WO2019092156A1 - Agricultural pesticide compositions - Google Patents

Agricultural pesticide compositions Download PDF

Info

Publication number
WO2019092156A1
WO2019092156A1 PCT/EP2018/080699 EP2018080699W WO2019092156A1 WO 2019092156 A1 WO2019092156 A1 WO 2019092156A1 EP 2018080699 W EP2018080699 W EP 2018080699W WO 2019092156 A1 WO2019092156 A1 WO 2019092156A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
guar
water
instance
control agent
Prior art date
Application number
PCT/EP2018/080699
Other languages
French (fr)
Inventor
Laurianne Françoise Marie MOITY
Monique Martine Françoise ADAMY
Original Assignee
Rhodia Operations
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 Rhodia Operations filed Critical Rhodia Operations
Publication of WO2019092156A1 publication Critical patent/WO2019092156A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system

Definitions

  • the present invention relates to an aqueous composition comprising at least an auxin herbicide and a drift control agent.
  • It relates more particularly to a concentrated blend of at least one water-soluble salt of an auxin herbicide and of a drift control agent.
  • auxin herbicides are a well-known class of herbicides used to kill weeds by inducing hormonal effects on sprayed plants. They are thus commonly used to control auxin- susceptible plant growth. Typical representatives of auxin herbicides include 2,4-D (2,4-dichlorophenoxyacetic acid) and dicamba (3,6-dichloro-2-methoxybenzoic acid).
  • Spray drift is a problem frequently faced when using this class of herbicides.
  • Spray drift is defined by the Environmental Protection Agency as the movement of pesticide dust or droplets through the air at the time of application or soon thereafter, to any site other than the area intended.
  • Non-target plant damage associated with auxin herbicide spray drift is a major concern for crop growers nowadays.
  • unintentional application of auxin herbicides to a sensitive plant generally causes severe injury, loss of yield, and even death of the non-target plants.
  • drift control agents can be defined as chemical agents that enhance drift control of spray applied pesticide composition and/or provides "anti-rebound" properties to the spray applied pesticide composition, that is, reduces rebound of the spray applied pesticide from a target substrate, such as e.g., the foliage of a target plant.
  • Typical examples of drift control agents include for instance polysaccharide polymers, polyacrylamide polymers and emulsified fatty compounds.
  • the drift control agent may be added to the spray tank (so-called tank-mix adjuvants) or may be incorporated directly into the concentrated herbicide composition (so- called built-in adjuvants).
  • Tank mixes are combinations of agricultural products (pesticide formulation and tank mix adjuvant compositions) that a farmer would pour into a tank (in which the tank mix is prepared), with water and perhaps other additives, mix (optionally by stirring) and then apply on the field shortly thereafter, as these mixes are typically not stable for extended periods of time.
  • tank mixes face a variety of issues such as use of incorrect ingredients, human error in measuring the relative component amounts, and improper mixing steps. This can result in reduced effectiveness of the spray formulation, precipitation or gelation in the tank, clogged spray nozzles or clogged screens, excessive residue or runoff, or plant phyto- toxicity.
  • drift control agents such as for instance polysaccharide polymers, polyacrylamide polymers and emulsified fatty compounds
  • concentrated compositions of at least one water-soluble salt of an auxin herbicide containing a relatively high amount of a water-soluble salt whether it be a water-soluble salt of said auxin herbicide alone or a combination of a water-soluble salt of said auxin herbicide with a water-soluble salt of an additional herbicide and/or with added water-soluble salt
  • drift control agents such as for instance polysaccharide polymers, polyacrylamide polymers and emulsified fatty compounds
  • typical polymeric drift control agents in particular water-soluble polymers such as polysaccharide polymers (e.g. guars) or polyacrylamide polymers, need to be added into such formulations in a suspended form (for instance in a incompletely hydrated form) to avoid a significant and detrimental increase in viscosity.
  • water-soluble polymers such as polysaccharide polymers (e.g. guars) or polyacrylamide polymers
  • drift control agent is in the form of an emulsified fatty compound
  • a suspending agent to favor long term stability of the emulsion in order to avoid phase separation which would be also detrimental to the formulation stability and/or to the drift control properties.
  • the main difficulty lies in the fact that the performances of traditional suspending agents, such as for instance xanthan gum, or silica used in the prior art, are reduced in the presence of a relatively high amount of a water-soluble salt, which may especially impact some target attributes, such as for instance storage stability over time.
  • a relatively high amount of a water-soluble salt and thus a high electrolytic level
  • the presence of a relatively high amount of a water-soluble salt (and thus a high electrolytic level) in the concentrated composition can potentially prevent the full hydration of such traditional suspending agents, thereby negatively impacting their performances.
  • a suspending agent exhibiting improved properties, especially in the presence of a relatively high amount of a water-soluble salt, and making it possible to prepare stable concentrated compositions of at least one water-soluble salt of an auxin herbicide and of at least one drift control agent, in particular in the case where said drift control agent is in the form of particles (for instance particles of an incompletely hydrated water-soluble polymer) or in the form of droplets (for instance droplets of a fatty drift control agent formulated as an emulsion).
  • the present invention relates to, in one aspect, a pesticide composition
  • a pesticide composition comprising, by total weight of the composition:
  • -a pesticide comprising at least one water-soluble salt of an auxin herbicide
  • a drift control agent suspended in an aqueous liquid medium a drift control agent suspended in an aqueous liquid medium
  • a suspending agent in an amount effective to impart shear thinning properties to the composition, the suspending agent comprising at least one organically modified and beneficiated smectite clay.
  • the suspending agent is present in an amount effective to impart shear thinning properties to the composition.
  • the drift control agent of the invention (which is either in the form of particles (for instance particles of an incompletely hydrated water-soluble polymer) or in the form of droplets (for instance droplets of a fatty drift control agent formulated as an emulsion)) will thus remain suspended if the yield strength in the medium is sufficient to overcome the effect of settling or buoyancy on those particles / droplets.
  • auxin herbicide refers to a herbicide that functions as a mimic of an auxin plant growth hormone, thereby affecting plant growth regulation.
  • auxin herbicides that are suitable for use in the herbicidal compositions of the present invention include, without limitation, benzoic acid herbicides, phenoxy herbicides, pyridine carboxylic acid herbicides, pyridine oxy herbicides, pyrimidine carboxy herbicides, quinoline carboxylic acid herbicides, and benzothiazole herbicides.
  • the auxin herbicide is selected in the group consisting of 2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB (4-(2,4- dichlorophenoxy)butanoic acid), dichloroprop (2-(2,4-dichlorophenoxy)propanoic acid), MCPA ((4-chloro-2-methylphenoxy)acetic acid), MCPB (4-(4-chloro-2- methylphenoxy)butanoic acid), aminopyralid (4-amino-3,6-dichloro-2-pyridinecarboxylic acid), clopyralid (3,6-dichloro-2-pyridinecarboxylic acid), fluoroxypyr ([(4-amino-3,5-dichloro-6- fluoro-2-pyridinyl)oxy]acetic acid), triclopyr ([(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid), diclopyr, mecoprop (2-
  • the auxin herbicide is dicamba, or an agriculturally acceptable salt or ester thereof, for instance dicamba sodium salt, dicamba potassium salt, dicamba monoethanolamine salt, dicamba diethanolamine salt, dicamba isopropylamine salt, dicamba diglycolamine salt, dicamba N,N-bis-(3- aminopropyl)methylamine salt or dicamba dimethylamine salt.
  • the dicamba salt is (i) a secondary, tertiary or quaternary alkylamine or (ii) a primary, secondary, tertiary or quaternary alkanolamine, alkylalkanolamine or alkoxyalkanolamine salt, wherein the alkyl and alkanol groups are saturated and contain from C1 -C4 carbon atoms.
  • the pesticide comprises a dicamba salt, wherein the salt is N,N-bis(3-aminopropyl)methylamine, diethanolamine, monoethanolamine, dimethylamine, isopropylamine, dimethylethanolamine, diglycolamine, potassium, choline, or sodium.
  • the pesticide comprises dicamba diglycolamine (DGA) salt or dicamba N,N-bis(3-aminopropyl)methylamine (BAPMA) salt.
  • dicamba salts that can be used according to the present invention, especially dicamba polyamine salts, are recited for instance in WO2013/189773 which is herein incorporated by reference in its entirety.
  • the herbicidal composition comprises at least 2,4-D, or an agriculturally acceptable salt or ester thereof.
  • a herbicidal composition of the invention may comprise a 2,4-D salt selected in the group consisting of : the choline, dimethylamine, and isopropylamine salts, and combinations thereof.
  • a herbicidal composition of the invention may comprise a 2,4-D ester selected in the group consisting of : the methyl, ethyl, propyl, butyl (2,4-DB), and isooctyl esters, and combinations thereof.
  • the concentrated composition of the invention contains at least one water-soluble salt of an auxin herbicide as described previously, in particular at least one agriculturally acceptable water-soluble salt of dicamba, for instance dicamba sodium salt, dicamba potassium salt, dicamba monoethanolamine salt, dicamba diethanolamine salt, dicamba isopropylamine salt, dicamba diglycolamine salt, dicamba N,N-bis-(3-aminopropyl)methylamine salt or dicamba dimethylamine salt, and combinations thereof.
  • dicamba for instance dicamba sodium salt, dicamba potassium salt, dicamba monoethanolamine salt, dicamba diethanolamine salt, dicamba isopropylamine salt, dicamba diglycolamine salt, dicamba N,N-bis-(3-aminopropyl)methylamine salt or dicamba dimethylamine salt, and combinations thereof.
  • the concentrated composition of the invention contains at least one water-soluble salt of an auxin herbicide as described previously, in particular at least one agriculturally acceptable water-soluble salt of 2,4-D, for instance 2,4-D choline salt, 2,4-D dimethylamine salt, or 2,4-D isopropylamine salt, and combinations thereof.
  • a concentrated composition of the invention usually contains at least 300 g/l, more preferably at least 400 g/l, and in particular at least 450 g/l acid equivalents (a.e.) of auxin herbicide, in particular dicamba.
  • the concentrated composition of the invention may comprise at least 300 g/L acid equivalents (a.e.) of at least one water-soluble salt of an auxin herbicide, in particular dicamba.
  • a concentrated composition of the invention contains usually up to 800 g/l, preferably up to 700 g/l, more preferably up to 650 g/l, and in particular up to 600 g/l acid equivalents (a.e.) of auxin herbicide, in particular dicamba.
  • a composition of the invention comprises an aqueous liquid medium.
  • aqueous medium means a single phase liquid medium that contains more than a trace amount of water, typically, based on 100 pbw of the aqueous medium, more than 0.1 pbw water. Suitable aqueous media more typically comprise, based on 100 pbw of the aqueous medium, greater than about 5 pbw water, even more typically greater than 10 pbw water. In one embodiment, the aqueous medium comprises, based on 100 pbw of the aqueous medium, greater than 40 pbw water, more typically, greater than 50 pbw water. The aqueous medium may, optionally, further comprise water soluble or water miscible components dissolved in the aqueous medium.
  • water miscible as used herein means miscible in all proportions with water.
  • Suitable water miscible organic liquids include, for example, (CrC 3 )alcohols, such as methanol, ethanol, and propanol, and (CrC 3 )polyols, such as glycerol, ethylene glycol, and propylene glycol.
  • a composition of the invention comprises greater than about 5 wt% of an aqueous liquid medium, for instance greater than about 10 wt%, for instance from about 10 wt% to about 80 wt%, for instance from about 15 wt% to about 75 wt% of an aqueous liquid medium relative to the total weight of the composition.
  • the suspending agent used in a composition of the present invention comprises at least one smectite clay
  • the smectite clay used in the present invention is an organically modified smectite clay (organoclay), i.e. a smectite clay modified with an organic chemical composition.
  • organoclay organically modified smectite clay
  • the smectite clay used in the present invention is the ion-exchanged reaction product of (a) a smectite clay and (b) one or more quaternary ammonium compounds and/or (c) one or more organic materials.
  • the organically modified smectite clay of the invention is an organic chemical/clay mixture prepared by the reaction of a smectite clay and one or more quaternary ammonium compounds, and/or optionally one or more organic materials.
  • Smectite clays are swellable layered clays which contain individual platelets.
  • Useful swellable layered materials include phyllosilicates such as smectite clay minerals, e.g., montmorillonite, particularly sodium montmorillonite; bentonite; hectorite; saponite; stevensite; beidellite; and the like.
  • smectite clay minerals e.g., montmorillonite, particularly sodium montmorillonite; bentonite; hectorite; saponite; stevensite; beidellite; and the like.
  • Smectite clays used according to the invention may typically be bentonite and hectorite.
  • Smectite clays possess some structural characteristics similar to the better-known minerals talc and mica.
  • Their crystal structures consist of two-dimensional layers formed by fusing two silica tetrahedral sheets to an edge-shared dioctahedral or trioctahedral sheet of either alumina (for example bentonite) or magnesia (for example hectorite) - each of the different smectite clays having somewhat different structures. Stacking of these layers in nature in depths of hundreds or more is caused by ionic and weak Van der Waals forces. The area between the platelets is occupied by cations which balance the charge deficiency that is generated by isomorphous substitution (often called disharmonies) within the platelet lattices.
  • interlayer spacing refers to the distance between the internal faces of adjacent smectite clay platelet layers, either in the dry state or as incorporated into a polymer. The interlayer spacing is measured by standard X-Ray Diffraction techniques.
  • the smectite clays which may be used in the present invention are preferably smectite-type clays having a cationic exchange capacity of at least 50 milliequivalents per 100 grams of clay, 100% active clay basis, as determined by the well-known ammonium acetate or methylene blue methods.
  • Smectite-type clays are well known in the art and are commercially available from a variety of sources.
  • the clays Prior to use in the invention, the clays may preferably be converted to the sodium form if they are not already in this form. This may be conveniently carried out by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form.
  • the clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide, etc., and the mixture sheared, such as with a pugmill or extruder.
  • Representative smectite clays useful in accordance with the present invention are the following:
  • 0.55 ⁇ x ⁇ 1 .10, f ⁇ 4 and R is selected from the group consisting of Na, Li, NH 4 , and mixtures thereof;
  • 0 ⁇ x ⁇ 1.10, 0 ⁇ y ⁇ 1 .10, 0.55 ⁇ (x + y) ⁇ 1 .10, f ⁇ 4 and R is selected from the group consisting of Na, Li, NH 4 , and mixtures thereof; Hectorite
  • 0.57 ⁇ x ⁇ 1 .15, f ⁇ 4 and R is selected from the group consisting of Na, Li, NH 4 , and mixtures thereof;
  • 0.58 ⁇ x ⁇ 1 .18, 0 ⁇ y ⁇ 0.66, f ⁇ 4 and R is selected from the group consisting of Na, Li, NH 4 , and mixtures thereof;
  • R is selected from the group consisting of Na, Li, NH 4 , mixtures thereof.
  • 0.55 ⁇ x ⁇ 1 .10, 0 ⁇ y ⁇ 0.44, f ⁇ 4 and R is selected from the group consisting of Na, Li, NH 4 , and mixtures thereof.
  • the preferred clays used in the present invention are bentonite and hectorite.
  • the smectite clay used in the present invention is a beneficiated smectite clay, that is to say a smectite clay that has been purified so that some or most of the impurities in the crude clay have been removed.
  • Crude smectite clay can be defined as smectite clay containing gangue or non-clay material.
  • Beneficiated smectite clay used in the present invention differs from crude smectite clay in that gangue has been removed.
  • Beneficiated smectite clays used in the present invention are smectite clays that have undergone clay beneficiation process.
  • Compound(s) (b) of the invention is one or more quaternary ammonium compounds. Particularly useful are quaternary ammonium compounds which include those having the formula:
  • R1 comprises a group selected from (i) linear or branched aliphatic, aralkyl, or aromatic hydrocarbon groups having from 8 to 30 carbon atoms or (ii) alkyl or alkyl-ester groups having 8 to 30 carbon atoms;
  • R2, R3, and R4 are independently selected from the group consisting of (a) linear or branched aliphatic hydrocarbon, fluorocarbon, or other halocarbon groups having from 1 to about 30 carbon atoms; (b) aralkyl or aromatic groups having from 6 to about 30 carbon atoms, (c) alkoxylated groups containing from 1 to about 80 moles of alkylene oxide; (d) amide groups, (e) oxazolidine groups, (f) allyl, vinyl, or other alkenyl or alkynyl groups possessing reactive unsaturation and having from 2 to about 30 carbon atoms, and (g) hydrogen: and X' comprises an anion selected from the group consisting of chloride, methyl s
  • quaternary phosphonium and sulfonium based salts are defined as within the definition of quaternary ammonium compound.
  • the raw materials used to make the quaternary amonium compounds can be derived from natural oils such as tallow, soya, coconut and palm oil.
  • Useful aliphatic groups in the above formula may be derived from other naturally occurring oils including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils or fats.
  • the aliphatic groups may likewise be petrochemically derived from, for example, alpha olefins.
  • Representative examples of useful branched, saturated radicals included 12-methylstearyl and 12-ethylstearyl.
  • useful aromatic groups include benzyl and benzylic-type materials derived from benzyl halides, benzhydryl halides, trityl halides, halophenylalkanes wherein the alkyl chain has from 1 to 30 carbon atoms, such as 1 -halo-1 -phenyloctadecane; substituted benzyl moieties, such as those derived from ortho-, meta-, and para-chlorobenzyl halides, para- methoxybenzyl halides, ortho-, meta-, and para-nitrilobenzyl halides, and ortho-, meta-, and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 30 carbon atoms; and fused ring benzyl-type moieties, such as those derived from 2-halomethylnaphthalene, 9-halomethylanthracene, and 9-halomethylphenanthrene, wherein the halo
  • aromatic groups include aromatic-type substituents such as phenyl and substituted phenyl; N-alkyl and ⁇ , ⁇ -dialkyl anilines, where the alkyl groups contain between 1 and 30 carbon atoms; ortho-, meta-, and para-nitrophenyl, ortho-, meta-, and para-alkyl phenyl, wherein the alkyl group contains between 1 and 30 carbon atoms; 2-, 3-, and 4-halophenyl wherein the halo group is defined as chloro, bromo, or iodo; and 2-, 3-, and 4-carboxyphenyl and esters thereof, where the alcohol of the ester is derived from an alkyl alcohol, wherein the alkyl group contains between 1 and 30 carbon atoms, aryl such as phenol, or aralkyl such as benzyl alcohols; and fused ring aryl moieties such as naphthalene, anthracene, and phenanthrene.
  • Preferred quaternary ammonium compounds for purposes of the invention comprises a quaternary ammonium salt that contains at least one, preferably two or three, hydrocarbon chains having from about 8 to about 30 carbon atoms and either no hydrophilic carbon chains or having hydrophilic radicals having a total of about 9 moles of ethylene oxide or less.
  • Some examples of preferred quaternary ammonium compounds to make the compositions of this invention are: dimethyl bis[hydrogenated tallow] ammonium chloride (2M2HT), methyl benzyl bis[hydrogenated tallow] ammonium chloride (MB2HT), and methyl tris[hydrogenated tallow alkyl] chloride (M3HT).
  • 2M2HT dimethyl bis[hydrogenated tallow] ammonium chloride
  • MB2HT methyl benzyl bis[hydrogenated tallow] ammonium chloride
  • M3HT methyl tris[hydrogenated tallow alkyl] chloride
  • Materials suitable for optional element (c) of this invention include materials listed as anionic components in US 4,412,018, 4,434,075, and 4,577,1 12. These include materials that are capable of reacting with component (b) of this invention and for intercalation with component (a) as an alkyl quarternary ammonium-organic anion complex.
  • the molecular weight (gram molecular weight) of the organic anion is preferably 3,000 or less, and most preferably 1 ,000 or less and contains at least one anionic moiety per molecule as disclosed herein.
  • the organic anion is preferably derived from an organic acid having a pKA less than about 1 1.0. As indicated, the source acid must contain at least one ionizable hydrogen having the preferred pKA in order to allow the formation of the alkyl quarternary ammonium- organic anion complex.
  • Exemplary types of suitable acidic functional organic compounds useful in this invention include:
  • Carboxylic acids including: a) benzene carboxylic acids such as benzoic acid; ortho-, iso- and terephthalic acid; 1 ,2,3-benzenetricarboxylic acid; 1 ,2,4-benzenetricarboxylic acid; 1 ,3,5-benzenetricarboxylic acid; 1 ,2,4,5-benzenetetracarboxylic acid; 1 ,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid); b) alkyl carboxylic acids having the formula CH3(CH2)n-COOH, wherein n is a number from 0 to 20; such compounds include acetic acid; pentanoic acid; hexanoic acid; heptanoic acid; octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; lauric acid; tridecanoic acid; tetradecanoic acid; pentadecano
  • Alkyl dicarboxylic acids having the formula HOOC-(CH2)n-COOH wherein n is 0 to 8 such as oxalic acid; malonic acid; succinic acid; glutaric acid; adipic acid; pimelic acid; suberic acid; azelaic acid; sebacic acid; d) Hydroxyalkyl carboxylic acids such as citric acid; tartaric acids; malic acid; mandelic acid; and 12-hydroxystearic acid; e) unsaturated alkyl carboxylic acids such as maleic acid; fumaric acid; and cinnamic acid; f) Fused ring aromatic carboxylic acids such as naphthalenic acid and anthracenecarboxylic acid; g) Cycloaliphatic acids such as cyclohexanecarboxylic acid; cyclopentanecarboxylic acid; furancarboxylic acids.
  • Organic sulfuric acids including: a) sulfonic acids including:
  • benzenesulfonic acids such as benzenesulfonic acid; phenolsulfonic acid; dodecylbenzenesulfonic acid; benzenedisulfonic acid; benzenetrisulfonic acids; para- toluenesulfonic acid; and
  • alkyl sulfonic acids such as methanesulfonic acid; ethanesulfonic acid; butanesulfonic acid; butanedisulfonic acid; sulfosuccinate alkyl esters such as dioctyl succinylsulfonic acid; and alkyl polyethoxy-succinyl sulfonic acid; and b) alkyl sulfates such as the lauryl half ester of sulfuric acid and the octadecyl half ester of sulfuric acid.
  • Organophosphorus acids including phosphonic acids, phosphinic acids, thiophosphinic acids, phosphites, and phosphates as described in US Patent No. 4,412,018.
  • Phenols such as phenol; hydroquinone; t-butylcatechol; p-methoxyphenol; and naphthols.
  • Amino acids such as the naturally occurring amino acids and derivatives thereof such as 6-aminohexanoic acid; 12-aminododecanoic acid; N-phenylglycine; and 3-aminocrotonic acid.
  • materials useful for element c) can be selected from a wide variety of non-anionic materials as described in U.S. Patent Application No. 09/064216, descriptions herein incorporated by reference. These materials are either water soluble, liquid, or can be made into a liquid at reaction temperature so that the aforementioned clay material absorbs them. These materials can be any of a wide range of materials and can have a wide range of molecular weights. Materials of this type suitable for element (c) of this invention include polyurethanes; polyamides; polyesters; polycarbonates; polyepoxides and polyolefins.
  • Such materials also include polyethers (polymers and copolymers) based on ethylene oxide, butylene oxide, propylene oxide, phenols and bisphenols; polyesters (polymers and copolymers) based on aliphatic and aromatic diols and polyurethanes based on aliphatic and aromatic diisocyanates, polyamides (polymers and copolymers) based on aliphatic and aromatic diamines, and polycarbonates (polymers and copolymers) based on aliphatic or aromatic diols; polycarboimides (polymers and copolymers) based on tetrabasic acids and diamines, vinyl polymers and copolymers based on vinyl monomers, styrene and derivatives of styrene; acrylic polymers and copolymers based on acrylic monomers; copolymers based on styrene, vinyl and acrylic monomers; polyolefin polymers and copolymers based
  • THIXATROL VF-10 and THIXATROL VF-20 which are liquid polyester amide copolymers made by RHEOX.
  • examples of other specific materials are polyvinylpyrrolidone (PVP) or its hydrolysis product, polyvinyl alcohol (PVA), polymethacrylamide, poly(N,N- dimethylacrylamide), poly(N-isopropylacrylamide), poly(N-acetamidacrylamide), poly(N- acetimidomethacrylamide), polyvinyloxazolidone, and polyvinylmethyl oxazolidone, polyoxypropylene, polyoxyethylene and copolymers thereof.
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • PVA polymethacrylamide
  • poly(N-isopropylacrylamide) poly(N-acetamidacrylamide)
  • poly(N- acetimidomethacrylamide) polyvinyloxazolidone
  • the materials (b) and (c) can be reacted together, or in any order, with the smectite clay.
  • the amount of quaternary compound and optional organic compound used can vary over wide ranges. This amount is defined as the millequivalent ratio which is the number of milliequivalents (m.e.) of the organic cation in the organoclay per 100 grams of clay, 100% active clay basis.
  • component (c), if present, is used at an amount of 5 to 100 milliequivalents, and more preferably 10 to 50 m.e., per 100g of clay, 100% active basis.
  • the organoclays useful in the composites of this invention may be prepared in a number of ways. One is to first disperse the smectite clay in water. The clay is preferably dispersed in water at a concentration of from about 1 to 80%, most preferably from about 2 to 8% by weight. Optionally, the slurry may be centrifuged to remove non-clay impurities that constitute about 10% to 50% of the starting clay composition. If the optional organic material is to be part of the composition, it is added to the clay/water dispersion and mixed.
  • This mixture can then be heated and is ion exchanged with a quaternary ammonium compound to form the final organoclay as a coagulate, which is washed with water and isolated by filtration. If only the optional organic material is used, it can be added to the purified clay/water slurry an adsorbed onto the clay. The clay is then isolated by drying.
  • a second general method to prepare this invention uses dry clay that is intimately mixed with the organic material in a heated device, such as an extruder.
  • the mixture can also have some water present to facilitate intercalation.
  • the quaternary ammonium compound and/or organic material is added and the final product is isolated. This composition can be washed with water and dried.
  • Both of the methods mentioned above where both components (b) and (c) are used can be modified by either: 1 ) reversing the order of addition, i.e., reacting the clay with the quaternary ammonium ion followed by the organic material; or 2) adding the quaternary ammonium compound and organic material to the clay simultaneously.
  • the reaction is preferably followed by drying and grinding the organoclay product.
  • the organoclay can further be incorporated into a polymer resin.
  • Suitable polymer resins include a very wide variety of resins. It can be any plastic material whether polar or non-polar. Such resins can include polyolefins which can consist of polyethylenes, polypropylenes, polybutylenes, polymethylpentane, polyisoprenes and copolymers thereof; copolymers of olefins and other monomers such as ethylene-vinyl acetate, ethylene acid copolymers, ethylene-vinyl alcohol, ethylene-ethyl acrylate, and ethylene-methyl acrylate. lonomers are also useful and comprise metal salts of polyolefins copolymerized with acrylic acid.
  • thermoplastic resins useful in this invention are acetals, acrylics, and cellulosics. Fluoropolymers and copolymers with other monomers are useful such as polytetrafluoroethylene (Teflon®), fluorinated ethylene-propylene, perfluoroalkoxy resins, polychlorotrifluoroethylene, ethylene-chlorofluoroethylene copolymer, polyvinylidene fluoride and polyvinylfluoride. Liquid crystal polymers, a family of polyester copolymers, can also be used. Additional polymers are nitrile resins, polyamides (nylons), polyphenylene ether and polyamide-imide copolymers.
  • polyesters are useful such as polyarylates, polybutylene terephthalate and polyethylene terephthalate.
  • Engineering resins such as polycarbonate, polyetherimide, polyetheretherketone, polyphenylene sulfide and thermoplastic polyimides are good candidates.
  • Polystyrene and copolymers such as ABS, SAN, ASA and styrene-butadiene are appropriate.
  • the sulfone based resins such as polysulfone, polyethersulfone and polyarylsulfone.
  • Elastomers comprising a wide variety of useful materials and include olefinic TPE's, polyurethane TPE's, and styrenic TPE's.
  • Chlorinated polymers such as PVC, and polyvinylidene dichloride can also be used.
  • miscible or immiscible blends and alloys of any of the above resin combinations are useful for this invention.
  • Thermoset polymers such as epoxies, polyester resins and curing rubbers can also be used.
  • Incorporation of the organoclay of the invention into a polymer resin can be accomplished by mixing or blending the organoclay by any means that can create sufficient shear.
  • the shear can be provided by any appropriate method such as mechanical, thermal shock, pressure changes, or ultrasonics as known in the art.
  • Particularly useful are methods where a flowable polymer is mixed with the organoclay by mechanical means such as extruders, roll mills, stirrers, Banbury® type mixers, Brabender® type mixers, and continuous mixers. Other methods for making this invention can be postulated by those knowledgeable in the art.
  • the organically modified and beneficiated smectite clay of the invention has a bulk density lower than 1 .5 g/cm 3 , for instance lower than 1 .0 g/cm 3 , for instance lower than 0.8 g/cm 3 , for instance lower than 0.7 g/cm 3 .
  • the organically modified and beneficiated smectite clay of the invention is in the form of a finely divided soft powder, with a particle size of 80% lower than 125 m (120#).
  • Bentone® DY CE (supplied by Elementis, and having a bulk density of 0.65 g/cm 3 ) is a typical example of organically modified and beneficiated smectite clay suitable according to the present invention.
  • a concentrated composition of the invention comprises greater than about 0.5wt% of an organically modified smectite clay of the invention, for instance greater than about 1wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
  • a concentrated composition of the invention comprises less than about 25wt% of an organically modified smectite clay of the invention, for instance less than about 15wt% of an organically modified smectite clay of the invention, for instance less than about 10wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
  • the present invention provides a pesticide composition characterized in that it comprises, as suspending agent, an organically modified smectite clay of the invention.
  • Another preferred subject matter of the invention is a process for the preparation of a concentrated composition of at least one water-soluble salt of an auxin herbicide exhibiting at the same time acceptable storage stability, dilution miscibility and stability and acceptable spray drift control properties when said concentrated composition is diluted in water in a spray tank, which is characterized in that an organically modified smectite clay of the invention, is added to the concentrated composition.
  • Another preferred subject matter of the invention is the use of an organically modified smectite clay of the invention for the improvement of the storage stability and of the suspending properties of a concentrated composition of the invention.
  • the suspension agent provides improved storage stability and suspending properties of a concentrated composition of the invention.
  • the suspension agent provides improved high temperature storage stability.
  • the suspending agent of the present invention in utilized in an amount that is effective, either alone or in combination with one or more other suspending agents, to impart shear thinning viscosity to the composition, typically in an amount, based on 100 pbw of the composition, of at least 0.5 pbw, for instance of from greater than 1 pbw, more typically from about 2 pbw, and even more typically from about 1 pbw, to about 10 pbw, more typically to about 8 pbw, and even more typically to about 5 pbw.
  • a concentrated composition of the invention comprises greater than about 0.5wt% of an organically modified smectite clay of the invention, for instance greater than about 1wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
  • a concentrated composition of the invention comprises less than about 25wt% of an organically modified smectite clay of the invention, for instance less than about 15wt% of an organically modified smectite clay of the invention, for instance less than about 10wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
  • drift refers to off-target movement of droplets of a pesticide composition that is applied to a target pest or environment for the pest.
  • Spray applied compositions typically exhibit decreasing tendency to drift with decreasing relative amount, typically expressed as a volume percentage of total spray applied droplet volume, of small size spray droplets, that is, spray droplets having a droplet size below a given value, typically, a droplet size of less than 150 micrometers (" ⁇ " ).
  • Spray drift of pesticides can have undesirable consequences, such as for example, unintended contact of phytotoxic pesticides with non-pest plants, such as crops or ornamental plants, with damage to such non-pest plants.
  • spray drift can me measured as follows : the aqueous pesticide compositions as described herein are sprayed through a nozzle under certain conditions, for example, a single, stationary XR1 1002 flat fan nozzle (Teejet) with an output of 0.64 liter in "1 at a pressure of 30 psi ( ⁇ 2 bar) in a flow-controlled hood (speed ⁇ 1 .6 MPH), and a droplet size distribution was measured perpendicular to the plane of spray pattern and below the nozzle tip, e.g., 35 cm.
  • An analyzer such as a HELOS VARIO particle size analyzer
  • VMD volume mean diameter
  • vol% percent by volume of the total spray volume
  • a composition of the invention may comprise any compound useful as drift control agent.
  • Water soluble polymers and fatty deposition control agents as described below are typical examples of suitable drift control agents according to the present invention.
  • Water soluble polymer as a drift control agent is typical examples of suitable drift control agents according to the present invention.
  • Suitable drift contol agents include water soluble polysaccharide polymers, for example, galactomannans such as guars, including guar derivatives, xanthans, polyfructoses such as levan, starches, including starch derivatives, such as amylopectin, and cellulose, including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • galactomannans such as guars, including guar derivatives, xanthans, polyfructoses such as levan
  • starches including starch derivatives, such as amylopectin
  • cellulose including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • Galactomannans are polysaccharides consisting mainly of the monosaccharides mannose and galactose.
  • the mannose-elements form a chain consisting of many hundreds of (1 ,4)- ⁇ - D-mannopyranosyl-residues, with 1 ,6 linked ⁇ -D-galactopyranosyl-residues at varying distances, dependent on the plant of origin.
  • Naturally occurring galactomannans are available from numerous sources, including guar gum, guar splits, locust bean gum and tara gum. Additionally, galactomannans may also be obtained by classical synthetic routes or may be obtained by chemical modification of naturally occurring galactomannans.
  • Guar gum refers to the mucilage found in the seed of the leguminous plant Cyamopsis tetragonolobus.
  • the water soluble fraction (85%) is called "guaran," which consists of linear chains of (1 ,4)-. ⁇ - ⁇ mannopyranosyl units-with a-D-galactopyranosyl units attached by (1 ,6) linkages.
  • the ratio of D-galactose to D-mannose in guaran is about 1 :2.
  • Guar gum typically has a weight average molecular weight of between 2,000,000 and 5,000,000 g/mol. Guars having a reduced molecular weight, such as for example, from about 50,000 to about 2,000,000 g/mol are also known.
  • Guar seeds are composed of a pair of tough, non-brittle endosperm sections, hereafter referred to as "guar splits," between which is sandwiched the brittle embryo (germ). After dehulling, the seeds are split, the germ (43-47% of the seed) is removed by screening, and the splits are ground. The ground splits are reported to contain about 78-82% galactomannan polysaccharide and minor amounts of some proteinaceous material, inorganic salts, water-insoluble gum, and cell membranes, as well as some residual seedcoat and embryo.
  • Locust bean gum or carob bean gum is the refined endosperm of the seed of the carob tree, Ceratonia siliqua. The ratio of galactose to mannose for this type of gum is about 1 :4. Locust bean gum is commercially available.
  • Tara gum is derived from the refined seed gum of the tara tree.
  • the ratio of galactose to mannose is about 1 :3.
  • Tara gum is commercially available.
  • native (i.e. not derivatized) polysaccharide gums such as for instance native guar gum, cassia gum or tamarind seed gum
  • Other galactomannans of interest are the modified galactomannans, including derivatized guar polymers, such as carboxymethyl guar, carboxymethylhydroxypropyl guar, cationic hydroxpropyl guar, hydroxyalkyl guar, including hydroxyethyl guar, hydroxypropyl guar, hydroxybutyl guar and higher hydroxylalkyl guars, carboxylalkyl guars, including carboxymethyl guar, carboxylpropyl guar, carboxybutyl guar, and higher carboxyalkyl guars, the hydroxyethylated, hydroxypropylated and carboxymethylated derivative of guaran, the hydroxethylated and carboxy
  • Xanthans of interest are xanthan gum and xanthan gel.
  • Xanthan gum is a polysaccharide gum produced by Xathomonas campestris and contains D-glucose, D-mannose, D-glucuronic acid as the main hexose units, also contains pyruvate acid, and is partially acetylated.
  • Levan is a polyfructose comprising 5-membered rings linked through ⁇ -2,6 bonds, with branching through ⁇ -2,1 bonds. Levan exhibits a glass transition temperature of 138°C and is available in particulate form. At a molecular weight of 1 -2 million, the diameter of the densely-packed spherulitic particles is about 85 nm.
  • Modified celluloses are celluloses containing at least one functional group, such as a hydroxy group, hydroxycarboxyl group, or hydroxyalkyl group, such as for example, hydroxymethyl cellulose, hydroxyethyl celluloses, hydroxypropyl celluloses or hydroxybutyl celluloses.
  • guar splits are reacted with one or more derivatizing agents under appropriate reaction conditions to produce a guar polysaccharide having the desired substituent groups.
  • Suitable derivatizing reagents are commercially available and typically contain a reactive functional group, such as an epoxy group, a chlorohydrin group, or an ethylenically unsaturated group, and at least one other substituent group, such as a cationic, nonionic or anionic substituent group, or a precursor of such a substituent group per molecule, wherein substituent group may be linked to the reactive functional group of the derivatizing agent by bivalent linking group, such as an alkylene or oxyalkylene group.
  • Suitable cationic substituent groups include primary, secondary, or tertiary amino groups or quaternary ammonium, sulfonium, or phosphinium groups.
  • Suitable nonionic substituent groups include hydroxyalkyl groups, such as hydroxypropyl groups.
  • Suitable anionic groups include carboxyalkyl groups, such as carboxymethyl groups. The cationic, nonionic and/ or anionic substituent groups may be introduced to the guar polysaccharide chains via a series of reactions or by simultaneous reactions with the respective appropriate derivatizing agents.
  • the guar may be treated with a crosslinking agent, such for example, borax (sodium tetra borate) is commonly used as a processing aid in the reaction step of the water-splits process to partially crosslink the surface of the guar splits and thereby reduces the amount of water absorbed by the guar splits during processing.
  • a crosslinking agent such for example, borax (sodium tetra borate) is commonly used as a processing aid in the reaction step of the water-splits process to partially crosslink the surface of the guar splits and thereby reduces the amount of water absorbed by the guar splits during processing.
  • crosslinkers such as, for example, glyoxal or titanate compounds, are known.
  • the drift control agent of the present invention is a non-derivatized galactomannan polysaccharide, more typically a non-derivatized guar gum.
  • non-derivatized guar gum is synonymous, and used interchangeably, with the terms “native guar” or "guar gum”.
  • the drift control agent is a derivatized galactomannan polysaccharide that is substituted at one or more sites of the polysaccharide with a substituent group that is independently selected for each site from the group consisting of cationic substituent groups, nonionic substituent groups, and anionic substituent groups.
  • the drift control agent of the present invention is derivatized galactomannan polysaccharide, more typically a derivatized guar.
  • Suitable derivatized guars include, for example, hydroxypropyl trimethylammonium guar, hydroxypropyl lauryldimethylammonium guar, hydroxypropyl stearyldimethylammonium guar, hydroxypropyl guar, carboxymethyl guar, guar with hydroxypropyl groups and hydroxypropyl trimethylammonium groups, guar with carboxymethyl hydroxypropyl groups and mixtures thereof.
  • the amount of derivatizing groups in a derivatized polysaccharide polymer may be characterized by the degree of substitution of the derivatized polysaccharide polymer or the molar substitution of the derivatized polysaccharide polymer.
  • the terminology "degree of substitution" in reference to a given type of derivatizing group and a given polysaccharide polymer means the number of the average number of such derivatizing groups attached to each monomeric unit of the polysaccharide polymer.
  • the derivatized galactomannan polysaccharide exhibits a total degree of substitution ("DS T ") of from about 0.001 to about 3.0, wherein:
  • DS T is the sum of the DS for cationic substituent groups ("DS ca tionic"), the DS for nonionic substituent groups ("DS n0 nionic”) and the DS for anionic substituent groups
  • DScationic is from 0 to about 3, more typically from about 0.001 to about 2.0, and even more typically from about 0.001 to about 1 .0,
  • DSnonionic is from 0 to 3.0, more typically from about 0.001 to about 2.5, and even more typically from about 0.001 to about 1 .0, and
  • DSanionic is from 0 to 3.0, more typically from about 0.001 to about 2.0.
  • molar substitution refers to the number of moles of derivatizing groups per moles of monosaccharide units of the guar.
  • the molar substitution can be determined by the Zeisel-GC method.
  • the molar substitution utilized by the present invention is typically in the range of from about 0.001 to about 3.
  • the drift control agent is a water soluble non-polysaccharide polymer.
  • Suitable water soluble non-polysaccaharide polymers include, for example, lecithin polymers, poly(alkyleneoxide) polymers, such as poly(ethylene oxide) polymers , and water soluble polymers derived from ethylenically unsaturated monomers.
  • Suitable water soluble polymers derived from ethylenically unsaturated monomers include water soluble polymers derived from acrylamide, methacrylamide, 2-hydroxy ethyl acrylate, and/or N-vinyl pyrrolidone, including homopolymers of such monomers, such as poly(acrylamide) polymers and polyvinyl pyrrolidone) polymers, as well as copolymers of such monomers with one or more comonomers.
  • Suitable water soluble copolymers derived from ethylenically unsaturated monomers include water soluble cationic polymers made by polymerization of at least one cationic monomer, such as a diamino alkyl (meth)acrylate or diamino alkyl (meth)acrylamide, or mixture thereof and one or more nonionic monomers, such as acrylamide or
  • the non-polysaccharide polymer exhibits a weight average molecular weight of greater than about 1 ,000,000 g/mol, more typically greater than about 2,000,000 g/mol to about 20,000,000 g/mol, more typically to about 10,000,000 g/mol.
  • the drift control agent comprises, for example, galactomannans such as guars, including guar derivatives, polyfructoses such as levan, starches, including starch derivatives, such as amylopectin, xyloglucans such as tamarind gum and tamarind gum derivatives such as hydroxypropyl tamarind gum, and cellulose, including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose,
  • hydroxyethylcellulose cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate, as well as cassia gum.
  • Tamarind (Tamahndus Indica) is a leguminous evergreen tall tree produced in the tropics.
  • Tamarind gum (tamarind powder or tamarind kernel powder), a xyloglucan polysaccharide, is obtained by extracting and purifying the seed powders, obtained by grinding the seeds of tamarind.
  • the polysaccharide molecule of the tamarind gum consists of a main linear chain of poly-glucose bearing xylose and galactoxylose substituents.
  • the drift control agent of the present invention is derivatized xyloglucan polysaccharide, more typically a derivatized tamarind.
  • Suitable derivatized tamarinds include, for instance, hydroxypropyl tamarind gum, which may further contain substituent groups such as carboxyalkyl substituents (e.g. carboxymethyl or carboxyethyl) or hydrophobic substituents (e.g. C4-C24 linear or branched alkyl chains), such as those described in WO2016/124467, which is incorporated by reference.
  • substituent groups such as carboxyalkyl substituents (e.g. carboxymethyl or carboxyethyl) or hydrophobic substituents (e.g. C4-C24 linear or branched alkyl chains), such as those described in WO2016/124467, which is incorporated by reference.
  • the drift control agent is a cationic tamarind gum derivative, for instance a cationic tamarind gum derivative having a cationic degree of substitution DScat ranging from about 0.001 to about 3.
  • the drift control agent is a tamarind gum derivative, such as a tamarind seed gum polymer, for instance a hydroxypropyl tamarind
  • the pesticide composition of the invention does not comprise a combination of dipotassium phosphate and tri-potassium citrate.
  • the pesticide composition of the invention does not comprise a combination of di- potassium phosphate, potassium nitrate and tri-potassium citrate.
  • the drift control agent is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 0.5 pbw, or of 1 pbw, or in another embodiment of 1.2 pbw, or in another embodiment, 1.4 pbw, or in another embodiment, 1 .6 pbw, or in another embodiment, 1.8 pbw, or in yet another further embodiment, 2 pbw, or in another embodiment, 2.4 pbw, or in a further embodiment, 3 pbw, or in another embodiment, 3.5 pbw, or in another embodiment, 3.8 pbw, or in another embodiment, 4 pbw, or in another embodiment, 4.5 pbw, or one embodiment, 5 pbw, or in another embodiment, 7 pbw, or in a further embodiment, 8 pbw, or in another embodiment, 10 pbw, or in yet another
  • the water-soluble polymer is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 1 .8 pbw.
  • the drift control agent for instance the water-soluble polymer, is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 3.8 pbw.
  • the drift control agent for instance the water-soluble polymer s present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 4 pbw.
  • the drift control agent for instance the water-soluble polymer, is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 2 pbw.
  • the drift control agent for instance the water-soluble polymer
  • the drift control agent is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 20 pbw, or in another embodiment of 18 pbw, or in another embodiment, 17 pbw, or in another embodiment, 16 pbw, or in another embodiment, 14 pbw, or in yet another further embodiment, 13 pbw, or in another embodiment, 12 pbw, or in a further embodiment, 10 pbw, or in another embodiment, 9 pbw, or in another embodiment, 8 pbw, or in another embodiment, 7 pbw, or in another embodiment, 6 pbw, or one
  • the drift control agent for instance the water-soluble polymer
  • the drift control agent is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 12 pbw.
  • the drift control agent for instance the water-soluble polymer
  • the drift control agent is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 8 pbw.
  • the drift control agent for instance the water-soluble polymer, is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 20 pbw.
  • a composition of the invention may comprise greater than about 1 wt% of a drift control agent suspended in a liquid medium, for instance greater than about 2wt%, for instance greater than about 3 wt%, for instance greater than about 4 wt%, for instance at least 5wt% of a drift control agent, for instance an incompletely hydrated water-soluble polymer, suspended in a liquid medium.
  • the pesticide composition of the present invention comprises:
  • hydration inhibitor which in one embodiment is a glycol, a glycol
  • Fatty deposition control agents are also suitable as drift control agents in a composition of the invention.
  • emulsified fatty deposition control agents in particular combinations of a fatty deposition control agent and of a surfactant, may be used according to the invention.
  • Any known emulsifying surfactant can be combined to a fatty deposition control agent of the invention to obtain an emulsified fatty deposition control agent useful as drift control agent according to the present invention.
  • Fatty compounds suitable as the fatty deposition control agent as described herein are typically insoluble in water and form a two phase mixture with water in all proportions.
  • the fatty deposition control agent comprises one or more fatty alkanes, fatty acids, fatty amines, fatty amides, fatty glycerides, fatty triglycerides, fatty acid esters, or any mixture thereof.
  • the fatty deposition control agent comprises one or more fatty alkanes, fatty acids, fatty amides, fatty glycerides, or any mixture thereof.
  • the fatty deposition control agent in one embodiment, is a mixture of a fatty acid and a fatty triglyceride.
  • the fatty deposition control agent comprises one or more fatty alkanes. In another embodiment, the fatty deposition control agent comprises one or more fatty acids. In another embodiment, the fatty deposition control agent comprises one or more fatty glycerides. In another embodiment, the fatty deposition control agent comprises one or more fatty triglycerides. In another embodiment, the fatty deposition control agent comprises one or more fatty acid esters. In another embodiment, the fatty deposition control agent comprises one or more fatty amines. In another embodiment, the fatty deposition control agent comprises one or more fatty amides. Suitable glycerides are mono- di-, and/or tri-esters of glycerol with one or more fatty acids. In one embodiment, the fatty deposition control agent comprises one or more fatty glycerides, which may comprise one or more fatty monoglycerides, fatty diglycerides, fatty triglycerides, or a mixture thereof.
  • the fatty glyceride or triglyceride comprises one or more compounds according to structure (I la)
  • R 20 , R 21 , and R 22 are each independently H, (C 6 -C 30 )alkyl, (Ci 0 -C 2 4)alkyl, or
  • R 20 , R 21 , and R 22 are each independently (Ci 4 -Ci 8 )alkyl. In one embodiment, R 20 , R 21 , and R 22 are each independently (Cio-C 24 )alkyl. In one embodiment, R 20 , R 21 , and R 22 are each independently (Ci 6 -Ci 8 )alkyl. In one embodiment, R 20 , R 21 , and R 22 are each independently (C 6 -C 3 o)alkyl. In one embodiment, R , R , and R are each independently (C 6 -C 3 o)alkenyl.
  • R 20 , R 21 , and R 22 are each independently (Ci 0 -C 24 )alkenyl.
  • R 20 , R 21 , and R 22 may each be linear or branched and may each, optionally, be substituted on one or more carbon atoms with hydroxyl, and provided that at least one of R 20 , R 21 , and R 22 is not H.
  • AlkyI moieties suitable as groups of structure (lla) include, for example, (C 4 -C 3 o)hydrocarbon group.
  • Alkenyl moieties suitable as groups of structure (lla) may be mono-unsaturated or poly- unsaturated.
  • the fatty glyceride comprises one or more fatty monoglyceride compounds according to structure (l la) wherein two of R 20 , R 21 and R 22 are each
  • R 20 , R 21 and R 22 independently H and the remaining one of R 20 , R 21 and R 22 is (C 6 -C 3 o)alkyl, more typically (C 6 -C 2 4)alkyl, or (C 6 -C 3 o)alkenyl, more typically (C 8 -C 2 4)alkenyl.
  • the fatty glyceride comprises one or more fatty diglyceride compounds according to structure (l la) wherein two of R 20 , R 21 and R 22 are each independently
  • (C 6 -C 30 )alkyl more typically (C 6 -C 2 4)alkyl, or (C 6 -C 30 )alkenyl, more typically (C 8 -C 24 )alkenyl, and the remaining one of R 20 , R 21 and R 22 is H.
  • the fatty glyceride comprises one or more fatty triglyceride compounds according to structure (l la) wherein R 20 , R 21 , and R 22 are each independently (C 6 -C 24 )alkyl, more typically (C 6 -C 24 )alkyl, or (C 8 -C 24 )alkenyl, more typically (C 8 -C 24 )alkenyl.
  • R 20 , R 21 , and R 22 are each independently a linear or branched (C 4 -C 30 )alkyl, more typically, linear or branched (C 8 -C 24 )alkyl, even more typically linear or branched (Ci 2 -C 22 )alkyl, or (C 5 -C 24 )cycloalkyl, or linear or branched (C 4 -C 30 )alkenyl, more typically, linear or branched (C 8 -C 24 )alkenyl, even more typically linear or branched (Ci 2 -C 22 )alkenyl, or (C 5 -C 24 )cycloalkenyl, or (C 4 -C 30 )alkaryl, more typically (C 8 -C 24 )alkaryl, or (C 4 -C 30 )aralkyl, more typically (C 8 -C 24 )aralkyl.
  • R 20 , R 21 , and R 22 are each independently a linear
  • (C 8 -C 24 )alkyl or in another embodiment is a linear or branched (Ci 2 -C 22 )alkyl; or in another embodiment is a (C 5 -C 24 )cycloalkyl; or in another embodiment is a linear or branched (C 4 -C 30 )alkenyl; or in another embodiment is a linear or branched (C 8 -C 24 )alkenyl; or in another embodiment is a linear or branched (Ci 2 -C 22 )alkenyl; or in another embodiment is a (C 5 -C 24 )cycloalkenyl; or in another embodiment is a (C 4 -C 30 )alkaryl; or in another embodiment is a (C 8 -C 24 )alkaryl, or (C 4 -C 30 )aralkyl, more typically (C 8 -C 24 )aralkyl.
  • the fatty glyceride or triglyceride comprises one
  • R 20 , R 21 , and R 22 are each independently H, carboxy(C 6 -C 3 o)alkyl, more typically carboxy(Ci 0 -C 2 4)alkyl, or carboxy(C 6 -C 3 o)alkenyl, more typically carboxy(Ci 0 -C 2 4)alkenyl.
  • R 20 , R 21 , and R 22 are each independently carboxy(Ci 4 -Ci 8 )alkyl.
  • R 20 , R 21 , and R 22 are each independently carboxy(Cio-C 24 )alkyl.
  • R 20 , R 21 , and R 22 are each independently carboxy(Ci 6 -Ci 8 )alkyl.
  • R 20 , R 21 , and R 22 are each independently carboxy(C 6 -C 3 o)alkyl. In one embodiment, R 20 , R 21 , and R 22 are each independently carboxy(C 6 -C 3 o)alkenyl. In one embodiment, R 20 , R 21 , and R 22 are each independently carboxy(Cio-C 24 )alkenyl.
  • the alkyl portions of the respective carboxyalkyi groups and the alkenyl portions of the respective carboxyalkenyl groups may each be linear or branched and may each, optionally, be substituted on one or more carbon atoms with hydroxyl, and provided that at least one of R 20 , R 21 , and R 22 is not H.
  • Alkyl moieties suitable as the alkyl portion of the carboxyalkyi groups of structure (II) include, for example, (C 4 -C 30 )hydrocarbon group.
  • Alkenyl moieties suitable as the alkenyl portion of the carboxyalkenyl groups of structure (II) may be mono-unsaturated or poly-unsaturated.
  • the fatty glyceride comprises one or more fatty monoglyceride compounds according to structure (II) wherein two of R 20 , R 21 and R 22 are each
  • R 20 , R 21 and R 22 independently H and the remaining one of R 20 , R 21 and R 22 is carboxy(C 6 -C 30 )alkyl, more typically carboxy(C 6 -C 24 )alkyl, or carboxy(C 6 -C 30 )alkenyl, more typically
  • the fatty glyceride comprises one or more fatty diglyceride compounds according to structure (II) wherein two of R 20 , R 21 and R 22 are each independently
  • the fatty glyceride comprises one or more fatty triglyceride compounds according to structure (I I) wherein R 20 , R 21 , and R 22 are each independently
  • carboxy(C 6 -C 2 4)alkyl more typically carboxy(C 6 -C 2 4)alkyl, or carboxy(C 8 -C 2 4)alkenyl, more typically carboxy(C 8 -C 2 4)alkenyl.
  • the fatty glyceride is a mixture comprising at least one fatty
  • Suitable sources of fatty glycerides include naturally occurring mixtures of fatty glycerides and which may further comprise one or more fatty acids, such as vegetable oils, including, for example, palm oil, soybean oil, rapeseed oil, high erucic acid rapeseed oil, sunflower seed oil, peanut oil, cottonseed oil, palm kernel oil, linseed oil, coconut oil, olive oil, safflower oil, sesame oil, tung oil, canola oil, castor oil, meadowfoam seed oil, hemp oil, as well as mixtures of such oils.
  • Suitable fatty acid glycol ester surfactants include glycol fatty acid monoesters and glycol fatty acid diesters, more typically mono- and di-esters of glycol s and saturated or
  • the drift control agent comprises a fatty deposition control agent comprising one or more fatty glycerides, more typically vegetable oils, and one or more surfactants selected from fatty acid glycol ester surfactants.
  • a concentrated composition of the invention may comprise a fatty deposition control agent as described previously in an amount greater than 1 % by weight of composition, for instance in an amount ranging from 1 % by weight to 50 % by weight, in particular from 5 % by weight to 30 % by weight, for instance from 10 % by weight to 25 % by weight, relative to the total weight of the composition.
  • composition of the invention may optionally further comprise at least one hydration inhibitor component.
  • the term "hydration" in reference to the drift control agent or water soluble polymer component of the present invention means association of substituent groups, typically hydrophilic subsitutent groups, such as hydroxyl groups, of the water soluble polymer with water molecules, such as water molecules of the aqueous medium through, for example, hydrogen bonding.
  • the degree to which the drift control agent or water soluble polymer is hydrated can range from non-hydrated to completely hydrated, with degrees of partial hydration extending between the two extremes.
  • the drift control agent or water soluble polymer is capable of contributing to the viscosity of the composition of the present invention with the magnitude of the contribution being dependent on the degree of hydration of the water soluble polymer.
  • the degree of hydration of the water soluble polymer can thus be characterized based on the magnitude of the contribution that the water soluble polymer makes to the viscosity of the composition:
  • non-hydrated water soluble polymer makes no significant contribution to the viscosity of the composition.
  • the non-hydrated water soluble polymer would be in the form of a discontinuous phase, for example, discrete particles, that is dispersed in a continuous phase of the liquid medium, ideally with no interaction between the hydrophilic substituents of the polymer and any water molecules present in the liquid medium.
  • an aqueous medium there will generally be at least some interaction between the hydrophilic groups of polymer and water molecules of the aqueous medium at interfaces between the phases, for example, at the outer surfaces of the particles.
  • a "completely hydrated" water soluble polymer makes the maximum contribution to the viscosity of the composition that the water soluble polymer is capable of making. It is believed that in a completely hydrated water soluble polymer, association between the hydrophilic substituent groups of the water soluble polymer and water molecules dominates over interaction among the hydrophilic substituent groups, that the polymer chains of a completely hydrated water soluble polymer are thus in an unfolded, random coil conformation, and in the case where the liquid medium is an aqueous medium, the aqueous medium and completely hydrated water soluble polymer form a single phase, that is, the completely hydrated water soluble polymer is dissolved in the aqueous medium.
  • a "partially hydrated" water soluble polymer is a water soluble polymer wherein some of the hydrophilic substituent groups of the polymer are associated with water molecules. At a relatively low level of hydration, the partially hydrated water soluble polymer makes a relatively small contribution to the viscosity of the composition, while at a relatively high level of hydration, the viscosity contribution of a given amount of a partially hydrated water soluble polymer in a given medium approaches, but is less than, the maximum contribution that the amount of water soluble polymer is capable of making in that medium when completely hydrated.
  • Non-hydrated and “partially hydrated” are collectively referred to herein as “incompletely hydrated”.
  • a “hydration inhibitor”, as referred to herein is any compound that may be added to an aqueous medium to inhibit hydration of a water soluble polymer in the aqueous medium.
  • the degree of hydration of the water soluble polymer can be characterized by viscosity measurements.
  • the viscosity of a given amount of a water soluble polymer, in a given amount of an aqueous medium, in the presence of a given amount of a proposed hydration inhibitor, and under given shear conditions, as described in more detail below can be compared to the viscosity of the same amount of the water soluble polymer in the same amount of the aqueous medium in the absence of the proposed hydration inhibitor (the "baseline composition"). If the viscosity of the test composition is equal to that of the baseline composition, then the water soluble polymer of the test composition is deemed to be completely hydrated (and the proposed hydration inhibitor is ineffective in the amount tested to inhibit hydration of the polymer). If the viscosity of the test composition is less than that of the baseline composition, then the water soluble polymer of the test composition is deemed to be incompletely hydrated (and the proposed hydration inhibitor is effective in the amount tested to inhibit hydration of the polymer).
  • the incompletely hydrated water soluble polymer comprises solid particles of the water soluble polymer.
  • the presence of such particles can be detected by various means, such as for example, by viewing a sample of the composition of the present invention under an optical microscope.
  • the liquid medium is an aqueous liquid medium and at least a portion of the water soluble polymer is in the form of particles of the water soluble polymer.
  • the liquid medium is an aqueous liquid medium, at least a portion of the water soluble polymer is in the form of particles of the water soluble polymer, and at least a portion of such particles are dispersed, more typically suspended, in the aqueous liquid medium.
  • the presence of such particles in the composition of the present invention is detectable by, for example, optical microscopy.
  • the composition of the present invention exhibits a viscosity of less than 10 Pa.s, more typically from about 0.1 to less than 10 Pa.s, and even more typically from about 0.1 to less than 5 Pa.s, at a shear rate of greater than or equal to 10 s '
  • the composition of the present invention exhibits a non-Newtonian "shear thinning" viscosity, that is, a viscosity that, within a given range of shear stress, decreases with increasing shear stress.
  • a non-Newtonian "shear thinning" viscosity that is, a viscosity that, within a given range of shear stress, decreases with increasing shear stress.
  • Two general generally recognized categories of flow behavior that is, plastic flow behavior and pseudoplastic flow behavior, each include shear thinning flow behavior.
  • the composition of the present invention exhibits plastic flow behavior.
  • plastic in reference to flow behavior of a composition means the composition that exhibits a characteristic "yield strength", that is, a minimum shear stress required to initiate flow of the composition, and exhibits shear thinning behavior over some range of shear stress above the yield strength.
  • a plastic composition exhibits no flow when subjected to shear stress below its yield strength, and flows when subjected to shear stress above its yield strength, wherein, over an intermediate range of shear stress above its yield strength, the composition typically exhibits a non-Newtonian viscosity that decreases with increasing shear stress, that is, shear thinning behavior, and, at shear stresses above the intermediate range of shear stress, the composition may exhibit a viscosity that does not vary with shear stress, that is, Newtonian flow behavior.
  • the composition of the present invention exhibits pseudoplastic flow behavior.
  • the term "pseudoplastic" in reference to the flow behavior of a composition means that the composition exhibits a viscosity that decreases with increasing shear stress, that is, shear thinning behavior.
  • a composition having plastic or pseudoplastic rheological properties resists flow at low shear stress, but that when subjected to an elevated shear stress, such as being shaken in a bottle or squeezed through an orifice, the composition flows and can be easily pumped, poured, or otherwise dispensed from a container.
  • sedimentation or storage condition is a low shear process, having a shear rate in the range of from about 10 "6 reciprocal seconds (1/s or, equivalently, s "1 ) to about 0.01 s "1 and pumping or pouring is a relatively high shear process with a shear rate in the range of greater than or equal to about 1 s "1 , more typically from 100s “1 to 10,000 s "1 , and even more typically, from 100s "1 to 1 ,000 s "1 .
  • the hydration inhibitor is selected from surfactants, water soluble non- surfactant salts, water dispersible organic liquids, and mixtures thereof.
  • non-surfactant salts as used herein means salts that are not anionic, cationic, zwitterionic or amphoteric surfactants includes active ingredients, such as pesticide salts, whose primary activity is other than modification of interfacial surface tension.
  • water dispersible organic liquids includes water miscible organic liquids and water immiscible organic liquids that may be dispersed in water, such as for example, in the form of an emulsion of the water immiscible organic liquid in water.
  • the hydration inhibitor or hydration inhibitor component comprises a water dispersible organic liquid.
  • Suitable water dispersible organic liquids include, for example, (C1 -C18)alcohols, such as, for example, monohydric alcohols, such as methanol, ethanol, isopropanol, cetyl alcohol, stearyl alcohol, benzyl alcohol, oleyl alcohol, and polyhydric alcohols, such as, for example, 2-butoxyethanol, ethylene glycol, and glycerol, alkylether diols such as, for example, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and diethylene glycol monomethyl ether, and mixtures thereof.
  • the hydration inhibitor component comprises choline chloride.
  • the hydration inhibitor is selected from glycol, a glycol derivative, a glycerol, a glycerol derivative, or any combination thereof.
  • Glycols, glycol derivatives, glycerols and/or glycerol derivatives include, but are not limited, to polyglycols, polyglycol derivatives, aliphatic dihydroxy (dihydric) alcohols, polypropylene glycol, triethylene glycol, glycol alkyl ethers such as dipropylene glycol methyl ether, diethylene glycol.
  • glycols, glycol derivatives, glycerols and/or glycerol derivatives include but are not limited to polyglycols such as polyethylene glycols (PEG) and polypropylene glycols.
  • polyglycols such as polyethylene glycols (PEG) and polypropylene glycols.
  • Glycols are represented by the general formula CnH2n(OH)2, where n is at least 2.
  • glycols include ethylene glycol (glycol), propylene glycol (1 ,2-propanediol), 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,8-octanediol, 1 ,3- propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 4,5-octanediol and 3,4-hexanediol, neopenty glycol, pinacol, 2,2-diethyl-1 ,3-propyl-1
  • glycols, glycol derivatives, glycerols and/or glycerol derivatives include but are not limited to glycol stearate, ethylene glycol monostearate, ethylene glycol distearate, ethylene glycol amido stearate, dilaurate glycol, propylene glycol monostearate, propylene glycol dicaprylate, propylene glycol dicaprate diacetate glycol, dipalmite glycol, diformate glycol, dibutyrate glycol, dibenzorate glycol, dipalmate glycol, dipropionate glycol, monoacetate glycol, monopalmitate glycol and monoformate glycol.
  • glycols, glycol derivatives, glycerols and/or glycerol derivatives also include polypropylene glycol, triethylene glycol, dipropylene glycol methyl ether, or diethylene glycol.
  • Polyglycol derivatives include but are not limited to polypropylene glycols, as well as polyethylene glycol (PEG) 200-6000 mono and dilaurates, such as, PEG 600 dilaurate, PEG 600 monolaurate, PEG 1000 dilaurate, PEG 1000 monolaurate, PEG 1540 dilaurate and PEG 1540 monolaurate, polyethylene glycol 200-6000 mono and dioleates, such as, PEG 400 monoleate, PEG 600 dioleate, PEG 600 monooleate, PEG 1000 monoleate, PEG 1540 dioleate, PEG 1540 monooleate and polyethylene glycol 200-6000 mono and distearates, such as, PEG 400 distearate, PEG 400 monostearate, PEG 600 distearate, PEG 600 monostearate, PEG 1000 distearate, PEG 1000 monostearate, PEG 1500 monostearate, PEG 1540 distearate, PEG 1540 monostearate
  • glycerol derivatives include but are not limited to glycerol monolaurate, glycerol monostearate, glycerol distearate, glycerol trioleate, glycerol monooleate, glycerol dilaurate, glycerol dipalmitate, glycerol triacetate, glycerol tribenzoate, glycerol tributyrate, glycerol monopalmitate, glycerol trimyristate, glycerol trilaurate, glycerol tripalmitate and glycerol tristearate.
  • the composition of the present invention exhibits a viscosity of less than 10 Pa.s, more typically from about 0.1 to less than 10 Pa.s, at a shear rate of greater than or equal to 10 s ' In one embodiment, the composition of the present invention exhibits a viscosity of less than 7 Pa.s, more typically from about 0.1 to less than 7 Pa.s, at a shear rate of greater than or equal to 10 s ' In one embodiment, the composition of the present invention exhibits a viscosity of less than 5 Pa.s, more typically from about 0.1 to less than 5 Pa.s, at a shear rate of greater than or equal to 10 s "1 .
  • such a viscosity profile equates to the composition being flowable, i.e., able to be pumped.
  • This characteristic is an advantage as end use applications from a storage container typically prefer to pump components into the final application tank for crop application. For example, typically farmers will add components for a final tank mix into separate tanks, such as a tank for water, a tank for an adjuvant composition, a tank for a water conditioner, and have those components pumped into a final end use application tank.
  • the composition of the present invention is prepared on an as needed basis and is sufficiently stable, that is, a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation, such as, separation into layers and/or precipitation of components, such as, for example, separation of incompletely hydrated water-soluble polymer from the liquid medium, within the anticipated time period.
  • the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, such as, for example, one week, more typically, one month, even more typically 3 months, under given storage conditions, such as, for example, at room temperature.
  • the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, which in one embodiment is one week, more typically, one month, even more typically 3 months, under high termperature storage conditions, e.g., greater than 50 °C.
  • the composition of the present invention is shelf stable (i.e., exhibits at least part of the good storage stability as detailed above) at a temperature greater than 50 °C for at least 24 hours, or 48 hours, or in yet another embodiment, 72 hours.
  • the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, such as, for example, 24 hours, more typically, four days, even more typically, one week, under accelerated aging conditions at an elevated storage temperature of up to, for example, 54°C, more typically, 45°C.
  • a concentrated composition of the invention exhibits a Brookfield viscosity at 25°C and at 20 rpm of less than or equal to about 5,000 centiPoise ("cP"), more typically of less than or equal to 2,500 cP, for example from about 10 to about 1 ,500 , especially from about 10 to about 1 ,000 cP.
  • cP centiPoise
  • a concentrated composition of the invention exhibits good storage stability.
  • the criteria for assessing storage stability are that the formulation remains substantially homogeneous in visual appearance during storage and does not separate into layers of mutually insoluble liquid phases and does not form any solid precipitate upon quiescent standing
  • the concentrated composition of the invention remains stable during storage at temperatures from -5°C to 54°C for greater than or equal to 7 days, more typically for greater than or equal to 14 days (adaptation of CIPAC test MT46.3).
  • the concentrated composition of the invention remains stable during storage at room temperature for more than or equal to 7 days, more typically for greater than or equal to 14 days and even more typically for greater than or equal to 30 days.
  • a concentrated composition of the invention also exhibits good dilution stability and/or provides a suitable dispersion.
  • suitable dispersion is intended to denote a dispersion after dilution in water (CIPAC standard waters A or D) which exhibits substantially no or little phase separation (sedimentation, creaming, etc)) over time, in particular when it is stored for 30 minutes in a water bath thermostatted at 30°C, preferably for 2 hours in a water bath thermostatted at 30°C and ideally for 24 hours in a water bath thermostatted at 30°C (adaptation of CIPAC test MT41 and MT184).
  • the concentrated composition of the invention may comprise additional pesticides in addition to the auxin herbicide.
  • Suitable additional pesticides are pesticides as defined below.
  • Preferred additional pesticides are herbicides, such as
  • glyphosate e.g. glyphosate free acid, glyphosate ammonium salt, glyphosate isopropylammonium salt, glyphosate trimethylsulfonium salt, glyphosate potassium salt, glyphosate dimethylamine salt
  • glufosinate e.g. glufosinate ammonium salt
  • sulfosate - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop. More preferred additional pesticides are glyphosate and glufosinate.
  • a concentrated composition of the invention may comprise, in addition to said water-soluble salt of an auxin herbicide, at least one water-soluble salt of at least one additional herbicide.
  • a concentrated composition of the invention may further comprise at least one water-soluble salt of glyphosate and/or at least one water-soluble salt of glufosinate.
  • the total amount of water-soluble salts (whether it be a water-soluble salt of said auxin herbicide alone or a combination of a water- soluble salt of said auxin herbicide with a water-soluble salt of an additional herbicide and/or with added water-soluble salt) may be of at least 300 g/L.
  • a concentrated composition of the invention may also comprise, in addition to said water-soluble salt of an auxin herbicide, at least one additional herbicide which is insoluble in said concentrated composition, for instance present in a dispersed form.
  • a concentrated composition of the invention may also comprise, in addition to said water-soluble salt of an auxin herbicide, at least one additional herbicide present in a soluble form in a liquid medium different from the aqueous continuous phase and which is non-miscible in said aqueous phase, with said liquid medium being present in an emulsified form in said concentrated composition.
  • Suspo- emulsions are typical examples of such compositions.
  • the concentrated composition of the invention may comprise auxiliaries, such as
  • volatilization reduction additives solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants.
  • Suitable solvents and liquid carriers are organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol,
  • cyclohexanol glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and
  • tridecylbenzenes sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • phosphates are phosphate esters.
  • carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • the alkoxylate of the formula (I) is not a nonionic surfactant within the meaning of this invention.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are for instance polysaccharides (e.g. xanthan gum,
  • carboxymethylcellulose anorganic clays (organically modified or unmodified),
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as
  • alkylisothiazolinones alkylchloroisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron
  • organic colorants e.g. alizarin-, azo- and phthalocyanine colorants.
  • the composition of the invention is free or substantially free of ammonium-containing water conditioning agent, in particular ammonium sulfate.
  • the composition is concentrated blend of a at least one an auxin herbicide or salt thereof, a drift control agent and suspending agent as defined previously, which composition is stable, has a low viscosity, is easily transportable, is pourable and pumpable under field conditions, and is dilutable with water under field conditions to form a dilute pesticide composition for spray application to target pests.
  • the concentrated pesticide composition of the present invention is diluted with water, typically in a ratio of from 1 :10 to 1 :1 ,000 parts by weight pesticide concentrate composition: parts by weight water, for instance in a ratio of from 1 :10 to 1 :100 parts by weight pesticide concentrate composition: parts by weight water to form a dilute pesticide composition for spray application to target plants.
  • other components such as additional pesticide, polymer, surfactants, fertilizer, and/or other adjuvants, may be added to the dilute pesticide composition.
  • the pesticide composition of the present invention is applied, in dilute form, to foliage of a target plant at a rate of from about 0.25 pint, more typically about 0.5 pint, to about 5 pints, even more typically from about 1 pint to about 4 pints, as expressed in terms of the above described pesticide concentrate embodiment of the pesticide composition of the present invention (that is, comprising, based on 100 pbw of such composition, up to about 70 pbw, more typically from about 10 to about 60 pbw, more typically from about 25 to about 55 pbw, pesticide) per acre.
  • the pesticide composition is spray applied in dilute form via conventional spray apparatus to foliage of one or more target plants present on an area of ground at a rate of from about 1 gallon to about 20 gallons, more typically about 3 gallons to 20 gallons, of the above described diluted pesticide composition per acre of ground.
  • the pesticide compositions of the invention may advantageously also be useful to reduce volatility of said auxin herbicide and off-site movement of said auxin herbicide.
  • Volatilization occurs when pesticide surface residues change from a solid or liquid to a gas or vapor after an application of a pesticide has occurred. Once airborne, volatile pesticides can move long distances off site (and in particular longer distances compared to spray drift).
  • Another object of the present invention is to provide auxin herbicide compositions having reduced volatility relative to currently available compositions, and preferably reduced- volatility compositions that exhibit no significant reduction in herbicidal effectiveness relative to currently available compositions.
  • compositions of the present invention provide enhanced protection from off-target crop injury while maintaining comparable herbicidal efficacy on auxin-susceptible plants located in the target area.
  • volatilization of an auxin herbicide can be assessed as follows : an auxin herbicide composition is heated, causing the auxin herbicide to volatilize from said composition into the gas phase. Weight of residual auxin herbicide composition is recorded against time (through thermogravimetric analyses), allowing indirect measurement of volatilization of the auxin herbicide.
  • Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
  • a pesticide N,N-bis(3-aminopropyl)methylamine salt of Dicamba
  • a water soluble polysaccharide polymer non-derivatized guar
  • a suspending agent Organic e clay
  • Comparative Example 1 was analogous to that of Example 1 , but with another suspending agent (Stearalkonium hectorite).
  • compositions were prepared as follows. During all the preparation, the medium was stirred using an inox deflocculating blade (diameter 35 mm) at a speed of 800 rpm. 94.7% wt. EngeniaTM (N,N-bis(3-aminopropyl)methylamine salt of Dicamba, 600 g/L a.e. BASF) were introduced in a plastic beaker. 0.01 %wt. preservative (Kathon CGTM, Dow) were added. Then 0.29% wt. suspending agent (Bentone DY-CETM, Elementis Specialties) were slowly added (gentle sprinkling using a spatula). The formulation was then left for 3 hours under stirring (800 rpm).
  • non-derivatized guar gum having a weight average molecular weight of about 2,000,000 g/mol
  • the formulation was then left for 1 hour under stirring (800 rpm).
  • compositions The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C1 was not stable as top syneresis appeared after 3 days at room temperature and 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
  • the viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute (“rpm").
  • Example 1 and C1 The materials and their relative amounts used to make the compositions of Examples 1 and C1 are set forth in Table I below and the stability and dilution results for Example 1 and Comparative Example C1 are set forth in Table l-A below.
  • the composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
  • a pesticide N,N-bis(3-aminopropyl)methylamine salt of Dicamba
  • a water soluble polysaccharide polymer non-derivatized guar
  • a suspending agent Organic e
  • the composition of Comparative Example 2 was analogous to that of Example 1 , but with another suspending agent (Quaternium-18 hectorite).
  • Example 2 were prepared in the same fashion of Example 1.
  • compositions The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C2 was not stable as top syneresis appeared after 3 days at room temperature and 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
  • the viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute (“rpm").
  • Example 1 and C2 The materials and their relative amounts used to make the compositions of Examples 1 and C2 are set forth in Table II below and the stability and dilution results for Example 1 and Comparative Example C2 are set forth in Table ll-A below.
  • Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
  • a pesticide N,N-bis(3-aminopropyl)methylamine salt of Dicamba
  • a water soluble polysaccharide polymer non-derivatized guar
  • a suspending agent Organic e clay
  • Comparative Example 3 was analogous to that of Example 1 , but with another suspending agent (Highly benefiated smectite clay).
  • Example 3 were prepared in the same fashion of Example 1.
  • compositions The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C3 was not stable as top syneresis appeared after 1 day at room temperature. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
  • the viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute (“rpm").
  • Example III The materials and their relative amounts used to make the compositions of Examples 1 and C3 are set forth in Table III below and the stability and dilution results for Example 1 and Comparative Example C3 are set forth in Table lll-A below.
  • the composition of Example 4 was an aqueous herbicide composition that contained a pesticide (Diglycolamine salt of Dicamba), a water soluble polysaccharide polymer (non- derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
  • a pesticide Diglycolamine salt of Dicamba
  • a water soluble polysaccharide polymer non- derivatized guar
  • a suspending agent Organically modified and beneficiated smectite clay
  • Comparative Example 4 was analogous to that of Example 4, but with another suspending agent (Hectorite and Hydroxy Ethyl Cellulose).
  • SL DGA Dicamba was prepared as follows. Preparation of diluted solution of DGA: 47.8% wt. deionized water were introduced in a glass bottle of 500 ml_. 52.2% wt. DGA (DiGlycolAmine, 98%, Merck) were added into the water. The solution was stirred (magnetic stirrer, 700 rpm) during 45 min.
  • Example 4 The compositions of Example 4 and comparative Example 4 were prepared in the same fashion of Example 1.
  • each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature conditions and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition was taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Comparative example C4 was not stable as top syneresis appeared after 3 days at room temperature. Example 4 was stable for 4 months at room temperature. The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
  • the composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
  • a pesticide N,N-bis(3-aminopropyl)methylamine salt of Dicamba
  • a water soluble polysaccharide polymer non-derivatized guar
  • a suspending agent Organic e clay
  • the comparative Example 5 was prepared in the same fashion of Example 1.
  • compositions The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C5 was not stable as top syneresis appeared after 4 days at 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
  • the viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute (“rpm").
  • compositions were diluted with water CIPAC D (342 ppm) at 30°C.
  • Example V The materials and their relative amounts used to make the compositions of Examples 1 and C5 are set forth in Table V below and the stability and dilution results for Example 1 and Comparative Example C5 are set forth in Table V-A below.
  • Example 1 and Engenia were made by diluting compositions Example 1 and EngeniaTM (BASF) in 342 ppm hardness CIPAC water to provide dilute aqueous mixtures containing the relative amount of the respective compositions Example 1 and EngeniaTM as percent by weight of the dilute composition in Table VI below.
  • the dilute aqueous compositions thus obtained were sprayed through a single flat fan nozzle AI 1 1003-VS at a pressure of 40 psi in a flow-controlled hood (speed 1.6 mph) and the droplet size distribution was measured perpendicular to the plane pf spray pattern and 12 inches below the nozzle tip.
  • a Sympatec Laser HELOS-VARIO/KR multi range (Sympatec GmbH, Germany) was used to measure the spray droplets using a R7 lens.

Abstract

The present invention relates to an aqueous composition comprising at least an auxin herbicide and a drift control agent. It relates more particularly to a concentrated blend of at least one water-soluble salt of an auxin herbicide and of a drift control agent.

Description

AGRICULTURAL PESTICIDE COMPOSITIONS
This application claims priority to U.S. provisional application No. 62/583781 filed on November 9, 2017, the whole content of this application being incorporated herein by reference for all purposes. The present invention relates to an aqueous composition comprising at least an auxin herbicide and a drift control agent.
It relates more particularly to a concentrated blend of at least one water-soluble salt of an auxin herbicide and of a drift control agent.
Auxin herbicides are a well-known class of herbicides used to kill weeds by inducing hormonal effects on sprayed plants. They are thus commonly used to control auxin- susceptible plant growth. Typical representatives of auxin herbicides include 2,4-D (2,4-dichlorophenoxyacetic acid) and dicamba (3,6-dichloro-2-methoxybenzoic acid).
Spray drift is a problem frequently faced when using this class of herbicides.
Spray drift is defined by the Environmental Protection Agency as the movement of pesticide dust or droplets through the air at the time of application or soon thereafter, to any site other than the area intended.
Non-target plant damage associated with auxin herbicide spray drift is a major concern for crop growers nowadays. As a matter of fact, unintentional application of auxin herbicides to a sensitive plant generally causes severe injury, loss of yield, and even death of the non- target plants.
This is the reason why there is an increasing demand today for auxin herbicide compositions with improved spray drift control properties. Various drift control agents are already known in the art. Drift control agents can be defined as chemical agents that enhance drift control of spray applied pesticide composition and/or provides "anti-rebound" properties to the spray applied pesticide composition, that is, reduces rebound of the spray applied pesticide from a target substrate, such as e.g., the foliage of a target plant. Typical examples of drift control agents include for instance polysaccharide polymers, polyacrylamide polymers and emulsified fatty compounds.
As a rule, the drift control agent may be added to the spray tank (so-called tank-mix adjuvants) or may be incorporated directly into the concentrated herbicide composition (so- called built-in adjuvants).
Tank mixes are combinations of agricultural products (pesticide formulation and tank mix adjuvant compositions) that a farmer would pour into a tank (in which the tank mix is prepared), with water and perhaps other additives, mix (optionally by stirring) and then apply on the field shortly thereafter, as these mixes are typically not stable for extended periods of time. However, tank mixes face a variety of issues such as use of incorrect ingredients, human error in measuring the relative component amounts, and improper mixing steps. This can result in reduced effectiveness of the spray formulation, precipitation or gelation in the tank, clogged spray nozzles or clogged screens, excessive residue or runoff, or plant phyto- toxicity.
The use of known drift control agents for preparing a tank mix composition of an auxin herbicide has already been reported in the past.
Given the drawbacks associated with tank mixes, there remains a need today for stable concentrated compositions of one water-soluble salt of an auxin herbicide that contain a sufficient amount of a drift control agent in a one-pack concept (built-in), that is to say for composition of one water-soluble salt of an auxin herbicide that comprises a relatively high concentration of an auxin herbicide, in particular a high concentration of a water-soluble salt of an auxin herbicide, and of a drift control agent, and that is intended to be heavily diluted at the point of use to provide an auxin herbicide composition for application to target pests exhibiting an improved drift control. In particular, there remains a need today for stable concentrated compositions of at least one water-soluble salt of an auxin herbicide that contain a relatively high amount of a water- soluble salt (whether it be a water-soluble salt of said auxin herbicide alone or a combination of a water-soluble salt of said auxin herbicide with a water-soluble salt of an additional herbicide and/or with added water-soluble salt) and a sufficient amount of a drift control agent and that does not require the use of a separate tank-mix adjuvant by the end user to realize the full biological potential of the dose of herbicide applied per unit crop area and/or to achieve acceptable drift control. There remains more particularly a need today for stable concentrated compositions of at least one water-soluble salt of an auxin herbicide that exhibit at the same time acceptable storage stability, dilution miscibility and stability and acceptable spray drift control properties when said concentrated composition is diluted in water in a spray tank for soil or foliar application.
One of the major challenges to resolve the above-mentioned technical problems is to incorporate significant amounts of known drift control agents, such as for instance polysaccharide polymers, polyacrylamide polymers and emulsified fatty compounds, into concentrated compositions of at least one water-soluble salt of an auxin herbicide containing a relatively high amount of a water-soluble salt (whether it be a water-soluble salt of said auxin herbicide alone or a combination of a water-soluble salt of said auxin herbicide with a water-soluble salt of an additional herbicide and/or with added water-soluble salt), while improving at least one of the target attributes of said concentrated composition, in particular storage stability, dilution miscibility and stability and acceptable spray drift control properties when said concentrated composition is diluted in water in a spray tank for soil or foliar application.
Incorporating significant amounts of drift control agents is critical in concentrated compositions since, as mentioned previously, said concentrated compositions are then intended to be heavily diluted at the point of use and the diluted composition shall include a minimum amount of said drift control agent to achieve acceptable drift control.
It is widely known that typical polymeric drift control agents, in particular water-soluble polymers such as polysaccharide polymers (e.g. guars) or polyacrylamide polymers, need to be added into such formulations in a suspended form (for instance in a incompletely hydrated form) to avoid a significant and detrimental increase in viscosity. As a matter of fact, even a low amount of water-soluble polymer, when in a hydrated state, can yield to a formulation that is no longer pourable, for example, as a gel.
When the drift control agent is in the form of an emulsified fatty compound, it is common to use a suspending agent to favor long term stability of the emulsion in order to avoid phase separation which would be also detrimental to the formulation stability and/or to the drift control properties.
The main difficulty lies in the fact that the performances of traditional suspending agents, such as for instance xanthan gum, or silica used in the prior art, are reduced in the presence of a relatively high amount of a water-soluble salt, which may especially impact some target attributes, such as for instance storage stability over time. As a matter of fact, the presence of a relatively high amount of a water-soluble salt (and thus a high electrolytic level) in the concentrated composition can potentially prevent the full hydration of such traditional suspending agents, thereby negatively impacting their performances.
This may result, for instance, in deteriorated suspending properties or in a negative impact on long term stability or in the presence of residual gel particles, or even in the hydration of water-soluble drift control polymers, leading to progressive viscosity increase of the composition or to rapid phase separation.
There remains thus a need for a suspending agent exhibiting improved properties, especially in the presence of a relatively high amount of a water-soluble salt, and making it possible to prepare stable concentrated compositions of at least one water-soluble salt of an auxin herbicide and of at least one drift control agent, in particular in the case where said drift control agent is in the form of particles (for instance particles of an incompletely hydrated water-soluble polymer) or in the form of droplets (for instance droplets of a fatty drift control agent formulated as an emulsion).
It is in particular desirable to provide a stable concentrated composition of at least one water- soluble salt of an auxin herbicide and of at least one drift control agent as described previously that exhibit improved properties especially in terms of storage stability, dilution miscibility and stability and/or acceptable spray drift control properties when said concentrated composition is diluted in water in a spray tank for soil or foliar application. It has now been discovered, unexpectedly, that the use of a specific suspending agent or a combination of specific suspending agents made it possible to achieve this goal.
In particular, it has been discovered that the specific suspending agent of the invention as described below was particularly effective to bring improved suspension properties under such conditions (namely in concentrated formulations containing a relatively high amount of a water-soluble salt and a drift control agent as described previously).
The present invention relates to, in one aspect, a pesticide composition comprising, by total weight of the composition:
-a pesticide comprising at least one water-soluble salt of an auxin herbicide;
-greater than about 0.5 wt% of a drift control agent suspended in an aqueous liquid medium; and - a suspending agent in an amount effective to impart shear thinning properties to the composition, the suspending agent comprising at least one organically modified and beneficiated smectite clay.
Advantageously, the suspending agent is present in an amount effective to impart shear thinning properties to the composition.
The drift control agent of the invention (which is either in the form of particles (for instance particles of an incompletely hydrated water-soluble polymer) or in the form of droplets (for instance droplets of a fatty drift control agent formulated as an emulsion)) will thus remain suspended if the yield strength in the medium is sufficient to overcome the effect of settling or buoyancy on those particles / droplets.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
AUXIN HERBICIDE
The term "auxin herbicide" refers to a herbicide that functions as a mimic of an auxin plant growth hormone, thereby affecting plant growth regulation. Examples of auxin herbicides that are suitable for use in the herbicidal compositions of the present invention include, without limitation, benzoic acid herbicides, phenoxy herbicides, pyridine carboxylic acid herbicides, pyridine oxy herbicides, pyrimidine carboxy herbicides, quinoline carboxylic acid herbicides, and benzothiazole herbicides.
According to anyone of the invention embodiments, the auxin herbicide is selected in the group consisting of 2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB (4-(2,4- dichlorophenoxy)butanoic acid), dichloroprop (2-(2,4-dichlorophenoxy)propanoic acid), MCPA ((4-chloro-2-methylphenoxy)acetic acid), MCPB (4-(4-chloro-2- methylphenoxy)butanoic acid), aminopyralid (4-amino-3,6-dichloro-2-pyridinecarboxylic acid), clopyralid (3,6-dichloro-2-pyridinecarboxylic acid), fluoroxypyr ([(4-amino-3,5-dichloro-6- fluoro-2-pyridinyl)oxy]acetic acid), triclopyr ([(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid), diclopyr, mecoprop (2-(4-chloro-2-methylphenoxy)propanoic acid) and mecoprop-P, dicamba (3,6-dichloro-2-methoxybenzoic acid), picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid), quinclorac (3,7-dichloro-8-quinolinecarboxylic acid), aminocyclopyrachlor (6-amino-5- chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid), agriculturally acceptable salts of any of these herbicides, racemic mixtures and resolved isomers thereof, and mixtures thereof. According to anyone of the invention embodiments, the auxin herbicide is dicamba, or an agriculturally acceptable salt or ester thereof, for instance dicamba sodium salt, dicamba potassium salt, dicamba monoethanolamine salt, dicamba diethanolamine salt, dicamba isopropylamine salt, dicamba diglycolamine salt, dicamba N,N-bis-(3- aminopropyl)methylamine salt or dicamba dimethylamine salt. In one embodiment, the dicamba salt is (i) a secondary, tertiary or quaternary alkylamine or (ii) a primary, secondary, tertiary or quaternary alkanolamine, alkylalkanolamine or alkoxyalkanolamine salt, wherein the alkyl and alkanol groups are saturated and contain from C1 -C4 carbon atoms. According to anyone of the invention embodiments, the pesticide comprises a dicamba salt, wherein the salt is N,N-bis(3-aminopropyl)methylamine, diethanolamine, monoethanolamine, dimethylamine, isopropylamine, dimethylethanolamine, diglycolamine, potassium, choline, or sodium. According to anyone of the invention embodiments, the pesticide comprises dicamba diglycolamine (DGA) salt or dicamba N,N-bis(3-aminopropyl)methylamine (BAPMA) salt.
Other dicamba salts that can be used according to the present invention, especially dicamba polyamine salts, are recited for instance in WO2013/189773 which is herein incorporated by reference in its entirety.
According to another one of the invention embodiments, the herbicidal composition comprises at least 2,4-D, or an agriculturally acceptable salt or ester thereof.
For instance, a herbicidal composition of the invention may comprise a 2,4-D salt selected in the group consisting of : the choline, dimethylamine, and isopropylamine salts, and combinations thereof.
For instance, a herbicidal composition of the invention may comprise a 2,4-D ester selected in the group consisting of : the methyl, ethyl, propyl, butyl (2,4-DB), and isooctyl esters, and combinations thereof.
According to anyone of the invention embodiments, the concentrated composition of the invention contains at least one water-soluble salt of an auxin herbicide as described previously, in particular at least one agriculturally acceptable water-soluble salt of dicamba, for instance dicamba sodium salt, dicamba potassium salt, dicamba monoethanolamine salt, dicamba diethanolamine salt, dicamba isopropylamine salt, dicamba diglycolamine salt, dicamba N,N-bis-(3-aminopropyl)methylamine salt or dicamba dimethylamine salt, and combinations thereof. According to anyone of the invention embodiments, the concentrated composition of the invention contains at least one water-soluble salt of an auxin herbicide as described previously, in particular at least one agriculturally acceptable water-soluble salt of 2,4-D, for instance 2,4-D choline salt, 2,4-D dimethylamine salt, or 2,4-D isopropylamine salt, and combinations thereof.
A concentrated composition of the invention usually contains at least 300 g/l, more preferably at least 400 g/l, and in particular at least 450 g/l acid equivalents (a.e.) of auxin herbicide, in particular dicamba.
According to anyone of the invention embodiments, the concentrated composition of the invention may comprise at least 300 g/L acid equivalents (a.e.) of at least one water-soluble salt of an auxin herbicide, in particular dicamba.
A concentrated composition of the invention contains usually up to 800 g/l, preferably up to 700 g/l, more preferably up to 650 g/l, and in particular up to 600 g/l acid equivalents (a.e.) of auxin herbicide, in particular dicamba.
AQUEOUS LIQUID MEDIUM
A composition of the invention comprises an aqueous liquid medium.
As used herein, the terminology "aqueous medium" means a single phase liquid medium that contains more than a trace amount of water, typically, based on 100 pbw of the aqueous medium, more than 0.1 pbw water. Suitable aqueous media more typically comprise, based on 100 pbw of the aqueous medium, greater than about 5 pbw water, even more typically greater than 10 pbw water. In one embodiment, the aqueous medium comprises, based on 100 pbw of the aqueous medium, greater than 40 pbw water, more typically, greater than 50 pbw water. The aqueous medium may, optionally, further comprise water soluble or water miscible components dissolved in the aqueous medium. The terminology "water miscible" as used herein means miscible in all proportions with water. Suitable water miscible organic liquids include, for example, (CrC3)alcohols, such as methanol, ethanol, and propanol, and (CrC3)polyols, such as glycerol, ethylene glycol, and propylene glycol.
According to anyone of the invention embodiments, a composition of the invention comprises greater than about 5 wt% of an aqueous liquid medium, for instance greater than about 10 wt%, for instance from about 10 wt% to about 80 wt%, for instance from about 15 wt% to about 75 wt% of an aqueous liquid medium relative to the total weight of the composition. SUSPENDING AGENT
The suspending agent used in a composition of the present invention comprises at least one smectite clay
The smectite clay used in the present invention is an organically modified smectite clay (organoclay), i.e. a smectite clay modified with an organic chemical composition.
More particularly, the smectite clay used in the present invention is the ion-exchanged reaction product of (a) a smectite clay and (b) one or more quaternary ammonium compounds and/or (c) one or more organic materials.
In other words, the organically modified smectite clay of the invention is an organic chemical/clay mixture prepared by the reaction of a smectite clay and one or more quaternary ammonium compounds, and/or optionally one or more organic materials.
Smectite clays are swellable layered clays which contain individual platelets.
Useful swellable layered materials include phyllosilicates such as smectite clay minerals, e.g., montmorillonite, particularly sodium montmorillonite; bentonite; hectorite; saponite; stevensite; beidellite; and the like.
Smectite clays used according to the invention may typically be bentonite and hectorite. Smectite clays possess some structural characteristics similar to the better-known minerals talc and mica. Their crystal structures consist of two-dimensional layers formed by fusing two silica tetrahedral sheets to an edge-shared dioctahedral or trioctahedral sheet of either alumina (for example bentonite) or magnesia (for example hectorite) - each of the different smectite clays having somewhat different structures. Stacking of these layers in nature in depths of hundreds or more is caused by ionic and weak Van der Waals forces. The area between the platelets is occupied by cations which balance the charge deficiency that is generated by isomorphous substitution (often called disharmonies) within the platelet lattices.
As used herein the term "interlayer spacing" refers to the distance between the internal faces of adjacent smectite clay platelet layers, either in the dry state or as incorporated into a polymer. The interlayer spacing is measured by standard X-Ray Diffraction techniques.
The smectite clays which may be used in the present invention are preferably smectite-type clays having a cationic exchange capacity of at least 50 milliequivalents per 100 grams of clay, 100% active clay basis, as determined by the well-known ammonium acetate or methylene blue methods.
Smectite-type clays are well known in the art and are commercially available from a variety of sources. Prior to use in the invention, the clays may preferably be converted to the sodium form if they are not already in this form. This may be conveniently carried out by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide, etc., and the mixture sheared, such as with a pugmill or extruder. Representative smectite clays useful in accordance with the present invention are the following:
Montmorillonite [(Al4-xMgx)Si802o(OH)4-fFf]xR+
where 0.55 < x < 1 .10, f < 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof;
Bentonite
[(AI4-xMgx)(Si8-yAly)O20(OH)4-fFf](x+y)R+
where 0 < x < 1.10, 0 < y < 1 .10, 0.55 < (x + y) < 1 .10, f < 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof; Hectorite
[(Mg6-xLix)Si8O20(OH)4-fFf]xR+
where 0.57 < x < 1 .15, f < 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof;
Saponite
[(Mg6-yAly)Si8-x-yAlx+y02o(OH)4-fFf]xR+
where 0.58 < x < 1 .18, 0 < y < 0.66, f <4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof; and
Stevensite
[Mg6-xSi8O20(OH)4-fFf]2xR+
where 0.28 < x < 0.57, f = 4 and R is selected from the group consisting of Na, Li, NH4, mixtures thereof.
Beidellite [(Al4+y)(Si8-x-yAlx+y)02o(OH)4-fFf]xR+
where 0.55 < x < 1 .10, 0 < y < 0.44, f < 4 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof.
The preferred clays used in the present invention are bentonite and hectorite.
Both sheared and non-sheared forms of the above-listed smectite clays may be employed. The smectite clay used in the present invention is a beneficiated smectite clay, that is to say a smectite clay that has been purified so that some or most of the impurities in the crude clay have been removed.
Crude smectite clay can be defined as smectite clay containing gangue or non-clay material. Beneficiated smectite clay used in the present invention differs from crude smectite clay in that gangue has been removed. Beneficiated smectite clays used in the present invention are smectite clays that have undergone clay beneficiation process.
Compound(s) (b) of the invention is one or more quaternary ammonium compounds. Particularly useful are quaternary ammonium compounds which include those having the formula:
Figure imgf000011_0001
wherein R1 comprises a group selected from (i) linear or branched aliphatic, aralkyl, or aromatic hydrocarbon groups having from 8 to 30 carbon atoms or (ii) alkyl or alkyl-ester groups having 8 to 30 carbon atoms; R2, R3, and R4 are independently selected from the group consisting of (a) linear or branched aliphatic hydrocarbon, fluorocarbon, or other halocarbon groups having from 1 to about 30 carbon atoms; (b) aralkyl or aromatic groups having from 6 to about 30 carbon atoms, (c) alkoxylated groups containing from 1 to about 80 moles of alkylene oxide; (d) amide groups, (e) oxazolidine groups, (f) allyl, vinyl, or other alkenyl or alkynyl groups possessing reactive unsaturation and having from 2 to about 30 carbon atoms, and (g) hydrogen: and X' comprises an anion selected from the group consisting of chloride, methyl sulfate, acetate, iodide, and bromide, preferably chloride.
For purposes of this invention, quaternary phosphonium and sulfonium based salts are defined as within the definition of quaternary ammonium compound. The raw materials used to make the quaternary amonium compounds can be derived from natural oils such as tallow, soya, coconut and palm oil. Useful aliphatic groups in the above formula may be derived from other naturally occurring oils including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils or fats. The aliphatic groups may likewise be petrochemically derived from, for example, alpha olefins. Representative examples of useful branched, saturated radicals included 12-methylstearyl and 12-ethylstearyl.
Examples of useful aromatic groups include benzyl and benzylic-type materials derived from benzyl halides, benzhydryl halides, trityl halides, halophenylalkanes wherein the alkyl chain has from 1 to 30 carbon atoms, such as 1 -halo-1 -phenyloctadecane; substituted benzyl moieties, such as those derived from ortho-, meta-, and para-chlorobenzyl halides, para- methoxybenzyl halides, ortho-, meta-, and para-nitrilobenzyl halides, and ortho-, meta-, and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 30 carbon atoms; and fused ring benzyl-type moieties, such as those derived from 2-halomethylnaphthalene, 9-halomethylanthracene, and 9-halomethylphenanthrene, wherein the halo group comprises chloro, bromo, or any other such group which serves as a leaving group in the nucleophilic attack of the benzyl type moiety by a nitrogen atom to generate a substituted amine. Examples of other aromatic groups include aromatic-type substituents such as phenyl and substituted phenyl; N-alkyl and Ν,Ν-dialkyl anilines, where the alkyl groups contain between 1 and 30 carbon atoms; ortho-, meta-, and para-nitrophenyl, ortho-, meta-, and para-alkyl phenyl, wherein the alkyl group contains between 1 and 30 carbon atoms; 2-, 3-, and 4-halophenyl wherein the halo group is defined as chloro, bromo, or iodo; and 2-, 3-, and 4-carboxyphenyl and esters thereof, where the alcohol of the ester is derived from an alkyl alcohol, wherein the alkyl group contains between 1 and 30 carbon atoms, aryl such as phenol, or aralkyl such as benzyl alcohols; and fused ring aryl moieties such as naphthalene, anthracene, and phenanthrene. Preferred quaternary ammonium compounds for purposes of the invention comprises a quaternary ammonium salt that contains at least one, preferably two or three, hydrocarbon chains having from about 8 to about 30 carbon atoms and either no hydrophilic carbon chains or having hydrophilic radicals having a total of about 9 moles of ethylene oxide or less.
Some examples of preferred quaternary ammonium compounds to make the compositions of this invention are: dimethyl bis[hydrogenated tallow] ammonium chloride (2M2HT), methyl benzyl bis[hydrogenated tallow] ammonium chloride (MB2HT), and methyl tris[hydrogenated tallow alkyl] chloride (M3HT).
Materials suitable for optional element (c) of this invention include materials listed as anionic components in US 4,412,018, 4,434,075, and 4,577,1 12. These include materials that are capable of reacting with component (b) of this invention and for intercalation with component (a) as an alkyl quarternary ammonium-organic anion complex. The molecular weight (gram molecular weight) of the organic anion is preferably 3,000 or less, and most preferably 1 ,000 or less and contains at least one anionic moiety per molecule as disclosed herein. The organic anion is preferably derived from an organic acid having a pKA less than about 1 1.0. As indicated, the source acid must contain at least one ionizable hydrogen having the preferred pKA in order to allow the formation of the alkyl quarternary ammonium- organic anion complex. Exemplary types of suitable acidic functional organic compounds useful in this invention include:
(1 ) Carboxylic acids including: a) benzene carboxylic acids such as benzoic acid; ortho-, iso- and terephthalic acid; 1 ,2,3-benzenetricarboxylic acid; 1 ,2,4-benzenetricarboxylic acid; 1 ,3,5-benzenetricarboxylic acid; 1 ,2,4,5-benzenetetracarboxylic acid; 1 ,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid); b) alkyl carboxylic acids having the formula CH3(CH2)n-COOH, wherein n is a number from 0 to 20; such compounds include acetic acid; pentanoic acid; hexanoic acid; heptanoic acid; octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; lauric acid; tridecanoic acid; tetradecanoic acid; pentadecanoic acid; hexadecanoicanoic acid; heptadecanoic acid; octadecanoic acid (stearic acid); nonadecanoic acid; eicosonic acid. c) Alkyl dicarboxylic acids having the formula HOOC-(CH2)n-COOH wherein n is 0 to 8 such as oxalic acid; malonic acid; succinic acid; glutaric acid; adipic acid; pimelic acid; suberic acid; azelaic acid; sebacic acid; d) Hydroxyalkyl carboxylic acids such as citric acid; tartaric acids; malic acid; mandelic acid; and 12-hydroxystearic acid; e) unsaturated alkyl carboxylic acids such as maleic acid; fumaric acid; and cinnamic acid; f) Fused ring aromatic carboxylic acids such as naphthalenic acid and anthracenecarboxylic acid; g) Cycloaliphatic acids such as cyclohexanecarboxylic acid; cyclopentanecarboxylic acid; furancarboxylic acids.
(2) Organic sulfuric acids including: a) sulfonic acids including:
1 ) benzenesulfonic acids such as benzenesulfonic acid; phenolsulfonic acid; dodecylbenzenesulfonic acid; benzenedisulfonic acid; benzenetrisulfonic acids; para- toluenesulfonic acid; and
2) alkyl sulfonic acids such as methanesulfonic acid; ethanesulfonic acid; butanesulfonic acid; butanedisulfonic acid; sulfosuccinate alkyl esters such as dioctyl succinylsulfonic acid; and alkyl polyethoxy-succinyl sulfonic acid; and b) alkyl sulfates such as the lauryl half ester of sulfuric acid and the octadecyl half ester of sulfuric acid.
(3) Organophosphorus acids including phosphonic acids, phosphinic acids, thiophosphinic acids, phosphites, and phosphates as described in US Patent No. 4,412,018.
(4) Phenols such as phenol; hydroquinone; t-butylcatechol; p-methoxyphenol; and naphthols.
(5) Thioacids as described in US Patent No. 4,412,018.
(6) Amino acids such as the naturally occurring amino acids and derivatives thereof such as 6-aminohexanoic acid; 12-aminododecanoic acid; N-phenylglycine; and 3-aminocrotonic acid.
Other materials useful for element c) can be selected from a wide variety of non-anionic materials as described in U.S. Patent Application No. 09/064216, descriptions herein incorporated by reference. These materials are either water soluble, liquid, or can be made into a liquid at reaction temperature so that the aforementioned clay material absorbs them. These materials can be any of a wide range of materials and can have a wide range of molecular weights. Materials of this type suitable for element (c) of this invention include polyurethanes; polyamides; polyesters; polycarbonates; polyepoxides and polyolefins. Such materials also include polyethers (polymers and copolymers) based on ethylene oxide, butylene oxide, propylene oxide, phenols and bisphenols; polyesters (polymers and copolymers) based on aliphatic and aromatic diols and polyurethanes based on aliphatic and aromatic diisocyanates, polyamides (polymers and copolymers) based on aliphatic and aromatic diamines, and polycarbonates (polymers and copolymers) based on aliphatic or aromatic diols; polycarboimides (polymers and copolymers) based on tetrabasic acids and diamines, vinyl polymers and copolymers based on vinyl monomers, styrene and derivatives of styrene; acrylic polymers and copolymers based on acrylic monomers; copolymers based on styrene, vinyl and acrylic monomers; polyolefin polymers and copolymers based on ethylene, propylene and other alphaolefin monomers; polymers and copolymers based on dienes, isobutylenes and the like; and copolymers based on dienes, styrene, acryl and vinyl monomers. Other organic materials can include monomeric materials that have the functionality of the materials described above. The definition of element c) does not include quaternary ammonium compounds.
Specific preferred examples of useful non-anionic organic materials include THIXATROL VF-10 and THIXATROL VF-20 which are liquid polyester amide copolymers made by RHEOX. Examples of other specific materials are polyvinylpyrrolidone (PVP) or its hydrolysis product, polyvinyl alcohol (PVA), polymethacrylamide, poly(N,N- dimethylacrylamide), poly(N-isopropylacrylamide), poly(N-acetamidacrylamide), poly(N- acetimidomethacrylamide), polyvinyloxazolidone, and polyvinylmethyl oxazolidone, polyoxypropylene, polyoxyethylene and copolymers thereof.
The materials (b) and (c) can be reacted together, or in any order, with the smectite clay.
The amount of quaternary compound and optional organic compound used can vary over wide ranges. This amount is defined as the millequivalent ratio which is the number of milliequivalents (m.e.) of the organic cation in the organoclay per 100 grams of clay, 100% active clay basis.
Normally, where only a quaternary is employed, at least 90 to 100 m.e. of organic cation, more typically 100 to 140 m.e. of quaternary salt based on 100 g of 100% active clay are preferred although lower and higher ratios are also useful.
It is typical that component (c), if present, is used at an amount of 5 to 100 milliequivalents, and more preferably 10 to 50 m.e., per 100g of clay, 100% active basis. The organoclays useful in the composites of this invention may be prepared in a number of ways. One is to first disperse the smectite clay in water. The clay is preferably dispersed in water at a concentration of from about 1 to 80%, most preferably from about 2 to 8% by weight. Optionally, the slurry may be centrifuged to remove non-clay impurities that constitute about 10% to 50% of the starting clay composition. If the optional organic material is to be part of the composition, it is added to the clay/water dispersion and mixed. This mixture can then be heated and is ion exchanged with a quaternary ammonium compound to form the final organoclay as a coagulate, which is washed with water and isolated by filtration. If only the optional organic material is used, it can be added to the purified clay/water slurry an adsorbed onto the clay. The clay is then isolated by drying.
A second general method to prepare this invention uses dry clay that is intimately mixed with the organic material in a heated device, such as an extruder. The mixture can also have some water present to facilitate intercalation. After the addition is complete, the quaternary ammonium compound and/or organic material is added and the final product is isolated. This composition can be washed with water and dried.
Both of the methods mentioned above where both components (b) and (c) are used can be modified by either: 1 ) reversing the order of addition, i.e., reacting the clay with the quaternary ammonium ion followed by the organic material; or 2) adding the quaternary ammonium compound and organic material to the clay simultaneously.
The reaction is preferably followed by drying and grinding the organoclay product.
The organoclay can further be incorporated into a polymer resin.
Suitable polymer resins include a very wide variety of resins. It can be any plastic material whether polar or non-polar. Such resins can include polyolefins which can consist of polyethylenes, polypropylenes, polybutylenes, polymethylpentane, polyisoprenes and copolymers thereof; copolymers of olefins and other monomers such as ethylene-vinyl acetate, ethylene acid copolymers, ethylene-vinyl alcohol, ethylene-ethyl acrylate, and ethylene-methyl acrylate. lonomers are also useful and comprise metal salts of polyolefins copolymerized with acrylic acid. Other families of thermoplastic resins useful in this invention are acetals, acrylics, and cellulosics. Fluoropolymers and copolymers with other monomers are useful such as polytetrafluoroethylene (Teflon®), fluorinated ethylene-propylene, perfluoroalkoxy resins, polychlorotrifluoroethylene, ethylene-chlorofluoroethylene copolymer, polyvinylidene fluoride and polyvinylfluoride. Liquid crystal polymers, a family of polyester copolymers, can also be used. Additional polymers are nitrile resins, polyamides (nylons), polyphenylene ether and polyamide-imide copolymers. Various polyesters are useful such as polyarylates, polybutylene terephthalate and polyethylene terephthalate. Engineering resins such as polycarbonate, polyetherimide, polyetheretherketone, polyphenylene sulfide and thermoplastic polyimides are good candidates. Polystyrene and copolymers such as ABS, SAN, ASA and styrene-butadiene are appropriate. Also included are the sulfone based resins such as polysulfone, polyethersulfone and polyarylsulfone. Elastomers comprising a wide variety of useful materials and include olefinic TPE's, polyurethane TPE's, and styrenic TPE's. Chlorinated polymers such as PVC, and polyvinylidene dichloride can also be used. In addition, miscible or immiscible blends and alloys of any of the above resin combinations are useful for this invention. Thermoset polymers such as epoxies, polyester resins and curing rubbers can also be used.
Incorporation of the organoclay of the invention into a polymer resin can be accomplished by mixing or blending the organoclay by any means that can create sufficient shear. The shear can be provided by any appropriate method such as mechanical, thermal shock, pressure changes, or ultrasonics as known in the art. Particularly useful are methods where a flowable polymer is mixed with the organoclay by mechanical means such as extruders, roll mills, stirrers, Banbury® type mixers, Brabender® type mixers, and continuous mixers. Other methods for making this invention can be postulated by those knowledgeable in the art.
According to anyone of the invention embodiments, the organically modified and beneficiated smectite clay of the invention has a bulk density lower than 1 .5 g/cm3, for instance lower than 1 .0 g/cm3, for instance lower than 0.8 g/cm3, for instance lower than 0.7 g/cm3.
According to anyone of the invention embodiments, the organically modified and beneficiated smectite clay of the invention is in the form of a finely divided soft powder, with a particle size of 80% lower than 125 m (120#).
Bentone® DY CE (supplied by Elementis, and having a bulk density of 0.65 g/cm3) is a typical example of organically modified and beneficiated smectite clay suitable according to the present invention.
According to anyone of the invention embodiments, a concentrated composition of the invention comprises greater than about 0.5wt% of an organically modified smectite clay of the invention, for instance greater than about 1wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
According to anyone of the invention embodiments, a concentrated composition of the invention comprises less than about 25wt% of an organically modified smectite clay of the invention, for instance less than about 15wt% of an organically modified smectite clay of the invention, for instance less than about 10wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
The present invention provides a pesticide composition characterized in that it comprises, as suspending agent, an organically modified smectite clay of the invention.
Another preferred subject matter of the invention is a process for the preparation of a concentrated composition of at least one water-soluble salt of an auxin herbicide exhibiting at the same time acceptable storage stability, dilution miscibility and stability and acceptable spray drift control properties when said concentrated composition is diluted in water in a spray tank, which is characterized in that an organically modified smectite clay of the invention, is added to the concentrated composition.
Another preferred subject matter of the invention is the use of an organically modified smectite clay of the invention for the improvement of the storage stability and of the suspending properties of a concentrated composition of the invention.
In one embodiment, the suspension agent provides improved storage stability and suspending properties of a concentrated composition of the invention. In another embodiment, the suspension agent provides improved high temperature storage stability. In one embodiment, the suspending agent of the present invention in utilized in an amount that is effective, either alone or in combination with one or more other suspending agents, to impart shear thinning viscosity to the composition, typically in an amount, based on 100 pbw of the composition, of at least 0.5 pbw, for instance of from greater than 1 pbw, more typically from about 2 pbw, and even more typically from about 1 pbw, to about 10 pbw, more typically to about 8 pbw, and even more typically to about 5 pbw.
According to anyone of the invention embodiments, a concentrated composition of the invention comprises greater than about 0.5wt% of an organically modified smectite clay of the invention, for instance greater than about 1wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition.
According to anyone of the invention embodiments, a concentrated composition of the invention comprises less than about 25wt% of an organically modified smectite clay of the invention, for instance less than about 15wt% of an organically modified smectite clay of the invention, for instance less than about 10wt% of an organically modified smectite clay of the invention, relative to the total weight of the concentrated composition. DRIFT CONTROL AGENT
As used herein, the term "drift" refers to off-target movement of droplets of a pesticide composition that is applied to a target pest or environment for the pest. Spray applied compositions typically exhibit decreasing tendency to drift with decreasing relative amount, typically expressed as a volume percentage of total spray applied droplet volume, of small size spray droplets, that is, spray droplets having a droplet size below a given value, typically, a droplet size of less than 150 micrometers ("μη" ). Spray drift of pesticides can have undesirable consequences, such as for example, unintended contact of phytotoxic pesticides with non-pest plants, such as crops or ornamental plants, with damage to such non-pest plants.
In one embodiment, spray drift can me measured as follows : the aqueous pesticide compositions as described herein are sprayed through a nozzle under certain conditions, for example, a single, stationary XR1 1002 flat fan nozzle (Teejet) with an output of 0.64 liter in"1 at a pressure of 30 psi (~ 2 bar) in a flow-controlled hood (speed ~1 .6 MPH), and a droplet size distribution was measured perpendicular to the plane of spray pattern and below the nozzle tip, e.g., 35 cm. An analyzer such as a HELOS VARIO particle size analyzer
(Sympatec) can be used to measure the spray droplets using a R7 lens. The volume mean diameter ("VMD") of the spray droplets, expressed in micrometers ("Mm"), and relative amount, expressed as percent by volume of the total spray volume ("vol%"), of droplets below 150 μηη can be ascertained. It is desireable for spray compositions to exhibit a smaller amount of small size spray droplets that are very susceptible to spray drift, i.e., droplets below 150 μηη in size, compared to respective analogous compositions or compositions without a drift control agent.
A composition of the invention may comprise any compound useful as drift control agent. Water soluble polymers and fatty deposition control agents as described below are typical examples of suitable drift control agents according to the present invention. Water soluble polymer as a drift control agent
Suitable drift contol agents include water soluble polysaccharide polymers, for example, galactomannans such as guars, including guar derivatives, xanthans, polyfructoses such as levan, starches, including starch derivatives, such as amylopectin, and cellulose, including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.
Galactomannans are polysaccharides consisting mainly of the monosaccharides mannose and galactose. The mannose-elements form a chain consisting of many hundreds of (1 ,4)-β- D-mannopyranosyl-residues, with 1 ,6 linked β-D-galactopyranosyl-residues at varying distances, dependent on the plant of origin. Naturally occurring galactomannans are available from numerous sources, including guar gum, guar splits, locust bean gum and tara gum. Additionally, galactomannans may also be obtained by classical synthetic routes or may be obtained by chemical modification of naturally occurring galactomannans.
Guar gum refers to the mucilage found in the seed of the leguminous plant Cyamopsis tetragonolobus. The water soluble fraction (85%) is called "guaran," which consists of linear chains of (1 ,4)-.β-ϋ mannopyranosyl units-with a-D-galactopyranosyl units attached by (1 ,6) linkages. The ratio of D-galactose to D-mannose in guaran is about 1 :2. Guar gum typically has a weight average molecular weight of between 2,000,000 and 5,000,000 g/mol. Guars having a reduced molecular weight, such as for example, from about 50,000 to about 2,000,000 g/mol are also known.
Guar seeds are composed of a pair of tough, non-brittle endosperm sections, hereafter referred to as "guar splits," between which is sandwiched the brittle embryo (germ). After dehulling, the seeds are split, the germ (43-47% of the seed) is removed by screening, and the splits are ground. The ground splits are reported to contain about 78-82% galactomannan polysaccharide and minor amounts of some proteinaceous material, inorganic salts, water-insoluble gum, and cell membranes, as well as some residual seedcoat and embryo.
Locust bean gum or carob bean gum is the refined endosperm of the seed of the carob tree, Ceratonia siliqua. The ratio of galactose to mannose for this type of gum is about 1 :4. Locust bean gum is commercially available.
Tara gum is derived from the refined seed gum of the tara tree. The ratio of galactose to mannose is about 1 :3. Tara gum is commercially available.
In one embodiment, native (i.e. not derivatized) polysaccharide gums, such as for instance native guar gum, cassia gum or tamarind seed gum, are suitable drift control agents according to the present invention. Other galactomannans of interest are the modified galactomannans, including derivatized guar polymers, such as carboxymethyl guar, carboxymethylhydroxypropyl guar, cationic hydroxpropyl guar, hydroxyalkyl guar, including hydroxyethyl guar, hydroxypropyl guar, hydroxybutyl guar and higher hydroxylalkyl guars, carboxylalkyl guars, including carboxymethyl guar, carboxylpropyl guar, carboxybutyl guar, and higher carboxyalkyl guars, the hydroxyethylated, hydroxypropylated and carboxymethylated derivative of guaran, the hydroxethylated and carboxymethylated derivatives of carubin, and the hydroxypropylated and carboxymethylated derivatives of cassia-gum. Xanthans of interest are xanthan gum and xanthan gel. Xanthan gum is a polysaccharide gum produced by Xathomonas campestris and contains D-glucose, D-mannose, D-glucuronic acid as the main hexose units, also contains pyruvate acid, and is partially acetylated.
Levan is a polyfructose comprising 5-membered rings linked through β-2,6 bonds, with branching through β-2,1 bonds. Levan exhibits a glass transition temperature of 138°C and is available in particulate form. At a molecular weight of 1 -2 million, the diameter of the densely-packed spherulitic particles is about 85 nm.
Modified celluloses are celluloses containing at least one functional group, such as a hydroxy group, hydroxycarboxyl group, or hydroxyalkyl group, such as for example, hydroxymethyl cellulose, hydroxyethyl celluloses, hydroxypropyl celluloses or hydroxybutyl celluloses.
Processes for making derivatives of guar gum splits are generally known. Typically, guar splits are reacted with one or more derivatizing agents under appropriate reaction conditions to produce a guar polysaccharide having the desired substituent groups. Suitable derivatizing reagents are commercially available and typically contain a reactive functional group, such as an epoxy group, a chlorohydrin group, or an ethylenically unsaturated group, and at least one other substituent group, such as a cationic, nonionic or anionic substituent group, or a precursor of such a substituent group per molecule, wherein substituent group may be linked to the reactive functional group of the derivatizing agent by bivalent linking group, such as an alkylene or oxyalkylene group. Suitable cationic substituent groups include primary, secondary, or tertiary amino groups or quaternary ammonium, sulfonium, or phosphinium groups. Suitable nonionic substituent groups include hydroxyalkyl groups, such as hydroxypropyl groups. Suitable anionic groups include carboxyalkyl groups, such as carboxymethyl groups. The cationic, nonionic and/ or anionic substituent groups may be introduced to the guar polysaccharide chains via a series of reactions or by simultaneous reactions with the respective appropriate derivatizing agents.
The guar may be treated with a crosslinking agent, such for example, borax (sodium tetra borate) is commonly used as a processing aid in the reaction step of the water-splits process to partially crosslink the surface of the guar splits and thereby reduces the amount of water absorbed by the guar splits during processing. Other crosslinkers, such as, for example, glyoxal or titanate compounds, are known.
In one embodiment, the drift control agent of the present invention is a non-derivatized galactomannan polysaccharide, more typically a non-derivatized guar gum.
It is understood that the term "non-derivatized guar gum" is synonymous, and used interchangeably, with the terms "native guar" or "guar gum".
In one embodiment, the drift control agent is a derivatized galactomannan polysaccharide that is substituted at one or more sites of the polysaccharide with a substituent group that is independently selected for each site from the group consisting of cationic substituent groups, nonionic substituent groups, and anionic substituent groups.
In one embodiment, the drift control agent of the present invention is derivatized galactomannan polysaccharide, more typically a derivatized guar. Suitable derivatized guars include, for example, hydroxypropyl trimethylammonium guar, hydroxypropyl lauryldimethylammonium guar, hydroxypropyl stearyldimethylammonium guar, hydroxypropyl guar, carboxymethyl guar, guar with hydroxypropyl groups and hydroxypropyl trimethylammonium groups, guar with carboxymethyl hydroxypropyl groups and mixtures thereof.
The amount of derivatizing groups in a derivatized polysaccharide polymer may be characterized by the degree of substitution of the derivatized polysaccharide polymer or the molar substitution of the derivatized polysaccharide polymer.
As used herein, the terminology "degree of substitution" in reference to a given type of derivatizing group and a given polysaccharide polymer means the number of the average number of such derivatizing groups attached to each monomeric unit of the polysaccharide polymer. In one embodiment, the derivatized galactomannan polysaccharide exhibits a total degree of substitution ("DST") of from about 0.001 to about 3.0, wherein:
DST is the sum of the DS for cationic substituent groups ("DScationic"), the DS for nonionic substituent groups ("DSn0nionic") and the DS for anionic substituent groups
( DSanionic )j
DScationic is from 0 to about 3, more typically from about 0.001 to about 2.0, and even more typically from about 0.001 to about 1 .0,
DSnonionic is from 0 to 3.0, more typically from about 0.001 to about 2.5, and even more typically from about 0.001 to about 1 .0, and
DSanionic is from 0 to 3.0, more typically from about 0.001 to about 2.0.
As used herein, the term "molar substitution" or "ms" refers to the number of moles of derivatizing groups per moles of monosaccharide units of the guar. The molar substitution can be determined by the Zeisel-GC method. The molar substitution utilized by the present invention is typically in the range of from about 0.001 to about 3.
In one embodiment, the drift control agent is a water soluble non-polysaccharide polymer. Suitable water soluble non-polysaccaharide polymers include, for example, lecithin polymers, poly(alkyleneoxide) polymers, such as poly(ethylene oxide) polymers , and water soluble polymers derived from ethylenically unsaturated monomers. Suitable water soluble polymers derived from ethylenically unsaturated monomers include water soluble polymers derived from acrylamide, methacrylamide, 2-hydroxy ethyl acrylate, and/or N-vinyl pyrrolidone, including homopolymers of such monomers, such as poly(acrylamide) polymers and polyvinyl pyrrolidone) polymers, as well as copolymers of such monomers with one or more comonomers. Suitable water soluble copolymers derived from ethylenically unsaturated monomers include water soluble cationic polymers made by polymerization of at least one cationic monomer, such as a diamino alkyl (meth)acrylate or diamino alkyl (meth)acrylamide, or mixture thereof and one or more nonionic monomers, such as acrylamide or
methacrylamide. In one embodiment, the non-polysaccharide polymer exhibits a weight average molecular weight of greater than about 1 ,000,000 g/mol, more typically greater than about 2,000,000 g/mol to about 20,000,000 g/mol, more typically to about 10,000,000 g/mol.
In one embodiment, the drift control agent comprises, for example, galactomannans such as guars, including guar derivatives, polyfructoses such as levan, starches, including starch derivatives, such as amylopectin, xyloglucans such as tamarind gum and tamarind gum derivatives such as hydroxypropyl tamarind gum, and cellulose, including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose,
hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate, as well as cassia gum.
Tamarind (Tamahndus Indica) is a leguminous evergreen tall tree produced in the tropics. Tamarind gum (tamarind powder or tamarind kernel powder), a xyloglucan polysaccharide, is obtained by extracting and purifying the seed powders, obtained by grinding the seeds of tamarind. The polysaccharide molecule of the tamarind gum consists of a main linear chain of poly-glucose bearing xylose and galactoxylose substituents.
In another embodiment, the drift control agent of the present invention is derivatized xyloglucan polysaccharide, more typically a derivatized tamarind.
Suitable derivatized tamarinds include, for instance, hydroxypropyl tamarind gum, which may further contain substituent groups such as carboxyalkyl substituents (e.g. carboxymethyl or carboxyethyl) or hydrophobic substituents (e.g. C4-C24 linear or branched alkyl chains), such as those described in WO2016/124467, which is incorporated by reference.
According to another one of the invention embodiments, the drift control agent is a cationic tamarind gum derivative, for instance a cationic tamarind gum derivative having a cationic degree of substitution DScat ranging from about 0.001 to about 3. According to one embodiment, in particular when the drift control agent is a tamarind gum derivative, such as a tamarind seed gum polymer, for instance a hydroxypropyl tamarind, the pesticide composition of the invention does not comprise a combination of dipotassium phosphate and tri-potassium citrate. According to another embodiment, in particular when the drift control agent is a tamarind gum derivative, such as a tamarind seed gum polymer, for instance a hydroxypropyl tamarind, the pesticide composition of the invention does not comprise a combination of di- potassium phosphate, potassium nitrate and tri-potassium citrate.
In another embodiment, the drift control agent is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 0.5 pbw, or of 1 pbw, or in another embodiment of 1.2 pbw, or in another embodiment, 1.4 pbw, or in another embodiment, 1 .6 pbw, or in another embodiment, 1.8 pbw, or in yet another further embodiment, 2 pbw, or in another embodiment, 2.4 pbw, or in a further embodiment, 3 pbw, or in another embodiment, 3.5 pbw, or in another embodiment, 3.8 pbw, or in another embodiment, 4 pbw, or in another embodiment, 4.5 pbw, or one embodiment, 5 pbw, or in another embodiment, 7 pbw, or in a further embodiment, 8 pbw, or in another embodiment, 10 pbw, or in yet another
embodiment, 12 pbw, or in another embodiment, 16 pbw, or in another embodiment, 20 pbw. In one particular embodiment, the water-soluble polymer is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 1 .8 pbw. In one particular embodiment, the drift control agent, for instance the water-soluble polymer, is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 3.8 pbw. In one particular embodiment, the drift control agent, for instance the water-soluble polymer s present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 4 pbw. In one particular embodiment, the the drift control agent, for instance the water-soluble polymer, is present in an amount having a lower limit, based on 100 pbw of aqueous solution or composition, of 2 pbw.
In yet another embodiment, the the drift control agent, for instance the water-soluble polymer, is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 20 pbw, or in another embodiment of 18 pbw, or in another embodiment, 17 pbw, or in another embodiment, 16 pbw, or in another embodiment, 14 pbw, or in yet another further embodiment, 13 pbw, or in another embodiment, 12 pbw, or in a further embodiment, 10 pbw, or in another embodiment, 9 pbw, or in another embodiment, 8 pbw, or in another embodiment, 7 pbw, or in another embodiment, 6 pbw, or one
embodiment, 5.5 pbw, or in another embodiment, 5 pbw, or in a further embodiment, 4.5 pbw, or in another embodiment, 3 pbw, or in yet another embodiment, 2.5 pbw, or in another embodiment, 2.2 pbw. In one particular embodiment, the drift control agent, for instance the water-soluble polymer, is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 12 pbw. In one particular embodiment, the drift control agent, for instance the water-soluble polymer, is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 8 pbw. In one particular embodiment, the drift control agent, for instance the water-soluble polymer, is present in an amount having an upper limit, based on 100 pbw of aqueous solution or composition, of 20 pbw.
According to anyone of the invention embodiments, a composition of the invention may comprise greater than about 1 wt% of a drift control agent suspended in a liquid medium, for instance greater than about 2wt%, for instance greater than about 3 wt%, for instance greater than about 4 wt%, for instance at least 5wt% of a drift control agent, for instance an incompletely hydrated water-soluble polymer, suspended in a liquid medium.
In one embodiment, the pesticide composition of the present invention comprises:
(a) at least one an auxin herbicide or salt thereof
(b) a liquid medium,
(c) an incompletely hydrated water-soluble polymer, more typically wherein at least a portion of a water-soluble polymer is in the form of particles of the water-soluble polymer, at least a portion of which are dispersed, more typically suspended in the liquid medium, and
(d) a suspending agent in an amount effective to impart shear thinning properties to the composition;
(e) optionally, a surfactant; and
(f) optionally, hydration inhibitor, which in one embodiment is a glycol, a glycol
derivative, a glycerol, a glycerol derivative, or any combination thereof.
Fatty deposition control agents as a drift control agent
Fatty deposition control agents are also suitable as drift control agents in a composition of the invention.
In particular, emulsified fatty deposition control agents, in particular combinations of a fatty deposition control agent and of a surfactant, may be used according to the invention.
Any known emulsifying surfactant can be combined to a fatty deposition control agent of the invention to obtain an emulsified fatty deposition control agent useful as drift control agent according to the present invention.
Fatty compounds suitable as the fatty deposition control agent as described herein are typically insoluble in water and form a two phase mixture with water in all proportions. In one embodiment, the fatty deposition control agent comprises one or more fatty alkanes, fatty acids, fatty amines, fatty amides, fatty glycerides, fatty triglycerides, fatty acid esters, or any mixture thereof. In another embodiment, the fatty deposition control agent comprises one or more fatty alkanes, fatty acids, fatty amides, fatty glycerides, or any mixture thereof. For example, the fatty deposition control agent, in one embodiment, is a mixture of a fatty acid and a fatty triglyceride. In another embodiment, the fatty deposition control agent comprises one or more fatty alkanes. In another embodiment, the fatty deposition control agent comprises one or more fatty acids. In another embodiment, the fatty deposition control agent comprises one or more fatty glycerides. In another embodiment, the fatty deposition control agent comprises one or more fatty triglycerides. In another embodiment, the fatty deposition control agent comprises one or more fatty acid esters. In another embodiment, the fatty deposition control agent comprises one or more fatty amines. In another embodiment, the fatty deposition control agent comprises one or more fatty amides. Suitable glycerides are mono- di-, and/or tri-esters of glycerol with one or more fatty acids. In one embodiment, the fatty deposition control agent comprises one or more fatty glycerides, which may comprise one or more fatty monoglycerides, fatty diglycerides, fatty triglycerides, or a mixture thereof.
In one embodiment, the fatty glyceride or triglyceride comprises one or more compounds according to structure (I la)
Figure imgf000026_0001
Wherein R20, R21, and R22 are each independently H, (C6-C30)alkyl, (Ci0-C24)alkyl, or
(C6-C3o)alkenyl, more typically (Ci0-C24)alkenyl. In one embodiment, R20, R21, and R22 are each independently (Ci4-Ci8)alkyl. In one embodiment, R20, R21, and R22 are each independently (Cio-C24)alkyl. In one embodiment, R20, R21, and R22 are each independently (Ci6-Ci8)alkyl. In one embodiment, R20, R21, and R22 are each independently (C6-C3o)alkyl. In one embodiment, R , R , and R are each independently (C6-C3o)alkenyl. In one embodiment, R20, R21 , and R22 are each independently (Ci0-C24)alkenyl. R20, R21 , and R22 may each be linear or branched and may each, optionally, be substituted on one or more carbon atoms with hydroxyl, and provided that at least one of R20, R21 , and R22 is not H.
AlkyI moieties suitable as groups of structure (lla) include, for example, (C4-C3o)hydrocarbon group.
Alkenyl moieties suitable as groups of structure (lla) may be mono-unsaturated or poly- unsaturated.
In one embodiment, the fatty glyceride comprises one or more fatty monoglyceride compounds according to structure (l la) wherein two of R20, R21 and R22 are each
independently H and the remaining one of R20, R21 and R22 is (C6-C3o)alkyl, more typically (C6-C24)alkyl, or (C6-C3o)alkenyl, more typically (C8-C24)alkenyl.
In one embodiment, the fatty glyceride comprises one or more fatty diglyceride compounds according to structure (l la) wherein two of R20, R21 and R22 are each independently
(C6-C30)alkyl, more typically (C6-C24)alkyl, or (C6-C30)alkenyl, more typically (C8-C24)alkenyl, and the remaining one of R20, R21 and R22 is H.
In one embodiment, the fatty glyceride comprises one or more fatty triglyceride compounds according to structure (l la) wherein R20, R21 , and R22 are each independently (C6-C24)alkyl, more typically (C6-C24)alkyl, or (C8-C24)alkenyl, more typically (C8-C24)alkenyl. In one embodiment R20, R21 , and R22 are each independently a linear or branched (C4-C30)alkyl, more typically, linear or branched (C8-C24)alkyl, even more typically linear or branched (Ci2-C22)alkyl, or (C5-C24)cycloalkyl, or linear or branched (C4-C30)alkenyl, more typically, linear or branched (C8-C24)alkenyl, even more typically linear or branched (Ci2-C22)alkenyl, or (C5-C24)cycloalkenyl, or (C4-C30)alkaryl, more typically (C8-C24)alkaryl, or (C4-C30)aralkyl, more typically (C8-C24)aralkyl. In one embodiment, R20, R21 , and R22 are each independently a linear or branched (C4-C30)alkyl; or in another embodiment is a linear or branched
(C8-C24)alkyl; or in another embodiment is a linear or branched (Ci2-C22)alkyl; or in another embodiment is a (C5-C24)cycloalkyl; or in another embodiment is a linear or branched (C4-C30)alkenyl; or in another embodiment is a linear or branched (C8-C24)alkenyl; or in another embodiment is a linear or branched (Ci2-C22)alkenyl; or in another embodiment is a (C5-C24)cycloalkenyl; or in another embodiment is a (C4-C30)alkaryl; or in another embodiment is a (C8-C24)alkaryl, or (C4-C30)aralkyl, more typically (C8-C24)aralkyl. In one embodiment, the fatty glyceride or triglyceride comprises one or more compounds according to structure (II):
Figure imgf000028_0001
wherein:
R20, R21, and R22 are each independently H, carboxy(C6-C3o)alkyl, more typically carboxy(Ci0-C24)alkyl, or carboxy(C6-C3o)alkenyl, more typically carboxy(Ci0-C24)alkenyl. In one embodiment, R20, R21, and R22 are each independently carboxy(Ci4-Ci8)alkyl. In one embodiment, R20, R21, and R22 are each independently carboxy(Cio-C24)alkyl. In one embodiment, R20, R21, and R22 are each independently carboxy(Ci6-Ci8)alkyl. In one embodiment, R20, R21, and R22 are each independently carboxy(C6-C3o)alkyl. In one embodiment, R20, R21, and R22 are each independently carboxy(C6-C3o)alkenyl. In one embodiment, R20, R21, and R22 are each independently carboxy(Cio-C24)alkenyl. The alkyl portions of the respective carboxyalkyi groups and the alkenyl portions of the respective carboxyalkenyl groups may each be linear or branched and may each, optionally, be substituted on one or more carbon atoms with hydroxyl, and provided that at least one of R20, R21, and R22 is not H.
Alkyl moieties suitable as the alkyl portion of the carboxyalkyi groups of structure (II) include, for example, (C4-C30)hydrocarbon group.
Alkenyl moieties suitable as the alkenyl portion of the carboxyalkenyl groups of structure (II) may be mono-unsaturated or poly-unsaturated. In one embodiment, the fatty glyceride comprises one or more fatty monoglyceride compounds according to structure (II) wherein two of R20, R21 and R22 are each
independently H and the remaining one of R20, R21 and R22 is carboxy(C6-C30)alkyl, more typically carboxy(C6-C24)alkyl, or carboxy(C6-C30)alkenyl, more typically
carboxy(C8-C24)alkenyl.
In one embodiment, the fatty glyceride comprises one or more fatty diglyceride compounds according to structure (II) wherein two of R20, R21 and R22 are each independently
carboxy(C6-C30)alkyl, more typically carboxy(C6-C24)alkyl, or carboxy(C6-C30)alkenyl, more typically carboxy(C8-C24)alkenyl, and the remaining one of R20, R21 and R22 is H. In one embodiment, the fatty glyceride comprises one or more fatty triglyceride compounds according to structure (I I) wherein R20, R21 , and R22 are each independently
carboxy(C6-C24)alkyl, more typically carboxy(C6-C24)alkyl, or carboxy(C8-C24)alkenyl, more typically carboxy(C8-C24)alkenyl.
In one embodiment, the fatty glyceride is a mixture comprising at least one fatty
monoglyceride compound and at least one fatty diglyceride compound, or at least one fatty monoglyceride compound and at least one fatty triglyceride compound, or at least fatty diglyceride compound and at least one fatty triglyceride compound, or at least one fatty monoglyceride compound, at least one fatty diglyceride compound, and at least one fatty triglyceride compound.
Suitable sources of fatty glycerides include naturally occurring mixtures of fatty glycerides and which may further comprise one or more fatty acids, such as vegetable oils, including, for example, palm oil, soybean oil, rapeseed oil, high erucic acid rapeseed oil, sunflower seed oil, peanut oil, cottonseed oil, palm kernel oil, linseed oil, coconut oil, olive oil, safflower oil, sesame oil, tung oil, canola oil, castor oil, meadowfoam seed oil, hemp oil, as well as mixtures of such oils. Suitable fatty acid glycol ester surfactants include glycol fatty acid monoesters and glycol fatty acid diesters, more typically mono- and di-esters of glycol s and saturated or
unsaturated (C8-C22), more typically (Ci2-Ci8), fatty acids and mixtures thereof, even more typically mono- and di-esters of poly(ethylene glycol) or poly(propylene glycol) and saturated or unsaturated (C8-C22 ), more typically (Ci2-Ci8), fatty acids and mixtures thereof, such as for example, poly(ethylene glycol) monomyristates, poly(ethylene glycol) monostearates, poly(ethylene glycol) distearates, poly(ethylene glycol) monooleates, poly(ethylene glycol) dioleates poly(propylene glycol) monooleates, and poly(ethylene glycol) linolenates, poly(ethylene glycol) dibehenates, poly(ethylene glycol) monobehenates poly(ethylene glycol) monoerucates.
In one embodiment, the drift control agent comprises a fatty deposition control agent comprising one or more fatty glycerides, more typically vegetable oils, and one or more surfactants selected from fatty acid glycol ester surfactants. In one particular embodiment, a concentrated composition of the invention may comprise a fatty deposition control agent as described previously in an amount greater than 1 % by weight of composition, for instance in an amount ranging from 1 % by weight to 50 % by weight, in particular from 5 % by weight to 30 % by weight, for instance from 10 % by weight to 25 % by weight, relative to the total weight of the composition.
HYDRATION INHIBITOR COMPONENT
According to anyone of the invention embodiments, a composition of the invention may optionally further comprise at least one hydration inhibitor component.
As used herein, the term "hydration" in reference to the drift control agent or water soluble polymer component of the present invention means association of substituent groups, typically hydrophilic subsitutent groups, such as hydroxyl groups, of the water soluble polymer with water molecules, such as water molecules of the aqueous medium through, for example, hydrogen bonding. The degree to which the drift control agent or water soluble polymer is hydrated can range from non-hydrated to completely hydrated, with degrees of partial hydration extending between the two extremes. As discussed more fully below, the drift control agent or water soluble polymer is capable of contributing to the viscosity of the composition of the present invention with the magnitude of the contribution being dependent on the degree of hydration of the water soluble polymer. The degree of hydration of the water soluble polymer can thus be characterized based on the magnitude of the contribution that the water soluble polymer makes to the viscosity of the composition:
(a) As referred to herein a "non-hydrated" water soluble polymer makes no significant contribution to the viscosity of the composition. In general, the non-hydrated water soluble polymer would be in the form of a discontinuous phase, for example, discrete particles, that is dispersed in a continuous phase of the liquid medium, ideally with no interaction between the hydrophilic substituents of the polymer and any water molecules present in the liquid medium. In the case of an aqueous medium, there will generally be at least some interaction between the hydrophilic groups of polymer and water molecules of the aqueous medium at interfaces between the phases, for example, at the outer surfaces of the particles. It is believed that in the case of a non- hydrated water soluble polymer, interaction among the hydrophilic substituent groups of the non-hydrated water soluble polymer dominates over interaction between the hydrophilic substituent groups of the polymer and any water molecules present in the aqueous medium, the polymer chains of the non-hydrated water soluble polymer are in a compact, folded conformation, and, in the case where the liquid medium is an aqueous medium, the non-hydrated water soluble polymer is not dissolved in the aqueous medium and remains in the form of a discontinuous phase dispersed in the continuous phase of the aqueous medium. (b) As referred to herein, a "completely hydrated" water soluble polymer makes the maximum contribution to the viscosity of the composition that the water soluble polymer is capable of making. It is believed that in a completely hydrated water soluble polymer, association between the hydrophilic substituent groups of the water soluble polymer and water molecules dominates over interaction among the hydrophilic substituent groups, that the polymer chains of a completely hydrated water soluble polymer are thus in an unfolded, random coil conformation, and in the case where the liquid medium is an aqueous medium, the aqueous medium and completely hydrated water soluble polymer form a single phase, that is, the completely hydrated water soluble polymer is dissolved in the aqueous medium.
(c) As referred to herein, a "partially hydrated" water soluble polymer is a water soluble polymer wherein some of the hydrophilic substituent groups of the polymer are associated with water molecules. At a relatively low level of hydration, the partially hydrated water soluble polymer makes a relatively small contribution to the viscosity of the composition, while at a relatively high level of hydration, the viscosity contribution of a given amount of a partially hydrated water soluble polymer in a given medium approaches, but is less than, the maximum contribution that the amount of water soluble polymer is capable of making in that medium when completely hydrated. It is believed that with increasing hydration, particles of the water soluble polymer swell, an increasing number of hydrophilic substituent groups of the water soluble polymer, including hydrophilic substituent groups within the mass of swollen water soluble polymer, become associated with water molecules, and, as complete hydration is approached, the water soluble polymer chains progressively unfold and approach an unfolded, randomly coiled configuration.
"Non-hydrated" and "partially hydrated" are collectively referred to herein as "incompletely hydrated". A "hydration inhibitor", as referred to herein is any compound that may be added to an aqueous medium to inhibit hydration of a water soluble polymer in the aqueous medium. The degree of hydration of the water soluble polymer can be characterized by viscosity measurements. For example, the viscosity of a given amount of a water soluble polymer, in a given amount of an aqueous medium, in the presence of a given amount of a proposed hydration inhibitor, and under given shear conditions, as described in more detail below (the "test composition"), can be compared to the viscosity of the same amount of the water soluble polymer in the same amount of the aqueous medium in the absence of the proposed hydration inhibitor (the "baseline composition"). If the viscosity of the test composition is equal to that of the baseline composition, then the water soluble polymer of the test composition is deemed to be completely hydrated (and the proposed hydration inhibitor is ineffective in the amount tested to inhibit hydration of the polymer). If the viscosity of the test composition is less than that of the baseline composition, then the water soluble polymer of the test composition is deemed to be incompletely hydrated (and the proposed hydration inhibitor is effective in the amount tested to inhibit hydration of the polymer).
In one embodiment, the incompletely hydrated water soluble polymer comprises solid particles of the water soluble polymer. The presence of such particles can be detected by various means, such as for example, by viewing a sample of the composition of the present invention under an optical microscope.
In one embodiment, the liquid medium is an aqueous liquid medium and at least a portion of the water soluble polymer is in the form of particles of the water soluble polymer. In one embodiment, the liquid medium is an aqueous liquid medium, at least a portion of the water soluble polymer is in the form of particles of the water soluble polymer, and at least a portion of such particles are dispersed, more typically suspended, in the aqueous liquid medium. The presence of such particles in the composition of the present invention is detectable by, for example, optical microscopy.
In one embodiment, the composition of the present invention exhibits a viscosity of less than 10 Pa.s, more typically from about 0.1 to less than 10 Pa.s, and even more typically from about 0.1 to less than 5 Pa.s, at a shear rate of greater than or equal to 10 s'
In one embodiment, the composition of the present invention exhibits a non-Newtonian "shear thinning" viscosity, that is, a viscosity that, within a given range of shear stress, decreases with increasing shear stress. Two general generally recognized categories of flow behavior, that is, plastic flow behavior and pseudoplastic flow behavior, each include shear thinning flow behavior.
In one embodiment, the composition of the present invention exhibits plastic flow behavior. As used herein, the term "plastic" in reference to flow behavior of a composition means the composition that exhibits a characteristic "yield strength", that is, a minimum shear stress required to initiate flow of the composition, and exhibits shear thinning behavior over some range of shear stress above the yield strength. A plastic composition exhibits no flow when subjected to shear stress below its yield strength, and flows when subjected to shear stress above its yield strength, wherein, over an intermediate range of shear stress above its yield strength, the composition typically exhibits a non-Newtonian viscosity that decreases with increasing shear stress, that is, shear thinning behavior, and, at shear stresses above the intermediate range of shear stress, the composition may exhibit a viscosity that does not vary with shear stress, that is, Newtonian flow behavior.
In one embodiment the composition of the present invention exhibits pseudoplastic flow behavior. As used herein, the term "pseudoplastic" in reference to the flow behavior of a composition means that the composition exhibits a viscosity that decreases with increasing shear stress, that is, shear thinning behavior.
In each case, a composition having plastic or pseudoplastic rheological properties resists flow at low shear stress, but that when subjected to an elevated shear stress, such as being shaken in a bottle or squeezed through an orifice, the composition flows and can be easily pumped, poured, or otherwise dispensed from a container. In general, sedimentation or storage condition is a low shear process, having a shear rate in the range of from about 10"6 reciprocal seconds (1/s or, equivalently, s"1) to about 0.01 s"1 and pumping or pouring is a relatively high shear process with a shear rate in the range of greater than or equal to about 1 s"1, more typically from 100s"1 to 10,000 s"1, and even more typically, from 100s"1 to 1 ,000 s"1.
In one embodiment, the hydration inhibitor is selected from surfactants, water soluble non- surfactant salts, water dispersible organic liquids, and mixtures thereof. The terminology "non-surfactant salts" as used herein means salts that are not anionic, cationic, zwitterionic or amphoteric surfactants includes active ingredients, such as pesticide salts, whose primary activity is other than modification of interfacial surface tension. The terminology "water dispersible organic liquids" includes water miscible organic liquids and water immiscible organic liquids that may be dispersed in water, such as for example, in the form of an emulsion of the water immiscible organic liquid in water. In one embodiment, the hydration inhibitor or hydration inhibitor component comprises a water dispersible organic liquid.
Suitable water dispersible organic liquids include, for example, (C1 -C18)alcohols, such as, for example, monohydric alcohols, such as methanol, ethanol, isopropanol, cetyl alcohol, stearyl alcohol, benzyl alcohol, oleyl alcohol, and polyhydric alcohols, such as, for example, 2-butoxyethanol, ethylene glycol, and glycerol, alkylether diols such as, for example, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and diethylene glycol monomethyl ether, and mixtures thereof. In one embodiment, the hydration inhibitor component comprises choline chloride. In one embodiment, the hydration inhibitor is selected from glycol, a glycol derivative, a glycerol, a glycerol derivative, or any combination thereof. Glycols, glycol derivatives, glycerols and/or glycerol derivatives include, but are not limited, to polyglycols, polyglycol derivatives, aliphatic dihydroxy (dihydric) alcohols, polypropylene glycol, triethylene glycol, glycol alkyl ethers such as dipropylene glycol methyl ether, diethylene glycol. In another embodiment, glycols, glycol derivatives, glycerols and/or glycerol derivatives include but are not limited to polyglycols such as polyethylene glycols (PEG) and polypropylene glycols. Glycols are represented by the general formula CnH2n(OH)2, where n is at least 2. Non-limiting examples of glycols include ethylene glycol (glycol), propylene glycol (1 ,2-propanediol), 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,8-octanediol, 1 ,3- propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 4,5-octanediol and 3,4-hexanediol, neopenty glycol, pinacol, 2,2-diethyl-1 ,3-propanediol, 2-ethyl-1 ,3-hexanediol, 2-ethyl-2-butyl-1 ,3-propanediol, isobutylene glycol, 2,3-dimethyl-1 ,3- propanediol, 1 ,3-diphenyl-1 ,3-propanediol, 3-methyl-1 ,3-butanediol. In another embodiment, glycols, glycol derivatives, glycerols and/or glycerol derivatives include but are not limited to glycol stearate, ethylene glycol monostearate, ethylene glycol distearate, ethylene glycol amido stearate, dilaurate glycol, propylene glycol monostearate, propylene glycol dicaprylate, propylene glycol dicaprate diacetate glycol, dipalmite glycol, diformate glycol, dibutyrate glycol, dibenzorate glycol, dipalmate glycol, dipropionate glycol, monoacetate glycol, monopalmitate glycol and monoformate glycol. In another embodiment, glycols, glycol derivatives, glycerols and/or glycerol derivatives also include polypropylene glycol, triethylene glycol, dipropylene glycol methyl ether, or diethylene glycol.
Polyglycol derivatives include but are not limited to polypropylene glycols, as well as polyethylene glycol (PEG) 200-6000 mono and dilaurates, such as, PEG 600 dilaurate, PEG 600 monolaurate, PEG 1000 dilaurate, PEG 1000 monolaurate, PEG 1540 dilaurate and PEG 1540 monolaurate, polyethylene glycol 200-6000 mono and dioleates, such as, PEG 400 monoleate, PEG 600 dioleate, PEG 600 monooleate, PEG 1000 monoleate, PEG 1540 dioleate, PEG 1540 monooleate and polyethylene glycol 200-6000 mono and distearates, such as, PEG 400 distearate, PEG 400 monostearate, PEG 600 distearate, PEG 600 monostearate, PEG 1000 distearate, PEG 1000 monostearate, PEG 1540 distearate, PEG 1540 monostearate and PEG 3000 monostearate.
Examples of glycerol derivatives include but are not limited to glycerol monolaurate, glycerol monostearate, glycerol distearate, glycerol trioleate, glycerol monooleate, glycerol dilaurate, glycerol dipalmitate, glycerol triacetate, glycerol tribenzoate, glycerol tributyrate, glycerol monopalmitate, glycerol trimyristate, glycerol trilaurate, glycerol tripalmitate and glycerol tristearate. In one embodiment, the composition of the present invention exhibits a viscosity of less than 10 Pa.s, more typically from about 0.1 to less than 10 Pa.s, at a shear rate of greater than or equal to 10 s' In one embodiment, the composition of the present invention exhibits a viscosity of less than 7 Pa.s, more typically from about 0.1 to less than 7 Pa.s, at a shear rate of greater than or equal to 10 s' In one embodiment, the composition of the present invention exhibits a viscosity of less than 5 Pa.s, more typically from about 0.1 to less than 5 Pa.s, at a shear rate of greater than or equal to 10 s"1. In one embodiment, such a viscosity profile equates to the composition being flowable, i.e., able to be pumped. This characteristic is an advantage as end use applications from a storage container typically prefer to pump components into the final application tank for crop application. For example, typically farmers will add components for a final tank mix into separate tanks, such as a tank for water, a tank for an adjuvant composition, a tank for a water conditioner, and have those components pumped into a final end use application tank.
In one embodiment, the composition of the present invention is prepared on an as needed basis and is sufficiently stable, that is, a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation, such as, separation into layers and/or precipitation of components, such as, for example, separation of incompletely hydrated water-soluble polymer from the liquid medium, within the anticipated time period.
In one embodiment, the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, such as, for example, one week, more typically, one month, even more typically 3 months, under given storage conditions, such as, for example, at room temperature. In another embodiment, the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, which in one embodiment is one week, more typically, one month, even more typically 3 months, under high termperature storage conditions, e.g., greater than 50 °C. In one embodiment, the composition of the present invention is shelf stable (i.e., exhibits at least part of the good storage stability as detailed above) at a temperature greater than 50 °C for at least 24 hours, or 48 hours, or in yet another embodiment, 72 hours.
In one embodiment, the composition of the present invention exhibits good storage stability and a quiescent sample of the composition shows no evidence, by visual inspection, of gravity driven separation within a given time, such as, for example, 24 hours, more typically, four days, even more typically, one week, under accelerated aging conditions at an elevated storage temperature of up to, for example, 54°C, more typically, 45°C.
In one embodiment, a concentrated composition of the invention exhibits a Brookfield viscosity at 25°C and at 20 rpm of less than or equal to about 5,000 centiPoise ("cP"), more typically of less than or equal to 2,500 cP, for example from about 10 to about 1 ,500 , especially from about 10 to about 1 ,000 cP.
A concentrated composition of the invention exhibits good storage stability. The criteria for assessing storage stability are that the formulation remains substantially homogeneous in visual appearance during storage and does not separate into layers of mutually insoluble liquid phases and does not form any solid precipitate upon quiescent standing
In one embodiment, the concentrated composition of the invention remains stable during storage at temperatures from -5°C to 54°C for greater than or equal to 7 days, more typically for greater than or equal to 14 days (adaptation of CIPAC test MT46.3).
The concentrated composition of the invention remains stable during storage at room temperature for more than or equal to 7 days, more typically for greater than or equal to 14 days and even more typically for greater than or equal to 30 days.
A concentrated composition of the invention also exhibits good dilution stability and/or provides a suitable dispersion.
The term "suitable dispersion" is intended to denote a dispersion after dilution in water (CIPAC standard waters A or D) which exhibits substantially no or little phase separation (sedimentation, creaming, etc)) over time, in particular when it is stored for 30 minutes in a water bath thermostatted at 30°C, preferably for 2 hours in a water bath thermostatted at 30°C and ideally for 24 hours in a water bath thermostatted at 30°C (adaptation of CIPAC test MT41 and MT184).
The concentrated composition of the invention may comprise additional pesticides in addition to the auxin herbicide.
Suitable additional pesticides are pesticides as defined below. Preferred additional pesticides are herbicides, such as
- amino acid derivatives: bilanafos, glyphosate (e.g. glyphosate free acid, glyphosate ammonium salt, glyphosate isopropylammonium salt, glyphosate trimethylsulfonium salt, glyphosate potassium salt, glyphosate dimethylamine salt), glufosinate (e.g. glufosinate ammonium salt), sulfosate; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop. More preferred additional pesticides are glyphosate and glufosinate.
According to anyone of the invention embodiments, a concentrated composition of the invention may comprise, in addition to said water-soluble salt of an auxin herbicide, at least one water-soluble salt of at least one additional herbicide.
For instance, a concentrated composition of the invention may further comprise at least one water-soluble salt of glyphosate and/or at least one water-soluble salt of glufosinate.
According to anyone of the invention embodiments, the total amount of water-soluble salts (whether it be a water-soluble salt of said auxin herbicide alone or a combination of a water- soluble salt of said auxin herbicide with a water-soluble salt of an additional herbicide and/or with added water-soluble salt) may be of at least 300 g/L.
According to anyone of the invention embodiments, a concentrated composition of the invention may also comprise, in addition to said water-soluble salt of an auxin herbicide, at least one additional herbicide which is insoluble in said concentrated composition, for instance present in a dispersed form.
According to another one of the invention embodiments, a concentrated composition of the invention may also comprise, in addition to said water-soluble salt of an auxin herbicide, at least one additional herbicide present in a soluble form in a liquid medium different from the aqueous continuous phase and which is non-miscible in said aqueous phase, with said liquid medium being present in an emulsified form in said concentrated composition. Suspo- emulsions are typical examples of such compositions.
The concentrated composition of the invention may comprise auxiliaries, such as
volatilization reduction additives, solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants.
Suitable solvents and liquid carriers are organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol,
cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and
tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. The alkoxylate of the formula (I) is not a nonionic surfactant within the meaning of this invention. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are for instance polysaccharides (e.g. xanthan gum,
carboxymethylcellulose), anorganic clays (organically modified or unmodified),
polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as
alkylisothiazolinones, alkylchloroisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron
hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
In one embodiment, the composition of the invention is free or substantially free of ammonium-containing water conditioning agent, in particular ammonium sulfate. In one embodiment, the composition is concentrated blend of a at least one an auxin herbicide or salt thereof, a drift control agent and suspending agent as defined previously, which composition is stable, has a low viscosity, is easily transportable, is pourable and pumpable under field conditions, and is dilutable with water under field conditions to form a dilute pesticide composition for spray application to target pests. In one embodiment, the concentrated pesticide composition of the present invention is diluted with water, typically in a ratio of from 1 :10 to 1 :1 ,000 parts by weight pesticide concentrate composition: parts by weight water, for instance in a ratio of from 1 :10 to 1 :100 parts by weight pesticide concentrate composition: parts by weight water to form a dilute pesticide composition for spray application to target plants. Optionally, other components, such as additional pesticide, polymer, surfactants, fertilizer, and/or other adjuvants, may be added to the dilute pesticide composition. In one embodiment, the pesticide composition of the present invention is applied, in dilute form, to foliage of a target plant at a rate of from about 0.25 pint, more typically about 0.5 pint, to about 5 pints, even more typically from about 1 pint to about 4 pints, as expressed in terms of the above described pesticide concentrate embodiment of the pesticide composition of the present invention (that is, comprising, based on 100 pbw of such composition, up to about 70 pbw, more typically from about 10 to about 60 pbw, more typically from about 25 to about 55 pbw, pesticide) per acre.
In one embodiment, the pesticide composition is spray applied in dilute form via conventional spray apparatus to foliage of one or more target plants present on an area of ground at a rate of from about 1 gallon to about 20 gallons, more typically about 3 gallons to 20 gallons, of the above described diluted pesticide composition per acre of ground.
The pesticide compositions of the invention may advantageously also be useful to reduce volatility of said auxin herbicide and off-site movement of said auxin herbicide.
Volatilization occurs when pesticide surface residues change from a solid or liquid to a gas or vapor after an application of a pesticide has occurred. Once airborne, volatile pesticides can move long distances off site (and in particular longer distances compared to spray drift).
Another object of the present invention is to provide auxin herbicide compositions having reduced volatility relative to currently available compositions, and preferably reduced- volatility compositions that exhibit no significant reduction in herbicidal effectiveness relative to currently available compositions.
Advantageously, it is believed that the compositions of the present invention provide enhanced protection from off-target crop injury while maintaining comparable herbicidal efficacy on auxin-susceptible plants located in the target area.
Impact on the auxin herbicide volatility can be measured by conventional means known to those skilled in the art.
For instance, volatilization of an auxin herbicide can be assessed as follows : an auxin herbicide composition is heated, causing the auxin herbicide to volatilize from said composition into the gas phase. Weight of residual auxin herbicide composition is recorded against time (through thermogravimetric analyses), allowing indirect measurement of volatilization of the auxin herbicide.
Some details or advantages of the invention will appear in the non-limitative examples below.
EXAMPLES
Example 1 and Comparative Example C1
The composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
The composition of Comparative Example 1 was analogous to that of Example 1 , but with another suspending agent (Stearalkonium hectorite).
The compositions were prepared as follows. During all the preparation, the medium was stirred using an inox deflocculating blade (diameter 35 mm) at a speed of 800 rpm. 94.7% wt. Engenia™ (N,N-bis(3-aminopropyl)methylamine salt of Dicamba, 600 g/L a.e. BASF) were introduced in a plastic beaker. 0.01 %wt. preservative (Kathon CG™, Dow) were added. Then 0.29% wt. suspending agent (Bentone DY-CE™, Elementis Specialties) were slowly added (gentle sprinkling using a spatula). The formulation was then left for 3 hours under stirring (800 rpm). Then 5.00%wt. non-derivatized guar gum (having a weight average molecular weight of about 2,000,000 g/mol) were slowly introduced (gentle sprinkling using a spatula). The formulation was then left for 1 hour under stirring (800 rpm).
The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C1 was not stable as top syneresis appeared after 3 days at room temperature and 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
Samples of the compositions of Example 1 were diluted with water CIPAC D (342 ppm) at 30°C.
The materials and their relative amounts used to make the compositions of Examples 1 and C1 are set forth in Table I below and the stability and dilution results for Example 1 and Comparative Example C1 are set forth in Table l-A below.
TABLE I. Concentrated aqueous BAPMA Dicamba herbicide compositions.
Figure imgf000041_0001
(Engenia ' M)
Preservative
0.01 0.09
(Kathon CG™, Dow)
suspending agent
0.29 -
(Bentone DY-CE™, Elementis Specialties)
suspending agent
- 0.50
(Bentone 27™, Elementis Specialties)
Non-derivatized guar
5.00 5.03
(Solvay)
TABLE l-A
Figure imgf000042_0001
Example 1 and Comparative Example C2
The composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay). The composition of Comparative Example 2 was analogous to that of Example 1 , but with another suspending agent (Quaternium-18 hectorite).
The comparative Example 2 were prepared in the same fashion of Example 1.
The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C2 was not stable as top syneresis appeared after 3 days at room temperature and 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
Samples of the compositions of Example 1 were diluted with water CIPAC D (342 ppm) at 30°C.
The materials and their relative amounts used to make the compositions of Examples 1 and C2 are set forth in Table II below and the stability and dilution results for Example 1 and Comparative Example C2 are set forth in Table ll-A below.
TABLE II. Concentrated aqueous BAPMA Dicamba herbicide compositions.
Figure imgf000043_0001
Non-derivatized guar
5.00 5.00
(Solvay)
TABLE ll-A
Figure imgf000044_0001
RT = Room Temperature
Example 1 and Comparative Example C3
The composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
The composition of Comparative Example 3 was analogous to that of Example 1 , but with another suspending agent (Highly benefiated smectite clay).
The comparative Example 3 were prepared in the same fashion of Example 1.
The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C3 was not stable as top syneresis appeared after 1 day at room temperature. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
Samples of the compositions of Example 1 were diluted with water CIPAC D (342 ppm) at 30°C.
The materials and their relative amounts used to make the compositions of Examples 1 and C3 are set forth in Table III below and the stability and dilution results for Example 1 and Comparative Example C3 are set forth in Table lll-A below.
TABLE III. Concentrated aqueous BAPMA Dicamba herbicide compositions.
Figure imgf000045_0001
TABLE lll-A
EX 1 CEX3 Viscosity
(Brookfield LV, 720 cP 100 cP SP62 @RT)
Before
storage Dilution (1 % in
CIPAC D 30°C) Acceptable dispersibility -
2h
3 weeks RT: Stable, 1 day, RT: 30% syneresis (gel)
Aspect
Homogeneous 3 days, 54°C: 45% syneresis
After
storage Viscosity
(Brookfield LV, 3 weeks RT: 1 140 cP
- 20rpm, SP62
2 weeks 54°C: 880 cP
@RT)
RT = Room Temperature
Example 4 and Comparative Example C4
The composition of Example 4 was an aqueous herbicide composition that contained a pesticide (Diglycolamine salt of Dicamba), a water soluble polysaccharide polymer (non- derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay).
The composition of Comparative Example 4 was analogous to that of Example 4, but with another suspending agent (Hectorite and Hydroxy Ethyl Cellulose).
SL DGA Dicamba was prepared as follows. Preparation of diluted solution of DGA: 47.8% wt. deionized water were introduced in a glass bottle of 500 ml_. 52.2% wt. DGA (DiGlycolAmine, 98%, Merck) were added into the water. The solution was stirred (magnetic stirrer, 700 rpm) during 45 min.
Preparation of SL DGA Dicamba: 35.7% wt. diluted solution of DGA were introduced in a glass bottle of 1 L. 64.3% wt. acid dicamba were added slowly under magnetic stirring (400rpm). The mixture is stirred during 1 hour at 700rpm (targeted value of pH: 6).
The compositions of Example 4 and comparative Example 4 were prepared in the same fashion of Example 1.
The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature conditions and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition was taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Comparative example C4 was not stable as top syneresis appeared after 3 days at room temperature. Example 4 was stable for 4 months at room temperature. The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
The materials and their relative amounts used to make the compositions of Examples 4 and C4 are set forth in Table IV below and the stability results for Example 4 and Comparative Example C4 are set forth in Table IV-A below.
TABLE IV. Concentrated aqueous DGA Dicamba herbicide compositions.
Figure imgf000047_0001
TABLE IV-A
Figure imgf000047_0002
Example 1 and Comparative Example C5
The composition of Example 1 was an aqueous herbicide composition that contained a pesticide (N,N-bis(3-aminopropyl)methylamine salt of Dicamba), a water soluble polysaccharide polymer (non-derivatized guar) and a suspending agent (Organically modified and beneficiated smectite clay). The composition of Comparative Example 5 was analogous to that of Example 1 , but with another suspending agent (Xanthan gum).
The comparative Example 5 was prepared in the same fashion of Example 1.
The stability of each of the compositions was evaluated by allowing a sample of the composition to sit undisturbed in a 100 milliLiter (mL) glass vial under room temperature and hot conditions (54°C, oven) and visually observing the composition to detect detrimental viscosity increase and/or separation of the components of the composition due to gravity. Separation of the components of the composition and significant viscosity increase were taken as evidence of instability. Compositions that did not exhibit separation within a given period of time were characterized as being stable for that period of time. Compositions that are easily pourable were characterized as being stable for that period of time. Comparative example C5 was not stable as top syneresis appeared after 4 days at 54°C. Example 1 was stable and showed no evidence of viscosity increase or phase separation for 2 weeks at room temperature (little phase separation was observed after 2 weeks at 54°C. Sample was easy to re-homogeneize).
The viscosity of each of the compositions was measured at room temperature using a Brookfield LV viscometer equipped with a SP62 spindle at 20 revolutions per minute ("rpm").
Samples of the compositions were diluted with water CIPAC D (342 ppm) at 30°C.
The materials and their relative amounts used to make the compositions of Examples 1 and C5 are set forth in Table V below and the stability and dilution results for Example 1 and Comparative Example C5 are set forth in Table V-A below.
TABLE V. Concentrated aqueous BAPMA Dicamba herbicide compositions.
EX 1 CEX5
Materials % wt. % wt.
Aqueous solution of N,N-bis(3- aminopropyl)methylamine salt of Dicamba 94.7 94.81
(Engenia™)
Preservative
0.01 0.06
(Kathon CG™, Dow)
suspending agent
0.29
(Bentone DY-CE™, Elementis Specialties)
suspending agent - 0.10 (Rhodopol 23, Solvay)
Non-derivatized guar
5.00 5.03
(Solvay)
TABLE V-A
Figure imgf000049_0001
Drift measurements
The aqueous spray compositions of Example 1 and Engenia were made by diluting compositions Example 1 and Engenia™ (BASF) in 342 ppm hardness CIPAC water to provide dilute aqueous mixtures containing the relative amount of the respective compositions Example 1 and Engenia™ as percent by weight of the dilute composition in Table VI below.
The dilute aqueous compositions thus obtained were sprayed through a single flat fan nozzle AI 1 1003-VS at a pressure of 40 psi in a flow-controlled hood (speed 1.6 mph) and the droplet size distribution was measured perpendicular to the plane pf spray pattern and 12 inches below the nozzle tip. A Sympatec Laser HELOS-VARIO/KR multi range (Sympatec GmbH, Germany) was used to measure the spray droplets using a R7 lens.
Two parameters V<150 (% of volume of spray droplets of less than 150 microns (i.e., representative of driftable fines)) and VMD (Volume Median Diameter (defined as the droplet size below which 50% volume of spray is contained)) are reported in the Table VI. The spray compositions of Example 1 exhibited a smaller amount of small size spray droplets that are very susceptible to spray drift, i.e. below 150 μηη in size, compared to respective analogous compositions of Engenia™. TABLE VI
Figure imgf000050_0001

Claims

C L A I M S
1 . A pesticide composition comprising, by total weight of the composition:
-a pesticide comprising at least one water-soluble salt of an auxin herbicide;
-greater than about 0.5 wt% of a drift control agent suspended in an aqueous liquid medium; and
- a suspending agent in an amount effective to impart shear thinning properties to the composition, the suspending agent comprising at least one organically modified and beneficiated smectite clay.
2. The composition of claim 1, wherein said organically modified and beneficiated smectite clay is the ion-exchanged reaction product of (a) a smectite clay and (b) one or more quaternary ammonium compounds and/or (c) one or more organic materials.
3. The composition of claim 1 , wherein said smectite clay (a) is selected from the group consisting of bentonite and hectorite.
4. The composition of claim 2, wherein said quaternary ammonium compound (b) has the formula:
R1
I
-N-R4
R3
wherein R1 comprises a group selected from (i) linear or branched aliphatic, aralkyl, or aromatic hydrocarbon groups having from 8 to 30 carbon atoms or (ii) alkyl or alkyl-ester groups having 8 to 30 carbon atoms; R2, R3, and R4 are independently selected from the group consisting of (a) linear or branched aliphatic hydrocarbon, fluorocarbon, or other halocarbon groups having from 1 to about 30 carbon atoms; (b) aralkyl or aromatic groups having from 6 to about 30 carbon atoms, (c) alkoxylated groups containing from 1 to about 80 moles of alkylene oxide; (d) amide groups, (e) oxazolidine groups, (f) allyl, vinyl, or other alkenyl or alkynyl groups possessing reactive unsaturation and having from 2 to about 30 carbon atoms, and (g) hydrogen: and X' comprises an anion selected from the group consisting of chloride, methyl sulfate, acetate, iodide, and bromide.
5. The composition of claim 1 , wherein said organically modified and beneficiated smectite clay has a bulk density lower than 1 .5 g/cm3, for instance lower than 1 .0 g/cm3, for instance lower than 0.8 g/cm3, for instance lower than 0.7 g/cm3.
6. The composition of claim 1 , wherein the composition comprises greater than about 0.5 wt% of organically modified and beneficiated smectite clay, for instance greater than 1 wt%, relative to the total weight of the composition.
7. The composition of claim 1 , wherein the composition comprises greater than about 5 wt% of an aqueous liquid medium, for instance greater than about 10 wt%, for instance from about 10 wt% to about 80 wt%, for instance from about 15 wt% to about 75 wt% of an aqueous liquid medium relative to the total weight of the composition.
8. The composition of claim 1 further comprising the presence of at least 300 g/L of water soluble salts.
9. The composition of claim 1 , wherein the composition comprises at least 300 g/L a.e. of at least one water-soluble salt of an auxin herbicide.
10. The composition of claim 1 wherein the pesticide comprises a dicamba salt, wherein the salt is N,N-bis(3-aminopropyl)methylamine, diethanolamine, monoethanolamine, dimethylamine, isopropylamine, dimethylethanolamine, diglycolamine, potassium, choline, or sodium.
1 1 . The composition of claim 1 wherein the pesticide comprises dicamba diglycolamine salt or dicamba N,N-bis(3-aminopropyl)methylamine salt.
12. The composition of claim 1 wherein the drift control agent is a water-soluble polymer.
13. The composition of claim 1 wherein the drift control agent comprises a guar derivative, the guar derivative comprising cationic guar, carboxymethyl guar (CM guar), hydroxyethyl guar (HE guar), hydroxypropyl guar (HP guar), carboxymethylhydroxypropyl guar (CMHP guar), hydrophobically modified guar (HM guar), hydrophobically modified carboxymethyl guar (HMCM guar), hydrophobically modified hydroxyethyl guar (HMHE guar), hydrophobically modified hydroxypropyl guar (HMHP guar), cationic hydrophobically modified hydroxypropyl guar (cationic HMHP guar), hydrophobically modified
carboxymethylhydroxypropyl guar (HMCMHP guar), hydrophobically modified cationic guar (HM cationic guar), guar hydroxypropyl trimonium chloride, or hydroxypropyl guar hydroxypropyl trimonium chloride.
14. The composition of claim 1 wherein the drift control agent is native guar, polyacrylamide, a cationic hydroxypropyl guar, a cationic guar, or a combination thereof.
15. The composition of claim 1 , wherein the drift control agent is a fatty deposition control agent, in particular an emulsified fatty deposition control agent.
16. The composition of claim 1 , wherein the composition further comprises a hydration inhibitor component.
17. The composition of claim 16, wherein said hydration inhibitor component comprises propylene glycol or poly(ethylene glycol).
18. The composition of claim 16, wherein the hydration inhibitor component further comprises choline chloride.
19. The composition of claim 1 further comprising one or more surfactants.
20. The composition of claim 1 wherein the composition exhibits a viscosity of less than 10 Pa.s at a shear rate of greater than or equal to 10 s"1.
21 . The composition of claim 1 wherein the composition comprises greater than about 1 wt% of a drift control agent suspended in a liquid medium, for instance greater than about 2wt%, for instance greater than about 3 wt%, for instance greater than about 4 wt%, for instance at least 5wt% of a drift control agent, for instance an incompletely hydrated water- soluble polymer, suspended in a liquid medium.
22. The composition of claim 1 wherein the composition exhibits:
(a) a viscosity of greater than or equal to 5 Pa.s at a shear rate of less than 0.01 s"1, and
(b) a viscosity of less than 5 Pa.s at a shear rate of greater than 10 s"1.
23. The composition of claim 1 wherein the composition is free or substantially free of ammonium-containing water conditioning agent, in particular ammonium sulfate.
PCT/EP2018/080699 2017-11-09 2018-11-08 Agricultural pesticide compositions WO2019092156A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762583781P 2017-11-09 2017-11-09
US62/583,781 2017-11-09

Publications (1)

Publication Number Publication Date
WO2019092156A1 true WO2019092156A1 (en) 2019-05-16

Family

ID=64267825

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/080699 WO2019092156A1 (en) 2017-11-09 2018-11-08 Agricultural pesticide compositions

Country Status (2)

Country Link
AR (1) AR114141A1 (en)
WO (1) WO2019092156A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412018A (en) 1980-11-17 1983-10-25 Nl Industries, Inc. Organophilic clay complexes, their preparation and compositions comprising said complexes
US4434075A (en) 1981-10-19 1984-02-28 Nl Industries, Inc. Anionically modified organophilic clays and their preparation
US4577112A (en) 1983-04-13 1986-03-18 Commissariat A L'energie Atomique Movable enclosure for the replacement and transportation of contaminated parts and complementary casing for such an enclosure
US6421698B1 (en) 1998-11-04 2002-07-16 Teleman Multimedia, Inc. Multipurpose processor for motion estimation, pixel processing, and general processing
WO2013189773A1 (en) 2012-06-21 2013-12-27 Basf Se An aqueous composition comprising dicamba and a drift control agent
WO2015091617A1 (en) * 2013-12-18 2015-06-25 Basf Se A composition comprising dicamba and a drift control agent comprising at least one fatty alcohol
WO2016124467A1 (en) 2015-02-06 2016-08-11 Lamberti Spa Aqueous adjuvant concentrates with improved spray drift properties
WO2017027250A1 (en) * 2015-08-07 2017-02-16 Rhodia Operations Choline salt and ammonium-free adjuvants for water conditioning and agricultural formulations
EP3135113A1 (en) * 2015-08-31 2017-03-01 Basf Se Use of herbicidal compositions for controlling unwanted vegetation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4412018A (en) 1980-11-17 1983-10-25 Nl Industries, Inc. Organophilic clay complexes, their preparation and compositions comprising said complexes
US4434075A (en) 1981-10-19 1984-02-28 Nl Industries, Inc. Anionically modified organophilic clays and their preparation
US4577112A (en) 1983-04-13 1986-03-18 Commissariat A L'energie Atomique Movable enclosure for the replacement and transportation of contaminated parts and complementary casing for such an enclosure
US6421698B1 (en) 1998-11-04 2002-07-16 Teleman Multimedia, Inc. Multipurpose processor for motion estimation, pixel processing, and general processing
WO2013189773A1 (en) 2012-06-21 2013-12-27 Basf Se An aqueous composition comprising dicamba and a drift control agent
WO2015091617A1 (en) * 2013-12-18 2015-06-25 Basf Se A composition comprising dicamba and a drift control agent comprising at least one fatty alcohol
WO2016124467A1 (en) 2015-02-06 2016-08-11 Lamberti Spa Aqueous adjuvant concentrates with improved spray drift properties
WO2017027250A1 (en) * 2015-08-07 2017-02-16 Rhodia Operations Choline salt and ammonium-free adjuvants for water conditioning and agricultural formulations
EP3135113A1 (en) * 2015-08-31 2017-03-01 Basf Se Use of herbicidal compositions for controlling unwanted vegetation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KNOWLES: "Agrow Reports DS256", 2006, T&F INFORMA, article "Adjuvants and additives"
MCCUTCHEON'S: "Emulsifiers & Detergents", vol. 1, 2008, MCCUTCHEON'S DIRECTORIES

Also Published As

Publication number Publication date
AR114141A1 (en) 2020-07-29

Similar Documents

Publication Publication Date Title
AU2018366265B2 (en) Aqueous compositions comprising dicamba and a built-in drift control agent
WO2019094687A1 (en) Aqueous compositions comprising dicamba and a built-in drift control agent
BR112014006545B1 (en) agricultural adjuvant composition, concentrated and aqueous pesticide compositions for final use, method of preparing these compositions and method for controlling a target parasite
US20120122688A1 (en) Agricultural pesticide compositions
AU2021201043B2 (en) Choline salt and ammonium-free adjuvants for water conditioning and agricultural formulations
ES2237198T3 (en) PESTICIDED FORMULATIONS CONTAINING ESTER TENSIOACTIVE HEMISULFATE TRIESTIRIL-PHENOL ALCOXYLATE NEUTRALIZED WITH ALCOXYLED AMINE.
EP1651048A1 (en) High-strength, low viscosity herbicidal formulations of glyphosate
JP2010163437A (en) Pesticide formulation containing alkoxylated amine-neutralized aromatic sulfonic acid surfactant
AU2018363781A1 (en) Agricultural pesticide compositions
BR112017021825B1 (en) ADJUVANT COMPOSITION AND METHOD FOR PREPARING A PESTICIDE COMPOSITION
EP3282843A1 (en) Dry ammonium-free adjuvant for drift reduction and water conditioning
WO2019092156A1 (en) Agricultural pesticide compositions
WO2019092158A1 (en) Agricultural pesticide compositions
US20220000100A1 (en) Water conditioning and drift control compositions and methods of use
WO2019092157A1 (en) Agricultural pesticide compositions
BR112019016187A2 (en) ams-free adjuvants for water conditioning and agricultural formulations
DE102008016620A1 (en) Pesticide formulations containing alkoxylated oligoamines and alkoxylated mono- and / or diamines

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18800149

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18800149

Country of ref document: EP

Kind code of ref document: A1