WO2007093298A1 - Gel formulations for arthropod and plathelminth control - Google Patents
Gel formulations for arthropod and plathelminth control Download PDFInfo
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- WO2007093298A1 WO2007093298A1 PCT/EP2007/000956 EP2007000956W WO2007093298A1 WO 2007093298 A1 WO2007093298 A1 WO 2007093298A1 EP 2007000956 W EP2007000956 W EP 2007000956W WO 2007093298 A1 WO2007093298 A1 WO 2007093298A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—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)
- A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—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
- A61K8/34—Alcohols
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; 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
- A61K8/72—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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/02—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings containing insect repellants
Definitions
- the present invention relates to "a ⁇ Formülie spang to AfthropöderT-ürld PlöhelmiritheifAbwehf based on piperidine derivatives in gel formulations.
- ethanol propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, ethylene or propylene oxide based copolymeric polyether polyols (both block copolymers and random copolymers), 2-ethyl-1,3 Hexanediol, glycerin, trimethylolpropane, etc.
- solubility series is given from a ternary system (icaridine, alcohol, water). These mixtures give each stable lotions.
- the viscosity of the formulations was determined in accordance with DIN 53019 of November 1983:
- gel formulations have become established in the pharmaceutical and cosmetic industry. They consist essentially of ternary systems of water, a thickener and alcohol. Thickeners are substances that increase the "consistency" of a medium, thus making it more viscous. The consistency is strongly related to the theological properties of the medium.This has an effect of viscosity, thixotropy, pouring properties, viscoelasticity and surface tension For example, carbomer, polyacrylic acid, polyacrylamide, polyvinylpyrrolidine or derivatives thereof are frequently used, and in many cases the gel formulation must additionally be adjusted to a cosmetically usable pH range by means of a so-called neutralizer.
- Insect repellent formulations as emulsions based on the active ingredient N, N-diethyl-m-toluamide (DEET) are already known.
- DEET N-diethyl-m-toluamide
- US 5,916,541 A1 describes emulsions containing a insect repellent, a sunscreen and a film former.
- US 5,989,529 A1 also describes emulsions which comprise a block polymer, a sunscreen agent and optionally a repellent.
- US Pat. No. 5,980,871 A1 describes emulsions which contain an insect repellent active ingredient, an inorganic sunscreen agent and an anionic emulsifier.
- the invention is therefore based on the object to provide stable gel formulations that have a high viscosity.
- the formulations are clear and stable.
- the formulation preferably has a viscosity of> 1000 mPas, very particularly preferably> 10000 mPas.
- the formulation preferably comprises as thickener polyacrylic acid, polymethacrylic acid, carbomer, polyvinylpyrrolidone, quaternary polyvinylpyrrolidone, vinylimidazole copolymer, dimethylaminoethyl methacrylate copolymer, poly (dimethyldiallylammonium chloride), dimethyldiallylammonium chloride copolymer, chitosan, vinylcaprolactam-v-pyrrolidone-dimethylaminoethyl methacrylate copolymer, tert-butylacrylamide-ethylacrylate acrylic acid copolymer, polyacrylamide or mixtures thereof.
- a neutralizer such as, for example, 2-arnano-2-methyl-1-propanol, triisopropanolamine (TIPA), 2-amino-2-methyl- l, 3-propanediol (AMPD), potassium hydroxide or sodium hydroxide solution in a pH neutral range, so it does not cause skin irritation.
- the formulation contains 0 to 35% by weight of N-methylpyrrolidone, phenethyl alcohol, benzyl alcohol, an aliphatic alcohol, aliphatic ethers, aliphatic polyethers and / or mixtures thereof.
- the formulation preferably additionally contains 0.1 to 20% by weight of ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, copolymeric polyether polyols based on ethylene or propylene oxide, 2-ethyl-1, 3-hexanediol, glycerol, trimethylolpropane and / or mixtures thereof.
- repellent is preferably a piperidine derivative of the general formula: - A -
- Ri 'and R 2 ' independently represent alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkoxy, cycloalkenoxy and cycloalkynoxy, and
- n 0 or 1 or mixtures thereof are used.
- the repellent used is preferably a piperidine derivative of the general formula where R 1 'and R 2 ' independently of one another are C 1 -C 2 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 1 -C -hydroxyalkyl, C 3 -C 4 -cycloalkyl.
- the repellent used is preferably 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester (icaridine) and 1- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine both as a racemic mixture and as a chiral compound, for example (1S, 2'S). - l- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine used.
- Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester, acrylic acid polymer, ethanol, 2-amino-2-methyl-1-propanol and water.
- Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, carbomer, ethanol, 2-amino-2-methyl-l-propanol and water.
- Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, polyvinylpyrrolidone, ethanol and water.
- a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, polyacrylamide, ethanol and water is particularly preferred.
- a formulation containing as a mixture 1-piperidinecarboxylic acid-2-hydroxyethyl-1-methylpropyl ester, acrylate / octylacrylamide copolymer, ethanol and water is particularly preferred.
- oils are used.
- hydrodispersion gels As oils are preferably mineral oils, polycyclic aromatic hydrocarbons, paraffin oils, silicone oils such as polysiloxane, cyclosiloxane, methicone.
- Animal oils such as mink oil, fish oils, natural vegetable oils such as olive oil, sesame oil linseed oil, palm oil,
- Sunflower oil peanut oil. Rapeseed oil, soybean oil, coconut oil, palm kernel oil, peach kernel oil, almond oil, castor oil, dehydrated castor oil, pine oil, tall oil and / or mixtures thereof.
- triglycerides such as caprylic / Caprinkladrebiglycerid, triglyceride mixtures with vegetable fatty acids of chain length Cr ⁇ or other natural fatty acids, specifically selected, partial glyceride are saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the C S / io fatty acids.
- Fatty acid ester such as ethyl stearate, di-n-butyl adipate, hexyl laurate, glykolpelargonat dipropylene, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length Q 6 - I s, isopropyl myristate, isopropyl palmitate, caprylic / CaprinTexreester of saturated fatty alcohols of chain length Cms, isopropyl stearate , isopropyl palmitate, caprylic / Caprinklareester of saturated fatty alcohols of chain length Q 2 - 1 8, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester such as dibutyl phthalate, diisopropyl adipate, related to the latter Estergemische inter alia fatty alcohols such as isotridecyl alcohol, 2-o
- Oxybenzone, sulisobenzone (2-hydroxy-4-methylbenzophenone-5-sulphonic acid), dioxybenzene (2,2'-dihydroxy-4-methoxybenzophenone), menthylanthranilate, avobenzone, para-aminobenzoic acid are particularly preferred as components for producing a UV filter effect , Octyhnethoxycinnamat, octocrylene, Drometrizoltrisiloxan, TEA salicylate octyl salicylate, homomenthyl salicylate, octyl dimethyl PABA, titanium dioxide, zinc oxide diendücamfersulfonkla, butylmethoxydibenzoylmethane, Metliylbenzylidenkamfer, octyl, terephthalyl, ethyl PABA, hydroxymethylphenyl-benzotriazole,
- biocides are preferably additionally used.
- Particularly preferred biocides are benzyl alcohol, trichlorobutanol, o-phenylphenol, para-hydroxybenzoic acid methyl ester, para-hydroxybenzoic acid ethyl ester.
- antioxidants preference is given to using butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tocopherol, sulfites, metabisulfites, such as potassium metabisulfite, ascorbic acid, and / or mixtures thereof.
- viscosity modifiers are carboxymethylcelMose, hydroxyethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, polyvinyl acetate, vinyl acetate-crotonic acid copolymer, alginates, gelatin, pectin, casein, agar-agar, gum arabic, aloe vera, polyvinylpyrrolidone , Polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, polypropylene glycols, block and / or random copolymer of propylene and ethylene glycol units, waxes, colloidal silicas, and / or mixtures thereof.
- dyes or color pigments it is particularly preferred to use all dyes approved for human or animal use in dissolved or suspended form and as pigments all pigments approved for human or animal use in dissolved or suspended form, and / or mixtures thereof.
- fragrances are preferably used in addition.
- Fragrances used are particularly preferably perfume oils and other low-boiling substances which are approved for use on humans or animals, and / or mixtures thereof.
- plasticizers are preferably additionally used.
- the plasticizers used are particularly preferably diethyl phthalate, di (ethylhexyl) phthalate, diethyl citrate, adipate, silicones, polyglycols and / or mixtures thereof.
- the invention also includes a process for the preparation of the formulation, characterized in that
- the invention also includes the use of the formulations for expelling arthropods and / or platinum bushes.
- the formulation is preferably used to ward off harmful or irritating sucking and biting arthropods, preferably insects, ticks and mites.
- the sucking insects mainly include the mosquitoes (for example Aedes aegypti, Aedes vexans, Aedes taeniorhynchus, Aedes albopictus, Culex pipiens fatigans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles dirus, Anopheles gambiae, Anopheles sinensis, Anopheles stephensi, Mansonia titillans), butterfly mosquitoes (for example Phlebotomus papatasii, Phlebotomus duboscqi), groats (for example Culicoides furens, Culicoides minimctatus), blackflies (for example Simulium damnosum, Simulium venustum), biting flies (for example Stomoxys calcitrans), tsetse flies (for example Glossina mors
- bugs for example Cimex lectularius, Rhodnius prolixus, Triatoma infestans
- lice for example Pediculus humanis, Haematopinus suis, Damalina ovis
- fleas for example Pulex irritans, Xenops
- the biting insects are essentially cockroaches (for example Blattella germanica, Periplaneta americana, Blatta orientalis, Supella longipalpa), beetles (for example Sitiophilus granarius, Tenebrio molitor, Dermestes lardarius, Stegobium paniceum, Anobium punctatum,
- Moths for example Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineola bisselliella, Tinea pellionella, Trichophaga tapetzella).
- the other arthropods include ticks (for example, Ixodes ricinus, Ixodes scapula ⁇ s, Argas reflexus, Omitliodorus moubata, Ripicephalus sangumeus, Boophihus microplus, Amblyomma hebraeum) and mites (for example Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides fa ⁇ nae, Dermanyssus galhnae, Acarus siro)
- ticks for example, Ixodes ricinus, Ixodes scapula ⁇ s, Argas reflexus, Omitliodorus moubata, Ripicephalus sangumeus, Boophihus microplus, Amblyomma hebraeum
- mites for example Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides fa ⁇ na
- the formulations are preferably used against platelets, in particular against infectious stages of platelets.
- the formulation is preferably used for repelling platelet tumors such as Schistosomahaematobium, Schistosoma japomcum, Tnchobilharzia spp and Ornithobilharzia spp, but also Echinostoma spp
- the formulations are preferably used by applying to the skin of humans or animals by means of dripping, brushing, rubbing, spraying, by dipping / dipping, bathing or washing
- the formulations are preferably used for the impregnation of a carrier or encapsulation / microencapsulation in a shell of liposomes and / or ureas or for filling a porous packaging or a container for later use on the body of a living being.
- the systems thus obtained can then be applied to the body of a living being
- the carrier used is preferably tissue, nonwoven, gel and / or polyacrylate
- the viscosity is determined according to DIN 53019 of November 1983.
- the stability of the formulation was determined by the centrifuge microwave assay.
- the test serves to evaluate the structure of disperse systems. The test method looks like this:
- test sample of the formulation to be tested is acclimated after preparation for about 2 days at room temperature. Approximately 10 g of product are weighed from the test sample into a centrifuge tube (25 ml nominal volume).
- the centrifuge tube is irradiated 75 seconds with stage 1 of the apparatus AEG Micromat ® 114 (corresponding to a Wegmanittlichen power output of 75 watts) in the microwave. Subsequently, this sample is acclimated for one hour at room temperature and centrifuged for 11 minutes at 4350 revolutions / minute in an Eppendorf centrifuge 5403.
- the test of the sample is done visually by the laboratory technician.
- the sample is examined for homogeneity of the formulation. Differing appearance to the untreated sample, for example occurring phase separation or bubbles in the centrifuge tube are described.
- a lotion of the following composition is applied:
- a gel formulation of the following composition is prepared:
- phase A is mixed at room temperature.
- phase B is mixed at room temperature for 15 minutes and slowly added to phase A with vigorous stirring.
- a pH control is carried out and adjusted by means of 2-amino-2-methyl-l-propanol in the range pH 5.5 to 7.0.
- a gel formulation of the following composition is prepared:
- phase A is mixed at room temperature.
- phase B is mixed at room temperature for 15 minutes and slowly added with vigorous stirring.
- a pH control is carried out and adjusted by means of 2-amino-2-methyl-l-propanol in the range pH 5.5 to 7.0.
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Abstract
Description
Gel-Formulierung zur Arthropoden- und Plathelminthen-Abwehr Gel formulation for arthropod and platelet defenses
Die vorliegende Erfindung betrifft "eine~Formüliefüng zur AfthropöderT-ürld PläthelmiritheifAbwehf auf Basis von Piperidin-Derivaten in Gel-Formulierungen.The present invention relates to "a ~ Formüliefüng to AfthropöderT-ürld PläthelmiritheifAbwehf based on piperidine derivatives in gel formulations.
Aus der EP 0 281 908 Al und EP 0 289 842 Al ist es bekannt, dass bestimmte Piperidin-Derivate als Mittel zur Abwehr von Arthropoden (insbesondere Insekten) und helminthischen Parasiten eingesetzt werden können. Als eine der wichtigsten Strukturen hat sich die Verbindung 1-It is known from EP 0 281 908 A1 and EP 0 289 842 A1 that certain piperidine derivatives can be used as agents for repelling arthropods (in particular insects) and helminthic parasites. One of the most important structures is compound 1-
Piperidincarbonsäure-2-Hydroxyethyl-l-Methylpropylester herausgestellt und am Markt unter demPiperidine carboxylic acid 2-hydroxyethyl-l-methylpropyl ester exposed and marketed under the
Wirkstoffhamen Icaridin und Bayrepel® etabliert. Diese Verbindung wird aber nicht alsActive substance Icaridin and Bayrepel ® established. This connection is not as
Reinsubstanz eingesetzt, sondern als formulierte Flüssigkeit in Form von Lotion vertrieben. Die üblichen Konzentrationen des Wirkstoffs betragen hier 1 bis 40 % bezogen auf die Masse derPure substance, but distributed as a formulated liquid in the form of lotion. The usual concentrations of the active ingredient here are 1 to 40% based on the mass of
Formulierung.Formulation.
Als stabile Formulierungen haben sich hier Lotionen auf Basis dieser Piperidin-Verbindungen sowie Wasser und einer leicht flüchtigen Alkoholkomponente etabliert. Als Alkohol werden hier physiologisch verträgliche flüchtige Lösungsmittel eingesetzt. Hierzu zählen neben Phenethylalkohol und Benzylalkohol auch mono- und mehrfiinktionale aliphatische Alkohole (Alkanole, Alkandiole, Alkantriole). Dies sind zum Beispiel Ethanol, Propanol, Isopropanol, n-Butanol, sec-Butanol, Propylenglycol, Polypropylenglycol, Ethylenglycol, Polyethylenglycol, copolymere Polyetherpolyole auf Ethylen- oder Propylenoxidbasis (sowohl Blockcopolymere als auch Random-Copolymere), 2- Ethyl-1,3-Hexandiol, Glycerin, Trimethylolpropan etc.As stable formulations have here lotions based on these piperidine compounds and water and a volatile alcohol component established. As alcohol, physiologically compatible volatile solvents are used here. In addition to phenethyl alcohol and benzyl alcohol, these include monofunctional and multifunctional aliphatic alcohols (alkanols, alkanediols, alkanetriols). These are, for example, ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, ethylene or propylene oxide based copolymeric polyether polyols (both block copolymers and random copolymers), 2-ethyl-1,3 Hexanediol, glycerin, trimethylolpropane, etc.
Als Beispiel für den Stand dieser Technik ist die folgende Löslichkeitsreihe aus einem ternären System (Icaridin, Alkohol, Wasser) gegeben. Diese Mischungen ergeben jeweils stabile Lotionen. Neben der Stabilität wurde an den Formulierungen auch deren Viskosität nach DIN 53019 von November 1983 bestimmt:As an example of the state of this art, the following solubility series is given from a ternary system (icaridine, alcohol, water). These mixtures give each stable lotions. In addition to the stability, the viscosity of the formulations was determined in accordance with DIN 53019 of November 1983:
!) Aufgrund des Messsystems konnte für verschiedene Formulierungen nur festgestellt werden, dass deren Viskositätswerte unterhalb von 10 mPas liegen. !) Due to the measuring system it could only be determined for different formulations that their viscosity values are below 10 mPas.
Diese Lotionen besitzen somit als wesentlichen technischen Nachteil eine sehr niedrige Viskosität.These lotions thus have a very low viscosity as a significant technical disadvantage.
Teilweise liegt diese so niedrig, dass die Viskosität außerhalb des Messbereichs von Messgeräten zur Viskositätsbestimmung liegen. Daher ist ein zielgerichteter und gleichmäßiger Produktauftrag für den Konsumenten problematisch. Ein weiterer technischer Nachteil der Lotionen liegt in dem sehr hohen Ethanolgehalt. Dieser führt zum einen zu verschlechterten KosmetikeigenschaftenIn some cases, this is so low that the viscosity is outside the measuring range of viscosity measuring instruments. Therefore, a targeted and consistent product order is problematic for the consumer. Another technical disadvantage of the lotions is the very high ethanol content. This leads to a deterioration in cosmetic properties
(Hautreizung). Zum anderen bereitet er mit Werten um 40 % auch Probleme hinsichtlich des(Skin irritation). On the other hand, with values around 40%, he also prepares problems regarding the
Brandverhaltens dieser Formulierungen. Diese bieten einen erheblichen Vorteil, da der Anteil der leicht brennbaren Formulierbestandteile deutlich reduziert werden kann.Fire behavior of these formulations. These offer a considerable advantage, since the proportion of highly flammable formulation constituents can be significantly reduced.
Als Alternative hierfür haben sich in der pharmazeutischen und kosmetischen Industrie Gel- Formulierungen etabliert. Sie bestehen im Wesentlichen aus ternären Systemen von Wasser, einem Verdicker und Alkohol. Verdicker sind Substanzen, die die „Konzistenz" eines Mediums erhöhen, es also zähflüssiger machen. Die Konsistenz hängt stark mit den Theologischen Eigenschaften des Mediums zusammen. Hier wirkt sich ein Zusammnspiel aus Viskosität, Thixotropie, Gießeigenschaften, Viskoelastizität und Oberflächenspannung aus. Als Verdicker werden zum Beispiel Carbomer, Polyacrylsäure, Polyacrylamid, Polyvinylpyrrolidin oder Derivate hiervon eingesetzt. Häufig muss die Gel-Formulierung noch zusätzlich mit Hilfe eines sogenannten Neutralisators in einen cosmetisch nutzbaren pH-Wertbereich eingestellt werden.As an alternative to this, gel formulations have become established in the pharmaceutical and cosmetic industry. They consist essentially of ternary systems of water, a thickener and alcohol. Thickeners are substances that increase the "consistency" of a medium, thus making it more viscous.The consistency is strongly related to the theological properties of the medium.This has an effect of viscosity, thixotropy, pouring properties, viscoelasticity and surface tension For example, carbomer, polyacrylic acid, polyacrylamide, polyvinylpyrrolidine or derivatives thereof are frequently used, and in many cases the gel formulation must additionally be adjusted to a cosmetically usable pH range by means of a so-called neutralizer.
Insektenrepellentformulierungen als Emulsionen sind auf Basis des Wirkstoffs N,N-diethyl-m- toluamid (DEET) sind bereits bekannt. Zum Beispiel beschreibt US 5,916,541 Al Emulsionen, die einen msektenrepellentwirkstoff, ein Sonnenschutzmittel und einen Filmbildner enthalten. Auch US 5,989,529 Al beschreibt Emulsionen, die ein Blockpolmer, ein Soπnenschutzmittel und optional einen Repellent beinhalten. US 5,980,871 Al beschreibt Emulsionen, die einen Insektenrepellent- Wirkstoff, ein anorganisches Sonnenschutzmittel und einen anionischen Emulgator beinhalten.Insect repellent formulations as emulsions based on the active ingredient N, N-diethyl-m-toluamide (DEET) are already known. For example, US 5,916,541 A1 describes emulsions containing a insect repellent, a sunscreen and a film former. US 5,989,529 A1 also describes emulsions which comprise a block polymer, a sunscreen agent and optionally a repellent. US Pat. No. 5,980,871 A1 describes emulsions which contain an insect repellent active ingredient, an inorganic sunscreen agent and an anionic emulsifier.
Der Erfindung liegt deshalb die Aufgabe zugrunde, stabile Gel-Formulierungen bereit zu stellen, die eine hohe Viskosität aufweisen.The invention is therefore based on the object to provide stable gel formulations that have a high viscosity.
Diese Aufgabe wurde gelöst durch eine Formulierung zur Abwehr von Arthropoden und Plathelminthen enthaltend die Mischung:This object was achieved by a formulation for the defense of arthropods and Plathelminthen containing the mixture:
• 1 bis 39 Gewichtsprozent eines Repellents• 1 to 39% by weight of a repellent
• 0 bis 35 Gewichtsprozent eines Alkohols • 0,05 bis 25 Gewichtsprozent eines Verdickers und• 0 to 35% by weight of an alcohol • 0.05 to 25% by weight of a thickener and
• 0,1 bis 98,95 Gewichtsprozent Wasser• 0.1 to 98.95 weight percent water
die eine Viskosität von > 20 mPas aufweist.which has a viscosity of> 20 mPas.
Die Formulierungen sind klar und stabil.The formulations are clear and stable.
Die Formulierung weist vorzugsweise eine Viskosität von > 1000 mPas, ganz besonders bevorzugt > lOOO mPas auf.The formulation preferably has a viscosity of> 1000 mPas, very particularly preferably> 10000 mPas.
Die Methode zur Messung der Viskosität ist in den Beispielen angegeben.The method for measuring the viscosity is given in the examples.
Die Formulierung weist vorzugsweise als Verdicker Polyacrylsäure, Polymethacrylsäure, Carbomer, Polyvinylpyrrolidon, quartemäres Polyvinylpyrrolidon, Vinylimidazol Copolymer, Dimethylamiαoethylmethacrylat Copolymer, Poly(dimethyldiallylammoniumchlorid), Dimethyl- diallylammoniumchlorid Copolymer, Chitosan, Vmylcaprolactam-vMpyrrolidon-dimethylamino- ethylmethacrylat Copolymer, tert-Butylacrylamid-ethylacrylat-acrylsäure Copolymer, Polyacrylamid oder deren Mischungen aus.The formulation preferably comprises as thickener polyacrylic acid, polymethacrylic acid, carbomer, polyvinylpyrrolidone, quaternary polyvinylpyrrolidone, vinylimidazole copolymer, dimethylaminoethyl methacrylate copolymer, poly (dimethyldiallylammonium chloride), dimethyldiallylammonium chloride copolymer, chitosan, vinylcaprolactam-v-pyrrolidone-dimethylaminoethyl methacrylate copolymer, tert-butylacrylamide-ethylacrylate acrylic acid copolymer, polyacrylamide or mixtures thereof.
Bei Einsatz von verschiedenen Verdickern (zum Beispiel Carbomer oder Acrylsäurepolymeren) ist es vorteilhaft, die Formulierung mit HiUe eines Neutralisators wie zum Beispiel 2-Arniao-2-methyl-l- propanol, Triisopropanolamin (TIPA), 2-Amiαo-2-methyl-l,3-propandiol (AMPD), Kalilauge oder Natronlauge in einen pH-Wert neutralen Bereich einzustellen, damit es nicht zu Hautreizungen kommt.When using various thickeners (for example carbomer or acrylic acid polymers), it is advantageous to use the formulation with a neutralizer such as, for example, 2-arnano-2-methyl-1-propanol, triisopropanolamine (TIPA), 2-amino-2-methyl- l, 3-propanediol (AMPD), potassium hydroxide or sodium hydroxide solution in a pH neutral range, so it does not cause skin irritation.
m der Formulierung sind 0 bis 35 Gew-% N-Methylpyrrolidon, Phenethylalkohol, Benzylalkohol, eines aliphatischen Alkohols, aliphatischer Ether, aliphatischer Polyether und/oder Mischungen davon enthalten.The formulation contains 0 to 35% by weight of N-methylpyrrolidone, phenethyl alcohol, benzyl alcohol, an aliphatic alcohol, aliphatic ethers, aliphatic polyethers and / or mixtures thereof.
Die Formulierung enthält vorzugsweise zusätzlich 0,1 bis 20 Gew-% an Ethanol, Propanol, Isopropanol, n-Butanol, sec-Butanol, Propylenglycol, Polypropylenglycol, Ethylenglycol, Polyethylenglycol, copolymere Polyetherpolyole auf Ethylen- oder Propylenoxidbasis, 2-Ethyl-l,3- Hexandiol, Glycerin, Trimethylolpropan und/oder Mischungen davon.The formulation preferably additionally contains 0.1 to 20% by weight of ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, copolymeric polyether polyols based on ethylene or propylene oxide, 2-ethyl-1, 3-hexanediol, glycerol, trimethylolpropane and / or mixtures thereof.
Als Repellent wird vorzugsweise ein Piperidin-Derivat der allgemeinen Formel: - A -As a repellent is preferably a piperidine derivative of the general formula: - A -
worin wherein
Ri' sowie R2' unabhängig voneinander für Alkyl, Alkenyl, Alkinyl, Hydroxyalkyl, Hydroxyalkenyl, Hydroxyalkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkinyl, Cycloalkoxy, Cycloalkenoxy und Cycloalkinoxy steht, undRi 'and R 2 ' independently represent alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkoxy, cycloalkenoxy and cycloalkynoxy, and
n für 0 oder 1 steht oder Mischungen davon verwendet.n is 0 or 1 or mixtures thereof are used.
Als Repellent wird vorzugsweise ein Piperidin-Derivat der allgemeinen Formel verwendet wo Rl' sowie R2' unabhängig voneinander für Ci-Ci2 Alkyl, C2-C20 Alkenyl, C2-C20 Alkinyl, Ci-Ci2 Hydroxyalkyl, C3-C20 Hydroxyalkenyl, C3-C20 Hydroxyalkinyl, C3-C20 Cycloalkyl, C3-C20 Cycloalkeyl, C3-C20 Cycloalkinyl, C3-C20 Cycloalkoxy, Ci-Ci2 Cycloalkenoxy und Ci-Ci2 Cycloalkinoxy steht, und n für 0 oder 1 steht oder Mischungen davon.The repellent used is preferably a piperidine derivative of the general formula where R 1 'and R 2 ' independently of one another are C 1 -C 2 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 1 -C -hydroxyalkyl, C 3 -C 4 -cycloalkyl. C 20 hydroxyalkenyl, C 3 -C 20 hydroxyalkynyl, C 3 -C 20 cycloalkyl, C 3 -C 20 Cycloalkeyl, C 3 -C 20 cycloalkynyl, C 3 -C 20 cycloalkoxy, Ci-Ci 2 Cycloalkenoxy and Ci-Ci 2 Cycloalkinoxy and n is 0 or 1 or mixtures thereof.
Als Repellent wird vorzugsweise l-Piperidincarbonsäure-2-Hydroxyethyl-l-Methylpropylester (Icaridin) und l-(3-cyclohexen-l-ylcarbonyl)-2-methylpiperidin sowohl als racemische Mischung als auch als chirale Verbindung zum Beispiel (1S,2'S)- l-(3-cyclohexen-l-ylcarbonyl)-2- methylpiperidin verwendet. Ganz besonders bevorzugt ist l-Piperidincarbonsäure-2-Hydroxyethyl-l- Methylpropylester (Icaridin).The repellent used is preferably 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester (icaridine) and 1- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine both as a racemic mixture and as a chiral compound, for example (1S, 2'S). - l- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine used. Very particular preference is given to 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester (icaridine).
Besonders bevorzugt ist eine Formulierung, die als Mischung l-Piperidincarbonsäure-2- Hydroxyethyl-1-Methylpropylester, Acrylsäurepolymer, Ethanol, 2-Amino-2-methyl-l-propanol und Wasser enthält.Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester, acrylic acid polymer, ethanol, 2-amino-2-methyl-1-propanol and water.
Besonders bevorzugt ist eine Formulierung, die als Mischung l-Piperidincarbonsäure-2- Hydroxyethyl-1-Methylpropylester, Carbomer, Ethanol, 2-Amino-2-methyl-l-propanol und Wasser enthält.Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, carbomer, ethanol, 2-amino-2-methyl-l-propanol and water.
Besonders bevorzugt ist eine Formulierung, die als Mischung l-Piperidincarbonsäure-2- Hydroxyethyl-1-Methylpropylester, Polyvinylpyrrolidon, Ethanol und Wasser enthält.Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, polyvinylpyrrolidone, ethanol and water.
Besonders bevorzugt ist auch eine Formulierung, die als Mischung l-Piperidincarbonsäure-2- Hydroxyethyl-1-Methylpropylester, Polyacrylamid, Ethanol und Wasser enthält. Besonders bevorzugt ist eine Formulierung, die als Mischung 1 -Piperidincarbonsäure-2- Hydroxyethyl-1-Methylpropylester, Acrylat/Octylacrylamid Copolymer, Ethanol und Wasser enthält.Also particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, polyacrylamide, ethanol and water. Particularly preferred is a formulation containing as a mixture 1-piperidinecarboxylic acid-2-hydroxyethyl-1-methylpropyl ester, acrylate / octylacrylamide copolymer, ethanol and water.
Bei der Formulierung werden vorzugsweise zusätzlich Komponenten zur Erzeugung eines Hautpflegeeffektes eingesetzt. Als Komponenten hierfür werden Öle eingesetzt. Es entstehen sogenannte Hydrodispersionsgele. Als Öle werden vorzugsweise Mineralöle, polycyclische aromatische Kohlenwasserstoffe, Paraffinöle, Silikonöle wie Polysiloxan, Cyclosiloxan, Methicon.In the formulation, it is preferable to additionally use components for producing a skin care effect. As components for this oils are used. The result is so-called hydrodispersion gels. As oils are preferably mineral oils, polycyclic aromatic hydrocarbons, paraffin oils, silicone oils such as polysiloxane, cyclosiloxane, methicone.
Tieröle wie Nerzöl, Fischöle, natürliche Pflanzenöle wie Olivenöl, SesamöL Leinöl, Palmöl,Animal oils such as mink oil, fish oils, natural vegetable oils such as olive oil, sesame oil linseed oil, palm oil,
Sonnenblumenöl, Erdnussöl. Rapsöl, Sojaöl, Kokosfett, Palmkernfett, Pfirsichkernöl, Mandelöl, Rizinusöl, dehydriertes Rizinusöl, Pinienöl, Tallöl und/oder Mischungen davon verwendet.Sunflower oil, peanut oil. Rapeseed oil, soybean oil, coconut oil, palm kernel oil, peach kernel oil, almond oil, castor oil, dehydrated castor oil, pine oil, tall oil and / or mixtures thereof.
Als zusätzliche Ölphasensysteme werden vorzugsweise synthetische Triglyceride wie Capryl/Caprinsäurebiglycerid, Triglyceridgemische mit Pflanzenfettsäuren der Kettenlänge Crπ oder anderen speziell ausgewählten natürlichen Fettsäuren, Partialglyceridgemische gesättigter oder ungesättigter eventuell auch hydroxylgruppenhaltiger Fettsäuren, Mono- und Diglyceride der CS/io- Fettsäuren. Fettsäureester wie Ethylstearat, Di-n-butyl-adipat, Laurinsäurehexylester, Dipropylen- glykolpelargonat, Ester einer verzweigten Fettsäure mittlerer Kettenlänge mit gesättigten Fettalkoholen der Kettenlänge Q6-Is, Isopropylmyristat, Isopropylpalmitat, Capryl/Caprinsäureester von gesättigten Fettalkoholen der Kettenlänge Cms, Isopropylstearat, Isopropylpalmitat, Capryl/Caprinsäureester von gesättigten Fettalkoholen der Kettenlänge Q2-18, Ölsäureoleylester, Ölsäuredecylester, Ethyloleat, Milchsäureethylester, wachsartige Fettsäureester wie Dibutylphthalat, Adipinsäurediisopropylester, letzterem verwandte Estergemische unter anderem Fettalkohole wie Isotridecylalkohol, 2-Octyldodecanol, Cetylstearyl-alkohol, Oleylalkohol und/oder Mischungen davon verwendet.As an additional oil phase systems preferably synthetic triglycerides such as caprylic / Caprinsäurebiglycerid, triglyceride mixtures with vegetable fatty acids of chain length Crπ or other natural fatty acids, specifically selected, partial glyceride are saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the C S / io fatty acids. Fatty acid ester such as ethyl stearate, di-n-butyl adipate, hexyl laurate, glykolpelargonat dipropylene, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length Q 6 - I s, isopropyl myristate, isopropyl palmitate, caprylic / Caprinsäureester of saturated fatty alcohols of chain length Cms, isopropyl stearate , isopropyl palmitate, caprylic / Caprinsäureester of saturated fatty alcohols of chain length Q 2 - 1 8, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester such as dibutyl phthalate, diisopropyl adipate, related to the latter Estergemische inter alia fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol and / or mixtures thereof.
Bei der Formulierung werden vorzugsweise zusätzlich Komponenten zur Erzeugung eines UV- Filtereffekts eingesetzt. Als Komponenten zur Erzeugung eines UV-Filtereffekts werden besonders bevorzugt Oxybenzon, Sulisobenzon (2-Hydroxy-4-methylbenzophenon-5-sulfonsäure), Dioxy- benzon (2,2'-Dihydroxy-4-methoxybenzophenon), Menthylanthranilat, Avobenzon, para Aminobenzoesäure, Octyhnethoxycinnamat, Octocrylen, Drometrizoltrisiloxan, Octylsalicylat, Homomenthylsalicylat, Octyldimethyl-PABA, TEA-salicylat, Titandioxid, Zinkoxid, Butylmethoxydibenzoylmethan, Metliylbenzylidenkamfer, Octyltriazon, Terephthalyl- diendücamfersulfonsäure, Ethyl-PABA, Hydroxymethylphenyl-benzotriazol, Methylen-bi- benzotriazoyltetramethylbutylphenol, Bis-octyloxyphenol-methoxy-phenol-triazin, Novantisol-säure und/oder Mischungen davon eingesetzt. In der Formulierung werden vorzugsweise zusätzlich Biozide eingesetzt. Als Biozide werden besonders bevorzugt Benzylakohol, Trichlorbutanol, o-Phenylphenol, Para-Hydroxybenzoesäure- methylester, Para-Hydroxybenzoesäureethylester. Para-Hydroxybenzoesäurepropylester, Para- Hydroxybenzoesäurebutylester, n-Butanol, Propanol, Iso-Propanol, Ethanol und/oder Mischungen davon eingesetzt.In the formulation, it is preferable to additionally use components for producing a UV filter effect. Oxybenzone, sulisobenzone (2-hydroxy-4-methylbenzophenone-5-sulphonic acid), dioxybenzene (2,2'-dihydroxy-4-methoxybenzophenone), menthylanthranilate, avobenzone, para-aminobenzoic acid are particularly preferred as components for producing a UV filter effect , Octyhnethoxycinnamat, octocrylene, Drometrizoltrisiloxan, TEA salicylate octyl salicylate, homomenthyl salicylate, octyl dimethyl PABA, titanium dioxide, zinc oxide diendücamfersulfonsäure, butylmethoxydibenzoylmethane, Metliylbenzylidenkamfer, octyl, terephthalyl, ethyl PABA, hydroxymethylphenyl-benzotriazole, methylene bi- benzotriazoyltetramethylbutylphenol, bis-octyloxyphenol methoxy-phenol-triazine, Novantisol acid and / or mixtures thereof used. In the formulation, biocides are preferably additionally used. Particularly preferred biocides are benzyl alcohol, trichlorobutanol, o-phenylphenol, para-hydroxybenzoic acid methyl ester, para-hydroxybenzoic acid ethyl ester. Para-Hydroxybenzoesäurepropylester, para-Hydroxybenzoesäurebutylester, n-butanol, propanol, iso-propanol, ethanol and / or mixtures thereof used.
In der Formulierung werden vorzugsweise zusätzlich Antioxydantien eingesetzt. Als Antioxydantien werden besonders bevorzugt butyliertes Hydroxytoluol (BHT), butyliertes Hydroxyanisol (BHA), Tocopherol, Sulfite, Metabisulfite wie Kaliummetabisulfit, Ascorbinsäure, und/oder Mischungen davon eingesetzt.In the formulation, it is preferable to additionally use antioxidants. As antioxidants, preference is given to using butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tocopherol, sulfites, metabisulfites, such as potassium metabisulfite, ascorbic acid, and / or mixtures thereof.
In der Formulierung werden vorzugsweise zusätzlich Viskositätsmodifizierer eingesetzt. Als Viskositätsmodifizierer werden besonders bevorzugt CarboxymethylcelMose, Hydroxyethyl- cellulose, Methylcellulose und andere Cellulose- und Stärke-Derivate, Polyacrylate, Polyvinylacetat, Vinylacetat-crotonsäure Copolymer, Alginate, Gelatine, Pektin, Casein, Agar-Agar, Gummi- Arabicum, Aloe Vera, Polyvinylpyrrolidon, Polyvinylalkohol, Copolymere aus Methylvinylether und Maleinsäuranhydrid, Polyethylenglycole, Polypropylenglycole, block und/oder random Copolymer aus Propylen- und Ethylenglycoleinheiten, Wachse, kolloidale Kieselsäuren, und/oder Mischungen davon eingesetzt.In the formulation, it is preferable to additionally use viscosity modifiers. Particularly preferred viscosity modifiers are carboxymethylcelMose, hydroxyethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, polyvinyl acetate, vinyl acetate-crotonic acid copolymer, alginates, gelatin, pectin, casein, agar-agar, gum arabic, aloe vera, polyvinylpyrrolidone , Polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, polypropylene glycols, block and / or random copolymer of propylene and ethylene glycol units, waxes, colloidal silicas, and / or mixtures thereof.
In der Formulierung werden vorzugsweise zusätzlich Farbstoffe oder Farbpigmente eingesetzt. Als Farbstoffe oder Farbpigmente werden besonders bevorzugt alle zur Anwendung am Menschen oder Tier zugelassenen Farbstoffe in gelöster oder suspendierter Form und als Pigmente alle zur Anwendung am Menschen oder Tier zugelassenen Pigmente in gelöster oder suspendierter Form, und/oder Mischungen davon eingesetzt.In the formulation, it is preferable to additionally use dyes or color pigments. As dyes or color pigments, it is particularly preferred to use all dyes approved for human or animal use in dissolved or suspended form and as pigments all pigments approved for human or animal use in dissolved or suspended form, and / or mixtures thereof.
In der Formulierung werden vorzugsweise zusätzlich Duftstoffe eingesetzt. Als Duftstoffe werden besonders bevorzugt Parfumöle und sonstige niedrig siedende Stoffe, die zur Anwendung am Menschen oder Tier zugelassen sind, und/oder Mischungen davon eingesetzt.In the formulation, fragrances are preferably used in addition. Fragrances used are particularly preferably perfume oils and other low-boiling substances which are approved for use on humans or animals, and / or mixtures thereof.
In der Formulierung werden vorzugsweise zusätzlich Weichmacher eingesetzt. Als Weichmacher werden besonders bevorzugt Diethylphthalat, Di(ethylhexyl)phthalat, Diethylcitrat, Adipat, Silikone, Polyglycole und/oder Mischungen davon eingesetzt.In the formulation, plasticizers are preferably additionally used. The plasticizers used are particularly preferably diethyl phthalate, di (ethylhexyl) phthalate, diethyl citrate, adipate, silicones, polyglycols and / or mixtures thereof.
Die Erfindung umfasst auch ein Verfahren zur Herstellung der Formulierung, dadurch gekennzeichnet, dassThe invention also includes a process for the preparation of the formulation, characterized in that
• 1 bis 39 Gewichtsprozent eines Repellents • 0 bis 35 Gewichtsprozent eines Alkohols• 1 to 39% by weight of a repellent • 0 to 35% by weight of an alcohol
• 0,05 bis 25 Gewichtsprozent eines Verdickers und• 0.05 to 25% by weight of a thickener and
« 0,1 bis 98,95 Gewichtsprozent Wasser«0.1 to 98.95 weight percent water
sowie gegebenenfalls zusätzliche Stoffe in jeder beliebige Reihenfolge miteinander vermischt werden.and, optionally, additional substances are mixed together in any order.
Die Erfindung umfasst auch die Verwendung der Formulierungen zur Vertreibung von Arthropoden und/oder Plathebninthen. Die Formulierung wird vorzugsweise zur Abwehr von schädlichen oder lästigen saugenden und beißenden Arthropoden, bevorzugt Insekten, Zecken und Milben verwendet.The invention also includes the use of the formulations for expelling arthropods and / or platinum bushes. The formulation is preferably used to ward off harmful or irritating sucking and biting arthropods, preferably insects, ticks and mites.
Zu den saugenden Insekten gehören im Wesentlichen die Stechmücken (zum Beispiel Aedes aegypti, Aedes vexans, Aedes taeniorhynchus, Aedes albopictus, Culex pipiens fatigans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles dirus, Anopheles gambiae, Anopheles sinensis, Anopheles stephensi, Mansonia titillans), Schmetterlingsmücken (zum Beispiel Phlebotomus papatasii, Phlebotomus duboscqi), Grützen (zum Beispiel Culicoides furens, Culicoides impunctatus), Kriebelmücken (zum Beispiel Simulium damnosum. Simulium venustum), Stechfliegen (zum Beispiel Stomoxys calcitrans), Tsetse-Fliegen (zum Beispiel Glossina morsitans morsitans), Bremsen (zum Beispiel Tabanus nigrovittatus, Haematopota pluvialis, Chrysops caecutiens), Echte Fliegen (zum Beispiel Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis), Fleischfliegen (zum Beispiel Sarcophaga carnaria), Myiasis erzeugende Fliegen (zum Beispiel Lucilia cuprina, Chrysomyia chloropyga, Hypoderma bovis, Hypoderma lineatum, Dermatobia hominis, Oestrus ovis, Gasterophilus intestinalis, Cochliomyia hominivorax), Wanzen (zum BeispielCimex lectularius, Rhodnius prolixus, Triatoma infestans), Läuse (zum Beispiel Pediculus humanis, Haematopinus suis, Damalina ovis), Flöhe (zum Beispiel Pulex irritans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides felis) und Sandflöhe (Dermatophilus penetrans).The sucking insects mainly include the mosquitoes (for example Aedes aegypti, Aedes vexans, Aedes taeniorhynchus, Aedes albopictus, Culex pipiens fatigans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles dirus, Anopheles gambiae, Anopheles sinensis, Anopheles stephensi, Mansonia titillans), butterfly mosquitoes (for example Phlebotomus papatasii, Phlebotomus duboscqi), groats (for example Culicoides furens, Culicoides impunctatus), blackflies (for example Simulium damnosum, Simulium venustum), biting flies (for example Stomoxys calcitrans), tsetse flies (for example Glossina morsitans morsitans), brakes (for example Tabanus nigrovittatus, Haematopota pluvialis, Chrysops caecutiens), True flies (for example Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis), flies (for example Sarcophaga carnaria), Myiasis-producing flies (cf. Example Lucilia cuprina, Chrysomyia chloropyga, Hypoderma bovi s, Hypoderma lineatum, Dermatobia hominis, Oestrus ovis, Gasterophilus intestinalis, Cochliomyia hominivorax), bugs (for example Cimex lectularius, Rhodnius prolixus, Triatoma infestans), lice (for example Pediculus humanis, Haematopinus suis, Damalina ovis), fleas (for example Pulex irritans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides felis) and sand fleas (Dermatophilus penetrans).
Zu den beißenden Insekten gehören im Wesentlichen Schaben (zum Beispiel Blattella germanica, Periplaneta americana, Blatta orientalis, Supella longipalpa), Käfer (zum Beispiel Sitiophilus granarius, Tenebrio molitor, Dermestes lardarius, Stegobium paniceum, Anobium punctatum,The biting insects are essentially cockroaches (for example Blattella germanica, Periplaneta americana, Blatta orientalis, Supella longipalpa), beetles (for example Sitiophilus granarius, Tenebrio molitor, Dermestes lardarius, Stegobium paniceum, Anobium punctatum,
Hylotrupes bajulus), Termiten (zum Beispiel Reticulitermes lucifugus), Ameisen (zum BeispielHylotrupes bajulus), termites (for example Reticulitermes lucifugus), ants (for example
Lasius niger, Monomorium pharaonis), Wespen (zum Beispiel Vespula germanica) und Larven vonLasius niger, Monomorium pharaonis), wasps (for example Vespula germanica) and larvae of
Motten (zum Beispiel Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineola bisselliella, Tinea pellionella, Trichophaga tapetzella). Zu den übrigen Arthropoden gehören Zecken (zum Beispiel Ixodes ricinus, Ixodes scapulaπs, Argas reflexus, Omitliodorus moubata, Ripicephalus sangumeus, Boophihus microplus, Amblyomma hebraeum) und Milben (zum Beispiel Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides faπnae, Dermanyssus galhnae, Acarus siro)Moths (for example Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineola bisselliella, Tinea pellionella, Trichophaga tapetzella). The other arthropods include ticks (for example, Ixodes ricinus, Ixodes scapulaπs, Argas reflexus, Omitliodorus moubata, Ripicephalus sangumeus, Boophihus microplus, Amblyomma hebraeum) and mites (for example Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides faπnae, Dermanyssus galhnae, Acarus siro)
Ferner werden die Formulierungen vorzugsweise gegen Plathelmmthen, insbesondere gegen infektiöse Stadien von Plathelmmthen, verwendet Bevorzugt wird die Formulierung zur Abwehr von Plathelrrunthen wie Schistosomahaematobium, Schistosoma japomcum, Tnchobilharzia spp und Ornithobilharzia spp , aber auch Echinostoma spp verwendetFurthermore, the formulations are preferably used against platelets, in particular against infectious stages of platelets. The formulation is preferably used for repelling platelet tumors such as Schistosomahaematobium, Schistosoma japomcum, Tnchobilharzia spp and Ornithobilharzia spp, but also Echinostoma spp
Die Formulierungen werden vorzugsweise durch Auftragen auf die Haut von Mensch oder Tier mittels Aufträufeln, Aufstreichen, Einreiben, Aufspritzen, Aufsprühen, durch Tauchen/Dippen, Baden oder Waschen verwendetThe formulations are preferably used by applying to the skin of humans or animals by means of dripping, brushing, rubbing, spraying, by dipping / dipping, bathing or washing
Die Formulierungen werden vorzugsweise zur Trankung emes Tragers oder Verkap- selung/Mikroverkapselung in einer Hülle aus Liposomen und/oder Harnstoffen oder zur Befüllung einer peπneablen Verpackung oder emes Containers zur spateren Verwendung am Korper eines Lebewesens verwendet Die damit erhaltenen Systeme können dann am Korper eines Lebewesens eingesetzt werden Als Trager wird vorzugsweise Gewebe, Nonwoven, Gel und/oder Polyacrylat verwendetThe formulations are preferably used for the impregnation of a carrier or encapsulation / microencapsulation in a shell of liposomes and / or ureas or for filling a porous packaging or a container for later use on the body of a living being. The systems thus obtained can then be applied to the body of a living being The carrier used is preferably tissue, nonwoven, gel and / or polyacrylate
Der Erfindungsgegenstand der vorliegenden Erfindung ergibt sich mcht nur aus dem Gegenstand der einzelnen Patentansprüche, sondern auch aus der Kombination der einzelnen Patentansprüche untereinander Gleiches gilt für alle in der Beschreibung offenbarten Parameter und deren beliebige KombinationenThe subject matter of the present invention can be found only in the subject matter of the individual patent claims, but also in the combination of the individual patent claims. The same applies to all parameters disclosed in the description and their arbitrary combinations
Anhand der nachfolgenden Beispiele wird die Erfindung naher erlautet, ohne das dadurch eine Einschränkung der Erfindung bewirkt werden soll On the basis of the following examples, the invention is explained in more detail, without thereby limiting the invention is to be effected
BeispieleExamples
I. Beschreibung der verwendeten MessmethodenI. Description of the measuring methods used
A. Bestimmung der ViskositätA. Determination of viscosity
Die Viskosität wird nach DIN 53019 von November 1983 bestimmt.The viscosity is determined according to DIN 53019 of November 1983.
B. Bestimmung der Stabilität der FormulierungB. Determination of the stability of the formulation
Der Stabilität der Formulierung wurde durch den Zentrifugen-Mikrowellen-Test bestimmt. Der Test dient zur Bewertung der Struktur von dispersen Systemen. Die Testmethode sieht wie folgt aus:The stability of the formulation was determined by the centrifuge microwave assay. The test serves to evaluate the structure of disperse systems. The test method looks like this:
Aufbereitungprocessing
Das Prüfmuster der zu untersuchenden Formulierung wird nach Herstellung ca. 2 Tage bei Raumtemperatur akklimatisiert. Circa 10 g Produkt werden aus dem Prüfmuster in ein Zentrifügenglas (25 ml Nennvolumen) eingewogen.The test sample of the formulation to be tested is acclimated after preparation for about 2 days at room temperature. Approximately 10 g of product are weighed from the test sample into a centrifuge tube (25 ml nominal volume).
Belastungstest der FormulierungStress test of the formulation
Das Zentrifugenglas wird 75 Sekunden mit Stufe 1 des Gerätes AEG Micromat® 114 (entspricht einer durchsclinittlichen Leistung von 75 Watt) in der Mikrowelle bestrahlt. Anschließend wird diese Probe eine Stunde bei Raumtemperatur akklimatisiert und 11 Minuten bei 4350 Umdrehungen /Minute in einer Eppendorf Zentrifuge 5403 zentrifugiert.The centrifuge tube is irradiated 75 seconds with stage 1 of the apparatus AEG Micromat ® 114 (corresponding to a durchsclinittlichen power output of 75 watts) in the microwave. Subsequently, this sample is acclimated for one hour at room temperature and centrifuged for 11 minutes at 4350 revolutions / minute in an Eppendorf centrifuge 5403.
Prüfungexam
Die Prüfung der Probe erfolgt visuell durch den Laboranten. Es wird die Probe auf Homogenität der Formulierung untersucht. Abweichendes Aussehen zur unbehandelten Probe, zum Beispiel auftretende Phasentrennung oder Blasen im Zentrifugenglas, werden beschrieben.The test of the sample is done visually by the laboratory technician. The sample is examined for homogeneity of the formulation. Differing appearance to the untreated sample, for example occurring phase separation or bubbles in the centrifuge tube are described.
IL VergleichsbeispielIL Comparative Example
Eine Lotion der folgenden Zusammensetzung wird angesetzt:A lotion of the following composition is applied:
Phase APhase A
16,8 % Gew.-% Wasser (dest. Wasser) Phase B16.8% by weight of water (distilled water) Phase B
40 % Gew.-% l-Piperidincarbonsäure-2-Hydroxyethyl-l-Methylpropylester (Icaridin, Bayrepel®)40% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ®)
43,2 % Gew.-% Ethanol (96%ig)43.2% by weight ethanol (96%)
Alle Stoffe werden bei Raumtemperatur gemischt bis sich eine klare Lösung einstellt.All substances are mixed at room temperature until a clear solution is obtained.
III. Beispiel 2III. Example 2
Eine Gel-Formulierung der folgenden Zusammensetzung wird angesetzt:A gel formulation of the following composition is prepared:
Phase APhase A
39,63 % Gew.-% Wasser (dest. Wasser)39.63% by weight of water (distilled water)
35,0 % Gew.-% Ethanol (96%ig)35.0% by weight ethanol (96%)
Phase BPhase B
25 % Gew.-% l-Piperidincarbonsäure-2-Hydroxyethyl-l-Methylpropylester (Icaridin, Bayrepel®)25% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ®)
0, 17 % Gew.-% Acrylsäurepolymer (Carbopol Ultrez 10)0, 17% by weight acrylic polymer (Carbopol Ultrez 10)
0,5 % Gew.-% 2-Amino-2-methyl-l-propanol (AMP 95)0.5% by weight of 2-amino-2-methyl-1-propanol (AMP 95)
Zunächst wird Phase A bei Raumtemperatur gemischt. Anschließend wird Phase B bei Raumtemperatur über 15 min gemischt und langsam unter starkem Rühren zur Phase A hinzugefügt. Anschließend wird eine pH-Wert Kontrolle durchgeführt und mittels 2-Amino-2-methyl-l-propanol in den Bereich pH 5,5 bis 7,0 eingestellt.First, phase A is mixed at room temperature. Subsequently, phase B is mixed at room temperature for 15 minutes and slowly added to phase A with vigorous stirring. Subsequently, a pH control is carried out and adjusted by means of 2-amino-2-methyl-l-propanol in the range pH 5.5 to 7.0.
IV. Beispiel 3IV. Example 3
Eine Gel-Formulierung der folgenden Zusammensetzung wird angesetzt:A gel formulation of the following composition is prepared:
Phase APhase A
39,63 % Gew.-% Wasser (dest. Wasser)39.63% by weight of water (distilled water)
35,0 % Gew.-% Ethanol (96%ig) Phase B35.0% by weight ethanol (96%) Phase B
25 % Gew.-% 1 -Piperidincarbonsäure-2-Hydroxyethyl- 1 -Methylpropylester (Icaridin, Bayrepel®)25% wt .-% 1 -Piperidincarbonsäure-2-hydroxyethyl 1 -Methylpropylester (Icaridin, Bayrepel ®)
0,3 % Gew.-% Carbomer (Pionier NP37K)0.3% by weight carbomer (pioneer NP37K)
0,07 % Gew.-% 2-Amino-2-methyl-l-propanol0.07% by weight of 2-amino-2-methyl-1-propanol
Zunächst wird Phase A bei Raumtemperatur gemischt. Anschließend wird Phase B bei Raumtemperatur 15 min gemischt und langsam unter starkem Rühren hinzugefügt. Anschließend wird eine pH-Wert Kontrolle durchgeführt und mittels 2-Amino-2-methyl-l-propanol in den Bereich pH 5,5 bis 7,0 eingestellt.First, phase A is mixed at room temperature. Subsequently, phase B is mixed at room temperature for 15 minutes and slowly added with vigorous stirring. Subsequently, a pH control is carried out and adjusted by means of 2-amino-2-methyl-l-propanol in the range pH 5.5 to 7.0.
Die so hergestellten Formulierungen wurden bei Raumtemperatur über eine Woche gelagert und danach visuell beurteilt und die Viskosität gemessen:The formulations thus prepared were stored at room temperature for one week and then visually assessed and the viscosity measured:
2) Da die Formulierung sehr niedrigviskos ist, kann die Viskosität für eine solche Formulierung nicht eindeutig bestimmt werden 2) Since the formulation is very low viscosity, the viscosity for such a formulation can not be determined unambiguously
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006007547.1 | 2006-02-16 | ||
| DE200610007547 DE102006007547A1 (en) | 2006-02-16 | 2006-02-16 | Gel formulation for arthropod and platelet defenses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007093298A1 true WO2007093298A1 (en) | 2007-08-23 |
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ID=38093016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2007/000956 Ceased WO2007093298A1 (en) | 2006-02-16 | 2007-02-05 | Gel formulations for arthropod and plathelminth control |
Country Status (2)
| Country | Link |
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| DE (1) | DE102006007547A1 (en) |
| WO (1) | WO2007093298A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093297A3 (en) * | 2006-02-16 | 2007-12-13 | Saltigo Gmbh | Water-in-oil formulation for arthropod and plathelminth control |
| WO2007093295A3 (en) * | 2006-02-16 | 2007-12-21 | Saltigo Gmbh | Oil-in-water formulation for arthropod and plathelminth control |
| US20230292754A1 (en) * | 2020-10-16 | 2023-09-21 | Sensorygen, Inc. | Pest Repellents and Uses Thereof |
| US12329164B2 (en) | 2020-09-14 | 2025-06-17 | Insight Pharmaceuticals Corporation | Repellant formulation and method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100272658A1 (en) * | 2009-04-27 | 2010-10-28 | Akzo Nobel Chemicals International B.V. | Enhanced efficiency of sunscreen compositions |
| US20250228245A1 (en) * | 2024-01-16 | 2025-07-17 | New Guinea Flatworm Spray, Inc. | Compositions and methods for treating flatworms |
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| EP0289842A1 (en) * | 1987-04-28 | 1988-11-09 | Bayer Ag | Remedy against insects and mites |
| WO1989006904A1 (en) * | 1988-01-27 | 1989-08-10 | Leuthold Serge Andre | Insect-repellent composition |
| JPH05331033A (en) * | 1992-05-25 | 1993-12-14 | Osaka Seiyaku:Kk | Gelatinous insect repellent |
| WO1996041614A1 (en) * | 1995-06-08 | 1996-12-27 | Johnson & Johnson Consumer Products, Inc. | Sunscreen compositions |
| WO1997049380A1 (en) * | 1996-06-26 | 1997-12-31 | S.C. Johnson & Son, Inc. | Insect repellent sunscreen |
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| EP1762221A1 (en) * | 2005-07-20 | 2007-03-14 | Beiersdorf AG | Insect repellent with long lasting affect |
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- 2006-02-16 DE DE200610007547 patent/DE102006007547A1/en not_active Withdrawn
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| EP0289842A1 (en) * | 1987-04-28 | 1988-11-09 | Bayer Ag | Remedy against insects and mites |
| WO1989006904A1 (en) * | 1988-01-27 | 1989-08-10 | Leuthold Serge Andre | Insect-repellent composition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093297A3 (en) * | 2006-02-16 | 2007-12-13 | Saltigo Gmbh | Water-in-oil formulation for arthropod and plathelminth control |
| WO2007093295A3 (en) * | 2006-02-16 | 2007-12-21 | Saltigo Gmbh | Oil-in-water formulation for arthropod and plathelminth control |
| US12329164B2 (en) | 2020-09-14 | 2025-06-17 | Insight Pharmaceuticals Corporation | Repellant formulation and method |
| US12329163B2 (en) | 2020-09-14 | 2025-06-17 | Insight Pharmaceuticals Corporation | Repellant formulation and method |
| US12342828B2 (en) | 2020-09-14 | 2025-07-01 | Insight Pharmaceuticals Corporation | Repellant formulation and method |
| US20230292754A1 (en) * | 2020-10-16 | 2023-09-21 | Sensorygen, Inc. | Pest Repellents and Uses Thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102006007547A1 (en) | 2007-08-30 |
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