![United States Patent 119] [11]‘ Patent Number: 5,022,917 Allan [45] Date of Patent: Jun](http://data.docslib.org/img/c92beceb22387b2fa69761f9e23f17d5-1.webp)
United States Patent 119] [11]‘ Patent Number: 5,022,917 Allan [45] Date of Patent: Jun. 11, 1991
[54] égqhgggggllgéglnALLy A ‘ OTHER PUBLICATIONS [75] Inventor. G Graham Allan Seattle wash Yarborough, Chemical Abstracts, vol. 94 #97896y, 1981 ' ' ’ ’ ' “Hexazinone pellet for spot treatment of woody weeds [73] Assignee: Melamine Chemicals, Inc., in lowbush blueberry ?elds”. Donaldsonville, La- Lane, ChemicalAbstracts. vol. 95 #l82l89k, 1981 “Con [21] Appl. No‘: 478,729 trol of certain hard to kill weed species in lucene with ' hexazinone”. [22] Filedi Feb- 12’ 1990 G. G. Allan et al., “Selective Suppression of Weeds and Deciduous Brush in the Presence of Conifers”, Interna Rel?ted US. Application Data tional Pest Control,’ vol. 14, No. 2, Mar/Apr. 1972. [63] Continuation of Ser. No. 671,731, Nov. 15, 1984, aban- G- G. Allan 6* 81» “Phi/toxicity Of some Systemic 111 doned, which is a continuation-in-part of Ser. No. secticides to Spanish Cedar”, International Pest Control, 518,281, Jul. 28, 1983, abandoned. v01. 15, N0. 1, Jan/Feb. 1973. [51] Im. c1.5 ...... A01N 43/64 G- C" Ana“ 6‘ 31‘: “Gmw‘h Enhancer?“ °fa Juvenili [52] US. Cl...... 71/93; 71/DIG. 1 COM“ Fm“ 5“ Y?“ After Apphcatio“ "f a C°“' [58] Field of Search ______“ 71/DIG_ 1, 65’ 79, 93, trolled Release Herb1c1de”, International Pest Control, V01. 20, NO. 2, Mar/Apr. _ G. G. Allan et al., “Controlled Release Growth Stimu [56] References Cited lants for Plants”, Biomedical Polymers: Polymeric Materi U_S_ PATENT DOCUMENTS als and Pharmaceuticals for Biomedical Use, 1980. 3,074,845 l/1963 Geary ...... 71/65 Primary Examiner-Frederick E. Weddell 3,223,513 12/1965 Geary ...... 71/92 Assistant Examiner—-Raymond Covington 3,813,236 5/1974 Allan ...... 7l/94 Attorney, Agent, or Firm-Brainer & Breiner
3,983,116 9/1976 Lin ...... 544/211 4,035,365 7/1977 Kay 544/211 [57] ABSTRACT 410602404 11/1977 Evans ' ' ~ ' ' ' - - " 544/211 Liquid compositions provide a source of a herbicide or
513x15 ' ' ' ' ‘ ' ' ' ' ' ‘ ' ‘ ' ' ' ‘ ' ' ' " other biologically active substance in combination with 4:l0l:308 7/1978 Och 544/211 a particular nitrogenous chemical, preferably melamine. 4,209,619 6/1980 Albert ...... 544/211 After application, the hcrbicid? is characterized by 4,283,387 8/1981 Young et a1...... 71/64 F enhanced ef?cacy as compared to the ef?cacy Observed when applied alone. FOREIGN PATENT DOCUMENTS 855166 9/1980 Belgium . 7 Claims, No Drawings 5,022,917 1 2 sure. The ?ne particle sizes of commercial dry crystal LIQUID HERBICIDALLY ACTIVE line melamine, as currently produced, make it difficult COMPOSITIONS to use as such, as a dry fertilizer material. An aqueous slurry of particulate melamine is suggested for use in the This is a continuation of application Ser. No. 671,731 5, Freepons application, above, for dispensing into a ?led Nov. 15, 1984 now abandoned; which in turn is a trench, where the ?ne melamine particles can easily be continuation-in-part of Ser. No. 518,281 ?led July 28, covered by a layer of soil, so they will not blow away. 1983 now abandoned. A somewhat related agricultural chemical problem is The subject matter of this application is related to the formulation of biocides, plant growth regulants, and that in commonly assigned US. patent application Ser. 10 other biologically active materials for slow or con No. 305,603, ?led Sept. 25, 1981, of Allan et al., which trolled rate release, and for improved efficacy. Biocides describes slow release fertilizer granules such as mela include such pesticides as insecticides, herbicides, and mine-urea agglomerates and prills. The subject matter fungicides. One basic purpose of prolonged activity of this application is also related to that of commonly formulations of biocides is to extend the time between assigned US. patent application Ser. No. 305,394, ?led repeat applications and thus effect a saving on the cost Sept. 25, 1981, of Freepons, which is concerned with of the labor involved in an application. A second impor methods of applying slow release nitrogen fertilizer tant purpose is to improve the effectiveness of a biocide materials, such as melamine-based granules, to the soil. by a sustained but more uniform activity over a period These applications, referred to above, are all ex of time, rather than the inef?cient technique of several pressly incorporated herein by reference. applications of the biocide alone, over a period of time, BACKGROUND OF THE INVENTION with concomitant short periods of high biocide concen tration and effectiveness together with the risk during 1. Field of the Invention such periods of pollution and phytotoxicity to crops, This invention relates to liquid, preferably sprayable, and long periods of low or zero concentration. compositions containing biologically active material, 25 particularly those that are useful in agriculture. These More prolonged activity for biologically active mate compositions provide for the release and often for the rials would permit extended time intervals between sustained action of biologically active substances. More treatments and the reduction of the application level for particularly, the invention relates to a preferably spray a given effect over a period of time, thus reducing envi ronmental impact. Thus, from an ecological standpoint, able liquid product that is formulated with a biologi 30 cally active substance such as a herbicide or other pesti the controlled release of a pesticide, for example, if cide for use in crop production. This product can be coupled with improved ef?cacy and a prolongation of applied to the soil or plant foliage using conventional effective activity, would enhance the lifetime of a non equipment. Its composition is such as to provide pro persistent agent at the site of treatment. longed activity or improved activity. 35 When only ferilizer is applied to slow growing crops 2. Description of the Prior Art such as trees, weeds that compete with tree seedlings Melamine and its hydrolysis products, ammeline, may be stimulated to grow to such an extent as to crowd ammelide, and cyanuric acid, and as well the related and compete with the seedlings. Thus the positive ef material dicyandiamide (cyanoguanidine), have often fects expected from fertilization may be negated by the been considered as potential sources of nitrogen for vigorous growth of weeds that compete with the trees incorporation in fertilizer compositions or for utilization for vital water, light, and nutrients. Also, if fertilizer as nitrogen sources per se. Melamine and dicyandiamide materials such as urea and/or ammonium salts are ap each have a nitrogen content of 66.67%; two-thirds of plied in sufficient quantity so that the effects can be their weight is nitrogen. When used as fertilizer materi observed over a signi?cant period of time, not only is als, they provide high percentages of nitrogen per unit 45 fertilization inef?cient but also there may be toxic ef weight applied. fects because of salt stress. Avoiding this by more fre Commercially produced melamine is available only_ quent multiple, small applications generally is not prac as a ?ne crystalline powder, because small size particles tical for tree crops. are required for the present major commercial end mar The controlled release of biocides has previously kets for melamine. A typical screen analysis for one been achieved by their incorporation within a matrix of commercially available (from Melamine Chemicals, a synthetic polymer, e.g., encapsulation wherein for Inc-MCI) dry melamine product, conducted with example a pest control agent is surrounded by an envel United States Standard Sieve screens, is as follows: oping wall of a synthetic polymer that permits loss through diffusion, permeation or degradation; disper Percent 55 sion of the pesticide in an elastomer or a synthetic plas Screen Analysis Retained tic wherein the pesticide is released through leaching or 40 Mesh 0-0.1 diffusion; or chemical combination of the pesticide with 40-50 Mesh 0-0.1 a high molecular weight synthetic polymer in such a 50-60 Mesh 0-0.3 manner that the appended pesticide is slowly released 60-80 Mesh 0.5-5.0 from the polymeric backbone upon exposure to the pest 80-100 Mesh 1.0-5.0 100-200 Mesh l3-30 infested environment. However, the prior art ap 200-325 Mesh 13-30 proaches often fall short of what is desired, in one or Thru 325 Mesh 40-60 more respects. Also, they tend to be expensive, and some of the synthetic polymeric materials suggested for Other commercially available melamine products may 65 use are either not biodegradable or degrade so slowly be somewhat coarser, but the majority of the particles that it is not a useful property. remain below 40 mesh. The smallest particles are very Some sustained action, biologically active composi ?ne and powdery, and their sizes are difficult to mea tions, such as insecticides, fungicides, herbicides, nema 5,022,917 3 4 tocides, and other biocides, and plant growth regula mixtures thereof, their and melamine’s physiologically tors, are disclosed in U.S. Pat. No. 3,074,845 to Geary. acceptable inorganic and organic salts, and mixtures The biologically active material is formulated with an thereof. Melamine and its salts are the preferred nitro inert carrier material and an amide-aldehyde resin. The gen source materials. These nitrogen sources generally formulation is prepared by ?rst impregnating the inert are compounds in crystalline or powdered form. carrier material with the biologically active substance, The mechanism for achieving the enhanced efficacy coating the impregnated carrier material with the is not fully understood. It is theorized, however, that amido-aldehyde resin, and then polymerizing the resin there may be either a chemical reaction of some sort, or in situ. Suitable resins include urea-formaldehyde, mela hydrogen bonding, or a combination of these, between mine~formaldehyde, and urea-melamine-formaldehyde the biologically active material and the nitrogen source resins. . material, particularly melamine, or a physiological re A later Geary patent, US. Pat. No. 3,223,513, dis sponse by the weed plant to the combined presence of closes similar sustained release compositions in which the BAM and melamine (or the like). The data that is the biologically active material is mixed with mono now available does not permit a de?nitive conclusion, meric amido and monomeric aldehyde reactants, and 5 but there appears to be an indication that with a given then the reactants are polymerized to form an amido BAM, to achieve a speci?ed result, the use of the pres aldehyde resin in situ. When the biologically active ent invention permits application of the BAM at a lower material and the resin-forming reactants are combined, rate than is possible when the BAM is applied alone in an occlusion of the active material with the resin is a conventional vehicle. obtained, which in physical form is sieve-like or sponge It can also be theorized that the melamine or other like in structure with the molecules of active material in poorly soluble nitrogen source has some kind of stimu the interstices of the polymer. ' latory or synergistic effect of a nature that cannot pres Belgian Pat. No. 885,166, of Allan (the applicant ently be explained. Whether that is the case or not, the herein), discloses a simple physical mixture of ?ne parti slow release nitrogen material, over a period of time, cles of (l), melamine that has been recrystallized to 25 does bene?t plant life by slow conversion in the soil to remove certain phytotoxic impurities and (2), a con a form in which it is useful to plant life growing in the trolled release form of 2,4-dichlorophenoxyacetic acid soil. The biologically active material that is selected for (2,4-D). The preferred controlled release form of 2,4-D use may be any such material that does not interfere is prepared by intimately mixing or melting together with the dissolution of the nitrogen source and the ac equal parts by weight of kraft lignin and 2,4-D and tion on it of microorganisms to produce nitrogen in a extruding the resulting mixture in pellet or ?ake form of form that is of nutrient value to plant life. the desired size. Most generally, liquid formulations prepared in ac More recently, US. Pat. No. 4,283,387 to Young et cordance with the invention will be in the form of slur al. discloses controlled release biologically active com ries or suspensions. However, they may also be in the positions similar to those disclosed in the later Geary form of solutions. patent mentioned above. In Young et al., a mixture In one preferred, broad embodiment of the invention, comprising a carbinol-containing organic polymer, the sprayable formulation comprises at leased one bio crosslinking agents for the polymer, and a biologically logically active material; a nitrogenous compound se active substance undergoes hydrolysis to form a poly lected from the group consisting of melamine, ben meric network capable of controlling the release of the 40 zoguanamine, dicyandiamide, ammeline, ammelide, biologically active substance. cyanuric acid, mixtures thereof, and the physiologically A different approach appears in Pierce, 3,172,752. In acceptable salts thereof, both organic and inorganic; one embodiment, a herbicide, fungicide, or insecticide is and a liquid vehicle in which these said components are mixed with activated sewage sludge. The mixture is dissolved and/ or suspended, to form a liquid, preferably then adsorbed into pores, some of which are capillary, 45 sprayable composition. The nitrogenous compound and in particles of expanded perlite. The particles are then the biologically active material are preferably present in sprayed with a urea-formaldehyde solution, which such proportions that the ratio is at least 3:1, by weight. forms a very slowly soluble sheath about each particle In a more specific preferred embodiment of the in upon curing and drying. vention, the liquid, preferably sprayable formulation is in the form of a liquid fertilizer composition having an SUMMARY OF THE INVENTION aqueous vehicle. There are dissolved in the aqueous In accordance with one embodiment of the present vehicle one or more sources of N, P, and K fertilizer invention, liquid compositions are prepared that, after values. The N source comprises at least one readily application, provide a source of a biologically active water soluble N source and at least one poorly water substance (BAM) characterized by enhanced efficacy, soluble high N source having a water solubility at 20° as compared to the efficacy that is observed when the C., at pH 7, not above 5 grams per 100 grams of water. BAM is applied alone, or when applied together with One useful such high N source is selected from the commonly used soluble nitrogen fertilizers, such as group ‘consisting of melamine, benzoguanamine, dicyan urea. diamide, ammeline, ammelide, cyanuric acid, mixtures One broad concept of the invention is that a biologi thereof, and the physiologically acceptable salts cally active material (BAM), when made up in intimate thereof, both organic and inorganic. In addition, the admixture with a high nitrogen source compound such composition may contain at least one emulsifying, sus as melamine, for example, into a liquid, preferably a pending, or stabilizing agent, or it may be mechanically sprayable liquid formulation, and applied appropriately, agitated. It also contains at least one biologically active exhibits more prolonged and/0r more effective activity. 65 material at a concentration that is useful, upon applica In place of melamine, other poorly soluble high nitro tion of the liquid fertilizer, to perform its intended func gen sources may be used, such as benzoguanamine, tion. Following application of the composition to a dicyandiamide, ammeline, ammelide, cyanuric acid, substrate, such as the soil, it is characterized by more 5,022,917 5 6 prolonged activity of the biologically active material The term “readily water soluble” refers to materials than would be the case of it alone had been applied. that dissolve in water at 20° C., pH 7, to the extent of 20 The efficacy of the biologically active material is grams per 100 grams or more, that is, materials that improved, although the theoretical reason for this is not form solutions of 16% or greater concentration. understood at the present time. Efficacy may be en Similar terms should be understood to have similar hanced as a result of a physiological or bichemical re meanings. For example, the expression “poor water sponse by the weed, insect, or other pest to the simulta solubility” is used to refer to materials that are “poorly neous presence of the pesticide and the melamine or water soluble”, as defined above. other poorly soluble nitrogenous source as speci?ed Based on available information, the solubilities in above, with which it was intimately brought into water at 20° C., pH 7, for several materials useful in contact for application. Such a physiological or bio connection with this invention, in grams per 100 grams chemical response by the weed, insect or other pest of water are: would presumably take place within the weed, insect, TABLE 1 or other pest following uptake, absorption, inhalation or ingestion. 15 Material Solubility (g/lOO g) Melamine 0.50 For example, certain grassy and herbaceous weeds Benzoguanamine 0.06 (22' C.) have been observed to be less tolerant of, that is, more Dicyandiamide 2.26 (at 13° C.) sensitive to, a speci?c triazine herbicide when that her Ammeline 0.008 bicide has been applied together with melamine, than Ammelide less than 0.008 Cyanuric Acid 0.27 when applied alone or with a highly soluble nitrogen Melamine Nitrate 0.85 fertilizer such as urea. This reduced tolerance for, or Ammonium Nitrate 192 greater sensitivity to, a herbicide may manifest itself in Ammonium Sulfate 75.4 one or more of several ways: earlier weed kill; higher Diammonium Phosphate 131 (at 15‘) initial kill; more chlorosis of the surviving weeds; and Potassium Acid Sulfate 51.4 25 Potassium Sulfate 11.1 /or prolonged duration of kill of newly germinating Urea ll9.3 (at 25° C.) weed seeds. DEFINITIONS In referring to particle sizes, the term “diameter” is used, as it commonly is, to refer to the largest dimension The term “biologically active material” (BAM) is of a particle, even though the particle is not spherical in w_used in a broad sense to refer to any of the common shape. biologically active substances in common use, for exam ple, in agricultural and turf grass treatment chemical DESCRIPTION OF THE PREFERRED applications. Thus the biologically active material EMBODIMENT (BAM) could be a herbicide, insecticide, fungicide, In a very simple formulation that embodies the inven fumigant, miticide, nematocide, or other form of bio tion, a sprayable liquid formulation comprises a biologi cide, or a plant growth regulator, a repellent, a rodenti cally active material (BAM), such as, for example, a cide, or the like. ‘ material exhibiting herbicidal activity. Such a material The term “granular” is employed herein in a broad may have one or several active ingredients, depending sense, to refer to granular products produced from upon its intended purpose. The formulation also in particles and a binder for the particles. The binder is cludes a nitrogenous compound that, generally, is settable and initially may be molten, to harden on set poorly water soluble, as defined above. Preferably, the ting, or moist, requiring drying for setting. Agglomer nitrogenous compound is a triazine, and most prefera ated granules may be formed by a binder that is applied bly, it is melamine or ammeline. A third essential com as an aqueous solution, and dried to cause binding. Urea 45 ponent is a liquid vehicle in which the other compo and similar fusible binders may be applied while molten, nents are suspended, dissolved, or both suspended and and typically produce very strong granules. Screening dissolved. An emulsifying, suspending or stabilizing and recycling may be used to achieve desired sizes. agent, or a combination of these, may be present in the Granules may also be formed by mixing ?ne particles in liquid vehicle to facilitate handling, storage, shipment a molten binder material, then chilling the mixture. The 50 and use. mixture may be chilled in block form then shaved, or While not wishing to be bound by any particular comminuted; it may be drum chilled and ?aked; or theory, it appears that there is a form of chemical reac drops of the mixture may be chilled. The term “granu tion, or hydrogen bonding, or a combination of these, lar” most often is used in connection with generally between the nitrogenous compound and the biologi spherically shaped materials, but also encompasses such 55 cally active material. Whether this is so or not, the products having other shapes, such as flakes and shav nitrogenous material exhibits an observable effect on mgs. the biological activity after the formulation has been The term “dispersed" is used to mean distributed, and applied. This effect may be to render the BAM, such as is intended to encompass suspended, dissolved, and a herbicide, more effective, or there may be a prolong both suspended and dissolved substances. The term 60 ing' action. Such a prolonging action is particularly “poorly water soluble” refers to materials that dissolve noted, as will be demonstrated, with certain combina in water at 20° C., pH 7, to the extent of 5 grams per 100 tions of melamine and herbicides. grams, or less; that is, materials that form solutions of Since the nitrogenous material has fertilizer value, 5% or less concentration. contributing nitrogen values that become available over The term “slightly water soluble” refers to materials 65 a long period of time following application, the amount that dissolve in water at 20° C., pH 7, to the extent of 1 of the nitrogenous compound that is applied may be gram per 100 grams or less; that is, materials that form adjusted to be quite large, to furnish a desired amount of solutions of 1% or less concentration. fertilizing activity. However, for developing the prop 5,022,917 7 8 erty of prolonging the activity of the biologically active include Lasso ® and Dual ®. These materials may be material, the ratio of the nitrogenous compound to the in solid or liquid form. biologically active material should preferably be at least The arsenicals include cacodylic acid and the salts of 3:], in parts by weight. Generally, the ratio will be monomethyl- and dimethylarsinic acids. The arsenical much higher than this, to take advantage of the fertiliz herbicides based on cacodylic acid are defoliating or ing properties of the nitrogenous compound. dessicating contact herbicides. The salts of the mono The prolonging and/or potentiating action of the methylarsinic acids have lower contact toxicity and act nitrogenous compound, such as melamine, on the bio through absorption. logically active material, such as a herbicide, while The carbamates and thiocarbamates are generally perhaps being attributable to some kind of chemical applied to the soil and are taken up through the root reaction or hydrogen bonding, does not require any systems. A few are foliar. Generally these compounds pre-reaction of these materials. Rather, the evidence are volatile and when applied they are frequently incor indicates that when the materials are brought together porated in the top few inches of soil to retard volatiliza in an aqueous medium, either in a liquid formulation or‘ tion. Herbicides of this type tend inhibit shoot growth in during the preparation of granules as will presently be grasses. Commercial examples of herbicides of this type described, the prolonging action may be observed after are sold under the trademarks Betanal ®, Betanex ®, application. There is also some indication that the reac Sutan ®, and Eptam ®. tion, bonding, or combination of these can occur in the Examples of carboxylic acid herbicides include phe presence of soil moisture. noxy and benzoic acids, aliphatic acids, and carboxylic Generally the biologically active materials that are acids with heterocyclic rings. Generally, these mole preferred for use in the invention are those herbicides cules contain chlorine atoms, i.e., 2,4-D. They include that have chemical structures indicating that they herbicides that are applied to the soil, that act through would be suitable for hydrogen bonding with highly foliar applications, that can be applied to grass, and that nitrogenous compounds such as the triazines, and par are effective against broad leaf weeds. Commercial ticularly with melamine. Such compounds generally 25 herbicides of this kind are sold under the trademarks may be the highly halogenated compounds, carboxylic Banvel ® and Garlon ®. acids, hydroxy compounds, and the like. Dinitroaniline herbicides are generally dinitrochloro The herbicides that are selected for use may be those benzene reacted products. These tend to inhibit root that become effective through contact and, as well, growth and shoot growth. They are generally applied those that are taken up from the soil. Suitable herbicides 30 to the soil and exhibit low translocation. To control include-defoliants, desiccants, eradicants, systemics and grass in soybeans and cotton, and weed germination, selective herbicides. The invention is useful for herbi herbicides of this kind are generally incorporated in the cides that are applied preplanting, after planting but soil. Commercial herbicides of this kind are sold under pre-emergence, “cracking” types, which operate on the the trademarks Balan @ and Treflan ®. plants as they emerge from the soil, and post-emergent 35 Herbicides based on heterocyclic nitrogen com herbicides that are effective after there has been exten pounds include the symmetrical triazine derivatives, sive emergence. pyridazones, and uracils. These are generally applied to The liquid compositions of the invention ’ may be the soil for pre-emergent control. They exhibit low to applied in the form of bands, by broadcasting from large high translocation, depending on the particular herbi spray nozzles, through the use of a directed sprayer, and 40 cide. They are believed to be effective because of inhibi through the use of sprays or curtains of liquid that are tion of oxygen production (the Hill reaction). Commer applied over the top of crops, either by ground mobile cial examples are sold under the trademarks Aatrex ®, equipment or by aerial application. The liquid composi Basagran ®, Sencor ®, and Velpar ®. tions of the invention may include two or more herbi While most of the organophosphates are best known cides in admixture, or in admixture with other materials 45 as insecticides, and as such are considered to be poten such as liquid fertilizer materials. The liquid composi tially useful biologically active materials in liquid com tions may be incorporated into the top few inches of the positions of this invention, a few are active as plant soil, which is a procedure that tends to inhibit photode growth regulators and herbicides. They have diverse composition and/or volatilization. Moreover, mixing structures and properties, and varied uses. Two com the liquid compositions into the top few inches of soil mercial examples of herbicides are sold under the trade promotes activation of the active ingredients through marks Bensulide ® and Betasan ®. normal soil moisture contents, if rain is insufficient. The urea herbicides generally are nonselective and Ordinarily soil incorporation would be used with herbi usually are soil applied. There is rapid translocation. cides applied pre-planting. However, sequential, over The herbicides are believed to be effective through lapping, and piggybacking applications may be made. 55 inhibition of oxygen production (the Hill reaction). For example, a pre-plant herbicide may be incorporated Commercial examples are sold under the trademarks in the soil, followed up by a subsequent surface applica Lorox ® and Tupersan ®. tion of a suitable liquid composition. The quaternary herbicides are usually. considered to Generally, those herbicides that are regarded as suit be contact foliars. Many of them are selective of annuals able include the amides, arsenicals, carbamates, thiocar among perrenials. Some commercial products are sold bamates, carboxylic acids and their derivatives, dini under the trademarks Avenge ®, Diquat ® and Para troanilines, heterocyclic N compounds, organophos quat ®. phates, substituted ureas, quaternary N compounds, and The inorganic herbicides generally are not selective. inorganics. They have diverse chemistry and include such unre The amide herbicides include a wide variety of chem 65 lated materials, for example, as sodium chlorate and ical types, properties, types of applications, and crops sodium azide. upon which the herbicides are effective. Most of these While herbicides are a preferred category of biologi are pre-emergent or pre-planting incorporated. They cally active materials considered useful, the potentially 5,022,917 9 10 useful materials also include a wide variety of insecti ferent classes of chemicals in common use against a cides. As available commercially, insecticides are gen variety of fungi. erally available mixed with adjuvants, such as spreader The aniline/anilide fungicides are relatively few in stickers; carriers such as a talc, bentonite, and diatoma number but important commercially. Botran® and ceous earth; and neutralizers to overcome the catalytic _Dyrene® are contact fungicides useful against foliar action of some carriers, which tend to accelerate break diseases. Vitavax ® fungicide is a systemic seed and soil down. Urea is sometimes used as a neutralizer. treatment material useful for peanuts and loose smut on For incorporation in a liquid composition of this wheat. invention, the insecticidal active ingredient must either The dithiocarbamate fungicides generally are protec go into solution or be capable of being placed in a sus tants against diseases of apples, potatoes, and several pension that is suf?ciently stable to permit application at vegetables. Products in this class include thiram, zineb, a reasonably uniform analysis. As purchased commer maneb, and Manzate ® 2000 fungicide. cially, the insecticidal material that is to be used or The halogenated fungicides are used predominantly evaluated may be‘ a dry formulation in the form of a dust in connection with the peanuts, vegetables, and seed or dry powder, containing anywhere from 0.5% to 10% markets. Among the commercial products are Bravo ® of the active ingredient. The insecticide may also be chlorothalonil fungicide; Terrachlor® fungicide, ef fective on contact; Terrazole ® fungicide, applied as a available in the form of granules. These tend to be seed treatment for the control of pythium and phytoph larger particles than the dust or dry powders, and most thora. often are made by spraying a solution or suspension of The heterocyclic nitrogen fungicides have protectant the active ingredient in a volatile solvent onto a pre or systemic activity. They hold a major share in every sized granular carrier. Generally sufficient active ingre market except potatoes and vegetables. Commercial dient is applied so that the dried granules contain from products of this kind include the phthalamides such as 7% to 10% by weight of the active ingredient. Captan; Difolatan® fungicide, useful as a protectant The insecticidal material may also be available in a contact fungicide; Benlate ® fungicide, which is widely liquid formulation, or in a wettable powder that is in used in connection with apples, peanuts and vegetables, tended to be made up into a liquid formulation. The and is a systemic fungicide; and Bayleton @ fungicide, usual wettable powder contains from 25% to 75% by which is often used on small grains to protect against weight of active ingredient, mixed with a clay-like dilu rust. ent or carrier, together with a wetting agent. Some In addition to these biocidal biologically active mate~ insecticides are available as soluble powders and are rials, there are a variety of other materials that can be miscible with water to rather high concentrations, on expected to exhibit unusual undesirable properties when the order of 75% to 90% by weight. incorporated in liquid compositions according to the Some of the insecticides that are expected to be useful invention. Such materials would include Actidione anti in liquid compositions of the invention include chlori biotic, many biologicals, and some metallics. Among nated hydrocarbons, organic phosphates, carbamates, the preferred biologically active materials for use in and synthetic pyrethroids. liquid compositions of the invention are those that are The chlorinated hydrocarbon insecticides typically useful as pre-emergent or post-emergent herbicides, contain, in their molecules, hydrogen, carbon, and chlo such as, for example, 2,4-D; trifluralin, which is tri rine. Generally these act as stomach and contact poi 40 ?uoro-Z,6-dinitro-N,N-dipropyl-p-toluidine; DCPA, sons affecting the nervous system. They are persistent in dimethyltetrachloroterephthalate; bensulide, [S-(0,0 the environment and tend to accumulate in animal fatty diisopropylphosphorodithioate) ester of N-(Z-mercap tissue. Examples are DDT and chlordane. toethyl) benzenesulfonamide; N-butyl-N-ethyl-a,a,a The organic phosphates generally are contact and/or trifluoro-Z,6-dinitro-p-toluidine; and atrazine and sima stomach poisons. They are chemically unstable and so 45 zine. are less persistent in the environment than the chlori While liquid formulations in accordance with the nated hydrocarbons. Generally they are metabolized invention may be made up by combining in a liquid readily in animals. They are considered highly toxic generally an aqueous vehicle, the selected biologically since they generally are cholinesterase inhibitors, inter active material or materials and the selected nitroge fering with nerve impulse transmission. Most of these 50 nous compound or compounds, together with any other materials are characterized by relatively low LD50 val desired materials, it is also convenient to form some or ues, although the value for malathion is 1400. Parathion all of the dry ingredients into granular form. The user is one of the best known organic phosphate insecticides can then place a quantity of the granules in the proper and is considered to be an extremely dangerous material amount of water or aqueous solution, and stir, allowing to handle. It is a systemic insecticide. 55 time for the soluble binder to dissolve to release the The carbamates generally are similar in action to the slightly soluble ?ne particles of melamine or other se organic phosphate insecticides. They may be highly lected nitrogenous compound. The formulation can toxic but some of them are of very limited toxicity. then be applied as by spraying. Generally, these insecticides are not magni?ed in the The dry ingredients can be granulated in a variety of food chain and are characterized by rather rapid break 60 ways, but the preferred processes for making such gran down, once applied. ular products are similar to those disclosed in copending The synthetic pyrethroids are commonly used in application Ser. No. 305,603, ?led Sept. 25, 1981, modi conjunction with other insecticides to provide quick ?ed however to accomplish the incorporation in or on knockdown. They react well with synergists and exhibit the granules of the biologically active substance. Some relatively low mammalian toxicity. Generally they 65 of the techniques for doing this are disclosed in copend breakdown quickly and leave little residue. ing application Ser. No. 518,281, ?led July 28, 1983. It appears that the principles of the invention are The latter application describes, as one embodiment equally applicable to fungicides. There are several dif of its disclosure, the formation of an intimate admixture 5,022,917 11 12 of a biologically active material with at least as large, be a readily soluble fertilizer material supplying nitro and preferably a larger, volume of particles of a nitroge gen, such as urea, in a preferred embodiment. The gran nous material of the kind described in this present appli ules must have strength, size and weight suitable for cation, preferably melamine, made up in granular form handling and storage, and preferably also for mechani with a soluble binder, preferably urea. In this form, the cal dispensing. The granules may be in the form of biologically active material is protected from the de— ‘agglomerates, prills or ?akes. gradative effects of sunlight and oxygen, the leaching In a more speci?c embodiment, the granular compo effect of water, the volatilization effects of wind and sition comprises a mixture of: (a) a BAM having herbi sun, as well as the microbiological breakdown initiated cidal properties; (b) particulate melamine having parti by microorganisms, following application of the gran cle sizes predominantly less than 40 mesh (about 4-00 ules to the soil. ‘ micrometers), and (c) a urea binder that holds the BAM, In the present case, the granules are not intended to the melamine particles, and any other materials present, be added to the soil, but rather, to an aqueous vehicle to in granular form. This embodiment of the composition form a liquid formulation that may be applied to the soil comprises: from about 1% or less up to about 30% by or to foliage, for example. 15 weight of the herbicidal material, and generally, not In the embodiment of the present invention where more than about 20%; from about 10% to about 95%, some or all of the components of the sprayable composi and more generally from 40% to 80%, by weight of tion are prepared in granular form, the processes used particulate melamine; and from about 15% to about for making the granules are similar to those disclosed in 90% and more generally from 20% to 60%, by weight copending application Ser. No. 305,603, ?led Sept. 25, 20 of the urea binder. 1981, modified however if desired to accomplish the Such granules then provide a convenient, readily incorporation in or addition to the granules of the bio handled and readily measurable means for adding the logically active substance, which is generally a biocide, granulated ingredients to an aqueous vehicle to make up and preferably a herbicide, most preferably one that has a liquid formulation that may be sprayable if desired. selective toxicity for weeds. 25 The preferred high nitrogen material is particulate It is possible to add the biologically active material to melamine. Experimental evidence demonstrates its effi granules prepared in accordance with the disclosures of cacy with certain herbicides in making them more effec either of these two just-mentioned patent applications, tive. It is believed that the nitrogen source may also be by spraying a solution or suspension of the biologically selected from the group consisting of melamine, ben active material on preformed granules. This places the 30 zoguanamine (2,4-diamino-6-phenyl-s-triazine), dicyan biologically active material on the outer surface of the diamide, ammeline, ammelide, cyanuric acid, mixtures granules as a coating or layer. thereof, their inorganic salts, their organic salts, and A preferred technique for making the granules in mixtures thereof. These salts are preferably selected volves the incorporation of the biologically active ma from the group consisting of the hydrochloride, hydroi terial in the form of a powder with melamine or other odide, metaphosphate, nitrate, orthophosphate, ortho like nitrogen compounds. This mixture is then continu phosphate dihydrate, pyrophosphate, potassium dihy ously tumbled in a rotary drum in a fashion that is well drogen phosphate, bisulfate, and sul?te, and, as well, the known in the fertilizer art, while molten urea or the like cyanurate, chloroacetate, and formate salts, and mix is sprayed into the tumbling bed in the form of small tures thereof. All of these materials are characterized by droplets. As the tumbling continues, this technique 40 poor or slight solubility in pH 7 water at 20° C., and by forms granules from the mixture in the bed and the slow conversion in the soil to a form in which the nitro molten binder material. Granules formed in this way are gen is useful to plant life growing in the soil. The useful characterized by high crush strengths. There are many salts also include those where the associated ions are possible variations to this technique, such as, for exam substantially or entirely comprised of one or more of the ple, spraying a solution or suspension of the biologically 45 nutrient elements recognized by the American Associa active material on the tumbling bed of melamine parti tion of Plant Food Control Of?cials, such as N, P, K, S, cles, then spraying that tumbling bed with droplets of Ca, Fe, Zn and B, among others, and represented by molten urea or other binder material. In another varia such compounds as melamine phosphate, nitrate, or tion, the biologically active material can simply be sulfate; melamine borate; and ureidomelamine. sprayed on the surfaces of such preformed granules, to 50 These nitrogen source materials, as ordinarily avail the desired concentration. able commercially or as prepared, are in the form of The composition of such granules comprises a mix very ?ne particles. In the case of melamine, for exam ture of: (a) the biologically active material; (b) one of ple, the commercially available product typically has the particulate sources of fertilizer nitrogen already crystalline particles that are smaller in size than 10 described, that is characterized by a particle size of 10 55 mesh, US. Standard Sieve size, that is, smaller than 2 mesh or less, preferably 40 mesh or less, and (c) a binder mm. (2,000 micrometers), and almost all of which are that holds the mixture in solid form. An inert or fertil smaller than about 40 mesh, that is, about 400 microme izer filler may also be used. Moreover, since the inten ters and less. Melamine as presently available commer tion is to add these granules to an aqueous vehicle, cially, from most sources, is a very fine, powdery, light emulsifying, stabilizing and suspending material may 60 material. For the purposes of the present invention, also be incorporated in the granules. The granules gen even extremely ?ne particles of melamine can be used. erally may be from 1 mm. to 10 mm. in size for conve In some commercial processes for making melamine, nience in applying using ordinary mechanical handling extremely ?ne particles are removed from vent gas in a and packaging of equipment of the type used for granu ?lter. Such ?ne particles have been utilized in preparing lar fertilizers. 65 liquid compositions of the invention. Their large surface The binder for holding the particles together in gran area can be expected to be advantageous upon applica ular form should be readily soluble and preferably tion to the soil, for releasing plant nutrient nitrogen at a should have plant nutrient value. Thus the binder may faster rate, and also for favoring hydrogen bonding and 5,022,917 13 14 any chemical reactions that may occur. Hence, no imparts greater strength. The granular products may lower limit on melamine particle size is speci?ed. The additionally comprise other fertilizer materials such as same is true of the materials that may be used in place of potassium, phosphorus, and micronutrients. Examples melamine. Very ?ne particles are also useful in forming of micronutrients include calcium, zinc, magnesium, stable suspensions. ‘iron, boron, cobalt, manganese, molybdenum and so When the BAM is in powder form, preferably with dium. particle sizes below 40 mesh, U.S. Standard Sieve, it The granular compositions that may be used in form may be mixed with dry crystals of or powdered mela ing liquid, sprayable compositions of the present inven mine (or other similar nitrogen source), then granu tion generally comprise an amount up to about 30% by lated. When the BAM is a liquid, it may be sprayed on weight of the BAM, preferably up to about 20%, and the melamine, or on_a powdered binder material such as from about 10% to about 95% by weight of melamine urea, or on both, then dried; or it may be mixed with a or other slow release source of fertilizer nitrogen, pref liquid binder component. It may also be sprayed di erably 10% to 85%; and more preferably up to about rectly on performed granules, which are then dried. It 10% by weight of BAM and from about 40% to about may also be ?rst converted to powder form, then used. 80% by weight of the melamine, with a soluble binder. Or the BAM, if not in liquid form, in some cases may be When the binder is urea, the amount used is from about converted to a solution or suspension, and used in whole 15% to 90% of the granule and preferably from about or part as the binder for making granules. 15%, preferably 20%, to 60% of the granule. When the In one preferred mode, to make granules, the parti binder is soluble resin, less may often be used, i.e., about cles of melamine or other similar slow release fertilizer 20 5%—l0%. material, and the particles of a BAM, preferably in Since the granules are intended to be dispersed in an admixture, are bound together in granular form with a aqueous vehicle, they may be any convenient size. Pref soluble binder material. The binder may be selected erably they have a size in the range of from about 1 mm from a broad spectrum of materials, but preferably is to about 10 mm, and more preferably, up to about 5 mm, 25 selected so that it is either inert, biodegradable, soil-con and most preferably, from 2 mm to 4 mm. Preferably, ditioning, or preferably, has plant nutrient value. the granules in the 2 mm to 4 mm size range exhibit an Among the preferred binders are those selected from the group consisting of urea, readily soluble protein average crush strength of at least 450 g (1 lb), and more preferably, at least 1350 g (3 lb). aceous materials, readily soluble resins, and water-solu In one method of making urea-melamine-BAM gran ble latices of synthetic polymeric materials. Binders that 30 have some plant nutrient value are most preferred, such ules, particles of melamine and particles of the BAM are blended together with particles of urea. This blend is as urea. The binder that is used should produce a granule that sprayed with water or with an aqueous solution of other is suf?ciently strong, upon hardening or curing, to im material, in an agglomerating device such as a disc part to the granule a crush strength of at least 450 g (1 pelletizer or a rotating drum. The blend becomes tacky lb), as determined by tests on ten granular agglomerates and agglomerates. The agglomerates are then dried in randomly selected, with sizes in the range from 3 mm to air by a conventional technique, as in a hot air over or ' 4 mm, the results being averaged. Preferably, however, ?uidized bed, generally at a temperature below the the crush strength is at least 900 g (2 lb), and more melting point of the binder material. preferably, 1350 g (3 lb). A crush strength of about 450 Although granules are usually prepared by the tech g is comparable to conventional, commercial prilled niques described above, they can be produced by extru urea and is adequate strength for use in most forms of sion, pressing and granulating, and briquetting. commercial handling, storage, and packaging equip If the granules contain all of the ingredients needed or ment. Higher crush strength values guard against break desired in the liquid formulation, the granules are sim age, as when the granules are bagged and the bags are 45 ply added to water and mixed. Depending upon the stacked, and during handling. composition and concentration, the resulting mixture When a readily soluble material such as urea or a salt, will be either a solution or a suspension of melamine such as ammonium nitrate or potassium dihydrogen particles in a solution. The ingredients employed can be phosphate, is employed as the binder for the granules, selected to accomplish a particular desired result. How the binder material will disintegrate rapidly in a liquid 50 ever, there should always be present in the formulation vehicle, and release the BAM and the slow release ni the combination of melamine, either in solution, in sus trogenous material, generally in the form of discrete pension, or partly dissolved and partly suspended, with particles of each, if that was their form when the gran the biologically active material. Then, when the formu ules were prepared. lation is applied, upon drying there will be present, Urea is the preferred binder, not only because it per 55 generally in intimate association, melamine together mits the production of granular products with sufficient with biologically active material. It appears that this crush strength, and having suitable weights, sizes and combination is responsible for the improved ef?cacy, shapes for convenient use, but also because it is readily such as the prolonged activity, that may be exhibited by soluble and adds a valuable fast release nutrient mate the biologically active material, as compared to the case rial. When urea is used as a binder with ?ne particles of 60 where the biologically active material is applied alone. melamine, the urea will dissolve rapidly in water and The melamine contributes slow release nitrogen fer release discrete particles of the melamine. Other readily tilizer values. For best results with many crops, the slow soluble, fast release binders include ammonium sulfate, release nitrogen should be complemented with fast re ammonium phosphate, diammonium phosphate, ammo lease nitrogen. It is therefore preferred that urea be nium nitrate, potassium nitrate, potassium sulfate, potas present in the sprayable formulation, or other fast re sium chloride, potassium dihydrogen phosphate, and lease nitrogen source either alone or in combination ammonium chloride. Preferably such salts are used in with urea. Urea is a material of choice, however, since combination with urea, a latex, or other binder that it is believed that the solubility of melamine in an aque 5,022,917 15 16 ous vehicle is increased when dissolved urea is present -continued in that vehicle. To prevent or minimize settling of melamine particles or other particles, it is preferred that the aqueous spray Component Weight % by Weight able formulation contain an additive or be mechanically Clay 20 lb 1.00% agitated. The additive may be an emulsifying agent, a 62% potash solution 390 lb 19.50% suspending agent, a stabilizing agent, or one or more Total 2000 lb 100.00% agents that combine some of these properties. The pres ence of a wetting agent may be desirable, to improve The melamine-urea granules were SUPER 60 ferti1— the wetting characteristics of the sprayable formulation izer granules manufactured and sold by Melamine when applied to some substrates such as plant leaves. Chemicals, Inc. They were made up by mixing together Other materials that may be incorporated in the liquid approximately 70 parts by weight of melamine and 30 vehicle include one or more materials contributing solu parts of pulverized urea powder, moistening, granulat ble, fast release nitrogen values; potassium values; and ing, holding for an annealing period, and then permit phosphorus values. ting the granules to cool. The amount of nitrogen con Many herbicides and other pesticides are sold in the tributed by the melamine was about 45%, and the form of wettable powders. This physical form of the amount contributed by the urea was about 15%, for a biologically active material is very convenient for in total of about 60% nitrogen by weight of the granules. corporation in a granule, and also for incorporation in the liquid vehicle of a sprayable formulation. Some 20 B. Liquid Herbicidal-Fertilizer Formulations biologically active materials are also available in spraya A biologically active material can easily be incorpo ble liquid form. Often, the most convenient and practi rated into this balanced liquid fertilizer base by simple cal way to use such a sprayable biologically active ma terial is by adding the other desired components to it, mixing. including more liquid if necessary for appropriate 25 The liquid suspension fertilizer is useful as a vehicle spraying consistency. for oxadiazon SOWP, sold under the trademark Ron The invention will be demonstrated in several spe star® as a herbicide for pre-emergent grass control. ci?c examples. These are intended to be illustrative only Ordinarily this herbicide is recommended for applica and are not intended to limit the invention. All parts and tion at l to 2 lb of the active ingredient per acre. When percentages are by weight, and all temperatures are incorporated in the liquid suspension fertilizer above, Celsius, unless expressly stated to be otherwise. application at the low end of the recommended range generally appears to be appropriate. EXAMPLE 1 This exemplary liquid suspension fertilizer is also . A. Liquid Suspension 14-9-12 Fertilizer, Useful as a valuable for formulation with pre-post emergent wheat Liquid Vehicle 35 control agents. One such agent is chlorsulfuron, sold This example illustrates the preparation of a liquid under the trademark Glean® as a 75% DF. This is suspension fertilizer formulation having a 14-9-12 analy recommended for application at the rate of 0.2 to 0.5 oz sis, that is useful as a liquid vehicle in making up a spray of active ingredient per acre, for good post-emergent able biocidal formulation. It was made up from several 40 control of weeds. It also has some potential for pre solid components that were formed into a suspension in emergent control. When formulated with the above water. One of these components was a batch of mela liquid fertilizer, superior efficacy can be expected. mine-urea granules. The other dry components in The liquid suspension fertilizer is also a useful vehicle cluded monoammonium phosphate, clay, and potash. for the application of plant growth regulators. For ex Another component was anhydrous ammonia. 45 ample, Embark ® 25 me?uidide is easily mixed into the Initially, a base composition, referred to as Base A, liquid suspension fertilizer. It can be applied at rates in was made up by mixing together the following compo the range of 0.125, or 0.25, or 0.375 lb of active ingredi nents: ent per acre, depending upon the effect desired, with good efficacy when applied in the above liquid fertil 50 izer. Base A Component Weight % by Weight In addition to the kinds of formulations suggested above, biologically active materials may be applied in Water 165 lb 30.75% Monoammonium phosphate 340 lb 62.50% combination. For example, combination of the post Anhydrous ammonia 30 lb 5.25% emergent herbicides 2,4-D plus MCPP plus dicamba Clay 10 lb 1.50% can be added to the liquid suspension fertilizer for use as a selective broad leaf weed control material, active The Base A composition prepared in this way amounted through foliar uptake. Other combinations with similar to 545 lb having the analysis 11-33-0. It was combined activities are: 2,4-D plus 2,4-DP plus dicamba; triclopyr with other ingredients to make a liquid suspension fertil 60 plus 2,4»D; and triclopyr plus chlorsulfuron. With these izer, as follows: ‘ also, good prolongation of activity can be expected. When the liquid suspension fertilizer described above is used as a BAM vehicle and applied at the rate of 500 Lig uid SusEnsion Fertilizer lb of liquid suspension per acre, the rate of nitrogen Component Weight % by Weight application per acre is 70 lb. Of this 70 lb, 28.75 lb is Water 675 lb 33.75% readily soluble nitrogen from the MAP, anhydrous Base A 545 lb 27.25% Melamine-urea 370 lb 18.50% ammonia, and urea, and the remainder, 41.25 lb, is de granules (60-0-0) rived from the melamine and is released slowly. 5,022,917 17 18 and like factors. However, whatever amount of mela EXAMPLE 2 mine remains undissolved becomes suspended in the Liquid Insecticidal Composition liquid vehicle so that the ?nal formulation becomes a Dursban ® insecticide, a product of Dow Chemical, suspension in a solution. The stability of the suspension is useful against chirch bugs, army worms, and blue _ is good even with very little agitation, because of the grass billbugs. It has residual activity of 7 through [4 very small size of the melamine particles. However, the days. It is usually applied at the rate of 1 lb of active presence of a suspending agent, or thickener, is useful in ingredient per acre. Often it is applied with readily further stabilization and in the prevention of settling. soluble fertilizer nitrogen at 1 lb of nitrogen per 1000 sq. When this formulation is applied by spraying, each ft. In a typical formulation, this amounts to 600 parts per individual drop will contain some particles of the Bal million of Dursban ® insecticide, active ingredient, for an® herbicide, usually some particles of suspended each 3% of nitrogen in the sprayable solution. melamine, and the liquid portion will contain dissolved Dursban® insecticide is normally supplied as an melamine. There may also be other chemicals present in emulsifiable liquid that contains 58% by weight of the each drop, such as urea. As the individual droplet dries active ingredient and 42% by weight of xylene. To use and the water present evaporates, the surface tension it in combination with melamine crystals, the desired forces within the drop will pull together the suspended amount of melamine is added together with a suitable particles of the Balan® herbicide and the suspended suspending agent, such as, for example, about 0.1% by melamine particles. The dissolved melamine particles weight of the total formulation of Drew Chemicals also begin to crystallize out, and to bond the already SPD 12-674 dispersant. Preferably, however, a source 20 present particles together. This action creates the equiv of soluble nitrogen is also incorporated in the formula tion. alent of a very small granule on the surface on which When such a formulation is applied to turf grass, for the drop has been applied and on which it dries. The example, the efficacy of the insecticide can be expected presence together of the melamine and the Balan® to be improved compared to that normally observed in 25 herbicide is believed to be responsible for the extended the absence of melamine. activity that can be expected to be observed for the When this kind of formulation or a similar formula herbicide. tion is applied to grass, drops ordinarily are deposited This type of herbicidal suspension is useful for appli on the blades of grass. Each drop contains very small cation to turf grass for the control of crabgrass. quantities of dissolved melamine, and some suspended In similar fashion, sprayable herbicidal compositions gnelamine, and either suspended and/or dissolved bio can be made up containing other herbicidal materials. logically active material, in this case, Dursban insecti For example, Betasan® brand of bensulide, (Stauffer cide. As the drop dries and the liquid evaporates, the Chemical Corp.), provides broad spectrum control of surface tension forces will tend to pull together and weeds. It has selected agricultural applications on some concentrate the melamine and the insecticide. The dis 35 vegetables such as carrots. The half-life is quite long, solved melamine will begin to crystallize out and to and the solubility is low, 20 ppm. Betasan ® herbicide , bind any pre-existing particles already present together. may be prepared into sprayable herbicidal suspensions It is theorized that this creates the equivalent of a small in the manner described in this example, using the ap granule on the surface of the blade of grass, or on the propriate amount of active ingredient per acre for mak soil, wherever the drying occurs. Thus, the physical 40 ing up the formulation. Generally the application rates protection afforded by the melamine is believed to sup are higher in the south than in the north for this particu plement the action of any hydrogen bonding or chemi lar herbicide, and multiple repeated small applications cal reaction that may take place or may have taken are more effective than one larger application. It is place between the melamine or other nitrogen source, believed that use of the present invention will eliminate and the biologically active material. 45 the need for multiple applications or make fewer appli EXAMPLE 3 cations possible, by prolonging activity substantially. Atrazine is a herbicide product of Ciba-Geigy [2 'Sprayable Herbicidal Formulation chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], Balan ® herbicide is sold as a wettable powder. It is which is useful on Saint Augustine grass and other ordinarily applied at the rate of 2 lb per acre of active warm season grasses during the fall-winter grass dor ingredient in a formulation that furnishes 40 lb of nitro mancy. It can be made up into sprayable suspensions in gen per acre. the manner described above, the appropriate applica A sprayable Balan® herbicide formulation is made tion rate being about 1 lb to a maximum of 2 lb of active up using 174 gallons of water for each acre to which the ingredient per acre. formulation is to be applied. Two lb of the commercial Balan ® wettable powder is added to each 174 gallons EXAMPLE 4 of water, together with 30 lb of ?ne particles of com Liquid Herbicides for Douglas-Fir Seedlings mercially available melamine having a particle size of 400 micrometers or less, predominantly. This amount of Granules containing herbicidal material were made melamine supplies 20 lb of nitrogen. 60 up in accordance with the following formulations: To make up the nitrogen content to the desired level (a) 2,4-D 5%, melamine 71%, urea 24%; of 40 lb per acre, urea is added. The requisite amount of (b) 2,4-D/KL (a controlled release formulation of 42.9 lb of urea dissolves readily in the water. 2,4-D with kraft lignin) 10%, melamine 72%, urea 18%. Ordinarily, 174 gallons of water would dissolve about To make up liquid herbicidal formulations, the gran 7 lb of melamine. Since melamine is somewhat more 65 ules (a) and (b) are each placed in appropriate quantities soluble in a urea solution than in plain water, more of water, with mixing. In addition, as a comparison melamine may actually dissolve than 7 lb, depending on control, 2,4-D in liquid form is made up for application temperature, the presence of other dissolved substances, at a conventional commercial rate. 5,022,917 19 20 To evaluate these formulations, Douglas-?r seedlings ble formulation is to add melamine/urea granules to a (2.0) are planted in 10” diameter pots. The several treat formulation of Velpar® L herbicide in an aqueous ments involved are each applied to three potted ?rs. vehicle. The granules can be made up with a combina One set of potted seedlings is selected as a control to tion of more than one herbicide, for example, the combi receive no treatment whatever. A second set of potted nation of both 2,4-D and Velpar @ herbicide. Such a seedlings is selected to receive a commercial rate appli ' combination can be dissolved in an aqueous vehicle to cation of the liquid form of 2,4-D made up as the com~ form a liquid herbicidal formulation. parison control. In this and in all other cases in this In using these herbicidal formulations, it is preferred example where 2,4-D is applied, it is applied at a rate that the liquid be applied as a spray directly to the earth, equivalent to 20 lb of active ingredient per acre. Liquid and that a heavy spray be used to minimize and prefera formulations made up from granule lots (a) and (b) are bly to eliminate drift. For aerial application, timing of also applied, each to a different set of potted seedlings. the application is important, since growth from buds is These sets are then monitored for seedling height sensitive. growth, growth, quality of the seedling, and weed growth surrounding the seedling represented as a per EXAMPLE 5 centage of soil surface. Initially, there should be no Liquid Herbicidal Formulations From Granules visible weeds present on the soil at the time of treat Having a Urea Binder ment. However, since volunteer weed seeds are always Several granule formulations were prepared using present in the atmosphere as well as in the soil, they melamine particles, powdered urea, and a BAM, in the daily settle on the surface of the soil in the pots, and all 20 form of a ?nely divided powder. The granules were pots are exposed in essentially the same way. The control plantings with no treatment generally are prepared by mixing the dry ingredients, tumbling, spraying to moisten the urea and make it tacky, and overrun with weeds in about 8 weeks, over 100% of the soil surface, with the weeds surrounding and overtow drying. Representative granule formulations included ering the seedlings. Normally all other treatments will 25 the following, where all parts and percentages are by exhibit better mean height growth. weight, dry basis, unless otherwise indicated. The commercial rate 2,4-D application initially will give good weed control, but since 2,4-D has a short A. Herbicide Formulations ~ Urea Binder period of activity, as soon as its effectiveness diminishes, 5A1 Melamine 78 g weeds invade. After 14 weeks, the weed population can Urea 20 g be expected to occupy about 90% of the soil surface. 2,4'dichlorophenoxybutyric acid (2,4-DB) 2 g Nevertheless, mean height growth can be expected to 5A2 Melamine 78 g be substantially better than that observed in the case of Urea 20 g Treflan ® brand of 2 g the no treatment control seedlings, by a substantial tri?uralin (a,a,a-tri?uoro-2,6-dinitro-N,N percentage. 35 dipropyl-p-toluidine) Both liquid formulations made up from the melamine 5A3 Malamine 78 g granules can be expected to give good, long lasting Urea 20 g Dicamba 2 g weed control, lasting up to 24 weeks. The correspond (3,6-dich1oro-o-anisic acid) ing growth of the seedlings should be excellent, and at 5A4 Melamine 63.3 pts. the end of this period, there should be a second bud Urea 31.6 pts flush. Mean growth can be expected to be at least 75% Cotoran ® brand of 4 pts. (as received) better than that of the no treatment control seedlings, at ?uometuron (l,l-dimethyl-3-(a,a,a least in part as a result of much reduced weed competi tri?uoro-m-to1y1)urea) tion. (80 wt. %) In place of the 2,4-D herbicide in either form, other 45 5A5 Melamine 63.3 pts Urea 31.6 pts. herbicides can be used. For Douglas-fir seedlings, Vel Dacthal ® brand of 20 pts. (as par ® herbicide is also favored. received) I-Iexazinone herbicide is a du Pont product believed DCPA (dimethyl tetrachloroterephthalate) to contain about 90% by weight of the active ingredient (75 wt. %) 5A6 Melamine 63.3 pts. hexazinone (3-cycl0hexyl-6-(dimethylamino)- 1 -methyl Urea 31.6 pts l,3,5-triazine-2,4(lH,3-H)-dione) plus 10% inert ingre Lorox ® brand of 5 pts. (as dients. Hexazinone is availabe commercially in both a received) solid and liquid form. The liquid form is available under linuron (3-(3,4-dichloropheny1)-l-methoxy l-methylurea); or, (N'-(3,4-dichlorophenyl)-N the traedemark Velpar® L, containing about 4 lb of methoxy-N-methylurea)) active ingredient per gallon. The liquid form is usually (50 wt. %) formulated into a sprayable composition. In the solid 5A7 Melamine 63.3 pts. form, the hexazinone is granular and contains from 5% Urea 31.6 pts. Prowl ® brand of 5.1 pts. (as to 10% by weight of the active ingredient on an inert received) clay substrate, available under the trademark Pronone N~(l-ethy1propy1)-2,6-dinitro-3,4-xylidine) 5G or 106. It is believed that moisture is required to about 1.68 pts. active ingredient) activate hexazinone in the soil. 5A8 Melamine 63.3 pts. Urea 31.6 pts. When melamine-urea granules are prepared contain Basalin ® brand of 5.1 pts. (as ing about 0.5% to 1.5% by weight of the active ingredi received) ent of Velpar ® hexazinone herbicide, and the granules N-(Z-chloroethyl)~a,a,a-trifluoro-2,6-dinitro are then made up into a liquid formulation, excellent N-propyl-p toluidine (4 lb/gallon) (about 244 pts. active ingredient) long term weed control, with accompanying good 5A9 Melamine 64 pts. growth benefits on the part of the seedlings, can be Urea 32 pts. expected. An alternative way to make up such a spraya Ronstar ® brand of 8 pts. (as 5,022,917 21 22 -continued EXAMPLE 7 A‘ Herbicide Fmmulmms ' Um Bind" Sprayable Herbicidal Compositions for Use on received) Soybeans oxadiazonisopropoxy(phenyl)-Ag-l,3f4-oxadiazolin-5eone) Z-tert-but 1-4- 2.,4-dichloro-5- 5 l A- Lasso ® Herblclde_ _ 5M0 Melamim 64 Pts' The herbicide employed was commercially available UreaDual ® brand of 324 pts.pm (as Lasso® alachlor herbicide,. . which. is. a liquid. . form of received) the herbicide containing 45.1% active ingredient per metolachlor (2-chloro~6’~ethyl-N-(Z-methyl- 10 gallon. lmethylcthy1)ac=H>-t<>luidide) Two batches of granules were made up with different 5A“ Mdamine 63-3 P‘s' contents of herbicide, one being twice as strong as the Ame,‘Urea ® brand of 3L65 pm. pts. (as other in~ terms of weight- of active- ingredient~ ~ used. - may“) In both cases, the production process was the same. atrazine(2-chloro-4(ethylamino)-6-(isopropyl- 15 Melamine and urea were mixed with the liquid herbi amin0)-s-m'azine) cide, and enough moisture was added to permit granula SAIZ Siam-i3’) 63 3 PIS tion. The two batches ofdried granules have the follow Urea 3L6 ms‘ mg respective compositions: Bladex @ brand of 5 pts. (as received) 20 cyanazine (2-[[4-chloro-6-(ethylamino)-s- Bach ILA-l Batch 7'A'2 triazin-Z-yl]amino]-2-methylpropionitrile) Wt. % Lasso ® 2.96 4.83 (80 wt. %) liquid (as is) in 5Al3 Melamine 63.3 pts. the granules Urea 3L6 pm Melamine % 40.76 39.97 propham 6 pts‘ 25 Urea % 56.28 55.20 (isopropyl carbanilate) Total 100.00 l00.00
Each of these granular formulations is easily made up Batch 7-A-l contains about 53% nitrogen, whereas into a sprayable liquid formulation upon addition of the 30 Batch 7-A-2 contains about 52% nitrogen. These appropriate amount of water and stirring until all of the batches of granules can be dissolved, respectively, in granules have disintegrated and all of the released mate- enough Water for convenient application at the rate of rial is distributed uniformly. The suspended solids are _1'5 1b 9f active ingmdiem Pf?!‘ acre, and 15 1b of active very ?ne and are readily sprayab1e_ ingredient per acre, respectively. Batch 7-A-l contains In each case, the applied sprayable formulation, upon 35 l'335% active mgredlent_ “1 fhe wnules’ and Batch drying, can be expected to exhibit improved efficacy; in 7'A'2 coniams 2-1789?’ active “igrefilem ‘P the, granules'v many cases, exhibiting activity substantially greater The time of mclamme to actwe mgrcd‘ent m_ the two than that of the herbicide if applied alone or in a con- batches 15’ respectively’ 30:1 and 18:1’ dry basis’ _ ventional commercial formulation. When sprayed in the manner recommended for this 40 herbicide, improved efficacy should be observed, be EXAMPLE 6 cause of the presence and intimate association of the sprayable Growth Regulating Formulations melamine particles with herbicide particles. Granules were prepared following the same tech- B‘ Lorox ® Herblclde niques as in the preceding example, but using a growth 45 Chemically, the active ingredient of this herbicide is retardant material as the biologically active material, as 3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea. When follows: used as recommended by the manufacturer, linuron ‘ herbicide selectively controls germinating and newly established broad leaf weeds and grasses in crops such 6A1 Mclamln’ 63-3 P‘s- 50 as soybeans, cotton, corn, sorghum, potatoes, carrots, static Hydmidc 31': 5:: and parsnips. It is generally sprayed on the soil as a 6A2 Melamine 63'; pm pre-emergence or post-emergence treatment, often in a Urea 31.6 pts, spray formulation with a suitable surfactant. Alar ® 6 Pts- As in Example 7A, granules were prepared. How brfmd °f dami"°zid°
As footnote 3 in connection with Table 8-1 indicates, 0, 100, and 200 lb N per acre. In assembling the raw of the total amount of nitrogen applied, half is from the data, the observations were made following the com readily soluble urea and half from the poorly soluble 15 mon practice in this art. Grass vigor was compared to a melamine. The readings on bare ground in Table 8-1, control. A positive reading meant that the herbaceous and on weed vigor reported below in Table 8-2, were material was more vigorous than the control. A nega taken about 6 weeks from the treatment date. At that tive reading indicated that the herbaceous material was time, the amount of nitrogen available from the rnela- 20 more chlorotic than the control in appearance. The mine would have been essentially negligible, whereas rating values fell in the range from —3 to +3, including substantially all of the nitrogen from the urea would 0, as is conventional. have been available, subject to such factors as rainfall, For the purposes of 8-2, and to make the results more translocation, and the like. easily understood without a great deal of study, the raw In analyzing the .data in Table 8-l,the values reported 25 data has been condensed. A single — sign for vigor for hexazinone applied at 2 lb per acre and for nitrogen rating means that generally the observations made (re applied to a total of 200 lb per acre are believed to be ported in Table 8-2 for 200 lb N/acre) were positive, in signi?cant. In analyzing the data, it is noted that the fast the range from O to +2. Where two + + appear, the release nitrogen from the urea tends to stimulate plant rating was above +2. A single negative sign in Table growth and’ vigor. The hexazinone, on the contrary, 30 8-2 means that generally the reported values were in the tends to limit plant growth and destroy plant vigor. range from O to -2. Thus, the results for plot group 3, where the hexazinone The reported values of weed vigor in Table 8-2 dem was incorporated in the granules, and for plot group 4, onstrate that a combined liquid application of hexazi where hexazinone and melamine particles were sprayed none and melamine resulted in much less weed vigor - simultaneously in a single liquid vehicle, appear to be 35 than the cases where the hexazinone was incorporated signi?cant by comparison with the values that are com- in melamine/urea granules, or where the hexazinone parable for plot group Nos. 1 and 2. At these levels of was applied separately from either urea prills or hexazinone and melamine, as reported in the results for melamine/urea granules. TABLE 8-2 Weed Vigor“) Average Three Sites Plot Group l-lexazinone Vigor Ratingm; No. Treatments Rates; lb/acre N applied at 200 lb/acre l Velpar @ L liquid spray, ‘ plus Urea prills separately applied 2 Velpar @ L liquid spray, plus MCI 55% N granules separately applied 3 l-Iexazinone incorporated at l.l% by weight into the MCI 55% N granule 4 Velpar ® L liquid spray with MCI 55% N granules dispersed into the liquid ("Vigor is degree of green color and apparent health of grasses and herbaceous vegetation remaining on the treatment plots. ating compares vigor of the weeds in the treatment plots with a control treatment of no application of hexazinone or nitrogen which was assigned a zero rating. A (+) rating is more vigorous than the control and a (—) rating less vigorous. plot group Nos. 3 and 4, there appears to have been signi?cant co-action. The herbicide appears to have 60 been potentiated and its efficacy increased, by co The studies in Tables 8-1 appear to indicate that the application of the hexazinone herbicide with melamine combined application of hexazinone with urea and mel particles, whether in granule form or in a common amine, whether in the form of granules or in the form of liquid vehicle. a liquid slurry, is more effective for weed kill or inhibi In Table 8-2 below, a summary report is presented of 65 tion, and for reducing the vigor of weeds that are pres average wheat vigor. The raw data from which this ent, than comparable applications of hexazinone in the table was prepared includes observations made when no form of a liquid spray combined with the separate appli herbicide was applied, and nitrogen application rates of cation of urea prills, or the separate application of hex 5,022,917 29 30 azinone in a liquid spray plus the separate application of razine, 2-chloro-4-(ethylamino)-6-(isopropylamino)-s urea-melamine granules containing 55% nitrogen. This triazine; barban, 4-chloro-2-butynyl-m-chlorocarbani increase in effectiveness of weed kill or inhibition is late; and cyanazine, 2-[[4-chloro-?-(ethylamino)-s-tria believed to be attributable to the coaction that appar zin-2-yl]amino]-2-methylpropionitrile. ently is observed when melamine and hexazinone are One very promising application of this invention applied together in such form as to permit co-action. relates to the use of liquid formulations containing The data reported in the two tables above demon Dursban ® brand of insecticide to lawns, for the con strate that when there is co-application of melamine trol of insects. Dursban® brand of insecticide is be with hexazinone herbicide, there is earlier activity and lieved to contain, as its active material, 0,0-diethyl the herbicide is more efficient. Other data, not reported 0-3,5,6-trichloro-2-pyridyl phosphorothionate (chlor above, indicated a prolongation of activity as measured pyrifos). against grass germination. When the poorly soluble, particulate nitrogen source CONCLUSION is melamine or its salts, and granules of melamine, BAM and water soluble binder are made up, the preferred There appears to be a de?nite improvement in effi proportions are from 60% to 85% melamine, from 15% cacy when a herbicidal biologically active material is to 40% of the soluble binder such as urea, and up to applied to plant life or to the soil, in either granular or 30% of a BAM. When the granules have been made by slurry/solution association with one of the enumerated nitrogenous materials, and particularly, with melamine. using molten urea or the like as the water-soluble This invention is particularly useful for aerial applica binder, the proportions may be from 10% to about 67% tion of a slurry/solution to a stand of trees or seedlings. melamine, from 33% to 90% urea binder, and again, up If so used, it should be applied prior to bud break in the to about 30% of the BAM. Thus, overall, the propor spring. While the improvement mechanism is not fully tions of preferred, granules may be from 10% to 85% understood, it is speculated that hydrogen bonding is melamine, from 15% to 90% of the urea binder, and up involved, and that accordingly, those biologically ac 25 to 30% of the BAM. Generally the minimum amount of tive materials that are susceptible to hydrogen bonding BAM is 1% but it could be less. It must be an effective with the nitrogenous material, such as melamine, are amount after being placed in the liquid vehicle and particularly useful. applied. It is also possible that the mechanism responsible for The improved efficacy of liquid herbicidal formula improved results has little to do with either hydrogen tions may take the form of improved weed kill, more .bonding or chemical reactivity, but rather depends prolonged activity, earlier manifestations of activity, upon some physiological factors. Thus the triazine, such lower permissible dosage level of active ingredient, or as melamine, may stimulate some sort of response in the the like. plant to make it more susceptible to the action of the While the invention has been disclosed in this patent herbicide. At present, the available evidence appears to application by reference to the details of preferred em favor hydrogen bonding or chemical reaction, since an bodiments of the invention, it is to be understood that essentially simultaneous but separate application of the this disclosure is intended in an illustrative rather than materials is not as effective as co-application either in in a limiting sense, as it is contemplated that modifica granular or liquid forms. tions will readily occur to those skilled in the art, within While the sprayable liquid formulations can be made the spirit of the invention and the scope of the appended up in many different ways, one preferred way is by ?rst claims. incorporating the biologically active material in What is claimed is: melamine/urea granules, then placing a quantity of the 1. A process for herbicidally treating an agricultural granules in water and agitating. The proportions can be substrate, comprising adjusted to suit the particular application and rate of 45 applying to said substrate in an agriculturally accept application. Generally, however, the weight ratio of able liquid: melamine to herbicide, or other nitrogenous compound (a) a herbicidally active hexazinone material, and to biologically active material, is preferred to be at least (b) a melamine component selected from the group 3:1, as a matter of empirical observation. Other desired consisting of melamine, physiologically accept components in the sprayable liquid formulation may be 50 able inorganic and organic salts thereof, and incorporated in the granules, or may be added to the liquid vehicle. Incorporation of all or at least a substan mixtures thereof; tial part of the solid components in granules facilitates said melamine component being partly dissolved in shipping and measurements, and offers convenience said liquid, and the undissolved melamine compo while at the same time decreasing the risk of human nent comprises particles primarily less than 440 error in formulating. micrometers in size that are dispersed in said liquid, Among those herbicides that are preferred for use by said herbicidally active hexazinone material being incorporation in melamine/urea granules, for subse applied at a concentration that is useful and effec quent mixing with water to make a sprayable liquid tive for the exertion of its herbicidal activity, formulation, the following are mentioned: tri?uralin, said herbicidally active hexazinone material and said a,a,a-tri?uoro-2,6-dinitro-N,N-dipropyl-p-toluidine; melamine component being applied to be present dicamba, 3,6-dichloro-o-anisic acid; ?uometuron, 1,1 on said substrate in such contact that they can dimethyl-3-(a,a,a-trifluoro-m-tolyl)urea; ?uorodifen, coact to improve the efficacy of said herbicidally p-nitrophenyl a,a,a-trifluoro-2-nitro-p-tolyl ether; linu active hexazinone material. ron, 3-(3,4-dichlorophenyl)- 1 -methoxy- l -methylurea; 65 2. The process of claim 1 wherein urea is also present, oxadiazon, 2-tert-butyl-4-(2,4-dichloro-S-isopropoxy dissolved in said liquid. phenyl)-A2-1,3,4-oxadiazolin-5-one; paraquat, 1,1’ 3. The process of claim 5 wherein said liquid com dimethyl-4,4'-bipyridinium ion [as dichloride salts]; at prises dissolved urea and a dispersant. 5,022,917 31 32 4' The process of claim 1 wherein Said liquid com- suspended in said liquid and that have particle sizes prises dissolved or suspended materials providing fertil- PredPmmamly ‘es? Fhan 400 lmcrometlars; and izer values an agricultural herbicidally active hexazinone mate rial at a concentration useful, upon application of 5~ A sprayable liquid Composition that is character‘ 5 said composition, to perform its intended function; ized by herbicidal and fertilizer activity, comprising whereby the combination of said poorly water solu an agriculturally acceptable liquid having dispersed ble N Source and sald agricultural herblcldally therein Sources of N fertilizer values Said N active hexazinone material, following application ’ of said composition, can coact for the improved Sources comprisi1_1g at least one pogrly water solu' 1O efficacy of said agricultural herbicidally active ble N source having a water solubility at 20° C., at hexazinone material, pH 7, not above 5 g per 100 g of water and being 6. The composition of claim 5 wherein the ratio of selected from the group consisting of melamine’ melamine t0 the material having herbicidal activity iS at the physiologically acceptable inorganic and OP least 3:1 by weight of melamine to the active herbicidal . h h f d . h f h . l5 ingredient. game sa S t ereo an mixtures t ereo W cm“ 7. The composition of claims wherein at leastapart of the Poorly water Soluble N Source, to the extent not said source of N fertilizer values comprises urea. dissolved in said liquid, consists of particles that are * " * * *
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