CA1190760A - Storage-stable, concentrated emulsion of herbicidally active phenoxyalkanecarboxylic acid esters, and a process for its preparation - Google Patents
Storage-stable, concentrated emulsion of herbicidally active phenoxyalkanecarboxylic acid esters, and a process for its preparationInfo
- Publication number
- CA1190760A CA1190760A CA000421714A CA421714A CA1190760A CA 1190760 A CA1190760 A CA 1190760A CA 000421714 A CA000421714 A CA 000421714A CA 421714 A CA421714 A CA 421714A CA 1190760 A CA1190760 A CA 1190760A
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- Prior art keywords
- emulsion
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- soluble
- polyethylene glycol
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
-
- 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
ABSTRACT
Storage-stable, herbicidally-active compositions in the form of a con-centrating aqueous emulsion comprising 30 to 75% by weight of one or more herbicidally-active phenoxyalkanecarboxylic acid esters, 0.1 to 5 parts by weight referred to the completed emulsion of one or more oil-soluble emulsifiers which are soluble in the esters and have an HLB value of 9 to 16, and 0.1 to 3 parts by weight referred to the completed emulsion of one or more alkali metal salts of single or multiple unsaturated fatty acid taurides orfatty acid alkyl taurides as watersoluble dispersants, the emulsion having a viscosity of 50 to 3,000 mPa.s., a droplet size of I to 5µm and a pH value of 6 to 9 and a process for the preparation of such emulsion which comprises forming a solution of the active ester and emulsifier and mixing it with an aqueous solution of the dispersant to form a homogeneous mixture.
Storage-stable, herbicidally-active compositions in the form of a con-centrating aqueous emulsion comprising 30 to 75% by weight of one or more herbicidally-active phenoxyalkanecarboxylic acid esters, 0.1 to 5 parts by weight referred to the completed emulsion of one or more oil-soluble emulsifiers which are soluble in the esters and have an HLB value of 9 to 16, and 0.1 to 3 parts by weight referred to the completed emulsion of one or more alkali metal salts of single or multiple unsaturated fatty acid taurides orfatty acid alkyl taurides as watersoluble dispersants, the emulsion having a viscosity of 50 to 3,000 mPa.s., a droplet size of I to 5µm and a pH value of 6 to 9 and a process for the preparation of such emulsion which comprises forming a solution of the active ester and emulsifier and mixing it with an aqueous solution of the dispersant to form a homogeneous mixture.
Description
This invention relates to a storage-s~able, herbicidally-active composi-tion in the form of a concentrated aqueous emulsion of one or more herbicidally ac~ive phenoxyalkanecarboxylic acid esters, and to a process for the preparation thereoi.
Phenoxyalkanecarboxylic acids are amon~st the most commonly used herbicides. They are employed in the form of their amine salts and mineral salts, and also as esters? for example the isopropyl, butyl9 butylglycol or 2-e~hylhexyl esters. The advantage of the esters is that they penetrate more rapidly into the plant and accordingly their use is less dependent on the weather. Their solubility in water is low, but they are soluble in oils, such asdiesel oil, kerosene9 petroleum ether9 xylenes, cyclohexanone, isophorone or highly refined hydrocarbcns. Usually, the ester is dissolved in one of these solvents, and an emulsifier is added to the solution, giving a concen-trated, clear, ernulsifiable solution treferred to as an emulsion concentrate or EC), which, for field use, is dilu~ed with water, thereby producing an oil-in-water emulsion.
According to Austrian Patent Specification 307,802 it is also possible to store pesticides by preparing a very viscous forrnulation of the oil-in-watertype, consisting of active ingredient9 mineral oil, water and formulation auxiliaries~ which, for application, is inverted before use, by means of an additive consistirlg of solvent and dispersant, ~ivin~ a mobile water-in-oil dispersion referred to as an "inverse emulsion".
~oth types of formulation, namely the conventionally used emulsion concentrate and the very viscous dispersion, however, have serious elisadvanta-~es, the causes of` which rest wi~h the solvent used. All solvents conventionally usecl for thls purpose are, like most or~anic solven~s, at least detrimental to health, but in particular also flammable. Thus, highly purified,predominantly aliphatic hydrocarbons have a flash point of 40 to 80C., isophorone has a flash point of 93 C., cyclohexanone has a flash point of 44C. and the most commonly used xylenes have a flash poin~ o only about 25C.
Accordin~ly, the emulsion concentra~e~ prepared with the aid of these solvents are also flammable, and in the past there have been a number of fires in stores of such concentrates, both on ~he manufac~urer's premises and also on the user's premises.
In contrast to the prior art described above, it has now been found that by using certain auxiliaries it is possible to produce a storage-stable, hi~hly concentraeed emulsion of herbicide esters, which is water-based and is therefore non-flammable and free from solvents detrimental to health. The ability to use an aqueous medium to produce storage-stable emulsions of phenoxy-esters is surprising since the esters are somewhat wa~er-soluble7 albeit only slightly, and can therefore undergo hydrolysis.
Accordingly9 the present invention provides a storage-stable herbicid-ally-active composition comprising a concentrated aqueous emulsion of one or more herbicidally active phenoxyalkanecarboxylic acid esters in which the emulsion contains 091 to 5 par~s by wei~ht, referred to ~he completed emulsion, of one or more oil-soluble emulsifiers which are soluble in the esters, have an HLa value of 9 to 167 and are selected from fatty acid polyethylene ~3ycol es~ers, polyethylene ~lycol ethers of fatty alcohols, polyethylene ~Iycol ethers of glycerides, polyethylene glycol ethers of alkyl-phenols, polyoxyethylene/polyoxypropylene block copolymers and mixtures of the said polyetllylene glycol esters, polyethylene glycol ethers or polyethyleneglycol/polypropylene glycol block copolymers with alkylarylsulphonates; and one or more water-soluble dispersant in an amount of 0,l to 3 parts by weight, referred to the compieted emulsion selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyltaurides, in which the amount of herbicidally actiYe ester is 30 to 75 ~6 by weight of the concentrated emulsion, the viscosity of the emulsion is 5d to 3,000 mPa.s9 the drople~ size is l to 5/um and the pH value is 6 to 9.
The concentrated aqueous emulsion of the invention optionally ma~ also contain one or more conventional anti~reeze a~ents, conventional anti-foam agents, thickeners or a rnixture thereof~
The highly concentra~ed emulsion according to the invention is prepared by mixing the ;ndividual reactants or by mixing 2 solutions. Solution I containsthe phenoxyester or phenoxy~esters and an emulsifier soluble in the es~ers, whilst solution 11 contains a dispersant, dissolved in wa~er, and optionally, anti-free2e a~ents, thickeners, anti-foam agents or colorants.
Thus, the invention also provides a process for the preparation of a storage-stable, herbicidally-active composi~ion in the form of a concen~rated 5 emulsion of herbicklally active phenoxyalkanecarboxylic acid esters contai-ning 30 to 75 % by weight of active compound having a ~iscosity of 50 to 3,000 mPa.s, which comprises preparing a solution I from one or more phenoxyalka-necarboxylic acid esters and at least one emulsifier which is soluble in the ester and has an HLB value of 9 to 16, in which the amount of emulsifier is 0,15 ~o lO parts by weight per 100 parts by weight of the solution 1, and mixingsolution I with an aqueous solution Il, whlch contains one or more water-soluble dispersants, selected from the group consisting of alkali metal salts ofsingle or rmultiple unsaturated fatty acid taurides or fatty acid alkyl tauridesin the amount of 0.2 to 10 parts by weight of dispersant per 100 parts of aqueous solution 11, and subsequently homogenizing the mixture at a tempera-ture within the range of 15 to 90C. until the droplet size is 1 to 5/um9 whilemaintaining the pH of the mixture at a value of from 6 to 9 and then dlluting the homogenizate to the desired final volume.
The emulsifiers which are soluble in the phenoxyesters, i.e. fat-soluble ernulsifiers, are responsible for the dispersion of the active substance in the continuous phase. Such emulsifiers, havin~ an HLB ( hydrophilic-lipophilic balance ) value of 9 to 1~ are fatty acid polyethylene glycol esters, the polyethylene ~Iycol ethers of fatty alcohols, of monoglycerides or diglycerides and of alkyl-phenols, and polyethylene glycol~polypropylene glycol block polymers. The emulsifiers may be used individually, as a mix~ure with one another or as a mixture with ammoniurn, calcium, magnesium, potassium, sodiurn Dr zinc salts of alkyl (C~-C24)-benzenesulphonic acids. Fatty acid polyethylene glycol esters or polyoxyethylene/polyoxypropylene block poly-mers used to~ether wi~h alkylarylsu1phonates are particularly suitable.
Solution I contains the fat-soluble emulsifiers in a concentration of O.lS
to 10 per cent by weight, per 100 parts of solution I the range of 2 to 4 parts by weight in solution 3 being particularly preferred. In the composition of ~he invention, the emulsifier is present in an amount of 0.1 to 5 % by weight, preferably 1 to 3 % by weight.
The water-soluble dispersant stabilizes the distribution of the disperse phase, for example through elec~rostatic charging of the particles or through other forces which cause repulsion, for example steric hindrance.
llle dispersants used are the alkali metal salts, especial3y ~he sodium salts, of fat~y acid taurides or fa~y acid alkyl-taurides. Examples s~f such fatty acids, which are ~requently used in the form of mixtures, are straight-5 chain or branched saturated or mono- or poly-unsaturated aliphatic carboxylic acids having about 10 ~o 2Q carbon atoms, such as lauric acid, palmitic acid, stearic acid, myristic acid and especially oleic acid. The alkyl radical in fat~y acid alkyl-~aurides is a lower alkyl radical with up to 4 C atoms, especially the methyl radical~
The dispersants can contain inorganic salts, but it is advantageous ~o keep ~he salt ccntent low, or avoid any salt content at all.
Solution 11 contains ~he water-soluble dispersant in a concentration of 0~2 to 10 parts by weight, preferably 1 to 3 parts by weight, per 100 par~s of solution 11. The dispersant concentration in the composition o~ the invention i5 0.1 to 3 % by weight, preferably 0.2 to I % by weight.
Usually, the storage-stable emulsion of the invention is prepared by preparing an aqueous solution 11 of a dispersant, which soiution optionally contains anti-freeze agents, anti-foam agents or ~hickeners, and stirring the liquid phenoxy-ester or phenoxy-esters, containinX the emulsifier dissolved 20 therein, and constituting solution 1, into solution 1I so as to form a homogene-ous mixture. This stirring-in is effected by means of apparatus which genera-tes a shearing rate of between 1 o2 and 10 sec 1 in the emulsion. This corresponds, at high viscosity (3,000 mPa.s~ to shearing stresses of 3.10 to 3.104Pa, for which an apparatus such as a Homorex or Ultra-Turrax or a 25 homo~enizer with a hornogenizing nozzle is suitable. At iow viscosity (50 mPa.s), the stated shearing rates correspond the shearing stresses of 5 to 500 Pa, for which an apparatus such as a vibrator, a low-speed mixer or a centrifugal pump is suitable. Since the viscosity decreases with increasing temperature, it is possible also to use a low-speed apparatus if an elevated 30 temperature, approximately from 50 to 90C., is employed. The mixing is in~ended to produce homogeneous droplet dispersion, with droplet sizes of 1 to S/um9 preferably of 2 to 3/um, but in addition to the size of the individual droplets a very narrow size distribution and, at the same time, a low viscosity of the emulsion are of impcrtance. It is also possible, to put both solutions into 35 a vessel with stirrer and mix subsequently, or to d~se both solutions simultane-ously via a suitable rnetering device in~o ~he vessel.
lhe viscosity of ~he concen~rated emulsion is an important factor in itsshelf life. The higher the viscosi~y, ~he better the shelf life. On the o~her hand, ~oo high a viscosi~y adversely effects the ease of dilution wi~h water and5 the spontaneous dispersibility on use IJsing the concentrated emulsion prepa-re i according to the inYention, it is possible ~o prepare stable, and at the same time still easily dilutable, formulations havin~ a YisCosity within the range of50 to 3,000 mPa.s. The best results in respect of dilutability and spontaneous dispersibility on the one hand, and stability, on the other hand, are achieved at viscosities of from 500 to 1,500 mPa.s.
Another essential factor in preparing a stable ernulsion is the adjust-ment of the pH value. For each combina~ion of active :ompound/emulsi-fier/dispersant there is an optimum pH Yalue a~ which the emulsion is most stable. This physical stability is bes~ in the alkaline range, but pH values of about 9 should be avoided, since in this range, on prolonged storage and at elevated temperature, partial hydrolysis of the ester may commerce. In an acid medium, pH values of less than 6 are to be avoided, since in this range, onprolon~ed storage, coalescence may occur, i.e. the emulsion increasin~ly becomes physically unstable. A pH range of 7 to 8 is especially preferred.
The cmposition according to the inven~ion may be prepared with any herbicidally ac~i~e phenoxyalkanecarboxylic acid esters, used individually or asmixtures with one another9 expecially the esters with alcohols of chain length C4-C8, for example the octyl esters of 2-(4-chloro-2-rnethylphenoxyl)-propio-nic acid ~CMPP-acid), (2-methyl-4-chlorophenoxy~acetic acid ~MCPA-acid) or
Phenoxyalkanecarboxylic acids are amon~st the most commonly used herbicides. They are employed in the form of their amine salts and mineral salts, and also as esters? for example the isopropyl, butyl9 butylglycol or 2-e~hylhexyl esters. The advantage of the esters is that they penetrate more rapidly into the plant and accordingly their use is less dependent on the weather. Their solubility in water is low, but they are soluble in oils, such asdiesel oil, kerosene9 petroleum ether9 xylenes, cyclohexanone, isophorone or highly refined hydrocarbcns. Usually, the ester is dissolved in one of these solvents, and an emulsifier is added to the solution, giving a concen-trated, clear, ernulsifiable solution treferred to as an emulsion concentrate or EC), which, for field use, is dilu~ed with water, thereby producing an oil-in-water emulsion.
According to Austrian Patent Specification 307,802 it is also possible to store pesticides by preparing a very viscous forrnulation of the oil-in-watertype, consisting of active ingredient9 mineral oil, water and formulation auxiliaries~ which, for application, is inverted before use, by means of an additive consistirlg of solvent and dispersant, ~ivin~ a mobile water-in-oil dispersion referred to as an "inverse emulsion".
~oth types of formulation, namely the conventionally used emulsion concentrate and the very viscous dispersion, however, have serious elisadvanta-~es, the causes of` which rest wi~h the solvent used. All solvents conventionally usecl for thls purpose are, like most or~anic solven~s, at least detrimental to health, but in particular also flammable. Thus, highly purified,predominantly aliphatic hydrocarbons have a flash point of 40 to 80C., isophorone has a flash point of 93 C., cyclohexanone has a flash point of 44C. and the most commonly used xylenes have a flash poin~ o only about 25C.
Accordin~ly, the emulsion concentra~e~ prepared with the aid of these solvents are also flammable, and in the past there have been a number of fires in stores of such concentrates, both on ~he manufac~urer's premises and also on the user's premises.
In contrast to the prior art described above, it has now been found that by using certain auxiliaries it is possible to produce a storage-stable, hi~hly concentraeed emulsion of herbicide esters, which is water-based and is therefore non-flammable and free from solvents detrimental to health. The ability to use an aqueous medium to produce storage-stable emulsions of phenoxy-esters is surprising since the esters are somewhat wa~er-soluble7 albeit only slightly, and can therefore undergo hydrolysis.
Accordingly9 the present invention provides a storage-stable herbicid-ally-active composition comprising a concentrated aqueous emulsion of one or more herbicidally active phenoxyalkanecarboxylic acid esters in which the emulsion contains 091 to 5 par~s by wei~ht, referred to ~he completed emulsion, of one or more oil-soluble emulsifiers which are soluble in the esters, have an HLa value of 9 to 167 and are selected from fatty acid polyethylene ~3ycol es~ers, polyethylene ~lycol ethers of fatty alcohols, polyethylene ~Iycol ethers of glycerides, polyethylene glycol ethers of alkyl-phenols, polyoxyethylene/polyoxypropylene block copolymers and mixtures of the said polyetllylene glycol esters, polyethylene glycol ethers or polyethyleneglycol/polypropylene glycol block copolymers with alkylarylsulphonates; and one or more water-soluble dispersant in an amount of 0,l to 3 parts by weight, referred to the compieted emulsion selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyltaurides, in which the amount of herbicidally actiYe ester is 30 to 75 ~6 by weight of the concentrated emulsion, the viscosity of the emulsion is 5d to 3,000 mPa.s9 the drople~ size is l to 5/um and the pH value is 6 to 9.
The concentrated aqueous emulsion of the invention optionally ma~ also contain one or more conventional anti~reeze a~ents, conventional anti-foam agents, thickeners or a rnixture thereof~
The highly concentra~ed emulsion according to the invention is prepared by mixing the ;ndividual reactants or by mixing 2 solutions. Solution I containsthe phenoxyester or phenoxy~esters and an emulsifier soluble in the es~ers, whilst solution 11 contains a dispersant, dissolved in wa~er, and optionally, anti-free2e a~ents, thickeners, anti-foam agents or colorants.
Thus, the invention also provides a process for the preparation of a storage-stable, herbicidally-active composi~ion in the form of a concen~rated 5 emulsion of herbicklally active phenoxyalkanecarboxylic acid esters contai-ning 30 to 75 % by weight of active compound having a ~iscosity of 50 to 3,000 mPa.s, which comprises preparing a solution I from one or more phenoxyalka-necarboxylic acid esters and at least one emulsifier which is soluble in the ester and has an HLB value of 9 to 16, in which the amount of emulsifier is 0,15 ~o lO parts by weight per 100 parts by weight of the solution 1, and mixingsolution I with an aqueous solution Il, whlch contains one or more water-soluble dispersants, selected from the group consisting of alkali metal salts ofsingle or rmultiple unsaturated fatty acid taurides or fatty acid alkyl tauridesin the amount of 0.2 to 10 parts by weight of dispersant per 100 parts of aqueous solution 11, and subsequently homogenizing the mixture at a tempera-ture within the range of 15 to 90C. until the droplet size is 1 to 5/um9 whilemaintaining the pH of the mixture at a value of from 6 to 9 and then dlluting the homogenizate to the desired final volume.
The emulsifiers which are soluble in the phenoxyesters, i.e. fat-soluble ernulsifiers, are responsible for the dispersion of the active substance in the continuous phase. Such emulsifiers, havin~ an HLB ( hydrophilic-lipophilic balance ) value of 9 to 1~ are fatty acid polyethylene glycol esters, the polyethylene ~Iycol ethers of fatty alcohols, of monoglycerides or diglycerides and of alkyl-phenols, and polyethylene glycol~polypropylene glycol block polymers. The emulsifiers may be used individually, as a mix~ure with one another or as a mixture with ammoniurn, calcium, magnesium, potassium, sodiurn Dr zinc salts of alkyl (C~-C24)-benzenesulphonic acids. Fatty acid polyethylene glycol esters or polyoxyethylene/polyoxypropylene block poly-mers used to~ether wi~h alkylarylsu1phonates are particularly suitable.
Solution I contains the fat-soluble emulsifiers in a concentration of O.lS
to 10 per cent by weight, per 100 parts of solution I the range of 2 to 4 parts by weight in solution 3 being particularly preferred. In the composition of ~he invention, the emulsifier is present in an amount of 0.1 to 5 % by weight, preferably 1 to 3 % by weight.
The water-soluble dispersant stabilizes the distribution of the disperse phase, for example through elec~rostatic charging of the particles or through other forces which cause repulsion, for example steric hindrance.
llle dispersants used are the alkali metal salts, especial3y ~he sodium salts, of fat~y acid taurides or fa~y acid alkyl-taurides. Examples s~f such fatty acids, which are ~requently used in the form of mixtures, are straight-5 chain or branched saturated or mono- or poly-unsaturated aliphatic carboxylic acids having about 10 ~o 2Q carbon atoms, such as lauric acid, palmitic acid, stearic acid, myristic acid and especially oleic acid. The alkyl radical in fat~y acid alkyl-~aurides is a lower alkyl radical with up to 4 C atoms, especially the methyl radical~
The dispersants can contain inorganic salts, but it is advantageous ~o keep ~he salt ccntent low, or avoid any salt content at all.
Solution 11 contains ~he water-soluble dispersant in a concentration of 0~2 to 10 parts by weight, preferably 1 to 3 parts by weight, per 100 par~s of solution 11. The dispersant concentration in the composition o~ the invention i5 0.1 to 3 % by weight, preferably 0.2 to I % by weight.
Usually, the storage-stable emulsion of the invention is prepared by preparing an aqueous solution 11 of a dispersant, which soiution optionally contains anti-freeze agents, anti-foam agents or ~hickeners, and stirring the liquid phenoxy-ester or phenoxy-esters, containinX the emulsifier dissolved 20 therein, and constituting solution 1, into solution 1I so as to form a homogene-ous mixture. This stirring-in is effected by means of apparatus which genera-tes a shearing rate of between 1 o2 and 10 sec 1 in the emulsion. This corresponds, at high viscosity (3,000 mPa.s~ to shearing stresses of 3.10 to 3.104Pa, for which an apparatus such as a Homorex or Ultra-Turrax or a 25 homo~enizer with a hornogenizing nozzle is suitable. At iow viscosity (50 mPa.s), the stated shearing rates correspond the shearing stresses of 5 to 500 Pa, for which an apparatus such as a vibrator, a low-speed mixer or a centrifugal pump is suitable. Since the viscosity decreases with increasing temperature, it is possible also to use a low-speed apparatus if an elevated 30 temperature, approximately from 50 to 90C., is employed. The mixing is in~ended to produce homogeneous droplet dispersion, with droplet sizes of 1 to S/um9 preferably of 2 to 3/um, but in addition to the size of the individual droplets a very narrow size distribution and, at the same time, a low viscosity of the emulsion are of impcrtance. It is also possible, to put both solutions into 35 a vessel with stirrer and mix subsequently, or to d~se both solutions simultane-ously via a suitable rnetering device in~o ~he vessel.
lhe viscosity of ~he concen~rated emulsion is an important factor in itsshelf life. The higher the viscosi~y, ~he better the shelf life. On the o~her hand, ~oo high a viscosi~y adversely effects the ease of dilution wi~h water and5 the spontaneous dispersibility on use IJsing the concentrated emulsion prepa-re i according to the inYention, it is possible ~o prepare stable, and at the same time still easily dilutable, formulations havin~ a YisCosity within the range of50 to 3,000 mPa.s. The best results in respect of dilutability and spontaneous dispersibility on the one hand, and stability, on the other hand, are achieved at viscosities of from 500 to 1,500 mPa.s.
Another essential factor in preparing a stable ernulsion is the adjust-ment of the pH value. For each combina~ion of active :ompound/emulsi-fier/dispersant there is an optimum pH Yalue a~ which the emulsion is most stable. This physical stability is bes~ in the alkaline range, but pH values of about 9 should be avoided, since in this range, on prolonged storage and at elevated temperature, partial hydrolysis of the ester may commerce. In an acid medium, pH values of less than 6 are to be avoided, since in this range, onprolon~ed storage, coalescence may occur, i.e. the emulsion increasin~ly becomes physically unstable. A pH range of 7 to 8 is especially preferred.
The cmposition according to the inven~ion may be prepared with any herbicidally ac~i~e phenoxyalkanecarboxylic acid esters, used individually or asmixtures with one another9 expecially the esters with alcohols of chain length C4-C8, for example the octyl esters of 2-(4-chloro-2-rnethylphenoxyl)-propio-nic acid ~CMPP-acid), (2-methyl-4-chlorophenoxy~acetic acid ~MCPA-acid) or
2 5 2,4,5-trichlorophenoxyacetic acid (2,4,5-T-acid).
Since technical-grade phenoxyalkanecarboxylic acid esters, because of their method of preparation, usually have a pH value of about 3 (measured in a 10 % strength aqueous dispersion~, the desired pH is obtained by use of a conventional caustic alkali, for example sodium hyd~oxide or potassium hydroxide. The pH may be adjusted to ~he desired value during or after preparation of the emulsion, but it is also possible to use purified neutral esters, which makes subsequent adjustment of the pH value u nnecessary.
To ensure adequate low temperature stabi~ity, conventional anti-freeze agents, such as ethylene ~Iycol~ glycerol, urea, ~Iycol ethers or other alcoholsmay be added to the emulsions. Furthermore, it is possible to add known - ~ -inor~anic or organic ~hickeners, for examples xan~han gum, sodium polyacryla-te, carboxymethylcellulose, colloidal silica or swelling clay minerals~ such as ben~onite, in order to adjust the viscosity to a particular value. To reduce foaming, anti-foam agents, such as long-chain alcohols, 2-ethylhexallol or 5 cetyl alcohol, high-polymer glycols and especially silicones may be added.
For field use, the concentreated emulsions prepared according to the invention are diluted with wa~er in exac~ly the same way as the hitherto customary flammable emulsion concentrates, and may be applied by means oE
the same spraying apparatus.
The Examples which follow describe the preparation, as well as the chemical and physical stability, of the compositions according to the inven tion. The technical-grade phenoxyalkanecarboxylic acid esters used conform to the guideline recommended by the Worlds Health Or~anization The stability was tested in a storage test, in which a 24-hour temperature cycle between 10C. and +50C. was followed. After storage for a period of 4 weeks, the following were measured:
1. Change in pH value 2. Consumption of 0.01 N sodium hydroxide solution, in order to restore the initial pl~.
Since technical-grade phenoxyalkanecarboxylic acid esters, because of their method of preparation, usually have a pH value of about 3 (measured in a 10 % strength aqueous dispersion~, the desired pH is obtained by use of a conventional caustic alkali, for example sodium hyd~oxide or potassium hydroxide. The pH may be adjusted to ~he desired value during or after preparation of the emulsion, but it is also possible to use purified neutral esters, which makes subsequent adjustment of the pH value u nnecessary.
To ensure adequate low temperature stabi~ity, conventional anti-freeze agents, such as ethylene ~Iycol~ glycerol, urea, ~Iycol ethers or other alcoholsmay be added to the emulsions. Furthermore, it is possible to add known - ~ -inor~anic or organic ~hickeners, for examples xan~han gum, sodium polyacryla-te, carboxymethylcellulose, colloidal silica or swelling clay minerals~ such as ben~onite, in order to adjust the viscosity to a particular value. To reduce foaming, anti-foam agents, such as long-chain alcohols, 2-ethylhexallol or 5 cetyl alcohol, high-polymer glycols and especially silicones may be added.
For field use, the concentreated emulsions prepared according to the invention are diluted with wa~er in exac~ly the same way as the hitherto customary flammable emulsion concentrates, and may be applied by means oE
the same spraying apparatus.
The Examples which follow describe the preparation, as well as the chemical and physical stability, of the compositions according to the inven tion. The technical-grade phenoxyalkanecarboxylic acid esters used conform to the guideline recommended by the Worlds Health Or~anization The stability was tested in a storage test, in which a 24-hour temperature cycle between 10C. and +50C. was followed. After storage for a period of 4 weeks, the following were measured:
1. Change in pH value 2. Consumption of 0.01 N sodium hydroxide solution, in order to restore the initial pl~.
3. Viscosity change (measured on a Brookfield LVT, viscometer, spindle 2, 6 rpm)
4. Change in the turbidity of a 0.01 % strength emuJsion, correlated with the change in droplet size (measured by means of a Lange turbidimeter in 100 ml cells).
5. Supernatant liquid, in %
6. Coalescence ~formation of an oily phase)
7. Re-emulsifiability.
The results of the measurements relating to ~he Examples have been summarized in a table. The resul~s of the measurement show that in none of ~he Examples in question was the change in 1., 2., 3., 4. and 5. more than 10 %
after a storage time of 4 weeks with a 24-hour ternperature cycle between -10C. and ~50C. No coalescence occurred and any non-coalesced sediment which might be present was completely re-ernulsifiable.
Example I
Solution 1: 64û ~ of 2,4,5-T-amyl ester, technical gr ~de g of fatty acid polye~hylene glycol ester Solution 11: 5 ~ of Na oleyl-methyl-tauride 195 % stren~th3 ~ of ethylene ~Iycol, technical grade 1.3 g of xanthane gum 443 ~ of distilled water.
SQlution 11 was ~aken and ~olu~ion I was stirred into it by means of Homorex mixer.
After completion of addition, s~irring was continued for 10 minutes at the highes~ speed, the pH value was then adjusted to 7.2S with half-normal 10 NaOH solution, and the mixture was again stirred briefly.
Example 2:
.. Solution 1: 350 ~ of MCPA-ethylhexyl ester, technical grade g of fatty acid polye~hylene glycol ester Solution ll: 2.5 g of the sodium salt of palm kernel fatty acicl methyl-tauride (30% strength aqueous solution containing 7% of NaCI) g of ethylen~ glycol 126 g of distilled water The method employed was as described in Example 1. The pH value 20 was adjusted to 7.55.
Example 3:
Solution 1: 350 g of 2,4-D-ethylhexyl ester g of fa~ty acid polyethylene glycol es~er Solu~ion 11: 2.5 ~ of the sodium salt of a fat~y acid me~hyl tauride (30% strength a~ueous solution contai-ning 7% of NaCI, fatty acid = palmitic/stearic acid) g of ethylene glycol 151 g of dis~illed water.
The method employed was as described in Example 1. The pH va3ue was adjusted to 7.6.
Example 4:
Solution 1 350 ~ of MCPA-ethylhexyl ester, technical grade g of faltty acid polyethylene ~Iyccl ester ~olution 11: 2.5 g of the sodium salt of a fat~y acid tauride kontaining inorganic and organk: salts, fatty acid = lauriclmyristic acid) g of ethylene glycol 125 8 Of distilled water The me~hod employed was as described in Example lo The pH value was adjusted to 7.5.
Example 5O
Solution 1: 350 ~ of CAlPP butylglycol ester g of fatty acid polyethylene glycol ester Solution 1l: 2.5 g of Na oleyl methyl tauride (25% strength aqueous solution) 1~5 g of distllled water The method employed was as described in Example 1. The pH value was adjusted to 7.5.
Example 6:
Solution 1: 350 g of 2,4,5-T-amyl ester g of a mixture of nonylphenyl-polyethylerle oxi-de, polyoxyethylene/polyoxyp~opylene block polymer (molecular weight 1,800 to 9,000) and alkylarylsulfonate Solution 11: 10 g of Na oleyl methyl tauride t25% strength aqueous solution) g of ethylene glycol 130 g of distilled water I g of antifQam agent (silicone emulsion) The method employed was as described in Exampie 1. The pH value was adjus~ed to 3Ø
Example 7:
Solution 1: 350 g of 2,4-D-butyl ester g of polyoxye~hylene triglyceride and alkylaryl-sulfonate Solution 11: iO g of Na oleyl methyl tauride (25% strength aqueous solution3 g of ethylene glycol 16S g of distilled wa~er 119~76~
.. ~
The method employed was as clescribed in Example l. The pH value was adjusted ~o 7Ø
Example 3:
Solution ~ 1,200 g ~of 2,4,5~T-ethylhexyl ester, technical grade S 30 g of fatty acid polyglycol ester Solution Il: g g sf Na oleyl methyl tauride ~25% strength aqueous solution) 105 g of ethylene glycol 6 g of xanthan ~um 1,830 g of distilled water 2 g of antifoam ~silicone ernulsion) 1.68 g of NaOH
In a prelirninary experiment, it was established that 0.56 g/li~re of NaOH are required ~o neutralize the formulation, after which the calculated 5 amoun~ of NaOH tl.68 g) was added to 5Olution 11. Thereupon, Solutions I and II
were fed by means of metering pumps to an apparatus which essentially consisted of a centrifugal pump with bypass for product recycling and pressure-maintaining valve at the exit. The optimum droplet distribution was obtained at a me~ering pump:centrifugal pump feed ratio of l: 15 to 1: 25.
20 The pH value was 7~8.
Example 9:
Solution 1: 4290S g of MCPA-ethylhexyl ester, technical grade 226.6 g of 2,4,5-T-ethylhexyl ester, ~echnical grade 1.2 g of fatty alcohol polyglycol ether Solution 11: 25 g of Na oleyl methyl rauride ~25% strength aqueous solution) ~ of ethylene glycol 0.6 g of xanthan gum 321 g of distilled water Solution 11 was taken, Soiution I was stirred in~o i~ by means of a Homorex mixer, and the pH of the mixture was adjusted to 8.30 with half-normal NaOH solution. For further homogenization, the emulsion was forced through a homogenizing head under a pressure of 90 bar.
_ 10 -Initial values after 4 weeks' s~orage at -10/~50C
ExamplepH-V21ue Yiscosity Turbidity pH-ValueViscosityTurbidity% of supernatant in mPa.s in rnPa.s liquid 7,25 1 300 85 ~,~01 ~80 85 2 7,55 75G 84 7jOû 740 86 3 7,60 275 86 6,95 280 80 4 7~50 1 750 88 7,301 580 83 0 7,50 425 82 6,80 400 79 5 6 8,00 ~00 86 7,35 ~5~ 7~ 9 7 ~,00 350 81 ~,50 320 73 7,~0 1 2û0 79 7,00~ 175 71 0 ;~
9 ~.30 ~ 450 88 7,552 200 88 9
The results of the measurements relating to ~he Examples have been summarized in a table. The resul~s of the measurement show that in none of ~he Examples in question was the change in 1., 2., 3., 4. and 5. more than 10 %
after a storage time of 4 weeks with a 24-hour ternperature cycle between -10C. and ~50C. No coalescence occurred and any non-coalesced sediment which might be present was completely re-ernulsifiable.
Example I
Solution 1: 64û ~ of 2,4,5-T-amyl ester, technical gr ~de g of fatty acid polye~hylene glycol ester Solution 11: 5 ~ of Na oleyl-methyl-tauride 195 % stren~th3 ~ of ethylene ~Iycol, technical grade 1.3 g of xanthane gum 443 ~ of distilled water.
SQlution 11 was ~aken and ~olu~ion I was stirred into it by means of Homorex mixer.
After completion of addition, s~irring was continued for 10 minutes at the highes~ speed, the pH value was then adjusted to 7.2S with half-normal 10 NaOH solution, and the mixture was again stirred briefly.
Example 2:
.. Solution 1: 350 ~ of MCPA-ethylhexyl ester, technical grade g of fatty acid polye~hylene glycol ester Solution ll: 2.5 g of the sodium salt of palm kernel fatty acicl methyl-tauride (30% strength aqueous solution containing 7% of NaCI) g of ethylen~ glycol 126 g of distilled water The method employed was as described in Example 1. The pH value 20 was adjusted to 7.55.
Example 3:
Solution 1: 350 g of 2,4-D-ethylhexyl ester g of fa~ty acid polyethylene glycol es~er Solu~ion 11: 2.5 ~ of the sodium salt of a fat~y acid me~hyl tauride (30% strength a~ueous solution contai-ning 7% of NaCI, fatty acid = palmitic/stearic acid) g of ethylene glycol 151 g of dis~illed water.
The method employed was as described in Example 1. The pH va3ue was adjusted to 7.6.
Example 4:
Solution 1 350 ~ of MCPA-ethylhexyl ester, technical grade g of faltty acid polyethylene ~Iyccl ester ~olution 11: 2.5 g of the sodium salt of a fat~y acid tauride kontaining inorganic and organk: salts, fatty acid = lauriclmyristic acid) g of ethylene glycol 125 8 Of distilled water The me~hod employed was as described in Example lo The pH value was adjusted to 7.5.
Example 5O
Solution 1: 350 ~ of CAlPP butylglycol ester g of fatty acid polyethylene glycol ester Solution 1l: 2.5 g of Na oleyl methyl tauride (25% strength aqueous solution) 1~5 g of distllled water The method employed was as described in Example 1. The pH value was adjusted to 7.5.
Example 6:
Solution 1: 350 g of 2,4,5-T-amyl ester g of a mixture of nonylphenyl-polyethylerle oxi-de, polyoxyethylene/polyoxyp~opylene block polymer (molecular weight 1,800 to 9,000) and alkylarylsulfonate Solution 11: 10 g of Na oleyl methyl tauride t25% strength aqueous solution) g of ethylene glycol 130 g of distilled water I g of antifQam agent (silicone emulsion) The method employed was as described in Exampie 1. The pH value was adjus~ed to 3Ø
Example 7:
Solution 1: 350 g of 2,4-D-butyl ester g of polyoxye~hylene triglyceride and alkylaryl-sulfonate Solution 11: iO g of Na oleyl methyl tauride (25% strength aqueous solution3 g of ethylene glycol 16S g of distilled wa~er 119~76~
.. ~
The method employed was as clescribed in Example l. The pH value was adjusted ~o 7Ø
Example 3:
Solution ~ 1,200 g ~of 2,4,5~T-ethylhexyl ester, technical grade S 30 g of fatty acid polyglycol ester Solution Il: g g sf Na oleyl methyl tauride ~25% strength aqueous solution) 105 g of ethylene glycol 6 g of xanthan ~um 1,830 g of distilled water 2 g of antifoam ~silicone ernulsion) 1.68 g of NaOH
In a prelirninary experiment, it was established that 0.56 g/li~re of NaOH are required ~o neutralize the formulation, after which the calculated 5 amoun~ of NaOH tl.68 g) was added to 5Olution 11. Thereupon, Solutions I and II
were fed by means of metering pumps to an apparatus which essentially consisted of a centrifugal pump with bypass for product recycling and pressure-maintaining valve at the exit. The optimum droplet distribution was obtained at a me~ering pump:centrifugal pump feed ratio of l: 15 to 1: 25.
20 The pH value was 7~8.
Example 9:
Solution 1: 4290S g of MCPA-ethylhexyl ester, technical grade 226.6 g of 2,4,5-T-ethylhexyl ester, ~echnical grade 1.2 g of fatty alcohol polyglycol ether Solution 11: 25 g of Na oleyl methyl rauride ~25% strength aqueous solution) ~ of ethylene glycol 0.6 g of xanthan gum 321 g of distilled water Solution 11 was taken, Soiution I was stirred in~o i~ by means of a Homorex mixer, and the pH of the mixture was adjusted to 8.30 with half-normal NaOH solution. For further homogenization, the emulsion was forced through a homogenizing head under a pressure of 90 bar.
_ 10 -Initial values after 4 weeks' s~orage at -10/~50C
ExamplepH-V21ue Yiscosity Turbidity pH-ValueViscosityTurbidity% of supernatant in mPa.s in rnPa.s liquid 7,25 1 300 85 ~,~01 ~80 85 2 7,55 75G 84 7jOû 740 86 3 7,60 275 86 6,95 280 80 4 7~50 1 750 88 7,301 580 83 0 7,50 425 82 6,80 400 79 5 6 8,00 ~00 86 7,35 ~5~ 7~ 9 7 ~,00 350 81 ~,50 320 73 7,~0 1 2û0 79 7,00~ 175 71 0 ;~
9 ~.30 ~ 450 88 7,552 200 88 9
Claims (10)
1. A storage-stable herbidically-active composition comprising a concentrated aqueous emulsion of one or more herbicidally active phenoxyalkanecarboxylic acid esters in which the emulsion contains 0.1 to 5 parts by weight, referred to the completed emulsion, of one or more oil-soluble emulsifiers which are soluble in the esters, have an HLB value of 9 to 16, and are selected from fatty acid polyethylene glycol esters, polyethylene glycol ethers of fatty alcohols, polyethylene glycol ethers of glycerides, polyethylene glycol ethers of alkylphenols, polyoxyethylene/
polyoxypropylene block copolymers and mixtures of the said polyethylene glycol esters, polyethylene glycol ethers or polyethylene glycol/polypropylene glycol block copolymers with alkylarylsulphonates; and one or more water-soluble dispersant in an amount of 0.1 to 3 parts by weight, referred to the completed emulsion selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyltaurides, in which the amount of herbicidally active ester is 30 to 75 % by weight of the concentrated emulsion, the viscosity of the emulsion is 50 to 3,000 mPa.s., the droplet size is 1 to 5 µm and the pH value is 6 to 9.
polyoxypropylene block copolymers and mixtures of the said polyethylene glycol esters, polyethylene glycol ethers or polyethylene glycol/polypropylene glycol block copolymers with alkylarylsulphonates; and one or more water-soluble dispersant in an amount of 0.1 to 3 parts by weight, referred to the completed emulsion selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyltaurides, in which the amount of herbicidally active ester is 30 to 75 % by weight of the concentrated emulsion, the viscosity of the emulsion is 50 to 3,000 mPa.s., the droplet size is 1 to 5 µm and the pH value is 6 to 9.
2. A composition according to claim 1, which additionally contains one or more conventional anti-freeze agents, convertional anti-foam agents, thickeners or a mixture thereof.
3. A composition according to claim 1 or 2, in which the ester soluble emulsifiers are one or more fatty acid polyethylene glycol esters.
4. A composition according to claim 1, in which the water soluble dispersant is Sodium-oleyl-methyltauride.
5. A composition according to claim 1, in which the herbicidally-active phenoxyalkanecarboxylic acid esters are the octyl esters.
6. A composition according to claim 1, in which the amount of emulsifier is 1 to 3 % by weight.
7. A composition according to claim 1, in which the amount of dispersant is 0.2 to 1 % by weight.
8. A composition according to claim 1, in which the viscosity is 500 to 1,500 mPa.s.
9. A composition according to claim 1, in which the pH-value is 7 to 8.
10. A process for the preparation of a storage-stable herbicidally-active composition in the form of concentrated emulsion of herbicidally active phenoxyalkanecarboxylic acid esters containing 30 to 75 % by weight of active compound having a viscosity of 50 to 3,000 mPa,s., which comprises preparing a solution I from one or more phenoxy-alkanecarboxylic acid esters and at least one emulsifier which is soluble in the ester and has an HLB value of 9 to 16, in which the amount of emulsifier is 0.15 to 10 parts by weight per 100 parts by weight of the solution I,
10. A process for the preparation of a storage-stable herbicidally-active composition in the form of concentrated emulsion of herbicidally active phenoxyalkanecarboxylic acid esters containing 30 to 75 % by weight of active compound having a viscosity of 50 to 3,000 mPa,s., which comprises preparing a solution I from one or more phenoxy-alkanecarboxylic acid esters and at least one emulsifier which is soluble in the ester and has an HLB value of 9 to 16, in which the amount of emulsifier is 0.15 to 10 parts by weight per 100 parts by weight of the solution I,
Claim 10 continued...
and mixing solution I with an aqueous solution II, which contains one or more water-soluble dispersants, selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyl taurides in the amount of 0.2 to 10 parts by weight of dispersant per 100 parts of aqueous solution II, and subsequently homogenizing the mixture at a temperature within the range of 15° to 90°C. until the droplet size is 1 to 5 µm, while maintaining the pH of the mixture at a value of from 6 to 9 and then diluting the homogenizate to the desired final volume.
and mixing solution I with an aqueous solution II, which contains one or more water-soluble dispersants, selected from the group consisting of alkali metal salts of single or multiple unsaturated fatty acid taurides or fatty acid alkyl taurides in the amount of 0.2 to 10 parts by weight of dispersant per 100 parts of aqueous solution II, and subsequently homogenizing the mixture at a temperature within the range of 15° to 90°C. until the droplet size is 1 to 5 µm, while maintaining the pH of the mixture at a value of from 6 to 9 and then diluting the homogenizate to the desired final volume.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3207661.4 | 1982-03-03 | ||
| DE19823207661 DE3207661A1 (en) | 1982-03-03 | 1982-03-03 | STORAGE-STABLE, CONCENTRATED EMULSION OF HERBICIDALLY ACTIVE PHENOXYALCANIC CARBONIC ACID ESTERS AND A METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1190760A true CA1190760A (en) | 1985-07-23 |
Family
ID=6157218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000421714A Expired CA1190760A (en) | 1982-03-03 | 1983-02-16 | Storage-stable, concentrated emulsion of herbicidally active phenoxyalkanecarboxylic acid esters, and a process for its preparation |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0088887B1 (en) |
| JP (1) | JPS58162505A (en) |
| AT (1) | ATE17636T1 (en) |
| AU (1) | AU551685B2 (en) |
| CA (1) | CA1190760A (en) |
| CS (1) | CS232748B2 (en) |
| DE (2) | DE3207661A1 (en) |
| DK (1) | DK76883A (en) |
| FI (1) | FI70769C (en) |
| GB (1) | GB2115285B (en) |
| GR (1) | GR78330B (en) |
| IE (1) | IE54701B1 (en) |
| MY (1) | MY8500689A (en) |
| NO (1) | NO830710L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3806294A1 (en) * | 1988-02-27 | 1989-09-07 | Hoechst Ag | HERBICIDES IN THE FORM OF AQUEOUS MICROEMULSIONS |
| US5674514A (en) * | 1992-09-21 | 1997-10-07 | Ciba-Geigy Corporation | Storage stable pesticidal aqueous emulsions |
| DE10059671A1 (en) * | 2000-12-01 | 2002-06-06 | Cognis Deutschland Gmbh | Effect enhancer for 2,4 dichlorophenoxyacetic acid and methyl chlorophenoxyacetic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2205590A1 (en) * | 1972-02-07 | 1973-08-16 | Hoechst Ag | ANTI-EVAPORATIVE ADDITIVE FOR CONCENTRATED PLANT PROTECTION DISPERSIONS |
-
1982
- 1982-03-03 DE DE19823207661 patent/DE3207661A1/en not_active Withdrawn
-
1983
- 1983-02-07 GR GR70428A patent/GR78330B/el unknown
- 1983-02-09 DE DE8383101235T patent/DE3361942D1/en not_active Expired
- 1983-02-09 AT AT83101235T patent/ATE17636T1/en not_active IP Right Cessation
- 1983-02-09 EP EP83101235A patent/EP0088887B1/en not_active Expired
- 1983-02-16 CA CA000421714A patent/CA1190760A/en not_active Expired
- 1983-02-22 GB GB08304840A patent/GB2115285B/en not_active Expired
- 1983-02-22 DK DK76883A patent/DK76883A/en not_active Application Discontinuation
- 1983-02-24 FI FI830610A patent/FI70769C/en not_active IP Right Cessation
- 1983-02-24 IE IE398/83A patent/IE54701B1/en not_active IP Right Cessation
- 1983-02-25 AU AU11848/83A patent/AU551685B2/en not_active Ceased
- 1983-02-28 CS CS831368A patent/CS232748B2/en unknown
- 1983-03-02 NO NO830710A patent/NO830710L/en unknown
- 1983-03-03 JP JP58033907A patent/JPS58162505A/en active Pending
-
1985
- 1985-12-30 MY MY689/85A patent/MY8500689A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO830710L (en) | 1983-09-05 |
| DE3361942D1 (en) | 1986-03-13 |
| MY8500689A (en) | 1985-12-31 |
| CS232748B2 (en) | 1985-02-14 |
| FI830610A0 (en) | 1983-02-24 |
| IE830398L (en) | 1983-09-03 |
| GB8304840D0 (en) | 1983-03-23 |
| DK76883A (en) | 1983-09-04 |
| IE54701B1 (en) | 1990-01-17 |
| FI830610L (en) | 1983-09-04 |
| ATE17636T1 (en) | 1986-02-15 |
| GB2115285B (en) | 1984-06-13 |
| GR78330B (en) | 1984-09-26 |
| AU551685B2 (en) | 1986-05-08 |
| FI70769C (en) | 1986-10-27 |
| GB2115285A (en) | 1983-09-07 |
| EP0088887B1 (en) | 1986-01-29 |
| EP0088887A1 (en) | 1983-09-21 |
| AU1184883A (en) | 1983-09-08 |
| DE3207661A1 (en) | 1983-09-08 |
| DK76883D0 (en) | 1983-02-22 |
| JPS58162505A (en) | 1983-09-27 |
| FI70769B (en) | 1986-07-18 |
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