JPS6145601B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water-based aerosol insecticides. Water-based aerosol insecticides are currently being actively developed because they have advantages such as significantly reduced risks such as flammability and toxicity to human stock, and low production costs. However, most of the currently known products are of the so-called separation type, in which water and insecticide components are separated. These should be shaken well before use. Therefore, it is desired to develop a homogeneous type of insecticide in which the insecticide component is uniformly dispersed in water and remains uniformly transparent for a long period of time. The only known homogeneous water-based aerosol insecticide is an aerosol insecticide in which a propellant is blended into a dispersion of a pyrethroid insecticide in water using a lower alcohol. Furthermore, with currently known water-based aerosol insecticides, whether separated or homogeneous, the insecticidal ingredients decompose over time, reducing their insecticidal efficacy and, therefore, decreasing their storage stability. cannot be avoided. In view of the current situation, the present inventors have conducted intensive research to develop a homogeneous water-based aerosol insecticide with excellent storage stability. As a result, the inventors discovered that the intended purpose of the present invention could be achieved only when a specific nonionic surfactant was used as a dispersant, leading to the completion of the present invention. That is, the present invention provides a water-based aerosol insecticide, which is a water-based aerosol insecticide prepared by blending a propellant of the same volume or less with a stock solution in which a pyrethroid insecticidal component is dispersed in water.
~15 polyoxyethylene hydrogenated castor oil fatty acid ester, HLB 10~15 polyoxyethylene hydrogenated castor oil, HLB 9~14 polyoxyethylene polyoxypropylene alkyl ether, and
A water-based aerosol insecticide characterized in that a pyrethroid insecticidal ingredient is dispersed in water using a surfactant containing at least 50% by weight of at least one selected from HLB 9 to 15 polyoxyethylene polypropylene glycol. Pertains to. The composition of the present invention is of a uniform type and can maintain a stable and uniformly transparent state, that is, a solubilized state, even under harsh conditions for a long period of time.Therefore, there is no need to shake it before use, and it can be sprayed into the air as fine particles with a single touch. obtain. Furthermore, the composition of the present invention has excellent storage stability and can exhibit an excellent insecticidal effect over a long period of time, and the insecticidal effect does not decrease with the passage of time. In the present invention, fatty acid ester of polyoxyethylene hydrogenated castor oil with HLB 10-15, polyoxyethylene hydrogenated castor oil with HLB 10-15, polyoxyethylene polyoxypropylene alkyl ether with HLB 9-14, and polyoxyethylene polypropylene with HLB 9-15 are used in the present invention. It is essential to use at least one surfactant selected from glycols. Surfactants other than the above nonionic surfactants, and even if the above nonionic surfactants are
If a substance outside the HLB range is used, it will not be a uniform type that can maintain a stable and transparent state, and it will not be possible to suppress the decomposition of the insecticidal component, so that the intended purpose of the present invention cannot be achieved. do not have. In the present invention, if the above-mentioned specific nonionic surfactant is contained in the surfactant used in an amount of 50% by weight or more, the desired effect of the present invention can be achieved regardless of the types of other surfactants mixed therein. It can be fully demonstrated. If the amount of the above-mentioned specific nonionic surfactant is less than 50% by weight, the intended purpose of the present invention cannot be achieved. As the fatty acid ester of polyoxyethylene hydrogenated castor oil, those having an HLB in the range of 10 to 15 can be widely used. As the fatty acid constituting the fatty acid ester of polyoxyethylene hydrogenated castor oil, any higher fatty acid having 8 to 22 carbon atoms can be used, and the number of moles of ethylene oxide added is selected so that the HLB is 10 to 15. Specifically, polyoxyethylene hydrogenated castor oil monolaurate (HLB12), polyoxyethylene hydrogenated castor oil monoisostearate (HLB12), polyoxyethylene hydrogenated castor oil monopalmitate (HLB12), polyoxyethylene hydrogenated castor oil Examples include monooleate (HLB12). As the polyoxyethylene hydrogenated castor oil, those having an HLB in the range of 10 to 15 can be widely used. In this case, the number of moles of ethylene oxide added is generally from 30 to 60. As polyoxyethylene polyoxypropylene alkyl ether
Those having an HLB in the range of 9 to 14 can be widely used. As the alkyl group constituting the polyoxyethylene polyoxypropylene alkyl ether, any alkyl group having 8 to 22 carbon atoms can be used, and the number of moles of ethylene oxide and propylene oxide added is
The HLB is selected to be between 9 and 14. Specific examples include polyoxyethylene polyoxypropylene cetyl ether (HLB10) and polyoxyethylene polyoxypropylene behenyl ether (HLB10). As polyoxyethylene polypropylene glycol, those with HLB 9 to 15 can be widely used, for example, 20 to 80% by weight of ethylene oxide and propylene glycol.
The average molecular weight with addition of 80 to 20% by weight is 1750 to
I can list things within the range of 3000.
A wide variety of known surfactants can be used as the surfactant mixed with the above-mentioned specific nonionic surfactant, such as polyoxyethylene styrenated phenol,
Polyoxyethylene polypropylene glycol monooleate, polyethylene glycol monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene castor oil, benzalkonium chloride, dioctyl sulfosuccinate soda salt, polyethylene glycol octyl phenyl ether, HLB Examples include polyoxyethylene polyoxypropylene cetyl ether other than 9 to 14, polyoxyethylene alkyl phenyl ether, polyoxyethylene monooleate, and the like. The amount of surfactant to be contained in the composition of the present invention is not particularly limited and can be appropriately selected from a wide range, but is usually 0.05 to 20% by weight (hereinafter simply referred to as "%"), preferably 0.1 to 20% by weight. It is best to set it at 5%. If the content of the surfactant is too high, the liquid becomes viscous, making it difficult to spray, and if the content is too low, the solubilizing effect is reduced, making it impossible to achieve the desired effect of the present invention. As the pyrethroid insecticidal ingredients used in the present invention, a wide range of known ones can be used, such as phthalthrin (N-(chrysansemoxymethyl)-3.
4,5,6-tetrahydrophthalimide), allethrin, resmethrin (5-benzyl-3-furylmethylchrysanthemate), propulthrin (2-methyl-5-propargyl-3-furylmethylchrysanthemate), flamethrin ( 5-propargyl furfuryl chrysanthemate), insecticidal chrysanthemum extract, permethrin (metaphenoxybenzyl-2,2-dimethyl-3 (β,β-dichlorovinylcyclopropane carboxylate) Natural or synthetic pyrethroid insecticidal ingredients such as enoxybenzyl chrysanthemate), stereoisomers, optical isomers, etc. of these insecticidal ingredients can be mentioned. 1-ethynyl-2-methyl-2-pentenyl alcohol represented by Propane-1-carboxylic acid and 2,2-dimethyl-
Esters with acids selected from the group consisting of 3-(2'-methyl-1'-propenyl)cyclopropanecarboxylic acids are also included. The amount of the pyrethroid insecticidal component blended into the composition of the present invention is not particularly limited and may be selected from a wide range, but is usually 0.01
-5%, preferably 0.05-1%.
If the amount of the insecticidal component is too large, the amount of surfactant used to maintain uniformity will be large, resulting in a viscous liquid, which is undesirable, and if the amount is too small, excellent insecticidal effects will not be exhibited, which is undesirable. As the propellant used in the present invention, a wide variety of known propellants can be used, such as dimethyl ether,
Examples include carbon dioxide gas, nitrogen gas, and laughing gas. Among these, it is preferable to use dimethyl ether. The amount of propellant to be incorporated into the composition of the present invention is equal to or less than the same volume as the total amount of the undiluted solution, ie, the surfactant, pyrethroid insecticidal component, and water. The composition of the present invention usually contains 5 to 50% propellant.
%, preferably 20 to 45%. In the present invention, if necessary, third components such as so-called synergists, rust preventives, preservatives, fragrances, etc., which enhance the insecticidal effect of the insecticidal components, may be appropriately added. As the third component, a wide variety of materials commonly used in this field can be used.
Specifically, the synergists include piperonyl butoxide, octachlorodipropyl ether,
MGK264, Cinepirin, etc., and as anti-rust agents, Curlene No.955, No.906, No.954, No.958, etc.
No. 970 (all trademarks: manufactured by Sanyo Chemical Industries, Ltd.), etc., and the preservatives include sodium salicylate, sodium benzoate, potassium sorbate,
Examples include sodium dehydroacetate. A wide variety of methods commonly used in the art may be used in preparing the water-based aerosol insecticides of the present invention. A typical method involves heating (50 to 60°C) and mixing a predetermined amount of pyrethroid insecticidal ingredients, specific nonionic surfactants, other surfactants, synergists, fragrances, etc. to create a uniform viscous liquid. After that, let it cool, add water, stir until it becomes a homogeneous liquid, add rust preventive agent, preservative, etc. at the same time, put the resulting stock solution into an aerosol can, fill it with a propellant, and make a product. be able to. The composition of the present invention thus obtained can maintain a stable and uniformly transparent state even under harsh conditions for a long period of time, and when desired, can be sprayed into the air as fine particles with a single touch. Examples and comparative examples are listed below to further clarify the present invention. Example 1 Mixed weight parts Allethrin 0.2 Polyoxyethylene polyoxypropylene cetyl ether (HLB10) 0.6 Polyethylene glycol monooleate (HLB14) 0.2 Polyoxyethylene polypropylene glycol monooleate (HLB18) 0.2 Water Approximately 74.0 Dimethyl ether 24.8 Total 100.0 Allethrin , heat and mix the above various surfactants in the above weight parts, add about 74 parts by weight of water, and make up the total amount.
After reducing the amount to 75.2 parts by weight, it is placed in an aerosol can and filled with 24.8 parts by weight of dimethyl ether. A sample of the resulting composition of the present invention was heated at 0°C and 40°C.
The compositions were left in a room maintained at a temperature of 0.degree. C. for 3 months, and the liquid state of each composition was examined, and all were found to be homogeneous transparent liquids. In addition, the amount of effective insecticidal ingredients contained in the composition of the present invention after being left for 3 months was measured using gas chromatography according to a conventional method, and the amount remained by dividing the amount by the amount added at the time of manufacturing the composition of the present invention. The rate (%) was calculated. The residual rate of allethrin when left at 0°C was 97.8%, and when left at 40°C it was 99.9%. Comparative Example 1 A sample of an insecticide composition was produced in the same manner as in Example 1, except that polyoxyethylene polyoxypropylene cetyl ether (HLB16) was used instead of polyoxyethylene polyoxypropylene cetyl ether (HLB10). Immediately after production, the composition is already cloudy and does not become a homogeneous transparent liquid. Samples of this insecticide composition were left in chambers maintained at temperatures of 0° C. and 40° C., and when the liquid state of the composition was examined, it was found that each layer had separated into two layers. In addition, the amount of effective insecticidal ingredients contained in the insecticide composition after being left for three months was measured, and the residual rate was determined in the same manner as in Example 1. At 0°C, the residual rate was 70.2.
%, and 43.5% at 40°C. Example 2 Compound weight parts Allethrin 0.4 Polyoxyethylene hydrogenated castor oil monolaurate (HLB12) 3.0 Polyoxyethylene polypropylene glycol monooleate (HLB18) 0.4 Polyoxyethylene styrenated phenol (HLB14) 0.4 Water Approximately 65.8 Dimethyl ether 30.0 Total 100.0 A sample of the composition of the present invention was prepared in the same manner as in Example 1 with the above formulation. The sample was heated to 0°C and 40°C.
Both were left for 3 months and a portion of the liquid was collected. 0
When left at ℃, allethrin survival rate is 97.8%, 40
When left at ℃, the residual rate of allethrin was 99.9%, and no decomposition was observed. Furthermore, it exhibited a uniform, transparent, and stable liquid state at both 0°C and 40°C. Comparative Example 2 A sample of an insecticide composition is obtained in the same manner as in Example 2, except that 35.8 parts by weight of water and 60.0 parts by weight of dimethyl ether are used. The composition was not uniformly transparent and became cloudy, and when the solution was collected after being left at 0°C and 40°C for 3 months, it was found to have separated into two layers. Example 3 Compound weight parts Phthalithrin 0.1 Allethrin 0.1 Polyoxyethylene polypropylene glycol (HLB10) 0.7 Polyethylene glycol octyl phenyl ether (HLB14) 0.3 Polyoxyethylene polypropylene glycol monooleate (HLB18) 0.3 Water Approximately 76.5 Dimethyl ether 22.0 Total 100.0 Above A sample of the composition of the present invention was obtained using the same formulation as in Example 1. When this sample was left at 0°C and 40°C for 3 months and a portion of the liquid was collected, both exhibited a uniform, transparent, and stable liquid state. 0 again
If left at ℃, Phthalthrin 98.2%, Allethrin
The residual rate is 97.9%, and when left at 40℃, the residual rate is 99.0% for phthalthrin and 98.5% for allethrin.
No decomposition was observed in either case. Comparative Example 3 Mixture parts by weight Phthalthrin 0.1 Allethrin 0.1 Ethanol 30.0 Water Approximately 30.0 Dimethyl ether 39.8 Total 100.0 A sample of an insecticide composition was obtained in the same manner as in Example 1 with the above formulation. When this sample was left at 0°C and 40°C for 3 months and a portion of the liquid was collected, both exhibited a uniform, transparent, and stable liquid state. 0 again
If left at ℃, Phthalthrin 54.2%, Allethrin
The residual rate is 70.0%, and when left at 40℃, the residual rate is 5.0% for phthalthrin and 46.8% for allethrin.
It can be seen that the addition of ethanol cannot prevent the decomposition of allethrin and phthalthrin. Example 4 Compound weight parts Phthalthrin 0.1 Allethrin 0.1 Polyoxyethylene polypropylene glycol (HLB10) 1.0 Polyoxyethylene styrenated phenol (HLB14) 0.3 Polyoxyethylene castor oil (HLB14) 0.3 Water Approximately 78.2 Dimethyl ether 20.0 Total 100.0 Implemented with the above formulation A sample of the composition of the present invention is obtained in the same manner as in Example 1. When this sample was left at 0°C and 40°C for 3 months and a portion of the liquid was collected, both exhibited a uniform, transparent, and stable liquid state. 0 again
If left at °C, phthalthrin 97.8%, allethrin
The residual rate is 98.0%, and when left at 40℃, the residual rate is 99.1% for phthalthrin and 98.6% for allethrin.
No decomposition was observed in either case. Comparative Example 4 A sample of an insecticide composition was obtained in the same manner as in Example 4, except that 1.0 parts by weight of an ionic surfactant fatty acid alkylolamide was used instead of polyoxyethylene polypropylene glycol (HLB10). When this sample was left at 0°C and 40°C for 3 months and a portion of the liquid was collected, both exhibited a uniform, transparent, and stable liquid state. When left at 0°C, the residual rate was 0% phthalthrin and 67.8% allethrin, and when left at 40°C, the residual rate was 0% phthalthrin and 34.3% allethrin. In particular, the decomposition of phthalthrin is remarkable. Example 5 An insecticidal composition was obtained using the surfactants listed in Table 1 below in the amounts listed in Table 2 below, and the remaining insecticidal components were evaluated in the same manner as in Example 1 after being left for 3 months. The rate and liquid state were investigated. These results are summarized in Table 2. The insecticide composition is prepared by adding water to the specified amount of surfactant and insecticidal ingredients listed in Table 2.
ml and filled with 100 ml of dimethyl ether gas. In addition, Neopinamine (trademark, manufactured by Sumitomo Chemical Industries, Ltd., generic name: phthalthrin) and Pinamin Fuorte (trademark, manufactured by Sumitomo Chemical Industries, Ltd.) were used as insecticidal ingredients.

【table】

【table】

【table】

[Table] Example 6 The surfactant, pyrethroid insecticidal ingredient, water and dimethyl ether listed in Table 1 above were added to the following Table 3.
An insecticide composition was obtained according to the mixing ratio shown in the table. In the same manner as in Example 1, the residual rate and liquid state of the insecticidal component after being left for 3 months was examined. These results are shown in Table 4.

【table】

【table】

【table】

[Table] Table 4 shows that when the amount of dimethyl ether gas exceeds the amount of water, cloudy separation occurs and the insecticidal component is also decomposed. Comparative Examples 5 to 10 Insecticide compositions having the following compositions were prepared according to the method described in JP-A-49-101522. Comparative example of blended weight part 5 A* 0.40 Polyglycerol oleate 0.80 Methylnaphthalene 0.38 Epoxidized soybean oil 0.50 Water 67.97 Isobutane 25.00 Comparative example 6 A* 0.40 BHA 0.10 Polyglycerol oleate 0.75 Methylnaphthalene 0.38 Light petroleum 6.5 Nitromethane 0.50 Water 56.42 Isobutane 35.00 Comparative example 7 A* 0.40 BHA 0.20 Polyglycerol oleate 0.60 Methylnaphthalene 0.38 Epoxidized soybean oil 0.75 Water 67.72 Isobutane 25.00 Propane 5.00 Comparative example 8 A* 0.23 Bioallethrin 0.16 Wingstay V 0.10 Polyglycerol oleate 0.75 Methyl Naphthalene 0.27 Epoxidized soybean oil 0.50 Water 62.99 Isobutane 35.00 Comparative example 9 A* 0.23 Bioallethrin 0.16 Wingstay V 0.20 Polyglycerol oleate 0.75 Nitromethane 0.75 Methylnaphthalene 0.27 Water 67.64 Isobutane 25.00 Propane 5.00 Comparative example 10 Pyrethrin 0. 25 Piperonyl butoxide 1.00 BHT 0.20 Polyglycerol oleate 0.75 Light oil 0.50 Water 60.80 Isobutane 25.00 Propane 5.00 A* indicates chrysanthemum acid ester of (±) trans-5-benzyl-3-furylmethyl alcohol. The mixture was left in a room maintained at 0°C and 40°C in the same manner as in Example 1, and its liquid state was examined. As a result, all compositions were separated into two layers.

Claims (1)

[Scope of Claims] 1. A water-based aerosol insecticide prepared by blending a propellant of the same volume or less with a stock solution of a pyrethroid insecticidal component dispersed in water, which is a fatty acid ester of polyoxyethylene hydrogenated castor oil with an HLB of 10 to 15. ,
A surfactant containing 50% by weight or more of at least one selected from polyoxyethylene hydrogenated castor oil with an HLB of 10 to 15, polyoxyethylene polyoxypropylene alkyl ether with an HLB of 9 to 14, and polyoxyethylene polypropylene glycol with an HLB of 9 to 15. A water-based aerosol insecticide characterized in that a pyrethroid insecticidal ingredient is uniformly dispersed in water. 2. The insecticide according to claim 1, wherein the pyrethroid insecticidal component is at least one selected from phthalthrin, allethrin, resmethrin, propulthrin, flamethrin, pyrethrum extract, permethrin, and phenothrin. 3. The insecticide according to claim 1 or 2, wherein the propellant is dimethyl ether. 4. The insecticide according to any one of claims 1 to 3, containing 0.05 to 20% by weight of a surfactant. 5. The insecticide according to claim 4, containing 0.1 to 5% by weight of a surfactant. 6. The insecticide according to any one of claims 1 to 5, containing 0.01 to 5% by weight of a pyrethroid insecticidal component. 7. The insecticide according to any one of claims 1 to 6, which contains 5 to 50% by volume of a propellant.