CA1054049A - Aqueous insecticidal concentrate composition - Google Patents
Aqueous insecticidal concentrate compositionInfo
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- CA1054049A CA1054049A CA265,888A CA265888A CA1054049A CA 1054049 A CA1054049 A CA 1054049A CA 265888 A CA265888 A CA 265888A CA 1054049 A CA1054049 A CA 1054049A
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Abstract
A NOVEL AQUEOUS INSECTICIDAL CONCENTRATE COMPOSITION
Abstract of the Disclosure .
A novel aqueous insecticidal concentrate composition comprising (a) an insecticidal organo-phosphorus compound, (b) water and (c) a surface active agent in an amount sufficient to render the organo-phosphorus compound soluble in the water, the pH of the composition being in the range of 3,0 to 8.5.
Abstract of the Disclosure .
A novel aqueous insecticidal concentrate composition comprising (a) an insecticidal organo-phosphorus compound, (b) water and (c) a surface active agent in an amount sufficient to render the organo-phosphorus compound soluble in the water, the pH of the composition being in the range of 3,0 to 8.5.
Description
~35~V~
This invention relates to a novel aqueous insecti-cidal concentrate composition. The term "insecticidal concentrate composition" used herein is intended to mean a solution, such as an emulsifiable concentrate, which contains insec-ticidal compound preferably in a concentration as high as 2% or more and is practically-applied after dilution with water to a concentration of below 1%.
An aqueous pesticidal concentrate composition containing a triazine derivative, a pyridine derivative, a chlorinated hydrocarbon or others as a pesticidal compound is disclosed in British Patent No. l,4~6,771. However, ~ .
the British Patent does not disclose an aqueous insecti-cidal concentrate composition containing an insecticidal organo-phosphorus compound as an active compound~ An insecticidal organo-phosphorus compound in such known aqueous pesticidal concentrate composition in which the .. :
. active compound is dispersed in water in the form of a : finely divided solid is very unstable and decomposes with the lapse of time.
Accordingly, an aqueous insecticidal concentrate composition containing an insecticidal organo-phosphorus compound is unknown. ~ .
I~nown concentxate compositions containing an insecticidal organo-phosphorus compound are generally ~:
~ composed of an insecticidal organo-phosphorus compound, an . organic solvent, a surface active agent and a stabilizer.
Water is scarcely contained in the compositions (e.g., the ` water content is generally below 1%). This is because organo-phosphorus compounds which serve as insecticide are usually poor in stability when water is present. Accordingly, it has been heretofore considered that the presence of ~1~
. A
~iL05~4~
water in the phosphorus compound-containing concentrate composition which is essentially required -to have relatively long shelf liEe must be avoicled.
A]most all of the organic solvents employed in the known concentrate compositions Eor agriculture or epidemic prevention, such as emulsiEiable concentrates have more or less toxity against animals and plants and take part in air or water pollution leading to many evils when used as insecticides. Further, the organic solvents employed in conventional insecticidal concentrate compositions are ordinarily combustible and have a danger of taking fire, so that the insecticidal concentrate compositions using such combustible organic solvents and containing no water must be handled or stored with the utmost care. ~ccordingly, use of watex instead of organic solvents is very convenient from every point of view. In addition, organic solvents which have been used in insecticides are important as starting materials for the synthesis of useful compounds or energy -~ sources. In the sense, the replacement of organic solvents by water is favourable from a social point of view.
We have found that the use of a surface active agent in an amount sufficient to render an insecticidal organo~
phosphorus compound soluble in water assuresl unexpectedly, formation of a stable concentrate composition, so that water ;~ `
may be used instead of organic solvent, and the prior art problems associated with the use of organic solvents are avoided.
In accordance with the present invention, there is provided an aqueous insecticidal concentrate composition comprising: (a) an insecticidal organo-phosphorus compound, (b) water, and ~c) a surface active agent in an amount : .
~OS4~
sufficient to render the organo-phosphorus compound soluble in -the water, the pEI of the composition ranging from 3.0 to :
8.5. The composition is obtainable as a clear solution ra-ther than a dispersion because the or~ano-phosphorus compound is entirely dlssolved in the aqueous medium.
There are usable in the present invention almost all insectlcidal organo-phosphorus compounds other than a very few of insecticidal organo-phosphorus compounds of a type which is very rapidly decomposed upon contact with water and is thus especially unstable in water. Preferred phosphorus compounds :'i . ', ' .
.`. ' .
' .
which are sparingly soluble in water, e.g., a solubility in water of below about 2 %, are expressed by the following general formula Xl ' Rl ~11 X R (I) (in which Rl represents a lower alkyl preferably having 1 to 3 carbon atoms, R2 represents a lower alkoxy preferably having 1 to 3 carbon atoms or phenyl, R3 represents a phenyl group having one to three substituents selected from the group consisting of CH3, NO2, CN, Cl and -S-CH3, 2-isopropyl 4-methyl-6-pyrimidlnyl group, 3,5,6-irichloro-2-pyridyl group, 1,2-diethoxycarbonyl group, or l-ethoxycarbonyl-l-phenylmethyl . group, and Xl and X2 are the same or different and are an oxygen a~om or a sulfur atom).
Most preferable compounds are expressed by the following general formula R O l~ (II) (in which R4 a Cd3- or C2}l5-, and R5 represents ~ -3-C33,
This invention relates to a novel aqueous insecti-cidal concentrate composition. The term "insecticidal concentrate composition" used herein is intended to mean a solution, such as an emulsifiable concentrate, which contains insec-ticidal compound preferably in a concentration as high as 2% or more and is practically-applied after dilution with water to a concentration of below 1%.
An aqueous pesticidal concentrate composition containing a triazine derivative, a pyridine derivative, a chlorinated hydrocarbon or others as a pesticidal compound is disclosed in British Patent No. l,4~6,771. However, ~ .
the British Patent does not disclose an aqueous insecti-cidal concentrate composition containing an insecticidal organo-phosphorus compound as an active compound~ An insecticidal organo-phosphorus compound in such known aqueous pesticidal concentrate composition in which the .. :
. active compound is dispersed in water in the form of a : finely divided solid is very unstable and decomposes with the lapse of time.
Accordingly, an aqueous insecticidal concentrate composition containing an insecticidal organo-phosphorus compound is unknown. ~ .
I~nown concentxate compositions containing an insecticidal organo-phosphorus compound are generally ~:
~ composed of an insecticidal organo-phosphorus compound, an . organic solvent, a surface active agent and a stabilizer.
Water is scarcely contained in the compositions (e.g., the ` water content is generally below 1%). This is because organo-phosphorus compounds which serve as insecticide are usually poor in stability when water is present. Accordingly, it has been heretofore considered that the presence of ~1~
. A
~iL05~4~
water in the phosphorus compound-containing concentrate composition which is essentially required -to have relatively long shelf liEe must be avoicled.
A]most all of the organic solvents employed in the known concentrate compositions Eor agriculture or epidemic prevention, such as emulsiEiable concentrates have more or less toxity against animals and plants and take part in air or water pollution leading to many evils when used as insecticides. Further, the organic solvents employed in conventional insecticidal concentrate compositions are ordinarily combustible and have a danger of taking fire, so that the insecticidal concentrate compositions using such combustible organic solvents and containing no water must be handled or stored with the utmost care. ~ccordingly, use of watex instead of organic solvents is very convenient from every point of view. In addition, organic solvents which have been used in insecticides are important as starting materials for the synthesis of useful compounds or energy -~ sources. In the sense, the replacement of organic solvents by water is favourable from a social point of view.
We have found that the use of a surface active agent in an amount sufficient to render an insecticidal organo~
phosphorus compound soluble in water assuresl unexpectedly, formation of a stable concentrate composition, so that water ;~ `
may be used instead of organic solvent, and the prior art problems associated with the use of organic solvents are avoided.
In accordance with the present invention, there is provided an aqueous insecticidal concentrate composition comprising: (a) an insecticidal organo-phosphorus compound, (b) water, and ~c) a surface active agent in an amount : .
~OS4~
sufficient to render the organo-phosphorus compound soluble in -the water, the pEI of the composition ranging from 3.0 to :
8.5. The composition is obtainable as a clear solution ra-ther than a dispersion because the or~ano-phosphorus compound is entirely dlssolved in the aqueous medium.
There are usable in the present invention almost all insectlcidal organo-phosphorus compounds other than a very few of insecticidal organo-phosphorus compounds of a type which is very rapidly decomposed upon contact with water and is thus especially unstable in water. Preferred phosphorus compounds :'i . ', ' .
.`. ' .
' .
which are sparingly soluble in water, e.g., a solubility in water of below about 2 %, are expressed by the following general formula Xl ' Rl ~11 X R (I) (in which Rl represents a lower alkyl preferably having 1 to 3 carbon atoms, R2 represents a lower alkoxy preferably having 1 to 3 carbon atoms or phenyl, R3 represents a phenyl group having one to three substituents selected from the group consisting of CH3, NO2, CN, Cl and -S-CH3, 2-isopropyl 4-methyl-6-pyrimidlnyl group, 3,5,6-irichloro-2-pyridyl group, 1,2-diethoxycarbonyl group, or l-ethoxycarbonyl-l-phenylmethyl . group, and Xl and X2 are the same or different and are an oxygen a~om or a sulfur atom).
Most preferable compounds are expressed by the following general formula R O l~ (II) (in which R4 a Cd3- or C2}l5-, and R5 represents ~ -3-C33,
2 ~ Cl or ~ J~ / 3 Examples of the compounds expressed by the general formulae (I) `20 and (II) include 0,0-dimethyl-0-(3-methyl-4-methylthiophenyl) - thiophosphate (hereinafter referred to simply as fenthion), ` - 5 -.. .
, . s~r ~
' ' ' . ' , ~ ' ' ~ .. ,. .. ~
,, , . : .. , : ' ~
105~04~
0,0-dimethyl-0-(3-methyl-4-rlitrophenyl)thiophosphate (hereinafter referred to simply as fenitrothion),0,0-diethyl-0-[2-isopropyl-~-methylpyrimidyl(6)]thiophosphate (hereinaEter referred -to simply as diazinon), S-(1,2-dicarboethoxyethyl)-0, 0-dimethyldithiophospha-te (hereinafter reEerred to simply as malathion), 0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate (hereinafter referred to simply as ronnel), 0,0,0',0'-tetramethyl-0,0'-thiodi-P-phenylene) thiophosphate, 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl) thiophosphate, 0,0-dimethyl-S-[(~ -ethoxycarbonyl)ben~yl]
dithio~hosphate, 0-ethyl-0-(4-nitrophenyl)-phenylphosphon-okhioate, O,o-dimethyl-0-(4-cyanophenyl)thiophosphate, etc.
The ratio of the phosphorus compound to the concentrate composition is preferably in the range of 2 to 50~.
The amount of water in the concentrate composition of the present invention is variable according to the content of an insecticidal organo-phosphorus compoun~ in the concen-trate composition but preferred amount is from 20% by weight ; to 96% by weight based on total weight of the concentrate composition. If circumstances require, the water may contain - an organic solvent in an amount of less than the water. Whenthe concentration of the insecticidal organo-phosphorus compound in the concentrate composition of the present invention exceeds 30%, it is preferred to use, in conjunction with water, an organic solvent, preferably a polar organic solvent, in an amount of below 15% based on the total weight of the concentrate composition. The polar organic solvents include ketones, cellosolve ethers, alcohols, etc. which have a boiling point of, preferably, not lower than 80C. Suitable polar organic solvents include, for example, cyclohexanone, isophorone, ethyl cellosolve, methyl cellosolve, iso~ropyl . .
;~ cellosolve, ~ - 6 -:. : . ~ , ~ . . .
1 ~354~9 cyclohexclnol, diacetone alcohol, butanol, bu-tyl glycol and the like. When dia~inon is used as the phosphorus compound, ketones and cellosolve ethers are most preferable.
The s~lrface active agcnt useful in the present invention depenclr~ on the nature of the insecticida] oryanic phosphoruc compound. Usable surface active agents inc1ude nonionic surface active agents, ionic surface active agents and ampholvtic ¦surface active agents. Polyoxyethylene alkylallylphenyl ethers ¦and homologues thereof are preferred due to a wide range of ¦application.
The surface active agent should be added in an amount ¦sufficient to make the insecticidal organo-phosphorus compound ¦soluble in said water, and the amount varies depending on the ¦kind and amount of insecticidal organo-phosphorus compound, and ¦also on the kind of the surface active agent itself. In ¦general, the preferred amount of surface active agent is in the range of 0.4 to 4 times the weight of an insecticidal organo--phosphorus compound and in the range of 2 to 30 % (by weight) of the composition. -~0 In practicing the present invention, the pH of the concentrate composition should be adjusted in the range of 3.0 to 8.5 so as to prevent the organo-phosphorus compound from being decomposed. The optimum pH of the composition varies depending on the kind of the organo-phosphorus compound. For example, with the malathion,the optimum pH is in the range o-f - ~ 3.0 to 4.0 with the diazinon, the pH in the range of 6.5 to8.5 is suitable. When a number of other phosphorus compounds are used, the composition in the pH range of 5 ~ to 6 .5 is most stable.
:
', : . , ,., , : .
~5~
When a relatively s-tabie insecticidal material such as fen-thion, ronnel or the like i5 used for preparing an aqueous insecticidal concentrate composition o~ the present invention, the composition may often fal] on a suitable range of pEI only with the use of a surface active agent and water and it is not necessary to use any pH-adjusting agent. With a relatively unstable insecticidal compound such as diazinon, however, it is necessary to use a buffer solution for pH adjustmen~ so as to suppress the change in quality of the insecticidal compound per se witl a lapse of time. In this case, the choice of the buffer solution should depend on the nature of the insecticidal compound. With the diazinon, for example, Sorensen's buffer solution composed of an aqueous solution of potassium dihydrogenphosphate and an aqueous solution of disodium hydrogenphosphate, Kolthhoff's buffer solution composed of an aqueous solution of potassium dihydrogenphosphate and an aqueous solution of borax or McIlvaine's buffer solution composed of an aqueous solution of disodium hydrogenphosphate and an aqueous solution of citric acid is suitable for the ;
pH adjustment.
In some cases, the aqueous insecticidal concentrate ` composition of the present invention may advantageously be improved in stability by addition of stabilizers. An epoxy-compound is a suitable stabilizer for the a~ueous insecticidal concentrate composition of the present invention. The epoxy : :
compounds are for example, epichlorohydrin, butyl glycidyl ~;
ether, phenyl glycidyl ether, cresyl glycidyl e~her, meth-- acrylic acid glycidyl ether, ethylene glycol glycidyl ether, ; 30 propylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, .
,:: , : : ~ ~ ' : `
.
~05~1349 butandlol diylycidyl ether, glycerol diglycidyl ether, etc.
These stabilizers are usually added in an amount of 0.5 to
, . s~r ~
' ' ' . ' , ~ ' ' ~ .. ,. .. ~
,, , . : .. , : ' ~
105~04~
0,0-dimethyl-0-(3-methyl-4-rlitrophenyl)thiophosphate (hereinafter referred to simply as fenitrothion),0,0-diethyl-0-[2-isopropyl-~-methylpyrimidyl(6)]thiophosphate (hereinaEter referred -to simply as diazinon), S-(1,2-dicarboethoxyethyl)-0, 0-dimethyldithiophospha-te (hereinafter reEerred to simply as malathion), 0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate (hereinafter referred to simply as ronnel), 0,0,0',0'-tetramethyl-0,0'-thiodi-P-phenylene) thiophosphate, 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl) thiophosphate, 0,0-dimethyl-S-[(~ -ethoxycarbonyl)ben~yl]
dithio~hosphate, 0-ethyl-0-(4-nitrophenyl)-phenylphosphon-okhioate, O,o-dimethyl-0-(4-cyanophenyl)thiophosphate, etc.
The ratio of the phosphorus compound to the concentrate composition is preferably in the range of 2 to 50~.
The amount of water in the concentrate composition of the present invention is variable according to the content of an insecticidal organo-phosphorus compoun~ in the concen-trate composition but preferred amount is from 20% by weight ; to 96% by weight based on total weight of the concentrate composition. If circumstances require, the water may contain - an organic solvent in an amount of less than the water. Whenthe concentration of the insecticidal organo-phosphorus compound in the concentrate composition of the present invention exceeds 30%, it is preferred to use, in conjunction with water, an organic solvent, preferably a polar organic solvent, in an amount of below 15% based on the total weight of the concentrate composition. The polar organic solvents include ketones, cellosolve ethers, alcohols, etc. which have a boiling point of, preferably, not lower than 80C. Suitable polar organic solvents include, for example, cyclohexanone, isophorone, ethyl cellosolve, methyl cellosolve, iso~ropyl . .
;~ cellosolve, ~ - 6 -:. : . ~ , ~ . . .
1 ~354~9 cyclohexclnol, diacetone alcohol, butanol, bu-tyl glycol and the like. When dia~inon is used as the phosphorus compound, ketones and cellosolve ethers are most preferable.
The s~lrface active agcnt useful in the present invention depenclr~ on the nature of the insecticida] oryanic phosphoruc compound. Usable surface active agents inc1ude nonionic surface active agents, ionic surface active agents and ampholvtic ¦surface active agents. Polyoxyethylene alkylallylphenyl ethers ¦and homologues thereof are preferred due to a wide range of ¦application.
The surface active agent should be added in an amount ¦sufficient to make the insecticidal organo-phosphorus compound ¦soluble in said water, and the amount varies depending on the ¦kind and amount of insecticidal organo-phosphorus compound, and ¦also on the kind of the surface active agent itself. In ¦general, the preferred amount of surface active agent is in the range of 0.4 to 4 times the weight of an insecticidal organo--phosphorus compound and in the range of 2 to 30 % (by weight) of the composition. -~0 In practicing the present invention, the pH of the concentrate composition should be adjusted in the range of 3.0 to 8.5 so as to prevent the organo-phosphorus compound from being decomposed. The optimum pH of the composition varies depending on the kind of the organo-phosphorus compound. For example, with the malathion,the optimum pH is in the range o-f - ~ 3.0 to 4.0 with the diazinon, the pH in the range of 6.5 to8.5 is suitable. When a number of other phosphorus compounds are used, the composition in the pH range of 5 ~ to 6 .5 is most stable.
:
', : . , ,., , : .
~5~
When a relatively s-tabie insecticidal material such as fen-thion, ronnel or the like i5 used for preparing an aqueous insecticidal concentrate composition o~ the present invention, the composition may often fal] on a suitable range of pEI only with the use of a surface active agent and water and it is not necessary to use any pH-adjusting agent. With a relatively unstable insecticidal compound such as diazinon, however, it is necessary to use a buffer solution for pH adjustmen~ so as to suppress the change in quality of the insecticidal compound per se witl a lapse of time. In this case, the choice of the buffer solution should depend on the nature of the insecticidal compound. With the diazinon, for example, Sorensen's buffer solution composed of an aqueous solution of potassium dihydrogenphosphate and an aqueous solution of disodium hydrogenphosphate, Kolthhoff's buffer solution composed of an aqueous solution of potassium dihydrogenphosphate and an aqueous solution of borax or McIlvaine's buffer solution composed of an aqueous solution of disodium hydrogenphosphate and an aqueous solution of citric acid is suitable for the ;
pH adjustment.
In some cases, the aqueous insecticidal concentrate ` composition of the present invention may advantageously be improved in stability by addition of stabilizers. An epoxy-compound is a suitable stabilizer for the a~ueous insecticidal concentrate composition of the present invention. The epoxy : :
compounds are for example, epichlorohydrin, butyl glycidyl ~;
ether, phenyl glycidyl ether, cresyl glycidyl e~her, meth-- acrylic acid glycidyl ether, ethylene glycol glycidyl ether, ; 30 propylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, .
,:: , : : ~ ~ ' : `
.
~05~1349 butandlol diylycidyl ether, glycerol diglycidyl ether, etc.
These stabilizers are usually added in an amount of 0.5 to
3% by weigh-t of a final composition. Further, addl-tion of sodium erythorba-te is effective, to some ex-tent, in improving the stability and more effective when used in combination with an epoxy compound. ~Iowever, the combination is disadvantageous due to formation of coloring material.
The storaye stability of the aqueous insecticidal concentrate composition of the present invention stands comparison with those of known emulsifiable concentrates using organic solvent. That is, the concentrate composition of the present invention is found to have a decomposition rate of an insecticidal organo-phosphorus compound as low as 3 to 5% when tested at room temperature (i.e., 5-34C) over one year.
The aqueous insectlcidal concentrate composition of the present invention is similar in nature to the known emulsifiable concentrate compositions and can be applied in the same manner and amount as the known compositions. In ~ ;- 20 comparison with the known emulsifiable concentrates, the- concentrate composition of the present invention exhibits the same or superior level of insecticidal effect to noxious insects such as larvae of mosquito, fly, midge, gnat, etc., when determined by an immersion method. Further, it has been ` found by a peroral test using larvae of Orthoptera and Lepidptera insects having mandibles that the concentrate ` composition of the present invention has the same efficacy -against the agricultural noxious insects as the known counter- ;
- parts. In addition, the concentrate composition of the invention is not inferior in residual efficacy to concentrates ; of other types. As for peroral acute toxicity, ~0% - lethal _ g _ - : ~ .,, -0~
doses of -the concen'rate composition of the present inven-tion for mice an~ rats is mueh more by about 30 to 50% than a known emulsifiable concentrate eontaining the same inseeticidal organo-phosphorus eompound as the present invention. This means -that the concentrate eomposition of the invention is less harmful than the ~nown emulsifi~ble eoncentra-ke. With regard to the percutaneous toxicity which may present a problem upon applying an insecticide by :
sprinkling, neither mouse nor rat dies when the eoncentrate eomposi~:ion of the invention is dosed at a level of 50~ -lethal dose of the known emulsifiable eoneentrate. From the above it will be elear that the eomposition of the invention is mueh less noxious. In a skin-irritating test, neither irritation nor inflammation is reeognized. Further, an inhalation test reveals that the eoncentrate eomposition of the invention is more harmless than lcnown emulsifiable con-centration. A fish test also reveals that the concentration of the concentrate. com.position of the invention required to attain the same mortality of, for example, goldfish and red killifish is about 1.5 to 2 times as great as that of an emul-sion~type insecticide, thus showing ani~provement in toxicity.
The reduction of toxicity of the concentrate .
: composition of the invention is considered to result from omission or reduetion in amount of organi.e solvent inherently possessed of toxieity and redueed synergistie toxieity of the other eomponents due to the omission of organie solvent, and also from reduetion in veloeity and amount of absorption of inseeticidal component through skin and mucouse membrane due to use of water as major proportion or all of solvent.
The eoncentrate eomposition of the present invention exerts on a mitigated action on plants. So far as a proper ~ ;
:
, -- 10 , 1~5~
insecticidal compound is properly used depen~ing on the kind of plantt the concentrate composition of the presen-t invention is hard to bring c~bout the ill effects on plant.
Furthe~, the concentra-te composition of the present invention is very conveniently used for the epidemic preven tion purpose since it has little or no tendency to damage of synthetic resin articles, rubber articles and coating surfaces when compaLed with known emulsifiable concentrates.
The present invention will be particularly illus~
trated by way of the following examples, which should not be construed as limitation thereof.
Example 1 - .
(1) Preparation of Insecticidal Concentrate Composition of Invention (Hereinafter the aqueous insecticidal composition of the present invention is referred to as "aqueous concen-trate") (a~ 5~ fenthion aqueous concentrate : --5 g of fenthion as an insecticidal organo ~` phosphorus compound and 15 g of polyoxyethylene dist~ryl-methylphenyl ether (ethylene mol number = 10) as a surface . . . ~ ~ . .
active agent were gradually added to 80 g of water with stirring to obtain a uniform clear solutionO The solution or preparation was adjusted to have a pH of 5~
(b) 5% fenthion emulsifiable concentrate reference insecticide ::
:
5 g of fenthion, S g of a mixture of polyoxyethylene nonylphenyl ether and sodium dodecylbenzenesulfonate, 20 g ;~
.~ ~
; of xylene and 70 g of kerosene were mixed together for dissolution.
-~` 30 (2) Comparative Test Results The above two insecticides were tested to determin~
- : :
.: - 11- . ' .
: ! ' :' '~
~1~5~04~
insecti^idal eficacy, acute toxity and s-tability. The test results are shown below.
(a) Insecticidal Efflcacy _ _ _ ___ __ Present ~<eference Invention .__ _ .
5%-fenthion 5%-emulsi Eiable kind of insect and test method aqueous o~ncentrate conoen trate Houseflies (larvae) immersion method(l) 0.13-0.15 0.15-0.33 ppm LC-50 ppm ~squitos (culex i~[mersion method 0.0018 ppm 0.0019 ppm pipiens) LC-50 ~Iouseflies (adult) filter ~er contact 3 hrs. & 36 3 hrs. & 22 min.
method ~cr-50 min.
~Iouseflies (adult) spray-dropping( ) 22 min. & 46 18 min. h 32 method (Nagasawa' s sec. sec.
Irethod) KT-50 Cockroaches plywood conta~) 7 hrs. 5 hrs.
(B.Germanica) method K~50 ~
20 Note:
(1) Immersion method: Each 5 ml of the insecticidal solution diluted to different concentrations was placed in a tall-skirted schale (i.e., small plate) having a diameter of 9 cm and a height of 6 cm, in which 30 worms to be tested were ` put. Thereafter, the schale was covered and allowed to stand at about 25C for 24 hours for determinlng the LC-50.
- ~ (2) Filter paper-contacting method: A schale having a diameter oE 9 cm and a height of 2 cm was covered with filter paper on the bottom thereof . O . 32 ml of a 0 . 596 - 30 insecticidal solution was uniformly applied to the filter paper by means of a 1 ml messpipet, in which 30 worms were put. The schale was maintained at about 25C to determine the KT-5 0 .
(3) Spray-dropping method (Nagasawa' s method):
A glass cylinder having an inner diameter of 20 cm and a , .
.
~05~L~49 height of 43 cm was covered at the top thereof with a glass plate having a circular through-hole with a diameter oE 2.5 cm at -the center thereof and was placed on a glass plate at the bottom thereof. Then, a tes-t pot containing 30 worms was set in th~ glass cylinder. Thereafter, 0.5 ml of a 0.5%
insectieidal sam~le solution was sprayed Erom the circular through-hole under a pressure of ~0 lb~in (i.e., 1.5 kg/cm2~.
10 seconds after the spraying, the glass plate at the bottom of the cylinder was removed so as to permit the fine particles of the sprayed solution to enter the worm-containing pot.
By the above procedure, the KT-50 was determined.
The storaye stability of the aqueous insecticidal concentrate composition of the present invention stands comparison with those of known emulsifiable concentrates using organic solvent. That is, the concentrate composition of the present invention is found to have a decomposition rate of an insecticidal organo-phosphorus compound as low as 3 to 5% when tested at room temperature (i.e., 5-34C) over one year.
The aqueous insectlcidal concentrate composition of the present invention is similar in nature to the known emulsifiable concentrate compositions and can be applied in the same manner and amount as the known compositions. In ~ ;- 20 comparison with the known emulsifiable concentrates, the- concentrate composition of the present invention exhibits the same or superior level of insecticidal effect to noxious insects such as larvae of mosquito, fly, midge, gnat, etc., when determined by an immersion method. Further, it has been ` found by a peroral test using larvae of Orthoptera and Lepidptera insects having mandibles that the concentrate ` composition of the present invention has the same efficacy -against the agricultural noxious insects as the known counter- ;
- parts. In addition, the concentrate composition of the invention is not inferior in residual efficacy to concentrates ; of other types. As for peroral acute toxicity, ~0% - lethal _ g _ - : ~ .,, -0~
doses of -the concen'rate composition of the present inven-tion for mice an~ rats is mueh more by about 30 to 50% than a known emulsifiable concentrate eontaining the same inseeticidal organo-phosphorus eompound as the present invention. This means -that the concentrate eomposition of the invention is less harmful than the ~nown emulsifi~ble eoncentra-ke. With regard to the percutaneous toxicity which may present a problem upon applying an insecticide by :
sprinkling, neither mouse nor rat dies when the eoncentrate eomposi~:ion of the invention is dosed at a level of 50~ -lethal dose of the known emulsifiable eoneentrate. From the above it will be elear that the eomposition of the invention is mueh less noxious. In a skin-irritating test, neither irritation nor inflammation is reeognized. Further, an inhalation test reveals that the eoncentrate eomposition of the invention is more harmless than lcnown emulsifiable con-centration. A fish test also reveals that the concentration of the concentrate. com.position of the invention required to attain the same mortality of, for example, goldfish and red killifish is about 1.5 to 2 times as great as that of an emul-sion~type insecticide, thus showing ani~provement in toxicity.
The reduction of toxicity of the concentrate .
: composition of the invention is considered to result from omission or reduetion in amount of organi.e solvent inherently possessed of toxieity and redueed synergistie toxieity of the other eomponents due to the omission of organie solvent, and also from reduetion in veloeity and amount of absorption of inseeticidal component through skin and mucouse membrane due to use of water as major proportion or all of solvent.
The eoncentrate eomposition of the present invention exerts on a mitigated action on plants. So far as a proper ~ ;
:
, -- 10 , 1~5~
insecticidal compound is properly used depen~ing on the kind of plantt the concentrate composition of the presen-t invention is hard to bring c~bout the ill effects on plant.
Furthe~, the concentra-te composition of the present invention is very conveniently used for the epidemic preven tion purpose since it has little or no tendency to damage of synthetic resin articles, rubber articles and coating surfaces when compaLed with known emulsifiable concentrates.
The present invention will be particularly illus~
trated by way of the following examples, which should not be construed as limitation thereof.
Example 1 - .
(1) Preparation of Insecticidal Concentrate Composition of Invention (Hereinafter the aqueous insecticidal composition of the present invention is referred to as "aqueous concen-trate") (a~ 5~ fenthion aqueous concentrate : --5 g of fenthion as an insecticidal organo ~` phosphorus compound and 15 g of polyoxyethylene dist~ryl-methylphenyl ether (ethylene mol number = 10) as a surface . . . ~ ~ . .
active agent were gradually added to 80 g of water with stirring to obtain a uniform clear solutionO The solution or preparation was adjusted to have a pH of 5~
(b) 5% fenthion emulsifiable concentrate reference insecticide ::
:
5 g of fenthion, S g of a mixture of polyoxyethylene nonylphenyl ether and sodium dodecylbenzenesulfonate, 20 g ;~
.~ ~
; of xylene and 70 g of kerosene were mixed together for dissolution.
-~` 30 (2) Comparative Test Results The above two insecticides were tested to determin~
- : :
.: - 11- . ' .
: ! ' :' '~
~1~5~04~
insecti^idal eficacy, acute toxity and s-tability. The test results are shown below.
(a) Insecticidal Efflcacy _ _ _ ___ __ Present ~<eference Invention .__ _ .
5%-fenthion 5%-emulsi Eiable kind of insect and test method aqueous o~ncentrate conoen trate Houseflies (larvae) immersion method(l) 0.13-0.15 0.15-0.33 ppm LC-50 ppm ~squitos (culex i~[mersion method 0.0018 ppm 0.0019 ppm pipiens) LC-50 ~Iouseflies (adult) filter ~er contact 3 hrs. & 36 3 hrs. & 22 min.
method ~cr-50 min.
~Iouseflies (adult) spray-dropping( ) 22 min. & 46 18 min. h 32 method (Nagasawa' s sec. sec.
Irethod) KT-50 Cockroaches plywood conta~) 7 hrs. 5 hrs.
(B.Germanica) method K~50 ~
20 Note:
(1) Immersion method: Each 5 ml of the insecticidal solution diluted to different concentrations was placed in a tall-skirted schale (i.e., small plate) having a diameter of 9 cm and a height of 6 cm, in which 30 worms to be tested were ` put. Thereafter, the schale was covered and allowed to stand at about 25C for 24 hours for determinlng the LC-50.
- ~ (2) Filter paper-contacting method: A schale having a diameter oE 9 cm and a height of 2 cm was covered with filter paper on the bottom thereof . O . 32 ml of a 0 . 596 - 30 insecticidal solution was uniformly applied to the filter paper by means of a 1 ml messpipet, in which 30 worms were put. The schale was maintained at about 25C to determine the KT-5 0 .
(3) Spray-dropping method (Nagasawa' s method):
A glass cylinder having an inner diameter of 20 cm and a , .
.
~05~L~49 height of 43 cm was covered at the top thereof with a glass plate having a circular through-hole with a diameter oE 2.5 cm at -the center thereof and was placed on a glass plate at the bottom thereof. Then, a tes-t pot containing 30 worms was set in th~ glass cylinder. Thereafter, 0.5 ml of a 0.5%
insectieidal sam~le solution was sprayed Erom the circular through-hole under a pressure of ~0 lb~in (i.e., 1.5 kg/cm2~.
10 seconds after the spraying, the glass plate at the bottom of the cylinder was removed so as to permit the fine particles of the sprayed solution to enter the worm-containing pot.
By the above procedure, the KT-50 was determined.
(4) Plywood contaet method: A 0.5% inseetieidal sample solution was uniformly brush applied to a plywood plate in an amount of 50 ml/m2, followed by allowing the stand as it is for drying. Then, a circular glass ring having a diameter of 9 cm and a height of 6 cm was placed on the applied faee in which 30 worms were let, thereby determining the KT-50. It will be noted that the LC-50 is intended to mean 50~ - lethal concentration and the KT-50 means 50% -lethal-knockdown time.
.
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1~54049 (b) Acute Toxicity __ kind of tcst animal and test method aqueous preparation emulsion for of invention reference ~ . ~
p~roral dos~ ddy mic~ LD-50 approximate].y 2.0 ml/kg (male) 2.8 ml/kg " ddy mice LD-50 3.6 m:L/kg 2.5 ml/k~
(f~male) " SD rats LD-50 4.98 ml/kg 2.9 ml/kg (male) .
" SD rats LD-50 4.16 ml/kg 3.1 ml/kg (female) " Wister rats LD-50 3.3~ to ~.30 ml/kg 2.8 ml/kg (female) .
_ ,, . , . ..
percutaneous ddy mi.ce LD-50 more than dose (male) 9.93 ml/kg 10 ~l/kg " ddy mice LD-50more than : (female) 11.3 ml/kg 11.3 ml/kg " Wister rats LD-50 approximately . (male) 18 ml/kg 9.8 ml/kg ~ ~ ____ , Note: LD-50 means 50 ~ ~ lethal dose. In the toxicity test, 10 mice were taken as one group and 6 to 7 groups were subjected to the test. With rats, 6 rats were taken as one group and 6 groups were used for the test. The observation was conducted for 7 days or 14 days.
The peroral toxicity was examined as follows: an insecti-cidal concentrate was forcibly dosed into the stomæh of a test animal by the use of a metal stomach probe. While, the ` 10 percutaneous toxicity was examined by shaving the back of a test animal and applying an insecticidal concentrate to the shaved back.
;
. The percutaneous toxicity of the aqueous insecticide of the invention against the mice ~male and female) was as follows:
no mice died when the aqueous insecticide was dosed in amounts of 9.93 ml/kg and 11.3 ml/kg to the male and female mice, ', . .' :~
~.i ~ , - .. .. . . .
respectively, without evidencing clear toxic symptons.
From this it is assumed that the LD~S0 i5 far greater than the above-indicated amounts.
(c) Decomposition Rate of EEfective Ingredient During Storage _ Present _ invention Reference storing conditions 5~ fenthion 5~ enthion emulsi-concentrate fiable concentrate _ _ 40C, 4 weeks 1.12~ 1.03%
40C, 8 weeks 2.63~ 2.72 room temperature, 3.30% 3.15 one year (S-34C) Note: ~he test was conducted by placing the sample in a hermetically sealed glass bottle and keeping the bottle in a light-shielded place of the predetermined temperature.
(3) Discussion As for the insecticidal efficacy, the aqueous ~ concentrate of the present invention is equivalent or rather -; 20 superior to the known emulsifiable concentrate with regard -~
to larvae o-f Houseflies and Mosquitoes, but the latter is ;~
superior with regard to adult of Houseflies, Mosquitoes and -German cockroach. However, the insecticidal efficacy of the ~ aqueous concentrate of the present invention is within a i range enough to stamp out the noxious insects when the insec~
;~ ticide is applied in a standard amount. ;~
There is little difference between the aqueous concentrate of the present invention and the known emulsi-` fiable concentrate ;
~ 30 .~ ~ '' ' .
.
:. . . . . .
:, . .- . ' ;: ' ` ' - , -concerning the decomposition rate with the lapse of time. As for the acute ~oxicity, the aqueous concentra-te of the present invention is less harmful than -the known emulsifiable concent-rate. Especially, the reduction in percutaneous toxicity is S considerable. ~s a whole, the aqueous concentrate of the present invention i5 similar in insecticidal efficacy and stability to the known emulsifiable concentrate and has reduced toxic characteristics.
Exam~le 2 (Comparative Test for ~esidual Efficacy) (1) Tested Insecticides (a) Aqueous 5 ~ fenthionaqueous concentrate prepared in the same manner as in Example l~ (a).
(b) 5 ~ fenthion emulsifiable concentrate prepared in the same manner as in Example l-(i)-(b).
(2) Tested insect: Adult of houseflies ; (3) Test Period: July 23, 1973 - August 16, 1973 - (4) Test Method: The respective concentrate were diluted ten times with water and were each sprayed over the inner surfaces of a room in an amount 50 ml/m2. 1, 5, lO, l~ and 25 days after the spraying treatment, each 200 flies were let in the room and the xoom was closed. 24 hours after the closing, the number of dead flies was examined. In the test results, the ~ term "closed division" is intended to mean that the windows in; the room were all closed during the course of the test, while ;; 25 the term "opened division" means that the windows were all opened during a period between an examined day and a next ~; ~1etting-in day ,. , . .
.' ~ -''' .
~.
.
~ , ,'.', ~ ' .: ' ' ~'~:"' '' ~
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:,: .. . : ;
,: ~ , ' : , . . , : . ., . : ; .
1~54049 (b) Acute Toxicity __ kind of tcst animal and test method aqueous preparation emulsion for of invention reference ~ . ~
p~roral dos~ ddy mic~ LD-50 approximate].y 2.0 ml/kg (male) 2.8 ml/kg " ddy mice LD-50 3.6 m:L/kg 2.5 ml/k~
(f~male) " SD rats LD-50 4.98 ml/kg 2.9 ml/kg (male) .
" SD rats LD-50 4.16 ml/kg 3.1 ml/kg (female) " Wister rats LD-50 3.3~ to ~.30 ml/kg 2.8 ml/kg (female) .
_ ,, . , . ..
percutaneous ddy mi.ce LD-50 more than dose (male) 9.93 ml/kg 10 ~l/kg " ddy mice LD-50more than : (female) 11.3 ml/kg 11.3 ml/kg " Wister rats LD-50 approximately . (male) 18 ml/kg 9.8 ml/kg ~ ~ ____ , Note: LD-50 means 50 ~ ~ lethal dose. In the toxicity test, 10 mice were taken as one group and 6 to 7 groups were subjected to the test. With rats, 6 rats were taken as one group and 6 groups were used for the test. The observation was conducted for 7 days or 14 days.
The peroral toxicity was examined as follows: an insecti-cidal concentrate was forcibly dosed into the stomæh of a test animal by the use of a metal stomach probe. While, the ` 10 percutaneous toxicity was examined by shaving the back of a test animal and applying an insecticidal concentrate to the shaved back.
;
. The percutaneous toxicity of the aqueous insecticide of the invention against the mice ~male and female) was as follows:
no mice died when the aqueous insecticide was dosed in amounts of 9.93 ml/kg and 11.3 ml/kg to the male and female mice, ', . .' :~
~.i ~ , - .. .. . . .
respectively, without evidencing clear toxic symptons.
From this it is assumed that the LD~S0 i5 far greater than the above-indicated amounts.
(c) Decomposition Rate of EEfective Ingredient During Storage _ Present _ invention Reference storing conditions 5~ fenthion 5~ enthion emulsi-concentrate fiable concentrate _ _ 40C, 4 weeks 1.12~ 1.03%
40C, 8 weeks 2.63~ 2.72 room temperature, 3.30% 3.15 one year (S-34C) Note: ~he test was conducted by placing the sample in a hermetically sealed glass bottle and keeping the bottle in a light-shielded place of the predetermined temperature.
(3) Discussion As for the insecticidal efficacy, the aqueous ~ concentrate of the present invention is equivalent or rather -; 20 superior to the known emulsifiable concentrate with regard -~
to larvae o-f Houseflies and Mosquitoes, but the latter is ;~
superior with regard to adult of Houseflies, Mosquitoes and -German cockroach. However, the insecticidal efficacy of the ~ aqueous concentrate of the present invention is within a i range enough to stamp out the noxious insects when the insec~
;~ ticide is applied in a standard amount. ;~
There is little difference between the aqueous concentrate of the present invention and the known emulsi-` fiable concentrate ;
~ 30 .~ ~ '' ' .
.
:. . . . . .
:, . .- . ' ;: ' ` ' - , -concerning the decomposition rate with the lapse of time. As for the acute ~oxicity, the aqueous concentra-te of the present invention is less harmful than -the known emulsifiable concent-rate. Especially, the reduction in percutaneous toxicity is S considerable. ~s a whole, the aqueous concentrate of the present invention i5 similar in insecticidal efficacy and stability to the known emulsifiable concentrate and has reduced toxic characteristics.
Exam~le 2 (Comparative Test for ~esidual Efficacy) (1) Tested Insecticides (a) Aqueous 5 ~ fenthionaqueous concentrate prepared in the same manner as in Example l~ (a).
(b) 5 ~ fenthion emulsifiable concentrate prepared in the same manner as in Example l-(i)-(b).
(2) Tested insect: Adult of houseflies ; (3) Test Period: July 23, 1973 - August 16, 1973 - (4) Test Method: The respective concentrate were diluted ten times with water and were each sprayed over the inner surfaces of a room in an amount 50 ml/m2. 1, 5, lO, l~ and 25 days after the spraying treatment, each 200 flies were let in the room and the xoom was closed. 24 hours after the closing, the number of dead flies was examined. In the test results, the ~ term "closed division" is intended to mean that the windows in; the room were all closed during the course of the test, while ;; 25 the term "opened division" means that the windows were all opened during a period between an examined day and a next ~; ~1etting-in day ,. , . .
.' ~ -''' .
~.
(5) Test Results ¦ Mortality (%) in a day in closed divis.ion . ~ ~
. ex~mined date7/23-7/2~ 7/27-7/28 8/1-8/2 8/9-8/10 8/16-B/17 l .-- . .
rreSent 5~ fenthion invention aqueous 100 100 100 100 100 l concentrate .
I -, ~ ~ , . _ Reference 5% fention emulsifiable 100 100 100 100 100 concentrate 1~ -- -- - - --- - - - ----- - - - -i room tempe~a- 30 O- 29 5-29.8- 31.5- 31.0-~: l ined day (C) 31.0 31.030.5 33 0 31.2 . . _ ~
~` I , ¦ Mortality (~) in a day in opened division I ,~
I . examlned date 7/23-7/24 7/27-7~23 8/1-8/2 8/9-8/10 8/16-8/17 :~ _ _ . - . '. .' `'.
. Present 5% fenthion invention aqueous 100 100 100 100 100 concentrate . . .
. _ __ __ __ Reference 5% fenthion I emulsifiable 100 100 100 100 100 .~ .... . . concentrate . .
_ oom ~ ~ ~
~:. temperature 30 5- 30 5- 28 7- 31 O- 31.5- : -~: of examined 32.0 32.0 30.5 35.1 33.0 _ _ . _ . ____ L . _ ¦
,~ . ',' E ~ (Comparative Test For Toxicity Against Fish) .
(1) Tested Insecticides l :
(a) 5 % fenthion aqueous concentrate prepared in the - same manner as in Example l-(l)-(a). I
(b) 5 % fenthion emulsifiable concentrate prepared in the same manner as in Example l-(l)-(b).
. (2) Tested Fish: Adult of red killifish ,.~ . .
. .
~ . - 17 -,. .
:: . - 1':'--~ 7 :' . . : ., ' ' ' , ' .. ~ ' . :: . . . .
': '' . ' ', '' ' ' . ' ' ' . : :
1115~049 (3~ Test Method: A number of red killifish were kept for 1 - 10 days, among which a predetermined number of sprightly fish with almost the same len~th were chosen for the test.
5 - 10 fish were placed in an enameled container(30 cm x 20 cm x 12 cm in depth) containing 4000 ml of an insecticidal solution Wit}l a predetermined concentration. 48 hours a~ter contact with the insecticidal solution, the number of the dead was counted. The dead fish was removed every 12 hours. The test was repeated 3 to 15 times at each concentration. During the test, the enameled container was immersed to a certain level i in a concrete vessel over the top of which well water invariab]y overflowed so as to maintain the solution at a temperature as constant as possible.
(4) Results -Mortality of red killifish 48 hours after contact with insecticidal solutlon :, ' , , , . , .__ ______ .~ ind of Present invention Reference :` , \ \ lnsecti-\ \ cide 5% fenthion aqueous ~
\ \ concentrate emulsifiable concentrate oncen-\ ` . - _ ~ ~
tration \ Number of Number of Mortality Number of Number of Mortallty \ tested dead fish tested dead fish \ fish fish . .- ... .. . _ . ~ . . _ ~ . ~ ...... ..
3.0 ppm70 32 45.7 _ _ _ . . 2.0 85 15 17.6 85 36 42.4 .. 1.0 65 ~ 6.2 85 7 8.2 ; 0.5 70 0 0 100 8 8.0 . 0.25 _ ~ _ 30 0 0 ~:
:', ` _ _ _ _ _ ._ ........... _ :' From the above results, it will be understood that the ~` aqueous concentrate of the present invention is far lower in .,.
. .
- 18 ~
-:
,:' ' ' . '~, ' ' : ~ -105404~ 1 toxicity agalnst fish than the known emulsifiable concentrate.
Example 4 (Cutaneous Irritation Test) ._ (1) Tested Insecticide 5 ~ fenthion aqueous concentrate prepared in the same S manner as in Example l~ (a).
(2) ~ested Animals Male rabbits each having a weight of 2.0 - 3.0 kg were used, six for reference and another six for application of the testing insecticide.
(3) Application Method The back of each rabbit was shaved in a circular shape of a radius of 2.0 - 3.0 cm. 24 hours after the shaving, remaining fur was fallen off by the use of a depilatory cream.
2 days after the falling-off, O.S ml of the insecticide to be tested was uniformly applied to the back.
(4) Estimation The degrees of rubefacient and scabbing formation and also of edema were estimated in accordance with the Dvaize method and were expressed in terms of marks. The intensity of the cutaneous irritation was determined from the average value of the marks obtained 24 hours and 48 hours after the application.
(5j Results As will be clear from the following Table, the 5 ~i fenthion aqueous concentrate has a final estimation mark of 0.33 and is thus found to give little cutaneous irritation aotion on the bits.
. ' .
.. ~ -' 19 -'.~ . .
1'''1'' 1~5~9 -- Kind of Days 1 2 3 4 5 6 7 Final ect:cide lo.l _ 10' ~_ 1 ~
.~ 5% fenthion aqueous~ 3 _ _ _ _ _ _ _ `
~c~nt ~ ¦ 4 2 ' "
Example 5 (Preparation of Various Aqueous Concentrate and ~ :
Insecticidal Efficacy and Stability Thereof) (1) Preparation of Insecticides (a) Diazinon insecticide of invention - 1. 5% diazinon aqueous concentrate ~. - .
. .
- 5 g of diazinon as an insecticidal organo-phosphorus ; :.
:............ compound, 14 g of polyoxyethylene diphenylmethylphenyl ether (mol number of ethylene = 12~ and 0.7 g of sodium lauryl-sulfate as a surface active agent were mixed together. Then, ~;
79.3 g of a mixture (having a pH of 7.0~ of an aqueous 1/20 mols potassium dihydrogenphosphate solution and an aqueous 1/20 mols disodium hydrogenphosphate solution in a mixing ratio by volume of 1:2 was gradually added, as a pH adjusting agent, to the above mixture with stirring, thereby to obtain : a uniform clear solution. Finally 1 g of polyethylene glycol .
.
l~S~
diglycidyl ether as a s-tabili~er was added -to the solution to obtain 5% diazinon aqueous concentrate.
2. 5~ diazinon aqueous concentrate 5.~ g o~ diazinon, ].0 g oE polyoxyethylene non-~lphenol ether (having an ethylene mol number of 10) and 5 g o sodium al~ylnaphthalenesulfonate were mixed together.
To the mixture was added a mixture (having a pll of 7.4) of an aqueous 1/15 mols potassium dihydrogenphosphate and an ~ .
aqueous 1/15 mols disodium hydrogenphosphate solution in a mixing ratio by volume of 1:4 with stirring to obtain a -~
~ uniform clear solution, to which was further added 0.2 g of : sodium dehydroacetate as an antifungal agent thereby obtaining 5% diazinon aqueous concentrate. :~
3. 20~ diazinon aqueous concentrate 23 g of diazinon, 20 g of polyoxyethylene nonyl-phenol ether (having an ethylene mol number of 10~ and 7 g of sodium alkylnaphthalenesulfonate were mixed together. To the mixture was added 47.9 g of a mixture (.having a pH of ~ 7.8) of an aqueous 1/10 mol potassium dihydrogenphosphate ~;; .
and an aqueous 1/20 mols borax solution in a mixing ratio .:
~` by volume of 1:1 with stirring to obtain a uniform clear solution, to which were added 2 g of a stabilizer, phenyl . glycidyl ether and 0.2 g of an antifungal agent to give 20%
:` diazinon aqueous concentrate~ :
: . : .
.~ 4. 45~ diazinon aqueous concen*rate ... :
. 45 g of diazinon aqueous concentrate, 15 g of :, polyoxyethylene nonylphenol ether ~.having an ethylene mol number of 10), 5 g of sodium al~ylnaphthalenesulfonate and ;~ :
10 g of ethyl cellosolve as an organic solvent were mixed . 30 together. To the mixture was further added 21.~5 g of a ;.
` mixture (.having a pH of 7.4) of an aqueous 1/5 mols potassium ~:
- 21 ~
.: . .. - , . ~ . , - :
.. . . .
~05~ 9 dihydrogenphosphate and disodium hydrogenphosphate in a mixing ratio by volume of 1:4 with stirring to obtain a uniform clear solution. ThereaEter, 3 g of a stabilizer, phenyl glycidyl e-ther and 0.05 g of an an-tifungal agent, henxoisoth:iazolone, were added -to the solution to obtain 45% diazinon aqueous concentrate.
(b) 10~ fenitrothion aqueous concentrate 10 g of fenitrothion as an insecticidal or~ano-phosphorus compound, and 20 g of polyoxyethylene distyryl-methylphenyl ether (having an ethylene mol number of 10), were mixed together. To the mixture was gradually added, as a pH adjusting agent, 69 g of a mixture (having a pH of
. ex~mined date7/23-7/2~ 7/27-7/28 8/1-8/2 8/9-8/10 8/16-B/17 l .-- . .
rreSent 5~ fenthion invention aqueous 100 100 100 100 100 l concentrate .
I -, ~ ~ , . _ Reference 5% fention emulsifiable 100 100 100 100 100 concentrate 1~ -- -- - - --- - - - ----- - - - -i room tempe~a- 30 O- 29 5-29.8- 31.5- 31.0-~: l ined day (C) 31.0 31.030.5 33 0 31.2 . . _ ~
~` I , ¦ Mortality (~) in a day in opened division I ,~
I . examlned date 7/23-7/24 7/27-7~23 8/1-8/2 8/9-8/10 8/16-8/17 :~ _ _ . - . '. .' `'.
. Present 5% fenthion invention aqueous 100 100 100 100 100 concentrate . . .
. _ __ __ __ Reference 5% fenthion I emulsifiable 100 100 100 100 100 .~ .... . . concentrate . .
_ oom ~ ~ ~
~:. temperature 30 5- 30 5- 28 7- 31 O- 31.5- : -~: of examined 32.0 32.0 30.5 35.1 33.0 _ _ . _ . ____ L . _ ¦
,~ . ',' E ~ (Comparative Test For Toxicity Against Fish) .
(1) Tested Insecticides l :
(a) 5 % fenthion aqueous concentrate prepared in the - same manner as in Example l-(l)-(a). I
(b) 5 % fenthion emulsifiable concentrate prepared in the same manner as in Example l-(l)-(b).
. (2) Tested Fish: Adult of red killifish ,.~ . .
. .
~ . - 17 -,. .
:: . - 1':'--~ 7 :' . . : ., ' ' ' , ' .. ~ ' . :: . . . .
': '' . ' ', '' ' ' . ' ' ' . : :
1115~049 (3~ Test Method: A number of red killifish were kept for 1 - 10 days, among which a predetermined number of sprightly fish with almost the same len~th were chosen for the test.
5 - 10 fish were placed in an enameled container(30 cm x 20 cm x 12 cm in depth) containing 4000 ml of an insecticidal solution Wit}l a predetermined concentration. 48 hours a~ter contact with the insecticidal solution, the number of the dead was counted. The dead fish was removed every 12 hours. The test was repeated 3 to 15 times at each concentration. During the test, the enameled container was immersed to a certain level i in a concrete vessel over the top of which well water invariab]y overflowed so as to maintain the solution at a temperature as constant as possible.
(4) Results -Mortality of red killifish 48 hours after contact with insecticidal solutlon :, ' , , , . , .__ ______ .~ ind of Present invention Reference :` , \ \ lnsecti-\ \ cide 5% fenthion aqueous ~
\ \ concentrate emulsifiable concentrate oncen-\ ` . - _ ~ ~
tration \ Number of Number of Mortality Number of Number of Mortallty \ tested dead fish tested dead fish \ fish fish . .- ... .. . _ . ~ . . _ ~ . ~ ...... ..
3.0 ppm70 32 45.7 _ _ _ . . 2.0 85 15 17.6 85 36 42.4 .. 1.0 65 ~ 6.2 85 7 8.2 ; 0.5 70 0 0 100 8 8.0 . 0.25 _ ~ _ 30 0 0 ~:
:', ` _ _ _ _ _ ._ ........... _ :' From the above results, it will be understood that the ~` aqueous concentrate of the present invention is far lower in .,.
. .
- 18 ~
-:
,:' ' ' . '~, ' ' : ~ -105404~ 1 toxicity agalnst fish than the known emulsifiable concentrate.
Example 4 (Cutaneous Irritation Test) ._ (1) Tested Insecticide 5 ~ fenthion aqueous concentrate prepared in the same S manner as in Example l~ (a).
(2) ~ested Animals Male rabbits each having a weight of 2.0 - 3.0 kg were used, six for reference and another six for application of the testing insecticide.
(3) Application Method The back of each rabbit was shaved in a circular shape of a radius of 2.0 - 3.0 cm. 24 hours after the shaving, remaining fur was fallen off by the use of a depilatory cream.
2 days after the falling-off, O.S ml of the insecticide to be tested was uniformly applied to the back.
(4) Estimation The degrees of rubefacient and scabbing formation and also of edema were estimated in accordance with the Dvaize method and were expressed in terms of marks. The intensity of the cutaneous irritation was determined from the average value of the marks obtained 24 hours and 48 hours after the application.
(5j Results As will be clear from the following Table, the 5 ~i fenthion aqueous concentrate has a final estimation mark of 0.33 and is thus found to give little cutaneous irritation aotion on the bits.
. ' .
.. ~ -' 19 -'.~ . .
1'''1'' 1~5~9 -- Kind of Days 1 2 3 4 5 6 7 Final ect:cide lo.l _ 10' ~_ 1 ~
.~ 5% fenthion aqueous~ 3 _ _ _ _ _ _ _ `
~c~nt ~ ¦ 4 2 ' "
Example 5 (Preparation of Various Aqueous Concentrate and ~ :
Insecticidal Efficacy and Stability Thereof) (1) Preparation of Insecticides (a) Diazinon insecticide of invention - 1. 5% diazinon aqueous concentrate ~. - .
. .
- 5 g of diazinon as an insecticidal organo-phosphorus ; :.
:............ compound, 14 g of polyoxyethylene diphenylmethylphenyl ether (mol number of ethylene = 12~ and 0.7 g of sodium lauryl-sulfate as a surface active agent were mixed together. Then, ~;
79.3 g of a mixture (having a pH of 7.0~ of an aqueous 1/20 mols potassium dihydrogenphosphate solution and an aqueous 1/20 mols disodium hydrogenphosphate solution in a mixing ratio by volume of 1:2 was gradually added, as a pH adjusting agent, to the above mixture with stirring, thereby to obtain : a uniform clear solution. Finally 1 g of polyethylene glycol .
.
l~S~
diglycidyl ether as a s-tabili~er was added -to the solution to obtain 5% diazinon aqueous concentrate.
2. 5~ diazinon aqueous concentrate 5.~ g o~ diazinon, ].0 g oE polyoxyethylene non-~lphenol ether (having an ethylene mol number of 10) and 5 g o sodium al~ylnaphthalenesulfonate were mixed together.
To the mixture was added a mixture (having a pll of 7.4) of an aqueous 1/15 mols potassium dihydrogenphosphate and an ~ .
aqueous 1/15 mols disodium hydrogenphosphate solution in a mixing ratio by volume of 1:4 with stirring to obtain a -~
~ uniform clear solution, to which was further added 0.2 g of : sodium dehydroacetate as an antifungal agent thereby obtaining 5% diazinon aqueous concentrate. :~
3. 20~ diazinon aqueous concentrate 23 g of diazinon, 20 g of polyoxyethylene nonyl-phenol ether (having an ethylene mol number of 10~ and 7 g of sodium alkylnaphthalenesulfonate were mixed together. To the mixture was added 47.9 g of a mixture (.having a pH of ~ 7.8) of an aqueous 1/10 mol potassium dihydrogenphosphate ~;; .
and an aqueous 1/20 mols borax solution in a mixing ratio .:
~` by volume of 1:1 with stirring to obtain a uniform clear solution, to which were added 2 g of a stabilizer, phenyl . glycidyl ether and 0.2 g of an antifungal agent to give 20%
:` diazinon aqueous concentrate~ :
: . : .
.~ 4. 45~ diazinon aqueous concen*rate ... :
. 45 g of diazinon aqueous concentrate, 15 g of :, polyoxyethylene nonylphenol ether ~.having an ethylene mol number of 10), 5 g of sodium al~ylnaphthalenesulfonate and ;~ :
10 g of ethyl cellosolve as an organic solvent were mixed . 30 together. To the mixture was further added 21.~5 g of a ;.
` mixture (.having a pH of 7.4) of an aqueous 1/5 mols potassium ~:
- 21 ~
.: . .. - , . ~ . , - :
.. . . .
~05~ 9 dihydrogenphosphate and disodium hydrogenphosphate in a mixing ratio by volume of 1:4 with stirring to obtain a uniform clear solution. ThereaEter, 3 g of a stabilizer, phenyl glycidyl e-ther and 0.05 g of an an-tifungal agent, henxoisoth:iazolone, were added -to the solution to obtain 45% diazinon aqueous concentrate.
(b) 10~ fenitrothion aqueous concentrate 10 g of fenitrothion as an insecticidal or~ano-phosphorus compound, and 20 g of polyoxyethylene distyryl-methylphenyl ether (having an ethylene mol number of 10), were mixed together. To the mixture was gradually added, as a pH adjusting agent, 69 g of a mixture (having a pH of
6.1) of an aqueous l/20 mols potassium dihydrogenphosphate and an aqueous 1/20 mols disodium hydrogenphosphate solution with stirring to give a uniform clear solution. Finally, l g of a stabilizer; polyethylene glycol diglycidyl ether, ~ was added to the solution to obtain 10% fenitrothion aqueous ; concentrate.
(c) 10% ronnel aqueous concentrate 15.4 g (with a pure ronnel of lO g) of ronnel solution (having a purity of 65% and being in the form of a methylene chloride solution) as an insecticidal organo-phosphorus compound and 20 g of polyoxyethylene distyryl-methylphenyl ether having an ethylene mol number o~ lO) were mixed together, to which 64.6 g of water was gradully added with stirring to give a uniform clear solution. The solution was adjusted to have a pH of S-6.
.. ~ ;
~2 ':
~ ~ 22 ~
:: , 11)54049 (2) Insecticidal efficacy and stability The i~secticidal efficacy and stability of the respective insecticides are shown in Table below.
.`
Insecticidal Efficacy . . ....... .. ,.. , .. ... ,.,........ ,........... ., r___ _ , _ _ v _ Kind of insecticide ~`
T e s t ;. ~ t ~ ~ ¦ ( b ) ( c ) Diazinon Fenitrothion Ronnel _._ . __ Larva of Immersion 0.036 ppm 0.0098 ppm 0.025 ppm Mosquitoes method LC-50 Adult of Spray-dropp-~ houseflies ing method 15 min. & 29 min. & 20 min. &
;~! (Nagasawa' 15 sec. 48 sec. 20 sèc.
method) KT-50 ' ~
,, _ ~ . - I
`, ' ".,' Note: The test methods are the same as in Example 1-(2)-(a), with the abbreviations, LC-50 and KT-50, having the same meanings as defined in Example 1-(2)-(a), respectively.
:' ., Decomposition Rate Of Effective Component During Storage :' . . . . . ................. ............................
-~ ~ ind of insec-,~ ~nt Dia~inon thion Ronnel Storing ~ nSec ~ _ ~ _ conditions \ ~ ~ 1 2 3 4 ~
Room temperature 4.0 % 2.5 %3.0 % 4 r 0 % 4.2 % 2.8 %
, (5 - 34C~
one year . . . ___ ., _ _ Note: Samples were each placed in a closed glass bottle and stored in light-shielded box. ' .'~', .
.
`` ` - 23 -..
ir~F- ~
.. ...
.
~. , . :, , . , - , ~
.
(c) 10% ronnel aqueous concentrate 15.4 g (with a pure ronnel of lO g) of ronnel solution (having a purity of 65% and being in the form of a methylene chloride solution) as an insecticidal organo-phosphorus compound and 20 g of polyoxyethylene distyryl-methylphenyl ether having an ethylene mol number o~ lO) were mixed together, to which 64.6 g of water was gradully added with stirring to give a uniform clear solution. The solution was adjusted to have a pH of S-6.
.. ~ ;
~2 ':
~ ~ 22 ~
:: , 11)54049 (2) Insecticidal efficacy and stability The i~secticidal efficacy and stability of the respective insecticides are shown in Table below.
.`
Insecticidal Efficacy . . ....... .. ,.. , .. ... ,.,........ ,........... ., r___ _ , _ _ v _ Kind of insecticide ~`
T e s t ;. ~ t ~ ~ ¦ ( b ) ( c ) Diazinon Fenitrothion Ronnel _._ . __ Larva of Immersion 0.036 ppm 0.0098 ppm 0.025 ppm Mosquitoes method LC-50 Adult of Spray-dropp-~ houseflies ing method 15 min. & 29 min. & 20 min. &
;~! (Nagasawa' 15 sec. 48 sec. 20 sèc.
method) KT-50 ' ~
,, _ ~ . - I
`, ' ".,' Note: The test methods are the same as in Example 1-(2)-(a), with the abbreviations, LC-50 and KT-50, having the same meanings as defined in Example 1-(2)-(a), respectively.
:' ., Decomposition Rate Of Effective Component During Storage :' . . . . . ................. ............................
-~ ~ ind of insec-,~ ~nt Dia~inon thion Ronnel Storing ~ nSec ~ _ ~ _ conditions \ ~ ~ 1 2 3 4 ~
Room temperature 4.0 % 2.5 %3.0 % 4 r 0 % 4.2 % 2.8 %
, (5 - 34C~
one year . . . ___ ., _ _ Note: Samples were each placed in a closed glass bottle and stored in light-shielded box. ' .'~', .
.
`` ` - 23 -..
ir~F- ~
.. ...
.
~. , . :, , . , - , ~
.
Claims (12)
- The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
l. An aqueous insecticidal concentrate composition comprising:
an insecticidal organo-phosphorus compound;
water; and a surface active agent in an amount sufficient to render said organo-phosphorus compound soluble in the water, the pH of said composition ranging from 3.0 to 8.5. - 2. The composition as defined by claim 1, wherein the content of said organo-phosphorus compound is between 2 and 50 % based on the weight of said composition and the content of said water is at least 20 % based on the weight of said composition.
- 3. The composition as defined by claim 2, wherein the content of said surface active agent ranges from 2 to 30 %
based on the weight of said composition. - 4. The composition as defined by claim 3, further comprising an organic solvent in an amount of less than that of said water.
- 5. The composition as defined by claim 4, wherein the organic solvent is a polar organic solvent in an amount of below 15 % based on the total weight of the composition.
- 6. The composition as defined by claim 1, wherein said organo-phosphorus compound has a solubility in water of not higher than 2%
- 7. The composition as defined by claim 6, further comprising an antifungal agent and a stabilizer.
- 8. The composition as defined by claim 7, wherein said antifungal agent is selected from sodium dehydroacetate and l,2-benzisothiazolone and is present in an amount of between 0.04 and 0.4% based on the weight of said composition and wherein said stabilizer is an epoxy compound and is present in an amount of between 0.3 and 3% based on the weight of said composition.
- 9. The composition as defined by claim 6, wherein said organo-phosphorus compound is expressed by the formula:
wherein R1 represents a lower alkyl, R2 represents a lower alkoxy or phenyl, R3 represents a phenyl having one to three substituents selected from the group consisting of methyl, nitro, cyano, chlorine and methylthio, 2-isopropyl-4-methyl-6-pyrimidinyl, 3,5,6-trichloro-2-pyridyl, 1,2-diethoxycarbonyl or l-ethoxy-carbonyl-l-phenylmethyl, and X1 and X2 are each oxygen or sulfur. - 10. The composition as defined by claim 9, wherein said organo-phosphorus compound is expressed by the formula:
wherein R4 is methyl or ethyl and R5 is or - 11. The composition as defined by claim 10, wherein said organo-phosphorus compound is O,O-diethyl-0-[2-isopropyl-4-methylpyrimidyl(6)]thiophosphate.
- 12. The composition as defined by claim 11, wherein the pH of said composition is in the value of between 6.5 and 8.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA265,888A CA1054049A (en) | 1976-11-17 | 1976-11-17 | Aqueous insecticidal concentrate composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA265,888A CA1054049A (en) | 1976-11-17 | 1976-11-17 | Aqueous insecticidal concentrate composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1054049A true CA1054049A (en) | 1979-05-08 |
Family
ID=4107305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,888A Expired CA1054049A (en) | 1976-11-17 | 1976-11-17 | Aqueous insecticidal concentrate composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1054049A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388297A (en) | 1980-06-19 | 1983-06-14 | The Dow Chemical Company | Stable tocicant compositions of chlorpyrifos |
-
1976
- 1976-11-17 CA CA265,888A patent/CA1054049A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388297A (en) | 1980-06-19 | 1983-06-14 | The Dow Chemical Company | Stable tocicant compositions of chlorpyrifos |
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