EP1496842A1 - Agent de soins capillaires contenant des derives d'amidon pregelatinises a reticulation transversale - Google Patents

Agent de soins capillaires contenant des derives d'amidon pregelatinises a reticulation transversale

Info

Publication number
EP1496842A1
EP1496842A1 EP03722430A EP03722430A EP1496842A1 EP 1496842 A1 EP1496842 A1 EP 1496842A1 EP 03722430 A EP03722430 A EP 03722430A EP 03722430 A EP03722430 A EP 03722430A EP 1496842 A1 EP1496842 A1 EP 1496842A1
Authority
EP
European Patent Office
Prior art keywords
hair
hair care
derivatives
pregelatinized
amphoteric
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.)
Ceased
Application number
EP03722430A
Other languages
German (de)
English (en)
Inventor
Michael Demitz
Horst Argembeaux
Stephan Ruppert
Ines Wallendszus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beiersdorf AG
Original Assignee
Beiersdorf AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beiersdorf AG filed Critical Beiersdorf AG
Publication of EP1496842A1 publication Critical patent/EP1496842A1/fr
Ceased legal-status Critical Current

Links

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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • 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
    • A61K8/416—Quaternary ammonium compounds
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/594—Mixtures of polymers

Definitions

  • the present invention relates to cosmetic hair care products containing polymers.
  • the present invention relates to hair care preparations or hair care compositions containing substances which have a particularly improved combability and improved grip.
  • the entire human body with the exception of the lips, the palms of the hands and the soles of the feet, is hairy, but for the most part with barely visible wool hairs. Because of the many nerve endings at the hair root, hair is sensitive to external influences such as wind or touch and is therefore a part of the sense of touch that should not be underestimated.
  • the most important function of the human head hair today should be to help shape the human appearance in a characteristic way. Similar to the skin, it fulfills a social function, since its appearance makes a significant contribution to interpersonal relationships and the self-esteem of the individual.
  • the hair consists of the hair shaft protruding freely from the skin - the keratinized (dead) part, which actually represents the visible hair - and the hair root stuck in the skin - the living part, in which the visible hair is constantly being newly formed.
  • the hair shaft for its part, is made up of three layers: a central part - the so-called hair mark (medulla), which, however, is regressed in humans and is often completely absent - as well as the marrow (cortex) and the outer cuticle layer (cuticle) up to ten layers thick that covers the whole hair.
  • Both UV-A and UV-B radiation have a damaging effect on the hair, which manifests itself, for example, in the fact that certain amino acids such as cystine and methionine are broken down or sulfur-sulfur bonds of keratin are broken, which in the worst case is a Destruction of the hair can result.
  • hair and scalp are parts of the body that are exposed to a significant amount of UV radiation due to their position when they are outdoors.
  • One goal of hair care is to maintain the natural state of freshly regrown hair for as long as possible and to restore it in the event of loss.
  • Silky shine, low porosity and a pleasant, smooth feeling are characteristics of natural, healthy hair.
  • hair care cosmetics are used nowadays which are either intended to be rinsed out of the hair again after exposure or which are intended to remain on the hair.
  • the latter can be formulated so that they not only serve the care of the individual hair, but also improve the overall look of a hairstyle.
  • Hair cared for in this way is characterized by a pleasant handle, natural shine, increased fullness, suppleness and thus good manageability and strength and thus good hairstyle fit.
  • hair conditioners Products that only serve to care for the hair are generally referred to as hair conditioners. These can be rinsed out on the hair after a more or less long dwell time (rinse-off products, eg rinses, hair treatments) or they remain on the hair after use (leave-on products).
  • the products can have different consistencies, so they are whole can be applied differently. It can be emulsions or gels or low-viscosity solutions, which are applied, for example, by spray applications, or foams, which are generated, for example, by suitable compressed gas packs or special foam pumps during application. Creamy, cloudy and clearly transparent products can be found on the market.
  • active ingredients or combinations of active ingredients can be found in such conditioners. Some that serve to protect the hair, such as antioxidants or UV filters, others that make the hair supple, e.g. cationic surfactants.
  • Polymeric active ingredients which have very different properties depending on the type, molecular weight and charge, are becoming increasingly important. However, the focus is clearly on improving the surface quality of the hair.
  • cosmetic hair care compositions either containing one or more pregelatinized, crosslinked starch derivatives and cationic polymers or containing one or more pregelatinized, crosslinked starch derivatives and nonionic, amphoteric and / or anionic polymers have the disadvantages of the prior art remedy.
  • hair treatment agents with excellent care performance are obtained, the combination of starch derivatives with cationic polymers synergistically improving the smoothness-improving care properties without weighing the hair down.
  • the combination of starch derivatives with nonionic, amphoteric and anionic polymers synergistically improves the setting properties, which is associated with a better hair volume.
  • the hair also has a pleasant feel and is easy to style. It is preferred if, as the pre-gelatinized, crosslinked starch derivatives, hydroxypropylated starch phosphate esters are particularly preferred
  • Hydroxypropyl distarch phosphates can be used.
  • Ammonium salts of hydroxyethyl cellulose which is modified with a trimethylammonium-substituted epoxide, depolymerized and then quaternized
  • Guar gum derivatives and / or quaternized guar derivatives can be used.
  • Group of the cationic cellulose derivatives is selected.
  • Amide / acrylate / methacrylate copolymers particularly preferably PVPA / A col polymers.
  • the content of pregelatinized, crosslinked is particularly preferred
  • Starch derivatives 20 to 99.9% by weight, very particularly preferably 25 to 95% by weight, based on the total content of polymers.
  • the total polymer content is preferably 0.1 to 3% by weight, particularly preferably 0.2 to 1.5% by weight, based on the total weight of the preparation.
  • hydroxypropylated phosphate esters are used as pregelatinized, crosslinked starch derivatives.
  • Starch derivatives such as those described in US Pat. No. 6,248,338 are particularly advantageous, and hydroxypropyl distarch phosphate is particularly advantageous. It is very particularly preferred to use a hydroxypropyl distarkphosphate, such as that sold as a product Structure® XL by National Starch.
  • Hydroxypropyl trimonium chloride Hydroxypropyl trimonium chloride
  • Rhodia Hydroxypropyl trimonium chloride
  • quaternized guar derivative Cosmedia Guar C 261 (Cognis)
  • nonionic PVP / VA copolymer Liviskol VA 64W, BASF
  • anionic acrylate copolymer Liviflex soft, BASF
  • amphoteric amide / acrylate / methacrylate copolymer Amphomer, National Starch
  • hydroxypropylated phosphate esters are used as the pregelatinized, crosslinked starch derivatives.
  • Starch derivatives such as those described in US Pat. No. 6,248,338 are particularly advantageous, and hydroxypropyl distarch phosphate is particularly advantageous.
  • Cosmetic and dermatological preparations according to the invention can be in various forms. So you can e.g. 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.
  • 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.
  • the hair care products are topical preparations. These can be composed as usual and can be used to treat and care for the scalp and / or hair or as a sunscreen preparation.
  • the preparations according to the invention are applied to the scalp and hair in a sufficient amount in the manner customary for cosmetics and hair care products.
  • Preparations in the sense of the present invention can advantageously be present as a hair treatment or conditioner.
  • the agents according to the invention can, for example, be sprayable from aerosol containers, squeeze bottles or by a pump, spray or foam device Preparations are available, but also in the form of an agent that can be applied from normal bottles and containers.
  • Suitable blowing agents for cosmetic or dermatological preparations which can be sprayed from aerosol containers for the purposes of the present invention are the customary known volatile, liquefied blowing agents, for example dimethyl ether, hydrocarbons (propane, butane, isobutane), which can be used alone or in a mixture with one another. Compressed air, nitrogen, nitrogen dioxide or carbon dioxide or mixtures of these substances can also be used advantageously.
  • preparations according to the invention advantageously also contain conventional active substances, ingredients, additives and / or auxiliaries.
  • hair care products A large number of products are referred to as hair care products, the most important representatives of which are pre-treatment agents, hair lotions and hair treatments.
  • Raw materials for hair care products are e.g. Fatty alcohols, waxes, paraffins, petroleum jelly, paraffin oil and solvents.
  • Fatty alcohols are e.g. straight or branched chain aliphatic monohydric alcohols with 6 - 22 C atoms in the molecule.
  • Straight-chain fatty alcohols with a chain length of 12-18 C atoms are preferably used in cosmetics. These fatty alcohols are soft, colorless masses, practically non-toxic and well tolerated by the skin.
  • Fatty alcohols are preferred for the production of hair treatments and hairdressing creams, with cetyl alcohol and stearyl alcohol being of particular importance.
  • Waxes are fatty acid esters that are found in animal and vegetable products, but can also be produced synthetically.
  • the best known naturally occurring wax is beeswax, which contains cerin and myricine as the main components.
  • Is wax however, a generic term for a number of naturally or artificially obtained substances, which are usually semi-solid, white, odorless and insoluble in water.
  • Paraffins in the cosmetic sense are white, odorless masses of straight-chain, high-molecular hydrocarbons. Because of their properties comparable to waxes, they are often referred to as petroleum waxes.
  • Vaseline is a mixture of branched-chain paraffins with a low proportion of cyclic paraffins. It is a soft, transparent and water-insoluble mass with a low odor that arises during the processing of the petroleum.
  • Paraffin oil is a mixture of saturated liquid hydrocarbons. It is insoluble in water, but miscible with fatty alcohols and waxes. It is used as an additive in hair care products to regulate the consistency.
  • Excipients can be used to improve certain properties of hair care products, e.g. To improve consistency, temperature and light stability, appearance and smell and to facilitate their manufacture. The following are added, for example upon need:
  • Emulsifiers to reduce the interfacial tension between two immiscible phases so far that their fine mixing is possible, thickeners to increase the stability of emulsions and adjust their viscosity,
  • UV absorber to improve the light stability of the dyes and other light-sensitive components contained in hair care products. In addition, they serve to protect the hair from the effects of light. Preservative to prevent microbial decomposition. Antioxidants to prevent odor changes that can be caused by oxidation processes. Dyes to give hair care products an attractive appearance. Perfume oils to give hair care products a pleasant fragrance and to mask the odors of the raw materials.
  • the amount of the base materials is, for example, 85 to 99.999% by weight, preferably 90 to 99.99% by weight, in each case based on the total weight of the preparation.
  • Quaternary ammonium compounds are an important group of the special active ingredients that are used in the manufacture of hair care products. Hair care products, in particular hair treatments, obtain essential properties such as improved combability and grip and prevention of static charging of the hair primarily through the use of quaternary ammonium compounds.
  • quaternary ammonium compounds are determined on the one hand by the cationic group and on the other hand by the nature of the lipophilic residues of this group.
  • Products of this type are preferably used as chlorides, bromides and methosulfates.
  • Polymeric quaternary ammonium compounds, macromolecules, whose essential feature is the presence of several quaternary ammonium groups in the molecule, are also suitable. This significantly increases their adhesion to the hair.
  • Quaternary surfactants contain at least one N atom that is 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 hydroxysultain are advantageous.
  • the cationic surfactants used according to the invention can furthermore preferably be selected from the group of the quaternary ammonium compounds, in particular benzyltrialkylammonium chloride, furthermore alkyltrialkylammonium salts, for example cetyltrimethylam- monium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, dialkyldimethylammonium chlorides or bromides, alkylamidethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl- or cetylpyrimidinium chloride, imidazoline derivatives and compounds with, for example, alkyldimideethylamidoethylaminoethyl amine oxides, such as cationic character amine oxides, such as amine methyl amine oxides, such as cationic character amine oxides such as amine methyl amine oxides, such as cationic
  • Monomeric or polymeric quaternary ammonium compounds are often used in hair conditioners and hair treatments e.g. used in concentrations of 0.5 - 5 wt .-%. These include cetrimonium chloride as offered by Henkel under the name Dehyquart A or distearoylethyl hydroxyethylmonium methosulfate as offered by Henkel under the name Dehyquart F 75.
  • emulsions 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.
  • a cosmetic preparation in the form of a lotion that is not rinsed out, in particular a lotion for inlaying the hair, a lotion that is used for blow-drying the hair, a styling and treatment lotion is generally an emulsion and contains the combinations according to the invention.
  • the lotion according to the invention is in the form of a microemulsion or an aqueous or aqueous-alcoholic solution.
  • cosmetic preparations for the treatment and care of the hair can be in the form of gels which contain organic thickeners, for example gum arabic, xanthan gum, sodium alginate, cellulose derivatives, preferably methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, for example aluminum silicates for example bentonites, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate.
  • the thickener 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 above percentages relate to the total weight of the preparations.
  • the preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. Preservatives, perfumes, substances to prevent foaming, foam stabilizers, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing and / or moisturizing substances, lipid-replenishing agents, fats, oils, waxes, alcohols, polyols and their toxicologically compatible ethers and esters, branched and / or unbranched hydrocarbons, further antioxidants, stabilizers, pH regulators, consistency regulators, bactericides, deodorants, antimicrobial substances, antistatic agents, UV absorbers, complexing and sequestering agents.
  • cosmetic auxiliaries e.g. Preservatives, perfumes, substances to prevent foaming, foam stabilizers, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing
  • Solution brokers e.g. for incorporating hydrophobic components such as of perfume preparations can be included.
  • the total amount of auxiliaries is, for example, 0.001 to 15% by weight, preferably 0.01 to 10% by weight, in each case based on the total weight of the preparation.
  • the amount of the thickener is, for example, 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, in particular 0.15 to 2.0% by weight, in each case based on the total weight of the Preparation.
  • the water content of the preparations is, for example, 60 to 95% by weight, preferably 75 to 95% by weight, in particular 80 to 90% by weight, in each case based on the total weight of the preparation.
  • antioxidants which are suitable or customary for cosmetic and / or dermatological applications can additionally be used as antioxidants.
  • the total amount of the antioxidants is, for example, 0.000.001 to 2% by weight, preferably 0.001 to 1% by weight, in each case based on the total weight of the preparation.
  • Other 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-camosine, D-carnosine, L- Camosin and its derivatives (eg anserine), carotenoids, carotenes (eg ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine
  • buthioninsulfoximines homocysteine sulfoximine, pentahione sulfonimine, buthione) , Hexa-, heptathioninsulfoximine
  • very low tolerable doses e.g. pmol to ⁇ mol / kg
  • metal chelators e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g.
  • citric acid citric acid, lactic acid , Malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives
  • unsaturated fatty acids and their derivatives e.g. ⁇ -linolenic acid, linoleic acid, oleic acid
  • folic acid and its derivatives vitamin C and derivatives (e.g. Ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g.
  • vitamin E acetate
  • vitamin A and derivatives vitamin A palmitate
  • D derivatives eg
  • Preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UV-B range, the total amount of the filter substances being, for example, 0.001% by weight to 30% by weight, preferably 0.05 to 10% by weight, in particular 0.1 to 1.0% by weight, based on the total weight of the preparations, in order to provide cosmetic preparations which protect the hair or the skin from the entire range of ultraviolet radiation. They can also serve as sunscreens for the hair or skin, especially the scalp. If the emulsions according to the invention contain UV-B filter substances, they can advantageously be water-soluble. Examples of advantageous water-soluble UV-B filters are:
  • 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanolammonium salt, and also 2-phenylbenzimidazole-5-sulfonic acid itself;
  • Sulfonic acid derivatives of behzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
  • UV-A filters can also be advantageous to add UV-A filters to the preparations according to the invention which have hitherto usually been found in cosmetic preparations.
  • the quantities used for the UV-B combination can be used.
  • the preparations according to the invention can be prepared in the customary manner by mixing the individual constituents.
  • the active ingredients of the combinations according to the invention or the premixed components of the combinations according to the invention can be added in the mixing process.
  • the pH of the preparations can be adjusted in a known manner by adding acids or bases, preferably by adding buffer mixtures, e.g. based on citric acid / citrate or phosphoric acid phosphate buffer mixtures.
  • buffer mixtures e.g. based on citric acid / citrate or phosphoric acid phosphate buffer mixtures.
  • the pH is below 10, e.g. in the range of 2-7, especially in the range of 3-5.
  • the pH is adjusted to 3.5.
  • the pH is adjusted to 5.5.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des agents de soins capillaires cosmétiques contenant soit un ou plusieurs dérivés d'amidon prégélatinisés à réticulation transversale et des polymères cationiques, soit un ou plusieurs dérivés d'amidon prégélatinisés à réticulation transversale et des polymères non ioniques, amphotères et/ou anioniques.
EP03722430A 2002-04-11 2003-04-09 Agent de soins capillaires contenant des derives d'amidon pregelatinises a reticulation transversale Ceased EP1496842A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10216500A DE10216500A1 (de) 2002-04-11 2002-04-11 Haarpflegemittel
DE10216500 2002-04-11
PCT/EP2003/003677 WO2003084487A1 (fr) 2002-04-11 2003-04-09 Agent de soins capillaires contenant des derives d'amidon pregelatinises a reticulation transversale

Publications (1)

Publication Number Publication Date
EP1496842A1 true EP1496842A1 (fr) 2005-01-19

Family

ID=28458813

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03722430A Ceased EP1496842A1 (fr) 2002-04-11 2003-04-09 Agent de soins capillaires contenant des derives d'amidon pregelatinises a reticulation transversale

Country Status (4)

Country Link
US (1) US20060039882A1 (fr)
EP (1) EP1496842A1 (fr)
DE (1) DE10216500A1 (fr)
WO (1) WO2003084487A1 (fr)

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DE10216500A1 (de) 2003-10-23
US20060039882A1 (en) 2006-02-23

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