CA2359491C - Mixture of plant treatment compositions with waxes, their preparation, and their use - Google Patents
Mixture of plant treatment compositions with waxes, their preparation, and their use Download PDFInfo
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- CA2359491C CA2359491C CA002359491A CA2359491A CA2359491C CA 2359491 C CA2359491 C CA 2359491C CA 002359491 A CA002359491 A CA 002359491A CA 2359491 A CA2359491 A CA 2359491A CA 2359491 C CA2359491 C CA 2359491C
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- wax
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- waxes
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Classifications
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- 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
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- 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
- A01N25/24—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 ingredients to enhance the sticking of the active ingredients
Abstract
The present invention relates to a mixture of plant-treatment agents and one or more waxes which are characterised by an acid value of 0-200 and a viscosity of 5 mPas (at 100° C) to 30.000 mPas (at 140° C). The volatility of active substances can thus be increased or toxicity in utilisation can be reduced and the effectiveness can be increased.
Description
Mixture of plant treatment compositions with waxes, their preparation, and their use.
Plant treatment compositions are combinations of acti-,Te substance or active substances and adjuvants such as, for example, solvents or emulsifiers, which allow an applicati"n in the form of an aqueous phase. To improve efficacy, they may comprise additions such as oily hydrocarbons cr emulsifier systems (for example ~N'0 97/47199). the addition of waxes in combination with fatty acid derivatives, other constituents or microencapsulation has also beer_ proposed, for example WO 95/34200, DE-A-3 334 198, WO 97/27932. Pz:oof of an improved activity in biotests was not provided.
There is therefore a demand for additions for plant treatment compositions which modify the action of the latter, in particular from the aspect of a reduced release of substances into the environment.
The present invention modifies plant treatment composition:
in such a way that they exhibit their entire action withouv hazardous substances being introduced ir_to the er,_virorlment .
Surprisingly, it has now been four:d that mixtures of x:lant treatment compositions with one or more waxes ha~,~e considerable advantages over the products which do not comprise waxes.
The invention therefore relates to mixtures of plant treatment compositions with one or more waxes, these waxes being characterized by an acid number of 0-200 and a viscosity of 5 mPas (at 100°C) to 30,000 mPas ;at 140°C.).
In one aspect, the invention provides a mixture of a plant treatment composition comprising an active substance and at la least one wax, wherein the wax has an acid number of 5-150 and a viscosity of 5-300 mPas at 100°C.
If desired, the following can be realized with these mixtures of plant treatment compositions with waxes:
~ reduced volatility of active substances reduced toxicity to the user ' CA 02359491 2001-07-18 ~ reduced phytotoxic effects of the active substances or the formulation ~ increased reliability of action . ~ increased rain fastness of the film ~ slow release of the active substance ~ protection from evaporation in the case of low-volume (or ultra low volume) application.
Depending on the desired effect, this allows the amounts of active substance to be reduced or the spray intervals to be extended or the number of treatments to be reduced or the phytotoxic effects to be reduced in favor of the desired action.
Well suited mixtures are those in which the waxes have an acid number of 0-150, in particular 5-150, and a viscosity of 5 mPas (at 100°C) to mPas (at 170 °C), in particular from 5 to 300 mPas (at 100°C).
Very particularly preferred mixtures are those in which the waxes have an acid number of 15 - 60 and a viscosity of 150 - 5000 mPas (at 140°C).
In general, the mixtures comprise 0.01 to 95, preferably 1 to 95% by weight of wax and 5 to 99.99, preferably 5 to 99% by weight of plant treatment composition.
Plant treatment compositions are to be understood as meaning all active substances and their formulations which are employed as insecticides, fungicides, herbicides and seed treatments. The following may be mentioned individually:
1. from the group of the phosphorus compounds acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, bromophos, bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon, dichlorphos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, fonofos, formothion, fosthiazate (ASC-66824) heptenophos, isozophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, ', ' CA 02359491 2001-07-18 salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosfolan, phosphocarb (BAS-301 ), phosmet, phosphamidon, phoxim, pirimiphos, pirimiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiodemeton, triazophos, trichlorphon, vamidothion;
2. from the group of the carbamates alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate 3. from the group of the carboxylic esters acrinathrin, allethrin, alphametrin, beta-cypermethrin, 5-benzyl 3-furylmethyl (E), (1 R)-cis-2,2-di-methyl-3-(2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1 RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate ((D) isomer), imiprothrin (S-41311 ), lambda-cyhalothrin, permethrin, phenothrin ((R) isomer), prallethrin, pyrethrins (natural materials), resmethrin, tefluthrin, tetramethrin, theta cypermethrin (TD-2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701 );
Plant treatment compositions are combinations of acti-,Te substance or active substances and adjuvants such as, for example, solvents or emulsifiers, which allow an applicati"n in the form of an aqueous phase. To improve efficacy, they may comprise additions such as oily hydrocarbons cr emulsifier systems (for example ~N'0 97/47199). the addition of waxes in combination with fatty acid derivatives, other constituents or microencapsulation has also beer_ proposed, for example WO 95/34200, DE-A-3 334 198, WO 97/27932. Pz:oof of an improved activity in biotests was not provided.
There is therefore a demand for additions for plant treatment compositions which modify the action of the latter, in particular from the aspect of a reduced release of substances into the environment.
The present invention modifies plant treatment composition:
in such a way that they exhibit their entire action withouv hazardous substances being introduced ir_to the er,_virorlment .
Surprisingly, it has now been four:d that mixtures of x:lant treatment compositions with one or more waxes ha~,~e considerable advantages over the products which do not comprise waxes.
The invention therefore relates to mixtures of plant treatment compositions with one or more waxes, these waxes being characterized by an acid number of 0-200 and a viscosity of 5 mPas (at 100°C) to 30,000 mPas ;at 140°C.).
In one aspect, the invention provides a mixture of a plant treatment composition comprising an active substance and at la least one wax, wherein the wax has an acid number of 5-150 and a viscosity of 5-300 mPas at 100°C.
If desired, the following can be realized with these mixtures of plant treatment compositions with waxes:
~ reduced volatility of active substances reduced toxicity to the user ' CA 02359491 2001-07-18 ~ reduced phytotoxic effects of the active substances or the formulation ~ increased reliability of action . ~ increased rain fastness of the film ~ slow release of the active substance ~ protection from evaporation in the case of low-volume (or ultra low volume) application.
Depending on the desired effect, this allows the amounts of active substance to be reduced or the spray intervals to be extended or the number of treatments to be reduced or the phytotoxic effects to be reduced in favor of the desired action.
Well suited mixtures are those in which the waxes have an acid number of 0-150, in particular 5-150, and a viscosity of 5 mPas (at 100°C) to mPas (at 170 °C), in particular from 5 to 300 mPas (at 100°C).
Very particularly preferred mixtures are those in which the waxes have an acid number of 15 - 60 and a viscosity of 150 - 5000 mPas (at 140°C).
In general, the mixtures comprise 0.01 to 95, preferably 1 to 95% by weight of wax and 5 to 99.99, preferably 5 to 99% by weight of plant treatment composition.
Plant treatment compositions are to be understood as meaning all active substances and their formulations which are employed as insecticides, fungicides, herbicides and seed treatments. The following may be mentioned individually:
1. from the group of the phosphorus compounds acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, bromophos, bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon, dichlorphos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, fonofos, formothion, fosthiazate (ASC-66824) heptenophos, isozophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, ', ' CA 02359491 2001-07-18 salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosfolan, phosphocarb (BAS-301 ), phosmet, phosphamidon, phoxim, pirimiphos, pirimiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiodemeton, triazophos, trichlorphon, vamidothion;
2. from the group of the carbamates alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate 3. from the group of the carboxylic esters acrinathrin, allethrin, alphametrin, beta-cypermethrin, 5-benzyl 3-furylmethyl (E), (1 R)-cis-2,2-di-methyl-3-(2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1 RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate ((D) isomer), imiprothrin (S-41311 ), lambda-cyhalothrin, permethrin, phenothrin ((R) isomer), prallethrin, pyrethrins (natural materials), resmethrin, tefluthrin, tetramethrin, theta cypermethrin (TD-2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701 );
4. from the group of the amidines amitraz, chlordimeform;
5. from the group of the tin compounds cyhexatin, fenbutatin oxide;
', ~ CA 02359491 2001-07-18 6. others abamectin, ABG-9008, acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassiana, bensultap, bifenazate (D-2341 ), binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap, chlorobenzilate, chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlorfentezine, chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, 2-naphthylmethyl cyclopropanecarboxylate (Rol2-04770), cyromazin, diacloden (thiamethoxam), diafenthiuron, ethyl N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzo-carboximidate, DDT, dicofol, diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, diofenolan, DPX-062, emamectin benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301 ), fenazaquin, fenoxycarb, fipronil, fluazuron, flumite (flufenzine, SZI-121 ), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345), halofenprox (MTI-732), hexaflumuron (DE 473), hexythiazox, HOI-9004, hydramethylnon (AC 217300), lufenuron, imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), M-20, MTI-446, ivermectin, M-020, methoxyfenozide (Intrepid, RH-2485), milbemectin, NC-196, Neemgard, nitenpyram (TI-304), 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD
35651 ), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (W L108477), pyriproxyfen (S-71639), NC-196, NC-1111, NNI-9768, novaluron (MCW-275), OK-9701, OK-9601, OK-9602, propargite, pymetrozine, pyridaben, pyrimidifen (SU-8801 ), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, SI-8601, silafluorfen, silomadine (CG-177), spinosad, SU-9118, tebufenozide, tebufenpyrad (MK-239), teflubenzuron, Tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, tolfenpyrad (OMI-88), triazamate (RH-7988), triflumuron, verbutin, vertalec (Mykotal), YI-5301;
Fungicides which are known from the literature and which can be combined in accordance with the invention with waxes are, for example, the following products:
aldimorph, andoprim, anilazine, azoxystrobin, azaconazole, BAS 450F, benalaxyl, benodanil, benomyl, bethoxazin, binapacryl, bion (CGA-245704), bitertanol, bromuconazole, buthiobate, captafol, captan, carbendazim, carboxin, carpropamide, CGA 173506, cymoxanil, cyprodinil, cyprofuram, diflumetorim, dichlofluanid, dichlomezin, diclobutrazol, diclocymet (S-2900), diclomezine, diethofencarb, 5 difenoconazol (CGA 169374), difluconazole, dimethirimol, dimethomorph, diniconazole, dinocap, dithianon, dodemorph, dodine, edifenfos, epoxiconazole, ethirimol, etridiazol, famoxadone, (DPX-JE874), fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferimzone (TF164), fluazinam, fluobenzimine, fludioxonil, flumetover (RPA-403397), fluquinconazole, fluorimide, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furconazol, furametpyr (S-82658), furmecyclox, guazatine, hexaconazole, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, Isoprothiolane, KNF-317, kresoxim-methyl (BAS-490F), copper compounds such as copper oxichloride, oxine-copper, copper oxide, mancozeb, maneb, mepanipyrim (KIF 3535), mepronil, metalaxyl, metalaxyl-M (CGA-329351), metconazole, methasulfocarb, methfuroxam, metominofen (SSF-126), metominostrobin (fenominostrobin, SSF-126), MON 24000, MON-6550, MON-41100, myclobutanil, nabam, nitrothalisopropyl, nuarimol, ofurace, OK-9601, OK-9603, oxadixyl, oxycarboxin, paclobutrazol, penconazole, pencycuron, PP 969, polyoxins, probenazole, propineb, prochloraz, procymidon, propamocarb, propiconazole, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen (DE-795), rabenzazole, RH-7592, RH-7281, sulfur, spiroxamine, SSF-109, tebuconazole, tetraconazole, TTF 167, thiabendazole, thicyofen, thifluzamide (RH-130753), thiofanate-methyl, thiram, TM-402, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichoderma harzianum(DHF-471 ), tricyclazole, tridemorph, triforine, triflumizole (UCC-A815), triticonazole, uniconazole, validamycin, vinchlozolin, XRD 563, zineb, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium C13/C15-alcohol ether sulfonate, sodium cetostearyl phosphate ester, sodium dioctylsulfosuccinate, sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, cetyltrimethylammonium chloride, salts of long-chain primary, secondary or tertiary amines, alkylpropyleneamine, laurylpyrimidinium bromide, ethoxylated quaternized fatty amines, alkyldimethylbenzylammonium chloride and 1-hydroxyethyl-2-alkylimidazolin.
' CA 02359491 2001-07-18 The abovementioned components in combinations are known active substances, most of which are described in C.D.S. Tomlin, S.B. Walker, The Pesticide Manual, 11th Edition (1997), British Crop Protection Council.
Substances which can be employed as components in combination with the waxes are, for example, known active substances as they are described in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 10th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1994 and the literature cited therein. Herbicides which are known from the literature and which can be combined with the waxes are the following active substances (note: either the common name of the International Organization for Standardization (ISO) or the chemical names of the compounds are given, if appropriate together with the customary code number):
acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]-oxy)acetic acid and its methyl ester; alachlor; alloxydim; ametryn;
amidosulfuron; amitrole; AMS, i.e. ammonium sulfamate; anilofos; asulam;
atrazine; azimsulfurone (DPX-A8947); aziprotryn; barbane; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin;
benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap;
benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;
bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos;
busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin;
butylate; cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051 );
CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e.. 2-chloroallyl diethyldithiocarbamate; chlomethoxyfen; chloramben; chlorazifop-butyl, chlormesulon (ICI-A0051 ); chlorbromuron; chlorbufam; chlorfenac;
chlorflurecol-methyl; chloridazon; chlorimuron-ethyl; chlornitrofen;
chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; clethodim; clodinafop and its ester derivatives (for example clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid;
cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104);
cycloxydim; cycluron; cyhalofop and its ester derivatives (for example the butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB;
dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil;
dichlorprop; diclofop and its esters such as diclofop-methyl; diethatyl;
difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor;
', ' CA 02359491 2001-07-18 _ 7 dimethametryn; dimethenamid (SAN-582H); dimethazone; clomazon;
dimethipin; dimetrasulfuron; dinitramine; dinoseb; dinoterb; diphenamid;
dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, i.e.
5-cyano-1-(1,1-dimethylethyl)-N-methyl-1 H-pyrazole-4-carboxamide;
endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl;
ethidimuron; ethiozin; ethofumesate; F5231, i.e.. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-ethane-sulfonamide; ethoxyfen and its esters (for example the ethyl ester, HN-252); etobenzanid (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron;
fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (for example the pentyl ester, S-23031 ); flumioxazin (S-482);
flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl;
flupropacil CUBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone;
fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen;
halosulfuron and its esters (for example the methyl ester, NC-319);
haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters;
hexazinone; imazamethabenz-methyl; imazapyr; imazaquin and salts, such as the ammonium salt; imazethamethapyr; imazethapyr;
imazosulfuron; ioxynil; isocarbamid; isopropalin; isoproturon; isouron;
isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA;
MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachlor;
methabenzthiazuron; metham; methazole; methoxyphenone;
methyldymron; metabenzuron; methobenzuron; metobromuron;
metolachlor; metosulam (XRD 511 ); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate;
monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamin; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; ~ naproanilide;
napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin;
nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin;
perfluidone; phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine;
prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn;
propachlor; propanil; propaquizafop and its esters; propazine; propham;
'. ~ CA 02359491 2001-07-18 '. 8 propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolynate; pyrazon; pyrazosulfuron-ethyl;
pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (for example the propargyl ester); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron;
rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazol; secbumeton;
sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and its methyl ester; sulfentrazon (FMC-97285, F-6285); sulfazuron;
sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544);
tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine;
terbutryn; TFH 450; i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1 H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron;
thiazopyr (Mon-13200); thidiazimin (SN-24085); thifensulfuron-methyl;
thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron;
triazofenamide;
tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin;
triflusulfuron and its esters (for example the methyl ester, DPX-66037); trimeturon;
tsitodef; vernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1 H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.
Waxes are known materials of natural or synthetic origin as they are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry Vol. A 28, 103. They constitute chemical substance mixtures which are usually defined by, for example, their viscosity and acid number. Pure hydrocarbon waxes do not contain functional groups and therefore have an acid number of 0. Their viscosity range can be between 5 mPas (at 100°C) and 30,000 mPas (at 140°C).
Preferred waxes are those which have an acid number of 0 - 150 and a viscosity of between 5 mPas and 2000 mPas (at 170°C) Examples which may be mentioned are: polyethylene waxes (homo- or copolymers), which are prepared by the Ziegler-method or the high-pressure method, or polypropylene waxes (synthesis or degradation product).
' CA 02359491 2001-07-18 Particularly preferred waxes are those which, owing to their acid number of y 5 - 150, have carboxyl groups and, if appropriate, other polar functional groups and which have viscosities of 5 mPas - 2000 mPas (at 170 °C).
Very particularly preferred waxes are those whose acid number is 5 - 150 and whose viscosity is 5 - 300 mPas or those whose acid number is - 60 and whose viscosity is 150 (at 100°C) - 5000 mPas (at 120°C).
Examples which may be mentioned are: montan wax acids, their soaps of 10 mono- and polyvalent cations, and montan wax esters of mono- and polyhydric alcohols, carnauba wax, candelilla wax, sugar cane wax, peat wax and hydrocarbon compounds which have been oxidized or grafted by a variety of processes.
15 The invention furthermore relates to methods for the preparation of the abovementioned mixtures. The ground wax, which has a particle size of less than 100 Nm and a d50 value (d50 = median of the particle size distribution) of 5 - 30,um is mixed with the active substance in suitable form and the mixture is incorporated into a suitable formulation. A
preferred process consists in coating the active substance with the wax in solid form, if appropriate ground or finely ground with particle size distribution in the region of < 40 ,um and d50 values of 3 - 15 ,um, or with the melt, with the aid of a mixer and converting this material into a formulation which can be applied, as is customary for the pure active substance.
However, the active substance may also be coated with wax by means of dispersing in a wax dispersion, where the finely divided wax precipitates onto the active substance by adding suitable adjuvants (such as, for example, CaCl2 solution, dilute acids).
Another preferred process for the preparation of the mixtures consists in treating formulated plant treatment compositions, for example an EC
(emulsifiable concentrate) with a wax or adding the desired amount of wax by adding a compatible wax dispersion, and, if appropriate, producing a stable preparation by means of heating.
293?4-385 A particularly preferred process for the preparation of the mixtures according to the invention consists in first preparing a ready to-use spray mixture of the plant treatment compositions in water and then adding the desired amount of a wax dispersion. The sequence of the addition can be 5 varied, and, if appropriate, it may be necessary to predilute the wax dispersion and/or the formulated plant treatment composition so as to avoid flocculation.
The use concentrations of the plant treatment compositions are 10 predetermined by the activity of the active substance and its approved application rate. The added amounts of wax, termed solids, may be varied within wide limits. They depend on the active substance of the plant treatment composition and, on the nature of the desired effect. They are within a range of 5 g/ha to 4 kg/ha of wax, with 5 g/ha to 1 kg/ha of wax being preferred and 10 g/ha to 0.5 kg/ha of wax being particularly preferred.
The invention furthermore relates to the use of the mixtures according. to the invention as plant treatment compositions.
Examples:
Example 1 In an IKA laboratory kneader (v = 500 mi) 65 g of Gol~ix~' vt~ 9c ars mix for 1 hour with 11.5 g of ~Hostalub WE 4 at a temperature of 90°C.
During this time, the wax absorbs the active substance. An analogous treatment was given to, for example, endosulfan.
Example 2 The active substance is dispersed or emulsified in water as fine particles.
The wax dispersion is added, and the dispersion is coagulated by changing the pH. Wax and active substance are bound to one another in the coagulate. When the procedure is carried out under controlled conditions, the particle size can be adjusted. Otherwise, the material is subjected to wet grinding, formulating and drying.
This process can be employed when the active substance is not highly sensitive to water and alkalis/acids. If the active substance is basic, precipitation can be provoked directly by adding a cationic dispersion. If the active Substance is aCldl(:, pieC:ipiiaiivi ~ i;ai ii be pr ovokcd vviti i a~~i i anionic dispersion. ' The quantity of wax and active substance can be matched to each other as desired if the precipitation conditions can be provoked.
To adjust redispersibility, the dried product must still undergo formulation.
In this manner, for example, Goltix VM 90 was coated from dispersion 04 with 5, 10, 15 and 20% by weight of wax.
Example 3 5 g of montanic acid polyglycol ester are dissolved in 95 g of ~Corbel (EC) with gentle warming. The resulting combination is to be brought with water to the required use concentration, as usual.
., Example 4 15.0 g of montan wax acids (AN = 140) + 4.5 g of sapogenatT"" z 50~~ are molten at 105°C. The melt is poured into 58.5 g of boiling drinking water in a thin stream, with stirring. Then, 22.0 g of cold ~Thiodan 35 are added.
The mixture is boiled up and rapidly cooled in a water-bath, with stirring.
The resulting wax-comprising dispersion, employed at the usual application rate, showed a markedly improved long-term action against Heliothis virescens larvae on cotton compared with Thiodan 35.
Analogously, montan wax acids can be incorporated into ~Desgan or OErestan.
Example 5 First, the ready-to-use spray mixture of the plant treatment composition is prepared in a suitable amount of water, and then such an amount of dispersion 02 as is required for achieving the desired effect is added, the dispersion 02 being obtained as follows:, 29.2 g of "wax LP" and 5.80 g of Sapogenat T 500 are melted at 105°C and, with stirring, poured into boiling drinking water. The mixture is boiled up and cooled in a water-bath, with stirring.
Example 6 In a drum, 100 g of wheat which has been dressed in the known manner with ~Landor are treated with 3 g of the dispersion 02, which had been adjusted to a solids content of 10% by dilution with water, mixing is then ~
continued for 10 minutes, and the mixture is allowed to dry. The thickness of the wax coating produced on the wheat kernel is approx. 3 Nm.
~ Example 7 ~Corbel with and without added wax dispersion is applied to a PE film, allowed to dry, and the decrease in the content of the active substance fenpropimorph is monitored by FTIR spectroscopy. For example, the combinations with the dispersions 01 and 02 show a markedly reduced volatility of fenpropimorph; while 50% of active substance were still detected after 4 days (23°C, atmospheric humidity 60%) without wax, 85 and 83% of active substance are still present when (1 kg of wax per ha) are added as dispersion 01 and dispersion 02, respectively.
Example 8 The dispersion 04 is diluted to almost the desired end concentration of the wax (0.5 kg of wax per hectare) in the spray mixture, plant treatment composition which has also been diluted with water is added, with stirring, and the mixture is finally diluted to the end concentration. When ~Folicur or ~Corbel were used and the mixture was applied to wheat, a markedly reduced phytotoxicity was observed, in particular at higher fungicide concentrations.
Example 9 (herbicide experiment) ~Basta and ~Roundup were used alone and in combination with waxes on non-resistant maize (site: Wolfsthal, Austria). A markedly improved initial action of Roundup against dicots is achieved by adding, for example, dispersions 01, 02, 03. In the case of both herbicides, a markedly improved long-term action is achieved by adding, for example, dispersions 01, 02 or 03.
Example 10 (fungicide experiment) Winter wheat (variety Monopol, site: Altenlengbuch, Austria), was treated once (5th May 1998) at stage 31-32 with the recommended application rates of the fungicides ~Amistar or ~Juwel, with or without addition of wax (1 kg/ha) and compared with untreated plots, and the disease level of Erysiphe graminis was scored. On the 15th June, the combination of Amistar or Juwel and dispersion 02, for example, showed no symptoms of mildew disease; untreated showed a disease level of 10%, Amistar 8%
' ~ CA 02359491 2001-07-18 ' 13 and Juwel 7%. The low disease levels achieved with the wax combinations were not even achieved by two treatments with Amistar or Juwel.
Example 11 Control of Phytophthora infestans in potatoes (variety: Quarta, outdoor conditions) A combination of ~Shirlane and the respective wax dispersion is prepared analogously to Example 5 and applied as usual. The number of spray treatments and the spray intervals was decided by the regional institute for agronomy. Weather and other parameters which allow infection constitute reasons for carrying out a spray treatment. ~Shirlane was very effective.
At the time of haulm wilting, a disease level of 30% was found.
Combinatiions of Shirlane with the wax emulsions 01, 02, 03 which were applied at the same spray timing showed an improved action resulting in a Phytophthora disease level which was up to 50% lower. A lower disease level did not produce a significant difference between the individual wax dispersions. However, the consistency of the effect is notable. The strips treated with wax emulsions had a healthier appearance until the time when the haulm was destroyed with a mechanical beater, while the crop in toto showed earlier wilting.
Example 12 Experiments with ~Juwel, ~Opus Top and ~Bion with and without wax were set up on winter wheat (variety Monopol, site: Paar, Germany) and evaluated analogously to Example 10. The combination of the fungicides with, for example, dispersion 02 (1 kg/ha wax) reduced the Erysiphe graminis and Septoria nodorum disease levels markedly compared with the fungicides ~Juwel and ~Opus Top alone. When the wax mixtures were used, the yields were up to 40% higher compared with the untreated control and up to 32% higher compared with the fungicide treatment without wax.
Example 13 Dispersion 01 At approximately 105°C, melt 25 g of montan wax ester + 5 g of "wax emulgator 4106", and portionwise stir 69.9 g of boiling drinking water into the melt. Boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROTT"" 94-08* and make up the water which has evaporated.
'Supplier: SANITIZED AG
Example 14 Dispersion 02 At approximately 105°C, melt 25 g of montan wax ester + 5 g of Sapogenat T 500, and portionwise stir 69.9 g of boiling drinking water into the melt.
Briefly boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT 94-OS and make up the water which has evaporated.
Example 15 Dispersion 03 s At approximately 105°C, melt 25 g of montan wax ester, bring 45 g of demineralized water to the. boil and stir portionwise into the molten wax.
Briefly boil up the emulsion, switch off the heating and then stir 29.9 g of cold demineralized water into the mixture and rapidly cool the emulsion to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT
94-08 and make up the water which has evaporated.
Example 16 Dispersion 04 At approximately 110-115°C, melt 20 g of montan wax ester + 5 g of "EmulgatorT"" S 3267/3", add 0.6 g of glacial acetic acid, and smartly stir the melt into 74.3 g of boiling drinking water.
Briefly boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT 94-08 and make up the water which has evaporated.
Example 17 Dispersion 05 At approximately 105°C, melt 25 g of montan wax ester + 5 g of "wax emulgator 4106°, and portionwise stir 69.9 g of boiling drinking water into the melt. Briefly boil up the emulsion and then rapidly cool to room torr;pcratyra in a wa_tPr-hath, Add 01 g of preservative SANIPROT 94-G8 and make up the water which has evaporated.
Example 18 5 Dispersion 06 A 1-liter autoclave is charged with 320 g of wax oxidate of AN 17; 60 g of GenapolT"" T 250; 20 g GenapolT"" T 500 and 2 g of sodium sulfite together with 597 g of drinking water. Within 30 minutes, tine 10 internal temperature of the autoclave is brought to 140-145°C:
while stirring with an anchor mixer. The mixture is then emulsified for 20 min at the same temperature and the same stirring speed and subsequently cooled to approximately 30°C in.
the course of 40 min. 1 g of preservative SANIPROT 94-08 is 15 stirred into the cold dispersion.
Example 19 Dispersion 07 Part I
A 1-liter autoclave is charged with 273 g of wax oxidate of AN 25; 68 g of emulsifier Synperonic'~' 13/12*; 2 g of sodium pyrosulfite (=Na2Sz05) and 7 g of potassium hydroxide purity 860 (= caustic potash) together with 649 g of demineralized water. Within 30 minutes, the internal temperature of the autoclave is brought to 130°C
while stirring with an anchor mixer. The mixture is then emulsified for 20 minutes at the same temperature and the same stirring speed and subsequently cooled to approximately 30°C :in the course of 40 minutes. 1 g of preservative SANIPROT 94-08 is stirred into the cold dispersion.
*Supplier: ICI, Essen Part II
33.7 g of the dispersion prepared in part I are diluted with 33.5 g of drinking water, and 32.8 g of dispersion 03 are then added and the mixture is stirred. The solids content of the mixture is 20%.
Example 20 Dispersion 08 . ' CA 02359491 2001-07-18 Part I
At approximately 110-115°C, 24.4 g of montan wax and 4.9 g of "wax emulgator 4106" are melted. The melt is saponified with 43% strength potassium hydroxide solution. The saponified melt is stirred as a thin stream into 69.2 g of boiling demineralized water, with mechanical stirring, briefly boiled up and rapidly cooled in a water-bath. The emulsion is stabilized with 0.1 g of preservative SANIPROT 94-08, and the lost water is made up.
Part II
38.7 g of the dispersion made as in part I is diluted with 27.7 g of drinking water, and 33.6 g of dispersion 03 are then added and the mixture is stirred. The solids content of the mixture is 20%.
', ~ CA 02359491 2001-07-18 6. others abamectin, ABG-9008, acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassiana, bensultap, bifenazate (D-2341 ), binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap, chlorobenzilate, chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlorfentezine, chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, 2-naphthylmethyl cyclopropanecarboxylate (Rol2-04770), cyromazin, diacloden (thiamethoxam), diafenthiuron, ethyl N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzo-carboximidate, DDT, dicofol, diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, diofenolan, DPX-062, emamectin benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301 ), fenazaquin, fenoxycarb, fipronil, fluazuron, flumite (flufenzine, SZI-121 ), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345), halofenprox (MTI-732), hexaflumuron (DE 473), hexythiazox, HOI-9004, hydramethylnon (AC 217300), lufenuron, imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), M-20, MTI-446, ivermectin, M-020, methoxyfenozide (Intrepid, RH-2485), milbemectin, NC-196, Neemgard, nitenpyram (TI-304), 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD
35651 ), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (W L108477), pyriproxyfen (S-71639), NC-196, NC-1111, NNI-9768, novaluron (MCW-275), OK-9701, OK-9601, OK-9602, propargite, pymetrozine, pyridaben, pyrimidifen (SU-8801 ), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, SI-8601, silafluorfen, silomadine (CG-177), spinosad, SU-9118, tebufenozide, tebufenpyrad (MK-239), teflubenzuron, Tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, tolfenpyrad (OMI-88), triazamate (RH-7988), triflumuron, verbutin, vertalec (Mykotal), YI-5301;
Fungicides which are known from the literature and which can be combined in accordance with the invention with waxes are, for example, the following products:
aldimorph, andoprim, anilazine, azoxystrobin, azaconazole, BAS 450F, benalaxyl, benodanil, benomyl, bethoxazin, binapacryl, bion (CGA-245704), bitertanol, bromuconazole, buthiobate, captafol, captan, carbendazim, carboxin, carpropamide, CGA 173506, cymoxanil, cyprodinil, cyprofuram, diflumetorim, dichlofluanid, dichlomezin, diclobutrazol, diclocymet (S-2900), diclomezine, diethofencarb, 5 difenoconazol (CGA 169374), difluconazole, dimethirimol, dimethomorph, diniconazole, dinocap, dithianon, dodemorph, dodine, edifenfos, epoxiconazole, ethirimol, etridiazol, famoxadone, (DPX-JE874), fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferimzone (TF164), fluazinam, fluobenzimine, fludioxonil, flumetover (RPA-403397), fluquinconazole, fluorimide, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furconazol, furametpyr (S-82658), furmecyclox, guazatine, hexaconazole, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, Isoprothiolane, KNF-317, kresoxim-methyl (BAS-490F), copper compounds such as copper oxichloride, oxine-copper, copper oxide, mancozeb, maneb, mepanipyrim (KIF 3535), mepronil, metalaxyl, metalaxyl-M (CGA-329351), metconazole, methasulfocarb, methfuroxam, metominofen (SSF-126), metominostrobin (fenominostrobin, SSF-126), MON 24000, MON-6550, MON-41100, myclobutanil, nabam, nitrothalisopropyl, nuarimol, ofurace, OK-9601, OK-9603, oxadixyl, oxycarboxin, paclobutrazol, penconazole, pencycuron, PP 969, polyoxins, probenazole, propineb, prochloraz, procymidon, propamocarb, propiconazole, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen (DE-795), rabenzazole, RH-7592, RH-7281, sulfur, spiroxamine, SSF-109, tebuconazole, tetraconazole, TTF 167, thiabendazole, thicyofen, thifluzamide (RH-130753), thiofanate-methyl, thiram, TM-402, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichoderma harzianum(DHF-471 ), tricyclazole, tridemorph, triforine, triflumizole (UCC-A815), triticonazole, uniconazole, validamycin, vinchlozolin, XRD 563, zineb, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium C13/C15-alcohol ether sulfonate, sodium cetostearyl phosphate ester, sodium dioctylsulfosuccinate, sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, cetyltrimethylammonium chloride, salts of long-chain primary, secondary or tertiary amines, alkylpropyleneamine, laurylpyrimidinium bromide, ethoxylated quaternized fatty amines, alkyldimethylbenzylammonium chloride and 1-hydroxyethyl-2-alkylimidazolin.
' CA 02359491 2001-07-18 The abovementioned components in combinations are known active substances, most of which are described in C.D.S. Tomlin, S.B. Walker, The Pesticide Manual, 11th Edition (1997), British Crop Protection Council.
Substances which can be employed as components in combination with the waxes are, for example, known active substances as they are described in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 10th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1994 and the literature cited therein. Herbicides which are known from the literature and which can be combined with the waxes are the following active substances (note: either the common name of the International Organization for Standardization (ISO) or the chemical names of the compounds are given, if appropriate together with the customary code number):
acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]-oxy)acetic acid and its methyl ester; alachlor; alloxydim; ametryn;
amidosulfuron; amitrole; AMS, i.e. ammonium sulfamate; anilofos; asulam;
atrazine; azimsulfurone (DPX-A8947); aziprotryn; barbane; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin;
benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap;
benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;
bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos;
busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin;
butylate; cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051 );
CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e.. 2-chloroallyl diethyldithiocarbamate; chlomethoxyfen; chloramben; chlorazifop-butyl, chlormesulon (ICI-A0051 ); chlorbromuron; chlorbufam; chlorfenac;
chlorflurecol-methyl; chloridazon; chlorimuron-ethyl; chlornitrofen;
chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; clethodim; clodinafop and its ester derivatives (for example clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid;
cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104);
cycloxydim; cycluron; cyhalofop and its ester derivatives (for example the butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB;
dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil;
dichlorprop; diclofop and its esters such as diclofop-methyl; diethatyl;
difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor;
', ' CA 02359491 2001-07-18 _ 7 dimethametryn; dimethenamid (SAN-582H); dimethazone; clomazon;
dimethipin; dimetrasulfuron; dinitramine; dinoseb; dinoterb; diphenamid;
dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, i.e.
5-cyano-1-(1,1-dimethylethyl)-N-methyl-1 H-pyrazole-4-carboxamide;
endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl;
ethidimuron; ethiozin; ethofumesate; F5231, i.e.. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-ethane-sulfonamide; ethoxyfen and its esters (for example the ethyl ester, HN-252); etobenzanid (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron;
fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (for example the pentyl ester, S-23031 ); flumioxazin (S-482);
flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl;
flupropacil CUBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone;
fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen;
halosulfuron and its esters (for example the methyl ester, NC-319);
haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters;
hexazinone; imazamethabenz-methyl; imazapyr; imazaquin and salts, such as the ammonium salt; imazethamethapyr; imazethapyr;
imazosulfuron; ioxynil; isocarbamid; isopropalin; isoproturon; isouron;
isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA;
MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachlor;
methabenzthiazuron; metham; methazole; methoxyphenone;
methyldymron; metabenzuron; methobenzuron; metobromuron;
metolachlor; metosulam (XRD 511 ); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate;
monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamin; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; ~ naproanilide;
napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin;
nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin;
perfluidone; phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine;
prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn;
propachlor; propanil; propaquizafop and its esters; propazine; propham;
'. ~ CA 02359491 2001-07-18 '. 8 propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolynate; pyrazon; pyrazosulfuron-ethyl;
pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (for example the propargyl ester); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron;
rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazol; secbumeton;
sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and its methyl ester; sulfentrazon (FMC-97285, F-6285); sulfazuron;
sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544);
tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine;
terbutryn; TFH 450; i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1 H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron;
thiazopyr (Mon-13200); thidiazimin (SN-24085); thifensulfuron-methyl;
thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron;
triazofenamide;
tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin;
triflusulfuron and its esters (for example the methyl ester, DPX-66037); trimeturon;
tsitodef; vernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1 H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.
Waxes are known materials of natural or synthetic origin as they are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry Vol. A 28, 103. They constitute chemical substance mixtures which are usually defined by, for example, their viscosity and acid number. Pure hydrocarbon waxes do not contain functional groups and therefore have an acid number of 0. Their viscosity range can be between 5 mPas (at 100°C) and 30,000 mPas (at 140°C).
Preferred waxes are those which have an acid number of 0 - 150 and a viscosity of between 5 mPas and 2000 mPas (at 170°C) Examples which may be mentioned are: polyethylene waxes (homo- or copolymers), which are prepared by the Ziegler-method or the high-pressure method, or polypropylene waxes (synthesis or degradation product).
' CA 02359491 2001-07-18 Particularly preferred waxes are those which, owing to their acid number of y 5 - 150, have carboxyl groups and, if appropriate, other polar functional groups and which have viscosities of 5 mPas - 2000 mPas (at 170 °C).
Very particularly preferred waxes are those whose acid number is 5 - 150 and whose viscosity is 5 - 300 mPas or those whose acid number is - 60 and whose viscosity is 150 (at 100°C) - 5000 mPas (at 120°C).
Examples which may be mentioned are: montan wax acids, their soaps of 10 mono- and polyvalent cations, and montan wax esters of mono- and polyhydric alcohols, carnauba wax, candelilla wax, sugar cane wax, peat wax and hydrocarbon compounds which have been oxidized or grafted by a variety of processes.
15 The invention furthermore relates to methods for the preparation of the abovementioned mixtures. The ground wax, which has a particle size of less than 100 Nm and a d50 value (d50 = median of the particle size distribution) of 5 - 30,um is mixed with the active substance in suitable form and the mixture is incorporated into a suitable formulation. A
preferred process consists in coating the active substance with the wax in solid form, if appropriate ground or finely ground with particle size distribution in the region of < 40 ,um and d50 values of 3 - 15 ,um, or with the melt, with the aid of a mixer and converting this material into a formulation which can be applied, as is customary for the pure active substance.
However, the active substance may also be coated with wax by means of dispersing in a wax dispersion, where the finely divided wax precipitates onto the active substance by adding suitable adjuvants (such as, for example, CaCl2 solution, dilute acids).
Another preferred process for the preparation of the mixtures consists in treating formulated plant treatment compositions, for example an EC
(emulsifiable concentrate) with a wax or adding the desired amount of wax by adding a compatible wax dispersion, and, if appropriate, producing a stable preparation by means of heating.
293?4-385 A particularly preferred process for the preparation of the mixtures according to the invention consists in first preparing a ready to-use spray mixture of the plant treatment compositions in water and then adding the desired amount of a wax dispersion. The sequence of the addition can be 5 varied, and, if appropriate, it may be necessary to predilute the wax dispersion and/or the formulated plant treatment composition so as to avoid flocculation.
The use concentrations of the plant treatment compositions are 10 predetermined by the activity of the active substance and its approved application rate. The added amounts of wax, termed solids, may be varied within wide limits. They depend on the active substance of the plant treatment composition and, on the nature of the desired effect. They are within a range of 5 g/ha to 4 kg/ha of wax, with 5 g/ha to 1 kg/ha of wax being preferred and 10 g/ha to 0.5 kg/ha of wax being particularly preferred.
The invention furthermore relates to the use of the mixtures according. to the invention as plant treatment compositions.
Examples:
Example 1 In an IKA laboratory kneader (v = 500 mi) 65 g of Gol~ix~' vt~ 9c ars mix for 1 hour with 11.5 g of ~Hostalub WE 4 at a temperature of 90°C.
During this time, the wax absorbs the active substance. An analogous treatment was given to, for example, endosulfan.
Example 2 The active substance is dispersed or emulsified in water as fine particles.
The wax dispersion is added, and the dispersion is coagulated by changing the pH. Wax and active substance are bound to one another in the coagulate. When the procedure is carried out under controlled conditions, the particle size can be adjusted. Otherwise, the material is subjected to wet grinding, formulating and drying.
This process can be employed when the active substance is not highly sensitive to water and alkalis/acids. If the active substance is basic, precipitation can be provoked directly by adding a cationic dispersion. If the active Substance is aCldl(:, pieC:ipiiaiivi ~ i;ai ii be pr ovokcd vviti i a~~i i anionic dispersion. ' The quantity of wax and active substance can be matched to each other as desired if the precipitation conditions can be provoked.
To adjust redispersibility, the dried product must still undergo formulation.
In this manner, for example, Goltix VM 90 was coated from dispersion 04 with 5, 10, 15 and 20% by weight of wax.
Example 3 5 g of montanic acid polyglycol ester are dissolved in 95 g of ~Corbel (EC) with gentle warming. The resulting combination is to be brought with water to the required use concentration, as usual.
., Example 4 15.0 g of montan wax acids (AN = 140) + 4.5 g of sapogenatT"" z 50~~ are molten at 105°C. The melt is poured into 58.5 g of boiling drinking water in a thin stream, with stirring. Then, 22.0 g of cold ~Thiodan 35 are added.
The mixture is boiled up and rapidly cooled in a water-bath, with stirring.
The resulting wax-comprising dispersion, employed at the usual application rate, showed a markedly improved long-term action against Heliothis virescens larvae on cotton compared with Thiodan 35.
Analogously, montan wax acids can be incorporated into ~Desgan or OErestan.
Example 5 First, the ready-to-use spray mixture of the plant treatment composition is prepared in a suitable amount of water, and then such an amount of dispersion 02 as is required for achieving the desired effect is added, the dispersion 02 being obtained as follows:, 29.2 g of "wax LP" and 5.80 g of Sapogenat T 500 are melted at 105°C and, with stirring, poured into boiling drinking water. The mixture is boiled up and cooled in a water-bath, with stirring.
Example 6 In a drum, 100 g of wheat which has been dressed in the known manner with ~Landor are treated with 3 g of the dispersion 02, which had been adjusted to a solids content of 10% by dilution with water, mixing is then ~
continued for 10 minutes, and the mixture is allowed to dry. The thickness of the wax coating produced on the wheat kernel is approx. 3 Nm.
~ Example 7 ~Corbel with and without added wax dispersion is applied to a PE film, allowed to dry, and the decrease in the content of the active substance fenpropimorph is monitored by FTIR spectroscopy. For example, the combinations with the dispersions 01 and 02 show a markedly reduced volatility of fenpropimorph; while 50% of active substance were still detected after 4 days (23°C, atmospheric humidity 60%) without wax, 85 and 83% of active substance are still present when (1 kg of wax per ha) are added as dispersion 01 and dispersion 02, respectively.
Example 8 The dispersion 04 is diluted to almost the desired end concentration of the wax (0.5 kg of wax per hectare) in the spray mixture, plant treatment composition which has also been diluted with water is added, with stirring, and the mixture is finally diluted to the end concentration. When ~Folicur or ~Corbel were used and the mixture was applied to wheat, a markedly reduced phytotoxicity was observed, in particular at higher fungicide concentrations.
Example 9 (herbicide experiment) ~Basta and ~Roundup were used alone and in combination with waxes on non-resistant maize (site: Wolfsthal, Austria). A markedly improved initial action of Roundup against dicots is achieved by adding, for example, dispersions 01, 02, 03. In the case of both herbicides, a markedly improved long-term action is achieved by adding, for example, dispersions 01, 02 or 03.
Example 10 (fungicide experiment) Winter wheat (variety Monopol, site: Altenlengbuch, Austria), was treated once (5th May 1998) at stage 31-32 with the recommended application rates of the fungicides ~Amistar or ~Juwel, with or without addition of wax (1 kg/ha) and compared with untreated plots, and the disease level of Erysiphe graminis was scored. On the 15th June, the combination of Amistar or Juwel and dispersion 02, for example, showed no symptoms of mildew disease; untreated showed a disease level of 10%, Amistar 8%
' ~ CA 02359491 2001-07-18 ' 13 and Juwel 7%. The low disease levels achieved with the wax combinations were not even achieved by two treatments with Amistar or Juwel.
Example 11 Control of Phytophthora infestans in potatoes (variety: Quarta, outdoor conditions) A combination of ~Shirlane and the respective wax dispersion is prepared analogously to Example 5 and applied as usual. The number of spray treatments and the spray intervals was decided by the regional institute for agronomy. Weather and other parameters which allow infection constitute reasons for carrying out a spray treatment. ~Shirlane was very effective.
At the time of haulm wilting, a disease level of 30% was found.
Combinatiions of Shirlane with the wax emulsions 01, 02, 03 which were applied at the same spray timing showed an improved action resulting in a Phytophthora disease level which was up to 50% lower. A lower disease level did not produce a significant difference between the individual wax dispersions. However, the consistency of the effect is notable. The strips treated with wax emulsions had a healthier appearance until the time when the haulm was destroyed with a mechanical beater, while the crop in toto showed earlier wilting.
Example 12 Experiments with ~Juwel, ~Opus Top and ~Bion with and without wax were set up on winter wheat (variety Monopol, site: Paar, Germany) and evaluated analogously to Example 10. The combination of the fungicides with, for example, dispersion 02 (1 kg/ha wax) reduced the Erysiphe graminis and Septoria nodorum disease levels markedly compared with the fungicides ~Juwel and ~Opus Top alone. When the wax mixtures were used, the yields were up to 40% higher compared with the untreated control and up to 32% higher compared with the fungicide treatment without wax.
Example 13 Dispersion 01 At approximately 105°C, melt 25 g of montan wax ester + 5 g of "wax emulgator 4106", and portionwise stir 69.9 g of boiling drinking water into the melt. Boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROTT"" 94-08* and make up the water which has evaporated.
'Supplier: SANITIZED AG
Example 14 Dispersion 02 At approximately 105°C, melt 25 g of montan wax ester + 5 g of Sapogenat T 500, and portionwise stir 69.9 g of boiling drinking water into the melt.
Briefly boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT 94-OS and make up the water which has evaporated.
Example 15 Dispersion 03 s At approximately 105°C, melt 25 g of montan wax ester, bring 45 g of demineralized water to the. boil and stir portionwise into the molten wax.
Briefly boil up the emulsion, switch off the heating and then stir 29.9 g of cold demineralized water into the mixture and rapidly cool the emulsion to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT
94-08 and make up the water which has evaporated.
Example 16 Dispersion 04 At approximately 110-115°C, melt 20 g of montan wax ester + 5 g of "EmulgatorT"" S 3267/3", add 0.6 g of glacial acetic acid, and smartly stir the melt into 74.3 g of boiling drinking water.
Briefly boil up the emulsion and then rapidly cool to room temperature in a water-bath. Add 0.1 g of preservative SANIPROT 94-08 and make up the water which has evaporated.
Example 17 Dispersion 05 At approximately 105°C, melt 25 g of montan wax ester + 5 g of "wax emulgator 4106°, and portionwise stir 69.9 g of boiling drinking water into the melt. Briefly boil up the emulsion and then rapidly cool to room torr;pcratyra in a wa_tPr-hath, Add 01 g of preservative SANIPROT 94-G8 and make up the water which has evaporated.
Example 18 5 Dispersion 06 A 1-liter autoclave is charged with 320 g of wax oxidate of AN 17; 60 g of GenapolT"" T 250; 20 g GenapolT"" T 500 and 2 g of sodium sulfite together with 597 g of drinking water. Within 30 minutes, tine 10 internal temperature of the autoclave is brought to 140-145°C:
while stirring with an anchor mixer. The mixture is then emulsified for 20 min at the same temperature and the same stirring speed and subsequently cooled to approximately 30°C in.
the course of 40 min. 1 g of preservative SANIPROT 94-08 is 15 stirred into the cold dispersion.
Example 19 Dispersion 07 Part I
A 1-liter autoclave is charged with 273 g of wax oxidate of AN 25; 68 g of emulsifier Synperonic'~' 13/12*; 2 g of sodium pyrosulfite (=Na2Sz05) and 7 g of potassium hydroxide purity 860 (= caustic potash) together with 649 g of demineralized water. Within 30 minutes, the internal temperature of the autoclave is brought to 130°C
while stirring with an anchor mixer. The mixture is then emulsified for 20 minutes at the same temperature and the same stirring speed and subsequently cooled to approximately 30°C :in the course of 40 minutes. 1 g of preservative SANIPROT 94-08 is stirred into the cold dispersion.
*Supplier: ICI, Essen Part II
33.7 g of the dispersion prepared in part I are diluted with 33.5 g of drinking water, and 32.8 g of dispersion 03 are then added and the mixture is stirred. The solids content of the mixture is 20%.
Example 20 Dispersion 08 . ' CA 02359491 2001-07-18 Part I
At approximately 110-115°C, 24.4 g of montan wax and 4.9 g of "wax emulgator 4106" are melted. The melt is saponified with 43% strength potassium hydroxide solution. The saponified melt is stirred as a thin stream into 69.2 g of boiling demineralized water, with mechanical stirring, briefly boiled up and rapidly cooled in a water-bath. The emulsion is stabilized with 0.1 g of preservative SANIPROT 94-08, and the lost water is made up.
Part II
38.7 g of the dispersion made as in part I is diluted with 27.7 g of drinking water, and 33.6 g of dispersion 03 are then added and the mixture is stirred. The solids content of the mixture is 20%.
Claims (7)
1. A mixture of a plant treatment composition comprising an active substance and at least one wax, wherein the wax has an acid number of 5-150 and a viscosity of 5-300 mPas at 100°C.
2. A process for the preparation of a mixture as claimed in claim 1, which comprises combining the active substance with the wax in solid form or melt.
3. A process for the preparation of a mixture as claimed in claim 1, wherein the active substance is combined with a wax which has been finely ground and has a particle size of <100 µm and a d50 of 5 µm-50 µm.
4. A process for the preparation of a mixture as claimed in claim 1, wherein the active substance is treated with a wax dispersion.
5. A process for the preparation of a mixture as claimed in claim 1, wherein a formulated plant treatment composition comprising the active substance is combined with a wax dispersion.
6. A process for the preparation of mixture as claimed in claim 1, wherein a ready-to-use spray mixture comprising the active substance is treated with a wax dispersion.
7. Use of a mixture as claimed in claim 1, as a plant treatment composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19906491A DE19906491A1 (en) | 1999-02-17 | 1999-02-17 | Agrochemical mixture of active agent, e.g. fungicide, and wax of specific acid index and viscosity, providing e.g. reduced volatility and toxicity, increased reliability and rain resistance and slow release |
| DE19906491.1 | 1999-02-17 | ||
| PCT/EP2000/000835 WO2000049107A1 (en) | 1999-02-17 | 2000-02-02 | Mixture of plant-treatment agents and waxes, method for producing same and the use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2359491A1 CA2359491A1 (en) | 2000-08-24 |
| CA2359491C true CA2359491C (en) | 2007-01-16 |
Family
ID=7897707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002359491A Expired - Fee Related CA2359491C (en) | 1999-02-17 | 2000-02-02 | Mixture of plant treatment compositions with waxes, their preparation, and their use |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1157085B1 (en) |
| JP (1) | JP2002537309A (en) |
| AT (1) | ATE281505T1 (en) |
| AU (1) | AU2668800A (en) |
| CA (1) | CA2359491C (en) |
| DE (2) | DE19906491A1 (en) |
| ES (1) | ES2231157T3 (en) |
| WO (1) | WO2000049107A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011344343B2 (en) * | 2010-12-17 | 2015-09-24 | Discovery Purchaser Corporation | Composition containing insecticide-wax particles |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10361497A1 (en) * | 2003-12-23 | 2005-07-28 | Heinrichs, Annette, Dr. | Use of alkoxylated waxes, natural or synthetic, as adjuvant in plant-protection or fertilizer compositions, improves activity of fungicides, insecticides and herbicides |
| EP2205067A1 (en) * | 2007-09-24 | 2010-07-14 | Basf Se | Compositions as wound sealant |
| WO2010031508A2 (en) * | 2008-09-16 | 2010-03-25 | Bayer Cropscience Aktiengesellschaft | Insecticidal gassing agent containing active ingredient in the form of wax particles |
| US10238102B2 (en) | 2010-04-12 | 2019-03-26 | Exosect Limited | Control of arthropods in animal environments |
| EP2575447B1 (en) * | 2010-05-27 | 2015-07-01 | Exosect Limited | Liquid compositions comprising a sustained release system for insecticides |
| GB201106741D0 (en) | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositions for pathogen control in monocotyledonous plants |
| GB201106744D0 (en) * | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositions for pathogen control in soybean |
| GB201106746D0 (en) | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositions for pathogen control in oilseeds |
| GB201106745D0 (en) * | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositons for pathogen control in ornamentals |
| GB201106747D0 (en) | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositions for pathogen control in vegetables |
| GB201106748D0 (en) * | 2011-04-20 | 2011-06-01 | Exosect Ltd | Coating compositions for pathogen control in cotton |
| ES2802127B2 (en) * | 2019-07-04 | 2021-10-04 | Moracho Jimenez Angel | Procedure to treat the vines, applied composition and method of obtaining it |
| US20220061314A1 (en) * | 2020-08-28 | 2022-03-03 | Grospurt | Plant growth regulator in a semisolid or viscous medium |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL284415A (en) * | 1961-10-19 | |||
| DE3061604D1 (en) * | 1979-06-11 | 1983-02-17 | Shell Int Research | Pesticidal, toxicant-containing compositions, their preparation and their use |
| DD214519A1 (en) * | 1983-04-13 | 1984-10-17 | Bitterfeld Chemie | MINERAL-OIL-FREE TANK MIXTURES |
| DD266726A1 (en) * | 1987-11-18 | 1989-04-12 | Zeitz Hydrierwerk | ADDITIONAL COMPONENTS FOR MONTANEWAX EMULSIONS FOR THE TREATMENT OF YOUNG PLANTS |
| WO1995034200A1 (en) * | 1994-06-10 | 1995-12-21 | Fernz Corporation Limited | Biodegradable sustained release composition |
| DE19829037A1 (en) * | 1998-06-30 | 2000-01-05 | Romonta Gmbh | Wax-based wood preservative useful for protecting wood from attack by moisture, water and pests |
-
1999
- 1999-02-17 DE DE19906491A patent/DE19906491A1/en not_active Withdrawn
-
2000
- 2000-02-02 ES ES00905006T patent/ES2231157T3/en not_active Expired - Lifetime
- 2000-02-02 WO PCT/EP2000/000835 patent/WO2000049107A1/en active IP Right Grant
- 2000-02-02 DE DE50008507T patent/DE50008507D1/en not_active Expired - Fee Related
- 2000-02-02 AT AT00905006T patent/ATE281505T1/en not_active IP Right Cessation
- 2000-02-02 EP EP00905006A patent/EP1157085B1/en not_active Expired - Lifetime
- 2000-02-02 JP JP2000599838A patent/JP2002537309A/en not_active Withdrawn
- 2000-02-02 AU AU26688/00A patent/AU2668800A/en not_active Abandoned
- 2000-02-02 CA CA002359491A patent/CA2359491C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011344343B2 (en) * | 2010-12-17 | 2015-09-24 | Discovery Purchaser Corporation | Composition containing insecticide-wax particles |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000049107A1 (en) | 2000-08-24 |
| EP1157085B1 (en) | 2004-11-03 |
| EP1157085A1 (en) | 2001-11-28 |
| DE50008507D1 (en) | 2004-12-09 |
| JP2002537309A (en) | 2002-11-05 |
| DE19906491A1 (en) | 2000-08-24 |
| ES2231157T3 (en) | 2005-05-16 |
| CA2359491A1 (en) | 2000-08-24 |
| AU2668800A (en) | 2000-09-04 |
| ATE281505T1 (en) | 2004-11-15 |
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