CA1142850A - Pesticidally-active concentrated oil-in- water emulsions - Google Patents
Pesticidally-active concentrated oil-in- water emulsionsInfo
- Publication number
- CA1142850A CA1142850A CA000346528A CA346528A CA1142850A CA 1142850 A CA1142850 A CA 1142850A CA 000346528 A CA000346528 A CA 000346528A CA 346528 A CA346528 A CA 346528A CA 1142850 A CA1142850 A CA 1142850A
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- 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
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- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT
PESTICIDALLY-ACTIVE CONCENTRATED OIL-IN-WATER
EMULSIONS
The invention is a pesticidally-active con-centrated emulsion comprising:-3.5-6.5 or 10-35 parts by weight of lipophilic pesticide, 3.5-6.5 or 10-35 parts by weight of hydrocarbon solvent, 0.1-10 parts by weight of an alkanol, 0.5-32 parts by weight of at least one non-ionic surfactant so stabilise the emulsion, and water to bring the total of all components of the emulsion to 109 parts by weight.
The emulsions have excellent freeze/thaw stability and are generally stable over a wide range of storage temperatures. A process for the preparation of the emulsions is also claimed.
PESTICIDALLY-ACTIVE CONCENTRATED OIL-IN-WATER
EMULSIONS
The invention is a pesticidally-active con-centrated emulsion comprising:-3.5-6.5 or 10-35 parts by weight of lipophilic pesticide, 3.5-6.5 or 10-35 parts by weight of hydrocarbon solvent, 0.1-10 parts by weight of an alkanol, 0.5-32 parts by weight of at least one non-ionic surfactant so stabilise the emulsion, and water to bring the total of all components of the emulsion to 109 parts by weight.
The emulsions have excellent freeze/thaw stability and are generally stable over a wide range of storage temperatures. A process for the preparation of the emulsions is also claimed.
Description
s~
PESTICIDALLY-ACT[~E C(~NCENTR~I'ED OIL-IN-~TER
EM[ILSIONS
m e present invention relates to a pesticidally-active con-centrated oil-in-water emulsion and to a process for its prepara-tion.
Because pesticide form~lations are stored over long periods of time under changing temperature conditions or extremes of weather, it is necessary that their formulations have a stability over the broad range of storage temperatures, including an ability to retain their integrity after being frozen.
While preformed emulsions of lipophilic substances in aqueous media are kno~n, mainly in the cosmetic, food and pharmaceu-tical industries, these emwlsions are incapable of undergoing re-peated freeze/thaw conditions without breaking. It was desirable, therefore, to devise new emulsions, capable of undergoing extremes of temperature.
m e present invention provides a pesticidally-active con-centrated emulsion comprising:-3.5-6.5 or 10-35 parts by weight of a lipophilic pesticide, 3.5-6.5 or 10-35 parts by weight of a hydrocarbon solvent, 0.1-10 parts by weight of an alkanol, 0.5-32 parts by weight of at least one nonionic surfactant to stabilise the emLlsion, and water to bring the total of all oomponents of the emulsion to 100 parts by weight.
In contrast to ordinary emulsions, which are simple mix-tures, i.e., dispersions of one immiscible liquid into another made relatively stable by an emulsifying agent, the subject of this inven-tion is stoichiometrically well-defined within the boundaries de-picted in a three phase diagram. Further, the unusual stability of these emulsions, at temperatures in the range -18 to 120C, appears to be associated with a definite structure which i5 made evident by the birefringent property of the em~lsions observed in a microoe ll with a polarizing microscope. Birefrigence is the numerical differ-ence between the ma~imum and minimum refractive indices in a sub-stance which is capable of having more than one refraction index.
me birefringenoe disappears when the emulsion is broken at 120&
and boiling occurs. Practical emulsions of this type were generally discussed by Stig Friberg and Inza Wirton in American Perfumes and Cosmetics 85 (12)27 (1970). me emulsions are believed to have this unusual stability due to the formation of a structure not unlike liquid crystals.
The lipophilic pesticide may be selected from a variety of broad spectrum or selective pesticides including insecticides, acaricides, fungicides and herbicides.
Any pes-ticide which has lipophilic properties and low water solubility, for example, a water solubility of 100 ppm or lower, is suitable for formulation into the concentrated oil-in-water emulsions of this invention. Such pesticides include lipophilic organophos-phates including organo~hosphorus oompounds such as diethyl (2-iso-propyl-4-methyl-6-pyrimidinyl)phosphorothioate or ~imethyl S-[(4-oxo-1,2,3-benzotriaz.in-3(4H)-yl)methyl]phosphorodithioate, par~icularly including lipophilic vinylorganophosphates such as dimethyl 1-(2,4/5-trichlorophenyl)-2-chlorovinyl p~osphate, natural products and deriva-tives thereof including pyrethrins, rotenones, tobacco extracts, pine oil, resin, tar or gum and the like, liphophilic al~line deriva-tives such as ~ -trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine and N-butyl-N-ethyl-2,6-dinitro-4-trifluoromethylaniline or chlorin-ated hydrocarbons such as chlordane and numerous other lipophilic pesticides.
A p æticularly suitable class of pesticides are those termed "synthetic pyrethroids". Preferably, the pesticidally-active pyrethroid has the formula I
0~
A -- C - O -- CH~_~
s~
wherein A is an optionally-substitu~ed aralkyl, alkyl or cycloalkyl group and R is hydrogen, cyano or ethynyl. Generally speaking, the alkyl, cycloalkyl, or aralkyl groups preferably co.ntain up to 10 carbon atoms.
When A represents an optionally-substituted cycloalkyl group in formula I, the preferred co~lpounds are those containing a cyclopropyl group of formwla II
R ~ R
a ~ b ~ II
c / - \ - H
Rd wherein Ra and Rb each represent an alkyl group containing 1 to 6 carbon atoms, especially methyl, or a halos-en atom having an atomic number of 9 to 35, inclusive, especially chlorine atom; or when Ra represents a hydrogen atom then Rb represents an alkenyl group con-taining 2 to 6 carbon atoms optionally-substituted by 1 to 3 chlorine or bromine atoms, especially isobutenyl or a m~no- or dichlorovinyl group; Rc and Rd each represent an alkyl group contain-ing 1 to 6 carbon atoms, or when Rc is hydrogen then Rd is an alkenyl group containing 2 to 6 carbon atoms optionally-substitu-ted by 1 to 3 chlorine or brc~une atoms, especially a mono- or dichlorovinyl group;
or at least one of Ra and Rb together or Rc and Rd together each represent an alkylene group containing 2 to 6, especially 3 carbon atoms.
~.~
S~
Preferred because of their inseeticidal properties are those pyrethroids wherein in the eyelopropyl group of formula II Ra and ~ eaeh is methyl, Rc and Rd eaeh is methyl or when Rc is a hydrogen atom then Rd is isobutenyl, 2,2-diehlorovinyl, or 2,2-dibromovinyl.
When A represents an aralkyl group in formula I, preferred eompounds are those containing a substituted benzyl group of formNla III H
wherein Z represents a halogen atcm having an atomie numker of 9 b~
35, inclusive, or an alkyl or alkoxy group of 1 to 4 carbon atoms, e.g. methyl or methoxy, and Q represents cm alkyl group of 1 to 6 earbon atoms, espeeially a branehed ehain group sueh as an isopropyl group.
m e most preferred pyrethroids for use in the pestieidal em~lsion aceording to the invention have the formula I wherein A is alpha-isopropyl-4-chlorokenzyl, 2,2,3,3-tetramethylcyelopropyl,
PESTICIDALLY-ACT[~E C(~NCENTR~I'ED OIL-IN-~TER
EM[ILSIONS
m e present invention relates to a pesticidally-active con-centrated oil-in-water emulsion and to a process for its prepara-tion.
Because pesticide form~lations are stored over long periods of time under changing temperature conditions or extremes of weather, it is necessary that their formulations have a stability over the broad range of storage temperatures, including an ability to retain their integrity after being frozen.
While preformed emulsions of lipophilic substances in aqueous media are kno~n, mainly in the cosmetic, food and pharmaceu-tical industries, these emwlsions are incapable of undergoing re-peated freeze/thaw conditions without breaking. It was desirable, therefore, to devise new emulsions, capable of undergoing extremes of temperature.
m e present invention provides a pesticidally-active con-centrated emulsion comprising:-3.5-6.5 or 10-35 parts by weight of a lipophilic pesticide, 3.5-6.5 or 10-35 parts by weight of a hydrocarbon solvent, 0.1-10 parts by weight of an alkanol, 0.5-32 parts by weight of at least one nonionic surfactant to stabilise the emLlsion, and water to bring the total of all oomponents of the emulsion to 100 parts by weight.
In contrast to ordinary emulsions, which are simple mix-tures, i.e., dispersions of one immiscible liquid into another made relatively stable by an emulsifying agent, the subject of this inven-tion is stoichiometrically well-defined within the boundaries de-picted in a three phase diagram. Further, the unusual stability of these emulsions, at temperatures in the range -18 to 120C, appears to be associated with a definite structure which i5 made evident by the birefringent property of the em~lsions observed in a microoe ll with a polarizing microscope. Birefrigence is the numerical differ-ence between the ma~imum and minimum refractive indices in a sub-stance which is capable of having more than one refraction index.
me birefringenoe disappears when the emulsion is broken at 120&
and boiling occurs. Practical emulsions of this type were generally discussed by Stig Friberg and Inza Wirton in American Perfumes and Cosmetics 85 (12)27 (1970). me emulsions are believed to have this unusual stability due to the formation of a structure not unlike liquid crystals.
The lipophilic pesticide may be selected from a variety of broad spectrum or selective pesticides including insecticides, acaricides, fungicides and herbicides.
Any pes-ticide which has lipophilic properties and low water solubility, for example, a water solubility of 100 ppm or lower, is suitable for formulation into the concentrated oil-in-water emulsions of this invention. Such pesticides include lipophilic organophos-phates including organo~hosphorus oompounds such as diethyl (2-iso-propyl-4-methyl-6-pyrimidinyl)phosphorothioate or ~imethyl S-[(4-oxo-1,2,3-benzotriaz.in-3(4H)-yl)methyl]phosphorodithioate, par~icularly including lipophilic vinylorganophosphates such as dimethyl 1-(2,4/5-trichlorophenyl)-2-chlorovinyl p~osphate, natural products and deriva-tives thereof including pyrethrins, rotenones, tobacco extracts, pine oil, resin, tar or gum and the like, liphophilic al~line deriva-tives such as ~ -trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine and N-butyl-N-ethyl-2,6-dinitro-4-trifluoromethylaniline or chlorin-ated hydrocarbons such as chlordane and numerous other lipophilic pesticides.
A p æticularly suitable class of pesticides are those termed "synthetic pyrethroids". Preferably, the pesticidally-active pyrethroid has the formula I
0~
A -- C - O -- CH~_~
s~
wherein A is an optionally-substitu~ed aralkyl, alkyl or cycloalkyl group and R is hydrogen, cyano or ethynyl. Generally speaking, the alkyl, cycloalkyl, or aralkyl groups preferably co.ntain up to 10 carbon atoms.
When A represents an optionally-substituted cycloalkyl group in formula I, the preferred co~lpounds are those containing a cyclopropyl group of formwla II
R ~ R
a ~ b ~ II
c / - \ - H
Rd wherein Ra and Rb each represent an alkyl group containing 1 to 6 carbon atoms, especially methyl, or a halos-en atom having an atomic number of 9 to 35, inclusive, especially chlorine atom; or when Ra represents a hydrogen atom then Rb represents an alkenyl group con-taining 2 to 6 carbon atoms optionally-substituted by 1 to 3 chlorine or bromine atoms, especially isobutenyl or a m~no- or dichlorovinyl group; Rc and Rd each represent an alkyl group contain-ing 1 to 6 carbon atoms, or when Rc is hydrogen then Rd is an alkenyl group containing 2 to 6 carbon atoms optionally-substitu-ted by 1 to 3 chlorine or brc~une atoms, especially a mono- or dichlorovinyl group;
or at least one of Ra and Rb together or Rc and Rd together each represent an alkylene group containing 2 to 6, especially 3 carbon atoms.
~.~
S~
Preferred because of their inseeticidal properties are those pyrethroids wherein in the eyelopropyl group of formula II Ra and ~ eaeh is methyl, Rc and Rd eaeh is methyl or when Rc is a hydrogen atom then Rd is isobutenyl, 2,2-diehlorovinyl, or 2,2-dibromovinyl.
When A represents an aralkyl group in formula I, preferred eompounds are those containing a substituted benzyl group of formNla III H
wherein Z represents a halogen atcm having an atomie numker of 9 b~
35, inclusive, or an alkyl or alkoxy group of 1 to 4 carbon atoms, e.g. methyl or methoxy, and Q represents cm alkyl group of 1 to 6 earbon atoms, espeeially a branehed ehain group sueh as an isopropyl group.
m e most preferred pyrethroids for use in the pestieidal em~lsion aceording to the invention have the formula I wherein A is alpha-isopropyl-4-chlorokenzyl, 2,2,3,3-tetramethylcyelopropyl,
2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl, or 2-(2,2-dibromovinyl)-
3,3~dimethyleyelopropyl; R is hydrogen, ethynyl or cyano.
,~ ~
.
It should ke noted that optical isomers, cis-trans isomers and other kinds of geometric isomers of the compounds according to formula I are within the scope of the present invention as well and mixtures of one or more of iscmers of the pesticidally active com-pounds according to formula I. The various isomers of the compounds according to formula I may have different pesticidal toxicities and/
or knock-down potency. m us, one may prefer to resolve mLxtures of isQmers to recover a more pesticidally-active isomer or diastereo-isomer pair or to prepare the more active forms directly for use in the em~lsions of the invention.
As stated hereinbefore, the lipophilic pesticide is pre-sent in amounts of 10-35 parts by weight. Preferably, emulsions are formulated in which the pesticide is present in amounts of 28-32 parts by weight. In the case of the synthetic pyrethroids descriked herein the amounts of about 30-31 parts by weight have been found especially suitable for the formation of stable emulsions.
The hydrocarbon solvent used may include any numker of alkane, cycloalkane, alkene, aromatic and alkyl-aromatic hydro-OE kons. Generally speaking, the alkanes, including cycloalkanes, and alkenes contain from 1 12 carbon atoms, for example, p~ntane, hexane, , .
85~
heptane, hexene, and cyclohexane, while the aromatic and alkyl-aromatics contain 6-20 carbon atoms and 1-2 hydrocarbyl rings, for example benzene, naphthalene, toluene, ethylbenzene, xylene, tri-methylbenzene, p-ethyltoluene; mixtures of any of the above hydro-carbons may be used. Particularly useful are mixtures of alkyl-benzenes. One such mixture is sold under the trademark Tenneco 500-100 by Tenneco Oil Company and contains predominantly p-ethyl-toluene and 1,2,4-trimethylbenzene with minor amounts of ~rtho-xylene, other alkylbenzenes, C10 and heavier aromatics and non-aromatics and is especially desirable because of its high flashpoint. Naphthas, petroluem distillates and certain lubricating fractions can also be used. In general, mixtures of aromatic hydro-carbons having a flash point by Tag Closed Cup Tester of over 100F
are preferred.
The hydrocarbon solvent is present in an amount sufficient to make the density of the solvent-pesticide phase equal to that of the water-alkanol phase of 10-35 parts by weightOPreferably, emulsions are formulated in which the solvent is present in amounts of 28-32 parts by weight, or more suitably in amount of about 30-31 parts by weight. In the case of formulations in which the above-described synthetic pyrethroids are used as the lipophilic ' pesticide, the solvent is preferably Tenneco 500-100. The solvent is preferably used in about the same amount (parts by weight) as the pyrethroid.
Exa~ples of the alkanol ccmponent include monohydroxy alcohols containing 1 to 4 carbon atoms and dihydro~y alcohols con-taining from 2 to 4 carbon atoms, for example methanol, ethanol, iso-propanol, ethylene glycol, propylene glycol, 1,3-propandiol, and 1,2-butandiol. Preferably, an alkandiol containing from 2 to 3 carbon atcms is used, especially ethylene glycol or propylene glycol.
A trihydroxy alcohol such as glycerol may also be used.
m e alkanol co~ponent of the emulsion is present in amounts of 0.1-10 parts by weight. Preferably, the aIkanol is pre-s~nt in amounts of 2-6 parts by weight, suitably 3-5 parts by weight.
Suitable nonionic surfactants (surface-active agents) can bP broadly defined as the emulsifying co~pounds required to give a stable em~lsion with the particular hydrophile/lipophile balanoe of the oil phase containing the pesticidally-active ingredient as deter-mined by the method descri~ed by A. Beerbower and M.W. Hill in M~Cutcheon's Detergents and Emulsifiers, page 223 (1971) and are usually compounds, aliphatic or aIkylaromatic in nature, which do not ionize in water solution. For example, a 35~
well-known class of nonionic agents is available under the trade-mark "Pluronic". These compounds are Eormed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propy-lene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a mole-cular weight of from about 1,500 to 1,800. The addition of poly-oxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxy-ethylene content is about 50~ of the total weight of the condensa-tion product.
Other suitable nonionic surfactants include:
(1~ The polyethylene oxide or propylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethy-lene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds is derived, for example, from polymerized propylene, di-isobutylene, octene, or nonene;
(2) The condensates derived from ethylene oxide ~L2~
and the product resulting rom the reaction of propylene oxide and ethylenediamine. For example, compounds containing about 40% to about 80% polyoxyethylene by weight and having a molecular weight of about 5,000 to about 11,000 resulting from the reaction of ethylene o~ide groups with a hydrophobic base constituted of -the reaction pro-duct of ethylene diamine and excess propylene oxide, said hydro-phobic bases having a molecular weight o the order of 2,500 to 3,000, are satisactory;
(3) The condensation product of fatty acids, hydrogenated fatty acids (including hydrogenated castor oil) or aliphatic alcohols having 8 to 18 carbon atcms, in ei-ther straight chain~or branched chain conflguration, with propylene oxide or ethylene oxide, e.g. a coco~ut alcohol-ethylene oxide condensate having 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 10 to 14 carbon atoms;
,~ ~
.
It should ke noted that optical isomers, cis-trans isomers and other kinds of geometric isomers of the compounds according to formula I are within the scope of the present invention as well and mixtures of one or more of iscmers of the pesticidally active com-pounds according to formula I. The various isomers of the compounds according to formula I may have different pesticidal toxicities and/
or knock-down potency. m us, one may prefer to resolve mLxtures of isQmers to recover a more pesticidally-active isomer or diastereo-isomer pair or to prepare the more active forms directly for use in the em~lsions of the invention.
As stated hereinbefore, the lipophilic pesticide is pre-sent in amounts of 10-35 parts by weight. Preferably, emulsions are formulated in which the pesticide is present in amounts of 28-32 parts by weight. In the case of the synthetic pyrethroids descriked herein the amounts of about 30-31 parts by weight have been found especially suitable for the formation of stable emulsions.
The hydrocarbon solvent used may include any numker of alkane, cycloalkane, alkene, aromatic and alkyl-aromatic hydro-OE kons. Generally speaking, the alkanes, including cycloalkanes, and alkenes contain from 1 12 carbon atoms, for example, p~ntane, hexane, , .
85~
heptane, hexene, and cyclohexane, while the aromatic and alkyl-aromatics contain 6-20 carbon atoms and 1-2 hydrocarbyl rings, for example benzene, naphthalene, toluene, ethylbenzene, xylene, tri-methylbenzene, p-ethyltoluene; mixtures of any of the above hydro-carbons may be used. Particularly useful are mixtures of alkyl-benzenes. One such mixture is sold under the trademark Tenneco 500-100 by Tenneco Oil Company and contains predominantly p-ethyl-toluene and 1,2,4-trimethylbenzene with minor amounts of ~rtho-xylene, other alkylbenzenes, C10 and heavier aromatics and non-aromatics and is especially desirable because of its high flashpoint. Naphthas, petroluem distillates and certain lubricating fractions can also be used. In general, mixtures of aromatic hydro-carbons having a flash point by Tag Closed Cup Tester of over 100F
are preferred.
The hydrocarbon solvent is present in an amount sufficient to make the density of the solvent-pesticide phase equal to that of the water-alkanol phase of 10-35 parts by weightOPreferably, emulsions are formulated in which the solvent is present in amounts of 28-32 parts by weight, or more suitably in amount of about 30-31 parts by weight. In the case of formulations in which the above-described synthetic pyrethroids are used as the lipophilic ' pesticide, the solvent is preferably Tenneco 500-100. The solvent is preferably used in about the same amount (parts by weight) as the pyrethroid.
Exa~ples of the alkanol ccmponent include monohydroxy alcohols containing 1 to 4 carbon atoms and dihydro~y alcohols con-taining from 2 to 4 carbon atoms, for example methanol, ethanol, iso-propanol, ethylene glycol, propylene glycol, 1,3-propandiol, and 1,2-butandiol. Preferably, an alkandiol containing from 2 to 3 carbon atcms is used, especially ethylene glycol or propylene glycol.
A trihydroxy alcohol such as glycerol may also be used.
m e alkanol co~ponent of the emulsion is present in amounts of 0.1-10 parts by weight. Preferably, the aIkanol is pre-s~nt in amounts of 2-6 parts by weight, suitably 3-5 parts by weight.
Suitable nonionic surfactants (surface-active agents) can bP broadly defined as the emulsifying co~pounds required to give a stable em~lsion with the particular hydrophile/lipophile balanoe of the oil phase containing the pesticidally-active ingredient as deter-mined by the method descri~ed by A. Beerbower and M.W. Hill in M~Cutcheon's Detergents and Emulsifiers, page 223 (1971) and are usually compounds, aliphatic or aIkylaromatic in nature, which do not ionize in water solution. For example, a 35~
well-known class of nonionic agents is available under the trade-mark "Pluronic". These compounds are Eormed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propy-lene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a mole-cular weight of from about 1,500 to 1,800. The addition of poly-oxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxy-ethylene content is about 50~ of the total weight of the condensa-tion product.
Other suitable nonionic surfactants include:
(1~ The polyethylene oxide or propylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethy-lene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds is derived, for example, from polymerized propylene, di-isobutylene, octene, or nonene;
(2) The condensates derived from ethylene oxide ~L2~
and the product resulting rom the reaction of propylene oxide and ethylenediamine. For example, compounds containing about 40% to about 80% polyoxyethylene by weight and having a molecular weight of about 5,000 to about 11,000 resulting from the reaction of ethylene o~ide groups with a hydrophobic base constituted of -the reaction pro-duct of ethylene diamine and excess propylene oxide, said hydro-phobic bases having a molecular weight o the order of 2,500 to 3,000, are satisactory;
(3) The condensation product of fatty acids, hydrogenated fatty acids (including hydrogenated castor oil) or aliphatic alcohols having 8 to 18 carbon atcms, in ei-ther straight chain~or branched chain conflguration, with propylene oxide or ethylene oxide, e.g. a coco~ut alcohol-ethylene oxide condensate having 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 10 to 14 carbon atoms;
(4) Long chain tertiary amine oxides corresponding to the following general formula, ~ ~ ~N -~ O, wherein ~ is alkyl of about 8 to 18 carbon atcms, and R2 and ~ are each methyl or ethyl radicals. Examples of amine oxides suitable for use in this inven-tion include dimethyldodecylamine oxide, dimethyloctylami~e o~ide, dimethyldecylamine oxide, ~l ~L~42856~
dimethyltetradecylamine oxide, dimethylhexadecylamine oxide;
dimethyltetradecylamine oxide, dimethylhexadecylamine oxide;
(5) Long chain tertiary phosphine oxides corresponding to the following formula RR'R"P O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R' and R" are each alkyl or monohydroxyalkyl groups containing 1 to 3 carbon atoms.
(6) Dialkyl sulphoxides corresponding to the following formula, RR'S ~O, wherein R is an alkyl, alkenyl, beta- or gamma-monohydroxyalkyl radical or an alkyl or beta- or gamma-monohydroxy-alkyl radical containing one or two other oxygen atoms in the chain, the R groups ranging from 10 to 18 carbon atoms in chain length, and wherein R' is methyl or ethyl;
(7) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of about 8 to about 18 carbon atoms;
(8) Mono-, poly- and di-glycerides of fat forming acids;
(9) A sorbitan monoester with one or more long chain fatty acids of 8 to 20 carbon atoms or resin acids which include those sold under the trademarks l~Atlox"and "Atpet", including those modified by reaction with ethylene oxide or propylene oxide;
(10) ~n alkylbenzene containing a straight-chain alkyl group. Suitable alkylbenzenes contain an aIkyl group of 8 to 20 carbon atoms; or
(11) Condensates of ethylene oxide or propylene oxide with fatty acids.
The use of mixtures of nonionic surfactants is also within the scope of the present invention.
me concentration of the surfactant must be higher than the critical micelle concentration (CMC). The surfactant(s) can be present in a total amount of 0.5 to 32 parts by weight, usually be-t~7een 1-16 parts by weight but preferably 1-2 parts by weight and especially about 1.5 parts by weight of the concentrated em~lsion according to the invention.
Preferred surfactants are one or more of polyethylene oxide condensates of alkyl phenols, C8-C18 alkanols or fatty acids, sorbitan esters of fatty acids, polyethylene oxide sorbitan esters of mixed fatty and resin acids and polyglycerides of fatty acids, for example, NEODOL~Detergent alcohols, T~eens and Igepals.
A preferred concentrated emulsion according to the inven-tion oomprises 28-32 parts by weight of lipophilic pesticide, 28-32 parts by weight of hydroc æbon solvent,
The use of mixtures of nonionic surfactants is also within the scope of the present invention.
me concentration of the surfactant must be higher than the critical micelle concentration (CMC). The surfactant(s) can be present in a total amount of 0.5 to 32 parts by weight, usually be-t~7een 1-16 parts by weight but preferably 1-2 parts by weight and especially about 1.5 parts by weight of the concentrated em~lsion according to the invention.
Preferred surfactants are one or more of polyethylene oxide condensates of alkyl phenols, C8-C18 alkanols or fatty acids, sorbitan esters of fatty acids, polyethylene oxide sorbitan esters of mixed fatty and resin acids and polyglycerides of fatty acids, for example, NEODOL~Detergent alcohols, T~eens and Igepals.
A preferred concentrated emulsion according to the inven-tion oomprises 28-32 parts by weight of lipophilic pesticide, 28-32 parts by weight of hydroc æbon solvent,
-12-- ~l 2-6 parts by weight of an aIkanol, 1-16 parts by weight oE at least one nonionic surfactant to stabilise the emulsion, and water -to bring the total of all com-ponents of the e~ulsion to 100 parts by weight.
In the concentrated ~mulsions of the invention water usually camprises about 48.9-17 parts by weight of the emulsion.
When the emulsions are formulated with the preferred amounts of ingredients previously specified above, then water is present in amounts of about 41-28 parts by weight or more suitably 36-21 parts by weight. The emulsion forms very readily when the ratio of oil phase (oil plus pesticide) to water phase (water plus emulsifier and alkanol) is about 1.6 to 1.
A separately-prepared stable, con oe ntrated emulsion within the scope of the present invention cc~,prises components of the same chemical co~positions as described in relation to preferred emul-sions but in different proportions. Broadly these proportions are:
3.5 to 6.5 parts by weight of at least one lipophilic pesticide, 3.5 to 6.5 parts by weight of a hydrocarbon solvent, 7 to 9.5 parts by weight of an alkanol
In the concentrated ~mulsions of the invention water usually camprises about 48.9-17 parts by weight of the emulsion.
When the emulsions are formulated with the preferred amounts of ingredients previously specified above, then water is present in amounts of about 41-28 parts by weight or more suitably 36-21 parts by weight. The emulsion forms very readily when the ratio of oil phase (oil plus pesticide) to water phase (water plus emulsifier and alkanol) is about 1.6 to 1.
A separately-prepared stable, con oe ntrated emulsion within the scope of the present invention cc~,prises components of the same chemical co~positions as described in relation to preferred emul-sions but in different proportions. Broadly these proportions are:
3.5 to 6.5 parts by weight of at least one lipophilic pesticide, 3.5 to 6.5 parts by weight of a hydrocarbon solvent, 7 to 9.5 parts by weight of an alkanol
-13-6 to 14 parts by weight of at least one nonionic surfact-ant to stabilise the emulsion and water to bring the total of all components of the emulsion to 100 parts by ~eightO
m e preferences expressed with regard to each particular component of the first concentrated emulsion also hold true for the second, only the proportions are different. ~he preferred formula-tions of the second ooncentrated emulsion of the invention are:
4.5 to 5.5 parts by weight of lipophilic pesticide, 4.5 to 5.5 parts by weight of hydrocarbon solven-t, 8 to 9 parts by weight of an alkanol, 9 to 11 parts by weight of at least one nonionic surfact-ant to stabilise the emulsion and water to bring the total of all ccmponents of the emulsion to 100 parts by weight.
m e above oil-in-water concentrated emulsions may be pre-pared by any convenient technique but are preferably prepared by the combination of the nonionic surfactant with a mlxture of the hydro-carbon solvent and lipophilic pesticide and subsequently the combina-tion of the resulting three-component mixture with the alkanol and water, the latter step being accompanied by agitation to form the emLlsion. A poorer quality emulsion results when the nonionic sur-
m e preferences expressed with regard to each particular component of the first concentrated emulsion also hold true for the second, only the proportions are different. ~he preferred formula-tions of the second ooncentrated emulsion of the invention are:
4.5 to 5.5 parts by weight of lipophilic pesticide, 4.5 to 5.5 parts by weight of hydrocarbon solven-t, 8 to 9 parts by weight of an alkanol, 9 to 11 parts by weight of at least one nonionic surfact-ant to stabilise the emulsion and water to bring the total of all ccmponents of the emulsion to 100 parts by weight.
m e above oil-in-water concentrated emulsions may be pre-pared by any convenient technique but are preferably prepared by the combination of the nonionic surfactant with a mlxture of the hydro-carbon solvent and lipophilic pesticide and subsequently the combina-tion of the resulting three-component mixture with the alkanol and water, the latter step being accompanied by agitation to form the emLlsion. A poorer quality emulsion results when the nonionic sur-
-14-~4~8~1 factant (emulsifler) is added to the water phase in the emulsifica-tion step.
me concentrated emulsions of-the present invention are superior in camparison with conventional concentrate formulations previously known in the art. In particular, the formulations of the invention are stable over a broad range of temperatures, e.g., from -18C to 120C. Furthermore, the emulsions of the invention are unusual in that freezing doe s not cause separation of the oil and water phase and on thawing the emulsion remains unchanged. me high thermal stability and optical (birefringent) properties of the con-centrated emwlsions of ~he invention are indicative of a specific three-dimensional structure having specific stoichicmetry. A phase diagram, Figure 1 of the accompanying drawings, supports this view.
me three variables used to plot this diayram are:
(1) me oil phase camprising a 50% by weight solution of lipophilic pesticide in a hydrocarbon solven~, e.g., 50~ ~-cyano-3-phenoxybenzyl ~-isopropyl-p-chloro phenylacetate in Tenneco 500-100.
(2) The aqueous phase comprising a 10~ by weight solution of alkanol in water, e.g., ethylene glycol in deion-ized water.
~ i (3) The nonionic surfactant, e.g., Atlox 8916-F. In the phase diagram there are two widely separated areas, "A" and "B", in which birefringent, stable emulsions are obtained. The products obtained in between these two areas are emulsions in which an aqueous layer forms below the emulsion in less than 24 hours. While the stable emulsions are formed in areas "A" and "B", the rheological properties of the two are different and it is likely that the products differ in spatial arrangements; i.e~, the~ have different crystalline structures.
An added advantage of the emulsions of the invention is quantity of character of solvent. Because part of the organic solvent normally used is replaced by water, the formulations of the invention are less eye irritating, the quantity of solvent evapor ated to the environment is reduced, and the formulations are less expensive. Addit~onally, the use of high flash point solvents such as Tenneco 500 ~ 100 results in safer formulations because of their lower fire hazard characteristics. The present emulsions requlre a~out less than hal~ the amount of solvent as conventional emuls~on concentrates.
The stable, concentrated oll-in-water emulsions of this invention are effective for use as pesticide formulations. In particular use will, of course, depend on the pesticide used, e.g., ~nsecticide, herbicide, or fungicide. For example, when the pesticide is an insecticide the formulations of the invention can be effective for (1) control of ectoparasites in warm-blooded animals, (2) control of insects on agricultural crops and in gardens, (3) control of insects in public places as fumigant or space spray, (4) control of insects attacking trees, and (5) use to control insects in and around the home. The stability, reduced eye irritation and lower fire hazard characteristics can be particularly advantageous for these uses. IJnder normal use, the concentrated emulsions are diluted with water prior to application.
It should ~e noted that the pyrethroids of formula I
are well-known for their pesticidal properties as insecticides for control of flies, mosquitoes, cockroaches, acarids, and ticks. Accordingly, the concentrated emulsions of the invention formulated using the p~rethroids of formula I are~useful for the above-noted pest~cidal applications.
The invent~on further illustrated by the follo~ing Examples:-Example 1 A typical concentrated o~l-in-water emulsion was formed havin~ the following ingredients in the indicated proportions:
5~
Percent Weight ~-cyano-3-phenoxybenzyl ~- 30.3 -isopropyl-p-chlorophenylacetate Tenneco 500 - 100 30.3 Atloxo~ 8916TF Emulsifiers 1.5 (Polyoxyethylene (20~ sorbitan monooleate mixed esters) Water 27.9 Ethylene glycol 10.0 100. 0 The first three ingredients were combined to form a clear yellow solution which was then swlrled into a water solution of ethylene glycol to obtain an opaque white oil-in-water emulsion. The emulsion was stable when held at -18C.
Examples 2 to`7 Further concentrated oil-in-water emulsions of this invention ware formed, the`details of which are shown in Table 1 below:-., I o l~ o o ~ o ~ o ~ ~ ~ o ~ ol o ~ o o ~ ~ u~o ~ ~ ~ o u~ n o o ~ ~ ~ o H .;: tv~ ~ ~ ~1 Cl~ t~
.~
~ ~ ~ . O
a ~ ~: O O ~ O
~ ~ ~ ~ ~ O
~ ~ ~ ~ .
~Z X ~ ~ O I O
o ~ O O ~, ~ ~ O
~ ~ ~ ~ ~0 E~
Z ~ O
H (N O O ~1 ~ O O : i ~:1 ~ ~1 .
H
H
E~
U~
a ~3 _l N ~ ~rl ~1 ~ ~ ~1 O ~1 ~ R ~ u~
E~ ~ O o ,~
O ~ ~1 ~ ~1 O
~2, 1 o E~ --i ~ o ~9 O O O a~
O ~ O
Sa~
Similar emulsions were formulated by substitution of ~-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecar-boxylate, ~-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichloro-vinyl)cyclopropanecarboxylate, or ~-cyano-3-phenoxybenzyl 2,2-di-methyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate for the ~-cyano-3-phenoxybenzyl ~-isopropyl-p-chlorophenylacetate.
Exa_ple 8 A further concentrated emulsion was prepared having the following ingredients:
Percent Weight Oil phase 62 (31% ~-cyano-3-pheno~ybenyl ~-isopropyl-p-chlorophenylacetate and 31% Tenneco 500-100) Surfactant Tween* 40 1,5 (polyoxyethylene(20)sorbitan mono~
palmitate) Water phase (10% solution of 36.5 propylene glycol in deionized water) The required amount of the sur~actant was weighed and dissolved in the oil phase. The required amount of water phase was then added and the mixture shaken vigorously for 30 seconds to form a stable oil-in-water concentrated emulsion.
* Trade Mark .~
~;~3 Examples 9 to 14 Following procedures similar to those of Example 8 above, stable oil-in-water concentrated emulsions were prepared using the surfactants shown in Table 2 below:
~g !
.
~Z8S~
o ~o ~ o ~i ~A
Q~ I u~
O O~1 $-~ OO O S~
Q, U~ O S l a~
O ~ O ~ .5::
Ul Or--l S-lrC ~ a) ~
tl~.,1 ~) ~ ~1) ~) ~ ~1) ~I
Z I a) ~
HO ~ ~ ~ ~ ~ ~ ~ O
U~ ~1 ~) O ~ ~ tJ~
~:1 ~ ,~ 1 o o O
D N ~ ~ ~ ~ h ~) ~: 0~ ~ ~ a~1 ~ A
~ ~1 O ~ td Q ~)h ~to ~ ~ ~) O
E~ ~ ~ o o o o n o E~ O ~ ~ ~ ~ ~ ~ ~ ~r O _ _ _ _ _ _ P~ O a~
Z Ql ~~0 ~ I tdr~
C~
Z 1 ~3 O O t)r-l~ ~ ~) ~ ~) ~1) 0 ~1 Aa~ a~ O a) t~Q a) o ~ ~ ~>1 C X ~&
~ O ~o~o ~ O O O O O O
E~ I a)o 3 o~O
, ~~0 rO O O O
rAO O a) r-l P IP I P~ Pl 14 ~1 Z r-l ~1 0\ N
H ~) O11') r l ~r-l ~
1:1 ~: ~ O
H o\ V~-~1 O ~ I O
U~
~ tn H
~ ~ U~
H ~ h E~ a U~ ~ ~ U~
1:~ ,~ ~ ~ 1:4 P~ o *;C ~
~ C~CO *
t~l C~In 1~ J *
~C O
4~ r7r~ O ~ a :l ~ r lr~ O
~1 ~
, s u~ ~ m ~
r-l k q) tl~ cn O r-lt~ r~
X ~I r-l~I r-l r-l td ~'1 E~
*
L
me concentrated emulsions of-the present invention are superior in camparison with conventional concentrate formulations previously known in the art. In particular, the formulations of the invention are stable over a broad range of temperatures, e.g., from -18C to 120C. Furthermore, the emulsions of the invention are unusual in that freezing doe s not cause separation of the oil and water phase and on thawing the emulsion remains unchanged. me high thermal stability and optical (birefringent) properties of the con-centrated emwlsions of ~he invention are indicative of a specific three-dimensional structure having specific stoichicmetry. A phase diagram, Figure 1 of the accompanying drawings, supports this view.
me three variables used to plot this diayram are:
(1) me oil phase camprising a 50% by weight solution of lipophilic pesticide in a hydrocarbon solven~, e.g., 50~ ~-cyano-3-phenoxybenzyl ~-isopropyl-p-chloro phenylacetate in Tenneco 500-100.
(2) The aqueous phase comprising a 10~ by weight solution of alkanol in water, e.g., ethylene glycol in deion-ized water.
~ i (3) The nonionic surfactant, e.g., Atlox 8916-F. In the phase diagram there are two widely separated areas, "A" and "B", in which birefringent, stable emulsions are obtained. The products obtained in between these two areas are emulsions in which an aqueous layer forms below the emulsion in less than 24 hours. While the stable emulsions are formed in areas "A" and "B", the rheological properties of the two are different and it is likely that the products differ in spatial arrangements; i.e~, the~ have different crystalline structures.
An added advantage of the emulsions of the invention is quantity of character of solvent. Because part of the organic solvent normally used is replaced by water, the formulations of the invention are less eye irritating, the quantity of solvent evapor ated to the environment is reduced, and the formulations are less expensive. Addit~onally, the use of high flash point solvents such as Tenneco 500 ~ 100 results in safer formulations because of their lower fire hazard characteristics. The present emulsions requlre a~out less than hal~ the amount of solvent as conventional emuls~on concentrates.
The stable, concentrated oll-in-water emulsions of this invention are effective for use as pesticide formulations. In particular use will, of course, depend on the pesticide used, e.g., ~nsecticide, herbicide, or fungicide. For example, when the pesticide is an insecticide the formulations of the invention can be effective for (1) control of ectoparasites in warm-blooded animals, (2) control of insects on agricultural crops and in gardens, (3) control of insects in public places as fumigant or space spray, (4) control of insects attacking trees, and (5) use to control insects in and around the home. The stability, reduced eye irritation and lower fire hazard characteristics can be particularly advantageous for these uses. IJnder normal use, the concentrated emulsions are diluted with water prior to application.
It should ~e noted that the pyrethroids of formula I
are well-known for their pesticidal properties as insecticides for control of flies, mosquitoes, cockroaches, acarids, and ticks. Accordingly, the concentrated emulsions of the invention formulated using the p~rethroids of formula I are~useful for the above-noted pest~cidal applications.
The invent~on further illustrated by the follo~ing Examples:-Example 1 A typical concentrated o~l-in-water emulsion was formed havin~ the following ingredients in the indicated proportions:
5~
Percent Weight ~-cyano-3-phenoxybenzyl ~- 30.3 -isopropyl-p-chlorophenylacetate Tenneco 500 - 100 30.3 Atloxo~ 8916TF Emulsifiers 1.5 (Polyoxyethylene (20~ sorbitan monooleate mixed esters) Water 27.9 Ethylene glycol 10.0 100. 0 The first three ingredients were combined to form a clear yellow solution which was then swlrled into a water solution of ethylene glycol to obtain an opaque white oil-in-water emulsion. The emulsion was stable when held at -18C.
Examples 2 to`7 Further concentrated oil-in-water emulsions of this invention ware formed, the`details of which are shown in Table 1 below:-., I o l~ o o ~ o ~ o ~ ~ ~ o ~ ol o ~ o o ~ ~ u~o ~ ~ ~ o u~ n o o ~ ~ ~ o H .;: tv~ ~ ~ ~1 Cl~ t~
.~
~ ~ ~ . O
a ~ ~: O O ~ O
~ ~ ~ ~ ~ O
~ ~ ~ ~ .
~Z X ~ ~ O I O
o ~ O O ~, ~ ~ O
~ ~ ~ ~ ~0 E~
Z ~ O
H (N O O ~1 ~ O O : i ~:1 ~ ~1 .
H
H
E~
U~
a ~3 _l N ~ ~rl ~1 ~ ~ ~1 O ~1 ~ R ~ u~
E~ ~ O o ,~
O ~ ~1 ~ ~1 O
~2, 1 o E~ --i ~ o ~9 O O O a~
O ~ O
Sa~
Similar emulsions were formulated by substitution of ~-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecar-boxylate, ~-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichloro-vinyl)cyclopropanecarboxylate, or ~-cyano-3-phenoxybenzyl 2,2-di-methyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate for the ~-cyano-3-phenoxybenzyl ~-isopropyl-p-chlorophenylacetate.
Exa_ple 8 A further concentrated emulsion was prepared having the following ingredients:
Percent Weight Oil phase 62 (31% ~-cyano-3-pheno~ybenyl ~-isopropyl-p-chlorophenylacetate and 31% Tenneco 500-100) Surfactant Tween* 40 1,5 (polyoxyethylene(20)sorbitan mono~
palmitate) Water phase (10% solution of 36.5 propylene glycol in deionized water) The required amount of the sur~actant was weighed and dissolved in the oil phase. The required amount of water phase was then added and the mixture shaken vigorously for 30 seconds to form a stable oil-in-water concentrated emulsion.
* Trade Mark .~
~;~3 Examples 9 to 14 Following procedures similar to those of Example 8 above, stable oil-in-water concentrated emulsions were prepared using the surfactants shown in Table 2 below:
~g !
.
~Z8S~
o ~o ~ o ~i ~A
Q~ I u~
O O~1 $-~ OO O S~
Q, U~ O S l a~
O ~ O ~ .5::
Ul Or--l S-lrC ~ a) ~
tl~.,1 ~) ~ ~1) ~) ~ ~1) ~I
Z I a) ~
HO ~ ~ ~ ~ ~ ~ ~ O
U~ ~1 ~) O ~ ~ tJ~
~:1 ~ ,~ 1 o o O
D N ~ ~ ~ ~ h ~) ~: 0~ ~ ~ a~1 ~ A
~ ~1 O ~ td Q ~)h ~to ~ ~ ~) O
E~ ~ ~ o o o o n o E~ O ~ ~ ~ ~ ~ ~ ~ ~r O _ _ _ _ _ _ P~ O a~
Z Ql ~~0 ~ I tdr~
C~
Z 1 ~3 O O t)r-l~ ~ ~) ~ ~) ~1) 0 ~1 Aa~ a~ O a) t~Q a) o ~ ~ ~>1 C X ~&
~ O ~o~o ~ O O O O O O
E~ I a)o 3 o~O
, ~~0 rO O O O
rAO O a) r-l P IP I P~ Pl 14 ~1 Z r-l ~1 0\ N
H ~) O11') r l ~r-l ~
1:1 ~: ~ O
H o\ V~-~1 O ~ I O
U~
~ tn H
~ ~ U~
H ~ h E~ a U~ ~ ~ U~
1:~ ,~ ~ ~ 1:4 P~ o *;C ~
~ C~CO *
t~l C~In 1~ J *
~C O
4~ r7r~ O ~ a :l ~ r lr~ O
~1 ~
, s u~ ~ m ~
r-l k q) tl~ cn O r-lt~ r~
X ~I r-l~I r-l r-l td ~'1 E~
*
L
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A pesticidally-active concentrated emulsion comprising:-3.5-6.5 or 10-35 parts by weight of lipophilic pesticide, 3.5-6.5 or 10-35 parts by weight of hydrocarbon solvent, 0.1-10 parts by weight of an alkanol, 0.5-32 parts by weight of at least one nonionic surfact-ant to stabilize the emulsion, and water to bring the total of all components of the emulsion to 100 parts by weight.
2. An emulsion according to claim 1 wherein the lipophilic pesticide is a synthetic pyrethroid.
3. An emulsion according to claim 1, wherein the alkanol is a monohydroxy alcohol containing 1 to 4 carbon atoms or a dihydroxy alcohol containing 2 to 4 carbon atoms.
4. An emulsion according to claim 1, wherein the solvent is selected from alkanes, cycloalkanes or alkenes containing 1 to 12 carbon atoms or aromatics or alkylaromatics containing 6 to 20 carbon atoms or mixtures of these hydrocarbons.
5. An emulsion according to claim 1, wherein the emulsifier is one or more of (a) polyethyleneoxide condensates of fatty acids, hydrogenated fatty adcids or alkyl phenols, (b) sorbitan esters of fatty acids, (c) polyethyleneoxide sorbitan esters of mixed fatty and resin acids, and (d) di or polyglycerides of fatty acids.
6. An emulsion according to claim 1, comprising:-28-32 parts by weight of lipophilic pesticide, 28-32 parts by weight of hydrocarbon solvent, 2-6 parts by weight of an alkanol, 1-16 parts by weight of at least one nonionic surfactant to stabilise the emulsion, and water to bring the total of all components of the emulsion to 100 parts by weight.
7. An emulsion according to claim 1, comprising:-3.5-6.5 parts by weight of lipophilic pesticide, 3.5-6.5 parts by weight of hydrocarbon solvent, 7-9.5 parts of an alkanol, 6-14 parts by weight of at least one nonionic surfactant to stabilise the emulsion, and water to bring the total of all components of the emulsion to 100 parts by weight.
8. An emulsion according to any one of claim 1, 6 or 7 wherein the lipophilic pesticide is a synthetic pyrethroid, the solvent is an aromatic hydrocarbon or a mixture of aromatic hydro-carbons, the alkanol is ethylene glycol or propylene glycol and the nonionic surfactant is a fatty acid ester of ethoxylated polyols.
9. A process for the preparation of an emulsion according to claim 1, 6 or 7, wherein the nonionic surfactant is combined with a mixture of the hydrocarbon solvent and liphophilic pesticide and the resulting three component mixture is combined with agitation with the alkanol and water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2385179A | 1979-03-26 | 1979-03-26 | |
| US23,851 | 1979-03-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142850A true CA1142850A (en) | 1983-03-15 |
Family
ID=21817569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000346528A Expired CA1142850A (en) | 1979-03-26 | 1980-02-27 | Pesticidally-active concentrated oil-in- water emulsions |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS55130901A (en) |
| AU (1) | AU535901B2 (en) |
| BR (1) | BR8001763A (en) |
| CA (1) | CA1142850A (en) |
| FR (1) | FR2452249A1 (en) |
| GB (1) | GB2048675B (en) |
| IT (1) | IT1130077B (en) |
| MX (1) | MX5939E (en) |
| NL (1) | NL8001713A (en) |
| ZA (1) | ZA801708B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP143A (en) * | 1989-03-13 | 1991-09-27 | Scient Chemicals Proprietory Ltd | Pesticidal Fomulation |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3004249A1 (en) * | 1980-02-06 | 1981-08-13 | Desowag-Bayer Holzschutz GmbH, 4000 Düsseldorf | WOOD PROTECTIVE CONCENTRATE AND PRODUCT MADE THEREOF FOR THE PRESERVATION OF WOOD AND WOOD MATERIALS |
| US4607050A (en) * | 1981-10-19 | 1986-08-19 | Wellcome Australia Limited | Method of controlling insects and parasites with an aqueous localized pour-on formulation |
| US4460406A (en) * | 1982-04-19 | 1984-07-17 | Monsanto Company | Herbicidal concentrated emulsions |
| EP0131735A1 (en) * | 1983-06-16 | 1985-01-23 | Itt Industries, Inc. | Insecticidal mixture |
| WO1986004214A1 (en) * | 1985-01-24 | 1986-07-31 | Takeda Chemical Industries, Ltd. | Agricultural chemical preparation having alleviated toxicity against fish |
| ZW3486A1 (en) * | 1985-03-12 | 1986-10-01 | Bayer Ag | Macroemulsions |
| ZW3586A1 (en) * | 1985-03-12 | 1986-06-11 | Bayer Ag | Macroemulsions |
| JPH0676281B2 (en) * | 1986-01-17 | 1994-09-28 | 住友化学工業株式会社 | Stabilized oil-in-water pesticide composition |
| JP2559704B2 (en) * | 1986-04-12 | 1996-12-04 | 有恒薬品工業 株式会社 | Oil-in-water composition of pesticide active ingredient |
| JP2579755B2 (en) * | 1986-07-17 | 1997-02-12 | 塩野義製薬株式会社 | New suspension pesticide formulation |
| GB2203339A (en) * | 1987-04-13 | 1988-10-19 | Ciba Geigy Ag | Microbicidal formulation |
| CA1336863C (en) * | 1988-05-25 | 1995-09-05 | Gottfried Lichti | Controlled release composition |
| EP0478578A4 (en) * | 1989-04-17 | 1992-10-07 | S.C. Johnson & Son, Inc. | Water-soluble stable arthropodicidally-active foam matrix and method of manufacture |
| US6039966A (en) * | 1997-12-30 | 2000-03-21 | Aquatrols Corporation Of America, Inc. | Agrochemical emulsion concentrates |
| SA06270491B1 (en) * | 2005-12-27 | 2010-10-20 | سينجنتا بارتيسبيشنز ايه جي | Herbicidal CompositionComprising of 2,2-Dimethyl-Propionic Acid 8-(2,6-Diethyl-4-Methyl-Phenyl)-9-Oxo-1,2,4,5-Tetrahydro-9H-Pyrazolo[1,2 d] [1,4,5]Oxadiazepin-7-yl Ester and an alcohol |
| CN104735986B (en) * | 2012-10-19 | 2018-08-31 | 先正达参股股份有限公司 | Liquid agrochemical composition including polymeric viscosifier and containing alcohol solvent system and with the liquid weeding composition containing alcohol solvent system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784140A (en) * | 1954-11-03 | 1957-03-05 | Rohm & Haas | Emulsifier composition and insecticidal emulsions obtained therewith |
-
1980
- 1980-02-27 CA CA000346528A patent/CA1142850A/en not_active Expired
- 1980-03-24 MX MX808720U patent/MX5939E/en unknown
- 1980-03-24 BR BR8001763A patent/BR8001763A/en not_active IP Right Cessation
- 1980-03-24 NL NL8001713A patent/NL8001713A/en not_active Application Discontinuation
- 1980-03-24 AU AU56766/80A patent/AU535901B2/en not_active Expired
- 1980-03-24 IT IT20874/80A patent/IT1130077B/en active
- 1980-03-24 JP JP3632380A patent/JPS55130901A/en active Granted
- 1980-03-24 FR FR8006486A patent/FR2452249A1/en active Granted
- 1980-03-24 ZA ZA00801708A patent/ZA801708B/en unknown
- 1980-03-24 GB GB8009793A patent/GB2048675B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP143A (en) * | 1989-03-13 | 1991-09-27 | Scient Chemicals Proprietory Ltd | Pesticidal Fomulation |
| US5194264A (en) * | 1989-03-13 | 1993-03-16 | Scientific Chemicals (Proprietary) Limited | Pesticidal formulation |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8001713A (en) | 1980-09-30 |
| JPS6362481B2 (en) | 1988-12-02 |
| GB2048675A (en) | 1980-12-17 |
| AU5676680A (en) | 1980-10-02 |
| BR8001763A (en) | 1980-11-18 |
| GB2048675B (en) | 1983-01-12 |
| FR2452249A1 (en) | 1980-10-24 |
| AU535901B2 (en) | 1984-04-12 |
| ZA801708B (en) | 1981-03-25 |
| IT8020874A0 (en) | 1980-03-24 |
| MX5939E (en) | 1984-08-30 |
| IT1130077B (en) | 1986-06-11 |
| JPS55130901A (en) | 1980-10-11 |
| FR2452249B1 (en) | 1984-10-19 |
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