KR100471016B1 - Insecticidal aerosol compositions and pesticidal compositions for preparing them - Google Patents

Abstract

The present invention relates to 2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisantemate (a) of 0.1 to 10% by weight and fatty acid ester of 16 to 19 carbon atoms (b). 2.5 to 50% by weight, sorbitan fatty acid ester (c) 2.5 to 30% by weight, ethanol, 1-propanol, 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol And 0.5 to 1% by weight of one or more alcohols selected from the group consisting of glycerin and 40 to 93.5% by weight of saturated hydrocarbons (e) having 8 to 18 carbon atoms, 5 to 30% by weight of the pesticidal composition, water An insecticidal aerosol composition comprising 40 to 85% by weight and 10 to 50% by weight of a propellant, and a method for controlling the pest by applying the insecticidal aerosol composition to the pest.

The insecticidal aerosol composition of the present invention is stable since the rate of separation into the aqueous phase and the organic phase after shaking is very low. Moreover, the pesticidal compositions of the present invention, which are preliminary mixtures of the pesticidal aerosol compositions of the present invention, are stable and have no problems such as precipitation during standing, and thus are suitable starting compositions suitable for transport and storage for the preparation of the pesticidal aerosol compositions of the present invention. to be.

Description

Insecticidal aerosol compositions and pesticidal compositions for preparing the same

The present invention relates to pesticidal aerosol compositions and pesticidal compositions used to prepare them.

2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisantemate is a pesticidal compound mentioned in US Pat. No. 4,176,189, and particularly some ester compounds having pesticidal activity against cockroaches. It is known from British Patent Publication No. 2,243,297 to be enhanced by the addition of.

However, insecticides containing 2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisantemate as active ingredients that enhance the inhibitory effect against cockroaches and have excellent stability are based on There is no known aerosol composition. In particular, in the case of aqueous aerosols, the aqueous phase (oil) and the organic phase are easily separated, so that even when shaken before spraying, separation of the aqueous and organic phases occurs during spraying, which often results in a change in pesticidal activity.

The present invention is an aqueous aerosol containing 2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisanthate as an active ingredient, which is then separated into an aqueous phase and an organic phase after shaking. Provides a pesticidal aerosol composition which occurs at a very low rate and is excellent in stability, and additionally a pesticidal composition used to prepare it.

Insecticidal composition of the present invention, 2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisanthate (a) 0.1 to 10% by weight, fatty acid ester having 16 to 19 carbon atoms (b) 2.5-50% by weight, sorbitan fatty acid ester (c) 2.5-30% by weight, ethanol, 1-propanol, 2-propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 0.5 to 1% by weight of one or more alcohols (d) selected from the group consisting of butylene glycol and glycerin and 40 to 93.5% by weight of saturated hydrocarbons (e) having 8 to 18 carbon atoms. The pesticidal composition of the present invention also has excellent storage stability of the active ingredient.

The insecticidal aerosol composition of the present invention comprising 5-30% by weight of the above-mentioned pesticidal composition, 40-85% by weight of water and 10-50% by weight of the propellant, has a very low separation rate between the aqueous phase and the organic phase after shaking and thus stability. This is an excellent aqueous aerosol. Moreover, the pesticidal aerosol compositions of the present invention have sufficient knock-down efficiency and pesticidal activity, and the active ingredient contained therein is stable during storage.

In the present invention, esters described in British Patent No. 2,243,297 are used as fatty acid esters having 16 to 19 carbon atoms, and monocarboxylic acid esters are preferable in terms of stability of the insecticidal composition, and examples thereof are isopropyl myristate and isopropyl palmi. Tate, hexyl laurate and the like.

Sorbitan fatty acid esters used in the present invention are generally known as emulsifiers, and examples of sorbitan fatty acid esters are sorbitan monolaurate, sorbitan monooleate and the like. Commercially available Leodol SP-L10 [Sorbitan monolaurate manufactured by Rheodol SP-L10, Kao Co., Ltd.] and Leodol SP-O10 (Rheodol SP-O10, Kao Company) Sorbitan monooleate manufactured by Limited) may be used.

Examples of saturated hydrocarbons having 8 to 18 carbon atoms used in the present invention include saturated straight chain hydrocarbons (n-paraffinic acid hydrocarbons), saturated branched hydrocarbons (iso-paraffinic acid hydrocarbons), and cyclic saturated hydrocarbons (naphthenic acid hydrocarbons). Commercially available hapa 15 [n-paraffinic acid hydrocarbons having 14 to 18 carbon atoms, manufactured by ExPon Chemical Co., Ltd.], neo-chiozol, Neo-chiozol, Chuo Kasei High School Campa N-paraffinic acid hydrocarbons having 12 to 14 carbon atoms manufactured by Chuo Kasei Kogyo Co., Ltd.], Exol D-40 (Exxsol D-40, 8 to 11 carbon atoms manufactured by Exxon Chemical Co., Ltd.) Naphthenic acid saturated hydrocarbons and paraffins), Exol D-80 (Exxsol D-80, naphthenic acid and paraffinic hydrocarbons having 10 to 13 carbon atoms manufactured by Exxon Chemical Company Limited) and Isopar G (Isopar G, Exon Chemical Campa Isoparaffinic acid saturated hydrocarbons having 9 to 11 carbon atoms produced by Nilimite) can be used.

In addition, the pesticidal composition of the present invention other than the above components (a) to (e) may contain other insecticidal active ingredients, synergists, stabilizers and the like.

Examples of other pesticidal active ingredients include phenothrin, cifenotrine, permethrin, cipermethrin, deltamethrin, fenvalrate, espenvalrate, etofenprox, propoxer and the like. Such ingredients comprise about 0-15% by weight of the pesticidal composition of the present invention. Examples of effect enhancers include piperonyl butoxide, MGK264, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo- [2.2.2] oct-5-ene-2,3-dica Voximide, octachlorodipropyl ether, and the like. The pesticidal composition of the present invention contains about 0 to 20% by weight of the effect synergist. Examples of stabilizers include phenol derivatives such as BHT and BHA, bisphenol derivatives, arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine and condensates of phenetidine and acetone And benzophenone compounds.

The insecticidal aerosol composition of the present invention is obtained by filling water and the pesticidal composition of the present invention into an aerosol container and filling it with a propellant. If desired, metal corrosion inhibitors and preservatives such as sodium benzoate and ammonium benzoate, perfumes and the like can be further added to the pesticidal aerosol compositions of the present invention.

Propellants include liquefied petroleum gas, dimethyl ether, mixtures thereof and the like.

The water used is preferably deionized or distilled water.

The insecticidal aerosol composition of the present invention is most suitable for the control of cockroaches using an extinction activity that acts exceptionally fast, and is suitable for the control of cockroaches, such as the German cockroach ( Blattella germanica ), the grayish brown cockroach ( Periplaneta fuliginosa ), the American cockroach ( Periplaneta americana ), and the brown cockroach ( Periplaneta brunnea ), Oriental Cockroach ( Blatta orientalis ), Lobster Cockroach ( Nauphoeta cinerea ), Japanese Cockroach ( Periplaneta japonica ), Australian Cockroach ( Periplaneta australasiae ), Brown-foot Cockroach ( Supella longipalpa ), Madeira cockroach ( Leucophaea maderae ) Neostylopy is used for the control of Neostylopyga rhombifolia . The composition also contains other pests, such as diphthera [eg mosquitoes such as Culex pipiens pallens , Culex tritaeniorhynchus , Aedes Aedes aegypti and Anopheles sinensis , Mice, housefly, for example Musca domestica , Muscina stabulans , Pannia cannicuris Fannia canicularis ), meat flies, arthomyiid flies, onion maggots, fruit flies, vinegar flies, moths, ghats, soldier flies, etc.] Bees, etc.), isopterra (eg, Coptotermes formosanus Shiraki , Reticulitermes speratus, etc.).

The pesticidal composition of the present invention is a so-called premix (industrial intermediate) used to prepare the pesticidal aerosol composition of the present invention. The pesticidal composition causes little problem of precipitation while standing at room temperature. Therefore, the pesticidal composition is a composition suitable for transportation and storage for preparing the pesticidal aerosol composition of the present invention.

The invention is illustrated in more detail by the following examples.

First, the preparation example of the pesticidal composition of this invention is described.

Example 1

2,4-dioxo-1- (2-propynyl) -imidazolidin-3-ylmethyl 1R-cis, trans-Chrysanthate (hereinafter referred to as "imiprothrin") 1.6 Pesticide composition of the present invention by mixing 20% by weight, 20% by weight isopropyl myristate, 6% by weight Leodol SP-L10 (mentioned above), 0.5% by weight propylene glycol and 71.9% by weight hag 15 (mentioned above) 1) is obtained.

The pesticidal composition (1) remains homogeneous after standing for 1 day at room temperature and no occurrence of precipitation is observed.

Example 2

The pesticidal composition 2 of the present invention is obtained in the same manner as in Example 1, except that 20% by weight of isopropyl palmitate is used instead of 20% by weight of isopropyl myristate.

The pesticidal composition (2) remains homogenized without precipitation occurring after one day at room temperature.

Example 3

2% by weight of imiprotrin, 22% isopropyl myristate, 10% by weight Leodol SP-L10 (mentioned above), 1% by weight propylene glycol and 65% by weight of neo-thiosol (mentioned above) The pesticidal composition (3) of the present invention is obtained.

Example 4

3% by weight of imiprotrin, 20% by weight of isopropyl myristate, 10% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 66.5% by weight of neo-thiosol (mentioned above) The pesticidal composition 4 of the present invention is obtained.

Example 5

The extinguishing composition of the invention in the same manner as in Example 4, except that 40% by weight instead of 20% by weight of isopropyl myristate and 46.5% by weight instead of 66.5% by weight of neo-thiosol (5) ).

Example 6

The present invention is prepared by mixing 1.6% by weight of imiprotrin, 21.6% by weight of isopropyl myristate, 6% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 70.3% by weight of NOPA 15 (mentioned above) Insecticidal composition (6) is obtained.

Example 7

1.6% by weight of imiprotrin, 4% by weight MGK 264 (elevating agent), 21.6% by weight of isopropyl myristate, 6% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 15 of the lobes (mentioned above) 66.3% by weight of the pesticidal composition 7 of the present invention is obtained.

Example 8

0.4% by weight of imiprotrin, 1.2% by weight of (S) -α-cyano-3-phenoxybenzyl 1R-trans-crystalante (other pesticidal active ingredient), 20% by weight of isopropyl myristate, leodol SP- 6% by weight of L10 (mentioned above), 0.5% by weight of propylene glycol and 71.9% by weight of hapa 15 (mentioned above) are obtained to obtain a pesticidal composition (8) of the invention.

Example 9

0.4% by weight of imiprotrin, 1.2% by weight of espenvalerate (other pesticidal active ingredients), 20% by weight of isopropyl myristate, 6% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and nopa 71.9% by weight of 15 (as mentioned above) were mixed to obtain a pesticidal composition 9 of the present invention.

Example 10

0.4% by weight of imiprotrin, 1.2% of cipermethrin (other pesticidal active ingredient), 20% by weight of isopropyl myristate, 6% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 15% of hapa (from above) 71.9% by weight of the pesticidal composition 10 of the present invention is mixed.

Example 11

1.6% by weight of imiprotrin, 10.0% by weight MGK 264 (effect synergist), 11.6% by weight of isopropyl myristate, 6.0% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 15% of hapa (from above) 70.3% by weight of the pesticidal composition 11 of the present invention is mixed.

Example 12

The present invention is prepared by mixing 1.6% by weight of imiprotrin, 21.6% by weight of isopropyl myristate, 5.0% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and 71.3% by weight of NOPA 15 (mentioned above) The pesticidal composition 12 is obtained.

Example 13

0.5% by weight of imiprotrin, 0.5% by weight of (S) -α-cyano-3-phenoxybenzyl 1R-trans-crystalante (other pesticidal active ingredient), 2.5% by weight of isopropyl myristate, Leodol SP- 2.5% by weight of L10 (mentioned above), 0.5% by weight of propylene glycol and 93.5% by weight of Axol D-40 were obtained to obtain the pesticidal composition 13 of the present invention.

Example 14

0.5% by weight of imiprotrin, 0.5% by weight of espenvalerate (other pesticidal active ingredients), 2.5% by weight of isopropyl myristate, 2.5% by weight of Leodol SP-O10 (mentioned above), 0.5% by weight of propylene glycol and axol 9-40% by weight of D-40 is mixed to obtain a pesticidal composition 14 of the present invention.

Example 15

0.5% by weight of imiprotrin, 0.5% by weight of espenvalerate (other pesticidal active ingredients), 2.5% by weight of isopropyl myristate, 2.5% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and axol 93.5% by weight of D-80 is mixed to obtain a pesticidal composition 15 of the present invention.

Example 16

0.4% by weight of imiprotrin, 0.4% by weight of (S) -α-cyano-3-phenoxybenzyl 1R-trans-crystalante (other pesticidal active ingredient), 20.4% by weight of isopropyl myristate, Leodol SP- 5.0% by weight L10 (mentioned above), 0.5% by weight propylene glycol and 73.3% by weight neo-thiosol (mentioned above) are obtained to obtain a pesticidal composition (16) of the invention.

Example 17

0.4% by weight of imiprotrin, 0.4% by weight of espenvalerate (other pesticidal active ingredients), 20.4% by weight of isopropyl myristate, 5.0% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and neo 73.3% by weight of a thiosol (mentioned above) is mixed to obtain a pesticidal composition 17 of the present invention.

Example 18

0.4% by weight of imiprotrin, 0.4% by weight of cipermethrin (other pesticidal active ingredients), 20.4% by weight of isopropyl myristate, 5.0% by weight of Leodol SP-L10 (mentioned above), 0.5% by weight of propylene glycol and neo-thio 73.3% by weight of the sol (mentioned above) is mixed to obtain the pesticidal composition 18 of the present invention.

Example 19

1.0% by weight of imiprotrin, 1.0% by weight of (S) -α-cyano-3-phenoxybenzyl 1R-trans-crystalante (other pesticidal active ingredient), 6.0% by weight of isopropyl myristate, leodol SP- 12.5% by weight L10 (mentioned above), 0.5% by weight propylene glycol and 79.0% by weight neo-thiosol (mentioned above) are obtained to obtain the pesticidal composition 19 of the present invention.

Example 20

Imiprotrin 1.5% by weight, (S) -α-cyano-3-phenoxybenzyl 1R-trans-crystalante (other pesticidal active ingredient) 0.5% by weight, isopropyl myristate 5.5% by weight, Leodol SP- 5.0% by weight of L10 (mentioned above), 0.5% by weight of propylene glycol and 87.0% by weight of Isopal G (mentioned above) are obtained to obtain a pesticidal composition 20 of the present invention.

Examples of stability tests for insecticidal aerosol compositions obtained from the pesticidal compositions of the present invention are described below.

Example 21

Using 20 parts by weight of the pesticidal composition, 50 parts by weight of deionized water and 30 parts by weight of liquefied petroleum gas, a glass aerosol is prepared in which the state of the contained liquid can be observed. After 1 week of storage at 25 ° C., the glass aerosol is stood 20 times at 2 second intervals and the inversion is repeated. The glass aerosol is then raised horizontally and the rate at which the mixture separates into the aqueous and oily phases of the mixture in the glass vessel is measured. The rate of separation is expressed as the time required for the width of the separated organic phase to be 20% of the total width. The results are shown in Table 1.

Comparative Example 1 of Table 1 shows the result of using the pesticidal composition obtained in the same manner as in Example 3, except that 1% by weight of neo-thiosol was used instead of 1% by weight of propylene glycol, Comparative Example 2 shows the result of using the pesticidal composition obtained in the same manner as in Example 3, except that 22% by weight of neo-thiosol was used instead of 22% by weight of isopropylene myristate.

As shown in Table 1 above, the insecticidal aerosol composition of the present invention can stably maintain an emulsion of the pesticidal composition, water, and propellant for a long time.

Example 22

25% by weight of the pesticidal composition of the present invention and 55% by weight of 0.2% by weight aqueous ammonium benzoate solution are filled into an aerosol container. After the vessel was fitted with an aerosol valve, 20 wt% of liquefied petroleum gas was filled into the valve portion to prepare an aerosol composition. The test aerosol composition is stored at 40 ° C. for 6 months. The component content is analyzed by gas chromatography to obtain the residual rate. The results are shown in Table 2.

Example 23

20% by weight of the pesticidal composition of the present invention and 60% by weight of deionized water are filled into an aerosol container. After attaching the valve to the vessel, 20% by weight of liquefied petroleum gas was charged to the valve portion to obtain an aerosol composition. The test aerosol composition is stored at 40 ° C. for 3 months. The active ingredient content is analyzed by gas chromatography to obtain the residual rate. The results are shown in Table 3.

Insecticidal test examples of the insecticidal aerosol compositions of the present invention are described below.

Example 24

Ten Blattella germanica (5 males and 5 females) are released in a cylindrical container (diameter: 13 cm, height 10 cm) with a mesh of 40 mesh wire 1 cm from the bottom. The container is placed in a glass cylinder (diameter: 20 cm, height 60 cm). The desired amount of aerosol to be tested is then sprayed onto the cockroach and the glass cylinder is quickly covered. 30 seconds after spraying, the container is removed from the glass cylinder. Count cockroaches killed 1, 2, 3, 5, 7, 10, 15 and 20 minutes after spraying. The test is repeated five times and the KT ₅₀ value (the time required for 50% of cockroach eradication) is obtained from the mean of the results calculated by the Blis' prohibit method. The results are shown in Table 4.

Example 25

25% by weight of the pesticidal composition of the present invention and 55% by weight of 0.2% by weight ammonium benzoate solution are introduced into an aerosol container. After the vessel was fitted with an aerosol valve, 20% by weight of liquefied petroleum gas was charged to the valve portion under reduced pressure to prepare an aerosol composition. 1.0 g of the aerosol composition is uniformly sprayed vertically over a 20 cm high 15 cm x 15 cm decorative laminate sheet. To prevent the escape of cockroaches, a cylindrical plastic 18 cm in diameter and 5 cm high with margarine in the inner surface is placed on each sheet. Ten of the German cockroaches ( Blattella germanica : pyrethroid resistant species) (5 males and 5 females) are released into a cylindrical plastic and forced to contact the test composition while testing for 2 hours. Subsequently, the number of exterminated cockroaches is counted. The test is repeated three times and the KT ₅₀ value (the time required for 50% of the cockroach to be eradicated) is obtained from the mortality ratio over time according to Finney's diagrammatic method. In addition, the cockroach under test is transferred into a cup containing water and bait and its mortality is observed after 3 days. 1, 5, 14, 21 and 28 days after the aerosol spray treatment, the test is repeated using the same decorative laminate sheet. The decorative laminate sheet is stored at 25 ° C. during the test. The results are shown in Tables 5 and 6.

The insecticidal aerosol compositions of the present invention have properties suitable for aqueous aerosols (i.e., separation of the aqueous and organic phases occurs at very low rates) and thus have a consistently excellent pesticidal effect. Moreover, the pesticidal compositions of the present invention, which are preliminary mixtures of aerosol compositions, are stable with little precipitation problems upon standing and are suitable starting compositions for transport and storage for preparing the pesticidal aerosol compositions of the present invention.

Claims (4)

(a) 0.1 to 10% by weight of 2,4-dioxo-1- (2-propynyl) imidazolidin-3-ylmethyl crisantemate, (b) 2.5 to 50% by weight of fatty acid ester having 16 to 19 carbon atoms %, (c) 2.5-30 weight percent sorbitan fatty acid ester, (d) propylene glycol_ 0.5-1 weight percent and (e) 40-93.5 weight percent saturated hydrocarbons having 8 to 18 carbon atoms. Insecticidal aerosol composition comprising 5 to 30% by weight of the pesticidal composition according to claim 1, 40 to 85% by weight of water and 10 to 50% by weight of propellant. A method of controlling pests, comprising applying the pesticidal aerosol composition according to claim 2 to the pests. A method for controlling cockroaches, comprising applying the insecticidal aerosol composition according to claim 2 to a cockroach.