecane
    2.5 Di-C12-13 Alkyl Malate
    3.0 Titanium Dioxide, Trimethoxycaprylylsilane
    C 5.0 Glycerin
    1.0 Sodium Cetearyl Sulfate
    0.5 Xanthan Gum
    1.0 C16-Microbead-Canthaxanthin
    59.7 Aqua dem.
    D 1.0 Phenoxyethanol, Methylparaben, Ethylparaben,
    Butylparaben, Propylparaben, Isobutylparaben
    0.3 Bisabolol
    Al
    5%:
    A 4.5 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    3.0 Octocrylene
    2.5 Di-C12-13 Alkyl Malate
    0.5 Tocopheryl Acetate
    4.0 Polyglyceryl-3 Methyl Glucose Distearate
    B 3.5 Cetearyl Isononanoate
    1.0 VP/Eicosene Copolymer
    5.0 Isohexadecane
    2.5 Di-C12-13 Alkyl Malate
    3.0 Titanium Dioxide, Trimethoxycaprylylsilane
    C 5.0 Glycerin
    1.0 Sodium Cetearyl Sulfate
    0.5 Xanthan Gum
    5.0 C16-Microbead-Canthaxanthin
    55.7 Aqua dem.
    D 1.0 Phenoxyethanol, Methylparaben, Ethylparaben,
    Butylparaben, Propylparaben, Isobutylparaben
    0.3 Bisabolol
  • Preparation: Heat the components of phase A and B separately from one another to about 80° C. Stir phase B into phase A and homogenize. Heat phase C to about 80° C. and stir into the combined phases A and B with homogenization. Cool to about 40° C. with stirring, add phase D and homogenize again.
    • Example 15 Use of C16-Microbead in a Sunscreen Lotion—O/W Type
  • % Ingredient (INCI)
    Al 1%:
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    3.0 Tribehenin
    2.0 Cetearyl Alcohol
    2.0 Cetearyl Ethylhexanoate
    5.0 Ethylhexyl Methoxycinnamate
    1.0 Ethylhexyl Triazone
    1.0 VP/Eicosene Copolymer
    7.0 Isopropyl Myristate
    B 5.0 Zinc Oxide, Triethoxycaprylylsilane
    C 0.2 Xanthan Gum
    0.5 Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    0.2 Disodium EDTA
    5.0 Propylene Glycol
    0.5 Panthenol
    1.0 C16-Microbead
    60.9 Aqua dem.
    D 0.5 Phenoxyethanol, Methylparaben, Butylparaben,
    Ethylparaben, Propylparaben, Isopropylparaben
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
    Al
    5%:
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    3.0 Tribehenin
    2.0 Cetearyl Alcohol
    2.0 Cetearyl Ethylhexanoate
    5.0 Ethylhexyl Methoxycinnamate
    1.0 Ethylhexyl Triazone
    1.0 VP/Eicosene Copolymer
    7.0 Isopropyl Myristate
    B 5.0 Zinc Oxide, Triethoxycaprylyisilane
    C 0.2 Xanthan Gum
    0.5 Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    0.2 Disodium EDTA
    5.0 Propylene Glycol
    0.5 Panthenol
    5.0 C16-Microbead
    56.9 Aqua dem.
    D 0.5 Phenoxyethanol, Methylparaben, Butylparaben,
    Ethylparaben, Propylparaben, Isopropylparaben
    1.0 Tocopheryl Acetate
    0.2 Bisabolol
  • Preparation: Heat phase A to about 80° C., stir in phase B and homogenize for 3 min. Heat phase C likewise to 80° C. and stir into the combined phases A and B with homogenization. Cool to about 40° C., stir in phase D and homogenize again.
    • Example 16 Use of C16-Microbead in a Sunscreen Lotion—O/W Type
  • % Ingredient (INCI)
    Al 1%:
    A 3.5 Ceteareth-6, Stearyl Alcohol
    1.5 Ceteareth-25
    7.5 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 Cyclopentasiloxane, Cyclohexasiloxane
    0.5 Bees Wax
    3.0 Cetearyl Alcohol
    10.0 Caprylic/Capric Triglyceride
    B 5.0 Titanium Dioxide, Silica, Methicone, Alumina
    C 3.0 Glycerin
    0.2 Disodium EDTA
    0.3 Xanthan Gum
    1.0 Decyl Glucoside
    2.0 Panthenol, Propylene Glycol
    1.0 C16-Microbead
    56.3 Aqua dem.
    D 1.0 Tocopheryl Acetate
    0.2 Bisabolol
    q.s. Perfume Oil
    q.s. Preservative
    Al
    5%:
    A 3.5 Ceteareth-6, Stearyl Alcohol
    1.5 Ceteareth-25
    7.5 Ethylhexyl Methoxycinnamate
    2.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.0 Cyclopentasiloxane, Cyclohexasiloxane
    0.5 Bees Wax
    3.0 Cetearyl Alcohol
    10.0 Caprylic/Capric Triglyceride
    B 5.0 Titanium Dioxide, Silica, Methicone, Alumina
    C 3.0 Glycerin
    0.2 Disodium EDTA
    0.3 Xanthan Gum
    1.0 Decyl Glucoside
    2.0 Panthenol, Propylene Glycol
    5.0 C16-Microbead
    52.3 Aqua dem.
    D 1.0 Tocopheryl Acetate
    0.2 Bisabolol
    q.s. Perfume Oil
    q.s. Preservative
  • Preparation: Heat phase A to about 80° C., stir in phase B and homogenize for 3 min. Likewise heat phase C to 80° C. and stir into the combined phases A and B with homogenization. Cool to about 40° C., stir in phase D and homogenize again.
    • Example 17 Use of C16-Microbead-Canthaxanthin in a Foot Balm
  • % Ingredient (INCI)
    Al 1%:
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    5.0 Cetearyl Ethylhexanoate
    4.0 Cetyl Alcohol
    4.0 Glyceryl Stearate
    5.0 Mineral Oil
    0.2 Menthol
    0.5 Camphor
    B 69.3  Aqua dem.
    1.0 C16-Microbead-Canthaxanthin
    q.s. Preservative
    C 1.0 Bisabolol
    1.0 Tocopheryl Acetate
    D 5.0 Witch Hazel Extract
    Al 5%:
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    5.0 Cetearyl Ethylhexanoate
    4.0 Cetyl Alcohol
    4.0 Glyceryl Stearate
    5.0 Mineral Oil
    0.2 Menthol
    0.5 Camphor
    B 65.3  Aqua dem.
    5.0 C16-Microbead-Canthaxanthin
    q.s. Preservative
    C 1.0 Bisabolol
    1.0 Tocopheryl Acetate
    D 5.0 Witch Hazel Extract
  • Preparation: Heat the components of phases A and B separately from one another to about 80° C. Stir phase B into phase A with homogenization. Cool to about 40° C. with stirring, add phases C and D and briefly after-homogenize. Cool to room temperature with stirring.
    • Example 18 Use of C18-Microbead-Canthaxanthin in a W/O Emulsion with Bisabolol
  • % Ingredient (INCI)
    Al 1%:
    A 6.0 PEG-7 Hydrogenated Castor Oil
    8.0 Cetearyl Ethylhexanoate
    5.0 Isopropyl Myristate
    15.0 Mineral Oil
    0.3 Magnesium Stearate
    0.3 Aluminum Stearate
    2.0 PEG-45/Dodecyl Glycol Copolymer
    B 5.0 Glycerin
    0.7 Magnesium Sulfate
    1.0 C16-Microbead-Canthaxanthin
    55.6 Aqua dem.
    C 0.5 Tocopheryl Acetate
    0.6 Bisabolol
    Al
    5%:
    A 6.0 PEG-7 Hydrogenated Castor Oil
    8.0 Cetearyl Ethylhexanoate
    5.0 Isopropyl Myristate
    15.0 Mineral Oil
    0.3 Magnesium Stearate
    0.3 Aluminum Stearate
    2.0 PEG-45/Dodecyl Glycol Copolymer
    B 5.0 Glycerin
    0.7 Magnesium Sulfate
    51.6 Aqua dem.
    5.0 C16-Microbead-Canthaxanthin
    C 0.5 Tocopheryl Acetate
  • Preparation: Heat phases A and B separately from one another to about 85° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phase C and briefly homogenize again. Cool to room temperature with stirring.
    • Example 19 Foam Conditioner with Setting Agent
  • % Ingredient (INCI)
    Al 1%
    A 10.0 PVP/VA Copolymer
    0.2 Hydroxyethyl Cetyldimonium Phosphate
    0.2 Ceteareth-25
    0.5 Dimethicone Copolyol
    q.s. Perfume Oil
    10.0 Alcohol
    1.0 C16-Microbead-Canthaxanthin
    68.1 Aqua dem.
    10.0 Propane/Butane
    Al
    5%
    A 10.0 PVP/VA Copolymer
    0.2 Hydroxyethyl Cetyldimonium Phosphate
    0.2 Ceteareth-25
    0.5 Dimethicone Copolyol
    q.s. Perfume Oil
    10.0 Alcohol
    5.0 C16-Microbead-Canthaxanthin
    64.1 Aqua dem.
    10.0 Propane/Butane
  • Preparation: Weigh the components of phase A together, stir until everything has dissolved and bottle.
    • Example 20 Foam Conditioner
  • % Ingredient (INCI)
    Al 1%
    A 1.0 Polyquaterntum-4
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    1.0 C16-Microbead
    q.s. Perfume Oil
    q.s. Preservative
    91.5  Aqua dem.
    6.0 Propane/Butane
    Al
    5%
    A 1.0 Polyquaternium-4
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    5.0 C16-Microbead-Canthaxanthin
    q.s. Perfume Oil
    q.s. Preservative
    87.5  Aqua dem.
    6.0 Propane/Butane
  • Preparation: Weigh the components of phase A together, stir until everything has dissolved to give a clear solution and bottle.
    • Example 21 Foam Conditioner
  • % Ingredient (INCI)
    Al 1%
    A 1.0 Polyquaternium-11
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    1.0 C16-Microbead
    q.s. Perfume Oil
    q.s. Preservative
    91.5  Aqua dem.
    6.0 Propane/Butane
    Al
    5%
    A 1.0 Polyquaternium-11
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    5.0 C16-Microbead
    q.s. Perfume Oil
    q.s. Preservative
    87.5  Aqua dem.
    6.0 Propane/Butane
  • Preparation: Weigh the components of phase A together, stir until everything has dissolved to give a clear solution and bottle.
    • Example 22 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 0.5 Laureth-4
    q.s. Perfume Oil
    B 77.3  Aqua dem.
    10.0  Polyquaternium-28
    1.0 C16-Microbead
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    0.2 Hydroxyethylcellulose
    C 10.0  HFC 152 A
    Al 5%
    A 0.5 Laureth-4
    q.s. Perfume Oil
    B 73.3  Aqua dem.
    10.0  Polyquaternium-28
    5.0 C16-Microbead
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    0.2 Hydroxyethylcellulose
    C 10.0  HFC 152 A
  • Preparation: Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
    • Example 23 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B 78.5  Aqua dem.
    6.7 Acrylates Copolymer
    0.6 AMP
    1.0 C16-Microbead-Canthaxanthin
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    0.2 Hydroxyethylcellulose
    C 10.0  HFC 152 A
    Al 5%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B 74.5  Aqua dem.
    6.7 Acrylates Copolymer
    0.6 AMP
    5.0 C16-Microbead-Canthaxanthin
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    0.2 Hydroxyethylcellulose
    C 10.0  HFC 152 A
  • Preparation: Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
    • Example 24 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B  7.70 Polyquaternium-44
    1.0 C16-Microbead-Canthaxanthin
    q.s. Preservative
    79.3  Aqua dem.
    C 10.0  Propane/Butane
    Al
    5%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B  7.70 Polyquaternium-44
    5.0 C16-Microbead-Canthaxanthin
    q.s. Preservative
    75.3  Aqua dem.
    C 10.0  Propane/Butane
  • Preparation: Mix the components of phase A. Dissolve the components of phase B to give a clear solution, then stir phase B into phase A. Adjust the pH to 6-7, bottle with phase C.
    • Example 25 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 2.00 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B 72.32  Aqua dem.
    2.00 VP/Acrylates/Lauryl Methacrylate Copolymer
    0.53 AMP
    1.00 C16-Microbead-Canthaxanthin
    0.20 Ceteareth-25
    0.50 Panthenol
    0.05 Benzophenone-4
    0.20 Amodimethicone, Cetrimonium Chloride, Trideceth-12
    15.00  Alcohol
    C 0.20 Hydroxyethylcellulose
    D 6.00 Propane/Butane
    Al
    5%
    A 2.00 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B 68.32  Aqua dem.
    2.00 VP/Acrylates/Lauryl Methacrylate Copolymer
    0.53 AMP
    5.00 C16-Microbead-Canthaxanthin
    0.20 Ceteareth-25
    0.50 Panthenol
    0.05 Benzophenone-4
    0.20 Amodimethicone, Cetrimonium Chloride, Trideceth-12
    15.00  Alcohol
    C 0.20 Hydroxyethylcellulose
    D 6.00 Propane/Butane
  • Preparation: Mix the components of phase A. Add the components of phase B one after the other and dissolve. Dissolve phase C in the mixture with A and B, then adjust the pH to 6-7. Bottle with phase D.
    • Example 26 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 2.00 Cetrimonium Chloride
    q.s. Perfume Oil
    B 67.85  Aqua dem.
    7.00 Potyquaternium-46
    1.00 C16-Microbead
    0.20 Ceteareth-25
    0.50 Panthenol
    0.05 Benzophenone-4
    0.20 Amodimethicone, Cetrimonium Chloride, Trideceth-12
    15.00  Alcohol
    C 0.20 Hydroxyethylcellulose
    D 6.00 Propane/Butane
    Al
    5%
    A 2.00 Cetrimonium Chloride
    q.s. Perfume Oil
    B 63.85  Aqua dem.
    7.00 Polyquaternium-46
    5.00 C16-Microbead
    0.20 Ceteareth-25
    0.50 Panthenol
    0.05 Benzophenone-4
    0.20 Amodimethicone, Cetrimonium Chloride, Trideceth-12
    15.00  Alcohol
    C 0.20 Hydroxyethylcellulose
    D 6.00 Propane/Butane
  • Preparation: Mix the components of phase A. Add the components of phase B one after the other and dissolve. Dissolve phase C in the mixture with A and B, then adjust the pH to 6-7. Bottle with phase D.
    • Example 27 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    85.5  Aqua dem.
    B 7.0 Sodium Polystyrene Sulfonate
    1.0 C16-Microbead-Canthaxanthin
    0.5 Cetrimonium Bromide
    q.s. Preservative
    C 6.0 Propane/Butane
    Styling foam
    Al
    5%
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    81.5  Aqua dem.
    B 7.0 Sodium Polystyrene Sulfonate
    5.0 C16-Mtcrobead-Canthaxanthin
    0.5 Cetrimonium Bromide
    q.s. Preservative
    C 6.0 Propane/Butane
  • Preparation: Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
    • Example 28 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    92.0  Aqua dem.
    B 0.5 Polyquaternium-10
    1.0 C16-Microbead
    0.5 Cetrimonium Bromide
    q.s. Preservative
    C 6.0 Propane/Butane
    Al
    5%
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    88.0  Aqua dem.
    B 0.5 Polyquaternium-10
    5.0 C16-Microbead
    0.5 Cetrimonium Bromide
    q.s. Preservative
    C 6.0 Propane/Butane
  • Preparation: Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
    • Example 29 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    82.5  Aqua dem.
    B 10.0  Polyquaternium-16
    1.0 C16-Microbead-Canthaxanthin
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    q.s. Preservative
    C 6.0 Propane/Butane
    Al
    5%
    % Ingredient (INCI)
    A q.s. PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    78.5  Aqua dem.
    B 10.0  Polyquaternium-16
    5.0 C16-Microbead-Canthaxanthin
    0.5 Hydroxyethyl Cetyldimonium Phosphate
    q.s. Preservative
    C 6.0 Propane/Butane
  • Preparation: Solubilize phase A. Weigh phase B into phase A and dissolve to give a clear solution. Adjust the pH to 6-7, bottle with phase C.
    • Example 30 Styling Foam
  • % Ingredient (INCI)
    Al 1%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume OH
    B 84.0  Aqua dem.
    2.0 Chitosan
    1.0 C16-Microbead
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    C 10.0  HFC 152 A
    Al 5%
    A 2.0 Cocotrimonium Methosulfate
    q.s. Perfume Oil
    B 80.0  Aqua dem.
    2.0 Chitosan
    5.0 C16-Microbead
    0.5 Dimethicone Copolyol
    0.2 Ceteareth-25
    0.2 Panthenol
    0.1 PEG-25 PABA
    C 10.0  HFC 152 A
  • Preparation: Mix the components of phase A. Add the components of phase B one after the other and dissolve. Bottle with phase C.
    • Example 31 Care Shampoo
  • % Ingredient (INCI)
    Al 1%
    A 30.0  Sodium Laureth Sulfate
    6.0 Sodium Cocoamphoacetate
    6.0 Cocamidopropyl Betaine
    3.0 Sodium Laureth Sulfate, Glycol Distearate,
    Cocamide MEA, Laureth-10
    1.0 C16-Microbead
    7.7 Polyquaternium-44
    2.0 Amodimethicone
    q.s. Perfume Oil
    q.s. Preservative
    1.0 Sodium Chloride
    43.3  Aqua dem.
    B q.s. Citric Acid
    Al
    5%
    A 30.0  Sodium Laureth Sulfate
    6.0 Sodium Cocoamphoacetate
    6.0 Cocamidopropyl Betaine
    3.0 Sodium Laureth Sulfate, Glycol Distearate,
    Cocamide MEA, Laureth-10
    5.0 C16-Microbead
    7.7 Polyquaternium-44
    2.0 Amodimethicone
    q.s. Perfume Oil
    q.s. Preservative
    1.0 Sodium Chloride
    39.3  Aqua dem.
    B q.s. Citric Acid
  • Preparation: Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
    • Example 32 Shower Gel
  • % Ingredient (INCI)
    Al 1%
    A 40.0  Sodium Laureth Sulfate
    5.0 Decyl Glucoside
    5.0 Cocamidopropyl Betaine
    1.0 C16-Microbead-Canthaxanthin
    1.0 Panthenol
    q.s. Perfume Oil
    q.s. Preservative
    2.0 Sodium Chloride
    46.0  Aqua dem.
    B q.s. Citric Acid
    Al
    5%
    A 40.0  Sodium Laureth Sulfate
    5.0 Decyl Glucoside
    5.0 Cocamidopropyl Betaine
    5.0 C16-Microbead-Canthaxanthin
    1.0 Panthenol
    q.s. Perfume Oil
    q.s. Preservative
    2.0 Sodium Chloride
    42.0  Aqua dem.
    B q.s. Citric Acid
  • Preparation: Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
    • Example 33 Shampoo
  • % Ingredient (INCI)
    Al 1%
    A 40.0  Sodium Laureth Sulfate
    5.0 Sodium C12-15 Pareth-15 Sulfonate
    5.0 Decyl Glucoside
    q.s. Perfume Oil
    0.1 Phytantriol
    44.6  Aqua dem.
    1.0 C16-Microbead
    0.3 Polyquaternium-10
    1.0 Panthenol
    q.s. Preservative
    1.0 Laureth-3
    2.0 Sodium Chloride
    Al
    5%
    A 40.0  Sodium Laureth Sulfate
    5.0 Sodium C12-15 Pareth-15 Sulfonate
    5.0 Decyl Glucoside
    q.s. Perfume Oil
    0.1 Phytantriol
    40.6  Aqua dem.
    5.0 C16-Microbead
    0.3 Polyquaternium-10
    1.0 Panthenol
    q.s. Preservative
    1.0 Laureth-3
    2.0 Sodium Chloride
  • Preparation: Mix the components of phase A and dissolve. Adjust the pH to 6-7 with citric acid.
    • Example 34 Shampoo
  • % Ingredient (INCI)
    Al 1%
    A 15.00  Cocamidopropyl Betaine
    10.00  Disodium Cocoamphodiacetate
    5.00 Polysorbate 20
    5.00 Decyl Glucoside
    q.s. Perfume Oil
    q.s. Preservative
    1.00 C16-Microbead
    0.15 Guar Hydroxypropyltrimonium Chloride
    2.00 Laureth-3
    58.00  Aqua dem.
    q.s. Citric Acid
    B 3.00 PEG-150 Distearate
    Al
    5%
    A 15.00  Cocamidopropyl Betaine
    10.00  Disodium Cocoamphodiacetate
    5.00 Polysorbate 20
    5.00 Decyl Glucoside
    q.s. Perfume Oil
    q.s. Preservative
    5.00 C16-Microbead
    0.15 Guar Hydroxypropyltrimonium Chloride
    2.00 Laureth-3
    54.00  Aqua dem.
    q.s. Citric Acid
    B 3.00 PEG-150 Distearate
  • Preparation: Weigh in the components of phase A and dissolve. Adjust the pH to 6-7. Add phase B and heat to about 50° C. Cool to room temperature with stirring.
    • Example 35 Moisturizing Bodycare Cream
  • % Ingredient (INCI)
    Al 1%
    A 2.0 Ceteareth-25
    2.0 Ceteareth-6, Stearyl Alcohol
    3.0 Cetearyl Ethylhexanoate
    1.0 Dimethicone
    4.0 Cetearyl Alcohol
    3.0 Glyceryl Stearate SE
    5.0 Mineral Oil
    4.0 Simmondsia Chinensis (Jojoba) Seed Oil
    3.0 Mineral Oil, Lanolin Alcohol
    B 5.0 Propylene Glycol
    1.0 C16-Microbead
    1.0 Panthenol
    0.5 Magnesium Aluminum Silicate
    q.s Preservative
    65.5  Aqua dem.
    C q.s. Perfume Oil
    D q.s. Citric Acid
    Al
    5%
    A 2.0 Ceteareth-25
    2.0 Ceteareth-6, Stearyl Alcohol
    3.0 Cetearyl Ethylhexanoate
    1.0 Dimethicone
    4.0 Cetearyl Alcohol
    3.0 Glyceryl Stearate SE
    5.0 Mineral Oil
    4.0 Simmondsia Chinensis (Jojoba) Seed Oil
    3.0 Mineral Oil, Lanolin Alcohol
    B 5.0 Propylene Glycol
    5.0 C16-Microbead
    1.0 Panthenol
    0.5 Magnesium Aluminum Silicate
    q.s Preservative
    61.5  Aqua dem.
    C q.s. Perfume Oil
    D q.s. Citric Acid
  • Preparation: Heat phases A and B separately to about 80° C. Briefly prehomogenize phase B, then stir phase B into phase A and homogenize again. Cool to about 40° C., add phase C and homogenize well again. Adjust the pH to 6-7 with citric acid.
    • Example 36 Moisturizing Bodycare Cream
  • % Ingredient (INCI)
    Al 1%
    A 6.0 PEG-7 Hydrogenated Castor Oil
    10.0  Cetearyl Ethylhexanoate
    5.0 Isopropyl Myristate
    7.0 Mineral Oil
    0.5 Shea Butter (Butyrospermum Parkii)
    0.5 Aluminum Stearate
    0.5 Magnesium Stearate
    0.2 Bisabolol
    0.7 Quaternium-18-Hectorite
    B 5.0 Dipropylene Glycol
    0.7 Magnesium Sulfate
    1.0 C16-MScrobead
    q.s. Preservative
    62.9  Aqua dem.
    C q.s. Perfume Oil
    Al
    5%
    A 6.0 PEG-7 Hydrogenated Castor Oil
    10.0  Cetearyl Ethylhexanoate
    5.0 Isopropyl Myristate
    7.0 Mineral Oil
    0.5 Shea Butter (Butyrospermum Parkii)
    0.5 Aluminum Stearate
    0.5 Magnesium Stearate
    0.2 Bisabolol
    0.7 Quaternium-18-Hectorite
    B 5.0 Dipropylene Glycol
    0.7 Magnesium Sulfate
    5.0 C16-Microbead
    q.s. Preservative
    58.9  Aqua dem.
    C q.s. Perfume Oil
  • Preparation: Heat phases A and B separately to about 80° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phase C and homogenize again. Allow to cool to room temperature with stirring.
    • Example 37 Liquid Make-Up—O/W Type
  • % Ingredient (INCI)
    Al 1%
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    6.0 Glyceryl Stearate
    1.0 Cetyl Alcohol
    8.0 Mineral Oil
    7.0 Cetearyl Ethylhexanoate
    0.2 Dimethicone
    B 3.0 Propylene Glycol
    1.0 Panthenol
    q.s. Preservative
    1.0 C16-Microbead-Canthaxanthin
    61.9  Aqua dem.
    C 0.1 Bisabolol
    q.s. Perfume Oil
    D 5.7 C.I. 77 891, Titanium Dioxide
    1.1 Iron Oxides
    Al
    5%
    A 2.0 Ceteareth-6, Stearyl Alcohol
    2.0 Ceteareth-25
    6.0 Glyceryl Stearate
    1.0 Cetyl Alcohol
    8.0 Mineral Oil
    7.0 Cetearyl Ethylhexanoate
    0.2 Dimethicone
    B 3.0 Propylene Glycol
    1.0 Panthenol
    5.0 C16-Microbead-Canthaxanthin
    q.s. Preservative
    57.9  Aqua dem.
    C 0.1 Bisabolol
    q.s. Perfume Oil
    D 5.7 C.I. 77 891, Titanium Dioxide
    1.1 Iron Oxides
  • Preparation: Heat phases A and B separately to about 80° C. Stir phase B into phase A and homogenize. Cool to about 40° C. with stirring, add phases C and D and thoroughly homogenize again. Allow to cool to room temperature with stirring.
    • Example 38
  • Dermocosmetic preparations according to the invention are described below, comprising the C16-microbead prepared according to Examples 1, or C16-microbead-canthaxanthin prepared according to Example 4. The following data are parts by weight of an aqueous solution.
  • Ingredients (INCI) 1 2 3 4 5
    Clear shampoo
    Sodium Laureth Sulfate 13.00 15.00 10.50 12.50 10.00
    Cocamidopropyl Betaine 7.50 7.00 5.00 5.50 10.00
    PEG-7 Glyceryl Cocoate 2.00 2.50 3.50 5.00 2.30
    Perfume Oil 0.10 0.10 0.10 0.10 0.10
    C16-Microbead- 1.0 5.0 0.1 0.5 10.0
    Canthaxanthin
    D-Panthenol USP 1.00 1.50 1.80 1.70 1.40
    Preservative 0.10 0.10 0.10 0.10 0.10
    Citric Acid 0.10 0.10 0.10 0.10 0.10
    Luviquat ® Ultra Care 1.50 1.00 1.50 1.20 1.10
    Sodium Chloride 1.50 1.40 1.40 1.30 1.50
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    Shampoo
    Sodium Laureth Sulfate 35.00 40.00 30.00 45.00 27.00
    Decyl Glucoside 5.00 5.50 4.90 3.50 7.00
    Cocamidopropyl Betaine 10.00 5.00 12.50 7.50 15.00
    Perfume Oil 0.10 0.10 0.10 0.10 0.10
    C16-Microbead- 1.0 5.0 0.1 0.5 10.0
    Canthaxanthin
    D-Panthenol USP 0.50 1.00 0.80 1.50 0.50
    Preservative 0.10 0.10 0.10 0.10 0.10
    Citric Acid 0.10 0.10 0.10 0.10 0.10
    Laureth-3 0.50 2.00 0.50 0.50 2.00
    Sodium Chloride 1.50 1.50 1.50 1.50 1.50
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    Clear conditioner shampoo
    ® Disodium 10.00 15.00 20.00 12.00 17.00
    Cocoamphodiacetate
    ® Decyl Glucoside 5.00 6.00 7.00 8.00 4.00
    ® Cocamidopropyl 15.00 12.00 10.00 18.00 20.00
    Betaine
    Luviquat ® FC 550 0.30 0.20 0.20 0.20 0.30
    Perfume Oil 0.10 0.10 0.10 0.10 0.10
    C16-Microbead 20.0 5.0 1.0 0.5 10.0
    Cremophor ® PS 20 5.00 1.00 1.00 7.00 5.00
    Preservative 0.10 0.10 0.10 0.10 0.10
    ® Laureth-3 2.00 1.00 0.50 2.00 2.00
    Citric Acid 0.20 0.20 0.20 0.20 0.20
    PEG-12 Distearate 3.00 2.00 2.00 3.00 2.50
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
  • Foam O/W emulsions
    Emulsion
    1 Emulsion 2
    % by wt. % by vol % by wt. % by vol
    Stearic Acid 5.00 1.00
    Cetyl Alcohol 5.50
    Cetearyl Alcohol 2.00
    PEG-40 Stearate 8.50
    PEG-20 Stearate 1.00
    Caprylic/Capric 4.00 2.00
    Triglyceride
    C12-15 Alkyl 10.00 15.00
    Benzoate
    Cyclomethicone 4.00
    Dimethicone 0.50
    C16-Microbead 5.0 10.0
    Ethylhexyl 5.00
    Isostearate
    Myristyl Myristate 2.00
    Ceresin 1.50
    Glycerin 3.00
    ??
    Hydroxypropyl 1.00 3.50
    Starch
    Phosphate
    BHT 0.02
    Disodium EDTA 0.50 0.10
    Perfume Oil, q.s. q.s.
    Preservative
    Colorant q.s. q.s.
    Potassium q.s. q.s.
    Hydroxide
    Aqua dem. ad 100 ad 100
    Adjust pH to Adjust pH to
    6.5-7.5 5.0-6.0
    Emulsion 1 70
    Emulsion 2 35
    Nitrogen 30
    Propane/Butane 65
  • 1 2 3
    Conditioner shampoo with pearlescence
    Polyquaternium-10 0.50 0.50 0.40
    Sodium Laureth Sulfate 9.00 8.50 8.90
    Codamidopropyl Betaine 2.50 2.60 3.00
    Uvinul ® MS 40 1.50 0.50 1.00
    C16-Microbead 1.0 5.0 0.5
    Pearlescent solution 2.00 2.50
    Disodium EDTA 0.10 0.15 0.05
    Preservative, Perfume Oil, Thickener q.s. q.s. q.s.
    Aqua dem. ad 100 ad 100 ad 100
    Adjust pH to 6.0
    Clear conditioner shampoo
    Polyquaternium-10 0.50 0.50 0.50
    Sodium Laureth Sulfate 9.00 8.50 9.50
    C16-Microbead 5.0 0.1 3.0
    Uvinul M ® 40 1.00 1.50 0.50
    0.20 0.20 0.80
    Preservative, Perfume Oil, Thickener q.s. q.s. q.s.
    Aqua dem. ad 100 ad 100 ad 100
    Adjust pH to 6.0
    Clear conditioner shampoo with volume effect
    Sodium Laureth Sulfate 10.00 10.50 11.00
    Uvinul ® MC 80 2.00 1.50 2.30
    C16-Microbead 10.0 0.1 0.5
    Cocamidopropyl Betaine 2.50 2.60 2.20
    Disodium EDTA 0.01 0.10 0.01
    Preservative, Perfume Oil, Thickener q.s. q.s. q.s.
    Aqua dem. ad 100 ad 100 ad 100
    Adjust pH to 6.0
  • Gel cream
    1 2 3 4
    Acrylates/C10-30 Alkylacrylate 0.40 0.35 0.40 0.35
    Crosspolymer
    Carbomer? 0.20 0.22 0.20 0.22
    Xanthan Gum 0.10 0.13 0.10 0.13
    Cetearyl Alcohol 3.00 2.50 3.00 2.50
    C12-15 Alkyl Benzoate 4.00 4.50 4.00 4.50
    Caprylic/Capric Triglyceride 3.00 3.50 3.00 3.50
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00
    UvaSorb ® k2A 3.00
    Ethylhexyl
    Bis-Isopentylbenzoxazolylphenyl
    Melamine
    Uvinul ® MC 80 3.00 1.00
    Bis-Ethylhexyloxyphenol 1.50 2.00
    Methoxyphenyl Triazine
    Butyl Methoxydibenzoylmethane 2.00
    Disodium Phenyl Dibenzimidazole 2.50 0.50 2.00
    Tetrasulfonate
    Uvinul ® T 150 4.00 3.00 4.00
    Octocrylene 4.00
    Diethylhexyl Butamido Triazone 1.00 2.00
    Phenylbenzimidazole 0.50 3.00
    Sulfonic Acid
    Methylene Bis-Benzotriazolyl 2.00 0.50 1.50
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00
    Drometrizole Trisiloxane 0.50
    Terephthalidene Dicamphor 1.50 1.00
    Sulfonic Acid
    Diethylhexyl
    2,6-Naphthalate 3.50 4.00 7.00 9.00
    Titanium Dioxide-microfine 1.00 3.00
    Zinc Oxide-microfine 0.25
    C16-Microbead 0.1 0.5 1.0 0.02
    Cyclomethicone 5.00 5.50 5.00 5.50
    Dimethicone 1.00 0.60 1.00 0.60
    Glycerin 1.00 1.20 1.00 1.20
    Sodium Hydroxide q.s. q.s. q.s. q.s.
    Preservative 0.30 0.23 0.30 0.23
    Perfume Oil 0.20 0.20
    Aqua dem. ad 100 ad 100 ad 100 ad 100
    Adjust pH to 6.0
  • OW sunscreen formulation
    1 2 3 4 5 6 7
    Glyceryl Stearate SE 0.50 1.00 3.00 1.50
    Glycerl Stearate Citrate 2.00 1.00 2.00 4.00
    Stearic Acid 3.00 2.00
    PEG-40 Stearate 0.50 2.00
    Cetyl Phosphate 1.00
    Sodium Cetearyl Sulfate 0.75
    Stearyl Alcohol 3.00 2.00 0.60
    Cetyl Alcohol 2.50 1.10 1.50 0.60 2.00
    C16-Microbead-Canthaxanthin 10.0 0.5 3.0 5.0 0.1 0.02 7.5
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10 4.50 5.00
    UvaSorb ® k2A
    Ethylhexyl Bis-
    Isopentylbenzoxazolylphenyl
    Melamine
    Ethylhexyl Methoxycinnamate 5.00 6.00 8.00
    Uvinul ® MC 80
    Bis-Ethylhexyloxyphenol 1.50 2.00 2.50 2.50
    Methoxyphenyl Triazine
    Butyl Methoxydibenzoylmethane 2.00 2.00 1.50
    Disodium Phenyl Dibenzimidazole 2.50 0.50 2.00 0.30
    Tetrasulfonate
    Ethyhexyl Triazone Uvinul ® T 150 4.00 3.00 4.00 2.00
    Octocrylene 4.00 7.50
    Diethylhexyl Butamido Triazone 1.00 2.00 1.00 1.00
    Phenylbenzimidazole Sulfonic Acid 0.50 3.00
    Methylene Bis-Benzotriazolyl 2.00 0.50 1.50 2.50
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00 5.00
    Drometrizole Trisiloxane 0.50 1.00
    Terephthalidene Dicamphor 1.50 1.00 1.00 0.50
    Sulfonic Acid
    Diethylhexyl 2,6-Naphthalate 3.50 7.00 6.00 9.00
    Titanium Dioxide-microfine 1.00 3.00 3.50 1.50
    Zinc Oxide-microfine 0.25 2.00
    C12-15 Alkyl Benzoate 0.25 4.00 7.00
    Dicapryl Ether 3.50 2.00
    Butylene Glycol 5.00 6.00
    Dicaprylate/Dicaprate
    Cocoglyceride 6.00 2.00
    Dimethicone 0.50 1.00 2.00
    Cyclomethicone 2.00 0.50 0.50
    Butyrospermum Parkii (Shea 2.00
    Butter)
    VP/Hexadecene Copolymer 0.20 0.50 1.00
    Glycerin 3.00 7.50 7.50 5.00 2.50
    Xanthan Gum 0.15 0.05 0.30
    Sodium Carbomer 0.20 0.15 0.25
    Vitamin E Acetate 0.60 0.23 0.70 1.00
    Biosaccaride Gum-1 3.00 10.00
    Glycine Soja (Soybean) Oil 0.50 1.50 1.00
    Ethylhexylglycerin 0.30
    DMDM Hydantoin 0.60 0.40 0.20
    Iodopropynyl Butylcarbamate 0.18 0.20
    Methylparaben 0.15 0.25 0.50
    Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
    Trisodium EDTA 0.02 0.05
    Tetrasodium Iminodisuccinate 0.25 1.00
    Ethanol 2.00 1.50 3.00 1.20 5.00
    Perfume Oil 0.10 0.25 0.30 0.40 0.20
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100
  • 1 2 3 4 5
    Hydrodispersion
    Ceteaereth-20 1.00 0.50
    Cetyl Alcohol 1.00
    Sodium Carbomer 0.20 0.30
    Acrylates/C10-30 Alkyl Acrylate 0.50 0.40 0.10 0.50
    Crosspolymer
    Xanthan Gum 0.30 0.15
    C16-Microbead-Canthaxanthin 5.0 0.5 3.0 0.1 10.0
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10
    UvaSorb ® k2A Ethylhexyl Bis- 3.50
    Isopentylbenzoxazolylphenyl Melamine
    Ethylhexyl Methoxycinnamate Uvinul ® 5.00
    MC 80
    Bis-Ethylhexyloxyphenol Methoxyphenyl 1.50 2.00 2.50
    Triazine
    Butyl Methoxydibenzoylmethane 2.00 2.00
    Disodium Phenyl Dibenzimidazole 2.50 0.50 2.00
    Tetrasulfonate
    Ethyhexyl Triazone Uvinul ® T 150 4.00 3.00 4.00
    Octocrylene 4.00
    Diethylhexyl Butamido Triazone 1.00 2.00 1.00
    Phenylbenzimidazole Sulfonic Acid 0.50 3.00
    Methylene Bis-Benzotriazolyl 2.00 0.50 1.50 2.50
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00
    Drometrizole Trisiloxane 0.50
    Terephthalidene Dicamphor Sulfonic Acid 1.50 1.00 1.00
    Diethylhexyl 2,6-Naphthalate 7.00 9.00
    Titanium Dioxide-microfine 1.00 3.00 3.50
    Zinc Oxide-microfine 0.25
    C12-15 Alkyl Benzoate 2.00 2.50
    Dicapryl Ether 4.00
    Butylene glycol Dicaprylate/Dicaprate 4.00 2.00 6.00
    Dicapryl Carbonate 2.00 6.00
    Dimethicone 0.50 1.00
    Phenyl Trimethicone 2.00 0.50
    Butyrospermum Parkii (Shea Butter) 2.00 5.00
    VP/Hexadecene Copolymer 0.50 0.50 1.00
    Tricontanyl PVP 0.50 1.00
    Ethylhexylglycerin 1.00 0.80
    Glycerin 3.00 7.50 7.50 8.50
    Glycine Soja (Soybean) Oil 1.50 1.00
    Vitamin E Acetate 0.50 0.25 1.00
    Glucosylrutin 0.60 0.25
    Biosaccaride Gum-1 2.50 0.50 2.00
    DMDM Hydantoin 0.60 0.45 0.25
    Iodopropynyl Butylcarbamate 0.20
    Methylparaben 0.50 0.25 0.15
    Phenoxyethanol 0.50 0.40 1.00
    Trisodium EDTA 0.01 0.05 0.10
    Ethanol 3.00 2.00 1.50 7.00
    Perfume Oil 0.20 0.05 0.40
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    WO Sunscreen Emulsion
    Cetyl Dimethicone 2.50 4.00
    Polyglyceryl-2 Dipolyhydroxystearate 5.00 4.50
    PEG-30 Dipolyhydroxystearate 5.00
    C16-Microbead 5.0 1.0 10.0 0.5 0.1
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10
    UvaSorb ® k2A 2.00
    Ethylhexyl Bis-Isopentylbenzoxazolylphenyl
    Melamine
    Ethylhexyl Methoxycinnamate Uvinul ® 5.00
    MC 80
    Bis-Ethylhexyloxyphenol Methoxyphenyl 1.50 2.00 2.50
    Triazine
    Butyl Methoxydibenzoylmethane 2.00 2.00
    Disodium Phenyl Dibenzimidazole 2.50 0.50 2.00
    Tetrasulfonate
    Ethyhexyl Triazone Uvinul ® T 150 4.00 3.00 4.00
    Octocrylene 4.00
    Diethylhexyl Butamido Triazone 1.00 2.00 1.00
    Phenylbenzimidazole Sulfonic Acid 0.50 3.00
    Methylene Bis-Benzotriazolyl 2.00 0.50 1.50 2.50
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00
    Drometrizole Trisiloxane 0.50
    Terephthalidene Dicamphor Sulfonic Acid 1.50 1.00 1.00
    Diethylhexyl 2,6-Naphthalate 7.00 4.00
    Titanium Dioxide-microfine 1.00 3.00 3.50
    Zinc Oxide-microfine 0.25
    Mineral Oil 12.00 10.00 8.00
    C12-15 Alkyl Benzoate 9.00
    Dicaprylyl Ether 10.00 7.00
    Butylene glycol Dicaprylate/Dicaprate 2.00 8.00 4.00
    Dicaprylyl Carbonate 5.00 6.00
    Dimethicone 4.00 1.00 5.00
    Cyclomethicone 2.00 25.00 2.00
    Butyrospermum Parkii (Shea Butter) 3.00
    Petrolatum 4.50
    VP/Hexadecene Copolymer 0.50 0.50 1.00
    Ethylhexylglycerin 0.30 1.00 0.50
    Glycerin 3.00 7.50 7.50 8.50
    Glycine Soja (Soybean) Oil 1.00 1.50 1.00
    Magnesium Sulfate MgSO4 1.00 0.50 0.50
    Magnesium ChlorideMgCl2 1.00 0.70
    Vitamin E Acetate 0.50 0.25 1.00
    Ascorbyl Palmitate 0.50 2.00
    Biosaccaride Gum-1 3.50 1.00
    DMDM Hydantoin 0.60 0.40 0.20
    Methylparaben 0.50 0.25 0.15
    Phenoxyethanol 0.50 0.40 1.00
    Trisodium EDTA 0.12 0.05 0.30
    Ethanol 3.00 1.50 5.00
    Perfume Oil 0.20 0.40 0.35
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
  • Sticks
    1 2 3 4
    Caprylic/Capric Triglyceride 12.00 10.00 6.00
    Octyldodecanol 7.00 14.00 8.00 3.00
    Butylene Glycol 12.00
    Dicaprylate/Dicaprate
    Pentaerythrityl Tetraisostearate 10.00 6.00 8.00 7.00
    Polyglyceryl-3 Diisostearate 2.50
    Bis-Diglyceryl Polyacyladipate-2 9.00 8.00 10.00 8.00
    Cetearyl Alcohol 8.00 11.00 9.00 7.00
    Myristyl Myristate 3.50 3.00 4.00 3.00
    Beeswax 5.00 5.00 6.00 6.00
    Copernicia Cerifera 1.50 2.00 2.00 1.50
    (Carnauba) Wax
    Cera Alba 0.50 0.50 0.50 0.40
    C16-40 Alkyl Stearate 1.50 1.50 1.50
    C16-Microbead 0.5 3.0 1.0 5.0
    Uvinul ® A Plus ™ 2.00 1.50 0.75 9.00
    UvaSorb ® k2A 2.00 4.00
    Ethylhexyl
    Bis-Isopentylbenzoxazolylphenyl
    Melamine
    Ethylhexyl Methoxycinnamate 3.00
    Uvinul ® MC 80
    Bis-Ethylhexyloxyphenol 1.50 2.00
    Methoxyphenyl
    Triazine
    Butyl Methoxydibenzoylmethane 2.00
    Disodium Phenyl Dibenzimidazole 2.50 0.50 2.00
    Tetrasulfonate
    Ethylhexyl Triazone 4.00 3.00 4.00
    Uvinul ® T 150
    Octocrylene 4.00
    Diethylhexyl Butamido Triazone 1.00 2.00
    Phenylbenzimidazole 0.50 3.00
    Sulfonic Acid
    Methylene Bis-Benzotriazolyl 2.00 0.50 1.50
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00
    Drometrizole Trisiloxane 0.50
    Terephthalidene Dicamphor 1.50 1.00
    Sulfonic Acid
    Diethylhexyl 2,6-Naphthalate 7.00
    Titanium Dioxide-microfine 1.00 3.00
    Zinc Oxide-microfine 0.25
    Vitamin E Acetate 0.50 1.00
    Ascorbyl Palmitate 0.05 0.05
    Buxux Chinensis (Jojoba) Oil 2.00 1.00 1.00
    Perfume Oil, BHT 0.10 0.25 0.35
    Ricinus Communis (Castor) Oil ad 100 ad 100 ad 100 ad 100
  • PIT-Emulsion
    1 2 3 4 5 6 7 8
    Glyceryl Monostearate SE 0.50 2.00 3.00 5.00 0.50 4.00
    Glyceryl Isostearate 3.50 4.00 2.00
    Isoceteth-20 0.50 2.00
    Ceteareth-12 5.00 1.00 3.50 5.00
    Ceteareth-20 5.00 1.00 3.50
    PEG-100 Stearate 2.80 2.30 3.30
    Cetyl Alcohol 5.20 1.20 1.00 1.30 0.50 0.30
    Cetyl Palmitate 2.50 1.20 1.50 0.50 1.50
    Cetyl Dimethicone 0.50 1.00
    Copolyol
    Polyglyceryl-2-Dioleate 0.75 0.30
    C16-Microbead- 0.1 5.0 0.01 0.5 3.0 0.25 10.0 3.0
    Canthaxanthin
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10 4.50 5.00 2.10
    UvaSorb ® k2A 4.00 1.50
    Ethylhexyl Bis-
    Isopentylbenzoxazolyl-
    phenyl Melamine
    Ethylhexyl 5.00 6.00 8.00 5.00
    Methoxycinnamate
    Uvinul ® MC 80
    Bis-Ethylhexyloxyphenol 1.50 2.00 2.50 2.50 2.50
    Methoxyphenyl Triazine
    Butyl Methoxydibenzoyl- 2.00 2.00 1.50 2.00
    methane
    Disodium Phenyl 2.50 0.50 2.00 0.30
    Dibenzimidazole
    Tetrasulfonate
    Ethyhexyl Triazone 4.00 3.00 4.00 2.00
    Uvinul ® T 150
    Octocrylene 4.00 7.50
    Diethylhexyl Butamido 1.00 2.00 1.00 1.00 1.00
    Triazone
    Phenylbenzimidazole 0.50 3.00
    Sulfonic Acid
    Methylene Bis- 2.00 0.50 1.50 2.50 2.50
    Benzotriazolyl
    Tetramethylbutylphenol
    Ethylhexyl Salicylate 3.00 5.00
    Drometrizole Trisiloxane 0.50 1.00
    Terephthalylidene 1.50 1.00 1.00 0.50 1.00
    Dicamphor Sulfonic Acid
    Diethylhexyl 7.00 10.00 7.50 8.00
    2,6-Naphthalate
    Titanium Dioxide- 1.00 3.00 3.50 1.50 3.50
    microfine
    Zinc Oxide-microfine 0.25 2.00
    C12-15 Alkyl Benzoate 3.50 6.35 0.10
    Cocoglyceride 3.00 3.00 1.00
    Dicapryl Ether 4.50
    Dicaprylyl Carbonate 4.30 3.00 7.00
    Dibutyl Adipate 0.50 0.30
    Phenyl Trimethicone 2.00 3.50 2.00
    Cyclomethicone 3.00
    C1-5 Alkyl 0.50 2.00
    Galactomannan
    Hydrogenated Coco- 3.00 4.00
    Glycerides
    Behenoxy Dimethicone 1.50 2.00
    VP/Hexadecene 1.00 1.20
    Copolymer
    Glycerin 4.00 6.00 5.00 8.00 10.00
    Vitamin E Acetate 0.20 0.30 0.40 0.30
    Butyrospermum Parkii 2.00 3.60 2.00
    (Shea Butter)
    Iodopropyl 0.12 0.20
    Butylcarbamate
    Biosaccaride Gum-1 0.10
    DMDM Hydantoin 0.10 0.12 0.13
    Methylparaben 0.50 0.30 0.35
    Phenoxyethanol 0.50 0.40 1.00
    Ethylhexylglycerin 0.30 1.00 0.35
    Ethanol 2.00 2.00 5.00
    Trisodium EDTA 0.40 0.15 0.20
    Perfume Oil 0.20 0.20 0.24 0.16 0.10 0.10
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100
  • Gel cream
    1 2 3 4
    Acrylates/C10-30 Alkylacrylate 0.40 0.35 0.40 0.35
    Crosspolymer
    Carbomer 0.20 0.22 0.20 0.22
    Luvigel ® EM 1.50 2.50 2.80 3.50
    Xanthan Gum 0.10 0.13 0.10 0.13
    Cetearyl Alcohol 3.00 2.50 3.00 2.50
    C12-15 Alkyl benzoate 4.00 4.50 4.00 4.50
    Caprylic/Capric Triglyceride 3.00 3.50 3.00 3.50
    Titanium Dioxide-microfine 1.00 1.50
    Zinc Oxide-microfine 2.00 0.25
    C16-Microbead 0.5 10.0 3.0 5.0
    Dihydroxyacetone 3.00 5.00
    Cyclomethicone 5.00 5.50 5.00 5.50
    Dimethicone 1.00 0.60 1.00 0.60
    Glycerin 1.00 1.20 1.00 1.20
    Sodium Hydroxide q.s. q.s. q.s. q.s.
    Preservative 0.30 0.23 0.30 0.23
    Perfume Oil 0.20 0.20
    Aqua dem. ad 100 ad 100 ad 100 ad 100
    Adjust pH to 6.0
  • 1 2 3 4 5 6 7
    OW self-tanning formulations
    Glyceryl Monostearate SE 0.50 1.00 3.00 1.50
    Glyceryl Stearate Citrate 2.00 1.00 2.00 4.00
    Stearic Acid 3.00 2.00
    PEG-40 Stearate 0.50 2.00
    Cetyl Phosphate 1.00
    Cetearyl Sulfate 0.75
    Stearyl Alcohol 3.00 2.00 0.60
    Cetyl Alcohol 2.50 1.10 1.50 0.60 2.00
    C16-Microbead- 0.1 0.5 0.025 5.0 3.0 10.0 1.0
    Canthaxanthin
    Dihydroxyacetone 3.00 5.00 4
    Titanium Dioxide-microfine 1.00 1.50 1.50
    Zinc Oxide-microfine 0.25 2.00
    C12-15 Alkyl Benzoate 0.25 4.00 7.00
    Dicapryl Ether 3.50 2.00
    Butylene glycol 5.00 6.00
    Dicaprylate/Dicaprate
    Cocoglycerides 6.00 2.00
    Dimethicone 0.50 1.00 2.00
    Cyclomethicone 2.00 0.50 0.50
    Butyrospermum Parkii 2.00
    (Shea)Butter
    VP/Hexadecene Copolymer 0.20 0.50 1.00
    Glycerin 3.00 7.50 7.50 5.00 2.50
    Xanthan Gum 0.15 0.05 0.30
    Sodium Carbomer 0.20 0.15 0.25
    Vitamin E Acetate 0.60 0.23 0.70 1.00
    Biosaccaride Gum-1 3.00 10.00
    Glycine Soja (Soybean) Oil 0.50 1.50 1.00
    Ethylhexylglycerin 0.30
    DMDM Hydantoin 0.60 0.40 0.20
    Iodopropynyl Butylcarbamate 0.18 0.20
    Methylparaben 0.15 0.25 0.50
    Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
    Trisodium EDTA 0.02 0.05
    Tetrasodium 0.25 1.00
    Iminodisuccinate
    Ethanol 2.00 1.50 3.00 1.20 5.00
    Perfume Oil 0.10 0.25 0.30 0.40 0.20
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100
    OW Make-Up
    Glyceryl Monostearate SE 0.50 1.00 3.00 1.50
    Glycerl Stearate Citrate 2.00 1.00 2.00 4.00
    Stearic Acid 3.00 2.00
    PEG-40 Stearate 0.50 2.00
    Cetyl Phosphate 1.00
    Cetearyl Sulfate 0.75
    Stearyl Alcohol 3.00 2.00 0.60
    Cetyl Alcohol 2.50 1.10 1.50 0.60 2.00
    C16-Microbead- 3.0 5.0 2.0 0.5 1.0 5.0 10.0
    Canthaxanthin
    Titanium Dioxide 10.00 12.00 9.00 8.50 11.00 9.50 10.00
    Iron Oxide 2.00 4.00 3.00 5.00 3.40 6.00 4.40
    Zinc Oxide 4.00 2.00 3.00
    C12-15 Alkyl Benzoate 0.25 4.00 7.00
    Dicapryl Ether 3.50 2.00
    Butylene glycol 5.00 6.00
    Dicaprylate/Dicaprate
    Cocoglycerides 6.00 2.00
    Dimethicone 0.50 1.00 2.00
    Cyclomethicone 2.00 0.50 0.50
    Butyrospermum Parkii 2.00
    (Shea Butter)
    VP/Hexadecene Copolymer 0.20 0.50 1.00
    Glycerin 3.00 7.50 7.50 5.00 2.50
    Xanthan Gum 0.15 0.05 0.30
    Sodium Carbomer 0.20 0.15 0.25
    Vitamin E Acetate 0.60 0.23 0.70 1.00
    Glycine Soja (Soybean) Oil 0.50 1.50 1.00
    Ethylhexylglycerin 0.30
    DMDM Hydantoin 0.60 0.40 0.20
    Iodopropynyl Butylcarbamate 0.18 0.20
    Methylparaben 0.15 0.25 0.50
    Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
    Trisodium EDTA 0.02 0.05
    Tetrasodium 0.25 1.00
    Iminodisuccinate
    Ethanol 2.00 1.50 3.00 1.20 5.00
    Perfume Oil 0.10 0.25 0.30 0.40 0.20
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100
  • 1 2 3 4 5
    Self-tanning hydrodispersion
    Ceteareth-20 1.00 0.50
    Cetyl Alcohol 1.00
    Luvigel ® EM 2.00 2.50 2.00
    Acrylates/C10-30 Alkyl Acrylate 0.50 0.40 0.10 0.50
    Crosspolymer
    Xanthan Gum 0.30 0.15
    C16-Microbead-Canthaxanthin 3.0 1.0 0.5 0.1 5.0
    Dihydroxyacetone 3.00 5.00
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10
    Titanium Dioxide-microfine 1.00 1.00 1.00
    Zinc Oxide-microfine 1.90 0.25
    C12-15 Alkyl Benzoate 2.00 2.50
    Dicapryl Ether 4.00
    Butylene glycol Dicaprylate/Dicaprate 4.00 2.00 6.00
    Dicapryl Carbonate 2.00 6.00
    Dimethicone 0.50 1.00
    Phenyl Trimethicone 2.00 0.50
    Butyrospermum Parkii (Shea Butter) 2.00 5.00
    VP/Hexadecene Copolymer 0.50 0.50 1.00
    Tricontanyl PVP 0.50 1.00
    Ethylhexylglycerin 1.00 0.80
    Glycerin 3.00 7.50 7.50 8.50
    Glycine Soja (Soybean) Oil 1.50 1.00
    Vitamin E Acetate 0.50 0.25 1.00
    Glucosylrutin 0.60 0.25
    DMDM Hydantoin 0.60 0.45 0.25
    Iodopropynyl Butylcarbamate 0.20
    Methylparaben 0.50 0.25 0.15
    Phenoxyethanol 0.50 0.40 1.00
    Trisodium EDTA 0.01 0.05 0.10
    Ethanol 3.00 2.00 1.50 7.00
    Perfume Oil 0.20 0.05 0.40
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    Aftersun hydrodispersion
    Ceteareth-20 1.00 0.50
    Cetyl Alcohol 1.00
    Luvigel ® EM 2.00 2.50 2.00
    Acrylates/C10-30 Alkyl Acrylate 0.50 0.30 0.40 0.10 0.50
    Crosspolymer
    Xanthan Gum 0.30 0.15
    C16-Microbead 0.1 5.0 0.5 3.0 1.0
    C12-15 Alkyl Benzoate 2.00 2.50
    Dicapryl Ether 4.00
    Butylene glycol Dicaprylate/Dicaprate 4.00 2.00 6.00
    Dicapryl Carbonate 2.00 6.00
    Dimethicone 0.50 1.00
    Phenyl Trimethicone 2.00 0.50
    Tricontanyl PVP 0.50 1.00
    Ethylhexylglycerin 1.00 0.80
    Glycerin 3.00 7.50 7.50 8.50
    Glycine Soja (Soybean) Oil 1.50 1.00
    Vitamin E Acetate 0.50 0.25 1.00
    Glucosylrutin 0.60 0.25
    Trisodium EDTA 0.01 0.05 0.10
    Ethanol 15.00 10.00 8.00 12.00 9.00
    Perfume Oil 0.20 0.05 0.40
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    WO Emulsions
    Cetyl Dimethicone 2.50 4.00
    Polyglyceryl-2 Dipolyhydroxystearate 5.00 4.50
    PEG-30 Dipolyhydroxystearate 5.00
    C16-Microbead 5.0 10.0 0.1 0.5 1.0
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10
    Titanium Dioxide-microfine 1.00 3.00 3.50
    Zinc Oxide-microfine 0.90 0.25
    Mineral Oil 12.00 10.00 8.00
    C12-15 Alkyl Benzoate 9.00
    Dicaprylyl Ether 10.00 7.00
    Butylene glycol Dicaprylate/Dicaprate 2.00 8.00 4.00
    Dicaprylyl Carbonate 5.00 6.00
    Dimethicone 4.00 1.00 5.00
    Cyclomethicone 2.00 25.00 2.00
    Butyrospermum Parkii (Shea Butter) 3.00
    Petrolatum 4.50
    VP/Hexadecene Copolymer 0.50 0.50 1.00
    Ethylhexylglycerin 0.30 1.00 0.50
    Glycerin 3.00 7.50 7.50 8.50
    Glycine Soja (Soybean) Oil 1.00 1.50 1.00
    Magnesium Sulfate 1.00 0.50 0.50
    Magnesium Chloride 1.00 0.70
    Vitamin E Acetate 0.50 0.25 1.00
    Ascorbyl Palmitate 0.50 2.00
    Biosaccaride Gum-1 3.50 7.00
    DMDM Hydantoin 0.60 0.40 0.20
    Methylparaben 0.50 0.25 0.15
    Phenoxyethanol 0.50 0.40 1.00
    Trisodium EDTA 0.12 0.05 0.30
    Ethanol 3.00 1.50 5.00
    Perfume Oil 0.20 0.40 0.35
    Aqua dem. ad 100 ad 100 ad 100 ad 100 ad 100
    Solids-stabilized emulsion
    (Pickering emulsions)
    Mineral Oil 16.00 16.00
    Octyldodecanol 9.00 9.00 5.00
    Caprylic/Capric Triglyceride 9.00 9.00 6.00
    C12-15 Alkyl Benzoate 5.00 8.00
    Butylene Glycol Dicaprylate/Dicaprate 8.00
    Dicaprylyl Ether 9.00 4.00
    Dicaprylyl Carbonate 9.00
    Hydroxyoctacosanyl Hydroxystearate 2.00 2.00 2.20 2.50 1.50
    Disteardimonium Hectorite 1.00 0.75 0.50 0.25
    Cera Microcristallina + Paraffinum Liquidum 0.35 5.00
    Hydroxypropyl Methylcellulose 0.10 0.05
    Dimethicone 3.00
    C16-Microbead 1.0 0.5 0.1 3.0 5.0
    Titanium Dioxide + Alumina + Simethicone + 3.00
    Aqua
    Titanium Dioxide + Trimethoxycaprylylsilane 2.00 4.00 2.00 4.00
    Silica Dimethyl Silylate 2.50 6.00 2.50
    Boron Nitride 1.00
    Starch/Sodium metaphosphate Polymer 2.00
    Tapioca Starch 0.50
    Sodium Chloride 5.00 7.00 8.50 3.00 4.50
    Glycerin 1.00
    Trisodium EDTA 1.00 1.00 1.00 1.00 1.00
    Vitamin E Acetate 5.00 10.00 3.00 6.00 10.00
    Ascorbyl Palmitate 1.00 1.00 1.00
    Methylparaben 0.60 0.20
    Propylparaben 0.20
    Phenoxyethanol 0.20
    Hexamidine Diisethionate 0.40 0.50 0.40
    Diazolidinyl Urea 0.08
    Ethanol 0.23 0.20
    Perfume Oil 5.00 3.00 4.00
    Aqua dem. 0.20 0.30 0.10
    ad 100 ad 100 ad 100 ad 100 ad 100
  • Sticks
    1 2 3 4
    Caprylic/Capric Triglyceride 12.00 10.00 6.00
    Octyldodecanol 7.00 14.00 8.00 3.00
    Butylene Glycol 12.00
    Dicaprylate/Dicaprate
    Pentaerythrityl Tetraisostearate 10.00 6.00 8.00 7.00
    Polyglyceryl-3 Diisostearate 2.50
    Bis-Diglyceryl Polyacyladipate-2 9.00 8.00 10.00 8.00
    Cetearyl Alcohol 8.00 11.00 9.00 7.00
    Myristyl Myristate 3.50 3.00 4.00 3.00
    Beeswax 5.00 5.00 6.00 6.00
    Copernicia Cerifera 1.50 2.00 2.00 1.50
    (Carnauba) Wax
    Cera Alba 0.50 0.50 0.50 0.40
    C16-40 Alkyl Stearate 1.50 1.50 1.50
    C16-Microbead 10.0 1.0 3.0 0.1
    Uvinul ® A Plus ™ 2.00 1.50 0.75 9.00
    Titanium Dioxide-microfine 1.00 3.00
    Zinc Oxide-microfine 1.00 0.25
    Vitamin E Acetate 0.50 1.00
    Ascorbyl Palmitate 0.05 0.05
    Buxux Chinensis (Jojoba) Oil 2.00 1.00 1.00
    Perfume Oil, BHT 0.10 0.25 0.35
    Ricinus Communis (Castor) Oil ad 100 ad 100 ad 100 ad 100
  • Self-tanning PIT emulsions
    1 2 3 4 5 6 7 8
    Glyceryl Monostearate SE 0.50 2.00 3.00 5.00 0.50 4.00
    Glyceryl Isostearate 3.50 4.00 2.00
    Isoceteth-20 0.50 2.00
    Ceteareth-12 5.00 1.00 3.50 5.00
    Ceteareth-20 5.00 1.00 3.50
    PEG-100 Stearate 2.80 2.30 3.30
    Cetyl Alcohol 5.20 1.20 1.00 1.30 0.50 0.30
    Cetyl Palmitate 2.50 1.20 1.50 0.50 1.50
    Cetyl Dimethicone Copolyol 0.50 1.00
    Polyglyceryl-2 0.75 0.30
    C16-Microbead-Canthaxanthin 0.1 0.5 0.01 5.0 0.5 3.0 0.025 10.0
    Dihydroxyacetone 3.00 5.00 4.00
    Uvinul ® A Plus ™ 2.00 1.50 0.75 1.00 2.10 4.50 5.00 2.10
    Titanium Dioxide-microfine 1.00 1.50 3.50 1.50 1.00
    Zinc Oxide-microfine 1.00 0.25 2.00 1.50
    C12-15 Alkyl Benzoate 3.50 6.35 0.10
    Cocoglycerides 3.00 3.00 1.00
    Dicapryl Ether 4.50
    Dicaprylyl Carbonate 4.30 3.00 7.00
    Dibutyl Adipate 0.50 0.30
    Phenyl Trimethicone 2.00 3.50 2.00
    Cyclomethicone 3.00
    C1-5 Alkyl Galactomannan 0.50 2.00
    Hydrogenated Coco-Glycerides 3.00 4.00
    Behenoxy Dimethicone 1.50 2.00
    VP/Hexadecene Copolymer 1.00 1.20
    Glycerin 4.00 6.00 5.00 8.00 10.00
    Vitamin E Acetate 0.20 0.30 0.40 0.30
    Butyrospermum Parkii 2.00 3.60 2.00
    (Shea Butter)
    Iodopropyl Butylcarbamate 0.12 0.20
    DMDM Hydantoin 0.10 0.12 0.13
    Methylparaben 0.50 0.30 0.35
    Phenoxyethanol 0.50 0.40 1.00
    Ethylhexylglycerin 0.30 1.00 0.35
    Ethanol 2.00 2.00 5.00
    Trisodium EDTA 0.40 0.15 0.20
    Perfume Oil 0.20 0.20 0.24 0.16 0.10 0.10
    Aqua dem. ad ad ad ad ad ad ad ad
    100 100 100 100 100 100 100 100
  • Oil gel
    1 2 3 4
    Caprylic/Capric Triglyceride 12.00 10.00 6.00
    Octyldodecanol 7.00 14.00 8.00 3.00
    Butylene Glycol 12.00
    Dicaprylate/Dicaprate
    Pentaerythrityl Tetraisostearate 10.00 6.00 8.00 7.00
    Polyglyceryl-3 Diisostearate 2.50
    Bis-Diglyceryl Polyacyladipate-2 9.00 8.00 10.00 8.00
    Myristyl Myristate 3.50 3.00 4.00 3.00
    Quaternium-18 Bentonite 5.00 5.00 6.00 6.00
    Propylene Carbonate 15.00 20.00 18.00 19.50
    C16-Microbead 1.0 0.5 3.0 5.0
    Vitamin E Acetate 0.50 1.00
    Ascorbyl Palmitate 0.05 0.05
    Buxus Chinensis (Jojoba) Oil 2.00 1.00 1.00
    Perfume Oil, BHT 0.10 0.25 0.35
    Ricinus Communis (Castor) Oil ad 100 ad 100 ad 100 ad 100
    • Example 39
  • The formulations below describe cosmetic sunscreen preparations comprising a combination of at least one inorganic pigment, preferably zinc oxide and/or titanium dioxide and organic UV-A and UV-B filters.
  • The formulations specified below are prepared in a customary manner known to a person skilled in the art.
  • The content of C16-microbead prepared according to Example 1 or C16-microbead-canthaxanthin prepared according to Example 4 refers to 100% active ingredient. The active ingredients according to the invention can be used either in pure form or in the form of an aqueous solution. In the case of the aqueous solution, the content of water dem. in the particular formulation must be adjusted.
  •
    A 7.50 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul M 40 Benzophenone-3
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead-Canthaxanthin
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 1.00 Sepigel 305 Polyacrylamide, C13-14 Isoparaffin, Laureth-7
    q.s. Preservative
    A 7.50 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul M 40 Benzophenone-3
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead-Canthaxanthin
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 7.50 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 4.00 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul T 150 Ethyl Hexyl Triazone
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 4.00 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul T 150 Ethyl Hexyl Triazone
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 4.00 Uvinul MC 80 Ethylhexyl Cinnamate
    2.00 Uvinul T 150 Ethyl Hexyl Triazone
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 4.00 Uvinul MC 80 Ethylhexyl Cinnamate
    1.00 Uvinul T 150 Ethyl Hexyl Triazone
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.70  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 4.00 Uvinul MC 80 Ethylhexyl Cinnamate
    1.00 Uvinul T 150 Ethyl Hexyl Triazone
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    67.10  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.10 Allantoin Allantoin
      1% C16-Microbead
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      2% C16-Microbead-Canthaxanthin
    0.10 Allantoin Allantoin
    65.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.5% C16-Microbead-Canthaxanthin
    0.10 Allantoin Allantoin
    66.70  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.10 Allantoin Allantoin
      1% C16-Microbead-Canthaxanthin
    2.0  Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydrobenzoyl Hexyl Benzoate
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and)Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.10 Allantoin Allantoin
      2% C16-Microbead
    2.0 Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    65.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.1% C16-Microbead
    0.10 Allantoin Allantoin
    67.10  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 5.00 Uvinul N 539 T Octocrylene
    2.00 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
    0.80 Rylo PG 11 Polyglyceryl Dimer Soyate
    1.00 Span 60 Sorbitan Stearate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    3.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Cremophor CO 410 PEG-40 Hydrogenated Castor Oil
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    1.00 Cetiol SB 45 Butyrospermum Parkii (Shea Butter)
    6.50 Finsolv TN C12-15 Alkyl Benzoate
    C 5.00 Butylene glycol Butylene Glycol
    0.30 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
      1% C16-Microbead
    0.10 Allantoin Allantoin
    66.20  Water dem. Aqua dem.
    D 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
    Taurate Copolymer, Squalane, Polysorbate 60
    q.s. Preservative
    A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    5.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    0.20 Keltrol Xanthan Gum
      2% C16-Microbead-Canthaxanthin
    0.50 Simulgel 600 Acrylamide/Sodium
    Acryloyldimethyltaurate Copolymer,
    Isohexadecane, Polysorbate 80
    ad 100 Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium
    Ascorbate, Tocopherol, Retinol
    A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    0.20 Keltrol Xanthan Gum
      2% C16-Microbead
    0.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    ad 100 Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E Acetate Tocopheryl Acetate
    2.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium
    Ascorbate, Tocopherol, Retinol
    A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    5.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    1.00 D-Panthenol 50 P Panthenol, Propylene Glycol
    0.20 Keltrol Xanthan Gum
    1.0% C16-Microbead
    0.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    ad 100 Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium Ascorbate,
    Tocopherol, Retinol
    A 5.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    3.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    0.20 Keltrol Xanthan Gum
      2% C16-Microbead-Canthaxanthin
    0.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    Ad 100 Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium
    Ascorbate, Tocopherol, Retinol
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Mexoryl XL Drometrizole Trisilioxane
    10.00  Witconol APM PPG-3 Myristyl Ether
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane
    5.00 Uvinul N 539 T Octocrylene
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 5.00 1,2-Propylene glycol Propylene Glycol
    1.00 Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    0.20 Keltrol Xanthan Gum
    0.06 Edeta BD Disodium EDTA
    0.04 TEA Triethanolamine
    0.30 Carbopol Ultrez 10P Carbomer
    63.50  Water dem. Aqua dem.
      1% C16-Microbead-Canthaxanthin
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 5.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    3.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    0.20 Keltrol Xanthan Gum
    0.5% C16-Microbead-Canthaxanthin
    2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    66.30  Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium
    Ascorbate, Tocopherol, Retinol
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 0.20 Keltrol Xanthan Gum
    0.5% C16-Microbead-Canthaxanthin
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    65.10  Water dem. Aqua dem.
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 0.50 Keltrol Xanthan Gum
    0.5% C16-Microbead
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    65.10 Water dem. Aqua dem.
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 0.50 Keltrol Xanthan Gum
      1% C16-Microbead
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    64.60  Water dem. Aqua dem.
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 0.50 Keltrol Xanthan Gum
      1% C16-Microbead-Canthaxanthin
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    64.10  Water dem. Aqua dem.
    2.00 Neoheliopan AP Disodium Phenyl Dibenzimidazole
    Tetrasulfonate
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    26
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    7.00 Uvinul N 539 T Octocrylene
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 0.50 Keltrol Xanthan Gum
      1% C16-Microbead-Canthaxanthin
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    64.60  Water dem. Aqua dem.
    1.00 Mexoryl SX Terephthalidene Dicamphor Sulfonic
    Acid
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    5.00 Uvinul N 539 T Octocrylene
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl palmitate Isopropyl Palmitate
    B 3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 0.50 Keltrol Xanthan Gum
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    65.10  Water dem. Aqua dem.
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.5% C16-Microbead-Canthaxanthin
    q.s. Preservative
    1.00 Urea Urea
    2.00 Neoheliopan AP Disodium Phenyl Dibenzimidazole
    Tetrasulfonate
    2.00 Glycerin 87% Glycerin
      5% C16-Microbead
    1.20 Aristoflex AVC Ammonium
    Acryloyldimethyltaurate/VP Copolymer
    71.30 Water dem. Aqua dem.
    B 3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    q.s. Perfume Oil
    5.00 Miglyol 812 Caprylic/Capric Triglyceride
    2.00 Uvinul N 539 T Octocrylene
    8.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    q.s. Preservative
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    1.00 Uvinul T150 Ethylhexyl Triazone
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul T 539 N Octocrylene
    0.50 Abil 350 Dimethicone
    2.75 Carnico wax LT 20 Carnauba (Copernica Cerifera) Wax,
    Paraffin
    3.70 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    1.80 Beeswax 3050 PH Bees Wax
    3.20 TeCero wax 30445 Microcrystalline Wax
    3.20 TeCero wax 1030 K Microcrystalline Wax
    1.34 Cutina CP Cetyl Palmitate
    6.40 Vaseline Petrolatum
    7.30 Softisan 100 Hydrogenated Coco-Glycerides
    10.00  Luvitol EHO Cetearyl Ethylhexanoate
    0.17 Bisabolol nat. Bisabolol
    1.84 Vitamin E Acetate Tocopheryl Acetate
    0.42 D,L-Alpha-Tocopherol Tocopherol
      1% C16-Microbead
    40.38 Castor oil Castor (Ricinus Communis) Oil
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    1.00 Uvinul T150 Ethylhexyl Triazone
    3.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul N 539 T Octocrylene
    0.50 Abil 350 Dimethicone
    2.75 Carnico wax LT 20 Carnauba (Copernica Cerifera) Wax,
    Paraffin
    3.70 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    1.80 Beeswax 3050 PH Bees Wax
    3.20 TeCero wax 30445 Microcrystalline Wax
    3.20 TeCero wax 1030 K Microcrystalline Wax
    1.34 Cutina CP Cetyl Palmitate
    6.40 Vaseline Petrolatum
    7.30 Softisan 100 Hydrogenated Coco-Glycerides
    10.00  Luvitol EHO Cetearyl Ethylhexanoate
    0.17 Bisabolol nat. Bisabolol
    1.84 Vitamin E Acetate Tocopheryl Acetate
    0.42 D,L-Alpha-Tocopherol Tocopherol
      1% C16-Microbead-Canthaxanthin
    40.38  Castor oil Castor (Ricinus Communis) Oil
    5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    3.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    0.50 Abil 350 Dimethicone
    2.75 Carnico wax LT 20 Carnauba (Copernica Cerifera) Wax,
    Paraffin
    3.70 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    1.80 Beeswax 3050 PH Bees Wax
    3.20 TeCero wax 30445 Microcrystalline Wax
    3.20 TeCero wax 1030 K Microcrystalline Wax
    1.34 Cutina CP Cetyl Palmitate
    6.40 Vaseline Petrolatum
    7.30 Softisan 100 Hydrogenated Coco-Glycerides
    10.00  Luvitol EHO Cetearyl Ethylhexanoate
    0.17 Bisabolol nat. Bisabolol
    1.84 Vitamin E Acetate Tocopheryl Acetate
    0.42 D,L-Alpha-Tocopherol Tocopherol
      2% C16-Microbead-Canthaxanthin
    39.38  Castor oil Castor (Ricinus Communis) Oil
    A 6.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    2.00 Elfacos ST 9 PEG-45/Dodecyl Glycol Copolymer
    3.00 Isopropyl myristate Isopropyl Myristate
    8.00 Jojoba oil Simmondsia Chinensis (Jojoba) Seed Oil
    4.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    1.00 Abil 350 Dimethicone
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 0.20 Edeta BD Disodium EDTA
    5.00 Glycerin 87% Glycerin
      1% C16-Microbead
    0.30 Chemag 2000 Imidazolidinyl Urea
    59.00  Water dem. Aqua dem.
    D q.s. Perfume Oil
    q.s. Preservative
    2.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Syncrowax HRC Tribehenin
    2.00 Lanette O Cetearyl Alcohol
    2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Ganex V-220 VP/Eicosene Copolymer
    7.00 Isopropyl myristate Isopropyl Myristate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 0.20 Keltrol Xanthan Gum
    1.5% C16-Microbead
    0.50 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    61.10  Water dem. Aqua dem.
    0.20 Edeta BD Disodium EDTA
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Luvitol EHO Cetearyl Ethylhexanoate
    5.00 Paraffin oil Mineral Oil
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    B 1.00 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Cremophor A 25 Ceteareth-25
    3.00 Glycerin monostearate Glyceryl Stearate
    4.00 Cetylstearyl alcohol Cetearyl Alcohol
    C 5.00 1,2-Propylene Glycol Care Propylene Glycol
    7.50 Luviquat Care Polyquaternium-44
    q.s. Preservative
    q.s. Perfume Oil
      1% C16-Microbead-Canthaxanthin
    64.50  Water dem. Aqua dem.
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    10.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    12.00 Beeswax 3044 PH Bees Wax
    8.00 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    5.00 Tegin Glyceryl Stearate SE
    5.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    5.00 Witconol APM PPG-3 Myristyl Ether
    5.00 Softisan 154 Hydrogenated Palm Oil
    8.00 Paraffin oil, high viscosity Mineral Oil
    3.00 Vaseline Petrolatum
      2% C16-Microbead
    32.00  Castor oil Castor (Ricinus Communis) Oil
    3.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul T 150 Ethylhexyl Triazone
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    10.00  Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    12.00  Beeswax 3044 PH Bees Wax
    3.00 Vaseline Petrolatum
    8.00 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    8.00 Paraffin oil, high viscosity Mineral Oil
    5.00 Tegin Glyceryl Stearate SE
    5.00 Softisan 154 Hydrogenated Palm Oil
    5.00 Witconol APM PPG-3 Myristyl Ether
    5.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    0.1% C16-Microbead-Canthaxanthin
    28.90  Castor oil Castor (Ricinus Communis) Oil
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    6.00 Finsolv TN C12-15 Alkyl Benzoate
    10.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    6.00 Miglyol 812 Caprylic/Capric Triglyceride
    5.00 Arlacel P 135 PEG-30 Dipolyhydroxystearate
    2.00 Ganex V 216 PVP/Hexadecene Copolymer
    2.00 Elfacos ST 9 PEG-45/Dodecyl Glycol Copolymer
    B 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.10 Edeta BD Disodium EDTA
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    59.40  Water dem. Aqua dem.
    0.5% C16-Microbead-Canthaxanthin
    q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    4.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul N 539 T Octocrylene
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    ad
    100 Water dem. Aqua dem.
    1.5% C16-Microbead-Canthaxanthin
    D q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    4.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul N 539 T Octocrylene
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
      1% C16-Microbead
    ad
    100 Water dem. Aqua dem.
    D q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    8.00 Uvinul A Plus B Ethylhexyl Methoxycinnamate and
    Diethylamino Hydroxybenzoyl hexyl
    Benzoate
    2.00 Uvinul N 539 T Octocrylene
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    0.1% C16-Microbead
    ad
    100 Water dem. Aqua dem.
    q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    8.00 Uvinul A Plus B Ethylhexyl Methoxycinnamate and
    Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    2.00 Uvinul N 539 T Octocrylene
    B 5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    Ad
    100 Water dem. Aqua dem.
    0.2% C16-Microbead-Canthaxanthin
    q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    8.00 Uvinul A Plus B Ethylhexyl Methoxycinnamate and
    Diethylamino Hydroxybenzoyl hexyl
    Benzoate
    2.00 Uvinul N 539 T Octocrylene
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    0.5% C16-Microbead
    ad
    100 Water dem. Aqua dem.
    q.s. Preservative
    A 4.00 Dehymuls SBL Polyglyceryl-2 Dipolyhydroxystearate,
    Dicaprylyl Ether, Cocoglycerides,
    Sorbitan Sesquioleate, Cera Alba,
    Aluminum Stearates, Dicocoyl
    Pentaerythrityl Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2 Dipolyhydroxystearate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Miglyol 812 Caprylic/Capric Triglyceride
    7.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    B 5.00 Z-COTE MAX Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Abiol Imidazolidinyl Urea
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    ad
    100 Water dem. Aqua dem.
    0.01% C16-Microbead-Canthaxanthin
    q.s. Preservative
    A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    1.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    1.50 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    0.05% C16-Microbead-Canthaxanthin
    B 3.50 Luvigel EM Caprylic/Capric Triglyceride, Sodium
    Acrylates Copolymer
    C 46.00  Water dem. Aqua dem.
    D 5.00 1,2-Propylene Glycol Care Propylene Glycol
    0.50 Cremophor A 25 Ceteareth-25
    20.00  Ethanol 96% Alcohol
    A 1.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    3.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    8.00 Miglyol 812 Caprylic/Capric Triglyceride
    1.50 Dow Corning 350 Fluid Dimethicone
    3.00 Z-COTE MAX Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    3.00 Finsolv TN C12-15 Alkyl Benzoate
    1.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    B 2.00 Luvigel EM Caprylic/Capric Triglyceride, Sodium
    Acrylates Copolymer
    C 54.80  Water dem. Aqua dem.
    D 15.00  Ethanol 96% Alcohol
    5.00 1,2-Propylene Glycol Care Propylene Glycol
    0.50 Cremophor A 25 Ceteareth-25
      1% C16-Microbead-Canthaxanthin
    1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 4.00 Dehymuls SBL Polyglyceryl-2
    Dipolyhydroxystearate, Dicaprylyl
    Ether, Cocoglycerides, Sorbitan
    Sesquloleate, Cera Alba, Aluminum
    Stearates, Dicocoyl Pentaerythrityl
    Distearyl Citrate
    1.00 Dehymuls PGPH Polyglyceryl-2
    Dipolyhydroxystearate
    6.00 Finsolv TN C12-15 Alkyl Benzoate
    6.00 Miglyol 812 Caprylic/Capric Triglyceride
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Neoheliopan HMS Homosalate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 3.00 1,2-Propylene Glycol Care Propylene Glycol
    0.30 Chemag 2000 Imidazolidinyl Urea
    0.1% C16-Microbead-Canthaxanthin
    1.00 Magnesium sulfate 7-hydrate Magnesium Sulfate
    65.10  Water dem. Aqua dem.
    q.s. Preservative
    A 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul T 150 Ethylhexyl Triazone
    0.50 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Isohexadecane Isohexadecane
    5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    0.2% C16-Microbead
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 60.00  Water dem. Water
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    D q.s. Preservative
    A 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Neoheliopan HMS Homosalate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Isohexadecane Isohexadecane
    5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    1.0% C16-Microbead
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 59.20  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    D q.s. Preservative
    A 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Neoheliopan OS Octisalate
    2.00 Neoheliopan HMS Homosalate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Isohexadecane Isohexadecane
    5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    0.05% C16-Microbead
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 60.15  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    D q.s. Preservative
    A 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    4.50 Uvinul N 539 T Octocrylene
    3.00 Neoheliopan OS Octisalate
    2.00 Neoheliopan HMS Homosalate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Isohexadecane Isohexadecane
    5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    0.01% C16-Microbead-Canthaxanthin
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 60.19  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    D q.s. Preservative
    A 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    4.50 Uvinul N 539 T Octocrylene
    3.00 Neoheliopan OS Octisalate
    2.00 Neoheliopan HMS Homosalate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Isohexadecane Isohexadecane
    5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 59.20  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.0% C16-Microbead-Canthaxanthin
    D q.s. Preservative
    A 8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    12.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    3.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    1.00 Vitamin E Acetate Tocopheryl Acetate
    B 4.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
      2% C16-Microbead
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    49.45  Water dem. Aqua dem.
    D q.s. Preservative
    A 8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    12.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    3.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    1.00 Vitamin E Acetate Tocopheryl Acetate
    B 4.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
    0.2% C16-Microbead
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    50.25  Water dem. Aqua dem.
    D 0.50 Citric acid Citric Acid
    q.s. Perfume Oil
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul T 150 Ethylhexyl Triazone
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    2.50 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
    1.0% C16-Microbead
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    42.00  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    10.00  Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydrobenzoyl Hexyl
    Benzoate
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    2.50 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
      2% C16-Microbead
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    41.00  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    10.00  Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydrobenzoyl Hexyl
    Benzoate
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    2.50 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
    0.5% C16-Microbead
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    42.50  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    10.00  Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    7.50 Uvinul N 539 T Octocrylene
    2.00 Mexoryl XL Drometrizole Trisiloxane
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
    1.0% C16-Microbead
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    40.50  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    10.00  Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.50 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydrobenzoyl Hexyl
    Benzoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    41.50  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    0.5% C16-Microbead-Canthaxanthin
    9.50 Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 5.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.50 Uvinul N 539 T Octocrylene
    2.00 Uvinul A Plus Diethylamino Hydrobenzoyl Hexyl
    Benzoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    B 4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    5.00 Isohexadecane Isohexadecane
    3.50 Cetiol SN Cetearyl Isononanoate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 5.00 Glycerin 87% Glycerin
    2.00 Lanette E Sodium Cetearyl Sulfate
    0.30 Keltrol Xanthan Gum
    1.00 Pationic 138 C Sodium Lauroyl Lactylate
    1.0% C16-Microbead
    1.00 Pationic SSL Sodium Stearoyl Lactylate
    40.50  Water dem. Aqua dem.
    D 5.00 Eusolex 232 Phenylbenzimidazole Sulfonic Acid
    10.00  Water dem. Aqua dem.
    E 0.70 Sodium hydroxide Sodium Hydroxide
    q.s. Preservative
    A 8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    10.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
      2% C16-Microbead-Canthaxanthin
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    ad
    100 Water dem. Aqua dem.
    D q.s. Perfume Oil
    q.s. Preservative
    A 8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    10.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl triazine
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Vitamin E Acetate Tocopheryl Acetate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
    1.0% C16-Microbead
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    ad
    100 Water dem. Aqua dem.
    D q.s. Perfume Oil
    q.s. Preservative
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    0.30 Keltrol T Xanthan Gum
    57.00  Water dem. Aqua dem.
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl
    Hexyl Benzoate
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
      2% C16-Microbead-Canthaxanthin
    0.20 Bisabolol rac. Bisabolol
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    1.0% C16-Microbead
    0.30 Keltrol T Xanthan Gum
    58.00  Water dem. Aqua dem.
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl
    Hexyl Benzoate
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    0.5% C16-Microbead
    0.30 Keltrol T Xanthan Gum
    58.50  Water dem. Aqua dem.
    B 5.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    C 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    5.00 Uvinul N 539 T Octocrylene
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    0.30 Keltrol T Xanthan Gum
    2.00 Mexoryl SL Terephthalidene Dicamphor
    Sulfonic Acid
    58.40  Water dem. Aqua dem.
    B 6.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    6.00 Uvinul N 539 T Octocrylene
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.1% C16-Microbead-Canthaxanthin
    0.20 Bisabolol rac. Bisabolol
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    0.30 Keltrol T Xanthan Gum
    0.05% C16-Microbead
    2.00 Mexoryl SL Terephthalidene Dicamphor
    Sulfonic Acid
    58.45  Water dem. Aqua dem.
    B 6.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    6.00 Uvinul N 539 T Octocrylene
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Abiol Imidazolidinyl Urea
    1.00 Plantacare 2000 Decyl Glucoside
    0.30 Keltrol T Xanthan Gum
    1.0% C16-Microbead
    2.00 Neoheliopan AP Disodium Phenyl Dibenzimidazole
    Tetrasulfonate
    57.50  Water dem. Aqua dem.
    B 6.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    6.00 Uvinul N 539 T Octocrylene
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 25.00  Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    20.00 Dow Corning 245 Fluid Cyclopentasiloxane
    8.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    4.00 Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone
    7.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    B 17.00  Ethanol 95% Alcohol
    10.00  Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    4.50 Water dem. Aqua dem.
    3.00 Glycerin 87% Glycerin
    0.5% C16-Microbead-Canthaxanthin
    1.00 Talc Talc
    A 25.00  Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    20.00  Dow Corning 245 Fluid Cyclopentasiloxane
    8.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    4.00 Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone
    7.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    B 17.00  Ethanol 95% Alcohol
    9.99 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    5.00 Water dem. Aqua dem.
    3.00 Glycerin 87% Glycerin
    0.01% C16-Microbead
    1.00 Talc Talc
    A 20.00  Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    10.00  Dow Corning 245 Fluid Cyclopentasiloxane
    7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul T 150 Ethylhexyl Triazone
    12.00  Cosmacol EMI Di-C12-13 Alkyl Malate
    4.00 Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone
    B 7.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 15.00  Ethanol 95% Alcohol
    10.00  Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    3.00 Glycerin 87% Glycerin
    1.5% C16-Microbead-Canthaxanthin
    8.00 Water dem. Aqua dem.
    A 20.00  Dow Corning 345 Fluid Cyclopentasiloxane,
    Cyclohexasiloxane
    10.00  Dow Corning 245 Fluid Cyclopentasiloxane
    7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    12.00  Cosmacol EMI Di-C12-13 Alkyl Malate
    4.00 Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone
    B 7.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 15.00  Ethanol 95% Alcohol
    10.00  Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    3.00 Glycerin 87% Glycerin
    0.5% C16-Microbead
    9.00 Water dem. Aqua dem.
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 7.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Uvinul T 150 Ethylhexyl Triazone
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
    1.0% C16-Microbead-
    0.20 Edeta BD Disodium EDTA
    61.30  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 7.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Uvinul T 150 Ethylhexyl Triazone
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
    0.1% C16-Microbead
    0.20 Edeta BD Disodium EDTA
    62.20  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 7.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
      2% C16-Microbead
    0.20 Edeta BD Disodium EDTA
    60.30  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    6.00 Z-COTE MAX Zinc Oxide (and)Diphenyl Capryl
    Methicone
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 4.00 Uvinul N 539 T Octocrylene
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
    0.2% C16-Microbead
    0.20 Edeta BD Disodium EDTA
    62.10  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    6.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 3.00 Uvinul N 539 T Octocrylene
    1.00 Mexoryl XL Drometrizole Trisiloxane
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
    0.20 Edeta BD Disodium EDTA
    1.0% C16-Microbead
    61.30  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 2.00 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    6.00 Abil B 8839 Cyclopentasiloxane,
    Cyclohexasiloxane
    6.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate,
    Alumina Hydrate,
    Methicone/Dimethicone Copolymer
    4.00 Isopropyl palmitate Isopropyl Palmitate
    1.00 Abil 350 Dimethicone
    B 3.00 Uvinul N 539 T Octocrylene
    1.00 Mexoryl XL Drometrizole Trisiloxane
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl
    PEG/PPG-10/1 Dimethicone, Hexyl
    Laurate
    C 0.50 Sodium chloride Sodium Chloride
    0.5% C16-Microbead-Canthaxanthin
    0.20 Edeta BD Disodium EDTA
    61.80  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    q.s. Preservative
    A 4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    1.00 Uvinul T 150 Ethylhexyl Triazone
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    B 0.50 Vitamin E Acetate Tocopheryl Acetate
    4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    C 3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Isohexadecane Isohexadecane
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    D 44.00  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    15.00  Luviquat Care Polyquaternium-44
    1.0% C16-Microbead
    0.50 Keltrol Xanthan Gum
    E 1.00 Phenonip
    A 4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    3.00 Uvinul N 539 T Octocrylene
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    B 0.50 Vitamin E Acetate Tocopheryl Acetate
    4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    C 3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Isohexadecane Isohexadecane
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    D 44.90  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    15.00  Luviquat Care Polyquaternium-44
    0.1% C16-Microbead
    0.50 Keltrol Xanthan Gum
    E 1.00 Phenonip
    A 1.50 Mexoryl XL Drometrizole Trisiloxane
    5.00 Uvinul N 539 T Octocrylene
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    B 0.50 Vitamin E Acetate Tocopheryl Acetate
    4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    C 3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Isohexadecane Isohexadecane
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    D 44.50  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    15.00  Luviquat Care Polyquaternium-44
    1.5% C16-Microbead-Canthaxanthin
    0.50 Keltrol Xanthan Gum
    E 1.00 Phenonip
    A 1.50 Mexoryl XL Drometrizole Trisiloxane
    5.00 Uvinul N 539 T Octocrylene
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol
    Methoxyphenyl Triazine
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    B 0.50 Vitamin E Acetate Tocopheryl Acetate
    4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose
    Distearate
    C 3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Isohexadecane Isohexadecane
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    D 45.00  Water dem. Aqua dem.
    5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    15.00  Luviquat Care Polyquaternium-44
    1.0% C16-Microbead-Canthaxanthin
    0.50 Keltrol Xanthan Gum
    E 1.00 Phenonip
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    10.00  Witconol APM PPG-3 Myristyl Ether
    2.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane
    5.00 Uvinul N 539 T Octocrylene
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 5.00 1,2-Propylene glycol Propylene Glycol
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    2.0% C16-Microbead-Canthaxanthin
    1.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    58.40  Water dem. Aqua dem.
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 2.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    4.00 Finsolv TN C12-15 Alkyl Benzoate
    1.50 Miglyol 812 Caprylic/Capric Triglyceride
    0.50 Vitamin E Acetate Tocopheryl Acetate
    7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    4.00 Cetiol B Dibutyl Adipate
    3.00 Luvitol EHO Cetearyl Ethylhexanoate
    1.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    1.00 Paraffin Oil, low viscosity Mineral Oil
    3.00 Plantacare 2000 Decyl Glucoside
    0.50 Phenonip
    q.s. Perfume Oil
    B 4.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    1.0% C16-Microbead
    64.20  Water dem. Aqua dem.
    A 6.00 Gilugel SIL 5 Cyclomethicone (and) Aluminium/Magnesium
    Hydroxide Stearate
    5.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    1.00 Uvinul T 150 Ethylhexyl Triazone
    7.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl PEG/PPG-
    10/1 Dimethicone, Hexyl Laurate
    2.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.00 Isopropyl palmitate Isopropyl Palmitate
    5.00 Abil B 8839 Cyclopentasiloxane, Cyclohexasiloxane
    0.50 Abil 350 Dimethicone
    B 0.50 Sodium chloride Sodium Chloride
    0.20 Edeta BD Disodium EDTA
    0.2% C16-Microbead
    62.10 Water dem. Aqua dem.
    C 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.50 Phenonip
    A 4.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl
    Triazine
    3.00 Uvinul N 539 T Octocrylene
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    0.50 Vitamin E Acetate Tocopheryl Acetate
    4.00 Tego Care 450 Polyglyceryl-3 Methyl Glucose Distearate
    B 3.50 Cetiol SN Cetearyl Isononanoate
    1.00 Ganex V-220 VP/Eicosene Copolymer
    5.00 Isohexadecane Isohexadecane
    2.50 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 5.00 Glycerin 87% Glycerin
    1.00 Lanette E Sodium Cetearyl Sulfate
    0.50 Keltrol Xanthan Gum
    1.0% C16-Microbead-Canthaxanthin
    59.70  Water dem. Aqua dem.
    D 1.00 Phenonip
    0.30 Bisabolol rac. Bisabolol
    A 2.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    4.00 Finsolv TN C12-15 Alkyl Benzoate
    1.50 Miglyol 812 Caprylic/Capric Triglyceride
    0.50 Vitamin E Acetate Tocopheryl Acetate
    7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    4.00 Cetiol B Dibutyl Adipate
    1.00 Luvitol EHO Cetearyl Ethylhexanoate
    1.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    1.00 Paraffin Oil, low viscosity Mineral Oil
    3.00 Plantacare 2000 Decyl Glucoside
    1.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    0.50 Phenonip
    2.50 Uvinul T 150 Ethylhexyl Triazone
    q.s. Perfume Oil
    B 4.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    C 2.00 Simulgel NS Hydroxyethyl Acrylate/Sodium
    Acryloyldimethyl Taurate Copolymer,
    Squalane, Polysorbate 60
    0.10 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.5% C16-Microbead
    59.90  Water dem. Aqua dem.
    A 4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    12.00  Myritol 331 Cocoglycerides
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    8.00 Cetiol B Dibutyl Adipate
    B 6.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 3.00 Glycerin 87% Glycerin
    0.10 Edeta BD Disodium EDTA
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    1.50 Lanette E Sodium Cetearyl Sulfate
      2% C16-Microbead
    0.30 Keltrol Xanthan Gum
    45.10  Water dem. Water
    D 1.00 Phenonip Phenoxyethanol, Methylparaben,
    Ethylparaben, Butylparaben, Propylparaben,
    Isobutylparaben
    A 4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    12.00  Myritol 331 Cocoglycerides
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    8.00 Cetiol B Dibutyl Adipate
    B 6.00 Uvinul N 539 T Octocrylene
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 3.00 Glycerin 87% Glycerin
    0.10 Edeta BD Disodium EDTA
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    1.50 Lanette E Sodium Cetearyl Sulfate
    0.30 Carbopol Ultrez 10 P Carbomer
    1.0% C16-Microbead-Canthaxanthin
    46.10  Water dem. Aqua dem.
    D 1.00 Phenonip Phenoxyethanol, Methylparaben,
    Ethylparaben, Butylparaben, Propylparaben,
    Isobutylparaben
    A 4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    2.00 Lanette O Cetearyl Alcohol
    10.00  Myritol 331 Cocoglycerides
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    8.00 Cetiol B Dibutyl Adipate
    B 2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 3.00 Glycerin 87% Glycerin
    0.10 Edeta BD Disodium EDTA
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    1.50 Lanette E Sodium Cetearyl Sulfate
    5.0% C16-Microbead-Canthaxanthin
    0.30 Carbopol Ultrez 10 P Carbomer
    ad Water dem. Water
    D 1.00 Phenonip Phenoxyethanol, Methylparaben,
    Ethylparaben, Butylparaben, Propylparaben,
    Isobutylparaben
    A 3.50 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    1.50 Cremophor A 25 Ceteareth-25
    7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    2.00 Dow Corning 345 Cyclopentasiloxane, Cyclohexasiloxane Fluid
    0.50 Beeswax 3044 PH Bees Wax
    3.00 Lanette O Cetearyl Alcohol
    10.00  Miglyol 812 Caprylic/Capric Triglyceride
    B 5.00 T-Lite SF-S Titanium Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    C 3.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    0.30 Keltrol T Xanthan Gum
    1.00 Plantacare 2000 Decyl Glucoside
    2.0% C16-Microbead
    57.30  Water dem. Aqua dem.
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    A 10.00  Uvinul A Plus B Ethylhexyl Methoxycinnamate, Diethylamino
    Hydroxybenzoyl Hexyl Benzoate
    10.00  Uvinul N 539 T Octocrylene
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    12.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    2.00 Lanette O Cetearyl Alcohol
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 35.08  Water dem. Aqua dem.
    0.38 Citric acid Citric Acid
    2.9  Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
    0.1% C16-Microbead-
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    D 0.50 Phenonip
    1.00 Vitamin E-Acetate Tocopheryl Acetate
    A 0.70 Cremophor A 25 Ceteareth-25
    1.70 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    3.00 Uvinul N 539 T Octocrylene
    3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    2.00 Abil B 8843 PEG-14 Dimethicone
    3.60 Lanette O Cetearyl Alcohol
    4.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    2.00 Cetiol B Dibutyl Adipate
    B 4.00 Glycerin 87% Glycerin
    1.0% C16-Microbead-Canthaxanthin
    0.20 Edeta BD Disodium EDTA
    71.00  Water dem. Panthenol
    C 4.00 Luvigel EM Caprylic/Capric Triglyceride, Sodium
    Acrylates Copolymer
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    q.s. Preservative
    A 7.50 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    5.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.50 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.50 Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminum Starch Octenylsuccinate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    0.03 Sicomet Blue P 77 007 C.I. 77 007, Ultramarines
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    2.00 D-Panthenol 50 P Panthenol, Propylene Glycol
    0.20 Keltrol Xanthan Gum
    0.50 Simulgel 600 Acrylamide/Sodium
    Acryloyldimethyltaurate Copolymer,
    Isohexadecane, Polysorbate 80
    0.5% C16-Microbead-Canthaxanthin
    65.27  Water dem. Aqua dem.
    q.s. Preservative
    0.50 Vitamin E-Acetate Tocopheryl Acetate
    A 6.00 Gilugel SIL 5 Cyclomethicone (and) Aluminium/Magnesium
    Hydroxide Stearate
    5.00 Uvinul N 539 T Octocrylene
    2.00 Mexoryl XL Drometrizole Trisiloxane
    1.00 Uvinul T 150 Ethylhexyl Triazone
    3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    5.00 Finsolv TN C12-15 Alkyl Benzoate
    4.00 Abil WE 09 Polyglyceryl-4 Isostearate, Cetyl PEG/PPG-
    10/1 Dimethicone, Hexyl Laurate
    2.00 Cosmacol EMI Di-C12-13 Alkyl Malate
    3.00 Isopropyl palmitate Isopropyl Palmitate
    5.00 Abil B 8839 Cyclopentasiloxane, Cyclohexasiloxane
    0.50 Abil 350 Dimethicone
    B 0.50 Sodium chloride Sodium Chloride
    0.20 Edeta BD Disodium EDTA
    1.0% C16-Microbead-Canthaxanthin
    61.30  Water dem. Aqua dem.
    C 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.50 Phenonip
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    5.00 Uvinul N 539 T Octocrylene
    10.00  Witconol APM PPG-3 Myristyl Ether
    2.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Silane
    C 5.00 1,2-Propylene glycol Propylene Glycol
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    1.0% C16-Microbead
    1.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    59.40  Water dem. Aqua dem.
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 7.00 Uvinul A Plus B Ethylhexyl Methoxycinnamate, Diethylamino
    Hydroxybenzoyl Hexyl Benzoate
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl
    Triazine
    1.00 Uvinul T 150 Ethylhexyl Triazone
    7.00 Uvinul N 539 T Octocrylene
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    12.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    2.00 Lanette O Cetearyl Alcohol
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 35.35  Water dem. Aqua dem.
    3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.1% C16-Microbead
    0.30 Keltrol Xanthan Gum
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    D 0.50 Phenonip
    1.00 Vitamin E Acetate Tocopheryl Acetate
    A 7.00 Uvinul A Plus B Ethylhexyl Methoxycinnamate, Diethylamino
    Hydroxybenzoyl Hexyl Benzoate
    1.00 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl
    Triazine
    1.00 Uvinul T 150 Ethylhexyl Triazone
    7.00 Uvinul N 539 T Octocrylene
    4.00 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2
    Dipolyhydroxystearate, Glycerin
    8.00 Cetiol B Dibutyl Adipate
    8.00 Finsolv TN C12-15 Alkyl Benzoate
    12.00  Myritol 331 Cocoglycerides
    1.00 Lanette E Sodium Cetearyl Sulfate
    2.00 Lanette O Cetearyl Alcohol
    B 5.00 T-Lite SF Titanium Dioxide, Alumina Hydrate,
    Dimethicone/Methicone Copolymer
    C 30.45  Water dem. Aqua dem.
    3.00 Glycerin 87% Glycerin
    0.05 Edeta BD Disodium EDTA
    0.20 Allantoin Allantoin
    0.30 Keltrol Xanthan Gum
    5.0% C16-Microbead-Canthaxanthin
    1.50 Veegum Ultra Magnesium Aluminum Silicate
    D 0.50 Phenonip
    1.00 Vitamin E Acetate Tocopheryl Acetate
    5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl
    Methicone
    2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl
    Benzoate
    2.00 Mexoryl XL Drometrizole Trisiloxane
    3.00 Uvinul MC 80 Ethylhexyl Methoxycinnamate
    0.50 Abil 350 Dimethicone
    2.75 Carnico wax LT 20 Carnauba (Copernica Cerifera) Wax,
    Paraffin
    3.70 Candelilla wax LT 281 LJ Candelilla (Euphorbia Cerifera) Wax
    1.80 Beeswax 3050 PH Bees Wax
    3.20 TeCero wax 30445 Microcrystalline Wax
    3.20 TeCero wax 1030 K Microcrystalline Wax
    1.34 Cutina CP Cetyl Palmitate
    6.40 Vaseline Petrolatum
    7.30 Softisan 100 Hydrogenated Coco-Glycerides
    10.00  Luvitol EHO Cetearyl Ethylhexanoate
    0.17 Bisabolol nat. Bisabolol
    1.84 Vitamin E Acetate Tocopheryl Acetate
    1.0% C16-Microbead
    0.42 D,L-Alpha-Tocopherol Tocopherol
    40.38  Castor oil Castor (Ricinus Communis) Oil
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    2.00 Mexoryl XL Drometrizole Trisiloxane
    10.00  Witconol APM PPG-3 Myristyl Ether
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane
    5.00 Uvinul N 539 T Octocrylene
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    C 5.00 1,2-Propylene glycol Propylene Glycol
    1.00 Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    1.0% C16-Microbead
    1.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    69.50  Water dem. Aqua dem.
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Mexoryl XL Drometrizole Trisiloxane
    10.00  Witconol APM PPG-3 Myristyl Ether
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentasiloxane, Cyclohexasiloxane
    5.00 Uvinul N 539 T Octocrylene
    B 3.00 T-Lite SF-S Titanium Dioxide, Silica Hydrate, Alumina
    Hydrate, Methicone/Dimethicone Copolymer
    C 5.00 1,2-Propylene glycol Propylene Glycol
    1.00 Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    0.2% C16-Microbead
    1.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    68.30  Water dem. Aqua dem.
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 0.70 Cremophor A 25 Ceteareth-25
    1.70 Cremophor A 6 Ceteareth-6, Stearyl Alcohol
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    5.00 Uvinul N 539 T Octocrylene
    4.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    2.00 Abil B 8843 PEG-14 Dimethicone
    3.60 Lanette O Cetearyl Alcohol
    1.00 Uvinul T150 Ethylhexyl Triazone
    2.00 Cetiol B Dibutyl Adipate
    B 4.00 Glycerin 87% Glycerin
    0.20 Edeta BD Disodium EDTA
    71.00  Water dem. Panthenol
    C 4.00 Luvigel EM Caprylic/Capric Triglyceride, Sodium
    Acrylates Copolymer
    1.0% C16-Microbead-Canthaxanthin
    D 1.00 Vitamin E Acetate Tocopheryl Acetate
    0.20 Bisabolol rac. Bisabolol
    q.s. Preservative
    A 1.00 Abil Care 85 Bis-PEG/PPG-16/16 PEG/PPG-16/16
    Dimethicone, Caprylic/Capric Triglyceride
    3.00 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil
    0.30 Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    2.00 Parsol 1789 Butyl Methoxydibenzoylmethane
    2.00 Mexoryl XL Drometrizole Trisiloxane
    10.00  Witconol APM PPG-3 Myristyl Ether
    1.00 Uvinul T 150 Ethylhexyl Triazone
    1.00 Dow Corning 345 Fluid Cyclopentaslioxane, Cyclohexasiloxane
    5.00 Uvinul N 539 T Octocrylene
    B 3.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 5.00 1,2-Propylene glycol Propylene Glycol
    1.00 Mexoryl SX Terephthalidene Dicamphor Sulfonic Acid
    0.20 Keltrol Xanthan Gum
    0.10 Edeta BD Disodium EDTA
    1.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    0.5% C16-Microbead
    68.00  Water dem. Aqua dem.
    D q.s. Perfume Oil
    0.50 Glidant DMDM Hydantoin
    A 2.00 Uvinul A Plus Diethylamino Hydroxybenzoyl Hexyl Benzoate
    3.00 Uvinul N 539 T Octocrylene
    3.00 Emulgade PL 68/50 Cetearyl Glucoside, Cetearyl Alcohol
    2.00 Dracorin 100 SE Glyceryl Stearate, PEG-100 Stearate
    1.00 Fitoderm Squalane
    0.5  Cremophor WO 7 PEG-7 Hydrogenated Castor Oil
    0.5  Cremophor PS 20 Polysorbate 20
    2.00 Dry Flo Pure Aluminium Starch Octenylsuccinate
    B 5.00 Z-COTE MAX Zinc Oxide (and) Diphenyl Capryl Methicone
    C 4.00 1,2-Propylene Glycol Care Propylene Glycol
    0.20 Keltrol Xanthan Gum
    1.0% C16-Microbead
    0.50 Simulgel 600 Acrylamide/Sodium Acryloyldimethyltaurate
    Copolymer, Isohexadecane, Polysorbate 80
    65.80  Water dem. Aqua dem.
    D 0.50 Euxyl K 300
    0.50 Vitamin E-Acetate Tocopheryl Acetate
    1.00 RetiSTAR Caprylic/Capric Triglyceride, Sodium
    Ascorbate, Tocopherol, Retinol

Claims (27)

1. (canceled)
2. (canceled)
3. (canceled)
4. (canceled)
5. (canceled)
6. (canceled)
7. (canceled)
8. (canceled)
9. (canceled)
10. A method for preparing a cosmetic comprising incorporating a protein microbead into the cosmetic.
11. The method of claim 10, wherein the protein microbead comprises silk protein.
12. The method of claim 10, wherein the protein microbead is produced from a predominantly intrinsically unfolded protein.
13. The method of claim 12, wherein more than 50% of amino acid radicals comprising the predominantly intrinsically unfolded protein have a value of >0.5 calculated by an IUpred algorithm.
14. The method of claim 13, wherein the protein microbead comprises a coupling a protein and an effector molecule.
15. The method of claim 14, wherein the effector molecule is a UV photoprotective filter.
16. The method of claim 12, wherein the predominantly intrinsically unfolded protein is a C16 spider silk protein.
17. The method of claim 12, wherein the protein microbead is produced by a method comprising the steps of: (1) dissolving a protein in a solvent, (2) inducing phase separation in the emulsified solvent phase and protein-rich phase through an additive, (3) curing the protein-rich phase, optionally, by adding a crosslinker, (4) isolating and, optionally, purifying the protein microbead of step (3).
18. The method of claim 10, wherein the cosmetic is a skin cosmetic.
19. A cosmetic composition comprising a protein microbead and an effector molecule.
20. The cosmetic composition of claim 19, wherein the effector molecule is a 1 UV photoprotective filter.
21. The cosmetic composition of claim 20, wherein the UV photoprotective filter is a UV-A filter.
22. The cosmetic composition of claim 20, wherein the UV photoprotective filter is a UV-B filter.
23. The cosmetic composition of claim 19, wherein the protein microbead is produced from a predominantly intrinsically unfolded protein.
24. The cosmetic composition of claim 23, wherein more than 50% of amino acid radicals comprising the predominantly intrinsically unfolded protein have a value of >0.5 calculated according to an IUpred algorithm.
25. The cosmetic composition of claim 19, wherein the protein microbead is produced from a predominantly intrinsically unfolded protein, wherein more than 50% of amino acid radicals comprising the predominantly intrinsically unfolded protein have a value of >0.5 calculated according to an IUpred algorithm, and the effector molecule is a UV photoprotective filter.
26. The cosmetic composition of claim 19, wherein the protein microbead is produced from a C16 spider silk protein, and the effector molecule is a UV photoprotective filter.
27. The cosmetic composition of claim 19, wherein the cosmetic is a skin cosmetic.
US12/161,352 2006-01-20 2007-01-19 Use of protein microbeads in cosmetics Abandoned US20100278882A1 (en)

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WO2007082936A1 (en) 2007-07-26
WO2007082923A2 (en) 2007-07-26
CA2637065C (en) 2014-03-18
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US20100278883A1 (en) 2010-11-04
CN104856962A (en) 2015-08-26
JP2009523766A (en) 2009-06-25
CA2637065A1 (en) 2007-07-26
US8288512B2 (en) 2012-10-16
EP1979055A2 (en) 2008-10-15
WO2007082923A3 (en) 2007-10-04
JP2009523767A (en) 2009-06-25

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