EP1575357A2 - Concentres de microemulsion - Google Patents

Concentres de microemulsion

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Publication number
EP1575357A2
EP1575357A2 EP03789129A EP03789129A EP1575357A2 EP 1575357 A2 EP1575357 A2 EP 1575357A2 EP 03789129 A EP03789129 A EP 03789129A EP 03789129 A EP03789129 A EP 03789129A EP 1575357 A2 EP1575357 A2 EP 1575357A2
Authority
EP
European Patent Office
Prior art keywords
methyl
alkyl
agrochemical
microemulsion
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03789129A
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German (de)
English (en)
Inventor
Gerhard Frisch
Detlev Haase
Thomas Maier
Gerhard Schnabel
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Bayer CropScience AG
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Bayer CropScience AG
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Publication date
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Publication of EP1575357A2 publication Critical patent/EP1575357A2/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to the field of crop protection formulations.
  • the invention relates to liquid formulations in the form of microemulsion concentrates which contain agrochemical active ingredients.
  • Active substances for crop protection are generally not used in their pure form. Depending on the field of application and the type of application, as well as on physical, chemical and biological parameters, the active ingredient is used in a mixture with customary auxiliaries and additives as a solid or liquid active ingredient formulation.
  • Liquid formulations are e.g. described in EP 0 261 492, EP 0 394 847, WO 95/17822, WO 98/31223, WO 89/03176, EP 0 357 149, WO 02/45507, GB 2 267 825 A, WO 94/23578, EP 0 330 904, EP 0 533 057, EP 0 533 057, DE 36 24 910, WO 01/74785, EP 0 400 585 and EP 0 118 579.
  • the object of the present invention was to provide an improved crop protection formulation which has a superior chemical and physical stability and agrochemical action.
  • the present invention thus relates to a microemulsion concentrate comprising a) one or more agrochemical active ingredients, b) one or more non-alcoholic organic solvents, c) one or more anionic surfactants, and d) one or more nonionic surfactants.
  • microemulsion concentrate may also contain customary auxiliaries and additives as further components.
  • microemulsion concentrate is understood to mean a composition which, when diluted with water, forms microemulsions, for example oil-in-water microemulsions or water-in-oil microemulsions.
  • a microemulsion is understood to mean an emulsion which is thermodynamically stable and has a droplet size of the emulsified phase which is generally in the range from 10 to 400 nm, preferably from 50 to 250 nm.
  • microemulsion concentrates according to the invention generally contain the following amounts of components a), b), c) and d)
  • % By weight here and in the entire description, unless otherwise defined, relates to the relative weight of the respective component based on the total weight of the formulation:
  • Component b) 10-90% by weight, preferably 20-85% by weight, particularly preferably
  • Component c) 0.1-25% by weight, preferably 1-20% by weight, particularly preferably 2
  • Component d) 0.1-60% by weight, preferably 1.5-45% by weight, particularly preferably
  • herbicides for example leaf-active herbicides such as ALS inhibitors (for example sulfonamides such as flucarbazone, propoxycarbazone or amicarbazone or sulfonylureas such as mesosulfuron, iodosulfuron, diflufenican, bromoxynil-containing, or loxynyloxy-containing products, of the class containing heroxylnyloxypropyl p-ethyl, beet herbicides such as Desmedipham, Phenmedipham, Ethofumesate or metamitron, glyphosate or glufosinate or also active substances from the class of the HPPD inhibitors (eg isoxaflutole, sulcotrione, mesotrione).
  • ALS inhibitors for example sulfonamides such as flucarbazone, propoxycarbazone or amicarbazone or sulfonylureas such as mesos
  • Herbicides contained in the microemulsion concentrates according to the invention are e.g. ALS inhibitors (acetolactate synthetase inhibitors) or herbicides other than ALS inhibitors, such as herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives, and heteroaryloxyphenoxy, phenoxyalkanecarboxylic acid derivatives , Quinoxalyloxy, pyridyloxy, benzoxazolyloxy and benzothiazolyloxyphenoxyalkane carboxylic acid esters, cyclohexanedione derivatives, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, and also S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester.
  • ALS inhibitors aceto
  • the ALS inhibitors are, in particular, imidazolinones, pyrimidinyloxy-pyridinecarboxylic acid derivatives, pyrimidyloxy-benzoic acid derivatives, triazolo-pyrimidine-sulfonamide derivatives and sulfonamides, preferably from the group of the sulfonylureas.
  • the active ingredients from the group of ALS inhibitors such as sulfonylureas, contained as a component in the microemulsion concentrates according to the invention always include not only the neutral compounds but also their salts with inorganic and / or organic counterions.
  • sulfonylureas can form salts, for example, in which the hydrogen of the —SO 2 —NH group is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines.
  • Suitable acids for this are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Preferred ALS inhibitors come from the series of sulfonylureas, for example pyrimidine- or triazinylaminocarbonyl- [benzene-, pyridine-, pyrazole-, thiophene- and (aIkylsuIfonyl) alkylamino -] - sulfamides.
  • Preferred substituents on the pyrimidine ring or triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or dimethylamino, where all substituents can be combined independently of one another.
  • Preferred substituents in the benzene, pyridine, pyrazole, thiophene or (alkylsulfonyl) alkylamino part are alkyl, alkoxy, halogen such as F, Cl, Br or J, amino, alkylamino, dialkylamino, acylamino such as formylamino, nitro, alkoxycarbonyl , Aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, haloalkyl, alkylcarbonyl, alkoxyalkyl, alkylsulfonylaminoalkyl, (alkanesulfonyl) alkylamino. Examples of such suitable sulfonylureas are
  • Phenyl and benzylsulfonyl ureas and related compounds e.g.
  • Alkoxyphenoxysulfonylureas e.g. are described in EP-A 0 342 569, preferably 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea (ethoxysulfuron) or its salts;
  • MON 37500 Sulfosulfuron (see Brighton Crop Prot. Conf. 'Weeds', 1995, p: 57), and other related sulfonylurea derivatives and mixtures thereof.
  • Typical representatives of these active ingredients include the compounds listed below and their salts: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, methyl-sulfuron-methyl, halopulfuron , imazosulfuron, Metsulfuron- methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron and its sodium salt, triflusulfuron-methyl, lodos
  • Suitable ALS inhibitors are e.g.
  • the herbicidal active substances contained in the microemulsion concentrates according to the invention which are different from ALS inhibitors are, for example: Herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives as well as heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxazolyloxycarboxy and benzpheniaalkoxyalkoxy -containing herbicides, e.g.
  • Phenoxyphenoxy- and heteroaryloxyphenoxycarboxylic acid esters and salts as well as herbicides such as bentazone, cyanazine, atrazine, dicamba and bromynoxynilitrile are preferred and their salts and esters and other leaf herbicides.
  • Suitable herbicidal active substances which differ from ALS inhibitors and which may be present as a component in the microemulsion concentrates according to the invention are, for example:
  • Phenoxyphenoxy and benzyloxyphenoxy carboxylic acid derivatives for example methyl 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate (diclofop-methyl), 2- (4- (4-bromo-2-chlorophenoxy) phenoxy ) methyl propionate (DE-A 26 01 548), 2- (4- (4-bromo-2-fluorophenoxy) phenoxy) methyl propionate (US-A 4,808,750), 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy ) methyl propionate (DE-A 24 33 067), Methyl 2- (4- (2-fluoro-4-trifluoromethylphenoxy) phenoxy) propionate (US-A, 808,750),
  • N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanide (metolachlor), N- (3-methyl-1, 2 , 4-oxadiazol-5-yl-methyl) -chloroacetic acid-2,6-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolylmethyl) -chloroacetic acid amide (metazachlor);
  • thiocarbamates e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylates);
  • S- (N-aryl-N-alkyl-carbamoylmethyl) dithiophosphonic acid esters such as S- [N- (4-
  • alkyl azines e.g. as described in WO-A 97/08156, WO-A-97/31904, DE-A-19826670, WO-A-98/15536, WO-A-8/15537, WO-A-98/15538, WO- A-98/15539 and also DE-A-19828519, WO-A-98/34925, WO-A-98/42684, WO-A-99/18100, WO-A-99/19309, WO-A-99 / 37627 and WO-A-99/65882, preferably those of the formula (I)
  • L) Phosphorus-containing herbicides e.g. of the glusosinate type such as glufosinate in the narrower sense, d. H. D, L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid, glufosinate monoammonium salt, L-glufosinate, L- or (2S) -2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid , L-glufosinate monoammonium salt or bialaphos (or bilanafos), ie L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoyl-L-alanyl-L-alanine, especially its sodium salt, or of the glyphosate type such as glyphosate, i.e.
  • the herbicides of groups B to L are, for example, from the publications mentioned above and from "The Pesticide Manual”, 12th edition, 2000, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -", by W.T. Thompson, Thompson Publications, Fresno CA, USA 1990 and “Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990.
  • microemulsion concentrates The following are preferred for the agrochemical active substances a) contained in the microemulsion concentrates according to the invention:
  • Suitable non-alcoholic organic solvents b) are solvents which do not contain any alcohol group, for example hydrocarbons, carboxylic acid derivatives, phosphoric acid esters, ethers, ketones or sulfoxides such as dimethyl sulfoxide.
  • hydrocarbons are preferably those which are liquid under normal conditions.
  • the hydrocarbons can be acyclic (aliphatic) hydrocarbons or cyclic hydrocarbons, e.g. aromatic or alicyclic (cycloaliphatic) hydrocarbons.
  • hydrocarbons b) are:
  • aromatic hydrocarbons e.g.
  • alkyl-substituted for example one, two or three times (C-i-C ⁇ o) alkyl-substituted
  • aromatics e.g. Benzenes such as toluene, xylenes, mesitylene, ethylbenzene, or
  • Hydrocarbons with condensed aromatic ring systems such as naphthalenes, e.g. 1-methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other condensed aromatic hydrocarbons such as indane or tetralin,
  • cycloaliphatic hydrocarbons for example saturated or unsaturated, optionally mono- or polysubstituted (for example mono-, di- or tris (C ⁇ -C ⁇ o) alkyl-substituted) cycloaliphatics such as cycloalkanes, cycloalkenes or cycloalkynes, for example cyclohexane or methylcyclopentane, 3) aliphatic hydrocarbons, for example linear or branched, saturated or unsaturated aliphatics, preferably C 5 -C 6 aliphates, for example alkanes, alkenes or alkynes, such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane.
  • cycloaliphatic hydrocarbons for example saturated or unsaturated, optionally mono- or polysubstituted (for example mono-, di- or tris (C ⁇ -C ⁇ o) alkyl-sub
  • Mixtures of one or more aromatic hydrocarbons and / or one or more cycloaliphatic hydrocarbons and / or one or more aliphatic hydrocarbons can also be present as component b).
  • examples are mixtures of several aliphatic hydrocarbons, for example commercially available solvents from the Exxs ⁇ L ® D series, IsoPAR ® series or BAY0L ® series, for example Bayol ® 82 (EXXONMOBIL CHEMICALS) or the ISANE ® IP series or HYDR0SEAL ® G series (TOTALFINAELF ), or mixtures of aromatic and aliphatic hydrocarbons, e.g. commercially available solvents from the S ⁇ Lv ⁇ sso ® series, e.g.
  • Solvesso ® 100, Solvesso ® 150 or Solvesso ® 200 EXXONMOBIL CHEMICALS
  • the S ⁇ LVAREx ® / S ⁇ LVAR ⁇ ® series TOTALFOMELF
  • ® series e.g. Caromax ® 28 (Petrochem Carless).
  • Aliphatic hydrocarbons in particular saturated aliphatic hydrocarbons such as C 5 -C 6 alkanes, for example from the Bayol ® series are preferred.
  • carboxylic acid derivatives are e.g. Esters or amides of carboxylic acids.
  • carboxylic acid derivatives are the esters and amides of monocarboxylic acids, dicarboxylic acids or polycarboxylic acids such as tri-, tetra- or also higher-functional carboxylic acids, preferably with 2-26 carbon atoms in question.
  • esters are the esters with C 1 -C 20 alcohols (for example methanol, ethanol, propanol or butanol), and in particular in the case of fatty acid esters, the glycerol and glycol esters are also preferred.
  • Internal esters such as lactones are also suitable as carboxylic acid esters.
  • monocarboxylic acid esters are the esters of aliphatic and aromatic monocarboxylic acids, for example aliphatic Ci-Cg-monocarboxylic acid esters such as formic acid esters, acetic acid esters and propionic acid esters, or aliphatic fatty acid esters such as C ⁇ o-C 22 fatty acid esters, for example of natural origin as they are contained in natural oils or vegetable oils, or synthetic Origin, or aromatic C 7 -C 22 monocarboxylic acid esters such as benzoic acid esters or phenylacetic acid esters.
  • aliphatic Ci-Cg-monocarboxylic acid esters such as formic acid esters, acetic acid esters and propionic acid esters
  • aliphatic fatty acid esters such as C ⁇ o-C 22 fatty acid esters, for example of natural origin as they are contained in natural oils or vegetable oils, or synthetic Origin
  • aromatic C 7 -C 22 monocarboxylic acid esters such as benzoic acid
  • fatty acid ester examples include, for example those of natural origin, for example natural oils such as animal oils or vegetable oils, or synthetic origin, for example Edenor ® MESU or AGNIQUE ® ME series (COGNIS), of the Salim ® ME series (SALIM), the STEPAN ® C series (STEPAN) or the W ⁇ coN ⁇ L ® 23 series (WITCO).
  • Preferred fatty acid esters are esters of C10-C22, preferably C-i2-C2o fatty acids.
  • the C10-C22 fatty acid esters are, for example, esters of unsaturated or saturated C 10 -C22 fatty acids, in particular with an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular C 8 fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.
  • fatty acid esters such as C 0 -C 22 fatty acid esters are glycerol and glycol esters of fatty acids such as C- ⁇ o-C 22 fatty acids or their transesterification products, for example alkyl fatty acid esters such as -C-C 2 o-alkyl-C ⁇ o-C 22 -Fatty acid esters, as can be obtained, for example, by transesterification of the aforementioned glycerol or glycol fatty acid esters such as C 1 -C 22 -fatty acid esters with CrC 2 o-alcohols (for example methanol, ethanol, propanol or butanol).
  • the transesterification can be carried out according to known methods, as described, for example, in the Römpp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.
  • Preferred fatty acid esters are, for example, oils from oil-producing plant species such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, safflower oil, walnut oil, peanut oil, olive oil or castor oil, in particular rapeseed oil, the transesterification products also being understood as vegetable oils, for example alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester.
  • oils from oil-producing plant species such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, safflower oil, walnut oil, peanut oil, olive oil or castor oil, in particular rapeseed oil
  • the transesterification products also being understood as vegetable oils, for example alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester.
  • dicarboxylic acid esters and polycarboxylic acid esters are the full esters of oxalic, malonic, amber, glutaric, adipine, pimeline, sebacic, azelaine, suberine, maleic, phthalic, terephthalic, mellitic, trimellitic and polymaleic acid, in particular the Ci-Cio-alkyl esters such as the methyl ester, ethyl ester, propyl ester such as n-propyl ester or iso-propyl ester, butyl ester such as n-butyl ester, isobutyl ester, sec-butyl ester or tert-butyl ester.
  • Ci-Cio-alkyl esters such as the methyl ester, ethyl ester, propyl ester such as n-propyl ester or iso-propyl ester, butyl ester such as n-butyl ester
  • carboxamides also come -C-C26-carboxylic acid-N, N-di (-C-C 2 o-alkyl) amides, for example -C-C 26 -carboxylic acid-N, N-dimethylamides such as N, N-dimethylformamide or N, N-dimethylacetamide into question, or internal amides such as lactams, for example pyrrolidones such as N-substituted C 1 -C 2 -alkyl pyrrolidones such as N-methyl-pyrrolidone, N-butyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone and N- cyclohexyl pyrrolidone.
  • N-substituted C 1 -C 2 -alkyl pyrrolidones such as N-methyl-pyrrolidone, N-butyl-
  • Suitable phosphoric acid esters are triesters of phosphoric acid with alcohols, the alcohols preferably being selected from the group consisting of
  • diols or polyols such as ethylene glycol, propylene glycol or glycerin
  • aryl, alkylaryl, poly (alkyl) aryl and poly (arylalkyl) aryl alcohols for example phenol and / or cresol, octylphenol, nonylphenol, triisobutylphenol, tristyrylphenol,
  • alkoxylated alcohols which are obtained by reacting the alcohols mentioned above under 1), 2) or 3) with alkylene oxides, preferably (-C-C) alkylene oxides.
  • Preferred phosphoric acid esters are triesters of orthophosphoric acid, in particular alkoxylated triesters of orthophosphoric acid such as tri (butoxyoxyethyl) phosphate.
  • suitable ketones are aromatic, cycloaliphatic or aliphatic ketones such as acetophenone, benzophenone, isophorone, cyclohexanone and methyl ethyl ketone, ethyl butyl ketone, diethyl ketone and dibutyl ketone.
  • Suitable ethers are aromatic, cycloaliphatic or aliphatic ethers such as anisole, tetrahydrofuron, oxirane, dibutyl ether, dipentyl ether, butylhexyl ether, methyl tert-butyl ether.
  • Preferred non-alcoholic solvents b) are aromatic hydrocarbons such as CrC 6 alkylbenzenes, for example toluene or xylene, C 1 -C 6 alkyl naphthalenes and aromatic mixtures such as the Solvesso® series from Exxon, ketones such as acetophenone, isophorone, cyclohexanone and methyl ethyl ketone, N-substituted C 1 -C 2 -alkyl pyrrolidones such as N-methyl-pyrrolidone, N-butyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone and N-cyclohexyl-pyrrolidone, cyclic aliphatic hydrocarbons such as decalin and cyclohexane, Acid amides such as dimethylformamide, dimethyl sulfoxide, lactones such as gamma
  • Suitable anionic surfactants c) are, for example, sulfates, sulfonates, phosphates and phosphonates of hydrocarbons, which may optionally contain alkylene oxide units.
  • the sulfates, sulfonates, phosphates and phosphonates can be in the form of the acids or as salts.
  • Anionic surfactants c) of the following formula (I) are preferred:
  • R is an unsubstituted or substituted C 1 -C 3 -hydrocarbon radical which can optionally be bonded via alkylene oxide units, or R is one
  • alkylene oxide units is understood in particular to mean units of C2-C10 alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, it being possible for the units within the surfactant to be the same or different and to be statistically mixed or arranged in blocks.
  • R is preferably a CrC 2 o -alkyl radical (for example methyl, ethyl, propyl, butyl) or a C 6 -C 24 aryl radical (for example phenyl, biphenyl, naphthyl) which can optionally carry one or more radicals, for example from the group C ⁇ -C -alkyl (eg linear or branched C ⁇ -C2o-alkyl such as sec.
  • butyl or dodecyl which comprises one or more radicals such as C 6 -C 2 o-aryl (eg, phenyl, biphenyl, naphthyl) can carry, and C 6 -C 2 o-aryl (eg, phenyl, biphenyl or naphthyl) which may carry one or more radicals optionally as C ⁇ -C ⁇ 0 alkyl (eg methyl, ethyl, propyl, butyl), or R a radical R 2 O- (AO) w , in which w is an integer from 1 to 100, and AO is an alkylene oxide unit, for example (EO) x (PO) ⁇ (BO) z, in which EO is an ethylene oxide unit, PO is a propylene oxide unit , BO is a butylene oxide unit, x is an integer from 0 to 100, y is an integer from 0 to 100, z is an integer from 0 to 100 and the sum x + y
  • R 2 is H, a C 1 -C 20 alkyl radical (for example methyl, ethyl, propyl, butyl) or a C 6 -C 24 aryl radical (for example phenyl, biphenyl, naphthyl), which can optionally carry one or more radicals, for example from the group CrC 2 o-alkyl (for example linear or branched Cr C 2 o -alkyl such as sec.
  • a C 1 -C 20 alkyl radical for example methyl, ethyl, propyl, butyl
  • a C 6 -C 24 aryl radical for example phenyl, biphenyl, naphthyl
  • CrC 2 o-alkyl for example linear or branched Cr C 2 o -alkyl such as sec.
  • CQ-C 2 o-aryl residues for example phenyl, biphenyl, naphthyl
  • C 6 -C o-aryl eg phenyl, biphenyl, naphthyl
  • R 2 is - O - S0 3 M, - SO 3 M, - O - PO 3 HM, H or PO 3 HM, preferably PO 3 HM, where M is H or is a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion.
  • Particularly preferred anionic surfactants c) are alkylarylsulfonates such as dodecylbenzenesulfonates, for example Erdalkalidodecylbenzolsulfonate such as calcium dodecylbenzenesulfonates (for example Phenylsulfonat CA100 ® from Clariant), Alkylaryl polyglycol ether sulfates and sulfonates, especially arylalkylaryl polyglycol ether sulfates such as tristyrylphenol polyglycol ether sulfates, especially the alkali or ammonium or triethanolamine salts (e.g.
  • alkyl ether sulfates and their salts e.g. from Genulfonate
  • Genulfonate L such as Genulfonate L, such as Genapolate® L, such as Genapolate® L Hostapur® series from Clariant
  • alkyl polyglycol ether phosphates especially the alkali salts (for example the Rhodafac® series Rhodia), alkylaryl polyglycol ether phosphates, especially in the form of the alkali metal salts.
  • the salts are generally preferred metal salts such as alkali or alkaline earth metal salts or ammonium or trialkylamine salts.
  • alkoxylates for example ethoxylates, propoxylates or butoxylates and their combinations.
  • alkoxylates are meant compounds containing alkylene oxide units, in particular units of C2 -C ⁇ 0 alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide, where the units may be different within the same or different and surfactant thereby randomly mixed or arranged in blocks.
  • alkoxylates d) are compounds of the following formula (II):
  • R 1 is selected from the group H, HO, C 1 -C 3 o-alkyl, which can be linear or branched (for example methyl, ethyl, propyl, butyl, pentyl, hexyl), dC 30 alkoxy, preferably C 1 -C 8 0 -alkoxy, which can be linear or branched (for example methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), C 6 -C 24 -aryl (for example phenyl), which can optionally carry one or more radicals such as C 1 -C 3 o-arylalkyl (eg styrylphenyl) or -C-C 30 alkyl, in which the alkyl groups can be linear or branched (eg butyl or dodecyl), C 6 -C 24 aryloxy (eg phenoxy), which can optionally carry one or more radicals such as dC 3 o-ary
  • R 2 is H or dC 6 alkyl, which may be linear or branched (e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl), and w is an integer from 1 to 100, AO is an alkylene oxide unit, e.g.
  • ( EO) ⁇ (PO) ⁇ (BO) z wherein EO is an ethylene oxide unit, PO is a propylene oxide unit, BO is a butylene oxide unit, x is an integer from 0 to 100, y is an integer from 0 to 100, z is an integer from 0 to 100 and the sum x + y + z is at least 1, and the alkylene oxide unit, for example (EO) ⁇ (PO) ⁇ (BO) z, is statistically mixed or built up in blocks.
  • Especially preferred nonionic surfactants d) are Alkylarylpolyalkoxylate, for example the ethoxylates, propoxylates and / or butoxylates, Arylalkylarylpolyalkoxylate as Tristyrylphenylpolyalkoxyiate (for example Soprophor ® series by Rhodia) and Alkylphenylpolyalkoxylate as Tributylphenylpolyalkoxlate (eg Sopagenat ® series by Clariant), alkylene oxide block copolymers such as ethylene oxide (EO ) -Propylene oxide (PO) - block copolymers or ethylene oxide (EO) -butylene oxide (BO) block copolymers (e.g.
  • Pluronic ® series from BASF polyalkylene oxides such as polyethylene oxides, polypropylene oxides or polybutylene oxides, which have dd ⁇ hydrocarbon radicals on one of the two terminal oxygen atoms, preferably C 10 -C 22 hydrocarbon radicals such as straight-chain or branched C ⁇ o-C 22 alkyl radicals (eg decyl, dodecyl, tetradecyl, hexadecyl) may be substituted, eg polyglycol ethers which may be isotridecyl-substituted (eg Genapol® series from Clariant), alkoxylated such as ethoxylated oils such as vegetable oils, for example alkoxy Treated and ethoxylated castor oil (Emulsogen® series Clariant), alkoxylated and ethoxylated (C 10 -C 22 ) fatty amines (e.g. Genamin® series from Clariant).
  • carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals
  • these radicals can be in the carbon skeleton each be straight or branched. If not specifically stated, these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, being preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1, 3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2-
  • a hydrocarbon residue means a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon residue, e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.
  • a carbon residue preferably has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms;
  • a hydrocarbon radical is particularly preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.
  • the heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as a mono-, bi- or polycyclic aromatic system, in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, Thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partially or completely hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydrofuryl.
  • heteroaryl such as a mono-, bi- or polycyclic aromatic system, in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidiny
  • Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo.
  • the oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, -alkenyl and -alkynyl are partially or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2 , CH 2 CH 2 CI;
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; the same applies to haloalkenyl and other halogen-substituted radicals.
  • Hydrocarbon radicals for example alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or heterocyclyl or heteroaryl, can be substituted, the substituents being, for example, one or more, preferably 1, 2 or 3, radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, Hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case, cyclo , also alkyl and haloalkyl and the above-mentioned saturated hydrocarbon-containing radicals are
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • substituents from the group halogen for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (C 1 -C 4 ) haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) alkoxy, preferably methoxy or are preferred Ethoxy, (-C-C) haloalkoxy, nitro and cyano.
  • the substituents methyl, methoxy and chlorine are particularly preferred.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (dC 4 ) alkyl, (C 1 -C 4 ) alkoxy, (dC 4 ) haloalkyl, (dC 4 ) haloalkoxy and nitro is substituted, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
  • An acyl residue means the residue of an organic acid which formally arises from the removal of an OH group from the organic acid, e.g. the rest of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residues of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • An acyl radical is preferably formyl or aliphatic acyl from the group CO-R x , CS-R X , CO-OR x , CS-OR x , CS-SR X , SOR ⁇ or SO 2 R ⁇ , where R x and R ⁇ each represents a C 1 -C 3 -hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the latter two radicals being unsubstituted, N-monosubstituted or N, N-disubstituted.
  • Acyl means, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (-C-C) alkylcarbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other Remains of organic acids.
  • Formula (I) and the other compounds mentioned in this description also encompass all stereoisomers and mixtures thereof.
  • Such compounds contain one or more asymmetric carbon atoms or double bonds, which are not specified separately in the general formula.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the respective formulas and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure ones Starting materials are produced.
  • microemulsion concentrates according to the invention can be prepared by customary processes, e.g. Mix by dissolving or emulsifying the individual components, preferably at room temperature. If further auxiliaries and additives are contained, these are also preferably entered at room temperature. The order of addition of the individual components is generally arbitrary.
  • auxiliaries such as inert materials and other additives are also known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, “Solvent Guide”; 2nd Ed., Interscience, NY 1963; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, “Encyclopedia of Surface Active Agents", Chem. Publ. Co.
  • combinations with agrochemical active ingredients other than component a), such as herbicides, fungicides, insecticides, safeners, fertilizers and / or growth regulators can also be prepared, e.g. in the form of a finished formulation or as a tank mix.
  • microemulsion concentrates according to the invention can be diluted with water to form microemulsions, which are also the subject of the present invention.
  • the weight ratio of microemulsion concentrate: water can be, for example, 1: 0.1 to 1: 100, preferably 1: 1 to 1: 100, which leads to concentrated microemulsions which, as such, are stable in storage.
  • these can be further diluted with water to give spray liquors which are generally in the form of emulsions such as microemulsions, aqueous solutions, suspensions or suspoemulsions.
  • Components a), b), c) and d) of the microemulsion concentrates and microemulsions according to the invention can be contained together in a finished formulation which is then usually, e.g. can be applied in the form of a spray mixture.
  • microemulsion concentrates and microemulsions according to the invention can also contain customary auxiliaries and additives, for example formulation auxiliaries such as anti- Drift agents, substances to influence moisture (humectants), fertilizers such as ammonium sulfate, urea or multi-component fertilizers, for example based on phosphorus, potassium and nitrogen, such as P, K, N fertilizers, or commercial surfactants such as components c) and d) betaine or polymeric surfactants, stabilizers such as pH stabilizers, bioeides, UV stabilizers, defoamers, synthetic or natural polymers, solvents, eg polar solvents such as water or non-polar solvents such as saturated or unsaturated aliphatic solvents, which can be branched or unbranched, or aromatic solvents such as So
  • formulation auxiliaries such as anti- Drift agents, substances to influence moisture (humectants)
  • fertilizers such as ammonium sulfate, urea or multi-component
  • Wetting agents such as Genapol ® LRO (0-20% by weight), dispersing agents such as Tamol ® (0-15% by weight) or other surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30% by weight) );
  • Inorganic salts such as NaCl, Na 2 SO 4 , MgC (0-50% by weight), (oligo-; poly -) - phosphates; Carbonates such as potassium carbonate;
  • fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus and potassium-containing components, optionally further trace elements (0-60% by weight);
  • defoamers such as Fluowet ® PP (0-2% by weight);
  • Binders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinyl pyrrolidone, polyacrylic acid derivatives, (0-15% by weight); or
  • Solvents such as water or organic solvents (0-15% by weight).
  • the agrochemical compositions according to the invention can be used, for example, by application to the harmful organisms or the locations where they occur, for example by spraying.
  • the agrochemical compositions according to the invention are generally applied in the form of a spray mixture which contains components a), b), c) and d) in effective amounts and, if appropriate, further components for the customary auxiliaries and additives, for example for formulation or use.
  • the spray liquor is generally prepared on the basis of water, it being possible to add customary auxiliaries and additives, for example oils, such as vegetable oils or high-boiling hydrocarbons such as kerosene or paraffin.
  • the concentration of agrochemical active ingredient a) is generally at 10 "6 to 0% by weight, preferably at 10 " 5 to 4% by weight in the applied agent, for example the spray liquor, at an application rate of 1 to 5000 l / ha, preferably 50 to 1000 l / ha ,
  • concentrated formulations present in commercial form are optionally diluted in the customary manner, by means of water. It may be advantageous to add further amounts of components b), c) and d) and / or other auxiliaries and additives customary for use, in particular self-emulsifying oils or paraffin oils, to the spray liquors. Additional components a) or other agrochemical active ingredients other than component a) can also be added.
  • the required application rate of the agrochemical active ingredients a) can vary with the external conditions such as temperature, humidity, type of herbicide used. It can fluctuate within wide limits, e.g. between 0.001 and 10 kg / ha or more of active substance, preferably between 0.005 and 5 kg / ha.
  • the agrochemical compositions according to the invention are preferably herbicidal compositions. These have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well recorded.
  • the funds can e.g. are applied in the pre-sowing, pre-emergence or post-emergence process.
  • some representatives of the monocotyledonous and dicotyledonous weed flora may be mentioned, which can be controlled by the herbicidal compositions according to the invention, without any restriction to certain species being mentioned.
  • Apera spica venti On the side of the monocotyledon weed species, for example, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp , and Bromus spp.
  • Apera spica venti On the side of the monocotyledon weed species, for example, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp , and Bromus spp.
  • bromus Catharticus like bromus Catharticus, bromus secalinus, bromus erectus, bromus tectorum and bromus japonicus and cyperus species from the annual group and on the part of the perennial species agropyron, cynodon, imperata and sorghum and also persistent cyperus species well recorded.
  • the spectrum of activity extends to species such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, and convolvulus, cirsium, rumex and artemisia in the perennial weeds.
  • Harmful plants occurring in rice under the specific crop conditions e.g. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also superbly combated by the agents according to the invention.
  • herbicidal compositions according to the invention are applied to the surface of the earth before germination, either weed seedlings are prevented completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
  • the herbicidal compositions according to the invention are notable for a rapid onset and long-lasting herbicidal action.
  • the rain resistance of the active ingredients in the combinations according to the invention is generally favorable.
  • a particular advantage is that those used in the herbicidal compositions and effective dosages of herbicidal compounds can be set so low that their soil effect is optimally low. This makes their use not only possible in sensitive crops, but groundwater contamination is practically avoided.
  • the combination of active substances according to the invention enables a considerable reduction in the amount of active substances required.
  • herbicidal compositions according to the invention have excellent herbicidal activity against mono- and dicotyledon weeds
  • crop plants of economically important crops are e.g. dicotyledonous crops such as soybeans, cotton, rapeseed, sugar beet, or Gramineae crops such as wheat, barley, rye, oats, millet, rice or corn, only slightly or not at all damaged.
  • the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
  • the herbicidal compositions according to the invention have excellent growth-regulating properties in crop plants. They intervene regulating the plant's own metabolism and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, for example by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesirable vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage. Because of their herbicidal and plant growth regulatory properties, the herbicidal compositions according to the invention can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties concern e.g. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.
  • the herbicidal compositions according to the invention can also be used in economically important transgenic crops of useful and ornamental plants, for.
  • B. Gramineae crops such as wheat, barley, rye, oats, millet, rice and corn or crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the agents according to the invention can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
  • the herbicidal compositions according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic crop, for example a changed or specially expanded weed spectrum which can be controlled, changed application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the present invention furthermore also relates to a process for controlling unwanted vegetation, preferably in crops such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soybeans, particularly preferably in monocotyledon crops such as cereals, for example wheat, barley, rye, oats, crosses thereof such as triticale, rice, corn and millet, the herbicidal composition according to the invention being applied to the harmful plants, parts of plants, plant seeds or the area on which the plants grow, for example the area under cultivation applied, for example in pre-emergence, post-emergence or in pre-and post-emergence, preferably in pre-emergence.
  • crops such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soybeans, particularly preferably in monocotyledon crops such as cereals, for example wheat, barley,
  • the plant cultures can also be genetically modified or obtained by mutation selection and are preferably tolerant of acetolactate synthase (ALS) inhibitors.
  • ALS acetolactate synthase
  • the invention also relates to the use of the herbicidal compositions according to the invention for controlling harmful plants, preferably in plant crops.
  • a preferred use relates to the use of herbicidal compositions which contain synergistic amounts of components a), b), c) and d).
  • herbicidal compositions according to the invention can also be used non-selectively for controlling unwanted vegetation, e.g. in plantation crops, on roadsides, squares, industrial plants or railway systems.
  • agrochemical compositions according to the invention in particular herbicidal compositions, can optionally be in the form of mixed formulations with further agrochemical active ingredients and customary auxiliaries and additives, which are then diluted with water in a customary manner, or as so-called tank mixes by diluting the separately formulated or partially separately formulated components can be made with water.
  • the combinations according to the invention achieve a reduction in the absolute application rate compared to the single application of a herbicidal active ingredient.
  • the invention therefore also relates to a process for the selective control of harmful plants in crops, characterized in that a herbicidally effective amount of the herbicides mentioned a) is applied in combination with components b), c) and d), e.g. pre-emergence, post-emergence or pre- and post-emergence, preferably pre-emergence, on the plants, parts of plants, plant seeds or the area on which the plants grow, e.g. the acreage.
  • a herbicidally effective amount of the herbicides mentioned a) is applied in combination with components b), c) and d), e.g. pre-emergence, post-emergence or pre- and post-emergence, preferably pre-emergence, on the plants, parts of plants, plant seeds or the area on which the plants grow, e.g. the acreage.
  • the herbicides a) are applied at rates of from 0.1 to 2,000 g of active substance / ha, preferably from 0.5 to 1,000 g of active substance / ha. Also particularly preferred is the application of the active ingredients in the form of a co-formulation or in the form of tank mixtures, the individual components, e.g. in the form of formulations, mixed together in the tank with water and the spray mixture obtained is applied.
  • herbicidal compositions with the active compound combinations according to the invention are therefore used for the selective control of undesired plants.
  • the herbicidal compositions of the present invention therefore contain an additional content of one or more compounds which act as safeners or antidotes.
  • antidotes or safeners or groups of compounds which are suitable as safeners or antidots for the herbicidal compositions of the invention described above include:
  • dichlorophenylpyrazole carboxylic acid preferably compounds such as ethyl 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylate (compound S1-2), 1- (2,4-dichlorophenyl) -5-isopropyl-pyrazole -3-carboxylic acid ethyl ester (compound S1 -3),
  • Active substances of the phenoxyacetic or propionic acid derivative type or aromatic carboxylic acids such as.
  • fenclorim 46-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512
  • Daimuron 1 - (1-methyl-1-phenylethyl) -3-p-tolylurea, Pesticide Manual, 11th edition, 1997 , P.
  • the safeners (antidotes) from groups a) to j) above reduce or prevent phytotoxic effects which can occur when the herbicidal compositions according to the invention are used in crops without impairing the effectiveness of the herbicides against harmful plants.
  • the field of use of the herbicidal compositions according to the invention can be expanded considerably and, in particular, the use of safeners enables the use of herbicidal compositions which have hitherto been able to be used only to a limited extent or with insufficient success, ie combinations which do not contain safeners low doses with little broad effect led to insufficient control of the harmful plants.
  • Components a), b), c) and d) of the herbicidal compositions according to the invention and the safeners mentioned can be applied together (for example as a finished formulation or in a tank mixing process) or in succession in any order.
  • the weight ratio of safener: herbicide can vary within wide limits and is preferably in the range from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1.
  • the optimal amounts of herbicide (s) and safener (s) are customary depending on the type of herbicidal composition and / or on the safener used and on the type of crop to be treated.
  • the safeners can be used for the pretreatment of the seed of the crop (dressing of the seeds) or introduced into the seed furrows before sowing or used together with the herbicide mixture before or after emergence of the plants.
  • Pre-emergence treatment includes both the treatment of the acreage before sowing and the treatment of the sown but not yet overgrown acreage.
  • Co-application with the herbicide mixture is preferred.
  • Tank mixes or ready-to-use formulations can be used for this.
  • the application rates of the safeners can vary within wide limits and are generally in the range from 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of active compound per hectare.
  • the herbicidal compositions according to the invention can be applied in a customary manner, for example using water as a carrier in spray liquor amounts of about 5 to 4000 liters / ha. It is also possible to use the funds in the so-called low-volume and ultra-low-volume process (ULV).
  • UUV ultra-low-volume process
  • one, two or more can additionally be used in the herbicidal compositions of the invention to round off the properties, usually in minor amounts from the herbicides a) different agrochemical active substances (eg insecticides, fungicides, safeners) may be contained.
  • agrochemical active substances eg insecticides, fungicides, safeners
  • agrochemical agents are combined with each other, e.g. Fenoxaprop-p-ethyl / loxynil octanoate, DicIofop / bromoxynil octanoate, CMPP / bromoxynil octanoate, MCPA / loxynil octanoate, bromoxynil octanoate / bromoxynil heptanoate, bromoxynil octanoate / bromoxynil CPA heptanoate / Bromoxynil heptanoate / 2,4-D, Phenmedipham / Desmedipham, Phenmedipham / Desmedipham / Ethofumesate, Metamitron / Ethofumesate, Phenmedipham / Ethofumesate / Metamitron, Fenoxaprop-p-
  • the herbicidal active ingredients a) and their mixtures can be combined with one or more safeners, in particular with the safeners mefenpyr-diethyl (S1-1), cloquintocet-mexyl (S2-1), isoxadifen-ethyl (S3-1) or fenchlorazole-ethyl (S1- 6), preferably with (S1-1), (S2-1) or (S3-1).
  • the safeners mefenpyr-diethyl (S1-1), cloquintocet-mexyl (S2-1), isoxadifen-ethyl (S3-1) or fenchlorazole-ethyl (S1- 6 preferably with (S1-1), (S2-1) or (S3-1).
  • microemulsion concentrates according to the invention without alcoholic solvent give stable microemulsions when diluted with water.
  • microemulsion concentrates and microemulsions according to the invention show an advantageous physical application behavior.
  • the agrochemical active ingredient remains evenly distributed in the spray tank during application, which enables even application to the crop or cultivated area.
  • Mixtures also formed in the spray tank (tank mixtures), such as aqueous solutions, Suspensions, emulsions or suspoemulsions are stable.
  • the agrochemical compositions according to the invention have an excellent biological action and are preferably synergistic. These effects allow, among other things, a reduction of the application rate, the fight against a broad spectrum of harmful organisms, the closing of gaps in effectiveness, a faster and safer effect, a longer lasting effect, a complete control of the harmful organisms with only one or a few applications, and an extension of the application period ,
  • the solvents were initially introduced and the agrochemical active ingredients and then the surfactants and customary auxiliaries and additives were added with stirring.
  • the microemulsion concentrates thus produced were then added to water in a ratio of 1:10, 1:30 and 1: 100. Microemulsions were obtained. The microemulsions were stored at 50 degrees Celsius for 3 months and were stable for the entire period.
  • Solvesso® 200 (Exxon): Aromatic mixture Arkopal® N 100 (Clariant): Nonylphenol ethoxylate with 10 ethylene oxide units
  • Sapogenat® T-100 (Clariant): triisobutylphenol ethoxylate with 10 ethylene oxide units
  • Emulsogen® V 1816 (Clariant): PO-EO block copolymer Triton® GR 7 ME (Union Carbide): di (2-ethylhexyl) sulfosuccinate Phenylsulfonat® Ca 100 (Clariant): calcium dodecylbenzenesulfonate Genapol® X-060 (Clariant): isotridecyl alcohol with 6 ethylene oxide units Genapol® X-080 (Clariant): isotridecyl alcohol with 8 ethylene oxide units Genapol® PF 40 (Clariant): EO-PO-EO block copolymer Edenol® D 81 (Cognis): epoxidized soybean oil

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un concentré de microémulsion, contenant : a) une ou plusieurs substance(s) active(s) agrochimique(s) ; b) un ou plusieurs solvant(s) organique(s) non alcoolique(s) ; c) un ou plusieurs tensioactif(s) anionique(s), et ; d) un ou plusieurs tensioactif(s) non anionique(s). Le concentré de microémulsion est conçu pour être utilisé dans le domaine de la protection phytosanitaire.
EP03789129A 2002-12-17 2003-12-04 Concentres de microemulsion Withdrawn EP1575357A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10258867 2002-12-17
DE10258867A DE10258867A1 (de) 2002-12-17 2002-12-17 Mikroemulsionskonzentrate
PCT/EP2003/013693 WO2004054360A2 (fr) 2002-12-17 2003-12-04 Concentres de microemulsion

Publications (1)

Publication Number Publication Date
EP1575357A2 true EP1575357A2 (fr) 2005-09-21

Family

ID=32477706

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03789129A Withdrawn EP1575357A2 (fr) 2002-12-17 2003-12-04 Concentres de microemulsion

Country Status (17)

Country Link
US (1) US20040132621A1 (fr)
EP (1) EP1575357A2 (fr)
JP (1) JP2006509807A (fr)
KR (1) KR20050088183A (fr)
CN (1) CN1725951A (fr)
AU (1) AU2003293763A1 (fr)
BR (1) BR0317398A (fr)
CA (1) CA2510028A1 (fr)
DE (1) DE10258867A1 (fr)
EA (1) EA200500965A1 (fr)
HR (1) HRP20050564A2 (fr)
IL (1) IL169126A0 (fr)
MX (1) MXPA05006483A (fr)
PL (1) PL377773A1 (fr)
RS (1) RS20050446A (fr)
WO (1) WO2004054360A2 (fr)
ZA (1) ZA200504443B (fr)

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Also Published As

Publication number Publication date
CN1725951A (zh) 2006-01-25
AU2003293763A1 (en) 2004-07-09
DE10258867A1 (de) 2004-07-08
US20040132621A1 (en) 2004-07-08
HRP20050564A2 (en) 2006-07-31
KR20050088183A (ko) 2005-09-02
RS20050446A (sr) 2008-04-04
WO2004054360A3 (fr) 2004-10-07
WO2004054360A2 (fr) 2004-07-01
ZA200504443B (en) 2005-11-22
BR0317398A (pt) 2005-11-16
IL169126A0 (en) 2009-02-11
CA2510028A1 (fr) 2004-07-01
PL377773A1 (pl) 2006-02-20
JP2006509807A (ja) 2006-03-23
EA200500965A1 (ru) 2005-12-29
MXPA05006483A (es) 2005-08-26

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