JPH069302A - Water-suspended agricultural chemical formulation - Google Patents

Abstract

PURPOSE:To obtain a water-suspended agricultural chemical formation, having excellent physical properties of formulation after long-term preservation, specific redispersibility of precipitate, comprising basic copper chloride as an active ingredient of agricultural chemical. CONSTITUTION:A polycarboxylic acid-based surfactant is dissolved in water and blended with at least one of calcium carbonate, basic magnesium carbonate and magnesium hydroxide and basic copper chloride as an active ingredient of agricultural chemical. A copolymer of isobutylene or diisobutylene and maleic anhydride, a copolymer of maleic anhydride and styrene, polyacrylic acid, etc., may be cited as the polycarboxylic acid-based surfactant and the amount of the surfactant blended is >=0.1wt.%, preferably 0.2-5wt.% in the formulation. The amount of the calcium carbonate is preferably 0.05-2 pts.wt. based on 1 pt.wt. basic copper chloride.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-suspended pesticide formulation, and more particularly to a water-suspended pesticide formulation having excellent physical properties of the formulation after long-term storage, particularly redispersibility of sediment.

[0002]

2. Description of the Related Art Several pesticide formulations in water are known in which pesticide active ingredients are suspended and dispersed in water.

For example, a method of wet pulverizing a hydrophobic solid agricultural chemical in water or a hydrophilic medium and suspending it in the medium as hydrophilic ultrafine particles (Japanese Patent Publication No. 46-20519), a solid hardly soluble in water. A pesticide or a system that simultaneously contains a solid pesticide that is poorly soluble in water and a water-soluble solid pesticide, a surfactant, a water-soluble polymer, and water, and has a formulation viscosity of 200 to 50 at 20 ° C.
Suspended pesticide with 0 cp (Japanese Patent Publication No. 58-2440), pesticide raw material insoluble or hardly soluble in water or organic solvent,
Suspended pesticide consisting of surfactant, xanthan gum and water (JP-A-57-58601), a solvent mainly composed of water and an organic solvent mixed therein, and water-insoluble at 50% by weight or less at room temperature Aqueous suspension type agricultural chemical preparations in which an agricultural chemical raw material, an aromatic sulfonic acid formalin condensate salt, an emulsifier and a heteropolysaccharide are suspended (JP-A-58-12470).
No. 2), 50 particles having a particle size of 0.5 μ or less
A biocide composition in the form of an aqueous suspension containing as a particle growth inhibitor a polymerized product of a monomer comprising a micronized biocide, an unsaturated carboxylic acid and its derivative in an amount of at least wt% (JP-A-62-62).
-126101).

On the other hand, basic copper chloride used as an agricultural chemical active ingredient in the present invention is a plague of potato, tomato and eggplant, a bacterial spot of cucumber, anthracnose, onion, Chinese cabbage, soft rot of radish, and citrus fruit. It has long been used as a fungicide against various diseases such as illness, scab, black spot, pear black spot, and late rot of grape. Also known is a method of adding magnesium hydroxide or magnesium carbonate as a chemical damage reducing agent for crops of an agricultural chemical formulation containing copper (Japanese Patent Laid-Open No. 56-79601). However, a water-suspended agricultural chemical preparation containing basic copper chloride as an agricultural chemical active ingredient is not known.

[0005]

Since a water suspension pesticide uses water as a medium, it is superior in safety and economy to emulsions using an organic solvent. However,
When basic copper chloride as a pesticide active ingredient is formulated into a water-suspended pesticide, since the active ingredient has a large specific gravity, the active ingredient precipitates during storage, and since the precipitate forms a hard caking layer, There are problems such as not easily re-dispersing. Therefore, as a method of suppressing the precipitation of the active ingredient, a method of increasing the viscosity of the preparation by adding a water-soluble polymer such as xanthan gum as described above is known. However, even in this case, for example, at 25 ° C., 3000 mPa.s. The precipitation of the active ingredient cannot be completely suppressed unless the viscosity is higher than s. Moreover, 3000 mPa. When the viscosity is s or more, it is not practical because the handling becomes extremely poor, such as the difficulty of discharging the medicine from the container during use.

[0006]

[Constitution of the invention]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, by dissolving the polycarboxylic acid-based surfactant in water and uniformly mixing at least one or more of calcium carbonate, basic magnesium carbonate, magnesium hydroxide and basic copper chloride as an agrochemical active ingredient, the agrochemical efficacy is improved. It was found that even if basic copper chloride as a component settles during storage, it can be easily redispersed by simply shaking the container by hand.

Therefore, the gist of the present invention is to dissolve a polycarboxylic acid type surfactant in water and to add at least one or more of calcium carbonate, basic magnesium carbonate and magnesium hydroxide and basic chloride as an agricultural chemical active ingredient. It is a pesticide formulation in water suspension prepared by mixing copper.

The amount of basic copper chloride, which is the active ingredient of the agricultural chemical of the present invention, added to the preparation is not particularly limited,
As basic copper chloride, 5 from the viewpoint of ease of use and economy.
-60 parts is preferable.

The polycarboxylic acid type surfactants used in the present invention include those shown in the following (1) to (5), and their molecular weights are usually 3,000 to 60,000.

(1) Copolymer of isobutylene or diisobutylene and maleic anhydride (2) Copolymer of maleic anhydride and styrene (3) Acrylic acid polymer (4) Copolymer of maleic anhydride and acrylic acid Polymers and salts of these with alkali metals, amines and ammonia (5) Copolymers of itaconic acid and acrylic acid and salts of these with alkali metals, amines and ammonia

There is no problem even if one or more of these polycarboxylic acid type surfactants are used in combination. These surfactants may be synthesized and used, but commercially available products may be used.

The amount of the polycarboxylic acid type surfactant used in the present invention may be appropriately changed depending on the content of the agrochemical active ingredient, and usually 0.1% by weight or more is used in the preparation, but preferably 0. 2 to 5% by weight.

There is no problem even if a commonly used surfactant is used in combination with the pesticide formulation in water suspension of the present invention. Examples of the surfactant include anionic surfactants and nonionic surfactants. Examples of the anionic surfactant include lignin sulfonate, alkylallyl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl allyl phosphate, polyoxyethylene alkyl allyl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene. There are styryl phenyl ether sulfates and the like, and as the nonionic surfactant, for example, polyoxyethylene alkyl allyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkylate, Examples include, but are not limited to, polyoxyethylene styryl phenyl ether polymers, polyoxyalkylene glycols, etc. Instead of, there is no problem even if a combination of more of these alone or two.

The amount of calcium carbonate, basic magnesium carbonate or magnesium hydroxide added to the pesticide formulation in the form of a water suspension of the present invention can be appropriately changed depending on the content of basic copper chloride, but preferably basic copper chloride. It is in the range of 0.05 to 2.0 parts by weight per 1 part by weight.

As an auxiliary agent for obtaining the pesticidal formulation of the present invention in the form of a water suspension, a viscosity modifier, an antiseptic / antifungal agent, an antifreezing agent, an antifoaming agent, a stabilizer of an agrochemical active ingredient and the like can be used.

Examples of the viscosity modifier include xanthan gum, guar gum, tragacanth gum, gum arabic, casein, dextrin, carboxymethyl cellulose, sodium carboxymethyl starch salt, sodium alginate, hydroxyethyl cellulose, carboxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, Polyvinyl alcohol, polyacrylic acid and its derivatives, colloidal hydrous magnesium silicate, colloidal hydrous aluminum silicate, magnesium, etc., are not limited to these, and these may be used alone or in combination of two or more. It can also be used.

Examples of the antiseptic / antifungal agent include p-chloro-
m-xylenol, p-chloro-m-cresol, p-
There are butyl oxybenzoate, sorbitan acid, potassium sorbate and the like, and these can be used alone or in combination of two or more kinds.

Examples of the antifreezing agent include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and methanol.
There is no problem even if one or more of these are used in combination.

As the defoaming agent, generally used ones such as silicone type, fatty acid type and mineral oil type are used.
It is not limited to these.

As a stabilizer for the active ingredient of agricultural chemicals, an antioxidant, an anti-UV agent or the like may be used in combination.

[0021]

In the present invention, basic copper chloride is an active ingredient of agricultural chemicals, and the polycarboxylic acid type surfactant has a function of dispersing basic copper chloride and calcium carbonate, basic magnesium carbonate, magnesium hydroxide in water, Along with calcium carbonate, basic magnesium carbonate and magnesium hydroxide, it has a function of improving the physical properties of the preparation after storage for a long time, especially the re-separability of the precipitate, and water is the dispersion medium.

[0022]

【Example】

Formulation Method In order to prepare the water-suspended pesticide formulation of the present invention, any special method or apparatus is not required, and a usual method for producing a water-suspended formulation may be used. For example, basic copper chloride and calcium carbonate, one kind of basic magnesium carbonate or magnesium hydroxide is added to water in which a polycarboxylic acid type surfactant is dissolved, and the mixture is mixed with a homomixer (Nippon Tokushu Kika Kogyo Co., Ltd.). By stirring and mixing at 5000 rpm for about 20 minutes, further adding xanthan gum and stirring and mixing with a three-one motor (manufactured by Fuji Film Co., Ltd.), the pesticidal formulation in water suspension of the present invention can be obtained.

Prior to use, the active ingredients of agricultural chemicals and calcium carbonate, basic magnesium carbonate and magnesium hydroxide are dry pulverized by Jet-O-mizer (manufactured by Seishin Enterprise Co., Ltd.) or Dynomill [Willie A. Baccofen]. (Willy
A. Manufactured by Bachofen), etc., and finely pulverized in advance to have an average particle diameter of about 0.5 to 4 μm.

Further, basic copper chloride and calcium carbonate, basic magnesium carbonate, one kind of magnesium hydroxide, a viscosity modifier, and if necessary, other auxiliary agents are added to a predetermined amount of water in which a surfactant is dissolved, It is also possible to uniformly mix with a three-one motor and then finely pulverize with a wet pulverizer such as Dynomill to obtain the water-suspended pesticide formulation of the present invention.

In the present invention, there is no problem in using basic copper chloride alone as the agrochemical active ingredient, and also using a mixture of two or more kinds of the agrochemical active ingredient. Other pesticide active ingredients include insecticides such as acephate, permethrin, NAC, and phenpropatorin, and fungicides include but are not limited to kasugamycin, streptomycin, oxadixyl, and the like.

The names of these pesticides are common names described in "Pesticide Handbook 1989 Edition" (published by the Japan Plant Protection Association).

Next, examples will be described, but the present invention is not limited to these examples.

All parts in the examples are parts by weight.

Example 1 To 28.6 parts of water, 3 parts of a polycarboxylic acid type surfactant (sodium salt of a copolymer of maleic anhydride and isobutylene, molecular weight 6000) and 0.2 part of polyoxyethylene nonylphenyl ether were added. 45 parts of basic copper chloride (25 parts as Cu) and 20 parts of calcium carbonate, p-chloro-m-xylenol 0.1 in which 3 parts of ethylene glycol were dissolved and previously crushed by a dry crusher to an average particle size of 3 μm
Parts, and stirred and mixed at 5000 rpm for 20 minutes with a homomixer, then xanthan gum 0.1% was added and stirred and mixed with a three-one motor to obtain a uniform pesticide in water.

Example 2 4 parts of a polycarboxylic acid type surfactant (sodium salt of a copolymer of maleic anhydride and diisobutylene, molecular weight 6000) and 3 parts of ethylene glycol were dissolved in 22.55 parts of water to prepare a base. Copper chloride 45 parts, basic magnesium carbonate 25 parts, p-chloro-m-xylenol 0.1 part, colloidal hydrous aluminum silicate 0.
3 parts of xanthan gum and 0.05 part of xanthan gum were added and uniformly mixed with a three-one motor, and then wet pulverized with a dyno mill to an average particle diameter of about 1 μm to obtain a uniform pesticide in an aqueous suspension.

[0031]

[Comparative example]

Comparative Example 1 3 parts of sodium alkylbenzenesulfonate, 0.2 parts of polyoxyethylene nonylphenyl ether and 3 parts of ethylene glycol were dissolved in 48.6 parts of water,
After adding 45 parts of basic copper chloride (25 parts as Cu) and 0.1 part of p-chloro-m-xylenol finely pulverized in advance to an average particle size of 3 μm by dry pulverization, and stirring with a homomixer at 5000 rpm for 20 minutes, Add 0.1 parts of xanthan gum, stir and mix with a three-one motor,
Obtain a uniform pesticide in water.

Comparative Example 2 To Comparative Example 1, 20 parts of calcium carbonate was added, and the amount of water in Comparative Example 1 was adjusted to 28.6 parts to obtain a uniform pesticide in water.

Comparative Example 3 A polycarboxylic acid type surfactant (copolymer of maleic anhydride and diisobutylene, molecular weight 6000) was added to 47.4 parts of water.
3 parts, 1 part of a sodium salt of β-naphthalene sulfonic acid formalin condensate and 3 parts of ethylene glycol were dissolved, and 45 parts of basic copper chloride (25 parts as Cu) p-chloro-m-xylenol 0.1 part, colloid Water-containing aluminum silicate (0.5 part) is added, and the mixture is wet-milled with a three-one motor to an average particle size of 1 μm to obtain a uniform pesticide in water.

[0034]

[Test Example] Next, a test example will be given in order to demonstrate the usefulness of the present invention. Test Example 1 Viscosity The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The conditions are rotor No. 2 was used, and the liquid temperature was set to 25 ° C. at a rotor rotation speed of 12 rpm. The results are shown in Table 1.
It is as follows.

Test Example 2 Sedimentation Test 450 g of a pesticide formulation in water suspension was put in a plastic bottle of 500 ml capacity.
After 1 hour, the mixture was allowed to stand for 3 months at 50 ° C., the heights of the sedimentation layer and the whole layer were measured, and the sedimentation state of the dispersoid at the bottom of the container was calculated as follows.

[0036]

[Equation 1] Sedimentability (%) = [height of sedimentation layer (cm) / height of all layers (cm)] × 100 The results are shown in Table 1.

Test Example 3 Redispersibility Test 450 ml of the water-suspended preparation was placed in a plastic bottle having a capacity of 500 ml, allowed to stand at 50 ° C. for 3 months, and then the container was repeatedly inverted.
The number of times until the sediment is completely dispersed is calculated and
It was evaluated according to the criteria of C.

A: Dispersion after 10 times of inversion B: Dispersion at 11 to 99 times of inversion C: Dispersion after 100 times of inversion The results are shown in Table 1.

[0039]

[Table 1]

[0040]

When the pesticide formulation in water suspension of the present invention is carried out, the following action and effects are brought about.

That is, first, good redispersibility is obtained with respect to the sediment formed during storage of the preparation. Second,
Since it is a water-based formulation, there is little danger of ignitability, flammability, etc., irritation to the human body, paint contamination,
Problems related to environmental hygiene such as odor are improved.
Thirdly, since the suspension has good redispersibility and becomes a uniform spraying liquid, when it is used, it exhibits a high disease control activity and does not cause phytotoxicity to crops.

Therefore, the present invention is useful as a novel formulation technique for an aqueous suspension formulation containing basic copper chloride as an agrochemical active ingredient.

Claims (1)

[Claims] A water suspension prepared by dissolving a polycarboxylic acid type surfactant in water and mixing at least one or more of calcium carbonate, basic magnesium carbonate and magnesium hydroxide with basic copper chloride as an agrochemical active ingredient. Agrochemical formulation.