IT8323066A1 - GRANULES OF PESTICIDES - Google Patents

Description

DOCUMENTATION

BOUND

Case 136-6946? Ng. Barzan? & zanardo

D E S C R I Z I O N

of the industrial invention entitled:

"Pesticide granules"

of the company SANDOZ AG.

of nationality? Swiss

based in BASEL (SWITZERLAND)

who appoints as? inventor: Tsuong Rung SHIEH filed on:

29 SEPT. 1983 2 3 06 6 A / 83

R I A S S U N T 0

The invention provides a new, freely flowing, water-floating granular form of a pesticide, for example a logical mosquito larvicide, the preparation of such a granular form and a process for combating mosquito pests using such granules.

DESCRIPTION

The present invention relates to granular forms of pesticides, for example biological pesticides, their preparation and their use.

In recent years, biological pesticides have assumed increasing interest and importance.

They are more? or less highly sensitive to a large variety? of factors such as heat, light, chemicals and other influences that are found when es-2- Ing. Barzan? & Zanardo are outside their natural environment. So, the stability? (heat stability, light stability and storage stability)? a key feature and main requirement of the organic pesticide.

The biological pesticides consequently allow less flexibility? in product forms compared to synthetic chemicals for similar use.

Are granular formulations of pesticides of substantial interest in combating harmful organisms ?. Until now granular formulations of unstable pesticides such as biological pesticides have not met the necessary stability requirements. The description of US patent 3,420,933 describes for example granular forms for the bacterial insecticide Bacillus sphaericus (a bacterium which is particularly toxic towards mosquito larvae), which for at least 20% are non-floating in water and are prepared by conventional granule materials that form the core such as vermicuiite and clays. Granular formulations of biological pesticides prepared with such conventional core materials exhibit a drastic loss of potency within one week of their preparation.

-3- Ing. Barzan? & zanardo

The purpose of the invention? that of providing a granular form suitable for use with stable pesticides and also with unstable pesticides, in particular for unstable pesticides, especially for biological pesticides. Another purpose of the invention? that of providing a granular form which is suitable for aquatic application (for example from air) and which is capable of releasing the pesticide substantially on the surface of the water. Yup ? found that the latter property? ? especially interesting when fighting mosquito larvae in water. The present invention provides a granular form of a pesticide freely flowing and floating on the water in which the granules comprise

a) a central part of solid wax or a central part coated with solid wax having a density? lower than that of water and what? inert towards the pesticide e

b) a pesticide fixed on the central part of wax or on the central part coated with wax by means of a matrix which? inert towards the pesticide and what? capable of releasing the pesticide when it comes into contact with water.

The use of wax as a central part of the granu-4- Ing. Barzan? & Zanardo the coating material not only allows the production of a buoyant granule but also

? * lizes the basis for a pesticide transfer system having a stable power and a number of other properties? desired for a granular pesticide in particular for a granular pesticide useful in water applications.

The expression "buoyant" is used to indicate that the density? of the granules of the invention must be lower than that of water and that, even in contact with water, the granules must remain on the surface for a period of time sufficient to allow the release of the pesticide at the surface of the water; suitably at least 95% of the granules of the invention must remain: on the top

* \

water surface 24 hours after application.

The term "wax" as used herein is intended to include any hydrophobic substance which meets the criteria of the invention (lighter than water, solid and inert to the pesticide). Suitable examples of such waxes are silicones and pararfinic ceers, in particular the latter.

The expression "solid" used in relation to the central part of wax or to the central part coated with wax means to indicate that the central part -5- Ing. Barzan? The wax or the wax coating must be solid at room temperature and must have a melting point above 30 ° C and preferably at least 40 ° C. Preferred waxes have a melting point between 45? C and 85? C, plus? preferably between 50 ° C and 75 ° C.

The wax used must be inert in the sense of not being harmful to the pesticide to be incorporated into the granule. Should particular importance be given to this requirement when the pesticide concerned? a biological pesticide. Inertia can be routinely ascertained by simple trial and error if necessary. However, in general the paraffin substances are inert towards biological pesticides and paraffin waxes are preferred as material for the central part of the granules of the invention. Paraffin waxes that have melting points in the pi? preferred are "readily commercially available in a suitable finely divided form (" granule "), for example, Sun Wax 4412 (PP 60? C) and Sun Vax Anticheck (PF 67? C), both available from the Sun Petroleum Products Company, Vayne, Pennsylvania.

The wax core or wax-coated core (hereinafter "core") can? be established es6- Ing. Barzan? & Zanardo essentially from the solid material consisting of wax or can? be a material that includes an internal base surrounded by the solid material of the wax to which it will come? fixed the matrix. In the latter case, all that is required is that the wax substantially completely coats the inner base and that this coating has a sufficient thickness so that the inner base does not adversely affect the pesticide and that water does not penetrate through the coating. of wax in order to make s? that the gra-. total nule does not submerge at least before its supported pesticide is substantially released onto the. the surface of the water.

Can you? employ a large variety? of finely divided materials or in particles as base material to be coated with wax (hereinafter referred to as "base material") so as to form the core of the particles coated with wax. Those basic materials by themselves? preferably have a density? lower than that of water and can be mineral in nature such as vermiculite or organic in nature such as finely divided corn cobs, for example the material known as corn cob granules.

The main advantage of using -7- Ing. Barzan? & zanardo a basic material? a decrease in the cost of the particle core. The quantity of base material compared to the wax in such cores coated with wax pu? vary quite widely and the base material can? easily make up the bulk of the core on a weight or volume basis.

Therefore in general it is preferred that such cores contain 10% to 60% wax and 40% to 90% base material by weight, plus? preferably 15% to 35% by weight of wax and 65% to 85% of base material, provided that the requirement is met that the wax substantially coats the base material.

For example, a basic material consisting of a grain of corn cob can? be used to prepare a wax-coated core containing 75-90% corncob and

10-25% wax on a weight basis. The particle diameter of the particulate base material to form such wax-coated base particle cores preferably? between 0.3 and 3.0 mil limeters (mm), pi? preferably between 1 and 2 mm.

The wax-coated cores can be prepared by a conventional process for the application of a normally so-8- Ing. Barzan? & Zanardo lido on a particle base, it is generally preferred to first liquefy the wax by heating well below its melting point, for example at least 50 ° C above its melting point, preferably at least 75 ° C. up to 125 ° C above its melting point and then distribute the

melted wax on the bulk of the base material in particles, for example by spraying., by effecting? also a mixing in order to ensure a complete and more? or less uniform than the wax

on the base material. Intensive mixing is desirable and such mixing is continued until the temperature of the wax? well below its melting point, for example? practically

at room temperature in order to avoid unwanted agglomeration of the individual wax granules or cores obtained. Can you? adopt a heating of the mixture by means of an external device or by introducing a heated gas

inert directly in the mass to ensure a uniform distribution of the wax before making s? that the mass cools to form the desired nuclei.

The particle diameter of the "core" suitably? between 0.5 and 5 mm. When the core? consisting of wax such a diameter? preferably

-9- ing. Barzan? & Zanardo between 0.5 and 3.0 min, plus? preferably between 1 and 2 mm. The wax-coated cores preferably have a particle diameter between 1 and 4 mm, plus? preferably between 2 and 3.5 mm.

As indicated, in the granules of the invention the pesticide? contained within a matrix which in turn is fixed to the underlying "core".

The term "matrix" as used herein is intended to include any system capable of attaching the pesticide to the wax core; such matrix? suitably .essentially pouch.

The expression "essentially dry" as used in relation to the matrix is meant to indicate that the properties? of the matrix - must allow a good flowability of the mass of particles.

The matrix can? be fixed directly on the "core" or indirectly through one or more? separate layers of a suitable inert coating.

Depending on the function of the matrix systems, a distinction is made below between "matrix coating material", which essentially acts to bind the pesticide, directly or indirectly, to the core and "encapsulation matrix", which? essentially a protective matrix meant to indicate a complete incorporation or av-10- ing. Barzan? If the pesticide changes in the matrix, although a smaller proportion of the pesticide may be present and usually? present or can it be exposed or? exposed at the surface of the matrix. It should be noted that the use of an encapsulation matrix? particularly suitable when? necessary to maintain stability? of the pest? i cida. Even in the pi? simple of the present invention, you can? consider that the pesticide is encapsulated within its matrix pi? immediate or adjacent, the expression "sistarna matrix" or "matrix system" will come? used hereinafter to denote the essential and total matrix system having a complete encapsulation effect and comprising or? consisting of an equally essential coating matrix.

The material of the matrix can? be uniform (or homogeneous) or can? be made up of different matrix materials that can each surround the core (thus forming a multiple matrix (multiple layer) and / or form a heterogeneous mixture of different matrix materials that involve for example a plurality of encapsulation matrices inside The action of water on the different matrices can be consequently different, therefore the different transfer systems can vary. be water-dispersible or water-soluble or practically non-humidable with water. The matrix material can substantially incorporate the pesticide or it can incorporate the pesticide only partially or it can consist of several matrix materials of which some or only one can substantially fully incorporate the pesticide and the other (the others) can incorporate re only partially the pesticide.

For example, moisturisable encapsulated pesticide particles? with water, for example, dispersible (such as biological pesticides) can be combined with a matrix coating which? substantially not humidifiable with water (respectively insoluble in water) so as to lead to the release of the toxic agent by humidifying the portion of dispersible particles

in water at the surface of the granule. Such action in correspondence of the surface in general will expose? other particles or other humidifiable portions originally inside the granule due to the action of humidification and cessation -12- Ing. Barzan? & Zanardo ne so that further quantities can be released? of the pesticide contained.

In general, however, it will be? Particularly preferable in the case of pesticide particles encapsulated in a water-dispersible matrix, to use a matrix coating which is essentially water-humidifiable, for example soluble or water-dispersible so that the entire matrix system is released from the core by the action of water.

The particular material to be used as a ma-? matrix terial of the system will depend? the particular pesticide to be developed and various choice factors. While ? a wide choice of matrix materials and coating vehicle substances is available. treatment with pesticides other than organic pesticides, the choice of such materials? pi? critical when a biological pesticide is used as the active ingredient. Types of materials suitable for use with biological pests are carbohydrates, protein materials of animal or vegetable origin and materials selected from a synthetic source. Suitable carbohydrate materials include starches such as corn starch and various cellulosic materials such as ethyl cellulose. Suitable protein materials include but not limited to casein, carrageenan, vege seed protein? -13- Ing. Barzan? & Zanardo such partially hydrolyzed as soy protein and partially hydrolyzed animal protein. Representative synthetic materials include normally solid polyethylene glycols and polyvinyl alcohol resins. The particular material suitable as a matrix and which makes the medium more? inert and more? stable for a particular pesticide usually will be? known. When not? known, as in the case of new materials intended for biological pesticides, the suitable material for matrix can? be determined by routine experimentation. In general, the protein materials provide a stable medium for biological pssticides such as bacteria, viruses and fungi which can be used in general.

As indicated, at least the coating matrix of the matrix system must have the function of securing the pesticide to the particulate wax core. Therefore, particularly in the embodiments in which the coating matrix? fixed directly to the "core", the fixing mechanism essentially? a surface bonding mechanism that is generally realized by the properties? adhesives of materials employed in the coating matrix and such materials are further selected accordingly. The expression "adhesive" and yes-14- Ing. Barzan? & zanardo mili how it is used here includes the different properties? by which adhesives can make a bond that include properties? and capacity? such as adhesiveness, penetration and the like and furthermore the advantages of cohesion as achieved in particular by film-forming adhesives.

When a coating matrix material that produces water-dispersible coatings or other coatings in a characteristic and essentially non-film-forming manner is employed, the property of the of adhesiveness? becomes a factor more? positive and you must also consider the fact of maintaining the adhesiveness? of these coatings leaving an appropriate moisture content? residual and carrying out the conservation in conditions that do not rapidly decrease the humidity? residual.

When film-forming coating materials are employed, the resulting film provides a particularly effective mechanism for bonding the coating matrix directly or indirectly to the " core, " even though such film may be bonded. be substantially interrupted by non-homogeneous particles contained therein.

The use of a film-forming coating matrix therefore? a pre-embodiment -15- Ing. Barzan? & Zanardo wound of the present invention. Suitable film-forming coating materials are suitably water-soluble adhesive materials such as hydrolyzed animal proteins (a known constituent for glue for wrappers). When the pesticide? a biological pesticide, the matrix material of the system can? be present in the organically manufactured product, as a result of the raw materials used in the manufacture, or can it? be chosen from a separate source or can? have both of these origins.

For example, bacteria and fungi useful as pesticides are usually produced commercially by fermentation in a nutrient medium which includes water, carbohydrates, proteins and several compatible inorganic salts. The product obtained on a dry basis usually contains a higher proportion typically at least 30 / -? by weight of carbohydrate and protein residues which are at least partially dispersible in water and such products may suitably be used as such as material for the system matrix or as a component thereof in the preparation of the granules of the present invention. Fermentation products in which the protein residue alone? at least 50% by weight of the product on -16- Ing, Barzan? & Zanardo a dry base are usual and are preferred in the case of fermentation products to be used alone or mixed with one or more? of other matrix materials to form a coating composition.

charged with

Such fermentation products can be used as a coating after making any adjustments required to bring the water content to the desired level, for example by evaporation under vacuum.

Alternatively, drying the product of a fermentation batch, for example spray drying according to known processes, produces a dry particle mass in which the particles constitute an encapsulation of the biological pesticide in a matrix consisting of the residue of the medium. fermentation nutrient. (A suitable example of such particle form is the technical powder form of a bacterial insecticide such as Bacillus thuringiensis Israeliensis). This particle mass can? be mixed with water to form a sticky paste-like composition that can be be applied on the "core" to form a granule in which the biological active material? fixed in a formed coating matrix

-17-? Ing. Barzan? & Zanardo from the residue of the nutrient medium. On the other hand, and according to the most embodiments? preferred of the invention, a dry powder, obtained for example by spray drying the fermentation charge,? a particularly suitable form to be applied to the " core " particles while still wetted by a first coating of matrix coating material.

Application of such a preferred embodiment to biological pesticides not normally produced by fermentation, e.g. virus pesticides, can be applied. it can also be accomplished for example by using fine particles which include a pesticide consisting of viruses encapsulated in a water-dispersible protein matrix.

The invention therefore carries out a process for preparing the granules of the invention which comprises the steps consisting of

i) applying to the "core" a liquid composition of coating matrix possibly containing the pesticide e

II) add the pesticide in solid form substantially after the completion of phase I) so phase II)? - optional in case the composition of the coating matrix contains

-18- Ing * Barzan? & Zanardo actually uses the pesticide.

The coating process can? be made according to coating techniques of however? no you, adopting for example

a) known methods of applying a liquid matrix material containing the pesticide to essentially dry particles, which are uncoated or have a previously dried coating (hereinafter referred to as variant A), b) known methods of applying a material in dry pesticide particles on particles of the "core" humidified by means of a previous coating (variant B), which is followed by drying if necessary to obtain a freely flowing mass.

The method of variant A is suitably carried out by intimately mixing the pesticide or the pesticide material with the liquid matrix material which mixture is then applied directly or indirectly on the "core".

According to the method of variant B, the pesticidal material in solid form, for example in the form of particles or in the form of powder, is applied to the "core" and / or is made to absorb on the "core" while? wet for a coating material-19- Ing. Barzan? & Zanardo matrix chin previously applied.

The term "pesticidal material" as used herein indicates that said material can? consist essentially of the pesticide or can? be in the form of a composition for example in the form of a moisturizable powder or it can be in the form of a composition. be encapsulated in a suitable inert material (OP-pure encapsulation matrix).

When using a liquid coating is the solvent or dispersant distribution vehicle preferably? water although organic solvents can be used. The matrix material used in the variant A method preferably must be essentially water dispersible or water soluble so as to allow the release of the pesticide when contact with water is made.

In the most embodiments? favorite

of the invention, fine dry particles which contain encapsulated pesticide in an encapsulation matrix are applied over and at least partially incorporated into an undried matrix coating which is previously applied to the "core". In such a process the material from the "core" in the form of desired particles (e.g. in granules) is mixed together e.g. by ba-20-Ing, Barzan? & Zanardo re-pressing in a suitable mixer and the coating matrix material is then sprayed (suitably in the form of an aqueous solution) or otherwise applied to the mass of the "core1 * followed by a continuous mixing sufficient to apply the matrix. coating substantially over the entire surface of the individual particles of the "core". For spray application in many cases, concentrations of the order of 20 to 50%, preferably 30% to 40%, are suitable for spray application. a weight / volume ratio.

The coating is preferably made more? or less at room temperature or otherwise below the melting point of the wax. The quantity of material of the coating matrix on a dry basis can? vary according to a number of factors which include the material used, the thickness of the coating desired, the capacity? coating and the like. In general, the quan-? tit? of coating? very small in relation to the weight of the material of the "core" and can? also be relatively minor in comparison to the quantity? of pesticidal material (e.g., a finely divided encapsulated biological pesticide) to be added later. For example, the coating matrix in the -21- Ing. Garzano & Zanardo the most suitable embodiments? do you prefer pu? represent a concentration between 0.5 and 5.0% by weight of the "core".

Will the mixing time to apply the coating matrix solution to the "core" vary? but can? be a relatively short time between 1 minute and 20 minutes, plus? specifically between 3 minutes and 10 minutes. When such a coating? complete, the mixing or another type of tumbling of the mass into particles of liquid coated wax is continued in order to avoid an undesirable agglomeration.

The addition of the pesticide in dry form (in finely divided encapsulated form or in powder form) can? be started immediately after cine coating? complete or with a certain delay depending on the drying characteristics of the matrix coating and the quantity? desired absorption or the degree of adsorption in the matrix coating. The addition of the pesticidal material is accomplished by controlled and / or intermittent introduction or by distributing the coated core particles in the tumbling mass in order to obtain a better application. or less uniform of pesticide particles -22- Ing. Barzan? & Zanardo on coated core particles.

The time of addition of the pesticide material? Can? be of the order of 1 minute up to 20 minutes, plus? in particular of 2 minutes up to 10 minutes; the addition is preferably carried out at room temperature and preferably below the melting point of the wax core or wax coating material. The quantity of the matrix material (dry weight) on which or in which the pesticide is applied pu? be relatively minor in comparison to the quantity? of pesticide material; for example it can? represent from 3.0 to 25%, more particularly from 5.0 to 20% on the weight of said pesticidal material. The quantity particular of pesticidal material to be used depend? among other things from the capacity? of the liquid matrix coating solution to absorb pesticide material, from the final desired characteristics of the product (such as power) and from practical considerations such as the time required to dry the product and the necessity of the product. to avoid unwanted agglomeration of the particles in the fluid mass of particles.

.When ? completes the addition of the pesticide material, the particle mass obtained is maintained-23- Ing. Barsan? & Zanardo is left in a state of agitation and is subjected to drying in order to obtain a freely flowing product in particles. Such drying can? suitably carried out with a heated inert gas, such as heated air which is introduced into the mass being stirred. When is an organic pesticide usually used as a pesticide? It is necessary to control the temperature of the drying conditions or of the gas heated to moderate levels. In general you can? adopt satisfactorily an air temperature between 38? C (iOO? F) and 7i? C (i60? F), plus? suitably, air temperatures between 43? C (110? F) and 60? C (140? F) can be adopted. In general not? it is necessary to completely dry the mass and you can? obtain a satisfactory product with a decrease in the moisture content? at most up to no more? of 10%, preferably up to no more? 8%. The retention of a certain humidity? can be desirable, as noted above.

Will the drying time vary? depending on particular cases and can? be between 15 minutes and 3 hours, for example can? be 1 hour.

The drying can? be facilitated or can? be carried out at a decreased temperature, for e-24- Ing. Barzan? & Zanardo sempio about at room temperature, by adding a substance that absorbs humidity? in quantity? substantial, for example 50% to 150% by weight of the mass of granular product. Such material can? therefore also serve as a diluent for the pr? learned. A suitable material for this purpose? a grain of corn cob (not coated with wax) even if this material is not? suitable as material - ?? of the core when not? coated with wax. Any agglomerates formed during drying can be separated, for example by hand.

The diameter of the particles of the product can? vary quite widely, for example from 0.5 to 5 mm. When using typical commercially available beaded wax forms, the diameter of the particles in the final product can? typically vary between 0.5 and 4 mm, pi? preferably between 1 mm and 2 mm. When using wax-coated base cores, the end products can typically have a diameter of between 1 mm and 5 mm, more so. typical between 2 mm and 4 mm.

The product obtained pui? then be mixed and coated with a small amount, for example from 0.1 to 4.0% by weight of the granule, preferably between 0.5 and 2%, of an anti-agglomeration agent such as -25- Ing. Barzan ? & Zanardo calcium stearate, different silicas-such as High Si, Aerosil and the like, if desired.

In the preferred embodiment in which. fine particles of an encapsulated biological pesticide are applied on wax which? wetted with a matrix coating material, the exact nature of the final product will vary, depending on several factors such as quantity. of encapsulated material applied to the coating matrix material. The use of quantity? only moderate of a finely divided encapsulated biological pesticide can? lead -as a result to an incorporation pi? or not substantially complete with the particles containing the biological pesticide in the matrix coating. The application of quantity? pi? large of biological pesticide that reach up to the capacity? of absorb- 'of the coating of

bimento / liquid matrix give? as a result that a significant portion of the particles containing the biological pesticide are less than completely incorporated and even in some cases are more adherent. between them and to the coating matrix. This last product will allow? the staggered release over time of a high or maximum dosage of highly charged particles. When is a -26 cladding matrix material used? Ing. Barzan? In film form some of the encapsulated particles containing the biological pesticide can penetrate the matrix coating without substantially affecting the cohesion advantage of said film coating matrix. These systems, in particular those in which water-soluble matrix coatings are used, produce a particularly good grain in accordance with the invention. The invention allows the preparation of granules which release at least 80% of the pesticide contained within 24 hours. The granules pi? favorites of the invention, which particularly include those with moisturizable matrix coatings, are readily capable of releasing at least 50% of the pesticide contained within 3 hours and 80% within 6 hours.

The present invention? particularly suitable for biological substances that are used as pesticides, for example bacteria, viruses and fungi, bacterial insecticides, in particular of the Bacillus type such as Bacillus thuringiensis (Berliner), and Bacillus sphaericus, represent a wide class of pesticides of particular interest to be used in the invention. Usual commercial products that employ Bacillus thuringiensis are represented by va-27- Ing. Barzan? & Zanardo riet? Kurstaici and Israelensis. The invention has the most interest? immediate for use with said variety? of Israelensis (B.t.i.) which currently? the pestici ^ da biological of choice for fighting mosquitoes, flies and related larvae in an aquatic environment.

The invention therefore also provides a process for combating mosquito larvae (culicidae) and similar harmful organisms in an aquatic environment which consists in applying a quantity to said place. insecticidal effective of a granular form of the invention which includes a biological mosquito larvicide.

The quantity to apply depend? by several factors such as the mode? of application, the development phase of the larvae, the habitat and the power of the granules.

For applications in the air, quantities will be needed. pi? larger than for application in the ground. When first to third stage larvae prevail in the insect population, lower application dosages will be required than if late third to early fourth stage larvae prevail in the insect population.

The power of the granules will depend? from the quantity? -28- Ing. B? Rzan? & Zanardo and the power of the biological insecticide introduced into the granules; it can? be determined by bioassay and for example can? be expressed in units? of Aedes Aegypti (AAU) per mg of formulated product (a bioassay method accepted by the US Environmental Protection Agency). The quantity to be applied accordingly will also depend on the power respectively of AAU / mg of the granules. In general, however, satisfactory results will be obtained with granules of the invention when they are applied in a dosage of between 2 and 7 kg / hectare. for example between

2 and 3 kg / hectare in river water, stagnant or still pools, ditches, inlets, in dosages between 3 and 5 kg / hectare in lagoons, tidal waters, salt marshes, and in dosages of 5 to 7 kg / hectare in polluted water with sewer. Suitable granules have for example a power of between 200 and 600 AAU / mg.

Granules having a power between 200 and

300 AAU / mg for example of 260 AAU / mg allow a perfect distribution of the active ingredient. Granules having a potency between 300 and 600 AAU / mg, for example a potency of 520 AAU / rng therefore will not necessarily allow a decrease in the application dosage, although with such granules a better persistence can be achieved.

-29- Ing. Barzan? & Zanardo While the invention? been described referring to applications in aquatic environments, sar? It is evident that it can be easily applied in non-aquatic uses of pesticides where granular applications are desired.

It should be noted that not? Is it necessary for the matrix that attaches the pesticide to the wax core to encapsulate the pesticide unless it is normally required to maintain its stability? in one way or another as a biological pesticide requires eg. evenings cos? protected. However, by employing matrix coating compositions in which the agent? intimately mixed, it will have? an essential encapsulation of the pesticide within the final granule in a system matrix attached to the wax core, particularly when the pesticide? fixed in conventional moisturizable powder form on the particle wax core. In the event that the wettable powder incorporating the agent is a water dispersible matrix, this is fixed to the wax core in a thinner coating matrix. or less underlying than preferably? soluble in water. Examples and Related Information

In the Examples that follow the mortality tests? were carried out by introducing them into basins

-30- Ing. Barzan? & Zanardo flat plastic plates having dimensions of

12.5 x 27.5 x 32.5 cm 8 liters of dechlorinated tap water so as to have a height of 10 cm and

2

a surface area of 0.093 m. For each test, 25 Aedes aegypt larvae (second or fourth stage) were introduced into the basin. In each basin, yes? also added brewer's yeast, in the quantity? of 25 mg per liter of water to provide feed for the larvae. The test is then carried out by distributing on the surface of the water a quantity? predetermined (dosage) of the granules, to be examined and determining the mortality? larvae as a percentage of all larvae initially present within 18 to 24-hours after the addition of the granules.

In the Examples, parts and percentages are in p? So and temperatures are in? C unless otherwise indicated.

EXAMPLE 1. ;

Into a coating mixer sa they introduce 95 parts of a paraffin wax in granules Sun Wax Antichek (Sun Petroleum Products Company, VJayne, Pennsylvania). The mixer is rotated and 20 parts of a paste-like composition prepared by mixing with

-31- Ing. Barzan? & zanardo bottoms 15 parts of water with 5 parts of a technical powder form of Bacillus thuringiensis

israelensis (B.t.i.) that? at least partially humidifiable and has a power of 2300 AAU / mg. The powder of 3.t.i. is prepared in a conventional way for the preparation of a powder B.t. technique by evaporating under vacuum the content of the fermentation vat (initially having a content in solid products of about 6% in an aqueous medium) up to a content in solid products of about 14-18% of which solid products about 40 -60%? consisting of protein material and 1-10%? consisting of starch at a temperature of 40? and under a void? of 625-575 mrnHg (Torr) (25-30 in / Hg) and spray drying the obtained mixture. The inlet temperature of the spray dryer? 177? or the temperature at the outlet? 66 ?. The mixing is continued after the addition of the 3, t.i. for about 3 minutes in order to apply the B._t.i paste evenly. on the wax. As you continue to mix, air heated to about 52 ° C is introduced. for a period of time of about 30 minutes and the freely flowing granular mass obtained is recovered. The granules are stored for 4 weeks at 409 and are then evaluated in the mortality test. in which the par-32- Ing. Bar z an? & zanardo ticelle float and give a mortality? 100% against fourth stage larvae 24 hours after application at a dosage of 3.6 kg / hectare (3 pounds per acre).

EXAMPLE 2

A humidable powder of B.t.i. prepared as described in Example 1 in an amount? of 5 parts is mixed with 10 parts of molten polyethylene glycol obtained under the name Polyglycol? 4000 ~ from the Dow Chemical Company. The mixing is continued for about 2 minutes at a temperature of 40 ?. The mixture obtained while? still in the molten state it is introduced into an operating coating mixer which contains 85 parts of Sun VJax Antichek paraffin wax in granules and the mixing is continued for about 3 minutes. The obtained granules are then?

stored at 40? for 2 weeks and then are evaluated in the mortality test? in which s? observes a mortality? 100% against the fourth stage of the larvae 24 hours after application in a dosage of 3.36 kg / hectare.

EXAMPLE 3

the

22.7 kg (50 lbs) of Sun - Wax Antichek granule paraffin wax is loaded into a Stockes tablet / coating machine. The rotor is spun and then slowly add to the -33- Ing, Barzan? SeZanardo spinning wax particles 550 ml of an aqueous solution of a colloidal protein. The colloidal protein solution is prepared by mixing 198 g of a partially hydrolyzed animal protein obtained under the name Colloid No. 1-V by Swift Adhesives & Coatings with water in quantity? sufficient heated to a temperature of 60 ° C to form a solution having a solids content of 36% by weight. The addition of the cooled protein solution takes about 3 minutes and the mixing is continued after the addition for about 3-5 minutes in order to uniformly apply the protein solution on the wax granules. Then 3000 g of humidifying powder of B.t.i, prepared as indicated in Example 1, are slowly added onto the rotating protein-coated wax granules. after adding for about 5 minutes in order to distribute more? or less uniform the humidifiable powder of B.t.i. on the protein-coated wax particles. While further mixing is continued, the mass of particles obtained is treated for about 30-45 minutes with dry air heated to a temperature of 50 ° C. in order to reduce the moisture content? to-34- Ing. Barzan? & Zanardo below about 8%. Any lumps present in the mass obtained are dissolved by hand and the mass is then sieved in order to separate any remaining lumps. The product obtained? consisting of brownish granules without excess dust formation and? freely sliding and the individual particles float on the water. The final formulation? '87, 2% of wax, 12.0% of humidiable powder B.t.i, and 0.8% of colloidal protein and the formulation has a specific weight of 1.88 liters / kg. Said final granular mass has a potency of 520 AAU / 'mg and after a storage of 4 weeks at 40? produces a mortality rate of 100% on fourth stage larvae 24 hours after application in a dosage of 3.36 kg / ha in the mortality test. The addition of High Si silica (1.0% of product obtained) improves the possibility? conservation of the granules avoiding the agglomeration of the granules.

EXAMPLE 4 - In a belt mixer (Day Model 758) running at 280 rpm and containing 80 parts (about 45 kg) of No. 2 corn cob granules (1.5 - 3 miri)) are added portions 20 parts of paraffin wax (the same wax used in Example 1) which? was added in about 4-6 portions from contain-35- Ing. Barzan? & zanardo state

bulls whose content? / evenly distributed on the mass of corn cob granules.

Yup ? continued stirring for about 4 minutes after adding all of the melted wax and during this

time the melted wax yes? applied in a more? or less uniform on the single corn cob granules and? solidified to form a dried wax coating. A charge of 88 parts of the cores consisting of wax-coated corn cob granules? was introduced into a similar belt mixer

and ? thoroughly mixed while 4.5 parts of the colloidal protein solution used in Example 1 were uniformly distributed over it.

Yup ? continued stirring for about 5 minutes later

this addition in order to uniformly distribute the colloidal protein solution on the surface

of wax of the nuclei. Continuing to mix, 10 par-? ti of powder, humidifiable 5.t.i. prepared as described in Example 1 and then yes? continued stirring for another 3-5 minutes to ensure even application of the powder to the protein-coated wax cores. They then joined

100 parts of No. 2 corn granules (not coated with wax) and 0.4 parts of hydrophobic silica obtained below

-36- Ing. Barzan? & Zanardo forms Aerosil R972 and continues to mix for 5 minutes in order to obtain a uniform mixture. The addition of non-wax-coated corn grains promotes drying of the mass and serves as a diluent in the product. The resulting mass is sieved through a No. 6 (0.33 cm) mesh sieve to obtain a final granular product. These granules produce a mortality? 100%. of the fourth stage of larvae after 24 hours in the mortality test? when applied in a dose of. 2.24 kg per hectare and after storage for 3 weeks at 40? realize a mortality? against the fourth stage in the mortality test? 85% and 100% when applied respectively in dosages of 2.24 and 4.48 kg / hectare. When applied to water by top-down free fall application approximately 98% of the coated granules remain floating on the water surface 24 hours after application.

Claims (11)

R I V E.-N D I C A Z I O N I 1. A free-flowing, water-buoyant granular form of a pesticide in which the granules comprise a) a core of solid wax or a core coated with solid wax having a density? lower than that of water and what? inert in the con-37- Ing. Barzan? & Zanardo pesticide fronts e b) a pesticide attached to the wax core or to the wax-coated core by means of a matrix which? inert towards the pesticide and what? able to release the pesticide when it comes into contact with the water 2. A granular pesticide according to claim 1 wherein the wax? a paraffin wax having a melting point of at least 40 ° C. A granular pesticide according to claim 2 wherein the core material coated with wax? a granul? of corn cob. 4. A granular pesticide according to any one of claims 1 to 3 wherein the pesticide? a biological pesticide. 5. A granular pesticide according to claim 4 wherein the biological pesticide? an organic mosquito larvicide. 6. A granular pesticide according to claim 5 wherein the pesticide? Bacillus thuringiensis var, Israelensis. 7. A granular pesticide according to any one of claims 1 to 6 wherein the matrix material represents 0.5 to 5% by weight of the "core" and represents 5.0 to 25% by weight of the "core". of the material pe -38- Ing. Barzan? & zanardo sticida. 8. A procedure for combating mosquito larvae and similar harmful organisms in an aquatic environment which consists in applying a quantity to that place? insecticidal effective of a granular pesticide according to claim 5. 9. A process of claim 8 in which, the modality? of application? an application from above. 10. A process for preparing granules according to claims 1-8, which consists of i) applying to the core a liquid coating matrix composition possibly containing the pesticide e II) add the pesticide in solid form substantially after completion of phase i) in which phase II)? optional in case the coating matrix composition contains the pesticide. \ MANDATORS 5 (signature) s? irpar gN others) 7685 / CORN. / Vf 507697 PATENT 1 <? Series \ eW_e of 1979) J? Series Filing date Class Sub Unit? tecni Class Examiner 06 / 507.697 24 JUNE 1983 424 ca of grujpo 123 and TSUONG R. SHIEH, BAKER SFIELD, CA, w to w w x or M PS ** CONTINUATION DATA ********************** VERIFIED This? a continuation question in _ part of Question No. 06/427 * 604 dated 29? 9? 1982 * ** FOREIGN APPLICATIONS / ^ WITHDRAWAL *? ************* - ** VERIFIED Priority foreign country claimed Osi Ono Conditions fulfilled Art. 35 US Code 119 Osi Ono Verified and Recognized. . Initials of the examiner ??? DE- State or Claims Boards Claim Wrapping Fee? SITATE Country drawings tions filing of the pro-? > totals indep. receipt of curator CA 3! $ 430.00 63C? 6946 / B s GERALD D. SHARKIN No. M 3AND0Z INC., 59 RT. 10 PS EAST HANOVER, NJ 0793 6 M. "PESTICIDE GRANULES" 1 M EH SU Ministry of Commerce - Patent and Trademark Office PTO-436 L. (Revised October 1978) . here I'm ? to certify that here annexed? a faithful copy, of the registrations of the United States Patent and Trademark Office, of the application ie? pi? above, how? was originally filed. On behalf of the PATENT AND TRADEMARK COMMISSIONER (SEAL) Signed: A.L. JACKSON Certifying officer Date: August 31, 1983 Round date stamp: < SHORT OFFICE MAIL SERVICE AND TRADEMARKS date: 24 JUNE 1983 507697 and? or? e "PESTICIDE GRANULES" This question? a continuation-in-part, of application series No. 427 * 604 filed September 29, 1982. The present invention relates to granular forms of pesticides, for example biological pesticides, their preparation and their use. Biological substances by nature feed or attack elytra substances and therefore have been considered for many years as a means of combating harmful organisms especially those found in agriculture and the like. For example, bacteria that are thus toxic to insects have long been known, and commercial insecticides based on such bacteria have now been available for several years. Similarly viruses are useful against insects while fungi have found use in fighting unwanted plants, biological pesticides have the clear substantial advantage of being selective or highly specific for particular purposes and in general they are Tax Registration: 29 JUNE 1983 507697 1 101 300.00 CI 29 JUNE 1983 507697 1 103 130.00 CI they are environmentally safe. Then? they have had considerable interest and have attracted in recent years. Again, is their selective advantage typical of biological pesticides? also one of their drawbacks, limiting the market for the effort spent on development and manufacturing. Most of the disadvantages of the organic pesticide are attributed to their origin as living natural substances, generally quiet in their native environment but otherwise more? or less sensitive for a wide variety? of factors, such as heat, light, chemicals and other influences encountered when they exist outside their native environment. So, stability, the capacity? to survive effectively outside the native environment? a fundamental thing and one or of the pi? pre-requisite components of the bacterial pesticide, stability? to heat, stability in the light and stability conservation are usually separate problems that need to be considered and solved. The manufacture of a bacterial pesticide? was therefore, very much, a matter of obtaining stability? necessary by simultaneously realizing all the other properties? and features required for a commercial product. The result ? been, as indicated, costs more? high, less flexibility? in product forms compared to synthetic chemicals for similar use. For example, Bacillus Thuringiensis, the most common bacterial insecticide? commercially known became available in humidifiable powder form, but separate development of highly specific technology was necessary to obtain an emulsifiable concentrate, see U.S. Pat. 3,271,243. A granular form of a bilogical insecticide, in barticular insecticidal bacterium useful in aquatic applications? it was also interesting, but? was generally difficult to develop and? typically accompanied by stability? and other problems. A previous proposal in US patent 3,420,933 focused on the bacterial insecticide Bacillus Sphaericus, a bacterium that is particularly toxic to mosquito larvae and the use of granules which at least 20% are non-floating in water and are prepared from. conventional granule materials that form the core such as vermiculite and clays. The recent discovery and the availability? of Bacillus Thuringiensis var. Israelensis (later called 'B.t.i. ") also particularly potent against insects such as mosquitoes and flies, have essentially increased interest in a granular form for a bacterial insecticide, particularly for aquatic applications. Working with that incentive, numerous have met Failures in providing a granular form for a biological material until the realization of the present invention.For example, granules prepared with cores of vermiculite, oil-coated clay and other traditional or branched materials exhibited a drastic loss of potency within about 1 week after preparation and therefore had inadequate storage stability Most, if not all test products prepared in a traditional manner were being dispensed with difficulty by conventional or other sprayers, and encountered similar problems. The direction of fall of the granules more? light to the aerial application was also difficult to control and unacceptable, moreover, in contrast to? suggestions by U.S. Pat * etto * 3,420,933, yes? found that a mosquito bacterium? pi? effective when dispersed and floating on the surface of the water where the larvae are present. Soaking granules such as those with clay cores have been found to be of low efficacy. The main object of the present invention is therefore in providing a new and improved form of dispensing a pesticide, particularly a biological pesticide. A further object of the invention is to provide a stable granular form of a biological insecticide which? able to float and release its toxic agent on the surface of the water. The objects will become apparent from the following description of the invention. In accordance with a preferred embodiment of the present invention yes? found that a new improved granular form for a diological pesticide comprises a granular mass in which the individual particles are characterized by having a biological pesticide attached to the surface of a normally solid core of wax particles in a matrix of the system. non-harmful to biological material and what? normally sufficiently dry so that the mass of the particles flows freely ? ? you but the matrix ones? sufficiently humidified in water so that a quantity? effective of the point of view, pesticide of the pesticide is released when the granule is placed in contact with water? The use of wax as a central part of the granule not only allows the production of a buoyant granule but yes? found below in the invention to create the basis for a biological pesticide release system having a stable power and a number of other properties? do you want for a granular pesticide in particular for a granular pesticide useful in water applications? Can the granules also be easily produced by various coating processes followed by drying necessary to obtain a free flowing mass? The invention can be carried out in various forms or re? ections that establish certain terms and appropriate definitions? In general, the biological pesticide in the final product? contained within a matrix which in turn is fixed to the underlying wax particle core. So, in the forms of realizations more? simple, a matrix material pi? or less uniform or homogeneous containing the biological pesticide pu? be directly coated on the surface of the wax core. In other preferred embodiments, the biological pesticide can? be already? encapsulated in an inert material, suitably, or protective matrix, and the resulting fine particles, or powder, coated on and / or absorbed into a first coating of a matrix material. coating the core with wax and agent so as to bind the particles containing biological pesticide to the core. The matrix that fixes biological matter to the nucleus can? be directly or indirectly attached to the core. So, can you? realizes? re indirect fixing before coating or fixing to the wax core one or more? separate layers of a suitable inert coating, not performing a matrix function and thus fixing the matrix on the exposed outer surface of the thus coated particle. The precise mechanism by which the biological pesticide is released into the water can? also vary according to the particular embodiment of the invention and the type of materials used. In the realizations more? simple in which the biological matter is kept in a uniform or homogeneous matrix, the water must act on the matrix to release the biological matter contained and this can? be made using a matrix material? that? disperse or soluble in water. On the other hand, when particles containing encapsulated biological matter are coated and / or absorbed into a matrix, the result may be. \ be a non-homogeneous system which, in a sense, ii>? plica a plurality? of matrices within a matrix e the action of water on different matrices can? be different and the total release mechanisms p? - vary accordingly. Thus, the encapsulated biological particles may, for example, be dispersible or soluble in water and the coating of matrix in which it is held and fixed pu? be water dispersible, water soluble or water insoluble, for example the combination of encapsulated biological particles dispersible with water on and / or in a matrix coating which? substantially insoluble in water can? be used in such a way as to lead to the release of the toxic agent by humidifying the portion of particles dispersed in water at the surface of the granule ^ - -1-_ and the resulting shrinkage of the same in the water. Such action -in correspondence of the surface in general will expose? other particles or elitre uraid portions? icabili originally inside the granule to the action of humidification and release so that further quantities can be released? of the biological pesticide in the water, and the granules having heavy and / or underlying biological content more? efficiently used. On the other hand, in other preferred embodiments, the plurality? of encapsulated biological particles? essentially water-dispersible in nature and fixed on and / or in an essentially water-soluble matrix coating so that the entire matrix system is freed from the wax core by the action of water with the individual encapsulated particles essentially dispersing from the place of application, in any case, since? different dispositions and sensitivities? of humidification as dispersibility? and solubility? the expressions "wettable in water? and the like used herein to refer generically such release mechanisms in water can be used and are applicable to the whole system or to any part of the biological pesticide-containing matrix system attached to the core of wax granules, as appropriate , to release the biological toxic agent in the presence of water. It will also be apparent that the term "matrix" is used in a broad sense to include systems in which there is substantially complete incorporation into the host matrix and systems. in which a substance? .incorporated only partially and therefore? simply held by the host matrix and also systems in which a substance is fixed by a combination of these two mechanisms. The terms "encapsulated" "encapsulated matrix" and the like are used herein with reference to the biological pesticide to indicate a substantially complete incorporation of either the biologically active substance into the host or matrix material, it will be understood? for? that biologically active pesticides can be encapsulated by processes basically involving mixing of the pesticide with the matrix material, so that a smaller portion of the quantity? total amount of biologically active substance can be and, usually,? present or exposed to the surface of the matrix, even if the pesticide? considered encapsulated as the expression used herein, furthermore, whether or not, as in certain preferred embodiments, vias are encapsulated or matrix particles within a matrix or other essentially non-homogeneous matrix systems, the biological matter is contained or protected within the grain in the sense of being encapsulated within its most immediate or adjacent matrix. Hence the expression "system matrix" or matrix system? is generally used> -ta without distinction to encompass all such matrices that surround and act to fix the organism biological directly and / or indirectly to the wax core, unless it is distinguished in this text as will often be the case * by distinction, the expressions "coating matrix" matrix coating "and the like will be used to indicate a stronger matrix. ? or less underlying, distinct in terms of representation of a single coating application or formed by two or more? applications of the same coating to be underlying, enclosing, incorporating and / or similar? the only or main component of the matrix system in terms of action to fix a biological pesticide directly or indirectly to the wax core, even if, as in certain realizations more? prefer, the coating matrix by weight can? be a small fraction of the system matrix. The coating matrix can? be made up of one or more? materials, not necessarily mutually soluble or homogeneous, what composition of coating matrix? generally uniform but, by definition, it will not include? materials separately applied or coated, for example the particles pi? or less separated of the biological pesticide in an ineapsu1ament matrix? o when not applied with the coating matrix material or composition? therefore, as contemplated here, the matrix of the system? the essential and total matrix which has a total encapsulation effect and which will constitute? or will it be? consisting of an essentially equal coating matrix. A mapia range of wax has a density? lower than water and can? be used in accordance with the invention to prepare pesticide granules similarly having a density less than water, it being noted that the additional materials needed to form the preferred granules of the invention are even more so. light water. If, for any reason, it might be desired to use a more coating or additive material? heavy of water, a wax can? usually be chosen, which will have? a density? sufficiently low so that the resulting granule will be? nevertheless floating, it being noted that the wax core will replace? generally the main burden of a large one I practice; On the other hand, the resulting wax and granules provided by the invention generally have sufficient weight to penetrate the stubble and other similar productions encountered in an aquatic environment and resist deflection by water streams when applied from the air. all there? ? the capacity? desired in a granule for the control of mosquitoes and the like? The waxes to be used in the invention are normally solid materials in order to retain integrity. of the granules and avoid any unwanted melting of the granules during storage. In practice it is desired that the wax have a melting point of at least 30 ° C and preferably at least 40 ° C. Preferred waxes have a melting point between 45? C and 85? C, plus? preferably between 50 ° C and 75 ° C. The wax used must be inert in the sense of not being harmful to the biological pathogen to be incorporated into the granule. Many waxes have a chemical composition that? inert to various biological substances and 1 * inertia pu? be ascertained routinely through simple tests and error if necessary. However, in general the paraffin substances are inert to biological pesticides and the paraffin waxes are preferred as the material for the core portion of the granules of the invention. Paraffin waxes that have melting points in the pi? prefer ?? to are readily available, commercially in a suitable finely divided form (egranule? 1), for example, Sun Wax 4412 (PP 60? C) and Sun wax Anticheck (PF 67? C) f both available from the Sun Petroleum Products Company, Wayne, Pennsylvania. The particle wax core can be essentially constituted by the solid material consisting of wax or can? be a material comprising your internal base surrounded by the solid material of the wax to which it will come? fixed the matrix, and in the latter case it only requires that the wax substantially completely coated the base and that this coating has a sufficient thickness so that the base does not adversely affect the insecticide and that the water does not penetrate through the wax coating so as to let s? that the total granule does not submerge at least before its supported pesticide is substantially released on the surface of the water. Can you? employ a large variety? of finely divided materials or in particles as base material to be coated with wax so as to form the core of the wax particles. Such raa> -terials per se? preferably have a density? lower than that of water and may be mineral in nature such as v * ermiculite or organic in nature such as finely divided corn cobs, for example the material known as corn cob granules. In any fall, any nucleod. There was what? a combination of a base material and the wax coating on it, desirably has a high density. lower than water, since? Not ? It is desirable to depend on the matrix of the system and its contained biological pesticide to provide a granular product which? floating for the desired time to leave the biological pesticide in the water? The quantity of base material compared to the wax in such cores of wax pu? vary quite widely and the base material can? easily make up the bulk of the core on a weight or volume basis, for example, a basic material consisting of a grain of corn cob can? be used to prepare a core that contains 75-90% corn cob and 10-25% wax on a weight basis? The main advantage of using a base material? a reduction, in the cost of the core in particular since? numerous basic materials readily available habit less expensive than waxes. Thus, it is generally preferred that such cores contain 10% to 60% of the wax and 40% to 90% of base material by weight, plus. preferably 15% to 25% by weight of wax and 65% to 85% of base material subject to the requirement that the wax substantially coats the base material. the particle diameter of the particulate base material to form such wax-coated base particle cores preferably? between 0.3 and 3.0 mm (ram), pi? preferably between 1 and 2 mm. The resulting particulate wax cores preferably have a particle size between 1 and 4 millimeters; pi? preferably 2 and 3.5 mm. Cores consisting mainly of the particle base material surrounded by normally solid wax material can be prepared by a conventional process for applying a normally solid liquefied material to a particle base, generally it is preferred to first liquefy the wax by heating well. below its melting point, for example at least 50 ° C above its melting point, preferably at least 75eC up to 125 ° C above its melting point and then distribute the melted wax over the mass of the melting material. base in particles, for example by spraying, also carrying out a mixing so as to assure a complete and better coating. or less uniform than the wax on the base material, intensive mixing is desirable and such mixing is continued until the temperature of the wax? well below its melting point, for example? practically at room temperature in order to avoid unwanted agglomeration of the individual wax granules or cores obtained. adopt a heating of the mixture by means of an external device or by introducing a heated inert gas directly into the mass to ensure a uniform distribution of the wax before making s? that the mass cools to form the desired nuclei. So a core? constituted by wax, the diameter of the finely divided wax particles for use as starting material in the preparation of the granules of the invention, comprised between 0.5 and 3.0 mm, plus? preferably between 1 and 2 mm. The system matrix serves two or more? functions, according to the particular embodiment of the invention to be employed. In general, the matrix system can? negatively affect the stability? of the organic pesticide and then? made up of material that? inert in the sense of being non-harmful to the biological toxic agent? while it encloses and thereby protects the organic pesticide? The coating matrix also serves to attach the biologically active pesticide to the wax core. Also when is the biologically active substance? substantially fully incorporated into the coating or otherwise non-releasable in water, the matrix system must also be fully or partially humidifiable in water in order to be able to release the active substance as a multiplicity. of fine particles of the biologically active substance or of the active encapsulated substance? The particular material -!? :? to be used as the matrix material of the system depend? from the particular biological pesticide to be developed and from different choice factors? While ? available a? wide choice of matrix materials and carrier substances for coating with pesticides other than biological pesticides, the choice of such materials? pi? critical when an organic pesticide is used as the active ingredient. Such materials can be carbohydrates, protein materials of animal or vegetable origin and materials selected from a synthetic source. Carbohydrates which represent the most important materials? suitable are processed from natural sources and include starches such as corn starch and various cellulosic materials such as ethyl cellulose. Protein materials include but are not limited to casein, carrageenan, partially hydrolyzed vegetable seed proteins such as soy protein and partially hydrolyzed animal proteins. Representative synthetic materials include normally solid polyethylene glycols and polyvinyl alcohol resins. The particular material suitable as a matrix and which makes the medium more? inert and more? stablepar a particular biological pesticide usually will be? known for biological pesticides and when not? known, as in the case of new materials intended for biological pesticides, the suitable material for matrix can? be determined by routine experimentation. In general, however, protein materials provide a stable medium for biological pesticides such as bacteria, viruses and fungi that can be used in general. as indicated, at least the coating matrix of the matrix system must have the function of securing the biological pesticide to the particulate wax core, as well as providing an inert environment from which the biological pesticide is preferably released into water. , a wax material can? to be intrinsically judged a poor and unlikely candidate for the nucleus of a granule since? its surface offers little opportunity? or no opportunity? by absorption which? the common or primary mechanism by which pesticides are fixed in many granular pesticides. Therefore, in particular in the forms of realization pi? practices in which the coating matrix? fixed directly to the wax "core" the bonding mechanism is essentially a surface bonding mechanism and generally in a physical sense, rather than a chemical reaction. This physiological surface bonding is generally achieved by the adhesive properties of materials used in the coating matrix. and such materials are further selected in a corresponding manner. The term "adhesive" and the like as used herein encompasses the various properties by which adhesives can bond which include properties and capabilities such as adhesiveness, penetration and the like. and also the advantages of cohesion as achieved in particular by film-forming adhesives. When is a ripple matrix material used? coating that produces coatings? disperse them in water or other coatings in a characteristic and essential non-film-forming way, the property? of adhesiveness? becomes a factor more? also positive for the fact that the oily nature of the wax itself does not provide an ideal bonding surface. of these coatings leaving an appropriate moisture content? residual and carrying out the conservation in conditions that do not rapidly decrease the humidity? residual * When using less tacky adhesives in dispersible coating matrices can? be therefore? preferred to avoid conservation as much as the good stability? the preservation of the product can allow and / or use granular applicators that do not exert a strong mechanical action on the granules. ? involved in the realization more? Preferred, since among other things, the contributed cohesion benefit of the resulting film, even if substantially disrupted by the non-homogeneous particles contained, is believed to provide a particularly effective mechanism for bonding the coating matrix directly or indirectly to the core in wax particles. The matrix material of the system can? be chosen from a separate source or even can? be present in the organically manufactured product, as a result of the raw materials used in the manufacture, or can it? be chosen from a separate source or can? have both of these origins. for example, bacteria and fungi useful as pesticides are usually produced commercially by fermentation in a nutrient medium which includes water, carbohydrates, proteins and several compatible inorganic salts, the product obtained on a dry basis usually contains a higher proportion typically at least 80 # by weight of carbohydrate and protein residues which are at least partially dispersible in water and such products may suitably be used as such as material for the system matrix or as a component thereof in the preparation of the granules of the present invention. Fermentation products in which the protein residue alone? at least 50% by weight of the product on a dry basis is usual and preferred in the case of products? of fermentation to be used alone or mixed with imo or pi? of other matrix materials to form a coating composition. Such fermentation filler products can be employed as a coating after making any adjustments required to bring the water content to the desired level, for example by evaporation under vacuum. Alternatively, drying the product of a fermentation batch, e.g. spray drying according to known processes, produces a dry particle mass in which the particles constitute an encapsulation of the biological pesticide in a matrix consisting of the residue of the nutrient medium of fermentation. This particle mass can? be mixed with water to form a sticky paste-like composition that can be be applied on the "nucleus" in order to form a large? I in which the biological active material? fixed in a coating matrix consisting of the residue of the nutrient medium. On the other hand, and according to the most embodiments? preferred of the invention, a dry powder, obtained for example by spray drying the fermentation charge,? a ? * 1 a particularly suitable shape to be applied to the " core &quot; particles while still wetted by a first coating of matrix coating materials. The application of such a preferred embodiment and biological pesticides not normally produced by fermentation, for example pesticides consisting of viruses, can be used. be realized, yes? described now for example, the production of fine particles comprising a pesticide consisting of viruses encapsulated in a water-dispersible protein matrix, in the British Patent 1557,668 issued on August 8, 1980, by Rogoff and Shieh. The process for preparing the granules of the invention will vary. according to the particular realization desired to be produced, but it will be? evident from the description of the invention. In general, methods of applying liquid compositions to particles which are uncoated or have a dried prior coating are known, as are also known methods of applying dry particles to wetting particles by means of a prior coating. When using a liquid coating the solvent or dispersant distribution vehicle ? ? preferably? water, organic solvents can be used, but they must usually be chosen carefully since? many can negatively affect the particular biological pesticide, pi? In the preferred embodiments of the invention, fine dry particles which contain the biological pesticide encapsulated in an encapsulation matrix, such as a so-called "so". said powdered form of bacterial insecticide such as Bacillus thuringiensis Israelensis are applied on and at least partially incorporated into an undried matrix coating which? been previously applied to the wax particle. In such a process the wax "core" material in the form of desired particles or granules is agitated or mixed together for example by tumbling in a suitable mixer and the coating matrix material is then sprayed (suitably in the form of a solution). aqueous) or otherwise applied to the mass of the "core" followed by a continuous mixture sufficient to apply the coating matrix substantially over the entire surface of the individual wax particles. This coating is preferably made more or less at room temperature or otherwise below the melting point of the wax. The coating matrix material? suitably applied in the form of an aqueous solution which readily coats the wax and which has sufficient water to make s? that the biological pesticide in finely divided encapsulated form can be absorbed to a substantial degree into the coating. On the other hand, concentration? sufficiently high to ensure that excessive drying can be avoided in a desirable way. In many cases, concentrations ranging from 20 to 50%, preferably 30% to 40%, on a weight / volume ratio, are suitable. The quantity of material of the coating matrix on a dry basis can? vary depending on a number of factors comprising the mate-. rial used, the thickness of the coating desired, the capacity? coating and the like. In general, the quantity? of coating? very small in relation to the weight of the wax core material and may even be relatively less in comparison to the amount of a finely divided encapsulated biological pesticide to be added later. for example, the coating matrix in the most embodiments? do you prefer pu? represent a concentration of between 0.5 and 5.0% by weight of the wax "core" material used, more typically 0.7 to 2.0% by weight of the core * Will the mixing time to apply the coating matrix solution to the "core" vary? but can? be a relatively short time between 1 minute and 20 minutes, plus? specifically between 3 minutes and 10 minutes. When such a coating? complete, the mixing or another type of tumbling of the mass into particles of liquid coated wax is continued in order to avoid an undesired agglomeration and the addition of the biogical pesticide in finely divided encapsulated form can? be started immediately after the coating? complete or with a certain delay depending on the drying characteristics? . ment of the matrix coating and of the quantity? desired absorption or the degree of adsorption in the matrix coating. Typically organic pesticide addition just starts? complete coating of the coating matrix, Is the addition of the biological pesticide in finely divided encapsulated form accomplished by controlled introduction? and / or intermittent or by distribution in the tumbling mass of the coated core particles in order to obtain a better application. ? less uniform than encapsulated biological pesticide particles - on the coated wax particles. The time of addition of the pesticide material can? be of the order of 1 minute up to 20 minutes, plus? in particular of 2 minutes up to 10 minutes. The addition of the biological pesticide is preferably carried out at room temperature and preferably below the melting point of the wax core material, as indicated above. of the matrix material on which or in which the biological pesticide is applied pu? be relatively minor in comparison to the quantity? of encapsulated biological pesticide material. for example, the coating matrix material in the preferred embodiments can represent, from 3.0 up to 20%, pi? in particular from 5.0 to 12% by weight of said encapsulated biological pesticide to be fixed to the wax core on and / or in the coating matrix material. Hence, the weight of the encapsulated biological pesticide can? be about 5 to 35 times, more? typically 8 to 20 times, the dry weight of the material, of but-. coating trice. The quantity particular of encapsulated biological pesticide material to be used pu? therefore vary? Very. While checked to its upper limit by the capacity? of the liquid matrix coating solution to absorb pesticidal, biological encapsulated material, the amount of said encapsulated material can be determined in general by preference factors and the final desired characteristics of the product such as power after consideration of the concentration. On the other hand, the limit of the quantity? from encapsulated material pu? be influenced by the time required to dry the product and the need? to avoid unwanted agglomeration of the particles in the fluid mass of particles. In any case, when? completes the addition of the pesticide material, the particle mass obtained is maintained in a state of agitation by mixing or tumbling and is subjected to drying in order to obtain a freely flowing particulate product. Such drying can? be suitably carried out with a heated inert gas, such as heated air which is introduced into the mass subjected to stirring, since biological pesticides even in the protected form are negatively affected by high temperatures, usually? it is necessary to control the temperature of the drying conditions or of the gas heated to moderate levels * In general you can? satisfactorily adopt an air temperature between 100? F ~ 160? F, plus? air temperatures between 110? F and 140? F can be used appropriately. In general not? it is necessary to completely dry the mass and you can? obtain a satisfactory product with a decrease in the moisture content? maximum cil up to no more? of 10%, preferably up to no more? 8%. The retention of a certain humidity? can be desirable, as noted above. Will the drying time vary? depending on particular cases and can? be between 15 minutes and 3 hours, but satisfactory drying can? typically be done from 25 minutes to 1 hour. On the other hand, drying can? be facilitated or can? essentially be carried out at a decreased temperature, for example at about room temperature, by adding a substance that absorbs moisture? in quantity? substantial, for example 50% to 150% by weight of the mass of granular product. Such material can? therefore also serve as a diluent for the product. A suitable material for this purpose? a grain of corn cob (not coated with wax) even if this material is not? suitable as core material when not? coated with wax. Any agglomerates formed during drying can be separated, for example by hand, and the final product is usually screened according to the specifications of the desired product. The diameter of the particles of the product can? vary quite widely, for example from 0.5 to 5 mm. When using typical commercially available beaded wax forms, the particle meter in the final product can be used. typically vary between 0.5 and 4 mm, pi? preferably between 1 mm and 2 mm. When using wax-coated base cores, the end products can typically have a diameter of between 1 mm and 5 mm, more so. typical between 2 mm and 4 mm. The product obtained can? then be mixed and coated with a small amount, for example from 0.1 to 4.0? on the weight of the granule, preferably between 0.5 and 2%, of an anti-agglomeration agent such as calcium stearate, various silicas such as High sii, Aerosil and the like, if desired. In the preferred embodiment and other embodiments wherein fine particles of an encapsulated biological pesticide are applied on wax which? wetted with a matrix coating material 1 * exact nature of the final product varier? depending on several factors such as the quantity? of encapsulated material applied to the coating matrix material. The use of quantity? only moderates of a finely divided encapsulated biological pesticide can? lead to an oi absorption as a result? or less substantially complete of the biological material in the liquid matrix coating and a pi? or less substantially complete of the biological pesticide-containing particles in the dried matrix coating. On the other hand, the application of quantity? pi? large of biological pesticide that reach the capacity? of absorption of the liquid matrix coating dar? as a result that a significant portion of the particles containing the biological pesticide are less than fully incorporated and only variable portions of some particles are held by the coating matrix and even in some cases are more adherent. between each other and the coating matrix. ? i In this case, the biological particles held. pi? read at the complete drying of the product, they may tend to fly away, but this result can? be tolerated and controlled and? minor disadvantage in relation to all the disadvantages offered by the product and the opportunity? to deliver a high or maximum dosage with highly charged particles, which will also release the total biological pesticide contained in ap? different in water. When using a coating matrix material in the form of a film in the most embodiments? as described above, some finely divided encapsulated particles that contain the biological pesticide will penetrate and be absorbed into the liquid matrix coating but the resulting dried coating, while non-homogeneous, will have? nevertheless, a lattice, cavity? honeycomb and / or other similar effect, wherein the matrix coating material remains substantially continuously interconnected to provide a cohesion gain. While not readily subject to description in further detail, these systems, especially employing matrix coating? water-soluble, they produce a particularly good granule in accordance with the invention. In general, the entity? of liberation and other characteristics ? ? * characteristics of the final product will also be determined in accordance with the type and quantity of material used, such as system matrix or matrix coating, as well as the? quantity of organic pesticide contained in it? Granules prepared in accordance with the invention will release a pesticide-effective amount of the biological pesticide contained within a reasonable time, e.g., up to 24 hours, and can generally be prepared in various embodiments to release at least 80% of the biological pesticide within that time period, for? Delayed or very slow release in a biological granule is usually not considered desirable once in contact with water and the granules of the invention, which particularly include those with a humidifiable matrix coating, are easily capable of releasing at least 50% of the pesticide content within 3 hours and 80% within 6 hours. The present invention can? be generally applied to biological substances that are used as pesticides, for example bacteria, viruses and fungi all of which classes are represented by various substances already? try in the field and which may be suitable for use in accordance with the invention and its description, here, bacterial insecticides, particularly of the Bacillus type, are currently analyzed more widely and represent a broad class of particular interest. How are bacterial insecticides, in particular of the Bacillus type, more? those identified as Bacillus thuringiensis (Berliner) are widely known, although other bacilli such as Bacillus dpaericus, will be of immediate interest to be used in the invention for their efficacy against mosquito larvae requiring aquatic application, see among others, U.S. Pat. 3271243 and the cited literature, usual commercial products that employ Bacillus thuringiensis are represented by the varieties? Kurstaki and Israelensis, The invention has the most interest. immediate for use with said variety? of Israelensis (B.t.i.) which currently? the biological pesticide of choice for combating mosquitoes, flies and related larvae in an aquatic environment, see U.S. Patent 4.166.113.1 While the invention? has been described referring to applications in aquatic environments and more? specifically to B.t.i. sar? evident that it can? be easily applied in non-aquatic uses of biological pesticides where granular applications are desired or sought to achieve, for example . . ? ? insects in depth? within the folds of the crop like corn. Furthermore, the invention has generally demonstrated certain advantages of a wax core for a pesticide granule prepared or readily adapted in accordance with the invention, in particular for, but not limited to aquatic applications, e.g. insecticides useful against mosquito larvae, where running granules are readily immersed and / or have disadvantages overcome by the invention. Thus, we contemplate the fact that the invention in its most important aspects? vast applies to all substances or agents of a chemical nature useful for combating harmful organisms including synthetic chemicals and natural non-biological substances as well as biological microorganisms. In applying the invention, it should be noted that no? Is it necessary for the matrix that attaches the pesticide to the wax core to encapsulate the pesticide unless it is normally required to maintain its stability? in one way or another as a biological pesticide requires to be so? protected. However in a practical sense, the invention as described and applied to biological substances will be herein? preferably made with all chemical agents to fight harmful organisms, for example insects, plants, fungi, etc. for example by employing matrix coating compositions in which Vagente? intimately mixed, for which one will have? an essential encapsulation within the final granule in a system matrix attached to the wax core, and in particular, coating traditional humidifiable powder forms of such agents on the wax particle core, while moist from a previous coating, of a composition coating matrix coating in accordance with all general and specific and preferred methods described herein, for biological substances whereby a granular product comprising the wettable powder incorporating the agent in a water dispersible matrix,? fixed to the wax core in a coating matrix pi? or less underlying than preferably? soluble in water. Result? It is evident, however, that a wide choice of matrix materials and coating vehicles will be available. available with agents other than biological pesticides, since? such other agents, usually, do not present stability problems? characteristic of biological pesticides, although the requirement of using matrix materials and processes that are not harmful to the agent, remains. Examples and Related Information In the Examples that follow the mortality tests? were made by introducing into flat plastic trays having dimensions of 5 x 11 x 13 'inches, - ????? ? ???? 8 liters of dechlorinated tap water in order to have a height of 10 cm and square. 1 foot surface area / 25 Aedes aegypt larvae (second or fourth stage) were introduced into the basin for each test. In each basin, yes? also added brewer's yeast in the quantity? of 25 mg per liter of water in order to provide feed for the larvae. The test is then carried out by distributing on the surface of the water a quantity? predetermined (dosage) of the granules to be examined and determining the mortality? larvae as a percentage of all larvae initially present within 18 to 24 hours after adding the granules. In the Examples parts and percentages are by weight and temperatures are in? C unless otherwise indicated. EXAMPLE 1 95 parts of a Sun Wax Antichelc granulated paraffin wax (Sun Petroleum Products Company, V / ayne, Pennsylvania) are introduced into a coating mixer. The mixer is turned and 20 parts of a paste-like composition prepared by thoroughly mixing 1.5 parts of water with 5 parts of a form are added to the tumbling mass. ? in powder technique of Bacillus thuringiensis ? israelensis (B.t.i.) that? at least partially humidifiable and has a power of 2300 AAU / mg. The powder of B.t.i. it is prepared in a conventional way for the preparation of a powder 3.t. technique by evaporating under vacuum the content of the fermentation vat (initially having a content of solid products of about 6% in an aqueous medium) up to a content of solid products of about 14-18% of which about 40-60 solid products %? consisting of protein material and? -10%? consisting of starch at a temperature of 40? and under a vacuum of . .? THE.. . 25-30 in / Hg and spray drying the obtained mixture. The inlet temperature of the spray dryer? 35CPF? the temperature at the outlet? 1 50 ?. The mixing is continued after the addition of the 3. t. i, for about 3 minutes in order to uniformly apply the E. t. the. on the wax. As you continue to mix, you intro- 125? F it feeds heated air to about / for a period of about 30 minutes and the freely flowing granular mass obtained is recovered. The granules are stored for 4 weeks at 40? and are then evaluated in the mortality test? in which the particles float and give a mortality? of 10C # , | against fourth stage larvae 24 hours after application at a dosage of. '' "3 pounds per acre. EXAMPLE 2 A humidable powder of B.t.i. prepared as described in Example 1 in an amount? of 5 par? ti is mixed with 10 parts of molten polyethylene glycol obtained under the name Polyglycol? 4000 from the Dow Chemical Company. The mixing is continued for about 2 minutes at a temperature of 40 ?. The mixture obtained while? still in the molten state it is introduced into an operating coating mixer which contains 85 parts of Sun Uax Antichek paraffin wax in granules and mixing is continued for about 3 minutes. The obtained granules are then stored at 40? for 2 weeks and then are evaluated in the mortality test? in which a mortality is observed? 100% against the fourth stage of larvae 24 hours after application in a dosage of _ 3 pounds per acre. EXAMPLE 3 the In a Stockes tablet / coating machine do they load? 50 lbs. Of Sun Wax Antichek granular paraffin wax. The rotor is spun and then 550 ml of an aqueous solution of a colloidal protein are slowly added to the spinning wax particles. The solution of. colloidal protein is prepared by mixing 198 g of a partially hydrolyzed animal protein obtained under the name Colloid No. i-V from Sv / ift Adhesives & Coatings with water in quantity? sufficient heated to a temperature of 60 ° C to form a solution having a solids content of 35% by weight. The addition of the cooled protein solution takes about 3 minutes and mixing is continued after addition for about 3-5 minutes to evenly apply the protein solution to the wax beads. Then slowly add onto the spinning protein-coated wax granules ^ 3000 g of 3.t.i. prepared as indicated in Example 1. For the addition it takes about 10 minutes and one continues to mix after the addition for about 5 minutes in order to distribute more. or less uniform the humidifiable powder of B, t.i. on the protein-coated wax particles. While further mixing is continued, the resulting mass of particles is treated for approximately 30-45 minutes with dry air heated to a temperature of 50 ° C. in order to reduce the moisture content? below about 8%. Any lumps present in the mass-? ' The obtained are dissolved by hand and the mass is then sieved in order to separate any remaining lumps. The product obtained? consisting of brownish granules without excess dust formation and? freely sliding and the individual parts cells float on water. The final formulation? 87, 2% wax, 1-2.0% wetting powder B.t, i. and 0.8% colloidal protein and the formulation has a pound. -specific weight of 0.9 quarter pec etta final granular mass has a potency of 520 AAU / mg and after 4 weeks storage at 40? produces a 100% mortar on fourth stage larvae 24 hours after application in a 3 lb.per acre dosage in the mortality assay. The addition of High Si silica (1.0% of product obtained) improves the possibility? conservation of the granules avoiding the agglomeration of the granules. EXAMPLE 4? In a belt mixer (Day Model 758) running at 280 rpm and containing 80 parts (approximately No. 2 corn cob granules (1.5 - 3 mm)), 20 parts of corn are added in portions. of paraffin (the same wax used in Example 1) that? been pre-heated to a temperature of: 1.50-170eC, The wax? has been added in about 4? 6 portions of content bulls whose content? / uniquely distributed ? * forms on the mass of corn cob granules. Yup ? continued stirring for about 4 minutes after adding all of the melted wax and during this time the melted wax yes? applied in a way, more? or less imiform on the single corn cob granules and? solidified to form a coating of dried wax. A charge of 88 parts of the cores consisting of wax-coated corn cob granules? was introduced into a similar belt mixer and ? was mixed thoroughly while 4.5 parts of the colloidal protein solution used in Example 1 were uniformly distributed over it. Yup ? continued stirring for about 5 minutes later this addition in order to uniformly distribute the colloidal protein solution on the surface of wax of the nuclei. Continuing to mix, 10 parts of humidifiable powder B, t? I were uniformly distributed on the obtained mass. prepared as described in Example 1 and then yes? continued mixing for another 3-5 minutes in order to ensure uniform application of the powder on the cores of wax coated with protein. They then joined 100 parts of No. 2 corn granules (not coated with wax) and 0.4 parts of hydrophobic silica obtained below form of Aerosil 'R972', then continuing to mix . . ? ? for 5 minutes to obtain a uniform mixture. The addition of the non-wax-coated corn grains promotes drying of the mass and serves as a diluent in the product. The resulting mass is sieved through a No. 6 mesh sieve (0.132 inch) in order to obtain a final granular product. These granules produce a mortality? of 100% of the fourth stage of larvae after 24 hours in the mortality test? when they are applied in a dose of 2 pounds x acre per hectare and after storage for 3 weeks at 40? realizing a mortality? against the fourth stage in the mortality test? 85% and 10056 when applied in dosages of 2 to 4 pounds x acre, respectively. When applied to water in free fall top-down application approximately 98% of the coated granules remain floating on the water surface 24 hours after 1 * application. * Granular spray and foliage penetration characteristics of the granules are judged to be excellent, as are the characteristics of the free fall granules. Result? It is evident that the products of the preceding examples and of other examples prepared in accordance with the invention to contain a mosquito larvicide provide a particularly useful and improved granule for fighting mosquito larvae in an aquatic environment, containing the same, for application from above , that is? above the water and above any vegetation, such as reeds, that grow there. While certain preferred embodiments have been described and highlighted in detail, it will turn out to be? It will be apparent that various other embodiments and modifications within the scope of the invention and its description hereinabove will be apparent to those skilled in the art. There? what do you claim ?: 1 A free-flowing, water-floating granular form of a biological pesticide comprising: ^ a particle mass in which the particles comprise said biological pesticide attached to the surface of a normally solid wax particle core in a system matrix which? inert to the biological pesticide and what? completely or partially humidifiable enough in water so that a quantity? pesticide-effective point of view of the biological pesticide content is released into the water, when the granular particle? , "'' in contact with water, said wax core having a? ? density lower than that of water as it is also inert towards the biological pesticide. The granular pesticide of claim 1 wherein the wax particle core comprises a wax-coated particle base material. 3. A granular pesticide according to claim 2 wherein the particle base material? a grain of corn cob. 4 Granular pesticide according to claim 1 wherein the wax particle core consists essentially of wax. 5. A granular pesticide according to claim 1 wherein the wax? a paraffin wax. 6. A granular pesticide according to claim 3 wherein the wax? a paraffin wax having a melting point of at least 40 ° C. 7 A granular pesticide according to claim 5 wherein the biological pesticide? a bilogical mosquito larvicide. 8. granular pesticide according to claim 7, wherein the bacterium? of the Bacillus type. 9. A granular pesticide according to claim? 8 where the bacillus? Bacillus Thuringiensis var. Israelensis The granular pesticide according to claim 1 wherein the system matrix comprises or? consisting of a coating matrix which? disperse them in water. The granular pesticide according to claim 1 wherein the system matrix comprises or? consisting of a coating matrix which? soluble in water. 12. Granular pesticide according to claim 6 wherein the biological pesticide? a bacterial pesticide of the Bacillus type. 13. granular pesticide according to claim 12 wherein the bacillus? Bacillus Thuringiensis var. Israelensis. The granular pesticide according to claim 13 wherein the system matrix comprises or? consisting of a coating matrix which? soluble in water. 15 A granular pesticide according to claim 14 wherein the biological pesticide encapsulated in a water dispersible matrix is fixed on or in a coating matrix substantially supporting that? soluble in water. 16. The granular pesticide according to claim 15 wherein the water-soluble coating matrix? consisting of adhesive film-forming material. ? ' 17. Granular pesticide according to claim 16 wherein the film-forming adhesive material? a hydrolyzed animal protein. A granular pesticide according to claim 17 wherein the matrix of coatings represents 0.5 to 5% by weight of the particulate wax "core" and represents 3.0 to 20% of the continued weight of the dispersible matrix in water and biological pesticide material that encapsulates it. 19. A process for producing a water-buoyant granular form of a biological pesticide will include coating a plurality of products. of normally solid wax core particles with an aqueous matrix coating composition, the mixing of the wax particles so coating while still moist with fine divided particles constituting an incorporation of a biological pesticide into a water dispersible matrix and drying the resulting mass to remove moisture. sufficient to obtain a mass of freely flowing particles, said wax core having a density? lower than water and said wax core, coating matrix and encapsulation matrix '? ? being inert with respect to the biological pesticide. 20. there is not. 21. A free-flowing, water-buoyant granular form of an agent useful in combating harmful organisms comprising a particulate mass in which the particles comprise said agent attached to the surface of a normally weak wax particle core in a matrix which? inert for the agent and what? completely or partially humidii icabile in water enough so that a quantity? effective to combat the harmful organism of the purpose to be released into the water, when the granular product? in contact with water, said wax core having a density? that ? lower than the density? of water and also inert for the agent. 22. A granular mass according to claim 21 wherein the wax particle core comprises a wax-coated particle base material. 23. A granular mass according to claim 22 wherein the base material of the particles? corn cob grain. 24. A granular mass according to claim 21 wherein the wax particle core consists essentially of wax. 25. A granular mass according to claim 21 wherein the wax? a paraffin wax. ? 1 26. A granular mass according to claim 25 wherein the paraffin wax has a melting point of at least 40 ° C. 27 A granular mass according to claim 26 wherein the agent? a synthetic chemical insecticide useful for fighting mosquito larvae in an aquatic environment. 28. A granular mass according to claim 25 wherein the matrix comprises or? consisting of a coating matrix which? dispersible in water. 29. A granular mass according to claim 25 wherein the matrix comprises or? consisting of an x. coating matrix which? soluble in water. 30. A granular mass according to claim 29 wherein the encapsulated agent in a water dispersible matrix is fixed onto and in a coating or substantially underlying matrix which is soluble in water, 31. A granular mass according to claim 30 wherein the water-soluble coating matrix? consisting of adhesive film-forming material. 32. A granular mass according to claim 31 wherein the adhesive film-forming material? a hydrolyzed animal protein. 33 A Procedure for Combating Zander Larvae . . in an aquatic environment which consists in applying a quantity to that environment. insecticidal effective of a mosquito larvae pesticide of a granular mass according to claim 27? by application from above. 34. A process for combating mosquito larvae in an aquatic environment comprising distributing a quantity in said environment by application from above. effective mosquito larvicide of a granular mass of claim 27? SUMMARY OF THE INVENTION Pesticide granules especially for dispensing a biological pesticide in aquatic applications have a wax core and the pesticide fixed to the core in a dispersible or water soluble matrix. DECLARATION AND LETTER OF APPOINTMENT FOR REQUEST FOR CONTINUATION-IN-PART '_ As inventor named below, I hereby declare that my residence, postal address and citizenship are as stated below next to My name; that I believe in truth? to be the original, first and only inventor of the invention with title: "PESTICIDE GRANULES" described and claimed in the attached description; which the present application partly describes and claims the matter described in the pending application, Series No. 427.604, filed on September 29, 1982 that I recognize my duty to disclose information referred to \ I am aware that they are a matter for the examination of this application; that, with regards to the matter of this question which? common to that previous question, i I do not know and do not believe that the same has ever been known or used in the United States of America before \ j \ of my related or patented invention or described in any printed publication in any country prior to my related invention or more? than a year earlier of said previous application; which dictates common matter was not in public use or for sale in the United States of America pi? one year prior to said previous application; that said common matter is not? been patented or subject to a certificate for inventor issued ? prior to the date of this previous application in any country foreign to the United States of America following an application submitted by me or by my legal representatives or most transferees. twelve months prior to said previous application; and that no patent application or certificate for inventor for said common subject? been filed in any country foreign to the United States of America by me or by my attorneys, representatives or assigns, which in regards to the matter of this application which is not? common to said earlier application, I do not know and do not believe that it was ever known or used in the United States of America prior to my related or patented invention or described in any publication printed in any country prior to my related or other invention. ? one year prior to the application; that this uncommon material was not in public use or for sale in the United States of America anymore? of a year before that question, that said uncommon matter is not? been patented or made the subject of an inventor certificate issued prior to the date of such application in any country foreign to the United States of America following an application filed by me or by my legal representatives or multiple assigns. from 1? ? '??!'.? ?? . -. twelve months before the said application; and that no patent application or certificate for inventor for said uncommon matter? been filed in any country foreign to the United States of America prior to said question; from me or my legal representatives or assigns. I hereby appoint the following: GERALD D.5 HARKIN Reg. No. 19.411 ROBERT E. HONOR Rcg. No. 22.801 FREDERICK H. WEINFELDT Reg. No. 22,619 RICHARD E. VILA? Reg. No. 20.728 WALTER F. JEWELL Reg. No. 24,414 THOMAS O. MCGOVERN Reg. No. 25,741 THOMAS C. DOYLE Reg. No. 22,340 MELVYN M. KASSENOFF Reg. No. 26,389 JOSEPH J. BOROVIAN Reg. No. 26,631 ??????? G. ROTHWELL Reg. No. 28,258 by SANDOZ INC., 59 Route 10, East Hanover, New Jersey 07936, U. S.A. , respectively, individually, my attorneys and / or agents, with full power of replacement and revocation to continue this request and deal with any matter relating to it at the Patent Office. Please address all communications to GERALD D. SHARKIN whose telephone number? 201-386-8485 I hereby declare that all statements made in the present of my own knowledge are true and that all statements made under to information and belief are to be considered true and furthermore that these affiliations have been made with the knowledge that deliberately false and similar statements made are punishable by fine or arrest, or both under Section 1001 of Title 18 of the United States Code and that such deliberately false statements may invalidate the validity? of the application or any patent issued as a result of it. N? Me complete of the inventor: TSUONG R. SHIEH Signature: Date: June 22, 1983 Citizenship: U.S.A. Residence: 13100 San Simeon Ave., Bakersfield, Cai. 93309 Mailing address: as residence. ***** For compliant translation '-' * T * f * ! MANMPii I. Doc. 12616l / s. / Pn. (signature) and pen walyi a? ltri) 427604 Date revised and PATENT Series ; ejhie of 1979) Series Filing date Class Sub Unit? tecni Examiner 06/427 or 604 29 SEPTEMBER 1982 class ca of grujpo 424. 1 25 H. u TSUDNG R. SHIEH, BAKER SF I ELD, C A (0 8M king oM Pi ** CONTINUATION DATA ********************** VERIFIED \. .... . ** FOREIGN AND / PRE CEDENT APPLICATIONS **** ************* VERIFIED Priority foreign Qs claimed? Dno Conditions fulfilled Art. 35 US Code 1 19 Osi [jno Verified and Acknowledged. Initials of the examiner : 0ME DE State or Claims Boards Claim? Wrapping tax POSITATO country designs tions pro -> total indep. receipt curator CA 31 4 0 235.00 '6946 S GERALD D. SHARKIN N M SANDOZ INC., 59 RT. 10 Pi M. 8 EAST HANOVER, m 07936 H. ? PESTICIDE GRANULES? 1 M 8 Ministry of Commerce SU - Patent and Trademark Office PTO-436 L. (Revis. October 1978) The present? to certify that here annexed? a faithful copy, of the United States Patent and Trademark Office registrations, of the? and? pi? above, how? was originally filed. on behalf of the PATENT AND TRADEMARK COMMISSIONER (SEAL) Signed: A.L. JACKSON Certifying officer Date: August 24, 1983 Round date stamp <65? * 00-101 MAIL SERVICE 165.00 -102 TO PATENT AND TRADEMARK OFFICE 427604 date:: (illegible) or? and? or "PESTICIDE GRANULES '* . The present invention relates to granular forms of pesticides, for example biological pesticides, their preparation and their use. Biological substances by nature feed or attack other substances and therefore have been considered for many years as a means of fighting harmful organisms especially those found in agriculture and the like. For example, bacteria that are thus toxic to insects have long been known, and commercial insecticides based on such bacteria have now been available for several years. Similarly viruses are useful against insects while fungi have found use in combating unwanted plants, biological pesticides have the clear substantial advantage of being selective or highly specific for particular purposes and in general they '?>,,> Tax Registration: SO511 NOVEMBER 16 1982427604 19-0134 1 604 6.00CR 1 102 - 176.00CK Case 6946 are environmentally safe. Hence, they have had considerable interest and have attracted in recent years. Again, is their selective advantage typical of biological pesticides? also one of their drawbacks, limiting the market for the effort spent on development and manufacturing. Most of the disadvantages of the organic pesticide are attributed to their origin as living natural substances, generally quiet in their native environment but otherwise more? or less sensitive for a wide variety? of factors, such as heat, light, chemicals and other influences encountered when they exist outside their native environment. So, stability, the capacity? to survive effectively outside the native environment? a fundamental thing and one or of the pi? pre-requisite components of the bacterial pesticide, stability? to heat, stability in the light and stability conservation are usually separate problems that need to be considered and solved. The manufacture of a bacterial pesticide? was I I ' therefore, very much a matter of obtaining stability. necessary by simultaneously realizing all the other properties? and features required for a commercial product. The result ? been, as indicated, costs more? high, less flexibility? in product forms compared to synthetic chemicals for similar use. For example, Bacillus Thuringiensis, 1 * bacterial insecticide pi? commercially known became available in humidifiable powder form, but separate development of highly specific technology was necessary to obtain an emulsifiable concentrate, see U.S. Pat. 3,271,243. A granular form of a bilogical insecticide, in barticular insecticidal bacterium useful in aquatic applications? it was also interesting, but? was generally difficult to develop and? typically accompanied by stability? and other problems. Previous proposed DNA in US patent 3,420,933 focused on the bacterial insecticide Bacillus Sphaericus, a bacterium that is particularly toxic to mosquito larvae and the use of granules which for at least 20% are non-floating in water and * are prepared by conventional granule materials ->? ? them that constitute the central part such as vermiculite and clays. The recent discovery and the availability? of Bacillus Thuringiensis var. Israelensis (later called ^ .t.l ?. '?) Also particularly potent against insects such as mosquitoes and flies, have essentially increased interest in a granular form for a bacterial insecticide, particularly for aquatic applications. In working with said incentive, numerous failures have been encountered in providing a granular form for a biological material until the present invention is made. for example, yes? found that granules prepared with cores of vermiculite, clay coated with oil and other traditional or branched materials showed a drastic loss of power within about 1 week of preparation and therefore presented inadequate stability. to conservation? Most, if not all of the test products prepared in a traditional way were dispensed with difficulty. from traditional sprayers or otherwise, and encountered similar problems. The direction of fall of the granules more? lightweight to aerial application was also difficult to control and unacceptable. Also, in contrast to U.S. Patent suggestions, 3 * 420.933 # yes? found that a mosquito bacterium? pi? effective when dispersed and floating on the surface of the water where the larvae are present. Soaking granules such as those with clay cores have been found to be of low efficacy. The main purpose of the present invention is therefore. in providing a new and improved form of dispensing a pesticide, particularly a biological pesticide. A further object of the invention is to provide a stable granular form of a biological insecticide which? able to float and release its toxic agent on the surface of the water. The objects will become apparent from the following description of the invention. In accordance with a preferred embodiment of the present invention yes? found that a new improved granular form for a diological pesticide comprises a granular mass in which the individual particles are characterized by having a biological pesticide attached to the surface of a normally solid core of wax particles in a matrix of the system. non-harmful to biological material and what? normally dry enough so that the mass of the particles is free flowing but the matrix? sufficiently humidifiable in water so that a quantity? effective of the point of view, pesticide of the pesticide is released when the granule is placed in contact with water. The use of wax as a central part of the granule not only allows the production of a buoyant granule but yes? found below in the invention to realize the basis for a biological pesticide release system having a stable power and a number of other properties? you want for a granular pesticide in particular for a granular pesticide useful in water applications. The granules can also be easily produced by various coating processes followed by drying necessary to obtain a free flowing mass. The invention can be realized in various forms or rt? .izations that establish certain terms and appropriate definitions. In general, the iliological pesticide in the final product? contained within a matrix which in turn is fixed to the underlying wax particle core. So, in the forms of realizations more? simple, a material of matrix pi? or less uniform: or homogeneous containing the biological pesticide pu? * be directly coated on the surface of the wax core. In other preferred embodiments, the organic pesticide can be used. be already? encapsulated in a suitably inert material or protective matrix, and the resulting fine particles, or powder, coated on and / or absorbed in a first coating of an already matrix material. coating the core with wax and agent so as to bind the particles containing biological pesticide to the core. The matrix that fixes biological matter to the nucleus can? be directly or indirectly attached to the core. So, can you? realize indirect fixing first by coating or fixing to the wax core one or more? separate layers of a suitable inert coating, not performing a matrix function and thus fixing the matrix on the exposed outer surface of the thus coated particle. The precise mechanism by which the biological pesticide is released into the water can? also vary according to the particular embodiment of the invention and the type of materials used. In the most pealizations? simple in which the biological matter is kept in a uniform or homogeneous matrix, the water must act on the matrix to free the biological matter contained and this can? be made? *. using a matrix material which? disperse them '*? ? k- or water soluble. On the other hand, when particles containing encapsulated biological matter are coated and / or absorbed into a matrix, the result may be. be a non-homogeneous system which, in a sense, implies a plurality? of matrices within a matrix and the action of water on different matrices can? be different and the total release mechanisms p? - vary accordingly. Thus, the encapsulated biological particles can, for example, be dispersible or soluble in water and the coating of matrix in which it is held and fixed pu? be water dispersible, water soluble or water insoluble. for example the combination of encapsulated biological particles dispersible with water on and / or in a matrix coating which? substantially insoluble in water can? be used in such a way as to lead to the release of the toxic agent by humidifying the portion of particles dispersible in water at the surface of the granule. ^? and the resulting shrinkage of the same in the water. Such action -in correspondence of the surface in general will expose? other particles or other moist portions! ible originally inside the granule to the action of humidification and cessation * * '' ne so that further quantities can be released? of the biological pesticide in the water, and the granules having heavy and / or underlying biological content more? efficiently used. On the other hand, in other preferred embodiments, the plurality? of encapsulated biological particles? essentially water-dispersible in nature and fixed on and / or in an essentially water-soluble matrix coating so that the entire matrix system is freed from the wax core by the action of water with the individual, essentially encapsulated particles of? dispersing from the place of application. In any case, since? different dispositions and sensitivities? of humidification as dispersdib? lit? and solubility? the expressions "wettable in water" and the like used herein to refer generically to such release mechanisms in water can be used and are applicable to the whole system or to any part of the biological pesticide-containing matrix system attached to the core of wax granules, as appropriate , to release the biological toxic agent in the presence of water. Result? also evident that the term "matrix" is used in a broad sense to include systems in which vi? a substantially complete incorporation into the host matrix and systems - in which a substance? incorporated only partially- *? ? ? . T mind and therefore? simply held by the host matrix and also systems in which each substance is fixed by a combination of these two )? * mechanisms. The terms "encapsulated" "encapsulated matrix" and the like are used herein with reference to the biological pesticide to indicate a substantially complete incorporation of either the biologically active substance into the host or matrix material. Will it be understood? for? that biologically active pesticides can be encapsulated by processes basically involving mixing of the pesticide with the matrix material, so that a smaller portion of the quantity? total amount of biologically active substance can be and, usually,? present or exposed to the surface of the matrix, even if the pesticide? considered encapsulated as the expression used here. Also, whether or not, as in certain preferred embodiments, are pathways encapsulated or matrix particles? In a matrix or other essentially non-homogeneous matrix systems, bioiogic matter? contained or protected within the grain in the sense of being encapsulated within its matrix pi? immediate or adjacent. So the expression "system matrix" or matrix system? generally use-? * 1 ta without distinction to understand all the matrices that surround and act to fix the biological organism directly and / or indirectly to the wax core, unless it is distinguished in this text as often will be the case, by distinction, the expressions " matrix coating "matrix coating" and the like will be used to indicate a more or less underlying matrix, distinct in terms of the representation of a single coating application or formed by two or more applications of the same coating to be underlying, enclosing, incorporating and / or similar to the sole or major component of the matrix system in terms of action to bind a biological pesticide directly or indirectly to the wax core, although, as in certain more preferred embodiments, the coating matrix in weight can be a small fraction of the system matrix.The coating matrix can be made of vat or more matter not necessarily mutually soluble or homogeneous, which coating matrix composition? generally uniform but, by definition, it will not include? materials separately applied or coated, for example the particles pi? or not separated of the biological pesticide in an encapsulation matrix or when not applied with the coating matrix material or composition? So, as contemplated here, the matrix of the system? the essential and total matrix which has a total encapsulation effect and which will constitute? or will it be? consisting of an essentially equal coating matrix. A mapia range of wax has a density? less than water and can? be used in accordance with the invention to prepare pesticide granules similarly having a density less than water, it being noted that the additional materials needed to form the preferred granules of the invention are even more so. light water. If, for whatever reason, it may be desired to use a more coating or additive material? heavy of water, a wax can? usually be chosen, which will have? a density? sufficiently low so that the resulting granule will be? nevertheless floating, it being noted that the wax core will replace? generally the main weight of a practical granule; On the other hand, the resulting wax and granules provided by the invention generally have sufficient weight to penetrate stubble and other similar productions encountered in an aquatic environment and to resist deflection by water currents when applied from air, all of which ? ? the capacity? desired in a granule for the control of mosquitoes and the like? The waxes to be used in the invention are normally solid materials in order to retain integrity. of the granules and avoid any unwanted melting of the granules during storage. In practice it is desired that the wax have a melting point of at least 30 ° C and preferably of at least 40 ° C. Preferred waxes have a melting point of between 45 ° C and 85 ° C plus? preferably between 50? C and 75? C, The wax used must be inert in the sense of not being harmful to the biological pathogen to be incorporated into the granule. Many waxes have a chemical composition that? inert to various biological substances and 1 * inertia pu? be ascertained routinely through simple tests and error if necessary. However, in general the paraffin substances are inert towards biological pesticides and paraffin waxes are preferred as the material for the central part of the granules of the invention. Paraffin waxes that have melting points in the pi? prefer ?? to are readily available in cpmmerpio in a suitable finely divided form (egranuloM), for example, Sun Wax 4412 (PF 60? c) and Sun Vax Anticheck (PF 67? C), both available from the Sun Petroleum Products Company, wayne, Pennsylvania . The diameter of the finely divided wax particles as the base material for forming the granules of the invention? preferably between 0.5 and 3.0 millimeters (mm), plus? preferably between 1 and 2 mm. The system matrix serves two or more? functions, according to the particular embodiment of the invention to be employed. In general, the matrix system can? negatively affect the stability? of the organic pesticide and then? consisting of material treated from natural sources and include starches such as corn starch and various cellulosic materials such as ethyl cellulose. Protein materials include but are not limited to casein, carrageenan, partially hydrolyzed vegetable seed proteins such as soy protein and partially hydrolyzed animal proteins. Do representative synthetics include polyets? lenglicoii normally solids and polyvinylal resins? cool. The particular material suitable as a matrix and which makes the medium more? inert and more? stablepar a particular biological pesticide usually will be? known for biological pesticides and when not? known, as in the case of new materials intended for biological pesticides, 1 * suitable material for matrix pu? be determined by routine experimentation. In general, however, protein materials provide a stable medium for biological pesticides such as bacteria, viruses and fungi that can be used in general. As indicated, at least the coating matrix of the matrix system must have the function of securing the biological pesticide to the particulate wax core, as well as providing an inert environment from which it is preferably released into water. inert in the sense of being non-harmful to ag-? ? ? ? the biological toxicant, while enclosing and thereby protecting the biological pesticide. The coating matrix also serves to attach the biologically active pesticide to the wax core. Also when is the biologically active substance? substantially fully incorporated into the coating or otherwise non-releasable in water, the matrix system must also be fully or partially humidifiable in water in order to be able to release the active substance as a multiplicity. of fine particles of the biologically active substance or of the active encapsulated substance. The particular s-material to be used as the matrix material of the system will depend the particular biological pesticide to be developed and various choice factors. While ? a * anq> ia choice of matrix materials and coating vehicle substances with pesticides other than biological pesticides, the choice of such materials? pi? critical when an organic pesticide is used as the active ingredient. Such materials can be carbohydrates, protein materials of animal or vegetable origin and materials selected from a synthetic source. Carbohydrates which represent the most important materials? suitable are organic pesticide, how will it be? appreciated, a materia-. ? ? the wax can to be intrinsically judged a poor and unlikely candidate for the nucleus of a granule since? its surface offers little opportunity? or no opportunity? by absorption which? the common or primary mechanism by which pesticides are fixed in many granular pesticides. Therefore, in particular in the forms of realization pi? practices in which the coating matrix? fixed directly to the "core" of wax the fixing mechanism essentially? a surface bonding mechanism and generally in a physical sense, rather than a chemical reaction. This superficial physiological bond is generally realized by the properties? adhesives of materials employed in the coating matrix and such materials are further selected in a corresponding manner. The term "adhesive" and the like as used herein encompasses the different properties. by which adhesives can make a bond that include properties? and capacity? such as adhesiveness, penetration and the like and furthermore the advantages of cohesion as achieved in particular by film-forming adhesives. When a coating matrix material is employed which produces dispersible coatings *? water or other coatings in a characteristic and essentially non-film-forming way, the property? of adhesiveness? becomes a factor more? also good for the fact that the oily nature of the wax itself does not provide an ideal bonding surface? Thus, in such non-film forming systems, the preservation of adhesiveness must also be considered. of these coatings leaving an appropriate moisture content? residual and carrying out the conservation in conditions that do not rapidly decrease the humidity? residual. When using less tacky adhesives in dispersible coating matrices can? be therefore? preferred to avoid conservation as much as the good stability? the preservation of the product can allow and / or use granular applicators which do not exert a strong mechanical action on the granules. ? involved in the realization more? preferred, since, among other things, the contributed cohesion benefit of the resulting film, even if substantially disrupted by the inhomogeneous particles contained, is believed to provide a mechanism? ? particularly effective for bonding the investment matrix directly or indirectly to the wax particle core. The matrix material of the system can? be chosen from a separate source or even can? be present in the organically manufactured product, as a result of the raw materials used in the manufacture, or can it? be chosen from a separate source or can? have both of these origins. for example, bacteria and fungi useful as pesticides are usually produced commercially by fermentation in a nutrient medium that includes water, carbohydrates, proteins and several compatible inorganic salts. The product obtained on a dry basis usually contains a greater proportion typically at least 80% by weight of carbohydrate and protein residues which are at least partially dispersible in water and such products may suitably be used as such as material for the system matrix or as a component thereof in the preparation of the granules of the present invention. Fermentation products in which the protein residue alone? at least 50% by weight of the product A dry base - are usual and are preferred in the case of fermentation products to be used alone or mixed with one or more products. of other matrix materials to form a coating composition. Such fermentation filler products can be employed as a coating after making any adjustments required to bring the water content to the desired level, for example by evaporation under vacuum. As an alternative, 1 * drying of the product? " of a fermentation charge, for example spray drying according to known processes, produces a dry particle mass in which the particles constitute an encapsulation of the biological pesticide in a matrix consisting of the residue of the fermentation nutrient medium. ? This particle mass can? be mixed with water to form a standard composition. sticky paste that can? be applied on the "core *" to form a bead in which the biological active material is fixed in a coating matrix consisting of the nutrient medium residue. On the other hand, and according to the most preferred embodiments. of the invention, a dry powder, obtained for example by spray drying the fermentation filler, is a particularly suitable form to be applied to the "core" particles while still wet from a first coating of matrix coating material. The application of such a preferred embodiment and biological pesticides not normally produced by fermentation, for example pesticides consisting of viruses, can be used. be realized, yes? described now for example, the production of fine particles comprising a pesticide consisting of a virus encapsulated in a water-dispersible protein matrix, in the British Patent 1557 * 668 issued on August 8, 1980, by Rogoff and shieh. The process for preparing the granules of the invention will vary. according to the particular realization desired to be produced, but it will be? evident from the description of the invention. In general, methods of applying liquid compositions to particles which are uncoated or have a dried prior coating are known, as are also known methods of applying dry particles to moistened particles by means of a prior coating. When using a liquid coating is the solvent or dispersant distribution vehicle preferably? water, organic solvents can be used, but they must usually be chosen carefully since? many can influence negatively- ~? mind the particular biological pesticide. pi? In the preferred embodiments of the invention, fine dry particles that contain the biological pesticide encapsulated in an encapsulation matrix, such as a cos? said powdered form of bacterial insecticide such as Bacillus thuringiensis Israelensis are applied on and at least partially incorporated into an undried matrix coating which? previously applied to the wax particle, in such a process the wax "core" material in the form of desired particles or granules is agitated or mixed together e.g. by tumbling in a suitable mixer and the coating matrix material is then sprayed (suitably in the form of an aqueous solution) or otherwise applied to the mass of the "core" followed by a continuous mixing sufficient to apply the coating matrix substantially over the entire surface of the individual wax particles. This coating is preferably made more? or less at room temperature or otherwise below the melting point of the wax. The coating matrix material? suitably applied in the form of an aqueous solution which readily coats the wax and which has sufficient water to make s? that the biological pesticide in finely divided encapsulated form can be absorbed to a substantial degree into the coating. On the other hand, concentration? sufficiently high so that excessive drying can be reliably avoided. In many cases, concentrations of the order of 20 to 50%, preferably 30% to 40%, on a weight / volume ratio, are suitable. The quantity of material of the coating matrix on a dry basis can? vary depending on a number of factors including the material used, the thickness of the coating desired, the capacity? coating and the like. In general, the quantity? of coating? very small in relation to the weight of the material of the "core" of wax and pu? also be relatively minor in comparison to the quantity? a finely divided encapsulated biological pesticide; to be added later. c for example, the coating matrix in the most embodiments? do you prefer pu? represent a concentration of between 0.5 and 5.0% of the weight of the wax "core" material used, plus? typically 0.7 to 2.0% by weight of the core. The mixing time for applying the coating matrix solution to the "core" will vary but can be a relatively short time between 1 minute and 20 minutes, more particularly between 3 minutes and 10 minutes, when such a coating is complete, the mixing is continued or another type of tumbling of the liquid coated wax particle mass to avoid unwanted agglomeration and the addition of the biogical pesticide in finely divided encapsulated form can be started immediately after the coating? depending on the drying characteristics of the matrix coating and the desired amount of absorption or the degree of adsorption in the matrix coating Typically addition of biological pesticide begins as soon as the coating of the coating matrix is complete The addition of the biological pesticide in finely divided encapsulated form is carried out m And? by controlled and / or intermittent introduction or by distribution in the tumbling mass of the coated core particles in order to obtain a better application. ? less uniform than encapsulated biological pesticide particles on coated wax particles. The time of addition of the pesticide material can? be of the order of 1 minute up to 20 minutes, plus? in particular of 2 minutes up to 10 minutes. The addition of the biological pesticide is preferably carried out at room temperature and preferably below the melting point of the wax core material, as indicated above, the quantity of the matrix material on which or in which the biological pesticide is applied pu? be relatively minor in comparison to the quantity? of encapsulated biological pesticidal material, for example, the coating matrix material in the preferred embodiments can represent, from 3.0 up to 20%, pi? in particular from 5-10 to 12% by weight of said encapsulated biological pesticide to be fixed to the wax core on and / or in the coating matrix material. Hence, the weight of the encapsulated biological pesticide can? be about 5 to 35 times, more? typically 8 to 20 times the dry weight of the coating matrix material. The quantity particular of encapsulated biological pesticide material to be used pu? therefore vary? Very. While coltroliata at its upper limit from the capacity? of the liquid matrix coating solution to absorb pesticidal, biological encapsulated material, the amount of said encapsulated material can be determined in general by preference factors and the final desired characteristics of the product such as power after consideration of the concentration. On the other hand, the limit of the quantity? from encapsulated material pu? be influenced by the time required to dry the product and the need? to avoid unwanted agglomeration of the particles in the fluid mass of particles. In any case, when? completes the addition of the pesticide material, the particle mass obtained is maintained in a state of agitation by mixing or tumbling and is subjected to drying in order to obtain a freely flowing particulate product. Such drying can? be suitably carried out with a heated inert gas, such as heated air which is introduced into the mass subjected to stirring, since biological pesticides even in their protected form are negatively affected by high temperatures, di usual ? It is necessary to control the temperature of the drying conditions or of the heated gas at moderate levels. In general you can? adopt in satisfactorily an air temperature between 100? F and 160eF, plus? air temperatures between 110 ° F and 110 ° F can be suitably adopted 140? F, in general not? it is necessary to completely dry the mass and you can? obtain a satisfactory product with a decrease in the moisture content? at most up to no more? 10%, preferably up to no more? of 8%, The retention of a certain humidity? can be desirable, as noted above. Will the drying time vary? depending on special cases and can? be between 15 minutes and 3 hours, but you can? carry out satisfactory drying typically from 25 minutes to 1 hour. ' Any agglomerates that form during drying can be separated, for example by hand and the final product is usually screened according to the specifications of the desired product. When using granular wax forms typical commercially available particle diameter in the final product can? typically vary between 0, 5 and 4 mm, pi? preferably between 1 mra and 2 mra. The product obtained can? then be mixed and coated with a small amount, for example from 0.1 to 4.0% by weight of the granule, preferably between 0.5 and 2%, of an anti-agglomeration agent such as calcium stearate, various silicas such as High sii, Aerosil and the like if desired. In the preferred embodiment and other embodiments wherein fine particles of an encapsulated biological pesticide are applied on wax which? um'.dified with a matrix coating material the exact nature of the final product will vary? depending on several factors such as the quantity? of encapsulated material applied to the coating matrix material. The use of quantity? only moderate of a finely divided encapsulated biological pesticide can? lead as a result to an absorption pi? or less substantially complete of the biological material in the liquid matrix coating and to a pi? or less substantially complete of the particles containing the biological pesticide in the dried matrix coating. On the other hand, the application of quantity? pi? large of biological pesticide that reach the capacity? absorption of the liquid matrix coating will be? as a result that a significant portion of the particles containing the biological pesticide are less than fully incorporated and only variable portions of some particles are held by the coating matrix and even in some cases are more adherent. between them and to the coating matrix. In his case, the biological particles held more? read at the complete drying of the product can tend to fly away, but this result can? be tolerated and controlled and? a minor disadvantage in relation to all the disadvantages offered by the product and the opportunity? to deliver a high or maximum dosage with highly charged particles which will also release the total biological pesticide contained in times ap? different in water. When using a coating matrix material in the form of a film in the preferred embodiments described above some or all finely divided encapsulated particles containing the biological pesticide will penetrate and be absorbed into the liquid matrix coating ^ JW? ? ,? ' but the resulting dried coating, while non-homogeneous, will have? nevertheless, a lattice, cavity? honeycomb and / or other similar effect, wherein the matrix coating material remains substantially continuously interlinked to provide a cohesive benefit. While not readily subject to description in further detail, these systems, especially employing water-soluble matrix coatings, produce a particularly good bead in accordance with the invention. In general, entities release and other characteristics of the final product will also be determined in accordance with the type and quantity. of material used, such as system matrix or matrix coating, as well as l? quantity of biological pesticide contained in it. Granules prepared in accordance with the invention will release a pesticide-effective amount of the contained biological pesticide within a reasonable time, e.g., up to 24 hours and can generally be prepared in various embodiments to deliver at least 80%. of the biological pesticide within this period of time, for? Delayed or very slow release in a biological granule is usually not considered desirable once in contact with water and the granules of the invention, which particularly include those with a humidifiable matrix coating, are readily capable of releasing at least 5056 of the pesticide. content within 3 hours and 1 * 80% within 6 hours. The present invention can? be generally applied to biological substances that are used as pesticides, for example bacteria, viruses and fungi all of which classes are represented by various substances already? try in the field and which may be suitable for use in accordance with the invention and its description, here. Bacterial insecticides, in particular of the Bacillus type, are currently being analyzed more. ' widely and represent a broad class of particular interest. How are bacterial insecticides, in particular of the Bacillus type, more? those identified as Bacillus thuringiensis (Berliner) are widely known, although other bacilli such as Bacillus? paericus, will be of immediate interest to be used in the invention for their efficacy against mosquito larvae requiring aquatic application. See, among other things, U.S. Patent 3271243 and the literature cited. Usual commercial products employing the Bacillus thuringiensis are represented by the varieties? Kurstcdci and Israelensis, The invention has the most interest? immediate for use with said variety? of Israelensis (B.t.i.) which currently? the biological pesticide of choice for combating mosquitoes, flies and related larvae in an aquatic environment, see U.S. Patent 4.166.113.7 While the invention? has been described referring to applications in aquatic environments and more? specifically to B.t.i. sar? evident that it can? be easily applied in the non-aquatic uses of biological pesticides where granular applications are desired or where, for example, an attempt is made to reach insects in depth? within the folds of the crop like corn. ? ^ Furthermore, the invention has generally demonstrated certain advantages of a wax core for a pesticide granule prepared or readily adapted in accordance with the invention, in particular for, but not limited to aquatic applications, e.g. insecticides useful against mosquito larvae, where current granules are readily immersed and / or have disadvantages overcome by the invention. Thus, we contemplate the fact that the invention in its most important aspects? vast applies to all substances or agents of a chemical nature useful for combating harmful organisms including synthetic chemicals and natural non-biological substances as well as biological microorganisms. In applying the invention, it should be noted that no? Is it necessary for the matrix that attaches the pesticide to the wax core to encapsulate the pesticide unless it is normally required to maintain its stability? in one way or another as a biological pesticide requires to be so? protected. However in a practical sense, the invention as described and applied to biological substances will be herein? preferably made with all chemical agents to combat harmful organisms, for example insects, plants, fungi, etc., for example using matrix coating compositions in which the agent is intimately mixed, for which one will have? an essential encapsulation within the final granule in a system matrix attached to the wax core, and in particular, coating traditional humidifiable powder forms of such agents on the core in wax particles, while moist from a previous coating, of a composition coating matrix coating in accordance with all general and specific and preferred methods described herein, for biological substances wherein a granular product comprising the wettable powder incorporating the agent in a water dispersible matrix,? fixed to the wax core in a coating matrix pi? or less underlying than preferably? soluble in water. Result? It is evident, however, that a wide choice of matrix materials and coating vehicles will be available. available with agents other than biological pesticides, since? such other agents, usually, do not present stability problems? characteristic of biological pesticides, although the requirement for the use of matrix materials and processes which are non-harmful to the agent, remains. Examples and Related Information In the Examples that follow the mortality tests? were carried out by introducing into basins - 35 -ii's. ; plastic flats having dimensions of 5 x 11 x 13 'inches? the? - - S liters of dechlorinated tap water so as to have a height of 10 cm and? 2 1 foot surface area. 25 Aedes aegypt larvae (second or fourth stage) were introduced into the basin for each test. In each basin, yes? also added brewer's yeast in the quantity? of 25 mg per liter of water in order to provide feed for the larvae. The test is then carried out by distributing on the surface of the water a quantity? predetermined (dosage) of the granules to be examined and determining the mortality? larvae as a percentage of all larvae initially present within 18 to 24 hours after adding the granules. In the Examples parts and percentages are by weight and temperatures are in? C unless otherwise indicated, EXAMPLE 1 95 parts of a Sun Vax Antichek (Sun Petroleum Products Company, V / ayne, Pennsylvania) granulated paraffin wax are introduced into a coating mixer. The mixer is turned and 20 parts of a paste-like composition prepared by thoroughly mixing 15 parts of water with 5 parts of a form are added to the tumbling mass. ? in powder technique of Bacillus thuriqgiensis? israelensis (B. t. i.) that? at least partially humidifiable and has a potency of 2300 AAU / mg. The powder of B, t. the? is prepared in a conventional way for the preparation of a powder B. t. eva- technique? by vacuuming the content from the fermentation vat (initially having a solid product content of about 6% in an aqueous medium) up to a solid product content of about 14-18% of which about 40-60% solid products ? consisting of protein material and 1 -10%? consisting of starch at a temperature of 40? and under a vacuum of . ... 25-30 in / Kg. and spray drying the obtained mixture. The inlet temperature of the spray dryer? 3 5CPF and the temperature at the outlet? 1 50 * ?. The mixing is continued after the addition of 3, t, i, for about 3 minutes in order to uniformly apply the B. t paste. the. on the wax. As you continue to mix, you intro-125? F it feeds heated air to about / for a period of about 30 minutes and the freely flowing granular mass obtained is recovered. The granules are stored for 4 weeks at 40? and are then evaluated in the mortality test? in which the particles float and give a mortality? of 10 (? against fourth stage larvae 24 hours after application at a dosage of. "* t 3 pounds per acre. EXAMPLE 2 A humidifiable powder of B.t.i. prepared as described in Example 1 in an amount? of 5 par-? ti is mixed with 10 parts of molten polyethylene glycol obtained under the name Polyglycol? 4,000 from the Dow Chemical Company. The mixing is continued for about 2 minutes at a temperature of 40 °. The mixture obtained while? still in the molten state it is introduced into an operating coating mixer which contains 85 parts of paraffin wax in Sun \ Jax Antichek granules and the mixing is continued for about 3 minutes. The obtained granules are then stored at 40? for 2 weeks and then are evaluated in the mortality test? in which a mortality is observed? of 100? against the fourth stage of the larvae 24 hours after application in a dosage of. . 3 pounds per acre. EXAMPLE 3 the 50 lbs of Sun Wax Antichek paraffin wax granules are loaded into a Stockes tablet / tablet coating machine. The rotor is spun and then 550 ml of an aqueous solution of a colloidal protein is slowly added to the spinning wax particles. The solution of. colloidal protein is prepared by mixing 198 g of a partially hydrolyzed animal protein obtained under the name Colloid No. 1-V by Svift Adhesives & Coatings with water in quantities? sufficient heated to a temperature of 60 ° C to form a solution having a solids content of 36% by weight. The addition of the cooled protein solution takes about 3 minutes and the mixing is continued after the addition for about 3-5 minutes in order to uniformly apply the protein solution on the wax granules. Then 3000 g of humidifiable powder of 3.t.i, prepared as indicated in Example 1, are slowly added onto the spinning protein-coated wax granules. It takes about 10 minutes to add. continue to mix after the addition for about 5 minutes in order to distribute more? or less uniform the humidifiable powder of B.t.i. on the protein-coated wax particles. While further mixing is continued, the mass of particles obtained is treated for approximately 30 to 45 minutes with dry Syria heated to a temperature of 50? in order to reduce the moisture content? beyond? below about 8%. Any lumps present in the mass obtained are dissolved by hand and the mass is then sieved in order to separate any remaining lumps. The product obtained? consisting of hrunastro colored granules without excess dust formation and? freely flowing and the individual particles float on the water. The final formulation? 87.2% wax, - 1-2.0% humidifiable powder B.t.i. and 0.8% colloidal protein 2 formulation has one pound. ? specific gravity of 0.9 quarter pec etta final granular mass has a potency of 520 AAU / mg and after 4 weeks storage at 40? produces 100% mortality on fourth stage larvae 24 hours after application in a 3 pound per acre dosage in the mortality assay. Result? It is evident that the products of the preceding examples and of other examples prepared in accordance with the invention to contain a mosquito larvicide provide a useful and improved granule for combating mosquito larvae in an aquatic environment containing the same for application from above, i.e. above the water and above any vegetation, such as reeds, that grow there. While determining preferred embodiments have been described and highlighted in detail. result? It will be apparent that various other embodiments and modifications within the scope of the invention and its description hereinabove will be apparent to those skilled in the art. There? what do you claim ?: 1, a free-flowing, water-buoyant granular form of a biological pesticide comprising a particulate mass in which the particles comprise said biological pesticide attached to the surface of a normally solid wax particle core in a system matrix which? inert to the biological pesticide and what? completely partially humidifiable in enough water so that a quantity? pesticide-effective point of view of the biological pesticide content is released into the water when the granular particle? in contact with water, said wax core having a density? lower than that of water and also being inert towards the biological pesticide, 2. A granular pesticide according to claim 1 wherein the wax? a paraffin wax, 3. A granular pesticide according to claim 1 wherein the wax? a paraffin wax having a melting point of at least 40 ° C, 4. A granular pesticide according to claim 3 wherein the biological pesticide? a bacterial insecticide. 5. A granular pesticide according to claim 4 wherein the bacterium? of the Bacillus type. 6. A granular pesticide according to claim 5 wherein the pesticide? Bacillus thuringiensis var. Israelensis. 7. Granular pesticide according to claims 1,2,3,4,5, 0 6 wherein the system matrix comprises or? consisting of a coating matrix which? dispersible in water. 8 granular pesticide according to claims 1,2,3,4, 5 or 6, wherein the matrix of the system comprises or? consisting of a coating matrix which? soluble in water. The granular pesticide of claim 8 wherein the biological pesticide encapsulated in a water-dispersible matrix is fixed on or in a substantially underlying coating matrix which? soluble in water. 10. granular pesticide according to claim 9 wherein the water-soluble coating matrix? consisting of adhesive film-forming material 11 Granular pesticide according to claim 10 wherein the film-forming adhesive material? hydrolyzed animal protein. 12. A granular pesticide according to claim 11 wherein the coating matrix represents from 0.5 to 5% by weight of the wax material and represents from 3.0 to 20% of the combined weight of the dispersible matrix in water and the biological substance that encapsulates it. 13. A process for producing a water-buoyant granular form of a biological pesticide comprising coating a plurality of pesticides. of normally solid wax core particles with an aqueous matrix coating composition, mix the thus coated wax particles while still moist with divided fine particles constituting an incorporation of a biological pesticide into a water dispersible matrix and dry the mass resulting to remove moisture? sufficient to obtain a mass of freely flowing particles, said wax core having a density? less than water is said wax core, a coating matrix and encapsulation matrix being inert with respect to the biological pesticide. 14. A method according to claim 11 in which the coating matrix is reduced? soluble in water. 15 Process according to claim 14 wherein the coating matrix? consisting of a film-forming adhesive material. 16. The method of claim 15 wherein the adhesive film-forming material? hydrolyzed animal protein. 17 A process according to claim 16 wherein the coating matrix by weight contains r 0.5 to% of the core or wax material and the coating matrix by weight contains 3 to 20% of the combined weight of the water-dispersible encapsulation of the biological pesticide. 18. Process according to claim 17 wherein the biological substance? a bacterium of the Bacillus type. 19. process according to claim 18 wherein the biological substance? Bacillus thuringuensis var. Israelensis. 20. granular pesticide whenever produced according to the process of claim 13? 14, 15? 16, 17, 18 or 19. 21 The granular pesticide of claim 7 wherein the system matrix especially comprises water dispersible coating matrix which? at least 5G% of proteinaceous material. . '* 22. Free flowing water buoyant granular form of an agent useful in combating harmful organisms comprising a particle mass in which the particles comprise said agent attached to the surface of a normally solid wax particle core in a matrix which? inert for the agent and what? completely or partially humidifiable in water sufficiently so that a quantity? effective to fight the harmful organism of the purpose to be released into the water, when the granular product? in contact with water, said wax core having a density? that ? lower than the density? of water and also inert for the agent, 23, Granular mass according to claim 22 wherein the wax? a paraffin wax. 24 A granular mass according to claim 23 wherein the paraffin wax has a melting point of at least 40 ° C. 25 Granular mass according to claim 24 wherein the agent? a synthetic chemical insecticide useful for fighting mosquito larvae in an aquatic environment. 26. A granular mass according to claim 23 wherein the matrix comprises or? consisting of a coating matrix which? dispersible in water. 27. Granular mass according to claim 22,23? 24? and 25 where the matrix includes or? consisting of a coating matrix which? soluble in water. 28. A granular mass according to claim 27 wherein the agent encapsulated in a water dispersible matrix is fixed on and in a substantially underlying coating matrix which? soluble in water. 29. A granular mass according to claim 28 wherein the water-soluble coating matrix? consisting of adhesive film-forming material. 30. A granular mass according to claim 29 wherein the film-forming adhesive material? a hydrolyzed animal protein. 31. A method for combating mosquito larvae in an aquatic environment comprising distributing a quantity in that environment by application from above. mosquito larvicide efficacy of a granular mass of claim 6 or 25 4 (date stamp: ? * illegible) SUMMARY OF DESCRIPTION Pesticide granules, especially for dispensing a biological pesticide in aquatic applications have a wax core and the pesticide fixed to the core in a dispersible or water soluble matrix. * DECLARATION AND LETTER OF APPOINTMENT FOR APPLICATION * _ ORIGINAL_ Case No. 6946 USA As the inventor named below, I hereby declare that my: residence, mailing address and citizenship are as set forth below next to my name; that I believe in truth? to be the original, first and only inventor of the invention with the title "PESTICIDE GRANULES" described and claimed in the attached description; p that, I do not know and I do not believe that the same has ever been known or used in the United States of America prior to my relative or patented invention or described in any printed publication in any country prior to my relative invention or more? one year prior to said previous application; that I do not know and I do not believe that it was ever known or used in the United States of America prior to my relative or patented invention or described in any printed publication in any country prior to my relative invention or more? one year before the previous application; that the same was not in public use or for sale in the United States of America oi? one year prior to said application; y what 1 * invention does not? been patented or made subject? casting of certificate for inventor issued before the date of said previous application in any country foreign to the United States of America following an application filed by me or by my legal representatives or most transferees? twelve months prior to said application; that I recognize my duty to disclose information of which I am aware is a matter for the issue of this request; that no patent application or certificate for inventor for said invention? been filed in any country outside the United States of America by me or my legal representatives or assigns, except as follows: NOBODY Hereby nq-nino the following GERALD D. SHARKIU Rey. I- 19.411 ROBERT S. HOHOR Rcg. I have. 22.801 FREDERICK 11. KEIHFELDT Rcy. I have. 22.619 RICHARD E. VILA Rcy? I have. 20.728 WALTER F. JEWELL Rey. I have. 24.414 THOMAS O. MCGOVERH Rcg. I have. 25.741 THOMAS C. DOYLE Rcy. I have. 22.340 HELVYH M. KASSEHOFF Rcg. I have. 26.389 JOSEm J. DOROVIAH .Rcy- Ho. 26.631 ??????? G. ROTHWELL Rcy. I have. 28,258 by SANDOZ INC. 59 Route 10, Esr Hanover, New Jersey 07936, * USA. , respectively and 'individ? imenfe, my attorneys and / or agents, with full power of replacement and revocation to continue said application and deal with and Trademarks at the Patent Office / any related matter to it, please address any communication to GERALD D. SHARKIN whose telephone number? 201 - 386-8485. I hereby declare that all statements made in the present of my own knowledge are true and that all statements made on the basis of information and belief are to be considered true and furthermore that these statements have been made with the knowledge that deliberately false and similar statements made are punishable by fine or arrest, or both under section 1001 of Title 18 of the United States Code and that such deliberately false claims may invalidate the validity? of the application or any patent issued as a result of it. Full name of the first or joint inventor: Tsuong R. Shich Signed: TSUONG R. SHICH Date: September 27, 1982 Citizenship: United States of America Residence 13100 san Simeon Ave. Bakersfield, California * '93309 Mailing address: as above Full name of the second or joint inventors: Signed: _ Date: Citizenship: Residence: Mailing address: ***** for compliant translation The VMs (signature) (pef s * ii / for others) II.Doc. 12616l / s. / Pn