EP1575357A2 - Microemulsion concentrates - Google Patents

Microemulsion concentrates

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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)
French (fr)
Inventor
Gerhard Frisch
Detlev Haase
Thomas Maier
Gerhard Schnabel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
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/en
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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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Abstract

The invention relates to a microemulsion concentrate containing a) at least one agrochemical active ingredient, b) at least one non-alcoholic organic solvent, c) at least one anionic surfactant, and d) at least one non-ionic surfactant. Said microemulsion concentrate is suitable for using in the field of crop protection.

Description

Beschreibungdescription
Mi roemulsionskonzentrateMicro emulsion concentrates
Die vorliegende Erfindung betrifft das Gebiet der Pflanzenschutzmittelformulierungen. Insbesondere betrifft die Erfindung flüssige Formulierungen in Form von Mikroemulsionskonzentraten, welche agrochemische Wirkstoffe enthalten.The present invention relates to the field of crop protection formulations. In particular, the invention relates to liquid formulations in the form of microemulsion concentrates which contain agrochemical active ingredients.
Wirkstoffe für den Pflanzenschutz werden im allgemeinen nicht in ihrer reinen Form eingesetzt. In Abhängigkeit von dem Anwendungsgebiet und der Anwendungsart, sowie von physikalischen, chemischen und biologischen Parametern wird der Wirkstoff in Mischung mit üblichen Hilfs- und Zusatzstoffen als feste oder flüssige Wirkstoffformulierung eingesetzt.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.
Flüssige Formulierungen sind z.B. beschrieben 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 und EP 0 118 579.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.
Die Aufgabe der vorliegenden Erfindung bestand darin, eine verbesserte Pflanzenschutzmittelformulierung zur Verfügung zu stellen, welche eine überlegene chemische und physikalische Stabilität und agrochemische Wirkung aufweist.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.
Überraschenderweise wurde nun gefunden, daß diese Aufgabe durch das spezielle Mikroemulsionskonzentrat (MC) der vorliegenden Erfindung gelöst wird.Surprisingly, it has now been found that this object is achieved by the special microemulsion concentrate (MC) of the present invention.
Die vorliegende Erfindung betrifft somit ein Mikroemulsionskonzentrat, enthaltend a) ein oder mehrere agrochemische Wirkstoffe, b) ein oder mehrere nicht-alkoholische organische Lösungsmittel, c) ein oder mehrere anionische Tenside, und d) ein oder mehrere nichtionische Tenside.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.
Darüber hinaus kann das erfindungsgemäße Mikroemulsionskonzentrat als weitere Komponenten gegebenenfalls noch übliche Hilfs- und Zusatzstoffe enthalten. Unter dem Begriff Mikroemulsionskonzentrat (MC) wird eine Komposition verstanden, die bei Verdünnung mit Wasser Mikroemulsionen bildet, z.B. Öl-in- Wasser-Mikroemulsionen oder Wasser-in-ÖI-Mikroemulsionen. Unter einer Mikroemulsion wird eine Emulsion verstanden, die thermodynamisch stabil ist und eine Tröpfchengröße der emulgierten Phase aufweist, die im allgemeinen im Bereicht von 10 - 400 nm, vorzugsweise 50 - 250 nm liegt.In addition, the microemulsion concentrate according to the invention may also contain customary auxiliaries and additives as further components. The term microemulsion concentrate (MC) 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.
Die erfindungsgemäßen Mikroemulsionskonzentrate enthalten im allgemeinen folgende Mengen an Komponenten a), b), c) und d), dabei bezieht sich die AngabeThe microemulsion concentrates according to the invention generally contain the following amounts of components a), b), c) and d)
„Gew.-%" hier und in der gesamten Beschreibung, wenn nicht anders definiert, auf das relative Gewicht der jeweiligen Komponente bezogen auf das Gesamtgewicht der Formulierung:"% 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:
Komponente a): 0,001 - 50 Gew.-%, bevorzugt 0,1 - 30 Gew.-%, besonders bevorzugt 2 - 25 Gew.-%.Component a): 0.001-50% by weight, preferably 0.1-30% by weight, particularly preferably 2-25% by weight.
Komponente b): 10 - 90 Gew.-%, bevorzugt 20- 85 Gew.-%, besonders bevorzugtComponent b): 10-90% by weight, preferably 20-85% by weight, particularly preferably
25 - 80 Gew.-%.25-80% by weight.
Komponente c): 0,1 - 25 Gew.-%, bevorzugt 1 - 20 Gew.-%, besonders bevorzugt 2Component c): 0.1-25% by weight, preferably 1-20% by weight, particularly preferably 2
- 15 Gew.-%.- 15% by weight.
Komponente d): 0,1 - 60 Gew.-%, bevorzugt 1 ,5 - 45 Gew.-%, besonders bevorzugtComponent d): 0.1-60% by weight, preferably 1.5-45% by weight, particularly preferably
2 - 40 Gew.-%.2 - 40% by weight.
Als agrochemische Wirkstoffe a) kommen z.B. Herbizide, Insektizide, Fungizide, Safener und Wachstumsregulatoren in Betracht. Bevorzugt sind Herbizide, z.B. blattaktive Herbizide wie ALS-Inhibitoren (z.B. Sulfonamide wie Flucarbazone, Propoxycarbazone oder Amicarbazone oder Sulfonylhamstoffe wie Mesosulfuron, lodosulfuron, Amidosulfuron, Foramsulfuron), Diflufenican, Bromoxynilhaltige oder loxynilhaltige Produkte, Herbizide aus der Klasse der Aryloxy-Phenoxypropionate wie Fenöxaprop-p-ethyl, Zuckerrübenherbizide wie Desmedipham, Phenmedipham, Ethofumesate oder Metamitron, Glyphosate oder Glufosinate oder auch Wirkstoffe aus der Klasse der HPPD-Inhibitoren (z.B. Isoxaflutole, Sulcotrione, Mesotrione).Herbicides, insecticides, fungicides, safeners and growth regulators come into consideration as agrochemical active ingredients a). Preference is given to 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).
In den erfindungsgemäßen Mikroemulsionskonzentraten enthaltene Herbizide sind z.B. ALS-Inhibitoren (Acetolactat-Synthetase-Inhibitoren) oder von ALS-Inhibitoren verschiedene Herbizide, wie Herbizide aus der Gruppe der Carbamate, Thiocarbamate, Halogenacetanilide, substituierte Phenoxy-, Naphthoxy- und Phenoxyphenoxycarbonsäure-Derivate sowie Heteroaryloxy- phenoxyalkancarbonsäure-Derivate, wie Chinolyloxy-, Chinoxalyl-oxy-, Pyridyloxy-, Benzoxazolyloxy- und Benzthiazolyloxyphenoxyalkan-carbonsäureester, Cyclo- hexandionabkömmlinge, Phosphor-haltige Herbizide, z.B. vom Glufosinate-Typ oder vom Glyphosate-Typ, sowie S-(N-Aryl-N-alkylcarbamoylmethyl)- dithiophosphorsäureester.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.
Bei den ALS-Inhibitoren handelt es sich insbesondere um Imidazolinone, Pyrimidinyloxy-pyridincarbonsäure-Derivate, Pyrimidyloxy-benzoesäure-Derivate, Triazolo-pyrimidin-sulfonamid-Derivate und um Sulfonamide, vorzugsweise aus der Gruppe der Sulfonylharnstoffe.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.
Unter den in den erfindungsgemäßen Mikroemulsionskonzentraten als Komponente enthaltenen Wirkstoffen aus der Gruppe der ALS-Inhibitoren wie Sulfonylharnstoffe sind im Sinne der vorliegenden Erfindung neben den neutralen Verbindungen stets auch deren Salze mit anorganischen und/oder organischen Gegenionen zu verstehen. So können z.B. Sulfonylharnstoffe z.B. Salze bilden, bei denen der Wasserstoff der -S02-NH-Gruppe durch ein für die Landwirtschaft geeignetes Kation ersetzt ist. Diese Salze sind beispielsweise Metallsalze, insbesondere Alkalimetallsalze oder Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, oder auch Ammoniumsalze oder Salze mit organischen Aminen. Ebenso kann Sälzbildühg durch Anlagerung einer Säure an basischen Gruppen, wie z.B. Amino und Alkylamino, erfolgen. Geeignete Säuren hierfür sind starke anorganische und organische Säuren, beispielsweise HCI, HBr, H2SO4 oder HNO3. Bevorzugte ALS-Inhibitoren entstammen aus der Reihe der Sulfonylharnstoffe, z.B. Pyrimidin- oder Triazinylaminocarbonyl-[benzol-, pyridin-, pyrazol-, thiophen- und (aIkylsuIfonyl)-alkylamino-]-sulfamide. Bevorzugt als Substituenten am Pyrimidinring oder Triazinring sind Alkoxy, Alkyl, Haloalkoxy, Haloalkyl, Halogen oder Dimethylamino, wobei alle Substituenten unabhängig voneinander kombinierbar sind. Bevorzugte Substituenten im Benzol-, Pyridin-, Pyrazol-, Thiophen- oder (Alkylsulfonyl)-alkylamino-Teil sind Alkyl, Alkoxy, Halogen wie F, Cl, Br oder J, Amino, Alkylamino, Dialkylamino, Acylamino wie Formylamino, Nitro, Alkoxycarbonyl, Aminocarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Alkoxyaminocarbonyl, Halogenalkoxy, Halogenalkyl, Alkylcarbonyl, Alkoxyalkyl, Alkylsulfonylaminoalkyl, (Alkansulfonyl)alkylamino. Solche geeigneten Sulfonylharnstoffe sind beispielsweiseIn the context of the present invention, 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. For example, 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. Sälzbildühg can also be carried out by the addition of an acid to basic groups such as amino and alkylamino. 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
A1) Phenyl- und Benzylsulfonylhamstoffe und verwandte Verbindungen, z.B.A1) Phenyl and benzylsulfonyl ureas and related compounds, e.g.
1-(2-Chlorphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)hamstoff1- (2-Chlorophenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea
(Chlorsulfuron),(Chlorsulfuron),
1-(2-Ethoxycarbonylphenylsulfonyl)-3-(4-chlor-6-methoxypyrimidin-2-yl)hamstoff1- (2-Ethoxycarbonylphenylsulfonyl) -3- (4-chloro-6-methoxypyrimidine-2-yl) urea
(Chlorimuron-ethyl),(Chlorimuron-ethyl),
1-(2-Methoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)harnstoff1- (2-methoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea
(Metsulfuron-methyl),(Metsulfuron-methyl),
1-(2-Chlorethoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)harnstoff1- (2-chloroethoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea
(Triasulfuron),(Triasulfuron),
1-(2-Methoxycarbonylphenylsulfonyl)-3-(4,6-dimethylpyrimidin-2-yl)hamstoff1- (2-Methoxycarbonylphenylsulfonyl) -3- (4,6-dimethylpyrimidin-2-yl) urea
(Sulfumeturon-methyl),(Sulfumeturon-methyl),
1-(2-Methoxycarbonylphenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3- methylharnstoff (Tribenuron-methyl),1- (2-methoxycarbonylphenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -3-methylurea (tribenuron-methyl),
1-(2-Methoxycarbonylbenzylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)harnstoff1- (2-Methoxycarbonylbenzylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea
(Bensulfuron-methyl),(Bensulfuron-methyl),
1-(2-Methoxycarbonylphenylsulfonyl)-3-(4,6-bis-(difluormethoxy)pyrimidin-2-yl)- harnstoff, (Primisulfuron-methyl),1- (2-methoxycarbonylphenylsulfonyl) -3- (4,6-bis- (difluoromethoxy) pyrimidin-2-yl) urea, (primisulfuron-methyl),
3-(4-EthyI-6-methoxy-1 ,3,5-triazin-2-yl)-1-(2,3-dihydro-1 ,1-dioxo-2-methylbenzo-3- (4-Ethyl-6-methoxy-1,3,5-triazin-2-yl) -1- (2,3-dihydro-1,1-dioxo-2-methylbenzo-
[b]thiophen-7-sulfonyl)hamstoff (EP-A 0 796 83), 3-(4-Ethoxy-6-ethyl-1 ,3,5-triazin-2-yI)-1-(2,3-dihydro-1 ,1-dioxo-2-methylbenzo[b]- thiophen-7-sulfonyl)hamstoff (EP-A 0 079 683),[b] thiophene-7-sulfonyl) urea (EP-A 0 796 83), 3- (4-ethoxy-6-ethyl-1, 3,5-triazin-2-yI) -1- (2,3-dihydro-1, 1-dioxo-2-methylbenzo [b] - thiophene-7- sulfonyl) urea (EP-A 0 079 683),
3-(4-Methoxy-6-methyI-1 ,3,5-triazin-2-yI)-1-(2-methoxycarbonyl-5-jod-phenyl- sulfonyl)-harnstoff (lodosulfuron-methyl und dessen Salze wie das Natriumsalz, WO3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yI) -1- (2-methoxycarbonyl-5-iodophenylsulfonyl) urea (iodosulfuron-methyl and its salts like that Sodium salt, WO
92/13845),92/13845)
DPX-66037, Triflusulfuron-methyl (s. Brighton Crop Prot. Conf. - Weeds - 1995, S.DPX-66037, triflusulfuron-methyl (see Brighton Crop Prot. Conf. - Weeds - 1995, p.
853),853),
CGA-277476, (s. Brighton Crop Prot. Conf. - Weeds - 1995, S. 79),CGA-277476, (see Brighton Crop Prot. Conf. - Weeds - 1995, p. 79),
Methyl-2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methansulfon-amido- methyl-benzoat (Mesosulfuron-methyl und dessen Salze wie das Natriumsalz, WOMethyl 2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-methanesulfonamido methyl benzoate (mesosulfuron methyl and its salts such as the sodium salt, WO
95/10507),95/10507)
N,N-Dimethyl-2-[3-(4,6-dimethoxypyrimjdin-2-yl)ureidosulfonyl]-4-formylamino- benzamid (Foramsulfuron und dessen Salze wie das Natriumsalz, WO 95/01344);N, N-dimethyl-2- [3- (4,6-dimethoxypyrimdin-2-yl) ureidosulfonyl] -4-formylamino-benzamide (foramsulfuron and its salts such as the sodium salt, WO 95/01344);
A2) Thienylsulfonylhamstoffe, z.B.A2) Thienylsulfonylureas, e.g.
1-(2-Methoxycarbonylthiophen-3-yl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2- yl)harnstoff (Thifensulfuron-methyl);1- (2-methoxycarbonylthiophene-3-yl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea (thifensulfuron-methyl);
A3) Pyrazolylsulfonylharnstoffe, z.B.A3) pyrazolylsulfonylureas, e.g.
1-(4-Ethoxycarbonyl-1-methylpyrazol-5-yl-sulfonyl)-3-(4,6-dimethoxypyrimidin-2- yl)hamstoff (Pyrazosulfuron-methyl);1- (4-Ethoxycarbonyl-1-methylpyrazol-5-yl-sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (pyrazosulfuron-methyl);
Methyl-3-chlor-5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methyl-pyrazol-Methyl 3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methyl-pyrazole
4-carboxylat (EP-A 0 282 613);4-carboxylate (EP-A 0 282 613);
5-(4,6-Dimethylpyrimidin-2-yl-carbamoylsulfamoyl)-1-(2-pyridyl)-pyrazol-4-car- bonsäuremethylester (NC-330, s. Brighton Crop Prot. Conference 'Weeds' 1991 , Vol.5- (4,6-Dimethylpyrimidin-2-yl-carbamoylsulfamoyl) -1- (2-pyridyl) -pyrazole-4-carboxylic acid methyl ester (NC-330, see Brighton Crop Prot. Conference 'Weeds' 1991, vol.
1 , S. 45 ff.),1, p. 45 ff.),
DPX-A8947, Azimsulfuron, (s. Brighton Crop Prot. Conf. 'Weeds' 1995, S. 65);DPX-A8947, Azimsulfuron, (see Brighton Crop Prot. Conf. 'Weeds' 1995, p. 65);
A4) Sülfondiamid-Derivate, z.B.A4) Sulphondiamide derivatives, e.g.
3-(4,6-Dimethoxypyrimidin-2-yl)-1-(N-methyl-N-methyIsulfonylaminosulfonyI)- hamstoff (Amidosulfuron) und dessen Strukturanaloge (EP-A 0 131 258 und Z. Pfl. Krankh. Pfl. Schutz, Sonderheft XII, 489-497 (1990)); A5) Pyridylsulfonylharnstoffe, z.B.3- (4,6-Dimethoxypyrimidin-2-yl) -1- (N-methyl-N-methyIsulfonylaminosulfonyI) - urea (Amidosulfuron) and its structural analogues (EP-A 0 131 258 and Z. Pfl. Krankh. Pfl. Schutz , Special Issue XII, 489-497 (1990)); A5) Pyridylsulfonylureas, e.g.
1-(3-N,N-DimethyIaminocarbonylpyridin-2-yIsulfonyl)-3-(4,6-dimethoxypyrimidin-2- yl)harnstoff (Nicosulfuron),1- (3-N, N-DimethyIaminocarbonylpyridin-2-yIsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (nicosulfuron),
1-(3-Ethylsulfonylpyridin-2-ylsulfonyl)-3-(-(4,6-dimethoxypyrimidin-2-yl)harnstoff (Rimsulfuron),1- (3-ethylsulfonylpyridin-2-ylsulfonyl) -3 - (- (4,6-dimethoxypyrimidin-2-yl) urea (rimsulfuron),
2-[3-(4,6-Dimethoxypyrimidin-2-yl)ureidosulfonyl]-6-trifluormethyl-3-pyridin- carbonsäuremethylester, Natriumsalz (DPX-KE 459, Flupyrsulfuron, s. Brighton Crop Prot. Conf. Weeds, 1995, S. 49), Trifloxysulfuron und dessen Natriumsalz;2- [3- (4,6-Dimethoxypyrimidin-2-yl) ureidosulfonyl] -6-trifluoromethyl-3-pyridinecarboxylic acid methyl ester, sodium salt (DPX-KE 459, Flupyrsulfuron, see Brighton Crop Prot. Conf. Weeds, 1995, P. 49), trifloxysulfuron and its sodium salt;
A6) Alkoxyphenoxysulfonylharnstoffe, wie sie z.B. in EP-A 0 342 569 beschrieben sind, vorzugsweise 3-(4,6-Dimethoxypyrimidin-2-yl)-1-(2- ethoxyphenoxy)-sulfonylhamstoff (Ethoxysulfuron) oder dessen Salze;A6) 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;
A7) Imidazolylsulfonylharnstoffe, z.B.A7) imidazolylsulfonylureas, e.g.
MON 37500, Sulfosulfuron (s. Brighton Crop Prot. Conf. 'Weeds', 1995, S: 57), und andere verwandte Sulfonylharnstoff-Derivate und Mischungen daraus.MON 37500, Sulfosulfuron (see Brighton Crop Prot. Conf. 'Weeds', 1995, p: 57), and other related sulfonylurea derivatives and mixtures thereof.
Typische Vertreter dieser Wirkstoffe sind unter anderem die nachfolgend aufgeführten Verbindungen und deren Salze: Amidosulfuron, Azimsulfuron, Bensulfuron-methyl, Chlorimuron-Ethyl, Chlorsulfuron, Cinosulfuron, Cyclosulfamuron, Ethametsulfuron-methyl, Ethoxysulfuron, Flazasulfuron, Flupyrsulfuron-Methyl-Natrium, Halosulfuron-Methyl, Imazosulfuron, Metsulfuron- Methyl, Nicosulfuron, Oxasulfuron, Primisulfuron-Methyl, Prosulfuron, Pyrazosulfuron-Ethyl, Rimsulfuron, Sulfometuron-Methyl, Sulfosulfuron, Thifensulfuron-Methyl, Triasulfuron, Tribenuron-Methyl, Trifloxysulfuron und dessen Natriumsalz, Triflusulfuron-Methyl, lodosulfuron-Methyl und dessen Natriumsalz (WO 92/13845), Mesosulfuron-Methyl und dessen Natriumsalz (Agrow Nr. 347, 3. März 2000, Seite 22 (PJB Publications Ltd. 2000)) und Foramsulfuron und dessen Natriumsalz (Agrow Nr. 338, 15. Oktober 1999, Seite 26 (PJB Publications Ltd. 1999)). Die vorstehend aufgeführten Wirkstoffe sind z.B. bekannt aus „The Pesticide Manual", 12. Auflage (2000), The British Crop Protection Council oder den nach den einzelnen Wirkstoffen aufgeführten Literaturstellen.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, lodosulfuron- Methyl and its sodium salt (WO 92/13845), mesosulfuron-methyl and its sodium salt (Agrow No. 347, March 3, 2000, page 22 (PJB Publications Ltd. 2000)) and foramsulfuron and its sodium salt (Agrow No. 338, 15 October 1999, page 26 (PJB Publications Ltd. 1999)). The active ingredients listed above are known, for example, from "The Pesticide Manual", 12th edition (2000), The British Crop Protection Council or the literature references listed according to the individual active ingredients.
Weitere geeignete ALS-Inhibitoren sind z.B.Other suitable ALS inhibitors are e.g.
B) Imidazolinone, z.B.B) Imidazolinones, e.g.
2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylbenzoesäure-methylester und 2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-4-methylbenzoesäure (Imazamethabenz),Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-methyl) -yl) -4-methylbenzoic acid (imazamethabenz),
5-Ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure (Imazethapyr),5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid (imazethapyr),
2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-chinolin-3-carbonsäure (Imazaquin), 2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure (Imazapyr), 5-Methyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure (Imazethamethapyr);2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -quinoline-3-carboxylic acid (imazaquin), 2- (4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl) pyridine-3-carboxylic acid (imazapyr), 5-methyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid ( imazethamethapyr);
C) Triazolopyrimidinsulfonamid-Derivate, z.B. N-(2,6-Difluorphenyl)-7-methyl-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2-sulfonamid (Flumetsulam),C) triazolopyrimidine sulfonamide derivatives, e.g. N- (2,6-difluorophenyl) -7-methyl-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (flumetsulam),
N-(2,6-Dichlor-3-methylphenyl)-5,7-dimethoxy-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2- sulfonamid,N- (2,6-dichloro-3-methylphenyl) -5,7-dimethoxy-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide,
N-(2,6-Difluorphenyl)-7-fluor-5-methoxy-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2-sulfonamid, N-(2,6-Dichlor-3-methylphenyl)-7-chlor-5-methoxy-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2- sulfonamid,N- (2,6-difluorophenyl) -7-fluoro-5-methoxy-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide, N- (2,6-dichloro-3-methylphenyl ) -7-chloro-5-methoxy-1, 2,4-triazolo [1, 5-c] pyrimidine-2-sulfonamide,
N-(2-Chlor-6-methoxycarbonyl)-5,7-dimethyl-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2- sulfonamid (EP-A 0 343 752, US-A 4,988,812);N- (2-chloro-6-methoxycarbonyl) -5,7-dimethyl-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (EP-A 0 343 752, US-A 4,988,812) ;
D)~ Pyrimidinyloxy-pyridincarbonsäure- bzw. Pyrimidinyloxybenzoesäure- Derivate, z.B.D) ~ pyrimidinyloxy-pyridinecarboxylic acid or pyrimidinyloxybenzoic acid derivatives, for example
3-(4,6-Dimethoxypyrimidin-2-yl)-oxy-pyridin-2-carbonsäurebenzyl-ester (EP-A 0 249 707), 3-(4,6-Dimethoxypyrimidin-2-yl)-oxy-pyridin-2-carbonsäuremethylester (EP-A3- (4,6-dimethoxypyrimidin-2-yl) -oxypyridine-2-carboxylic acid benzyl ester (EP-A 0 249 707), 3- (4,6-Dimethoxypyrimidin-2-yl) -oxypyridine-2-carboxylic acid methyl ester (EP-A
0 249 707),0 249 707),
2,6-Bis[(4,6-dimethoxypyrimidin-2-yl)-oxy]-benzoesäure (EP-A 0 321 846),2,6-bis [(4,6-dimethoxypyrimidin-2-yl) -oxy] -benzoic acid (EP-A 0 321 846),
2,6-Bis[(4,6-dimethoxypyrimidin-2-yl)-oxy]-benzoesäure-1-(ethoxycarbonyl-oxyethyl)- ester (EP-A 0 472 113).2,6-bis [(4,6-dimethoxypyrimidin-2-yl) -oxy] -benzoic acid 1- (ethoxycarbonyl-oxyethyl) ester (EP-A 0 472 113).
Bei den in den erfindungsgemäßen Mikroemulsionskonzentraten enthaltenen von ALS-Inhibitoren verschiedenen herbiziden Wirkstoffen handelt es sich z.B. Herbizide aus der Gruppe der Carbamate, Thiocarbamate, Halogenacetanilide, substituierte Phenoxy-, Naphthoxy- und Phenoxyphenoxycarbonsäure-Derivate sowie Heteroaryloxy-phenoxyalkancarbonsäure-Derivate, wie Chinolyloxy-, Chinoxalyl- oxy-, Pyridyloxy-, Benzoxazolyloxy- und Benzthiazoϊyloxyphenoxyalkan- carbonsäureester, Cyclohexandionabkömmlinge, Phosphor-haltige Herbizide, z.B. vom Glufosinate-Typ oder vom Glyphosate-Typ, sowie S-(N-Aryl-N- alkylcarbamoylmethy -dithiophosphorsäureester. Bevorzugt sind dabei Phenoxyphenoxy- und Heteroaryloxyphenoxycarbonsäureester und -salze sowie Herbizide wie Bentazon, Cyanazin, Atrazin, Dicamba oder Hydroxybenzonitrile wie Bromoxynil und loxynil und deren Salze und Ester und andere Blattherbizide.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. of the glufosinate type or of the glyphosate type, as well as S- (N-aryl-N-alkylcarbamoylmethydithiophosphoric acid esters. 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.
Geeignete von ALS-Inhibitoren verschiedene herbizide Wirkstoffe, die in den erfindungsgemäßen Mikroemulsionskonzentraten als Komponente enthalten sein können, sind beispielsweise: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:
E) Herbizide vom Typ der Phenoxyphenoxy- undE) Herbicides of the phenoxyphenoxy and
Heteroaryloxyphenoxycarbonsäure-Derivate, wieHeteroaryloxyphenoxycarboxylic acid derivatives, such as
E1) Phenoxyphenoxy- und Benzyloxyphenoxy-carbonsäure-Derivate, z.B. 2-(4- (2,4-Dichlorphenoxy)-phenoxy)-propionsäuremethylester (Diclofop-methyl), 2-(4-(4-Brom-2-chlorphenoxy)phenoxy)propionsäuremethylester (DE-A 26 01 548), 2-(4-(4-Brom-2-fluorphenoxy)phenoxy)propionsäuremethylester (US-A 4,808,750), 2-(4-(2-Chlor-4-trifluormethylphenoxy)phenoxy)propionsäuremethylester (DE-A 24 33 067), 2-(4-(2-Fluor-4-trifluormethylphenoxy)phenoxy)propionsäuremethylester (US-A ,808,750),E1) 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),
2-(4-(2,4-Dichlorbenzyl)phenoxy)propionsäuremethylester (DE-A 24 17 487), -(4-(4-Trifluormethylphenoxy)phenoxy)pent-2-en-säureethylester, 2-(4-(4-Trifluormethylphenoxy)phenoxy)propionsäuremethylester (DE-A 24 33 067);Methyl 2- (4- (2,4-dichlorobenzyl) phenoxy) propionate (DE-A 24 17 487), - (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-enoic acid ethyl ester, 2- (4- (4 -Trifluoromethylphenoxy) phenoxy) propionic acid methyl ester (DE-A 24 33 067);
E2) "Einkernige" Heteroaryloxyphenoxy-alkancarbonsäure-Derivate, z.B. 2-(4-(3,5-Dichlorpyridyl-2-oxy)phenoxy)propionsäureethylester (EP-A 0 002 925), 2-(4-(3,5-Dichlorpyridyl-2-oxy)phenoxy)propionsäurepropargylester (EP-A 0 003 114),E2) "Mononuclear" heteroaryloxyphenoxy alkane carboxylic acid derivatives, e.g. 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid ethyl ester (EP-A 0 002 925), 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid propyl ester (EP- A 0 003 114),
2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)phenoxy)propionsäure-methylester (EP-A 0 003 890),Methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A 0 003 890),
2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)phenoxy)propionsäureethylester (EP-A 0 003 890),Ethyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A 0 003 890),
2-(4-(5-Chlor-3-fluor-2-pyridyloxy)phenoxy)propionsäurepropargylester (EP-A 0 191 736),Propargic acid 2- (4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy) propionate (EP-A 0 191 736),
2-(4-(5-Trifluormethyl-2-pyridyloxy)phenoxy)propionsäurebutylester (Fluazifop-butyl);2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid butyl ester (fluazifop-butyl);
E3) "Zweikernige" Heteroaryloxyphenoxy-alkancarbonsäure-Derivate, z.B. 2-(4-(6-Chlor-2-chinoxalyloxy)phenoxy)propionsäuremethylester und -ethylester (Quizalofopmethyl und Quizalofopethyl),E3) "dinuclear" heteroaryloxyphenoxy alkane carboxylic acid derivatives, e.g. 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionic acid methyl ester and ethyl ester (quizalofopmethyl and quizalofopethyl),
2-(4-(6-Fluor-2-chinoxalyloxy)phenoxy)propionsäuremethylester (s. J. Pest. Sei. Vol. 10, 61 (1985)),Methyl 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionate (see J. Pest. Sci. Vol. 10, 61 (1985)),
2-(4-(6-Chlor-2-chinoxalyloxy)phenoxy)propionsäure-2-isopropylidenaminooxy- ethylester (Propaquizafop),2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionic acid 2-isopropylideneaminooxy ethyl ester (propaquizafop),
2-(4-(6-Chlorbenzoxazol-2-yl-oxy)phenoxy)propionsäureethylester (Fenoxaprop- ethyl), dessen D(+) Isomer (Fenoxaprop-P-ethyl) und 2-(4-(6-Chlorbenzthiazol-2- ylöxy)phenoxy)propionsäureethylester (DE-A 26 40 730),2- (4- (6-Chlorobenzoxazol-2-yl-oxy) phenoxy) propionic acid ethyl ester (fenoxaprop-ethyl), its D (+) isomer (fenoxaprop-P-ethyl) and 2- (4- (6-chlorobenzthiazol-2 yloxy) phenoxy) propionic acid ethyl ester (DE-A 26 40 730),
2-(4-(6-Chlorchinoxalyloxy)phenoxy)propionsäure-tetrahydro-2-furylmethylester (EP- A 0 323 727); F) Chloracetanilide, z.B.2- (4- (6-chloroquinoxalyloxy) phenoxy) propionic acid tetrahydro-2-furylmethyl ester (EP-A 0 323 727); F) chloroacetanilides, e.g.
N-Methoxymethyl-2,6-diethyl-chloracetanilid (Alachlor), N-(3-Methoxyprop-2-yl)-2-methyl-6-ethyl-chloracetaniIid (Metolachlor), N-(3-Methyl-1 ,2,4-oxadiazol-5-yl-methyl)-chloressigsäure-2,6-dimethyIanilid, N-(2,6-Dimethylphenyl)-N-(1-pyrazolylmethyl)-chloressigsäureamid (Metazachlor);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);
G) Thiocarbamate, z.B. S-Ethyl-N,N-dipropylthiocarbamat (EPTC), S-Ethyl-N,N-diisobutylthiocarbamat (Butylate);G) thiocarbamates, e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylates);
H) Cyclohexandionoxime, z.B.H) cyclohexanedione oximes, e.g.
3-(1-AIIyloxyiminobutyl)-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-encarbon- säuremethylester, (Alloxydim),3- (1-Alyloxyiminobutyl) -4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-encarboxylic acid methyl ester, (alloxydim),
2-(1-Ethoxyiminobutyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1-on2- (1-Ethoxyiminobutyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one
(Sethoxydim),(Sethoxydim),
2-(1-Ethoxyiminobutyl)-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-1-on2- (1-Ethoxyiminobutyl) -5- (2-phenylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one
(Cloproxydim),(Cloproxydim),
2-(1-(3-Chlorallyloxy)iminobutyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1-on,2- (1- (3-chloroallyloxy) iminobutyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one,
2-(1-(3-Chlorallyloxy)iminopropyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1- on (Clethodim),2- (1- (3-chloroallyloxy) iminopropyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one (clethodim),
2-(1-Ethoxyiminobutyl)-3-hydroxy-5-(thian-3-yl)-cyclohex-2-enon (Cycloxydim),2- (1-ethoxyiminobutyl) -3-hydroxy-5- (thian-3-yl) cyclohex-2-enone (cycloxydim),
2-(1-Ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxy-cyclohex-2-en-1-on2- (1-Ethoxyiminopropyl) -5- (2,4,6-trimethylphenyl) -3-hydroxy-cyclohex-2-en-1-one
(Tralkoxydim);(Tralkoxydim);
I) Benzoylcyclohexandione, z.B.I) benzoylcyclohexanediones, e.g.
2-(2-Chlor-4-methylsulfonylbenzoyl)-cyclohexan-1 ,3-dion (SC-0051 , EP-A2- (2-chloro-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione (SC-0051, EP-A
0 137 963), 2-(2-Nitrobenzoyl)-4,4-dimethyl-cyclohexan-1 ,3-dion (EP-A 0 274 634),0 137 963), 2- (2-nitrobenzoyl) -4,4-dimethyl-cyclohexane-1,3-dione (EP-A 0 274 634),
2-(2-Nitro-4-methylsulfonylbenzoyl)-4,4-dimethylcyclohexan-1 ,3-dion (WO 91/13548,2- (2-nitro-4-methylsulfonylbenzoyl) -4,4-dimethylcyclohexan-1, 3-dione (WO 91/13548,
Mesofriöne);Mesofriöne);
J) S-(N-Aryl-N-alkyl-carbamoylmethyl)-dithiophosphonsäureester, wie S-[N-(4-J) S- (N-aryl-N-alkyl-carbamoylmethyl) dithiophosphonic acid esters, such as S- [N- (4-
Chlorphenyl)-N-isopropyl-carbamoylmethyl]-O,O-dimethyl-dithiophosphat (Anilophos).Chlorophenyl) -N-isopropyl-carbamoylmethyl] -O, O-dimethyl dithiophosphate (Anilophos).
K) Alkylazine, z.B. wie beschrieben 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 sowie auch DE-A-19828519, WO-A-98/34925, WO-A-98/42684, WO-A-99/18100, WO-A-99/19309, WO-A-99/37627 und WO-A-99/65882, vorzugsweise solche der Formel (I)K) 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)
worin Rx (Cι-C4)-Alkyl oder (d-C4)-Haloal yl; Rγ (C1-C4)-Alkyl, (C3-C6)-Cycloalkyl oder (C3-C6)-Cycloalkyl-(C -C4)-Alkyl und A -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-, -CH2-CH2-O-, -CH2-CH2-CH2-O- bedeuten, besonders bevorzugt solche der Formel 11-17 wherein R x (-CC 4 ) alkyl or (dC 4 ) -halo yl; R γ (C 1 -C 4 ) alkyl, (C 3 -C 6 ) cycloalkyl or (C 3 -C 6 ) cycloalkyl (C -C 4 ) alkyl and A -CH2-, -CH2-CH2 -, -CH2-CH2-CH 2 -, -O-, -CH2-CH2-O-, -CH2-CH2-CH2-O-, particularly preferably those of the formula 11-17
L) Phosphor-haltige Herbizide, z.B. vom GIusosinate-Typ wie Glufosinate im engeren Sinne, d. h. D,L-2-Amino-4-[hydroxy(methyl)phosphinyl]-butansäure, Glufosinate-monoammoniumsalz, L-Glufosinate, L- oder (2S)-2-Amino-4- [hydroxy(methyl)phosphinyl]-butansäure, L-Glufosinate-monoammoniumsalz oder Bialaphos (oder Bilanafos), d.h. L-2-Amino-4-[hydroxy(methyl)phosphinyl]-butanoyl- L-alanyl-L-alanin, insbesondere dessen Natriumsalz, oder vom Glyphosate-Typ wie Glyphosate, d. h. N-(Phosphonomethyl)-glycin, Glyphosate-monoisopropylammoniumsalz, Glyphosate-natriumsalz, oder Sulfosate, d. h. N-(Phosphonomethyl)-glycin-trimesiumsalz = N-(Phosphonomethyl)-glycin- trimethylsulfoxoniumsalz.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. H. N- (phosphonomethyl) glycine, glyphosate monoisopropylammonium salt, glyphosate sodium salt, or sulfosate, i.e. H. N- (phosphonomethyl) glycine trimesium salt = N- (phosphonomethyl) glycine trimethylsulfoxonium salt.
Die Herbizide der Gruppen B bis L sind beispielsweise aus den oben jeweils genannten Schriften und aus "The Pesticide Manual", 12. Auflage, 2000, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -", by W.T. Thompson, Thompson Publications, Fresno CA, USA 1990 und "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990, bekannt.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.
Bei den in den erfindungsgemäßen Mikroemulsionskonzentraten enthaltenen agrochemischen Wirkstoffen a) sind bevorzugt:The following are preferred for the agrochemical active substances a) contained in the microemulsion concentrates according to the invention:
Acetochlor, Aclonifen, Alachlor, Amidochlor, Amidosulfuron, Bensulfuron-methyl, Bromoxyniloctanoat, Butachlor, Chlorsulfuron, Cinosulfuron, Clodinafop-propargyl, Cypermethrin, 2,4-D-Ester, 2,4-DB-Ester, 2,4-DP-Ester, CMPP-Ester, MCPA-Ester, Deltamethrin, Desmedipham, Diclofop-methyl, Diflufenican, Ethofumesat, Fenxoapropethyl, Fipronil, Fluoroglykofen, Foramsulfuron, Imazapyr, Imazosulfuron, lodosulfuron-methyl, Imidocloprid, loxyniloctanoat, Isoxaflutol, Lactofen, Mesosulfuron-methyl, Metolachlor, Metsulfuron-methyl, Metamitron, Nicosulfuron, Oxyfluorfen, Pendimethalin, Phenmedipham, Primisulfuron-methyl, Propaquizafop, Pyrazosulfuron-methyl, Rimsulfuron, Triflusulfuron-methyl, Trifluralin, lodosulfuron, Prochloraz, Amitraz, Oxazinon, Oxadiargyl, Metamitron, Mefenpyrdiethyl, Phenmedipham, Desmedipham, Isoxadifen-ethyl, und deren Salze, z.B. die Natriumsalze.Acetochlor, Aclonifen, Alachlor, Amidochlor, Amidosulfuron, Bensulfuron-methyl, Bromoxyniloctanoat, Butachlor, Chlorsulfuron, Cinosulfuron, Clodinafop-propargyl, Cypermethrin, 2,4-D-Ester, 2,4-DB-Ester, 2,4-DP- Esters, CMPP esters, MCPA esters, deltamethrin, desmedipham, diclofop-methyl, diflufenican, ethofumesate, fenxoapropethyl, fipronil, fluoroglycofen, foramsulfuron, imazapyr, imazosulfuron, iodosulfuron-methyl, imidoclopafano, loxynoxo lactol, loxynoxo lactol, loxynoxo lactol, loxynoxopro Mesosulfuron-methyl, Metolachlor, Metsulfuron-methyl, Metamitron, Nicosulfuron, Oxyfluorfen, Pendimethalin, Phenmedipham, Primisulfuron-methyl, Propaquizafop, Pyrazosulfuron-methyl, Rimsulfuron, Triflusulfuron-methyl, Trifluralin, Prochlorosulfononyl, Prozosulfononyl, Prozosulfononyl, Prozosulfononyl, Prozosulfononyl, Prozosulfonon Mefenpyrdiethyl, Phenmedipham, Desmedipham, Isoxadifen-ethyl, and their salts, for example the sodium salts.
Als nicht-alkoholische organische Lösungsmittel b) eignen sich Lösungsmittel, die keine Alkohol-Gruppe enthalten, beispielsweise Kohlenwasserstoffe, Carbonsäurederivate, Phosphorsäureester, Ether, Ketone oder Sulfoxide wie Dimethylsulfoxid.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.
Beispiele für Kohlenwasserstoffe (siehe z.B. Römpp Lexikon Chemie, 10. Auflage, Band 3, Seite 2202 (1997), Georg Thieme Verlag Stuttgart / New York) sind bevorzugt solche, die bei Normalbedingungen flüssig sind. Die Kohlenwasserstoffe können acyclische (aliphatische) Kohlenwasserstoffe sein, oder cyclische Kohlenwasserstoffe, z.B. aromatische oder alicyclische (cycloaliphatische) Kohlenwasserstoffe.Examples of hydrocarbons (see e.g. Römpp Lexikon Chemie, 10th edition, volume 3, page 2202 (1997), Georg Thieme Verlag Stuttgart / New York) 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.
Beispiele für Kohlenwasserstoffe b) sind:Examples of hydrocarbons b) are:
1) aromatische Kohlenwasserstoffe, z.B.1) aromatic hydrocarbons, e.g.
• ein- oder mehrfach alkyl-substituierte (z.B. ein-, zwei- oder dreifach (C-i- Cιo)alkyl-substituierte) Aromaten, z.B. Benzole wie Toluol, Xylole, Mesitylen, Ethylbenzol, oderOne or more alkyl-substituted (for example one, two or three times (C-i-Cιo) alkyl-substituted) aromatics, e.g. Benzenes such as toluene, xylenes, mesitylene, ethylbenzene, or
• Kohlenwasserstoffe mit kondensierten aromatischen Ringsystemen wie Naphthaline, z.B. 1 -Methylnaphthalin, 2-Methylnaphthalin oder Dimethylnaphtalin, oder andere kondensierte aromatische Kohlenwasserstoffe wie Indan oder Tetralin,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,
2) cycloaliphatische Kohlenwasserstoffe, z.B. gesättigte oder ungesättigte, gegebenenfalls ein oder mehrfach alkyl- substituierte (z.B. ein-, zwei- oder dreifach (Cι-Cιo)alkyl-substituierte) Cycloaliphaten wie Cycloalkane, Cycloalkene oder Cycloalkine, z.B. Cyclohexan oder Methylcyclopentan, 3) aliphatische Kohlenwasserstoffe, z.B. lineare oder verzweigte, gesättigte oder ungesättigte Aliphaten, bevorzugt C5- Ci6-Aliphaten, z.B. Alkane, Alkene oder Alkine, wie Pentan, Hexan, Octan, 2- Methylbutan oder 2,2,4-Trimethylpentan.2) cycloaliphatic hydrocarbons, for example saturated or unsaturated, optionally mono- or polysubstituted (for example mono-, di- or tris (Cι-Cιo) 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.
Als Komponente b) können auch Gemische eines oder mehrerer aromatischer Kohlenwasserstoffe und/oder eines oder mehrerer cycloaliphatischer Kohlenwasserstoffe und/oder eines oder mehrerer aliphatischer Kohlenwasserstoffe enthalten sein. Beispiele sind Gemische mehrerer aliphatischer Kohlenwasserstoffe, z.B. kommerziell erhältliche Lösungsmittel der ExxsθL®D-Reihe, lsoPAR®-Reihe oder BAY0L®-Reihe z.B. Bayol®82 (EXXONMOBIL CHEMICALS) oder der ISANE®IP-Reihe oder HYDR0SEAL®G-Reihe (TOTALFINAELF), oder Gemische von aromatischen und aliphatischen Kohlenwasserstoffen, z.B. kommerziell erhältliche Lösungsmittel der SθLvεsso®-Reihe z.B. Solvesso®100, Solvesso®150 oder Solvesso®200 (EXXONMOBIL CHEMICALS), der SθLVAREx®/SθLVARθ®-Reihe (TOTALFINAELF) oder der Caromax®-Reihe z.B. Caromax®28 (Petrochem Carless).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 ExxsθL ® 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 SθLvεsso ® series, e.g. Solvesso ® 100, Solvesso ® 150 or Solvesso ® 200 (EXXONMOBIL CHEMICALS), the SθLVAREx ® / SθLVARθ ® series (TOTALFOMELF) or ® series e.g. Caromax ® 28 (Petrochem Carless).
Bevorzugt sind aliphatische Kohlenwasserstoffe, insbesondere gesättigte aliphatische Kohlenwasserstoffe wie C5-Ci6-Alkane, z.B. aus der Bayol®-Reihe.Aliphatic hydrocarbons, in particular saturated aliphatic hydrocarbons such as C 5 -C 6 alkanes, for example from the Bayol ® series are preferred.
Beispiele für Carbonsäurederivate sind z.B. Ester oder Amide von Carbonsäuren.Examples of carboxylic acid derivatives are e.g. Esters or amides of carboxylic acids.
Als Carbonsäurederivate kommen z.B. die Ester und Amide von Monocarbonsäuren, Dicarbonsäuren oder Polycarbonsäuren wie Tri-, Tetra- oder auch höherfunktionellen Carbonsäuren, vorzugsweise mit 2-26 C-Atomen in Frage.Examples of 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.
Bevorzugte Ester sind die Ester mit Cι-C2o-Alkoholen (z.B. Methanol, Ethanol, Propanol oder Butanol), insbesondere bei Fettsäureestern sind auch die Glycerin- und Glykolester bevorzugt. Als Carbonsäureester kommen auch innere Ester wie Lactone in Frage. Beispiele für Monocarbonsäureester sind die Ester aliphatischer und aromatischer Monocarbonsäuren z.B. aliphatische Ci-Cg-Monocarbonsäureester wie Ameisensäureester, Essigsäureester und Propionsäureester, oder aliphatische Fettsäureester wie Cιo-C22-Fettsäureester, z.B. natürlichen Ursprungs wie sie in natürlichen Ölen oder Pflanzenölen enthalten sind, oder synthetischen Ursprungs, oder aromatische C7-C22-Monocarbonsäureester wie Benzoesäureester oder Phenylessigsäureester.Preferred 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. Examples of 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 Cιo-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.
Beispiele für Fettsäureester sind, z.B. solche natürlichen Ursprungs, z.B. natürliche Öle wie tierische Öle oder Pflanzenöle, oder synthetischen Ursprungs, z.B. Edenor®MESU oder AGNIQUE®ME-Reihe (COGNIS), der SALiM®ME-Reihe (SALIM), der STEPAN®C-Reihe (STEPAN) oder der WιτcoNθL®23-Reihe (WITCO). Als Fettsäureester sind bevorzugt Ester von C10-C22-, vorzugsweise C-i2-C2o-Fettsäuren. Die C10-C22- Fettsäureester sind beispielsweise Ester ungesättigter oder gesättigter C10-C22- Fettsäuren, insbesondere mit gerader Kohlenstoffatomzahl, z.B. Erucasäure, Laurinsäure, Palmitinsäure und insbesondere Cι8-Fettsäuren wie Stearinsäure, Ölsäure, Linolsäure oder Linolensäure.Examples of fatty acid ester are, 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 WιτcoNθL ® 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.
Beispiele für Fettsäureester wie Cι0-C22-Fettsäure-Ester sind Glycerin- und Glykolester von Fettsäuren wie C-ιo-C22-Fettsäuren oder deren Umesterungsprodukte, z.B. Alkyl-Fettsäureester wie Cι-C2o-Alkyl-Cιo-C22-Fettsäure- Ester, wie sie z.B. durch Umesterung der vorgenannten Glycerin- oder Glykol- Fettsäureester wie Cιo-C22-Fettsäure-Ester mit CrC2o-Alkoholen (z.B. Methanol, Ethanol, Propanol oder Butanol) erhalten werden können. Die Umesterung kann nach bekannten Methoden erfolgen, wie sie z.B. beschrieben sind im Römpp Chemie Lexikon, 9. Auflage, Band 2, Seite 1343, Thieme Verlag Stuttgart.Examples of fatty acid esters such as C 0 -C 22 fatty acid esters are glycerol and glycol esters of fatty acids such as C-ιo-C 22 fatty acids or their transesterification products, for example alkyl fatty acid esters such as -C-C 2 o-alkyl-Cιo-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.
Bevorzugte Fettsäureester sind z.B. Öle aus ölliefernden Pflanzenarten wie Sojaöl, Rapsöl, Maiskeimöl, Sonnenblumenöl, Baumwollsaatöl, Leinöl, Kokosöl, Palmöl, Distelöl, Walnussöl, Erdnussöl, Olivenöl oder Rhizinusöl, insbesondere Rapsöl, wobei unter den Pflanzenölen auch deren Umesterungsprodukte verstanden werden, z.B. Alkylester wie Rapsölmethylester oder Rapsölethylester. Beispiele für Dicarbonsäureester und Polycarbonsäureester sind die Vollester von Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Sebacin-, Azelain-, Suberin-, Malein-, Phthal-, Terephthal-, Mellit-, Trimellit- und Polymaleinsäure, insbesondere die C-i-Cio-Alkylester wie die Methylester, Ethylester, Propylester wie n-Propylester oder iso-Propylester, Butylester wie n-Butylester, iso-Butylester, sec-Butylester oder tert-Butylester.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. Examples of 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.
Als Carbonsäureamide kommen auch Cι-C26-Carbonsäure-N,N-di(Cι-C2o- alkyl)amide z.B. Cι-C26-Carbonsäure-N,N-dimethylamide wie N,N-Dimethylformamid oder N,N-Dimethylacetamid in Frage, oder innere Amide wie Lactame, z.B. Pyrrolidone wie N-substituierte Cι-Ci2-Alkyl-pyrrolidone wie N-methyl-pyrrolidon, N- butyl-pyrrolidon, N-octyl-pyrrolidon, N-dodecyl-pyrrolidon und N-cyclohexyl- pyrrolidon.As 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.
Als Phosphorsäureester kommen beispielsweise Triester der Phosphorsäure mit Alkoholen in Frage, wobei die Alkohole bevorzugt ausgewählt sind aus der Gruppe bestehend aus,Examples of suitable phosphoric acid esters are triesters of phosphoric acid with alcohols, the alcohols preferably being selected from the group consisting of
1) einwertige Alkanole mit 1 bis 22 C-Atomen, z.B. n-, i- oder neo-Pentanol, n- Hexanol, n-Octanol, 2-Ethylhexanol,1) monovalent alkanols with 1 to 22 carbon atoms, e.g. n-, i- or neo-pentanol, n-hexanol, n-octanol, 2-ethylhexanol,
2) Diole oder Polyole, wie Ethylenglykol, Propylenglykol oder Glycerin,2) diols or polyols, such as ethylene glycol, propylene glycol or glycerin,
3) Aryl-, Alkylaryl-, Poly(alkyl)aryl- und Poly(arylalkyl)arylalkohole, beispielsweise Phenol und/oder Kresol, Octylphenol, Nonylphenol, Triisobutylphenol, Tristyrylphenol,3) aryl, alkylaryl, poly (alkyl) aryl and poly (arylalkyl) aryl alcohols, for example phenol and / or cresol, octylphenol, nonylphenol, triisobutylphenol, tristyrylphenol,
4) alkoxylierte Alkohole, die durch Umsetzung der vorstehend unter 1), 2) oder 3) genannten Alkohole mit Alkylenoxiden, vorzugsweise (Cι-C )Alkylenoxiden erhalten werden.4) alkoxylated alcohols which are obtained by reacting the alcohols mentioned above under 1), 2) or 3) with alkylene oxides, preferably (-C-C) alkylene oxides.
Bevorzugte Phosphorsäureester sind Triester der ortho-Phosphorsäure, insbesondere alkoxylierte Triester der ortho-Phosphorsäure wie Tri(butyoxyethyI)phosphat. Als Ketone kommen beispielsweise aromatische, cycloaliphatische oder aliphatische Ketone in Frage wie Acetophenon, Benzophenon, Isophoron, Cyclohexanon und Methylethylketon, Ethylbutylketon, Diethylketon, Dibutylketon.Preferred phosphoric acid esters are triesters of orthophosphoric acid, in particular alkoxylated triesters of orthophosphoric acid such as tri (butoxyoxyethyl) phosphate. Examples of 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.
Als Ether kommen beispielsweise aromatische, cycloaliphatische oder aliphatische Ether in Frage wie Anisol, Tetrahydrofuron, Oxiran, Dibutylether, Dipentylether, Butylhexylether, Methyl-tert.Buthylether.Examples of suitable ethers are aromatic, cycloaliphatic or aliphatic ethers such as anisole, tetrahydrofuron, oxirane, dibutyl ether, dipentyl ether, butylhexyl ether, methyl tert-butyl ether.
Bevorzugte nicht-alkoholische Lösungsmittel b) sind aromatische Kohlenwasserstoffe wie, CrC6-Alkyl-benzole z.B. Toluol oder Xylol, Cι-C6- Alkylnaphthaline und Aromatengemische wie die Solvesso®-Reihe von Exxon, Ketone wie Acetophenon, Isophoron, Cyclohexanon und Methylethylketon, N- substituierte Cι-Ci2-Alkyl-pyrrolidone wie N-methyl-pyrrolidon, N-butyl-pyrrolidon, N- octyl-pyrrolidon, N-dodecyl-pyrrolidon und N-cyclohexyl-pyrrolidon, cyclische aliphatische Kohlenwasserstoffe wie Decalin und Cyclohexan, Säureamide wie Dimethylformamid, Dimethylsulfoxid, Lactone wie Gamma-Butyrolacton, Di- oder Polycarbonsäureester wie Cι-Cι2-Alkyl-Phthalsäureester, Adipinsäureester z.B. Diisopropyladipat, Dimethyladipat und Diisobutyladipat, sowie Fettsäureester.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-butyrolactone, di- or polycarboxylic acid esters such as -CC 2 alkyl phthalic acid esters, adipic acid esters, for example diisopropyl adipate, dimethyl adipate and diisobutyl adipate, and also fatty acid esters.
Als anionische Tenside c) eignen sich beispielsweise Sulfate, Sulfonate, Phosphate und Phosponate von Kohlenwasserstoffen, die optional Alkylenoxideinheiten enthalten können. Die Sulfate, Sulfonate, Phosphate und Phosponate können in Form der Säuren oder als Salze vorliegen. Bevorzugt sind anionische Tenside c) der nachfolgenden Formel (I):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 - Q (I) worin Q - O - SO3 M, - SO3 M, - O - PO3H M oder PO3H M ist, worin M gleich H oder ein Kation ist, insbesondere ein Metallkation wie einR - Q (I) where Q is - O - SO 3 M, - SO 3 M, - O - PO3H M or PO 3 HM, where M is H or a cation, especially a metal cation such as a
Alkalimetallion oder Erdalkalimetallion, oder ein Ammoniumion, R ein unsubstituierter oder substituierter Cι-C3o-Kohlenwasserstoffrest ist, der optional über Alkylenoxideinheiten gebunden sein kann, oder R ist eineAlkali metal ion or alkaline earth metal ion, or an ammonium ion, 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
Alkylenoxideinheit. Unter dem Begriff Alkylenoxideinheiten werden insbesondere Einheiten von C2-C10- Alkylenoxiden, wie Ethylenoxid, Propylenoxid oder Butylenoxid verstanden, wobei die Einheiten innerhalb des Tensids gleich oder voneinander verschieden und dabei statistisch gemischt oder blockweise angeordnet sein können.Alkylene oxide. The term 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.
Bevorzugt ist R ein CrC2o-Alkylrest (z.B. Methyl, Ethyl, Propyl, Butyl) oder ein C6- C24-Arylrest (z.B. Phenyl, Biphenyl, Naphthyl), der optional einen oder mehrere Reste tragen kann, z.B. aus der Gruppe Cι-C o-Alkyl (z.B. lineares oder verzweigtes C-ι-C2o-Alkyl wie sec. Butyl oder Dodecyl), welches einen oder mehrere Reste wie C6-C2o-Arylreste (z.B. Phenyl, Biphenyl, Naphthyl) tragen kann, und C6-C2o-Aryl (z.B. Phenyl, Biphenyl oder Naphthyl), welches optional einen oder mehrere Reste tragen kann wie Cι-Cι0-Alkyl (z.B. Methyl, Ethyl, Propyl, Butyl), oder R ist ein Rest R2O-(AO)w, worin w eine ganze Zahl von 1 bis 100 ist, und AO eine Alkylenoxideinheit ist, z.B. (EO)x(PO)γ(BO)z, worin EO eine Ethylenoxideinheit, PO eine Propylenoxideinheit, BO eine Butylenoxideinheit, x eine ganze Zahl von 0 - 100, y eine ganze Zahl von 0 - 100, z eine ganze Zahl von 0 bis 100 und die Summe x + y + z mindestens 1 ist, und die Alkylenoxideinheit, z.B. (EO)χ(PO)γ(BO)z, statistisch gemischt oder blockweise aufgebaut sein kann, undR 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 Cι-C -alkyl (eg linear or branched Cι-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 Cι-Cι 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) γ (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 + z is at least 1, and the alkylene oxide unit, for example (EO ) χ (PO) γ (BO) z, statistically mixed or can be built up in blocks, and
R2 ist H, ein C1-C20-Alkylrest (z.B. Methyl, Ethyl, Propyl, Butyl) oder ein C6-C24- Arylrest (z.B. Phenyl, Biphenyl, Naphthyl), der optional einen oder mehrere Reste tragen kann, z.B. aus der Gruppe CrC2o-Alkyl (z.B. lineares oder verzweigtes Cr C2o-Alkyl wie sec. Butyl oder Dodecyl), welches einen oder mehrere Reste wie CQ- C2o-Arylreste (z.B. Phenyl, Biphenyl, Naphthyl) tragen kann, und C6-C o-Aryl (z.B. Phenyl, Biphenyl, Naphthyl), welches optional einen oder mehrere Reste tragen kann wie d-do-Alky! (z.B. Methyl, Ethyl, Propyl, Butyl), oder R2 ist - O - S03 M, - SO3 M, - O - PO3H M, H oder PO3H M, vorzugsweise PO3H M, worin M gleich H oder ein Kation, insbesondere ein Metallkation wie ein Alkalimetallion oder Erdalkalimetallion, oder ein Ammoniumion ist.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. butyl or dodecyl) which carry one or more residues such as CQ-C 2 o-aryl residues (for example phenyl, biphenyl, naphthyl) can, and C 6 -C o-aryl (eg phenyl, biphenyl, naphthyl), which can optionally carry one or more radicals such as d-do-alky! (eg methyl, ethyl, propyl, butyl), or 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.
Besonders bevorzugte anionische Tenside c) sind Alkylarylsulfonate wie Dodecylbenzolsulfonate, z.B. Erdalkalidodecylbenzolsulfonate wie Calcium- dodecylbenzolsulfonate (z.B. Phenylsulfonat® Ca100 von Clariant), Alkylarylpolyglykolethersulfate und -sulfonate, insbesondere Arylalkylarylpolyglykolethersulfate wie Tristyrylphenolpolyglykolethersulfate, insbesondere die Alkali- oder Ammonium- oder Triethanolaminsalze (z.B. Soprophore®-Reihe von Rhodia), Alkylethersulfate und deren Salze (z.B. wie Genapol® LRO von Clariant), Alkylsulfate und Alkylsulfonate (z.B. wie die Hostapur® Reihe von Clariant), Alkylpolyglykoletherphosphate, insbesondere die Alkalisalze (z.B. die Rhodafac®-Reihe Rhodia), Alkylarylpolyglykoletherphosphate, insbesondere in Form der Alkalimetallsalze. Die Salze sind im allgemeinen bevorzugt Metallsalze wie Alkali- oder Erdalkalimetallsalze oder Ammonium- oder Trialkylaminsalze.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. Soprophore® series from Rhodia), alkyl ether sulfates and their salts (e.g. from Genulfonate), such as from 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.
Als nichtionische Tenside d) eignen sich beispielsweise Alkoxylate, z.B. Ethoxylate, Propoxylate oder Butoxylate und deren Kombinationen. Unter dem Begriff Alkoxylate werden Verbindungen verstanden, die Alkylenoxideinheiten enthalten, insbesondere Einheiten von C2-Cι0-Alkylenoxiden, wie Ethylenoxid, Propylenoxid oder Butylenoxid, wobei die Einheiten innerhalb des Tensids gleich oder voneinander verschieden und dabei statistisch gemischt oder blockweise angeordnet sein können. Beispiele für Alkoxylate d) sind Verbindungen der nachfolgenden Formel (II):Examples of suitable nonionic surfactants d) are alkoxylates, for example ethoxylates, propoxylates or butoxylates and their combinations. The term alkoxylates are meant compounds containing alkylene oxide units, in particular units of C2 -Cι 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. Examples of alkoxylates d) are compounds of the following formula (II):
R1-(AO)w-R2 (II)R 1 - (AO) wR 2 (II)
.worin.wherein
R1 ausgewählt ist aus der Gruppe H, HO, Cι-C3o-Alkyl, welches linear oder verzweigt sein kann, (z.B. Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl), d-C30-Alkoxy, vorzugsweise Cι-Cι0-Alkoxy, welches linear oder verzweigt sein kann (z.B. Methoxy, Ethoxy, Propoxy, Butoxy, Pentoxy, Hexoxy), C6-C24-Aryl (z.B. Phenyl), welches optional einen oder mehrere Reste tragen kann wie Cι-C3o-Arylalkyl (z.B. Styrylphenyl) oder Cι-C30-Alkyl, worin die Alkylgruppen linear oder verzweigt sein können (z.B. Butyl oder Dodecyl), C6-C24-Aryloxy (z.B. Phenoxy), welches optional einen oder mehrere Reste tragen kann wie d-C3o-Arylalkyl (z.B. Styrylphenyl), oder Cι-C30-Alkyl, worin die Alkylgruppen linear oder verzweigt sein können (z.B. Butyl oder Dodecyl), oder R1 ist ein Sorbitanesterrest, ein Glycerinesterrest, oder Cι-C3o-Alkyl-NR4, vorzugsweise Cιo-C o-Alkyl-NR4, worin die d-C2o-Alkylgruppe linear oder verzweigt sein kann (z.B. Dodecyl, Hexadecyl, Octadecyl) und worin R4 gleich H oder C1-C-10- Alkyl ist (z.B. Methyl, Ethyl, Propyl, Butyl),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-arylalkyl (eg styrylphenyl), or -CC 30 alkyl, in which the alkyl groups can be linear or branched (eg butyl or dodecyl), or R 1 is a sorbitan ester residue, a glycerol ester residue, or -C-C 3 o-alkyl-NR 4 , preferably Cιo-C o-alkyl-NR 4 , in which the dC 2 o-alkyl group can be linear or branched (for example dodecyl, hexadecyl, Octadecyl) and in which R 4 is H or C 1 -C 10 alkyl (for example methyl, ethyl, propyl, butyl),
R2 gleich H oder d-C6-AIkyl, welches linear oder verzweigt sein kann (z.B. Methyl, Ethyl, Propyl, Butyl, Pentyl oder Hexyl) ist, und w ist eine ganze Zahl von 1 bis 100, AO ist eine Alkylenoxideinheit, z.B. (EO)χ(PO)γ(BO)z, worin EO eine Ethylenoxideinheit, PO eine Propylenoxideinheit, BO eine Butylenoxideinheit, x eine ganze Zahl von 0 - 100, y eine ganze Zahl von 0 - 100, z eine ganze Zahl von 0 bis 100 und die Summe x + y + z mindestens 1 ist, und die Alkylenoxideinheit, z.B. (EO)χ(PO)γ(BO)z, statistisch gemischt oder blockweise aufgebaut ist.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) χ (PO) γ (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) χ (PO) γ (BO) z, is statistically mixed or built up in blocks.
Besonders bevorzugte nichtionische Tenside d) sind Alkylarylpolyalkoxylate, z.B. die Ethoxylate, Propoxylate und/oder Butoxylate, Arylalkylarylpolyalkoxylate wie Tristyrylphenylpolyalkoxyiate (z.B. Soprophor® Reihe von Rhodia) und Alkylphenylpolyalkoxylate wie Tributylphenylpolyalkoxlate (z.B. Sopagenat® Reihe von Clariant), Alkylenoxid-Blockcopolymere wie Ethylenoxid(EO)-Propylenoxid(PO)- Blockcopolymere oder Ethylenoxid(EO)-Butylenoxid(BO)-Blockcopolymere (z.B. Pluronic® Reihe von BASF), Polyalkylenoxide wie Polyethyenoxide, Polypropylenoxide oder Polybutylenoxide, die an einem der beiden endständigen Sauerstoffatome mit d-d∑-Kohlenwasserstoffresten, vorzugsweise C10-C22- Kohlenwasserstoffresten wie geradkettigen oder verzweigten Cιo-C22-Alkylresten (z.B. Decyl, Dodecyl, Tetradecyl, Hexadecyl) substituiert sein können, z.B. Polyglykolether, die isotridecylsubstituiert sein können (z.B. Genapol®-Reihen von Clariant), alkoxylierte wie ethoxylierte Öle wie Pflanzenöle, z.B. alkoxyliertes wie ethoxyliertes Rhizinusöl (Emulsogen® Reihe Clariant), alkoxylierte wie ethoxylierte (C10-C22)-Fettamine (z.B. Genamin®Reihe von Clariant).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 Cιo-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).
Soweit in dieser Beschreibung kohlenstoffhaltige Reste genannt werden wie Alkyl, Alkoxy, Haloalkyl, Haloalkoxy, Alkylamino und Alkylthio sowie die entsprechenden ungesättigten und/oder substituierten Reste, können diese im Kohlenstoffgerüst jeweils geradkettig oder verzweigt sein. Wenn nicht speziell angegeben, weisen diese Reste im allgemeinen 1 bis 30 C-Atome auf, wobei die niederen Kohlenstoffgerüste, z.B. mit 1 bis 6 C-Atomen bzw. bei ungesättigten Gruppen mit 2 bis 6 C-Atomen, bevorzugt sind. Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw., bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder sec-Butyl, Pentyle, Hexyle, wie n-Hexyl, i-Hexyl und 1 ,3-Dimethylbutyl, Heptyle, wie n-Heptyl, 1 -Methylhexyl und 1 ,4-Dimethylpentyl; Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten Reste; Alkenyl bedeutet z.B. 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 und 1-Methyl-but-2-en-1-yl; Alkinyl bedeutet z.B. Propargyl, But-2-in-1-yl, But-3-in-1-yl, 1-Methyl-but-3-in-1-yl.To the extent that carbon-containing radicals are mentioned in this description, such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals, these 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-en-1-yl; Alkynyl means, for example, propargyl, but-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.
Alkenyl in der Form (C3-C4)Alkenyl, (C3-C5)Alkenyl, (C3-C6)Alkenyl, (C3-C8)Alkenyl oder (C3-Ci2)-Alkenyl bedeutet vorzugsweise einen Alkenylrest mit 3 bis 4, 3 bis 5, 3 bis 6, 3 bis 8 bzw. 3 bis 12 C-Atomen, bei dem die Doppelbindung nicht an dem C-Atom liegt, das mit dem übrigen Molekülteil der Verbindung der Formel (I) verbunden ist ("yl"-Position). Entsprechendes gilt für (C3-C )Alkinyl etc., (C3- C )Alkenyloxy etc. und (C3-C4)Alkinyloxy etc.Alkenyl in the form of (C 3 -C 4 ) alkenyl, (C 3 -C 5 ) alkenyl, (C 3 -C 6 ) alkenyl, (C 3 -C 8 ) alkenyl or (C 3 -Ci 2 ) alkenyl preferably an alkenyl radical having 3 to 4, 3 to 5, 3 to 6, 3 to 8 or 3 to 12 carbon atoms, in which the double bond is not due to the carbon atom which is associated with the rest of the molecular part of the compound of the formula ( I) is connected ("yl" position). The same applies to (C 3 -C) alkynyl etc., (C 3 - C) alkenyloxy, etc., and (C 3 -C 4) alkynyloxy etc.
Ein Kohlenwasserstoffrest bedeutet ein geradkettiger, verzweigter oder cyclischer und gesättigter oder ungesättigter aliphatischer oder aromatischer Kohlenwasserstoffrest, z.B. Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl oder Aryl. Ein Kohlen wasserstoffrest weist bevorzugt 1 bis 40 C-Atome, vorzugsweise 1 bis 30 C-Atome auf; besonders bevorzugt bedeutet ein Kohlenwasserstoffrest Alkyl, Alkenyl oder Alkinyl mit bis zu 12 C-Atomen oder Cycloalkyl mit 3, 4, 5, 6 oder 7 Ringatomen oder Phenyl.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 bedeutet ein mono-, bi- oder polycyclisches aromatisches System, beispielsweise Phenyl, Naphthyl, Tetrahydronaphthyl, Indenyl, Indanyl, Pentalenyl, Fluorenyl und ähnliches, vorzugsweise Phenyl. Ein heterocyclischer Rest oder Ring (Heterocyclyl) kann gesättigt, ungesättigt oder heteroaromatisch und unsubstituiert oder substituiert sein; er enthält vorzugsweise ein oder mehrere Heteroatome im Ring, vorzugsweise aus der Gruppe N, O und S; vorzugsweise ist er ein aliphatischer Heterocyclyl rest mit 3 bis 7 Ringatomen oder ein heteroaromatischer Rest mit 5 oder 6 Ringatomen und enthält 1 , 2 oder 3 Heteroatome. Der heterocyclische Rest kann z.B. ein heteroaromatischer Rest oder Ring (Heteroaryl) sein, wie z.B. ein mono-, bi- oder polycyclisches aromatisches System, in dem mindestens 1 Ring ein oder mehrere Heteroatome enthält, beispielsweise Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, Triazinyl, Thienyl, Thiazolyl, Oxazolyl, Furyl, Pyrrolyl, Pyrazolyl und Imidazolyl, oder ist ein partiell oder vollständig hydrierter Rest wie Oxiranyl, Oxetanyl, Pyrrolidyl, Piperidyl, Piperazinyl, Dioxolanyl, Morpholinyl, Tetrahydrofuryl. Als Substituenten für einen substituierten heterocyclischen Rest kommen die weiter unten genannten Substituenten in Frage, zusätzlich auch Oxo. Die Oxogruppe kann auch an den Heteroringatomen, die in verschiedenen Oxidationsstufen existieren können, z.B. bei N und S, auftreten.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 (heterocyclyl) 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. 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 bedeutet beispielsweise Fluor, Chlor, Brom oder lod. Haloalkyl, -alkenyl und -alkinyl bedeuten durch Halogen, vorzugsweise durch Fluor, Chlor und/oder Brom, insbesondere durch Fluor oder Chlor, teilweise oder vollständig substituiertes Alkyl, Alkenyl bzw. Alkinyl, z.B. CF3, CHF2, CH2F, CF3CF2, CH2FCHCI, CCI3, CHCI2, CH2CH2CI; Haloalkoxy ist z.B. OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 und OCH2CH2CI; entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierte Reste.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.
Kohlenwasserstoffreste, z.B. Alkyl, Alkenyl, Alkinyl, Aryl, Phenyl und Benzyl, oder Heterocyclyl oder Heteroaryl, können substituiert sein, wobei die Substituenten beispielsweise einen oder mehrere, vorzugsweise 1 , 2 oder 3 Reste aus der Gruppe Halogen, Alkoxy, Haloalkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy, Cyano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyl, Mono- und Dialkylaminocarbonyl, substituiertes Amino, wie Acylamino, Mono- und Dialkylamino, und Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl und, im Falle cyclischer Reste, auch Alkyl und Haloalkyl sowie den genannten gesättigten kohlenwasserstoffhaltigen Resten entsprechende ungesättigte aliphatische Reste, wie Alkenyl, Alkinyl, Alkenyloxy, Alkinyloxy etc. bedeuten. Bei Resten mit C-Atomen sind solche mit 1 bis 4 C-Atomen, insbesondere 1 oder 2 C-Atomen, bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, (Cι-C4)Alkyl, vorzugsweise Methyl oder Ethyl, (Cι-C )Haloalkyl, vorzugsweise Trifluormethyl, (Cι-C4)Alkoxy, vorzugsweise Methoxy oder Ethoxy, (Cι-C )Haloalkoxy, Nitro und Cyano. Besonders bevorzugt sind dabei die Substituenten Methyl, Methoxy und Chlor.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 corresponding unsaturated aliphatic radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. In the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. As a rule, 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.
Gegebenenfalls substituiertes Phenyl ist vorzugsweise Phenyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach durch gleiche oder verschiedene Reste aus der Gruppe Halogen, (d-C4)Alkyl, (Cι-C )Alkoxy, (d-C4)Halogenalkyl, (d-C4)Halogenalkoxy und Nitro substituiert ist, z.B. o-, m- und p-Tolyl, Dimethylphenyle, 2-, 3- und 4-Chlorphenyl, 2-, 3- und 4-Trifluor- und -Trichlorphenyl, 2,4-, 3,5-, 2,5- und 2,3-Dichlorphenyl, o-, m- und p-Methoxyphenyl.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.
Ein Acylrest bedeutet den Rest einer organischen Säure, der formal durch Abspaltung einer OH-Gruppe aus der organischen Säure entsteht, z.B. der Rest einer Carbonsäure und Reste davon abgeleiteter Säuren wie der Thiocarbonsäure, gegebenenfalls N-substituierten Iminocarbonsäuren oder die Reste von Kohlensäuremonoestern, gegebenenfalls N-substituierter Carbaminsäuren, Sulfonsäuren, Sulfinsäuren, Phosphonsäuren, Phosphinsäuren.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.
Ein Acylrest ist bevorzugt Formyl oder aliphatisches Acyl aus der Gruppe CO-Rx, CS-RX, CO-ORx, CS-ORx, CS-SRX, SORγ oder SO2Rγ, wobei Rx und Rγ jeweils einen Cι-C3o-Kohlenwasserstoffrest bedeutet, der unsubstituiert oder substituiert ist, oder Aminocarbonyl oder Aminosulfonyl, wobei die beiden letztgenannten Reste unsubstituiert, N-monosubstituiert oder N,N-disubstituiert sind. Acyl bedeutet beispielsweise Formyl, Halogenalkylcarbonyl, Alkylcarbonyl wie (Cι-C )Alkylcarbonyl, Phenylcarbonyl, wobei der Phenylring substituiert sein kann, z.B. wie oben für Phenyl angegeben, oder Alkyloxycarbonyl, Phenyloxycarbonyl, Benzyloxycarbonyl, Alkylsulfonyl, Alkylsulfinyl, N-Alkyl-1-iminoalkyl und andere Reste von organischen Säuren.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 γ or SO 2 R γ , where R x and R γ 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.
Von Formel (I) und den anderen in dieser Beschreibung genannten Verbindungen sind auch alle Stereoisomeren und deren Gemische umfaßt. Solche Verbindungen der enthalten ein oder mehrere asymmetrische C-Atome oder auch Doppelbindungen, die in der allgemeinen Formel nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind alle von den jeweiligen Formeln umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.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.
Die Herstellung der erfindungsgemäßen Mikroemulsionskonzentrate kann durch übliche Verfahren erfolgen, z.B. Mischen durch Lösen oder Emulgieren der Einzelkomponenten, bevorzugt bei Raumtemperatur. Sofern weitere Hilfs- und Zusatzstoffe enthalten sind, werden diese ebenfalls bevorzugt bei Raumtemperatur eingetragen. Die Zugabereihenfolge der Einzelkomponenten ist dabei im allgemeinen beliebig.The 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.
Die Herstellprozesse sind im Prinzip bekannt und beispielsweise beschrieben in Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London; H. Mollet, A. Grubenmann, "Formulierungstechnik", Wiley-VCH, Weinheim 2000.The manufacturing processes are known in principle and are described, for example, in Winnacker-Küchler, "Chemical Technology", volume 7, C. Hauser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London; H. Mollet, A. Grubenmann, "Formulation Technology", Wiley-VCH, Weinheim 2000.
Die Formulierungshilfsstoffe wie Inertmaterialien und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvente Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Athylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The formulation 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. Inc., NY 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit von Komponente a) verschiedenen agrochemischen Wirkstoffen, wie Herbiziden, Fungiziden, Insektiziden, Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix.Based on these formulations, 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.
Die erfindungsgemäßen Mikroemulsionskonzentrate lassen sich mit Wasser zu Mikroemulsionen verdünnen, die ebenfalls Gegenstand der vorliegenden Erfindung sind. Dabei kann das Gewichtsverhältnis Mikroemulsionskonzentrat : Wasser beispielsweise 1 :0,1 bis 1 :100, vorzugsweise 1 :1 bis 1 :100 betragen, was zu konzentrierten Mikroemulsionen führt, die als solche lagerstabil sind. Diese können für Applikationszwecke mit Wasser weiter zu Spritzbrühen verdünnt werden, die im allgemeinen in Form von Emulsionen wie Mikroemulsionen, wäßrigen Lösungen, Suspensionen oder Suspoemulsionen vorliegen.The 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. For application purposes, 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.
Die Komponenten a), b), c) und d) der erfindungsgemäßen Mikroemulsionskonzentrate und Mikroemulsionen können zusammen in einer Fertigformulierung enthalten sein, die dann in üblicherweise, z.B. im Form einer Spritzbrühe appliziert werden kann.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.
Die erfindungsgemäßen Mikroemulsionskonzentrate und Mikroemulsionen einschließlich der daraus erhältlichen Spritzbrühen (nachstehend gemeinsam als erfindungsgemäße agrochemische Mittel bezeichnet) können neben den Komponenten a), b), c) und d) als weitere Komponente noch übliche Hilfs- und Zusatzstoffe enthalten, z.B. Formulierungshilfsstoffe wie Anti-Driftagentien, Stoffe zur Beeinflussung der Feuchtigkeit (Humectants), Dünger wie Ammoniumsulfat, Harnstoff oder Mehrkomponenten-Dünger z.B. auf Phosphor-, Kalium- und Stickstoffbasis wie P,K,N-Dünger, oder handelsübliche von Komponenten c) und d) verschiedene Tenside wie betainische oder polymere Tenside, Stabilisatoren wie pH-Stabilisatoren, Bioeide, UV-Stabilisatoren, Entschäumer, synthetische oder natürliche Polymere, Lösemittel, z.B. polare Lösungsmittel wie Wasser oder unpolare Lösemittel wie gesättigte oder ungesättigte aliphatische Lösemittel, die verzweigt oder unverzweigt sein können, oder aromatische Lösemittel, wie Solvesso® 100, Solvesso® 150 oder Solvesso® 200 oder Xylol. Diese agrochemischen Mittel sowie deren Herstellung und Anwendung sind ebenfalls neu und Gegenstand dieser Erfindung.The microemulsion concentrates and microemulsions according to the invention, including the spray liquors obtainable therefrom (hereinafter collectively referred to as agrochemical compositions according to the invention), in addition to components a), b), c) and d), 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 Solvesso® 100, Solvesso® 150 or Solvesso® 200 or xylene. These agrochemical compositions, as well as their production and use, are also new and the subject of this invention.
Bevorzugte Beispiele für übliche Hilfs- und Zusatzstoffe sindPreferred examples of customary auxiliaries and additives are
• Netzmittel wie Genapol® LRO (0-20 Gew.-%), Dispergiermittel wie Tamol® (0-15 Gew.-%) oder weitere Tenside (nichtionische, kationische, anionische, polymere Tenside) (0-30 Gew.-%);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) );
• Anorganische Salze wie NaCI, Na2SO4, MgC (0-50 Gew.-%), (oligo-; poly-)- Phosphate; Carbonate wie Kaliumcarbonat;• Inorganic salts such as NaCl, Na 2 SO 4 , MgC (0-50% by weight), (oligo-; poly -) - phosphates; Carbonates such as potassium carbonate;
• Dünger wie Ammoniumsulfat, Ammoniumnitrat, Harnstoff, Phosphor- und Kalium- haltige Komponenten, gegebenenfalls weitere Spurenelemente (0-60 Gew.-%);• fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus and potassium-containing components, optionally further trace elements (0-60% by weight);
• Entschäumer wie Fluowet® PP (0-2 Gew.-%);• defoamers such as Fluowet ® PP (0-2% by weight);
• Bindemittel wie geeignete natürliche oder synthetische Stoffe wie Polyaminosäuren, Polyvinylalkohole, Polyvinylpyrrolidon, Polyacrylsäure- Derivate, (0-15 Gew.-%); oderBinders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinyl pyrrolidone, polyacrylic acid derivatives, (0-15% by weight); or
• Lösemittel wie Wasser oder organische Solventien (0-15 Gew.-%).• Solvents such as water or organic solvents (0-15% by weight).
Der Einsatz der erfindungsgemäßen agrochemischen Mittel kann z.B. geschehen durch Applikation auf die Schadorgansimen oder die Orte, an denen sie auftreten, z.B. durch Spritzung. Die erfindungsgemäßen agrochemischen Mittel werden in der Regel in Form einer Spritzbrühe ausgebracht, welche die Komponenten a), b), c) und d) in wirksamen Mengen und gegebenenfalls weitere für die übliche Hilfs-und Zusatzstoffe, z.B. für die Formulierung oder Anwendung enthält. Die Spritzbrühe wird im allgemeinen auf Basis von Wasser hergestellt, wobei übliche Hilfs- und Zusatzstoffe z.B. Öle, wie Pflanzenöle oder hochsiedende Kohlenwasserstoffe wie Kerosin oder Paraffin zugesetzt werden können. Bei der Applikation ist die Konzentration an agrochemischem Wirkstoff a) im allgemeinen bei 10"6 bis 0 Gew.-%, vorzugsweise bei 10"5 bis 4 Gew.-% in dem applizierten Mittel, z.B. der Spritzbrühe, bei einer Aufwandmenge von 1 bis 5000 l/ha, vorzugsweise 50 bis 1000 l/ha.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. When applied, 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 ,
Zur Anwendung werden in handelsüblicher Form vorliegende konzentrierte Formulierungen gegebenenfalls in üblicherweise verdünnt, z.B. mittels Wasser. Es kann vorteilhaft sein, den Spritzbrühen weitere Mengen an Komponenten b), c) und d) und/oder andere zur Anwendung übliche Hilfs- und Zusatzstoffe, insbesondere selbstemulgierende Öle oder Paraffinöle zuzugeben. Auch können zusätzliche Komponenten a) zugegeben werden oder andere von Komponente a) verschiedene agrochemische Wirkstoffe.For use, 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.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, Art des verwendeten Herbizids, kann die erforderliche Aufwandmenge der agrochemischen Wirkstoffe a) variieren. Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,001 und 10 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie zwischen 0,005 und 5 kg/ha.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.
Die erfindungsgemäßen agrochemischen Mittel, sind bevorzugt herbizide Mittel. Diese weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler Schadpflanzen auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden gut erfaßt. Dabei können die Mittel z.B. im Vorsaat-, Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen herbiziden Mittel kontrolliert werden können, ohne daß durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.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. In particular, 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.
Auf der Seite der monokotylen Unkrautarten werden z.B. Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. sowie Bromus spp. wie Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum und Bromus japonicus und Cyperusarten aus der annuellen Gruppe und auf Seiten der perennierenden Spezies Agropyron, Cynodon, Imperata sowie Sorghum und auch ausdauernde Cyperusarten gut erfaßt.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. 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.
Bei dikotylen Unkrautarten erstreckt sich das Wirkungsspektrum auf Arten wie z.B. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. wie Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp.,Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. und Viola spp., Xanthium spp., auf der annuellen Seite sowie Convolvulus, Cirsium, Rumex und Artemisia bei den perennierenden Unkräutern.With dicotyledon weed species, 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.
Unter den spezifischen Kulturbedingungen im Reis vorkommende Schadpflanzen wie z.B. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus und Cyperus werden von den erfindungsgemäßen Mitteln ebenfalls hervorragend bekämpft.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.
Werden die erfindungsgemäßen herbiziden Mittel vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.If the 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.
Bei Applikation der erfindungsgemäßen herbiziden Mittel auf die grünen Pflanzenteile im Nachauflaufverfahren tritt ebenfalls sehr rasch nach der Behandlung ein drastischer Wachstumsstop ein und die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so daß auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird.When the herbicidal compositions according to the invention are applied to the green parts of the plant in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage present at the time of application or die completely after a certain time, so that one for harmful crop competition is eliminated very early and sustainably.
Die erfindungsgemäßen herbiziden Mittel zeichnen sich durch eine schnell einsetzende und lang andauernde herbizide Wirkung aus. Die Regenfestigkeit der Wirkstoffe in den erfindungsgemäßen Kombinationen ist in der Regel günstig. Als besonderer Vorteil fällt ins Gewicht, daß die in den herbizide Mitteln verwendeten und wirksamen Dosierungen von herbiziden Verbindungen so gering eingestellt werden können, daß ihre Bodenwirkung optimal niedrig ist. Somit wird deren Einsatz nicht nur in empfindlichen Kulturen erst möglich, sondern Grundwasser- Kontaminationen werden praktisch vermieden. Durch die erfindungsgemäßen Kombination von Wirkstoffen wird eine erhebliche Reduzierung der nötigen Aufwandmenge der Wirkstoffe ermöglicht.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.
Die genannten Eigenschaften und Vorteile sind in der praktischen Unkrautbekämpfung von Nutzen, um landwirtschaftliche Kulturen von unerwünschten Konkurrenzpflanzen freizuhalten und damit die Erträge qualitativ und quantitativ zu sichern und/oder zu erhöhen. Der technische Standard wird durch diese neuen Mittel hinsichtlich der beschriebenen Eigenschaften deutlich übertroffen.The properties and advantages mentioned are useful in practical weed control in order to keep agricultural crops free of undesired competing plants and thus to ensure and / or increase the yields qualitatively and quantitatively. These new means significantly exceed the technical standard in terms of the properties described.
Obgleich die erfindungsgemäßen herbiziden Mittel eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. zweikeimblättriger Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben, oder Gramineen-Kulturen wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis oder Mais, nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Nutzpflanzungen oder in Zierpflanzungen.Although the 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. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
Darüber hinaus weisen die erfindungsgemäßen herbiziden Mittel hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da das Lagern hierdurch verringert oder völlig verhindert werden kann. Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die erfindungsgemäßen herbiziden Mittel auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z. B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt.In addition, 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.
Die Anwendung der erfindungsgemäßen herbiziden Mittel kann auch in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen erfolgen, z. B. von Gramineen-Kulturen wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten. Vorzugsweise können die erfindungsgemäßen Mittel als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind.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.
Bei der Anwendung der erfindungsgemäßen herbiziden Mittel in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen. Gegenstand der vorliegenden Erfindung ist weiterhin auch ein Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, vorzugsweise in Pflanzenkulturen wie Getreide (z.B. Weizen, Gerste, Roggen, Hafer, Reis, Mais, Hirse), Zuckerrübe, Zuckerrohr, Raps, Baumwolle und Soja, besonders bevorzugt in monokotylen Kulturen wie Getreide, z.B. Weizen, Gerste, Roggen, Hafer, Kreuzungen davon wie Triticale, Reis, Mais und Hirse, wobei man das erfindungsgemäße herbizide Mittel auf die Schadpflanzen, Pflanzenteile, Pflanzensamen oder die Fläche auf der die Pflanzen wachsen, z.B. die Anbaufläche appliziert, z.B. im Vorauflauf, Nachauflauf oder im Vor- und Nachauflauf, vorzugsweise im Vorauflauf.When 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.
Die Pflanzen kulturen können auch gentechnisch verändert oder durch Mutationsselektion erhalten sein und sind bevorzugt tolerant gegenüber Acetolactatsynthase (ALS)-Inhibitoren.The plant cultures can also be genetically modified or obtained by mutation selection and are preferably tolerant of acetolactate synthase (ALS) inhibitors.
Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen herbiziden Mittel zur Bekämpfung von Schadpflanzen, vorzugsweise in Pflanzenkulturen. Eine bevorzugte Verwendung betrifft den Einsatz von herbiziden Mitteln, die synergistische Mengen an Komponenten a), b), c) und d) enthalten.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).
Die erfindungsgemäßen herbiziden Mittel können auch nicht-selektiv zur Bekämpfung unerwünschten Pflanzenwuchses eingesetzt werden, z.B. in Plantagenkulturen, an Wegrändern, Plätzen, Industrieanlagen oder Eisenbahnanlagen.The 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.
Die erfindungsgemäßen agrochemischen Mittel, insbesondere herbiziden Mittel, können gegebenenfalls als Mischformulierungen mit weiteren agrochemischen Wirkstoffen und üblichen Hilfs- und Zusatzstoffen vorliegen, die dann in üblicher Weise mit Wasser verdünnt zur Anwendung gebracht werden, oder als sogenannte Tankmischungen durch gemeinsame Verdünnung der getrennt formulierten oder partiell getrennt formulierten Komponenten mit Wasser hergestellt werden.The 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.
Aufgrund der relativ geringen Aufwandmenge der erfindungsgemäßen herbiziden Mittel ist deren Verträglichkeit im allgemeinen sehr gut. Insbesondere wird durch die erfindungsgemäßen Kombinationen eine Senkung der absoluten Aufwandmenge erreicht, verglichen mit der Einzelanwendung eines herbiziden Wirkstoffs.Because of the relatively low application rate of the herbicides according to the invention Their tolerance is generally very good. In particular, the combinations according to the invention achieve a reduction in the absolute application rate compared to the single application of a herbicidal active ingredient.
Gegenstand der Erfindung ist deshalb auch ein Verfahren zur selektiven Bekämpfung von Schadpflanzen in Pflanzenkulturen, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge der genannten Herbizide a) in Kombination mit den Komponenten b), c) und d) appliziert, z.B. im Vorauflauf, Nachauflauf oder im Vor- und Nachauflauf, vorzugsweise im Vorauflauf, auf die Pflanzen, Pflanzenteile, Pflanzensamen oder die Fläche auf der die Pflanzen wachsen, z.B. die Anbaufläche.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.
In bevorzugter Verfahrensvariante werden die Herbizide a) in Aufwandmengen von 0,1 bis 2.000 g Aktivsubstanz/ha, bevorzugt von 0,5 bis 1.000 g Aktivsubstanz/ha, ausgebracht. Weiterhin besonders bevorzugt ist die Ausbringung der Wirkstoffe in Form einer Co-Formulierung oder in Form von Tankmischungen, wobei die Einzelkomponenten, z.B. in Form von Formulierungen, gemeinsam im Tank mit Wasser gemischt werden und die erhaltene Spritzbrühe ausgebracht wird.In a preferred process variant, 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.
Da die Kulturpflanzenverträglichkeit der erfindungsgemäßen Kombinationen bei gleichzeitig sehr hoher Kontrolle der Schadpflanzen ausgesprochen gut ist, können diese als selektiv angesehen werden. In bevorzugter Verfahrensabwandlung werden herbizide Mittel mit den erfindungsgemäßen Wirkstoffkombinationen daher zur selektiven Bekämpfung unerwünschter Pflanzen eingesetzt.Since the crop plant tolerance of the combinations according to the invention is extremely good with very high control of the harmful plants at the same time, these can be regarded as selective. In a preferred modification of the process, herbicidal compositions with the active compound combinations according to the invention are therefore used for the selective control of undesired plants.
Um die Verträglichkeit und/oder Selektivität der erfindungsgemäßen herbiziden Mittel gewünschtenfalls noch zu steigern kann es von Vorteil sein, diese gemeinsam in Mischung oder zeitlich - getrennt nacheinander zusammen mit Safenern oder Antidots anzuwenden.In order to further increase the tolerance and / or selectivity of the herbicidal compositions according to the invention, if desired, it can be advantageous to use them together in a mixture or in succession - separately in succession together with safeners or antidotes.
Als Safener oder Antidots für die erfindungsgemäßen herbiziden Mittel in Frage kommende Verbindungen sind z. B. aus EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A-4,891,057), EP-A-346 620 (AU-A-89/34951) und den internationalen Patentanmeldungen PCT/EP 90/01966 (WO-91108202) und PCT/EP 90102020 (WO-911078474) und dort zitierter Literatur bekannt oder können nach den dort beschriebenen Verfahren hergestellt werden. Weitere geeignete Safener kennt man aus EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4, 881 ,966) und EP-A-0 492 366 und der dort zitierten Literatur.Compounds suitable as safeners or antidots for the herbicidal compositions according to the invention are, for. B. from EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A-4,891,057), EP-A-346 620 (AU-A-89/34951) and the international patent applications PCT / EP 90/01966 (WO-91108202) and PCT / EP 90102020 (WO-911078474) and the literature cited therein, or can be prepared by the processes described therein. Other suitable safeners are known from EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4, 881, 966) and EP-A-0 492 366 and the literature cited therein ,
In einer bevorzugten Ausführungsform enthalten die herbiziden Mittel der vorliegenden Erfindung daher einen zusätzlichen Gehalt an einer oder mehrerer Verbindungen, die als Safener oder Antidots wirken.In a preferred embodiment, the herbicidal compositions of the present invention therefore contain an additional content of one or more compounds which act as safeners or antidotes.
Besonders bevorzugte Antidots oder Safener oder Gruppen von Verbindungen die sich als Safener oder Antidots für die oben beschriebenen herbiziden Mittel der Erfindung eignen sind unter anderem:Particularly preferred antidotes or safeners or groups of compounds which are suitable as safeners or antidots for the herbicidal compositions of the invention described above include:
a) Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure, vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)- 5-methyl-2-pyrazolin-3-carbonsäureethylester (Verbindung S1 -1 , Mefenpyr- diethyl) und verwandte Verbindungen, wie sie in der internationalen Anmeldung WO 91/07874 (PCT/EP 90102020) beschrieben sind;a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (compound S1-1, mefenpyr- diethyl) and related compounds as described in international application WO 91/07874 (PCT / EP 90102020);
b) Derivate der Dichlorphenylpyrazolcarbonsäure, vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäureethylester (Verbindung S1-2), 1-(2,4-Dichlorphenyl)-5-isopropyl-pyrazol-3- carbonsäureethylester (Verbindung S1 -3),b) Derivatives of 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),
1-(2,4-Dichlorphenyl)-5-(1,1-dimethyl-ethyl)pyrazol-3-carbonsäureethylester (Verbindung S1-4), 1-(2,4-Dichlorphenyl)-5-phenyl- pyrazol-3-carbonsäureethylester (Verbindung S1-5) und verwandte Verbindungen, wie sie in EP-A-0 333 131 und EP-A-0 269 806 beschrieben sind;1- (2,4-dichlorophenyl) -5- (1,1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (compound S1-4), 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3 -carboxylic acid ethyl ester (compound S1-5) and related compounds as described in EP-A-0 333 131 and EP-A-0 269 806;
c) Verbindungen vom Typ der Triazolcarbonsäuren, vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-trichlormethyl-(1 H)-1 ,2,4-triazol-3- carbonsäureethylester (Verbindung S1-6, Fenchlorazol) und verwandte Verbindungen (siehe EP-A-0 174 562 und EP-A-0 346 620);c) Compounds of the triazole carboxylic acid type, preferably compounds such as 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (compound S1-6, fenchlorazole) and relative Compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Verbindungen vom Typ der Dichlorbenzyl-2-isoxazolin-3-carbonsäure, Verbindungen vom Typ der 5-Benzyl- oder 5-PhenyI-2-isoxazolin-3- carbonsäure, vorzugsweise Verbindungen wied) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type, compounds of the 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid type, preferably compounds such as
5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (Verbindung S1 -7) oder 5-Phenyl-2-isoxazolin-3-carbonsäureethylester (Verbindung S1-8) und verwandte Verbindungen wie sie in der internationalen Patentanmeldung WO 91/08202 (PCT/EP 90/01966) beschrieben sind;Ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (compound S1 -7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (compound S1-8) and related compounds as described in the international patent application WO 91/08202 (PCT / EP 90/01966) are described;
e) Verbindungen vom Typ der 8-Chinolinoxyessigsäure, vorzugsweise Verbindungen wie (5-Chlor-8-chinolinoxy)-essigsäure-(1 -methyl-hex-1-yl)- ester (S2-1; Cloquintocet-mexyl),e) compounds of the 8-quinolinoxyacetic acid type, preferably compounds such as (5-chloro-8-quinolinoxy) acetic acid (1-methyl-hex-1-yl) ester (S2-1; cloquintocet-mexyl),
(5-Chlor-8-chinolinoxy)-essigsäure-(1 ,3-dimethyl-but-1-yl)- ester (S2-2), (5-Chlor-8-chinolinoxy)-essigsäure-4-allyl-oxy-butylester (S2-3), (5-Chlor-8-chinolinoxy)-essigsäure-1 -allyl-oxy-prop-2-ylester (S2-4), (5-Chlor-8-chinolinoxy)-essigsäureethylester (S2-5), (5-Chlor-8-chinolinoxy)-essigsäuremethylester (S2-6), (5-Chlor-8-chinolinoxy)-essigsäureallylester (S2-7), (5-Chlor-8-chinolinoxy)-essigsäure-2-(2-propyliden-iminoxy)-1-ethylester (S2-8), (5-Chlor-8-chinolinoxy)-essigsäure-2-oxo-prop-1 -ylester (S2-9) und verwandte Verbindungen wie sie in EP-A-0 086 750, EP-A-0 094 349 und EP-A-0 191 736 oder EP-A-0 492 366 beschrieben sind;(5-Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid-4-allyl-oxy -butyl ester (S2-3), (5-chloro-8-quinolinoxy) -acetic acid-1-allyl-oxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) -acetic acid ethyl ester (S2 -5), (5-chloro-8-quinolinoxy) -acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy) -acetic acid allyl ester (S2-7), (5-chloro-8-quinolinoxy) -acetic acid- 2- (2-propylidene-iminoxy) -1-ethyl ester (S2-8), (5-chloro-8-quinolinoxy) acetic acid-2-oxo-prop-1-ethyl ester (S2-9) and related compounds like them in EP-A-0 086 750, EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366;
f) Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)-malonsäure, vorzugsweise Verbindungen wie (5-Chlor-8-chinolinoxy)-malonsäurediethylester, (5-Chlor-8- chinolinoxy)-malonsäurediallylester, (5-Chlor-8-chinolinoxy)- malonsäuremethylethylester und verwandte Verbindungen wie sie in der deutschen Patentanmeldung EP-A-0 582 198 beschrieben und vorgeschlagen worden sind;f) Compounds of the (5-chloro-8-quinolinoxy) malonic acid type, preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester, (5-chloro 8-quinolinoxy) methyl malonate and related compounds as described and proposed in German patent application EP-A-0 582 198;
g) Wirkstoffe vom Typ der Phenoxyessig- bzw. -propionsäurederivate bzw. der aromatischen Carbonsäuren, wie z. B. 2,4-Dichlorphenoxyessigsäure(ester) (2,4-D), 4-Chlor-2-methyl-phenoxy-propionsäure (Mecoprop), MCPA oder 3,6-Dichlor-2-methoxy-benzoesäure(ester) (Dicamba).g) Active substances of the phenoxyacetic or propionic acid derivative type or aromatic carboxylic acids, such as. B. 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methyl-phenoxypropionic acid (mecoprop), MCPA or 3,6-dichloro-2-methoxy-benzoic acid (ester) ( dicamba).
h) Verbindungen vom Typ der 5,5-Diphenyl-2-isoxazoIin-3-carbonsäure, vorzugsweise 5,5-Diphenyl-2-isoxazolin-3-carbonsäureethylester (S3-1 , Isoxadifen-ethyl).h) Compounds of the type of 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S3-1, isoxadifen-ethyl).
i) Verbindungen, die als Safener z.B. für Reis bekannt sind wie Fenclorim (= 4,6-Dichlor-2-phenylpyrimidin, Pesticide Manual, 11. Auflage, 1997, S. 511-512), Dimepiperate (= Piperidin-1 -thiocarbonsäure-S-1 -methyl-1 -phenylethylester, Pesticide Manual, 11. Auflage, 1997, S. 404-405), Daimuron (= 1 -(1 -Methyl- 1-phenylethyl)-3-p-tolyl-harnstoff, Pesticide Manual, 11. Auflage, 1997, S. 330), Cumyluron (= 3-(2-ChlorphenylmethyI)-1 -(1 -methyl-1 -phenyl-ethyl)- harnstoff, JP-A-60/087254), Methoxyphenon (= 3,3'-Dimethyl-4-methoxy- benzophenon, CSB (= 1-Brom-4-(chlormethylsulfonyl)-benzol, CAS-Reg. Nr. 54091-06-4).i) compounds which, as safeners, e.g. known for rice are fenclorim (= 4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512), dimepiperate (= piperidine-1-thiocarboxylic acid-S-1-methyl-1 -phenylethyl ester, Pesticide Manual, 11th edition, 1997, pp. 404-405), Daimuron (= 1 - (1-methyl-1-phenylethyl) -3-p-tolylurea, Pesticide Manual, 11th edition, 1997 , P. 330), cumyluron (= 3- (2-chlorophenylmethyl) -1 - (1-methyl-1-phenyl-ethyl) - urea, JP-A-60/087254), methoxyphenone (= 3,3'- Dimethyl-4-methoxybenzophenone, COD (= 1-bromo-4- (chloromethylsulfonyl) benzene, CAS Reg. No. 54091-06-4).
Die genannten Verbindungen sind außerdem zumindest teilweise in der EP-A-0 640 587 beschrieben, auf die hiermit zu Offenbarungszwecken Bezug genommen wird.The compounds mentioned are also at least partially described in EP-A-0 640 587, to which reference is hereby made for the purposes of disclosure.
j) Weitere wichtige Gruppen von als Safenern und Antidoten geeignetenj) Other important groups of safeners and antidotes
Verbindungen sind aus der WO 95/07897 und der WO 99/16744 bekannt.Compounds are known from WO 95/07897 and WO 99/16744.
Die Safener (Antidote) der vorstehenden Gruppen a) bis j) reduzieren oder unterbinden phytotoxische Effekte, die beim Einsatz der herbiziden Mittel gemäß der Erfindung in Nutzpflanzenkulturen auftreten können, ohne die Wirksamkeit der Herbizide gegen Schadpflanzen zu beeinträchtigen. Hierdurch kann das Einsatzgebiet der erfindungsgemäßen herbiziden Mittel erheblich erweitert werden und insbesondere ist durch die Verwendung von Safenern der Einsatz von herbiziden Mitteln möglich, die bislang nur beschränkt oder mit nicht ausreichendem Erfolg eingesetzt werden konnten, d. h. von Kombinationen, die ohne Safener in niedrigen Dosierungen mit wenig Breitenwirkung zu nicht ausreichender Kontrolle der Schadpflanzen führten.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. As a result, 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.
Die Komponenten a), b), c) und d) der herbiziden Mittel gemäß der Erfindung und die erwähnten Safener können zusammen (z.B. als fertige Formulierung oder im Tankmisch-Verfahren) oder in beliebiger Reihenfolge nacheinander ausgebracht werden. Das Gewichtsverhältnis Safener: Herbizid kann innerhalb weiter Grenzen variieren und liegt vorzugsweise im Bereich von 1 : 100 bis 100 : 1 , insbesondere von 1 : 100 bis 50: 1. Die jeweils optimalen Mengen an Herbizid(en) und Safener(n) sind üblicherweise vom Typ des herbiziden Mittels und/oder vom verwendeten Safener sowie von der Art des zu behandelnden Pflanzenbestandes abhängig.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.
Die Safener können je nach ihren Eigenschaften zur Vorbehandlung des Saatgutes der Kulturpflanze (Beizung der Samen) verwendet werden oder vor der Saat in die Saatfurchen eingebracht oder zusammen mit der Herbizidmischung vor oder nach dem Auflaufen der Pflanzen angewendet werden. Vorauflaufbehandlung schließt sowohl die Behandlung der Anbaufläche vor der Aussaat als auch die Behandlung der angesäten, aber noch nicht bewachsenen Anbauflächen ein. Bevorzugt ist die gemeinsame Anwendung mit der Herbizidmischung. Hierzu können Tankmischungen oder Fertigformulierungen eingesetzt werden.Depending on their properties, 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.
Die benötigten Aufwandmengen der Safener können je nach Indikation und verwendetem Herbizid innerhalb weiter Grenzen schwanken und liegen in der Regel im Bereich von 0,001 bis 1 kg, vorzugsweise 0,005 bis 0,2 kg Wirkstoff je Hektar.Depending on the indication and the herbicide used, 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.
Die Ausbringung der erfindungsgemäßen herbiziden Mittel kann in üblicherweise erfolgen, zum Beispiel mit Wasser als Träger in Spritzbrühmengen von etwa 5 bis 4000 Liter/ha. Eine Anwendung der Mittel im sog. Low-Volume- und Ultra-Low- Volume-Verfahren (ULV) ist ebenso möglich.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).
Daneben können in den herbiziden Mitteln der Erfindung zur Abrundung der Eigenschaften, meist in untergeordneten Mengen, zusätzlich ein, zwei oder mehrere von den Herbiziden a) verschiedene agrochemische Wirkstoffe (z.B. Insektizide, Fungizide, Safener) enthalten sein.In addition, 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.
Damit ergeben sich zahlreiche Möglichkeiten mehrere agrochemische Wirkstoffe miteinander zu kombinieren und gemeinsam zur Bekämpfung von Schadorganismen wie Schadpflanzen in Pflanzenkulturen einzusetzen, ohne vom Gedanken der Erfindung abzuweichen.This results in numerous possibilities for combining several agrochemical active ingredients with one another and using them together to control harmful organisms such as harmful plants in plant crops without departing from the concept of the invention.
In einer Ausführungsform können z.B. verschiedene agrochemische Wirkstoffe miteinander kombiniert werden, z.B. Fenoxaprop-p-ethyl/loxynil-octanoat, DicIofop/Bromoxynil-octanoat, CMPP/Bromoxynil-octanoat, MCPA/loxynil-octanoat, Bromoxynil-octanoat/Bromoxynil-heptanoat, Bromoxynil-octanoat/Bromoxynil- heptanoat/MCPA, Bromoxynil-octanoat/Bromoxynil-heptanoat/2,4-D, Phenmedipham/Desmedipham, Phenmedipham/Desmedipham/Ethofumesate, Metamitron/Ethofumesate, Phenmedipham/Ethofumesate/Metamitron, Fenoxaprop- p-ethyl/lodosulfuron-methyl-natrium, Deltametrin/Cypermetrin.In one embodiment, e.g. different 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-ethyl / Iodosulfuron-methyl-sodium, Deltametrin / Cypermetrin.
Die herbiziden Wirkstoffe a) und deren Mischungen, z.B. die vorgenannten Wirkstoffmischungen, können mit einem oder mehreren Safenern kombiniert werden, insbesondere mit den Safenern Mefenpyr-diethyl (S1-1), Cloquintocet-mexyl (S2-1), Isoxadifen-ethyl (S3-1) oder Fenchlorazol-ethyl (S1-6), vorzugsweise mit (S1-1), (S2-1) oder (S3-1).The herbicidal active ingredients a) and their mixtures, e.g. the aforementioned active ingredient 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).
Überraschenderweise ergeben die erfindungsgemäßen Mikroemulsionskonzentrate ohne alkoholisches Lösungsmittel bei Verdünnung mit Wasser stabile Mikroemulsionen.Surprisingly, the microemulsion concentrates according to the invention without alcoholic solvent give stable microemulsions when diluted with water.
Die erfindungsgemäßen Mikroemulsionskonzentrate und Mikroemulsionen zeigen ein vorteilhaftes physikalisches Applikationsverhalten. Der agrochemische Wirkstoff bleibt während der Applikation gleichmäßig im Spritztank verteilt, wodurch eine gleichmäßige Ausbringung auf die Kultur bzw. Anbaufläche ermöglicht wird. Auch im Spritztank gebildete Mischungen (Tank-Mischungen) wie wäßrige Lösungen, Suspensionen, Emulsionen oder Suspoemulsionen sind stabil.The 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.
Die erfindungsgemäßen agrochemischen Mittel weisen eine ausgezeichnete biologische Wirkung auf und sind bevorzugt synergistisch. Diese Effekte erlauben unter anderem eine Reduzierung der Aufwandmenge, die Bekämpfung eines breiteren Spektrums von Schadorganismen, die Schließung von Wirkungslücken, eine schnellere und sicherere Wirkung, eine längere Dauerwirkung, eine komplette Kontrolle der Schadorganismen mit nur einer oder wenigen Applikationen, und eine Ausweitung des Anwendungszeitraumes.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 ,
Die nachfolgenden Ausführungsbeispiele erläutern die Erfindung und haben keinerlei limitierenden Charakter.The following exemplary embodiments explain the invention and have no limiting character.
BeispieleExamples
Herstellung der FormulierungenPreparation of the formulations
Es wurden die Lösungsmittel vorgelegt und unter Rühren zunächst die agrochemischen Wirkstoffe und dann die Tenside und üblichen Hilfs- und Zusatzstoffe zugegeben. Die so hergestellten Mikroemulsionskonzentrate wurden anschließend in einem Verhältnis von 1 :10, 1 :30 und 1 :100 in Wasser gegeben. Dabei wurden Mikroemulsionen erhalten. Die Mikroemulsionen wurden über einen Zeitraum von 3 Monaten bei 50 Grad Celsius gelagert und waren während der gesamten Zeitdauer stabil.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.
Die Mengen an zusammengegebenen Komponenten sind in den nachfolgenden Tabellen 1 und 2 in Gew.-% angegeben. Tabelle 1The amounts of components added are given in Tables 1 and 2 below in% by weight. Table 1
Tabelle 2Table 2
Die verwendeten Handelsprodukte sind nachfolgend erläutert:The commercial products used are explained below:
Solvesso® 200 (Exxon): Aromatengemisch Arkopal® N 100 (Clariant): Nonylphenolethoxylat mit 10 EthylenoxideinheitenSolvesso® 200 (Exxon): Aromatic mixture Arkopal® N 100 (Clariant): Nonylphenol ethoxylate with 10 ethylene oxide units
Sapogenat® T-100 (Clariant): Triisobutylphenolethoxylat mit 10 EthylenoxideinheitenSapogenat® T-100 (Clariant): triisobutylphenol ethoxylate with 10 ethylene oxide units
Emulsogen® V 1816 (Clariant): PO-EO-Blockcopolymer Triton® GR 7 ME(Union Carbide): Di(2-ethylhexyl)sulfosuccinat Phenylsulfonat® Ca 100 (Clariant): Calciumdodecylbenzolsulfonat Genapol® X-060 (Clariant): Isotridecylalkohol mit 6 Ethylenoxideinheiten Genapol® X-080 (Clariant): Isotridecylalkohol mit 8 Ethylenoxideinheiten Genapol® PF 40 (Clariant): EO-PO-EO-Blockcopolymer Edenol® D 81 (Cognis): Epoxidiertes Sojabohnenöl 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

Claims

Patentansprüche: claims:
1. Mikroemulsionskonzentrat, enthaltend a) ein oder mehrere agrochemische Wirkstoffe, b) ein oder mehrere nicht-alkoholische organische Lösungsmittel, c) ein oder mehrere anionische Tenside, und d) ein oder mehrere nichtionische Tenside.1. microemulsion concentrate containing a) one or more agrochemical active substances, b) one or more non-alcoholic organic solvents, c) one or more anionic surfactants, and d) one or more nonionic surfactants.
2. Mikroemulsionskonzentrat gemäß Anspruch 1 , worin als Komponente a) enthalten sind, ein oder mehrere herbizide Wirkstoffe.2. Microemulsion concentrate according to claim 1, which contains as component a), one or more herbicidal active ingredients.
3. Mikroemulsionskonzentrat gemäß Anspruch 1 oder 2, worin als Komponente b) enthalten sind, ein oder mehrere Lösungsmittel aus der Gruppe Kohlenwasserstoffe, Carbonsäurederivate, Phosphorsäureester, Ether, Ketone und Sulfoxide.3. Microemulsion concentrate according to claim 1 or 2, wherein component (b) contains one or more solvents from the group consisting of hydrocarbons, carboxylic acid derivatives, phosphoric acid esters, ethers, ketones and sulfoxides.
4. Mikroemulsionskonzentrat gemäß einem oder mehreren der Ansprüche 1 bis4. Microemulsion concentrate according to one or more of claims 1 to
3, worin als Komponente c) enthalten sind, ein oder mehrere anionische Tenside aus der Gruppe Sulfate, Sulfonate, Phosphate und Phosphonate von Kohlenwasserstoffen, die optional alkoxyliert sein können, vorzugsweise Alkylarylsulfonate, Alkylarylpolyglykoletherphosphatsulfate, Alkylar lpolyglykoletherphosphatsulfonate, Alkylethersulfate, Alkylsulfate, Alkylsulfonate, Alkylpolyglykoletherphosphate und Alkylarylpolyglykoletherphosphate.3, which contains as component c), one or more anionic surfactants from the group of sulfates, sulfonates, phosphates and phosphonates of hydrocarbons, which may optionally be alkoxylated, preferably alkylarylsulfonates, alkylarylpolyglycol ether phosphate sulfates, alkylar polyglycol ether phosphate sulfonates, alkyl ether sulfates, alkyl sulfates, alkyl sulfate, alkyl sulfate and alkyl sulfate Alkylarylpolyglykoletherphosphate.
5. Mikroemulsionskonzentrat gemäß einem oder mehreren der Ansprüche 1 bis5. Microemulsion concentrate according to one or more of claims 1 to
4, worin als Komponente d) enthalten sind, ein oder mehrere nichtionische Tenside aus der Gruppe Alkoxylate, vorzugsweise Alkylarylpolyalkoxylate, Alkylenoxid- Blockcopolymere, Polyalkylenoxide, die mit Cιo-C22-Kohlenwasserstoffresten substituiert sein können, alkoxylierte Öle, alkoxylierte Cι0-C22-Fettamine. 4, wherein as component d) are included, one or more nonionic surfactants from the group alkoxylates, preferably Alkylarylpolyalkoxylate, alkylene oxide block copolymers, polyalkylene oxides, which may be substituted with Cιo-C 22 hydrocarbon radicals, alkoxylated oils, alkoxylated C22 Cι 0 fatty amines.
6. Mikroemulsionskonzentrat gemäß gemäß einem oder mehreren der Ansprüche 1 bis 5, zusätzlich enthaltend übliche Hilfs- und Zusatzstoffe.6. microemulsion concentrate according to one or more of claims 1 to 5, additionally containing conventional auxiliaries and additives.
7. Verfahren zur Herstellung eines Mikroemulsionskonzentrats gemäß einem oder mehreren der Ansprüche 1 bis 6, worin die Komponenten gemischt werden.7. A method for producing a microemulsion concentrate according to one or more of claims 1 to 6, wherein the components are mixed.
8. Verwendung eines Mikroemulsionskonzentrats gemäß einem oder mehreren der Ansprüche 1 bis 6, zur Herstellung einer Mikroemulsion.8. Use of a microemulsion concentrate according to one or more of claims 1 to 6, for producing a microemulsion.
9. Agrochemisches Mittel, enthaltend a) ein oder mehrere agrochemische Wirkstoffe, b) ein oder mehrere nicht-alkoholische organische Lösungsmittel, c) ein oder mehrere anionische Tenside, d) ein oder mehrere nichtionische Tenside und e) Wasser.9. Agrochemical composition containing a) one or more agrochemical active ingredients, b) one or more non-alcoholic organic solvents, c) one or more anionic surfactants, d) one or more nonionic surfactants and e) water.
10. Agrochemisches Mittel gemäß Anspruch 9, zusätzlich enthaltend übliche Hilfs- und Zusatzstoffe.10. Agrochemical composition according to claim 9, additionally containing conventional auxiliaries and additives.
11. Agrochemisches Mittel gemäß Anspruch 9 oder 10, in Form einer Mikroemulsion oder der daraus erhältlichen Spritzbrühe.11. Agrochemical composition according to claim 9 or 10, in the form of a microemulsion or the spray mixture obtainable therefrom.
12. Agrochemisches Mittel, erhältlich durch Verdünnen eines Mikroemulsionskonzentrats gemäß einem oder mehreren der Ansprüche 1 bis 6, mit Wasser.12. Agrochemical agent obtainable by diluting a microemulsion concentrate according to one or more of claims 1 to 6 with water.
13. Verfahren zur Herstellung eines agrochemischen Mittels gemäß einem oder mehreren der Ansprüche 9 - 12, worin die Komponenten gemischt werden.13. A method for producing an agrochemical composition according to one or more of claims 9-12, wherein the components are mixed.
14. Verfahren zur Bekämpfung von Schadorganismen, worin eine wirksame Menge eines agrochemischen Mittels gemäß einem oder mehreren der Ansprüche 1 bis 6 oder 9 bis 12 auf die Schadorganismen oder die Orte an denen sie auftreten appliziert wird.14. A method for controlling harmful organisms, wherein an effective amount of an agrochemical agent according to one or more of claims 1 to 6 or 9 to 12 is applied to the harmful organisms or the places where they occur.
15. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, worin eine wirksame Menge eines agrochemischen Mittels gemäß einem oder mehreren der Ansprüche 1 bis 6 oder 9 bis 12 auf die Schadpflanzen, Teile der Pflanzen, Pflanzensamen, die Fläche auf der Pflanzen wachsen appliziert wird.15. A method for controlling undesirable plant growth, in which an effective amount of an agrochemical composition according to one or more of claims 1 to 6 or 9 to 12 is applied to the harmful plants, parts of the plants, plant seeds, the area on which the plants grow.
16. Verwendung eines agrochemischen Mittels gemäß einem oder mehreren der Ansprüche 1 bis 6 oder 9 bis 12, zur Bekämpfung von Schadorganismen.16. Use of an agrochemical agent according to one or more of claims 1 to 6 or 9 to 12, for controlling harmful organisms.
17. Verwendung gemäß Anspruch 16, worin die Schadorganismen Schadpflanzen sind. 17. Use according to claim 16, wherein the harmful organisms are harmful plants.
EP03789129A 2002-12-17 2003-12-04 Microemulsion concentrates Withdrawn EP1575357A2 (en)

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