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WO2018090072A1 - Co-formulation comprenant un régulateur de croissance végétale et une huile, et procédés de préparation et d'utilisation de ladite co-formulation - Google Patents

Co-formulation comprenant un régulateur de croissance végétale et une huile, et procédés de préparation et d'utilisation de ladite co-formulation Download PDF

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Publication number
WO2018090072A1
WO2018090072A1 PCT/AU2017/000216 AU2017000216W WO2018090072A1 WO 2018090072 A1 WO2018090072 A1 WO 2018090072A1 AU 2017000216 W AU2017000216 W AU 2017000216W WO 2018090072 A1 WO2018090072 A1 WO 2018090072A1
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Prior art keywords
oil
plant growth
growth regulator
formulation
dispersion
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PCT/AU2017/000216
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English (en)
Inventor
Rowan BROWN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Indorama Ventures Oxides Australia Pty Ltd
Original Assignee
Huntsman Corp Australia Pty Ltd
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Filing date
Publication date
Priority claimed from AU2016904732A external-priority patent/AU2016904732A0/en
Application filed by Huntsman Corp Australia Pty Ltd filed Critical Huntsman Corp Australia Pty Ltd
Priority to JP2018551098A priority Critical patent/JP7015787B2/ja
Priority to AU2017361105A priority patent/AU2017361105B2/en
Priority to CA3017030A priority patent/CA3017030A1/fr
Priority to CN201780020812.4A priority patent/CN109068629A/zh
Priority to BR112018069842A priority patent/BR112018069842A2/pt
Priority to EP17871625.4A priority patent/EP3541183A4/fr
Priority to MX2018011686A priority patent/MX392364B/es
Publication of WO2018090072A1 publication Critical patent/WO2018090072A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the invention generally relates to the co-formulation of at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, or mixtures thereof, with various oils to form agricultural oil-based dispersions or oil dispersions. More particularly, the present invention relates to an oil-dispersion containing a plant growth regulator, or a mixture of a plant growth regulator and an herbicide, which may subsequently be used as a defoliant. It will be convenient to hereinafter describe the invention in relation to the use of the oil dispersion as a defoliant, particularly upon cotton crops. It should be appreciated, however, that the present invention is not limited to that application only.
  • One common formulation design strategy for achieving such requirements is the combination or co-formulation of agrochemicals and/or specific formulation auxiliaries, which might otherwise be applied individually.
  • the primary logic is that one of the more effective methods for fulfilment of the aforementioned requirements, for example, the co- formulation of agrochemicals and/or specific formulation auxiliaries, which previously might have been applied as separate, individual delivery systems, could potentially be applied as one formulation. This would result in reduced waste, reduced labour inputs, reduced application complexity, as well as possible synergistic benefits with respect to efficacy.
  • One particular formulation type that is well suited to this delivery strategy is the dispersion of an agriculturally active solid in oi l, forming either an oil dispersi on (hereinafter “OD”) concentrate, or an oil-miscible flowable (hereinafter “OF”) concentrate, as defined by CropLife International, an international trade association of agribusiness companies that was founded in 2001.
  • OD oil dispersi on
  • OF oil-miscible flowable
  • Such common delivery systems may include, but are not limited to, wettable powders, soluble powders, water dispersible granules, water soluble granules, dusts, suspension concentrates, emulsifiable concentrates, and emulsions.
  • an OD or an OF formulation for an OD or an OF formulation to be optimally efficacious, it will also preferably contain a significant concentration of non-aqueous media, preferably an oil, where the concentration of the oil relative to the remaining components that facilitate effective delivery of the formulation, such as one or more emulsifying agent co-solvent, is significantly higher.
  • a significant concentration of non-aqueous media preferably an oil
  • concentration of oil relative to the remaining components that facilitate effective delivery of the formulation such as one or more emulsifying agent co-solvent
  • high concentrations of oil, particularly mineral or base oils are generally detrimental to formulation stability, owing to their low-polarity and the resultant impact upon the performance of functional formulation auxiliaries, such as di spersants and rheology modifi ers, for example.
  • thidiazole-urea plant growth regulators such as thidiazuron
  • the present inventor therefore sought to prepare useful compositions comprising a plant growth regulator.
  • thidiazuron, or mixtures of thidiazuron with diuron appear to have been inefficiently applied and more than was actually required for optimal efficacy has been used, resulting in wastage. This has had disadvantageous consequences from an environmental and an economical perspective.
  • the present invention seeks to overcome, or at least substantially ameliorate, some of the disadvantages and shortcomings of the prior art.
  • an agricultural co-formulation comprising:
  • the final concentration of the at least one plant growth regulator, or the at least one plant growth regulator and the additional biologically active ingredient is optionally adjusted by adding additional oil and one or more rheology modifiers and/or activation agents as required to substantially stabilise the co-formulation; and wherein the efficacy of the plant growth regulator is substantially maintained or improved.
  • the form of the co-formulation of the present invention may be selected from an oil dispersion ("OD") concentrate, an oil-miscible flowable (“OF”) concentrate, an oil-based suspension concentrate (“SC”), or an oil-based suspoemulsion (“SE”).
  • OD oil dispersion
  • OF oil-miscible flowable
  • SC oil-based suspension concentrate
  • SE oil-based suspoemulsion
  • the co-formulation is an oil-based dispersion concentrate, i.e. an OD formulation.
  • the term "effective amount” means an amount of a component of the co-formulation according to the invention that is sufficient for enhancing the plant growth, yield and/or vigour and that does not entail any appreciable symptom of phytotoxicity for the plant or crop. Such an amount can vary within a wide range depending on the type of plant or crop, the climatic conditions and the components included in the co-formulation according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
  • plant growth regulator includes compounds eliciting a response in terms of plant organ number modulation in a dose-dependent manner.
  • Plant organ number modulation refers to the enhancement or inhibition of plant organ growth or development. Inhibition may be complete blockage or partial blockage.
  • plant organ number modulation can relate to inhibition of shoot branchin g or enh ancement of root formation.
  • Shoot branching means the process of outgrowth of axillary or adventitious buds, resulting in the formation of vegetative shoots, flowers or inflorescences.
  • Inhibition means to permanently or temporarily suppress the growth of buds or inhibit the formation of roots.
  • the inhibition can be complete, by affecting all axillary/adventitious buds, or partial, affecting only a subset of axillary/adventitious buds.
  • Examples of plant growth regulators include, but are not limited to, antiauxins, such as clofibric acid or 2,3,5-tri- iodobenzoic acid; auxins, such as 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA, I BA, naphthaleneacetamide, a-naphthaleneacetic acid, 1 -naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T; cytokinins, such as 2iP, benzyladeine kinetin, zeatin; defoliants, such as calcium cyanamide, dimethipin, endothal, ethephon, merphos, metoxuron, pentachlorophenol, thidiazuron, tribufos; ethylene inhibitors, such as avigly, antiauxins, such as clofibric
  • the term also includes other active ingredients such as benzofiuor, buminafos, carvone, ciobutide, clofencet, cloxyfonac, cyclanilide, cycloheximide, epocholeone, ethychlozate, ethylene, fenridazon, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, prohexadione, pydanon, sintofen, triapenthenol, and trinexapac.
  • active ingredients such as benzofiuor, buminafos, carvone, ciobutide, clofencet, cloxyfonac, cyclanilide, cycloheximide, epocholeone, ethychlozate, ethylene, fenridazon, heptopargil, holos
  • Plant growth regulators such as indolinone derivative plant stimulators, described in WO 2005/107466; 3,4-disubstituted maleimide derivatives described in WO 2005/107465; fused azepinone derivatives described in WO 2005/107471 ; and 2-amino-6-oxyp urine derivatives described in WO 2005/1 07472 are also included in the term.
  • plant or “crop” as referred to herein may be any plant or crop in plantation or in culture, especially agricultural crops, horticultural crops or silvicultural crops, and more preferably, cotton plants, including transgenic cotton plants.
  • the plant growth regulator is thidiazuron.
  • thidiazuron is present in a concentration range of from 1 to 500g/L, or more preferably, from 1 to 250g/L, or more preferably, from 1 to 200g/L, or more preferably, from 1 to 150g/L, or more preferably, from 1 to 120g/L, or more preferably, from 1 to lOOg/L, or more preferably, from 1 to 80g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L, or more preferably, from 50 to 1 OOg/L, or more preferably, from 50 to 150g/L, or more preferably, from 100 to 150g/L, or more preferably, from 100 to 200g/L, or more preferably, from 150 to 250g/L.
  • thidiazuron is present in a concentration ran ge of from 60 to 120g/L and most preferably, in a concentration of l OOg/L.
  • the plant growth regulator is other than thidiazuron, the plant growth regulator is present in a concentration range of from 1 to 500g/L, or more preferably, from 1 to 200g/L, or more preferably, from 1 to 120g/L, or further more preferably, from 1 to lOOg/L.
  • the co-formulation further comprises at least one additional biologically active ingredient selected from a fungicide; an insecticide; an herbicide; a miticide; a nematocide; a molluscicide; an algicide; or a pesticide; or any mixture thereof.
  • a fungicide an insecticide
  • an herbicide a miticide
  • a nematocide a molluscicide
  • an algicide or a pesticide
  • the co-fonnulation comprises thidiazuron in combination with a fungicide.
  • the co- formulation comprises thidiazuron in combination with an insecticide.
  • the co-fonnulation comprises thidiazuron in combination with a miticide. In yet another preferred form, the co-fonnulation comprises thidiazuron in combination with a nematocide. In yet another preferred form, the co-fonnulation comprises thidiazuron in combination with a molluscicide. In a most prefened form of the invention, the co- formulation comprises thidiazuron in combination with an herbicide.
  • the additional biologically active ingredient is present in a concentration range of from 1 to 250g/L, or more preferably, from 1 to lOOg/L, or more preferably, from 1 to 80g/L, or more preferably, from 1 to 60g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L, or more preferably, from 80 to lOOg/L, or more preferably, from 50 to l OOg/L, or more preferably, from 50 to 80g/L, or more preferably, from 30 to 50g/L, or more preferably, from 20 to 30g/L.
  • the concentration of the additional biologically active ingredient is most preferably selected from 48, 30 or 15g/L, respectively. In the most prefened form, the additional biologically active ingredient is present in a concentration of 30g/L.
  • the additional biologically active ingredient is preferably at least one herbicide, it may be selected from, but is not to be taken as being limited to: a dinitroaniline herbicide; a diphenylether herbicide; a phenoxypropionate herbicide; and including atrazine, nicosulfuron, carfentrazone, naptalam, 2,4-D, quizalofop, benefin, bentazon, prometryn, mesotrione, flumioxazin, clomazone, ethalfluralin, napropamide, diquat, s-metolachlor, ametryn, dimethenamid, fiuazifop, oxyfiuorfen, paraquat, topramezone, diuron, pronamide, alachlor, tembotrione, linuron, rimsulfuron, sethoxydim, bensulide, pendimethalin, pyrazon, cycloate,
  • thidiazuron is preferably present in a concentration range of from 1 to 250g/L, or more preferably, from 1 to 200g/L, or more preferably, from 1 or lOOg/L, or more preferably, from 1 to 80g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L and most preferably, in a concentration of 60 g/L; and diuron is preferably present in a concentration range of from 1 to 250 g/L, or more preferably, from 1 to 1 OOg/L, or more preferably, from 1 to 80 g/L, or more preferably, from 1 to 60g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L, or more preferably, from 1 to 250g/L, or more preferably, from 1 or lOOg/L, or more
  • the co-formulation has been found to display surprisingly synergistic defoliation efficacy on crops, when compared to existing defoliants used in accordance with existing defoliation practices.
  • the plant growth regulator and/or the active ingredient be finely divided via, for example, comminution or other means for the purposes of ensuring that the di spersion concentrate is maintained in a substantially stable form.
  • machines like the ball mill, vertical roller mill, hammer mill, roller press or high compression roller mill, vibration mill, jet mill and the like can be used.
  • ultra finer particle sizes which are sometimes referred to as "ultrafme grinding”
  • specialist mills can be used.
  • the comminution of the at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, of the present invention results in an average particle size of the components in the range of from 1 to 12 microns, or more preferably, of from 1 to 8 microns, or even more preferably, of from 1 to 6 microns.
  • comminution may be carried out using wet grinding via a horizontal mill, for example, one supplied by Engineered Mills, Inc. of Grayslake, Illinois, to produce a co-formulation with an average (d0.5) particle size of less than 5 microns, with the particle size analysis being determined by microscopic approximation, or by the use of an acceptable Grind Gauge or Hegman Gauge.
  • the at least one oil, which forms the continuous phase of the co-formulation is preferably selected from a paraffin oil, such as a kerosene, for example, one of the EXXSOL ® D range available from ExxonMobil Chemical Company of Spring, Texas; YUBASE 3 ® available from SK Corporation of Seoul, Republic of Korea; PROPAR ® 12 available from Caltex; JEFFSOL ® AG 1555 solvent available from Huntsman Corporation; a seed oil, such as methyl and ethyl oleate, methyl and ethyl soyate and their corresponding fatty acids; an aromatic hydrocarbon, such as an alkyl benzene and an alkyl naphthalene, such as SOLVESSO ® 150 available from ExxonMobil Chemical Company; a polyalkylene glycol ether; a fatty acid diester; a fatty alkylamide or diamide; a dialkylene carbonate; a ketone; an alcohol; or
  • the at least one oil is used in a concentration range of from 1 to 700g/L, or more preferably, of from 100 to 700g/L, or more preferably, of from 100 to 450g/L, or more preferably, of from 100 to 300g/L, or more preferably, of from 1 to 450g/L, or more preferably, of from 300 to 450g/L, or even more preferably, of from 450 to 700g/L.
  • the at least one oil is used in a concentration of greater than 500g/L.
  • the addition of at least one oil-soluble surfactant dispersing agent is preferably selected from a fatty acid-polyalkylene glycol condensate, such as TERSPERSE ® 2510 dispersant; or a polyamine-fatty acid condensate, such as TERSPERSE ® 4850 dispersant or TERSPERSE ® 4890 dispersant; a random polyester condensate, such as TERSPERSE ® 2520 dispersant; and a salt of a polyolefin condensate, such as TERSPERSE ® 2422 dispersant, which are all products of Huntsman Corporation.
  • a fatty acid-polyalkylene glycol condensate such as TERSPERSE ® 2510 dispersant
  • a polyamine-fatty acid condensate such as TERSPERSE ® 4850 dispersant or TERSPERSE ® 4890 dispersant
  • a random polyester condensate such as TERSPERSE ® 2520 dispersant
  • the at least one dispersing agent is a condensation product of the reaction of polyalkylene glycol or polyalkylene glycol ether and a fatty acid, such as TERSPERSE ® 2510 dispersant or a random polyester condensate, such as TERSPERSE ® 2520 dispersant.
  • the surfactant dispersing agent is used in a concentration range of from 1 to 70g/L, or more preferably, of from 1 to 40g/L, or more preferably, of from 40 to 70g/L, or more preferably, of from 1 to 15g/L.
  • condensate refers to the reaction product of a condensation reaction following the elimination of water or a small molecule, or to the reaction product of an addition reaction.
  • the co-formulation of the present invention further preferably comprises at least one rheology modifier to overcome the strong tendency of the finely dispersed plant growth regulator when on its own or when in combination with the active ingredient, or the dispersed phase, to settle or consolidate over time.
  • the rheology modifier is used in an amount of from 1 to 20g/L, or more preferably, of from 1 to 15g/L, or more preferably, of from 1 to l Og/L, or more preferably, of from 1 to 5g/L.
  • the at least one rheology modifier is preferably selected from fumed silica, both hydrophobic and hydrophilic variants, such as one provided by the AEROSIL ® range from EVONIK; a gelling clay, such as one provided by the hydrophobic members of the BENTONE ® range from ELEMENTIS ® , and more particularly, either BENTONE ® 38, a hydrophobically modified hectorite clay, or BENTONE ® SD-1 , a hydrophobically modified organic derivative of bentonite; a triglyceride or other fatty acid ester of glycerol; a rubber-type co-polymer, particularly one containing styrene residues, such as styrene-butadiene co-polymers, such as K RATON ' G1701, available from KRATON Corporation; and a co-polymer, block or otherwise, such as a polyester and/or a polyamides.
  • fumed silica both hydro
  • the rheology modifier is BENTONE® SD-1, or even more preferably, the combination of BENTONE® SD-1 , a hydrophobically modified organic derivative of bentonite, which is used in an amount of from 1 to 20g/L, or more preferably, of from 1 to 15g/L, or more preferably, of from 1 to lOg/L; and AEROSIL ® 200, a hydrophilic fumed silica, which is used in an amount of from 1 to 40g/L, or more preferably, of from 1 to 20g/L, or more preferably, of from 1 to 10g/L, or more preferably, of from 1 to 5g/L.
  • the co-formulation may further comprise at least one secondary activation agent to yield optimal performance.
  • the secondary activation agent comprises a gelling clay
  • the addition of polar solvents including water, methanol, ethanol, propylene carbonate, or any mixtures thereof may be required.
  • the co-formulation may further preferably comprise at least one secondary activation agent to facilitate highly improved rheological modification performance.
  • the co-formulation preferably further comprises at least one inert solid filler, including, but not limited to, titanium dioxide, such as TIONA 625 available from CRISTAL Global and one or more rheologically inactive phyllosilicates, which can also act as activation agents that assist in stabilising the co-formulation.
  • inert solid filler including, but not limited to, titanium dioxide, such as TIONA 625 available from CRISTAL Global and one or more rheologically inactive phyllosilicates, which can also act as activation agents that assist in stabilising the co-formulation.
  • the choice of an emulsifying agent is somewhat governed by the type of oil/s used as the continuous phase. Generally, an emulsifying agent having a low hydrophobic-lipophobic balance (“HLB”) is most suitable.
  • HLB hydrophobic-lipophobic balance
  • the HLB required for most oil phases used in the present co-formulation is usually below 10.
  • Such an emulsifying agent is preferably selected from one or more alkoxylated fatty alcohol/s, sorbitan ester/s and their corresponding ethoxylate/s, ethoxylated fatty acid/s, ethoxylated castor oil/s, calcium and ammonium and alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salt/s, ethylene oxide-propylene oxide block copolymer/s, ethoxylated alkylamine/s and ethoxylated alkyl phenol/s, or any mixtures thereof.
  • the at least one emulsifying agent is most preferably selected from the group of castor oil ethoxylates, in particular, TERMUL ® 3201 emulsifier, TERMUL ® 3512 emulsifier; alcohol ethoxylates, in particular, TERIC ® 12A3N, 12A4N, 13A7, 13A9, 17A2 and SURFONIC ® TDA-6; alcohol alkoxylates, such as TERMUL ® 5429, 5459 and 5500; fatty acid ethoxylates, such as TERIC ® OF6; sorbitan ester ethoxylates, such as ECOTERIC ® T85; a sulphosuccinate, such as TERMUL ® 3665 emulsifier, all of which are available from Huntsman Corporation; and amine and calcium salts of dode
  • the most preferred emulsifying agent comprises any one or any combination of calcium salt of dodecylbenzene sulphonate, at least one alcohol alkoxylate, and sorbitan ester ethoxylate in an amount of from 1 to 300g/L, or more preferably, of from 1 to 250g/L, or more preferably, of from 1 to 175g/L, or more preferably, of from 1 to 150g/L, or more preferably, of from 175 to 250g/L, or more preferably, of from 150 to 175g/L, or more preferably, of from 100 to 150g/L, or more preferably, of from 1 to lOOg/L.
  • the co-formulation of the present invention exists as a continuous phase in oil/s, which may further be diluted in water as facilitated by the presence of an emulsifying agent/s, the invention may further comprise water-soluble surfactant dispersing agents that help maintain the pre-broadcast aqueous dispersion in a substantially stable form.
  • the at least one water-soluble surfactant dispersing agent is preferably selected from, but not limited to, sodium or ammonium salts of alkyl naphthalene sulphonate formaldehyde condensates, such as TERSPERSE® 2020; sodium, calcium and ammonium salts of lignosulphonates; sodium or ammonium salts of co-polymers, such as TERSPERSE® 2700; sulfonates of cumene or xylene, such as the ELTESOL SC or SX ran ge of products available from INNOSPEC Inc.
  • the scope of the present invention further extends to a method of preparing the co- formulation of the invention comprising the following steps, wherein steps c) and d) may be carried out in any order or simultaneously:
  • step b) adding at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, to the oil from step a) either by stirring or high- shear mixing to create an oil dispersion;
  • step c) comminuting the oil dispersion of step c) to achieve an average particle size of the at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, in the range of from 1 to 12 microns;
  • step c) comminuting the oil dispersion of step c) to achieve an average particle size of the at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, in the range of 1 to 12 microns; and optionally e) adjusting the temperature of the oil dispersion to between about 60° C and 70° C with stirring; and optionally
  • the present invention provides a method of preparing a substantially homogenous and stable co-formulation comprising the following steps, wherein steps a) to d) are carried out before or after steps e) to g) and before step h):
  • step d) comminuting the oil dispersion of step c) to produce a substantially homogeneous first dispersion concentrate wherein at least one plant growth regulator, or at least one plant growth regulator and an additional biologically active ingredient, has an average particle size in the range of 1 to 12 microns;
  • step g) adding at least one other rheology modifier to the gel of step g) under low-shear mixing to form a pre-mix carrier;
  • step f) occurs once the emulsifying agent has been added.
  • the gel is improved in that while it maintains similar rheological traits, it is easier to handle having a lower viscosity which allows for better mixing in step (i). It is also thermodynamically preferable to form a stable second dispersion concentrate, which assists in substantially avoiding the unwanted side-effects of adding concentrated emulsifiers to the millbase pre-mix.
  • the scope of the present invention also extends to a method for applying the present co-formulation to a crop requiring defoliation, whereby it is expected that the synergistic benefit of co-formulating at least one plant growth regulator, or at least one plant growth regulator in combination with an additional biologically active ingredient, with at least one oil, may yield benefits with respect to improved formulation efficiency and biological efficacy. More particularly, the present inventor has found that the application of the co- formulation of the present invention when used as a defoliant maintains or yields improvements in defoliation efficiency in crops and in particular, in cotton crops.
  • the co-formulation of the present invention removes the need to apply or mix the at least one plant growth regulator and/or the at least one active ingredient separately as has been done in the past, which is advantageous from a handling and ease-of-use perspective. Due to the synergism that exists between at least one plant growth regulator, or at least one plant growth regulator in combination with an additional biologically active ingredient and the at least one oil, the present invention therefore results in substantially improved efficiency of defoliation.
  • Figure 1 illustrates the results of flow assessments conducted on particular examples, which show rheological features attributed to dispersion instability. This instability has been linked to further catastrophic destabilisation phenomena exhibited by complete co-formulation examples, and highlights the significant improvements afforded by the present invention which surprisingly manage to diminish the unwanted effects of these challenges.
  • thidiazuron is most preferably present in a concentration range of 1 to 250g/L, or more preferably, from 1 to 200g/L, or more preferably, from 1 or 1 OOg/L, or more preferably, from 1 to 80g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L and most preferably, in a concentration of 60 g/L.
  • thidiazuron is most preferably present in a concentration range of 1 to 250g/L, or more preferably, from 1 to 200g/L, or more preferably, from 1 or 1 OOg/L, or more preferably, from 1 to 80g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L and most preferably, in a concentration of 60 g/L; and diuron is preferably present in a concentration range of from 1 to 250 g/L, or more preferably, from 1 to 1 OOg/L, or more preferably, from 1 to 80 g/L, or more preferably, from 1 to 60g/L, or more preferably, from 1 to 50g/L, or more preferably, from 1 to 30g/L, or more preferably, from 1 to 20g/L, or more preferably, from 1 to 250g/L, or more preferably, from 1 or 1 OOg/L, or more
  • the at least one oil is a Group 3 Base Oil with a Viscosity Index of between 110 and 120, which is used in a concentration range of 450 to 700g/L.
  • the at least one oil-soluble surfactant dispersing agent is most preferably a condensation product of the reaction of polyalkylene glycol or polyalkylene glycol ether and a fatty acid, such as TERSPERSE ® 2510 dispersant, or a random polyester condensate, such as TERSPERSE ® 2520 dispersant, which is used in a concentration range of from 1 to 70g/L, or more preferably, of from 1 to 40g/L, or more preferably, of from 40 to 70g/L, or more preferably, of from 1 to 15g/L.
  • a condensation product of the reaction of polyalkylene glycol or polyalkylene glycol ether and a fatty acid, such as TERSPERSE ® 2510 dispersant, or a random polyester condensate, such as TERSPERSE ® 2520 dispersant which is used in a concentration range of from 1 to 70g/L, or more preferably, of from 1 to 40g/L, or more preferably, of from 40 to
  • the at least one emulsifying agent required for the co-formulation comprising thidiazuron, or thidiazuron and diuron is most preferably selected from the group of sorbitan ester ethoxylates, in particular, ECOTERICTM T85 fatty acid ethoxylate; alcohol alkoxylates, such as TERMUL ® 3201 , 5429, 5459 and 5500 emulsifiers; alcohol ethoxylates, in particular, TERIC ® 12A3N and TERIC ® 13A7 fatty acid ethoxylates, most of which are available from Huntsman Corporation; and amine and calcium salts of dodecylbenzene sulphonate, such as the NANSA ® EVM range of surfactant products, and more preferably, NANSA ® EVM 70/2E surfactant.
  • sorbitan ester ethoxylates in particular, ECOTERICTM T85 fatty acid ethoxylate
  • the most preferred emulsifying agent is the combination of at least one or any calcium salt of dodecylbenzene sulphonate, at least one alcohol alkoxylate, and sorbitan ester ethoxylate, each in amount of from 1 to 175g/L.
  • a hydrophobic ally modified organic derivative of bentonite namely, BENTONE ® SD-1
  • BENTONE ® SD-1 a hydrophobic ally modified organic derivative of bentonite, namely, BENTONE ® SD-1
  • BENTONE ® SD-1 a hydrophobically modified organic derivative of bentonite, namely, BENTONE ® SD-1
  • AE OSIL ® 200 a hydrophilic fumed silica
  • the secondary activation agent which may be required to yield further improved performance, is most preferably selected from a gelling clay, which may also require the addition of polar sol vents including water, methanol, ethanol, propylene carbonate, or any mixtures thereof
  • a typical oil dispersion formulation known in the art has a composition as described in Table A below.
  • Table 2 provides an example of a commercial aqueous suspension concentrate ("SC") containing both diuron and thidiazuron:
  • Such a formulation would be prepared in a manner familiar to those skilled in the art.
  • a pre-mix 'masterbatch' of activated hydrophobically-modified hectonte was prepared via the dispersion of lOg BENTONE ® 38 (ELEMENTIS) in 86.66g of YUBASE 3 ® via a SILVERSON high-shear mixer.
  • ELEMENTIS lOg BENTONE ® 38
  • SILVERSON high-shear mixer 3.34g JEFFSOL ® AG 1555 was added with continued shear until a homogeneous gel-like substance was afforded. This was set aside.
  • TERSPERSE ® 2510 dispersant was dissolved in an amount of YUBASE 3 ® that would allow for a thidiazuron concentration in the vicinity of 7% w/w.
  • Diuron and thidiazuron technical were then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using an horizontal mill (Engineered Mills, Inc.) to produce a concentrate containing components having an average (d0.5) particle size of less than 5 ⁇ . Particle size analysis was determined by microscopic approximation.
  • TERMUL ® 3201 emulsifier NANS A ® EVM 70/2E surfactant, TERMUL* 5459 emulsifier and the pre-prepared rheology modifier, prepared as described above, were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenised via low to moderate shear mixing.
  • the composition was then observed as displaying satisfactory stability and dilution behaviour. This is also an example of the methodology of add ing a rheol ogy modifier post-comminuti on.
  • EXAMPLE 4 Higher-loading variant of EXAMPLE 3 and exemplified in-field.
  • TERSPERSE* 2510 dispersant was dissolved in an amount of YUBASE 3 ® that would allow for a thidiazuron concentration in the vicinity of 12% w/w. Diuron and thidiazuron technical were then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • TERSPERSE ® 2510 dispersant was dissolved in an amount of YUBASE 3 ® that would allow for a thidiazuron concentration in the vicinity of 17 to 18% w/w. Diuron and thidiazuron technical were then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This mixing was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , detennined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally detennined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • TERMUL ® 3201 emulsifier, NA SA ® EVM 70/2E surfactant and the pre-prepared rheology modifier as described in EXAMPLE 3 were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenised via low to moderate shear mixing. The composition was then observed as displaying satisfactory stability and dilution behaviour. This is another example of the methodology of adding rheology modifiers post-comminution.
  • a millbase concentrate for use in the preparation of a complete oil-based suspension co- formulation of thidiazuron according to the present invention was prepared as follows:
  • TERSPERSE ® 4850 dispersant was dissolved in an amount of pre-mixed YUBASE 3* and SOLVESSO 150. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a millbase concentrate for use in the preparation of a complete oil-based suspension co- formulation of thidiazuron according to the present invention was prepared as follows:
  • TERSPERSE ® 2510 dispersant was dissolved in an amount of pre-mixed YUBASE 3 ® and SOLVESSO 150. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded. [0076] This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge.
  • Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a millbase concentrate for use in the preparation of a complete oil-based suspension co- formulation of thidiazuron according to the present invention was prepared as follows:
  • TERSPERSE ® 2520 dispersant was dissolved in an amount of pre-mixed YUBASE 3 ® and SOLVESSO 150. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a millbase concentrate for use in the preparati on of a complete oil-based suspension co- formulation of thidiazuron according to the present invention was prepared as follows:
  • TERSPERSE ® 4890 dispersant was dissolved in an amount of pre-mixed YUBASE 3 s and SOLVESSO 150. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a millbase concentrate for use in the preparation of a complete oil -based suspension co- formulation of thidiazuron according to the present invention was prepared as follows:
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • EXAMPLE 8 shows significant improvement with initial measurements displaying only minor thixotropy and viscosity readings of « 1 Pa across the measured shear rate range. After 6 days however, EXAMPLE 8 is shown to display onset of the same de-stabilising phenomena with viscosity approaching 1 Pa, or a nearly 1000-fold increase in shear viscosity.
  • EXAMPLE 10 is an anomalous example, which highlights further improved dispersion stability, where a lack of thixotropy and time-dependent rheological changes are displayed. However, this further improvement unexpectedly shows no benefit when utilised in the preparation of a complete composition, as exemplified by EXAMPLE 20, thus highlighting further unprecedented complexity.
  • the required amount of BENTONE* 38 was added to an amount of YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%.
  • the resultant suspension was then subject to mixing at high-shear (SILVERSON) for a specific duration, followed by drop-wise addition of JEFFSOL ® AG 1555 solvent with continued shear to develop the appropriate rheology.
  • the rate of shear was then decreased, and the required mass of AEROSIL ® 200 (EVONIK) was added followed by continued shear for a specific duration.
  • TERSPERSE ® 2510 dispersant was then dissolved in the mixture ensuring homogeneity, followed by dispersion of diuron and thidiazuron technical.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • TERMUL ® 3201 emulsifier and ANS A ® EVM 70/2E surfactant were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenised via low-shear (overhead stirring).
  • the composition was shown to display satisfactory stability and dilution behaviour. This is an example of a methodology, whereby the rheology modifiers were added prior to comminution.
  • the required amount of BENTONE* 38 was added to an amount of YUBASE 3 ® , which equated to roughly 50% of the total requirement, and SOLVESSO ® 150 (EXXON Chemical).
  • the resultant suspension was then subject to mixing at high-shear (SILVERSON) for a specific duration, followed by drop-wise addition of JEFFSOL ® AG 1555 solvent with continued shear to develop the appropriate rheology.
  • the rate of shear was then decreased, and the required mass of AEROSIL ® 200 (EVONIK) was added followed by continued shear for a specific duration.
  • TERSPERSE ® 2510 dispersant was then dissolved in the mixture ensuring homogeneity, followed by dispersion of thidiazuron technical.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.). The process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • TERMUL ® 3201 emulsifier and NANS A ® EVM 70/2E surfactant were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenized via low-shear overhead stirring.
  • the composition was shown to display satisfactory stability and dilution behaviour. This is an example of a methodology, whereby rheology modifiers were added prior to comminution.
  • a pre-mix "masterbatch" gel was prepared via the dispersion of 14.8 l g BENTONE ® SD-1 (ELEMENTIS) in 80.25g of YUBASE 3 ® via a SILVERSON high-shear mixer. To the resultant homogeneous dispersion, 4.94g SOLVESSO ® 150 was added with continued shear until a gel-like substance was afforded. This was set aside.
  • a pre-mix "masterbatch" gel was prepared via the addition of 4.23g AEROSIL ® 200 to 95.77g of YUBASE ® 3 under high shear until a gel-like substance was afforded. This was set aside.
  • TERSPERSE ® 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVES SO ® 150 and YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • TERMUL ® 3201 emulsifier, NANSA ® EVM 70/2E surfactant, TERIC ® 13A7 emulsifier and the pre-prepared masterbatch gels were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenised via low-shear mixing.
  • the composition was then shown to display satisfactory stability and further improved dilution behaviour, which meets the desired commercial performance criteria. This is another example of the methodology of adding rheology modifiers post-comminution.
  • a pre-mix "masterbatch" gel was prepared via the dispersion of 14.81 g BENTONE ® SD-1 (ELEMENTIS) in 83.19g of YUBASE 3 ® via a SILVERSON high-shear mixer. To the resultant homogeneous dispersion, 2.00g SOLVESSO ® 150 was added with continued shear until a gel-like substance was afforded. This was set aside.
  • a further pre-mix "masterbatch" gel was prepared via the addition of 4.23g AEROSIL ® 200 to 95.74g of YUBASE ® 3 under high shear until a gel-like substance was afforded. This was set aside.
  • TERSPERSE* 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • TERMUL ® 3201 emulsifier NANS A ® EVM 70/2E surfactant, TERIC ® 13 A7 emulsifier and the pre-prepared masterbatch gels were added, followed by the remaining quantity of YUBASE 3 ® .
  • the resulting oil-based suspension was then homogenised via low shear mixing.
  • the composition was then shown to display satisfactory stability and further improved dilution behaviour which meets the desired commercial performance criteria. This is another example of the methodology of adding rheology modifiers post-comminution.
  • a pre-mix "masterbatch" gel was prepared via the dispersion of 14.21 g BENTONE ® SD-1 (ELEMENTIS) in 76.39g of YUBASE 3 ® via a S1LVERSON high-shear mixer.
  • 9.40g SOLVESSO ® 150 was added with continued shear until a gel-like substance was afforded. This was set aside.
  • a further pre-mix "masterbatch" gel was prepared via the addition of 4.24g AEROSIL ® 200 to 95.76g of YUBASE ® 3 under high shear until a gel-like substance was afforded. This was set aside.
  • the required amount of TERSPERSE ® 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO* 150 and YUBASE 3*, where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge.
  • Particle size analysis was additionally determined by microscopic approximation.
  • Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a pre-mix carrier was prepared via the dispersion of 14.21g BENTONE* SD-1 (ELEMENTIS) in 200g of YUBASE 3 ® via a SILVERSON high-shear mixer.
  • 14.21g BENTONE* SD-1 ELEMENTIS
  • YUBASE 3 ® YUBASE 3 ®
  • SILVERSON high-shear mixer To the resultant homogeneous dispersion, 9.40g SOLVESSO* 1 0 was added with continued shear until a gellike consistency was afforded. Finally, 4.23g AEROSIL ® 200 was added under low-shear mixing until a homogeneous albeit flowable gel was afforded. The mixture was set aside.
  • TERSPERSE ® 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%. Diuron and thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SIL VERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopy, where the dispersion displayed weak to moderate flocculation of active ingredient crystals.
  • a pre-mix carrier was prepared via the dispersion of 14.21g BENTONE ® SD-1 (ELEMENTIS) in 200g of YUBA SE 3 ® via a SILVERSON high-shear mixer.
  • 14.21g BENTONE ® SD-1 ELEMENTIS
  • YUBA SE 3 ® SILVERSON high-shear mixer.
  • 9.40g SOLVESSO ® 150 was added with continued shear until a gellike consistency was afforded.
  • 4.24g AEROSIL ® 200 was added under low-shear mixing until a homogeneous albeit flowable gel was afforded. The mixture was set aside.
  • TERSPERSE* 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation. This concentrate was briefly set aside.
  • a pre-mix carrier was prepared via the dispersion of 3.90g BENTONE ® SD-1 (ELEMENTIS) in 47.83g of YUBASE 3 ® via a SILVERSON high-shear mixer, yielding a very fine suspension.
  • 2.57g SOLVESSO ® 150 was added with continued shear until a gel-like consistency was afforded.
  • 27.41 g TERMUL® 3201 , 6.85g NANSA® EVM70/2E, and 10.28g TERIC® 13A7 were then added to the mixture followed by low-speed mixing to homogenise.
  • 1.15g AEROSIL* 200 was added slowly under low-shear mixing until a homogeneous, weakly gelled mixture was afforded. The mixture was set aside.
  • TERSPERSE ® 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3 ® , where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 20%.
  • Thidiazuron technical and TIONA 625 were then dispersed in the resultant mixture under high-shear using a SrLVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • a pre-mix "carrier-base” was prepared via the dispersion of 14.21g BENTONE* SD-1 (ELEMENTIS) in 200g of YUBASE 3 ® via a SILVERSON high-shear mixer.
  • 9.40g SOLVESSO* 1 0 was added with continued shear until a gellike consistency was afforded.
  • 4.24g AEROSIL ® 200 was added under low-shear mixing until a homogeneous albeit flowable gel was afforded. The mixture was set aside.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • a pre-mix carrier was prepared via the dispersion of 3.90g BENTONE ® SD-1 (ELEMENTIS) in 47.83g of YUBASE 3 ® via a SILVERSON high-shear mixer, yielding a very fine suspension.
  • 2.57g SOLVESSO ® 150 was added with continued shear until a gel-like consistency was afforded.
  • 27.41 g TERMUL® 3201 , 6.85g NANSA® EVM70/2E, and 10.28g TERIC® 13A7 were then added to the mixture followed by low-speed mixing to homogenise.
  • 1.15g AEROSIL ® 200 was added slowly under low-shear mixing until a homogeneous, weakly gelled mixture was afforded. The mixture was set aside.
  • TERSPERSE ® 2520 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3*, where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 15%.
  • Thidiazuron technical and TIONA 625 were then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80% of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge.
  • Particle size analysis was additionally determined by microscopic approximation.
  • a pre-mix carrier was prepared via the dispersion of 3.90g BENTONE ® SD-1 (ELEMENTIS) in 47.83g of YUBASE 3 ® via a SIL VERSON high-shear mixer, yielding a very fine suspension.
  • 2.57g SOLVESSO ® 150 was added with continued shear until a gel-like consistency was afforded.
  • 27.4 lg TERMUL® 3201 , 6.85g NANSA® EVM70/2E, and 10.28g TERIC® 13A7 were then added to the mixture followed by low-speed mixing to homogenise.
  • 1.15g AEROSIL ® 200 was added slowly under low-shear mixing until a homogeneous, weakly gelled mixture was afforded. The mixture was set aside.
  • TERSPERSE ® 4890 dispersant was dissolved in a mixture comprising the remaining amount of SOLVESSO ® 150 and YUBASE 3*, where the latter equated to an amount that would allow for a thidiazuron concentration in the vicinity of 15%. Thidiazuron technical was then dispersed in the resultant mixture under high-shear using a SILVERSON mixer. This was continued until a homogeneous mixture was afforded.
  • This slurry was then comminuted using a horizontal mill (Engineered Mills, Inc.).
  • the process involved slowly feeding the concentrate into the milling apparatus operating at a low rotational speed of from 500 to 1000 RPM, wherein the mill grinding chamber had been preloaded with from 1 to 1.6mm diameter glass, or more preferably, zirconium silica media from 60 to 80%) of total volume capacity, and the jacketed coolant temperature was pre-set and maintained at an externally controlled temperature of from 15 to 25° C.
  • Rotational speed was slowly increased from 2000 to 2500 RPM for a period of from 30 to 45 minutes, producing a concentrate with an average (d0.5) particle size of roughly 5 ⁇ , determined by approximation using a 0 to 100 Grind Gauge, or a 8 to 0 Hegman Gauge. Particle size analysis was additionally determined by microscopic approximation.
  • DC-TRON is a spray oil which contains 827g/L petroleum oil and between 80-lOOg/L of emulsifying agent/s.
  • DC-T ON is a spray oil which contains 827g/L petroleum oil and between 80-lOOg/L of emulsifying agent/s.
  • EXAMPLE 24.1 highlights the synergistic effects afforded by co-formulation of an oil with either a plant growth regulator on its own, or with a mixture of a plant growth regulator and an herbicide, in comparison to the customary use of a plant growth regulator or a mixture of a plant growth regulator and an herbicide in combination with a formulated spraying oil.
  • Treatment 13 With respect to the co-formulation of an oil and a plant growth regulator used on its own, the synergism is best represented by Treatment 13 in Table 24.1, where thidiazuron is applied as an oil-based co-formulation or OD formulation. At 4, 7 and 14 days after treatment (“DAT"), this treatment consistently shows statistically improved defoliation when compared to Treatment 2, where thidiazuron is applied alongside a spraying oil fonnulation in a customary fashion. These results have been achieved through a 34.8% reduction in total agrochemical input per hectare. Additionally, Treatment 13 may be viewed as comparable to Treatment 3 in terms of defoliation performance, whereby the total agrochemical input and biologically active defoliant applied per hectare have been reduced by 37.5% and 25%, respectively.
  • Example 24.2 highlights the synergistic effects afforded by co-formulation of an oil with a plant growth regulator, or with a mixture of a plant growth regulator and an herbicide, in comparison to the use of a traditional plant growth regulator or a mixture of plant growth regulator and herbicide in combination with a spray oil as shown in Examples 1 and 2.
  • Treatment 10 With respect to the co-formulation of an oil and a mixture of a plant growth regulator and an herbicide, the synergism is best represented by Treatment 10 in Table 24.2. At 8 DAT, this treatment shows marginally improved defoliation performance when compared to Treatment 4. At 14 DAT, Treatment 10 is statistically superior. These results have been achieved through a 60%o reduction in total agrochemical input per hectare.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une co-formulation agricole comprenant : une quantité efficace d'au moins un régulateur de croissance végétale, ou d'au moins un régulateur de croissance végétale et un ingrédient additionnel biologiquement actif, sous une forme finement broyée présentant une taille moyenne de particule située dans la plage de 1 à 12 microns ; au moins une huile ; au moins un agent de dispersion type tensioactif soluble dans l'huile ; et au moins un agent émulsifiant, la concentration finale dudit régulateur de croissance végétale, ou dudit régulateur de croissance végétale et d'un ingrédient additionnel biologiquement actif, étant éventuellement ajustée en ajoutant de l'huile additionnelle et un ou plusieurs agents de modification de la rhéologie et/ou agents d'activation tel que requis pour stabiliser sensiblement la co-formulation ; et l'efficacité du régulateur de croissance végétale étant sensiblement conservée ou améliorée ; et un ou plusieurs procédés de fabrication de la co-formulation.
PCT/AU2017/000216 2016-11-18 2017-10-12 Co-formulation comprenant un régulateur de croissance végétale et une huile, et procédés de préparation et d'utilisation de ladite co-formulation Ceased WO2018090072A1 (fr)

Priority Applications (7)

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JP2018551098A JP7015787B2 (ja) 2016-11-18 2017-10-12 植物成長調節剤及び油を含む混合配合物ならびに該混合配合物の配合方法及び使用方法
AU2017361105A AU2017361105B2 (en) 2016-11-18 2017-10-12 Co-formulation comprising a plant growth regulator and an oil, and methods of preparing and using said co-formulation
CA3017030A CA3017030A1 (fr) 2016-11-18 2017-10-12 Co-formulation comprenant un regulateur de croissance vegetale et une huile, et procedes de preparation et d'utilisation de ladite co-formulation
CN201780020812.4A CN109068629A (zh) 2016-11-18 2017-10-12 包含植物生长调节剂和油的共制剂以及制备和使用所述共制剂的方法
BR112018069842A BR112018069842A2 (pt) 2016-11-18 2017-10-12 coformulação agrícola, e, método de preparar a coformulação.
EP17871625.4A EP3541183A4 (fr) 2016-11-18 2017-10-12 Co-formulation comprenant un régulateur de croissance végétale et une huile, et procédés de préparation et d'utilisation de ladite co-formulation
MX2018011686A MX392364B (es) 2016-11-18 2017-10-12 Co-formulacion que comprende un regulador de crecimiento de plantas y un aceite, y metodos para preparar y utilizar la co-formulacion

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AU2016904732 2016-11-18
AU2016904732A AU2016904732A0 (en) 2016-11-18 Co-formulation

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CN109673657B (zh) * 2019-01-23 2020-11-27 中国农业科学院棉花研究所 一种复合增效脱叶催熟剂及其应用
CN110754479A (zh) * 2019-12-03 2020-02-07 山东华阳农药化工集团有限公司 一种12%噻苯·敌草隆油悬浮剂及其制备方法

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CA3017030A1 (fr) 2018-05-24
AR110167A1 (es) 2019-03-06
AU2017361105A1 (en) 2018-09-20
AU2017361105B2 (en) 2021-12-16
JP7015787B2 (ja) 2022-02-03
CN109068629A (zh) 2018-12-21
EP3541183A1 (fr) 2019-09-25
MX392364B (es) 2025-03-24
EP3541183A4 (fr) 2020-05-20
BR112018069842A2 (pt) 2019-01-29
MX2018011686A (es) 2019-01-30

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