United States Patent c19J
`Chan et al.
`
`[11] Patent Number:
`[45] Date of Patent:
`
`5,075,058
`Dec. 24, 1991
`
`[54] PROCESS FOR PREPARING PELLETS
`COMPRISING INSECTICIDAL
`N-HYDROCARBOYL
`PHOSPHOROAMIDOTHIOATES AND/OR
`PHOSPHOROAMIDODITHIOATES, AND
`FUNGICIDES, HERBICIDES, FERTILIZERS
`OR OTHER INSECTICIDES
`
`[75]
`
`Inventors: Jim H. Chan, Martinez; Kent A.
`Hasse, El Sobrante; Roderick I.
`Satre, Point Richmond; James H.
`Trusler, Pleasant Hill, all of Calif.
`
`[73] Assignee: Chevron Research and Technology
`Company, San Francisco, Calif.
`
`[21] Appl. No.: 472,353
`
`Jan. 30, 1990
`(22] Filed:
`Int. a.s ................................................ B29B 9/08
`[51]
`[52] U.S. Cl ..................................... 264/118; 264/141;
`424/405; 424/408;424/489; 514/120
`[58] Field of Search ............... 264/118, 141, 142, 143,
`264/117; 71/64.04;424/408,489,405; 514/120
`
`[56]
`
`References Cited
`U.S. PATENT DOCUMENTS
`3,914,417 10/1975 Magee ................................. 514/120
`4,048,268 9/ 1977 Ludwig ............................... 264/ 118
`4,374,082 2/1983 Hochschild ......................... 264/ 129
`4,446,086 5/1984 Molenaar et al. ................... 264/ 118
`4,542,162 9/1985 Rutherford et al. .................. 521/79
`4,636,343 1/1987 Shibanai .............................. 264/118
`4,665,100 5/1987 Ludwig ............................... 514/ 778
`4,668,455 5/1987 Hansen et al. ...................... 264/ 143
`4,678,594 7/1987 Parfomak et al. .................. 264/ 118
`4,683,224 7/1987 Fahmy ................................ 514/ 120
`4,722,815 2/1988 Shibanai .............................. 264/ 117
`4,767,773 8/1988 Ayad ................................... 514/351
`4,769,242 9/1988 Shibanai .............................. 424/ 411
`Primary Examiner-Mary Lynn Theisen
`Attorney, Agent, or Firm-Heller, Ehrman, White &
`McAuliffe
`[57]
`ABSTRACT
`A method of making insecticidal pellet compositions of
`N-hydrocarboyl phosphoroamidothioates and phos(cid:173)
`phoroamidodithioates, combined with a herbicide, fun(cid:173)
`gicide, fertilizer or other insecticide is provided.
`
`11 Claims, No Drawings
`
`

`

`1
`
`5,075,058
`
`PROCESS FOR PREPARI:'\G PELLETS
`COMPRISl:'\G l:'\SECTICIDAL
`N-HYDROCARBOYL
`PHOSPHOROAMIDOTHIOATES AND/OR
`PHOSPHOROAMIDODITHIOATES, A1'D
`FUNGICIDES, HERBICIDES, FERTILIZERS OR
`OTHER INSECTICIDES
`
`2
`consumer on the basis of price and empty container
`disposal requirements.
`An agglomerate form of ORTHENE@ which also
`minimizes airborne contamination due to dust, has been
`5 constrained to dilute concentrations of ORTHENE@
`applied to large particles by spraying and then dried, or
`as a dilute concentration of ORTHENE@ combined
`with binders and anti-caking agents to form agglomer-
`ates via processes known to those skilled in the art, such
`as, pan granulation, extrusion, fluid granulation, pellet(cid:173)
`izing. The concentration of ORTHENE@ via Jhese
`methods has heretofore been limited to a concentration
`no greater than about 36% to 50%, with known com(cid:173)
`mercial products typically no more than 5% OR-
`IS THENE. The limit on concentration ofORTHENE@
`was due to the melt property of ORTHENE ® limiting
`the feasible operability of this form ofproduct. Concen(cid:173)
`tration of active ingredient is further limited by the
`ability of binding agents to form agglomerates, i.e. a
`minimum amount of any particular binding agent is
`required in order to meet physical properties of attrition
`resistance, crush strength and bulk density. In the case
`where liquid ORTHENE@ solutions were sprayed on
`agglomerates and then dried, the limitation of concen(cid:173)
`tration was due to the practical wetting ability of the
`receiving agglomerate. Too much liquid applied would
`form a mud. At these low levels of ORTHENE@
`concentration, commercial products are more costly to
`produce and are not suitable for applications of.ORTH(cid:173)
`ENE@ made via solution spraying.
`The ORTHENE@ xxS formulations have problems
`due to the inorganic anti-caking agent ingredients.
`These anti-caking agents are not soluble in water (the
`typical application spray solvent) or other normal sol(cid:173)
`vents. Due to their insolubility, they can settle in the
`applicator's spray tank. The settled anti-caking agents
`plug spray nozzles which detracts from the marketabil(cid:173)
`ity of the ORTHENE@ xxS product line. This spray
`nozzle plugging problem can occur when ORTH(cid:173)
`ENE@ xxS products are tank mixed with other com(cid:173)
`mercial pesticides, which is a normal farming industry
`practice. While methods to minimize the occurrence of
`anti-caking agent settling have evolved, they require
`special procedures to avoid nozzle plugging conditions,
`which adds to the inconvenience of using OR TH(cid:173)
`ENE@ xxS.
`Furthermore, an anti-caking agent(s) segregates in
`the manufacturing process equipment during material
`handling procedures and forms insoluble bits of anti(cid:173)
`caking agent which can cause spray nozzle plugging.
`This may lead to inconsistent application of the correct
`amount of active ingredient.
`Therefore, alternative forms to OR THENE ® pow(cid:173)
`ders, that resolve problems characteristic of dusts are
`desired by both the manufacturer and the marketplace.
`One possible alternative to a powdered ORTHENE@
`is in the form of a pellet: a cylindrically shaped solid.
`Pellets practically eliminate the dust problems and re(cid:173)
`duce the surface area-to-weight ratio which mitigates
`the odor problem.
`However, currently available granular ORTH(cid:173)
`ENE @, as mentioned above, contains relatively small
`amounts of ORTHENE@, typically no more than 5%
`active ingredient. Attempts to manufacture technical
`assay (approximately 97% active ingredient) ORTH(cid:173)
`ENE@ pellets from the dry ORTHENE@ technical
`powder have heretofore been unsuccessful. The anti(cid:173)
`caking agents and binders needed to make the currently
`
`60
`
`25
`
`45
`
`The present invention is directed to a method of 10
`making pelletized insecticidal N-hydrocarboyl phos(cid:173)
`phoroamidothioates and/or and phosphoroamidodithi(cid:173)
`oate formulations containing fungicides, herbicides,
`fertilizers or other insecticides.
`BACKGROUND OF THE INVENTION
`Certain N-hydrocarboyl phosphoroamidothioates
`and phosphoroamidodithioates have high insecticidal
`activity. A particularly important commercial insecti(cid:173)
`cide within these classes of compounds is the insecticide 20
`ORTHENE@, which can be systemically taken up by
`a plant so. that insects which feed and/or live on the
`plant are killed, in addition to those insects which di(cid:173)
`rectly ingest or are contacted by the insecticide. See
`U.S. Patent Nos. 3,716,600, 3,845,172 and 3,914,417.
`ORTHENE@ is commercially produced as technical
`grade chemical of about 97 to 99.5% purity. One
`method of formulating technical grade ORTHENE ®
`for commercial use is to mix the technical grade powder 30
`with an anti-caking agent, such as fumed silica, and a
`wetting agent. The wetting agent is utilized to assist the
`wetting of silica (if present) and to improve the spread(cid:173)
`out of ORTHENE@ and the anti-caking agent is used
`to prevent agglomeration of the ORTHENE@ in its 35
`container.
`The wetting agent is utilized to assist the wetting of
`silica (if present) and to improve the spread-out of
`ORTHENE@ when it is applied to crops as a spray
`solution, or when applied as a dust, after exposure to 40
`moisture via rain, dew, or irrigation. The powdered
`commercial forms of ORTHENE@ are available in
`dilutions referred to as ORTHENE@ 90S, ORTH(cid:173)
`ENE@ 75S, OR THENE@ 50S. and in other commer-
`cial dilutions.
`The powder form allows formulations of ORTH(cid:173)
`ENE ® to relatively high concentrations, e.g., ORTH(cid:173)
`ENE ® 90S. Other, lower concentrate formulations arc
`targeted to discrete markets using a soluble powder
`signified as -xxS. In most cases, the application of so
`ORTHENE@ XXS to the crop is via a water solution
`spray. The anti-caking agents, while promoting product
`flowabi)ity during the solution/mixing process, do not
`enhance the solution method of application. On the
`other hand, inherent to all powders, handling difficul- 55
`ties due to dust make this form of product less desirable
`than liquids and agglomerate forms. Furthermore,
`ORTHENE@ has a characteristically mercaptan odor
`(believed to be organothio compounds) which is com-
`pounded by the problems with dust.
`ORTHENE@ is available in liquid form, which
`minimizes or eliminates airborne contamination due to
`dust. However, due to solubility and storage stability
`limitations of solutions, its concentration is limited to a
`maximum of 25o/c, the balance being solvent and adju- 65
`vants. ORTHENE@ in a liquid formulation has a sol(cid:173)
`vent and packaging expense as well as a container dis(cid:173)
`posal requirement that makes it less attractive to the
`
`

`

`3
`available granular ORTHENE@ add to product cost.
`can cause excess wear and tear on equipment, and by
`dint of being a major fraction of the product formula,
`require more bulk product than the concentrated po,v(cid:173)
`ders in order to deliver effective amounts of ORTH- 5
`ENE® to the protected crop.
`Additionally, the anti-caking agents and binders used
`to form the currently available granular ORTHENE ®
`have the sam·e water insolubility problem that the anti-
`caking agent has in.ORTHENE ® powdered formulae.
`Because of that. commercial granular ORTHENE ®
`products are limited to use by direct application to the
`crop; i.e., placing granules on or around each plant,
`which is impractical for most commercial farming ven- 15
`tures. Furthermore, occasionally there are compatibil-
`ity problems in tank mixes containing OR THENE ®
`and other pesticides. It would thus be desirable to de(cid:173)
`velop compatible cocktails of pesticides or mixes of
`pesticides with fertilizers.
`It would therefore be desirable to provide a method
`for making pellets containing ORTHENE ® as well as
`other fertilizers, herbicides, fungicides or even other
`insecticides for delivery of these active ingredients
`without the above problems.
`It is thus an object of the present invention to provide
`pelletized forms of insecticidal N-hydrocarboyl phos(cid:173)
`!Ind phosphoroamidodithioates
`phoroamidothioates
`containing fertilizers, herbicides, fungicides, or other
`insecticides.
`This and other objects of the invention will be appar(cid:173)
`ent from the following description and from the prac(cid:173)
`tice of the invention.
`
`IO
`
`20
`
`30
`
`. 5,075,058
`
`4
`
`0
`'
`II
`C-R-
`
`wherein R, R 1, R2, R3 and Y are as described herein(cid:173)
`above. Particularly preferred compounds are those in
`which R and RI are independently methyl, ethyl, ally!
`or alkenyl; R2 is Hor alkyl; and R3 is hydrogen; and Y
`is oxyge·n .. The most preferred compound is that in
`which R, RI, and R2 are methyl, R3 is hydrogen and Y
`is oxygen. Compounds of the above formula may be
`prepared as described in technical form in U.S. Pat.
`Nos. 3,716,600, 3,845,172 and 3,914,417 which usually
`provide compositions of about 97-98.5% purity. This
`technical grade insecticide will be mixed in a dry form
`with one or more solid or liquid active ingredients prior
`to being pelletized as described herein.
`The mixture described above may also contain inert
`diluents, such as ammonium sulfate, in an amount less
`than about 5% by weight ofthe total pellet composi-
`25 tion, preferably 2% or less by weight of the total pellet
`composition.
`Surfactants may also be added, such as polymeric
`surfactants known by the trade names "Pluronic @" or
`"Tetronic @" (sold by BASF). Usually, less than about
`5% by weight of the total pellet composition may com(cid:173)
`prise a surfactant. The surfactants used in accordance
`with the present invention are polymeric and, in order
`to form an extrudable solid composition. should be
`softenable within the temperature range of about 80. to
`35 130.F and have melting points greater than about 130 F .
`Such nonionic surfactants include the generic types
`alkyl or aryl alcohol ethylates. These surfactants are
`commercially available under the trade names Uni-
`thox TM (520, 580, 480 etc.) made by Petrolite Chemi(cid:173)
`cal; Pluronic ® (BAS}:), Sellogen TM (Henkel), Tet(cid:173)
`ronic ® surfactants, block copolymers of propylene
`and ethylene oxides of ethylenediamine; and Al(cid:173)
`kasurf TM, Alkatronic TM, Alkapol TM (glycols) made
`by Alkaril Chemicals.
`The particular surfactant used will depend in part on
`the intended use of the pellets. Those surfactants having
`an HLB in the range of about 16 to greater than 20 will
`be substantially water soluble and therefore be usable in
`conventional mixing tanks used to distribute sprays.
`Pellets made from surfactants having an HLB lower
`than about 16 will have lower water solubility and will
`be useful, for example, in direct application on the
`plants or their environment for controlled release of the
`active ingredients of the pellet.
`Particularly preferred surfactants for imparting high
`water solubility to the pellets are Unithox 480. Particu(cid:173)
`larly preferred surfactants for imparting low solubility
`to the pellets are Unithox 520.
`It will be appreciated that combinations of different
`surfactants may also be utilized to modify the solubility
`properties of the pellet as desired.
`Optionally, solid and/or liquid additives may be in(cid:173)
`cluded in the dry mixture. Additives may include anhy(cid:173)
`drous magnesium sulfate, in amount up to about 5% by
`65 weight of the total pellet composition, preferably 2% or
`less by weight. This serves as a dehydrating agent and
`will absorb trace amounts of water present in the pellets
`to prevent hydrolysis of the insecticide. Small amounts
`
`SUMMARY OF THE INVENTION
`The present invention provides a method for prepar(cid:173)
`ing pelletized insecticidal compositions comprising pel(cid:173)
`lets which contain as one of the active ingredients, an
`insecticidal compound or mixture of compounds of the
`formula:
`
`40
`
`45
`
`50
`
`wherein R and RI individually are alkyl, alkenyl or
`alkynyl ofup to 6 carbon atoms, R3 is hydrogen or alkyl
`of 1-6 carbon atoms, R2 is hydrogen, alkyl of 1-18
`carbon atoms, cycloalkyl of 3-8 carbon atoms, alkenyl
`of 2-18 carbon atoms or alkynyl of 3-18 carbon atoms,
`and Y is oxygen or sulfur. The pellets are characterized 55
`by an attrition resistance of at least about 92%, a mean
`hardness of greater than about 1.5 lb-F and a bulk den(cid:173)
`sity of at least about 39 lb/ft3 (about 0.63 gm/cc). The
`pellets are made by extrusion of a solid composition.
`The concentration of the insecticidal ingredient in these 60
`pellets is in the range of about 2% to 80% a.i., with the
`most likely concentration of 70% a.i.
`
`DESCRIPTION OF THE PREFERRED
`EMBODIMENTS
`One of the active insecticidal ingredient of the pellets
`will be a compound or a mixture ofcompounds of the
`formula:
`
`

`

`5,075,058
`
`5
`of deodorants and anti-foam agents may also be used as
`additives.
`As discussed above, it is a particular advantage of the
`present invention to provide pelletized compositions
`which contain active ingredients in addition to the in- 5
`secticidal composition described above. In particular, it
`will particularly advantageous to combine the ORTH(cid:173)
`ENE ® insecticides in a pellet with other insecticides,
`particularly pyrethroid insecticides such as DECIS TM
`(also known as deltamethrin, melting point 98' -101 "C.), 10
`PYDRIN TM and ASANA TM (Fenvalerate), DANI(cid:173)
`TOL TM, CASCADE TM
`(Flufenoxuron), DURS(cid:173)
`BAN TM (chlorpyrifos), DIBROM TM ("Naled"), etc.
`Most of these insecticides are solids, thus to prepare a
`pellet with ORTHENE ® they are preferably milled, if 15
`necessary, to fine partide grain size (1-8 microns aver(cid:173)
`age diameter), and mixed with a solid dispersant, solid
`wetting agent, and/or solid surfactant. A particularly
`preferred composition is a mixture of 13:1 ORTH(cid:173)
`ENE@ to ASANA TM containing 6% by weight of 20
`Morwet TM D425 dispersant: 0.5% wetting agent and
`7% Unithox TM 480 surfactant formed into pellets.
`Some of the above insecticides are liquids, such as
`PYDRIN TM (yellow liquid, melting point 23' C.). In
`such cases the liquid may be first absorbed onto a car- 25
`rier such as a diatomaceous earth (such as Celatom TM )
`and then the two solids (the ORTHENE@ and the
`PYDRIN TM saturated Celatom TM) may be mixed
`with a solid dispersant, solid wetting agent and solid
`surfactant.
`In some instances, the second insecticide, such as
`DANITOL TM is highly toxic and therefore to allevi-
`ate the hazard of handling the pellets, the DANI(cid:173)
`TOL TM may first be encapsulated by mixing with a
`surfactant such as Pluronic@ series (F-108) Tet- 35
`ronic TM series (such as 908), Unithox TM series (such
`as 480, 550 or 520) by milling the DANITOL TM with
`the surfactant. The ORTHENE ® is then mixed with
`the milled DANITOL TM /surfactant and pelletized in
`a~~~L
`Similarly, solid or liquid fungicides, herbicides, or
`fertilizers may be pelletized with the ORTHENE@ in
`accordance with the methods described above.
`In addition, in some instances, particularly when a
`fertilizer is an active ingredient. the direct contact of the 45
`ORTHENE ® insecticide with the fertilizer (or fungi(cid:173)
`cide, herbicide or other insecticide) may chemically
`degrade the OR THENE ® or vice versa, thereby de(cid:173)
`tracting from the desired activity of the pellet. In such
`instance each of the active ingredients may be pelletized 50
`separately and then blended thereby retaining the stabil-
`ity of each of the active. ingredients. For example,
`KOCIDE TM
`(copper hydroxide) is not chemically
`compatible with OR THENE ® and therefore first,
`KOCIDE TM /Unithox TM 480 pellets may be made 55
`into a stable combination, then it is combined with
`ORTHENE ® pellets to form a stable physical insec(cid:173)
`ticide/fungicide formulation. Other fungicides include
`SPOTLESS TM , FOLPET TM , CAPT AN TM , etc.
`Herbicides which may be utilized include DEUR!- 60
`NOLTM,DURNOLTM,ODRAM,SURFLANTM,
`BENCHMARK TM , SELECT TM , etc. Fertilizers
`include various formulations of NPK fertilizers such as
`23-19-17, etc.
`In some instances, the physical dry mixture from 65
`which the pellets are formed will need to be intimately
`mixed by evaporation from a solution. For example,
`ORTHENE ® can be protected by a surfactant by first
`
`6
`mixing ORTHENE ® and a surfactant such as Uni(cid:173)
`thox TM 480 (typically I :4 ratio) to form a solution in
`methylene chloride, alcohol, or water. By evaporation
`of the solvent, the remaining solid may be ground and
`sieved to an appropriate size (such as 20 mesh). Then
`the dry powder may be mixed with a solid fertilizer
`(such as 23-19-17) and pelletized as described above. In
`this instance the OR THENE ® is protected from the
`fertilizer by the surfactant.
`In the most preferred embodiment according to the
`present invention the pellets are made by forming a dry,
`extrudable mixture of the solid technical insecticide
`composition and the other active ingredients, optionally
`containing other dry additives described above. The
`dry ingredients should be ground or provided in a pow(cid:173)
`dered form. In some instances a diluent such as ammo-
`nium sulfate will also be utilized usually in an amount
`less than about 5% and usually around I o/c by weight of
`the total composition. No solvent is added to this com(cid:173)
`position. However. it is realized that many commercial
`versions of surfactants contain small amounts (typically
`about 2 % by weight of the surfactant) of moisture. The
`presence of such moisture is not deleterious to the prep-
`aration of the pellet, and the pellet may be later dried, if
`desired.
`As the extrusion product exits the extruding orifice,
`the product is cut to appropriate size, usually about 3
`mm to IO mm in length. Useful pellets will be extrudates
`30 of about 3 mm to 25 mm in length with diameters from
`about 1.5 mm to 7 mm. Spherical pellets are also useful
`having diameters of about I mm to 5 mm.
`
`EXAMPLE I
`In a Hobart (C-147) mixer 171g of ASANA TM tech
`(75%) insecticide was added slowly to 243g Cela(cid:173)
`tom TM MN-47 diatomaceous earth. After mixing for
`15 minutes 165g of Morwet TM D-425, 15g of Mor(cid:173)
`wet TM EFW (dispersants) were. added. This was
`mixed ,vith 210g Unithox TM 480 (surfactant), 2196g
`~
`ORTHENE@ Tech (98%) and 1.5g of an anti-foam
`agent (Antifoam A). )"he mixture was screened to
`break-up lumps of the insecticides, then extruded into
`pellets.
`
`EXAMPLE 2
`A pre-mix consisting of 177g. SPOTLESS TM Tech
`(81%), 165g. Morwet TM D-425 and 45g. MorwetTM
`EFW were mixed in a Hobart mixer. This pre-mix was
`then mixed with 2463g ORTHENE@ Tech (98%),
`150g Unithox TM 480 and 1.5g Antifoam A. The mix(cid:173)
`ture was extruded into pellets at about 100' F.
`
`EXAMPLE 3
`In a Hobart mixer 210 DIBROM TM (insecticide)
`was added to 300g Celatom TM and mixed for 15 min(cid:173)
`utes. This premix was then mixed with 2100g ORTH(cid:173)
`ENE@ Tech (98%), 165g Morwet TM D-425, 15g
`Morwet TM EFW, 210g Unithox TM 480 and 1.5g An(cid:173)
`tifoam A. The mixture was extruded into pellets at
`about 91' F.
`
`EXAMPLE 4
`To a pre-mix containing 2700g Fertilizer 23-19-17 and
`240g Unithox TM 480 were added 60g ORTHENE@
`Tech (97%) and 1.5g Antifoam A. The mixture was
`extruded to 3/32" pellets in a California Pellet Mill,
`then dried.
`
`

`

`7
`
`5,075,058
`
`8
`5. A method according to claim 4 wherein said ex(cid:173)
`trudable mixture further comprises a solid dispersant,
`wetting agent and/or surfactant.
`6. A method according to claim 4 wherein said insec-
`5 ticide comprises a solid pyrethroid.
`7. A method according to claim 4 wherein said insec(cid:173)
`ticide comprises a liquid pyrethroid absorbed in a solid
`inert carrier.
`8. A method according to claim 5 wherein said step
`10 (a) comprises mixing said second active ingredient with
`a surfactant to form surfactant-coated particles of said
`second active ingredient, and mixing said compound
`with said surfactant-coated particles.
`9. A method according to claim 7 wherein said solid
`15 inert carrier comprises diatomaceous earth.
`10. A method for preparing solid insecticidal pellets
`comprising (i) a compound or mixture of compounds of
`·
`the formula:
`
`EXAMPLE 5
`A pre-mix of 60g ORTHENE@ Tech (97'ic) and
`240g Unithox TM· 480 was ground to a powder, then .
`methylene chloride was added and the mixture was
`stirred until uniform. The methylene chloride was evap(cid:173)
`orated, the solids were ground and dried, then placed in
`a Hobart mixer. To the mixer 2700g of Fertilizer
`23-19-17 was added, followed by 1.5g Antifoam A . The
`mixture was extruded into pellets at a die temperature of
`about 95.F into 3/ 32" pellets, then dried.
`What is claimed is:
`1. A method for preparing insecticidal pellets com(cid:173)
`prising i) a compound or mixture of compounds of the
`formula:
`
`20
`
`25
`
`where Rand R1 individually are alkyl, alkenyl or alky(cid:173)
`nyl of up to 6 carbon atoms, R3 is hydrogen or alkyl of
`1-6 carbon toms, R2 is hydrogen, alkyl of 1-18 carbon
`atoms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-18 30
`carbon atoms or alkynyl of 3-18 carbon atoms, and Y is
`oxygen or sulfur; ii) a second active ingredient selected
`from the group consisting of fungicides, herbicides,
`fertilizers and other insecticides; comprising the steps of
`(a) forming an extrudable mixture comprising said 35
`compound and said second active ingredient;
`(b) forming said pellets by extrusion of said mixture
`extrudable and cutting the extrudate.
`2. A method according to claim 1 wherein R and RI 40
`are independently methyl, ethyl, ally) or alkenyl; R 2 is
`H or alkyl; R3 is hydrogen and Y is oxygen.
`3. A method according to claim 2 wherein R, R 1, and
`R2 are methyl; R3 is hydrogen.
`4. A method according to claim 1 wherein said sec(cid:173)
`ond active ingredient comprises an insecticide.
`
`45
`
`where Rand Rl individually are alkyl, alkenyl or alky(cid:173)
`nyl of up to 6 carbon atoms, R3 is hydrogen or alkyl of
`1-6 carbon atoms, R2 is hydrogen, alkyl of 1-18 carbon
`toms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-18
`carbon atoms or alkynyl of 3-18 .carbon atoms and Y is
`oxygen or sulfur; and (ii) a second active ingredient
`selected from the group consisting of fungicides. herbi(cid:173)
`cides, fertilizers and other insecticides; comprising the
`steps of:
`(a) forming a suspension or solution containing said
`compound and a dispersant, wetting agent and/ or
`surfactant;
`(b) evaporating the solvent from said solution .or
`dispersion;
`(c) dividing the remaining so]ids into particles; and
`(d) mixing said particles with said second active in(cid:173)
`gredient and forming the resultant mixture into
`pellets.
`11. A method according to claim 10 wherein said
`second active ingredient comprises a solid fertilizer.
`• • • • •
`
`50
`
`55
`
`60
`
`65
`
`

`

`UNITED STATES PATENT AND TRADEMARK OFFICE
`CERTIFICATE OF CORRECTION
`
`PATENT NO.
`5,075,058
`DATED
`December 24, 1991
`INVENTOR(S): Chan, Hasse, Satre, and Trusler
`It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
`corrected as shown below:
`
`column 1, line 51: •.• XXS to the crop •.• should read
`... xxs to the crop .•.
`
`Column 7, line 28: ... carbon toms, R2 ••• should read
`... carbon atoms, R ...
`2
`Column 8, line 30: ... toms, cyclolkyl. .. should read
`... atoms, cycloalkyl ...
`
`Signed and Sealed this
`Twentieth Day of July, 1993
`
`Attest:
`
`Attesting Officer
`
`Acting Commissioner of Patents and Trade_marks
`
`MICHAEL K. KIRK
`
`