PL167656B1 - Insecticide preparation PL - Google Patents

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.

Description

The invention relates to insecticidal formulations which are two-phase formulations which contain two incompatible active ingredients.

The spectrum that an anhydrous pesticide formulation, that is, one that does not contain an aqueous phase, may be juxtaposed with a second incompatible phase that includes the second pesticide. The advantage of this is that the incompatible pesticides can be incorporated in the same formulation.

The present invention relates to a two-phase formulation, the first phase of which comprises a first active ingredient, a stabilizer, and optionally an emulsifier or wetting or dispersing agent, and a carrier or solvent for the active ingredient; and the second phase immiscible with the first comprises the second active ingredient and, optionally, an emulsifier or wetting or dispersing agent, and a carrier or solvent for the second active ingredient.

167 656

The insecticide preparation according to the invention is a two-phase preparation in which the first phase of the preparation follows the formula:

mass of oil phase Moi-, _ RLN (¼) -l- (Z) ln (AX ^B) and the mass of the stabilizer ^_ M _standing biiizator ^E C ^T L is less than or equal to 15, A = 700376, B = -1, 51, C = 0.8472.

Mok. j — j lUedn ^- ° relative relative molar mass f ^ sy of oil, -MSta ^j ; i ₁ z.ator ^{is -} mean molar mass of mtabn ^ ator ,!

_v _ ljt x- er where Y is the molar solubility index of the preparation, defined as the minimum Feet mole ⁽ fczy - ^ οζ-βί, which may be ^p zsrcofd sdbiUtot. subteton ^ aez Umoto mai ^- yja ^c iliyatora, po ^y verorildef ^ ża w ^ wj ^ s ^ waorza wyłducz onyjoeik & żty eo zpusbcdolnik ^b oóryniema ^r and u ⁿ d of ^a funnel MTEM pfraκn: m ρη ^^ ζ.-η ^ ιη ejmor ^c eΓ ^s ClOtym irowibsa j ako składóik aktymnymetylkcłjtóropiiyfosurzz sOtbiUoatco :! (cited ^ e ^ w C ^k niebmg ^e o (or TOB ^- rndek zwUżającytob dis ^ rgmjący orao nośnUf ΗΛ rozpybpczalo ^g of sUfoktadoito ζ wnegua ^ro ^ d ^ ^g a Uwamemieszaj as ^g e u ο ρ ^ ^^ f ^ jιpawibrgts ^of uskładnik ^ ^ wz rtywnytotometrynęw eMddztó -ym ^m ewantualme zmg ^- gajoflub ^- rade ^k owUtojod ⁰ jub or dis ^ agi-jaty orrw ntonik lu ^g aar ^d nrddzalg ⁱⁿ : ^nt u ustdito i ^ tywnugo.

W ^ better first ^- s ^ ada ^ a.tywgy is dissolved or dispersed in the first phase, levz ^ y pk ^ nte p ^ o. kesto ⁰ - ^-00 . wówrops wduUfik otejesi raw-re

Bottom ^g a mtosya o ^bl et ^o e ^ a: ^^ ffó. towiera dredges octótoik acts of exfoliation - zczogy or dispersed ^f w (kzgtój phase. Ko ^ s fmz pizowsza phara ms mitwoa o ^ r water zdra ^ foom jub ^ wrclna.

Hewoszyi, the second active ingredient is preferably physically and / or chemically incompatible, I know the tedas^aty: ^^^, that is, nbedno ^ -oilne ^ t^aeand^withnikaa^aboutP.^gsnake^witho w^bo ^⁽^ ίtfg (^ i ^ r zwyMe ^ ρΖο-ζζριο.ο w ^ wa nn stz^yUnośćtó⁰ toytwsmość of the second s.Mnika^rg^withkgic^pFr Parladjoo^ear^gn^rb (Ktywpyw piaowsobj^funtil^jabout mbreby. tba ^ tosytob sokodliwyw ^ sias^- pso, Pregowo^andnaop^jthey know^οsporzadzejff^aboutre^dora1 mod ^ ηϊ ^ εΐζ — οϊβο w / mtodsi.^fijⁱⁿmaybe ^ e-eac wsre^dmd (seams (wosprg^ands Pwst^andzh^andtotal of missing sMKtóikijw ^^ n.ch preparations; preparas^- inb^olat^and you always posed^volkn^dgtd.kjsgodrpżg^andema.for k-kteto and^kvol^ywa^y mind © o © by^sl2^gand a^andf-b^andola^atictoliεlyk ibia^-about^oic ^ n © rzyom b^kactive^οκ^οηοθ. r ^ ¢ ^ <^^dabout^g wyoⁿPz^pk ap selected a msectbyols. foósa p^r (.razto-doi is able to increase its compatibility^-1 with other active groups. freparat o ^ r ^ ir^fy aaw © seniekom^gand^κCand^coerk^padm⁰ⁱ active absences from piπpgo combrnsor^anddg-^sflZdnsttyny [y⁰) -Oi-o^fjggo-3-fandksy^ybnay^jD-w⁰R. (- aiSi3-i2,2-diblΌCovinyl) -2.2-^0tmethylog^r0dupsopicot]^yfyaboks y^-an^j b organophosphate mrecticide 0, 0-dimethyl-0-3,5,6-trichloro-2-pyridylthiopho sPaseaem (mCylocdtgi'Ootryifof).

K © κgoos Cz ^ ie ^ y kotayrgtiz gOyrbergowada in the second phase. The stabilizer creates a barrier on the counties of the counties ϋS (pZzyοdysgeraowaaą pSsrwrdO fzzątdruoo oasis.t ^^ yil · Ozo ^ 1g ^ l Oorzoftp1g te $ (a] Worlolem create-sym ΠΟ ^ η; on-ykSad ο rlsa-s sί, which aroZοb opóygisjocyoOpcowćw © wmfadzie fozpylοke-wokoatslcgi, oz0dwown _- oοoajsrom aptzió paientowymgr .004. Wosayotoie jesno oUio ho d-erwszuszęOkvrz; oOF _{S y} y _y jsie not więZsrz ilgfpOs or mó.aOzo That brcznepzOsbsw © nlawybrane zgrupymstylawzr, stylish Wiflaossmrjylowpd of dfomucdlaiOwcz (e.g. .fluonil or ahibraf with iakimi zzdsww © _f eamtfoszdlUmezddrlrfymi odgrapealkohatowaf o coog-jnlek of atomswfg1a _P d ζπιΡΥ hyiOΌksytdwet) ϊΖο (^ (irtówikanol n © jj (iwrz ^ ^ ^ mkaw. constant ϋΚοο ^ ορίπζε nfCS Kosbystnκ (οs t aK] o0bkae4-ο-, a ^ Όρ ₀ ζ ₀ ζζ noSοcraOanj jtr ^ i. Hok ^ sadoł ^ irn- llZliegoaysó woież jKroiWkiOujo cetya-riektwylfjoiej jKroiWkiOujo cetya-riewylodwyliego osf iąóWodecane-t -olu (WkohοlrWοrο1owy- ikdw riS-lZοO fftostedsοiawzjesjzuοojoiz fay bwelrjacy. HsotzaoOsb-t-ol-dateówn1eżοdpfwiedni _j 1 ^^^ 1 cw © ledrożsry. Snnzrodkl jwdrzfoe fUm owy-dk © isksrl cwdośc-obrκ _t Zr- _P g _S OsaZ _CZ ο1o _i

167,656 amine, 1-heptadecylamine and 1-octadecylamine. Less preferred film-forming agents include hexadecan-2-ol, 1,2-hexadecanediol, methyl stearate, stearyl acetate, methyl palmitate and 1,2-octadecanediol. May employ N-alkoxyalkanols, for example, CH3 (CH2) 2lOC ₂ H4OH, CH3 (CH2) 2lOC3H6OH, CH3 (CH2) 17OC2H4OH or CH3 (CH2) l ₅ OC2H4OH, and oxyethylene-docosanol and mixtures of any of the compounds mentioned above film-forming .

The emulsifier may be any convenient compound or mixture of compounds. Cationic emulsifiers can be used, but tend to irritate the eyes of the user. Anionic emulsifiers such as calcium dodecylbenzene sulfate (CDBS) or sodium diisopropyl naphthalene sulfonate (SDNS) may also be used, but are not as effective in stabilizing the emulsion while maintaining evaporation retarding properties. Preferably the emulsifier is a nonionic compound or a mixture of nonionic compounds having an HLB (hydrophilic / lipophilic balance) of 6-20, preferably 8-18. Suitable compounds include polyoxyethylene stearyl ethers (PSE), polyoxyethylene monolaurates (PEM), polyoxyethylene monooleates (PMO), sorbitan monooleate (SMO), nonylphenol ethoxylate (NPE), polyethylene glycol (PEG) and blends of oleyl ethoxylate (10 mole) and PEG20 glycerin oleate (De / PGO).

The following emulsifiers are available:

Shortcut trade name Provider OE / PGO TegoplantEM11 Th.Goldschmidt Ltd. PSE Brij 72, Brij 76, Brij 78 ICI Specialty Chemicals PEM Tween 20 ICI Specialty Chemicals SMO Span 80 ICI Specialty Chemicals PMO Tween 80 ICI Specialty Chemicals NPE Ethylan, KEO, 55, BV Lankro Chemicals Limited CDBS Arylate CA Lankro Chemicals Limited SDN Aerosol OS Cyanamid GB Ltd.

The solvent for the first phase preferably has a relatively low molecular weight, namely less than about 200. Suitable compounds include aromatic hydrocarbons, lower alkyl esters, lower ketones, lower alkanols and lower alkanes, lower being C1-12, preferably C1-10 and especially preferably C1-8.

Particular solvents include the following compounds, all from Exxon Chemicals Limited:

Solvesso 150 - aromatic hydrocarbon solvent (C9 to C11) distilling in the temperature range 190 to 210 ° C.

Solvesso 200 - aromatic hydrocarbon solvent (C10 to C12) distilling in the temperature range of 226 to 290 ° C.

Exxate 700 - 99% pure heptyl acetate, or Odorless kerosene - a mixture of high-boiling non-aromatic hydrocarbons containing paraffins and naphthenes, distilling in the temperature range of 180 to 270 ° C.

The first phase may contain more than one active ingredient (optionally with a synergist or enhancer which is considered the active ingredient in the formula below), more than one solvent, more than one emulsifier and / or more than one stabilizer, together with the others ingredients such as fragrances and dyes. In a preferred aspect, the first formulation phase follows the formula:

weight of the oil phase Mpie, weight of the stabilizer “Mct _? ha; _{73 | n} r

Exp + CIn (AX ^B) 167 656 where L is less than or equal to 15, A = 700376, B = -1.51, C = 0.8472, Molej is the weight average of the relative molar mass of the oil phase, M Stabilizer is the average molar mass of stabilizer, and _Y _ (Lower) 1.8 X γ where Y is the molar solubility index defined as the minimum number of moles of the oil phase that will dissolve the stabilizer divided by the number of moles of the stabilizer, provided that any solvent that is excluded in the formula above is there is no liquid phase at 27 ° C under atmospheric pressure.

The oil phase is a non-aqueous liquid phase that will contain one or more active ingredients, a solvent for them, and in some cases an emulsifier.

For the avoidance of doubt and to clarify the ambiguities that may arise when printing and copying the description, it is noted that the relation symbol in the formula means less than or equal to, Exp means the exponent of what follows in parentheses, In means the natural logarithm, i.e. loge, L is divided by 4, X is divided to the B power, B is negative (minus 1.51), and in the definition of X, Molej is raised to the 1.8 power.

Preferably the L is less than 12, 10 or 8 and most preferably less than 5. The spray jet of the distilled water stream has an L value of about 26 and most conventional dilute formulations are about 22-30. In the formulations according to the invention, L may be set to a desired value in order to calculate the desired ingredient ratios.

Moles, average molecular weight times oil, is the weight average, that is, used to calculate the relative ratios of the components.

The value of Y, namely the molar solubility index of the formulation, can be determined empirically by preparing a series of mixtures at 40 ° C with different oil to alkanol ratios, allowing the mixtures to cool to 27 ° C, then allowing the cooled mixtures to cool for at least 48 hours at 27 ° C and the mole determination of the amount of oil phase that is needed to completely dissolve the given amount of retardant, in moles. The first of the two values is then divided by the second to give Y.

Preferred film-forming compounds include saturated C16-20 alkanols such as hexadecan-1-ol and saturated C16-18 amines.

Preferred solvents and emulsifiers for the first phase are as previously described in European Patent 331474, which is hereby incorporated by reference.

The use of the formulations according to the invention will depend on the nature of the active ingredients contained in the formulation, but the formulations will normally be used to control pest infestation such as insects, mites or worms or microbial infestation. The dose of active ingredients employed will correspond to the doses of those active ingredients conventionally used for the purpose in question.

A preferred formulation according to the invention contains 20% methylchlorpyrifos and 1% deltamethrin and cetyl alcohol as a stabilizer. The formulation is useful for the treatment of stored crops such as cereals, in particular against the action of harmful insects of the order Coleoptera (e.g. Anobium, Ceutorhynchus, Rhynchophorus, Cosmopolites, Lissorhoptus, Meligethes, Hypothenemus, Hylesinus, Acalymma, Lema, Psylliodes, Gonocinephalarsa, Gonocinephalliodesa, , Dermalepida, Heteronychus, Phaedon, Tribolium, Sitophilus, Oryzaephilus, Rhyzopertha, Prostephanus, Cryptoletes, Trogoderma, Typheae, Diabrotica, Anthonomus or Anthrenus spp), Lepidoptera (e.g. Ephestia, Mamestra, Earioplusia, Plusia, Pierisoplusinia, , Sitotroga, Corcyra, Laphygma, Agrotis, Amathes, Wiseana, Tryporysa, Diatrae, Sporganothis, Cydia, Archips, Plutella, Chilo, Heliothis, Spodoptera or Tineola spp.), Diptera (e.g. Musca, Aedes, Anopheles, Culex, Glossina Simulium, Stomoxys, Haematobia, Tabanus, Hydrotaea, Lucilia, Chrysomia, Callitroga, Dermatobia, Gasterophilus, Hydroderma, Hylemila, Atherigona, Chlorops, Phytomyza, Ceratitis, Li riomyza and Melophagus spp.), Phthi6

167 656 raptera (Malophaga, e.g. Damalina spp. And Anoplura, e.g. Linognathus and Haematopinus spp.), Hemiptera (e.g. Aphis, Bemisia, Phorodon, Aeneolamina, Empoasca, Parkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococus, Lygus, Helopeltis , Dysdercus, Oxycarenus, Nezara, Aleurodes, Triatoma, Psylla, Mysus, Megoura, Phylloxera, Adelves, Niloparvata, Nephrotetix or Cimex spp.), Orthoptera (e.g. Locusta, Gryllus, Schistocerca or Acheta spoptera.), Dictyatellaa (e.g. , Periplaneta or Blatta spp.), Hymenoptera (e.g. Athalia, Cephus, Atta, solenopsis or Monomorium spp.), Isoptera (e.g. Odontotermes 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.) And Thysanoptera (e.g. Thrips tabaci). Harmful mites include ticks, e.g., members of the genera Boophilus, Ornithodorus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermacentor and Anocentor, and mites and scabies such as Acarus, Tyrophagus, Glycyphagus, Tetranyus, Psoroptes, Psoroptes, Notoedes, Choroptes. Eutrombicula, Demodex, Panonychus, Bryobia, Eriophyes, Blaniulus, Polyphagotarsonemus, Scutigerella and Oniscus spp and Periplaneta, Blatta, Blattella and Lapisma.

The formulations according to the invention can be prepared as follows:

1) The first compound is active in the solvent to form, or the smn is the first phase.

2) The stabilizer dissolves in the first phase.

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

4) The surfactants are dispersed either in the first part of the second phase containing the second active ingredient.

5) At this point, there are no dispersions in the expensive phase, which differ from the other active ingredient.

6) The erggic rawieric residue of the ruggi skUdi-iik kt ^ t ^ wzya measured with i ^ emi ^ in the first phase and the second part of the second phase.

Step (6) is not conducted under high shear conditions. Therefore, the second part of the second phase containing the second active ingredient is easily combined with the first part of the second phase and results in a dispersion or emulsions of the first phase in the second phase.

The invention will now be described in detail by means of the following examples. Example 1 describes formulations according to the invention containing pyrethroid and an organophosphate insecticide. Example II shows the results of tests demonstrating the stability of the formulations according to the invention. Example III shows the results of biological tests on various harmful insects.

Example I. Preparations

Components % wt / wt methylchloropieyfoe 19.15 solvesso 150 19.15 water (djmineralirowrnr) 51.40 emulsifiers 2.00 deltamethrin (20% SC) 5.20

Deltamethrin (20% SC) contains deltamethrin (20%) in water with surfactant, thickeners and biological preservatives.

The oil phase was prepared by dissolving cetyl alcohol in a solution of methylchloropyrifos in Solvesso 150 at a temperature of up to 50 ° C. The emulsifiers were added to water at 60 ° C and the resulting aqueous solution was cooled to 50 ° C (water phase). The oil phase was added to the water phase at 50 ° C with vigorous stirring and the resulting emulsion was cooled to 20 ° C. A 20% aqueous deltamethrin suspension was added while stirring at 20-25 ° C.

167 656

Example II. Stability tested

Tests were carried out on the stability of the active ingredients in the formulation according to the invention (A) and in a two-phase formulation that does not contain a stabilizer (B).

Results for formulation A

A formulation of methylchlorpyrifos / deltamethrin with a film former was prepared in a similar manner to that described in Example 1 above.

Typical stability data: Methylchlorpyrifos (CPMe) tests (± 10% digits)

Time in months 25 ° C 38 ° C 50 ° C (M) Initially 100 100 1100 3M or 4M 101 103 103 6M 102 100 103 12 M. 101 94 101

Typical Stability Data: Deltamethrin (DLTM)

Time in months 25 ° C 38 ° C 50 ° C (M) Initially 100 100 1 (X) 3M or 4M 96 99 98 6M 97 103 103 12 M. 98 94 76

Preparations B - results

Preparation of methylchlorpyrifos / deltamethrin without film forming agent. Typical stability data: CPME

Time in months 25 ° C 38 ° C 50 ° C (M) Initially 100 100 100 3 M 112 106 71

Typical DLTM Stability Data:

Time in months 25 ° C 38 ° C 50 ° C (M) Initially 1100 100 100 3 M 77 77 16

The results show formulations (B) without a film forming agent that are relatively unstable.

Example III. Biological tests.

Procedure. Suitably diluted with water, the formulation was sprayed onto 400 t of grain at Wail, Victoria. It was applied to the grain stream during inversion at a rate of one liter per ton. The treated cereals were sampled at intervals by means of a vacuum test. Biotests were performed by keeping 100 adult insects per 150 or 300 g of grain. After incubation for 3 weeks at 25 ° C and 55-60% relative humidity, the insects were screened out and the mortality was counted. The grain was then screened at 7, 9, and 11 weeks to remove and count mortality in the mature progeny.

(1) 0.24: 4.9 mg / kg deltamethrin: methylchlorpyrifos

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Tested insects Storage months after treatment % mortality the amount of offspring Suppression offspring % living killed Sitophilus ory- 0 100 0 4 99.8 zae 1.5 100 0 0 100 3 100 0 0 100 4.5 100 0 0 100 6 100 0 0 100 9 100 0 0 100 Rhyzopertha do- 0 100 0 0 100 minica 1.5 100 0 0 100 3 100 0 0 100 4.5 100 0 0 100 6 100 0 0 100 9 100 0 0 100 Tnbolium casta- 0 100 0 0 100 neume 1.5 100 0 1 99.7 3 100 0 0 100 4.5 100 0 1 99.5 6 100 0 4 99.0 9 100 0 0 100 Queensland 0 100 0 0 100 Tribolium casta- 1.5 100 0 2 97 neume 3 99 0 0 100 279 4.5 99 0 1 99.7 6 100 0 4 99.0 9 95 0 0 100 Oryzaephilus su- 0 100 0 0 100 rinamensis 1.5 100 0 0 100 3 100 0 2 99.7 4.5 99 0 0 100 6 95 0 1 99.9 9 100 0 0 100

The results show good insect pest control when stored for up to 9 months after treatment.

Publishing Department of the UP RP. Circulation of 90 copies

Price PLN 1.50

Claims (6)

Patent claims 1. An insecticide preparation which is a two-phase preparation, characterized in that the first phase of the preparation meets the formula: mass of the oil phase <Molar mass of the oil phase _< May rlnO / b) + (with htAX ^B) ~ | stabilizer mass “C ^J where L is less than or equal to 15, A = 700376, B = -1.51, C = 0.8472. Mdej is the weight average of the relative molar molar mass of the oil, Mstabiizator is the average molar mass of the stabilizer, and _Y _ (Molej) 1.8 X- γ where Y is the molar solubility index of the formulation, defined as the minimum number of moles of the oil phase that will dissolve the stabilizer divided by the number of moles of the stabilizer, provided that any solvent which does not have a liquid phase at 27 ° C under atmospheric pressure is excluded in the above formula and which contains methylchloropyrifos as active ingredient and a stabilizer and optionally an emulsifier or wetting or dispersing agent and a carrier or solvent for the active ingredient, and a second immiscible phase with the first phase, it contains as active ingredient deltamethrin in an aqueous system and, optionally, an emulsifier or wetting or dispersing agent, and a carrier or solvent for the active ingredient. 2. A formulation according to claim 1 The process of claim 1, wherein the first phase is a water-immiscible phase. 3. The formulation according to claim 1 The process of claim 1, wherein the second phase is an aqueous phase. 4. A formulation according to claim 1 The process of claim 1, wherein the first and second active ingredients are physically and / or chemically incompatible when in the same phase. 5. The formulation according to claim 1 The method of claim 1, wherein L is less than 5. 6. A formulation according to claim 1 The process of claim 1, wherein the stabilizer is saturated C16-20 alkanol or saturated C16 -samine.