WO1999033340A1 - Concentres agrochimiques emulsionnables - Google Patents

Concentres agrochimiques emulsionnables Download PDF

Info

Publication number
WO1999033340A1
WO1999033340A1 PCT/US1998/027358 US9827358W WO9933340A1 WO 1999033340 A1 WO1999033340 A1 WO 1999033340A1 US 9827358 W US9827358 W US 9827358W WO 9933340 A1 WO9933340 A1 WO 9933340A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkoxylated
acid
methyl
weight
pyridyl
Prior art date
Application number
PCT/US1998/027358
Other languages
English (en)
Inventor
Stanley J. Kostka
Rennan Pan
Original Assignee
Aquatrols Holding Co., Inc.
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
Priority claimed from US09/212,994 external-priority patent/US6200961B1/en
Application filed by Aquatrols Holding Co., Inc. filed Critical Aquatrols Holding Co., Inc.
Priority to CA002317542A priority Critical patent/CA2317542C/fr
Priority to EP98964873A priority patent/EP1043927A1/fr
Priority to AU20099/99A priority patent/AU752966B2/en
Publication of WO1999033340A1 publication Critical patent/WO1999033340A1/fr

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
    • 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
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • A01N33/22—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group having at least one oxygen or sulfur atom and at least one nitro group directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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 instant invention relates to highly concentrated, low volatile organic compound (low VOC) aqueous agrochemical compositions and methods for preparing same.
  • the invention also relates to bioefficaciously enhanced organophosphorous insecticidal formulations comprising said active and low volatile organic compound (low VOC) compositions; processes for preparing same; and methods of use.
  • agrochemical actives When agrochemical actives are relatively water soluble, preparing, storing, and shipping same in a commercially acceptable form can be a relatively simple matter. However, many, if not most, agrochemical actives are not very water soluble and formulators are constantly using their ingenuity to find means for preparing these materials in stable formulations that deliver maximum loading of active ingredient per unit volume to the end-user.
  • One means of doing this is to prepare dry formulations such as wettable dispersible granules (WDG's) or wettable powders (WP's) encapsulated, for example, in water soluble bags or containers.
  • WDG's wettable dispersible granules
  • WP's wettable powders
  • Insecticides miticides, aphicides, fungicides, bacteriocides, acaricides, nematicides
  • these pesticides will be generically referred to for conciseness as "insecticides” as the term “insecticidally” will similarly represent generically miticidally, nematicidally, etc.
  • Insecticides are expected to display ideal properties of a wide array including broad-spectrum activity concomitant with safety to beneficial insects, low mammalian and fish toxicity, and sufficiently long residual action yet with insignificant, harmless residue levels.
  • ECs emulsiflable concentrates
  • aromatic organic solvent systems such as xylene or kerosene are used to solubilize the pesticidal compound of interest.
  • surfactants are also added to the insecticide-solvent compositions to form emulsiflable concentrates.
  • the surfactant-emulsifiers interact with the insecticides in a number of ways both before and during actual use, i.e., application to the locus.
  • the surfactants often a pair of nonionic and anionic surfactants, can initially disperse and/or emulsify the insecticide in the solvent or in an inert carrier media and may also act as spreader, sticker, stabilizer, wetting agent, and defoamer.
  • the surfactant composition may affect the rate of drying of a droplet on a surface and the nature of a residue liquid or crystal.
  • Lubetzky, et al. in EP publication numbers 669,078 and 670,113 have disclosed the use of rosin and rosin derivatives that are insoluble in water to "plasticize” certain pesticides and thus to prepare pesticidal emulsions in water (EW's) and emulsiflable concentrates (EC's).
  • composition having from greater than 25 to about 60 weight percent alkoxylated rosin acids and from about 40 to less than 75 weight percent alkoxylated fatty acids with about 9 to 20 alkoxy moieties per molecule of acid; and c) at least one nonionic surfactant.
  • alkoxylated acid compositions possess very unique solvent characteristics with respect to certain relatively water insoluble pesticides.
  • This invention relates to stable, low VOC pesticidal emulsiflable concentrates
  • a pesticide having a melting point of 120°C or less, preferably 110° C or
  • a solvent for said pesticide comprising an alkoxylated fatty acid and rosin acid composition having from greater than about 25 to about 60 weight percent alkoxylated rosin acids and from about 40 to less than about 75 weight percent alkoxylated fatty acids — the weight percents of the fatty acids and rosin acids being based on the total weight of the alkoxylated acid composition wherein the alkoxylated composition contains an average molar addition of from about 9 to 20 alkoxy moieties per molecule of acid; and c) at least one nonionic surfactant.
  • the instant invention also relates to the discovery that said alkoxylated fatty/rosin acid formulations not only provide extremely stable, highly loaded solvent systems, but that these formulations also significantly enhance the bioefficacy of specific organophosphorous insecticidal compounds.
  • water-soluble fatty acid/rosin acid alkoxylated compositions possess very unique solvent characteristics with respect to certain water insoluble pesticides. Specifically, it has been discovered that water insoluble pesticides having low to medium melting points can be melted and readily dissolved in a low VOC water-soluble solvent prepared by highly alkoxylating a mixture of fatty acids and rosin acids; preferably a tall oil mixture.
  • a preferred method of preparing emulsiflable concentrates of these components is to melt the organophosphorous insecticide and dissolve same in the highly ethoxylated mixture of the fatty acids and rosin acids; preferably a tall oil mixture.
  • the primary fatty acids useful in the process of this invention are the C 14 to C 20 unsaturated acids, especially the fatty acids selected from the group consisting of oleic, linoleic, conjugated linoleic acids, palmitic, stearic, and mixtures thereof.
  • the primary rosin acids useful in the process of this invention are the C 19 - C 20 aromatic acids, especially the rosin acids selected from the group consisting of abietic, neoabietic, dehydroabietic, tetrahydroabietic, palustric, pimaric acids and mixtures thereof.
  • the final acid compositions whose components are subsequently alkoxylated either prior to being mixed together to form the composition or after the acid composition mixture is present, comprise from greater than about 25 to about 60 weight percent alkoxylated rosin acids, preferably from 30 to 40 weight percent alkoxylated rosin acid; and from about 40 to less than about 75 weight percent, preferably from about 60 to about
  • the water-soluble alkoxylated compositions should contain an average molar addition of from about 6 to about 20 alkoxy moieties per molecule of acid; preferably from about 9 to about 16.
  • the rosin acids can be obtained individually from natural products such as wood and gum resins and the fatty acids can be obtained individually, for example, from natural oils and fats such as olive oil, peanut oil, butter fat, cottonseed, soybean and so on, the fatty acid/rosin acid compositions of this invention are preferably obtained from certain tall oil products.
  • the pine tree is the source of tall oil which is liberated when wood is converted to paper pulp by the sulfate or Kraft process.
  • black liquor alkaline digestion liquor
  • Rosin soaps and fatty acid soaps are skimmed off of this black liquor and acidification releases free rosin and fatty acids.
  • This mixture was originally called Tallolja (Swedish for pine oil) and the term “tall oil” was eventually adapted as a standard by the United States.
  • palmitoleic acid [1.5%]; and to a small extent, higher molecular weight saturated acids such as arachidic (C 20 ), behinic (C 22 ), lignoceric (C 24 ) and cerotic (C 26 ) acids, C 20 and higher molecular weight unsaturated and polyunsaturated acids, and small amounts of low boiling point monobasic and dibasic acids.
  • higher molecular weight saturated acids such as arachidic (C 20 ), behinic (C 22 ), lignoceric (C 24 ) and cerotic (C 26 ) acids, C 20 and higher molecular weight unsaturated and polyunsaturated acids, and small amounts of low boiling point monobasic and dibasic acids.
  • rosin acids in crude tall oil are similar to those occurring in wood and gum rosin and typically consist mainly of abietic acid [30 - 40%] in equilibrium with its isomer neoabietic acid [4 - 20%], palustric acid [7%], dehydroabietic acid [5 - 17%], pimaric acid [8 - 16%], with dehydroabietic and tetrahydroabietic acids comprising 2 to 28%.
  • fatty acid/rosin acid compositions of this invention are alkoxylated, i.e., polyoxyalkylene esters are prepared, by using art-recognized, standard condensation techniques readily available; known to those skilled in the art; and described in numerous publications, for example, on pages 142 to 170 of chapter 5 of the book "Nonionic Surfactants" by W. B. Satkowski, S. K. Huang, and R. L. Liss, edited by M. J. Schick, Lever Bros. Co. Research Center, Edgewater, New Jersey (Marcel Dekker, Inc., New York). Typical procedures are set forth in U.S. Patent Nos. 2,586,767 and 2,610,966.
  • the organic carboxylic acids may be either directly esterified with alkylene oxide or through a reaction with polyalkylene glycol intermediates.
  • the alkylene oxides which may be used to prepare the nonionic monofunctional polyoxyalkylene esters or polyalkylene glycol intermediates include ethylene oxide, propylene oxide and butylene oxide. Tetrahydrofuran may also be used.
  • Preferred alkylene oxides are ethylene oxide and propylene oxide. When both of these oxides are utilized, they may be added simultaneously or in sequence to prepare statistic or block polymer surfactants.
  • the alkylene oxides for example, ethylene oxide, may also be used alone.
  • Pesticides which are useful in the formulations of this invention are those that are useful in the formulations of this invention.
  • Suitable pesticides can be selected for example from the following classes of pesticidally active substances: acetanilides nitroxylenes benzoates organophosphorous compounds benzofurans oxidiazoles chlorinated hydrocarbons phenoxyphenoxyalkane carboxylic acid derivatives hydroxybenzonitriles pyrethroids and imidazoles triazoles nitroanilines
  • Suitable acetanilides are in particular compounds of the type described in United States patent numbers 3,442,945 and 3,547,620, especially 2-chloro-2'6'-diethyl-N- (methoxymethyl)-acetanilide (alachlor).
  • Suitable benzoates are in particular compounds of the type described in Great Britain patent number 1,247,817 especially 3-chloro- -ethoxyimino-2,6-dimethyloxybenzyl benzoate (benzoximate).
  • Suitable benzofurans are in particular compounds of the type described in Great Britain patent number 1,271,659, especially 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methane sulfonate (ethofiimesate).
  • Suitable chlorinated hydrocarbons are in particular compounds of the type described in United States patent number 2,799,685, especially 6,7,8,9,10,10- hexachloro-l,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzo-dioxathiepin-3-oxide (endosulfan).
  • Suitable hydroxybenzonitriles are in particular compounds of the type described in United States patent numbers 3,397,054 and 4,332,613, especially the esters of 3,5-dibromo-4-hydroxyphenyl cyanide (bromoxynil) and 3,5-diiodo-4-hydroxyphenyl cyanide (ioxynil).
  • Suitable imidazoles are in particular compounds of the type described in Great Britain patent number 1,469,772, especially N-propyl-N-[2-(2,4,6- trichlorophenoxy)-ethyl]-lH-imidazole-l-carboxamide; also compounds described in United States patent number 3,658,813, especially l-[2-(2,4-dichlorophenyl)-2-(2- propenyloxy)-ethyl]-lH-imidazole (imazalil).
  • Suitable nitroanilines are in particular compounds of the type described in United States patent number 3,257,190, especially N- butyl-N-ethyl-2,6-dinitro-4-trifluoromethyl-aniline (benfluralin) or 2,6-dinitro-N,N- dipropyl-4-trifluoro-methyl aniline (trifluralin).
  • Suitable nitroxylenes are in particular compounds of the type described in United States patent number 3,385,862, especially N- l(l-ethylpropyl)-2,6-dinitro-3,4-xylidine (pendimethalin).
  • Suitable organophosphorous compounds are in particular compounds of the type described in United States patent number 3,244,586, especially O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)-phosphorothioate (chlorpyrifos ethyl) and O,O-dimethyl-O-(3,5,6-trichloro-2-pyridyl)-phosphorothioate (chlorpyrifos methyl); also the compounds described in Great Britain patent number 974,138, especially l,3-dithiolan-2-ylidene-phosphorimidate (phospholan); also the compounds described in United States patent numbers 3,230,230 and 3,240,668, especially S- [ ⁇ 5-methoxy-2-oxo- 1 ,3 ,4-thiadiazol-3 -(2H)-yl ⁇ -methyl ⁇ -O,O- dimethylphosphoro-dithioate (methidathion); also the compounds described in United States patent
  • Suitable oxidiazoles are in particular compounds of the type described in United States patent number 3,385,862 especially 3- [2,4-dichloro-5-(l-methyl-ethoxy)-phenyl]-5-(l,l-dimethyl-ethyl)-l,3,4-oxadiazole-2- (3H)-one (oxadiazon).
  • Suitable phenoxy-phenoxy-alkane-carboxylic acid derivatives are in particular compounds of the type described in West German patent number 2,136,828 and 2,223,804, especially methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propanoate (diclofop methyl).
  • Suitable pyrethroids are in particular compounds of the type described in Great Britain patent number 1,413,491 especially (3-phenoxy-phenyl)-methyl-3-(2,2- dichloroethenyl)-2,2-dimethyl-cyclopropane-carboxylate (permethrin) and cyano-(3- phenoxy-phenyl)-methyl-3-(2,2-dichloroethenyl)-2,2-dimethyl-cyclopropane-carboxylate (cypermethrin); also 2-methyl-biphenyl-3-yl-methyl-(Z)-(IRS)-cis-3-(2-chloro-3,3,3- trifluoro-prop-1-enyl) - 2,2-dimethyl-cyclopropane-carboxylate (bifenthrin); also the compounds described in United States patent number 4,062,698, especially cyano-(3- phenoxy-phenyl)-methyl-(RS)-2-(4-ch
  • Suitable triazoles are in particular compounds of the type described in Israel patent number 73,450, especially 2-(4-chlorophenyl)-2-(lH)-(l,2,4-triazole-l-yl-methyl) hexanitrile (myclobutanil); also the compounds described in Great Britain patent number 1,522,657, especially l-[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2-yl-]-methyl-lH- 1,2,4-triazole (propiconazole).
  • the preferred pesticidal actives include dithiopyr (S,S' -dimethyl 2- (difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridine dicarbothioate; chlorpyrifos (0,0-diethyl 0-(3,5,6-trichloro-2-pyridyl)-phosphorothioate; iprodione (3- (3 ,5-dichlorophenyl)-N-( 1 -methylethyl)-2,4-dioxo- 1 -imidazolidine carboxamide); and oxyfluorfen (2-chloro-l-(3-ethoxy-4-nitrophenoxy)-4-(trifluoro methyl benzene).
  • Organophosphorous compounds are antichlolinesterase chemicals which damage or destroy chlolinesterase, the enzyme required for nerve function in the animal body.
  • Organophosphorous insecticides owing primarily to their ester nature, offer fundamental advantages in that they can be easily degraded hydrolytically, enzymatically, or biologically.
  • Organophosphorous compounds including those disclosed in U. S. Patent 3,244,586 and specifically those with a halogen substitution, are known to be extremely useful as insecticides and are especially adapted to be employed as active toxicants in compositions for the control of a number of mite, insect, bacterial, and fungal organisms, such as beetles, ticks, worms, aphids, flies, roaches, cattle grubs, screw worms, trash fish, snails, ascarids, nematodes, roundworms, and Rhizoctonia solani (a plant pathogenic fungus).
  • mite, insect, bacterial, and fungal organisms such as beetles, ticks, worms, aphids, flies, roaches, cattle grubs, screw worms, trash fish, snails, ascarids, nematodes, roundworms, and Rhizoctonia solani (a plant pathogenic fungus).
  • the organophosphorous insecticides of the instant invention are preferably the phosphorothioates, phosphorodithioates, phosphoroamidates, phosphoroamidothioates, and phosphonothioates which have melting points below about 120°C.
  • organophosphorous compounds are of the following formulas:
  • X is each individually O or S
  • R 1 is substituted or unsubstituted, branched or unbranched lower alkyl, aryl, or aralkyl;
  • R 3 is XR 4 or NHR 5 ;
  • R 4 is substituted or unsubstituted lower alkyl, lower alkylene, vinyl, aryl, aralkyl, cyanoaryl, carboalkoxyalkyl, alkoxyalkyl, alkoxyaryl, alkoxycarbonylalkyl, aminocarbonyalkyl, alkylcarbamoylalkyl, alkylthioalkyl, or alkylthioaryl;
  • R 5 is H, acetyl, or lower alkyl
  • R 6 is lower alkyl, dioxanyl, or thiodi-p-phenylene wherein, in the specification and claims of this disclosure "aryl” includes heteroaryl compounds and “substituted” includes halogen substitutions. Also, in the present specification and claims, the term “lower alkyl” and “lower alkoxy” refer to radicals of from 1 to 8 inclusive, carbon atoms.
  • the aryl radicals are selected from the group consisting of substituted or unsubstituted phenyl, pyridinyl, pyrimidinyl, cyanophenyl, alkylthiophenyl, benzotriazinyl, phthalimidinyl, oxobenzoxazolyl, oxothiadiazolyl, carbalkoxybenzyl, morpholinocarbonylalkyl, nitrophenyl, oxobenzopyranyl, quinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, pyrazolyl, triazolyl, and thiadiazolinonyl.
  • the most preferred insecticides of the instant invention are selected from the group consisting of: O, O-diethyl 0-3.5-dibromo-6-chloro-2-pyridyl phosphorothioate,
  • O-methyl O-3,5-dichloro-2-pyridyl isopropyl phosphoroamidothioate, O-methyl O-3,5-dibromo-2-pyridyl methyl phosphoroamidothioate, O-ethyl O-3,5-dibromo-2-pyridyl methyl phosphoroamidothioate, O-ethyl O-3,5-dichloro-2-pyridyl methyl phosphoroamidothioate, O-methyl O-3,5-dichloro-2-pyridyl methyl phosphoroamidothioate,
  • the very most preferred insecticide for use in the instant invention is O,O-diethyl O-(3,5,6-trichloropyridine-2-yl) phosphorothioate also known as chlorpyrifos.
  • organophosphorous compounds are known to be very effective for the control of many parasitic organisms, particularly those found on the roots or aerial portions of growing plants inclusive of aphids, mites, plant pathogens, and insects. These compounds are effective at low concentrations, against chewing and sucking types of insects, such as southern armyworm (Prodema eridania), California red scale (Aonidiella aurantil), and Mexican bean beetle (Epilachna yarivestis). They are also extremely useful for the impregnation of soil in nematocidal concentrations for the control of nematodes such as the root-knot nematode. An additional advantage to the use of these compounds is that they can be applied to soil in and around growing vegetation in amounts required for pest control without significant injury to plants.
  • organophosphorous compounds which are particularly useful in this invention are those that have melting points below about 120°C; preferably below about 110°C; and most preferably below about 90°C.
  • the aforementioned solid insecticides are melted and dissolved in a low VOC water-soluble solvent prepared by highly alkoxylating a mixture of fatty acids and rosin acids; preferably a tall oil mixture.
  • the nonionic surfactants useful in the formulations of this invention must have significant solubility in water.
  • the H.L.B. of the nonionic surfactants should preferably be in the solubilizer/wetting agent range of from about 12 to about 20.
  • nonionic materials are the following:
  • block-polymeric polyether glycols obtained, for example, by the addition of ethylene oxide on a condensation product of propylene oxide with propylene glycol;
  • alkoxylated alkyl phenols i.e., alkylphenol-polyalkylene oxide condensates which are condensation products of alkylphenols with at least one alkylene oxide;
  • polysiloxanes preferably the alkoxylated polysiloxanes
  • the preferred nonionic surfactants are the condensation products of aliphatic alcohols with at least one alkylene oxide and the alkoxylated alkyl phenols, especially the aliphatic ethoxylates and the alkylphenol polyethoxylates; the alkoxylated triglycerides such as ethoxylated and ethoxylated-propoxylated castor oil; and the alkoxylated sorbitol fatty esters.
  • aliphatic alcohol ethoxylates which are aliphatic alcohol polyethylene oxide condensates of aliphatic alcohols wherein the aliphatic chain contains from about 4 to about 20, preferably about 5 to about 12 carbon atoms in either a straight chain or branched chain configuration and condensed with ethylene oxide, the said ethylene oxide being present in amounts equal to 2 to 50 moles of ethylene oxide per mole of aliphatic alcohol; preferably 5 to 25, most preferably 8-15.
  • the aliphatic alcohol may be of primary, secondary or tertiary structure; preferably of a secondary structure.
  • the most preferred alcohol ethoxylate is an ethoxylated trimethyl secondary nonanol.
  • Examples of the ethoxylated alkyl phenols include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol, diamyl phenol condensed with about 9 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mold of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • nonionic surfactants of this type include the IGEPAL series of nonionics, e.g., those sold under the trademarks CO-630 and DAP-9 by Rhodia Inc.
  • n is from about 2 to about 6; a is from about 8 to about 25; and b is from 0 to about 25; and the oxyalkylene groups may be random or block mixtures; y is from 0 to about 5; x is from about 1 to about 5; and R is selected from the group consisting of hydrogen, C, - C 4 alkyl, and a C,-C 4 alkyl ester; or
  • A is a linear or branched alkyl having about 6 to about 30 carbon atoms
  • G is a glycol moiety of the formula -R' (OCH 2 CH 2 ) m OR" wherein R' is a divalent alkylene group having about 2 to about 6 carbon atoms; R" is selected from the group consisting of hydrogen, C, - C 4 alkyl, and a C, - C 4 alkyl ester; m is about 8 to about 100; y is 0 to about 5; x is about 0.1 to about 2.5; and z is about 0.1 to about 5.0.
  • the primary components of the low VOC pesticidal emulsiflable concentrates of the instant invention have the following concentration ranges: the pesticide is present from 10 to 60 weight percent, preferably from 10 to 40 weight percent; the alkoxylated fatty acid/rosin acid mixture from 20 to 60 weight percent, preferably from 30 to 55 weight percent; and the nonionic surfactant from 15 to 45 weight percent, preferably from 20 to 40 weight percent; all weight percents being based on the total weight of the emulsion concentrate.
  • the liquid pesticide, alkoxylated fatty acid/rosin acid mixture, and nonionic surfactant concentrates can be used to prepare stable oil-in-water emulsions.
  • the preferred concentration ranges of the components based on the total weight of the aqueous emulsion are as follows: the pesticide should be present from 1 to 50 weight percent; the alkoxylated fatty acid/rosin acid composition should be present from 2 to 55 weight percent; and the nonionic surfactant from about 1.5 to 35 weight percent.
  • the water can be present up to about 78 weight percent.
  • the ability of the concentrates of this invention to form stable emulsions when diluted with water is especially important for the dispersion stability allows for a homogeneous distribution of active ingredients on application targets, which assists in enhancing biological efficacy.
  • the agrochemical compositions according to the invention may optionally comprise: a) an anionic surfactant, such as i) partial sulfate and phosphate esters of polyoxyalkylene or (ii) carboxylate surfactants and their salts; and/or b) other nonionic surfactants, for example, polyoxyalkylene ethers of aliphatic alcohol having from 6 to 30, preferably from 10 to 20, and more particularly from 12 to 16 carbon atoms in the aliphatic residue; and/or c) a long chain carboxylic acid having from 10 to 25 carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and arachidic acid; and/or d) a lower alkanol ester of a long chain C, 0 - C 22
  • the agrochemical compositions of this invention may also comprise anti-freezing agents, anti-foam agents, compatibility agents, oxidation and UN. protectants, bactericides, and pH buffering agents.
  • Anti-foam agents decrease and/or prevent foaming when the solution containing the pesticidally-active formulation is agitated or sprayed.
  • Compatibility agents function to allow and maintain an emulsification of two or more ingredients that would otherwise separate when mixed.
  • Buffering agents function to moderate the pH of the water in the tank solution.
  • the concentrated formulations of this invention can be prepared preferably by melting one or more of the water-insoluble pesticidally-active ingredients and physically blending this molten material with the alkoxylated fatty acid/rosin acid solvent.
  • the nonionic surfactant composition and any optional ingredients are then added to the mixture using standard emulsiflable concentrate preparation methods well known in the art.
  • the sequence of addition is not a critical feature of the invention.
  • the ingredients can also be premixed prior to the application of heat.
  • the undesirable pests can be controlled by contacting the organism, its habitat, and/or its food supply prior to ingestion with a pesticidally effective amount of a formulation comprising the emulsiflable concentrates of this invention containing the agrochemical active.
  • a formulation comprising the emulsiflable concentrates of this invention containing the agrochemical active.
  • the term "comprising the emulsiflable concentrate(s)” is meant to include the emulsion concentrate(s) of this invention neat or after being diluted with water. These liquid formulations can be applied to living plants without substantial injury to the foliage thereof.
  • the compositions of the instant invention are applied as emulsiflable concentrates, the toxicant can be present in a concentration of from about 10 to about 60 percent by weight based on the total weight of the emulsion concentrate.
  • the exact concentration of the organochemical pesticide employed in an aqueous emulsion for application to the pest, its habitat or food can vary provided a pesticidal dosage of toxicant is supplied either on the organism, to its environment, or in its food. This dosage of toxicant is primarily dependent upon the susceptibility of a particular organism to the specific pesticide compound.
  • the emulsiflable concentrates of this invention are readily emulsified in water to form sprays containing the active toxicant in any commercially desired amount. Good results are obtained with the aqueous emulsiflable concentrates of this invention so diluted with water to form, for example, spray mixtures that the toxicant is present in the final diluted aqueous composition from about 0.5 to 2000 parts or more by weight per million.
  • Rosin acid-fatty acid (RFA) compositions having approximately the following characteristics:
  • composition abietic acid (21-22 weight percent), palustric acid (2-3 weight percent),
  • pimaric acid (7-8 weight percent), various isomers of the abietic, palustric and primaric
  • dimer and higher fatty acids (17-18 weight percent) are ethoxylated such that a series of ethoxylated rosin acid-fatty acid compositions are prepared having a molar
  • Varying amounts of dithiopyr, a pre-emergent herbicide, are blended with the
  • composition as a control.
  • the samples are heated in an oven to a temperature above the
  • melting point of the dithiopyr i.e., in the range of from about 65°C - 70°C.
  • chlo ⁇ yrifos is an
  • the dithiopyr a pre-emergent herbicide
  • the oxyfluorfen a pre-and post-
  • Example II Four samples are prepared by mixing in a weight ratio of 4:1, the RFA (9EO) composition of Example I with nonionic surfactant, namely, ethoxylated diamylphenol.
  • nonionic surfactant namely, ethoxylated diamylphenol.
  • the average ethylene oxide molar addition per mole of the diamylphenol is 9.
  • Dithiopyr is blended into the RFA (9EO)/nonionic surfactant solvent system at various concentrations; heated; agitated; and cooled to room temperature as in Example I.
  • the samples are stored for three weeks and solubility/stability observations made at the end of that time. The results are as set forth in Table IV.
  • nonionic surfactant is present as a co-solvent/ solubility aid.
  • pesticidal loading levels can be increased and the stability of the overall formulations can be increased.
  • Example I 2) a nonylphenol ethoxylate (9EO Av.); and 3) a 4:1 (WeightiWeight) blend
  • the dithiopyr loading limit in the nonylphenol ethoxylate is about 10% in the rosin acid- fatty acid ethoxylate (16EO) about 20%; and in the rosin acid-fatty acid ethoxylate (16EO) - NP9 blend, it synergistically increased to about 25 weight percent.
  • Emulsifiable concentrates (EC's) of the instant invention with pesticidal compositions as indicated in Table VII below are prepared as in Example V. The compositions are then diluted with water in a 10 water to 1 EC ratio to form aqueous spray emulsions. Two commercial emulsifiable concentrates, both containing high
  • VOC's i.e., MICRO-FLO chlo ⁇ yrifos, a 2E emulsifiable concentrate trademark of the
  • Micro Flo Company and DIMENSION IE a trademark of Rohm & Haas for a 12.7 weight percent dithiopyr in a heavy aromatic petroleum naphtha emulsifiable concentrate, are similarly diluted to form aqueous spray emulsions.
  • the aqueous spray emulsions prepared from the low VOC emulsifiable concentrates of the instant invention exhibit improved stability as compared to standard, commercially available emulsifiable concentrates containing high VOC's.
  • VOC pesticidal compositions include reduced worker exposure to high VOC's; greater options for shipping formulated pesticides; advantageous labeling options; and decreased regulatory issues.
  • Formulations of chlo ⁇ yrifos in the ethoxylated fatty acid/rosin acid and/or ethoxylated fatty acid/rosin acid-nonionic surfactant solvent systems of this invention significantly reduce the odor of the pesticide in both the formulated emulsifiable concentrate and the diluted aqueous spray preparations. The odor reduction was apparent even when a low odor chlo ⁇ yrifos technical active material was used.
  • Rosin acid-fatty acid (RFA) compositions having approximately the following characteristics:
  • composition abietic acid (21-22 weight percent), palustric acid (2-3 weight percent),
  • pimaric acid (7-8 weight percent), various isomers of the abietic, palustric and primaric
  • ethoxylated rosin acid-fatty acid compositions are prepared having a molar addition of
  • ethoxylate i.e., Tergitol TMN-6, a trademark of Union Carbide for an ethoxylated
  • the mixture is heated in an oven to above the melting point of the chlo ⁇ yrifos,
  • the sample is well agitated and subsequently cooled to room temperature.
  • the low VOC, emulsifiable concentrate has the following formulation (in weight
  • Example IX The low VOC, emulsifiable chlo ⁇ yrifos concentrate of Example VIII, having about 2 pounds of chlo ⁇ yrifos per gallon hereinafter identified as Chlo ⁇ yrifos 2E, is diluted in water to form an aqueous spray composition.
  • Chlo ⁇ yrifos 2E formulation of the instant invention is applied at 1, 2, and 3 pounds of active ingredient per acre.
  • Dursban 4E a commercial chlo ⁇ yrifos insecticide formulation sold by The Dow Chemical Company is also applied at 1, 2, and 3 pounds of active ingredient per acre.
  • Orthene 75 S an acephate, i.e., O,S-dimethyl acetyl phosphoramidothioate insecticide formulation sold by the Valent U.S.A. Co ⁇ . is applied at 2.25 pounds active ingredient per acre. Control data, i.e., non-treated plot data is also monitored.
  • Mole Cricket damage ratings are determined prior to the treatment applications and subsequently at 1-2 week intervals. Treatments are applied with standard research plot equipment. The results of these trials are as indicated in Table VIII. Table VIII
  • the low VOC Chlo ⁇ yrifos 2E formulations of the instant invention consistently reduce Mole Cricket damage better than the commercial 4E Dursban formulation when applied at the same rate. More importantly, the low VOC Chlo ⁇ yrifos 2E formulation applied at the 2.0 lb. ai/acre rate, while using one-third less active ingredient, is as efficacious as the 3.0 lb. ai/acre treatment rate of the commercial Dursban formulation.
  • the low VOC Chlo ⁇ yrifos 2E formulation is significantly more efficacious than the same treatment rate of the commercial Dursban 4E formulation.
  • the target pest is the 3rd to 5th instars of the Southern Masked Chafer.
  • the Chloripyrifos 2E formulation of the instant invention is applied at 2 and 3 pounds of active ingredient per acre.
  • Dursban 4E chlo ⁇ yrifos insecticide formulation is also applied at the identical rates of 2 and 3 pounds of active ingredient per acre.
  • Control data i.e., non- treated plot data is also monitored.
  • the live grub damage ratings are determined prior to treatment application and subsequently at 1-2 week intervals. Treatments are applied with standard research plot equipment. The results of these trials are as indicated in Table IX.
  • the most effective chlo ⁇ yrifos formulation evaluated at this test location is the low VOC Chloripyrifos 2E formulation of the instant invention. Numbers of live larvae are significantly lower in plots receiving the 3.0 lb. ai/acre treatment rate of the low VOC formulation. Neither the 2 nor the 3 pound per acre treatment rates of the Dursban chlo ⁇ yrifos formulation provides commercially acceptable larvae control.
  • Orthene 75 S acephate insecticidal formulation is applied at 2.25 pounds of active ingredient per acre. Control data, i.e., non-treated plot data is also monitored.
  • Tawny Mole Cricket damage ratings are determined as in Example IX.
  • both the treatments i.e., the 2 and 3 pounds ai/acre of the low VOC Chlo ⁇ yrifos 2E formulations of the instant invention provide significantly better control than one achieves by similar rates with the commercial Dursban 4E chlo ⁇ yrifos insecticidal formulation.
  • the 3.0 lb. ai/acre low VOC Chlo ⁇ yrifos 3E formulation is significantly more efficacious than the 2.0 lb. /acre treatment rate.
  • the 2.0 lb. ai/acre treatment by the Chlo ⁇ yrifos 2E formulation of the instant invention is equivalent to the 3.0 lb. ai/acre rate of the commercial Dursban formulation. While the commercial Dursban formulation significantly reduces mole cricket damage as compared to the untreated control, performance is inferior to the low VOC Chlo ⁇ yrifos 2E formulation. Similar results are obtained at the other two locations where the low VOC chlo ⁇ yrifos formulations of the instant invention are evaluated.

Landscapes

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

Abstract

L'invention concerne un système de cosolvants de composés organiques peu volatils, utile pour préparer des concentrés émulsionnables de pesticides insolubles dans l'eau qui présentent un point de fusion inférieur à environ 120 degrés C, de préférence des insecticides organophosphoreux à point de fusion bas dans lesquels l'efficacité biologique de la substance active de l'insecticide est considérablement accrue. Le système de cosolvants comporte une composition d'acide gras alcoxylé soluble dans l'eau/ tensioactif non ionique d'acide résinique.
PCT/US1998/027358 1997-12-30 1998-12-23 Concentres agrochimiques emulsionnables WO1999033340A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002317542A CA2317542C (fr) 1997-12-30 1998-12-23 Concentres agrochimiques emulsionnables
EP98964873A EP1043927A1 (fr) 1997-12-30 1998-12-23 Concentres agrochimiques emulsionnables
AU20099/99A AU752966B2 (en) 1997-12-30 1998-12-23 Agrochemical emulsifiable concentrates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US7010197P 1997-12-30 1997-12-30
US60/070,101 1997-12-30
US09/212,994 US6200961B1 (en) 1998-12-16 1998-12-16 Concentrates of organophosphorous insecticides
US09/212,994 1998-12-16

Publications (1)

Publication Number Publication Date
WO1999033340A1 true WO1999033340A1 (fr) 1999-07-08

Family

ID=26750775

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/027358 WO1999033340A1 (fr) 1997-12-30 1998-12-23 Concentres agrochimiques emulsionnables

Country Status (4)

Country Link
EP (1) EP1043927A1 (fr)
AU (1) AU752966B2 (fr)
CA (1) CA2317542C (fr)
WO (1) WO1999033340A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6566305B1 (en) 1998-07-03 2003-05-20 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Phytosanitary treatment by foliar absorption using a modified oil
EP1649748A1 (fr) * 2003-07-18 2006-04-26 Mitsui Chemicals, Inc. Preparation d'une suspension aqueuse d'un bactericide a action foliaire
CN101703045B (zh) * 2009-12-01 2013-03-20 江苏龙灯化学有限公司 一种毒死蜱水分散组合物及其制备方法
CN111109284A (zh) * 2019-12-30 2020-05-08 江苏腾龙生物药业有限公司 一种含稻丰散的乳油
US20200345004A1 (en) * 2019-05-03 2020-11-05 Ingevity South Carolina, Llc Use of natural oils and their derivatives in agricultural formulations
WO2024052332A1 (fr) * 2022-09-08 2024-03-14 Lamberti Spa Nouveaux tensioactifs dérivés d'esters glycidyliques d'acides de colophane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2588318A (en) * 1949-02-07 1952-03-04 Monsanto Chemicals Water emulsifiable soil-poison concentrate
GB717279A (en) * 1952-06-16 1954-10-27 Herbert Lionel Sanders Toxicants containing emulsifiers
US3424847A (en) * 1963-11-18 1969-01-28 Witco Chemical Corp Toxicant concentrates containing acetonitrile and emulsifiers
JPH02108602A (ja) * 1988-10-19 1990-04-20 Toho Chem Ind Co Ltd 安定な水中油型乳濁状農薬組成物
EP0669078A1 (fr) * 1994-02-22 1995-08-30 Makhteshim Chemical Works Limited Concentrés émulsionnables de pesticides moins nuisibles pour l'environnement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2588318A (en) * 1949-02-07 1952-03-04 Monsanto Chemicals Water emulsifiable soil-poison concentrate
GB717279A (en) * 1952-06-16 1954-10-27 Herbert Lionel Sanders Toxicants containing emulsifiers
US3424847A (en) * 1963-11-18 1969-01-28 Witco Chemical Corp Toxicant concentrates containing acetonitrile and emulsifiers
JPH02108602A (ja) * 1988-10-19 1990-04-20 Toho Chem Ind Co Ltd 安定な水中油型乳濁状農薬組成物
EP0669078A1 (fr) * 1994-02-22 1995-08-30 Makhteshim Chemical Works Limited Concentrés émulsionnables de pesticides moins nuisibles pour l'environnement

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 314 (C - 0737) 5 July 1990 (1990-07-05) *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6566305B1 (en) 1998-07-03 2003-05-20 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Phytosanitary treatment by foliar absorption using a modified oil
EP1094704B1 (fr) * 1998-07-03 2003-10-22 Societe D'exploitation De Produits Pour Les Industries Chimiques-Seppic Traitement phytosanitaire par absorption foliaire utilisant une huile modifiee
EP1649748A1 (fr) * 2003-07-18 2006-04-26 Mitsui Chemicals, Inc. Preparation d'une suspension aqueuse d'un bactericide a action foliaire
EP1649748A4 (fr) * 2003-07-18 2010-08-25 Mitsui Chemicals Agro Inc Preparation d'une suspension aqueuse d'un bactericide a action foliaire
CN101703045B (zh) * 2009-12-01 2013-03-20 江苏龙灯化学有限公司 一种毒死蜱水分散组合物及其制备方法
US20200345004A1 (en) * 2019-05-03 2020-11-05 Ingevity South Carolina, Llc Use of natural oils and their derivatives in agricultural formulations
WO2020226825A1 (fr) * 2019-05-03 2020-11-12 Ingevity South Carolina, Llc Utilisation d'huiles naturelles et de leurs dérivés dans des formulations agricoles
CN114071996A (zh) * 2019-05-03 2022-02-18 英格维蒂南卡罗来纳有限责任公司 天然油和其衍生物在农业制剂中的用途
CN111109284A (zh) * 2019-12-30 2020-05-08 江苏腾龙生物药业有限公司 一种含稻丰散的乳油
WO2024052332A1 (fr) * 2022-09-08 2024-03-14 Lamberti Spa Nouveaux tensioactifs dérivés d'esters glycidyliques d'acides de colophane

Also Published As

Publication number Publication date
AU752966B2 (en) 2002-10-03
CA2317542C (fr) 2007-11-13
EP1043927A1 (fr) 2000-10-18
AU2009999A (en) 1999-07-19
CA2317542A1 (fr) 1999-07-08

Similar Documents

Publication Publication Date Title
Foy Adjuvants: terminology, classification, and mode of action
JP4255283B2 (ja) マイクロエマルジョン化可能な農薬組成物
CA2269823C (fr) Microemulsion et procede
US6451731B1 (en) Stable concentrated pesticidal suspension
JP2008534684A (ja) 安定な農薬濃縮物及び最終用途乳剤
US11980193B2 (en) Natural oil pesticidal compositions
CN102088846A (zh) 用于农业的表面活性剂共混物
US5407920A (en) Treatment of wood and timber with pesticidal formulations
EA013077B1 (ru) Гербицидная композиция
US6039966A (en) Agrochemical emulsion concentrates
KR100835473B1 (ko) 유기인 조성물
EP2260075B1 (fr) Compositions de tensioactifs
CA2317542C (fr) Concentres agrochimiques emulsionnables
US6200961B1 (en) Concentrates of organophosphorous insecticides
EP1608220B1 (fr) Preparations pesticides
CA2383763C (fr) Suspension pesticide concentree stable
KR100350922B1 (ko) 제초제조성물
BG64330B1 (bg) Течна форма на етил-(z)-2-хлоро-3-[2-хлор-5-(4,5,6,7- тетрахидро-1,3-диоксоизоиндолдион-2-ил)фенил]акрилат
US20050244357A1 (en) Oil-containing emulsifiable formulations containing active agents
JP4578943B2 (ja) 農薬組成物
GB1562908A (en) Insecticidal compostions
CA3096436A1 (fr) Compositions pesticides presentant des caracteristiques physiques ameliorees
WO1990003112A1 (fr) Lutte antiparasitaire
WO2002035932A1 (fr) Compositions de concentres colloides emulsionnables
JPH06227909A (ja) 殺虫組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

ENP Entry into the national phase

Ref document number: 2317542

Country of ref document: CA

Ref country code: CA

Ref document number: 2317542

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 20099/99

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1998964873

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1998964873

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998964873

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 20099/99

Country of ref document: AU