CA1239804A - Process for the preparation of plant protection agent dispersions containing swelling agents - Google Patents
Process for the preparation of plant protection agent dispersions containing swelling agentsInfo
- Publication number
- CA1239804A CA1239804A CA000458299A CA458299A CA1239804A CA 1239804 A CA1239804 A CA 1239804A CA 000458299 A CA000458299 A CA 000458299A CA 458299 A CA458299 A CA 458299A CA 1239804 A CA1239804 A CA 1239804A
- Authority
- CA
- Canada
- Prior art keywords
- agent
- plant protection
- swelling agent
- protection agent
- colloid mill
- 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.)
- Expired
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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dentistry (AREA)
- Dispersion Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Fertilizers (AREA)
Abstract
Abstract of the disclosure:
The invention relates to a process for the pre-paration of aqueous plant protection agent dispersions containing swelling agents, in which an aqueous plant protection agent dispersion is mixed with a swelling agent in a colloid mill.
The invention relates to a process for the pre-paration of aqueous plant protection agent dispersions containing swelling agents, in which an aqueous plant protection agent dispersion is mixed with a swelling agent in a colloid mill.
Description
2 ~
HOE 83/F 12Ci Conimerc;atly available plan-~ protection agent d;spersions usually also conta;n swell;ng agents~ in addition to water~ as the carrier liquid, the active ingredient and wetting and dispe~s;ng agents and ant;-foam;ng agents. The swell;ng agents serve, for example,to increase the storage stability of the dispersions and to prevent sedimentat;on~
The preparation of plant protection agent dis-persions by wet grinding of the materials by means of grind-ing ball rn;lls ;s known from German Offenlegungsschrift2,924~403. ~his preparation is effected by mixing the romponents in a stirred kettle ancl then grinding the mix-ture in grinding ball mills. In processes used hitherto, the swelling agent, such asO for example~ polysaccharides, aluminosil;cates, ~anthan gum and the like, was added in the -form of aqueous concPntrated solu-tions to the premix thus prepared.
The decis;ve disadvantage of this procedure is that the swelLing agent solut;ons added become very highly ~iscous and accordingly difficult to handle, in sp;te of a low content of swelling agent. Aqueous solut;ons of swell;ng agents obtained from naturally occurr;ng sub-stances, such as polysaccharides, ~end to form mold very rapidly when left to stand, so that ~ne solut;ons become useless. ~nother particular disadvantage is the fact that the swelling agent solutions change as a result of 31L~3~
the grinding process ;n the bead m;lls to the extent that their stabilizing properties are reduced or even completely lost~
An undes;rable d;lution effect of the plant pro-tection agent dispersions is usually produced on addition of aqueous s~:elling agent solutions. In order to ach;eve high concentrations of active ;ngredient in the disper sion, it is therefore necessary to use correspondingly concentrated active ingredient dispersions in ~he ~rind-ing process in order to compensate this dilution effect.Agglomeration and caking may arise when dispers;ons with ;ncreased active ;ngredient concentrations are ground, especially if active ingredients hav;ng melting points between 70 and 100C are used; as a consequence, the 1S grinding process may come to a complete standstill. If active ingred;ents w;th melting points above 100C are used, for example isoproturon or carbendazim, h;~hly v;s cous dispersion concentrates which cannot be ground are l;kewise frequently obtainedD
The addition of swelling agents by simple admix ing to the plant protection agent dispersions hitherto presented particular problems, since good dispersion of the s~elling agent in the active ingredient dispersion ;s not achieved here. The reason for th;s ;s that the s~lelling agent is present in a very lo~l concentration of only about 0.1% by weight, based on the plant protection agent d;spersion~ Thus~ only 4 kg of swelling ayent are added to an amount of 4 tonnes of plant protection agent d;spersion~ When the swelling agent is stirred into th~
:~23~
~t --~ . ~
a~ueous dispersion, the formation of lumps accordingly eas;ly occurs; in addit;on, the swell;ng agent can also easily stick to the st;rrer.
The object of the present ;nvention was thus to discover a process which enables swell;ng agents to be added to plant protection agent dispersions without the abovement;oned problems arisins.
It has no~J been found, surpris;ngly, that the swelling agent can be added to the plant protection 3gent d;spersion after the customary gr;nd;ng processes and that superior properties of the plant protectior agent d;spers;ons, conta;ning swelling 3gent~ thus prepared can be achieved here ;f a collo;d m;ll ;s used for the m;x;ng operat;on.
The present ;nvention thus relates to a process for the preparat;on of aqueous plant protect;on agent dispers;ons containing swell;ng agents, wh;ch compr;ses mix;ng an aqueous plant protect;on agent dispers;on ~Jith a swelling agent ;n a colloid m;ll.
2D Colloid mills ~h;ch can be used are, for example, toothed d;sc~ corundum disc or wet cutt;ng mills (c.f.
D~ Seidel, Masch;nenmarkt, Wurzburg 85 (1979), page 44), preferably the toothed d;sc collo;d m;ll. Only the use of such collo;d mills for pre-comm;nut;on of act;ve ;ngred;ents for the protec~;on of plants has hitherto been d;sclosed~ However, ;n the process accord;ng to the ;nvent;on, no actual gr;nding operat;on takes place~
s;nce the act;ve ;ngredients ;n the dispersion are already ;n an extremely f;n2ly ground state.
1~23~
In the process according to the invention, the plant protection agent dispersion is advantageously ;ntroduced into the collo;d mill via a su;table attach-ment, exped;ently a funnel-shaped attachment, such that a funnel-shaped indentation, hereafter called a whirl~ is ~ormed in the dispersion as a result of the suction effect. The swelling agent is metered into this whirl in ~iquid, i~e. dissolved or suspendedr form, ;n which case water or organic solvents~ such as, for example, poly glycols, can be used as the liquidr or in solid form, in particular in solid form. A customary metering device, for example a Gericke metering device, is used for this purpose.
In the colloid mill, the dispersion and the s~elling a~ent added are mixed very intimately on the basis of the high shearing forces on passage through the mill. The desired spread;ng of the swelling agent thereby occurs~
The plant protection agent dispersions thus pre-pared can be stored without problems and have highstabil;tiesO D;str;bution of the swelling agent in the d;spers;on ;s opt;mum.
Aqueous plant protection agent dispersions which can be used are all the custom3ry plant protection agent dispersions prepared, as described above, for example according -to German Offenlegungsschrift 2,924,403, by we. grind;ng by means of bead mills. The dispersions thus contain the customary wett;ng agents, adhesivesr emulsif;ers and d;spersing agents and other additives, ~3~
such as anti~foaming agents, preservatives and the like.
Examples 3T wetting agents are polyoxyethylated alkyl-phenols, polyoxyethylated oleylam;nes or stearylamines and alkyl or alkylphenyl-sulfonates. ExaMples of sult-able d;spers;ng agents are sodium lign;n-sulfonate, sodium 2,Z'~dinaphthyl-methane-6,6'~disulfonate, sodium dibu~ylnaphthalenesulfonate, sodium oleyl-methyl~taurate, Na lauryl ether-phosphate, condensation products prepared from polyglycol ethers (prepared from nonylphenol, ethylene oxide and formaldehyde), Na sulfite and maleic anhydride (~erman Patent 2,132~405, so-called alkali metal salts of sulfosuccinic acid esters) or condensation products of cresol, formaldehyde and sodium b;sulfite.
Examples of enulsifiers ~hich can be used areO calcium alkylarylsulfonates, fatty acid polyglycol esters, alkyl-aryl polyglycol ethers, fatty alcohol polyglycol ethers~
polyethoxylated oleylamines or stearylamines, propylene oxide/ethylene oxide condensation products, alkyl poly-ethers, sorbitan fatty acid esters, alkylaryl/propylene oxide/ethylene oxide condensation products and the like.
Furtherrnore, any des;red customary active ;ngredients can be used for the d;spers;ons~ for example the active ;ngredients carbendazim, ;soproturon, l;nuron, endosulf2n and rnonol;nuron.
The s~lelling agents used can be all the customary swelling agents, such as, for example, polysaccharidesr - for example those wh;ch can be prepare(i from the corres-ponding naturally occurring products by means of Xantho-monas bacteria, alumino-il;cates, such as montmorilloniLes o~
or benton;te grades~ for example RHectorit, xanthan gum~
gum arabic or algina.es~ in particular polysaccharides.
These are usuaLly employed in concentrations of 0.01 to 1X by weight, in particular 0c04 to 0.3% by weight, based S on the total plant protection agent dispersion.
The process according to the invention is illus-trated by the following examplesO
1 a) 99.9 parts by weight of an aqueous carbendazim dispers;on (carbendaz;m - 2-methoxycarbonylamino-benz-imidazole~ of the following compos;t;on: ~OX by we;ght of active ;ngred;entO 12X by weight of dispersing agent tsod;um sal~ of a sulfosuccinic acid half-ester, pfepared by react;ng a polyglycol ether based on nonylphenol~
ethylene oxide and formaldehyde with sodium sulfite and maleic anhydride), 2X by weight of Na lignin~sulfonate, 2% by we;ght of ant; foaming agent (type SE 2, Wacker Chem;e, Mun;ch)~ 4% by we;ght of alkyl polyglycol ether, 5X by weight of ethylene glycol and 35X by ~Je;ght or water~
wh;ch has been f;nely ground ;n a gr;nd;ng ball mill, are introduced into a toothed d;sc collo;d mill (type: RPUC
m;ll from Probst und Clasen) via a funnel attachment, unt;l a wh;rl forms ;n the dispersion. 0.1 part by weight of a polysacchar;de (~Rhodophol 23) in solid form is metered ;nto th;s wh;rl via a Ger;cke meter;ng dev;ce ;n the course of about 2 minutes, and the t~o components are mixed intensively w;th one another in the m;ll.
The plant protect;on agent d;spersion thus pre pared was stable at S0C over a period of 3 months.
~;2 3~
1 b) A similarLy good stability is obtained if the swelling agent is metered ;n as a 2% strength aqueous solution or suspension ;n water or an organic solvent.
However, the extremely finely ground dispersion experi-ences a dilution effect.
Example 2 99.95 parts by weight of a finished aqueous iso-proturon d;spers;on (isoproturon ~ N-4-isopropylphenyl-N,N'-dimethylurea~ of the following composition: 46.5%
of act;ve ingredient, 6% of dispersing agent tcondensa-tion product of cresol, formaldehyde and sodium bisul~
flte), 3% of Na lauryl ether-phosphate (tR)Forlanit P~
Henkel), 1X of anti-foaming agent (type SE2), 1 OX of ethylene glycol, O.OS~ of preservative (~R)Bronidox L, ~S Henkel) and 33.45% of water, are mixed ~ith 0~05 part by eight of (R)Kelzan S (a polysaccar;de) ;n the (R~PUC
m;ll as descr;bed ;n Example 1. The dispersion, contain ing swelling agent, thus prepared was stable to storage at 50C over a period of 3 months.
HOE 83/F 12Ci Conimerc;atly available plan-~ protection agent d;spersions usually also conta;n swell;ng agents~ in addition to water~ as the carrier liquid, the active ingredient and wetting and dispe~s;ng agents and ant;-foam;ng agents. The swell;ng agents serve, for example,to increase the storage stability of the dispersions and to prevent sedimentat;on~
The preparation of plant protection agent dis-persions by wet grinding of the materials by means of grind-ing ball rn;lls ;s known from German Offenlegungsschrift2,924~403. ~his preparation is effected by mixing the romponents in a stirred kettle ancl then grinding the mix-ture in grinding ball mills. In processes used hitherto, the swelling agent, such asO for example~ polysaccharides, aluminosil;cates, ~anthan gum and the like, was added in the -form of aqueous concPntrated solu-tions to the premix thus prepared.
The decis;ve disadvantage of this procedure is that the swelLing agent solut;ons added become very highly ~iscous and accordingly difficult to handle, in sp;te of a low content of swelling agent. Aqueous solut;ons of swell;ng agents obtained from naturally occurr;ng sub-stances, such as polysaccharides, ~end to form mold very rapidly when left to stand, so that ~ne solut;ons become useless. ~nother particular disadvantage is the fact that the swelling agent solutions change as a result of 31L~3~
the grinding process ;n the bead m;lls to the extent that their stabilizing properties are reduced or even completely lost~
An undes;rable d;lution effect of the plant pro-tection agent dispersions is usually produced on addition of aqueous s~:elling agent solutions. In order to ach;eve high concentrations of active ;ngredient in the disper sion, it is therefore necessary to use correspondingly concentrated active ingredient dispersions in ~he ~rind-ing process in order to compensate this dilution effect.Agglomeration and caking may arise when dispers;ons with ;ncreased active ;ngredient concentrations are ground, especially if active ingredients hav;ng melting points between 70 and 100C are used; as a consequence, the 1S grinding process may come to a complete standstill. If active ingred;ents w;th melting points above 100C are used, for example isoproturon or carbendazim, h;~hly v;s cous dispersion concentrates which cannot be ground are l;kewise frequently obtainedD
The addition of swelling agents by simple admix ing to the plant protection agent dispersions hitherto presented particular problems, since good dispersion of the s~elling agent in the active ingredient dispersion ;s not achieved here. The reason for th;s ;s that the s~lelling agent is present in a very lo~l concentration of only about 0.1% by weight, based on the plant protection agent d;spersion~ Thus~ only 4 kg of swelling ayent are added to an amount of 4 tonnes of plant protection agent d;spersion~ When the swelling agent is stirred into th~
:~23~
~t --~ . ~
a~ueous dispersion, the formation of lumps accordingly eas;ly occurs; in addit;on, the swell;ng agent can also easily stick to the st;rrer.
The object of the present ;nvention was thus to discover a process which enables swell;ng agents to be added to plant protection agent dispersions without the abovement;oned problems arisins.
It has no~J been found, surpris;ngly, that the swelling agent can be added to the plant protection 3gent d;spersion after the customary gr;nd;ng processes and that superior properties of the plant protectior agent d;spers;ons, conta;ning swelling 3gent~ thus prepared can be achieved here ;f a collo;d m;ll ;s used for the m;x;ng operat;on.
The present ;nvention thus relates to a process for the preparat;on of aqueous plant protect;on agent dispers;ons containing swell;ng agents, wh;ch compr;ses mix;ng an aqueous plant protect;on agent dispers;on ~Jith a swelling agent ;n a colloid m;ll.
2D Colloid mills ~h;ch can be used are, for example, toothed d;sc~ corundum disc or wet cutt;ng mills (c.f.
D~ Seidel, Masch;nenmarkt, Wurzburg 85 (1979), page 44), preferably the toothed d;sc collo;d m;ll. Only the use of such collo;d mills for pre-comm;nut;on of act;ve ;ngred;ents for the protec~;on of plants has hitherto been d;sclosed~ However, ;n the process accord;ng to the ;nvent;on, no actual gr;nding operat;on takes place~
s;nce the act;ve ;ngredients ;n the dispersion are already ;n an extremely f;n2ly ground state.
1~23~
In the process according to the invention, the plant protection agent dispersion is advantageously ;ntroduced into the collo;d mill via a su;table attach-ment, exped;ently a funnel-shaped attachment, such that a funnel-shaped indentation, hereafter called a whirl~ is ~ormed in the dispersion as a result of the suction effect. The swelling agent is metered into this whirl in ~iquid, i~e. dissolved or suspendedr form, ;n which case water or organic solvents~ such as, for example, poly glycols, can be used as the liquidr or in solid form, in particular in solid form. A customary metering device, for example a Gericke metering device, is used for this purpose.
In the colloid mill, the dispersion and the s~elling a~ent added are mixed very intimately on the basis of the high shearing forces on passage through the mill. The desired spread;ng of the swelling agent thereby occurs~
The plant protection agent dispersions thus pre-pared can be stored without problems and have highstabil;tiesO D;str;bution of the swelling agent in the d;spers;on ;s opt;mum.
Aqueous plant protection agent dispersions which can be used are all the custom3ry plant protection agent dispersions prepared, as described above, for example according -to German Offenlegungsschrift 2,924,403, by we. grind;ng by means of bead mills. The dispersions thus contain the customary wett;ng agents, adhesivesr emulsif;ers and d;spersing agents and other additives, ~3~
such as anti~foaming agents, preservatives and the like.
Examples 3T wetting agents are polyoxyethylated alkyl-phenols, polyoxyethylated oleylam;nes or stearylamines and alkyl or alkylphenyl-sulfonates. ExaMples of sult-able d;spers;ng agents are sodium lign;n-sulfonate, sodium 2,Z'~dinaphthyl-methane-6,6'~disulfonate, sodium dibu~ylnaphthalenesulfonate, sodium oleyl-methyl~taurate, Na lauryl ether-phosphate, condensation products prepared from polyglycol ethers (prepared from nonylphenol, ethylene oxide and formaldehyde), Na sulfite and maleic anhydride (~erman Patent 2,132~405, so-called alkali metal salts of sulfosuccinic acid esters) or condensation products of cresol, formaldehyde and sodium b;sulfite.
Examples of enulsifiers ~hich can be used areO calcium alkylarylsulfonates, fatty acid polyglycol esters, alkyl-aryl polyglycol ethers, fatty alcohol polyglycol ethers~
polyethoxylated oleylamines or stearylamines, propylene oxide/ethylene oxide condensation products, alkyl poly-ethers, sorbitan fatty acid esters, alkylaryl/propylene oxide/ethylene oxide condensation products and the like.
Furtherrnore, any des;red customary active ;ngredients can be used for the d;spers;ons~ for example the active ;ngredients carbendazim, ;soproturon, l;nuron, endosulf2n and rnonol;nuron.
The s~lelling agents used can be all the customary swelling agents, such as, for example, polysaccharidesr - for example those wh;ch can be prepare(i from the corres-ponding naturally occurring products by means of Xantho-monas bacteria, alumino-il;cates, such as montmorilloniLes o~
or benton;te grades~ for example RHectorit, xanthan gum~
gum arabic or algina.es~ in particular polysaccharides.
These are usuaLly employed in concentrations of 0.01 to 1X by weight, in particular 0c04 to 0.3% by weight, based S on the total plant protection agent dispersion.
The process according to the invention is illus-trated by the following examplesO
1 a) 99.9 parts by weight of an aqueous carbendazim dispers;on (carbendaz;m - 2-methoxycarbonylamino-benz-imidazole~ of the following compos;t;on: ~OX by we;ght of active ;ngred;entO 12X by weight of dispersing agent tsod;um sal~ of a sulfosuccinic acid half-ester, pfepared by react;ng a polyglycol ether based on nonylphenol~
ethylene oxide and formaldehyde with sodium sulfite and maleic anhydride), 2X by weight of Na lignin~sulfonate, 2% by we;ght of ant; foaming agent (type SE 2, Wacker Chem;e, Mun;ch)~ 4% by we;ght of alkyl polyglycol ether, 5X by weight of ethylene glycol and 35X by ~Je;ght or water~
wh;ch has been f;nely ground ;n a gr;nd;ng ball mill, are introduced into a toothed d;sc collo;d mill (type: RPUC
m;ll from Probst und Clasen) via a funnel attachment, unt;l a wh;rl forms ;n the dispersion. 0.1 part by weight of a polysacchar;de (~Rhodophol 23) in solid form is metered ;nto th;s wh;rl via a Ger;cke meter;ng dev;ce ;n the course of about 2 minutes, and the t~o components are mixed intensively w;th one another in the m;ll.
The plant protect;on agent d;spersion thus pre pared was stable at S0C over a period of 3 months.
~;2 3~
1 b) A similarLy good stability is obtained if the swelling agent is metered ;n as a 2% strength aqueous solution or suspension ;n water or an organic solvent.
However, the extremely finely ground dispersion experi-ences a dilution effect.
Example 2 99.95 parts by weight of a finished aqueous iso-proturon d;spers;on (isoproturon ~ N-4-isopropylphenyl-N,N'-dimethylurea~ of the following composition: 46.5%
of act;ve ingredient, 6% of dispersing agent tcondensa-tion product of cresol, formaldehyde and sodium bisul~
flte), 3% of Na lauryl ether-phosphate (tR)Forlanit P~
Henkel), 1X of anti-foaming agent (type SE2), 1 OX of ethylene glycol, O.OS~ of preservative (~R)Bronidox L, ~S Henkel) and 33.45% of water, are mixed ~ith 0~05 part by eight of (R)Kelzan S (a polysaccar;de) ;n the (R~PUC
m;ll as descr;bed ;n Example 1. The dispersion, contain ing swelling agent, thus prepared was stable to storage at 50C over a period of 3 months.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for mixing a solid swelling agent with an aqueous plant protection agent dispersion which comprises mixing said solid swelling agent with said aqueous plant protection agent dispersion in a colloid mill.
2. The process as claimed in claim 1, wherein a plant protection agent dispersion is introduced into a colloid mill until a whirl forms, and the swelling agent is metered into this whirl.
3. The process as claimed in claim 1, wherein a toothed disc, corundum disc or wet cutting mill is used as the colloid mill.
4. The process as claimed in claim 1, 2 or 3, wherein a toothed disc is used as the colloid mill.
5. The process as claimed in claim 1, 2 or 3 wherein a polysaccharide, aluminosilicate, xanthan gum, gum arabic or algin-ate is used as the swelling agent.
6. The process as claimed in claim 1, 2 or 3 wherein 0.01 to 1% by weight of swelling agent, based on the total plant pro-tection agent dispersion, is used.
7. The process as claimed in claim 1, 2 or 3, wherein a polysaccharide, aluminosilicate, xanthan gum, gum arabic or algin-ate is used as the swelling agent, and a toothed disc is used as the colloid mill.
8. The process as claimed in claim 1, 2 or 3 wherein 0.01 to 1% by weight of swelling agent, based on the total plant pro-tection agent dispersion, is used, and a toothed disc is used as the colloid mill.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3324499.5 | 1983-07-07 | ||
| DE19833324499 DE3324499A1 (en) | 1983-07-07 | 1983-07-07 | METHOD FOR PRODUCING PLANT PROTECTANT DISPERSIONS CONTAINING SOURCES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239804A true CA1239804A (en) | 1988-08-02 |
Family
ID=6203387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000458299A Expired CA1239804A (en) | 1983-07-07 | 1984-07-06 | Process for the preparation of plant protection agent dispersions containing swelling agents |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0134462B1 (en) |
| JP (1) | JPH0637361B2 (en) |
| AT (1) | ATE36443T1 (en) |
| AU (1) | AU580557B2 (en) |
| CA (1) | CA1239804A (en) |
| DE (2) | DE3324499A1 (en) |
| DK (1) | DK172536B1 (en) |
| HU (1) | HU199232B (en) |
| IL (1) | IL72319A (en) |
| ZA (1) | ZA845218B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763364A (en) * | 1994-09-21 | 1998-06-09 | Hoechst Schering Agrevo Gmbh | Thixotropic aqueous plant protection agent suspensions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679618A (en) * | 1990-07-06 | 1997-10-21 | Hoechst Aktiengesellschaft | Antifoams for solid crop protection agents |
| DE4313093C2 (en) * | 1993-04-22 | 1996-01-11 | Stefes Pflanzenschutz Gmbh | Suspension concentrates containing metamitron based on water as the only carrier |
| EP1246527A1 (en) * | 1999-08-26 | 2002-10-09 | Bayer CropScience S.A. | Preparation of aqueous suspension concentrates containing a pyrethrinoid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2614061A (en) * | 1948-05-03 | 1952-10-14 | Sherwin Williams Co | Method of preparing ddt dispersions using carboxy methyl cellulose |
| FR1252027A (en) * | 1958-04-22 | 1961-01-27 | Progil | Pesticide pastes |
| FR1285930A (en) * | 1960-11-01 | 1962-03-02 | Du Pont | New pesticide compositions and their manufacture which can be used in particular in agriculture |
| AU469384B2 (en) * | 1972-12-05 | 1976-02-12 | Mono Pumps (Engineering) Limited | Method and apparatus for mixing a powder witha flowable substance |
| US4061770A (en) * | 1976-04-15 | 1977-12-06 | Diamond Shamrock Corporation | Flowable, aqueous pesticide compositions of improved activity |
| JPS57209201A (en) * | 1981-06-16 | 1982-12-22 | Shinto Paint Co Ltd | Water-suspending slime control composition for paper making |
| NZ201065A (en) * | 1981-07-06 | 1984-09-28 | Merck & Co Inc | Microbiocidal dispersion containing methylene bis(thiocyanate) |
| JPS5872501A (en) * | 1981-10-24 | 1983-04-30 | Toagosei Chem Ind Co Ltd | Liquid agricultural chemical |
-
1983
- 1983-07-07 DE DE19833324499 patent/DE3324499A1/en not_active Withdrawn
-
1984
- 1984-06-30 AT AT84107608T patent/ATE36443T1/en not_active IP Right Cessation
- 1984-06-30 EP EP84107608A patent/EP0134462B1/en not_active Expired
- 1984-06-30 DE DE8484107608T patent/DE3473401D1/en not_active Expired
- 1984-07-02 HU HU842564A patent/HU199232B/en unknown
- 1984-07-06 CA CA000458299A patent/CA1239804A/en not_active Expired
- 1984-07-06 JP JP59139165A patent/JPH0637361B2/en not_active Expired - Lifetime
- 1984-07-06 DK DK198403351A patent/DK172536B1/en not_active IP Right Cessation
- 1984-07-06 IL IL8472319A patent/IL72319A/en not_active IP Right Cessation
- 1984-07-06 AU AU30373/84A patent/AU580557B2/en not_active Ceased
- 1984-07-06 ZA ZA845218A patent/ZA845218B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763364A (en) * | 1994-09-21 | 1998-06-09 | Hoechst Schering Agrevo Gmbh | Thixotropic aqueous plant protection agent suspensions |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3324499A1 (en) | 1985-01-17 |
| IL72319A0 (en) | 1984-11-30 |
| JPS60155101A (en) | 1985-08-15 |
| HUT34867A (en) | 1985-05-28 |
| DK335184D0 (en) | 1984-07-06 |
| JPH0637361B2 (en) | 1994-05-18 |
| DK172536B1 (en) | 1998-11-30 |
| AU580557B2 (en) | 1989-01-19 |
| EP0134462A1 (en) | 1985-03-20 |
| AU3037384A (en) | 1985-01-10 |
| DK335184A (en) | 1985-01-08 |
| DE3473401D1 (en) | 1988-09-22 |
| EP0134462B1 (en) | 1988-08-17 |
| ATE36443T1 (en) | 1988-09-15 |
| ZA845218B (en) | 1985-02-27 |
| IL72319A (en) | 1987-10-30 |
| HU199232B (en) | 1990-02-28 |
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