Milled Submicron Organic Biocides With Narrow Particle Size Distribution, and Uses Thereof

Abstract

A method of milling substantially insoluble solid organic biocides to form a micron or sub-micron product having a narrow particle size distribution is presented. The milling involves wet milling of the organic biocide with high density milling media having a diameter between 0.1 mm and 0.8 mm, preferably between 0.2 mm and 0.7 mm, and a density equal to or greater than 3.8 g/cc, preferably greater than 5.5 g/cc, in a ball mill using between about 40% and 80% loading of the mill volume with milling media, and having the organic biocide suspended in an aqueous milling liquid which comprises one or more surface active agents. The milling speed is preferably high, for example from about 1000 rpm to about 4000 rpm. The milled product can be used in foliar applications at a lower effective dosage than prior art formulations, can be used in improved antifouling paint formulations, and can be used in new applications such as the direct injection of solid organic biocide particulates in wood to act as a long lasting wood preservative.

1 : A method of preparing a particulate organic biocide product comprising the steps of:
 1) providing an solid substantially water-insoluble organic biocide, an aqueous liquid comprising a surface-active agent, and a milling media to a mill, wherein the milling media comprises an effective amount of milling beads having a density of about 3.5 grams/cm 3  or greater, and a diameter between about 0.1 mm and about 0.8 mm; and   2) milling the material for a time sufficient to obtain a milled organic biocide product having a mean volume particle diameter d 50  of about 0.05 microns to about 1 micron.   
     
     
         2 : The method of  claim 1  wherein the milling media comprises an effective amount of milling beads comprising zirconia and having a density or about 5.5 grams/cm 3  or greater. 
     
     
         3 : The method of  claim 1  wherein 10% or more by weight of the milling media comprises zirconium oxide-containing milling beads having a diameter between about 0.1 and about 0.7 mm. 
     
     
         4 . (canceled) 
     
     
         5 : The method of  claim 4  wherein the milled organic biocide product has a diameter d 90 , such that 90 volume percent of the product has a diameter of the d 90  or less, of less than 4 times the d 50 . 
     
     
         6 - 7 . (canceled) 
     
     
         8 : The method of  claim 3  wherein the product has a mean volume particle diameter d 50  of between about 0.1 microns and about 0.3 microns. 
     
     
         9 - 11 . (canceled) 
     
     
         12 : The method of  claim 1  wherein at least 25% by weight of the milling media consists of milling beads having a diameter between about 0.1 mm and about 0.8 mm which consist essentially of zirconium oxide, doped zirconium oxide, stabilized zirconium oxide, or mixture thereof. 
     
     
         13 : The method of  claim 1  wherein at least 5% by weight of the milling media consists of milling beads having a diameter between about 0.2 mm and about 0.7 mm and a density greater than about 5.5 grams per cubic centimeter. 
     
     
         14 - 16 . (canceled) 
     
     
         17 : The method of  claim 3  wherein the milling media consists essentially of milling beads having a diameter between about 0.3 and about 0.7 mm and a density of 5.5 g cc or greater, and wherein the milling media occupies between about 40 and 80 volume % of the mill. 
     
     
         18 : The method of claim  16  wherein the mill speed is between about 1000 and about 4000 rpm. 
     
     
         19 : The method of  claim 1  wherein at least 10% by weight of the milling media consists of steel milling beads having a diameter between about 0.2 and about 0.7 mm and a density of 6 g/cc or greater. 
     
     
         20 . (canceled) 
     
     
         21 : The method of  claim 1  wherein the milling media comprises steel. 
     
     
         22 - 30 . (canceled) 
     
     
         31 : The method of  claim 1  wherein the organic biocide is selected from the group consisting of Metaldehyde, triphenyltin hydroxide, Maneb, Mancozeb, Zineb, Ziram, and Ferbam, and wherein the milled organic biocide product has a volume mean diameter d 50  between about 0.1 and 0.3 microns and a d 90 , such that 90 volume percent of the product has a diameter of the d 90  or less, of less than about 3 times the d 50 . 
     
     
         32 - 33 . (canceled) 
     
     
         34 : A method of treating crops comprising:
 milling an organic biocide product according to claim  28 , wherein the milled organic biocide product further comprises the surface active agents;   adding the milled organic biocide product to water to form slurry; and   spraying the slurry over the crops.   
     
     
         35 . (canceled) 
     
     
         36 : The method of  claim 1  wherein the organic biocide is selected from the group consisting of imidazolinones, sulfonylureas, triazolopyrimidine sulfonamides, aryloxyphenoxy propionates, triazines, chloroacetanilides, pyrazoles, and diphenyl ethers. 
     
     
         37 - 39 . (canceled) 
     
     
         40 : A method of treating crops comprising:
 milling an organic biocide product according to  claim 36 , wherein the milled organic biocide product further comprises the surface active agents;   adding the milled organic biocide product to water to form slurry; and   spraying the slurry over the crops.   
     
     
         41 : The method of  claim 1  wherein the organic biocide is selected from the group consisting of amitraz, azinphos-ethyl, azinphos-methyl, benzoximate, fenobucarb, gamma-HCH, methidathion, deltamethrin, dicofol, dioxabenzafos, dioxacarb, dinobuton, endosulfan, bifenthrin, binapacryl, bioresmethrin, chlorpyrifos, chlorpyrifos-methyl, EPNethiofencarb, cyanophos, cyfluthrin, tetradifon, cypermethrin, tralomethrin, bromophos, N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-xylidene, 2,4-parathion methyl, bromopropylate, butacarboxim, butoxycarboxin, chlordimeform, phosalone, chlorobenzilate, phosfolan, chloropropylate, phosmet, chlorophoxim, promecarb, fenamiphos, quinalphos, resmethrin, temephos, pirimiphos-ethyl, tetramethrin, pirimiphos-methyl, xylylcarb, profenofos, acrinathrin, propaphos, allethrin, propargite, benfuracarb, propetamphos, bioallethrin, pyrachlofos, bioallethrin S, tefluthrin, bioresmethrin, terbufos, buprofezin, tetrachlorinphos, chlorfenvinphos, tralomethrin, chlorflurazuron, triazophos, chlormephos, pyrachlofos, tefluthrin, terbufos, tetrachlorinphos, cycloprothrin, betacyfluthrin, cyhalothrin, cambda-cyhalothrin, tralomethrin, alpha-cypermethrin, triazophos, beta-cypermethrin, cyphenothrin, demeton-5-methyl, dichlorvos, disulfoton, edifenphos, empenthrin, esfenvalerate, ethoprophos, etofenprox, etrimphos, fenazaquin, fenitrothion, fenthiocarb, fenpropathrin, fenthion, fenvalerate, flucythrinate, flufenoxuron, tau-fluvalinate, formothion, hexaflumuron, hydroprene, isofenphos, isoprocarb, isoxathion, malathion, mephospholan, methoprene, methoxychlor, mevinphos, permethrin, phenothrin, phenthoate, benalaxyl, biteranol, bupirimate, cyproconazole, carboxin, tetraconazole, dodemorph, difenoconazole, dodine, dimethomoph, fenarimol, diniconazole, ditalimfos, ethoxyquin, myclobutanil, etridiazole, nuarimol, fenpropidin, oxycarboxin, fluchloralin, penconazole, flusilazole, prochloraz, imibenconazole, tolclofos-methyl, myclobutanil, triadimefon, propiconazole, triadimenol, pyrifenox, azaconazole, tebuconazole, epoxyconazole, tridemorph, fenpropimorph, triflumizole, 2,4-D esters, diclofop-methyldiethatyl, 2,4-DB esters, dimethachlor, acetochlor, dinitramine, aclonifen, ethalfluralin, alachlor, ethofumesate, anilophos, fenobucarb, benfluralin, fenoxapropethyl, benfuresate, fluazifop, bensulide, fluazifop-P, benzoylprop-ethyl, fluchloralin, bifenox, flufenoxim, bromoxynil esters, flumetralin, bromoxynil, flumetralin, butachlor, fluorodifen, butamifos, fluoroglycofen ethyl, butralin, fluoroxypyr esters, butylate, carbetamide, chlornitrofen, chlorpropham, cinmethylin, clethodim, clomazone, clopyralid esters, CMPP esters, cycloate, cycloxydim, desmedipham, dichlorprop esters, flurecol butyl, fluorochloralin, haloxyfop, ethoxyethyl, haloxyfop-methyl, ioxynil esters, isopropalin, MCPA esters, mecoprop-P esters, metolachlor, monalide, napropamide, nitrofen, oxadiazon, oxyfluorfen, pendimethalin, phenisopham, phenmedipham, picloram esters, pretilachlor, profluralin, propachlor, propanil, propaquizafop, pyridate, quizalofop-P, triclopyr esters, and tridiphane. 
     
     
         42 : The method of  claim 41  wherein the milled organic biocide product has a volume mean diameter d 50  between about 0.1 and 0.3 microns and a d 90 , such that 90 volume percent of the product has a diameter of the d 90  or less, of less than about 3 times the d 50 . 
     
     
         43 - 44 . (canceled) 
     
     
         45 : A method of treating crops comprising:
 milling an organic biocide product according to  claim 41 , wherein the milled organic biocide product further comprises the surface active agents;   adding the milled organic biocide product to water to form slurry; and   spraying the slurry over the crops.   
     
     
         46 - 54 . (canceled)