AU2021106535A4 - Herbicide formulations comprising flumioxazin and means to monitor the stability thereof - Google Patents

Abstract

The present invention relates to a herbicide formulation comprising: flumioxazin; a pH indicator, a surfactant, optionally a solvent, optionally an agriculturally acceptable filler, and optionally a pH modifier for establishing a neutral or slightly acidic environment. The invention also relates to a method of preparing a herbicide formulation, and a method of controlling or inhibiting the growth of and/or killing grass or weeds associated with crops, the method comprising the step of applying a herbicidally effective amount of a composition according to the invention.

Description

HERBICIDE FORMULATIONS COMPRISING FLUMIOXAZIN AND MEANS TO MONITOR THE STABILITY THEREOF FIELD OF THE INVENTION

[0001] The present invention relates to formulations comprising the herbicide flumioxazin, the

common name for which is N-(7-fluoro-3,4-dihydro-3-oxo-4-prop-2-ynyl-2H-1,4

benzoxazin-6-yl) cyclohex-1-ene-1,2-dicarboxamide. In particular, the invention relates

to a water dispersible granule which is highly loaded with flumioxazin and a means to

monitor the stability thereof. The invention also relates to methods of preparing and

using said herbicide formulations. However, it will be appreciated that the invention is

not limited to this particular field of use, or formulation type.

BACKGROUND OF THE INVENTION

[0002] The following discussion of the prior art is provided to place the invention in an

appropriate technical context and enable the advantages of it to be more fully

understood. It should be appreciated, however, that any discussion of the prior art

throughout the specification should not be considered as an express or implied

admission that such prior art is widely known or forms part of the common general

knowledge in the field.

[0003] Flumioxazin is a benzoxazine that is N-(prop-2-yn-1-yl)-2H-1,4-benzoxazin-3(4H)-one,

which is substituted at position 6 by a 1,3-dioxo-1,3,4,5,6,7-hexahydro-2H-isoindol-2-y

group, and at position 7 by a fluorine. As a protoporphyrinogen oxidase inhibitor, it is

used for the control of many annual broad-leaved weeds and some annual grasses pre

and post-emergence in a variety of crops, such as soya beans, peanuts, and orchards,

including a variety of vegetable and fruit crops. It has a role as a herbicide, an

agrochemical, an EC 1.3.3.4 (protoporphyrinogen oxidase) inhibitor and a teratogenic

agent. When used as a herbicide, it is absorbed by foliage and germinating seedlings,

and is generally understood to induce accumulation of porphyrins and enhance peroxidation of membrane lipids (in the presence of light and oxygen), which leads to irreversible damage of the membrane function and structure of susceptible plants.

[0004] Flumioxazin was first introduced as a herbicide in Argentina in 1992 and is widely

marketed around the world. For example, use of flumioxazin is approved in at least one

jurisdiction for use in fruit, vegetable and ornamental crops as well as for weed control

in industrial plants against ragweed, dandelion and nightshade plants. It has also been

approved for use on peanuts and soybeans.

[0005] Flumioxazin is applicable for use in Australia when registered by the Australian

Pesticides and Veterinary Medicines Authority (APVMA). The active ingredient is

typically presented in commercial products as a dispersible concentrate - i.e.

suspension concentrate, wettable powder or water dispersible granule. However, when

flumioxazin is provided in a product that is in granular form, the active is only provided in

relatively low concentrations, such as below around 50 wt% (i.e., 500g/kg). For

example, the herbicide marketed by Sumitomo (i.e., Valor 500 WG Herbicide APVMA

No. 61622) contains 500g/kg flumioxazin presented as a water dispersible granule.

One more recent product on the Australian market, however, provides flumioxazin at a

maximum of 750g/kg, i.e. Payload Herbicide APVMA No. 86471.

[0006] Notwithstanding the commercial availability of a range of flumioxazin compositions,

there remains a need for improved flumioxazin-based compositions for use in an

agricultural setting that overcomes one or more of the limitations of commercially

available flumioxazin compositions.

[0007] In the case of concentrated formulations, prior to application the concentrate is typically

diluted to an appropriate herbicidally-active concentration. Flumioxazin is subject to

degradation through hydrolysis and hydrolysis/photolysis, and the rate of degradation is

substantial with a half-life as low as 1.7 hours in slightly alkaline waters of pH of around

8.5, and even more aggressive deterioration in contact with water at pH 9 (half-life of

around 0.25 hours). The degradation may be exacerbated by other factors, such as

being in combination with other herbicides, exposure to visible and UV radiation,

presence of contaminants and other substances.

[0008] Prior art solutions aimed at keeping the diluted herbicide in the neutral-to-acidic pH

range, and preferably an acidic pH range in the case of flumioxazin, to avoid or

minimise these degradation issues include the use of buffers to pre-treat the water or

water-containing dilution liquid to ensure that the pH is kept to within an optimal and

narrow pH range. This is expensive, time consuming, and can be inconvenient. Other

options known in the art are to use only fresh water (having a pH of about 7), and to

avoid the use of tank or bore water, where the pH can be detrimental to the stability of

the herbicide formulation. Again, this is inconvenient and can be expensive. Other

options in the art are to sample and test the diluted herbicide, potentially repeatedly

over time, and adjust the pH as necessary to avoid the pH being detrimental to the

stability of the herbicide formulation.

[0009] It is an object of the present invention to overcome or ameliorate at least one of the

disadvantages of the prior art, or to provide a useful alternative.

[0010] It is a preferred object of at least one form of the present invention to provide a

herbicide composition comprising flumioxazin, whereby the composition is in the form of

a water-dispersible granule, and the concentration of flumioxazin is relatively high, and

in particular is higher than prior art compositions.

[0011] Various advantages may be achieved by the claimed invention, including economies of

manufacturing, packaging, handling and storage, relative to lower concentration

alternatives. Additionally, there is a commensurate reduction in the amount of

packaging that needs to be recycled or disposed of. Further advantages of the invention

relate to a reduction in the cost of freight (volume and weight basis) in transporting the

flumioxazin formulation from factory to field.

SUMMARY OF THE INVENTION

[0012] In a first aspect, the invention provides a herbicide formulation comprising:

flumioxazin;

a pH indicator;

a surfactant, and optionally an agriculturally acceptable filler, and optionally a pH modifier for establishing a neutral or slightly acidic environment.

[0013] It will be appreciated that the terms "formulation" and "composition" may be used

interchangeably herein.

[0014] In a second aspect, the invention provides a herbicide formulation according to the first

aspect, wherein:

the pH indicator is selected from the group consisting of: cresol red, bromocresol

purple, neutral red, and phenol red; and

wherein:

if the herbicide formulation is in the form of a water dispersible granule or wettable

powder, then the flumioxazin is present at a concentration of at least about 500

g/kg and the pH indicator is present at a concentration of between about 0.01 and

20 g/kg; or

if the herbicide formulation is in the form of a liquid suspension concentrate, then

the flumioxazin is present at a concentration of at least about 250 g/L and the pH

indicator is present at a concentration of between about 0.01 and 20 g/L.

[0015] In a third aspect, the invention provides either:

a herbicide formulation in the form of a water dispersible granule or wettable powder,

comprising:

flumioxazin at a concentration of greater than about 500 g/kg;

pH indicator is present at a concentration of between about 0.01 and 20 g/kg; and

a surfactant;

or

a herbicide formulation in the form of a liquid suspension concentrate comprising:

flumioxazin at a concentration of about 250 g/L;

pH indicator is present at a concentration of between about 0.01 and 20 g/L.

[0016] In some embodiments, flumioxazin is present at a concentration of at least about 250

g/L, or between about 250 g/L and about 1250 g/L for liquid formulations such as liquid

suspension concentrates, or at least about 500 g/kg, or between about 500 g/kg to about 999 g/kg of the total weight of the herbicide formulation for solid formulations such as water dispersible granules or wettable powders.

[0017] In a fourth aspect, the invention provides a method of preparing a herbicide formulation

including the steps of:

(a) combining flumioxazin, a pH indicator, a surfactant, optionally an agriculturally

acceptable filler, optionally a pH modifier; and

(b) mixing the mixture of step (a) to thereby prepare the herbicide formulation.

[0018] In some embodiments, the agriculturally acceptable filler can comprise a single

agriculturally acceptable filler, or a combination of agriculturally acceptable fillers. In

some embodiments, the agriculturally acceptable filler comprises one or more of:

amorphous silica, sodium sulfate, bentonite, calcium chloride dihydrate and talc, or

combinations thereof.

[0019] In some embodiments, an auxiliary agent may also be included, which comprises one or

more agents selected from the group consisting of a fertilizer, a natural polymer, a

silicate, a gum, a sugar and a synthetic organic polymer. In some embodiments, the

auxiliary agent comprises one or more agents selected from the group consisting of

potassium sulphate, sodium hydrogen phosphate, cellulose, talc, gum arabic, sucrose

and polyvinyl alcohol.

[0020] The method of the fourth aspect may further comprise the step of adding water or a

water-containing liquid to the mixture before or during step (b).

[0021] In a fifth aspect, the invention provides a herbicide formulation when produced

according to the method of the fourth aspect.

[0022] In a sixth aspect, the invention provides a method of controlling or inhibiting the growth

of and/or killing grass or weeds associated with crops, the method comprising the step

of applying a herbicidally effective amount of a composition according to any one of the

first, second, third or fifth aspects to said crop.

[0023] The method optionally further comprising the step of adjusting the pH of the composition

based on the colour of the composition. In some embodiments, the pH of the

composition is adjusted by the addition of a suitable acid. In some embodiments, the suitable acid can be any acid or other compound suitable for lowering the pH of a solution. In some embodiments, the suitable acid is selected from the group consisting of carbon dioxide, carbonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, propionic acid, citric acid, lactic acid, pyruvic acid, any salt or solution thereof, or any combination thereof. In some embodiments the suitable acid can further comprise water or any other neutral solvent. In some embodiments, the suitable acid is a commercially available pH adjustment solution.

[0024] In some embodiments, the pH of the composition is adjusted by the addition of a

suitable base. In some embodiments, the suitable base can be any base or other

compound suitable for raising the pH of a solution. In some embodiments, the suitable

base is selected from the group consisting of sodium hydroxide, sodium carbonate,

calcium hydroxide, magnesium hydroxide, potassium hydroxide, ammonia and any salt

or solution thereof, or any combination thereof. In some embodiments the suitable base

can further comprise water or any other neutral solvent. In some embodiments, the

suitable base is a commercially available pH adjustment solution.

[0025] In some embodiments, the pH is adjusted such that the pH indicator visually indicates

that the composition is of neutral or mildly acidic pH. In some embodiments, the pH is

adjusted such that the pH indicator visually indicates that the pH of the composition in

the range of between about 5.5 and 8, or between about 5.5 and 7.5. In some

embodiments the pH is adjusted such that the pH indicator visually indicates that the pH

of the composition is below about 8, below about 7, or below about 6.

[0026] In some embodiments, the herbicide formulation comprises a surfactant, and the

surfactant comprises sodium diisopropyl naphthalene sulfonate, sodium naphthalene

sulphonate, an alkylnaphthalene sulfonate, a sodium dodecyl sulfate salt, a sodium

neutralized styrene/acrylic acid copolymer and an alpha olefin sulfonate

[0027] In preferred embodiments, the auxiliary agent comprises one or more agents selected

from the group consisting of potassium sulphate, sodium hydrogen phosphate, cellulose

and sucrose.

[0028] In some cases, it may be preferable to sequentially, or concurrently apply two or more

of the inventive herbicide formulations described herein (mixed with water or a water

containing liquid).

[0029] According to a first embodiment, the present invention provides a solid herbicide

composition comprising:

flumioxazin at a concentration of greater than 750 g/kg,

optionally an agriculturally acceptable filler, and

a surfactant.

[0030] Preferably the herbicide formulation according to the first embodiment is in a granular

form, and is water dispersible or emulsifiable.

[0031] In some embodiments, the flumioxazin concentration is between 750 g/kg and 950 g/kg.

[0032] In some embodiments, the filler may be selected from the group consisting of

amorphous silica, sodium sulfate, calcium chloride dihydrate and talc, or combinations

thereof or any other agriculturally acceptable filler. It will be appreciated that the filler of

the first aspect may also fulfil other roles, such as a binder or a chelating agent, as well.

[0033] In certain embodiments, the surfactant may be an anionic surfactant. The anionic

surfactant may be selected from the group consisting of sodium diisopropyl naphthalene

sulfonate, sodium naphthalene sulphonate, an alkylnaphthalene sulfonate, a sodium

dodecyl sulfate salt, a sodium-neutralized styrene/acrylic acid copolymer and an alpha

olefin sulfonate, or mixtures thereof, or any other agriculturally acceptable anionic

surfactant.

[0034] In a preferred embodiment, the solid herbicide composition comprises flumioxazin at a

concentration of 850.1 g/kg, a first surfactant comprising sodium naphthalene

sulphonate formaldehyde concentrate at a concentration of 40.0 g/kg (e.g. Morwet D

425), a second surfactant comprising an anionic surfactant at a concentration of 30.0

g/kg (e.g. Geropon Ultrasperse), a third surfactant comprising sodium diisopropyl

naphthalene sulfonate at a concentration of 20.0 g/kg (e.g., Solvay Supragil WP), and

sodium sulfate filler at a concentration of 51.4 g/kg.

[0035] According to a second embodiment, the present invention provides a method of

preparing a herbicide composition, the method comprising the steps of:

a.) combining flumioxazin, optionally an agriculturally acceptable filler, and a

surfactant, and

b.) mixing the mixture of step a.) and forming into a solid granule to thereby provide

said herbicide composition,

wherein said flumioxazin is present at a concentration of greater than 750 g/kg in

said herbicide composition.

[0036] It will be appreciated that step (b) may be performed by any method known in the art.

By way of example, the granulation step (b) may be carried out by conventional

processes, such as extruding, which can be performed in any suitable apparatus known

to the person skilled in the art. Methods of granulation that may be used for preparation

of the solid granular herbicide composition provided herein include, but are not limited

to, wet granulation, dry granulation, pan granulation, compaction granulation, centrifugal

granulation, fluidized bed granulation, extrusion granulation and any combination

thereof.

[0037] According to a third embodiment, the present invention provides a herbicide

composition produced by the method according to the second embodiment.

[0038] According to a fourth embodiment, the present invention provides a method of

controlling or inhibiting the growth of and/or killing grass weeds or broadleaf weeds

associated with crops, the method comprising the step of applying a herbicidally

effective amount of a composition according to the first or fourth embodiments.

[0039] The method of the fourth embodiment may further comprise the step of mixing the

composition with a water-containing solvent before the applying step. The mixing may

be carried out using any suitable method or apparatus.

[0040] According to a fifth embodiment, the present invention provides use of a composition

according to the first embodiment as a herbicide in the protection of crops.

Active ingredient

[0041] It will be appreciated that the flumioxazin is present in the solid concentrates at a

concentration of greater than 500 g of the total weight of the composition (i.e., greater

than 500 g/kg; or greater than 50.0 wt.%). In particular embodiments, the flumioxazin is

present at a concentration of 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750,

760,770,780,790,800,810,820,830,840,850,860,870,880,890,900,910,920,

930, 940, 950, 960, 970, 980, 990, 991, 992, 993, 994, 995, 996, 997, 998 or 999 g/kg

(i.e., or the equivalent in wt/wt.%).

[0042] It will be appreciated that the flumioxazin is present in the liquid concentrates at a

concentration of greater than 250 g of the total volume of the composition (i.e., greater

than 250 g/L; or greater than 25.0 wt./volume%). In particular embodiments, the

flumioxazin is present at a concentration of 250, 300, 350, 400, 450, 500, 525, 550, 575,

600,625,650,675,700,725,750,760,770,780,790,800,810,820,830,840,850,

860,870,880,890,900,910,920,930,940,950,960,970,980,990,1000,1010,

1020,1030,1040,1050,1060,1070,1080,1090,1100,1110,1120,1130,1140,1150,

1160, 1170, 1180, 1190, 1200, 1210, 1220, 1230, 1240 or 1250 g/L (i.e., or the

equivalent in wt/volume.%).

[0043] It will be appreciated that other herbicides can be also included in the herbicide

composition according to the invention, provided that the flumioxazin is present at a

concentration of greater than 250 g/kg. For example, other suitable active ingredients

may be selected from the group consisting of: phenmedipham, pendimethalin, trifluralin,

iodosulfuron, mesosulfuron, isoproturon (IPU), chlorotoluron (CTU), flufenacet,

diflufenican (DFF), flurtamone, picolinofen, tribenuron, fenoxaprop, clodinafop,

bromoxynil, ioxynil, flupyrsulfuronmethyl, pinoxaden, pyroxsulam and mixtures and

combinations thereof.

pH indicator

[0044] Advantageously the present application provides a formulation comprising flumioxazin

which addresses at least some of the issues of the prior art, for example by avoiding the

need to continually monitor pH over time (potentially using unreliable and expensive equipment), by including a pH indicator so that there is an immediate and easy visual identification of the pH conditions. Typical pH indicators that may be used with the invention are halochromic chemical compounds that enable the visual determination of the approximate pH of a solution by functioning as chemical detectors for hydronium ions (H30+) or hydrogen ions (H+) under the Arrhenius model. Examples of pH indicators covering the neutral-alkaline range include bromocresol purple, cresol red, neutral red, phenol red and others. Disclosed herein are herbicide formulations comprising flumioxazin and a pH indicator, and methods of preparing and using said herbicide concentration formulation. The present invention provides a means to continually determine, on a convenient visual basis, whether the pH of a solution is in the optimal range after diluting a flumioxazin concentrate or herbicide formulation. This is a significant advance in the art and is convenient, inexpensive, enables the use of a wide range of sources of dilution water and provides a visual confirmation that the herbicide will be effective when applied.

[0045] Preferably the pH indicator is suitable for indicating approximate pH values in the

alkaline and/or neutral range. Preferably the pH indicator can also be suitable for

indicating approximate pH values in the acidic range. Preferably, the pH indicator is

suitable for indicating approximate pH values over a pH range of at least 4-10, at least

6-9, at least 5-6, at least 6-7, at least 7-8, or at least 8-9. Suitably, the pH indicator is

selected from the group consisting of a universal pH indicator, bromocresol purple,

neutral red, cresol red, azolitmin, 2-(2,4-dinitrophenylazo 1-napthol-3,6-disulfonic acid,

bromothymol blue, 6,8-dinitro-2,4-(1H) quinazolinedione, brilliant yellow, phenol red, m

nitrophenol, curcumin, metacresol purple, naphtholphthalein, 4-4'bis(4-amino-1

napthylazo)-2,2'-stilbenedisulfonic acid, thymol blue, p-naphtholbenzein,

cresolphthalein, phenolphthalein, ethyl bis (2,4-dimethylphenyl) ethanoate, any suitable

salt thereof, and any combination thereof. In one embodiment, the indicator is phenol

red (CAS# 143-74-8; yellow at pH : 6.8, pink at pH > 8.2). Phenol red is a useful

alternative to bromocresol purple, neutral red and cresol red.

[0046] In some embodiments, the pH indicator comprises cresol red, which is known to be

coloured yellow below about pH 7.2 and violet above about pH 8.8. In some

embodiments, the cresol red is present in an amount of at least about 0.01 g/L or at

least about 0.01 g/kg of the total weight of the herbicide formulation. More particularly,

the cresol red is suitably present in an amount ranging between about 0.01 g/L to about

20 g/L; or between about 0.01 g/kg to about 20 g/kg.

[0047] In some embodiments, the pH indicator comprises bromocresol purple, which is known

to be coloured yellow below about pH 5.2 and violet above about pH 6.8. In some

embodiments, the bromocresol purple is present in an amount of at least about 0.01 g/L

or at least about 0.01 g/kg of the total weight of the herbicide formulation. More

particularly, the bromocresol purple is suitably present in an amount ranging between

about 0.01 g/L to about 20 g/L; or between about 0.01 g/kg to about 20 g/kg.

[0048] In some embodiments, the pH indicator comprises neutral red, which is known to be

coloured red below about pH 6.8 and yellow above about pH 8.0. In some

embodiments, the neutral red is present in an amount of at least about 0.01 g/L or at

least about 0.01 g/kg of the total weight of the herbicide formulation. More particularly,

the neutral red is suitably present in an amount ranging between about 0.01 g/L to

about 20 g/L; or between about 0.01 g/kg to about 20 g/kg.

[0049] In some embodiments, the pH indicator comprises phenol red, which is known to be

coloured yellow below about pH 6.8 and pink above about pH 8.8. In some

embodiments, the neutral red is present in an amount of at least about 0.01 g/L or at

least about 0.01 g/kg of the total weight of the herbicide formulation. More particularly,

the neutral red is suitably present in an amount ranging between about 0.01 g/L to

about 20 g/L; or between about 0.01 g/kg to about 20 g/kg.

[0050] A non-exhaustive selection of suitable pH indicators is detailed below:

Indicator Chemical name (CAS #) Colour change

common name

Neutral red 3-Amino-7-dimethylamino-2- Yellow above -pH 8

methylphenazine Red below pH -6.8

(CAS# 553-24-2)

Phenol red Phenolsulfonphthalein Yellow below pH -6.5

(CAS# 143-74-8) Red above pH -8

Cresolred o-Cresolsulfonphthalein Yellow at neutral to acid pH's

(CAS# 1733-12-6) Red/purple for pH -8.5 and above

Bromocresol 5',5"-dibromo-o-cresolsulfophthalein Yellow at below pH -5.2

purple (CAS: 115-40-2) Purple at above pH -6.8

[0051] The term "pH indicator" as used herein refers to any compound or composition suitable

for determining the approximate pH of a liquid. Such pH indicators in solution typically

have known colours associated with particular pH ranges, with a change in colour

associated with a change in pH of the solution. The pH indicator of the herbicide

formulations herein may comprise one pH indicator, or may comprise two or more pH

indicators. The pH indicator may comprise a halochromatic pH indicator. The pH

indicator may comprise any halochromatic compound suitable for determining the

approximate pH of a liquid.

[0052] In some embodiments the pH indicator is suitable for indicating approximate pH values

in the alkaline and/or neutral range. In some embodiments the pH indicator is suitable

for indicating approximate pH values in the acidic range. In some embodiments the pH

indicator is suitable for indicating approximate pH values in the alkaline, neutral and

acidic range. In some embodiments, the pH indicator is suitable for indicating

approximate pH values in a pH range of between at least about 0-14, at least about 1

13, atleastabout4-10, atleast about6-9, atleastabout5-6, at leastabout6-7, at least

about 7-8, at least about 8-9, or any range therein. In some embodiments the pH indicator can be a universal pH indicator. In some embodiments, the pH indicator is selected from the group consisting of a universal pH indicator, bromocresol purple, neutral red, cresol red, azolitmin, 2-(2,4-dinitrophenylazo 1-napthol-3,6-disulfonic acid, bromothymol blue, 6,8-dinitro-2,4-(1H) quinazolinedione, brilliant yellow, phenol red, m nitrophenol, curcumin, metacresol purple, naphtholphthalein, 4-4'bis(4-amino-1 napthylazo)-2,2'-stilbenedisulfonic acid, thymol blue, p-naphtholbenzein, cresolphthalein, phenolphthalein, ethyl bis (2,4-dimethylphenyl) ethanoate, any suitable salt thereof, and any combination thereof.

[0053] In some embodiments, the pH indicator comprises cresol red. Cresol red is the common

name for o-cresolsulfonephthalein (CAS# 1733-12-6). Cresol red is a triarylmethane dye

and a pH indicator. Cresol red transitions from yellow at pH 7.2 to reddish-purple at pH

8.8. In some embodiments, the cresol red is present in an amount of at least about 0.01

g/kg or at least about 0.01 g/L of the total weight of the herbicide formulation. In some

embodiments, the cresol red is suitably present in an amount ranging between about

0.01 g/kg to about 20 g/kg; or between about 0.01 g/L to about 20 g/L of the total weight

of the herbicide formulation. In some embodiments, the cresol red is present at a

concentration of about 0.5 g/kg of the total weight of the herbicide formulation. In some

embodiments, the cresol red is present at a concentration of about 2 g/kg of the total

weight of the herbicide formulation.

[0054] In some embodiments, the pH indicator comprises bromocresol purple. Bromocresol

purple is the common name for 5',5"-Dibromo-o-cresolsulfonphthalein (CAS# 115-40-2).

Bromocresol purple is a dye of the triphenylmethane family (triarylmethane dyes) and a

pH indicator. Bromocresol purple is coloured yellow below pH 5.2, and violet above pH

6.8. In some embodiments, the bromocresol purple is present in an amount of at least

about 0.01 g/kg or at least about 0.01 g/L of the total weight of the herbicide formulation.

In some embodiments, the bromocresol purple is suitably present in an amount ranging

between about 0.01 g/kg to about 20 g/kg; or between about 0.01 g/L to about 20 g/L of

the total weight of the herbicide formulation. In some embodiments, the bromocresol

purple is at a concentration of about 1.0 g/kg of the total weight of the herbicide formulation. In some embodiments, the bromocresol purple is at a concentration of about 1.1 g/kg of the total weight of the herbicide formulation. In some embodiments, the bromocresol purple is at a concentration of about 1.5 g/kg of the total weight of the herbicide formulation. In some embodiments, the bromocresol purple is at a concentration of about 2.0 g/kg of the total weight of the herbicide formulation.

[0055] In some embodiments, the pH indicator comprises neutral red. Neutral red is the

common name for 3-amino-7-dimethylamino-2-methylphenazine hydrochloride (CAS#

553-24-2). Neutral red is a eurhodin dye and a pH indicator. Neutral red acts as a pH

indicator, transitioning from red at pH 6.8 to yellow at pH 8.0. In some embodiments, the

neutral red is present in an amount of at least about 0.01 g/kg or at least about 0.01 g/L

of the total weight of the herbicide formulation. In some embodiments, the neutral red is

suitably present in an amount ranging between about 0.01 g/kg to about 20 g/kg; or

between about 0.01 g/L to about 5 g/L of the total weight of the herbicide formulation. In

some embodiments, the neutral red is present at a concentration of about 1.0 g/kg of

the total weight of the herbicide formulation. In some embodiments, the neutral red is

present at a concentration of about 2.9 g/L of the total weight of the herbicide

formulation.

[0056] In some embodiments, the pH indicator comprises phenol red. Phenol red is the

common name for phenolsulfonphthalein (CAS# 143-74-8). Phenol red is a water

soluble dye and a pH indicator. Phenol red transitions from yellow at pH 6.8 to bright

pink (fuchsia) at pH 8.2. In some embodiments, the phenol red is present in an amount

of at least about 0.01 g/kg or at least about 0.01 g/L of the total weight of the herbicide

formulation. In some embodiments, the cresol red is suitably present in an amount

ranging between about 0.01 g/kg to about 10 g/kg; or between about 0.01 g/L to about

20 g/L of the total weight of the herbicide formulation. In some embodiments, the cresol

red is present at a concentration of about 0.9 g/kg of the total weight of the herbicide

formulation. In some embodiments, the cresol red is present at a concentration of about

1.2 g/L of the total weight of the herbicide formulation. In some embodiments, the cresol red is present at a concentration of about 1.5 g/kg of the total weight of the herbicide formulation.

[0057] In some embodiments, in relation to herbicide formulations such as soluble granules,

soluble powders, or soluble liquid concentrates, the pH indicator (e.g., bromocresol

purple, cresol red or neutral red) may be present in an amount from about 0.01 g/L to

about 20 g/L or any range therein such as, but not limited to, about 0.01 g/L to about 1.5

g/L, about 0.1 g/L to about 10 g/L, about 0.1 g/L to about 3 g/L; or between about 0.01

g/kg to about 20 g/kg or any range therein such as, but not limited to, about 0.01 g/kg to

about 1.5 g/kg, about 0.1 g/kg to about 20 g/kg, about 0.1 g/kg to about 3 g/kg, of the

herbicide formulation. In particular embodiments of the present invention, the pH

indicator is present in an amount of about 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4,

0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,

1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7,

3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8,

5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9,

8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10,

20 g/L, or any range therein, or about 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4,

0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,

1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7,

3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8,

5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9,

8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10,

20 g/kg, or any range therein, of the herbicide formulation.

[0058] The ratio of the total amount of flumioxazin to pH indicator (e.g., bromocresol purple,

neutral red, phenol red or cresol red) may be between about 100000:1 and about 30:1

or any range therein, such as between 10000:1 and 100:1, or between 1000:1 and

100:1, or between 100:1 and 30:1, or it may be about 100000:1, 90000:1, 80000:1,

70000:1, 60000:1, 50000:1, 40000:1, 30000:1, 20000:1, 10000:1, 9000:1, 8000:1,

7000:1, 6000:1, 5000:1, 4000:1, 3000:1, 2000:1, 1000:1, 900:1, 800:1, 700:1, 600:1,

500:1, 400:1, 300:1, 200:1, 100:1, 95:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1,

50:1, 45:1, 40:1, 35:1, 30:1, or any range therein in the herbicide formulation.

[0059] In some embodiments, the pH of the composition is adjusted by the addition of a

suitable acid. The term "suitable acid" as used herein refers to any acid or any other

compound suitable for lowering the pH of a solution that is agriculturally acceptable. In

some embodiments, the suitable acid is selected from the group consisting of carbon

dioxide, carbonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid,

acetic acid, butyric acid, propionic acid, citric acid, lactic acid, pyruvic acid, any salt or

solution thereof, or any combination thereof. In some embodiments the suitable acid

can further comprise water or any other neutral solvent. In some embodiments, the

suitable acid is a commercially available pH adjustment solution.

[0060] In some embodiments, the pH of the composition is adjusted by the addition of a

suitable base. The term "suitable base" as used herein refers to any base or any other

compound suitable for raising the pH of a solution that is agriculturally acceptable. In

some embodiments, the suitable base is selected from the group consisting of sodium

hydroxide, sodium carbonate, calcium hydroxide, magnesium hydroxide, potassium

hydroxide, ammonia, any salt or solution thereof, or any combination thereof. In some

embodiments the suitable base can further comprise water or any other neutral solvent.

In some embodiments, the suitable base is a commercially available pH adjustment

solution.

[0061] In some embodiments, the pH is adjusted such that the pH indicator visually indicates

that the composition is of neutral or mildly acidic pH. In some embodiments, the pH is

adjusted such that the pH indicator visually indicates that the pH of the composition in

the range of between about 4 and about 10, or between about 5.5 and 9.5, or between

about 5.5 and 8. In some embodiments the pH is adjusted such that the pH indicator

visually indicates that the pH of the composition is below about 9, below about 8, or

below about 7. In particular embodiments of the present invention, the pH is adjusted

such that the pH indicator visually indicates that the pH of the composition is less than 4

or about4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6,4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8,

5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9,

8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10,

or greater than 10, or any range therein.

[0062] Suitably, the method of this aspect further includes the initial step of mixing the

herbicide formulation with water or a water-containing liquid.

Agriculturally acceptable filler

[0063] The herbicide composition of the present invention includes an optional filler (or carrier),

and preferably a solid filler. It will be appreciated that the filler may also act as a binder

which functions to at least partially bind the ingredients or components of the

composition of the invention into a granular or pelleted form, which preferably resists

attrition and will not rapidly degrade, and therefore substantially maintains particle size

during handling. To this end, the optional filler may facilitate the formulation of a

granular or pelleted composition that typically requires no further preparation,

processing, dilution, combination etc before application thereof to a target area. The

filler may also act as a complexing agent which can bind to metal ions, either within the

formulation or when dispersed.

[0064] Non-limiting examples of fillers include: (i) pulverized natural minerals, such as kaolin

clay, talc, chalk, quartz, and diatom earth; (ii) pulverized minerals, such as dispersed

silica (amorphous), aluminium oxide, sodium sulfate and silicate; (iii) size reduced and

fractionated natural stone materials such as calcite, marble, sepiolite and dolomite; (iv)

synthetic granulates from inorganic and organic powders such as from polymers; and

(v) granulates from organic materials, such as coconut shells, corn cobs and tobacco

stems. Preferred fillers are selected from the group consisting of: silica (amorphous),

sodium sulfate, talc, and calcium chloride dihydrate.

[0065] Other examples of fillers, which also tend to have a binding effect, include calcium

stearate, polyhydroxymethyl urea, methyl cellosolve (2-methoxyethanol),

polyvinylpyrrolidone, polyvinyl alcohol, polyacrylates, polymethacrylates, natural waxes,

chemically modified waxes and synthetic waxes, sugars, starch, alginates, agar,

lignosulphonates and gum arabic.

[0066] In particular embodiments, one or a plurality of fillers are present in the herbicide

composition of the invention at a concentration of between about 10 g/kg and up to 250

g/kg (e.g., about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,

100, 110, 120, 130, 140, 150, 160,170, 180, 190,200,210,220,230,240,and 250

g/kg, and any range therein) by weight of the herbicide composition of the invention.

The skilled person will appreciate that suitable amounts of the filler can be chosen to

suit the particular application in which the herbicide composition of the invention is to be

used. Particular concentrations may be selected from the group consisting of: about 35,

50, 125, 135 and 185 g/kg.

Auxiliary agents

[0067] One or more additional auxiliary agents, such adjuvants, dispersants, disintegrating

agents, lubricants, wetting agents, preservatives, parting agents, colouring agents (e.g.,

dyes) and the like, can also be added where desired to modify the properties of the

herbicide composition of the invention as required. Additionally, it will be appreciated

that the herbicide composition of the invention may further include, for example, an

emetic agent and/or an embittering agent, such as Bitrex@ (denatonium benzoate), to

thereby prevent or inhibit other animals, such as humans, domestics pets, birds and the

like from ingesting the herbicide composition of the invention.

[0068] In particular embodiments, the herbicide composition of the invention further includes a

bird repellent agent. The bird repellent agent can be any known in the art, including, for

example, aluminium ammonium sulphate, an anthranilate (and related compounds e.g.,

methyl anthranilate, isobutyl anthranilate, ethyl anthranilate, isobutyl N-methyl

anthranilate and methyl N-methyl anthranilate) and a fatty acid (and related

compounds).

[0069] Suitable preservatives may include, for example, 1,2- benzisothiazolin-3-one and/or 2

methyl-2H-isothiazol-3-one or sodium benzoate or benzoic acid, epoxidized soybean oil,

epoxidized linseed oil, ethylene glycol and any combination thereof.

[0070] Suitable lubricants may include, for example, artificial and natural fats and oils, such as

calcium stearate, liquid paraffin, polyethylene glycol as well as inorganic lubricants such

as talc.

[0071] In one embodiment, substances which are suitable as complexing agent are included in

the herbicide composition of the invention. Suitable complexing agent are selected from

EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), EDDHA

(ethylenediaminedi(ortho-hydroxyphenyl)acetic acid), DTPA

(diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylenediaminetriacetic acid),

preferably ethylenediaminetetraacetic acid and/or diethylenetriaminepentaacetic acid.

One preferred complexing agent is disodium EDTA dehydrate. Substances which are

suitable as polymeric complexing agents are polyacrylic acid and its salts, in particular

the sodium salts, polymethacrylic acid and its salts, in particular the sodium salts,

polymaleic acid, prepared for example by hydrolyzing polymaleic anhydride, in particular

the sodium salts, polyvinylpyrrolidone, acrylic acid/maleic acid copolymers, in particular

the sodium salts, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone and C2o-a

olefin graft copolymers, vinylpyrrolidone/acrylic acid copolymers,

vinylpyrrolidone/dimethylaminoethyl acrylate copolymers, copolymers of methyl vinyl

ether and maleic acid anhydride (derivatives), styrene/maleic anhydride copolymers,

polyaspartic acid and its salts, poly-p-vinylbenzenesulfonic acid and its salts,

copolymers of ethylene and/or propylene and/or isobutene and (meth)acrylic acid,

modified starches, modified celluloses, for example carboxymethylcellulose, alginates,

lignin derivatives such as lignosulfonates, chitosans, modified polysaccharides,

phenolsulfonic acid/formaldehyde condensates, and naphthalenesulfonic

acid/formaldehyde condensates.

[0072] In preferred embodiments, one or more complexing agents are present in the herbicide

composition of the invention at a concentration of between about 10 g/kg and up to 150

g/kg (e.g., about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,

100, 110, 120, 130, 140, and 150 g/kg, and any range therein) by weight of the

herbicide composition of the invention. In particular embodiments, the complexing agent may be disodium EDTA dihydrate, present in the herbicide at a concentration of about

30 g/kg.

[0073] By way of example, the auxiliary agent may comprise filling or carrying agents such as

clay, kaolin, diatomaceous earth, pyrophyllite, fertilizers or fertilizing agents (e.g.

potassium sulphate), synthetic silicas, mineral earths such as silicic acid, silica gels,

silicates, talc, sub-bentonites, bentonites, attapulgites, limestone, lime, chalk, bole,

less, clay, dolomite, montmorinonites, bauxite, gums (e.g., gum arabic or xantham

gum), hydrated or calcined aluminas, prophyllites, vermiculites, synthetic organic

polymers, calcium silicate, calcium sulfate, magnesium sulfate, magnesium oxide and

the like; binding agents such as sugars (e.g., sucrose), carbon, charcoal, wood flour,

ground corn cobs, synthetic organic polymers (e.g., polyvinyl alcohol), lignins and

derivatives thereof, polycarboxylates and derivatives thereof, and the like; fertilizing

agents such as ammonium-, phosphate-, sodium-, zinc-, copper-, manganese-, iron

and/or nitrogen- based fertilizers or fertilizing agents, boric acid, potash, and the like;

polymers such as synthetic polymers (e.g., polyvinyl alcohol, polystyrene,

polyacrylamide, polymethylacrylate, polyamides, polyesters, polyanhydrides,

polyurethanes, amino resins and polycyanoacrylates etc.), natural polymers including

polysaccharides (e.g., cellulose, agarose, dextran, alginates, carrageenans, starch,

chitosan) and proteins (e.g., gelatin and albumin) and the like; emulsifiers such as

polyoxyethylene esters or ethers (e.g., castor oil polyoxyethyl ether, alkyl phenyl

polyethyl ether, etc.), Turkish red oil, diglycerin sodium laurate, sodium hydrogen

phosphate and the like; stabilizing agents, sustained release agents, anti-drift agents

such as polysaccharide gum, alginate derivatives, hydroxyethyl cellulose, sodium

polyacrylate, polyacrylamide, fatty acid alkyl ammonium salts, sodium polyacrylate and

the like; antifoaming agents such as emulsified silicone oil, high-carbon alcohol fatty

acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether,

polyoxyethylene polyoxypropylene alcohol ether, polyoxygen. Acrylglycerol ether,

polydimethylsiloxane and the like; adjuvants, preservatives, colouring agents (e.g., dyes), odourants, synergists, solvents, embittering agents, and other deterrents and the like, as are known in the art.

[0074] In one particular embodiment, the auxiliary agent comprises a fertilizing agent. More

particularly, the auxiliary agent comprises potassium sulphate. In some embodiments,

the auxiliary agent further comprises one or more auxiliary agents selected from the

group consisting of a natural polymer, a silicate, a gum, a sugar and a synthetic organic

polymer. More specifically, in some embodiments the auxiliary agent further comprises

one or more auxiliary agents selected from the group consisting of cellulose, talc, gum

arabic, sucrose, and polyvinyl alcohol.

[0075] In one particular embodiment, the auxiliary agent comprises a sugar, more particularly,

the auxiliary agent comprises sucrose.

[0076] In one particular embodiment the auxiliary agent comprises a natural polymer, more

particularly, the auxiliary agent comprises cellulose.

[0077] In one particular embodiment the auxiliary agent comprises an emulsifier, more

particularly, the auxiliary agent comprises sodium hydrogen phosphate.

[0078] Where present, such auxiliary agents may be used in isolation or in combination as a

mixture of two, three, four, five or more auxiliary agents. In one particular embodiment,

the solvent comprises first and second auxiliary agents. It will be appreciated that the

first and second solvents may be or comprise any auxiliary agent known in the art

and/or as defined above.

[0079] For the present aspect, the ratio of the first auxiliary agent to the second auxiliary agent

may suitably be between 1 and 20 parts of the first auxiliary agent, and between 1 and

20 parts of the second auxiliary agent. For example, the ratio may be about 20:1; 19:1,

18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2.9:1,

2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1,

1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4:, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9,

1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8,

1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20 and any range

therein.

[0080] For the above aspects, where present, the auxiliary agent of the herbicide formulations,

including soluble granule, soluble powder and soluble liquid concentrate formulations,

may be present in an amount from about 1 g/kg to about 100 g/kg or any range therein

such as, but not limited to, about 1 g/kg to about 20 g/kg, about 20 g/kg to about 80

g/kg, or about 80 g/kg to about 100 g/kg of the herbicide formulation. In particular

embodiments of the present invention, the auxiliary agent is present in an amount of

about1,2,3,4, 5,6,7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19,20,21,22,23,24,

25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,

48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,

71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,

94, 95, 96, 97, 98, 99, 100, g/kg, or any range therein, of the herbicide formulation.

[0081] Further to the above, the auxiliary agent provided herein is preferably an agriculturally

acceptable auxiliary agent. The term "agriculturally acceptable auxiliary agent" as used

herein refers to an auxiliary agent that is not unacceptably damaging to a plant and/or

its environment, and/or not unsafe to the user or others that may be exposed to the

auxiliary agent when used as described herein.

[0082] One or more additional auxiliary agents, can also be added where desired to modify the

properties of the herbicide formulation, including the soluble granule formulation, soluble

powder formulation, and soluble liquid concentrate formulation as required. In some

embodiments, one or more anti-freezing agents, a thickening agents and/or biocidal

agents are included. In some embodiments, one or more acidifying agents are included,

in order to pre-emptively avoid or lessen alkaline hydrolysis of flumioxazin once

prepared (diluted) for use.

Surfactants

[0083] One or a plurality of agriculturally acceptable surfactants are present in the herbicide

composition of the invention at a concentration of between about 10 g/kg and up to 250

g/kg (e.g., about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,

100, 110, 120, 130, 140, 150, 160, 170, 180, 190,200,210,220,230,240and 250

g/kg, and any range therein) by weight of the herbicide composition of the invention.

The skilled person will appreciate that suitable types and amounts of surfactants can be

chosen to suit the particular application in which the herbicide composition of the

invention is to be used. It will be appreciated that the surfactant fulfils the general roles

of wetting and dispersing the active ingredient(s), which are generally insoluble in water,

or have a very low solubility. Additionally, the surfactant can be chosen to additionally

assist with a binding role to bind the granule together at least initially and prior to

exposure to water. Particular concentrations may be selected from the group consisting

of: about 60, 70, 80, and 90 g/kg.

[0084] The surfactant of the herbicide compositions of the invention disclosed herein may

comprise one surfactant, or may comprise two or more surfactants. The surfactant may

be an anionic surfactant, or it may be a non-ionic surfactant, as discussed further below.

[0085] For the present invention, the surfactant is suitably selected from the group consisting of

non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants,

cation-anion composite surfactants and any combination thereof. Suitable non-ionic

surfactants may include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl

ethers, polyoxyethylene polyoxypropylene ethers, polyoxyethylene alkyl esters,

polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene block

copolymers, sorbitan alkyl esters, higher fatty acid alkanolamides and any combination

thereof. Suitable cationic surfactants may include alkylamine salts, quaternary

ammonium salts and combinations thereof. Further, suitable anionic surfactants may

include naphthalenesulfonic acid polycondensate, alkenylsulfonate,

naphthalenesulfonate, alkyl naphthalene sulfonate, alpha olefin sulfonate, formalin

condensate of a naphthalenesulfonate, formadehyde condensate of an

alkylnaphthalenesulfonate, lignin sulfonate, alkylarylsulfonate, alkylaryl sulfonate

sulfate, polystyrene sulfonate, polycarboxylate, polyoxyethylenealkyl ether sulfate,

polyoxyethylenealkylaryl ether sulfate, alkylsulfosuccinate, alkyl sulfate, alkyl ether

sulfonate, a higher fatty acid alkali salt and any combination thereof.

[0086] Other agriculturally acceptable surfactants may be chosen from the group consisting of

calcium alkylbenzenesulfonate, alkylphenol ether sulphate/alkylamine ethoxylate salt, alcohol ether sulphate/alkylamine ethoxylate salt, alkylphenol alkoxylates, fatty acid alkoxylates, alkoxylated triglycerides and EO/PO diblock materials, wherein alkoxylate includes ethoxylate, propoxylate and mixed ethoxylate-propoxylate, including multi block ethoxylate/propoxylate materials.

[0087] In certain preferred embodiments, the one or more surfactants to be included in the

herbicide composition of the invention, include an anionic surfactant. As generally used

herein, the term "anionic surfactant" refers to a surfactant comprising, as ionic or

ionizable groups, only anionic groups. Such anionic groups may include, for example,

C02H, -C02, -SO3H, -S03, -OSO3H, -OS03,-H2PO3, -HP03, -P 2 3 -, -H2PO2,

=HPO2, -HPO2, =P0 2 -, =POH, and =PO- groups. Suitable anionic surfactants may

include those hereinbefore described. Such anionic surfactants may be used alone or in

combination as a mixture of two, three, four, five or more anionic surfactants. In certain

embodiments, the one or more surfactants to be included in the herbicide composition

of the invention, may comprise a non-ionic surfactant. As generally used herein, the

term "non-ionic surfactant" refers to a surfactant that does not contain or comprise an

ionic or ionizable group. Suitable non-ionic surfactants may include those hereinbefore

described. Such non-ionic surfactants may be used alone or in combination as a

mixture of two, three, four, five or more non-ionic surfactants. In certain embodiments,

the surfactant may comprise a combination of one or more anionic surfactant and one

or more non-ionic surfactant. In such embodiments, the ratio by weight of total anionic

surfactant to total non-ionic surfactant may be between about 20:1 and about 1:20, or

between 10:1 and 1:10, or between 15:1 and 1:1, or between 5:1 and 1:15, or between

5:1 and 1:5, or between 3:1 and 1:1, or between 2:1 and 1:2, or between 2:1 and 1:3, or

about 1:1 or any range therein, or it may be about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1,

14:1, 13:1, 12:1, 11:1, 10:1;3,:1;4:1 :1, 6:1 , 51:17, :1 2.9:1,2.8:1, 2.7:1, 2.6:1,

2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1,

1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4:, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2,

1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11,

1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, or any range therein.

[0088] It will be appreciated that the surfactant may be any suitable surfactant known in the art.

Exemplary surfactants include an alkylphenol alkoxylate (e.g., Termul 200), a

polyoxyalkylene ether (e.g., Termul 203), an alkoxylated oil (e.g., -54 x ethoxylated

(e.g., Termul 1285)), an alkylphenol alkoxylate (e.g., -10 x ethoxylated (e.g.,

TericN10)), an alkoxylated alcohol (Alcohol C12 - C15, -23 x ethoxylated (e.g. Teric

12A23); Alcohol C12, -3 x ethoxylated (e.g. Surfactant 12A3)), an alkoxylated polyaryl

phenol (e.g., Tristyryl Phenol, -16 x ethoxylated (e.g. TSP15)), an alkoxylated block co

polymer (Ethoxylate-Propoxylate copolymer (e.g. Teric PE64)), an

alkylbenzenesulphonate (e.g., Calcium C10-16 alkylbenzyl sulphonate, branched or

linear chain in solvent (e.g. Ninate 60E, NANSA EVM70/2E, Kemmat HF60)), an alkyl

naphthalene sulfonate (e.g., Solvay Gerapon SC/213), an alpha olefin sulfonate (e.g.,

Solvay Gerapon L Wet F), an alcohol ether sulphate (e.g. Toximul TANS-5), an

alkylamine ethoxylate (e.g. Toximul TAABS-5), a silicone polymer, inclusive of

polysiloxanes (e.g., Evonik Break-Thru OE 446, Evonik Break-Thru AF 9903, Jiangxi

Tiansheng QS-302) and silicone glycol copolymers (e.g., Xiameter OFX-5211), a block

co-polymer (e.g., Teric PE64), an alkoxylated nonylphenol (e.g., Teric N10), an

alkoxylated alcohol (e.g., Teric BL8), an alkyl polyglucoside (e.g., Croda AL-2575), an

ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate (branched or

linear in solvent), a branched alcohol ether sulphate, a tallowamine alkoxylated salt, and

a mineral oil (e.g., Rhodoline DF5888).

[0089] In particular embodiments, the surfactant is selected from the group consisting of an

alkylphenol alkoxylate (e.g., Termul 200), a polyoxyalkylene ether (e.g., Termul 203), an

alkylbenzenesulphonate (e.g., Ninate 60E, NANSA EVM70/2E, Kemmat HF60), an

alkoxylated styryl phenol (e.g., alkoxylated monostyryl phenols, alkoxylated distyryl

phenols, alkoxylated tristyryl phenols, such as Termul 3150), an alkoxylated oil, such as

an alkoxylated vegetable oil (e.g., Termul 1284 and Termul 1285) and any combination

thereof.

[0090] More particularly, the surfactant can be selected from the group consisting of an

alkoxylated alkylphenol (e.g., Termul 200), an alkyl polyoxyalkalene ether (e.g., Termul

203), calcium C10-16 alkylbenzyl sulphonate (branched or linear chain in solvent) (e.g.,

Ninate 60E, NANSA EVM70/2E, Kemmat HF60), an ethoxylated tristyryl phenol (e.g.,

Termul 3150), an alkyl naphthalene sulfonate (e.g., Solvay Gerapon SC/213), an alpha

olefin sulfonate (e.g., Solvay Gerapon L Wet F) and any combination thereof.

[0091] Particular preferred surfactants may be chosen from the group consisting of: sodium

naphthalene sulphonate formaldehyde concentrate, sodium naphthalene sulphonate,

sodium diisopropyl naphthalene sulfonate, sodium-neutralized styrene/acrylic acid

copolymer and dodecyl sulphate (sodium salt).

Application rate

[0092] For control of various broadleaved weeds and grasses, the herbicide composition of the

invention is preferably applied at a rate of around 5 to 1000 g/Ha. For example, 10, 20,

30,40,50,60,70,80,90,100,120,140,160,180,200,250,300,350,400,450,500,

550, 600, 650, 700, or 750, 800, 850, 900, 950 or 1000 g/Ha of the composition of the

invention. Given the concentration of the flumioxazin is present in the herbicide

composition of the invention at a concentration of greater than 250 g/L for liquid

concentrates and greater than 500 g/kg for solid concentrates, it will be appreciated that

an application rate of, say, 100 mL/ha or 100 g/Ha equates to 25 g/Ha or 50 g/Ha

respectively of flumioxazin active ingredient.

Viscosities

[0093] It will be understood that it is desirable for liquid forms of the herbicide formulation,

including liquid suspension concentrates described herein to be readily or easily

pumped or poured from a storage vessel. Preferably, liquid herbicide formulations have

a viscosity at room temperature (i.e., 200C) of no more than 2000 cPs (e.g., 1, 5, 10, 20,

30,40,50,100,200,300,400,500,600,700,800,900,1000,1100,1200,1300,1400,

1500, 1600, 1700, 1800, 1900, 2000 cPs and any range therein), as viscosities above

this typically make it difficult or impractical to pump or pour the formulation. Preferably, the liquid herbicide formulations of the invention have a viscosity at room temperature of aboutor less than 800 cPs.

Herbicide formulation types

[0094] It is envisaged that the herbicide formulation may take the form of any herbicide

formulation known in the art. Exemplary formulations include oil-miscible liquids, soluble

concentrates, soluble granules, soluble powders, soluble liquids, ultra-low-volume (ULV)

liquids, emulsifiable concentrates, emulsions including oil-in-water and micro-emulsions,

suspension concentrates, suspoemulsions, solutions, dusts, baits, granules, pellets,

wettable powders, flowables, water-dispersible granules, microencapsulated materials,

and aerosols.

[0095] In some embodiments, the herbicide formulations described herein, including water

dispersible granular and wettable powder herbicide formulations may be presented in

water soluble packets to avoid any handling issues noting that the product is an

organophosphate insecticide with a degree of toxicity. Such water-soluble packets

containing said soluble granular or powdered herbicide formulation may be prepared

according to any suitable method known or used in the art.

DEFINITIONS

[0096] In describing and claiming the present invention, the following terminology will be used

in accordance with the definitions set out below. It is also to be understood that the

terminology used herein is for the purpose of describing particular embodiments of the

invention only and is not intended to be limiting.

[0097] Unless defined otherwise, all technical and scientific terms used herein have the same

meaning as commonly understood by one having ordinary skill in the art to which the

invention pertains.

[0098] Unless the context clearly requires otherwise, throughout the description and the claims,

the terms "comprise", "'comprising", and the like are to be construed in an inclusive

sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of

"including, but not limited to". For example, a composition, mixture, process or method

that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

[0099] The transitional phrase "consisting of" excludes any element, step, or ingredient not

specified. If in the claim, such would close the claim to the inclusion of materials other

than those recited except for impurities ordinarily associated therewith. When the

phrase "consisting of" appears in a clause of the body of a claim, rather than

immediately following the preamble, it limits only the element set forth in that clause;

other elements are not excluded from the claim as a whole.

[0100] The transitional phrase "consisting essentially of" is used to define a composition,

process or method that includes materials, steps, features, components, or elements, in

addition to those literally disclosed, provided that these additional materials, steps,

features, components, or elements do not materially affect the basic and novel

characteristic(s) of the claimed invention. The term "consisting essentially of" occupies a

middle ground between "comprising" and "consisting of".

[0101] Where applicants have defined an invention or a portion thereof with an open-ended

term such as "comprising", it should be readily understood that (unless otherwise

stated) the description should be interpreted to also describe such an invention using

the terms "consisting essentially of"or "consisting of." In other words, with respect to

the terms "comprising", "consisting of", and "consisting essentially of", where one of

these three terms is used herein, the presently disclosed and claimed subject matter

may include the use of either of the other two terms. Thus, in some embodiments not

otherwise explicitly recited, any instance of "comprising" may be replaced by "consisting

of" or, alternatively, by "consisting essentially of".

[0102] Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to

an exclusive or. For example, a condition A or B is satisfied by any one of the following:

A is true (or present) and B is false (or not present), A is false (or not present) and B is

true (or present), and both A and B are true (or present).

[0103] Also, the indefinite articles "a" and "an" preceding an element or component of the

invention are intended to be non-restrictive regarding the number of instances (i.e., occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

[0104] Other than in the operating examples, or where otherwise indicated, all numbers

expressing quantities of ingredients or reaction conditions used herein are to be

understood as modified in all instances by the term "about". The examples are not

intended to limit the scope of the invention. In what follows, or where otherwise

indicated, "%" will mean "weight %", "ratio" will mean "weight ratio" and "parts" will mean

"weight parts".

[0105] The terms "predominantly" and "substantially" as used herein shall mean comprising

more than 50% by weight, unless otherwise indicated.

[0106] The recitation of a numerical range using endpoints includes all numbers subsumed

within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5).

[0107] The terms "preferred" and "preferably" refer to embodiments of the invention that may

afford certain benefits, under certain circumstances. However, other embodiments may

also be preferred, under the same or other circumstances. Furthermore, the recitation of

one or more preferred embodiments does not imply that other embodiments are not

useful, and is not intended to exclude other embodiments from the scope of the

invention.

[0108] As used herein, the terms "granule" or "granular" refer to solid pellets, granules, grains

and the like. Such granules can include those in which there is no discreet core or

coatings (i.e., a granule having a substantially uniform composition throughout) or those

having a discreet core and a coating thereover.

[0109] By "agriculturally acceptable filler" it is meant any substance which is agriculturally inert

and has no significant detrimental effect on, for example, the soil, equipment, desirable

plants, or the agronomic or agricultural environment. Such a filler can also be used to

aid the dispersion of the active ingredient without impairing the active ingredient's

effectiveness, and can be used to reduce the overall cost of the formulation and can be

used as a binder to assist in binding the other ingredients of the formulation together.

Suitable carriers are preferably solid carriers such as those described in more detail

above.

[0110] The terms "target area", "locus" or "space" refer to any area, location or habitat where a

herbicide is needed or expected to be needed.

[0111] The term "agriculturally acceptable solvent" as used herein refers to a solvent that is not

unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user

or others that may be exposed to the solvent when used as described herein.

[0112] The complete disclosures of the patents, patent documents and publications cited

herein are incorporated by reference in their entirety as if each were individually

incorporated.

EXAMPLES

[0113] The present invention will now be described with reference to the following examples

which should be considered in all respects as illustrative and non-restrictive.

[0114] A number of embodiments of flumioxazin water dispersible granules are provided

below, including ranges of active ingredient, types and concentrations of surfactants,

and types and concentrations of fillers.

EXAMPLE 1

[0115] Recipe for a nominally 900g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 1 and, as shown in Table 2, has been determined via assay

as having adequate active ingredient concentration at the point of manufacturing, and

again after accelerated aging to approximate two years of shelf life.

[0116] The composition of Example 1 is as follows in Table 1.

Table 1:

Ingredient Role Concentration Flumioxazin Active herbicidal 908.7g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 901.4g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 45.1g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Sodium naphthalene sulphonate Surfactant 12.1g/kg

(CAS# Proprietary; e.g. Morwet EFW) Silica, amorphous Filler 34.1g/kg (CAS# 7631-86-9) (to 1000g/kg total)

[0117] Chemical and physical parameters of Example 1 is as follows in Table 2.

Table 2:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 907.0g/kg 908.0g/kg Require: 875g/kg Flumioxazin 925g/kg Wet sieve: 0.02% 0.02% Require: 2% retained on a 75pm sieve. Dispersibility 97.4% 98.0% Require: 60%:5 % residues 105% Suspensibility 81.3% 83.8% Require: 60%:5 % residues 105% pH1% 7.2 6.8 Nominally: 5.5 to 9.5 Persistent foaming 10mL 5mL Require: 5 60mL foam after 1 min Attrition resistance 99.8% 99.5% Require: 98% passes thru 4mm sieve

EXAMPLE 2

[0118] Recipe for a nominally 850g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 3 and, as shown in Table 4, has been determined via assay

as having adequate active ingredient concentration at the point of manufacturing and

again after accelerated aging to approximate two years of shelf life.

[0119] The composition of Example 2 is as follows in Table 3.

Table 3:

Ingredient Role Concentration Flumioxazin Active herbicidal 858.6g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 850.1g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 40.0g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Anionic surfactant Surfactant 30.0g/kg (CAS# proprietary; e.g. Geropon Ultrasperse) Sodium diisopropyl naphthalene sulfonate Surfactant 20.0g/kg (CAS# 1322-93-6; e.g. Solvay Supragil WP) Sodium sulfate Filler 51.4g/kg (CAS# 7757-82-6) (to 1000g/kg total)

[0120] Chemical and physical parameters of Example 2 is as follows in Table 4.

Table 4:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 850.2g/kg 853.2g/kg Require: 825g/kg Flumioxazin 875g/kg Wet sieve: 0.01% 0.01% Require: 2% retained on a 75pm sieve. Dispersibility 98.8% 97.5% Require: 60%:5 % residues 105% Suspensibility 86.3% 87.4% Require: 60%:5 % residues 105% pH1% 7.5 7.8 Nominally: 5.5 to 9.5 Persistent foaming 25mL 30mL Require: 5 60mL foam after 1 min Attrition resistance 99.8% 99.9% Require: 98% passes thru 4mm sieve

EXAMPLE 3

[0121] Recipe for a nominally 800g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 5 and, as shown in Table 6, has been determined via assay

as having adequate active ingredient concentration at the point of manufacturing and

again after accelerated aging to approximate two years of shelf life.

[0122] The composition of Example 3 is as follows in Table 5.

Table 5:

Ingredient Role Concentration Flumioxazin Active herbicidal 806.1g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 799.7g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 46.0g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Sodium naphthalene sulphonate Surfactant 13.0g/kg (CAS# Proprietary; e.g. Morwet EFW) Calcium chloride dihydrate Filler 82.8g/kg (CAS# 10035-04-8) Sodium sulfate Filler 52.1g/kg (CAS# 7757-82-6) (to 1000g/kg total)

[0123] Chemical and physical parameters of Example 3 is as follows in Table 6.

Table 6:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 802.6g/kg 806.4g/kg Require: 775g/kg Flumioxazin 825g/kg Wet sieve: 0.25% 0.30% Require: 2% retained on a 75pm sieve. Dispersibility 75.6% 72.8% Require: 60%:5 % residues 105% Suspensibility 69.6% 73.8% Require: 60%:5 % residues 105% pH1% 6.9 6.8 Nominally: 5.5 to 9.5 Persistent foaming 15mL 20mL Require: 60mL foam after 1 min Attrition resistance 99.4% 99.5% Require: 98% passes thru 4mm sieve

EXAMPLE4

[0124] Recipe for a nominally 800g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 5 and, as shown in Table 6, has been determined via assay

as having adequate active ingredient concentration at the point of manufacturing and

again after accelerated aging to approximate two years of shelf life.

[0125] The composition of Example 4 is as follows in Table 7.

Table 7:

Ingredient Role Concentration Flumioxazin Active herbicidal 808.1g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 801.6g/kg Flumioxazin) Sodium-neutralized styrene/acrylic acid Surfactant 51.1g/kg copolymer (CAS# proprietary; e.g. Atlox Metasperse 550S) Dodecyl sulphate, sodium salt Surfactant 18.5g/kg (CAS# 151-21-3) Talc Filler 122.3g/kg (CAS# 14807-96-6) (to 1OOOg/kg total)

[0126] Chemical and physical parameters of Example 4 is as follows in Table 8.

Table 8:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 808.3g/kg 808.4g/kg Require: 775g/kg Flumioxazin 825g/kg Wet sieve: 0.02% 0.02% Require: 2% retained on a 75pm sieve.

Dispersibility 95.2% 95.5% Require: 60%:5 % residues 105% Suspensibility 77.3% 86.2% Require: 60%:5 % residues 105% pH1% 8.1 7.9 Nominally: 5.5 to 9.5 Persistent foaming 30mL 25mL Require: 60mL foam after 1 min Attrition resistance 99.8% 99.8% Require: 98% passes thru 4mm sieve

EXAMPLE 5

[0127] Recipe for a nominally 800g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 9 and, as shown in Table 10, has been determined via

assay as having adequate active ingredient concentration at the point of manufacturing

and again after accelerated aging to approximate two years of shelf life.

[0128] The composition of Example 5 is as follows in Table 9.

Table 9:

Ingredient Role Concentration Flumioxazin Active herbicidal 806.4g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 799.9g/kg Flumioxazin) Mixture of surfactants Surfactant 45.8g/kg (CAS# proprietary; e.g. Solvay Geropon SC/213 Fatty Alcohol derivative powder Surfactant 14.0g/kg (CAS# Proprietary; e.g. Rhodia Geropon WET F) Talc Filler 133.8g/kg (CAS# 14807-96-6) (to 1OOOg/kg total)

[0129] Chemical and physical parameters of Example 5 is as follows in Table 10.

Table 10:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 803.4g/kg 803.3g/kg Require: 775g/kg Flumioxazin 825g/kg Wet sieve: 0.24% 0.12% Require: 2% retained on a 75pm sieve. Dispersibility 94.5% 94.2% Require: 60%:5 % residues 105% Suspensibility 67.6% 74.5% Require: 60%:5 % residues 105% pH1% 9.1 9.0 Nominally: 5.5 to 9.5 Persistent foaming 25mL 30mL Require: 60mL foam after 1 min Attrition resistance 99.5% 99.7% Require: 98% passes thru 4mm sieve

EXAMPLE 6

[0130] Recipe for a nominally 755g/kg flumioxazin water dispersible granule. The granule is

produced as below in Table 11 and, as shown in Table 12, has been determined via

assay as having adequate active ingredient concentration at the point of manufacturing

and again after accelerated aging to approximate two years of shelf life.

[0131] The composition of Example 6 is as follows in Table 11.

Table 11:

Ingredient Role Concentration Flumioxazin Active herbicidal 756.5g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 750.4g/kg Flumioxazin) Mixture of surfactants Surfactant 49.4g/kg (CAS# proprietary; e.g. Solvay Geropon SC/213 Fatty Alcohol derivative powder Surfactant 9.5g/kg (CAS# Proprietary; e.g. Rhodia Geropon WET F) Disodium EDTA dehydrate Filler/complexing 30.3g/kg

(CAS# 6381-92-6; e.g. Trilon BD) agent Talc Filler 154.3g/kg (CAS# 14807-96-6) (to 1000g/kg total)

Chemical and physical parameters of Example 6 is as follows in Table 12.

Table 12:

Test As manufactured Accelerated Aged Result Appearance Beige granule Beige granule Assay: 754.4g/kg 751.1g/kg Require: 730g/kg Flumioxazin 780g/kg Wet sieve: 0.37% 0.26% Require: 2% retained on a 75pm sieve. Dispersibility 93.9% 93.7% Require: 60%:5 % residues 105% Suspensibility 73.8% 77.5% Require: 60%:5 % residues 105% pH1% 6.9 6.8 Nominally: 5.5 to 9.5 Persistent foaming 25mL 30mL Require: 5 60mL foam after 1 min Attrition resistance 99.5% 99.5% Require: 98% passes thru 4mm sieve

EXAMPLE 7

[0132] An example formulation combining about 860g/kg flumioxazin is provided below in

Table 13, which includes the purity (where known), source and technical details of the

components. The flumioxazin technical and the other stated components are the same

as that used in the formulations of Examples 1 to 6.

[0133] The composition of Example 7 is as follows in Table 13.

Table 13:

Ingredient Purchased from (incl. trade name) Parts by weight (g/kg) Flumioxazin 99.2% Flumioxazin (CAS# 103361-09-7) 858.6 technical Manufactured by: Lier Chemical Co. Ltd., Economic and Technological Development Zone, Mianyang Sichuan Province PR China Sodium napthalene 40.0 Proprietary Name = Morwet D425 (CAS# sulphonate formaldehyde Proprietary) condensate (e.g. Morwet Manufactured or marketed by Akzo Nobel D425) Anionic surfactant (e.g. Proprietary Name = Geropon Ultrasperse 30.0 Solvay Geropon (CAS# Proprietary) Ultrasperse) Manufactured or marketed by Solvay (previously Rhodia) Sodium diisopropyl Proprietary Name = Supragil WP (CAS# 20.0 naphthalene sulfonate (e.g. 1322-93-6) Solvay Supragil WP) Manufactured or marketed by Solvay (previously Rhodia) Sodium sulfate Sodium sulfate (CAS# 7757-82-6) 51.4 Manufactured unknown

EXAMPLE 8

[0134] Recipe for a nominally 900g/kg flumioxazin water dispersible granule containing pH

indicator. The granule is produced as below in Table 14 and, as shown in Table 15, has

been determined via assay as having adequate active ingredient concentration at the

point of manufacturing and again after accelerated aging to approximate two years of

shelf life

[0135] The composition of Example 8 is as follows in Table 14.

Table 14:

Ingredient Role Concentration Flumioxazin Active herbicidal 908.5g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 901.2g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 45.3g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Sodium naphthalene sulphonate Surfactant 12.2g/kg (CAS# Proprietary; e.g. Morwet EFW) Bromocresol purple Indicator 2.0g/kg (CAS# 115-40-2) Silica, amorphous Filler 32.0g/kg (CAS# 7631-86-9) (to 10OOg/kg total)

Chemical and physical parameters of Example 8 is as follows in Table 15.

Table 15:

Test As-manufactured Appearance Yellow granule Assay: 898.7g/kg Require: 875g/kg Flumioxazin5 925g/kg Wet sieve: 0.00% Require: 2% retained on a 75pm sieve. Dispersibility 95.2% Require: 60%:5 % residues 105% Suspensibility 82.0% Require: 60%:5 % residues 105% pH1% 7.4 Nominally: 4.5 to 9.5 Persistent foaming 1OmL Require:5 60mL foam after 1 min Attrition resistance 99.8% Require: 98% passes thru 4mm sieve

EXAMPLE 9

[0136] Recipe for a nominally 850g/kg flumioxazin water dispersible granule containing pH

indicator. The granule is produced as below in Table 16 and, as shown in Table 17, has

been determined via assay as having adequate active ingredient concentration at the

point of manufacturing and again after accelerated aging to approximate two years of

shelf life

[0137] The composition of Example 9 is as follows in Table 16.

Table 16:

Ingredient Role Concentration Flumioxazin Active herbicidal 857.8g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 850.9g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 40.2g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Anionic surfactant Surfactant 30.2g/kg (CAS# proprietary; e.g. Geropon Ultrasperse) Sodium diisopropyl naphthalene sulfonate Surfactant 20.4g/kg (CAS# 1322-93-6; e.g. Solvay Supragil WP) Bromocresol purple Indicator 1.2g/kg (CAS# 115-40-2) Sodium sulfate Filler 50.2g/kg (CAS# 7757-82-6) (to 1000g/kg total)

Chemical and physical parameters of Example 9 is as follows in Table 17.

Table 17:

Test As-manufactured Appearance Blue granule Assay: 850.9g/kg Require: 825g/kg Flumioxazin 875g/kg Wet sieve: 0.00% Require: 2% retained on a 75pm sieve. Dispersibility 98.7%

Require: 60%:5 % residues 105% Suspensibility 85.3% Require: 60%:5 % residues 105% pH1% 8.9 Nominally: 4.5 to 9.5 Persistent foaming 25mL Require: 60mL foam after 1 min Attrition resistance 99.9% Require: 98% passes thru 4mm sieve

EXAMPLE 10

[0138] Recipe for a nominally 850g/kg flumioxazin water dispersible granule containing pH

indicator. The granule is produced as below in Table 18 and, as shown in Table 19, has

been determined via assay as having adequate active ingredient concentration at the

point of manufacturing and again after accelerated aging to approximate two years of

shelf life

[0139] The composition of Example 10 is as follows in Table 18.

Table 18:

Ingredient Role Concentration Flumioxazin Active herbicidal 857.5g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 850.6g/kg Flumioxazin) Sodium naphthalene sulphonate formaldehyde Surfactant 39.9g/kg concentrate (CAS# proprietary; e.g. Morwet D 425) Mixture of surfactants Surfactant 20.0g/kg (CAS# proprietary; e.g. Solvay Geropon SC/213 Sodium diisopropyl naphthalene sulfonate Surfactant 15.0g/kg (CAS# 1322-93-6; e.g. Solvay Supragil WP) Bromocresol purple Indicator 1.1g/kg (CAS# 115-40-2) Ammonium chloride pH adjustment 25.4g/kg (CAS# 12125-02-9) Citric acid, anhydrous pH adjustment 12.2g/kg

(CAS# 77-92-9) Bentonite Filler 28.9g/kg (CAS# 1302-78-9) (to 1000g/kg total)

Chemical and physical parameters of Example 10 is as follows in Table 19.

Table 19:

Test As manufactured Appearance Yellow granule Assay: 847.3g/kg Require: 825g/kg Flumioxazin 875g/kg Wet sieve: 1.00% Require: 2% retained on a 75pm sieve. Dispersibility 91.6% Require: 60%:5 % residues 105% Suspensibility 81.9% Require: 60%:5 % residues 105% pH1% 5.4 Nominally: 4.5 to 9.5 Persistent foaming 10mL Require: 60mL foam after 1 min Attrition resistance 99.9% Require: 98% passes thru 4mm sieve

EXAMPLE 11

[0140] Recipe for a nominally 800g/kg flumioxazin water dispersible granule containing pH

indicator. The granule is produced as below in Table 20 and, as shown in Table 21, has

been determined via assay as having adequate active ingredient concentration at the

point of manufacturing and again after accelerated aging to approximate two years of

shelf life

[0141] The composition of Example 11 is as follows in Table 20.

Table 20:

Ingredient Role Concentration Flumioxazin Active herbicidal 807.0g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 800.5g/kg Flumioxazin) Sodium-neutralized styrene/acrylic acid Surfactant 51.5g/kg copolymer (CAS# proprietary; e.g. Atlox Metasperse 550S) Dodecyl sulphate, sodium salt Surfactant 18.7g/kg (CAS# 151-21-3) Phenol red Indicator 5.1g/kg (CAS# 143-74-8) Talc Filler 117.7g/kg (CAS# 14807-96-6) (to 1000g/kg total)

Chemical and physical parameters of Example 11 is as follows in Table 21.

Table 21:

Test As manufactured Appearance Orange granule Assay: 799.3g/kg Require: 775g/kg Flumioxazin 825g/kg Wet sieve: 0.00% Require: 2% retained on a 75pm sieve. Dispersibility 98.2% Require: 60%:5 % residues 105% Suspensibility 88.3% Require: 60%:5 % residues 105% pH1% 7.4 Nominally: 4.5 to 9.5 Persistent foaming 30mL Require:5 60mL foam after 1 min Attrition resistance 99.9% Require: 98% passes thru 4mm sieve

EXAMPLE 12

[0142] Recipe for a nominally 750g/kg flumioxazin water dispersible granule containing pH

indicator. The granule is produced as below in Table 22 and, as shown in Table 23, has

been determined via assay as having adequate active ingredient concentration at the

point of manufacturing and again after accelerated aging to approximate two years of

shelf life

[0143] The composition of Example 12 is as follows in Table 22.

Table 22:

Ingredient Role Concentration Flumioxazin Active herbicidal 756.9g/kg (CAS# 103361-09-7, Technical material, 99.2%) ingredient (yields 750.8g/kg Flumioxazin) Mixture of surfactants Surfactant 49.0g/kg (CAS# proprietary; e.g. Solvay Geropon SC/213 Fatty Alcohol derivative powder Surfactant 9.5g/kg (CAS# Proprietary; e.g. Rhodia Geropon WET F) Disodium EDTA dihydrate Filler/complexing 30.2g/kg (CAS# 6381-92-6; e.g. Trilon BD) agent Neutral red Indicator 10.2g/kg (CAS# 553-24-2) Talc Filler 144.2g/kg (CAS# 14807-96-6) (to 1000g/kg total)

Chemical and physical parameters of Example 12 is as follows in Table 23.

Table 23:

Test As-manufactured Appearance Purple granule Assay: 747.0g/kg Require: 725g/kg : Flumioxazin 5 775g/kg Wet sieve: 0.00% Require: : 2% retained on a 75pm sieve. Dispersibility 93.3% Require: 60%:5 % residues 5 105%

Suspensibility 65.2% Require: 60%:5 % residues 5 105% pH1% 6.4 Nominally: 4.5 to 9.5 Persistent foaming 20mL Require: 5 60mL foam after 1 min Attrition resistance 99.8% Require: > 98% passes thru 4mm sieve

EXAMPLE 13

[0144] Recipe for a nominally 850g/kg flumioxazin water dispersible granule containing pH

indicator. The composition of Example 13 is as follows in Table 24.

Table 24:

Purchased from (incl. trade name) Parts by weight (g/kg) Flumioxazin Flumioxazin (CAS# 103361-09-7) 857.5 99.2% technical Manufactured by: Lier Chemical Co. Ltd., Economic and Technological Development Zone, Mianyang Sichuan Province PR China Sodium 39.9 napthalene Proprietary Name = Morwet D425 (CAS# sulphonate Proprietary) formaldehyde condensate (e.g. Manufactured or marketed by Akzo Nobel Morwet D425) Anionic surfactant Proprietary Name = Geropon SC/213 (CAS# 20.0 (e.g. Solvay Proprietary) Geropon SC/213) Manufactured/marketed by: Solvay (previously Rhodia) Sodium Proprietary Name = Supragil WP (CAS# 1322-93- 15.0 diisopropyl 6) naphthalene sulfonate (e.g. Manufactured or marketed by Solvay (previously Solvay Supragil Rhodia)

WP) Bromocresol Bromocresol purple (CAS# 115-40-2) 1.1 purple Manufactured/marketed by: Sigma-Aldrich Pty Ltd Ammonium Ammonium chloride (CAS# 12125-02-9) 25.4 Chloride Manufactured/marketed by: Rowe Scientific Citric acid Citric acid (CAS# 77-92-9) 12.2

Manufactured/marketed by: Rowe Scientific Bentonite Bentonite (CAS# 1302-78-9) 28.9

Manufactured unknown

EXAMPLE 14 - Method of manufacture of high-loadinq flumioxazin WG herbicide

[0145] Formulation of a nominally 1000kg batch of product, inclusive of quality control

measures, is as follows.

Formulation Procedure

[0146] 1. Ensure formulation line is empty and clean.

[0147] 2. Charge active ingredient (flumioxazin technical material) to the blending vessel with

continuous agitation.

[0148] 3. Charge the surfactant(s) and other excipients (including pH indicator and pH modifier

as appropriate) to the blending vessel.

[0149] 4. Continue agitating this dry mixture until a homogeneous free-flowing blend is

achieved.

[0150] 5. Where particle size reduction is required, feed the blended ingredients to the jet mill

and process until the desired particle size is achieved (typically less than 20pm).

[0151] 6. Add water to the milled material with mixing to achieve a dough-like mixture and

extrude to produce columnar granules of the desired dimensions, or otherwise granulate

by other methods, drying the product.

Quality Control Procedure

[0152] 1. Sample approximately 1kg of product, ensuring it is representative.

[0153] 2. Sub-sample approximately 250g and subject it to the following testing regime.

[0154] 2.1 Active constituent (flumioxazin) content (appropriately validated method:

specificity; linearity of response with correlation coefficient R>0.99; accuracy of mean

measured assay as a proportion of true content 100±2%; reproducibility of response :

2% relative standard deviation).

[0155] 2.2 pH of a 1% aqueous solution/dispersion (CIPAC MT75.3).

[0156] 2.3 Wet sieve test (CIPAC MT185).

[0157] 2.4 Wettability (CIPAC MT53.3).

[0158] 2.5 Persistent foaming (CIPAC MT 47.2).

[0159] 3. If pH 1% aqueous is satisfactory, record results and proceed to the next test. If pH

1% aqueous is outside the bounds of the acceptable range listed in the specification,

quarantine the batch for further investigations and possible rework.

[0160] 4. If the wet sieve testing is satisfactory (generally:52% w/w retention on a 75pm

aperture sieve after dispersion in water), record results and proceed to the next test. If

the wet sieve testing is outside the bounds of the acceptable range listed in the

specification, quarantine the batch for further investigations and possible rework

including but not limited to recycling through the milling stage of processing to further

reduce particle size.

[0161] 5. If wettability is satisfactory (generally 51 minute) record results and proceed to the

next test. If wettability is outside the bounds of the acceptable range listed in the

specification, quarantine the batch for further investigations and possible rework

including but not limited to recycling through the process.

[0162] 6. If persistent foaming characteristics are satisfactory (generally 560mL), record results

and proceed to the next test. If persistent foaming characteristics are outside the

bounds of the acceptable range quarantine the batch for further investigations and

possible rework.

[0163] 7. If active constituent level is satisfactory, record results. If active constituent level is

outside the bounds of the acceptable range listed in the specification, adjust the level

accordingly by adding additional components other than active ingredient (for a high

active content) or additional flumioxazin technical active constituent (for a low active

content) to the batch with subsequently reprocessing. Repeat the adjustment process

until active constituent levels are within the bounds of the acceptable range.

[0164] 8. Catalogue and store a retention sample of approximately 200g.

[0165] 9. Generate a certificate of analysis noting results of testing.

[0166] 10. Issue quality clearance giving authority to package goods.

[0167] 11. Package the finished goods noting the batch number and manufacturing date.

[0168] Although the invention has been described with reference to specific examples, it will be

appreciated by those skilled in the art that the invention may be embodied in many other

forms in particular features of any one of the various described examples may be

provided in any combination in any of the other described examples. Various

modifications and alterations to this invention will become apparent to those skilled in

the art without departing from the scope and spirit of this invention. It should be

understood that this invention is not intended to be unduly limited by the illustrative

embodiments and examples set forth herein and that such examples and embodiments

are presented by way of example only with the scope of the invention intended to be

limited only by the claims set forth herein as follows.

[0169] Other embodiments of the invention as described herein are defined in the following

paragraphs:

1. A solid herbicide composition comprising:

flumioxazin at a concentration of greater than 750 g/kg,

optionally an agriculturally acceptable filler, and

a surfactant.

2. The solid herbicide composition of paragraph 1, wherein the flumioxazin concentration is

greater than 750 g/kg and up to 950 g/kg.

3. The solid herbicide composition of paragraph 1 or paragraph 2, wherein the filler is selected

from the group consisting of amorphous silica, sodium sulfate, calcium chloride dihydrate and talc, or

combinations thereof.

4. The solid herbicide composition of any one of paragraphs 1 to 3, wherein the filler is present

in the herbicide composition at a concentration of between about 10 g/kg and up to 250 g/kg.

5. The solid herbicide composition of any one of paragraphs 1 to 4, wherein the surfactant is an

anionic surfactant.

6. The solid herbicide composition of paragraph 5, wherein the anionic surfactant is selected

from the group consisting of sodium diisopropyl naphthalene sulfonate, sodium naphthalene

sulphonate, an alkylnaphthalene sulfonate, a sodium dodecyl sulfate salt, a sodium-neutralized

styrene/acrylic acid copolymer and an alpha olefin sulfonate, or mixtures thereof.

7. The solid herbicide composition of any one of paragraphs 1 to 6, wherein the surfactant is

present in the herbicide composition at a concentration of between about 10 g/kg and up to 250 g/kg.

8. The solid herbicide composition of any one of the preceding paragraphs, wherein the

composition is in a water-dispersible granule form.

9. A solid herbicide composition comprising flumioxazin at a concentration of about 850 g/kg, a

first surfactant comprising sodium naphthalene sulphonate formaldehyde concentrate at a

concentration of about 40.0 g/kg, a second surfactant comprising an anionic surfactant at a

concentration of about 30.0 g/kg, a third surfactant comprising sodium diisopropyl naphthalene

sulfonate at a concentration of about 20.0 g/kg, and a filler comprising sodium sulfate at a

concentration of about 50 g/kg .

10. A method of preparing a herbicide composition, the method comprising the steps of:

a.) combining flumioxazin, optionally an agriculturally acceptable filler, and a surfactant, and

b.) mixing the mixture of step a.) and forming into a solid granule to thereby provide said

herbicide composition,

wherein said flumioxazin is present at a concentration of greater than 750 g/kg in said herbicide

composition.

11. The method of paragraph 10, wherein the granulation step (b) is carried out by wet

granulation, dry granulation, pan granulation, compaction granulation, centrifugal granulation,

fluidized bed granulation, extrusion granulation and any combination thereof.

12. A herbicide composition produced by the method according to any one of paragraphs 10 or

11.

13. A method of controlling or inhibiting the growth of and/or killing grass or weeds associated

with crops, the method comprising the step of applying a herbicidally effective amount of a

composition according to any one of paragraphs 1 to 9 or the herbicide composition according to

paragraph 12.

14. The method of paragraph 13, further comprising the step of mixing the composition with a

water-containing solvent before the applying step.

15. Use of a composition according to any one of paragraphs 1 to 9 as a herbicide in the

protection of crops.

16. Use according to paragraph 15 wherein the herbicide composition is applied at a rate of

around 5 to 1000 g/Ha.

Claims (5)

1. A herbicide formulation comprising:

flumioxazin;

a pH indicator;

a surfactant, and

optionally a solvent,

optionally an agriculturally acceptable filler, and

optionally a pH modifier for establishing a neutral or slightly acidic environment.

2. A herbicide formulation according to claim 1, wherein:

the pH indicator is selected from the group consisting of: cresol red, bromocresol purple,

neutral red, and phenol red; and

wherein:

if the herbicide formulation is in the form of a water dispersible granule or wettable

powder, then the flumioxazin is present at a concentration of at least about 500 g/kg

and the pH indicator is present at a concentration of between about 0.01 and 20 g/kg; or

if the herbicide formulation is in the form of a liquid concentrate, then the flumioxazin is

present at a concentration of at least about 250 g/L and the pH indicator is present at a

concentration of between about 0.01 and 20 g/L.

3. A method of preparing a herbicide formulation including the steps of:

(a) combining flumioxazin, a pH indicator, a surfactant, , optionally an agriculturally

acceptable filler, optionally a pH modifier; and

(b) mixing the mixture of step (a) to thereby prepare the herbicide formulation.

4. A method of controlling or inhibiting the growth of and/or killing grass or weeds associated

with crops, the method comprising the step of applying a herbicidally effective amount of a

composition according to claims 1 or 2, or the herbicide produced according to the method

of claim 3, to said crop.

5. Use of a composition according to claims 1 or 2, or the herbicide produced according to the

method of claim 3 in the protection of crops.