JP2767707B2 - Solid insecticidal miticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound of the general formula (I) dissolved in an alkyl phthalate having an alkyl group having 9 to 13 carbon atoms. (Wherein, R a lower alkyl group or a halomethyl group, R ¹
Represents a hydrogen atom or a fluorine atom. The present invention relates to a solid insecticidal and miticidal preparation in which the ether derivative represented by the formula (1) is carried on a solid carrier, the fish poison is reduced, and a high insecticidal effect is stably exhibited.

[Conventional technology]

General formula (I) (Wherein, R a lower alkyl group or a halomethyl group, R ¹
Represents a hydrogen atom or a fluorine atom. ) Are disclosed in JP-B-61-21615 and JP-A-63-4.
It has an extremely high insecticidal and acaricidal activity described in Japanese Patent No. 5233, is excellent in quick action and residual effect, and is an active ingredient of insecticides and acaricides with low toxicity to humans and fishes.

In general, when an active ingredient such as a pesticide is used in actual use, it is usually used in various formulations such as emulsions, wettable powders, powders, granules, and flowables. The idea has been made. For example, granules are prepared by supporting an active ingredient on a mineral carrier and granulating the formulation. Various auxiliary materials such as a binder, a disintegration aid, Agents, dispersants, absorbents, solvents, lubricants, and stabilizers are used. In particular, a small amount of active ingredient is uniformly adsorbed and supported on a large amount of carrier,
In order to maintain a high effect of the active ingredient and stabilize the effect, generally various high-boiling solvents, for example, heavy oil, hydrocarbons such as kerosene, aromatic hydrocarbons such as methylnaphthalene, dibutyl phthalate, dioctyl phthalate, Plasticizers such as tricresyl phosphate, diethylene glycol,
Glycol derivatives such as butyl cellosolve and animal and vegetable oils such as soybean oil are used. Further, JP-A-61-171402 discloses a pesticide solid formulation containing a phthalic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms as a fish poison-reducing agricultural chemical formulation, wherein alkyl esters having 1 to 8 carbon atoms are more preferred. It is disclosed that it is preferable. JP-A-63-107902 discloses a pesticidal solid preparation in which an agrochemical component is dissolved in an aromatic carboxylic acid ester and supported on a solid carrier to prevent a change over time, and an alkyl phthalate having 1 to 12 carbon atoms is disclosed. Esters are disclosed, but the examples show ethyl benzoate as an example of an aromatic carboxylic acid ester.

[Problems to be solved by the invention]

An object of the present invention is to provide a solid insecticidal and acaricidal preparation which has an ether derivative represented by the general formula (I) as an active ingredient and is supported on a solid carrier, in which fish poison is reduced and which exhibits a high insecticidal effect stably. And

That is, a solid insecticide exhibiting a stable and high insecticidal effect, in which the ether derivative represented by the general formula (I) exhibits properties such as high insecticidal activity, acaricidal activity, low human animal toxicity and low fish toxicity to the maximum in practical use. It is an object to provide an acaricidal preparation.

[Means and actions for solving the problem]

The present inventors have developed a solid insecticidal acaricidal preparation which exerts the properties of the ether derivative represented by the general formula (I) such as high insecticidal activity, acaricidal activity, low human toxicity and low fish toxicity to the maximum in practical use. As a result of studying various formulation auxiliaries to provide, a solid carrier in which an ether derivative represented by the general formula (I) dissolved in a phthalic acid alkyl ester having an alkyl group having 9 to 13 carbon atoms as a solvent is supported on a solid carrier Insecticidal and acaricide preparations exhibit a stable and high insecticidal and acaricidal activity,
Furthermore, they have found that they show low fish toxicity, and completed the present invention.

That is, the present invention provides a compound represented by the general formula (I) dissolved in an alkyl phthalate having an alkyl group having 9 to 13 carbon atoms: (Wherein, R a lower alkyl group or a halomethyl group, R ¹
Represents a hydrogen atom or a fluorine atom. The present invention relates to a solid insecticidal acaricidal preparation in which the ether derivative represented by the formula (1) is supported on a solid carrier.

As described above, it is known that alkyl phthalate is used as a solvent for dissolving an active ingredient in a solid formulation of an agricultural chemical. However, the carbon number of 9 to 9 of the present invention.
A solid insecticidal and mite-killing preparation in which an ether derivative represented by the general formula (I) dissolved in an alkyl phthalate having an alkyl group of 13 is supported on a solid carrier has a known alkyl group having 1 to 8 carbon atoms. Compared to a solid insecticidal and mite-killing preparation in which an ether derivative represented by the general formula (I) dissolved in an alkyl phthalate is supported on a solid carrier, not only the insecticide and mite-killing activity is unexpectedly improved, but also it is stably high. It was surprising that the insecticidal and acaricidal effects were exhibited and fish toxicity was significantly reduced.

The solid insecticidal and mite-killing preparation of the present invention in which an ether derivative represented by the general formula (I) dissolved in an alkyl phthalate having an alkyl group having 9 to 13 carbon atoms is supported on a solid carrier is known. Compared with a solid insecticidal acaricidal preparation in which an ether derivative represented by the general formula (I) dissolved in a phthalic acid alkyl ester having an alkyl group of 8 to 8 is supported on a solid carrier, the insecticidal acaricidal activity is improved. It shows a stable effect and it is not clear whether fish toxicity is reduced.
However, the physicochemical similarity between the ether derivative of the active ingredient of the present invention and the alkyl phthalate having an alkyl group having 9 to 13 carbon atoms, which is the other ingredient of the present invention, increases the compatibility and increases the solubility in water. And the like, and it is considered that the insecticidal and acaricidal composition of the present invention produces an unexpected effect.

Such an effect cannot be obtained when an alkyl phthalate having an alkyl group having 1 to 8 carbon atoms is used as a solvent.

The substituent R of the ether derivative represented by the general formula (I) of the active ingredient according to the present invention is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group or the like. Lower alkyl group or difluoromethyl group,
Represents a halomethyl group such as a trifluoromethyl group, a chlorodifluoromethyl group, and a bromodifluoromethyl group. Representative ether derivatives are shown in Table 1.

As the phthalic acid alkyl ester having an alkyl group having 9 to 13 carbon atoms according to the present invention, di-n-nonyl phthalate, diisononyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, di-n-undecyl phthalate, Di-n-dodecyl phthalate, di-n-tridecyl phthalate and the like can be mentioned. Of course, if the alkyl group has 9 to 13 carbon atoms, the alkyl group may be different, but industrially or naturally available alkyl phthalate is sufficient. These alkyl phthalates may be used alone or as a mixture of several types.

The solid insecticidal and acaricide formulation of the present invention contains an ether derivative of the active ingredient in a weight ratio of 0.1 to 40 parts, an alkyl phthalate of 0.1 to 40 parts, and a solid carrier as a balance. Agents, sizing agents and stabilizers can also be used as adjuvants. As a solid carrier, vegetable powders such as soy flour and wood flour, bentonite, clay, talc,
Inorganic mineral powders such as calcium carbonate, diatomaceous earth, stone powder, radiolite, and zeolite, and in some cases, water-soluble solids such as potassium chloride, sodium chloride, ammonium sulfate, and urea.One or more of these can be used. It can be mixed and used. Examples of the surfactant include anionic surfactants such as lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl ether, and polyoxyalkylene. Nonionic surfactants such as alkylaryl ethers, polyoxyalkylenealkylamines, polyoxyalkylenealkylamides, polyoxyalkylenealkylthioethers, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, and sorbitan fatty acid esters can be used.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto. The active ingredient compounds used are indicated by symbols in Table 1.

Example 1 2- (4-difluorobromomethoxyphenyl) -2
-Methylpropyl 3-phenoxy-4-fluorobenzyl ether (Compound I) (0.2 part by weight) was dissolved in diisononyl phthalate (0.4 part by weight), and white carbon 1 was added thereto.
0 parts by weight and 0.5 parts by weight of Drilles A.
The mixture is added and mixed and pulverized to obtain 100 parts by weight of a powder.

Example 2 0.5 parts by weight of 2- (4-trifluoromethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (Compound B), 0.5 important part of diisodecyl phthalate,
Irganox 1010 (antioxidant manufactured by Ciba-Geigy) 0.
05 parts by weight were mixed and heated and melted. To this, 5 parts by weight of white carbon and 93.95 parts by weight of clay were added and mixed and pulverized to obtain 100 parts by weight of a powder.

Example 3 0.5 parts by weight of Compounds C, D, F, J, K or L and Agrisol AC-100 (trade name of Kao Corporation: phthalic acid whose main component is a phthalate ester having an alkyl group having 10 to 12 carbon atoms) 0.8 part by weight of ester) and 0.1 part by weight of Irganox 1010 (antioxidant manufactured by Ciba Geigy) were mixed, 10 parts by weight of white carbon and 0.5 parts by weight of Drilles B were added, and 88.9 parts by weight of clay was further added. , Uniformly mixed and crushed,
100 parts by weight of each powder are obtained.

Example 4 2- (4-difluorobromomethoxyphenyl) -2
20 parts by weight of -methylpropyl 3-phenoxybenzyl ether (compound C) were heated and melted in 15 parts by weight of diisononyl phthalate, and 5 parts by weight of Discol NF (a surfactant manufactured by Daiichi Kogyo Co., Ltd.) and 25 parts by weight of white carbon And 35 parts by weight of radiolite are added and mixed and pulverized to obtain 100 parts by weight of wettable powder.

Example 5 10 parts by weight of 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (Compound F) was added to Agrisol AC-100 (trade name of Kao Corporation: phthalate having 10 to 12 carbon atoms in the alkyl group). 10 parts by weight of phthalic acid ester whose main component is an acid ester) is heated and melted. To this, 3 parts by weight of Disksol WK (a surfactant manufactured by Daiichi Kogyo Co., Ltd.) and 10 parts by weight of white carbon are added, followed by mixing and grinding. And wettable powder 10
Obtain 0 parts by weight.

Example 6 10 parts by weight of Compounds A, B, H, I, J or K were dissolved by heating in 10 parts by weight of dinormal decyl phthalate, 5 parts by weight of Emal 10 (surfactant manufactured by Kao Corporation), 20 parts of white carbon Parts by weight and 55 parts by weight of radiolite are uniformly mixed and pulverized to obtain 100 parts by weight of wettable powder.

Example 7 86 parts by weight of clay and 2 parts by weight of cellogen 7A (carboxymethylcellulose manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were pulverized and mixed, granulated after water addition, and dried to obtain a particle core. 1 part by weight of 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (compound F) and 0.1 part by weight of Irganox 1010 (an antioxidant manufactured by Ciba-Geigy) were added to 10.9 parts by weight of diisodecyl phthalate. Impregnated with a liquid material that has been melted to obtain 100 parts by weight of granules.

Example 8 Using a mixture of clay and talc (mixing ratio = 7: 3), a particle nucleus of 88 parts by weight was obtained in the same manner as in Example 7. To this 2-
(4-ethoxyphenyl) -2-methylpropyl 3-
0.5 parts by weight of phenoxy-4-fluorobenzyl ether (compound L) and 0.05 parts by weight of Irganox 1010 (antioxidant manufactured by Ciba Geigy) are heated and dissolved in 11.45 parts by weight of agrizole AC-110 (dinordecyl phthalate manufactured by Kao Corporation). The obtained liquid is impregnated to obtain 100 parts by weight of granules.

Example 9 86 parts by weight of a mixture of clay and talc (mixing ratio = 7: 3) and 2 parts by weight of cellogen PR (carboxymethylcellulose manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were pulverized and mixed. Get the nucleus. Compounds B, C, D, H, I or J
And 1 part by weight of Irganox 1010 (an antioxidant manufactured by Ciba-Geigy Co., Ltd.) is impregnated with 8.9 parts by weight of dinonyl phthalate, which is then heated and dissolved to obtain 100 parts by weight of granules.

Comparative Example 1 A powder was obtained in the same manner as in Example 1 except that dimethyl phthalate was used instead of diisononyl phthalate.

Comparative Example 2 In place of diisodecyl phthalate of Example 2, di-2
-A powder is obtained in the same manner using ethylhexyl phthalate.

Comparative Example 3 A hydrating agent was obtained in the same manner as in Example 4 except that dimethyl phthalate was used instead of diisononyl phthalate.

COMPARATIVE EXAMPLE 4 Instead of Agrizole AC-100 of Example 5, di-n-
A wettable powder is similarly obtained using octyl phthalate.

Comparative Example 5 Granules were obtained in the same manner as in Example 7, except that dimethyl phthalate was used instead of diisodecyl phthalate.

Comparative Example 6 Instead of agrizole AC-110 of Example 8, di-n-
Granules are obtained in the same manner using octyl phthalate.

Test Example 1 Paddy rice was planted in a resin pot of 1/10000 are, flooded, a PVC cylinder was set up, and dust equivalent to 3 kg / 10 are was sprayed with a bell jar duster. The treated pot was placed in a greenhouse, and the pot was covered with a wire mesh cylinder over time, and 10 adult female brown planthoppers were released therein.After 24 hours, the number of dead insects was counted, and the mortality was measured. I asked. The test was performed in triplicate. Table 2 shows the test results.

As a result of the test, the powders of Examples 1 and 2 using diisononyl phthalate and diisodecyl phthalate exhibited a more stable effect than the powders of Comparative Examples 1 and 2 using dimethyl phthalate and di-2-ethylhexyl phthalate.

Test Example 2 A perilla grown after transplanting in a greenhouse for 20 days was placed on a turntable, and a wettable powder was sprayed at a concentration equivalent to 50 ppm with a spray gun. Place the treated pot in the greenhouse,
The leaves were cut off daily, placed in a round cup, and 10 larvae of the third cutworm cutworm were released here. After 24 hours, the number of dead insects was counted to determine the mortality. The test was performed in duplicate.
Table 3 shows the test results.

As a result of the test, diisononyl phthalate and agrisol AC-100 (trade name of Kao Corporation: alkyl group having 10 to 1 carbon atoms)
The hydrating agents of Examples 4 and 5 using the phthalic acid ester having a phthalic acid ester as the main component (2) are different from the hydrating agents of Comparative Examples 3 and 4 using dimethyl phthalate and di-n-octyl phthalate. Excellent and stable effect was shown.

Test Example 3 Paddy rice was planted in a resin pot of 1/10000 ares and was flooded, and 2 kg of granules were applied to the water surface. The treated pot was placed in a greenhouse, and the pot was covered daily with a wire mesh cylinder, and 10 adult water weevil adults were released therein.The number of dead insects was counted 24 hours later to determine the mortality. . The test was performed in triplicate. Table 4 shows the test results.

As a result of the test, the granules of Examples 7 and 8 using diisodecyl phthalate and Agrisol AC-110 (trade name: dinormal decyl phthalate) were used as Comparative Examples 5 and 8 using dimethyl phthalate and di-n-octyl phthalate. No. 6 exhibited a more stable effect.

〔The invention's effect〕

The solid insecticidal and acaricidal preparation of the present invention enables the effective ingredient represented by the general formula (I) to be used more effectively, and has a longer effect duration than conventional preparations. It showed a stable and high insecticidal and acaricidal effect.

──────────────────────────────────────────────────続 き Continued on the front page Examiner Hiroko Fujiwara (56) References JP-A-63-107902 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 31/14 A01N 25 / 08

Claims (1)

(57) [Claims] 1. A compound of the formula (I) dissolved in an alkyl phthalate having an alkyl group having 9 to 13 carbon atoms. (Wherein, R a lower alkyl group or a halomethyl group, R ¹
Represents a hydrogen atom or a fluorine atom. ) A solid insecticidal miticide comprising an ether derivative represented by the formula