AU654965B2 - Pesticidal formulations - Google Patents

Description

OPI DATE 17/03/92 F AOJP DATE 30/04/92 APPLN. ID 84309 91 PCT NUMBER PCT/GB91/01413 ,54Z INTERNATIonL- _EATY

(PCT)

(51) International Patent Classification 5 (11) International Publication Number: WO 92/03047 A01N 25/22 (A01N 25/22 Al A01N 25/00, 25/02, 25/04 A (43) International Publication Date: 5 March 1992 (05.03.92) A01N 53/00, 57/08) (21) International Application Number: PCT/GB91/01413 (72) Inventors; and Inventors/Applicants (for US only) CRAMPTON, Peter, (22) International Filing Date: 20 August 1991 (20.08.91) Leslie [GB/GB]; HUSON. Andrew, John [GB/GB]; JEFFRIES, David, Alan [GB/GB]; Ravens Lane, Berkhamsted, Hertforshire HP4 2DY (GB).

Priority data: 9018227.0 20 August 1990 (20.08.90) GB (74) Agent: ROLLINS, The Wellcome Foundation Limited, Langley Court, Beckenham, Kent BR3 3BS (GB).

Parent Applications or Grants (6 1 Related by Addition (81) Designated States: AT (European patent), AU, BE (Euro- AU 32914/89 pean patent), BG, BR, CA, CH (European patent), CS.

(63) Related by Continuation DE (European patent), DK (European patent), ES (Eu- US 438,399 (CIP) ropean patent), FI, FR (European patent), GB (Euro- Filed on 1 March 1989 (01.03.89) pean patent), GR (European patent), HU, IT (European patent), JP, KR, LK, LU (European patent), MC. NL (European patent), NO, PL, RO, SE (European patent), (71)Appleant (f all i ne Slu .p US). THE WEtLL- SU+,US.

~COMn E F UN rDATION IMI u rEB a[l L Un- IiLul |o 0et-er4o-oen Roadt Londn-nWmt--BP-(6B)- Published ifijft -i 2eap*/ 0. j E0 7 2 3 (54)Title: PESTICIDAL FORMULATIONS (57) Abstract Pesticidal formulations are provided which allow incompatible pesticides to be incorporated in the same formulation. The formulations comprise a two-phase formulation, the first phase of which comprises a first active ingredient, a stabiliser 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. Methods for making such formulations and their use in controlling pests are 'provided.

-1 See back of page L. i F i I L iC ni WO 92/03047 PCT/GB91/01413 -1- PESTICIDAL FORMULATIONS 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.

It has been found that an anhydrous formulation of a pesticide, i.e.

one which does not contain an aqueous phase, may be formulated with a second immiscible phase which contains a second pesticide. This has the advantage that incompatible pesticides may be incorporated in the same formulation.

Accordingly, the present invention provides a two-phase formulation, the first phase of which comprises a first active ingredient, a stabiliser, 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.

Normally, 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. Preferably, 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. In addition, 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. Thus, it may have- ieem-a ssible previously to prepare stable but irritant iii i WO 92/03047 PCT/GB91/01413 -2 formulations of the active ingredients; formulations according to the present invention may avoid such irritancy. By active ingredient we mean both non-biologically and biologically active compounds. For example, the active ingredients may be selected from insecticides, acaricides, herbicides, fungicides, insect and plant growth regulators, pheromones, insect behaviour modifiers, biological control agents 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. Examples of incompatible actives include combinations of pesticides selected from arthropodicides (insecticides, acaricides), herbicides, fungicides or insect and plant growth regulators.

Examples of incompatible pesticides are the pyrethroids and organophosphate insecticides, the pyrethroid and formamidine insecticides, a-cyano-pyrethroid insecticides and thiazole anthelmintic- Ad pyrethroids and tributyl tin fungicides.

Examples of pyrethroid insecticides include those of the formula (I) x 0 I I o C- (I) 0 0 where R is CHC.3 _S j ii I- c' i;I ii:| WO 91/03047 WO 9203047PC[/GB9]/01413 -3

KH

and n is 0 or 1, R 1is halo, CF 3or CHF 20, R 2is hydrogen or halo, and Z and Z 1are each independently selected from halo, CF 3and methyl, X is hydrogen or halo, and X is H, CN or C-CH C

CH

C R5 C CHOCH2.

I

Examples of pyrethroids are 3-phenox~ybenzyl- (lRS)-cji.,trans-3- (2,2dichlorovinyl-2 ,2-di- methyl- cyclopropane- 1-carboxylate (permethrin), (RS)-at-cyano-3-phenoxybenzyl-(lRS)-cji.,trans-3-(2,2-dichlorovinyl)- 2, 2-dimethylcyclopropane-l-carboxylate (cyperinethrin) and its indivi- Mond WO 92/03047 PCr/GB9'/01413 dual isomers such as the (iRS) cis isomer (alpha-methrin), (S)-c-cyano-3-phenoxybenzyl-(IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethy1 cyclopropane-l-carboxylate (deltamethrin), or a reaction mixture comprising two enantiomeric pairs in approximately ratio 2:3 -a-cyano-3-phenoxybenzyl- (IR) -cis-3- 2-dichlorovinyl) 2-dimethylcyclopropanecarboxylate and -a-cyano-3--phenoxybenzyl (IS) -cis-3 2-dichiorovinyl) 2-dimethylcyclopropanecarboxylate with cyano-3-phenoxybenzyl (IR)-trans-3-(2,2-dichlorovinyl) -2 ,2-dimethylcyclopropanecarboxylate and (R)-a-cyano-3-phenoxybenzyl(IS)-trans-3- (2,2-dichlorovinyl)-2,2--dimethylcyclopropanecarboxylate (beta-cypermethrin), (RS)-a-cyano-3-phenoxybenzyl-(7Z)-(IRS)-cis-3-(2-chloro-3,3,- 3-trifluoro propenyl)-2, 2-dimethylcyclopropanecarboxylate (cyhalothrin) and a mixture of its and (R)(Z)-(IS)-cis-isomers; (RS) -a-cyano-3-phenoxybenzyl (4-chlorophenyl) -3-methylbutyrate (fenvalerate) and the single isomer (esfenvalerate) (RS) -a-cyano-3-phenoxybenzyl (4-difluoromethoxyphenyl) -3-methyl butyrate (flucythinate), (RS) -a-cyano-3-phenoxybenzyl N(2-chloroa,cz,a-trifluoro-p-tolyl)-D- valinate (fluvalinate), (RS)-a-cyano-4fluoro-3-phenoxybenzyl(IRS) -cis-trans-3- 2-dichiorovinyl) 2-dimethylcyclopropanecarboxy late (cyfluthrin), (RS) -a-cyano-4-fluoro-3phenoxybenzyl(IRS)-cis-trans-3- (2-chloro-2(4-chlorophenyl)vinyl)-2, 2dimethylcyclopropanecarboxylate (fluxnethrin), 2-methylbiphenyl-3-ylmethyl(Z) -(IRS, 3RS) (2-chloro-3 3-trifluoroprop-l-enyl)2 ,2-dimethyl cyclopropane carboxylate (Bifenthrin); the allethrins, for example (iRS) -3-allyl-2-methyl-4-oxocylopent-2enyl (lR,3R)-2,2-dimethyl-3- (2-methylprop-l-enyl)cyclopropanecarboxylate (bioallethrin), (lS)-allyl-2-methyl-4-oxocyclopent-2-enyl (lR, 3R) 2-dimethyl-3- (2-methylprop-l-enyl)cyclopropanecarboxylate (S-bioallethrin), and mixtures of allethrin isomers (esbiothrin); the resmethrins, for example 5-benzyl-3-furylmethyl(IRS, 3RS; IRSA 3SR)-2, 2-dimethyl-3- (2-methyl-prop-l-enyl)cyclopropanecarboxylateI (resmethrin) and 5-benzyl-3-furylmethyl (lR,3R)-2,2-dimethyl-3-(2methylprop-l-enyl)cyclopropanecarboxylate (bioresmethrin).

WO 92/03047 PCT/GB91/01413 Examples of organophosphate insecticides are: 0,0-dimethyl-0-3,5,6-trichloro-2-pyridylphosphorothioate (Chloropyrifos-methyl) Examples of formamidine insecticides include N-methyl bis(2,4-xylylaminomethyl)amine (Amitraz). Examples of thiazole anthelmintics include 2,3,5,6-tetrahydro-6-phenylimidazo[2,l-b]thiazole(levamisole).

Examples of fungicides include tributyl tin oxide.

Particularly preferred examples of 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 fluoro or chloro), with such substitutions preferably remote from the alcohol group (preferably at least 7 carbon atoms away from the hydroxyl group), and preferably the alkanol is not substituted at all; preferably C 16 20 preferably saturated; and preferably a solid at 270C, Octadecan-l-ol and, particularly, hexadecan-l-ol are preferred. Hexadecan-l-ol (also known as cetyl alcohol) is usually available commercially as a mixture with a minor proportion of octadecan-l-ol (stearyl alcohol) and such "cetostearyl alcohol" is quite satisfactory. Heptadecan-l-ol performs adequately but is much more expensive. Other highly effective film-forming agents include 1-hexadecylamine, 1-heptadecylamine and 1-octadecylamine. Less preferred film-forming agents include hexadecan-2-ol, 1,2-hexadecandiol, methyl stearate, stearyl acetate, methyl palmitate and 1,2-mctateandiol. N-alkoxyalkanols may be used, i i 1': iT:I i i; I WO 92/03047 PCT/GB91:'01413 6 for example CH 3

(CH

2 21 0C2H4OH, CH3(CH2)210C3H6OH, CH 3

(CH

2 17 OC2H4OH or

CH

3

(CH

2 15 OC2H OH, as may oxyethylene-docosanol and mixtures of any of the said film-forming compounds.

The ei. ifier 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. Preferably, 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 mole), and PEG20 glyceryl oleate (OE/PGO).

These emulsifiers are available as follows: Abbrev.

OE/PGO

PSE

PEM

Trade name Tegoplant EM11 Brij 72, Brij 76, Brij 78 Tween 20 Span 80 Tween 80 Supplier Th.

Goldschmidt Ltd.

ICI Speciality Chemicals ICI Speciality Chemicals ICI Speciality Chemicals ICI Speciality Chemicals 11'-i ri.

WO 92/03047 PCT/GB91/01413 7 NPE Ethylan Lankro Chemicals Limited CDBS Arylan CA Lankro Chemicals Limited SDN Aerosol OS Cyanamid GB Ltd.

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- 12 preferably C1- 10 and more preferably C1- 8 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 2100C.

"Solvesso 200" An aromatic hydrocarbon solvent (ClO to C12) with a distillation range 226 to 2900C.

"Exxate 700" Heptyl acetate 99% pure, or Odourless kerosene A mixture of high boiling non-aromatic hydrocarbons consisting of paraffins and naphthenes with a distillation range of 180 to 2700C.

The first phase may comprise more than one active ingredient (optionally with a synergist or potentiator, which is regarded as an S..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.

I f 1- h-i -li; -i ll IX -I WO 92/03047 PCT/GB91/01413 8 a. H. f.

the formula The first phase of the formulation satisfies

M

oil Exp ln(L/4)+C In(AXB) Mstabiliser c mass of oil phase mass of stabiliser where L is less than or equal to 15, A 700376, B -1.51, C 0.8472 oil is the weighted average relative molar mass of the oil phase

M

stabiliser is the average molar mass of the stabiliser, and stabiliser is the average molar mass of the stabiliser, and X (Moil)1.8 where 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 0 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.

For the avoidance of doubt, and to clarify any ambiguities which may arise in the printing or copying of this specification, it is to be noted that the relational symbol in the Formula is "less than or equal to", "Exp" means the exponential of what follows in brackets, "ln" means the natural logarithm, i.e. loge, L is divided by 4, X is raised to the power B, B is a negative value (minus 1.51) and, in the definition of X, Moil is raised to the power 1.8.

Preferably L is less than 12, 10, or 8 and is most preferably less than 5. A distilled water spray has an value of about 26, and most conventional diluted formulations have a value of about 22-30.

jl

I~

i r iIi i 1 i: :e u _1 _I I_ i i ~.c f"' WO 92/03047 PCT/GB91/01413 9 In the formulations of the value in order to calculate

M

oil, the average molecular average, i.e. taking into ingredients.

invention, can be set at a desired the required ratios of the ingredients.

weight of the oil phase, is the weighted account the relative proportions of the The value namely the molar solubility ratio of the formulation, may be derived empirically by making up at 400C 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 1-ast 48 hours at 27 0 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 6-20 saturated alkanols such as hexadecan-l-ol and C 16 18 saturated amines.

Preferred emulsifiers and solvents for the first phase are as described hereinbefore for European Patent Specificativ 331474, which is incorporated herein by reference.

The use of the 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 Anobium, Ceutorhynchus, Rhynchophorus, Cosmovolites, 1

I

:4 j'* I l t I 1' WO 92/03047 PCT/GB91I/01413 10 Lissorhoptrus, Meligethes, Hypothenemus, Hylesinus, Acalymnma, Leina, Psylliodes, Leptinotarsa. Gonocephalum, Ag-*Lrs Dermolerpida, Heteronychus, Phaedon, Tribolium, Sitophilus, Oryzae-Philus, Rhyzopertha, Pros tephanus, Cryvv-l1etes., Trogoderma. Typheae, Diabrotica, Anthonomus or Anthrenus spp.), Lepidoptera Ephestia, MAMestra, Earias, Pectinophora, Ostrinia, Trichoplusia, Pieris, Plodia, Sitotroga, Corcyra, Laphvyma, Agrotis, Amathes, Wiseana, )ryrsa, Diatrae, Sporganothis, Cydia, Archips, Plutella, Chilo, _Heliothis, Svodo-t' ra or Tineola spp.), Diptera Musca, Aedes, Anopheles, Culex, Clossina, Simulium, Stomoxys, Haematobia, Tabanus, Hydrotaea, Lucilia, Chrysomia, Callitrova, Dermatobia, Gastero-philus, Hypoderma, Hylemyia, Atherigona, Chlorops, Phytomyza, Geratitis, Liriomyza and Melophagus spp.), Phthiraptera (Malopha-a e.g. Damalina spp. and Anotlura e.g. Linognathus. and H-aematoyinus. spp.), Hemiptera Aphis, Bemisia, Phorodon, Aeneolamia, Empoat'.ca, Parkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococus, Helopelt s, Lyus Dysdercus, Oxvcarenus, Nezara, Aleurodes, Triatoma, Psylla, Mysus, Me~oura, Phylloxera, Adelyes, Niloparvata, Nephrotetix or Gimex spp.), Orthoptera Locusta, Gryilus, Schistocerca or Acheta spp.), Dictyoptera Blattella, Periplaneta or Blatta spp.) Hymnenoptera Atchalia, Cephus, Atta, Solenopsis or Monomoriun spp.), Isoptera Odontotermes and Reticulitermes spp.), Siphonaptera (e.g.

Ctencetihalides or Pulex spp.), Thysanura Lepisina spp.), Dermapteia Forficula spp.), Pscoptera Peripsocus. spp.) and Thysanoptera Thrips tabaci),. Acarine pests include ticks, e.g'.

members of the genera Boophilus, Ornithodorus, Rhi icephalus, Amibivomna, hyalomma, Ixodes, Haemaphysalis, Dermacentor and Anocentor, and mites and manges such as Acarus, Tyro~hagus, Glycvtha:us, Tetranychus, Psoroptes, Notoednes, arcptes, Psorergates, Chorioptes, Eutrombicula, Demodex, Panonvychus, Bryobia, Eriophyes, Alaniulus, Poly~hagotarsonemus, Scutigerella, and Oniscus spp. and Periplaneta, Blatta, Blattella and Lapisma.

V

.i 1 WO 92/03047 PCT/GB91/01413 The formulations of the present invention may be prepared as follows: 1) The first active is dissolved in a solvent to form, or is itself, the first phase.

2) The stabiliser is dissolved into the first phase.

3) The second active ingredient is dispersed in part of the second phase.

4) 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.

6) The remainder of the second phase containing the second active ingredient is mixed with the mixture of the first phase and the other part of the second phase.

Step 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.

The present invention will now be described in more detail by way of the following examples. 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.

I?

j

Y"

where Y is the molar solubility ratio of the formulation, defined as the minimum number of moles of oil phase which will dissolve the stabiliser, WO 92/03047 PCT/GB91/01413 12 Example 1 Formulations Ingredients w/w chlorpyrifos methyl 19.15 solvesso 150 19.15 water (deionised) 51.40 emulsifiers 2.00 Deltamethrin (20% SC) 5.20 The deltamethrin (20% SC) contains deltamethrin 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 0

C.

The emulsifiers were added to the water at 60 0 °C and the resultant aqueous solution cooled to 50 0 C (aqueous phase).

The oil phase was added to- the aqueous phase at 50 0 °C with vigorous mixing and the resultant emulsion cooled to 20 0

C.

A 20% aqueous suspension of deltamethrin was added with stirring at 20-25 0

°C

Example 2 Stability testing Tests were carried out on the stability of active ingredients in a formulation according to the present invention and in a two-phase formulation that does not contain stabiliser Formulation A Results A chlorpyrifos methyl/Deltamethrin Formulation with film forming agent was prepared in a similar manner to Example 1 above.

.e-Tyit! Stability D-ata: hlr;yrifeg mathyl (CPMa) tests (figurS I i W 9/03 \C~G 9/ 1 -1 e,

VI

1 2a The stability data figures which follow are expressed in percentage of the initial concentration of the active ingredient.

Typical Stability Data: chlorpyrifos Methyl (CPMe) tests (figures +j 1 0%) 0000 o 00 0 4 0040 0 0 4004 00 OS 00 0 0 0000 0004 0 00 00 0 00 0 0 00 0

C

t (Cit

CCCI

C

CC

C CCC'' C 1 8 /8/9 4 DK84309.SPE1 2a +See back of page WO 92/03047 PCT/GB91/01413 -13 Time in months 25 00 38 0 C 50 00

(M)

Initial 100 100 100 3 Mor 4M 101 103 103 6 M 102 100 103 12 M 101 94 101 Typical Stability Data :Deltamethrin (DLTM) Time in months 25 00 38 00 50 00

(M)

Initial 100 100 100 3 Mor 4M 96 99 98 6KM 97 103 103 12 M 98 94 76 Formulations B -results A chlorpyrifos methyl/Deltanethrin Formulation without film forming agent.

Typical Stability Data CPEE Time in months 2500 3800 5000 (14) Initial 100 100 100 3KM 112 106 71 i It~ f-

F'-

WO 92/03047 PCT/GB91/01413 14 Typical Stability Data DLTM Time in months

(M)

Initial 3M 25°C 380C The results show formulations (B) relatively unstable.

Example 3 Biological testing without film forming agent are 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 3 0 0g 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.

'4 4 0.24:4.9mg/kg deltamethrin:chlorpvrifos-methyl Insects tested Months of post-treatment Mortality storage Progeny numbers living dead Progeny suppression Sitophilus oryzae 99.8 100 100 100 100 100 i: a" i i; 1 i iB!_li d~

I

WO 92/03047 PCr/GB91/01413 15 Rhyzopertha dominica Tribolium cas taneum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 99 99 100 95 100 100 100 99 95 100 100 100 100 100 100 100 100 99.7 100 99.5 99.0 100 100 97 100 99.7 99.0 100 100 100 99.7 100 99.9 100 Queensland Triboliui cas taneum 279

I

Oryzaephilus surinamensis 0 1.5 3 4.5 6 9 0 1.5 3 6 9 control of Results show good up to 9 months.

insect pests for post-treatment storage

Claims (2)

1. A pesticidal formulation comprising a two-phase formulation, the first phase of which comprises a first active ingredient, a stabiliser, and optionally an emulsifier or wetting or dispersing agent, and a carrier or solvent for the active ingredient wherein said first phase satisfies the formula: mass of oil phase mass of stabiliser Moil tabiliser "stabiliser Exp [1 n(L/4)+C ln(AXB") C J where L is less than or equal to 15, A 700376, B -1.51, C 0.8472 Moil is the weighted average relative molar mass of the oil phase Mstabiliser is the average molar mass of the stabiliser, and X (Moil)' 8 o o a o u, orr o a o OIPq or IV a o oo r orro o oi .00:2 *00 0000n~ where 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 nunoer of moles of stabiliser, provided that, in the Formula above, any solvent which has no liquid phase at 270C at atmospheric pressure is excluded; 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. A pesticidal formulation according to claim 1 wherein the first phase is a water immiscible phase. A pesticidal formulation according to claim 2 wherein the second phase is a water phase. A pesticidal formulation according to any preceding claim wherein.the first and second active ingredients are physically and/or chemically 18/8/94DK84309.SPE,16a I=r fl ~Usi F 17 incompatible when contained in a single phase. A pesticidal formulation according to claim 4 wherein the incompatible actives include the pyrethroids and organophosphate insecticides. A pesticidal formulation according to claim 5 wherein the insecticides are deltamethrin and chlorpyrifos methyl in an aqueous system. A pesticidal formulation according to any one of the preceding claims wherein L is less than A pesticidal formulation according to any one of the preceding claims wherein the stabiliser is a C16.20 saturated alkanol, or C,,16 saturated amine. Use of a pesticidal formulation according to any preceding claim to control pesticidal infestations such as insect, acarine or helminth or microbial infestations. DATED this 18th 15 o t o a a o t o o a e t o e« o fl a o day of August 1994. ROUSSEL-UCLAF By their Patent Attorneys: CALLINAN LAWRIE U o o eoo o a e o6 o •o a o* a a 1 a j I 18/8/94DK84309.SPE,17a LC~ e~lllC-P LI i y I -U ~1 It- L II_ Ii i r L-~ 171 b INTERNATIONAL SEARCH REPORT International Application No PC !GB 91/01413 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC A 01 N 25/22//(A 01 N 25/22, 25:00, 25:02, 25:04, 53:00 57 08n) II. FIELDS SEARCHED Minimum Documentation Searched' Classification System Classification Symbols A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in Fields Searched 8 III. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category Citation of Document., 1 with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. X WO, Al, 8607525 (ROBERT YOUNG COMPANY LIMITED) 1-10 31 December 1986, see the whole document X GB, A, 2095109 (THE WELLCOME FOUNDATION LIMITED) 1-10 29 September 1982, see the whole document X WO, Al, 8807326 (NC DEVELOPMENT INC) 1-10 6 October 1988, see page 11, line 31 page 12, line 11; page 16, lines 5-22; page 30, lines

10-29; page 31, line 16 page 32, line 3 SSpecial categories of cited documents: 0 T" .;ter document published after the international filing date or priority date and not in conllict with the application but document definirg the general state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or alter the international document of particular relevance, the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance, the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive steD when the document is combined with one or more other such docu- document referring to an oral disclosure, use, exhibition or ments, such combination being obvious to a person skilled other means in the art. document published prior to the international filing date but document memb(r of the same patent family later than the priority date claimed IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 21st November 1991 1 7 DEC 1991 International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE Mme N. KUPER Form PCT/ISA210 (second sheet) (January 1985) it ss f; c, j, ;i I' ii- C- j- e 1 i !rr i. 1 International Application No. PCT/GB 91/01413 III. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Document, with indication, where appropriate, of the relevant passages Relevant to Claim No EP, Al, 0331474 (THE WELLCOME FOUNDATION LIMITED) 6 September 1989, see the whole document EP, Al, 0304492 (SUMITOMO CHEMICAL COMPANY, LIMITED) 1 March 1989, see the whole document Patent Abstracts of Japan, Vol 13, No 115, C578, abstract of JP 63-290803, publ 1988-11-28 SUMITOMO CHEM CO LTD WO, Al, 9003112 (NC DEVELOPMENT, April 1990, see page 12, 2:nd paragraph; 29, 31 WO, Al, 9003111 (NC DEVELOPMENT, April 1990, see page 9, line 13; page 13 page 15, line 1 INC.) page 16, 17, INC.) line 28 1-10 1-10 1-10 1-10 1-10 1-10 1-10 WO, Al, 8903176 (DOW CH April 1989, see claims 1, 9, WO, Al, 8903175 (DOW CH April 1989, see claims 1, 8, 11 page 18, lines 9-11 EMICAL COMPANY LIMITED) EMICAL COMPANY LIMITED) page 16, lines 1-29; i orm PCT/ISA/Z10 (extra sheot) (January 1985) i'j g- ANNEX TO THE INTERN iuNAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO.PCT/GB 91/01413 SA 50701 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 27/09/91 The European Patent office is in no way liable for theseparticulars which are merely given for the purpose ol information. Patent document Publication Patent family Publication cited in search report date member(s) date WO-A1- 8607525 31/12/86 AU-B- 595225 29/03/90 AU-D- 6126386 13/01/87 EP-A- 0259340 16/03/88 GB-A-B- 2176706 07/01/87 GB-A- 2095109 29/09/82 NONE WO-A1- 8807326 06/10/88 AU-B- 605855 24/01/91 AU-D- 1493488 02/11/88 EP-A- 0354212 14/02/90 JP-T- 2502821 06/09/90 US-A- 5037653 06/08/91 WO-A- 90/03111 05/04/90 WO-A- 90/03112 05/04/90 EP-A1- 0331474 06/09/89 AU-B- 610717 23/05/91 AU-D- 3291489 22/09/89 WO-A- 89/07888 08/09/89 EP-A1- 0304492 01/03/89 WO-A- 88/06842 22/09/88 WO-Al- 9003112 05/04/90 AU-B- 605855 24/01/91 AU-D- 1493488 02/11/88 EP-A- 0354212 14/02/90 JP-T- 2502821 06/09/90 US-A- 5037653 06/08/91 WO-A- 88/07326 06/10/88 WO-A- 90/03111 05/04/90 EP-A- 0439477 07/08/91 WO-Al- 9003111 05/04/90 AU-B- 605855 24/01/91 AU-D- 1493488 02/11/88 EP-A- 0354212 14/02/90 JP-T- 2502821 06/09/90 US-A- 5037653 06/08/91 WO-A- 88/07326 06/10/88 WO-A- 90/03112 05/04/90 EP-A- 0436651 17/07/91 WO-A1- 8903176 20/04/89 EP-A- 0381691 16/08/90 JP-T- 3501845 25/04/91 JP-T- 3501846 25/04/91 WO-A- 89/03175 20/04/89 WO-A1- 8903175 20/04/89 EP-A- 0381691 16/08/90 For more details about this annex: see Official Journal of the European patent Office, No. 12/82 EPO FORM P0479 as, 1 _I_ i la~ -r ,i: -r ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO.PCT/GB 91/01413 SA 50701 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 27/09/91 The European Patent office is in no way liable for theseparticulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date WO-A1- 8903175 20/04/89 JP-T- 3501845 25/04/91 JP-T- 3501846 25/04/91 WO-A- 89/03176 20/04/89 For more details about this annex: see Official Journal of the European patent Office, No. 12/82 EPO FORM P0479 r