p..
`
`(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2017/0086454 Al
`Mar. 30, 2017
`(43) Pub. Date:
`NETTLETON-HAMMOND et al.
`
`US 20170086454A1
`
`(54) AGROCHEMICAL FORMULATION
`
`(30)
`
`Foreign Application Priority Data
`
`(71) Applicant: SYNGENTA PARTICIPATIONS AC,
`Basel (CH)
`
`(72)
`
`Thvcntors: John Henry
`NETTLETON.HAMMOND.
`Brackne]], Berkshire (GB); Niall Rae
`THOMSON. Bracknell. Berkshire
`(GD); Dirk Armand Win,
`STANSSENS. Houthalen (BE)
`
`Apr. 28, 2014
`
`(GD)
`
`1407384.5
`
`Publication Classification
`
`(51) mt. CI.
`A01iV25/04
`401N37/?6
`(52) U.S. Cl.
`CPU
`
`(2006.01)
`(2006.01)
`
`All/N 25/04 (2013.01); AOIN 37/36
`(2013.01)
`
`(73) Assignee: SYNGENTA PARTICIPATIONS AG.
`Basel (CH)
`
`(57)
`
`ABSTRACT
`
`(21) AppI. No.:
`
`15/302,242
`
`(22)
`
`PUT Filed:
`
`Apr. 28, 2015
`
`(86)
`
`PUT No.:
`§ 371 (cXl),
`(2) Date:
`
`PCTIEP2OIS/o59233
`
`Oct. 6, 2016
`
`The preseot invention relates to a composition compnsing
`an aqueous continuous phase; a first dispersed phase which
`comprises stvrene-rnalemnde copo[ynier particles: and a
`second dispersed phase which is either oil droplets. sus
`pended particles or a capsule suspension: and to use of those
`compositions to control agricultural pests or discascs. tt also
`relates to use of such cornsitions where rathThstness is
`important.
`
`5.*/Yz ri4o’
`
`Exhibit No.
`Datel _.rLQ_J%
`T. Alfarc
`
`SYNGENTA EXHIBIT 1041
`Syngenta v. UPL, PGR2023-00017
`
`

`

`US 20 17/0086454 Al
`
`Mar. 30, 2017
`
`I
`
`AGROCHEMICAL FORMULATION
`100011 The present invention relates to compositions com
`prising an aqueous continuous phase; a first dispersed phase
`which comprises slyrene-maleimide co-polymer particles:
`and a second dispersed phase which is either oil droplets,
`suspended particles or a capsule suspension; in particular it
`relates to such compositions in the agrochetiucal field; and
`to use of those compositions to control agricultural pests or
`diseases It also relates to use of such compositions where
`rninfnstness is important.
`the main application of agxochemical active ingrc
`100021
`dients is by spray application, often foliar spray application,
`to a
`but this means that the agrochemical may be subject
`variety of loss mechanisms before it is able to reach its
`iotended site of action in. say. a weed, insect or fungus. the
`main causes of loss of an agrochemical include rainwashing.
`photodegradation and insufficient retention on the intended
`surface. [here is therefore a need to be able to improve the
`physiocheruical characteristics of sprayed agrochemica]
`to good retention of the
`deposits such that subsequent
`sprayed deposit on a surface, for example a leaf surface, the
`is not washed off by any rain and is not
`agrochemical
`degraded by sunlight, yet the agrochcmical nit. st neverthe
`less remain bioavailablc so as to kill or control any uowaoted
`pests [including weeds, fungi, insects and netnatodes].
`100031 A variety of adjuvants have been proposed and
`used in the past, seeking to improve rainfastness and u.v.
`protectioit. W02012048176 discloses an array of polymer
`types that may be used to improve herbicide performance as
`a soil application (rather than a foliar application) and is
`dependent upon intimate systems in which pi-pi stackiitg is
`possible but this document is not concerned with rainfast
`ness
`[00041 The use of polymers to encapsulate active ingre
`dients and alter release rates under a range of conditions is
`well k]lowtl (a good summary is provided by W002/l00525,
`in particular pages 2 to 4)—exainples include polyurea walls
`as described in U.S. Pat. No. 4,280,833. Vive Nano’s
`W0100351 IS gives a further example where poly(acrylic
`acid), poly(melhacrylic acid) and poly(styrene sulfonate) are
`used to encapsulate active ingredients.
`10005] W02012/048176 teaches the encapsulation of an
`agrochemica] with an SMI polymer, where the encapsulation
`unsurprisingly a]ters the properties of the active ingredients.
`To achieve the eacapsu]ation the SMI polymer must first be
`the
`dissolved by lowering the pH of an aqueous dilution,
`active ingredient is then encapsulated by the polymer when
`thc pH is raised: as described in W02012/048 176 example
`for polymer encapsulation processes
`typical
`6 and is
`W020 I 2/048176 goes to great length to teach how the SM I
`could be intimately linked to achieve encapsulation but at no
`point foresees the application of dispersed SMI polymer
`within an aqueous continuous phase with a second, cotn
`pletely separate, dispersed phase. Surprisingly we have now
`found that advantageous properties can be gained by form
`ing such a two part dispersion.
`100061 We have now unexpectedly and surprisingly
`achieved improved rainfastncss of biologically active tngrc
`dients through the usc of a stvrene-maleimide co-polymer.
`which is formti]ated as an aqueous dispersion of panicles
`which comprise a styrene-malcimidc co-polymer. Further
`more, not only may rainfastness of a biologically active
`ingredient be intproved but the biological activity of that
`active ingredient, and possibly accompanying active ingre
`
`dients, may be uncompromised (or not significantly com
`promised). Accordingly, by reducing loss of an active ingre
`dient. the biological effect of a particular dose of that active
`ingredient may be increased or the biological effect may bc
`prolonged. At the same time, the uptake or biological effect
`of any partner active ingredient may be unimpaired.
`(0007] The aqueous dispersion of particles of a styrene
`naleimide co-polymer may therefore comprise a suspension
`in the continuous
`of solid particles of an agmchemical
`aqueous phase; or alternatively the ngrochemical may be
`present as an oil which is dispersed as emulsion droplets in
`tlte continuous aqueous phase; or an agroclteinical may even
`be dissolved in an oil which is dispersed as emulsion
`droplets in the continuous aqueous phase; or an agrochemi
`cal ntay be contained within capsules (microcapsules) sus
`pended in the continuous aqneoeus phase. The suspended
`particles, emulsion dioplets or suspended capsules will have
`conventional dimensions (that is, typically of the order of
`one to ten microns). Such a formulation approach provides
`boll] the styrene-malehnide co-polymer and an agruchemi
`cal together in a single formulattnn. which may be applied
`either directly to a target or maybe diluted ma coiiventiona]
`spray tank before being sprayed onto a target. When applied
`via a spray tank, other conventional adjuvants [such as
`surfactants or oil adjuvant compositionsi may be added to
`tlte spray tank prior to spraying.
`(00081 Alternatively, the aqueous dispersion of particles of
`a styreae-maleimide co-polymer tnay comprise an emulsion
`lipophilic hioperlbrmance
`is, a
`(that
`of an oil adjnvant
`enhancing adjuvant), whereby oil droplets are dispersed in
`the continuous aqueous phase. Suitably the oil adjuvniit may
`be selected from mineral oils, vegetable oils, derivatives
`thereof and also plasticiser adjuvants. Such a composition
`may then be added to a conventional spray tank, to be diluted
`in water along with a separate fonnulation containing an
`agrochemical (of course, that formulation could also be a
`formulation according to the present invention, as described
`above) prior to spraying. Examples of commercially avail
`able tank mix adjuvants include the mineral oil based
`NimbusTM and non-ionic wetting agent Activator POTM.
`Furthennore, an aqueous dispersion according to
`10009]
`the present invention may be provided within a conventional
`spray tank, for example by adding, say, both a conventional
`agrochemical suspension concentrate fonnulation and a sty
`rene-maleimide co-polymer dispersion to water in the spray
`tank.
`[00101 Therefore the present invention provides a compo
`sition contprising:
`(i) an aqueous continuous phase:
`100111
`(ii) a first dispersed phase which is particles which
`100121
`themselves comprise a styrene-maleimtde co-polymer;
`atid
`is either
`(iii) a second dispersed phasc wl,icl,
`[00131
`droplets comprising an oil; is suspended solid particles; or
`is a capsule suspension.
`100141 Clearly, both dispersed phases (ii) and (iii) arc each
`dispersed in continuous phase (i). Accordingly the present
`invention provides a composition comprising:
`(i) an aqueous continuous phase:
`100151
`(ii) a first dispersed phase dispersed in (i) which is
`(00161
`particles which themselves comprise a styrene-nialeimide
`co-polymer; and
`
`

`

`US 2017/0086454 Al
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`Mar. 30, 2017
`
`2
`
`100171
`(iii) a second dispersed phase dispersed in (i) which
`is either droplets comprising an oil;
`is suspended solid
`particles; or is suspended capsules.
`conventional microcapsules
`(0018] Capsules may be
`which comprise a polymer shell wall within which there is
`a core, which may be solid but is more suitably a liquid core.
`10019] The styrene-maleimide co-polymerparticle may be
`a random co-polymer or a block co-polymer; preferably is a
`random co-polymer.
`inveution provides a
`the present
`tn one aspect,
`100201
`composition as above where the second dispersed phase
`comprises an agrochemical where the amuchemical is either
`the suspended solid particles; is in the oil droplets: or is
`present within capsules of the capsule suspension; and in an
`alternative aspect. thc present invention provides a compo
`sition as described above where the second dispersed phase
`is droplets of an oil adjuvant.
`Furthennore, rhe continuous aqueous phase may
`100211
`contain both an emulsified oil adjuvant. as described above.
`and an agrochcmieal as described above [that is, the agro
`chenucal is either in suspended. emulsified or encapsulated
`form].
`100221 The composition of the present invention may also
`contain conventional fonnulation aids, such as suspending
`agents, wetting agents, emulsifying agents, antifoams, anti
`freeze agents, pH adjusters, buffers and viscosity control
`agents. It is also possible for a water soluble agrochemical
`to be dissolved in the aqueous continuous phase.
`10023] The stvrene-maleimide co-polymer particles may
`be prepared by known methods.
`[0024j The stvrene-maleimide co-polymer paxticle may be
`a random co-polymer or a block co-polymer and may be
`prepared from cyclic anhvdrides and vinyl monomer units,
`which have been subjected to an imidization reaction
`wherein the degree of imidization is below 90%.
`[00251 Those skilled in the art will know that styreue
`maleimide copolymers and dispersions thereof can be pre
`pared by a number of routes, such as those discussed in
`Hanson and Zmimcnnan. Ind. Eng. Chem. Vol 49 ur.
`11
`(1957), p. 1803-1807. WO 2000;34362, W020t1/098574
`and that
`the co-polymer may be present
`in a core/shell
`system, as discussed in W02011/110498.
`Suitable monomers
`for
`the polymer are for
`10026]
`example a-n-unsaturated diearboxylic aahydridcs such as
`maleic anhydride, alkyl or alkenyl maleie anhydrides, cit
`raconic anhydndc, itaconic anhydride and mixtures thereof.
`Preferably the co-polymer contains maleic anhydride mono
`mer units.
`Suitable vinyl monomers for use in the cu-polymer
`0027]
`include vinyl aromatic monomers (such as styrene. a-methyl
`styrene, vinyl toluene and indene) and mono-olefinic unsatu
`rated hydrocarbons (such as ethylene, propylene and isobu
`tyleae) (for example, please see W02011/098574).
`10028] The anhydride monomer content of the co-polymer
`tnay be from 15 to 50 mole %, preferably from 15 to 43 mole
`more preferably from 20 to 36 mole % and most
`preferably from 22 to 32 mole %; and the vinyl monomer
`content of the co-polymer may be from 85 to 50 mole %;
`preferably from 85% to 67%; more preferably from 80 to 67
`mole %.
`[0029j The co-polymer has a weight averaged molecular
`weight (Mw) ranging from 4000 to 500000 g/mole, prefer
`ably from 10000 to 300000 glmole, more preferably from
`
`8000 to 12000 g!mole as determined by get permeation
`chromatography using a polystyrene standard itt tetrahydro
`fttran.
`100301 The styrene mateimide random or block eopolymer
`is insoluble ii’ water and will forni a dispersion, with the size
`(average dimneter) of the primary particles ranging from
`20-200 nra, and an average particle diameter being 70-100
`nm as determined by tight scattering measurements. Pref
`erably the average is the D, average. Those skilled In the art
`will be aware that the primary particles can form agglom
`erates.
`(0031] The slyrene maleimide random (or block) copoly
`mer siructure may be defined by the general stmcture in
`lhrrnula (1)
`
`ii;
`
`where in, the number average of vinyl units is from 250 to
`800; and a, the ntimber average of cyclic anhydride units, is
`from 100 to 400. More preferably mis from 550 to 575; and
`a is from 200 to 22&
`[0032] The particles may be composed entirely of a sty
`rene-maleimide co-polymer or may be just partially styrene
`maleimide co-polymer When the polymerisation is carried
`out in the presence of another water insoluble species (that
`the second
`is a second component. such as vax or oil),
`component can be encapsulated. In the case where the core
`is a wax, paraffin wax can be used. In the case where a shell
`formed around the oil, suitable oils
`of the copolymer is
`inciude mineral oils; vegetable oils and esters of vegetable
`oils (for example, please see W020t 1/093574). Such a core
`may comprise an oil and such an oil may provide bioper
`formnance advantages for an agrochetuical (that is, it may be
`an oil adjavant. as discussed above). An example of such an
`is soybean oil. An example of such a commercially
`oil
`available styrene maleimide copolymer which contains soy
`bean oil is NanotopeTM 26 5050 WA5O-30 which is used in
`the examples herein. The ratio of the oil
`in the core to the
`co-polymer may be from 70:30 to 30:70 (preferably about
`50:50) by weight.
`[00331 The concentration of the styrene-maleimide eo
`polymer in the composilion is preferably from 2 to 50% by
`weight: more preferably from 3 10 3O%; even more prefer
`ably from 4 to 10% by weigin.
`]n one aspecl. the present invention provides the
`100341
`use of a core/shell styrene-maleimide co-polymer with an
`agroehemical.
`The term agrochemical includes herbicides, fungi
`[0035]
`cides, insecticides. neamticides and plant growth regulators.
`is an herbicide, a fungicide, a
`Suitably an agrochemical
`nematieide oran insecticide; more suitably it is an herbicide,
`a fungicide or an insecticide; even more suitably it
`is a
`fungicide or an insecticide.
`[00361 Examples of agrochemical active ingredients suit
`able for use within the continuous phase (i) or disperse phase
`(iii) in accordance with the present invention include, but are
`not limited to: fungicides such as azoxystrobin, chlorotha
`lonil, cyprodinil, cyproconazole, difeooconazole, fiudioxo
`
`

`

`US 2017/0086454 Al
`
`Mar. 30, 2017
`
`3
`
`nil. mandipropamid, picoxystrobin. propiconazole, pyra
`trifloxystrobha,
`ihiabeudazule,
`tebuconazule,
`closlrobin,
`bixafen, fluxapyroxad, furamelpyr, isopyrazam. penfluflen,
`penihiopyrath sedaxanc, boscalid. fenfuram. benofanil, Our
`tolanil. taepronil, thifluzarnide. carboxin. oxycarboxin. acid
`benxolar-S-methyl, oxathiapiprolin: and insecticides such as
`carbamates such as aldicarb, bendiocarb. bcnfuracarb, car
`fenobucarb,
`baryl. carbofi,raa, carbosulfan,
`feuoxycarb,
`jnethiocarb, methomyl, oxaowl. pirimicarb, thiodicarb, tn
`azamate; organophosphates such as acephate, chiorpyrifos,
`diazinon, malathion. methamidophos. methidathion. mono
`crolophos. parathion-methyl. pirinsiphos-inethvl. profeno
`fos. terbufos: fiproles such as ethiprole. liproail; pvretbroids
`such as allelhrin, bifenthrin, cytluthrin, cyhalolhrio. cyper
`metlu’in, alpha-cypennethrin, beta-cypennethrin, zeta-cy
`permethrin, deltarnethrin, esfenvalerate, etofenprox. fenva
`tau
`lambda-cyhalothrin. pennethrin, pyrethrin,
`lerate,
`fluvalinate, tefluthrin, tetramethrin; neanicotinoids such as
`imidacloprid,
`ifupyradiflirone,
`clothianidin, dinotefuran,
`thiamethoxarn, nitenpyram, acelamiprid, thiacloprid; spino
`syns such as spinosad, spinetorain; avermectins such as
`abamectin, emamectin benzoylureas such as buprofezin,
`clofentazine. diflubenzuron,
`cyramazin,
`chioriluazuron,
`diofenolan. etoxazole, flucycloxaron, flufenoxuron, hexaflu
`triflurnuron;
`teflubeozuron,
`tufenuron, novaluron,
`muron,
`tetronic and tetrarnic acid derivatives such as spirodiclofen,
`spiromesifen, spiratetratnat pymetrozine. flonicamid, etox
`az.ole. indoxacarb; ryanoids such as cyaatraniliprole.
`a contact agro
`is
`Preferably the agrochemical
`10037]
`chemical (rather than a systemic agrochemical).
`Suitable fungicides may be seiected from azox
`100381
`ystrubin. chIorothalonil. cyprodinil, difcnuconazole. tiudi
`oxonil. mandipropamid, picoxystrubin, pyraclostrobin and
`thfloxvstrobin. Preferably the fungicide is a soobilurin;
`is azoxystrobin
`more preferably it
`Suitable insecticides may be selected from abam
`100391
`ectin, clothianidin. emamectin henzoate, garnnsa cyhalo
`thrin, cyhalotbrin and its enantiomers such as lambda cyha
`and
`resmethrin
`permethrin.
`tefluthnn.
`lothrin,
`thiametlioxain.
`Preferably, when (he composition of the present
`100401
`invention contains an agrochensical [such as a strobilurin] it
`further contains a triazole fungicide such as cyproconazole,
`difenoconazole, propiconazole or tebuconazole.
`Preferably the total agrochemical concentration in
`[00411
`the composition is from 5% to 4/o by weight; more
`preferably from 15% to 30%.
`The compositions of the present invention may be
`100421
`used to improve the rainfasiness of an agrochemical.
`100431 The compositions of the present invention may he
`used to combat or control an agricultural pest or disease
`[such as a weed, a fungus. a nemalode or an insect].
`Stable compositions according to the present
`100441
`invention can be prepared readily using standard techniques,
`without having to take any special measures.
`[00451 The present invention is illustrated by the follow
`ing examples. The styrene maleintide copolymer used in all
`the following examples was Naootope1 265050 WA5O-30.
`supplied by TopChim.
`Suitable agrochemicals are azoxystrobin, cypro
`100461
`conazole, isopyrazam, cyantranilipole and chlorothalonil, as
`shown by the examples.
`
`EXAMPLE I
`Improved rainfastness ofazoxysirohin with styrene
`[00471
`maleisnide copolmer on corn.
`[00481 This study demonstrates that the addition of styrene
`maleinide copolymer cnn reduce the loss of an active
`ingredient from a leaf surface during rainfall.
`.4 range of substrates can be used in this test with
`100491
`in this example being a maize leaf.
`the chosen material
`Herein the maize plants. avenir variety, were grown for 3
`weeks to the 5 leaf stage. these leaves were mounted using
`double sided tape to flat tiles (30 cm by 30 cm at an even
`spacing of 3 leaves per tile.
`the
`A deposition solution was then prepared at
`10050]
`concentration which would be used under commercial appli
`cation conditions. In this case 0.67 g of an azoxystrobin 200
`gil SC fonnulation and 0.25 g Activator 90°’ (non-ionic
`surfactant) were added to 9858 g water for the control and
`the effect of the styrene malemide polymer determined by
`creating a similar sample with 0.3% w/w of the water
`replaced by styreoe malemide copolynier.
`[00511 Twenty 0.2 tI droplets were applied to each sub
`strate using a micro applicator. The substrate was allowed to
`dry for 2 hours. Aller the drying period one board containing
`6 leaves per treatment were ‘rained on’, at 10 mm/hour for
`one hotir while the other board was sampled by washing
`each leaf with 20 mIs of acetonitrile (Sigma Aldrich) and
`gentle agitation for 20 seconds. The rainfall was simulated
`using a rain lower which combines the rate of water flow and
`shutter opening to achieve the target intensity ofraiofall. The
`the droplets reached
`rain tower was positioned such that
`their terminal velocity before hitting the targct surface. After
`the raining period, the ‘rained on’ leaves were washed using
`the same protocol (gentle agitation in 20m1 acetonitrile for
`20 seconds).
`100521 The quantities of azoxystrobiii in the acetonitrile
`solutions were determined via LCMS (Thermo TSQ Quan
`tum LC/MSMS. Column 845) and the % active ingredient
`remaining after rainfall was detenniised by dividing the
`quantity of azoxystrobin on each leaf after rainfall by that
`before rainfall.
`[°°‘I Azoxystrobin SC+Activator OOTM: 3.5% azox
`ystrobin remained on the leaves.
`9OTM+styrene
`SC+Activator
`[00541 Azoxystrobin
`nvtlemide copolymer: 29% azoxystrobin remained on the
`leaves.
`
`EXAMPLE 2
`Improved rainfastness of azoxysimbin with styrene
`[0055]
`maleitnide copolymer on soya. This study demonstrates that
`the addition of styrene malemide copolymer can reduce the
`loss of an active ingredient from a lcaf surface during
`rainfall.
`100561 A range of substrates can be used in this test with
`the chosen material in this example being a soya leaf. Herein
`tlte soya. Glycine Mar (Williams variety), was grow-n for 4
`weeks in 4 inch pots with the top 2 tn-foliates used in the
`study. The leaves were mounted using double sided tape to
`flat tiles (30cm by 30cm) at an even spacing of 6 leaves per
`tile.
`the
`[00571 A deposition solution was then prepared at
`concentration which would be used under commercial appli
`calioo conditions. In this case 0.375 g of an azoxystrobin SC
`fornu,lation (containing 200 g/l azoxystrobin) and 7.5 g
`
`

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`US 2017/0086454 Al
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`Mar. 30, 2017
`
`4
`
`NirnbusTM were added to 98.6 g waler for the control and the
`effect of the styrene malemide co-polymer determined by
`creating a similar sample with 0.3%w/w of the water
`replaced by styrene malemide co-polymer.
`[0058] Twenty 0.2 d droplets were applied to each sub
`strate using a micro applicator. The substrate was allowed to
`dry for 2 hours. After the drying period one board containing
`6 leaves per treatment wean rained on’, at 10mm/hour for
`one hour while the olhcr board was sampled by washing
`each leaf with 20 mIs of acelonitrile (Sigma Aldrich) and
`gentle agilation for 20 seconds. The rainfall was simulated
`using a rain lower which combines the rate of water flow and
`shutter opening to achieve the target intensity of rainfa]l. The
`rain tower was positioned snch that the droplets reached
`their ten13anal velocity beibre hitting the target surface. After
`lhe raining period, the ‘mined on leaves were washed using
`the same protocol (gentle ablation in 20 ml acelonitrile for
`20 seconds).
`[00591 The quantities of azoxystrobin in the acetonitrile
`solutions determined via LCMS (Thermo TSQ Quantum
`LC/MS/MS. Column 845) and the % active ingredient
`remaining aftcr rainthll dctcrmined by dividing the quantity
`of AZ on each leaf afler rainfall by Ihat before rainfall.
`100601 Azoxystrobin SC+Nimbus13t: 15% azoxystrobin
`remained on the leaves.
`SCTM+NimbusTM:
`styrene
`100611 Azoxystrobin
`maemide copolymer 55% remained on the leaves.
`
`EXAMPLE 3
`
`[00621 This example demonstrates that while acrylic poly
`mets known for their water barrier properties can improve
`the rainfastoess of the active ingredient
`they can also,
`disadvantageously, reduce the bioavailability.
`100631 The method described in Example 2 was used to
`assess the rainfastness of azoxystrobin in the presence of
`NimbusIM on Soya leaves wilh the addition of various
`acrylic emulsion used was NeocrylTM
`polymers. The
`XK-230 (DSM) and the acrylic latex (NeocrylTM XK-90).
`100641 The bioavailability of
`azoxvstrobin was
`the
`assessed by spraying lhrcc week old soya plant (William’s
`variety) using a track sprayer and a standard fiat fan nozzle
`at an equivalent water volume of 50 I/ha conlaining 9 g /laa
`of aznxystrobin, 30 gJha NimbusTM and 0.3% w/w of the
`‘The plants were inoculated with I
`tested copolymers.
`spores per ml of waler one day after spray application and
`the first tn-foliates were assessed for fungal control afler a
`further 14 days.
`
`‘tABLE I
`
`% of azoxystrobia
`remanD8 on the
`leaf sorface
`
`control of
`Pimakqpsora
`pachyrhizia
`
`15
`55
`
`66
`20
`
`tOO
`tOO
`
`It
`43
`
`Compound
`
`nettle
`Styrene Maleimide
`copelyner
`Acrylic emulsion
`Acrylic alex
`
`100651 The data within ttie table show that while polymers
`improve the nainfastncss of azoxystrobin surprisingly only
`the stvrene mateimide allows the active ingredient to deliver
`acceptable biological perfomaance.
`
`EXAMPLE 4
`
`This example demonstrates the lack of impact on
`[0066]
`uptake of cyproconazole by the styrene inaleimide copoly
`mer.
`4” pots of soya, Williams’s variety, were grown in
`[0067!
`the glasshouse for four weeks until the plants reached the 3-4
`tnifoliate stage. These plants were tracksprayed with the
`treatmeat list below at a rate of 24 g a.i./ha in a waler volume
`of 80 I/ha. All treatments included NilnbusTM at a rate of 600
`mi/ha.
`[00681 At time zero, 5 hours after application and I, day
`after fully expanded leaves were cut off, weighed and shaken
`in 10 ml of acetonitrile to remove the unabsorbed foliar
`deposits. Ten replicate leaves were sampled per treatment
`and the samples analysed by LCMS (Thernmn TSQ Quantum
`LC/MS/MS. Column 845).
`
`TABLE 2
`
`% of cvprocorazole
`e.thrn the piart
`(5 hours after
`applicatloat
`
`¼ of cyproconazole
`within the plan
`(I day after
`applicatlon)
`
`67
`
`73
`
`45
`
`92
`
`87
`
`75
`
`Conpound
`
`cyp:ocoriazole SOgil SC +
`NtMOUS
`Cvprocorazole hog/I SC +
`Styrcec ?t4aleimide
`ccpolvmcr + lcMatjs
`Cvprcconazole SOmE SC +
`ArrvEEc alex + MNtBtES
`
`[00691 The treatment containing the acrylic latex is has a
`statistically significant lower uptake of cyproconazole than
`the treatments containing no additional polymer and the
`statistically
`copolymer, which are
`styrene maleimide
`equivalent.
`
`EXAMPLE 5
`
`[0070]
`Effect of stvrene maleimide rate on the rainfastness
`of an azoxystrobin 200 g/t SC. This study demonstrates that
`the amount of styrene matemide copolymer used posItively
`correlates with the rainfastncss of the resulting azox
`ystrobin-containing formulation.
`[0071] A range of substrates can be used in this test with
`the chosen material in this example being a soya leaf Herein
`the soya. Give me Ma.v, was grown for4 weeks in 4 inch pots
`with Ihe lop 2 tri-foliates used in the study. The leaves were
`mounted usilig double sided lape to flat tiles (30 cm by 30
`cln) at an even spacing of 6 leaves per tile.
`[0072] A deposition solution was then prepared at
`the
`concentration which would be uscd tllider commercial appli
`cation conditions. In this case 0,2 g of an azoxystrobin SC
`formulation (containing 200 gIl azoxystrobin) altd 0.4 g
`NimbusTM were added to 99.4 g water for the control and the
`effect of the styrene maleimide co-polymer determined by
`creating similar samples with 0.003, 0.006, 0.06, 0.t2,
`0.30% w/w of the water replaced by slyrene rnalemide
`co-polymer.
`[00731 Twenty 0.2 ii droplets were applied to each sub
`strate using a micro applicator. The substrate was allowed to
`dry for 2 hours. After the drying period one board containing
`6 leaves per treatment were ‘rained on’, at 10 mm/hour for
`one hour while the other board was sampled by washing
`each leaf with 20 mIs of acetonitrile (Siglna Aldrich) and
`
`

`

`US 2017/0086454 Al
`
`Mar. 30, 2017
`
`5
`
`gentle agitation for 20 seconds. The rainfall was simulated
`using a raia Lower which combines the rale of water flow aad
`shutter opening to achieve the target intensity of rainfall. The
`the droplets reached
`rain tower was positioned such that
`their terminal velocity before hilling the target surface, After
`the raining period, the ‘rained on’ leaves were washed using
`the same protocol (gentle atation in 20 ml acetouitrilc for
`20 seconds).
`The quantities of azoxystrobin in the acetonitrile
`100741
`solutions determined via LCMS (LC7MS/MS comprising of
`Acquity LC and Thernio TSQ-Ultra) and the % active
`ingredient remaining after rainfall determined by dividing
`the quantity of AZ on each leaf after rainfall by thai before
`rainfall.
`
`‘lADLE 3
`
`Tmatzreat
`
`Azoxystrobin SC
`Azoxystrotha SC + C.003%
`stvrene marim:ce ce-pelymer
`Azo’cycuobai SC ÷ O.0C6%
`stvrer.e msleirnrde cc-polyner
`.kzoxystrob:n Sc + 306%
`sterece malcinude cc-polymer
`.Azoxystrohn Sc + 012%
`etsrene rzaleimide cs-polymer
`MoY.ystschr sc + 0.3u%
`etvrese nateimide co-ao,ymer
`
`% azotsvstxob’n renaming
`oa Leaves &fter rainjill
`
`3.t
`I 1.0
`
`5.6
`
`15.9
`
`173
`
`312
`
`EXAMPLE 6
`
`Preparation of a Built-In Forrmilatioit
`Formulations containing the styrene maleimidc
`[0075]
`copolymer were prepared by the substitution of water from
`a typical SC [example compositions of which are given
`below]. These were prepared using standard preparation
`methods. As is common in suspension concentrate feamu
`lations the active ingredients were bead milled to improve
`colloidal stability to a size of around 1-2 microns and added
`those skilled in the art will appreciate the
`as a millbase.
`increase thc cthcicncy of the
`addition of dispcrsants will
`milling step. During addition of these components the fonn
`the polymer containing SC the formulation was mixed under
`high shear in a jacketed vessel at 10° C. for 10 minutes. The
`output was free flowing suspension concentrates.
`
`Coniponent
`
`AzoxIustrobin
`cypmconnzole
`Styrene ninlemide
`copolyner
`KelzsnM
`‘Vater make-up
`
`TABLE 4
`
`Order of
`addition
`
`Quantity in
`(WL)
`
`Quantity in
`giLt
`
`2
`4
`2
`
`5
`1
`
`83
`33
`340
`
`83
`33
`t20
`
`2
`make-up to
`litre
`I
`
`2
`make-up to
`t
`litre
`
`EXAMPLE 7
`
`10076] Rainfastness of an azoxystrobio 200 WI SC when
`mixed with a styrene maleinude-contaimng tank-mix adju
`vant.
`
`styrene
`the
`that
`demonstrates
`example
`The
`[0077]
`malemide copolymer can be combined with commercial
`tank-mix adjuvants to form emulsions which retains their
`rainfastness properties on spray tank dilution. Those skilled
`in the art will recogn se such a composition would make a
`powerful tank mix adjuvnnt.
`
`Preparation of Mix 1
`[0078] NimbusTM oil (6.0 ml) was added to a dispersion of
`NanotopeTM 26 5050 WA5O-30 (4.5 ml) in water (5.5 ml).
`The resulting mixture was rolled overnight.
`
`Preparation of Mix 2
`10079] NimbosTM oil (3.0 ml) was added to a dispersion of
`NanotopeTM 26 5050 WA5O-30 (4.5 ml) in water (2.0 ml).
`The resulting mixture was rolled overmght.
`
`Preparation of Mix 3
`[0080] NintbusM oil (5.0 ml) was added to a dispersinn of
`NanotopetM 26 5050 WA5O-30 (2.0 ml) in water (3.0 ml).
`The resulting mixture was rolled overnight.
`The rainfastness study was conducted ill the same
`[0081]
`manner as Example 2. Spray dilutions of 80 1/ha were
`prepared, comprising azoxystrobin SC at 300 mI/ha and the
`other components at the rate stated in the table below.
`
`TABLE S
`
`iecaoncnt
`
`Azoxystrobia sc + 0-6 I/ha Nimbus
`Azoxystrobia sc + 0.6 IJha Nimbus +
`26 5050 WASO-30
`450 mt’lrn Narotope
`Azoxystrobin SC + 1.6 ‘ha raaiLmix
`Azoxystrobia Sc + 0.7 i/ba Iankxnix I
`Azoxys’sobin sc + 0.55 ‘ha Taakrnix 2
`Azoxystrobin SC + 0.7 Lbs Tankex 2
`
`% A
`Remain ing
`en leaves
`after Rrafa!l
`
`Siardard
`Dcviatior
`
`7
`44
`
`40
`47
`72
`St
`
`6.1
`H.O
`
`24.7
`t9.4
`5.2
`6.5
`
`EXAMPLE 8
`Improved rainfastness of izopyrazam with styrene
`[0082]
`maleimide copnlymer on soya. this study demonstrates that
`the addition of styrene malernide copolymer can reduce tbe
`from a leaf surface dunno
`loss of an active ingredient
`rainfall.
`[0083] A range of substrates could have been used in this
`test but the chosen material in this example was soya leaf;
`soya, Gljcine Wox (Williams variety), was grown for 4
`weeks in 4 inch pots with the top 2 tri-foliates used in the
`study. The leaves were mounted, using double sided tape. to
`flat tiles (30cm by 30cm) at an even spacing of 6 leaves per
`tile.
`[0084] A deposition solution was then prepared at a con
`centration which could be used under commercial applica
`tion conditions. In this case 0.25 g of an isnpyrazam SC
`formulation (containing 250 g/l isopyrazam) was added to
`99.58 g water as the control sample whilst the effect of the
`styrene malemide co-polymer was determined by creating a
`similar sample in which 0.5 g of the water was replaced by
`styrene maleniide co-polymer.
`[0085] Twenty 0.2 tI droplets were applied to each sub
`state using a micro applicator. The substrate was allowed to
`
`

`

`US 2017/0086454 Al
`
`Mar. 30, 2017
`
`6
`
`day for 2 hours. After the drying period, one board contain
`ing 6 leaves per trealment was ‘rained on’, at 10 mm/hour
`for one hour while the other board was sampled by washing
`each leaf with 30 in! of acetonitrile (Sigma Aldrich) with
`gentle agtation for 20 seconds. The rainfall was simulated
`using a rain tower which combines the rate of water flow and
`shutter opening to achieve the target intensity of rainfall. The
`rain tower was positioned such that the droplets reached
`their tenninal velocity before hitting the target surface. After
`the raining period, the ‘mined on’ leaves were washed using
`the same protocol (gentle agitation in 30 ntt acetonitrile for
`20 seconds).
`100861 The quantities of izopyrazam in the acetonitrile
`solutions were determined by mass spectroinetry using a
`Waters Acquity UPLC and Thermo TSQ Quantum Ultra
`Triple Quadrupole MS Instrument or just LC/MS/MS.
`[0087] Column:
`Phase Kinetex CtS
`10088]
`10089] Length (mm) 50
`Internal diameter (mm) 3.0
`100901
`Particle Size (pm) 2.6
`100911
`the % active ingredient remaining
`tests,
`For all
`100921
`after rainfall determined by dividing the q