JPS63179802A - Herbicide composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized solid agricultural chemical composition suppressing hydrolysis reaction of active ingredients during preservation of product, preservable for a long period of time, by blending an agricultural chemical composition with a water absorbing resin such as starch-acrylic acid copolymer. CONSTITUTION:A solid agricultural chemical composition obtained by blending 1pt.wt. of one or more agricultural chemical compounds such as acephate, allethrin, isoxathion. ethiofencarb, carbosulfan, salithione, pyrethrin, malathione, etc., (especially preferably combination of two different compounds) with 0.05-5 pts.wt., preferably 0.2-2pts.wt. water-absorbing resin (e.g. salt of styrene-maleic anhydride copolymer, crosslinked sodium polyacrylate, crosslinked polyalkylene oxide, etc.). The composition slightly decomposes, has stable activity even after long-period preservation and provides extremely excellent stability.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to the stabilization of solid agricultural chemical compositions.

More specifically, the present invention relates to a stabilized solid agrochemical composition characterized by containing one or more kinds of agrochemical compounds and a water-absorbing resin.

(Prior art) Pesticides have stable active ingredients (pesticide compounds) during storage, and after being sprayed and acting on target pest fungi or grass, they disappear quickly and do not remain in crops or soil. ideal. Currently, commonly used organic phosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, etc. have ester bonds as their chemical structures, and these easily disappear from the environment through hydrolysis reactions.

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

Conventionally, methods for suppressing the gradual decomposition of active ingredients in products include, for example, adding alkyl phosphates (Japanese Patent Publication No. 45-9199) or higher fatty acids (Japanese Patent Publication No. 35-6399) to organic phosphorus preparations; Carboxylic acid or phosphoric acid (PTK
1-38766) is known.

These suppress the base-catalyzed hydrolysis reaction, so
However, active ingredients that undergo acid hydrolysis, such as urea-based compounds or nitromethylene derivatives, undergo a hydrolysis reaction in the presence of acids, and the above-mentioned stabilizers is not universally valid for all compounds.

As a means to suppress hydrolysis caused by an acid catalyst, it is known to neutralize by adding a base. For example, 2H-1,3-
thiazinetetrahydro-2-totromethylene).

Addition of aromatic secondary amines (JP-A-59-134703) Addition of potassium salts of organic acids and phosphoric acids (JP-A-57-1988)
No. 18604), but on the other hand, these have the drawback of promoting the hydrolysis reaction by a base catalyst such as an organic phosphorous agent.

In addition, in recent years, with the labor saving in agriculture, there has been a large demand for insecticidal and sterilized mixed lumber, and there are combinations of active ingredients that are hydrolyzed by acid catalysts and active ingredients that are hydrolyzed by base catalysts. Promoting the decomposition of any of the active ingredients to obtain a stable mixed preparation is more convenient than stabilizing a single ingredient, but it has often been difficult to obtain a preparation that can be stored for a long period of time.

(Problems to be Solved by the Invention) The present invention has been made to solve these conventional problems, and by blending a water-absorbing resin with an agricultural chemical compound, the active ingredient can be absorbed during product storage. The purpose of this invention is to suppress hydrolysis reactions and provide a stabilized solid agricultural chemical composition that can be stored for a long period of time.

(Means for Solving the Problems) The present invention is a stabilized solid agricultural chemical composition characterized by blending one or more agricultural chemical compounds and a water-absorbing resin.

The agricultural chemical compound used in the present invention can be any compound such as an insecticide, fungicide, herbicide, or plant growth regulator, and compounds that decompose by a hydrolysis reaction in the presence of an acid or a base are particularly preferred.

Examples of compounds are given below, but the present invention is not limited thereto in any way.

[ ] indicates an abbreviation.

o,S-dimethyl-N-acetyl-phosphoroamidothioate [acephate corethrin [allethrin] 0.0-diethyl-〇-(5-phenyl-3-inxazolyl) phosphorothioate [inxathion] 2-(ethylthiomethyl) Phenyl-methylcarbamate [ethiophenecarb] ○, o, o', o'-tetraethyl-s, s'-methylenebisphosphorodithioate [Nithion] ○, O-diethyl-5-2-(ethylthio)ethylphosphoro Dithioate [ethylthiometone] methyl-N-N'-dimethyl-N-[(methylcarbamoyl)oxyph-1-thioxamimidate [oxamyl] 2.3-dihydro-2,2-dimethyl-7-benzo(b
) Furanyl = N-dibutylaminothio-N-methylcarbamate○,O-dimethyl-〇-(3,5.6-dolychloro-2
-pyridyl)phosphorothioate [chlorpyrifosmethyl]2-methoxy-4. H-1, 3,
2-benzodioxaphosphorine-2-sulfide
[Salichione] 2-chlor-1-(2.4
-dichlorophenyl)vinyl dimethyl phosphate
[Dimethylvinphos]0,○-dimethyl-S
-(N-methylcarbamoylmethyl)dithiophosphate [dimethoate]1-(4-chlorophenyl)-1-(2,6-difluorobenzoyl)
Urea [Diflubenzuron] (2-isopropyl-4-methylpyrimidyl-6)-diethylthiophosphate [Diazinon] Dimethyl-methylcarbamoylethioethyl-phosphorothiolate [Bamidothion] 0
, 0-diethyl-〇-(3-oxo-2-phenyl-2
H-pyridazin-6-yl) phosphorothioate [pyridafenthione] pyrethrin [pyrethrin] (RS)-α-cyano-3-phenoxybenzyl-(
RS)-2-(4-chlorophenyl)-3-methylbutanoate [fenvalate] 2-tert-butylimino-3-isopropyl-5
-Phenyl-3,4,5.6-titrahydro 2H-1
．． 3.

5-Thiadiazine [buprofezin] dimethyl dirubethoxyethyl dithiosulfate [
Marathon] 2-Secocidalybutylphenyl-N-methylcarbamate (BPM
C) 5-benzyl-3-furylmethyldisis, trans-chrysanthemate [resmethrin] dimethyl-2,2-dichlorovinylphosphate [)DVP) 0.0-dimethyl-8(5-methoxy-1,3, 4-thiadiazole-2(3H)onyl-(3)-methyl)dithiophosphate
(DMTP)0.0-dimethyl-〇-(3-methyl-4
-nitrophenyl)thiophosphate
(MEP)0.0-dimethyl-〇-[3-methyl-4-(methylthio)phenyl cothiophosphate
(MPP) Methalyl-N-methylcarbamate (MTMC) Ethyl dimethyldithiophosphorylphenylacetate (PAP) 2-isopropoxyphenyl-N-methylcarbamate (PHC) Diisopropyl-1,3-dithiolan-2-ylidene-
Malonate [isobrothiolane] zinc ethylene bisdithiocarbamate [zineb] = 7- 3,5-dimethyltetrahydro-2H-1,3,5-thiadiazine-2-thione [dazomet] methyl-1-(butylcarbamoyl)-2 -Benzimidazole carbamate [Benomyl] Manganese ethylene bisdithiocarbamate [
maneb] 1-(4-chlorobenzyl)-1-cyclopentyl-3
-Phenylurea [Benziclon] 0-ethyl-8,S-diphenyldithiophosphate (EDDP) 0.0-diisopropyl-8-benzylthiophosphate
(I
BP) 1-(α,α-dimethylbenzyl)-3-(paratolyl)urea
[Daimron] Mildiomycin [Mildiomycin] 4-(2,4-dichlorobenzoyl)-
1,3-dimethyl-5-pyrazolyl-P-toluenesulfonate [virazolate] 3-(3,4-dichlorophenyl)-1-methoxy-1
-Methylurea [linuron] 2H-1,3-thiazine-tetrahydro-2-totromethylene) (
TTNM) 2-((4,6-Simethoxypyrimidin-2-yl)aminocarbonyl-aminosulfonyl)benzoic acid methyl ester [pensulfuron methyl] The following margins The water-absorbing resin used in the present invention is a polymer electrolyte. The water-absorbing resin here is one that swells in water but does not dissolve, and absorbs and retains more than several tens of times its own weight in water.For example, starch acrylic resin Acid copolymer, polyvinyl alcohol soda acrylic acid graft polymer, styrene maleic anhydride copolymer salt, polysodium acrylate crosslinked product, polyvinyl alcohol acrylic acid graft polymer.

Starch acrylonitrile graft copolymer.

Crosslinked polyalkylene oxides, saponified products of vinyl ester ethylenically unsaturated carboxylic acids or derivatives thereof, etc. can be mentioned. Examples of product names include Turfine KP-6201 (Kao Corporation) and Mizumochi Ichiban 0KS-7703 (Nippon Gosei Kagaku Kogyo Co., Ltd.).

Mizuace IM-100,0 (Sanyo Chemical Industries, Ltd.)
, Arasorb KR-713 (Arakawa Chemical Industry Co., Ltd.),
Acryhope GH-5 (Nippon Shokubai Chemical Co., Ltd.),
Examples include Diawet BS (Mitsubishi Yuka Co., Ltd.).

Next, these properties are shown in Table 1.

Margins below In the solid agrochemical composition of the present invention, the blending ratio of the water-absorbing resin to the agrochemical compound can be changed freely;
The appropriate amount is usually 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 1 part by weight of the agricultural chemical compound.

The dosage forms used in the present invention are solid dosage forms such as powders, granules, and wettable powders, and agricultural chemical compounds, additives for water-absorbing resins, fillers, etc. can be optionally used.

Auxiliary agents include surfactants, physical property improvers, binders, coloring agents, etc. Extending agents include minerals such as clay, talc, bentonite, and diatomaceous earth, calcium carbonate,
Examples include inorganic salts such as calcium sulfate and barium sulfate, and oil-absorbing powders such as white carbon.

The solid agricultural chemical composition of the present invention can be manufactured by a conventional manufacturing method for agricultural chemical formulations. The manufacturing method for each type is shown below, but the present invention is not limited thereby.

■Powder Powder is obtained by uniformly mixing and pulverizing the pesticide compound, water-absorbing resin, adjuvant, and bulking agent.

■Granes Pesticide compound and water-absorbing resin are mixed and ground into a uniform powder.
Granules are obtained by coating natural or artificial granular carriers with a binder.

II- (1) Wettable powder A pesticide compound, a water-absorbing resin, a surfactant, an auxiliary agent, and a filler are uniformly mixed and pulverized to obtain an irrigant.

(Effects of the Invention) The solid agricultural chemical composition of the present invention has extremely high storage stability of the compound by blending the water-absorbing resin with the agricultural chemical compound, suppresses hydrolysis during storage, and improves the stability after long-term storage. also shows high activity.

Furthermore, the present invention is effective when producing a mixed preparation of a pesticide compound that is easily decomposed with an acid catalyst and an agrochemical compound that is easily decomposed with a base catalyst.

(Examples) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Note that all parts and % on each side indicate parts and % by weight. The water-absorbing resins used in the examples are shown in Table 1, and their respective trade names are used.

<Example 1> Powder 20 parts of chlorpyrifos methyl, Turfine KP-62
011.0 parts, white carbon 1o parts, clay 960
The mixture was uniformly mixed and ground to obtain a powder containing 2% of chlorpyrifosmethyl.

<Example 2> Powder agent 20 parts of MPP, 25 parts of EDDP, 15 parts of Benziclone.

Mizu Ace IM-100020 parts, White Carbon 4
5 parts and 885 parts of clay were uniformly mixed and pulverized, and MPP 2%
A mixed powder containing 2.5% of EDDP and 1.5% of Benziclone is obtained.

<Example 3> Irrigation agent fenvalerate 100 parts, sodium lauryl sulfate 3
0 parts, 30 parts of sodium alkylbensene sulfonate,
130 parts of Turfine KP-620, 100 parts of white carbon, and 710 parts of clay are uniformly mixed and ground to obtain a wettable powder containing 10% of fenvalerate.

<Example 4> Granules Carbosulfan 50 parts, Turfine KP-6201
After finely pulverizing 50 parts and 100 parts of white carbon into a uniform powder, silica sand (φ850 to 1700 μm
) to 750 parts of polyethylene glycol (average molecular weight 38
0 to 420) as a binder to obtain granules containing 5% carbosulfan.

<Example 5> Granules Buprofezin 10 parts, MEP 30 parts, Mizumochi Ichiban○
350 parts of KS-770, 20 parts of white carbon, and 890 parts of clay were uniformly mixed and ground, and buprofezin 1%,
A mixed powder containing 3% MEP is obtained.

<Example 6> Granules 20 parts of dimethylvinphos, 15 parts of benzicron, 115 parts of Turfine KP-620, 10 parts of white carbon, 300 parts of calcium carbonate, and 640 parts of clay were uniformly mixed and ground, and 2% dimethylvinphos, Benjikron 1゜5
A mixed powder containing % is obtained.

<Example 7> Granules: 20 parts of dimethylvinphos, 20 parts of TTNM, 30 parts of Mizuace IM-1000, 30 parts of white carbon, and 900 parts of clay were uniformly mixed and pulverized, and dimethylvinphos 2%
, a mixed powder containing 2% of TTNM is obtained.

<Reference Example 1> Turfine KP-6201 in Example 1 was replaced with clay to obtain a powder containing 2% chlorpyrifosmethyl.

<Reference Example 2> MizuAce IM-1000 in Example 2 was replaced with stearic acid to obtain a mixed powder containing 2% MPP, 2.5% EDDP, and 1.5% Benziclone.

Reference Example 3 Turfine KP-6201 in Example 3 was replaced with clay to obtain a wettable powder containing 10% fenvalerate.

<Reference Example 4> In the turfine of Example 4, 'p-6201' was replaced with white carbon to obtain granules containing 5% carbosulfan.

<Reference Example 5> 350 parts of Mizumochi Ichiban 0KS-770 of Example 5 was mixed with isopropyl hydrogen phosphonate (PAP,
(Nihon Kagaku Kogyo) and 45 parts of clay to obtain a mixed powder containing 1% buprofezin and 3% MEP.

Reference Example 6> 115 parts of Turfine KP-620 of Example 6 was PAP
Part B is replaced with 10 parts of white carbon to obtain a mixed powder containing 2% dimethylvinphos and 1.5 parts of pencyclo.

<Reference Example 7> Substituting Mizuace IM-1000IN-isopropyl N'-phenyl-P-phenylenediamine in Example 7 to obtain a mixed powder containing 2% dimethylvinphos and TTNM25.

<Test Example 1> The samples of Examples 1 to 7 and Reference Examples 1 to 7 were placed in kraft bags and stored in a constant temperature and humidity chamber maintained at 40°C and 70% relative humidity for 30 days, 60 days, and 90 days. . Table 2 shows the residual rate of each pesticide compound after 30 days, 60 days, and 90 days for each sample.

In addition, the residual rate (%) was calculated|required from the following following formula.

Table 2 <Test Example 2> The powders of Example 2.6 and Reference Example 2.6 were placed in a kraft bag and placed in a constant temperature and humidity chamber maintained at 40°C and 75% relative humidity for 30 minutes.
A rice sheath blight control test was conducted using the rice stored for 1, 60, and 90 days.

<Method> In a white porcelain pot with a diameter of 9 cm, transplant 3 plants with 3 stems as 1 plant.
Powder was applied to the grown rice (variety: Zennanfu) at the 7th to 8th leaf stage. The amount of chemical sprayed is equivalent to 2 kg per 10 are. Three days after spraying, the sheath blight fungus cultured on a flat potato medium was inoculated onto the leaf sheaths of paddy rice, and kept in a greenhouse set up inside a greenhouse.
Eight days later, the length of the sheath blight disease ring formed on the paddy rice leaf sheath was measured. This test was repeated in 5 pots.

The control value was calculated using the following formula.

The results are shown in Table 3.

Margin Table 3 Below: From the above results, the solid agricultural chemical composition of the present invention shows extremely excellent stability, with less decomposition and remaining stable activity even after long-term storage, compared to the comparative formulations. It will be done.

Claims (2)

[Claims] (1) A solid agrochemical composition comprising one or more agrochemical compounds and a water-absorbing resin. (2) The solid agricultural chemical composition according to claim 1, wherein the agricultural chemical compound is a combination of two different compounds.