WO1995031101A1

WO1995031101A1 - Sprayable particulate derived from seed

Info

Publication number: WO1995031101A1
Application number: PCT/US1995/006309
Authority: WO
Inventors: Lucia G. I. Marshall; Steven H. Bixby
Original assignee: Nurture, Inc.; Monsanto Co.
Priority date: 1994-05-18
Filing date: 1995-05-17
Publication date: 1995-11-23
Also published as: AU2595695A

Abstract

A proteinaceous particulate material derived from dehaired oats or other grains, wherein the grain has been dehaired prior to production of the proteinaceous particulate material through milling and solvent extraction; the active ingredient is mixed with the particulate; and an aqueous formulation containing the active ingredient and particulate has enhanced sprayability and will promote a sustained or controlled release of active ingredient.

Description

SPRAYABLE PARTICULATE DERIVED FROM SEED

Field of the Invention

The present invention relates to sprayable particulate materials derived from whole seed grains. More specifically, it relates to controlled release compositions or emulsions comprising oat or other seed proteinaceous particulate material and active ingredients such as pesticides.

Background of the Invention Oats have unique characteristics which distinguish them from other cereal grains. Oats contain a significantly higher protein concentration than other cereal grains and have one of the highest oil contents of the cereal grains. As with other cereal grains, oats can be milled, extracted with organic solvents, typically hexanes or heptanes, to remove lipids, and dried to form proteinaceous particulate materials for use as an emulsifier. U.S. Patent 5,079,005 describes the production of the proteinaceous particulate materials and the use of these materials as controlled release agents for the delivery of active ingredients. Oat particulate materials are also known to form highly effective emulsifiers. When these proteinaceous materials are combined with an aqueous phase and a lipophilic phase, an oil- in-water emulsion can be formed spontaneously at room temperature and with minimal agitation. When active ingredients are added to this mixture, they become emulsified by or entrapped within the microporous protein structure and are slowly released from the particles.

The range of active ingredients that can be incorporated into oat-derived particulates is broad. Active ingredients may include flavors, fragrances, oils, cosmetics, pharmaceuticals, and the like. In the agricultural area, oat- derived particulates have shown significant promise in delivering pesticides, including herbicides, fungicides, gametocides, nematicides, insecticides, safeners, adjuvants and surfactants.

Agricultural pesticides have revolutionized modern farming practices. These materials have made possible the economical, large scale production of crops at high yield per acre. However, environmental and cost concerns dictate that the minimum effective amount of pesticides be used. In order to achieve this goal, oat particulate materials have been used experimentally to deliver the pesticide directly to the target, to increase the adherence of the pesticide to the target, to minimize the dissipation losses of the pesticide to the environment, to prolong the life of the pesticide as applied, and to reduce the total amount of pesticide required for biological control. By minimizing the dissipation losses to the environment, the active ingredient of the pesticide is protected from rapidly evaporating or volatilizing from the spray formulation, from photodegradation by ultraviolet radiation due to environmental exposure, and from leaching from the application area into soil ground water. Reducing the volatility not only means the reduction of the amount of pesticide needed for biological control, but also the reduction of crop injury that a volatile pesticide can cause to neighboring crops or vegetation. Once sprayed in aqueous form, pesticides made with the oat particulate tend to form films on their target area, thus providing a reservoir for the active ingredient to slowly dissipate and biodegrade, releasing the active ingredient for biological control. Significant success has been achieved toward these goals. A notable difficulty in the agricultural use of such proteinaceous adjuvants has been the tendency of the particles derived from the trichomes (hairs) of the oat seed to clog the spray apparatus in certain applications. The present invention addresses this problem, providing a proteinaceous particulate for delivery of active ingredients, including pesticides, that has improved sprayability.

Summary of the Invention One embodiment of the present invention is a sprayable composition, comprising a particulate material derived from a seed grain by dehairing of the seed, milling, solvent extraction, and physical separation of milled particulates, such that the median particle size of the particulate material is between about 0.1 μm and 500 μm, and an active ingredient in intimate physical association with the particulate. In a further aspect of this preferred embodiment, the composition comprises an aqueous vehicle in which the particulate is suspended or dispersed. Preferably, the active ingredient and its associated particulate material on the one hand and the aqueous vehicle on the other hand are respectively combined in a ratio of about 0.01:1 to about 2:1. Advantageously, the active ingredient is a bioaffecting material. Preferably, the active ingredient is a pesticide, herbicide, insecticide, fungicide, nematicide, acaricide, gametocide, rodenticide, algicide, bactericide, molluscicide, growth regulator, safener, defoliant, desiccant, anti-desiccant, phero one, repellent, seed treater, ripener, synergist, wood preservative, adjuvant, surfactant, antifoam/defoaming agent, compatibility agent, deposition agent, dispersant, penetrant, spreading agent, wetting agent, adhesive agent, suspending agent, glidant or the like. Most preferably, the active ingredient is a pesticide, herbicide, fungicide, insecticide or surfactant.

In another aspect of the invention, there is provided a method for preparing a particulate material from seeds adapted to carry an active ingredient, wherein the seeds have hairs thereon, comprising the steps of dehulling the seeds, dehairing the seeds, milling the seeds, extracting the milled seeds in an organic solvent; and removing the solvent from the extracted milled seeds to obtain desolventized proteinaceous particulate material adapted to be combined with active ingredient and formed into a suspension capable of being sprayed without clogging of spray equipment. Preferably, the milling occurs in a pin mill and results in a proteinaceous particle size of about 100 μm to about 500 μm. In another aspect of this embodiment, the particles are further milled in a jet mill, resulting in a proteinaceous particle size between about 40 μm and about 200 μm. Preferably, the seeds are barley or sorghum; most preferably, the seeds are oats. Advantageously, the organic solvent is hexane. In another aspect of the invention, the particulate is combined with a pesticide. Advantageously, the oat hairs are removed by brushing or paddling.

Still another embodiment of the invention is an improved process for preparing a particulate oat fraction for use in delivering active ingredient wherein oats are milled into particulates and solvent extracted, the improvement comprising removing at least a portion of oat hairs from the oats prior to milling. Detailed Description of the Invention

We have discovered that removal of hairs from the seed material, preferably at a point prior to milling, significantly improves the sprayability of the final proteinaceous material. The present invention may be utilized with any combination of milling, extraction, and other processing steps. In other words, the removal of hairs from the seed, especially from oats, improves the sprayability of the resulting product, regardless of the other steps involved in the preparation of the particulate material.

In accordance with one embodiment of the present invention, the proteinaceous particulate material is prepared from seeds, by milling, extracting with organic solvents, typically hexanes or heptanes, to remove lipids, physically separating the particulates, and drying the resulting material . Although any seed from legumes or grains having hairs or hair-like projections can be used as the starting material, including barley, sorghum and oats, oats are highly preferred. Various milling, extracting and drying steps known in the art are contemplated. Dried oats may be ground by conventional techniques such as an attrition mill . As will be understood, in the grinding process, a broad spectrum of particle sizes are formed, for "fines" to "roughs". These particles may be separated using a conventional sieving apparatus. The fines, suitable for refined emulsion and fat substitute preparation (U.S. Patent No. 009A) , generally have an average particle size range from about 1 to about 100 μm, and the roughs generally have a particle size range from about 100 to about 600 μm. The sized particles are extraced with an organic solvent to remove lipids, followed by removal of excess solvent and drying of the remaining proteinaceous material.

Another suitable process for separating fractions of differing compositions of comminuted proteinaceous material from a variety of food sovrces including wheat, rye and barley is described by Oughton in U.S. Patent No. 4,154,728. The Oughton process comprises mixing the proteinaceous material with an aliphatic hydrocarbon or alcohol suitable to dissolve the lipids in the material. The wet slurry is distributed by centrifugation into frac ions which differ primarily in protein composition as well as starch composition. A similar process is applied in U.S. Patent Nos. 4,211,695 and 4,211,801, also to Oughton.

Regardless of the process by which the oats or other grains are milled, extra..ted, and separated, an important aspect of the present invention is the removal of the hairs from the grain, to reduce or substantially eliminate the presence of oat hairs in the final product. In practicing the invention with oats, for example, the raw oats are processed to remove larger debris, dehulled, and put on a gravity table to separate the oat groats from various contaminants, including hulls, weed seeds and the like. The resulting groats are then subjected to a polishing and brushing process to remove longitudinal projections called hairs. These hairs are found at one end of the groat as well as within the crease. They are formed of the same material as the pericarp (outer coating of the groat) and remain virtually intact during the milling process.

The dehairing process may be accomplished, for example, using a commercially available polishing/brushing machine. One such suitable machine consists of a mantle, a wire mesh cylinder, and rotating longitudinal brushes, and is a polishing/brushing machine sold under the trademark HA-800 by Westrup Corp. of Slagelse, Denmark, distributed by Westrup, Piano, TX. Other brush machines include those from Delta of Denmark, sold through Bratney Equipment Co., Des Moines, IA and Carter Day International, Minneapolis, MN. The use of other types of machines capable of removing oat hairs is also contemplated. For example, paddle-type machines are routinely used in the barley industry to remove the "beard", a tuft of hairs on one end of the roat. Such paddle-type machines are available from a number of manufacturers including Buhler, Minneapolis, MN; S. Howes Co., Inc., Silver Creek, NY; Codema, Inc., Minneapolis, MN; Forsbergs, Inc., Thief River Falls, MN and Crippen Manufacturing Co., Inc., Alma, MI. A more detailed description of the polishing/brushing process may be found in Example 1. In a preferred embodiment, the dehaired seeds are ground in an attrition mill. In a particularly preferred process, the dehaired oats are ground in a conventional (pin) mill to obtain a binodal distribution of median proteinaceous particle sizes. One node ranges from about 1 μm to about 100 μm. The larger node ranges from about 100 μm to about 1000 μm. In addition to milling parameters, median particle size can also be determined using a series of graduated sieves or particle size analysis. Screening and centrifugation may also be used to select desired particle size for the finished product. We have found that the intermediate sieve products having a median particle size of about 100 μm to about 500 μm, has the best starch/protein balance and physical properties for use as a controlled release ingredient.

The milled material in then extracted with a suitable nonpolar or polar organic solvent, such as isopropyl alcohol, methanol, ethanol, hexane, or heptane. Nonpolar solvents such as hexanes are particularly preferred. The lipid-extracted material is collected on a vibrating wire mesh screen and centrifuged. The material may also be subjected to a second solvent extraction, collection and centrifugation. Any residual solvent is then removed from the delipidated material by any number of known techniques, such as decanting, filtration, oven drying at slightly elevated temperatures (e.g., below about 90°C) , or subjecting the material to vacuum with or without the addition of minimal heat, or any combination of these techniques. In a preferred embodiment, the resulting particulates are advantageously carefully dried to remove any water, indigenous volatiles or residual solvents, maintaining an overall temperature in the production and drying processes of below about 90°C. The resulting proteinaceous particulate material is then collected. In a preferred embodiment, the material undergoes a final milling process to reduce the particle size to a range of about 1, 10, or 20 μm to about 100, 150, or 200 μm. One particularly suitable mill for such use is a jet mill such as that available from Hosoka a Micron Powder Systems, Summit, NJ under the trademark Alpine AFG Model 400 fluidized bed jet mill. Jet milling relies on air streams to propel the particles into each other and against the walls of the apparatus and is used to further reduce the size of conventionally ground material. In a particularly preferred embodiment, this final milling step is used to obtain a median proteinaceous particle si e of about 1 μm to about 200 μm, preferably about 20, 40, or 60 μm to about 80 or 120 μm.

After the initial pin milling, we have found that the particles having a median size greater than about 100 μm are more absorptive, and are better suited for use in carrying active ingredients, than the fines having a median particle size less than about 100 μm. For this reason, we prefer to separate the materials based on particle size after the initial pin milling, before or after extraction, and then reduce the particle size of the more absorptive particles into the desired range for spraying.

It should be noted that in a preferred embodiment of the present invention, the oats are prepared by a process that significantly modifies the native seed material only by milling, solvent extraction (preferably inorganic solvent extraction) , and physical separation of milled materials. In a preferred process, no water, polar solvent, alkaline extraction, or denaturing heat is utilized.

The proteinaceous material may then be used to form an emulsion by combining with an aqueous phase, a lipophilic phase, and a desired active ingredient spontaneously forming an oil-in-water emulsion at room temperature and with minimal agitation. Applicable emulsion composition ranges are from about 6 to about 60% weight of proteinaceous material (1-100% protein content dry weight) , from about 3 to about 50% weight lipophilic phase and froir about 30 to about 80% weight aqueous phase.

More preferably, tne proteinaceous material may be impregnated with the active ingredient, and can then be used to form an aqueous suspension or dispersion of the active ingredient, in which he particulate/active ingredient combination comprises from about 0.0_ % to about 10% by weight of the resulting aqueous composition. Specifically, the particulate material may ce used to entrap an active agent by mixing the material with t.ie agent, optionally with a suitable organic solvent. Such solvents include aliphatic hydrocarbons such as hexane and heptane as well as alcohols including isopropanol and ethanol. One of ordinary skill in the art will appreciate that many suitable polar and nonpolar organic solvents are within the scope of the present invention. In a preferred embodiment, the amount of active agent added is between about 10% and about 60%, based on the total weight of the final product. In a particularly preferred embodiment, the amount of active agent added is between about 25% and about 50%, based on the total weight of the final product. The solvent is then removed and the resulting proteinaceous material is dried. Advantageously, the dried powder is jet milled or air milled to obtain smaller particle sizes and to remove agglomerated material. However, if the proteinaceous material containing the active ingredient is processed through an extruder, the final jet milling or air-milling is not required since extruders have sufficient temperature controlled grinding capabilities that reduce particle size for spray applications. Proteinaceous carriers from which the hairs have not been removed can cause problems in agricultural use because suspensions containing pesticides trapped within oat proteinaceous particulate material sometimes clogs these sprayers. This problem is addressed through use of the present invention. In another preferred embodiment, the proteinaceous material containing an adsorbed active agent is diluted into a tank containing water and optionally one or more of a dispersion agent, antifoaming agent or surfactant to enhance dispersion of the material in the water. The concentration of the product containing the proteinaceous carrier in the tank is preferably between about 0.01% and 5%. The resulting suspension will advantageously not clog the nozzles of industrial sprayers equipped with a 50 mesh (300 μm) screen. The preparations using proteinaceous material derived from dehaired grains does not obstruct these screens and provides good sprayability.

The particular active ingredients incorporated into the particulate emulsion include those used in the cosmetic, pharmaceutical, food and pesticide industries. These ingredients include, for example, insecticides, insecticidal proteins such as those isolated from the bacterium Bacillus thuringiensis (BT toxin) , insect repellents (e.g. N,N-diethyl- m-toluamide) , herbicides, fungicides, fertilizers, micronutrients, surfactants, fragrances, deodorants, food flavoring agents, pharmaceuticals, bactericides or any material that may advantageously be applied to a surface in a proteinaceous particulate emulsion, suspension, or dispersion.

Nonlimiting examples of suitable herbicides include: thiazopyr, dithiopyr, asula , bromacil, bromoxynil, butachlor, butylate, chloroxuron, chlorotoluron, clomazone, desmediphan, diallate, triallate, dichlobenil, dichlofop methyl, diphenamid, dipropetryn, diuron, EPTC, thiameturon, fenac, fenuron, fluometuron, hexazinone, isoproturon, isouron, lactofen, alachlor, acetochlor, trifluralin, methabenzthiazuron, metolachlor, metribuzin. norflurazon, oryzalin, oxyfluorfen, phenmedipha , propachlor, propanil, prometryn, pronamide, siduron, tebuthiuron, terbutryn, etc.

Nonlimiting examples of suitable fungicides include: chloroneb, cymoxanil, captan, thiophanate methyl, thiabendazole, chlorothalonil, dichloran, captafol, prochloraz, iprodione, vinclozolin, metalaxyl, flutriafol, flusilazol, hexaconazole, fenarimol, etc.

Nonlimiting examples of suitable insecticides include: aldicarb, parathion, chlorpyrifos, synthetic pyrethroids, carbofuron, carbaryl, deltamethrin, tetrachlorvinphos, etc. Any relevant compound able to be incorporated into or emulsified or dispersed by the proteinaceous particulate material is within the scope of the present invention.

The use of the present invention is particularly advantageous for pesticides, such as fungicides, insecticides, nematicides, gametocides, safeners, adjuvants and herbicides, because the proteinaceous material aids in the adherence of the active agent to the target and promotes prolonged action of the active compounds as they are released over time. Thus, less material may be used since the proteinaceous particle protects the compounds from immediate dispersal and degradation. Consequently, less pesticide is released into the environment. The compounds will also persist at the site of application for a longer period of time. In addition, since the protein particles are fully biodegradable, no toxic degradation products are released.

The quantity of the active ingredient will vary depending on the desired dosage or amount of active ingredient to be delivered in terms of either total volume or total' elapsed delivery time, the viscosity and/or volatility of the active ingredient, and other parameters that will be apparent to one of skill in the art. Typically, as a starting point, one should combine the active ingredient with an equivalent weight of particulate material, disperse that material in an aqueous vehicle (using a conventional surfactant if necessary) to give perhaps 50% of the conventional dose or concentration of active ingredient, and then spray the material on the target to determine the efficacy of the resulting composition. By increasing or decreasing the amount of active ingredient and the ratio of active ingredient to particulate material, one can readily determine the optimum parameters for any particular application. The following examples illustrate particular preferred embodiments of the invention; however, it is intended that the entire disclosure, and not just the examples, be used to determine the scope of the present invention.

Example 1 Production of dehaired proteinaceous particulate material

Dried, dehulled Tibor oats, a patented strain developed by Agriculture Canada, were dehaired using a Westrup HA-800 polishing/brushing machine. The unit consists of a mantle, wire mesh cylinder and four rotating longitudinal brushes. Both the screens and the brushes are removable and can vary in coarseness. In addition, the distance between the screens and the brushes can be changed. Other variables include the rpm of the brushes, the input rate of the groats (500 to 1300 kg/hr) and the retention time within the unit. A 15 mesh screen (fairly coarse) with an extremely pliable brush having two inch bristles was used, although coarser brushes and finer screens are also contemplated. The distance between the brushes and mantle was about 1.5 to about 2 inches initially. The success of the hair removal was determined by microscopic examination of a sample of the groats using a dissecting microscope. Samples were taken from the outlets of both the brush machine and the screen. Nearly all of the groats lost the "tuft" of hair at the end, along with the majority of hairs in the crease. Samples were taken about every 15 minutes, and adjustments were made to the feed rate, retention time and brush clearance as necessary.

Dehaired oats were ground using a pin mill . During the grinding process, a broad spectrum of particle sizes are formed, from "fines" to "roughs" which are separated using conventional sieving apparatus. The fines were collected and extracted with 2.5 to 3 parts hexane by stirring for between 1 and 3 hours to solubilize the lipid materials. The solid material was collected on a 200 mesh vibratory screen and subjected to another round of hexane extraction. The solution was centrifuged at 4,500 x g to layer out the insoluble proteinaceous materials. The hexane was then carefully decanted and the solid materials dried at room temperature and at reduced humidity (i.e., relative humidity not exceeding 50%), resulting in a particulate proteinaceous material.

The proteinaceous particulate material from dehaired oats was used to form a sprayable aqueous composition containing an active agent as described in the following example.

Example 2 Formation of pesticide-containing composition A stable herbicide-containing particulate preparation was prepared in the following manner. Two hundred and twenty grams of the large proteinaceous particle prepared in accordance with Example 1 and 8 grams of Stepsperse DF-200

(Stepan Chemical Co., Chicago, IL) were slurried with 684 grams of acetone in a 2 liter flask using manual agitation.

To this slurry was added 171 grams of technical oxyfluorofen (70% active) dissolved in 170 grams of acetone at a temperature of about 50°C. The resulting mixture was manually agitated until it was visually homogenous. The resulting material was attached to a rotary evaporator and the acetone was removed at a temperature of about 40°C and a vacuum of approximately 15 psi. The resulting powder was air dried to remove residual solvent. The powder was then jet milled using a 2 inch Micronizer (Sturtevant, Inc., Boston, MA) . Ten grams of the resulting powder was added to one liter of water and the mixture was shaken for 5 minutes. The resulting product was sprayed using a standard C0₂-powered backpack sprayer equipped with eight 8002 flat fan spray nozzles equipped with 50 mesh nozzle screens. The spray patterns were observed during spraying and when spraying was complete, the nozzle screens were examined. No changes in the spray pattern which would have indicated plugged nozzles were observed and only a small amount of residue was observed on the nozzle screens. Example 3

Sprayability of proteinaceous emulsion without dehairing

A product identical to that of Example 2, except that the dehairing step was omitted from the production of the large proteinaceous particles was prepared and sprayed under the identical test conditions. Variations in the spray patterns of more than one nozzle that were attributable to plugging of the nozzles was observed. When the nozzles were disassembled after spraying, a considerably larger amount of residue was observed on the nozzle screens than in Example 2. In addition, one nozzle was observed to be partially blocked by a long, thin particle which had passed through the screen and lodged in the nozzle orifice. The appearance of this particle under the microscope was consistent with that of an oat hair.

Claims

WHAT IS CLAIMED IS:

I. A sprayable composition, comprising: a particulate material derived from a seed grain by dehairing of the seed, milling, solvent extraction, and physical separation of milled particulates, such that the median particle size of the particulate material is between about 0.1 μm and about 500 μm; and an active ingredient in intimate physical association with said particulate.

2. The composition of Claim 1, further comprising an aqueous vehicle in which said particulate is suspended or dispersed.

3. The composition of Claim 2, wherein the active ingredient and its associated particulate material on the one hand and the aqueous vehicle on the other hand are respectively combined in a ratio of about 0.01:1 to about 2:1.

4. The composition of Claim 1, wherein the active ingredient is a bioaffecting material.

5. The composition of Claim 1, wherein the active ingredient is a pesticide.

6. The composition of Claim 1, wherein the active ingredient is an herbicide.

7. The composition of Claim 1, wherein the active ingredient is an insecticide.

8. The composition of Claim 1, wherein the active ingredient is a fungicide.

9. The composition of Claim 1, wherein the active ingredient is a nematicide.

10. The composition of Claim 1, wherein the active ingredient is an acaricide.

II. The composition of Claim 1, wherein the active ingredient is a gametocide.

12. The composition of Claim 1, wherein the active ingredient is a rodenticide.

13. The composition of Claim 1, wherein the active ingredient is a safener.

14. The composition of Claim 1, wherein the active ingredient is an algicide.

15. The composition of Claim 1, wherein the active ingredient is a bactericide.

16. The composition of Claim 1, wherein the active ingredient is a biocontrol agent.

17. The composition of Claim 1, wherein the active ingredient is a defoliant.

18. The composition of Claim 1, wherein the active ingredient is a desiccant.

19. The composition of Claim 1, wherein the active ingredient is an anti-desiccant.

20. The composition of Claim 1, wherein the active ingredient is an insect growth regulator.

21. The composition of Claim 1, wherein the active ingredient is a molluscicide.

22. The composition of Claim 1, wherein the active ingredient is a pheromone.

23. The composition of Claim 1 wherein the active ingredient is a repellent.

24. The composition of Claim 1 wherein the active ingredient is a seed treater.

25. The composition of Claim 1, wherein the active ingredient is a synergist.

26. The composition of Claim 1, wherein the active ingredient is a wood preservative.

27. The composition of Claim 1, wherein the active ingredient is an adjuvant.

28. The composition of Claim 1, wherein the active ingredient is a surfactant.

29. The composition of Claim 1, wherein the active ingredient is an antifoam or defoaming agent.

30. The composition of Claim 1, wherein the active ingredient is a compatibility agent.

31. The composition of Claim 1, wherein the active ingredient is a deposition agent.

32. The composition of Claim 1, wherein the active ingredient is a dispersant.

33. The composition of Claim 1, wherein the active ingredient is a penetrant.

34. The composition of Claim 1, wherein the active ingredient is a spreader or wetting agent.

35. The composition of Claim 1, wherein the active ingredient is a sticker, extender or wetting agent.

36. The composition of Claim 1, wherein the active ingredient is a suspending agent.

37. The composition of Claim 1, wherein the active ingredient is a glidant.

38. A method for preparing a particulate material from seeds adapted to carry active ingredient, wherein said seeds have hairs thereon, comprising the steps of: dehulling said seeds; dehairing said seeds; milling said seeds; extracting said milled seeds in an^' organic solvent; removing said solvent from said extracted milled seeds to obtain desolventized proteinaceous particulate material adapted to be combined with active ingredient and formed into a suspension capable of being sprayed without clogging of spray equipment.

39. The method of Claim 38, wherein said milling occurs in a pin mill.

40. The method of Claim 39, wherein said milling results in a proteinaceous particle size of about 100 μm to about 1000 μm.

41. The method of Claim 39, further comprising milling in a jet mill.

42. The method of Claim 39, further comprising milling in an air mill.

43. The method of Claim 41, wherein said jet milling results in a proteinaceous particle size between about 40 μm and about 200 μm.

44. The method of Claim 38, wherein said seeds are barley or sorghum.

45. The method of Claim 38, wherein said seeds are oats.

46. The method of Claim 38, wherein said organic solvent is hexane.

47. The method of Claim 38, further comprising the step of combining said particulate with a pesticide.

48. The method of Claim 38, wherein said hairs are removed by brushing.

49. The method of Claim 38, wherein said hairs are removed by paddling.

50. In a process for preparing a particulate oat fraction for use in delivering active ingredient wherein oats are milled into particulates and solvent extracted, the improvement comprising removing at least a portion of oat hairs from the oats prior to milling.