CA1279770C - Combination carrier granules - Google Patents
Combination carrier granulesInfo
- Publication number
- CA1279770C CA1279770C CA000501857A CA501857A CA1279770C CA 1279770 C CA1279770 C CA 1279770C CA 000501857 A CA000501857 A CA 000501857A CA 501857 A CA501857 A CA 501857A CA 1279770 C CA1279770 C CA 1279770C
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- Prior art keywords
- active compound
- liquid
- solid
- biocidally active
- combination carrier
- 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.)
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Abstract
ABSTRACT OF THE DISCLOSURE
New combination carrier granulars are disclosed which comprise a granular carrier material having a compact surface and having applied thereto at least one liquid biocidally active compound, at least one solid biocidally active compound, polyvinyl acetate and polyvinyl alcohol.
These combination carrier granules exhibit unexpectedly better activity than prior are materials and have unexpectly high abrasion resistance.
New combination carrier granulars are disclosed which comprise a granular carrier material having a compact surface and having applied thereto at least one liquid biocidally active compound, at least one solid biocidally active compound, polyvinyl acetate and polyvinyl alcohol.
These combination carrier granules exhibit unexpectedly better activity than prior are materials and have unexpectly high abrasion resistance.
Description
The present inventioll reLates to new combination carrier granules which contain solid and liquid biocidal active compounds. The invention furthermore relates to a process for the preparat;on of the new combination carrier granules and their use.
~ umerous carrier granules which con~ain solid or liquid biocidal active compounds on a granular carrier material are already kno~n (compare Buchel "Pflanzenschutz und Schàdlingsbekàmpfung" ("Plant protection and combating pests")~ Georg Thieme Verlag, Stuttgart 1977, pages 198 and 199~.
Carrier granules with solid active compounds can thus be prepared, for example, by fixing the active compon-ents, if appropriate mixed with additives, in finely divided form to the compact surface of the carrier material with the aid of adhesives A disadvantage is, however, that liquid active compounds cannot be applied to carr;er materials by this method since the kno~n adhesives do not harden in the presence of liquid active compounds.
Carrier granules which contain liquid herbicidal active compounds can be prepared~ for example, by impregnat-ing porous or absorbent carrier mater-als with liquid active compounds or with solutions of liquid active compounds in suitable solvents, in each case, if appropriate, mixed with 2~ additives. Carrier granules containing both solid and liquid biocidal active compounds can indeed be prepared by impregnating porous or absorbent carrier materials with solutions of solid and liquid active compounds and, if appropriate, additives in suitable solvents if solvents of this type can be discovered. However, the properties of these granules are not always satisfactory~ Amongst other thinys, in particular, blocking of the pores or capillaries of the carrier material frequently occurs due to the ,olid active compounds crystallising out, so that the active com-Le A 23 328 7~7r~
ponents are not released in the desired manner at the place of use.
New combination carrier granules which contain granular carrier material with a compact surface, at least one solid biocidal active compound, at least one liquid biocidal active compound, polyvinyl acetate and polyvinyl alcohol andt if appropriate, additives, have now been found.
It has furthermore been found that the combination carrier granules according to the invention are prepared by a process in ~hich granular carrier material with a compact surface is sprayed with an aqueous dispersion of polyvinyl acetate and polyvinyl alcohol in a mixer and then sprayed with at least one solid biocidal active compound, at least one liquid biocidal active compound, if appropriate addi-tives and if appropriate an aqueous dispersion of polyvinylacetate and polyvinyl alcohol, and the granular products thus obtained are dried.
Finally, it has been found that the combination carrier granules according to the invention can be used for the most diverse purposes in agriculture and in horticulture depending on the active components contained therein.
It is to be described as extremely surprising that the combination carrier granules according to the invention exhibit a better activity than the previously known granules in which solid and liquid active compounds are absorbed in the form of a solution onto porous or absorbent carrier mater;als. It is also unexpected that the products accord-ing to the invention are stable under conditions in practice.
On ~he basis of the known prior art, it was to be assumed, in fact, that carrier granules with liquid active compounds would necessarily have to contain porous or absorbent carrier materials.
The combination carrier granules according to the invention are distinguished by a number of advantages.
Thus, problem-free joint application of solid and liquid biocidal active compounds is made possible by these products.
Le A 23 328 '' 7~ ~
~he active components contained in these granules are f~rthermore released ;n the particular des;red manner at their place of use. ~oreover, the combination carrier gran-ules according to the invention are products which are dis-tinguished by a very high abrasion resistance.
The products according to the invention are calLed combination carrier granules in the present case since they contain solid and liquid biocidal active compounds in com-bination with one another.
All the customary granular carrier substances with a compact surface which are conta;ned in such granules can be present as carrier materials in the combination carrier granules according to the invention. Calcite, dolomite and sand, such as, for example, quartz sand, are preferably suitable.
The average particle diameter of the carrier mater-ials can be varied within a certain range~ The average part;cle d;ameter ;s ;n general between 0.1 and 3 mm, pre-ferably between 0O3 and 1 mm.
B;oc;dal active compounds in the present case are to be understood as all the active compounds which can usually be employed in plant protection. These ;nclude, preferably, insect;c;des~ acaricides~ nematic;des, fungi c;des, herb;c;des and plant growth regulators.
The granules accord;ng to the invent;on conta;n at least one biocidal act;ve compound which is solid at room temperature and at least one bioc;dal act;ve compound ~h;ch ;s l;qu;d at room temperature.
Carbamates can preferably be used as biocidal active compounds which are sol;d at room temperature. Examples which may be mentioned are: 2-;sopropoxy-phenyl N-methyl-carbamate, 2f3-dihydro-2,2-dimethyl~7-benzofuranyl N-methyl-carbamate~ ~3,5-dimethyl-4-methylthio-phenyl) N-methyl-carbamate and (naphthyl-1-yl) N-methyl-carbamate.
Phosphoric ac;d derivatives are preferably suitable as bioc;dal active compounds which are liquid at room tem-Le A 23 328 9 ~
perature. Examples ~hich may be mentioned are: 0,0-d;ethyL
Q-t4-nitro-phenyl) thionophosphate, 0,0-dimethyl 0-t4-nitro-phenyl) thionophosphate, 0-ethyl D-(4-methylthio-phenyl) S-propyl dithiophosphate, (0,0-diethyl-thionophosphoryL)-~-oximinophenylacetonitrile, 0,0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl) thiophosphate, S-C1,2-bis-(ethoxy-carbonyl)-ethyl] 0,0-dimethyl dithiophosphate, 0,0-dimethyl 0-~4-methylmercapto-3-methyl-phenyl) thionophosphate and 0-ethyL-0-(2-isopropoxycarbonyL-phenyL) N-isopropyL-thiono-phosphoric acid ester-amide.
A mixture of polyvinyl acetate and poLyvinyl aLcohoL
functions as the binder in the combination carrier granules according to the invention.
PossibLe additives which can be present in the com-bination carrier granuLes accord;ng to the invent;on areextenders, grinding auxiLiaries, dyestuffs, water and organic solvents~
Preferred possibLe extenders here are fine-grained inorganic soLids, such as naturaL rock powders, for exampLe kaoLins, aLuminas, taLc, chaLk, Quartz powder, attapuLgite, montmoriLLonite~ sepioLith or diatomaceous earth, and furthermore synthetic rock powders, such as highly disperse silica.
Possible grinding auxiliaries are all the substances uhich can usuaLly be employed for this purpose. KaoLins, aLuminas, taLc, chaLk and quartz powder may be mentioned as preferred.
Dyestuffs ~hich may be mentioned which are suitabLe as additives are inorganic pigments, such as iron oxide, titanium dioxide and Prussian bLue, and organic dyestuffs~
such as anthraquinone dyestuffs, azo dyestuffs and metaL
phthaLocyanine dyestuffs.
PossibLe organic soLvents are aLl the organic sol-vents which can usualLy be empLoyed for the preparation of carrier granuLes. Preferred possibLe soLvents are Low-boiLing organic soLvents, such as methanoL, ethanoL, butanol Le A 23 3Z8 3r~J7~) and methylene chloride.
The granules according to the invention consist of granular carrier materials, on the compact surface of which is an enveloping layer containing at least one solid bio-cidal active compound and at least one liquid biocidalactive compound as well as a mixture of polyvinyl acetate and polyvinyl alcohol, acting as a binder, and, if approp-riate, additives. The components present in the enveloping layer can partly also penetrate into depressions in the carrier material.
The percentage contents of the components contained in the combination carrier granules according to the inven-tion can be varied within substantial ranges. The content of carrier material is in general between S0 and 98% by weight, preferably between 60 and 92X by weight. The con-tent of liquid and also o-f solid biocidal active compounds is in géneral between 0.1 and 20% by weight, preferably between 0~5 and 15X by weight. The content of the mixture of polyvinyl acetate and polyvinyl alcohol functioning as the binder is in general between 0.1 and 4X by ~eight~ pre-ferably between 0~3 and 3% by weight~ in general D.~S to .25 part by weight, preferably 0.1 to 0.2 part by weight~
of polyvinyl alcohol being present per part of polyvinyl aceta~e~ The granules contain additives, if appropriate9 in amounts of 1 to 40 parts by ~eight, preferably 2 to 30 parts by weight.
All those components ~hich have already been men-tioned as preferred in connection with the description of the combination carrier granules according to the invention 3~ can preferably be used in the preparation of the combination carrier granules according to the invention.
It is necessary to employ the solid bioc;dal active compounds in finely divided form in the preparation of the granules according to the invention. For this, the biocidal active compounds which are solid at room temperature are in general used in the finely ground state, if appropriate Le A 23 328 ' ~ ~t~`9~7~7~
mixed w;th grinding auxiliaries. The b;ocidal active com-pounds which are liquid at room temperature are in generaL
used as a mixture with extenders, such as attapulgite, mont-morillonite, sepiolith or highly disperse silica. However, it is also possible to employ a mixture of liquid and solid biocidal active compounds, if appropr;ate mixed with grind-ing auxiliaries, in the finely divided state~
The mi~ture of polyvinyl acetate and polyvinyl alcohol functioning as the binder (adhesive) is employed in the form of an aqueous dispers;on. Poss;ble diluents here are, in addition to water, also organic solvents, preferably low-boiling organic solvents, such as methanol~ ethanol, butanol and methylene chloride.
In carrying out the process according to the inven-tion, a procedure is in general followed in ~hich granularcarrier material with a compact surface is introduced into a mixer and sprayed, while mixing continuously, with an aqueous dispersion of polyvinyl acetate and polyvinyl alco-hol and then either, in succession, at least one solid bio-cidal active compound, if appropriate mixed w;th additives~and at least one liqu;d biocidal active compound, if approp-r;ate m;xed with additives, are added, or a m;xture of at least one solid biocidal active compound and at least one liquid b;ocidal active compound, ;f appropriate m;xed w;th addit;ves, is added~ if appropriate the product is sprayed again ~ith an aqueous dispersion of polyv;nyl acetate and polyvinyl alcohol, and the granular products thus obtained are dried.
The sequence in which the components are applied to the carrier material can be varied in the particular manner desired.
The process according to the ;nvention ;s in general carried out at room temperature. Ho~ever, it is also possible to carry out the process at a somewhat ele-vated temperature.
The drying temperature can be varied within aLe A 23 328 ' 7~
substantial range. In general, drying is carried out at granule temperatures of between ~0C and 70C, preferably between 30C and 65C. If appropr;ate, dry;ng can be carried out under redused pressure. Prying can furthermore be carried out either in the mixer used to coat the carrier material or in a separate drying apparatus.
The process according to the invent;on can be carried out either batchwise or continuously in customary apparatuses.
The combination carrier granules according to the invention can be employed for ~he most diverse purposes, depending on the active components contained therein. Thus, they can be used, for example, for combating animal pests, fungi and/or weeds. If they contain plant growth regulators, they can also be employed for influencing the growth of crop plants.
The combination carrier granules ~ccording to the invention can be applied by customary methods, such as, for example, scattering.
The preparation of the combination carrier granules according to the invention can be seen from the following examples.
Preparation Examples Comparison Example 176.94 g of qùartz sand granules ~i~h a diameter of 0.4 to 0.8 mm are sprayed in a mixer, ~hile continuously mixing at room temperature, ~ith an aqueous dispersion con-taining 1~6 9 of polyvinyl acetate. Thereafter, 13.~6 9 of a commercially available finely ground pulverulent mixture 30 containing 10.47 9 of ~3-dihydro-2,2-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 .
t~ 7~3 H3C ,~ ~1 ~
and 0.6 9 of blue dyestuff and 7 9 of a m;xture consisting to the extent of 65.21 per cent by weight of 0-ethyl 0-(2--isopropoxycarbonyl-phenyl) N-isopropyl-thionophosphoric acid S ester-amide of the Formula p ,0 OCH2H5 (2) NH-CX(CH3)2 Co~-cH(cH3~2 and to the extent of 34.79 per cent by weight of highly dis-perse silica, are added at room temperature. The components are mixed at room temperature for a further 10 minutes and lD then dried in the mixer at a maximum temperature of the material to be dried of 60C~ 200 9 of comb;nation carr;er granules containing 5.2 per cent by weight of active com-pound of the formula (1) and 2.1 per cent by weight of active compound of the formula (2) are obtained in this manner.
The result;ng granules exhibited severe abrasion and softening, so that they ~ere unsui~able for use in practice.
Example 1 88.8 kg of quartz sand granules with a d;ameter of 0.3 to 0.7 mm are sprayed in a mixer, whilst m;xing con-tinuously at room temperature, with 3.34 kg of an aqueous d;spersion containing û.8 kg of polyvinyl acetate and 0.1 kg of polyvinyl alcohol. Thereafter, 6.62 kg of a commer-cially ava;lable f;nely ground pulverulent m;xture conta;n-;ny 5 kg of 2,3-d;hydro-Z,Z-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 ~ ' .
: `:
H3C _;~ t 1 ) and a mixture of 2 kg of 0-ethyl 0-(2-isopropoxycarbonyl-phenyl) N-isopropylthionophosphoric acid ester-amide of the formula ~ ,,, OC2H5 \=~ NH-CH ~ C~ 3 ) 2 ( 2 ) Ct)O-CH ( CH 3 ) 2 are added at room temperature to 0.37 kg of blue dyestuff and 0.37 kg of highly disperse silica. The components are mixed àt room temperature for a further 10 minutes and then dried in the mixer at a maximum temperature of the ma~erial to be dried of 60C. 100 kg of combination carrier gran-ules containing 5% by weight of active compound of the for-mula t1) and 2~ by wei0ht of active compound of the formula t2) are obtained in this manner.
The granules are distinguished by a high abrasion resistance.
Example 2 90.1 kg of quartz sand granules w;th a diameter of 0.3 to 0.7 mm are sprayed ;n a mixer, while cont;nuously mixing at room temperature, with 3.34 kg of an aqueous dis-persion containing 0.75 kg of polyvinyl acetate and 0.15 kgof poly~inyl alcohol. Thereafter~ 5.3 kg of a commercially available finely ground pulverulent mixture contain;ng 4 kg of 2,3-dihydro-Z,Z-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 :
~: . ' ' -- ~
9~77~) H3C ~ t1) and a mixture of 2 kg of 0-ethyl 0- (2-isopropoxycarbonyl-phenyl) N-isopropylthi onophosphoric acid ester-amide of the formula ~ o p _ OCH2H5 NH-CH(CH3)2 S2) COO-CH(CH3)2 are added at room temperature to 0.37 kg of blue dyestuff and 1.34 kg of highly disperse silica. The components are mixed at room temperature for a further 10 minutes and then dried in the mixer at a maximum temperature of the material 10 to be dried of 60C. 100 kg of combination carrier granules containing 4% by weight of active compound of the formula (1) and 2X by weight of active compound of the formula (2) are obtained in this manner.
The granules are distinguished by a high abrasion resistance.
Le A 23 328 :. :
~ umerous carrier granules which con~ain solid or liquid biocidal active compounds on a granular carrier material are already kno~n (compare Buchel "Pflanzenschutz und Schàdlingsbekàmpfung" ("Plant protection and combating pests")~ Georg Thieme Verlag, Stuttgart 1977, pages 198 and 199~.
Carrier granules with solid active compounds can thus be prepared, for example, by fixing the active compon-ents, if appropriate mixed with additives, in finely divided form to the compact surface of the carrier material with the aid of adhesives A disadvantage is, however, that liquid active compounds cannot be applied to carr;er materials by this method since the kno~n adhesives do not harden in the presence of liquid active compounds.
Carrier granules which contain liquid herbicidal active compounds can be prepared~ for example, by impregnat-ing porous or absorbent carrier mater-als with liquid active compounds or with solutions of liquid active compounds in suitable solvents, in each case, if appropriate, mixed with 2~ additives. Carrier granules containing both solid and liquid biocidal active compounds can indeed be prepared by impregnating porous or absorbent carrier materials with solutions of solid and liquid active compounds and, if appropriate, additives in suitable solvents if solvents of this type can be discovered. However, the properties of these granules are not always satisfactory~ Amongst other thinys, in particular, blocking of the pores or capillaries of the carrier material frequently occurs due to the ,olid active compounds crystallising out, so that the active com-Le A 23 328 7~7r~
ponents are not released in the desired manner at the place of use.
New combination carrier granules which contain granular carrier material with a compact surface, at least one solid biocidal active compound, at least one liquid biocidal active compound, polyvinyl acetate and polyvinyl alcohol andt if appropriate, additives, have now been found.
It has furthermore been found that the combination carrier granules according to the invention are prepared by a process in ~hich granular carrier material with a compact surface is sprayed with an aqueous dispersion of polyvinyl acetate and polyvinyl alcohol in a mixer and then sprayed with at least one solid biocidal active compound, at least one liquid biocidal active compound, if appropriate addi-tives and if appropriate an aqueous dispersion of polyvinylacetate and polyvinyl alcohol, and the granular products thus obtained are dried.
Finally, it has been found that the combination carrier granules according to the invention can be used for the most diverse purposes in agriculture and in horticulture depending on the active components contained therein.
It is to be described as extremely surprising that the combination carrier granules according to the invention exhibit a better activity than the previously known granules in which solid and liquid active compounds are absorbed in the form of a solution onto porous or absorbent carrier mater;als. It is also unexpected that the products accord-ing to the invention are stable under conditions in practice.
On ~he basis of the known prior art, it was to be assumed, in fact, that carrier granules with liquid active compounds would necessarily have to contain porous or absorbent carrier materials.
The combination carrier granules according to the invention are distinguished by a number of advantages.
Thus, problem-free joint application of solid and liquid biocidal active compounds is made possible by these products.
Le A 23 328 '' 7~ ~
~he active components contained in these granules are f~rthermore released ;n the particular des;red manner at their place of use. ~oreover, the combination carrier gran-ules according to the invention are products which are dis-tinguished by a very high abrasion resistance.
The products according to the invention are calLed combination carrier granules in the present case since they contain solid and liquid biocidal active compounds in com-bination with one another.
All the customary granular carrier substances with a compact surface which are conta;ned in such granules can be present as carrier materials in the combination carrier granules according to the invention. Calcite, dolomite and sand, such as, for example, quartz sand, are preferably suitable.
The average particle diameter of the carrier mater-ials can be varied within a certain range~ The average part;cle d;ameter ;s ;n general between 0.1 and 3 mm, pre-ferably between 0O3 and 1 mm.
B;oc;dal active compounds in the present case are to be understood as all the active compounds which can usually be employed in plant protection. These ;nclude, preferably, insect;c;des~ acaricides~ nematic;des, fungi c;des, herb;c;des and plant growth regulators.
The granules accord;ng to the invent;on conta;n at least one biocidal act;ve compound which is solid at room temperature and at least one bioc;dal act;ve compound ~h;ch ;s l;qu;d at room temperature.
Carbamates can preferably be used as biocidal active compounds which are sol;d at room temperature. Examples which may be mentioned are: 2-;sopropoxy-phenyl N-methyl-carbamate, 2f3-dihydro-2,2-dimethyl~7-benzofuranyl N-methyl-carbamate~ ~3,5-dimethyl-4-methylthio-phenyl) N-methyl-carbamate and (naphthyl-1-yl) N-methyl-carbamate.
Phosphoric ac;d derivatives are preferably suitable as bioc;dal active compounds which are liquid at room tem-Le A 23 328 9 ~
perature. Examples ~hich may be mentioned are: 0,0-d;ethyL
Q-t4-nitro-phenyl) thionophosphate, 0,0-dimethyl 0-t4-nitro-phenyl) thionophosphate, 0-ethyl D-(4-methylthio-phenyl) S-propyl dithiophosphate, (0,0-diethyl-thionophosphoryL)-~-oximinophenylacetonitrile, 0,0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl) thiophosphate, S-C1,2-bis-(ethoxy-carbonyl)-ethyl] 0,0-dimethyl dithiophosphate, 0,0-dimethyl 0-~4-methylmercapto-3-methyl-phenyl) thionophosphate and 0-ethyL-0-(2-isopropoxycarbonyL-phenyL) N-isopropyL-thiono-phosphoric acid ester-amide.
A mixture of polyvinyl acetate and poLyvinyl aLcohoL
functions as the binder in the combination carrier granules according to the invention.
PossibLe additives which can be present in the com-bination carrier granuLes accord;ng to the invent;on areextenders, grinding auxiLiaries, dyestuffs, water and organic solvents~
Preferred possibLe extenders here are fine-grained inorganic soLids, such as naturaL rock powders, for exampLe kaoLins, aLuminas, taLc, chaLk, Quartz powder, attapuLgite, montmoriLLonite~ sepioLith or diatomaceous earth, and furthermore synthetic rock powders, such as highly disperse silica.
Possible grinding auxiliaries are all the substances uhich can usuaLly be employed for this purpose. KaoLins, aLuminas, taLc, chaLk and quartz powder may be mentioned as preferred.
Dyestuffs ~hich may be mentioned which are suitabLe as additives are inorganic pigments, such as iron oxide, titanium dioxide and Prussian bLue, and organic dyestuffs~
such as anthraquinone dyestuffs, azo dyestuffs and metaL
phthaLocyanine dyestuffs.
PossibLe organic soLvents are aLl the organic sol-vents which can usualLy be empLoyed for the preparation of carrier granuLes. Preferred possibLe soLvents are Low-boiLing organic soLvents, such as methanoL, ethanoL, butanol Le A 23 3Z8 3r~J7~) and methylene chloride.
The granules according to the invention consist of granular carrier materials, on the compact surface of which is an enveloping layer containing at least one solid bio-cidal active compound and at least one liquid biocidalactive compound as well as a mixture of polyvinyl acetate and polyvinyl alcohol, acting as a binder, and, if approp-riate, additives. The components present in the enveloping layer can partly also penetrate into depressions in the carrier material.
The percentage contents of the components contained in the combination carrier granules according to the inven-tion can be varied within substantial ranges. The content of carrier material is in general between S0 and 98% by weight, preferably between 60 and 92X by weight. The con-tent of liquid and also o-f solid biocidal active compounds is in géneral between 0.1 and 20% by weight, preferably between 0~5 and 15X by weight. The content of the mixture of polyvinyl acetate and polyvinyl alcohol functioning as the binder is in general between 0.1 and 4X by ~eight~ pre-ferably between 0~3 and 3% by weight~ in general D.~S to .25 part by weight, preferably 0.1 to 0.2 part by weight~
of polyvinyl alcohol being present per part of polyvinyl aceta~e~ The granules contain additives, if appropriate9 in amounts of 1 to 40 parts by ~eight, preferably 2 to 30 parts by weight.
All those components ~hich have already been men-tioned as preferred in connection with the description of the combination carrier granules according to the invention 3~ can preferably be used in the preparation of the combination carrier granules according to the invention.
It is necessary to employ the solid bioc;dal active compounds in finely divided form in the preparation of the granules according to the invention. For this, the biocidal active compounds which are solid at room temperature are in general used in the finely ground state, if appropriate Le A 23 328 ' ~ ~t~`9~7~7~
mixed w;th grinding auxiliaries. The b;ocidal active com-pounds which are liquid at room temperature are in generaL
used as a mixture with extenders, such as attapulgite, mont-morillonite, sepiolith or highly disperse silica. However, it is also possible to employ a mixture of liquid and solid biocidal active compounds, if appropr;ate mixed with grind-ing auxiliaries, in the finely divided state~
The mi~ture of polyvinyl acetate and polyvinyl alcohol functioning as the binder (adhesive) is employed in the form of an aqueous dispers;on. Poss;ble diluents here are, in addition to water, also organic solvents, preferably low-boiling organic solvents, such as methanol~ ethanol, butanol and methylene chloride.
In carrying out the process according to the inven-tion, a procedure is in general followed in ~hich granularcarrier material with a compact surface is introduced into a mixer and sprayed, while mixing continuously, with an aqueous dispersion of polyvinyl acetate and polyvinyl alco-hol and then either, in succession, at least one solid bio-cidal active compound, if appropriate mixed w;th additives~and at least one liqu;d biocidal active compound, if approp-r;ate m;xed with additives, are added, or a m;xture of at least one solid biocidal active compound and at least one liquid b;ocidal active compound, ;f appropriate m;xed w;th addit;ves, is added~ if appropriate the product is sprayed again ~ith an aqueous dispersion of polyv;nyl acetate and polyvinyl alcohol, and the granular products thus obtained are dried.
The sequence in which the components are applied to the carrier material can be varied in the particular manner desired.
The process according to the ;nvention ;s in general carried out at room temperature. Ho~ever, it is also possible to carry out the process at a somewhat ele-vated temperature.
The drying temperature can be varied within aLe A 23 328 ' 7~
substantial range. In general, drying is carried out at granule temperatures of between ~0C and 70C, preferably between 30C and 65C. If appropr;ate, dry;ng can be carried out under redused pressure. Prying can furthermore be carried out either in the mixer used to coat the carrier material or in a separate drying apparatus.
The process according to the invent;on can be carried out either batchwise or continuously in customary apparatuses.
The combination carrier granules according to the invention can be employed for ~he most diverse purposes, depending on the active components contained therein. Thus, they can be used, for example, for combating animal pests, fungi and/or weeds. If they contain plant growth regulators, they can also be employed for influencing the growth of crop plants.
The combination carrier granules ~ccording to the invention can be applied by customary methods, such as, for example, scattering.
The preparation of the combination carrier granules according to the invention can be seen from the following examples.
Preparation Examples Comparison Example 176.94 g of qùartz sand granules ~i~h a diameter of 0.4 to 0.8 mm are sprayed in a mixer, ~hile continuously mixing at room temperature, ~ith an aqueous dispersion con-taining 1~6 9 of polyvinyl acetate. Thereafter, 13.~6 9 of a commercially available finely ground pulverulent mixture 30 containing 10.47 9 of ~3-dihydro-2,2-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 .
t~ 7~3 H3C ,~ ~1 ~
and 0.6 9 of blue dyestuff and 7 9 of a m;xture consisting to the extent of 65.21 per cent by weight of 0-ethyl 0-(2--isopropoxycarbonyl-phenyl) N-isopropyl-thionophosphoric acid S ester-amide of the Formula p ,0 OCH2H5 (2) NH-CX(CH3)2 Co~-cH(cH3~2 and to the extent of 34.79 per cent by weight of highly dis-perse silica, are added at room temperature. The components are mixed at room temperature for a further 10 minutes and lD then dried in the mixer at a maximum temperature of the material to be dried of 60C~ 200 9 of comb;nation carr;er granules containing 5.2 per cent by weight of active com-pound of the formula (1) and 2.1 per cent by weight of active compound of the formula (2) are obtained in this manner.
The result;ng granules exhibited severe abrasion and softening, so that they ~ere unsui~able for use in practice.
Example 1 88.8 kg of quartz sand granules with a d;ameter of 0.3 to 0.7 mm are sprayed in a mixer, whilst m;xing con-tinuously at room temperature, with 3.34 kg of an aqueous d;spersion containing û.8 kg of polyvinyl acetate and 0.1 kg of polyvinyl alcohol. Thereafter, 6.62 kg of a commer-cially ava;lable f;nely ground pulverulent m;xture conta;n-;ny 5 kg of 2,3-d;hydro-Z,Z-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 ~ ' .
: `:
H3C _;~ t 1 ) and a mixture of 2 kg of 0-ethyl 0-(2-isopropoxycarbonyl-phenyl) N-isopropylthionophosphoric acid ester-amide of the formula ~ ,,, OC2H5 \=~ NH-CH ~ C~ 3 ) 2 ( 2 ) Ct)O-CH ( CH 3 ) 2 are added at room temperature to 0.37 kg of blue dyestuff and 0.37 kg of highly disperse silica. The components are mixed àt room temperature for a further 10 minutes and then dried in the mixer at a maximum temperature of the ma~erial to be dried of 60C. 100 kg of combination carrier gran-ules containing 5% by weight of active compound of the for-mula t1) and 2~ by wei0ht of active compound of the formula t2) are obtained in this manner.
The granules are distinguished by a high abrasion resistance.
Example 2 90.1 kg of quartz sand granules w;th a diameter of 0.3 to 0.7 mm are sprayed ;n a mixer, while cont;nuously mixing at room temperature, with 3.34 kg of an aqueous dis-persion containing 0.75 kg of polyvinyl acetate and 0.15 kgof poly~inyl alcohol. Thereafter~ 5.3 kg of a commercially available finely ground pulverulent mixture contain;ng 4 kg of 2,3-dihydro-Z,Z-dimethyl-7-benzofuranyl N-methyl-carbamate of the formula Le A 23 328 :
~: . ' ' -- ~
9~77~) H3C ~ t1) and a mixture of 2 kg of 0-ethyl 0- (2-isopropoxycarbonyl-phenyl) N-isopropylthi onophosphoric acid ester-amide of the formula ~ o p _ OCH2H5 NH-CH(CH3)2 S2) COO-CH(CH3)2 are added at room temperature to 0.37 kg of blue dyestuff and 1.34 kg of highly disperse silica. The components are mixed at room temperature for a further 10 minutes and then dried in the mixer at a maximum temperature of the material 10 to be dried of 60C. 100 kg of combination carrier granules containing 4% by weight of active compound of the formula (1) and 2X by weight of active compound of the formula (2) are obtained in this manner.
The granules are distinguished by a high abrasion resistance.
Le A 23 328 :. :
Claims (20)
1. A combination carrier granule, wherein said combination carrier granule comprises a granular carrier material with a com-pact surface coated with at least one solid biocidally active compound, at least one liquid biocidally active compound, polyvinyl acetate and polyvinyl alcohol.
2. A combination carrier granule according to claim 1, wherein said solid biocidally active compound is a carbamate.
3. A combination carrier granule according to claim 1 or 2, wherein said liquid biocidally active compound is a phosphoric acid derivative.
4. A combination carrier granule according to claim 1, wherein said solid biocidally active compound is 2,3-dihydro-2,2-dimethyl-7-benzofuranyl N-methyl-carbamate.
5. A combination carrier granule according to claim 1 or 4 wherein said liquid biocidally active compound is 0-ethyl 0-(2-isopropoxycarbonylphenyl) N-isopropylthionophosphoric acid ester-amide.
6. A combination carrier granule according to claim 1, comprising 0.1 to 20% by weight of said biocidally active compounds.
7. A combination carrier granule according to claim 1, further comprising an additive selected from an extender, grinding auxiliary, dyestuff, water and an organic solvent.
Le A 23 328-CA 11
Le A 23 328-CA 11
8. A process for the preparation of a combination carrier granule, comprising spraying granular carrier material having a compact surface with an aqueous dispersion of polyvinyl acetate and polyvinyl alcohol in a mixer and then spraying with at least one solid biocidally active compound, at least one liquid biocidal-ly active compound, and drying the granular product thus obtained.
9. A process according to claim 8 wherein after spraying with said solid and liquid biocidally active compounds the granule is sprayed again with an aqueous dispersion of polyvinyl acetate and polyvinyl alcohol.
10. A process according to claim 8 wherein at least one of said solid or liquid biocidally active compounds comprises an additive selected from an extender, grinding auxiliary, dyestuff, water and organic solvent.
11. A process according to claim 8, wherein said solid biocidally active compound is a carbamate.
12. A process according to claim 8 or 11, wherein said liquid biocidally active compound is a phosphoric acid derivative.
13. A process according to claim 8, wherein said solid bio-cidally active compound is 2,3-dihydro-2,2-dimethyl-7-benzo-furanyl N-methyl-carbamate.
14. A process according to claim 8 or 13, wherein said liquid biocidally active compound is 0-ethyl 0-(2-isopropoxycar-bonylphenyl) N-isopropyl-thionophosphoric acid esteramide.
15. A method of applying liquid and solid biocidally active compounds to plants or their environment comprising applying to said plants or their environment a combination carrier granule according to claim 1.
16. A method according to claim 15, wherein said solid bio-cidally active compound is a carbamate.
17. A method according to claim 15 or 16, wherein said liquid biocidally active compound is a phosphoric acid derivative.
18. A method according to claim 15, wherein said solid bio-cidally active compound is 2,3-dihydro-2,2-dimethyl-7-benzofuranyl N-methyl-carbamate.
19. A method according to claim 15 or 18, wherein said liquid biocidally active compound is 0-ethyl 0-(2-isopropoxycar-bonylphenyl) N-isopropyl-thionophosphoric acid esteramide.
20. A combination carrier granule according to claim 1 comprising 50 to 98% by weight of said granular carrier material and 0.1 to 4% by weight of polyvinyl acetate and polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000501857A CA1279770C (en) | 1985-02-16 | 1986-02-14 | Combination carrier granules |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3505424.7 | 1985-02-16 | ||
| CA000501857A CA1279770C (en) | 1985-02-16 | 1986-02-14 | Combination carrier granules |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1279770C true CA1279770C (en) | 1991-02-05 |
Family
ID=4132472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000501857A Expired - Lifetime CA1279770C (en) | 1985-02-16 | 1986-02-14 | Combination carrier granules |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1279770C (en) |
-
1986
- 1986-02-14 CA CA000501857A patent/CA1279770C/en not_active Expired - Lifetime
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