JPS611A - Pesticide powder composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a fatty acid metal salt and a specific silicone compound in combination with an active pesticidal component and having mitigated toxicity to fish and other aquatic life. CONSTITUTION:The objective composition contains (A) an active pesticidal component such as fungicide, insecticide, herbicide, etc. and (B) a fatty acid metal salt, preferably a bivalent or trivalent metal salt of a 12-20C fatty acid (e.g. Ca, Mg or Al salt of stearic acid, lauric acid, palmitic acid, etc.) and (C) a silicone compound of formula (R is lower alkyl or phenyl; n is 1-100). Preferably, the weight ratios of A:B and A:C are 1:(0.5-10) and 1:(0.1-2), respectively, and the amounts of the component B and the component C in the whole pesticide powder are 3-5wt% and 0.1-2wt%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an agrochemical powder composition with reduced toxicity to fish and other aquatic organisms.

[Conventional technology]

Pesticides, such as insecticides, fungicides, and herbicides, have greatly contributed to the development of modern agriculture, and in Japan they are also used to control pests and diseases related to rice cultivation, which is the staple food, and to save labor in agriculture due to the recent decrease in the number of farmers. It has contributed to many things, and its usefulness is enormous.

On the other hand, certain pesticides are harmful to aquatic organisms including fish, and cause acute toxicity or residual toxicity in the food chain and bioaccumulation, causing not only destruction of the ecosystem but also great harm to the human body. For this reason, even though they are highly effective as agricultural chemicals, due to these drawbacks, there are currently many regulations that prohibit their use or limit the situations in which they can be used. In Japan in particular, there are many rice paddies, and the problem of toxicity to fish is very serious, so not only developers and farmers, but also many other environmental stakeholders are looking for technology to overcome this problem. .

Possible ways to reduce fish toxicity caused by pesticides include:

■Method of spraying antidotes for pesticide components at the same time.

■A method that eliminates the elution of pesticide components into water when a pesticide powder composition is dropped into water.

■Or by gradually dissolving it into water.

A method of constantly reducing the concentration in water to a level that does not affect fish, etc., and waiting for the pesticide components to disappear from the water due to the decomposition ability of light, water, air, soil microorganisms, etc.

On the other hand, ■Technology of adding metal salts of fatty acids to pesticide powder (Special Publication No. 38-12000) and ■Technology of adding liquid silicone resin to pesticide powder (Special Publication No. 39-20735)
is also known.

[Problem that the invention seeks to solve]

However, in method (1) above, biological activity, which is the original purpose of pesticide spraying, is also lost, or it is not practical from an economic standpoint. Method (2) cannot be applied to drugs whose pesticide components are eluted after falling into rice fields and become active when absorbed into rice bodies, etc., and the results will be even worse if they are eaten by fish, etc. Therefore, method (2) is the most practical, but no specific effective method is known yet.

In addition, those containing metal salts of fatty acids in (■) are intended to improve the amphoteric resistance of the sprayed powder and the ability to wet plants, and are required to be used in combination with fatty alcohol polyalkylene glycol ether. However, the method of adding a silicone compound (■) is to prevent the ingredients from changing over time and obtain a stable formulation. There is no known method to reduce the negative impact on

The present invention is intended to solve the above-mentioned problems, and by combining a pesticide active ingredient with a specific compound, even if a highly fish-toxic pesticide active ingredient is blended, the toxicity to fish and other aquatic organisms can be practically reduced. The purpose of the present invention is to propose an agrochemical powder composition that can reduce the amount of harmful substances to a certain extent.

C. Means for Solving Problems] The present invention comprises one or more compounds selected from metal salts of fatty acids and silicon compounds represented by the following general formula [I], and one or more agricultural chemical active ingredients. This is an agrochemical powder composition characterized by the following.

(However, R represents hydrogen, a lower alkyl group, or a phenyl group, and n represents 1 to 100.) The metal salt of a fatty acid that can be used in the present invention has a carbon number of 12
-20 di- or trivalent metal salts are preferred.

Examples include calcium salts, magnesium salts, and aluminum salts of stearic acid, lauric acid, palmitic acid, oleic acid, or linoleic acid, and one or more of these can be used.

In general formula [1), the lower alkyl group represented by R preferably has 1 to 4 carbon atoms, and examples of R include hydrogen, methyl group, ethyl group, propyl group, butyl group,
Examples include phenyl group.

Each R may be the same or different.

n is preferably 10-80, particularly preferably 20-30. One or more compounds of general formula (I) can be used depending on the selection of R and n.General formula [I]
The silicon compound has reactive hydrogen in [ ] and has different chemical properties from the liquid silicone resin used in conventional examples, so it is thought that it can reduce the fish toxicity of agricultural chemical active ingredients. Guessed.

Either one of the metal salt of a fatty acid and the compound of general formula CI) may be used, or both may be used. When using both, one or more of each can be used.

The agrochemical active ingredients used in the present invention can be those commonly used as fungicides, insecticides, herbicides, etc.
Examples thereof are listed below, but are not limited thereto.

2-Chlor-1-(2,4-dichlorophenyl)vinyldimethylphosphate (Compound 1) 0.0-dimethyl-0-3,5,6-dolychloro-2-pyridylphosphorothiony 1-(Compound 2) 1 .3-bis(carbamoylthio)-2-(N.

N-dimethylamino)propane hydrochloride (compound 3) 2-
Methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide (Compound 4) (2-isopropyl-4-methylpyrimidyl-6)-diethylthiophosphate (Compound 5) O20-dipropyl-〇-4
-Methylthiophenyl phosphate
(Compound 6) Dimethylcarbethoxyethyldithiobosphate (Compound 7) S-Methyl-N-[(methylcarbamoyl)oxycothioacetimidate (Compound 8) 2-Secondarybutylphenyl-N-methylcarbamate
(Compound 9) 2-chloro-1-(2,
4,5-Trichlorophenyl)vinyldimethylphosphate (Compound 10) Dimethyldichlorovinylphosphate (Compound 11) Dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (Compound 12) o,o-dimef)Lt -S -(5-Methoxy-1,3゜4-thiadiazol-2(3H)-onyl(3)-methyl)dithiophosphate (Compound 13) Dimethyl(3-methyl-4-nitrophenyl)thiophosphate
(Compound 14) 2-isopropylphenyl-
N-methyl carbamate
(Compound 15) 3.4-xylyl-N-methylcarbamate (Compound 16) o,o-dimethyl-〇-[3-methyl-4-(methylthio)phenyl cothiophosphate (Compound 17) Methalyl-N-methylcarbamate (Compound 18) 1-Naphthyl-N-methylcarbamate (Compound 19) Dimethyldithiophosphorylphenyl acetate (Compound 20) 2-isopropoxyphenyl-N-methylcarbamate (Compound 21) OlO-
Dimethyl-8-phthalimidomethyl-dithiophosmaate (Compound 22) 3,5-xylyl-
N-methylcarbame-1-(compound 23) diisopropyl-1,3-dithiolane-2-ylidene-
Malonate (Compound 24)〇-Ethyl8. S-diphenyldithiophosphate
(Compound 25) o,O-diisopropyl-8-benzyl-thiophosphate
(Compound 26) Tetrachloroisophthalonitrile (Compound 27) 3'-isopropoxy-2-methylbenzanilide (Compound 28) 3-(4-chlorophenoxy)-benzyl-3-(2,
2-Dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Compound 29) (α-cyano-3
-phenoxybenzyl)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Compound 30) 5-tert-butyl-3-(2
,4-dichloro-5-isopropoxyphenyl)-1,
3,4-oxadiazolin-2-one (compound 31
) ~ Potassium α-(2-methyl-4-chlorophenoxy)propionate (Compound 32) The above pesticide active ingredients can be used alone or in combination of two or more.

The agrochemical powder composition of the present invention contains a metal salt of a fatty acid and a silicon compound of general formula (1) as essential components, and these components are combined with talc, kaolin, clay, calcium carbonate,
Zeolite, bentonite, silica sand, white carbon,
It can be diluted with fine mineral powder such as perlite and slaked lime, and further, adjuvants such as physical property improvers and stability improvers can be added as appropriate.

Pesticide active ingredient: The blending ratio of metal salts of fatty acids is 1 by weight.
: 0.1-20, preferably 1 : 0.5-10,
The compounding ratio of the pesticide active ingredient to the silicon compound of general formula (1) is 1:0.05 to 5 by weight, preferably 1:0.
1 to 2 is appropriate. The proportion of fatty acid metal salts and the compound of general formula (1) in the entire pesticide powder is 0.5 to 10% by weight, preferably 3 to 5% by weight.
, 0.03 to 3% by weight of silicon compound, preferably 0
．． The content is preferably 1 to 2% by weight.

The agrochemical powder composition of the present invention can be prepared by simultaneously powdering a metal salt of a fatty acid, an active ingredient of an agrochemical, a fine mineral powder, etc., dissolving a silicon compound in a volatile solvent, adding fine mineral powder thereto, and evaporating the solvent for 120 minutes. A method of heat treatment at ~150°C for 1 to 2 hours, adding pesticide active ingredients, etc., and powdering;
It can be produced by a method in which an agrochemical active ingredient and a metal salt of a fatty acid are added to a silicon compound and suspended, and a fine mineral powder or the like is added thereto to form a powder, or by a method in which these methods are combined.

[For production]

The agrochemical powder composition obtained in the above manner is sprayed on agricultural and horticultural crops or soil in the same manner as conventional agrochemical powders, and is used as a fungicide and
Used as an insecticide, herbicide, etc.

In the application state, there is little elution of pesticide active ingredients, so
Toxicity to fish and other aquatic organisms is low, but activity against harmful organisms remains high. Therefore, even if the powder drifts into nearby rivers or fishponds during spraying, it will not kill fish or aquatic organisms, and even if the powder flows into rivers due to unexpected accidents such as heavy rain after spraying, it will not kill fish or aquatic organisms. It does not kill fish or aquatic organisms.

〔Effect of the invention〕

As described above, according to the present invention, since a specific compound is blended into the pesticide active ingredient, there is little elution of the active ingredient, the toxicity to fish and other aquatic organisms is low, and the activity against pests is maintained at a high level. There is.

Example C] Next, the present invention will be specifically described with reference to Examples, but the Examples are not intended to limit the present invention in any way.

In each example, parts and percentages indicate parts and percentages by weight.

Example 1 (1) 1.0 part of a silicon compound (general formula (in formula 13, R = methyl, n 420) was dissolved in 300 parts of chloroform, and 99.0 parts of Heckley was mixed with the solution, and after evaporating the chloroform, The powder was heat-treated at 120°C for 2 hours.

(2) Compound 7 2-part compound 26
2 parts calcium stearate 5 parts white carbon 3 parts At least 88 parts of the silicone-treated clay of (1) were mixed and ground to form a powder according to a conventional method.

Example 2 (1) Compound 7 40 parts, Compound 2640 parts.

and 5 parts of aluminum stearate to a silicon compound (in the general formula (1), R=n-butyl, n~30) 15
Mix and suspend.

(2) Suspension of (1) 5 parts aluminum stearate 3 parts white carbon
3 parts Example 3 (1) 0.5 parts of a silicon compound (general formula (in formula 13, R=phenyl group, n-10) was dissolved in 300 parts of methylene chloride, and 99.5 parts of clay were mixed therein.

After methylene chloride was evaporated, heat treatment was performed at 150° C. for one hour.

(2) Compound 17 2 parts Compound 9
2 parts magnesium stearate 5 parts white carbon 3 parts At least 88 parts of the silicone-treated clay (1) was made into a powder according to a conventional method.

Example 4 Compound 26 2 parts magnesium oleate 5 parts white carbon 2 parts clay
At least 91 parts were made into a powder according to a conventional method.

Example 5 Compound 26 2 parts Magnesium oleate 5 parts White carbon 2 parts At least 91 parts of the silicon-treated clay of Example 3-(1) was made into a powder according to a conventional method.

Example 6 Compound 7 1.5 parts Compound 9
2 parts white carbon 3 parts Example 1-(1) 93.5 parts or more of the silicon-treated clay was made into a powder according to a conventional method.

Example 7 (1) Silicon compound (general formula (1), where R=hydrogen,
n=80) was dissolved in 300 parts of chloroform, 99.0 parts of clay was added, and after evaporating the chloroform, 1.0 parts of
Heat treatment was performed at 0°C for 2 hours.

(2) Compound 7 1.5 parts Compound 9
2 parts calcium palmitate 3 parts white carbon 3 parts At least 90.5 parts of silicone-treated clay with [I] was made into a powder according to a conventional method.

Example 8 Compound 29 0.5 parts Magnesium linoleate 3 parts White carbon 1 part Example? -95.5 parts or more of the silicone-treated clay (1) was made into a powder according to a conventional method.

Example 9 Compound 7 2 parts Compound 26 2 parts White carbon 3 parts 93 parts or more of the silicon-treated clay of Example 1-(1) was made into a powder according to a conventional method.

Example 10 Compound 7 2 parts Compound 26 2 parts Calcium stearate 5 parts White carbon 3 parts Clay 88 copies The above was made into a powder according to a conventional method.

Comparative example 1 Compound 7 2 parts Compound 26 2 parts White carbon 3 parts Clay 93 copies The above was made into a powder according to the usual method 6 Comparative example 2 Compound 17 2 parts Compound 9 2 parts White carbon 3 parts Clay 93 copies The above was made into a powder according to a conventional method.

Comparative example 3 Compound 26 2 parts White carbon 2 parts Clay 96 copies The above was made into a powder according to a conventional method.

Comparative Example 4 Compound 7 1.5 parts Compound 9
2 parts white carbon 3 parts clay 93.5 parts or more were made into a powder according to a conventional method.

Comparative Example 5 Compound 29 0.5 parts White carbon 1 part Clay 98.5 parts or more were made into a powder according to a conventional method.

Comparative Example 6 (1) 2.0 parts of the silicon compound of formula (n) was dissolved in 300 parts of chloroform, 99.0 parts of clay was added, and after the chloroform was evaporated, heat treatment was performed at 120° C. for 2 hours.

(However, n gradient is 30) (2) Compound 7 2-part compound 26
2 parts white carbon 3 parts (1) At least 93 parts of silicone-treated clay were made into a powder according to a conventional method.

Comparative Example 7 (1) 2.0 parts of the silicon compound of formula (III) was dissolved in 300 parts of chloroform, 99.0 parts of clay was added, and after the chloroform was evaporated, heat treatment was performed at 120° C. for 2 hours.

(However, n illusion 85) (2) Compound 7 Bipartite compound 26
At least 93 parts of silicone-treated clay of 2 parts white carbon and 3 parts (]) was made into a powder according to a conventional method.

Test Example 1 Compound 7 and Compound 2 of Examples 1, 2.9 and Comparative Example 1
The 6 test method used to test the water dissolution of the pesticide active ingredient for the mixed powder of 6 was to use the dissolution tester described in the section of the dissolution test method in the 10th edition of the Japanese Pharmacopoeia, General Test Methods.
The test was conducted using the following method.

<Water dissolution test method> ■ Add 900 m Q of 3 degree hard water and 450 g of paddy soil to a round bottom flask and let stand until the soil settles.

(500 mg of powder is dropped onto the water surface, and the concentration of the active ingredient in water is measured 1, 24 and 48 hours later.

■ After 48 hours, go underwater with the paddle shaft for 20 hours.
Stir for 1 minute at Orpm.

■ Measure the concentration of the active ingredient in water after standing for 5 hours (assuming the rice field is disturbed due to heavy rain, etc.).

The test results are shown in Table 1-. In Table 1, the concentrations of active ingredients Compound 7 and Compound 26 in water were determined by gas chromatography.

Table 1 From the above results, it can be seen that the elution of the active ingredient in the Examples was lower than that in the Comparative Examples.

Test Example 2 A fish toxicity test was conducted on the mixed powders of Compound 7 and Compound 26 of Examples 1 and 2 and Comparative Example 1. The test fish, water quality, and test method are as follows.

Test fish: Carp (Cyprinus carpio), body length 5 cm, weight 3.5 g, 5 fish per group Water quality: Water temperature 20 ± 0.5°C, pH 7.6, dissolved oxygen (D, 0.) 7.5 ± 0. 5mg/m Q〈Fish toxicity test method〉 (Common to test examples 2 to 6) Water tank
5×25×30cn+) Water amount: 20Q Lighting: The lighting time was 12 hours from 7 a.m. to 7 p.m.

Illuminance: 250 Lux at 85 cm above the floor. Weigh the powder to the specified concentration and drop it onto the water surface.
Mortality rates (%) after 8 and 96 hours were examined.

The test results are shown in Table 2.

Table 2 Test Example 3 Regarding the powders of Examples 3 and 6.7 and Comparative Examples 2 and 4,
A fish toxicity test was conducted on carp. The test method was the same as Test Example 2, and the test points and water quality were as follows.

Test point: Carp (Cyprinus carpio), weight 1.5g, 1 group, 10 fish Water quality: Water temperature 22.5+1.0℃, pH 7.6+0.1
．． 0.0. 7.5±1, 0 mg/m Q test results are shown in Table 3.

Table 3 Test Example 4 The powders of Examples 1 to 8 and Comparative Examples 1 to 5 were similarly tested for fish toxicity against eels.

Test fish: European eel (^ngui11.aang
uilla), weight 3g, 1 group 10 fish Water quality: Water temperature 20
．． 0±2.0°C, pl+7.6±0.1.0.0.7.
5±0.5mg/mfl The test results are shown in Table 4.

Table 4 Test Example 5 The powders of Examples 1, 2, 3, and 6.7 and Comparative Examples 1 and 2°4 were similarly tested for fish toxicity against black shrimp.

Test sample: Kuruma shrimp (Penaqueus, japon)
, tcus) Weight 25 g, 10 animals in group i Water quality: Water temperature 20.0±2.0℃, PH7.6±0.1
．． 0.0.7.5±0.5-g/mQ The test results are shown in Table 5.

Table 5 Test Example 6 Examples 1, 2, 9 and 10 and comparative powders of 6°7 were similarly tested for fish toxicity against carp. The concentration in water was set at 500pp, and the mortality rate was observed over time.

Test fish: Carp (Cyprinus carpLo) weight 3.5g, 1 group lO tail water Quality: Water temperature 20±0.5℃, pl+7.6±0.10
．． 0. 7.5±0.5 fog g/s Q test results are shown in Table 6.

From the above results, it is recognized that the pesticide powder composition according to the present invention reduces toxicity to aquatic organisms including fish.

Test Example 7 The following biological test was conducted using powders containing 0.5% of Compound 29 of Example 8 and Comparative Example 5.

Biological tests were conducted using plants with a height of 2 grown in magnetic pots with a diameter of 12 cm.
Paddy rice (variety: Aichi) measuring 0 to 25 cm was covered with a wire mesh gauge, and approximately 20 end-instar leafhopper larvae resistant to organophosphates and carbamates were released per bot. ejector,
Powder was applied in amounts equivalent to 1 kg, 2 kg, and 4 kg per 10 a using a Pelger duster with an inner diameter of 40 cm and a height of 55 cm. However, the pressure should be reduced to 20+m), and the standing time should be 20+ m).

It was set to 2 minutes. After spraying, keep the pot in the greenhouse and spray 4
Number of viable insects after 8 hours.

The number of dead and alive was investigated to determine the mortality rate. In the test, 3 pots were tested for each drug, and the pots were kept submerged in water to a depth of 2 cm during the test period.

The results are shown in Table 7.

Table 7 From the results in Table 7, it can be seen that there is no difference in biological activity between the examples and the comparative examples.

As is clear from the above test results, the pesticide powder composition according to the present invention suppresses the release of components into water without decreasing biological activity, and reduces toxicity to aquatic organisms including fish. Is recognized.

Procedure Neho J-1, Mi-1F 1980 711//I-1 Commissioner of the Patent Office Manabu Shiga 1, Indication of the case 1982 Patent Application No. 119468/2, Name of the invention Pesticide powder composition 3. Relationship with the case of the person making the amendment Patent applicant address: 14-26, Ikenohata 1rE, Taito-ku, Tokyo
(016) Representative of Kumiai Chemical Co., Ltd.
Nobuhiko Mochizuki 4, Agent 105 Telephone 436-4700 Address
3-15-8-6 Nishi-Shinbashi, Minato-ku, Tokyo Number of inventions increased by the amendment 07 Target of the amendment Detailed explanation of the invention in the specification Column 8 Contents of the amendment Table 2 on page 23 of the specification [60] in the column after 96 hours in Comparative Example 1 is set to rlooJ, and rlooJ is set to r60. Revised to l.

Claims (3)

[Claims] (1) A pesticide powder composition comprising one or more compounds selected from metal salts of fatty acids and silicon compounds represented by the following general formula [I] and one or more pesticide active ingredients. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, R represents hydrogen, a lower alkyl group, or a phenyl group, and n represents 1 to 100.) (2) The agrochemical powder composition according to claim 1, wherein the metal salt of fatty acid is a calcium salt, magnesium salt, or aluminum salt of stearic acid, lauric acid, palmitic acid, oleic acid, or linoleic acid. (3) The agrochemical powder composition according to claim 1, wherein R is hydrogen, methyl group, ethyl group, propyl group, butyl group, or phenyl group.