The present invention relates to storage stable, liquid, pesticidal compositions, the preparation of such compositions and a method of using such compositions to combat pests or as plant growth regulators.

Alkylphenol ethoxylates, for example nonylphenol ethoxylates, and alkylbenzene sulfonates and its salts, for example dodecylbenzene sulfonate calcium salt, are commonly used and well known surfactants in water-emulsifiable pesticidal compositions.

Some of these surfactants are not entirely satisfactory; in particular with respect to their ecological and toxicological properties.

There is still a need for further water-emulsifiable or water soluble, liquid, homogeneous pesticidal compositions which are storage stable, ecological and toxicological favourable and which have good pesticidal efficacy.

Fatty alcohol ethoxylates, e.g. Cι ₀ -Cι ₄ alcohol ethoxylates (EP-A-400,585) and tristyrenephenol-ethoxylates (EP-A-102,003) have been proposed, both in combination with alkylbenzene sulfonates, as surfactants in water-emulsifiable pesticidal compositions. C ₁ -C ₁₀ Alkyl ethoxylate/propoxylate-blockcopolymers and tristyrenephenol-ethoxylates have been disclosed as surfactants in aqueous suspensions (EP-A-261 ,492).

A novel combination of surfactants for water-emulsifiable or water-soluble pesticidal compositions has now been found; the novel compositions are storage stable, easy to apply, ecological and toxicological favourable and have good pesticidal efficacy.

Accordingly, the present invention provides a water-emulsifiable or water-soluble, storage stable, liquid, pesticidal composition, which is substantially free of water, comprising a hydrophobic pesticide or mixture of pesticides dissolved in an organic solvent and comprising as surfactants

(1) a butanole-ethoxylate/propoxylate-blockcopolymer having 12-30 mol ethoxylate and 16-48 mol propoxylate, in combination with

(2) a branched C ₈ -C _β alcohol ethoxylate having 5-10 mol ethoxylate, and/or

(3) a tristyrenephenol-ethoxylate having 8-30 mol ethoxylate, or its phosphate or salt thereof.

Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium calcium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower aikylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propylamine, or a mono-, di- or tri-hydroxy-lower aikylamine, for example mono-, di- or tri-ethanolamine.

The compositions also include gels having a viscosity of 500 to 20O00 mPas and comprising additionally a gelling agent.

The compositions according to the invention are stable for at least 12 months at 25°C. They are very well miscible with water, even at higher concentrations.

The surfactants can be combined, depending for example on the kind of pesticide and the preferred solvents, as follows:

(1 ) in combination with (2) and (3); (1) in combination with (2); (1 ) in combination with (3).

The surfactants mentioned above can be prepared by methods known per se; they are also commercially available. Preferred are surfactants, wherein

(1 ) the butanole-ethoxylate/propoxyiate-blockcopolymer has 20-24 mol, preferably 22 mol ethoxylate, and 30-36 mol, most preferably 34 mol propoxylate;

(2) the branched C ₈ -Cιβ alcohol ethoxylate is isotridecanol ethoxylate having 5-10 mol, most preferably 6-8 mol ethoxylate; and

(3) the tristyrenephenol-ethoxylate has 16-18 mol ethoxylate.

The composition of the invention is substantially free of water, i.e. the amount of water is less that 0.5%. Some commercially available materials may contain a small amount of water, which, when more than about 0.1% can be removed for example in a separator.

In another aspect of the invention the composition is a gel with a viscosity of 500 - 20O00 mPas; preferably 800 to 10OOO mPas and particularly 1000-5000 mPas.

The viscosity of the composition can be measured using for example a BROOKFIELD viscosimeter with spindles 1 to 3 at 30 rpm.

In this case the composition additionally has to contain a gelling agent, for example oxypropylated cellulose, precipitated or fused silica (hydrophobizised or non- hydrophobizised), gelatine, polysaccharides, tetramethyl decyne diol, ethoxylated dialkyl

phenol, methylated clay, propylene carbonate, hydrogenated castor oil, ethoxylated vegetable oil, sodium benzoate and hexanediol. Preferred gelling agent is oxypropylated cellulose.

Gels are particularly suitable for pesticides packing into water soluble bags or sachets, which quickly dissolve when put into the water.

The organic solvents wherein the pesticide has to be dissolved may be water-immiscible or water miscible or a mixture thereof.

Suitable water-immiscible solvents in which the pesticides may be dissolved are aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosin, mixtures or substituted naphthalenes, mixtures of mono- and polyalkylated aromatics commercially available under the registered trademarks SOLVESSO and SHELLSOL and PETROL SPEZIAL, halogenated hydroarbons such as methylene chloride, chloroform and o-dichlorobenzene; phthalates, such as dibutyl phthalate or dioctyl phthalate; ethers and esters, such as ethylene glycol monomethyl or monoethyl ether, fatty acid esters; lactones such as butyrolactone, ketones, such as cyclohexanone; plant oils such as castor oil, soybean oil, cottonseed oil and possible methyl esters thereof; as well as epoxidised coconut oil or soybean oil. Preferred water-immiscible solvents are aliphatic and aromatic hydrocarbons, fatty acid esters {e.g. WITCONOL 2309), dipropyleneglycol monomethylether (e.g. DOWANOL DPM) and castor oil. Suitable water-miscible solvents in which the pesticides may be dissolved are alcohols and glycols, such as ethanol, ethylene glycol, strongly polar solvents, such as N-methyl-2- pyrrolidone, tetramethylurea, gamma-butyrolacone.dimethyl sulfoxide, N,N- dimethylacetamid and dimethylformamide; preferred are N-methyl-2-pyrrolidone and gamma-butyrolacone.

Suitable pesticides are those which are substantially insoluble in water (hydrophobic), but soluble in the organic solvent.

The term pesticide is understood to encompass herbicides, insecticides, acaricides, nemati- cides, ectoparasiticides, fungicides and plant growth regulators.

With respect to their chemical constitution, these pesticides may belong to a very wide range of compound classes. Examples of compound classes to which the suitable pesticide may belong are: acylalanines, haloacetanilides, triazole derivatives, phosphoric acid esters, pyrethroids, benzilic acid esters, polycyclic halogenated hydrocarbons, diphenyl ether derivates, formamidines, strobilurines, aryloxyphenoxy-alkanoic acid derivatives. Examples of suitable individual compounds of the above mentioned compound classes are listed

below. Where known, the common name is used to designate the individual compounds

(q.v. the Pesticide Manual, 10th edition, 1994,British Crop Protection Council).

Haloacetanilides: Dimethachlor, Metolachlor, Pretilachlor, 2-chloro-N-(1-methyl-2-methoxy- ethyl)-acet-2,6-xylidide, Alachlor, Butachlor, Propachlor, Dimethenamid.

Diphenyl ether derivates: Bifenox, 4-(4-Pentyn-1-yloxy)diphenylether, Acifluorfen, Oxyfluor- fen, Fluoroglycofen-ethyl, Fomesafen, cis-trans- (±)2-ethyl-5-(4-phenoxy-phenoxymethy!)-

1 ,3-dioxolane ("diofenolan").

Phenoxypropionic acid derivatives: Fluazifop-butyl, Haloxyf op-methyl, Haloxyfop-(2-ethoxy- ethyl), Fluorotopic, Fenoxapropethyl, Quizalofop-ethyl, Propaquizafop, Diclofop-methyl.

Acylalanines: Furalaxyl, etalaxyl, R- Metalaxyl, Benzoylprop ethyl, Benalaxyl, Oxadixyl,

Flamprop methyl.

Triazole derivatives: Difenoconazole, Etaconazol, Propiconazole, Penconazole,

Triadimefon, Epoxiconazole, Tebuconazole, Bromuconazole, Fenbuconazole,

Cyproconazole.

Phosphoric acid esters: Piperophos, Anilofos, Butamifos, Azamethiphos, Chlorfenvinphos,

Dichlorvos, Diazinon, Methidathion, Azinphos ethyl, Azinphos methyl, Chlorpyrifos, Chlor- thiofos, Crotoxyphos, Cyanophos, Demeton, Dialifos, Dimethoate, Disulfoton, Etrimfos,

Famphur, Flusulfothion, Fluthion, Fonofos, Formothion, Heptenophos, Isofenphos,

Isoxathion, Malathion, Mephospholan, Mevinphos, Naled, Oxydemeton methyl, Oxy- deprofos, Parathion, Phoxim, Pyrimiphos methyl, Profenofos, Propaphos, Propetamphos,

Prothiophos, Quinalphos, Sulprofos, Phemephos, Terbufos, Triazophos, Trichloronate,

Fenamipos, Isazophos, s-benzyl-o,o-diisopropylphosphorothioate, Edinphos, Pyrazophos.

Pyrethroids: Allethrin, Bioallethrin, Bioresmethrin, Cyhalotrin, Cypermethrin, α-Cypermethrin, φ-Cypermethrin, Deltamethrin, Fenpropathrin, Fenvalerate, s-Fenvalerate, Flucythrinate,

Fluvalinate, Permethrin, Pyrethrine, Resmethrin, Tetramethrin, Tralomethrin, Ethophenprox,

Cyfluthrin, Cycloprothrin, Tefluthrin, Flufenprox, Silafluofen, Bifenthrin, Fenfluthrin,

Bromfenprox.

Benzilic acid esters: Brompropylate, Chlorbenzylate, Chlorpropylate.

Polvcvclic halogenated hydrocarbons: Aldrin, Endosulfan.

Strobilurines: Kresoxim-methyl, Azoxystrobin (BAS 490F), Methoxyimino-{2-[1-(3- trifluoromethyl-phenyl)- ethylideneaminooxymethyl]-phenyl}-acetic acid methyl ester.

Miscellaneous: Tridemorph, Bromoxynil, Carboxin, Prochloraz, Propargite, Dicamba,

Fenpiclonil, Fenpropimorph, Fenpropidin, Fludioxonil, Pymetrozine, Pyrifenox, Pyriproxyfen,

Trinexapac-ethyl, Fluazinam.

Preferred pesticides are

herbicides, as Propaquizafop, Piperophos and Propanil; fungicides, as Methoxyimino-{2-[1-(3-trifluoromethyl-phenyl)- ethylideneaminooxymethyl]- phenyl}-acetic acid methyl ester, Propiconazole, Cyproconazole, Fluazinam, Metalaxyl or R-

Metalaxyl (enantiomer of Metalaxyl), or a mixture thereof; insecticides, as Diazinon; plant growth regulators, as Trinexapac-ethyl.

Suitable concentrations in relation to the composition are (% weight per volume of the total composition; 1000 g per liter correspond to 100%) a) of the hydrophobic pesticide or mixture of pesticides: 1 to 99 %, preferably 10 to 90% and 20 to 50%; b) of the organic solvent: 1 to 96%, preferably 10 to 80% and 20 to 70%; c) of the surfactants: 3 to 80%, preferably 10 to 40% and 20 to 30%; wherein of surfactant (1): 2 to 25%, preferably 5 to 20%, surfactant (2): 2 to 40%, preferably 5 to 25%, surfactant (3): 2 to 20%, preferably 5 to 15%; d) of the gelling agent: 0.1 to 10 % preferably 0.5 to 5%.

It may be advantageous to add additionally an alkylbenzene sulfonate or its salt, preferably dodecylbenzene sulfonate calcium salt in an amount of 1 to 10%, preferably 2 to 4 % by weight in relation to the volume of the composition. It may be advantageous to combine the pesticide or mixture of pesticides with a safener.

Another object of the invention is a process for preparing a liquid pesticidal composition as herein described, by intimateley mixing, optionally by warming, until a homogeneous phase is achieved.

In another aspect of the invention the composition is an aqueous spray mixture.

Before the application, the composition of the invention may be diluted with water by simple mixing at ambient temperature in order to get a ready for use spray mixture.

This spray mixture may be an aqueous emulsion or a solution or a suspension, depending on the kind of composition.

The resulting spray mixtures are stable, i.e. they remain as a homogeneously emulsified phase, as a solution or as a homogeneously distributed suspension on standing without agitation for at least one hour to 12 hours or even more.

Preferred concentrations of the spray mixture are 0.1 to 5 %, more preferred 0.5 to 2% pesticide in relation to the spray mixture.

Further aspects of the invention include a method of preventing or combatting infestation of plants or animals by pests and regulating plant growth by diluting the composition with water and applying a pesticidally effective amount to the plant, animal or locus as desired.

Preparation examples

The following Examples illustrate the invention in more detail. The registered trademarks and other designations denote the following products:

(1 ) WITCONOL NS 500 K ^® (WITCO) Copolymer of butanol-34 PO/22 EO,

(2) GENAPOL X-080 ^® (HOECHST) lsotridecanol-8 EO GENAPOL X-060 ^® (HOECHST) lsotridecanol-6 EO

(3) SOPROPHOR BSU ^® (RHONE-P) Tristyrenephenole-16 EO

,®

SOPROPHOR 3D33 ^1* (RHONE-P) Tristyrenephenol-poly-EO-phosphate

WITCONOL 2309^ Fatty acid methylester EMULSOGEN EL ^® castor oil-36 EO PETROL SPEZIAL 200* Mixture of aromatic hydrocarbons KLUCEL M ^® Oxypropylated cellulose (gelling agent) DOWANOL DPM ^® Dipropyleneglycol monomethylether (mixture of isomers) EO = ethyleneoxid PO = propyleneoxid

% in weight per volume of the total composition (i.e.1000 g per liter correspond to 100%) The components are intimateley mixed, optionally by warming, until a homogeneous phase is achieved.

ExamD e 1

% component type

10 0 Propaquizafop herbicide

5.0 WITCONOL NS 500 K ^® surfactant (1)

35.0 GENAPOL X-060 ^® surfactant (2)

10.0 1 -Methyl-2-pyrrolidone solvent

40.0 PETROL SPEZIAL 200 solvent

Density: 1.02 g/cπT

ExamD e 2

% component type

14.5 Piperophos herbicide

25.0 Propanil herbicide

8.0 WITCONOL NS 500 K ^® surfactant (1 )

12.0 GENAPOL X-060 ^® surfactant (2)

40.5 Dipropyleneqlycol monomethyl ether solvent

Density: 1.065 g/crτr

Exam pie 3

Density: 1.11 g/cm"

Density: 1.07 g/cm

Exam pie 5

Density: 1.095 g/cm ³

Density: 1.1 g/cm

xam pie 7

Density: 1.073 g/cπr

Exam pie 8

Density: 1.07 g/crrf

Exam pie 9

Density: 1.09 g/cm'

Example 10

% component type

15.0 Methoxyimino-{2-[1 -(3-trifluoromethyl-phenyl)- ethylidene- fungicide aminooxvmethyl]-phenyl}-acetic acid methyl ester

7.0 R-Metalaxyl funqicide

12.5 WITCONOL NS 500 K surfactant (1 )

12.5 SOPROPHOR BSU® surfactant (3)

53.0 1 -Methyl-2-pyrrolidone solvent

Density: 1.081 g/crτr

Example 11

% component type

12.5 Methoxyimino-{2-[1 -(3-trifluoromethyl-phenyl)- ethylidene- fungicide aminooxymethγl]-phenyl}-acetic acid methyl ester

7.5 R-Metalaxyl fungicide

3.0 WITCONOL NS 500 K surfactant (1)

3.0 GENAPOL X-080 ^® surfactant (2)

45.5 1 -Methyl-2-pvrrolidone solvent

27.5 Aromatic solvent 230 solvent

Density: 1.081 g/cm ³

Example 12

% component type

9.3 R-Metalaxyl fungicide

4.0 WITCONOL NS 500 K surfactant (1 )

16.0 GENAPOL X-080 ^® surfactant (2)

5.0 Gamma-Butyrolactone solvent

27.0 Fatty acid methyl ester Me C 6-10 solvent

Density: 1.035 g/cm

ExamD e 13

% component tvpe

17.7 R-Metalaxyl funqicide

26.0q Fluazinam funqicide

5.0 WITCONOL NS 500 K surfactant (1)

5.0 GENAPOL X-060® surfactant (2)

5.0 SOPROPHOR BSU ^® surfactant (3)

16.0 PETROL SPEZIAL 200 ^® solvent

25.3 Gamma-Butyrolactone solvent

Density: 1.184 g/cm ²

Density: 1.073 g/crrf

Examp e 15 (Gel)

% component type

26 Trinexapac-ethyl plant growth regulator

21.0 WITCONOL NS 500 K surfactant (1)

7.0 GENAPOL X-060 ^® surfactant (2)

0.8 KLUCEL M ^® gelling agent

45.2 DOWANOL DPM ^® solvent

Density: 1.027 g/cm ³ ; Viscosity: ca. 2700 mPas (Spindle 3 / 30 rpm)

ExamDl e 16

% component type

26.3 Trinexapac-ethyl plant growth requlator

21.4 WITCONOL NS 500 K surfactant (1)

7.1 GENAPOL X-060 ^® surfactant (2)

45.2 WITCONOL 2309® solvent

Density: 0.98 g/cm"

All the compositions according to the examples are stable for at least 12 months at 25°C.

After diluting with water the compositions form an emulsion or, depending on the pesticide, solvent and concentration, a clear solution. Both the emulsions and solutions are stable without agitation for at least one to 12 hours or even more.