KR820001492B1 - Oil-in-water insecticidal and acaricidal emulsion - Google Patents

Abstract

Oil-in-water pyrethroid emulsions were prepd., contg. I(X = H, Cl, Br, F; Y = II, III; R1 = Me, TV; R2 = Me; R3 = Cl, Br, F, t-butyl; R4 = isopropyl, cyclopropyl; R5 = Cl, Br, F, Me), as well as gum arabic or polyvinyl alc. and a thickening agent. Thus, an emulsion is given, contg. 10 % polyvinyl alc. 40 g, (+)-2-cyano-3-phenoxybenzyl(+)-2-(4-chlorophenyl)isovalerorate 10 g, and Agrisol FL-100F 50 g. When stored at 40≰C for 6 months, the emulsion was stable, and showed only 0.5% degrdn. of the active ingredient.

Description

Process for preparing oil-in-water insecticide and acaricide emulsion

The present invention relates to a method for preparing oil-in-water pesticides and acaricide emulsion compositions.

The present invention is based on the weight of at least one ester of the formula (I) 1 to 5% hydrophobic insecticide, acaricide active liquid component and the weight of the polyvinyl alcohol or gum arabic 2 to 10% and the weight of the electrodeposition agent in equilibrium with water A novel oil-in-water pesticide, acaricide emulsion, composed of 0.1 to 20% (generally called an "aqueous fluid formulation").

In the above structural formula

X is hydrogen, chlorine, bromine or fluorine

Y is a group of the following structural formula

Where R ₁ is a methyl group or a group of

Wherein R ₅ is chlorine, bromine, fluorine atom or methyl group; R ₂ is a hydrogen atom or a methyl group; R ₃ is a chlorine, bromine, fluorine atom or tri-butyl group; R ₄ is isopropyl group or cyclopropyl group. The insecticidal, acaricide emulsion of the present invention exhibits acaricide and insecticidal action equivalent to conventional formulations and at the same time is safe and easy to use.

Emulsifying concentrates, which are commonly used in liquid form, as a killing agent, synthetic surfactants and large amounts of organic solvents, are combustible or odorous, toxic or irritating to humans, dairy cows or other livestock or poultry, plants against crops. It is flawed because of the organic solvents contained therein, such as poisons. Hydrating ingredients that do not use an organic solvent are not completely satisfactory. This is because spraying liquids cannot be easily produced due to the fine powder powder and low volume airborne spraying at high concentrations (less than 300 per 10 ares) is not possible.

For this reason, research has been directed to aqueous emulsions of clear emulsions and pesticides with water instead of clear organic solvents or powdery weight agents to suspend or disperse microparticles of hydrophobic pesticidal active ingredients.

Since such aqueous flow preparations and clear emulsions are handled in liquid form, the spray liquid can be prepared without making a powder; Volumetric and dilution and other necessary manipulations can be easily accomplished as with conventional liquid formulations. In addition, they have no or only slight problems causing phytotoxicity to crops, as well as toxicity or irritation to humans, cows or other livestock or poultry caused by organic solvents. However, the aqueous rheological agents of the pesticides proposed by the Contributions are suspensions using solid hydrophobic pesticidal active ingredients (Japanese Patent Application (OPI) Nos. 126635/74, 76236/75 and 148625/77 "Unexamined Japan"). Patent applications) and US Pat. No. 4,071,617. As time passes, oil-in-water emulsions that use pesticidal active ingredients in oil forms that have not yet been developed due to difficulties in stabilizing their physical properties are not yet practical.

Transparent emulsions used as a water-borne pesticide composition are described in Japanese Patent Application Nos. 20520/71 and Japanese Patent Applications (OPI) 54547/74 and 122628/77, but these transparent emulsions have a particle size of less than 0.1 μm of the pesticidal active ingredient. It is unsatisfactory to reduce the mass of general purpose synthetic surfactants in water-soluble form and to address the toxicity and the toxicity issues due to the high use of surfactants.

Several studies have shown higher alcohol sulfates, higher alcohol sulfonates, alkylsulfonates, arylsulfonates, alkarylarylsulfonates, or formalin concentrates thereof, fatty acid ester compounds, polyoxyethylene alkyl ethers, polyoxyethylene atyl ethers, polyoxy It differs from conventional formulations without the use of organic solvents or general synthetic synthetic surfactants such as ethylenealkylarylethers, polyoxyethylene phenyl phenol derivatives or polyoxyethylene sorbitan alkylates, and has the same pesticidal and acaricidal effects as the conventional formulations described above. It is concentrated in the process for preparing oil-in-water pesticides and acaricide emulsions, which can retain the chemical and physical properties over time and contain the compound of formula (I) as a hydrophobic active liquid component. As a result of this study, the present invention found that the most suitable dispersant for the compound of formula (I) is polyvinyl alcohol or gum arabic.

Therefore, the main object of the present invention is to provide an insecticidal and acaricide active oil-in-water emulsion in which physical and chemical properties are maintained over time.

More particularly, it is an object of the present invention to provide an insecticidal, non-water-in-water, emulsion-in-water emulsion that solves the shortcomings of conventional use of general purpose active surfactants and organic solvents.

Another object of the present invention is to provide an insecticidal, acaricide active oil-in-water emulsion based on the compound of formula (I).

Insecticidal and acaricide emulsions meeting the above requirements are dispersed in an aqueous solution of polyvinyl alcohol or gum arabic to disperse the fine particles (or microdroplets) of the compound of formula (I) and stably suspend the suspended fine particles of the compound. It can be produced economically by a simple method consisting of adding.

A brief description of the method for preparing the oil-in-water pesticide and acaricide emulsion of the present invention is as follows.

First, the hydrophobic insecticidal and acaricide active ingredient of formula (I) was added to an aqueous solution of 2 to 20% by weight polyvinyl alcohol or gum arabic and prepared by T.K.K., Homogenous Mixture (Tokushu Kika Koguo Co., Ltd.). Prepared by the Shin-Nai Seisaku Sho, Ltd. to disperse the particles of the active ingredient (AI) during conventional agitation, such as a maternal niger, or while heating the aqueous solution at 60 to 70 ° C. The size of the emulsified particles of the active ingredient may vary within the range of about 1 to 200 μ depending on the content or stirring force of the polyvinyl alcohol or gum arabic. Finally, an aqueous solution of a weighting agent is added to an appropriate amount of emulsion to prevent fixation of the emulsified particles and to improve dispersion stability. It will remain the long-term stability.

Typical examples of the compounds of the formula (I) according to the invention are shown below and they are to be understood that they are not limited by the scope of the invention and that the optical isomers and / or geometric isomers of these examples are included in the scope of the compounds and the compounds are room temperature In (about 20 ° C.) liquid.

Representative examples are as follows.

α-cyano-3-phenoxybenzyl 2- (4-chlorophenyl) isovalerate,

α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalate,

A mixture comprising at least 60% of (-)-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalate and (+)-α-cyano-3-phenoxybenzyl (-)-2- (4-chlorophenyl) isovalate, α-cyano-3- (4-bromophenoxy) benzyl 2- (4-chlorophenyl) isovalerate, α-cyano-3 -Phenoxybenzyl 2- (4-tert-butylphenyl) isovalorate, α-cyano-3- (4-fluorophenoxy) benzyl 2- (4-chlorophenyl) isovalorate, α-cya No-3- (4-bromophenoxy) benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, α-cyano-3- (4-fluorophenoxy)- Benzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, α-cyano-3-phenoxybenzyl chrysatemate, α-cyano-3-phenoxybenzyl 2,2- Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, and α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethyl-cyclopropanecarboxylate.

Oil-in-water pesticides and acaricide emulsions according to the present invention are hydrophobic insecticide and acaricide active liquid component of at least one ester of formula (I), 1 to 50% by weight, preferably 1 to 40% by weight; 2 to 10% by weight of polyvinyl alcohol or gum arabic; The weight of the weightant balanced with water is comprised between 0.1 and 20%, preferably between 0.4 and 10%.

Suitable examples of polyvinyl alcohols that may be used in the present invention have a degree of hydrolysis between about 70 and 90 mole percent and a degree of polymerization of less than about 1500. One such example is Goshenol GL-05. Polyvinyl alcohol, manufactured by Nippon Synthetic Chemicals Co., Ltd., has a degree of polymerization of less than 1000 and a degree of hydrolysis of 86.5 to 89 mol%.

Examples of extenders that can be used in the present invention include tragacand gum, guar gum, sodium alginate, carboxymethyl cellulose methylcellulose, polyacrylic acid or derivatives thereof. Commercially available extenders include Agrisol FL-100F (manufactured by Kao-Atlas Co., Ltd.), Primal ASE-60 Japan Acrylic Chemicals Co., Ltd., and Leogin 250H (Nihon Chuyaku Industrial Co., Ltd.). . These extenders are used in amounts ranging from 0.1 to 20% by weight and the optimal amount of addition varies depending on the extender and is preferably in the range from 0.4 to 10% by weight.

Since the oil-in-water pesticides and acaricide emulsions of the present invention contain no organic solvents, such as the burnability and odor of organic solvents and the potential for irritation or toxicity due to solvents for human cows or other livestock or poultry or poisoning against crops. Free from damage In addition, volumetric, dilution and other necessary manipulations and water used as diluents for the preparation of spray solutions have high mixing properties and can be easily performed as in the case of conventional liquid formulations.

The invention will be further illustrated and illustrated according to the following examples without being limited to the scope of the invention.

Example 1

10 g of (+)-2-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate was added to 40 g of 10% by weight aqueous gocenol GL-05 solution and the mixture was .K. Stir at 5000 vpm and 70 ° C. for 5 minutes with a homomixer.

50 g of neutral Agrisol FL-100F 20% by weight aqueous solution was added to the mixture at ambient temperature and the resulting mixture was stirred with a slight moisture to 10% by weight of α-cyano-3-phenoxybenzyl (+)-2- ( A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing 4-chlorophenyl) isovalerate is obtained. The particles of emulsified active ingredient are in the range of 1 to 60 in size.

As clearly shown in Table 1, the test results of the dispersion stability of the insecticidal, acaricide emulsion of the present invention indicates that the chemical and physical properties are stable.

TABLE 1

Example 2

T.K. The process of Example 1 was repeated except that the homogeneous mixer was rotated at 2500 rpm. The product is an oil-in-water pesticide and acaricide emulsion containing 10% by weight of (+)-α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate. The particle size of the emulsified active ingredient is in the range of 5 to 160 microns.

As clearly shown in Table 2, the test results of the dispersion stability of the insecticidal, acaricide emulsion of the present invention indicates that the chemical and physical properties are stable.

TABLE 2

Example 3

10 g of (+)-α-cyano-3-phenoxybenzyl (+)-1- (4-chlorophenyl) isovalorate was added to 40 g of 10% by weight aqueous solution of gum arabic and the mixture was allowed to run at 5000 rpm 70 for 5 minutes. T. K at ° C. Stir with a homogeneous mixer. To this mixture was added 0.8 g of 0.8% by weight aqueous solution of rheazine 250H at ambient temperature and the resulting mixture was stirred with a little moisture to give 10% by weight of (+)-α-cyano-3-phenoxybenzyl (+)-2- A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing (4-chlorophenyl) isovalerate is obtained. The particle size of the active ingredient is in the range of 1 to 80.

Example 4

T.K. The procedure of Example 3 is repeated except that the apparatus is rotated at 2500 rpm with a uniform mixer. The product is 100 g of a steamed pesticide and acaricide emulsion containing 10% by weight of (+)-α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate. The particle size of the emulsified active ingredient is in the range of 6 to 200 mu.

Example 5

20 g of (+)-α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate is added to 10 g of 10% by weight aqueous solution of 40 g of goshenol GL-05 and the mixture is T.K. at 5000 rpm for 70 minutes. Stir with a homogeneous mixer.

To this mixture was added 40 g of 25% by weight neutralized aqueous solution of Agrisol FL-100F at ambient temperature and the resulting mixture was gently stirred with water to obtain 20% by weight of (+)-α-cyano-3-phenoxybenzyl ( +)-2- (4-chlorophenyl) yields 100 g of a homogeneous oil-in-water pesticide and acaricide emulsion containing sovalerate. The particle size of the emulsified active ingredient is 1 to 60 mu.

Example 6

1 g of (±) -α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate was added to 40 g of 5% by weight aqueous solution of high ceenol GL-05 and the mixture was Stir with a T. K. uniform mixer at 5000 rpm for 70 minutes.

To this mixture was added 50 g of a 17% by weight aqueous solution of neutralized Agrisol FL-100F at ambient temperature and the resulting mixture was gently stirred with 1% by weight of (+)-α-cyano-3-phenoxybenzyl ( +)-2- (4-chlorophenyl) yields 100 g of a homogeneous oil-in-water pesticide and acaricide emulsion containing sovalerate. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 7

40 g of (±) -α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate were added to 20 g of 20% by weight aqueous solution of 50 g of high cesenol GL-05 and the mixture was T.K. at 5000 rpm for 70 minutes. Stir with a homogeneous mixer.

To this mixture was added 10 g of neutralized Agrisol FL-100F 50% by weight aqueous solution and the resulting mixture was gently stirred for a few minutes to 40% by weight of (±) -α-cyano-3-phenoxybenzyl (+)- A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing 2- (4-chlorophenyl) isovalerate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 40 mu.

Example 8

20 g of α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate were added to 10 g of 10% by weight of an aqueous solution of 40 g of gosenol GL-05 and the mixture was allowed to run at 5000 rpm, 70 for 5 minutes. T. K at ° C. Stir with a homogeneous mixer.

To this mixture is added 40 g of neutralized Agrisol FL-100F 25% by weight aqueous solution at ambient temperature and the resulting mixture is stirred gently for several minutes. 20% by weight of α-cyano-3-phenoxybenzyl (+)-2 A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing-(4-chlorophenyl) isovalerate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 40 mu.

Example 9

40 g of α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate were added to 10 g of 10% by weight aqueous solution of 50 g of goshenol GL-05 and the mixture was allowed to run at 5000 rpm, 70 for 5 minutes. Stir with a T. K. uniform mixer at ° C.

To this mixture is added 10 g of an aqueous solution of 50% by weight of aqueous Agrisol FL-100F at ambient temperature and the resulting mixture is stirred gently for several minutes. 40% by weight of α-cyano-3-phenoxybenzyl (+) A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing 2- (4-chlorophenyl) isovalerate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 30 mu.

Example 10

80% of (-)-α-cyano-3-phenoxybenzyl (+)-2- (4-chlorophenyl) isovalerate and (+)-α-cyano-3-phenoxybenzyl (-) 20 g of a mixture of -2- (4-chlorophenyl) isovalerate was added to 10 g of 10% by weight aqueous solution of 40 g of gosenolic GL-05 and the mixture was stirred at 5000 rpm for 5 minutes at 70 ° C. with a T.K.uniform mixer. do.

To this mixture was added 25 g of a 25% by weight aqueous solution of neutralized Agrisol FL-100F at main temperature and the resultant mixture was gently stirred for several minutes. Obtain heavy oil pesticides and acaricide emulsions. The particle size of the emulsified active ingredient is in the range of 1 to 40 mu.

Example 11

20 g of (+)-α-cyano-3- (4-bromophenoxy) benzyl (+)-2- (4-chlorophenyl) isovalerate to 10 g of 10% by weight aqueous solution of 40 g of high-enol GL-05 And the mixture was stirred at 5000 rpm for 5 minutes at 70 ° C. Stir with a homogeneous mixer.

To this mixture was added 25 g of an aqueous solution of 40% neutralized Agrisol FL-100F at ambient temperature and the resulting mixture was stirred gently for several minutes. 20% by weight of (+)-α-cyano-3- (4- A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing bromophenoxy) benzyl (+)-2- (4-chlorophenyl) isovalerate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 12

20 g of (±) -α-cyano-3-phenoxybenzyl (±) -2- (4-tert-butylphenyl) isovalerate was added to 40 g of goshenol GL-05 and the mixture was subjected to 5000 rpm for 5 minutes, Stir at 70 ° C. with a T. K. uniform mixer.

To this mixture was added 40 g of neutralized Agrisol FL-100F 25% by weight aqueous solution at ambient temperature and the resulting mixture was gently stirred for several minutes. 20% by weight of (+)-α-cyano-3-phenoxybenzyl 2 A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing-(4-tert-butylphenol) isovalerate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 60 microns.

Example 13

20 g of (±) -α-cyano-3- (4-fluorophenoxy) benzyl (+)-2- (4-chlorophenyl) isovalerate 10 g of 10% by weight of 40 g of Goshenol GL-05 The solution is added and the mixture is stirred with a T. K. uniform mixer at 5000 rpm for 5 minutes at 70 ° C.

To this mixture was added 40 g of neutralized Agrisol FL-100F 25% by weight aqueous solution at ambient temperature and the resultant mixture was stirred gently for several minutes. 20% by weight of (±) -α-cyano-3- (4-fluoro 100 g of a homogeneous oil-in-water pesticide and acaricide emulsion containing lofenoxy) benzyl (±) -2- (4-chlorophenyl) isovalerate are obtained. The particle size of the emulsified active ingredient is in the range of 1 to 70 mu.

Example 14

20 g of (±) -α-cyano-3- (4-bromophenoxy) benzyl (±) -cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate To 40 g of 10% by weight aqueous solution of Gocenol GL-05 is added and the mixture is stirred with a T. K. uniform mixer at 5000 rpm for 5 minutes at 70 ° C.

To this mixture is added 40 g of neutralized Agrisol FL-100F 25 wt% aqueous solution at ambient temperature and the resulting mixture is gently stirred for a few minutes, followed by 100 g of homogeneous water-pesticide and acaricide containing 20 wt% of the active ingredient. Obtain an emulsion. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 15

20 g of (☆) -α-cyano-3- (4-fluorophenoxy) benzyl (±) -cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate To 40 g of 10% by weight aqueous solution of Gocenol GL-05 is added and the mixture is stirred with a T.K.uniform mixer at 5000 rpm for 5 minutes at 70 ° C.

To this mixture was added 25 g aqueous solution of 40 g of neutralized Agrisol FL-100F at ambient temperature and the resulting mixture was gently stirred for a few minutes, followed by 100 g homogeneous oil-in-water pesticide containing 20 wt% of the active ingredient, and Get a salvi emulsion. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 16

20 g of (+)-α-cyano-3-phenoxybenzyl (+)-cis, trans-cristamate was added to 10 g of 10% by weight of an aqueous solution of 40 g of gosenol GL-05 and the mixture was allowed to react at 5000 rpm, 70 ° C. for 5 minutes. Stir with a T. K. uniform mixer.

To this mixture was added 40 g of neutralized Agrisol FL-100F 25% by weight aqueous solution at ambient temperature and the resulting mixture was gently stirred for a few minutes. 20% by weight of (+)-α-cyano-3-phenoxy (+ 100 g of a homogeneous oil-in-water pesticide and acaricide emulsion containing) -cis, trans crismate are obtained. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

TABLE 3

Example 17

The procedure of Example 16 is repeated except that the T. K. uniform mixer is rotated at 2500 rpm. The product is an oil-in-water pesticide and acaricide emulsion containing 20% by weight of (+)-α-cyano-3-phenoxybenzyl (+)-cis, trans-crisanthate. The particle size of the emulsified active ingredient is in the range of 1 to 130 mu.

Example 18

40 g of α-cyano-3-phenoxybenzyl (+)-cis, transantate were added to 5 g of 5% by weight aqueous solution of 40 g of gosenool GL-05 and the mixture was allowed to react at T.K. Stir with a homogeneous mixer.

To this mixture was added 20 g of neutralized Agrisol FL-100F 50% by weight aqueous solution at ambient temperature and the resulting mixture was gently stirred for a few minutes to 40% by weight of α-cyano-3-phenoxybenzyl (+)-cis. 100 g of a homogeneous oil-in-water pesticide and acaricide emulsion containing trans-antmate are obtained. The particle size of the emulsified active ingredient is in the range of 1 to 60 mu.

Example 19

25 g-α-cyano-3-phenoxybenzyl (+)-trans crisantate is added to 10 g of 10% by weight aqueous solution of arabic gum and the mixture is stirred with a T.K.uniform mixer at 5000 rpm for 5 minutes at 70 ° C. do.

To this mixture was added 25 g of 20% by weight aqueous solution of sodium alkate at ambient temperature and the resulting mixture was stirred gently for several minutes. 25% by weight of α-cyano-3-phenoxybenzyl (+)-trans-cristenate was added. 100 g of oil-in-water pesticide and acaricide emulsion containing are obtained. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 20

20 g of (±) -α-cyano-3-phenoxybenzyl (±) -cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate to 40 g of goshenol GL Add to -10 10% by weight of the aqueous solution and the mixture is stirred for 5 minutes at 5000 rpm, 70 ℃ in a T. K. uniform mixer.

To this mixture was added 40 g of neutralized Agrisol FL-100F 25% by weight aqueous solution at ambient temperature and the resulting mixture was gently stirred for a few minutes. 20% by weight of (+)-α-cyano-3-phenoxybenzyl ( A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing +)-cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

TABLE 4

Example 21

1 g of (±) -α-cyano-3-phenoxybenzyl (±) -cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate in 40 g of gum arabic 5% by weight of the aqueous solution is added and the mixture is stirred at 5000 rpm for 5 minutes at 70 ° C. with a T. K. uniform mixer.

59 g of 2% by weight aqueous solution of carboxymethyl cellulose gutlium was added to the mixture at ambient temperature, and the resulting mixture was gently stirred for several minutes. 1% by weight of (±) -α-cyano-3-phenoxybenzyl (± A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing) -cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 40 mu.

Example 22

30 g of α-cyano-3-phenoxybenzyl (+)-cis, trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane 50 g of 10% by weight aqueous of gosenol GL-05 The solution is added and the mixture is stirred with a T. K. uniform mixer at 5000 rpm for 5 minutes at 70 ° C.

To this mixture is added 20 g of neutralized Agrisol FL-100F 50% by weight aqueous solution at ambient temperature and the resulting mixture is stirred gently for several minutes. A homogeneous oil-in-water pesticide and acaricide emulsion of 100 g of trans-2,2-3- (2,2-dimethyldichlorovinyl) are obtained. The particle size of the emulsified active ingredient is in the range of 1 to 50 mu.

Example 23

5 g of α-cyano-3-phenoxybenzyl (+)-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was added to 45 g of 5% by weight aqueous solution of arabic gum. The mixture was added for 5 minutes at 2500 rpm at 70 ° C. Stir with a homogeneous mixer.

The mixture was added 50 g of 0.8 g of Leogin 250H aqueous solution at ambient temperature and the resulting mixture was stirred gently for several minutes. 5% by weight of α-cyano-3-phenoxybenzyl-trans-2,2-dimethyl-3 A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing-(2,3-dichlorovinyl) cyclopropane carboxylate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 140 mu.

Example 24

20 g of (±) -α-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclo propane carboxylate are added to 10 g of 10% by weight aqueous solution of 40 g of high-enol GL-05 and the mixture is Stir with a T. K. uniform mixer at 5000 rpm for 70 minutes.

To this mixture was added 40 g of neutralized Agrisol GL-100F 25% by weight aqueous solution at ambient temperature and the resultant mixture was gently stirred for several minutes. 20 parts of (±) -α-cyano-3-phenoxybenzyl-2 were added. A 100 g homogeneous oil-in-water pesticide and acaricide emulsion containing 2,3,3-tetramethylcyclopropane carboxylate is obtained. The particle size of the emulsified active ingredient is in the range of 1 to 40 mu.

The following experiment was conducted to show the effect of gum gum and polyvinyl alcohol as a dispersant compared to other water soluble polymers.

[Experiment 1]

180 g of each 2% by weight aqueous solution of the following materials are prepared. Albumin, Cellulose Sulfate Derivative Alginate, sodium, carrageenan, polyvinyl carboxymethylcellulose, lignin sulfonate sodium, gelatin gum, and gosenol GL-05 Aqueous solution of racemate shown in Table 5 Nine hydrophobic insecticidal and acaricide active liquid components of 20 g each of) are added. T. K. homogeneous mixer is used to disperse the active ingredient at 70 ° C. until the emulsified particle size is 1 to 100 μm, and each obtained emulsion is placed in a sealed glass container and suited overnight in a room temperature dryer and its dispersion Observe stability. The observation results are shown in Table 5 below.

In Table 5, the insecticidal and acaricide compounds (1) to (9) have the following structural formulas.

TABLE 5

Distributed Stability Criteria

○… No signs of solidification of active ingredient particles.

? Active ingredient particles solidify, but no separation between oil and water phases occurs.

×… The particles of the active ingredient solidify until the oil phase separates from the water phase.

Table 5 shows the effects of gum arabic and polyvinyl alcohol as dispersants.

The following experiment was carried out to show the effect of oil-in-water pesticide and acaricide emulsion prepared by the present invention.

[Test 2]

Examples 5, 8, 10, 11, 12, 13, 14, 15, 16, 20, 24 (5, 8, 10, 11, 12, 13, 14, 15, 16, 20 and 24 are each defined as emulsions 11 oil-in-water pesticides and acaricide emulsions containing 20% by weight of the active ingredient prepared in One emulsifier concentrate and control agent is C-5, C-8, C-10, C-11, C-12, C-13, C-14, C-15, C-16, C-20 and C- Each defined as 24).

In each concentrate indicated in Example 6 below, a solution or control formulation containing an oil-in-water pesticide and acaricide was used for the young cabbage leaves on a turn table in a 30 ml / 2pot ratio. After drying in the air, 10 (3-4 instar) spodoptera litura larvae were added to the treated leaves, covered with a plastic cup, and the number of deaths was observed on day 2. The results of the death test are shown in Table 6 below.

TABLE 6

As shown in the table above, all samples of the oil-in-water pesticides and acaricide emulsions of the present invention have demonstrated the same excellent effects as the control preparations in dilution and the emulsions of the present invention are easy to use.

[Experiment 6]

Twenty female females of mature red citrus mite (panonychus citri) are placed on each leaf of the citrus on the back, and the front side is in direct contact with cotton wool containing water. Emulsion solutions 5, 8, 10, 11, 12, 13, 14, 15, 16, 20, 24 and control formulations C-5, C-8, C- prepared by diluting the emulsion or control formulation to a concentration of 500 ppm Three of 10, C-12, C-13, C-14, C-15, C-16, C-10, C-24 were used for the leaves. The number of ticks that survived 24 hours after use was observed. Three trials yielded an average mortality of red citrus mites (panonychus citri).

The results are shown in Table 7.

TABLE 7

As shown in the table above, all samples of the oil-in-water pesticides and acaricide emulsions of the present invention have demonstrated the same excellent effect as the control in dilution rate and the emulsions of the present invention are identical in terms of use.

Comparisons with the oil-in-water pesticide and acaricide suspensions of the present invention, previous pesticide and acaricide formulations, have been conducted in other experiments demonstrating little irritation to the eyes of rabbits as examples of humans, cattle, other livestock and poultry.

[Experiment 4]

To assess the irritant effect of oil-in-water pesticides and acaricide emulsions on mucous membranes, the irritant effect of emulsions in rabbit eyes was tested according to the Environmental Protection Agency Guideline [Federal Register 43, 3735937360 (1978)].

Five oil-in-water pesticide and acaricide emulsions containing 20% by weight of the active ingredients made in Examples 5, 8, 10, 20 and 24 in this test. Emulsion concentrates and control formulations containing 20% by weight of the same active ingredient used were compared to C-5, C-8, C-10, C-20, C-24, respectively.

The results are shown in Table 9, where the maximum total scores of the strong stimulus response and the strong stimulus were obtained according to the criteria listed in the following Table 9.

TABLE 8

TABLE 9

Size of vision disorder monopoly

Cornea

(A) Opacity-the degree of density (reading range)

(B) the range including the cornea

2. Hong Che

(A) value

3. Diaphragm

(A) redness (only relevant to the eyelid conjunctiva)

(B) conjunctival edema

(C) feces

It was demonstrated in Table 8 above that the degree of irritation of the oil-in-water pesticides and acaricides of the present invention was weaker than the control formulation containing the same active ingredient in the emulsion of the present invention.

As demonstrated by other experiments, the oil-in-water pesticides and acaricide emulsions of the present invention are less toxic to humans, cattle, other livestock animals and poultry compared to previous pesticide and acaricide preparations, and are considered to be less harmful in handling them. do.

[Experiment 5]

To evaluate the toxicity of oil-in-water pesticides and acaricides of the present invention, rats were examined for oral toxicity of emulsions. Sample and control formulations were the same as those used in Experiment 4 above.

The test was administered orally with a diluting solution of each sample (diluted with distilled water) to a group of dd-Strain rats (group 1 = 10 males, 10 females) at a dose of 20 ml / kg per rat. Many rats were observed dead. As shown in Table 9 below, LD _{50 was} obtained by the method proposed by Litchfield and Wilcoxon (J. Pharmacol. Exptl. Therp 96, 99 (1949)).

TABLE 10

As is evident from Table 10, the oral acute toxicity of the documentation of the oil-in-water pesticides and acaricides of the present invention is lower than that of the control formulation containing the same active ingredient as that of the emulsion of the present invention.

Having described the present invention in detail and with specific reference, it is apparent that various changes and adjustments have been made without apparently favoring the scope and technology of the present invention over ordinary knowledge.

Claims (1)

The hydrophobic insecticide and acaricide active liquid component of the following formula (I) is added to polyvinyl alcohol or gum arabic and heated at 60 to 70 ° C., and the mixture is stirred to emulsify the particles of the active ingredient and to add a weighting agent to stabilize the emulsion. A method for producing oil-in-water insecticide, acaricide emulsion composition, characterized in that.

In the above structural formula X is hydrogen, chlorine, bromine or fluorine Y is a group of the following structural formula

Where R ₁ is a methyl group or a group of

Wherein R ₅ is chlorine, bromine, fluorine atom or methyl group; R ₂ is a hydrogen atom or a methyl group; R ₃ is a chlorine, bromine, fluorine atom or tert-butyl group; R ₄ is isopropyl group or cyclopropyl group.