EP1414398A2 - Cosmetic or dermatological preparations having a long-term cooling action - Google Patents
Cosmetic or dermatological preparations having a long-term cooling actionInfo
- Publication number
- EP1414398A2 EP1414398A2 EP02754879A EP02754879A EP1414398A2 EP 1414398 A2 EP1414398 A2 EP 1414398A2 EP 02754879 A EP02754879 A EP 02754879A EP 02754879 A EP02754879 A EP 02754879A EP 1414398 A2 EP1414398 A2 EP 1414398A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- preparations
- polyethylene glycol
- substances
- acid
- cosmetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
-
- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/24—Thermal properties
- A61K2800/244—Endothermic; Cooling; Cooling sensation
Definitions
- the present invention relates to cosmetic and dermatological preparations with a long-lasting cooling effect, in particular skin-care cosmetic and dermatological preparations.
- the skin is the largest human organ. Among its many functions (for example for heat regulation and as a sensory organ), the barrier function that prevents the skin (and ultimately the entire organism) from drying out is probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of substances coming from outside. This barrier function is brought about by the epidermis, which as the outermost layer forms the actual protective cover against the environment. At around a tenth of the total thickness, it is also the thinnest layer of the skin.
- the outermost layer of the epidermis is of particular importance as an important barrier layer. for protection against environmental influences and dehydration.
- the horny layer is constantly worn out in contact with the environment and must therefore be renewed continuously.
- the corneocytes homo cells
- the complex lipid membrane in the intercellular spaces corresponds to the mortar.
- the epidermal lipids In addition to their barrier effect against external chemical and physical influences, the epidermal lipids also contribute to the cohesion of the horny layer and have an influence on the smoothness of the skin. In contrast to the sebum lipids, which do not form a closed film on the skin, the epidermal lipids are distributed over the entire horny layer.
- Cosmetic skin care is primarily understood to mean that the natural function of the skin as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the loss of the body's own substances (e.g. water, natural fats, electrolytes) is strengthened or restored.
- environmental influences e.g. dirt, chemicals, microorganisms
- loss of the body's own substances e.g. water, natural fats, electrolytes
- the aim of skin care is also to compensate for the loss of fat and water in the skin caused by daily washing. This is especially important when the natural regeneration ability is insufficient.
- skin care products are intended to protect against environmental influences, particularly sun and wind, and to delay skin aging.
- Medical topical compositions usually contain one or more drugs in effective concentration.
- Common cosmetic dosage forms are emulsions, that is, metastable two- or multi-phase systems in which the individual phases are in the liquid state.
- the most common emulsions are O / W and W / O emulsions.
- More rare forms of administration are multiple emulsions, i.e. those which themselves contain droplets of a further dispersed phase in the droplets of the dispersed (or discontinuous) phase, e.g. W / O / W emulsions and O / W / O emulsions.
- emulsifiers In order to guarantee the metastability of emulsions, surface-active substances, i.e. emulsifiers, are generally necessary.
- emulsifier-free preparations which, for example, have oil droplets dispersed in an aqueous phase, similar to an O / W emulsion.
- a prerequisite for this may be that the continuous aqueous phase has a gel structure stabilizing the dispersed phase and other circumstances more.
- Such systems are sometimes called hydrodispersions or oleodispersions, depending on which is the disperse phase and which is the continuous phase.
- Gels are the usual and increasingly popular cosmetic and dermatological preparation forms.
- gels are understood to mean: Relatively dimensionally stable, easily deformable disperse systems composed of at least two components, which as a rule consist of a - usually solid - colloidally divided substance made up of long-chain molecular groups (e.g. gelatin, silica, polysaccharides) as a scaffold and a liquid dispersant (e.g. water) exist.
- the colloidally divided substance is often referred to as a thickening or gelling agent. It forms a spatial network in the dispersant, whereby individual colloidal particles are involved via electrostatic interaction.
- T ⁇ TIGINGSKOPIE can be more or less firmly linked.
- the dispersing agent that surrounds the network is characterized by electrostatic affinity for the gelling agent, ie a predominantly polar (in particular: hydrophilic) gelling agent preferably gels a polar dispersing agent (in particular: water), whereas a predominantly non-polar gelling agent preferably gels non-polar dispersing agent.
- Lipogels and oleols are also common in cosmetic and pharmaceutical galenics.
- oleogels which are practically anhydrous
- hydrogels which are practically fat-free.
- gels are transparent.
- gels are usually characterized by a semi-solid, often flowable consistency.
- surfactant gels are also common preparations of the prior art. This is understood to mean systems which, in addition to water, have a high concentration of emulsifiers, typically more than about 25% by weight, based on the overall composition. If oil components are solubilized in these surfactant gels, also called “surfactant gels” in technical terms, microemulsion gels are obtained, which are also referred to as “ringing gels”. By adding nonionic emulsifiers, for example alkyl polyglycosides, it is possible to obtain cosmetically more elegant microemulsion gels.
- the cooling effect of cosmetic preparations has so far been based on two basic principles: Use of components which volatilize in gaseous form after topical application and remove the required amount of energy, the so-called enthalpy of vaporization, for the most part from the skin surface. Suitable liquid components are therefore used in corresponding non-occlusive cosmetics. Ethanol has proven to be particularly suitable here, and formulations with a high water content also have a clear cooling effect.
- cooling agents that interact with the skin's heat receptors and thus trigger a feeling of cold without generating a measurable physical cooling.
- menthol and various menthol derivatives are used for this.
- high ethanol contents as well as menthol and its derivatives are not suitable for numerous applications from an olfactory point of view, in addition to their irritative potential, in particular because of their distinct odor. Frequently enough, such substances also cause an increase in blood circulation, which on the contrary creates a feeling of warmth.
- cooling agents In the literature, for example, ionic compounds, especially ammonium salts, are described as cooling agents. Isopropanolic gels with camphor and menthol additives are also widely used as cooling preparations.
- the object of the present invention was therefore to provide nourishing cosmetic and medical preparations which do not have the disadvantages of the prior art, in particular those which, when applied to the skin or mucous membranes, have a moisturizing and / or cooling effect.
- phase transition from the solid to the liquid state is also characterized by the occurrence of heat of transformation in numerous compounds. Endothermic melting processes take place with the absorption of energy that originates from the environment and thus leads to a lowering of the temperature there.
- cooling cosmetic or medical topical preparations characterized by a content of one or more substances, the melting point or melting interval of which is chosen in the range between 28 ° C. and 40 ° C., and the positive enthalpy of fusion have, which substance or substances are present in the preparations in the solid state.
- ° C is selected and which have a positive enthalpy of fusion for the production of cooling cosmetic or medical topical preparations
- preparations according to the invention develop their cooling effect within a wide range of use concentrations of the underlying substances, for example 0.5-50% by weight, advantageously 1-20% by weight, based on the total weight of the preparations. They are easy to formulate and make no great demands on manufacturing processes.
- lipophilic substances are selected whose melting point or melting interval is in the range between 28 ° C and 40 ° C and which have a positive enthalpy of fusion
- hydrophilic cosmetic or dermatological bases are to be considered to which the substance or as the substances whose melting point or melting interval is in the range between 28 ° C. and 40 ° C. and which have a positive enthalpy of fusion are then particularly preferably in particulate suspension, for example in aqueous gel formulations.
- Particularly advantageous substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C and which have a positive melting enthalpy are selected from the group of lipophilic substances, in particular the esters of C 14 -C 8 fatty acids, with low molecular weight ( C 1 - C 5 ) alcohols, the fatty alcohols C 8 - C 22 , the branched or unbranched fatty acids, the hydrocarbons C 16 - C 22 .
- Methyl palmitate is particularly preferred for the purposes of the present invention.
- cooling active ingredients for example menthol or menthol derivatives, can be added to these formulations for sensory modification or for enhancing the cooling effect.
- BEST ⁇ TIGINGSKOPIE sen are also collectively referred to in the context of the present disclosure as the active ingredient according to the invention or provided with similar synonyms.
- preparations containing the active compound combinations according to the invention, customary antioxidants can be used.
- the antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L- Carnosine and its derivatives (e.g. anserine), carotenoids, carotenes (e.g. ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
- amino acids eg glycine, histidine, tyrosine, tryptophan
- imidazoles eg urocanic acid
- peptides such as D, L-carnosine, D-carnosine, L
- thioredoxin glutathione , Cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g.
- buthioninsulfoximines homocysteine sulfoximine, buthioninsulfones, penta-, hexa-, hexa- foximin) in very low tolerable doses (e.g.
- chelators eg ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin, hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA , EGTA and its derivatives, unsaturated fatty acids and their derivatives (eg ⁇ -linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, alanine diacetic acid, flavonoids, polyphenols, catechins, vitamin C and derivatives (eg ascorbyl palmitate, Mg-ascorbyl phosphate , Ascorbylacetate), tocopherols and derivatives (eg vitamin E acetate), as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and
- hydroxy acids eg citric acid, lactic acid,
- BEST ⁇ TIGINGSKOPIE their derivatives, zinc and their derivatives (for example ZnO, ZnSO 4 ) selenium and their derivatives (for example selenium methionine), stilbenes and their derivatives (for example stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides) , Nucleosides, peptides and lipids) of these active ingredients.
- the amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 1 to 10% by weight, based on the total weight of the preparation ,
- the prophylaxis or the cosmetic or dermatological treatment with the active ingredient used according to the invention or with the cosmetic or topical dermatological preparations with an effective content of active ingredient used according to the invention is carried out in the usual way, namely in such a way that the active ingredient used according to the invention or the cosmetic or topical dermatological preparations with an effective content of active ingredient used according to the invention is applied to the affected skin areas.
- the active ingredient used according to the invention can advantageously be incorporated into customary cosmetic and dermatological preparations, which can be in various forms. So you can e.g. a solution, an emulsion of the type water-in-oil (W / O) or of the type oil-in-water (O / W), or a multiple emulsions, for example of the type water-in-oil-in-water (W / O / W) or oil-in-water-in-oil (O / W / O), a hydro-dispersion or lipodispersion, a gel, a solid stick or an aerosol.
- Emulsions according to the invention in the sense of the present invention are advantageous and contain e.g. Fats, oils, waxes and / or other fat bodies, as well as water and one or more emulsifiers, as are usually used for such a type of formulation.
- Medical topical compositions in the sense of the present invention generally contain one or more medicaments in an effective concentration.
- medicaments in an effective concentration.
- cosmetic or topical dermatological compositions within the meaning of the present invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritional cream, day or night cream, etc. It may be possible and advantageous to add the compositions according to the invention as the basis for pharmaceutical formulations use.
- cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.
- these preferably additionally contain at least one UVA filter substance and / or at least one UVB filter substance and / or at least one inorganic pigment.
- UV-A or UV-B filter substances are usually incorporated into day creams.
- Preparations according to the invention can advantageously contain substances which absorb UV radiation in the UVB range, the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the preparations.
- the UVB filters can be oil-soluble or water-soluble.
- oil-soluble substances e.g. to call:
- 4-aminobenzoic acid derivatives preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
- Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
- Esters of salicylic acid preferably salicylic acid (2-ethylhexyl) ester, salicylic acid
- Esters of benzalmalonic acid preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;
- Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid and their salts;
- UVB filters which can be used according to the invention, is of course not intended to be limiting.
- the invention also relates to the combination of a UVA filter according to the invention with a UVB filter or a cosmetic or dermatological preparation according to the invention which also contains a UVB filter.
- UVA filters in the preparations according to the invention, which are usually contained in cosmetic and / or dermatological preparations.
- Such filter substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- ( 4'-isopropylphenyl) propane-1,3-dione.
- Preparations containing these combinations are also the subject of the invention.
- the same amounts of UVA filter substances that were mentioned for UVB filter substances can be used.
- Cosmetic and / or dermatological preparations in the sense of the present invention can also contain inorganic pigments which are usually used in cosmetics to protect the skin from UV rays. These are oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as modifications in which the oxides are the active agents. It is particularly preferred to use pigments based on titanium dioxide. The amounts given for the above combinations can be used.
- the cosmetic preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, for example preservatives, bactericides, deodorising substances, antiperspirants, insect repellents, vitamins, agents for preventing foaming, dyes, pigments with a coloring effect, thickeners, softening substances , moisturizing and / or moisturizing substances, fats, oils, waxes or other usual substances components of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
- cosmetic auxiliaries as are usually used in such preparations, for example preservatives, bactericides, deodorising substances, antiperspirants, insect repellents, vitamins, agents for preventing foaming, dyes, pigments with a coloring effect, thickeners, softening substances , moisturizing and / or moisturizing substances, fats, oils, waxes or other usual substances components of a cosmetic formulation such as alcohols, polyols, polymers
- Preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UVB range, the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1.0 to 6.0% by weight, based on the total weight of the preparations, in order to prepare cosmetic preparations To provide that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair.
- the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1.0 to 6.0% by weight, based on the total weight of the preparations, in order to prepare cosmetic preparations To provide that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair.
- UVB filter substances if they contain UVB filter substances, they can be oil-soluble or water-soluble.
- Oil-soluble UVB filters which are advantageous according to the invention are, for example:
- 4-aminobenzoic acid derivatives preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
- Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
- esters of salicylic acid preferably salicylic acid (2-ethylhexyl) ester, salicylic acid (4-isopropylbenzyl) ester, salicylic acid homomethyl ester,
- Esters of benzalmalonic acid preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester,
- Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself;
- BEST ⁇ TIG ⁇ NGSKOPIE Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid and their salts;
- Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and their salts and 1,4-di (2-oxo-10-sulfo 3-bornylidene methyl) -benzene and its salts (the corresponding 10-sulfato compounds, e.g. the corresponding sodium, potassium or triethanolammonium salt), also as benzene-1,4-di (2-oxo-3-bornylidene methyl) Designated 10-sulfonic acid
- UVB filters which can be used in combination with the active compound combinations according to the invention, is of course not intended to be limiting.
- UVA filters that are usually contained in cosmetic preparations.
- These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.
- the quantities used for the UVB combination can be used.
- Cosmetic and dermatological preparations according to the invention advantageously also contain inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular the oxides of titanium (Ti0 2 ), zinc (ZnO), iron (eg Fe 2 0 3 ), zirconium (Zr0 2 ), silicon (Si0 2 ), manganese (eg MnO), aluminum (Al 2 0 3 ), cerium (eg Ce 2 0 3 ), mixed oxides of the corresponding metals and mixtures of such oxides. It is particularly preferred to use pigments based on TiO 2 .
- the inorganic pigments are in hydrophobic form, i.e. that they have been treated to be water-repellent on the surface.
- This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer by methods known per se.
- BEST ⁇ TIGINGSKOPIE One such method consists, for example, in that the hydrophobic surface layer after a rectification
- n and m are stoichiometric parameters to be used at will, R and R 'are the desired organic radicals.
- hydrophobized pigments shown in analogy to DE-OS 33 14 742 are advantageous.
- Advantageous Ti0 2 pigments are available, for example, under the trade names MT 100 T from TAYCA, M 160 from Kemira and T 805 from Degussa.
- Preparations according to the invention can also contain anionic, nonionic and / or amphoteric surfactants, especially if crystalline or microcrystalline solids, for example inorganic micropigments, are to be incorporated into the preparations according to the invention.
- Surfactants are amphiphilic substances that can dissolve organic, non-polar substances in water.
- hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO " , -0S0 3 2" , -S0 3 " , while the hydrophobic parts generally represent non-polar hydrocarbon residues.
- Surfactants are generally classified according to Art and charge of the hydrophilic part of the molecule. There are four groups:
- Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In an aqueous solution they form negatively charged organic ions in an acidic or neutral environment. Cationic surfactants are characterized almost exclusively by the presence of a quaternary ammonium group. In water
- BEST ⁇ TIGIIMGSKOPIE solution they form positively charged organic ions in an acidic or neutral environment.
- Amphoteric surfactants contain both anionic and cationic groups and accordingly behave like anionic or cationic surfactants in aqueous solution depending on the pH. They have a positive charge in a strongly acidic environment and a negative charge in an alkaline environment. In the neutral pH range, however, they are zwitterionic, as the following example should illustrate:
- Non-ionic surfactants do not form ions in an aqueous medium.
- acylglutamates for example sodium acylglutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
- acyl peptides for example palmitoyl-hydrolyzed milk protein, sodium cocoyl-hydrolyzed.es soy protein and sodium / potassium cocoyl-hydrolyzed collagen,
- sarcosinates for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
- taurates for example sodium lauroyl taurate and sodium methyl cocoyitaurate
- carboxylic acids for example lauric acid, aluminum stearate, magnesium alkanolate and zinc undecylenate,
- ester carboxylic acids for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauram idcarboxylate,
- ether carboxylic acids for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,
- BEST ⁇ TIGINGSKOPIE Phosphoric acid esters and salts such as DEA-oleth-10-phosphate and dilureth-4-phosphate,
- acyl isethionates e.g. Sodium / ammonium cocoyl isethionate
- alkyl sulfonates for example sodium cocosmonoglyceride sulfate, sodium C 12 . 14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
- Sulfosuccinates for example dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate
- sulfuric acid esters such as
- alkyl ether sulfate for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C 12 . 13 pareth sulfate,
- Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate.
- Quaternary surfactants contain at least one N atom which is covalently linked to 4 alkyl or aryl groups. Regardless of the pH value, this leads to a positive charge.
- Alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysulfain are advantageous.
- the cationic surfactants used in the invention can also preferably be chosen from the group of quaternary ammonium compounds, especially benzyltrialkylammonium chlorides or bromides, such as rylammoniumchlorid Benzyldimethylstea-, further alkyltrialkylammonium salts, for example cetyltrimethylammonium chloride or bromide, niumchloride Alkyldimethylhydroxyethylammo- or bromides, dialkyldimethylammonium chlorides or bromides , Alkyl amide
- BEST ⁇ TIGINGSKOPiE ethyltrimethylammonium ether sulfates alkylpyridinium salts, for example lauryl or cetylpyrimidinium chloride, imidazoline derivatives and compounds with a cationic character such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous.
- acyl / dialkyl ethylenediamine for example sodium acyl amphoacetate, disodium acyl amphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydroxy propyl sulfonate, disodium acyl amphodiacetate and sodium acyl amphopropionate,
- N-alkylamino acids for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
- alkanolamides such as Cocamide MEA / DEA MIPA
- amine oxides such as cocoamidopropylamine oxide
- esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
- ethers for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterol esters, ethoxylated / propoxylated triglyceride esters, ethoxylated.es propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, and propoxylated POE ethers Alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.
- the surface-active substance can be present in the preparations according to the invention in a concentration between 1 and 95% by weight, based on the total weight of the preparations.
- Oils such as triglycerides of capric or caprylic acid as well as natural oils such as e.g. Castor oil;
- Fats, waxes and other natural and synthetic fat bodies preferably
- Esters of fatty acids with low C alcohols e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with lower C- alkanoic acids
- Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
- the oil phase of the emulsions of the present invention is advantageously selected from the group of the esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms.
- ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethyl-2-ethylhexyl palmitate 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semisynthetic and natural mixtures of such esters, for example Jojoba oil.
- the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or
- BEST ⁇ TIGINGSKOPIE saturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 carbon atoms.
- the fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, for example olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
- any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
- the oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C 12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.
- hydrocarbons paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.
- the oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.
- Such silicones or silicone oils can be present as monomers, which are generally characterized by structural elements, as follows:
- n can take values from 3/2 to 20. Broken values for n take into account that there may be odd numbers of siloxyl groups in the cycle.
- Cyclomethicone e.g. decamethylcyclopentasiloxane
- silicone oils can also be used advantageously for the purposes of the present invention, for example undecamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone.
- silicone oils of a similar constitution to the compounds described above, the organic side chains of which are derivatized, for example polyethoxylated and / or polypropoxylated.
- these include, for example, polysiloxane-polyalkyl-polyether copolymers such as the cetyl-dimethicone copolyol, the (cetyl-dimethicone copolyol (and) polyglyceryl-4-isostearate (and) hexyl laurate)
- the aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, di - Ethylene glycol monomethyl or monoethyl ether and similar products, furthermore alcohols with a low C number, for example Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide and aluminum silicates.
- alcohols, diols or polyols of low C number and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol
- Preparations according to the invention which are present as emulsions particularly advantageously contain one or more hydrocolloids.
- hydrocolloids can advantageously be selected from the group of the gums, polysaccharides, cellulose derivatives, layered silicates, polyacrylates and / or other polymers.
- Preparations according to the invention which are present as hydrogels contain one or more hydrocolloids. These hydrocolloids can advantageously be selected from the aforementioned group.
- Gums include plant or tree sap that harden in the air and form resins or extracts from aquatic plants. Gum arabic, locust bean gum, tragacanth, karaya, guar gum, pectin, gellan gum, carrageenan, agar, algine, chondrus, xanthan gum can advantageously be selected from this group for the purposes of the present invention.
- derivatized gums such as hydroxypropyl guar (Jaguar® HP 8) is also advantageous.
- polysaccharides and derivatives are e.g. Hyaluronic acid, chitin and chitosan, chondroitin sulfates, starch and starch derivatives.
- cellulose derivatives are e.g. Methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose.
- Layered silicates contain naturally occurring and synthetic clays such as Montmorillonite, bentonite, hectorite, laponite, magnesium aluminum silicates such as Veegum®. These can be used as such or in a modified form such as e.g. Stearylalkonium hektorite.
- silica gels can also advantageously be used.
- the polyacrylates include e.g. Carbopol types from Goodrich (Carbopol 980, 981, 1382, 5984, 2984, EDT 2001 or Pemulen TR2).
- polymers e.g. Polyacrylamides (Seppigel 305), polyvinyl alcohols, PVP, PVP / VA copolymers, polyglycols.
- Preparations according to the invention in the form of emulsions contain one or more emulsifiers.
- emulsifiers can advantageously be selected from the group of nonionic, anionic, cationic or amphoteric emulsifiers.
- the nonionic emulsifiers include a) partial fatty acid esters and fatty acid esters of polyhydric alcohols and their ethoxylated derivatives (e.g. glyceryl monostearates, sorbitan stearates, glyceryl stearyl citrates, sucrose stearyl citrates, b) ethoxylated fatty alcohols and fatty acids c) alkyl acid phenol amide fatty amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, e.g. Triton X)
- the anionic emulsifiers include a) soaps (e.g. sodium stearate) b) fatty alcohol sulfates c) mono-, di- and trialkylphosphonic acid esters and their ethoxylates
- the cationic emulsifiers include a) quaternary ammonium compounds with a long-chain aliphatic radical, e.g. Distearyldimonium Chloride
- amphoteric emulsifiers include a) alkylamininoalkane carboxylic acids b) betaines, sulfobetaines c) imidazoline derivatives
- emulsifiers which include beeswax, wool wax, lecithin and sterols.
- O / W emulsifiers can, for example, advantageously be selected from the group of polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated products, for example: the fatty alcohol ethoxylates of the ethoxylated wool wax alcohols, the polyethylene glycol ethers of the general formula R-0 - (- CH 2 -CH 2 - 0-) n -R ', the fatty acid ethoxylates of the general formula
- the polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated O / W emulsifiers used are selected with particular advantage from the group of substances with HLB values of 11-18, particularly preferably
- fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
- cetyl alcohols cetylstearyl alcohols
- cetearyl alcohols cetearyl alcohols
- Polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolureth-12).
- Sodium laureth-11 carboxylate can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt.
- Sodium laureth 1-4 sulfate can advantageously be used as alkyl ether sulfate.
- polyethylene glycol glycerol fatty acid esters from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl 20-caprate / caprin ) glyceryl oleate, polyethylene glycol (20) glyceryl iso stearate, polyethylene glycol (18) glyceryl oleate / cocoate.
- sorbitan esters from the group polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
- W / O emulsifiers that can be used are: fatty alcohols with 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18, carbon atoms, diglycerol esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 - 18 C atoms, monoglycerol ethers saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 8 to 24, in particular 12 - 18 C - Atoms, diglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and /
- W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl
- BEST ⁇ TIGINGSKOPiE monoisostearate colmonocaprylat propylene glycol monostearate, propylene glycol monoisostearate glycol, propylene, sorbitan monoisostearate, propylene glycol monolaurate Sorbitanmo-, sorbitan, Sorbitanmonoisooleat, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, Isobehenylalkohol, Selachyl- alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth 2), glyceryl mono laurate, glyceryl monocaprinate, glyceryl monocaprylate.
- phases (A) and (B) are combined at about 80 ° C and stirred until the phases appear homogeneous. Then phases (A) and (B) are combined and cooled to approx. 40 ° C. The perfume phase (C) is added to the combined phases (A) and (B) at about 40 ° C., whereupon the mixture is cooled to room temperature.
- phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous.
- the phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified by vigorous stirring.
- the preservation phase (C) is added to the combined phases (A) and (B) at about 50 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
- phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous.
- the phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified and homogenized by vigorous stirring.
- the preservation phase (C) is added to the combined phases (A) and (B) at approx. 55 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
- phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous.
- the phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified and homogenized by vigorous stirring.
- the perfume phase (C) is added to the combined phases (A) and (B) at about 55 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
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Abstract
The invention relates to cooling cosmetic or medical topical preparations, characterised in that they contain at least one substance having a melting point or a melting interval between 28 °C and 40 °C, and in that they have a positive melting enthalpy. Said substance(s) are in the solid state in the preparations.
Description
Beschreibung description
Kosmetische oder dermatologische Zubereitungen mit langanhaltender kühlenderCosmetic or dermatological preparations with long-lasting cooling
Wirkungeffect
Die vorliegende Erfindung betrifft kosmetische und dermatologische Zubereitungen mit langanhaltender kühlender Wirkung, insbesondere hautpflegende kosmetische und dermatologische Zubereitungen.The present invention relates to cosmetic and dermatological preparations with a long-lasting cooling effect, in particular skin-care cosmetic and dermatological preparations.
Die Haut ist das größte Organ des Menschen. Unter ihren vielen Funktionen (beispielsweise zur Wärmeregulation und als Sinnesorgan) ist die Barrierefunktion, die das Austrocknen der Haut (und damit letzlich des gesamten Organismus) verhindert, die wohl wichtigste. Gleichzeitig wirkt die Haut als Schutzeinrichtung gegen das Eindringen und die Aufnahme von außen kommender Stoffe. Bewirkt wird diese Barrierefunktion durch die Epidermis, welche als äußerste Schicht die eigentliche Schutzhülle gegenüber der Umwelt bildet. Mit etwa einem Zehntel der Gesamtdicke ist sie gleichzeitig die dünnste Schicht der Haut.The skin is the largest human organ. Among its many functions (for example for heat regulation and as a sensory organ), the barrier function that prevents the skin (and ultimately the entire organism) from drying out is probably the most important. At the same time, the skin acts as a protective device against the penetration and absorption of substances coming from outside. This barrier function is brought about by the epidermis, which as the outermost layer forms the actual protective cover against the environment. At around a tenth of the total thickness, it is also the thinnest layer of the skin.
Die äußerste Schicht der Epidermis, das Stratum corneum (Hornschicht), ist als wichtige Barriereschicht von besonderer Bedeutung u.a. für den Schutz vor Umwelteinflüssen und Austrocknung. Die Hornschicht wird im Kontakt mit der Umwelt ständig abgenutzt und muß deshalb ununterbrochen erneuert werden.The outermost layer of the epidermis, the stratum corneum (horny layer), is of particular importance as an important barrier layer. for protection against environmental influences and dehydration. The horny layer is constantly worn out in contact with the environment and must therefore be renewed continuously.
Ein heute in der Fachwelt weitverbreitetes Hautmodell faßt das Stratum corneum als Zwei-Komponenten-System, ähnlich einer Ziegelsteinmauer (Ziegelstein-Mörtel-Modell), auf. In diesem Modell entsprechen die Korneozyten (Homzellen) den Ziegelsteinen, die kompliziert zusammengesetzte Lipidmembran in den Interzellularräumen entspricht dem Mörtel.A skin model that is widespread among experts today regards the stratum corneum as a two-component system, similar to a brick wall (brick-mortar model). In this model, the corneocytes (hom cells) correspond to the bricks, the complex lipid membrane in the intercellular spaces corresponds to the mortar.
UNGSK0P1E
Außer ihrer Barrierewirkung gegen externe chemische und physikalische Einflüsse tragen die epidermalen Lipide auch zum Zusammenhalt der Hornschicht bei und haben Einfluß auf die Hautglätte. Im Gegensatz zu den Talgdrüsenlipiden, die keinen geschlossenen Film auf der Haut ausbilden, sind die epidermalen Lipide über die gesamte Hornschicht verteilt.UNGSK0P1E In addition to their barrier effect against external chemical and physical influences, the epidermal lipids also contribute to the cohesion of the horny layer and have an influence on the smoothness of the skin. In contrast to the sebum lipids, which do not form a closed film on the skin, the epidermal lipids are distributed over the entire horny layer.
Das äußerst komplexe Zusammenwirken der feuchtigkeitsbindenden Substanzen und der Lipide der oberen Hautschichten ist für die Regulation der Hautfeuchte sehr wichtig. Daher enthalten Kosmetika in der Regel, neben ausgewogenen Lipidabmischungen und Wasser, wasserbindende Substanzen.The extremely complex interaction of the moisture-binding substances and the lipids of the upper skin layers is very important for the regulation of skin moisture. Therefore, in addition to balanced lipid blends and water, cosmetics usually contain water-binding substances.
Neben der chemischen Zusammensetzung ist jedoch auch das physikalische Verhalten dieser Substanzen von Bedeutung. Daher ist die Entwicklung von sehr gut bioverträglichen Emulgatoren bzw. Tensiden mit flüssigkristallinen Eigenschaften wünschenswert. Damit formulierte Produkte unterstützen die flüssigkristalline Organisation der Interzellu- larlipide des Stratum Corneums und verbessern so die Barriereeigenschaften der Hornschicht. Besonders vorteilhaft ist es, wenn deren Molekülbestandteile aus natürlicherweise in der Epidermis vorkommenden Substanzen bestehen.In addition to the chemical composition, the physical behavior of these substances is also important. It is therefore desirable to develop very well biocompatible emulsifiers or surfactants with liquid-crystalline properties. Products formulated in this way support the liquid-crystalline organization of the intercellular lipids of the stratum corneum and thus improve the barrier properties of the horny layer. It is particularly advantageous if their molecular components consist of substances that occur naturally in the epidermis.
Unter kosmetischer Hautpflege ist in erster Linie zu verstehen, daß die natürliche Funktion der Haut als Barriere gegen Umwelteinflüsse (z.B. Schmutz, Chemikalien, Mikroorganismen) und gegen den Verlust von körpereigenen Stoffen (z.B. Wasser, natürliche Fette, Elektrolyte) gestärkt oder wiederhergestellt wird.Cosmetic skin care is primarily understood to mean that the natural function of the skin as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the loss of the body's own substances (e.g. water, natural fats, electrolytes) is strengthened or restored.
Wird diese Funktion gestört, kann es zu verstärkter Resorption toxischer oder allergener Stoffe oder zum Befall von Mikroorganismen und als Folge zu toxischen oder allergischen Hautreaktionen kommen.If this function is disturbed, there may be an increased absorption of toxic or allergenic substances or an infestation of microorganisms and, as a result, toxic or allergic skin reactions.
Ziel der Hautpflege ist es ferner, den durch tägliche Waschen verursachten Fett- und Wasserverlust der Haut auszugleichen. Dies ist gerade dann wichtig, wenn das natürliche Regenerationsvermögen nicht ausreicht. Außerdem sollen Hautpflegeprodukte vor Umwelteinflüssen, insbesondere vor Sonne und Wind, schützen und die Hautalterung verzögern.
Medizinische topische Zusammensetzungen enthalten in der Regel ein oder mehrere Medikamente in wirksamer Konzentration. Der Einfachheit halber wird zur sauberen Unterscheidung zwischen kosmetischer und medizinischer Anwendung und entsprechenden Produkten auf die gesetzlichen Bestimmungen der Bundesrepublik Deutschland verwiesen (z.B. Kosmetikverordnung, Lebensmittel- und Arzneimittelgesetz).The aim of skin care is also to compensate for the loss of fat and water in the skin caused by daily washing. This is especially important when the natural regeneration ability is insufficient. In addition, skin care products are intended to protect against environmental influences, particularly sun and wind, and to delay skin aging. Medical topical compositions usually contain one or more drugs in effective concentration. For the sake of simplicity, reference is made to the legal provisions of the Federal Republic of Germany (e.g. cosmetics regulation, food and drug law) for a clear distinction between cosmetic and medical use and corresponding products.
Übliche kosmetische Darreichungsformen sind Emulsionen, also metastabile Zwei- oder Mehrphasensysteme bei welchen die einzelnen Phasen im flüssigen Zustande vorliegen. Die gängigsten Emulsionen sind O/W- und W/O-Emulsionen. Seltenere Darreichungsformen sind multiple Emulsionen, also solche, welche in den Tröpfchen der dispergierten (oder diskontinuierlichen) Phase ihrerseits Tröpfchen einer weiteren dispergierten Phase enthalten, z.B. W/O/W-Emulsionen und O/W/O-Emulsionen.Common cosmetic dosage forms are emulsions, that is, metastable two- or multi-phase systems in which the individual phases are in the liquid state. The most common emulsions are O / W and W / O emulsions. More rare forms of administration are multiple emulsions, i.e. those which themselves contain droplets of a further dispersed phase in the droplets of the dispersed (or discontinuous) phase, e.g. W / O / W emulsions and O / W / O emulsions.
Um die Metastabilität von Emulsionen gewährleisten zu können, sind in der Regel grenzflächenaktive Substanzen, also Emulgatoren, nötig.In order to guarantee the metastability of emulsions, surface-active substances, i.e. emulsifiers, are generally necessary.
Es ist möglich, etnulgatorfreie Zubereitungen herzustellen, welche beispielsweise in einer wäßrigen Phase dispergierte Öltröpfchen, ähnlich einer O/W-Emulsion, aufweisen. Voraussetzung dafür kann sein, daß die kontinuierliche wäßrige Phase ein die dispergierte Phase stabilisierendes Gelgerüst aufweist und andere Umstände mehr. Solche Systeme werden gelegentlich Hydrodispersionen oder Oleodispersionen genannt, je nachdem, welches die disperse und welches die kontinuierliche Phase darstellt.It is possible to prepare emulsifier-free preparations which, for example, have oil droplets dispersed in an aqueous phase, similar to an O / W emulsion. A prerequisite for this may be that the continuous aqueous phase has a gel structure stabilizing the dispersed phase and other circumstances more. Such systems are sometimes called hydrodispersions or oleodispersions, depending on which is the disperse phase and which is the continuous phase.
Übliche, und sich gerade in neuerer Zeit immer weiter verbreitende kosmetische und dermatologische Zubereitungsformen sind Gele.Gels are the usual and increasingly popular cosmetic and dermatological preparation forms.
Im technischen Sinne werden unter Gelen verstanden: Relativ formbeständige, leicht verformbare disperse Systeme aus zumindest zwei Komponenten, welche in der Regel aus einem - meist festen - kolloid zerteilten Stoff aus langkettigen Molekülgruppierungen (z.B. Gelatine, Kieselsäure, Polysaccharide) als Gerüstbildner und einem flüssigen Dispersionsmittel (z.B. Wasser) bestehen. Der kolloidal zerteilte Stoff wird oft als Verdickungs- oder Geliermittel bezeichnet. Er bildet ein räumliches Netzwerk im Dispersionsmittel, wobei einzelne kolloidal vorliegende Partikel über elektrostatische Wechselwirkung mit-In the technical sense, gels are understood to mean: Relatively dimensionally stable, easily deformable disperse systems composed of at least two components, which as a rule consist of a - usually solid - colloidally divided substance made up of long-chain molecular groups (e.g. gelatin, silica, polysaccharides) as a scaffold and a liquid dispersant (e.g. water) exist. The colloidally divided substance is often referred to as a thickening or gelling agent. It forms a spatial network in the dispersant, whereby individual colloidal particles are involved via electrostatic interaction.
TÄTIGINGSKOPIE
einander mehr oder weniger fest verknüpft sein können. Das Dispersionsmittel, welches das Netzwerk umgibt, zeichnet sich durch elektrostatische Affinität zum Geliermittel aus, d.h., ein vorwiegend polares (insbesondere: hydrophiles) Geliermittel geliert vorzugsweise ein polares Dispersionsmittel (insbesondere: Wasser), wohingegen ein vorwiegend unpolares Geliermittel vorzugsweise unpolare Dispersionsmittel geliert.TÄTIGINGSKOPIE can be more or less firmly linked. The dispersing agent that surrounds the network is characterized by electrostatic affinity for the gelling agent, ie a predominantly polar (in particular: hydrophilic) gelling agent preferably gels a polar dispersing agent (in particular: water), whereas a predominantly non-polar gelling agent preferably gels non-polar dispersing agent.
Starke elektrostatische Wechselwirkungen, welche beispielsweise in Wasserstoffbrückenbindungen zwischen Geliermittel und Dispersionsmittel, aber auch zwischen Dispersionsmittelmolekülen untereinander verwirklicht sind, können zu starker Vernetzung auch des Dispersionsmittels führen. Hydrogele können zu fast 100 % aus Wasser bestehen (neben beispielsweise ca. 0,2 - 1 ,0 % eines Geliermittels) und dabei durchaus feste Konsistenz besitzen. Der Wasseranteil liegt dabei in eisähnlichen Strukturelementen vor, so daß Gele daher ihrer Namensherkunft [aus lat. „gelatum" = „Gefrorenes" über den alchimistischen Ausdruck „gelatina" (16. Jhdt.) für nhdt. „Gelatine"] durchaus gerecht werden.Strong electrostatic interactions, which are realized, for example, in hydrogen bonds between the gelling agent and the dispersing agent, but also between the dispersing agent molecules with one another, can also lead to strong crosslinking of the dispersing agent. Hydrogels can consist of almost 100% water (in addition to, for example, about 0.2-1.0% of a gelling agent) and have a firm consistency. The water content is in ice-like structural elements, so that gels therefore do justice to their origin [from Latin "gelatum" = "frozen" via the alchemical expression "gelatina" (16th century) for nhdt. "Gelatin"].
In der kosmetischen und pharmazeutischen Galenik sind ferner auch Lipogele und Oleo- gele (aus Wachsen, Fetten und fetten Ölen) sowie Carbogele (aus Paraffin oder Pe- trolatum) geläufig. In der Praxis unterscheidet man Oleogele, welche praktisch wasserfrei vorliegen, Hydrogele, welche praktisch fettfrei sind. Meistens sind Gele durchsichtig. In der kosmetischen bzw. pharmazeutischen Galenik zeichnen sich Gele in aller Regel durch halbfeste, oft fließfähige Konsistenz aus.Lipogels and oleols (from waxes, fats and fatty oils) and carbogels (from paraffin or petrolatum) are also common in cosmetic and pharmaceutical galenics. In practice, a distinction is made between oleogels, which are practically anhydrous, and hydrogels, which are practically fat-free. Most of the time, gels are transparent. In cosmetic or pharmaceutical galenics, gels are usually characterized by a semi-solid, often flowable consistency.
Ferner sind sogenannte Tensidgele gebräuchliche Zubereitungen des Standes der Technik. Darunter versteht man Systeme, die neben Wasser eine hohe Konzentration an E- mulgatoren aufweisen, typischerweise mehr als ca. 25 Gew.-%, bezogen auf die Gesamtzusammensetzung. Solubilisiert man in diese Tensidgele, fachsprachlich auch „surfactant gels" genannt, Ölkomponenten, werden Mikroemulsionsgele erhalten, welche auch als „ringing gels" bezeichnet werden. Durch Zusatz von nichtionischen Emulgatoren, beispielsweise Alkylpolyglycosiden, lassen sich kosmetisch elegantere Mikroemulsionsgele erhalten.So-called surfactant gels are also common preparations of the prior art. This is understood to mean systems which, in addition to water, have a high concentration of emulsifiers, typically more than about 25% by weight, based on the overall composition. If oil components are solubilized in these surfactant gels, also called “surfactant gels” in technical terms, microemulsion gels are obtained, which are also referred to as “ringing gels”. By adding nonionic emulsifiers, for example alkyl polyglycosides, it is possible to obtain cosmetically more elegant microemulsion gels.
Die Kühlwirkung kosmetischer Zubereitungen beruht bisher auf zwei Grundprinzipien:
Einsatz von Komponenten die sich nach topischer Applikation gasförmig verflüchtigen und die hierfür erforderlich Energiemenge, die sog. Verdampfungsenthalpie, zu einem Großteil der Hautoberfläche entnehmen. Es werden daher in entsprechenden nicht okklusiven Kosmetika geeignete flüssige Komponenten eingesetzt. Als besonders geeignet hat sich hier Ethanol erwiesen, daneben zeigen Formulierungen mit hohem Wassergehalt ebenfalls eine deutliche Kühlwirkung.The cooling effect of cosmetic preparations has so far been based on two basic principles: Use of components which volatilize in gaseous form after topical application and remove the required amount of energy, the so-called enthalpy of vaporization, for the most part from the skin surface. Suitable liquid components are therefore used in corresponding non-occlusive cosmetics. Ethanol has proven to be particularly suitable here, and formulations with a high water content also have a clear cooling effect.
Einsatz von sogenannten Cooling Agents, die mit den Wärmerezeptoren der Haut in Wechselwirkung treten und somit ein Kälteempfinden auslösen, ohne eine meßbare physikalische Abkühlung zu generieren. Hierfür kommen insbesondere Menthol und diverse Mentholderivate (Frescolate, Physcool, Questice L, etc.) zum Einsatz. Insbesondere hohe Ethanolgehalte sowie Menthol und seine Derivate sind, neben dem irritativen Potential, insbesondere aufgrund ihres deutlichen Eigengeruchs für zahlreiche Einsatzzwecke unter olfaktorischen Gesichtspunkten nicht geeignet. Häufig genug bewirken solche Substanzen darüberhinaus gleichzeitig eine Durchblutungssteigerung, die im Gegenteil ein Wärmegefühl hervorruft.Use of so-called cooling agents that interact with the skin's heat receptors and thus trigger a feeling of cold without generating a measurable physical cooling. In particular menthol and various menthol derivatives (Frescolate, Physcool, Questice L, etc.) are used for this. In particular, high ethanol contents as well as menthol and its derivatives are not suitable for numerous applications from an olfactory point of view, in addition to their irritative potential, in particular because of their distinct odor. Frequently enough, such substances also cause an increase in blood circulation, which on the contrary creates a feeling of warmth.
In der Literatur werden beispielsweise ionische Verbindungen, insbesondere Ammoniumsalze, als kühlende Agenzien beschrieben. Als kühlende Zubereitungen werden auch verbreitet isopropanolische Gele mit Campher- und Mentholzusatz angewandt.In the literature, for example, ionic compounds, especially ammonium salts, are described as cooling agents. Isopropanolic gels with camphor and menthol additives are also widely used as cooling preparations.
Die Anwendung dieser Substanzen, namentlich auf gereizter Haut, ist jedenfalls problematisch. Darüber hinaus sind viele dieser Verbindungen schlecht wasserlöslich. Ihre Verwendung ist folglich auf wenige Kosmetika und Der atika beschränkt.The use of these substances, especially on irritated skin, is problematic in any case. In addition, many of these compounds are poorly water-soluble. Their use is therefore limited to a few cosmetics and cosmetics.
Aufgabe der vorliegenden Erfindung war es also, pflegende kosmetische und medizinische Zubereitungen zur Verfügung zu stellen, die nicht die Nachteile des Standes der Technik haben, insbesondere solche, welche, auf der Haut oder Schleimhäuten angewandt, befeuchtend und/oder kühlend wirken.The object of the present invention was therefore to provide nourishing cosmetic and medical preparations which do not have the disadvantages of the prior art, in particular those which, when applied to the skin or mucous membranes, have a moisturizing and / or cooling effect.
Die DE 43 12 656 beschreibt die Verwendung kosmetisch oder pharmazeutisch unbedenklicher Substanzen mit positiver Lösungsenthalpie in kosmetischen oder medizinischen topischen Zubereitungen, dadurch gekennzeichnet, daß die Substanz oder die Substanzen in den Zubereitungen in einem weitgehend wasserfreien Medium vorliegenDE 43 12 656 describes the use of cosmetically or pharmaceutically acceptable substances with a positive enthalpy of solution in cosmetic or medical topical preparations, characterized in that the substance or substances are present in the preparations in a largely anhydrous medium
BE ÄTIGINGSKOPI
und/oder durch eine stoffliche Barriere von einem wasserhaltigen Medium abgeschirmt werden.BE ÄTIGINGSKOPI and / or be shielded from a water-containing medium by a material barrier.
Obwohl dieses Vorgehen grundsätzlich zu kosmetisch befriedigenden Zubereitungen führen kann, sind diese jedoch galenisch äußerst aufwendig herzustellen.Although this procedure can fundamentally lead to cosmetically satisfactory preparations, these are, however, extremely complex to produce galenically.
Es war also die Aufgabe, der vorliegenden Erfindung, den Übelständen des Standes der Technik abzuhelfen und kühlende kosmetische oder dermatologische Zubereitungen zur Verfügung zu stellen, welche einfach herzustellen sind, keine Reizwirkung auf Haut oder Schleimhäute ausüben sowie bei bestimmungsgemäßer Anwendung angenehme Kühlung spenden.It was therefore the object of the present invention to remedy the shortcomings of the prior art and to provide cooling cosmetic or dermatological preparations which are simple to prepare, have no irritating effect on the skin or mucous membranes and, when used as intended, provide pleasant cooling.
Der Phasenübergang vom festen in den flüssigen Zustand ist bei zahlreichen Verbindungen ebenfalls durch das Auftreten von Umwandlungswärmen gekennzeichnet. Endotherme Schmelzvorgänge finden unter Aufnahme von Energie statt, die der Umgebung entstammt und dort somit zu einer Temperaturerniedrigung führt.The phase transition from the solid to the liquid state is also characterized by the occurrence of heat of transformation in numerous compounds. Endothermic melting processes take place with the absorption of energy that originates from the environment and thus leads to a lowering of the temperature there.
Es war jedoch erstaunlich und für den Fachmann nicht vorhersehbar, daß kühlende kosmetische oder medizinische topische Zubereitungen, gekennzeichnet durch einen Gehalt an einer oder mehreren Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, wobei diese Substanz oder Substanzen in den Zubereitungen in festem Zustand vorliegen.However, it was surprising and unforeseeable for the person skilled in the art that cooling cosmetic or medical topical preparations, characterized by a content of one or more substances, the melting point or melting interval of which is chosen in the range between 28 ° C. and 40 ° C., and the positive enthalpy of fusion have, which substance or substances are present in the preparations in the solid state.
Erfindungsgemäß ist ferner die Verwendung einer oder mehrerer Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40According to the invention, the use of one or more substances, their melting point or melting interval in the range between 28 ° C and 40 is also
°C gewählt wird, und die positive Schmelzenthalpie aufweisen, zur Herstellung kühlend wirkender kosmetischer oder medizinischer topischer Zubereitungen,° C is selected and which have a positive enthalpy of fusion for the production of cooling cosmetic or medical topical preparations,
N
wobei diese Substanz oder Substanzen in den Zubereitungen in festem Zustand vorliegen.N this substance or substances are present in the preparations in the solid state.
Diese erfindungsgemäßen Zubereitungen entfalten ihre kühlende Wirkung innerhalb eines breiten Einsatzkonzentrationsbereichs der zugrundeliegenden Substanzen, beispielsweise 0,5 - 50 Gew.-%, vorteilhaft 1 - 20 Gew.-% dieser Substanzen, bezogen auf das Gesamtgewicht der Zubereitungen. Sie sind einfach zu formulieren und stellen keine großen Anforderungen an Herstellungsvorgänge.These preparations according to the invention develop their cooling effect within a wide range of use concentrations of the underlying substances, for example 0.5-50% by weight, advantageously 1-20% by weight, based on the total weight of the preparations. They are easy to formulate and make no great demands on manufacturing processes.
Werden, wie es erfindungsgemäß von besonderem Vorteil ist, lipophile Substanzen gewählt, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C liegt, und die positive Schmelzenthalpie aufweisen, so sind insbesondere ausgeprägt hydrophile kosmetische oder dermatologische Grundlagen hierfür in Betracht, in denen die Substanz oder als die Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C liegt, und die positive Schmelzenthalpie aufweisen, dann besonders bevorzugterweise feinpartikulär suspendiert vorliegen, beispielsweise in wäßrigen Gelformulierungen.If, as is particularly advantageous according to the invention, lipophilic substances are selected whose melting point or melting interval is in the range between 28 ° C and 40 ° C and which have a positive enthalpy of fusion, then in particular pronounced hydrophilic cosmetic or dermatological bases are to be considered to which the substance or as the substances whose melting point or melting interval is in the range between 28 ° C. and 40 ° C. and which have a positive enthalpy of fusion are then particularly preferably in particulate suspension, for example in aqueous gel formulations.
Insbesondere vorteilhafte Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, werden gewählt aus der Gruppe der lipophilen Substanzen, insbesondere der Ester der C14-Cι8 Fettsäuren, mit niedermolekularen (C1 - C5) Alkoholen, der Fettalkohole C8 - C22, der verzweigten oder unverzweigten Fettsäuren, der Kohlenwasserstoffe C16 - C22.Particularly advantageous substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C and which have a positive melting enthalpy are selected from the group of lipophilic substances, in particular the esters of C 14 -C 8 fatty acids, with low molecular weight ( C 1 - C 5 ) alcohols, the fatty alcohols C 8 - C 22 , the branched or unbranched fatty acids, the hydrocarbons C 16 - C 22 .
Besonders bevorzugt im Sinne der vorliegenden Erfindung ist das Methylpalmitat.Methyl palmitate is particularly preferred for the purposes of the present invention.
Diesen Formulierungen können gegebenenfalls darüber hinaus noch weitere kühlende Wirkstoffe, beispielsweise Menthol oder Mentholderivate zur sensorischen Modifizierung oder zur Verstärkung des Cooling-Effekts zugesetzt werden.In addition, further cooling active ingredients, for example menthol or menthol derivatives, can be added to these formulations for sensory modification or for enhancing the cooling effect.
Die Substanz oder die Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufwei-The substance or substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C and the positive melting enthalpy
BESTÄTIGINGSKOPIE
sen, werden im Rahmen der vorliegenden Offenbarung auch kollektiv als erfindungsgemäßer Wirkstoff bezeichnet bzw. mit ähnlichen Synonymen versehen.BESTÄTIGINGSKOPIE sen, are also collectively referred to in the context of the present disclosure as the active ingredient according to the invention or provided with similar synonyms.
Es ist erfindungsgemäß insbesondere äußerst vorteilhaft, den erfindungsgemäß verwendeten Wirkstoff bzw. kosmetische oder topische dermatologische Zubereitungen mit einem wirksamen Gehalt an erfindungsgemäß verwendetem Wirkstoff zur kosmetischen oder dermatologischen Behandlung oder Prophylaxe unerwünschter Hautzustände zu verwenden.It is particularly advantageous according to the invention to use the active ingredient or cosmetic or topical dermatological preparations used according to the invention with an effective content of active ingredient used according to the invention for cosmetic or dermatological treatment or prophylaxis of undesirable skin conditions.
Erfindungsgemäß können Zubereitungen, welche die erfindungsgemäßen Wirkstoffkombinationen enthalten, übliche Antioxidantien eingesetzt werden.According to the invention, preparations containing the active compound combinations according to the invention, customary antioxidants can be used.
Vorteilhaft werden die Antioxidantien gewählt aus der Gruppe bestehend aus Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z.B. Uro- caninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z.B. Anserin), Carotinoide, Carotine (z.B. α-Carotin, ß-Carotin, Lycopin) und deren Derivate, Liponsäure und deren Derivate (z.B. Dihydroliponsäure), Au- rothioglucose, Propylthiouracil und andere Thiole (z.B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulf- oximinverbindungen (z.B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsul- fone, Penta-, Hexa-, Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z.B. pmol bis μmol/kg), ferner (Metall)-Chelatoren (z.B. α-Hydroxyfettsäuren, Palmitin- säure, Phytinsäure, Lactoferrin), -Hydroxysäuren (z.B. Citronensäure, Milchsäure, Apfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ-Linolensäure, Linol- säure, Ölsäure), Folsäure und deren Derivate, Alanindiessigsäure, Flavonoide, Polyphe- nole, Catechine, Vitamin C und Derivate (z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascorbylacetat), Tocopherole und Derivate (z.B. Vitamin-E-acetat), sowie Koni- ferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, Ferulasäure und deren Derivate, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihy- droguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose undThe antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L- Carnosine and its derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione , Cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, buthioninsulfones, penta-, hexa-, hexa- foximin) in very low tolerable doses (e.g. pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA , EGTA and its derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, alanine diacetic acid, flavonoids, polyphenols, catechins, vitamin C and derivatives (eg ascorbyl palmitate, Mg-ascorbyl phosphate , Ascorbylacetate), tocopherols and derivatives (eg vitamin E acetate), as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydonroxy acid, trihydonroxy acid, trihydonroxy acid, trihydonroxy acid, trihydonroxy Mannose and
BESTÄTIGINGSKOPIE
deren Derivate, Zink und dessen Derivate (z.B. ZnO, ZnSO4) Selen und dessen Derivate (z.B. Selenmethionin), Stilbene und deren Derivate (z.B. Stilbenoxid, Trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.BESTÄTIGINGSKOPIE their derivatives, zinc and their derivatives (for example ZnO, ZnSO 4 ) selenium and their derivatives (for example selenium methionine), stilbenes and their derivatives (for example stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides) , Nucleosides, peptides and lipids) of these active ingredients.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 - 20 Gew.-%, insbesondere 1 - 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 1 to 10% by weight, based on the total weight of the preparation ,
Die Prophylaxe bzw. die kosmetische oder dermatologische Behandlung mit dem erfindungsgemäß verwendeten Wirkstoff bzw. mit den kosmetischen oder topischen dermatologischen Zubereitungen mit einem wirksamen Gehalt an erfindungsgemäß verwendetem Wirkstoff erfolgt in der üblichen Weise, und zwar dergestalt, daß der erfindungsgemäß verwendete Wirkstoff bzw. die kosmetischen oder topischen dermatologischen Zubereitungen mit einem wirksamen Gehalt an erfindungsgemäß verwendetem Wirkstoff auf die betroffenen Hautstellen aufgetragen wird.The prophylaxis or the cosmetic or dermatological treatment with the active ingredient used according to the invention or with the cosmetic or topical dermatological preparations with an effective content of active ingredient used according to the invention is carried out in the usual way, namely in such a way that the active ingredient used according to the invention or the cosmetic or topical dermatological preparations with an effective content of active ingredient used according to the invention is applied to the affected skin areas.
Vorteilhaft kann der erfindungsgemäß verwendete Wirkstoff eingearbeitet werden in übliche kosmetische und dermatologische Zubereitungen, welche in verschiedenen Formen vorliegen können. So können sie z.B. eine Lösung, eine Emulsion vom Typ Wasser-in-ÖI (W/O) oder vom Typ Öl-in-Wasser (O/W), oder eine multiple Emulsionen, beispielsweise vom Typ Wasser-in-ÖI-in-Wasser (W/O/W) oder Öl-in-Wasser-in-ÖI (O/W/O), eine Hydro- dispersion oder Lipodispersion, ein Gel, einen festen Stift oder auch ein Aerosol darstellen.The active ingredient used according to the invention can advantageously be incorporated into customary cosmetic and dermatological preparations, which can be in various forms. So you can e.g. a solution, an emulsion of the type water-in-oil (W / O) or of the type oil-in-water (O / W), or a multiple emulsions, for example of the type water-in-oil-in-water (W / O / W) or oil-in-water-in-oil (O / W / O), a hydro-dispersion or lipodispersion, a gel, a solid stick or an aerosol.
Erfindungsgemäße Emulsionen im Sinne der vorliegenden Erfindung, z.B. in Form einer Creme, einer Lotion, einer kosmetischen Milch sind vorteilhaft und enthalten z.B. Fette, Öle, Wachse und/oder andere Fettkörper, sowie Wasser und einen oder mehrere Emul- gatoren, wie sie üblicherweise für einen solchen Typ der Formulierung verwendet werden.Emulsions according to the invention in the sense of the present invention, e.g. in the form of a cream, a lotion, a cosmetic milk are advantageous and contain e.g. Fats, oils, waxes and / or other fat bodies, as well as water and one or more emulsifiers, as are usually used for such a type of formulation.
Es ist auch möglich und vorteilhaft im Sinne der vorliegenden Erfindung, den erfindungsgemäß verwendeten Wirkstoff in wäßrige Systeme bzw. Tensidzubereitungen zur Reinigung der Haut und der Haare einzufügen.It is also possible and advantageous for the purposes of the present invention to insert the active ingredient used according to the invention in aqueous systems or surfactant preparations for cleaning the skin and hair.
BESTÄTIGINGSKOPIE
Es ist dem Fachmanne natürlich bekannt, daß anspruchsvolle kosmetische Zusammensetzungen zumeist nicht ohne die üblichen Hilfs- und Zusatzstoffe denkbar sind. Darunter zählen beispielsweise Konsistenzgeber, Füllstoffe, Parfüm, Farbstoffe, Emulgatoren, zusätzliche Wirkstoffe wie Vitamine oder Proteine, Lichtschutzmittel, Stabilisatoren, Insek- tenrepellentien, Alkohol, Wasser, Salze, antimikrobiell, proteolytisch oder keratolytisch wirksame Substanzen usw.BESTÄTIGINGSKOPIE It is of course known to the person skilled in the art that sophisticated cosmetic compositions are usually inconceivable without the customary auxiliaries and additives. These include, for example, consistency agents, fillers, perfumes, dyes, emulsifiers, additional active ingredients such as vitamins or proteins, light stabilizers, stabilizers, insect repellents, alcohol, water, salts, antimicrobial, proteolytic or keratolytically active substances, etc.
Mutatis mutandis gelten entsprechende Anforderungen an die Formulierung medizinischer Zubereitungen.Mutatis mutandis, corresponding requirements apply to the formulation of medical preparations.
Medizinische topische Zusammensetzungen im Sinne der vorliegenden Erfindung enthalten in der Regel ein oder mehrere Medikamente in wirksamer Konzentration. Der Einfachheit halber wird zur sauberen Unterscheidung zwischen kosmetischer und medizinischer Anwendung und entsprechenden Produkten auf die gesetzlichen Bestimmungen der Bundesrepublik Deutschland verwiesen (z.B. Kosmetikverordnung, Lebensmittel- und Arzneimittelgesetz).Medical topical compositions in the sense of the present invention generally contain one or more medicaments in an effective concentration. For the sake of simplicity, reference is made to the legal provisions of the Federal Republic of Germany (e.g. cosmetics regulation, food and drug law) for a clear distinction between cosmetic and medical use and corresponding products.
Es ist dabei ebenfalls von Vorteil, den erfindungsgemäß verwendeten Wirkstoff als Zusatzstoff zu Zubereitungen zu geben, die bereits andere Wirkstoffe für andere Zwecke enthalten.It is also advantageous to add the active ingredient used according to the invention as an additive to preparations which already contain other active ingredients for other purposes.
Entsprechend können kosmetische oder topische dermatologische Zusammensetzungen im Sinne der vorliegenden Erfindung, je nach ihrem Aufbau, beispielsweise verwendet werden als Hautschutzcreme, Reinigungsmilch, Sonnenschutzlotion, Nährcreme, Tagesoder Nachtcreme usw. Es ist gegebenenfalls möglich und vorteilhaft, die erfindungsgemäßen Zusammensetzungen als Grundlage für pharmazeutische Formulierungen zu verwenden.Accordingly, cosmetic or topical dermatological compositions within the meaning of the present invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritional cream, day or night cream, etc. It may be possible and advantageous to add the compositions according to the invention as the basis for pharmaceutical formulations use.
Günstig sind gegebenenfalls auch solche kosmetischen und dermatologischen Zubereitungen, die in der Form eines Sonnenschutzmittels vorliegen. Vorzugsweise enthalten diese neben dem erfindungsgemäß verwendeten Wirkstoff zusätzlich mindestens eine UVA-Filtersubstanz und/oder mindestens eine UVB-Filtersubstanz und/oder mindestens ein anorganisches Pigment.
Es ist aber auch vorteilhaft im Sinne der vorliegenden Erfindungen, solche kosmetischen und dermatologischen Zubereitungen zu erstellen, deren hauptsächlicher Zweck nicht der Schutz vor Sonnenlicht ist, die aber dennoch einen Gehalt an UV-Schutzsubstanzen enthalten. So werden beispielsweise in Tagescremes gewöhnlich UV-A- bzw. UV-B- Filtersubstanzen eingearbeitet.If appropriate, cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable. In addition to the active ingredient used according to the invention, these preferably additionally contain at least one UVA filter substance and / or at least one UVB filter substance and / or at least one inorganic pigment. However, it is also advantageous in the sense of the present inventions to create cosmetic and dermatological preparations whose main purpose is not protection against sunlight, but which nevertheless contain UV protection substances. For example, UV-A or UV-B filter substances are usually incorporated into day creams.
Vorteilhaft können erfindungsgemäße Zubereitungen Substanzen enthalten, die UV- Strahlung im UVB-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z.B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 bis 6 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitungen.Preparations according to the invention can advantageously contain substances which absorb UV radiation in the UVB range, the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the preparations.
Die UVB-Filter können öllöslich oder wasserlöslich sein. Als öllösliche Substanzen sind z.B. zu nennen:The UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
3-Benzylidencampher und dessen Derivate, z.B. 3-(4-Methylbenzyliden)campher,3-benzylidene camphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor,
4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2- ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Meth- oxyzimtsäureisopentylester;Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
Ester der Salicylsäure, vorzugsweise Salicylsäure(2-ethylhexyl)ester, Salicylsäure-Esters of salicylic acid, preferably salicylic acid (2-ethylhexyl) ester, salicylic acid
(4-isopropylbenzyl)ester, Salicylsäurehomomenthylester;(4-isopropylbenzyl) ester, salicylic acid homomethyl ester;
Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophe- non;Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethyl- hexyl)ester;Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;
2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1 ,3,5-triazin.2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine.
Als wasserlösliche Substanzen sind vorteilhaft:The following are advantageous as water-soluble substances:
2-Phenylbenzimidazol-5-sulfonsäure und deren Salze, z.B. Natrium-, Kalium- oder2-phenylbenzimidazole-5-sulfonic acid and its salts, e.g. Sodium, potassium or
Triethanolammonium-Salze,Triethanolammonium salts,
Sulfonsäure-Derivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxy- benzophenon-5-sulfonsäure und ihre Salze;Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid and their salts;
Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornyliden-Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornyliden-
BESTÄTIGSNGSKOPIE
methyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und ihre Salze.BESTÄTIGSNGSKOPIE methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their salts.
Die Liste der genannten UVB-Filter, die erfindungsgemäß Verwendung finden können, soll selbstverständlich nicht limitierend sein.The list of UVB filters mentioned, which can be used according to the invention, is of course not intended to be limiting.
Gegenstand der Erfindung ist auch die Kombination eines erfindungsgemäßen UVA-Fil- ters mit einem UVB-Filter bzw. eine erfindungsgemäßes kosmetische oder dermatologische Zubereitung, welche auch einen UVB-Filter enthält.The invention also relates to the combination of a UVA filter according to the invention with a UVB filter or a cosmetic or dermatological preparation according to the invention which also contains a UVB filter.
Es kann auch von Vorteil sein, in erfindungsgemäßen Zubereitungen UVA-Filter einzusetzen, die üblicherweise in kosmetischen und/oder dermatologischen Zubereitungen enthalten sind. Bei solchen Filtersubstanzen handelt es sich vorzugsweise um Derivate des Dibenzoylmethans, insbesondere um 1-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)- propan-1 ,3-dion und um 1-Phenyl-3-(4'-isopropylphenyl)propan-1 ,3-dion. Auch Zubereitungen, die diese Kombinationen enthalten, sind Gegenstand der Erfindung. Es können die gleichen Mengen an UVA-Filtersubstanzen verwendet werden, welche für UVB- Filtersubstanzen genannt wurden.It can also be advantageous to use UVA filters in the preparations according to the invention, which are usually contained in cosmetic and / or dermatological preparations. Such filter substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- ( 4'-isopropylphenyl) propane-1,3-dione. Preparations containing these combinations are also the subject of the invention. The same amounts of UVA filter substances that were mentioned for UVB filter substances can be used.
Kosmetische und/oder dermatologische Zubereitungen im Sinne der vorliegenden Erfindung können auch anorganische Pigmente enthalten, die üblicherweise in der Kosmetik zum Schütze der Haut vor UV-Strahlen verwendet werden. Dabei handelt es sich um Oxide des Titans, Zinks, Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums, Cers und Mischungen davon, sowie Abwandlungen, bei denen die Oxide die aktiven Agentien sind. Besonders bevorzugt handelt es sich um Pigmente auf der Basis von Titandioxid. Es können die für die vorstehenden Kombinationen genannten Mengen verwendet werden.Cosmetic and / or dermatological preparations in the sense of the present invention can also contain inorganic pigments which are usually used in cosmetics to protect the skin from UV rays. These are oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as modifications in which the oxides are the active agents. It is particularly preferred to use pigments based on titanium dioxide. The amounts given for the above combinations can be used.
Die erfindungsgemäßen kosmetischen Zubereitungen können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen verwendet werden, z.B. Konservierungsmittel, Bakterizide, desodorierend wirkende Substanzen, Antitranspirantien, Insektenrepellentien, Vitamine, Mittel zum Verhindern des Schäumens, Farbstoffe, Pigmente mit färbender Wirkung, Verdickungsmittel, weichmachende Substanzen, anfeuchtende und/oder feuchthaltende Substanzen, Fette, Öle, Wachse oder andere übliche Be-
standteile einer kosmetischen Formulierung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösungsmittel oder Silikonderivate.The cosmetic preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, for example preservatives, bactericides, deodorising substances, antiperspirants, insect repellents, vitamins, agents for preventing foaming, dyes, pigments with a coloring effect, thickeners, softening substances , moisturizing and / or moisturizing substances, fats, oils, waxes or other usual substances components of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
Vorteilhaft können erfindungsgemäße Zubereitungen außerdem Substanzen enthalten, die UV-Strahlung im UVB-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z.B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 ,0 bis 6,0 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar dienen.Preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UVB range, the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1.0 to 6.0% by weight, based on the total weight of the preparations, in order to prepare cosmetic preparations To provide that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair.
Enthalten die erfindungsgemäßen Zubereitungen UVB-Filtersubstanzen, können diese öl- löslich oder wasserlöslich sein. Erfindungsgemäß vorteilhafte öllösliche UVB-Filter sind z.B.:If the preparations according to the invention contain UVB filter substances, they can be oil-soluble or water-soluble. Oil-soluble UVB filters which are advantageous according to the invention are, for example:
3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-
Benzylidencampher;benzylidenecamphor;
4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2- ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Me- thoxyzimtsäureisopentylester;Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
Ester der Salicylsäure, vorzugsweise Salicylsäure(2-ethylhexyl)ester, Salicylsäu- re(4-isopropylbenzyl)ester, Salicylsäurehomomenthylester,Esters of salicylic acid, preferably salicylic acid (2-ethylhexyl) ester, salicylic acid (4-isopropylbenzyl) ester, salicylic acid homomethyl ester,
Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophe- non;Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethyl- hexyl)ester,Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester,
2,4,6-Trianilino-(p-carbo-2'-ethyl-1 '-hexyloxy)-1 ,3,5-triazin.2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine.
Vorteilhafte wasserlösliche UVB-Filter sind z.B.:Advantageous water-soluble UVB filters include:
Salze der 2-Phenylbenzimidazol-5-sulfonsäure wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz, sowie die Sulfonsäure selbst;Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself;
BESTÄTIGΪNGSKOPIE
Sulfonsäure-Derivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxy- benzophenon-5-sulfonsäure und ihre Salze;BESTÄTIGΪNGSKOPIE Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid and their salts;
Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornyliden- methyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und ihre Salze sowie das 1 ,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol und dessen Salze (die entprehenden 10-Sulfato-verbindungen, beispielsweise das entsprechende Natrium-, Kalium- oder Triethanolammonium-Salz), auch als Benzol-1 ,4- di(2-oxo-3-bornylidenmethyl-10-Sulfonsäure bezeichnetSulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and their salts and 1,4-di (2-oxo-10-sulfo 3-bornylidene methyl) -benzene and its salts (the corresponding 10-sulfato compounds, e.g. the corresponding sodium, potassium or triethanolammonium salt), also as benzene-1,4-di (2-oxo-3-bornylidene methyl) Designated 10-sulfonic acid
Die Liste der genannten UVB-Filter, die in Kombination mit den erfindungsgemäßen Wirkstoffkombinationen verwendet werden können, soll selbstverständlich nicht limitierend sein.The list of UVB filters mentioned, which can be used in combination with the active compound combinations according to the invention, is of course not intended to be limiting.
Es kann auch von Vorteil sein, UVA-Filter einzusetzen, die üblicherweise in kosmetischen Zubereitungen enthalten sind. Bei diesen Substanzen handelt es sich vorzugsweise um Derivate des Dibenzoylmethans, insbesondere um 1-(4'-tert.Butylphenyl)-3-(4'-methoxy- phenyl)propan-1 ,3-dion und um 1-Phenyl-3-(4'-isopropylphenyl)propan-1 ,3-dion. Es können die für die UVB-Kombination verwendeten Mengen eingesetzt werden.It can also be advantageous to use UVA filters that are usually contained in cosmetic preparations. These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. The quantities used for the UVB combination can be used.
Erfindungsgemäße kosmetische und dermatologische Zubereitungen enthalten vorteilhaft außerdem anorganische Pigmente auf Basis von Metalloxiden und/oder anderen in Wasser schwerlöslichen oder unlöslichen Metallverbindungen, insbesondere der Oxide des Titans (Ti02), Zinks (ZnO), Eisens (z.B. Fe203), Zirkoniums (Zr02), Siliciums (Si02), Mangans (z.B. MnO), Aluminiums (Al203), Cers (z.B. Ce203), Mischoxiden der entsprechenden Metalle sowie Abmischungen aus solchen Oxiden. Besonders bevorzugt handelt es sich um Pigmente auf der Basis von Ti02.Cosmetic and dermatological preparations according to the invention advantageously also contain inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular the oxides of titanium (Ti0 2 ), zinc (ZnO), iron (eg Fe 2 0 3 ), zirconium (Zr0 2 ), silicon (Si0 2 ), manganese (eg MnO), aluminum (Al 2 0 3 ), cerium (eg Ce 2 0 3 ), mixed oxides of the corresponding metals and mixtures of such oxides. It is particularly preferred to use pigments based on TiO 2 .
Es ist besonders vorteilhaft im Sinne der vorliegenden Erfindung, wenngleich nicht zwingend, wenn die anorganischen Pigmente in hydrophober Form vorliegen, d.h., daß sie oberflächlich wasserabweisend behandelt sind. Diese Oberflächenbehandlung kann darin bestehen, daß die Pigmente nach an sich bekannten Verfahren mit einer dünnen hydrophoben Schicht versehen werden.It is particularly advantageous within the meaning of the present invention, although not mandatory, if the inorganic pigments are in hydrophobic form, i.e. that they have been treated to be water-repellent on the surface. This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer by methods known per se.
BESTÄTIGINGSKOPIE
Eines solcher Verfahren besteht beispielsweise darin, daß die hydrophobe Oberflächenschicht nach einer Rektion gemäßBESTÄTIGINGSKOPIE One such method consists, for example, in that the hydrophobic surface layer after a rectification
n TiO2 + m (RO)3 Si-R* -> n Ti02 (oberfl.)n TiO 2 + m (RO) 3 Si-R * -> n Ti0 2 (surface)
erzeugt wird, n und m sind dabei nach Belieben einzusetzende stöchiometrische Parameter, R und R' die gewünschten organischen Reste. Beispielsweise in Analogie zu DE- OS 33 14 742 dargestellte hydrophobisierte Pigmente sind von Vorteil.is generated, n and m are stoichiometric parameters to be used at will, R and R 'are the desired organic radicals. For example, hydrophobized pigments shown in analogy to DE-OS 33 14 742 are advantageous.
Vorteilhafte Ti02-Pigmente sind beispielsweise unter den Handelsbezeichnungen MT 100 T von der Firma TAYCA, ferner M 160 von der Firma Kemira sowie T 805 von der Firma Degussa erhältlich.Advantageous Ti0 2 pigments are available, for example, under the trade names MT 100 T from TAYCA, M 160 from Kemira and T 805 from Degussa.
Erfindungsgemäße Zubereitungen können, zumal wenn kristalline oder mikrokristalline Festkörper, beispielsweise anorganische Mikropigmente in die erfindungsgemäßen Zubereitungen eingearbeitet werden sollen, auch anionische, nichtionische und/oder amphote- re Tenside enthalten. Tenside sind amphiphile Stoffe, die organische, unpolare Substanzen in Wasser lösen können.Preparations according to the invention can also contain anionic, nonionic and / or amphoteric surfactants, especially if crystalline or microcrystalline solids, for example inorganic micropigments, are to be incorporated into the preparations according to the invention. Surfactants are amphiphilic substances that can dissolve organic, non-polar substances in water.
Bei den hydrophilen Anteilen eines Tensidmoleküls handelt es sich meist um polare funk- tionelle Gruppen, beispielweise -COO", -0S03 2", -S03 ", während die hydrophoben Teile in der Regel unpolare Kohlenwasserstoffreste darstellen. Tenside werden im allgemeinen nach Art und Ladung des hydrophilen Molekülteils klassifiziert. Hierbei können vier Gruppen unterschieden werden:The hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO " , -0S0 3 2" , -S0 3 " , while the hydrophobic parts generally represent non-polar hydrocarbon residues. Surfactants are generally classified according to Art and charge of the hydrophilic part of the molecule. There are four groups:
• anionische Tenside,Anionic surfactants,
• kationische Tenside,Cationic surfactants,
• amphotere Tenside und• amphoteric surfactants and
• nichtionische Tenside.• nonionic surfactants.
Anionische Tenside weisen als funktionelle Gruppen in der Regel Carboxylat-, Sulfatoder Sulfonatgruppen auf. In wäßriger Lösung bilden sie im sauren oder neutralen Milieu negativ geladene organische Ionen. Kationische Tenside sind beinahe ausschließlich durch das Vorhandensein einer quaternären Ammoniumgruppe gekennzeichnet. In wäß-Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In an aqueous solution they form negatively charged organic ions in an acidic or neutral environment. Cationic surfactants are characterized almost exclusively by the presence of a quaternary ammonium group. In water
BESTÄTIGIIMGSKOPIE
riger Lösung bilden sie im sauren oder neutralen Milieu positiv geladene organische Ionen. Amphotere Tenside enthalten sowohl anionische als auch kationische Gruppen und verhalten sich demnach in wäßriger Lösung je nach pH-Wert wie anionische oder kationische Tenside. Im stark sauren Milieu besitzen sie eine positive und im alkalischen Milieu eine negative Ladung. Im neutralen pH-Bereich hingegen sind sie zwitterionisch, wie das folgende Beispiel verdeutlichen soll:BESTÄTIGIIMGSKOPIE solution, they form positively charged organic ions in an acidic or neutral environment. Amphoteric surfactants contain both anionic and cationic groups and accordingly behave like anionic or cationic surfactants in aqueous solution depending on the pH. They have a positive charge in a strongly acidic environment and a negative charge in an alkaline environment. In the neutral pH range, however, they are zwitterionic, as the following example should illustrate:
RNH2 +CH2CH2C00H X" (bei pH=2) X" = beliebiges Anion, z.B. Cl' RNH 2 + CH 2 CH 2 C00H X " (at pH = 2) X " = any anion, e.g. Cl '
RNH2 +CH2CH2COO- (bei pH=7)RNH 2 + CH 2 CH 2 COO- (at pH = 7)
RNHCH2CH2COO- B+ (bei pH=12) B+ = beliebiges Kation, z.B. Na+ RNHCH 2 CH 2 COO- B + (at pH = 12) B + = any cation, e.g. Na +
Typisch für nicht-ionische Tenside sind Polyether-Ketten. Nicht-ionische Tenside bilden in wäßrigem Medium keine Ionen.Polyether chains are typical of non-ionic surfactants. Non-ionic surfactants do not form ions in an aqueous medium.
A. Anionische TensideA. Anionic surfactants
Vorteilhaft zu verwendende anionische Tenside sindAnionic surfactants to be used advantageously
Acylaminosäuren (und deren Salze), wieAcylamino acids (and their salts), such as
1. Acylglutamate, beispielsweise Natriumacylglutamat, Di-TEA-palmitoylaspartat und Natrium Caprylic/ Capric Glutamat,1. acylglutamates, for example sodium acylglutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
2. Acylpeptide, beispielsweise Palmitoyl-hydrolysiertes Milchprotein, Natrium Cocoyl- hydrolysiert.es Soja Protein und Natrium-/ Kalium Cocoyl-hydrolysiertes Kollagen,2. acyl peptides, for example palmitoyl-hydrolyzed milk protein, sodium cocoyl-hydrolyzed.es soy protein and sodium / potassium cocoyl-hydrolyzed collagen,
3. Sarcosinate, beispielsweise Myristoyl Sarcosin, TEA-Iauroyl Sarcosinat, Natrium- lauroylsarcosinat und Natriumcocoylsarkosinat,3. sarcosinates, for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
4. Taurate, beispielsweise Natriumlauroyltaurat und Natriummethylcocoyitaurat,4. taurates, for example sodium lauroyl taurate and sodium methyl cocoyitaurate,
5. AcylLactylate, lauroyllactylat, Caproyllactylat5. Acyl lactylates, lauroyl lactylate, caproyl lactylate
6. Alaninate Carbonsäuren und Derivate, wie6. Alaninate carboxylic acids and derivatives such as
1. Carbonsäuren, beispielsweise Laurinsäure, Aluminiumstearat, Magnesiumalkanolat und Zinkundecylenat,1. carboxylic acids, for example lauric acid, aluminum stearate, magnesium alkanolate and zinc undecylenate,
2. Ester-Carbonsäuren, beispielsweise Calciumstearoyllactylat, Laureth-6 Citrat und Natrium PEG-4 Lauram idcarboxylat,2. ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauram idcarboxylate,
3. Ether-Carbonsäuren, beispielsweise Natriumlaureth-13 Carboxylat und Natrium PEG-6 Cocamide Carboxylat,3. ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,
BESTÄTIGINGSKOPIE
Phosphorsäureester und Salze, wie beispielsweise DEA-Oleth-10-Phosphat und Dilau- reth-4 Phosphat,BESTÄTIGINGSKOPIE Phosphoric acid esters and salts, such as DEA-oleth-10-phosphate and dilureth-4-phosphate,
Sulfonsäuren und Salze, wieSulfonic acids and salts such as
1. Acyl-isethionate, z.B. Natrium-/ Ammoniumcocoyl-isethionat,1. acyl isethionates, e.g. Sodium / ammonium cocoyl isethionate,
2. Alkylarylsulfonate,2. alkylarylsulfonates,
3. Alkylsulfonate, beispielsweise Natriumcocosmonoglyceridsulfat, Natrium C12.14 Ole- fin-sulfonat, Natriumlaurylsulfoacetat und Magnesium PEG-3 Cocamidsulfat,3. alkyl sulfonates, for example sodium cocosmonoglyceride sulfate, sodium C 12 . 14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
4. Sulfosuccinate, beispielsweise Dioctylnatriumsulfosuccinat, Dinatriumlaurethsulfo- succinat, Dinatriumlaurylsulfosuccinat und Dinatriumundecylenamido MEA-Sul- fosuccinat4. Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate
sowie Schwefelsäureester, wieas well as sulfuric acid esters, such as
1. Alkylethersulfat, beispielsweise Natrium-, Ammonium-, Magnesium-, MIPA-, TIPA- Laurethsulfat, Natriummyrethsulfat und Natrium C12.13 Parethsulfat,1. alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C 12 . 13 pareth sulfate,
2. Alkylsulfate, beispielsweise Natrium-, Ammonium- und TEA- Laurylsulfat.2. Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.
B. Kationische TensideB. Cationic surfactants
Vorteilhaft zu verwendende kationische Tenside sindCationic surfactants to be used advantageously
1. Alkylamine,1. alkylamines,
2. Alkylimidazole,2. alkylimidazoles,
3. Ethoxylierte Amine und3. Ethoxylated amines and
4. Quaternäre Tenside.4. Quaternary surfactants.
5. Esterquats5. Esterquats
Quaternäre Tenside enthalten mindestens ein N-Atom, das mit 4 Alkyl- oder Arylgruppen kovalent verbunden ist. Dies führt, unabhängig vom pH Wert, zu einer positiven Ladung. Vorteilhaft sind, Alkylbetain, Alkylamidopropylbetain und Alkyl-amidopropylhydroxysulfain. Die erfindungsgemäß verwendeten kationischen Tenside können ferner bevorzugt gewählt werden aus der Gruppe der quaternären Ammoniumverbindungen, insbesondere Benzyltrialkylammoniumchloride oder -bromide, wie beispielsweise Benzyldimethylstea- rylammoniumchlorid, ferner Alkyltrialkylammoniumsalze, beispielsweise beispielsweise Cetyltrimethylammoniumchlorid oder -bromid, Alkyldimethylhydroxyethylammo- niumchloride oder -bromide, Dialkyldimethylammoniumchloride oder -bromide, Alkylamid-Quaternary surfactants contain at least one N atom which is covalently linked to 4 alkyl or aryl groups. Regardless of the pH value, this leads to a positive charge. Alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysulfain are advantageous. The cationic surfactants used in the invention can also preferably be chosen from the group of quaternary ammonium compounds, especially benzyltrialkylammonium chlorides or bromides, such as rylammoniumchlorid Benzyldimethylstea-, further alkyltrialkylammonium salts, for example cetyltrimethylammonium chloride or bromide, niumchloride Alkyldimethylhydroxyethylammo- or bromides, dialkyldimethylammonium chlorides or bromides , Alkyl amide
BESTÄTIGINGSKOPiE
ethyltrimethylammoniumethersulfate, Alkylpyridiniumsalze, beispielsweise Lauryl- oder Cetylpyrimidiniumchlorid, Imidazolinderivate und Verbindungen mit kationischem Charakter wie Aminoxide, beispielsweise Alkyldimethylaminoxide oder Alkylamino- ethyldimethylaminoxide. Vorteilhaft sind insbesondere Cetyltrimethylammoniumsalze zu verwenden.BESTÄTIGINGSKOPiE ethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl or cetylpyrimidinium chloride, imidazoline derivatives and compounds with a cationic character such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous.
C. Amphotere TensideC. Amphoteric surfactants
Vorteilhaft zu verwendende amphotere Tenside sindAmphoteric surfactants to be used advantageously
1. Acyl-/dialkylethylendiamin, beispielsweise Natriumacylamphoacetat, Dinatriumacyl- amphodipropionat, Dinatriumalkylamphodiacetat, Natriumacylamphohydroxy- propylsulfonat, Dinatriumacylamphodiacetat und Natriumacylamphopropionat,1. acyl / dialkyl ethylenediamine, for example sodium acyl amphoacetate, disodium acyl amphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydroxy propyl sulfonate, disodium acyl amphodiacetate and sodium acyl amphopropionate,
2. N-Alkylaminosäuren, beispielsweise Aminopropylalkylglutamid, Alkylaminopropion- säure, Natriumalkylimidodipropionat und Lauroamphocarboxyglycinat.2. N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
D. Nicht-ionische TensideD. Non-ionic surfactants
Vorteilhaft zu verwendende nicht-ionische Tenside sindNon-ionic surfactants to be used advantageously
1. Alkohole,1. alcohols,
2. Alkanolamide, wie Cocamide MEA/ DEA MIPA,2. alkanolamides, such as Cocamide MEA / DEA MIPA,
3. Aminoxide, wie Cocoamidopropylaminoxid,3. amine oxides, such as cocoamidopropylamine oxide,
4. Ester, die durch Veresterung von Carbonsäuren mit Ethylenoxid, Glycerin, Sorbitan oder anderen Alkoholen entstehen,4. esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
5. Ether, beispielsweise ethoxylierte/propoxylierte Alkohole, ethoxylierte/ propoxylier- te Ester, ethoxylierte/ propoxylierte Glycerinester, ethoxylierte/ propoxylierte Cho- lesterine, ethoxylierte/ propoxylierte Triglyceridester, ethoxyliert.es propoxyliertes Lanolin, ethoxylierte/ propoxylierte Polysiloxane, propoxylierte POE-Ether und Al- kylpolyglycoside wie Laurylglucosid, Decylglycosid und Cocoglycosid.5. ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterol esters, ethoxylated / propoxylated triglyceride esters, ethoxylated.es propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, and propoxylated POE ethers Alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.
6. Sucroseester, -Ether6. sucrose esters, ether
7 Polyglycerinester, Diglycerinester, Monoglycerinester 8. Methylglucosester, Ester von Hydroxysäuren7 polyglycerol esters, diglycerol esters, monoglycerol esters 8. methyl glucose esters, esters of hydroxy acids
Vorteilhaft ist ferner die Verwendung einer Kombination von anionischen und/oder amphoteren Tensiden mit einem oder mehreren nicht-ionischen Tensiden.It is also advantageous to use a combination of anionic and / or amphoteric surfactants with one or more nonionic surfactants.
BESTÄTIGINGSKOPIE
Die oberflächenaktive Substanz kann in einer Konzentration zwischen 1 und 95 Gew.-% in den erfindungsgemäßen Zubereitungen vorliegen, bezogen auf das Gesamtgewicht der Zubereitungen.BESTÄTIGINGSKOPIE The surface-active substance can be present in the preparations according to the invention in a concentration between 1 and 95% by weight, based on the total weight of the preparations.
Die Lipidphase der erfindungsgemäßen kosmetischen oder dermatologischen Emulsionen kann vorteilhaft gewählt werden aus folgender Substanzgruppe:The lipid phase of the cosmetic or dermatological emulsions according to the invention can advantageously be selected from the following group of substances:
Mineralöle, MineralwachseMineral oils, mineral waxes
Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z.B. Rizinusöl;Oils such as triglycerides of capric or caprylic acid as well as natural oils such as e.g. Castor oil;
Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweiseFats, waxes and other natural and synthetic fat bodies, preferably
Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propy- lenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Esters of fatty acids with low C alcohols, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with lower C- alkanoic acids
Zahl oder mit Fettsäuren;Number or with fatty acids;
Alkylbenzoate;benzoates;
Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
Die Ölphase der Emulsionen der vorliegenden Erfindung wird vorteilhaft gewählt aus der Gruppe der Ester aus gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkancarbonsäuren einer Kettenlänge von 3 bis 30 C-Atomen und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen, aus der Gruppe der Ester aus aromatischen Carbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten Alkoholen einer Kettenlänge von 3 bis 30 C-Atomen. Solche Esteröle können dann vorteilhaft gewählt werden aus der Gruppe Isopropylmyristat, Isopropylpalmitat, Isopropylstearat, Iso- propyloleat, n-Butylstearat, n-Hexyllaurat, n-Decyloleat, Isooctylstearat, Isononylstearat, Isononylisononanoat, 2-Ethylhexylpalmitat, 2-Ethylhexyllaurat, 2-Hexyldecylstearat, 2-Oc- tyldodecylpalmitat, Oleyloleat, Oleylerucat, Erucyloleat, Erucylerucat sowie synthetische, halbsynthetische und natürliche Gemische solcher Ester, z.B. Jojobaöl.The oil phase of the emulsions of the present invention is advantageously selected from the group of the esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethyl-2-ethylhexyl palmitate 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semisynthetic and natural mixtures of such esters, for example Jojoba oil.
Ferner kann die Ölphase vorteilhaft gewählt werden aus der Gruppe der verzweigten und unverzweigten Kohlenwasserstoffe und -wachse, der Silkonöle, der Dialkylether, der Gruppe der gesättigten oder ungesättigten, verzweigten oder unverzweigten Alkohole, sowie der Fettsäuretriglyceride, namentlich der Triglycerinester gesättigter und/oder un-Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or
BESTÄTIGINGSKOPIE
gesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen. Die Fettsäuretriglyceride können beispielsweise vorteilhaft gewählt werden aus der Gruppe der synthetischen, halbsynthetischen und natürlichen Öle, z.B. Olivenöl, Sonnenblumenöl, Sojaöl, Erdnußöl, Rapsöl, Mandelöl, Palmöl, Kokosöl, Palmkernöl und dergleichen mehr.BESTÄTIGINGSKOPIE saturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 carbon atoms. The fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, for example olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
Auch beliebige Abmischungen solcher Öl- und Wachskomponenten sind vorteilhaft im Sinne der vorliegenden Erfindung einzusetzen. Es kann auch gegebenenfalls vorteilhaft sein, Wachse, beispielsweise Cetylpalmitat, als alleinige Lipidkomponente der Ölphase einzusetzen.Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
Vorteilhaft wird die Ölphase gewählt aus der Gruppe 2-Ethylhexylisostearat, Octyldode- canol, Isotridecylisononanoat, Isoeicosan, 2-Ethylhexylcocoat, C12-15-Alkylbenzoat, Capryl-Caprinsäure-triglycerid, Dicaprylylether.The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C 12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.
Besonders vorteilhaft sind Mischungen aus C12-15-Alkylbenzoat und 2-Ethylhexylisostea- rat, Mischungen aus Cι2-i5-Alkylbenzoat und Isotridecylisononanoat sowie Mischungen aus Cι2-15-Alkylbenzoat, 2-Ethylhexylisostearat und Isotridecylisononanoat.Mixtures of C 12-15 alkyl benzoate and 2-ethylhexyl isostate, mixtures of C 2- i5 alkyl benzoate and isotridecyl isononanoate and mixtures of C 2-15 alkyl benzoate, 2-ethyl hexyl isostearate and isotridecyl isononanoate are particularly advantageous.
Von den Kohlenwasserstoffen sind Paraffinöl, Squalan und Squalen vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden.Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.
Vorteilhaft kann die Ölphase ferner einen Gehalt an cyclischen oder linearen Silikonölen aufweisen oder vollständig aus solchen Ölen bestehen, wobei allerdings bevorzugt wird, außer dem Silikonöl oder den Silikonölen einen zusätzlichen Gehalt an anderen Ölpha- senkomponenten zu verwenden. Solche Silicone oder Siliconöle können als Monomere vorliegen, welche in der Regel durch Strukturelemente charakterisiert sind, wie folgt:The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils. Such silicones or silicone oils can be present as monomers, which are generally characterized by structural elements, as follows:
Als erfindungsgemäß vorteilhaft einzusetzenden linearen Silicone mit mehreren Siloxyl- einheiten werden im allgemeinen durch Strukturelemente charakterisiert wie folgt:Linear silicones with a plurality of siloxyl units which can advantageously be used according to the invention are generally characterized by structural elements as follows:
BESTÄTΪQINGS
wobei die Siliciumatome mit gleichen oder unterschiedlichen Alkylresten und/oder Aryl- resten substituiert werden können, welche hier verallgemeinernd durch die Reste R^ - R4 dargestellt sind (will sagen, daß die Anzahl der unterschiedlichen Reste nicht notwendig auf bis zu 4 beschränkt ist), m kann dabei Werte von 2 - 200.000 annehmen.BESTÄTΪQINGS wherein the silicon atoms can be substituted with the same or different alkyl radicals and / or aryl radicals, which are generally represented here by the radicals R ^ - R 4 (to say that the number of different radicals is not necessarily limited to up to 4) , m can assume values from 2 to 200,000.
Erfindungsgemäß vorteilhaft einzusetzende cyclische Silicone werden im allgemeinen durch Strukturelemente charakterisiert, wie folgtCyclic silicones to be used advantageously according to the invention are generally characterized by structural elements as follows
wobei die Siliciumatome mit gleichen oder unterschiedlichen Alkylresten und/oder Aryl- resten substituiert werden können, welche hier verallgemeinernd durch die Reste RT - R dargestellt sind (will sagen, daß die Anzahl der unterschiedlichen Reste nicht notwendig auf bis zu 4 beschränkt ist), n kann dabei Werte von 3/2 bis 20 annehmen. Gebrochene Werte für n berücksichtigen, daß ungeradzahlige Anzahlen von Siloxylgruppen im Cyclus vorhanden sein können. wherein the silicon atoms can be substituted with the same or different alkyl radicals and / or aryl radicals, which are generally represented here by the radicals R T - R (to say that the number of different radicals is not necessarily limited to up to 4), n can take values from 3/2 to 20. Broken values for n take into account that there may be odd numbers of siloxyl groups in the cycle.
Vorteilhaft wird Cyclomethicon (z.B. Decamethylcyclopentasiloxan) als erfindungsgemäß zu verwendendes Silikonöl eingesetzt. Aber auch andere Silikonöle sind vorteilhaft im Sinne der vorliegenden Erfindung zu verwenden, beispielsweise Undecamethylcyclotrisi- loxan, Polydimethylsiloxan, Poly(methylphenylsiloxan), Cetyldimethicon, Behenoxydi- methicon.Cyclomethicone (e.g. decamethylcyclopentasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example undecamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone.
Vorteilhaft sind ferner Mischungen aus Cyclomethicon und Isotridecylisononanoat, sowie solche aus Cyclomethicon und 2-Ethylhexylisostearat.Mixtures of cyclomethicone and isotridecyl isononanoate and those of cyclomethicone and 2-ethylhexyl isostearate are also advantageous.
BESTÄTIGINGSKOPIE
Es ist aber auch vorteilhaft, Silikonöle ähnlicher Konstitution wie der vorstehend bezeichneten Verbindungen zu wählen, deren organische Seitenketten derivatisiert, beispielsweise polyethoxyliert und/oder polypropoxyliert sind. Dazu zählen beispielsweise Po- lysiloxan-polyalkyl-polyether-copolymere wie das Cetyl-Dimethicon-Copolyol, das (Cetyl- Dimethicon-Copolyol (und) Polyglyceryl-4-lsostearat (und) Hexyllaurat)BESTÄTIGINGSKOPIE However, it is also advantageous to choose silicone oils of a similar constitution to the compounds described above, the organic side chains of which are derivatized, for example polyethoxylated and / or polypropoxylated. These include, for example, polysiloxane-polyalkyl-polyether copolymers such as the cetyl-dimethicone copolyol, the (cetyl-dimethicone copolyol (and) polyglyceryl-4-isostearate (and) hexyl laurate)
Besonders vorteilhaft sind ferner Mischungen aus Cyclomethicon und Isotridecylisononanoat, aus Cyclomethicon und 2-Ethylhexylisostearat.Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.
Die wäßrige Phase der erfindungsgemäßen Zubereitungen enthält gegebenenfalls vorteilhaft Alkohole, Diole oder Polyole niedriger C-Zahl, sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Glycerin, Ethylenglykol, Ethylenglykolmonoethyl- oder -monobutylether, Propylenglykolmonomethyl, -monoethyl- oder -monobutylether, Di- ethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, ferner Alkohole niedriger C-Zahl, z.B. Ethanol, Isopropanol, 1 ,2-Propandiol, Glycerin sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate.The aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, di - Ethylene glycol monomethyl or monoethyl ether and similar products, furthermore alcohols with a low C number, for example Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide and aluminum silicates.
Erfindungsgemäße als Emulsionen vorliegenden Zubereitungen enthalten insbesondere vorteilhaft ein oder mehrere Hydrocolloide. Diese Hydrocolloide können vorteilhaft gewählt werden aus der Gruppe der Gummen, Polysaccharide, Cellulosederivate, Schichtsilikate, Polyacrylate und/oder anderen Polymeren.Preparations according to the invention which are present as emulsions particularly advantageously contain one or more hydrocolloids. These hydrocolloids can advantageously be selected from the group of the gums, polysaccharides, cellulose derivatives, layered silicates, polyacrylates and / or other polymers.
Erfindungsgemäße als Hydrogele vorliegenden Zubereitungen enthalten ein oder mehrere Hydrocolloide. Diese Hydrocolloide können vorteilhaft aus der vorgenannten Gruppe gewählt werden.Preparations according to the invention which are present as hydrogels contain one or more hydrocolloids. These hydrocolloids can advantageously be selected from the aforementioned group.
Zu den Gummen zählt man Pflanzen- oder Baumsäfte, die an der Luft erhärten und Harze bilden oder Extrakte aus Wasserpflanzen. Aus dieser Gruppe können vorteilhaft im Sinne der vorliegenden Erfindung gewählt werden beispielsweise Gummi Arabicum, Johannisbrotmehl, Tragacanth, Karaya, Guar Gummi, Pektin, Gellan Gummi, Carrageen, Agar, Algine, Chondrus, Xanthan Gummi.
Weiterhin vorteilhaft ist die Verwendung von derivatisierten Gummen wie z.B. Hydro- xypropyl Guar (Jaguar® HP 8).Gums include plant or tree sap that harden in the air and form resins or extracts from aquatic plants. Gum arabic, locust bean gum, tragacanth, karaya, guar gum, pectin, gellan gum, carrageenan, agar, algine, chondrus, xanthan gum can advantageously be selected from this group for the purposes of the present invention. The use of derivatized gums such as hydroxypropyl guar (Jaguar® HP 8) is also advantageous.
Unter den Polysacchariden und -derivaten befinden sich z.B. Hyaluronsäure, Chitin und Chitosan, Chondroitinsulfate, Stärke und Stärkederivate.Among the polysaccharides and derivatives are e.g. Hyaluronic acid, chitin and chitosan, chondroitin sulfates, starch and starch derivatives.
Unter den Cellulosederivaten befinden sich z.B. Methylcellulose, Carboxymethylcellulose, Hydroxyethylcellulose, Hydroxypropylmethylcellulose.Among the cellulose derivatives are e.g. Methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose.
Unter den Schichtsilikaten befinden sich natürlich vorkommende und synthetische Tonerden wie z.B. Montmorillonit, Bentonit, Hektorit, Laponit, Magnesiumaluminiumsilikate wie Veegum®. Diese können als solche oder in modifizierter Form verwendet werden wie z.B. Stearylalkonium Hektorite.Layered silicates contain naturally occurring and synthetic clays such as Montmorillonite, bentonite, hectorite, laponite, magnesium aluminum silicates such as Veegum®. These can be used as such or in a modified form such as e.g. Stearylalkonium hektorite.
Weiterhin können vorteilhaft auch Kieselsäuregele verwendet werden.Furthermore, silica gels can also advantageously be used.
Unter den Polyacrylaten befinden sich z.B. Carbopol Typen der Firma Goodrich (Carbo- pol 980, 981 , 1382, 5984, 2984, EDT 2001 oder Pemulen TR2).The polyacrylates include e.g. Carbopol types from Goodrich (Carbopol 980, 981, 1382, 5984, 2984, EDT 2001 or Pemulen TR2).
Unter den Polymeren befinden sich z.B. Polyacrylamide (Seppigel 305), Polyvinylalko- hole, PVP, PVP / VA Copolymere, Polyglycole.Among the polymers are e.g. Polyacrylamides (Seppigel 305), polyvinyl alcohols, PVP, PVP / VA copolymers, polyglycols.
Erfindungsgemäße als Emulsionen vorliegenden Zubereitungen enthalten einen oder mehrere Emulgatoren. Diese Emulgatoren können vorteilhaft gewählt werden aus der Gruppe der nichtionischen, anionischen, kationischen oder amphoteren Emulgatoren.Preparations according to the invention in the form of emulsions contain one or more emulsifiers. These emulsifiers can advantageously be selected from the group of nonionic, anionic, cationic or amphoteric emulsifiers.
Unter den nichtionischen Emulgatoren befinden sich a) Partialfettsäureester und Fettsäureester mehrwertiger Alkohole und deren ethoxylierte Derivate (z. B. Glycerylmonostearate, Sorbitanstearate, Glycerylstearylcitrate, Sucro- sestearate) b) ethoxilierte Fettalkohole und Fettsäuren c) ethoxilierte Fettamine, Fettsäureamide, Fettsäurealkanolamide d) Alkylphenolpolyglycolether (z.B. Triton X)The nonionic emulsifiers include a) partial fatty acid esters and fatty acid esters of polyhydric alcohols and their ethoxylated derivatives (e.g. glyceryl monostearates, sorbitan stearates, glyceryl stearyl citrates, sucrose stearyl citrates, b) ethoxylated fatty alcohols and fatty acids c) alkyl acid phenol amide fatty amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, fatty acid glycol amides, e.g. Triton X)
BESTÄTIGINGS
Unter den anionischen Emulgatoren befinden sich a) Seifen (z. B. Natriumstearat) b) Fettalkoholsulfate c) Mono-, Di- und Trialkylphosphosäureester und deren EthoxylateBESTÄTIGINGS The anionic emulsifiers include a) soaps (e.g. sodium stearate) b) fatty alcohol sulfates c) mono-, di- and trialkylphosphonic acid esters and their ethoxylates
Unter den kationischen Emulgatoren befinden sich a) quaternäre Ammoniumverbindungen mit einem langkettigen aliphatischen Rest z.B. Distearyldimonium ChlorideThe cationic emulsifiers include a) quaternary ammonium compounds with a long-chain aliphatic radical, e.g. Distearyldimonium Chloride
Unter den amphoteren Emulgatoren befinden sich a) Alkylamininoalkancarbonsäuren b) Betaine, Sulfobetaine c) ImidazolinderivateThe amphoteric emulsifiers include a) alkylamininoalkane carboxylic acids b) betaines, sulfobetaines c) imidazoline derivatives
Weiterhin gibt es natürlich vorkommende Emulgatoren, zu denen Bienenwachs, Wollwachs, Lecithin und Sterole gehören.There are also naturally occurring emulsifiers, which include beeswax, wool wax, lecithin and sterols.
O/W-Emulgatoren können beispielsweise vorteilhaft gewählt werden aus der Gruppe der polyethoxylierten bzw. polypropoxylierten bzw. polyethoxylierten und polypropoxylierten Produkte, z.B.: der Fettalkoholethoxylate der ethoxylierten Wollwachsalkohole, der Polyethylenglycolether der allgemeinen Formel R-0-(-CH2-CH2-0-)n-R', der Fettsäureethoxylate der allgemeinen FormelO / W emulsifiers can, for example, advantageously be selected from the group of polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated products, for example: the fatty alcohol ethoxylates of the ethoxylated wool wax alcohols, the polyethylene glycol ethers of the general formula R-0 - (- CH 2 -CH 2 - 0-) n -R ', the fatty acid ethoxylates of the general formula
R-COO-(-CH2-CH2-0-)n -H , der veretherten Fettsäureethoxylate der allgemeinen FormelR-COO - (- CH 2 -CH 2 -0-) n -H, the etherified fatty acid ethoxylates of the general formula
R-COO-(-CH2-CH2-0-)n-R', der veresterten Fettsäureethoxylate der allgemeinen FormelR-COO - (- CH 2 -CH 2 -0-) n -R ', the esterified fatty acid ethoxylates of the general formula
R-COO-(-CH2-CH2-0-)n -C(0)-R\ der Polyethylenglycolglycerinfettsäureester der ethoxylierten Sorbitanester der Cholesterinethoxylate der ethoxylierten Triglyceride der Alkylethercarbonsäuren der allgemeinen FormelR-COO - (- CH 2 -CH 2 -0-) n -C (0) -R \ the polyethylene glycol glycerol fatty acid ester of ethoxylated sorbitan esters of cholesterol ethoxylates of ethoxylated triglycerides of alkyl ether carboxylic acids of the general formula
BESTÄTIGINGSKOPIE
R-0-(-CH2-CH2-0-)n-CH2-COOH nd n eine Zahl von 5 bis 30 darstellen, der Polyoxyethylensorbitolfettsäureester, der Alkylethersulfate der allgemeinen Formel R-0-(-CH2-CH2-0-)n-S03-H der Fettalkoholpropoxylate der allgemeinen Formel R-0-(-CH2-CH(CH3)-0-)n-H, der Polypropylenglycolether der allgemeinen Formel R-0-(-CH2-CH(CH3)-0-)n-R\ der propoxylierten Wollwachsalkohole, der veretherten Fettsäurepropoxylate R-COO-(-CH2-CH(CH3)-0-)n-R', der veresterten Fettsäurepropoxylate der allgemeinen Formel R-COO-(-CH2-CH(CH3)-0-)n-C(0)-R', der Fettsäurepropoxylate der allgemeinen Formel R-COO-(-CH2-CH(CH3)-0-)n-H, der Polypropylenglycolglycerinfettsäureester der propoxylierten Sorbitanester der Cholesterinpropoxylate der propoxylierten Triglyceride der Alkylethercarbonsäuren der allgemeinen Formel R-0-(-CH2-CH(CH3)0-)n-CH2-COOH der Alkylethersulfate bzw. die diesen Sulfaten zugrundeliegenden Säuren der allgemeinen Formel R-0-(-CH2-CH(CH3)-0-)n-S03-H der Fettalkoholethoxylate/propoxylate der allgemeinen Formel R-0-Xn-Ym-H, der Polypropylenglycolether der allgemeinen Formel R-0-Xn-Ym-R', der veretherten Fettsäurepropoxylate der allgemeinen Formel R-COO-Xn-Ym-R\ der Fettsäureethoxylate/propoxylate der allgemeinen Formel
BESTÄTIGINGSKOPIE R-0 - (- CH 2 -CH 2 -0-) n -CH 2 -COOH and n represent a number from 5 to 30, the polyoxyethylene sorbitol fatty acid esters, the alkyl ether sulfates of the general formula R-0 - (- CH 2 -CH 2 -0-) n -S0 3 -H of the fatty alcohol propoxylates of the general formula R-0 - (- CH 2 -CH (CH 3 ) -0-) n -H, the polypropylene glycol ether of the general formula R-0 - (- CH 2 -CH (CH 3 ) -0-) n -R \ of the propoxylated wool wax alcohols, the etherified fatty acid propoxylates R-COO - (- CH 2 -CH (CH 3 ) -0-) n -R ', the esterified fatty acid propoxylates of the general formula R-COO - (- CH 2 -CH (CH 3 ) -0-) n -C (0) -R ', the fatty acid propoxylates of the general formula R-COO - (- CH 2 -CH (CH 3 ) -0- ) n -H, the polypropylene glycol glycerol fatty acid ester of the propoxylated sorbitan esters of the cholesterol propoxylates of the propoxylated triglycerides of the alkyl ether carboxylic acids of the general formula R-0 - (- CH 2 -CH (CH 3 ) 0-) n -CH 2 -COOH of the alkyl ether sulfates or these sulfates underlying acids of the general formula R-0 - (- CH 2 -CH (CH 3 ) -0-) n-S0 3 -H of the fatty alcohol ethoxylates / propoxylates of the general formula R-0-X n -Y m -H, the polypropylene glycol ether of the general formula R-0-X n -Y m -R ', the etherified Fatty acid propoxylates of the general formula R-COO-X n -Y m -R \ of the fatty acid ethoxylates / propoxylates of the general formula
Erfindungsgemäß besonders vorteilhaft werden die eingesetzten polyethoxylierten bzw. polypropoxylierten bzw. polyethoxylierten und polypropoxylierten O/W-Emulgatoren gewählt aus der Gruppe der Substanzen mit HLB-Werten von 11 - 18, ganz besonders vor-According to the invention, the polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated O / W emulsifiers used are selected with particular advantage from the group of substances with HLB values of 11-18, particularly preferably
BESTÄTIGINGSKOPiE
teilhaft mit mit HLB-Werten von 14,5 - 15,5, sofern die O/W-Emulgatoren gesättigte Reste R und R' aufweisen. Weisen die O/W-Emulgatoren ungesättigte Reste R und/oder R' auf, oder liegen Isoalkylderivate vor, so kann der bevorzugte HLB-Wert solcher Emulgatoren auch niedriger oder darüber liegen.BESTÄTIGINGSKOPiE partly with HLB values of 14.5 - 15.5, provided the O / W emulsifiers have saturated residues R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R 'or if there are isoalkyl derivatives, the preferred HLB value of such emulsifiers can also be lower or higher.
Es ist von Vorteil, die Fettalkoholethoxylate aus der Gruppe der ethoxylierten Stearylal- kohole, Cetylalkohole, Cetylstearylalkohole (Cetearylalkohole) zu wählen. Insbesondere bevorzugt sind:It is advantageous to choose the fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). The following are particularly preferred:
Polyethylenglycol(13)stearylether (Steareth-13), Polyethylenglycol(14)stearylether (Stea- reth-14), Polyethylenglycol(15)stearylether (Steareth-15), Polyethylenglycol(16)stea- rylether (Steareth-16), Polyethylenglycol(17)stearylether (Steareth-17), Polyethylenglycol- (18)stearylether (Steareth-18), Polyethylenglycol(19)stearylether (Steareth-19), Polyethy- lenglycol(20)stearylether (Steareth-20),Polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene glycol ( 17) stearyl ether (Steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (Steareth-19), polyethylene glycol (20) stearyl ether (Steareth-20),
Polyethylenglycoi(12)isostearylether (lsosteareth-12), Polyethylenglycol(13)isostearyl- ether (lsosteareth-13), Polyethylenglycol(14)isostearylether (lsosteareth-14), Polyethylen- glycol(15)isostearylether (lsosteareth-15), Polyethylenglycol(16)isostearylether (Iso- steareth-16), Polyethylenglycol(17)isostearylether (lsosteareth-17), Polyethylenglycol- (18)isostearylether (Isosteareth-18), Polyethylenglycol(19)isostearylether (lsosteareth-19- ), Polyethylenglycol(20)isostearylether (lsosteareth-20),Polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol ( 16) isostearyl ether (isosteareth-16), polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19-), polyethylene glycol (20) isostearyl ether (isosteareth-20),
Polyethylenglycol(13)cetylether (Ceteth-13), Polyethylenglycol(14)cetylether (Ceteth-14), Polyethylenglycol(15)cetylether (Ceteth-15), Polyethylenglycol(16)cetylether (Ceteth-16), Polyethylenglycol(17)cetylether (Ceteth-17), Polyethylenglycol(18)cetylether (Ceteth-18), Polyethylenglycol(19)cetylether (Ceteth-19), Polyethylenglycol(20)cetylether (Ceteth-20),Polyethylene glycol (13) cetyl ether (ceteth-13), polyethylene glycol (14) cetyl ether (ceteth-14), polyethylene glycol (15) cetyl ether (ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether ( Ceteth-17), polyethylene glycol (18) cetyl ether (ceteth-18), polyethylene glycol (19) cetyl ether (ceteth-19), polyethylene glycol (20) cetyl ether (ceteth-20),
Polyethylenglycol(13)isocetylether (lsoceteth-13), Polyethylenglycol(14)isocetylether (Iso- ceteth-14), Polyethylenglycol(15)isocetylether (lsoceteth-15), Polyethylenglycol(16)- isocetylether (lsoceteth-16), Polyethylenglycol(17)isocetylether (lsoceteth-17), Polyethy- lenglycol(18)isocetylether (lsoceteth-18), Polyethylenglycol(19)isocetylether (Isoceteth- 19), Polyethylenglycol(20)isocetylether (lsoceteth-20),Polyethylene glycol (13) isocetyl ether (isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) - isocetyl ether (isoceteth-16), polyethylene glycol (17 ) isocetyl ether (isoceteth-17), polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (isoceteth-19), polyethylene glycol (20) isocetyl ether (isoceteth-20),
BESTÄTIGINGSKOPiE
Polyethyienglycol(12)oleylether (Oleth-12), Polyethylenglycol(13)oleylether (Oleth-13), Polyethylenglycol(14)oleylether (Oleth-14), Polyethylenglycol(15)oleylether (Oleth-15),BESTÄTIGINGSKOPiE Polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15),
Polyethylenglycol(12)laurylether (Laureth-12), Polyethylenglycol(12)isolaurylether (Isolau- reth-12).Polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolureth-12).
Polyethylenglycol(13)cetylstearylether (Ceteareth-13), Polyethylenglycol(14)cetylstearyl- ether (Ceteareth-14), Polyethylenglycol(15)cetylstearylether (Ceteareth-15), Polyethylen- glycol(16)cetylstearylether (Ceteareth-16), Polyethylenglycol(17)cetylstearylether (Cetea- reth-17), Polyethylenglycol(18)cetylstearylether (Ceteareth-18), Polyethylenglycol(19)- cetylstearylether (Ceteareth-19), Polyethylenglycol(20)cetylstearylether (Ceteareth-20),Polyethylene glycol (13) cetylstearyl ether (ceteareth-13), polyethylene glycol (14) cetylstearyl ether (ceteareth-14), polyethylene glycol (15) cetylstearyl ether (ceteareth-15), polyethylene glycol (16) cetylstearyl ether (ceteareth-16), polyethylene glycol 17) cetylstearyl ether (Ceteareth-17), polyethylene glycol (18) cetylstearylether (Ceteareth-18), polyethylene glycol (19) - cetylstearylether (Ceteareth-19), polyethylene glycol (20) cetylstearylether (Ceteareth-20),
Es ist ferner von Vorteil, die Fettsäureethoxylate aus folgender Gruppe zu wählen:It is also advantageous to choose the fatty acid ethoxylates from the following group:
Polyethylenglycol(20)stearat, Polyethylenglycol(21 )stearat, Polyethylenglycol(22)stearat, Polyethylenglycol(23)stearat, Polyethylenglycol(24)stearat, Polyethylenglycol(25)stearat,Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate,
Polyethylenglycol(12)isostearat, Polyethylenglycol(13)isostearat, Polyethylenglycol(14)- isostearat, Polyethylenglycol(15)isostearat, Polyethylenglycol(16)isostearat, Polyethylen- glycol(17)isostearat, Polyethylenglycol(18)isostearat, Polyethylenglycol(19)isostearat, Polyethylenglycol(20)isostearat, Polyethylenglycol(21 )isostearat, Polyethylenglycol- (22)isostearat, Polyethylenglycol(23)isostearat, Polyethylenglycol(24)isostearat, Polyethy- lenglycol(25)isostearat,Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol (14) - isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate , Polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,
Polyethylenglycol(12)oleat, Polyethylenglycol(13)oleat, Polyethylenglycol(14)oleat, Poly- ethylenglycol(15)oleat, Polyethylenglycol(16)oleat, Polyethylenglycol(17)oleat, Polyethy- lenglycol(18)oleat, Polyethylenglycol(19)oleat, Polyethylenglycol(20)oleatPolyethylene glycol (12) oleate, Polyethylene glycol (13) oleate, Polyethylene glycol (14) oleate, Polyethylene glycol (15) oleate, Polyethylene glycol (16) oleate, Polyethylene glycol (17) oleate, Polyethylene glycol (18) oleate, Polyethylene glycol (19) oleate, polyethylene glycol (20) oleate
Als ethoxylierte Alkylethercarbonsäure bzw. deren Salz kann vorteilhaft das Natriumlau- reth-11 -carboxylat verwendet werden.Sodium laureth-11 carboxylate can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt.
Als Alkylethersulfat kann Natrium Laureth 1-4 sulfat vorteilhaft verwendet werden.Sodium laureth 1-4 sulfate can advantageously be used as alkyl ether sulfate.
BESTÄTIGINGSKOPiE
Als ethoxyliert.es Cholesterinderivat kann vorteilhaft Polyethylenglycol(30)Cholesteryl- ether verwendet werden. Auch Polyethylenglycol(25)Sojasterol hat sich bewährt.BESTÄTIGINGSKOPiE Polyethylene glycol (30) cholesteryl ether can advantageously be used as the ethoxylated cholesterol derivative. Polyethylene glycol (25) soyasterol has also proven itself.
Als ethoxylierte Triglyceride können vorteilhaft die Polyethylenglycol(60) Evening Primrose Glycerides verwendet werden (Evening Primrose = Nachtkerze)Polyethylene glycol (60) evening primrose glycerides can advantageously be used as ethoxylated triglycerides (evening primrose = evening primrose)
Weiterhin ist von Vorteil, die Polyethylenglycolglycerinfettsäureester aus der Gruppe Po- lyethylenglycol(20)glyceryllaurat, Polyethylenglycol(21)glyceryllaurat, Polyethylenglycol- (22)glyceryllaurat, Polyethylenglycol(23)glyceryllaurat, PolyethylengIycol(6)glyceryl- caprat/caprinat, Polyethylenglycol(20)glyceryloleat, Polyethylenglycol(20)glyceryliso~ stearat, Polyethylenglycol(18)glyceryloleat/cocoat zu wählen.It is also advantageous to use the polyethylene glycol glycerol fatty acid esters from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl 20-caprate / caprin ) glyceryl oleate, polyethylene glycol (20) glyceryl iso stearate, polyethylene glycol (18) glyceryl oleate / cocoate.
Es ist ebenfalls günstig, die Sorbitanester aus der Gruppe Polyethylenglycol(20)sorbitan- monolaurat, Polyethylenglycol(20)sorbitanmonostearat, Polyethylenglycol(20)sor- bitanmonoisostearat, Polyethylenglycol(20)sorbitanmonopalmitat, Polyethylenglycol(20)- sorbitanmonooleat zu wählen.It is also favorable to choose the sorbitan esters from the group polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
Als vorteilhafte W/O-Emulgatoren können eingesetzt werden: Fettalkohole mit 8 bis 30 Kohlenstoffatomen, Monoglycerinester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen, Diglycerinester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen, Monoglycerinether gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen, Diglycerinether gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen, Propylenglycolester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C- Atomen sowie Sorbitanester gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkancarbonsäuren einer Kettenlänge von 8 bis 24, insbesondere 12 - 18 C-Atomen.Advantageous W / O emulsifiers that can be used are: fatty alcohols with 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18, carbon atoms, diglycerol esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 - 18 C atoms, monoglycerol ethers saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 8 to 24, in particular 12 - 18 C - Atoms, diglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 C atoms and sorbitan esters saturated and / or uns saturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 carbon atoms.
Insbesondere vorteilhafte W/O-Emulgatoren sind Glycerylmonostearat, Glycerylmonoiso- stearat, Glycerylmonomyristat, Glycerylmonooleat, Diglycerylmonostearat, Diglyceryl-Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl
BESTÄTIGINGSKOPiE
monoisostearat, Propylenglycolmonostearat, Propylenglycolmonoisostearat, Propylengly- colmonocaprylat, Propylenglycolmonolaurat, Sorbitanmonoisostearat, Sorbitanmo- nolaurat, Sorbitanmonocaprylat, Sorbitanmonoisooleat, Saccharosedistearat, Cetyl- alkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol, Isobehenylalkohol, Selachyl- alkohol, Chimylalkohol, Polyethylenglycol(2)stearylether (Steareth-2), Glycerylmono- laurat, Glycerylmonocaprinat, Glycerylmonocaprylat.BESTÄTIGINGSKOPiE monoisostearate, colmonocaprylat propylene glycol monostearate, propylene glycol monoisostearate glycol, propylene, sorbitan monoisostearate, propylene glycol monolaurate Sorbitanmo-, sorbitan, Sorbitanmonoisooleat, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, Isobehenylalkohol, Selachyl- alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth 2), glyceryl mono laurate, glyceryl monocaprinate, glyceryl monocaprylate.
Die folgenden Beispiele sollen die Erfindung erläutern, aber nicht einschränken. Die Zahlenangaben beziehen sich auf Gew.-%, sofern nichts Anderes angegeben ist.The following examples are intended to illustrate but not limit the invention. The figures relate to% by weight, unless stated otherwise.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen.The following examples are intended to illustrate the present invention.
BESTÄTIGINGSKOPiE
Beispiel 1BESTÄTIGINGSKOPiE example 1
Die Bestandteile der Phasen (A) und (B) werden jeweils bei ca. 80 °C zusammengegeben und verrührt, bis die Phasen homogen erscheinen. Sodann werden die Phasen (A) und (B) vereinigt und auf ca. 40 °C abgekühlt. Die Parfumphase (C) wird bei ca. 40 °C zu den vereinigten Phasen (A) und (B) gegeben, woraufhin auf Raumtemperatur abgekühlt wird.The components of phases (A) and (B) are combined at about 80 ° C and stirred until the phases appear homogeneous. Then phases (A) and (B) are combined and cooled to approx. 40 ° C. The perfume phase (C) is added to the combined phases (A) and (B) at about 40 ° C., whereupon the mixture is cooled to room temperature.
BESTÄTIGINGSKOPiE
Beispiel 2BESTÄTIGINGSKOPiE Example 2
Die Bestandteile der Phasen (A) und (B) werden jeweils bei ca. 70 - 75 °C zusammengegeben und verrührt, bis die Phasen homogen erscheinen. Sodann werden die Phasen (A) und (B) vereinigt und auf ca. 60 °C abgekühlt, wo sie durch kräftiges Verrühren emulgiert werden. Die Konservierungsphase (C) wird bei ca. 50 °C zu den vereinigten Phasen (A) und (B) gegeben, woraufhin die gesamte Mischung unter fortgesetztem Rühren bei auf Raumtemperatur abgekühlt wird.The components of phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous. The phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified by vigorous stirring. The preservation phase (C) is added to the combined phases (A) and (B) at about 50 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
BESTÄTIGINGSKOPiE
Beispiel 3BESTÄTIGINGSKOPiE Example 3
Die Bestandteile der Phasen (A) und (B) werden jeweils bei ca. 70 - 75 °C zusammengegeben und verrührt, bis die Phasen homogen erscheinen. Sodann werden die Phasen (A) und (B) vereinigt und auf ca. 60 °C abgekühlt, wo sie durch kräftiges Verrühren emulgiert und homogenisiert werden. Die Konservierungsphase (C) wird bei ca. 55 °C zu den vereinigten Phasen (A) und (B) gegeben, woraufhin die gesamte Mischung unter fortgesetztem Rühren bei auf Raumtemperatur abgekühlt wird.The components of phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous. The phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified and homogenized by vigorous stirring. The preservation phase (C) is added to the combined phases (A) and (B) at approx. 55 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
BESTÄTIGINGSKOPiE
Beispiel 4BESTÄTIGINGSKOPiE Example 4
Die Bestandteile der Phasen (A) und (B) werden jeweils bei ca. 70 - 75 °C zusammengegeben und verrührt, bis die Phasen homogen erscheinen. Sodann werden die Phasen (A) und (B) vereinigt und auf ca. 60 °C abgekühlt, wo sie durch kräftiges Verrühren emulgiert und homogenisiert werden. Die Parfumphase (C) wird bei ca. 55 °C zu den vereinigten Phasen (A) und (B) gegeben, woraufhin die gesamte Mischung unter fortgesetztem Rühren bei auf Raumtemperatur abgekühlt wird.The components of phases (A) and (B) are combined at approx. 70 - 75 ° C and stirred until the phases appear homogeneous. The phases (A) and (B) are then combined and cooled to about 60 ° C., where they are emulsified and homogenized by vigorous stirring. The perfume phase (C) is added to the combined phases (A) and (B) at about 55 ° C., whereupon the entire mixture is cooled to room temperature with continued stirring.
BESTÄTIGINGSKOPiE
BESTÄTIGINGSKOPiE
Claims
1. Kühlende kosmetische oder medizinische topische Zubereitungen, gekennzeichnet durch einen Gehalt an einer oder mehreren Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, wobei diese Substanz oder Substanzen in den Zubereitungen in festem Zustand vorliegen.1. Cooling cosmetic or medical topical preparations, characterized by a content of one or more substances, the melting point or melting interval of which is selected in the range between 28 ° C and 40 ° C, and which have a positive enthalpy of fusion, this substance or substances in the preparations be in a solid state.
2. Verwendung einer oder mehrerer Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, zur Herstellung kühlend wirkender kosmetischer oder medizinischer topischer Zubereitungen, wobei diese Substanz oder Substanzen in den Zubereitungen in festem Zustand vorliegen.2. Use of one or more substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C and which have a positive enthalpy of fusion for the production of cooling cosmetic or medical topical preparations, this substance or substances in the preparations in solid state.
3. Zubereitungen nach Anspruch 1 oder Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß die Substanz oder die Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C liegt, und die positive Schmelzenthalpie aufweisen, in Konzentrationen von 0,5 - 50 Gew.-% vorliegen, vorteilhaft 1 - 20 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitungen.3. Preparations according to claim 1 or use according to claim 2, characterized in that the substance or substances whose melting point or melting interval is in the range between 28 ° C and 40 ° C, and have the positive enthalpy of fusion, in concentrations of 0.5 - 50 wt .-% are present, advantageously 1 - 20 wt .-%, based on the total weight of the preparations.
4. Zubereitungen nach Anspruch 1 oder Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß als die Substanz oder als die Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C liegt, und die positive Schmelzenthalpie aufweisen, eine oder mehrere lipophile Substanzen gewählt werden.4. Preparations according to claim 1 or use according to claim 2, characterized in that as the substance or as the substances whose melting point or melting interval is in the range between 28 ° C and 40 ° C and have the positive enthalpy of fusion, one or more lipophilic Substances can be chosen.
5. Zubereitungen oder Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß die Zubereitungen auf ausgeprägt hydrophile kosmetische oder dermatologische Grundlagen5. Preparations or use according to claim 4, characterized in that the preparations on a pronounced hydrophilic cosmetic or dermatological basis
BESTÄTIGINGSKOPiE beruhen, in denen die Substanz oder als die Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C liegt, und die positive Schmelzenthalpie aufweisen, dann bevorzugt feinpartikulär suspendiert vorliegen, beispielsweise in wäßrigen Gelformulierungen.BESTÄTIGINGSKOPiE are based, in which the substance or as the substances whose melting point or melting interval is in the range between 28 ° C. and 40 ° C. and which have a positive enthalpy of fusion are then preferably in finely particulate suspension, for example in aqueous gel formulations.
6. Zubereitungen nach Anspruch 1 oder Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß die Substanz oder Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, gewählt werden aus der Gruppe der lipophilen Substanzen, insbesondere der Ester der C1 -C18 Fettsäuren, mit niedermolekularen C^ - C5) Alkoholen, der Fettalkohole C8 - C22, der verzweigten oder unverzweigten Fettsäuren, der Kohlenwasserstoffe C16 - C22.6. Preparations according to claim 1 or use according to claim 2, characterized in that the substance or substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C, and have the positive enthalpy of melting are selected from the group of lipophilic substances, especially the esters of C 1 -C 18 fatty acids, with low molecular weight C ^ - C 5 ) alcohols, the fatty alcohols C 8 - C 22 , the branched or unbranched fatty acids, the hydrocarbons C 16 - C 22 .
7. Zubereitungen nach Anspruch 1 oder Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß die Substanz oder Substanzen, deren Schmelzpunkt oder Schmelzintervall im Bereich zwischen 28 °C und 40 °C gewählt wird, und die positive Schmelzenthalpie aufweisen, das Methylpalmitat gewählt wird..7. Preparations according to claim 1 or use according to claim 2, characterized in that the substance or substances whose melting point or melting interval is selected in the range between 28 ° C and 40 ° C, and have the positive enthalpy of fusion, the methyl palmitate is selected ..
BESTÄTIGINGSKOPiE BESTÄTIGINGSKOPiE
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DE10134607 | 2001-07-17 | ||
DE10134607A DE10134607A1 (en) | 2001-07-17 | 2001-07-17 | Cosmetic or dermatological preparations with a long-lasting cooling effect |
PCT/EP2002/007784 WO2003007908A2 (en) | 2001-07-17 | 2002-07-12 | Cosmetic or dermatological preparations having a long-term cooling action |
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EP (1) | EP1414398A2 (en) |
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CA2490343A1 (en) * | 2003-12-17 | 2005-06-17 | Cordis Neurovascular, Inc. | Activatable bioactive implantable medical device and method of use |
AU2005262354B2 (en) * | 2004-07-01 | 2008-10-23 | E-L Management Corp. | Cosmetic compositions and methods for sensory cooling |
US20060062811A1 (en) | 2004-09-21 | 2006-03-23 | Szymczak Christopher E | Medicinal cooling emulsions |
EP1901631B1 (en) * | 2005-06-16 | 2012-03-21 | Colgate-Palmolive Europe SARL | Water-based antiperspirant and aerosol dispenser therefor |
US8039011B2 (en) * | 2006-10-10 | 2011-10-18 | Kimberly-Clark Worldwide, Inc. | Skin cooling compositions |
US8029771B2 (en) * | 2007-06-29 | 2011-10-04 | Mary Kay Inc. | Guar gum containing compounds |
US20090110656A1 (en) * | 2007-10-31 | 2009-04-30 | Lemke Sarah A | Skin cooling composition |
US20090130042A1 (en) * | 2007-11-16 | 2009-05-21 | Conopco, Inc., D/B/A Unilever | Topical composition |
US20090157153A1 (en) * | 2007-12-13 | 2009-06-18 | Sarah Anne Lemke | Skin cooling system |
US9480633B2 (en) | 2011-04-28 | 2016-11-01 | Kimberly-Clark Worldwide, Inc. | Temperature management composition |
US9084764B2 (en) | 2012-08-16 | 2015-07-21 | Exert Co. | Epidermal cooling |
KR20150122204A (en) * | 2013-02-27 | 2015-10-30 | 이엘씨 매니지먼트 엘엘씨 | Compositions with thermally-regulating material |
FR3029777B1 (en) * | 2014-12-15 | 2019-11-29 | L'oreal | USE OF THE ASSOCIATION OF AN ASSOCIATIVE NON-IONIC POLYURETHANE POLYETHER AND A CYCLOHEXANOL DERIVATIVE AS A SKIN-REFRESHING AGENT |
US11826440B2 (en) | 2016-05-11 | 2023-11-28 | Formulated Solutions, Llc | Thermal-stable whipped formulations |
EP3634363A1 (en) * | 2017-05-11 | 2020-04-15 | Beiersdorf Ag | Gel formulations |
JP6776301B2 (en) * | 2018-07-10 | 2020-10-28 | 株式会社カナエテクノス | Manufacturing method for external patches and gel bases |
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US4605670A (en) * | 1984-02-01 | 1986-08-12 | Nitto Electric Industrial Co., Ltd. | Method for percutaneously administering metoclopramide |
US4855127A (en) * | 1986-07-07 | 1989-08-08 | Dow Corning Corporation | Lattice-entrapped composition |
US5026556A (en) * | 1988-11-10 | 1991-06-25 | Norwich Eaton Pharmaceuticals, Inc. | Compositions for the transdermal delivery of pharmaceutical actives |
US5674504A (en) * | 1989-07-12 | 1997-10-07 | L'oreal | Cosmetic composition in the form of an aqueous gel containing in suspension spheroids of a non-hydrophilic, lipoidal substance |
US5109022A (en) * | 1990-10-24 | 1992-04-28 | Wisconsin Alumni Research Foundation | Non-insecticidal insect repellent |
DE4312656C2 (en) * | 1993-04-19 | 1996-01-25 | Beiersdorf Ag | Cooling cosmetic or dermatological compositions |
WO1995016824A1 (en) * | 1993-12-13 | 1995-06-22 | The Procter & Gamble Company | Lotion composition for imparting soft, lubricious feel to tissue paper |
FR2720934B1 (en) * | 1994-06-14 | 1996-07-12 | Oreal | Oil-in-water cleaning emulsion with the appearance of milk. |
FR2721210B1 (en) * | 1994-06-17 | 1996-08-02 | Oreal | Cleaning composition containing lipid grains. |
US5665426A (en) * | 1995-02-06 | 1997-09-09 | Kimberly-Clark Corporation | Soft treated tissue |
US5601871A (en) * | 1995-02-06 | 1997-02-11 | Krzysik; Duane G. | Soft treated uncreped throughdried tissue |
US5637140A (en) * | 1995-06-21 | 1997-06-10 | Brother Kogyo Kabushiki Kaisha | Water-based ink composition and ink-jet recording process |
ATE182068T1 (en) * | 1996-01-10 | 1999-07-15 | Oreal | USE OF A POLYHOLOSIDE IN A CLEANSING OR MAKEUP REMOVAL COMPOSITION AND COMPOSITION CONTAINING A POLYHOLISIDE |
US6187695B1 (en) * | 1998-12-08 | 2001-02-13 | Kimberly-Clark Worldwide, Inc. | Cool feeling tissue product and method |
US6444219B2 (en) * | 1998-10-09 | 2002-09-03 | Allor Foundation | Antiseptic packaged polyvinylpyrrolidone-cinnamic alcohol solid products and the like and method of preparing the same |
EP1196053B1 (en) * | 1999-05-21 | 2007-01-10 | Outlast Technologies, Inc. | Temperature-stabilized articles |
DE20011491U1 (en) * | 2000-06-30 | 2000-10-12 | Kampffmeyer Mühlen GmbH, 21107 Hamburg | Skin care products |
EP1250914B2 (en) * | 2001-04-17 | 2015-11-25 | The Procter & Gamble Company | Cooling compositions |
-
2001
- 2001-07-17 DE DE10134607A patent/DE10134607A1/en not_active Withdrawn
-
2002
- 2002-07-12 EP EP02754879A patent/EP1414398A2/en not_active Withdrawn
- 2002-07-12 WO PCT/EP2002/007784 patent/WO2003007908A2/en not_active Application Discontinuation
- 2002-07-12 JP JP2003513517A patent/JP2004536126A/en active Pending
-
2004
- 2004-01-16 US US10/759,946 patent/US20050053632A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO03007908A2 * |
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WO2003007908A3 (en) | 2003-12-04 |
US20050053632A1 (en) | 2005-03-10 |
WO2003007908A2 (en) | 2003-01-30 |
JP2004536126A (en) | 2004-12-02 |
DE10134607A1 (en) | 2003-02-06 |
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