EP1515604A1 - Formulations pulverulentes - Google Patents
Formulations pulverulentesInfo
- Publication number
- EP1515604A1 EP1515604A1 EP03735508A EP03735508A EP1515604A1 EP 1515604 A1 EP1515604 A1 EP 1515604A1 EP 03735508 A EP03735508 A EP 03735508A EP 03735508 A EP03735508 A EP 03735508A EP 1515604 A1 EP1515604 A1 EP 1515604A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder formulations
- acrylonitrile
- styrene
- formulations according
- agrochemical active
- 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.)
- Withdrawn
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
- A01N25/12—Powders or granules
Definitions
- the present invention relates to new powder formulations containing agrochemical active ingredients and polymers, a process for the preparation of these formulations and their use for the application of agrochemical active ingredients.
- Microparticles are already known from WO 99-00 013, which contain certain polymers in a mixture with agrochemical active substances. These preparations are prepared by dissolving polymers and agrochemical active ingredients in a water-immiscible organic solvent, then dispersing this solution in water using emulsifiers, then evaporating the solvent and the microparticles thus produced by decanting and / or filtration separated from the aqueous phase and then dried.
- a disadvantage of this method is that many and complex measures have to be carried out and the use of relatively large apparatus is required when working on an industrial scale. It is also unfavorable that the organic solvents required to dissolve the components must subsequently be removed again.
- At least one agrochemical active ingredient At least one agrochemical active ingredient
- the powder formulations according to the invention can be produced by mixing a mixture
- At least one agrochemical active ingredient At least one agrochemical active ingredient
- powder formulations according to the invention are very well suited for the application of the agrochemical active ingredients contained to plants and / or their habitat.
- powder formulations according to the invention are better suited for applying the agrochemical active ingredients contained than the constitutionally most similar, known preparations. Above all, it is unexpected that the active components are released in the desired amount over a relatively long period of time.
- the powder formulations according to the invention contain one or more agrochemical active ingredients.
- agrochemical active substances are understood to mean all substances customary for plant treatment. May be mentioned
- Fungicides Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators. Plant nutrients and repellents. Solid agrochemical active ingredients are preferred.
- fungicides are:
- Difenoconazole dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
- Edifenphos epoxyconazole, ethirimol, etridiazole, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Aluminum, Futolanilyl, Folutrianyl, Folutrianil, Flutrianyl, Folut Fuberidazole, furalaxyl, furmecyclox, fenhexamide,
- Iprovalicarb Iprovalicarb, kasugamycin, copper preparations such as: copper hydroxide, copper phthalate,
- Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol.
- insecticides examples include: Abamectin, Acephat, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azo-cyclotinos, Bacill -2- (4-cl lorphenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb , Buprofezin, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophen
- Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenöphos, Prome- carb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetroos, Pyrachi daphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos,
- Tebufenozide Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temefos, Terbam, Terbufos, Tetrachlorvinphos, Thiacloprid, Tlriafenox, Thiamethoxam, Thiodicarb, Thiofanox, Thiomethonien, Triniazin, Triniazin, Triniazin Trimethacarb, vamidothione, XMC, xylylcarb, zetamethrin.
- herbicides are: anilides, such as diflufenican and propanil; Aryl carboxylic acids such as dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones such as chloridazon and norflurazon; Carbamates, such as, for example, chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides, such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor;
- Fluorochloridones Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
- Chlorcholine chloride and ethephon are examples of plant growth regulators.
- Typical inorganic or organic substances are examples of plant nutrients
- Fertilizer for supplying plants with macro and / or micronutrients called.
- repellents are diethyl tolylamide, ethylhexanediol and butopyronoxyl.
- insecticides which can preferably be contained in the powder formulations according to the invention:
- the powder formulations according to the invention contain one or more copolymers of styrene and acrylonitrile, the proportion of acrylmtrile being between 20 and 40% by weight. Such copolymers with an acrylonitrile content of between 25 and 35% by weight are preferred.
- copolymers of styrene and acrylonitrile contained in the powder formulations according to the invention are known as SAN polymers (cf. plastics 85, 1550 (1995); Encycl. Polym. Sei. Eng. 1, 452-470; Encycl. Polym. Sei. Eng. 16, 38 f. And 72 f; as well as Ullmanns Encyklopadie der technical chemistry, 4th ed. Vol. 19, pages 123-131).
- SAN polymers cf. plastics 85, 1550 (1995); Encycl. Polym. Sei. Eng. 1, 452-470; Encycl. Polym. Sei. Eng. 16, 38 f. And 72 f; as well as Ullmanns Encyklopadie der technical chemistry, 4th ed. Vol. 19, pages 123-131).
- the production of styrene-acrylonitrile polymers is described for example in Houben-Weyl "Methods of Organic Chemistry", Vol. E 20, Macromolecular Substance
- Copolymers with a statistical distribution of styrene and acrylonitrile are obtained by radical polymerization.
- the reaction is often started thermally, especially in industrial bulk or solution polymerization; radical initiators are used in suspension or emulsion polymerizations.
- radical initiators are used in suspension or emulsion polymerizations.
- azo compounds dominate, especially azo-bis-isobutyronitrile, and potassium peroxodisulfate in emulsion polymerization.
- the procedure is generally such that the components in the desired amounts are dispersed in water at room temperature, then heated with stirring, cooled after the reaction has ended and the resulting bead-shaped product is filtered off, washed and dried.
- the emulsion polymerization is generally carried out in such a way that a separately prepared mixture of styrene and acrylonitrile is added to the heated aqueous phase, with a proportion of 5 to 20% of this mixture being added in one pour and the rest after heating again is added dropwise over a longer period of time.
- the mixture is worked up in the customary manner by separating, washing and drying the copolymer.
- SAN polymers have a glass transition temperature of approximately 97 ° C and a melting range of approximately 110-116 ° C.
- the powder formulations according to the invention can also contain copolymers of methylstyrene and acrylonitrile. These polymers can also be prepared by a radical polymerization reaction. Further information on methylstyrene-acrylonitrile copolymers can be found in "Ullmann's Encyclopedia of Industrial Chemistry" ISBN 3-527-20100-9 and ISBN 3-527-20121-1,
- Additives which can be contained in the powder formulations according to the invention are all substances which are customarily used in polymer preparations of this type. Fillers from which plastic are supplied
- fillers are: titanium dioxide, barium sulfate, furthermore aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, and phosphates.
- lubricants and lubricants are: magnesium stearate. Stearic acid, talc and bentonite.
- concentrations of the individual components can be varied within a substantial range in the powder formulations according to the invention. That's the salary
- Agrochemical active ingredients generally between 1 and 50% by weight, preferably between 5 and 40% by weight,
- Additives generally between 0 and 30% by weight, preferably between 0 and 20% by weight.
- the procedure is generally such that styrene-acrylonitrile copolymers are used at temperatures between 120 ° C. and 230 ° C., preferably between 120 ° C. and 180 ° C., particularly preferably between 140 ° C. and 170 ° C melts and then enters one or more agrochemical active ingredients and any additives with stirring.
- the resulting liquid and homogeneous mixture is transported on cooling belts or cooling rollers using conventional discharge devices. After cooling, the solidified product is removed from the cooling device and broken. The resulting raw granulate is then crushed and sieved using conventional grinding equipment so that a powder is formed in which the particles have a diameter below 125 ⁇ m.
- All grinders that are usually used for such purposes can be considered as grinding devices.
- Pin mills, ball mills, jet mills or classifying mills can preferably be used, a mill of the ACM 2 type from Hosokawa Mikropul being mentioned as an example.
- the powder formulations according to the invention can be used as such or after the addition of further formulation auxiliaries for the application of agrochemical active ingredients in crop protection both in agriculture and forestry and in horticulture.
- All customary components which can be used in plant treatment compositions are considered as formulation auxiliaries, such as, for example, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, components which delay drying, anti-freeze agents, secondary thickeners, solvents and, in the case of the manufacture of mordants, also Glue.
- Suitable dyes which can be used for the further preparation of the powders according to the invention as plant treatment agents are all dyes customary for such purposes. Both pigments that are sparingly soluble in water and dyes that are soluble in water can be used. Examples include those under the names Rhodamine B, CIPigment Red 112 and
- Suitable wetting agents which can be used to formulate the powders according to the invention are all substances which are customary in the formulation of agrochemical active substances and which promote wetting.
- Alkyl naphthalene sulfonates such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.
- Suitable dispersants and / or emulsifiers which can be used to formulate the powders according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active ingredients.
- Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants are preferably usable.
- Suitable nonionic dispersants include, in particular, ethylene oxide / propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
- Suitable anionic dispersants are, in particular, lignin sulfonates. Polyacrylic acid salts and aryl sulfonate formaldehyde condensates.
- Defoamers which can be used to formulate the powders according to the invention are all foam inhibitors which are customary for formulating active agrochemicals. Silicone defoamers and magnesium stearate can preferably be used.
- the preservatives which can be used for the formulation of the powders according to the invention are all for such purposes for the formulation of agrochemical active substances in question. Examples include dichlorophene and benzyl alcohol hemiform.
- All components which can be used for such purposes in agrochemical compositions are suitable as components which delay drying and as anti-freeze agents which can be used to formulate the powders according to the invention.
- Polyhydric alcohols such as glycerol, ethanediol, propanediol and polyethylene glycols of different molecular weights are preferred.
- Secondary thickeners which can be used to formulate the powders according to the invention are all substances which can be used for such purposes in agrochemical compositions.
- Cellulose derivatives, acrylic acid derivatives are preferred.
- Xanthan, modified clays and highly disperse silica are preferred.
- Suitable solvents which can be used to formulate the powders according to the invention are all organic solvents which can be used in agrochemical compositions.
- Ketones such as methyl isobutyl ketone and cyclohexanone
- furthermore amides such as dimethylformamide
- strongly polar solvents such as dimethyl sulfoxide
- aromatic hydrocarbons such as xylene
- esters such as propylene glycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, acetic acid heptyl ester, citric acid butyl tri esters,
- alcohols such as ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and l-methoxy-2-propanol.
- Water can also be used as a diluent.
- adhesives can also be used to formulate the powders according to the invention.
- binders that can be used in pickling agents.
- Dispersions of biodegradable polyester-polyurethane-polyureas in water are also particularly preferred as adhesives. Such dispersions are known (cf. WO 01-17347).
- the powder formulations according to the invention can be used in practice as such or after mixing with further formulation auxiliaries and / or plant treatment agents and, if appropriate, after further dilution with water.
- the application is carried out according to conventional methods, for example by scattering, pouring, spraying or spraying.
- the powders according to the invention can particularly advantageously be added by adding appropriate formulation auxiliaries and, if appropriate, diluents
- Transfer seed dressings with which seed of the most varied kind can be treated are suitable for dressing the seeds of cereals, such as wheat, barley, rye, oats and triticale, as well as the seeds of rice, corn, rapeseed, peas, field beans, cotton, sunflowers and beets or also vegetable seeds of the most varied of natures.
- the seed dressing formulations can also be used for dressing seeds of transgenic plants. In cooperation with the substances formed by expression, synergistic effects can also occur.
- the dressing is carried out by placing the seed in a mixer, adding the desired amount of dressing formulation either as such or after prior dilution with water and mixing until the formulation is evenly distributed on the seed. If necessary, a drying process follows.
- the powder formulations according to the invention and the formulation oranges which can be prepared therefrom by further mixing with formulation auxiliaries and / or plant treatment compositions are outstandingly suitable for the application of agrochemical active substances to plants and / or their habitat. You guarantee that
- the application rate of the powder formulations according to the invention and of the preparations which can be prepared therefrom by further mixing with formulation auxiliaries can be varied within a substantial range. It depends on the agrochemical active substances present, on their content in the plant treatment products, on the respective indication and the field of application.
- 1.5 l of deionized water 950 g (9.1 mol) are in a 5-1 stainless steel pressure vessel (design pressure: 2.5 MPa) with Bla1 stirrer, thermometer, heating and cooling jacket and filler and outlet nozzle.
- Styrene 330 g ' (6.2 mol) acrylonitrile, 16 g 4-isopropenyl-1-methylcyclohexane (dipentene) as regulator, 0.5 g di-tert-butyl peroxide, 15 g poly (l-vinyl) -2-pyrrolidone) and 7.5 g of poly (vinyl alcohol) and 0.5 g of disodium phosphate.
- a solution of 49 parts by weight of styrene, 21 parts by weight of acrylonitrile and 30 parts by weight of ethylbenzene is continuously fed to a stirred tank.
- the same amount of product is also continuously discharged from the bottom of the boiler.
- the heat of reaction is removed by evaporative cooling (reaction temperature: 150 ° C; operating pressure: 0.3 MPa).
- the turnover is 20-30%.
- the reaction melt is freed of volatile constituents in several stages of draining (500 Torr / 66 kPa; 100 Torr / 13 kPa) at 230 ° C and worked up in a degassing extruder.
- the volatile components are returned to the company.
- a homogeneous product strand approximately 2 mm in diameter is continuously drawn off from the extruder nozzle. This is first cooled in a water bath and then comminuted in a granulator into cylindrical particles with a length of about 4 mm.
- the granules obtained consist of 29% by weight of imidacloprid and 71% by weight of styrene-aconitrile copolymer. Before use, the product is ground to the desired grain size using a ball mill.
- Imidacloprid has a water solubility of about 700 mg / liter at 25 ° C. Samples are taken from the stirred mixture after the stirring times given in Table 3 below, which are filtered through a 0.2 ⁇ m microfilter. The concentration of imidacloprid is determined in each case in the filtrate. The active substance concentration is determined by means of HPLC:
- Formulation is released over a long period of time.
- the weighed amount of imidacloprid is 1,000 mg.
- Imidacloprid has a water solubility of approx. 700 mg / liter at 25 ° C.
- Samples are taken from the stirred mixture after the times given in Table 4, filtered through a 0.2 ⁇ m microfilter, and the active ingredient content is determined by means of HPLC.
- adhesive impranil DLN D50, Bayer AG
- 1 g of a 1% strength by weight aqueous solution of the dye LEVANYL RED BB-LF Bayer AG
- the trays are then placed in a chamber in which the relative humidity is 90% and in which the temperature is 24 ° C during the day and 15 ° C at night.
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 pulvérulentes qui renferment au moins une substance active agrochimique, au moins un copolymère de styrène et d'acrylonitrile, la proportion d'acrylonitrile étant comprise entre 20 et 40 % en poids, ainsi qu'éventuellement des additifs, le diamètre des particules desdites formulations étant inférieur à 125 ?m. L'invention concerne également un procédé de production des nouvelles formulations pulvérulentes et l'utilisation de ces dernières pour l'application de substances actives agrochimiques sur des plantes et/ou dans leur espace vital.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10226222 | 2002-06-13 | ||
DE10226222A DE10226222A1 (de) | 2002-06-13 | 2002-06-13 | Pulver-Formulierungen |
PCT/EP2003/005706 WO2003105584A1 (fr) | 2002-06-13 | 2003-05-30 | Formulations pulverulentes |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1515604A1 true EP1515604A1 (fr) | 2005-03-23 |
Family
ID=29719007
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03735508A Withdrawn EP1515604A1 (fr) | 2002-06-13 | 2003-05-30 | Formulations pulverulentes |
Country Status (9)
Country | Link |
---|---|
US (1) | US20060111242A1 (fr) |
EP (1) | EP1515604A1 (fr) |
JP (1) | JP2005529173A (fr) |
AU (1) | AU2003238181A1 (fr) |
BR (1) | BR0312131A (fr) |
DE (1) | DE10226222A1 (fr) |
MX (1) | MXPA04012358A (fr) |
WO (1) | WO2003105584A1 (fr) |
ZA (1) | ZA200409971B (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4820523B2 (ja) * | 2002-09-11 | 2011-11-24 | 日本曹達株式会社 | 微生物生育抑制剤含有樹脂微粒子および該微粒子を含む水性エマルジョン塗料 |
GB0412974D0 (en) * | 2004-06-10 | 2004-07-14 | Syngenta Participations Ag | Method of applying active ingredients |
DE102006006618A1 (de) * | 2006-02-14 | 2007-08-16 | Bayer Technology Services Gmbh | Herstellung mikroskaliger Polymer-,Wirkstoff-oder Polymer-Wirkstoff-Partikel durch Sprüh-Mahl-Trocknung einer Lösung in einer Mühle |
DE102008050415A1 (de) | 2008-10-04 | 2010-04-08 | Bayer Technology Services Gmbh | Freisetzungs-System zur kontrollierbaren Freisetzung einer Substanz |
EP2380438A1 (fr) * | 2010-04-22 | 2011-10-26 | LANXESS Deutschland GmbH | Matières biocides |
WO2015005487A1 (fr) * | 2013-07-12 | 2015-01-15 | 住友化学株式会社 | Préparation agrochimique solide |
US10653136B2 (en) * | 2016-07-11 | 2020-05-19 | Covestro Llc | Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds |
US10750750B2 (en) * | 2016-07-11 | 2020-08-25 | Covestro Llc | Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds |
US10653135B2 (en) * | 2016-07-11 | 2020-05-19 | Covestro Llc | Methods for treating seeds with an aqueous composition and seeds treated therewith |
US20210400975A1 (en) | 2020-06-26 | 2021-12-30 | Lonza Solutions Ag | Methods and Compositions for Use in Glued-Wood Products |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5420242A (en) * | 1986-10-22 | 1995-05-30 | Kaare M. Gautvik | Production of human parathyroid hormone from microorganisms |
JPH0624903A (ja) * | 1992-04-09 | 1994-02-01 | Nippon Bayeragrochem Kk | 植物処理剤 |
US5725869A (en) * | 1994-06-20 | 1998-03-10 | Zeneca Limited | Microsphere reservoirs for controlled release application |
US5589544A (en) * | 1994-07-06 | 1996-12-31 | Advanced Elastomer Systems, L.P. | Soft thermoplastic elastomers having improved resistance to oil swell and compression set |
DE4443966A1 (de) * | 1994-12-09 | 1996-06-13 | Basf Ag | Thermoplastische Formmassen |
DE19645842A1 (de) * | 1996-11-07 | 1998-05-14 | Bayer Ag | Pflanzenbehandlungsmittel |
SG55424A1 (en) * | 1996-12-03 | 1998-12-21 | Gen Electric | Modified polycarbonate-polyester composition |
DE19652958A1 (de) * | 1996-12-19 | 1998-06-25 | Bayer Ag | ABS-Formmassen mit verbessertem Geruchsverhalten |
DE69821940T2 (de) * | 1997-06-30 | 2005-03-17 | Monsanto Technology Llc | Landwirtschaftlich aktive inhaltsstoffe enthaltende mikropartikel |
DE19805248A1 (de) * | 1998-02-10 | 1999-08-12 | Bayer Ag | Perlpolymerisat-Formulierungen |
JPH11315004A (ja) * | 1998-03-04 | 1999-11-16 | Nippon Bayer Agrochem Co Ltd | 水面施用製剤 |
KR100327501B1 (ko) * | 1998-07-14 | 2002-10-11 | 제일모직주식회사 | 난연성열가소성수지조성물 |
DE19834025A1 (de) * | 1998-07-28 | 2000-02-03 | Aventis Res & Tech Gmbh & Co | Mikrokapseln hergestellt aus Cycloolefinpolymeren oder Cycloolefincopolymeren und deren Verwendung zur kontrollierten Wirkstoffabgabe |
DE19933832A1 (de) * | 1999-07-20 | 2001-01-25 | Bayer Ag | Streugranulate |
US20050054537A1 (en) * | 2002-01-10 | 2005-03-10 | Hanns-Peter Muller | Powder formulations |
-
2002
- 2002-06-13 DE DE10226222A patent/DE10226222A1/de not_active Withdrawn
-
2003
- 2003-05-30 AU AU2003238181A patent/AU2003238181A1/en not_active Abandoned
- 2003-05-30 WO PCT/EP2003/005706 patent/WO2003105584A1/fr not_active Application Discontinuation
- 2003-05-30 EP EP03735508A patent/EP1515604A1/fr not_active Withdrawn
- 2003-05-30 MX MXPA04012358A patent/MXPA04012358A/es active IP Right Grant
- 2003-05-30 JP JP2004512503A patent/JP2005529173A/ja active Pending
- 2003-05-30 US US10/517,504 patent/US20060111242A1/en not_active Abandoned
- 2003-05-30 BR BR0312131-3A patent/BR0312131A/pt not_active IP Right Cessation
-
2004
- 2004-12-09 ZA ZA200409971A patent/ZA200409971B/xx unknown
Non-Patent Citations (1)
Title |
---|
See references of WO03105584A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2005529173A (ja) | 2005-09-29 |
WO2003105584A1 (fr) | 2003-12-24 |
DE10226222A1 (de) | 2004-01-08 |
US20060111242A1 (en) | 2006-05-25 |
BR0312131A (pt) | 2005-09-27 |
ZA200409971B (en) | 2006-02-22 |
MXPA04012358A (es) | 2005-02-25 |
AU2003238181A1 (en) | 2003-12-31 |
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