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WO2003007712A1 - Granules contenant de la streptomycine et procede de fabrication de ceux-ci - Google Patents

Granules contenant de la streptomycine et procede de fabrication de ceux-ci Download PDF

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Publication number
WO2003007712A1
WO2003007712A1 PCT/EP2002/008076 EP0208076W WO03007712A1 WO 2003007712 A1 WO2003007712 A1 WO 2003007712A1 EP 0208076 W EP0208076 W EP 0208076W WO 03007712 A1 WO03007712 A1 WO 03007712A1
Authority
WO
WIPO (PCT)
Prior art keywords
antibiotic
granules
water
process according
salt
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
PCT/EP2002/008076
Other languages
English (en)
Inventor
Wolfgang Kempe
Constant Johan Van Lookeren Campagne
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.)
Koninklijke DSM NV
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
DSM NV
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 DSM IP Assets BV, DSM NV filed Critical DSM IP Assets BV
Publication of WO2003007712A1 publication Critical patent/WO2003007712A1/fr
Anticipated expiration legal-status Critical
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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof

Definitions

  • the present invention relates to the formulation of agricultural antibiotics. More specifically, the present invention discloses an antibiotic-containing water dispersible granule for application in crop protection and methods for the preparation thereof.
  • Fire blight is a destructive infectious fruit disease caused by the bacterium Erwinia amylovora. The disease kills blossoms, fruit, shoots, limbs and tree trunks and is characterized by its fast infection patterns leading to a scorched appearance of the foliage and branches it leaves behind. Following a heavy outbreak of fire blight in the early nineties in Southwest Germany, application of the antibiotic streptomycin has been allowed during bloom of apple and pear since 1994.
  • streptomycin The main drawbacks of the use of streptomycin are that severe risks are taken with regard to dust-inhalation incidences with workers during preparation of the liquid to be sprayed, using state of the art powder formulations.
  • the well known wettable powder formulations of streptomycin have led to unwanted exposure of users to dust when opening packages and preparing the spray.
  • continuous use has led to increased residues of streptomycin found in honey collected by bees in orchards that were treated with streptomycin sprays. These effects can easily give rise to resistance problems. Because of this resistance issue, all existing antibiotic formulations for agricultural purposes were eventually banned in some European countries, such as Germany.
  • a possible solution to this problem is formulating the antibiotic in dust-free granules that are dispersible in water and can be applied in the spraying equipment.
  • Water dispersible granules containing active chemical components with herbicidal-, fungicidal-, or insecticidal modes of action for application in crop-protection and processes for making such granules are known from International Patent Application WO89/00079.
  • the particular problem in making these antibiotic-containing granules for crop protection is that they have to fulfill many performance criteria, which are often narrowly defined, such as dispersibility, flowability, low dust content, particle size distribution, shelf life, and solubility.
  • a novel granule and a process for the preparation of said granule is disclosed. Surprisingly, this granule provides a controlled release of the antibiotic and complies with all of the abovementioned specifications that are to be met.
  • a process for the preparation of an antibiotic-containing granule suitable for use in crop protection the antibiotic-containing granules are obtained by mixing the desired ingredients of the granules in a form suitable for application in a granulator. After mixing, the granulation is performed and the resulting granules are dried.
  • the second aspect of the present invention relates to antibiotic-containing granules obtainable by the process of the first aspect, which seeks to solve the problems encountered in the prior art.
  • the ingredients of the granule comprise an antibiotic, a water-insoluble carrier, a water-soluble salt of an alkaline (-earth) metal and/or an ammonium salt, water, optionally one or more thickening agents, optionally one or more tracer molecules, and optionally one or more surfactants.
  • w/w is defined as the amount relative to the total weight of the granule after drying, unless specified otherwise.
  • a dried granule may contain residual water ranging from 1 -8% (w/w).
  • Antibiotics are substances from all classes of compounds that are known to have antibiotic activity against bacteria, such as amino glycosides, ⁇ -lactams, macrolides, quinolones, tetracyclines, and salts and esters thereof.
  • Preferred antibiotics are amino glycosides such as streptomycin and its salts and quinolones such as flumequine.
  • the amount of antibiotic as present in the granule should be at least 10% (w/w), preferably at least 15% (w/w), more preferably at least 20% (w/w). Upper levels of antibiotic are influenced by the amounts of other components in the mixture.
  • the amount of carrier ranges from a minimal value of 1-30% (w/w), preferably 20-30% (w/w), more preferably 25-30% (w/w), to a maximal value of 30-80% (w/w), preferably 30-50% (w/w), more preferably 30-40% (w/w).
  • the carrier has an Al 2 0 3 content ranging from a minimal value of 5-35% (w/w), preferably 20-35% (w/w), more preferably 30-35% (w/w), to a maximal value of 35-65% (w/w), preferably 35-50% (w/w), more preferably 35-40% (w/w).
  • the carrier may further contain SiO 2 , its content ranging from a minimal value of 20-50% (w/w), preferably 35-50% (w/w), more preferably 45-50% (w/w), to a maximal value of 50-80% (w/w), preferably 50-65% (w/w), more preferably 50-55% (w/w).
  • the SiO 2 may be present naturally or added to the carrier.
  • the carrier should have an aluminum oxide content of more than 35% (w/w) and be added such, that the ratio of aluminum oxide/antibiotic in the granule is at least 0.1 (w/w), preferably at least 0.2 (w/w), more preferably at least 0.3 (w/w), still more preferably at least 0.4 (w/w), most preferably at least 0.5 (w/w).
  • the upper limit of said ratio is limited by physical boundaries, as the person skilled in the art will understand.
  • a substantial part of the carrier particles should have a particle size ranging from 2 ⁇ m to 10 ⁇ m.
  • the granule further contains a water-soluble salt of an alkaline (-earth) metal and/or an ammonium salt.
  • a salt for instance is ammonium benzoate, ammonium sulfate, magnesium sulfate, potassium benzoate, potassium sulfate (K 2 SO 4 ), sodium benzoate, sodium chloride, and/or sodium sulfate.
  • the salt can be a single salt or a mixture of more than one salt.
  • the salt is added in order to improve the processing and storage stability of the dry antibiotic granulates and/or to improve the antimicrobial and/or antifungal properties of the antibiotic granulates.
  • a preferred water-soluble salt of an alkaline (-earth) metal is K 2 SO 4 .
  • the person skilled in the art will understand that salt can be added as such but can also, in some cases, be formed in situ by addition of the corresponding acid at any point during the mixing process.
  • the amount of salt ranges from a minimal value of 1-20% (w/w), preferably 10-
  • thickening agent is used in the broad sense and includes materials that can improve the pelleting stabilization. Suitable thickening agents are hydroxylated or carboxylated cellulose, polysaccharides such as alginates and gums, biopolymers such as xanthan gum, and polycarboxylates such as sodium polycarboxylate.
  • the thickening agent is sodium polycarboxylate based Geropon T/36, the amount ranging from a minimal value of 1-25% (w/w), preferably 15-25% (w/w), more preferably 20-25% (w/w), to a maximal value of 25-50% (w/w), preferably 25-35% (w/w), more preferably 25-30% (w/w).
  • surfactant is used in the broad sense to include materials, which may be referred to as emulsifying agents, dispersing agents, and wetting agents.
  • the surfactant component may comprise one or more surfactants from the anionic, cationic and/or non-ionic type.
  • anionic surfactants are aliphatic sulfonic ester salts like lauryl sulfate, aromatic sulfonic acid salts, salts of lignosulfates, and soaps.
  • non- ionic surfactants are the condensation products of ethylene oxide with fatty alcohols such as oleylalcohol, alkyl phenols, lecithins, and phosphorylated surfactants such as phosphorylated ethylene oxide/propylene oxide block copolymer and ethoxylated and phosphorylated styryl-substituted phenol.
  • Preferred surfactants are anionic wetting agents such as sodium salts of sulfated alkyl carboxylate, and/or alkyl naphtalenesulphonate and/or dispersing agents such as naphthalene formaldehyde condensate.
  • the amount of surfactant ranges from a minimal value of 0.1-1% (w/w) to a maximal value of 1-10% (w/w).
  • Water is added to the mixture of ingredients to be processed to granules to improve the mixing granulation process.
  • the order of addition of the ingredients is not a critical parameter, although it is well known that gradual addition of water often leads to the best mixing results.
  • the amount of added water typically is determined by the process conditions.
  • the mixing of the antibiotic, the carrier, and water may additionally comprise kneading of the mixture. This may improve the plasticity of the mixture in order to facilitate granulation (e.g. extrusion).
  • the mechanical processes that are applied in the present invention for processing the mixture of the antibiotic, water and the solid carrier into granules are frequently used in food, feed and enzyme formulation processes, where they occur in a number of ways such as drum granulation, expansion, extrusion, fluid bed agglomeration, high shear granulation, pelleting, spheronization, or a combination thereof.
  • These processes are characterized by an input of mechanical energy, such as the drive of a screw, the rotation of a mixing mechanism, the pressure of a rolling mechanism of a pelleting apparatus, the movement of particles by a rotating bottom plate of a fluid bed agglomerator or the movement of the particles by a gas stream, or a combination thereof.
  • These processes allow the solid carrier (e.g.
  • the solid carrier can be mixed with the antibiotic (e.g. in a powder form) to which water is added, which acts as granulating liquid.
  • the granule e.g. an agglomerate
  • the granule is formed by spraying an antibiotic-containing liquid onto the carrier in a fluid bed agglomerator.
  • the resulting granules can include an agglomerate as can be produced in a fluid bed agglomerator.
  • the granules are formed by extrusion. Preferably, extrusion is performed at low pressure.
  • Low-pressure extrusion offers the advantage that the temperature in the extruded mixture will not, or only slightly, increase.
  • Low-pressure extrusion includes extrusion in, for example, a Fuji Paudal basket- or dome-extruder.
  • the extrusion may naturally produce granules (the granules may break off after passage through a die) or a cutting device may be employed.
  • the granulator is a low-pressure basket extruder equipped with a perforated screen and a temperature indicator.
  • the diameter of the holes ranges has a minimal value of 0.2-1.2 mm, more preferably 0.8-1.2 mm, most preferably 1.0-1.2 mm.
  • the maximal value of the holes is 1.2-2.5 mm, more preferably 1.2-1.6 mm, most preferably 1.2-1.4 mm.
  • the temperature of the extrusion process can be controlled by increasing or reducing the speed of the paddles and has a minimal value of 5-40°C, preferably 25-40°C, more preferably 35-40°C.
  • the maximal temperature value is 40-75°C, preferably 50-65°C, more preferably 55-60°C.
  • the granules obtained can be subjected to rounding off (e.g. spheronization), such as in an spheronizer, e.g. a MarumeriserTM machine and/or compaction machine.
  • the granules can be spheronized prior to drying since this may reduce dust formation in the final granules and/or may facilitate any coating of the granules.
  • the granules can then be dried, such as in a fluid bed drier or, in case of the fluid bed agglomeration, can be immediately dried (in the agglomerator) to obtain (solid dry) granules.
  • Other known methods for drying granules in the food, feed or enzyme industry can be used by the skilled person.
  • the granules are flowable.
  • the discharged particles are dried using a fluid bed drier.
  • Particles are dried to a final moisture content that has a minimal value of 0.5-2.5% (w/w), preferably 1.5-2.5% (w/w), more preferably 2.0-2.5% (w/w).
  • the maximal value of the moisture content is 2.5-10% (w/w), preferably 2.5-5.0% (w/w), more preferably 2.5-3.0% (w/w).
  • the third aspect of the present invention relates to the use of the granules of the second aspect dispersed in, or as a component of, a fluid that is applied to crops, fruit, plants or trees using spraying or pouring equipment with the aim of preventing, suppressing, or treating infectious diseases in agriculture such as fire blight.
  • Geropon T/36 a sodium polycarboxylate based thickening agent.
  • Morwet EFW a wetting agent containing sodium salts of sulfated alkyl carboxylate and alkyl naphtalenesulphonate - 4.0 kg Morwet D245 dispersing agent, a naphtalene formaldehyde condensate
  • the formulated streptomycin sulfate water dispersible granule has the following properties:
  • Geropon T/36 a sodium polycarboxylate based thickening agent.
  • 5.0 Kg Morwet EFW a wetting agent containing sodium salts of sulfated alkyl carboxylate and alkyl naphtalenesulphonate - 15.0 Kg Morwet D245 dispersing agent, a naphtalene formaldehyde condensate
  • the formulated streptomycin sulfate water dispersible granule has the following properties:

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

Abstract

L'invention concerne un procédé de fabrication de granulés contenant un antibiotique solubles dans l'eau à utiliser dans la protection de récoltes et les granulés contenant un antibiotique solubles dans l'eau que l'on peut obtenir par ledit procédé. De plus, cette invention concerne l'utilisation desdits granulés solubles dans ou comme composant de, un fluide qui est appliqué aux récoltes, fruits, plantes ou arbres par vaporisation ou déversement dans le but de prévenir, supprimer ou traiter des maladies connues de l'agriculture comme le feu bactérien par exemple. Ce procédé consiste à traiter un antibiotique ou un sel de celui-ci, un excipient contenant de l'oxyde d'aluminium insoluble dans l'eau, un sel soluble dans l'eau d'un métal alcalin(terreux) et/ou un sel d'ammonium, de l'eau et éventuellement des surfactants et des agents épaississants afin d'obtenir des granulés contenant un antibiotique et sécher les granulés, caractérisé par le fait que le taux oxyde d'aluminum/antibiotique est au moins égal à 0,1 (poids/poids) et la quantité d'antibiotique dans les granulés contenant ledit antibiotique est de 10% (poids/poids) au moins.
PCT/EP2002/008076 2001-07-19 2002-07-17 Granules contenant de la streptomycine et procede de fabrication de ceux-ci Ceased WO2003007712A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01202777 2001-07-19
EP01202777.7 2001-07-19

Publications (1)

Publication Number Publication Date
WO2003007712A1 true WO2003007712A1 (fr) 2003-01-30

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PCT/EP2002/008076 Ceased WO2003007712A1 (fr) 2001-07-19 2002-07-17 Granules contenant de la streptomycine et procede de fabrication de ceux-ci

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WO (1) WO2003007712A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120107422A1 (en) * 2009-07-10 2012-05-03 Chevita Tierarzneimittel Gmbh Compositions and method for preventing and treating fire blight

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB788668A (en) * 1954-06-14 1958-01-08 Pfizer & Co C Improvements in or relating to antibiotic compositions for treating plants
JPS5212925A (en) * 1975-07-19 1977-01-31 Microbial Chem Res Found A plant disease controlling agent
JPS55153706A (en) * 1979-05-17 1980-11-29 Hokko Chem Ind Co Ltd Fungicide for agriculture and gardening
JPS60224608A (ja) * 1984-04-23 1985-11-09 Takeda Chem Ind Ltd 安定な農園芸用殺菌組成物
JPS6299356A (ja) * 1985-10-25 1987-05-08 Nippon Niyuukazai Kk 顆粒状水和剤組成物
WO1989000079A1 (fr) * 1987-07-01 1989-01-12 Ici Australia Operations Proprietary Limited Granules se dispersant dans l'eau
JPH09124406A (ja) * 1995-11-06 1997-05-13 Takeda Chem Ind Ltd 顆粒状水和剤

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB788668A (en) * 1954-06-14 1958-01-08 Pfizer & Co C Improvements in or relating to antibiotic compositions for treating plants
JPS5212925A (en) * 1975-07-19 1977-01-31 Microbial Chem Res Found A plant disease controlling agent
JPS55153706A (en) * 1979-05-17 1980-11-29 Hokko Chem Ind Co Ltd Fungicide for agriculture and gardening
JPS60224608A (ja) * 1984-04-23 1985-11-09 Takeda Chem Ind Ltd 安定な農園芸用殺菌組成物
JPS6299356A (ja) * 1985-10-25 1987-05-08 Nippon Niyuukazai Kk 顆粒状水和剤組成物
WO1989000079A1 (fr) * 1987-07-01 1989-01-12 Ici Australia Operations Proprietary Limited Granules se dispersant dans l'eau
JPH09124406A (ja) * 1995-11-06 1997-05-13 Takeda Chem Ind Ltd 顆粒状水和剤

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1977-18789Y, XP002219598, "Agricultural germicide contg. negamycin (salt)-used against e.g. Pseudomonas lachrymans, glumae, mori and solancearum, and streptomyces scables" *
DATABASE WPI Derwent World Patents Index; AN 1981-08481D, XP002219597, "Agricultural fungicide-contains active mixt. of kasugamycin (salt) with polyoxin Gp. antibiotic salt." *
DATABASE WPI Derwent World Patents Index; AN 1985-320774, XP002219599, "Stabilised agricultural fungicide compsn.-contg. valinomycin, mineral carrier and preservative e.g. benzoic acid" *
DATABASE WPI Derwent World Patents Index; AN 1987-167067, XP002219594, "Granular wettable agrochemical composition-contains alkyl di:phenyl ether di:sulphonic acid." *
DATABASE WPI Derwent World Patents Index; AN 1994-190416, XP002219596, "Antibiotic tablets prodn.-by drying and simultaneous granulation, in fluidised layer, of inert fillers, sprayed with aq. soln. of antibiotic and starch" *
DATABASE WPI Derwent World Patents Index; AN 1997-316417, XP002219595, "Granular water dispersible agent-comprises chemical active agent and metal oxide e.g. aluminium oxide, and may additionally include anionic or non-ionic surfactant." *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120107422A1 (en) * 2009-07-10 2012-05-03 Chevita Tierarzneimittel Gmbh Compositions and method for preventing and treating fire blight
US9149043B2 (en) * 2009-07-10 2015-10-06 Ulf Abele Compositions and method for preventing and treating fire blight

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