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EP1056337A1 - Formulations de polymeres en perles - Google Patents

Formulations de polymeres en perles

Info

Publication number
EP1056337A1
EP1056337A1 EP99908866A EP99908866A EP1056337A1 EP 1056337 A1 EP1056337 A1 EP 1056337A1 EP 99908866 A EP99908866 A EP 99908866A EP 99908866 A EP99908866 A EP 99908866A EP 1056337 A1 EP1056337 A1 EP 1056337A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
bead polymer
agrochemical active
active ingredient
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99908866A
Other languages
German (de)
English (en)
Inventor
Wolfgang Podszun
Hilmar Wolf
Rafel Israels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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 AG filed Critical Bayer AG
Publication of EP1056337A1 publication Critical patent/EP1056337A1/fr
Ceased legal-status Critical Current

Links

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
    • 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 are not always released at the rate necessary for the biological action.
  • formulations which contain easily washable agrochemical active ingredients in microencapsulated form in unsaturated polyester resins (cf. EP-A 0 517 669).
  • release kinetics of the microencapsulated active ingredients do not always meet the practical requirements. Hydrophobic active ingredients are released very slowly from these formulations.
  • 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.
  • agrochemical active ingredient is between 5 and 75% by weight and the solid phase having an average particle size between 1 and 100 ⁇ m
  • bead polymer formulations according to the invention can be produced by:
  • the bead polymer formulations according to the invention are notable for a number of advantages. This enables them to release the active components in a uniform amount over a fairly long period of time. It is particularly favorable that the release rate of the active ingredient can be controlled within wide limits by the content of water-soluble monomer.
  • copolymers present in the bead polymer formulations according to the invention are characterized by the constituents listed under (a) to (c).
  • water-insoluble monomers (a) is to be understood as meaning monoethylenically unsaturated compounds which dissolve in water at less than 5% by weight at 20 ° C.
  • Preferred water-insoluble monomers (a) are the alkyl esters of acrylic acid and methacrylic acid, styrene, styrene derivatives and mixtures of styrene and acrylonitrile and vinyl derivatives.
  • Examples include: styrene, alpha Methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl laurate, vinyl adipate, methyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate Hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate,
  • water-soluble monomers (b) are monoethylenically unsaturated compounds which dissolve in water at 20 ° C. to more than 5% by weight.
  • examples include: acrylic acid and its alkali metal and ammonium salts, methacrylic acid and its alkali metal and ammonium salts, hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol tetramonomethyl methacrylate, triethylene glycol tetramonomethacrylate, methacrylate methacrylate, triethylene glycol tetramonomethyl methacrylate, , Acrylamide, methacrylamide, vinyl pyrolidone and vinyl imidazole. Hydroxyethyl methacrylate is preferred.
  • the proportion of water-soluble monomer (b) is essential for the active ingredient release.
  • the release rate of the agrochemical active substance can be controlled within wide limits via the proportion of (b).
  • the proportion of (b) is in the range from 5 to 35% by weight. In many cases, particularly good effects are achieved with a proportion of (b) in the range from 7.5 to 20% by weight.
  • Crosslinkers (c) are compounds having at least two ethylenically unsaturated groups in the molecule. Examples include: allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, - 6 -
  • the proportion of crosslinking agent (c) in the copolymer can be varied within a certain range.
  • the (crosslinker (c) content is generally between 0 and 25% 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:
  • Imazalil Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutan
  • Nickel dimethyldithiocarbamate Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,
  • Tebuconazole Tebuconazole, tecloftalam, Techazen, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
  • bactericides are:
  • insecticides examples include acaricides and nematicides.
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-
  • Fipronil fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron,
  • Flufenprox Fluvahnate, Fonophos, Formothion, Fosthiazat, Fubfenprox,
  • 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
  • Triazophos triazuron, trichlorfon, triflumuron, trimethacarb,
  • 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 such as, for example, chloropropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroaniline such as Oryzalin, Pendimethalin and Trifl uralin; Diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz - 10 -
  • Hydroxylamines e.g. Alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim
  • Imidazolinones e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin
  • Nitriles e.g. Bromoxynil, dichlobenil and ioxynil
  • Oxyacetamides e.g. Mefenacet
  • Sulfonylureas e.g.
  • Amidosulfuron bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g.
  • Atrazin cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, 4-amino-N- (l, l-dimetylethyl) -4,5-dihydro-3- (l-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamide, benfuresate, Bentazone, Cin- methylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
  • Triazinones e.g. Hexazinone, metami
  • Chlorcholine chloride and ethephon are examples of plant growth regulators.
  • plant nutrients are customary inorganic or organic
  • Fertilizer for supplying plants with macro and / or micronutrients called.
  • repellents are diethyltolylamide, ethylhexanediol and butopyronoxyl.
  • Suitable additives which can be present in the solid phase in the bead polymer formulations according to the invention are all those substances which are customarily usable as additives in plant treatment compositions. These include plasticizers, dyes, antioxidants, cold stabilizers and fillers. - 11 -
  • 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.
  • 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.
  • fillers come primarily inorganic particles, such as. B. carbonates, silicates and oxides with an average particle size of 0.005 to 5 microns, preferably 0.02 to 2 microns into consideration. Silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates are particularly suitable.
  • 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
  • copolymer (A) generally between 25 and 95% by weight, preferably between 40 and 90% by weight, - 12 -
  • 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.
  • 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.
  • It can also contain components which are used in the preparation of the bead polymer formulations according to the invention and remain in the liquid phase. Possible components of this type 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
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and dichloroethane
  • esters such as ethyl acetate.
  • loose esters and cellulose ethers also polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, and also also copolymers of methacrylic acid and methacrylic acid ester neutralized with alkali metal hydroxide.
  • 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 distributed and cured by increasing the temperature with stirring. Further details of the suspension polymerization are, for example, in the publication "Polymer Processes", edited by C.E. Schildknecht, published in 1956 by Interscience
  • the monomer mixtures required as starting materials when carrying out the process according to the invention are those listed under (a) to (c)
  • initiators When carrying out the process according to the invention, all substances which can usually be used for initiating polymerizations can be used as initiators. Oil-soluble initiators are preferred.
  • Peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert.-butyl peroctoate, 2,5-bis (2-ethylhexanoyl peroxi) -2,5-dimethylhexane and tert.-amylhexoxane-2-may be mentioned as examples , further azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-methylisobutyronitrile).
  • 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 (a - c), 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 ingredients) or bead mills / ball mills (preferably in the case of solid active ingredients).
  • the process according to the invention can be carried out by using the mixture of monomer mixture, agrochemical active ingredient and optionally additives in the form of a solution, with the
  • auxiliary solvent is used to improve the solubility of the agrochemical active ingredient.
  • Suitable auxiliary solvents are organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the respective agrochemical active ingredient well.
  • the organic diluents already mentioned can preferably be used.
  • 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. - 16 -
  • 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 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 agrochemical active ingredient.
  • the amount of aqueous phase is generally between 75 and
  • 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. - 17 -
  • 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 reached per minute.
  • the polymerization temperature can be varied within a wide range. It depends on the decomposition temperature of the initiator used. Generally one works at 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
  • Low temperature polymerization e.g. 70 ° C is started and the reaction temperature is increased as the polymerization conversion progresses.
  • 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. - 18 -
  • the bead polymer formulations according to the invention are outstandingly suitable for applying agrochemical active ingredients to plants and / or their habitat. 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 mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted with sodium hydroxide solution to pH 8 50 wt .-% methyl methacrylate was filled.
  • the stirring speed is set to 700 revolutions per minute, and the temperature is kept at 60 ° C. for 3 hours, then at 78 ° C. for 10 hours and then at 85 ° C. for 2 hours.
  • the mixture is then cooled to room temperature within 2 hours. Dispersions of active ingredient-containing pearl polymers are obtained.
  • BeiX y z content of middle game no. (in g) (in g) (in g) Hydroxyethyl particle diameter methacrylate in the bead polymer copolymer particles
  • 3 different bead polymers with different copolymer compositions are produced.
  • x g of methyl methacrylate, y g of hydroxyethyl methacrylate, z g of ethylene glycol dimethacrylate, 100 g of imidachlopride and 30 g of finely divided silicon dioxide (HDK H2000 from Wacker) are mixed in a ball mill for 2 hours and then mixed with 3 g of dibenzoyl peroxide at room temperature with stirring.
  • the mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% strength by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted to pH 8 with sodium hydroxide solution .-% methyl methacrylate was filled.
  • the stirring speed is set to 500 revolutions per minute and the temperature is kept at 78 ° C. for 8 hours and then at 85 ° C. for 2 hours.
  • the mixture is then cooled to room temperature within 2 hours.
  • the bead polymer is isolated by settling and decanting, washed with cold water and dried at 50 ° C. in a drying cabinet.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne de nouvelles formulations de polymères en perles, constituées I) d'une phase solide à particules et II) éventuellement d'une phase liquide. La phase solide contient A) un copolymère composé a) de 40 à 95 % en poids d'un monomère non soluble dans l'eau, b) de 5 à 35 % en poids d'un monomère soluble dans l'eau et c) de 0 à 25 % en poids d'un agent de réticulation, B) au moins un agent agrochimique et C) éventuellement des additifs. La teneur en agent agrochimique est comprise entre 5 et 75 % en poids et la phase solide présente une taille moyenne de particule comprise entre 1 et 100 νm. L'invention concerne également un procédé pour la production de ces nouvelles formulations et leur utilisation pour l'application d'agents agrochimiques.
EP99908866A 1998-02-20 1999-02-09 Formulations de polymeres en perles Ceased EP1056337A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19807118A DE19807118A1 (de) 1998-02-20 1998-02-20 Perlpolymerisat-Formulierungen
DE19807118 1998-02-20
PCT/EP1999/000843 WO1999041982A1 (fr) 1998-02-20 1999-02-09 Formulations de polymeres en perles

Publications (1)

Publication Number Publication Date
EP1056337A1 true EP1056337A1 (fr) 2000-12-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99908866A Ceased EP1056337A1 (fr) 1998-02-20 1999-02-09 Formulations de polymeres en perles

Country Status (12)

Country Link
EP (1) EP1056337A1 (fr)
JP (1) JP2002503679A (fr)
KR (1) KR20010041045A (fr)
CN (1) CN1298278A (fr)
AU (1) AU2832699A (fr)
BR (1) BR9908109A (fr)
CA (1) CA2321440A1 (fr)
DE (1) DE19807118A1 (fr)
ID (1) ID26656A (fr)
MX (1) MXPA00008102A (fr)
PL (1) PL342472A1 (fr)
WO (1) WO1999041982A1 (fr)

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EP1656883A1 (fr) 2004-11-10 2006-05-17 Universite Libre De Bruxelles Appareil de mesure portable d'un signal EMG
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JP6083936B2 (ja) * 2011-03-11 2017-02-22 大阪ガスケミカル株式会社 徐放性粒子の製造方法
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Also Published As

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BR9908109A (pt) 2000-10-31
KR20010041045A (ko) 2001-05-15
CN1298278A (zh) 2001-06-06
AU2832699A (en) 1999-09-06
ID26656A (id) 2001-01-25
MXPA00008102A (es) 2001-04-01
WO1999041982A1 (fr) 1999-08-26
JP2002503679A (ja) 2002-02-05
CA2321440A1 (fr) 1999-08-26
DE19807118A1 (de) 1999-08-26
PL342472A1 (en) 2001-06-04

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