Herbicidal Composition comprising Polymeric Microparticles containing a Herbicide
The present invention relates to a new herbicidal composition, e.g. for controlling weeds in
crops of useful plants, especially in crops of non-oat cereals such as wheat and/or barley,
which composition comprises (a) polymeric microparticles containing a first herbicide,
wherein the first herbicide is a synthetic auxin herbicide or an ALS inhibitor herbicide (e.9. as
defined herein), and (b) pinoxaden (which is an ACCase inhibitor herbicide). The present
invention also relates to a herbicidal compositon comprising (a) polymeric microparticles
containing a first herbicide, wherein the first herbicide is a synthetic auxin herbicide or an
ALS inhibitor herbicide (e.9. as defined herein), and either (x) a nonionic surfactant (e.9. as
defined herein) or (y) a surface-modified clay (e.9. as defined herein).
Background of the lnvention
It is known, for example, from R.J.A. Deschamps, A.l. Hsiao and W.A. Quick, "Antagonistic
effect of MCPA on fenoxaprop activity" , Weei Scr., 38 (1990), pp. 62-66, that the
commercially available synthetic auxin herbicide MCPA tends to antagonise the herbicidal
efficacy of the herbicide fenoxaprop, which inhibits ACCase (acetyl coenzyme A
carboxylase), in view of the control of grass in cereals.
This antagonistic effect is sometimes also observed when different synthetic auxin
herbicides, such as dicamba or 2,4-D, are used in combination with a different ACCase
inhibitor herbicide, pinoxaden. Specifically, the herbicidal efficacy of the pinoxaden versus
certain grassy weeds is sometimes reduced, depending on the conditions and/or depending
on the application rates of the pinoxaden and of the dicamba or 2,4-D and/or depending on
the grassy weeds to be controlled. This sometimes affects the use of tank-mixtures of
pinoxaden mixed with a synthetic auxin herbicide such as dicamba or 2,4-D, in that the
grass-herbicidal (graminicidal) activity of pinoxaden can sometimes be negatively affected,
although the herbicidal activity against dicotyledonous weeds (provided by the synthetic
auxin herbicide) is usually excellent.
Antagonism of the herbicidal activity of pinoxaden is also sometimes seen when pinoxaden is
mixed with certain herbicidal inhibitors of acetolactate synthase (ALS) such as triasulfuron or
tribenuron-methyl (e.9. see results shown hereinafter in Biological Examples 4 and 5).
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Pinoxaden is a herbicide suitable for use on non-oat cereals such as wheat, barley, rye
andior triticale, especially wheat and/or barley (i.e. is selective for non-oat cereals), and is
typically applied post-emergence for control of grassy weeds such as Alopecurus, Apera,
Avena, Lolium, Phalaris or Setaria species, e.g. at application rates of from 30 to 60 g active
ingredient / ha (ha = hectare) (these features, e.g. uses or application rates can be used in
the present invention). Pinoxaden is typically and preferably used in admixture with
cloquintocetmexyl as a safener. Pinoxaden is disclosed as compound 1.008 in WO
99147525 A1 (Novartis AG); herbicidal compositions comprising pinoxaden and various coherbicides
are disclosed in WO 01117351A1 (Syngenta Participations AG); an emulsifiable
concentrate herbicidal composition comprising pinoxaden, an emulsifier(s), a water-insoluble
solvent(s) (e.9. aromatic hydrocarbons), an alcohol as a solvent (preferably benzyl alcohol,
tetrahydrofurfuryl alcohol ('THFA'), or 2-methyl-2,4-pentanediol), and optionally a further
herbicide, are disclosed WO 200T1073933 A2 (Syngenta Participations AG); and a liquid
herbicidal composition containing pinoxaden and a built-in phosphate adjuvant such as tris-
(2-ethylhexyl) phosphate is disclosed in WO 2008/049618 42 (Syngenta Participations AG);
all of which are incorporated herein by reference, and all of which are referred to in respect
of, and/or can be utilized in embodiments of, the present invention. Pinoxaden and its
herbicidal uses are disclosed in: M. Muehlebach el al., Bioorganic & Medicinal Chemistry,
2009, vol. 17 , pp. 42414256; M. Muehlebach et al., in "Pestickle Chemistry. Crop
Protection, Public Health, EnvironmentalSafetf', ed. H. Ohkawa eta1.,2007, Wiley,
Weinheim, pp. 101-110; U. Hofer et al. Joumal of Plant Dr'seases and Protection,2006,
Special lssue XX, pp. 989-995;and"The Pesticide Manuaf', ed. C.D.S. Tomlin, 1Sth edition,
2009, British Crop Production Council, UK, see entry 687 "pinoxaden" on pp. 911-912; all ot
which are incorporated herein by reference. Pinoxaden has the following structure:
(pinoxaden)
The synthetic auxin herbicides dicamba [3,6-dichloro-2-methorybenzoic acidl,2,4-D l(2,4-
dichlorophenoxy)acetic acidl, and MCPA [(4-chloro-2-methylphenoxy)acetic acid], and their
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herbicidaluses, are disclosed interaliain"The Pesticide Manuaf', ed. C.D.S. To, 1Sth
edition,2009, British Crop Production Council, UK, see entry 226"2,4-D" (pp.294-300), entry
245"dicamba" (pp. 323-325), and entry 535 "MCPA" (pp. 709-712); atl of which are
incorporated herein by reference. Dicamba or a salt thereof (e.9. sodium, potiassium, or
dimethylammonium salt, all of which are commercially available in formulations) is typically
used for control of annual and/or perennial broad-leaved weeds, or brush species; e.g. in the
following crops: cereals (e.9. wheat, badey, rye or oats, in particular spring or winter wheat,
spring barley or spring rye), maize, sorghum, sugar cane, asparagus, perennial seed
grasses, or turf; or in pastures, rangeland or non-crop land; e.g. at application rates in crops
of from 80 to 400 g or from 100 to 400 g active ingredient / ha, measured as the free acid; or
higher rates in pastures; the application rates vary with the specific use; for example, the
approved application rate in Canada for the BANVEL GM) ll herbicide (BASF Canada lnc.)
containing as active ingredient dicamba as the diglycolamine salt, in wheat, barley, rye or oat
crops, is from ca. 110 to ca. 140 g dicamba / ha, measured as the free acid (any of these
features e.g. uses or application rates can be used, separately or together, in the present
invention). 2,4-D or a salt thereof (e.9. sodium or dimethylammonium salt) is typically used
for post-emergence control of annual and/or perennial broad-leaved weeds, e.g. in various
crops including cereals, maize, established turf, orchards, sugar cane, rice, etc; e.g. at
application rates of from 280 to 2300 g active ingredient / ha, measured as the free acid
(these features, e.g. uses or application rates can be used in the present invention). MCPA
or a salt thereof (e.9. sodium, potassium, or dimethylammonium salt, all of which are
commercially available in formulations) is typically used for post-emergence control of annual
and/or perennial broad-leaved weeds; e.g. in the following crops: cereals, herbage seed
crops, flax, rice, vines, peas, potatoes, asparagus, grassland, turf, underfruit trees; or on
roadside verges or embankments; e.g. at application rates of from 280 to 2250 g active
ingredient / ha, measured as the free acid (these features, e.g. uses or application rates can
be used in the present invention). The structures of dicamba ,2,4-D, and MCPA are shown
below; and are characterised by the presence of a carboxylic acid moiety:
HrC... ooao "ff", .4X:*"-.q:J"'
dicamba 2,4-D MCPA
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Triasulfuron, tribenuron-methyl, iodosulfuron-methyl (as the sodium salt), mesosulfuronmethyl,
and pyroxsulam are disclosed in"The Pesticide Manuaf', ed. C.D.S. Tomlin, 1Sth
edition, 2009, British Crop Production Council, UK, see entry 494 "iodosutfuron-methylsodium"
(pp. 658-660), entry 550 "mesosutfuron-methyl" (pp. 733-734), entry 753
"pyroxsulam" (pp. 1001-1002), entry 868 "triasulfuron" (pp. 1 150-1151), and entry 873
"tribenuron-methyl" (pp. 1156-1158); all of which are incorporated herein by reference.
Triasutfuron is an ALS inhibitor, of the sutfonyl urea structural class, which is typically used
pre- or post- emergence for control of broad-leaved weeds, e.g. in cereal crops such as
wheat, barley or triticale, e.g. at application rates of from 5 to 10 g active ingredient / ha,
measured as the free compound (these features, e.g. uses or application rates can be used
in the present invention). Tribenuron-methyl is an ALS inhibitor, of the sulfonyl urea
structural class, which is typically used post-emergence for control of broad-leaved weeds,
e.g. in cereal crops such as wheat, barley, oats, rye or triticale, e.g. at application rates of
from 7.5 to 30 g active ingredient / ha, measured as the free compound (these features, e.g.
uses or application rates can be used in the present invention). lodosutfuron-methyl (usually
in the form of the sodium salt) is an ALS inhibitor, of the sulfonyl urea structural class, which
is typically used post-emergence for control of grass weeds and/or broad-leaved weeds, e.g.
in cereal crops such as winter, spring or durum wheat, triticale, rye or spring barley, e.g. at
an application rate of 10 g active ingredient / ha, measured as the free compound (these
features, e.g. uses or application rates can be used in the present invention). Typically,
iodosulfuron-methyl is used in admixture with mefenpyr-diethyl as a safener. MesosuJfuronmethyl
is an ALS inhibitor, of the sulfonyl urea structural class, which is typically used early to
mid post-emergence for control of grass weeds and/or (some) broad-leaved weeds, e.g. in
cereal crops such as winter, spring or durum wheat, triticale or rye, e.g. at an application rate
of 15 g active ingredient / ha, measured as the free compound (these features, e.g. uses or
application rates can be used in the present invention). Pyroxsulam is an ALS inhibitor, of
the triazolopyrimidine structural class, which is typically used post-emergence for control of
annual grasses and/or broad-leaved weeds; e.g. in cereal crops such as spring or winter
wheat, winter rye or winter triticale; e.g. at application rates of from 9 to 18.75 g active
ingredient / ha, measured as the free compound (these features, e.g. uses or application
rates can be used in the present invention). Pyroxsulam is typically used in admixture with
cloquintocet-mexyl as a safener.
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The structures of triasulfuron, tribenuron-methyl, iodosulfuron-methyl, mesosulfuron-methyl,
and pyroxsulam are shown below:
.CH"
o'cH' o
^o ,A*
N:YaNAnAA",.
Uo"X,"r,J,
triasulfuron
- CH.
o
,ocH.
mesosulfuron-methyl
o'cH'
)
,,,^i+io,u",. ll lHr
%/o. cH.
l/ cH.
o
tribenuron-methyl
*A
*Ar, H
N A"r,
ocH.
rodosulfuron-methyl
o'cHt
)
A+E-\7)-o-c,." \r-Ao_cn,
py'oxsulam
WO 20111162944 Al (Syngenta Participations AG), a copending PCT application filed on 7
June 2011 and published on 29 December 2011, discloses an aqueous liquid dispersion
concentrate composition comprising (a) a continuous aqueous liquid phase, and (b) at least
one dispersed, solid phase comprising polymer particles having a mean particle size of at
least one micron and prepared from either a curable or a polymerizable resin or a solidifiable
thermoplastic polymer, wherein the outside surfaces of the polymer particles comprise a
colloidal solid material and wherein the polymer particles have at least one chemical agent
(e.9. agrochemically active ingredient) distributed therein.
EP 0 517 669 A1 (Sandoz Ltd) discloses a process for micro-encapsulating a rapidly
leaching agrochemical (e.9. dicamba, MCPA or 2,4-D) comprising the steps of: (a) dissolving
or suspending the agrochemical in a nonaqueous liquid mixture comprising unsaturated
polyester resin and vinyl monomer; (b) emulsifying said solution or suspension in water to a
desired particle size; and (c) effecting crosslinking of the unsaturated polyester resin and
vinyl monomer to produce the microcapsules. Example 1 of EP 0 517 669 A1 discloses
polymeric microcapsules (formed from polymerizing / crosslinking a polyester/styrene liquid
resin mixed with dicamba and a peroxyester) suspended in an aqueous medium containing a
low amount of polyvinyl alcohol and significant amounts of two anionic surfactants
(lignosulfonate, and methylvinylether/maleic acid copolymer). The polymeric microcapsules
of EP 0 517 669 41 are disclosed as potentially reducing leaching below the targeted soil
(rt
H
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zone, for rapidly leaching agrochemicals. However, EP 0 517 669 41 does not disclose or
suggest that the polymeric microcapsules therein can be tank-mixed with pinoxadencontaining
compositions, and there is no suggestion therein of their suitability (or otherwise)
for reducing auxin- (e.9. dicamba-) generated antagonism of pinoxaden grass-herbicidal
activity.
Also, it is now thought that the specific dicamba microcapsule composition disclosed in
Example 1 of EP 0 517 669 A1 is not ideal for tank-mixing in water with a mixture of the
commercially-available pinoxaden-containing emulsifiable concentrate CEC") compositon
Axial rM lOOEC (a THFA-containing EC of the type disclosed and claimed in WO
20071073933 A2) and the associated tank-mix adjuvant Adigor tu ("n EC composition
comprising methylated rapeseed oil as an adjuvant), because of the flocculation which is
thought to result, which increases the risk of nozzle blockage and/or impaired sprayability in
agricultural spray equipment (see Polymeric Microparticle Example 14 hereinafter for
details). So it would be preferable, if possible, to improve the dicamba-microcapsule
compositons of EP 0 517 669 A1 so as to make them more clearly sprayable after tankmixing
in water with typical pinoxaden-containing EC compositions and/or Adigor rM.
Brief Summary of the lnvention
Surprisingly, it has now been found that, in a mixture of a synthetic auxin herbicide
(preferably dicamba and/or an agrochemically acceptable salt thereof) with the ACCase
inhibitor herbicide pinoxaden, where the mixture is at risk of the pinoxaden-mediated grassyweed
control being antagonised (reduced) by the presence of the synthetic auxin herbicide,
then this potential antagonism can be reduced, when the synthetic auxin herbicide is
contained within polymeric microparticles.
Preferably, the polymeric microparticles containing the synthetic auxin herbicide are
characterised by a reduced rate of release or reduced amount released over a specified time
period, e.g. within t hour or 3 hours, of the synthetic auxin herbicide (e.9. dicamba andlor a
salt thereof) from the microparticles into an aqueous medium in which the micropadicles are
suspended or dispersed, compared to the rate of release or dissolution or amount released
or dissolved of the same synthetic auxin herbicide (e.9. dicamba and/or a salt thereof) from a
substantially pure sample of the same synthetic auxin herbicide (e.9. dicamba and/or a salt
thereof) which is not contained within polymeric microparticles.
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It is thought likely that the same technical effect is likely to be achievable when an
acetolactate synthase (ALS) inhibitor herbicide, instead of the synthetic auxin herbicide, is
contained within polymeric microparticles.
Therefore, a first aspect of the present invention provides a herbicidal composition
comprising a mixture of (e.9. a herbicidally effective amount of a mixture of):
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (b) pinoxaden;
wherein the polymeric microparticles are controlled-release matrices, within which is the first
herbicide, and which function in such a way as to control and/or slow down the release of the
first herbicide from the polymeric microparticles into a liquid medium (preferably an aqueous
liquid medium) when the polymeric microparticles are placed (preferably dispersed) in and in
contact with the liquid medium.
The relevance, importance and/or technical significance of the first aspect of the invention is
thought to be as follows. Without being bound by theory, the first herbicide being contained
within polymeric microparticles which function as a controlled-release matrices is thought to
be an important factor as follows. When the herbicidal composition of the invention is
applied to the foliage, e.g. cuticula, of a plant such as a weed, it is thought that the polymeric
microparticles functioning as controlled-release matrices help to mitigate (reduce) the
tendency in some circumstances of the first herbicide to reduce (antagonise) the
monocotyledonous weed (e.9. grass-weed) herbicidal activity of pinoxaden. Such
antagonism of the activity of pinoxaden might otherwise be caused to an extent by the first
herbicide if it were released onto the plant at the same time as the pinoxaden, dependent on
the circumstances such as e.g. the application rates of the pinoxaden and/or of the first
herbicide and/or the weed type.
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Without being bound by theory, it is thought that the polymeric microparticles functioning as
controlled-release matrices slow down the release of the first herbicide in such a way as to
allow the pinoxaden to enter the plant first, thereby damaging or controlling
monocotyledonous e.g. grassy weeds, while much or most of the first herbicide enters the
plant later (e.9. ca. 30-60 minutes or ca. 30-180 minutes later). Without being bound by
theory, it is thought that because much or most of the first herbicide enters the plant after the
pinoxaden has entered the plant and after the pinoxaden has already had its herbicidal
effect, then the first herbicide therefore has a reduced opportunity to antiagonise the
pinoxaden herbicidal activity by whatever biochemical and/or other pathway(s) by which
antagonism takes place.
All this happens while retaining the convenience of applying to the crops and/or weeds
(preferably post-emergence)a single herbicidal composition containing both the first
herbicide and pinoxaden, i.e. allowing just a single spraying of the field, which reduces the
monetary costs (herbicide, fuel and labour costs) and environmental costs of spraying.
Where the first herbicide controls dicotyledonous weeds, this allows monocotyledonous e.g.
grassy weed control to be obtained via pinoxaden and dicotyledonous weed control to be
obtained via the first herbicide in a single spraying.
Further, a second aspect of the present invention provides a herbicidal composition,
comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (x) a nonionic surfactant (preferably comprising a nonionic polymeric barrier surfactant,
more preferably polyvinyl alcohol);
wherein the herbicidal composition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
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and wherein the nonionic surfactant is present in the continuous liquid phase or medium,
such that the nonionic surfactant stabilizes the dispersion of the polymeric microparticles in
the continuous liquid phase or medium,
and wherein the weight ratio of the polymeric microparticles to the nonionic surfactant in the
herbicidal composition is from 40 : 1 to 1 :2;
and wherein either the composition comprises no ionic surfactant, or the composition
comprises an ionic surfactant and the weight ratio of the polymeric microparticles to the ionic
surfactant in the herbicidal composition is 200:1or more.
Further, a third aspect of the present invention provides a herbicidal composition,
comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (y) a surface-modified clay;
wherein the herbicidalcomposition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
and wherein the surface-modified clay is present in the continuous liquid phase or medium
and/or is present at the interface between the continuous liquid phase or medium and the
polymeric microparticles, such that the surface-modified clay stabilizes the dispersion of the
polymeric microparticles in the continuous liquid phase or medium.
ln these second and third aspects of the invention, the herbicidal dispersion compositions, as
defined herein, comprising (a) polymeric microparticles ("PMPs") as defined herein
containing the first herbicide (e.9. synthetic auxin herbicide), and either (x) a nonionic
surfactant (e.9. as defined herein) or (y) a surface-modified clay, are novel PMP-containing
compositions. These compositions may optionally be marketed as a source of PMPs
wo 2013/034513 PCTtBP20t2l067072
containing the first herbicide. These compositions may optionally be mixed in a tank (tankmixed),
e.g. just before spraying on a field, with an emulsifiable concentrate ("EC")
composition containing pinoxaden (e.9. a pinoxaden EG containing an alcohol solvent such
as THFA, as disclosed such as claimed in WO 20071073933 A2 which en@mpasses the
commercial EC composition Axial rM 10OEC e.g. available from Syngenta), and optionally
atso with a tank-mix adjuvant such as Adigor rM
lwhich is an emulsifiable concentrate
containing 47% by weight of the formulation of methylated rapeseed oil as an adjuvant, e.g.
available from Syngenta), usually together with water. The resulting tank mixtures, which are
within the first aspect of the invention, may serve to reduce antagonism of pinoxaden grassherbicidal
activity.
More importantly for the second or third aspects of the invention, the Polymeric Microparticle
Examples 1 , 2, 4 to 9, 10 to 13, and 16 as disclosed hereinafter, which are embodiments of
the PMP-containing compositions according to the second or third aspects of the invention,
have been found to be suitable for tank mixing with all of: (i) a pinoxaden-containing EC of
the type used in AxialrM lOOEC (e.g. as disclosed such as claimed in WO 2007t073933 M),
and (ii) the Adigor rM adjuvant EC containing methylated rapeseed oil, and (iii) water. This
tank-mixability is shown in or suggested by Biological Examples 1-2,3, and 6-11 and
Polymeric Microparticle Example 16 hereinafter. More specifically, these tank mixtures
containing: one PMP composition selected from PMP Examples 1,2,4 to 9, 10 to 13, and
16; plus Axial rM 100EC; plus Adigor rM; plus water; appear to be sprayable. By "sprayable",
it is meant that any flocullation (e.9. heteroflocullation) that occurs (if it does occur) in the
tank-mixture is thought not generally to be serious enough so as to cause significant
blockage of spray nozzles (e.9. typical spray nozzles) of agricultural spraying equipment.
This sprayability, and/or this zero blockage or functionally-insignificant blockage of
agricultural spray nozzles, can for example be characterized by a generally low (functionallyinsignificant)
or zero amount of solid residue collected on a sieve of 150 micrometre aperture
size when a tank-mixture containing:
- a composition according to a second or third aspect of the invention, such as one PMP
composition selected from PMP Examples 1,2, 4 to 9, 10 to 13, and 16;
- plus (i) a pinoxaden-containing EC of the type used in Axial rM 1O0EC e.g. available from
Syngenta (i.e. an emulsifiable concentrate ("EC") containing 1009/L of pinoxaden, plus 25
g/L of cloquintocet-mexylas a safener, plus tetrahydrofurfurylalcohol and aromatic
hydrocarbons as solvents, plus one, two or three surfactiants; such as an EC as disclosed in
or similar to Example 1 (EC3) and/or Example 4 disclosed on pages 5-6 and 7 of WO
20071073933 A2, incorporated herein by reference);
10-
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- plus (ii) a tank-mix adjuvant of the type used in Adigor t'
".g.
available from Syngenta (i.e.
an emulsifiable concentrate containing 47% by weight of the formulation of methylated
rapeseed oil as an adjuvant);
- plus (iii) water;
is passed through the 1S0-micrometre-aperture sieve, e.g. at a time 0.5 to 24 hours, such as
1-4 hours or 10-24 hours, after the tank-mixture is first prepared. For example, see
Polymeric Microparticle Example 16 hereinafter to show how this sieve test works to
determine sprayability.
ln contrast to the second and third aspects of the invention, Example 1 of EP O 517 669 A1
(Sandoz Ltd) discloses polymeric microcapsules (formed from polymerizing / crosslinking a
polyester/styrene liquid resin mixed with dicamba and a peroxyester) suspended in an
aqueous medium containing a low amount of polyvinyl alcohol and significant amounts of two
anionic suffactants (lignosulfonate, and methylvinyl ether/maleic acid copolymer). A
substantial repeat of Example 1 of EP O 517 669 A1 has been performed in Polymeric
Microparticle Example 14 disclosed hereinafter. lt appears from PMP Example 14 that the
dicamba-PMPs produced by Example 1 of EP 0 517 669 Al, though they could be used as a
solo herbicide, cannot easily satisfactorily be tank-mixed with all of: (i) a pinoxadencontaining
EC of the type used in Axial rM 10OEC, plus (ii) Adigor rM; plus (iii) water; because
this tank-mixture flocullates (e.9. heteroflocullates) in a way that is likely to block typical spray
nozzles of agricultural spraying equipment, as measured by significant solid residues
collected on a 150-micrometre-aperture-sieve. See Polymeric Microparticle Example 14
disclosed hereinafter.
It is thought, e.g. from the data shown in PMP Example 16, that the PMP-containing
compositions according to the second and third aspects of the invention should mitigate this
problem of the poor-sprayability of [Axial
rM 10OEC + Adigor TM + water] tank-mixtures of the
dicamba-PMPs disclosed in Example 1 of EP 0 517 669 A1.
Also, with respect to the third aspect of the invention, the mentioned surface-modified clay
(particularly the amino-silane-modified clay e.g. as used in some of the Examples herein) is
thought to be superior to regular clay (e.9. china clay), in that the quality of the final aqueous
dispersion (and/or the quality of the aqueous emulsion, before curing of a polyester resin to
form the PMPs) is superior when an amino-silane-modified kaolin clay is used instead of
regular china clay, for dicamba-containing PMPs based on a crosslinked polyester. Without
being bound by theory, it is postulated that the surface modification helps the clay to sit
11
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better at the interface between the PMPs and the aqueous continuous phase of an aqueous
dispersion.
Further, a fourth aspect of the present invention provides a herbicidal composition,
comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (x) a nonionic surfactant (preferably comprising a nonionic polymeric banier surfactant,
more preferably polyvinyl alcohol);
wherein the herbicidalcomposition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
and wherein the nonionic surfactant is present in the continuous liquid phase or medium,
such that the nonionic surfactant stabilizes the dispersion of the polymeric microparticles in
the continuous liquid phase or medium,
wherein the polymer microparticles comprise a polymeric matrix or matrices comprising a
crosslinked polyester polymer or co-polymer (preferably a crosslinked polyester polymer
formed from the polymerization of an unsaturated (alkene-containing) polyester resin mixed
with an alkenyl-group-containing monomer);
and wherein the mean diameter by volume of the polymeric microparticles containing the first
herbicide is from 0.5 to 15 micrometres (preferably from 0.7 to 15 micrometres or from 1 .0 to
15 micrometres or from 2.0 to 15 micrometres, more preferably from 0.7 to 13 micrometres or
from 1.0 to 13 micrometres orfrom 2.0 to 13 micrometres orfrom 2.5 to 13 micrometres or
from 3.0 to 13 micrometres, most preferably from 2.0 to 12 micrometres or from 3.0 to 12
micrometres or from 4.0 to 12 micrometres), as measured by light scattering laser diffraction
(such as dynamic or static light scattering laser diffraction).
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With respect to the fourth aspect of the invention, Polymeric Microparticle (PMP) Examples
10 and 1 1 , which have good properties (especially PMP Example 1 1, whose herbicidal field
trial results are shown in Biological Example no. 3), are preferred embodiments of the fourth
aspect of the invention. The particle size (especially, the mean diameter by volume (i.e.
volume-weighted mean diameter), as measured by light scattering laser diffraction) of the
dicamba polymeric microparticles defined in the fourth aspect of the invention (and within
PMP Examples 10 and 11 - see Figures 4 and 5 herein) is thought to be smaller than the
particle size of the dicamba polymeric microparticles prepared in PMP Example 14 (see
Figure 8 herein)which is a substantial repeat of Example 1 of EP 0 517 669 A1 (Sandoz
Ltd). ln PMP Example 14 the dispersion includes a large number of quite large polymeric
microparticles whose diameters are in the 13 to 50 micrometre, or 15 to 50 micrometre,
range.
Brief Description of the Drawings
Figure 1 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 1, wherein the scale-bar shown is
10 micrometres.
Figure 2 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 2, in which the scale-bar shown is
10 micrometres.
Figure 3 is a graph of percentage dicamba released versus time (hours), showing the release
and release rate data, into water, for Polymeric Microparticle Examples 1, 2 and 3.
Figure 4 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 10, wherein the scale-bar shown is
50 micrometres.
Figure 5 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 11, wherein the scale-bar shown is
20 micrometres.
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Figure 6 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 12, wherein the scale-bar shown is
50 micrometres.
Figure 7 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 13, wherein the scale-bar shown is
50 micrometres.
Figure 8 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 14 (experiment SJH001/0351002, a
substantial repeat of Example 1 of EP 0 517 669 A1 (Sandoz Ltd)), wherein the two scalebars
shown are 20 micrometres (at left side of photograph) and 50 micrometres (at bottom of
photograph).
Figure 9 is an optical microscope photograph, taken after 5 minutes of mixing, of the tank
mixture comprising Polymeric Microparticle Example 14, AxialrM 100EC (an emulsifiable
concentrate ("EC") containing pinoxaden), Adigor " (rn emulsifiable concentrate containing
methylated rapeseed oil as an adjuvant), and water; in Figure 9, the scale-bar shown is 500
micrometres.
Figure 10 is an optical microscope photograph, taken atter 2.5 hours of mixing, of the tank
mixture comprising Polymeric Microparticle Example 14, Axial r' 10OEC, Adigor rM, and
water; in Figure 10, the scale-bar shown is 200 micrometres.
Figure 11 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 15 (experiment SJH001/035/003),
wherein the scale-bar shown is 20 micrometres.
Figure 12 is an optical microscope photograph, taken after 5 minutes of mixing, of the tank
mixture comprising Polymeric Microparticle Example 15, Axialr' 100EC (an emulsifiable
concentrate containing pinoxaden), Adigor t* (rn emulsifiable concentrate containing
methylated rapeseed oil as an adjuvant), and water; in Figure 12, the scale-bar shown is 200
micrometres.
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Figure 13 is an optical microscope photograph, taken atter 2.5 hours of mixing, of the tank
mixture comprising Polymeric Microparticle Example 15, Axial r' 100EC, Adigor rM, and
water; in Figure 13, the scale-bar shown is 1000 micrometres.
Figure 14 is an optical microscope photograph of the dicamba-containing polymeric
microparticles formed in Polymeric Microparticle Example 16 (experiment SJH001/035/004),
wherein the scale-bar shown is 20 micrometres.
Figure 15 is an optical microscope photograph, taken after 5 minutes of mixing, of the tank
mixture comprising Polymeric Microparticle Example 16, AxialrM 10OEC (an emulsifiabte
concentrate containing pinoxaden), Adigor " ("n emulsifiable concentrate containing
methylated rapeseed oil as an adjuvant), and water; in Figure 15, the two scale-bars shown
are 20 micrometres (top left of photograph) and 200 micrometres (bottom left of photograph).
Figure 16 is an optical microscope photograph, taken atler 2.5 hours of mixing, of the tank
mixture comprising Polymeric Microparticle Example 16, Axial rM 100EC, Adigor rM, and
water; in Figure 16, the scale-bar shown is 100 micrometres.
Figure 17 is a graph of the release and release rate data, for water as receiving material, for
Polymeric Microparticle Example 11 (experiment SJH001 10111002), plotting the
concentration of dicamba acid (in g/L) released from the polymeric microparticles versus time
(hours).
Figure 18 is a graph of the release and release rate data, for water as receiving material, for
Polymeric Microparticle Example 11 (experiment SJH001 10111002), plotting the percentage
of total dicamba acid released from the polymeric microparticles versus time (hours); based
on a theoretical 0.5095 g/L dicamba acid concentration for 100o/o dicamba release.
Figure 19 is an optical microscope photograph of thetriasulfuron-containing polymeric
microparticles formed in Polymeric Microparticle Example 18, in which the scale-bar shown is
20 micrometres.
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16-
Detailed Description of the lnvention
Preferred, particular and/or optional embodiments of the first, second, third and/or fourth
aspects of the present invention are presented hereinafer. Unless mentioned otherwise, and
except when inappropriate, these preferred, particular and/or optional embodiments apply to
any and all of the first, second, third and/orfourth aspects of the present invention, with any
necessary changes to the wording being made.
Preferred, particular and/or optional embodiments of the Polymeric Microparticles
Preferably, in allaspects (e.g.the first, second, third and/orfourth aspects) of the present
invention, the polymeric microparticles are controlled-release polymeric microparticles.
Preferably, the polymeric microparticles are controlled-release matrices, within which is the
first herbicide, and which function in such away as to control and/or slow down the release
of the first herbicide from the polymeric microparticles into a liquid medium (preferably an
aqueous liquid medium) when the polymeric microparticles are placed (preferably dispersed)
in and in contact with the liquid medium.
Preferably, the polymeric microparticles containing the first herbicide are controlled-release
matrices within which is the first herbicide, and which are characterized by:
an amount of the first herbicide released, over a specified time period (preferably over the
first t hour of contact, or over the first 3 hours of contact), from the polymeric microparticles
into a liquid medium (preferably an aqueous liquid medium e.g. water) after the polymeric
microparticles are placed (preferably dispersed) in and in contact with the liquid medium,
which is reduced (typically reduced by at least 30%, preferably by at least 40o/o or at least
50%, more preferably by at least 60% or by at least 70o/o ot by at least 75o/o, typically
measured by numbers of moles of the first herbicide or measured by weight of the first
herbicide calculated in a salt-free form),
compared to an amount of the same first herbicide released or dissolved over the same
specified time period, from a sample (typically a solid sample)of the same first herbicide
which is in substantially pure form (e.9. at least 85%, preferably at least 97o/o ot at least 98%
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or at least 997o pure, by weight) and in which the first herbicide is not contained within
polymeric microparticles, into the same liquid medium (preferably the same aqueous liquid
medium e.g. water) used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed (preferably dispersed) in and in
contact with the liquid medium.
More preferably, the polymeric microparticles are controlled-release matrices within which is
the first herbicide, and which are such that the amount of the first herbicide released, over
the first 3 hours of contact, from the polymeric microparticles into an aqueous liquid medium
(preferably water) after the polymeric microparticles are placed (preferably dispersed) in and
in contact with the liquid medium, is equal to or less than 35% (more preferably equal to or
less than 30%, still more preferably equalto or less lhan260/o, typically measured by
numbers of moles of the first herbicide or measured by weight of the first herbicide calculated
in a salt-free form),
compared to an amount of the same first herbicide released or dissolved, over the first 3
hours of contact, from a sample (typically a solid sample) of the same first herbicide which is
in substantially pure form (e.9. at least 85%, preferably at leastgTo/o or at least 98o/o or at
least 99% pure, by weight) and in which the first herbicide is not contained within polymeric
microparticles, into the same aqueous liquid medium (preferably water) used for the
polymeric microparticle release analysis, after the substantially pure sample of the first
herbicide is placed (preferably dispersed) in and in contact with the liquid medium.
Alternatively or additionally, more preferably, the polymeric microparticles are controlledrelease
matrices within which is the first herbicide, and which are such that the amount of the
first herbicide released, over the first t hour of contact, from the polymeric microparticles into
an aqueous liquid medium (preferably water) after the polymeric microparticles are placed
(preferably dispersed) in and in contact with the liquid medium, is equal to or less than 32o/o
(more preferably equal to or less lhan 28o/o, still more preferably equal to or less lhan 24o/o,
typically measured by numbers of moles of the first herbicide or measured by weight of the
first herbicide calculated in a salt-free form),
compared to an amount of the same first herbicide released or dissolved, over the first t hour
of contact, from a sample (typically a solid sample) of the same first herbicide which is in
substantially pure form (e.9. at least 85%, preferably at least 97o/o or at least 98% or at least
99% pure, by weight) and in which the first herbicide is not contained within polymeric
microparticles, into the same aqueous liquid medium (preferably water) used for the
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polymeric microparticle release analysis, after the substantially pure sample of the first
herbicide is placed (preferably dispersed) in and in contact with the liquid medium.
Alternatively or additionally, preferably, the polymeric microparticles containing the first
herbicide are controlled-release matrices within which is the first herbicide, characterized by:
a rate of release, over a specified time period (preferably over the first t hour of contact, or
over the first 3 hours of contact), of the first herbicide from the polymeric microparticles into a
liquid medium (preferably an aqueous liquid medium e.g. water) after the polymeric
microparticles are placed (preferably dispersed) in and in contact with the liquid medium,
which is reduced (typically reduced by at least 30%, preferably by at least 40o/o or at least
50%, more preferably by at least 60% or by at least 70% or by at least 75%, typically
measured by numbers of moles of the first herbicide or measured by weight of the first
herbicide calculated in a salt-free form),
compared to a rate of release or dissolution of the same first herbicide over the same
specified time period, from a sample (typically a solid sample) of the same first herbicide
which is in substantially pure form (e.9. at least 857o, preferably at least 97o/o ot at least g8%
or at least 99% pure, by weight) and in which the first herbicide is not contained within
polymeric microparticles, into the same liquid medium (preferably the same aqueous liquid
medium e.g. water) used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed (preferably dispersed) in and in
contact with the liquid medium.
Preferably, in allaspects (e.g.in thefirst, second, third and/orfourth aspects)of the
invention, the polymeric microparticles containing the first herbicide have a particle size as
defined in the following paragraphs.
Particle size(s), e.g. of the polymeric microparticles containing the first herbicide, is or are
typically measured by microscopy (e.9. optical microscopy or electron microscopy), or by
laser dffiaction and/or by light scattering. ln one preferred embodiment, particle size is
measured by optical or electron microscopy; more preferably by optical microscopy (light
microscopy); in the optical microscopy particle size measurements, $pically the particle size
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(e.9. of the polymeric microparticles containing the first herbicide) is measured or stated by
number. ln an alternative preferred embodiment, particle size (e.9. of the polymeric
microparticles containing the first herbicide) is measured by laser diffraction and/or by light
scattering, more preferably by light scattering laser diffraction (in particular by dynamic or
static light scattering laser diffraction, typically using a Malvern Mastersizer rM instrument e.g.
Malvern Mastersizer rM 20OO instrument, e.g. available from Malvern lnstruments, UK); in
these laser diffraction and/or light scattering particle size measurements, preferably the
particle size is measured or stated by volume (e.g. by stating the mean diameter by volume =
the volume-weighted mean diameter).
Generally, for particle size analysis, sphericity of the particles is assumed. Typically, in the
present invention, the polymeric microparticles are substantially spherical.
When measuring particle size(s) (e.g. by number or by volume), especially by optical
microscopy, particles which are generally too smallto be detected by particle size analysis
method (e.g. by the microscope such as an optical microscope) are preferably ignored (i.e.
not taken into account) in the particle size analysis (e.9., depending on the microscope such
as an optical microscope, ignoring particles smaller than 0.5 micrometres in diameter). For
example, particles smaller than 0.5 micrometres in diameter are preferably ignored when
measuring using a Leica Diaplan optical microscope, because 0.5 micrometres is the limit of
resolution of this optical microscope (e.9. as was done in the Examples hereinafter).
Preferably, 90% or more (e.9. by volume or by number) of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 100 micrometres
(microns). More preferably, 90% or more (e.g. by volume or by number) of the polymeric
microparticles containing the first herbicide have a particle size of less than or equal to 50
micrometres (microns). Still more preferably, 90% or more (e.9. by volume or by number) of
the polymeric microparticles containing the first herbicide have a particle size of less than or
equalto 30 micrometres (microns). Yet more preferably, 90% or more (e.g. by volume or by
number) of the polymeric microparticles containing the first herbicide have a particle size of
less than or equalto 10 micrometres (microns). Most preferably, 90% or more (e.g. by
volume or by number) of the polymeric microparticles containing the first herbicide have a
particle size of less than or equal to B micrometres (microns). ln one particular embodiment,
these particle sizes are as measured by optical microscopy (especially when measured or
stated by number); more particularly as measured by optical microscopy and ignoring
particles smaller than 0.5 micrometres in diameter. ln an alternative preferred embodiment,
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these particle sizes are measured by laser diffraction and/or by light scattering (especially
when measured or stated by volume), in particular by light scattering laser ditfraction, such
as by dynamic or static light scattering laser diffraction (e.g. using a Malvern Mastersizer rM
instrument).
Preferably, 50% or more (e.9. by volume or by number) of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 50 micrometres
(microns). More preferably, 50% or more (e.g. by volume or by number) of the polymeric
microparticles containing the first herbicide have a particle size of less than or equal to 25
micrometres (microns). Still more preferably, 50o/o or more (e.9. by volume or by number) of
the polymeric microparticles containing the first herbicide have a particle size of less than or
equal to 15 micrometres (microns). Yet more preferably, 50% or more (e.g. by volume or by
number) of the polymeric microparticles containing the first herbicide have a particle size of
less than or equal to 7 micrometres (microns). Most preferably, 50o/o ot more (e.9. by volume
or by number) of the polymeric microparticles containing the first herbicide have a particle
size of less than or equalto 5 micrometres (microns). ln one particular embodiment, these
particle sizes are as measured by optical microscopy (especially when measured or stated
by number); more particularly as measured by optical microscopy and ignoring particles
smaller than 0.5 micrometres in diameter. ln an alternative preferred embodiment, these
particle sizes are measured by laser diffraction and/or by light scattering (especially when
measured or stated by volume), in particular by light scattering laser diffraction, such as by
dynamic or static light scattering laser diffraction (e.g. using a Malvem Mastersizer rM
instrument).
Preferably, 90o/o ot more (e.9. by volume or by number) of the polymeric microparticles
containing the first herbicide have a particle size of more than or equal to 0.1 micrometres
(microns). More preferably, 90% or more (e.g. by volume or by number) of the polymeric
microparticles containing the first herbicide have a particle size of more than or equal to 0.3
micrometres (microns). Still more preferably, 90% or more (e.9. by volume or by number) of
the polymeric microparticles containing the first herbicide have a particle size of more than or
equal to 0.5 micrometres (microns). Most preferably, 90% or more (e.9. by volume or by
number) of the polymeric microparticles containing the first herbicide have a particle size of
more than or equal to 0.7 micrometres (microns). ln one particular embodiment, these
particle sizes are as measured by optical microscopy (especially when measured or stated
by number); more particularly as measured by optical microscopy and ignoring paflicles
smaller than 0.5 micrometres in diameter. ln an alternative preferred embodiment, these
20-
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-21 -
particle sizes are measured by laser diffraction and/or by light scattering (especially when
measured or stated by volume), in particular by light scattering laser ditfraction, such as by
dynamic or static light scattering laser diffraction (e.g. using a Malvern Mastersizer rM
instrument).
Preferably, 90o/o or more by number or by volume of the polymeric microparticles containing
the first herbicide have a particle size of less than or equal to 50 micrometres (microns); and
50% or more by number or by volume of the polymeric microparticles containing the first
herbicide have a particle size of less than or equalto 25 micrometres (microns); and 90% or
more by number or by volume of the polymeric microparticles containing the first herbicide
have a particle size of more than or equal to 0.1 micrometres (microns) (or more than or
equal to 0.3 micrometres, or more than or equalto 0.5 micrometres). ln one particular
embodiment, these particle sizes are as measured by optical microscopy (especially when
measured or stated by number); more particularly as measured by optical microscopy and
ignoring particles smaller than 0.5 micrometres in diameter. ln an altemative preferred
embodiment, these particle sizes are measured by laser diffraction and/or by light scattering
(especially when measured or stated by volume), in particular by light scattering laser
diffraction, such as by dynamic or static light scattering laser diffraction (e.9. using a Malvern
Mastersizer rM instru ment).
More preferably, 90% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 30 micrometres
(microns); and 50% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 15 micrometres
(microns); and 90% or more by number or by volume of the polymeric microparticles
containing the first hefuicide have a particle size of more than or equal to 0.1 micrometres
(microns) (or more than or equal to 0.3 micrometres, or more than or equalto 0.5
micrometres). ln one particular embodiment, these particle sizes are as measured by optical
microscopy (especially when measured or stated by number); more preferably as measured
by optical microscopy and ignoring particles smaller than 0.5 micrometres in diameter. ln an
alternative preferred embodiment, these particle sizes are measured by laser diffraction
and/or by light scattering (especially when measured or stated by volume), in particular by
light scattering laser diffraction, such as by dynamic or static light scattering laser diffraction
(e.g. using a Malvern Mastersizer rM instrument).
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Yet more preferably, 90Yo or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 10 micrometres
(microns); and 50% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 7 micrometres
(microns); and 90% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of more than or equa! to 0.3 micrometres
(microns) (or more than or equal to 0.5 micrometres). ln one particular embodiment, these
particle sizes are as measured by optical microscopy (especially when measured or stated
by number); more preferably as measured by optical microscopy and ignoring particles
smaller than 0.5 micrometres in diameter. ln an alternative preferred embodiment, these
particle sizes are measured by laser diffraction and/or by light scattering (especially when
measured or stated by volume), in particular by light scattering laser diffraction, such as by
dynamic or static light scattering laser diffraction (e.g. using a Malvem Mastersizer rM
instrument).
Most preferably, 90% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to B micrometres
(microns); and 50% or more by number or by volume of the polymeric microparticles
containing the first herbicide have a particle size of less than or equal to 5 micrometres
(microns); and 90% or more by number or by volume of the polymeric micropadicles
containing the first herbicide have a particle size of more than or equal to 0.3 micrometres
(microns) (or more than or equal to 0.5 micrometres, or more than or equalto 0.7
micrometres). ln one particular embodiment, these particle sizes are as measured by optical
microscopy (especially when measured or stated by number); more preferably as measured
by optical microscopy and ignoring particles smaller than 0.5 micrometres in diameter. ln an
alternative preferred embodiment, these particle sizes are measured by laser ditfraction
and/or by light scattering (especially when measured or stated by volume), in particular by
light scattering laser diffraction, such as by dynamic or static light scattering laser diffraction
(e.g. using a Malvern Mastersizer rM instrument).
Preferably, the mean diameter (preferably by number (e.9. when measured by optical
microscopy) or by volume (e.9. when measured by laser diffraction and/or by light
scattering)) of the polymeric microparticles containing the first herbicide is from 0.2 to 50 or
from 0.5 to 50 micrometres (microns), more preferably from 0.2 to 30 or from 0.5 to 30
micrometres, still more preferably from 0.5 to 20 micrometres or from 0.7 to 20 micrometres,
yet more preferably from 0.5 to 15 micrometres or from 0.7 to 15 micrometres or from 1 .0 to
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15 micrometres; further more preferably from 0.5 to 10 micrometres or from 0.7 to 10
micrometres or from 1 .0 to 10 micrometres, most preferably from 1 .0 to 7 micrometres or
from 1.0 to 5 micrometres or from 1.5 to 5 micrometres. Preferably, the standard deviation of
the diameter (e.9. by number or by volume) of the polymeric microparticles containing the
first herbicide is from 0.3 to 15 or from 0.5 to 10 or from 0.5 to 5 or from 0.7 to 4 micrometres.
ln one particular embodiment, these particle sizes (mean diameter and/or standard
devisation of diameter) are as measured by optical microscopy, especially when measured
or stated by number; more particularly as measured by optical microscopy and ignoring
particles smaller than 0.5 micrometres in diameter. ln an altemative preferred embodiment,
these particle sizes are measured by laser diffraction and/or by light scattering (especially
when measured or stated by volume), in particular by light scattering laser ditfraction, such
as by dynamic or static light scattering laser dffiraction (e.g. using a Malvern Mastersizer rM
instrument).
Preferably, the polymer microparticles comprise a polymeric matrix or matrices comprising:
- a crosslinked polyester polymer or co-polymer, preferably a crosslinked polyester polymer
formed from the polymerization of an unsaturated (alkene-containing) polyester resin mixed
with an alkenyl-group-conta in ing (e. g. vinyl-groupcontain ing ) monomer;
- an epoxy polymer or co-polymer;
- a phenolic, urea or melamine polymer or co-polymer;
- a silicone or rubber polymer or co-polymer;
- a polyisocyanate, polyamine or polyurethane polymer or co-polymer;
- an acrylic polymer or co-polymer; such as a polymer or co-polymer of an acrylate, C1-
Czalkyl acrylate, a methacrylate or Cr-Czalkyl methacrylate; in particular poly(acrylic acid), an
alkali metal (e.9. sodium, potassium or lithium) polyacrylate, a poly(methyl acrylate),
poly(methacrylic acid), an alkali metal (e.9. sodium, potassium or lithium) polymethacrylate,
or a poly(methyl methacrylate), as a polymer or co-polymer;
- a polymer or co-polymer of styrene, vinyltoluene, alpha-methylstyrene, divinylbenzene, or
diallylphthalate; such as polystyrene, polystyrene-co-butadiene, polystyrene-co-acrylonitrile,
poly(vinyltoluene), poly(alpha-methylstyrene), poly(divinylbenzene), a copolymer of
divinylbenzene with sodium or potiassium methacrylate, or poly(diallylphthalate);
- a polyacrylonitrile polymer or co-polymer;
- a polyalkylacetate polymer or co-polymer;
- a cellulose derivative; e.g. a Cr-Csalkyl and/or hydroxypropyl derivative of cellulose (e.9.
hydrorypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), ethylcellulose (EtC) or
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methylcellulose (MeC)), or carboxymethylcellulose (CMC), sodium carboxymethylcellulose
(NaCMC) or calcium carboxymethylcellulose (CaCMC); e.g. a cellulose derivative (e.9.
HPMC, HPC, EtC, MeC, CMC, NaCMC or CaCMC) having a molecular weight of from 2000
to 4000000 or more typically from 20000 to 1000000 or from 50000 to 1000000;
- polyvinylpyrrolidone (PVP) (crosslinked or non-crosslinked), e.g. PVP having a molecular
weight of from 30000 to 400000;
- a polyoxyethylene-polyorypropylene copolymer (poloxamer); and/or
- a cured aminoplast resin polymer.
See for example WO 201 11162944 Al (e.9. see pages 3-9, claims 18-26, claims 30-33,
and/or Examples 1-24 therein) for more details of potentially suitable polymers (often
prepared from curable resins) which may be comprised in (or which may be) the polymeric
matrix or matrices according to the present invention.
More preferably, the polymer microparticles comprise a polymeric matrix or matrices
comprising:
- a crosslinked polyester polymer or co-polymer, preferably a crosslinked polyester polymer
formed from the polymerization of an unsaturated (alkene-containing) polyester resin mixed
with an alkenyl-group-containing (e.g.vinyl-group+ontaining) monomer; and/or
- an epoxy polymer or co-polymer.
Still more preferably, the polymer microparticles comprise a polymeric matrix or matrices
comprising a crosslinked polyester polymer or co-polymer, preferably a crosslinked polyester
polymer formed from the polymerization of an unsaturated (alkene-containing) polyester
resin mixed with an alkenyl-group-containing (e.g.vinyl-group-containing) monomer.
ln this crosslinked polyester polymer or co-polymer embodiment of the invention, preferably,
the alkenyl-group-containing (e.9. vinyl-group-containing) monomer comprises (e.9. consists
essentially of) styrene, vinyltoluene, alpha-methylstyrene, divinylbenzene, diallylphthalate,
acrylonitrile, an acrylate, Cr-Czalkyl acrylate, a methacrylate or Cr-Czalkyl methacrylate.
More preferably, the alkenyl-group-containing (e.9. vinyl-group-containing) monomer
comprises (e.9. consists essentially of) styrene, vinyltoluene, alpha-methylstyrene or
divinylbenzene. Most preferably, the alkenyl-group-containing (e.9. vinyl-group-containing)
monomer comprises (e.9. consists essentially of) styrene.
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ln this crosslinked polyester polymer or co-polymer embodiment of the invention, preferably,
the unsaturated (alkene-containing) polyester resin has been formed from a non-alkenecontaining
di-carboxylic acid (such as ortho-phthalic acid) polymerised with a
alkene-containing diol or glycol.
ln particular, a highly preferred crosslinked polyester polymer is formed from the
polymerization of a resin mixture of (i) an unsaturated (alkene-containing) polyester resin
formed from ortho-phthalic acid polymerised with an alkene-containing diol or glycol, and (ii)
styrene. A preferred example of such an uncured (unpolymerised) resin mixture, having a
styrene content of about 45o/o by weight of the resin mixture, is for example available as
VIAPAL rM VUP 4779l55,from Gytec lndustries lnc., Smyrna, GA, USA, orfrom Cytec
Surface Specialities in Belgium and Germany (www.cytec.com). Polymerization (curing) of
such a resin mixture (e.g. VIAPAL " VUP 4779t55), typically in the presence of a radical
initiator such as AIBN or a suitable peroxy compound such as a peroxyester, preferably at a
temperature sufficiently high so as to initiate the radical curing reaction typically at a
temperature of 55-95 oC (such as at 65-90 oC, preferably at 70-85 oC), and/or preferably for
from 0.3 to 15 hours (in particular 0.7 to 8 hours), leads to formation of a crosslinked
polyester polymer. Preferably, the uncured polyester-containing resin mixture is liquid at
room temperature (e.9. at 15-30 oC).
ln an altemative optional embodiment of the crosslinked polyester polymer or co-polymer
embodiment of the invention, the unsaturated (alkene-containing) polyester resin can have
been formed at least partly from an alkene-containing di-carboxylic acid (such as fumaric
acid, alone or with a further di-carboxylic acid such as isophthalic acid) polymerised with a
saturated diol or glycol such as ethylene glycol. See for example EP 0 517 669 Al, page 3
lines 19-28, and Example 1 section b and Example 2 section b, all incorporated herein by
reference, for unsaturated polyester resins formed from fumaric acid + isophthalic acid +
glycol, thought to be available from Ashland Chemicals e.g. under the AROPOL trademark.
Preferably, in the crosslinked polyester polymer formed from the polymerization of the
unsaturated (alkene-containing) polyester resin mixed with the alkenyl-group-containing (e.9.
vinyl-group-containing) monomer, and/or in the uncured (unpolymerized) mixture of the
unsaturated (alkene-containing) polyester resin and the alkenyl-group-containing (e.9. vinylgroup-
containing) monomer, the alkenyl-group-containing (e.9. vinyl-group-containing)
monomer, such as e.g. styrene, is (or was before polymerization) present at a concentration
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of from 25o/o to 60% (e.9. from 35 to 55%, e.g. about 45o/o)by weight of the crosslinked
polyester polymer and/or by weight of the pre-polymerization resin.
When the polymer microparticles comprise a polymeric matrix or matrices comprising an
epoxy polymer or co-polymer, then preferably the polymeric matrix or matrices comprise (e.9.
are) a cured epoxy resin polymer matrix prepared from curing an epoxy resin mixed with a
hardener, optionally also mixed with a tertiary amine catalyst (e.9. an aliphatic, cycloaliphatic
and/or aromatic tertiary amine catalyst). Preferably, the epory resin is selected from di- and
poly-epoxide monomers, prepolymers and blends thereof. ln particular, in the epoxy resin, a
di- or poly-epoxide can be aliphatic, rycloaliphatic or aromatic, with typical examples
including the diglycidyl ethers of bisphenolA, glycerol or resorcinol. More preferably, the
epoxy resin comprises resorcinoldiglycidylether. Preferably, the epoxy resin is liquid at
room temperature (e.9. at 15 to 30 oC). Preferably, the hardener, e.g. for curing the epory
resin, is selected from primary and secondary amines and their adducts, cyanamide,
dicyandiamide, polycarboxylic acids, anhydrides of polycarboxylic acids (e.9. phthalic
anhydride, or a methyl-substituted derivative and/or a tetrahydro- or hexahydro- derivative of
phthalic anhydride, or nadic anhydride), polyamines (e.9. a diamine and/or a triamine, such
as polyoxypropylene diamine), polyamides, polysulfides, mercaptanes, polyamino-amides,
polyadducts of amines and polyepoxides, polyols, and mixtures thereof. ln a particular
embodiment, the hardener, e.g. for curing the epoxy resin, comprises a diamine andior
triamine such as an aliphatic, cycloaliphatic or aromatic diamine and/or triamine, in padicular
polyoxypropylene d iamine, d iaminocyclohexane, xylene diamine, phenylene d iamine,
diethylene triamine and/or polyorypropylene triamine. ln an altemative particular
embodiment, the hardener, e.g. for curing the epoxy resin, comprises an anhydride of a
polycarboxylic acid, in particular phthalic anhydride, or a methyl-substituted derivative and/or
a tetrahydro- or hexahydro- derivative of phthalic anhydride, or nadic anhydride. Preferably,
where the hardener comprises an anhydride of a polycarboxylic acid, the hardener is mixed
with a tertiary amine catalyst such as an aliphatic, cycloaliphatic and/or aromatic tertiary
amine catalyst. Typically, in order to cure the epoxy resin, a mixture comprising the epoxy
resin and the hardener, and optionally also a tertiary amine catalyst (e.9. the mixture being
dispersed in a continuous liquid (e.9. aqueous) phase or medium), is held at a temperature of
from 30 to 120 oC (e.9. from 60-95 oC or from 70-90 oC) for from 0.1 to 15 hours (e.9. from 1-
12 hours), in order to effect the curing reaction to prepare the cured epoxy resin polymer
matrix.
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Preferably, the amount of the first herbicide contained within the polymeric microparticles is
up to 50%, preferably from 1 to 50% or from 5 to 50%, by weight of the polymeric
micropadicles containing the first herbicide.
More preferably, the amount of the first herbicide contained within the polymeric
microparticles is up lo 40o/o, preferably from 1 lo 40o/o or from 5 to 40Yo or from 10 to 40%, in
particular from 15 to 40o/o, by weight of the polymeric microparticles containing the first
herbicide.
Still more preferably, the amount of the first herbicide contained within the polymeric
microparticles is up to 35%, preferably from 1 to 35% or from 5 to 35% or from 10 to 35olo, in
particular from 15 to 35%, by weight of the polymeric microparticles containing the first
herbicide.
Yet more preferably, the amount of the first herbicide contained within the polymeric
microparticles is up to 30%, preferably from 5 to 30o/o or from 10 to 30o/o, in particular from 15
to 30% or from 15 to 25o/o, by weight of the polymeric microparticles containing the first
herbicide.
Preferably, in all aspects of the present invention, the amount of the first herbicide present in
the herbicidal composition is up to 50%, or from 1 to 50% or from 5 to 50%; or more
preferably up to 40%, or from 1 lo 40o/o or from 5 to 40% or from 10 lo 4Oo/o or from 15 to
40o/oi ot still more preferably up to 35%, or from 1 to 35% or from 5 to 35% or from 10 to 35%
or from 15 to 35%; or yet more preferably up to 30%, or from 1 to 30% or from 5 to 30% or
from 10 to 30% or from 15 to 30%; of the weight of the polymeric microparticles present in
the herbicidal composition.
For the polymeric microparticles, when the polymer has been formed by radical initiation,
then preferably the polymeric microparticles contain a radical initiator and/or the reacted
residue(s) therefrom, generally present in from 0.3 to 5%, preferably from 0.5 to 4o/o ot from 1
to 3o/o, by weight of the polymeric microparticles containing the first herbicide. The radical
initiator preferably comprises an azo compound such as azo-bis-isobutyronitrile (AIBN), or a
suitable peroxy compound such as: a di(C1-Csalkyl) peroxide such as di-tert-butyl peroxide, a
peroxyacid such as benzoylperoxide, a ketone peroxide such as methyl ethyl ketone
peroxide, a peroxyketalsuch as 1,1-di(tert-amylperoxyfcyclohexane, a peroxyester such as
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tert-butyl peroxy benzoate or 2,5-dimethyl-2,5{i(2-ethylhexanoylperoxy)hexane, a
hydroperoxide such as cumene hydroperoxide, or a peroxyerrlconate such as tert-butyl
peroxy-2-ethylhexyl carbonate. Preferably, the radical initiator comprises
azo-bis-isobutyronitrile (AIBN). For example, a radical initiator is suitably used, e.g. for
forming the polymer, when the polymeric microparticles comprise a polymeric matrix or
matrices comprising a crosslinked polyester polymer formed from the polymerization of an
unsaturated (alkene-containing) polyester resin mixed with an alkenyl-group-containing (e.9.
vinyl-group-contain ing) monomer.
Optionally, the polymeric microparticles can contain a non-volatile solvent, an oil and/or a
plasticizer (in particular a plasticizer); which for example can be present in up to about 30%
(e.9. 0.1 to 30%), in particular up to about 20o/o (e.9.0.1 to about 20o/o) and more parlicularly
up to about 10% (e.g. 0.1 to about 10o/o), by weight of the polymeric microparticles containing
the first herbicide. Particularly, the non-volatile solvent, oil and/or plasticizer is a phthalate
ester such as dibutylphthalate, a polyadipate such as Edenol 1215rM (from Cognis), a
benzoate ester such as methyl benzoate, dipropylene glycol dibenzoate (e.9. Benzoflex g-88
rM, from Genovique), or diethylene glycol dibenzoate (e.g. Benzoflex24S rM, from
Genovique), a polybutene such as the lndopol H rM series e.g. lndopol HOSO (from lneos), an
aromatic hydrocarbon solvent such as Solvesso 200, or a Cr-C+alkyl fatty acid ester such as
methyloleate.
Preferably, however, the polymeric microparticles either contain no non-volatile solvent, oilor
plasticizer, or contain up to 5% (e.9. 0.1 to 5%), or more preferably up lo 2o/o (e.g. 0.1 to 2o/o)
or up to 1o/o (e.9.0.1 to 1Yo) of the non-volatile solvent, oiland/or plasticizer (in particular
plasticizer), by weight of the polymeric microparticles containing the first herbicide. As is
shown by Polymeric Microparticle Examples 2 and 3, higher percentages of non-volatile
solvent, oil and/or plasticizer (in particular plasticizer), e.g. ca. 10o/o or ca. 2OYo of plasticizer,
by weight of the polymeric microparticles containing the first herbicide, are generally best
avoided, at least when the polymeric micropadicles comprise a polymeric matrix or matrices
comprising a crosslinked polyester polymer or co-polymer.
ln all aspects of the invention, especially in the second, third, fourth and/or later aspects of
the invention, preferably, the polymeric microparticles are present in from 0.3 to 70% orfrom
1 to 60%, more preferably from 3 to 50% or from 7 lo 50o/o, still more preferably from 10 to
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45Yo, yel more preferably from 13 to 40o/o, most preferably from 18 to 35%, by weight of the
herbicidal composition (e.g. by weight of a or the dispersion or dispersion composition).
ln all aspects of the invention, especially in the second, third, fourth and/or later aspects of
the invention, preferably, the amount of the first herbicide present in the composition (or the
amount of the first herbicide contained within the polymeric microparticles) is from 0.1 to
25o/o, more preferably from 0.5 lo 20o/o or from 1 lo 20o/o, still more preferably from 0.5 to 15o/o
orfrom 1 to 15% orfrom 2to 15o/o, yet more preferably from 1 to 10% orfrom 2lo 1|o/o,by
weight of the herbicidal composition (e.g. by weight of a or the dispersion or dispersion
composition).
Typically, in a composition comprising pinoxaden (such as in the first aspect of the invention
and later methods of use referring back to this first aspect, which compositions are usually
diluted e.g. aqueous diluted compositions suitable for spraying directly onto a field), the
polymeric microparticles are present in from 0.0003 to 10% orfrom 0.001 to 5%, more
preferably from 0.005 lo 1o/o or from 0.01 to 0.5%, by weight of the herbicidal composition
(e.g. by weight of a or the diluted e.g. aqueous diluted composition suitable for spraying
directly onto a field).
Preferred, particular and/or optional embodiments of the the First Herbicide
The preferreil, particular, suitable or optionalfeatures of the first herbicide are now
described, for all aspects of the invention.
Preferably, the synthetic auxin herbicide is defined as a compound that is a herbicide and
that, either itsetf or after the removal of any procide groups present thereon, stimulates the
expression of B-glucuronidase (GUS) in transgenic Arabidopsis plantlets line AtEM101 (e.g.
as disclosed in Lindsey and Topping, Ihe Plant Ce\|,1997, vol. 9, pp. 1713-1725)in an
assay / test in which:
- seeds of AtEM101 are germinated aseptically on half-strength Murashige and Skoog
medium containing a test compound at a range of doses between 0 and 200 uM and
assayed for GUS activity at 6 days post-germination; and
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- either, for a quantitative GUS assay, protein crude extracts of the plantlets are prepared
and a fluorometric assay is used, e.g. as described by Jefferson el al. EMBO J., 1987 , vol. 6,
pp. 3901-3907;
- or, whole plantlets are transferred to 100 mM sodium phosphate buffer at pH 7.0 containing
10 mM EDTA, 0.1% Triton X-100, 1mM potassium ferricyanide, 1 mM potassium
ferrocyanide and 1 mM S-bromo4-chloro-3-indolyl B-D-glucuronic acid (Xgluc) and
incubated tor 12 hours at 37 "C; stained plantlets are then removed and cleared of
chlorophyll by soaking in70o/o (v/v) ethanol; the amount of overall blue staining is then
assessed and compared visually; and
- a synthetic auxin is defined in this assay/test as a test compound which exhibits a dose
response of GUS activity or blue staining dependent on the concentration of test compound
present during the germination and growth of the AtEM101 Arabidopsis plantlet (and for
example can be as depicted in Figure 4A of Lindsey and Topping, The Plant Cell, 1997, vol.
9, pp. 1713-1725 and in respect of napthylacetic acid); and
- a synthetic auxin is further defined in this assay/test as a compound that, when assayed /
tested under the above conditions, and at a concentration of 50 pM (50 micromolar), results
in at least about a doubling (e.9. a doubling or more) of GUS activity or of the amount of blue
staining, relative to the amount of GUS activity or blue staining obtained with like AIEM101
plantlets like-grown in the absence of the test compound.
Preferably, an acetolactate synthase (ALS) inhibitor herbicide is defined as a compound that
is a herbicide and that, either itself or after the removal of any procide groups present
thereon, inhibits, at a concentration less than 100 UM, the specific activity of acetolactate
synthase by more than 90% relative to similar controls run in the absence of the compound;
and preferably where the comparative rate measurements are made at or after a reaction
time of at least 200 minutes. Preferably, the acetolactate synthase is a non-herbicideresistant
version of ALS. Preferably, the acetolactate synthase has been prepared as
described in T. Hawkes et al., in'Herbicides and Plant Metabolism': ed. A.D. Dodge, Society
for Experimental Biology Seminar Series 38, Gambridge University Press, Unitied Kingdom,
1989, pp. 1 13-136; or more preferably has been prepared according to the Legend to Table
1 on page 119 of said publication.
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More preferably, an ALS inhibitor herbicide is defined as a compound that is a herbicide and
that, either itself or after the removal of any procide groups present thereon, inhibits
acetolactate synthase according to a assay (test) method comprising the steps of:
- providing an ALS enzyme which has been prepared as described in the Legend to Table 1
on page 119 of T. Hawkes et al., in 'Herbicides and Plant Metabolism': ed. A.D. Dodge,
Society for Experimential Biology Seminar Series 38, Cambridge University Press, Unitied
Kingdom, 1989, pp. 113-136;and
- assaying (testing) the compound at a range of doses between 0 and 200 pM, in the
presence of the ALS enzyme, according to the method described in the legend of Figure 3 on
page 124 of T. Hawkes et al. (from'Herbicides and Plant Metabolism': ed. A.D. Dodge,
Society for Experimental Biology Seminar Series 38, Cambridge University Press, Unitied
Kingdom, 1989, pp. 113-136);and
- defining the test compound as being an ALS inhibitor if it inhibits, at a concentration less
than 100 pM, the specific activity of ALS by more than 90% relative to similar controls run in
the absence of the test compound, and where the comparative rate measurements are made
at or after a reaction time of at least 200 minutes.
ln the invention, the first herbicide, when in a salt-free form or when in a non-aluminium salt
form, antagonises the herbicidal activity of pinoxaden. This can be measured using the
glasshouse assay for pinoxaden antagonism as described in Assay 3 hereinafter.
Preferably, the first herbicide, contained within polymeric microparticles, is selective on (i.e.
suitable for use on) non-oat cereal crops, such as wheat, barley, rye and/or triticale, more
preferably wheat and/or barley. This can be measured using the glasshouse assay as
described in Assay 4 hereinafter ["glasshouse assay for measuring the selectivity on, i.e.
suitability for use on, non-oat cereals (e.9. wheat and/or barley) of the first herbicide"l.
When the first herbicide is a synthetic auxin herbicide, then preferably it is dicamba, 2,4-D or
MCPA; or an agrochemically acceptable salt thereof.
Dicamba is 3,6-dichloro-2-methoxybenzoic acid. 2,4-D is (2,4-dichlorophenoxy)acetic acidl.
MCPA is (4-chloro-2-methylphenoxy)acetic acid.
When the first herbicide is an ALS inhibitor herbicide, then preferably it is:
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- a sulfonyl urea herlcicide , preferably triasutfuron, tribenuron-methyl, iodosulfuron-methyl,
mesosulfuron-methyl, sulfosulfuron, orflupyrsulfuron-methyl; or an agrochemically
acceptable salt thereof ;
- or a lriazolopyrimidine herbicide, preferably pyroxsulam or an agrochemically acceptable
salt thereof.
More preferably, when the first herbicide is an ALS inhibitor herbicide, then it is: triasuJfuron,
tribenuron-methyl, iodosulfuron-methyl, mesosulfuron-methyl, suJfosuJfuron, flupyrsulfuronmethyl,
or pyroxsulam; or an agrochemically acceptable salt thereof.
Still more preferably, when the first herbicide is an ALS inhibitor herbicide, then it is:
triasuJfuron, tribenuron-methyl, or pyroxsulam; or an agrochemically acceptable salt thereof.
Preferably, the first herbicide is: dicamba ,2,4-D, MCPA, triasutfuron, tribenuron-methyl,
iodosulfuron-methyl, mesosulfuron-methyl, suJfosulfuron, flupyrsulfuron-methyl, or
pyroxsulam; or an agrochemically acceptable salt thereof.
More preferably, the first herbicide is: dicamba,2,4-D, MCPA, triasuJfuron, tribenuron-methyl,
or pyroxsulam; or an agrochemically acceptable salt thereof.
Still more preferably, the first herbicide is: dicamba, MCPA, triasuJfuron, or pyroxsulam; or an
agrochemically acceptable salt thereof.
ln the composition, the weight ratio of dicamba or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden preferably is 80:1 to 4:3, more preferably is 16:1 to
4;3, or still more preferably is 14:3 to 5:3, or yet more irreferably is from 14:3 to 20:9.
ln the composition, the weight ratio of MCPA or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden preferably is from 450:1 to 14:3, more preferably
from 1 10:1 to 35:6, or still more preferably is from 1 10:3 to 35:6.
ln the composition, the weight ratio of 2,4-D or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden preferably is from 460:1 to 14:3, or more preferably
is from 110:1 to 35:6, or still more preferably is from 100:3 to 20:3.
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ln the composition, the weight ratio of triasulfuron or an agrochemically acceptable salt
thereof (measured as the free acid) to pinoxaden preferably is from 3:1 to 1:12, or more
preferably is from 1:1 to 1 :12, or still more preferably is from 1:3 to 1:12.
ln the composition, the weight ratio of tribenuron-methyl or an agrochemically acceptable salt
thereof (measured as the free acid) to pinoxaden preferably is from 6:1 to 1:8, or more
preferably is from 2:1 to 5:24, or still more preferably is from 1:1 to 1:4.
ln the composition, the weight ratio of iodosulfuron-methyl or an agrochemically acceptable
salt thereof (measured as the free acid) to pinoxaden preferably is from 3:1 to 1:12, or more
preferably is from 1:1 to 1:12, or still more preferably is from 1:3 to 1:6.
ln the composition, the weight ratio of mesosulfuron-methyl or an agrochemically acceptable
salt thereof (measured as the free acid) to pinoxaden preferably is from 4:1 to 1:6, or more
preferably is from 4:3 to 1:6, or still more preferably is from 1:2 to 1:4.
ln the composition, the weight ratio of sulfosuifuron or an agrochemically acceptable salt
thereof (measured as the frce acid) to pinoxaden preferably is from 7:1 to 1:6, or more
preferably is from 7:3 to 1:6, or still more preferably is from 7:6 to 1:6.
ln the composition, the weight ratio of flupyrsulfuron-methyl or an agrochemically acceptable
salt thereof (measured as the free acid) to pinoxaden preferably is from 3:1 to 1;12, or more
preferably is from 1:1 to 1:12, or still more preferably is from 1:3 to 1:6.
ln the composition, the weight ratio of pyroxsulam or an agrochemically acceptable salt
thereof (measured as the free acid) to pinoxaden preferably is from 15:4 to 3:20, or more
preferably is from 15:121o 3:20, or still more preferably is from 1:2 to 1 1:60.
ln a particular embodiment of the herbicidal composition (e.9. liquid or solid composition), at
least pad of, preferably 50% or more (more preferably 70o/o ot more, e.g. 90% or more, e.g.
95o/o ot more) by weight of, the first herbicide contained within the polymeric microparticles
(e.9. a synthetic auxin herbicide or an ALS inhibitor herbicide) is present within the polymeric
microparticles in non-crystallline form; especially for a synthetic auxin herlcicide such as
dicamba or a salt thereof.
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ln an altemative particular embodiment of the herbicidal composition (e.9. liquid or solid
composition), at least part of, preferably 50o/o or more (more preferably 70o/o ot more, e.g.
90o/o ot more, e.g. 95% or more) by weight of, the first herbicide contained within the
polymeric microparticles (e.9. a synthetic auxin herbicide, such as MCPA or 24-D or a salt
thereof, or more preferably for an ALS inhibitor herbicide, such as a sulfonyl urea herbicide)
is present as solid (e.9. milled solid) particles of the first herbicide dispersed within the
polymeric microparticles, in particular as solid particles (e.9. crystalline or amorphous solid
particles) of the first herbicide whose "mean" or "D90" particle size is less than 10
micrometres, more preferably less than 5 micrometres or less than 3 micrometres.
Preferred, particular and/or optional embodiments of the Herbicidal Composition
Preferred, particular and/or optional embodiments of the herbicidal composition, for any or all
aspects (especially the first, second, third and/or fourth aspects) of the present invention,
except where mentioned otherwise and except where inappropriate, are as follows.
Preferably, in the first aspect of the invention, the herbicidal composition is a dispersion
composition (preferably aqueous)in which the polymeric microparticles are dispersed in a
continuous (preferably aqueous) liquid phase or medium, a suspension concentrate
composition (e.9. aqueous or non-aqueous), a suspoemulsion composition (e.9. aqueous
suspoemulsion, in particular a suspoemulsion comprising an emulsified oily and/or nonaqueous
liquid phase and a dispersed/suspended solid both in a continuous [preferably
aqueousl liquid phase or medium), or a solid composition (e.9. granule or powder
composition). ln these compositions, in a particular embodiment at least part of, preferably
50% of more (more preferably 70Yo or more, e.g. 90% or more, e.g. 95% or more) by weight
of, the first herbicide contained within the polymeric microparticles is present within the
polymeric microparticles in non-crystalline form.
ln all aspects (especially the first, second, third and/or fourth aspects) of the present
invention, in one particularly preferred embodiment, the herbicidal composition (and/or the
first herbicidal composition e.g. as described in the seventh (tank-mixing) aspect of the
invention hereinafter) is a dispersion composition (preferably aqueous) in which the
polymeric microparticles are dispersed in a continuous (preferably aqueous) liquid phase or
medium. ln these compositions, in a particular embodiment at least part of, preferably 50%
of more (more preferably 70o/o or more, e.g. 90% or more, e.g. 95o/o or more) by weight of,
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the first herbicide contained within the polymeric microparticles is present within the
polymeric microparticles in non-crystalline form.
ln all aspects of the present invention, "dispersion composition" means any composition in
which the polymeric microparticles are dispersed in a continuous liquid phase or medium The
continuous liquid phase or medium can be aqueous (preferably water, but altematively a
mixture of water and a water-miscible organic solvent), or can be non-aqueous e.g.
comprising one or more organic solvents. Therefore, in all aspects of the present invention,
the term "dispersion composition" encompasses, for example, a type of suspoemulsion in
which an oily and/or non-aqueous liquid phase is emulsified in, and a dispersed/suspended
solid comprising the polymeric microparticles is dispersed in, the continuous (preferably
aqueous) liquid phase or medium.
ln the dispersion composition embodiments of the present invention, preferably, the
dispersion of the polymeric microparticles in the continuous (preferably aqueous) liquid
phase or medium is stabilised by a stabilizer and/or a dispersant and/or a surfactant.
ln the dispersion composition embodiments or aspects of the invention, the stabilizer and/or
the dispersant and/or the surfactant (e.9. nonionic surfactant) is preferably present in from
0.2to 30%, or more preferably is present in from 0.3 to 20o/o or from 1 to 15o/o orfrom 1 to
10% (most preferably (especially for polyvinyl alcohol) from 3 to 6 %) by weight of the
dispersion (d ispersion composition).
More preferably, the stabilizer and/or dispersant and/or surfactant comprises:
- a polymeric barrier dispersant or surfactant (preferably nonionic) such as polyvinyl alcohol;
and/or
- a dispersant comprising an alkali metal (e.9. sodium) or alkaline earth metal (e.9. calcium)
lignosulfonate (e.9. which generally acts as a dispersant with also some emulsifying activity),
an alkali metal (e.9. sodium) or alkaline earth metal (e.9. calcium) naphthalenesulfonate (e.9.
which generally acts as a dispersant with also some emulsifying activity), a
naphthalenesuJfonate-formaldehyde copolymer, poly(methylvinylether/maleic acid), andior a
polyethyleneoxide/polypropyleneoxide (EO-PO) block copolymer (e.g. Pluronic rM, from
BASF);and/or
- a surfactant (e.9. non-ionic, anionic and/or cationic surfactant; e.g. as disclosed
hereinafter).
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The above listed stabilizers and/or dispersants generally give "regular" dispersions of the
polymeric microparticles.
ln the first, second, fourth, and/or later aspects of the invention, a polymeric barrier
dispersant or surfactant (particularly nonionic, more preferably polyvinyl alcohol) is the
preferred stabilizer and/or d ispersant.
ln the first, second, fourth, and/or later aspects of the invention, preferably, the composition
comprises a nonionic surfactant (preferably a nonionic polymeric barrier sudactant, more
preferably polyvinyl alcohol).
Typical nonionic surfactants, e.g. for use in the present invention, include polyglycol ether
derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of
alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and
approximately B to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical
or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
Also typical are water-soluble polyethylene oxide adducts with polypropylene glycol,
ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately
10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene
glycol ether groups and approximately 10 to approximately 100 propylene glycol ether
groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene
glycol units per propylene glycol unit. Examples which may be mentioned are
nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene
glycol/polyethylene oxide adducts, tributylphenorypolyethoxyethanol, polyethylene glycolor
octylphenorypolyethoxyethanol. Also typical are fatty acid esters of polyoxyethylene sorlcitan,
such as polyoxyethylene sorbitan trioleate.
When the herbicidal composition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium, then preferably a or the
nonionic surfactant (preferably a nonionic polymeric barrier sudactant, more preferably
polyvinyl alcohol) is present in the continuous liquid phase or medium, such that the nonionic
surfactant stabilizes the dispersion of the polymeric microparticles in the continuous liquid
phase or medium (e.9. as in the second or fourth aspects of the invention - but also
preferred for other aspects eg the first aspect of the invention).
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ln all aspects (e.9. the first, second, fourth and/or later aspects) of the present invention,
especially for a dispersion composition, preferably, the weight ratio of the polymeric
microparticles to a or the nonionic sudactant (preferably a nonionic polymeric barrier
surfactant, more preferably polyvinyl alcohol) in the herbicidal composition is from 40 : 1 to 1
: 2. This feature is always mentioned in the second aspect of the invention.
ln all aspects (especially the second aspect) of the present invention, especially for a
dispersion composition, more preferably, the weight ratio of the polymeric microparticles to a
or the nonionic surfactant (preferably a nonionic polymeric barrier surfactant, more preferably
polyvinylalcohol)intheherbicidalcomposition isfrom20:1to 1 :1.5orfrom20:1to 1 :1
orfrom 20:1to1.25:1, still more preferablyfrom 15:1 to 1.25:l orfrom 15:1 to 2.0:1,
even more preferablyfrom 10 :11o2.0:1 orfrom 10:1 to 2.5:1, yet more preferablyfrom
7.5:1to2.O:1 orfrom 7.5:1to2.5: 1 orfrom 7.5:1to3.0:l,furthermore preferably
from 6.8:11o2.5:1 orfrom 6.8:1 to 3.0:1 orfrom 6.3:1 to3.0:1, mostpreferablyfrom
6.0: 1 to 4.0: 1 from 6.0: 1 to 3.5: 1 ororfrom 5.0: 1 to4.0: 1.
ln all aspects of the present invention, especially for a dispersion composition and/or
especially where a nonionic surfactant is present, then preferably, either the composition
comprises no ionic surfactant, or the composition comprises an ionic surfactant and the
weight ratio of the polymeric microparticles to the ionic surfactant in the herbicidal
composition is 200 : 1 or more (e.9. from 200 : 1 to 50000 : 1). This feature is always
mentioned in the second aspect of the invention.
ln all aspects (especially the second aspect) of the present invention, especially for a
dispersion composition, more preferably, either the composition comprises no ionic
surfactant, or the composition comprises an ionic surfactant and the weight ratio of the
polymeric microparticles to the ionic surfactant in the herbicidal composition is 300 : 1 or
more (e.9. from 300 : 1 to 50000 : 1), still more preferably no ionic surfactant or the weight
ratio is 330 : 1 or more (e.9. from 330 : 1 to 50000 : 1), even more preferably no ionic
surfactant or the weight ratio is 500 : 1 or more (e.9. from 500 : 1 to 50000 : 1), yet more
preferably no ionic surfactant or the weight ratio is 670 : 1 or more (e.9. from 670 : 1 to 50000
: 1), further more preferably no ionic surfactant or the weight ratio is 1200 :1 or more (e.9.
from 1200 : 1 to 50000 : 1). Most preferably, the composition comprises essentially no (or
no) ionic sudactant.
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ln an altemative particular embodiment (e.9. an embodiment of the first aspect of the
invention), especially in a dispersion composition, the stabilizer or dispersant comprises a
colloidal and/or nanoparticulate solid which is capable of staying at the interface between a
continuous and dispersed phase, such as silicon dioxide or clay (e.9. to give "Pickering"
dispersions of the polymeric microparticles).
When the stabilizer or dispersant comprises a colloidal and/or nanoparticulate clay solid, the
clay typically comprises (i) a kaolin group clay such as kaolinite, dicksite, halloysite, nacrite
or serpentine (typically kaolinite), (ii) a smectite group clay such as montmorillonite,
nontronite or saponite (typically montmorillonite), (iii) an illite group clay such as illite, and/or
(iv) attapulgite or sepiolite. Preferably, the clay comprises (e.9. is) a kaolin group clay
(typically kaolinite) or montmorillonite. For example, the clay can be bentonite, which is an
impure clay comprising montmorillonite, a particular example of bentonite being a mixture of
montmorillonite and kaolinite. More preferably, however, the clay comprises (e.9. is) a kaolin
group clay, typically kaolinite. ln one particular embodiment, in a composition according to
any aspect of the invention, the composition comprises a clay stabilizer or dispersant
comprising (e.9. being) a kaolin group clay, such as kaolinite, and a xanthan gum capable of
contacting the kaolin group clay.
More preferably, the clay stabilizer or dispersant is a surface-modified clay (e.9. smectite
group or preferably kaolin group clay). The presence of a surface-modified clay is mentioned
in the third aspect of the invention.
Even more preferably, e.g. in the first and/or third aspects of the invention, the clay stabilizer
or dispersant (or the surface-modified clay) is a clay (in particular, an aminated clay, such as
an aminated smectite group or preferably kaolin group clay) which has been surfacemodified
such that the surface-modified clay (i) is capable of being at least partially wetted by
an aqueous liquid phase, (ii) is capable of being at least partially wetted by a non-aqueous oil
liquid phase, and (iii) is capable of stablizing an oil-and-water-containing emulsion (e.9.
Pickering emulsion) through adsorption at a or the oil/water interface.
Still more preferably, e.g. in the first and/or third aspects of the invention, the clay stabilizer
or dispersant (or the surface-modified clay) is an amino-silane-modified clay (e.9. an aminosilane-
modified smectite group or preferably kaolin group clay). The amino-silane-modified
clay is preferably prepared by reacting or adsorbing the silane group of an amino-silane
wo 2013/034513 PCTtEP20t2t067072
surface-modifying agent with or to the surface of the clay so as to form free amine groups
attached to the clay surface. Preferably, in the amino-silane-modified clay, the free amine
groups are attached via a Cz-oalkylene linker, such as a propylene or ethylene linker, to the
clay surface (see e.g. page 8 line 26 to page 9 line 17 of WO2009/063257 , incorporated
herein by reference). Preferably, the amino-silane surface-modifying agent is an (amino-C2-
5alkylenelsubstituted silane wherein the amino-C26alkylene substituent is bonded to the
silicon atom though a carbon atom; more preferably the surface-modifying agent is
aminopropyltriethoxysilane; e.g. see pages 8-9 and Example 1 of WO20091063257
incorporated herein by reference. Most preferably, the amino-silane-modified clay is lmerys
rM RLO 7645, which is generally described in Example 1 of patent application
WO2009/063257 (incorporated herein by reference), and which is available from lmerys
Group, USA (www.imerys.com). More specifically, lmerys rM RLO 7645 is a tabutar ultrafine
kaolin clay that has been surface-modified by the addition of 1.60/o by weight of
aminopropyltriethoxysilane. ln lmerys rM RLO 7645, the kaolin clay is tabular (ie "blocky", flat
or plate-like in shape), and the surface-modified (amino-silane modified) kaolin clay is
ultrafine, typically having a particle size distribution in which: at least 98% of the particles are
smaller than 1 micron (micrometre),82o/o of the particles are smaller than 0.25 microns
(micrometres), and the D50 (median diameter) is 0.12 microns (micrometres). As an
example only, it is thought that a surface-modified (amino-silane-modified) kaolin clay should
be capable of being prepared by mixing the clay with a solution of an amino-silane surfacemodifying
agent (e.9. aminopropyltriethoxysilane) in a solvent (e.9. aqueous and/or organic
solvent), typically in a suitable mixer such as food blender.
The clay, in particular the sudace-modified clay, typically has a particle size defined by a
median diameter (e.g. by number) of from 0.01 to 2 microns, in particular from 0.05 to 0.5
microns (micrometres), e.g.as measured by scanning electron microscopy. The clay's
particle size is small.
ln dispersion compositions, especially in the third aspect of the invention, preferably, the clay
(especially surface-modified clay) is present in from 0.21o 2Oo/o, morc preferably from 0.5 to
12o/o, stil more preferably from 1 to 7o/o, yet more preferably from 1 .25 lo 5o/o, by weight of the
dispersion composition.
ln all aspect of the invention, especially in the third aspect of the invention (relating to
surface-modified clay), preferably, the weight ratio of the polymeric microparticles to the clay
(in particular surface-modified clay) in the herbicidal composition is from 100 : 1 to 2: 1 or
-39
from
to4:
to6:
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100 : 1 to 3 : 1, more preferablyfrom40 : 1 lo2: 1 orfrom 40 : 1 to 3 : 1 orfrom 40 : 1
l,yetmorepreferablyfrom20:1to4:1orfrom20:1to5:l,inparticularfrom15:1
1.
ln the third aspect of the invention (relating to surface-modified clay), typically, the mean
diameter by volume of the polymeric micropadicles containing the first herbicide is from 1.0
to 50 micrometres, in particularfrom 5 to 40 micrometres such as from from 10 to 35
micrometres, as measured by light scattering laser dffiraction (e.9. by Malvern Mastersizer
rM;. This type of particle size measurement probably includes in the measured diameter a
small or very small contribution attributable to any attached or adsorbed surface-modified
clay, as well as the greater part of the measured diameter attributrable to the polymeric
microparticle (PMP) itself. However, it is clearly seen from PMP Examples 12 and 13 and
Figures 6 and 7 herein that that PMPs according to the third aspect of the invention,
stabilized by surface-modified clay, tend to have a larger particle size than PMPs according
to the second aspect of the invention stabilized by polyvinyl alcohol (for polyvinyl alcohol
stabilized PMPs, see e.g. Figures 1,2,4,5 and 14).
ln a particularly preferred embodiment of the first aspect of the present invention, the
herbicidal composition of the first aspect of the invention comprises a mixture of (e.9. a
herbicidally effective amount of a mixture of):
a) polymeric microparticles containing a synthetic auxin herbicide being dicamba, 2,4-D or
MCPA, or an agrochemically acceptable salt thereof; and
b) pinoxaden.
The synthetic auxin and ALS inhibitor herbicides mentioned above are generally known
products and commercially available. The ACCase inhibitor herbicide pinoxaden can be used
in the composition according to this invention in any available or preparable form.
Preferably in the herbicidal composition according to the invention, (a) are polymeric
microparticles contiaining dicamba ,2,4-D or MCPA, or an agrochemically acceptable salt
thereof. More preferably, (a) are polymeric microparticles containing dicamba or MCPA, or
an agrochemically acceptable salt thereof.
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Most preferably, (a) are polymeric microparticles containing dicamba or an agrochemically
acceptable salt thereof .
ln the present invention, (b) is pinoxaden.
Preferably, the herbicidal composition according to the invention additionally contain
optionally (c) a safener and, optionally, (d) an additional herbicide and, optionally, (e) an oil
additive.
Preferably, a safener (c) is present and comprises cloquintocet-mexyl, cloquintocet acid or
an agrochemically acceptable salt thereof, fenchlorazole, or mefenpyr-diethyl. Preferably, in
the composition, the weight ratio of the pinoxaden to the safener is 20:1 to 1:1, e.g. 20:1 to
2:1, e.9.10:1 to 2:1, e.g. 4:1. Preferably, the safener is cloquintocet-mexyl or mefenpyrd
iethyl, more preferably cloqu i ntocet-mexyl.
Preferred additionalherbicides (d) are sulfonyl urea herbicides selected from triasulfuron,
tri ben u ron-methyl, iod osu lfu ron-methyl, mesosu lfuron-methyl, su lfosu Jf u ron an d
flupyrsulfuron-methyl, or triazolopyrimidine herlcicides selected from pyroxsulam and
penoxsulam, or sulphonylamino-carbonyl-triazolinone herbicides selected from flucarbazonesodium,
propoxycarbazone-sodium and thiencarbazone.
ln one particular embodiment, (e) is present and is an oil additive selected from an oil of
vegetable or animal origin, a mineral oil, alkyl esters of such oils, mixtures of such oils and oil
derivatives, tris-esters of phosphoric acid with aliphatic or aromatic alcohols and bis-esters of
alkyl phosphonic acids with aliphatic or aromatic alcohols.
Methods of Use
A fifth aspect of the present invention provides a method of reducing the antagonistic effect
on the control of weeds (preferably monocotyledonous weeds e.g. grassy weeds) in cereals
(preferably non-oat cereals, such as wheat, barley, rye and/or triticale, more preferably wheat
and/or barley) which is shown by an herbicidal mixture of either a synthetic auxin herbicide
with pinoxaden or an ALS inhibitor herbicide with pinoxaden, which comprises: applying a
herbicidal composition according to the first aspect of the present invention, or applying a
herbicidal composition according to the second, third and/or fourth aspects of the present
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invention mixed (e.9. in water) with pinoxaden or a herbicidal composition (e.g. EC
composition) comprising pinoxaden, to the plants (i.e. to the weeds and/or to the cereal
crops) or to the locus thereof.
A sixth aspect of the present invention provides a method of controlling weeds (preferably
monocotyledonous weeds e.g. grassy weeds) in cereal crops (preferably non-oat cereal
crops, such as wheat, barley, rye and/or triticale, more preferably wheat and/or barley)
comprising: applying a herbicidalcomposition according to a first aspect of the present
invention, or applying a herbicidal composition according to the second, third and/or fourth
aspects of the present invention mixed (e.9. in water) with pinoxaden or a herbicidal
composition (e.9. EC composition) comprising pinoxaden, to the plants (i.e. to the weeds
and/or to the cereal crops) or to the locus thereof.
A seventh aspect of the present invention provides a method of controlling weeds
(preferably monocotyledonous weeds e.g. grassy weeds) in cereal crops (preferably non-oat
cerealcrops, such as wheat, barley, rye and/or triticale, more preferably wheat and/or
barley), comprising the steps of:
(i) mixing in a tank a first herbicidal composition and a second herbicidal composition, and
optionally a solvent suitable for applying the first and second compositions to plants or to a
locus thereof (preferably an aqueous solvent such as water), and optionally a tank-mix
adjuvant (e.9. comprising methylated rapeseed oil), to provide a tank-mixed herbicidal
composition;
wherein the first herbicidal composition (which can for example be a dispersion (e.g. a
dispersion and/or suspension concentrate), or a granule or powder composition) comprises
polymeric microparticles containing a first herbicide, wherein the first herbicide is a synthetic
auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden; and
wherein the second herbicidal composition (preferably a liquid composition, e.g. an
emulsifiable concentrate composition) comprises pinoxaden; and
(ii) applying the tank-mixed herbicidal composition to the plants (i.e. to the weeds and/or to
the cereal crops) or to the locus thereof.
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ln the seventh aspect of the invention, the polymeric microparticles andlor the first herbicide
and/or the pinoxaden can be as defined herein in any of the first, second, third and/or fourth
aspects of the invention in their broadest aspects or in any preferred embodiment(s) thereof.
ln the seventh aspect of the invention, the first herbicidal composition is preferably as defined
in any of the second, third and/or fourth aspects of the invention in their broadest aspects or
in any preferred embodiment(s) thereof.
ln the seventh aspect of the invention, the tank-mixed herbicidal composition can for
example be as defined for the herbicidal composition of the first aspect of the present
invention in their broadest aspects or in any prefened embodiment(s) thereof.
Preferred aspects of the fifth, sixth and/or seventh aspects of the invention are as follows.
Preferably, for pinoxaden (e.9. on cereal crops, preferably non-oat cereal crops, such as
wheat, barley, rye and/or triticale, more preferably wheat and/or barley, e.g. spring or winter
wheat or spring or winter barley), an application rate of from 5 to 60 g pinoxaden / ha is used,
more preferably from 15 to 60 g or from 15 to 45 g or from 30 to 60 g or from 30 to 45 g
pinoxaden / ha, still more preferably 30, 40,45 or 60 g pinoxaden / ha, most preferably 30,
40 or 45 g pinoxaden / ha.
Preferably, for polymeric microparticles containing dicamba or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cerealcrops, e.g. wheat, barley and/or
rye, e.g. spring or winter wheat, spring barley or spring rye), an application rate of from 80 to
400 g or from 100 to 400 g of dicamba i ha, measured as the free acid, is used. More
preferably, from 80 to 240 g or from 100 to 240 g or from 120 to 240 g of dicamba / ha,
measured as the free acid (such as for example from 100 to 140 g such as 120 g, or 150 g,
or 240 g, of dicamba I ha, measured as the free acid) is used.
Preferably, for a mixture of (a) polymeric microparticles containing dicamba or an
agrochemically acceptable salt thereof and (b) pinoxaden (e.9. on cereal crops, preferably
non-oat cereal crops, such as wheat, barley, rye and/or triticale, more preferably wheat
and/or barley, e.g. spring or winter wheat or spring or winter barley), an application rate of
from 80 to 400 g or from '100 to 400 g of dicamba / ha, measured as the free acid, and from 5
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to 60 g or from 10 to 60 g pinoxaden / ha, is used. More preferably, from 80 to 240 g or from
100 to 240 g or from 120 to 240 g of dicamba / ha, measured as the free acid (still more
preferably from 100 to 140 g, in particular 120 g, or 240 g, of dicamba I ha, measured as the
free acid), and from 10 to 60 g or from 15 to 60 g or more preferably from 30 to 60 g or from
30 to 45 g pinoxaden / ha, is used.
Specifically preferred examples of application rates, for a mixture of (a) polymeric
microparticles containing dicamba or an agrochemically acceptable salt thereof and (b)
pinoxaden (e.9. on cereal crops, preferably non-oat cereal crops, such as wheat, barley, rye
and/or triticale, more preferably wheat and/or barley, e.g. spring or winter wheat or spring or
winter barley), are:
- from 100 to 140 g, in particular 120 g, of dicamba / ha, measured as the free acid, and from
30 to 60 g (e.9. 30, 40, 45 or 60 g) or from 30 to 45 g (e.9. 30 or 45 g) pinoxaden / ha; or
- 240 g of dicamba / ha, measured as the free acid, and from 10 to 60 g (e.9. 10, 20, 30, 40,
45 or 60 g) or from 30 to 60 g (e.9. 30, 40, 45 or 60 g) or from 30 to 45 g (e.9. 30, 40 or 45 g)
pinoxaden / ha.
Preferably, for polymeric microparticles containing MCPA or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat and/or barley),
an application rate of from 280 to 2250 g of MCPA / ha, measured as the free acid, is used.
More preferably, from 350 to 1650 g of MCPA / ha, measured as the free acid, is used. Still
more preferably, from 350 to 1100 g of MCPA / ha, measured as the free acid (e.9. from 400
to 900 g, such as 500 g, of MCPA / ha, measured as the free acid) is used.
Preferably, for polymeric microparticles containing 2,4-D or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat and/or barley),
an application rate of from 280 to 2300 g of 2,4-D / ha, measured as the free acid, is used.
More preferably, from 350 to 1650 g of 2,4-D / ha, measured as the free acid (e.9. from 400
to 1000 g of 2,4-D / ha, measured as the free acid) is used.
Preferably, for polymeric microparticles containing triasulfuron or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, such as wheat,
barley and/or triticale), an application rate of from 5 to 15 g (more preferably from 5 to 10 g)
of triasulfuron / ha, measured as the free compound, is used.
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Preferably, for polymeric microparticles containing tribenuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cerealcrops, preferably nonoat cereal crops, such as wheat,
barley, rye and/or triticale), an application rate of from 7.5 to 30 g (more preferably trom 12.5
to 30 g or from 15 to 30 g (e.9. 15,20 or 30 g), still more preferably from 20 to 30 g) of
tribenuron-methyl / ha, measured as the free compound, is used.
Preferably, for polymeric microparticles containing iodosulfuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat,
barley, triticale and/or rye, such as winter, spring or durum wheat, triticale, rye or spring
barley), an application rate of from 5 to 15 g (more preferably 10 g) of iodosuJfuron-methyl/
ha, measured as the free compound, is used. Preferably, polymeric microparticles
containing iodosutfuron-methyl or an agrochemically acceptable salt thereof are used in
admixture with a safener such as mefenpyr-diethyl or cloquintocet-mexyl.
Preferably, for polymeric microparticles containing mesosulfuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat,
triticale and/or rye, such as winter, spring or durum wheat, triticale or rye), an application rate
of from 10 to 20 g (more preferably 15 g) of mesosulfuron-methyl / ha, measured as the free
compound, is used.
Preferably, for polymeric microparticles containing sutfosulfuron or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat), an
application rate of from 10 to 35 g of sulfosulfuron / ha, measured as the free compound, is
used.
Preferably, for polymeric microparticles containing flupyrsulfuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat), an
application rate of from 5 to 15 g (more preferably 10 g) of flupyrsulfuron-methyl/ ha,
measured as the free compound, is used.
Preferably, for polymeric microparticles containing pyroxsulam or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat, rye
andlor triticale, such as spring or winter wheat, winter rye or winter triticale), an application
rate of from 9 to 18.75 g (e.9. from 1 1 to 15 g) of pyroxsulam / ha, measured as the free
compound, is used. Preferably, polymeric microparticles containing pyroxsulam or an
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agrochemically acceptable salt thereof are used in admixture with a safener, more preferably
cloquintocet-mexyl or cloquintocet acid or an agrochemically acceptable salt thereof.
Compositions - miscellaneous
The herbicidal compositions of the present invention can be prepared in a variety of ways
using formulation additives, such as carriers, solvents and surface-active substances. The
resulting formulations can be in various physical forms, for example in the form of
suspension concentrates, dusting powders, gels, wettable powders, water-dispersible
granules, water-dispersible tablets, efferves@nt compressed tablets, emulsifiable
concentrates, microemulsifiable concentrates, oil-in-water emulsions, oilflowables, aqueous
dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules,
soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as
canier), impregnated polymer films or in other forms known, for example, from the Manual on
Development and Use of FAO Specifications for Plant Protection Products, Sth Edition, 1999.
Such formulations can either be used directly or are diluted prior to use. Diluted formulations
can be prepared, for example, with water, liquid fertilisers, micronutrients, biological
organisms, oil or solvents.
The formulations (compositions) can be prepared, for example, by mixing the active
ingredient with formulation additives in order to obtain compositions in the form of finely
divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also
be formulated with other additives, for example finely divided solids, mineral oils, vegetable
oils, modified vegetable oils, organic solvents, water, surface-active substances or
combinations thereof.
The formulation additives suitable for the preparation of the composition according to the
invention are generally known perse.
As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils,
acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone,
amyl acetate, 2-butanone, butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol,
alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, pdiethylbenzene,
diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether,
diethylene glycolethyl ether, diethylene glycol methyl ether, N,N-dimethytformamide,
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dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether,
dipropylene glycoldibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl hexanol,
ethylene carbonate, 1,1,1-trichloroethane,2-heptanone, alpha-pinene, d-limonene, ethyl
lactate, ethylene glycol, ethylene glycol butylether, ethylene glycol methyl ether, gammabutyrolactone,
glycerol, glycerol acetate, glyceroldiacetate, glyceroltriacetate, hexadecane,
hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone,
isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide,
methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl
octanoate, methyloleate, methylene chloride, m-xylene, n-hexane, n-octylamine,
octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene
glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol,
propylene glycol methylether, p-xylene, toluene, triethyl phosphate, triethylene glycol,
rylenesutfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethylacetate,
amyl acetate, butylacetate, propylene glycolmethyl ether, diethylene glycol methylether,
methanol, ethanol, isopropanol, or higher molecular weight alcohols, such as amyl alcohol,
tetrahydrofurfurylalcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, Nmethyl-
2-pyrrolidone, or the like. Water is generally the carrier of choice for the dilution of the
concentrates, e.g. suspension concentrates and dispersions.
Suitrable solid caniers are, for example, talc, kaolin, titanium dioxide, pyrophyllite clay, silica,
attiapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium
montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground
walnut shells, lignin, or similar materials, as described, for example, in CFR 180.1001. (c) &
(d).
ln general, surface-active compounds are, depending on the type of the active ingredient to
be formulated, non-ionic, cationic andlor anionic surfactants or surfactant mixtures which
have good emulsifying, dispersing and/or wetting properties. However, as mentioned
previously herein, nonionic surfactants are preferred; separately, ionic (anionic and/or
cationic) surfactants are not preferred and are best avoided in the present invention. The
surfactants mentioned below are only to be considered as examples; a large number of
further surfactants which are conventionally used in the art of formulation and suitable
according to the invention are described in the relevant literature.
Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or
cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may
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contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to
approximately 20 €rbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6
to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are
water-soluble polyethylene oxide adducts with polypropylene glycol,
ethylenediaminopolypropylene glycolor alkyl polypropylene glycol having 1 to approximately
10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene
glycolether groups and approximately 10 to approximately 100 propylene glycol ether
groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene
glycol units per propylene glycol unit. Examples which may be mentioned are
nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene
glycol/polyethylene oxide adducts, tributylphenorypolyethoxyethanol, polyethylene glycolor
octylphenorypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene
sorbitan, such as polyoryethylene sorbitan trioleate.
Cationic surfactants can include, for example, quaternary ammonium salts which generally
have at least one alkyl radical of approximately 8 to approximately 22 C atoms as
substituents and as further substituents (unhalogenated or halogenated) lower alkyl or
hydroryalkyl or benzyl radicals. The salts can for example be in the form of halides,
methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and
benzylbis(2-chloroethyl)ethyl-ammoniu m bromide.
Examples of anionic surfactants are water-soluble soaps or water-soluble synthetic surfaceactive
compounds. Examples of soaps are the alkali, alkaline earth or (unsubstituted or
substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C
atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid
mixtures which are obtainable for example from coconut or tall oil; mention must also be
made of the fatty acid methyl taurates. However, synthetic surfactants are optionally used, in
particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl
sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline
earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl
radical of approximately 8 to approximalely 22 C atoms, alkyl also to be understood as
including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium
or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate
mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric
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esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated
benzimidazole derivatives in particular contain 2 sulfonyl groups and a fatty acid radical of
approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the
sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of
dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of
a p-nonylphenol/(4-'14)ethylene oxide adduct, or phospholipids. Further suitable phosphates
are tris-esters of phosphoric acid with aliphatic or aromatic alcohols and/or bis-esters of alkyl
phosphonic acids with aliphatic or aromatic alcohols, which are a high performance oil-type
additive. These tris-esters have been described, for example, in WOO1/47356, WO00/56146,
EP-A-0579052 or EP-A-1018299 or are commercially available under their chemical name.
Preferred tris-esters of phosphoric acid for use in the new compositions are tris-(2-ethylhexyl)
phosphate, tris-n-octyl phosphate and tris-butoxyethyl phosphate, where tris-(2-ethylhexyl)
phosphate is most preferred. Suitable bis-ester of alkyl phosphonic acids are bis-(2-
ethylhexyl|(2-ethylhexyllphosphonate, bis-(2-ethylheryl}'(n-octyl)",phosphonate, dibutyl-butyl
phosphonate and bis(2-ethylhexylltripropylene-phosphonate, where bis-(2-ethylheryl)-(noctyl
)i'phosph onate is pa rticu la rly preferred.
The compositions according to the invention can preferably additionally include an additive
comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or
mixtures of such oils and oil derivatives. The amount of oil additive used in the composition
according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For
example, the oil additive can be added to the spray tank in the desired concentration after
the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of
vegetable origin, for example rapeseed oil such as MERO@, olive oil or sunflower oil,
emulsified vegetable oil, such as AMIGO@ (Rhone-Poulenc Canada lnc.), alkyl esters of oils
of vegetable origin, for example methyl esters such as methylated rapeseed oil (which is
contained in ADIGOR@, which is an emulsifiable concentrate containing 47o/o by weight of
the formulation of methylated rapeseed oil as an adjuvant, available from Syngenta), or an oil
of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as
active components essentially 80 o/o by weight alkyl esters of fish oils and 15 o/o by weight
methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
Especially preferred oil additives comprise alkyl esters of Ca-Czzfatty acids, especially the
methyl derivatives of Crz-Crs fatty acids, for example the methyl esters of lauric acid, palmitic
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acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-111-
82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112$2-9). A preferred fatty
acid methyl ester derivative is Emery@ 2230 and 2231 (Cognis GmbH). Those and other oil
derivatives are also known from the Compendium of Herbicide Adjuvants, Sth Edition,
Southern lllinois University, 2000. Also, alkoxylated fatty acids can be used as additives in
the inventive compositions as wellas polymethylsiloxane based additives, which have been
described in WO2008 lO37 37 3.
The application and action of the oil additives can be further improved by combining them
with surface-active substiances, such as non-ionic, anionic or cationic surfactants. Examples
of such anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of
WO 97134485. Examples of surface-active substances are anionic surfactants of the
dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic
surfactants of the fatty alcohol ethoxylate type. Further examples are ethorylated Ce-Cn
fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially
available surfactants are the Genapol types (Clariant AG). Further examples are silicone
surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are
commercially available e.g. as Silwet L-77@, and also perfluorinated surfactants. The
concentration of surface-active substances in relation to the total additive is generally from 1
to 30 % by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or
derivatives thereof with surfactants are Edenor ME SU@, Turbocharge@ (Syngenta AG) and
Actipron@ (BP Oil UK Limited).
The said surface-active substances may also be used in the formulations alone, that is to say
without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can
contribute to a further enhancement of action. Suitable solvents are, for example, Solvesso@
(ESSO) and Aromatic Solvent@ (Exxon Corporation). The concentration of such solvents
can be from 10 to 80 % by weight of the totalweight. Such oil additives, which may be in
admixture with solvents, are described, for example, in US-A-4 834 908. A commercially
available oil additive disclosed therein is known by the name MERGE@ (BASF Corporation).
A further oil additive that is preferred according to the invention is SCORE@ (Syngenta Crop
Protection Canada.)
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ln addition to the oil additives listed above, in order to enhance the activity of the composition
according to the invention it is also possible for formulations of alkylpyrrolidones, (e.9.
Agrimax@) to be added to the spray mixture. Formulations of synthetic latices, such as, for
example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.9. Bond@, Courier@
or Emerald@) can also be used. Solutions that contain propionic acid, for example Eurogkem
Pen-e{rate@, can also be mixed into the spray mixture as activity-enhancing agents.
Further additives which can usually be used in pesticidalformulations include crystallisation
inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming
agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pHmodifying
substances and buffers, corrosion-inhibitors, fragrances, wetting agents,
absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants,
thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.
The herbicidal formulations (compositions), especially according to the first aspect of the
invention, generally contain from 0.001 to g9% or 0.01 to 99% or 0.1 to 99 % by weight,
especially from 0.1 to 95 % (e.9. from 1 to g5 o/o, a.g. from 1 to 50 %), in particular from 0.001
to 30% orfncm 0.01 to 30% such as from 0.02 to 20o/o andlor from 0.01 to 107o, by weight, of
herbicide (a) and (b), and from 1 to 99.9 o/o (e.9. 10 to 99.9 % or 50 to 99.9 % or 50 to 99 %)
by weight of one or more formulation additives, which preferably includes from 0 to 25 o/o
(e.9. from 0.05 to 25o/o, e.e. from 1 to25oh) by weight of a suface-active substance.
Whereas commercial products willgenerally be formulated as a concentrate (e.9. suspension
concentrate or dispersion concentrate) or as a solid composition, the end user will normally
employ dilute formulations.
The formulations may also comprise additional active substances, for example plant growth
regulators, fungicides or insecticides, and in particular further herbicides or herbicide
safeners.
The rate of application of the herbicides (first herbicide (a) in admixture with pinoxaden (b))
may vary within wide limits and depends upon the nature of the soil, the method of
application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage
application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic
conditions, and other factors governed by the method of application, the time of application
and the target crop. The mixture according to the invention (first herbicide (a) together with
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pinoxaden (b)) for example can be applied at a rate of 1 to 4000 g/ha, especially from 5 to
1000 g/ha.
Preferably, for pinoxaden (e.9. on cereal crops, preferably non-oat cereal crops, such as
wheat, barley, rye and/or triticale, more preferably wheat and/or barley, e.g. spring or winter
wheat or spring or winter barley), an application rate of from 5 to 60 g pinoxaden / ha is used,
more preferably from 15 to 60 g or from 15 to 45 g or from 30 to 60 g or from 30 to 45 g
pinoxaden / ha, still more preferably 30, 40,45 or 60 g pinoxaden / ha, most preferably 30,
40 or 45 g pinoxaden / ha.
Preferably, for polymeric microparticles containing dicamba or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat, barley and/or
rye, e.g. spring or winter wheat, spring barley or spring rye), an application rate of from 80 to
400 g or from 100 to 400 g of dicamba / ha, measured as the free acid, is used. More
preferably, from 80 to240 g orfrom 100 to 240 g orfrom 120 to 240 g of dicamba / ha,
measured as the free acid (still more preferably from 100 to 140 g, such as 120 g, or 240 g,
of dicamba / ha, measured as the free acid) is used.
Preferably, for a mixture of (a) polymeric microparticles containing dicamba or an
agrochemically acceptable salt thereof and (b) pinoxaden (e.9. on cereal crops, preferably
non-oat cereal crops, such as wheat, barley, rye and/or triticale, more preferably wheat
and/or barley, e.g. spring or winter wheat or spring or winter barley), an application rate of
from 80 to 400 g or from 100 to 400 g of dicamba / ha, measured as the free acid, and from 5
to 60 g or from 10 to 60 g pinoxaden / ha, is used. More preferably, from 80 to 240 g or from
100 to 240 g orfrom 120 to240 g of dicamba / ha, measured as the free acid (still more
preferably from 100 to 140 g, in particular 120 g, or 240 g, of dicamba I ha, measured as the
free acid), and from 10 to 60 g or from 15 to 60 g or more preferably from 30 to 60 g or from
30 to 45 g pinoxaden / ha, is used.
Specifically preferred examples of application rates, for a mixture of (a) polymeric
microparticles containing dicamba or an agrochemically acceptable salt thereof and (b)
pinoxaden (e.9. on cereal crops, preferably non-oat cereal crops, such as wheat, barley, rye
andlor triticale, more preferably wheat and/or barley, e.g. spring or winter wheat or spring or
winter barley), are:
- from 100 to 140 g, in particular 120 g, of dicamba / ha, measured as the free acid, and from
30 to 60 g (e.9. 30, 40, 45 or 60 g) or from 30 to 45 g (e.9. 30 or 45 9) pinoxaden / ha; or
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- 240 g of dicamba / ha, measured as the free acid, and from 10 to 60 g (e.g. 10, 20, 30, 40,
45 or 60 g) or from 30 to 60 g (e.9. 30, 40, 45 or 60 g) or from 30 to 45 g (e.9. 30, 40 or 45 g)
pinoxaden / ha.
Preferably, for polymeric microparticles containing MCPA or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat and/or barley),
an application rate of from 280 to 2250 g of MCPA / ha, measured as the free acid, is used.
More preferably, from 350 to 1650 g of MCPA / ha, measured as the free acid, is used. Still
more preferably, from 350 to 1100 g of MCPA / ha, measured as the free acid (e.9. from 400
to 900 g, such as 500 g, of MCPA / ha, measured as the free acid) is used.
Preferably, for polymeric micropailicles containing 2,4-D or an agrochemically acceptable
salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat and/or barley),
an application rate of from 280 to 2300 g of 2,4-D / ha, measured as the free acid, is used.
More preferably, from 350 to 1650 g of 2,4-D / ha, measured as the free acid (e.9. from 400
to 1000 g of 2,4-D / ha, measured as the free acid) is used.
Preferably, for polymeric microparticles containing triasulfuron or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, such as wheat,
barley and/or triticale), an application rate of from 5 to 15 g (more preferably from 5 to 10 g)
of triasulfuron / ha, measured as the free compound, is used.
Preferably, for polymeric microparticles containing tribenuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, such as wheat,
barley, rye and/or triticale), an application rate of from 7.5 to 30 g (more preferably from 12.5
to 30 g or from 15 to 30 g (e.9. 15,20 or 30 g), still more preferably from 20 to 30 g) of
tribenuron-methyl/ ha, measured as the free compound, is used.
Preferably, for polymeric microparticles containing iodosulfuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat,
barley, triticale and/or rye, such as winter, spring or durum wheat, triticale, rye or spring
barley), an application rate of from 5 to 15 g (more preferably 10 g) of iodosutfuron-methyl /
ha, measured as the free compound, is used. Preferably, polymeric microparticles
containing iodosulfuron-methyl or an agrochemically acceptable salt thereof are used in
admixture with a safener such as mefenpyr-diethyl or cloquintocet-mexyl.
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Preferably, for polymeric microparticles containing mesosulfuron-methyl or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably nonoat cereal crops, e.g. wheat,
triticale and/or rye, such as winter, spring or durum wheat, triticale or rye), an application rate
of from 10 to 20 g (more preferably 15 g) of mesosulfuron-methyl / ha, measured as the free
compound, is used.
Preferably, for polymeric microparticles containing suffosulfuron or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat), an
application rate of from 10 to 35 g of sulfosulfuron / ha, measured as the frce compound, is
used.
Preferably, for polymeric microparticles containing flupyrsulfuron-methylor an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably non-oat cereal crops, e.g. wheat), an
application rate of from 5 to 15 g (more preferably 10 g) of flupyrsutfuron-methyl / ha,
measured as the free compound, is used.
Preferably, for polymeric microparticles containing pyroxsulam or an agrochemically
acceptable salt thereof (e.9. on cereal crops, preferably nonoat cereal crops, e.g. wheat, rye
and/or triticale, such as spring or winter wheat, winter rye or winter triticale), an application
rate of from 9 to 18.75 g (e.9. from 11 to 15 g) of pyroxsulam / ha, measured as the free
compound, is used. Preferably, polymeric microparticles contiaining pyroxsulam or an
agrochemically acceptable salt thereof are used in admixture with a safener, more preferably
cloquintocehmexyl or cloquintocet acid or an agrochemically acceptable salt thereof.
Preferred formulations have especially the following compositions:
(% = percent by weight):
Emulsifiable concentrates:
active ingredient:
surface-active agent:
liquid carrier:

CLAIMS
1. A herbicidal composition, comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (x) a nonionic surfactant;
wherein the herbicidal composition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
and wherein the nonionic surfactant is present in the continuous liquid phase or medium,
such that the nonionic surfactant stabilizes the dispersion of the polymeric microparticles in
the continuous liquid phase or medium,
and wherein the weight ratio of the polymeric microparticles to the nonionic surfactant in the
herbicidal composition is from 40 : 1 to 1 :2;
and wherein either the composition comprises no ionic surfactant, or the composition
comprises an ionic surfactant and the weight ratio of the polymeric microparticles to the ionic
surfactant in the herbicidal composition is 200 :1or more.
2. A herbicidal composition as claimed in claim 1, wherein the nonionic sudactant is
present in from 0.2 to 30% by weight of the dispersion composition.
3. A herbicidal composition as claimed in claim 2, wherein the nonionic surfactant is
present in from 1 to 10o/o by weight of the dispersion composition.
4. A herbicidal composition as claimed in claim 1,2 or 3, wherein the nonionic surfactant
is a nonionic polymeric barrier surfactant.
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5. A herbicidal composition as claimed in claim 1,2,3 or 4, wherein the nonionic
surfactant comprises polyvinyl alcohol.
6. A herbicidal composition as claimed in claim 1,2,3,4 or 5, wherein the weight ratio of
the polymeric microparticles to the nonionic surfactant in the herbicidal composition is from
20:1 lo 1 :1.
7. A herbicidal composition as claimed in claim 6, wherein the weight ratio of the
polymeric microparticles to the nonionic surfactant in the herbicidal composition is from 10 : 1
to 2.5 : 1.
8. A herbicidal composition as claimed in claim 7, wherein the weight ratio of the
polymeric microparticles to the nonionic surfactant in the herbicidalcomposition is from 7.5 :
1 to 2.5: 1.
9. A herbicidal composition as claimed in any of the preceding claims, wherein either the
composition comprises no ionic surfactant, or the composition comprises an ionic surfactant
in which the weight ratio of the polymeric microparticles to the ionic surfactant in the
herbicidal composition is 330 : 1 or more.
10. A herbicidal composition as claimed in claim 9, wherein either the composition
comprises no ionic surfactant, or the composition comprises an ionic surfactant in which the
weight ratio of the polymeric microparticles to the ionic surfactant in the herbicidal
composition is 670 : 1 or more.
11. A herlcicidal composition as claimed in any of the preceding claims, wherein the
herbicidal composition is an aqueous dispersion composition in which the polymeric
microparticles are dispersed in a continuous aqueous liquid phase or medium.
12. A herbicidal composition as claimed in any of the preceding claims, wherein the
polymeric microparticles are controlled-release matrices, within which is the first herbicide,
and which function in such a way as to control and/or slow down the release of the first
herbicide from the polymeric microparticles into a liquid medium when the polymeric
microparticles are placed in and in contact with the liquid medium.
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13. A herbicidal composition as claimed in any of the preceding claims, wherein the
polymeric microparticles containing the first herbicide are controlled-release matrices within
which is the first herbicide, characterized by:
an amount of the first herbicide released, over a specified time period which is the first t hour
of contact or the first 3 hours of contact, from the polymeric microparticles into a liquid
medium after the polymeric microparticles are placed in and in contact with the liquid
medium,
which is reduced by at least 40olo, measured by numbers of moles of the first herbicide or
measured by weight of the first herbicide calculated in a salt-free form,
compared to an amount of the same first herbicide released or dissolved over the same
specified time period, from a sample of the same first herbicide which is in substantially pure
form and in which the first herbicide is not contained within polymeric microparticles, into the
same liquid medium used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed in and in contact with the liquid
medium.
14. A herbicidal composition as claimed in any of the preceding claims, wherein the mean
diameter by volume of the polymeric microparticles containing the first herbicide is from 0.5
to 15 micrometres, as measured by light scattering laser diffraction.
15. A herbicidal composition as claimed in any of the preceding claims, wherein the
polymer microparticles comprise a polymeric matrix or matrices comprising:
- a crosslinked polyester polymer or co-polymer;
- an epoxy polymer or co-polymer;
- a phenolic, urea or melamine polymer or co-polymer;
- a silicone or rubber polymer or co-polymer;
- a polyisocyanate, polyamine or polyurethane polymer or co-polymer;
- an acrylic polymer or co-polymer;
- a polymer or co-polymer of styrene, vinyltoluene, alpha-methylstyrene, divinylbenzene, or
diallylphthalate;
- a polyacrylonitrile polymer or co-polymer;
- a polyalkylacetate polymer or co-polymer;
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- a Cr-Gsalkyl and/or hydroxypropyl derivative of cellulose, or carboxymethylcellulose, sodium
carboxymethylcellulose, or calciu m carboxymethylcellulose;
- polyvinylpyrrolidone (PVP) (crosslinked or non-crosslinked); andlor
- a polyoxyethylene-polyorypropylene copolymer (poloxamer).
16. A herbicidal composition as claimed in claim 15, wherein the polymer microparticles
comprise a polymeric matrix or matrices comprising:
- a crosslinked polyester polymer formed from the polymerization of an unsaturated (alkenecontaining)
polyester rcsin mixed with an alkenylgroup-containing monomer; and/or
- an epoxy polymer or co-polymer.
17. A herbicidal composition as claimed in claim 16, wherein the polymer microparticles
comprise a polymeric matrix or matrices comprising a crosslinked polyester polymer formed
from the polymerization of an unsaturated (alkene-containing) polyester resin mixed with a
vinyl-group-containing monomer.
18. A herbicidal composition as claimed in any of the preceding claims, wherein the
polymeric microparticles are present in from 1 to 60% by weight of the dispersion
composition.
19. A herbicidal composition as claimed in any of the preceding claims, wherein the
polymer microparticles either contain no non-volatile solvent, oil or plasticizer, or contain up
to 5% of a non-volatile solvent, oil and/or plasticizer, by weight of the polymer microparticles
containing the first herbicide.
20. A herbicidal composition as claimed in any of the preceding claims, wherein the
amount of the first herbicide contained within the polymer microparticles is from 5 to 40o/o, by
weight of the polymer microparticles containing the first herbicide.
21. A herbicidal composition as claimed in any of the preceding claims, wherein the
amount of the first herbicide present in the composition is from 0.5 to 20o/o, by weight of the
d ispersion composition.
22. A herbicidal composition as claimed in any of the preceding claims, wherein:
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the synthetic auxin herbicide is defined as a compound that is a herbicide and that, either
itself or after the removal of any procide groups present thereon, stimulates the expression of
B-glucuronidase (GUS) in transgenic Anbidopsr's plantlets line AIEM101 in an assay in
which:
- seeds of AIEM101 are germinated aseptically on half-strength Murashige and Skoog
medium containing a test compound at a range of doses between 0 and 200 uM and
assayed for GUS activity at 6 days post-germination; and
- either, for a quantitative GUS assay, protein crude extracts of the plantlets are prepared
and a fluorometric assay is used;
- or, whole plantlets are transfened to 100 mM sodium phosphate buffer at pH 7.0 containing
10 mM EDTA,0.1% Triton X-100, 1mM potassiumferricyanide, 1 mM potassium
fenocyanide and 1 mM S-bromo4-chloro-3-indolyl B-D-glucuronic acid (Xgluc) and
incubated tor 12 hours at 37 "C; stained plantlets are then removed and cleared of
chlorophyll by soaking in70o/o (v/v) ethanol; the amount of overall blue staining is then
assessed and compared visually; and
- a synthetic auxin is defined in this assay as a test compound which exhibits a dose
response of GUS activity or blue stiaining dependent on the concentration of test compound
present during the germination and growth of the AtEM101 Arabidopsis plantlet; and
- a synthetic auxin is further defined in this assay as a compound that, when assayed under
the above conditions, and at a concentration of 50 pM (50 micromolar), results in at least
about a doubling of GUS activity or of the amount of blue staining, relative to the amount of
GUS activity or blue staining obtained with like AIEM101 plantlets like-grown in the absence
of the test compound;
and wherein an acetolactate synthase (ALS) inhibitor herbicide is defined as a compound
that is a herbicide and that, either itself or after the removal of any procide groups present
thereon, inhibits, at a concentration less than 100 pM, the specific activity of acetolactate
synthase by more than 90% relative to similar controls run in the absence of the compound,
wherein the comparative rate measurements are made at or after a reaction time of at least
200 minutes;
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and wherein the acetolactate synthase has been prepared as described in T. Hawkes
et al., in 'Herbicides and Plant Metabolism': ed. A.D. Dodge, Society for Experimental Biology
Seminar Series 38, Cambridge University Press, Unitied Kingdom, 1989, pp. 113-136.
23. A herbicidal composition as claimed in any of the preceding claims, wherein the first
herbicide is: dicamba ,2,4-O, MCPA, triasulfuron, tribenuron-methyl, iodosulfuron-methyl,
mesosutfuron-methyl, sulfosulfuron, flupyrsutfuron-methyl, or pyroxsulam; or an
agrochemica lly acceptable salt thereof.
24. A herbicidal composition as claimed in claim 23, wherein the first herbicide is dicamba
or an agrochemically acceptable salt thereof.
25. A herlcicidal composition, comprising a mixture of:
(a) polymeric microparticles contiaining a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (y) a surface-modified clay;
wherein the herbicidalcomposition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
and wherein the surface-modified clay is present in the continuous liquid phase or medium
and/or is present at the interface between the continuous liquid phase or medium and the
polymeric microparticles, such that the surface-modified clay stabilizes the dispersion of the
polymeric microparticles in the continuous liquid phase or medium.
26. A herbicidal composition as claimed in claim 25 wherein the surface-modified clay is a
clay which has been surface-modified such that the surface-modified clay (i) is capable of
being at least partially wetted by an aqueous liquid phase, (ii) is capable of being at least
partially wetted by a non-aqueous oil liquid phase, and (iii) is capable of stablizing an oil-andwater-
containing emulsion through adsorption at a or the oil/water interface.
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27. A herbicidal composition as claimed in claim 25 or 26, wherein the surface-modified
clay comprises an amino-silane-modified clay.
28. A herbicidalcomposition as claimed in claim 25,26 or27, wherein the surfacemodified
clay is a smectite group clay or kaolin group clay.
29. A herbicidal composition as claimed in any of claims 25lo 28, wherein the surfacemodified
clay is present in from 0.2 to 20o/o by weight of the dispersion composition.
30. A herbicidal composition as claimed in claim 29, wherein the surface-modified clay is
present in from 1to7"/o by weight of the dispersion composition.
31. A herbicidal composition as claimed in any of claims 25 to 30, wherein the weight
ratio of the polymeric microparticles to the surface-modified clay in the herbicidal composition
isfrom100:1to3:1.
32. A herbicidal composition as claimed in claim 31, wherein the weight ratio of the
polymeric microparticles to the surface-modified clay in the herbicidal composition is from 20
:1to4:1.
33. A herbicidal composition as claimed in any of claims 25lo 32, wherein the herbicidal
composition is an aqueous dispersion composition in which the polymeric microparticles are
dispersed in a continuous aqueous liquid phase or medium.
34. A herbicidal composition as claimed in any of claims 25 to 33, wherein the polymeric
microparticles are controlled-release matrices, within which is the first herbicide, and which
function in such away as to control and/or slow down the release of the first herbicide from
the polymeric microparticles into a liquid medium when the polymeric microparticles are
placed in and in contact with the liquid medium.
35. A herbicidal composition as claimed in any of claims 251o34, wherein the polymeric
microparticles containing the first herbicide are controlled-release matrices within which is
the first herbicide, characterized by:
an amount of the first herbicide released, over a specified time period which is the first t hour
of contact or the first 3 hours of contact, from the polymeric microparticles into a liquid
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medium after the polymeric microparticles are placed in and in contact with the liquid
medium,
which is reduced by at least 40%, measured by numbers of moles of the first herbicide or
measured by weight of the first herbicide calculated in a salt-free form,
compared to an amount of the same first herbicide released or dissolved over the same
specified time period, from a sample of the same first herbicide which is in substantially pure
form and in which the first herbicide is not contained within polymeric micropadicles, into the
same liquid medium used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed in and in contact with the liquid
medium.
36. A herbicidal composition as claimed in any of claims 25 to 35, wherein the mean
diameter by volume of the polymeric microparticles containing the first herbicide is from 1.0
to 50 micrometres, as measured by light scattering laser diffraction.
37. A herbicidal composition as claimed in any of claims 25 to 36, wherein the herbicidal
composition and/or the polymeric microparticles and/or the firct herbicide is or are as defined
in one or more of claims 9, 10, or 15to24.
38. A herbicidal composition comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (b) pinoxaden;
wherein the polymeric microparticles are controlled-release matrices, within which is the first
herbicide, and which function in such a way as to control and/or slow down the release of the
first hebicide from the polymeric microparticles into a liquid medium when the polymeric
microparticles are placed in and in contact with the liquid medium.
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39. A herbicidal composition as claimed in claim 38, wherein the polymeric microparticles
containing the first herbicide are controlled-release matrices within which is the first
herbicide, characterized by:
an amount of the first herbicide released, over a specified time period which is the first t hour
of mntact or the first 3 hours of contact, from the polymeric microparticles into a liquid
medium after the polymeric microparticles are placed in and in contact with the liquid
medium,
which is reduced by at least 40%, measured by numbers of moles of the first herbicide or
measured by weight of the first herbicide calculated in a salt-free form,
compared to an amount of the same first herbicide released or dissolved over the same
specified time period, from a sample of the same first herbicide which is in substantially pure
form and in which the first herbicide is not contained within polymeric microparticles, into the
same liquid medium used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed in and in contact with the liquid
medium.
40. A herbicidal composition as claimed in claim 38 or 39, wherein the polymeric
microparticles containing the first herbicide are controlled-release matrices within which is
the first herbicide, characterized by:
an amount of the first herbicide released, over a specified time period which is the first t hour
of contact or the first 3 hours of contact, from the polymeric micropadicles into a liquid
medium after the polymeric microparticles are placed in and in contact with the liquid
medium,
which is reduced by at least 507o, measured by numbers of moles of the first herbicide or
measured by weight of the first herbicide calculated in a salt-free form,
compared to an amount of the same first herbicide released or dissolved over the same
specified time period, from a sample of the same first herbicide which is in substantially pure
form and in which the first herbicide is not contained within polymeric microparticles, into the
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same liquid medium used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed in and in contact with the liquid
medium.
41. A herbicidal composition as claimed in claim 39 or 40, wherein:
the specified time period is the first t hour of contact,
the liquid medium is water, and
the reduction in the amount of the first herbicide released over the specified time period is
measured by weight of the first herbicide calculated in a saltfree form.
42. A herbicidal composition as claimed in claim 38, 39, 40 or 41, wherein the polymeric
microparticles are controlled-release matrices within which is the first herbicide, and wtrich
are such that the amount of the first herbicide released, over the first 3 hours of contact, from
the polymeric microparticles into an aqueous liquid medium after the polymeric microparticles
are placed in and in contact with the liquid medium, is equal to or less than 35%, measured
by numbers of moles of the first herbicide or measured by weight of the first herbicide
calculated in a salt-free form,
compared to an amount of the same first herbicide released or dissolved, over the first 3
hours of contact, from a sample of the same first herbicide which is in substantially pure form
and in which the first herbicide is not contained within polymeric microparticles, into the same
aqueous liquid medium used for the polymeric microparticle release analysis, after the
substantially pure sample of the first herbicide is placed in and in contact with the liquid
medium;and
wherein "substantially pure form" means at least 85% pure by weight.
43. A herbicidal composition as claimed in any of claims 38lo 42, wherein 90% or more
by volume of the polymeric microparticles containing the first herbicide have a particle size of
less than or equal to 50 micrometres (microns); and wherein 50% or more by volume of the
polymeric microparticles containing the first herbicide have a particle size of less than or
equal to 25 micrometres; as measured by laser diffraction.
44. A herbicidal composition as claimed in any of claims 38 to 43, wherein 907o or more
by volume of the polymeric microparticles containing the first herbicide have a particle size of
less than or equalto 30 micrometres; and 50% or more by volume of the polymeric
microparticles containing the first herbicide have a particle size of less than or equal to 15
micrometres; as measured by laser diffraction.
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45. A herbicidal composition as claimed in any of claims 38 to 44, wherein the mean
diameter of the polymeric microparticles containing the first herbicide is from 0.7 to 15
micrometres.
46. A herbicidal composition as claimed in any of claims 38 to 45, wherein the polymer
microparticles comprise a polymeric matrix or matrices comprising:
- a crosslinked polyester polymer or co-polymer;
- an epoxy polymer or co-polymer;
- a phenolic, urea or melamine polymer or co-polymer;
- a silicone or rubber polymer or co-polymer;
- a polyisocyanate, polyamine or polyurethane polymer or co-polymer;
- an acrylic polymer or co-polymer;
- a polymer or co-polymer of styrene, vinyltoluene, alpha-methylstyrene, divinylbenzene, or
diallylphthalate;
- a polyacrylonitrile polymer or co-polymer;
- a polyalkylacetate polymer or co-polymer;
- a Cr-Cgalkyl and/or hydrorypropyl derivative of cellulose, carboxymethylcellulose, sodium
ca rboxymethylcel I u lose, or ca lci u m ca rboxymethylcel lu lose ;
- polyvinylpyrrolidone (PVP) (crosslinked or non-crosslinked); and/or
- a polyoxyethylene-polyoxypropylene copolymer (poloxamer).
47. A herbicidal composition as claimed in claim 46, wherein the polymer microparticles
comprise a polymeric matrix or matrices comprising:
- a crosslinked polyester polymer formed from the polymerization of an unsaturated (alkenecontaining)
polyester resin mixed with an alkenylgroup-containing monomer; and/or
- an epoxy polymer or co-polymer.
48. A herbicidal composition as claimed in claim 46, wherein the polymer microparticles
comprise a polymeric matrix or matrices comprising a crosslinked polyester polymerformed
from the polymerization of an unsaturated (alkene-containing) polyester resin mixed with a
vinyl-group-contain ing monomer.
49. A herbicidal composition as claimed in any preceding claim, wherein:
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the synthetic auxin herbicide is defined as a compound that is a herbicide and that, either
itself or after the removal of any procide groups present thereon, stimulates the expression of
B-glucuronidase (GUS) in transgenic Anbidopsls plantlets line AIEM101 in an assay in
which:
- seeds of AIEM101 are germinated aseptically on half-strength Murashige and Skoog
medium containing a test compound at a range of doses between 0 and 200 uM and
assayed for GUS activity at 6 days post-germination; and
- either, for a quantitative GUS assay, protein crude extracts of the plantlets are prepared
and a fluorometric assay is used;
- or, whole plantlets are transferred to 100 mM sodium phosphate buffer at pH 7.0 containing
10 mM EDTA,0.1% Triton X-100, 1mM potassium ferricyanide, 1 mM potassium
fenocyanide and 1 mM 5-bromo-4-chloro-3-indolyl p-D-glucuronic acid (Xgluc) and
incubated tor 12 hours at 37'C; stained plantlets are then removed and cleared of
chlorophyll by soaking in 70o/o (v/v) ethanol; the amount of overall blue staining is then
assessed and compared visually; and
- a synthetic auxin is defined in this assay as a test compound which exhibits a dose
response of GUS activity or blue straining dependent on the concentration of test compound
present during the germination and growth of the AtEM101 Arabidopsis plantlet; and
- a synthetic auxin is further defined in this assay as a compound that, when assayed under
the above conditions, and at a concentration of 50 pM (50 micromolar), results in at least
about a doubling of GUS activity or of the amount of blue staining, relative to the amount of
GUS activity or blue staining obtained with like AtEM101 plantlets like-grown in the absence
of the test compound;
and wherein an acetolactate synthase (ALS) inhibitor herbicide is defined as a compound
that is a herbicide and that, either itself or after the removal of any procide groups present
thereon, inhibits, at a concentration less than 100 pM, the specific activity of acetolactate
synthase by more than 90% relative to similar controls run in the absence of the compound,
wherein the comparative rate measurements are made at or after a reaction time of at least
200 minutes;
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and wherein the acetolactate synthase has been prepared as described in T. Hawkes
et al., in 'Herbicides and Plant Metabolism': ed. A.D. Dodge, Society for Experimental Biology
Seminar Series 38, Cambridge University Press, Unitied Kingdom, 1989, pp. 1 13-136.
50. A herbicidal composition as claimed in any of claims 38 to 49, wherein the first
herbicide, contained within the polymeric microparticle, is selective on, i.e. is suitable for use
on, wheat and/or barley.
51. A herbicidal composition as claimed in any of claims 38 to 50, wherein the first
herbicide is: dicamba ,2,4-D, MCPA, triasutfuron, tribenuron-methyl, iodosulfuron-methyl,
mesosulfuron-methyl, sulfosulfuron, flupyrsulfuron-methyl, or pyroxsulam; or an
agrochemically acceptable salt thereof.
52. A herbicidal composition as claimed in claim 51, wherein:
the weight ratio of dicamba or an agrochemically acceptable salt thereof (measured as the
free acid) to pinoxaden is 16:1 to 4:3;
the weight ratio of MCPA or an agrochemically acceptable salt thereof (measured as the free
acid) to pinoxaden is from 110:1 to 35:6;
the weight ratio of 2,4-D or an agrochemically acceptable salt thereof (measured as the free
acid) to pinoxaden is from 110:1 to 35:6;
the weight ratio of triasulfuron or an agrochemically acceptable salt thereof (measured as the
free acid) to pinoxaden is from 1:1 to 1:12;
the weight ratio of tribenuron-methyl or an agrochemically acceptable salt thereof (measured
as the free acid) to pinoxaden is from 2:1 lo 5;24;
the weight ratio of iodosulfuron-methyl or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden is from 1:1to 1:12:
the weight ratio of mesosulfuron-methyl or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden is from 4:3 to 1:6; and
the weight ratio of sulfosulfuron or an agrochemically acceptable salt thereof (measured as
the free acid) to pinoxaden is from 7:3 to 1:6;
the weight ratio of flupyrsulfuron-methyl or an agrochemically acceptable salt thereof
(measured as the free acid) to pinoxaden is from 1:1 to 1 :12; and
the weight ratio of pyroxsulam or an agrochemically acceptable salt thereof (measured as the
free acid) to pinoxaden is from 15:12 to 3:20.
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53. A herbicidal composition as claimed in any of claims 38 to 52, wherein 50% or more
by weight of the first herbicide contained within the polymeric microparticles, is present within
the polymeric microparticles in non-crystalline form.
54. A herbicidal composition as claimed in any of claims 38 to 53, comprising a mixture
of:
(a) polymeric microparticles containing a synthetic auxin herbicide being dicamba, 2,4-D, or
MCPA, or an agrochemically acceptable salt thereof; and
(b) pinoxaden.
55. A herbicidal composition as claimed in claim 54, wherein (a) are polymeric
microparticles containing dicamba or an agrochemically acceptable salt thereof.
56. A herbicidal composition as claimed in any of claims 38 to 55, wherein the amount of
the first herbicide contained within the polymeric microparticles is from 1 to 50%, by weight of
the polymeric microparticles containing the first herbicide.
57. A herbicidal composition as claimed in any of claims 38 to 56, wherein the polymeric
microparticles either contain no non-volatile solvent, oil or plasticizer, or contain up to 5olo of
a non-volatile solvent, oil and/or plasticizer, by weight of the polymeric microparticles
containing the first herbicide.
58. A herbicidal composition as claimed in any of claims 38 to 57, which is a dispersion
composition in which the polymeric microparticles are dispersed in a continuous liquid phase
or medium.
59. A herbicidal composition as claimed in claim 58, which is an aqueous dispersion
composition in which the polymeric microparticles are dispersed in a continuous aqueous
liquid phase or medium; and wherein the dispersion of the polymeric microparticles in the
continuous liquid phase or medium is stabilised by a stabilizer and/or a dispersant.
60. A herbicidal composition as claimed in any of claims 38 to 59, comprising optionally
(c) a safener and, optionally, (d) an additional herbicide and, optionally, (e) an oil additive.
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61. A herbicidal composition as claimed in claim 60, wherein a safener (c) is present and
comprises cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt
th ereof , fen ch lorazol e, or mefen pyr-d ieth yl.
62. A herbicidal composition as claimed in claim 60 or 61, wherein (e) is present and is
an oil additive selected from an oil of vegetable or animal origin, a mineraloil, alkyl esters of
such oils, mixtures of such oils and oil derivatives, tris-esters of phosphoric acid with aliphatic
or aromatic alcohols and bis-esters of alkyl phosphonic acids with aliphatic or aromatic
alcohols.
63. A method of reducing the antagonistic effect on the control of monocotyledonous
weeds in non-oat cereals which is shown by a herbicidal mixture of either a synthetic auxin
herbicide with pinoxaden or an ALS inhibitor herbicide with pinoxaden, which comprises
applying a herbicidal composition as defined in any one of claims 38 to 62 to the plants or to
the locus thereof.
64. A method of controlling weeds in non-oat cereal crops comprising applying a
herbicidal composition as defined in any one of claims 1 to 63 to the plants or to the locus
thereof.
65. A method of controlling weeds in non-oat cerealcrops, comprising the steps of:
(i) mixing in a tank a first herbicidal composition and a second herbicidal composition, and
optionally a solvent suitable for applying the first and second compositions to plants or to a
locus thereof, and optionally a tank-mix adjuvant, to provide a tank-mixed herbicidal
composition;
wherein the first herbicidal composition comprises polymeric microparticles containing a first
herbicide, wherein the first hebicide is a synthetic auxin herbicide or an acetolactate
synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a saltfree form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden; and
wherein the polymeric microparticles are controlled-release matrices, within which is the first
herbicide, and which function in such a way as to control and/or slow down the release of the
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first herbicide from the polymeric microparticles into a liquid medium when the polymeric
microparticles are placed in and in contact with the liquid medium; and
wherein the second herbicidal composition comprises pinoxaden; and
(ii) applying the tank-mixed herbicidal composition to the plants or to the locus thereof.
66. A method as claimed in claim 63, 64 or 65, wherein the first herbicide is as defined in
any one of claims 49 to 56.
67. A method as claimed in claim 63, 64, 65 or 66, wherein pinoxaden or the pinoxaden is
applied at an application rate of from 15 to 60 g pinoxaden / ha.
68. A method as claimed in claim 67, wherein pinoxaden or the pinoxaden is applied at
an application rate of from 30 to 45 g pinoxaden / ha.
69. A method as claimed in any of claims 63 to 68, wherein the polymeric microparticles
contiain dicamba or an agrochemically acceptable salt thereof, and the dicamba or the
agrochemically acceptable salt thereof is applied at an application rate of from 80 to 240 g of
dicamba / ha, measured as the free acid.
70. A method as claimed in any one of claims 63 to 69, wherein the weeds comprise
Avena, Lolium, andlor Alopecurus species.
71. A herbicidal composition, comprising a mixture of:
(a) polymeric microparticles containing a first herbicide, wherein the first herbicide is a
synthetic auxin herbicide or an acetolactate synthase (ALS) inhibitor herbicide;
wherein the first herbicide, when in a salt-free form and when not contained within polymeric
microparticles, antagonises the herbicidal activity of pinoxaden;
and (x) a nonionic surfactant;
wherein the herbicidalcomposition is a dispersion composition in which the polymeric
microparticles are dispersed in a continuous liquid phase or medium,
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and wherein the nonionic surfactant is present in the continuous liquid phase or medium,
such that the nonionic surfactant stabilizes the dispersion of the polymeric microparticles in
the continuous liquid phase or medium,
wherein the polymer microparticles comprise a polymeric matrix or matrices comprising a
crosslinked polyester polymer or co-polymer;
and wherein the mean diameter by volume of the polymeric microparticles contiaining the first
herbicide is from 0.5 to 15 micrometres, in particularfrom 2.0 to 13 micrometres, as
measured by light scattering laser diffraction.
72. A herbicidal compositon as claimed in claim 71, wherein the nonionic surfactant
comprises polyvinyl alcohol.
73. A herbicidalcomposition as claimed in claim 71 or72, wherein:
the polymeric microparticles are controlled-release matrices, within which is the first
herbicide, and which function in such away as to control and/or slow down the release of the
first herbicide from the polymeric microparticles into a liquid medium when the polymeric
microparticles are placed in and in contact with the liquid medium; and
the crosslinked polyester polymer or co-polymer is a crosslinked polyester polymer formed
from the polymerization of an unsaturated (alkene-containing) polyester resin mixed with an
alkenyl-group-containing monomer.