Title of Invention	"A COATING MEMBRANE"
Abstract	A coating membrane comprising of one or more particulate layers such as herein described, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate.

Full Text

-1A Cross-reference to Related Applications This application is a continuation-in-part of U.S. Patent Application No. 08/812301, filed March 5, 1997, which is incorporated herein by reference for its teachings related to the invention disclosed herein. Field of the Invention The present invention is directed to horticultural substrates treated with a particulate membrane and methods for controlling pests associated with such substrates and for providing enhanced horticultural effects. Background of the Invention The prior art has discussed the use of certain inert particulate solids as insecticides, see for example; Driggers, B.F., "Experiments with Talc and Other Dusts Used Against Recently Hatched Larvae of the Oriental and Codling Moths," J. Econ. Ent., 22 327-334 (1929); Hunt, C.R., "Toxicity of Insecticide Dust Diluents and Carriers to Larvae of the Mexican Bean Beetle," J. Econ. Ent., 40 215-219 (1947); p. Alexander, J. A. Kitchener and H. V. A. Briscoe, "Inert Dust Insecticides," Parts I, II, and III, Ann. Appl. Biol., 31 143-159, (1944); and US patents 3,159,536 (1964) and 5,122,518 (1992), each of which is incorporated herein by reference with regard to its teachings relating to particulate materials. -2- Plant diseases are caused by various pathogens, e.g., fungi, bacteria and virus, and these diseases have generally been controlled commercially by the use of chemical pesticides. For example, commercial fungicides generally belong to the following types of chemical compounds: inorganic (copper or sulfur based), organic {anilines, anilides, dithiocarbamates, halogen compounds and heterocyclic nitrogen compounds), antibiotics and biologicals. Chemically toxic fungicides and bactericides are often formulated with inert particulates. Inert particulates, however, have been shown to be ineffective toward these plant pests when applied by themselves (see W. 0. Cline and R. D. Milholland, "Root Dip Treatments for Controlling Blueberry Stem Blight Caused by Botryosphaeria dothidea in Container-Grown Nursery Plants," Plant Disease 76 136-138 {1992)). Furthermore, not only have inert particulates been shown to be ineffective in plant disease control, but it has been reported by S. K. Bhattacharyya and M. K. Basu, "Kaolin Powder as a Fungal Carrier," Appl. Envir. Microbio. 44. 751-753 (1982) that kaolin powder may be used to carry and preserve an Aspergillus sp. for at least 90 days. In another report, S. M. Lipson and G. Stotzky, "Effect of Kaolinite on the Specific Infectivity of Reovirus," FEMS Micr. Let. XL 83-88 (1986), it was reported that the infectivity of enteric viruses (e.g., poliovirus, rotavirus and reovirus) is prolonged when these viruses are adsorbed on naturally occurring particulates (sediments, clay materials) in terrestrial and aquatic environments. -3 O. Ziv and R.A. Frederiksen, "The Effect of Film-forming Anti-transpirants on Leaf Rust and Powdery Mildew Incidence on Wheat," Plant Path. 36 242-245 (1987); M. Kamp, "Control of Erysiphe cichoracearum on Zinnia elegans, with a Polymer-based Antitranspirant," Hort. Sci. 20 879-881 (1985); and J. zekaria-Oren and Z. Eyal, "Effect of Film-forming Compounds on the Development of Leaf Rust on Wheat Seedlings," Plant Dis. 75 231-234 (1991)} discuss the use of anti-transpirant polymer films to control disease. Of course, the use of anti-transpirants is undesirable because they reduce the exchange of necessary gases on the surface of living plants. For prior art regarding horticultural effects see, for example, Byers, R.E., K.S. Yoder, and G. E. Mattus, "Reduction in Russetting of 'Golden Delicious' Apples with 2,4,5-TP and Other Compounds," HortScience 18:63-65); Byers, R.E., D.H. Carbaugh, and C.N. Presley, "'Stayman' Fruit Cracking as Affected by Surfactants, Plant Growth Regulators, and Other Chemicals," J, Amer. Soc. Hort, Sci. 115:405-411 (1990); Durner, E.F., and T.J. Gianfagna, "Peach Pistil Growth Inhibition and Subsequent Bloom Delay by Midwinter Bud Whitewashing," HortScience 25:1222-1224 (1990); and M.N. Westwood, Temperate -zone Pomology. page 313 W.H. Freeman and Co. (1978) . Therefore, there is still a need for cost effective inert, nontoxic improved agents for pest control and for enhanced horticultural effects and methods for their use. -4 - Summary of the Invention This invention relates to horticultural substrates where the surface of said substrates is coated with a particulate membrane and to methods for pest control and enhanced horticultural effects by forming said membrane on the surface of the horticultural substrate. In one embodiment, this invention relates to coated substrates comprising a horticultural substrate wherein the surface of said substrate is coated with a membrane comprising one or more particulate layers, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate. In another embodiment, this invention relates to a method for pest control on horticultural substrates which comprises forming on the surface of said substrate a membrane comprising one or more particulate layers, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate. In still another embodiment, this invention relates to a method for providing enhanced horticultural effects which comprises forming on the surface of a horticultural substrate a membrane comprising one or more particulate layers, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate. -5- Brief Description of the Drawings Figure 1 is a scanning electron micrograph of an untreated petunia petal. Figure 2 is a scanning electron micrograph of a petunia petal coated with a membrane of octylsilane treated calcined kaolin particles. Figure 3 is a scanning electron micrograph of a petunia petal coated with a membrane of vinyl silane calcined kaolin particles. Figure 4 is a scanning electron micrograph of a petunia petal coated with a membrane of methylethoxysiloxane treated calcined kaolin particles. Figure 5 is a scanning electron micrograph of a petunia petal coated with a membrane of a calcined kaolin treated with a siloxane material. Figure 6 is a scanning electron micrograph of a petunia petal coated with a membrane of a calcined kaolin. Detailed Description of the Invention The horticultural substrates to which this invention relates are agricultural and ornamental crops, including those selected from the group consisting of fruits, vegetables, trees, flowers, grasses, seeds, roots, and landscape and ornamental plants. The membranes of this invention comprise one or more particulate layers, said layers comprising one or more particulate materials, said particulate materials being finely divided. The finely divided particulate materials which make up the particulate membrane of this invention may be -6- hydrophilic or hydrophobia materials and the hydrophobic materials may be hydrophobic in and of themselves, e.g., mineral talc, graphite, and Teflon® or may be hydrophilic materials that are rendered hydrophobic by application of an outer coating of a suitable hydrophobic wetting agent (e.g., the particulate material has a hydrophilic core and a hydrophobic outer surface). Typical particulate hydrophilic materials useful for the purposes of this invention include: minerals, such as calcium carbonate, talc, kaolin (both hydrous and calcined kaolins, with calcined kaolins being preferred), bentonites, clays, attapulgite, pyrophyllite, wollastonite, silica, feldspar, sand, quartz, chalk, limestone, precipitated calcium carbonate, diatomaceous earth and barytes; functional fillers such as microspheres (ceramic, glass and organic), aluminum trihydrate, pyrogenic silica, ceramic fibers and glass fibers; and pigments such as colorants or titanium dioxide. The surfaces of such materials can be made hydrophobic by addition of hydrophobic wetting agents. Many industrial mineral applications, especially in organic systems such as plastic composites, films, organic coatings or rubbers, are dependent upon just such surface treatments to render the mineral surface hydrophobic; see, for example, Jesse Edenbaum, Plastics Additives and Modifiers Handbook. Van Nostrand Reinhold, New York, 1992, pages 497-500 which is incorporated herein by reference for teachings of such surface treatment materials and their application. So-called coupling agents such as fatty acids and silanes are -7- commonly used to surface treat solid particles as fillers or additives targeted to these industries. Such hydrophobic agents are well known in the art and common examples include: chrome complexes such as Volvan® and Quilon® obtained from DuPont; organic titanates such as Tilcom® obtained from Tioxide Chemicals; organic zirconate or aluminate coupling agents obtained from Kenrich Petrochemical, Inc.; organofunctional silanes such as Silquest® products obtained from Witco or Prosil® products obtained from PCR; modified silicone fluids such as the DM-Fluids obtained from Shin Etsu; and fatty acids such as Hystrene® or Industrene® products obtained from Witco Corporation or Emersol® products obtained from Henkel Corporation (stearic acid and stearate salts are particularly effective fatty acids and salts thereof for rendering a particle surface hydrophobic). Examples of preferred particulate materials suitable for the purposes of this invention that are commercially available from Engelhard Corporation, Iselin, NJ are the siloxane treated calcined kaolins sold under the trademark Translink®, and stearic acid treated ground calcium carbonates commercially available from English China Clay under the trademarks Supercoat® and Kotamite® The term "finely divided" when utilized herein means that the particulate materials have a median individual particle size below about 10 microns and preferably below about 3 microns and more preferably the median particle size is about one micron or less. Particle size and particle size distribution as used herein are measured with a Micromeritics Sedigraph 5100 Particle Size Analyzer. Measurements were recorded in deionized water - 8 - for hydrophilic particles. Dispersions were prepared by weighing 4 grams of dry sample into a plastic beaker adding dispersant and diluting to the 80 ml mark with deionized water. The slurries were then stirred and set in an ultrasonic bath for 290 seconds. Typically, for kaolin 0.5% tetrasodium pyrophosphate is used as a dispersant; with calcium carbonate 1.0% Calgon T is used. Typical densities for the various powders are programmed into the sedigraph , e.g., 2.58 g/ml for kaolin. The sample cells are filled with the sample slurries and the X-rays are recorded and converted to particle size distribution curves by the Stokes equation. The median particle size is determined at the 50% level. Preferably, the particulate material has a particle size distribution wherein up to 90% by weight of the particles have a particle size of under about 10 microns, preferably below about 3 microns and more preferably about one micron or less. The particulate materials particularly suitable for use in this invention are inert, nontoxic and hydrophobic. As used herein "inert" particulate materials are particles that are not physiological poisons, that is, the particulate materials of this invention do not, as their primary function, kill pests. While not being bound by theory, it is believed that the pest control of this invention is achieved primarily by prophylactic means rather than primarily through the destruction of the unwanted pests. The particulate materials are preferably nontoxic meaning that in the limited quantities needed for -9- effective pest control or enhanced horticultural effect such materials are not considered harmful to horticultural substrate, animals, the environment, the applicator and the ultimate consumer. The preferred particulate materials of the instant invention are hydrophobic. Hydrophobicity refers to the physical property of a surface to dislike or repel water. Most mineral particle surfaces are hydrophilic, i.e., water liking. The terms hydrophobic and hydrophilic are. not always accurately used in the literature and both are often confused with similar terms such as, lipophilic or lipophobic, oleophilic or oleophobic, lyophilic or lyophobic, and polar or nonpolar. Hydrophobicity can be described in more quantitative terms by using contact angle measurements. The contact angle is defined by the equilibrium forces that occur when a liquid sessile drop is placed on a smooth surface. The tangent to the surface of the convex liquid drop at the point of contact among the three phases, solid (S), liquid (L) and vapor (V) is the contact angle as illustrated in the following figure. The relationship between the surface tension of the solid-vapor (Ysv) , liquid-vapor (YLV ) and solid-liquid (YSL) can be defined by the following Young's equation: F = Ypcos -10- where F = wetting force; Y = liquid surface tension; and p = wetting perimeter. If the water droplet spreads out on the surface the contact angle is less than 90 degrees and the surface is hydrophilic. If the surface is hydrophobic then the contact angle is greater than 90 degrees. Thus, 180 degrees is the maximum hydrophobicity that a surface can have. Many surfaces change their surface energy upon contact with water (see J. Domingue, Amer. Lab, Oct 1990). Dynamic contact angle measurements provide both an advancing and receding contact angle. The advancing contact angle is a measurement of the surface hydrophobicity upon initial contact with a liquid, while the receding contact angle measures the hydrophobicity after the surface has been wetted with a liquid. Thus, for the purposes of this invention, "hydrophobic" or "hydrophobicity," when used in reference to the particulate materials useful for the purposes of this invention, such particles may have either an advancing and/or receding contact angle of greater than 90°. Preferred materials have receding contact angles of greater than 90°. The dynamic contact angles referred to herein are based on a gravimetric principle of the Wilhelmy plate technique and are determined by measurement on the Dynamic Contact Angle Instrument which can measure both advancing and receding contact angles of powdered samples. A dynamic contact angle analysis system (model DCA 315) from ATI Cahn Instruments Inc. was used for all -11- contact angle measurements referred to and reported herein. The surface tension (Y) of deionized water was determined with a standard platinum calibration plate. Powder samples were deposited on dual sided adhesive tape. The perimeter (p) of the tape was determined with a caliper. The impregnated tape was placed in the DCA 315 and lowered and raised in the deionized water at a rate of 159 microns/second for two immersion cycles. The contact angles were determined from the advancing and receding wetting hysteresis curves of the first immersion cycle. Most samples were prepared and run in duplicate and the results averaged. The data analysis was made with a WinDCA software for Windows diagnostic package from the manufacturer, ATI Cahn Instruments Inc. Representative contact angle values for a variety of inert particulate materials are given in Table I. Although many of the powders listed are hydrophilic and have advancing and receding contact angles less than 90°, some hydrophobic particles as measured by the advancing contact angle, for example talc, become hydrophilic upon wetting. -12- Table I Contact Angle Values of Powders Particle Advancing Contact Angle (°) Receding Contact Angle (°) Calcium Carbonate1 28.4 32.5 Calcium Carbonate2 37.8 38.1 Calcium Carbonate3 (ST) 180 171.1 Barytes4 32.2 30.3 Mica5 42.3 39.9 Mica6 31.5 25.0 Silica7 38.5 38.2 Diatomite8 39.4 35.3 ATH9 38.7 0 Wollastonite 10 23.1 27.5 Wollastonite 11 9.4 14.1 Talc12 180 12.8 Talc11 159. 2 11.5 Feldspar14 35.9 39.2 Nepheline Syenite14 19.4 25.4 Kaolin hydrous14 29 30.1 Kaolin calcined14 26 20.5 ST= Surface Treated 1. Atomite (ECC Int.) 2. GS 6532 (Georgia Marble) 3. Kotamite (ECC Int.) 4. Bartex 65 (Hitox) 5. WG 325 (KMG Minerals ) 6. C-3000 (KMG Minerals) 7. Novacite* L-207A (Malvern Min Co.) 8. Diafil 340 (CR Mineral Corp.) 9.Alcan SF (Alcan Chemicals) 10. NYAD 1250 (NYCO) 11. Wollastokup(NYAD) 12. Vantalc 6H (RT Vanderbilt) 13. Vertal 710 (Luzenac Amer Inc.) 14. Minspar 4 (K-T Feldspar Corp) 15. Minex 10 (Unimin) 16. ASP 900 (Engelhard Corp) 17. Satintone W (Engelhard Corp) Hydrophilic surfaces can be made hydrophobic by-addition of hydrophobic wetting agents as shown in Table -13- II for hydrous and calcined kaolin. However, not all hydrophobic surface treatments render hydrophobicity to a particle as shown in Table II. Table II Surface Treated Kaolin Particles Surface Treatment (1%) Hydrous Kaolin Advancing Angle (°) Hydrous Kaolin Receding Angle (°) Calcined Kaolin Advancing Angle (°) Calcined Kaolin Receding Angle (°) no treatment 31 30 26 21 Stearic acid1 155.5 0 166 102 Octyltriethoxysilane3 158 0 180 180 Vinyltriethoxysilane3 120 22 164 140 polydimethylsiloxane4 linear 27 26 24 26 methylethoxysiloxane polymer3 89 24 180 154 polydimethyl siloxane cyclic 112 45 155 154 1. Industrene 7018 (Witco) 2. A-137 (Witco) 3. A-151 (Witco) 4. L-45 (Witco) 5. A-272 (Witco) 6. CG-4491 (HULS America Inc.) The preferred hydrophilic core particles are those, which when treated with a hydrophobic wetting agent and are applied to the surface of a horticultural substrate, form a membrane on the substrate. Examples of such particles are calcium carbonate and kaolin. Calcined kaolin is preferred to hydrous kaolin. As previously discussed, this invention relates to horticultural substrates wherein the surface of said substrate is coated with a membrane comprising one or more particulate layers. This membrane allows for the exchange of gases on the surface of said substrate. The -14- gases which pass through the membrane are those which are typically exchanged through the surface skin of living plants. Such gases typically include water vapor, carbon dioxide, oxygen, nitrogen and volatile organics. The portion of a substrate to be covered with said membrane is within the skill of the ordinary artesian. Optimally, the substrate is fully covered with said membrane, and although diminished disease control and/or horticultural effects may result, less than full substrate coverage is within the scope of this invention; preferably, however, the substrate is substantially covered. Reference is made to U.S. Serial No. , filed concurrently herewith on , entitled "Method for Providing Enhanced Photosynthesis" and to U.S. Serial No. , filed concurrently herewith on , entitled "Method for Protecting Surfaces from Arthropod Infestation" which are incorporated herein by reference for their teachings regarding methods for insect control and improved photosynthesis. Preferably, the membranes of this invention are sufficiently continuous so as to provide effective control of disease. The membrane may have imperfections such as gaps or voids, but such imperfections should not be so large as to materially affect the disease control of such membrane. Such gaps or voids typically will not exceed about 5 , and are preferably less than about 1 . In another preferred embodiment, the membrane is water repellent. The membrane may be formed by applying one or more layers of finely divided particulate material until a membrane is formed of sufficient thickness and continuity to be an effective -15- disease control barrier, i.e., the particles on the surface of the substrate are so closely associated that pathogens are unable to penetrate the particulate coating and infect the underlying horticultural substrate. For example, this can typically be accomplished by applying in a uniform manner from about 25 up to about 3000 micrograms of particulate material/cm2 of substrate for particles having specific density of around 2-3 g/cm3. In addition, environmental conditions such as wind and rain may reduce coverage of the membrane and, therefore, it is3 within the scope of this invention to apply the particles one or more times during the growing season of said horticultural crop so as to maintain the desired effect of invention. This particulate membrane may be prepared by applying a slurry of finely divided particles in a volatile liquid such as water, a low boiling organic solvent or low boiling organic solvent/water mixture. One or more layers of this slurry can be sprayed or otherwise applied to the substrate. The volatile liquid is preferably allowed to evaporate between coatings. Surfactants or dispersants may be useful in preparing an aqueous slurry of the particulate materials of this invention. The membrane of this invention may be hydrophilic or hydrophobic, but is preferably hydrophobic. Normal dusting of particles, aside from not being commercially practical on a large scale due to drift and inhalation hazards, is not effective at forming a membrane on a horticultural substrate suitable for disease control. The membrane of this invention may be formed, however, by carefully applying the finely divided -16- particles to the substrate, e.g., with a paint brush. While not being bound by theory, it is believed that the one or more layers of finely divided particulate material form a membrane due to particle to particle cohesion of evenly distributed, closely associated particles. The low boiling organic liquids useful in the present invention are preferably water-miscible and contain from 1 to 6 carbon atoms. The term "low boiling" as used herein shall mean organic liquids which have a boiling point generally no more than 100°C. These liquids enable the particulate solids to remain in finely divided form without significant agglomeration. Such low boiling organic liquids are exemplified by: alcohols such as methanol, ethanol, propanol, i-propanol, i-butanol, and the like, ketones such as acetone, methyl ethyl ketone and the like, and cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran. Combinations of the above-mentioned liquids can also be employed. Methanol is the preferred low boiling organic liquid. Low boiling organic liquids may be employed in applying the particles to form the membranes of this invention. Typically, the liquids are used in an amount sufficient to form a dispersion of the particulate material. The amount of liquid is typically up to about 30 volume percent of the dispersion, preferably from about 3 up to about 5 volume percent, and most preferably from about 3.5 to about 4.5 volume percent. The particulate material is preferably added to a low boiling organic liquid to form a slurry and then this slurry is diluted with water to form an aqueous dispersion. The -17- resulting slurry retains the particles in finely divided form wherein most of the particles are dispersed to a particle size of less than about 10 microns. This invention also provides methods for pest control and enhanced horticultural effects by forming said membrane on the surface of the horticultural substrate. The foregoing discussions regarding i) said membrane being comprised of one or more layers of particulate material, ii) said particulate material being finely divided, iii) said membrane allowing for the transpiration of water vapor from said substrate through said membrane, and iv) application techniques for applying said layers to the horticultural substrate, as well as the specific embodiments discussed herein, also apply to these methods. The pests controlled by this invention refer to arthropods including insects, mites, spiders and related animals and diseases of various pathogens such as fungi, bacteria and virus. Diseases can be transmitted in a number of ways such as wind currents, water splash and/or arthropod transmission. Examples of diseases commonly caused by wind currents and water splash include: Fire blight (bacteria--Erwinia amylovora) , apple scab (fungus--Venturia inaequalis), Potato Blight (fungus-Phytophthora infestans), Soft rots (fungus--Botrytis cinerea), Leaf blight and leaf spot (bacteria--Xanthomonas sp.), and bacterial leaf spot and leaf blight (bacteria--Pseudomonas sp.). Examples of diseases commonly caused by arthropod transmission are the fungus disease, Dutch Elm disease, of American Elm by the European elm beetle; the bacterial disease, Fire blight, -18 of apples and pears by flies, beetles and other insects; the virus disease, Curly Top, of sugar beets by the beet leaf hopper. Disease control also applies to those secondary infections of wound sites on a plant that results from arthropod feeding such as brown rot infection of stone fruits that results when the disease organism enters the plant through plum curculio feeding sites. This invention can also provide the benefit of enhanced horticultural effects including improved color, smoother fruit surface, increased soluble solids, e.g., sugars, acidity, etc., reduced bark and fruit cracking, reduced plant temperature and reduced russetting. The following examples are illustrative of embodiments of the invention and are not intended to limit the invention as encompassed by the claims forming part of the. application. EXAMPLE 1 This example demonstrates that coating a plant substrate with a membrane of finely divided particles greatly reduces the degree of infection as compared to a substrate not coated with a particulate membrane. Efficacy of various particulate membranes toward disease control was demonstrated by screening evaluations of Botrytis cinerea on strawberry petals {Fragaria x ananassa Pucheene). All preparations in Tables III and IV were made by applying suspensions of the particles listed in the table prepared by first dispersing 5 grams of the identified particle in 10 ml methanol which is then brought to 100 ml with deionized water. Petals were then -19 sprayed with this suspension using a Paasche air brush to run off. The petals were allowed to air dry and then 10 l of Botrytis inoculum (3,6 x 107 spores/ml) was added over the petals. The petals were then incubated in a 100% humidity chamber for 24 hours. Table III Fungus Efficacy of surface treated and untreated particles Particle % Infection after 24 hrs Advancing Contact Angle (°) Receding Contact Angle Control - no particles 88.9 ~ - Methanol 76.5 - - Kaolin hydrous [ST]1 73.0 155.5 0 Kaolin calcined7 68.0 19.4 20.5 Kaolin hydrous3 63.8 29 30.1 Kaolin calcined 1ST]* 62.0 166 102 Calcium Carbonate* S7.0 23.4 32.5 Talc* 49.3 180 12.8 Calcined Kaolin (ST]' 44.7 146 128 Calcium Carbonate CSTj* 36.8 180 171 Translink® 77 23.6 153 120 1. ASP 900 {Engelhard Corporation) treated with stearate 2. Satintone w {Engelhard Corporation) 3. ASP 900 (Engelhard Corporation) 4. Satintone w (Engelhard Corporation) treated with stearate 5. Atomite* (ECC Int.) 6. Vantalc* 6H Infection was measured by the presence of a necrotic -20- lesion characteristic of a Botrytis infection. The data was analyzed by the Duncan's multiple range test (P=0.05) on the arcsine transformed percentages and are presented as untransformed mean for convenience). EXAMPLE 2 Performing the same evaluations and comparing surface treated particles to untreated particles of calcined kaolin gave the results in Table IV. Table Iv Fungus Efficacy of surface treated calcined kaolin Particles % Infection after 24 hrs Advancing Contact Angle Control - no particles 8B ™ Figure 1 octylsilane treated1 o Satintone W 25 180 180 Figure 2 vinylsilane treated1 o Satintone w 29 164 140 Figure 3 methylethoxysil oxane treated1 o Satintone w 25 180 154 Figure 4 Translink* 77 0 153 120 Figure 5 Satintone* W - - Figure 6 1. 1% A-137 {Witco) 2. 1% A-151 (Witco) 3. 1% A-272 {Witco) Scanning electron micrographs shown in Figures 1-6 -21- were collected with a Philips XL 30 FEG scanning electron microscope (SEM) at 1 Kv accelerating voltage and 1 x 10(-5) mbar vacuum. Samples of petunia petals were coated with particle membranes as described in Example 1 and placed in the instrument without any additional sample preparation. The vacuum caused a collapse of the surface irregularities of the petal substrate, but did not affect the particle membranes as illustrated in Figures 2-6. All images are presented at 400X magnification. Figure 1 illustrates the uneven surface of an uncoated petunia petal. Under an ordinary optical microscope one observes a surface containing many peaks and valleys. These peaks are collapsed under the conditions necessary to collect the SEM image. Ordinary optical images, however, often do not show the membrane surface because the membranes are very thin and transparent to visible light. SEM techniques, however, can capture an image of the surface of such membranes. Figures 2-4 illustrate the membrane surface prepared from calcined kaolin particles (1.2 micron median particle size) treated with the various hydrophobic wetting agents listed in Table IV. Figure 5 illustrates the surface of the membrane prepared from Translink® 77 which has fewer and smaller voids than those voids appearing in Figures 2-4. Figure 6 illustrates the surface of the membrane prepared from the same calcined kaolin particles {0.8 micron medium particle size) used in the manufacture of Translink® 77. The image clearly shows regularly spaced large voids on the order of 20 microns diameter. -22- Example 3 "Seckel" pear trees received the following treatments: 1) conventional pesticide applications applied according to the presence of economic levels of pests using the Virginia, West Virginia and Maryland Cooperative Extension 1997 Spray Bulletin for Commercial tree Fruit Growers publication 456-419, 2) no treatment, 3) weekly application of Translink® 77 beginning in April 29, 1997, 4) weekly application of calcined kaolin (Satintone® 5HP). beginning in April 29,1997, 5) weekly application of treated calcium carbonate (SuperCoat® - commercially available from English China Clay) beginning in April 29, 1997. 6) weekly application of Translink 37® beginning in April 29, 1997. Treatments (3), (5) and (6) applied 25 pounds material suspended in 4 gal methanol and added to 100 gal water. Treatment (4) applied 25 pounds material suspended in 100 gal water with the addition of 27oz Ninex® MT-603 and 2 pints Toximul. These treatments were applied at the rate of 125 gal/acre using an orchard sprayer. This mixture was applied at the rate of 125 gal/acre using an orchard sprayer. Treatments ended September 15, 1997. The treatments were arranged in a randomized complete block design with 2 replications and 4 trees/plot. A freeze of 25 °F occurred on October 23, 1997 and freeze damage of foliage was evaluated on October 28, 1997. Freeze damage was evaluated by collecting 40 leaves/plot (10 from each tree). Leaves with necrosis on the leaf margin to the midvein that extended to the abaxial side of the leaf exhibited freeze damage. Undamaged leaves lacked this necrosis. Each leaf was categorized as damaged or undamaged and 23 percentage undamaged from each plot calculated. Data were analyzed using Analysis of variance using a randomized complete block design. Table-V Treatment Undamaged leaves (%) Conventiona1 2.5 Control 2.5 Translink 77 81. 5 Satintone 5HP 11.5 Supercoat 67.0 Translink 37 69.0 These data demonstrate that freeze damage was extensive when no particles were applied (conventional and control* 2.5% each). Freeze damage was extensive when a hydrophilic particle was applied to the tree (Satintone SHP, 11.5 %). Freeze damage was moderated when hydrophobic particles were applied to the trees {Translink 77, Supercoat, and Translink 37, 81.5%, 67%, and 69%, respectively). These data demonstrate that the presence of a hydrophobic particle membrane will moderate freeze damage. Example 4 "Red Delicious" apple trees received the following treatments; 1) Conventional pesticide applications applied according to the presence of economic levels of pests using the Virginia, West Virginia and Maryland Cooperative Extension 1997 Spray Bulletin for Commercial tree Fruit Growers publication 456-419, 2) no treatment, -24- 3) weekly application of Translink® 77 beginning in March 11, 1997, 4) weekly application of calcined kaolin (Satintone® 5HP) beginning in April 29,1997, and 5) weekly application of treated calcium carbonate (SuperCoat® - commercially available from English China Clay) beginning in April 29, 1997. Treatments (3), and (5) applied 25 pounds material suspended in 4 gal methanol and added to 100 gal water. Treatment (4) applied 25 pounds material suspended in 100 gal water with the addition of 27oz Ninex® MT-603 and 2 pints Toximul. These treatments were applied at the rate of 125 gal/acre using an orchard sprayer. This mixture was applied at the rate of 125 gal/acre using an orchard sprayer. The treatments were arranged in a randomized complete block design with 4 replications and 3 trees/plot. Treatments were not irrigated and received 21.58 cm of precipitation from 1 May to 30 August 1997. Fruit were harvested at maturity; fruit number were measured at harvest. Data were analyzed using Analysis of variance using a randomized complete block design. Table VI Treatment Fruit number/tree Conventional 322 Control 246 Translink 77 applied 3/11/97 382 Satintone SHB applied 4/29/97 302 Supercoat applied 4/29/97 301 -25- The weekly application of Translink® 77 before bud break and the occurrence of a severe frost on April 9, 1997 with a minimum temperature of 20 °F, moderated the frost damage as demonstrated by a larger number of fruit (382) reaching maturity compared to Satintone® HB (302) or Supercoat® (301). The weekly application of Translink® 77 before bud break also moderated the frost damage to fruit compared to the conventional treatment and the untreated control (322 and 246 respectively), neither of which received any pesticide applications prior to the frost. The application after the frost of Supercoat®, a hydrophobic particle, or Satintone® 5HB, a hydrophilic particle, did not increase the number of fruit/tree. Example 5 "Golden Delicious" apples received 3 treatments: 1) commercial pesticide application applied according to the presence of economic levels of pests using the Virginia, West Virginia and Maryland Cooperative Extension 1997 Spray Bulletin for Commercial tree Fruit Growers publication 456-419, 2) full rate of Translink® 77, and 3) half rate of Translink® 77. Treatments (2) and (3) applied 25 and 12.5 pounds material, respectively, suspended in 4 and 2 gal methanol, respectively, and added to 100 gal water. This mixture was applied at the rate of 200 gal/acre using an orchard sprayer. The treated area was approximately 1 acre plots with 2 replications of each treatment in a randomized block design. At harvest the plots were commercially harvested and processed by a commercial grading line. At the time of grading, 100 fruit from each plot were randomly chosen to determine surface defects. The data are reported in Table VII. Table VII Treatment Russetting downgrade (%) Translink® 77 full rate 3.3 Translink® 77 half race 3.9 Conventional 13.8 Application of Translink® 77 at the full and half rate reduced russetting on the apple surface compared to the conventional treatment. Example 6 "Stayman" apples received 2 treatments: 1) commercial pesticide application applied according to the presence of economic levels of pests using the Virginia, West Virginia and Maryland Cooperative Extension 1997 Spray Bulletin for Commercial tree Fruit Growers publication 456-419, 2) Translink® 77 treatment applied 25 pounds material suspended in 4 gal methanol and added to 96 gal water. This mixture was applied at the rate of 200 gal/acre using an orchard sprayer. Each treatment was applied to 1 acre blocks with no randomization. Apples were harvested commercially and processed on a commercial grading line. Data presented represent percent packout from the commercial grading line. At time of grading 100 fruit each treatment were randomly chosen to evaluate for surface defects. Cracking percentage was the percentage of fruit with visible cracks in the fruit. The data are reported in Table VIII. -27 Table VIII Treatment Fruit cracking {%) Translink® 77 2 Conventional 22 5 The application of Translink® 77 deceased the cracking of apple fruit compared to the conventional treatment. -28-WE CLAIM: 1. A coating membrane comprising of one or more particulate layers such as herein described, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate. 2. The coating membrane as claimed in claim 1, wherein said particulate materials are hydrophobia 3. The coating membrane as claimed in claim 1, wherein said particulate material has a Receding Contact Angle of greater than 90°. 4. The coating membrane as claimed in claim 1, wherein the particulate material has a particle size distribution wherein up to 90% of the particles have a particle size of under 10 microns. 5. The coating membrane as claimed in 1 wherein the particulate material comprises a hydrophilic core and a hydrophilic core and a hydrophobic outer surface. 6. The coating membrane as claimed in 5, wherein said hydrophillic core materials are selected from the group consisting of calcium carbonate, mice, kaolin, bentonite, clays, attepulgite, pyrophyllite, wollastonite, silica, feldspar, sand, quertz, chalk, limestone, diatomaceous earth, baryte, ceramic, glass and organic mlcrospheres, aluminum trihydrate, ceramic fibers, glass fibers, colorants and titanium dioxide. 7. The coating membrane as claimed in 5, wherein said hydrophobic outer surface materials are selected from the group consisting of chrome complexes, organic titenates, organic zirconate or aluminate coupling agents, organofunctional silanes, modified silicone fluids and fatty acids and salts thereof. 8. The coating membrane as claimed in claim 1 wherein the finely divided particulate materials have a median individual particle size below 3 microns. -28- 9. The coating membrane at claimed in claim 5, wherein the hydrophillic core particulate material are selected from the group consisting of calcium carbonate, calclned kaolin and members thereof. A coating membrane comprising of one or more particulate layers such as herein described, said layers comprising one or more particulate materials, said particulate materials being finely divided, and wherein said membrane allows for the exchange of gases on the surface of said substrate.

Documents:

00324-cal-1998-abstract.pdf

00324-cal-1998-claims.pdf

00324-cal-1998-correspondence.pdf

00324-cal-1998-description(complete).pdf

00324-cal-1998-drawings.pdf

00324-cal-1998-form-1.pdf

00324-cal-1998-form-18.pdf

00324-cal-1998-form-2.pdf

00324-cal-1998-form-5.pdf

00324-cal-1998-letters patent.pdf

00324-cal-1998-p.a.pdf

00324-cal-1998-priority document.pdf