WO2020225276A1 - Agrochemical formulation with enhanced performance and enhanced performance at low spray volumes and by uav application - Google Patents

Abstract

The present invention relates to novel aqueous agrochemical compositions; their use for foliar application, their use at conventional spray volumes, their use at low spray volumes, their use by unmanned areal vehicles (UAV) and their application for controlling agricultural pests, weeds or diseases and reducing the wash-off of active ingredients by rainfall, as well as reducing the rebound of droplets, in particular on waxy leaves.

Description

Agrochemical formulation with enhanced performance and enhanced performance at low spray volumes and by UAV application

The present invention relates to novel aqueous agrochemical compositions, their use for foliar application, their use at conventional spray volumes, their use at low spray volumes, their use by unmanned aerial or land vehicles (UAV), and their application for controlling agricultural pests, weeds or diseases and reducing the wash-off of active ingredients by rainfall, as well as reducing the rebound of droplets, in particular on waxy leaves.

Another invention relates to adjuvant combination for agrochemical formulations with low spray volumes.

The agrochemical compounds used in the compositions according to the instant invention are selected from the group comprising herbicides, fungicides, insecticides, host defence inducers and safeners, as well as mixtures thereof. A key requirement of agrochemical formulations is to deliver active ingredients as effectively as possible to the target while minimising off-target losses to the environment. Designing formulations to achieve this is complex since optimising a formulation for one property often has unwanted effects on other important properties. For example formulants that improve the wetting of crops and the biodelivery of active ingredients often enhance losses to the environment through wash-off by rainfall.

In this invention aqueous formulation suspensions and specific surfactant combinations have been designed which surprisingly give enhanced biological control of target pests, excellent wetting and coverage of the crop and low off-target losses to the environment including low rebound of the spray from waxy crops and low wash-off by rainfall.

Formulations known in the prior art generally exhibit at least one of the following disadvantages like high wash-off of the active ingredient by rainfall, poor coverage at lower spray volumes, as well as high rebound, in particular on waxy leaves, or combinations thereof.

An important requirement of the formulations, also in view of the limited cargo load of UAVs, is that they deliver enhanced performance not only at conventional spray volumes, typically 80 to 1000 1/ha, but also at reduced spray volumes, typically 2 to 60 1/ha, preferably 4 to 25 1/ha, where new application practices such as UAV application including unmanned helicopters and drones can offer faster and lower cost application, as well as spot applications if required. There is an urgent need in the industry for formulations which can fulfill this requirement.

A further requirement of the formulations are that they exhibit excellent physical stability and have a shelf life of two or more years over a wide range of climates. Accordingly there is still a need to develop storage stable compositions which deliver active ingredients as effectively as possible to the target, exhibit excellent wetting and coverage while minimising off-target losses to the environment including rebound of the spray from waxy crops and wash-off by rainfall at both conventional spray volumes and low spray volumes including application by UAVs.

The object of the present invention was therefore to provide highly storage-stable aqueous suspension concentrates, aqueous suspensions, and capsule suspensions which show excellent biological performance, excellent wetting and coverage of the crop, low rebound of the spray and low wash-off by rainfall for use in foliar applications at conventional spray volumes and low spray volumes including application by UAVs. However, designing such formulations is a challenge since these objectives cannot be simply obtained by adding components of each functionality together since they are often antagonistic and/or unstable, and designing formulations that avoid these antagonisms and instabilities is complex.

Therefore, the objective of the instant invention was solved by the present invention with agrochemical compositions comprising: an aqueous dispersion of a) at least one agrochemical active compound, which is solid at room temperature,

b) at least one compound of the group selected from mono- and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular alkali metal salts, more particular sodium salts, and most particular sodium dioctylsulfosuccinate;

c) at least one polyalkyleneoxide modified heptamethyltrisiloxane,

d) at least one emulsion polymer or polymer dispersion with a glass transition temperature (Tg) in the range from -100°C to 30°C,

e) optionally additives selected from the group consisting of non-ionic surfactants, anionic surfactants and dispersing aids,

f) optionally a rheological modifier,

g) optionally an antifoam agent,

h) optionally other formulants, and

i) at least one compatibilizer.

In one preferred embodiment of the agrochemical compositions, compounds e, f and g are mandatory.

In a further preferred embodiment, the agrochemical compositions comprise: a) an aqueous dispersion of at least one agrochemical active compound, which is solid at room temperature, wherein the agrochemical compound is selected from the group consisting of herbicides, insecticides, fungicides, host defence inducers and safeners,

b) sodium dioctylsulfosuccinate; c) at least one polyalkyleneoxide modified heptamethyltrisiloxane,

d) at least one emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C, wherein the polymers are selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and derivatives thereof, polyolefins, polyurethanes and natural polymers and derivatives thereof;

e) one or more additives selected from the group consisting of non-ionic or anionic surfactants or dispersing aids,

f) at least one rheological modifier,

g) at least one antifoam agent,

h) optionally other formulants, and

i) at least one compatibilizer selected from the group of polyalkylene oxide block copolymers.

In a more preferred embodiment, the agrochemical compositions comprise: a) an aqueous dispersion of at least one agrochemical active compound, which is solid at room temperature, wherein the agrochemical compound is selected from the group consisting of herbicides, insecticides, fungicides, host defence inducers and safeners,

b) sodium dioctylsulfosuccinate;

c) polyalkyleneoxide modified heptamethyltrisiloxane,

d) an emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C, selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolysed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymer, polyurethane, cellulose, gelatine, caesin, oxidised starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose,

most preferably the polymer is selected from copolymers of an acrylate and a styrene, wherein said acrylate is selected from the group consisting of 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof, and said styrene is selected from the group consisting of styrene, tert-butyl styrene, para-methyl styrene, or combinations thereof,

e) one or more additives selected from the group consisting of non-ionic or anionic surfactants or dispersing aids,

f) a rheological modifier,

g) an antifoam agent,

h) other formulants, and i) a compatibilizer selected from the group of polyalkylene oxide block copolymers having a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%, more preferably a molecular weight of 2,000 to 4,000 g/mol and an ethylene oxide content of 15 to 30% and especially preferred a molecular weight of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%.

In a preferred embodiment the compounds a) to i) are present in an amount of a) 10 to 600 g/1, preferably 50 to 400 g/1, more preferably 100 to 400 g/1, most preferred 200 to 360 g/1 b) 1 to 80 g/1, preferably 4 to 60 g/1, more preferably 4 to 50 g/1, most preferred 10 to 30 g/1 c) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 d) 1 to 80 g/1, preferably 2.5 to 60 g/1, more preferably 5 to 55 g/1, most preferred 10 to 50 g/1 e) 0 to 100 g/1, preferably 2.5 to 80 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 f) 0 to 60 g/1, preferably 1 to 40 g/1, more preferably 1 to 20 g/1, most preferred 1 to 15 g/1

g) 0 to 25 g/1, preferably 1 to 20 g/1, more preferably 1 to 15 g/1, most preferred 1 to 10 g/1

h) 0 to 150 g/1, preferably 1 to 100 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 i) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 wherein water is added to volume (1 litre).

In a preferred embodiment, the ratios and amounts for the surfactants b), c) and i) as described below apply.

In an alternative embodiment, wherein the formulation of the instant invention is used without dilution (e.g. direct application by UAVs), the compounds a) to i) are present in an amount of a) 10 to 600 g/1, preferably 50 to 400 g/1, more preferably 100 to 300 g/1, most preferred 150 to 270 g/1 b) 1 to 80 g/1, preferably 4 to 60 g/1, more preferably 4 to 50 g/1, most preferred 10 to 30 g/1 c) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 d) 1 to 80 g/1, preferably 2.5 to 60 g/1, more preferably 5 to 50 g/1, most preferred 10 to 45 g/1 e) 0 to 100 g/1, preferably 2.5 to 80 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 f) 0 to 60 g/1, preferably 1 to 40 g/1, more preferably 1 to 20 g/1, most preferred 1 to 15 g/1

g) 0 to 25 g/1, preferably 1 to 20 g/1, more preferably 1 to 15 g/1, most preferred 1 to 10 g/1

h) 0 to 150 g/1, preferably 1 to 120 g/1, more preferably 1 to 60 g/1, most preferred 20 to 45 g/1 i) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 wherein water is added to volume (1 liter).

Moreover, an alternative embodiment of the present invention is directed to agrochemical compositions as described above, however, with components b) and d) as optional components: Therefore, an aqueous dispersion containing the following components is also enclosed by the present invention: a) at least one agrochemical active compound, which is solid at room temperature,

b) optionally mono- and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular alkali metal salts, more particular sodium salts, and most particular sodium dioctylsulfosuccinate;

c) at least one polyalkyleneoxide modified heptamethyltrisiloxane,

d) optionally an emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C, e) optionally additives selected from the group consisting of non-ionic surfactants, anionic surfactants and dispersing aids,

f) optionally a rheological modifiers

g) optionally an antifoam agent,

h) optionally other formulants,

i) at least one polyalkylene oxide block copolymer, preferably a polyalkylene oxide block copolymer having a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%, more preferably a molecular weight of 2,000 to 4,000 g/mol and an ethylene oxide content of 15 to 30% and especially preferred a molecular weight of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%.

If not otherwise indicated, % in this application means percent by weight.

The weight ratios specified above also apply for this alternative, however, the broadest range given for components b, d and h would start at 0 instead of 1.

In the above mentioned compositions compatibilizer i) not only improves wetting properties of the composition, but also enhances solubility of compound c), thus stabilizing the composition.

Moreover, it was found that the objective of the instant invention, as described above, was solved by compositions, comprising adjuvant combinations comprising at least one of each compounds b), c) and i).

Therefore, another aspect of the present invention is an adjuvant combination for agrochemical compositions with low spray volumes.

Hence, an adjuvant combination comprising the compounds b), c) and i) - as defined above - is claimed.

In said adjuvant combination preferably compound b) is sodium dioctylsulfosuccinate, c) is polyalkyleneoxide modified heptamethyltrisiloxane, i) is a polyalkylene oxide block copolymer.

In said adjuvant combination more preferred compound b) is sodium dioctylsulfosuccinate, compound c) is polyalkyleneoxide modified heptamethyltrisiloxane, preferably selected from the group consisting of the siloxane groups Poly(oxy-l,2-ethanediyl),.alpha.-methyl-.omega.-[3-[l,3,3,3-tetramethyl-l- [(trimethylsilyl)oxy]disiloxanyl]propoxy] (CAS No (27306-78-1), Poly(oxy-l,2-ethanediyl),.alpha.-[3- [l,3,3,3-tetramethyl-l-[(trimethylsilyl)oxy]disiloxanyl]propyl]-.omega.-hydroxy (CAS No 67674-67-3), and oxirane, methyl-, polymer with oxirane, mono3-l,3,3,3-tetramethyl-l-

(trimethylsilyl)oxydisiloxanylpropyl ether (CAS No 134180-76-0), compound i) is a polyalkylene oxide block copolymer having a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%, more preferably a molecular weight of 2,000 to 4,000 g/mol and an ethylene oxide content of 15 to 30% and especially preferred a molecular weight of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%.

In a preferred embodiment, the compounds b, c and i are present in a ratio from 1 : 1 : 1 to 1 :4:3, preferably from 1 : 1 : 1 to 1 :3 :3, and most preferred in a ratio from 1 : 1.5: 1.5 to 1 : 2.5:2.5.

In a preferred embodiment, the compounds c and i are present in a ratio from 4: 1 to 1 :4, preferably from 2: 1 to 1 :2, and most preferred in a ratio from 4:3 to 3:4.

Moreover, the amount of said surfactants b, c and i in the agrochemical compositions of the present invention is from 10 to 200 g/1, preferable from 15 to 150 g/1, more preferred from 20 to 120 g/1, and most preferred from 40 to 100 g/1, wherein preferably ratios given above apply.

The present invention is also directed to the use of the compositions according to the invention for foliar application.

Further, the present invention is directed to the use of the surfactant combination of b), c) and i) described above for the production of compositions with low spray volumes.

In the context of the present invention aqueous based agrochemical compositions are by definition suspension concentrates, aqueous suspensions, suspo-emulsions or capsule suspensions, preferably suspension concentrates and aqueous suspensions. Furthermore, it was found that the objective of the instant invention, as described above, was solved by compositions, comprising alternative adjuvant combinations comprising at least one of each compounds b), c) and d).

Therefore, another aspect of the present invention is an adjuvant combination for agrochemical compositions with low spray volumes.

Hence, an adjuvant combination comprising the compounds b), c) and d) - as defined above - is claimed. In said adjuvant combination preferably compound b) is sodium dioctylsulfosuccinate, c) is polyalkyleneoxide modified heptamethyltrisiloxane, d) at least one emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C.

In said adjuvant combination more preferred compound b) is sodium dioctylsulfosuccinate, compound c) is polyalkyleneoxide modified heptamethyltrisiloxane, preferably selected from the group consisting of the siloxane groups Poly(oxy-l,2-ethanediyl),.alpha.-methyl-.omega.-[3-[l,3,3,3-tetramethyl-l- [(trimethylsilyl)oxy]disiloxanyl]propoxy] (CAS No (27306-78-1), Poly(oxy-l,2-ethanediyl),.alpha.-[3- [l,3,3,3-tetramethyl-l-[(trimethylsilyl)oxy]disiloxanyl]propyl]-.omega.-hydroxy (CAS No 67674-67-3), and oxirane, methyl-, polymer with oxirane, mono3-l,3,3,3-tetramethyl-l-

(trimethylsilyl)oxydisiloxanylpropyl ether (CAS No 134180-76-0), compound d) is an emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C, selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolysed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, isopropylene- maleic anhydride copolymer, polyurethane, cellulose, gelatine, caesin, oxidised starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose, most preferably the polymer is selected from copolymers of an acrylate and a styrene, wherein preferably said acrylate is selected from the group consisting of 2-ethyl -hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof, and said styrene is selected from the group consisting of styrene, tert-butyl styrene, para-methyl styrene, or combinations thereof. In a preferred embodiment, the compounds b, c and d are present in a ratio from 1 : 1 : 1 to 1 :6:3, preferably from 1 : 1 : 1 to 1 :5 :3, and most preferred in a ratio from 1 : 1.5: 1.5 to 1 :3:3.

In a preferred embodiment, the compounds c and d are present in a ratio from 4: 1 to 1 :4, preferably from 3: 1 to 1 :3, and most preferred in a ratio from 2: 1 to 1 :2.

Moreover, the amount of said surfactants b, c and d in the agrochemical compositions of this example is from 10 to 200 g/1, preferable from 15 to 160 g/1, more preferred from 20 to 140 g/1, and most preferred from 40 to 130 g/1, wherein preferably ratios given above apply.

The present invention is also directed to the use of the compositions according to the invention for foliar application.

Further, the present invention is directed to the use of the surfactant combination of b), c) and d) described above for the production of compositions with low spray volumes.

A further aspect of the present invention is the use of agrochemical compositions according to the invention to combat or control an agricultural pest, weed or disease.

The present invention is directed to the use of the agrochemical compositions according to the invention to improve the rainfastness of an agrochemical active ingredient as well as the resistance to wash-off by rain of an agrochemical active ingredient.

The present invention is also directed to the use of the compositions according to the invention to reduce off-target losses to the environment of an agrochemical active ingredient.

A Suitable compounds a) of the compositions according to the invention are agrochemical active compounds which are solid at room temperature.

Solid, agrochemical active compounds a) are to be understood in the present composition as meaning all substances customary for plant treatment, whose melting point is above 20°C. Fungicides, bactericides, insecticides, acaricides, nematicides, molluscicides, herbicides, plant growth regulators, plant nutrients, biological actives substances and repellents may preferably be mentioned.

The active compounds identified here by their common names are known and are described, for example, in the pesticide handbook (“The Pesticide Manual” 16th Ed., British Crop Protection Council 2012) or can be found on the Internet (e.g. http://www.alanwood.net/pesticides). The classification is based on the current IRAC Mode of Action Classification Scheme at the time of filing of this patent application.

Preferred insecticides a) are for example one or more of: abamectin; acetamiprid; acrinathrin; acynonapyr; benzpyrimoxan; broflanilide; clothianidin; cyantraniliprole; chlorantraniliprole; cyclaniliprole; dicloromezotiaz; dodecadienol; flubendiamide; fluhexafon; imidacloprid; nitenpyram, chlorfenapyr; emamectin; ethiprole; fipronil; flonicamid; flupyradifurone; indoxacarb; metaflumizone; methoxyfenozid; milbemycin; oxazosulfyl; pyridaben; pyridalyl; silafluofen; spinosad; spirodiclofen; spiromesifen; spirotetramat; sulfoxaflor; tetraniliprole; thiacloprid; thiamethoxam; triflumezopyrim; triflumuron.

More preferred insecticides a) are imidacloprid, acetamiprid, thiacloprid, thiamethoxam, cyantraniliprole, chlorantraniliprole, flubendiamide, tetraniliprole, cyclaniliprole, spiromesifen, spirotetramat, ethiprole, fipronil, flupyradifurone, methoxyfenozid, sulfoxaflor and triflumuron.

Most preferred insecticides a) is thiacloprid.

Preferred fungicides a) are for example one or more of: amisulbrom; bixafen; fenamidone; fenhexamid; fluopicolide; fluopyram; fluoxastrobin; iprovalicarb; isotianil; pencycuron; penflufen; propineb; prothioconazole; tebuconazole; trifloxystrobin; ametoctradin; amisulbrom; azoxystrobin; benthiavalicarb- isopropyl; benzovindiflupyr; boscalid; carbendazim; chlorothanonil; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; dichlobentiazox; difenoconazole; dipymetitrone; ethaboxam; epoxiconazole; famoxadone; fenpicoxamid; florylpicoxamid; fluazinam; fluopimomide; fludioxonil; fluindapyr; fluquinconazole; flusilazole; flutianil; fluxapyroxad; ipfentrifluconazole; ipflufenoquin; isopyrazam; kresoxim-methyl; lyserphenvalpyr; mancozeb; mandipropamid; mefentrifluconazole; oxathiapiprolin; penthiopyrad; picarbutrazox; picoxystrobin; probenazole; proquinazid; pydiflumetofen; pyraclostrobin; pyraziflumid; pyridachlometyl; quinofumelin; sedaxane; tebufloquin; tetraconazole; valiphenalate; zoxamide; N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-l-methyl-lH-pyrazole-4- carboxamide; 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}-piperidin-4-yl)-l,3-thiazol- 4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonat; and other fungicides can be used.

More preferred fungicides a) are for example such as bixafen, fenamidone, fluopicolide, fluopyram, fluoxastrobin, isotianil, penflufen, propineb, prothioconazole, tebuconazole, trifloxystrobin, ametoctradin, amisulbrom, azoxystrobin, benthiavalicarb-isopropyl, benzovindiflupyr, boscalid, chlorothanonil, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, difenoconazole, ethaboxam, epoxiconazole, fluazinam, fluquinconazole, fluxapyroxad, isopyrazam, lyserphenvalpyr, mancozeb, oxathiapiprolin, penthiopyrad, picoxystrobin, probenazole, proquinazid, pydiflumetofen, pyraclostrobin, tetraconazole, valiphenalate, zoxamide, isoflucypram , 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l, 3-thiazol-4-yl]-4, 5-dihydro- l,2-oxazol-5-yl}-3-chlorophenyl

methanesulfonate .

Most preferred fungicides a) are tebuconazole, penflufen, trifloxystrobin and isotianil. Preferred herbicides a) are for example (always comprise all applicable forms such as acids, salts, ester, with at least one applicable form): aclonifen; amidosulfuron; bensulfuron-methyl; bromoxynil; bromoxynil potassium; chlorsulfuron; clodinafop; clodinafop-propargyl; clopyrabd; cyclopyranil; 2,4-D, 2,4-D-dimethylammonium, -diolamin, -isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine; 2,4-DB, 2,4-DB dimethylammonium, -potassium, and -sodium; desmedipham; dicamba; diflufenican; diuron; ethofumesate; ethoxysulfuron; fenoxaprop-P; fenquinotrione; flazasulfuron; florasulam; florpyrauxifen; florpyrauxifen-benzyl; flufenacet; fluroxypyr; flurtamone; fomesafen; fomesafen-sodium; foramsulfuron; glufosinate; glufosinate-ammonium; glyphosate; glyphosate- isopropylammonium, -potassium, and trimesium; halauxifen; halauxifen-methyl; halosulfuron-methyl; indaziflam; iodosulfuron-methyl-sodium; isoproturon; isoxaflutole; lenacil; MCPA; MCPA- isopropylammonium, -potassium, and sodium; MCPB; MCPB-sodium; mesosulfuron-methyl; mesotrione; metosulam; metribuzin; metsulfuron-methyl; napropamide; napropamide-M; nicosulfuron; pendimethabn; penoxsulam; phenmedipham; picolinafen ; pinoxaden; propoxycarbazone-sodium; pyrasulfotole; pyroxasulfone; pyroxsulam; rimsulfuron; saflufenacil; sulcotrion; tefuryltrione; tembotrione; thiencarbazone-methyl; tolpyralate; topramezone; triafamone; tribenuron-methyl; trifludimoxazin; and other herbicides can be used.

Preferred safeners a) or h) are: Mefenpyr-diethyl, Cyprosulfamide, Isoxadifen-ethyl, (RS)-l-methylhexyl

(5-chloroquinobn-8-yloxy)acetate (Cloquintocet-mexyl, CAS-No. : 99607-70-2),

metcamifen.

More preferred herbicides a) are for example (always comprise all applicable forms such as acids, salts, ester, with at least one applicable form): amidosulfuron, bensulfuron-methyl, chlorsulfuron, diflufenican, ethoxysulfuron, fenquinotrione, flaza-sulfuron, flufenacet, fluroxypyr, foramsulfuron, halauxifen, halauxifen-methyl, halosulfuron-methyl, iodosulfuron-methyl-sodium, mesosulfuron-methyl, mesotrione, metsulfuron-methyl, nicosulfuron, penoxsulam, pinoxaden, propoxycarbazone-sodium, pyrasulfotole, pyroxasulfone, rimsulfuron, tembotrione, thien-carbazone-methyl, tribenuron-methyl.

Most preferred herbicides a) is diflufenican.

Preferred safeners a) or h) are: Mefenpyr-diethyl, Cyprosulfamide, Isoxadifen-ethyl, (RS)-l-methylhexyl (5-chloroquinobn-8-yloxy)acetate (Cloquintocet-mexyl, CAS-No. : 99607-70-2).

Suitable active ingredients according to the invention may optionally additionally include soluble active ingredients for example dissolved in the aqueous carrier phase and/or liquid active ingredient(s) for example dispersed as an emulsion in the aqueous carrier phase.

All named active ingredients as described here above can be present in the form of the free compound and/or, if their functional groups enable this, an agriculturally acceptable salt thereof. Furthermore, mesomeric forms as well as stereoisomeres or enantiomeres, where applicable, shall be enclosed, as these modifications are well known to the skilled artisan, as well as polymorphic modifications.

B Suitable alkylsulfosuccinates b) are mono-and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular alkali metal salts, more particular sodium salts, and most particular sodium dioctylsulfosuccinate;

C Suitable organosilicone ethoxylates c) are organomodified polysiloxanes/ trisiloxane alkoxylates with the following CAS No. 27306-78-1, 67674-67-3, 134180-76-0, e.g., Silwet^® L77, Silwet^® 408, Silwet® 806, BreakThru^® S240, BreakThru^® S278;

D Suitable acrylic based emulsion polymers or polymer dispersions and styrene based emulsion polymers or polymer dispersions d) are aqueous polymer dispersions with a Tg in the range from -100°C to 30°C, preferably between -60°C and 20°C, more preferably between -50°C and 10°C, most preferably between -45 °C and 5°C, for example Acronal V215, Acronal 3612, Licomer ADH 205 and Atplus FA. Particularly preferred are Licomer ADH205, and Atplus FA.

Preferably, the polymer is selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and derivatives thereof, polyolefins, polyurethanes and natural polymers and derivatives thereof.

More preferably, the polymer is selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolysed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymer, polyurethane, cellulose, gelatine, caesin, oxidised starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose.

Most preferably the polymer is selected from copolymers of an acrylate and a styrene. Said acrylate selected from the list comprising 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof. Said styrene selected from the list comprising styrene, tert-butyl styrene, para-methyl styrene, or combinations thereof.

In a preferred embodiement the polymer, as described above, has a molecular weight of no more than 40000, preferably no more than 10000.

In a preferred embodiment the polymer D is an emulsion polymer as described in WO 2017/202684. The glass transition temperature (Tg) is known for many polymers and is determined in the present invention, if not definded otherwise, according to ASTM E1356-08 (2014) "Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry" wherein the sample is dried prior to DSC at 110°C for one hour to eliminate effect of water and/or solvent, DSC sample size of 10-15 mg, measured from -100°C to 100°C at 20°C/min under N2, with Tg defined as midpoint of the transition region.

E Suitable non-ionic surfactants or dispersing aids e) are all substances of this type which can customarily be employed in agrochemical agents. Preferably, polyethylene oxide-polypropylene oxide block copolymers, preferably having a molecular weight of more than 6,000 g/mol or a polyethylene oxide content of more than 45%, more preferably having a molecular weight of more than 6,000 g/mol and a polyethylene oxide content of more than 45%, polyethylene glycol ethers of branched or linear alcohols, reaction products of fatty acids or fatty acid alcohols with ethylene oxide and/or propylene oxide, furthermore polyvinyl alcohol, polyoxyalkylenamine derivatives, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters, furthermore branched or linear alkyl ethoxylates and alkylaryl ethoxylates, where polyethylene oxide-sorbitan fatty acid esters may be mentioned by way of example. Out of the examples mentioned above selected classes can be optionally phosphated, sulphonated or sulphated and neutralized with bases.

Possible anionic surfactants e) are all substances of this type which can customarily be employed in agrochemical agents. Alkali metal, alkaline earth metal and ammonium salts of alkylsulphonic or alkylphospohric acids as well as alkylarylsulphonic or alkylarylphosphoric acids are preferred. A further preferred group of anionic surfactants or dispersing aids are alkali metal, alkaline earth metal and ammonium salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of alkylnaphthalene sulphonic acids, salts of naphthalene-sulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.

F A rheological modifier is an additive that when added to the recipe at a concentration that reduces the gravitational separation of the dispersed active ingredient during storage results in a substantial increase in the viscosity at low shear rates. Low shear rates are defined as 0.1 s ¹ and below and a substantial increase as greater than x2 for the purpose of this invention. The viscosity can be measured by a rotational shear rheometer.

Suitable rheological modifiers f) by way of example are:

Polysaccharides including xanthan gum, guar gum and hydroxyethyl cellulose. Examples are Kelzan^®, Rhodopol^® G and 23, Satiaxane^® CX911 and Natrosol^® 250 range. Clays including montmorillonite, bentonite, sepeolite, attapulgite, laponite, hectorite. Examples are Veegum^® R, Van Gel^® B, Bentone^® CT, HC, EW, Pangel^® M100, M200, M300, S, M, W, Attagel^® 50, Laponite^® RD,

Fumed and precipitated silica, examples are Aerosil^® 200, Siponat^® 22.

Preferred are xanthan gum, montmorillonite clays, bentonite clays and fumed silica.

G Suitable antifoam substances g) are all substances which can customarily be employed in agrochemical agents for this purpose. Silicone oils, silicone oil preparations are preferred. Examples are Silcolapse^® 426 and 432 from Bluestar Silicones, Silfoam^® SRE and SC132 from Wacker, SAF-184^® fron Silchem, Foam- Clear ArraPro-S^® from Basildon Chemical Company Ltd, SAG^® 1572 and SAG^® 30 from Momentive [Dimethyl siloxanes and silicones, CAS No. 63148-62-9] Preferred is SAG^® 1572.

H Suitable other formulants h) are selected from biocides, antifreeze, colourants, pH adjusters, buffers, stabilisers, antioxidants, inert filling materials, humectants, crystal growth inhibitors, micronutirients by way of example are:

Possible preservatives are all substances which can customarily be employed in agrochemical agents for this purpose. Suitable examples for preservatives are preparations containing 5-chloro-2-methyl-4- isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1.2- benzisothiazol-3(2H)-one [CAS-No. 2634-33-5] Examples which may be mentioned are Preventol^® D7 (Lanxess), Kathon^® CG/ICP (Dow), Acticide^® SPX (Thor GmbH) and Proxel^® GXL (Arch Chemicals).

Suitable antifreeze substances are all substances which can customarily be employed in agrochemical agents for this purpose. Suitable examples are propylene glycol, ethylene glycol, urea and glycerine.

Possible colourants are all substances which can customarily be employed in agrochemical agents for this purpose. Titanium dioxide, carbon black, zinc oxide, blue pigments, Brilliant Blue FCF, red pigments and Permanent Red FGR may be mentioned by way of example.

Possible pH adjusters and buffers are all substances which can customarily be employed in agrochemical agents for this purpose. Citric acid, sulfuric acid, hydrochloric acid, sodium hydroxide, sodium hydrogen phosphate (Na₂HPC>₄), sodium dihydrogen phosphate (NaH₂PC>₄), potassium dihydrogen phosphate (KΉ₂RO₄), potassium hydrogen phosphate (K₂HPO₄), may be mentioned by way of example.

Suitable stabilisers and antioxidants are all substances which can customarily be employed in agrochemical agents for this purpose. Butylhydroxytoluene [3.5-Di-tert-butyl-4-hydroxytoluol, CAS-No. 128-37-0] is preferred. I Suitable compatibilizers i) are i. polyalkylene oxide block copolymers, preferably a polyalkylene oxide block copolymer which has a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, more preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%, even more preferably a molecular weight of 2,000 to 4,000 g/mol and an ethylene oxide content of 15 to 30% and especially preferred a molecular weight of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%; polyalkylene oxide block copolymers according to i. are preferably selected from the group consisting of polyethylene oxide-polypropylene oxide block copolymers and polyethylene oxide-polybutylene oxide block copolymers, more preferably from the group of polyethylene oxide-polypropylene oxide block copolymers;

ii. ethoxylated branched alcohols (e.g. Genapol^® X-type) with 2-20 EO units;

iii. methyl end-capped, ethoxylated branched alcohols (e.g. Genapol^® XM-type) comprising 2-20 EO units;

iv. ethoxylated coconut alcohols (e.g. Genapol^® C-types) comprising 2-20 EO units;

v. ethoxylated C12/15 alcohols (e.g. Synperonic^® A-types) comprising 2-20 EO units;

vi. propoxy-ethoxylated alcohols, branched or linear, e.g. Antarox^® B/848, Atlas^® G5000, Lucramul^® HOT 5902;

vii. ethoxylated diacetylene-diols (e.g. Surfynol^® 4xx-range);

viii. propoxy-ethoxylated fatty acids, Me end-capped, e.g. Leofat^® OC0503M;

ix. alkyl ether citrate surfactants (e.g. Adsee^® CE range, Akzo Nobel);

x. alkylpolysaccharides (e.g. Agnique^® PG8107, PG8105, Atplus^® 438, AL-2559, AL-2575); xi. ethoxylated mono- or diesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 10-40 EO units (e.g. Crovol^® range);

xii. castor oil ethoxylates comprising an average of 5-40 EO units (e.g. Berol^® range, Emulsogen^® EL range).

In a most preferred embodiment the compatibilizer is polyalkylene oxide block copolymer i., more preferred with a molecular weight of 2,400 to 2,500 g/mol and an ethylene oxide content of 20%.

If not otherwise defined in this application, the molecuar weight refers to the weight-average molecular weight M_w which is determined by GPC in methylene chloride at 25 °C with polystyrene as the standard. The formulations according to the invention constitute formulations which remain stable even following prolonged storage at elevated temperatures or in the cold, since no significant thickening or aggregation is observed. By dilution with water they can be converted into homogeneous spray liquids. These spray liquids are applied by customary methods, i.e., for example, by spraying, pouring or injecting, in particular by spraying, and most particular by spraying by UAV. The application rate of the formulations according to the invention can be varied within a relatively wide range. It is guided by the particular active agrochemicals and by their amount in the formulations.

With the aid of the formulations according to the invention it is possible to deliver active agrochemical to plants and/or their habitat in a particularly advantageous way.

The present invention is also directed to the use of agrochemical compositions according to the invention for the application of the agrochemical active compounds contained to plants and/or their habitat.

With the formulations of the invention it is possible to treat all plants and plant parts. By plants here are meant all plants and plant populations, such as desirable and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and gene-technological methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by varietal property rights. By plant parts are to be meant all above-ground and below-ground parts and organs of the plants, such as shoot, leaf, flower and root, an exemplary listing embracing leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. The plant parts also include harvested material and also vegetative and generative propagation material.

What may be emphasized in this context is the particularly advantageous effect of the formulations according to the invention with regard to their use in cereal plants such as, for example, wheat, oats, barley, spelt, triticale and rye, but also in maize, sorghum and millet, rice, sugar cane, soya beans, sunflowers, potatoes, cotton, oilseed rape, canola, tobacco, sugar beet, fodder beet, asparagus, hops and fruit plants (comprising pome fruit such as, for example, apples and pears, stone fruit such as, for example, peaches, nectarines, cherries, plums and apricots, citrus fruits such as, for example, oranges, grapefruits, limes, lemons, kumquats, tangerines and satsumas, nuts such as, for example, pistachios, almonds, walnuts and pecan nuts, tropical fruits such as, for example, mango, papaya, pineapple, dates and bananas, and grapes) and vegetables (comprising leaf vegetables such as, for example, endives, com salad, Florence fennel, lettuce, cos lettuce, Swiss chard, spinach and chicory for salad use, cabbages such as, for example, cauliflower, broccoli, Chinese leaves, Brassica oleracea (L.) convar. acephala var. sabellica L. (curly kale, feathered cabbage), kohlrabi, Brussels sprouts, red cabbage, white cabbage and Savoy cabbage, fruit vegetables such as, for example, aubergines, cucumbers, capsicums, table pumpkins, tomatoes, courgettes and sweetcom, root vegetables such as, for example celeriac, wild turnips, carrots, including yellow cultivars, Raphanus sativus var. niger and var. radicula, beetroot, scorzonera and celery, legumes such as, for example, peas and beans, and vegetables from the Allium family such as, for example, leeks and onions. The treatment of the plants and plant parts in accordance with the invention with the inventive formulations is carried out directly or by action on their environment, habitat or storage area in accordance wih the customary treatment methods, for example by dipping, spraying, vaporizing, atomizing, broadcasting or painting on and, in the case of propagation material, especially seeds, additionally by single or multiple coating.

The active agrochemicals comprised develop a better biological activity than when applied in the form of the corresponding conventional formulations.

The invention is illustrated by the following examples.

Examples

A) Methods

The formulations were prepared according to the following methods.

Method 1:

The method of the preparation of suspension concentrate formulations are known in the art and can be produced by known methods familiar to those skilled in the art. A 2% gel of the xanthan (f) in water and the biocides (h) was prepared with low shear stirring. The active ingredient(s) (a), non-ionic and anionic dispersants (e), a portion of the antifoam (g) and other formulants (h) were mixed to form a slurry, first mixed with a high shear rotor-stator mixer (Ultra-Turrax^®) to reduce the particle size D(v,0.9) to approximately 50 microns, then passed through one or more bead mills (Eiger^® 250 Mini Motormill) to achieve a particles size D(v,0.9) typically 1 to 15 microns as required for the biological performance of the active ingredient(s). Those skilled in the art will appreciate that this can vary for different active ingredients. The remaining components: mono-and diesters of sulfosuccinate metal salts (b), polyalkyleneoxide modified heptamethyltrisiloxane (c), emulsion polymer or polymer dispersion (d), portion of the antifoam (g) and xanthan gel prepared above were added and mixed in with low shear stirring until homogeneous. Finally the pH was adjusted to 7.0 (+/- 0.2) with acid or base (h).

The formulation stability was determined according to the following method.

Method 2:

The stability of the example formulations was determined by storing samples at a range of temperatures including 45 °C, 40°C, 30°C, RT (22°C), -10°C and -15/30°C cycling (7 days cycle) over storage times up to 24 months. They were then examined visually for any thickening, gravitational separation (total height of sample H and height of sediment phase Ht), aggregation of the active ingredient particles in a 1% dilution in water in a microscope, particle size (D90) from laser diffraction (Malvern Mastersizer) and viscosity at a shear rate of 20s ¹ and a temperature of 20°C. Storage tests at higher temperatures (40°C and 45 °C) over shorter time scales may be used as accelerated storage tests for an indication of product stability at normal temperatures (20°C and 30°C) and normal product shelf life (2 years). The D90 is the particle diameter where 90% of the particles by volume are less than this value. The viscosity may be measured with a rotational shear rheometer according to CIPAC MT192.

B) Materials

Table I: Exemplified trade names and CAS-No’s of preferred compounds b)

Table II: Exemplified trade names and CAS-No’s of preferred compounds c)

Table HE Exemplified trade names and CAS-No’s of preferred compounds d)

Table IV: Exemplified trade names and CAS-No’s of preferred compounds e)

Table V : Exemplified trade names and CAS-No’s of preferred compounds f)

Table VI: Exemplified trade names and CAS-No’s of preferred compounds g)

Table VII: Exemplified trade names and CAS-No’s of preferred compounds h)

Table VIII: Exemplified trade names and CAS-No’s of preferred compounds i)

Example 1:

Formulations were prepared with the following recipes: Table IX: Recipes 1, 2 and 3.

The method of preparation used was according to Method 1.

The recipes 1 and 2 according to the invention exhibited good stability during storage testing for up to 2 years according to Method 2. Table X: Storage stability for recipes 1 and 2.

The biological performance of recipe 1 (according to the invention) and recipe 3 was compared outdoors in paddy rice at spray volumes of 400 to 600 L/ha. The biological efficacy for leaf and neck rice blast disease was assessed 7-15 days after the second foliar spray application (assessment 1) and again after 19- 22 days (assessment 2) and the yield measured at harvest. Table XI: Biological efficacy and yield results from example 1.

The results show that recipe 1 according to the invention gave superior biological control and an increased yield compared to the reference recipe 3. Example 2:

In an other example 1 litre each of recipes 2 and 3 were diluted in 7 litres of water and sprayed by a Maruyama MMC940AC drone fitted with two Yamaha flat fan nozzles flying at a height of 2 m at an application rate of 8 1/ha onto leaf sections taken from rice, soybean and com plants. A fluorescent marker (Tinopal OB®) was added and the spray coverage determined from analysis of images obtained under UV illumination. The drone flew at a height of 2 m and a speed of 15-20 km/h.

Table XII: Leaf coverage after srpay application by drone at 8 1/ha.

The results shown in table XII demonstrate that recipe 2 (according to the invention) showed a much improved wetting and coverage of each of the leaf surfaces. Example 3:

In another example recipes 2 and 3 were diluted at a rate of 1 litre of SC in 7 litres of water and sprayed by a Maruyama MMC940AC drone fitted with two Yamaha flat fan nozzles flying at a height of 2 m at an application rate of 8 1/ha onto rice plants (cv. Koshihikari) in pots at the growth stage of full tillering with the same application conditions as above. The rice plants were inoculated with rhizoctonia solani 17 days after application followed by incubation at 25 °C and 100% relative humidity for 7 days under dark conditions. The rice plants were then grown in a greenhouse for 18 days and assessed for disease control.

Table XIII: Disease control after srpay application by drone at 8 1/ha.

The results in table XIII demonstrate that recipe 2 (according to the invention) gave enhanced control of disease.

Example 3b:

In an example recipes 2 and 3 were diluted at a rate of 1 litre of SC in a range of water volumes ranging from 1200 1/ha to 4 1/ha and along with a small amount of a fluorescent label and were sprayed by a back- pack sprayer onto outdoor rice plants (japonica) fitted with (Teejet) Conejet^® TXVS nozzles (1200-600 1/ha TXVS-8, 300-4 1/ha TXVS-2) at the growth stage of ripening. The spray deposits on isolated rice leaves were photographed under UV illumination and the coverage of the spray and mean spray deposit area was measured using ImageJ image analysis software (Fiji package, www.fiji.com).

Table XIV : Leaf coverage and spray deposit area at different spray volumes.

The results in table XIV demonstrate that recipe 2 (for the described sprayable liquid for low volume spray application) remarkably gave significantly improved coverage at 50 to 4 1/ha compared to the reference recipe 3. At 100 1/ha the coverage was significantly lower for recipe 2 demonstrating the importance of low spray volumes less than or equal to 50 1/ha for achieving a significantly higher leaf coverage of the spray mixture. At 200 to 1200 1/ha a higher coverage was observed from the greater spray volume. Importantly, recipe 2 sprayed at 4 to 50 1/ha achieved a comparable coverage to the reference recipe 3 at 600 1/ha demonstrating that the described sprayable liquid for low volume spray application can achieve comparable coverage to reference formulations sprayed at much higher conventional spray volumes. However, the reference formulation 3 did not achieve comparable coverage at low spray volumes less than 100 1/ha.

The same enhancement of coverage can be seen with the mean spray deposit area, recipe 2 (for the described sprayable liquid for low volume spray application) remarkably also produced spray deposits with significantly higher spreading between 50 and 4 1/ha. Higher spray volumes of 100 and 200 1/ha produced deposits with much lower areas as did the reference recipe at 4 to 300 1/ha. The results from table XIV are plotted in Fig. 2.

Both of these results demonstrate the advantage of the described sprayable liquid at low volume spray application between 4 and 50 litres per hectare for application by an unmanned aerial vehicle as described here.

Example 4:

Formulations were prepared with the following recipes: Table XV : Recipes 4, 5 and 6.

The method of preparation used was according to Method 1.

The recipes 4 and 6 according to the invention exhibited good stability during storage testing according to Method 2.

Table XVI: Storage stability for recipes 4 and 6.

Example 5:

In another example Nativo^® WG (Bayer AG) containing 25%w/w trifloxystrobin and 50%w/w tebuconazole and Recipe 5 were sprayed onto greenhouse grown rice plants (growth satge 21) at a spray rate of 0.2 kg/ha for Nativo^® WG and 0.5 1/ha for recipe 5 in a water volume of 100 1/ha.

Table XVII: Amount of active ingredient remaining on and in the plants after spray application.

The results show that recipe 5 according to the invention demonstrated significantly higher retention on rice plants than Nativo^® WG. Example 6: Low spray volumes

In an example recipe 4 for the described sprayable liquid for low volume spray application and the commercial product Nativo^® 300 SC (Bayer AG, registration number L8942 South Africa, code 102000008381) which contains 100 g/1 of trifloxystrobin and 200 g/1 of tebuconazole were applied by spray application to paddy rice using a low spray volume of 60 1/ha and assessed for control of neck blast disease after two applications. The treated crops were then harvested and the yield measured. Table XVIII: Biological results for recipe 4 and Nativo^® SC.

The results show that at the low spray volume of 60 1/ha recipe 4 according to the invention gave both significantly higher disease control and increased yield compared to the commercial reference Nativo^® SC.

Example 7:

Formulations were prepared with the following recipes: Table XIX: Recipes 7 and 8.

The method of preparation used was according to Method 1.

The recipes 9 (according to the invention) and 10 exhibited good stability during accelerated storage testing of 8 weeks according to Method 2.

Table XX: Storage stability for recipes 7 and 8.

Example 8: Insecticides

Table XXI: Formulations were prepared with the following recipes:

The method of preparation used was according to Method 1

Recipes 9, 10 and 11 along with a small amount of a fluorescent label were sprayed onto rice leaves at a spray volume of 10 1/ha and formulation rate of 1.0 1/ha and the coverage of the spray measured from the fluorescence under UV illumination using ImageJ image analysis software (Fiji package, www.fiji.com).

Table XXII: Leaf coverage results

The results show that recipe 9 according to the invention showed significantly higher coverage than the reference recipes 10 and 11.

Example 9: Herbicide

Formulations were prepared with the following recipes: Table XXIII: Recipes 12 and 13.

The method of preparation used was according to Method 1

Recipes 12 and 13 along with a small amount of a fluorescent label were sprayed onto rice leaves at a spray volume of 10 1/ha and formulation rate of 0.5 1/ha and the coverage of the spray measured from the fluorescence under UV illumination using ImageJ image analysis software (Fiji package, www.fiji.com).

Table XXIV : Leaf coverage results

The results show that recipe 12 according to the invention showed significantly higher coverage than the reference recipe 13.

Claims

Patent claims

1. Agrochemical compositions comprising an aqueous dispersion of a) at least one agrochemical active compound, which is solid at room temperature,

b) at least one compound of the group selected from mono- and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular alkali metal salts, more particular sodium salts, and most particular sodium dioctylsulfosuccinate;

c) at least one polyalkyleneoxide modified heptamethyltrisiloxane,

d) at least one emulsion polymer or polymer dispersion with a glass transition temperature (Tg) in the range from -100°C to 30°C,

e) optionally additives selected from the group consisting of non-ionic surfactants, anionic surfactants and dispersing aids,

f) optionally a rheological modifier,

g) optionally an antifoam agent,

h) optionally other formulants, and

i) at least one compatibilizer.

2. Agrochemical composition according to claim 1, wherein compounds e, f and g are mandatory.

3. Agrochemical compositions according to claim 1 or 2, wherein

a) is selected from the group consisting of herbicides, insecticides, fungicides, host defence inducers and safeners;

b) is sodium dioctylsulfosuccinate;

d) the polymers are selected from the group consisting of acrylic polymers, styrene polymers, vinyl polymers and derivatives thereof, polyolefins, polyurethanes and natural polymers and derivatives thereof; and

e) is selected from the group of polyalkylene oxide block copolymers.

4. Agrochemical compositions according to to one or more of the preceeding claims, wherein in d) the polymers are selected from the group consisting of acrylic polymers, styrene butadiene copolymers, styrene-maleic anhydride copolymers, polyvinyl alcohol, polyvinyl acetate, partially hydrolysed polyvinyl acetate, methyl vinyl ether-maleic anhydride copolymers, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, isopropylene-maleic anhydride copolymer, polyurethane, cellulose, gelatine, caesin, oxidised starch, starch-vinyl acetate graft copolymers, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose; and i) the compatibilizer is selected from the group of polyalkylene oxide block copolymers having a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%.

5. Agrochemical compositions according to one or more of the preceeding claims, wherein in

d) the polymer is a copolymer of an acrylate and a styrene, wherein said acrylate is selected from the group consisting of 2-ethyl-hexyl acrylate, butyl acrylate, sec-butyl acrylate, ethyl acrylate, methyl acrylate, acrylic acid, acrylamide, iso-butyl acrylate, methyl methacrylate, or combinations thereof, and said styrene is selected from the group consisting of styrene, tert-butyl styrene, para- methyl styrene, or combinations thereof.

6. Agrochemical compositions according to one or more of the preceeding claims, wherein in

i) the compatibilizer is selected from the group of polyalkylene oxide block copolymers having a molecular weight (weight-average molecular weight M_w) of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%.

7. Agrochemical compositions according to one or more of the preceeding claims, wherein the compounds a) to i) are present in an amount of

a) 10 to 600 g/1, preferably 50 to 400 g/1, more preferably 100 to 400 g/1, most preferred 200 to 360 g/1 b) 1 to 80 g/1, preferably 4 to 60 g/1, more preferably 4 to 50 g/1, most preferred 10 to 30 g/1 c) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 d) 1 to 80 g/1, preferably 2.5 to 60 g/1, more preferably 5 to 55 g/1, most preferred 10 to 50 g/1 e) 0 to 100 g/1, preferably 2.5 to 80 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 f) 0 to 60 g/1, preferably 1 to 40 g/1, more preferably 1 to 20 g/1, most preferred 1 to 15 g/1

g) 0 to 25 g/1, preferably 1 to 20 g/1, more preferably 1 to 15 g/1, most preferred 1 to 10 g/1

h) 0 to 150 g/1, preferably 1 to 100 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 i) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 wherein water is added to volume (1 litre).

8. Agrochemical compositions according to one or more of claims 1 to 6 without dilution, wherein the compounds a) to i) are present in an amount of

a) 10 to 600 g/1, preferably 50 to 400 g/1, more preferably 100 to 300 g/1, most preferred 150 to 270 g/1 b) 1 to 80 g/1, preferably 4 to 60 g/1, more preferably 4 to 50 g/1, most preferred 10 to 30 g/1 c) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 d) 1 to 80 g/1, preferably 2.5 to 60 g/1, more preferably 5 to 50 g/1, most preferred 10 to 45 g/1 e) 0 to 100 g/1, preferably 2.5 to 80 g/1, more preferably 5 to 60 g/1, most preferred 20 to 45 g/1 f) 0 to 60 g/1, preferably 1 to 40 g/1, more preferably 1 to 20 g/1, most preferred 1 to 15 g/1

g) 0 to 25 g/1, preferably 1 to 20 g/1, more preferably 1 to 15 g/1, most preferred 1 to 10 g/1

h) 0 to 150 g/1, preferably 1 to 120 g/1, more preferably 1 to 60 g/1, most preferred 20 to 45 g/1 i) 1 to 70 g/1, preferably 2.5 to 50 g/1, more preferably 5 to 45 g/1, most preferred 10 to 40 g/1 wherein water is added to volume (1 liter).

9. Use of an agrochemical composition according to one or more of the preceeding claims in application of the agrochemical compounds for controlling harmful organisms, wherein the composition is applied by a UAV.

10. Method of controlling harmful organisms, comprising the contacting of the harmful organisms, their habitat, their hosts, such as plants and seed, and the soil, the area and the environment in which they grow or could grow, but also of materials, plants, seeds, soil, surfaces or spaces which are to be protected from attack or infestation by organisms that are harmful to plants, with an effective amount of the formulations according to one or more of Claims 1 to 8, characterized in that the composition is applied by a UAV.

11. Process for producing liquid formulations according to one or more of Claims 1 to 8 by mixing components a), b), c), d), e), f), g) and i) and optional further additives h).

12. Adjuvant combination for low spray volume agrochemical combinations consisting of b) sodium dioctylsulfosuccinate, c) a polyalkyleneoxide modified heptamethyltrisiloxane, i) a polyalkylene oxide block copolymer, wherein the compounds b), c) and i) are defined as in the compositions above.

13. Adjuvant combination for low spray volume agrochemical combinations according to claim 12, wherein compound i) is selected from the group of polyalkylene oxide block copolymers having a molecular weight (weight-average molecular weight M_w) of 1,500 to 6,000 g/mol and an ethylene oxide content of 8 to 45%, preferably a molecular weight of 1,800 to 5,000 g/mol and an ethylene oxide content of 10 to 35%.

14. Adjuvant combination for low spray volume agrochemical combinations according to claim 12 or 13, wherein compound i) is selected from the group of polyalkylene oxide block copolymers having a molecular weight (weight-average molecular weight M_w) of 2,200 to 3,000 g/mol and an ethylene oxide content of 18 to 22%.

15. Adjuvant combination for low spray volume agrochemical combinations according to any of claims 12 to 14, wherein the compounds b, c and i are present in a ratio from 1 : 1 : 1 to 1 :4:3, preferably from 1: 1 : 1 to 1:3:3, and most preferred in a ratio from 1: 1.5: 1.5 to 1: 2.5:2.5.

16. Adjuvant combination for low spray volume agrochemical combinations according to any of claims 12 to 14, wherein the compounds c and i are present in a ratio from 4: 1 to 1:4, preferably from 2: 1 to 1:2, and most preferred in a ratio from 4:3 to 3:4.

17. Adjuvant combination for low spray volume agrochemical combinations according to any of claims 12 to 14, wherein the amount of said surfactants b, c and i in the agrochemical compositions according to claims 1 to 6 is from 10 to 200 g/1, preferable from 15 to 150 g/1, more preferred from 20 to 120 g/1, and most preferred from 40 to 100 g/1.

18. Adjuvant combination for low spray volume agrochemical combinations consisting of b) sodium dioctylsulfosuccinate, c) a polyalkyleneoxide modified heptamethyltrisiloxane, d) at least one emulsion polymer or polymer dispersion with Tg in the range from -100°C to 30°C, wherein the compounds b), c) and d) are defined as in the compositions above.