JPH07116001B2 - Pesticide composition in suspension - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pesticidal composition in suspension which contains a pesticidal active ingredient which is poorly soluble in water as an active ingredient, has a low viscosity and retains stable properties over a long period of time. .

[Conventional technology]

Conventionally, agricultural chemical raw materials which are poorly soluble in water or courageous solvents have been difficult to make into liquids or emulsions, and thus have been used in the form of powders, wettable powders and the like. Among them, powders have many advantages such as being able to spray the formulation as it is, and being easy to formulate, but have drawbacks such as scattering to the surroundings at the time of spraying. In addition, since the wettable powder is diluted with water and then sprayed, there is an advantage that the pesticide active ingredient uniformly and efficiently adheres to the crop using water as a medium, but it is powdered when the wettable powder is diluted with water. However, it is not preferable in terms of user safety and health.

On the other hand, in recent years, many suspension-type agrochemical compositions in which finely divided agrochemical active ingredients are suspended in water or the like, that is, a liquid formulation form called a sol or flowable (hereinafter sometimes referred to as a sol formulation) are often used. It came to be used. The sol preparation is diluted with water like the wettable powder or is sprayed in the state of undiluted solution. Since this preparation is liquid, it does not cause powdering when diluted with water, and it is an excellent preparation form in that it is easier to measure than a wettable powder.

Conventionally, as a sol formulation, a formulation obtained by adding water, a solvent, a surfactant and a water-soluble polymer such as carboxymethylcellulose to a poorly water-soluble pesticide active ingredient and suspending it (Japanese Patent Publication No.
58-24401), a nonionic surfactant, a heteropolysaccharide gum and powdered silica and suspended in water (JP-A-49-133531), a nonionic surfactant and a heteropolysaccharide gum. And a suspension suspended in water (JP-A-52-128226), a suspension added with a surfactant and colloidal hydrous aluminum silicate (Japanese Patent Publication No.
54-11368) etc.

[Problems to be solved by the invention]

However, none of the sol preparations produced by these known techniques can satisfy various physical properties required for the sol preparation, and the storage stability of the preparation is improved, resulting in long-term suspension uniformity. A high viscosity is required in order to keep it for a long time. Therefore, it is not easy to fill the storage container, the remaining amount of the formulation in the container is large when the formulation is taken out from the container, and it is not easy to check the remaining amount of the drug solution in the container, and the weighing becomes inaccurate. Disturbance occurs in the undiluted solution spraying in the air. Further, if the viscosity is lowered to the extent that there is no problem in practical use, the storage stability will deteriorate, and the precipitated particles will eventually form a hard caking layer that cannot be redispersed.

The present invention has been made to solve the problems of these conventional techniques, and satisfies the physical properties required for a sol formulation,
It is an object of the present invention to provide a pesticidal suspension composition which is excellent in storage stability and can be adjusted to have a viscosity that causes no practical problems.

[Means for solving problems]

 The present invention is the following agricultural chemical composition in suspension.

(1) One or more poorly water-soluble pesticide active ingredients,
A pesticide composition in suspension, comprising a bentonite mineral substance and colloidal silicon oxide.

(2) One or more poorly water-soluble pesticide active ingredients,
A suspended pesticide composition comprising a bentonite mineral substance, colloidal silicon oxide, and a hydrocarbon solvent containing 90% by weight or more of a methane series hydrocarbon having 9 to 17 carbon atoms.

The physical properties required for sol preparations are as follows.

Excellent storage stability. Therefore, even if it is stored for a long period of time, the suspended particles do not settle to form a separation layer from the solvent, and the precipitated particles do not form a hard caking layer that cannot be redispersed.

The formulation has low viscosity. This makes it easy to fill the storage container with the formulation, and when the formulation is taken out of the container, the remaining amount in the container is small and can be used without waste.
In addition, accurate metering is possible, the remaining amount in the container can be easily checked, it has excellent dispersibility in water, and the nozzle part has good passage properties when spraying the undiluted solution in the air, and a certain amount of drug can be sprayed. To be. Such a viscosity is 10
~ 300 cPs, preferably 10-200 cPs.

When colloidal silicon oxide is used alone in a sol formulation, a formulation with low viscosity and good storage stability cannot be obtained, and when a bentonite mineral substance is used alone, the viscosity does not change over time. However, in the present invention, by using them together,
Alternatively, by adding a hydrocarbon solvent containing 90% by weight or more of a methane-series hydrocarbon having 9 to 17 carbon atoms, good physical properties such as excellent storage stability and low viscosity can be obtained.

The pesticidal active ingredient applicable to the present invention is not particularly limited as long as it is poorly soluble in water, and the compounding amount is usually 10 to 60% by weight based on the pesticidal composition in suspension. Examples of such agrochemical active ingredients include 5-methyl-1,2,4-triazolo (3,4-b)
Benzothiazole (tricyclazole), 2-methyl-
3'-isopropoxybenzanilide (mepronil),
4,5,6,7-Tetrachloroisophthalonitrile (TPN), Manganese ethylene bis (dithiocarbamate) (manneb), dimethyl 4,4'-O-phenylene bis (3-thioallophanate) (thiophanate methyl), 8 -Fungicides such as copper oxyquinoline, cupric hydroxide, and sulfur; dimethyl-2-chloro-1- (2,4-dichlorophenyl) vinyl phosphate (dimethylvinphos), 1-naphthylmethylcarbamate (NAC) , M-tolylmethylcarbamate (MTMC), 3,4-xylylmethylcarbamate (MPMC), O, S-dimethyl = N-acetylphosphoramidothioate (acephate), 2-sec-butyl-4,6- Dinitrophenyl-3-methylcrotonate (vinapacryl), tricyclohexyltin hydroxide (prectran), S-4-phenoxyb Chill = N,
N-dimethyl thiocarbamate (phenothiocarb),
2-sec-Butylphenyl-N-methylcarbamate (B
PMC), 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether (ethofenprox) and other insecticides or acaricides; 2-chloro-4,6-bis (ethylamino)- 1,3,5-triazine (CAT), 2-chloro-4-ethylamino-6-
Isopropylamino-1,3,5-triazine (gezaprim), N- (1-ethylpropyl) 3,4-dimethyl-2,6
Examples include, but are not limited to, herbicides such as dinitroaniline (Stomp). These pesticidal active ingredients may be used alone or in combination of two or more kinds, and in this case, a mixture agent exceeding the kinds of fungicides, insecticides and herbicides is also possible.

The bentonite mineral material used in the present invention is a group of typical minerals constituting clay, and means montmorillonite group minerals and those containing them as a main component, and the structure thereof is a phyllosilicate mineral having a three-layer structure. In some cases, some of them are replaced with other metals such as magnesium, iron and sodium, and may be treated. Particularly in the present invention, high-purity sodium montmorillonite containing a large amount of sodium is preferable.

The colloidal silicon oxide used in the present invention is represented by SiO ₂ .nH ₂ O as a general formula, and is a high-purity silicon oxide that is usually obtained by rapidly decomposing a vapor-phase or liquid-phase silicic acid source. The particle diameter is 3 to 100 mμ, which are extremely fine and amorphous particles.

The amount of bentonite ore and colloidal silicon oxide used in the present invention is usually different with respect to the agrochemical composition.
0.1 to 5% by weight, the viscosity of the formulation is 10 to 300 cPs,
Desirably, the respective blending amounts are adjusted so as to be 10 to 200 cPs.

The pesticidal composition in the form of a suspension according to the first aspect of the present invention comprises the pesticidal active ingredient, bentonite mineral and colloidal silicon oxide suspended in an aqueous solvent. Here, the aqueous solvent is water or a mixture of water and another solvent. Water is usually 20 to 60% by weight, preferably 30 to
40% by weight is blended.

The suspension-type agricultural chemical composition of the second invention of the present invention is obtained by further mixing the above composition with a hydrocarbon solvent having 90% by weight or more of a methane series hydrocarbon having 9 to 17 carbon atoms and suspending it in an aqueous solvent. By incorporating such a hydrocarbon solvent, dispersibility and storage stability are further improved.

Examples of the hydrocarbon solvent having 90% by weight or more of methane series hydrocarbons having 9 to 17 carbon atoms include petroleum hydrocarbon solvents,
In particular, the following compositions and properties are preferable.

(Composition) Paraffin hydrocarbon 99 (% by weight) Naphthene hydrocarbon 0.5 Aromatic hydrocarbon 0.5 (Paraffin hydrocarbon) C _{9 to} C ₁₇ (95% distillation temperature of the above composition) 270 ° C Hydrocarbon solvent The compounding amount is usually 1 to 25 with respect to the agrochemical composition.
It is about 5% by weight, preferably about 5 to 20% by weight.

In the suspension agricultural chemical composition of the present invention, in order to disperse the agricultural chemical active ingredient in water, as the surfactant, sodium lignin sulfonate, sodium alkylnaphthalene sulfonate, polyoxyethylene styrenated phenyl ether sulfate, malein. One or more kinds of anionic surfactants such as acid styrene copolymers and nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene fatty acid ester, sorbitan oleic acid ester may be used. The blending amount is usually 1 to 10% by weight of the pesticide composition.

In addition, in the pesticidal composition of the present invention, a hydrophilic organic solvent such as propylene glycol, ethylene glycol and glycerin, and an antifreezing agent such as ammonium sulfate and ammonium chloride are usually used in an amount of 5 to 15 relative to the pesticidal composition.
%, A defoaming agent such as silicone is usually added to the agrochemical composition in an amount of 100 to 1000 ppm, and a coloring agent, a decomposition inhibitor and the like can be added in a necessary amount.

The suspension-type agricultural chemical composition of the present invention has a formulation viscosity of 10 to 30 at 20 ° C. in order to improve storage stability over a long period of time.
It is set to 0 cPs, preferably 10 to 200 cPs. Formulation viscosity here is B type rotational viscometer (BL type, manufactured by Tokyo Keiki Co., Ltd.)
Is the value measured using, and the measurement conditions are rotor No. 2, rotor speed 30 rpm, and formulation temperature 20 ° C. to measure viscosity.

Next, an example of a method for producing the suspension composition of the present invention will be shown.

First, a predetermined amount of bentonite mineral substance and colloidal silicon oxide are added to a predetermined amount of water and dispersed by a stirrer. Next, a surfactant and an agrochemical raw material which has been roughly crushed in advance are added, and if necessary, an antifreezing agent, an antifoaming agent and the like are further added, and mixed and dispersed by a high speed stirrer. Next, this mixture is wet-milled, for example, sand grinder SL type (Igarashi Kikai Co., Ltd., trade name), Attritor MA-1S type (Mitsui Miike Seisakusho, trade name), die KDL type mill. (WAB Co., trade name) etc. are used to obtain the desired preparation by wet pulverization so that most of the pesticide raw material has an average particle size of 4 μm or less, preferably 0.1 to 2 μm.

The order of adding the raw materials such as the drug substance and the surfactant may be appropriately changed depending on the convenience of the process such as foaming.
The bentonite mineral and colloidal silicon oxide are preferably sufficiently dispersed in water beforehand.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. All "parts" in the examples are "parts by weight".

Example 1 0.4 parts of bentonite minerals and 0.5 parts of colloidal silicon oxide were mixed and dispersed in 48.1 parts of water, and coarsely pulverized into 40 parts of 2-methyl-3′-isopropoxybenzanilide 40 parts and sodium β-naphthalenesulfonate formalin. Condensate 3.5
Parts, sodium alkylbenzene sulfonate 0.5 parts, ethylene glycol 7 parts, and silicone AF
-118N (trade name, manufactured by Asahi Chemical Industry Co., Ltd.) 20
After adding 0 ppm and mixing for 30 minutes with a high speed stirrer, the mixture was ground with a wet grinder to obtain a homogeneous sol preparation.

Example 2 Bentonite mineral substance 0.2 parts and colloidal silicon oxide 0.5 part were mixed and dispersed in water 38.3 parts, and coarsely pulverized to this, 40 parts of 2-methyl-3′-isopropoxybenzanilide 40 parts of sodium β-naphthalenesulfonate formalin. Condensate 3.5
Parts, 0.5 parts of sodium alkylbenzene sulfonate, 7 parts of ethylene glycol, and 10 parts of petroleum-based hydrocarbon solvent (manufactured by Nippon Petrochemical Co., Ltd.) containing 96% by weight of methane hydrocarbon having 11 to 13 carbon atoms, and silicone. AF-118N
Was added to the preparation in an amount of 200 ppm, mixed with a high-speed stirrer for 30 minutes, and then ground with a wet grinder to obtain a homogeneous sol preparation.

Example 3 Bentonite mineral material 0.7 parts and colloidal silicon oxide 0.5 parts were mixed and dispersed in water 47.8 parts, and coarsely pulverized into 4,5,6,7.
-Add 40 parts of tetrachloroisophthalonitrile, 3 parts of polyoxyethylene styrenated phenyl ether sulfate and 8 parts of ethylene glycol, and add silicone AF-11.
8N was added to the formulation in an amount of 500 ppm, mixed with a high-speed stirrer for 30 minutes, and then pulverized with a wet pulverizer to obtain a homogeneous sol formulation.

Example 4 0.5 part of bentonite ore and 0.5 part of colloidal silicon oxide were mixed and dispersed in 38 parts of water, and coarsely pulverized into 4,5,6,7-.
Tetrachloroisophthalonitrile 40 parts, polyoxyethylene styrenated phenyl ether sulphate 3 parts, ethylene glycol 8 parts, carbon number 11-13 methane series hydrocarbons 96
While adding 10 parts of petroleum hydrocarbon solvent containing 10% by weight,
Silicone AF-118N was added to the preparation in an amount of 500 ppm, mixed with a high-speed stirrer for 30 minutes, and then ground with a wet grinder to obtain a homogeneous sol preparation.

Example 5 0.5 part of high-purity sodium montmorillonite and 0.6 part of colloidal silicon oxide were mixed and dispersed in 56.9 parts of water, and coarsely pulverized into dimethyl-2-chloro-1- (2,4-dichlorophenyl) vinyl phosphate. 30 parts, 2 parts of maleic acid styrene copolymer, 2 parts of polyoxyethylene nonylphenyl ether, and 8 parts of propylene glycol are added, 300 ppm of silicone AF-118N is added to the preparation, and the mixture is mixed for 30 minutes with a high-speed stirrer, then wet It was crushed with a crusher to obtain a homogeneous sol preparation.

Example 6 Bentonite mineral material (1.5 parts) and colloidal silicon oxide (1.5 parts) were mixed and dispersed in water (47 parts), and coarsely crushed 5-methyl-1,2,4-triazolo (3,4-b) benzothiazole 12
Parts, 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether, 10 parts, sodium ligninsulfonate 2 parts, polyoxyethylene nonylphenyl ether 1 part, ethylene glycol 10 parts, carbon number
Add 15 parts of petroleum hydrocarbon solvent containing 98% by weight of 13-14 hydrocarbons in methane series, add 200 ppm of silicone AF-118N to the formulation, mix for 30 minutes with a high-speed stirrer, then wet crusher Was pulverized to obtain a uniform sol preparation.

Reference Example 1 0.4 parts of bentonite minerals and 0.5 parts of colloidal silicon oxide in Example 1 were replaced with 0.2 parts of heteropolysaccharide rubber, and water was changed from 48.1 parts to 48.8 parts, and 2-methyl-3'-isopropoxybenzanilide was homogeneous. A sol formulation was obtained.

Reference Example 2 0.4 parts of bentonite ore and 0.5 parts of colloidal silicon oxide of Example 1 were replaced with 0.07 parts of heteropolysaccharide rubber, and water was changed from 48.1 parts to 48.93 parts.
A homogeneous sol formulation of methyl-3'-isopropoxybenzanilide was obtained.

Reference Example 3 0.4 parts of bentonite ore and 0.5 part of colloidal silicon oxide of Example 1 were replaced with 0.6 part of bentonite ore and water was changed from 48.1 to 48.4 parts 2-methyl-3 ′.
A homogeneous sol formulation of isopropoxybenzanilide was obtained.

Reference Example 4 0.4 part of the bentonite ore and 0.5 part of colloidal silicon oxide of Example 1 were replaced with 1.5 parts of colloidal silicon oxide, and water was changed from 48.1 parts to 47.5 parts by 2-methyl-.
A homogeneous sol formulation of 3'-isopropoxybenzanilide was obtained.

Reference Example 5 0.7 parts of bentonite minerals and 0.5 parts of colloidal silicon oxide in Example 3 were replaced with 0.9 parts of bentonite minerals, and water was changed from 47.8 parts to 48.1 parts to 4,5,6,7-tetrachloroisophthalonitrile. A homogeneous sol formulation of

Reference Example 6 The bentonite mineral material of Example 3 (0.7 parts) and colloidal silicon oxide (0.5 parts) were replaced with colloidal silicon oxide (1.4 parts), and water was changed from 47.8 parts to 47.6 parts of 4,5,6,7-tetrachloroisophthalo. A homogeneous sol formulation of nitrile was obtained.

Reference Example 7 0.5 part of high-purity sodium montmorillonite of Example 5,
Replace 0.6 parts of colloidal silicon oxide with 0.8 parts of bentonite mineral and add 56.9 parts to 57.2 parts of water as dimethyl-2-chloro-1- (2,4-dichlorophenyl).
A homogeneous sol formulation of vinyl phosphate was obtained.

Reference Example 8 0.5 part of high-purity sodium montmorillonite of Example 5,
0.6 parts of colloidal silicon oxide to 1.6 parts of colloidal silicon oxide
The amount of water was changed from 56.9 parts to 56.4 parts to obtain a homogeneous sol preparation of dimethyl-2-chloro-1- (2,4-dichlorophenyl) vinyl phosphate.

Reference Example 9 0.5 part of high-purity sodium montmorillonite of Example 5,
Replace 0.6 parts of colloidal silicon oxide with 0.07 parts of carboxymethyl cellulose and add 56.9 parts to 57.9 parts of water.
A homogeneous sol formulation of dimethyl-2-chloro-1- (2,4-dichlorophenyl) vinyl phosphate as 3 parts was obtained.

Reference Example 10 98% by weight of methane hydrocarbon having 13 to 14 carbon atoms of Example 6
Excluding 15 parts of petroleum hydrocarbon solvent containing 1.5 parts of bentonite ore and 1.5 parts of colloidal silicon oxide were replaced with 0.13 parts of heteropolysaccharide rubber, and water was changed from 47 parts to 64.87 parts of 5-methyl-1,2,4. − Triazolo (3,4
-B) A homogeneous mixed sol formulation of benzothiazole and 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether was obtained.

Next, test examples and test results conducted on the samples prepared in Examples 1 to 6 and Reference Examples 1 to 10 will be shown.

Test Example 1 Measurement of Storage Stability The sol preparation was put in a 500 ml glass bottle and stored in a thermostat at 40 ° C. for 3 months, and the separation and sedimentation property of the sol preparation was measured every month. The investigation was calculated by the ratio (%) of the height of the supernatant part to the height of the whole liquid. After the measurement was completed, the glass rod was gently put in and the presence or absence of the hard caking layer was confirmed.

Storage stability is better the smaller the proportion of the supernatant,
Further, the formation of the hard caking layer is unsuitable as a sol formulation.

Test Example 2 Viscosity Measurement After the sample used in Test Example 1 was inverted 30 times,
The viscosity was measured. In this case, the same operation was performed on the hard caking layer formed, that is, the hard caking layer was measured with a glass rod or the like without breaking or dispersing.

A B type rotational viscometer (BL type, manufactured by Tokyo Keiki Co., Ltd.) was used for the measurement, and the measurement conditions were rotor No. 2, rotor rotation speed 30 rpm, and formulation temperature 20 ° C.

Test Example 3 Dispersibility in Water 250 ml of water was placed in a graduated cylinder of 250 ml volume, and the sol preparation was added dropwise with a pipette to observe the dispersed state, and the following four-stage evaluation was performed.

◎ …… The dispersion state is extremely good. The drug disperses so as to diffuse in water.

○: The dispersed state is good. The drug drops in the form of droplets while partially diffusing in the water, but is dispersed by the time it reaches the bottom.

△ …… The dispersion is a little bad. Most of the drug drops to the bottom in the form of droplets, but it is dispersed by shaking the measuring cylinder.

×: The dispersion is poor. The drug drops to the bottom in the form of droplets,
Shaking the graduated cylinder does not disperse easily.

The better the dispersed state, the more preferable.

Test Example 4 Measurement of remaining amount in storage container 500 ml of sol formulation was placed in a 500 ml polyethylene container with a diameter of 6.5 cm and a height of 15 cm for general liquid pesticide storage, and stored in a 40 ° C incubator for 3 months. The storage container remaining amount was measured for each. The method is to repeat the inversion of the polyethylene container 30 times, then invert the container and take out the sol formulation, measure the weight when the interval of droplets falling from the mouth of the container is 10 seconds or more, and measure the polyethylene container. The remaining weight of the storage container was subtracted from the weight of the storage container.

In this case, the same operation was carried out for the hard caking layer formed and the gelled one, and the weight of the hard caking layer portion and the gelled portion were taken as the remaining amount of the storage container.

The smaller the remaining amount in the storage container, the more preferable.

The above test results are shown in Table 1.

From the results shown in Table 1, it can be seen that the examples have better dispersibility and storage stability than the reference examples, and have low viscosity and good handleability. In particular, as is clear by comparing Examples 3 and 4, it can be seen that even more excellent effects can be obtained by adding a hydrocarbon solvent.

[Effects of the Invention] As described above, according to the pesticide composition in suspension of the present invention, the following effects can be obtained.

Even if it is stored for a long period of time, it hardly causes sedimentation and separation, and does not form an undispersible hard caking layer.

Low viscosity. Therefore, in the manufacturing scene, a) productivity is improved by improving wet grinding efficiency.

b) It is easy to fill and package the storage container.

In use, c) Stable pest control effect can be obtained by accurate measurement.

d) It is easy to check the remaining amount of the drug solution in the container.

e) Good dispersibility in water and easy preparation of spray liquid.

f) In spraying the undiluted solution in the air, there is no clogging in the spraying device and stable drug spraying is possible.

 It has stable viscous properties over a long period of time.

A mixture of a hydrocarbon solvent containing 90% by weight or more of methane-series hydrocarbons having 9 to 17 carbon atoms provides a further excellent effect.

Claims (4)

[Claims] 1. A suspension-type agricultural chemical composition comprising one or more kinds of sparingly water-soluble agricultural chemical active ingredients, bentonite mineral substances and colloidal silicon oxide. 2. The pesticidal composition in suspension according to claim 1, wherein the viscosity of the preparation is 10 to 300 cPs. 3. One or more kinds of sparingly water-soluble pesticidal active ingredients, bentonite minerals, colloidal silicon oxide, and methane series hydrocarbons having 9 to 17 carbon atoms containing 90% by weight or more of a hydrocarbon solvent. A pesticidal composition in the form of a suspension. 4. The suspended pesticide composition according to claim 3, wherein the formulation has a viscosity of 10 to 300 cPs.