WO2004052332A1 - Cleansing preparations containing fatty acid salts - Google Patents
Cleansing preparations containing fatty acid salts Download PDFInfo
- Publication number
- WO2004052332A1 WO2004052332A1 PCT/EP2003/050960 EP0350960W WO2004052332A1 WO 2004052332 A1 WO2004052332 A1 WO 2004052332A1 EP 0350960 W EP0350960 W EP 0350960W WO 2004052332 A1 WO2004052332 A1 WO 2004052332A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- use according
- cleaning
- skin
- acid salts
- fatty acid
- 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
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
- A61K8/30—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
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/007—Soaps or soap mixtures with well defined chain length
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/225—Polymers
Definitions
- the present invention relates to the use of fatty acid salts to achieve or increase the selectivity of cosmetic or dermatological cleaning preparations.
- Known agents for cleaning and simultaneous care of the skin are e.g. B. oil-containing cleaning preparations or cleaning preparations with different moisturizers or skin moisturized, which are to re-grease or moisturize the skin during cleaning.
- B. oil-containing cleaning preparations or cleaning preparations with different moisturizers or skin moisturized which are to re-grease or moisturize the skin during cleaning.
- the prior art knows, for example, various types of oil bath preparations, shower oils, cleaning creams and the like.
- the content of one or more fatty acid salts is advantageously from 1.0 to 50% by weight and preferably from 5 to 40% by weight, in each case based on the total weight of the formulation.
- the soaps according to the invention are formed from the corresponding fatty acids by reaction with bases.
- the fatty acids lauric acid (dodecanecarboxylic acid), myristic acid (tetradecanecarboxylic acid), palmitic acid (hexadecanecarboxylic acid), stearic acid (octadecanecarboxylic acid) are advantageous according to the invention.
- one or more fatty acid salts are preferably selected from the group of the lauric, myristic and / or stearic acid salts.
- Bases preferred according to the invention are, for example, sodium hydroxide, potassium hydroxide and / or triethanolamine.
- advantageous preparations in which fatty acid salts are used according to the invention can contain one or more further surface-active compounds, in particular surfactants.
- acylglutamates for example sodium acylglutamate, 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
- 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 Dilureth-4 phosphate,
- acyl isethionates e.g. Sodium / ammonium cocoyl isethionate
- alkylsulfonates for example sodium, 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 .1 3 pareth sulfate,
- Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate.
- Quaternary surfactants contain at least one N atom that is covalently linked to 4 alkyl or aryl groups. Regardless of the pH value, this leads to a positive charge.
- Benzalkonium chloride, alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous.
- acyl-dialkylethylenediamine for example sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,
- N-alkylamino acids for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
- N-alkyl or N-alkenyl betaines with at least 12 carbon atoms such as.
- Nonionic surfactants to be used advantageously are I. alcohols,
- alkanolamides such as cocamides 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, 5.
- ethers for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterols, ethoxylated / propoxylated Triglyceride esters, ethoxylated propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside. 6. sucrose esters, ether
- the cleaning preparations within the meaning of the present invention particularly advantageously contain one or more wash-active surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, very particularly those which have an HLB value of more than 35.
- the content of one or more detergent surfactants in the cosmetic or dermatological cleaning preparation is in the range from 2.0 to 25% by weight, very particularly advantageously from 2.5 to 15% by weight. % is selected, based in each case on the total weight of the preparation.
- alkyl ether sulfate or a monoalkyl phosphate is used as further surface-active compounds.
- the preparations in which the fatty acid salts are used according to the invention contain one or more gel formers.
- Gel formers from the group of polyacrylates and / or acrylate copolymers are preferred according to the invention.
- one or more polyacrylates in a total concentration of 0.3 to 5.0% by weight, preferably in a concentration of 1.0 to 2.0% by weight, in each case based on the total weight of the preparation ,
- Polyacrylates which are advantageous according to the invention are polymers of acrylic acid, in particular those selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of the BF Goodrich Company). Polyacrylates are compounds of the general structural formula whose molecular weight can be between approximately 400,000 and more than 4,000,000. The group of polyacrylates also includes acrylate-alkyl acrylate copolymers, for example those which are distinguished by the following structure:
- R ' represents a long-chain alkyl radical and x and y numbers which symbolize the respective stoichiometric proportion of the respective comonomers.
- Advantageous carbopoles are, for example, types 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342, 1382, 2984 and 5984 or types ETD (Easy-to-disperse) 2001, 2020, 2050, where these compounds can be present individually or in any combination with one another.
- ETD Easy-to-disperse
- Carbopol 981, 1382 and ETD 2020 are particularly preferred.
- copolymers of CIO- 30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters which are comparable to the acrylate-alkyl acrylate copolymers.
- the INCI names for such compounds are, for example, “Acrylates / C 10-30 Alkyl Acrylate Crosspolymer” or “Acrylates Copolymer”.
- Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 and Carbopol Aqua-SF 1 polymer from NOVEON. According to the invention, it is advantageous to choose one or more polyacrylates from the group of acrylate-alkyl acrylate copolymers.
- polyacrylates and cellulose derivatives it is preferred to use a combination of polyacrylates and cellulose derivatives as the polymeric thickener.
- the preparation according to the invention advantageously contains the cellulose derivatives in a total concentration of 0.1 to 1.0% by weight, preferably in a total concentration of 0.2 to 0.5% by weight, based in each case on the total weight of the preparation.
- Preferred cellulose derivatives in the sense of the present invention are hydroxyalkyl celluloses. It is particularly preferred if one or more hydroxyalkyl celluloses are selected, such as. B. carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and hydroxypropyl methyl cellulose.
- xanthan (CAS No. 11138-66-2), also known as xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2x106 to 24x106.
- compositions within the meaning of the present invention further advantageously contain water and optionally the additives customary in cosmetics, e.g. B. preservatives, preservation aids, bactericides, perfumes, dyes, pigments that have a coloring effect, solubilizers, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, waxes or other common components of a cosmetic or dermatological formulation.
- the additives customary in cosmetics e.g. B. preservatives, preservation aids, bactericides, perfumes, dyes, pigments that have a coloring effect, solubilizers, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, waxes or other common components of a cosmetic or dermatological formulation.
- the water phase of the preparations can advantageously comprise customary cosmetic auxiliaries, such as, for example, alcohols, in particular those with a low C number, preferably ethanol and / or isopropanol, diols or polyols with a low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl - or - monoethyl ether and analog products, polymers, foam stabilizers, electrolytes, dihydroxyacetone and in particular one or more thickeners, which or which can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g.
- customary cosmetic auxiliaries such as, for example, alcohols, in particular those with a low C number, preferably ethanol and / or isopropan
- Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also called trans-epidermal water joss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.
- TEWL trans-epidermal water joss
- moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. It is also particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides.
- antioxidants are used as additives or active ingredients.
- the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive, but nevertheless optional, antioxidants.
- Water-soluble antioxidants such as vitamins, e.g. B. ascorbic acid and its derivatives.
- Preferred antioxidants are also vitamin E and its derivatives and vitamin A and its derivatives.
- 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 0.1 to 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 add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.
- the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, preferred active ingredients being antioxidants which can protect the skin and / or the hair from oxidative stress.
- active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as.
- the preparation according to the invention advantageously contains one or more conditioners.
- Conditioners preferred according to the invention are, for example, all compounds which are in the International Cosme ⁇ c Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) under Section 4 under the keywords Hair Conditioning Agents, Humectants, Skin-Conditioning Agents, Skin-Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occiusive and Skin Protectans are listed as well as all of them in EP 0934956 (p.11-13) under water soluble conditioning agent and oil soluble conditioning agent listed connections.
- Further conditioners which are advantageous according to the invention are, for example, the compounds named polyquaternium according to the international nomenclature for cosmetic ingredients (INCI).
- polyquaternium-1 to polyquaternium-56 but also the polyethylene glycols and polyproylene glycols which are advantageous according to the invention.
- the preparations in which the fatty acid salts are advantageously used according to the invention have a pH of greater than 7 and preferably a pH of greater than 8.
- the cleaning preparations in which the fatty acid salts are used according to the invention are advantageously used in liquid or semi-liquid form.
- Liquid means preparations according to the invention which have a viscosity of 1500 to 5000 mPas.
- “Semi-liquid” means preparations according to the invention which have a viscosity of greater than 5000 mPas. The viscosity values of the preparations and individual substances listed in the context of the preceding document were determined with the aid of a Viscotester VT 02 viscometer from Haake.
- the cleaning compositions containing fatty acid salts used according to the invention can be composed as usual and can be used for cosmetic and / or dermatological body cleaning such as cleaning the skin and / or hair, as a make-up removal product for decorative cosmetics and for facial cleaning.
- the cleaning preparations in which the fatty acid salts are used according to the invention are advantageously used for cleaning oily and / or impure skin / scalp.
- the compositions comprising fatty acid salts used according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
- the preparations in which the fatty acid salts are advantageously used according to the invention can be used as the impregnation medium for an insoluble substrate, for example a nonwoven or cloth, the substrate also being able to be in the form of a substrate which appears to be dry or as a substrate which appears to be moist.
- the preparations in which the fatty acid salts are advantageously used according to the invention can be used as a shampoo, shower gel, foam bath or tub bath and as a hand wash lotion or shaving cream. According to the invention, they can advantageously be stored in double-chamber packaging or foam dispensers (mechanical pump dispensers (pump foamers) or aerosol cans).
- the preparations in which the fatty acid salts are advantageously used according to the invention can be used for cleaning and washing clothes and textiles (“detergents”) and for cleaning everyday objects (for example dishes, table and cupboard surfaces, cars).
- the selectivity is that dirt and impurities are removed from the textiles and objects of daily life with high selectivity and the skin's own lipids, which are essential for preventing the skin from drying out, are protected.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Abstract
Description
FETTSÄURESALZE ENTHALTENDE REINIGUNGSZUBEREITUNGEN CLEANING PREPARATIONS CONTAINING FATTY ACID SALTS
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von Fettsäuresalzen zum Erzielen oder Erhöhen der Selektivität von kosmetischen oder dermatologischen Reinigungszubereitungen.The present invention relates to the use of fatty acid salts to achieve or increase the selectivity of cosmetic or dermatological cleaning preparations.
Bereits bei einer Reinigung der Haut mit Hilfe eines einfachen Wasserbads - ohne Zusatz von Tensiden - kommt es zunächst zu einer Quellung der Hornschicht der Haut. Der Grad dieser Quellung hängt u. a. von der Dauer des Bades und dessen Temperatur ab. Gleichzeitig werden wasserlösliche Stoffe ab- bzw. ausgewaschen, wie z. B. wasserlösliche Schmutzbestandteile, aber auch hauteigene Stoffe, die für das Wasserbindungsvermögen der Hornschicht verantwortlich sind. Durch hauteigene oberflächenaktive Stoffe werden außerdem auch Hautfette (Oberflächen- und Barrierelipide) in gewissem Ausmaß gelöst und ausgewaschen.When the skin is cleaned with the help of a simple water bath - without the addition of surfactants - the horny layer of the skin swells. The degree of this swelling depends on a. on the duration of the bath and its temperature. At the same time, water-soluble substances are washed off or washed out, e.g. B. water-soluble dirt components, but also the skin's own substances, which are responsible for the water retention capacity of the horny layer. Skin oils (surface and barrier lipids) are also dissolved and washed out to a certain extent by the skin's own surface-active substances.
Während die gemeinsame Entfernung von Oberflächenschmutz und Oberflächenlipiden, welche vornehmlich aus den Talgdrüsen stammen und maßgeblich für das Erscheinungsbild der fettigen Haut verantwortlich sind, kosmetisch durchaus gewünscht ist, kann durch Auswaschen von Barrierelipiden die Funktion der Hautbarriere gestört werden, womit ein Feuchtigkeitsverlust der Haut verbunden ist. Dies geht einher mit einer zeitweisen Erhöhung des transepidermalen Wasserverlusts (TEWL) und einer zeitweisen Verringerung der Hautfeuchte. Vor allem bei Produkten zur Reinigung der empfindlichen Gesichtshaut und hier besonders bei Produkten für fettige Haut ist eine möglichst selektive Entfernung von Oberflächenschmutz, Make-up und Hauttalg für den Verbraucher besonders wichtig. Auf der anderen Seite bedarf vor allem die Gesichtshaut einer besonders schonenden Reinigung.While the joint removal of surface dirt and surface lipids, which originate primarily from the sebaceous glands and are largely responsible for the appearance of oily skin, is cosmetically desirable, washing out the barrier lipids can disrupt the function of the skin barrier, which is associated with a loss of moisture in the skin , This is accompanied by a temporary increase in transepidermal water loss (TEWL) and a temporary decrease in skin moisture. Especially in the case of products for cleaning the sensitive facial skin and especially in the case of products for oily skin, the most selective removal of surface dirt, make-up and skin sebum is particularly important for the consumer. On the other hand, the facial skin in particular needs particularly gentle cleaning.
Bei gesunder Haut sind die durch das Waschen verursachten Störungen im allgemeinen zeitlich begrenzt, da die Schutzmechanismen der Haut solche leichten Störungen der oberen Hautschichten ohne weiteres kompensieren können. Aber bereits im Fall nichtpathologischer Abweichungen vom Normalstatus - z. B. durch umweltbedingte Abnutzungsschäden bzw. Irritationen, Lichtschäden, Altershaut usw. - ist der Schutzmechanismus der Hautoberfläche gestört. Unter Umständen ist er dann aus eigener Kraft nicht mehr imstande, seine Aufgabe zu erfüllen und muss durch externe Maßnahmen regeneriert werden. Es hat daher nicht an Versuchen gefehlt, geeignete Reinigungszubereitungen zur besseren bzw. schnelleren Regeneration der Haut zu finden, die der Haut helfen, ihre natürliche Balance zu erhalten.In the case of healthy skin, the disorders caused by washing are generally limited in time, since the protective mechanisms of the skin prevent such mild disorders from occurring can easily compensate the upper skin layers. But already in the case of non-pathological deviations from normal status - e.g. B. by environmental wear and tear or irritation, light damage, aging skin, etc. - the protective mechanism of the skin surface is disturbed. Under certain circumstances, he may no longer be able to fulfill his task on his own and must be regenerated by external measures. There has been no shortage of attempts to find suitable cleaning preparations for better or faster regeneration of the skin, which help the skin to maintain its natural balance.
Bekannte Mittel zur Reinigung und gleichzeitigen Pflege der Haut sind z. B. ölhaltige Reinigungszubereitungen oder Reinigungszubereitungen mit verschiedenen Rückfettern bzw. Hautbefeuchtem, welche die Haut bei der Reinigung gleichzeitig rückfetten bzw. befeuchten sollen. Der Stand der Technik kennt zu diesem Zweck beispielsweise Olbadzubereitungen verschiedener Art sowie Duschöle, Reinigungscremes und dergleichen mehr.Known agents for cleaning and simultaneous care of the skin are e.g. B. oil-containing cleaning preparations or cleaning preparations with different moisturizers or skin moisturized, which are to re-grease or moisturize the skin during cleaning. For this purpose, the prior art knows, for example, various types of oil bath preparations, shower oils, cleaning creams and the like.
Der Hauptnachteil derartiger Zubereitungen ist, daß ein Teil der Barrierelipide zunächst entfernt wird und eine Rückfettung der Haut anschließend mit Hilfe der zugesetzten ölkomponenten erfolgt. Außerdem werden derartige Reinigungszubereitungen nach der Anwendung abgewaschen, so dass nur geringe Mengen der eingesetzten Additive auf der Haut verbleiben.The main disadvantage of such preparations is that part of the barrier lipids is first removed and the skin is then regreased with the help of the added oil components. In addition, cleaning preparations of this type are washed off after use, so that only small amounts of the additives used remain on the skin.
Es war daher Aufgabe der vorliegenden Erfindung, kosmetische oder dermatologische Zubereitungen zur Verfügung zu stellen, welche den Zustand der Haut deutlich verbessern, insbesondere die Hautrauhigkeit vermindern und welche sich durch eine Selektivität der Reinigungsleistung auszeichnen.It was therefore an object of the present invention to provide cosmetic or dermatological preparations which significantly improve the condition of the skin, in particular reduce the roughness of the skin and which are distinguished by a selectivity of the cleaning performance.
Es war überraschend und für den Fachmann in keiner Weise vorhersehbar, daß die Verwendung einer oder mehrerer grenzflächenaktiver Substanzen, gewählt aus der Gruppe der Fettsäuresalze zum Erzielen oder Erhöhen der Selektivität von kosmetischen oder dermatologischen Reinigungszubereitungen die Nachteile des Standes der Technik beseitigen würde.It was surprising and in no way predictable for the person skilled in the art that the use of one or more surface-active substances, selected from the group of the fatty acid salts, to achieve or increase the selectivity of cosmetic or dermatological cleaning preparations would eliminate the disadvantages of the prior art.
Selektive Reinigungszubereitungen im Sinne der vorliegenden Erfindung waschen deutlich mehr Oberflächen- bzw. Sebumlipide als Barrierelipide aus. Bestimmt man also das Verhältnis von ausgewaschenen Oberflächen- bzw. Sebumlipiden zu ausgewaschenen Barrierelipiden, so ist dies für Zubereitungen enthaltend erfindungsgemäß verwendete Fettsäuresalze (die auch als „Seifen" bezeichnet werden) deutlich größer als 1. Die Steigerung der Selektivität einer Reinigungszubereitung läßt sich erfindungsgemäß z. B. im Vergleich zu Wasser bestimmen. Gemäß der vorliegenden Erfindung lassen sich Produkte formulieren, die mit hoher Selektivität Schmutz und überschüssiges Sebum (bzw. allgemein den „Oberflächenschmutz'' auf der Haut) entfernen und dabei die hauteigenen Lipide schonen, welche für die Verhinderung der Austrocknung der Haut essentiell sind.Selective cleaning preparations in the sense of the present invention wash out significantly more surface or sebum lipids than barrier lipids. So you determine the ratio of washed-out surface or sebum lipids to washed-out barrier lipids, this is significantly greater than 1 for preparations containing fatty acid salts used according to the invention (which are also referred to as "soaps"). According to the invention, the selectivity of a cleaning preparation can be increased, for example In comparison to water, products can be formulated which remove dirt and excess sebum (or in general the "surface dirt" on the skin) with high selectivity and thereby protect the skin's own lipids, which are used to prevent dehydration of the skin are essential.
Bei der erfindungsgemäß vorteilhaften Verwendung der Fettsäuresalze beträgt der Gehalt an einem oder mehreren Fettsäuresalzen vorteilhaft 1,0 bis 50 Gew.-% und bevorzugt 5 bis 40 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Formulierung.When the fatty acid salts are used advantageously according to the invention, the content of one or more fatty acid salts is advantageously from 1.0 to 50% by weight and preferably from 5 to 40% by weight, in each case based on the total weight of the formulation.
Die erfindungsgemäßen Seifen werden aus den entsprechenden Fettsäuren durch Umsetzung mit Basen gebildet. Erfindungsgemäß vorteilhaft sind dabei die Fettsäuren Laurinsäure (Dodecancarbonsäure), Myristinsäure (Tetradecancarbonsäure), Palmitinsäure (Hexadecancarbonsäure), Stearinsäure (Octadecancarbonsäure). Erfindungsgemäß bevorzugt werden ein oder mehrere Fettsäuresalze gewählt aus der Gruppe der Laurin-, Myristin- und/oder Stearinsäuresalze. Erfindungsgemäß bevorzugte Basen sind beispielsweise Natriumhydroxid, Kaliumhydroxid und/oder Triethanolamin.The soaps according to the invention are formed from the corresponding fatty acids by reaction with bases. The fatty acids lauric acid (dodecanecarboxylic acid), myristic acid (tetradecanecarboxylic acid), palmitic acid (hexadecanecarboxylic acid), stearic acid (octadecanecarboxylic acid) are advantageous according to the invention. According to the invention, one or more fatty acid salts are preferably selected from the group of the lauric, myristic and / or stearic acid salts. Bases preferred according to the invention are, for example, sodium hydroxide, potassium hydroxide and / or triethanolamine.
Auch ist es erfindungsgemäß bevorzugt die Natrium-, Kalium- und/oder Triethanolammoniumsalze der erfindungsgemäßen Fettsäuren einzusetzen.It is also preferred according to the invention to use the sodium, potassium and / or triethanolammonium salts of the fatty acids according to the invention.
Erfindungsgemäß können vorteilhafte Zubereitungen, in denen Fettsäuresalze eine erfindungsgemäße Verwendung finden, ein oder mehrere weitere grenzflächenaktive Verbindungen, insbesondere Tenside enthalten.According to the invention, advantageous preparations in which fatty acid salts are used according to the invention can contain one or more further surface-active compounds, in particular surfactants.
Die Reinigungszubereitungen im Sinne der vorliegenden Erfindung enthalten dabei vorteilhaft eines oder mehrere waschaktive Tenside der folgenden vier Gruppen A bis D:The cleaning preparations within the meaning of the present invention advantageously contain one or more detergent surfactants from the following four groups A to D:
A. Anionische TensideA. Anionic surfactants
Vorteilhaft zu verwendende anionische Tenside sind Acylaminosäuren (und deren Salze), wieAnionic surfactants to be used advantageously Acylamino 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 hydrolysiertes Soja Protein und Natrium-/ Kalium Cocoyl hydrolysiertes Kollagen,2. acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen,
3. Sarcosinate, beispielsweise Myristoyl Sarcosin, TEA-Iauroyl Sarcosinat, Natriumlau- roylsarcosinat und Natriumcocoylsarkosinat,3. sarcosinates, for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
4. Taurate, beispielsweise Natriumlauroyltaurat und Natriummethylcocoyltaurat,4. taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,
Carbonsäuren und Derivate, wieCarboxylic 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 Lauramidcarboxylat, 3. Ether-Carbonsäuren, beispielsweise Natriumlaureth-13 Carboxylat und Natrium PEG-6 Cocamide Carboxylat,2. ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate, 3. ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,
Phosphorsäureester und Salze, wie beispielsweise DEA-Oleth-10 Phosphat und Dilau- reth-4 Phosphat,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 Olefin - sulfonat, Natriumlaurylsulfoacetat und Magnesium PEG-3 Cocamidsulfat,3. alkylsulfonates, for example sodium, 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-Sulfosuccinat4. 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 .1 3 pareth sulfate,
2. Alkylsulfate, beispielsweise Natrium-, Ammonium- und TEA- Laurylsulfat. B. Kationische Tenside2. Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate. B. Cationic surfactants
Vorteilhaft zu verwendende kationische Tenside sindCationic surfactants to be used advantageously
1. Alkylamine,1. alkylamines,
2. Alkylimidazole, 3. Ethoxylierte Amine und 4. Quartemäre Tenside.2. alkylimidazoles, 3. ethoxylated amines and 4. quaternary surfactants.
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 Benzalkoniumchlorid, Alkylbetain, Alkylamidopropylbetain und Alkyl-ami- dopropylhydroxysultain.Quaternary surfactants contain at least one N atom that is covalently linked to 4 alkyl or aryl groups. Regardless of the pH value, this leads to a positive charge. Benzalkonium chloride, alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous.
C. Amphotere TensideC. Amphoteric surfactants
Vorteilhaft zu verwendende amphotere Tenside sindAmphoteric surfactants to be used advantageously
1. Acyl-tdialkylethylendiamin, beispielsweise Natriumacylamphoacetat, Dinatriumacyl- amphodipropionat, Dinatriumalkylamphodiacetat, Natriumacylamphohydroxypropylsulfo- nat, Dinatriumacylamphodiacetat und Natriumacylamphopropionat,1. acyl-dialkylethylenediamine, for example sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,
2. N-Alkylaminosäuren, beispielsweise Aminopropylalkylglutamid, Alkylaminopropion- säure, Natriumalkylimidodipropionat und Lauroamphocarboxyglycinat.2. N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
3. N-Alkyl- oder N-Alkenylbetaine mit mindestens 12 C-Atomen, wie z. B. Lauryl- amidopropylbetain und Oleylamidopropylbetain3. N-alkyl or N-alkenyl betaines with at least 12 carbon atoms, such as. B. lauryl amidopropyl betaine and oleyl amidopropyl betaine
D. Nicht-ionische TensideD. Non-ionic surfactants
Vorteilhaft zu verwendende nicht-ionische Tenside sind I. Alkohole,Nonionic surfactants to be used advantageously are I. alcohols,
2. Alkanolamide, wie Cocamide MEA/ DEA/ MIPA,2. alkanolamides, such as cocamides 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, 5. Ether, beispielsweise ethoxylierte/propoxylierte Alkohole, ethoxylierte/ propoxy- lierte Ester, ethoxylierte/ propoxylierte Glycerinester, ethoxylierte/ propoxylierte Cholesterine, ethoxylierte/ propoxylierte Triglyceridester, ethoxyliertes propoxylier- tes Lanolin, ethoxylierte/ propoxylierte Polysiloxane, propoxylierte POE-Ether und Alkylpolyglycoside wie Laurylglucosid, Decylglycosid und Cocoglycosid. 6. Sucroseester, -Ether4. esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols, 5. ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterols, ethoxylated / propoxylated Triglyceride esters, ethoxylated propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside. 6. sucrose esters, ether
7. Polyglycerinester, Diglycerinester, Monoglycerinester7. Polyglycerol esters, diglycerol esters, monoglycerol esters
8. Methylglucosester, Ester von Hydroxysäuren8. Methyl glucose esters, esters of hydroxy acids
Die Reinigungszubereitungen im Sinne der vorliegenden Erfindung enthalten besonders vorteilhaft eines oder mehrere erfindungsgemäße waschaktive Tenside aus den Gruppe der Tenside, welchen einen HLB-Wert von mehr als 25 haben, ganz besonders solche, welchen einen HLB-Wert von mehr als 35 haben .The cleaning preparations within the meaning of the present invention particularly advantageously contain one or more wash-active surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, very particularly those which have an HLB value of more than 35.
Es ist vorteilhaft im Sinn der vorliegenden Erfindung, wenn der Gehalt an einem oder mehreren waschaktiven Tensiden in der kosmetischen oder dermatologischen Reinigungszubereitung aus dem Bereich von 2,0 bis 25 Gew.-%, ganz besonders vorteilhaft von 2,5 bis 15 Gew.-% gewählt wird, jeweils bezogen auf das Gesamtgewicht der Zubereitung.It is advantageous in the sense of the present invention if the content of one or more detergent surfactants in the cosmetic or dermatological cleaning preparation is in the range from 2.0 to 25% by weight, very particularly advantageously from 2.5 to 15% by weight. % is selected, based in each case on the total weight of the preparation.
Es ist erfindungsgemäß bevorzugt, wenn als weitere grenzflächenaktive Verbindungen ein Alkylethersulfat oder ein Monoalkylphosphat eingesetzt werden.It is preferred according to the invention if an alkyl ether sulfate or a monoalkyl phosphate is used as further surface-active compounds.
Es ist erfindungsgemäß von Vorteil, wenn die Zubereitungen, in denen die Fettsäuresalze erfindungsgemäß verwendet werden, ein oder mehrere Gelbildner enthalten. Erfindungsgemäß bevorzugt sind dabei Gelbildner aus der Gruppe der Polyacrylate und/oder Acrylat Copolymere.It is advantageous according to the invention if the preparations in which the fatty acid salts are used according to the invention contain one or more gel formers. Gel formers from the group of polyacrylates and / or acrylate copolymers are preferred according to the invention.
Es ist bei erfindungsgemäßen Zubereitungen vorteilhaft, ein oder mehrere Polyacrylate in einer Gesamtkonzentration von 0,3 bis 5,0 Gewichts-%, bevorzugt in einer Konzentration von 1,0 bis 2,0 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung einzusetzen.With preparations according to the invention, it is advantageous to use one or more polyacrylates in a total concentration of 0.3 to 5.0% by weight, preferably in a concentration of 1.0 to 2.0% by weight, in each case based on the total weight of the preparation ,
Erfindungsgemäß vorteilhafte Polyacrylate sind Polymere der Acrylsäure, insbesondere solche, die aus der Gruppe der sogenannten Carbomere oder Carbopole (Carbopol® ist eigentlich eine eingetragene Marke der B. F. Goodrich Company) gewählt werden. Polyacrylate sind Verbindungen der allgemeinen Strukturformel deren Molgewicht zwischen ca. 400 000 und mehr als 4 000 000 betragen kann. In die Gruppe der Polyacrylate gehören ferner Acrylat-Alkylacrylat-Copolymere, beispielsweise solche, die sich durch die folgende Struktur auszeichnen:Polyacrylates which are advantageous according to the invention are polymers of acrylic acid, in particular those selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of the BF Goodrich Company). Polyacrylates are compounds of the general structural formula whose molecular weight can be between approximately 400,000 and more than 4,000,000. The group of polyacrylates also includes acrylate-alkyl acrylate copolymers, for example those which are distinguished by the following structure:
Darin stellen R' einen langkettigen Alkylrest und x und y Zahlen dar, welche den jeweiligen stöchiometrischen Anteil der jeweiligen Comonomere symbolisieren. Auch diese Polyacrylate sind vorteilhaft im Sinne der vorliegenden Erfindung.R 'represents a long-chain alkyl radical and x and y numbers which symbolize the respective stoichiometric proportion of the respective comonomers. These polyacrylates are also advantageous for the purposes of the present invention.
Vorteilhafte Carbopole sind beispielsweise die Typen 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342, 1382, 2984 und 5984 oder auch die Typen ETD (Easy-to-disperse) 2001, 2020, 2050, wobei diese Verbindungen einzeln oder in beliebigen Kombinationen unter- einander vorliegen können.Advantageous carbopoles are, for example, types 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342, 1382, 2984 and 5984 or types ETD (Easy-to-disperse) 2001, 2020, 2050, where these compounds can be present individually or in any combination with one another.
Besonders bevorzugt sind Carbopol 981, 1382 und ETD 2020 (sowohl einzeln als auch in Kombination).Carbopol 981, 1382 and ETD 2020 (both individually and in combination) are particularly preferred.
Ferner vorteilhaft im Sinne der vorliegenden Erfindung sind die den Acrylat-Alkylacrylat- Copolymeren vergleichbaren Copolymere aus Cιo-30-Alkylacrylaten und einem oder mehreren Monomeren der Acrylsäure, der Methacrylsäure oder deren Ester. Die INCI-Be- zeichnung für solche Verbindungen sind beispielsweise „Acrylates/C 10-30 Alkyl Acrylate Crosspolymer" oder „Acrylates Copolymer". Insbesondere vorteilhaft sind die unter den Handelsbezeichnungen Pemulen TR1 und Pemulen TR2 sowie Carbopol Aqua-SF 1 Polymer bei der NOVEON erhältlichen. Es ist erfindungsgemäß vorteilhaft ein oder mehrere Polyacrylate aus der Gruppe der Acrylat-Alkylacrylat-Copolymeren zu wählen.Also advantageous for the purposes of the present invention are the copolymers of CIO- 30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are comparable to the acrylate-alkyl acrylate copolymers. The INCI names for such compounds are, for example, “Acrylates / C 10-30 Alkyl Acrylate Crosspolymer” or “Acrylates Copolymer”. Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 and Carbopol Aqua-SF 1 polymer from NOVEON. According to the invention, it is advantageous to choose one or more polyacrylates from the group of acrylate-alkyl acrylate copolymers.
Es ist erfindungsgemäß bevorzugt als polymere Verdickungsmittel eine Kombination aus Polyacrylaten und Cellulosederivaten einzusetzen.According to the invention, it is preferred to use a combination of polyacrylates and cellulose derivatives as the polymeric thickener.
Dabei enthält die erfindungsgemäße Zubereitung die Cellulosederivate vorteilhaft in einer Gesamtkonzentration von 0,1 bis 1,0 Gewichts-%, bevorzugt in einer Gesamtkonzentration von 0,2 bis 0,5 Gewichts-% jeweils bezogen auf das Gesamtgewicht der Zubereitung.The preparation according to the invention advantageously contains the cellulose derivatives in a total concentration of 0.1 to 1.0% by weight, preferably in a total concentration of 0.2 to 0.5% by weight, based in each case on the total weight of the preparation.
Bevorzugte Cellulosederivate im Sinne der voriiegenden Erfindung sind Hydroxyalkylcellulosen. Dabei ist es besonders bevorzugt, wenn ein oder mehrere Hydroxyalkylcellulosen gewählt werden, wie z. B. Carboxymethylcellulose und andere Celluloseether, Hydroxyethyl- und -propylcellulose sowie Hydroxypropyl Methylcellulose.Preferred cellulose derivatives in the sense of the present invention are hydroxyalkyl celluloses. It is particularly preferred if one or more hydroxyalkyl celluloses are selected, such as. B. carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and hydroxypropyl methyl cellulose.
Bevorzugt im Sinne der vorliegenden Erfindung ist femer Xanthan (CAS-Nr. 11138-66-2), auch Xanthan Gummi genannt, welches ein anionisches Heteropolysaccharid ist, das in der Regel durch Fermentation aus Maiszucker gebildet und als Kaliumsalz isoliert wird. Es wird von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen mit einem Molekulargewicht von 2x106 bis 24x106 produziert.For the purposes of the present invention, preference is also given to xanthan (CAS No. 11138-66-2), also known as xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2x106 to 24x106.
Die Zusammensetzungen im Sinne der vorliegenden Erfindung enthalten ferner vorteilhaft Wasser und gegebenenfalls die in der Kosmetik üblichen Zusatzstoffe, z. B. Konservierungsmittel, Konservierungshelfer, Bakterizide, Parfüme, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Lösungsvermittler, anfeuchtende und/oder feuchhaltende Substanzen, Füllstoffe, die das Hautgefühl verbessern, Fette, öle, Wach- se oder andere übliche Bestandteile einer kosmetischen oder dermatolog ischen Formulierung.The compositions within the meaning of the present invention further advantageously contain water and optionally the additives customary in cosmetics, e.g. B. preservatives, preservation aids, bactericides, perfumes, dyes, pigments that have a coloring effect, solubilizers, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, waxes or other common components of a cosmetic or dermatological formulation.
Die Wasserphase der Zubereitungen im Sinne der vorliegenden Erfindung kann vorteilhaft übliche kosmetische Hilfsstoffe enthalten, wie beispielsweise Alkohole, insbesondere solche niedriger C-Zahl, vorzugsweise Ethanol und/oder Isopropanol, Diole oder Polyole niedriger C-Zahl sowie deren Ether, vorzugsweise Propylenglykol, Glycerin, Ethylenglykol, Ethylenglykolmonoethyl- oder -monobutylether, Propylenglykolmo- nomethyl, -monoethyl- oder -monobutylether, Diethylenglykolmonomethyl- oder - monoethylether und analoge Produkte, Polymere, Schaumstabilisatoren, Elektrolyte, Dihydroxyaceton sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aluminiumsilikate, Polysaccharide bzw. deren Derivate, z. B. Hyaluronsäure, Xanthangummi, Hydro- xypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevor- zugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981, 1382, 2984, 5984, jeweils einzeln oder in Kombination. Auch Moisturizer können bevorzugt verwendet werden.For the purposes of the present invention, the water phase of the preparations can advantageously comprise customary cosmetic auxiliaries, such as, for example, alcohols, in particular those with a low C number, preferably ethanol and / or isopropanol, diols or polyols with a low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl - or - monoethyl ether and analog products, polymers, foam stabilizers, electrolytes, dihydroxyacetone and in particular one or more thickeners, which or which can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. B. 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, each individually or in combination. Moisturizers can also be used with preference.
Als Moisturizer werden Stoffe oder Stoffgemische bezeichnet, welche kosmetischen oder dermatologischen Zubereitungen die Eigenschaft verleihen, nach dem Auftragen bzw. Verteilen auf der Hautoberfläche die Feuchtigkeitsabgabe der Hornschicht (auch trans- epidermal water joss (TEWL) genannt) zu reduzieren und/oder die Hydratation der Hornschicht positiv zu beeinflussen.Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also called trans-epidermal water joss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.
Vorteilhafte Moisturizer im Sinne der vorliegenden Erfindung sind beispielsweise Glycerin, Milchsäure und/oder Lactate, insbesondere Natriumlactat, Butylenglykol, Propylenglykol, Biosaccaride Gum-1, Glycine Soja, Ethylhexyloxyglycerin, Pyrrolidoncarbonsäure und Harnstoff. Femer ist es insbesondere von Vorteil, polymere Moisturizer aus der Gruppe der wasserlöslichen und/oder in Wasser quellbaren und/oder mit Hilfe von Was- ser gelierbaren Polysaccharide zu verwenden. Insbesondere vorteilhaft sind beispielsweise Hyaluronsäure, Chitosan und/oder ein fucosereiches Polysaccharid, welches in den Chemical Abstracts unter der Registraturnummer 178463-23-5 abgelegt und z. B. unter der Bezeichnung Fucogel®1000 von der Gesellschaft SOLABIA S.A. erhältlich ist.Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. It is also particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.
Besonders vorteilhafte Zubereitungen werden ferner erhalten, wenn als Zusatz- oder Wirkstoffe Antioxidantien eingesetzt werden. Erfindungsgemäß enthalten die Zubereitungen vorteilhaft eines oder mehrere Antioxidantien. Als günstige, aber dennoch fakultativ zu verwendende Antioxidantien können alle für kosmetische und/oder dermatologische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden. Besonders vorteilhaft im Sinne der voriiegenden Erfindung können wasserlösliche Antioxidantien eingesetzt werden, wie beispielsweise Vitamine, z. B. Ascorbinsäure und deren Derivate.Particularly advantageous preparations are also obtained if antioxidants are used as additives or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive, but nevertheless optional, antioxidants. Water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its derivatives.
Bevorzugte Antioxidantien sind ferner Vitamin E und dessen Derivate sowie Vitamin A und dessen Derivate.Preferred antioxidants are also vitamin E and its derivatives and vitamin A and its derivatives.
Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 bis 20 Gew.-%, insbesondere 0,1 bis 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 0.1 to 10% by weight, based on the total weight the preparation.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.
Sofern Vitamin A bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.
Es ist insbesondere vorteilhaft, wenn die kosmetischen Zubereitungen gemäß der vorliegenden Erfindung kosmetische oder dermatologische Wirkstoffe enthalten, wobei bevorzugte Wirkstoffe Antioxidantien sind, welche die Haut und/oder die Haare vor oxidativer Beanspruchung schützen können.It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, preferred active ingredients being antioxidants which can protect the skin and / or the hair from oxidative stress.
Weitere vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung sind natürliche Wirkstoffe und/oder deren Derivate, wie z. B. alpha-Liponsäure, Phytoen, D-Biotin, Coenzym Q10, alpha-Glucosylrutin, Carnitin, Camosin, natürliche und/oder synthetische Isoflavo- noide, Kreatin, Taurin und/oder ß-Alanin.Further advantageous active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, camosin, natural and / or synthetic isoflavonoids, creatine, taurine and / or ß-alanine.
Die erfindungsgemäße Zubereitung enthält vorteilhafter Weise einen oder mehrere Konditionierer. Erfindungsgemäß bevorzugte Konditionierer sind beispielsweise alle Verbindungen, welche im International Cosmeϋc Ingredient Dictionary and Handbook (Volume 4, Herausgeber: R. C. Pepe, J.A. Wenninger, G. N. McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9. Auflage, 2002) unter Section 4 unter den Stichworten Hair Conditioning Agents, Humectants, Skin-Conditioning Agents, Skin- Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occiusive und Skin Protectans aufgeführt sind sowie alle in der EP 0934956 (S.11-13) unter water soluble conditioning agent und oil soluble conditioning agent aufgeführten Verbindungen. Weitere erfindungsgemäß vorteilhafte Konditionierer stellen beispielsweise die nach der internationalen Nomenklatur für kosmetische Inhaltsstoffe (INCI) als Polyquatemium benannten Verbindungen dar. So sind beispielsweise Polyquaternium-1 bis Polyquatemium-56 aber auch die Polyethylenglycole und Polyproylenglycole erfindungsgemäß vorteilhafte Konditionierungsmittel.The preparation according to the invention advantageously contains one or more conditioners. Conditioners preferred according to the invention are, for example, all compounds which are in the International Cosmeϋc Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) under Section 4 under the keywords Hair Conditioning Agents, Humectants, Skin-Conditioning Agents, Skin-Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occiusive and Skin Protectans are listed as well as all of them in EP 0934956 (p.11-13) under water soluble conditioning agent and oil soluble conditioning agent listed connections. Further conditioners which are advantageous according to the invention are, for example, the compounds named polyquaternium according to the international nomenclature for cosmetic ingredients (INCI). For example, polyquaternium-1 to polyquaternium-56, but also the polyethylene glycols and polyproylene glycols which are advantageous according to the invention.
Erfindungegemäß vorteilhaft weisen die Zubereitungen, in denen die Fettsäuresalze erfindungsgemaß vorteilhaft verwendet werden, einen pH-Wert von größer als 7 und bevorzugt einen pH-Wert von größer als 8 auf.Advantageously according to the invention, the preparations in which the fatty acid salts are advantageously used according to the invention have a pH of greater than 7 and preferably a pH of greater than 8.
Erfindungsgemäß vorteilhaft werden die Reinigungszubereitungen, in denen die Fettsäuresalze erfindungsgemäß verwendet werden, in flüssiger oder halbflüssiger Form eingesetzt. Dabei wird unter „flüssig" erfindungsgemäß Zubereitungen, die eine Viskosität von 1500 bis 5000 mPas aufweisen. Unter „halbflüssig" werden erfindungsgemaß Zubereitungen verstanden, die eine Viskosität von größer 5000 mPas aufweisen. Die im Rahmen der voriiegenden Schrift aufgeführten Viskositätswerte der Zubereitungen und Einzelsubstanzen wurden dabei mit Hilfe eines Viskosimeters des Typs Viskotester VT 02 der Gesellschaft Haake ermittelt.According to the invention, the cleaning preparations in which the fatty acid salts are used according to the invention are advantageously used in liquid or semi-liquid form. "Liquid" means preparations according to the invention which have a viscosity of 1500 to 5000 mPas. "Semi-liquid" means preparations according to the invention which have a viscosity of greater than 5000 mPas. The viscosity values of the preparations and individual substances listed in the context of the preceding document were determined with the aid of a Viscotester VT 02 viscometer from Haake.
Die Reinigungszusammensetzungen enthaltend erfindungsgemäß verwendete Fettsäuresalze können wie üblich zusammengesetzt sein und der kosmetischen und/oder dermatologischen Körperreinigung wie der Reinigung der Haut und/oder der Haare, als Abschminkprodukt für dekorative Kosmetik und zur Gesichtsreinigung dienen.The cleaning compositions containing fatty acid salts used according to the invention can be composed as usual and can be used for cosmetic and / or dermatological body cleaning such as cleaning the skin and / or hair, as a make-up removal product for decorative cosmetics and for facial cleaning.
Erfindungsgemäß vorteilhaft werden die Reinigungszubereitungen, in denen die Fettsäuresalze erfindungsgemäß verwendet werden, zur Reinigung fettiger und/oder unreiner Haut/Kopfhaut eingesetzt. Zur Anwendung werden die Zusammensetzungen enthaltend erfindungsgemäß verwendete Fettsäuresalze in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausreichender Menge aufgebracht.According to the invention, the cleaning preparations in which the fatty acid salts are used according to the invention are advantageously used for cleaning oily and / or impure skin / scalp. For use, the compositions comprising fatty acid salts used according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
Erfindungsgemäß vorteilhaft können die Zubereitungen, in denen die Fettsäuresalze erfindungsgemäß vorteilhaft verwendet werden, als Tränkmedium für ein unlösliches Substrat, beispielsweise ein Vlies oder Tuch, eingesetzt werden, wobei das Substrat auch in Form eines trocken anmutenden Substrates oder als feucht anmutendes Substrat vorliegen kann.According to the invention, the preparations in which the fatty acid salts are advantageously used according to the invention can be used as the impregnation medium for an insoluble substrate, for example a nonwoven or cloth, the substrate also being able to be in the form of a substrate which appears to be dry or as a substrate which appears to be moist.
Erfindungsgemäß vorteilhaft können die Zubereitungen, in denen die Fettsäuresalze erfindungsgemäß vorteilhaft verwendet werden, als Shampoo, Duschgel, Schaum- oder Wannenbad sowie als Handwaschlotion oder Rasierschaum eingesetzt werden. Sie können erfindungsgemäß vorteilhaft in Doppelkammerverpackungen oder Schaumspendem (mechanischen Pumpspendem (Pumpfoamer) oder Aerosoldosen) aufbewahrt werden.Advantageously according to the invention, the preparations in which the fatty acid salts are advantageously used according to the invention can be used as a shampoo, shower gel, foam bath or tub bath and as a hand wash lotion or shaving cream. According to the invention, they can advantageously be stored in double-chamber packaging or foam dispensers (mechanical pump dispensers (pump foamers) or aerosol cans).
Erfindungsgemäß vorteilhaft können die Zubereitungen, in denen die Fettsäuresalze erfindungsgemäß vorteilhaft verwendet werden, zur Reinigung und Wäsche von Kleidungsstücken und Textilien („Waschmittel") und zur Reinigung von Gegenständen des täglichen Lebens (z.B. Geschirr, Tisch- und Schrankflächen, Autos) eingesetzt werden. In derartigen Fällen besteht die Selektivität darin, dass mit hoher Selektivität Schmutz und Verunreinigungen von den Textilien und Gegenständen des täglichen Lebens entfernt und dabei die hauteigenen Lipide, welche für die Verhinderung der Austrocknung der Haut essentiell sind, geschont werden.According to the invention, the preparations in which the fatty acid salts are advantageously used according to the invention can be used for cleaning and washing clothes and textiles (“detergents”) and for cleaning everyday objects (for example dishes, table and cupboard surfaces, cars). In such cases, the selectivity is that dirt and impurities are removed from the textiles and objects of daily life with high selectivity and the skin's own lipids, which are essential for preventing the skin from drying out, are protected.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen. Die Zahlenwerte in den Beispielen bedeuten Gewichtsprozente, bezogen auf das Gesamtgewicht der jeweiligen Zubereitungen. Beispiele:The following examples are intended to illustrate the present invention. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations. Examples:
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10257984A DE10257984A1 (en) | 2002-12-12 | 2002-12-12 | Cosmetic or dermatological skin cleansing agent e.g. for reducing skin roughness, comprises fatty acid salt surfactants |
| DE10257984.9 | 2002-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004052332A1 true WO2004052332A1 (en) | 2004-06-24 |
Family
ID=32336219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/050960 Ceased WO2004052332A1 (en) | 2002-12-12 | 2003-12-08 | Cleansing preparations containing fatty acid salts |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE10257984A1 (en) |
| WO (1) | WO2004052332A1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106193A2 (en) * | 1982-09-20 | 1984-04-25 | Union Carbide Corporation | Liquid skin cleanser composition |
| EP0203750A2 (en) * | 1985-05-13 | 1986-12-03 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
| JPH06256165A (en) * | 1993-03-05 | 1994-09-13 | Noevir Co Ltd | Liquid detergent |
| JPH07138127A (en) * | 1993-11-12 | 1995-05-30 | Kose Corp | Pack cosmetic |
| JPH11189788A (en) * | 1997-12-26 | 1999-07-13 | Nof Corp | Transparent gel-like detergent composition |
| JP2001031560A (en) * | 1999-07-15 | 2001-02-06 | Sakamoto Yakuhin Kogyo Co Ltd | Skin cleansing preparation |
| WO2001041729A1 (en) * | 1999-12-06 | 2001-06-14 | Unilever Plc | Stable, high glycerol liquids comprising sulfosuccinic acid monoesters |
| JP2002322498A (en) * | 2001-04-27 | 2002-11-08 | Mandom Corp | Detergent composition |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0115252A3 (en) * | 1982-12-29 | 1985-12-27 | Ciba-Geigy Ag | Mixtures of quaternary polymer ammonium salts, surfactants and fatty acids, their preparation and use in cosmetic compositions |
| JP2567277B2 (en) * | 1988-10-27 | 1996-12-25 | 川研ファインケミカル株式会社 | Liquid detergent composition |
| US5234619A (en) * | 1989-05-05 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
| US5132037A (en) * | 1989-05-05 | 1992-07-21 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
| JP3346420B2 (en) * | 1991-07-26 | 2002-11-18 | 花王株式会社 | Detergent composition |
| AU3811193A (en) * | 1992-03-25 | 1993-10-21 | Procter & Gamble Company, The | Cleansing compositions |
| EG20886A (en) * | 1993-06-18 | 2000-05-31 | Procter & Gamble | Personal cleansing system comprising a plolymeric diamon-mesh bath sponge and a liquid cleanser with moisturizer |
| CA2207031A1 (en) * | 1994-12-06 | 1996-06-13 | The Procter & Gamble Company | Shelf stable skin cleansing liquid with gel forming polymer, lipid and crystalline ethylene glycol fatty acid ester |
| EP0728475A3 (en) * | 1995-02-21 | 1997-03-19 | Kao Corp | Skin cleanser |
| JP3620140B2 (en) * | 1996-02-26 | 2005-02-16 | 株式会社ツムラ | Liquid detergent composition for skin |
| DE19649102A1 (en) * | 1996-11-27 | 1998-05-28 | Henkel Kgaa | cleaning supplies |
| DE19735518C1 (en) * | 1997-08-16 | 1999-03-11 | Friedrun Geier | Rinsable emulsions for use as tallow-dissolving preparations |
| JP2000192078A (en) * | 1998-12-25 | 2000-07-11 | Lion Corp | Liquid detergent composition |
| DE19916036A1 (en) * | 1999-04-09 | 2000-10-12 | Cognis Deutschland Gmbh | Hand washing pastes |
| JP2001213763A (en) * | 2000-02-03 | 2001-08-07 | Kanebo Ltd | Skin cleaning agent |
-
2002
- 2002-12-12 DE DE10257984A patent/DE10257984A1/en not_active Withdrawn
-
2003
- 2003-12-08 WO PCT/EP2003/050960 patent/WO2004052332A1/en not_active Ceased
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106193A2 (en) * | 1982-09-20 | 1984-04-25 | Union Carbide Corporation | Liquid skin cleanser composition |
| EP0203750A2 (en) * | 1985-05-13 | 1986-12-03 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
| JPH06256165A (en) * | 1993-03-05 | 1994-09-13 | Noevir Co Ltd | Liquid detergent |
| JPH07138127A (en) * | 1993-11-12 | 1995-05-30 | Kose Corp | Pack cosmetic |
| JPH11189788A (en) * | 1997-12-26 | 1999-07-13 | Nof Corp | Transparent gel-like detergent composition |
| JP2001031560A (en) * | 1999-07-15 | 2001-02-06 | Sakamoto Yakuhin Kogyo Co Ltd | Skin cleansing preparation |
| WO2001041729A1 (en) * | 1999-12-06 | 2001-06-14 | Unilever Plc | Stable, high glycerol liquids comprising sulfosuccinic acid monoesters |
| JP2002322498A (en) * | 2001-04-27 | 2002-11-08 | Mandom Corp | Detergent composition |
Non-Patent Citations (5)
Also Published As
| Publication number | Publication date |
|---|---|
| DE10257984A1 (en) | 2004-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69330565T2 (en) | LAUNDRY DETERGENT | |
| DE69930089T3 (en) | Foaming and conditioning cleansing composition | |
| DE202011110814U1 (en) | Body cleanser with mild surfactant systems | |
| EP0965322B1 (en) | Hair cleansing composition and personal cleansing composition with low skin irritancy | |
| DE102005014423A1 (en) | Care system of PVP and acrylate polymers | |
| EP2654705A2 (en) | Active ingredient combinations of glyceryl glucosides and one or more mild surfactants | |
| DE10234257A1 (en) | Self-warming cosmetic cleansing cloth is impregnated with a polyalcohol (e.g. polyethyleneglycol) which generates heat on contact with water | |
| DE60310856T2 (en) | Liquid cleaners based on soaps and synthetic surfactants; Their use for cleaning human keratin materials | |
| EP1432401A1 (en) | Use of surfactants with a ratio of hemolysis value to denaturation index of greater than or equal to 1 for obtaining or increasing the selectivity of cleansing preparations | |
| WO2004073666A1 (en) | Foamable cosmetic cleansing preparation | |
| DE10236063A1 (en) | Non-allergenic aqueous cosmetic composition for use in skin cleansing contains at least two surfactants, hydrocolloid(s) and water-soluble salt(s) | |
| EP1443887A2 (en) | Use of alkyl glucosides to obtain or enhance selectivity of cleaning formulations | |
| EP2654694A2 (en) | Active ingredient combinations of glyceryl glucosides and one or more pearlescent agents and/or opacifiers | |
| DE10157543A1 (en) | Cloths impregnated with an emulsion containing chitosan and/or lecithin, useful for skin cleansing and make-up removal | |
| EP2654703A2 (en) | Active substance combinations of glucosyl glycerides and one or more partially highly ethoxylated esters of polyols and fatty acids | |
| EP1496856A1 (en) | Foaming cleaning emulsions containing starch | |
| WO2007042410A1 (en) | Deodorizing cleansing preparation | |
| WO2004052332A1 (en) | Cleansing preparations containing fatty acid salts | |
| EP1505954A1 (en) | Highly foaming cleansing gel containing acylamino acid surfactants | |
| DE10237735A1 (en) | Composition especially for skin cleansing comprises a cleansing component and a stearate-emulsified oil-in-water component and is stored in a package with one or two exit openings | |
| EP3122318B1 (en) | Thickened transparent surfactant systems having a flow limit, containing 4-hydroxyacetophenone | |
| DE10216509A1 (en) | Free-flowing cosmetic or dermatological cleansing gel contains 12-22C fatty acid as alkali(ne earth) soap together with pre-gelatinized crosslinked starch derivative | |
| EP1494643A2 (en) | Use of alkyl glucosides in order to obtain or increase the selectivity of cleaning preparations | |
| EP1366739A1 (en) | Conditioning shampoo | |
| EP1660622B1 (en) | Multiphase surfactant product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: JP |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |