WO1999040786A1 - Formulations de polymeres en perles - Google Patents

Formulations de polymeres en perles Download PDF

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Publication number
WO1999040786A1
WO1999040786A1 PCT/EP1999/000562 EP9900562W WO9940786A1 WO 1999040786 A1 WO1999040786 A1 WO 1999040786A1 EP 9900562 W EP9900562 W EP 9900562W WO 9940786 A1 WO9940786 A1 WO 9940786A1
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WO
WIPO (PCT)
Prior art keywords
weight
bead polymer
agrochemical active
active ingredient
polymer formulations
Prior art date
Application number
PCT/EP1999/000562
Other languages
German (de)
English (en)
Inventor
Wolfgang Podszun
Uwe Priesnitz
Jürgen KÜHNHOLD
Helmut Lembrich
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU32514/99A priority Critical patent/AU3251499A/en
Publication of WO1999040786A1 publication Critical patent/WO1999040786A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—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 solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • the present invention relates to new bead polymer formulations of agrochemical active substances, a process for the preparation of these preparations and their use for the application of agrochemical active substances.
  • EP-A 0 201 214 already discloses microparticles which can be prepared from ethylenically unsaturated monomers and which contain pesticidal active ingredients and have a particle diameter of between approximately 0.01 and 250 ⁇ m.
  • a disadvantage of these preparations is that the active components, especially when they are substances with a relatively high vapor pressure, are not always released over a sufficiently long period of time and in the amount desired in each case.
  • formulations have been described which contain easily washable agrochemical active ingredients in microencapsulated form in unsaturated polyester resins (cf. EP-A 0 517 669).
  • EP-A 0 517 669 unsaturated polyester resins
  • EP-A 0 281 918 shows that macroporous, crosslinked polystyrene bead polymers are suitable as carriers for agricultural chemicals and can be used in crop protection. Even when these preparations are used, however, the speed and the amount in which the agricultural chemicals are released often leave something to be desired.
  • the solid phase contains, the content of agrochemical active ingredient between 5 and 75 wt .-% and the solid phase has an average particle size between 1 and 100 microns
  • bead polymer formulations according to the invention can be prepared by
  • bead polymer formulations according to the invention are very suitable for the application of agrochemical active ingredients.
  • bead polymer formulations according to the invention are better suited for the application of agrochemical active ingredients, in particular of active components with a relatively high vapor pressure, than the most similar, known preparations.
  • the bead polymer formulations according to the invention are notable for
  • the styrene copolymers present in the bead polymer formulations according to the invention are characterized by the constituents listed under (a) to (d).
  • (meth) acrylonitrile (b) means both acrylonitrile and methacrylonitrile.
  • (meth) acrylic acid ester (c) means both esters of acrylic acid and methacrylic acid. Esters which are derived from optionally substituted, aliphatic, cycloaliphatic, aromatic or mixed aromatic-aliphatic alcohols having 4 to 18 carbon atoms are preferred.
  • the aliphatic radicals can be straight-chain as well as branched and interrupted by oxygen.
  • Examples of particularly preferred (meth) acrylic acid esters are: n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-octyl acrylate, n- octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, decyl methacrylate Do-, methacrylate stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl, 4-tert-butylcyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate,
  • lenglycol monoacrylate diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, furfurylacrylate, furfuryl methacrylate, tetrahydrofur- fururyl methacrylate and tetrahydrofuryl methacrylate and.
  • Suitable vinyl monomers (d) are preferably (meth) acrylic acid esters with 1 to 3 carbon atoms in the alcohol radical, such as, for example, methyl methacrylate, ethyl acrylate and hydroxylethyl methacrylate, furthermore acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylpyrrolidone, vinyl chloride, vinyli denchloride, vinyl acetate, vinyl propionate, vinyl laurate and vinyl adipate.
  • acrylic acid esters with 1 to 3 carbon atoms in the alcohol radical such as, for example, methyl methacrylate, ethyl acrylate and hydroxylethyl methacrylate, furthermore acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinylpyrrolidone, vinyl chloride, vinyli denchloride, vinyl acetate, vinyl propionate, vinyl laurate and vinyl adipate.
  • multifunctional vinyl monomers which act as crosslinking agents, can also be present in the styrene copolymer at least in part as further vinyl monomers (d).
  • examples include allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimethacrylate,
  • the proportion of multifunctional vinyl monomers in the styrene copolymer can be varied within a certain range.
  • the content of multifunctional vinyl monomers (d) is generally between 0 and 30% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight.
  • agrochemical active substances are understood to mean all substances customary for plant treatment. Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients and repellents may preferably be mentioned.
  • fungicides are: 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 3 -thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl ⁇ -3 methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), Aldimo ⁇ h, ampropylfo
  • bactericides are:
  • insecticides examples include: Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus Bruringomis 4-chl ⁇ henyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, - 9 -
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
  • Fipronil Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
  • Mecarbam Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrach
  • Tebufenozide Tebufenpyrad
  • Tebupirimiphos Teflubenzuron
  • Tefluthrin Temefos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Transalonium, Tronomethrin, Transion Vamidothione, XMC, xylylcarb, zetamethrin.
  • herbicides examples are:
  • Anilides e.g. Diflufenican and Propanil
  • Aryl carboxylic acids e.g. Dichloropicolinic acid, dicamba and picloram
  • Aryloxyalkanoic acids e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr
  • Aryloxy-phenoxy-alkanoic acid esters e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl
  • Azinones e.g.
  • Chloridazon and norflurazon Carbamates, e.g. Chlo ⁇ ropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolochlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, e.g.
  • Nitriles e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfiiron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tri-benuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialates, EPTC,
  • Triazines e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin
  • Triazinones e.g. Hexazinone, metamitron and metribuzin
  • Others such as Aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralide, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate,
  • Chlorcholine chloride and ethephon are examples of plant growth regulators.
  • plant nutrients are customary inorganic or organic fertilizers for supplying plants with macro and / or micronutrients.
  • repellents are diethyl tolylamide, ethylhexanediol and butopyronoxyl.
  • the bead polymer formulations according to the invention contain one or more agrochemical active ingredients.
  • Agrochemical active substances which have a vapor pressure between 5 and 10 6 mPa, particularly preferably between 50 and 10 5 mPa at 20 ° C. are preferably contained. Examples of such active substances are the substances listed in the following tables.
  • Suitable additives which can be present in the solid phase in the bead polymer formulations according to the invention are all those substances which can normally be used as additives in plant treatment compositions. These include, for example, plasticizers, dyes, antioxidants and cold stabilizers.
  • Suitable plasticizers in the present case are liquid or solid indifferent substances with a low vapor pressure and a molecular weight between 150 and 1000, which interact without a chemical reaction, preferably through their solvent or swelling capacity, with highly polymeric substances and thereby a homogeneous physical system with them form.
  • Derivatives of organic and inorganic acids are particularly suitable as plasticizers, in particular esters, amides and imides of organic acids. Esters and imides with C 12 -C 12 alkyl units are particularly preferred.
  • Examples include:
  • plasticizers are alkyl and aryl esters of hydroxy acids, such as hydroxybenzoic acid and salicylic acid, and N-alkylphthalimides.
  • Examples include:
  • ethylhexyl terephthalate diisooctyl sebacate, triisooctyl trimellitate, salicylic acid methyl ester, salicylic acid phenyl ester, butyl phthalimide, 4-hydroxybenzoic acid n-propyl ester, tri-2-ethylhexyl phosphate, triphenylphosphate, diphenyloctylphosphate, desphosphate, tri-phenylphosphate, di-phosphylsulfate, di-phenylphosphate, desphosphate, di-phenylphosphate, tri-phenylphosphate, and di-phosphylsulfate, as well
  • plasticizers in the present case also include oligomers with no more than 4 repeating units, e.g. Oligomers of aliphatic or aromatic polyesters based on, for example, adipic acid, succinic acid, sebacic acid,
  • Oligomers of hydroxycarboxylic acids such as e.g. Polycaprolactone, polyhydroxystearic acid and polyhydroxybutyric acid and polyols such as e.g. Polyethylene oxide, polypropylene oxide,
  • Colorants which are soluble or sparingly soluble are pigments, such as, for example, titanium dioxide, carbon black or zinc oxide.
  • Suitable antioxidants are all substances which can normally be used for this purpose in plant treatment products. Sterically hindered phenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes are preferred.
  • Suitable cold stabilizers are all substances which can normally be used for this purpose in plant treatment products. Urea, glycerol or propylene glycol are preferred.
  • the content of the individual components can be varied within a substantial range in the bead polymer formulations according to the invention.
  • the concentrations are in the solid phase - 15 -
  • styrene copolymer (A) generally between 25 and 95% by weight, preferably between 40 and 90% by weight,
  • agrochemical active ingredients (B) in general between 5 and 75% by weight, preferably between 10 and 60% by weight and
  • additives (C) generally between 0 and 30% by weight, preferably between 0 and 15% by weight.
  • the particle size of the solid particles can be varied within a certain range. It is generally between 1 and 100 ⁇ m, preferably between 5 and 50 ⁇ m, particularly preferably between 5 and 30 ⁇ m.
  • the bead polymer formulations according to the invention can be present either as a particulate solid phase or as a dispersion of solid particles in a liquid phase.
  • liquid phase If a liquid phase is present, it essentially consists of water.
  • components can be included which are used in the preparation of the bead polymer formulations according to the invention and remain in the liquid phase. Possible such components are water-immiscible organic solvents, dispersants (protective colloids) and buffer reagents.
  • Suitable organic solvents are all customary organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the agrochemical active ingredients well.
  • Aromatic hydrocarbons such as toluene and xylene may also be mentioned as examples of such solvents - 16 -
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and dichloroethane, and also esters, such as ethyl acetate.
  • Natural and synthetic water-soluble polymers such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, furthermore polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, and also also include Alkali metal hydroxide neutralized copolymers of methacrylic acid and methacrylic acid ester.
  • the amounts of the additional substances mentioned in the aqueous phase can be varied within a substantial range.
  • the concentration depends on the amounts in which these substances are used in the preparation of the bead polymer formulations according to the invention, and on the manner in which they are worked up after the polymerization.
  • the bead polymer formulations according to the invention are prepared by the suspension polymerization procedure.
  • suspension polymerization is understood to mean a process in which a monomer or a monomer-containing mixture which contains an initiator which is soluble in the monomer (s) in the form in a phase which is essentially immiscible with the monomer (s) and which contains a dispersant of droplets, optionally in a mixture with small, solid particles, is broken up and cured by increasing the temperature with stirring. Further details of the suspension polymerization are described, for example, in the publication "Polymer Processes", published by CESchildknecht, published in 1956 by Interscience Publishers, - 17 -
  • the monomer mixtures required as starting materials when carrying out the process according to the invention are those listed under (a) to (d)
  • Initiators which can be used in carrying out the process according to the invention are all substances which can customarily be used to initiate polymerizations. Oil-soluble initiators are preferred. Peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide,
  • organic solvents which are not very miscible with water can be used as auxiliary solvents. All those organic diluents which have already been mentioned in connection with the description of the aqueous phase of the bead polymer formulations according to the invention are suitable.
  • the procedure is generally such that a homogeneous mixture of monomer mixture, one or more agrochemical active ingredients and optionally additives is first prepared.
  • This homogeneous mixture can be a solution or a finely divided dispersion.
  • an agrochemical active ingredient is insoluble or insufficiently soluble in the monomer mixture, it can be in finely divided form.
  • finely divided means that the active substance particles or active substance droplets have an average particle size of less than 2 ⁇ m, preferably less than 1 ⁇ m.
  • a finely divided dispersion can be produced with the aid of high-speed stirrers (preferably in the case of liquid active substances) or bead mills / ball mills (preferably in the case of solid active substances).
  • the process according to the invention can be carried out by using the mixture of monomer mixture, agrochemical active substance and optionally additives in the form of a solution, an auxiliary solvent being used to improve the solubility of the agrochemical active substance.
  • Suitable auxiliary solvents are organic solvents which, on the one hand, are not very miscible with water, but on the other hand, the respective agrochemical - 19 -
  • the process according to the invention can be carried out by adding a buffer reagent to the aqueous phase (B), so that the pH of the aqueous phase at the start of the polymerization is between 12 and 5, preferably between 10 and 6 having.
  • the amounts of monomer mixture and agrochemical active ingredient are generally chosen so that in the homogeneous mixture used between 25 and 95% by weight of monomer mixture and between 5 and 75% by weight of agrochemical active ingredient, preferably between 40 and 90% by weight. % of monomer mixture and between 10 and 60% by weight of agrochemical active ingredient are present.
  • Initiators are generally used in amounts between 0.05 and 2.5% by weight, preferably between 0.2 and 1.5% by weight, based on the monomer mixture.
  • the amount of auxiliary solvent is generally between 30 and 300% by weight, based on the sum of the monomer mixture and the agrochemical active ingredient.
  • the amount of aqueous phase is generally between 75 and 1200% by weight, preferably between 100 and 500% by weight, based on the sum of the monomer mixture and agrochemical active ingredient. - 20 -
  • the amount of dispersant is generally between 0.05 and 2% by weight, preferably between 0.1 and 1% by weight, based on the aqueous phase.
  • the organic phase is added to the aqueous phase with stirring.
  • the temperature can be varied within a certain range. In general, temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 50 ° C.
  • the polymerization takes place in the second step of the process according to the invention.
  • the stirring speed is important for setting the particle size.
  • the mean particle size of the bead polymer decreases with increasing stirring speed.
  • the exact stirring speed for setting a certain predetermined bead size depends in individual cases on the reactor size, the reactor geometry and the stirrer geometry. It has proven to be expedient to determine the necessary stirring speed experimentally.
  • bead sizes are generally between 6 and 30 ⁇ m at speeds between 300 and 500 revolutions per minute reached.
  • the polymerization temperature can be varied within a wide range. It depends on the decomposition temperature of the initiator used. In general, temperatures between 50 ° C and 150 ° C, preferably between 55 ° C and 100 ° C.
  • the duration of the polymerization depends on the reactivity of the components involved.
  • the polymerization generally lasts between 30 minutes and several hours. It has proven useful to use a temperature program in which the polymerization is started at a low temperature, for example 70 ° C., and the reaction temperature is increased as the polymerization conversion progresses. - 21 -
  • the bead polymer can be isolated, for example by filtration or decanting, and, if appropriate, dried after washing. If it is desired to prepare a suspension of bead polymer in the aqueous phase, in most cases a further work-up is unnecessary. Any auxiliary solvent contained can be removed by distillation from the resulting mixture, optionally together with part of the water.
  • the bead polymer formulations according to the invention are outstandingly suitable for applying agrochemical active ingredients to plants and / or their habitat.
  • the bead polymer formulations according to the invention can be used particularly advantageously in order to apply agrochemical active ingredients with a relatively high vapor pressure. They ensure the release of the active components in the desired amount over a longer period of time.
  • bead polymer formulations according to the invention can be used as such either in solid form or as suspensions, if appropriate after prior dilution with water.
  • the application is carried out according to conventional methods, for example by pouring, spraying, spraying or
  • the application rate of the bead polymer formulations according to the invention can be varied within a substantial range. It is based on the respective agrochemical active ingredients and their content in the bead polymers.
  • the solids concentration is adjusted to 15% by weight by adding water. 22 kg of a dispersion of a bead polymer with an active ingredient content of 1.1% by weight are obtained.
  • the average particle size is 12 ⁇ m.
  • the surfaces coated in this way were each placed in a gas space which was flushed at a temperature of 40 ° C. with a stream of nitrogen in an amount of 16 liters per hour.
  • the concentration of active substance in the purge gas was determined as a function of time.
  • the spray liquid was applied with the help of a spraying vehicle onto a heavily weed track over a length of 400 m and a width of 5 m.

Abstract

L'invention concerne de nouvelles formulations de polymères en perles, constituées de (I) une phase solide particulaire contenant (A) un copolymère styrénique de (a) 15 à 75 % en poids de styrène, (b) 5 à 40 % en poids de (méth)acrylnitrile, (c) 10 à 70 % en poids de (méth)acrylate avec 4 à 18 atomes de carbone dans la fraction ester et (d) 0 à 30 % en poids d'autres monomères vinyliques, et (B) au moins un principe actif agrochimique ainsi que (C) éventuellement des additifs, la teneur en principe actif agrochimique se situant entre 5 et 75 % en poids et la phase solide présentant une dimension particulaire moyenne comprise entre 1 et 100 νm, et de (II) éventuellement une phase liquide. L'invention concerne également un procédé pour la préparation de ces nouvelles formulations et leur utilisation pour l'application de principes actifs agrochimiques.
PCT/EP1999/000562 1998-02-10 1999-01-28 Formulations de polymeres en perles WO1999040786A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32514/99A AU3251499A (en) 1998-02-10 1999-01-28 Pearl polymer formulations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19805248.0 1998-02-10
DE1998105248 DE19805248A1 (de) 1998-02-10 1998-02-10 Perlpolymerisat-Formulierungen

Publications (1)

Publication Number Publication Date
WO1999040786A1 true WO1999040786A1 (fr) 1999-08-19

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AU (1) AU3251499A (fr)
DE (1) DE19805248A1 (fr)
WO (1) WO1999040786A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0981956A2 (fr) * 1998-08-19 2000-03-01 Nova Chemicals Inc. Dissolution des insecticides dans des monomères
WO2001005223A1 (fr) * 1999-07-20 2001-01-25 Bayer Aktiengesellschaft Granules a repandre
WO2001057097A1 (fr) * 2000-02-04 2001-08-09 Bayer Aktiengesellschaft Suspensions polymeres non aqueuses a comportement rheoepaississant prononce
JP2005529173A (ja) * 2002-06-13 2005-09-29 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 散剤

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001045513A1 (fr) * 1999-12-21 2001-06-28 Dsm N.V. Preservation de l'activite fongicide en solution aqueuse
MXPA00012167A (es) * 1999-12-24 2002-08-06 Bayer Ag Procedimiento para la obtencion de polimeros en perlas, reticulados, monodispersados.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201214A2 (fr) * 1985-04-10 1986-11-12 Nippon Paint Co., Ltd. Procédé de fabrication de microparticules de polymére ayant une activité pesticide
EP0281918A2 (fr) * 1987-03-11 1988-09-14 BASF Aktiengesellschaft Agent de protection des plantes contenant un ingrédient actif
JPH0753291A (ja) * 1993-08-17 1995-02-28 Chisso Corp 微量要素含有被覆粒状肥料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201214A2 (fr) * 1985-04-10 1986-11-12 Nippon Paint Co., Ltd. Procédé de fabrication de microparticules de polymére ayant une activité pesticide
EP0281918A2 (fr) * 1987-03-11 1988-09-14 BASF Aktiengesellschaft Agent de protection des plantes contenant un ingrédient actif
JPH0753291A (ja) * 1993-08-17 1995-02-28 Chisso Corp 微量要素含有被覆粒状肥料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 122, no. 23, 5 June 1995, Columbus, Ohio, US; abstract no. 289895, KIMOTO, SHIGETOSHI ET AL: "Fertilizer granules coated with trace elements and polymeric binders" XP002105291 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0981956A2 (fr) * 1998-08-19 2000-03-01 Nova Chemicals Inc. Dissolution des insecticides dans des monomères
EP0981956A3 (fr) * 1998-08-19 2000-08-30 Nova Chemicals Inc. Dissolution des insecticides dans des monomères
WO2001005223A1 (fr) * 1999-07-20 2001-01-25 Bayer Aktiengesellschaft Granules a repandre
WO2001057097A1 (fr) * 2000-02-04 2001-08-09 Bayer Aktiengesellschaft Suspensions polymeres non aqueuses a comportement rheoepaississant prononce
JP2005529173A (ja) * 2002-06-13 2005-09-29 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 散剤

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DE19805248A1 (de) 1999-08-12
AU3251499A (en) 1999-08-30

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