Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/12—Powders or granules
  • A01N25/14—Powders or granules wettable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/006—Coating of the granules without description of the process or the device by which the granules are obtained
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05C—NITROGENOUS FERTILISERS
  • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
  • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
  • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants

Definitions

• the present invention relates to pesticidal granules containing rapidly dissolutioning or dispersing fertilizer and surfactant compositions. More particularly, the fertilizers are water-soluble nitrogen-containing and the surfactant 0 compositions comprise solid, nonionic surfactants.
• the surfactant is hydrophilic enough to solubilize the herbicide in water and lipophilic enough to penetrate the cuticle of a 0 leaf.
• the surfactants are hypothesized to form onolayers on the leaf surfaces with the lipophilic portion along the waxes and the hydrophilic portion forming "hydrophilic channels" through surface imperfections such as cracks, punctures, and pores. These channels absorb water and 5 slightly swell to allow herbicides to diffuse through the cuticle into the cell walls.
• the surfactants preferred by the art and which can realize the above-described properties when admixed with pesticides in aqueous medium, are the nonionics.
• the solid, nonionic surfactants are desired by the end-user, usually a farmer, for ease of handling such as when preparing a pesticidal spray tank mix.
• the solid nonionics are also preferred to eliminate the need for triple rinsing of the liquid surfactant containers, e.g., the 2.5 gallon jugs, 5 usually used to deliver liquid surfactant concentrates to farmers and to avoid the attendant jug disposal problem.
• dry water-soluble nitrogen fertilizers such as urea, ethylurea, mono and diammonium phosphate; mono and diammonium sulfate, and mixtures thereof can enhance the 0 efficacy of pesticides, especially the herbicides.
• This significant increase in herbicide phytotoxicity in the presence of nitrogen fertilizers has been especially observed with the use of diammonium sulfate adjuvant.
• Large increases in herbicidal efficacy have been reported (Adjuvants and 5 Agrochemicals, Vol. II, Chapter 34) when diammonium sulfate was used as an adjuvant in combination with methylated seed oil, a known cuticle "softener".
• Glyphosate one of the most frequently used herbicides worldwide, usually has diammonium sulfate added to its spray tank solution to enhance its 0 herbicidal efficacy.
• diammonium sulfate appears to have at least two modes of action when coupled to glyphosates: firstly, by directly increasing the glyphosates phytotoxicity and secondly, by overcoming antagonism from certain cations. It has been theorized that the sulfate ions 5 precipitate calcium and sodium ions by forming calcium and sodium sulfates which have low water solubility. The ammonium ions form the more toxic glyphosate-ammonium complex and prevent formation of the less phytotoxic glyphosate - sodium complex during droplet drying.
• Extrusion processing to prepare mel -admixed granules such as is taught in EP 501,798A1, wherein pesticides, binders and diluents are extruded together, has the disadvantage of always intimately admixing all of the components thus inherently placing a restriction on the individual components that can be utilized in such a process. For example, in many situations, the individual components sought to be used are incompatible in intimate contact. Furthermore, in extruded granules, all of the material components will be exposed to the aqueous medium simultaneously, i.e., one cannot program for differing dissolution rates.
• multi-component particles are desirable in many end-use applications such as when they are to be used in pesticidal tank mixes for they are more stable during storage and transport than mere physical mixtures of the dry individual components and provide ease of handling.
• dry water-soluble nitrogen- containing fertilizers preferably diammonium sulfate can provide excellent substrates for certain solid nonionic surfactants when the surfactant composition is dry bonded onto
• adjuvants that require a longer exposure time to a given aqueous medium for optimum efficiency as an inherent 5 part of the granule, for example, guar particles that require additional hydration time; pH buffers, etc., they can be preferentially or sequentially released by not having the adjuvant incorporated uniformly throughout the particle as would occur using the processing of the prior art, but rather 0 having the adjuvant adhered to the outer surfactant coating of the granule.
• spray-coated is meant that the solid surfactant is melted and coated upon a substrate comprising the fertilizer while still in the molten state. This is done by spraying the 5 molten surfactant onto the substrate, most preferably the diammonium sulfate particles in a coating blender. Complete coating of the substrate particles is not always necessary but, rather, the degree of completeness of the coating is often determined by specific requirements such as the need to isolate the fertilizer from other added incompatible 5. adjuvants. The sprayed material, while still-in a sticky state is then continuously tumbled to partially agglomerate or granulate the individual particles while preferably the pesticide is added and bonded so as to yield dry bonded flowable granules. 0
• the solid, nonionic surfactants that can be used in the process of this invention are those known in the art which are solid or of a hard, nontacky wax consistency at room temperature.
• Nonionics are the following: 5 A) Amides such as: i) Alkanolamides of the formula -
• R' and R" each can be -H, -CH 2 CH 2 OH, or
• esters such as: 5 i) fatty acid esters of the formula -
• R is a fatty alkyl group, preferably a C s - C 22 fatty alkyl group, most preferably a C ⁇ - C l ⁇ fatty alkyl group;
• R is -H or a fatty alkyl group, preferably -H 5. or a Cj ⁇ C 22 fatty alkyl group, most preferably -
• oxide and/or propylene oxide units are such that the surfactant composition is a solid at room temperature (24 * C), preferably a solid at 50 * C.
• liquid surfactant 20 that alone are liquid even at room temperature may be acceptable provided that the amount or nature of the liquid surfactant is such that the final particulate product does not exhibit tackiness at room temperature.
• tackiness is not exhibited even at 50 * C.
• the more preferred solid nonionic surfactants are the aforedescribed alkyl alcohol ethoxylates and alkylphenol ethoxylates.
• the solid, nonionic surfactant composition of the instant granules should be from about 1 to about 99 weight percent, preferably from about 3 to about 95 weight percent based on 5. the total granule formulation weight.
• the most preferred solid nonionic surfactant is dinonylphenol ethoxylate ⁇ ) 100 EO) for it has been discovered that this compound possesses the ability to provide excellent wetting characteristics together with a high melting point. 0 Furthermore, the material exhibits an ability to dissolve in aqueous medium without formation of a gel phase.
• the amount of the dry water-soluble nitrogen-containing fertilizer to be spray-coated by the solid nonionic composition can be from about 1 to about 99 weight percent, 5 preferably from about 1 to about 95 weight percent based on the total weight of the final spray-coated composition.
• the pesticides contemplated for use in the granules of this invention are those active ingredients well known to be of value to agriculture and are normally distributed to loci 0 via aqueous spray means such as herbicides, fungicides, bactericides, insecticides, insect antifeedants, acaricides, miticides, nematocides, and plant growth regulants.
• Preferred pesticides are the herbicides selected from the group consisting of the herbicidal sulfonyl ureas, imidazolines, and 25 glyphosates.
• the active ingredients should be present in the granules in pesticidally effective amounts, preferably from about 0.01 to about 90 weight percent, most preferably from about 0.03 to about 80 weight percent based on the total granule formulation weight.
• the essence of the preferred embodiment of the instant 5. invention lies in the discovery that if solid nonionic surfactant compositions are spray-coated upon dry, water- soluble nitrogen-containing fertilizers such as diammonium sulfate, the dissolution rate of the dry surfactant particulate composition in aqueous solution can be greatly 10. enhanced. It is also hypothesized that in addition to the action of the fertilizer per se upon the dissolution rate of the solid, nonionic surfactant composition, the coating/granulation process tends to entrap air within the coated granules thereby increasing the surface area ultimately 15 exposed to the aqueous medium which increases the dissolution rate (as opposed to compaction and extrusion processes which tend to compress air out of the particles) .
• the preferred process of the instant spray-coating invention comprises the steps of: a) adding the dry water-soluble nitrogen-containing fertilizer, preferably diammonium sulfate to a blender chamber; 25 b) mixing said fertilizer to ensure uniform distribu ion; c) melting the initially solid nonionic surfactant composition, preferably at a temperature of from about 65 * to about 95'C. (149 - 203 * F) ; d) spraying the molten surfactant composition onto 5.
• the fertilizer particles in said blender chamber e) blending continuously to effect a uniform coating and granulation of the fertilizer particles; f) admixing pesticide particles while the surfactant composition is still tacky; and 0 g) cooling the pesticide-containing granules, preferably to less than 50 * C (122 * F) .
• the fertilizer particles are initially blended for at least 10 minutes before the spraying step to ensure that the initial crystal or particle sizes are 5 uniformly distributed throughout the batch.
• the preferred spray blender-mixers are those of the Mark VI design manufactured by Continental Rollo or an equivalent.
• the mixture should continue to be blended for at 0 least three additional minutes after the spraying has ceased. If it is desired to have any additional components adhere to the surface of the coated granules, e.g., if an additional additive is a fine powder and one desires to reduce dusting in the final product, the material can also be added while the 5 coated granules are still tacky to obtain adherence, i.e., the material can be added before the granules are completely cooled.
• optional additional components include anti-foam agents, flow agents, anti-caking agents, stabilizers, inert fillers, gas-generating agents, dyes, and/or any adjuvants particular to the specific end-use 5. application of the resulting product.
• Optional adjuvants can be added from about 0 to about 20 weight percent of the granular composition. Inert ingredients can be added up to about 80 weight percent.
• additional adjuvant components which normally would be incompatible with the fertilizer, specifically the diammonium sulfate can be made a part of the coated granule by introducing the component after the pesticide granulation process is essentially completed, but 0 while the multi-layered material is still tacky so that the adjuvant can be adhered to the outer surface, i.e., the component would only be in contact with the pesticide and the nonionic composition layer.
• the fertilizer of the instant process preferably should be of a coarse grade,* most preferably 95 weight percent of the material should have an average particle size diameter of from about 200 to about 600 microns, i.e., 95 weight percent should pass through a 30 mesh (U. S. Standard) screen and not pass through a 70 mesh (U. S. Standard) screen. Elimination of fines is preferred to minimize compaction or agglomeration of the fertilizer particles during the coating process.
• the granules may be used as is or, if preferred, screened to a desired particle size.
• the following specific examples are further illustrative of the present invention, but it is understood that the invention is not limited thereto. All amounts of various ingredients are by weight or weight percent unless otherwise specified. In all of the following Examples, the dissolution rates were determined as follows:
• a calculated amount of product such that the surfactant weight remained at 2.0 grams is added into a 250 ml beaker filled with 98 ml of deionized water at room temperature while stirring with a magnetic stirrer set to a speed of about 30-50% full scale and a stopwatch started. When complete dissolution is observed, i.e., the solution becomes completely clear, the time is recorded.
• a flaked dinonylphenol ethoxylate ()l00 EO) (sold under the Rhone-Poulenc trademark Igepal DM-970 FLK) is blended with a sufficient amount of a liquid isodecyl alcohol ethoxylate (4 EO) (sold under the Rhone-Poulenc trademark Rhodasurf DA-530) 0 to produce a non-tacky, solid mixture with a 85:15 respectively weight ratio surfactant Composition A (said blend also sold by Rhone-Poulenc under the trademark AgRH ⁇ DS 420) .
• isodecyl alcohol ethoxylate has an adverse effect on the melting point of the solid dinonylphenol ethoxylated 5 surfactant, its presence is useful for the improved wetting characteristic it provides, i.e., the lower surface tension realized in the final aqueous solution as a result of its incorporation.
• dry diammonium sulfate is added to 0 the dry Composition A prepared above in a Sigma Blade Mixer in a weight ratio of approximately 85:15 weight percent sulfate to surfactant. Blending is unable to be accomplished because the materials compress together and cake.
• the test is run again utilizing solely the flaked 5 dinonylphenol ethoxylate ()l00 EO) , i.e., Igepal DM-970 FLK in lieu of Composition A. Again, the blending is unsuccessful because, even at room temperature, the surfactant and diammonium sulfate compact to form cakes.
• Diammonium sulfate is charged into a Continental Rollo mixer Mark VI blender. The sulfate is rotationally blended for about 10 minutes.
• a solid nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate
• the resulting dissolution time of the solid nonionic surfactant composition indicates the significantly enhanced
• the dissolution times of the resulting coated granules are less than half that of the solid nonionic surfactant composition alone.
• Example V The process of Example IV is followed utilizing the following weight percentages: ammonium sulfate - 93.15%; AgRH ⁇ 5 DS 420 - 6.0%; Rhodorsil EP 6703 - 0.1%; and Tixosil 38 AB - 0.75%.
• the dissolution times of the resulting coated granules are again less than half that of the solid nonionic surfactant compositions alone.
• the spray-admixed compositions of 5 this invention do not suffer from particle separation that can occur with simple solid blends of the same materials.
• the coated products of this invention also realize a very uniform granule size together with excellent attrition
• Adjuvant A Twenty five pounds of Adjuvant A is prepared by charging 93.15 weight percent diammonium sulfate into a Continental Rollo Mixer Mark VI Blender. The sulfate is rotationally blended for about 10 minutes. 6.0 weight percent of a solid
• nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate () 100 EO) (Igepal DM 970) to isodecyl alcohol ethoxylate (4 EO) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-Poulenc trademark AgRH ⁇ DS 420) is heated at
• the following table illustrates the enhanced phytotoxicity realized by the use of the dry bonded pesticidal-adjuvant systems of the instant invention prepared as above described compared to that realized by standard liquid adjuvant-pesticide blends.
• the carrier for the compositions listed in Table II is water at ten gallons per acre.
• Kinetic (a trademark of Helena Chemical Co.) is a proprietary liquid surfactant adjuvant system comprising a polyorganosilicone and an ethyleneoxide/propyleneoxide block copoly er.
• Dynamic (a trademark of Helena Chemical Co.) is a proprietary liquid adjuvant system comprising methylated seed oil (MSO) and a polyorganosilicone.
• MSO methylated seed oil
• C.O.C. is a crop oil concentrate usually about 83 weight percent paraffinic crop oil and 17 weight percent emulsifier.
• Beacon is a trademark of Ciba Geigy for a sulfonyl urea formulation.
• Accent, Classic and Pinnacie are trademarks of DuPont for sulfonyl urea formulations.
• Pursuit is a trademark of American Cyanamid for an lmidazoline formulation.
• _0 Poast Plus is a trademark of BASF for a proprietary cyclohexanedione formulation.
• Butyrac 200 is a trademark for a 2,4 DB formulation sold by Rhone-Poulenc Inc. 5
• the above results illustrate the significantly enhanced herbicidal activity that can be realized via the use of the dry bonded pesticidal-adjuvant granules of the instant invention over the activity levels when standard liquid adjuvant systems are used.
• Examples XVI - XVII The following examples illustrate the enhanced phytotoxicity realized by the use of a glyphosate herbicide incorporated into the granulated products of the surfactant- 5 fertilizer carrier systems of this invention prepared as described in Examples VI - XV with the following changes to the pesticidal granular composition: 84.05 weight percent diammonium sulfate; 15.0 weight percent AgRH ⁇ DS 420; 1.6 oz. Rhodorsil Silicone EP 6703; and 6.0 oz . of Tixosil 38 AB.
• the 10 herbicide used is Roundup which is a trademark of Monsanto for a glyphosate herbicidal formulation. Quest is a proprietary ammonia-based water conditioner of Helena Chemical Co.
• the carrier for the compositions is again ten gallons of water per acre . 15. Table in

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Organic Chemistry (AREA)
• General Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
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• Engineering & Computer Science (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Fertilizers (AREA)

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• 1996
  • 1996-01-31 JP JP8523671A patent/JPH10513148A/ja active Pending
  • 1996-01-31 AU AU47728/96A patent/AU4772896A/en not_active Abandoned
  • 1996-01-31 BR BR9607573-2A patent/BR9607573A/pt not_active Application Discontinuation
  • 1996-01-31 CA CA002211996A patent/CA2211996A1/en not_active Abandoned
  • 1996-01-31 EP EP96903745A patent/EP0806893A1/en not_active Ceased
  • 1996-01-31 WO PCT/US1996/001233 patent/WO1996023408A1/en not_active Application Discontinuation

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