EP1294351A1 - Verwendung von calcium freisetzenden oder bindenden substanzen zur gezielten schwächung oder stärkung der barrierefunktion der haut - Google Patents
Verwendung von calcium freisetzenden oder bindenden substanzen zur gezielten schwächung oder stärkung der barrierefunktion der hautInfo
- Publication number
- EP1294351A1 EP1294351A1 EP01947333A EP01947333A EP1294351A1 EP 1294351 A1 EP1294351 A1 EP 1294351A1 EP 01947333 A EP01947333 A EP 01947333A EP 01947333 A EP01947333 A EP 01947333A EP 1294351 A1 EP1294351 A1 EP 1294351A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- skin
- calcium
- acid
- preparations
- substances
- 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- Withdrawn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
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- 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
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- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
Definitions
- the present invention relates to the use of calcium-releasing or binding substances for the targeted weakening or strengthening of the barrier function of the skin.
- the skin is the largest human organ. Among its many functions (for example for heat regulation and as a sensory organ), the most important is the barrier function that prevents the skin (and ultimately the entire organism) from drying out. 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 epidermis is a stratified tissue in which the outer layer, the horny layer (stratum corneum), is the important part for the barrier function. It is worn away in contact with the environment and is therefore in a constant renewal process, with fine flakes being continuously released to the outside and corneal and lipid material horned from the inside being reproduced.
- the skin model recognized by experts today (PM Elias, Structure and Function of the Stratum Corneum Permeability Bar er, Drug Dev. Res. 13, 1988, 97-105) describes the horny layer as a two-component system, similar to a brick wall (brick - mortar model).
- the horny cells (komeocytes) correspond to the bricks
- the complex lipid membrane in the intercellular spaces corresponds to the mortar.
- This system essentially represents a physical barrier against hydrophilic substances, but can because of its narrow and multilayer structure equally, it is difficult for lipophilic substances to pass through.
- the special structure of the horny layer protects the skin on the one hand and on the other hand stabilizes its own flexibility by binding a defined amount of water.
- the regulation of water and moisture content is one of the most important functions of the epidermal lipid membrane. However, it not only has a barrier effect against external chemical and physical influences, but also contributes to the cohesion of the horny layer.
- the lipids of the horny layer consist essentially of ceramides, free fatty acids, triglycerides, cholesterol, cholesterol esters and cholesterol sulfate and are distributed over the entire horny layer.
- the composition of these lipids is of crucial importance for the intact function of the epidermal barrier and thus for the water impermeability of the skin.
- the barrier effect of the skin can be quantified by determining the transepidermal water loss (TEWL - transepidermal water ioss). This is the evaporation of water from the inside of the body without including the loss of water when sweating.
- the determination of the TEWL value has proven to be extremely informative and can be used to diagnose cracked or chapped skin, to determine the compatibility of chemically differently structured surfactants and the like.
- the water content in the top layer of skin is of the utmost importance. It can be influenced to a limited extent by introducing moisture regulators.
- Anionic surfactants which are generally components of cleaning preparations, can increase the pH value in the horny layer for a long time, which greatly hinders regenerative processes that serve to restore and renew the barrier function of the skin. In this case, between regeneration and the loss of essential substances through regular extraction, a new, often very, arises in the horny layer unfavorable state of equilibrium, which decisively affects the external appearance of the skin and the physiological functioning of the horny layer.
- Skin care in the sense of the present invention is to be understood primarily as meaning that the natural function of the skin acts as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the loss of the body's own substances (e.g. water, lipids) , Electrolytes) is strengthened or restored.
- environmental influences e.g. dirt, chemicals, microorganisms
- the loss of the body's own substances e.g. water, lipids
- Electrolytes e.g. water, lipids
- the effect of ointments and creams on the barrier function and the hydration of the horny layer is based essentially on the covering (occlusion) of the treated skin areas.
- the ointment or cream is, so to speak, a (second) artificial barrier that is supposed to prevent water loss from the skin.
- This physical barrier can be removed correspondingly easily, for example with cleaning agents, as a result of which the original, impaired state is reached again.
- the skin care effect can decrease with regular treatment. After stopping the application of the product, the skin quickly returns to the state before the start of treatment. With certain products, the condition of the skin may even temporarily deteriorate. A sustainable product effect is therefore generally not achieved or only to a limited extent.
- the effect of nourishing cleaning products essentially consists in an efficient regreasing with sebum lipid-like substances.
- the simultaneous reduction in the surfactant content of such preparations can further limit the damage to the homolayer barrier.
- the prior art lacks preparations which positively influence the barrier function and the hydration of the horny layer and which strengthen or even restore the physicochemical properties of the horny layer and in particular of the lamellae from intercellular lipids.
- the skin of newborns and toddlers is particularly thin and is characterized by a weak and permeable barrier in the horny layer.
- the pH buffer capacity of the baby skin is severely limited, so that changes in the pH value on the skin very quickly lead to skin irritation.
- the accumulation of urine and faeces in the baby diaper can lead to the release of ammonia from urea with the help of microorganisms. This ammonia very quickly penetrates the living cells through the horny layer barrier and can increase the pH of the tissue. With a longer incubation period, this pH increase can lead to diaper rash (dermatitis ammoniacalis).
- the epidermis is richly equipped with nerves and nerve end devices such as Father Pacini lamellar bodies, Merkel cell neurite complexes and free nerve endings for sensation of pain, cold, heat and itching.
- nerves and nerve end devices such as Father Pacini lamellar bodies, Merkel cell neurite complexes and free nerve endings for sensation of pain, cold, heat and itching.
- This "sensitive skin” differs fundamentally from “dry skin” with thickened and hardened hom layers.
- Typical reactions of "stinging" to sensitive skin are reddening, tension and burning of the skin as well as itching.
- Typical disturbing neurosensory phenomena associated with the terms "stinging” or “sensitive skin” are reddening of the skin, tingling, tingling, tension and burning of the skin and itching.
- the object of the present invention was therefore to eliminate the disadvantages of the prior art.
- skin-care preparations and preparations for cleaning the skin should be made available which maintain or restore the skin's barrier properties, especially when the natural regeneration of the skin is not sufficient. They are also intended for the treatment and prophylaxis of consequential damage Drying out of the skin, for example fissures or inflammatory or allergic processes or also neurodermatitis, may be suitable.
- Ca 2+ serves as a versatile messenger (second messenger), with its concentration changing in the range 0.1-10 mmol / l.
- sarcoplasmic reticulum is infiltrated by calcium pumps, bound to calreticulin and calsequestrin and can be released through calcium channels, which are activated by the messenger substances inositol 1, 4,5-trisphosphate and cyclic ADP-ribose.
- the function of the Ca 2 + as a cellular regulator is linked to many calcium-binding proteins.
- cosmetic products or other products that come into contact with human skin are added, such as diapers, handkerchiefs, plasters, wound dressings, bath water, textiles, rubber gloves, disinfectants, with builders, sparingly soluble calcium salts (e.g.
- phosphates such as NaH 2 PO 4 , but also zeolites and / or layered silicates with calcium binding capacity and / or as substances known in detergent technology under the term “builder”, for example water-soluble, linear polymers with numerous carboxy groups) or calcium complexing agents (for example polyphosphates, tannic acids, EDTA (ethylenediaminetetraacetic acid), EGTA (ethylenebis (oxyethylenenitri - lo) -tetraacetic acid), citric acid, oxalic acid, free fatty acids etc.) and if this is applied to the skin or if it brings it into contact with human skin, the trans-epidermal water loss as a measure of the quality of the skin barrier is reduced to 80 - 90% of the initial value is reduced, which is accompanied by a thickening of the stratum comeum.
- builder for example water-soluble, linear polymers with numerous carboxy groups
- calcium complexing agents for example polyphosphates, tannic acids, EDTA (
- the pH of the skin and the skin flora are normalized. Allergens and irritants are less able to penetrate, there are less and less violent irritative or allergic reactions barrier-damaging effects of occlusion and calcium-containing substance Fixed a colonization with pathogenic germs, soreness and inflammation is counteracted.
- Complexing agents form complexes with metal atoms which, if one or more polybasic complexing agents, ie chelators, are metalacycles.
- Chelates are compounds in which a single ligand occupies more than one coordination site on a central atom. In this case, normally elongated compounds are closed to form rings by complex formation via a metal atom or ion. The number of ligands bound depends on the coordination number of the central metal. The prerequisite for chelation is that the compound reacting with the metal contains two or more atom groups which act as electron donors.
- the calcium complexing agent (s) can advantageously be selected from the group of the usual compounds, preferably at least one substance from the group consisting of tartaric acid and its anions, citric acid and its anions, amino polycarboxylic acids and their anions (such as, for example, ethylenediaminetetraacetic acid (EDTA) and their Anions, nitrilotriacetic acid (NTA) and their anions, hydroxyethylenediaminotriesacetic acid (HOEDTA) and their anions, diethylenaminopentaacetic acid (DPTA) and their anions, trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) and their anions).
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- HOEDTA hydroxyethylenediaminotriesacetic acid
- DPTA diethylenaminopentaacetic acid
- CDTA trans-1,2-
- the calcium-binding substances and / or calcium complexing agents are advantageous in cosmetic or dermatological preparations, preferably at 0.01 % By weight to 10% by weight, preferably 0.05% by weight to 5% by weight, particularly preferably 0.1-2.0% by weight, based on the total weight of the preparations ,
- barrier strengthening or “strengthening the barrier function of the skin” is to be understood in particular to mean the following effect: the active compounds according to the invention interact with the lipids of the horny layer in such a way that the arrangement of these lipids in the horny layer at the molecular level is improved. This means that the natural function of the skin as a barrier against environmental influences and against the loss of the body's own substances is strengthened or restored.
- a second or alternate effect of the invention in terms of strengthening the skin barrier can consist in that the lipid synthesis system of the keratinocytes is stimulated or is stimulated by the combination of active substances used according to the invention.
- calcium is preferably used in corresponding products to 0.01% by weight to 10% by weight, preferably to 0.05% by weight to 5% by weight, particularly preferably to 0, 1 - 2.0 wt .-%, based on the total weight of the preparations.
- Products of this type are suitable, for example, as 1. Pre-Sun products for building up a “light callus”, 2. nasal cream against soreness in case of runny nose,
- the cosmetic or dermatological preparations according to the invention can be composed as usual and can be used for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics. Correspondingly, depending on their structure, they can be used, for example, as a skin protection cream, cleansing milk, sunscreen lotion, nutritional cream, day or night cream, etc. It may be possible and advantageous to use the preparations according to the invention as the basis for pharmaceutical formulations.
- the preparations according to the invention contain z. B.
- 0.001 to 30 wt .-% preferably 0.01 wt .-% to 10 wt .-%, but in particular 0.01 wt .-% to 0.5 wt .-%, each based on the total weight of the preparations on the active compounds according to the invention.
- the active compound combinations used according to the invention are particularly preferably used in pH-buffered preparations, a pH range from 6 to 7, in particular about 6.5, being very particularly preferred.
- Cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.
- these preferably contain at least one UV-A filter substance and / or at least one UV-B filter substance and / or at least one inorganic pigment.
- the cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations, e.g. B. preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing and / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
- cosmetic auxiliaries e.g. B. preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing and / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, poly
- Preparations for the treatment and care of the skin are particularly preferred.
- the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
- Cosmetic and dermatological preparations according to the invention can be in various forms. So you can z. B. a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) or oil-in-water (O / W) type, a multiple emulsions, for example of the water-in-oil type Oil-in-water (W / O / W), a gel, a solid stick, an ointment or an aerosol. It is also advantageous to present the active compounds according to the invention in encapsulated form, e.g. B. in collagen matrices and other common encapsulation materials, e.g. B. as cellulose encapsulation, encapsulated in gelatin, wax matrices or liposomal.
- encapsulated form e.g. B. in collagen matrices and other common encapsulation materials, e.g. B. as cellulose encapsulation, encapsulated in gelatin,
- the cosmetic and dermatological preparations according to the invention can also contain antioxidants.
- all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
- the antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-camosine, L-carnosine and their Derivatives (e.g. anserine), carotenoids, carotenes (e.g. ⁇ -carotene, ß-carotene, ⁇ -lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g.
- amino acids e.g. glycine, histidine, tyrosine, tryptophan
- imidazoles e.g. urocanic acid
- peptides such as D, L-carnosine, D-camosine, L-carnosine and their Derivatives (e.g. an
- thioglucose e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, Palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g.
- metal chelators e.g. ⁇ -hydroxyfatty acids, palmitic acid, Phytic acid, lactoferrin
- ⁇ -hydroxy acids e.g. citric acid, Mil chic acid, malic acid
- humic acid bil
- B ⁇ -linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. Ascorbylpaimitat, Mg-Ascorbylphosphat, Aseorbylacetat), Tocopherols and derivatives (z Vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, ⁇ -glycosyl rutin, ferric acid, furfurylidene glucitol, camosin, butylated hydroxytoluene, butylated hydroxyanisole, noradehydrogenated hydrochloric acid , Trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g.
- ZnO, ZnSO 4 selenium and its derivatives (e.g. selenomethionine), stilbenes and their derivatives (e.g. 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 substances.
- selenium and its derivatives e.g. selenomethionine
- stilbenes and their derivatives e.g. stilbene oxide , Trans-stilbene oxide
- the derivatives suitable according to the invention salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
- the amount of the aforementioned antioxidants (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight the preparation.
- vitamin E and / or its derivatives represent the antioxidant (s)
- vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.
- Emulsions according to the invention are advantageous and contain e.g. the fats, oils, waxes and other fat bodies mentioned, as well as water and an emulsifier, as is usually used for such a type of formulation.
- the lipid phase can advantageously be selected from the following group of substances: mineral oils, mineral waxes
- 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 alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids; benzoates;
- Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
- the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of 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 with a chain length of 3 to 30 carbon atoms, from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms 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-ethylhexyl, ethyl-2-ethylhexyl, ethyl-2-ethylhexyl 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semi-synthetic and natural mixtures of such esters, for example jojoba oil.
- the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also fatty acid triglycerides, especially the triglycerol 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.
- 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 2- i 5 -alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.
- Particularly advantageous are mixtures of C ⁇ -2- i5 AIkylbenzoat and 2-ethylhexyl isostearate, mixtures of d 2- i5-alkyl benzoate and isotridecyl isononanoate and mixtures of C 12- 15 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
- hydrocarbons paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.
- the oil phase can advantageously also contain 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.
- Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention.
- silicone oils are also advantageous in the sense of to use the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
- Mixtures of cyclomethicone and isotridecyl isononanoate, of cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.
- Advantageous emulsifiers are, for example, glyceryl stearate in a mixture with ceteareth-20; sorbitan; sorbitan; Ceteareth-25; Ceteareth-6 in a mixture with stearyl alcohol; Cetylstearyl alcohol mixed with PEG-40 castor oil and sodium cetylstearyl sulfate; Triceteareth-4 phosphate; Glyeerylstearat; sodium cetylstearyl; lecithin; Trilaureth-4 phosphate; Laureth-4 phosphate; stearic acid; Propylene glycol stearate SE; PEG-25 hydrogenated castor oil; PEG-54 hydrogenated castor oil; PEG-6 caprylic acid / capric acid glycerides; sorbitan; Glyceryl oleate in a mixture with propylene glycol; PEG-9 stearate; glyceryl; Ceteth-2; Ceteth-20; Polysorbate 60; Lanolin; G
- the aqueous phase of the preparations according to the invention advantageously 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 ether or monobutyl ether, propylene glycol monomethyl or monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, furthermore alcohols of low C number, for example Ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickening agents, which one or more can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g.
- Hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, in each case individually or in combination.
- Water can also be a component of alcoholic solvents.
- Emulsions according to the invention are advantageous and contain e.g. the fats, oils, waxes and other fat bodies mentioned, as well as water and an emulsifier, as is usually used for such a type of formulation.
- Gels according to the invention usually contain alcohols of low C number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and water or an oil mentioned above in the presence of a thickener which, in the case of oily alcoholic gels, preferably silicon dioxide or an aluminum silicate aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
- Suitable propellants for preparations according to the invention which can be sprayed from aerosol containers are the customary, known volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or in a mixture with one another. Compressed air can also be used advantageously.
- 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 to provide preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.
- 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 to provide preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.
- 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,
- benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
- 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;
- Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
- Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bomylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their Salts as well as the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and its salts (the corresponding 10-sulfato compounds, for example the corresponding sodium, potassium or triethanolammonium salt), too referred to as benzene-1,4-di (2-oxo-3-bornylidenemethyl-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.
- the invention also relates to the use of a combination of the active compound combinations used according to the invention with at least one UVB filter as an antioxidant or the use of a combination of the active compound combinations used according to the invention with at least one UVB filter as an antioxidant in a cosmetic or dermatological preparation.
- UVA filters which have hitherto usually been contained in cosmetic preparations.
- These substances are preferably derivatives of di-benzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.
- These combinations or preparations containing these combinations are also the subject of the invention.
- the quantities used for the UVB combination can be used.
- the invention also relates to the use of a combination of active ingredient combinations according to the invention with at least one UVA filter as an antioxidant or the use of a combination of the active ingredient combinations according to the invention with at least one UVA filter as an antioxidant in a cosmetic or dermatological preparation.
- the invention also relates to the use of a combination of active ingredient combinations according to the invention with at least one UVA filter and at least one UVB filter as an antioxidant, or the use of a combination of active ingredient combinations with at least one UVA filter and at least one UVB filter as Antioxidant in a cosmetic or dermatological preparation.
- Cosmetic and dermatological preparations with an effective content of active ingredient combinations used according to the invention can also contain inorganic pigments which are usually used in cosmetics to protect the skin from UV rays. be applied. These are oxides of titanium, zinc, zirconium, silicon, manganese, 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.
- UVA filter and pigment or preparations containing this combination are also the subject of the invention.
- the amounts given for the above combinations can be used.
- Cosmetic and dermatological preparations for protecting the hair from UV rays according to the invention are, for example, shampooing agents, preparations which are used when rinsing the hair before or after the shampooing, before or after the permanent wave treatment, before or after the coloring or discoloration of the Hair is applied to preparations for blow-drying or pickling hair, preparations for coloring or decolouring, to a styling and treatment lotion, a hair lacquer or to permanent waving agents.
- the cosmetic and dermatological ingredients contain active ingredients and auxiliary substances, as are usually used for this type of preparations for hair care and hair treatment.
- Auxiliaries are preservatives, surface-active substances, substances to prevent foaming, thickeners, emulsifiers, fats, oils, waxes, organic solvents, bactericides, perfumes, dyes or pigments, the task of which is to add hair or the cosmetic or dermatological preparation itself dye, electrolytes, substances against greasing the hair.
- Electrolytes for the purposes of the present invention are water-soluble alkali metal, ammonium, alkaline earth metal (including magnesium) and zinc salts of inorganic anions and any mixtures of such salts, it being necessary to ensure that these salts are pharmaceutically or cosmetically harmless distinguished.
- the anions according to the invention are preferably selected from the group of chlorides, sulfates and hydrogen sulfates, phosphates, hydrogen phosphates and linear and cyclic oligophosphates as well as carbonates and hydrogen carbonates.
- Cosmetic preparations which are a skin cleansing agent or shampooing agent preferably contain at least one anionic, nonionic or amphoteric surface-active substance, or mixtures of such substances, the active substance combinations used according to the invention in the aqueous medium and auxiliaries, as are usually used therefor.
- the surface-active substance or the mixtures of these substances can be present in the shampoo in a concentration between 1% by weight and 50% by weight.
- a lotion that is rinsed out and e.g. before or after decolorization, before or after shampooing, between two shampooing steps, before or after permanent wave treatment, these are e.g. around aqueous or aqueous-alcoholic solutions, which may contain surface-active substances, the concentration of which may be between 0.1 and 10% by weight, preferably between 0.2 and 5% by weight.
- These cosmetic or dermatological preparations can also be aerosols with the auxiliaries usually used for them.
- a cosmetic preparation in the form of a lotion that is not rinsed out, in particular a lotion for inlaying the hair, a lotion used for blow-drying the hair, a styling and treatment lotion generally provides an aqueous, alcoholic or aqueous-alcoholic solution represents and contains at least one cationic, anionic, non-ionic or amphoteric polymer or mixtures thereof, as well as active ingredient combinations used according to the invention in effective concentration.
- the amount of the polymers used is e.g. between 0.1 and 10% by weight, preferably between 0.1 and 3% by weight.
- Cosmetic preparations for the treatment and care of the hair which contain the active compound combinations used according to the invention, can be present as emulsions which are of the non-ionic or anionic type.
- non-ionic emulsions contain oils or fatty alcohols, which can also be polyethoxylated or polypropoxylated, for example, or also mixtures of the two organic components.
- These emulsions may contain cationic surface-active substances.
- cosmetic preparations for the treatment and care of the hair can be in the form of gels which, in addition to an effective content of active substances according to the invention and, if appropriate, solvents conventionally used therefor, preferably water, and also organic thickeners, for example gum arabic, xanthan gum, sodium malginate, cellulose derivatives , preferably methyl cellulose, hydroxymethyl cellulose, hydro- xyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, for example aluminum silicates such as bentonites, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate.
- the thickening agent is contained in the gel, for example, in an amount between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight.
- the amount of active compounds according to the invention in an agent intended for the hair is preferably 0.05% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, based on the total weight of the agent.
- Aqueous cosmetic cleaning agents according to the invention or water-free or water-free cleaning agent concentrates intended for aqueous cleaning can contain anionic, nonionic and / or amphoteric surfactants.
- Surfactants are amphiphilic substances that can dissolve organic, non-polar substances in water. Due to their specific molecular structure with at least one hydrophilic and one hydrophobic part of the molecule, they ensure a reduction in the surface tension of the water, wetting of the skin, facilitating dirt removal and removal, easy rinsing and, if desired, foam regulation.
- hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO " , -OSO 3 2" , -SO 3 ' , while the hydrophobic parts generally represent non-polar hydrocarbon radicals.
- Surfactants are generally classified according to the type and charge of the hydrophilic part of the molecule. There are four groups:
- Anionic surfactants generally have carboxylate, sulfate or functional groups
- Sulfonate 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 an aqueous 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.
- Anionic surfactants to be used advantageously are acylamino acids (and their salts), such as
- acyl glutamates for example sodium acyl glutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate
- acyl peptides for example palmitoyl-hydrolyzed milk protein, sodium cocoyl-hydrolyzed 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 cocoyl taurate
- acyl lactylates lauroyl lactylate, caproyl lactylate
- Carboxylic acids and derivatives such as
- 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-lauramide carboxylate,
- ether carboxylic acids for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, Phosphoric acid esters and salts, such as DEA-oleth-10-phosphate and dilaureth-4-phosphate,
- acyl isethionates e.g. Sodium / ammonium cocoyl isethionate
- alkyl sulfonates for example sodium cocosmonoglyceride sulfate, sodium C ⁇ 2- ⁇ olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate
- sulfosuccinates for example dioctyl sodium sulfosuccinate, disodium laureth sulfosate cinate, disodium auccinate succulate sulfate,
- alkyl ether sulfate for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium and sodium C ⁇ 2 - 13 -Parethsulfat, 2. alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.
- Cationic Surfactants Cationic surfactants to be used advantageously are
- Quaternary surfactants contain at least one N atom which is covalently linked to 4 alkyl and / or aryl groups. Regardless of the pH value, this leads to a positive charge.
- Advantageous quaternary surfactants are alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysulfain.
- Cationic surfactants can furthermore preferably be selected for the purposes of the present invention from the group of the quaternary ammonium compounds, in particular benzyltrialkylammonium chlorides or bromides, such as, for example, benzyldimethylstearylammonium chloride, furthermore alkyltrialkylammonium salts, for example cetyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium or bromides, dialkyldimethylammonium chlorides or bromides, alkylamidethyltrimethylammonium 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 acylamphohydroxypropyl sulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,
- 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 cholesteresters, ethoxylated / propoxylated triglyceride esters, ethoxylated / propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and such as lauryl glucoside, decyl glycoside and cocoglycoside.
- Cosmetic preparations which are cosmetic cleaning preparations for the skin, can be in liquid or solid form.
- active ingredient combinations used according to the invention they preferably contain at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, if desired one or more electrolytes and auxiliaries, as are usually used for this.
- the surface-active substance can be present in the cleaning preparations in a concentration between 1 and 94% by weight, based on the total weight of the preparations.
- cosmetic preparations which are a shampooing agent preferably contain at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, optionally an electrolyte and auxiliary according to the invention, as are usually used therefor.
- the surface-active substance can be present in the shampoo in a concentration between 1% by weight and 94% by weight.
- compositions according to the invention contain water and, if appropriate, the additives customary in cosmetics, for example perfume, thickeners, dyes, deodorants, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active substances and the like.
- the additives customary in cosmetics for example perfume, thickeners, dyes, deodorants, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active substances and the like.
- Complexing agents are known auxiliaries in cosmetology and medical galenics.
- the complexation of interfering metals such as Mn, Fe, Cu and others can, for example, prevent undesired chemical reactions in cosmetic or dermatological preparations.
- the present invention also includes a method for protecting cosmetic or dermatological preparations against oxidation or photooxidation, these preparations being, for example, preparations for the treatment and care of the hair, in particular hair colorants, hair lacquers, shampooing agents, color shampooing agents, also make-up products such as nail polishes, Lipsticks, complexion bases, washing and shower preparations, creams for the treatment or care of the skin or for all other whose cosmetic preparations are concerned, the components of which can cause stability problems due to oxidation or photooxidation during storage, characterized in that the cosmetic preparations have an effective content of active compound combinations used according to the invention.
- these preparations being, for example, preparations for the treatment and care of the hair, in particular hair colorants, hair lacquers, shampooing agents, color shampooing agents, also make-up products such as nail polishes, Lipsticks, complexion bases, washing and shower preparations, creams for the treatment or care of the skin or for all other whose cosmetic preparations are concerned, the components of which can cause stability problems due to oxidation
- the amount of active compound combinations used according to the invention in these preparations is preferably 0.01-10% by weight, preferably 0.05-5% by weight, in particular 0.1-2.0% by weight, based on the total weight of the preparations.
- the invention also relates to the process for the preparation of the cosmetic compositions according to the invention, which is characterized in that active ingredient combinations according to the invention are incorporated into cosmetic and dermatological formulations in a manner known per se.
- Glyceryl caprylate q.s.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10031703 | 2000-06-29 | ||
DE10031703A DE10031703A1 (de) | 2000-06-29 | 2000-06-29 | Verwendung von Calcium freisetzenden oder bindenden Substanzen zur gezielten Schächung oder Stärkung der Barrierefunktion der Haut |
PCT/EP2001/006262 WO2002000185A1 (de) | 2000-06-29 | 2001-06-01 | Verwendung von calcium freisetzenden oder bindenden substanzen zur gezielten schwächung oder stärkung der barrierefunktion der haut |
Publications (1)
Publication Number | Publication Date |
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EP1294351A1 true EP1294351A1 (de) | 2003-03-26 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01947333A Withdrawn EP1294351A1 (de) | 2000-06-29 | 2001-06-01 | Verwendung von calcium freisetzenden oder bindenden substanzen zur gezielten schwächung oder stärkung der barrierefunktion der haut |
Country Status (5)
Country | Link |
---|---|
US (1) | US20040086538A1 (ja) |
EP (1) | EP1294351A1 (ja) |
JP (1) | JP2004501872A (ja) |
DE (1) | DE10031703A1 (ja) |
WO (1) | WO2002000185A1 (ja) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10129973A1 (de) | 2001-06-21 | 2003-01-02 | Beiersdorf Ag | Kosmetische oder dermatologische getränkte Tücher |
DE10214273A1 (de) * | 2002-03-28 | 2003-10-23 | Schott Glas | Glas- und/oder Glaskeramikpulver oder-fasern zur kontrollierten Ionenabgabe |
DE10221812A1 (de) * | 2002-05-16 | 2003-11-27 | Beiersdorf Ag | Multifunktionelle kosmetische Reinigungszubereitung |
DE10311852A1 (de) * | 2003-03-17 | 2004-10-14 | Henkel Kgaa | Textilbehandlungsmittel |
US8147825B2 (en) | 2004-01-22 | 2012-04-03 | University Of Miami | Topical co-enzyme Q10 formulations and methods of use |
WO2006074177A2 (en) * | 2005-01-06 | 2006-07-13 | Mary Kay Inc. | Alcohol-free microemulsion composition |
JP4526469B2 (ja) * | 2005-11-02 | 2010-08-18 | 株式会社ピカソ美化学研究所 | 化粧料 |
ES2688931T3 (es) | 2006-05-05 | 2018-11-07 | Blaa Lonid Hf. | Uso farmacéutico y cosmético de la sílice |
DE102006035040A1 (de) * | 2006-07-28 | 2008-01-31 | Beiersdorf Ag | Wirkstoffkombinationen aus Ascorbylverbindung und hydriertem Lecithin |
MX352434B (es) | 2007-03-22 | 2017-11-24 | Berg Llc | Formulaciones topicas que tienen biodisponibilidad aumentada. |
JP2008273874A (ja) * | 2007-04-27 | 2008-11-13 | Fuji Chem Ind Co Ltd | 頭皮外用剤 |
CN102083424B (zh) | 2008-04-11 | 2013-08-28 | 细胞研究有限公司 | 诱导癌细胞凋亡的方法和应用 |
EP2233128A1 (en) * | 2009-03-25 | 2010-09-29 | Cognis IP Management GmbH | Cosmetic composition |
SG10201402288RA (en) | 2009-05-11 | 2014-07-30 | Berg Llc | Methods for the diagnosis of oncological disorders using epimetabolic shifters, multidimensional intracellular molecules, or environmental influencers |
KR102008658B1 (ko) | 2010-03-12 | 2019-08-08 | 베르그 엘엘씨 | 코엔자임 Q10(CoQ10)의 정맥내 제형 및 이의 사용 방법 |
CN103608323B (zh) | 2011-04-04 | 2016-08-17 | 博格有限责任公司 | 治疗中枢神经系统肿瘤的方法 |
MY183615A (en) | 2011-06-17 | 2021-03-03 | Berg Llc | Inhalable pharmaceutical compositions |
CN113797343A (zh) | 2013-04-08 | 2021-12-17 | 博格有限责任公司 | 使用辅酶q10联合疗法治疗癌症 |
HUE050060T2 (hu) | 2013-09-04 | 2020-11-30 | Berg Llc | Eljárások rák kezelésére koenzim Q10 folyamatos infúziójával |
DE202017107326U1 (de) * | 2017-12-01 | 2018-11-21 | Kerstin Kräft | Hautpflegeemulsion |
CN112137995A (zh) | 2019-06-28 | 2020-12-29 | 默克专利股份有限公司 | 增加皮肤细胞中钙的细胞利用率的方法和混合物 |
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DE955541C (de) * | 1953-06-02 | 1957-01-03 | Sandoz Akt Ges | Verfahren zur Herstellung einer haltbaren, leicht resorbierbaren Antihistamin-Salbe |
US2967131A (en) * | 1954-02-08 | 1961-01-03 | Charles J Nemanick | Therapeutic composition |
FR2073271A1 (en) * | 1969-12-11 | 1971-10-01 | Boivin Jean | Calcium salt - vitamin d2 compn - for treatment of decalcification of |
FR2618333B1 (fr) * | 1987-07-20 | 1990-07-13 | Merck Sharp & Dohme | Composition pharmaceutique et/ou cosmetique a usage topique contenant de la gomme rhamsam |
AU662101B2 (en) * | 1990-04-26 | 1995-08-24 | Procter & Gamble Company, The | Chelator compositions comprising oxime compounds |
DE19725405A1 (de) * | 1997-06-17 | 1998-12-24 | Kramer Axel Prof Dr Med Sc | Physiologische Wirkstoffkombination zur Förderung der Abwehrleistung der Haut gegenüber Noxen |
DE19754659C2 (de) * | 1997-12-09 | 2000-09-07 | Hans Joachim Schwanitz | Verwendung von Kohlensäure zur Stabilisierung oder Erhöhung der epidermalen Ceramidsyntheserate |
JP3948588B2 (ja) * | 1998-03-05 | 2007-07-25 | 株式会社資生堂 | 皮膚バリアー機能回復促進剤 |
DE19824727A1 (de) * | 1998-06-03 | 1999-12-09 | Beiersdorf Ag | Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Catechinen oder einem Gehalt an Extrakt von grünem Tee |
DE19834814A1 (de) * | 1998-08-01 | 2000-02-03 | Beiersdorf Ag | Kosmetische und dermatologische Zubereitungen mit einem wirksamen Gehalt an Gallensäuren, ihren Salzen und/oder ihren Derivaten |
DE19843566A1 (de) * | 1998-09-23 | 2000-03-30 | Beiersdorf Ag | Verwendung von Wirkstoffen, gewählt aus der Gruppe der 1,2-Diacylglycerole, zur Stärkung der Barrierefunktion der Haut |
DE19962267A1 (de) * | 1999-12-23 | 2001-06-28 | Beiersdorf Ag | Verwendung von Wirkstoffkombinationen aus einem oder mehreren NO-Synthasehemmern und einer oder mehreren Ascorbylverbindungen zur Stärkung der Barrierefunktion der Haut |
DE19962369A1 (de) * | 1999-12-23 | 2001-06-28 | Beiersdorf Ag | Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an Catechinen oder einem Gehalt an Extrakt von grünem Tee und einem weiteren Gehalt an Ascorbinsäure |
-
2000
- 2000-06-29 DE DE10031703A patent/DE10031703A1/de not_active Withdrawn
-
2001
- 2001-06-01 JP JP2002504967A patent/JP2004501872A/ja active Pending
- 2001-06-01 WO PCT/EP2001/006262 patent/WO2002000185A1/de not_active Application Discontinuation
- 2001-06-01 EP EP01947333A patent/EP1294351A1/de not_active Withdrawn
-
2002
- 2002-12-26 US US10/329,956 patent/US20040086538A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO0200185A1 * |
Also Published As
Publication number | Publication date |
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US20040086538A1 (en) | 2004-05-06 |
WO2002000185A1 (de) | 2002-01-03 |
DE10031703A1 (de) | 2002-01-10 |
JP2004501872A (ja) | 2004-01-22 |
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