[go: up one dir, main page]

MXPA99003845A - Composition and method for treating plants with exogenous chemicals - Google Patents

Composition and method for treating plants with exogenous chemicals

Info

Publication number
MXPA99003845A
MXPA99003845A MXPA/A/1999/003845A MX9903845A MXPA99003845A MX PA99003845 A MXPA99003845 A MX PA99003845A MX 9903845 A MX9903845 A MX 9903845A MX PA99003845 A MXPA99003845 A MX PA99003845A
Authority
MX
Mexico
Prior art keywords
further characterized
composition according
composition
excipient substance
carbon atoms
Prior art date
Application number
MXPA/A/1999/003845A
Other languages
Spanish (es)
Other versions
MX9903845A (en
Inventor
L Gillespie Jane
J Ward I Anthony
Ge Jisheng
C Xu Xiaodong
J Sandbrink Joseph
Original Assignee
Monsanto Technology Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Technology Llc filed Critical Monsanto Technology Llc
Publication of MX9903845A publication Critical patent/MX9903845A/es
Publication of MXPA99003845A publication Critical patent/MXPA99003845A/en

Links

Abstract

A composition is disclosed for application to a plant that comprises an exogenous chemical (for example, a postemergent herbicide), an aqueous diluent, and a first excipient substance that is amphiphilic. The weight/weight ratio of the first excipient substance to the exogenous chemical is between about 1:3 and about 1:100. The aqueous composition forms anisotropic aggregates on a wax layer, and the presence of the anisotropic aggregates can be detected by a test described herein. Compositions of the present invention, when applied to plants, provide enhanced biological activity per unit amount of exogenous chemical, as compared to otherwise similar compositions containing surfactants that do not form anisotropic aggregates. Without being bound by theory, it is presently believed that this enhanced biological activity results from the formation or enlargement of hydrophilic channels through the epicuticular wax of the plant.

Description

COMPOSITION AND METHOD FOR TREATING PLANTS WITH EXOGENOUS CHEMICAL COMPOUNDS BACKGROUND OF THE INVENTION This invention relates to formulations and methods for increasing the effectiveness of exogenous chemicals used to treat plants. An exogenous chemical, as defined herein, is any chemical substance, either naturally or synthetically derived, that (a) has biological activity or is capable of releasing a ion, portion or derivative having biological activity in a plant, and (b) is applied to a plant with the intention or result that the chemical or its biologically active ion, portion, or depilate enters living cells or tissues of the plant and produces a stimulatory, inhibitory, regulatory, therapeutic, toxic, or lethal in the plant itself or in a pathogen, parasite or feeding organism present in or on the plant.
Examples of exogenous chemical substances include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bectericides, viricides, insecticides, aphids, miticides, nematicides, molluscicides and the like), plant growth regulators, fertilizers and nutrients, gemetocides, flashers, desiccants, mixtures thereof and the like. Exogenous chemicals, including herbicides applied to foliage, have sometimes been formulated with surfactants, so when water is added, the resulting spray composition is retained in easier and more effective way on the foliage (eg, leaves or other photosynthetic organs) of the plants. Surfactants also bring with them other benefits, including improved contact of spray droplets with a waxy sheet surface and, in some cases, improved penetration of the accompanying exogenous chemical into the interior of the sheets. Through these and perhaps other effects, it has been known for a long time that the surfactants increase the biological effectiveness of the herbicidal compositions, or of other exogenous chemical compositions, when they are added or included in said compositions. Thus, for example, the herbicide glyphosate (N-phosphonomethylglycine) has been formulated with surfactants such as polyoxyalkylene type surfactants which include, among other surfactants, polyoxyalkylenealkylamines. Commercial formulations of glyphosate herbicides marketed under the trademark ROUNDUP® have been formulated with a surfactant composition based on said polyoxyalkylene alkylamine, in particular a polyethoxylated seboamine, this surfactant composition being identified as MON 0818. The surfactants have been generally combined with glyphosate or other exogenous chemicals either in a commercial concentrate (here called a "co-formulation"), or in a diluted mixture that is prepared from separate compositions, one comprising an exogenous chemical (e.g., glyphosate) and another comprising surfactant, before being used in the field (ie, a tank mixture).
In the past several combinations of exogenous chemicals and surfactants or other adjuvants have been tried. In some cases, the addition of a particular surfactant has not produced uniformly positive or negative changes in the effect of the exogenous chemical on the plant (e.g., a surfactant that could increase the activity of a particular herbicide on certain weeds). could interfere with, or antagonize, herbicidal efficacy in other weed species). Some surfactants tend to degrade very rapidly in aqueous solutions. As a result, surfactants that exhibit this property can only be used effectively in tank mixes (ie, mixed with the other ingredients in solution or dispersion in the tank just before the spraying takes place), instead of being co-formulated in an aqueous composition with the other ingredients in the first instance. This lack of stability, or inadequate counter life, has prevented the use of certain surfactants in some formulations of exogenous chemicals. Other surfactants, although chemically stable, are physically incompatible with certain exogenous chemicals, particularly in concentrated coformulations. For example, most classes of nonionic surfactants, including polyoxyletylene alkyl ether surfactants, do not tolerate solutions of high ionic strength, such as in a concentrated aqueous solution of a glyphosate salt. Physical incompatibility can also lead to inadequate counter life. Others Problems that may originate from said incompatibility include the formation of agergadas large enough to interfere with commercial handling and application, for example blocked spray nozzles. Another problem that has been observed in the past is the effect of environmental conditions on the assimilation of an exogenous chemical composition in the foliage of a plant. For example, conditions such as temperature, relative humidity, presence or absence of sunlight and the health of the plant that will be treated can affect the assimilation of a herbicide in the plant. As a result, sprinkling exactly the same herbicidal composition in two different situations can result in a different herbicidal control of the sprayed plants. A consequence of the variability described above is that a greater amount of herbicide is commonly applied per unit area than would actually be necessary in that situation, to ensure that adequate control of the undesirable plants will be achieved. For similar reasons, other exogenous chemicals applied to the foliage are also typically applied in quantities significantly greater than those necessary to give the desired biological effect in the particular situation in which they are used, to allow for the natural variability that exists in the efficiency of assimilation. fuck. There is therefore a need for exogenous chemical compositions which, through a more efficient assimilation in the foliage of the plant, allow for reduced amounts of use.
Many exogenous chemicals are packaged commercially as a liquid concentrate that contains a significant amount of water. The packed concentrate is sent to distributors or wholesalers. Finally, the packed concentrate ends up in the hands of an end user, who dilutes the concentrate more by adding water according to the instructions on the package label. The diluted composition prepared in this way is then sprinkled on the plants. A significant portion of the cost of such packaged concentrates is the cost of transporting the concentrate from the manufacturing site to the place where the end user buys it. Any concentrated liquid formulation containing relatively less water and therefore more exogenous chemical would reduce the cost per unit amount of the exogenous chemical. However, an important limit on the manufacturer's ability to increase the exogenous chemical load in the concentrate is the stability of that formulation. With certain combinations of ingredients, a limit will be reached in which any further reduction of the water content in the concentrate will cause it to become unstable (eg, separate into discrete layers), which could be done commercially. unacceptable. Accordingly, there is a need for formulations of improved exogenous chemicals, particularly herbicides, that are stable, effective, less sensitive to environmental conditions, and that allow the use of small amounts of exogenous chemical to achieve the desired biological effect in or on the plants. There is also a need for formulations liquid and stable concentrates of exogenous chemicals that contain less water and more exogenous chemical than concentrates of the prior art.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to novel methods and compositions wherein exogenous chemicals are applied to plants to generate a desired biological rnse. One embodiment of the present invention is a method for applying an exogenous chemical to a plant, comprising the steps of (a) contacting the foliage of the plant with a biologically effective amount of the exogenous chemical and (b) contacting the plant. same foliage with an aqueous composition comprising a first excipient substance which is amphiphilic. The weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100. further, the aqueous composition forms anisotropic aggregates in or on a wax layer as explained below. "Contact" in this context means applying the substance or composition on the foliage. "Amphiphilic" means that it has at least one water-soluble and polar main group that is hydrophilic and at least one organic residue insoluble in water that is hydrophilic, contained within the same molecule. In this method, step (b) can occur simultaneously with or within about 96 hours before or after step (a). In modalities of the method in which the two steps occur simultaneously, the exogenous chemical and the aqueous composition can be applied to the plant separately, for example by two spray nozzles directed to the same foliage, or the exogenous chemical can be contained within the composition aqueous, for example in a mixture for tank or co-formulation. The formation of anisotropic aggregates in or on a wax layer is determined by a test described in detail hereinafter. In general, the test, as applied to a composition comprising ? k an exogenous chemical, comprises the steps of (1) providing a slide of microscope glass coated with a thin and uniform layer of wax, such that the wax layer on the slide exhibits a dark field when illuminated by polarized light transmitted and examined through a microscope, (2) preparing a sample of an aqueous solution or dispersion of the composition that will be tested, diluted or concentrated if necessary so that the The concentration of exogenous chemical is from about 15% to about 20% by weight of the composition, (3) placing the slide coated with wax on the slide of a microscope that transmits polarized light through the slide, (4) placing a drop of the sample on the wax on the slide to form a test slide, (5) keep the test slides at about room temperature for a period of about 5 to about 20 minutes; and (6) determine, at the end of that period, whether when the polarized light is transmitted the drop site on the slide displays birefringence. The birefringence to -20 minutes indicates the presence of anisotropic aggregates in or on the wax layer, while the absence of birefringence at that time indicates the absence of anisotropic aggregates as defined herein. The test, as applied to an aqueous composition of one or more excipient substances, that does not contain an exogenous chemical but is designed for application to the foliage of a plant in conjunction with an exogenous chemical, is as just described, except that in Step (2) The composition is diluted or concentrated such that the concentration of the first excipient substance is from about 5% to 7% by weight. A "excipient substance", as that term is used in this patent, is any substance that is not an exogenous chemical, and water is added to the composition. "Excipient substances" include inert ingredients, although an excipient substance useful in the present invention does not have to lack biological activity. Another embodiment of the present invention is a plant treatment composition comprising (a) an exogenous chemical and (b) a first excipient substance that is amphiphilic. As described above, the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100, and in the presence of water said composition forms anisotropic aggregates in or on a wax layer. This composition can be used in a method for treating plants, in which the foliage of the plant is put in contact with an amount biologically effective of a composition as described above, and further comprising an aqueous diluent. ^ -J A wide variety of exogenous chemicals can be used in the compositions and methods of the present invention. A preferred class of exogenous chemicals applied to foliages, that is exogenous chemicals that are normally applied after the emergence of foliage of plants. A preferred subclass of exogenous chemicals applied to foliage is that of those that are water-soluble. By "water-soluble" it is meant in this context that f has a solubility in distilled water at 25 ° C of more than about 1% in weight. The water-soluble exogenous chemicals that are especially preferred are the salts having an anionic portion and a cationic portion. In one embodiment of the invention, at least one of the anionic and cationic portions is biologically active and has a molecular weight of less than about 300. Particular examples of said exogenous chemicals in ^ p 15 those that the cationic portion is biologically active are paraquat, dicuat and chlormequat. The anionic potion that is biologically active is more common. Another preferred subclass of exogenous chemicals is those that exhibit systemic biological activity in the plant. Within this subclass, an especially preferred group of exogenous chemicals is N-phosphonomethylglycine 20 and its herbicidal derivatives. N-phosphonomethylglycine, commonly called by its common name glyphosate, can be used in its acid phase, but is more preferably used in the form of a salt. Any water-soluble glyphosate salt can be used in the practice of this invention. Some salts that they preferably include the sodium, potassium, ammonium, mono-, di-, tri- and tetraalkylammonium salts of C 1 -C 4, mono-, di- and trialkanolammonium of C 1 -C 4, di- and trialkylsulfonium of C 1 -C 4 and sulfoxonium. Especially preferred are the ammonium, monoisopropylammonium and trimethylsulfonium salts of glyphosate. Mixtures of salts can also be useful in certain situations. A composition of the present invention comprising an exogenous chemical and a first excipient substance as described above may have a number of different physical forms. For example, the composition may further comprise water in an effective amount such as to make the composition a dilute aqueous composition ready for application to the foliage of a plant. Said composition typically contains about 0.02 to about 2 weight percent of the exogenous chemical, but for some purposes may contain up to about 10 weight percent or even more of the exogenous chemical. Alternatively, the composition can be a stable, counter-stable concentrate composition comprising the exogenous chemical substance in an amount of about 10 percent to about 90 percent by weight. By "shelf stable" is meant in this context that the composition does not exhibit phase separation when stored at room temperature for a period of time depending on the particular circumstances. Such stable counter concentrates may be, for example, (1) a solid composition comprising the exogenous chemical substance in an amount of about 30 to about 90 percent by weight, such as a granular formulation soluble or dispersible in water or (2) a composition further comprising a liquid diluent, wherein the composition comprises the exogenous chemical substance in an amount of about 10 to about 60 percent by weight. weight. In this latter embodiment, it is especially preferred that the exogenous chemical substance be water-soluble and be present in an aqueous phase of the composition in an amount of about 15 to about 45 percent by weight of the composition. In particular, said composition may be, for example, a concentrate of aqueous solution or an emulsion having an oil phase. If it is an emulsion, it may be more specifically, for example, an oil-in-water emulsion, a water-in-oil emulsion or a water-in-oil-in-water multiple emulsion. In a particular embodiment of the invention, the solid or aqueous composition further comprises a solid inorganic particulate colloidal material. As described above, one embodiment of the invention is a sprayable composition having the property of forming anisotropic aggregates in or on a wax layer. This composition comprises an exogenous chemical, an aqueous diluent and a first excipient substance which is amphiphilic. In the sprayable composition, the weight / weight ratio of the first substance excipient to the exogenous chemical is between about 1: 3 and about 1: 100. A sprayable composition conforms to this embodiment of the invention even if the formation of anisotropic aggregates in or on a wax layer occurs only after the concentration of the composition on the wax layer by the evaporation of water. The term "spray composition" is sometimes used herein to mean a sprayable composition. In a related embodiment of the invention, a a concentrated composition which, after dilution, dispersion or dissolution in water, forms the aspermable composition just described. The concentrated composition contains a reduced amount of the aqueous diluent, or, in a particular embodiment, is a dry composition having less than about 5% water by weight. Typically, a composition The concentrate of the invention contains at least about 10% by weight of the exogenous chemical, preferably at least about 15%. An alternative embodiment is a composition that does not comprise an exogenous chemical itself, but that is designed for application to a plant in conjunction with or as a vehicle for the application of an exogenous chemical. This composition comprises a first excipient substance as described above. Said composition may be sprayable, in which case it will also comprise an aqueous diluent, or it may be a concentrate that requires dilution, dispersion or dissolution in water to provide a spreadable composition. Thus, this embodiment of the invention can be provided as an individual product and applied to a plant, diluted as appropriate with water, simultaneously with the application of an exogenous chemical, or before or after the application of the exogenous chemical.
In all embodiments, it is believed that the first excipient substance forms supramolecular aggregates in aqueous solution or dispersion.
In particular, it is believed that the aqueous compositions of the present invention form aggregates in aqueous solution or dispersion, most of which are not simple micelles. "Majority" means that more than 50% by weight of the first excipient substance present is in the form of complex aggregates that are not simple micelles, e.g., as double layers or multilamellar structures.
Preferably, more than 75% by weight is in the form of complex aggregates that are not simple micelles. Whether or not an amphiphilic substance forms said aggregates depends on its molecular architecture. The effects of molecular architecture on the supramolecular self-assembly of amphiphilic molecules are well known and understood, as established for example by J.N. Israelachvill, D.J.
Mitchell and B. W. Ninham in Faradav Transactions II, volume 72, pp. 1525-1568 (1976) and in numerous recent articles and monographs. An important aspect is the "critical packing parameter" (P) that is defined in the literature by the following equation: P = V / IA where V is the volume of the hydrophobic residue of the molecule, / is the effective length of the residue hydrophobic and A is the area occupied by the upper hydrophilic group. These dimensions can be calculated from physical measurements such as those described in the literature and have been published for numerous amphiphilic compounds.
It is believed that useful amphiphilic substances such as the present carrier excipient substance have a critical packing parameter of more than 1/3. The excipient substance ppmera forms aggregates in aqueous solution or dispersion which preferably have at least one dimension that is greater than two times the molecular length of the first excipient substance. In one embodiment of the invention, an aqueous composition comprises supramolecular aggregates of the excipient substance ppmera having an average diameter of at least 20 nm, preferably at least 30 nm. These supramolecular aggregates can have a variety of forms. In a preferred embodiment, the first excipient substance is a vesicle-forming amphiphilic substance, such as a vesicle-forming lipid, and when the substance is dispersed in water, the majority (more than 50% by weight, preferably more than 75%) by weight of the first excipient substance is present as vesicles or liposomes. In another preferred embodiment, the first excipient substance is present as double layers or multilamellar structures that are not organized as vesicles or liposomes. The compositions of the present invention may also include, without limitation, colloidal systems such as emulsions (water / oil, oil / water or multiples, e.g., water / oil / water), foams, microemulsions and suspensions or dispersions of micromaterials. in particles, nanomaterials in particles or microcapsules. The compositions of the invention may include more than one type of aggregate or colloidal system; examples include liposomes or vesicles dispersed in a microemulsion, and compositions having characteristics of both emulsions and suspensions, e.g., suspo-emulsions. The present invention also encompasses any formulation, which may or may not contain a significant antity of water, which when diluted in an aqueous medium forms such colloidal systems and / or systems comprising vesicles, liposomes, double layers or multilamellar structures, as long as the other requirements stipulated in this one are satisfied. The weight ratio of the first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100. The high level of biological effectiveness, specifically herbicidal effectiveness of a glyphosate composition, exhibited at such low ratios of excipient to exogenous chemical has been surprising. Higher ratios may also be effective, but may not be economical in most situations and may increase the risk of producing an antagonistic effect on the effectiveness of the exogenous chemical. The exogenous chemical compositions of the prior art that have included liposome-forming excipients have typically contained a higher percentage of the liposome-forming excipient substance than the exogenous chemical. In contrast, the compositions of the present invention contain less excipient than exogenous chemical, and in some embodiments much less. This makes the compositions of the present invention much less expensive than the prior art compositions described above. It is surprising that the increase in activity The biological behavior that has been observed when using the present invention can be achieved with the addition of relatively small amounts of said excipient substances. In one embodiment of the invention, the first excipient substance is a liposome-forming material comprising an amphiphilic compound or mixture of said compounds having two hydrophobic portions, each of which is an alkyl or saturated acyl chain having from about 8 to about 22 carbon atoms. The amphiphilic compound or mixture of said compounds having said two portions hydrophobic with about 8 to about 22 carbon atoms constitutes about 40 to 100 weight percent of all amphiphilic compounds having two hydrophobic portions present in the liposome-forming material. Preferably, the liposome-forming material has a hydrophilic main group comprising a cationic group. Very Preferably, the cationic group is an amine or ammonium group. In a preferred embodiment of the invention, the first excipient substance comprises a liposome-forming compound having a hydrophobic portion comprising two saturated or unsaturated hydrocarbyl groups R1 and R2 each having about 7 to about 20 carbon atoms. A number of subclasses of said liposome-forming compounds are known. A subclass has the formula: N + (CH2R1) (CH2R2) (R3) (R4) Z 'I wherein R 3 and R 4 are independently hydrogen, C 1-4 alkyl or C 1-4 hydroxyalkyl and Z is a suitable anion. A second subclass has the formula: N + (R5) (R1) (R7) CH2CH (OCH2R1) CH2 (OCH2R2) Z "II wherein R5, R6 and R7 are independently hydrogen, C1-4 alkyl or C1- hydroxyalkyl and Z is a suitable anion A third subclass has the formula: N + (R5) (R6) (R7) CH2CH (OCOR1) CH2 (OCOR2) Z- Mi where R5, R6, R7 and Z are as defined above. fourth subclass has the formula: N + (R5) (R6) (R7) CH2CH-P04-CH2CH (OCOR1) CH2 (OCOR2) IV wherein R5, Rβ, R7 and Z are as defined above The compounds of the formulas -IV will have the indicated formulas at a pH of 4 and may have the same formulas at other pH's as well, however, it should be understood that the compositions of the present invention are not limited to being used at a pH of 4. R1 and R2 are preferably straight chain alkyl groups independently saturated each having about 7 to about 21 carbon atoms Examples of suitable agriculturally acceptable anions Z include hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. In all the above subclasses of liposome forming substances, the hydrophilic portion comprises a cationic group, specifically an amine or ammonium group. The compound as a whole is in some cases cationic (as in I, II and III) and in some cases neutral (as in IV). When the amine group is quaternary, it behaves as a cationic group independently of the pH. When the amine group is secondary or tertiary, it behaves as a cationic group when it is protonated, ie, in an acid medium, for example at a pH of 4. In a preferred embodiment, the first excipient substance is a phospholipid selected from the group which consists of dialkanoylphosphatidyl-hills C8--2 and dialkanoylphosphatidylethanolamines of Cß-. In a particularly preferred embodiment, the first excipient substance is a dipalmitoyl or distearoyl ester of phosphatidylcholine or a mixture thereof. Other subclasses of liposome-forming substances having two hydrophobic chains each comprising a hydrocarbyl group of C7-21 can also be used as the first excipient substance in the compositions of the present invention. Although substances having a cationic group in the hydrophilic portion are preferred, nonionic or anionic substances may be used if desired. In another embodiment of the invention, the first excipient substance is an amphiphilic quaternary ammonium compound or mixture of said compounds. The hydrophobic portion of the quaternary ammonium compound is a saturated alkyl or halogenoalkyl group having about 6 to about 22 carbon atoms. In this modality, the first excipient substance is not necessarily a substance that forms liposomes, but are believed to form aggregates in aqueous solution or dispersion as described by arpba. Preferred quaternary ammonium compounds (other than those that are liposome forming and having two hydrocarbyl chains) to be used as the first excipient substance in the compositions of the invention have the formula: R8-Wa-X-Yb- (CH2) n-N + (R9) (R10) (R11) TV wherein R8 represents the hydrophobic portion and is a hydrocarbyl or haloalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH , a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S02, n is 2 to 4, R9, R10 and R1 are independently C1-4 alkyl and T is an anion suitable. R8 in a particular embodiment is hydrocarbyl having about 12 to about 18 carbon atoms, R8 can also be fluorinated. In a specific embodiment, R8 is perfluorinated and preferably has about 6 to about 12 carbon atoms. Suitable T anions include hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. In a particularly preferred embodiment, R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S02, Y is NH, a is 0, b is 1, n is 3, R9, R10 and R11 are methyl and T is selected from the group consisting of chloride, bromide and iodide.
In a further embodiment of the invention, the first excipient substance is an alkyl ether surfactant or mixture of said surfactants having the formula: R12-0- (CH2CH20) "(CH (CH3) CH20) m-R13 VI in where R12 is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R13 is hydrogen or C1-6alkyl Four. Preferably, R 2 is a saturated straight-chain alkyl group, R 13 is hydrogen, m is 0 and n is from about 10 to about 40, most preferably about to about 40. More preferably, the alkyl ether surfactant is a polyoxyethylene cetyl or stearyl ether or mixture thereof having 20-40 moles of ethylene oxide (EO). The term "alkyl ether", as used herein, should be understood to include alkenyl ether surfactants. The compositions of the present invention may optionally further comprise a second excipient substance having at least one hydrophobic portion, wherein if the second excipient substance has a hydrophobic portion, the hydrophobic portion is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms, and wherein if the second excipient substance has a plurality of hydrophobic portions, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality of hydrophobic portions has a total of about 12 to about 40 carbon atoms. The second excipient substance, if present, may or may not be one that forms supramolecular aggregates as described above. In a particular embodiment of the invention wherein the first excipient substance is a liposome-forming substance of formula I, II, III or IV above, a second excipient substance is present which is a quaternary ammonium compound or mixture of said compounds. Among the quaternary ammonium compounds to be used as the second excipient substance in this embodiment are the compounds of formula V above. In another particular embodiment of the invention wherein the first excipient substance is a liposome-forming substance of formula I, II, II or IV above, a second excipient substance is present which is a compound or mixture of compounds of the formula: R1 -CO-A-R15 VII wherein R14 is a hydrocarbyl group having about 5 to about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or NH. R14 preferably has about 11 to about 21 carbon atoms, R15 preferably has 1 to about 6 carbon atoms and A is preferably O. Most preferably, the second substance excipient is a C1-4 alkyl ester of a C? 2-? S fatty acid, for example a propyl, isopropyl or butyl ester of a C? 2.? s fatty acid- Butyl stearate is an especially preferred example. The aqueous composition in the embodiments comprising a compound of the formula VII is preferably an emulsion comprising an oil phase containing said second excipient substance, for example a multiple emulsion of water in oil in water or an emulsion of oil in water. As an alternative, a second excipient substance of the formula VII is associated in some way ^ h with a first liposome-forming excipient substance. In another particular embodiment of the invention, the first excipient substance is an alkyl ether tetrodioactive agent of the formula VI and a second excipient substance is present which is a compound or mixture of compounds of the formula VII. In any of the above particular embodiments, the exogenous chemical and / or second excipient substance can be encapsulated within or associated with aggregates (e.g., liposomes) formed by the first excipient substance, but does not necessarily have to be encapsulated or associated "Associated" in this context means attached to, or at least partially interspersed in some way in a vesicle wall, unlike encapsulated. In yet another embodiment of the invention wherein the first excipient substance forms liposomes, the exogenous chemical and / or the second excipient substance is not encapsulated or associated with the liposomes at all. Although the present invention does not exclude the possibility of epcapsular or associate with the exoge- nous chemist, a diluted sprinkling iiposomal composition encapsulates less than 5% by weight of the exogenous chemical that is present in the total composition. Another dilute liposomal sprayable modality of the present invention does not have a substantial amount (i.e., less than 1% by weight) of the exogenous chemical encapsulated in the liposomes. When a drop of said liposome composition is dried on the foliage of a plant, the proportion of the exogenous chemical that is encapsulated in the liposomes may change. The compositions of the present invention that include an exogenous chemical can be applied to the foliage of plants in an amount that is effective to achieve the desired biological effect of the exogenous chemical. For example, when the exogenetic chemical is a post-emergence herbicide, the composition can be applied to a plant in a herbicidally effective amount. Without being limited by theory, it is believed that the method and compositions of the present invention create or enlarge the hydrophilic channels through the epicuticular wax of the cuticle of the plant, these channels being capable of receiving the mass transfer of a water-soluble exogenous chemical within the plant, and thus transport the exogenous chemical to the interior of the plant more quickly or more completely than a layer of epicuticular wax lacking such formation or enlargement of the hydrophilic channels. Of course, certain compositions of the present invention can also enter a plant through the stomata, but this generally requires a very low surface tension which is not a characteristic. essential of the present compositions. The increased cuticular penetration that is believed to be achieved by the compositions of the present invention increases the total supply and effectiveness of the exogenous chemical. While an exogenous chemical such as glyphosate, formulated as an aqueous solution or dispersion with surfactants that do not have the property of forming anisotropic aggregates in or on a wax layer, normally penetrates through the epicuticular wax very slo(v. ., in 1-4 days), a substantial portion of the exogenous chemical in the compositions of the present invention penetrates much more rapidly (e.g., in about 10 minutes to a few hours, preferably in less than about 30 minutes). Thus, it is believed that the superior effectiveness of the methods and compositions of the invention is due at least in part to an accelerated assimilation in the foliage of the plant. In conventional methods for treating plants with exogenous chemicals, in particular exogenous polar chemicals, the epicuticular wax layer presents an almost continuous barrier through which said exogenous chemicals diffuse with difficulty, even in the presence of surfactants that increase mobility diffuser but that do not introduce the possibility of a rapid transfer of mass through the hydrophilic channels. Again, without being limited by theory, it is believed that hydrophilic channels are created within the epicuticular wax layer by self-assembling the molecules of the first excipient substance that has a hydrophobic portion that is associated with the wax and a hydrophilic portion that attracts water to form an aqueous continuum through the layer of epicuticular wax that is linked with hydrophilic trajectories in the cuticle itself. A polar exogenous chemical can be moved by mass transfer along said continuum to enter the plant. Again, without attempting to be limited by theory, it is believed that when the composition is present on the leaf of a plant as a drop of aqueous solution or dispersion, in an aqueous microdomain on the cuticular surface (ie, the aucose region in the between the drop of water and the epicuticular wax), the majority (ie, more than 50% by weight) of the aggregate filler substance is present in a form that is not a monolayer, for example, as a double layer or structure (liquid crystalline) multilaminar. The aggregate-forming substances employed have several preferred characteristics that are believed to contribute to the formation of transcuticular hydrophilic channels. For example, they have a tendency to form self-assembled structures extended in the presence of water and the types of waxes found in cuticles. Generally, materials that form non-simple aggregates (ie, non-small spherical micellar structures) are preferred in solution, such as cylindrical, discoidal or tape-like micellar vesicles or structures. These tend to form more complex adsorbed layers and adsorbed layers with hydrophobic substrates than those simple micellar systems that tend to produce simple mono-aldosteric monolayers. These substances also tend to produce lyotropic mesophases such as lamellar phases, hexagonal or inverted in the compositions established in the aqueous microdomains in or on the cuticle. In one embodiment of the invention, a cationic main group on the first excipient substance is also preferred. It is believed that the cathiopic group increases initial adhesion to the surface of the sheet, since most of these surfaces carry a global negative charge. It is also believed that the cationic group contributes to the hydrophilicity of the channels in the epicuticular wax formed or enlarged by the method and composition of the invention. Cationic groups, in particular the amine or ammonium groups, attract water molecules that further enlarge the hydrophilic channels and thus provide an improved entry path for exogenous chemicals than polar or water soluble ones. It is further believed that the creation or enlargement of the hydrophilic channels in the epicuticular wax results in the wax being plastified. A further embodiment of the invention is then a method for applying an exogenous chemical to a plant having an epicuticular wax layer, comprising (a) plasticizing the epicuticular wax layer in conjunction with (b) contacting the epicuticular wax layer with the exogenous chemical. In this embodiment, the step of plasticizing the epicuticular wax layer is achieved by contacting the layer with an aqueous composition comprising a first excipient substance as defined above and optionally a second excipient substance as defined above. The weight ratio of the first Exogenous chemical ai excipient substance is between about 1: 3 and about 1: 100. The herbicidal compositions according to the present They are also useful in methods to increase the production of a field. Said method may comprise the steps of (a) planting a crop in a field, (b) substantially freeing the field from one or more weed species that could decrease crop production by applying a herbicidally effective amount to the weed species. of a composition as described above, (c) allow the crop to mature and (d) harvest the crop. Alternatively, the method may comprise the steps of (a) substantially freeing the field from one or more weed species that could decrease crop production by applying a herbicidally effective amount of a composition to the weed species, (b) planting cultivation in the field, (c) allow the crop to mature and (d) harvest the crop. In a particular method according to the present invention, a herbicidal composition as described above can be applied to a complex of weeds that are present in a single field, the weeds being, for example, hobby, marigold and spiny dibetu. . The composition is applied in a herbicidally effective amount, and provides herbicidal control of each of the weed species in the complex.
Another effective embodiment of the present invention is a herbicidal method, which comprises contacting the foliage of a plant with a herbicidally effective amount of a composition as described above, whereby the herbicidal effectiveness of the composition on the plant to which it is applied is visibly better than the herbicidal effectiveness on that same plant species, under substantially the same conditions, of a composition that contains a similar amount of surfactant but does not form anisotropic aggregates. The term "visibly better" is this context means that the difference in the herbicidal effect of the two compositions on the plants is easily noticeable by the eye of an experienced weed scientist. Another embodiment of the present invention is a herbicidal method that can be used in a field that contains both weeds and crop plants, where the crop plants are resistant to the effects of a particular herbicide to the amount at which the herbicide is used. herbicide. The method comprises contacting the foliage of both the weeds and the crops in the field with a composition as described above. The composition will have a herbicidal effect on the weeds (that is, it will partially or completely eliminate the weeds) but will not damage the crops. This herbicidal method applies to any combination of a selective postemergence herbicide (e.g., 2,4-D) and a crop on which that herbicide can be used selectively to remove weeds (e.g., in the case of 2,4-D, wheat). This herbicidal method also applies to any combination of a normally nonselective post-emergence herbicide and a reproduced or genetically modified crop to be resistant to that herbicide. An example of a suitable combination of herbicide and herbicide-resistant crop is ROUNDUP® herbicide and ROUNDUP READY® crops, developed by Monsanto Company. The compositions and methods of the present invention have a number of advantages. They provide increased biological activity of the exogenous chemicals in or on plants compared to the prior art formulations, either in terms of a higher final biological effect, or by obtaining an equivalent biological effect using a reduced application amount of the exogenous chemical. Certain herbicidal formulations of the present invention can avoid the antagonism that has been observed in some prior art herbicidal formulations., and can minimize the rapid production of necrotic lesions on leaves that in some situations prevent the global translocation of the herbicide in the plant. Certain herbicidal compositions of the invention modify the spectrum of activity of the herbicide through a range of plant species. For example, certain glyphosate-containing formulations of the present invention can provide adequate herbicidal activity against broadleaf weeds without losing herbicide effectiveness in narrowleaf weeds. Others may increase herbicidal effectiveness in narrow leaf weeds to a greater degree than in broadleaf weeds. Others may also have increased effectiveness that is specific to a limited range of species or even a single species.
Another advantage of the present invention is that it employs relatively small amounts of the first and second excipients in relation to the amount of exogenous chemical employed. This makes the compositions and methods of the present invention relatively inexpensive, and also tends to reduce problems of instability in specific compositions wherein one or both excipient substances are physically incompatible with the exogenous chemical (e.g., ether surfactants). alkyl in solutions of high ionic strength, such as concentrated solutions of glyphosate salt). Even at the low concentrations of excipients used in the present invention, there may be limits on the maximum concentration of exogenous chemical that is used without causing compatibility problems (e.g., separation of the composition into discrete layers). In some preferred embodiments of the invention, the stability of the composition at high exogenous chemical loads is maintained by adding other ingredients such as, for example, colloidal particle materials. Some compositions of the present invention exhibit increased biological activity and have a higher exogenous chemical load than is possible in the prior art compositions. In addition, the compositions of the present invention are less sensitive in some cases to environmental conditions such as relative humidity at the time of application to the plant. Likewise, the present invention allows the use of smaller amounts of herbicides or other pesticides, still obtaining the necessary degree of control of weeds or other unwanted organisms.
DESCRIPTION OF SPECIFIC MODALITIES When the phrase "anisotropic aggregates in or on a wax layer" is used herein, it shall refer to determinations made by means of the following test procedure. The present inventors have found this test to predict with a high degree of confidence whether a composition comprising water and an exogenous chemical, or a composition comprising water and which will be used in conjunction with an exogenous chemical will show increased biological effectiveness when applied to the foliage of the plants. Modifications to the test can be made; however, a modified procedure in some main aspect will not necessarily give the same results and will not necessarily predict the increased effectiveness as reliably as the procedure described herein. The first step of the process is to prepare a slide coated with wax. The present inventors have found a preferred wax for the purpose of being a mixture of carnauba wax and beeswax in a weight / weight ratio of about 10: 1. A clear wax mixture consisting of 5% carnauba wax and 0.5% beeswax in isopropanol is prepared and maintained at a temperature of about 82 ° C. The end of a glass microscope slide of 2.4 cm x 7.2 cm It is dipped perpendicularly into the wax mixture to a depth of about one third of the length of the slide. After 10 to 15 seconds, the slide is removed very slowly and carefully from the wax mixture and allowed to cool, leaving a layer of wax deposited on both sides of the slide. The visual examination of the slide can give a preliminary indication of the thickness and uniformity of the wax coating. If the imperfections are evident the slide is rejected. If the slide does not show obvious imperfections, the wax coating is carefully removed from one side of the slide by rubbing with acetone. The subsequent evaluation of the acceptability of the slide coated with wax for the test is done by examining the slide under a microscope. The slide is selected for use in the test if, under microscopic examination using a 4.9X lens, the wax coating is of a uniform thickness and there is a uniform density of the wax particles through the slide. Preference is given to a coating that has few observable wax particles and exhibits a very dark field when examined under polarized light. The next stage of the procedure is to carry out the test. For this purpose, samples of an exogenous chemical composition to be tested are diluted, if necessary, to 15% to 20% by weight of the exogenous chemical. In the case of glyphosate, the desired concentration in a composition sample is 15% to 20% acid equivalent (a.e.). I also know prepare samples of reference compositions; in the case of glyphosate, Formulations B and J are suitable as defined in the examples herein. For a composition of the first excipient substance which does not contain an exogenous chemical but which will be applied in conjunction with an exogenous chemical, the desired concentration is from about 5% to 7% by weight of the first excipient substance. The following instrumentation or its equivalent is required or useful: Nikon SMZ-10A stereoscopic microscope equipped for observation with polarized light, photomicrography and observation and video recording. 3CCD MTl camera. Diagnostic instruments with power supply 150 IL-PS. Sony Trinitron color video monitor, model PVM-1353MD. Time lapse VCR Mitsubishi, model HS-S5600.
Hewlett Packard Pavilion 7270 computer, with Windows 95 and image-Pro Plus version 2.0 electronic imaging program installed. Hewlett Packard Deskjet 870Cse printer. A slide covered with wax, prepared and selected as described above, is placed on the microscope stage, with the system to provide transmitted light, both straight and polarized. A drop of 1 μl of the sample to be tested is applied to the wax surface using a 1 μl Hamilton syringe carefully cleaned. This and subsequent operations are followed through the microscope with a 4.9X lens. Tests are done in duplicate or triplicate for each composition. Numerous tests can be carried out simultaneously on a single slide. The progress of the change in the microscopic appearance of the sample is observed through the microscope and recorded at designated time intervals. Useful intervals of 1 minute, 10 minutes, 2 hours and > 24 hours after the application of the drop to the surface of wax. Observations can also be made at intermediate time intervals to capture possible significant transitions occurring in those intervals. The temperature of the wax layer tends to increase with prolonged exposure to the light of the microscope. It has been found in many cases that this does not interfere significantly with the results obtained. However, in some cases the temperature does not affect the result of the test and in such cases it is preferred to illuminate the sample only during the short periods necessary to make the observations, so that the temperature of the wax layer remains close to the room temperature. An example of a composition of the invention where it is believed that it is important to maintain the temperature close to room temperature is one that contains a fatty acid ester, such as butyl stearate. In a dark field (polarized light) it is observed if there is blrrefrigencia in the layer of wax, and in a field of light the character of the surface of the drop at each time interval. The following records are made: birefringence (yes / no); Initial appearance time of birefringence; character of birefringence; appearance of the surface of the drop when the composition "dries"; degree of dispersion of the drop; effects of temperature (heating the slide) if there are any; other notorious changes. Optionally, images are recorded at significant times using the 3CCD MTl camera and the Image-Pro Plus program as documentation of the observed changes. You can also record the video evidence if desired, especially during the first 15 minutes. In addition to the images captured using the 4.9X lens, full field views can be recorded using a 0.75X lens to provide clear comparisons of different samples tested on the same slide. A particularly useful parameter for predicting increased effectiveness is the observation of birefringence (yes / no) 5-20 minutes after the deposition of the test drop on the wax-coated slide.
It has been found that 10-15 minutes after deposition is a particularly suitable time for observing this parameter. The following Results for oil-in-water emulsion compositions comprising IPA salt of glyphosate, butyl stearate and alkaline ether surfactants are typical of those obtained. Each of the compositions WCS-1 through WCS-5 contained 5% w / w of a.e. of glyphosate, 0.5% w / w of butyl stearate and 5% w / w of alkyl ether surfactant. Formulations B and J are standard commercial glyphosate compositions defined in the Examples section hereinafter, and were diluted to 15% a.e. of glyphosate for the test.
It will be noted that when the hydrophobic portion of the alkyl ether was a hydrocarbyl group of Cu (WCS-5) or C-? 2 (WCS-4), the composition did not show anisotropic properties in the form of birefringence 10 minutes after its application to the slide. coated with wax. However, when the hydrophobic portion had a carbon chain length of 16 to 18 (WCS-1 to WCS-3), the birefringence was evident, indicating the presence of anisotropic aggregates in or on the wax layer. The intensity of the birefringence was higher with WCS-1 (containing steareth-20), followed by WCS-2 (containing ceteareth-27) and then WCS-3 (oleth-20).
Tests of the alkyl ether compositions, as evident in the examples herein, have shown that in general those containing alkyl ethers with a hydrophobic carbon chain length of 16 or more show greater biological effectiveness than those that have a shorter hydrophobe. In general, greater biological effectiveness has been obtained when the hydrophobe is saturated (as, for example, in steareth-20 and ceteareth-27) than when it is unsaturated (as, for example, in oleth-20).
The following compositions containing 15% a.e. of glyphosate and 5% of alkyl ether surfactant, but without butyl stearate. In WCS-10 the surfactant was steareth-10, in WCS-11 oleth-10 and in WCS-12 steareth-8 (laboratory sample of Sigma).
The property of forming anisotropic aggregates as determined by this test appears to require, in a straight chain C-ie-iß alcohol, a minimum of about 10 moles of ethylene oxide (EO). When alcohol is oleyl, an EO chain of 10 units is very short, but when the alcohol is stearyl, an EO chain even as short as 8 units seems to be sufficient. However, it should be noted that the steareth-8 used in the WCS-12 composition was obtained as a laboratory sample and is almost chemically purer than commercial surfactants. used in other compositions. The commercial grade steareth-8 will not necessarily give the same result. As further evidence of the utility of the present anisotropy test for predicting the biological effectiveness of the exogenous chemical compositions, the compositions WCS-6, WCS-7 and WCS-8, each containing 30% of a.e. of glyphosate by weight, and were then diluted to 15% a.e. of glyphosate for the test. All contained soy lecithin (45% phospholipid, Avanti) and were prepared by procedure (v) as detailed in the examples herein. The composition WCS-6, before dilution, contained 5% lecithipa, 5% Fluorad FC-754 and 0.75% Ethomeen T / 25. The WCS-7 composition, before dilution, contained 2% lecithin and 2% Fluorad FC-754. The WCS-8 composition, before dilution, contained 2% lecithin and 0.75% Ethomeen T / 25. In addition, the WCS-9 composition was prepared containing 15% a.e. of glyphosate and 5% soy lecithin (45% phospholipid, Avanti). The following results were obtained.
As is evident from the examples herein, increased biological effectiveness is a feature of compositions containing lecithin as the first excipient substance and Fluorad FC-754 as the second excipient substance. In the absence of Fluorad FC-754 or similar material, lecithin, either alone or together with a tertiary alkylamine surfactant such as Ethomeen T / 25 or MON 0818, does not consistently generate the desired increase. As an additional demonstration of the utility of the present anisotropy test, the WCS-13 and WCS-14 compositions, each containing 20% a.e. of glyphosate by weight, and were then diluted to 15% a.e. of glyphosate for the test. Both contained soy lecithin (45% phospholipid, Avanti). The WCS-13 composition was made by the procedure (x) as described in the examples herein and, before dilution, contained 6% lecithin, 6% Ethomeen T / 25 and 1.5% butyl stearate. The WCS-14 composition was identical, except that it did not contain butyl stearate. Particular care was taken in this study to avoid excessive heating of the slide coated with wax by prolonged illumination. The following results were obtained.
The addition of a small amount of butyl stearate was then sufficient to confer, in a glyphosate + lecithin + thomeen T / 25 composition, the property of forming anisotropic aggregates in or on a wax layer. The examples herein illustrate the unexpected increase in biological effectiveness observed when an exogenous chemical is formulated with lecithin and a fatty acid ester such as butyl stearate.
In this way, when for reasons of economy, compatibility with the exogenous chemical or other consideration it is desired to provide an exogenous chemical composition which has a relatively low content of excipients (for example a weight ratio of each excipient chemical substance to an exogenous chemical of approximately 1: 3 or less), the anisotropy test provided herein is an in vitro test method that can be used to identify biologically effective compositions prior to extensive in vivo testing. The in vitro test method just described, together with modifications thereof which will be readily apparent to those skilled in the art, is a further embodiment of the present invention. Examples of exogenous chemical substances that may be included in the compositions of the present invention include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, aphids, miticides, molluscicides and the like), regulators of plant growth, fertilizers and nutrients, gemetocides, defoliators, desiccants, mixtures thereof and the like. In one embodiment of the invention, the exogenous chemical is polar. A preferred group of exogenous chemicals are those that are normally applied after emergence to the foliage of plants, that is, exogenous chemicals applied to the foliage. Some exogenous chemicals useful in the present invention are water soluble, for example salts comprising biologically active ions, and that also comprise counterions, which may be biologically inert or relatively inactive. A particularly preferred group of these water-soluble exogenous chemicals or their biologically active portions or portions are systemic in plants, i.e., they are to some extent translocated from the point of entry into the foliage to other parts of the plant where they can exert themselves. its desired biological effect. Especially preferred among these are the herbicides, plant growth regulators and nematlcides, particularly those having a molecular weight, excluding the counterions, of less than about 300. Especially preferred among these are the exogenous chemical compounds having one or more functional groups selected from amine, carboxylate, phosphonate and phosphinate groups. Among such compounds, a group that is even more preferred are the exogenous herbicidal chemical compounds or plant growth regulators having at least one of each amine functional group., carboxylate and either phosphonate or phosphinate. The N-phosphonomethylglycine salts are examples of this group of exogenous chemicals. Additional examples include the glufosinate salts, for example the ammonium salt (DL-homoalanin-4-yl (methylene) ammonium phosphinate). Another preferred group of exogenous chemicals that can be applied by the method of the invention are nematlcides such as those described in the U.S. patent. No. 5,389,680, the disclosure of which is incorporated herein by reference. The nematicides of this group that they prefer the salts of 3,4,4-trifluoro-3-butenoic acid or of N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine. Exogenous chemicals that can be usefully applied by the method of the present invention are usually, but not exclusively, those which are expected to have a beneficial effect on the total growth or production of desired plants such as crops, or a harmful or lethal effect on the growth of undesirable plants such as weeds. The method of the present invention is particularly useful for herbicides, especially those that are normally applied after emergence to the foliage of an unwanted vegetation. Herbicides that can be applied by the method of the present invention include but are not limited to any of those listed in standard reference works such as the "Herbicide Handbook," Weed Science Societv of America, 1994, 7th edition, or " Farm Chemicals Handbook, "Meister Publishing Company, 1997 edition. Illustratively, these herbicides include acetanilides such as acetochlor, alachlor and metolachlor, aminotriazole, asulam, bentazon, bialaphos, bipyridyls such as paraquat, bromacil, cyclohexenones such as clethodim and sethoxydim. , dicamba, diflufenican, dynitroanilines such as pendimethalin, diphenylether ethers such as acifluorfen, fomesafen and oxyfluorfen, fatty acids such as Cg ^ o fatty acids, fosamine, flupoxam, glufosinate, glyphosate, hydroxybenzonitriles such as bromoxynil, imidazolinones such as mazaquin and Mazetapir, soxaben, norflurazon, phenoxies such as 2,4-D, phenoxypropionates such as diclof op, fluazifop and quizalofop, picloram, propanil, substituted ureas such as flumeturon and isoproturon, sulfonylureas such as chlorimuron, chlorsulfuron, halogensulfuron, metsulfuron, primisulfuron, sulfometuron and sulfosulfuron, thiocarbamates such as trialate, triazines such as atrazine and metribuzin, and triclopir. The herbicidally active derivatives of any known herbicide are also within the scope of the present invention. A herbicidally active derivative is any compound that is a minor structural modification, most commonly but not restrictively a salt or ester, of a known herbicide. These compounds retain the essential activity of the herbicide of origin, but may not necessarily have a potency equal to that of the herbicide of origin. These compounds can become the herbicide of origin before or after they enter the treated plant. Likewise, mixtures or co-formulations of a herbicide with other ingredients, or of more than one herbicide can be used. A herbicide that is especially preferred is N-phosphonomethylglycine (glyphosate), a salt, adduct or ester thereof, or a compound that is converted into glyphosate in the tissues of the plant or that otherwise provides a glyphosate ion. The glyphosate salts that may be used in accordance with this invention include but are not limited to alkali metal salts, for example sodium and potassium, ammonium salt; alkylamine salts, for example dimethylamine and isopropylamine; alkanolamine salts, for example ethanolamine; alkylsulfonium salts, for example trimethylsulfonium; sulfoxonium salts, and mixtures thereof. The herbicidal compositions sold by Monsanto Company such as ROUNDUP® and ACCORD® contain the monoisopropylamine salt (IPA) of N-phosphonomethyl glycine. The herbicidal compositions sold by Monsanto Company as ROUNDUP® Dry and RIVAL® contain the monoammonium salt of N-phosphonomethylglycine. The herbicidal composition sold by Monsanto Company as ROUNDUP® Geoforce contains the monosodium salt of N-phosphonomethylglycine. The herbicidal composition sold by Zeneca as TOUCHDOWN® contains the trimethylsulfonium salt of N-phosphonomethylglycine. The herbicidal properties of N-phosphonomethylglycine and its derivatives were first discovered by Franz, and then described and patented in the US patent. 3, 799,758, issued March 26, 1974. A number of herbicidal salts of N-phosphonomethylglycine were patented by Franz in the US patent. 4,405,531, issued September 20, 1983. The descriptions of both of these patents are incorporated herein by reference. Since the most important commercially available herbicide derivatives of N-phosphonomethylglycine are certain salts thereof, the glyphosate compositions useful in the present invention will be described in more detail with respect to said salts. These salts are well known and include the ammonium, IPA, alkali metal salts (such as the mono-, di- and trisodium salts and the mono-, di- and tripotassium salts) and trimethylsulfonium salts. The salts of N-phosphonomethylglycine are commercially significant in part because they are soluble in water. The salts listed above are highly water soluble, thus allowing highly concentrated solutions that can be diluted in the place of use. According to the method of this invention, as regards the glyphosate herbicide, an aqueous solution containing a herbicidally effective amount of glyphosate and other components according to the invention is applied to the foliage of the plants. Said aqueous solution can be obtained by diluting a concentrated glyphosate salt solution with water, or dissolving or dispersing in water a dry glyphosate formulation (eg, granulated, powder, tablet or tablet). The exogenous chemicals must be applied to the plants in an amount sufficient to give the desired biological effect. These application rates are usually expressed as exogenous chemical amount per unit area treated, eg, grams per hectare (g / ha). What constitutes a "desired effect" varies according to the standards and practice of those who investigate, develop, commercialize and use a specific class of exogenous chemicals. For example, in the case of a herbicide, the amount applied per unit area to give 85% control of a plant species measured by growth reduction or mortality is commonly used to define a commercially effective amount. Herbicidal effectiveness is one of the biological effects that can be increased by means of this invention. The term "herbicidal effectiveness", as used herein, refers to any observable measure of growth control of the plant, which may include one or more of the actions of (1) eliminating, (2) inhibiting growth , reproduction or proliferation and (3) remove, destroy or otherwise reduce the occurrence and activity of the plants. The herbicide effectiveness data set forth herein report "inhibition" as a percentage after a standard procedure in the art that reflects a visual determination of mortality and reduction of plant growth as compared to untreated plants, made by specially trained technicians to make and record such observations. In all cases, a single technician makes all determinations of percent inhibition in any experiment or test. These measurements are based on and are regularly reported by Monsanto Company in the course of its herbicide business. The selection of application quantities that are biologically effective for a specific exogenous chemical is within the skill of the ordinary agricultural scientist. Those skilled in the art will recognize in the same way that individual plant conditions, climate conditions and growth, as well as the specific exogenous chemical and formulation thereof selected, will affect the effectiveness achieved in carrying out this invention. The amounts of application useful for the exogenous chemicals employed may depend on all the above conditions. With respect to the use of the method of this invention for glyphosate herbicides, too much information is known about the appropriate application amounts. Over the course of two decades of glyphosate use and published studies that refer to this use, abundant information has been provided about which weed control practitioner can select application amounts of glyphosate that are herbicidally effective in particular species during particular growth stages and at particular environmental conditions. The herbicidal glyphosate compositions or derivatives thereof are used to control a very wide variety of plants throughout the world. Said compositions can be applied to a plant in a herbicidally effective amount, and can effectively control one or more plant species from one or more of the following genera, without restriction: Abutillon, Amaranthus, Artemisia, Asclepias, Oats, Axonopus, Botreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Erodium, Helianthus, Imperata, Ipomoea, Kochia, Lolium, Mlava, Oryza, Ottochloa, Panicum, Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium , Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium and Zea. Particularly important species for which the glyphosate compositions are used, are exemplified without limitation by means of the following: Annual broadleaf: Alcotán (Abutilón theophrasti) amaranth (Amaranthus spp.) Button (Borreria spp.) oilseed rape, canola, Indian mustard, etc. (Brassica spp.) Cornelina (Commelina spp.) Filamentous plant (Erodium spp.) Sunflower (Helianthus spp.) Marigold (Ipomoea spp.) Cochia (Kochia scoparia) mallow (Malva spp.) Wild buckwheat, water pepper, etc. . (Poligonum spp.) Purslane (Portulaca spp.) Russian thistle (Salsola spp.) Dibetu (Sida spp.) Wild mustard (Sinapis arvensis) ajonjera (Xanthium spp.) Annual stenofoliads: wild oats (Avena fatua) carpet grass (Axonopus spp.) Pubescent bromeliad (Bromus tßctorum) crabgrass (Digitaria spp.) Farm pasture (Echinochloa crus-galli) goose grass (Eleusine indica) annual rye (Lolium multiforum) ) rice (Oryza sativa) otocloa (Ottochloa nodosa) bay pasture (Paspalum notatum) birdseed (Phalaris spp.) 5 foxtail (Setaria spp.) wheat (Triticum aßstivum) corn (Zea mays) f Peridian broadleaves: 10 Sticky Artemis (Artemisia spp.) Asclepiada (Asclepias spp.) Canadian thistle (Cirsium arvense) field bindweed (Convolvulus arvensis) kudzu (Pueraria spp.) f 15 Perennial stenofoliads: Brachiaria (Brachiaria spp.) grass Bermuda (Cynodon dactylon) yellow sedge (Cyperus esculentus) 20 purple sedge (C. rotundus) grass (Elymus repens) lalanga (Imperata cylindrica) perennial ryegrass (Lolium perenne) Guinea grass (Panicum máximum) expanded grass (Pasapalum dilatatum) cane (Phragmites spp.) Sorghum of Aleppo (Sorghum halepense) bulrush (Typha spp.) Other perennial: horsetail (Equisßtum spp.) Fern (Pteridium aquilinum) blackberry (Rubus spp.) Gorse (Ulex europaeus) In this way, the method of the present invention, as regards glyphosate herbicide, can be useful in any of the above species. The effectiveness in greenhouse tests, usually in exogenous chemical quantities lower than those normally effective in the field, is a proven indicator of the consistency of yield in the field in normal use quantities. However, even the most promising composition fails sometimes to exhibit increased yield in individual greenhouse tests. As illustrated in the examples herein, an increment pattern emerges over a series of greenhouse tests; When this pattern is identified, it is strong evidence of a biological increase that will be useful in the field.
The aggregate-forming substances useful as the first excipient substance in the compositions of the present invention include a wide variety of amphiphilic materials, of which three classes are preferred.
The first preferred class of aggregate-forming substances can be defined as amphiphilic liposome-forming substances. These include various lipids of synthetic, animal or plant origin, including phospholipids, ceramides, sphingolipids, dialkyl surfactants and polymeric surfactants. A variety of these materials are known to those skilled in the art and are commercially available. Lecithins are particularly rich in phospholipids and can be derived from a number of animal and plant sources. Soy lecithin is a particular example of a relatively inexpensive and commercially available material that includes such substances. Many other substances that can be used to form liposomes have been described; The present invention includes compositions comprising any of said liposome-forming substances, as long as the other requirements set forth above are met, and the use of said compositions to increase the biological effectiveness of the exogenous chemicals applied to the foliage of the plants. For example, the US patent. No. 5,580,859, incorporated herein by reference, discloses liposome forming substances having a cationic group, including N- (2,3-di- (9- (Z) -octadecenyloxy)) -prop-1 chloride. -il-N, N, N-trimethylammonium (DOTMA) and 1,2-bis (oleoyloxy) -3- (trimethylammonio) propane (DOTAP). Liposome-forming substances that are not cationic in themselves, but that do contain a cathiopic group as part of the hydrophilic moiety, include for example dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylethanolamine (DOPE). Liposome-forming substances that do not contain a cationic group include dioleoylphosphatidylglycerol (DOPG). Any of these liposome-forming substances can be used, with or without the addition of cholesterol. These substances contain portions that are hydrophilic and hydrophobic within the same molecule. They have the ability to self-assemble in aqueous solution or dispersion to form structures that are more complex than simple micelles. The nature of the aggregate that will be formed can be related to the critical packing parameter P by the following equation: P = V / IA where V is the volume of the hydrophobic residue of the molecule, / is the effective length of the hydrophobic residue and A is the area occupied by the upper hydrophilic group on the surface of the aggregate. The most likely self-assembled structures are spherical micelles when P is less than 1/3, barlet micelles when P is between 1/3 and 14, laminar when P is between 1 and Vi, and inverse structures when P is greater than 1. materials that are preferred in the present invention have P greater than 1/3. Cationic liposome-forming substances having a hydrophobic portion comprising two hydrocarbyl chains are accompanied by a counterion (anion), identified as Z in formulas I, II and III above. Any suitable anion can be used, including agriculturally acceptable anions such as hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. In a specific modality in which the exogenous chemical has a anion biologically active, that anion can serve as the counter ion for the liposome-forming substance. For example, glyphosate in its acid form can be used together with the hydroxide of a liposome-forming substance such as a compound of formula I. e? The compounds of the formula I known in the art as liposome formers include chloride and distearyldimethylammonium bromide (also known in the art as DODAC and DODAB, respectively). Compounds of formula II known in the art as liposome formers include DOTMA, mentioned above, and dimyristoxypropyl dimethylhydroxyethylammonium bromide (DMRIE). Compounds of formula 15 15 known in the art as liposome formers include dioleoyloxy-3- (dimethylammonium) propane (DODAP) and DOTAP mentioned am'ba. Compounds of formula IV known in the art as liposome formers include DOPC and DOPE, both mentioned above. In many liposome-forming substances known in the art In the art, the hydrophobic hydrocarbyl chains are unsaturated, having one or more double bonds. Used particularly in a common form in the pharmaceutical technique are the dioleyl or dioleoyl compounds. A potential problem with these is that in an oxidizing environment they can be oxidized at the site of the double link. This can be inhibited by including in the formulation an antioxidant such as ascorbic acid. Alternatively, the problem can be avoided by the use of liposome-forming substances in which a high proportion of the hydrophobic hydrocarbyl chains are completely saturated. Thus, in a preferred embodiment of the invention, R1 and R2 in the formulas I-IV are straight chain alkyl groups independently saturated. Particularly preferred compositions use liposome-forming substances in which R1 and R2 are both palmityl (cetyl) or plamitoyl groups or, alternatively, are both stearyl or stearoyl groups. Phospholipids, thanks to their low cost and favorable environmental properties, are particularly preferred among the liposome-forming substances of the method and compositions of the invention. Plant lecithins, such as soy lecithin, have been used successfully in accordance with the invention. The phospholipid content of the lecithin product can vary from about 10% to almost 100%. Although acceptable results have been obtained with crude lecitin (10-20% phospholipids), it is generally preferred to use lecithin which is at least partially deoiled, so that the content of phospholipids is in the region of about 45% or more. Higher grades such as 95% provide excellent results, but the much higher cost will not be justified for most applications. The phospholipid component of the lecithin, or any phospholipid composition used in the present invention, may comprise one or more phosphatides of natural or synthetic origin. Each of these phosphatides is generally a phosphoric ester which in the hydrolysis produces phosphoric acid, fatty acid (s), polyhydric alcohol and, typically, a nitrogenous base.
A phosphatide component may be present in a partially hydrolyzed form, e.g., as phosphatidic acid. Suitable phosphatides include, without limitation, phosphatidylcholine, hydrogenated phosphatidylcholine, phosphatidylinositol, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylethanolamine, N-acyl phosphatidylethanolamine and mixtures of any of these. In plant lecithins, a high proportion of the hydrophobic hydrocarbyl chains of the phospholipid compounds are typically unsaturated. A preferred embodiment of compositions according to the present invention comprises both saturated phospholipid and unsaturated phospholipid, the weight ratio of saturated phospholipid to unsaturated phospholipid being greater than about 1: 2. In several particularly preferred embodiments, (1) at least 50% by weight of the phospholipids are saturated C12-22 dialkanoylphospholipid, (2) at least 50% by weight of the phospholipids are saturated C1S-18 dialkanoylphospholipid, (3) ) at least 50% by weight of the phospholipids are distearoylphospholipid, (4) at least 50% by weight of the phospholipids are dipalmitoylphospholipid or (5) at least 50% by weight of the phospholipids are distearoylphosphatidylcholine, dipalmitoylphosphatidylcholine or a mixture from the same. Higher proportions of saturated alkanoyl phospholipids are generally found in lecithins of animal origin, such as for example egg yolk lecithin, than in lecithins of vegetable origin.
It is known that phospholipids are chemically stable, at least in acidic media, where they tend to degrade to their smooth counterparts. Thus, when phospholipids are used in place of more stable liposome forming substances, it is usually preferable to adjust the pH of the composition upwards. In the case of glyphosate compositions, the pH of a composition based on a mono-salt such as the monoisopropylammonium salt (IPA) is typically about 5 or less. When phospholipids are used as the first excipient substance in a glyphosate composition of the invention, it will therefore be preferable to raise the pH of the composition, for example to about 7. Any suitable base can be used for this purpose; it will be much more convenient to use the same base in the glyphosate salt, for example isopropylamine in the case of the glyphosate IPA salt. The amphiphilic compounds useful as the first excipient substance herein are not limited to those having two hydrophilic hydrophobic groups such as the compounds of the formulas I to IV. The second preferred class of aggregate-forming substances useful in the present invention are the cationic surfactant compounds having the formula V above. In the compounds of formula V, R8 unless perfluorinated, preferably has about 12 to about 18 carbon atoms. R8 is preferably perfluorinated, in which case it preferably has about 6 to about 12 carbon atoms. Preferably, n is 3. The R9 groups are preferably methyl.
Especially preferred are the sulfonylamino compounds of the formula V. Suitable examples include 3- (((heptadecafluorooctyl) sulfonyl) amino) -N, N, N-trimethyl-1-propaminium iodide, available for example as Fluorad FC-135 from 3M Company, and the corresponding chloride. It is believed that Fluorad FC-754 from 3M Company is the corresponding chloride. The fluorine-organic surfactants such as the cationic types falling within the formula V belong to a functional category of surfactants known in the art as "super-extenders" or "super-humectants", since a class of "superexpansors" or "super-humectants" "are very effective in reducing the surface tension of aqueous compositions containing relatively low concentrations of these surfactants. In many applications, the fluorine-organic surfactants can be replaced by organosilicon surfactants, which are also "super-expanding" or "super-moisturizing". One example is found in European patent application 0 394 211, which discloses that organisilicon or fluorine-organic surfactants can be used interchangeably in solid granulated pesticide formulations to improve the rate of dissolution. Two major problems have limited the interest in "superexpansors" and "superhumectants" by exogenous chemical formulators such as pesticides. The first is a high unit cost. The second is that although surfactants in this functional category can increase the performance of an exogenous chemical in certain species, example helping the penetration of the exogenous chemical into the leaves through the stomata, can be antagonistic, sometimes severely, for the performance of the same chemical exogenous in other species. Surprisingly, it has now been found that a subclass of fluorine-organic surfactants is essentially non-antagonistic at concentrations which nonetheless provide useful adjuvant effects. This subclass comprises cationic fluorine organic surfactants of the formula V and others having a property profile in common with those of the formula V. The lack of antagonism makes this sub-class very different from other "super-extenders" and "super-humectants" fluorine -organic In addition, it has been found that these non-antagonistic fluorine-organic surfactants can be useful at concentrations low enough to be cost-effective. The data in the examples herein for the compositions comprising Fluorad FC-135 or Fluorad FC-754 illustrate the unexpected profiles of this subclass. The Fluorad derivatives FC-754, described herein as "FC-acetate" and "FC-salicllate", have been prepared by the following procedure. (1) The solvent in a sample of Fluorad FC-754 is gently evaporated by heating in a glass beaker at 70-80 ° C to leave a solid residue. (2) The solid residue is allowed to cool to room temperature. (3) An aliquot of 1 g of the residue is placed in a centrifuge tube and dissolved in 5 ml of sodium propane. (4) A saturated solution of potassium hydroxide (KOH) in isopropanol is prepared. (5) This solution is added dropwise to the FC-754 residue solution; this results in the formation of a precipitate and the addition of KOH solution continues until no more precipitate forms. (6) The tube is centrifuged at 4000 rpm for 5 minutes. (7) Add more KOH solution to check if the precipitation is complete; If not, the tube is centrifuged again. (8) The supernatant is decanted in another glass tube. (9) A saturated solution of acetic acid (or salicylic acid) in isopropanol is prepared. (10) This solution is added to the supernatant in an amount sufficient to reduce the pH to 7. (11) Isopropanol is evaporated from this neutralized solution by heating at 60 ° C until it is completely dry. (12) The residue (either the acetate salt or salicylate) is dissolved in an adequate amount of water and is then ready to be used. The third preferred class of aggregate-forming substance useful as the first excipient substance in accordance with the present invention is a long-chain alkyl ether surfactant having the formula VI above. R12 can be branched or unbranched, saturated or unsaturated. R12 is preferably saturated straight chain Cyl (straight) alkyl or saturated straight chain C-? 8 alkyl (stearyl). In preferred alkyl ethers m is 0, n is an average number of about 20 to about 40 and R13 is preferably hydrogen. Among the especially preferred alkyl ether surfactants are those identified in the International Directory of Cosmetic Ingredients such as ceteth-20, ceteareth-20, ceteareth-27, steareth-20 and steareth-30.
Of the classes of aggregate-forming substances useful as the first excipient substance, not all of them give rise to anisotropic aggregates in or on a wax layer, as required by the present invention, when they are used as the sole excipient substance in the composition to a Weight ratio of 1: 3 to 1: 100 with the exogenous chemical. Many compounds of the formulas V and VI are sufficient in the absence of a second excipient substance, but in general, the liposome-forming substances of formulas I to IV require the presence of a second excipient substance to exhibit the required anisotropic behavior. However, even in the presence of a first excipient substance of the formulas V or VI, there may be advantages in including also a second excipient substance as defined herein. The second excipient substance has one or more hydrophobic portions. If there is only one hydrophobic portion, this is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms. If there is more than one hydrophobic portion, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, and the total number of carbon atoms in the hydrophobic portions is from about 12 to about 40. Second class of excipient useful in the present They are the quaternary ammonium compounds. Among the quaternary ammonium compounds that may be used are the compounds of the formula: N + (R16) (R17) (R18) (R19) Q- VIII wherein R16, R17, R13 and R19 are independently C3.6 alkyl groups and Q is a suitable anion, such as for example hydroxide, chloride, bromide, iodide, sulfate, phosphate or acetate. In preferred compounds of the formula VIII all the R groups are the same. Particularly preferred compounds of the formula VIII are the tetrabutylammonium salts. When the exogenous chemical comprises a biologically active anion, a salt of formula VIII wherein Q is that anion is an option that will provide both the exogenous chemical and the second excipient substance. An example is the tetrabutylammonium salt of glyphosate. Other quaternary ammonium compounds that may be useful include the compounds having a single hydrocarbyl group of Ci2-2-: and three C1-4 alkyl groups attached to the quaternary nitrogen atom. One or more of the alkyl groups of C- ^ in said compounds can be replaced by a benzyl group. Specific examples include cetyltrimethylammonium bromide and benzalkonium chloride. Other quaternary ammonium compounds useful as the second excipient substance include the compounds of the formula I, wherein the first excipient substance does not have the formula I. The preferred quaternary ammonium compounds and useful as the second excipient substance are the compounds of the formula V, wherein the first excipient substance is not of the formula V. The same specific compounds of the formula V are especially preferred if a compound of the formula V is the first or the second excipient substance. Particularly good results have been obtained when the first excipient substance is Lecithin and the second excipient substance is Fluorad FC-135 or FC-754 or chemical equivalents thereof. Another class of compound useful as the second excipient substance is an amide or ester of the formula VII above. R14 in the formula VII is preferably aliphatic and has from about 7 to about 21 carbon atoms, most preferably from about 13 to about 21 carbon atoms. It is especially preferred that R14 is a saturated straight-chain alkyl group. R15 is preferably an aliphatic group having 1-6 carbon atoms, most preferably alkyl and alkenyl having 2-4 carbon atoms. A compound of the formula V1 especially preferred for use as the second excipient substance is butyl stearate. Since the compounds of the formula VII, including butyl stearate, are generally oily liquids, the aqueous compositions containing them are typically emulsions having at least one aqueous phase and at least one oil phase, the compound of the formula VII predominantly in the oil phase. Said emulsions can be water in oil, oil in water or multiple emulsions of water in oil in water (W / O /). Concentrated aqueous compositions in which the first excipient substance is an alkyl ether of the formula VI and the second excipient substance, if present, is a fatty acid ester of the formula VII are limited in the degree to which a carrier can be charged. exogenous chemical such as glyphosate. At a certain point, as the exogenous chemical load increases, the composition will not remain adequately stable. It has surprisingly been found that the addition of a small amount of colloidal particle material to said compositions greatly increases the loading capacity while retaining the desired stability. The silicon, aluminum and titanium oxides are preferred colloidal particle materials. The particle size is preferably such that the specific surface area is in the range of about 50 to about 400 m2 / g. When the exogenous chemical is glyphosate, the use of colloidal particulate material enables fillers of at least 30% by weight for compositions containing sufficient alkyl ether and fatty acid to show improved herbicidal effectiveness, or at least 40% for compositions containing alkyl ether but not fatty acid ester, and showing herbicidal effectiveness at least equal to current commercial products loaded at approximately 30%. The present inventors have discovered that an especially useful improvement in storage stability can be obtained by using colloidal particle materials having a specific surface area of between about 180 and about 400 m2 / g. Other means for improving the stability of highly charged compositions comprising alkyl ether of formula VI, with or without a fatty acid ester, may also be possible and are within the scope of the present invention.
The compositions according to the present invention are typically prepared by combining water, the exogenous chemical (unless it is "- 'a formulation that will not contain an exogenous chemical) and the aggregate-forming substance When the aggregate-forming substance is one that is easily disperse in water, as is the case for example with Fluorad FC-135 or Fluorad FC-754, simply mixing with gentle agitation may be sufficient.
However, when the aggregate-forming substance requires high shear stress to be dispersed in water, as is the case, for example, with the For most forms of lecithin, it is currently preferred to sonicate or microfluidize the aggregate-forming substance in water. This can be done before or after a surfactant and / or the exogenous chemical is added. Sonification or microfluidization will generally produce liposomes or other aggregate structures that are not simple micelles. The precise nature, including the average size, of the liposomes or other aggregates depends among other things on the energy consumption during sonification or microfluidization. Higher energy consumption generally results in smaller liposomes. Although it is possible to trap or otherwise bind loosely or tightly the exogenous chemical in or on the liposomes with other supramolecular aggregates, the exogenous chemical does not need to be entrapped or bound in this manner, and in fact the present invention is effective when the exogenous chemical is not trapped or bound in the aggregates at all.
In a particular embodiment of the invention, liposomes or other aggregates have an average diameter of at least 20 nm, most preferably at least 30 nm. It has been determined by light scattering that certain liposomal compositions of the invention have average liposome diameters ranging from 54 to 468 nm, calculated using linear adaptation and from 38 to 390 nm, calculated using quadratic adaptation. The concentrations of the different components will vary, in part depending on whether a concentrate is being prepared that will be diluted further before being sprayed on a plant, or if a solution or dispersion is prepared that can be sprayed without further dilution. In a formulation of aqueous glyphosate including dialkyl surfactant, for example a dlalkyl surfactant of the formula I, the suitable concentration scales are: glyphosate 0.1-400 grams of acid equivalent (ae) / liter, and surfactant of dialkyl 0.001 -10% by weight. In an aqueous glyphosate formulation using a cationic fluorine-organic surfactant and lecltin, suitable concentrations may be glyphosate 0.1-400 g ae / l, fluorine-organic surfactant 0.001 -10% by weight and soy lecitin 0.001-10. % in weigh. In an aqueous formulation that includes an alkyl ether surfactant of C-ie-iß and butyl stearate, suitable concentrations may be: glyphosate 0.1-400 g a.e./l, alkyl ether surfactant 0.001 - 10% by weight and butyl stearate 0.001 - 10% by weight. To achieve the highest concentrations in these scales, it is commonly beneficial to add other ingredients to provide stability under acceptable storage, for example silica in colloidal particles or aluminum oxide at 0.5-2.5% by weight. In an aqueous glyphosate formulation which includes an alkyl ether surfactant of dß-iß but not of butyl stearate, the concentration of glyphosate can be suitably increased to 500 g ae / l or more, in the presence of a colloidal particle material at 0.5 - 2.5% by weight. In aqueous glyphosate formulations, higher ingredient concentrations are possible thanks to the removal of most water. The weight / weight ratios of ingredients may be more important than the absolute concentrations. For example, in a glyphosate formulation containing lecithin and cationic fluorine-organic surfactant, the ratio of lecithin to a.e. of glyphosate is on the scale from about 1: 3 to about 1: 100. It is generally preferred to use a ratio of lecithin to a.e. of glyphosate near as high as it can be incorporated in the formulation while maintaining the stability thereof, in the presence of an amount of the fluorine-organic surfactant sufficient to give the desired increase in herbicidal effectiveness. For example, a lecithin / a.e ratio. of glyphosate on the scale of about 1: 3 to about 1: 10 will be generally useful, although lower ratios of about 1:10 to about 1: 100 may have benefits on particular weed species in particular situations. The ratio of fluorine-organic surfactant, when present, to a.e. of glyphosate will preferably be on the scale from about 1: 3 to about 1: 100. Since fluorine-organic surfactants tend to have a relatively high cost, it will generally be desirable to keep this ratio as low as possible in order to achieve the desired herbicidal effectiveness. The ratio of fluorine-organic surfactant, when present, to lecithin is preferably in the range of about 1: 10 to about 10: 1, most preferably in the range of about 1: 3 to about 3: 1 and more preferably about of 1: 1. The scales described herein may be used by one skilled in the art to prepare compositions of the invention having suitable concentrations and ratios of ingredients. The optimal and preferred ingredients and concentrations of ingredients for any particular use or situation can be determined by routine experimentation. Although the combination of the components can be made in a tank mix, it is preferred in the present invention that the combination be made before application to the plant, to simplify the tasks required of the person applying the material to the plants. However, the present inventors have discovered that in some cases the biological effectiveness of a liposome-containing composition prepared from starting material as a diluted spray composition is superior to that of a composition having the same ingredients at the same concentrations but diluted from a previously prepared concentrated formulation.
Although various compositions of the present invention are described herein as comprising certain listed materials, in some preferred embodiments of the invention the compositions consist essentially of the indicated materials. Optionally, other agriculturally acceptable materials may be included in the compositions. For example, more than one exogenous chemical may be included. Likewise, various agriculturally acceptable adjuvants may be included, whether or not their purpose is to contribute directly to the effect of the exogenous chemical in a plant. For example, when the exogenous chemical is a herbicide, liquid nitrogen or ammonium sulfate fertilizer may be included in the composition. As another example, stabilizers can be added to the composition. In some cases it may be desirable to include microencapsulated acid in the composition, to lower the pH of a spray solution in contact with a sheet. One or more surfactants may also be included. The surfactants mentioned herein by trade name, and other surfactants that may be useful in the method of the invention, are listed in standard reference works such as McCutcheon's Emulsifiers and Detergents, 1997 edition, Handbook of Industrial Surfactants, 2nd. edition, 1997, published by Gower and International Cosmetic Ingredient Dictionary, 6th. Edition, 1995. The compositions of the present invention can be applied to plants by spraying, using any conventional means for spraying liquids, such as spray nozzles, sprays or the like.
The compositions of the present invention can be used in precision farming techniques, in which an apparatus is used to vary the amount of exogenous chemical applied to different parts of a field, depending on variables such as the particular plant species, composition for land and similar. In one embodiment of said techniques, a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the composition to different parts of a field. At the time of its application to the plants, the composition is preferably sufficiently diluted to be easily sprayed using normal agricultural spraying equipment. Preferred application amounts for the present invention vary depending on a number of factors, including the type and concentration of active ingredient and the species of plant involved. The amounts useful for applying an aqueous composition to a foliage field can vary from about 25 to about 1,000 liters per hectare (l / ha) by spray application. The preferred application rates for aqueous solutions are in the range of about 50 to about 300 l / ha. Many exogenous chemicals (including glyphosate herbicide) must be picked up by the living tissues of the plant and translocated into the plant to produce the desired biological effect (eg, herbicide). In this way, it is important that a herbicidal composition is not applied in such a way as to injure and excessively interrupt the normal operation of the local tissue of the plant so quickly that translocation is reduced. However, a limited degree of local injury may be insignificant, or even beneficial, in its impact on the biological effectiveness of certain exogenous chemicals. A large number of compositions of the invention are illustrated in the following examples. Many concentrated glyphosate compositions have provided sufficient herbicide effectiveness in greenhouse tests to warrant in-field testing of a wide variety of weed species under a variety of application conditions. Water-in-oil-in-water multiple emulsion compositions tested in the field have included: The above compositions were prepared by process (vi) as described in the examples. Aqueous compositions tested in the field having an alkyl ether surfactant as the first excipient substance and / or containing a fatty acid ester have included: The above compositions were prepared by process (vii) if they contain fatty acid ester and by procedure (viii) if they do not contain it. Both procedures are described in the examples. Aqueous compositions tested in the field containing colloidal particle materials have included: Mixture of Aerosil 1: Aerosil MOX-80 + Aerosil MOX-170 (1: 1) Mixture of Aerosil 2: Aerosil MOX-80 + Aerosil 380 (1: 2) The above compositions were prepared by the procedure described in the examples. Aqueous compositions tested in the field having soy lecithin (45% phospholipid, Avanti) as the first excipient substance and a cationic fluorine-organic surfactant as the second excipient substance have included: The above compositions were prepared by process (v) as described in the examples. The aqueous compositions tested in the field having soy lecithin (45% phospholipid, Avanti) as the first excipient substance and a fatty acid ester as the second excipient substance have included: The above compositions were prepared by the process (x) as described in the examples. The dry compositions tested in the field have included: Mixture of Aerosil 1: Aerosil MOX-80 + Aerosil MOX-170 (1: 1) The above compositions were prepared by the method described for dry granular compositions in the examples.
EXAMPLES In the following examples illustrating the invention, greenhouse tests were carried out to evaluate the relative herbicidal effectiveness of the glyphosate compositions. Compositions included for comparison purposes included the following: Formulation B: which consists of 41% by weight of IPA salt of glyphosate in aqueous solution. This formulation is sold in the USA by Monsanto Company under the trademark ACCORD®. Formulation C: which consists of 41% by weight of glyphosate IPA salt in aqueous solution with a co-formulant (15% by weight) of a surfactant (MON 0818 from Monsanto Company) based on polyoxyethylene (15) seboamine. This formulation is sold in Canada by Monsanto Company under the trademark ROUNDUP®. Formulation J: which consists of 41% by weight of IPA salt of glyphosate in aqueous solution. This formulation is sold in the USA by Monsanto Company under the trademark ROUNDUP® ULTRA. Formulation K: which consists of 75% by weight of ammonium salt of glyphosate together with a surfactant, such as a water-soluble dry granulated formulation. This formulation is sold in Australia by Monsanto Company under the trademark ROUNDUP * DRY. Formulations B, C and J contain 356 grams of glyphosate acid equivalent per liter (g a.e./l). Formulation K contains 680 grams of glyphosate acid equivalent per kilogram (g a.e./kg).
Several proprietary excipients were used in the example compositions. They can be identified as follows: Fluorad FC-135, although defined only generically as am'ba in the 3M product literature and in normal directories, has been specifically defined as: C8F17S? 2NH (CH2) 3N + (CH3) 3 I "in a document by J Linert &JN Chasman of 3M, entitled "The effects of fluorochemical surfactants on recoatability" in the December 20, 1993 edition of the American Painy &Coatings Journal, and reprinted as a commercial brochure by 3M.It is believed that Fluorad FC -750 is based on the same surfactant.It is believed that Fluorad FC-754 has the structure: CßF17S? 2NH (CH2) 3N + (CH3) 3 Cies say, identical to Fluorad FC-135 but with a chloride anion replacing iodide.
The following surfactants, identified in the examples as "Suri H1" to "Surf H5", have hydrocarbyl groups as the hydrophobic portion but otherwise bear some structural similarity with the above Fluorad surfactants. They were synthesized and characterized under contract with Monsanto Company. Surf H1: C12H25S02NH (CH2) 3N + (CH3) 3 I "Surf H2: C? 7H35C? NH (CH2) 3N + (CH3) 3 I 'Surf H4: cis-C8H17CH = CH (CH2) 7CONH (CH2) 3N + (CH3 ) 3 I "Surf H5: C7H15CONH (CH2) 3N + (CH3) 3 I 'The ethoxylated fatty alcohol surfactants are called in the examples by their generic names as given in International Cosmetic Ingredient Dictionary, 6th. 1995 edition (Cosmetic, Toiletry and Fragrance Association, Washington, DC). They were obtained interchangeably from several manufacturers, for example: Laureth-23: Brij 35 (ICI), Trycol 5964 (Henkel). Ceteth-10: Brij 56 (ICI). Ceteth-20: Brij 58 (ICI). Steareth-10: Brij 76 (ICI). Steareth-20: Brij 78 (ICI), Emthox 5888-A (Henkel), STA-20 (Heterene). Steareth-30: STA-30 (Heterene). Steareth-100: Brij 700 (ICI).
Ceteareth-15: CS-15 (Heterene). Ceteareth-20: CS-20 (Heterene). Ceteareth-27: Plurafac A-38 (BASF). Ceteareth-55: Plurafac A-39 (BASF). Oleth-2: Brij 92 (ICI). Oleth-10: Brij 97 (ICI). Oleth-20: Brij 98 (ICI), Trycol 5971 (Henkel). When a proprietary excipient is a surfactant provided as a solution in water or another solvent, the amount that will be used was calculated on a real surfactant base, not a "as-is" basis. For example, Fluorad FC-135 is provided as a 50% real surfactant, together with 33% isopropanol and 17% water; in this way to provide a composition containing 0.1% w / w of Fluorad FC-135 as reported herein, 0.2 g of the product as provided was included in 100 g of the composition. The spray compositions of the examples contained an exogenous chemical, such as glyphosate IPA salt, in addition to the listed excipient ingredients. The amount of exogenous chemical was selected to provide the desired amount in grams per hectare (g / ha) when applied in a spray volume of 93 l / ha. Various amounts of exogenous chemical were applied for each composition. Thus, except where otherwise indicated, when the spray compositions were tested, the exogenous chemical concentration varied in direct proportion to the amount of exogenous chemical, but the concentration of excipient ingredients remained constant throughout different amounts of exogenous chemical. The concentrated compositions were tested by dilution, dissolution or dispersion in water to form spray compositions. In these spray compositions prepared from concentrates, the concentration of excipient ingredients varied with that of exogenous chemical. Except where otherwise indicated, these aqueous spray compositions were prepared by one of the following procedures (?), (N) or (¡¡). (i) For compositions that do not contain lecithin or phosphoiipids, the aqueous compositions were prepared by simply mixing the ingredients under mild agitation. (i) A weighted amount of lecithin in powder form was dissolved in 0.4 ml of chloroform in a 100 ml bottle. The resulting solution was air dried to leave a thin film of lecithin, to which 30 ml of deionized water was added. The bottle and its contents were then sonicated in a Fisher Sonic Desmembrator, model 550, equipped with a 2.4 cm probe tip, set at an output level of 8 and continuously operated for 3 minutes. The resulting aqueous dispersion of lecithin was then allowed to cool to room temperature, and a lecithin supply material was formed which was then mixed in the required amounts with other ingredients under mild agitation. In some cases, as indicated in the examples, certain ingredients were added to the lecithin in water before sonification, so lecithin and these ingredients were sonified together. Without being limited by theory, it is believed that by sounding an ingredient of the formulation together with lecithin, at least a portion of that ingredient is encapsulated within, or otherwise bound to, or entrapped by, vesicles or other aggregates formed by the phospholipids present in the lecithin. (iii) The procedure of the method (i) was followed, except that, before sonification, the step of forming a solution of lecithin in chloroform was omitted. Instead, lecithin was placed in powder form in a beaker, water was added and the beaker and contents were then sonicated. Except where otherwise indicated, aqueous concentrated compositions were prepared by one of the following procedures (iv) to (x). (iv) A weighted amount of powdered lecithin of the indicated type was placed in a beaker and deionized water was added in no more than the amount required for the desired final composition. The glass and its contents were then placed in a Físher Sonic Dismembrator, model 550, equipped with a probe tip of 2.4 cm, set at an output level of 8 and continuously operated for 5 minutes. The resulting lecithin dispersion formed the base to which other ingredients with mild agitation were added to make the aqueous concentrate formulation. The order of addition of these ingredients was varied and was found to sometimes affect the physical stability of the concentrated formulation. When a fluorine-organic surfactant such as Fiuorad FC-135 or FC-754 was to be included, it was generally added first, followed by other surfactants if required and then by the exogenous chemical. When the exogenous chemical used was IPA salt of glyphosate, it was added in the form of a 62% solution (45 amp a.e.) by weight, at a pH of 4.4 to 4.6. A final adjustment with water took place when necessary as the last step. In some cases certain ingredients of the concentrated formulation were added before, instead of after sonification, to be sonified with the lecithin. (v) A weighted amount of powdered lecithin of the indicated type was placed in a beaker and deionized water was added in an amount sufficient to provide, after sonification as detailed below, a lecithin supply material at a concentration convenient, usually in the range of 10% to 20% p / p and typically 15% p / p. The beaker and its contents were placed in a Fisher Sonic Dismembrator, model 550, equipped with a probe tip of 2.4 cm with the pulse period set to 15 seconds with intervals of 1 minute between pulses to allow cooling. The power output was set to level 8. After a total of 3 minutes of sonification (periods of 12 pulses) the resulting lecithin supply material was finally adjusted to the desired concentration when necessary with deionized water. To prepare a concentrated aqueous formulation, the following ingredients were mixed in the appropriate proportions with mild agitation, usually in the established order, although this was sometimes varied and found that in some cases affected the physical stability of the concentrated formulation: (a) exogenous chemical, for example glyphosate IPA salt as a 62% solution p / pa pH 4.4 -4.6; (b) lecithin supply material; (c) other ingredients when necessary and (d) water. (vi) Multiple emulsions of water in oil in water (W / O / W) were prepared as follows. First, a water-in-oil emulsion was prepared. To do this, the required amounts of the selected oil and a first emulsifier (called in the examples "emulsifier # 1") were mixed thoroughly. If it was desired to prepare the formulation with glyphosate in the internal aqueous phase, a measured amount of concentrated aqueous solution (62% w / w) of glyphosate IPA salt was added to the oil mixture and first emulsifiable with stirring to ensure homogeneity. The amount of water required in the internal aqueous phase was then added to complete the water-in-oil emulsion, which was finally subjected to high shear mixing, typically using a Silverson L4RT-A mixer equipped with a fine emulsifier screen operated during 3 minutes at 10,000 rpm. The required amount of a second emulsifier (called in the examples "emulsifier # 2") was then added to the water-in-oil emulsion with stirring to ensure homogeneity. If it was desired to prepare the formulation with glyphosate in the external aqueous phase, a measured amount of concentrated aqueous solution (62% w / w) of glyphosate IPA salt was added to the water-in-oil emulsion mixture and the second emulsifier with additional agitation. For completing the multiple emulsion composition of water in oil in water, the amount of water required in the external aqueous phase was added. The composition was finally subjected to high shear mixing, typically using a Silverson L4RT-A mixer equipped with a medium emulsion sieve operated for 3 minutes at 7,000 rpm. (vii) Oil-in-water emulsions were prepared as follows. The required amount of the selected oil and surfactant (sometimes called in the examples "emulsifier # 2" corresponding to the second emulsifier in the process (vi)) were mixed thoroughly. If the selected tepsioactive agent did not flow freely at room temperature, heat was applied to bring the surfactant to a flowable condition before mixing it with the oil. A measured amount of concentrated aqueous solution (62% w / w) of glyphosate IPA salt was added to the surfactant-oil mixture with stirring. The required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The composition was finally subjected to high shear mixing, typically using a Silverson L4RT-A mixer equipped with a medium emulsion sieve operated for 3 minutes at 7,000 rpm. (viii) Aqueous concentrates containing surfactant and having no oil component were prepared as follows. A concentrated aqueous solution (62% w / w) of glyphosate IPA salt in the desired amount was added to a weighted amount of the selected surfactant (s). If the selected surfactant did not flow freely to At room temperature, heat was applied to bring the surfactant to a flowable condition before adding the glyphosate solution. The required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The composition was finally subjected to high shear mixing, typically using a Silverson L4RT-A mixer equipped with a medium emulsion sieve operated for 3 minutes at 7,000 rpm. (ix) For compositions containing a colloidal particulate material, the required amount by weight of the selected colloidal particle material was suspended in a concentrated aqueous solution (62% w / w) of glyphosate IPA salt and stirred with cooling to ensure homogeneity. The required amount by weight of the selected surfactant (s) was added to the resulting suspension. If the selected surfactant did not flow freely at room temperature, heat was applied to bring the surfactant to a flowable condition before adding it to the suspension. In those cases in which an oil, such as butyl stearate, would also be included in the composition, the oil was first mixed thoroughly with the surfactant and the surfactant-oil mixture added to the suspension. To complete the aqueous concentrate, the required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The concentrate was finally subjected to high shear mixing, typically using a Silverson L4RT-A mixer equipped with a medium emulsion sieve operated for 3 minutes at 7,000 rpm. (x) The procedure for preparing aqueous concentrated formulations containing lecithin and butyl stearate was different from that followed for other concentrates containing lecithin. First exogenous chemical, for example glyphosate 1PA salt, was added with mild agitation, to deionized water in a formulation jar. The selected surfactant (which was not lecithin) was then added, continuing at the same time with stirring, to form a preliminary mixture of exogenous chemical / surfactant. When the surfactant did not flow freely at room temperature, the order of addition was not as above. Conversely, the free flowing agent or surfactant was first added to water together with any other surfactant (other than lecithin) required in the composition, and was then heated to 55 ° C in an agitation bath for 2 hours. The resulting mixture was allowed to cool, then exogenous chemical was added with mild agitation to form the preliminary mixture of exogenous chemical / surfactant. A weighted amount of the selected lecithin was added to the preliminary mixture of exogenous chemical / surfactant, with agitation to break up lumps. The mixture was left for about 1 hour to allow the lecithin to be hydrated, then butyl stearate was added with further stirring until phase separation no longer occurred. The mixture was then transferred to a microfluidizer (Microfluidics International Corporation, model M-110F) and microfluidized for 3 to 5 cycles at 69 MPa. In each cycle, the formulation bottle was rinsed with microfluidized mixture. In the last cycle, the finished composition was collected in a dry and clean beaker. The following procedure was used to test compositions of the examples to determine herbicidal effectiveness, except where otherwise indicated. Seeds of the indicated plant species were planted in 85 mm square pots in a soil mix that was previously steam sterilized and pre-fertilized with a 14-14-14 NPK slow release fertilizer at a rate of 3.6 kg / m3. The pots were placed in a greenhouse with sub-irrigation. Approximately one week after the emergence, seedlings were thinned as needed, including the removal of any unhealthy or abnormal plants, to create a uniform series of test pots. The plants were maintained for the duration of the test in the greenhouse where they received a minimum of 14 hours of light per day. If natural light was insufficient to achieve the daily requirement, artificial light with an intensity of approximately 475 microeinsteins was used to establish the difference. Exposure temperatures were not controlled accurately but averaged approximately 27 ° C during the day and approximately 18 ° C during the night. The plants were sub-irrigated throughout the test to ensure adequate levels of soil moisture. The pots were assigned to different treatments in a completely randomized experimental design with 3 replications. A set of pots were left untreated as a reference against which the effects of the treatments could be evaluated afterwards. The application of the glyphosate compositions was made by spraying with a lane sprinkler equipped with a 9501 E nozzle calibrated to provide a spray volume of 93 liters per hectare (i / ha) at a pressure of 166 kilopascals (kPa). After the treatment, the pots were returned to the greenhouse until they were ready for evaluation. The treatments were made using dilute aqueous compositions. These can be prepared as spray compositions directly from their ingredients, or by diluting preformulated concentrated compositions with water. To evaluate the herbicidal effectiveness, all the plants in the test were examined by a single expert technician, who recorded the percentage of inhibition, a visual measurement of the effectiveness of each treatment by comparison with untreated plants. An inhibition of 0% indicates no effect, and a 100% inhibition indicates that all plants are completely dead. An inhibition of 85% or more is considered in many cases acceptable for normal herbicidal use; however, in greenhouse tests such as those in the examples, it is normal to apply compositions in amounts that give less than 85% inhibition, since this makes it easier to discriminate between compositions having different levels of effectiveness.
EXAMPLE 1 Spray compositions containing glyphosate were prepared by mixing in formula B and C formulations with the excipients shown in Table 1. Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown. and were treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicide inhibition was made 18 days after application. The results, averaged for all replicates of each treatment, are shown in Table 1.
Table 1 The tank mixes of Fluorad FC-135 with Formulation B showed a markedly superior herbicidal effectiveness in ABUTH by comparison with Formulation C, but did not coincide with the herbicidal effectiveness of Formulation C in ECHCF. The antagonism of the glyphosate activity in ECHCF observed with the organosilicon non-ionic surfactant Silwet L-77 did not occur with the cationic fluoro-organic surfactant Fluorad FC-135.
EXAMPLE 2 Spray compositions containing sodium glyphosate or IPA salts and excipient ingredients as shown in Table 2a were prepared. The procedure (ii) was followed for all the compositions, using soy lecithin (10-20% phospholipid, Sígma Type ll-S). Without adjustment, the pH of the compositions was about 5. For the compositions having a pH of about 7 as shown in Table 2a, the pH was adjusted using the same base (sodium hydroxide or IPA) which formed the salt of glyphosate.
Table 2a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 17 days after application. Formulation C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 2b.
Table 2b A strong herbicidal effectiveness was observed with compositions 2-10 and 2-11 containing lecithin and Fluorad FC-135 in both ABUTH and ECHCF, by comparison with otherwise similar compositions (2-09 and 2-01) that lacked of Fuorad FC-135. The herbicidal effectiveness of composition 2-11 in the amount of 100 g ae / ha of glyphosate was superior to that of formulation C to a quantity three times higher in ABUTH and higher than that of formulation C in a quantity twice as much in ECHCF EXAMPLE 3 Spray compositions containing sodium salt were prepared IPA of glyphosate and excipient ingredients as shown in Table 3a. Procedure (ii), indicated in Table 3a involving "high" sonification power for all compositions, was followed, except that for composition 3-06 a different sonification procedure, called "low" sonication power, was used. . In this procedure, the lecithin in water was sonicated in an ultrasonic bath Fiser model FS 14H for 30 minutes. Soy lecltin (10-20% phospholipid, Sigma Type ll-S) was used for all the compositions. Without adjustment, the pH of the compositions was about 5. For the compositions having a pH of about 7 as shown in Table 3a, the pH was adjusted using the same base (sodium hydroxide or IPA) which formed the salt of glyphosate.
Table 3a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 3b.
Table 3b Composition 3-12 containing lecithin and Fluorad FC-135 showed surprisingly high herbicidal effectiveness again compared to composition 3-01, which lacked Fluorad FC-135, and also compared to formulation C. When efforts were made To encapsulate Fluorad FC-135 or glyphosate (compositions 3-13 or 3-14 respectively) in lecithin liposomes by sonification in the presence of the ingredients to be encapsulated, some additional increase in herbicidal effectiveness was evident in ABUTH, but was reduced the effectiveness in ECHCF. Of all, the best activity in this test was obtained without encapsulation.
EXAMPLE 4 In this example, compositions 3-01 to 3-12 of Example 3 were tested. Black nightshade plants (Solanum nigrum, SOLNI) were grown and treated by the normal procedures given above. The spray applications were made 26 days after planting SOLNI and the evaluation of the herbicide effectiveness was made 16 days after the application. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 4.
Table 4 Composition 3-12 containing lecithin and Fluorad FC-135, as in the test of Example 3, showed remarkably strong herbicidal effectiveness, this time in SOLNI. EXAMPLE 5 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 5a were prepared. The procedure (i) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was approximately 5.
TABLE 5a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicide inhibition was made 17 days after application. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 5b. TABLE 5b The glyphosate activity in ECHCF in this test was too high to make significant somatizations. However, in ABUTH, composition 5-20 containing lecithin and Fluorad FC-135 exhibited markedly strong herbicidal effectiveness compared to composition 5-01 (without Fluorad FC-135) and formulation C. As in previous tests, it was obtained a slight additional advantage in ABUTH making efforts to encapsulate glyphosate in lecithin loposomes, as in composition 5-21 Compositions 5-22 and 5-23, which contained both Fluorad FC-135 and Sllwet L-77 in addition to lecithin, they also showed remarkably good herbicidal effectiveness EXAMPLE 6 In this example, compositions 5-01 to 5-23 of example 5 were tested. Maravilla plants (Ipomoea spp, IPOSS) were grown and treated by the normal procedures given arpba. The applications of the spray compositions were made 14 days after plant IPOSS and the evaluation of herbicide effectiveness was made 19 days after the application Formulations B and C, alone and mixed in tank with Sllwet L-77 at 05%, were applied as comparative treatments The results, averaged for all replicates of each treatment, are shown in table 6 TABLE 6 Once again, a surprisingly strong herbicidal effectiveness, this time in IPOSS, was exhibited by compositions 5-20 to 5-23, all of which contain lecithin and Fluorad FC-135.
EXAMPLE 7 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 7a were prepared. Procedure (ii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was about 7.
TABLE 7a Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, S1DSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF. The SIDP planting date was not recorded. The evaluation of the herbicide inhibition was made 19 days after the application. Formulations B and C, alone and mixed in tank with Silwet L-77 at 0.5%, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 7b.
Table 7b 15 20 .fifteen Compositions 7-14 to 7-16, which contained 0.25% lecithin together with Fluorad FC-135, provided excellent herbicidal effectiveness in all three species tested. Even at the lowest concentration of Fluorad FC-20 135 (0.1% in composition 7-16), effectiveness remained substantially in ABUTH and ECHCF, although some loss of effectiveness was evident in SIDSP. Compositions 7-11 to 7-13, which contained lecithin, Fluorad FC-135 and Silwet L-77, also performed well in this test, showing no antagonism in ECHCF characteristic of compositions containing Silwet L-77 but not Fluorad FC-135.
EXAMPLE 8 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 8a were prepared. Procedure (ii) was followed for all compositions, using soy lecithin (20% phospholipid, Avapti). Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 8a were prepared. The pH of all the compositions was adjusted to approximately 7.
Table 8a Plants of yellow sedge (Cyperus esculentus, CYPES) were cultivated and treated by the normal procedures given above. Applications of the spray compositions were made 21 days after planting CYPES, and the evaluation of herbicide effectiveness was made 27 days after application. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 8b. Table 8b The normal standard C formulation exhibited very high herbicidal effectiveness in this test and for this reason it is not possible to discern increases. There is a suggestion to the lowest amount of giifosate (500 g a.e./ha), the effectiveness of the compositions containing lecithin and Fluorad FC-135 (8-14 to 8-16) in CYPES improved surprisingly by decreasing the concentration of Fluorad FC-135.
EXAMPLE 9 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 9a were prepared. Procedure (ii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 9a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by normal procedures given above. There was no record of planting dates. The evaluation of the herbicide inhibition was made 16 days after the application. In addition to compositions 9-01 to 9-21, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at 0.5%. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 9b.
Table 9b i 15 The compositions of this example (9-17 to 9-21) containing very low concentrations of lecithin and Fluorad FC-135 exhibited remarkably high herbicidal effectiveness. Even a composition (9-19) with only 0.1% lecithin and 0.1% Fluorad FC-135 was much more effective in ABUTH than the commercial standard formulation C, and equally as effective in ECHCF as formulation C. Apparently strong antagonism in ECHCF observed when formulation B was mixed in tank with 0.5% Fluorad FC-135 in this test is not characteristic and has not been observed in other tests (see, eg, example 12 in the present); in fact, the data for this set of treatments are so out of line that it is believed that they may be due to an error in the application.
EXAMPLE 10 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 10a were prepared. The procedure (iii) was followed for all compositions, using soy lecithipa (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 10a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
In addition to compositions 10-01 to 10-17, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at varying concentrations. Formulations B and C, alone and mixed in tank with Sllwet L-77 at 0 5%, were applied as comparative treatments The results, averaged for all replicates of each treatment, are shown in Table 10b Table 10b The tank mix of Fluorad FC-135 at concentrations as low as 0.05% with formulation B resulted in efficacy W herbicide remarkably strong in this test. The antagonism in ECHCF observed with the organosilicon non-ionic surfactant Silwet L-77 does not occurred with the cationic fluoro-organic surfactant Fluorad FC-135. It is worth mentioning the surprising herbicidal effectiveness provided by a composition (10-15) that only contained 0.05% lecithin and 0.05% Fluorad FC-135. In this test, the addition of 0.1% methyl caprate to 0.25% lecithin, being ^ The methyl caprate together with the lecithin, improved the performance in ECHCF but not in ABUTH (compare compositions 10-16 and 10-04).
EXAMPLE 11 Compositions 10-01 to 10-17 of Example 10, and tank mixes of Formulations B and C with Fluorad FC-135 were tested in this example M 5. Spiny dibetu plants (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 22 days after planting SIDP, and evaluation of herbicide inhibition was made 19 days after application. Formulations B and C, alone and mixed in tank with Silwet 20 L-77 at 0.5%, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in table 11.
Table 11 The herbicidal effectiveness of formulation C was very high in SIDSP in this test and consequently improvements are difficult to discern. However, a remarkably strong performance was observed again with composition 10-15, which contained only 0.05% lecithin and 0.05% Fluorad FC-135.
EXAMPLE 12 Aqueous spray compositions were prepared containing IPA salt of glyphosate and excipient ingredients as shown in Table 12a. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and marigold (Ipomoea spp, IPOSS) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH, 18 days after planting ECHCF and 9 days after planting IPOSS. The evaluation of the herbicide inhibition was made 15 days after the application In addition to compositions 12-01 to 12-14, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C, alone and mixed in tank with 0.5% Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 12b.
Table 12b Tank mixtures of Formulation B with Fluorad FC-135 gave greater herbicide effectiveness than formulation C alone, without the corresponding antagonism in ECHCF so characteristic of Silwett L-77. The addition of Fluorad FC-135 to glyphosate compositions containing 0.25% lecithipa improved herbicidal effectiveness in ABUTH and ECHCF, but not in this test, in IPOSS (compare compositions 12-04 and 12-06 with composition 12-03) EXAMPLE 13 Compositions 12-01 to 12-14 of Example 12, and tank mixes of Formulations B and C with Fluorad FC-135 were tested in this example. Spiny dibetu plants (Sida spinosa) were grown., SIDSP) and were treated by the normal procedures given above The applications of spray compositions were made 23 days after planting SIDP, and the evaluation of herbicide inhibition was made 19 days after application Formulations B and C, alone and mixed in tank with Sllwet L-77 at 05%, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in table 13 Table 13 In SIDSP in this test, the addition of the tank mix of Fluorad FC-135 to formulation B increased the herbicide effectiveness over that obtained with formulation C alone, only at the concentration of 0 5% of Fluorad FC-135 Equal Thus, when added to a glyphosate composition containing 025% lecithin, Fluorad FC-135 increased herbicide effectiveness very significantly at the 0-5% concentration (composition 12-04) EXAMPLE 14 Aqueous spray compositions containing IPA salt of glyphosate and excipient ingredients as shown in Table 14a were prepared. The procedure (m) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The following compositions had a pH of about 5 14-01, 14-03, 14-07, 14-08, 14-10 and 14-12 to 14-17 All the others were adjusted to a pH of about 7 Table 14a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 28 days after planting ECHCF, and evaluation of herbicide inhibition was made 20 days after application. In addition to compositions 14-01 to 14-17, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C, alone and mixed in tank with 0.5% and 0.25% of Silwet L-77, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 14b.
Table 14b ^ k \ Compositions 14-12 to 14-15, which contained 025% leatipa together with Fluorad FC-135, exhibited much higher herbicidal effectiveness on both ABUTH and ECHCF than composition 14-03, which contained 025% lecithin but not Fluorad FC-135, or even composition 14-01, which contained 0 5% lecithin but not Fluorad FC-135 No large or consistent difference was observed between the compositions in which the glyphosate had been sonified A 15 together with the lecithm (14-13 and 14-15) that in which the lecitme had been sonified alone (14-12 and 14-14) EXAMPLE 15 Compositions 14-01 to 14-17 of Example 14, and mixtures in tanks of formulations B and C with Fluorad FC-135 were tested in this example. Spiny dibetu plants (Sida spinosa, SIDSP) were grown and treated by the normal procedures given arpba.
Spray compositions were made 22 days after planting SIDP, and evaluation of herbicide inhibition was made 19 days after application Formulations B and C, alone and mixed in tank with 0 5% and 025% Sllwet L-77 , were applied as comparative treatments The results, averaged for all the replicas of each treatment are shown in table 15 Table 15 Compositions 14-12 to 14-15, which contained 0.25% lecithin together with Fluorad FC-135, exhibited much greater herbicidal effectiveness on ABUTH as on ECHCF than composition 14-03, which contained 0.25% lecithin but no Fluorad FC -135, or even composition 14-01, which contained 0.5% lecithin but not Fluorad FC-135. There was not a wide or consistent difference between the compositions in which the glyphosate had been sonified together with the lecithin (14-13 and 14-15) that in which the lecithin had been sonified alone (14-12 and 14-14). ).
EXAMPLE 16 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 16a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
TABLE 16a Alcotán plants were cultivated (Abutilón theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) and were treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 17 days after application. In addition to compositions 16-01 to 16-19, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C, alone and mixed in tank with 0.5% of Sllwet 800, were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 16b. TABLE 1b As in Example 10, the glyphosate compositions (16-10 and 16-11) containing only 0.05% lecithin and 0.05% Fluorad FC-135 exhibited surprisingly broad herbicidal effectiveness in this test. The sonification of lecithin in the presence of glyphosate in an effort to yield on the sonification of lecithin alone (composition 16-10); in fact, in ECHCF the herbicide effectiveness was slightly better without such efforts to encapsulate glyphosate. Addition of methyl caprate to compositions containing lecithin with or without Fluorad FC-135 (16-13 to 16-15) improved herbicidal effectiveness in ABUTH but had very little effect on ECHCF.
EXAMPLE 17 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 17a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 17a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 16 days after application. In addition to compositions 17-01 to 17-19, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 17b.
Table 17b In compositions containing lecithin and Fluorad FC-135, no consistent difference in herbicidal effectiveness was observed between those in which lecithin was sonified alone (17-02, 17-07, 17-09) and those in which glyphosate and lecithin were sonified together (17-03, 17-08, 17-10). It is believed that the anomalous inversion of the apparent quantity response observed with composition 17-18 is the result of an error in the application or record, and the data for this composition should be ignored in this example.
EXAMPLE 18 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 18a were prepared. The procedure (ii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 18a Hemp plants (Sesbania exaltata, SEBEX) were grown and treated by the normal procedures given above. The applications of the spray compositions were made 22 days after planting SEBEX, and the evaluation of the herbicide inhibition was made 21 days after the application. In addition to compositions 18-01 to 18-11, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone, and formulation B mixed in tank with 0.1% PVA (polyvinyl alcohol), were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 18b.
Table 18b The glyphosate activity in SEBEX was extremely weak in this test and no firm conclusions can be drawn.
EXAMPLE 19 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Example 1 were prepared. table 19a. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avapti). The pH of all the compositions was adjusted to approximately 7.
Table 19a Sickle-pod plants (Cassia obtusifolia, CASOB) and were treated by the normal procedures given above. Applications of spray compositions were made 22 days after planting CASOB, and evaluation of herbicide inhibition was made 21 days after application. In addition to the compositions 19-01 to 19-06, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 19b.
Table 19b In CASOB, the addition of Fluorad FC-135 to a glyphosate composition containing lecithin siginficatively increased the herbicidal effectiveness (purchase compositions 19-05 and 19-02. However, when the glyphosate was sonified together with the lecithipase (composition 19-). 06), herbicide effectiveness was reduced.
EXAMPLE 20 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 20a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avapti). The pH of all the compositions was adjusted to approximately 7.
Table 20a Common orzaga plants (Chenopodium album, CHE? AL) were grown and treated by the normal procedures given above. The applications of the spray compositions were made 31 days after planting CHEAL, and the evaluation of the herbicide inhibition was made 18 days after the application. In addition to compositions 20-01 to 20-07, spray compositions were prepared by tank mixing formulations B and C with 0. 5% of Fluorad FC-135. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 20b.
TABLE 20b The glyphosate activity in CHEAL was very weak in this test and no definitive conclusions could be drawn. However, none of the compositions of the invention performed as well in this test as the commercial standard C formulation. Fluorad FC-135 at the extremely low concentration of 0.05% was ineffective as an additive for tank mixing, but the addition of 0.05% of Fluorad FC-135 did increase the performance of the compositions containing lecithin (compare compositions 20-04 to 20-06 with 20-01 to 20-03).
EXAMPLE 21 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 21a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 21a Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galii, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. The Applications of spray compositions were made 19 days after planting ABUTH and 22 days after planting ECHCF The date of planting SIDP was not recorded. The evaluation of the herbicide inhibition was made 20 days after the application. In addition to compositions 21-01 to 21-19, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in table 21 b.
Table 21b In this test, the glyphosate concentration that had to have been added in the tank mixture to Formulation B to bring its herbicidal yield up to that of Formulation C was approximately 0. 25% for ECHCF, 0.1% for SIDSP and 0.02% for ABUTH. The herbicidal effectiveness of composition 21-12 (0.25% lecithin, 0.25% Fluorad FC-135) was uncharacteristically weak in this test. However, composition 21-13 (0.05% lecithin, 0.05% Fluorad FC-135) performed well as in previous tests, exceeding the herbicidal effectiveness of formulation C in ABUTH, at least equaling it in SIDSP and not completely equaling it in ECHCF. Contrary to the results obtained in other tests, improved effectiveness in ECHCF and SI DSP was obtained by sonification of glyphosate with lecithin (composition 21-14 versus 21-13). The inclusion of methyl caprate (compositions 21 -15 and 21-16) also improved efficacy in these species. A surprisingly high herbicidal effectiveness was observed in this test with the compositions containing ultra low concentrations of lecithin and Fluorad FC-135 (0.02% of each, 21-17 and 21-18).
EXAMPLE 22 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 22a were prepared. The procedure (iv) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of these compositions was not recorded.
Table 22a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echmochloa crus-galli, ECHCF) were grown and treated by the normal procedures given arpba. Applications of spray compositions were made 14 days after planting ABUTH and 16 days after ECHCF, and the evaluation of herbicide inhibition was made 14 days after application Formulation C was applied as a comparative treatment The results, averaged for all replicates of each treatment, are shown in Table 22b Table 22b None of the concentrated compositions of this example containing 10% a.e. of glyphosate and variable amounts of Fluorad FC-135 (22-01 to 22-06) exhibited a greater herbicidal activity than the commercial standard formulation C. It should be noted that the quantities of Fluorad FC-135 used in this example were extremely high, varying the weight / weight ratio of Fluorad FC-135 to a.e. of glyphosate from 1: 2 to 3: 1.
EXAMPLE 23 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 23a were prepared. The procedure (iv) was followed for all compositions, using soy lecithipase (20% phospholipid, Avanti). The pH of all the compositions was approximately 5. Table 23a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 18 days after plant ECHCF, and the evaluation of herbicide inhibition was made 14 days after application. Formulations B and C were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 23b.
Table 23b Concentrated composition 23-05 (5% lecithin, 2% MON 0818, 5% Fluorad FC-135) did not exhibit greater herbicidal effectiveness in this test than composition 23-01 lacking Fluorad FC-135.
EXAMPLE 24 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 24a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avapti). The pH of these compositions was not recorded.
Table 24a Plants of yellow sedge (Cyperus esculentus, CYPES) and were treated by the normal procedures given above. Applications of spray compositions were made 29 days after planting CYPES, and evaluation of herbicide effectiveness was made 33 days after application. In addition to compositions 24-01 to 24-16, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 24b.
Table 24b The tank mixes of this example show a surprisingly small effect on the herbicidal effectiveness of CYPES to reduce the concentration of Fluorad FC-135 from 0.25% to 0.01%. At this exceedingly low concentration, the tank mixture of formulation B with Fluorad FC-135 still acted the same or better than formulation C alone. Leatin alone was an unexpectedly effective excipient for glyphosate in this test (see compositions 24-01 to 24-05) and the addition of Fluorad FC-135 to lecithin did not in each case give an additional increase in herbicidal effectiveness.
EXAMPLE 25 Spray compositions containing glyphosate were prepared by tank mixing formulation B with excipients as shown in Table 25. Soy lecithin (20% phospholipid, Avanti) was used in the form of a 10% dispersion prepared by sonification as in the procedure (i¡¡). Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 21 days after application. The results, averaged for all replicates of each treatment, are shown in Table 25.
Table 25 This test was a titration study of expanded amount of MON 0818, Fluorad FC-135 and lecithin as tank mix adjuvants for glyphosate as formulation B. In ABUTH, the optimal concentration of adjuvant was 2.0% for MON 0818, 0.2 % for Fluorad FC-135 and 0.2% or more for lecithin. At ECHCF, the optimal adjuvant concentration was 0.5% at 2.0% for MON 0818, 0.2% at Fluorad FC-135 and 2.0% at lecithipa.
EXAMPLE 26 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 26a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 26a Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SI DSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH, 19 days after planting ECHCF and 26 days after planting SIDSP. The evaluation of herbicide inhibition was made for ABUTH and ECHCF 15 days after the application and for SIDSP 21 days after the application. In addition to compositions 26-01 to 26-18, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 26b.
Table 26b This test was designed in part to explore the relative contribution of Fluorad FC-135 and lecithin to the herbicidal effectiveness of glyphosate compositions comprising both of these excipient substances. Fluorad FC-135 was applied as the only excipient at concentrations of 1.0%, 0.5% and 0.2% (see tank mix treatments with formulation B). Lecithin was applied as the sole excipient at the same three concentrations in compositions 26-09, 26-11 and 26-15. The combinations of the two excipients at equal concentrations were applied in the corresponding compositions 26-10, 26-13 and 26-17. The data are highly variable but a global trend can be discerned. When only one of the two excipients was present, the herbicidal effectiveness tended to fall as the concentration of that excipient decreased. When both excipients were present, there was hardly any decline in herbicidal effectiveness as the excipient concentration was reduced. Although the data averages of three amounts of glyphosate across three species may not lead to anything, it is useful in this case to reduce the mass of the individual data to the following percentage inhibition averages: Glyphosate (Formulation B) 68% Glyphosate + 0.1% Fluorad FC-135 81% Glyphosate + 0.05% Fluorad FC-135 71% Glyphosate + 0.02% Fluorad FC-135 63% Glyphosate + 0.1% Lecithin 76% Glyphosate + 0.05% Lecithin 74% Glyphosate + 0.02% Lecithin 68% Glyphosate + 0.1% Fluorad FC-135 + 0.1% Iecitin 77% Glyphosate + 0.05% Fluorad FC-135 + 0.05% Lecithin 76% Glyphosate + 0.02% of Fluorad FC-135 + 0.02% of lecithin 75% Commercial parameter of glyphosate (formulation C 73% Thus, when both excipients are used together, a five-fold decrease in excipient concentration results in a decrease in overall herbicidal effectiveness of only 2 percentage points, while still retaining an overall effectiveness at least equal to that of the parameter commercial.
EXAMPLE 27 Spray compositions containing glyphosate were prepared by tank mixing formulation B with excipients as shown in Table 27. Soy lecithin (20% phospholipid, Avanti) was used in the form of a % dispersion prepared by sonification as in procedure (iii). Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 15 days after planting ECHCF, and evaluation of herbicide inhibition was made 19 days after application. The results, averaged for all replicates of each treatment, are shown in Table 27.
Table 27 This tank mixing study clearly demonstrates the surprising interaction observed in example 26 between lecithin and Fluorad FC-135 as excipients for glyphosate. For example, glyphosate alone over four amounts gave a percentage inhibition of ABUTH of 32%. The addition of Fluorad FC-135 at a concentration of 0.5% promoted the percentage of inhibition to 55%, but the addition of lecithin at the same concentration did not raise the inhibition percentage more than 32%. A 1: 1 combination of both excipients at the same total concentration gave a percentage inhibition of 51% At a concentration of 0.1%, Fluorad FC-135 gave a 50% inhibition percentage, 21% lecithin (ie, a reduction in glyphosate effectiveness) and the 1: 1 48% combination. In this way, as in the example 26, the decrease in herbicidal effectiveness with the reduction in the amount of excipient was much less pronounced with the combination than with each excipient alone.
EXAMPLE 28 Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 28a. The procedure (i) was followed for compositions 28-01 to 28-06. The procedure (iv) was followed for compositions 28-07 to 28-11, using soybean (20% phospholipid, Avanti). Process (iv) was also used for compositions 28-12 and 28-13, but OT in aerosol was the aggregate-forming material used in place of lecithin. The pH of all the compositions was approximately 5.
TABLE 28a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicide inhibition was made 38 days after application. Formulations B and C were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 28b.
Table 28b Concentrated compositions 28-08 and 28-09 did not exhibit in this test herbicidal effectiveness equal to that of formulation C.
EXAMPLE 29 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 29a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% or 45% phospholipid as indicated below, both obtained from Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 29a Plants of yellow sedge (Cyperus esculentus, CYPES) were cultivated and treated by the normal procedures given above. The applications of the spray compositions were made 27 days after planting CYPES. The evaluation was made 27 days after the application. In addition to compositions 29-01 to 29-16, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 29b.
Table 29b This test was carried out to investigate the effect of the phospholipid content of lecithin on the herbicidal efficacy of the gyphosphate compositions containing lecithin. A clear pattern of this study did not emerge, but above all it appeared that crude lecithin (20% phospholipids) provided greater herbicidal effectiveness in CYPES than deoiled lecithin (45% phospholipids), suggesting that the oil present in raw lecithin could have had an adjuvant effect on this species.
EXAMPLE 30 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 30a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20%, 45% or 95% phospholipid as indicated below, both obtained from Avanti) The pH of all the compositions was adjusted to approximately 7. Table 30a Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH, 19 days after planting ECHCF and 23 days after planting SIDSP. The evaluation of the herbicide inhibition was made 15 days after the application. In addition to compositions 30-01 to 30-18, spray compositions were prepared by mixing tank B and C formulations with Fluorad FC-135 at various concentrations. The results, averaged for all replicates of each treatment, are shown in Table 30b.
Table 30b fifteen In general, through the three species included in this test, the compositions containing the 45% degree of soy lecithin phospholipids provided a slightly higher herbicidal effectiveness than those containing the 20% grade. Any additional improvement obtained using the degree 95% was minimal and probably would not justify the considerably increased cost of this grade. The data from this test clearly show a non-additive interaction between lecithin and Fluorad FC-135. To cite just one example for illustration, glyphosate alone (formulation B) at 200 g a.e./ha gave 22% ^ inhibition of ABUTH, 29% inhibition of ECHCF and 49% inhibition of SIDSP. The addition of 0.02% of Fluorad FC-135 led these percentages of inhibition to 64%, 40% and 46% respectively. Alternatively, the addition of the 45% degree of lecithin to 0.02% (compositions 30-05) resulted in inhibition percentages of 32%, 35% and 36% respectively. The addition of both excipients, each at 0.02% (composition 30-14) gave percentages of inhibition of 90%, 49% and 72% respectively. Even the addition of both excipients so that the total excipient concentration was 0.02% (composition 30-17) resulted in inhbition percentages of 92%, 27% and 73% respectively. In this way, at least in hardwood species (ABUTH and SIDSP) there is strong evidence of a synergistic interaction between these two excipient substances.
EXAMPLE 31 Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 31 a. Process (iii) was followed for all compositions, using soy lecithin (20% or 95% soy phospholipids, or 95% egg yolk phospholipids, all obtained from Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 31a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after ABUTH plants and 19 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
In addition to compositions 31-01 to 31 -14, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-754 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 31b.
Table 31b In this test, glyphosate compositions containing egg yolk lecithin (31 -01 to 31-03) acted similarly to those containing soy lecithin (31 -04 to 31-06) in ABUTH, but were generally more effective than those containing soy lecithin in ECHCF, at least in the absence of Fluorad FC-135. The addition of Fluorad FC-135, as in the compositions 31-07 to 31-12, increased the effectiveness of all the compositions.
EXAMPLE 32 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 32a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (20% phospholipid, Avanti). The pH of all the compositions was adjusted to approximately 7. I15 Table 32a twenty Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and 27 days after planting SIDSP. The evaluation of the herbicide inhibition was made 15 days after the application. In addition to compositions 32-01 to 32-11, spray compositions were prepared by tank mixing formulations B and C with various fluorine-organic surfactants of the Fluorad class, all at 0.02%. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 32b.
Table 32b Composition 32-07, which contained 0.02% lecithin and 0.02% Fluorad FC-754 was equal to or greater than composition 32-02, which contained f 0.02% lecithin and 0.02% Fluorad FC-135, in herbicidal effectiveness. This indicates that Fluorad FC-754 is an acceptable substitute for Fluorad FC-135 in said compositions. The other fluorine-organic surfactants tested in this example, none of which is cationic, were less effective than the fluoro-organic surfactants Fluorad FC-135 and Fiuorad FC-754 as A excipients in combination with lecithin. One possible exception was Fluorad FC-10 170C, which gave an adequate increase in the effectiveness of glyphosate only in ECHCF.
EXAMPLE 33 A15 Concentrated aqueous compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 33a. The procedure (v) was followed for all compositions, using soy lecithin (20% phospholipids, Avanti). The pH of all the compositions was adjusted to approximately 5.
Table 33a Alcotan plants (Abutilon theophrasti, Abuth) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicide inhibition was made 19 days after application. Formulations C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 33b.
Table 33b Concentrated compositions containing lecithin and Fluorad FC-135 did not exhibit a herbicidal effectiveness superior to the normal commercial P formulations C and J in this test.
EXAMPLE 34 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 34a were prepared. The procedure (iii) was followed for all compositions, ^ using soy lecithin (20% phospholipids, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 34a Guinea grass plants were grown (Panicum maximun, ANMA) and treated by the normal procedures given above. Applications of spray compositions were made 78 days after planting PANMA, and evaluation of herbicide inhibition was made 20 days after application. In addition to compositions 34-01 to 34-08, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 34b.
Table 34b Exceptionally high glyphosate activity was observed in this test even with formulation B and no firm conclusions can be drawn. However, none of the compositions containing lecithin and Fluorad FC-135 exceeded the effectiveness of the commercial standard formulation C in PANMA under the conditions of this test.
EXAMPLE 35 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 35a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (20% phospholipids, Avanti). The pH of all the compositions was adjusted to approximately 5.
Table 35a Grass plants (Elymus repßns, AGRRE) were cultivated and treated by the normal procedures given above. Applications of spray compositions were made 56 days after planting AGRRE, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 35b.
Table 35b Compositions of the invention exhibiting herbicide effectiveness superior to that of the commercial standard formulation C in this test in AGRRE included 35-01, 35-02, 35-03, 35-13 and 35-15 to 35-18. Compositions 35-17 and 35-18 were the most effective in this test, surpassing in performance the commercial standard formulation J, as well as formulation C.
EXAMPLE 36 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 36a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (20% phospholipids, Avanti). The order of addition of the ingredients was varied in the compositions 36-15 to 36-20 as shown below. The pH of all the compositions was approximately 5.
Table 3a (*) Order of addition: Plants d? alcotán (Abutilón theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) and were treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 22 days after planting ECHCF, and evaluation of herbicide inhibition was made 17 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 36b.
Table 3b Apparently, the order of addition of the ingredients had some influence on the herbicidal effectiveness of the compositions 36-09 to 36-20. However, since most of these compositions showed poor short-term stability, it is possible that in at least one of the cases the uniformity of the spray application was affected and the results are therefore difficult to interpret.
EXAMPLE 37 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 37a were prepared. The procedure (vi) was followed for all compositions, using soy lecithin (20% phospholipids, Avanti). The pH of all the compositions was approximately 5.
Table 37a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 13 days after planting ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
The compositions containing PVA were very viscous to be sprayed and their herbicidal effectiveness was not tested. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 37b.
Table 37b Concentrated compositions containing lecithin and Fluorad FC-754 or methyl caprate did not exhibit a herbicidal effectiveness equal to that of the normal commercials in this test.
EXAMPLE 38 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 38a were prepared. The procedure (ili) was followed for all compositions, using soy lecithin (20% phospholipids, Avanti). The pH of all the compositions was approximately 5.
Table 38a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 14 days after application. In addition to compositions 38-01 to 38-17, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 38b.
Table 38b Since the concentrated compositions of the above examples have tended to exhibit a weaker herbicidal effectiveness than that which has been observed with the ready-made spray compositions, this test was carried out to determine whether the degree of concentration at which a composition is prepared before the dilution to sprinkle had influence on the effectiveness. No consistent trend was observed in this test.
EXAMPLE 39 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 39a were prepared. The procedure (iii) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti). The pH of all the compositions was approximately 5.
Picture 39a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicide inhibition was made 21 days after application. Formulation C was applied as a comparative treatment. The results, averaged for all replicates of each treatment, are shown in Table 39b.
Table 39b No difference in herbicidal effectiveness was observed between compositions 39-03 and 39-04. The only difference between these compositions is that 39-03 contained Fluorad FC-135 and 39-04 contained Fluorad FC-754.
EXAMPLE 40 Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 40a. The procedure (iii) was followed for all compositions, using soy lecithin (20% or 45% phospholipids as indicated below, both obtained from Avanti). The pH of all the compositions was about 7.
Table 40a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 21 days after planting ECHCF, and the evaluation of herbicide inhibition was made 18 days S after application. In addition to compositions 40-01 to 40-11, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 or Fluorad FC-754 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment are shown in Table 40b.
Table 40b There was a tendency, although not sufficiently robust, for the compositions of this example containing Fluorad FC-754, to show a slightly weaker herbicidal effectiveness than the corresponding compositions containing Fluorad FC-135.
EXAMPLE 41 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 41a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti). The pH of all the compositions was approximately 5. Table 41a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application. In addition to compositions 41-01 to 41-18, spray compositions were prepared by tank mixing formulations B and J with Fluorad FC-135 in two concentrations. Formulations B and J alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 41b. Table 41b An adequate herbicidal effectiveness was obtained with the concentrated compositions of this example which contained lecithin and Fluorad FC-135 or Fluorad FC-754. There was not a wide or consistent difference between the compositions containing Fluorad FC-135 and its counterparts containing Fluorad FC-754.
EXAMPLE 42 Concentrated compositions containing sodium salt were prepared IPA of glyphosate and excipient ingredients as shown in Table 42a. The procedure (v) was followed for all compositions, using soy lecithin (95% phosphoiipid, Avanti). The pH of all the compositions was approximately 5. Table 42a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application. In addition to compositions 42-01 to 42-16, spray compositions were prepared by tank mixing formulations B with Fluorad FC-135 at two concentrations. Formulations B and J alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 42b.
Table 42b The only compositions concentrated in this test that exhibited excellent performance, at least in ABUTH, were 42-15 and 42-16. EXAMPLE 43 Concentrated aqueous compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 43a. The procedure (viii) was followed for compositions 43-02, and the procedure (x) for compositions 43-03 and 43-13, which contained a colloidal particulate material together with surfactant. Composition 43-01 contains colloidal particulate material but no surfactant. The pH of all the compositions was approximately 5.
Table 43a The velvet leaf plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated with the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicide inhibition was made 23 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 43b.
Table 43b The more concentrated compositions containing Fluorad FC-135 showed increased herbicidal effectiveness as compared to formulation B, but the yield was not equal to that of the commercial standard formulations under the conditions of this test.
EXAMPLE 44 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 44a were prepared. The procedure (viii) was followed for compositions 44-01, 44-03, 44-06, 44-07, 44-10, 44-14, 44-15, 44-18 and 44-19, and the procedure ( ix) for compositions 44-02, 44-08, 44-09, 44-16 and 44-17, which contained a colloidal particulate material together with surfactant. Compositions 44-04, 44-05, 44-12 and 44-13 contain colloidal particulate material but no surfactant. The pH of all the compositions was approximately 5. Table 44a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicide inhibition was made 25 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 44b. Table 44b Concentrated compositions containing Fluorad FC-135 showed increased herbicidal effectiveness compared to formulation B, but did not provide a herbicidal effectiveness equal to that of formulations C and J commercial standards in this test.
EXAMPLE 45 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 45a were prepared. Procedure (i) was followed for compositions 45-10 to 45-12, and procedure (ii) for compositions 45-01 to 45-09, using lecithin soybean (45% phospholipids, Avanti). The pH of all the compositions was adjusted to approximately 7.
Table 45a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 23 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application. In addition to compositions 45-01 to 45-12, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 45b.
Table 45b An extremely high herbicidal effectiveness was noted on ABUTH with compositions 45-04 to 45-06 containing lecithin and Fluorad FC-135. The replacement of Fluorad FC-135 by "Surf H1", a hydrocarbon-based surfactant of the formula Ci2H25S? 2NH (CH2) 3N + (CH3) 3 1", gave compositions 45-07 to 45-09) an effectiveness in ABUTH still exceeds low amounts of glyphosate than formulations C and J commercial standards, but not as great as that of compositions 45-04 to 45-06 The performance of compositions 45-04 to 45-12 in ECHCF was relatively low in this test, but the performance in ABUTH was remarkably high considering the very low concentrations of surfactant present EXAMPLE 46 Aqueous spray compositions containing sai of glyphosate IPA or tetrabutylammonium salt and excipient ingredients as shown in Table 46a. Procedure (i) was followed for compositions 46-10 to 46-13 and 46-15, and procedure (m) for compositions 46-01 to 46-09, using soy lecithin (45% phospholipids, Avanti) The pH of all the compositions was adjusted to approximately 7 M 5 Table 46a twenty Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicide inhibition was made 14 days after application. In addition to compositions 46-01 to 46-15, spray compositions were prepared by tank mixing formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone and formulation J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 46b. Table 46b As in the previous example, compositions containing "Surf H1" did not show as strong an increase in glyphosate activity as counterpart compositions containing Fluorad FC-135.
The tetrabutylammonium salt of glyphosate (compositions 46-13 to 46-15) exhibited an extremely high herbicidal effectiveness in this test.
EXAMPLE 47 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 47a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti), except that several orders of addition were attempted as indicated below. The pH of all the compositions was approximately 5.
Table 47a (*) Order of addition MON / PG means MON 0818 Agrimul PG-2069 Alcotan plants (Abutilon theophrasti, ABUTH), and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of Spray compositions were made 15 days after planting ABUTH and 18 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application. Formulations C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 47b. Table 47b No large or consistent differences in herbicide effectiveness were observed with different orders of ingredient addition EXAMPLE 48 Concentrated aqueous compositions containing IPA salt of glyphosate and excipient ingredients as shown in Table 48a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% Avanti phospholipids) The order of addition of the ingredients was washed as indicated below. The pH of all the compositions was approximately 5 Table 48a (*) Order of addition: Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of ECHCF planting compositions, and evaluation of herbicide inhibition were made 15 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 48b.
Table 48b No large or consistent differences in herbicide effectiveness were observed with different orders of addition of ingredients EXAMPLE 49 Concentrated aqueous compositions containing IPA salt of glyphosate and excipient ingredients as shown in Table 49a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti) pH of all the compositions was approximately 5 Table 49a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echmochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. sprinkling were done 22 days after planting ABUTH and 23 days after planting ECHCF, and evaluation of herbicide inhibition was made 17 days after application. Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 49b.
Table 49b These test compositions prepared with Fluorad FC-754 tended to provide greater herbicidal effectiveness in ECHCF than their counterparts prepared with Fluorad FC-135.
EXAMPLE 50 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 50a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti). The pH of all the compositions was approximately 5.
Picture 50a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicide inhibition was made 15 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 50b.
Table 50b Concentrated compositions having a high (20-30% ae) glyphosate load and consequently a relatively low load of excipients, showed an increase in herbicidal effectiveness over that obtained with formulation B, but in this test they did not provide a efficiency equal to that of formulations C and J commercial standards.
EXAMPLE 51 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 51a were prepared. Procedure (i) for compositions 51-13 to 51-20, and process (v) for compositions 51-01 to 51-12 were followed using soy lecithin (45% phospholipids, Avanti). The compositions were stored in different conditions as indicated below before testing to verify their herbicidal effectiveness. The pH of all the compositions was approximately 5.
Table 51a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galii, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 18 days after planting ECHCF, and evaluation of herbicide inhibition was made 18 days after application. Formulations B were applied as comparative treatments. The results, prompted for all replicates of each treatment, are shown in Table 51b.
Table 51b A broad or consistent effect of the storage conditions on the herbicidal effectiveness of the compositions was not observed in this test.
EXAMPLE 52 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 52a were prepared. The procedure (v) was followed for all compositions, using soy lecithin (45% phospholipids, Avanti). The pH of all the compositions was approximately 5.
Table 52a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulation J was applied as a comparative treatment. The results, averaged for all replicates of each treatment, are shown in Table 52b.
Table 52b , A very high herbicidal effectiveness was obtained in this test with the concentrated compositions containing lecithin and Fluorad FC-754. Composition 52-14, which contained each of these excipients at the very low weight / weight ratio to ae, of glyphosate of 1: 10, was at least as effective as the commercial standard formulation J, while the compositions 52- 15 and 52-16 were even more effective. They also performed very well in this Test, particularly in ECHCF, a number of concentrated compositions containing lecithin and butyl stearate.
EXAMPLE 53 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 53a were prepared. The procedure (v) was followed for all compositions using soy lecithin (45% phospholipids, Avanti). The order of addition of the ingredients was varied for certain compositions as indicated below. The pH of all the compositions was approximately 5.
Table 53a (*) Order of addition: Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 21 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 53b.
Table 53b fifteen twenty Most of the concentrated compositions of this example showed an effectiveness of glycemic enhanced compared to formulation B, but did not match the efficacy of the commercial standard formulation J in this test.
EXAMPLE 54 Concentrated aqueous and spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 54a. Process (i) was followed for spray compositions 54-37 to 54-60, and procedure (iii) for spray compositions 54-01 to 54-36 using soy lecithin (45% phospholipids, Avanti) . The process (v) for the concentrated compositions 54-61 to 54-63 was followed using soy lecithin (45% phospholipids, Avanti). The pH of all the compositions was about 5, Table 54a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicide inhibition was made 16 days after application. Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 54b.
Table 54b In this test a surprising herbicidal effectiveness was obtained, even in comparison with the formulation J, from the compositions containing lecithin and Fluorad FC-754 (54-01 to 54-04), the replacement of Fluorad FC-754 with other fluorine-organic surfactants gave variable results.
Fluorad FC-750 (compositions 54-05 to 54-08) was an acceptable substitute; without However, Fluorad FC-751, Fluorad FC-760, Fluorad FC-120, Fluorad FC-171, Fluorad FC-129 and Fluorad FC-170C (compositions 54-09 to 54-32) provided less increase. A similar pattern was observed with the spray compositions (54-33 to 54-60) containing the same organic fluorine surfactants, with the exception of Fluorad FC-751, but without lecithin. It is worth mentioning that of all the fluorine-organic surfactants included in this test, only Fluorad FC-754 and Fluorad FC-750 are cationic. An excellent herbicidal effectiveness was also noted in this test from concentrated glyphosate compositions containing lecithin and Fluorad FC-10 754, especially composition 54-63.
EXAMPLE 55 Concentrated aqueous compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 55a. The concentrated compositions 55-01 to 55-07, 55-17 and 55-18 were prepared by process (v). The concentrated compositions 55-08 to 55-15 were prepared by the procedure (x). The other concentrated compositions of this example were included for comparison purposes.
Table 55a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echmochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of 1 15 sprays were made 17 days after planting ABUTH and ECHCF, and the evaluation of herbicide inhibition was made 18 days after application Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 55b Table 55b - = @ 15 Concentrated compositions 55-01 to 55-07 containing lecithin and Fluorad FC-754 exhibited a surprisingly effective herbicidal effectiveness. At ABUTH, several of these were almost as effective at 100 g a.e./ha as the commercial standard formulation J at 200 g a.e./ha. In ECHCF, all exhibited a strong increase over formulation B, but most did not match formulation J in this species. The performance of composition 55-07, which contained lecithin and Fluorad FC-754, each at the extremely high weight / weight ratio of a.e. was remarkably high. of glyphosate of approximately 1: 30. The inclusion of a relatively high concentration of Ethomeen T / 25, as in the compositions 55-02 and 55-03, was not helpful for herbicidal effectiveness in the presence of lecithin and Fluorad FC-754, and may even have been harmful The relatively poor performance of composition 55-18 which had a high concentration of Ethomeen T / 25 but in this case no Fluorad FC-754, is consistent with this observation. Without being limited by theory, it is believed that the presence of such high concentrations of Ethomeen T / 25 together with lecithin results in the formation of mixed micelles instead of liposomes in the aqueous dispersion. The composition 55-16 containing Fluorad FC-754 at a weight to weight ratio a.e. of glyphosate of approximately 1:10, but no lecithin, exhibited a herbicidal effectiveness similar to that of composition 55-01, suggesting that under the conditions of this test a large part of the increase due to the combination of lecithin / Fluorad FC-754 was attributable to the Fluorad FC-754 component.
Compositions 55-08 to 55-15, which contained lecithin, butyl stearate, Ethomen T / 25 and an alkyl ether surfactant of Ciß-iß (ceteareth-20 or ceteareth-27) exhibited a very high degree of herbicidal effectiveness . Not only was the yield, at least 55-08 to 55-13, in ABUTH 5 substantially better than that of the J formulation, but also these compositions performed considerably better than formulation J in ECHCF.
EXAMPLE 56 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 56a were prepared. Process (i) was followed for compositions 56-61 to 56-64, 56-67, 56-69 and 56-71, and procedure (iii) for compositions 56-01 to 56-15 15, 56- 66, 56-68, 56-70 and 56-72 using soy lecithin (45% phospholipids, Avanti). The ph of the compositions was approximately 5.
Table 56a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulation J was applied as a comparative treatment. The results, averaged for all replicates of each treatment, are shown in Table 56b.
Table 5b All the compositions in this example that contained Fluorad FC-754 showed a much higher herbicidal effectiveness in ABUTH at 187 g ae / ha than formulation J at the same amount, in many cases giving an inhibition of ABUTH equal to or greater than that provided by formulation J at 300 g ae / ha . The only compositions in the example that did not show a strong improvement over formulation J in ABUTH were 56-61 to 56-64, 56-68, 56-70 and 56-72. These are the only formulations in the example that do not contain Fluorad FC-754.
EXAMPLE 57 Aqueous spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 57a were prepared. The procedure (i) was followed for compositions 57-02, 57-04, 57-06, 57-08, 57-10, 57-12, 57-14 and 57-16 to 57-18, and the procedure ( Ii) for compositions 57-01, 57-03, 57-05, 57-07, 57-09, 57-11 and 57-13 using soy lecithin (45% phospholipids, Avanti). The ph of all the compositions was approximately 5. Table 57a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochioa crus-gaiii, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 57b.
Table 57b In this test the herbicidal activity was very high with the compositions 57-13 to 57-18, based on alkylamine-based surfactants known in the art. Compositions 57-01 to 57-12 of the present invention also exhibited excellent herbicidal effectiveness. Of all, surfactants "Surf H1" to "Surf H5 ° having hydrocarbon hydrophobes were not as effective as Fluorad FC-754 having a fluorocarbon hydrophobe, either when used as the sole excipient substance or together with lecithin .
EXAMPLE 58 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 58a were prepared. These compositions are multiple emulsions of water in oil in water and were prepared by the process (vi) described above.
Table 58a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 35 days after planting ABUTH and 33 days after planting ECHCF, and evaluation of herbicide inhibition was made 17 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 58b.
Table 58b There was considerable variation in the herbicidal effectiveness of the multiple water-in-oil-in-water emulsions of this example, especially in ECHCF. Among the most effective were 58-08, 58-10, 58-12, 58-14 and 58-16. All of these contained Ci6-? B alkyl ether surfactant, ceteareth-55. When Tergitol 15-S-30, a surfactant of C? 2-fs secondary alkyl ether, replaced ceteareth-55, as in 58-09, 58-11, 58-13, 58-15 and 58-17, the herbicidal effectiveness, at least in ECHCF was in many markedly reduced cases.
EXAMPLE 59 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 59a were prepared. Concentrated compositions 59-01 and 59-02 are multiple emulsions of water in oil in water and were prepared by the procedure (vi), using Span 80 as the emulsifier # 1. The concentrated compositions 59-03 to 59-12 and 59-14 to 59-17 are oil-in-water emulsions and were prepared by the process (vii). Concentrated composition 59-13 is a concentrate in aqueous solution and was prepared by process (viii), the component indicated below as "emuslificapte # 2" being the surfactant component.
Table 59a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicide inhibition was made 18 days after application. Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 59b.
Table 59b A very high herbicidal effectiveness was evident in compositions 59-13 to 59-17, which have a very high ratio of surfactant to a.e. of glyphosate of 1: 1. The activity was too high to clearly distinguish between these compositions, but 59-16 and 59-17, which contained steareth-20 and oleth-20 respectively, exhibited greater effectiveness in ABUTH at the lower glyphosate amount than 59-14. and 59-15, which contained Neodol 25-20 and Neodol 25-12 respectively.
EXAMPLE 60 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 60a Concentrated compositions 60-01 and 60-02 are multiple emulsions of water in oil in water and were prepared by procedure (vi), using Span 80 as emulsifier # 1 Concentrated compositions 60-03 to 60- 12 and 60-14 to 60-17 are oil-in-water emulsions and were prepared by the procedure (vn) The concentrated composition 60-13 is a concentrate in aqueous solution and was prepared by the procedure (vin), the component indicated below as' emusiificante # 2"being the surfactant component Table 60a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-gailt, ECHCF) were grown and treated by standard procedures given arpba. sprinkling were done 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicide inhibition was made 18 days after application Formulations B, C and J were applied as comparative treatments The results, averaged for all the replicas of each treatment are shown in Table 60b Table 60b Compositions 60-16 and 60-17, which contain steareth-20 and oleth-20 respectively, exhibited a very high herbicidal activity in ABUTH. Very high ratio of surfactant to a.e. of glyphosate (1: 1) of these compositions, no difference was evident between these compositions and another similarly similar composition (60-15) containing Neodol 25-20 instead of steareth-20 or oleth-20.
EXAMPLE 61 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 61a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii).
Table 61 a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 19 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 61 b.
Table 61b At a weight / weight ratio of surfactant to a.e. of glyphosate of approximately 1: 1.5, the compositions containing steareth-20 or oleth-20 (61-04 and 61-05 respectively) exhibited herbicidal effectiveness in ABUTH similar to that containing Neodol 25-20 (61-03).
EXAMPLE 62 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 62a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii). Table 62a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese mijo (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 21 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 62b.
Table 62b In this test, the total herbicidal effectiveness was lower than in the previous example, particularly in ABUTH. In these circumstances, at a ^ weight / weight ratio of surfactant to a.e. of glyphosate of about 1: 1.5, the compositions containing steareth-20 or oleth-20 (62-04 and 62-05 respectively) exhibited greater herbicidal effectiveness in both ABUTH and ECHCF than that in Neodol 25-20 (62-03).
EXAMPLE 63 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 63a were prepared. Concentrated composition 63-01 is a water-in-oil-in-water multiple emulsion and was prepared by procedure (vi), using Span 80 as the # 1 emulsifier. The concentrated compositions 63-02 and 63-) 15 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 63-12 to 63-16 are concentrated in aqueous solution and were prepared by the process (viii), the component indicated below as "emulsifier # 2 ° being the surfactant component.
Table 63a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 63b.
Table 63b Compositions containing steareth-20 or oleth-20 (63-05, 63-06, 63-10, 63-11, 63-15, 63-16) generally exhibited a herbicidal effectiveness above their counterparts containing Neodol 25- 20 (63-04, 63-09, 63-14), at least in ABUTH. The presence of a small amount of butyl stearate tended to increase effectiveness in ABUTH (compare 63-05 and 63-06 with 63-15 and 63-16).
EXAMPLE 64 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 64a were prepared. Concentrated composition 64-01 is a multiple emulsion of water in oil in water and was prepared by method (vi), using Span 80 as emulsifier # 1. The concentrated compositions 64-02 to 64-08, 64-14, 64-16 and 64-17 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 64-13 and 64-15 are concentrated in aqueous solution and were prepared by the process (viii), the component indicated below as "emulsifier # 2" being the surfactant component.
Table 64a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 64b.
Table 64b The highest herbicidal effectiveness in this test was exhibited by the compositions containing an alkyl ether surfactant of C-iß-iß (oleth-20, ceteareth-27 or ceteareth-55).
EXAMPLE 65 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 65a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii). Table 65a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 23 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 65b.
Table 65b The overall activity in this test was very high, and the differences between the compositions in herbicidal effectiveness are difficult to discern clearly. EXAMPLE 66 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 66a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii). The pH of all the compositions was approximately 5. Table 66a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 66b.
Table 66b Composition 66-04 containing 1% butyl stearate and 10% oleth-20 (weight / weight ratio of surfactant to glyphosate ae of about 1: 1.5) exhibited a herbicidal effectiveness marginally greater than the composition 66-03 containing 1% butyl stearate and 10% Neodol 25-20. However, at this very high level of glyposate-active agent, both performed extremely well. Surprisingly, when the concentrations of butyl stearate and oleth-20 were significantly decreased, this high level of yield was maintained to a remarkable degree. Even when the butyl stearate was reduced to 0.25% and the oleth-20 to 2.5% (surfactant ratio to glyphosate ae of approximately 1: 6), as in composition 66-06, the herbicidal effectiveness was still similar to that obtained with formulations C and J commercial standards.
EXAMPLE 67 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 67a were prepared. The concentrated compositions 67-01 to 67-08 and 67-11 to 67-16 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 67-09 and 67-10 are concentrated in aqueous solution and were prepared by the process (viii). The pH of all the compositions was approximately 5.
Table 67a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of Sprays were made 12 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 67b.
Table 67b An extremely high herbicidal effectiveness was again observed with a composition (67-15) containing 15% a.e. of glyphosate and only 2.5% of oleth-20 together with 0.25% of butyl stearate. A comparison of the compositions of 1% a.e. of glyphosate containing 5% alkyl ether surfactant and 0.25% butyl stearate provided the following classification of alkyl ethers in descending order of effectiveness; oleth-20 (67-14) > ceteth-20 (67-05) > Neodol 25-20 (67-03) = laureth-23 (67-04).
EXAMPLE 68 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 68a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii).
Table 68a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 68b.
Table 68b All compositions containing butyl stearate and oleth-20 or steareth-20 showed a very high level of performance compared to formulations C and J commercial standards.
EXAMPLE 69 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 69a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii).
Table 69a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 69b.
Table 69b All compositions containing butyl stearate and oleth-20 or steareth-20 showed a very high level of performance compared to formulations C and J commercial standards.
EXAMPLE 70 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 70a were prepared. All contain materials in colloidal particles and were prepared by the procedure (ix). All the compositions of this example showed stability under acceptable storage. The compositions containing oleth-20 were not acceptable in storage stability in the absence of the colloidal particulate material. Table 70a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 70b.
Table 70b Significantly high herbicide effectiveness benefits were obtained in this test with the compositions containing oleth-20 at a weight / weight ratio at a.e. of glyphosate of about 1: 14, and stabilized with materials in colloidal particles. In some cases the material in Colloidal particles alone contributed a large part of the increase in effectiveness. The results with composition 70-90 are out of line with other data and an application problem is suspected.
EXAMPLE 71 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 71a were prepared. The concentrated compositions 71-01 to 71-04, 71-06, 71-08, 71-09, 71-11, 71-12, 71-14 and 71-16 are oil-in-water emulsions and were prepared by the process (vii) The concentrated compositions 71-05, 71-07, 71-10, 71-13, 71-15 and 71-17 are concentrated in aqueous solution and were prepared by the process (viii). Table 71a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 71b.
Table 71b In combination with butyl stearate, steareth-20 (composition 71-04) gave a greater herbicidal effectiveness than steareth-10 (71-03) in ABUTH. Similarly, oleth-20 (71-09) was more effective than oleth-10 (71-08) and ceteth-20 (71-12) than ceteth-10 (71-11). In the absence of butyl stearate, ceteareth-55 (71-17) was markedly weaker in ECHCF than ceteareth-27 (71-15) but the inclusion of butyl stearate (71-16) tended to correct this weakness. Note that although compositions 71-14 and 71-15 contained a double the concentration of excipients than the other test compositions, the glyphosate concentration was also twice as high, and thus the concentrations sprayed were the same .
EXAMPLE 72 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 72a were prepared. The concentrated compositions 72-01 to 72-05, 72-07, 72-08, 72-10 and 72-12 to 72-16 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 72-06, 72-09 and 72-11 are concentrated in aqueous solution and were prepared by the process (viii).
Frame 72a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 72b.
Table 72b Composition 72-04 containing steareth-20 exceeded in performance its counterpart 72-03 containing steareth-10, although both gave greater herbicide effectiveness, especially in ECHCF, than 72-02 contained laureth-23 or 72-01 that contained Neodol 1-12.
EXAMPLE 73 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 73a were prepared. The concentrated compositions 73-01 to 73-07 and 73-09 to 73-15 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 73-08 and 73-16 are concentrated in aqueous solution and were prepared by the process (viii).
Table 73a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 19 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 73b.
Table 73b Composition 73-08, which contained oleth-20 as the sole excipient substance at a weight / weight ratio a.e. of glyphosate, exhibited high herbicidal effectiveness, at least equal to those of the formulations C and J commercial standards in ABUTH, but a little weaker in ECHCF. In comparison, composition 73-16, in which the only excipient substance was Neodol 1-9 at the same ratio to glyphosate, had a much weaker activity. The addition of a small amount of fatty acid ester increased the effectiveness in many cases, especially in ECHCF. In this study, the most effective composition was 73-01, which contained oleth-20 and methyl stearate. When added to Neodol 1-9, butyl stearate was more effective than methyl stearate, methyl oleate or butyl oleate. The Orchex 796 mineral oil did not effectively replace butyl state, neither with oleth-20 nor with Neodol 1-9.
EXAMPLE 74 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 74a were prepared. The concentrated compositions 74-01, 74-03, 74-05 to 74-08, 74-10 and 74-14 to 74-17 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 74-02, 74-04, 74-09 and 74-11 to 74-13 are concentrated in aqueous solution and were prepared by the process (viii). Some composicones contained a coupling agent as indicated in Table 74a; the coupling agent was added with the surfactant.
Table 74a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 74b.
Table 74b The superiority of the herbicidal effectiveness provided by the alkyl ethers (oleth-20, ceteareth-27, steareth-20) over that provided by the shorter chain alkyl ethers (Neodol 1-9, laureth-23) was very pronounced in this proof.
EXAMPLE 75 Concentrated aqueous compositions were prepared containing glyphosa ICP salt and excipient ingredients as shown in Table 75a. The concentrated compositions 75-01 to 75-07 and 75-09 to 75-15 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 75-08 and 75-16 are concentrated in aqueous solution and were prepared by the procedure (v? ¡) Table 75a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galll, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 75b.
Table 75b Steareth-20 and ceteareth-27, as the only excipient substances (compositions 75-08 and 75-16 respectively) provided excellent herbicidal effectiveness, but additional increases, especially in ECHCF, were obtained by including a small amount of acid ester fatty in the composition.
EXAMPLE 76 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in 1 5 table 76a. The concentrated compositions 76-13 and 76-14 are concentrated in aqueous solution and were prepared by the process (viii). The concentrated compositions 76-01 to 76-12 and 76-15 are concentrated in aqueous solution containing colloidal particle materials and were prepared by the procedure (ix). Concentrated compositions 76-10 16 and 76-17 contained colloidal particulate materials but no surfactant. Compositions 76-13 and 76-14 (both containing 162 g a.e./l glyphosate) showed stability under acceptable storage. However, at glyphosate loads > 480 g a.e./l (as compositions 76-01 a [15 76-12 and 76-15) stable compositions under storage containing 3% oleth-20 could not be made, except with the addition of colloidal particulate material as shown below.
Table 76a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 76b.
Table 7b Several highly charged glyphosate compositions (492 g ae / l) containing oleth-20 at only 3% exhibited a highly high herbicidal effectiveness, reaching or matching that of the commercial standard formulation J, which is charged at only about 360 g ae / He has a much higher ratio of tepsioactive agent to glyphosate.
EXAMPLE 77 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 77a were prepared. The concentrated compositions 77-08 to 77-14 oil-in-water emulsions were prepared by the process (vii). The concentrated compositions 77-15 to 77-17 are concentrated in aqueous solution and were prepared by the procedure (viii). The concentrated compositions 77-01 to 77-07 contain colloidal particle materials and were prepared by the method (ix). Compositions 77-08 to 77-17 (all containing 163 g a.e./l glyphosate) showed stability under acceptable storage. However, at a glyphosate loading 400 g ae / l (as compositions 77-01 to 77-07) the compositions stable under storage containing 0.5-1% butyl stearate and 5-10% ether surfactant Alkyl could not be made, except with the addition of colloidal particle material as shown below.
Table 77a Alcotán plants (Abutilón theophrasti, ABUTH) were cultivated and The Japanese miracle (Echinochloa crus-galli, ECHCF) was treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 19 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 77b.
Table 77b A surprising herbicidal effectiveness was provided by the compositions containing C ß-? Β alkyl ether surfactants (ceteareth-27, steareth-20, steareth-30, oleth-20, ceteth-20). Highly charged giifosate compositions (400 g ae / l) containing an alkyl ether surfactant of C-iß-iß, butyl stearate and a colloidal particulate material (Aerosil 90) to stabilize the compositions performed impressively in this test.
EXAMPLE 78 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 78a were prepared. Concentrated compositions 78-01 to 78-09, 78-14, 78-16 and 78-17 are oil-in-water emulsions and were prepared by process (vii). Concentrated compositions 78-10 and 78-15 are concentrated in aqueous solution and prepared by the procedure (vili).
Table 78a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 20 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 78b.
Table 78b A broad or consistent increase in the herbicidal effectiveness of the glyphosate compositions containing oleth-20 was not obtained by adding a small amount of any of a variety of fatty acid esters in this study (compare 78-10 with 78-01 to 78 -09).
EXAMPLE 79 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 79a were prepared. The concentrated compositions 79-01 to 79-09, 79-11 to 79-14, 79-16 and 79-17 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 79-10 and 79-15 are concentrated in aqueous solution and were prepared by the procedure (viii) Table 79a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 79b.
Table 79b In this study, isopropyl myristate (composition 79-01) was the most effective of the fatty acid esters tested as additives for oleth-20 (79-10) in the glyphosate compositions.
EXAMPLE 80 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 80a were prepared. The concentrated compositions 80-01 to 80-13 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 80-14 and 80-17 are concentrated in aqueous solution and were prepared by the process (viii).
Table 80a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 24 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 80b.
Table 80b Herbicidal effectiveness exceeding that of the commercial standard J composition, at least at ABUTH, was recorded with several compositions, including 80-02 (steareth-20 plus butyl stearate), 80-03 (ceteareth-20 plus butyl stearate ), 80-04 (ceteareth-15 plus butyl stearate), 80-10 (steareth-20 plus methyl palmitate), 80-11 (ceteareth-20 plus methyl palmitate) and 80-12 (ceteareth-15 plus palmltate) of methyl). The compositions that lacked fatty acid ester acted slightly less better in everything than those containing butyl stearate or methyl palmitate. EXAMPLE 81 Spray compositions containing sodium glyphosate or IPA salts and excipient ingredients as shown in Table 81a were prepared. The compositions were prepared by simply mixing the ingredients. Soy lecithin (45% phospholipid, Avanti) was first prepared, when included, with sonification in water to make an aqueous composition. Four different concentrations of glyphosate were prepared (not shown in Table 81a), calculated to provide, when applied in a spray volume of 93 l / ha, the amounts of glyphosate shown in Table 81b.
Table 81a Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 14 days after planting ECHCF and 21 days after planting SIOSP. The evaluation of the herbicide inhibition was made 14 days after the application. Formulations B and C were applied as comparative treatments, representing IPA salt of glyphosate technique and a commercial salt formulation of commercial IPA, respectively. The results, averaged for all replicates of each treatment, are shown in Table 81b. Table 81b The results of this test using glyphosate as the exogenous chemical are summarized as follows. At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (81-03) was a much more effective excipient than the lecithin-based adjuvant LI-700 (81-06) widely used in the technique. Butyl stearate alone at 0.05% (81-05) did not increase the effectiveness too much. The combination of lecithin and butyl stearate (81-02) gave a surprisingly strong increase in effectiveness, suggesting a synergistic interaction between these two excipient substances. Fluorad FC-754, either alone (81-04) or in combination with lecithin (81-01) gave an extremely high effectiveness, superior to that obtained with the commercial standard formulation. ? leth-20 at the low concentration of 0.05% (81-09) gave an extremely high effectiveness, higher than that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (81-07) or 0.01% methyl oleate (81-08) did not provide an additional increase.
EXAMPLE 82 Spray compositions containing paraquat dihydrochloride and excipient ingredients were prepared. The compositions 82-01 a 82-12 were exactly the same as compositions 81-01 to 81-12, except that a different active ingredient was used and a scale of concentrations of active ingredient was selected that was suitable for the active ingredient applied. Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. The evaluation of the herbicide inhibition was made 12 days after the application. Standard formulations included technical paraquat dihydrochloride and Gramoxone, a commercial paraquat formulation from Zeneca. The results, averaged for all replicates of each treatment, are shown in Table 82.
Table 82 Results of this test using paraquat as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (82-03) was a much more effective excipient on SIDSP than the lecithin-based adjuvant LI-700 (82-06) widely used in the art. Butyl stearate alone at 0.05% (82-05) did not increase the effectiveness too much. The combination of lectalin and butyl stearate (82-02) gave a surprisingly strong increase in effectiveness, suggesting a synergistic interaction between these two excipient substances. Fluorad FC-754 (82-04) gave an extremely high effectiveness, superior to that obtained with the commercial standard formulation. In the presence of lecithin (82-01), the effectiveness was additionally increased in dramatic, suggesting a synergistic interaction between these two excipient substances. ? leth-20 at the low concentration of 0.05% (82-09) gave an extremely high effectiveness, exceeding that obtained with the normal commercial formulation The addition of 0.005% butyl stearate (82-07) or 0.01% oleate of methyl (82-08) did not provide an additional increase.
EXAMPLE 83 Spray compositions containing acifluorfen sodium salt and excipient ingredients were prepared. Compositions 83-01 to 83-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient applied was selected. . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 15 days after planting ABUTH, 9 days after planting ECHCF and 22 days after planting SIDSP. The evaluation of the herbicide inhibition was made 10 days after the application.
Standard formulations included technical sodium acifluorfen and Blazer, a commercial formulation of acifluorfen from Rohm & Haas. The results, averaged for all replicates of each treatment, are shown in Table 83. Table 83 Results of this test using acifluorfen as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (83-03) gave effectiveness similar to that obtained with the lecithin-based adjuvant LI-700 (83-06) widely used in the art. Butyl stearate at 0.05% alone (83-05) and in combination with lecithin (83-02) increased effectiveness, particularly in ECHCF Fluorad FC-754, either alone (83-04) or in combination with lecithin (83 -01) gave greater effectiveness in ABUTH and SIDSP than that obtained with the commercial standard formulation.
Oleth-20 at the low concentration of 0.05% (83-09) gave an efficiency superior to that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (83-07) or 0.01% methyl oleate (83-08) did not provide an additional increase.
EXAMPLE 84 Spray compositions containing asulam and excipient ingredients were prepared. Compositions 84-01 to 84-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient applied was selected. . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given both. Applications of spray compositions were made 15 days after planting ABUTH, 11 days after planting ECHCF and 21 days after planting SIDSP. The evaluation of the herbicide inhibition was made 14 days after the application. Standard formulations included technical asulam and Asulox, a commercial formulation of Rhulae-Poulenc asulam. The results, averaged for all replicates of each treatment, are shown in Table 84.
Table 84 The results of this test using asulam as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (84-03) gave an effectiveness similar to that obtained with the lecithin-based adjuvant LI-700 (84-06) widely used in the art. Butyl stearate at 0.05% (84-05) increased effectiveness, particularly in ECHCF. The combination of lecithin and butyl stearate (84-02) gave a greater increase in effectiveness than the excipient substance alone. Fiuorad FC-754, either alone (84-04) or in combination with lecithin (84-01) gave an effectiveness equal to that obtained with the commercial standard formulation.
Oleth-20 at the low concentration of 0.05% (84-09) gave, at low amounts of exogenous chemical, an effectiveness in ECHCF higher than that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (84-07) ) or 0.01% methyl oleate (84-08) did not provide an additional increase.
EXAMPLE 85 Spray compositions containing dicamba sodium salt and excipient ingredients were prepared. Compositions 85-01 to 85-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient applied was selected. . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) and were treated by the normal procedures given both. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. The evaluation of the herbicide inhibition was made 17 days after the application. Standard formulations included technical sodium dicamba and Banvel, a commercial formulation of Sandoz dicamba. The results, averaged for all replicates of each treatment, are shown in Table 85. Table 85 The results of this test using dicamba as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (85-03) gave an effectiveness similar to that obtained with the adjuvant based on lecithin LI-700 (85-06) widely used in the art. Butyl stearate alone at 0.05% (85-05) provided a slight increase in effectiveness. The combination of lecithin and butyl stearate (85-02) gave a greater increase in SIDSP effectiveness than either of these two excipient substances alone.
Fluorad FC-754 (85-04) provided an effectiveness similar to that obtained with the commercial standard formulation. A further increase in SIDSP was obtained with the combination of Fluorad FC-754 and lecithin (85-01) OIeth-20 at the low concentration of 0.05% (85-09) gave an effectiveness in SIDSP superior to that obtained with the commercial formulation normal. The addition of 0.005% butyl stearate (85-07) or 0.01% methyl oleate (85-08) did not provide a significant additional increase.
EXAMPLE 86 Spray compositions containing metsulfuropomethyl and excipient ingredients were prepared. Compositions 86-01 to 86-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient applied was selected. . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. The evaluation of the herbicide inhibition was made 14 days after the application.
Standard formulations included technical metsulfuron-methyl and Ally, a commercial formulation of Du Pont's metsulfuron. The results, averaged for all replicates of each treatment, are shown in Table 86.
Table 86 The results of this test using metsulfuron as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (86-03) was a slightly more effective excipient than the adjuvant based on lecithin LI-700 (86-06) widely used in the art to improve the yield in ABUTH at the lowest exogenous chemical amount tested.
Butyl stearate alone at 0.05% (86-05) increased the effectiveness to a level higher than that obtained with the commercial standard formulation. The combination of lecithin and butyl stearate (86-02) gave a greater increase in effectiveness than that obtained with each of these two excipient substances alone. Fluorad FC-754 either alone (86-04) or in combination with lecithin (86-01), gave high effectiveness, higher than that obtained with the commercial standard formulation,? Leth-20 at the low concentration of 0.05% (86 -09) gave a high effectiveness, superior to that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (86-07) or 0.01% methyl oleate (86-08) did not provide an additional increase.
EXAMPLE 87 Spray compositions containing imazethapyr and excipient ingredients were prepared. Compositions 87-01 to 87-12 were exactly equal to compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of active ingredient concentrations that was suitable for the active ingredient was selected. applied. Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, S1DSP) and were treated by the normal procedures given both. Applications of spray compositions were made 14 days after planting ABUTH, 14 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicide inhibition was made 14 days after application. Standard formulations included mazetapir technical and Pursuit, a commercial formulation of imazethapyr from American Cyanamid. The results, averaged for all replicates of each treatment, are shown in Table 87.
Table 87 The results of this test using imazetapir as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (87-03) was a less effective excipient than the LI-700 lecithin adjuvant (87-06). Butyl stearate alone at 0.05% (87-05) significantly increased the effectiveness in ECHCF and slightly in SIDSP. The combination of lecithin and butyl stearate (87-02) gave an increase in ECHCF effectiveness greater than that obtained with each of these two excipient substances alone. Fluorad FC-754 (87-04) gave an ECHCF effectiveness higher than that obtained with the commercial standard formulation. The combination of Fluorad FC-754 and lecitin (87-01), provided a slightly additional increase in SIDSP effectiveness. Oleth-20 at the low concentration of 0 05% (87-09) gave an extremely high effectiveness, much higher than that obtained with the normal commercial formulation, especially in ECHCF. The addition of 0.005% butyl stearate (87-07) further increased the yield of low amounts of exogenous chemical in ABUTH, more effectively than the addition of 0.01% methyl oleate (87-08).
EXAMPLE 88 Spray compositions containing fluazifop-p-butyl salt and excipient ingredients were prepared. Compositions 88-01 to 88-12 were exactly equal to compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient was selected. applied. Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and broadleaved grass (Brachiaria platyphylla, BRAPP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 15 days after planting ABUTH, 15 days after planting ECHCF and 16 days after planting BRAPP. Evaluation of herbicide inhibition was made 10 days after application. Standard formulations included technical fluazifop-p-butyl and Fusilade 5, a commercial formulation of fluazifop-p-butyl from Zeneca. The results, averaged for all replicates of each treatment, are shown in Table 88.
Table 88 The results of this test using fluazifop-p-butyl as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, the soybean lecithin containing 45% phospholipids (88-03) was a less excipient effective in ECHCF than the lecithin-based adjuvant Ll-700 (88-06). Butyl stearate alone at 0.05% (88-05) and in combination with lecithin (88-02) increased effectiveness, especially in ECHCF. Fluorad FC-754, either alone (88-04) or in combination with lecithin 15 (88-01) gave an effectiveness equal to or superior to that obtained with the commercial standard formulation. ? Ith-20 at the low concentration of 0.05% (88-09) gave an extremely high ECHCF effectiveness, much higher than that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (88-20%) or 0.01% methyl oleate (88-08) did not provide a significant additional increase.
EXAMPLE 89 Spray compositions were prepared containing alachlor and Ingredients excipients. Compositions 89-01 to 89-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient that was suitable for the active ingredient applied was selected. . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 14 days after planting SIDSP. The evaluation of herbicide inhibition was made 9 days after application. Standard formulations included technical alachlor and Lasso, a commercial formulation of alachlor from the Monsanto Company. The results, averaged for all replicates of each treatment, are shown in Table 89.
Table 89 None of the tested compositions increased the post-emergence herbicidal effectiveness applied to the alachlor foliage in this test. The aladro is not known as a foliar applied herbicide.
EXAMPLE 90 Spray compositions containing glufosinate ammonium salt and excipient ingredients were prepared. Compositions 90-01 to 90-12 were exactly the same as compositions 81-01 to 81-12 respectively, except that a different active ingredient was used and a scale of concentrations of active ingredient was selected that was suitable for the active ingredient applied . Alcotan plants (Abutilon theophrasti, ABUTH), Japanese millet (Echinochloa crus-galli, ECHCF) and spiny dibetu (Sida spinosa, SIDSP) were grown and treated by the normal procedures given above. The Applications of spray compositions were made 14 days after planting ABUTH, 10 days after planting ECHCF and 17 days after planting SIDSP. The evaluation of the herbicide inhibition was made 11 days after the application. Standard formulations included glufosinate ammonium salt technique and Liberty, a commercial formulation of glufosinate from AgrEvo. The results, averaged for all replicates of each treatment, are shown in Table 90. Table 90 The results of this test using glufosinate as the exogenous chemical are summarized as follows: At the low concentration of 0.05% used here, soy lecithin containing 45% phospholipids (90-03) was a more effective excipient than the adjuvant Lecithin base LI-700 (90-06) widely used in the art. Butyl stearate alone at 0.05% (90-05) increased the effectiveness of ECHCF.
The combination of lecithin and butyl stearate (90-02) gave a greater increase in effectiveness than each of these two excipient substances alone. Fluorad FC-754, either alone (90-04) or in combination with lecithin (90-01) gave a remarkably high effectiveness, similar to that obtained with the commercial standard formulation. ? leth-20 at the low concentration of 0.05% (90-09) gave an extremely high effectiveness, superior in SIDSP to that obtained with the normal commercial formulation. The addition of 0.005% butyl stearate (90-07) or 0.01% methyl oleate (90-08) did not provide an additional increase.
EXAMPLE 91 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 91a were prepared. The concentrated compositions 91-01 to 91-12 are concentrated in aqueous solution containing colloidal particulate materials and prepared by the procedure (ix). Concentrated compositions 91-13 to 91-18 contain colloidal particulate materials but no surfactant. The colloidal particle materials of this example were generally too large to confer stability under adequate storage to the tested compositions.
Table 91a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 14 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 91b.
Table 91b Many of the high load formulations (488 g a.e./l) of glyphosate of this example exhibited herbicidal effectiveness equal to or superior to that obtained with the commercial standard J formulation, although they only contained 3% alkyl ether surfactant.
EXAMPLE 92 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 92a were prepared. Concentrated compositions 92-01 to 92-12 and 92-14 to 92-16 are oil-in-water emulsions and were prepared by process (vii). The concentrated composition 92-13 is a concentrate in aqueous solution and was prepared by the process (viii).
Frame 92a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 20 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 16 days after application.
Formulations B, C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 92b.
Table 92b Extremely high herbicidal effectiveness was provided by ceteareth-27 (composition 92-13); this was further increased by the addition of a small amount of butyl stearate (92-10, 92-11) or methyl stearate (92-14). Compositions that performed better than standard C and J commercial formulations, at least on ABUTH, included those that contained steareth-30, steareth-20 or ceteareth-27; In this test, oleth-20 was not as effective as these saturated alkyl ethers.
EXAMPLE 93 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 93a were prepared. All are oil-in-water emulsions and were prepared by process (vii). First, lecithin (45% phospholipids, Avanti) was dispersed in water using sonification.
Table 93a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 23 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 93b.
Table 93b A surprising herbicidal effectiveness was provided with composition 93-18 which contained lecithin, ceteareth-27 and butyl stearate. The addition of 3% Ethomeen T / 25 (93-16) increased the effectiveness more. A slightly reduced effect was observed at the lowest amount of giifosate in ABUTH when the concentration of butyl stearate was cut in half (93-15).
EXAMPLE 94 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 94a were prepared. The concentrated compositions 94-01 to 94-04, 94-06, 94-08, 94-10 and 94-18 are oil-in-water emulsions and were prepared by the process (vii). The concentrated compositions 94-05, 94-07 and 94-09 are concentrated in aqueous solution and prepared by the procedure (vii). Concentrated compositions 94-11 to 94-17 contain colloidal particulate materials and were prepared by process (ix). All the compositions of this example showed stability under acceptable storage. The compositions shown as containing colloidal particle material were not stable under storage unless the colloidal particulate material was included as shown.
Table 94a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 22 days after planting ABUTH and ECHCF, and the evaluation of herbicide inhibition was made 18 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 94b.
Table 94b Compositions that exhibited a greater herbicidal effectiveness than that provided by the commercial standard J formulation included 94-01 (steareth-20 plus butyl stearate), 94-09 (ceteareth-15) and 94-10 (steareth-20 plus stearate-20 stearate). butyl).
EXAMPLE 95 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 95a were prepared. All are oil-in-water emulsions and were prepared by the procedure (vii). Table 95a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 95b.
Table 95b Compositions that had a weight / weight ratio of 1: 3 or less of surfactant to a.e. of glyphosate, but exceeding the commercial standard J formulation at least in ABUTH in this trial, included those containing only 1% alkyl ether surfactant (ratio of approximately 1: 15) together with 0.25% butyl stearate , wherein the alkyl ether surfactant was steareth-20 (95-12), oleth-20 (95-15) or ceteareth-27 (95-18).
EXAMPLE 96 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 96a were prepared. All are concentrated in aqueous solution containing colloidal particle materials and were prepared by the procedure (ix). The compositions of this example showed stability under acceptable storage. The compositions shown as containing colloidal particle material were not stable under storage unless the colloidal particulate material was included as shown.
Table 96a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
The formulations B and were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 96b.
Table 96b Many high load compositions (488 g a.e./l) of glyphosate exhibited herbicidal effectiveness in ABUTH equal to the commercial standard J formulation, but none was equal to formulation J in ECHCF in this test.
EXAMPLE 97 Dry granular concentrate compositions containing glyphosate ammonium salt and excipient ingredients as shown in Table 97a were prepared. The preparation procedure was as follows. Ammonium glyphosate powder was added to a mixer. The excipient ingredients were added slowly, together with enough water to moisten the powder and form a firm dough. The mixer was operated for a sufficient time to completely mix all the ingredients. The mass was then transferred to an extrusion apparatus and extruded to form granules, which were finally dried in a fluid bed dryer.
Table 97a (*) Aerosil MOX-80 + Aerosil MOX-170 (1: 1) Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application.
Formulations J and K were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 97b.
Table 97b Several dry granular compositions of this example exceeded in performance the commercial standard K composition, at least in ABUTH. These included 97-01 to 97-04 and 97-10 to 97-16, all containing alkyl ether surfactant steareth-20, oleth-20 or ceteth-20).
EXAMPLE 98 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 98a were prepared. All are oil-in-water emulsions and were prepared by The procedure (vii) Lecithin (45% phospholipids, Avanti) was first dispersed in water by ultrasonification or by using a microfluidizer as indicated in the column of Table 98a entitled "Procedure".
Table 98a (* Procedure) A Ultrasonic B Microfluidized, 3 cycles Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 19 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 98b.
Table 98b Many compositions of this test that contained lecithin and butyl stearate exceeded in performance the commercial standard J formulation in this test EXAMPLE 99 Concentrated aqueous compositions containing / IPA salt of glyphosate and excipient ingredients as shown in Table 99a were prepared. The concentrated compositions 99-04 and 99-05 are concentrated in aqueous solution and prepared by the process (vii). The concentrated compositions 99-06 to 99-13 are concentrated in aqueous solution containing colloidal particle materials and were prepared by the process (ix). Concentrated compositions 99-01 to 99-03 contained colloidal particle materials but no surfactant. The compositions of this example containing colloidal particulate material all exhibited stability under acceptable storage. Of those that contained steareth-20 but not colloidal particle material, composition 99-04 was stable under storage, but composition 99-05 was not.
Table 99a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF, and the evaluation of herbicide inhibition was made 19 days after application.
The B J formulations were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 99b.
Table 99b A remarkably strong herbicidal effectiveness was provided by composition 99-05, despite its very low ratio of surfactant (steareth-20) to a.e.de glyphosate of about 1: 13. The activity, at least in ABUTH, was further enhanced to a significant degree by the inclusion in the composition of colloidal particle materials such as Aerosil MOX-170 (99-06), Aerosil 380 (99-07), a mixture of Aerosil MOX-80 and Aerosil 380 (99-08) and a mixture of Aerosil MOX-80 and Aerosil MOX-170 (99-09).
-EJEMPL0 100 Concentrated aqueous and granular dry compositions were prepared as shown in Table 100a. The dried granulated concentrate compositions 100-01 to 100-11 contain ammonium salt of glyphosate and were prepared by the procedure described in example 97. Concentrated aqueous compositions 100-12 to 100-16 contain IPA salt of glyphosate and were prepared by process (v), using soy lecithin (45% phospholipids, Avanti).
Picture 100a Aerosil mixture: Aerosil MOX-80 + Aerosil MOX-170 (1: 1) Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of Spraying was done 20 days after planting ABUTH and ECHCF, and the evaluation of herbicide inhibition was made 16 days after application.
Formulations J and K were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 100b.
Table 100b All the compositions of the invention in this study showed greater herbicidal effectiveness in both ABUTH and ECHCF, in some cases by a very substantial margin, than the commercial standard K formulation.
EXAMPLE 101 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 101a were prepared. All contain materials in colloidal particles and were prepared by the procedure (ix). The compositions of this example all showed stability under acceptable storage. The compositions shown as containing colloidal particle material were not stable under storage unless the colloidal particulate material was included as shown. Table 101a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 19 days after application.
The formulations B and were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 101 b.
Table 101b The percent inhibition data for the glyphosate amount of 400 g a.e./ha in this test are unreliable and should be ignored. Neither oleth-20 (composition 101-05) nor steareth-20 (101-10) provided herbicidal effectiveness equal to that of formulation J in this study, and no additional large or consistent increase by adding butyl stearate.
EXAMPLE 102 Concentrated aqueous compositions were prepared containing the glyphosate IPA salt and excipient ingredients as shown in Table 102a. The concentrated compositions 102-01 to 102-03 are oil-in-water emulsions and were prepared by the process (vii). Compositions 102-04 to 102-18 contain all colloidal particle materials and were prepared by process (ix). 15 different mixing methods were used in the final stage of preparation of these compositions, as cated in the column of Table 102a entitled "Procedure". The compositions of this example all showed stability under acceptable storage. The compositions shown as containing material in colloidal particles were not stable under storage unless the colloidal particulate material was included as shown.
Table 102a (*) Process: A Sllverson Mixer, medium sieve, 3 minutes at 7000 m B Silverson mixer, coarse sieve, 3 minutes at 7000 fm C Fanp mixer, 50% emission, 5 minutes D Turrax mixer, 3 minutes at 8000 fm E Top-head agitator, low-speed F Top-head agitator, high-speed G Manual agitation, 3 minutes Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 19 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 102b.
Table 102b The results obtained with composition 102-06 are out of line with other data in this example and an error in the formulation or application is suspected. Some differences in herbicidal effectiveness were evident when a composition containing 360 g ae / l of glyphosate, 1% of butyl stearate, 10% of oleth-20 and 1.25% of Aerosil 380 was processed in different ways (102-11 to 102). -17). However, since compositions 102-07 and 102-11 were processed identically but differed in effectiveness, firm conclusions can not be drawn from this test.
EXAMPLE 103 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 103a were prepared. The concentrated compositions 103-01 to 103-09 are concentrated in aqueous solution and prepared by the procedure (viil). The concentrated compositions 103-10 to 103-18 are concentrated in aqueous solution containing colloidal particulate materials and prepared by the method (ix) The compositions of this example containing 3% or 6% surfactant were not stable under storage in an acceptable form, except in the presence of colloidal particulate material as it shows Table 103a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and the evaluation of herbicide inhibition was made 18 days after application Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 103b.
Table 103b In the high load compositions (488 g a.e. I) of glyphosate, 3% or 6% steareth-20 provided a greater herbicidal effectiveness in this test than the same concentrations of oleth-20. Even only 3%, steareth-20 (composition 103-02) gave an effectiveness equal to that of the commercial standard J formulation. The addition of a mixture of materials in colloidal particles to stabilize the composition (103-11) slightly reduced the effectiveness in this study.
EXAMPLE 104 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 104a were prepared. The concentrated compositions 104-01 to 104-04 are concentrated in aqueous solution and prepared by the process (viii). The concentrated compositions 104-08 to 104-18 are concentrated in aqueous solution containing colloidal particulate materials and prepared by process (ix). The concentrated compositions 104-05 to 104-07 contain particulate materials but no surfactant.
All the compositions of this example except 104-01 to 104-03 were stable under storage in acceptable form.
Table 104a Alcotan plants (Abutilon theophrasti, ABUTH) and 77 Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 21 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 104b.
Table 104b Among the high load compositions (488 g ae / l) of glyphosate stabilized that provided herbicide effectiveness superior to that of the commercial standard J formulation, at least in ABUTH, they were 104-10 and 104-11 (respectively 4.5% and 6%). % of steareth-20 + MON 0818 + 1.5% of Aerosil 380), 104-13 (4 5% steareth-20 + 3% MON 0818 + 1.5% mixed Aerosil MOX-80 / MOX-170) and 104-16 (4.5% steareth-20 + 3% MON 0818 + 1.5% mixture of Aerosil MOX-80/380). The relatively poor performance of the composition 104-04 and the good performance of the composition 104-02 shows that the excellent results obtained with the stabilized compositions listed above are mainly attributable to the steareth-20 component.
EXAMPLE 105 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 105a were prepared. The concentrated compositions 105-01 to 105-09 are concentrated in aqueous solution and prepared by the process (viii) The concentrated compositions 105-10 to 105-18 are concentrated in aqueous solution containing colloidal particle materials and prepared by the procedure (ix). The compositions of this example containing 3% or 6% surfactant were not stable under storage in an acceptable form, except in the presence of colloidal particulate material as shown.
Table 105a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 22 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 105b.
Table 105b The compositions containing steareth-20 acted generally better than their counterparts containing oleth-20 in this study, both in the presence and in the absence of materials in colloidal particles.
EXAMPLE 106 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 106a were prepared. All contain materials in colloidal particles and were prepared by the procedure (ix). The compositions of this example showed all stability under acceptable storage. The compositions shown as containing colloidal particle material were not stable under storage unless the colloidal particulate material was included as shown.
Table 106a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The treatments were applied in four different hours of the day. The applications of spray compositions are They did 16 days after planting ABUTH and ECHCF, and the evaluation of the herbicide inhibition was done 22 days after the application. Formulation J was applied as a comparative treatment. The results, averaged for all replicates of each treatment, are shown in Table 106b.
Table 106b Composition 106-03 illustrates the consistency of the high level yield obtainable with, in this case, steareth-20 at a weight / weight ratio a a.e. of glyphosate of approximately 1: 3 together with a small amount of butyl stearate and Aerosii 380. An average percentage of inhibition of ABUTH across all four amounts of glyphosate shows the following comparison of 106-03 with formulation J, applied to four different hours of the day: EXAMPLE 107 Concentrated aqueous compositions containing IPA salt of glyphosa and excipient ingredients as shown in Table 107a were prepared. The concentrated compositions 107-01 to 107-07 are concentrated in aqueous solution and prepared by the process (viii). The concentrated compositions 107-08 to 107-18 are concentrated in aqueous solution containing colloidal particulate materials and prepared by the procedure (x). Compositions 107-01 to 107-06 were not stable under storage in acceptable form. All other compositions showed stability under acceptable storage.
Table 107a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 23 days after application.
The formulations B and were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 107b.
Table 107b Several high load glyphosate compositions (488 g a.e./l) stabilized from this example provided equal or superior herbicidal effectiveness, at least in ABUTH, to that obtained with the commercial standard J formulation.
EXAMPLE 108 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 108a were prepared. The concentrated compositions 108-12 to 108-14 are concentrated in aqueous solution and prepared by the process (viií). The concentrated compositions 108-01 to 108-11 and 108-15 to 108-17 are concentrated in aqueous solution containing colloidal particulate materials and prepared by the process (ix).
Table 108a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 20 days after application. Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 108b.
Table 108b Several stabilized high load (488 g a.e./l) compositions of this example provided equal or superior herbicidal effectiveness, both in ABUTH and in ECHCF, to that obtained with the commercial standard J formulation.
EXAMPLE 109 Spray compositions containing glyphosate were prepared by tank mixing formulation B with excipients as shown in Table 109. Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 22 days after application. The results, averaged for all replicates of each treatment, are shown in Table 109.
Table 109 Steareth-20, steareth-30 and cetearet-30 were more effective additives for formulation B than steareth-20 in this study.
EXAMPLE 110 Spray compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 110a were prepared. The procedure (ii) was followed for the spray compositions 110-01 to 110-22 and 110-26 to 110-72, using soy lecithin (45% phospholipids, Avanti). The procedure (i) was followed for the spray compositions 110-23 to 110-25.
Table 110a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. The applications of compositions of sprinkling were done 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application. Formulations C and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 110b.
Table 110b Compositions that outperformed the commercial standard C and J formulations in both ABUTH and ECHCF in this test included 110-26, 110-27, 110-30, 110-34, 110-35, 110-51 and 110- 57, all containing lecithin, butyl stearate and MON 0818.
EXAMPLE 111 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 111a were prepared. Concentrated compositions 111-01 to 111-06 were prepared by procedure (x), using soy lecithin (45% fbsfolip.dos, Avanti). Composition 111-07 was prepared by the procedure (viií).
Picture 111a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 15 days after application.
Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 111b.
Table 111b The data for the glyphosate amount of 450 g a.e./ha in this study are not reliable. An application error is suspected. The high levels of Ethomeen T / 25 included in the compositions of this example tend to obscure the effects of lecithin and butyl stearate, but composition 111-05, for example, showed surprising effectiveness.
EXAMPLE 112 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 112a were prepared. The procedure (vii) was followed for the concentrated composition 112-08 and the procedure (x) for the concentrated compositions 112-01 a 112-07 and 112-09, using soy lecithin (45% phospholipids, Avapti).
Table 112a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application.
Formulations B and C were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 112b.
Table 112b The overall herbicidal effectiveness was very high under the conditions of this study, but a tendency can be discerned in the compositions 112-01 to 112-04 to improve the yield because the concentration of butyl stearate was increased from zero to 2%.
EXAMPLE 113 Aqueous spray compositions were prepared containing various tetraalkylammonium salts of glyphosate and excipient ingredients as shown in Table 113a. The procedure (i) was followed for the spray compositions 113-02 to 113-04, 113-06 to 113-08, 113-10 to 113-12 and 113-14 to 113-16, using soy lecithin (45% phospholipids, Avanti). Compositions 113-01, 113-05, 113-09 and 113-13 are simple solutions of tetraalkylammonium salts of gylphosate in water.
Picture 113a Alcotan plants (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were grown and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicide inhibition was made 16 days after application. Formulations B, C and J were applied as comparative treatments. In addition, formulations B and C were tank-mixed with a predispersed lecithin composition prepared from soy lecithin (45% phospholipids, Avanti). The results, averaged for all replicates of each treatment, are shown in Table 113b.
Table 113b The addition of lecithin to composition B (glyphosate IPA salt) did not provide a significant increase in herbicidal effectiveness. However, when lecithin was added to glyphosate tetraalkylammonium salts, significant improvements were obtained. In some cases the addition of a very small amount of lecithin (0-02%) gave better results than the addition of a larger amount (0.1%). A striking effectiveness was obtained, for example, with the composition 113-16, which contained the tetrabutylammonium salt of glyphosate and 0.02% lecithin.
EXAMPLE 114 Concentrated aqueous compositions containing glyphosate IPA salt and excipient ingredients as shown in Table 114a were prepared. The procedure (v) was followed for all the concentrated compositions, using soy lecithin (45% phospholipids, Avanti).
Frame 114a Alcotán plants (Abutilón thßophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were cultivated and treated by the normal procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicide inhibition was made 18 days after application. Formulations B and J were applied as comparative treatments. The results, averaged for all replicates of each treatment, are shown in Table 114b.
Table 114b The overall herbicidal effectiveness in this study was extremely high and the improvements over the commercial standard J formulation are therefore difficult to discern However, a particularly surprising performance was obtained with compositions 114-10, 114-11 and 114-13 to 114-16 containing lecithin and benzalkonium chloride. The above description of specific embodiments of the present invention is not intended to be a complete list of each possible modality of the invention. Those skilled in the art will recognize that modifications may be made to the specific embodiments described herein that will be within the scope of this invention.

Claims (5)

  1. NOVELTY OF THE INVENTION CLAIMS 1. - A method for applying an exogenous chemical to a plant, comprising the steps of (a) contacting the foliage of a plant with a biologically effective amount of the exogenous chemical, and (b) contacting the same foliage with a composition aqueous comprising a first excipient substance that is aphylic, wherein the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100; wherein said aqueous composition forms anisotropic aggregates in or on a wax layer; and wherein step (b) occurs simultaneously with or within approximately 96 hours after or before step (a).
  2. 2. The method according to claim 1, further characterized in that said first excipient substance is a liposome-forming material comprising an amphiphilic compound or mixture of said compounds having two hydrophobic portions, each of which is an alkyl chain or saturated acyl having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of said compounds having two hydrophobic portions constitutes approximately 40 to 100 weight percent of all amphiphilic compounds having two hydrophobic portions present in said liposome-forming material.
  3. 3. The method according to claim 2, further characterized in that the liposome framing material has a hydrophilic main group comprising a cationic group.
  4. 4. The method according to claim 3, further characterized in that the cationic group is an amine or ammonium group.
  5. 5. The method according to claim 1, further characterized in that the first excipient substance comprises a liposome-forming compound having a hydrophobic portion comprising two saturated or unsaturated hydrocarbyl groups R1 and R2 each having about 7 to about 21 carbon atoms, said liposome-forming compound has, at a pH of 4, a formula selected from the group consisting of: (a) N + (CH2R1) (CH2R2) R3) (R4) Z "wherein R3 and R4 are independently hydrogen, C 1-4 alkyl or C 1-4 hydroxyalkyl and Z is a suitable anion; (b) N + (R 5) (R 6) (R 7) CH 2 CH (OCH 2 R 1) CH 2 (? CH 2 R 2) Z- wherein R 5, R 6 and R7 are independently hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl and Z is a suitable anion, (c) N + (R5) (R6) (R7) CH2CH (0C0R1) CH2 (0C0R2) Z- wherein R6, Rβ, R7 and Z are as defined above, and (d) N + (R5) (R6) (R7) CH2CH2-P? 4 -CH2CH (OC? R1) CH2 (? C? R2) wherein R5, R? R7 are as defined above. 6. - The method according to claim 5, further characterized in that Z is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 7. The method according to claim 6, further characterized in that R1 and R2 are independently saturated straight chain alkyl groups each having about 7 to about 21 carbon atoms. 8. The method according to claim 5, further characterized in that the substance substance is a phospholipid selected from the group consisting of di-C8-22-alkanoylphosphatidylcholines and d-C8-α-alkanoylphosphatidylethanolamines. 9. The method according to claim 8, further characterized in that the excipient substance ppmera is a dipalmitoyl or distearoyl ester of phosphatidylcholine or a mixture thereof. 10. The method according to claim 1, further characterized in that said first excipient substance is a quaternary ammonium compound or mixture of said compounds having a hydrophobic portion which is a saturated alkyl or halogenoalkyl group having from about 6 to about 22 carbon atoms. 11. The method according to claim 10, further characterized in that said first excipient substance has the formula: R8-Wa-X-Yb- (CH2) n-N + (Rβ) (R10) (R11) r wherein R8 represents said hydrophobic portion and is a hydrocarbyl or halogenoalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S02, n is 2 to 4, R9, R10 and R11 are independently C1-4 alkyl and T is a suitable anion. 12. The method according to claim 11, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 13. The method according to claim 11, further characterized in that R8 is fluorinated. 14. The method according to claim 11, further characterized in that R8 is perfluorinated. 15. The method according to claim 14, further characterized in that R8 has about 6 to about 12 carbon atoms 16. The method according to claim 11, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 17. The method according to claim 11, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S? 2, Y is NH, a is O, b is 1, R9, R10 and R11 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 18. The method according to claim 17, further characterized in that X is S02, n is 3 and T is chloride, bromide or iodide. 19. The method according to claim 1, further characterized in that the aqueous composition further comprises a second excipient substance having at least one hydrophobic portion, wherein if the second excipient substance has a hydrophobic portion, the hydrophobic portion, is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms, and wherein if the second excipient substance has a plurality of hydrophobic portions, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms; carbon, said plurality of hydrophobic portions have a total of about 12 to about 40 carbon atoms. 20. The method according to claim 19, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a quaternary ammonium compound or mixture of said compounds. 21. The method according to claim 20, further characterized in that said quaternary ammonium compound has the formula: R8-WsrX-Yb- (CH2) rrN + (R9) (R10) (R11) T- wherein R8 represents said hydrophobic portion and is a hydrocarbyl or haloalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S? 2, n is 2 to 4, R9, R10 and R11 are independently C1-4 alkyl and T is a suitable anion. 22. The method according to claim 21, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 23. The method according to claim 21, further characterized in that R8 is fluorinated. 24 - The method according to claim 21, further characterized in that R8 is perfluorinated. 25. The method according to claim 24, further characterized in that R8 has about 6 to about 12 carbon atoms. 26. The method according to claim 21, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 27. The method according to claim 21, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S02, Y is NH, a is O, b is 1, R9, R1C and R11 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 28. The method according to claim 27, further characterized in that X is S? 2, n is 3 and T is chloride, bromide or iodide. 29. The method according to claim 19, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a compound or mixture of compounds of the formula: R14-C? -A-R15 in where R14 represents said hydrophobic portion, R15 is an alkyl group of C? _ ß and A is O or NH 30.- The method according to claim 19, further characterized in that said first excipient substance is a liposome-forming substance and said Second excipient substance is a compound or mixture of compounds of the formula: R14-C? -A-R15 wherein R14 is a hydrocarbyl group having about 5 to about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or NH. 31. The method according to claim 30, further characterized in that R14 has approximately 11 a about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 32.- The method according to claim 31, further characterized in that said second excipient substance is a C1-4 alkyl ester of an acid fatty acid of C12-18. 33. The method according to claim 30, further characterized in that said second excipient substance is a C 1-4 alkyl ester of a saturated C? 2-18 fatty acid. 34. The method according to claim 30, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C? 2-? B fatty acid. 35. The method according to claim 30, further characterized in that said second excipient substance is butyl stearate. 36. The method according to claim 1, further characterized in that said first excipient substance is an alkyl ether surfactant or mixture of said surfactants having the formula: R12 -? - (CH2CH20) n (CH (CH3) CH2?) M-R13 wherein R12 is an alkyl or alkeniion group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R13 it is hydrogen or C1-4 alkyl. 37. - The method according to claim 36, further characterized in that m is 0 and R13 is hydrogen. 38. The method according to claim 36, further characterized in that n is from about 20 to about 40. 39. The method according to claim 37, further characterized in that R12 is a saturated straight-chain alkyl group. 40. - The method according to claim 39, further characterized in that the alkyl ether surfactant is a cetyl or stearyl ether or mixture thereof. 41. The method according to claim 36, further comprising a second excipient substance comprising a compound or mixture of compounds of the formula: R14-C? -A-R15 wherein R14 is a hydrocarbyl group having about 5? to about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or NH. 42. The method according to claim 41, further characterized in that R14 has about 11 to about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 43. - The method according to claim 42, further characterized in that said second excipient substance is a C1-4 alkyl ester of a C? 2-? β fatty acid. 44. The method according to claim 42, further characterized in that said second excipient substance is a C 1-4 alkyl ester of a saturated C 12-1 s fatty acid. 45. The method according to claim 42, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C12-18 fatty acid. 46. The method according to claim 42, further characterized in that said second excipient substance is butyl stearate. 47. The method according to claim 1, further characterized in that the first excipient substance has a critical packing parameter of more than 1/3. 48. The method according to claim 1, further characterized in that the first excipient substance forms aggregates in aqueous solution or dispersion, most of which are not simple micelles. 49. The method according to claim 1, further characterized in that the exogenous chemical is an exogenous chemical applied to the foliage. 50. - The method according to claim 49, further characterized? because the exogenous chemical is a pesticide, gametocide or plant growth regulator. 51.- The method according to claim 50, further characterized in that the exogenous chemical is a herbicide, nematicide or plant growth regulator. 52. The method according to claim 51, further characterized in that the exogenous chemical is a herbicide. 53. The method according to claim 52, further characterized in that the herbicide is selected from the group consisting of acetanilides, bipyridyls, cyclohexenones, dlnitroanilines, dyphenyl ethers, fatty acids, hydroxybenzonitriles, imidazolinones, phenoxies, phenoxypropionates, substituted ureas, sulfonllureas , thiocarbamates and triazines. 54. The method according to claim 52, further characterized in that the herbicide is selected from the group consisting of acetochlor, alachlor, metolachlor, aminotriazole, asulam, bentazon, bialaphos, dicuat, paraquat, bromacil, cletodim, sethoxydim, dicamba, diflufenican, pendimethalin, acifluorfen, fomesafen, oxyfluorfen, C9-10 fatty acids, fosamine, flupoxam, glufosinate, glyphosate, bromoxynil, imazaquin, imazetapyr, isoxaben, norflurazon, 2,4-D, diclofop, fluazifop, quizalofop, picloram, propanil , fluometuron, isoproturon, chlorimuron, chlorsulfuron, halogensulfuron, metsulfuron, primisulfuron, sulfbmeturon, sulfosulfuron, trialate, atrazine, metribuzin, triclopir and herbicidal derivatives thereof. 55. - The method according to claim 54, further characterized in that the herbicide is glyphosate or a herbicidal derivative thereof. 56. The method according to claim 55, further characterized in that the herbicide is glyphosate in its acid form. 57. The method according to claim 51, further characterized in that the exogenous chemical is water-soluble. 58. The method according to claim 57, further characterized in that the exogenous chemical is a salt having an anionic portion and a cationic portion. 59. The method according to claim 58, further characterized in that at least one of said anionic and cationic portions is biologically active and has a molecular weight of less than about 300. The method according to claim 59 , further characterized because the exogenous chemical is paraquat or dicuat. 61.- The method according to claim 59, further characterized in that the exogenous chemical exhibits systemic biological activity in the plant. 62. The method according to claim 61, further characterized in that the exogenous chemical has one or more functional groups selected from the group consisting of amine, amide, carboxylate, phosphonate and phosphinate groups. 63. - The method according to claim 62, further characterized in that the exogenous chemical is a salt of 3,4,4-trifluoro-3-butenoic acid or of N- (3,4,4-trifluoro-1-oxo-3) -bute? l) glycine exhibiting nematicidal activity. 64.- The method according to claim 62, further characterized in that the exogenous chemical is a herbicidal compound or plant growth regulator having at least one of each of the functional groups amine, carboxylate or one of the functional groups phosphonate or phosphinate. The method according to claim 64, further characterized in that the herbicidal compound or plant growth regulator is a glufosinate salt. 66. The method according to claim 65, further characterized in that the glufosinate salt is the ammonium salt. 67.- The method according to claim 64, further characterized in that the herbicidal compound or plant growth regulator is a salt of N-phosphonomethylglycine. 68.- The method according to claim 67, further characterized in that the N-phosphonomethylglycine salt is selected from the group consisting of sodium, potassium, ammonium, mono-, di-, tri- and tetraalkylammonium salts of C 1-4. , mono-, di- and tri-alkanolammonium of CM, mono-, di- and tri-alkylsulfonium of C1- and sulfoxonium. 69. - The method according to claim 68, further characterized in that the N-phosphonomethylglycine salt is the ammonium, monoisopropylammonium or trimethylsulfonium salt 70. The method according to claim 1, further characterized in that the aqueous composition comprises supramolecular aggregates of the first excipient substance having an average diameter of at least 20 nm 71.- The method according to claim 1, further characterized in that the aqueous composition comprises supramolecular aggregates of the carrier material substance having an average diameter of at least 30 nm. 72. The method according to claim 41, further characterized in that the aqueous composition is an emulsion comprising an oil phase comprising said second excipient substance. 73. The method according to claim 72, further characterized in that the emulsion is a multiple emulsion of water in oil in water. 74. The method according to claim 72, characterized in that the emulsion is an oil-in-water emulsion. 75.- The method according to claim 1, further characterized in that the aqueous composition on a layer of epicuticular wax on the surface of a plant forms or enlarges the channels hydrophilic through the epicuticular wax layer, hydrophilic channels being able to transport the exogenous chemical into the plant more quickly or more completely than a layer of epicuticular wax lacking such formation or enlargement of the hydrophilic channels . The method according to claim 1, further characterized in that the composition forms an aqueous microdomain in or on a layer of epicuticular wax on the surface of a plant, said first excipient substance in the aqueous microdomain being present as double layers or multilaminar structures. 77. The method according to claim 1, further characterized in that step (b) occurs simultaneously with step (a). 78. The method according to claim 77, further characterized in that the exogenous chemical is contained within said aqueous composition. 79. An aqueous composition for application to a plant in conjunction with the application of an exogenous chemical to the plant, comprising: (a) a first excipient substance that is amphiphilic and (b) a second excipient substance having less a hydrophobic portion, wherein if the second excipient substance has a hydrophobic portion, the hydrophobic portion, is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms, and wherein if the second excipient substance has a plurality of hydrophobic portions, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality of hydrophobic portions having a total of about 12 to about 40 carbon atoms; wherein the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100; and wherein said aqueous composition forms anisotropic aggregates in or on a wax layer. 80.- The composition according to claim 79, further characterized in that said first excipient substance is a liposome-forming material comprising an amphiphilic compound or mixture of said compounds having two hydrophobic portions, each of which is an alkyl chain or saturated acid having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of said compounds having two hydrophobic portions constitutes from about 40 to 100 weight percent of all amphiphilic compounds having two hydrophobic portions present in said liposome-forming material. 81. The composition according to claim 80, further characterized in that the liposome-forming material has a hydrophilic main group comprising a cationic group. 82. The composition according to claim 81, further characterized in that the cationic group is an amine or ammonium group. 83. The composition according to claim 79, further characterized in that the excipient substance ppmera comprises a liposome-forming compound having a hydrophobic portion comprising two saturated or unsaturated hydrocarbyl groups R 1 and R 2 each having about 7 to about 21 carbon atoms. carbon, said liposome-forming compound has, at a pH of 4, a formula selected from the group consisting of: (a) N + (CH2R1) (CH2R2) (R4) -T wherein R3 and R4 are independently hydrogen, C1- or C 1-4 hydroxyalkyl and Z is a suitable anion; (bJ ^ ^ XR ^ CHZCHÍOCHsR ^ CH-íOCH? R ^ r where R5, Rβ and R7 are independently hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl and Z is a suitable anion, (c) N + (R5 ) (R6) (R7) CH2CH (? C? R1) CH2 (? C? R2) Z "wherein R5, R?, R7 and Z are as defined above, and (d) N + (R5) (R?) ( R7) CH2CH2-P04"-CH2CH (0C0R1) CH2 (0C0R2) wherein R5, R6 and R7 are as defined above 84. The composition according to claim 83, further characterized in that Z is selected from the group consisting of of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate 85. The composition according to claim 84, further characterized in that R1 and R2 are independently alkyl groups of saturated straight chain each having about 7 to about 21 carbon atoms. 86.- The composition according to claim 83, further characterized in that the excipient substance ppmera is a phospholipid selected from the group consisting of dialkyl-phosphatidylcholines of Cß-22 and alkanoylphosphatidyethanolamines of Ce -.-- 87.- The composition in accordance with claim 86, further characterized in that the first excipient substance is a dipalmitoleyl or distearoyl ester of phosphatidylcholine or a mixture thereof. 88.- The composition according to claim 79, further characterized in that said first excipient substance is a quaternary ammonium compound or mixture of said compounds having a hydrophobic portion which is a saturated alkyl or halogenoalkyl group having from about 6 to about 22 carbon atoms. 89.- The composition according to claim 88, further characterized in that said first excipient substance has the formula: R8-Wa-X-Yb- (CH2) n-N + (R9) (R10) (R11) r wherein R8 represents said hydrophobic portion and is a hydrocarbyl or haloalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S02, n is 2 to 4, R9, R10 and R are independently CH alkyl and T is a suitable anion. 90. The composition according to claim 89, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 91.- The composition according to claim 89, further characterized in that R8 is fluorinated. 92. The composition according to claim 89, further characterized in that R8 is perfluorinated. 93. The composition according to claim 92, further characterized in that R8 has about 6 to about 12 carbon atoms. 94. The composition according to claim 89, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 95.- The composition according to claim 89, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S? 2, Y is NH, a is 0, b is 1, R9, R10 and R11 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 96. The composition according to claim 95, further characterized in that X is S? 2, n is 3 and T is chloride, bromide or iodide. 97. - The composition according to claim 79, further characterized in that the second excipient substance has a plurality of hydrophobic portions, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality of hydrophobic portions they have a total of about 12 to about 40 carbon atoms. The composition according to claim 79, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a quaternary ammonium compound or mixture of said compounds. 99.- The composition according to claim 98, further characterized in that said quaternary ammonium compound has the formula "R8-Wa-X-Yb- (CH2)" - N + (R9) (R10) (R11) r wherein R8 represents said hydrophobic portion and is a hydrocarbyl or haiogenoalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S? 2, n is 2 to 4, R9, R10 and R11 are independently C1-4 alkyl and T is a suitable anion. 100.- The composition according to claim 99, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 101. - The composition according to claim 99, further characterized in that R8 is fluorinated. 102. The composition according to claim 99, further characterized in that R8 is perfluorinated. 103. The composition according to claim 102, further characterized in that R8 has about 6 to about 12 carbon atoms. 104. The composition according to claim 99, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. The composition according to claim 99, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S? 2, Y is NH, a is 0, b is 1, R9, R10 and R1 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 106. The composition according to claim 105, further characterized in that X is S02, n is 3 and T is chloride, bromide or iodide. 107. - The composition according to claim 79, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a compound or mixture of compounds of the formula: R14-CO-A-R15 wherein R14 represents said hydrophobic portion, R15 is an alkyl group of Ci-6 and A is O or NH. 108. The composition according to claim 79, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a compound or mixture of compounds of the formula: R14-C? -A-R15 in where R14 is a hydrocarbyl group having about 5 to about 21 carbon atoms, R16 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27 , and A is O or NH. 109. The composition according to claim 108, further characterized in that R14 has about 11 to about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 110.- The composition according to claim 109, further characterized in that said second excipient substance is an alkyl ester of C- of a C-? 2-? Β fatty acid. 111. The composition according to claim 108, further characterized in that said second excipient substance is an alkylic ester of CM of a saturated C? 2-? 8 fatty acid. 112. The composition according to claim 108, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C? 2-? Β fatty acid. 113. The composition according to claim 108, further characterized in that said second excipient substance is butyl stearate. 114. The composition according to claim 79, further characterized in that said excipient substance is an alkyl ether surfactant or mixture of said surfactants having the formula: R12-0- (CH2CH20) n (CH (CH3 CH20) m-R13 wherein R12 is an alkyl or aannyl group having from about 16 to about 22 carbon atoms, n is an average number from about 10 to about 100, m is an average number from 0 to about 5 and R13 is hydrogen or C? - alkyl? The composition according to claim 114, further characterized in that m is 0 and R13 is hydrogen. The composition according to claim 114, further characterized in that n is from about 20 to about 20 40. 117. The composition according to claim 115, further characterized in that R12 is a saturated straight-chain alkyl group. 118. The composition according to claim 117, further characterized in that the alkyl ether surfactant is a cetyl or stearyl ether or mixture thereof. 119.- The composition according to claim 114, further comprising a second excipient substance consisting of a compound or mixture of compounds of the formula: R 1 -CO-A-R 15 wherein R 14 is a hydrocarbyl group having about 5. at about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or NH. 120.- The composition according to claim 119, further characterized in that R14 has about 11 to about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 121.- The composition according to the claim 120, further characterized in that said second excipient substance is a C1-4 alkyl ester of a C? 2-? 8 fatty acid. 122. The composition according to claim 120, further characterized in that said second excipient substance is an amino acid ester of C-M of a saturated C 12 -? S fatty acid. 123. The composition according to claim 120, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C? 2-? Β fatty acid. 124. The composition according to claim 120, further characterized in that said second excipient substance is butyl stearate. 125. The composition according to claim 79, further characterized in that the first excipient substance has a critical packing parameter of more than 1/3. 126. The composition according to claim 79, further characterized in that the first excipient substance forms aggregates in aqueous solution or dispersion, most of which are not simple micelles. 127.- The composition according to claim 79, further characterized in that the exogenous chemical is an exogenous chemical applied to the foliage. 128. The composition according to claim 79, further characterized in that the aqueous composition comprises supramolecular aggregates of the first excipient substance having an average diameter of at least 20 nm. 129.- The composition according to claim 79, further characterized in that the aqueous composition comprises aggregates supramolecular of the first excipient substance having an average diameter of at least 30 nm. 130.- The composition according to claim 119, further characterized in that the aqueous composition is an emulsion comprising an oil phase comprising said second excipient substance. 131. The composition according to claim 130, further characterized in that the emulsion is a multiple emulsion of water in oil in water. 132. The composition according to claim 130, further characterized in that the emulsion is an oil-in-water emulsion. 133. The composition according to claim 79, further characterized in that the aqueous composition on a layer of epicuticular wax on the surface of a plant fopna or enlarges the hydrophilic channels through the layer of epicuticular wax, the hydrophilic channels being capable to transport the exogenous chemical into the interior of the plant more quickly or more completely than a layer of epicuticular wax lacking such formation or enlargement of the hydrophilic channels. 134. The composition according to claim 79, further characterized in that the composition forms an aqueous microdomain in or on a layer of epicuticular wax on the surface of a plant, said first excipient substance in the aqueous microdomain being present as double or double layers. multilaminar structures. 135. - A treatment composition for plants comprising (a) an exogenous chemical, and (b) a first excipient substance that is amphiphilic; wherein the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100; and wherein in the presence of water said aqueous composition forms anisotropic aggregates in or on a wax layer. The composition according to claim 135, further comprising water in an amount effective to make the composition a dilute aqueous composition ready for application to the foliage of a plant. 137. The composition according to claim 135, further characterized in that the composition is a concentrated stable composition on the counter comprising the exogenous chemical substance in an amount of about 15 to about 90 weight percent. 138. The composition according to claim 137, further characterized in that the composition is a solid composition comprising the exogenous chemical substance in an amount of about 30 to about 90 weight percent. 139.- The composition according to claim 138, further characterized in that the composition is a granular formulation soluble in water or dispersible in water. The composition according to claim 137, further comprising a liquid diluent, and wherein the composition comprises the exogenous chemical substance in an amount of about 15 to about 60 weight percent. 141. The composition according to claim 140, further characterized in that the exogenous chemical substance is water-soluble and is present in an aqueous phase of the composition in an amount of about 15 to about 45 percent by weight of the composition. 142. The composition according to claim 141, further characterized in that the composition is a concentrate in aqueous solution. 143. The composition according to claim 141, further characterized in that the composition is an emulsion having an oil phase. 144. The composition according to claim 143, further characterized in that the composition is an oil-in-water emulsion. 145. The composition according to claim 143, further characterized in that the composition is a water-in-oil emulsion. 146. The composition according to claim 143, further characterized in that the composition is a multiple emulsion of water in oil in water. 147 -. 147 - The composition according to claim 141, further comprising a solid inorganic particulate colloidal material. 148. The composition according to claim 136, further characterized in that the composition comprises supramolecular aggregates of the excipient substance ppmera having an average diameter of at least 20 nm. 149. The composition according to claim 136, further characterized in that the composition comprises supramolecular aggregates of the first excipient substance having an average diameter of at least 30 nm. 150.- The composition according to claim 135, further characterized in that the composition in the presence of water on a layer of epicuticular wax on the surface of a plant, forms or enlarges the hydrophilic channels through the layer of epicuticular wax, being capable hydrophilic channels to transport the exogenous chemical into the plant more quickly or more completely than a layer of epicuticular wax lacking such formation or enlargement of hydrophilic channels. 151. The composition according to claim 135, further characterized in that the composition in the presence of water forms an aqueous microdomain in or on a layer of epicuticular wax on the surface of a plant, said first excipient substance in the aqueous microdomain being present as double layers or multi-layer structures. 152. - The composition according to claim 135, further characterized in that said excipient substance ppmera is a liposome-forming material comprising an amphiphilic compound or mixture of said compounds having two hydrophobic portions, each of which is an alkyl or acyl chain saturated having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of said compounds having two hydrophobic portions constitutes about 40 to 100 weight percent of all amphiphilic compounds having two hydrophobic portions present in said liposome-forming material. 153. The composition according to claim 152, further characterized in that the liposome-forming material has a hydrophilic main group comprising a cationic group. 154. The composition according to claim 153, further characterized in that the cationic group is an amine or ammonium group. 155. The composition according to claim 135, further characterized in that the first excipient substance comprises a liposome-forming compound having a hydrophobic portion comprising two saturated or unsaturated hydrocarbyl groups R and R2 each having about 7 to about 21 carbon atoms, said liposome-forming compound has, at a pH of 4, a formula selected from the group consisting of: (a) N * (CH2R1) (CH2R2) (R4) Z- wherein R 3 and R 4 are independently hydrogen, C 1-4 alkyl or hydroxyalkyl of C? _4 and Z is a suitable anion; (b) N + (R5) (Rβ) (R7) CH2CH (CH CH2R1) CH2 (OCH2R2) Z- wherein R5, R6 and R7 are independently hydrogen, Ci ^ alkyl or hydroxyalkyl of CH and Z is a suitable anion; (c) N * (R5) (Rβ) (R7) CH2CH (CC ?R1) CH2 (OCOR2) Z- wherein R5, Rß, R7 and Z are as defined above; and (d) N + (R5) (Re) (R7) CH2CH2-P04-CH2CH (0C0R1) CH2 (0C0R2) wherein R5, R6 and R7 are as defined above. 156. The composition according to claim 155, further characterized in that Z is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 157. The composition according to claim 156, further characterized in that R1 and R2 are independently saturated straight chain alkyl groups each having about 7 to about 21 carbon atoms. 158. The composition according to claim 155, further characterized in that the first excipient substance is a phospholipid selected from the group consisting of dialkyl-phosphatidylcholines of Cß- ?? and alkanoylphosphatidylethanolamines of Ca-22 159. The composition according to claim 158, further characterized in that the first excipient substance is a dipalmitoyl or distearoyl ester of phosphatidylcholine or a mixture thereof. 160. - The composition according to claim 135, further characterized in that said first excipient substance is a quaternine ammonium compound or mixture of said compounds having a hydrophobic portion which is a saturated alkyl or halogenoalkyl group having from about 6 to about 22 carbon atoms. carbon. 161. The composition according to claim 160, further characterized in that said first excipient substance has the formula: R8-Wa-X-Yb- (CH2) n-N + (R) (R10) (R11) T wherein R8 represents said hydrophobic portion and is a hydrocarbyl or halogenoalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S? 2, n is 2 to 4, R?, R10 and R11 are independently alkyl of CM and T is a suitable anion. 162. The composition according to claim 161, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 163. The composition according to claim 161, further characterized in that R8 is fluorinated. 164. The composition according to claim 161, further characterized in that Rs is perfluorinated. 165. - The composition according to claim 164, further characterized in that R8 has about 6 to about 12 carbon atoms 166. The composition according to claim 161, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 167. The composition according to claim 161, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S? 2, Y is NH, a is 0, b is 1, R9, R10 and R11 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 168. The composition according to claim 167, further characterized in that X is S02, n is 3 and T is chloride, bromide or iodide. 169. The composition according to claim 135, further characterized in that the aqueous composition further comprises a second excipient substance that at least a hydrophobic portion, wherein if the second excipient substance has a hydrophobic portion, the hydrophobic portion is a hydrocarbyl group or haloalkyl having about 6 to about 22 carbon atoms, and wherein if the second excipient substance has a plurality of hydrophobic portions, each of said hydrophobic portions is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality from Hydrophobic portions have a total of about 12 to about 40 carbon atoms. 170. The composition according to claim 169, further characterized in that said first excipient substance is a liposome-forming substance and said second excipient substance is a quaternary ammonium compound or mixture of said compounds. 171. The composition according to claim 170, further characterized in that said quaternary ammonium compound has the formula: R8-Wa-X-Yb- (CH2) p-N + (R9) (R10) (R11) r wherein R8 represents said hydrophobic portion and is a hydrocarbyl or haiogenoalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1, but at least one of a and b is 1, X is CO, SO or S? 2, n is 2 to 4, R9, R0 and R11 are independently alkyl of CM and T is a suitable anion. 172. The composition according to claim 171, further characterized in that R8 is hydrocarbyl and has about 12 to about 18 carbon atoms. 173. The composition according to claim 171, further characterized in that R8 is fluorinated. 174. The composition according to claim 171, further characterized in that R8 is perfluorinated. 175. - The composition according to claim 174, further characterized in that R8 has about 6 to about 12 carbon atoms. 176. The composition according to claim 171, further characterized in that T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 177. The composition according to claim 171, further characterized in that R8 is saturated perfluoroalkyl having from about 6 to about 12 carbon atoms, X is CO or S? 2, Y is NH, a is 0, b is 1, R9, R10 and R11 are methyl, and T is selected from the group consisting of hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. 178. The composition according to claim 177, further characterized in that X is S02, n is 3 and T is chloride, bromide or iodide. 179. - The composition according to claim 169, further characterized in that said excipient substance ppmera is a liposome-forming substance and said second excipient substance is a compound or mixture of compounds of the formula: R14-C? -A-R15 wherein R14 represents said hydrophobic portion, R15 is an alkyl group of C? -β and A is O or NH. 180.- The composition according to claim 169, further characterized in that said first excipient substance is a Liposome forming substance and said second excipient substance is a compound or mixture of compounds of the formula: R 14 -CO-A-R 15 wherein R 14 is a hydrocarbyl group having about 5 to about 21 carbon atoms, R 1 S is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or H. 181. The composition according to claim 180, further characterized because R14 has about 11 to about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 182. The composition according to claim 181, further characterized in that said second excipient substance is an alkyl ester of CM of a fatty acid of C? 2_i8. 183. The composition according to claim 180, further characterized in that said second excipient substance is an alkyl ester of CM of a saturated C 12-18 fatty acid. 184. The composition according to claim 180, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C12-18 fatty acid. 185. - The composition according to claim 180, further characterized in that said second excipient substance is butyl stearate. 186. The composition according to claim 135, further characterized in that said first excipient substance is an aikenic ether surfactant or mixture of said surfactants having the formula. R12-0- (CH2CH20) n (CH (CH3) CH20) r "-R13 wherein R12 is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100 , m is an average number from 0 to about 5 and R13 is hydrogen or C1-4 alkyl. 187. The composition according to claim 186, further characterized in that m is 0 and R13 is hydrogen. 188. The composition according to claim 186, further characterized in that n is from about 20 to about 40. 189. The composition according to claim 187, further characterized in that R12 is a saturated straight-chain alkyl group. 190. The composition according to claim 189, further characterized in that the alkyl ether surfactant is a cetyl or stearyl ether or mixture thereof. 191. - The composition according to claim 186, further comprising a second excipient substance consisting of a compound or mixture of compounds of the formula: R14-C? -A-R15 wherein R14 is a hydrocarbyl group having about 5 a about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is from about 11 to about 27, and A is O or NH. 192.- The composition according to claim 191, further characterized in that R14 has about 11 to about 21 carbon atoms, R15 has 1 to about 6 carbon atoms and A is O. 193.- The composition according to the claim 192, further characterized in that said second excipient substance is a C 1-4 alkyl ester of a C? 2-? Β fatty acid. 194. The composition according to claim 192, further characterized in that said second excipient substance is a C 1-4 alkyl ester of a saturated C 12-18 fatty acid. 195. The composition according to claim 192, further characterized in that said second excipient substance is a propyl, isopropyl or butyl ester of a C? 2-? B- fatty acid. 196. The composition according to claim 192, further characterized in that said second excipient substance is butyl stearate. 197.- The composition according to claim 135, further characterized in that the first excipient substance has a critical packing parameter of more than 1/3. 198. The composition according to claim 135, further characterized in that the first excipient substance forms aggregates in aqueous solution or dispersion, most of which are not simple micelles 199. The composition according to claim 135, further characterized because the exogenous chemical is an exogepous chemical applied to the foliage. 200-- The composition according to claim 199, further characterized in that the exogenous chemical is a pesticide, gametocide or plant growth regulator. 201.- The composition according to claim 200, further characterized in that the exogenous chemical is a herbicide, nematicide or plant growth regulator. 202. The composition according to claim 201, further characterized in that the exogenous chemical is a herbicide. 203. The composition according to claim 202, further characterized in that the herbicide is selected from the group consisting of of acetanilides, bipipdilos, cyclohexenones, díntroanilines, diphenyl ethers, fatty acids, hydroxybenzonitriles, midazolinas, phenoxies, phenoxypropionates, substituted ureas, sulfonylureas, thiocarbamates and triazines. 204 - The composition according to claim 202, further characterized in that the herbicide is selected from the group consisting of acetochlor, alachlor, metolachlor, aminotriazole, asulam, bentazon, bialaphos, dicuat, paraquat, bromacil, cletodim, sethoxydim, dicamba, diflufenican , pendimethalin, acifluorfen, fomesafen, oxyfluorfen, C9-10 fatty acids, fosamine, flupoxam, glufosinate, glyphosate, bromoxynil, mazaquin, imazetapyr, soxaben, norflurazon, 2,4-D, diclofop, fluazifop, quizalofop, picloram, propanil, fluometuron, isoprophoturon, chlorimuron, chlorsulfuron, halogensulfuron, metsulfuron, primisulfuron, sulfometuron, sulfosulfuron, trialate, atrazine, metribuzin, triclopir and herbicidal derivatives thereof. 205. The composition according to claim 204, further characterized in that the herbicide is glyphosate or a herbicidal derivative thereof. 206. The composition according to claim 205, further characterized in that the herbicide is glyphosate in its acid form. 207. The composition according to claim 201, further characterized in that the exogenous chemical is water-soluble. 208. The composition according to claim 207, further characterized in that the exogenous chemical is a salt having an anionic portion and a cationic portion. 209. - The composition according to claim 208, further characterized in that at least one of said anionic and cationic portions is biologically active and has a molecular weight of less than about 300. 210.- The composition according to claim 209, characterized also because the exogenous chemical is paraquat or dicuat. 211. The composition according to claim 209, further characterized in that the exogenous chemical exhibits systemic biological activity in the plant, 212. The composition according to claim 211, further characterized in that the exogenous chemical has one or more functional groups. selected from the group consisting of amine, amide, carboxylate, phosphonate and phosphinate groups. 213. The composition according to claim 212, further characterized in that the exogenous chemical is a salt of 3,4,4-trifluoro-3-butenoic acid or of N- (3,4,4-trifluoro-1-oxo) -3-butenyl) glycine exhibiting nematicidal activity. 214. The composition according to claim 212, further characterized in that the exogenous chemical is a herbicidal compound or plant growth regulator having at least one of each of the functional groups amine, carboxylate or one of the functional groups phosphopate or phosphinate. 215 -. 215 - The composition according to claim 214, further characterized in that the herbicidal compound or plant growth regulator is a glufosinate salt. 216. The composition according to claim 215, further characterized in that the glufosinate salt is the ammonium salt. 217. The composition according to claim 214, further characterized in that the herbicidal compound or plant growth regulator is a salt of N-phosphonomethylglycine. 218. The composition according to claim 217, further characterized in that the N-phosphonomethyglycine salt is selected from the group consisting of sodium, potassium, ammonium, mono-, di-, tri- and tetraalkylammonium salts of C 1-4. , mono-, di- and tri-alkanolammonium of C1-, mono-, di- and tri-alkylsulfbium of C1-4 and sulfoxonium. 219. The composition according to claim 218, further characterized in that the N-phosphonomethylglycine salt is the ammonium, monoisopropylammonium or trimethisulfonium salt. 220. The composition according to claim 135, further characterized in that the aqueous composition comprises supramolecular aggregates of the first excipient substance having an average diameter of at least 20 nm. 221. The composition according to claim 135, further characterized in that the aqueous composition comprises aggregates supramolecular of the first excipient substance having an average diameter of at least 30 nm. 222. The composition according to claim 191, further characterized in that the aqueous composition is an emulsion comprising an oil phase comprising said second excipient substance. 223. The composition according to claim 222, further characterized in that the emulsion is a multiple emulsion of water in oil in water. 224. The composition according to claim 222, further characterized in that the emulsion is an oil-in-water emulsion. 225. - A method of treating plants, comprising the step of contacting the foliage of the plant with a biologically effective amount of a composition according to any of claims 135, 136 or 148 to 224. 226.- A method for increase the production of a crop field, comprising the steps of: (a) planting a crop in a field, (b) substantially freeing the field from one or more weed species that could decrease crop production by applying to the weed species a herbicidally effective amount of a composition comprising (i) a foliar herbicide, (ii) an aqueous diluent, (iii) a first excipient substance that is amphiphilic; characterized in that the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1.3 and about 1: 100; and wherein said composition forms anisotropic aggregates in or on a wax layer; (c) allow the crop to mature and (d) harvest the crop. 227.- A method to increase the production of a crop field, comprising the steps of: (a) substantially freeing the field from one or more weed species that could decrease crop production by applying to the weed species a herbicidally effective amount of a composition comprising (i) a foliar herbicide, (i) an aqueous diluent, (iii) a first excipient substance that is amphiphilic; further characterized in that the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100; and wherein said composition forms apisotropic aggregates in or on a wax layer; (b) plant the crop in the field, (c) allow the crop to mature, and (d) harvest the crop. 228. A plant treatment method comprising contacting the foliage with a composition comprising (a) water, (b) a biologically effective amount of an exogenous chemical and (c) a first excipient substance that is amphiphilic; characterized in that the weight / weight ratio of said first excipient substance to the exogenous chemical is between about 1: 3 and about 1: 100; and wherein said composition forms anisotropic aggregates in or on a wax layer, and wherein the biological effectiveness of the composition is greater than that of otherwise similar compositions that do not form said anisotropic aggregates. 229. - The method according to claim 10, further characterized in that the first excipient substance is Fluorad FC-135 or Fluorad FC-754. 230. The method according to claim 20, further characterized in that the second excipient substance is Fluorad FC-135 or Fluorad FC-754 231. The composition according to claim 88, further characterized in that the first excipient substance is Fluorad. FC-135 or Fluorad FC-754. 232. The composition according to claim 98, further characterized in that the second excipient substance is Fluorad FC-135 or Fluorad FC-754. 233. The composition according to claim 160, further characterized in that the first excipient substance is Fluorad FC-135 or Fluorad FC-754. 234. The composition according to claim 170, further characterized in that the second excipient substance is Fluorad FC-135 or Fluorad FC-754. 235.- An in vitro test method for selecting an exogenous chemical composition that has increased biological effectiveness when applied to plants, which comprises the steps of: (1) providing a microscope glass slide coated with a thin uniform layer of wax, so that the wax layer on the slide shows a dark field when illuminated by polarized light transmitted and examined through a microscope, (2) prepare a sample of an aqueous solution or dispersion of an exogenous chemical composition, diluted or concentrated if necessary so that the concentration of exogenous chemical is from about 15% to about 20% by weight of the composition, (3) placing the slide on a stage of a microscope that transmits polarized light through the slide, (4) placing a drop of the sample on the layer of wax for forming a test slide, (5) holding the test slide approximately at room temperature for a period of about 5 to about 20 minutes, (6) determining at the end of that period whether when the polarized light is transmitted the drop site on the test slide displays birefringence and (7) selecting for biological evaluation a composition in which birefringence is deployed. 236.- An in vitro test method for selecting a composition of an excipient substance that provides increased biological effectiveness of an exogenous chemical when applied together with the plant, which comprises the steps of: (1) providing a slide of microscope glass coated with a thin, uniform layer of wax, such that the wax layer on the slide exhibits a dark field when illuminated by polarized light transmitted and examined through a microscope, (2) preparing a sample of an aqueous solution or dispersion of a composition of a excipient substance, diluted or concentrated if necessary so that the concentration of excipient substance is about 5% to about 7% by weight of the composition, (3) placing the slide on a slide of a microscope that transmits polarized light through the slide, (4) placing a drop of the sample on the wax layer to form a test slide, (5) maintain the test slide at approximately room temperature for a period of about 5 to about 20 minutes, (6) determine at the end of said test pad whether when transmitting polarized light the site of the drop on the test slide displays birefringence and (7) select for biological evaluation a composition in which birefringence is displayed.
MXPA/A/1999/003845A 1996-10-25 1999-04-23 Composition and method for treating plants with exogenous chemicals MXPA99003845A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US2931796P 1996-10-25 1996-10-25
US60/029,317 1996-10-25
US3488797P 1997-01-31 1997-01-31
US60/034,887 1997-01-31
US3978997P 1997-03-04 1997-03-04
US60/039,789 1997-03-04

Publications (2)

Publication Number Publication Date
MX9903845A MX9903845A (en) 1999-08-01
MXPA99003845A true MXPA99003845A (en) 1999-10-14

Family

ID=

Similar Documents

Publication Publication Date Title
JP4160123B2 (en) Compositions and methods for treating plants with exogenous chemicals
JP4155601B2 (en) Compositions and methods for treating plants with exogenous chemicals
MXPA99003845A (en) Composition and method for treating plants with exogenous chemicals
MXPA99003847A (en) Composition and method for treating plants with exogenous chemicals
CN101422148A (en) Composition and method for treating plants with exogenous chemicals
BR9713324B1 (en) aqueous and liquid concentrates, plant treatment composition and plant treatment processes for increasing yield of a field crop and in vitro test process.
MXPA99003839A (en) Composition and method for treating plants with exogenous chemicals
HK1022076B (en) Composition and method for treating plants with exogenous chemicals
HK1022076A (en) Composition and method for treating plants with exogenous chemicals
MXPA99003840A (en) Composition and method for treating plants with exogenous chemicals
PL190108B1 (en) Composition for and method of treating plants with exogenous chemicals
MXPA99003842A (en) Composition and method for treating plants with exogenous chemicals