EP1253824A2 - Fluid insecticidal formulations for treatment of parasitic insect larvae by dermal application - Google Patents

Fluid insecticidal formulations for treatment of parasitic insect larvae by dermal application

Info

Publication number
EP1253824A2
EP1253824A2 EP00990645A EP00990645A EP1253824A2 EP 1253824 A2 EP1253824 A2 EP 1253824A2 EP 00990645 A EP00990645 A EP 00990645A EP 00990645 A EP00990645 A EP 00990645A EP 1253824 A2 EP1253824 A2 EP 1253824A2
Authority
EP
European Patent Office
Prior art keywords
spp
formulations
spot
larvicidal
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00990645A
Other languages
German (de)
French (fr)
Inventor
Kirkor Sirinyan
Dorothee Stanneck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1253824A2 publication Critical patent/EP1253824A2/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • 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
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides

Definitions

  • Insecticidal liquid formulations that can be applied dermally to combat parasitic insect larvae
  • the present invention relates to the use of polysiloxanes containing at least one quaternary ammonium group for the preparation of new, storage-stable.
  • Active substances in the form of liquid formulations that can be applied dermally it is therefore necessary to prepare homogeneous solutions based on organic solvents and insecticidal active substances.
  • the active compounds are usually dissolved in organic solvents such as isopropanol, 2-butoxyethyl acetate, ethylene glycol diacetate and, if appropriate, mixed with other additives.
  • organic solvents such as isopropanol, 2-butoxyethyl acetate, ethylene glycol diacetate and, if appropriate, mixed with other additives.
  • the preparation of such formulations is described in US Pat. No. 4,874,753, EP-A 137 627 and GB-A 2 135 886 described.
  • Active ingredients in high-boiling solvents such as monopropylene glycol, which also contain natural, skin-compatible oils such as pine oil, sunflower oil or soybean oil. Furthermore, it can be seen from the patent specification WO 91/13545 that well-effective, skin-compatible liquid formulations can be produced by aliphatic said substances in amounts of> 50%
  • Emulsions based on the said active ingredients with long-chain, aliphatic amines or alcohols such as hexadecan-1-ol, 1-octadecylamine are proposed.
  • the disadvantage of using the long-chain amines is that they degrade the active substances in question over time. In most cases, the formulations based on long-chain alcohols do not have a sufficient long-term effect.
  • the object of the present invention is therefore to provide a skin-friendly and environmentally compatible, user-friendly formulation which is excellently stable in the conventional spot on primary packaging materials in accordance with the pharmaceutical guidelines and is highly effective against parasitic insect larvae on the basis of larvicidal and / or ovicidal active ingredients.
  • the present invention accordingly relates to the use of polysiloxanes containing at least one quaternary ammonium group as formulation auxiliaries in formulations of larvicidal and / or ovicidal active substances.
  • the present application also relates to new compositions containing
  • the agents according to the invention are particularly suitable for the production of spot on and pour on s for use in combating parasites on animals.
  • Larvicidal and / or ovicidal active ingredients based on juvenile hormones and fluorobenzoyl ureas can be used to prepare the liquid formulations according to the invention, juvenile hormones with activity against flea larvae being particularly preferred. Juvenile hormones with anti-parasitic effect
  • Insect larvae are known (see GB-A 2 140 010, DE-OS 37 00 881, DE-OS 38 25 172).
  • the larvicidal and / or ovicidal activity of fluorobenzoylureas is also known and can be found in the literature (see, for example, EP-A 343 110, DE-OS 38 27 133, EP-A 230 400, EP-A 255 803).
  • Juvenile hormones and juvenile hormone-like substances such as:
  • Benzoyl ureas such as:
  • the amounts of active ingredient can be varied widely between 0.1-15%. Amounts in the range 0.1-7.5% are preferred. Quantities of 0.1-5% are particularly preferably used. Quantities in the range of 0.2-2.0% are very particularly preferably used for the production of the new formulations according to the invention. Percentages relate to percent by weight.
  • Combination active ingredients which may be mentioned are the insecticides used in the field of controlling ectoparasitic insects, such as nicotinyl and, in particular, chloronicotinyl insecticides, N-phenylpyrazoles, carbamates, phosphoric and phosphonic acid esters, growth inhibitors or mixtures of these active ingredients with one another and their mixtures with synergists.
  • insecticides used in the field of controlling ectoparasitic insects, such as nicotinyl and, in particular, chloronicotinyl insecticides, N-phenylpyrazoles, carbamates, phosphoric and phosphonic acid esters, growth inhibitors or mixtures of these active ingredients with one another and their mixtures with synergists.
  • synergists are understood to mean compounds which themselves do not have the desired activity, but which, as a mixing partner, increase the insecticides used in the field of controlling ectoparasitic insects, such as nicotinyl and
  • chloronicotinyl insecticides are compounds of the formulas (I), (II) and (III):
  • n 1 or 2
  • n 0, 1 or 2
  • Substituted phenyl and naphthyl carbamates may be mentioned as carbamates.
  • Juvenile hormones and juvenile hormone-like substances such as:
  • Benzoyl ureas such as:
  • Triazines such as:
  • the amounts of the combination active ingredients can be varied widely between 0.1 to 12.5%, the amounts in the range 0.1 to 10.0% being particularly preferred and the amounts in the range 0.5 to 7.5% being particularly preferred , Percentages are to be understood here as percentages by weight.
  • Piperonyl butoxide and sesame oil are preferred as synergists for these compounds. These synergists are described, for example, in patent specification EP-413 610.
  • the selected formulation aids based on polydimethylsiloxanes with cationic quaternary amine groups of the formula
  • Polysiloxanes with both mono- and polyquaternary amine groups can be used to prepare the agents according to the invention.
  • said polydimethylsiloxanes can have further functional groups such as carboxylic acid, amine, hydroxyl, carboxylic ester groups.
  • the most particularly preferred functional groups are hydroxyl and carboxylic acid groups.
  • Their viscosity can be varied widely in the range from 200 to 17,500 mm 2 s ⁇ l (at 25 ° C), measured in accordance with DIN 53 019 as a 50% aqueous solution, with a viscosity in the range from 250 to 10,000 mm 2 s " l (at 25 ° C) particularly, and which are particularly preferred with a viscosity in the range from 250 to 1 350 mm 2 s ⁇ l (at 25 ° C).
  • Polysiloxanes of the formula (V) are very particularly preferred
  • R long-chain alkyl radical
  • the amounts of polydimethylsiloxane used can be varied widely between 0.1-15%; the amounts in the range 0.1-5% are preferred. Amounts between 0.1 and 2.5% are particularly preferred. The amounts in the range 0.25-2.5% are used with very particular preference for the production of the formulations according to the invention. The percentages are to be understood as percentages by weight.
  • Aliphatic polyethers such as diethylene glycol monomethyl ether, dipropylene glycol monopropyl ether; cyclic carbonates such as propylene carbonate, ethylene carbonate, aliphatic and aromatic alcohols such as ethanol, isopropanol; Acetates such as benzyl acetate, benzyl benzoate or mixtures thereof are used with one another.
  • Aliphatic polyethers in particular diethylene glycol monomethyl ether, dipropylene glycol monopropyl ether or diethylene glycol monomethyl ether, are particularly preferred as solvents.
  • Dipropylene glycol monopropyl ether is used with particular preference for the production of the new liquid formulations. Possibly mixtures of the abovementioned solvents can also be used.
  • the organic solvent content is 2.5 to 99.8% by weight, preferably 60 to 99.0% by weight, particularly preferably 60 to 93.7% by weight, very particularly preferably 65 -90% by weight and especially 75-83% by weight.
  • the proportion of water in the new formulations can be varied widely by 0-95% by weight, 0-30% by weight being preferred, being particularly preferred
  • 7.5-30% by weight very particularly preferred are 7.5-25% by weight and in particular 12.5-17.5% by weight.
  • formulations according to the invention can contain customary auxiliaries such as antioxidants or odor masking agents.
  • Stabilizers and antioxidants that may be mentioned are sulfites or metabisulfites such as potassium metabisulfite; organic acids such as citric acid; ascorbic acid; Phenols, butylated hydroxytoluene, butylated hydroxyanisole, tocopherol, the organic acids citric acid and malic acid being preferred.
  • Very particularly preferred stabilizers are citric acid and butylated hydroxytoluene. Their proportion can be varied widely in the range 0.05 to 2.5% by weight, quantities in the range 0.075-0.15% by weight being particularly preferred.
  • Odor masking agents are e.g. Mixtures of organic fatty acid esters. They are preferably present in the formulations according to the invention in 0.1 to 2% by weight.
  • liquid formulations according to the invention are distinguished by an excellent storage stability of several years in all climatic zones, skin, user and environmental compatibility. Surprisingly, they are ideal for filling and dispensing in normally storage-critical "single dose polypropylene plastic tubes" with a wall thickness of 300-500 ⁇ m and a filling volume of 1.0 to 4.0 ml.
  • liquid formulations according to the invention also show an unexpected synergistic, i.e. Effect-increasing effect, for example when using pyriproxyfen as an active ingredient.
  • the agents according to the invention are environmentally friendly and user-friendly due to their very low toxicity.
  • the agents according to the invention are suitable for combating parasitic insects which occur in animal husbandry and animal breeding in domestic and farm animals as well as zoo, laboratory, experimental and hobby animals. They are effective against all or individual stages of development of the pests and against resistant and normally sensitive types of pests.
  • the pests include:
  • anoplura e.g. Haematopinus spp., Linognathus spp., Solenopotes spp., Pediculus spp., Pthirus spp .; from the order of the Mallophaga e.g. Trimenopon spp., Menopon spp., Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp.,
  • Bovicola spp from the order of the Diptera e.g. Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fan- nia spp., Glossina spp., Lucilia spp., Calliphora spp ., Auchmeromyia spp., Cordylobia spp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp.,
  • Gasterophilus spp. Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp., Rhinoestrus spp., Melophagus spp., Hippobosca spp ..
  • Ixodes spec Rhipicephalus spec, Dermacentor spec, Haemaphysalis spec, Boophilus spec; Hyalomma spec mentioned.
  • Livestock and breeding animals include mammals such as Cattle, horses, sheep, pigs, goats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer, fur animals such as Mink, chinchilla, raccoon, and birds such as Chickens, geese, turkeys, ducks.
  • Laboratory and experimental animals include mice, rats, guinea pigs, golden hamsters, dogs and cats.
  • the pets include dogs and cats.
  • the application can be prophylactic as well as therapeutic.
  • the desired constituents are mixed with one another in appropriate amounts, e.g. through the use of conventional stirred tanks or other suitable devices.
  • ingredients require it, it can also be used under a protective atmosphere or others
  • Abil Quat 3274 is a 50% polydimethylsiloxane solution with a diquatera
  • Abil Quat 3274 is a 50% polydimetylsiloxane solution with a diquaternary ammonium group and a viscosity range of 5000 - 15000 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen.
  • Counterexample 1 is a 50% polydimetylsiloxane solution with a diquaternary ammonium group and a viscosity range of 5000 - 15000 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen.
  • flea-fixed cats were divided into 2 groups of 10 cats.
  • One group received 0.1 ml / kg pyriproxyfen spot on 1% as a spot on in the neck, the other group served as an untreated control.
  • the cats were reinfested at weekly intervals and falling flea eggs were collected over a period of 24 hours. These eggs were at 85% rel. Humidity and 28 ° C incubated and observed for the development of fleas over a period of 30 days.
  • Gmppe served as an untreated control. At weekly intervals over the The cats were placed on fleece blankets for 6 hours each for a period of 4 weeks. The blankets were sprinkled with floating egg at 85% rel. Humidity and 28 ° C and observed for the development of fleas over a period of 30 days.
  • Cats were 95% or more suppressed over a 17 day period.
  • the dogs were placed on fleece blankets for 6 hours at weekly intervals over a period of 4 weeks.
  • the blankets were sprinkled with floating egg, at 85% rel. Humidity and 28 ° C and incubated on the
  • Table 1 shows that Formulations 1-4 meet the stability requirements of the drug guidelines.
  • the formulation bars listed in counterexamples 1-2 are unfortunately not stable in storage.
  • the respective amounts of active substance decrease> 10% during storage.
  • the table shows that the new spot-on formulas have excellent target animal and environmental compatibility as well as user safety.

Abstract

The invention relates to the use of polysiloxanes, comprising at least one quaternary ammonium group as adjuncts in formulations containing larvicidal and/or ovicidal active ingredients and agents which contain a) a larvicidal and/or ovicidal active ingredient and b) a polysiloxane derivative, with at least one quaternary ammonium group per molecule and optionally further adjuncts and vehicles.

Description

Dermal applizierbare insektizide Flflssigformulierungen zur Bekämpfung von parasitierenden InsektenlarvenInsecticidal liquid formulations that can be applied dermally to combat parasitic insect larvae
Die vorliegende Erfindung betπfft die Verwendung von Polysiloxanen enthaltend mindestens eine quartäre Nrnrnoniumgruppe zur Herstellung neuer, lagerungsstabiler. hautverträglicher, dermal applizierbarer Flussigformulierungen larvizider und/oder ovizider Wirkstoffe zur Bekämpfung von parasitierenden Insektenlarven an Tieren.The present invention relates to the use of polysiloxanes containing at least one quaternary ammonium group for the preparation of new, storage-stable. Skin-compatible, dermally applicable liquid formulations of larvicidal and / or ovicidal active ingredients for controlling parasitic insect larvae on animals.
Bei der Herstellung von Wirkstoff-Formulierungen auf dem Gebiet der Pharmazie und der Veterinärmedizin stellt sich häufig und insbesondere bei wässπgen Formulierungen das Problem mangelnder Loshchkeit der Wirkstoffe und damit zusammenhängend auch einer mangelnden Lagerstabihtät der fertigen FormulierungenIn the manufacture of active ingredient formulations in the field of pharmacy and veterinary medicine, the problem of inadequate solubility of the active ingredients and, associated therewith, also a lack of storage stability of the finished formulations frequently arises, and in particular in the case of aqueous formulations
Bei der Nnwendung zum Teil schwer wasserlöslicher, larvizider und/oder oviziderWhen used, it is partially water-soluble, larvicidal and / or ovicidal
Wirkstoffe in Form von dermal applizierbaren Flussigformulierungen ist es daher notwendig, homogene Lösungen auf Basis von organischen Lösungsmitteln und insektiziden Wirkstoffen herzustellen. Dazu werden die Wirkstoffe zumeist in organischen Lösungsmitteln wie Isopropanol, 2-Butoxy-ethylacetat, Ethylenglycol- diacetat gelöst und gegebenenfalls mit weiteren Zusatzstoffen vermischt Die Herstellung solcher Formulierungen ist in US 4 874 753, EP-A 137 627 und GB-A 2 135 886 beschrieben. Die Nachteile der besagten Systeme liegen bei der Verwendung von larviziden und/oder oviziden Wirkstoffen dann, dass sie m vielen Fällen zur Hautirritationen führen und ferner m den üblichen Spot on Primärpackmitteln immer noch eine relativ geπnge Langzeitstabi tat aufweisen und somit die Grundanforderungen der behördlichen Arzneimittelregulaπen zum Langzeitstabilitätsver- halten nicht erfüllenActive substances in the form of liquid formulations that can be applied dermally, it is therefore necessary to prepare homogeneous solutions based on organic solvents and insecticidal active substances. For this purpose, the active compounds are usually dissolved in organic solvents such as isopropanol, 2-butoxyethyl acetate, ethylene glycol diacetate and, if appropriate, mixed with other additives. The preparation of such formulations is described in US Pat. No. 4,874,753, EP-A 137 627 and GB-A 2 135 886 described. The disadvantages of the said systems when using larvicidal and / or ovicidal active ingredients are that in many cases they lead to skin irritation and, furthermore, in the usual spot on primary packaging, they still have a relatively narrow long-term stability and thus meet the basic requirements of the official pharmaceutical regulations Long-term stability behavior does not meet
Es ist wünschenswert, diese Formulierungen durch solche zu ersetzen, die hervor- ragend hautverträglich sowie toxikologisch unbedenklich sind und ferner sich durch ihre sehr gute Langzeitwirkung von mehreren Wochen sowie durch ihre Langzeitstabilität von mehreren Jahren in allen Klimazonen in den herkömmlichen Spot on Primärpackmitteln auszeichnen.It is desirable to replace these formulations with those which are outstandingly skin-friendly and toxicologically harmless, and which also have a very good long-term effect of several weeks and their Characterize long-term stability of several years in all climate zones in the conventional spot on primary packaging.
Um den besagten Nachteil beispielsweise der bekannten Formulierungen zu beheben wird in den Patentschriften AU-A 627 847, EP-A 413 610 vorgeschlagen, dieseIn order to remedy the said disadvantage of the known formulations, for example, it is proposed in the patents AU-A 627 847, EP-A 413 610
Wirkstoffe in hochsiedenden Lösungsmitteln wie Monopropylenglykol, die zusätzlich noch natürliche, hautverträgliche Öle wie Pinienöl, Sonnenblumenöl oder Sojaöl enthalten, zu lösen. Ferner kann der Patentschrift WO 91/13545 entnommen werden, dass gut wirksame, hautverträgliche Flüssigformulierungen hergestellt werden können, indem man die besagten Wirkstoffe in Mengen von >50% in aliphatischenActive ingredients in high-boiling solvents such as monopropylene glycol, which also contain natural, skin-compatible oils such as pine oil, sunflower oil or soybean oil. Furthermore, it can be seen from the patent specification WO 91/13545 that well-effective, skin-compatible liquid formulations can be produced by aliphatic said substances in amounts of> 50%
Lösungsmitteln wie 2-(2-Butoxyethoxy)ethanol oder 2-(2-Methoxy-ethoxy)ethanol löst. Der Nachteil dieser Formulierungen liegt darin, dass sie den Einsatz größerer Wirkstoff-Mengen benötigen und zudem bei sensiblen Tierrassen zu Hautirritationen führen. Um durch Einsatz geringer Wirkstoffmengen eine akzeptable biologische Wirkung zu erreichen, wird in der Patentschrift US 5 466 458 die Verwendung vonSolvents such as 2- (2-butoxyethoxy) ethanol or 2- (2-methoxy-ethoxy) ethanol dissolves. The disadvantage of these formulations is that they require the use of larger amounts of active ingredient and also lead to skin irritation in sensitive animal breeds. In order to achieve an acceptable biological effect through the use of small amounts of active substance, the use of is described in US Pat. No. 5,466,458
Emulsionen auf Basis der besagten Wirkstoffe mit langkettigen, aliphatischen A inen oder Alkoholen wie Hexadecan-1-ol, 1-Octadecylamine vorgeschlagen. Die Verwendung der langkettigen Amine hat den Nachteil, dass sie die besagten Wirkstoffe im Laufe der Zeit abbauen. Die Formulierungen auf Basis langkettiger Alkohole weisen in den meisten Fällen keine ausreichende Langzeitwirkung auf.Emulsions based on the said active ingredients with long-chain, aliphatic amines or alcohols such as hexadecan-1-ol, 1-octadecylamine are proposed. The disadvantage of using the long-chain amines is that they degrade the active substances in question over time. In most cases, the formulations based on long-chain alcohols do not have a sufficient long-term effect.
Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung einer haut- und umweltverträglichen, anwenderfreundlichen, in den herkömmlichen Spot on Primärpackmitteln gemäß der Arzneimittelrichtlinien hervorragend stabilen sowie gegen parasitierende Insektenlarven hochwirksamen Formulierung auf Basis von larviziden und/oder oviziden Wirkstoffen.The object of the present invention is therefore to provide a skin-friendly and environmentally compatible, user-friendly formulation which is excellently stable in the conventional spot on primary packaging materials in accordance with the pharmaceutical guidelines and is highly effective against parasitic insect larvae on the basis of larvicidal and / or ovicidal active ingredients.
Aus EP-A 0 017 121, 0 017 122, 0 282 720, 0 294 642, 0 166 122 und 0 164 668 ist eine Vielzahl von Polysiloxanen mit endständigen quartären Aminogruppen und deren Verwendung als sogenannte "Conditioner" in Haarwasch- und Haarpflegemitteln bekannt. Überraschenderweise werden nun die zuvor genannten Aufgaben durch die erfindungsgemäßen Mittel unter Verwendung der oben genannten Polysiloxane gelöst. Es entstehen klare Lösungen oder Emulsionen von hoher Lagerstabilität.From EP-A 0 017 121, 0 017 122, 0 282 720, 0 294 642, 0 166 122 and 0 164 668 a multitude of polysiloxanes with terminal quaternary amino groups and their use as so-called "conditioners" in shampoo and hair care products are known , Surprisingly, the aforementioned objects are now achieved by the agents according to the invention using the above-mentioned polysiloxanes. Clear solutions or emulsions with high storage stability result.
Weiterhin erreicht man durch die erfindungsgemäße Verwendung dieser Polysiloxane erstaunlicherweise eine verbesserte Verträglichkeit und einen wirkungs- steigernden, synergistischen Effekt.Furthermore, the use of these polysiloxanes according to the invention surprisingly achieves improved tolerance and an activity-increasing, synergistic effect.
Die vorliegende Erfindung betrifft demnach die Verwendung von Polysiloxanen enthaltend mindestens eine quartäre Ammoniumgruppe als Formulierhilfsmittel in Formulierungen larvizider und/oder ovizider Wirkstoffe.The present invention accordingly relates to the use of polysiloxanes containing at least one quaternary ammonium group as formulation auxiliaries in formulations of larvicidal and / or ovicidal active substances.
Weiterhin Gegenstand der vorliegenden Anmeldung sind neue Mittel, enthaltendThe present application also relates to new compositions containing
a) einen larviziden und/oder oviziden Wirkstoff unda) a larvicidal and / or ovicidal active ingredient and
b) ein Polysiloxanderivat enthaltend mindestens eine quartäre Ammoniumgruppe pro Molekül,b) a polysiloxane derivative containing at least one quaternary ammonium group per molecule,
sowie gegebenenfalls weitere Hilfs- und Trägerstoffe.and, if appropriate, further auxiliaries and carriers.
Die erfindungsgemäßen Mittel eignen sich insbesondere hervorragend zur Herstellung von Spot on und Pour on s für den Einsatz bei der Parasitenbekämpfung am Tier.The agents according to the invention are particularly suitable for the production of spot on and pour on s for use in combating parasites on animals.
Zur Herstellung der erfindungsgemäßen Flüssigformulierungen können larvizide und/oder ovizide Wirkstoffe auf Basis Juvenilhormonen und Fluorbenzoylharn- stoffen eingesetzt werden, wobei Juvenilhormone mit Wirkung gegen Flohlarven be- sonders bevorzugt werden. Juvenilhormone mit Wirkung gegen parasitierendenLarvicidal and / or ovicidal active ingredients based on juvenile hormones and fluorobenzoyl ureas can be used to prepare the liquid formulations according to the invention, juvenile hormones with activity against flea larvae being particularly preferred. Juvenile hormones with anti-parasitic effect
Insektenlarven sind bekannt (s. hierzu GB-A 2 140 010, DE-OS 37 00 881, DE-OS 38 25 172). Ebenso ist die larvizide und/oder ovizide Wirkung von Fluorbenzoyl- harnstoffen bekannt und kann der Literatur (s. z.B. EP-A 343 110, DE-OS 38 27 133, EP-A 230 400, EP-A 255 803) entnommen werden.Insect larvae are known (see GB-A 2 140 010, DE-OS 37 00 881, DE-OS 38 25 172). The larvicidal and / or ovicidal activity of fluorobenzoylureas is also known and can be found in the literature (see, for example, EP-A 343 110, DE-OS 38 27 133, EP-A 230 400, EP-A 255 803).
Insbesondere geeignet sind die folgenden Wirkstoffe:The following active ingredients are particularly suitable:
Juvenilhormone und juvenilhormonartigenn Substanzen wie:Juvenile hormones and juvenile hormone-like substances such as:
Substituierte Diarylether wie:Substituted diaryl ethers such as:
Benzoylhamstoffe wie:Benzoyl ureas such as:
Insbesondere hervorgehoben sei der Einsatz von Pyriproxyfen: The use of pyriproxyfen should be particularly emphasized:
Die Wirkstoff-Mengen können zwischen 0,1-15 % breit variiert werden. Mengen im Bereich 0,1 - 7,5 % sind bevorzugt. Besonders bevorzugt werden Mengen von 0,1 - 5 % eingesetzt. Mengen im Bereich 0,2 - 2,0 % werden zur Herstellung der erfindungsgemäßen, neuen Formulierungen ganz besonders bevorzugt eingesetzt. Prozentangaben beziehen sich dabei auf Gewichtsprozent.The amounts of active ingredient can be varied widely between 0.1-15%. Amounts in the range 0.1-7.5% are preferred. Quantities of 0.1-5% are particularly preferably used. Quantities in the range of 0.2-2.0% are very particularly preferably used for the production of the new formulations according to the invention. Percentages relate to percent by weight.
Selbstverständlich können in den erfindungsgemäßen Mitteln weitere Wirkstoffe als Kombinationspartner eingesetzt werden.Of course, further active ingredients can be used as combination partners in the agents according to the invention.
Als Kombinationswirkstoffe seien bevorzugt genannt die im Bereich zur Be- kämpfung von ektoparasitierenden Insekten eingesetzten Insektizide wie Nicotinyl- sowie insbesondere Chlornicotinyl-Insektizide, N-Phenylpyrazole, Carbamate, Phosphor- und Phosphonsäureester, Wachstumshemmer bzw. Mischungen dieser Wirkstoffe untereinander sowie deren Mischungen mit Synergisten. Als Synergisten im Sinne dieser Anmeldung werden Verbindungen verstanden, die selbst nicht die gewünschte Wirksamkeit aufweisen, als Mischpartner jedoch zu einer Steigerung derCombination active ingredients which may be mentioned are the insecticides used in the field of controlling ectoparasitic insects, such as nicotinyl and, in particular, chloronicotinyl insecticides, N-phenylpyrazoles, carbamates, phosphoric and phosphonic acid esters, growth inhibitors or mixtures of these active ingredients with one another and their mixtures with synergists. For the purposes of this application, synergists are understood to mean compounds which themselves do not have the desired activity, but which, as a mixing partner, increase the
Wirksamkeit der eigentlichen Wirkstoffe führen.Effectiveness of the actual active ingredients lead.
Als Chlornicotinyl-Insektizide seien genannt Verbindungen der Formeln (I), (II) und (III):Examples of chloronicotinyl insecticides are compounds of the formulas (I), (II) and (III):
in welchenin which
n für 1 oder 2 steht,n represents 1 or 2,
m für 0, 1 oder 2 steht,m represents 0, 1 or 2,
Subst. für einen der oben aufgeführten Substituenten, insbesondere für Halogen, ganz besonders für Chlor, steht, undSubst. Stands for one of the substituents listed above, in particular for halogen, very particularly for chlorine, and
A, Z, X und E die oben angegebenen Bedeutungen haben.A, Z, X and E have the meanings given above.
Im einzelnen seien folgende Verbindungen genannt:The following connections are specifically mentioned:
Imidacloprid imidacloprid
AKD1022AKD1022
1 — I1 - I
CH2-N^ ^NHCH 2 -N ^ ^ NH
S.. ^ .NHH /S .. ^ .NHH /
Y ϊl CH a~i N NY ϊl CH a ~ i NN
\\
I NO, NO, I NO, NO,
Besonders hervorgehoben seien die Verbindungen The connections are particularly noteworthy
Weiterhin besonders hervorgehoben seien die VerbindungenThe connections are also particularly emphasized
Als Carbamate seien genannt substituierte Phenyl- und Naphthylcarbamate. Substituted phenyl and naphthyl carbamates may be mentioned as carbamates.
Als Phenylpyrazole seien zum Beispiel die folgenden Verbindungen genannt:The following compounds may be mentioned as phenylpyrazoles:
Bevorzugt seien genannt:May be mentioned:
2-Osobutylphenyl-N-methylcarbamat,2-Osobutylphenyl N-methylcarbamate,
4-Dimethylamino-3-methyl-phenyl-N-methylcarbamat, - 2-isopropoxy-phenyl-N-methylcarbamat,4-dimethylamino-3-methyl-phenyl-N-methylcarbamate, 2-isopropoxy-phenyl-N-methylcarbamate,
1 -Naphthyl-N-methylcarbamat, m-Tolyl-N-methylcarbamat,1-naphthyl-N-methyl carbamate, m-tolyl-N-methyl carbamate,
3 ,4-Xylyl-N-methylcarbamat,3,4-xylyl-N-methylcarbamate,
3,5-Xylyl-N-methylcarbamat, - 2-[l,3-Dioxolan-2-yl]-phenyl-N-methylcarbamat.3,5-xylyl-N-methyl carbamate, 2- [1,3-dioxolan-2-yl] phenyl-N-methyl carbamate.
Als Phosphorsäureester seien bevorzugt genannt die Verbindungen mit den Common Names Phoxim, Fenitrothion, Dichlorvos, Trichlorfon und Malathion.The compounds with the common names Phoxim, Fenitrothion, Dichlorvos, Trichlorfon and Malathion may be mentioned as preferred phosphoric acid esters.
Juvenilhormone und juvenilhormonartigenn Substanzen wie:Juvenile hormones and juvenile hormone-like substances such as:
Substituierte Diarylether wie:Substituted diaryl ethers such as:
Benzoylhamstoffe wie:Benzoyl ureas such as:
Triazine wie: Triazines such as:
NH-R1 NH-R 1
(Fortsetzung)(Continuation)
(Fortsetzung) (Continuation)
Die Mengen der Kombinationswirkstoffe können zwischen 0,1 bis 12,5 % breit variiert werden, wobei die Mengen im Bereich 0,1 bis 10,0 % besonders und die Mengen im Bereich 0,5 bis 7,5 % ganz besonders zu bevorzugen sind. Prozentangaben sind hier als Gewichtsprozente zu verstehen. The amounts of the combination active ingredients can be varied widely between 0.1 to 12.5%, the amounts in the range 0.1 to 10.0% being particularly preferred and the amounts in the range 0.5 to 7.5% being particularly preferred , Percentages are to be understood here as percentages by weight.
Als Synergist für diese Verbindungen seien bevorzugt genannt Piperonylbutoxid und Sesamöl. Diese Synergisten sind beispielsweise in der Patentschrift EP-413 610 beschrieben.Piperonyl butoxide and sesame oil are preferred as synergists for these compounds. These synergists are described, for example, in patent specification EP-413 610.
Die ausgewählten Formulierungshilfsmittel auf Basis von Polydimethylsiloxanen mit kationischen Quartemären- Amingruppen der FormelThe selected formulation aids based on polydimethylsiloxanes with cationic quaternary amine groups of the formula
R' = unterschiedliche organische Reste,R '= different organic residues,
sind bekannte polymere oder oligomere Verbindungen. Beispielhaft, aber nicht einschränkend seien die in EP-A 0 017 121, S. 2, Z. 11 bis S. 3, Z. 3, EP-A 0 017 122, S. 2, Z. 11 bis S. 3, Z. 13, EP-A 0 166 122, S. 4, Z. 31 bis S. 7 ganz, EP-A 0 294 642, S. 5, Z. 10 bis S. 8, Z. 51, EP-A 282 720, S. 6, Z. 10 bis S. 14, Z. 54 sowie die in EP-A 0 164 668 auf S. 4, Z. 31 bis S. 8, Z. 3 beschriebenen Polysiloxane genannt.are known polymeric or oligomeric compounds. Examples, but not restrictive, are those in EP-A 0 017 121, p. 2, lines 11 to p. 3, line 3, EP-A 0 017 122, p. 2, lines 11 to p. 3, Line 13, EP-A 0 166 122, page 4, line 31 to page 7 whole, EP-A 0 294 642, page 5, line 10 to page 8, line 51, EP-A 282 720, page 6, line 10 to page 14, line 54 and the polysiloxanes described in EP-A 0 164 668 on page 4, line 31 to page 8, line 3.
Zur Herstellung der erfindungsgemäßen Mittel können Polysiloxane sowohl mit Mono- als auch mit Polyquarternären- Amingruppen eingesetzt werden. Selbstverständlich können die besagten Polydimethylsiloxane weitere funktionale Gruppen wie Carbonsäure-, Amin-, Hydroxyl-, Carbonsäureestergruppen aufweisen. Die ganz besonders bevorzugten funktionellen Gruppen sind Hydroxyl- und Carbonsäuregruppen. Ihre Viskosität kann im Bereich 200 bis 17 500 mm2s~l (bei 25°C), gemessen entsprechend DIN 53 019 als 50 %ige, wässrige Lösung, breit variiert werden, wobei die mit einer Viskosität im Bereich 250 bis 10 000 mm2s"l (bei 25°C) besonders, sowie die mit einer Viskosität im Bereich 250 bis 1 350 mm2s~l (bei 25 °C) ganz besonders zu bevorzugen sind.Polysiloxanes with both mono- and polyquaternary amine groups can be used to prepare the agents according to the invention. Of course, said polydimethylsiloxanes can have further functional groups such as carboxylic acid, amine, hydroxyl, carboxylic ester groups. The most particularly preferred functional groups are hydroxyl and carboxylic acid groups. Their viscosity can be varied widely in the range from 200 to 17,500 mm 2 s ~ l (at 25 ° C), measured in accordance with DIN 53 019 as a 50% aqueous solution, with a viscosity in the range from 250 to 10,000 mm 2 s " l (at 25 ° C) particularly, and which are particularly preferred with a viscosity in the range from 250 to 1 350 mm 2 s ~ l (at 25 ° C).
Ganz besonders bevorzugt sind Polysiloxane der Formel (V)Polysiloxanes of the formula (V) are very particularly preferred
R = langkettiger Alkylrest,R = long-chain alkyl radical,
die unter dem Handelsnamen ABIL® von der Firma Goldschmidt vertrieben werden.which are sold by the Goldschmidt company under the trade name ABIL®.
Die eingesetzten Polydimethylsiloxan-mengen können zwischen 0,1- 15 % breit variiert werden; wobei die Mengen im Bereich 0,1-5 % zu bevorzugen sind. Besonders bevorzugt sind Mengen zwischen 0,1 und 2,5 %. Die Mengen im Bereich 0,25-2,5 % werden zur Herstellung der erfindungsgemäß neuen Formulierungen ganz besonders bevorzugt eingesetzt. Die Prozentangaben sind hierbei als Gewichtsprozente zu verstehen.The amounts of polydimethylsiloxane used can be varied widely between 0.1-15%; the amounts in the range 0.1-5% are preferred. Amounts between 0.1 and 2.5% are particularly preferred. The amounts in the range 0.25-2.5% are used with very particular preference for the production of the formulations according to the invention. The percentages are to be understood as percentages by weight.
Als erfindungsgemäße Lösungsmittel werden aliphatische Polyether wie Diethylen- glykolmonomethylether, Dipropylenglykolmonopropylether; cyclische Carbonate wie Propylencarbonat, Ethylencarbonat, aliphatische und aromatische Alkohole wie Ethanol, Isopropanol; Acetate wie Benzylacetat, Benzylbenzoat bzw. deren Mischungen untereinander eingesetzt.Aliphatic polyethers such as diethylene glycol monomethyl ether, dipropylene glycol monopropyl ether; cyclic carbonates such as propylene carbonate, ethylene carbonate, aliphatic and aromatic alcohols such as ethanol, isopropanol; Acetates such as benzyl acetate, benzyl benzoate or mixtures thereof are used with one another.
Besonders bevorzugt als Lösungsmittel sind aliphatische Polyether, insbesondere Di- ethylenglykolmonomethylether, Dipropylenglykolmonopropylether oder Diethylen- glykolmonomethylether. Dipropylenglykolmonopropylether wird zur Herstellung der neuen Flüssigformulierungen ganz besonders bevorzugt eingesetzt. Gegebenenfalls können auch Mischungen der vorstehend genannten Lösungsmittel eingesetzt werden.Aliphatic polyethers, in particular diethylene glycol monomethyl ether, dipropylene glycol monopropyl ether or diethylene glycol monomethyl ether, are particularly preferred as solvents. Dipropylene glycol monopropyl ether is used with particular preference for the production of the new liquid formulations. Possibly mixtures of the abovementioned solvents can also be used.
In der erfindungsgemäßen Formulierung liegt der organische Lösungsmittelanteil bei 2,5 bis 99,8 Gew.-%, bevorzugt bei 60 bis 99,0 Gew.-% besonders bevorzugt bei 60 bis 93,7 Gew.-%, ganz besonders bevorzugt bei 65-90 Gew.-% und insbesondere bei 75-83 Gew.-%.In the formulation according to the invention, the organic solvent content is 2.5 to 99.8% by weight, preferably 60 to 99.0% by weight, particularly preferably 60 to 93.7% by weight, very particularly preferably 65 -90% by weight and especially 75-83% by weight.
Der Anteil an Wasser in den neuen Formulierungen kann durch 0-95 Gew.-% breit variiert werden, wobei 0-30 Gew.-% bevorzugt sind, besonders bevorzugt sindThe proportion of water in the new formulations can be varied widely by 0-95% by weight, 0-30% by weight being preferred, being particularly preferred
7,5-30 Gew-%, ganz besonders zu bevorzugen sind 7,5 - 25 Gew.-% und insbesondere 12,5 - 17,5 Gew.-%.7.5-30% by weight, very particularly preferred are 7.5-25% by weight and in particular 12.5-17.5% by weight.
Zusätzlich können die erfindungsgemäßen Formulierungen übliche Hilfsmittel wie Antioxidantien oder Geruchsmaskierungsmittel enthalten.In addition, the formulations according to the invention can contain customary auxiliaries such as antioxidants or odor masking agents.
Als Stabilisatoren und Antioxidantien seien genannt Sulfite oder Metabisulfite wie Kaliummetabisulfit; organische Säuren wie Citronensäure; Ascorbinsäure; Phenole, Butylhydroxytoluol, Butylhydroxyanisol, Tocopherol, wobei die organischen Säuren Citronensäure und Äpfelsäure zu bevorzugen sind. Ganz besonders bevorzugte Stabilisatoren sind Citronensäure und Butylhydroxytoluol. Ihr Anteil kann im Bereich 0,05 bis 2,5 Gew.-% breit variiert werden, wobei Mengen im Bereich 0,075-0,15 Gew.-% besonders bevorzugt werden.Stabilizers and antioxidants that may be mentioned are sulfites or metabisulfites such as potassium metabisulfite; organic acids such as citric acid; ascorbic acid; Phenols, butylated hydroxytoluene, butylated hydroxyanisole, tocopherol, the organic acids citric acid and malic acid being preferred. Very particularly preferred stabilizers are citric acid and butylated hydroxytoluene. Their proportion can be varied widely in the range 0.05 to 2.5% by weight, quantities in the range 0.075-0.15% by weight being particularly preferred.
Geruchsmaskierungsmittel sind z.B. Mischungen organischer Fettsäureester. Sie sind bevorzugt zu 0,1 bis 2 Gew.-% in den erfindungsgemäßen Formulierungen enthalten.Odor masking agents are e.g. Mixtures of organic fatty acid esters. They are preferably present in the formulations according to the invention in 0.1 to 2% by weight.
Überraschenderweise zeichnen sich die erfmdungsgemäßen Flüssigformulierungen durch eine hervorragende Lagerungsstabilität von mehreren Jahren in allen Klima- zonen, Haut-, Anwender- sowie Umweltverträglichkeit aus. Sie eignen sich überraschenderweise hervorragend zum Abfüllen und Ausbieten in normalerweise lagerungskritischen „Single dose Polypropylenkunststofftuben" der Wandstärke von 300-500 μm und des Abfüllvolumens 1,0 bis 4,0 ml.Surprisingly, the liquid formulations according to the invention are distinguished by an excellent storage stability of several years in all climatic zones, skin, user and environmental compatibility. Surprisingly, they are ideal for filling and dispensing in normally storage-critical "single dose polypropylene plastic tubes" with a wall thickness of 300-500 μm and a filling volume of 1.0 to 4.0 ml.
Die erfindungsgemäßen Flüssigformulierungen zeigen zudem einen nicht zu erwar- tenden synergistischen, d.h. wirkungssteigernden Effekt, beispielsweise bei Verwendung von Pyriproxyfen als Wirkstoff.The liquid formulations according to the invention also show an unexpected synergistic, i.e. Effect-increasing effect, for example when using pyriproxyfen as an active ingredient.
Die erfindungsgemäßen Mittel sind umweltverträglich und aufgrund der sehr geringen Toxizität anwenderfreundlich.The agents according to the invention are environmentally friendly and user-friendly due to their very low toxicity.
Die erfindungsgemäßen Mittel eignen sich bei günstiger Warmblütertoxizität zur Bekämpfung von parasitierenden Insekten, die in der Tierhaltung und Tierzucht bei Haus- und Nutztieren sowie Zoo-, Labor-, Versuchs- und Hobbytieren vorkommen. Sie sind dabei gegen alle oder einzelne Entwicklungsstadien der Schädlinge sowie gegen resistente und normal sensible Arten der Schädlinge wirksam.With favorable warm-blood toxicity, the agents according to the invention are suitable for combating parasitic insects which occur in animal husbandry and animal breeding in domestic and farm animals as well as zoo, laboratory, experimental and hobby animals. They are effective against all or individual stages of development of the pests and against resistant and normally sensitive types of pests.
Zu den Schädlingen gehören:The pests include:
Aus der Ordnung der Anoplura z.B. Haematopinus spp., Linognathus spp., Solen- opotes spp., Pediculus spp., Pthirus spp.; aus der Ordnung der Mallophaga z.B. Trimenopon spp., Menopon spp., Eomena- canthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp.,From the order of the anoplura e.g. Haematopinus spp., Linognathus spp., Solenopotes spp., Pediculus spp., Pthirus spp .; from the order of the Mallophaga e.g. Trimenopon spp., Menopon spp., Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp.,
Bovicola spp; aus der Ordnung der Diptera z.B. Chrysops spp., Tabanus spp., Musca spp., Hydro- taea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fan- nia spp., Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylo- bia spp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp.,Bovicola spp; from the order of the Diptera e.g. Chrysops spp., Tabanus spp., Musca spp., Hydrotaea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fan- nia spp., Glossina spp., Lucilia spp., Calliphora spp ., Auchmeromyia spp., Cordylobia spp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp.,
Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp., Rhinoestrus spp., Melophagus spp., Hippobosca spp..Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma spp., Oestrus spp., Rhinoestrus spp., Melophagus spp., Hippobosca spp ..
Aus der Ordnung der Siphonaptera z.B. Ctenocephalides spp., Echidnophaga spp.,From the order of the Siphonaptera e.g. Ctenocephalides spp., Echidnophaga spp.,
Ceratophyllus spp.. Besonders hervorgehoben sei die Wirkung gegen Flöhe und Zecken.Ceratophyllus spp .. The effect against fleas and ticks should be particularly emphasized.
Als Zeckenarten seien Ixodes spec, Rhipicephalus spec, Dermacentor spec, Haemaphysalis spec, Boophilus spec; Hyalomma spec erwähnt.Ixodes spec, Rhipicephalus spec, Dermacentor spec, Haemaphysalis spec, Boophilus spec; Hyalomma spec mentioned.
Zu den Nutz- und Zuchttieren gehören Säugetiere wie z.B. Rinder, Pferde, Schafe, Schweine, Ziegen, Kamele, Wasserbüffel, Esel, Kaninchen, Damwild, Rentiere, Pelztiere wie z.B. Nerze, Chinchilla, Waschbär, sowie Vögel wie z.B. Hühner, Gänse, Puten, Enten.Livestock and breeding animals include mammals such as Cattle, horses, sheep, pigs, goats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer, fur animals such as Mink, chinchilla, raccoon, and birds such as Chickens, geese, turkeys, ducks.
Zu Labor- und Versuchstieren gehören Mäuse, Ratten, Meerschweinchen, Goldhamster, Hunde und Katzen.Laboratory and experimental animals include mice, rats, guinea pigs, golden hamsters, dogs and cats.
Zu den Hobbytieren gehören Hunde und Katzen.The pets include dogs and cats.
Insbesondere hervorgehoben sei die Anwendung bei Katze und Hund.The use in cats and dogs is particularly emphasized.
Die Anwendung kann sowohl prophylaktisch als auch therapeutisch erfolgen.The application can be prophylactic as well as therapeutic.
Zur Herstellung der erfindungsgemäßen Formulierung werden die gewünschten Bestandteile in entsprechenden Mengen miteinander vermischt, z.B. durch den Einsatz konventioneller Rührkessel oder anderer geeigneter Geräte.To produce the formulation according to the invention, the desired constituents are mixed with one another in appropriate amounts, e.g. through the use of conventional stirred tanks or other suitable devices.
Falls die Inhaltsstoffe es erfordern, kann auch unter Schutzatmosphäre oder anderenIf the ingredients require it, it can also be used under a protective atmosphere or others
Methoden des Sauerstoffausschlusses gearbeitet werden.Methods of oxygen exclusion are worked.
Die nachfolgenden Beispiele sollen die Erfindung erläutern: Beispiel 1The following examples are intended to explain the invention: example 1
Eine homogene Spot on Formulierung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1,00 g Pyriproxyfen (2-[l-Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine (PPF)1.00 g pyriproxyfen (2- [l-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine (PPF)
82,00 g Diethylenglykolmonoethylether82.00 g diethylene glycol monoethyl ether
15,00 g Wasser15.00 g water
2,00 g Abil Quat 3272 (1)2.00 g Abil Quat 3272 (1)
Abil Quat 3272, 50 %ige Ware- ist ein Polydimethylsiloxan mit DiquatemärerAbil Quat 3272, 50% product - is a polydimethylsiloxane with diquaternary
Ammoniumgruppe und dem Viskositätsbereich von 1000 +/- 200 [mm2.s-l] bei 25°C der Fa. Goldschmidt AG, D-4300 Essen.Ammonium group and the viscosity range of 1000 +/- 200 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen.
Beispiel 2Example 2
Eine homogene Spot on Formulierung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1 ,00 g Pyriproxyfen (2-[ 1 -Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine1.00 g of pyriproxyfen (2- [1-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine
82,00 g Dipropylenglykolmonomethylether 15,00 g Wasser82.00 g dipropylene glycol monomethyl ether 15.00 g water
2,00 g Abil Quat 3272 (1)2.00 g Abil Quat 3272 (1)
Abil Quat 3272, 50 %ige Ware- ist ein Polydimethylsiloxan mit Diquatemärer Ammoniumgruppe und dem Viskositätsbereich von 1000 +/- 200 [mm2.s-l] bei 25°C der Fa. Goldschmidt AG, D-4300 Essen. Beispiel 3Abil Quat 3272, 50% product - is a polydimethylsiloxane with a diquaternary ammonium group and a viscosity range of 1000 +/- 200 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen. Example 3
Eine homogene Spot on Formuli erung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1,00 g Pyriproxyfen (2-[l-Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine1.00 g pyriproxyfen (2- [l-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine
82,00 g Dipropylenglykolmonomethylether82.00 g dipropylene glycol monomethyl ether
15,00 g Wasser15.00 g water
2,00 g Abil Quat 3274 (2)2.00 g Abil Quat 3274 (2)
(2) Abil Quat 3274 ist eine 50 %ige Polydimetylsiloxan-Lösung mit Diquatemäre(2) Abil Quat 3274 is a 50% polydimethylsiloxane solution with a diquatera
Ammoniumg ppe und dem Viskositätsbereich von 5000 - 15000 [mm2.s-l] bei 25°C der Fa. Goldschmidt AG, D-4300 Essen.Ammonium g ppe and the viscosity range of 5000 - 15000 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen.
Beispiel 4Example 4
Eine homogene Spot on Formulierung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1 ,00 g Pyriproxyfen (2-[ 1 -Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine1.00 g of pyriproxyfen (2- [1-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine
82,00 g Diethylenglykolmonoethylether 15,00 g Wasser82.00 g diethylene glycol monoethyl ether 15.00 g water
2,00 g Abil Quat 3274 (2)2.00 g Abil Quat 3274 (2)
(2) Abil Quat 3274 ist eine 50 % ige Polydimetylsiloxan-Lösung mit Diquatemäre Ammoniumgmppe und dem Viskositätsbereich von 5000 - 15000 [mm2.s-l] bei 25°C der Fa. Goldschmidt AG, D-4300 Essen. Gegenbeispiel 1(2) Abil Quat 3274 is a 50% polydimetylsiloxane solution with a diquaternary ammonium group and a viscosity range of 5000 - 15000 [mm 2 .sl] at 25 ° C from Goldschmidt AG, D-4300 Essen. Counterexample 1
Eine homogene Spot on Formulierung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1,00 g Pyriproxyfen (2-[l-Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine1.00 g pyriproxyfen (2- [l-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine
99,00 g Diethylenglykolmonoethylether99.00 g diethylene glycol monoethyl ether
Gegenbeispiel 2Counterexample 2
Eine homogene Spot on Formulierung (100 g) bestehend ausA homogeneous spot on formulation (100 g) consisting of
1 ,00 g Pyriproxyfen (2- [ 1 -Methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine 99,00 g Dipropylenglykolmonomethylether1.00 g of pyriproxyfen (2- [1-methyl-2- (4-phenoxyphenoxy) ethoxy] pyridine 99.00 g of dipropylene glycol monomethyl ether
Untersuchungen zur Wirksamkeit der Spot On Formulierungen gemäß Beispielen 1-Studies on the effectiveness of the spot-on formulations according to Examples 1-
4 auf Flöhe an Katzen4 on fleas on cats
Die Studien wurden durchgeführt, um die Wirksamkeit der einprozentigen Pyriproxyfen-Lösungen gemäß den Beispielen zur Sterilisierung von Flöhen an Katzen nachzuweisen.The studies were conducted to demonstrate the effectiveness of the 1% pyriproxyfen solutions according to the flea sterilization examples in cats.
Je 20 flohinfestierte Katzen wurden in 2 Gmppen zu 10 Katzen aufgeteilt. Eine Gruppe erhielt 0.1 ml/kg Pyriproxyfen spot on 1% als spot on im Nacken, die andere Gmppe diente als unbehandelte Kontrolle. In wöchentlichen Intervallen wurden die Katzen reinfestiert und herabfallende Floheier über einen Zeitraum von 24 Stunden gesammelt. Diese Eier wurden bei 85% rel. Luftfeuchtigkeit und 28°C inkubiert und auf die Entwicklung von Flöhen hin über einen Zeitraum von 30 Tagen beobachtet.20 flea-fixed cats were divided into 2 groups of 10 cats. One group received 0.1 ml / kg pyriproxyfen spot on 1% as a spot on in the neck, the other group served as an untreated control. The cats were reinfested at weekly intervals and falling flea eggs were collected over a period of 24 hours. These eggs were at 85% rel. Humidity and 28 ° C incubated and observed for the development of fleas over a period of 30 days.
Weiterhin wurden je 20 Katzen in 2 Gmppen zu 10 Katzen aufgeteilt. Eine G ppe erhielt jeweils 0.1 ml/kg Pyriproxyfen spot on 1 % als spot on im Nacken, die andereFurthermore, 20 cats each were divided into 2 groups of 10 cats. One G ppe each received 0.1 ml / kg pyriproxyfen spot on 1% as spot on in the neck, the other
Gmppe diente als unbehandelte Kontrolle. In wöchentlichen Intervallen über den Zeitraum von 4 Wochen wurden die Katzen für jeweils 6 Stunden auf Fleece-Decken gesetzt.Die Decken wurden mit Floheiem bestreut, bei 85 % rel. Luftfeuchtigkeit und 28°C inkubiert und auf die Entwicklung von Flöhen hin über einen Zeitraum von 30 Tagen beobachtet.Gmppe served as an untreated control. At weekly intervals over the The cats were placed on fleece blankets for 6 hours each for a period of 4 weeks. The blankets were sprinkled with floating egg at 85% rel. Humidity and 28 ° C and observed for the development of fleas over a period of 30 days.
Die Entwicklung erwachsener Flöhe aus Eiem der Behandlungsgmppe wurde über einen Zeitraum von 7 Wochen zu mindestens 95 % im Vergleich zur Kontrollgruppe unterdrückt. Die Wirksamkeit betrag am Tag 56 p.appl. 92 %.The development of adult fleas from eggs of the treatment group was suppressed by at least 95% over a period of 7 weeks compared to the control group. The effectiveness on day 56 is p.appl. 92%.
Die Entwicklung erwachsener Flöhe auf Decken nach Kontakt zu behandeltenThe development of adult fleas to be treated on blankets after contact
Katzen wurde über einen Zeitraum von 17 Tagen zu 95 % oder mehr unterdrückt.Cats were 95% or more suppressed over a 17 day period.
Untersuchungen zur Wirksamkeit der Spot On Formulierungen gemäß Beispielen 1 - 4 auf Flöhe an HundenStudies on the effectiveness of the spot-on formulations according to Examples 1-4 on fleas in dogs
Die Studien wurden durchgeführt, um die Wirksamkeit der einprozentigen Pyriproxyfen-Lösungen gemäß den Beispielen zur Sterilisierung von Flöhen an Hunden nachzuweisen.The studies were carried out to demonstrate the effectiveness of the 1% pyriproxyfen solutions according to the examples for sterilizing fleas in dogs.
Je 20 flohinfestierte Hunde wurden in 2 Gmppen zu 10 Hunden aufgeteilt. Eine20 flea-fixed dogs were divided into 2 groups of 10 dogs. A
Gruppe erhielt 0.04 ml/kg Pyriproxyfen spot on 1 % Lösungen gemäß den Beispielen 1-4 als spot on im Nacken, die andere Gmppe diente als unbehandelte Kontrolle. In wöchentlichen Intervallen über einen Zeitraum von 11 Wochen wurden die Hunde reinfestiert und herabfallende Floheier über einen Zeitraum von 24 Stunden ge- sammelt. Diese Eier wurden bei 85 % rel. Luftfeuchtigkeit und 28°C inkubiert und auf die Entwicklung von Flöhen hin über einen Zeitraum von 30 Tagen beobachtet.Group received 0.04 ml / kg pyriproxyfen spot on 1% solutions according to Examples 1-4 as spot on in the neck, the other group served as an untreated control. The dogs were reinfested at weekly intervals over a period of 11 weeks and falling flea eggs were collected over a period of 24 hours. These eggs were at 85% rel. Humidity and 28 ° C incubated and observed for the development of fleas over a period of 30 days.
Weiterhin wurden in wöchentlichen Intervallen über den Zeitraum von 4 Wochen die Hunde für jeweils 6 Stunden auf Fleece-Decken gesetzt Die Decken wurden mit Floheiem bestreut, bei 85% rel. Luftfeuchtigkeit und 28°C inkubiert und auf dieFurthermore, the dogs were placed on fleece blankets for 6 hours at weekly intervals over a period of 4 weeks. The blankets were sprinkled with floating egg, at 85% rel. Humidity and 28 ° C and incubated on the
Entwicklung von Flöhen hin über einen Zeitraum von 30 Tagen beobachtet. Über einen Zeitraum von 10 Wochen wurde die Entwicklung erwachsener Flöhe aus Eiem der Behandlungsgmppe zu 100 % unterdrückt.Development of fleas was observed over a period of 30 days. Over a period of 10 weeks, the development of adult fleas from Eiem of the treatment group was 100% suppressed.
Die Entwicklung erwachsener Flöhe auf Decken nach Kontakt zu behandeltenThe development of adult fleas to be treated on blankets after contact
Hunden wurde über den gesamten Prüfzeitraum von 24 Tagen zu 100 % unterdrückt.Dogs were 100% suppressed over the entire 24 day test period.
Ermittlung des LangzeitstabilitätsverhaltensDetermination of the long-term stability behavior
Hierzu wurden die herkömmlichen PP-Spot on Tuben der mittleren Wandstärke von ca. 350 μm mit je 0,4 ml Spot on Lösung befüllt und 6 Monate bei 40°C und 75 % relativer Luftfeuchtigkeit gelagert. Die Ergebnisse dieser Studien sind in der Tabelle 1 dargestellt. For this purpose, the conventional PP spot on tubes with an average wall thickness of approx. 350 μm were filled with 0.4 ml spot on solution and stored for 6 months at 40 ° C and 75% relative humidity. The results of these studies are shown in Table 1.
Tab. 1: Langzeitstabilitätsverhalten der Spot on LösungenTab. 1: Long-term stability behavior of the spot on solutions
Der Tabelle 1 wird entnommen, dass die Formulierungen 1 — 4 die Stabilitätsanforderungen der Arzneimittelrichtlinien erfüllen. Die in den Gegenbeispielen 1-2 aufgeführten Formulierangen sind leider nicht Lagerangsstabil. Die jeweiligen Wirkstoffmengen nehmen während der Lagerung > 10 % ab.Table 1 shows that Formulations 1-4 meet the stability requirements of the drug guidelines. The formulation bars listed in counterexamples 1-2 are unfortunately not stable in storage. The respective amounts of active substance decrease> 10% during storage.
Die toxikologischen Eigenschaften der jeweiligen Formulierungen sind in der Tabelle 2 dargestellt. The toxicological properties of the respective formulations are shown in Table 2.
Tab. 2: Die toxikologischen Eigenschaften der Spot on LösungenTab. 2: The toxicological properties of the spot on solutions
Aus Tabelle geht hervor, dass die neuen Spot on Formulierangen eine hervorragende Zieltier- und Umweltverträglichkeit sowie Anwendersicherheit aufweisen. The table shows that the new spot-on formulas have excellent target animal and environmental compatibility as well as user safety.

Claims

Patentansprüche claims
1. Verwendung von Polysiloxanen, enthaltend mindestens eine quartäre Ammoniumgruppe als Formulierhilfsmittel in Formuliemngen larvizider und/oder ovizider Wirkstoffe.1. Use of polysiloxanes containing at least one quaternary ammonium group as formulation auxiliaries in formulations of larvicidal and / or ovicidal active substances.
2. Mittel, enthaltend2. Means containing
a) einen larviziden und /oder oviziden Wirkstoff unda) a larvicidal and / or ovicidal active ingredient and
b) ein Polysiloxanderivat mit mindestens einer quartären Ammonium- grappe pro Molekül,b) a polysiloxane derivative with at least one quaternary ammonium group per molecule,
gegebenenfalls weitere Hilfs- und Trägerstoffe.optionally other auxiliaries and carriers.
3. "Single-Dose" Polypropylenkunststofftübchen, dadurch gekennzeichnet, dass sie mit einem Mittel gemäß Anspruch 2 befüllt sind. 3. "Single-can" polypropylene plastic tub, characterized in that they are filled with an agent according to claim 2.
EP00990645A 1999-12-16 2000-12-05 Fluid insecticidal formulations for treatment of parasitic insect larvae by dermal application Withdrawn EP1253824A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19960775 1999-12-16
DE19960775A DE19960775A1 (en) 1999-12-16 1999-12-16 Dermal insecticidal liquid formulations for controlling parasitic insect larvae
PCT/EP2000/012194 WO2001043545A2 (en) 1999-12-16 2000-12-05 Fluid insecticidal formulations for dermal treatment of parasitic insect larvae

Publications (1)

Publication Number Publication Date
EP1253824A2 true EP1253824A2 (en) 2002-11-06

Family

ID=7932945

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00990645A Withdrawn EP1253824A2 (en) 1999-12-16 2000-12-05 Fluid insecticidal formulations for treatment of parasitic insect larvae by dermal application

Country Status (11)

Country Link
US (1) US20030109496A1 (en)
EP (1) EP1253824A2 (en)
JP (1) JP2003516943A (en)
CN (1) CN1411335A (en)
AR (1) AR026960A1 (en)
AU (1) AU3006101A (en)
BR (1) BR0016413A (en)
CA (1) CA2391802A1 (en)
DE (1) DE19960775A1 (en)
HU (1) HUP0203738A2 (en)
WO (1) WO2001043545A2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4443888A1 (en) * 1994-12-09 1996-06-13 Bayer Ag Dermally administrable formulations of parasiticides
JP2006213616A (en) * 2005-02-02 2006-08-17 Osaka Seiyaku:Kk Animal ectoparasite expelling agent
GB201019975D0 (en) * 2010-11-25 2011-01-05 Excella Tec Ltd A composition and method for the control of arthropods
AU2013204386B2 (en) * 2012-11-01 2016-04-14 Intervet International B.V. Topical parasiticidal formulation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2135886A (en) * 1983-02-22 1984-09-12 Wellcome Found Pesticidal pour-on formulations
DE4318537A1 (en) * 1993-06-04 1994-12-08 Bayer Ag Cationic siloxanyl modified polyhydroxylated hydrocarbons
DE19807630A1 (en) * 1998-02-23 1999-08-26 Bayer Ag Water-based composition useful for controlling parasitic insects and mites, especially lice, on humans
DE19954394A1 (en) * 1999-11-12 2001-05-17 Bayer Ag Use of polysiloxanes with quaternary amino groups as formulation aids and agents contain the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0143545A2 *

Also Published As

Publication number Publication date
DE19960775A1 (en) 2001-06-21
JP2003516943A (en) 2003-05-20
AU3006101A (en) 2001-06-25
WO2001043545A2 (en) 2001-06-21
CN1411335A (en) 2003-04-16
HUP0203738A2 (en) 2003-04-28
CA2391802A1 (en) 2001-06-21
US20030109496A1 (en) 2003-06-12
BR0016413A (en) 2002-08-20
WO2001043545A3 (en) 2001-12-20
AR026960A1 (en) 2003-03-05

Similar Documents

Publication Publication Date Title
EP1624756B1 (en) Agents for controlling parasites on animals
EP1587368B1 (en) Repellent
EP1379138B1 (en) Liquid formulations for dermal application in treatment of parasitic insects in animals
EP2104428B1 (en) Combination product for controlling parasites on animals
DE60006556T2 (en) METHOD AND COMPOSITION FOR COMBATING ARTHROPODES
EP1241943B1 (en) Use of polysiloxanes containing quaternary amino groups as formulation auxiliary agents, and agents containing the same
DE60116379T3 (en) USE OF COMPOSITIONS FOR IMPROVING ACARIC EFFICACY
EP1056343B1 (en) Aqueous formulations of parasiticides for skin application
EP2104426B1 (en) Agents for controlling parasites on animals
EP1089625B1 (en) Ectoparasiticide agents
WO2013000572A1 (en) Composition for controlling parasites on animals
EP1253824A2 (en) Fluid insecticidal formulations for treatment of parasitic insect larvae by dermal application
EP1869979A2 (en) Agent for protection against mites and insects
WO1997046101A1 (en) Pesticides based on cyclic polysiloxanes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020716

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20021120

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030531