WO1998001032A1 - Arthropod repellant - Google Patents

Arthropod repellant Download PDF

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Publication number
WO1998001032A1
WO1998001032A1 PCT/EP1997/003436 EP9703436W WO9801032A1 WO 1998001032 A1 WO1998001032 A1 WO 1998001032A1 EP 9703436 W EP9703436 W EP 9703436W WO 9801032 A1 WO9801032 A1 WO 9801032A1
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WIPO (PCT)
Prior art keywords
arthropod
repellant
weight
deet
mixtures
Prior art date
Application number
PCT/EP1997/003436
Other languages
German (de)
French (fr)
Inventor
Jochen Kalbe
Günther Nentwig
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU34413/97A priority Critical patent/AU3441397A/en
Publication of WO1998001032A1 publication Critical patent/WO1998001032A1/en

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Classifications

    • 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
    • A01N37/20—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 containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • 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
    • 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
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • 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
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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 arthropod repellants based on a combination of arthropod repellents and cyclic silicone compounds
  • Arthropod repellents are known and are used.
  • 3-Methylbenzoic acid diethylamide (Deet) dimethyl phthalate and 2-ethylhexanediol-1,3 (Rutgers 612), of which Deet in particular has gained considerable importance in practice (see e.g. RK Kocher, RS Dixit, CI Somaya, Ind. J. Med.
  • the present invention relates to arthropod repellant mixtures consisting of the components
  • the mixtures according to the invention are notable for improved repellant activity and, at the same time, excellent skin tolerance - 2nd
  • Arthropod-repellant active ingredients are 3-methylbenzoic acid diethylamide (DEET), dimethyl phthalate, 2-ethyl-hexanediol-1,3 and the active ingredients known from EP-A 281 908 and EP-A 289 842.
  • DEET 3-methylbenzoic acid diethylamide
  • dimethyl phthalate 2-ethyl-hexanediol-1,3
  • active ingredients known from EP-A 281 908 and EP-A 289 842 are known from EP-A 281 908 and EP-A 289 842.
  • Combinations of repellant active ingredients can also be used.
  • the mixture claimed is preferably used with repellant carboxylic acid amides, 1,3-alkanediols, carboxylic acid esters, lactone derivatives and ß-alanine derivatives disubstituted on nitrogen.
  • repellant carboxylic acid amides 1,3-alkanediols, carboxylic acid esters, lactone derivatives and ß-alanine derivatives disubstituted on nitrogen.
  • 3-methyl-benzoic acid diethylamide (Deet) may be mentioned by way of example,
  • Linear polyorganosiloxanes of the general formula (I) may be mentioned as silicone polymers
  • R for OH or C 1 . 4 -Alkyl is preferably methyl or ethyl
  • cyclic polysiloxanes of the formula (II) may be mentioned as cyclic silicones (SiR - O) -
  • R represents identical or different radicals from the group methyl, ethyl, propyl,
  • n stands for integers from 3 to 6.
  • R represents identical or different radicals from the group methyl, ethyl, propyl
  • n stands for integers from 3 to 6
  • auxiliaries that may be mentioned are solvents (for example xylene, chlorobenzenes, paraffins, methanol, ethanol, isopropanol, water), emulsifiers (for example polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylsulfonates, arylsulfonates) and dispersants (for example Lignin, sulfate waste liquors, methyl cellulose) and customary auxiliaries for the production of microcapsules (for example based on gum arabic, gelatin, urea) or aerosols, sprays, pump sprays, solutions, emulsions, gels, ointments, pastes, soaps, shampoos, creams, powders ,
  • solvents for example xylene, chlorobenzenes, paraffins, methanol, ethanol, isopropanol, water
  • emulsifiers for example polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol
  • the agents according to the invention can be mixed with other agents or can also be used in mixtures with other known active ingredients (e.g. sunscreens).
  • the preparations generally contain between 0.1 and 95% by weight of the active ingredient combination, preferably between 0.5 and 90
  • the agents according to the invention are either applied to human or animal skin or hair or fur, or articles of clothing and other objects are treated with them.
  • the materials according to the invention are suitable for packaging materials and as an additive to polishing, cleaning and window cleaning agents.
  • the agents according to the invention serve to ward off harmful or troublesome sucking and biting arthropods, preferably insects, ticks and mites
  • the sucking insects essentially include the mosquitoes (e.g. Aedes aegypti, Aedes vexans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles stephensi, Mansonia titillans), butterfly mosquitoes (e.g. Phlebotomus papatasii), gnats (e.g. Culico) Simulium damnosum), sting flies (e.g. Steomxys calcitrans), tsetse flies (e.g. Glossina marsitans morsitans), brakes (e.g.
  • mosquitoes e.g. Aedes aegypti, Aedes vexans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles stephensi, Mansonia titi
  • real flies e.g. Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis
  • flesh flies e.g. Sarcophaga camaria
  • myiasis-producing flies e.g. Lucilia cuprina, Chrysomyia chloro
  • Bedbugs e.g. Cimex lectularius, Rhodnius prolixus, Triatoma infestans
  • lice e.g. Pediculus humanis, Haematopinus suis, Damalina ovis
  • fleas e.g. Pulex ir ⁇ tans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides fehs
  • Sandflophus e.g. Cimex lectularius, Rhodnius prolixus, Triatoma infestans
  • lice e.g. Pediculus humanis, Haematopinus suis, Damalina ovis
  • fleas e.g. Pulex ir ⁇ tans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides fehs
  • Sandflophus e.g. Cimex lectularius, Rhodnius prolixus, Triatoma
  • Biting insects essentially include cockroaches (e.g. Blattella germanica, Periplaneta mericana, Blatta orientalis, Supella longipalpa), beetles (e.g. Sitiophilus granarius, Tenebrio molitor, Dermestes Iarda ⁇ us. Stegobium paniceum, Anobium punctatum, Hylotrupiten (zajulus) B Reticulitermes lucifugus), ants (e.g. Lasius niger, Monomo ⁇ um pharaonis), wasps (e.g. Vespula germanica) and larvae of moths (e.g. Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineea pisselellaella, Tineea bisselliella )
  • cockroaches e.g. Blattella germanica, Periplaneta mericana,
  • the other arthropods include ticks (e.g. Ixodes ⁇ cmus, Argas reflexus, Omithodorus moubata, Boophilius microplus, Amblyomma hebraeum) and mites (e.g. Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermanyssus salliroe)
  • ticks e.g. Ixodes ⁇ cmus, Argas reflexus, Omithodorus moubata, Boophilius microplus, Amblyomma hebraeum
  • mites e.g. Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermanyssus salliroe
  • agents according to the invention which can be used diluted or preferably undiluted, can be used in the formulations customary for repellents
  • a repellent in the form of a lotion for use on human or animal skin is made by mixing 20 parts of a repellent, 15 parts of a polymer, 63.5 parts of cyclic silicone compound and 1.5 parts of perfume
  • a repellant in the form of an aerosol for spraying on human or animal skin consists of 40% active ingredient solution (consisting of 20 parts of a repellant, 15 parts of polymer, 64 parts of cyclic silicone compound and 1
  • Gauze cages measuring 50 x 60 x 60 cm contain mixed-sex populations of all ages, the number of which includes around 5,000 mosquitoes
  • the guinea pig and box are placed in a cage containing the test animals
  • the last determined value is updated for the following evaluation times and included in the calculation of the mean values of the following evaluation times
  • E expected duration of protection of the formulation according to the invention with E50 + D4
  • the mixtures according to the invention give protection that is up to three times longer compared to an ethanolic solution of the repellent

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention concerns arthropod-repellant mixtures comprising the following components: 1. between 1 and 15 wt.% of an arthropod-epelling active substance; 2. between 1 and 10 wt.% of a silicone polymer; 3. between 50 and 98 wt.% of one or a plurality of cyclic silicones with between four and eight ring members; and 4. optionally further auxiliary agents or solvents.

Description

Arthropodenrepellierende MittelArthropod repellant
Die vorliegende Erfindung betrifft arthropodenrepellierende Mittel auf der Basis einer Kombination aus Arthropodenrepellentien und cyclischen SilikonverbindungenThe present invention relates to arthropod repellants based on a combination of arthropod repellents and cyclic silicone compounds
Arthropodenrepellents sind bekannt und in Gebrauch Genannt seien 3-Methyl- benzoesaurediethylamid (Deet), Dimethylphthalat und 2-Ethyl-hexandiol-l,3 (Rutgers 612) von denen vor allem das Deet in der Praxis eine erhebliche Be- deutung erlangt hat (siehe z.B. R.K. Kocher, R.S. Dixit, C.I. Somaya, Ind. J. Med.Arthropod repellents are known and are used. 3-Methylbenzoic acid diethylamide (Deet), dimethyl phthalate and 2-ethylhexanediol-1,3 (Rutgers 612), of which Deet in particular has gained considerable importance in practice (see e.g. RK Kocher, RS Dixit, CI Somaya, Ind. J. Med.
Res 62, 1 (1974)).Res 62, 1 (1974)).
Bekannt ist aber auch die arthropodenrepellierende Wirkung der aus EP-A 281 908 und 289 842 bekannten Verbindungen auf die hier besonders Bezug genommen wirdHowever, the arthropod repellant effect of the compounds known from EP-A 281 908 and 289 842 is also known and is particularly referred to here
Es ist ferner bekannt geworden in repellierende Mittel einen geringen Anteil eines cyclischen Silikons einzuarbeiten um die Hautverträglichkeit der Mischung zu verbessern (vgl die aus JP-A 4 244 001 bekannte Mischung von DEET mit einem Gehalt an 1 bis 2 % cyclischem Silikon).It has also become known to incorporate a small proportion of a cyclic silicone into repellant agents in order to improve the skin compatibility of the mixture (cf. the mixture of DEET known from JP-A 4 244 001 with a content of 1 to 2% cyclic silicone).
Die vorliegende Erfindung betrifft arthropodenrepellierende Mischungen bestehend aus den KomponentenThe present invention relates to arthropod repellant mixtures consisting of the components
1 1 bis 15 Gew -% eines arthropodenrepellierenden Wirkstoffs,1 1 to 15% by weight of an arthropod repellant,
2 1 bis 10 Gew.-% eines Silikonpolymers,2 1 to 10% by weight of a silicone polymer,
3 50 bis 98 Gew -% eines oder mehrerer cyclischer Silikone mit 4 bis 8 Ringgliedern,3 50 to 98% by weight of one or more cyclic silicones with 4 to 8 ring members,
4 gegebenenfalls weitere Hilfsstoffe oder Losungsmittel4 if necessary, other auxiliaries or solvents
Die erfindungsgemäßen Mischungen zeichnen sich durch verbesserte repellierende Wirkung bei gleichzeitiger hervorragender Hautvertraglichkeit aus - 2The mixtures according to the invention are notable for improved repellant activity and, at the same time, excellent skin tolerance - 2nd
Als arthropodenrepellierende Wirkstoffe seien genannt 3-Methylbenzoesauredi- ethylamid (DEET), Dimethylphthalat, 2-Ethyl-hexandiol-l,3, sowie die aus EP-A 281 908 und EP-A 289 842 bekannten Wirkstoffe.Arthropod-repellant active ingredients are 3-methylbenzoic acid diethylamide (DEET), dimethyl phthalate, 2-ethyl-hexanediol-1,3 and the active ingredients known from EP-A 281 908 and EP-A 289 842.
Besonders bevorzugt seien genannt DEET sowie der Wirkstoff der FormelDEET and the active ingredient of the formula are particularly preferred
Figure imgf000004_0001
Es können auch Kombinationen repellierender Wirkstoffe eingesetzt werden
Figure imgf000004_0001
Combinations of repellant active ingredients can also be used
Im Falle der Repellentkombinationen wird das beanspruchte Gemisch bevorzugt mit repellenten Carbonsaureamiden, 1,3-Alkandiolen, Carbonsaureestern, Lacton- Derivaten und am Stickstoff disubstituierten ß-Alaninderivaten verwendet Im einzelnen seien beispielhaft genannt 3-Methyl-benzoesaurediethylamid (Deet),In the case of the repellent combinations, the mixture claimed is preferably used with repellant carboxylic acid amides, 1,3-alkanediols, carboxylic acid esters, lactone derivatives and ß-alanine derivatives disubstituted on nitrogen. 3-methyl-benzoic acid diethylamide (Deet) may be mentioned by way of example,
Diethylphenylacetamid (DEPA), 2-Ethyl-hexandiol- l ,3 (Rutgers 612), Phthalsäuredimethylester, 1 , 1 ,4,5,6,7,8,8a-Octahydro-3H-2-benzopyran-3-on und 3-(N-n-Butyl-N-acetyI)-aminopropionsäure-ethylesterDiethylphenylacetamide (DEPA), 2-ethyl-hexanediol-1, 3 (Rutgers 612), dimethyl phthalate, 1, 1, 4,5,6,7,8,8a-octahydro-3H-2-benzopyran-3-one and 3 - (Nn-Butyl-N-acetyI) aminopropionic acid ethyl ester
Als Silikonpolymere seien genannt lineare Polyorganosiloxane der allgemeinen Formel (I)Linear polyorganosiloxanes of the general formula (I) may be mentioned as silicone polymers
Figure imgf000004_0002
in welcher
Figure imgf000004_0002
in which
R für OH oder C1.4-Alkyl bevorzugt Methyl oder Ethyl stehtR for OH or C 1 . 4 -Alkyl is preferably methyl or ethyl
für ganze Zahlen von 10 bis 10 000 bevorzugt 100 bis 5 000 stehtstands for integers from 10 to 10,000, preferably 100 to 5,000
Als cyclische Silikone seien die cyclischen Polysiloxane der Formel (II) genannt (SiR — O)-The cyclic polysiloxanes of the formula (II) may be mentioned as cyclic silicones (SiR - O) -
(II)(II)
in welcherin which
R für gleiche oder verschiedene Reste der Gruppe Methyl, Ethyl, Propyl steht,R represents identical or different radicals from the group methyl, ethyl, propyl,
n für ganze Zahlen von 3 bis 6 steht.n stands for integers from 3 to 6.
Bevorzugt sind Polysiloxane der Formel (II), in denen der Index n *= 5 ist.Polysiloxanes of the formula (II) in which the index n * = 5 are preferred.
Besonders bevorzugt sind Mischungen von cyclischen Polysiloxanen der Formel (II)Mixtures of cyclic polysiloxanes of the formula (II) are particularly preferred
-(SiR — O)-- (SiR - O) -
(II),(II),
in welcherin which
R für gleiche oder verschiedene Reste der Gruppe Methyl, Ethyl, Propyl stehtR represents identical or different radicals from the group methyl, ethyl, propyl
n für ganze Zahlen von 3 bis 6 steht,n stands for integers from 3 to 6,
wobei die Bestandteile der Formel (II) mit den Indices 4 und 5 im Gewichtsverhältniswherein the components of formula (II) with the indices 4 and 5 in the weight ratio
n = 4 < 85 % (Gewicht) n = 5 > 15 % (Gewicht)n = 4 <85% (weight) n = 5> 15% (weight)
vorliegen.available.
Ganz besonders bevorzugt sind Mischungen von cyclischen Polysiloxanen, in denen die Bestandteile der Formel (II) mit den Indices 4 und 5 im Gewichtsver- hältnis n = 4 80 bis 60 Gew.-% n = 5 20 bis 40 Gew.-%Mixtures of cyclic polysiloxanes in which the constituents of the formula (II) with the indices 4 and 5 in the weight ratio are very particularly preferred n = 4 80 to 60% by weight n = 5 20 to 40% by weight
vorliegen.available.
Als zusätzliche Hilfsstoffe seien genannt Lösungsmittel (z.B. Xylol, Chlorbenzole, Paraffine, Methanol, Ethanol, Isopropanol, Wasser), Emulgiermittel (z.B. Polyoxy- ethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate, Aryl- sulfonate) und Dispergiermittel (z.B. Lignin-, Sulfatablaugen, Methylcellulose) ferner übliche Hilfsstoffe zur Herstellung von Mikrokapseln (z.B. auf Basis von Gummi arabicum, Gelatine, Harnstoff) oder Aersolen, Sprays, Pumpsprays, Lösungen, Emulsionen, Gele, Salben, Pasten, Seifen, Schampoos, Cremes, Pulver,Additional auxiliaries that may be mentioned are solvents (for example xylene, chlorobenzenes, paraffins, methanol, ethanol, isopropanol, water), emulsifiers (for example polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylsulfonates, arylsulfonates) and dispersants (for example Lignin, sulfate waste liquors, methyl cellulose) and customary auxiliaries for the production of microcapsules (for example based on gum arabic, gelatin, urea) or aerosols, sprays, pump sprays, solutions, emulsions, gels, ointments, pastes, soaps, shampoos, creams, powders ,
Stifte, getränkte Schwämme.Pens, soaked sponges.
Die erfindungsgemäßen Mittel können mit anderen Mitteln gemischt oder auch in Mischungen mit anderen bekannten Wirkstoffen (z.B. Sonnenschutzmittel) verwendet werden. Die Zubereitungen enthalten im allgemeinen zwischen 0,1 und 95 Gew.-% der Wirkstoff-Kombination, vorzugsweise zwischen 0,5 und 90The agents according to the invention can be mixed with other agents or can also be used in mixtures with other known active ingredients (e.g. sunscreens). The preparations generally contain between 0.1 and 95% by weight of the active ingredient combination, preferably between 0.5 and 90
Gew.-%.% By weight.
Zum Schutz gegen die Arthropoden werden die erfindungsgemäßen Mittel entweder auf die menschliche oder tierische Haut oder Haare bzw. Fell aufgebracht oder Kleidungsstücke und andere Gegenstände damit behandelt.To protect against arthropods, the agents according to the invention are either applied to human or animal skin or hair or fur, or articles of clothing and other objects are treated with them.
Auch als Zusatz von Imprägniermitteln für z.B Textilbahnen, Kleidungsstücke,Also as an additive for impregnating agents for e.g. textile webs, clothing,
Verpackungsmaterialien, sowie als Zusatz zu Polier-, Putz- und Fensterreinigungsmitteln sinddie erfindungsgemäßen Mittel geeignet.The materials according to the invention are suitable for packaging materials and as an additive to polishing, cleaning and window cleaning agents.
Die erfindungsgemäßen Mittel dienen zur Abwehr von schädlichen oder lästigen saugenden und beißenden Arthropoden, bevorzugt Insekten, Zecken und MilbeThe agents according to the invention serve to ward off harmful or troublesome sucking and biting arthropods, preferably insects, ticks and mites
Zu den saugenden Insekten gehören im wesentlichen die Stechmücken (z.B. Aedes aegypti, Aedes vexans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles stephensi, Mansonia titillans), Schmetterlingsmücken (z.B. Phlebotomus papatasii), Gnitzen (z.B. Culicoides furens), Kribelmücken (z.B. Simulium damnosum), Stechfliegen (z.B. Steomxys calcitrans), Tsetse-Fliegen (z.B. Glossina marsitans morsitans), Bremsen (z.B Tabanus nigrovittatus, Haematopota pluvialis, Chrysops caecuties), Echte Fliegen (z.B Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis), Fleischfliegen (z B Sarcophaga camaria), Myiasis erzeugende Fliegen (z B Lucilia cuprina, Chrysomyia chloropyga, Hypoderma bavis, Hypoderma Iineatum, Dernatibua hominus, Oestrus ovis, Gasterophilus intestmalis, Cochliomyia hominivorax),The sucking insects essentially include the mosquitoes (e.g. Aedes aegypti, Aedes vexans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles stephensi, Mansonia titillans), butterfly mosquitoes (e.g. Phlebotomus papatasii), gnats (e.g. Culico) Simulium damnosum), sting flies (e.g. Steomxys calcitrans), tsetse flies (e.g. Glossina marsitans morsitans), brakes (e.g. Tabanus nigrovittatus, Haematopota pluvialis, Chrysops caecuties), real flies (e.g. Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis), flesh flies (e.g. Sarcophaga camaria), myiasis-producing flies (e.g. Lucilia cuprina, Chrysomyia chloropyga, Hypoderma bavisum, Hypoderma Iin Dernatibua hominus, Oestrus ovis, Gasterophilus intestmalis, Cochliomyia hominivorax),
Wanzen (z.B Cimex lectularius, Rhodnius prolixus, Triatoma infestans), Lause (z B Pediculus humanis, Haematopinus suis, Damalina ovis), Flohe (z B Pulex irπtans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides fehs) und Sandflohe (Dermatophilus penetrans)Bedbugs (e.g. Cimex lectularius, Rhodnius prolixus, Triatoma infestans), lice (e.g. Pediculus humanis, Haematopinus suis, Damalina ovis), fleas (e.g. Pulex irπtans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides fehs) and Sandflophus
Zu den beißenden Insekten gehören im wesentlichen Schaben (z B Blattella germanica, Periplaneta mericana, Blatta orientalis, Supella longipalpa), Käfer (z B Sitiophilus granarius, Tenebrio molitor, Dermestes Iardaπus. Stegobium paniceum, Anobium punctatum, Hylotrupes bajulus), Termiten (z B Reticulitermes lucifugus), Ameisen (z B Lasius niger, Monomoπum pharaonis), Wespen (z B Vespula germanica) und Larven von Motten (z B Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineola bisselliella, Tinea pelhonella, Trichophaga tapetzella)Biting insects essentially include cockroaches (e.g. Blattella germanica, Periplaneta mericana, Blatta orientalis, Supella longipalpa), beetles (e.g. Sitiophilus granarius, Tenebrio molitor, Dermestes Iardaπus. Stegobium paniceum, Anobium punctatum, Hylotrupiten (zajulus) B Reticulitermes lucifugus), ants (e.g. Lasius niger, Monomoπum pharaonis), wasps (e.g. Vespula germanica) and larvae of moths (e.g. Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineea pisselellaella, Tineea bisselliella )
Zu den übrigen Arthropoden gehören Zecken (z B Ixodes πcmus, Argas reflexus, Omithodorus moubata, Boophilius microplus, Amblyomma hebraeum) und Milben (z B Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermanyssus galhnae, Acarus siro)The other arthropods include ticks (e.g. Ixodes πcmus, Argas reflexus, Omithodorus moubata, Boophilius microplus, Amblyomma hebraeum) and mites (e.g. Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermanyssus salliroe)
Die erfϊndungsgemaßen Mittel, die verdünnt oder vorzugsweise unverdünnt eingesetzt werden können, lassen sich in den für Repellents üblichen Formulierungen einsetzen The agents according to the invention, which can be used diluted or preferably undiluted, can be used in the formulations customary for repellents
Die folgenden Beispiele dienen der weiteren Erläuterung der ErfindungThe following examples serve to further explain the invention
Formulierungsbeispiel 1Formulation example 1
Ein Repelientmittel in Form einer Lotion zur Anwendung auf der menschlichen oder tierischen Haut wird hergestellt durch Vermischen von 20 Teilen eines Repellents, 15 Teilen eines Polymers, 63,5 Teilen cyclischer Silikonverbindung und 1,5 Teilen ParfümA repellent in the form of a lotion for use on human or animal skin is made by mixing 20 parts of a repellent, 15 parts of a polymer, 63.5 parts of cyclic silicone compound and 1.5 parts of perfume
Formulierungsbeispiel 2Formulation example 2
Ein Repelientmittel in Form eines Aerosols zum Aufsprühen auf die menschliche oder tierische Haut setzt sich aus 40 % Wirkstofflosung (bestehend aus 20 Teilen eines Repellents, 15 Teilen Polymer, 64 Teilen cyclischer Silikonverbindung und 1A repellant in the form of an aerosol for spraying on human or animal skin consists of 40% active ingredient solution (consisting of 20 parts of a repellant, 15 parts of polymer, 64 parts of cyclic silicone compound and 1
Teil Parfüm) und 60 % Propan/Butan (Verhältnis 15 85) zusammenPart of perfume) and 60% propane / butane (ratio 15 85) together
Es wurden individuelle Formulierungen entsprechend den Formulierungsbeispielen 1 und 2 unter Einsatz der folgenden Stoffe hergestelltIndividual formulations corresponding to formulation examples 1 and 2 were produced using the following substances
Repellent DEET Polymer E50 (Polyorganosiloxan der Formel (I) R=OHRepellent DEET polymer E50 (polyorganosiloxane of formula (I) R = OH
MG ca 50 000) cyclisches Silikon D4 (Octamethylcyclotetrasiloxan)MG ca 50 000) cyclic silicone D4 (octamethylcyclotetrasiloxane)
Biologische WirksamkeitBiological effectiveness
Die folgenden biologischen Beispiele belegen die synergistische Verlängerung der Wirksamkeit eines α,ω-Aminoalkohol -Derivates durch den Zusatz fraktionierterThe following biological examples demonstrate the synergistic extension of the effectiveness of an α, ω-amino alcohol derivative by the addition of fractionated ones
FettsaurenFatty acids
Methodemethod
50 x 60 x 60 cm messende Gazekafige enthalten gemischtgeschlechtliche Populationen aller Altersstufen, deren Anzahl ca 5000 Mucken umfaßt Die Tiere werden ausschließlich mit Zuckerwasser ernährtGauze cages measuring 50 x 60 x 60 cm contain mixed-sex populations of all ages, the number of which includes around 5,000 mosquitoes
Ein Meerschweinchen, dessen Rucken am Vortag in einem Bereich von 50 cm2 rasiert und danach mit Enthaarungscreme behandelt worden war (Creme an- schließend mit Wasser entfernt), wird in einem Käfig (Box) so fixiert, daß nur die rasierte Flache den Mucken zugänglich istA guinea pig, the back of which had been shaved the previous day in an area of 50 cm 2 and then treated with depilatory cream (cream applied then removed with water), is fixed in a cage (box) so that only the shaved area is accessible to the mosquitoes
Nach Behandeln der Flache mit 0,4 ml Präparat (mit Pipette) wird das Meerschweinchen samt Box in einen die Testtiere enthaltenden Käfig gestelltAfter treating the area with 0.4 ml of preparation (with pipette), the guinea pig and box are placed in a cage containing the test animals
Es wird 5 Minuten lang beobachtet, wieviele Mucken das Meerschweinchen stechen Anschließend wird dieses herausgenommen und der Rest nach einer Stunde wiederholt Der Versuch wird maximal 9 Stunden lang durchgeführt oder solange bis die Wirkung abbricht (>5 Einstiche)It is observed for 5 minutes how many mosquitoes bite the guinea pig, then the guinea pig is removed and the rest is repeated after one hour. The test is carried out for a maximum of 9 hours or until the effect stops (> 5 punctures)
Pro Präparat werden 3 Versuchsglieder angelegt und nach Beendigung der Mittelwert pro Auswertungszeitpunkt berechnet3 test elements are created for each preparation and, after completion, the mean value for each evaluation time is calculated
Bricht bei einem Versuchsglied die Wirkung früher ab, wird der zuletzt ermittelte Wert für die folgenden Auswertungszeitpunkte fortgeschrieben und in die Berechnung der Mittelwerte der folgenden Auswertungszeitpunkte einbezogenIf the effect terminates earlier in a test element, the last determined value is updated for the following evaluation times and included in the calculation of the mean values of the following evaluation times
Der Synergismus wird mit der Formel nach S R Colby, Weeds 15, 20 bis 22, 1967, nachgewiesenThe synergism is demonstrated with the formula according to SR Colby, Weeds 15, 20 to 22, 1967
X • YX • Y
E=X + Y-E = X + Y-
100100
E = erwartete Schutzdauer der erfindungsgemaßen Formulierung mit E50 + D4E = expected duration of protection of the formulation according to the invention with E50 + D4
X = tatsachliche Schutzdauer des Repellents alleineX = Actual protection period of the repellant alone
Y = tatsachliche Schutzdauer von E50 + D4 alleineY = actual protection period of E50 + D4 alone
Ist E kleiner als die tatsachlich gefundene Schutzdauer der Kombination, so liegt ein Synergismus vor, wie in Tabelle 1 dargestellt /01032If E is less than the protection period of the combination actually found, there is a synergism, as shown in Table 1 / 01032
- 8- 8th
ErgebnisseResults
Temperatur 25 bis 27°C, rel Luftfeuchte ca 60 %, 0,4 ml Formulie- rung/Meersch wei nchenTemperature 25 to 27 ° C, relative humidity approx. 60%, 0.4 ml formulation / guinea pig
Tabelle 1 Deet mit D4 + E50 E = 3hTable 1 Deet with D4 + E50 E = 3h
Anzahl der Einstiche am Meerschweinchen nachNumber of punctures on the guinea pig after
Präparat Oh 1 h 2h 3h 4h 5 h 6h 7 h 8h 9hPreparation Oh 1 h 2h 3h 4h 5 h 6h 7 h 8h 9h
3,0 % Deet 0 0 1,0 1,5 6,53.0% Deet 0 0 1.0 1.5 6.5
97,0 % Ethanol97.0% ethanol
3,0 % Deet3.0% deet
8,0 % E50 0 0 0 0 0 0 1,0 0,5 0,5 2,58.0% E50 0 0 0 0 0 0 1.0 0.5 0.5 2.5
89,0 % D489.0% D4
3,0 % Deet3.0% deet
4,0 % E50 0 0 0 0 0 0 0,5 1,0 1,0 04.0% E50 0 0 0 0 0 0 0.5 1.0 1.0 0
93,0 % D493.0% D4
3,0 % Deet3.0% deet
2,0 % E50 0 0 0 0 0 0 1,5 2,0 6,02.0% E50 0 0 0 0 0 0 1.5 2.0 6.0
95,0 % D495.0% D4
Die erfindungsgemäßen Mischungen geben einen um bis zu 3-fach längeren Schutz im Vergleich zu einer ethanolischen Losung des Repellents The mixtures according to the invention give protection that is up to three times longer compared to an ethanolic solution of the repellent

Claims

- 9 -Patentanspruch1. Arthropodenrepellierende Mischungen bestehend aus den Komponenten - 9 - Patent claim 1. Arthropod repellant mixtures consisting of the components
1. 1 bis 15 Gew -% eines arthropodenrepellierenden Wirkstoffs,1. 1 to 15% by weight of an arthropod-repelling active substance,
2. 1 bis 10 Gew.-% eines Silikonpolymers,2. 1 to 10% by weight of a silicone polymer,
3. 50 bis 98 Gew.-% eines oder mehrerer cyclischer Silikone mit 4 bis 8 Ringgliedern,3. 50 to 98% by weight of one or more cyclic silicones with 4 to 8 ring members,
4. gegebenenfalls weitere Hilfsstoffe oder Lösungsmittel. 4. optionally other auxiliaries or solvents.
PCT/EP1997/003436 1996-07-10 1997-07-01 Arthropod repellant WO1998001032A1 (en)

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DE1996127778 DE19627778A1 (en) 1996-07-10 1996-07-10 Arthropod repellant

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WO2001019190A1 (en) * 1999-09-16 2001-03-22 Durminster Limited Method and composition for the control of arthropods
GB2357972A (en) * 1999-09-16 2001-07-11 Ansell Jayne Optionally substituted siloxane containing liquid composition for the eradication of head lice
EP1337145A1 (en) * 2000-11-28 2003-08-27 Avon Products, Inc. Anhydrous insect repellent composition
EP2254311A1 (en) 1999-06-15 2010-11-24 Tectia Oyj Maintaining address translations for data communications
TWI845581B (en) 2018-12-28 2024-06-21 日商花王股份有限公司 Pest repellent composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2254311A1 (en) 1999-06-15 2010-11-24 Tectia Oyj Maintaining address translations for data communications
WO2001019190A1 (en) * 1999-09-16 2001-03-22 Durminster Limited Method and composition for the control of arthropods
GB2357972A (en) * 1999-09-16 2001-07-11 Ansell Jayne Optionally substituted siloxane containing liquid composition for the eradication of head lice
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EP1337145A1 (en) * 2000-11-28 2003-08-27 Avon Products, Inc. Anhydrous insect repellent composition
EP1337145A4 (en) * 2000-11-28 2009-05-27 Avon Prod Inc Anhydrous insect repellent composition
TWI845581B (en) 2018-12-28 2024-06-21 日商花王股份有限公司 Pest repellent composition

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AU3441397A (en) 1998-02-02

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