JP2518631B2 - Solid / pesticidal composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to stabilization of a solid pesticide composition, and more specifically, to a pesticide compound that is easily decomposed with an acid catalyst and a pesticide compound that is easily decomposed with a base catalyst. The present invention relates to a solid pesticide composition in which a pesticide compound is stabilized, which is characterized by comprising a water-absorbent resin.

(Prior art) Agricultural chemicals are those in which the pesticidal compound that is the active ingredient is stable during storage, and after spraying, after acting on the target pest fungus or grass, it quickly disappears and does not remain in the crop or soil. Ideal. At present, commonly used organic phosphorus compounds, carbamate compounds, synthetic pyrethroid compounds and the like have an ester bond as a chemical structure, and these are easily eliminated from the environment by a hydrolysis reaction.

However, even during storage of the preparation, the value of the active ingredient decreases due to hydrolysis, which may lead to decrease in activity and economic loss.

Conventionally, as means for suppressing the gradual decomposition of the active ingredient in the product, for example, in organic phosphorus preparations, alkyl phosphate (Japanese Patent Publication No. 45-9199) and higher fatty acids (Japanese Patent Publication No. 35-63).
No. 99), a method of adding a carboxylic acid or phosphoric acid (Japanese Patent Publication No. 51-38766) to an N-alkyl carbamate insecticide is known. In order to suppress the hydrolysis reaction by a base catalyst, these try to stabilize by adding an acid.On the other hand, an active ingredient that undergoes acid hydrolysis, such as a urea-based compound or a nitromethylene derivative, is not stable. The hydrolysis reaction occurs in the presence and the stabilizers mentioned are not universally effective for all compounds.

As a means for suppressing acid-catalyzed hydrolysis, it is known to add a base to neutralize, for example, for 2H-1,3-thiazinetetrahydro-2- (nitromethylene),
Addition of aromatic secondary amines (JP-A-59-134703) Addition of potassium salts of organic acids and phosphoric acids (JP-A-57-18604)
However, on the other hand, they have the drawback of promoting the hydrolysis reaction by a base catalyst such as an organic phosphorus agent.

Further, with the labor saving of agriculture in recent years, there is a great demand for insecticidal sterilization mixed preparations, and there is a combination of an active ingredient which is hydrolyzed by an acid catalyst and an active ingredient which is hydrolyzed by a base catalyst. It was more difficult than the stabilization of a single component to accelerate the decomposition of any active ingredient and obtain a stable mixed preparation, and it was often difficult to obtain a preparation that could be stored for a long period of time.

(Problems to be Solved by the Invention) The present invention has been made in order to solve such conventional problems and provides an agricultural chemical compound which is easily decomposed by an acid catalyst and an agricultural chemical compound which is easily decomposed by a base catalyst. It is an object of the present invention to provide a stabilized solid pesticide composition that can be stored for a long period of time by suppressing a hydrolysis reaction of an active ingredient during product storage by incorporating a water absorbent resin.

(Means for Solving the Problems) The present invention is characterized in that a water-absorbent resin is blended with an agrochemical compound which is easily decomposed by an acid catalyst and an agrochemical compound which is easily decomposed by a base catalyst. It is a pesticide composition.

As the agrochemical compound used in the present invention, any compound such as an insecticide, a fungicide, a herbicide or a plant growth regulator can be used, and a compound which is decomposed by a hydrolysis reaction in the presence of an acid or a base is particularly preferable.

Examples of the compound will be given below, but the present invention is not limited thereto.

Abbreviations are shown in []. Compounds that are easily decomposed by an acid catalyst are indicated by ◯, and compounds that are easily decomposed by a base catalyst are indicated by *.

O, S-Dimethyl-N-acetyl-phosphoroamidothioate [acephate] Allethrin [Allethrin] O, O-diethyl-O- (5-phenyl-3-isoxazolyl) phosphorothioate * [Isoxathione] α-ethylthio-O- Toluyl methyl carbamate *
[Ethiophenecarb] O, O, O ', O'-tetraethyl-S, S'-methylenebisphosphorodithioate [Ethion] O, O-diethyl-S-2- (ethylthio) ethylphosphorodithioate [Ethylthiomethone] Methyl-N, N'-dimethyl-N-[(methylcarbamoyl) oxy] -1-thiooxamimidate * [oxamyl] 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminothio ) Methyl carbamate [carbosulfan] O, O-dimethyl-O- (3,5,6-trichloro-2-pyridyl) phosphorothioate [chloropyrifosmethyl] 2-methoxy-4H-1,3,2-benzodioxaphospho Phosphorus
2-Sulfide * [salithione] 2-chloro-1- (2,4-dichlorophenyl) vinyldimethylphosphate * [dimethylbinphos] O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate * [ Dimethoate] 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea [Diflubenzuron] O, O-diethyl-O- (2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate O [Diazinon] Dimethyl-methylcarbamoylethylthioethyl-phosphorothiolate [bamidothione] O, O-diethyl-O- (3-oxo-2-phenyl-2H
-Pyridazin-6-yl) phosphorothioate * [pyridaphenthione] pyretrin * [pyretrin] (RS) -α-cyano-3-phenoxybenzyl (RS)-
2- (4-chlorophenyl) -3-methylbutyrate *
[Fenvalerate] 2-tert-butylimino-3-isopropyl-5
-Phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazine ○ [buprofezin] dimethyldicarbetoxyethyldithiophosphate * ○
[Marathon] 2-Secondary butylphenyl-N-methylcarbamate * ○ [BPMC] 5-benzyl-3-furylmethyl dl-cis, trans-
Chrysanthemate * [resmethrin] Dimethyl-2,2-dichlorovinyl phosphate * ○ [DDV
P] O, O-dimethyl-S- [5-methoxy-1,3,4-thiadiazol-2 (3H) onyl- (3) -methyl] -dithiophosphate * [DMTP] O, O-dimethyl-O- (3-Methyl-4-nitrophenyl) thiophosphate * [MEP] O, O-dimethyl-O- [3-methyl-4- (methylthio) phenyl] thiophosphate [MPP] Metatryl-N-methylcarbamate * [MTMC ] Ethyl dimethyldithiophosphoryl phenylacetate * [PA
P] 2-isopropoxyphenyl-N-methylcarbamate * [PHC] diisopropyl-1,3-dithiolane-2-ylidene-malonate [isoprothiolane] zinc ethylene bisdithiocarbamate * [dineb] 3,5-dimethyltetrahydro-2H- 1,3,5-thiadiazin-2-thione * ○ [Dazomet] bis (dimethylthiocarbamoyl) disulfide [thiuram] methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate [Benomyl] Manganese ethylene bisdithiocarbamate [ Manneb] 1- (4-chlorobenzyl) -1-cyclopentyl-3
-Phenylurea * ○ [Pencyclone] O-ethyl-S, S-diphenyldithiophosphate * [E
DDP] O, O-diisopropyl-S-benzylthiophosphate
[IBP] 1- (α, α-dimethylbenzyl) -3- (paratolyl) urea [Daimuron] Mildiomycin * ○ [Mildiomycin] 4- (2,4-dichlorobenzoyl) -1,3-dimethyl- 5
-Pyrazolyl-P-toluenesulfonate * ○ [pyrazolate] 3- (3,4-dichlorophenyl) -1-methoxy-1-
Methylurea * ○ [linuron] 2H-1,3-thiazine-tetrahydro-2- (nitromethylene) [TTNM] 2-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl-aminosulfonyl] benzoic acid Methyl Ester (Bensulfuron Methyl) The water-absorbent resin used in the present invention is a polymer electrolyte physically or chemically crosslinked. The water-absorbent resin referred to here is one that swells in water but does not dissolve, and absorbs and retains several tens of times its own weight or more of water. For example, starch acrylic acid copolymer, polyvinyl alcohol sodium acrylate graft polymer, styrene maleic anhydride copolymer salt, polyacrylic acid sodium crosslinker, polyvinyl alcohol acrylic acid graft polymer, starch acrylonitrile graft copolymer Examples thereof include coalesce, crosslinked polyalkylene oxide, and saponified product of vinyl ester ethylenically unsaturated carboxylic acid or its derivative.

Product names include, for example, Turfine KP-6201 (Kao Corporation), Mizumochi Ichiban OKS-7703 (Nippon Gosei Kagaku Kogyo Co., Ltd.), Mizuace Ace IM-1000 (Sanyo Kasei Co., Ltd.), Arasorb KR-713 ( Arakawa Chemical Industry Co., Ltd.),
Acryhope GH-5 (Nippon Shokubai Kagaku Kogyo Co., Ltd.), Diawet BS (Mitsubishi Yuka Co., Ltd.) and the like can be mentioned.

Next, these properties are shown in Table 1.

In the solid agricultural chemical composition of the present invention, the compounding ratio of the water absorbent resin to the agricultural chemical compound which is easily decomposed by an acid catalyst and the agricultural chemical compound which is easily decomposed by a base catalyst can be freely changed. On the other hand, it is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight.

The dosage form used in the present invention is a solid dosage form such as powder, granules or wettable powders, and in addition to agrochemical compounds, water absorbent resins, auxiliary agents, extenders and the like can be optionally used.

As the auxiliary agent, a surfactant, a physical property improver, a binder,
Examples of the extender include colorants and the like. Mineral substances such as clay, talc, bentonite, diatomaceous earth, inorganic salts such as calcium carbonate, calcium sulfate and barium sulfate, and oil absorbing powder such as white carbon.

The solid agrochemical composition of the present invention can be produced by a usual method for producing an agrochemical formulation. The production method is shown below for each mold, but the present invention is not limited thereto.

Dust agent A pesticide compound that is easily decomposed by an acid catalyst, a compound that is easily decomposed by a base catalyst, a water absorbent resin, an auxiliary agent, and a filler are uniformly mixed and pulverized to obtain a dust agent.

Granules A pesticide compound that is easily decomposed by an acid catalyst, a compound that is easily decomposed by a base catalyst, and a water-absorbent resin are mixed and pulverized to obtain a uniform powder, which is coated on a natural or artificial granular carrier through a binder to obtain a granule.

Wettable powder An agrochemical compound that is easily decomposed by an acid catalyst, a compound that is easily decomposed by a base catalyst, a water absorbent resin, a surfactant, an auxiliary agent, and an extender are uniformly mixed and pulverized to obtain a wettable powder.

(Effect of the invention) The solid pesticide composition of the present invention has extremely high storage stability by mixing a water-absorbent resin with an agrochemical compound that is easily decomposed by an acid catalyst and an agrochemical compound that is easily decomposed by a base catalyst. It is highly active and suppresses hydrolysis during storage, and exhibits high activity even after long-term storage.

Further, the present invention is effective when producing a mixed preparation of an agrochemical compound which is easily decomposed by an acid catalyst and an agrochemical compound which is easily decomposed by a base catalyst.

(Examples) Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

All parts and% in each example are parts by weight. The water absorbent resins used in the examples are those shown in Table 1 and each trade name is used.

<Example 1> Powder MP20 (20 parts), EDDP (25 parts), Penciclone (15 parts), Mizuace I
20 parts of M-1000, 45 parts of white carbon, 885 parts of clay are mixed and pulverized uniformly, and MPP2%, EDDP2.5%, pencyclone 1.5
% To obtain a mixed powder.

<Example 2> Wetting powder Fenvalerate 100 parts, DDVP 100 parts, sodium lauryl sulfate 30 parts, sodium alkylbenzene sulfonate
30 parts, Tarfine KP-6201 30 parts, white carbon 10
0 part and 610 parts of clay are uniformly mixed and pulverized to obtain a mixed wettable powder containing 10% fenvalerate and 10% DDVP.

<Example 3> Powder buprofezin 10 parts, MEP 30 parts, Mizumochi Ichiban OKS-770
3 50 parts, white carbon 20 parts and clay 890 parts are uniformly mixed and pulverized to obtain a mixed powder containing 1% buprofezin and 3% MEP.

<Example 4> Dust agent 20 parts of dimethyl vinphos, 15 parts of pencyclone, 15 parts of Turfine KP-6201, 10 parts of white carbon, 300 parts of calcium carbonate, 640 parts of clay are uniformly mixed and pulverized, and 2% of dimethyl vinphos, A mixed powder containing 1.5% of pencyclone is obtained.

<Example 5> Powder dimethylvinphos 20 parts, BPMC 20 parts, Mizuace IM-100
30 parts, 30 parts of white carbon and 900 parts of clay are uniformly mixed and pulverized to obtain a mixed powder containing 2% of dimethylvinphos and 2% of BPMC.

Reference Example 1 Mizuace Ace IM-1000 of Example 1 was replaced with stearic acid to obtain a mixed powder containing 2% MPP, 2.5% EDDP and 1.5% pencyclone.

<Reference Example 2> Turfin KP-6201 of Example 2 was replaced with clay to obtain a mixed wettable powder containing 10% fenvalerate and 10% DDVP.

<Reference Example 3> 50 parts of OKS-7703, which is the only mochi mochi in Example 3, was treated with isopropyl hydrogen phosphate (physical property improver, PAP,
(Nippon Kagaku Kogyo Co., Ltd.) 5 parts and 45 parts of clay are replaced to obtain a mixed powder containing 1% buprofezin and 3% MEP.

<Reference Example 4> 15 parts of Turfine KP-6201 of Example 4 was replaced with 5 parts of PAP (physical property improver) and 10 parts of white carbon to obtain a mixed powder containing 2% of dimethylvinphos and 1.5% of pencyclone. .

<Reference Example 5> The Mizuace IM-1000 of Example 5 was replaced with N-isopropyl N'-phenyl-P-phenylenediamine,
A mixed powder containing 2% dimethylvinphos and 2% BPMC is obtained.

<Test Example 1> The samples of Examples 1 to 5 and Reference Examples 1 to 5 were placed in a kraft bag and stored in a thermo-hygrostat kept at 40 ° C and 70% relative humidity for 30, 60 and 90 days. . 30 days for each sample,
Table 2 shows the residual rate of each pesticide compound after 60 days and 90 days.

 The residual rate (%) was calculated by the following formula.

<Test Example 2> The powders of Examples 1 and 4 and Reference Examples 1 and 4 were put in a kraft bag and placed in a thermo-hygrostat kept at 40 ° C and a relative humidity of 75% for 30 days.
Using the ones stored for 60 days and 90 days, a rice crest blight control test was conducted.

<Method> Three strains were transplanted in a white porcelain pot having a diameter of 9 cm, with three stems as one strain, and the 7 to 8 leaf stage paddy rice (cultivar: Kinnanfeng) was sprayed with a dusting agent. The amount of drug sprayed is equivalent to 2 kg per 10 ares. 3 days after spraying, inoculate the leaf sheath of paddy rice with the bacterial wilt disease cultivated in a flat potato medium, and keep it in a wet room installed in a greenhouse.
After 8 days, the length of the blotch spot formed on the rice leaf sheath was measured. The test was repeated in 5 pots.

 The control value was calculated by the following formula.

The results are shown in Table 3.

From the above results, the solid pesticide composition according to the present invention is less decomposed than the preparations given as the comparative section, retains stable activity even after long-term storage, and has extremely excellent stability.

Claims (1)

(57) [Claims] 1. A stabilized solid pesticide composition comprising a pesticide compound which is easily decomposed by an acid catalyst and a pesticide compound which is easily decomposed by a base catalyst, and a water absorbent resin.