JPH03181405A - Stabilized agricultural chemical composition - Google Patents

Abstract

PURPOSE:To provide a stabilized agricultural chemical composition by adding a specific amorphous silica and preferably further a compound containing a polyethylene glycol chin, polypropylene glycol chain, etc., to a mixture comprising a specific nitro compound and an organic phosphorus compound. CONSTITUTION:A surface silanol group-reduced silica prepared by silylating or calcining water-containing amorphous silica produced by a wet synthetic method, amorphous silica anhydride or a silylated product thereof is added to a mixture containing a nitro compound of the formula [R<1> is H or alkyl; R<2> is -S-R<3> (R<3> is alkyl) or -N(R<4>)R<5> (R<4> and R<5> are H or alkyl); Y is CH or N] and an organic phosphorus compound (e.g. edifenphos) as active ingredients to provide a stabilized agricultural chemical composition. A compound containing a polyethylene glycol chain, polypropylene glycol chain or ethylene glycol-propylene glycol copolymer chain is further preferably added to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel stabilized agrochemical compositions, processes for their production and their uses.

-a It is known in Japanese Patent Application No. 1-561 that a mixture containing the nitro compound represented by formula (I) and other insecticides including organic phosphorus compounds as active ingredients is useful as an agricultural insecticidal composition.
No. 24, and Japanese Patent Application No. 1-56125 describes that a mixture containing a fungicide containing an organic phosphorus compound as an active ingredient is useful as an agricultural insecticidal and fungicidal composition.

According to this application, it is stated that these mixtures exhibit synergistic effects by mixing them rather than using a single active ingredient.

However, among these mixtures, the mixture of a nitro compound and an organic phosphorus compound represented by the general formula (I) is
There is no problem with other mixtures, but when the two are mixed together to form a formulation, the active ingredients act together and mutually promote decomposition, resulting in an extremely large degree of decomposition compared to the case of a single formulation of each. Therefore, long-term storage is virtually impossible.
The present applicant has clarified this problem, and it is desired to solve the problem of stabilization.

The present invention relates to a mixture containing a nitro compound represented by the general formula (I) and an organic phosphorus compound as active ingredients, in which the silanol groups of hydrous amorphous silica are partially silylated by a wet synthesis method, or Stabilization characterized by using etherified silica by firing, anhydrous amorphous silica produced by dry synthesis, or partially silylated silica (hereinafter collectively referred to simply as amorphous silica) The present invention provides an agrochemical composition. In addition, the above composition may contain polyethylene glycol chains, polypropylene glycol chains, or ethylene glycol, propylene glycol,
The present invention also provides a stabilized agrochemical composition characterized in that a compound containing a copolymer chain is added alone or in combination.

Furthermore, the present invention provides an agrochemical composition stabilized by using the above amorphous silica in a mixture containing a nitro compound represented by the general formula (I) and an organic phosphorus compound as active ingredients. A manufacturing method is provided. The present invention also provides a method for producing an agrochemical composition stabilized by adding a compound containing a polyethylene glycol chain, a polypropylene glycol chain, or an ethylene glycol/propylene glycol/copolymer chain to the above composition alone or in combination. This is what we provide.

Finally, it has been found that the stabilized agrochemical compositions according to the invention can be used for various purposes in agriculture and horticulture.

Surprisingly, the present inventors have found that the present invention has been formulated using the above amorphous silica in a mixture containing a nitro compound represented by general formula (I) and an organic phosphorus compound as active ingredients. It was discovered that the agrochemical composition according to the present invention stabilizes the active ingredients of the agrochemical mixture and does not have any adverse effect on the physical properties, and the present invention has been developed.

Therefore, the stabilized agrochemical composition according to the present invention provides an excellent technology in the field of agrochemical production, and also provides extremely outstanding technological progress in terms of industrial utility.

Examples of the nitro compound represented by general formula (I) used in the stabilized agricultural chemical composition according to the present invention include the following compounds.

1-(2-chloro-5-pyridylmethylamino) -methylthio 2-nitroethylene, 1-(2-chloro-5
-pyridylmethylamino)-1-methylamino-2-nitroethylene, 1-(2-chloro-5-pyridylmethyl)-3nitro-2-methylisothiourea, 3-(2-chloro-5-pyridylmethyl) -1 methyl'
-2-nitroguanidine, 1-(2-chloro-5-pyridylmethylaξ))-■-
Dimethylamino-2-nitroethylene, 1- (N-(
2-chloro-5-pyridylmethyl)-N-methylamino]-1-methylamino-2-nitroethylene, 1-(N-(2-chloro-5-pyridylmethyl)-N
-Methylaminoco-1-dimethylamino-2nitroethylene, 3-(2-chloro-5-pyridylmethyl)-1゜1-dimethyl-2-nitroguanidine, -(2-chloro-5
-Biridylmethyl(alpha))-1-ethylamino-2-nitroethylene, l-amino-1-(N-(2-chloro-
5-pyridylmethyl)-N-methylamino)-2-nitroethylene, 3-(2-chloro-5-pyridylmethyl)-1°3-dimethyl-2-nitroguanidine, and 3-(2-chloro- 5-pyridylmethyl)-1゜1.3~trimethyl-2
- Nitroguanidine.

The organophosphorus compound, which is one component of the stabilized agrochemical composition according to the present invention, means an active compound that can be used in the field of plant protection.

These are preferably insecticides, fungicides and the like.

Examples of active compounds of this type include the following: However, it is not limited only to these.

O~ethyl S,S-diphenyl phosphorodithioate (edifenphos), S-benzyl 0.0-di-isopropyl phosphorothioate (IBP), ○,○-dimethyl 0-4-methylthio-m-tolyl phosphorothioate (fenthion)
), 0.0-dimethyl 0-4-nitro m-tolyl phosphorothioate (fenitroth
ion), 0.0-dimethyl ○-3,5,6-)dichloro-2-
Pyridyl phosphorothioate (chlorpyrifos-methyl), S
-1,2-bis(ethoxycarbonyl)ethyl 01O-
Dimethyl phosphorodithioate (mala)
thlon).

S-α-ethoxycarbonylbenzyl o.

-dimethyl phosphorodithioate (fenthoate)
phenthoate).

dimethyl 2.2.2-) dichloro-1-hydroxyethyl phosphonate (trichloro-1-hydroxyethyl phosphonate)
rphon).

0-2,4-dichlorophenyl 0-ethyl S-propyl phosphorodithioate (prothiophos pro
thiofos), 〇-ethyl 0-4-methylthiophenyl S-brovyl phosphorodithioate (sulprofos 5ulp
rofos), 5-2-ethylsulfinyl-
1-Methyl ethyl 0,0-dimethyl phosphorothioate (oxydeprofos)
, 0.0-dimethyl 5-2-ethylthioethyl phosphorodithioate (dfsulfoton)
2.2-dichlorovinyldimethylphosphate (dichlorvos), (Z)-2-chloro-1-(2,4,5-trichlorophenyl)vinyl
Dimethyl phosphate (tetrachlorvin phosphate)
trachlorvinphos), 0.0-diethyl ○-2-iso-propyl-6-methylpyrimidin-4-yl phosphorothioate (diazinon di
azinon), 2,3-dihydro-3-oxo-2-
Phenyl-6-pyridazinyl diethyl phosphorothionate (pyridaphention)
hion), 〇-ethyl 0 2-iso-propoxycarbonylphenyl-isopropylphosphoroamidothioate (isofenphos)
.

Stabilizers for the agrochemical composition according to the present invention include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ether, polyoxyethylene/polyoxypropylene block polymer polyethylene Examples include glycol and polypropylene glycol.

The compound containing a polyethylene glycol chain, a polypropylene glycol chain, or a compound containing an ethylene glycol/propylene glycol/copolymer chain used in the present invention stabilizes the active acid component of the pesticide mixture of the present invention and causes no physical effects when formulated. Effective without affecting sexuality.

Therefore, the mixed active ingredients include polyethylene glycol chains,
A compound containing a polypropylene glycol chain, or a compound containing an ethylene glycol/propylene glycol/copolymer chain is added alone or in combination, and a solid diluent is prepared by a method commonly used in the drug manufacturing field. or a carrier, and in some cases a surfactant, and can be manufactured into various formulations.

Solid diluents include vegetable powders: mineral powders: clay minerals (clay) [for example, kaolinite group, montmorillonite group, attapulgite group, etc.], talc (talc)
, pyrophyllite, mica, calcite, pumice (
Vermiculite), dolomite, apatite, diatoms, synthetic inorganic materials (for example, synthetic alumina, etc.), di-synthetic resins (for example, phenolic resin, urea resin, vinyl chloride, etc.), and the like.

Examples of surfactants include anionic surfactants: alkyl sulfate esters [e.g., sodium lauryl sulfate, etc.], aryl sulfonic acids [e.g., alkylaryl sulfonate, sodium alkylnaphthalene sulfonate, etc.], polycarbonate, etc. Acid salts [e.g., Na salt of copolymer of maleic acid and olefin, etc.], nonionic surfactants: polyhydric alcohol esters [e.g., glycerin fatty acid esters, sorbitan fatty acid esters, etc.], etc. be able to.

Sticking agents can also be used in the formulation and can include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Coloring agents may also be used, including inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also iron Mention may be made of such trace elements as their salts of , manganese, boron, copper, cobalt, molybdenum, zinc.

As mentioned above, the stabilized agrochemical composition according to the present invention can be made into conventional formulations such as powders, wettable powders, and granules.

The formulations may generally contain from 0.05 to 95% by weight, preferably from 0.1 to 80% by weight of said active ingredient.

The amount of the compound containing polyethylene glycol chain, polypropylene glycol chain, or compound containing ethylene glycol/propylene glycol/copolymer chain used in the stabilized agricultural chemical composition according to the present invention is as follows:
Usually 0.1 to 30% by weight in the preparation, preferably 0.5 to 30% by weight
It is 15% by weight.

More specifically, it is 0.1 to 20% by weight for powders, preferably 0.5 to 10% by weight, and 0.1% for wettable powders.
-30% by weight, preferably 1-15% by weight, and in granules, 0.1-30% by weight, preferably 0.5-15% by weight.

The agrochemically active compound of the present invention may be used in combination with other known active compounds such as fungicides (fungicides, bactericides), insecticides, acaricides, herbicides, bird repellents, growth regulators, fertilizers and / Or a soil conditioner may also be present. Here, examples of the insecticides/agents include carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced from microorganisms.

Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto.

As the active ingredient used in the examples, 1-(2-
Chloro-5-pyridylmethylac))-1-methylamino-2-nitroethylene (compound (A)) 0-ethyl S,S-diphenyl phosphorodithioate (-ship name: nidifenphos) as an organophosphorus compound , 0, O-dimethyl 0-4-methylthio-mtolylphosphorothioate (-Ship name: Fenthion).

Example 1-a (powder) Compound (A) 1.5 parts by weight Nidifenphos 2.5 parts by weight Aerosil (dry synthetic silica) 4.5 parts by weight Clay
91.5 parts by weight Example 1-b (powder) Compound (A) 1.5 parts by weight Nidifenphos 2.5 parts by weight Aerosil (dry synthetic silica) 4.5 parts by weight Polyoxyethylene nonylphenyl ether clay Comparative Example 1 ( Powder) Compound (A) Nidifenphos hydrous amorphous silica clay Example 2-a (powder) Compound (A) Fenthion Aerosil (dry synthetic silica) Clay Example 2-b (powder) Compound (A) Fenthion Aerosil (dry synthetic silica) Polyoxyethylene nonylphenyl ether clay 2.5 parts by weight 89.0 parts by weight 1.5 parts by weight 2.5 parts by weight 4.5 parts by weight 91.5 parts by weight 1.5 parts by weight 2.5 parts by weight 4.5 parts by weight Parts by weight 91.5 parts by weight 1.5 parts by weight 2.5 parts by weight 4.5 parts by weight 2.5 parts by weight 89.0 parts by weight Comparative Example 2 (powder) Compound (A) 1.5 parts by weight Fenthion 2. 5 parts by weight hydrated amorphous silica 4.5 parts by weight...
91.5 parts by weight of each were ground and mixed to form a powder.

Experimental example 1. Stabilization test of active ingredients (powders) Each of the prepared powders was placed in a glass bottle and stored in a dark place at 40°C for 60 days, and the decomposition rate was investigated. The results are shown in Table 1.

Example 3-a (hydrating agent) Compound (A) Nidifenphos Sodium lignin sulfonate Aerosil (dry synthetic silica) clay Example 3-b (hydrating agent) Compound (A) Nidifenphos Aerosil (dry synthetic silica) polyoxyethylene nonylphenyl ether Sodium lignin sulfonate clay Comparative example 3 (hydrating powder) Compound (A) Nidifenphos Sodium lignin sulfonate Hydrous amorphous silica clay 15.0 parts by weight 10.0 parts by weight 5.0 parts by weight 17.0 parts by weight 53.0 parts by weight 15.0 parts by weight 10.0 parts by weight 17.0 parts by weight 5.0 parts by weight 5.0 parts by weight 48.0 parts by weight 15.0 parts by weight 10.0 parts by weight 5.0 parts by weight 17.0 parts by weight 53.0 parts by weight Example 4-a (hydrating agent) compound (,A) Fenthion Sodium lignin sulfonate Aerosil (dry synthetic silica) clay Example 4-b (hydrating agent) Compound (A) Fenthion Aerosil (dry synthetic silica) polyoxyethylene nonylphenyl ether Sodium lignin sulfonate clay Comparative example 4 (hydrating agent) Compound (A) Fenthion Sodium lignin sulfonate Hydrous amorphous silica clay 15.0 parts by weight 10.0 parts by weight 5.0 parts by weight 17.0 parts by weight 53.0 parts by weight 15.0 parts by weight 10.0 parts by weight 17.0 parts by weight 5.0 parts by weight 5.0 parts by weight 48.0 parts by weight 15.0 parts by weight 10.0 parts by weight 5.0 parts by weight 17.0 parts by weight 53.0 parts by weight Grind and mix each to make a wettable powder.

Experimental example 2. Stabilization test of active ingredients (hydrating powders) Each of the prepared hydrating powders was placed in a glass bottle and stored in a dark place at 40°C for 60 days, and its decomposition rate was investigated.

The results are shown in Table 2.

Example 5-a (granules) Compound (A) Fenthion Aerosil (dry synthetic silica) bentonite clay Example 5-b (granules) Compound (A) Fenthion Aerosil (dry synthetic silica) polyoxyethylene nonylphenyl ether bentonite clay Comparative example 5 (granules) Compound (A) Fenthion Hydrous amorphous silica bentonite clay 3.0 parts by weight 3.0 parts by weight 4.5 parts by weight 35.0 parts by weight 54.5 parts by weight 3.0 parts by weight 3.0 parts by weight 4.5 parts by weight 2.5 parts by weight 35.0 parts by weight 52.0 parts by weight 3.0 parts by weight 3.0 parts by weight 4.5 parts by weight 35.0 parts by weight 54.5 parts by weight They are mixed and kneaded, and made into granules by extrusion granulation.

Experimental example 3. Stabilization test of active ingredients (granules) Each prepared granule was placed in a glass bottle and stored in a dark place at 40°C for 60 days, and its decomposition rate was investigated.

The results are shown in Table 3.

The following compounds included in general formula (I) also include nidifenphos, fenthion, chlorpyrifos-methyl,
The mixed composition according to the invention with prothiofos, sulprofos, disulfoton, tetrachlorvinphos, pyridafenthion made the respective active ingredients stable.

1-(2-chloro-5-pyridylmethylamino)-1-
Dimethylamino-2-nitroethylene, 1- (N-(
2-chloro-5-pyridylmethyl)-N-methylaminoco-1-dimethylagono, 2-nitroethylene, 3-(2-chloro-5-pyridylmethyl)-1゜1-dimethyl-2-nitroguanidine, 3- (2-chloro-5
-pyridylmethyl)-l.

3-Dimethyl-2-nitroguanidine.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, R^1 represents a hydrogen atom or a C_1_-_4 alkyl group, and R^2 represents -S-R^ 3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R^3 is C_1_-_4
represents an alkyl group, R^4 and R^5 each represent a hydrogen atom or a C_1_-_4 alkyl group, and Y is CH
or a mixture containing a nitro compound and an organic phosphorus compound represented by N as active ingredients, which have a reduced number of surface silanol groups by silylating hydrous amorphous silica by wet synthesis or etherifying it by calcination; Alternatively, a stabilized agricultural chemical composition characterized by using anhydrous amorphous silica produced by a dry synthesis method, or a silylated version thereof. 2. In a mixture containing a nitro compound and an organic phosphorous compound represented by the general formula (I) as active ingredients, the surface silanol groups are reduced by silylating the hydrated amorphous silica by wet synthesis or by etherifying it by calcination. or anhydrous amorphous silica by dry synthesis method,
Or, in addition to using a silylated version of this, polyethylene glycol chains, polypropylene glycol chains,
Alternatively, a stabilized agrochemical composition characterized in that a compound containing ethylene glycol, propylene glycol, or a copolymer chain is added alone or in combination.