CA2091746C - Antifoams for solid crop protection agents - Google Patents
Antifoams for solid crop protection agents Download PDFInfo
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- CA2091746C CA2091746C CA002091746A CA2091746A CA2091746C CA 2091746 C CA2091746 C CA 2091746C CA 002091746 A CA002091746 A CA 002091746A CA 2091746 A CA2091746 A CA 2091746A CA 2091746 C CA2091746 C CA 2091746C
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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
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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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
- A01N25/12—Powders or granules
-
- 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
- A01N25/30—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 characterised by the surfactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to solid active substance formula-tions which contain wetting agents in combination with a surfactant (antifoam) from the group comprising per-fluoroalkylphosphinic acid/perfluoroalkylphosphonic acids or their salts. The invention also relates to the use of these formulations, in particular in the preparation of spray slurries.
Description
~a~~~~~
HOECHST AKTIEN~ESELLSCHAFT HOE 92/F 063 Dr.WS/sch Description Antifoams fox solid crop protection agents Ths invention relates to the use of specific perfluoro alkylphosphinic acids and perfluoroalkylphosphonic acids as antifoams in solid crop~protection agents.
Solid crop protection agents are currently usually supplied in the farm of wettable powders and granules, in particular in the form of water-dispersible granules.
It is known that herbicidal, fungicidal or insecticidal active substances. are used alongside inert fillers, such as chalk, kaolin or silica, in particular surface-active substances, in the preparation of these formulations so that the preparations axe well wetted and dispersed in water when they are used. In the case of the water-dispersible granules, rapid disintegration should addi-tionally take place after introduction into water.
In addition, it is known that the surface-active sub-stances, in particular wetting agents, frequently con-tribute to intensification of the action, in particular of foliaz-acting herbicides, and then are used in a particularly high proportion in the formulations (DE-A-2 926 800).
Wetting agents also lower the surface tension of the spray slurry. As a result, uniform wetting of the leaf surface and, associated with this, frequently a better absorption of the active substances are ensured. However, because of the low surface tension, these spray slurries also tend to foam. This can lead to overflow of the spray tank and to irregular spray coatings on the plants.
HOECHST AKTIEN~ESELLSCHAFT HOE 92/F 063 Dr.WS/sch Description Antifoams fox solid crop protection agents Ths invention relates to the use of specific perfluoro alkylphosphinic acids and perfluoroalkylphosphonic acids as antifoams in solid crop~protection agents.
Solid crop protection agents are currently usually supplied in the farm of wettable powders and granules, in particular in the form of water-dispersible granules.
It is known that herbicidal, fungicidal or insecticidal active substances. are used alongside inert fillers, such as chalk, kaolin or silica, in particular surface-active substances, in the preparation of these formulations so that the preparations axe well wetted and dispersed in water when they are used. In the case of the water-dispersible granules, rapid disintegration should addi-tionally take place after introduction into water.
In addition, it is known that the surface-active sub-stances, in particular wetting agents, frequently con-tribute to intensification of the action, in particular of foliaz-acting herbicides, and then are used in a particularly high proportion in the formulations (DE-A-2 926 800).
Wetting agents also lower the surface tension of the spray slurry. As a result, uniform wetting of the leaf surface and, associated with this, frequently a better absorption of the active substances are ensured. However, because of the low surface tension, these spray slurries also tend to foam. This can lead to overflow of the spray tank and to irregular spray coatings on the plants.
The use of an antifoam as additive, which is added separately to the spray slurry, can frequently provide a remedy. However, the use as additives requires the use of a further agent in addition to the crop protection agent and, optionally, an additional wetting agent and in practice is not readily used because of the requisite additional metering and storage.
The obaect is, therefore, to find antifoams for solid formulations, which antifoams are simple to handle and do not lose their activity in the course of the formulation process and the activity of which is retained during storage of the preparations for 2 to 4 years.
A multiplicity of antifoams axe known and are reported, for example, in "Ullmanns Enzyklopadie der technischen Chemie" ("Ullmanns Encyclopedia of Industrial Chemistry"), 4th edition, volume 20, pages 411-414 and by W. Schonfeldt in "Grenzflachenaktive Alkylenoxid-Addukte"
("Surface-active alkylene oxide adducts°'), Wissenschaftliche Verlagsgesellschaft MBM, Stuttgart 1973, pages 805-853.
However, the substances mentioned in these publications axe not always suitable for the preparation of solid formulations because they cannot be used in the prepara-tion of wettable powders by grinding because of their liquid or pasty nature or their low melting point, ox because they lose their activity during the formulation process. Thus, for example, highly active silicone antifoam emulsions partly lose their antifoam properties if they are exposed to high shear forces such as occur, for example, in the preparation of water-dispersible granules by spray drying or fluidized bed granulation of aqueous suspensions. If the highly effective silicone antifoams based on powders are used, they must be added to the solid formulations by mixing after the latter have been produced. The process requires the use of suitable mixing equipment and an additional operation. Built-up granules sensitive to abrasion can be damaged by the mixing operation.
Other solid antifoams, such as, for example, E~ aluminum stearate, are not sufficiently effective, especially when large amounts of wetting agent are used in the formulation.
The use of antifoams from the group of chemicals comprising the perfluoro(C6-C18)alkylphosphinic acids and/or perfluoro(C6-C18)alkylphosphonic acids and/or their salts in liquid, surfactant-containing systems has also been disclosed (DE-A-22 33 941 and DE-A-21 336). The incorporation of the antifoams in the liquid systems is as a rule effected by addition with slow stirring.
Surprisingly, it has now been found that these substances do not lose their antifoam action even under severe mechanical stress - such as occurs, for example, when grinding wettable powder formulations in hammer mills or when wet-grinding active substances in bead mills to give aqueous suspensions and during the subsequent granulation thereof by spray drying by means of a single substance nozzle or in a fluidized bed.
The invention therefor relates to solid formulations of active substances, which are used in crop protection, and which.contain surface-active substances (wetting agents), in combination with a surfactant (antifoam) from the group of chemicals comprising the perfluoroalkylphosphinic acids and/or perfluoroalkylphosphonic acids and/or their salts.
In one aspect, the invention provides a solid formulation, comprising: 1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by - 3a -weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant {antifoam) selected from the group consisting of perfluoro- (C6-C18) -alkylphosphinic acids, perfluoro-(C6-Cl8)-alkylphosphonic acids, salts of the acids and mixtures thereof; wherein the solid formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
In a further aspect, the invention provides a wettable granular formulation for the use in crop protection, comprising: 1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant (antifoam) selected from the group consisting of perfluoro- (C6-C1$) -alkylphosphinic acids, perfluoro-(C6-C18)-alkylphosphonic acids, salts of the acids and mixtures thereof; wherein the wettable granular formulation is prepared from a mixture of formulation constituents under exposure of high shear farces in the presence of one or more of the antifoams.
The invention also provides processes for preparing the solid formulations of the invention, comprising: grinding together the active substances with any further components and optionally preparing an aqueous suspension from the solid formulation, which is subsequently granulated; or mixing the solid formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
The proportion of antifoam in the formulation can be up to 10% by weight, but in general 0.1 to 5% by weight, preferably 0.1 to 5% by weight and in particular 0.2 to 2%
by weight are used.
The obaect is, therefore, to find antifoams for solid formulations, which antifoams are simple to handle and do not lose their activity in the course of the formulation process and the activity of which is retained during storage of the preparations for 2 to 4 years.
A multiplicity of antifoams axe known and are reported, for example, in "Ullmanns Enzyklopadie der technischen Chemie" ("Ullmanns Encyclopedia of Industrial Chemistry"), 4th edition, volume 20, pages 411-414 and by W. Schonfeldt in "Grenzflachenaktive Alkylenoxid-Addukte"
("Surface-active alkylene oxide adducts°'), Wissenschaftliche Verlagsgesellschaft MBM, Stuttgart 1973, pages 805-853.
However, the substances mentioned in these publications axe not always suitable for the preparation of solid formulations because they cannot be used in the prepara-tion of wettable powders by grinding because of their liquid or pasty nature or their low melting point, ox because they lose their activity during the formulation process. Thus, for example, highly active silicone antifoam emulsions partly lose their antifoam properties if they are exposed to high shear forces such as occur, for example, in the preparation of water-dispersible granules by spray drying or fluidized bed granulation of aqueous suspensions. If the highly effective silicone antifoams based on powders are used, they must be added to the solid formulations by mixing after the latter have been produced. The process requires the use of suitable mixing equipment and an additional operation. Built-up granules sensitive to abrasion can be damaged by the mixing operation.
Other solid antifoams, such as, for example, E~ aluminum stearate, are not sufficiently effective, especially when large amounts of wetting agent are used in the formulation.
The use of antifoams from the group of chemicals comprising the perfluoro(C6-C18)alkylphosphinic acids and/or perfluoro(C6-C18)alkylphosphonic acids and/or their salts in liquid, surfactant-containing systems has also been disclosed (DE-A-22 33 941 and DE-A-21 336). The incorporation of the antifoams in the liquid systems is as a rule effected by addition with slow stirring.
Surprisingly, it has now been found that these substances do not lose their antifoam action even under severe mechanical stress - such as occurs, for example, when grinding wettable powder formulations in hammer mills or when wet-grinding active substances in bead mills to give aqueous suspensions and during the subsequent granulation thereof by spray drying by means of a single substance nozzle or in a fluidized bed.
The invention therefor relates to solid formulations of active substances, which are used in crop protection, and which.contain surface-active substances (wetting agents), in combination with a surfactant (antifoam) from the group of chemicals comprising the perfluoroalkylphosphinic acids and/or perfluoroalkylphosphonic acids and/or their salts.
In one aspect, the invention provides a solid formulation, comprising: 1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by - 3a -weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant {antifoam) selected from the group consisting of perfluoro- (C6-C18) -alkylphosphinic acids, perfluoro-(C6-Cl8)-alkylphosphonic acids, salts of the acids and mixtures thereof; wherein the solid formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
In a further aspect, the invention provides a wettable granular formulation for the use in crop protection, comprising: 1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant (antifoam) selected from the group consisting of perfluoro- (C6-C1$) -alkylphosphinic acids, perfluoro-(C6-C18)-alkylphosphonic acids, salts of the acids and mixtures thereof; wherein the wettable granular formulation is prepared from a mixture of formulation constituents under exposure of high shear farces in the presence of one or more of the antifoams.
The invention also provides processes for preparing the solid formulations of the invention, comprising: grinding together the active substances with any further components and optionally preparing an aqueous suspension from the solid formulation, which is subsequently granulated; or mixing the solid formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
The proportion of antifoam in the formulation can be up to 10% by weight, but in general 0.1 to 5% by weight, preferably 0.1 to 5% by weight and in particular 0.2 to 2%
by weight are used.
The formulation also contains 2 to 60~ by weight, prefer-ably 5 to 50~ by weight, of one or more wetting agents, preferably from the group comprising the alkanesulfon-ates,alkylnaphthalenesulfonates,alkylbenzenesulfonates, alkylpolyglycol ether-sulfonates, alkylsulfosuccinic acid half-esters, fatty acid N-methyltaurides or mixtures of the above wetting agents.
The active substances, which can be supplied in the form of solid formulations, include all suitable biologically active organic compounds, preferably herbicides and safeners, insecticides, fungicides, acaricides, nematicides, pheromones and repellents, in particular herbicidal active substances, such as glufosinate-ammonium, glyphosate, bialaphos, active substances from the phenoxy series, such as CMPP, MCPA, 2,4-D, active substances from the phenoxyphenoxy series, such as diclofopmethyl, or the heteroaryloxyphenoxy series, such as phenoxapropethyl, phenoxaprop-P-ethyl, active substances from the urea series, such as isoproturon, diuron, linuron, monolinuron and chlortoluron, active substances from the series comprising the sulfonylureas, such as amidosulfuron, tribenuron (DPX-L5300), thiameturon-methyl (DPX-M6316), metsulfuron-methyl (DPX-T6376), primisulfuron-methyl and nicosulfuron, active substances from the series comprising the triazines, such as atrazine or simazine, active substances from the series comprising the imidazolinones, such as imazapyr, imazac,~uin, imazethapyr and imazamethabenz, and diphenyl ether derivatives, for example acifluorfen, fluoroglycofen, lactofen and bifenox, dicotylene herbicides, for example ioxynil, bromoxynil, dicamba, diflufenican, fluroxypyr, phen-medipham, desmedipham, bentazone, metamitron, metribuzin, chloridazon, ethofumesate or the active substance trifluralin, and safeners, such as, for example, the compounds described in EP-A-86750, EP-A-94349, EP-A-191736, EP-A-346620, EP-A-333131, EP-A-269806, EP-A-159290, DE-A-2546845, PCT/EP-90/02020 and PCT/EP-90/01966;
fungicidal active substances, such as, for example, active substances from the series comprising the azoles, for example triadimefon, cyproconazole, myclobutanil and dichlobutrazol, active substances from the series comprising the dithiocarbamates, such as maneb, zineb and mancozeb, the benzimidazoles, for example carbendazime, or active substances such as, for example, procymidone, iprodione, vinchlozoline, thiophanate-methyl, cymoxanil, folpet, copper oxychloride, sulfur or TPTH; insecticidal active substances, such as, for example, active substances from the series comprising the pyrethroids, such as deltamethrin, acrinathrin, tralomethrin, permethrin and cypermethrin, active substances from the benzoylurea series, such as diflubenzuron, or active substances such as, for example, endosulfan, pirimicarb or silafluofen.
The said active substances can also be supplied in com-bination with one another in the form of solid formula-tions. The active substance content is as a rule 1 to 80~ by weight, preferably 5 to 60~ by weight.
Suitable perfluoroalkyl group-containing surfactants are, in particular, perfluoro(C6-Clz)alkylphosphinic acids and perfluoro(C6-Clz)alkylphosphonic acids and their alkali metal salts, such as sodium or potassium salts, their ammonium salts, (Cz-Cle)-alkylammonium salts and also salts with (Clo-Clay-alkylamineethoxylates and ethylene-diamineethoxylates or mixtures thereof. The perfluoro-alkyl group-containing surfactants are commercially available, for example ~Fluowot PP (mixture of (C6-Clz)-perfluoroalkylphosphinic acids and (Cs-Clz)-Perfluoro-alkylphosphonic acids, Hoechst) or can be prepared by known methods (DE-A 21 11 167).
~~9~.'~4~
The active substances, which can be supplied in the form of solid formulations, include all suitable biologically active organic compounds, preferably herbicides and safeners, insecticides, fungicides, acaricides, nematicides, pheromones and repellents, in particular herbicidal active substances, such as glufosinate-ammonium, glyphosate, bialaphos, active substances from the phenoxy series, such as CMPP, MCPA, 2,4-D, active substances from the phenoxyphenoxy series, such as diclofopmethyl, or the heteroaryloxyphenoxy series, such as phenoxapropethyl, phenoxaprop-P-ethyl, active substances from the urea series, such as isoproturon, diuron, linuron, monolinuron and chlortoluron, active substances from the series comprising the sulfonylureas, such as amidosulfuron, tribenuron (DPX-L5300), thiameturon-methyl (DPX-M6316), metsulfuron-methyl (DPX-T6376), primisulfuron-methyl and nicosulfuron, active substances from the series comprising the triazines, such as atrazine or simazine, active substances from the series comprising the imidazolinones, such as imazapyr, imazac,~uin, imazethapyr and imazamethabenz, and diphenyl ether derivatives, for example acifluorfen, fluoroglycofen, lactofen and bifenox, dicotylene herbicides, for example ioxynil, bromoxynil, dicamba, diflufenican, fluroxypyr, phen-medipham, desmedipham, bentazone, metamitron, metribuzin, chloridazon, ethofumesate or the active substance trifluralin, and safeners, such as, for example, the compounds described in EP-A-86750, EP-A-94349, EP-A-191736, EP-A-346620, EP-A-333131, EP-A-269806, EP-A-159290, DE-A-2546845, PCT/EP-90/02020 and PCT/EP-90/01966;
fungicidal active substances, such as, for example, active substances from the series comprising the azoles, for example triadimefon, cyproconazole, myclobutanil and dichlobutrazol, active substances from the series comprising the dithiocarbamates, such as maneb, zineb and mancozeb, the benzimidazoles, for example carbendazime, or active substances such as, for example, procymidone, iprodione, vinchlozoline, thiophanate-methyl, cymoxanil, folpet, copper oxychloride, sulfur or TPTH; insecticidal active substances, such as, for example, active substances from the series comprising the pyrethroids, such as deltamethrin, acrinathrin, tralomethrin, permethrin and cypermethrin, active substances from the benzoylurea series, such as diflubenzuron, or active substances such as, for example, endosulfan, pirimicarb or silafluofen.
The said active substances can also be supplied in com-bination with one another in the form of solid formula-tions. The active substance content is as a rule 1 to 80~ by weight, preferably 5 to 60~ by weight.
Suitable perfluoroalkyl group-containing surfactants are, in particular, perfluoro(C6-Clz)alkylphosphinic acids and perfluoro(C6-Clz)alkylphosphonic acids and their alkali metal salts, such as sodium or potassium salts, their ammonium salts, (Cz-Cle)-alkylammonium salts and also salts with (Clo-Clay-alkylamineethoxylates and ethylene-diamineethoxylates or mixtures thereof. The perfluoro-alkyl group-containing surfactants are commercially available, for example ~Fluowot PP (mixture of (C6-Clz)-perfluoroalkylphosphinic acids and (Cs-Clz)-Perfluoro-alkylphosphonic acids, Hoechst) or can be prepared by known methods (DE-A 21 11 167).
~~9~.'~4~
In addition to the said active substances, the effective antifoams found and wetting agents, the solid formulations can also contain further conventional formulating auxiliaries, such as, for example, dispers-ants, agglomeration auxiliaries, stabilizers, inert fillers and water-soluble substances, for example ammonium sulfate, urea or sodium sulfate, the content of these substances as a rule being 0 to 70~ by weight, preferably 5 to 50~ by weight.
The said active substances are also known and are described in "Pesticide Manual'° (by the British Crop Protection Council) or in "Farm Chemicals Handbook 91"
(Meister Publishing Company, Willoughby, Ohio).
The said perfluoroalkyl group-containing antifoams can also be used in combination with antifoams belonging to other substance categories, in particular in combination with silicone-based antifoams.
By means of the perfluoroalkyl group-containing surfact-ants used according to the invention it is possible to provide wettable powder formulations and granule formula-tions, and in particular also water-emulsifiable granules, with antifoams which do not lose their activity either during the preparation or during storage of the products for 2 to 4 years.
In addition to the said active substances, the perfluoro-alkoxy graup-containing surfactants and wetting agents and also, optionally, further conventional formulating auxiliaries, the said water-emulsifiable granules can contain a high-boiling solvent or solvent mixture. They also contain an at least partially water-soluble casing-and structure-forming material, which preferably essen-tially comprises at least one substance from the group comprising gelatin, gum arabic, cellulose derivatives, starch derivatives, sodium alginates, polyvinyl alcohols and polyvinylpyrrolidones. Its content is 10 to 80~ by weight, prefer«bly 25 to 60~ by weight. A casing- and structure-forming material which essentially comprises a polyvinyl alcohol obtained by partial hydrolysis of polyvinyl acetate or a mixture of such polyvinyl alcohols is preferred. Polyvinyl alcohols, or mixtures thereof, with a degree of hydrolysis of preferably 72 to 99 mold and a viscosity of preferably 2 to l8cP, determined in a 4~ strength aqueous solution at 20°C (for example ~Mowiol grades), are obtained by hydrolysis, preferably partial hydrolysis, of polyvinyl acetate. The polyvinyl alcohols preferred for the present invention have a molar mass of preferablX 10,000 to 20,000. They are prepared by partial, preferably 72 to 99 mold, alkaline hydrolysis of corresponding polyvinyl acetates.
When the said water-soluble materials are used, in particular when specific polyvinyl alcohol grades or mixtures thereof are used, water-emulsifiable granules which have an average particle diameter of 0.3 to 5 mm, preferably 0.5 to 2 mm, and which do not produce dust, are free-flowing, can readily be metered volumetrically and are readily emulsifiable in water are formed, for example by the fluidized bed process using the counter-current principle.
Suitable high-boiling organic solvents are mainly high-boiling aromatic compounds, such as, for example, 1- or 2-methylnaphthalene, dimethylnaphthalenes and other polynuclear aromatic compounds. However, other water-immiscible solvents axe also suitable, for example aromatic compounds, such as alkylbenzenes and xylenes, aliphatic compounds, such as paraffin oils, vegetable oils, alicyclic compounds, alkanols, such as cyclohexanol and isooctyl alcohol, ethers, ketones, such as cyclo-hexanone, 4-methylcyclohexanone and isophorone, and esters, such as ethyl benzoate and tri-n-butyl phosphate.
Liquid pesticide active substances can also be used without organic solvents. The high-boiling solvent or solvent mixture content is 0 to 80~, preferably 20 to 60~.
The antifoams are also effective if they are added to the aqueous sprax slurries of the formulations before these are applied.
The invention therefore also relates to the dilute formulations (spray slurries) which contain the constituents of the solid formulations described in approximately 50- to 500-fold dilution.
The following examples illustrate the invention without restricting the invention thereto. The percentages are by weight.
Example 1 Glufosinate-ammonium 20 WG
20$ glufosinate-ammonium 40~ ~Hostapur OS
39~ ammonium sulfate 1 ~ ~Fluowet PP
The granules are prepared in accordance with DE-A-39 26 800 by spraying an aqueous solution of glufosinate-ammonium onto the pulverulent mixture of the remaining constituents of the formulation in a fluidized bed.
Example 2 Glufosinate-ammonium + diuron (12 + 18) WG
12.0 glufosinate-ammonium 18.2$ diuron, 99~ strength 16.0 ~Hostapur OS
12.0$ ~Genapol LRO
~~91~4f~
_ g 5.0$ ~Vanisperx GB
1.8$ ~Fluowet PP
35.0 kaolin The granules are prepared in accordance with IDE-A-39 26 800 from an aqueous suspension having a solids content of 40~ by granulation in a fluidized bed. The suspension is prepared by grinding all of the formulation constituents extremely finely in water with the aid of a bead mill.
Example 3 Isoproturon + amidosulfuron (60 + 1.5) WP
60.61$ IPU, technical grade, 99~ strength 1.56$ amidosulfuron, technical grade, 96~ strength 10.00 ~Geropon SC 213 6.00 ~Texapon K12 21.OO~k kaolin 1777 0.83 ~'Fluowet PP
The wettable powder is prepared by grinding all of the formulation constituents in a hammer mill.
Example 4 Isoproturon -~ amidosulfuron (75 + 1.5) WG
75.76 IPU, technical grade, 99$ strength 1.56 amidosulfuron, technical grade, 96~ strength 10.00 ~Geropon SC213 6.00 ~Texapon K12 0.30 ~Forlanit P
5.20$ kaolin 1777 0.50 silicone antifoam SE2 0.68 ~'Fluowet PP-potassium The granules are prepared by spraying an aqueous suspen-sion having a solids content of 50$ by means of a single substance nozzle and drying in a conventional spraying tower using the co-current principle.
The aqueous suspension is prepared by grinding all of the formulation constituents in a bead mill.
Example 5 Amidosulfuron + bromoxynil + diflufenican (2.2 + 37.5 +
7.5) WG
40.32 bromoxynil, technical grade, 93~ strength 2.37 amidosulfuron, technical grade, 93~ strength 7.73 diflufenican, technical grade, 97~ strength 8.00 ~Geropon SC 213 4.00 ~Texapon K 12 2.00$ ~Luviskol K 30 34.58 kaolin 1777 0.50$ silicone antifoam SE 2 0.2.5 antifoam 416 0.25 ~Fluowet PP
The granules are prepared from an aqueous suspension having a solids content of 50~ in a fluidized bed. For preparation of the aqueous suspension, the formulation constituents with the exception of antifoam 416 are ground in a bead mill and antifoam 416 is then added with slow stirring.
Example 6 Amidosulfuron 50 WP
52.08 amidosulfuron, technical grade, 96$ strength 10.00 ~Tamol NNO
6.00 ~Texapon K 12 20.00$ kaolin 1777 11.40$ ~Wessalon S
0.52 ~Fluowet PP
The wettable powder is prepared by grinding all of the formulation constituents in a hammer mill.
Example 7 Carbendazim 80 WG
80.88 carbendazim, technical grade, 99~ strength 5.62 ~Tamol NNO
2.90 ~Mowiol 3/83 5.60$ starch 0 . 2 ~ ~'Bronidox L
0,2$ silicone antifoam SE 2 3.60$ ~Forlanit P
The granules are prepared by spray drying an aqueous suspension having a solids content of 55~ in a conven-tional spray drier and the aqueous suspension is prepared by grinding all of the formulation constituents in a bead mill.
Example 8 Fluoxaprop-P-ethyl -E fenchlorazole-ethyl (12 + 6) WEG
12.50 fluoxaprop-P-ethyl, technical grade, 96~ strength 6.15 fenchlorazole-ethyl, technical grade, 97.6$
strength 43.50 ~'Solvesso 200 (Exxon Chemical) 20.00 ~'Mowiol 3/83 11.35 ~'Mowiol 4/88 5.00 ~'I~Tostapur OSB
0.50$ ~Fluowet PP
1.00 residuvl moisture 101 g of a polyvinyl alcohol prepared by partial saponi-fication of polyvinyl acetate and having a viscosity of 3 cP (determined in 4~ strength aqueous solution at 20°C) and a degree of hydrolysis of 83 mold are dissolved in 600 g of water and 57.3 g of a polyvinyl alcohol prepared in the same way and having a viscosity of 4 cP and a degree of hydrolysis of 88 mold are added slowly, with vigorous stirring. The aqueous phase is then homogenized.
A solution of 63 g of fenoxaprop-P-ethyl and 31 g of fenchlorazole-ethyl in 220 g of ~Solvesso 200 is then allowed to run into the aqueous phase while continuing to stir and the speed of rotation of the stirrer is then increased so that the oily droplets formed in the aqueous phase have an average diameter of 5 to 10 Vim.
The resulting suspension is then metered into a laboratory fluidized bed drier. The water-dispersible granules thus obtained have a particle diameter of 0.5 to 2 mm. A stable suspoemulsion forms in water.
The surfactants and auxiliaries listed in Examples 1 to 8 are known and can be obtained from Hoechst AG (~Hostapur OS, ~Genapol LRO, ~Mowiol) Henkel KG (~Texapon K12, ~Forlanit P, ~Bromidox L) BASF (~Taniol NNO, ~'Zuxiskol K 30 ) blacker Chemie GmbH (Silicone antifoam SE 2) Rhone-Poulenc (~Geropon SC 213, Antifoam 416) Borregaard A.S. (~Vanisperse CB) Exxon Chemical (~Solvesso) Foam test A 1 1 measuring cylinder (diameter: 5 cm) closeable with a glass stopper is filled with 500 ml of standard water D (342 ppm CaC03 hardness according to CIPAC Handbook 1, p. 878). After adding 5 g of product, the closed cylinder is turned 10 times through 180° and back again. Immedi-ately thereafter the time taken for the foam formed to collapse is measured.
Result:
~(f~1'~4 When formulations which contain the antifoams according to the invention are used, 90~ of the foam disappears within 2 to 3 min and frequently the entire foam also collapses within 1 min.
When formulations are used which are prepared by the processes indicated in the examples and which do not contain the antifoams according to the invention or silicone-based antifoams, the foam frequently remains stable for more than 30 min.
The said active substances are also known and are described in "Pesticide Manual'° (by the British Crop Protection Council) or in "Farm Chemicals Handbook 91"
(Meister Publishing Company, Willoughby, Ohio).
The said perfluoroalkyl group-containing antifoams can also be used in combination with antifoams belonging to other substance categories, in particular in combination with silicone-based antifoams.
By means of the perfluoroalkyl group-containing surfact-ants used according to the invention it is possible to provide wettable powder formulations and granule formula-tions, and in particular also water-emulsifiable granules, with antifoams which do not lose their activity either during the preparation or during storage of the products for 2 to 4 years.
In addition to the said active substances, the perfluoro-alkoxy graup-containing surfactants and wetting agents and also, optionally, further conventional formulating auxiliaries, the said water-emulsifiable granules can contain a high-boiling solvent or solvent mixture. They also contain an at least partially water-soluble casing-and structure-forming material, which preferably essen-tially comprises at least one substance from the group comprising gelatin, gum arabic, cellulose derivatives, starch derivatives, sodium alginates, polyvinyl alcohols and polyvinylpyrrolidones. Its content is 10 to 80~ by weight, prefer«bly 25 to 60~ by weight. A casing- and structure-forming material which essentially comprises a polyvinyl alcohol obtained by partial hydrolysis of polyvinyl acetate or a mixture of such polyvinyl alcohols is preferred. Polyvinyl alcohols, or mixtures thereof, with a degree of hydrolysis of preferably 72 to 99 mold and a viscosity of preferably 2 to l8cP, determined in a 4~ strength aqueous solution at 20°C (for example ~Mowiol grades), are obtained by hydrolysis, preferably partial hydrolysis, of polyvinyl acetate. The polyvinyl alcohols preferred for the present invention have a molar mass of preferablX 10,000 to 20,000. They are prepared by partial, preferably 72 to 99 mold, alkaline hydrolysis of corresponding polyvinyl acetates.
When the said water-soluble materials are used, in particular when specific polyvinyl alcohol grades or mixtures thereof are used, water-emulsifiable granules which have an average particle diameter of 0.3 to 5 mm, preferably 0.5 to 2 mm, and which do not produce dust, are free-flowing, can readily be metered volumetrically and are readily emulsifiable in water are formed, for example by the fluidized bed process using the counter-current principle.
Suitable high-boiling organic solvents are mainly high-boiling aromatic compounds, such as, for example, 1- or 2-methylnaphthalene, dimethylnaphthalenes and other polynuclear aromatic compounds. However, other water-immiscible solvents axe also suitable, for example aromatic compounds, such as alkylbenzenes and xylenes, aliphatic compounds, such as paraffin oils, vegetable oils, alicyclic compounds, alkanols, such as cyclohexanol and isooctyl alcohol, ethers, ketones, such as cyclo-hexanone, 4-methylcyclohexanone and isophorone, and esters, such as ethyl benzoate and tri-n-butyl phosphate.
Liquid pesticide active substances can also be used without organic solvents. The high-boiling solvent or solvent mixture content is 0 to 80~, preferably 20 to 60~.
The antifoams are also effective if they are added to the aqueous sprax slurries of the formulations before these are applied.
The invention therefore also relates to the dilute formulations (spray slurries) which contain the constituents of the solid formulations described in approximately 50- to 500-fold dilution.
The following examples illustrate the invention without restricting the invention thereto. The percentages are by weight.
Example 1 Glufosinate-ammonium 20 WG
20$ glufosinate-ammonium 40~ ~Hostapur OS
39~ ammonium sulfate 1 ~ ~Fluowet PP
The granules are prepared in accordance with DE-A-39 26 800 by spraying an aqueous solution of glufosinate-ammonium onto the pulverulent mixture of the remaining constituents of the formulation in a fluidized bed.
Example 2 Glufosinate-ammonium + diuron (12 + 18) WG
12.0 glufosinate-ammonium 18.2$ diuron, 99~ strength 16.0 ~Hostapur OS
12.0$ ~Genapol LRO
~~91~4f~
_ g 5.0$ ~Vanisperx GB
1.8$ ~Fluowet PP
35.0 kaolin The granules are prepared in accordance with IDE-A-39 26 800 from an aqueous suspension having a solids content of 40~ by granulation in a fluidized bed. The suspension is prepared by grinding all of the formulation constituents extremely finely in water with the aid of a bead mill.
Example 3 Isoproturon + amidosulfuron (60 + 1.5) WP
60.61$ IPU, technical grade, 99~ strength 1.56$ amidosulfuron, technical grade, 96~ strength 10.00 ~Geropon SC 213 6.00 ~Texapon K12 21.OO~k kaolin 1777 0.83 ~'Fluowet PP
The wettable powder is prepared by grinding all of the formulation constituents in a hammer mill.
Example 4 Isoproturon -~ amidosulfuron (75 + 1.5) WG
75.76 IPU, technical grade, 99$ strength 1.56 amidosulfuron, technical grade, 96~ strength 10.00 ~Geropon SC213 6.00 ~Texapon K12 0.30 ~Forlanit P
5.20$ kaolin 1777 0.50 silicone antifoam SE2 0.68 ~'Fluowet PP-potassium The granules are prepared by spraying an aqueous suspen-sion having a solids content of 50$ by means of a single substance nozzle and drying in a conventional spraying tower using the co-current principle.
The aqueous suspension is prepared by grinding all of the formulation constituents in a bead mill.
Example 5 Amidosulfuron + bromoxynil + diflufenican (2.2 + 37.5 +
7.5) WG
40.32 bromoxynil, technical grade, 93~ strength 2.37 amidosulfuron, technical grade, 93~ strength 7.73 diflufenican, technical grade, 97~ strength 8.00 ~Geropon SC 213 4.00 ~Texapon K 12 2.00$ ~Luviskol K 30 34.58 kaolin 1777 0.50$ silicone antifoam SE 2 0.2.5 antifoam 416 0.25 ~Fluowet PP
The granules are prepared from an aqueous suspension having a solids content of 50~ in a fluidized bed. For preparation of the aqueous suspension, the formulation constituents with the exception of antifoam 416 are ground in a bead mill and antifoam 416 is then added with slow stirring.
Example 6 Amidosulfuron 50 WP
52.08 amidosulfuron, technical grade, 96$ strength 10.00 ~Tamol NNO
6.00 ~Texapon K 12 20.00$ kaolin 1777 11.40$ ~Wessalon S
0.52 ~Fluowet PP
The wettable powder is prepared by grinding all of the formulation constituents in a hammer mill.
Example 7 Carbendazim 80 WG
80.88 carbendazim, technical grade, 99~ strength 5.62 ~Tamol NNO
2.90 ~Mowiol 3/83 5.60$ starch 0 . 2 ~ ~'Bronidox L
0,2$ silicone antifoam SE 2 3.60$ ~Forlanit P
The granules are prepared by spray drying an aqueous suspension having a solids content of 55~ in a conven-tional spray drier and the aqueous suspension is prepared by grinding all of the formulation constituents in a bead mill.
Example 8 Fluoxaprop-P-ethyl -E fenchlorazole-ethyl (12 + 6) WEG
12.50 fluoxaprop-P-ethyl, technical grade, 96~ strength 6.15 fenchlorazole-ethyl, technical grade, 97.6$
strength 43.50 ~'Solvesso 200 (Exxon Chemical) 20.00 ~'Mowiol 3/83 11.35 ~'Mowiol 4/88 5.00 ~'I~Tostapur OSB
0.50$ ~Fluowet PP
1.00 residuvl moisture 101 g of a polyvinyl alcohol prepared by partial saponi-fication of polyvinyl acetate and having a viscosity of 3 cP (determined in 4~ strength aqueous solution at 20°C) and a degree of hydrolysis of 83 mold are dissolved in 600 g of water and 57.3 g of a polyvinyl alcohol prepared in the same way and having a viscosity of 4 cP and a degree of hydrolysis of 88 mold are added slowly, with vigorous stirring. The aqueous phase is then homogenized.
A solution of 63 g of fenoxaprop-P-ethyl and 31 g of fenchlorazole-ethyl in 220 g of ~Solvesso 200 is then allowed to run into the aqueous phase while continuing to stir and the speed of rotation of the stirrer is then increased so that the oily droplets formed in the aqueous phase have an average diameter of 5 to 10 Vim.
The resulting suspension is then metered into a laboratory fluidized bed drier. The water-dispersible granules thus obtained have a particle diameter of 0.5 to 2 mm. A stable suspoemulsion forms in water.
The surfactants and auxiliaries listed in Examples 1 to 8 are known and can be obtained from Hoechst AG (~Hostapur OS, ~Genapol LRO, ~Mowiol) Henkel KG (~Texapon K12, ~Forlanit P, ~Bromidox L) BASF (~Taniol NNO, ~'Zuxiskol K 30 ) blacker Chemie GmbH (Silicone antifoam SE 2) Rhone-Poulenc (~Geropon SC 213, Antifoam 416) Borregaard A.S. (~Vanisperse CB) Exxon Chemical (~Solvesso) Foam test A 1 1 measuring cylinder (diameter: 5 cm) closeable with a glass stopper is filled with 500 ml of standard water D (342 ppm CaC03 hardness according to CIPAC Handbook 1, p. 878). After adding 5 g of product, the closed cylinder is turned 10 times through 180° and back again. Immedi-ately thereafter the time taken for the foam formed to collapse is measured.
Result:
~(f~1'~4 When formulations which contain the antifoams according to the invention are used, 90~ of the foam disappears within 2 to 3 min and frequently the entire foam also collapses within 1 min.
When formulations are used which are prepared by the processes indicated in the examples and which do not contain the antifoams according to the invention or silicone-based antifoams, the foam frequently remains stable for more than 30 min.
Claims (22)
1. A solid formulation, comprising:
1 to 80% by weight of a solid active substance for use in crop protection; and
1 to 80% by weight of a solid active substance for use in crop protection; and
2 to 60% by weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant (antifoam) selected from the group consisting of perfluoro- (C6-C18) -alkylphosphinic acids, perfluoro- (C6-C18) -alkylphosphonic acids, salts of the acids and mixtures thereof;
wherein the solid formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
2. The solid formulation as claimed in claim 1, wherein the antifoam content is 0.2 to 2% by weight.
wherein the solid formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
2. The solid formulation as claimed in claim 1, wherein the antifoam content is 0.2 to 2% by weight.
3. The solid formulation as claimed in claim 1 or 2, comprising at least one active substance selected from the group consisting of herbicides, safeners, fungicides and insecticides.
4. The solid formulation as claimed in any one of claims 1 to 3, wherein the antifoam is selected from the group consisting of perfluoro-(C6-C18)-alkylphosphinic acids, perfluoro-(C6-C18)-alkylphosphonic acids, alkali metal salts of the acids, ammonium salts of the acids, C2-C18-alkylammonium salts of the acids, salts of the acids with C10-C18-alkylamineethoxylates or ethylenediamineethoxylates mixtures thereof.
5. The solid formulation as claimed in any one of claims 1 to 4, further comprising conventional formulating auxiliaries selected from the group consisting of dispersants, agglomeration auxiliaries, stabilizers and fillers.
6. The solid formulation as claimed in any one of claims 1 to 5, which is granules.
7. The solid formulation as claimed in claim 6, which is water-emulsifiable granules.
8. The solid formulation as claimed in any one of claims 1 to 5, which is a wettable powder.
9. A process for the preparation of a solid formulation as claimed in any one of claims 1 to 8, wherein the active substances are ground together with any further components.
10. The process as claimed in claim 9, further comprising preparing an aqueous suspension from the solid formulation, which is subsequently granulated.
11. Use of a solid formulation as claimed in any one of claims 1 to 8, in the preparation of dilute formulations (spray slurries).
12. Use of a wetting agent in combination with a surfactant (antifoam) as defined in claim 1 or 4, in the preparation of a solid active substance formulation.
13. A wettable granular formulation for the use in crop protection, comprising:
1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant (antifoam) selected from the group consisting of perfluoro- (C6-C18) -alkylphosphinic acids, perfluoro- (C6-C18) -alkylphosphonic acids, salts of the acids and mixtures thereof;
wherein the wettable granular formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
1 to 80% by weight of a solid active substance for use in crop protection; and 2 to 60% by weight of one or more wetting agents in combination with 0.1 to 10 percent by weight of a surfactant (antifoam) selected from the group consisting of perfluoro- (C6-C18) -alkylphosphinic acids, perfluoro- (C6-C18) -alkylphosphonic acids, salts of the acids and mixtures thereof;
wherein the wettable granular formulation is prepared from a mixture of formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
14. A wettable granular formulation as claimed in claim 13, wherein the granulation was effected by spray-drying of an aqueous suspension of constituents comprising one or more of the antifoams.
15. A wettable granular formulation as claimed in claim 13 or 14, wherein the antifoam content is 0.2 to 2 percent by weight.
16. A wettable granular formulation as claimed in any one of claims 13 to 15, wherein the granules have an average particle size of 0.3 to 5 mm.
17. A wettable granular formulation as claimed in claim 16, wherein the granules have an average particle size of 0.5 to 2 mm.
18. A process for the preparation of a solid formulation as claimed in any one of claims 1 to 8, comprising mixing of the solid formulation constituents under exposure of high shear forces in the presence of one or more of the antifoams.
19. The process as claimed in claim 18, wherein the solid formulation is a wettable granule prepared by spray-drying of an aqueous suspension of constituents comprising one or more of the antifoams.
20. The process as claimed in claim 19, wherein the aqueous suspension is prepared by wet-grinding of the solids before the spray-drying granulation.
21. The process as claimed in claim 19 or 20, wherein the granules have an average particle size of 0.3 to 5 mm.
22. The process as claimed in claim 21, wherein the granules have an average particle size of 0.5 to 2 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4208514 | 1992-03-17 | ||
| DEP4208514.4 | 1992-03-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2091746A1 CA2091746A1 (en) | 1993-09-18 |
| CA2091746C true CA2091746C (en) | 2003-11-25 |
Family
ID=6454276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002091746A Expired - Fee Related CA2091746C (en) | 1992-03-17 | 1993-03-16 | Antifoams for solid crop protection agents |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0561265B1 (en) |
| JP (1) | JP3717190B2 (en) |
| KR (1) | KR100564514B1 (en) |
| AT (1) | ATE139908T1 (en) |
| AU (1) | AU665060B2 (en) |
| CA (1) | CA2091746C (en) |
| DE (1) | DE59303101D1 (en) |
| DK (1) | DK0561265T3 (en) |
| ES (1) | ES2090739T3 (en) |
| HU (1) | HU213861B (en) |
| IL (1) | IL105056A (en) |
| MX (1) | MX9301474A (en) |
| ZA (1) | ZA931856B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2713045B1 (en) * | 1993-12-03 | 1996-08-09 | Roussel Uclaf | Granules emulsifiable in water, their preparation process and their application as pesticides. |
| EP0878128A1 (en) * | 1997-05-07 | 1998-11-18 | American Cyanamid Company | Solid formulations |
| US6030924A (en) * | 1997-05-07 | 2000-02-29 | American Cyanamid Company | Solid formulations |
| US6599625B2 (en) * | 2001-10-31 | 2003-07-29 | E. I. Du Pont De Nemours And Company | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2233941C3 (en) * | 1972-07-11 | 1978-03-02 | Cassella Farbwerke Mainkur Ag, 6000 Frankfurt | Use of perfluoroalkylphosphorus compounds as foam suppressants |
| DE2546845A1 (en) * | 1975-10-18 | 1977-04-28 | Basf Ag | Herbicidal (iso)quinolyloxy-alkanoic acid derivs. - prepd. e.g. by reacting hydroxy-(iso)quinoline cpds. with halo-alkanamides |
| DE4021336A1 (en) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | Aq. compsns. contg. anionic wetting agent and foam inhibitor |
| DE3926800A1 (en) * | 1989-08-14 | 1991-02-21 | Hoechst Ag | WATER-DISPERSIBLE GRANULES FOR USE IN PLANT PROTECTION |
-
1993
- 1993-03-10 ES ES93103853T patent/ES2090739T3/en not_active Expired - Lifetime
- 1993-03-10 EP EP93103853A patent/EP0561265B1/en not_active Revoked
- 1993-03-10 AT AT93103853T patent/ATE139908T1/en not_active IP Right Cessation
- 1993-03-10 DE DE59303101T patent/DE59303101D1/en not_active Expired - Fee Related
- 1993-03-10 DK DK93103853.3T patent/DK0561265T3/en active
- 1993-03-15 IL IL10505693A patent/IL105056A/en not_active IP Right Cessation
- 1993-03-16 MX MX9301474A patent/MX9301474A/en not_active IP Right Cessation
- 1993-03-16 ZA ZA931856A patent/ZA931856B/en unknown
- 1993-03-16 AU AU35274/93A patent/AU665060B2/en not_active Ceased
- 1993-03-16 HU HU9300745A patent/HU213861B/en not_active IP Right Cessation
- 1993-03-16 KR KR1019930004001A patent/KR100564514B1/en not_active IP Right Cessation
- 1993-03-16 CA CA002091746A patent/CA2091746C/en not_active Expired - Fee Related
- 1993-03-16 JP JP05607793A patent/JP3717190B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| HU213861B (en) | 1997-11-28 |
| JP3717190B2 (en) | 2005-11-16 |
| DE59303101D1 (en) | 1996-08-08 |
| DK0561265T3 (en) | 1996-10-14 |
| ZA931856B (en) | 1993-10-05 |
| MX9301474A (en) | 1994-01-31 |
| JPH0641510A (en) | 1994-02-15 |
| HUT63588A (en) | 1993-09-28 |
| AU3527493A (en) | 1993-09-23 |
| HU9300745D0 (en) | 1993-05-28 |
| KR100564514B1 (en) | 2006-06-14 |
| CA2091746A1 (en) | 1993-09-18 |
| KR930019108A (en) | 1993-10-18 |
| ATE139908T1 (en) | 1996-07-15 |
| IL105056A0 (en) | 1993-07-08 |
| ES2090739T3 (en) | 1996-10-16 |
| EP0561265A1 (en) | 1993-09-22 |
| EP0561265B1 (en) | 1996-07-03 |
| AU665060B2 (en) | 1995-12-14 |
| IL105056A (en) | 1999-11-30 |
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