The present invention relates to a liquid herbicidal composition, comprising pinoxaden, mesosulfuron, and a built-in oil-type adjuvant. The present invention also relates to methods for controlling and/or inhibiting the growth of weeds, such as monocotyledonous and/or dicotyledonous weeds, comprising applying to the weeds or to their locus a liquid herbicidal composition, comprising pinoxaden, mesosulfuron, and a built-in oil-type adjuvant.

Liquid herbicidal compositions comprising an oil-type adjuvant are known from WO 2008/049618. Pinoxaden is a herbicide suitable for the control of grass weeds in certain cereals, and is known from WO 99/47525. Mesosulfuron is a herbicide suitable forthe control of grasses and otherweeds in cereals, and is known from WO 95/10507.

Many grass herbicides (graminicides) for cereals require an adjuvant to develop full biological activity. In many cases the physico-chemical properties of the active ingredients make it difficult to add an adjuvant to the composition. Either because the chemical or physical stability of the active ingredient suffers from the added adjuvant or because biological performance is insufficient. It is in particular very challenging to make a biologically efficient and stable composition due to the chemical and physical instability of the herbicides used.

In general, formulated pinoxaden products are always applied in combination with adjuvants which may be built-in or added to the spray tank (so-called tank-mix adjuvants). The application of pinoxaden and tank-mix adjuvants is problematic in that physical incompatibilities often exist which may lead to poor biological efficacy and/or problematic application of the admixtures. These incompatibilities also lead to increased levels of flocculation which can result in the blocking of application equipment.

Adjuvants may also be incorporated into the herbicide composition (so-called built-in adjuvants). The use of a built-in adjuvant provides the advantage of ensuring the correct dosage of the adjuvant is used in practice. Iftoo little adjuvant is used, the full efficacy potential of the formulation is not achieved. If too high a dose of adjuvant is administered, however, there is the possibility of damage to the crop.

Compositions of pinoxaden comprising a built-in adjuvant are challenging to formulate due to both the instability of pinoxaden, and also difficulties achieving physical compatibility between the built-in adjuvant and the rest of the formulation.

Thus, there is need for a formulated composition comprising pinoxaden, mesosulfuron and a built- in adjuvant which demonstrates a high degree of both chemical and physical stability.

It has now been found that a composition comprising the herbicides pinoxaden and mesosulfuron shows excellent biological efficacy as well as chemical and physical stability when oil-type adjuvants, in particular polypropylene glycol ethers, are used as built-in adjuvants, in a one-pack concept that does not require the use of a separate tank- mix adjuvant by the end user. Such a composition results in easier handling, especially in markets where products are sold in bulk. It may also lead to significant cost savings during manufacture because the production and packaging of a separate tank-mix adjuvant is no longer required.

It has also been found that the new compositions with built-in adjuvants, in particular in the form of an oil dispersion (OD), match or even exceed the efficacy of corresponding conventional compositions with a tank-mix adjuvant.

In a first embodiment, there is provided a liquid herbicidal composition, comprising:

(a) Pinoxaden;

(b) Mesosulfuron; and

(c) An adjuvant, wherein the adjuvant is a built-in oil-type adjuvant.

In a second embodiment, there is provided a method for inhibiting or controlling undesirable plant growth, wherein a herbicida lly effective amount of the composition according to the invention, is applied to the plants or their habitat.

Pesticidal Active Ingredients

Pinoxaden (known from WO 99/47525), may be present at a percentage (%) of weight/volume of from 0.5 to 50% w/v, preferably from 2 to 30% w/v, more preferably from 5 to 25% w/v, and most preferably from 10 to 15% w/v.

Mesosulfuron (known from WO 95/10507) may be present at a percentage (%) of weight/volume of from 0.1 to 20% w/v, preferably from 0.5 to 15% w/v, more preferably from 1 to 10% w/v, and most preferably from 1 to 5% w/v.

Safeners

The composition according to the present invention may contain a safener. Preferably, the safener is selected from cloquintocet, cloquintocet acid, cloquintocet-mexyl, mefenpyr-diethyl, cy prosulfa mid, metcamifen, and isoxadifen-ethyl. These safeners are known and are described, for example, in The Pesticide Manual, 18th Ed., British Crop Protection Council 2018, or other readily available resources. In a preferred embodiment the safener is cloquintocet-mexyl or mefenpyr-diethyl. In another preferred embodiment, the safener is mefenpyr-diethyl. The safener may be present at a percentage (%) of weight/volume of from 0.1 to 50% w/v, preferably from 0.5 to 20% w/v, more preferably from 1 to 18% w/v, and most preferably from 3 to 12% w/v.

Oil-Type Adjuvants

As stated above, polypropylene glycol ethers are a high-performance oil-type adjuvant which has allowed a chemically and physically stable, active one-pack composition to be developed.

Polypropylene glycol ethers include polypropylene glycol stearyl ethers, polypropylene glycol butyl ethers, polypropylene glycol cetyl ethers, and polypropylene glycol myristyl ethers. The polypropylene glycol ethers useful in the new composition are polypropylene glycol stearyl ethers, which have been described, for example, in WO 03/022048. Their structure is described below:

R-(O-CH ₂ CH(CH ₃ ))n-O-R ¹ wherein R is a C12 to Cis straight- or branched-chain alkyl or alkenyl group, n is 1 to 30, and R ¹ is H or methyl.

Preferably, R is a Cu to Cis straight- or branched-chain alkyl or alkenyl group, and more preferably R is a Cis to Cis straight- or branched-chain alkyl group.

Preferably n is 2 to 20; more preferably 5 to 18; and even more preferably 8 to 15. More preferably still, n is 11 or 15.

Preferably, R ¹ is H.

Preferred polypropylene glycol stearyl ethers for use in the new compositions are stearyl ethers having between 10 and 20 polypropylene glycol units. Particularly preferred stearyl ethers include polypropylene- 15-stearyl ethers and polypropylene-1 1 -stearyl ethers. Polypropylene-15-stearyl ethers and polypropylene-11 -stearyl ethers include Acconon® E (ABITEC), Arlamol™ PS15 (Croda Chem. Europe Ltd), Arlamol™ PS15E (Croda Inc), Finsolv® TPP (Innospec), Jeecol PSA-11 (Jeen International), Jeecol PSA-15 (Jeen International), Lipocol® P-15 (Lipo Chemicals), Lumisolve CSA-70 (Lambent Tech), Lumisolve CSA-75 (Lambent Tech), Procol™ PSA-11 (Protameen), Procol™ PSA-15 (Protameen), Sympatens ASP-150 (Kolb), Varonic® APS (Evonik), Witconol™ APS (Evonik), Finsolv® P (Innospec), and Prox-onic SA1-015/P (Protex International).

A particularly preferred polypropylene glycol stearyl ether is Arlamol™ PS15E, a stearyl ether having 11 polypropylene glycol units (Croda Chemicals Ltd. Goole, England).

The oil-type adjuvant may be present at a percentage (%) of weight/volume of from 15 to 65% w/v, preferably from 20 to 55% w/v, more preferably from 25 to 40% w/v, even more preferably from 28 to 37% w/v, and more preferably still from 30 to 37% w/v.

Surfactants

Surfactants are included as emulsifiers, dispersants, and wetting agents. The surfactants useful in the new compositions are known in the art and comprise, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of arylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as ethoxylated sorbitol hexaoleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; fatty alcohol alkoxylates which may be alkyl end-capped; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; alkylated polyvinylpyrrolidone, and also further substances described e.g. in “McCutcheon's Emulsifiers & Detergents”, North American Edition, MC Publishing Co., 2018. It is also possible to use a mixture of one or more of these surfactants.

Each surfactant may be present at a percentage (%) of weight/volume from 0.1 to 20%. Preferably from 0.5 to 10% w/v, more preferably from 0.75 to 8% w/v, and more preferably still from 1 to 6% w/v.

The total amount of surfactant may be comprised from 3 to 30% w/v, preferably from 5 to 25% w/v, more preferably 10 to 20% w/v, and most preferably 14 to 18% w/v.

Oil carrier

Oil carriers serve as a medium to disperse active ingredients. Oil carriers suitable for use in the composition of the present invention may be selected from rape seed oil, methylated rape seed oil, synthetic paraffins (e.g. (C12-C16), (Cu-Cis), (C15-C21), and (C18-C26)) , dipropylene glycol dibenzoate, hydrocarbons (e.g. Cn-Cu, n-alkanes, isoalkanes, cyclics, and <2% aromatics), aromatic hydrocarbons (e.g. C10-C13, and <1 % naphthalene), aromatic hydrocarbons (e.g. Cg, and benzene <0.1%), mixtures of petroleum extracts comprising solvent-dewaxed light paraffinic and solvent-dewaxed heavy paraffinic distillates, solvent naphtha, citrate ester based solvents, tris (2-ethylhexyl) O-acetylcitrate, cyclohexanedicarboxylic acid, dinonyl ester, tri-n-hexyl-trimellitate, 1 ,2,4-benzenetricarboxylicacid, trihexylester, isopropyl myristate, decanedioic acid, bis(1 -methylethyl) ester, isobornyl acetate (IBA, >94%), Cs-Cio fatty acids methyl esters, triacetyl glycerine, and isoparaffinic hydrocarbon, or mixtures thereof.

Preferably, the oil carrier is selected from rape seed oil, methylated rape seed oil, synthetic paraffins (e.g. (C12-C16), (Cu-Cu), (C15-C21), and (C18-C26)), dipropylene glycol dibenzoate, hydrocarbons (e.g. Cn-Cu, n-alkanes, isoalkanes, cyclics, and <2% aromatics), aromatic hydrocarbons (e.g. C10-C13, and <1 % naphthalene), aromatic hydrocarbons (e.g. Cg, and benzene <0.1%), mixtures of petroleum extracts comprising solvent-dewaxed light paraffinic and solvent-dewaxed heavy paraffinic distillates, and isoparaffinic hydrocarbon, or mixtures thereof.

More preferably, the oil carrier is selected from rape seed oil, methylated rape seed oil, and mixtures of petroleum extracts comprising solvent-dewaxed light paraffinic and solvent-dewaxed heavy paraffinic distillates, or mixtures thereof.

In one embodiment, the oil carrier is selected from synthetic paraffins (e.g. (C12-C16), (Cu-Cis) , (C15-C21), and (C18-C26)), dipropylene glycol dibenzoate, hydrocarbons (e.g. Cn-Cu, n-alkanes, isoalkanes, cyclics, and <2% aromatics), aromatic hydrocarbons (e.g. C10-C13, and <1% naphthalene), aromatic hydrocarbons (e.g. Cg, and benzene <0.1 %), mixtures of petroleum extracts comprising solvent-dewaxed light paraffinic and solvent-dewaxed heavy paraffinic distillates, and isoparaffinic hydrocarbon, or mixtures thereof. Preferably, the oil carrier is a mixture of petroleum extracts comprising solvent-dewaxed light paraffinic and solvent-dewaxed heavy paraffinic distillates.

The oil carrier or mixtures thereof may be present at a percentage (%) of weight/volume (w/v) from 10 to 90% w/v, preferably from 15 to 40% w/v, more preferably from 17 to 35% w/v, and more preferably still from 20 to 25% w/v.

Additional Formulation Ingredients

The new compositions may also comprise additional formulation aids known in the art such as crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH- modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.

Each additional formulation ingredient may be present at a percentage (%) of weight/volume of from 0.01 to 5% w/v, preferably from 0.05 to 4% w/v, more preferably from 0.1 to 3% w/v, and more preferably still from 0.5 to 1 .5% w/v.

Co-herbicides

Optionally, an additional co-herbicide for pinoxaden and mesosulfuron may be incorporated into the compositions according to the present invention. It is preferred to select the co-herbicide from the group consisting of aryloxyphenoxy and heteroaryloxyphenoxy propionic acids, cyclohexandiones, sulfonyl urea, triazolopyrimidines, nitriles, thiocarbamates, dinitroanilines, benzoic acids, phenoxy acids and pyridine carboxylic acids. Of particular interest are clodinafop, fenoxaprop, tralkoxydim, prosulfocarb, triasulfuron, prosulfuron, amidosulfuron, iodosulfuron, chlorsulfuron, flupyrsulfuron, metsulfuron, sulfosulfuron, thifensulfuron, tribenuron, tritosulfuron, florasulam, metosulam, flumetsulam, pyroxsulam, 2,4-D, 2,4-DP, dichlorprop-p, MCPA, mecoprop, mecoprop-p, MCPB, clopyralid, bromoxynil, bromoxynil-octanoate, ioxynil, ioxynil-octanoate, fluroxypyr, trifluralin, diflufenican, picolinafen, pendimethalin and triallate, where tralkoxydim, triasulfuron, diflufenican, florasulam, pyroxsulam, pyroxsulam in combination with cloquintocet and clodinafop are preferred.

Formulation Type

Preferably, the compositions according to the present invention are prepared in the form of an oil dispersion (OD). However, it is also envisaged that the compositions according to the present invention may also be prepared in the form of a suspo-emulsion (SE) or suspension concentrate (SC). Such formulations are diluted prior to use. Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil, or solvents.

The compositions according to the present invention are biologically highly effective and chemically and physically stable. Preferably, the compositions are characterized by a breakdown of less than 10% pinoxaden and 10% mesosulfuron after 8 weeks storage at a temperature of 40 °C. The compositions according to the invention may also be characterized in a 10% reduction in crystal growth.

In a first embodiment, there is provided a liquid herbicidal composition, comprising:

(a) Pinoxaden;

(b) Mesosulfuron; and

(c) An adjuvant, wherein the adjuvant is a built-in one oil-type adjuvant.

In a further embodiment, there is provided a liquid herbicidal composition, comprising:

(a) Pinoxaden;

(b) Mesosulfuron; and

(c) A built-in polypropylene glycol ether adjuvant.

In a further embodiment, there is provided a liquid herbicidal composition, comprising:

(a) Pinoxaden;

(b) Mesosulfuron; and

(c) A built-in polypropylene glycol stearyl ether adjuvant.

In one embodiment, the composition according to the present invention comprises:

0.5 - 50% pinoxaden;

0.1 - 20% mesosulfuron;

0.1 - 50% safener;

15 - 65% oil-type adjuvant;

0.1 - 5% thickener;

3 - 30% total emulsifiers;

10 - 90% oil carrier (different from the oil-type adjuvant).

In another embodiment, the composition according to the present invention comprises:

2 - 30% pinoxaden;

0.5 - 15% mesosulfuron;

0.5 - 20% safener;

20 - 55% oil-type adjuvant;

0.05 - 4% thickener;

5 - 25% total emulsifiers;

15 - 40% oil carrier (different from the oil-type adjuvant).

In a further embodiment, the composition according to the present invention comprises:

5 - 25% w/v pinoxaden;

1 - 10% w/v mesosulfuron;

1 - 18% w/v safener;

25 - 40% w/v oil-type adjuvant; 0.1 - 3% thickener;

10 - 20% total emulsifiers;

17 - 35% oil carrier (different from the oil-type adjuvant).

In a still further embodiment, the composition according to the present invention comprises:

10 - 15% pinoxaden;

1 - 5% mesosulfuron;

3 - 12% safener;

28 - 37% oil-type adjuvant;

0.5 - 1 .5% thickener;

14 - 18% total emulsifiers;

20 - 25% oil carrier (different from the oil-type adjuvant).

The formulations may be prepared, for example, by mixing the active ingredients (i.e. pinoxaden and mesosulfuron, optionally in combination with a safener) with formulation adjuvants and other co- formulants in order to obtain compositions in the form of solutions or dispersions.

The invention also relates to a method for inhibiting or controlling undesirable plant growth, wherein a herbicidally effective amount of the composition according to the present invention is applied to the plants or their habitat.

Crops of useful plants in which the compositions according to the invention can be used include especially cereals, in particular wheat, durum wheat, triticale, rye and barley. The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant e.g. to imidazolinones, such as imazamox, by conventional methods of breeding is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Apera, Avena, Setaria, Sinapis, Lolium, Echinochloa, Bromus, Alopecurus, Phalaris, Amaranthus, Chenopodium, Convolvulus, Chrysanthemum, Papaver, Cirsium, Polygonum, Matricaria, Galium, Viola and Veronica.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples oftransgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33BC (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant. The term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).

Areas under cultivation are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.

The following Examples illustrate the invention.

Example 1 : A.I./Co-formulant Compatibility - It is well known that pinoxaden is incompatible with certain chemicals. The below table shows the loss of active ingredients pinoxaden and mesosulfuron in the presence of various co-formulants. Each composition comprised 10% w/w of each A. I. at the start ofthe study, the compositions were stored fortwo weeks at 54 °C after which the percentage (%) of A. I. loss was measured, as shown below in Table 1 .

Table 1 : Chemical stability of A.I.s (PXD/MSU) in diverse solvents/adjuvants:

Preparations of formulations F1 to F7

The thickener system was activated in the adjuvant/oil carrier blend with high shear mixing. The surfactants were added and the safener solubilized in the blend before the active ingredients were dispersed during high shear. The resulting mixtures were ground in a bead mill.

The amounts of the components present in samples F1 to F7 are given in Table 2 below. The values are referred in % w/v.

Table 2: Formulation Composition Examples

Example 2: Formulation Stability

The stability data provided below show the amount of decomposition of pinoxaden and mesosulfuron in various oil dispersions after storage for 8 weeks at 40 °C, as shown below in Table 3.

Table 3: Decomposition (%) of formulation examples after storage for 8 weeks at 40 °C

It can be seen that the stability of both pinoxaden and mesosulfuron is markedly improved in compositions comprising polypropylene glycol stearyl ether (adjuvant) and an appropriate co-formulant system compared to compositions devoid of polypropylene glycol stearyl ether. The chemical stability of a formulation is an important criterion, but equally important is the physical stability. The following table summarises physical stability of the various compositions after storage. Table 4: Physical Properties of Formulation Examples

‘Viscometer, sp.3, 30 rpm.

‘‘1 % in Cipac D water, mL.

These results show the overall superiority of formulation F7 in terms of physical stability when compared to the other formulations.

Table 5: Assessment of flocculation under shear after shaking the sample for 30 min in Cipac D water

In a spray tank, the dilution of formulations experience high shear, which can lead to flocculation and thus nozzle blockage. Therefore, dilutions of the formulation (1 %, in Cipac D water, 80 mL) were tested in a Burrell wrist shaker test. The dilutions were shaken for 30 min and the dilution passed through a 100 pm sieve. The residues formed were collected, dried, and the percentage residue calculated.

Table 6: Control of weeds (%) The test plants were sprayed with formulations F1 to F7 using a 200 L/ha spray volume. The results were obtained by visual assessments 21 to 28 days are summarized below in Table 6.