Europäisches Patentamt

(19) European Patent Office *EP001339281B1*

Office européen des brevets (11) EP 1 339 281 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: A01N 25/02
of the grant of the patent:
11.08.2004 Bulletin 2004/33 (86) International application number:
PCT/EP2001/013658
(21) Application number: 01985335.7
(87) International publication number:
(22) Date of filing: 23.11.2001 WO 2002/043488 (06.06.2002 Gazette 2002/23)

(54) OIL-IN-WATER EMULSION FORMULATION OF INSECTICIDES

INSEKTIZIDE ÖL IN WASSER EMULSIONEN
FORMULATION D’EMULSION HUILE DANS L’EAU D’INSECTICIDES

(84) Designated Contracting States: • MANSOUR, Peter

AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU 65203 Wiesbaden (DE)
MC NL PT SE TR • BOURGOGNE, Michel
Designated Extension States: 69005 Lyon (FR)
LT LV RO SI • HENRIET, Michel
40764 Langenfeld (DE)
(30) Priority: 01.12.2000 EP 00126276
(74) Representative: Rippel, Hans Christoph, Dr.
(43) Date of publication of application: Bayer CropScience GmbH,
03.09.2003 Bulletin 2003/36 Patent- und Lizenzabteilung,
Industriepark Höchst,
(73) Proprietor: Bayer CropScience S.A. Gebäude K 607
69009 Lyon (FR) 65926 Frankfurt am Main (DE)

(72) Inventors: (56) References cited:

• TARANTA, Claude EP-A- 1 025 757 WO-A-90/09103
65760 Eschborn (DE) WO-A-96/01047
EP 1 339 281 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 339 281 B1

Description

[0001] The invention relates to liquid formulations of insecticides, in particular pyrethroids, in the form of oil-in-water
(EW) emulsions, to a process for the production of such EW formulations and to their use for pest control.
5 [0002] Due to the enormous damage that is caused by pests on crops, woods, textiles and so on and due to their
role in causing and transmitting diseases of human beings, animals and crops, the use of chemical pesticides is still
unavoidable.
[0003] Insecticides play an important role in integrated pest control, and they are essential in guaranteeing acceptable
yields of harvests all over the world.
10 [0004] Pyrethroids (natural and synthetic ones) in particular are an important class of lipophilic pesticides. Their
arthropodicidal properties are based on a strong influence on the sodium channels in the nerve membranes of the
arthropods.
[0005] The use of liquid formulations for spray applications is a convenient tool for the end-user to protect their crops
against pests. Liquid products are easily dosed prior to incorporation into water and are readily dispersed and diluted
15 upon addition in the spray tank.
[0006] This applies particularly to liquid insecticidal formulations, especialy to liquid formulations containing one or
more pyrethroid as active substances.
[0007] The customary liquid insecticide and in particular pyrethroid formulations are emulsifiable concentrates (EC)
which are usually based on aromatic hydrocarbon solvents such as xylene and the like.
20 [0008] In WO-A 90/09 103 oil-in-water emulsion formulations of pyrethroids are disclosed.
[0009] In such formulations part of the organic solvent is substituted by water in order to provide a more environmental
friendly product.
[0010] EW's are also advantageous for the end-user, because unlike EC's, EW-formulations are already emulsions
before the preparation of the actually applied spray mixture and, thus, can be easily diluted. It will be readily appreciated
25 that the technical problems associated with producing stable EW-formulations are quite different and more complex
than those encountered in the production of EC's.
[0011] Although the known EW formulations of pyrethroids already show very favourable properties, there is still
room for improvement, e.g. for the toxicological profile of such formulations.
[0012] It has now surprisingly been found that stable EW-formulations, containing an insecticide, in particular a py-
30 rethroid, of significantly reduced toxicity can be prepared, based on carboxylic acid esters as organic solvent.
[0013] Unlike the formulations disclosed in WO-A 90/09103 the formulations according to the invention do not need
aromatic hydrocarbons as a solvent or cosolvent.
[0014] EP-A 0 567 368 discloses EC's containing pyrethroids, in which aromatic hydrocarbons have been replaced
by a combination of one or more biphenyl derivatives, a polar co-solvent and a vegetable oil, to achieve an improved
35 inhalation tolerance. WO-A 96/01047 discloses pyrethroid containing EC's with an improved eye tolerance containing
vegetable oils or other esters as an organic solvent. However, these documents are completely silent on EW-formu-
lations.
[0015] Accordingly, in one aspect of the invention there is provided an oil-in-water emulsion, comprising

40 a) one or more insecticides, in particular pyrethroids;

b) one or more solvents from the group of esters of aliphatic monocarboxylic acids, esters of aliphatic dicarboxylic
acids, esters of aromatic monocarboxylic acids esters of aromatic dicarboxylic acids and tri-n-alkylphosphates;
c) an emulsifier system comprising one or more anionic surfactants and two or more non ionic surfactants, one of
which has a HLB value between 4 and 12 and one of which has a HLB value between 12 and 20;
45 d) one or more film forming agents/thickeners; and
e) water.

[0016] EW's according to the invention show a remarkably reduced acute toxicity profile; in many cases they are
non classified in terms of acute oral toxicity. This means, inter alia, that the acute oral LD 50 on rats is higher than
50 2000 mg/kg body weight and that the formulation is non irritant for both skin and eyes.
[0017] At the same time the formulations show excellent bioefficacy and all further advantages customary to EW's,
like user friendliness and a reduced content of aromatic solvents.
[0018] The term EW formulation means the undiluted formulation.
[0019] The formulations according to the invention comprise one or more, preferably 1 or 2, in particular 1, insecti-
55 cides, preferably from the group of the natural or synthetic pyrethroids.
[0020] Suitable examples of insecticides are e.g.:

1. from the group of the phosphorus compounds

2
 EP 1 339 281 B1

acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos (F-67825),

chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl,
demeton-S-methyl sulfone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, EPN, ethion, etho-
prophos, etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion, fenthion, fonofos, formothion, fosthiazate
5 (ASC-66824) heptenophos, isazophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, me-
thidathion, salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-
methyl, phenthoate, phorate, phosalone, phosfolan, phosphocarb (BAS-301), phosmet, phosphamidon, phoxim,
pirimiphos, primiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, py-
ridapenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiometon, triazophos,
10 trichlorphon, vamidothion;

2. from the group of the carbamates

alanycarb (OK-135), aldicarb, 2-sec-butyl phenylmethyl carbamate (BPMC), carbaryl, carbofuran, carbosulfan,
cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl m-cumenylbutyryl
15 (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino)-N-me-
thyl-N-(morpholinothio)carbamate (UC 51717), triazamate;

3. from the group of the pyrethroids

acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-, (1R)-cis-2,2-di-methyl-3-(2-oxothiolan-3-yliden-
20 emethyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl
isomer), bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1 RS)-trans-3-(4-tert-butylphe-
nyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin, cyper-
methrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythri-
nate, flumethrin, fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin, permethrin, phenothrin ((R)
25 isomer), praftethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin (TD-
2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701);

4. from the group of the amidines

amitraz, chlorodimeform;
30
5. from the group of the tin compounds
cyhexatin, fenbutatin oxide;

6. others
35 abamectin, ABG-9008, acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis,
Beauveria bassiana, bensultap, bifenazate (D-2341), binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505,
buprofezin, camphechlor, cartap, chlorbenzilate, chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylth-
iophene (UBI-T 930), chlorfentezine, chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, (2-naph-
thylmethyl)cyclopropanecarboxylate (Ro12-0470), cyromazin, diacloden (thiamethoxam), diafenthiuron, ethyl
40 N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzocarboximidate, DDT, di-
cofol, diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, diofenolan,
DPX-062, emamectin benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301),
fenazaquin, fenoxycarb, fipronil, fluazuron, flumite (Flufenzine, SZI-121), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-
1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, fluben-
45 zimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345),
halofenprox (MTI-732), hexaflumuron (DE_473), hexythiazox, HOI-9004, hydramethylnon (AC 217300), lufenuron,
imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), M-020, MTI-446, ivermectin, M-020, methoxy-
fenozide (intrepid, RH-2485), milbemectin, NC-196, neemgard, nitenpyram (TI-304), 2-nitromethyl-4,5-dihydro-
6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-ylcar-
50 bamaldehyde (WL 108477), pyriproxyfen (S-71639), NC-196, NC-1111, NNI-9768, novaluron (MCW-275), OK-
9701, OK-9601, OK-9602, propargite, pymethrozine, pyridaben, pyrimidifen (SU-8801), RH-0345, RH-2485, RYI-
210, S-1283, S-1833, SB7242, SI-8601, silafluofen, silomadine (CG-177), spinosad, SU-9118, tebufenozide, te-
bufenpyrad (MK-239), teflubenzuron, tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, totfenpyrad (OMI-88),
triazamate (RH-7988), triflumuron, verbutin, vertalec (Mykotal), YI-5301.
55
[0021] A preferred group of insecticides are natural or synthetic pyrethroids, e.g.:

acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)- (1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylideneme-

3
 EP 1 339 281 B1

thyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentylisomer),

bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1RS)-trans-3-(4-tert-butylphenyl)-
2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin, cypermethrin,
cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate,
5 flumethrin, fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin, permethrin, phenothrin ((R) isomer),
prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, theta-Cypermethrin (TD-2344), tral-
omethrin, transfluthrin and zeta-cypermethrin (F-56701).

[0022] Preferred are acrinathrin, bioallethrin, (S)-bioallethrin and deltamethrin. Especially preferred are acrinathrin
10 and/or deltamethrin, deltamethrin being particularly preferred.
[0023] It is also preferred to use a mixture of one or more pyrethroids and one or more non-pyrethroid insecticides
such as fiproles, nitromethylenes, carbamates.
[0024] Of the non-pyrethroid insecticides fiproles, acetamiprid and pirimicarb are especially preferred.
[0025] The concentration of the active substance(s) is generally 0.05 to 200 g/l, preferably 0.1 to 50 g/l, in particular
15 1 to 25 g/l.
[0026] The pyrethroids and other insecticides referred to are well known and usually commercially available. They
are described, e.g., in The Pesticide Manual, 11th ed., British Crop Protection Council, Farnham 1997.
[0027] The ester used as an organic solvent is from the group of esters of aliphatic monocarboxylic acids, esters of
aliphatic di- or tricarboxylic acids, esters of aromatic monocarboxylic acids, esters of aromatic di- or tricarboxylic acids
20 and tri-n-alkylphosphates, preferably tri-n-(C1-C6)alkylphosphates, such as tri-n-butylphosphate.
[0028] Preferably it is from the group of esters of aliphatic monocarboxylic acids, esters of aliphatic di- or tricarboxylic
acids and esters of aromatic monocarboxylic acids.
[0029] Examples of aliphatic monocarboxylic esters are aliphatic (such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, ethylhexyl, n-nonyl and isononyl)
25 and aromatic (such as benzyl) esters of fatty acids, such as acetic acid (such as ethyl acetate and n-butyl acetate),
caproic acid, caprylic acid, capric acid, a mixture of caprylic and capric acids, lauric acid, myristic acid, a mixture of
lauric and myristic acids, palmitic acid, stearic acid, a mixture of palmitic and stearic acids, myristoleic acid, palmitoleic
acid, oleic acid, linoleic acid or linolenic acid, or carboxylic acids with further functional groups, such as lactic acid
(such as ethyl lactate, butyl lactate, ethylhexyl lactate or 1-methoxy-2-propyl acetate).
30 [0030] A preferred group of aliphatic monocarboxylic acid esters are vegetable and animal oils. The term vegetable
oil as used herein includes oils from oil producing plants, such as rape oil, soya oil, palm oil, sunflower oil, cotton oil,
maize oil, linseed oil, coconut oil, thistle oil or castor oil. The term animal oil as used herein includes oils from oil
producing animals, such as tallow oil. Other examples of monocarboxylic acid esters are the transesterification products
of these oils such as alkyl esters, like rapeseed oil methyl ester, such as Radia 7961 (Fina Chemicals, Belgium), or
35 rapeseed oil ethyl ester.
[0031] Vegetable oils are preferably esters of C10-C22, preferably C12-C20, fatty acids. Those C10-C22 fatty acid esters
are, by way of example, esters of unsaturated or saturated C10-C22 fatty acids, especially with an even number of
carbon atoms, e.g. cis-erucic acid, iso-erucic acid, lauric acid, palmitic acid, myristic acid, particularly C18-fatty acids,
like stearic acid, linoleic acid or linolenic acid.
40 [0032] Examples of C10-C22 fatty acid esters are esters, which are obtainable by reacting glycerol or glycol with
C10-C22 fatty acids, and which are contained, e.g., in oils from oil producing plants, as well as (C1-C20)-alkyl (C10-C22)-
fatty acid esters which can be obtained, e.g., by transesterification of said glycerol- or glycol C10-C22 fatty acid esters
with C1-C20 alcohols (such as methanol, ethanol, propanol or butanol). The transesterification can be achieved ac-
cording to processes well known in the art, which are described, e.g., in Römps Chemie Lexikon, 9th edition, Volume
45 2, page 1343, Thieme Verlag, Stuttgart.
[0033] Preferred as C1-C20-alkyl C10-C22 fatty acid esters are methyl esters, ethyl esters, n-propyi-esters, isopropyl
esters, n-butyl-esters, isobutyl esters, n-pentyl esters, isopentyl esters, neopentyl esters, n-hexyl esters, isohexyl es-
ters, n-heptyl esters, isoheptyl esters, n-octyl esters, 2-ethyl-hexyl esters, n-nonyl esters, isononyl esters, and dodecyl
esters. As glycerol and glycol C10-C22 fatty acid esters the uniform or mixed glycerol or glycol esters of C10-C22 fatty
50 acids are preferred, particularly of fatty acids with an even number of carbon atoms, such as cis-erucic, iso-erucic acid,
lauric acid, palmitic acid, myristic acid, particularly C18-fatty acid, like stearic acid, linoleic acid or linolenic acid.
[0034] The EW formulations according to the invention may contain vegetable oils in the form of commercially avail-
able oily formulation auxiliaries, e.g. based on rape oil, like Hasten® (Victorian Chemical Company, Australia, main
component rape oil ethyl ester), Actirob® B (Novance, France, main component rape oil methyl ester), Rako-Binol®
55 (Bayer AG, Germany, main component rape oil), Renol® (Stefes, Germany, main component rape oil methyl ester) or
Stefes Mero® (Stefes, Germany, main component rape oil methyl ester).
[0035] Examples of esters of aromatic monocarboxylic acids include esters of benzoic acid (such as n-butyl benzoate,
benzyl benzoate, decyl benzoate, dodecyl benzoate, hexyl benzoate, isostearyl benzoate, methyl benzoate, octadecyl

4
 EP 1 339 281 B1

benzoate, C12-C15 alkyl benzoate) or salicylic acid.

[0036] Examples of aliphatic di- or tricarboxylic acid esters include esters of maleic acid (methyl, ethyl), diesters or
triesters derivatives of adipic acid (such as diisopropyl adipate (such as Crodamol® DA (Croda Oleochemicals, UK),
diisobutyl adipate), citric acid (such as tributyl citrate, acetyl tributyl citrate), glutaric acid, succinic acid (such as dibasic
5 esters: a mixture of methyl esters of adipic, glutaric and succinic acids), or sebecic acid (such as n-octyl sebecate).
[0037] Examples of aromatic dicarboxylic acid esters include the phthalates (such as dimethyl phthalate, diethyl
phthalate, dibutyl phthalate or diisononyl phthalate).
[0038] Beside using one ester as a solvent it is also preferred to use two or more.
[0039] It may be advantageous, especially when the active substance is not very soluble in the ester-solvent, to
10 incorporate one or more polar co-solvents.
[0040] Polar co-solvents, as used herein, means co-solvents which are totally or partially soluble in water (e.g. from
0.1 up to 100 %) . The co-solvent is generally selected with a view to low toxicity and a low potential as irritant for skin
and eyes.
[0041] Examples of polar co-solvents are ketones (such as cyclohexanone, acetophenone, methyl n-amyl ketone or
15 2-heptanone), alcohols (such as benzyl alcohol), alkyl amides (such as n,n-dimethylacetamide), alkylpyrrolidones (such
as n-methylpyrrolidone, n-octylpyrrolidone, n-dodecylpyrrolidone or n-hydroxy 2-ethylpyrrolidone), dialkylsulfoxides
(such as dimethylsulfoxide), ethers (such as anisole and 1-methoxy-2-propanol) or derivatives of urea (such as dimeth-
ylpropylene urea).
[0042] Preferred polar co-solvents are cyclohexanone (solubility in water: 8 % at room temperature), 2-heptanone,
20 benzyl alcohol (solubility in water: 4 % at room temperature), n,n-dimethylacetamide (solubility in water: soluble, no
data), n-methylpyrrolidone (solubility in water 100 % at room temperature), dimethylsulfoxide (solubility in water: 100
% at room temperature) and 1-methoxy 2-propanol (solubility in water: 100 % at room temperature), especially in
combination with deltamethrin as active substance.
[0043] The polar co-solvent content in generally 1 to 25 % by weight, preferably 2 to 20 % by weight, in particular 8
25 to 20 % by weight The content of the co-solvent will generally be chosen as low as possible but high enough to increase
the solubility of the active substance to obtain the targeted loading of the active substance in the finished product and
to avoid crystallization during the dilution before application.
[0044] In a preferred embodiment the formulation according to the invention does not comprise any further solvent
apart from the ester compound(s) as main solvent and the optional polar co-solvent, i. e. that the solvent part of the
30 formulation consists essentially of the ester component and optionally one or more polar co-solvents.
[0045] The formulations further comprise an emulsifier system comprising one or more anionic emulsifiers and two
or more non ionic emulsifiers.
[0046] Examples of anionic emulsifiers are phosphate esters and sulfate esters of poly (preferably 2 to 30) ethoxy-
lated (preferably C6 to C22) fatty alcohols such as ethoxylated (2 EO (EO means an ethylene oxyde unit) oleyl alcohol
35 phosphate ester (e.g. Empiphos® O3D, Albright & Wilson, UK), ethoxylated oleyl alcohol phosphate esters (e.g. Cro-
dafos® N serie, Croda Oleochemicals, UK), ethoxylated (2-10 EO) ceto/stearyl alcohol phosphate esters (e.g. Croda-
fos® CS serie, Croda Oleochemicals, UK), ethoxylated (4-6 EO) tridecyl alcohol phosphate esters (e.g.Emphos® PS
serie, CK Witco, USA), ethoxylated fatty alcohol phosphate esters (e.g. Crafol® AP serie, Henkel Iberica, Spain),
ethoxylated (3-6 EO) fatty alcohol phosphate esters (e.g. Rhodafac® serie, Rhodia Chimie, France), free acids of
40 complex organic phosphate esters (e.g. Beycostat® serie, Ceca S.A., France), phosphate esters of polyethoxylated
(8 to 25 EO) arylphenols (such as polyethoxylated di- and tristyrylphenols) (e.g. Soprophor 3D33, Rhodia Chimie,
France), sulfate esters of polyethoxylated arylphenols (such as polyethoxylated di- and tristyrylphenols) (e.g. Soprophor
DSS/7, Soprophor 4D384, Rhodia Chimie, France), inorganic salts of alkylbenzenesulfonate (such as calcium dodecyl-
benzenesulfonate) or inorganic salts of polycarboxlic acids, such as sodium and potassium salts are preferred.
45 [0047] Non ionic emulsifiers are generally from the class of polyethoxylated alkylphenols. Examples of suitable non
ionic emulsifiers are polyethoxylated (30 to 40 EO) castor oils, polyethoxylated (6 to 20 EO) fatty (C8 to C22) alcohols,
polyethoxylated (8 to 25 EO) arylphenols (such as polyethoxylated di- and tristyrylphenols), tridecyl alcohol polyglycol
ethers (such as ethoxylated (6 EO) tridecyl alcohol: Genapol® X-060, Clariant, Germany) polyalkoxylated alkyl ethers
(such as polyalkoxylated butyl ether Witconol® NS 500 K, CK Witco, USA), ethylene oxide propylene oxide block
50 copolymers (molecular weight ranging from 4,000 to 20,000 preferably ranging from 6,500 to 15,000).
[0048] A combination is generally used of an anionic emulsifier with a combination of two or more, preferably two,
non ionic emulsifiers where one non ionic emulsifier has a HLB ranging from 4 to 12, preferably 8 to 12, one non ionic
emulsifier has a HLB ranging from 12 to 20, preferably 14 to 18. This will ensure a particularly good physicochemical
behaviour of the EW formulation at high and low temperatures.
55 [0049] The HLB (Hydrophile-Lipophile-Balance) is an empirical scale defined by W.C. Griffin (J. Soc. Cosmetic Chem-
ists, 1, 311 (1949)) which expresses the amphiphilic nature of emulsifying agents (particularly non ionic surfactants).
The least hydrophilic surfactants are assigned the lowest HLB values.
[0050] The formulation generally comprises 0.01 to 20 % by weight, preferably 0.1 to 10 % by weight of a combination

5
 EP 1 339 281 B1

of anionic and non ionic emulsifiers, more preferably a combination of 0.01 to 10 % by weight, more particularly 0.1 to
3 % by weight of an anionic emulsifier and 0.01 to 15 % by weight, more particularly 0.1 to 7 % by weight of two ore
more non ionic emulsifiers.
[0051] The formulation further comprises one or more filmforming agent/thickener. Examples of suitable film-forming
5 agents/thickeners are thermoplastic resins such as polyvinyl pyrrolidones (such as ® Luviskol K 90 characterized by
a K index between 88 and 96 which refers to the viscosity of an aqueous solution containing 1 % w/w of the polyvinyl
pyrrolidone grade, BASF AG, Germany), or polyvinyl alcohols obtained by partial hydrolysis of polyvinyl acetates (such
as Mowiol products characterised by the viscosity of an aqueous solution containing 4 % w/w of the Mowiol grade,
Clariant, Germany), or vinylpyrrolidone/vinyl acetate copolymers (e.g. Agrimer VA 6, which is 60 % vinylpyrrolidone,
10 ISP, USA).
[0052] The use of adequate emulsifiers combined with film forming agents/thickeners is a particularly advantageous
way to ensure a good stability of the formulation.
[0053] Film-forming agents/thickeners are generally added in an amount of 0.1 to 5.0 % by weight, particularly 0.5
to 3.0 % by weight.
15 [0054] The formulation generally comprises 5 to 99% by weight, preferably 10 to 85 % by weight, more preferably
45 to 65 % by weight, of water.
[0055] The formulation optionally comprises further additives or auxiliaries, preferably antifreeze agents, stabilizing
agents, antifoams and defoamers, preservatives, colouring agents and/or odour masking products.
[0056] Examples of suitable antifreeze agents are ethylene glycol, monopropylene glycol, glycerol, hexylene glycol,
20 1-methoxy-2-propanol, cyclohexanol, in particular monopropylene glycol.
[0057] They are optionally added in an amount of preferably 1 to 30 % by weight, particularly 5 to 15 % by weight.
[0058] Stabilizing agents which are optionally added in the formulation are acids, preferably organic acids, such as
dodecylbenzene sulfonic acid, acetic acid, propionic acid or citric acid, in particular citric acid and antioxidants, such
as butyl hydroxy toluene (BHT), butyl hydroxy anisole (BHA), in particular butyl hydroxy toluene.
25 [0059] The stabilizing agent is optionally added in an amount of generally 0.01 to 2 % by weight, particularly 0.1 to
1 % by weight.
[0060] Preferred antifoams and defoamers are based on silicone, particularly preferred are an aqueous emulsion of
dialkylpolysiloxanes commercially available as Rhodorsil® 426R from Rhodia Chimie France, Wacker SE serie from
Wacker, Germany and a mixture of dialkylpolysiloxanes as an oil, commercially available as Rhodorsil® 416 from
30 Rhodia Chimie France, Wacker S184 or Wacker SL from Wacker, Germany.
[0061] Antifoams/defoamers are optionally added in an amount of generally 0.01 to 2 % by weight, preferably 0.1 to
1.5 % by weight.
[0062] Customary preservatives are optionally added such as, inter alia, derivatives of benzoic acid, sorbic acid,
formaldehyde, in particular a combination of methyl parahydroybenzoate (such as Preserval® M (Laserson & Sabetay,
35 France)) and propyl parahydroxybenzoate (such as Preserval® P (Laserson & Sabetay, France)), generally in an
amount of 0.1 to 1.0 % by weight, particularly 0.2 to 0.5 % by weight.
[0063] Further preferred optional additives are colouring agents such as Vitasyn® Patentblau (Clariant, Germany)
and odour masking products such as a mixture of numerous natural and synthesis perfumes, such as Perfume® TM
4242 (Technicoflor, France).
40 [0064] They are optionally added in amounts of generally 0.01 to 1 % by weight, particularly 0.1 to 0.5 % by weight
of colouring agent and 0.02 to 2 % by weight, particularly 0.1 to 1 % by weight of odour masking products.
[0065] In a further aspect of the invention there is provided a process for the manufacture of the insecticide, in
particular pyrethroid, oil-in-water (EW) emulsion described above, which comprises a three-step process:

45 - A Preparation of the organic phase comprising the dissolution of the insecticide, in particular pyrethroid, active
substance(s) in one or several organic solvents and, optionally, the polar co-solvent(s), and further addition of the
emulsifiers and optionally a stabilizing agent and/or a preservative using preferably a mixer, such as a paddle
agitator.
Optionally, a warming up (up to 30°C) step is included in order to make the solubilization of the hydrophilic emulsifier
50 easier.

- B preparation of the aqueous phase comprising the mixing of water with an optional antifreeze agent using for
example a rotor-stator Ultra-Dispersor (low speed) followed by the incorporation of a film-forming agent/thickener.
It is advantageous to sprinkle the polymeric powder (film forming agent) over the aqueous phase to control the
55 formation of lumps.
The following optional ingredients can be incorporated in the above-mentioned liquid phase at room temperature
using a mixer, such as a paddle agitator:

6
 EP 1 339 281 B1

- colouring agent and

- odour masking products
- defoaming agents

5 The mixing operation is maintained until a homogeneous aqueous phase is obtained.

- C/ The third step comprises preparing the finished pyrethroid insecticide oil-in-water (EW) emulsion by dispersing
water or the aqueous phase obtained in step B/ in the organic phase obtained in A/ at preferably room temperature
and under high shear using e.g. a high shear mixer, such as a rotor stator mixer available from companies such
10 as Silverson (UK) and IKA (Germany). The two phases are preferably first put together without any stirring. This
mixture is then strongly subjected to high shearing effects (T = 35°C max).

[0066] Insecticide, in particular pyrethroid, oil-in-water (EW) emulsion obtainable by said process preferably show
the following characteristics:
15
- the viscosity value of the EW formulation according to the invention is in the range of 50-150 mPas using a Brook-
field apparatus equipped with a LV2 module rotating at 30 and 60 rpm. The measurement is carried out at a
temperature of 25 ± 5°C;
- the blooming or spontaneity of the formulation when further diluted in water (by mixing from 0.01 to 5 % w/v of the
20 formulation with water in a cylinder of 100 ml capacity) is outstanding as a result of the low viscosity;
- the droplet size distribution characterized by a mean diameter ranging from 0.3 to 0.8 microns and 80 % of the
total population below 1 micron as measured using a laser particle size analyzer such as equipments commer-
cialized by Cilas and Malvern companies.

25 [0067] The EW formulation(s) according to the invention are preferably stable for at least 2 weeks at 54°C, 6 weeks
at 50°C and -10°C and at least two years under room temperature conditions.
[0068] The invention also relates to a method of controlling pests, such as harmful arthropods, like harmful insects
and acarians, which comprises applying an effective amount of the above-mentioned insecticide, in particular pyre-
throid, oil-in-water (EW) composition, preferably in the form of an aqueous dilution, to these pests or to the plants,
30 soils, surfaces, and the like infested with them, and to the use of the insecticide, in particular pyrethroid, oil-in-water
(EW) formulation in crop protection, further pest control uses, such as vector control, household uses, pet environments,
etc and in veterinary applications.
[0069] The compositions according to the invention are simply applied by diluting the oil-in-water (EW) emulsions
with the desired amount of water, stirring the mixture briefly and applying it to the plants, soils, surfaces and the like.
35 [0070] The invention is further illustrated by the examples, which are compiled in Table 1, without limiting the invention
thereto.

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 EP 1 339 281 B1

Claims

1. An oil-in-water emulsion formulation, comprising

5 a) one or more insecticides, in particular pyrethroids;

b) one or more solvents from the group of esters of aliphatic monocarboxylic acids, esters of aliphatic dicar-
boxylic acids, esters of aromatic monocarboxylic acids esters of aromatic dicarboxylic acids and tri-n-alkyl-
phosphates;
c) an emulsifier system comprising one or more anionic surfactants and two or more non ionic surfactants,
10 one of which has a HLB value between 4 and 12 and one of which has a HLB value between 12 and 20;
d) one or more film forming agents/thickeners; and
e) water.

2. The formulation as claimed in claim 1, wherein the insecticide is a pyrethroid.

15
3. The formulation as claimed in claim 2, wherein the pyrethroid is deltamethrin.

4. The formulation as claimed in any of the preceding claims, comprising a polar cosolvent.

20 5. The formulation as claimed in any of the preceding claims comprising further additives and/or auxiliaries from the
groups of, antifreeze agents, stabilizing agents, antifoams/defoamers, preservatives, colouring agents and odor
masking products.

6. The formulation as claimed in any of the preceding claims comprising 0.05 to 200 g/l of the active ingredient(s).
25
7. A process for producing an oil-in-water emulsion formulation as claimed in any of claim 1 to 6, comprising the
steps of

A. the preparation of an organic phase containing the insecticide(s), the emulsifier system and optionally further
30 auxiliaries in the organic solvent(s) and optionally a polar co-solvent;
B. the preparation of an aqueous phase containing water, the film forming agent/thickener and further hy-
drophilic auxiliaries; and
C. the mixing of the organic phase and the aqueous phase under high shear to obtain the oil-in-water emulsion.

35 8. The process as claimed in claim 7, wherein the insecticide is a pyrethroid.

9. The process as claimed in claim 8, wherein the pyrethroid is deltamethrin.

10. The use of an oil-in-water emulsion formulation as claimed in any of claims 1 to 6 for pest control.
40
11. The use as claimed in claim 10, wherein the insecticide is a pyrethroid.

12. The use as claimed in claim 11, wherein the pyrethroid is deltamethrin.

45 13. A method of controlling pests comprising applying an aqueous dilution of an oil-in-water emulsion formulation as
claimed in claim 1 to the pests or to plants or other locuses infected with or frequented by the pests.

14. The method as claimed in claim 13, wherein the insecticide is a pyrethroid.

50 15. The method as claimed in claim 14, wherein the pyrethroid is deltamethrin.

Patentansprüche

55 1. Öl-in-Wasser-Emulsionsformulierung, umfassend

a) ein oder mehrere Insektizide, insbesondere Pyrethroide;

b) ein oder mehrere Lösungsmittel aus der Gruppe von Estern von aliphatischen Monocarbonsäuren, Estern

10
 EP 1 339 281 B1

von aliphatischen Dicarbonsäuren, Estern von aromatischen Monocarbonsäuren, Estern von aromatischen
Dicarbonsäuren und Tri-n-alkylphosphaten;
c) ein Emulgatorsystem, das ein oder mehrere anionische grenzflächenaktive Mittel und zwei oder mehrere
nichtionische grenzflächenaktive Mittel umfaßt, von denen eines einen HLB-Wert zwischen 4 und 12 und eines
5 einen HLB-Wert zwischen 12 und 20 aufweist;
d) einen oder mehrere Filmbildner/Verdicker; und
e) Wasser.

2. Formulierung nach Anspruch 1, worin das Insektizid ein Pyrethroid ist.

10
3. Formulierung nach Anspruch 2, worin das Pyrethroid Deltamethrin ist.

4. Formulierung nach einem der vorstehenden Ansprüche, umfassend ein polares Co-Lösungsmittel.

15 5. Formulierung nach einem der vorstehenden Ansprüche, umfassend weitere Additive und/oder Hilfsmittel aus den
Gruppen von Gefrierschutzmitteln, stabilisierenden Mitteln, Antischaummitteln/Entschäumern, Konservierungs-
mitteln, Färbemitteln und Geruchsüberdeckungsprodukten.

6. Formulierung nach einem der vorstehenden Ansprüche, umfassend 0,05 bis 200 g/l an dem (den) wirksamen
20 Bestandteil(en).

7. Verfahren zur Herstellung einer Öl-in-Wasser-Emulsionsformulierung nach einem der Ansprüche 1 bis 6, umfas-
send die Schritte

25 A. Ausbilden einer organischen Phase, die das (die) Insektizid(e), das Emulgatorsystem und gegebenenfalls
weitere Hilfsstoffe in dem (den) organischen Lösungsmittel(n) und gegebenenfalls ein polares Co-Lösungs-
mittel enthält;

B. Ausbilden einer wässerigen Phase, die Wasser, Filmbildner/Verdicker und weitere hydrophile Hilfsmittel
30 enthält; und

C. Mischen der organischen Phase und der wässerigen Phase unter hoher Scherung zur Ausbildung der Öl-
in-Wasser-Emulsion.

35 8. Verfahren nach Anspruch 7, worin das Insektizid ein Pyrethroid ist.

9. Verfahren nach Anspruch 8, worin das Pyrethroid Deltamethrin ist.

10. Verwendung einer Öl-in-Wasser-Emulsionsformulierung nach einem der Ansprüche 1 bis 6 zur Schädlingsbe-
40 kämpfung.

11. Verwendung nach Anspruch 10, worin das Insektizid ein Pyrethroid ist.

12. Verwendung nach Anspruch 11, worin das Pyrethroid Deltamethrin ist.
45
13. Verfahren zur Bekämpfung von Schädlingen, umfassend das Aufbringen einer wässerigen Verdünnung einer Öl-
in-Wasser-Emulsionsformulierung nach Anspruch 1 auf die Schädlinge oder auf Pflanzen oder andere Stellen, die
mit den Schädlingen infiziert sind oder von den Schädlingen frequentiert werden.

50 14. Verfahren nach Anspruch 13, worin das Insektizid ein Pyrethroid ist.

15. Verfahren nach Anspruch 14, worin das Pyrethroid Deltamethrin ist.

55 Revendications

1. Formulation d'émulsion huile dans l'eau, comprenant

11
 EP 1 339 281 B1

a) un ou plusieurs insecticides, en particulier les pyréthrinoïdes ;

b) un ou plusieurs solvants choisis dans le groupe constitué par les esters d'acides monocarboxyliques ali-
phatiques, les esters d'acides dicarboxyliques aliphatiques, les esters d'acides monocarboxyliques aromati-
ques, les esters d'acides dicarboxyliques aromatiques et les tri-n-alkylphosphates ;
5 c) un système émulsifiant comprenant un ou plusieurs tensioactifs anioniques et deux ou plus tensioactifs non
ioniques, dont un présente une valeur HLB comprise entre 4 et 12 et dont un présente une valeur HLB comprise
entre 12 et 20 ;
d) un ou plusieurs agents filmogènes/épaississants ; et
e) de l'eau.
10
2. Formulation selon la revendication 1, dans laquelle l'insecticide est un pyréthrinoïde.

3. Formulation selon la revendication 2, dans laquelle le pyréthrinoïde est la deltaméthrine.

15 4. Formulation selon l'une quelconque des revendications précédentes, comprenant un cosolvant polaire.

5. Formulation selon l'une quelconque des revendications précédentes, comprenant d'autres additifs et/ou adjuvants
choisis dans le groupe constitué par les produits antigels, les agents stabilisants, les agents antimousses, les
conservateurs, les agents colorants et les produits désodorisants.
20
6. Formulation selon l'une quelconque des revendications précédentes, comprenant de 0,05 à 200 g/l du ou des
ingrédients actifs.

7. Procédé de fabrication d'une formulation d'émulsion huile dans l'eau selon l'une quelconque des revendications
25 1 à 6, comprenant les étapes de

A. préparation d'une phase organique contenant le ou les insecticides, le système émulsifiant et éventuelle-
ment d'autres adjuvants dans le ou les solvants organiques et éventuellement un cosolvant polaire ;
B. préparation d'une phase aqueuse contenant de l'eau, l'agent filmogène/épaississant et d'autres adjuvants
30 hydrophiles ; et
C. mélange de la phase organique et de la phase aqueuse sous un fort cisaillement afin d'obtenir l'émulsion
huile dans l'eau.

8. Procédé selon la revendication 7, dans lequel l'insecticide est un pyréthrinoïde.

35
9. Procédé selon la revendication 8, dans lequel le pyréthrinoïde est la deltaméthrine.

10. Utilisation d'une formulation d'émulsion huile dans l'eau selon l'une quelconque des revendications 1 à 6, pour la
lutte contre les insectes nuisibles.
40
11. Utilisation selon la revendication 10, dans laquelle l'insecticide est un pyréthrinoïde.

12. Utilisation selon la revendication 11, dans laquelle le pyréthrinoïde est la deltaméthrine.

45 13. Procédé de lutte contre les insectes nuisibles comprenant l'application d'une dilution aqueuse d'une formulation
d'émulsion huile dans l'eau selon la revendication 1 aux insectes ou aux plantes ou à d'autres cites infestés avec,
ou fréquentés par, les insectes nuisibles.

14. Procédé selon la revendication 13, dans lequel l'insecticide est un pyréthrinoïde.
50
15. Procédé selon la revendication 14, dans lequel le pyréthrinoïde est la deltaméthrine.

55

12