EP0544751A1 - Formulations pesticides - Google Patents

Formulations pesticides

Info

Publication number
EP0544751A1
EP0544751A1 EP91915097A EP91915097A EP0544751A1 EP 0544751 A1 EP0544751 A1 EP 0544751A1 EP 91915097 A EP91915097 A EP 91915097A EP 91915097 A EP91915097 A EP 91915097A EP 0544751 A1 EP0544751 A1 EP 0544751A1
Authority
EP
European Patent Office
Prior art keywords
phase
formulation according
stabiliser
active ingredient
pesticidal
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Withdrawn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
EP91915097A
Other languages
German (de)
English (en)
Inventor
Peter Leslie Crampton
Andrew John Huson
David Alan Jeffries
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.)
Sanofi Aventis France
Original Assignee
Roussel Uclaf SA
Wellcome Foundation Ltd
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 Roussel Uclaf SA, Wellcome Foundation Ltd filed Critical Roussel Uclaf SA
Publication of EP0544751A1 publication Critical patent/EP0544751A1/fr
Withdrawn legal-status Critical Current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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals

Definitions

  • the present invention relates to formulations, particularly pesticidal formulations which contain two incompatible pesticides, to methods for making such formulations and their use in controlling pests.
  • an anhydrous formulation of a pesticide i.e. one which does not contain an aqueous phase
  • a second immiscible phase which contains a second pesticide.
  • the present invention provides a two-phase formulation, the first phase of which comprises a first active ingredient, a stabi ⁇ liser, and optionally an emulsifier or wetting or dispersing agent, and a carrier or solvent for the active ingredient; and a second phase immiscible with the first phase which comprises a second active ingredient and optionally an emulsifier or wetting or dispersing agent and a carrier or solvent for the second active ingredient.
  • the first active ingredient is dissolved or dispersed into the first phase but when the active ingredient is a liquid a solvent is not always required.
  • the second phase which is immiscible with the first phase contains the second active ingredient either dissolved or dispersed in the- second phase.
  • the first phase is a water immiscible phase and the second phase is a water phase.
  • the first and second active ingredients are preferably physically and/or chemically incompatible when contained in a single phase, i.e. the presence of one of the actives in a formulation normally affects adversely the stability or utility of the other active.
  • the active ingredient in the first phase may be one which has properties, for example irritancy or noxious vapour, which may be avoided by formulating it according to the present invention.
  • active ingredient we mean both non-biologically and biologically active compounds.
  • the active ingredients may be selected from insecticides, acaricides, herbicides, fungicides, insect and plant growth regulators, pheromones, insect behaviour modifiers, biological control agents (e.g. viruses, bacteria and eggs of parasites), dyes, perfumes, flavours, bactericides, lubricants, medicaments, food supplements, paints, polishes, lacquers (including hair lacquer), textile treatments (including sizes), or other active ingredients which are limited in their use by their incompatibility with other active ingredients.
  • incompatible actives include combinations of pesticides selected from arthropodicides (insecticides, acaricides), herbicides, fungicides or insect and plant growth regulators.
  • incompatible pesticides are the pyrethroids and organophosphate insecticides, the pyrethroid and formamidine insecticides, a-cyano-pyrethroid insecticides and thiazole anthelmintics, and pyrethroids and tributyl tin fungicides.
  • pyrethroid insecticides include those of the formula (I)
  • n 0 or 1
  • Examples of pyrethroids are 3-phenoxybenzyl-(IRS)-cis.trans-3-(2.2- dichlorovinyl-2,2-di- methyl- cyclopropane-1-carboxylate (permethrin) , (RS) -a-cyano-3-phenoxybenzyl-(IRS)-cis.trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-l-carboxylate (cypermethrin) and its indivi- dual isomers such as the (IRS) cis isomer (alphamethrin) , (S)- ⁇ -cyano-3-phenoxybenzyl-(IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane-1-carboxylate (deltamethrin) , or a reaction mixture comprising two enantiomeric pairs in approximately ratio 2:3 (S)- ⁇ -
  • Examples of formamidine insecticides include N-methyl bis(2,4-xylyl- aminomethyl)amine (A itraz) .
  • Examples of thiazole anthelmintics include 2,3,5,6-tetrahydro-6-phenylimidazo[2,1-b]thiazole(levamisole) .
  • Examples of fungicides include tributyl tin oxide.
  • incompatible actives in the formulations of the present invention include deltamethrin and chlorpyrifos methyl in an aqueous system.
  • the first phase is preferably dispersed within the second phase.
  • the stabiliser forms a barrier at the interface between the dispersed first phase and the second phase.
  • the stabiliser is preferably a film-forming alkanol eg. an alkanol which can act as an evaporation retardant in an aqueous spray system as described in European Patent Specification 331474. It is preferably a primary alcohol; preferably with no more than one or two side substitutions selected from methyl, ethyl, trifluoromethyl and halo (e.g.
  • cetostearyl alcohol is quite satisfactory. Heptadecan-1-ol performs adequately but is much more expensive. Other highly effective film-forming agents include 1-hexadecylamine, 1-heptadecylamine and
  • film-forming agents include hexadecan-2-ol, 1,2-hexadecandiol, methyl stearate, stearyl acetate, methyl palmitate and 1,2-octadecandiol.
  • N-alkoxyalkanoIs may be used, for example or CH_(CH-).-OC-H.OH, as may oxyethylene-docosanol and mixtures of any of the said film-forming compounds.
  • the emulsifier may be any suitable compound or mixture of compounds. Cationic emulsifiers can be used, but they tend to irritate the user's eyes. Anionic emulsifiers such as calcium dodecyl benzene sulphate (CDBS) or sodium d-isopropyl naphthalene sulphonate (SDNS) can also be used, but these are not as effective at stabilising the emulsion whilst maintaining evaporation retarding properties.
  • the emulsifier is a non-ionic compound, or mixture of non-ionic compounds, having an HLB (hydrophilic/lipophilic balance) of 6-20 and preferably 8-18.
  • Suitable compounds include polyoxyethylene stearyl ethers (PSE) , polyoxyethylene monolaurates (PEM) , polyoxyethylene mono-oleates (PMO) , sorbitan mono-oleate (SMO) , nonylphenol ethoxylate (NPE) , polyethylene glycol (PEG) and blends of oleyl ethoxylate (10 mole) , and PEG20 glyceryl oleate (OE/PGO) .
  • PSE polyoxyethylene stearyl ethers
  • PEM polyoxyethylene monolaurates
  • PMO polyoxyethylene mono-oleates
  • SMO sorbitan mono-oleate
  • NPE nonylphenol ethoxylate
  • PEG polyethylene glycol
  • OE/PGO PEG20 glyceryl oleate
  • the solvent, for the first phase preferably has a low relative molecular mass, namely less than about 200.
  • Suitable compounds include aromatic hydrocarbons, lower alkyl esters, lower ketones, lower alkanols and lower alkanes, the term "lower" meaning C,
  • Particular solvents include the following, all available from Exxon Chemicals Limited;
  • Solvesso 150 An aromatic hydrocarbon solvent (C9 to Cll) with a distillation range 190 to 210°C.
  • Solvesso 200 An aromatic hydrocarbon solvent (CIO to C12) with a distillation range 226 to 290°C.
  • Odourless kerosene - A mixture of high boiling non-aromatic hydrocarbons consisting of paraffins and naphthenes with a distillation range of 180 to 270°C.
  • the first phase may comprise more than one active ingredient (optionally with a synergist or potentiator, which is regarded as an active ingredient for the purpose of the Formula below) , more than one solvent, more than one emulsifier and/or more than one stabiliser, together with other ingredients such as perfumes and dyes.
  • the first phase of the formulation satisfies the formula :
  • L is less than or equal to 15, A - 700376, B - -1.51, C - 0.8472
  • M M coil is the weighted average relative molar mass of the oil phase
  • M stabiliser is the average molar mass of the stabiliser
  • Y is the molar solubility ratio of the formulation, defined as the minimum number of moles of oil phase which will dissolve the stabiliser, divided by the number of moles of stabiliser, provided that, in the Formula above, any solvent which has no liquid phase at 27 C at atmospheric pressure is excluded.
  • the “oil phase” is the liquid non aqueous phase and will comprise one or more of the active ingredient, the solvent therefor and in some cases the emulsifier.
  • L is less than 12, 10, or 8 and is most preferably less than 5.
  • a distilled water spray has an "L” value of about 26, and most conventional diluted formulations have a value of about 22-30.
  • "L” can be set at a desired value in order to calculate the required ratios of the ingredients.
  • M oil the average molecular weight of the oil phase, is the weighted average, i.e. taking into account the relative proportions of the ingredients.
  • Y namely the molar solubility ratio of the formulation
  • Y may be derived empirically by making up at 40 C a series of mixtures with different ratios of oil phase to alkanol, allowing the mixtures to cool to 27 C, leaving the cool mixtures for at least 48 hours at 27 C, and determining the amount, in moles, of the oil phase which is needed to dissolve completely a given amount of retardant, in moles. The former is then divided by the latter to give Y.
  • Preferred film-forming compounds include C.. ⁇ saturated alkanols io- U such as hexadecan-1-ol and C. - - discipline saturated amines. lo-lo
  • Preferred emulsifiers and solvents for the first phase are as described hereinbefore for European Patent Specification 331474, which is incorporated herein by reference.
  • formulations of the present invention will be dependent upon the nature of the active ingredients included within the formulation but the formulations will commonly be used to control pesticidal infestations such as insect, acarine or helminth or microbial infestations.
  • the application rate of the active ingredients will correspond to the application rates of these actives when applied conventionally for that particular use.
  • a preferred formulation of the present invention contains 20% chlorpyrifos methyl and 1% deltamethrin, cetyl alcohol being the stabiliser.
  • This formulation is useful for the treatment of stored crops such as grain, in particular against insect pests, of the orders Coleoptera (e.g. Anobium. Ceutorhvnchus. Rhvnchophorus. Cosmopolites. Lissorhoptrus. Melipethes. Hvpothenemus. Hylesinus. Acalymma. Lema. Psylliodes. Leptinotarsa. Gonocephalum. Agriotes. Dermolepida. He eronvchus. Phaedon. Tribolium. Sitophilus. Orvzaephilus.
  • Rhvzoperth Prostephanus. Crvptoletes. Trogoderma. Typheae. Diabrotica. Anthonomus or Anthrenus spp.
  • Lepidoptera e.g. Ephestia. Mamestra. Earlas. Pectinophora. Ostrinia. Trichoplusia. Pieris. Plodia, Sitotroga. Corcyra. T_.phy —nn . Agrotis, Amathes. Wiseana. Tryporysa. Diatrae. Sporganothis. Cydia. Archips. Plutella. Chilo. Heliothis. Spodoptera or Tineola spp.), Diptera (e.g.
  • Hymenoptera e.g. Athalia. Cephus, Atta. Solenopsis or Monomorium spp.
  • Isoptera e.g. Odontoter es and Reticulitermes spp.
  • Siphonaptera e.g. Ctencephalides or Pulex spp.
  • Thysanura e.g. Lepisma spp.
  • Dermaptera e.g. Forficula spp.
  • Pscoptera e.g. Peripsocus spp.
  • Thysanoptera e.g. Thrips tabaci
  • Acarine pests include ticks, e.g.
  • the first active is dissolved in a solvent to form, or is itself, the first phase.
  • the second active ingredient is dispersed in part of the second phase.
  • the surfactants are dispersed either into the first phase or into the part of the second phase containing the second active ingredient.
  • the first phase is then dispersed into that part of the second phase that does not contain the second active ingredient.
  • Step (6) is not carried out under high sheer conditions. Therefore the second portion of the second phase simply combines with the first portion of the second phase and the end result is a first-phase-in-second-phase dispersion or emulsion.
  • Example 1 describes formulations according to the present invention containing pyrethroid and an organophosphorus insecticide.
  • Example 2 shows the result of tests to demonstrate the stability of formulations according to the present invention.
  • Example 3 shows the results of biological tests on various insect pests.
  • the deltamethrin (20% SC) contains deltamethrin (20%) in water with surfactant, thickening agents and biological preservative.
  • the oil phase was prepared by dissolving cetyl alcohol in a solution of chlorpyrifos methyl in Solvesso 150 at a temperature up to 50 C.
  • the emulsifiers were added to the water at 60 C and the resultant aqueous solution cooled to 50 C (aqueous phase) .
  • the oil phase was added to the aqueous phase at 50 C with vigorous mixing and the resultant emulsion cooled to 20 C.
  • Tests were carried out on the stability of active ingredients in a formulation according to the present invention (A) and in a two-phase ' formulation that does not contain stabiliser (B) .
  • a chlorpyrifos methyl/Deltamethrin Formulation with film forming agent was prepared in a similar manner to Example 1 above.
  • a chlorpyrifos methyl/Deltamethrin Formulation without film forming agent A chlorpyrifos methyl/Deltamethrin Formulation without film forming agent.
  • Protocol Appropriately water-diluted formulation was sprayed on to 400 tonnes of grain at Wail, Victoria. It was applied to the grain stream during turning at one litre spray per tonne. Treated grain was sampled at intervals by means of a vacuum probe. Bioassays were conducted by holding 100 adult insects on 150g or 300g grain. After 3 weeks incubation at 25 C, 55-60% relative humidity the insects were sieved off and mortality counted. The grain was further sieved at 7, 9, and 11 weeks to remove and mortality count adult progeny.
  • Results show good control of insect pests for post-treatment storage up to 9 months.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

L'invention concerne des formulations pesticides qui permettent d'incorporer des pesticides incompatibles dans la même formulation. Ces formulations comprennent une formulation à deux phases. La première phase comporte un premier ingrédient actif, un stabilisateur et facultativement un émulsifiant ou un agent mouillant ou dispersant, et un support ou un solvant pour l'ingrédient actif. La deuxième phase immiscible avec la première phase, comprend un deuxième ingrédient actif et facultativement un émulsifiant ou un agent mouillant ou dispersant, et un support ou un solvant pour le deuxième ingrédient actif. L'invention concerne également des procédés de préparation et d'utilisation de ces formulations pour éliminer les parasites.
EP91915097A 1990-08-20 1991-08-20 Formulations pesticides Withdrawn EP0544751A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909018227A GB9018227D0 (en) 1990-08-20 1990-08-20 Pesticidal formulations
GB9018227 1990-08-20

Publications (1)

Publication Number Publication Date
EP0544751A1 true EP0544751A1 (fr) 1993-06-09

Family

ID=10680932

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91915097A Withdrawn EP0544751A1 (fr) 1990-08-20 1991-08-20 Formulations pesticides

Country Status (15)

Country Link
EP (1) EP0544751A1 (fr)
JP (1) JPH06500324A (fr)
AU (1) AU654965B2 (fr)
BG (1) BG97459A (fr)
BR (1) BR9106776A (fr)
CA (1) CA2075303A1 (fr)
CZ (1) CZ380692A3 (fr)
FI (1) FI930692A (fr)
GB (1) GB9018227D0 (fr)
HU (1) HUT62432A (fr)
MC (1) MC2231A1 (fr)
NO (1) NO930132D0 (fr)
PL (1) PL167656B1 (fr)
WO (1) WO1992003047A1 (fr)
ZA (1) ZA916557B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2830518C (fr) * 2011-04-20 2019-07-16 Huntsman Petrochemical Llc Agents de reduction de la derive de produits pulverises comprenant des agents tensioactifs a valeur d'equilibre hydrophile-lipophile basse
AU2018272316B2 (en) * 2017-05-25 2022-06-02 Upl Ltd A stable agrochemical composition and process thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2095109B (en) * 1981-03-09 1984-07-18 Wellcome Found Insecticidal compositions
GB8515459D0 (en) * 1985-06-19 1985-07-24 Young Robert Co Ltd Parasitical compositions
EP0304492B1 (fr) * 1987-03-13 1994-12-07 Sumitomo Chemical Company, Limited Preparation pesticide stable sous forme solide
WO1990003112A1 (fr) * 1987-03-30 1990-04-05 Nc Development, Inc. Lutte antiparasitaire
GB8822937D0 (en) * 1988-09-30 1988-11-09 Nc Dev Inc Chemical formulations
CA1301642C (fr) * 1987-03-30 1992-05-26 Howard Bernard Dawson Formulations chimiques
DE3875251T2 (de) * 1987-10-14 1993-02-25 Dowelanco Agrochemische zusammensetzungen auf basis von latex.
GB8804988D0 (en) * 1988-03-02 1988-03-30 Wellcome Found Sprayable formulations
US5049182A (en) * 1989-02-03 1991-09-17 Ici Americas Inc. Single-package agricultural formulations combining immediate and time-delayed delivery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9203047A1 *

Also Published As

Publication number Publication date
NO930132L (no) 1993-01-14
JPH06500324A (ja) 1994-01-13
CZ380692A3 (en) 1993-10-13
FI930692A0 (fi) 1993-02-17
BR9106776A (pt) 1993-08-17
CA2075303A1 (fr) 1992-02-21
GB9018227D0 (en) 1990-10-03
HU9203752D0 (en) 1993-03-29
PL167656B1 (pl) 1995-10-31
NO930132D0 (no) 1993-01-14
MC2231A1 (fr) 1993-02-23
AU8430991A (en) 1992-03-17
BG97459A (en) 1994-03-24
AU654965B2 (en) 1994-12-01
WO1992003047A1 (fr) 1992-03-05
FI930692A (fi) 1993-02-17
HUT62432A (en) 1993-05-28
ZA916557B (en) 1993-04-28

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