CA1187409A - Insecticide mixtures containing fatty acids - Google Patents
Insecticide mixtures containing fatty acidsInfo
- Publication number
- CA1187409A CA1187409A CA000421187A CA421187A CA1187409A CA 1187409 A CA1187409 A CA 1187409A CA 000421187 A CA000421187 A CA 000421187A CA 421187 A CA421187 A CA 421187A CA 1187409 A CA1187409 A CA 1187409A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- insecticide
- fatty acid
- meo
- insects
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Abstract
ABSTRACT OF THE DISCLOSURE
Mixtures of organic insecticides of the organochlorine type or of selected organophosphate types or of the carbamate type, with certain fatty acids or their salts, have been found to have enhanced insecticidal activity. The fatty acids found operative are the unsaturated 18-carbon atom ones. The mixtures are toxic to both sucking insects and defolia-tors. The weight ratio of organochlorine or organophosphate or carbamate to fatty acid can range from about 1:1 to about 1:200, respectively. The amounts of the organochlorine, organophosphate or carbamate required for substantial effectiveness can be reduced significantly by concurrent use of the fatty acid. The fatty acid is more environmentally acceptable than the other types of insecticides mentioned. A broader spectrum of insects can be protected against.
Mixtures of organic insecticides of the organochlorine type or of selected organophosphate types or of the carbamate type, with certain fatty acids or their salts, have been found to have enhanced insecticidal activity. The fatty acids found operative are the unsaturated 18-carbon atom ones. The mixtures are toxic to both sucking insects and defolia-tors. The weight ratio of organochlorine or organophosphate or carbamate to fatty acid can range from about 1:1 to about 1:200, respectively. The amounts of the organochlorine, organophosphate or carbamate required for substantial effectiveness can be reduced significantly by concurrent use of the fatty acid. The fatty acid is more environmentally acceptable than the other types of insecticides mentioned. A broader spectrum of insects can be protected against.
Description
~7~
This invention is concerlled Witll insecticides and enhancing their insecticldal effect using partial replacement compounds whlch are more environmentally acceptable.
One of the main means of controlling lnsect infestation has been through the use of chemical insecticides. ~t the present time there are 15,000 registered pecticides within North America of which about 6,000 are sold in Canada. The pesticides generally fall into five major categories viz: chlorinated hydrocarbons e.g. DDT, lindane, metho~ychlor, etc.; organophosphates e.g. malathion, dibrom, dia~inon [trademarkl, phosphamedon9 etc.; carbamate compounds e.g. baygon [trademark], sevin [trademark], ~ectran ~trademark], etc.; inorganic compounds e.g. arsenic, sulphur, borax, etc.; and botanical compounds e.g. pyrethrum, strychnine, nicotine, etc. The chemical insecticides have been frequently used against major forest pests, e.g. DDT against spruce budworm, and have in many cases, been quite successful.
The chemical insecticides, with the exception of the botanical ones, have several disadvantages. Most of them are highly toxic to Eish, wildlife, and humans and must be used with caution. They are usually not natural biological constituents and tend to persist for long lengths of time after their initial application. This i8 best exèmplified by the chlorinated hydrocarbons which because o~ their persistence have passed througll the animal food chain and caused egg shell thinning and egg breakage in many species of blrds.
BesLdes their initial toxic effect, these compounds can have sub-acute effects on non-target fauna and flora thereby causing biochemi-cal, behavioural and physiological changes as well as reproductive fail-ure. Most of the chemical insecticides are ~uite expensive and with the current petroleum shortage, difficult to obtain. The breakdown products and secondary metabolites of most petrochemical pesticldes and their impact on humans and other living organisms are poorly understood.
Recent research has shown that the unsaturated C18 fatty acids or their salts (C18:X) are highly toxic to soft bodied insects including aphids, mealybugs, whitefly, pear psylla, rose slugs, etc. (G. Puritch, 1978 Symposium on the Pharmacological ~ffects of LipLds AOCS monograph No. 5, 105-112). During investigations, it was further discovered that .~
3~
combination of the unsaturated 1~ carbon fatty acids and/or salts with either organochlorines or organophosphates or carbamate insecticides gave an unexpectedly high degree of ~nsecticidal activity when topically appliedO Thls unique finding has permitted a reduction of the petrochem ical pesticide required for suitable pest control and has provided an increase in the spectrum of insect pests controlled. For example, we found the C18:X acids, especially oleic and linoleic and their salts in solution in concentrations from 0~25 to 5~0% in combination with the or~anochlorines, especially methoxychlor in A conceDtration range of 50 ppm to 50,000 ppm or in combination with organophosphates, especially diazinon in a concentration range of 50 ppm to 50,000 ppm, effective for the control of insect pests.
Summary of the In~ention The invention thus provides a mixture having enhanced insecti-cidal activity comprlsing:
(a) an insecticide active against defoliating insects selected from organochlorlne compounds, organic esters of phosphoric or thiophosphoric acids and carbamates, and mixtures thereof, and tb) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by weight of (a) + (b~.
The invelltion includes a method of protecting susceptible plants agains~ both sucking lnsects and defoliating insects comprisLng providing concurrently on the plant surEaces or directly on the insects, both (a) an insecticide active against defoliating insects selected from organochlorine compounds, organic eseers of phosphoric or thiophosphoric acids and carbamates, and mixtures thereof, and (b) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by wt. of (a) + (~). Preferably (a) and (b) are applied together as a mixture.
The fatty acid (b) is selected from oleic acid, linoleic acid, their soaps ~salts) and mixtures thereof. Linolenic acid or ricinoleic acid may be present~ The cation forming the salt o~ soap with the fatty acid usually is selected from sodium, potassium or ammonium. Other cations that may be utllized include ~inc, copper and mono-, di- or tri-ethanolamines.
In the mixture, or in use, the proportions of ln6ecticide (a) to fatty acid (b) may range from about 1:200 to about 1:1 by wt., prefer-ably about 1:20 to about 1:2.
The mixture may be used in the form of a solution in any suit-able solvent. In one preferred embodiment an aqueous solution i8 used inwhich the concentration of insecticide (a) ranges from about 0~005 to about 5% by wt., and the concentration of fatty acid or its salt (b) ranges from about 0.25 to about 5% by wt. P~eferably the soap of the fatty acid is used in aqueous solution.
In another preferred aspec~, we formulate the concentrated soaps with alcohols consisting of methanol, ethanol or lsopropanol at various concentrations up to 35%. Preferably, we also use xylene in the methoxychlor combination (xylene can reach up to 25% concentration).
Other suitable organic solvents such as kerosene~ hexane or acetone could also be used in the formulation. In the acid form the fatty acids are substantially water insoluble and along with ~08~ of ~he petrochemical pesticides in the mixture, elther have to be solubllized ln organic solvents or as emulsiflable concentrates.
We have used varlous anionic/nonionic blends of emulsifiers such as Witco Chem. Canada Ltd. Sponto~ 300T and 500T partlcularly for our methoxychlor-soap mixtures. Other types of emulsifiers; anionlc, cationic and nonionic could all be used in the various mixtures. Concen-tration~ would vary up to 10~ by weight.
Other solvents, detergents, wetting agents, carriers, ad~u-vants, etc., may be used as known in the art.
Suitable organochlorine insecticides include methoxychlor[1~ trichloro-2,2-bistp-methoxyphenyl)ethane], lindane, benzene hexa-chloride, endosulfan, fenitrothion, and pentachlorophenol.
Suitable insecticidal esters of phosphoric and thiophosphoric acids include dia~inon ~ [phosphorothioic acid 0~0-diethyl-0-(2-isopro-pyl-6-methyl-4-pyrimidinyl)ester], malathion [S-(1,2-dicarbethoxyethyl)-O,O-dimethyldithiophosph~te], phosphamedon, meta-systox ~ trlchlorofon~
Abate ~ , dichlorovos and Dur~ban ~, also dimethoate.
Suitable carbamate insecticides include Sevln ~ [1-naphthyl-N-methycarbamate], Zectran ~ , Baygon ~ and Matacil ~ O
The following examples are illustrative.Example 1 Test of unsaturated C18 salts (soaps) in combinatlon with methoxychlor for wintermoth (Operophtera brumata) control.
Host plant: Apples, cv. Spartan Sample Unlt and Procedure: Wintermoth larvae (4th or 5th lnstar) were separated from their foliage and separated into groups of 25. ~Iree groups were selected at random and assigned to the following 22 treatments:
(a) H20 (1) 0.005 MeO + 1~0 KO
10 (b) 0.001% MeO (methoxychlor) (m) 0.01 MeO + 1.0 KO
(c) 0.005 MeO (n) 0.05 MeO + 1.0 KO
(d) 0.01 MeO (o) 0.1 MeO + 1.0 KO
~e) 0.05 MeO (p) 0.01 MeO ~ 0.25 KO
(f) 0.10 MeO (q~ 0.01 MeO ~ 0O5 KO
15 (g) 0.5% KO (C18:X salts) (r) 0.01 MeO + 2.0 KO
(h) 1.0% KO (s) 0.01 MeO ~ 5.0 K0 (i) 2.0 KO (t) lZ Coco soap (~) 5.0 KO (u) 2% Coco soap (k~ 0.001 MeO ~ 1.0 KO (v~ 1% Coco soap ~ 0.05 MeO
These solutions were made up fresh be~ore use. The unsaturated fatty acld salts were made by neutralizing oleic and l~noleic (77.0%:7.0%) with potassium hydroxide (KO). The methoxyc~lor (MeO) was a standard retall grade. Larvae were sprayed to wetting with a hand pump sprayer, blotted dry and returned to fresh apple leaves. Mortality was assessed by count-ing living and dead larvae 24 hours after treatment~ "Coco soap" is thepotassium soap of coconut oil fatty acids.
Results are given in Table 1.
Table 1 Percent Mortality Solution % H20 0.25K0 005KO1.0KO2.0KO5,0K0 1%Coco 2%Coco H20 0 ' 24.0 18.7 81.390.093.0 97.3 0.001 MeO 8.0 88.0 0.005 MeO 1.3 96.0 0.01 MeO 1.3 47.7 91.0 98.694.3100.0 0.05 ~feO 8.7 100.0 100.0 0.10 MeO 60.0 93.0 .
1/ Average of 3 replicates, each replicate had 25 larvae ~7~3~
l'he synergistic interactlon of the methoxychlor with ~he unsaturated Cl8 salts is clearly evident. A combination of 1.0% KO with about 0.01% MeO
would provide a suitable degree of wintermoth control.
Example 2 Test of unsaturated C18 fatty acid salts (soaps) in S combination with methoxychlor for control of wintermoth (Operophtera brumata).
. .
Materials and Methods:
Larvae were obtained from a Gary oak and separated into groups of 25. The insects were sprayed to wetting with the solutions using a common hand-pump sprayer. Three groups of 25 were used for each treat-ment concentration. After spraylng, the insects were put on fresh foli-age in a plastic container and msintained for 24 hours before assessment.
Treatments conslsted of the following:
(a) O.Ol~ MeO (methoxychlor) (i) 0.13% MeO + 1% KO
(b) 0.03% MeO (~) 0.19% MeO + 1% KO
(c) 0.06% MeO (k) l.O% KO
(d) 0.13 MeO (1) H20 (control) (e) 0.19 MeO (m) untreated control (f) 0.01% MeO ~ l% KO (Clg:X salts) 2n (g) 0.03% MeO + 1% KO
(h) 0.06% MeO + 1% KO
The fatty acid treatment consisted of potassium oleate plus potassium linoleate (77:7%)~
Results:
Results of this experltnent are shown in Table 2. The methoxy-chlor (MeO)-soap combination gave higher mortallty than either the MeO or soap alone, thus they acted synergistically. Increasing the MeO concen-tration for .01% to 0.19% had virtually no effect on mortsllty. Even when combined with soap, increasing the MeO concentration did not increase mortality.
3~
Table 2 Effect of methoxychlor and soap on mortality of wintermoth larvae % Mortality Solution % Rep 1 Rep 2 Rep 3 Aver 0.01 MeO 20* 44 35 32.9 0.03 MeO 46 56 52 51.3 0.06 MeO 44 56 52 50.6 0.13 MeO 50 52 44 48.6 0.19 MeO ~2 56 48 65.3 0.01 MeO ~ 1% KO 92 92 88 90.7 0.03 MeO + 1% KO 92 73 69 88.3 0.06 MeO ~ 1% KO 77 88 80 81.7 0.13 MeO + 1% KO 84 96 96 92.0 0.19 MeO + 1% KO 92.3 84 96 90.7 1% KO 48 48 68 54.7 Control (treated) 0 4 4 2.7 Control (untreated) O 4 4 2.7 -- -- ._ n,. ~_ _ _ r * each repllcation contained 25 larvae Exflmple 3 Test of unsaturated Clg salts (soaps) in combination with methoxychlor for control of gypsy moth (Lymantrla dispar L.) Host plant: Oak Materials and Methods:
A solution of 18 carbon atom, unsaturated fatty acid salts oleate and linoleate (C18:1 ~ C18:2; 77%:7%) was made up fresh. ~irst or second instar larvae of gypsy moth were selected and separated in~o groups of 25, three groups were randomly selected and assigned to the following treatments:
(a) 1% Clg:l + Clg:2 (77%:7%) salts (KO) (b) 2~ KO
(c) 1% KO + 0.17 MeO
(d) 2% KO + 0.1% MeO
(e) Control~
Larvae were sprayed to wetting with a hand sprayer, placed on oak leaves and mortality assessed after 24 hours.
Results are shown in Table 3.
Table 3 % Mortality Solution Ist Instar 2nd Instar 1% KO 52 0 5i.3
This invention is concerlled Witll insecticides and enhancing their insecticldal effect using partial replacement compounds whlch are more environmentally acceptable.
One of the main means of controlling lnsect infestation has been through the use of chemical insecticides. ~t the present time there are 15,000 registered pecticides within North America of which about 6,000 are sold in Canada. The pesticides generally fall into five major categories viz: chlorinated hydrocarbons e.g. DDT, lindane, metho~ychlor, etc.; organophosphates e.g. malathion, dibrom, dia~inon [trademarkl, phosphamedon9 etc.; carbamate compounds e.g. baygon [trademark], sevin [trademark], ~ectran ~trademark], etc.; inorganic compounds e.g. arsenic, sulphur, borax, etc.; and botanical compounds e.g. pyrethrum, strychnine, nicotine, etc. The chemical insecticides have been frequently used against major forest pests, e.g. DDT against spruce budworm, and have in many cases, been quite successful.
The chemical insecticides, with the exception of the botanical ones, have several disadvantages. Most of them are highly toxic to Eish, wildlife, and humans and must be used with caution. They are usually not natural biological constituents and tend to persist for long lengths of time after their initial application. This i8 best exèmplified by the chlorinated hydrocarbons which because o~ their persistence have passed througll the animal food chain and caused egg shell thinning and egg breakage in many species of blrds.
BesLdes their initial toxic effect, these compounds can have sub-acute effects on non-target fauna and flora thereby causing biochemi-cal, behavioural and physiological changes as well as reproductive fail-ure. Most of the chemical insecticides are ~uite expensive and with the current petroleum shortage, difficult to obtain. The breakdown products and secondary metabolites of most petrochemical pesticldes and their impact on humans and other living organisms are poorly understood.
Recent research has shown that the unsaturated C18 fatty acids or their salts (C18:X) are highly toxic to soft bodied insects including aphids, mealybugs, whitefly, pear psylla, rose slugs, etc. (G. Puritch, 1978 Symposium on the Pharmacological ~ffects of LipLds AOCS monograph No. 5, 105-112). During investigations, it was further discovered that .~
3~
combination of the unsaturated 1~ carbon fatty acids and/or salts with either organochlorines or organophosphates or carbamate insecticides gave an unexpectedly high degree of ~nsecticidal activity when topically appliedO Thls unique finding has permitted a reduction of the petrochem ical pesticide required for suitable pest control and has provided an increase in the spectrum of insect pests controlled. For example, we found the C18:X acids, especially oleic and linoleic and their salts in solution in concentrations from 0~25 to 5~0% in combination with the or~anochlorines, especially methoxychlor in A conceDtration range of 50 ppm to 50,000 ppm or in combination with organophosphates, especially diazinon in a concentration range of 50 ppm to 50,000 ppm, effective for the control of insect pests.
Summary of the In~ention The invention thus provides a mixture having enhanced insecti-cidal activity comprlsing:
(a) an insecticide active against defoliating insects selected from organochlorlne compounds, organic esters of phosphoric or thiophosphoric acids and carbamates, and mixtures thereof, and tb) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by weight of (a) + (b~.
The invelltion includes a method of protecting susceptible plants agains~ both sucking lnsects and defoliating insects comprisLng providing concurrently on the plant surEaces or directly on the insects, both (a) an insecticide active against defoliating insects selected from organochlorine compounds, organic eseers of phosphoric or thiophosphoric acids and carbamates, and mixtures thereof, and (b) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by wt. of (a) + (~). Preferably (a) and (b) are applied together as a mixture.
The fatty acid (b) is selected from oleic acid, linoleic acid, their soaps ~salts) and mixtures thereof. Linolenic acid or ricinoleic acid may be present~ The cation forming the salt o~ soap with the fatty acid usually is selected from sodium, potassium or ammonium. Other cations that may be utllized include ~inc, copper and mono-, di- or tri-ethanolamines.
In the mixture, or in use, the proportions of ln6ecticide (a) to fatty acid (b) may range from about 1:200 to about 1:1 by wt., prefer-ably about 1:20 to about 1:2.
The mixture may be used in the form of a solution in any suit-able solvent. In one preferred embodiment an aqueous solution i8 used inwhich the concentration of insecticide (a) ranges from about 0~005 to about 5% by wt., and the concentration of fatty acid or its salt (b) ranges from about 0.25 to about 5% by wt. P~eferably the soap of the fatty acid is used in aqueous solution.
In another preferred aspec~, we formulate the concentrated soaps with alcohols consisting of methanol, ethanol or lsopropanol at various concentrations up to 35%. Preferably, we also use xylene in the methoxychlor combination (xylene can reach up to 25% concentration).
Other suitable organic solvents such as kerosene~ hexane or acetone could also be used in the formulation. In the acid form the fatty acids are substantially water insoluble and along with ~08~ of ~he petrochemical pesticides in the mixture, elther have to be solubllized ln organic solvents or as emulsiflable concentrates.
We have used varlous anionic/nonionic blends of emulsifiers such as Witco Chem. Canada Ltd. Sponto~ 300T and 500T partlcularly for our methoxychlor-soap mixtures. Other types of emulsifiers; anionlc, cationic and nonionic could all be used in the various mixtures. Concen-tration~ would vary up to 10~ by weight.
Other solvents, detergents, wetting agents, carriers, ad~u-vants, etc., may be used as known in the art.
Suitable organochlorine insecticides include methoxychlor[1~ trichloro-2,2-bistp-methoxyphenyl)ethane], lindane, benzene hexa-chloride, endosulfan, fenitrothion, and pentachlorophenol.
Suitable insecticidal esters of phosphoric and thiophosphoric acids include dia~inon ~ [phosphorothioic acid 0~0-diethyl-0-(2-isopro-pyl-6-methyl-4-pyrimidinyl)ester], malathion [S-(1,2-dicarbethoxyethyl)-O,O-dimethyldithiophosph~te], phosphamedon, meta-systox ~ trlchlorofon~
Abate ~ , dichlorovos and Dur~ban ~, also dimethoate.
Suitable carbamate insecticides include Sevln ~ [1-naphthyl-N-methycarbamate], Zectran ~ , Baygon ~ and Matacil ~ O
The following examples are illustrative.Example 1 Test of unsaturated C18 salts (soaps) in combinatlon with methoxychlor for wintermoth (Operophtera brumata) control.
Host plant: Apples, cv. Spartan Sample Unlt and Procedure: Wintermoth larvae (4th or 5th lnstar) were separated from their foliage and separated into groups of 25. ~Iree groups were selected at random and assigned to the following 22 treatments:
(a) H20 (1) 0.005 MeO + 1~0 KO
10 (b) 0.001% MeO (methoxychlor) (m) 0.01 MeO + 1.0 KO
(c) 0.005 MeO (n) 0.05 MeO + 1.0 KO
(d) 0.01 MeO (o) 0.1 MeO + 1.0 KO
~e) 0.05 MeO (p) 0.01 MeO ~ 0.25 KO
(f) 0.10 MeO (q~ 0.01 MeO ~ 0O5 KO
15 (g) 0.5% KO (C18:X salts) (r) 0.01 MeO + 2.0 KO
(h) 1.0% KO (s) 0.01 MeO ~ 5.0 K0 (i) 2.0 KO (t) lZ Coco soap (~) 5.0 KO (u) 2% Coco soap (k~ 0.001 MeO ~ 1.0 KO (v~ 1% Coco soap ~ 0.05 MeO
These solutions were made up fresh be~ore use. The unsaturated fatty acld salts were made by neutralizing oleic and l~noleic (77.0%:7.0%) with potassium hydroxide (KO). The methoxyc~lor (MeO) was a standard retall grade. Larvae were sprayed to wetting with a hand pump sprayer, blotted dry and returned to fresh apple leaves. Mortality was assessed by count-ing living and dead larvae 24 hours after treatment~ "Coco soap" is thepotassium soap of coconut oil fatty acids.
Results are given in Table 1.
Table 1 Percent Mortality Solution % H20 0.25K0 005KO1.0KO2.0KO5,0K0 1%Coco 2%Coco H20 0 ' 24.0 18.7 81.390.093.0 97.3 0.001 MeO 8.0 88.0 0.005 MeO 1.3 96.0 0.01 MeO 1.3 47.7 91.0 98.694.3100.0 0.05 ~feO 8.7 100.0 100.0 0.10 MeO 60.0 93.0 .
1/ Average of 3 replicates, each replicate had 25 larvae ~7~3~
l'he synergistic interactlon of the methoxychlor with ~he unsaturated Cl8 salts is clearly evident. A combination of 1.0% KO with about 0.01% MeO
would provide a suitable degree of wintermoth control.
Example 2 Test of unsaturated C18 fatty acid salts (soaps) in S combination with methoxychlor for control of wintermoth (Operophtera brumata).
. .
Materials and Methods:
Larvae were obtained from a Gary oak and separated into groups of 25. The insects were sprayed to wetting with the solutions using a common hand-pump sprayer. Three groups of 25 were used for each treat-ment concentration. After spraylng, the insects were put on fresh foli-age in a plastic container and msintained for 24 hours before assessment.
Treatments conslsted of the following:
(a) O.Ol~ MeO (methoxychlor) (i) 0.13% MeO + 1% KO
(b) 0.03% MeO (~) 0.19% MeO + 1% KO
(c) 0.06% MeO (k) l.O% KO
(d) 0.13 MeO (1) H20 (control) (e) 0.19 MeO (m) untreated control (f) 0.01% MeO ~ l% KO (Clg:X salts) 2n (g) 0.03% MeO + 1% KO
(h) 0.06% MeO + 1% KO
The fatty acid treatment consisted of potassium oleate plus potassium linoleate (77:7%)~
Results:
Results of this experltnent are shown in Table 2. The methoxy-chlor (MeO)-soap combination gave higher mortallty than either the MeO or soap alone, thus they acted synergistically. Increasing the MeO concen-tration for .01% to 0.19% had virtually no effect on mortsllty. Even when combined with soap, increasing the MeO concentration did not increase mortality.
3~
Table 2 Effect of methoxychlor and soap on mortality of wintermoth larvae % Mortality Solution % Rep 1 Rep 2 Rep 3 Aver 0.01 MeO 20* 44 35 32.9 0.03 MeO 46 56 52 51.3 0.06 MeO 44 56 52 50.6 0.13 MeO 50 52 44 48.6 0.19 MeO ~2 56 48 65.3 0.01 MeO ~ 1% KO 92 92 88 90.7 0.03 MeO + 1% KO 92 73 69 88.3 0.06 MeO ~ 1% KO 77 88 80 81.7 0.13 MeO + 1% KO 84 96 96 92.0 0.19 MeO + 1% KO 92.3 84 96 90.7 1% KO 48 48 68 54.7 Control (treated) 0 4 4 2.7 Control (untreated) O 4 4 2.7 -- -- ._ n,. ~_ _ _ r * each repllcation contained 25 larvae Exflmple 3 Test of unsaturated Clg salts (soaps) in combination with methoxychlor for control of gypsy moth (Lymantrla dispar L.) Host plant: Oak Materials and Methods:
A solution of 18 carbon atom, unsaturated fatty acid salts oleate and linoleate (C18:1 ~ C18:2; 77%:7%) was made up fresh. ~irst or second instar larvae of gypsy moth were selected and separated in~o groups of 25, three groups were randomly selected and assigned to the following treatments:
(a) 1% Clg:l + Clg:2 (77%:7%) salts (KO) (b) 2~ KO
(c) 1% KO + 0.17 MeO
(d) 2% KO + 0.1% MeO
(e) Control~
Larvae were sprayed to wetting with a hand sprayer, placed on oak leaves and mortality assessed after 24 hours.
Results are shown in Table 3.
Table 3 % Mortality Solution Ist Instar 2nd Instar 1% KO 52 0 5i.3
2% KO 48.7 1% KO + 0.1% MeO 100.0 86.6 2% KO ~ 0.1% MeO
Control 0~0 0.0 These results show that a comblnation of methoxychlor plus the unsaturated C18 fatty acids gives a high degree of mortality to gypsy moth larvae. Although methoxychlor alone was not incl~lded in this test, results Erom tests by other groups have shown that it is relatively ineffective against gypsy moth larvae.
E~ample 4 Test of unsaturated C18 salts (soaps) in combination with methoxychlor for elm leaf beetle control Test: cond~lcted by Dr. T.R. Renault, Canadian Forest~y Service, Maritime Forest Research Center, P.O. Box 4000, Fredericton, New Brunswick, Materi~ls and ~lethods:
~ duLt elm leaf beetles were collected and placed in three plas~
tlc transparent cages (30 x 30 x 46 cm) with nylon mesh tops. Beetles were topically tre~ted and then returned to hardwood folLage in the cages.
Solutiolls were made up before use and consisted of (a) 3~0~ potassium oleate ~ potassium linoleate; 77%:7% (KO)~ or KO + 0.01% methoxychlor (KO
MeO). ~fortality was assessed after 24 hours.
Results are given in Table 4. Table 4 shows the effect of KO and KO + MeO combination on elm leaf beetle mortality.
Table 4 . _ . ... ~
Treanlent Cage #1 Cage #2 (Mean) Control Spray Regime % % % % % ~O % %
living dead living dead living dead living dead _ . .... _ __ ~
Control 0~0 0.0 These results show that a comblnation of methoxychlor plus the unsaturated C18 fatty acids gives a high degree of mortality to gypsy moth larvae. Although methoxychlor alone was not incl~lded in this test, results Erom tests by other groups have shown that it is relatively ineffective against gypsy moth larvae.
E~ample 4 Test of unsaturated C18 salts (soaps) in combination with methoxychlor for elm leaf beetle control Test: cond~lcted by Dr. T.R. Renault, Canadian Forest~y Service, Maritime Forest Research Center, P.O. Box 4000, Fredericton, New Brunswick, Materi~ls and ~lethods:
~ duLt elm leaf beetles were collected and placed in three plas~
tlc transparent cages (30 x 30 x 46 cm) with nylon mesh tops. Beetles were topically tre~ted and then returned to hardwood folLage in the cages.
Solutiolls were made up before use and consisted of (a) 3~0~ potassium oleate ~ potassium linoleate; 77%:7% (KO)~ or KO + 0.01% methoxychlor (KO
MeO). ~fortality was assessed after 24 hours.
Results are given in Table 4. Table 4 shows the effect of KO and KO + MeO combination on elm leaf beetle mortality.
Table 4 . _ . ... ~
Treanlent Cage #1 Cage #2 (Mean) Control Spray Regime % % % % % ~O % %
living dead living dead living dead living dead _ . .... _ __ ~
3.Q%KO 62(34) 38(21) 60(27) 40(18) 61(61) 39(39) 96(22) 4(1) 1.0%KO+0.01% MeO 15(3) 85(71) 17(4) 83(19 ¦16(7) 84(36) 98(62) 2(1) 3.0~KO+0.01% MeO 10(3) 90(28) 8(2) 92(24) 9(5) 91(52) 100(63) 0(0) ~ . . _ .................... . . __ Note: Bracketed figures accompanying percentages represent actual number of larvae.
It is apparent from these results that both the soap/methoxy-chlor ~ixture and soap alone produced significant kill when compared to the small degree of mortality in the control (1ess than 3%). It also shows that a combination of KO soap + methoxychlor is more effective than soap alone. Although metho~ychlor alone was not tr-led, label recommenda-tions indicate that 6.0% active ingredient is needed for acceptable con-trol. ~lis is substantially greater than the 0.01% methoxychlor used in the combination with the C1g unsaturated salts.
The eEfect of treatment on beetle mortality over ti~e is~ shown in Table 5. For thls test, beetles in cage 1 were treated w1th water, those in cage 2 w,ith 3.0% KO and those in Cage 3 with 3.0% KO + O.OlX MeO.
It is evident that tllere was little increase in mortality after the first four hours after treatmellt.
Table S
. __ .~ ~ . ...
H20 treated 3.0% RO 3.0% KO + O.OlX MeO
CaRe ~1 Cage #2 Cage #3 . ~ _ (111 beeties = (116 beetles) Mortallty: Cumulative Total _____ ____ No. (%) No (%) No (%) _ .. __ ... _.
It is apparent from these results that both the soap/methoxy-chlor ~ixture and soap alone produced significant kill when compared to the small degree of mortality in the control (1ess than 3%). It also shows that a combination of KO soap + methoxychlor is more effective than soap alone. Although metho~ychlor alone was not tr-led, label recommenda-tions indicate that 6.0% active ingredient is needed for acceptable con-trol. ~lis is substantially greater than the 0.01% methoxychlor used in the combination with the C1g unsaturated salts.
The eEfect of treatment on beetle mortality over ti~e is~ shown in Table 5. For thls test, beetles in cage 1 were treated w1th water, those in cage 2 w,ith 3.0% KO and those in Cage 3 with 3.0% KO + O.OlX MeO.
It is evident that tllere was little increase in mortality after the first four hours after treatmellt.
Table S
. __ .~ ~ . ...
H20 treated 3.0% RO 3.0% KO + O.OlX MeO
CaRe ~1 Cage #2 Cage #3 . ~ _ (111 beeties = (116 beetles) Mortallty: Cumulative Total _____ ____ No. (%) No (%) No (%) _ .. __ ... _.
4 hrs. after treatment l (0.8) 44 (39) 96 (83) 8 hrs. after treatment 2 (1.7) 46 ~41) 105 (91) 16 hrs. after treatment 2 (1.7) 48 (43) 113 (97) 24 hrs. after treatment 2 (1.7) 51 (46) 113 (97) 48 hrs. after treatment 3 (2.5) ~4 (67) _ (97) Example 5 Test of unsaturated C18 fatty acid salts (soaps) in combination with dlazlnon ~ for control of earwigs (Forficula auricularia).
Materials and ~1ethods:
Adult F. auricularia were collected from the field and separated into groups of 25. Three replicates of each group were assigned to the following treatments:
(a) water (~) 0.8% C18:1 + C18:2 (77:7%) salts (KO) (c) 0.01 ~iazinon ~ (D2) (d) 0.8% KO ~ 0.01% D2 Insects were treated topically to wetting with a hand pump æprayer and returned to rearing containers. Mortality was assessed after 24 hours at room temperature.
Results are given ln Table 6.
Ta % Mortality Rep 1Rep 2 Rep 3 _ Rep 4 Rep 5_ AverO
Control 0* 0 0 0.8% K0 20 40 20 40 0 24 0.01X D2 20 8 12 16 8 12.8 0.8% K0 ~ 0.1% D2 100 92 100 100 100 98.4 * % mortality out of 25 insects These results clearly show the synergism between the fatty acid salts and diazinon ~
Exa~ple 6 Test of unsaturated C18 salts (soaps) in combination with Malathion, Diazlnon ~ and Sevin ~ for control of cabbage aphid Brevicoryne brassicae (L.) .
Material and Methods:
Cabbage aphids, Brevicoryne brassicae (L.), were collected off of field cabbage and were used as the target insect. Five hundred ml of each treatment solution was made up fresh prior to use. Unsaturated fatty acid salts were made by neutralizing oleic and 1inolPic (77.0%:7~0% KO) with potassium hydroxide and a tall oil with its oleic and linoleic fatty acids (59.2%:40.8%~ F4) also converted to their potassium salts. These were formulated as a 50% liquid concentrate containing less than 0.03%
excess alkali from which the appropriate dilu~Lons were made. The malathion, Diazinon ~ and Sevin ~ were standard retail grade and used at the concentrations recommen~d by the label~ Ftve replicates each con-taining 20 aphids were randomly assigned to the following treatments.
Materials and ~1ethods:
Adult F. auricularia were collected from the field and separated into groups of 25. Three replicates of each group were assigned to the following treatments:
(a) water (~) 0.8% C18:1 + C18:2 (77:7%) salts (KO) (c) 0.01 ~iazinon ~ (D2) (d) 0.8% KO ~ 0.01% D2 Insects were treated topically to wetting with a hand pump æprayer and returned to rearing containers. Mortality was assessed after 24 hours at room temperature.
Results are given ln Table 6.
Ta % Mortality Rep 1Rep 2 Rep 3 _ Rep 4 Rep 5_ AverO
Control 0* 0 0 0.8% K0 20 40 20 40 0 24 0.01X D2 20 8 12 16 8 12.8 0.8% K0 ~ 0.1% D2 100 92 100 100 100 98.4 * % mortality out of 25 insects These results clearly show the synergism between the fatty acid salts and diazinon ~
Exa~ple 6 Test of unsaturated C18 salts (soaps) in combination with Malathion, Diazlnon ~ and Sevin ~ for control of cabbage aphid Brevicoryne brassicae (L.) .
Material and Methods:
Cabbage aphids, Brevicoryne brassicae (L.), were collected off of field cabbage and were used as the target insect. Five hundred ml of each treatment solution was made up fresh prior to use. Unsaturated fatty acid salts were made by neutralizing oleic and 1inolPic (77.0%:7~0% KO) with potassium hydroxide and a tall oil with its oleic and linoleic fatty acids (59.2%:40.8%~ F4) also converted to their potassium salts. These were formulated as a 50% liquid concentrate containing less than 0.03%
excess alkali from which the appropriate dilu~Lons were made. The malathion, Diazinon ~ and Sevin ~ were standard retail grade and used at the concentrations recommen~d by the label~ Ftve replicates each con-taining 20 aphids were randomly assigned to the following treatments.
5 (a) 1% KO (g) 1% K0 ~ 1% Diazinon (b) 1% F4 (h) 1% KO + 0~31% Sevin (c) 1% malathion (i) l~ F4 + 1% malathion (d) 1% Diazlnon ~ (~) 1% F4 ~ 1% Dlazinon (e) 0.31% Sevirl ~ (k) 1% F4 ~ 0.31% Sevin lO (f) 1% KO + 1% malathion (l) H20 Control Aphids were sprayed to wetting (3 ~L/replicate) on a glass plate, uslng a hand pump sprayer, allowed to soak one minute in the solution, before being transferred to petri plates (10 cm) lined with 9 cm Whatman filter paper #1. Mortality was assessed by counting living and dead aphids 24 hours after treatment.
Results are gLven ln Tflble 7.
, --The interaction of the malathion, Diazinon ~ and Sevin ~ with the unsaturated C18 salts i8 again clearly evldent~ The combinations in all cases showed enhanced activity greater than the individual formula-tions.
Table 7 . . , _ Aphid Mortality (5 r~plicates eucll co~l~ainirlg % MorL.
20 aph;ds~
~ . . _____._ Replicates ( ) = Moribund TREATMF.NTS 1 2 3 4 5 ._ ~
~120 ' O O ~ O O () 1% K0 16 12 17 16 198() 1% F4 15 15 16 15 1273 1% Malathion 16 15(5) 19 1517 82 1% Uiazinon(~) 14(5) 15(5) 17(3) 13(7) 16(4) 75 0.31% Sevin~ 13 14 19 1720 83 1% K0 + 1%
Mul.aLI)ion 20 20 20 2020 100 1% K0 -~ 1%
Diaz;no~ 20 20 19 20 2099 1% K0 -~ 0.31%
S~vi~i~` 20 20 20 20 20100 IX F4 -t 1% 20 20 20 20 2U100 Mula~l~i on l% F4 + 1%~, Diazillo ~ 18(2) 19(1) 20 19(r) 17(3) 93 1% F4 -t Q.31~
S~vi~l~ 20 20 20 2() 20100
Results are gLven ln Tflble 7.
, --The interaction of the malathion, Diazinon ~ and Sevin ~ with the unsaturated C18 salts i8 again clearly evldent~ The combinations in all cases showed enhanced activity greater than the individual formula-tions.
Table 7 . . , _ Aphid Mortality (5 r~plicates eucll co~l~ainirlg % MorL.
20 aph;ds~
~ . . _____._ Replicates ( ) = Moribund TREATMF.NTS 1 2 3 4 5 ._ ~
~120 ' O O ~ O O () 1% K0 16 12 17 16 198() 1% F4 15 15 16 15 1273 1% Malathion 16 15(5) 19 1517 82 1% Uiazinon(~) 14(5) 15(5) 17(3) 13(7) 16(4) 75 0.31% Sevin~ 13 14 19 1720 83 1% K0 + 1%
Mul.aLI)ion 20 20 20 2020 100 1% K0 -~ 1%
Diaz;no~ 20 20 19 20 2099 1% K0 -~ 0.31%
S~vi~i~` 20 20 20 20 20100 IX F4 -t 1% 20 20 20 20 2U100 Mula~l~i on l% F4 + 1%~, Diazillo ~ 18(2) 19(1) 20 19(r) 17(3) 93 1% F4 -t Q.31~
S~vi~l~ 20 20 20 2() 20100
Claims (14)
1. A mixture having enhanced insecticidal activity comprising:
(a) an insecticide active against defoliating insects selected from organochlorine compounds, organic esters of phosphoric or thiophos-phoric acids and carbamates, and mixtures thereof; and (b) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by weight of (a) (b).
(a) an insecticide active against defoliating insects selected from organochlorine compounds, organic esters of phosphoric or thiophos-phoric acids and carbamates, and mixtures thereof; and (b) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by weight of (a) (b).
2. The mixture of claim 1 wherein the insecticide (a) comprises an organochlorine insecticide.
3. The mixture of claim 1 wherein the insecticide (a) comprises a phosphoric or thiophosphoric acid ester insecticide.
4. The mixture of claims 1, 2 or 3 wherein the fatty acid (b) is selected from oleic acid, linoleic acid, their soaps and mixtures thereof.
5. The mixture of claims 1, 2 or 3 wherein a fatty acid salt is present in (b), the salt-forming cation being selected from sodium, potassium and ammonium.
6. The mixture of claims 1, 2 or 3 wherein the proportion of (a):(b) by wt. ranges from about 1:200 to about 1:1.
7. The mixture of claims 1, 2 or 3 wherein the proportion of (a):(b) by wt. ranges from about 1:20 to about 1:2.
8. The mixture of claims 1, 2 or 3 in the form of an aqueous solution in which the concentration of insecticide (a) ranges from about 0.005 to about 5% by wt. and the concentration of fatty acid or its salt (b) ranges from about 0.25 to about 5% by wt.
9. The mixture of claims 1, 2 or 3 wherein the insecticide (a) is the organochlorine 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane.
CLAIMS (cont.):
CLAIMS (cont.):
10. The mixture of claims 1, 2 or 3 wherein the insecticide (a) com-prises a thiophosphate selected from phosphorothioic acid 0,0-diethyl-0-(2-isopropyl-6-methyl-4-pyrimidinyl)ester and S-(1,2-dicarbethoxyethyl)-0,0-dimethyldithiophosphate.
11. The mixture of claims 1, 2 or 3 wherein the insecticide (a) com-prises the carbamate 1-naphthyl-N-methylcarbamate.
12. The mixture of claims 1, 2 or 3 wherein the insecticide (a) com-prises phosphorothioic acid 0,0-diethyl-0-(2-isopropyl-6-methyl-4-pyrimi-dinyl)ester.
13. A method of protecting susceptible plants against both sucking insects and defoliating insects comprising providing concurrently on the plant surfaces or directly on the insects, both (a) an insecticide active against defoliating insects selected from organochlorine compounds, organic esters of phosphoric or thiophosphoric acids and carbamates, and mixtures thereof, and (b) an unsaturated fatty acid having 18 carbon atoms or its salt; the fatty acid compound being at least about 50% by wt. of (a) + (b).
14. The method of claim 13 wherein (a) and (b) are applied together as a mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000421187A CA1187409A (en) | 1983-02-09 | 1983-02-09 | Insecticide mixtures containing fatty acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000421187A CA1187409A (en) | 1983-02-09 | 1983-02-09 | Insecticide mixtures containing fatty acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187409A true CA1187409A (en) | 1985-05-21 |
Family
ID=4124521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000421187A Expired CA1187409A (en) | 1983-02-09 | 1983-02-09 | Insecticide mixtures containing fatty acids |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1187409A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0413765A1 (en) * | 1988-05-04 | 1991-02-27 | Safer, Inc. | Enhanced activity arthropodicidal solution |
| EP0736251A1 (en) * | 1995-04-07 | 1996-10-09 | Joseph Benwaiche | Antiparasitic lotion |
| WO1998031223A1 (en) * | 1997-01-20 | 1998-07-23 | Action Pin | Additive composition for plant protection |
| WO2001089500A3 (en) * | 2000-05-24 | 2002-04-25 | Jordan Loyal Holtzman | Agents and methods for increasing brain chaperonin levels |
| FR2899061A1 (en) * | 2006-03-31 | 2007-10-05 | Cid Lines Nv | Hygienic, cosmetic and/or disinfectant composition, useful for treating and/or washing of teats and/or udder of mammals e.g. cow, comprises a fatty acid as repellent and/or insecticide composition against arthropods e.g. flies |
| US20120251641A1 (en) * | 2009-04-03 | 2012-10-04 | Tyra Tech, Inc, | Methods for pest control employing microemulsion-based enhanced pest control formulations |
-
1983
- 1983-02-09 CA CA000421187A patent/CA1187409A/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0413765A1 (en) * | 1988-05-04 | 1991-02-27 | Safer, Inc. | Enhanced activity arthropodicidal solution |
| EP0413765A4 (en) * | 1988-05-04 | 1992-05-13 | Safer, Inc. | Enhanced activity arthropodicidal solution |
| EP0736251A1 (en) * | 1995-04-07 | 1996-10-09 | Joseph Benwaiche | Antiparasitic lotion |
| FR2732557A1 (en) * | 1995-04-07 | 1996-10-11 | Benwaiche Joseph | PEST CONTROL LOTION |
| WO1998031223A1 (en) * | 1997-01-20 | 1998-07-23 | Action Pin | Additive composition for plant protection |
| FR2758436A1 (en) * | 1997-01-20 | 1998-07-24 | Action Pin | ADJUVANT COMPOSITION FOR PHYTOSANITARY USE |
| WO2001089500A3 (en) * | 2000-05-24 | 2002-04-25 | Jordan Loyal Holtzman | Agents and methods for increasing brain chaperonin levels |
| FR2899061A1 (en) * | 2006-03-31 | 2007-10-05 | Cid Lines Nv | Hygienic, cosmetic and/or disinfectant composition, useful for treating and/or washing of teats and/or udder of mammals e.g. cow, comprises a fatty acid as repellent and/or insecticide composition against arthropods e.g. flies |
| EP1842425A1 (en) | 2006-03-31 | 2007-10-10 | Cid Lines N.V. | Hygienic and/or cosmetic and/or disinfectant composition containing at least one anti-parasite and/or insect repellent agent |
| US20120251641A1 (en) * | 2009-04-03 | 2012-10-04 | Tyra Tech, Inc, | Methods for pest control employing microemulsion-based enhanced pest control formulations |
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