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EP1022940A1 - Dispersion agent for granulates which contain water-insoluble agrochemical agents - Google Patents

Dispersion agent for granulates which contain water-insoluble agrochemical agents

Info

Publication number
EP1022940A1
EP1022940A1 EP98954333A EP98954333A EP1022940A1 EP 1022940 A1 EP1022940 A1 EP 1022940A1 EP 98954333 A EP98954333 A EP 98954333A EP 98954333 A EP98954333 A EP 98954333A EP 1022940 A1 EP1022940 A1 EP 1022940A1
Authority
EP
European Patent Office
Prior art keywords
granules
granules according
weight
monomer
radically polymerizable
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Withdrawn
Application number
EP98954333A
Other languages
German (de)
French (fr)
Inventor
Hans-Georg Mainx
Ingo Wegener
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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 Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1022940A1 publication Critical patent/EP1022940A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable

Definitions

  • the present invention relates to granules which, in addition to water-insoluble agrochemical active ingredients and optionally other auxiliaries, contain a particular copolymeric dispersant, the use of certain copolymers as dispersants in such granules and a process for protecting plants against pests.
  • Water-insoluble agrochemical active ingredients such as, for example, fertilizers, herbicides, pesticides, insecticides or seed treatment agents, can be used in a large number of formulations. This includes e.g. aqueous dispersions or solutions in suitable organic solvents.
  • the active ingredients can also be prepared in the form of sprays or pastes. They can also be used in solid form, for example as dusts in a mixture with suitable extenders, such as stone powder, in tablet form or as granules.
  • suitable extenders such as stone powder
  • the latter formulation is particularly suitable since highly concentrated, storage-stable and easy-to-handle preparations are obtained in this way.
  • the granules are dispersed in water shortly before the actual application, the user being able to set the concentration specified for the particular application.
  • these granules usually also contain fillers and / or carriers and further auxiliaries.
  • Such granules can be produced either by impregnating a suitable porous carrier with the liquid active ingredient (or a liquid formulation of a solid active ingredient), for example by spraying on the Active ingredient on the porous carrier material, or by granulating the active ingredient with suitable carriers and auxiliary substances in the presence of an auxiliary liquid, for example water.
  • Extruders are also used in the production of such granules, but this exposes the batch to be granulated to high pressures. It is then frequently observed that the granules are no longer sufficiently dispersible in water.
  • auxiliaries are added which should enable better dispersion of the granules, e.g. B. anionic surfactants (see R. Wengler, Chemistry of Plant Protection and Pest Control, Springer-Verlag, 1970, Volume 1, pages 41 to 54).
  • the invention therefore relates, in a first embodiment, to granules containing at least one water-insoluble agrochemical active ingredient and a polymeric dispersant and, if appropriate, further auxiliaries, the polymeric dispersant being a copolymer which can be prepared by polymerizing a) from 1 to 99% by weight of radically polymerizable, ethylenically unsaturated acids and / or their anhydrides b) 99 to 1% by weight of radically polymerizable ethylenically unsaturated esters and optionally c) 0.5 to 20% by weight of further free-radically polymerizable co-monomers.
  • Agrochemical active substances are those chemical compounds that are used in the field of agriculture. These include, in particular, pesticides and pesticides (Römpp Chemie Lexikon, Volume 6, 9th edition, 1991, page 3323). Examples of suitable connections can be found in the work by R. Wegler cited above. However, only those compounds are selected which are not or hardly soluble in water at room temperature (20 ° C.), that is to say that they have a solubility of at most 0.1% by weight in one liter of water at room temperature. Particularly preferred are those granules which contain crop protection agents as active ingredients, e.g.
  • Suitable water-insoluble agrochemical active ingredients can be both solid and liquid at room temperature - preferred in terms of application technology and solid active ingredients are particularly suitable for use in granules.
  • Water-insoluble active substances from the classes of nitrophenol derivatives, phosphoric acid esters, phenylurea or thiourea derivatives, triazines, dimethylmorpholines, diphenylsulfones, methylcarbamates, naphthylcarbamates, piperonylurea derivatives, thiophosphates or trichloroethane derivatives are particularly preferred.
  • the granules according to the invention preferably contain the water-insoluble agrochemical active ingredient in amounts between 0.5 and 90% by weight. However, granules with a high proportion of active ingredients, preferably between 30 and 90% by weight, are particularly preferred.
  • the polymeric dispersing agents contained in the granules according to the invention are known compounds.
  • EP 372 746 A1 describes copolymers of acrylic acid or methacrylic acid with esters of acrylic or methacrylic acid with long-chain alcohols. However, these are only described as water repellents for leather finishing.
  • DE 4129244 AI discloses copolymers of half-esters of maleic acid with oleophilic alcohols and acrylic acid and / or methacrylic acid and optionally further co-monomers, which can be used in the form of aqueous dispersions as auxiliaries for the oiling of leather and fur skins.
  • DE 4223111 AI describes copolymers of fatty crotonates and maleic acid or maleic anhydride and their use in leather finishing. None of the cited documents describes the use of such copolymers in crop protection agents or as dispersing agents.
  • copolymers used in the granules according to the invention can be produced by all known processes for free-radical polymerization.
  • the monomers are usually dissolved in water and then a polymerization reaction is initiated by adding suitable radical initiators or by UV light.
  • the copolymers are prepared by the simultaneous reaction of at least two different monomer units a) and b) and optionally c).
  • the monomers of group a) are free-radically polymerizable ethylenically unsaturated, preferably mono-unsaturated acids and / or their anhydrides. Suitable monomers are organic carboxylic acids with 3 to 10 carbon atoms, e.g. Acrylic and methacrylic acid, crotonic acid, maleic and fumaric acid or their anhydrides. Mixtures of component a) can also be used as monomers. Copolymers whose monomer component a) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid or maleic anhydride are particularly preferred.
  • Free-radically polymerizable ethylenically unsaturated esters are used as monomer block b).
  • Suitable acid components are the mono- and dicarboxylic acids mentioned under a), which are esterified with alcohols having 1 to 40 carbon atoms. Compounds which are obtained by esterification of acrylic, methacrylic, crotonic or maleic acid with fatty alcohols of chain length C 12 to C 22 are particularly preferred. Both half and full esters are suitable for the esters of dicarboxylic acids. However, copolymers which contain, as monomer b), the half esters of maleic acid with fatty alcohols having 12 to 22 carbon atoms are particularly preferred.
  • the copolymers can also be built up in minor amounts from monomers of group c).
  • monomers of group c These are compounds known to the person skilled in the art which can be polymerized by free radicals. Examples of such compounds are, on the one hand, compounds containing ethylenic double bonds, such as vinylsulfosuccinic acid, and, on the other hand, polymerizable silanes, such as trimethoxychlorosilane.
  • Copolymers which, in addition to the monomers a) and b), are also composed of trimethoxychlorosilane are preferred as dispersants in the granules according to the invention.
  • the copolymers are built up from the stated amounts of the monomers a), b) and optionally c). Preference is given to those granules which, as dispersing aids, are copolymers of 5 to 50% by weight, based on the copolymer, of monomers a) and 95 to 50% by weight of monomers b). In the case of polymers which additionally contain monomer units from group c), these monomer units are preferably present in amounts of between 1 and 5% by weight.
  • the granules according to the invention preferably contain the polymeric dispersing aid in amounts of between 1 and 50% by weight, granules which contain between 5 and 15% by weight of the dispersing aid being particularly suitable.
  • the granules can also contain auxiliary substances. These include, for example, fillers or carriers, surfactants or other dispersing agents. As a filler or carrier, the granules can be any of the compounds known to those skilled in the art to be suitable contain. These include, for example, clay minerals, such as zeolites or bentonites, silicic acid or organic and inorganic salts. Granules are preferred which contain sodium sulfate or sodium citrate as filler or carrier. The granules preferably contain the filler or carrier in amounts of between 1 and 90% by weight.
  • Anionic, nonionic or cationic surfactants are suitable as surfactants.
  • Preferred anionic surfactants are fatty alcohol sulfates, naphthalene sulfonates or lignin sulfonates.
  • the granules according to the invention are preferably free from surfactants.
  • the granules can also contain other suitable auxiliaries and additives, such as disintegrants, binders, defoamers, colorants and / or fragrances.
  • the granules according to the invention can be produced by the granulation processes known in the prior art.
  • Granules which are produced by extrusion are particularly preferred.
  • the agrochemical active ingredients are mixed with a dispersing aid and, if appropriate, with further auxiliaries, then molded into a compressible mass and then extruded under pressure, copolymers of the type described above being used as dispersing aids.
  • the strand-like mass emerging from the extruder is divided into the actual granules by rotating knives.
  • the extrusion is preferably carried out at pressures between 2 and 200 bar, preferably at pressures from 5 to 150 bar.
  • the granules thus obtained have particle sizes between 0.01 and 5.0 mm, preferably between 0.5 and 2.0 mm.
  • the granules according to the invention are stable on storage and can be easily dispersed in water.
  • the granules can be dispersed by using low shear forces - for example, by simply stirring them by hand.
  • suitable auxiliaries for example a mechanical stirrer.
  • copolymers of the type described above as dispersing agents for granules which contain water-insoluble agrochemical active ingredients and, if appropriate, further auxiliaries.
  • Another object of the present application is a method for protecting plants, in which a granulate of the type described above is dispersed in water and this dispersion is applied to the plants.

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

The invention relates to granulates containing at least one water-insoluble agrochemical agent, one polymer dispersion agent and optionally one carrier, whereby the polymer dispersion agent is a copolymer which can be produced by polymerization of; a) 1 to 99 wt. % radical polymerizable, ethylene unsaturated acids and/or anhydrides thereof; b) 99 to 1 wt. % radical polymerizable, ethylene unsaturated esters and optionally; c) 0.5 to 20 wt. % additional radical polymerizable comonomers.

Description

„Dispergierhilfsmittel für Granulate, die wasserunlösliche agrochemische Wirkstoffe enthalten" "Dispersing agents for granules containing water-insoluble agrochemical active ingredients"
Die vorliegende Erfindung betrifft ein Granulat, welches neben wasserunlöslichen agrochemischen Wirkstoffen und gegebenenfalls weiteren Hilfsstoffen ein bestimmtes copolymeres Dispergierhilfsmittel enthält, die Verwendung bestimmter Copolymere als Dispergierhilfsmittel in solchen Granulaten und ein Verfahren zum Schutz von Pflanzen gegen Schädlinge.The present invention relates to granules which, in addition to water-insoluble agrochemical active ingredients and optionally other auxiliaries, contain a particular copolymeric dispersant, the use of certain copolymers as dispersants in such granules and a process for protecting plants against pests.
Wasserunlösliche agrochemische Wirkstoffe, wie beispielsweise Düngemittel, Herbizide, Pestizide, Insektizide oder Saatgutbehandlungsmittel können in einer Vielzahl von Formulierungen eingesetzt werden. Darunter fallen z.B. wäßrige Dispersionen oder Lösungen in geeigneten organischen Lösungsmitteln. Die Wirkstoffe können auch in Form von Sprays oder Pasten zubereitet werden. Sie können auch in fester Form verwendet werden, beispielsweise als Stäubemittel in Abmischung mit geeigneten Streckmitteln, wie Gesteinsmehl, in Tablettenform oder als Granulate. Letztere Formulierung ist besonders geeignet, da auf diese Weise hochkonzentrierte, lagerstabile und leicht handhabbare Zubereitungen erhalten werden. Die Granulate werden kurz vor der eigentlichen Anwendung in Wasser dispergiert, wobei der Anwender die für den jeweiligen Verwendungszweck vorgegebene Konzentration einstellen kann.Water-insoluble agrochemical active ingredients, such as, for example, fertilizers, herbicides, pesticides, insecticides or seed treatment agents, can be used in a large number of formulations. This includes e.g. aqueous dispersions or solutions in suitable organic solvents. The active ingredients can also be prepared in the form of sprays or pastes. They can also be used in solid form, for example as dusts in a mixture with suitable extenders, such as stone powder, in tablet form or as granules. The latter formulation is particularly suitable since highly concentrated, storage-stable and easy-to-handle preparations are obtained in this way. The granules are dispersed in water shortly before the actual application, the user being able to set the concentration specified for the particular application.
Diese Granulate enthalten neben dem eigentlichen Wirkstoff bzw. den Wirkstoffmischungen üblicherweise noch Füll- und/oder Trägerstoffe sowie weitere Hilfsstoffe. Solche Granulate können entweder durch Imprägnieren eines geeigneten porösen Trägerstoffs mit dem flüssigen Wirkstoff (oder einer flüssigen Formulierung eines festen Wirkstoffs) hergestellt werden, beispielsweise durch Aufsprühen des Wirkstoffs auf das poröse Trägermaterial, oder durch Granulieren des Wirkstoffs mit geeigneten Träger- und Hilfsstoffen in Gegenwart einer Hilfsflüssigkeit, z.B. Wasser. Bei der Herstellung solcher Granulate werden auch Extruder eingesetzt, wodurch das zu granulierende Gemenge aber hohen Drücken ausgesetzt wird. Man beobachtet dann häufig, daß die Granulate nicht mehr in ausreichender Menge in Wasser dispergierbar sind. Daher werden bei der Herstellung hochkonzentrierter Granulate, insbesondere bei durch Extrusion hergestellten Granulaten, Hilfsmittel zugegeben, die eine bessere Dispergierung der Granulate ermöglichen sollen, z. B. anionische Tenside (vgl. R. Wengler, Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel, Springer- Verlag, 1970, Band 1, Seiten 41 bis 54).In addition to the actual active ingredient or the active ingredient mixtures, these granules usually also contain fillers and / or carriers and further auxiliaries. Such granules can be produced either by impregnating a suitable porous carrier with the liquid active ingredient (or a liquid formulation of a solid active ingredient), for example by spraying on the Active ingredient on the porous carrier material, or by granulating the active ingredient with suitable carriers and auxiliary substances in the presence of an auxiliary liquid, for example water. Extruders are also used in the production of such granules, but this exposes the batch to be granulated to high pressures. It is then frequently observed that the granules are no longer sufficiently dispersible in water. Therefore, in the production of highly concentrated granules, in particular in the case of granules produced by extrusion, auxiliaries are added which should enable better dispersion of the granules, e.g. B. anionic surfactants (see R. Wengler, Chemistry of Plant Protection and Pest Control, Springer-Verlag, 1970, Volume 1, pages 41 to 54).
Allerdings erfüllen auch diese Dispergiermittel enthaltenden Granulate nicht immer alle Forderungen nach leichter Dispergierbarkeit. Es war daher die Aufgabe der vorliegenden Anmeldung, Hilfsmittel zu finden, die das Dispergieren von wasserunlöslichen agrochemischen Wirkstoffen, die in Form von Granulaten eingesetzt werden, zu verbessern.However, these granules containing dispersants also do not always meet all requirements for easy dispersibility. It was therefore the object of the present application to find auxiliaries which improve the dispersion of water-insoluble agrochemical active ingredients which are used in the form of granules.
Es wurde gefunden, daß bestimmte Copolymere als Dispergierhilfsmittel für diese Granulate hervorragend geeignet sind.It has been found that certain copolymers are outstandingly suitable as dispersing aids for these granules.
Gegenstand der Erfindung ist daher in einer ersten Ausfuhrungsform ein Granulat, enthaltend mindestens einen wasserunlöslichen agrochemischen Wirkstoff und ein polymeres Dispergierhilfsmittel sowie gegebenenfalls weitere Hilfsstoffe, wobei das polymere Dispergierhilfsmittel ein Copolymer ist herstellbar durch Polymerisation von a) 1 bis 99 Gew.-% radikalisch polymerisierbarer, ethylenisch ungesättigter Säuren und/oder deren Anhydriden b) 99 bis 1 Gew.-% radikalisch polymerisierbarer ethylenisch ungesättigter Ester und gegebenenfalls c) 0,5 bis 20 Gew.-% weiterer radikalisch polymerisierbarer Co-Monomeren. Zur Herstellung der erfmdungsgemäßen Granulate können alle dem Fachmann bekannten Granulierverfahren eingesetzt werden, wie sie beispielsweise in Hagers Handbuch der pharmazeutischen Praxis, Springer Verlag, Band 2, 1991, Seiten 724 bis 742, beschrieben werden. Insbesondere sind Granulate geeignet, die durch Extrusion erhalten werden.The invention therefore relates, in a first embodiment, to granules containing at least one water-insoluble agrochemical active ingredient and a polymeric dispersant and, if appropriate, further auxiliaries, the polymeric dispersant being a copolymer which can be prepared by polymerizing a) from 1 to 99% by weight of radically polymerizable, ethylenically unsaturated acids and / or their anhydrides b) 99 to 1% by weight of radically polymerizable ethylenically unsaturated esters and optionally c) 0.5 to 20% by weight of further free-radically polymerizable co-monomers. All granulation methods known to the person skilled in the art can be used to produce the granules according to the invention, as described, for example, in Hager's Handbook of Pharmaceutical Practice, Springer Verlag, Volume 2, 1991, pages 724 to 742. Granules obtained by extrusion are particularly suitable.
Als agrochemische Wirkstoffe werden solche chemischen Verbindungen verstanden, die im Bereich der Landwirtschaft eingesetzt werden. Darunter fallen insbesondere Pflanzenschutz- bzw. Schädlingsbekämpfungsmittel (Römpp Chemie Lexikon, Band 6, 9. Auflage, 1991, Seite 3323). Beispiele für geeignete Verbindungen finden sich in dem oben zitierten Werk von R. Wegler. Dabei sind aber nur solche Verbindungen ausgewählt, die bei Raumtemperatur (20 °C) in Wasser nicht oder kaum löslich sind, daß heißt, das sie bei Raumtemperatur eine Löslichkeit von maximal 0,1 Gew.-% in einem Liter Wasser aufweisen. Besonders bevorzugt sind solche Granulate, die als Wirkstoffe Pflanzenschutzmittel enthalten, z.B. Verbindungen aus den Gruppen der Akarizide, Algizide, Aphizide, Bakterizide, Fungizide, Herbizide, Insektizide, Molluskizide, Nematizide, Rodentizide und Viruzide.Agrochemical active substances are those chemical compounds that are used in the field of agriculture. These include, in particular, pesticides and pesticides (Römpp Chemie Lexikon, Volume 6, 9th edition, 1991, page 3323). Examples of suitable connections can be found in the work by R. Wegler cited above. However, only those compounds are selected which are not or hardly soluble in water at room temperature (20 ° C.), that is to say that they have a solubility of at most 0.1% by weight in one liter of water at room temperature. Particularly preferred are those granules which contain crop protection agents as active ingredients, e.g. Compounds from the groups of acaricides, algicides, aphicides, bactericides, fungicides, herbicides, insecticides, molluscicides, nematicides, rodenticides and virucides.
Geeignete wasserunlösliche agrochemische Wirkstoffe können bei Raumtemperatur sowohl fest als auch flüssig sein - anwendungstechnisch bevorzugt und für die Verwendung in Granulaten besonders geeignet sind aber feste Wirkstoffe. Besonders bevorzugt sind wasserunlösliche Wirkstoffe aus den Klassen der Nitrophenolderivate, Phosphorsäureester, Phenylharnstoff bzw. -thioharnstoffderivaten, Triazinen, Dimethylmorpholinen, Diphenylsulfonen, Methylcarbamaten, Naphthylcarbamaten, Piperonylharnstoffderivaten, Thiophosphaten oder Trichlorethanderivaten.Suitable water-insoluble agrochemical active ingredients can be both solid and liquid at room temperature - preferred in terms of application technology and solid active ingredients are particularly suitable for use in granules. Water-insoluble active substances from the classes of nitrophenol derivatives, phosphoric acid esters, phenylurea or thiourea derivatives, triazines, dimethylmorpholines, diphenylsulfones, methylcarbamates, naphthylcarbamates, piperonylurea derivatives, thiophosphates or trichloroethane derivatives are particularly preferred.
Die erfindungsgemäßen Granulate enthalten den wasserunlöslichen agrochemischen Wirkstoff vorzugsweise in Mengen zwischen 0,5 und 90 Gew.-%. Besonders bevorzugt sind aber Granulate mit hohen Anteilen an Wirkstoffen, vorzugsweise zwischen 30 und 90 Gew.-%. Die in den erfmdungsgemäßen Granulaten enthaltenen polymeren Dispergierhilfsmittel sind an sich bekannte Verbindungen. So beschreibt die EP 372 746 AI Copolymere aus Acrylsäure- bzw. Methacrylsäure mit Estern aus Acryl- oder Methacrylsäure mit langkettigen Alkoholen. Diese werden aber nur als Hydrophobierungsmittel für die Lederausrüstung beschrieben. Die DE 4129244 AI offenbart Copolymere aus Halbestern der Maleinsäure mit oleophilen Alkoholen und Acrylsäure und/oder Methacrylsäure und gegebenenfalls weiteren Co-Monomeren, die in Form von wäßrigen Dispersionen als Hilfsmittel für die fettende Ausrüstung von Leder und Pelzfellen verwendet werden können. Die DE 4223111 AI beschreibt Copolymere aus Fettcrotonaten und Maleinsäure bzw. Maleinsäureanhydrid und deren Verwendung in der Lederausrüstung. Keines der zitierten Dokumente beschreibt die Verwendung derartiger Copolymere in Pflanzenschutzmitteln oder als Dispergierhilfsmittel.The granules according to the invention preferably contain the water-insoluble agrochemical active ingredient in amounts between 0.5 and 90% by weight. However, granules with a high proportion of active ingredients, preferably between 30 and 90% by weight, are particularly preferred. The polymeric dispersing agents contained in the granules according to the invention are known compounds. EP 372 746 A1 describes copolymers of acrylic acid or methacrylic acid with esters of acrylic or methacrylic acid with long-chain alcohols. However, these are only described as water repellents for leather finishing. DE 4129244 AI discloses copolymers of half-esters of maleic acid with oleophilic alcohols and acrylic acid and / or methacrylic acid and optionally further co-monomers, which can be used in the form of aqueous dispersions as auxiliaries for the oiling of leather and fur skins. DE 4223111 AI describes copolymers of fatty crotonates and maleic acid or maleic anhydride and their use in leather finishing. None of the cited documents describes the use of such copolymers in crop protection agents or as dispersing agents.
Die in den erfmdungsgemäßen Granulaten eingesetzten Copolymere können durch alle bekannten Verfahren zur radikalischen Polymerisation hergestellt werden. Üblicherweise werden die Monomeren in Wasser gelöst und dann durch Zugabe geeigneter Radikalstarter oder durch UV-Licht eine Polymerisationsreaktion eingeleitet.The copolymers used in the granules according to the invention can be produced by all known processes for free-radical polymerization. The monomers are usually dissolved in water and then a polymerization reaction is initiated by adding suitable radical initiators or by UV light.
Die Copolymere werden durch gleichzeitige Reaktion von mindestens zwei verschiedenen Monomerbausteinen a) und b) sowie gegebenenfalls c) hergestellt. Die Monomeren der Gruppe a) sind radikalisch polymerisierbare ethylenisch ungesättigte, vorzugsweise mono-ungesättigte Säuren und/oder deren Anhydride. Geeignete Monomere sind organische Carbonsäuren mit 3 bis 10 C- Atomen, z.B. Acryl- und Methacrylsäure, Crotonsäure, Malein- und Fumarsäure oder deren Anhydride. Es können auch Mischungen der Komponente a) als Monomeren verwendet werden. Besonders bevorzugt sind solche Copolymeren, deren Monomerbaustein a) ausgewählt ist aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure oder Maleinsäureanhydrid.The copolymers are prepared by the simultaneous reaction of at least two different monomer units a) and b) and optionally c). The monomers of group a) are free-radically polymerizable ethylenically unsaturated, preferably mono-unsaturated acids and / or their anhydrides. Suitable monomers are organic carboxylic acids with 3 to 10 carbon atoms, e.g. Acrylic and methacrylic acid, crotonic acid, maleic and fumaric acid or their anhydrides. Mixtures of component a) can also be used as monomers. Copolymers whose monomer component a) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid or maleic anhydride are particularly preferred.
Als Monomerbaustein b) werden radikalisch polymerisierbare ethylenisch ungesättigte Ester eingesetzt. Als Säurekomponente sind die unter a) genannten Mono- und Dicarbonsäuren geeignet, welche mit Alkoholen mit 1 bis 40 C-Atomen verestert sind. Besonders bevorzugt sind dabei solche Verbindungen, die durch Veresterung von Acryl-, Methacryl-, Croton- oder Maleinsäure mit Fettalkoholen der Kettenlänge C12 bis C22 erhalten werden. Bei den Estern der Dicarbonsäuren sind sowohl die Halb- als auch die Vollester geeignet. Besonders bevorzugt sind aber solche Copolymeren, die als Monomer b) die Halbester der Maleinsäure mit Fettalkoholen mit 12 bis 22 C- Atomen enthalten.Free-radically polymerizable ethylenically unsaturated esters are used as monomer block b). Suitable acid components are the mono- and dicarboxylic acids mentioned under a), which are esterified with alcohols having 1 to 40 carbon atoms. Compounds which are obtained by esterification of acrylic, methacrylic, crotonic or maleic acid with fatty alcohols of chain length C 12 to C 22 are particularly preferred. Both half and full esters are suitable for the esters of dicarboxylic acids. However, copolymers which contain, as monomer b), the half esters of maleic acid with fatty alcohols having 12 to 22 carbon atoms are particularly preferred.
Neben den Monomeren a) und b) können die Co-Polymeren auch in untergeordneten Mengen aus Monomeren der Gruppe c) aufgebaut sein. Dabei handelt es sich um dem Fachmann bekannte Verbindungen, die sich radikalisch polymerisieren lassen. Beispiele für solche Verbindungen sind zum einen ethylenische Doppelbindungen enthaltene Verbindungen, wie Vinylsulfobernsteinsäure, zum anderen aber auch polymerisierbare Silane, wie das Trimethoxychlorsilan. Copolymere, die neben den Monomeren a) und b) auch aus Trimethoxychlorsilan aufgebaut sind, sind als Dispergierhilfsmittel in den erfindungsgemäßen Granulaten bevorzugt.In addition to the monomers a) and b), the copolymers can also be built up in minor amounts from monomers of group c). These are compounds known to the person skilled in the art which can be polymerized by free radicals. Examples of such compounds are, on the one hand, compounds containing ethylenic double bonds, such as vinylsulfosuccinic acid, and, on the other hand, polymerizable silanes, such as trimethoxychlorosilane. Copolymers which, in addition to the monomers a) and b), are also composed of trimethoxychlorosilane are preferred as dispersants in the granules according to the invention.
Die Copolymeren sind aus den angegebenen Mengen der Monomeren a), b) und gegebenenfalls c) aufgebaut. Bevorzugt sind dabei solche Granulate, die als Dispergierhilfsmittel Copolymere aus 5 bis 50 Gew.-% - bezogen auf das Copolymer - an Monomeren a) und 95 bis 50 Gew.-% an Monomeren b) aufgebaut sind. Bei Polymeren, die zusätzlich noch Monomerbausteine der Gruppe c) enthalten, sind diese Monomerbausteine bevorzugt in Mengen zwischen 1 und 5 Gew.-% enthalten.The copolymers are built up from the stated amounts of the monomers a), b) and optionally c). Preference is given to those granules which, as dispersing aids, are copolymers of 5 to 50% by weight, based on the copolymer, of monomers a) and 95 to 50% by weight of monomers b). In the case of polymers which additionally contain monomer units from group c), these monomer units are preferably present in amounts of between 1 and 5% by weight.
Die erfindungsgemäßen Granulate enthalten das polymere Dispergierhilfsmittel vorzugsweise in Mengen zwischen 1 und 50 Gew.-%, wobei insbesondere solche Granulate geeignet sind, die zwischen 5 und 15 Gew.-% des Dispergierhilfsmittels enthalten.The granules according to the invention preferably contain the polymeric dispersing aid in amounts of between 1 and 50% by weight, granules which contain between 5 and 15% by weight of the dispersing aid being particularly suitable.
Die Granulate können noch Hilfsstoffe enthalten. Dazu zählen beispielsweise Füll- oder Trägerstoffe, Tenside oder andere Dispergierhilfsmittel. Als Füll- oder Trägerstoff können die Granulate alle dem Fachmann als geeignet bekannten Verbindungen enthalten. Darunter fallen beispielsweise Tonmineralien, wie Zeolithe oder Bentonite, Kieselsäure oder organische und anorganische Salze. Bevorzugt sind Granulate, die als Füll- oder Trägerstoff Natriumsulfat oder Natriumeitrat enthalten. Die Granulate enthalten den Füll- oder Trägerstoff vorzugsweise in Mengen zwischen 1 und 90 Gew.- %.The granules can also contain auxiliary substances. These include, for example, fillers or carriers, surfactants or other dispersing agents. As a filler or carrier, the granules can be any of the compounds known to those skilled in the art to be suitable contain. These include, for example, clay minerals, such as zeolites or bentonites, silicic acid or organic and inorganic salts. Granules are preferred which contain sodium sulfate or sodium citrate as filler or carrier. The granules preferably contain the filler or carrier in amounts of between 1 and 90% by weight.
Als Tenside kommen anionische, nichtionische bzw. kationische Tenside in Frage. Bevorzugte anionische Tenside sind Fettalkoholsulfate, Napthalinsulfonate oder Ligninsulfonate. Vorzugsweise sind die erfmdungsgemäßen Granulate aber frei von Tensiden. Neben den bereits genannten Verbindungen können die Granulate noch weitere geeignete Hilfs- und Zusatzstoffe wie Sprengmittel, Bindemittel, Entschäumer, Färb- und/oder Duftstoffe enthalten.Anionic, nonionic or cationic surfactants are suitable as surfactants. Preferred anionic surfactants are fatty alcohol sulfates, naphthalene sulfonates or lignin sulfonates. However, the granules according to the invention are preferably free from surfactants. In addition to the compounds already mentioned, the granules can also contain other suitable auxiliaries and additives, such as disintegrants, binders, defoamers, colorants and / or fragrances.
Die Herstellung der erfindungsgemäßen Granulate kann nach den im Stand der Technik bekannten Granulierverfahren erfolgen. Besonders bevorzugt sind Granulate, die durch Extrusion hergestellt werden. Dazu werden die agrochemischen Wirkstoffe mit einem Dispergierhilfsmittel und gegebenenfalls mit weiteren Hilfsstoffen vermischt, anschließend zu einer verpressbaren Masse geformt und dann unter Druckanwendung extrudiert, wobei als Dispergierhilfsmittel Copolymere der oben beschriebenen Art verwendet werden. Die aus dem Extruder austretende strangförmige Masse wird durch rotierende Messer zu den eigentlichen Granulaten zerteilt. Bei der Extrusion wird vorzugsweise mit Drücken zwischen 2 und 200 bar, vorzugsweise mit Drücken von 5 bis 150 bar gearbeitet. Die so erhaltenen Granulate weisen Teilchengrößen zwischen 0,01 und 5,0 mm, vorzugsweise zwischen 0,5 und 2,0 mm auf.The granules according to the invention can be produced by the granulation processes known in the prior art. Granules which are produced by extrusion are particularly preferred. For this purpose, the agrochemical active ingredients are mixed with a dispersing aid and, if appropriate, with further auxiliaries, then molded into a compressible mass and then extruded under pressure, copolymers of the type described above being used as dispersing aids. The strand-like mass emerging from the extruder is divided into the actual granules by rotating knives. The extrusion is preferably carried out at pressures between 2 and 200 bar, preferably at pressures from 5 to 150 bar. The granules thus obtained have particle sizes between 0.01 and 5.0 mm, preferably between 0.5 and 2.0 mm.
Die erfindungsgemäßen Granulate sind lagerstabil und lassen sich leicht in Wasser dispergieren. In der Regel können die Granulate durch Einsatz geringer Scherkräfte dispergiert werden - z.B. durch einfaches Umrühren per Hand. Es kann aber, in Abhängigkeit von den verwendeten Wirkstoffen auch notwendig sein, die Granulate unter Einsatz geeigneter Hilfsmitteln, z.B. einem mechanischen Rührer, zu dispergieren. Beansprucht wird weiterhin die Verwendung von Copolymeren der oben beschriebenen Art als Dispergierhilfsmittel für Granulate, die wasserunlösliche agrochemische Wirkstoffe und gegebenenfalls weitere Hilfsstoffe enthalten.The granules according to the invention are stable on storage and can be easily dispersed in water. As a rule, the granules can be dispersed by using low shear forces - for example, by simply stirring them by hand. However, depending on the active ingredients used, it may also be necessary to disperse the granules using suitable auxiliaries, for example a mechanical stirrer. Also claimed is the use of copolymers of the type described above as dispersing agents for granules which contain water-insoluble agrochemical active ingredients and, if appropriate, further auxiliaries.
Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein Verfahren zum Schutz von Pflanzen, in dem ein Granulat der oben beschriebenen Art in Wasser dispergiert und diese Dispersion auf die Pflanzen aufgebracht wird. Another object of the present application is a method for protecting plants, in which a granulate of the type described above is dispersed in water and this dispersion is applied to the plants.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Granulat enthaltend mindestens einen wasserunlöslichen agrochemischen Wirkstoff und ein polymeres Dispergierhilfsmittel, sowie gegebenenfalls weitere Hilfsstoffe, dadurch gekennzeichnet, daß das polymere Dispergierhilfsmittel ein Copolymer ist herstellbar durch Polymerisation von a) 1 bis 99 Gew.-% radikalisch polymerisierbarer, ethylenisch ungesättigter Säuren und/oder deren Anhydride b) 99 bis 1 Gew.-% radikalisch polymerisierbarer ethylenisch ungesättigter Ester und gegebenenfalls c) 0,5 bis 20 Gew.-% weiterer radikalisch polymerisierbarer Co-Monomeren.1. Granules containing at least one water-insoluble agrochemical active ingredient and a polymeric dispersing agent, and optionally further auxiliaries, characterized in that the polymeric dispersing agent is a copolymer which can be prepared by polymerizing a) from 1 to 99% by weight of radically polymerizable, ethylenically unsaturated acids and / or their anhydrides b) 99 to 1% by weight of radically polymerizable ethylenically unsaturated esters and optionally c) 0.5 to 20% by weight of further free-radically polymerizable co-monomers.
2. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß das polymere Dispergierhilfsmittel ein Copolymer ist herstellbar durch Polymerisation von 5 bis 50 Gew.-% eines Monomers a), 95 bis 50 Gew.-% eines Monomers b) und gegebenenfalls 1 bis 5 Gew.-% eines Monomers c).2. Granules according to claim 1, characterized in that the polymeric dispersant is a copolymer can be prepared by polymerization of 5 to 50 wt .-% of a monomer a), 95 to 50 wt .-% of a monomer b) and optionally 1 to 5 wt .-% of a monomer c).
3. Granulat nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das polymere Dispergierhilfsmittel ein Copolymer ist dessen Monomer a) ausgewählt ist aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure oder Maleinsäureanhydrid.3. Granules according to claim 1 or 2, characterized in that the polymeric dispersing aid is a copolymer whose monomer a) is selected from the group acrylic acid, methacrylic acid, maleic acid or maleic anhydride.
4. Granulat nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das polymere Dispergierhilfsmittel ein Copolymer ist dessen Monomer b) ausgewählt ist aus der Gruppe der Ester der Acryl-, Methacryl, Croton- oder Maleinsäure mit Alkoholen mit 1 bis 40 C- Atomen und vorzugsweise 10 bis 22 C-Atomen.4. Granules according to claim 1 to 3, characterized in that the polymeric dispersant is a copolymer whose monomer b) is selected from the group of the esters of acrylic, methacrylic, crotonic or maleic acid with alcohols having 1 to 40 carbon atoms and preferably 10 to 22 carbon atoms.
5. Granulat nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß das polymere Dispergierhilfsmittel ein Copolymer ist dessen Co-Monomer c) Trimethoxychlorsilan ist. 5. Granules according to claim 1 to 4, characterized in that the polymeric dispersant is a copolymer whose co-monomer c) is trimethoxychlorosilane.
6. Granulat nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es das polymere Dispergierhilfsmittel in Mengen zwischen 1 bis 50, vorzugsweise 5 bis 15 Gew.- % enthält.6. Granules according to claim 1 to 5, characterized in that it contains the polymeric dispersing agent in amounts between 1 to 50, preferably 5 to 15% by weight.
7. Granulat nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es als wasserunlöslichen agrochemischen Wirkstoff Pflanzenschutzmittel enthält.7. Granules according to one of claims 1 to 6, characterized in that it contains pesticides as the water-insoluble agrochemical active ingredient.
8. Granulat nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es die wasserunlöslichen agrochemischen Wirkstoffe in Mengen zwischen 0,5 und 90 Gew.-% enthält.8. Granules according to one of claims 1 to 7, characterized in that it contains the water-insoluble agrochemical active ingredients in amounts between 0.5 and 90 wt .-%.
9. Granulat nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß es als Hilfsstoffe Träger- oder Füllstoffe ausgewählt aus der Gruppe Natriumsulfat oder Natriumeitrat enthält.9. Granules according to claim 1 to 8, characterized in that it contains carrier or fillers selected from the group sodium sulfate or sodium citrate as auxiliary substances.
10. Granulat nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es den Träger- oder Füllstoff in Mengen zwischen 1 und 90 Gew.-% enthält.10. Granules according to one of claims 1 to 9, characterized in that it contains the carrier or filler in amounts between 1 and 90 wt .-%.
11. Granulat nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es durch Extrusion hergestellt wird.11. Granules according to one of claims 1 to 10, characterized in that it is produced by extrusion.
12. Verwendung von Copolymeren herstellbar durch Polymerisation von a) 1 bis 99 Gew.-% radikalisch polymerisierbarer, ethylenisch ungesättigter Säuren und/oder deren Anhydride b) 99 bis 1 Gew.-% radikalisch polymerisierbarer ethylenisch ungesättigter Ester und gegebenenfalls c) 0,5 bis 20 Gew.-% weiterer radikalisch polymerisierbarer Co-Monomeren als Dispergierhilfsmittel in Granulaten, die mindestens einen wasserunlöslichen agrochemische Wirkstoffe und gegebenenfalls weitere Hilfsstoffe enthalten. 12. Use of copolymers which can be prepared by polymerizing a) 1 to 99% by weight of radically polymerizable, ethylenically unsaturated acids and / or their anhydrides b) 99 to 1% by weight of free-radically polymerizable ethylenically unsaturated esters and, if appropriate, c) 0.5 up to 20% by weight of further radically polymerizable co-monomers as dispersing agents in granules which contain at least one water-insoluble agrochemical active ingredient and, if appropriate, further auxiliaries.
13. Verfahren zum Schutz von Pflanzen gegen Schädlinge, dadurch gekennzeichnet, daß eine wäßrige Dispersion eines Granulats gemäß Anspruch 1 auf die Pflanzen aufgebracht wird. 13. A method for protecting plants against pests, characterized in that an aqueous dispersion of a granulate according to claim 1 is applied to the plants.
EP98954333A 1997-10-13 1998-10-05 Dispersion agent for granulates which contain water-insoluble agrochemical agents Withdrawn EP1022940A1 (en)

Applications Claiming Priority (3)

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DE19745174 1997-10-13
DE1997145174 DE19745174A1 (en) 1997-10-13 1997-10-13 Agrochemical granules containing polymer dispersant
PCT/EP1998/006309 WO1999018783A1 (en) 1997-10-13 1998-10-05 Dispersion agent for granulates which contain water-insoluble agrochemical agents

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DE10157350A1 (en) * 2001-11-22 2003-05-28 Stockhausen Chem Fab Gmbh Production of controlled release plant treatment composition, comprises kneading water-absorbing polymer containing absorbed water with active agent, e.g. fungicide or insecticide

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JPS481501B1 (en) * 1970-08-21 1973-01-18
BE861231A (en) * 1977-11-25 1978-03-16 Delong Charles F COMPOSITIONS INHIBITING PLANT GROWTH AND METHOD FOR USING THEM
JPS59231001A (en) * 1983-06-14 1984-12-25 Sanyo Chem Ind Ltd Dispersant for agricultural and horticultural granule
JPH0720842B2 (en) * 1986-03-12 1995-03-08 花王株式会社 Granular biocide composition
JPH035405A (en) * 1989-06-01 1991-01-11 Sanyo Chem Ind Ltd Dispersant for granular wettable powder
DE4327514A1 (en) * 1993-08-17 1995-02-23 Basf Ag Aqueous copolymer dispersions

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