JP3041709B2 - Pyrethroid-based compound stabilizer and pyrethroid-based compound stabilization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a stabilizing agent for a pyrethroid compound and a method for stabilizing the compound, and more particularly to a method for stabilizing a pyrethroid compound by killing insects. The present invention relates to a light and / or ultraviolet light stabilizer for a pyrethroid compound and a method for stabilizing the compound against light and / or ultraviolet light.

[Conventional technology]

Conventionally, various drugs have been used as active ingredients in insecticide or acaricidal compositions for home use, epidemic control, and horticulture. For example, examples of the insecticide include organic chlorine compounds, organic phosphorus compounds, carbamate compounds, pyrethroid compounds, pyrethroid-like compounds, and oxadiazole compounds. Examples of the acaricide include organic phosphorus compounds, carbamate compounds, pyrethroid compounds, pyrethroid-like compounds, carbinol compounds, diazo compounds, and organic acids. Among these compounds, relatively safe compounds are used for home use, and typical examples thereof include pyrethroid compounds.

This pyrethroid compound is used for fly, mosquito, cockroach,
It shows a high insecticidal and acaricidal effect against sanitary pests such as acarid mites and dust mites, but has a significantly lower toxicity to humans and animals than pyrethroid-like compounds compared to other insecticides or acaricides. It is widely used as an active ingredient in acaricidal compositions.

However, this pyrethroid compound has heat, light,
Furthermore, since it has been pointed out that the stability is poor due to oxidation by oxygen, etc., the pyrethroid compound itself is being studied as a more stable derivative, while the pyrethroid compound in a composition containing the active ingredient as an active ingredient is considered. In order to stabilize the compound, a compound such as an antioxidant is added to the composition, the composition is stored in a cool and dark place, or the composition is placed in a sealed package, or a pyrethroid compound. In microcapsules and still used as a household insecticidal or acaricidal composition.

For example, introduction of halogen into the pyrethroid compound itself, addition of an antioxidant such as butylhydroxyanisole (BHA) or butylhydroxytoluene (BHT), addition of linolenic oil, tall oil, drill oil or sodium carbonate or potassium carbonate ( JP-A-59-202020), inclusion with cyclodextrin (JP-A-51-81888, JP-A-62-267)
No. 203), benzophenone derivatives, triazole derivatives, substituted acrylonitrile compounds, sterically hindered amines and the like (JP-A-59-39807, JP-A-59-116202)
No.), addition of a benzoic acid derivative (JP-A-60-136504),
Many measures have been taken, such as adsorption to mineral powder (talc).

JP-A-50-142728 discloses a method for maintaining the efficacy of a pyrethroid-based insecticide, which comprises adding at least one surfactant to at least one pyrethroid-based insecticide. This uses a pyrethroid-based insecticide in an electric mosquito catcher, using a surfactant to maintain its effectiveness for a time equivalent to its use time and to suppress its thermal decomposition rate. Several compounds are illustrated.

Further, JP-A-2-73001 describes that a powder for insect pests containing an amphoteric surfactant together with an insecticidal component such as a pyrethroid-based insecticide has an improved immediate effect.

[Problems to be solved by the invention]

When a conventionally known pyrethroid-based insecticide composition containing BHT or BHA is spray-coated on a window glass that stops pests for the purpose of controlling flies and the like, the insecticide is often exposed to light and air. Due to the exposure, the pyrethroid insecticidal component lost its efficacy due to decomposition and the like, and its stability was not sufficient, and the sustainability of the insecticidal efficacy was not satisfactory.

Japanese Patent Application Laid-Open No. 50-142728 discloses that a surfactant is effective in maintaining the efficacy of a pyrethroid insecticide, but in fact, all surfactants have the effect. Rather, it appears to have rather limited practical effects. In addition, it is the electric mosquito trap that has the efficacy lasting, and the volatility under the condition of electric heating does not decrease so much, and the intended duration is also the electric mosquito trap. Seems to have mainly used bedtime in mind, and therefore, the intended use is also considered in such a range.

By the way, in the use mode in which the pyrethroid-based insecticide composition is spray-coated on a window glass where insect pests are stopped for the purpose of controlling flies and the like as described above, an interface exemplified as being effective in the above-mentioned publication is used. Even when an activator was used, it did not have sufficient stability and was found to be unsuitable for practical use.

The present invention relates to a stabilizer capable of increasing the stability of a pyrethroid-based compound even in a place exposed to a large amount of light, particularly exposed to ultraviolet rays, and thereby increasing the persistence of insecticidal or acaricidal efficacy. And a stabilization method.

[Means for solving the problem]

The present invention has been made based on the discovery that certain surfactants can sufficiently stabilize a pyrethroid compound even under the above-described conditions or locations.

That is, the present invention has achieved the above object by the following means.

(1) Polyoxyethylene alkylamino ether, polyoxyethylene castor oil, polyoxyethylene polypropylene glycol monooleate, polyether-modified silicone oil, perfluoroalkyl carboxylate, fatty acid alkanolamide, alkyl sulfate, polyoxyethylene A stabilizer for a pyrethroid-based compound, comprising as a stabilizing component a surfactant comprising at least one member of the group consisting of alkyl ethers.

(2) Pyrethroid compounds are polyoxyethylene alkylamino ether, polyoxyethylene castor oil, polyoxyethylene propylene glycol monooleate,
Pyrethroids characterized by being stabilized by a surfactant comprising at least one member selected from the group consisting of polyether-modified silicone oil, perfluoroalkyl carboxylate, fatty acid alkanolamide, alkyl sulfate, and polyoxyethylene alkyl ether. Compound stabilization method.

Pyrethroid compounds to be stabilized in the present invention include all those known to be included therein, for example, pyrethrin, allethrin, resmethrin, permethrin, cypermethrin, phenothrin, cyphenothrin, empentrin , Fenfluthrin, terarethrine, phthalthrine, framethrin,
Examples include praletrin, fluvalinate, etofenprox, fenvalerate, benfluthulin, tralomethrin, and isomers, analogs and derivatives thereof.

The compounds include various commonly used potency enhancers,
Volatility improvers, antioxidants, fragrances, UV inhibitors, repellents, other insecticides, bactericides, rust inhibitors, fungicides, deodorants and the like can be added.

The mixing ratio of these additives to the above compound is determined by the dosage form,
The amount of the active ingredient or the amount up to the dissolved amount can be generally added to the whole composition, although it varies depending on the use scene, the target pest, and the like.

In the present invention, as the surfactant used for stabilizing the above compound, any surfactant can be used as long as it has a stabilizing action. Specifically, polyoxyethylene alkylamino ether, At least one of the group consisting of oxyethylene castor oil, polyoxyethylene polypropylene glycol monooleate, polyether-modified silicone oil, perfluoroalkyl carboxylate, fatty acid alkanolamide, alkyl sulfate, polyoxyethylene alkyl ether
Seed surfactants can be used.

Among these, typical commercially available ones are shown in Table 1.

In addition, (a) a mixture of a polyoxyethylene alkyl allyl ether polymer and an alkyl allyl sulfonate (trade name: Solpol 3080 (Yin), manufactured by Toho Chemical Co., Ltd.), (b) methyl tauride soda salt of oleic acid Product name: Marpon, manufactured by Matsumoto Yushi Co., Ltd., (c) dioctyl sulfosuccinate Na Product name: Marpomase PT (Yin),
Matsumoto Yushi Co., Ltd., (d) A mixture of 70% (polyoxyethylene styryl phenyl ether and polyoxyethylene styryl phenyl polymer) and 30% alkyl allyl sulfonate. (Product name: Solpol SM100P (Yin), manufactured by Toho Chemical Co., Ltd.) , (E) polyoxyethylene (10 mol) nonylphenyl ether {trade name: Penelol NP-10 (non), manufactured by Matsumoto Yushi Co., Ltd.), (f) perfluoroalkyloxyethylene adduct {trade name: SURFLON S-145 ( Non), made by Asahi Glass,
(G) Polyoxyethylene (30 mol) polyoxypropylene (6 mol) decyltetradecyl ether
NIKKOL PEN-4630 (non), Nikko Chemicals Co., Ltd. and the like can also be used as having the same effect.

The surfactant used in the present invention can be expected to be sufficiently effective at an equivalent mixing ratio (1: 1) to the pyrethroid compound. Even if the surfactant is mixed twice as much with the pyrethroid compound, the effect is hardly changed.

The addition amount of these surfactants to the entire composition (including additives and the like) can be in the range of 0.01 to 1 wt%, but is preferably 0.1 to 0.5 wt%.

Examples of the dosage form of the insecticidal or danicidal composition obtained by adding the stabilizer of the present invention or obtained by the stabilizing method of the present invention include ethanol, methanol, water, and mixtures thereof. Dissolve a pyrethroid compound and an appropriate amount of a stabilizer in a solvent such as to form a liquid formulation, dilute it to an appropriate concentration at the time of use and use it as a spray, or use LPG (liquefied natural gas), DME (dimethyl ether), A propellant such as a gas and a liquid comprising a pyrethroid compound, a stabilizer and a solvent may be blended and used as an aerosol. In the case of an aerosol, in addition to the one-pack type in which all the agents are contained in one container, a combination of a container containing only the propellant and a container containing the pyrethroid compound, a stabilizer and a solvent is used. A two-liquid type using an isolated injection device can also be used. In addition, a pump dispenser or the like may be used.

Furthermore, a sheet-like dosage form in which a pyrethroid-based compound, a solvent, and a stabilizer are impregnated into a nonwoven fabric, paper, or the like can be used.

The place where the insecticidal or danicidal composition obtained by the addition of the stabilizer of the present invention is specifically applied, that is, as a use scene, a glass window of a general house or a store exposed to outside light, for example, a show window, or In the place where various pests gather by the light source, such as screen doors, electric display surface of vending machines, indoor lights, or external lighting such as street lights,
The composition can be effectively used by spraying, applying, or the like, onto the composition containing a pyrethroid compound in an appropriate concentration.

At that time, the target pests that can effectively exert their effects are sanitary pests, agricultural pests, discomfort pests, grain storage pests, wood pests, and the like.Specific examples of these include planthoppers, leafhoppers, mosquitoes, flies, Chironomus, feather ants, stink bugs and the like can be exemplified.

[Action]

The surfactant used as a stabilizer in the present invention has an action of protecting a pyrethroid compound from ultraviolet rays, and this action has an ultraviolet protection activity.
In the case of a polyoxyethylene alkylamino ether-based compound, it is presumed that an amino group contributes to the improvement of the ultraviolet ray protection activity in a nonionic surfactant, and in the case of a polyoxyethylene alkylamino ether compound, the number of moles of oxyethylene added is large. Therefore, it is considered that the contribution of the polyoxyethylene group, which is a hydrophilic group, is small.

Further, in the case of the polyether-modified silicone oil, some types have a particularly large ultraviolet protection activity, and this is considered to be due to slight differences in the chemical structure and physical properties of the ultraviolet protection activity.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these Examples.

Example 1 In order to examine the stabilizing action of a polyether-modified silicone oil, and to determine the activity difference and the alkyl difference in the number of moles of a polyoxyethylene group in polyoxyethylene alkyl ether, chryslon forte, a kind of pyrethroid compound, In order to check the photostability against (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd.), the surfactants shown in Table 2 were subjected to a bioassay as follows. In this case, the evaluation was performed using an ultraviolet lamp.

Bioassay and results Prepare an ethanol solution containing 0.3% of each of Chrisron Forte and surfactant, and prepare 0.1 ml of the sample.
Was dropped onto the upper and lower pigs of a glass Petri dish (9 cm in diameter), respectively, and spread over the entire inner surface. The petri dish was placed 84 cm below two ultraviolet tubes (40 W), and the petri dish was collected over time and subjected to a bioassay. In the bioassay, a housefly adult was placed in a petri dish, and the number of knockdowns was examined over time (the knockdown rate after 5 minutes is shown in the table). As a control, a surfactant-free additive was used.

As a result, in the control, the deactivation increased 6 hours after the light exposure, whereas the addition of a specific surfactant increased the photostability of Chrislon Walte, and was particularly high in Nos. 7 and 10. Protective activity was observed.

Table 3 shows the measurement results.

Example 2 Bioassay method and results Test solution (base is a commercially available glass cleaner) in which two kinds of pyrethroid compounds shown in Table 4 and a surfactant (Zontes AL-10) were mixed at a ratio of 0.3%, respectively, and pyrethroid. An ethanol solution containing 0.3% of only the system compound (control) was prepared. 0.1 ml of each sample was dropped on the upper and lower pigs of a glass petri dish (diameter 9 cm), respectively, and spread over the entire inner surface. After placing it under natural light, the petri dish was collected over time and subjected to a bioassay to examine the residual effect. The activity was evaluated by releasing the house fly adult in a petri dish and counting the number of knockdown insects over time (100% in Table 4).
The time required to obtain a knockdown rate of

As a result, in the control plots of Chrisron Forte and Pinamine Forte (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd.), the cells were completely inactivated 1-2 hours after light exposure, whereas the treatment with the addition of a surfactant was performed. In the plot, the stability increased, and the activity was maintained for nearly 20 hours.

Example 3 The following stability test was performed to determine the time-dependent decomposition rate of the pyrethroid compound.

Stability test In order to see the stabilizing action of polyoxyethylene (10 mol addition) lauryl amino ether (hereinafter referred to as "surfactant A"), the stability of chryslon forte to ultraviolet light was examined as follows.

(Test method) Chrislon Forte and surfactant A are mixed by equal weight,
Samples were prepared in ethanol at a concentration of 0.5 (w / w)% and 2.0 (w / w)% of chrysron forte, and 0.1% of each sample was prepared.
1 ml is dropped on a glass Petri dish (85 mm in diameter),
It extended to the entire inner surface. Put the petri dish in an ultraviolet tube (40w)
The two pieces were placed 45 cm below each other, and the chryslon forte of the petri dish was quantified over time (in Table 5, the rate of chryslon forte degradation was shown in%). As a control, surfactant A
The same test was carried out using 0.1 ml of a 0.6% (w / w) ethanol solution of Chrisron Forte to which no phenol was added.

In the quantitative method, chryslon forte in each petri dish was collected with acetone and analyzed by gas chromatogram.

(Results) Table 5 shows the analysis results.

[Effect of the Invention] The stabilizer of the present invention stabilizes the pyrethroid-based compound by selecting a specific surfactant, particularly increases the stability to light, and exposes the insecticide composition to light. Even when applied to the surface of window glass or the like, extremely high insecticidal or acaricidal efficacy can be obtained.

The stabilization method of the present invention can have the above-mentioned effect by adding the above-mentioned surfactant to a pyrethroid compound.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A01N 53/00 A01N 25/22-25/30 CA (STN) WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. Polyoxyethylene alkylamino ether, polyoxyethylene castor oil, polyoxyethylene propylene glycol monooleate, polyether-modified silicone oil, perfluoroalkyl carboxylate, fatty acid alkanolamide, alkyl sulfate, polysulfone A light and / or ultraviolet light stabilizer of a pyrethroid compound containing, as a stabilizing component, at least one surfactant selected from the group consisting of oxyethylene alkyl ethers. 2. A pyrethroid compound comprising polyoxyethylene alkylamino ether, polyoxyethylene castor oil, polyoxyethylene propylene glycol monooleate, polyether-modified silicone oil, perfluoroalkyl carboxylate, fatty acid alkanolamide, alkyl sulfate A method for stabilizing a pyrethroid compound, characterized in that the compound is stabilized against light and / or ultraviolet light by a surfactant comprising at least one member selected from the group consisting of an ester salt and a polyoxyethylene alkyl ether.