[go: up one dir, main page]

CA1285785C - Aqueous emulsions of plant protection agents - Google Patents

Aqueous emulsions of plant protection agents

Info

Publication number
CA1285785C
CA1285785C CA000524055A CA524055A CA1285785C CA 1285785 C CA1285785 C CA 1285785C CA 000524055 A CA000524055 A CA 000524055A CA 524055 A CA524055 A CA 524055A CA 1285785 C CA1285785 C CA 1285785C
Authority
CA
Canada
Prior art keywords
weight
agent
ethyl
methyl
group
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 - Lifetime
Application number
CA000524055A
Other languages
French (fr)
Inventor
Konrad Albrecht
Rudolf Heinrich
Hans Schumacher
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.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Application granted granted Critical
Publication of CA1285785C publication Critical patent/CA1285785C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—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
    • 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
    • A01N25/30—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 characterised by the surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid

Landscapes

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

Abstract

Abstract of the disclosure:

The invention describes plant protection agents based on aqueous emulsions and, in addition to the active compound, containing, as the dispersing agent, an ethylene oxide/
propylene oxide/ethylene oxide block copolymer which is phosphorylated in the alpha-position and the omega-posi-tion, or a salt thereof. These formulations have a low solvent content and possess a high stability.

Description

HOECHST AKTIENGESELLSCHAFT HOE 85/F 269 Dr.AU/ml New aqueous emulsions of plant protection agents It is known, and described in European Patent Application 47,396, to prepare concentrated emulsions, stable on storage, of herbicidally active phenoxyalkanecarboxylic acid esters, having an aqueous base, using ester-soluble emulsifiers and water-soluble dispersing agents. The ester-soluble emulsifiers used, if appropriate as a mix-ture with alkylarylsulfonates, are polyethylene glycol esters of fatty acids, polyethylene glycol ethers of fatty alcohols, of glycerides or of alkylphenols and also poly-oxyethylene and polyoxypropylene block polymers. The dispersing agents used are phosphated alkylarylpolyethy-lene oxides, the ammonium, sodium or potassium salts of phosphorylated polystyrylphenylpolyethylene oxide or ethylene oxide condensates of fatty amines.

The amounts of oil-soluble emulsifiers added are between 1.01 and 11.1 parts by weight per 100 parts by weight of phenoxyalkanecarboxylic acid ester. The amounts of dis-persing agent are 0.5 to 5 parts by weight per 100 parts by weight of aqueous solution. Anti-foaming agents based on long-chain alcohols and silicones are added in order to avoid the formation of foam which takes place in this operation.

Attempts to extend the use of the water-soluble ammonium, sodium or potassium salts of phosphorylated alkylarylpoly-ethylene oxides mentioned above to other active compounds than those mentioned in European Patent Application 47,396 result in considerable technical problems in use.
In storage tests of over 3 months at 50C, demixing phe-nomena which are reversible only to a limited extent occur in a number of preparations.
Similar problems are observed with the phosphorylated polystyrylphenylpolyethylene oxides described in European 128~78~
Patent Application 33,291; in the same way it is only possible to obtain colloidal emulsions of limited heat stability using alkylaryl polyglycol ether compounds described in DE-A 3,111,934.
Furthermore, it is descr:Lbed in EP-A 118,759 that t.erminally monophosphorylated ethy:Lene oxide/propylene oxide/
ethylene oxide block copolymers or salts thereof can be employed as dispersing agents in order to obtain aqueous pesticide formulations.
It has now been found, surprisingly, that certain wetting and dispersing agents which are soluble in water and organic solvents can be used advantageously in comparison with the water-soluble dispersing agents of the phosphorylated alkylarylpolyethylene oxide type described in EP-A 47,396 and in comparison with the terminally monophosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers described in EP-A 118,759.
The present invention therefore provides a plant protection ayent based on aqueous emulsions containing 5-60~ by weight of one or more active compounds which are soluble in water only to a slight extent or not at all, 10-90'~ by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I

1l (H)2P-[-(CH2-cH2-)x-(cjH-cH2-o)y-(cH2-cH2-o)z] 1 0 CH3 P(OH)m (I) 2 ( 2 CH2-)x-(~H-CH2-)y~(CH2~CH2~) ]
in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.

~?
.~

;,; ;. .

- 12857~
-2a- 23221-4322 Suitable salts are, in particular, the alkali metal, alkaline earth metal, ammonium, monoalkylammonium, dialkylammonium or trialkylammonium or monoalkanolammonium, dialkanolammonium or trialkanolammonium salts. These contain, in particular, 1 to 5 carbon atoms in the alkyl or alkanol moiety, respectively.
The preparations according to the invention are substantially free from organic solvents and inorganic salts.
They can therefore be handlecl without risk, especially in transport and storage. The viscosity of the finished preparation can be adjusted witlout problems to the desired r;
value by varying the polyethylene glycol content, so that it is possible to dispense with the dlspersing and thickening agents which are otherwise customary.
5uitahle phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers to be used in accordance with the invention are, in particular, those of the formula I and salts thereof:

(HO)2~-[O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z] O
CH3 P(OH)m (I) [(HO)2~-O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z]n in which x, y and z independently of one another denote a number from 2 to 200 and m and n denote 0, 1 or 2, it being necessary for the sum of n ~ m to be 2.
Preferably, x and z have the same meaning and represent, in particular, a number from 30 to 100; y denotes, in particular, a number from 20 to 100 and n is, in particular, 0. These block polymers can be employed ln the form of mixtures. Their preparation is described in Japanese Laid Open Patent Application JP-A-72/47982 t1972) of Kanebo & Co. Ltd. or in German Offenlegungsschrift No. 3,542,441 of June 4, 1987 (priority November 30, 1985) of Hoechst Aktiengesellschaft.
The formulations according to the invention can also contain, in addition, anti-freezing agents. These include, for example: ethylene glycol, propylene glycol, butanediol, urea, glycerol, polyethylene glycols and polypropylene glycols. They can also contain further formulation auxiliaries, such as ~28S785 -3a- 23221-4322 customary dlspersing agents, emulsifiers, thickeners and -especially for solid active compounds - also minor constituents of organic solvents.
Active compounds which can be employed for these preparations are, in particular, those which, by virtue of their low mel~ing point, can only be converted with difficulty or not at all into a finely disperse aqueous phase by lZ8~

means of grinding devices, or those in the case of which the grinding process demands special safety precautions.

Suitable active compounds for plant protection agents which can be employed are herbicides, insecticides, acari-cides, nematocides, pheromones or repellents, it being necessary for these to be soluble in water only to a slight extent or not at all. Solid active compounds should, however, have a good to very good solubility in one of the organic solvents mentioned below.

ExampLes of suitable herbicidal active compounds are alkyl phenoxyphenoxypropionates or alkyl heteroaryloxyphenoxy-propionates, such as methyl ~-4-(2',4'-dichlorophenoxy)-phenoxypropionate [common name: diclofopmethyl] (A), ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate (B) or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate [common name: fenoxapropethyl] (C), dinitroaniline com-pounds, such as 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline [common name: trifluralin] (D) or 2,6-dinitro-4-isopropyl-N,N-dipropylaniline Ccommon name: isopropa-lin] (E), hydroxybenzonitrile derivatives, such as 2,6-dibromo-4-hydroxybenzonitrile octanoate (F), or dinitro-phenol compounds, such as 2-sec.-butyl-4,6-dinitrophenol Ccommon name: dinoterb] (G).

The following are examples of suitable insecticides:
1,4,5,6,7,7-hexachloro-8,9,1û-trinorborn-5-en-2,3-ylene dimethyl sulfite [common name: endosulfan], 2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate Ccommon name: binapacryl], phosphoric acid esters, such as 0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate Ccommon name: triazophos] or pyrethroids, such as (S)-~-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dibromovinyl) 2,2-dimethylcyclopropanecarboxylate [common name: deltame-thrin].

Ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazoloC1,5a]-128578~i pyrim;d;ne-6-carboxylate [common name: pyrazophos] should be ment;oned as an example of suitable fungic;des, and the compounds (E)-8-(E)-10-dodecadienol or (Z)-7,8-epoxy-2-methyloctadecane should be mentioned as pheromones, and dimethyL phthalate should be mentioned as an example of repellents.

With the exception of the compounds (B) and (C), the abovementioned herbicides and the insecticides and the repellent are known from H. Martin, Pesticide Manual 6th edition 1979. The herbicides B) and C) are described in German Offenlegungsschrift 2,640,730, and the two phero-mones in M. Beroza, Chem. Controlling Insect Behaviour, Academic Press, N.Y. 1970.
Customary dispersing agents which may be employed in par-t;cular cases are preferably lignosulfonates, Na salts of dinaphthylmethanedisulfonic acids, the Na salt of a sul-fon;c ac;d formed from cresol, formaldehyde, Na sulfite and hydroxynaphthalenesulfonic acid, the Na salt of a sulfonic acid formed from m-cresol, formaldehyde and Na sulfite, condensation products formed from arylsulfonic acids and formaldehyde-Na salts, triethanolam;ne salts of phosphorylated polystyrylphenylpolyethylene oxides, poly-v;nyl alcohol, calcium dodecylbenzenesulfonate and alkyl-naphthalenesulfonates of vary;ng alkyl chain length.

Su;table emulsifiers are nonionic, anionic or cationic surface-active substances, mixtures of nonionic and anionic components being used predominantly. Combinations of nonion;c and cat;on;c surface-act;ve agents can also be used, however. The emuls;f;ers which can be employed preferentially ;nclude calc;um phenylsulfonate, ethoxy-lated nonylphenols, ethoxylated aliphatic alcohols, ethoxylated castor oil, polyglycol esters of fatty acids, propylene glycol/ethylene glycol block polymers and mix-tures thereof.

Water-soluble polymers, such as, for example, polyvinyl 12~s7~;

alcohol, polyvinylpyrrolidone and cellulose der;vatives, can be used as thickening agents.

Suitable organic solvents are any water-immiscible sol-vents, for example aromatic compounds, such as toluene, xylenes, 1/2 methylnaphthylene or dimethylnaphthalenes, aliphatic compounds, such as paraffin oils or vegetable oils, alicyclic compounds, such as cyclohexane, alkanols, such as cyclohexanol or i-octyl alcohol, ethers, such as diethyl ether, ketones, such as cyclohexanone, 4-methyl-cyclohexanone or isophorone, or esters, such as ethyl acetate and tri-n-butyl phosphate.

The plant protection agents according to the invention contain, in particular, 5-60% by weight of active com-pound, 10-90% by weight, preferably 15-40% by weight, of water and 0.5-20% by weight, preferably 1-10% by weight, of a compound of the formula I or salts thereof, and cus-tomary additives, if appropriate 5 to 50% by weight of an Z0 anti-freezing agent and/or 1-10% by weight of a dispers-ing agent and/or 1-15% by weight of an emulsifier and/or 1-10% by we;ght of a thickener and/or 1 to 30% by weight of an organic solvent.

The invention also relates to a process for the prepara-tion of the agents according to the invention. For this purpose, the abovementioned components are stirred or shaken, in the required amounts, at temperatures between 0 and 60C, preferably at room temperature, in a zone of high turbulence until the desired stable emulsion has been formed; in the course of this the particle diameter is adjusted to, preferably, 1-15 ~m.

In order to carry out the process in practice, the aque-ous phase (carrier phase) is first prepared by stirring the diols or polyols and the dispersing agent into water.
After this the emusifier component is added to the ac-tive compound to be emulsified, and the mixture is finely dispersed in the aqueous phase. In the case of active compounds having a melting point of approx. 0C and higher, it can be necessary to prepare concentrated solu-tions thereof in one or more of the abovementioned organic solvents and to disperse these solutions in the aqueous phase after adding emulsifiers and, if appropriate, sta-bilizers.

lt is also possible, however, first to mix the dispersing agent into the active compound and then to disperse the mixture into the aqueous phase.

Dispersing can be effected by a stirring process or, if appropriate, also a shaking process, and is preferably continued until the organic phase corresponds to the desired droplet size. A droplet diameter of 1-15 ~m is advisable. The dispersing process is preferably carried out at room temperature, but can, however, also be carried out under cold conditions or at elevated temperatures.

Z0 The following examples are intended to illustrate the present invention in greater detail.

Formulation examples Example 1 36X by we;ght of methyl 2-(4-(2',4'-dichlorophenoxy)-phenoxy)-propionate are dissolved by stirring in 18% by weight of xylene at 20-25C, and 6~ by weight of a polygly-col fatty acid ester (containing 40 E0) are added. 2% byweight of the potassium salt of the phosphorylated ethy-lene oxide/propylene oxide/ethylene oxide block polymer of the abovementioned formula 1, n = 0 (containing 68% of ethylene oxide in the end product) are also dissolved in 28% by weight of water at room temperature, and 10% by weight of ethylene glycol are then added. The abovemen-tioned organic phase is allowed to flow slowly into this aqueous phase, with vigorous stirring by means of a blade stirrer, and the resulting white emulsion is stirred for 128~

approx. 15 minutes further. One sample is stored for 3 months at 50C; another is stored for the same period at -10C. The preparation is stable both to chemicals and in use.
s Example 2 32.3% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 4~ by weight of the diethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (containing 55% of ethylene oxide in the end product) are added. 8% by weight of glycerol are dissolved at room temperature in 34.7% by weight of water. The organic phase is allowed to flow slowly into this solution, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 minutes further.
The preparation is stable to chemicals and in use.

Example 3 30% by weight of ethyl 2-diethoxythiophosphoryloxy-5-methylpyrazolo[1,5a]pyrimidine-6-carboxylate (pyrazophos) are dissolved, with stirring and at 20-25C, in 18% by weight of xylene, and 6% by weight of a polyglycol ester (containing 40 EO) are added~ 4% by weight of the pota-sium salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I, n = o (containing 50% of ethylene oxide in the end product), are also dissolved at room temperature in 32% by weight of water, and 10% by weight of ethylene gly-col are then added. The abovementioned organic phase is allowed to flow slowly, with vigorous stirring by means of a paddle stirrer, into this aqueous phase, and the resulting white emulsion is stirred for approx. 15 minutes further. One sample is stored for 3 months at 50C;
another is stored for the same period at -10C. The lZ8~;785 g preparation is stable both to chemicals and in use.

Example 4 6.0% by weight of a polyglycol fatty acid ester (36 E0), 3% by weight of the free acid of the phosPhoryLated ethy-lene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (having a total content of 40% of ethylene oxide) and 10% by weight of glycerol are disso-lved in 49% by weight of water. 32.û% by weight of (E)-8-(E)-10-dodecadienol are then run in, with vigor-ous stirring. The resulting white emulsion is stirred for a further 15 to 20 minutes.

The preparation is stable to chemicals and in use.

Example 5 30.0% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 3% by weight of the free acid of the phosphorylated ethylene oxide/propy-lene oxide/ethylene oxide block copolymer of the above-mentioned formula I (containing 55% of ethylene oxide in the end product) are added. 12% by weight of polyethylene glycol (MW 1,000) are dissolved at room temperature in 34.0% by weight of water. The organic Phase is then run in slowly, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 min-utes further.

~he preparation is stable to chemicals and in use.

Example 6 3520% by weight of ethyl Z-(4-(6-chlor-2-benzothiazolyloxy)-phenoxypropanoate are dissolved in 36% by weight of xylene at 40-45C, with stirring, and 4% by weight of the potas-sium salt of the phosphorylated ethylene oxide/propylene --- 12B578~i oxide/ethylene oxide block copolymer of the formula I, n = o, having a total content of 6û% of ethylene oxide, and 2% by we;ght of the triethanolamine salt of a phos-phorylated polystyrylphenylpolyethylene oxide and 4% by weight of calcium dodecylbenzenesulfonate are added.

9% by weight of ethylene glycol are dissolved at room tem-perature in 25% by weight of water. The abovementioned organic phase is run into this aqueous solution, with vigorous stirring by means of a paddle stirrerj and the resulting white emulsion is stirred for approx. 15 minutes further at room temperature. A sample is stored for 3 months at 50C. The preparation is stable to chemicals and in use.
Example 7 35% by weight of 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline (trifluralin) are dissolved in 20% by weight of xylene at 20-25C, with stirring, and 3% by weight of the triethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the formula I (containing 55% of ethylene oxide) and 2%
by weight of the triethanolamine salt of a phosphorylated polystyrylphenylpolyethylene oxide and 3% by weight of a polyglycol fatty acid ester (36 E0) are added. 6% by we;ght of polypropylene glycol (molecular weight S00) are dissolved at room temperature in 31% by weight of water.
The organic phase is allowed to flow slowly into this aqueous solution, with vigorous stirring, and the result-ing yellow emulsion is stirred for approx. 20-25 minutes further, until the pale yellow color shade of the emulsion undergoes no further change. The preparation is stable in use and to chemicals even after storage at various temperatures.

Claims (6)

1. A plant protection agent based on aqueous emulsions containing 5-60% by weight of one or more active compounds which are soluble in water only to a slight extent or not at all, 10-90%
by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I

(I) in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.
2. An agent as claimed in claim 1, which comprises, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
3. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a herbicide selected from the group consisting of alkyl phenoxyphenoxypropionates or alkyl heteroaryloxyphenoxypropionates, dinitroaniline compounds, hydroxybenzonitrile derivatives or dinitrophenyl compounds, or an insecticide selected from the group consisting of endosulfan, binapacryl, phosphoric acid esters or pyrethroids, or a fungicide, or a pheromone or a repellant.
4. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a herbicide selected from the group consisting of alkyl phenoxyphyhenoxypropionates or alkyl heteroaryloxyphenoxypropionates, dinitroaniline compounds, hydroxybenzonitrile derivatives or dinitrophenyl compounds, or an insecticide selected from the group consisting of endosulfan, binapacryl, phosphoric acid esters or pyrethroids, or a fungicide, or a pheromone or a repellant and, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% hy weight of thickener or 1 - 30% by weight of organic solvent.
5. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a compound selected from the group consisting of diclofopmethyl (methyl .alpha.-4-(2',4'-dichlorophenoxy)-phenoxypropionate), fenoxapropethyl (ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate), trifluoralin (2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline), isopropalin (2,6-dinitro-4-isopropyl-N,N-dipropylaniline), 2,6-dibromo-4-hydroxybenzonitrile octanoate, dinoterb (2-sec.-butyl-4,6-dinitrophenol), endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylene dimethyl sulfite), binapacryl (2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate), triazophos (0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate), deltamethrin ((S)-.alpha.-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl)2,2-dimethylcyclopropanecarboxylate), pyrazophos (ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazolo[1,5a]-pyrimidine-6-carboxylate), dimethyl phthalate, (E)-8-(E)-10-dodecadienol or (Z)-7,8-epoxy-2-methyloctadecane.
6. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a compound selected from the group consisting of diclofopmethyl (methyl .alpha.-4-(2',4'-dichlorophenoxy)-phenoxypropionate), fenoxapropethyl (ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate), trifluoralin (2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline), isopropalin (2,6-dinitro-4-isopropyl-N,N-dipropylaniline), 2,6-dibromo-4-hydroxybenzonitrile octanoate, dinoterb (2-sec.-butyl-4,6-dinitrophenol), endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylene dimethyl sulfite), binapacryl (2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate), triazophos (0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate), deltamethrin (S)-.alpha.-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl) 2,2-dimethylcyclopropanecarboxylate), pyrazophos (ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazolo[1,5a]-pyrimidine-6-carboxylate), dimethyl phthalate, (E)-8-(E)-10-dodecadienol or (Z)- 7,8-epoxy-2-methyloctadecane and, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
CA000524055A 1985-11-30 1986-11-28 Aqueous emulsions of plant protection agents Expired - Lifetime CA1285785C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3542439.7 1985-11-30
DE19853542439 DE3542439A1 (en) 1985-11-30 1985-11-30 NEW AQUEOUS PLANT PROTECTION EMULSIONS

Publications (1)

Publication Number Publication Date
CA1285785C true CA1285785C (en) 1991-07-09

Family

ID=6287311

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000524055A Expired - Lifetime CA1285785C (en) 1985-11-30 1986-11-28 Aqueous emulsions of plant protection agents

Country Status (14)

Country Link
EP (1) EP0224846B1 (en)
JP (1) JP2581682B2 (en)
AR (1) AR243318A1 (en)
AT (1) ATE57061T1 (en)
AU (1) AU597314B2 (en)
CA (1) CA1285785C (en)
CZ (1) CZ416891A3 (en)
DE (2) DE3542439A1 (en)
DK (1) DK174127B1 (en)
GR (1) GR3001158T3 (en)
HU (1) HU202714B (en)
PL (1) PL262649A1 (en)
SK (1) SK416891A3 (en)
ZA (1) ZA869001B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3542440A1 (en) * 1985-11-30 1987-06-04 Hoechst Ag NEW WATER DISPERSIBLE GRANULES
FR2643223B1 (en) * 1989-02-17 1991-12-13 Roussel Uclaf NOVEL CONCENTRATED AQUEOUS EMULSIONS, THEIR PREPARATION PROCESS AND THEIR APPLICATION IN THE PESTICIDE FIELD
DE3917959A1 (en) * 1989-06-02 1990-12-06 Hoechst Ag LIQUID HERBICIDES
NZ239522A (en) * 1990-09-04 1993-10-26 Chapman Chem Co Pesticidal compositions containing an amine salt of a phosphonic or orthophosphoric acid
US5674514A (en) * 1992-09-21 1997-10-07 Ciba-Geigy Corporation Storage stable pesticidal aqueous emulsions
WO1994010839A1 (en) * 1992-11-18 1994-05-26 Hoechst Aktiengesellschaft Oil in water emulsions
DE4343857A1 (en) * 1993-12-22 1995-06-29 Hoechst Ag Oil-in-water emulsions
DE4343856A1 (en) * 1993-12-22 1995-06-29 Hoechst Ag Oil-in-water emulsions
GB9609436D0 (en) * 1996-05-04 1996-07-10 Zeneca Ltd Composition and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4220611A (en) * 1978-06-29 1980-09-02 Sandoz, Inc. Polyoxyalkylene bridged phosphate esters
HU202052B (en) * 1983-02-11 1991-02-28 Hoechst Ag Aqueous emulsion-based plant protective compositions

Also Published As

Publication number Publication date
AU597314B2 (en) 1990-05-31
HU202714B (en) 1991-04-29
ZA869001B (en) 1987-07-29
DK573486D0 (en) 1986-11-28
AR243318A1 (en) 1993-08-31
PL262649A1 (en) 1987-11-30
SK416891A3 (en) 1994-06-08
DE3542439A1 (en) 1987-06-04
EP0224846A1 (en) 1987-06-10
AU6582186A (en) 1987-06-04
DK573486A (en) 1987-05-31
HUT43228A (en) 1987-10-28
JPS62132801A (en) 1987-06-16
EP0224846B1 (en) 1990-10-03
DK174127B1 (en) 2002-07-01
DE3674734D1 (en) 1990-11-08
ATE57061T1 (en) 1990-10-15
JP2581682B2 (en) 1997-02-12
CZ416891A3 (en) 1993-07-14
GR3001158T3 (en) 1992-06-30

Similar Documents

Publication Publication Date Title
US4966621A (en) Finely dispersed liquid plant protection agents
RU2255473C2 (en) Method of preparing aqueous formulations
JP2894733B2 (en) Auxiliaries suitable for use in combination with plant-wide plant protection agents
EP0498231B1 (en) Biocidal and agrochemical suspensions
US5334585A (en) Pyrethroid microemulsion compositions and method for controlling insects therewith
US5154754A (en) Oil-in-water emulsions and a process for their preparation and their use
US3894149A (en) Pesticidal Concentrates
CZ20022241A3 (en) Systems based on surface-active compounds and solvents
CA1285785C (en) Aqueous emulsions of plant protection agents
EP0131762B1 (en) Agricultural chemical preparation in the form of aqueous suspension
RU2105475C1 (en) Liquid herbicide agent as an emulsion
JPH09506878A (en) Oil-in-water emulsion
US6342466B1 (en) Biodegradable solutions of biologically active compounds
US4150968A (en) Emulsifiable liquid concentrates containing 4-amino-6-t-butyl-3-(methylthio)-1,2,4-triazin-5-one and 2-chloro-N-(2,6-diethylphenyl)-N-methoxymethylacetamide
UA45328C2 (en) OIL-IN-WATER EMULSION
US5354739A (en) Highly concentrated emulsifiable concentrates of neophanes and azaneophanes for use in plant protection
HU202051B (en) Square fishing-net particularly for fishing purpose
DE3304677A1 (en) Finely-dispersed liquid crop protection agents
CN102271500A (en) Agrochemical compositions comprising branched alcooxyalkanoates

Legal Events

Date Code Title Description
MKEX Expiry