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WO1996003041A1 - Microparticules spheriques pourvues d'un revetement de cire interieur depose autour de composes biologiquement actifs - Google Patents

Microparticules spheriques pourvues d'un revetement de cire interieur depose autour de composes biologiquement actifs Download PDF

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Publication number
WO1996003041A1
WO1996003041A1 PCT/EP1995/002729 EP9502729W WO9603041A1 WO 1996003041 A1 WO1996003041 A1 WO 1996003041A1 EP 9502729 W EP9502729 W EP 9502729W WO 9603041 A1 WO9603041 A1 WO 9603041A1
Authority
WO
WIPO (PCT)
Prior art keywords
wax
microparticles
biologically active
active compound
microparticles according
Prior art date
Application number
PCT/EP1995/002729
Other languages
English (en)
Inventor
Rudolf Nastke
Ernst Neuenschwander
Original Assignee
Ciba-Geigy 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 Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Priority to AU30780/95A priority Critical patent/AU3078095A/en
Priority to EP95943508A priority patent/EP0772395A1/fr
Priority to JP8505406A priority patent/JPH11505466A/ja
Publication of WO1996003041A1 publication Critical patent/WO1996003041A1/fr

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
    • A01N25/26—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 in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules

Definitions

  • Spherical microparticles having an inner wax coating deposited around biologically active compounds Spherical microparticles having an inner wax coating deposited around biologically active compounds
  • the present invention relates to a process for the preparation of spherical microparticles which contain biologically active compounds and which are provided at the inner capsule wall with an additional wax layer deposited around the biologically active compound.
  • the invention also relates to the use of said microparticles for the preparation of a composition for controlling plant pests, weeds or animal parasites as well as to aqueous spray mixtures containing the microparticles obtained in the practice of this invention.
  • microencapsulation of active ingredients in polymeric materials with different polymers is known and can be carried out by various methods, as described for example in Encyclopedia of Polymer Science, John Wiley Sons, 1968, Vol. 8, pp. 719-736.
  • microencapsulation methods are: coacervation, interfacial polymerisation at liquid-liquid surfaces or interfacial polycondensation, for example at a solid phase boundary.
  • other suitable methods are physical methods such as the microencapsulation of aerosols.
  • Amino resins are often used as polymeric encapsulating materials for microparticles that contain agrochemical compounds. An overview of the broad field of use of these resins for microencapsulation is given, inter alia, in Acta Polymerica 40, (1989) No. 4, pp. 243-251.
  • the applied microparticles must be comparably active in field application to e.g. emulsif ⁇ able concentrates.
  • they shall release the active ingredient uniformly over an extended period of time.
  • v-rtually no active ingredient shall be released on skin contact, so that a high degree of handling safety is ensured.
  • microparticles prepared with self-crosslinking amino resins are described in Acta Polymerica 40, (1989) No. 5, pp. 325-331.
  • the starting materials are solid compounds which are e.g. additionally ground to give a fine dispersion in the aqueous polymer solution and are then encapsulated.
  • the drawback of this process is that the solid materials have to be ground to an average particle size of c. 10-30 ⁇ m.
  • the addition of active ingredients in the liquid, dissolved or melt state is therefore usually of interest.
  • EP-A-0 368 576 teaches, inter alia, that the insecticide chlorpyrifos is unstable to hydrolysis and, depending on the pH range, can rapidly lose its biological activity under the influence of water.
  • the active ingredient must have good stability to hydrolysis in the alkaline range, as it is frequently applied to concrete.
  • Another solution is to provide formulations in which the contact with water is greatly retarded, while the biological activity still remains intact. Such formulations must have release properties sufficiently effective to ensure reliable control of the termites.
  • another usual requirement is that of superior long-term stability under all climatic conditions, especially rain and tropical climate. Microencapsulations having more or less strongly hydrophilic capsule walls - depending on the polymer employed - can have drawbacks as regards their long-term stability.
  • the microcapsules contain, in addition to the active ingredient, a hydrophobic wax such that the wax forms a film that surrounds the active ingredient on the inner microcapsule wall. Penetration of water into the capsule core is thereby hindered, while the release properties remain effective enough to achieve sufficiently good activity.
  • the active ingredient is released approximately uniformly over an extended period of time from the microparticles, so that a good activity is achieved.
  • the invention relates to essentially spherical microparticles comprising a biologically active compound as core substance and a polymeric capsule material, wherein a hydrophobic wax forms a wax film as interlayer on the inner polymeric capsule wall and wholly or partially encapsulates the active ingredient.
  • the average thickness of the wax layer can be from 1 nm to 1 ⁇ m. Preferably it is from 5 nm to 100 nm.
  • the wax layers are not completely uniform, but have slightly different thicknesses.
  • the spherical microparticles preferably have an average diameter of 0.5 to 500 ⁇ m. More preferably the microparticles have an average diameter of 0.5 to 100 ⁇ m and, most preferably, of 0.5 to 20 ⁇ m.
  • the polymeric wall material is preferably 5 to 40 % by weight of the total weight of the microparticles.
  • the polymeric wall material may consist of a polyacrylate, a polyurethane, a polyester or an amino resin.
  • the polymeric wall material is preferably an amino condensation resin, most preferably a polycondensate of melamine and formaldehyde, a wholly or partially etherified melamine-formaldehyde condensate, a urea-formaldehyde condensate, a urea-glutaralde- hyde condensate, a benzoguanamine-formaldehyde condensate, or a urea-glyoxal condensate.
  • an amino condensation resin most preferably a polycondensate of melamine and formaldehyde, a wholly or partially etherified melamine-formaldehyde condensate, a urea-formaldehyde condensate, a urea-glutaralde- hyde condensate, a benzoguanamine-formaldehyde condensate, or a urea-glyoxal condensate
  • the molar ratios of urea to formaldehyde are 1:2.5 to 1:3.5, preferably 1:2.7 to 1: 3.2.
  • the molar ratios may be 1:1.5 to 1:2.5, preferably 1:1.8 to 1: 2.2.
  • the molar ratios of melamine to formaldehyde can be 1:3.5 to 1:8, preferably 1:4 to 1:6.
  • the degree of etherification of these resins can be adjusted by the molar ratio of melamine to methanol and is typically c. 1:10 to 1:20, preferably c. 1:15 to 1:18.
  • Suitable amino resins for forming microparticles will be found, inter alia, in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol. 2, pp. 440-469.
  • the polycondensate is most preferably a melamine-formaldehyde condensate, a wholly or partially etherified melamine-formaldehyde condensate, or a urea-formaldehyde condensate.
  • the biologically active compound is preferably a pesticide or a mixture of pesticides, and is most preferably a herbicide, an insecticide, an acaricide, a nematicide, an ectoparasiti- cide, a fungicide or a mixture thereof.
  • pesticides are: urea derivatives, triazines, triazoles, carbamates, phosphoric acid esters, dinitroanilines, morpholines, acylalanines, pyrethroids, benzilic acid esters and polycyclic halogenated hydrocarbons.
  • specific examples of pesticides suitable for use in the practice of this invention are listed hereinbelow (common names as given in The Pesticide Manual, 9th Edition, British Crop Protection Council):
  • Halogenated acetanilides Dimethachlor, alachlor, propachlor.
  • Atrazine propazine, terbuthylazine, ametryn, aziprotryne, cyromazine.
  • Etaconazole 1 -[2-(2,4-dichlorophenyl)-pent- 1 -yl]- 1H- 1 ,2,4-triazole, triadimefon, difenoconazole.
  • the hydrophobic wax may be a natural wax, a modified natural wax, or a semi-synthetic or fully synthetic wax.
  • the hydrophobic wax is preferably a vegetable wax, an animal wax, a montan wax, a paraffin wax, a polyolefin wax or an amide wax. Most preferably the hydrophobic wax is a macrocrystalline paraffin wax, a microcrystalline paraffin wax or a polyethylene wax.
  • the wax preferably has a melting point of 30 to 80°C.
  • the wax is used in an amount of 1 to 20 % by weight, most preferably of 5 to 15 % by weight, based on the biologically active compound or mixture thereof in the microcapsules.
  • the invention in another of its aspects, relates to a process for encapsulating biologically active compounds in the form of essentially spherical microcapsules, comprising the steps of a) preparing an aqueous solution of surfactants, catalysts and monomers, prepolymers or polymers which are suitable for forming a capsule wall, b) forming an emulsion or dispersion of the substantially water-insoluble biologically active compound or mixture thereof in the solution a) by adding said solution under high shear force, and c) forming a solid capsule wall around the biologically active compound or mixture thereof, which process comprises blending the biologically active compound with a hydrophobic wax before forming the emulsion or dispersion b), melting the wax and adding the melt to the solution a).
  • a preferred embodiment of the process comprises fusing the biologically active compound and the wax together and adding the co-melt blend to the polymer solution. It is particularly preferred to fuse the wax and the biologically active compound or mixture thereof together and to add this co-melt to the reaction solution a) at a temperature higher than that of said reaction solution a).
  • Another preferred embodiment of the process comprises dissolving the wax in a solvent, adding the solid active ingredient and cautiously evaporating the solvent, with stirring, to give a wax-coated active ingredient powder which can be used direct for the preparation of the microparticles.
  • the aqueous solution may contain, in addition to the monomers, prepolymers or polymers that form the capsule wall, one or more than one water-soluble monomer, oligomer or polymer as emulsifier or dispersant.
  • Suitable emulsifiers or dispersants are anionic, canonic or nonionic substances.
  • the surfactants customarily used in formulation technology are described, inter alia, in the following publications:
  • the surfactants are polyethylene glycols, polyethylene glycol monoalkyl ethers, polyethylene glycol-polypropylene glycol copolymers, polyvinyl pyrrolidones and acrylic acid-acrylamide copolymers.
  • the invention in another of its aspects, relates to a process for controlling plant pests, weeds or animal parasites, which comprises suspending the novel microparticles in a biologically active concentration in water and applying the suspension so obtained to the pests or to the locus thereof.
  • the invention relates to the use of the novel microparticles for the preparation of a composition for controlling plant pests, weeds or animal parasites, and to water-dilutable powders, water-dispersible granules or aqueous spray mixtures containing said microparticles.
  • Example Al Preparation of a modified melamine-formaldehyde precondensate With stirring, 28 g of melamine (0.22 mol) are added to 124 ml of a 30 % aqueous solution of formaldehyde. The reaction mixture is adjusted with 1 N aqueous NaOH to pH 9 and heated to 94°C, whereupon the melamine dissolves while reacting with the aldehyde. The reaction mixture is then cooled to 62°C and, after addition of 120 ml of methanol (3.75 mol) and 7 ml of a 15 % aqueous solution of hydrochloric acid, the reaction is carried out at 62°C for 30 minutes.
  • Example A2 Preparation of a urea-glutaraldehyde precondensate With stirring, 60 g (1 mol) of urea are dissolved in 800 g (2 mol) of a 25 % aqueous solu ⁇ tion of glutardiol aldehyde. The pH is adjusted with 1 N aqueous NaOH to 7-8 and the solution is then heated to a temperature of 70°C and stirred for 40 minutes at this temperature. The solution is afterwards cooled to room temperature.
  • Example Bl 60 ml of water and 3 g of the precondensate prepared according to Example Al as well as 0.15 g of polyethylene glycol (molecular weight 300) are charged to a reactor with temperature control.
  • the reaction mixture is heated to 40°C and acidified with 2.1 ml of 2N aqueous citric acid. Then 12.6 g of methidathion and 1.26 g of paraffin wax (m.p. 53°C) are fused together and homogenised.
  • the melt is added rapidly to the reaction mixture, with stirring (TJlfc-aturrax, 12000 rpm), and stirred for 10 minutes at this speed.
  • Example B2 25 g of chlortoluron are mixed in a rotary evaporator with a 5 % solution of paraffin wax (m.p. 85°C) in petroleum spirit and the petroleum spirit phase is removed by evaporation until a finely particulate free-flowing powder is obtained. Then 140 ml of water and 30 g of the precondensate prepared in Example Al as well as 21 ml of a 2N aqueous solution of citric acid are charged to a reactor with temperature control and the wax-treated chlortoluron is dispersed therein. The mixture is heated to 60°C and further stirred for 120 minutes. After cooling, a suspension of fine spherical particles having diameters of 1 to 10 ⁇ m is obtained. The suspension can be further used direct for a formulation or the particles can be dried to give a free-flowing powder. Electron micrographs show that the wax has deposited mainly on the inner wall of the microcapsule.
  • Example B3 The procedure of Example B2 is repeated, but using 70 g of the precondensate of Example A2, giving a suspension which can be further used direct for a formulation or the particles can be dried to give a free-flowing powder. Electron micrographs show that the wax has deposited mainly on the inner wall of the microcapsule.

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  • 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 des microparticules sensiblement sphériques comprenant un composé biologiquement actif, qui forme le noyau, et un matériau polymère, qui forme une capsule dont la paroi intérieure est revêtue d'une couche de cire hydrophobe qui forme une couche intermédiaire qui encapsule complètement ou partiellement l'ingrédient actif. La présente invention concerne également un procédé permettant de préparer ces microparticules, l'utilisation de ces microparticules pour préparer une composition destinée à la lutte contre les parasites végétaux, les mauvaises herbes ou les parasites animaux, ainsi que des mélanges aqueux à pulvériser, des granulés dispersibles dans l'eau ou des poudres diluables dans l'eau contenant les microparticules selon l'invention.
PCT/EP1995/002729 1994-07-22 1995-07-12 Microparticules spheriques pourvues d'un revetement de cire interieur depose autour de composes biologiquement actifs WO1996003041A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU30780/95A AU3078095A (en) 1994-07-22 1995-07-12 Spherical microparticles having an inner wax coating deposited around biologically active compounds
EP95943508A EP0772395A1 (fr) 1994-07-22 1995-07-12 Microparticules spheriques pourvues d'un revetement de cire interieur depose autour de composes biologiquement actifs
JP8505406A JPH11505466A (ja) 1994-07-22 1995-07-12 生物学的に活性な化合物の周りに付着された内部ワックスコーティングを有する球状微粒子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2330/94-0 1994-07-22
CH233094 1994-07-22

Publications (1)

Publication Number Publication Date
WO1996003041A1 true WO1996003041A1 (fr) 1996-02-08

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PCT/EP1995/002729 WO1996003041A1 (fr) 1994-07-22 1995-07-12 Microparticules spheriques pourvues d'un revetement de cire interieur depose autour de composes biologiquement actifs

Country Status (4)

Country Link
EP (1) EP0772395A1 (fr)
JP (1) JPH11505466A (fr)
AU (1) AU3078095A (fr)
WO (1) WO1996003041A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997027939A1 (fr) * 1996-01-31 1997-08-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Microparticules contenant une substance active et un materiau polymere formant la paroi d'une capsule, leur procede de fabrication et leur utilisation
US6113950A (en) * 1996-10-07 2000-09-05 E. I. Du Pont De Nemours And Company Process for coating biological pesticides and compositions therefrom
WO2003077651A1 (fr) * 2002-03-15 2003-09-25 Cheminova A/S Formulation de microparticules a toxicite aquatique reduite
WO2004016234A1 (fr) * 2002-08-14 2004-02-26 Quest International Services B.V. Compositions comprenant une matiere encapsulee
WO2008062221A2 (fr) * 2006-11-23 2008-05-29 Exosect Limited Comprime
AU2006327936B2 (en) * 2005-12-23 2013-05-02 Syngenta Limited. Formulation
EP2801256A1 (fr) * 2013-05-08 2014-11-12 LANXESS Deutschland GmbH Microcapsules contenant un agent algicide et un polymère mélamine-formaldéhyde
WO2017037210A1 (fr) 2015-09-03 2017-03-09 BASF Agro B.V. Compositions de microparticules comprenant du saflufénacil
WO2017068024A1 (fr) 2015-10-22 2017-04-27 Basf Se Procédé de préparation d'une dispersion aqueuse de microparticules
WO2017097282A1 (fr) * 2015-12-11 2017-06-15 Katz Biotech Ag Capsules à noyau liquide pour lutter contre des parasites
WO2019180328A1 (fr) 2018-03-20 2019-09-26 Ab7 Innovation Composition contenant un traceur de substance active ingérée et procédé de détection dudit traceur
US11064697B2 (en) 2015-07-24 2021-07-20 Basf Se Pyridine compounds useful for combating phytopathogenic fungi
EP4011208A1 (fr) 2020-12-08 2022-06-15 BASF Corporation Compositions de microparticules comprenant du fluopyram
EP4011205A1 (fr) 2020-12-08 2022-06-15 Basf Se Compositions de microparticules comprenant de la trifludimoxazine

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102806A (en) * 1975-08-18 1978-07-25 Takeda Chemical Industries, Ltd. Method of producing microcapsules and resulting product
JPS6413002A (en) * 1987-07-06 1989-01-17 Sumitomo Chemical Co Organic phosphorus insecticide composition for controlling insect pest in forest
WO1990000005A1 (fr) * 1988-06-30 1990-01-11 Redding Bruce K Jr Pesticides microencapsules a leurre
WO1990002655A1 (fr) * 1988-09-06 1990-03-22 Encapsulation Systems, Inc. Microcapsules facilitant la liberation de l'agent actif

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102806A (en) * 1975-08-18 1978-07-25 Takeda Chemical Industries, Ltd. Method of producing microcapsules and resulting product
JPS6413002A (en) * 1987-07-06 1989-01-17 Sumitomo Chemical Co Organic phosphorus insecticide composition for controlling insect pest in forest
WO1990000005A1 (fr) * 1988-06-30 1990-01-11 Redding Bruce K Jr Pesticides microencapsules a leurre
WO1990002655A1 (fr) * 1988-09-06 1990-03-22 Encapsulation Systems, Inc. Microcapsules facilitant la liberation de l'agent actif

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8908, Derwent World Patents Index; Class A97, AN 89-059198 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997027939A1 (fr) * 1996-01-31 1997-08-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Microparticules contenant une substance active et un materiau polymere formant la paroi d'une capsule, leur procede de fabrication et leur utilisation
DE19603453C1 (de) * 1996-01-31 1997-10-02 Fraunhofer Ges Forschung Mikropartikel, enthaltend einen Wirkstoff und ein polymeres Kapselwandmaterial, ein Verfahren zu deren Herstellung und deren Verwendung
US6113950A (en) * 1996-10-07 2000-09-05 E. I. Du Pont De Nemours And Company Process for coating biological pesticides and compositions therefrom
WO2003077651A1 (fr) * 2002-03-15 2003-09-25 Cheminova A/S Formulation de microparticules a toxicite aquatique reduite
AU2009243427B2 (en) * 2002-08-14 2011-06-02 Givaudan Nederland Services B.V. Compositions comprising encapsulated material
US7799752B2 (en) 2002-08-14 2010-09-21 Quest International Services B.V. Compositions comprising encapsulated material
WO2004016234A1 (fr) * 2002-08-14 2004-02-26 Quest International Services B.V. Compositions comprenant une matiere encapsulee
AU2006327936B2 (en) * 2005-12-23 2013-05-02 Syngenta Limited. Formulation
AU2006327942B2 (en) * 2005-12-23 2013-09-12 Syngenta Limited Formulation
WO2008062221A2 (fr) * 2006-11-23 2008-05-29 Exosect Limited Comprime
WO2008062221A3 (fr) * 2006-11-23 2009-04-16 Exosect Ltd Comprime
GB2456261A (en) * 2006-11-23 2009-07-15 Exosect Ltd A compact
GB2456261B (en) * 2006-11-23 2012-02-29 Exosect Ltd A compact
US9894900B2 (en) 2006-11-23 2018-02-20 David Webster Compact for insect control
WO2014180890A1 (fr) * 2013-05-08 2014-11-13 Lanxess Deutschland Gmbh Microcapsules contenant un algicide et un polymère de mélamine et de formaldéhyde
EP2801256A1 (fr) * 2013-05-08 2014-11-12 LANXESS Deutschland GmbH Microcapsules contenant un agent algicide et un polymère mélamine-formaldéhyde
US11064697B2 (en) 2015-07-24 2021-07-20 Basf Se Pyridine compounds useful for combating phytopathogenic fungi
WO2017037210A1 (fr) 2015-09-03 2017-03-09 BASF Agro B.V. Compositions de microparticules comprenant du saflufénacil
US11317628B2 (en) 2015-09-03 2022-05-03 BASF Agro B.V. Microparticle compositions comprising saflufenacil
WO2017068024A1 (fr) 2015-10-22 2017-04-27 Basf Se Procédé de préparation d'une dispersion aqueuse de microparticules
WO2017097282A1 (fr) * 2015-12-11 2017-06-15 Katz Biotech Ag Capsules à noyau liquide pour lutter contre des parasites
US11140897B2 (en) 2015-12-11 2021-10-12 Katz Biotech Ag Liquid-core capsules for pest control
WO2019180328A1 (fr) 2018-03-20 2019-09-26 Ab7 Innovation Composition contenant un traceur de substance active ingérée et procédé de détection dudit traceur
FR3079303A1 (fr) * 2018-03-20 2019-09-27 Ab7 Innovation Procede pour la detection de la presence d'un traceur dans les excrements
EP4011208A1 (fr) 2020-12-08 2022-06-15 BASF Corporation Compositions de microparticules comprenant du fluopyram
EP4011205A1 (fr) 2020-12-08 2022-06-15 Basf Se Compositions de microparticules comprenant de la trifludimoxazine
WO2022122520A1 (fr) 2020-12-08 2022-06-16 Basf Corporation Compositions de microparticules comprenant des fongicides
WO2022122526A1 (fr) 2020-12-08 2022-06-16 Basf Se Compositions de microparticules comprenant de la trifludimoxazine

Also Published As

Publication number Publication date
JPH11505466A (ja) 1999-05-21
EP0772395A1 (fr) 1997-05-14
AU3078095A (en) 1996-02-22

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