CA1209361A - Microemulsions - Google Patents
MicroemulsionsInfo
- Publication number
- CA1209361A CA1209361A CA000437476A CA437476A CA1209361A CA 1209361 A CA1209361 A CA 1209361A CA 000437476 A CA000437476 A CA 000437476A CA 437476 A CA437476 A CA 437476A CA 1209361 A CA1209361 A CA 1209361A
- Authority
- CA
- Canada
- Prior art keywords
- dimethyl
- formula
- microemulsion according
- microemulsion
- thionophosphate
- 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
-
- 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
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
-
- 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
- C09K23/017—Mixtures of compounds
Abstract
ABSTRACT OF THE DISCLOSURE
An aqueous microemulsion comprising at least one agrochemically active compound of low solubility in water, one active compound for combating pests in the household and hygiene sectors, a mixture of emulsifiers consisting of at least one alkylaryl polyglycol ether and at least one alkylarylsuphonic acid salt, or at least one alkylaryl polyglycol ether and at least one alkylarylsuponic acid salt and also water. Disclosed also, are methods for the preparation of such an aqueous microemulsion and the use of the same as an agrochemically active composition, or as an agent for combating pests in the household or hygiene sectors.
An aqueous microemulsion comprising at least one agrochemically active compound of low solubility in water, one active compound for combating pests in the household and hygiene sectors, a mixture of emulsifiers consisting of at least one alkylaryl polyglycol ether and at least one alkylarylsuphonic acid salt, or at least one alkylaryl polyglycol ether and at least one alkylarylsuponic acid salt and also water. Disclosed also, are methods for the preparation of such an aqueous microemulsion and the use of the same as an agrochemically active composition, or as an agent for combating pests in the household or hygiene sectors.
Description
:12~93~1 ., The present invent;on relates to aqueous micro-emulsions of agrochemical active compounds and/or active compounds for combating pests in the domestic and hygiene 5 sectors. The inv~ntion also relates to a process for the preparation of these microemulsions and to their use.
Oil-in-water emulsions of numerous agrochemical active compounds of low solubility in water are already known, in addition to the active compounds, these 10 emulsions also contain, in each case, either a surface-active substance and a thickener or else a relatively large quantity of surface-active substances (compare DE-A ~German Published Specification) 3,009,94~, DE A
(German Published Specification) 3,011,611 and JP-A
15 (Japanese Published Specification) 12Z,628-77). This addition of thickeners or of large quantities of surfac-tant is associated with additional expense and thus con-stitutes a serious disadvantage of the known oil-in-water emulsions. In addition to this, the preparation which 20 has hitherto been described of emulsions of this type is not generally applicable. This is because, essentially, it is possible to emulsify by this process only those active compounds of low solubility in water which are liquid at room temperature or at least have a very low 25 melting point. It is also disadvantageous that the known oil-in-water emuLsions are frequently not adequately stable under cold conditions and that, in some cases, forced emulsification using homogenisers is required~
Aqueous m;croemulsions which contain 30 - 0.1 to 8û,~ by weight of at least one agrochemical active compound of low solubility in water and/or one active compound ~or combating pests in the household and hygiene sectors, Le A 21 929 1~9~61 1 to 20% by weight of a mixture of emulsifiers consisting of ~ `
a) at least one alky~aryl çolyglycol ether of the formula S ~) O (X)m~ (Y)n~H (I) in which R represents alkyl having 8 to 20 carbon atoms, X and Y each represent a -CHz-CH2-O-, -CH2-CH-0- or -CH-CH2-0- group, but X and Y
do not simultaneously represent an oxyethylene or oxypropylene unit, m represents numbers from 10 to 45 and n represents numbers from 10 to 45, and Z0 at least one alkylarylsulphonic acid salt of the formula R 1 ~ ~ ~ ( I I ) in which R1 represents alkyl having 8 to 35 carbon atoms and Me~ represents an alkali metal cation, an equivalent of an alkaline earth metal cation or a cation of the formula R"
R' - N - R" ' RIV
wherein R', Rl', R"' and RIV independently of one Le A 21 929 ~2~361 another represent hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 1 to 4 carbon atoms, o~
b~ at least one alkylaryl polyglycol ether of the formula ~ O-(CH~-C~ -O) -H (III) in which p represents numbers from 5 to 20 and q represents numbers from 1 to 3, and at least one alkyLarylsulphonic acid salt of the formula R1 ~ ~ Me~ (II) in which R1 and M ~ have the meaning indicated above, - and also water and - if appropriate, 1 to 30% by weight of at least one organic solvent of low miscibility with water and/or of a solubiliser and also, - if appropriate, 0.05 to 15~ by weight of additives, the sum of the components being in each case 100% by weight, have been found.
It has also been found that the microemul5jons according to the invention can be prepared by adding, while stirring, to water optionally containing additives, a homogeneous mixture consisting of - at least one agrochemical active compound of low solubiLity in water and/or one active compound for combating pests in the household and hygiene Le A 21 929 . ~ ~
~Z~!~3~
sectors~
a mixture of emuls;fiers consist;ng of a) at least one alkylaryl polyglycol ether of the formula R~ ( ) m ( ) n ( 1 ) in which R, X, Y, m and n have the meaning indicated above, and at least one alkylarylsulphonic acid salt of the formula R ~ 5O3 Me ~II) in which R1 and Me~ have the meaning indicated above, lS or b) at least one alkylaryl polyglycol ether of the formula O-(CH2-CH2-O) - H
(CH2~)q ~III) in whirh p and q have the meaning indicated abover and at least one alkylarylsulphonic acid salt of the formula (II) R1_ ~ _502 Me2 Le A 21 929 ~L2~
in wh;ch R1 and Me~ have the meaning indicated above, - if appropriate, at least one organic solvent of low miscibility with water and/or a solubiliser, and aLso, - if appropriate, additives.
FinaLly, it has been found that - depending on the active compounds they contain - the microemulsions according to the invention can be used for various pur-poses in agriculture or horticulture, or in the household and hygiene sectors.
It must be described as extremely surprising that the microemulsions according to the invention are stable, since it would have been expected on the basis of the known state of the art that emulsions of this type, which contain no th;ckeners and also only a small proportion of surfactant, would not be stable for a prolonged period.
Thus it is apparent from DE~A (German Published Specifi-cation) 3,009,944 and DE-A (German Published Specification) 3,011,611 that the oil-in-water emulsions described in those texts necessarily contain a thickener as a stabili-ser. The emulsions disclosed in JP-A (Japanese Published Specification) 122,628-77 have a very high proportion of surfactant in relation to the quantity of active com-pound. The excellent stability of the microemulsions according to the invention could not, therefore, have been foreseen.
The microemulsions according to the invention are distinguished by a number of advantages. Thus the expen-3Q sive addition of thickeners or large quantities of emulsi-fiers is not necessary in their preparation. Furthermore, these emulsions contain either only an extremely small quantity of organic solvents or none at all. Therefore, they are incombustible and free, or at least virtually free, from odour troubles caused by organic solvents, and have a lower toxicity or phytotoxicity than corresponding Le A 21 929 12~93~
formulations conta;ning organic solvents in the concen-trations otherwise customary In addition, the micro-emulsions according to the invention are stable under the conditions which prevail in practice. When stored for long periods, these emulsions remain unchanged both at temperatures of 50C and at low temperatures. Finally, the microemulsions according to the invention can be pre-pared in a simple manner. Forced emulsification using homogenisers is not necessary. In addition, a very con-siderable acdvantage consists in the fact that active com-pounds of low solubility in water which are solid or liquid at room temperature can be emulsified with equal ease.
Furthernore, the microemulsions according to the invention have a relatively low viscos;ty, so that accurate metering presents no difficulties. Finally, the microemulsions according to the invention are completely transparent pre-parat;ons which can be diluted without problems in any desired ratio with water before use, stablej sprayable formulations beins thus formed.
The microemulsions according to the invention con-tain at least one agrochemical active compound of low solubility in water and/or one active compound for co~-bating pests in the household and hygiene sectors. These active compounds are present in the liquid state in the oil phase.
Suitable active compounds are substances which are liquid at room temperature, as well as those which are solid at room temperature. The only requirement for liquid active compounds is that they should be sparingly soluble in water. Compounds of this type are to be under-stood here as meaning substances which are soluble to the - extent of not more than 0.5% by weight in water at 20C.
Solid active compounds must, however, additionally be adequately soluble in an organic solvent of low misci-bility with water and/or in a solubiliser.
Agrochemical substances are to be understood in Le A 21 929 the present case as meaning any active compounds which can customariLy be used in plant protection. These include, ~or example, insect;cides, acaricides, nematocides, fungi-cides, herbicides, growth regulators and fertilisers~ The following may be mentioned as individual examples of active compounds of this type:
0~0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, 0 (ethyl) 0-(4-methylthiophenyl) S-propyl dithiophosphate, (0,0-diethylth;onophosphoryl)-~-oximinophenylacetonitrile,
Oil-in-water emulsions of numerous agrochemical active compounds of low solubility in water are already known, in addition to the active compounds, these 10 emulsions also contain, in each case, either a surface-active substance and a thickener or else a relatively large quantity of surface-active substances (compare DE-A ~German Published Specification) 3,009,94~, DE A
(German Published Specification) 3,011,611 and JP-A
15 (Japanese Published Specification) 12Z,628-77). This addition of thickeners or of large quantities of surfac-tant is associated with additional expense and thus con-stitutes a serious disadvantage of the known oil-in-water emulsions. In addition to this, the preparation which 20 has hitherto been described of emulsions of this type is not generally applicable. This is because, essentially, it is possible to emulsify by this process only those active compounds of low solubility in water which are liquid at room temperature or at least have a very low 25 melting point. It is also disadvantageous that the known oil-in-water emuLsions are frequently not adequately stable under cold conditions and that, in some cases, forced emulsification using homogenisers is required~
Aqueous m;croemulsions which contain 30 - 0.1 to 8û,~ by weight of at least one agrochemical active compound of low solubility in water and/or one active compound ~or combating pests in the household and hygiene sectors, Le A 21 929 1~9~61 1 to 20% by weight of a mixture of emulsifiers consisting of ~ `
a) at least one alky~aryl çolyglycol ether of the formula S ~) O (X)m~ (Y)n~H (I) in which R represents alkyl having 8 to 20 carbon atoms, X and Y each represent a -CHz-CH2-O-, -CH2-CH-0- or -CH-CH2-0- group, but X and Y
do not simultaneously represent an oxyethylene or oxypropylene unit, m represents numbers from 10 to 45 and n represents numbers from 10 to 45, and Z0 at least one alkylarylsulphonic acid salt of the formula R 1 ~ ~ ~ ( I I ) in which R1 represents alkyl having 8 to 35 carbon atoms and Me~ represents an alkali metal cation, an equivalent of an alkaline earth metal cation or a cation of the formula R"
R' - N - R" ' RIV
wherein R', Rl', R"' and RIV independently of one Le A 21 929 ~2~361 another represent hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 1 to 4 carbon atoms, o~
b~ at least one alkylaryl polyglycol ether of the formula ~ O-(CH~-C~ -O) -H (III) in which p represents numbers from 5 to 20 and q represents numbers from 1 to 3, and at least one alkyLarylsulphonic acid salt of the formula R1 ~ ~ Me~ (II) in which R1 and M ~ have the meaning indicated above, - and also water and - if appropriate, 1 to 30% by weight of at least one organic solvent of low miscibility with water and/or of a solubiliser and also, - if appropriate, 0.05 to 15~ by weight of additives, the sum of the components being in each case 100% by weight, have been found.
It has also been found that the microemul5jons according to the invention can be prepared by adding, while stirring, to water optionally containing additives, a homogeneous mixture consisting of - at least one agrochemical active compound of low solubiLity in water and/or one active compound for combating pests in the household and hygiene Le A 21 929 . ~ ~
~Z~!~3~
sectors~
a mixture of emuls;fiers consist;ng of a) at least one alkylaryl polyglycol ether of the formula R~ ( ) m ( ) n ( 1 ) in which R, X, Y, m and n have the meaning indicated above, and at least one alkylarylsulphonic acid salt of the formula R ~ 5O3 Me ~II) in which R1 and Me~ have the meaning indicated above, lS or b) at least one alkylaryl polyglycol ether of the formula O-(CH2-CH2-O) - H
(CH2~)q ~III) in whirh p and q have the meaning indicated abover and at least one alkylarylsulphonic acid salt of the formula (II) R1_ ~ _502 Me2 Le A 21 929 ~L2~
in wh;ch R1 and Me~ have the meaning indicated above, - if appropriate, at least one organic solvent of low miscibility with water and/or a solubiliser, and aLso, - if appropriate, additives.
FinaLly, it has been found that - depending on the active compounds they contain - the microemulsions according to the invention can be used for various pur-poses in agriculture or horticulture, or in the household and hygiene sectors.
It must be described as extremely surprising that the microemulsions according to the invention are stable, since it would have been expected on the basis of the known state of the art that emulsions of this type, which contain no th;ckeners and also only a small proportion of surfactant, would not be stable for a prolonged period.
Thus it is apparent from DE~A (German Published Specifi-cation) 3,009,944 and DE-A (German Published Specification) 3,011,611 that the oil-in-water emulsions described in those texts necessarily contain a thickener as a stabili-ser. The emulsions disclosed in JP-A (Japanese Published Specification) 122,628-77 have a very high proportion of surfactant in relation to the quantity of active com-pound. The excellent stability of the microemulsions according to the invention could not, therefore, have been foreseen.
The microemulsions according to the invention are distinguished by a number of advantages. Thus the expen-3Q sive addition of thickeners or large quantities of emulsi-fiers is not necessary in their preparation. Furthermore, these emulsions contain either only an extremely small quantity of organic solvents or none at all. Therefore, they are incombustible and free, or at least virtually free, from odour troubles caused by organic solvents, and have a lower toxicity or phytotoxicity than corresponding Le A 21 929 12~93~
formulations conta;ning organic solvents in the concen-trations otherwise customary In addition, the micro-emulsions according to the invention are stable under the conditions which prevail in practice. When stored for long periods, these emulsions remain unchanged both at temperatures of 50C and at low temperatures. Finally, the microemulsions according to the invention can be pre-pared in a simple manner. Forced emulsification using homogenisers is not necessary. In addition, a very con-siderable acdvantage consists in the fact that active com-pounds of low solubility in water which are solid or liquid at room temperature can be emulsified with equal ease.
Furthernore, the microemulsions according to the invention have a relatively low viscos;ty, so that accurate metering presents no difficulties. Finally, the microemulsions according to the invention are completely transparent pre-parat;ons which can be diluted without problems in any desired ratio with water before use, stablej sprayable formulations beins thus formed.
The microemulsions according to the invention con-tain at least one agrochemical active compound of low solubility in water and/or one active compound for co~-bating pests in the household and hygiene sectors. These active compounds are present in the liquid state in the oil phase.
Suitable active compounds are substances which are liquid at room temperature, as well as those which are solid at room temperature. The only requirement for liquid active compounds is that they should be sparingly soluble in water. Compounds of this type are to be under-stood here as meaning substances which are soluble to the - extent of not more than 0.5% by weight in water at 20C.
Solid active compounds must, however, additionally be adequately soluble in an organic solvent of low misci-bility with water and/or in a solubiliser.
Agrochemical substances are to be understood in Le A 21 929 the present case as meaning any active compounds which can customariLy be used in plant protection. These include, ~or example, insect;cides, acaricides, nematocides, fungi-cides, herbicides, growth regulators and fertilisers~ The following may be mentioned as individual examples of active compounds of this type:
0~0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, 0 (ethyl) 0-(4-methylthiophenyl) S-propyl dithiophosphate, (0,0-diethylth;onophosphoryl)-~-oximinophenylacetonitrile,
2-isopropoxyphenyl N-methylcarbamate,
3-methylthio-4-amino-6-tert.-butyl-1,2,4-triazin-5-one~
3-methylthio~4-isobutylideneamino-6 tert.-butyl-1,2,4 triazin-5-one, 15 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methyLcarbamate, 3,5-dimethyl-4-methylthiophenyL N-methylcarbamate, 0~0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl~ thiophos-phate, 20 6,7,8,9,10,10-hexachloro-1,5,5A,6,9~9A hexahydro-6,9-methane-2,3,4-benzodioxathiepin-3-oxide, 1,4,5,6,708,8-heptachloro-4,7-endomethylene-3A,4,7,7A
tetrahydroindene, Z-(2-furyl)-benzimidazole, 25 5-amino-1-bis-tdimethylamido)-phosphoryl-3-phenyl-1,2,4-triazole,
3-methylthio~4-isobutylideneamino-6 tert.-butyl-1,2,4 triazin-5-one, 15 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methyLcarbamate, 3,5-dimethyl-4-methylthiophenyL N-methylcarbamate, 0~0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl~ thiophos-phate, 20 6,7,8,9,10,10-hexachloro-1,5,5A,6,9~9A hexahydro-6,9-methane-2,3,4-benzodioxathiepin-3-oxide, 1,4,5,6,708,8-heptachloro-4,7-endomethylene-3A,4,7,7A
tetrahydroindene, Z-(2-furyl)-benzimidazole, 25 5-amino-1-bis-tdimethylamido)-phosphoryl-3-phenyl-1,2,4-triazole,
4-hydroxy-3-(1,2,3,4-tetrahydro-1-naphthyl)-coumar;n, S-C1,2-bis-(ethoxycarbonyl)-ethyl~ 0,0-dimethyl dithio-phosphate, 30 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thiono-phosphate, 0-ethyl-0-(2-isopropoxycarborlylphenyl)-N-isopropylthiono-phosphoric acid ester-amide, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-35 2 butanone,(S)-d-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-Le A 21 929 - ~2~9;~6~
2,2-dimethylcyclopropanecarboxylate and ~-cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl~3~ -dichloro-vinyl)-cyclopropanecarboxylate.
Active compounds for combating pests in the domestic and hygiene sectors are to be understood, in the present case, as meaning any customary active compounds of low solubility in water which are suitable for indications of this type. The following may be mentioned as individual examples of active compounds of this type:
2-isopropoxyphenyl N-methylcarbamate, 0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, s-~1,2-bis-(etho~ycarbonyl)-ethyl] 0,0-dimethyl dithiophosphate, 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate, ~-hexachlorocyclohexane and (cyclohex-l-ene-1,2-dicarboximidomethyl) 2,2-d'methyl-3-(2-methylpropenyl)-cyclopropanecarboxylate.
The emulsifier mixtures present in the microemulsions according to the invention consist of either at least one alkyl-aryl polyglycol ether of the formula (I) and at least one alkyl-arylsulphonic acid salt of the formula (II), or at least one alkylaryl polyglycol ether of the formula (III) and at least one alkylarylsulphonic acid salt of the formula (II).
The alkylaryl polyglycol ethers of the formula (I) are defined in a general manner by the ormula 93~, indicated. In this formula, R preferably represents alkyl having 10 to 18 carbon atoms. X and Y each represent a -CH2-CH2-0-, -CH2-CH-0- or -CH-CH2-0- group, but X and Y do not simultaneously represent an oxyethylene or oxypropylene unit. The index m preferably represents numbers from 12 to 30 and the ;ndex n preferably repre-sents numbers from 12 to 40. The numbers for the indices m and n represent average values.
The emulsifiers of this type which are used in practice are ~enerally mixtures composed of several com-pounds of the formula (I). In particular, they are mix-tures composed of substances of the formula (I), differing in the number of oxyethylene and/or oxypropylene units.
Calculation thus also yields fractional numbers as average values for the indices m and n. Substances for which the following average compositions result may be mentioned as examples:
C9H19~ CH3 (CH2-C~d20) 30 H
9 19 ' 2) (CH2~CH20)35 3 H
~0- (CH2-CHO) 24--(CH2 CH2) 36 CgHl g CH3 Le A 21 929 ~ 10 -~O~ (CH2-CH-0) 24 (CH2 CH2O) 40 CgH1 9 CH3 ~ O- ( CH-CH20 ) 2 7 ~ CH2 CH2 ) 3 9 ~ 5 ~' ~T
~_9n 19 J
~ O- (CH2 -CH20 ) 2 7 ~ ( CH2 CHO ) 2 7 CgH1 9 CH3 The alkylaryl polyglycol ethers of the formula ~I) are known.
The aLkylarylsulphonic acid salts present in the microemulsions according to the invention are defined in a general manner by the formula (II). In this formula, R1 preferably represents straight-chain or branched alkyl having 9 to 30 carbon atoms~ Me~ preferably repre-sents a sodium cation, one equivalent of a calcium cation or a cation of the formula R"
R' - N - R"' RIV
wherein R', R", R"' and RIV independently of one another preferably represent hydrogen, alkyl having 1 or 2 carbon atoms or hydroxyalkyl having 1 to 2 carbon atoms.
The following may be mentioned as individual 2~ examples of alkylarylsulphonic acid salts of the formula Le A 21 929 ~0~36J.
sodium 4~5n-nonyl)-phenylsuLphonate, calcium 4-(n~dodecyl)-phenylsulphonate~
sodium 4-(tetrapropylene)-phenylsulphonate, calcium 4-(n-nonyl)-phenylsulphonate,
2,2-dimethylcyclopropanecarboxylate and ~-cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl~3~ -dichloro-vinyl)-cyclopropanecarboxylate.
Active compounds for combating pests in the domestic and hygiene sectors are to be understood, in the present case, as meaning any customary active compounds of low solubility in water which are suitable for indications of this type. The following may be mentioned as individual examples of active compounds of this type:
2-isopropoxyphenyl N-methylcarbamate, 0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, s-~1,2-bis-(etho~ycarbonyl)-ethyl] 0,0-dimethyl dithiophosphate, 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate, ~-hexachlorocyclohexane and (cyclohex-l-ene-1,2-dicarboximidomethyl) 2,2-d'methyl-3-(2-methylpropenyl)-cyclopropanecarboxylate.
The emulsifier mixtures present in the microemulsions according to the invention consist of either at least one alkyl-aryl polyglycol ether of the formula (I) and at least one alkyl-arylsulphonic acid salt of the formula (II), or at least one alkylaryl polyglycol ether of the formula (III) and at least one alkylarylsulphonic acid salt of the formula (II).
The alkylaryl polyglycol ethers of the formula (I) are defined in a general manner by the ormula 93~, indicated. In this formula, R preferably represents alkyl having 10 to 18 carbon atoms. X and Y each represent a -CH2-CH2-0-, -CH2-CH-0- or -CH-CH2-0- group, but X and Y do not simultaneously represent an oxyethylene or oxypropylene unit. The index m preferably represents numbers from 12 to 30 and the ;ndex n preferably repre-sents numbers from 12 to 40. The numbers for the indices m and n represent average values.
The emulsifiers of this type which are used in practice are ~enerally mixtures composed of several com-pounds of the formula (I). In particular, they are mix-tures composed of substances of the formula (I), differing in the number of oxyethylene and/or oxypropylene units.
Calculation thus also yields fractional numbers as average values for the indices m and n. Substances for which the following average compositions result may be mentioned as examples:
C9H19~ CH3 (CH2-C~d20) 30 H
9 19 ' 2) (CH2~CH20)35 3 H
~0- (CH2-CHO) 24--(CH2 CH2) 36 CgHl g CH3 Le A 21 929 ~ 10 -~O~ (CH2-CH-0) 24 (CH2 CH2O) 40 CgH1 9 CH3 ~ O- ( CH-CH20 ) 2 7 ~ CH2 CH2 ) 3 9 ~ 5 ~' ~T
~_9n 19 J
~ O- (CH2 -CH20 ) 2 7 ~ ( CH2 CHO ) 2 7 CgH1 9 CH3 The alkylaryl polyglycol ethers of the formula ~I) are known.
The aLkylarylsulphonic acid salts present in the microemulsions according to the invention are defined in a general manner by the formula (II). In this formula, R1 preferably represents straight-chain or branched alkyl having 9 to 30 carbon atoms~ Me~ preferably repre-sents a sodium cation, one equivalent of a calcium cation or a cation of the formula R"
R' - N - R"' RIV
wherein R', R", R"' and RIV independently of one another preferably represent hydrogen, alkyl having 1 or 2 carbon atoms or hydroxyalkyl having 1 to 2 carbon atoms.
The following may be mentioned as individual 2~ examples of alkylarylsulphonic acid salts of the formula Le A 21 929 ~0~36J.
sodium 4~5n-nonyl)-phenylsuLphonate, calcium 4-(n~dodecyl)-phenylsulphonate~
sodium 4-(tetrapropylene)-phenylsulphonate, calcium 4-(n-nonyl)-phenylsulphonate,
5 ammonium 4-(i-dodecyl)-phenylsulphonate and ~2-hydroxyethyl)-ammonium 4-tn-dodecyl)-phenylsulphonate.
The alkylarylsulphonic acid salts of the formula ~II) are known. They are generally employed in the form of 50-75~ strength solutions in organic solvents, for example n-butanol, i~butanol or benzyl alcohol, but can, in principle, also be used without a solvent.
The alkylaryl polyglycol ethers of the formula (III) are defined ;n a general manner by the formula indi-cated. In this formula, the index p preferably represents numbers from 8 to 18, and the index q preferably repre-sents numbers from 1 to 2. The numbers for the indices p and q represent average values.
The emulsifiers of this type which are used in practice are generally mixtures composed of several com-Z0 pounds of the formula (III). In particular they are mix-tures composed of substances of the formula (III), differ-ing in th~ number of oxyethylene units and/or in the deqree of substitution on the phenyl radical. Calculation can thus also yield fractional numbers as average values for the indices p and q. Substances for which the follow-ing average compositions result may be mentioned as examples:
~-0- (CH2-CH2-0) 11-H
(CH2 ~ )1,35 and Le A 21 929 9~6~
(CH2~) ~ 1, 7 O- (CH2-CH2 ) 12 H
The aLkyLaryL polyglycol ethers of the formula (III) are also known.
Any customary organic soLvents of Low miscibility with water are suitable as the organic solvents which can, if appropriate, be present in the microemuLsions according to the invention. Solvents which may be mentioned pre-ferentially are aromatic hydrocarbons, such as xylene, toluene and dimethylnaphthalene, and also chlorinated aromatic hydrocarbons, such as chlorobenzenes, and also aliphatic hydrocarbons, such ligroin and petroleum ether, additionaLly halogenated aliphatic hydrocarbons, such as methylene chloride and chloroform, add;tionally cyclo-aliphatic hydrocarbons, such as cyclohexane, and also alcohols and ketones, such as n-butanol~ n-hexanol, iso-hexanol, n-octanol, cyclohexanol, benzyl alcohol, di-n-butyl ketone and isophorone, and also ethers and esters, such as glycol monomethyl ether and glycol monomethyl ether-acetate, and, furthermore, also triethyl phosphate.
Any customary solubilisers are suitable as the solubilisers which can be present in the microemulsions according to the invention. Solubilisers which can be used preferentially are alkylphenols or cresols which have been subjected to a condensation reaction with, per mol, ZS 1 to 8 mols of ethylene oxide. p-Gresol which has been subjected to a condensation reaction with, p~r mol, 1 to 8 mols of ethylene oxide should be mentioned specially in this connection.
Suitable additives which can, if appropriate, be present in the microemulsions according to the invention are preservativesr dyestuffs, cold stabilisers and Le A 21 929 ,3~2~
synergists.
2-Hydroxybiphenyl and sorbic acid may be mentioned as examples of preservatives. Azo dyestuffs and phthalo-cyanine dyestuffs may be mentioned as examples of dye-S stuffs. Urea, sugars and salts, such as ammonium sul-phate and sodium oleate, may be mentioned as examples of cold stab;lisers. 3,4-Me~hylenedioxy-6-propylbenzyl-n-butyldiethylene glycol ether (piperonyl butoxide) may be mentioned as an example of a synergista The percentage proportions of the components pre-sent in the microemulsions according to the invention can be varied within specific ranges. In general, the propor-tion of active compound or active compounds is between 0.1 and ~0~ by weight, preferably between 5 and 80% by weight. The proportion of emulsifier mixture is, in general, 1 to 20% by weight, preferably 3 to 16% by weight, and the ratio of the emulsifiers to one another can also be varied within a specific range. In general, there is 0.2 to 1.2, preferably 0.4 to 1, part of emulsifier of the formula (II) to 1 part of emulsifier of the formula (I).
Furthermore, there is, in general, 0.1 to 1.2 parts, pre-ferabLy 0~2 to 1.0 part, of emulsifier of the formula (II) to 1 part of emulsifier of the formula (III).
Organic solvents of low miscibility with water and/or solubilisers can be present in proportions of 1 to 30% by weight, preferably 5 to 20% by weight. Additives can be present in proportions of 0.05 to 15% by weight, preferably 0.1 to 10~ by weight. The percentage propor-tion of water in the microemulsions according to the invent;on is in each case the difference between 100% by weight and the total of the percentage proportions of the other components.
The ratio of active compound(s), on the one hand, optionally mixed with organic solvents and/or solubilisers, to the emusifier mixture on the other hand can be varied within a specific range in the microemulsions according to Le A 21 929 the invention. In general, there are 1 to 1S parts by weight, preferably 2 to 10 parts by weight, of active com-poundts), if appropriate mixed with organic solvents and/
or soLubilisers~ to 1 part of emulsifier mixture.
S In preparing the microemulsions according to the invention ;t can be preferable to use all the components which have already been mentioned preferentially in con-nection with the description of the microemulsions accord-ing to the invention~
If an active compound which is in the liquid state at temperatures up to 40C is used in the process accord ing to the invention, it is generally unnecessary to add an organ;c solvent and/or a solubiliser of low miscibility with water.
If, on the other hand, an active compound whish is in the solid state at temperatures up to 4ûC is used ;n the process according to the invention, it is necessary to dissolve the active compound concerned in an organic solvent of low miscibility with water andJor a solubiliser before emulsification. The quantity of organic solvent and/or solubiliser in this case is such that it is exactly sufficient to dissolve the solid substance.
The reaction temperatures in the process according to the invention can be varied within a fairly wide range.
In general, the process is carried out at temperatures between 10C and 80C~ preferably between ~0C and 60C.
The method generally followed in carrying out the process according to the invention is first to prepare a homogeneous solution consisting of one or more active com-pounds, an emulsifier mixture, if appropriate an organicsolvent of low m;scibility with water and/or a solubiliser and, if appropriate, additives, and then to add this mix-ture, while stirring, to water, if appropriate containing additives~ In doing so, the quantities of the components are selected in such a way that the components in the resulting microemulsion are present in the concentration Le A 21 929 ~2~93'6~
desired in the particular case. The sequence in which the components of the organic phase are combined can be varied.
The addition of the organic phase to the aqueous phase is advantageously effected slowly, while stirring uniformly with customary stirring equipment. In the course of this, a finely disperse, transparent microemulsion which can no longer be distinguished optically from a solution, is formed.
The microemulsions according to the inven~ion can be applied either in the form in which they have been pre-pared or after prior dilution. The quantity applied depends on the concentration of the active compounds in the microemulsion and on the particular indication.
The use of the microemulsions according to the invention is effected by the customary methods, that is to say, for exampLe, by spraying, sprinkling or pouring.
The preparation of the microemulsions according to the invention can be seen from the following examples.
Preparation E~amples Example 1 ~ g of an emulsifier mixture consisting of - ~ parts by weight of a nonylphenol polyglycol ether which has an average of 27 oxyethylene and 27 oxypropylene units per molecule, and - 4 parts by weight of calcium 4-(n-dodecyl)-phenyl-sulphonate (dissolved in n-butanol), is added, at temperatures bet~een 20C and 40C and while stirring, to 70 g of the insecticidal active compound 0,0-dimethyl 0-(4-methyLmercapto-3-methylphenyl) thiono-phosphate. The homogeneous solution thus formed is poured, in the course of 2 minutes and while stirring vigorously, in~o 22 g of deionised water. When the addition is com-plete, stirring is continued for a further 5 minutes. A
transparent microemulsion is formed, which exhibits no physi-cal or chemical changes even after storage at elevated Le A Z1 9Z9 -- ~X~9~6~
temperature for several weeks.
Example 2 14 9 of an emulsifier mixture consisting of 10 parts by weight of an alkylaryl polyglycol ether, the average composition of which can be seen from the following formula (CH2 ~ )l,7 O-(CH2-CH2O)12 H
and - 4 parts by weight of calcium 4-(n~dodecyl)-phenylsulphonate (dissolved in n butanol), are added, at temperatures between 2~ and 40C and while stirring, to 50 9 of 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate. ~he homogeneous solution thus formed is added, in the course of 2 minutes and while stirring vigorously, to 36 9 of deionised water. When the addition is complete, stirring is continued for a further 5 minutes. A transparent microemulsion is formed, which exhibits no physical or chemical changes even after storage at elevated temperature for several weeks.
Le A 21 529
The alkylarylsulphonic acid salts of the formula ~II) are known. They are generally employed in the form of 50-75~ strength solutions in organic solvents, for example n-butanol, i~butanol or benzyl alcohol, but can, in principle, also be used without a solvent.
The alkylaryl polyglycol ethers of the formula (III) are defined ;n a general manner by the formula indi-cated. In this formula, the index p preferably represents numbers from 8 to 18, and the index q preferably repre-sents numbers from 1 to 2. The numbers for the indices p and q represent average values.
The emulsifiers of this type which are used in practice are generally mixtures composed of several com-Z0 pounds of the formula (III). In particular they are mix-tures composed of substances of the formula (III), differ-ing in th~ number of oxyethylene units and/or in the deqree of substitution on the phenyl radical. Calculation can thus also yield fractional numbers as average values for the indices p and q. Substances for which the follow-ing average compositions result may be mentioned as examples:
~-0- (CH2-CH2-0) 11-H
(CH2 ~ )1,35 and Le A 21 929 9~6~
(CH2~) ~ 1, 7 O- (CH2-CH2 ) 12 H
The aLkyLaryL polyglycol ethers of the formula (III) are also known.
Any customary organic soLvents of Low miscibility with water are suitable as the organic solvents which can, if appropriate, be present in the microemuLsions according to the invention. Solvents which may be mentioned pre-ferentially are aromatic hydrocarbons, such as xylene, toluene and dimethylnaphthalene, and also chlorinated aromatic hydrocarbons, such as chlorobenzenes, and also aliphatic hydrocarbons, such ligroin and petroleum ether, additionaLly halogenated aliphatic hydrocarbons, such as methylene chloride and chloroform, add;tionally cyclo-aliphatic hydrocarbons, such as cyclohexane, and also alcohols and ketones, such as n-butanol~ n-hexanol, iso-hexanol, n-octanol, cyclohexanol, benzyl alcohol, di-n-butyl ketone and isophorone, and also ethers and esters, such as glycol monomethyl ether and glycol monomethyl ether-acetate, and, furthermore, also triethyl phosphate.
Any customary solubilisers are suitable as the solubilisers which can be present in the microemulsions according to the invention. Solubilisers which can be used preferentially are alkylphenols or cresols which have been subjected to a condensation reaction with, per mol, ZS 1 to 8 mols of ethylene oxide. p-Gresol which has been subjected to a condensation reaction with, p~r mol, 1 to 8 mols of ethylene oxide should be mentioned specially in this connection.
Suitable additives which can, if appropriate, be present in the microemulsions according to the invention are preservativesr dyestuffs, cold stabilisers and Le A 21 929 ,3~2~
synergists.
2-Hydroxybiphenyl and sorbic acid may be mentioned as examples of preservatives. Azo dyestuffs and phthalo-cyanine dyestuffs may be mentioned as examples of dye-S stuffs. Urea, sugars and salts, such as ammonium sul-phate and sodium oleate, may be mentioned as examples of cold stab;lisers. 3,4-Me~hylenedioxy-6-propylbenzyl-n-butyldiethylene glycol ether (piperonyl butoxide) may be mentioned as an example of a synergista The percentage proportions of the components pre-sent in the microemulsions according to the invention can be varied within specific ranges. In general, the propor-tion of active compound or active compounds is between 0.1 and ~0~ by weight, preferably between 5 and 80% by weight. The proportion of emulsifier mixture is, in general, 1 to 20% by weight, preferably 3 to 16% by weight, and the ratio of the emulsifiers to one another can also be varied within a specific range. In general, there is 0.2 to 1.2, preferably 0.4 to 1, part of emulsifier of the formula (II) to 1 part of emulsifier of the formula (I).
Furthermore, there is, in general, 0.1 to 1.2 parts, pre-ferabLy 0~2 to 1.0 part, of emulsifier of the formula (II) to 1 part of emulsifier of the formula (III).
Organic solvents of low miscibility with water and/or solubilisers can be present in proportions of 1 to 30% by weight, preferably 5 to 20% by weight. Additives can be present in proportions of 0.05 to 15% by weight, preferably 0.1 to 10~ by weight. The percentage propor-tion of water in the microemulsions according to the invent;on is in each case the difference between 100% by weight and the total of the percentage proportions of the other components.
The ratio of active compound(s), on the one hand, optionally mixed with organic solvents and/or solubilisers, to the emusifier mixture on the other hand can be varied within a specific range in the microemulsions according to Le A 21 929 the invention. In general, there are 1 to 1S parts by weight, preferably 2 to 10 parts by weight, of active com-poundts), if appropriate mixed with organic solvents and/
or soLubilisers~ to 1 part of emulsifier mixture.
S In preparing the microemulsions according to the invention ;t can be preferable to use all the components which have already been mentioned preferentially in con-nection with the description of the microemulsions accord-ing to the invention~
If an active compound which is in the liquid state at temperatures up to 40C is used in the process accord ing to the invention, it is generally unnecessary to add an organ;c solvent and/or a solubiliser of low miscibility with water.
If, on the other hand, an active compound whish is in the solid state at temperatures up to 4ûC is used ;n the process according to the invention, it is necessary to dissolve the active compound concerned in an organic solvent of low miscibility with water andJor a solubiliser before emulsification. The quantity of organic solvent and/or solubiliser in this case is such that it is exactly sufficient to dissolve the solid substance.
The reaction temperatures in the process according to the invention can be varied within a fairly wide range.
In general, the process is carried out at temperatures between 10C and 80C~ preferably between ~0C and 60C.
The method generally followed in carrying out the process according to the invention is first to prepare a homogeneous solution consisting of one or more active com-pounds, an emulsifier mixture, if appropriate an organicsolvent of low m;scibility with water and/or a solubiliser and, if appropriate, additives, and then to add this mix-ture, while stirring, to water, if appropriate containing additives~ In doing so, the quantities of the components are selected in such a way that the components in the resulting microemulsion are present in the concentration Le A 21 929 ~2~93'6~
desired in the particular case. The sequence in which the components of the organic phase are combined can be varied.
The addition of the organic phase to the aqueous phase is advantageously effected slowly, while stirring uniformly with customary stirring equipment. In the course of this, a finely disperse, transparent microemulsion which can no longer be distinguished optically from a solution, is formed.
The microemulsions according to the inven~ion can be applied either in the form in which they have been pre-pared or after prior dilution. The quantity applied depends on the concentration of the active compounds in the microemulsion and on the particular indication.
The use of the microemulsions according to the invention is effected by the customary methods, that is to say, for exampLe, by spraying, sprinkling or pouring.
The preparation of the microemulsions according to the invention can be seen from the following examples.
Preparation E~amples Example 1 ~ g of an emulsifier mixture consisting of - ~ parts by weight of a nonylphenol polyglycol ether which has an average of 27 oxyethylene and 27 oxypropylene units per molecule, and - 4 parts by weight of calcium 4-(n-dodecyl)-phenyl-sulphonate (dissolved in n-butanol), is added, at temperatures bet~een 20C and 40C and while stirring, to 70 g of the insecticidal active compound 0,0-dimethyl 0-(4-methyLmercapto-3-methylphenyl) thiono-phosphate. The homogeneous solution thus formed is poured, in the course of 2 minutes and while stirring vigorously, in~o 22 g of deionised water. When the addition is com-plete, stirring is continued for a further 5 minutes. A
transparent microemulsion is formed, which exhibits no physi-cal or chemical changes even after storage at elevated Le A Z1 9Z9 -- ~X~9~6~
temperature for several weeks.
Example 2 14 9 of an emulsifier mixture consisting of 10 parts by weight of an alkylaryl polyglycol ether, the average composition of which can be seen from the following formula (CH2 ~ )l,7 O-(CH2-CH2O)12 H
and - 4 parts by weight of calcium 4-(n~dodecyl)-phenylsulphonate (dissolved in n butanol), are added, at temperatures between 2~ and 40C and while stirring, to 50 9 of 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate. ~he homogeneous solution thus formed is added, in the course of 2 minutes and while stirring vigorously, to 36 9 of deionised water. When the addition is complete, stirring is continued for a further 5 minutes. A transparent microemulsion is formed, which exhibits no physical or chemical changes even after storage at elevated temperature for several weeks.
Le A 21 529
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous microemulsion comprising:
A. 0.1 to 80% by weight of at least one agrochemically active compound of low solubility in water and/or one active compound for combating pests in the household and hygiene sectors, and B. 1 to 20% by weight of a mixture of emulsifiers selected from a) a mixture of at least one alkylaryl polyglycol ether of the formula (I) in which R represents alkyl having 8 to 20 carbon atoms, X and Y each represent a -CH2-CH2-O-, or group, but X and Y do not simultaneously represent an oxyethylene or oxypropylene unit, m represents numbers from 10 to 45 and n represents numbers from 10 to 45, with at least one alkylarylsulphonic acid salt of the formula ? Me ? (II) in which R1 represents alkyl having 8 to 35 carbon atoms and Me? represents an alkali metal cation, an equivalent of an alkaline earth metal cation or a cation of the formula wherein R', R'', R''' and RIV independently of one another represent hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 1 to 4 carbon atoms, or b) a mixture of at least one alkylaryl polyglycol ether of the formula (III) in which p represents numbers from 5 to 20 and q represents numbers from 1 to 3, with at least one alkylarylsulphonic acid salt of formula (II) defined above, the sum of the recited components and the water being in each case 100% by weight.
A. 0.1 to 80% by weight of at least one agrochemically active compound of low solubility in water and/or one active compound for combating pests in the household and hygiene sectors, and B. 1 to 20% by weight of a mixture of emulsifiers selected from a) a mixture of at least one alkylaryl polyglycol ether of the formula (I) in which R represents alkyl having 8 to 20 carbon atoms, X and Y each represent a -CH2-CH2-O-, or group, but X and Y do not simultaneously represent an oxyethylene or oxypropylene unit, m represents numbers from 10 to 45 and n represents numbers from 10 to 45, with at least one alkylarylsulphonic acid salt of the formula ? Me ? (II) in which R1 represents alkyl having 8 to 35 carbon atoms and Me? represents an alkali metal cation, an equivalent of an alkaline earth metal cation or a cation of the formula wherein R', R'', R''' and RIV independently of one another represent hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 1 to 4 carbon atoms, or b) a mixture of at least one alkylaryl polyglycol ether of the formula (III) in which p represents numbers from 5 to 20 and q represents numbers from 1 to 3, with at least one alkylarylsulphonic acid salt of formula (II) defined above, the sum of the recited components and the water being in each case 100% by weight.
2. An aqueous microemulsion according to Claim 1, wherein the microemulsion contains 1 to 30% by weight of at least one organic solvent of low miscribility with water and/or a solubilizer.
3. An aqueous microemulsion according to Claim 1, wherein the microemulsion contains 0.05 to 15% by weight of an additive.
4. A microemulsion according to Claim 2, wherein said organic solvent is an aromatic hydrocarbon, chlorinated aromatic hydrocarbon, aliphatic hydrocarbon, chlorinated aliphatic hydrocarbon, alcohol, ketone, ether, ester or trialkyl phosphate.
5. A microemulsion according to Claim 4, wherein said organic solvent is selected from the group consisting xylene, toluene, dimethylnaphthalene, ligroin, petroleum ether, methylene chloride, chloroform, cyclohexane, n-butanol, n-hexanol, isohexanol, n-octanol, cyclohexanol, benzyl alcohol, di-n-butyl ketone =, isophorone, glycol monomethyl ether, glycol monomethyl ether-acetate and triethyl phosphate.
6. A microemulsion according to Claim 3, containing as an additive, a preservative, dyestuff, cold stabilizer or synergist.
7. A microemulsion according to Claim 1, wherein component A is an agrochemically active compound.
8. A microemulsion according to Claim 7, wherein said agrochemically active compound is an insectide, acaricide, nematocide, fungicide, herbicide, plant growth regulator or fertilizer.
9. A microemulsion according to Claim 8, wherein said agrochemically active compound is a compound selected from the group consisting of:
0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, 0-(ethyl) 0-(4-methylthiophenyl) S-propyl dithiophosphate, (0,0-diethylthionophosphoryl)-.alpha.-oximinophenylacetonitrile, 2-isopropoxyphenyl N-methylcarbamate, 3-methylthio-4-amino-6-tert.-butyl-1,2,4-triazin-5-one, 3-methylthio-4-isobutylideneamino-6-tert.-butyl-1,2,4-triazin-5-one, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate, 3,5-dimethyl-4-methylthiophenyl N-methylcarbamate, 0,0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl) thiophosphate, 6,7,8,9,10,10-hexachloro-1,5,5A,6,9,9A-hexahydro-6,9-methane-2,3,4-benzodioxathiepin-3-oxide, 1,4,5,6,7,8,8-heptachloro-4,7-endomethylene-3A,4,7,7A-tetrahydroindene, 2-(2-furyl)-benzimidazole, 5-amino-1-bis-(dimethylamido)-phosphoryl-3-phenyl-1,2,4-triazole, 4-hydroxy-3-(1,2,3,4-tetrahydro-1-naphthyl)-coumarin, S-[1,2-bis-(ethoxycarbonyl)-ethyl] 0,0-dimethyl dithio-phosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thiono-phosphate, 0-ethyl-0-(2-isopropoxycarbonylphenyl)-N-isopropylthiono-phosphoric acid ester-amide, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone, (S)-a-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate and .alpha.-cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylate.
0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, 0-(ethyl) 0-(4-methylthiophenyl) S-propyl dithiophosphate, (0,0-diethylthionophosphoryl)-.alpha.-oximinophenylacetonitrile, 2-isopropoxyphenyl N-methylcarbamate, 3-methylthio-4-amino-6-tert.-butyl-1,2,4-triazin-5-one, 3-methylthio-4-isobutylideneamino-6-tert.-butyl-1,2,4-triazin-5-one, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate, 3,5-dimethyl-4-methylthiophenyl N-methylcarbamate, 0,0-diethyl 0-(3-chloro-4-methyl-7-coumarinyl) thiophosphate, 6,7,8,9,10,10-hexachloro-1,5,5A,6,9,9A-hexahydro-6,9-methane-2,3,4-benzodioxathiepin-3-oxide, 1,4,5,6,7,8,8-heptachloro-4,7-endomethylene-3A,4,7,7A-tetrahydroindene, 2-(2-furyl)-benzimidazole, 5-amino-1-bis-(dimethylamido)-phosphoryl-3-phenyl-1,2,4-triazole, 4-hydroxy-3-(1,2,3,4-tetrahydro-1-naphthyl)-coumarin, S-[1,2-bis-(ethoxycarbonyl)-ethyl] 0,0-dimethyl dithio-phosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thiono-phosphate, 0-ethyl-0-(2-isopropoxycarbonylphenyl)-N-isopropylthiono-phosphoric acid ester-amide, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone, (S)-a-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate and .alpha.-cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylate.
10. A microemulsion according to Claim 19 wherein component A is a compound for combating pests in the domestic and hygiene sectors.
11. A microemulsion according to Claim 10, wherein component A
is selected from the group consisting of:
2-isopropoxyphenyl N-methylcarbamate, 0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, S-[1,2-bis-(ethoxycarbonyl)-ethyl] 0,0-dimethyl dithio-phosphate, 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thiono-phosphate, .gamma.-hexachlorocyclohexane and (cyclohex-1-ene-1,2-dicarboximidomethyl) 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate.
is selected from the group consisting of:
2-isopropoxyphenyl N-methylcarbamate, 0,0-diethyl 0-(4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-nitrophenyl) thionophosphate, S-[1,2-bis-(ethoxycarbonyl)-ethyl] 0,0-dimethyl dithio-phosphate, 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) thionophosphate, 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thiono-phosphate, .gamma.-hexachlorocyclohexane and (cyclohex-1-ene-1,2-dicarboximidomethyl) 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate.
12. A microemulsion according to Claim 1, wherein component B is a) a mixture of at least one alkylaryl polyglycol ether of the formula (I) with at least one alkylarylsulphonic acid salt of the formula (II).
13. A microemulsion according to Claim 1, wherein component B is b) a mixture of at least one alkylaryl polyglycol ether of the formula (III) with at least one alkylarylsulphonic acid salt of the formula (II).
14. A microemulsion according to Claim 12, wherein m represents a number from 12 to 30 and n represents a number from 12 to 40 and the alkylarylsulphonic acid salt of formula (II) is calcium 4-(n-dodecyl)-phenylsulphonate.
15. A microemulsion according to Claim 14, wherein component A is 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate.
16. A microemulsion according to Claim 13, wherein p is a number from 8 to 18, q is a number from 1 to 2 and said alkylarylsulphonic acid salt of formula (II) is 4-(n-dodecyl)-phenylsulphonate.
17. A microemulsion according to Claim 16, wherein component A is 0,0-dimethyl 0-(4-methylmercapto-3-methylphenyl) thionophosphate.
18. A process for beneficially affecting a plant or for protecting a household or hygiene sector against a pest which comprises applying to a plant, or a household or hygiene sector an effective amount of the aqueous microemulsion according to Claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3235612.9 | 1982-09-25 | ||
| DE19823235612 DE3235612A1 (en) | 1982-09-25 | 1982-09-25 | MICROEMULSIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1209361A true CA1209361A (en) | 1986-08-12 |
Family
ID=6174194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000437476A Expired CA1209361A (en) | 1982-09-25 | 1983-09-23 | Microemulsions |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0107009A3 (en) |
| JP (1) | JPS5980321A (en) |
| KR (1) | KR840005648A (en) |
| AU (1) | AU1929383A (en) |
| BR (1) | BR8305232A (en) |
| CA (1) | CA1209361A (en) |
| DD (1) | DD211056A5 (en) |
| DE (1) | DE3235612A1 (en) |
| DK (1) | DK437883A (en) |
| ES (1) | ES8501638A1 (en) |
| IL (1) | IL69776A0 (en) |
| NZ (1) | NZ205688A (en) |
| ZA (1) | ZA837087B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814167A (en) * | 1985-03-12 | 1989-03-21 | Bayer Aktiengesellschaft | Pyrettroid macroemulsions containing polyvinyl alcohol |
| US4824663A (en) * | 1985-03-12 | 1989-04-25 | Bayer Aktiengesellschaft | Biocidal macroemulsions containing polyvinyl alcohol |
| US5037653A (en) * | 1987-03-30 | 1991-08-06 | Nc Development Inc. | Pesticidal chemical formulations |
| US5154754A (en) * | 1987-03-11 | 1992-10-13 | Hoechst Aktiengesellschaft | Oil-in-water emulsions and a process for their preparation and their use |
| US5242907A (en) * | 1988-03-30 | 1993-09-07 | Nc Development, Inc. | Pesticidal control |
| US5334585A (en) * | 1991-02-22 | 1994-08-02 | Rhone-Poulenc Chimie | Pyrethroid microemulsion compositions and method for controlling insects therewith |
| EP0648414A2 (en) * | 1993-10-01 | 1995-04-19 | Rohm And Haas Company | Fully water-dilutable microemulsions |
| US5741512A (en) * | 1988-09-16 | 1998-04-21 | Novartis Corporation | Pharmaceutical compositions comprising cyclosporins |
| US6007840A (en) * | 1988-09-16 | 1999-12-28 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US6214771B1 (en) | 1995-11-06 | 2001-04-10 | American Cyanamid Company | Aqueous spray compositions |
| US6258808B1 (en) | 1991-06-27 | 2001-07-10 | Novartis Ag | Pharmaceutical composition |
| US6420355B2 (en) | 1992-09-25 | 2002-07-16 | Novartis Ag | Pharmaceutical compositions containing cyclosporins |
| US6475519B1 (en) | 1997-01-30 | 2002-11-05 | Novartis Ag | Oil-free pharmaceutical compositions containing cyclosporin A |
| US6486124B2 (en) | 1994-11-03 | 2002-11-26 | Novartis Ag | Cyclosporin compositions and process therefor |
| US6582718B2 (en) | 1992-05-13 | 2003-06-24 | Novartis Ag | Cyclosporin compositions |
| US6667276B1 (en) | 1997-11-27 | 2003-12-23 | Hoechst Schering Agrevo Gmbh | Surfactant systems for liquid aqueous preparations |
| US6951841B2 (en) | 1995-11-29 | 2005-10-04 | Novartis Ag | Pharmaceutical compositions of macrolides or cyclosporine with a polyethoxylated saturated hydroxy-fatty acid |
| US11116208B2 (en) | 2016-07-12 | 2021-09-14 | Monsanto Technology Llc | Pesticidal compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990003112A1 (en) * | 1987-03-30 | 1990-04-05 | Nc Development, Inc. | Pesticidal control |
| GB8822937D0 (en) * | 1988-09-30 | 1988-11-09 | Nc Dev Inc | Chemical formulations |
| HU199234B (en) * | 1987-05-18 | 1990-02-28 | Chinoin Gyogyszer Es Vegyeszet | Microemulsion composition comprising phosphoric acid ester or thiophosphoric acid ester as active ingredient |
| US4954338A (en) * | 1987-08-05 | 1990-09-04 | Rohm And Haas Company | Microbicidal microemulsion |
| HU204393B (en) * | 1988-12-22 | 1992-01-28 | Chinoin Gyogyszer Es Vegyeszet | Insecticide aqouos solutions containing piretroides as active components and microemulsion compositions containing former solutions |
| FR2787348B1 (en) * | 1998-12-18 | 2002-06-28 | Arcane Ind | MICRO-EMULSIONS, PREPARATION METHOD AND APPLICATIONS |
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| US6299622B1 (en) | 1999-08-19 | 2001-10-09 | Fox Hollow Technologies, Inc. | Atherectomy catheter with aligned imager |
| ES2436668T3 (en) | 2000-12-20 | 2014-01-03 | Covidien Lp | Catheter to remove atheromatous or thrombotic occlusive material |
| US8246640B2 (en) | 2003-04-22 | 2012-08-21 | Tyco Healthcare Group Lp | Methods and devices for cutting tissue at a vascular location |
| JP4025735B2 (en) * | 2003-08-21 | 2007-12-26 | ローム アンド ハース カンパニー | Method for treating aqueous systems |
| DE102005049765A1 (en) * | 2005-10-18 | 2007-04-19 | Forschungszentrum Jülich GmbH | Method for increasing the efficiency of surfactants, for widening the temperature window, for suppressing lamellar mesophases in microemulsions by means of additives, and microemulsions |
| US20070276419A1 (en) | 2006-05-26 | 2007-11-29 | Fox Hollow Technologies, Inc. | Methods and devices for rotating an active element and an energy emitter on a catheter |
| EP1891855A1 (en) * | 2006-08-05 | 2008-02-27 | Bayer CropScience AG | Novel microemulsion concentrates |
| US8784440B2 (en) | 2008-02-25 | 2014-07-22 | Covidien Lp | Methods and devices for cutting tissue |
| KR101645754B1 (en) | 2008-10-13 | 2016-08-04 | 코비디엔 엘피 | Devices and methods for manipulating a catheter shaft |
| WO2010126882A1 (en) | 2009-04-29 | 2010-11-04 | Fox Hollow Technologies, Inc. | Methods and devices for cutting and abrading tissue |
| RU2509538C2 (en) | 2009-05-14 | 2014-03-20 | ТАЙКО ХЕЛСКЕА ГРУП эЛПи | Cleanable atherectomy catheters and methods for using them |
| WO2011068932A1 (en) | 2009-12-02 | 2011-06-09 | Fox Hollow Technologies, Inc. | Methods and devices for cutting tissue |
| JP5511107B2 (en) | 2009-12-11 | 2014-06-04 | コヴィディエン リミテッド パートナーシップ | Substance removal device and method with improved substance capture efficiency |
| KR101493138B1 (en) | 2010-06-14 | 2015-02-12 | 코비디엔 엘피 | Material removal device |
| EP2632352B1 (en) | 2010-10-28 | 2017-04-12 | Covidien LP | Material removal device |
| CA2817213C (en) | 2010-11-11 | 2016-06-14 | Covidien Lp | Flexible debulking catheters with imaging and methods of use and manufacture |
| WO2013033426A2 (en) | 2011-09-01 | 2013-03-07 | Covidien Lp | Catheter with helical drive shaft and methods of manufacture |
| US9532844B2 (en) | 2012-09-13 | 2017-01-03 | Covidien Lp | Cleaning device for medical instrument and method of use |
| US9943329B2 (en) | 2012-11-08 | 2018-04-17 | Covidien Lp | Tissue-removing catheter with rotatable cutter |
| WO2015200702A1 (en) | 2014-06-27 | 2015-12-30 | Covidien Lp | Cleaning device for catheter and catheter including the same |
| US10314667B2 (en) | 2015-03-25 | 2019-06-11 | Covidien Lp | Cleaning device for cleaning medical instrument |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE824949C (en) * | 1948-11-26 | 1951-12-17 | Bayer Ag | Emulsifiers and dispersants |
| GB1215108A (en) * | 1969-03-25 | 1970-12-09 | Sanyo Chemical Ind Ltd | Emulsifiers and emulsifiable toxicant compositions |
| DE2041480C3 (en) * | 1970-08-20 | 1974-05-02 | Vyzkumny Ustav Agrochemickej Technologie, Pressburg (Tschechoslowakei) | Nonionic surface-active compounds based on polyglycol ethers benzylated phenols |
| DE2053356B2 (en) * | 1970-10-30 | 1978-09-21 | Basf Ag, 6700 Ludwigshafen | Two-component emulsifier system for the formulation of pesticides |
-
1982
- 1982-09-25 DE DE19823235612 patent/DE3235612A1/en not_active Withdrawn
-
1983
- 1983-09-14 EP EP83109051A patent/EP0107009A3/en not_active Withdrawn
- 1983-09-20 AU AU19293/83A patent/AU1929383A/en not_active Abandoned
- 1983-09-21 IL IL69776A patent/IL69776A0/en unknown
- 1983-09-22 NZ NZ205688A patent/NZ205688A/en unknown
- 1983-09-23 KR KR1019830004459A patent/KR840005648A/en not_active Application Discontinuation
- 1983-09-23 DD DD83255092A patent/DD211056A5/en unknown
- 1983-09-23 BR BR8305232A patent/BR8305232A/en unknown
- 1983-09-23 ZA ZA837087A patent/ZA837087B/en unknown
- 1983-09-23 ES ES525901A patent/ES8501638A1/en not_active Expired
- 1983-09-23 CA CA000437476A patent/CA1209361A/en not_active Expired
- 1983-09-23 DK DK437883A patent/DK437883A/en not_active Application Discontinuation
- 1983-09-24 JP JP58175224A patent/JPS5980321A/en active Pending
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4824663A (en) * | 1985-03-12 | 1989-04-25 | Bayer Aktiengesellschaft | Biocidal macroemulsions containing polyvinyl alcohol |
| US4814167A (en) * | 1985-03-12 | 1989-03-21 | Bayer Aktiengesellschaft | Pyrettroid macroemulsions containing polyvinyl alcohol |
| US5154754A (en) * | 1987-03-11 | 1992-10-13 | Hoechst Aktiengesellschaft | Oil-in-water emulsions and a process for their preparation and their use |
| US5407920A (en) * | 1987-03-30 | 1995-04-18 | Nc Development, Inc. | Treatment of wood and timber with pesticidal formulations |
| US5037653A (en) * | 1987-03-30 | 1991-08-06 | Nc Development Inc. | Pesticidal chemical formulations |
| US5242907A (en) * | 1988-03-30 | 1993-09-07 | Nc Development, Inc. | Pesticidal control |
| US5916589A (en) * | 1988-09-16 | 1999-06-29 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US7235248B2 (en) | 1988-09-16 | 2007-06-26 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US5741512A (en) * | 1988-09-16 | 1998-04-21 | Novartis Corporation | Pharmaceutical compositions comprising cyclosporins |
| US5866159A (en) * | 1988-09-16 | 1999-02-02 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US5962014A (en) * | 1988-09-16 | 1999-10-05 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US5962017A (en) * | 1988-09-16 | 1999-10-05 | Novartis G | Pharmaceutical compositions comprising cyclosporins |
| US6007840A (en) * | 1988-09-16 | 1999-12-28 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US6024978A (en) * | 1988-09-16 | 2000-02-15 | Novartis Ag | Pharmaceutical compositions comprising cyclosporins |
| US5334585A (en) * | 1991-02-22 | 1994-08-02 | Rhone-Poulenc Chimie | Pyrethroid microemulsion compositions and method for controlling insects therewith |
| US6844459B2 (en) | 1991-06-27 | 2005-01-18 | Novartis Ag | Pharmaceutical Composition |
| US6258808B1 (en) | 1991-06-27 | 2001-07-10 | Novartis Ag | Pharmaceutical composition |
| US6582718B2 (en) | 1992-05-13 | 2003-06-24 | Novartis Ag | Cyclosporin compositions |
| US6262022B1 (en) | 1992-06-25 | 2001-07-17 | Novartis Ag | Pharmaceutical compositions containing cyclosporin as the active agent |
| US6420355B2 (en) | 1992-09-25 | 2002-07-16 | Novartis Ag | Pharmaceutical compositions containing cyclosporins |
| CN1064212C (en) * | 1993-10-01 | 2001-04-11 | 罗姆和哈斯公司 | Fully water-dilutable microemulsions |
| EP0648414A3 (en) * | 1993-10-01 | 1995-10-25 | Rohm & Haas | Fully water-dilutable microemulsions. |
| US5444078A (en) * | 1993-10-01 | 1995-08-22 | Rohm And Haas Company | Fully water-dilutable microemulsions |
| EP0648414A2 (en) * | 1993-10-01 | 1995-04-19 | Rohm And Haas Company | Fully water-dilutable microemulsions |
| US6486124B2 (en) | 1994-11-03 | 2002-11-26 | Novartis Ag | Cyclosporin compositions and process therefor |
| US6214771B1 (en) | 1995-11-06 | 2001-04-10 | American Cyanamid Company | Aqueous spray compositions |
| US6951841B2 (en) | 1995-11-29 | 2005-10-04 | Novartis Ag | Pharmaceutical compositions of macrolides or cyclosporine with a polyethoxylated saturated hydroxy-fatty acid |
| US6475519B1 (en) | 1997-01-30 | 2002-11-05 | Novartis Ag | Oil-free pharmaceutical compositions containing cyclosporin A |
| US6723339B2 (en) | 1997-01-30 | 2004-04-20 | Novartis Ag | Oil-free pharmaceutical compositions containing cyclosporin A |
| US6667276B1 (en) | 1997-11-27 | 2003-12-23 | Hoechst Schering Agrevo Gmbh | Surfactant systems for liquid aqueous preparations |
| US11116208B2 (en) | 2016-07-12 | 2021-09-14 | Monsanto Technology Llc | Pesticidal compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ205688A (en) | 1985-08-30 |
| EP0107009A2 (en) | 1984-05-02 |
| ZA837087B (en) | 1984-05-30 |
| IL69776A0 (en) | 1983-12-30 |
| JPS5980321A (en) | 1984-05-09 |
| EP0107009A3 (en) | 1985-07-10 |
| AU1929383A (en) | 1984-03-29 |
| DE3235612A1 (en) | 1984-03-29 |
| BR8305232A (en) | 1984-05-02 |
| ES525901A0 (en) | 1984-12-01 |
| DD211056A5 (en) | 1984-07-04 |
| DK437883D0 (en) | 1983-09-23 |
| KR840005648A (en) | 1984-11-16 |
| DK437883A (en) | 1984-03-26 |
| ES8501638A1 (en) | 1984-12-01 |
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