United States Patent (19) (11) Patent Number: 4,994,261 Scher et al. 45) Date of Patent: Feb. 19, 1991

(54) PESTCDE COMPOST ONS AND (56) References Cited METHOD U.S. PATENT DOCUMENTS

2,988,474 6/196l Szabo et al...... 54/141 (75) Inventors: Herbert B. Scher, Moraga; Marius 3,959,464 5/1976 DeSavigny. ... 424/78 Rodson, El Cerrito; Ronald L. 4,140,516 2/1979 Scher .. . 71/88 Morgan, Daly City, all of Calif. 4,285,720 8/1981 Scher ...... 71/88 (73) Assignee: ICI Americas Inc., Wilmington, Del. FOREIGN PATENT DOCUMENTS 0.134674 9/1988 European Pat. Off...... 514/14 (21) Appl. No.: 232,193 Primary Examiner-Allen J. Robinson Attorney, Agent, or Firm-Denis A. Polyn 22 Filed: Aug. 15, 1988 57) ABSTRACT Toxicant, especially pesticide compositions, having Related U.S. Application Data lowered dermal toxicity are provided. The composi. (63) Continuation of Ser. No. 846,183, Mar. 31, 1986, aban tions include a lipophilic-pesticide, a nonionic surfac doned. tant and a dry inert diluent carrier. Methods for reduc ing the dermal toxicity of lipophilic toxicants, especially (51) Int. Cl...... A01N 57/18 pesticides are provided, as well as methods for control (52) U.S. C...... 424/10; 514/141; ling insect pests using the disclosed compositions. 514/974 (58) Field of Search ...... 424/10; 514/141, 974 12 Claims, No Drawings 4,994,261 1. 2 serve the pesticidal effectiveness of the compounds as PESTICIDE COMPOSITIONS AND METHOD applied to the pest or the locus where the pest may be found. This is a continuation of application Ser. No. 846,183, filed Mar. 31, 1986, now abandoned. SUMMARY OF THE INVENTION There has now been discovered a pesticidal composi FIELD OF THE INVENTION tion that maintains high biological effectiveness against The invention relates to dermally toxic pesticide pests when used in the field and has reduced dermal compositions consisting of the pesticide and a dry, inert toxicity. diluent carrier, that have been additionally safened for 10 The compositions comprise a biologically effective handling by addition thereto of a nonionic surfactant amount of a dermally toxic pesticide, a nonionic surfac having an HLB of from about 17 to about 20. tant having an HLB of from about 17 to about 20 and a dry inert diluent carrier. BACKGROUND OF THE INVENTION More particularly, the compositions comprise A wide variety of pesticides are commonly used in 15 (a) a biologically effective amount of a dermally toxic agronomic and horticultural pursuits. As used herein pesticide; the term "pesticide' means any chemical compound or (b) a dinonyl phenol ethoxylate surfactant; and composition which displays biological activity in an (c) a dry inert diluent clay carrier, in granular form. agricultural field site or at any locus where control of Dermal toxicity includes systemic toxic effects that biological growth is desired. The biological activity or 20 occur in an animal or human as a result of dermal control contemplated herein includes all forms of contact with a toxic substance for a defined period of growth modification, ranging from regulation and re time. Dermal toxicity may be defined as the LD-50 tardation to killing, and extends to all forms of plant and (lethal dose to 50% of the animals in a test group) animal life found in an agricultural environment during caused by a 24 hour exposure to a toxic substance. some time during the pest's life cycle. Pesticides within 25 this invention include anti-foulants, plant growth regu Pesticides of the composition disclosed herein include lants, soil fumigants, molluscicides, , herbi dermally toxic organophosphorus, , phos cides, fungicides, rodenticides, nematocides, algicides, phonate and thiophosphonate compounds. The follow predator control agents, and insect and animal repel ing are examples of such compounds, followed in paren lents. Additional biologically active compounds can 30 thesis by their common names, where available: also be present in admixture with the primary ingredi S-tert-butylthiomethyl O,O-diethyl phosphorodithioate ent, such as synergists, antidotes, fertilizers, soil life () extenders, and additional pesticides. O,O-diethyl-O-4-methylsulphinylphenyl phosphorothi The term "biologically effective amount' is used oate (fensulfothion) herein to denote any quantity of pesticide or pesticide 35 O,O-diethyl O-2-isopropyl-6-methylpyridimidin-4-yl composition, which when applied to an agricultural site phosphorothioate () in any conventional manner causes the occurrence of O,O-diethyl S-2-ethylthioethyl phosphorodithioate (di one or more of the biological effects mentioned above. sulfoton) As further explained in the latter portion of this specifi S-chloromethyl O,O-diethyl phosphorodithioate cation, the quantity of pesticide applied in a given situa 40 (chlormephos) tion depend on the pesticide itself, on the type of biolog O-ethyl S,S-dipropyl phosphorodithioate (ethopro ical activity inherent in the pesticide, and the degree of phos) such activity sought to be achieved. The selection of the O,O-diethyl S-ethylthiomethyl phosphorodithioate proper quantity to be applied, however, is within the () expertise of one skilled in the art. 45 O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phos Some pesticides, such as the chlorinated hydrocarbon phorodithioate (prophenofos) insecticides and the organophosphorus pesti S-1,2-di(ethoxycarbonyl)ethyl O,O-dimethyl phos cide compounds, including phosphonate, organophos phorodithioate () phate and organothiophosphate compounds present a O,O,O',O'-tetraethyl S,S'-methylene di(phosphorodi problem of dermal toxicity to persons handling these 50 thioate) () substances. O-(4-bromo-2,5-dichlorophenyl) O,O-diethyl phos If handled carelessly, improperly or in disregard of phorothioate (bromophos-ethyl) directions, the pesticide, depending upon its toxicity, S-4-chlorophenylthiomethyl O,O-diethyl phosphorodi may present a hazard to those handling the pesticide thioate () whether in packaging it for sale, handling it for ship 55 2-chloro-1-(2,4-dichlorophenyl) vinyl diethyl phosphate ment, mixing it for field application or applying it in the (chlorphenvinphos) field. The toxicity of the pesticide will vary depending O-2,5-dichloro-4-(methylthio) phenyl O,O-diethyl upon a number of factors, including the inherent toxic phosphorodithioate (chlorthiophos) ity of the pesticide substance at its site of biological O-4-cyanophenyl O,O-dimethyl phosphorothioate action. Various physical properties of the pesticide in () cluding the hydrophilic-lipophilic balance of the pesti O,O-dimethyl O-2-methylthioethyl phosphorothioate cide affect the adsorption to and absorption by various (demiphion) tissues of the person handling the pesticide compound, O,O-diethyl O-2-ethylthioethyl phosphorothioate and thus affect the toxicity of the compound to the (demeton) person handling it. 65 O-2,4-dichlorophenyl O,O-diethyl phosphorothioate Thus, it is desirable to develop formulations for these (dichlorofenthion) pesticide compounds that reduce the dermal toxicity of O-2,4-dichlorophenyl O-ethyl phenylphosphonothioate the compounds to persons handling them yet still pre (EPBP) 4,994,261 3 4. O,O-diethyl O-5-phenylisoxazol-3-yl phosphorothioate R X () Nil 1,3-di(methoxycarbonyl)-1-propen-2-yl dimethyl phos P-R phate / 1,4-dioxan-2,3-diyl S,S-di(o,O-diethyl phosphorothioate R () O,O-dimethyl-O-4-nitro-m-tolyl phosphorothioate in which X is oxygen or ; and R, R and R2 are () independently selected from the group consisting of O,O-dimethyl O-4-methylthio-m-tolyl phosphorothio C1-C5 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C2-C6 ate () 10 alkenyl, C2-C6 alkenoxy, C2-C6 alkenylthio, phenyl, O-(5-chloro-1-isopropyl-1,2,4-triazol-3-yl) O,O-diethyl phenoxy, phenylthio, C7-C9 phenylalkyl, C7-C9 pheny phosphorothioate (isazophos) lalkoxy, and C7-C9 phenylalkylthio, each member of S-2-isopropylthioethyl O,O-dimethyl phosphorodithio such group optionally substituted with up to three sub ate (isothioate) stituents selected from halogen, C1-C4 alkyl, C1-C4 4-(methylthio)phenyl dipropyl phosphate (propaphos) 15 alkoxy, cyano, and nitro. 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate (na The terms "alkyl,” "alkoxy," etc., are intended to include both straight-chain and branched-chain groups, led) and all carbon atoms ranges are inclusive. More pre O,O-diethyl al-cyanobenzylideneamino-oxyphosphono ferred organophosphorus compounds are those in thioate () 20 which X is sulfur, and R, R and R2 are independently O,O-diethyl O-4-nitrophenyl phosphorothioate (para C1-C4 alkoxy or phenoxy, the phenyl ring optionally thion) substituted with up to three groups selected from O-2-diethylamino-6-methylpyrimidin-4-yl O,O-diethyl C1-C3 alkyl, nitro, cyano, and halogen. Highly pre phosphorothioate (piriniphos-ethyl) ferred are those in which X is sulfur, R is C1-C4 alkoxy, O-2-diethylamino-6-methylpyrimidin-4-yl 25 R1 is C1-C4 alkoxy, and R2 is phenoxy substituted with dimethyl phosphorothioate (pirimiphos-methyl) up to three substituents selected from C1-C3 alkyl and O,O,O',O'-tetraethyldithiopyrophosphate (sulfotep) nitro. O,O,O',O'-tetramethyl O,O'-thiodi-p-phenylene diphos Specific preferred pesticide compounds include S phorothioate (ternephos) tert-butylthiomethyl-O,O-diethylphosphorodithioate S-2-ethylthioethyl O,O-dimethyl phosphorodithioate 30 and O,O-diethyl-S-ethylthiomethylphosphorothioate. (thiometon) O,O-diethyl O-1-phenyl-1,2,4-triazol-3-yl phosphoro The most highly preferred are compounds of the thioate (triazophos) general formula: O-ethyl O-2,4,5-trichlorophenyl ethylphosphonothioate () 35 R3 S (-)-3-allyl-2-methyl-4-oxocyclopent-2-enyl N trans-chrysanthemate (allethrin) p-s (-)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (-)-trans RO chrysanthemate (bioallethrin) 3-phenoxybenzyl (-)-cis, trans-chrysanthemate (phe wherein R3 and R4 are selected from the group consist nothrin) ing of methyl and ethyl and Y is selected from the group consisting of hydrogen and alkyl groups having up to 4 2-(2-butoxyethoxy)ethyl thiocyanate carbon atoms. isobornyl thiocyanoacetate (terpinyl thiocyanoacetate) The most highly preferred pesticide compounds serv 45 ing as the active ingredients in the compositions of this carbon disulfide invention are those described in U.S. Pat. No. 2,988,474, 2-(4-tert-butylphenoxy)cyclohexyl prop-2-ynyl sulphite with the most preferred compound being o-ethyl-S- (propargite) phenylethyl phosphonodithioate, sold under the trade 4,6-dinitro-6-octylphenyl crotonates (dinocap) name Dyfonate (R) by Stauffer Chemical Company. ethyl 4,4'-dichlorobenzilate (chlorobenzilate) 50 Surfactants which are suitable for use in the composi S.S.S-tributyl phosphorotrithioate tions are nonionic and have an HLB (hydrophilic-lipo tributyl phosphorotrithioite (merphos) philic balance) of from about 17 to about 20. copper naphthenates The most preferred surfactant is manufactured under 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole the tradename Igepal (R) DM 970 by the GAF Corpora (etridiazole) 55 tion, and under different tradenames by various compa O-ethyl S.S.-diphenyl phosphorodithioate (edifenphos) nies, and is a dinonyl phenyl-150 mole ethoxylate. It has 6-butoxycarbonyl-2,3-dihydro-2,2-dimethylpyran-4-one an HLB of 19.0. (butopyronoxyl) The inclusion of the nonionic surfactant in this formu N,N-diethyl-m-toluamide (deet) lation serves to chemically stablize the organophospho dibutyl phthalate rus or other active pesticide compound on the clay dibutyl succinate granules, and also has the effect of reducing the dermal 1,5a,6,9,9a,9b-hexahydro-4-a(4H)-dibenzofurancarbox toxicity of the organophosphorus/clay granule formu aldehyde lation. dipropyl pyridine-2,5-dicarboxylate Other suitable surfactants of the general composition Of the many different types of pesticides useful in the 65 are, for example, alkyl and dialkylphenoxy poly(ethy present composition, certain classes are preferred. One leneoxy) ethanols. Suitable surfactants of the above preferred class is that of organosphosphorus com mentioned HLB range are exemplified by surfactants of pounds, particularly those of the formula: the following structural formula 4,994,261 6 While the formulation set forth above is described in terms of an organophosphorus compound such as de (C9H19) scribed in U.S. Pat. No. 2,988,474, it is also contem plated that other hydrophobic pesticides-clay granule 5 formulations can be dermally safened using this class of O(CH2CH2O)100-150H surfactants as described herein. wherein n is 1 or 2. Formulations of the type described herein are set Further examples of appropriate surfactants accord forth below. ing to the invention are summarized in Table I. 10 TABLE I Counter (R) 15% Thimet (R** 20% attapulgite 80% attapulgite 75% HLB Commercial Name Structure clay granules clay granules 17.9 Myrj 53 polyoxyethylene (50) stearate Igepal DM 970 5% Igepal DM 970 5% 18.0 Etocas 100 ethoxylated (100) castor oil 100% 100% 18.0 Lantrol AWS alkoxylated lanolin oil 15 Dyfonate (R) 15% Dyfonate (R) 20% 8.0 Veronic L67 ethoxylated coco mono-glyceride attapulgite 80% attapulgite 75% 18. Alcasurf CO200 ethoxylated castor oil clay granules clay granules 18.1 Chennax CO-200/50 ethoxylated castor oil Igepal DM 970 5% Igepal DM 970 5% 18.1 Pegosperse CO200 POE 200, castor oil 100% 00% 8. Veronic Li48 ethoxylated mono and diglyceride * = S-tert-butylthiomethyl O,O-diethyl phosphorodithioate 18.0 Tergitol 15-S-50 secondary alcohol PEG ether 20 as O,O-diethyl S-ethylthiomethylphosphorodithioate 18.3 Kessco polyethylene esters, PEG 4000 monoleate glycol 18.8 Brig 700 polyethylene 100 stearyl ether The Igepal DM970 has the structural formula 18.8 Kessco PEG esters PEG monostearate 8.5 Pluronic L-35 7.0 Pluronic P-65 25 Preferred clays for use as the inert diluents in the compositions of this invention are those from the atta pulgite group and those from the montmorillonoid group. The attapulgite clays have the prototype for 30 mula MgsSigO20(OH)28H2O and those of the mont morillonoid group have the prototype formula Al2. The pesticide formulation is normally prepared by (SiO10(OH)2. taking a quantity of Dyfonate (R) and mixing therewith The attapulgite clays are most effective for use in the the desired quantity of Igepal DM970 and applying that compositions of the invention as inert diluent carriers. 35 mixture to clay granules, and mixing the clay granules Both of these types of clays are well known to those with the active ingredient thoroughly. A typical pro skilled in the art and are described in the Handbook of cess is as follows. Dust Diluents and Carriers, by T.C. Watkins and L.B. Norton, Dorland Books, Caldwell, N.J. EXAMPLE 1. (1955). Five grams (5 g) of Igepal DM970 was dissolved in a Other conventional diluent carriers can be used, but solution of 15.82 g of Dyfonate (R) technical material the clays are preferable. (95% active ingredient) in a water bath heated between The active ingredients (pesticide and surfactant) are 55-75 C. This solution was then added with a pipette sprayed onto the clays and blended to yield formula to a quantity (79.18 g) of clay granules in a rotating tions with the active component distributed uniformly 45 beaker. The tumbling was continued for approximately throughout the mass. The granular compositions of this one hour after the addition of the active ingredient to invention are most useful in a size range of from 10-60, effect mixing of all of the components. preferably 18-48 mesh, U.S. Sieve Series Number. The pesticide compositions according to the inven Accordingly, the preferred composition of this inven 50 tion may have various amounts of pesticide, surfactant tion comprises and dry inert diluent carrier. (a) from about 1 to about 45 percent by weight of a The amount of pesticide compound included in the biologically effective amount of an organophosphorus pesticidal granule composition depends on the absorp compound of the formula tion capacity of the inert carrier and the spreading effi 55 cacy of the application equipment. In general, the pesti cide may comprise from 1% to about 45% of the com R. SiS position on a weight basis, preferably about 15%. P-s Expressed as a weight percent of the whole composi RO tion, the surfactant may range between about 0.1% and about 10% with a preferred range of between 1% and wherein R3 and R4 are selected from the group consist 6% and an optimal range of between 2% and 5%, de ing of methyl and ethyl and Y is selected from the group pending upon the exact composition of the surfactant. consisting of hydrogen and alkyl groups having up to 4 The amount of dry inert diluent carrier in pesticidal carbon atons. compositions may vary between 50% and about 98%, (b) from about 0.1 to about 10 percent by weight of 65 most preferably about 80%. dinonyl phenol 150 mole ethoxylate; and The invention will be better understood with respect (c) from about 50 to about 98 percent by weight clay to the following examples which are intended by the granules. inventors to be exemplary only and non-limiting. 4,994,261 7 8 The reduction in dermal toxicity achieved by the use animals. The results of these tests are reported in Table of the compositions of the invention is demonstrated in II. accordance with the following examples. TABLE II In conducting the dermal toxicity tests in Example II, Determination of LD50. According to a comparison was made between two formulations: one the Method of Litchfield and Wilcoxon of these formulations containing the Igepal DM 970 Route: Derfna Species: Rabbit Sex: Both nonionic surfactant, and the other containing a conven Formulation Dermal LD50 tional chemical stabilizer, dipropylene glycol. The der 1. 15% Dyfonate (R) 254 (163-394)* mal toxicity was measured in accordance with the fol 5% dipropylene glycol lowing technique. 10 80% attapulgite clay granules 100% EXAMPLE II 2. 15% Dyfonate (R) 453 (307-667)* Dermal Toxicity 5% Igepal DM 970 80% attapulgite clay, granules Acute dermal toxicity was determined in accordance 15 100% with the Environmental Protection Agency's Proposed Values in parentheses are 95% confidence limits, Guidelines for Registering Pesticides in the U.S.; Ha LD50 is measured in mg of composition per kg of body weight. zard Evaluation: Humans and Domestic Animals, Fed. Reg. 43:163, 37336-37402 (Aug. 22, 1978). It can be seen by comparing the application of the Albino rabbits (Stauffland White strain, Phillips Rab two formulations above that the pesticide formulation bitry, Soquel, Calif.) were housed in temperature con 20 containing the Dyfonate (R), Igepal DM 970 and attapul trolled animal rooms (65-70' F.), two to a cage in gite clay was about one-half as dermally toxic as was the suspended steel cages (24'x 16.5'x14"). Feed (Special comparison formulation containing Dyfonate (R), dipro Mixture, Gunter Bros., Morgan Hill, Calif.) and water pylene glycol and attapulgite clay. were provided ad libitum. Prior to treatment, the rabbits were randomly se 25 EXAMPLE III lected and individually identified using numbered ear Similar tests were conducted with additional formu tags. The day before treatment the skin areas to be lations wherein the active ingredient was varied by treated were closely clipped and the rabbits were fasted replacing the Dyfonate (R) pesticide with other pesti overnight with water available. cides of the organophosphorus-type. The results of The first dose tested was 501 mg/kg in 10 rabbits, 5 30 males and 5 females. Doses were thereafter selected at these tests, along with the formulations, are set forth in logarithmically spaced intervals. The levels selected Table III below. produced at least three test groups with mortality rates TABLE III between 10% and 90% and permitted calculation of the Determination of LD50 According to LD50 (abraded skin and/or intact skin) of males and 35 the Method of Litchfield and Wilcoxon females with a 95% confidence interval of 20% or less. Route: Dernal Species: Rabbit Sex: Both At least three dose levels and controls were tested. Formulation Dermal LD50 Four male and four female rabbits were used for each 1. 20%. Thimet (R) 162 (136-182)* 5% dipropylene glycol succeeding dose level. In some of the tests, half of the 75% attapulgite clay rabbits at each dose level were further prepared by 100% making epidermal abrasions with a needle in a cross 2. 20% Thimet (R) 231 (208-258)" hatch manner over the entire exposure area. The abra 5% Igepal DM 970 sions were sufficiently deep to penetrate the stratum 75% attapulgite clay corneum, but not the dermis. A single application of the 100% 45 3. 15% Counter (R) 23.5 (19.7-28. 1) composition was applied neat to the dose site. The com 5% dipropylene glycol position was held in contact with the skin by a non 80% attapulgite clay absorbent binder. To insure the integrity of the binder 100% an outer wrapping of gauze was applied. At the end of 4. 15% Counter (8) 42.9 (36.7-50.3) the 24 hour exposure period, the wrappings were re 5% Igepal DM 970 moved and the skin wiped and/or washed to remove 50 80% attapulgite clay any remaining test substance. The animals were then 100% wrapped with fresh gauze which was left in place for 72 Values in parentheses are 95% confidence limits. hours. LDso is measured in mg of composition per kg of body weight. Four rabbits (two of each sex) were sham-treated by wrapping each in a similar manner. 55 Again it will be seen that the substitution of the sur Animals were observed for at least 14 days after dos factant Igepal DM 970 for dipropylene glycol was ef ing or until all signs of reversible toxicity in survivors fective in reducing the dermal toxicity of the formula subsided, whichever occurred later. tion by a factor of about 2. Observation for clinical signs and mortality were recorded frequently the first day, and early morning INSECTICIDAL EFFECTIVENESS and late afternoon thereafter. The animals were ob The insecticidal effectiveness of the composition was served once a day during weekends and holidays. All tested in the following manner: clinical signs were recorded for the onset, duration and One cubic centimeter (cc) of Western spotted cucum severity. Rabbits were weighed on days 0 (prior to ber beetle larvae (Diabrotica undecimpunctata) supplied treatment), 7, 14 or at death, with the mean body weight 65 by Mannerheim containing about 7,000 eggs was di calculated for each day. luted to a final concentration of 250 eggs/cc by sus The acute dermal toxicity in these tests was found to pending 0.5 cc of undiluted eggs in 14 cc of water con be unaffected by prior abrasion of the skin of the test taining 0.2% Dacagin (Diamond Alkali Co.). Eggs may 4,994,261 10 be stored in this suspension for 5 days at 5 C. without 3. The pesticide composition of claim 1 wherein said significant loss of viability. pesticide compound comprises those of the formula Ten grams (10 g) of moist "Supersoil" (Wonderline, Rod McLellan Co., San Francisco, Calif.) were placed R X in a one ounce clear plastic cup (Thunderbird Container 5 N P-R Corporation, El Paso, Tex.). The test material was dis / solved in acetone or an appropriate solvent. A 0.05 R milliliter (ml) aliquot of the test sample that had been diluted to the desired concentration was added to the soil. The cup was capped and the soil was mixed on a O in which X is oxygen or sulfur; and R, R and R2 are Vari-Whirl mixer for approximately 15 seconds. An independently selected from the group consisting of indentation was made on the surface of the soil and 0.2 C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C2-C6 cc of the egg suspension was added. The eggs were alkenyl, C2-C6 alkenoxy, C2-C6 alkenylthio, phenyl, covered with soil and maintained at room temperature phenoxy, phenylthio, C7-C9 phenylalkyl, C7-C9 pheny (approximately 70 F). Four days later a section of 15 lalkoxy, and C7-C9 phenylalkylthio, wherein each Romaine lettuce leaf was placed in the treated cups. member of such group optionally substituted with up to One week later the cups were examined for live larvae. three substituents selected from halogen, C1-C4 alkyl, Test concentrations range from 10 ppm down to that C1-C4 alkoxy, cyano, and nitro. at which approximately 50% mortality occurs. 4. The pesticide composition of claim 2 wherein said There were two test compositions used to compare 20 organophosphorus pesticide compound comprises those the insecticidal effectiveness of the compositions of this of the formula invention. The first composition (1) formulated in ac cordance with the compositions of the invention con tained 15% Dyfonate (R), 5% Igepal EM 970 and 80% R3 S attapulgite, and the second (2) contained 20% Dyfona 25 N te (R), 5% dipropylene glycol and 75% attapulgite. The p-s results of these tests are set forth in Table IV below. RO TABLE IV in which R3 and R4 are selected from the group consist Diabrotica LCso Value (ppm) 30 ing of methyl and ethyl and Y is selected from the group Composition No. 1 0.4 consisting of hydrogen and alkyl groups having up to 4 Composition No. 2 0.4 carbon atoms. 5. The composition of claim 1 wherein said surfactant As can be seen from the results set forth above, the is dinonyl phenol-150 mole ethoxylate. LCso value against Diabrotica of the composition of the 35 6. The composition of claim 1 wherein said organo invention was the same as that of a similar composition phosphorus compound comprises about 15% on a containing the conventional chemical stabilizer, dipro weight basis of said composition. pylene glycol. This demonstrates that the substitution of the Igepal DM 970 for dipropylene glycol does not 7. The composition of claim 1 wherein the dry inert adversely effect the biological effectiveness of the ac 40 diluent carrier is an attapulgite clay and comprises at tive ingredient. least about 50% on a weight basis of said composition. It will be readily apparent to those skilled in the art 8. The method of reducing dermal toxicity to a mam that the compositions of the invention offer markedly mal exposed to a biologically effective amount of a reduced dermal toxicity without significantly reducing granular, dermally toxic organophosphorus pesticide the biological effectiveness of the pesticidal compound 45 compound comprising the steps of adding to said der used in the composition. mally toxic organophosphorus compound an amount of What is claimed is: a nonionic surfactant of the formula 1. A granular organophosphorus pesticide composi tion that has been safened for handling comprising: (a) from about 1 to about 45 percent by weight of a 50 (C9H19) biologically effective amount of a dermally toxic organophosphorus pesticide compound; (b) from about 0.1 to about 10 percent by weight of a nonionic surfactant of the formula 55 wherein n is 1 or 2 sufficient to reduce the dermal toxic ity of said dermally toxic organophosphorus compound. (C9H19) 9. The method of claim 8 wherein said dermally toxic compound is O-ethyl-S-phenyl-ethyl phosphonodithio ate. O(CH2CH2O)100-150H 10. The method of controlling an insect pest compris wherein n is 1 or 2; and ing applying to the locus where said insect pest is found (c) from about 50 to about 98 percent by weight of a during some part of its life cycle an insecticidally effec dry inert diluent carrier. tive amount of a granular insecticidal composition con 2. The pesticide composition of claim 1 wherein said 65 prising: organophosphorus pesticide compound is selected from (a) from about 1 to about 45 percent by weight of a the group consisting of phosphonates and thiophos biologically effective amount of an organophos phonates. phate compound having the formula 4,994,261 11 12 11. The method of claim 10 wherein said organophos phate compound is O-ethyl-S-phenyl-ethyl phos R. X NII phonodithioate. P-R 12. A granular organophosphorus pesticide composi / 5 tion that has been safened for handling comprising: R (a) from about 1 to about 45 percent by weight of a biologically effective amount of a dermally toxic in which X is oxygen or sulfur; and R, R and R2 O-ethyl-S-phenyl-ethyl-phosphonodithioate; are independently selected from the group consist (b) from about 0.1 to about 10 percent by weight of a ing of C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, 10 nonionic surfactant of the formula C2-C6 alkenyl, C2-C6 alkenoxy, C2-C6 alkenylthio, phenyl, phenoxy, phenylthio, C7-C9 phenylalkyl, C7-C9 phenylalkoxy, and C7-C9 phenylalkylthio, (C9H19) each member of such group optionally substituted with up to three substituents selected from halogen, 15 O(CH2CH2O)100-150H C1-C4 alkyl, C1-C4 alkoxy, cyano, and nitro; (b) from about 0.1 to about 10 percent by weight of a wherein n is 1 or 2; and dinonyl phenyl ethoxylate surfactant and (c) from about 50 to about 98 percent by weight of a (c) from about 50 to about 98 percent by weight of a 20 dry inert diluent carrier. dry inert diluent carrier. k

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