US00876 5697B2

(12) United States Patent (10) Patent No.: US 8,765,697 B2 Wilson et al. (45) Date of Patent: *Jul. 1, 2014

(54) PESTICIDE COMPOSITIONS EXHIBITING 6,001,981 A 12/1999 DeAmicis et al. ENHANCED ACTIVITY 6,090,399 A 7/2000 Ghosh et al. 6,143,526 A 11/2000 Baltz et al. 6,455,504 B1 9, 2002 Lewer et al. (75) Inventors: Stephen L. Wilson, Indianapolis, IN 6,585,990 B1 7/2003 Huang (US); Lei Liu, Carmel, IN (US); James 6,733,802 B1 5/2004 Moorty et al. D. Thomas, Fishers, IN (US); Raymond 6,919,464 B1 7/2005 Crouse et al. E. Boucher, Jr., Lebanon, IN (US); 6,927.210 B1* 8/2005 Thompson et al...... 514, 28 6,955,818 B1 10/2005 Hacket et al. James E. Dripps, Carmel, IN (US); 2003, OO82236 A1 5/2003 Mathiowitz et al. Margaret S. Kempe, Greenfield, IN 2003. O108585 A1 6/2003 Roe et al. (US) 2003. O138500 A1 7/2003 Parker et al. 2005, 0112235 A1 5/2005 Shefer et al. (73) Assignee: Dow AgroSciences, LLC., Indianapolis, 2005/0203034 A1 9, 2005 Ahn et al. 2007/0020304 A1 1/2007 Tamarkin et al. IN (US) 2007/0104.750 A1 5/2007 Wilson et al. 2007/0280981 A1 12/2007 Birthsel (*) Notice: Subject to any disclaimer, the term of this 2008.0031832 A1 2/2008 Wakefield et al. patent is extended or adjusted under 35 2008. O108800 A1 5/2008 Podhorez et al. U.S.C. 154(b) by 114 days. This patent is Subject to a terminal dis FOREIGN PATENT DOCUMENTS claimer. DE 10037670 2, 2002 EP O111808 A2 6, 1984 (21) Appl. No.: 12/768,057 EP O3O3477 2, 1989 EP 0826376 A1 3, 1998 EP O877603 11, 1998 (22) Filed: Apr. 27, 2010 GB 92.9210 6, 1963 WO WO 88O3755 6, 1988 (65) Prior Publication Data (Continued) US 2010/O298247 A1 Nov. 25, 2010 OTHER PUBLICATIONS Related U.S. Application Data Getchell and BH Subramanyam A I:"Evaluation of a Dry Spinosad (60) Provisional application No. 61/214,952, filed on Apr. Formulation on Two Extruded Pet Foods for Controlling Four Stored 30, 2009. Product Insects' Biopesticides International, Koul Research Foun dation, vol. 3, No. 2, Jan. 1, 2007, pp. 108-116, XP007914136:ISSN: (51) Int. Cl. 0973-483X: *abstract “Pet Foods” p. 109 “Treatment of Pet Foods A6 IK3I/70 (2006.01) with spinosad’:p. 109-p. 110 “Discussion':p. 112-p. 114. (52) U.S. Cl. Demchak, R J et al: “Photostability of Abamectin/Zein USPC ...... S14/30 Microspheres' Journal of Agricultural and Food Chemistry, Ameri (58) Field of Classification Search can Chemical Society, US LNKD- DOI: 10.1021/JF960356N,vol. USPC ...... 536/7.1: 514/30 45, No. 1, Jan. 1, 1997, pp. 260-262, XP002457256 ISSN: 0021-8561 See application file for complete search history. Introduction; p. 260. Dog Food Analysis: “Purina One Adult Dog Chicken & Rice For (56) References Cited mula Internet Citation; Mar. 5, 2006, XP007914143 Retrieved from the Internet: URL: http://www.dogfooddnalysis.com/dog food re U.S. PATENT DOCUMENTS views/showproduct.php?product=258&cat=7 retrieved on Jul. 27. 2010. The whole document. 3,886,125 A 5, 1975 Chromecek 3,929,453 A 12/1975 Dimitri et al. (Continued) 4,056,610 A 1 1/1977 Barber, Jr. et al. 4,184.866 A 1, 1980 Dellicolli et al. Primary Examiner — Elli Peselev 4,244,728 A 1/1981 Dellicolli et al. 4,485,103 A 11, 1984 Pasarella (74) Attorney, Agent, or Firm — Carl D. Corvin; Maschoff 4497,793 A 2f1985 Simkin Brennan 4,557,755 A 12/1985 Takahashi et al. 4,622,315 A 1 1/1986 Dureja et al. (57) ABSTRACT 5,024,832 A 6, 1991 Omata et al. 5, 190,764 A 3, 1993 Chiba et al. Pest controlling compositions exhibiting enhanced pesticidal 5,202,242 A 4/1993 Mynderse et al. activity levels are disclosed. In one embodiment, a composi 5,227,295 A 7, 1993 Baker tion includes at least one pesticide, at least one proteinaceous 5,246,936 A 9/1993 Treacy et al. 5,362,634 A 11/1994 Boecket al. material and at least one polymeric material. In this embodi 5,436,355 A 7, 1995 Demchak ment, the composition exhibits enhanced pesticidal activity 5,529,772 A 6/1996 Lebo, Jr. levels compared to a composition dissimilar only in not hav 5,539,089 A 7/1996 Broughton et al. ing the at least one proteinaceous material and the at least one 5,571.901 A 11/1996 Beocket al. 5,591,606 A 1/1997 Turner et al. polymeric material. Still, alternative embodiment pesticide 5,670,364 A 9/1997 Mynderse et al. compositions exhibiting enhanced activity levels are dis 5,750,126 A 5, 1998 Smith et al. closed. 5,750.467 A 5, 1998 Shasha et al. 5,939,089 A 8, 1999 Wirtz et al. 6 Claims, No Drawings US 8,765,697 B2 Page 2

(56) References Cited International Search Report and Written Opinion of the International Searching Authority, PCT/US2010/001246. International Search Report, Written Opinion, and Preliminary FOREIGN PATENT DOCUMENTS Report on Patentability of the International Searching Authority, PCT/US 2006/042912. WO WO9203927 3, 1992 WO WO9628O23 9, 1996 R.J. Demchak, and R. A. Dybas; Photostability of Abamectin/Zein WO WO9639842 12/1996 Microspheres; J. Agric. Food Chem. 1997, 45, p. 260-262:Agricul WO WO9905250 2, 1999 tural Research and Development, Merck Research Laboratories. WO WO99.39576 A1 8, 1999 Latch, Douglas E., et al.; Aqueous Photochemistry of Triclosan, WO WOOO42990 T 2000 Formation of 2, 4-dichlorophenol, 2.B-dichlorodibenzo-p-dioxin WO WOO145513 6, 2001 and oligomerization products; Dept. CHem. University of Minne WO WO 03/003831 A1 1, 2003 sota; Environmental Toxicology and Chemistry, Mar. 2005, vol. 24. WO WO 03/030644 A1 4/2003 pp. 517-525. WO WO 2004/016252 A1 2, 2004 Biebel R., et al.; Action of pyrethrum-based forumulations against WO WO 2004/043147 A1 5, 2004 WO WO 2004/095926 11, 2004 grain weevils; International Journal of Pharmaceutics; Apr. 30, 2003, WO WO 2005/O13714 A1 2, 2005 vol. 256, pp. 175-181, XP002457258. WO WO 2005, O72695 A1 8, 2005 Nogueira, Costa G.H., Antiparasitic for Cattle Comprises Two WO WO 2007/031565 A2 3, 2007 Macrocylclic Lactones with Bensyl alcohol, Tocopherol and Olive WO WO 2007/053760 5/2007 Oil: Ins Pesquisa Em Saude Animal Ltda; Aug. 12, 2003. WO WO 2007/053760 A2 5/2007 Clements Pauletal.; Soil Sensitised Generation of Singlet Oxygen in WO WO 2007/126915 A1 11/2007 the Photodegradation of Biorsmethrin; School of Applied Chemistry, WO WO 2008/093347 8, 2008 Revised manuscript Aug. 12, 1991; accepted Sep. 15, 1991. WO WO 2008, 134819 A1 11, 2008 Palumbo, Maria C., et al.; On the Mechanism of Quenching of Singlet Oxygen by Chlorinated Phenolic Pesticides; Toxilogical and Envi OTHER PUBLICATIONS ronmental Chemistry; vol. 18, pp. 103-116. Martire, Daniel O., et al.; Singlet Molecular Oxygen (O2(1 Ag) International Preliminary Report on Patentability; PCT/US2010/ Production and Quenching by Hydroxybiphenyls; Chemosphere, OO1246. vol. 26, No. 9, pp. 1691-1701, 1993. International Preliminary Report on Patentability; PCT/US2010/ OO1238. * cited by examiner US 8,765,697 B2 1. 2 PESTICIDE COMPOSITIONS EXHIBITING In another embodiment, a composition includes from ENHANCED ACTIVITY about 2% to about 25% by weight of spinetoram, from about 15% to about 75% by weight of a proteinaceous material, and CROSS-REFERENCE TO RELATED from about 5% to about 70% by weight of a polymeric mate APPLICATIONS rial. In one aspect of this embodiment, the proteinaceous material includes egg albumin and the polymeric material The subject application claims priority to U.S. Provisional includes polyvinyl alcohol. Application No. 61/214,952 filed Apr. 30, 2009, the contents In one other embodiment, a composition includes from of which are incorporated herein by reference in their entirety. about 15% to about 60% by weight of spinetoram and from 10 about 30% to about 75% by weight of at least one polymeric FIELD OF THE INVENTION material. In this embodiment, the composition exhibits enhanced pesticidal activity levels compared to a composi The invention disclosed in this document is related to the tion dissimilar only in not having the at least one polymeric field of pesticides and their use in controlling pests. material. In one form of this embodiment, the at least one 15 pesticide is a photo-labile pesticide. In a particular form, the BACKGROUND OF THE INVENTION at least one pesticide is a spinosyn Such as spinetoram or spinosad. Pests cause millions of human deaths around the world In yet another embodiment, a method includes applying to each year. Furthermore, there are more than ten thousand a locus where control is desired an insect-inactivating amount species of pests that cause losses in agriculture. These agri of a pesticide composition. cultural losses amount to billions of U.S. dollars each year. Still, further embodiments, forms, features, aspects, ben Termites cause damage to various structures such as homes. efits, objects, and advantages of the present invention shall These termite damage losses amount to billions of U.S. dol become apparent from the detailed description and examples lars each year. As a final note, many stored food pests eat and provided. adulterate stored food. These stored food losses amount to 25 billions of U.S. dollars each year, but more importantly, DETAILED DESCRIPTION OF THE INVENTION deprive people of needed food. Many pesticide compositions have been developed over Throughout this document, all temperatures are given in time to destroy pests and alleviate the damages they cause. degrees Celsius, and all percentages are weight percentages These compositions are often applied to the environment in 30 unless otherwise stated. which the insects or other pests live or where their eggs are Pesticide compositions exhibiting increased stability and present, including the air surrounding them, the food they eat, enhanced pesticidal activity are described in this document. or objects which they contact. Several of these compositions More particularly, in one or more embodiments, the pesticide are vulnerable to chemical and physical degradation when compositions exhibit enhanced residual pesticidal activity. A applied to these environments. If these types of degradation 35 pesticide is herein defined as any compound which shows occur, the pesticidal activity of the pesticides can be adversely Some pesticidal or biocidal activity, or otherwise participates affected, commonly necessitating an increase in the concen in the control or limitation of pest populations. Such com tration at which the pesticides are applied and/or more fre pounds include fungicides, insecticides, nematocides, miti quent applications of the pesticides. As a result, user costs and cides, termiticides, rodenticides, molluscides, arthropodi the cost to consumers can escalate. Therefore, a need exists 40 cides, herbicides, biocides, as well as pheromones and for new pesticide compositions that exhibit increased stability attractants and the like. and enhanced activity compared to existing pesticide compo Examples of pesticides that can be included in the compo sitions when, for example, the pesticide compositions are sitions described herein include, but are not limited to, anti applied to an environment to control pests. biotic insecticides, macrocyclic lactone insecticides (for 45 example, avermectin insecticides, milbemycin insecticides, SUMMARY OF THE INVENTION and spinosyn insecticides), arsenical insecticides, botanical insecticides, carbamate insecticides (for example, benzofura The present invention concerns novel pesticide composi nyl methylcarbamate insecticides, dimethylcarbamate insec tions and their use in controlling insects and certain other ticides, oxime carbamate insecticides, and phenyl methylcar invertebrates. In one embodiment, a composition includes at 50 bamate insecticides), diamide insecticides, desiccant least one pesticide, at least one proteinaceous material and at insecticides, dinitrophenol insecticides, fluorine insecticides, least one polymeric material. In this embodiment, the com formamidine insecticides, fumigant insecticides, inorganic position exhibits enhanced pesticidal activity levels com insecticides, insect growth regulators (for example, chitin pared to a composition dissimilar only in not having the at synthesis inhibitors, juvenile hormone mimics, juvenile hor least one proteinaceous material and the at least one poly 55 mones, moulting hormone agonists, moulting hormones, meric material. In one form, the at least one pesticide is a moulting inhibitors, precocenes, and other unclassified insect photo-labile pesticide. In another form, the at least one pes growth regulators), nereistoxin analogue insecticides, nicoti ticide is a macrocyclic lactone insecticide. noid insecticides (for example, nitroguanidine insecticides, In a more particular form, the at least one pesticide is a nitromethylene insecticides, and pyridylmethylamine insec spinosyn, such as spinetoram or spinosad, the at least one 60 ticides), organochlorine insecticides, organophosphorus proteinaceous material includes at least one of bovine serum insecticides, oxadiazine insecticides, oxadiazolone insecti albumin, egg albumin, whey, gelatin or Zein and the at least cides, phthalimide insecticides, pyrazole insecticides, pyre one polymeric material includes at least one of polyvinyl throid insecticides, pyrimidinamine insecticides, pyrrole alcohol, polyvinyl pyrrolidone, a latex or a terpene polymer. insecticides, tetramic acid insecticides, tetronic acid insecti However, it should be appreciated that alternatives for the at 65 cides, thiazole insecticides, thiazolidine insecticides, thio least one pesticide, proteinaceous material and polymeric urea insecticides, urea insecticides, as well as, other unclas material are contemplated. sified insecticides. US 8,765,697 B2 3 4 Some of the particular insecticides that can be employed in fenozide, methyl bromide, methylchloroform, methylene the compositions described in this document include, but are chloride, metofluthrin, metolcarb, metoxadiaZone, not limited to, the following: 1,2-dichloropropane, 1.3 mevinphos, mexacarbate, milbemectin, milbemycin oxime, dichloropropene, abamectin, acephate, acetamiprid, mipafox, mirex, monocrotophos, morphothion, moxidectin, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, naftalofos, naled, naphthalene, nicotine, nifluridide, niten aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxy pyram, nithiazine, nitrilacarb, novaluron, noviflumuron, carb, alpha-cypermethrin, alpha-endosulfan, amidithion, omethoate, oxamyl, Oxydemeton-methyl, oxydeprofos, oxy aminocarb, amiton, amitraz, anabasine, athidathion, aza disulfoton, para-dichlorobenzene, parathion, parathion-me dirachtin, azamethiphos, azinphos-ethyl, azinphosmethyl, thyl, penfluron, pentachlorophenol, permethrin, phenkapton, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, 10 phenothrin, phenthoate, phorate, phosalone, phosfolan, phos benfiiracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, met, phosnichlor, phosphamidon, phosphine, phoxim, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, bioresmethrin, bistrifluron, borax, boric acid, boric acid, bro mfenVinfos, bromocyclen, bromo-DDT, bromophos, bro pirimiphos-methyl, potassium arsenite, potassium thiocyan mophosethyl, bufencarb, buprofezin, butacarb, butathiofos, 15 ate, pp'-DDT, prallethrin, precocene I, precocene II, pre butocarboxim, butonate, butoxycarboxim, cadusafos, cal cocene III, primidophos, profenofos, profluthrin, promacyl, cium arsenate, calcium polysulfide, camphechlor, carbano promecarb, propaphos, propetamphos, propoXur, prothi late, carbaryl, carbofuran, carbon disulfide, carbon tetrachlo dathion, prothiofos, prothoate, protrifenbute, pyraclofos, ride, carbophenothion, carbosulfan, cartap, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyre chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, thrin D, pyridubto, pyridalyl pyridaphenthion, pyriflu chlordimeform, chlorethoxyfos, chlorfeinapyr, chlorfenvin quinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, phos, chlorfluaZuron, chlormephos, chloroform, chloropi quassia, quinalphos, quinalphosmethyl, quinothion, rafox crin, chlorphoxim, chlorpraZophos, chlorpyrifos, chlorpyri anide, resmethrin, rotenone, ryania, Sabadilla, Schradan, sel foS-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin amectin, Silafluofen, silica gel, sodium arsenite, Sodium fluo II, cismethrin, cloethocarb, closantel, clothianidin, copper 25 ride sodium hexafluorosilicate, Sodium thiocyanate, acetoarsenite, copper arsenate, copper naphthenate, copper sophamide, spinetoram, spinosad, spiromesifen, spirotetra oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, mat, Sulcofuron, Sulfluramid, Sulfotep, Sulfuryl fluoride, Sul crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, profos, tau-fluvalinate, tazimcarb, IDE, tebufenozide, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cyper tebufenpyrad, tebupirimfos, teflubenZuron, tefluthrin, teme methrin, cyphenothrin, cyromazine, cythioate, DDT, decar 30 phos, TEPP, terallethrin, terbufos, tetrachloroethane, tetra bofuran, deltamethrin, demephion, demephion-O, deme chlorvinphos, tetramethrin, theta-cypermethrin, thiacloprid, phion-S, demeton, demeton-methyl, demeton-O, demeton thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodi O-methyl, demeton-S, demeton-S-methyl, demeton-S- carb, thiofanox, thiometon, thiosultap, thuringiensin, tolfen methylsulphon, diafenthiuron, dialifos, diatomaceous earth, pyrad, tralomethrin, transfluthrin, transpermethrin, triarath diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl 35 ene, triazamate, triaZophos, trichlorfon, trichlorimetaphos-3. dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dime trichloronat, trifenofos, triflumuron, trimethacarb, triprene, fluthrin, dimefox, dimetan, dimethoate, dimethrin, dimeth vamidothion, vaniliprole. XMC, xylylcarb, Zeta-cyper ylvinphos, dimetilan, dinex, dinoprop, dinosam, dinotefuran, methrin, Zolaprofos, and C-ecdysone. diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfo Additionally, it is contemplated that any combination of ton, dithicrofos, d-limonene, DNOC, doramectin, ecdyster 40 the above insecticides can be employed in the compositions one, emamectin, EMPC, empenthrin, endosulfan, endothion, described herein. For more information consult “COMPEN endrin, EPN, epolfenonane, eprinomectin, esfenvalerate, eta DIUM OF PESTICIDE COMMON NAMES located at phos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethop http://www.alanwood.net/pesticides/index.html. Also con rophos, ethyl formate, ethyl-DDD, ethylene dibromide, eth sult “THE PESTICIDE MANUAL 14th Edition, edited by C ylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, 45 D S Tomlin, copyright 2006 by British Crop Production famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, Council. fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxy Various pesticides are Susceptible to chemical and physical carb, fempirithrin, fempropathrin, fensulfothion, fenthion, degradation in the presence of certain environmental influ fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendia ences, such as heat and/or light. Pesticides that are susceptible mide, flucofuron, flucycloxuron, flucythrinate, flufenerim, 50 to degradation with respect to the latter of these influences are flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, commonly referred to as “photo-labile.” With respect to at formothion, formparanate, foSmethilan, fospirate, fosthietan, least some photo-labile pesticides, it is believed that their furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, degradation can be attributed to a reaction with singlet oxy halfenprox, halofenozide, HCH, HEOD, heptachlor, hep gen. Examples of pesticides that are reactive with singlet tenophos, heterophos, hexaflumuron, HHDN, hydramethyl 55 oxygen include, but are not limited to, certain olefins, aro non, hydrogen cyanide, hydroprene, hyduincarb, imidaclo matics, phenols, naphthols, furans, pyrans and other hetero prid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, cycles containing oxygen; pyrroles, oxazoles, imidazoles, isobenzan, isocarbophos, isodrin, isofenphos, isoprocarb, indoles and other heterocycles containing nitrogen; aliphatic, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I. alicyclic and aromatic amines; amino acids, peptides and jasmolin II, jodfenphos, juvenile hormone I, juvenile hor 60 proteins; and Sulfur containing compounds such as mercap mone II, juvenile hormone III, kelevan, kinoprene, lambda tans and Sulfides; and the like. Further details regarding the cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, determination of whether a pesticide is reactive with singlet lirimfos, lufenuron, lythidathion, malathion, malonoben, oxygen are provided in International Patent Publication No. maZidox, mecarbam, mecarphon, menazon, mephosfolan, WO 2007/053760. It should be appreciated that any one or mercurous chloride, meSulfenfos, metaflumizone, methacri 65 combination of the aforementioned photo-labile, singlet oxy fos, methamidophos, methidathion, methiocarb, methocroto gen reactive pesticides could be included in the compositions phos, methomyl, methoprene, methoxychlor, methoxy described herein. US 8,765,697 B2 5 6 More particular examples of photo-labile, singlet oxygen As used herein, the term “polymeric material is used to reactive pesticides that could be included either alone or in describe a material, compound or composition that is defined combination with each other in the compositions described by or includes at least one polymer or a derivative thereof. In herein include, but are not limited to, natural products which one non-limiting example, the polymeric material includes are microorganisms, microbial products, and materials 5 polyvinyl alcohol. In other examples, the polymeric material derived or extracted from plants, animals, or mineral-bearing may include derivatives of polyvinyl alcohol; polyvinyl pyr rocks. These natural products include products derived from rolidone and/or one or more derivatives thereof natural or naturally derived soil dwelling organisms such as actino synthetic latexes; a polysaccharide or a terpene polymer. In mycete bacteria Such as, for example, macrocyclic lactone one specific example, the polymeric material is a high 10 molecular weight vinyl-acrylic latex, such as UCARTM Latex insecticides. One exemplary macrocyclic lactone insecticide 379G commercially available from Dow Chemical Company, includes avermectins and derivatives thereof. Such as abam 2030 Dow Center, Midland, Mich. 48674. In another specific ectin, doramectin, emamectin, eprinomectin, ivermectin and example, the polymeric material is a terpene polymer, Such as Selamectin. Another exemplary macrocyclic lactone insecti NU FILM 17R) commercially available from Miller Chemical cide includes milbemycins and derivatives thereof such as 15 and Fertilizer Corporation, P.O. Box 333, 120 Radio Road, lepimectin, milbemectin, milbemycin oxime and moxidectin. Hanover, Pa. 17331. It should be appreciated that a mixture of Yet another exemplary macrocyclic lactone insecticide two or more of the foregoing non-limiting polymeric material includes spinosyns, such as spinosad, and derivatives thereof examples could also be included in one or more of the com Such as synthetically produced spinetoram as disclosed in positions described in this document. U.S. Pat. Nos. 5,227,295; 5,670,364; 5,591,606; 6,001,981; The proteinaceous material and polymeric material are 6,143,526, 6,455,504; 6,585,990; 6,919,464; 5,362,634; typically present within the compositions described in this 5.539,089; and 5,202,242, each of which is hereby incorpo document in an activity enhancing amount. An activity rated herein by reference in its entirety. Other natural prod enhancing amount is an amount which increases the halflife ucts include Sabadilla or Veratrine, pyrethrum or pyrethrin, of the composition, or alternatively will enable the composi neem oil or azadirachtin, rotenone, ryania or ryanodine, 25 tion to achieve the same control of pests at a level which is less Bacillus thuringiensis (B. t.), Bacillus subtilis, pheromones, than the amount required for the same pesticidal protection or natural attractants and the like. Other pesticides that could be control of the composition in the absence of the proteinaceous included in the compositions described herein can include material and the polymeric material. In other words, the pro synthetically produced pesticides which are reactive toward teinaceous material and the polymeric material will either singlet oxygen. Examples include, but are not limited to 30 reduce the rate required for protection or extend the residu indoxacarb, imazalil and fempropimorph. In addition to the ality of the composition. foregoing, it should be appreciated that the compositions In one embodiment, a composition may include a ratio, by described herein could also include at least one pesticide weight, between the proteinaceous material and the pesticide which is reactive with singlet oxygen and at least one other between about 1:100 and about 100:1, about 1:50 and about pesticide which is not reactive with singlet oxygen or other 35 50:1, about 1:25 and about 25:1, about 1:5 and about 15:1, wise photo-labile. about 1:2 and about 12:1, about 1:1 and about 10:1, or about In one embodiment, a composition includes at least one or 2:1 and 8:1. In another embodiment, a composition may a mixture of the aforementioned pesticides, at least one pro include a ratio by weight between the polymeric material and teinaceous material and at least one polymeric material. In the pesticide between about 1:100 and about 100:1, about this embodiment, the composition exhibits enhanced pesti 40 1:50 and about 50:1, about 1:25 and about 25:1, about 1:8 and cidal activity compared to a composition dissimilar only in about 15:1, about 1:4 and about 12:1, about 1:2 and about not having the proteinaceous material and the polymeric 10:1, or about 1:1 and about 8:1. In yet another embodiment, material. For example, it is contemplated that the activity or a composition may include a ratio, by weight, between the half-life of the composition is extended and therefore the proteinaceous material and the polymeric material between same activity can be achieved with a lower amount of the 45 about 1:100 and about 100:1, about 1:50 and about 50:1, composition when compared to a composition dissimilar only about 1:25 and about 25:1, about 1:12 and about 12:1, about in not having the proteinaceous material and the polymeric 1:8 and about 10:1, about 1:6 and about 8:1, or about 1:4 and material. Additionally or alternatively, it is contemplated that about 5:1. Still, it is also contemplated that a composition improved pesticidal control over time is achieved with the could include a combination of one or more the weight ratios composition including the proteinaceous material and the 50 set forth above between the proteinaceous material and the polymeric material when compared to a composition dissimi pesticide, the polymeric material and the pesticide and the lar only in not having the proteinaceous material and the proteinaceous material and the polymeric material. polymeric material. In one more particular embodiment, a composition As used herein, the term “proteinaceous material' is used includes a ratio, by weight, between the proteinaceous mate to describe a material, composition or compound that is 55 rial and the pesticide between about 3:1 and about 10:1, defined by a protein, includes at leas one protein or is a basic between the polymeric material and the pesticide between element of a protein. In one form, the proteinaceous material about 1:4 and about 5:1 and between the proteinaceous mate may be a water-soluble protein. Further non-limiting rial and the polymeric material between about 1:1 and about examples of proteinaceous aterials include albumin, Such as 7:1. In another more particular embodiment, a composition egg albumenorbovine serum albumin (BSA); casein, gelatin: 60 includes a ratio, by weight, between the proteinaceous mate Zein; a whey composition, such as a mixture of lactose and rial and the pesticide between about 2:1 and about 8:1, whey protein; whey protein and amino acids such as cysteine, between the polymeric material and the pesticide between methionine, trytophan, histidine, and tyrosine, just to name a about 1:2 and about 3:1 and between the proteinaceous mate few possibilities. It is also contemplated that a mixture of two rial and the polymeric material between about 2:1 and about or more of the foregoing non-limiting proteinaceous material 65 5:1. Still, in yet another more particular embodiment, a com examples could be included in one or more of the composi position includes a ratio, by weight, between the proteina tions described in this document. ceous material and the pesticide from about 4:1 to about 7:1, US 8,765,697 B2 7 8 between the polymeric material and the pesticide from about particular embodiment, a composition includes from about 1:1 to about 2.5:1 and between the proteinaceous material and 2% to about 25% by weight of the pesticide, from about 20% the polymeric material from about 2:1 to about 5:1. to about 70% by weight of the proteinaceous material and In another particular embodiment, a composition includes from about 5% to about 25% by weight of the polymeric a ratio, by weight, between the proteinaceous material and the material. In an even more particular embodiment, a compo pesticide between about 1:4 and about 8:1, between the poly sition includes from about 10% to about 20% by weight of the meric material and the pesticide between about 2:1 and about pesticide, from about 40% to about 60% by weight of the 12:1 and between the proteinaceous material and the poly proteinaceous material and from about 5% to about 20% by meric material between about 1:10 and about 2:1. In yet weight of the polymeric material. In one other embodiment, a another more particular embodiment, a composition includes 10 composition includes from about 5% to about 25% by weight a ratio, by weight, between the proteinaceous material and the of the pesticide, from about 60% to about 80% by weight of pesticide between about 1:2 and about 4:1, between the poly the proteinaceous material and from about 5% to about 25% meric material and the pesticide between about 4:1 and about by weight of the polymeric material. In another embodiment, 10:1 and between the proteinaceous material and the poly a composition includes from about 5% to about 15% by meric material between about 1:8 and about 1:1. In another 15 weight of the pesticide, from about 65% to about 75% by particular embodiment, a composition includes a ratio, by weight of the proteinaceous material and from about 10% to weight, between the proteinaceous material and the pesticide about 20% by weight of the polymeric material. from about 1:1 to about 2:1, between the polymeric material Still, in another more particular embodiment, a composi and the pesticide from about 6:1 to about 8:1 and between the tion includes from about 2% to about 25% by weight of the proteinaceous material and the polymeric material from pesticide, from about 5% to about 30% by weight of the about 1:6 to about 1:2. proteinaceous material and from about 55% to about 85% by It should be appreciated however that alternative values for weight of the polymeric material. In another more particular the weight ratios between the proteinaceous material and the embodiment, a composition includes from about 3% to about pesticide, the polymeric material and the pesticide and the 20% by weight of the pesticide, from about 5% to about 25% proteinaceous material and the polymeric material are con 25 by weight of the proteinaceous material and from about 60% templated. For example, in one embodiment, it is contem to about 80% by weight of the polymeric material. In yet plated that a composition may include a ratio, by weight, another particular embodiment, a composition includes from between the proteinaceous material and the pesticide between about 5% to about 15% by weight of the pesticide, from about about 1:100 and about 100:1, between the polymeric material 10% to about 20% by weight of the proteinaceous material and the pesticide between about 1:100 and about 100:1 and 30 and from about 65% to about 75% by weight of the polymeric between the proteinaceous material and the polymeric mate material. rial between about 1:100 and about 100:1. In another embodi Still, it should be appreciated that alternative values for the ment, it is contemplated that a composition may include a weight percentages of the pesticide, proteinaceous material ratio, by weight, between the proteinaceous material and the and polymeric material are contemplated. For example, in pesticide between about 1:50 and about 50:1, between the 35 one embodiment, it is contemplated that a composition may polymeric material and the pesticide between about 1:50 and include between about 0.1% and about 50% by weight of the about 50:1 and between the proteinaceous material and the pesticide, between about 2% and about 90% by weight of the polymeric material between about 1:50 and about 50:1. Still, proteinaceous material and between about 1% to about 90% in another embodiment, it is contemplated that a composition by weight of the polymeric material. Still, in another embodi may include a ratio, by weight, between the proteinaceous 40 ment, it is contemplated that a composition may include material and the pesticide between about 1:25 and about 25:1, between about 0.1% and about 75% by weight of the pesti between the polymeric material and the pesticide between cide, between about 0.1% and about 95% by weight of the about 1:25 and about 25:1 and between the proteinaceous proteinaceous material and between about 0.1% and about material and the polymeric material between about 1:25 and 95% by weight of the polymeric material. about 25:1. 45 In another embodiment, a composition includes at least one In still another embodiment, a composition includes from or a mixture of the aforementioned pesticides and at least one about 1% to about 35% by weight of the pesticide, from about polymeric material. In this embodiment, the composition 5% to about 85% by weight of the proteinaceous material and exhibits enhanced pesticidal activity compared to a compo from about 2% to about 80% by weight of the polymeric sition dissimilar only in not having the polymeric material. material. In another embodiment, a composition includes 50 For example, it is contemplated that the activity or half-life of from about 1% to about 30% by weight of the pesticide, from the composition is extended and therefore the same activity about 10% to about 80% by weight of the proteinaceous can be achieved with a lower amount of the composition when material and from about 3% to about 75% by weight of the compared to a composition dissimilar only in not having the polymeric material. In still another embodiment, a composi polymeric material. Additionally or alternatively, it is con tion includes from about 2% to about 25% by weight of the 55 templated that improved pesticidal control over time is pesticide, from about 15% to about 75% by weight of the achieved with the composition including the polymeric mate proteinaceous material and from about 5% to about 70% by rial when compared to a composition dissimilar only in not weight of the polymeric material. having the polymeric material. In one more particular embodiment, a composition The polymeric material may be one or a mixture of more includes from about 1% to about 35% by weight of the pes 60 than one of the polymeric materials described above and is ticide, from about 10% to about 85% by weight of the pro typically present within the composition in an activity teinaceous material and from about 1% to about 35% by enhancing amount. An activity enhancing amount is an weight of the polymeric material. In another more particular amount which increases the half life of the composition, or embodiment, a composition includes from about 1% to about alternatively will enable the composition to achieve the same 30% by weight of the pesticide, from about 15% to about 75% 65 control of pests at a level which is less than the amount by weight of the proteinaceous material and from about 3% to required for the same pesticidal protection or control of the about 30% by weight of the polymeric material. In yet another composition in the absence of the polymeric material. In other US 8,765,697 B2 10 words, the polymeric material will either reduce the rate the spray drying. In yet another form, the Solid composition required for protection or extend the residuality of the com includes from about 0.001% to about 15% by weight of water position. after the spray drying. In still another form, the Solid compo In one form of this embodiment, the composition includes sition includes from about 0.001% to about 10% by weight of a ratio, by weight, between the polymeric material and the water after the spray drying. In another form, the Solid com pesticide from about 1:4 to about 10:1. In another form, the position includes from about 0.001% to about 5% by weight ratio, by weight, between the polymeric material and the of water after the spray drying. In yet another form, the solid pesticide is from about 1:4 to about 8:1. In a more particular composition includes from about 0.001% to about 4% by form, the ratio, by weight, between the polymeric material weight of water after the spray drying. Still, in another form and the pesticide is from about 1:2 to about 4:1. In an even 10 the solid composition includes from about 0.001% to about more particular form, the ratio, by weight, between the poly 2% by weight of water after the spray drying. In another form, meric material and the pesticide is from about 1:1 to about the solid composition includes from about 0.001% to about 2:1. It should be appreciated however that alternative values 1% by weight of water after the spray drying. However, it for the weight ratios between the polymeric material and the should be appreciated that alternatives values for the weight pesticide are contemplated. For example, in one form, it is 15 percentage of water in the solid composition after the spray contemplated that a composition may include a ratio, by drying are contemplated. weight, between the polymeric material and the pesticide Accordingly, in one embodiment, a method includes pro between about 1:100 and about 100:1. In another form, it is viding a liquid composition that includes at least one pesti contemplated that a composition may include a ratio, by cide, at least one proteinaceous material, at least one poly weight, between the polymeric material and the pesticide meric material and water, and spray drying the liquid between about 1:50 and about 50:1. In yet another form, it is composition to provide a solid composition. In another contemplated that a composition may include a ratio, by embodiment, a method includes providing a liquid composi weight, between the polymeric material and the pesticide tion that includes at least one pesticide, at least one polymeric between about 1:25 and about 25:1. material and water, and spray drying the liquid composition to In another form of this embodiment, the composition 25 provide a solid composition. In one particular form of these includes between about 5% and about 75% by weight of the embodiments, the spray drying includes Substantially remov pesticide and between about 20% and about 90% by weight of ing all of the water from the liquid compositions as they are the polymeric material. In a more particular form, the com converted to the solid compositions. While not previously position includes between about 10% and about 70% by discussed, any other volatile materials besides water, if weight of the pesticide and between about 25% and about 30 present in the liquid compositions, will typically be entirely 80% by weight of the polymeric material. In another form, the or Substantially removed as the liquid compositions are con composition includes from about 15% to about 60% by verted to the solid compositions during the spray drying. weight of the pesticide and from about 30% to about 75% by However, it is contemplated that residual volatile materials weight of the polymeric material. Still, in another form, the other than water could be present in the solid compositions composition includes from about 20% to about 50% by 35 after the spray drying. Additionally, the pesticide and the weight of the pesticide and from about 40% to about 70% by proteinaceous and polymeric materials are generally not weight of the polymeric material. In yet another form, the volatile and will generally not be affected by the spray drying. composition includes from about 20% to about 45% by Thus, it should be appreciated that the solid compositions weight of the pesticide and from about 45% to about 65% by after spray drying will include ratios by weight between the weight of the polymeric material. In another form, the com 40 proteinaceous material and the pesticide, the polymeric mate position includes from about 25% to about 40% by weight of rial and the pesticide and the proteinaceous material and the pesticide and from about 50% to about 65% by weight of polymeric material, as appropriate, that are the same as or the polymeric material. It should be appreciated however that substantially equivalent to the ratios by weight between these alternative we ratios between the polymeric material and the ingredients in the liquid composition. pesticide, along with the weight percentages for the pesticide 45 and polymeric material, are contemplated. Pests The compositions described above can be prepared and provided in any Suitable manner and also include other com In one or more additional embodiments, the invention dis ponents, further details of which will be provided below. In closed in this document can be used to control pests. one exemplary form, the pesticide, polymeric material, pro 50 In one embodiment, the invention disclosed in this docu teinaceous material, if present, water and any other compo ment can be used to control pests of the Phylum Nematoda. nents, if present, are mixed together, homogenized and pro In another embodiment, the invention disclosed in this vided as a liquid composition. The liquid composition may document can be used to control pests of the Phylum Arthro then be spray dried to provide a solid composition which may poda. be in a powder or granular form, just to name a few possibili 55 In another embodiment, the invention disclosed in this ties. During the spray drying, the liquid composition is at least document can be used to control pests of the Subphylum partially dehydrated or dried, with such dehydration or drying Chelicerata. resulting in the conversion of the liquid composition to the In another embodiment, the invention disclosed in this Solid composition which includes a Smaller percentage by document can be used to control pests of the Class Arachnida. weight of water than the liquid composition. In one or more 60 In another embodiment, the invention disclosed in this forms, the spray drying will remove all or substantially all of document can be used to control pests of the Subphylum the water from the liquid composition as it is converted to the Myriapoda. solid composition. However, it should be appreciated that In another embodiment, the invention disclosed in this residual water may be present in one or more forms of the document can be used to control pests of the Class Symphyla. Solid composition. 65 In another embodiment, the invention disclosed in this For example, in one form, the Solid composition includes document can be used to control pests of the Subphylum between about 0.001% to about 20% by weight of water after Hexapoda. US 8,765,697 B2 11 12 In another embodiment, the invention disclosed in this Periplaneta americana (American cockroach), Periplaneta document can be used to control pests of the Class Insecta. australoasiae (Australian cockroach), Periplaneta brunnea In another embodiment, the invention disclosed in this (brown cockroach), Periplaneta fuliginosa (Smokybrown document can be used to control Coleoptera (beetles). A cockroach), Pyncoselus Suninamensis (Surinam cockroach), non-exhaustive list of these pests includes, but is not limited and Supella longipalpa (brownbanded cockroach). to, Acanthoscelides spp. (weevils). Acanthoscelides Obtectus In another embodiment, the invention disclosed in this (common bean weevil). Agrilus planipennis (emerald ash document can be used to control Diptera (true flies). A non borer). Agriotes spp., (wireworms). Anoplophora glabripen exhaustive list of these pests includes, but is not limited to, nis (Asian longhorned beetle), Anthonomus spp. (weevils), Aedes spp. (mosquitoes), Agromyza frontella (alfalfa blotch Anthonomus grandis (boll weevil), Aphidius spp., Apion spp. 10 leafminer), Agromyza spp. (leafminer flies), Anastrepha spp. (weevils), Apogonia spp. (grubs). Ataenius spretulus (Black (fruit flies), Anastrepha suspensa (Caribbean fruit fly), Turgrass Ataenius), Atomaria linearis (pygmy mangold Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), beetle), Aulacophore spp., Bothy noderes punctiventris (beet Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (ori root weevil), Bruchus spp. (weevils), Bruchus pisorum (pea ental fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata weevil), Cacoesia spp., Callosobruchus maculatus (Southern 15 (Mediterranea fruit fly). Chrysops spp. (deer flies), cowpea weevil), Carpophilus hemipteras (dried fruit beetle), Cochliomyia spp. (screwworms), Contarinia spp. (Gall Cassida vittata, Cerosterna spp., Cerotoma spp. (chry midges), Culex spp. (mosquitoes), Dasineura spp. (gall Someids), Cerotoma trifurcata (bean leaf beetle), Ceutorhyn midges), Dasineura brassicae (cabbage gall midge), Delia chus spp. (weevils). Ceutorhynchus assimilis (cabbage seed spp., Delia platura (seedcorn maggot), Drosophila spp. (vin pod weevil), Ceutorhynchus napi (cabbage curculio), egar flies), Fannia spp. (filth flies), Fannia canicularis (little Chaetocnema spp. (chrysomelids), Colaspis spp. (soil house fly), Fannia scalaris (latrine fly), Gasterophilus intes beetles), Conoderus scalaris, Conoderus stigmosus, tinalis (horse botfly), Gracillia perseae, Haematobia irritans Conotrachelus menuphar (plum curculio), Cotinus initidis (horn fly), Hvlemyia spp. (root maggots), Hypoderma linea (Green June beetle), Crioceris asparagi (asparagus beetle), tum (common cattle grub), Liriomyza spp. (leafminer flies), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes 25 Liriomyza brassica (serpentine leafminer), Mellophagus Ovi pusillus (flat grain beetle), Cryptolestes turcicus (Turkish nus (sheep ked), Musca spp. (muscid flies), Musca autumna grain beetle), Ctenicera spp. (wireworms), Curculio spp. lis (face fly), Musca domestica (house fly), Oestrus Ovis (weevils), Cyclocephala spp. (grubs), Cylindrocpturus (sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beet adspersus (Sunflower stem weevil), Deporaus marginiatus leafminer), Phorbia spp., Psila rosae (carrotrust fly), Rhago (mango leaf-cutting weevil), Dermestes lardarius (larder 30 letis cerasi (cherry fruit fly), Rhagoletis pomonella (apple beetle), Dermestes maculates (hide beetle), Diabrotica spp. maggot), Sitodiplosis mosellana (orange wheat blossom (chrysolemids), Epilachna varivestis (Mexican bean beetle), midge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. flies), and Tipula spp. (crane flies). (weevils), Hypera postica (alfalfa weevil), Hyperdocs spp. In another embodiment, the invention disclosed in this (Hyperodes weevil), Hypothenemus hampei (coffee berry 35 document can be used to control Hemiptera (true bugs). A beetle), Ips spp. (engravers), Lasioderma serricorne (ciga non-exhaustive list of these pests includes, but is not limited rette beetle), Leptinotarsa decemlineata (Colorado potato to. Acrosternum hilare (green Stink bug). Blissus leucopterus beetle), Liogenys uscus, Liogenys suturalis, Lissorhoptrus (chinch bug), Calocoris norvegicus (potato mind), Cimex Oryzophilus (rice water weevil). Lyctus spp., (wood beetles/ hemipterus (tropical bedbug), Cimex lectularius (bed hug), powder post beetles), Maecolaspis joliveti, Megascelis spp., 40 Dagbertus faciatus, Dichelaps furcatus, Dysdercus suturellus Melanotus communis, Melligethes spp., Melligethes aeneus (cotton stainer), Edessa meditabunda, Eurygaster maura (ce (blossom beetle) Melolontha melolontha (common European real bug), Euschistus heros, Euschistus servus (brown Stink cockchafer), Oberea brevis, Oberea linearis, Oryctes rhinoc bug), Helopeltis antonii, Helopeltis theivora (tea blight plant eros (date palm beetle). Oryzaephilus mercator (merchant bug), Lagynotomus spp. (stink bugs), Leptocorisa Oratorius, grain beetle). Oryzaephilus surinamensis (Sawtoothed grain 45 Leptocorisa varicornis, Lygus spp. (plant bugs), Lygus hes beetle), Otiorhynchus spp. (weevils), Oulema melanopus (ce perus (western tarnished plant bug), Maconellicoccus hirsu real leaf beetle), Oulema Oryzae, Pantomorus spp. (weevils), tus, Neurocolpus longirostris, Nezara viridula (Southern Phyllophaga spp. (May/June beetle), Phyllophaga cuyabana, green Stink bug), Phytocoris spp. (plant bugs), Phytocoris Phyllotreta spp. (chrysomelids), Phynchites spp., Popillia Californicus, Phytocoris relativus, Piezodorus guildingi, japonica (Japanese beetle), Prostephanus truncates (larger 50 Poecilocapsus lineatus (fourlined plant bug), Psallus vaccini grain borer), Rhizopertha dominica (lesser grain borer), cola, Pseudacy.sta perseae, Scaptocoris Castanea, and Tri Rhizotrogus spp. (Eurpoean chafer), Rhynchophorus spp. atoma spp. (bloodsucking conenose bugs/kissing bugs). (weevils), Scolytus spp. (wood beetles). Shenophorus spp. In another embodiment, the invention disclosed in this (Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. document can be used to control Homoptera (aphids, scales, (grain weevils), Sitophilus granaries (granary weevil), Sito 55 whiteflies, leafhoppers). A non-exhaustive list of these pests philus Oryzae (rice weevil), Stegobium paniceum (drugstore includes, but is not limited to, Acrythosiphon pisum (pea beetle), Tribolium spp. (flour beetles), Tribolium castaneum aphid), Adelges spp. (adelgids), Aleurodes proletella (cab (red flour beetle), Tribolium confilsum (confused flour bage whitefly), Aleurodicus disperses, Aleurothrixus flocco beetle), Trogoderma variabile (warehouse beetle), and sus (woolly whitefly), Aluacaspis spp., Amrasca biguitella Zabrus tenebioides. 60 bigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii In another embodiment, the invention disclosed in this (California red scale), Aphis spp. (aphids), Aphis gossypii document can be used to control Dermaptera (earwigs). (cotton aphid), Aphis pomi (apple aphid), Aulacorthum Solani In another embodiment, the invention disclosed in this (foxglove aphid), Bemisia spp. (whiteflies), Bemisia argenti document can be used to control Dictyoptera (cockroaches). folii, Bemisia tabaci (sweetpotato whitefly), Brachycolus A non-exhaustive list of these pests includes, but is not lim 65 noxius (Russian aphid), Brachycorynella asparagi (aspara ited to, Blattella germanica (German cockroach), Blatta ori gus aphid), Brevennia rehi, Brevicogne brassicae (cabbage entalis (oriental cockroach), Parcoblatta pennylvanica, aphid), Ceroplastes spp. (scales), Ceroplastes rubens (red US 8,765,697 B2 13 14 wax scale), Chionaspis spp. (scales), Chrysomphalus spp. cutworm), Alabama argillacea (cotton leafworm), Amorbia (scales), Coccus spp. (scales), Dysaphis plantaginea (rosy cuneana, Amyelosis transitella (navel orangeworm), Ana apple aphid), Empoasca spp. (leafhoppers), Eriosoma lani camptodes defectaria, Anarsia lineatella (peach twig borer), gerum (woolly apple aphid), Icerva purchasi (cottony cush Anomis Sabulijera (jute looper), Anticarsia gemmatalis (vel ion scale), Idioscopus initidulus (mango leafhopper), Laodel 5 vetbean caterpillar), Archips argyrospila (fruit tree leafrol phax striatellus (Smaller brown planthopper), Lepidosaphes ler), Archips rosana (rose leafroller), Argyrotaenia spp. (tor spp., Macrosiphum spp., Macrosiphum euphorbiae (potato tricid moths), Argyrotaenia citrana (orange tortrix), aphid), Macrosiphum granarium (English grain aphid), Mac Autographa gamma, Bonagota Cranaodes, Borbo cinnara rosiphum rosae (rose aphid), Macrosteles quadrilineatus (as (rice leaf folder), Bucculatrix thurberiella (cotton leaf perfo ter leafhopper), Mahanarva fimbiolata, Metopolophium 10 rator), Caloptilia spp. (leaf miners), Capua reticulana, Car dirhodun (rose grain aphid), Mictis longicornis, Myzus per posina niponensis (peach fruit moth). Chilo spp., Chlumetia sicae (green peach aphid), Nephotettix spp. (leafhoppers), transversa (mango shoot borer), Choristoneura rosaceana Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (oblique banded leaf roller), Chrysodeixis spp., Cnaphalo (brown planthopper), Parlatoria pergandii (chaff scale), Par cerus medinalis (grass leafroller), Colias spp., Compomorpha latoria Ziziphi (ebony scale), Peregrinus maidis (corn delpha 15 cramerella, Cossus Cossus (carpenter moth), Crambus spp. cid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (Sod webworms), Cydia funebrana (plum fruit moth), Cydia (grape phylloxera), Physokermes piceae (spruce bud scale), molesta (oriental fruit moth), Cydia nignicana (pea moth), Planococcus spp. (mealybugs), Pseudococcus spp. (mealy Cydia pomonella (codling moth), Darna diducta, Diaphania bugs), Pseudococcus brevipes (pine apple mealybug). Ouad spp. (stem borers), Diatraea spp. (stalk borers), Diatraea raspidiotus perniciosus (San Jose scale), Rhapalosiphun saccharalis (Sugarcane borer), Diatraea graniosella (South spp. (aphids), Rhapalosiphum maida (corn leaf aphid), wester corn borer), Earias spp. (bollworms), Earias insulata Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. (Egyptian bollworm), Earias vitella (rough northern boll (scales), Saissetia oleae (black scale), Schizaphis graminum worm), Ecdytopopha aurantianum, Elasmopalpus lignosel (greenbug). Sitobion avenae (English grain aphid), Sogatella lus (lesser cornstalk borer), Epiphysia's postruttana (light fircifera (white-backed planthopper). Therioaphis spp. 25 brown apple moth), Ephestia spp. (flour moths), Ephestia (aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids), cautella (almond moth), Ephestia elutella (tobbaco moth), Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum Ephestia kuehniella (Mediterranean flour moth), Epimeces (greenhouse whitefly), Trialeurodes abutiloneus (banded spp., Epinotia aporema, Erionota thrax (banana skipper), wing whitefly). Unaspis spp. (scales), Unaspis yanonensis Eupoecilia ambiguella (grape berry moth), Euxoa auxiliaris (arrowhead scale), and Zulia entreriana. 30 (army cutworm), Feltia spp. (cutworms), Gortyna spp. (stem In another embodiment, the invention disclosed in this borers), Grapholita molesta (oriental fruit moth), Hedylepta document can be used to control Hymenoptera (ants, wasps, indicata (bean leaf webber), Helicoverpa spp. (noctuid and bees). A non-exhaustive list of these pests includes, but is moths), Helicoverpa armigera (cotton bollworm), Helicov not limited to, Acromyrrmex spp., Athalia rosae, Atta spp. erpa zea (bollworm/corn earworm), Heliothis spp., (noctuid (leafcutting ants), Camponotus spp. (carpenterants), Diprion 35 moths), Heliothis virescens (tobacco budworm), Hellula spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis undalis (cabbage webworm), Indarbela spp., (root borers), (Argentine ant), Monomorium ssp., Monontorium minumum Keiferia lycopersicella (tomato pinworm), Leucinodes (little black ant), Monomorium pharaonis (Pharaoh ant), Orbonalis (eggplant fruit borer), Leucoptera malifoliella, Neodiprion spp. (sawflies), Pogonomyrmex spp. (harvester Lithocollectis spp., Lobesia botrana (grapefruit moth), LOxa ants), Polistes spp. (paper wasps), Solenopsis spp. (fire ants), 40 grotis spp. (noctuid moths), Loxagrotis albicosta (western Tapoinoma sessile (odorous house ant), Tetranomorium spp. bean cutworm), Lymantria dispar (gypsy moth), Lyonetia (pavementants), Vespula spp. (yellowjackets), and Xylocopa clerkella (apple leaf miner), Mahasena corbetti (oil palm spp. (carpenter bees). bagworm), Malacosoma spp. (tent caterpillars), Mamestra In another embodiment, the invention disclosed in this brassicae (cabbage armyworm), Maruca testulalis (bean pod document can be used to control Isoptera (termites). A non 45 borer), Metisa plana (bagworm), Mythinna unipuncta (true exhaustive list of these pests includes, but is not limited to, armyworm), Neoleucinodes elegantalis (Small tomato borer) Coptotermes spp., Coptotermes curvignathus, Coptotermes Nymphula depunctalis (rice caseworm), Operophthera bru frenchi, Coptotermes formosanus (Formosan Subterranean mata (winter moth), Ostrinia nubilalis (European corn termite), Cornitermes spp. (nasute termites), Cryptotermes borer), Oxydia vesulia, Pandemis cerasana (common currant spp. (drywood termites), Heterotermes spp. (desert Subterra 50 tortrix), Pandemis heparana (brown apple tortrix), Papilio nean termites), Heterotermes aureus, Kalotermes spp. (dry demodocus, Pectinophora gossypiella (pink bollworm), wood termites). Incistitermes spp. (drywood termites), Mac Peridroma spp. (cutworms), Peridroma saucia (variegated rotermes spp. (fungus growing termites), Marginitermes spp. cutworm), Perileucoptera coffeella (white coffee leafminer), (drywood termites), Microcerotermes spp. (harvester ter Phthorimaea operculella (potato tuber moth), Phyllocnisitis mites), Microtermes obesi, Procornitermes spp., Reticuliter 55 citrella, Phyllonorycter spp. (leafminers), Pieris rapae (im mes spp. (Subterranean termites). Reticulitermes banyulensis, ported cabbageworm), Plathypena scabra, Plodia interpunc Reticulitermes grassei, Reticulitermes flavipes (eastern Sub tella (Indian meal moth), Plutella xylostella (diamondback terranean termite), Reticulitermes hageni, Reticulitermes moth), Polychrosis viteana (grape berry moth), Prays hesperus (western Subterranean termite), Reticulitermes San endocarpa, Prays oleae (olive moth), Pseudaletia spp. (noc tonensis, Reticulitermes speratus, Reticulitermes tibialis, 60 tuid moths), Pseudaletia unipunctata (armyworm), Reticulitermes virginicus, Schedorhinotermes spp., and Zoo Pseudoplusia includens (soybean looper), Rachiplusia nu, termopsis spp. (rotten-wood termites). Scirpophaga incertulas, Sesamia spp. (stemborers), Sesamia In another embodiment, the invention disclosed in this inferens (pink rice stem borer), Sesamia nonagrioides, Setora document can be used to control Lepidoptera (moths and nitens, Sitotroga cerealella (Angoumois grain moth), Spar butterflies). A non-exhaustive list of these pests includes, but 65 ganothis pilleriana, Spodoptera spp. (armyworms), is not limited to, Achoea janata, Adoxophyes spp., Adoxo Spodoptera exigua (beet armyworm), Spodopterafiugiperda phyes Orana, Agrotis spp. (cutworms), Agrotis ipsilon (black (fall armyworm), Spodoptera oridania (Southern army US 8,765,697 B2 15 16 worm), Synanthedon spp. (root borers). Thecla basilides, (bulb mites), Sarcoptes scabiei (itch mite), Tegolophus per Thermisia gemmatalis, Tineola bisselliella (webbing clothes seaflorae, Tetranychus spp., Tetranychus urticae (twospotted moth), Trichoplusia ni (cabbage looper), Tuta absoluta, spider mite), and Varroa destructor (honeybee mite). Yponomeuta spp., Zeuzera coffeae (red branch borer) and In another embodiment, the invention disclosed in this Zeuzera pyrina (leopard moth). document can be used to control Nematoda (nematodes). A In another embodiment, the invention disclosed in this non-exhaustive list of these pests includes, but is not limited document can be used to control Mallophaga (chewing lice). to, Aphelenchoides spp. (bud and leaf & pine wood nema A non-exhaustive list of these pests includes, but is not lim todes), Belonolaimus spp. (sting nematodes), Criconemella ited to, Bovicola Ovis (sheep biting louse), Menacanthus stru spp. (ring nematodes), Dirofilaria immitis (dog heartworm), mineus (chicken body louse), and Menopon gallinea (com 10 Dity lenchus spp. (stem and bulb nematodes), Heterodera spp. mon hen house). (cyst nematodes), Heterodera zeae (corn cyst nematode), In another embodiment, the invention disclosed in this Hirschmanniella spp. (root nematodes), Hoplolaimus spp. document can be used to control Orthoptera (grasshoppers, (lance nematodes), Meloidogyne spp. (root knot nematodes), locusts, and crickets). A non-exhaustive list of these pests Meloidogyne incognita (root knot nematode). Onchocerca includes, but is not limited to, Anabrus simplex (Mormon 15 volvulus (hook-tail worm), Pratylenchus spp. (lesion nema cricket), Gryllotalpidae (mole crickets), Locusta migratoria, todes), Radopholus spp. (burrowing nematodes), and Roty Melanoplus spp. (grasshoppers), Microcentrum retinerve lenchus reniformis (kidney-shaped nematode). (angular winged katydid), Pterophylla spp. (kaydids), chis In another embodiment, the invention disclosed in this tocerca gregaria, Scudderia furcata (fork tailed bush katy document can be used to control Symphyla (Symphylans). A did), and Valanga nigricorni. non-exhaustive list of these pests includes, but is not limited In another embodiment, the invention disclosed in this to, Scutigerella immaculata. document can be used to control Phthiraptera (Sucking lice). For more detailed information consult “HANDBOOK OF A non-exhaustive list of these pests includes, but is not lim PEST CONTROL THE BEHAVIOR, LIFE HISTORY, ited to, Haematopinus spp. (cattle and hog lice), Linognathus AND CONTROL OF HOUSEHOLD PESTS” by Arnold Ovillus (sheep louse), Pediculus humanus capitis (human 25 Mallis, 9th Edition, copyright 2004 by GIE Media Inc. body louse), Pediculus humanus humanus (human body lice), and Pthirus pubis (crab louse). Mixtures In another embodiment, the invention disclosed in this document can be used to control Siphonaptera (fleas) A non The compositions disclosed in this document can also be exhaustive list of these pests includes, but is not limited to, 30 used, for reasons of economy, physical and chemical stability Ctenocephalides canis (dog flea), Ctenocephalides felis (cat and synergy, with acaricides, algicides, antifeedants, avi flea), and Pulex irritans (human flea). cides, bactericides, bird repellents, chemosterilants, fungi In another embodiment, the invention disclosed in this cides, herbicide Safeners, herbicides, insect attractants, insect document can be used to control Thysanoptera (thrips). A repellents, mammal repellents, mating disrupters, mollusci non-exhaustive list of these pests includes, but is not limited 35 cides, other insecticides, other pesticides, plant activators, to, Frankliniella fisca (tobacco thrips), Frankliniella Occi plant growth regulators, rodenticides, synergists, defoliants, dentalis (western flower thrips). Frankliniella Shultzei Fran desiccants, disinfectants, semiochemicals, and virucides Kliniella williamsi (corn thrips), Heliothrips haemorrhaidalis (these categories not necessarily mutually exclusive (greenhouse thrips), Riphiphorothrips cruentatus, Scirto thrips spp., Scirtothrips citri (citrus thrips), Scirtothrips dor 40 Formulations salis (yellow tea thrips), Taeniothrips rhopalantennalis, and Thrips spp. The compositions described in this document may also be In another embodiment, the invention disclosed in this provided with phytologically-acceptable inert ingredients to document can be used to control Thysanura (bristletails). A provide or complement a carrier and can be formulated into, non-exhaustive list of these pests includes, but is not limited 45 for example, baits, concentrated emulsions, dusts, emulsifi to, Lepisma spp. (silverfish) and Thermobia spp. (firebrats). able concentrates, fumigants, gels, granules, microencapsu In another embodiment, the invention disclosed in this lations, seed treatments, Suspension concentrates, Suspo document can be used to control Acarina (mites and ticks). A emulsions, tablets, water soluble liquids, water dispersible non-exhaustive list of these pests includes, but is not limited granules or dry flowables, wettable powders, and ultra low to, Acarapsis woodi (tracheal mite of honeybees), Acarus 50 Volume solutions. spp. (food mites), Acarus siro (grain mite), Aceria For further information on formulation types see "CATA mangiferae (mango bud mite), Aculops spp., Aculops lyco LOGUE OF PESTICIDE FORMULATION TYPES AND persici (tomato russet mite), Aculops pelekasi, Aculus pelle INTERNATIONAL CODING SYSTEM Technical Mono kassi, Aculus Schlechtendali (apple rust mite), Amblyomma graph n° 2, 5th Edition by CropLife International (2002). americanum (lone startick), Boophilus spp. (ticks), Brevipal 55 Pesticide compositions can be frequently applied as aque pus Obovatus (privet mite), Brevipalpus phoenicis (red and ous Suspensions or emulsions prepared from concentrated black flat mite), Demodex spp. (mange mites), Dermacentor formulations of Such compositions. Such water-soluble, spp. (hard ticks), Dermacentor variabilis (american dog water-suspendable, or emulsifiable formulations are either tick), Dermatophagoides pteronyssinus (house dust mite), Solids, usually known as wettable powders, or water dispers Eotetranycus spp., Eotetranychus carpini (yellow spider 60 ible granules, or liquids usually known as emulsifiable con mite), Epitimerus spp., Eriophyes spp., Ixodes spp. (ticks), centrates, aqueous Suspensions or oil suspensions. Wettable Metatetranycus spp., Notoedres cati, Oligonychus spp., Oli powders, which may be compacted to form water dispersible gonychus coffee, Oligonychus ilicus (Southern red mite), granules, comprise an intimate mixture of the pesticide com Panonychus spp., Panonychus citri (citrus red mite), Panony position, a carrier, and Surfactants. The carrier is usually chus ulmi (European red mite), Phyllocoptruta oleivora (cit 65 chosen from among the attapulgite clays, the montmorillonite rus rust mite), Polyphagotarisonemun latus (broad mite), Rhi clays, the diatomaceous earths, or the purified silicates. Effec picephalus sanguinous (brown dog tick), Rhizoglyphus spp. tive surfactants, which can comprise from about 0.5% to US 8,765,697 B2 17 18 about 10% of the wettable powder, are found among sul and act by penetrating the pest's respiratory system or being fonated lignins, condensed naphthalenesulfonates, naphtha absorbed through the pest’s cuticle. Fumigants are applied to lenesulfonates, alkylbenzenesulfonates, alkyl Sulfates, and control stored product pests under gas proof sheets, in gas nonionic Surfactants such as ethylene oxide adducts of alkyl sealed rooms or buildings or in special chambers. phenols. Oil Solution concentrates are made by dissolving a pesti Emulsifiable concentrates comprise a convenient concen cide composition in a solvent that will hold the pesticide tration of a pesticide composition dissolved in a carrier that is composition in solution. Oil Solutions of a pesticide compo either a water miscible solvent or a mixture of water-immis sition usually provide faster knockdown and kill of pests than cible organic solvent and emulsifiers. Useful organic solvents other formulations due to the solvents themselves having include aromatics, especially Xylenes and petroleum frac 10 pesticidal action and the dissolution of the waxy covering of tions, especially the high-boiling naphthalenic and olefinic the integument increasing the speed of uptake of the pesti portions of petroleum Such as heavy aromatic naphtha. Other cide. Other advantages of oil solutions include better storage organic solvents may also be used, such as the terpenic Sol stability, better penetration of crevices, and better adhesion to vents including rosin derivatives, aliphatic ketones Such as greasy Surfaces. cyclohexanone, and complex alcohols such as 2-ethoxyetha 15 Another embodiment is an oil-in-water emulsion, wherein nol. Suitable emulsifiers for emulsifiable concentrates are the emulsion comprises oily globules which are each pro chosen from conventional anionic and nonionic Surfactants. vided with a lamellar liquid crystal coating and are dispersed Aqueous Suspensions comprise Suspensions of water-in in an aqueous phase, wherein each oily globule comprises at soluble pesticide compositions dispersed in an aqueous car least one compound which is agriculturally active and is rier. Suspensions are prepared by finely grinding the pesticide individually coated with a monolamellar or oligolamellar composition and vigorously mixing it into a carrier com layer comprising: (1) at least one non-ionic lipophilic Sur prised of water and Surfactants. Ingredients, such as inorganic face-active agent, (2) at least one non-ionic hydrophilic Sur salts and synthetic or natural gums, may also be added, to face-active agent and (3) at least one ionic Surface-active increase the density and viscosity of the aqueous carrier. It is agent, wherein the globules having a mean particle diameter often most effective to grind and mix the pesticide composi 25 of less than 800 nanometers. Further information on the tion at the same time by preparing the aqueous mixture and embodiment is disclosed in U.S. patent publication homogenizing it in an implement Such as a sand mill, ball 20070027034 published Feb. 1, 2007, having patent applica mill, or piston-type homogenizer. tion Ser. No. 1 1/495,228. For ease of use this embodiment Pesticide compositions may also be applied as granular will be referred to as “OIWE. formulations that are particularly useful for applications to 30 For further information consult “INSECT PEST MAN the soil. Granular formulations contain the pesticide compo AGEMENT' 2nd Edition by D. Dent, copyright CAB Inter sition dispersed in a carrier that comprises clay or a similar national (2000). Additionally, for more detailed information Substance. Such formulations are usually prepared by dis consult HANDBOOK OF PEST CONTROL THE Solving the pesticide composition in a suitable solvent and BEHAVIOR, LIFE HISTORY AND CONTROL OF applying it to a granular carrier which has been pre-formed to 35 HOUSEHOLDPESTS’ by Arnold Mallis, 9th Edition, copy the appropriate particle size, in the range of from about 0.5 to right 2004 by GIE Media Inc. 3 mm. Such formulations may also be formulated by making a dough or paste of the carrier and pesticide composition and Other Formulation Components crushing and drying to obtain the desired granular particle size. 40 Generally, when the compositions disclosed in this docu Dusts containing a pesticide composition are prepared by ment are used in a formulation, Such formulation can also intimately mixing the pesticide composition in powdered contain other components. These components include, but form with a Suitable dusty agricultural carrier, Such as kaolin are not limited to, (this is a non-exhaustive and non-mutually clay, ground Volcanic rock, and the like. Dusts can be applied exclusive list) wetters, spreaders, Stickers, penetrants, buff as a seed dressing, or as a foliage application with a dust 45 ers, sequestering agents, drift reduction agents, compatibility blower machine. agents, anti-foam agents, cleaning agents, rheology agents, It is equally practical to apply a pesticide composition in stabilizers, dispersing agents, and emulsifiers. A few compo the form of a solution in an appropriate organic solvent, nents are described forthwith. usually petroleum oil. Such as the spray oils, which are widely A wetting agent is a Substance that when added to a liquid used in agricultural chemistry. 50 increases the spreading or penetration power of the liquid by Pesticide compositions can also be applied in the form of reducing the interfacial tension between the liquid and the an aerosol formulation. In Such formulations, the pesticide Surface on which it is spreading. Wetting agents are used for composition is dissolved or dispersed in a carrier, which is a two main functions in agrochemical formulations: during pressure-generating propellant mixture. The aerosol formu processing and manufacture to increase the rate of wetting of lation is packaged in a container from which the mixture is 55 powders in water to make concentrates for soluble liquids or dispensed through an atomizing valve. Suspension concentrates; and during mixing of a product with Pesticide baits are formed when the pesticide composition water in a spray tank to reduce the wetting time of wettable is mixed with food oran attractant or both. When the pests eat powders and to improve the penetration of water into water the bait they also consume the pesticide composition. Baits dispersible granules. Examples of wetting agents used in may take the form of granules, gels, flowable powders, liq 60 wettable powder, Suspension concentrate, and water-dispers uids, or Solids. They may be used in or around pest harbor ible granule formulations are: sodium lauryl Sulphate; sodium ageS. dioctyl Sulphosuccinate; alkyl phenol ethoxylates; and ali Fumigants are pesticides that have a relatively high vapor phatic alcohol ethoxylates. pressure and hence can exist as a gas in Sufficient concentra A dispersing agent is a Substance which adsorbs onto the tions to kill pests in soil or enclosed spaces. The toxicity of the 65 surface of particles and helps to preserve the state of disper fumigant is proportional to its concentration and the exposure sion of the particles and prevents them from reaggregating. time. They are characterized by a good capacity for diffusion Dispersing agents are added to agrochemical formulations to US 8,765,697 B2 19 20 facilitate dispersion and Suspension during manufacture, and tion of pesticides when the formulation is emulsified into to ensure the particles redisperse into water in a spray tank. water. Alcohols are sometimes used as cosolvents to increase They are widely used in wettable powders, Suspension con Solvent power. centrates and water-dispersible granules. Surfactants that are Thickeners or gelling agents are used mainly in the formu used as dispersing agents have the ability to adsorb strongly 5 lation of suspension concentrates, emulsions and Suspoemul onto a particle Surface and provide a charged or Steric barrier sions to modify the rheology or flow properties of the liquid to reaggregation of particles. The most commonly used Sur and to prevent separation and settling of the dispersed par factants are anionic, non-ionic, or mixtures of the two types. ticles or droplets. Thickening, gelling, and anti-settling For wettable powderformulations, the most common dispers agents generally fall into two categories, namely water-in ing agents are sodium lignoSulphonates. For Suspension con 10 soluble particulates and water-soluble polymers. It is possible centrates, very good adsorption and stabilization are obtained to produce Suspension concentrate formulations using clays using polyelectrolytes, such as sodium naphthalene Sulpho and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium nate formaldehyde condensates. Tristyrylphenol ethoxylate aluminum silicate; and attapulgite. Water-soluble polysac phosphate esters are also used. Non-ionics such as alkylaryl 15 charides have been used as thickening-gelling agents for ethylene oxide condensates and EO-POblock copolymers are many years. The types of polysaccharides most commonly Sometimes combined with anionics as dispersing agents for used are natural extracts of seeds and seaweeds are synthetic Suspension concentrates. In recent years, new types of very derivatives of cellulose Examples of these types of materials high molecular weight polymeric Surfactants have been include, but are not limited to, guar gum, locust bean gum, developed as dispersing agents. These have very long hydro carrageenam; alginates; methyl cellulose; sodium carboxym phobic backbones and a large number of ethylene oxide ethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). chains forming the teeth of a comb surfactant. These high Other types of anti-settling agents are based on modified molecular weight polymers can give very good long-term starches, polyacrylates, polyvinyl alcohol and polyethylene stability to Suspension concentrates because the hydrophobic oxide. Another good anti-settling agent is Xanthan gum. backbones have many anchoring points onto the particle Sur 25 Microorganisms cause spoilage of formulated products. faces. Examples of dispersing agents used in agrochemical Therefore preservation agents are used to eliminate or reduce formulations are: Sodium lignoSulphonates; sodium naphtha their effect. Examples of Such agents include, but are not lene Sulphonate formaldehyde condensates; tristyrylphenol limited to: propionic acid and its sodium salt; Sorbic acid and ethoxylate phosphate esters; aliphatic alcohol ethoxylates; its sodium or potassium salts; benzoic acid and its Sodium alky ethoxylates; EO-PO block copolymers; and graft salt; p-hydroxybenzoic acid sodium salt: methyl p-hydroxy copolymers. benzoate: and 1,2-benzisothiazalin-3-one (BIT). An emulsifying agent is a Substance which stabilizes a The presence of surfactants, which lower interfacial ten Suspension of droplets of one liquid phase in another liquid Sion, often causes water-based formulations to foam during phase. Without the emulsifying agent the two liquids would mixing operations in production and in application through a 35 spray tank. In order to reduce the tendency to foam, anti-foam separate into two immiscible liquid phases. The most com agents are often added either during the production stage or monly used emulsifier blends contain alkylphenol oraliphatic before filling into bottles. Generally, there are two types of alcohol with 12 or more ethylene oxide units and the oil anti-foam agents, namely silicones and non-silicones. Sili soluble calcium salt of dodecylbenzene sulphonic acid. A cones are usually aqueous emulsions of dimethyl polysilox range of hydrophile-lipophile balance (“HLB) values from 8 40 ane while the non-silicone anti-foam agents are water-in to 18 will normally provide good stable emulsions. Emulsion soluble oils, such as octanol and nonanol, or silica. In both stability can sometimes be improved by the addition of a cases, the function of the anti-foam agent is to displace the small amount of an EO-PO block copolymer surfactant. surfactant from the air-water interface. A solubilizing agent is a Surfactant which will form For further information See “CHEMISTRY AND TECH micelles in water at concentrations above the critical micelle 45 NOLOGY OF AGROCHEMICAL FORMULATIONS concentration. The micelles are then able to dissolve or solu edited by D. A. Knowles, copyright 1998 by Kluwer Aca bilize water-insoluble materials inside the hydrophobic part demic Publishers. Also see 'INSECTICIDES INAGRICUL of the micelle. The types of surfactants usually used for solu TURE AND ENVIRONMENT RETROSPECTS AND bilization are non-ionics: Sorbitan monooleates; Sorbitan PROSPECTS’ by A. S. Perry, Yamamoto, I. Ishaaya, and R. monooleate ethoxylates; and methyl oleate esters. 50 Perry, copyright 1998 by Springer-Verlag. Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to Applications spray-tank mixes to improve the biological performance of the pesticide on the target. The types of Surfactants used for The actual amount of a pesticide composition to be applied bioenhancement depend generally on the nature and mode of 55 to loci of pests is generally not critical and can readily be action of the pesticide. However, they are often non-ionics determined by those skilled in the art. In general, concentra Such as: alky ethoxylates; linear aliphatic alcohol ethoxy tions from about 0.01 grams of pesticide per hectare to about lates; aliphatic amine ethoxylates. 5000 grams of pesticide per hectare are expected to provide Organic solvents are used mainly in the formulation of good control. emulsifiable concentrates, ULV formulations, and to a lesser 60 The locus to which a pesticide composition is applied can extent granular formulations. Sometimes mixtures of Sol be any locus inhabited by a pest, for example, vegetable vents are used. The first main groups of solvents are aliphatic crops, fruit and nut trees, gape vines, ornamental plants, paraffinic oils such as kerosene or refined paraffins. The sec domesticated animals, the interior or exterior Surfaces of ond main group and the most common comprises the aro buildings, and the soil around buildings. Controlling pests matic solvents such as Xylene and higher molecular weight 65 generally means that pest populations, activity, or both, are fractions of C9 and C10 aromatic solvents. Chlorinated reduced in a locus. This can come about when: pest popula hydrocarbons are useful as cosolvents to prevent crystalliza tions are repulsed from a locus; when pests are incapacitated US 8,765,697 B2 21 22 in or around a locus; or pests are exterminated, in whole or in Thereafter, in that locality where the product registration is part, in or around a locus. Of course a combination of these granted and Supported. Such user or seller may use or sell Such results can occur. Generally, pest populations, activity, or pesticide. both are desirably reduced more than fifty percent, preferably more than 90 percent. EXAMPLES Generally, with baits, the baits are placed in the ground where, for example, termites can come into contact with the The following examples are for illustration purposes and bait. Baits can also be applied to a Surface of a building, are not to be construed as limiting the invention disclosed in (horizontal, Vertical, or Slanted, Surface) where, for example, this document to only the embodiments disclosed in these ants, termites, cockroaches, and flies, can come into contact 10 examples. with the bait. Because of the unique ability of the eggs of Some pests to Example Compositions resist pesticide compositions repeated applications may be desirable to control newly emerged larvae. Example compositions A-I described below each include Systemic movement of pesticides in plants may be utilized 15 spinetoram. Spinetoram is a mixture of 50-90% (2R.3aR, to control pests on one portion of the plant by applying the 5aR,5bS.9S.13S, 14R,16aS,16bR)-2-(6-deoxy-3-O-ethyl-2, pesticide composition to a different portion of the plant. For 4-di-O-methyl-O-L-mannopyranosyloxy)-13-(2R,5S,6R)- example, control of foliar-feeding insects can be controlled 5-(dimethylamino)tetrahydro-6-methylpyran-2-yloxy-9- by drip irrigation or furrow application, or by treating the seed ethyl-2,3,3a,4,5,5a5b,6,9,10,11,12,13,14,16a, 16b before planting. Seed treatment can be applied to all types of hexadecahydro-14-methyl-1H-as-indaceno.3,2-d seeds, including those from which plants genetically trans oxacyclododecine-7, 15-dione and 50-10% (2R.3aR.5aS, formed to express specialized traits will germinate. Repre 5bS,9S,13S, 14R,16aS,16bS)-2-(6-deoxy-3-O-ethyl-2,4-di sentative examples include those expressing proteins toxic to O-methyl-O-L-mannopyranosyloxy)-13-(2R,5S,6R)-5- invertebrate pests, such as Bacillus thuringiensis or other 25 (dimethylamino)tetrahydro-6-methylpyran-2-yloxy-9- insecticidal toxins, those expressing herbicide resistance, ethyl-2,3,3a.5a5b,6,9,10,11,12,13,14,16a, 16b such as “Roundup Ready’ seed, or those with “stacked' for tetradecahydro-4, 14-dimethyl-1H-as-indaceno.3.2-d eign genes expressing insecticidal toxins, herbicide resis oxacyclododecine-7, 15-dione. Spinetoram is synthetically tance, nutrition-enhancement or any other beneficial traits. derived from a natural product and is typically accompanied 30 by various impurities. Accordingly, for each of the composi Furthermore, such seed treatments with the invention dis tions prepared below in Examples A-I, an assay was per closed in this document can further enhance the ability of a formed on the spinetoram used to make the Examples to plant to better withstand stressful growing conditions. This determine the presence of impurities. results in a healthier, more vigorous plant, which can lead to For each assay, a calibration stock Solution sample was higher yields at harvest time. 35 prepared by adding approximately 43 mg of an analytically It should be readily apparent that the invention can be used standard form of spinetoram with 10.0 mL of purified water with plants genetically transformed to express specialized into a 125 mL glassjar. The glassjar was gently Swirled until traits, such as Bacillus thuringiensis or other insecticidal the spinetoram was dispersed into the purified water. 100.0 toxins, or those expressing herbicide resistance, or those with mL of methanol was then added to the water/spinetoram 'stacked' foreign genes expressing insecticidal toxins, her 40 mixture in the glass jar. A second solution was prepared by bicide resistance, nutrition-enhancement or any other benefi adding 10 mL of purified water and approximately 50 mg of cial traits. the spinetoram product used in each of Examples A-I to a 125 The invention disclosed in this document is suitable for mL glass jar. The glass jar was gently Swirled until the spin controlling endoparasites and ectoparasites in the Veterinary etoram dispersed into the purified water. 100.0 mL of metha medicine sector or in the field of animal keeping. Composi 45 nol was then added to the mixture. Each sample was then tions are applied in a known manner. Such as by oral admin analyzed using liquid chromatography performed with the istration in the form of for example, tablets, capsules, drinks, following instrumentation and under the following condi granules, by dermal application in the form of for example, tions: dipping, spraying, pouring on, spotting on, and dusting, and Chromatograph: Agilent (formally Hewlett Packard) by parenteral administration in the form of, for example, an 50 model 1100 or equivalent injection. Column: Phenomenex Luna, C8(2)3 um, 150 mx4.6 mm The invention disclosed in this document can also be column employed advantageously in livestock keeping, for example, Mobile Phase A: water with 2 g/L ammonium acetate, pH cattle, sheep, pigs, chickens, and geese. Suitable formulations adjusted to 5.5 with acetic acid are administered orally to the animals with the drinking water 55 Mobile Phase B: acetonitrile/methanol (80:20, viv) or feed. The dosages and formulations that are suitable Isocratic elution: 20% A/80% B depend on the species. Flow: 1.0 mL/minute Before a pesticide composition can be used or sold com Injection volume: 10.0 LL mercially, Such composition undergoes lengthy evaluation Detector: UV (a 250 nm. processes by various governmental authorities (local, 60 Run Time: 20 minutes regional, state, national, international). Voluminous data Integrator: Agilent EZChrom Elite data acquisition sys requirements are specified by regulatory authorities and must tem, or equivalent be addressed through data generation and Submission by the Based on the results of the liquid chromatography, the weight product registrant or by another on the product registrants percentage of the pure spinetoram component of each of the behalf. These governmental authorities then review such data 65 spinetoram products used in Examples A-I was calculated. and if a determination of safety is concluded, provide the The weight percentage of impurities was then calculated by potential user or seller with product registration approval. Subtracting the weight percentage of the pure spinetoram US 8,765,697 B2 23 24 component from 100. The weight percentage of spinetoram glass jar was gently Swirled until the composition dispersed impurities in each of Examples A-I, based from these calcu into the purified water. 100.0 mL of methanol was then added lations, is provided below. to the mixture and the mixture was shaken for at least about 5 minutes on a mechanical shaker. An aliquot of the mixture Example A was then filtered through a 0.45 um nylon syringe filter, with the first few filtered drops being discarded, and the remaining A liquid composition including spinetoram, egg albumen filtrate providing a sample for liquid chromatography. Each and polyvinyl alcohol, among other ingredients, was pre sample was then analyzed using liquid chromatography per pared according to the following. Spinetoram, Reax(R) 88A, a formed with the following instrumentation and under the dispersant commercially available from MeadWestvaco Cor 10 poration, P.O. Box 118005, Charleston, S.C. 29423, following conditions: Geroponr) SDS, a surfactant commercially available from Chromatograph: Agilent (formally Hewlett Packard) Rhodia, Inc., 8 Cedar Brook Drive, Cranbury N.J., 08512, and model 1100 or equivalent a balance of water to provide a suspension concentrate having Column: Phenomenex Luna, C8(2)3 um, 150 mx4.6 mm column 25-50% w/w of spinetoram were mixed together. The result 15 ing mixture was milled in an Eiger MiniMotormill media mill Mobile Phase A: water with 2 g/L ammonium acetate, pH from Eiger Machinery, Inc., 888 East Belvidere Road, Gray adjusted to 5.5 with acetic acid slake, Ill., 60030, to a particle size of 1-10 um (volume Mobile Phase B: acetonitrile/methanol (80:20, viv) weighted mean diameter). The particle size was measured Isocratic elution: 20% A/80% B using a Malvern Mastersizer 2000 laser diffraction particle Flow: 1.0 mL/minute analyzer from Malvern Instruments Ltd., Enigma Business Injection volume: 10.0 LL Park, Grovewood Road, Malvern, Worcestershire WR14 Detector: UV (a 250 nm. 1XZ, United Kingdom, After milling, egg albumen from Run Time: 20 minutes Grade II chicken egg whites from Sigma Aldrich Corpora Integrator: Agilent EZChrom Elite data acquisition sys tion, 3050 Spruce St., St. Louis, Mo., 63103 and a 15% w/w 25 tem, or equivalent aqueous solution of CelvolR 205 polyvinyl alcohol from Based on the results of the liquid chromatography, the weight Celanese Corporation, 1601 West LBJ Freeway, Dallas, Tex., percentage of the pure spinetoram component for the com 75234, were added to the mixture under agitation. The 15% position of Example A was calculated to be 3.1%. w/w aqueous solution of CelvolR 205 polyvinyl alcohol was Example B prepared according to manufacturer instructions. The total 30 Solids concentration of the mixture was adjusted in the range of 20-50% by weight by adding water. The mixture was then A liquid composition including spinetoram, egg albumen homogenized with a Silverson L4RT-A homogenizer from and polyvinyl alcohol, among other ingredients, was pre Silverson Machines Inc., 355 Chestnut St., East Long pared according to the following, Spinetoram, Reax(R 88A, meadow, Mass., 01028, for about 15-30 minutes. The weight 35 Geroponr) SDS and a balance of water to provide a suspen percentages for the foregoing ingredients, calculated by com sion concentrate having 25-50% w/w of spinetoram were paring the weight of each respective ingredient relative to the mixed together. The resulting mixture was milled in an Eiger total weight of the composition, are provided in Table 1. Table Mini Motormill media mill from Eiger Machinery, Inc. to a 1 also provides the weight percentage of spinetoram impuri particle size of 1-10 Lum (Volume weighted mean diameter). ties in the composition based on the values determined by the 40 The particle size was measured using a Malvern Mastersizer assay procedure described above. 2000 laser diffraction particle analyzer from Malvern Instru ments Ltd. After milling, egg albumen from Grade II chicken egg whites from Sigma Aldrich Corporation and a 15% w/w TABLE 1. aqueous solution of CelvolR 205 polyvinyl alcohol from Example A Celanese Corporation were added to the mixture under agi 45 tation. The 15% w/w aqueous solution of Celvol(R) 205 poly Ingredients Wt.% vinyl alcohol was prepared according to manufacturer Spinetoram 3.1 instructions. The total Solids concentration of the mixture was Spinetoram impurities O.63 adjusted in the range of 20-50% by weight by adding water. Egg Albumen 21.86 PVA 4.96 50 The mixture was then homogenized with a Silverson L4RTA Reax (R) 88A 0.37 homogenizer from Silverson Machines Inc. for about 15-30 Geropon (R) SDS O.O7 minutes. The weight percentages for the foregoing ingredi Water 69.01 ents, calculated by comparing the weight of each respective ingredient relative to the total weight of the composition The liquid composition of Example A was later used for 55 exclusive of water, are provided in Table 2. Table 2 also bio-efficacy experiments, but an assay was performed before provides the weight percentage of spinetoram impurities in hand to determine its proportion by weight of pure spineto the composition based on the values determined by the assay ram so appropriate concentrations for testing could be pre procedure described above. pared. For this assay procedure, a calibration stock Solution sample was prepared by adding approximately 43 mg of an 60 TABLE 2 analytically standard form of spinetoram with 10.0 mL of Example B purified water into a 125 mL glassjar. The glassjar was gently swirled until the spinetoram was dispersed into the purified Ingredients Wt.% water. 100.0 mL of methanol was then added to the water/ Spinetoram 1O.O spinetoram mixture in the glass jar. A second solution was 65 Spinetoram impurities 2.05 prepared by adding 10 mL of purified water and approxi Egg Albumen 70.51 mately 130 mg of the composition to a 125 mL glass jar. The US 8,765,697 B2 25 26 TABLE 2-continued instructions. The total Solids concentration of the mixture was adjusted in the range of 20-50% by weight by adding water. Example B The mixture was then homogenized with a Silverson L4RTA Ingredients Wt.% homogenizer from Silverson Machines Inc. for about 15-30 minutes. The weight percentages for the foregoing ingredi PVA 16.0 Reax (R) 88A 1.2O ents, calculated by comparing the weight of each respective Geropon (R) SDS O.24 ingredient relative to the total weight of the composition, are provided in Table 3. Table 3 also provides the weight percent age of spinetoram impurities in the composition based on the The liquid composition was then spray-dried using a 10 Buchi(R) Model 190 bench top spray dryer from Buchi Cor values determined by the assay procedure described above. poration, 19 Lukens Drive, Suite 400, New Castle, Del. TABLE 3 19720, at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure, 115-140°C. inlet temperature and 50-100° C. outlet Example C temperature to provide a solid composition. It is believed that 15 the spray drying process removes all or Substantially all of the water and other Volatile ingredients from the liquid compo Ingredients Wt.% sition as it is converted to the Solid composition. Since none of Spinetoram 4.0 the ingredients in Example Bapart from the water is believed Spinetoram impurities O.8 to be volatile, it is contemplated that the solid composition Egg Elbumen 28.22 includes weight percentages for each of the ingredients Sub PVA 6.4 stantially similar to those provided in Table 2. The solid Reax (R) 88A O48 composition of Example B was later used for bio-efficacy Geropon SDS O.1 experiments, but anassay was performed beforehand to deter Water 6O.O mine its proportion by weight of pure spinetoram so appro 25 priate concentrations for testing could be prepared. For this assay procedure, a calibration stock Solution The liquid composition of Example C was later used for sample was prepared by adding approximately 43 mg of an bio-efficacy experiments, but an assay was performed before analytically standard form of spinetoram with 10.0 mL of hand to determine its proportion by weight of pure spineto purified water into a 125 mL glassjar. The glassjar was gently 30 swirled until the spinetoram was dispersed into the purified ram so appropriate concentrations for testing could be pre water. 100.0 mL of methanol was then added to the water/ pared. The assay was performed according to the procedure spinetoram mixture in the glass jar. A second solution was described above with respect to Example A and the weight prepared by adding 10 mL of purified water and approxi percentage of the pure spinetoram component for the com mately 130 mg of the Solid composition to a 125 mL glassjar. 35 position was calculated to be 4.0%. The glass jar was gently Swirled until the Solid composition dispersed into the purified water. 100.0 mL of methanol was Example D then added to the mixture and the mixture was shaken for at least about 5 minutes on a mechanical shaker. An aliquot of the mixture was then filtered through a 0.45um nylon Syringe 40 A liquid composition including spinetoram, egg albumen filter, with the first few filtered drops being discarded, and the and polyvinyl alcohol, among other ingredients, was pre remaining filtrate providing a sample for liquid chromatog pared according to the following. Spinetoram, Reax(R 88A, raphy. Each sample was then analyzed using liquid chroma Geroponr) SDS and a balance of water to provide a suspen tography performed with the instrumentation and in accor sion concentrate having 25-50% w/w of spinetoram were dance with the parameters set forth above in Example A. 45 mixed together. The resulting mixture was milled in an Eiger Based on the results of the liquid chromatography, the weight Mini Motormill media mill from Eiger Machinery, Inc. to a percentage of the pure spinetoram component for the Solid particle size of 1-10 Lum (Volume weighted mean diameter). composition of Example B was calculated to be 9.8%. The particle size was measured using a Malvern Mastersizer 2000 laser diffraction particle analyzer from Malvern Instru Example C 50 ments Ltd. After milling, egg albumen from Grade II chicken egg whites from Sigma Aldrich Corporation and a 15% w/w A liquid composition including spinetoram, egg albumen aqueous solution of CelvolR 205 polyvinyl alcohol from and polyvinyl alcohol, among other ingredients, was pre Celanese Corporation were added to the mixture under agi pared according to the following. Spinetoram, Reax(R 88A, tation. The 15% w/w aqueous solution of Celvol(R) 205 poly Geroponr) SDS and a balance of water to provide a suspen 55 sion concentrate having 25-50% w/w of spinetoram were vinyl alcohol was prepared according to manufacturer mixed together. The resulting mixture was milled in an Eiger instructions. The total Solids concentration of the mixture was Mini Motormill media mill from Eiger Machinery, Inc. to a adjusted in the range of 20-50% by weight by adding water. particle size of 1-10 um (Volume weighted mean diameter). The mixture was then homogenized with a Silverson L4RTA The particle size was measured using a Malvern Mastersizer 60 homogenizer from Silverson Machines Inc. for about 15-30 2000 laser diffraction particle analyzer from Malvern Instru minutes. The weight percentages for the foregoing ingredi ments Ltd. After milling, egg albumen from Grade II chicken ents, calculated by comparing the weight of each respective egg whites from Sigma Aldrich Corporation and a 15% w/w ingredient relative to the total weight of the composition aqueous solution of CelvolR 205 polyvinyl alcohol from exclusive of water, are provided in Table 4. Table 4 also Celanese Corporation were added to the mixture under agi 65 provides the weight percentage of spinetoram impurities in tation. The 15% w/w aqueous solution of Celvol(R) 205 poly the composition based on the values determined by the assay vinyl alcohol was prepared according to manufacturer procedure described above. US 8,765,697 B2

TABLE 4 TABLE 5

Example D Example E

Ingredients Wt.% Ingredients Wt.%

Spinetoram 1O.O Spinetoram 1O.O Spinetoram impurities 2.0 Spinetoram impurities 2.05 Egg Albumen 70.56 Egg Albumen 16.81 PVA 16.0 10 PVA 69.7 Reax (R) 88A 1.2 Reax (R) 88A 1.20 Geropon SDS O.24 Geropon SDS O.24

The liquid composition was then spray-dried using a 15 The liquid composition was then spray-dried using a Buchi(R) Model 190 bench top spray dryer from Buchi Cor Buchi(R) Model 190 bench top spray dryer from Buchi Cor poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure, 115-140°C. inlet temperature and 50-100° C. outlet pressure, 115-140°C. inlet temperature and 50-100° C. outlet temperature to provide a solid composition. It is believed that temperature to provide a solid composition. It is believed that the spray drying process removes all or Substantially all of the the spray drying process removes all or Substantially all of the water and other Volatile ingredients from the liquid compo water and other Volatile ingredients from the liquid compo sition as it is converted to the Solid composition. Since none of sition as it is converted to the Solid compositions. Since none the ingredients in Example Dapart from the water is believed of the ingredients in Example E apart from the water is to be volatile, it is contemplated that the solid composition believed to be volatile, it is contemplated that the solid com includes weight percentages for each of the ingredients Sub 25 position includes weight percentages for each of the ingredi stantially similar to those provided in Table 4. The solid ents substantially similar to those provided in Table 5. The composition of Example D was later used for bio-efficacy solid composition of Example E was later used for bio-effi experiments, but anassay was performed beforehand to deter cacy experiments, but an assay was performed beforehand to mine its proportion by weight of pure spinetoram so appro determine its proportion by weight of pure spinetoram so priate concentrations for testing could be prepared. The assay 30 appropriate concentrations for testing could be prepared. The was performed according to the procedure described above assay was performed according to the procedure described with respect to Example B and the weight percentage of the above with respect to Example B and the weight percentage pure spinetoram component for the Solid composition was of the pure spinetoram component for the Solid composition calculated to be 9.6%. 35 was calculated to be 7.1%. Example E Example F

A liquid composition including spinetoram, egg albumen 40 A liquid composition including spinetoram, egg albumen and polyvinyl alcohol, among other ingredients, was pre and polyvinyl alcohol, among other ingredients, was pre pared according to the following. Spinetoram, Reax(R 88A, pared according to the following. Spinetoram. Re 88A, Geroponr) SDS and a balance of water to provide a suspen Geroponr) SDS and a balance of water to provide a suspen sion concentrate having 25-50% w/w of spinetoram were sion concentrate having 25-50% w/w of spinetoram were mixed together. The resulting mixture was milled in an Eiger 45 mixed together. The resulting mixture was milled in an Eiger Mini Motormill media mill from Eiger Machinery, Inc. to a Mini Motormill media mill from Eiger Machinery, Inc. to a particle size of 1-10 um (Volume weighted mean diameter). particle size of 1-10 Lum (Volume weighted mean diameter). The particle size was measured using a Malvern Mastersizer The particle size was measured using a Malvern Mastersizer 2000 laser diffraction particle analyzer from Malvern Instru 2000 laser diffraction particle analyzer from Malvern Instru ments Ltd. After milling, egg albumen from Grade II chicken 50 ments Ltd. After milling, egg albumen from Grade II chicken egg whites from Sigma Aldrich Corporation and a 15% w/w egg whites from Sigma Aldrich Corporation and a 15% w/w aqueous solution of CelvolR 205 polyvinyl alcohol from aqueous solution of CelvolR 205 polyvinyl alcohol from Celanese Corporation were added to the mixture under agi Celanese Corporation were added to the mixture under agi tation. The 15% w/w aqueous solution of Celvol(R) 205 poly tation. The 15% aqueous solution of Celvol(R) 205 polyvinyl vinyl alcohol was prepared according to manufacturer 55 alcohol was prepared according to manufacturer instructions. instructions. The total Solids concentration of the mixture was The total solids concentration of the mixture was adjusted in adjusted in the range of 20-50% by weight by adding water. the range of 20-50% by weight by adding water. The mixture The mixture was then homogenized with a Silverson L4RTA was then homogenized with a Silverson L4RTA homog homogenizer from Silverson Machines Inc. for about 15-30 enizer from Silverson Machines Inc. for about 15-30 minutes. minutes. The weight percentages for the foregoing ingredi 60 The weight percentages for the foregoing ingredients, calcu ents, calculated by comparing the weight of each respective lated by comparing the weight of each respective ingredient ingredient relative to the total weight of the composition relative to the total weight of the composition exclusive of exclusive of water, are provided in Table 5. Table 5 also water, are provided in Table 6. Table 6 also provides the provides the weight percentage of spinetoram impurities in 65 weight percentage of spinetoram impurities in the composi the composition based on the values determined by the assay tion based on the values determined by the assay procedure procedure described above. described above. US 8,765,697 B2

TABLE 6 TABLE 7

Example F Example G

Ingredients Wt.% Ingredients Wt.% Spinetoram 2O.O Spinetoram impurities 4.10 Spinetoram 1O.O Egg Albumen S8.11 Spinetoram impurities 2.05 PVA 14.90 Egg albumen 47.07 Reax (R) 88A 2.41 10 Min-U-Gel (R) 400 16.00 Geropon SDS O48 Vinyl acrylic latex 22.0 Reax (R) 88A 240 Geropon (R) SDS O48 The liquid composition was then spray-dried using a Buchi(R) Model 190 bench top spray dryer from Buchi Cor 15 poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle The liquid composition was then spray-dried using a pressure, 115-140°C. inlet temperature and 50-100° C. outlet Buchi(R) Model 190 bench top spray dryer from Buchi Cor temperature to provide a solid composition. It is believed that poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle the spray drying process removes all or Substantially all of the pressure, 115-140°C. inlet temperature and 50-100° C. outlet water and other Volatile ingredients from the liquid compo temperature to provide a solid composition. It is believed that sition as it is converted to the Solid composition. Since none of the spray drying process removes all or Substantially all of the the ingredients in Example Fapart from the water is believed water and other Volatile ingredients from the liquid compo to be volatile, it is contemplated that the solid composition sition as it is converted to the Solid composition. Since none of includes weight percentages for each of the ingredients Sub the ingredients in Example G apart from the water is believed stantially similar to those provided in Table 6. The solid 25 to be volatile, it is contemplated that the solid composition composition of Example F was later used for bio-efficacy includes weight percentages for each of the ingredients Sub experiments, but anassay was performed beforehand to deter stantially similar to those provided in Table 7. The solid mine its proportion by weight of pure spinetoram so appro composition of Example G was later used for bio-efficacy priate concentrations for testing could be prepared. The assay experiments, but anassay was performed beforehand to deter was performed according to the procedure described above 30 mine its proportion by weight of pure spinetoram so appro with respect to Example B and the weight percentage of the priate concentrations for testing could be prepared. The assay pure spinetoram component for the Solid composition was was performed according to the procedure described above calculated to be 19.6%. with respect to Example B and the weight percentage of the 35 pure spinetoram component for the Solid composition was Example G calculated to be 10.5%. A liquid composition including spinetoram, egg albumen Example H and a vinyl acrylic latex, among other ingredients, was pre 40 pared according to the following. Spinetoram, Reax(R 88A, A liquid composition including spinetoram, egg albumen Geroponr) SDS and a balance of water to provide a suspen and a terpene polymer, among other ingredients, was pre sion concentrate having 25-50% w/w of spinetoram were pared according to the following. Spinetoram, Reax(R 88A, mixed together. The resulting mixture was milled in an Eiger Geroponr) SDS and a balance of water to provide a suspen Mini Motormill media mill from Eiger Machinery, Inc. to a 45 sion concentrate having 25-50% w/w of spinetoram were particle size of 1-10 um (Volume weighted mean diameter). mixed together. The resulting mixture was milled in an Eiger The particle size was measured using a Malvern Mastersizer Mini Motormill media mill from Eiger Machinery. Inc. to a 2000 laser diffraction particle analyzer from Malvern Instru particle size of 1-10 Lum (Volume weighted mean diameter). ments Ltd. After milling, egg albumen from Grade II chicken The particle size was measured using a Malvern Mastersizer egg whites from Sigma Aldrich Corporation, Min-U-Gel R. 50 2000 laser diffraction particle analyzer from Malvern Instru 400, a magnesium aluminum siliate from Active Minerals ments Ltd. After milling, egg albumen from Grade II chicken Internatinal, LLC, 6 North Park Drive, Suite 105, Hunt Valley, egg whites from Sigma Aldrich Corporation and a terpene Md., 21030, and a vinyl acrylic latex in the form of UCARTM polymer in the form of NU FILM 17R from Miller Chemical Latex 379G from Dow Chemical Company, 2030 Dow Cen and Fertilizer Corporation, P.O. Box 333, 120 Radio Road, ter, Midland, Mich. 48674 were added to the mixture under 55 Hanover, Pa. 17331, were added to the mixture under agita agitation. The total Solids concentration of the mixture was tion. The total solids concentration of the mixture was adjusted in the range of 20-50% by weight by adding water. adjusted in the range of 20-50% by weight by adding water. The mixture was then homogenized with a Silverson L4RTA The mixture was then homogenized with a Silverson L4RTA homogenizer from Silverson Machines Inc. for about 15-30 homogenizer from Silverson Machines Inc. for about 15-30 minutes. The weight percentages for the foregoing ingredi 60 minutes. The weight percentages for the foregoing ingredi ents, calculated by comparing the weight of each respective ents, calculated by comparing the weight of each respective ingredient relative to the total weight of the composition ingredient relative to the total weight of the composition exclusive of water, are provided in Table 7. Table 7 also exclusive of water, are provided in Table 8. Table 8 also provides the weight percentage of spinetoram impurities in 65 provides the weight percentage of spinetoram impurities in the composition based on the values determined by the assay the composition based on the values determined by the assay procedure described above. procedure described above. US 8,765,697 B2 31 32 TABLE 8 TABLE 9-continued Example H Example I Ingredients Wt.% Ingredients Wt.% Spinetoram 1O.O PVA 56.97 Spinetoram impurities 2.05 Reax (R) 88A 3.84 Egg albumen 48.95 Geropon SDS O.77 Nu-Film 17 24.00 Reax (R) 88A 13.20 Geropon SDS 18O 10 The liquid composition was then spray-dried using a Buchi(R) Model 190 bench top spray dryer from Buchi Cor The liquid composition was then spray-dried using a poration at about a 300-400 ml/h feed rate, 4-6 bar nozzle Buchi(R) Model 190 bench top spray dryer from Buchi Cor pressure, 115-140°C. inlet temperature and 50-100° C. outlet poration at about a 300-400 ml/hr feed rate, 4-6 bar nozzle temperature to provide a solid composition. It is believed that pressure, 115-140°C. inlet temperature and 50-100° C. outlet 15 the spray drying process removes all or Substantially all of the temperature to provide a solid composition. It is believed that water and other Volatile ingredients from the liquid compo sition as it is converted to the Solid composition. Since none of the spray drying process removes all or Substantially all of the the ingredients in Example I apart from the water is believed water and other Volatile ingredients from the liquid compo to be volatile, it is contemplated that the solid composition sition as it is converted to the Solid composition. Since none of includes weight percentages for each of the ingredients Sub the ingredients in Example Hapart from the water is believed stantially similar to those provided in Table 9. The solid to be volatile, it is contemplated that the solid composition composition of Example I was later used for bio-efficacy includes weight percentages for each of the ingredients Sub experiments, but anassay was performed beforehand to deter stantially similar to those provided in Table 8. The solid mine its proportion by weight of pure spinetoram so appro composition of Example H was later used for bio-efficacy 25 priate concentrations for testing could be prepared. The assay experiments, but anassay was performed beforehand to deter was performed according to the procedure described above mine its proportion by weight of pure spinetoram so appro with respect to Example B and the weight percentage of the priate concentrations for testing could be prepared. The assay pure spinetoram component for the Solid composition was was performed according to the procedure described above calculated to be 27.7%. with respect to Example B and the weight percentage of the 30 pure spinetoram component for the Solid composition was Bio-Efficacy Testing calculated to be 10.4%. Biological efficacy experiments in Examples I-V were Example I conducted according to the following parameters. A spineto A liquid composition including spinetoram and polyvinyl 35 ram control solution was prepared utilizing either Radiant(R), alcohol, among other ingredients, was prepared according to a Suspension concentrate formulation of spinetoram, or Del the following. Spinetoram, Reax(R) 88A, Geroponr) SDS and egate R, a water-dispersible granule formulation of spineto a balance of water to provide a suspension concentrate having ram, in water to obtain a spinetoram concentration in Solution 25-50% w/w of spinetoram were mixed together. The result of 125 ppm. Radiant(R) and Delegate(R) are commercially ing mixture was milled in an Eiger MiniMotormill media mill 40 available from Dow AgroSciences LLC, 9330 Zionsville from Eiger Machinery, Inc. to a particle size of 1-10 um Road, Indianapolis, Ind., 46268. Test solutions were also (volume weighted mean diameter). The particle size was prepared utilizing the liquid compositions of Examples A and measured using a Malvern Mastersizer 2000 laser diffraction C and the solid compositions of Examples B and D-I (collec particle analyzer from Malvern Instruments Ltd. After mill tively the Example A-I solutions) in water to obtain a spin ing, a 15% w/w aqueous solution of CelvolR 205 polyvinyl 45 etoram concentration in each solution of 125 ppm. These alcohol from Celanese Corporation was added to the mixture Solutions, plus a water-only control, were applied to potted under agitation. The 15% w/w aqueous solution of CelvolR) pepper plants (Capsicum annuum) using a Mandel track 205 polyvinyl alcohol was prepared according to manufac sprayer calibrated to deliver the equivalent of 200 L/Ha of turer instructions, The total solids concentration of the mix spray. Treated plants were allowed to dry and then were aged ture was adjusted in the range of 20-50% by weight by adding 50 outdoors in natural Sunlight or under a set of lamps emitting water. The mixture was then homogenized with a Silverson ultraviolet light at levels comparable to natural Sunlight. At L4RT-A homogenizer from Silverson Machines Inc. for the appropriate time after treatment, i.e., at 4, 7 and 10 or 4, 7 about 15-30 minutes. The weight percentages for the forego ing ingredients, calculated by comparing the weight of each and 11 days after treatment, 2.5 cm diameter disks were cut respective ingredient relative to the total weight of the com from treated leaves. One leaf disk was placed in each well of position exclusive of water, are provided in Table 9. Table 9 55 a 32 well plastic tray, which also contained a thin layer of agar also provides the weight percentage of spinetoram impurities to provide moisture. There were 8 replicate disks per treat in the composition based on the values determined by the ment. Each well was infested with three second instar beet assay procedure described above. armyworm (Spodoptera exigua) larvae, and the well was sealed with plastic film. Larvae were held in an environmental 60 chamber at 25°C./40 percent relative humidity. At 48 hours TABLE 9 after infestation, the larvae were graded for mortality. A larva Example I was considered dead if it could not move after being prodded, and the percent mortality (percent control) was calculated. Ingredients Wt.% For each of Examples I-V, Table 10 below provides the Spinetoram 33.50 65 percent control of the insect associated with the spinetoram Spinetoram impurities 4.92 control solution relative to an untreated standard. For Example A-I solutions, Table 10 provides the improvement in US 8,765,697 B2 33 34 percent control relative to the spinetoram control Solution claim to only one item unless specifically stated to the con (i.e., (percent control by Example A-I solutions)-(percent trary in the claim. Further, when the language "at least a control by spinetoram control solution)). Table 10 also pro portion' and/or “a portion' is used the item may include a vides the average improvement over the spinetoram control portion and/or the entire item unless specifically stated to the Solution which was calculated by Summing the individual contrary. While the invention has been illustrated and improvements for each of the days relative to the control and described in detail in the drawings and foregoing description, then dividing by the number of measurements. For Examples the same is to be considered as illustrative and not restrictive I, II and V, the spinetoram control solution included Radiant(R) in character, it being understood that only the selected and for Examples III and IV, the spinetoram control solution embodiments have been shown and described and that all included Delegate(R). changes, modifications and equivalents that come within the TABLE 10

3 4 5 6 7 9 10 11 12 13 14 Average Solution DAT DAT DAT DAT DAT DAT DAT DAT DAT DAT DAT Improvement Example I

Spinetoram 88 25

S4 33 32

50 29 29

67 33 25

21 29 -21 10

33 58 29 40

92 21 17

29 29 21

92 67 33

17 50 24

-13 17

Spine 33 Contro Solution Examp 34 38 25 Solution Examp 30 30 21 Solution

The headings in this document are for convenience only spirit of the invention as defined herein or by any of the and must not be used to interpret any portion thereof. following claims are desired to be protected. Any theory, mechanism of operation, proof, or finding What is claimed is: 55 1. A composition, comprising from about 2% to about 25% stated herein is meant to further enhance understanding of the by weight of spinetoram, from about 15% to about 75% by present invention and is not intended to make the present weight of egg albumen, and from about 15% to about 70% by invention in any way dependent upon Such theory, mecha weight of a polymeric material selected from the group con nism of operation, proof, or finding. It should be understood sisting of polyvinyl alcohol, a vinyl acrylic latex and a terpene that while the use of the word preferable, preferably or pre 60 polymer, wherein the weight percentages of spinetoram, egg ferred in the description above indicates that the feature so albumen and the polymeric material are based on the total described may be more desirable, it nonetheless may not be weight of the composition. necessary and embodiments lacking the same may be con 2. The composition of claim 1, wherein the polymeric templated as within the scope of the invention, that scope material is polyvinyl alcohol. being defined by the claims that follow. In reading the claims 65 3. The composition of claim 1, which includes from about it is intended that when words such as an.” “at least one.” 5% to about 15% by weight of spinetoram and from about “at least a portion” are used there is no intention to limit the 65% to about 75% by weight of egg albumen. US 8,765,697 B2 35 36 4. The composition of claim 1, which includes from about 5% to about 15% by weight of spinetoram, from about 10% to about 20% by weight of egg albumen, and from about 65% to about 75% by weight of the polymeric material. 5. A method of controlling insects which comprises apply ing to a locus where control is desired an insect-inactivating amount of a composition according to claim 1. 6. A composition, comprising from about 15% to about 60% by weight of spinetoram and from 30% to 75% by weight of polyvinyl alcohol, wherein the weight percentages 10 of spinetoram and polyvinyl alcohol are based on the total weight of the composition. k k k k k