MXPA01001138A - Microencapsulation formulations of cadusafos - Google Patents

Abstract

Pesticidal formulations of cadusafos are provided. An aqueous capsule suspension is provided, containing from about 150 to 360 grams of cadusafos per liter of formulation and having lower mammalian toxicity than aqueous cadusafos microemulsion formulations is prepared by interfacial polymerization of a first polyfunctional compound, such as a polymethylene polyphenyl isocyanate, with a second polyfunctional compound, such as a polyfunctional amine or mixtures of polyfunctional amines, in an aqueous phase optionally containing from about 0.05 to about 0.50 xanthan gum viscosity modifier/stabilizer. A granular form of the microencapsulated cadusafos is also provided. Several such formulations and the method of their preparation are described.

Description

FORM U LATION IS OF MICROENCAPSULATION OF CADUSAFOS Field of the Invention The present invention relates to organophosphate pesticide formulations. In particular, the invention provides microencapsulated insecticide / nematicide formulations, cadphefoss, which are equally effective, although with reduced toxicity, compared to conventional formulations.

Background of the Invention The organophosphate compound, S, S-di-sec-butyl-O-ethyl phosphorodithioate, (cadusafos), is an effective insecticide and nematicide. However, the toxicity of cadusafos spoils its safe use. For example, it is currently recommended that for an aqueous microemulsion formulation of 1 00 g / l of cadusafos, the user should use a full-body protection for the handling and application of said formulation. The label also indicates that the formulation is highly toxic to mammals, fish, arthropods and birds. Therefore, there is a need to develop formulations of cadusafos, which maintain their effectiveness as an insecticide or nematicidca, but which reduce their toxicity in mammals, birds, fish and other non-target organisms. Such formulations would improve safety for humans, and could minimize any negative impact on the environment, which is the result of the use of this compound.

Summary of the Invention In accordance with the present invention, microencapsulated formulations of cadusafos, effective as pesticides, having among other advantages, low or moderate toxicity for non-target organisms are provided.

According to one aspect of the invention, the formulation comprises an aqueous suspension of microcapsules, which are composed of a polyurea shell surrounding a cadusafos nucleus. The polyurea coating is formed by the interfacial polymerization of a polyisocyanate and one or more polyfunctional amines, the polyurea coating being sufficiently impenetrable for cadusafos, so that a reduction in the toxicity of the formulation in mammals is effected mentioned, compared to that of known formulations of aqueous microemulsion cadusafos of an equivalent or lower concentration of cadusafos. According to another aspect of the invention, a formulation of granular cadusafos, which comprises the aforementioned microcapsules, containing the cadusafos bound to a granular carrier, is provided. In addition, according to the present invention, processes are provided for making the microcapsulated granular or aqueous capsule suspension (CS) formulations. The microencapsulated cadusafos of the present invention has a lower toxicity in the skin, oral, and inhalation of mammals, thus making it possible to handle and use the safest pesticide. In accordance with the guidelines of the United States Environmental Protection Agency ("EPA"), the formulations of the present invention are as- classified as Category I I (warning) or Category I (l precaution) compositions, twice the concentration of non-microencapsulated liquid formulations of the same active ingredient, which are classified in Category I I. The microencapsulated formulations do not exhibit loss of pesticidal activity or physical and chemical stability, compared to that of non-microencapsulated formulations. In addition, the microencapsulated formulations of the present invention are consistent in color, which is not the case in aqueous microemulsion formulations of the compound, if the technical cadusafos is previously treated with copper salts to remove the unpleasant odor for commercial use.

Detailed Description of the Invention The microencapsulated cadusafos of the invention is made in accordance with the following basic steps: (a) providing an aqueous phase (also referred to in this description as a "continuous" phase) containing an emulsifier and an antifoam agent; (b) providing a non-miscible phase in water (also referred to in this description as a "discontinuous" phase), which contains the cadusafos together with a first polyfunctional compound; (c) emulsifying the aqueous phase with the non-miscible phase in water, to form a dispersion of non-miscible pills in water in the aqueous phase; and (d) adding to the dispersion, either dry or in an aqueous solution, a second polyfunctional compound, thereby forming a polymeric coating here known as a microcapsule around the non-water miscible pills; for example, forming microcapsules of cadusafos. The first polyfunctional compound is any suitable compound having two or more reactive groups, such as, but not limited to, an isocyanate monomer. The second polyfunctional compound is any suitable compound having two or more reactive groups, such as, but not limited to, a polyfunctional amine; wherein the first and the second polyfunctional compounds are different. The convenience of the first and second polyfunctional compounds is that they have the ability to form a heteromeric structure at the interface between the dispersed cadusafos and the aqueous phase. Said compounds will include both hydrophilic and hydrophilic groups between the two compounds, so that said groups, both can be in a single compound or can be exclusive for one or the other of said compounds. The last step is referred to as an internal polymerization due to the fact that the polyurea shell is formed through the polymerization of the first and second polyfunctional compounds, which preferably are an isocyanate and a polyfunctional amine (s). at the interface of the non-miscible phase in water (the pills) and the aqueous phase, thereby forming, preferably, a polyurea shell. Once the microcapsules are formed, the suspension is preferably cured, for example, heated moderately to complete the polymerization, after which one or more additives may be added, such as propylene glycol, xanthan gum, urea, bactericides , amphoteric surfactants, inert dyes or ion dispersion agents (for example, alkyl naphthalene sulfonate). The addition of materials after encapsulation and cure to adjust the viscosity, stability and suspension / dispersion characteristics, it preferably does not affect the reduction of toxicity or the pesticidal efficacy of the formulation. A further preferred step comprises neutralizing the pH of the formulation, for example, from about pH 6.5 to about pH 7.5, which results in improved stability. The use of the modifier "approximately" with respect to the pH, here is used to indicate a variation of at least one half of a pH unit, and preferably indicates a variation of one half of a pH unit. In other contexts of this description, when the modifier "approximately" is used to quantify a unit without registration, the "approximately" is intended to indicate a variation of ± 1 5%, still more preferably a variation of ± 1 0%. Typically, the aqueous phase contains from about 0.3 to about 3.0, preferably from about 0.7 to about 2.5, percent by weight of one or more emulsifiers. The preferred emulsifier for use in the present invention is polyvinyl alcohol. Other emulsifiers suitable for use in the present invention, include, but are not limited to, non-phenyl ethoxylate, sorbitan mono- and trioleate and ethoxylated oleate. The aqueous phase also contains from about 0.1 to about 1.0, preferably from about 0.3 to about 0.9 percent by weight of one or more antifoaming agents. Suitable antifoam agents for use in the present invention, include, but are not limited to, silicone-based antifoam agents, such as Dow Corning Antifoam DC1 500 and DC 1 520.

The aqueous phase may also optionally include a viscosity modifier / stabilizer, such as a xanthan gum from about 0.05 to about 0.50, preferably from about 0.06 to about 0.40 percent by weight, to itself as one or more bactericides from about 0.02 to about. about 0.1-0, preferably from about 0.03 to about 0.05 percent by weight. Bactericides useful for the present invention, include, but are not limited to, Legend MK (Rohm &Haas Co.), Proxel GXL (Zeneca, I nc.) And Dowicide A (Dow Chemical). The non-miscible phase in water (also referred to in the examples as the polyisocyanate solution), typically contains from about 50 to about 98, preferably from about 53 to about 92 weight percent cadusafos, and from about 2 to about 35, preferably from about 4 to about 25 percent by weight of the first polyfunctional compound, preferably an isocyanate monomer. The polyphenyl polymethylene isocyanate (PM PPI) is particularly preferred for use in the present invention; for example, Mondur M R (Miles, I nc.), Papi 27 or 1 35 (Dow Chemical) and Desmodur (Bayer). Also, according to the present invention, other suitable first polyfunctional compounds can be used, provided that they possess appropriate chemical and physical characteristics (e.g., chain length, functionality), so that the polimeric shell formed around the cadusafos, acts as a barrier to the discharge of cad microphones from the microcapsules. The first suitable polyfunctional compounds will be appreciated by those skilled in the art. The non-miscible phase in water may also contain a hydrocarbon solvent, such as, for example, a vegetable oil. However, the solvent is optional in the preparation of cadusafos microcapsule formulations, particularly with respect to formulations containing more than about 240 grams of cadusafos per liter. The hydrocarbon solvents useful in the practice of the present invention, include, but are not limited to, petroleum hydrocarbon, such as Aromatic 200, Aromal ic 1 50 and Exxate 1 000 (all from Exxon Chemicals), or vegetable oils, such as corn oils. The solvent, if used, is present in a percentage by weight of the non-miscible phase in water from about 15 to about 30, preferably from about 20 to about 25. An advantage of the present invention is that the Formulations can be prepared either with any cadusafos untreated or with a cadusafos that has been treated with a copper salt. Copper salts are added to cadusafos to reduce its odor. Normally, copper salts interfere with the formation of microcapsules by interfacial polymerization, but it was discovered that this is not the case in this process. The solution of the second polyfunctional compound usually contains from about 10 to about 100, preferably from about 20 to about 70, percent by weight of a second compound or polyfunctional mixture of said second polyfunctional compounds. The second examples & amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; polyfunctional amines, such as, but not limited to: diethylenetriamine (DETA), triethylenetetramine (TETA), and 1, 6 - hexanodiam ina (H DA). According to the example chemistry below, using PM PP I as the first polyfunctional compound and a generic amine for the second polyfunctional compound, the interfacial polymerization of the first and second polyfunctional compounds forms the polymeric microcapsules surrounding the cadusafos : O = C = N-R-N = C = O + H2N-R'-N H2 - ® -NHCON H-R-N HCON H-R'-NHCONH- R- A B Where A is PMPPI with an average functionality from about 2.3 to about 2.6, and B is a polyfunctional amine.

Various parameters of the process of the invention contribute to the characteristics of the final formulation. Preferably, the emulsification step is carried out using a superior cutting mixture to produce small pills of the non-miscible phase in water. The average size of the microcapsules of the invention is from about 5 to about 25 microns. The factors that influence the size of the microcapsules, as well as the stability of the emulsion, include: (1) total amount of cut applied during emulsification; (2) type and amount of surfactant or hydrocarbon solvent in the fa discontinuous, if used; (3) temperature or viscosity of the mixture; and, if present, (4) presence and amount of xanthan gum or naphthalene sulfonate dispersion agent alkyl in the mixture.

The selection of relative percentages of the first and second monomers of the polyfunctional compound (e.g., PM PPI and amines) in the discontinuous phase to achieve adequate microencapsulation requires a balance between competition factors. In general, by increasing the percentage of the monomers in the discontinuous phase, the toxicity of the final formulation is decreased. Similarly, decreasing the percentage of monomers results in greater toxicity of the final formulation. In an optimum general formulation of the invention, a balance between high efficiency and low toxicity is achieved including in the discontinuous phase from about 5 to about 35, preferably from about 7 to about 30 percent by weight of monomers. The operating conditions necessary to produce microcapsules from the appropriate monomer concentrations depend on the type of emulsification used; the determination of said conditions is within the skill level of the experts in the field.

In contrast to the vigorous conditions necessary for the emulsification step, the agitation during the addition of the second polyfunctional compound should be low cut, as achieved through the use of a mechanical blade agitator. Once the second polyfunctional compound has been added, agitation continues while the suspension is cured, for example, by heating it to a temperature of from about 20 ° C to about 60 ° C, preferably from about 30 ° C to about 50 ° C. C, for about one to about 10 hours, preferably about three to about four hours.

Once the encapsulation is complete, one or more substances can be added to the formulation. These substances are usually selected from the following, although other substances that are not specifically described will be apparent to those skilled in the art: (1) propylene glycol, preferably from about 1.3 to about 6.0 percent by weight; (2) urea, preferably from about 5.0 to about 5.5 p Dr percent by weight; (3) xanthan gum, preferably from about 0.003 to about 0.30 percent by weight; (4) one or more bactericides up to a percentage by total weight from about 0.01 to about 0.10; (5) one or more inert dyes in a percentage by total weight of up to about 0.05; and (6) one or more surfactants of up to a percentage by total weight of about 7.0; each percentage by weight is relative to the weight of the formulation after the addition of the additives.

The preferred practice, after curing the microcapsules, is to neutralize the formulation, with for example, phosphoric, acetic or hydrochloric acid, although other acids will suffice. Subsequently, the ? U post-encapsulation additives and stirring of the formulation continues for about four hours with heating at a moderate temperature (e.g., 50 ° C).

Capsule Suspension (CS) formulations of cadusafos 5 prepared through the methods described above, have the following characteristics of general composition: they contain from about 150 to about 360 grams of cadusafos per liter of formulation, and comprise an aqueous suspension of microcapsules made from a polyurea shell surrounding a nucleus of cadusafos, and optionally, a hydrocarbon solvent, and additionally comprise an emulsifier, from about 0.3 to about 3.0 percent by weight of polyvinyl alcohol, and an antifoam agent from about 0.05 to about 0.5 percent by weight. Also, the formulation can contain in a Optionally from about 0.06 to about 0.4 percent by weight of xanthan gum or other viscosity modifier / stabilizer, from about 0.02 to about 0.1 percent by weight of one or more bactericides, from about 0.7 ha to about 6.7 percent. percent by weight of one or more surfactants and, from About 1.2 to about 5.8 percent by weight of propylene glycol or urea, or a combination thereof. Preferred formulations contain about 200 g / l cadusafos, ranging from about 53 to about 92 weight percent cadusafos and from about 4 to about 25 weight percent. percent by weight of PM PPI in the non-miscible phase in water, and use DETA, TETA or DA as the polyfunctional amine.

In another aspect of this invention, the CS cadusafos formulations described above are used to prepare formulations of granular microemulsion cadusafos (G-M E). The G-M E formulations are prepared according to the following steps: (a) to provide a homogeneous mixture of cadusafos formulation of capsule suspension (CS) or microencapsulated and an adhesive agent; (b) dispersing the mixture in a vehicle; and (c) allowing the vehicle to dry, thereby forming the granular formulation.

The G-ME formulation will usually contain from about 5.0 to about 30.0, preferably from about 1.0 to about 20.0 percent by weight of cadusafos CS formulation, from about 60.0 to about 95.0, preferably from about 70.0 to about 80.0 by percent by weight of a vehicle, and from about 0.05 ha to about 5.0, preferably from about 0.1 to about 2.0 percent by weight of an adhesive agent.

Adhesive agents useful for the practice of the invention, include, but are not limited to, calcium and sodium lignosulfonates, polyalkylene glycols, and other polymer solutions, such as resins. Those skilled in the art will readily appreciate other suitable adhesives.

Examples of vehicles that can be used in the present invention include, but are not limited to, cellulose complexes, clays and attapulgite, silica complexes, and plant materials, such as corn cobs. Those skilled in the art will readily appreciate other suitable vehicles, The time required for the mixture of the CS formulation and the adhesive to reach homogeneity is not critical, but is usually from about one to about twenty minutes. The dispersion in the vehicle continues until the mixture has run out. Subsequently, the granular formulation is dried for several hours.

The examples that follow are provided to illustrate the embodiments of the invention. Said examples are not intended to limit the invention in any way.

EXAMPLE 1 Preparation of a Formulation of Suspension of Cadusafos Capsules (CS) of 200 q / l (Formulation PP).

A 20% (w / w) aqueous partially hydrolyzed polyvinyl alcohol stocking solution (Airvol® 203) was prepared by stirring and heating the appropriate amounts of polyvinyl alcohol and water at a temperature of about 80-90 ° C during one hour. The cooled solution was stored for later use.

The aqueous phase for microencapsulation was prepared in a four liter stainless steel vessel, mixing 92 g of the 20% aqueous polyvinyl alcohol solution, 68.6 g of 2% aqueous xanthan gum (Kelzan® S), and 8.2 g of polydimethyl siloxane antifoam agent (Dow Corning® 1 520) in 1832 g of water. Subsequently, 332.5 g of this mixture was transferred to a one liter vessel. The mixture was mixed for one minute at high speed, then a premixed solution of 140.0 g of cadusafos (previously treated with 2.5% copper naphthenate), 60.0 g of petroleum solvent (a mixture of hydrocarbons decreased by naphthalene, aromas of C9-C15, point flas h of 95 ° C, Aromatic 200 ND), and 43.0 g of PM PPI (Mondur® MR), and the mixture was emulsified for one minute. Subsequently, the mixture was placed in a one liter three-necked round bottom flask equipped with a mechanical stirrer, and 27.0 g of a 70% aqueous solution of HDA in 1.0 g of water was added over a period of 30 minutes. seconds. Upon completion of the addition, the mixture was heated to a temperature of 50 ° C and maintained for four hours. After this time, the mixture was cooled to a temperature of 30 ° C and 35.0 g of urea were added, followed by 25.0 g of 2% aqueous xanthan gum (Kelzan® S). Subsequently, the formulation was mixed gently for about an hour and stored. The formulations described in Tables 1 and 2 were prepared in this manner.

EXAMPLE 2 Large Scale Preparation of a Suspension Formulation of Cadusafos Capsule (CS) of 200 q / l (Formulation PB-8PG).

A solution of 2.09 pounds of a polyvinyl alcohol, 0.1 6 pounds of 2% aqueous xanthan gum, 0.9 pounds of a siloxane polydimethyl antifoam agent, 7.62 pounds of a sodium salt of a sulfonate and naphthalene alkyl and 0.07 pounds was placed. of a 1,2-benzisothiazolin-3-one bactericide in 5 226.2 pounds of water, in a 1-gallon stainless steel container, and stirred at a temperature of 80 ° C for one hour. After this time, the solution was cooled to a temperature of 20 ° C and placed in a 1 20-gallon stainless steel batch homogenizer. The homogenizer was left until reaching an approximate speed: e 3500 rpm, and a pre-blended solution of 82 6 pounds of cadusafos technician (which was previously treated with 2.1 pounds of copper naphthenate) was fed and 1 5.1 pounds of PMPPI were fed at 10 psi into the homogenizer. The mixture was homogenized for about one minute. When the homogenization is complete, the mixture s.e poured rapidly into a 1 00 gallon stainless steel reactor with a double-angle propulsion agitation. An amine mixture consisting of 9.4 pounds of 70% aqueous HDA solution in 4.4 pounds of water was quickly added. Once the addition of amine was completed, the mixture was vigorously stirred for ten minutes, and subsequently heated to a temperature of 50 ° C, where it was cured for a period of three to four hours with slow mixing. At the end of the curing period, the mixture was cooled to a temperature of 35 ° C and subsequently neutralized to a pH of 6.5 to 7.5 with 2.2 pounds of phosphoric acid or concentrate. Upon completion of the addition, they were added to the formulation 1 5.51 pounds of 2% aqueous xanthan gum, 22.0 pounds of propylene glycol, 0.14 ^^^^^^^^^^^^^^^ g ^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^ jg ^ £ ^^ pounds of a 1,2-benzisothiazolin-3-one bactericide and 0.81 pounds of polydimethyl siloxane anti-foam agent. The formulation after mixing for one hour had a viscosity of 325 cps and a suspension capacity of 98%.

EXAMPLE 3 Large Scale Preparation of a Cadusafos Capsule Suspension Formulation (200 CS) (Formulation PB-C14U-N D).

To a stirred solution of 7.24 pounds of a polyvinyl alcohol, 0.22 pounds of 2% aqueous xanthan gum, 3.33 pounds of a siloxane polydimethyl antifoam agent (Dow Corning® 1 520), 7.53 pounds of a sodium salt of a sulfonate Naphthalene alkyl and 0.20 pounds of a 1,2-benzisothiazolin-3-one bactericide in 391.3 pounds of water in a 1 20-gallon stainless steel batch homogenizer was added a pre-mixed solution of 1 72.6 pounds of cadusafos technical (which was previously treated with 4.21 pounds of copper naphthenate), 53.0 pounds of PM PPI, and 74.1 pounds of an oil solvent (a mixture of hydrocarbons decreased by naphthalene, C9-C15 aromatics flash point of 95 ° C) . Upon completion of the addition, the mixture was stirred in the homogenizer at a rate of about 3,500 rpm for about 10 minutes. Upon completion of homogenization, an amine mixture consisting of 33.3 pounds of a 70% aqueous solution of HDA in 12.3 pounds of water was added. Once the addition of amine was complete, the mixture was stirred for ten minutes and then heated to a temperature of 50 ° C, where it was cured for three to four hours. To the * afe- - ^ s- ^ s- íw? At the end of the curing period, the mixture was cooled to a temperature of 35 ° C and subsequently neutralized, to a pH of 6.5 to 7.5 with 7.47 pounds of 85% phosphoric acid. Upon completion of the addition, 32.04 pounds of 2% aqueous xanthan gum, 44.6 pounds of urea and 0.1 7 pounds of an inert dye (Tricon Green 1 8800) were added to the formulation. Subsequently, the formulation was mixed for one hour and stored.

EXAMPLE 4 Large Scale Preparation of a Cadusafos Capsule Suspension Formulation of 200 q / L (200 CS) (Formulation PB-C14U-ND), At a current of 14.6 pounds per minute from a stirred solution of 1. 77% of a polyvinyl alcohol, 0.08% xanthan gum, 0.81% of a polydimethyl siloxane antifoam agent (Dow Corning® 1 520), 1.84% of a sodium salt of an alkyl naphthalene sulfonate (Lomar® LS -1), 0.05% of a bactericide 1, 2-benzisothiazolin-3-one (Proxel® GXL) and 95.46% of water, a current of 0.9 0.9 pounds per minute of 57.55% technical cadusafos pre-mixed solution was combined, 1 7.75% of PMPPI and 24.70% of a petroleum solvent (a mixture of hydrocarbons, decreased by naphthalene, aromatic of C9-C1 5, flash point 95 ° C). The combined stream was fed through an inline homogenizer that produces a suitable cut to obtain the desired particle size. To the discharge stream of the homogenizer a stream of 1.6 pounds per minute of the amine mixture consisting of 73% of a 70% aqueous HDA solution in 27% water was fed to it, and the resulting stream was fed into the stream. a reactor The water is stirred at a temperature of 35 ° C. The mixture was continuously discharged from the reactor into a second 1,000 gallon reactor, while a constant residence time of 20-30 min was maintained. When the second 1000 gallon reactor was filled (5420 pounds), the mixture was heated to a temperature of 50 ° C where it was cured for three to four hours. At the end of the curing period, the mixture was cooled to a temperature of 35 ° C and subsequently neutralized to a pH of 6.5 to 7.5 with 75.0 pounds of 85% phosphoric acid. Upon completion of the addition, 230.6 pounds of a 2% aqueous xanthan gum, 321 .6 pounds of urea, and 1.3 pounds of an inert dye (Tricon Green 1 8800) were added to the formulation. Subsequently, the formulation was mixed for one hour, filtered and stored. The formulations described in Tables 3 and 4 were prepared in the form of Examples 2, 3, and 4.

EXAMPLE 5 Preparation of a 3% Weight / Weight Micro-Weight Granular Formulation of Cadusafos (3G-M E). In a one liter container were placed 83.0 grams of the 200 CS cadusafos formulation, prepared as described above, and 1.0 grams of calcium lignosulfonate (Norling® A). The mixture was mixed until homogeneous (approximately ten minutes) and subsequently sprayed on a commercially available mixer / mixer containing 41.7 grams of a cellulose complex consisting of paper filler, kaolin clay, calcium carbonate and dioxide of titanium (Biodac® 20/50), until all the mixture had been exhausted. Upon completion of the exhaustion of the mixture, the agitator / mixer was stopped, and the formulation allowed to air dry for about 16 hours.

Example 6 Toxicity Studies. Laboratory tests demonstrating the reduced mammalian dermal toxicity of the cadusafos (CS) capsule suspension formulations were carried out in the following manner. For each formulation that will be tested (referred to as the test material), six Sprague-Dawley rats (3 males and 3 non-pregnant non-pregnant females) were treated with the formulation of cadusafos CS at dosage levels of 50, 200, 400 and 2000 mg / kg. One day before the test materials were applied, the trunk of each rat was clamped and released from hair to expose at least 10% of the body surface of the rat. The test materials were applied to a 2x2-inch 4-ply gauze pad, which was secured at the rat test site. An elastic self-adhesive bandage lined with plastic was wrapped around the rat's trunk to ensure that the test material remained in contact with the skin. After approximately twenty-four hours, the wrappings and pads were removed and any remaining test material was cleaned with a clean gauze pad moistened with tap water. The mortality observations were carried out twice a day. Animals were observed for approximately 3 hours after dosing on day 0, and daily for 14 days. The nature, irruption and duration of the s A-ad = h a * ts > »- = * visible toxicological or pharmacological effects were recorded daily, with the exception of local irritation on the test site. The time of death (or the discovery of death) was also observed. The body weights of the rats were recorded before dosing and on days 7 and 14. Those animals that did not survive the observation period were weighed as soon as possible after the discovery of their death. Necropsies were performed on all animals that died during the tests. The animals that survived the observation period (Day 14) were sacrificed and examined exhaustively. All internal abnormalities were recorded. The LD50 were approximated from the dosage levels. The results of the tests, shown in Table 5, indicate that the CS formulations of the present invention are effective in reducing the dermal toxicity of cadusafos in mammals. Although all the formulations showed reduced dermal toxicity, Formulations K, KK, LL, M M, PB-9PG and PB-1 1 PG reduced toxicity to Category 11, and Formulation PB-14U-N D reduced toxicity to Category IV. See the definitions of Categories I through IV below. Laboratory tests that showed reduced oral toxicity of the The suspension formulations of cadusafos (CS) capsules in mammals were carried out in a manner similar to that described above. The tests differed in that the test materials were administered by oral intubation, using a round tip intubation needle, at dosing levels of 25, 50, 200 and 500 mg / kg, instead of , 200, 400, and 2000 mg / kg, and in which the rats were not fed during the ?-go - . »-» -,.,. 'Ss'? Nr £ .. 'K "' * • - * íaa ft approximately 1 8 hours before the tests are done The results of the tests, shown in Table 6, indicate that the CS formulations of the present invention are effective in reducing the oral toxicity of cadusafos in mammals.Although all formulations showed reduced oral toxicity, Formulations B, PP, Q, and PB-14U-ND reduced toxicity to Category III. the reduced inhalation toxicity of Formulations PB-8PG and PB-C 14U-ND in mammals, as follows: Six Sprague-Dawley rats (3 males and 3 non-pregnant nulliparous females) were exposed, for four hours, to a atmosphere of the test material in a 1 liter single nostril inhalation chamber operated under dynamic air flow conditions.The concentration level of the test material was> 0.5 mg / l and> 0.05 mg / l. They made observations of xicity and mortality every hour during the exposure period, until the camera is removed, and at least once a day for the next 14 days. The individual body weights were recorded before exposure (Day 0) and on Days 7 and 14. Animals that did not survive until the end of the observation period were weighed as soon as possible after the discovery of their death. Necropsies were performed on all animals who died during the study. All the animals that survived on Day 14 were anesthetized and sacrificed before the exhaustive examination. All internal abnormalities were recorded. The results of the inhalation study indicated that Formulations PB-8PG and PB-C 14U-N D estimated for four hours LC50's ~ ^ A. '^^ pf f ^ - \ &Já b greater than 1 .04 mg / l and 3.87 mg / l, respectively. These data show that the inhalation toxicity is reduced from a Category I to a Category l l l. Acute inhalation of a known cadusafos 1 00 M E formulation (100 g / l aqueous microemulsion of cadusafos) by a rat is 0.026 mg / l / 4 hours. The terms "Category I", "Category M", "Category I I" and "Category IV" refer to the category of EPA assignments for a chemical compound based on its toxicity. The criteria for classifying a compound as "Category I", "Category I I", "Category I I" or "Category IV" are the following: Category Indicators Category Category Category Hazard I IV Oral LD50 Up to > 50 a > 500 a > 5000 including 500 mg / kg 5000 mg / kg 50 mg / kg mg / kg Dermal LD50 Until e > 200 a > 2000 a > 5000 including 2000 5000 mg / kg 200 mg / kg mg / kg mg / kg Measurement of the Up to > 0.05 a > 0.5 to 5 »5 mg / L concentration of the including 0.5 mg / L mg / L chamber of 0.05 mg / L inhalation LC50 (Actual) during a 4-hour exposure ! 3 »w». * Example 7 Efficacy Studies It has been found, in a generalized manner, that the formulations of the present invention are effective against a number of pests. The following methods are representative of the efficacy of the formulations of the present invention, and are not intended to limit in any way, the scope of the invention. The effectiveness and persistence of the formulations from the AA to the FF, excluding DD, was tested to control the root button nematode (RKN), incognito Meloidogine, in tomato. A three-week-old tomato (Lycopersicon esculentum, var "Rutgers") was planted in a 1 0 cm square container containing a mixture of sand: 50:50 earth, non-sterile. Ten replicate containers (five replicates for two test groups) were prepared for each application range of the test formulation. Dispersions of the stock of each of the test formulations were prepared by dispersing a sufficient amount of the test material in 100 ml of water, to provide application ranges of 0.25, 0.5, 1, and 2 kg a. i / ha. Each container received 10 ml of the appropriate suspension on the immediate surface around the tomato, and a control treatment for each of the two groups of experiment vessels received only water. The containers were also prepared as indicated above with the same ranges of cadusafos 1 00 M E and cadusafos technical formulation. The RKN eggs used in the experiment were separated from a gelatinous matrix by vigorously shaking the roots of tomato plants that were heavily scraped for four minutes.

? "- - B - * '• -. -? * ~ ¿¿*. a solution of 1% aqueous sodium hypochlorite. The suspension of the resulting eggs was quickly poured into sieves of 60 mesh, 325 mesh, and 500 nested sieves. The eggs were collected on the 500 sieve and rinsed generously with water, to remove any excess of sodium hypochlorite. The eggs were collected in water, and the resulting aqueous suspension was suitably diluted with water to provide approximately 2000 eggs per plant, which results in an effective inoculation level from approximately 1000 infective larvae per container. The eggs were counted using a division microscope. All the containers were infested with nematodes by pipetization of the inoculate in the openings around the roots of the tomato transplants previously treated. In the following, the containers infested with nematodes 48 hours before the treatment with earth, will be referred to as "group 1". The containers for the examination of the residual activity, which in the following will be referred to as "group 2", were treated and maintained in the greenhouse for seven days before the infestations of nematodes. At the time of the nematode infestation, the containers were kept in the greenhouse for 28 days and symptoms of phytotoxicity were monitored. At the conclusion of the 28-day period, the soil was washed from the roots of the tomato plants and classified according to the scheme below: ! ^ áL ^ grf * Scraping Range Description 0 Complete and Healthy Root System, No Infestation Very few small scrapes could be detected in 1 the close examination. 2 Small root scratches as in "1", but more numerous and easily detected. 3 The root system is characterized by numerous small scrapes, some of which may have grown together, although the function of the roots is still not seriously affected. 4 In addition to the numerous small scrapings, some large scrapes are present, but most of the roots are still working. 5 Approximately 25% of the root system is out of function due to severe scaling. 6 Up to 50% of the root system is out of function due to severe scraping. 7 Approximately 75% of the root system is very shaved and lost for production. 8 The unhealthy roots are left, the plant's food is interrupted, but the plant is still green. 9 The completely scraped root system is rotten, the plant is dying. 1 0 The plant and the roots are dead.

The results of the test shown in Tables 7 and 8 indicate that all formulations of cadusafos CS were effective to control nematodes in tomatoes, and that there are no clear differences between the formulations. In Table 7, only the data of the two lowest application ranges are shown, because all the treatments completely controlled the nematodes in 1 and 2 kg a. i. /he has. Formulations B, E, F, G, and H were tested against southern corn rootworm (SCR) larvae to determine the initial and residual soil activity of CS cadusafos formulations. Each formulation was evaluated using three replications of 5000 grams of two types of soil (clay soil and sandy mulch soil). The sandy mulch soil consisted of 30% clay, 30% sand and 3% organic material, while clay mulch soil consisted of 87% sand, 3% clay, and 0.9% organic material. Prior to treatment, the lands were placed in a five gallon pot, dried by air and then adjusted to a 50% soil wetting holding capacity. Each formulation was sprayed at 20 psi in the sifted soil in application ranges of 0.1, 0.2, 0.5 and 1.5 ppm in sandy mulch soil, and 0.1 and 0.2 ppm in clay mulch soil. The boats of the two types of land were also sprayed as indicated above, with the same formulation ranges of cadusafos 1 00 ME. At the time of treatment, the soil was mixed for five minutes and then transferred to a container of 2.84 liters. The soil was covered and subsequently maintained at a temperature of 26 ° C, and from 40 to 50% of the soil moisture in the greenhouse, until it was necessary for the elaboration of the tests. In each sampling period, 50 grams of the treated soil will be added to a 1 1 3.4 grams plastic cup containing two seeds of two corn seeds a day of germination, which completely covered the seeds. Fifteen SCR larvae of the advanced second-instar were added to each cup. Each cup was covered with a tight fitting cap and placed in an environmental chamber maintained at a temperature of 24 to 26 ° C. After 96 hours, 226.8 grams of paper cups corresponding to each soil container were filled with soapy water to a depth of approximately 1.27. ? £? '£ • i. ^ F. ^ A.JStíSSSatIT: cm. A funnel with a plastic mesh was placed in the bottom of each paper cup. Subsequently, every 50 grams of soil extracted in the funnel was placed in the corresponding paper cup. The earth remained in the funnel until it dried completely, and all the live larvae that had crawled down into the cup. The number of SCR larvae at the bottom of the rate was recorded as alive. From these data, the percentage of mortality in each sample was determined. The results of the tests indicated that the CS cadusafos formulations of the present invention were equal or slightly more active residually than the cadusafos 1 00 M E formulation. For example, at 0.2 ppm in soil of clay mulch, Formulation G caused 97% mortality 84 days after treatment, while the cadusafos 1 00 ME formulation caused a 40% mortality. These data are presented in Tables 9 and 1. The present invention is not limited to the modalities described therein, but may be varied and modified within the scope of the appended References. Said variation, includes, but is not limited to, mixtures of one or more pesticides, whether encapsulated or not, wherein the microencapsulated cadusafo of the present invention is part of the mixture.

Table 1 Preparation of Formulations for Cadusafos Suspension Capsules (CS) (Components and Quantities) Weight (grams) Formulation (grs./L) A (240) B (200) C (180) D (200) E (200) E-1 (200) E-2 (200) F (200) G (240) H (220) J (270) Component Aqueous Solution Water 430.7 430.7 430.7 316.0 394.1 1182.3 2364.6 394.1 394.1 394.1 394.1 PVA 4.0 4.0 4.0 4.0 3.98 1 1.94 23.88 3.98 3.98 3.98 3.98 3.98 Rubber Xantan 0.3 0.3 0.3 - 0.28 0.84 1.68 0.28 0.28 0.28 0.28 Anti-foam 1.8 1.8 1.8 1.8 1.64 4.92 9.84 1.64 1.64 1.64 1.64 Isocyanate Solution Cadusafos 170.0 140.0 140.0 140.0 140.0 420.0 840.0 140.0 140.0 140.0 140.0 140.0 Oil Solvent - 30.0 30.0 30.0 30.0 90.0 180.0 30.0 30.0 30.0 - PMPPI 36.0 30.0 30.0 30.0 30.0 90.0 180.0 15.0 7.5 12.0 30.0 r 00 Solution Amina TETA 19.0 19.0 19.0 19.0 - - - - - - - DETA - - - - 19.0 57.0 1 14.0 9.5 4.75 7.22 8.5 Water 31.0 31.0 31.0 31.0 31.0 93.0 186.0 15.5 7.75 11.78 - Stabilizers After Encapsulation Propylene Glycol - ... 9.3 9.3 9.0 27.0 54.0 9.0 9.0 9.0 9.0 Rubber Xantan 0.03 0.02 1.0 1.0 1.0 3.0 6.0 1.0 1.0 1.0 1.0 Water 1.47 0.98 - - - - - - - - - Con. H3PO4 - ... 18.0 ... 18.0 54.0 108.0 11.0 - 4.0 - Con. HCl - - - 15.5 - - - - - - 11.9 Sulfonate Na - - - - 5.0 15.0 30.0 5.0 5.0 5.0 5.0 Bactericide A - - - - 0.3 - 1.8 0.3 0.3 0.3 - (continued) Table 1 Weight (grams) Formulation (grs./L) K (200) L (240) M (240) N (240) O (240) P (250) Q (250) R (250) S ( 250) T (250) Component Aqueous Solution Water 207.06 281.01 319.8 319.8 325.38 261.29 239.6 261.29 239.6 288.6 288.6 PVA 19.32 2.62 8.76 8.76 3.04 2.44 2.23 2.44 2.23 2.23 2.23 Xantan rubber 1.45 0.2 0.21 0.21 0.23 0.18 0.17 0.18 0.17 1.17 Antifoam 8.61 1.17 1.23 1.23 1.35 1.09 1.0 1.09 1.0 1.0 Cadusafos Isocyanate Solution 840.0 140.0 140.0 140.0 140.0 170.0 140.0 140.0 140.0 140.0 140.0 140.0 140.0 Oil Solvent 180.0 - - - - - - - - - PMPPI 180.0 15.0 15.0 15.0 15.0 15.0 15.0 24.0 15.0 24.0 24.0 NJ Solution Amina CD DETA 114.0 10.0 9.5 9.5 9.5 9.5 15.6 5.7 14.44 14.44 Water 186.0 - 15.5 15.5 15.5 15.5 25.4 9.3 23.56 23.56 Stabilizers After Encapsulation Propylene Glycol 60.0 28.0 28.0 28.0 28.0 28.0 28.0 28.0 28.0 28.0 Rubber Xantan 6.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - Water 294.0 49.0 - ... - 49.0 49.0 49.0 49.0 - Con. H3PO4 99.0 11.0 11.0 6.84 6.84 8.5 11.4 2.5 11.4 11.4 Sulfonate Na 30.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 4.0 4.0 Bactericide A 1.0 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Amphoteric surfactant - 15.0 - - - - - - - - (continued) Table 1 Weight (grams) Formulation (grs./L) U (250) V (250) W-1 (360) W-2 (360) W-3 (360) X (250) Y (250) Z (250) AA (250) BB (200) BB-1 (200) Component Aqueous Solution Water 264.1 261.14 270.42 270.42 270.42 261.14 261.22 261.29 251.42 374.68 384.54 PVA 2.23 2.21 5.0 5.0 5.0 2.21 2.35 2.44 2.35 3.5 3.59 Rubber Xantan 0.67 0.67 0.22 0.22 0.22 0.67 0.38 0.18 0.18 0.26 0.27 Antifoam 1.0 0.98 2.28 2.28 2.28 0.98 1.05 1.09 1.05 1.56 1.6 Sulfonate Na - - - - - - - 5.0 5.0 5.0 5.0 Cadusafos Isocyanate Solution 140.0 140.0 289.8 289.8 289.8 140.0 140.0 140.0 140.0 140.0 140.0 140.0 Oil Solvent - - 31.2 31.2 31.2 - - - - - - PMPPI 24.0 15.0 62.5 62.5 62.5 15.0 15.0 15.0 15.0 15.0 12.0 Naphthalene Cu - - - ... - - - - 1.4 0.7 0.7 Solution Amine co 0 DETA 14.44 9.5 25 25 25 9.5 9.5 9.5 9.5 9.5 0.4 Water 23.56 15.5 - ... - 15.5 15.5 15.5 15.5 15.5 19.6 Stabilizers After Encapsulation Propylene Glycol 28.0 28.0 - - 40.0 28.0 28.0 28.0 28.0 35.0 35.0 Xantan Rubber - 0.5 0.52 0.52 0.52 0.5 0.5 0.5 0.7 0.7 0.7 Water - 24.5 25.68 25.68 25.68 24.5 24.5 24.5 34.3 34.3 34.3 34.3 Con. H3PO4 11.4 8.5 - - - - - - - - - Con. HCl - - 16.0 16.0 16.0 22.0 11.8 10.4 12.0 12.0 12.0 Sulfonate Na 4.0 5.0 54.4 54.4 59.4 12.5 12.5 7.5 7.5 7.5 7.5 Bactericide A - 0.3 - - - - - - - - - Bactericide B - - - - 0.4 0.3 0.3 0.3 0.3 0.3 0.3 Amphoteric surfactant - 25.0 - 26.0 26.0 - - - - - - Antifoam ... ... - ... 2.02 ... ... ... ... ... - Ni Ol O Ü1 cn (continued) Table 1 Weight (grams) Formulation (grs./L) CC (150) DD (150) EE (200) FF (200) GG (200) HH (200) JJ (200) KK (200) LL ( 200) MM (200) NN (200) Component Aqueous Solution Water 606.39 591.60 354.96 374.68 374.68 374.68 369.77 1109.26 1123.22 1123.22 1123.22 PVA 5.66 5.52 3.31 3.5 3.5 3.5 6.78 10.35 10.36 10.36 10.36 Rubber Xantan 0.43 0.42 0.25 0.26 0.26 0.26 0.3 0.78 0.82 0.82 0.82 Antifoam 2.52 2.46 1.48 1.56 1.56 1.56 3.09 4.61 4.59 4.59 4.59 Sulfonate Na 5.0 5.0 5.0 5.0 5.0 12.5 12.56 37.5 37.92 37.92 37.92 Bactericide A ... - ... - ... - - - 0.59 0.59 0.59 Cadusafos Isocyanate Solution 140.0 140.0 140.0 140.0 140.0 137.86 136.5 409.5 409.5 409.5 409.5 PMPPI 12.0 15.0 25.0 10.0 15.0 15.0 15.0 60.0 45.0 45.0 90.0 Naphthalene Cu 0.7 0.7 0.7 0.7 1.4 3.54 3.5 10.5 10.5 10.5 10.5 co Solution Amina DETA 7.6 9.5 15.2 6.1 9.5 3.8 - - - 28.5 - HDA - - - - - - 6.51 26.04 19.5 - 39.06 Water 12.4 15.5 24.8 9.9 15.5 6.2 18.49 48.96 55.5 46.5 36.74 Stabilizers After Encapsulation Propylene Glycol 35.0 35.0 35.0 35.0 35.0 35.0 35.0 105.0 105.0 105.0 105.0 Rubber Xantan 0.7 0.7 0.7 0.7 0.5 0.5 0.5 1.5 1.5 1.5 1.5 Water 34.3 34.3 34.3 34.3 24.5 24.5 24.5 73.5 73.5 73.5 73.5 Con. H3PO4 - - - ... - - 0.1 1.0 - 20.0 - With. HCl 12.0 12.0 17.0 17.0 12.0 0.6 - - - - - Sulfonate Na 7.5 7.5 7.5 7.5 7.5 - - - - - - Bactericide B 0.3 0.3 0.3 0.3 0.3 0.3 - 1.0 1.0 1.0 - Formulation (grs./L) PP (200) QQ (200) RR (200) Component Aqueous Solution Water 3 32277..8855 3 32277..8855 6 60077..1155 PVA 3 3..0066 3 3..0066 5 5..6633 Rubber Xantan 0 0..2233 0 0..2233 0 0..4455 Antifoam 1 1..3366 1 1..3366 2 2..3399 Sulfonate Na - ... - - 2 200..4422 Bactericide B - ... - ... 0 0..2211 Isocyanate solution Cadusafos 1 13366..55 1 13366..55 2 22211..6633 Naphthalene Cu 3 3..55 3 3..55 5 5 .. 5522 Oil Solvent 6 600..00 - - - - Corn Oil. - .. 6 600..00 - - PMPPI 4 433..00 4 433..00 4 400..6644 Solution Amina HDA 1 188..99 1 188..99 2 255..1111 Water 1 188..11 1 188..11 1 111..7733 Stabilizers After Encapsulation Con. H3PO4 - - 5.11 Water 24.5 24.5 39.98 Rubber Xantan 0.5 0.5 0.80 Urea 35.0 35.0 53.24 Antifoam 1.36 1.36 1.99 Inert Paint - 0.21 Polyvinyl alcohol PVA-Airvol ® Rubber Xantan - Kelzan® M and Kelzan® S, xantan gums differ in that the S has been treated on the surface to improve the ease of dispersion. M was used in the preparation of the aqueous solution for Formulations from A to R, while Formulations from S to Z used S. The xanthan gum used in post-encapsulation stabilization was Kelzan® S. Antiespuma - Dow Corning® 1500 is 100% polydimethyl siloxane. Dow Corning® 1520 is a 20% solution. The 1500 was used in Formulations A and B; 1520 in all the others. Oil solvents Aromatic 200 ND, a mixture of hydrocarbons decreased by naphthalene, C9-C15 aromatics, flash point 95 ° C, or Exxate® 1000, C9-C11 branched alkyl esters of acetic acid. The Exxato 1000 was used only in the RR Formulation. PMPPI - polymethylene polyphenyl isocyanate, Mondur® MR or Papi 27. The Papi 27 was used for the QQ Formulation, while the Mondur® MR was used for the others. TETA -trietilenotetramine; DETA - triethylenediamine; HDA-1, 6-hexanediamine sulfonate Na-sodium sulfonate alkyl naphthalene, Lomar® PW, Emery® 5355, or Lomar® LS-1. Formulations from A to GG used Lomar PW, formulation HH used Emery 5355 and formulations from JJ to ZZ used Lomar® LS-1. Bactericidal A - mixture of 2-methyl-4-isothiazolin-3-ones, Legend® MK; Bactericide B - 1, 2-benzisothiazolin-3-one, Proxel® GXL Amphoteric surfactant - sodium lauriminodipropionate, Mirataine ™ H2-C-HA Inert dye - Green Tricon 18800 ! & 4 * ^ •. ^. ^ -MMMMittt .. 1,, tUU £ ^ Table 2 Formulations (CS) of Suspension of Cadusafos Capsules (Components and Weight / Weight Percentages) Weight / weight percentages Formulation A (240) B (200) C (180) D (200) E and E-2 E-1 F (200) G (240) H (220) J (270) Components PVA 0.58 0.58 0.56 0.67 0.58 0.58 0.63 0.66 0.64 0.66 Rubber Xantan 0.05 0.05 0.18 0.17 0.19 0.19 0.20 0.21 0.21 0.21 Anti-foam 0.26 0.26 0.25 0.30 0.24 0.24 0.26 0.27 0.26 0.27 Cadusafos 24.49 20.35 19.58 23.43 20.49 20.50 22.00 23.13 22.57 23.13 Petroleum Solvent - 4.36 4.20 5.02 4.39 4.39 4.71 4.96 4.84 - PMPPI 5.19 4.36 4.20 5.02 4.39 4.39 2.36 1.24 1.93 4.96 CO TETA 2.74 2.76 2.66 3.18 - - - - - - co DETA - - - - 2.78 2.78 1.49 0.78 1.16 1.40 1.40 1.40 - 0.64 - Con. HCl - - - 2.59 - - 1.97 Sulfonate Na - - - - 0.73 0.73 0.79 0.83 0.81 0.83 Bactericidal A - - - - 0.04 - 0.05 0.05 0.05 - Water 66.69 67.28 64.55 58.06 62.22 62.24 64.37 66.38 65.44 65.08 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 2 (continued) Percentages weight / weight Formulation K (200) L (240) M (240) N (240) O (240) P (250) Q (250) R (250) S (250) T (250) PVA components 0.47 0.47 1.58 1.59 0.52 0.45 0.41 0.47 0.41 0.41 Rubber Xantan 0.18 0.21 0.22 0.22 0.21 0.22 0.22 0.23 0.22 0.22 Antis foam 0.21 0.21 0.22 0.22 0.23 0.20 0.18 0.21 0.19 0.19 Cadusafos 20.54 25.03 25.21 25.40 29.25 26.08 25.80 26.88 25.99 25.99 Oil Solvent 4.40 - - - - - - - - - PMPPI 4.40 2.68 2.70 2.72 2.58 2.79 4.42 2.88 4.46 4.46 DETA 2.79 1.79 1.71 1.72 1.63 1.77 2.87 1.09 2.68 2.68 CO Propylene Glycol 1.47 5.01 5.04 5.08 4.82 5.22 5.16 5.38 5.20 5.20 JI- With H3P04 2.42 1.97 1.98 1.24 1.18 1.58 2.10 0.48 2.12 2.12 2.12 Sulfonate Na 0.73 0.89 0.90 0.91 0.86 0.93 0.92 0.96 0.74 0.74 Bactericidal A 0.02 0.05 0.05 0.05 0.05 0.06 0.06 0.06 0.06 0.06 Amphoteric - 2.68 ... - - - - - - - Water 62.37 59.01 60.39 60.85 58.67 60.70 57.86 61.36 57.93 57.93 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ro ro n or cp cn Table 2 (continued) Percentage weight / weight Formulation U (250) V (250) W-1 W-2 W-3 X (250) Y (250) Z (250) AA BB BB-1 Components PVA 0.43 0.41 0.64 0.62 0.58 0.41 0.45 0.47 0.45 0.45 0.53 0.55 Rubber Xantan 0.13 0.22 0.09 0.09 0.09 0.22 0.17 0.13 0.17 0.15 0.15 Cadusafos 27.27 26.08 37.01 35.82 33.84 26.28 26.79 26.86 26.71 21.36 21.29 Oil Solvent - - 3.98 3.86 3.64 - - - - - - PMPPI 4.67 2.79 7.98 7.73 7.30 2.30 2.82 2.87 2.88 2.88 2.86 2.29 1.83 Naphthalene CU - - - - - - - 0.27 0.11 0.11 DETA 2.81 1.77 3.19 3.09 2.92 1.78 1.82 1.82 1.81 1.45 0.06 Glycope Propylene 5.45 5.22 - - 4.67 5.26 5.36 5.37 5.34 5.34 5.32 co Con. H3P04 2.22 1.58 - - - - - - - - - cn Con. HCl - - 2.04 1.98 1.87 4.13 2.26 2.00 2.29 1.83 1.83 Sulfonate Na 0.78 0.93 6.95 6.72 6.94 2.35 2.39 2.40 2.38 1.91 1.90 1.90 Bactericidal A - 0.06 - - - - - - - - - Bactericidal B - - - - 0.05 0.06 0.06 0.06 0.06 0.05 0.05 Amfoterico - 4.66 - 3.21 3.04 - - - - - - Antiespuma 0.19 0.18 0.29 0.28 0.50 0.18 0.20 0.21 0.20 0.24 0.24 Water 56.05 56.10 37.83 36.60 34.56 56.51 57.63 57.80 57.46 64.74 66.67 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ro ro Ol o n I heard Table 2 (contii num) Percentages weight / weight Formulation CC DD EE FF (200) GG HH JJ (200) KK LL (200) MM NN Components PVA 0.64 0.63 0.50 0.54 0.54 0.56 1.07 0.54 0.55 0.54 0.53 Rubber Xantan 0.13 0.13 0.14 0.15 0.12 0.12 0.12 0.13 0.28 0.22 0.24 0.24 0.25 0.49 0.24 0.24 0.24 0.24 0.24 0.12 0.12 0.29 0.28 0.22 0.24 0.12 0.12 0.12 0.12 0.12 0.24 0.24 0.24 0.24 0.24 0.27 0.25 0.27 0.22 0.22 0.24 0.24 0.25 0.49 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.27 0.21 0.21 0.21 0.21 0.49 0.49 0.49 0.49 0.75 2.37 3.37 2.37 2.35 4.63 Naphthalene Cu 0.08 0.08 0.11 0.11 0.22 0.57 0.55 0.55 0.55 0.55 0.54 DETA 0.86 1.09 2.28 0.94 1.47 0.61 0.00 0.00 0.00 1.49 0.00 HDA 0.00 0.00 0.00 0.00 0.00 0.00 1.03 1.37 1.03 0.00 2.01 co O) Glycol Propylene 3.97 4.00 5.26 5.41 5.42 5.65 5.53 5.53 5.53 5.47 5.40 Con. H3PO4 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.05 0.00 1.04 0.00 Con. HCl 1.36 1.37 2.55 2.63 1.86 0.10 0.00 0.00 0.00 0.00 0.00 Sulfonate Na 1.42 1.43 1.88 1.93 1.93 2.02 1.99 1.97 2.00 1.98 1.95 Bactericidal A - - - - - - - - 0.03 0.03 0.03 Bactericidal B 0.03 0.03 0.05 0.05 0.05 0.05 - 0.05 0.05 0.05 - Water 74.00 73.26 62.21 64.79 64.16 65.41 65.24 64.86 65.96 64.80 63.48 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ro ro Ül o 01 01 Table 2 (continued) Percentages weight / weight Formulation (grms / L) PP (200) QQ (200) RR (200) Components PVA 0.46 0.46 0.54 Rubber Xantan 0.11 0.11 0.12 Antifoaming 0.20 0.20 0.42 Cadusafos 20.30 20.30 21.27 Naphthalene Cu 0.52 0.52 0.53 Oil Solvent 8.92 - - Corn Oil - 8.92 - PMPPI 6.39 6.39 3.90 co HDA 2.41 ^ 1 2.81 2.81 Urea 5.20 5.20 5.11 Con. H3P04 - ... 0.49 Sulfonate Na - - 1.96 Bactericide B - - 0.02 Inert Ink - - 0.02 Water 55.09 55.09 63.21 Total 100.00 100.00 100.00 ro r 01 or Ol Ol Table 3 Large Scale Preparation of Cadusafos Formulations (CS) of 200 grs / Liter) (Components and Quantities) Weight (pounds) Formulation PB-1 PB-2 PB-3 PB-4 PB-5PG PB-5U PB-6PG PB-6U PB-7PG PB-7U Component Cadusafos Isocyanate Solution 189.2 165.8 165.8 113.7 83.3 82.6 83.3 82.6 83.3 82.6 Naphthalene Cu 4.7 4.1 4.1 2.8 2.1 2.1 2.1 2.1 2.1 2.1 PMPPI 24.0 24.0 24.0 25.0 9.1 9.1 9.1 9.1 12.2 12.1 Aqueous solution Water 449.0 449.3 454.6 454.6 229.2 227.3 229.4 227.4 227.6 225.3 223.6 PVA 4.14 4.14 4.22 4.22 2.11 2.09 2.11 2.09 2.08 2.06 Xantan rubber 0.33 0.33 0.33 0.33 0.17 0.16 0.17 0.16 0.17 0.16 or 00 Antifoam 1.80 1.80 1.90 1.90 0.90 0.90 0.92 0.91 0.90 0.90 Sulfonate Na 15.10 15.10 15.30 15.30 0.28 0.28 0.23 0.23 7.58 7.58 7.52 Bactericide B 0.15 0.15 0.15 0.15 0.07 0.07 0.07 0.07 0.07 0.07 Solution Amine HDA 10.5 10.5 13.2 15.8 - - - - 5.3 5.2 DETA - - - - 5.8 5.7 5.8 5.7 - - Water 19.7 19.7 13.7 14.9 9.4 9.4 9.4 9.4 9.9 9.8 Additives After Encapsulation Con. H3P04 2.9 4.3 3.7 7.4 3.5 3.4 3.5 3.4 1.2 1.2 Water 0.5 0.8 0.7 1.3 0.6 0.6 0.6 0.6 0.2 0.2 Rubber Xantan 0.59 0.61 0.86 0.61 0.30 0.30 0.30 0.30 0.30 0.30 Water 29.0 29.9 42.2 29.9 14.9 14.8 14.7 14.8 14.7 14.7 Glycol Propylene 42.5 42.5 42.5 42 5 21.0 - 21.0 - 22.0 - Urea - - - - - 20.0 - 20.0 - 20.0 Bactericide B 0.27 0.27 0.39 0.27 0.14 - 0.14 - 0.14 0.14 Antiespuma 1.56 1.56 1.56 1.56 - - - - 0.78 co CD ro ro Ol o Oí Ol Formulation PB-8 PG PB-8U PB-9PG PB-9U PB-11 PG PB-11U PB-12PG PB-12U PB-13U-I Component Isocyanate Solution Cadusafos Isocyanate Solution 82.6 83.2 81.9 83.9 82.6 83.2 83.3 82.6 165.8 172.6 1254.68 Naphthalene Cu 2.1 2.1 2.0 2.1 2.1 2.1 2.1 2.1 4.1 4.21 PMPPI 15.1 15.3 18.0 18.5 15.1 15.3 9.1 9.1 56.5 53.0 386.86 Oil Solvent - ... - ... - ... ... - 73.0 74.1 538.47 Aqueous Solution Aqueous Solution Water 226.2 227.8 224.2 229.8 234.1 235.7 227.9 226.1 397.9 391.3 2795.06 PVA 2 09 2.11 2.07 2.13 2.09 2.11 2.1 2.1 3.7 7.24 51.71 Xantan rubber 0.16 0.17 0.16 0.17 0.15 0.15 0.2 0.2 0.26 0.32 2.27 Antifoam 0 90 0 90 0.89 0.91 0.91 0.91 0.9 0.9 1.8 3.33 23.76 Sulfonate Na 7 62 7.68 7.56 7.74 7.62 7.68 7.7 7.6 - 7.53 53.6 Bactericide B 0.07 0.07 0.07 0.08 0.05 0.05 0.1 0.1 ... 0.20 1.4 O Solution Amine Solution Amine HDA 6.6 6.6 7.8 8.0 6.6 6.6 4.0 3.9 32.8 33.3 166.52 DETA Water 7 2 7 2 7.3 7.5 6.8 6.9 11.1 11.0 12.1 12.3 159.48 After Encapsulation Additives After Encapsulation With. H3PO4 1.9 1.9 2.1 2.1 1.9 1 9 1.7 1.7 4.2 6.34 63.75 Water 0.3 0.3 0.4 0.4 0.3 0.3 0.3 0.3 0.8 1.13 11.25 Xantan rubber 0.31 0.3 0.31 0.30 0.3 0.31 0.31 0.3 0.61 0.64 4.6 Water 15.2 14.7 15.2 14.7 14.7 15.2 15.2 14.7 29.9 31.4 226.0 Propylene glycol 22.0 - 22.0 - 20.0 - 22.0 - - - - Urea - 20.0 - 20.0 - 22.0 - 20.0 42.5 44.6 321.6 Bactericide B 0.14 0.14 0.14 0 14 - - - - - - - Antiespuma 0.81 0.75 0.81 0.75 0.76 0.8 0.8 0.8 - - - Ink Inert - - - - - - - - - 0.17 1.3 Table 4 Large Scale Preparation of Cadusafos (CS) Formulations of 200 g / Liter (Components and Weight / Weight Percentages) Percentage (weight / weight) Formulation (grms / L) PB-1 PB-2 PB-3 PB-4 PB-5PG PB-5U PB-6PG PB-6U PB-7PG PB-7U Component Cadusafos 23.77 21.4 21.01 15.38 21.75 21.8 21.75 21.79 21.44 21.55 Copper Naphthenate 0.59 0.54 0.53 0.39 0.54 0.55 0.54 0.55 0.54 0.54 PMPPI 3.01 3.10 3.04 3.41 2.39 2.39 2.39 2.39 3.14 3.16 PVA 0.52 0.53 0.53 0.58 0.55 0.55 0.55 0.55 0.54 0.54 Xantan rubber 0.12 0.12 0.15 0.13 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Antista foam 0.42 0.43 0.44 0.47 0.24 0.24 0.24 0.24 0.43 0.44 ro HDA 1.32 1.35 1.67 2.16 - - - - 1.36 1.36 DETA - - - - 1.51 1.51 1.51 1.51 - - Glycolopropylene 5.34 5.48 5.38 5.80 5.49 - 5.49 - 5.67 - Urea - - - - - 5.28 - 5.28 - 5.22 Con. H3PO4 0.36 0.56 0.47 1.01 0.90 0.91 0.90 0.90 0.32 0.32 Sulfonate Na 1.90 1.95 1.94 2.09 0.07 0.07 0.06 0.06 1.95 1.96 Bactericide B 0.05 0.05 0.07 0.06 0.06 0.02 0.05 0.02 0.05 0.02 Water 62.60 64.49 64.77 68.38 66.38 66.56 66.40 66.59 64.44 64.75 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ro ro n Formulation (grms / L) PB-8PG PB-8U PB-9PG PB-9U PB-11PG PB-11U PB-12PG PB-12U PB-13U-ND PB-C14U-ND PB-C18U Component Cadusafos 21.11 21.27 20.84 21.03 20.86 20.74 21.42 21.54 20.08 20.46 20.7 Copper Naphthenate 0.53 0.53 0.52 0.53 0.52 0.52 0.54 0.54 0.50 0.50 - PMPPI 3.87 3.90 4.59 4.63 3.82 3.80 2.35 2.36 6.84 6.28 6.38 Petroleum Solvent - - - - - - - - 8.84 8.78 8.88 PVA 0.53 0.54 0.53 0.53 0.53 0.53 0.54 0.55 0.45 0.45 0.86 0.85 Xantan rubber 0.12 0.12 0.12 0.12 0.11 0.11 0.12 0.12 0.11 0.11 0.04 Antis foam 0.44 0.42 0.43 0.42 0.42 0.43 0.44 0.44 0.22 0.39 0.39 HDA 1.68 1.69 1.99 2.01 1.65 1.65 1.02 1.03 3.97 3.95 3.92 -fc > .

Propylene glycol 5.62 - 5.60 - 5.05 - 5.66 - - - - CO Urea - 5.11 - 5.01 - 5.48 - 5.22 5.14 5.29 5 30 Con. H3PO4 0.49 0.49 0.53 0.54 0.48 0.48 0.44 0.44 0.51 0.76 1 24 Sulfonate Na 1.95 1.96 1.92 1.94 1.92 1.91 1.99 1.99 - 0.89 0.89 Bactericidal B 0.05 0.05 0.05 0.05 0.01 0.01 0.02 0.02 - 0.02 0.02 Inert Ink - - - - - - - - - 0.02 0.02 Water 63.61 63.92 62.88 63.19 64.63 64.34 65.46 65.75 53.34 51.69 51.37 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 6 Acute Dermal Toxicity in Cadusafos Mammals CS Formulations Formulation LD5o (mg / kg) Category Probable EPA B > 500 G > 50 and < 500 PP1 > 500 lll QQ > 500 PB-8PG < 500 PB-8U < 500 PB-9PG > 200 and < 500 PB-11 PG > 50 and < 2002 PB-12PG > 50 and < 2002 PB-C14U-ND > 500 and < 5,000 Formulation tested twice. 2 Toxicity based on the most sensitive females the acute oral toxicity LD50 of the Rat, of a known formulation of Cadusafos 100ME is 371 mg / kg or Category II Table 7 Mean score of root scrapings caused by the nematode knotted to the root, incognito M., in tomatoes after 48 hours of treatment with formulations of Cadusafos CS Average Scratch Rating by Root in Formulation Q.25 5 Range (Kg / Ha) AA 0 0 BB 0.8 0 BB-1 1.8 0 CC 0.4 0 EE 0 0 FF 0.2 0 100 ME 0 0 Technical 2.4 1.2 Table 8 Average score of root scrapings caused by the nematode knotted to the root, incognito M., in tomatoes treated with formulations of Cadusafos CS 7 days before the infestation of the ground with nematodes Average Scratch Rating by Root Knots Formulation 0.25 Í 5 1? 2? Range (Kg / Ha) YYYY 11..22 00 00 0 BB 0.8 0 0 0 BB-1 0.6 0.2 0 0 CC 0.8 0 0 0 EE 0.6 0 0 0 FF 0.8 0 0 0 100 ME 0 0 0 0 Technical 4.4 3.0 0.6 0.4 Scratch Rating: 0 without scratches, 10 is an intense scrape * & js & amp? & t Table 9 Residual Land Activity of Cadusafos CS Formulations against Southwestern Rootworm Larva on Clay and Sand Terrain Residual Period (days) Percentage of Mortality Formulation range (ppm)? 1 4 1 14 21 35 42 £ 3 84 B 0.2 63 72 75 47 78 89 47 35 49 E 0.2 77 33 55 43 75 60 51 30 35 9 F 0.2 90 98 92 63 88 78 33 68 33 - ^ 1 G 0.2 98 98 85 60 95 96 75 52 75 97 H 0.2 10 82 60 63 83 73 47 42 22 ... 0 PB-C14U-ND 0.2 3 23 23 30 28 100ME 0.2 93 92 83 67 78 85 49 30 31 40 BiodadOG 0.2 ... 14 55 15 5 30 - - - - ro ro 01 o Oí Oí Table 10 Residual Land Activity of Cadusafos CS Formulations against Southern Corn Root Worm in Sandy Terrain Rich in Clay and Sand Residual Period (days) Percentage of Mortality Formulation range (ppm)? 1 4 1 21 35 49 m 84 112 B 1.5 100 100 100 97 97 98 98 97 100 62 oo E 1.5 100 100 100 100 100 98 100 100 100 70 F 1.5 100 100 100 97 97 98 98 97 100 62 G 1.5 100 100 100 97 100 98 100 100 100 75 H 1.5 100 100 100 100 97 98 100 100 100 73 100ME 1.5 100 100 100 100 100 100 100 100 100 33

Claims (9)

1. CLAIMING IS 1 .- A process for preparing a microencapsulated cadusafos formulation, comprising the steps of: a) providing an aqueous phase containing one or more emulsifiers and an antifoaming agent; b) providing a non-miscible phase in water comprising up to 98 percent by weight of cadusafos, from 2 to 35 percent by weight of a first polyfunctional compound; c) emulsifying the non-miscible phase in water in the aqueous phase, forming a dispersion of droplets immiscible in water in the aqueous phase; d) adding to the dispersion an aqueous solution of one or more of the second polyfunctional compounds, in an effective amount pat to achieve interfacial polymerization with the first or polyfunctional compound, thereby forming microcapsules of cadusafos.
2. 2. - The process of Claim 1, wherein the non-miscible phase in water additionally comprises a hydrocarbon solvent.
3. 3. - The process of Claim 1, wherein the first polyfunctional compound is an isocyanate monomer.
4. 4. - The process of Claim 1, wherein the second polyfunctional compound is selected from the group consisting of DETA, r, TETA, DA, and a combination of any two or more of DETA, TETA, and HDA.
5. 5. - The process of Claim 1, further comprising curing the microcapsules.
6. 6. - The process of Claim 5, further comprising neutralizing the pH of the microencapsulated cadusafos formulation.
7. 7. - The process of Claim 6, wherein: i) the aqueous phase comprises from about 0.3 hasl to about 5.0 by weight of one or more emulsifiers, and from about 0.1 to about 1.0 percent by weight of the antifoaming agent; ii) the non-miscible phase in water comprises from about 50 to about 98 percent by weight of cadusafos and the first polyfunctional compound is polymethylene polyphenyl isocyanate (PMPPI); iii) the curing of the microcapsules comprises the continuation of the emulsification while the dispersion is heated to a temperature within the range of from about 20 to about 60 ° C for a period of one to ten hours.
8. 8. - The process of Claim 7, wherein the aqueous phase further comprises from about 0.05 to about 0.50 percent by weight of a viscosity modifier / stabilizer of xanthan gum and 0.02 to 0.1 percent by weight of a bactericide.
9. 9. - The process of Claim 8, wherein the non-miscible phase in water further comprises from about 1.5 to about 30 percent by weight of a hydrogen solvent. 1 - The process of Claim 9, wherein the emulsifier is a polyvinyl alcohol; the antifoam agent is a polydimethyl siloxane; The percentage by weight of the hydrocarbon solvent is from approximately 20 to about 25 percent by weight of non-miscible phase in water; the percentage by weight of the cadusafos is from approximately 53 to approximately 92 percent of the non-miscible phase in water; the percentage by weight of the PMPPI is from about 4 hasl to about 25 percent of the non-miscible phase in water; the percentage by weight of the second polyfunctional compound is from about 20 to about 70 percent of an aqueous amine solution; and the microcapsules are cured at a temperature of from about 30 to about 50 ° C, for about three to about four hours. 1 - The process of Claim 1 0, wherein one or more additives are added to the formulation after completing the cure step, wherein the additives are selected from the group consisting of from about 1.3 to about 6.0 percent by weight of propylene glycol, from about 5.0 to about 5.5 percent by weight of urea, from about 0.003 to about 0.30 percent by weight of xanthan gum, from about 0.01 to about 0.1 percent by weight of one or more bactericides, up to about 0.05 percent by weight of an inert dye and up to about 7.0 percent by weight of one or more surfactants, each percentage by weight is relative to the weight of the formulation after the addition of the additives.

   2. The process of Claim 11, wherein the amounts of aggregate additives are from about 1.2 to about 5.8 percent by weight of propylene glycol or urea, from about 0.004 to about 0.1 7 percent by weight. weight of xanthan gum, from about 0.01 to about 0.08 percent by weight of one or more bactericides, to about 0.04 percent by weight of an inert dye and from about 0.7 to about 6.7 percent by weight of one or more surfactants.

   3. The process of claim 1, wherein the cadusafos is pretreated with a copper salt.

   14. - A pesticide formulation prepared according to the process of the Claim 1 ^ aS. * ~ Fi? JBJÑgSfe afc- ¿U «mmM m > i s -. -i ^ & VÁJi

   5. A process for preparing a microencapsulated cadusafos formulation, comprising the steps of: a) providing an aqueous phase comprising from about 0.3 to about 5.0 percent by weight of one or more 5 emulsifiers and from about 0.1 to about 1.0 percent by weight of the antifoam agent, and optionally further comprising from about 0.05 percent by weight to about 0.50 percent by weight of a viscosity modifier / stabilizer of xanthan gum, and so optional, from about 0.02 to about 0.1 percent by weight of a bactericide; b) providing a non-miscible phase in water comprising from about 50 to about 98 percent by weight of cadusafos optionally pre-treated with a copper salt, from about 2 to about 35 percent by weight polymethylene polyphenyl isocyanate ( PM PPI) and, optionally, from about 1 5 to about 30 percent by weight of a hydrocarbon solvent; c) emulsifying the non-miscible phase in water in the aqueous phase, forming a dispersion of water-immiscible droplets throughout the entire aqueous phase; d) stirring the dispersion while adding thereto an aqueous solution of from about 10 to about 1000 percent by weight of one or more polyfunctional amines; - &"-" -. -. "" 5r ai (te-gfe? e) cure the microcapsules continuing the agitation while heating the dispersion to a temperature within the range of from about 20 to about 60 ° C during from one to ten hours, and 5 f) neutralizing, optionally, the pH of the formulation with an acid. 1 6.- A pesticide formulation prepared according to the process of the Claim 1 5.

   10. A pesticidal formulation of cadusafos comprising ur to aqueous suspension of microcapsules, the microcapsules comprising a polyurea shell surrounding a nucleus of the cadusafos, having formed or formed the polyurea shell from interfacial polymerization of an isocyanate. and one or more polyfunctional amines, the polyurea coating being 15 sufficiently waterproof for cadusafos, so that a reduction in the toxicity of the formulation in mammals was made, compared with the aqueous microemulsion formulations having an equivalent or lower concentration of cadusafos. The pesticidal formulation of Claim 1 6, which contains from about 150 to about 360 grams of cadusafos per liter of formulation, and comprising the aqueous suspension of microcapsules; from about 0.7 to about 2.5 weight percent polyvinyl alcohol; and from > feBI- * * • * »*«,. . tf - a, '' M? Ü¿A, 1J.A- Jjte ^ 'a gfe > i "&"; fcaS? fc «t approximately 0.3 to approximately 0.9 percent by weight of antifoaming agent. 1 9. The pesticidal formulation of Claim 1 9, comprising from about 200 grams of cadusafos per liters of formulation, in which the percentage by weight of the cadusafos is from approximately 53 to approximately 92 percent of water immiscible phase provided for the interfacial polymerization, the percentage by weight of the isocyanate is from approximately 4 to approximately 25 percent of phase not miscible in water and the percentage by weight of the hydrocarbon solvent, if used, is from about 20 hasl to about 25 percent of the immiscible phase in water.

   20. - The pesticidal formulation of Claim 1 7, wherein the isocyanate is polymethylene polyphenyl isocyanate (PMPPI).

   21. The pesticidal formulation of Claim 16, wherein the polyfunctional amine is selected from the group consisting of TETA, DETA, DA and a combination of one or more of TETA, DETA, and DA.

   22. The pesticidal formulation of Claim 1 7, which additionally comprises: d) optionally, from about 0.06 to about 0.4 percent by weight modifier / viscosity stabilizer of xanthan gum; e) optionally, from about 0.03 to about 0.05 of one or more bactericides; f) optionally, from about 0.7 to about 6.7 percent by weight of one or more surfactants; and g) optionally, from about 1.2 to about 5.8 percent by weight of propylene glycol or urea.

   23. - A granular pesticidal formulation of cadusafos, comprising carrier particles covered with the microcapsules of Claim 16.

   24. - The granular formulation of Claim 23, comprising from about 5 to about 30 percent by weight of microcapsules, from about 60 to about 95 percent by weight of vehicle and from about 0.05 to about 5.0 percent by weight of a adhesive agent.

   25. - A pesticidal formulation of from about 150 to about 360 grams of cadusafos per liter of formulation, from about 0.7 to about 2.5 percent by weight of polyvinyl alcohol and from about 0.3 to about 0.9 percent by weight of antifoam agent, comprising formulating an aqueous suspension of microcapsules, the microcapsules comprising a polyurea shell surrounding a nucleus of the cadusafos, the polyurea shell having been formed from interfacial polymerization of PM PPI and one or more polyfunctional amines, wherein the percentage by weight of cadusafos is from about 53 to about 92 percent of a non-miscible phase in water provided for interfacial polymerization, the percentage by weight of the PMPPI is from about 4 to about 25 percent of the non-miscible phase in water, and the optional amine is selected from the group consisting of TETA, DETA, and HDA, and a combination of one or more of TETA, DETA, and HDA.

   26. - A granular pesticidal formulation of cadusafos, comprising carrier particles covered with the microcapsules of Claim 25. f ^ E * > & amp; & amp;