JPH0899802A - Water-floating pesticide granules with controlled disintegration dispersibility on the water surface and their carriers - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a pesticide formulation that can be easily treated and does not harm the sprayer or the environment. [Structure] Granulation type agricultural chemical granules having controlled floating properties on water surface and disintegration dispersibility, and carrier thereof, and product form for paddy rice transfer in which the granules are packed in boxes, bags or bottles with a transfer port , A product form for throwing rice paddy in which the granules are packaged in water-soluble paper. [Effect] Contribute to the development of the agricultural and agrochemical industries where safety and labor saving are required.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION It is an object of the present invention to provide a pesticide formulation which can be easily treated and does not harm the sprayer or the environment.

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granule carrier for water-floating pesticides with controlled disintegration dispersibility on the water surface, a water-floating pesticide granule, and a pesticide for paddy field transfer using the pesticide granule. Formulation and pesticide formulation for paddy field throwing.

[0003]

Conventionally, agricultural chemicals for paddy fields have been formulated into various dosage forms, such as powders, wettable powders, emulsions, granules, etc., and sprayed on the surface of water or rice plants for convenient use. .

However, powders and wettable powders have health problems for users and producers due to dusting and environmental pollution.
In the case of emulsions, there are problems of toxicity of organic solvents and fire. Granules have few such drawbacks, but are not only disadvantageous in terms of physical distribution and economical efficiency, but also often have insufficient control effects depending on the active ingredient.

For these reasons, recently, floorable (hereinafter abbreviated as FL) and dry floorable (hereinafter abbreviated as DF)
A new dosage form has been developed. These are diluted with water and used as an aqueous solution, suspension or emulsion. These dosage forms called FL and DF are said to be the dosage forms that have solved the above-mentioned drawbacks of wettable powders in that they have no powdering and are fluid, but these dosage forms are sprayed including conventional dosage forms. In order to do so, it must first be dissolved or dispersed in water, then often a spraying device is required,
In addition, it is necessary to enter the paddy field when spraying. Especially for a small-scale part-time farmer, it is not only economically and safety-intensive, but also laborious and time-consuming to prepare a container and a spraying device to dissolve or disperse and to spray the rice in a paddy field. Is big. Especially for modern farmers, who depend heavily on the elderly and women, such burdens are unbearable.

For this reason, recently, as a method that can be easily sprayed without requiring a special tool for spraying, there is a method in which the herbicide FL is put in a plastic bottle and sprinkled into the paddy field through a small hole formed in the cap portion. It has been developed. This method has the advantage that it can be sprayed easily without the need for special equipment for spraying, but the spraying of the chemical liquid may be necessary due to the fact that it is still necessary to enter the paddy field for spraying, and depending on the spraying method and wind direction. Has some drawbacks such as being
It cannot always be said that the drawbacks of the conventional method could be completely eliminated. In addition, disposal of used empty bottles may cause safety and environmental problems.

As the water-floating granules, (1) those which are suspended using a water-floating carrier (Japanese Patent Publication No. 48-1)
5613, Japanese Patent Publication No. 47-1240),
(2) Pumice or fluke having a specific water-absorbing ability as a carrier (Japanese Patent Publication No. 44-8600), (3) Granules using a volatile insecticidal compound (Japanese Patent Publication No. 49-11421), (4) A carbamate-based pesticide active ingredient and an organic compound having a distribution system of 10 ² or more with respect to water held on a solid carrier (JP-A-2-174702),
(5) A composition comprising a solid carrier, a fungicide, a herbicide or an active ingredient capable of controlling plant growth, and an oil (JP-A-3-1933).
No. 705) is disclosed. However, these cannot replace the conventional granules in terms of the spraying method and cannot reduce the spraying labor.

Further, recently, a herbicide for paddy field, which contains a surfactant and a foaming agent as active ingredients (Japanese Patent Laid-Open No. 128301/1993).
Gazette), an active ingredient, a surfactant, and a binder or herbicide tablet or capsule for paddy field control (JP-A-3-1738).
No. 02) has been disclosed. In treating these preparations, from the viewpoint of the safety of the sprayer and the protection of the environment, it is an effective method to wrap these preparations in a water-soluble paper such as a film of polyvinyl alcohol and throw them into paddy fields ( JP-A-4-226901).

Although such a paddy-thrown-in formulation has the advantage that paddy field pesticides can be easily treated, it is not uniformly sprayed like conventional granules and powders, and when these solid formulations are thrown into water, the formulation is Will settle on the soil surface and will be foamed here to disperse the active ingredient in the paddy water, so undissolved drug particles will settle around the dropping point and the dissolved active ingredient will also be near the dropping point. Since it forms a high-concentration solution near the soil surface, it is easily adsorbed to the soil. Therefore, even if the active ingredient is a compound whose water solubility is considerably high, the active ingredient is adsorbed at a high concentration on the soil near the dropping point of the formulation, and depending on field conditions, weather conditions, etc. There is a drawback that defects such as unevenness and, in some cases, effects on the subsequent crops are likely to occur. In order to eliminate such uneven distribution of the active ingredient as much as possible, a foaming agent is usually added to the thrown-in formulation so that the solid agent is disintegrated and dispersed as soon as possible, and the active ingredient is diffused by the foaming force. It is often done. At this time, the foaming agent is compounded with an organic acid and a carbonate, and the mechanism in which both react in the presence of water to generate carbon dioxide gas is used, while the formulation containing the foaming agent is stored during storage. It has the drawback that both react depending on the components in the formulation, and often causes problems such as swelling of the packaging and weak foaming during use. In particular, the throw-in formulation causes a decrease in foaming power because it is necessary to disperse the active ingredient in water by the foaming power even in a paddy field where the water temperature is low and to dissolve and diffuse it as soon as possible to form a uniform treatment layer on the soil surface. Therefore, there is a concern that the diffusion of the active ingredient becomes insufficient and causes the above defects.

For this reason, recently, the technology of the injectable preparation containing no effervescent agent has been developed. For example, Japanese Patent Laid-Open No. 5-
Japanese Patent No. 78207 discloses a water-spreadable agricultural chemical formulation package packaged with a water-soluble film. This technique is to dissolve an active ingredient of an agricultural chemical in an organic solvent or the like to obtain a water-spreading oily substance, and to retain this as it is or as a solid substance to enclose it in a water-soluble film. If it is packed as it is, there is a problem of dangerous substances that accompany the use of organic solvents.If the solid substance is to be retained, the solid substance must be water-soluble and the oily substance cannot completely float up. Since it remains at the dropping point, it causes chemical damage and lack of efficacy. When the solid substance is water-soluble, there are problems such as equipment corrosion during granulation and stability of the active ingredient.

Further, in JP-A-5-58804 and JP-A-5-78204, each is composed of an agricultural chemical active ingredient, a glass hollow body having an average particle diameter of 250 μm or less, and a water-soluble polymer. 10 to 1 of a solid composition having a particle size of 600 μm or less containing a floating pesticide formulation for water surface molding and a pesticide active ingredient, an inorganic floating substance having an average particle size of 250 μm or less, and a high boiling point solvent, which is molded to a weight of 100 g.
A technique relating to a water-applied floating agrochemical formulation in which 00 g is packaged in a water-soluble polymer film is disclosed. However, the former has the problem of economy in the molding method, and the latter has the problem of the formulation method and the problem that it does not exhibit sufficient spreadability on the water surface depending on the physical properties of the active ingredient.

Further, Japanese Patent Laid-Open No. 5-155703 discloses an agrochemical formulation in which a granular core having an apparent specific gravity of less than 1 is coated with an oily substance as a pesticide active ingredient and a substance that changes the air / water interfacial tension. There is. This method is certainly advantageous in terms of economy and manufacturing method, but in the case of a certain type of particle nucleus, particularly in the case of a liquid drug substance, the active ingredient is adsorbed to the particle nucleus, and the whole amount does not elute or the volume is large. There are problems that it becomes too large and difficult to process, and that it is difficult to coat the active ingredient. These are biological effects, phytotoxicity, productivity,
It becomes a serious problem that affects distribution.

JP-B-44-8600 discloses a technique relating to a floating granular pesticide composition in which a main agent is adsorbed on a carrier made of granular pumice or leeks and coated with a higher fatty acid, and is disclosed in JP-B-47-1240. In Japanese Patent Publication No. 48-1179, Japanese Patent Publication No. 48-1179 discloses a technique of floating granules in which an insecticide is fixed to baked perlite with polybutene. The technology of the granules to be disclosed in JP-B-48-1181 is a technology of water-floating granules in which foamed perlite is loaded with an insecticide and a water-generating agent, and in JP-B-48-1182. The technology of granules in which an emulsion of a herbicide is supported on an inorganic carrier that floats in water is disclosed in Japanese Patent Publication No. 4815612, in which a cellulose ether or a polycarboxylic acid type polymer surfactant is supported as a spreading agent. Grain floating in water Technical agrochemical composition, JP-B 64
No. 25702 discloses a technique relating to a water-suspending solid preparation prepared by blending a main agricultural chemical and a polyoxyalkylene silicone in a solid carrier, and Japanese Patent Publication No. 3-76281 discloses an active ingredient and an emulsifier. Techniques relating to an easily-dissolvable underwater emulsifying powdery granule in which the contained liquid undiluted solution is stored in a thermally expanded rock powdery granule are disclosed. However, these techniques are similar to the above-mentioned techniques in that they are not different from conventional powders and granules in terms of the spraying method and cannot reduce the spraying labor, and for the purpose of labor saving, a special spraying device is used. Without using, put the granules in a suitable container with a transfer port and transfer them into the paddy field from a ridge or the like, or throw a few pesticide pouches into the paddy field from several to several dozen per 10a and throw them in. Spread the pesticide formulation on the surface of the water as soon as possible, then release the active ingredient from the surface-floating particle nuclei within a short time, dissolve and disperse it in water, and prevent the wind from blowing. The composition of the invention essentially differs from the idea and technical content of the invention.

JP-A-58-65203 (Japanese Patent Publication No.
-56323), a biologically active ingredient is attached to an inorganic or organic porous body or hollow body by a synthetic resin or gypsum, and a hole communicating with the outside is closed to form a hollow body, and
A technology relating to a composition containing a molded water surface floating bioactive substance prepared to have a specific gravity of 1.0 or less and a particle diameter of 5 mm or less is disclosed, and diazinon 5% powder granules using shirasu balloon or MIPC4 using cork powder are disclosed. % Powder is exemplified. However, this technique is not similar to the above-mentioned technique in that it is not different from conventional powders and granules in terms of the spraying method, and it cannot reduce the spraying effort. The present invention relates to a composition having an effect of physicochemically controlling the expression rate of an active substance, and the concept and technical content of the invention are essentially different from the composition of the present invention described below.

[0015]

Therefore, no special equipment is required for spraying, which is labor-saving. Safe for sprayers and the environment. Easy treatment of containers. There is a risk of insufficient drug effect or drug damage due to segregation of active ingredients. There has been a demand for a formulation and a treatment method that satisfy the requirement that the formulation is stable over time.

In view of the above situation, the inventors of the present invention have made extensive studies with the aim of developing a formulation and a treatment method which satisfy the above conditions.

As a result, in the pesticide formulation using the granulation carrier of the present invention and the pesticide granules of the present invention, most of the active ingredients are released into water while the granules spread on the water surface,
It was found that the uneven distribution of the active ingredient hardly occurred regardless of the weather conditions, and it was not a problem. In addition, since the active ingredient is released on the surface of the water and disperses and dissolves in water, adsorption by the soil and sedimentation on the soil surface are slow. Since it is adsorbed and forms a treated layer, there is little concern about chemical damage and uneven efficacy in this sense as well. From these facts, the obtained granules can produce good results even if they are not evenly sprayed like ordinary granules without causing chemical damage. The present invention has been completed by finding that it can be a formulation suitable for frame spraying from A. et al.

[0018]

Configuration of the Invention

[0019]

The present invention is for agricultural chemicals containing expanded perlite, expanded shirasu, and / or cork, and having the physical properties of (1) to (4) below, which are suspended on the water surface and disintegrated and dispersed. Granulation carrier, (1) The apparent specific gravity is 0.10 to 0.40 (2) The particle size classification of 0.710 to 4.760 mm is 90% or more (3) The suspension degree after 3 minutes is 0.5 ml or less (4 ) Water surface floating rate after 2 hours is 30% or less Contains a carrier selected from foamed perlite, foamed shirasu, and / or cork and an agrochemical active ingredient, and has the following physical properties (1) to (4), Preferably, after being put in water, the spread distance after 3 minutes is 4 m or more, and as the water surface spreadability improver, one kind selected from acetylene-based surfactants, silicone-based surfactants and fluorine-based surfactants or Floating on the water surface, it is desirable to mix two or more Granulated pesticide granules that disintegrate and disperse, (1) The apparent specific gravity is 0.10 to 0.70 (2) The particle size classification of 0.710 to 4.760 mm is 90% or more (3) Suspension after 3 minutes Degree is 0.5 ml or less (4) Water surface floating rate after 2 hours is 30% or less 1 selected from wood powder, sawdust, chaff powder, coconut shell powder, coffee bean powder, rice bran, bran, licorice powder and cellulose powder 1 Containing seeds or two or more vegetable powders,
The above-mentioned pesticide granulation carrier and pesticide granules, a pesticide formulation for paddy field transfer characterized by packaging the pesticide granules in a box with a transfer port, a bag, and a bottle, and the above pesticide granules into water-soluble paper. It is a pesticide formulation for paddy field throwing, which is characterized as a package.

The obsidian, pearlite, and pinelite, which are the raw materials for the pearlite used in the present invention, are mainly distributed in relatively new volcanic rock areas after the Tertiary era, and in the world, they are iced through the western part of the Americas and Europe. From the southern part of the land to the Mediterranean Sea, from Japan to New Zealand,
It is a kind of natural glass distributed over Australia. Also in Japan, it is produced in various places such as Akita, Yamagata, Fukushima, Nagano, Saga, Oita and Hokkaido. Perlite is obtained by heating and burning these obsidian, pearlite, and pinelite rocks at a high temperature of around 1000 ° C. to vaporize crystal water and volatile components, thereby rapidly expanding the softened glassy material.
It is a pumice stone with pearly air bubbles inside, and is widely used for construction, heat insulation, gardening, etc. 1mm in particle size
There are many grades from the following fine to those including 5 mm and above. The shape, density, particle size distribution, etc. of the product change depending on the type and particle size of the rough stone and the expansion conditions.
Generally, pearlite and pinelite are used for the production of a proper mixture of particles of each size, and obsidian is used for fine-grained and extremely lightweight products. Obsidian gives round and relatively hard particles.

Shirasu, which is a raw material for the foamed shirasu used in the present invention, has a pumice-falling pumice layer widely distributed mainly in southern Kyushu and a secondary sedimentary layer of amorphous volcanic glass showing about 70%. In Japan, in addition to this, it is partially produced in Hokkaido, around Towada Lake, and the Kanto region. The foamed shirasu is a hollow one obtained by treating the volcanic glass in the shirasu at a high temperature to foam it, and is a fine particle to granular material having a low bulk specific gravity, inertness, and good mixing and fluidity. Those treated at a relatively low temperature have a film thickness of about 6 μm and have a relatively large bulk specific gravity and are hard to float in water. The film thickness is 3 when processed at high temperature
When it is about μm, the bulk specific gravity is small and it easily floats on water. But,
If it is treated at a higher temperature, the balloon will be torn and it will sink into the water. With respect to particle size, there are various grades ranging from fine particles having an average particle diameter of several tens of μm to particles having a large average particle diameter of several mm. A normal foamed shirasu has a balloon ratio of about 65 to 95%, but a grade with a high balloon ratio can also be obtained by separating only the light portion by blowing or squeezing the foamed shirasu.
In the present invention, of these, any grade can be used as long as it is of the type that floats on water.

The cork used in the present invention is obtained by crushing the bark portion of the cork oak mainly produced in Portugal into powder or granules, and generally it is processed into various shapes to obtain bottle stoppers or coasters. It is used for interiors, boards such as bulletin boards, and ignition agents. There are various grades of cork, which is a raw material, depending on its particle size and the mixing ratio of recycled recycled scraps from the above-mentioned processing manufacturers. In the present invention, any of these grades can be used, but those crushed to a particle size of about 1 mm or less are easier to use than those that are too large.

The substances for imparting water-floating property to the granules used in the present invention may be of any grade, but the present invention utilizes the property that these substances float in water.
Since the purpose is to spread the pesticide granules on the water surface and uniformly treat the active ingredient in the paddy field, at least until the granules spread the water surface and spread over a wide area. Need to be floating. Therefore, if you use an unfoamed part, a crushed segment, or a heavy cork bark part that contains a large amount of components that do not float in water, the particles will not float easily and the amount must be increased. It is not preferable because it disappears. Further, if the particle size is too coarse, the balloon may be broken or cannot be granulated during granulation. Therefore, too coarse a particle is difficult to use, and a particle size of 1 mm or less, preferably 0 or 5 mm or less is fine. If these are crushed, the particles will not float easily, so crushing should be avoided.

The amount of the foamed perlite, the foamed shirasu, and the cork to be compounded is sufficient if the granulation carrier and the pesticide granules are suspended in water. In the case of foamed perlite and foamed shirasu, it depends on the type and grade of these, the type of active ingredient and the type of other auxiliaries, and the formulation such as the compounding amount
In order to provide the pesticide granules with the floating property which is the object of the present invention, it is usually necessary to be 15% or more, preferably 30 to 90.
% Compound. In the case of cork, it can be floated in a smaller amount than these, but usually 3% or more is necessary,
It is preferably blended at 5% or more. When these are mixed to prepare a granulation carrier or a pesticide granule, it may be prepared so that the pesticide granule floats in water using the above as a guide.

The pesticide granulation carrier of the present invention comprises a raw material for imparting floating properties to these granules, and other auxiliary agents such as other extenders, binders, disintegrating dispersants, wetting agents, and granulation improving agents. After wet granulation with agents, water surface spreaders, etc., dry granulate, measure by the method described below, and have physical properties of (1) to (4) below, and mold into particles that float and disperse on the water surface. To do.

(1) 90% or more of the particle size classification of apparent specific gravity of 0.10 to 0.40 (2) 0.710 to 4.760 mm (3) Suspension degree of 0.5 ml or less after 3 minutes (4) The water surface floating rate after 2 hours is 30% or less. The granulation carrier may be prepared by any of the following methods, but if the physical properties are not satisfied, the pesticide granules do not float on the water surface or the active ingredient May be blown on the surface of the water, or may settle in the vicinity of the dropping point and segregate, which may cause chemical damage and insufficient efficacy.

Since the degree of disintegration of the granulated carrier depends on the type of binder, it is necessary to select an appropriate binder. The binder is a relatively low molecular weight dextrin or pregelatinized starch, various other water-soluble starch derivatives, polyvinylpyrrolidone, salts of polyacrylic acid,
Examples thereof include salts of carboxymethyl cellulose, polyvinyl alcohol having a relatively low molecular weight and a low saponification rate, salts of ligninsulfonic acid, water-soluble polymer substances such as gum arabic, and montmorillonite-based fine mineral powders such as bentonite.

Among these, bentonite, sodium salt of ligninsulfonic acid, dextrin, and pregelatinized starch are relatively inexpensive and easy to use. In addition, there are various grades of carboxymethyl cellulose salts, which have swelling properties by themselves, so that the disintegration dispersibility can be adjusted by adjusting the quality and the blending amount, which is particularly useful.

The amount of the binder to be blended depends on the formulation composition, the granulation method,
The amount is usually about 0.1 to 30%, preferably about 0.5 to 10% in the granulated carrier, although it depends on the size of the particles and the like. Bentonite is inexpensive and useful as a bulking agent and a granulating property improving agent, and can be added in a larger amount.

When only the floating property-imparting substance has poor granulation properties, when the obtained particles are too light to handle easily, and when the economical efficiency is poor, a filler is added. The extenders include bentonite, talc, calcium carbonate, diatomaceous earth, amorphous silicon dioxide, clay, which are generally used as pesticide carriers, as well as starch, wood flour, sawdust, coffee bean powder, tab powder, cellulose powder, and fine powder. Vegetable powders such as crystalline cellulose, rice husk powder, rice bran, bran, and coconut shell powder can be used. Among these, in particular, many plant powders are relatively cheap and themselves are relatively light, so that there is an advantage that the amount of the flotation imparting substance can be reduced. Bentonite is advantageous because it has plasticity by itself and serves as a granulating property improving agent and a binder. Calcium carbonate often does not adversely affect the stability of the active ingredient and is easy to use.

The compounding amount of these fillers is usually about 0 to 80% in the granulated carrier. As the granulating property improving agent, various surfactants generally used as a granulating property improving agent for agricultural chemical granules, and those having a viscosity for imparting plasticity to the composition are useful. Nonionic surfactants such as polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene aryl aryl ethers, anions such as sodium salts of dialkyl sulfosuccinates and sodium salts of alkylbenzene sulfonic acids. In addition to the surfactant, bentonite is useful because it is inexpensive and can be used as a bulking agent.

The amount of the granulating property compounding agent to be compounded in the granulating carrier varies depending on what is used, but it is usually about 0.02 to 3% in the case of a surfactant and 1 to 50% in the case of bentonite. It is a degree.

Anionic surfactants are often used as disintegrants and dispersants. Suitable disintegrators and dispersants include, for example, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate condensate, maleic acid and styrene sulfonate. Salt of condensate with acid, salt of carboxylic acid condensate such as acrylic acid and maleic acid, polyacrylic acid salt, salt of acrylic acid and maleic acid copolymer, salt of maleic anhydride methyl vinyl ether copolymer, alkylene And maleic acid copolymer salt, diisobutylene and maleic acid copolymer salt, alkylbenzene sulfonate, dialkylsulfosuccinate, lauryl sulfate salt, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylaryl Ether sulphate salt, polyoxyethylene Kill ether phosphate and salts thereof, anionic surfactants and sodium tripolyphosphate such as polyoxyethylene alkylaryl ether phosphoric acid esters and salts thereof, may be mentioned phosphate sodium hexametaphosphate and the like. Many of these disintegrants and dispersants are also useful as wetting agents. Disintegrators, dispersants and wetting agents are not limited to these,
Suitable nonionic, cationic or zwitterionic surfactants can be used. Further, starch, carboxymethyl cellulose, carboxymethylated starch and salts thereof, cross-linked polyvinylpyrrolidone, microcrystalline cellulose, superabsorbent resins, and the like having properties of swelling by absorbing water are also particularly useful as disintegrating dispersants. Is.

Examples of the water surface extender include copolymers of carboxylic acids such as acrylic acid and maleic acid, and poly-one such as sodium salt, potassium salt and ammonium salt of those obtained by copolymerizing styrene sulfonic acid, vinyl group and the like. Carboxylic acid type polysoap, sodium salt of polystyrene sulfonic acid,
Polysulfonic acid type polysoap such as potassium salt and ammonium salt, soaps such as sodium oleate and potassium stearate, sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, perfluoroalkylcarboxylate, etc. Nonionic surfactants such as anionic surfactants, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, etc.
Various nonionic surfactants such as silicone-based surfactants, acetylene-based surfactants, and pluronic-type surfactants, and further, these nonionic surfactants are phosphoric acid or sulfuric acid esters, and depending on the case, they are suitable. Such as surfactants neutralized with various alkalis, surfactants containing fluorine, various cation or zwitterionic surfactants, liquid paraffin and naphthenic high boiling solvents, low viscosity polybutene, silicone oil, machine oil, etc. Mineral oils,
Various animal and vegetable oils, various resins such as pine resin, camphor white oil, α-pinene, camphor, naphthalene and the like can be used.

Of these, acetylene type surfactants, silicone type surfactants, and fluorine type surfactants are particularly useful.

The acetylene-based surfactant includes acetylene alcohol, acetylene diol, and surfactants obtained by adding alkylene oxide to these.

Acetylene alcohol is HOCR ¹ R ²
A series of compounds represented by —C≡CH (R ¹ and R ² each represent an alkyl group having 1 to 8 carbon atoms), R ¹
Is a methyl group, R ² is an isobutyl group is Surfynol 61, R ¹ and R ² are methyl groups are Olfine B, R ¹ is a methyl group, and R ² is an ethyl group is a trade name of Olfine P It is commercially available.

Acetylene diol is HOCR ¹ R ^2-
A series of compounds represented by C≡C-CR ¹ R ² OH (R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms), and R ¹ is Methyl group, R ² is ethyl group, Surfynol 82, R ¹
Are commercially available under the trade name of Olphin Y, and those having R ² and M ² are methyl groups and R ² is an isobutyl group are Surfynol 104, and those having R ¹ and R ² are methyl groups.

The surfactant having alkylene oxide added thereto is, for example, a surfactant obtained by adding ethylene oxide and / or propylene oxide to the above acetylene alcohol or acetylene diol. As the alkylene oxide-added product, a product obtained by adding ethylene oxide to Surfynol 104 is commercially available under the trade name of Surfynol 400 series. In addition, Surfynol 104S is a mixture of Surfynol 104 (wax-like) and amorphous silicon dioxide 40:
It is a powdery premix obtained by mixing and pulverizing at a weight ratio of 60. These are manufactured by Air Products Co., Ltd., and are sold by Nissin Chemical Co., Ltd. in Japan as an exclusive agent.

The silicone-based surfactant is used in the terminal and / or part of the side chain methyl group of dimethylpolysiloxane.
Silgard series (Dow Corning Silicone) is a nonionic surfactant mainly composed of polyether-modified silicone oil, in which polyethylene oxide and / or polypropylene oxide is introduced, and the terminal OH group is etherified with an alkyl group in some cases. (Trade name), Silwet series (manufactured by Unicar Co., Ltd.), silicone oil KF series (manufactured by Shin-Etsu Chemical Co., Ltd.), kinetic (manufactured by Helena Chemical Co., Ltd.) and the like.

The fluorinated surfactant is a surfactant in which a part or all of the hydrogen atoms of ordinary anion, nonion, cation and zwitterionic surfactants are replaced with fluorine atoms, and is excellent in surface tension lowering power. Are known. In Japan, Unidyne series (Daikin Industries, Ltd.)
), Megafac series (manufactured by Dainippon Ink and Chemicals, Inc.), Futgent series (manufactured by Neos, Inc.), Surflon series (manufactured by Asahi Glass Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.) It is sold under the product name such as.

The blending amount of these water surface spreaders varies depending on the formulation and dosage form, such as the type and content of the active ingredient, the type of water surface spreader, and the type and blending amount of other components, but is usually 0.1.
It is about 10%, preferably about 0.3-5%, and more preferably about 0.5-3%.

These raw materials are pulverized if necessary, then wet granulated using a suitable granulator, dried and sized to obtain a granulated carrier that floats in water.

For the granulation, a granulator such as a horizontal or basket type extrusion granulator, a mixing granulator, a fluidized bed granulator, a tumbling granulator and a spray dryer can be used. When foamed shirasu or foamed perlite is strongly pressed, the balloon is crushed and the buoyancy is reduced. Further, if the cork is also strongly pressed, the buoyancy decreases, so it is preferable to use a granulator that does not apply strong pressure or shearing force, such as a basket-type extrusion granulator or a fluidized bed granulator.

If the particle size of the granulation carrier is too fine,
In the case of the transfer process, it is easily affected by the wind, and in the case of the throw process, the particles become agglomerated in the bag and the spread is not sufficiently exhibited. On the other hand, if it is too large, it becomes difficult to dry the granules, and it becomes difficult to coat a large amount of the active ingredient. Furthermore, the granules are more susceptible to wind on the water surface. Therefore, about 0.710 to 4.760 mm, preferably 1 to
A diameter of about 3 mm is desirable. The shape of the particles may be cylindrical, spherical, or irregular. Further, the apparent specific gravity of the granulated carrier is preferably 0.15 to 0.35, the suspension degree after 3 minutes is preferably 0.3 ml or less, and the water surface floating rate after 2 hours is further increased. , 25%
The following is preferred.

The pesticidal granules of the present invention which float on the water surface and disintegrate and disperse are prepared by blending the pesticidal active ingredient in any step for producing the above granulated carrier or by adding the granulated carrier obtained by the above method. It can be obtained by impregnating or coating an agrochemical active ingredient. The granulation carrier is
Furthermore, the pesticide active ingredient must be coated, and the apparent specific gravity must be small, but since the pesticide granules already contain the active ingredient, even if the pesticide granule has a larger apparent specific gravity than the granulation carrier. I don't care.

The physical properties required for the pesticide granules that float on the water surface and disintegrate and disperse according to the present invention are as follows, as measured by the method described below. Further, if the spreading distance after 3 minutes from being placed in water is 4 m or more as measured by the method described below, more preferable results are obtained.

(1) Apparent specific gravity is 0.10 to 0.70, preferably 0.25 to 0.55 (2) 0.710 to 4.760 mm, preferably 1 to 3 m
The particle size classification of m is 90% or more, preferably 95% or more (3) The degree of suspension after 3 minutes is 0.5 ml or less, preferably 0.
3 ml or less (4) The water surface floating rate after 2 hours is 30% or less, preferably 2
It is 5% or less. In the case of insecticides and fungicides, the pesticide active ingredient that can be used in the present invention is preferably one that has the property of being absorbed and transferred to the rice plant, but even if it does not have the permeation transfer property, it may be insects or insects that live in water or on the water surface. Is effective against fungi that infect water or water. In any case, it is necessary for the compound to have low phytotoxicity. In the case of a herbicide, it is desirable to select a compound that is particularly harmless from the viewpoint of its original properties and the time of use.
The active ingredient may be water-soluble or sparingly soluble in water, and may be solid or liquid. The solid agent of the present invention may contain two or more kinds of active ingredients.

The active ingredient suitable for the present invention is an insecticide,
Isoxathion, Propaphos, Trichlorfon, Diazinon, Disulfotone, Formothione, Dimethoate, Monocrotofos, Acephate, Carbofuran, Carbosulfan, Thiocyclam, Cartap, Bensultap, Benfuracarb, Fratiocarb, Carbaryl, Buprofezin, Fenobucarb, Metholcarb, Propoxurmeso. , Imidacloprid,
Nittenpyram, N- (2-chloro-5-pyridylmethyl) -N'-cyano-N-methylacetamidine (NI
-25, acetamiprid) and the like, and a synthetic pyrethroid effective against insects such as cycloprotoline, etofenprox, and silafluofen that live in water or near the surface of water such as rice weevil and rice dwarf beetle. As the fungicides, blast agents such as probenazole, isoprothiolane, iprobenphos, tricyclazole, pyroquilon, and an active ingredient of 0301, flutolanil, mepronil, MON-240, S-
658 (Furametopyr), (RS) -2- (4-fluorophenyl) -1- (1H-1,2,4-triazol-1-yl) -3-trimethylsilyl-propane-2-
Examples thereof include rubs such as oat (F-155), teclophthalam, benomyl and the like. Herbicides include pyrazolate, benzophenap, pyrazoxifene, pyributycarb, bromobutide, butamifos, mefenacet, bensulfuron-methyl, anilophos, butachlor, pretilachlor, thiobencarb, chlornitrophen, clomethoxyphene, dimuron, bifenox, naproanilide, oxadiazone, bendazone,
Molinate, piperophos, dimepiperate, esprocarb, dithiopyr, imazosulfuron, benfresate, quinoclamin, simmethyline, MCPA and its salts, esters such as sodium and potassium salts, 2,4-
D and its salts such as sodium and potassium salts and esters, MCPB, quinchlorac, pyrazosulfuron-ethyl, 3-N- (2-fluoro-4-chloro-5-cyclopentyloxyphenyl) -5-isopropylidene-1 ，
3-oxazolidine-2,4-dione (KPP-31
4), N- [2- (3-methoxy) thienylmethyl]-
N-chloroaceto-2,6-dimethylanilide (NSK
-850, tenylchlor), 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (JC
-940), cinosulfuron, cimetrin, dimetamethrin, n-butyl- (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy] propionate (DEH-112, cyhalofop-butyl), 2 ', 3 '
-Dichloro-4-ethoxymethoxybenzanilide (HW-52, ethbenzanide), 1- (diethylcarbamoyl) -3- (2,4,6-trimethylphenylsulfonyl) -1,2,4-triazole (CH-90)
0, cafenstrol), HOE-404, 1H-pyrazole-5-sulfonamide, N-{[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]}.
-1-Methyl-4- (2-methyl-2H-tetrazol-5-yl) (DPX47, azimsulfuron), N-
[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -3-methyl-5- (2-chloro-2,2
-Difluoroethoxy) -4-isothiazolesulfonamide, 2- [2- (3-chlorophenyl) -2,3-
Epoxypropyl] -2-ethylindan-1,3-dione (MK243), methyl-2-[(4,6-dimethoxypyrimidin-2-yl) oxy] -6- [1- (methoxyimino) ethyl] benzoate (KUH92
0), MY-100, NBA061 and other paddy field herbicides. As a plant growth regulator, it can be applied to inabenfide, paclobutrazol, uniconazole, triapentenol and the like.

The pesticide granules of the present invention can be applied to any of these active ingredients, but they are particularly effective when the active ingredient has a low melting point, a liquid state, or a low solubility in water. In these compounds, when the granules are non-disintegrating, it takes time for the active ingredient to dissolve in water,
The active ingredient floats on the water surface and is blown by the wind, or the active ingredient settles at a high concentration at the dropping point of the granules, which is likely to cause drug damage and uneven efficacy. On the other hand, in the case of the granules of the present invention, which are suspended and spread on the water surface, disintegrate and disperse, and the active ingredient is dissolved and diffused in water within a relatively short period of time, they are blown by the wind or locally settled. The segregation of the active ingredient due to such factors is small, and it can be the most suitable formulation for the transfer treatment from the ridge and the throwing treatment. Moreover, after the granules spread on the water surface and disintegrate and disperse, most of the granule composition disperses in water, so the amount of suspended solids on the water surface is extremely small, and the product value is also extremely excellent. Becomes

When the particle size is coarse, the solid active ingredient cannot sufficiently cover the particle nucleus, and causes the active ingredient to be densely settled at the input point of the paddy field. It is necessary for the active ingredient to dissolve and diffuse in the paddy water as soon as possible after it is put into the paddy field, and to exert its effect. It goes without saying that localization of the active ingredient over a long period of time causes inconveniences such as insufficient efficacy and drug damage. Therefore, even if it has a high solubility in water, it needs to be pulverized to some extent in the case of a solid. Fine pulverization is especially necessary for those having low solubility in water. For this reason, dry crushing with a hammer mill, jet mill or the like or wet crushing with a sand mill or an attritor is performed.

The wet pulverized active ingredient is dried by a method such as spray drying and then pulverized, or it is absorbed in a carrier having a suitable oil absorption property such as amorphous silicon dioxide, diatomaceous earth, calcium silicate, and a highly oil-absorbing resin. If so, dry-pulverize and handle in the same manner as dry-pulverized active ingredient. Alternatively,
When wet granulating the granules of the present invention, it is also possible to add a slurry that has been wet ground with kneading water to knead and granulate.

In the case of a liquid drug substance or a low melting point compound, if necessary, it may be dissolved in a suitable solvent or emulsifying agent and absorbed by the granulation carrier itself of the present invention to prepare a product, or the oil absorbing property as described above. Or a highly oil-absorbent dextrin, a highly oil-absorbent resin, or the like, or a solid solution is formed with a resin or a chemical substance that is compatible with the liquid drug substance or other solid pesticide active ingredient. If pulverized, it can be handled like a solid active ingredient.

In order to incorporate the pesticidal active ingredient into the granules, any of the steps for producing the above granulated carrier may be used.
Method of blending the pesticide active ingredient or a concentrated premix thereof to granulate the surface of the granulated carrier obtained by the method described above,
Method of coating pulverized pesticide active ingredient or concentrated premix The method may be any one of a method of absorbing a liquid or a liquid pesticide active ingredient or a concentrated premix thereof in the above-mentioned granulated carrier.

It goes without saying that the pesticide granules of the present invention may contain two or more pesticide active ingredients.
Therefore, the above method may be properly used according to the physical properties of the active ingredient. For example, granules containing individual active ingredients are first prepared, and the obtained granules may be appropriately selected such as coating a premix of other active ingredients or absorbing a liquid active ingredient.

In the case of the granulation method, a concentrated premix containing an agrochemical active ingredient is prepared in advance, and this is mixed with various components described in the section of the granulation carrier, and granulated, dried and granulated. good.

In the case of the coating method, the granulated carrier prepared above is charged into a stirring mixer, and if necessary, a liquid binder is added to wet the surface of the carrier,
The most convenient method is to add the above-mentioned concentrated premix of the active ingredient and further stir to coat the surface of the particles. In the premix, if necessary, a wetting agent, a dispersant, an emulsifier and a water surface developing agent as described in the section of the granulation carrier can be mixed and placed.

The stirring mixer used is a Nauta mixer,
It is desirable to select a model such as a ribbon blender, a rotary blender, or a V-type mixer that mixes at a low speed and has a small particle crushing.

Further, a method of coating the water surface spreader on the outermost layer after coating the concentrated premix of the active ingredient is effective in maximizing the effect of the water surface spreader.

The binder may be evaporated after coating, but if an oily (or liquefied) binder which is hard to volatilize is used for coating and these binders are left in the product, the drying step can be omitted. , An advantageous method. In this case, it is preferable that the binder has a property that the surface of the water-floating particle nuclei can be uniformly coated with the active ingredient without adversely affecting the active ingredient such as particle growth and decomposition. Generally, a solvent having a high boiling point, low toxicity, low flammability, low viscosity, specific gravity of less than 1 and low dissolving power for the active ingredient is preferable. Examples of such oily binders include low-viscosity liquid paraffin, chlorinated paraffin, isoparaffin, machine oil, polybutene, paraffin-based, naphthene-based, aromatic high-boiling point mineral oils, coconut oil, etc. Soybean oil, vegetable oil such as rapeseed oil, animal oil such as whale oil and sardine oil, silicone oil and its derivatives, oleic acid, coconut oil fatty acid, maleic acid, fumaric acid, phthalic acid, adipic acid and other mono- or di-carboxylic acids , Plasticizers such as various esters of phosphoric acid such as tributyl phosphate and trischloroethyl phosphate, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and butanediol and their various esters and ( Or) ethers, ε-caprolactone, γ-bu Examples thereof include lactones such as tyrolactone, N-methylpyrrolidone, various liquid surfactants, etc. Among them, liquid paraffin, machine oil, polybutene, carboxylic acid ester, etc. are relatively inexpensive and do not adversely affect the active ingredient. Many of them are stable and have low volatility, which is preferable.

Of course, these oily binders can be used by mixing two or more kinds.

The amount of the oily binder used for this purpose is
The type and composition of water-floating particle nuclei, the type of oily binder, the type and physical properties of active ingredients, the type and blending amount of other auxiliaries, etc. vary, but usually about 3 to 50%, preferably 10 to It is about 40%.

In the case of the absorption method, a general method is to charge the above granulated carrier into the above stirring mixer, and add the liquid or liquefied active ingredient or a concentrated premix thereof under stirring to absorb it. . If necessary, auxiliary agents such as a solvent and an emulsifier can be added to the premix.

The solvent is added as necessary when diluting the liquid raw material or making the low melting point raw material liquid. Therefore, it has a dissolving power for the drug substance, does not affect the stability of the drug substance,
Select a substance with high boiling point and low toxicity and low flammability.
For example, fatty acids, phthalic acid, adipic acid, and phosphoric acid obtained from various animal and vegetable oils such as oleic acid, maleic acid, fumaric acid, and coconut oil used as paraffin-based, aromatic-based, naphthene-based high-boiling solvents and plasticizers. And the like, vegetable oils such as palm oil and rapeseed oil, and animal oils such as whale oil and sardine oil can be used. In general, many pesticide active substances have a specific gravity of 1 or more. In such a case, it is often better to use a solvent having a specific gravity of less than 1 and a low viscosity in order to keep the emulsified particles in water for as long as possible and diffuse them widely in the paddy field. In this sense, liquid paraffin and low molecular weight polybutene are particularly preferable.

The emulsifier is used for emulsifying a liquid drug substance or a solution of the drug substance in water. The emulsifier emulsifier is selected and used in the same manner as the emulsion emulsifier is selected according to the drug substance and the solvent. Unlike ordinary emulsions, there is no artificial stirring at the time of use, so a surfactant that has a good self-emulsifying property and finely emulsifies should be selected.

The thus obtained pesticide granules of the present invention float on the surface water of the rice field and spread over a wide area within a short period of time.
It is necessary to release the active ingredient in water as soon as possible.
However, if the release of the active ingredient is too early, the active ingredient is released in a narrow range before the granule spreads on the water surface, so that the active ingredient is unevenly distributed at the dropping points of the particles. vice versa,
If the release of the active ingredient is too slow, the active ingredient is also blown along with the blowing of the particles, and the active ingredient is unevenly distributed at the blown point. For this reason, the granules must be prepared so as to have the following physical properties (1) to (4) as measured by the following measuring methods to eliminate such defects.

(1) The apparent specific gravity is 0.10 to 0.70, and (2) the particle size classification of 0.710 to 4.760 mm is 90.
% Or more, (3) Suspension degree after 3 minutes is 0.5 ml or less, (4) Water surface floating rate after 2 hours is 30% or less, and granules spread 4 m or more after 3 minutes It is desirable to do.

(Measurement method of apparent specific gravity) 20 mm from the upper end of a metal cylindrical container having a diameter of 50 mm and an internal volume of 100 ml.
A standard sieve with a mesh having an opening diameter of 4.760 mm is installed above the cm. Take a small amount of granules into a sieve, and almost every time, gently scrape off the whole amount with a brush and continue until it rises like a cone from the upper edge of the receiver. Correctly scrape the surface, weigh the sample (g), and the obtained value is 1
The apparent specific gravity value is obtained by dividing by 00.

(Measurement method of particle size distribution) Using a standard sieve having an inner diameter of 20 cm and a depth of 4.5 cm, a receiver, a standard sieve having an opening diameter of 0.710 mm, a standard sieve having an opening diameter of 4.760 mm and a lid are arranged in this order from the bottom. set. In the upper sieve,
Put 50 g of granules, tap the sieve frame with one hand at a speed of 150 times per minute, and rotate the sieve about 90 degrees every 25 times. In this way, the amount of passing through the sieve for 1 minute is 0.
When the weight is less than 1g, remove the sample remaining on the sieve screen and calculate the percentage of the sample in each category.

(Measurement Method of Suspension) 500 ml of 3 degree hard water at 25 ° C. is put into the suspension tester shown in FIG. 1g granule
, And after 3 minutes, read the number of ml of the sample that settled on the scale and use it as the suspension degree.

(Measurement Method of Water Surface Floating Rate) 1 L of 3 degree hard water at 25 ° C. is put into a glass beaker having a capacity of 1 L. After adding 0.5 g of granules and allowing to stand for 2 hours, the mixture is stirred 50 times at a rate of 1 rotation per second using a glass rod, and further 10 times.
Let stand for minutes. The whole amount of the suspended solid on the water surface is collected using an aspirator, filtered through a G-2 glass filter, and the residue on the filter is dried in a drier and weighed. The ratio with respect to the added granules is calculated in%, which is taken as the water surface floating rate after 2 hours.

(Measurement Method of Spreading Distance on Water Surface 3 Minutes After Submersion in Water) A frame having a width of 90 cm, a length of 7 m, and a depth of 10 cm is made of styrofoam and placed horizontally in a windless room. Put a black vinyl sheet on the inner surface and add water to adjust the depth to 5 cm. 2g of granules 50cm from the edge
3 minutes after the injection, the distance the tip of the preparation has moved is measured. If the water becomes dirty, the spreading distance will differ greatly, so replace the water and vinyl sheet for each test.

The thus obtained pesticide granules of the present invention are directly transferred into the paddy field from a box, bottle, bag or the like having a suitable transfer port, or thrown into a water-soluble paper as a package from a ridge or the like. To process. Since the pesticide formulation of the present invention releases the active ingredient while spreading on the water surface, it is sufficient to appropriately treat the pesticide from the ridge or the like into the paddy field without evenly spraying it into the paddy field like general granules. It is possible to bring about various biological effects.

In the case of direct transfer into paddy fields using boxes, bottles, bags, etc., the packaging form is paper, synthetic resin, glass,
A metal box, bottle, or bag with a suitable transfer port is convenient. The transfer port may be as simple as a resin cap with a hole of several mm to several cm.
As the product form, the granules of the present invention may be directly enclosed in such a container, or the product prepared in the usual packaging form may be transferred to a dedicated container having a transfer port for processing.
If the packaging material is paper, it is advantageous because it can be incinerated immediately after use.

In the case of the throw-in treatment, the preparation of the present invention is divided into suitable water-soluble papers. Water-soluble paper means a film or sheet having the property of being dissolved or dispersed in water. Examples of the water-soluble paper include those made of polyvinyl alcohol or its derivative, those made of pullulan film, those made of sodium salt of carboxymethyl cellulose and cellulose, those made of polyethylene oxide and its derivative, and the like.

The pesticide granules prepared to have floating spreadability on the water surface of the present invention inhibits spread of the pesticide granules when the pesticide granules are divided into water-soluble papers having no spreadability. It may happen. During this period, the water surface spreader dissolves in water and loses its spreading power, so that the water surface spreadability that can be expected from the state of treating the water surface without packaging is not seen. For this reason, the active ingredient is localized in a narrow range near the dropping point, and a desirable result cannot be obtained. Therefore, it is desirable to use spreadable water-soluble paper in the present invention.

The spreadable water-soluble paper is a film or sheet which itself has a property of being easily dispersed or dissolved in water to spread the pesticide granules on the water surface. Examples of such spreadable water-soluble paper include a film made of polyvinyl alcohol and / or a derivative thereof (hereinafter abbreviated as PVA film).

The PVA film has a degree of polymerization (Mn) of 1000.
~ 2000, saponification degree 85 ~ 95% polyvinyl alcohol with a small amount of plasticizers, stabilizers, etc. into a film, a film containing a small amount of a copolymer such as carboxylic acid in the polymer Also includes. The film is required to have high mechanical strength and high cold resistance and be water-soluble, and in that sense, if the degree of polymerization of polyvinyl alcohol as a raw material is too high, or if the degree of saponification is too high, it becomes difficult to dissolve in cold water, which is preferable. Absent. The film thickness is 25
The film strength of about 70 μm can be used,
It is preferably about 30 to 50 μm in terms of dissolution time.

The edges of the water-soluble paper may be sealed with glue, but there is a problem in workability and the glued portion is often difficult to dissolve. In this respect, what can be heat-sealed is convenient.

The weight of one packet when divided into packets is about 30-
150g is easy to throw. With this weight, even children, women, and the elderly can easily throw the ball into a target point within 15 m. If it is heavier than this, it will be a pain to throw and it will not be easy to handle a large area. Also, below this, the target point cannot be reached due to the influence of the wind.

Since the pesticide granules of the present invention spread over a wide range on the water surface and the diffusion of the active ingredient reaches a wide range, it is not necessary to force them into a normal paddy field to a far distance.
It is enough to drop it on the water surface 3 m ahead.

If the number of packets to be thrown into the paddy field is too large, it is troublesome to throw them in, labor is not saved, and it is economically disadvantageous. On the other hand, if the amount is too small, the pesticide granules may not be sufficiently spread. Generally, the number is about several to several tens per 10a, preferably about 5 to 20.

The agricultural chemical granules of the present invention thus obtained must immediately disperse / dissolve in water after spreading on the water surface, and then sequentially dissolve and diffuse. If the granules seem to settle, segregation of the active ingredient occurs at the settling point. Further, if the active ingredient is not dispersed from the granules and is floating on the water surface for a long time, the wind blows.

Therefore, the pesticide granules of the present invention are required to have the above-mentioned suspension degree and water surface floating rate, and it is desirable to have the above spreading distance.

When the obtained granules are subjected to transfer treatment, a bag, a box or a bottle made of paper, resin, or those obtained by laminating aluminum foil or vapor-depositing aluminum or silica, glass, metal, wood or the like. To package. It is convenient if these containers are provided with appropriate transfer ports so that they can be transferred as they are from a ridge.

When the sachet is thrown in, it is packaged in a bag or box made of paper, resin, or aluminum foil or aluminum or silica vapor-deposited thereon, metal, wood or the like.

In terms of physical properties, the granules of the present invention are stable with respect to moisture absorption over time. Therefore, it is not necessary to pay as much attention to moisture absorption as an effervescent preparation, but since water-soluble paper is broken when exposed to water, it is preferable to use an exterior that is appropriately waterproofed.

[0088]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these.

[0089]

Examples 1 to 10 (Examples of granulation carrier) 1 kg of each mixture having the formulation shown in Table 1 was charged in a kneader,
Newcol 291PG (manufactured by Nippon Emulsifier Co., Ltd., J (2
-Ethylhexyl) surfactant containing sodium salt of sulfosuccinate as a main component) and kneaded in a 0.2% solution in an amount shown in Table 1 to form a basket type granulator L-5 type (Kikusui Seisakusho Co., Ltd.). Extruded and granulated from a screen having an extrusion particle size of 1.5 mm. It was dried at a hot air temperature of 100 ° C. using a fluidized bed drier, a sieve having an opening diameter of 4.760 mm was forced through, and a fine grain portion was removed by a sieve of 0.297 mm. The physical properties of the obtained granulated carrier are shown in Table 2 below.
I wrote it in.

[0090]

[Table 1]

[0091]

Examples 11 to 15 Examples 1, 2, 3 shown in Table 1
According to the same prescription as in 4 and 6, granulation and drying were performed using a flow coater FL mini type (fluidized bed granulator, manufactured by Freund Sangyo Co., Ltd.), and the granulated product had an opening diameter of 4.760 mm and 0.5.
Sieve using a 90 mm sieve, 4.760
A particle size classification of 0.590 mm was obtained. The physical properties of the obtained granulated carrier are shown in Table 2 below.

[0092]

Examples 16 to 20 Examples 1, 2, 3 shown in Table 1
Granulate with the same recipe as 4 and 6 using a Spartan Luzer (mixing type granulator, manufactured by Fuji Paudal Co., Ltd.),
Example 16 of the granules dried with a fluidized bed dryer at a drying temperature of 100 ° C., and the granules are sieved using a sieve having an opening diameter of 4.760 mm and 0.590 mm, and having a particle size classification of 4.760 to 0.590 mm. 20 were obtained respectively. The physical properties of the obtained granulated carrier are shown in Table 2.

[0093]

[Table 2] ─────────────────────────────────── Example No. Apparent specific gravity Granularity (%) ¹⁸⁾ Suspension (ml) ¹⁹⁾ Floating rate (%) ²⁰⁾ ──────────────────────────────────── 1 0.19 97 0.20 22.0 2 0.19 99 0.10 23.4 3 0.19 95 0 21.3 4 0.23 96 0 6.6 5 0.23 94 0.01 8.5 6 6 0.25 92 0.25 12.2 7 0.22 93 0 11.0 8 0.21 97 0 9.5 9 0.28 93 0.30 13.8 10 0.22 90 0.28 20.1 11 0.17 99 0.20 19.2 12 0.16 98 0.12 14.0 13 0.17 99 0.01 12.0 14 0.21 99 0 1.3 15 0.22 98 0.23 2.2 16 0.28 99 0.10 20.5 17 0.30 99 0.03 24.2 18 0.29 99 0 19.7 19 0.30 99 0 0.5 20 0.28 98 0.04 2.4 ──────────────────────────────────── 18) 0.710 to 4.760 mm division 19) 3 minutes After suspension 20) 2 hours later

[0094]

[Examples 21 to 40] Granule Example A mixture of 24 parts of pyroquilon drug substance, 3 parts of talc (Pharmacopoeia), and 1 part of Carplex # 80 (amorphous silicon dioxide manufactured by Shionogi Pharmaceutical Co., Ltd.), and a hammer mill To obtain a premix containing 85% pyroquilon. Example 1
73.4 parts of 20 granulation carriers were charged into a Nauta mixer, 10.0 parts of Super Oil C (manufactured by Nippon Oil Co., Ltd., crude liquid paraffin) was added to moisten the surface of the particles, and the premix 14.1 was prepared. Parts were added and mixed to coat the surface of the particles. Next, 2.5 parts of Surfynol 104S was added and mixed and coated to obtain a granule containing 12% of pyroquilon. The physical properties of the obtained granules are shown in Table 3 below.

[0095]

[Example 41] Granule example F-155 drug substance 85.0 parts, Carplex # 100
(Shionogi Pharmaceutical Co., Ltd., amorphous silicon dioxide) 11.5
Department, Neoperex No. 6F (Kao Co., Ltd., surfactant containing sodium salt of dodecylbenzene sulfonic acid as a main component) 3.5 parts is mixed, and Jet omizer 0
A premix containing 85% of F-155 was obtained by pulverizing with a 101 type (jet mill manufactured by Seishin Enterprise Co., Ltd.). 15.0 parts of cork (0.2-0.5 mm classification),
4.0 parts of serogen 7A, 40.0 of bentonite 1
Part, wood flour 24.9 parts, Surfynol 104S 2.0
Part, F-155 premix 14.1 parts were charged into a kneader, and 0.2% liquid of Newcol 291PG (powder part 1
90 parts) was kneaded, and the mixture was extruded and granulated from a screen having an extrusion particle size of 1.5 mm using a basket type granulator L-5 type. Drying was carried out at a hot air temperature of 70 ° C. using a fluidized bed dryer, a sieve having an opening diameter of 4.760 mm was forced, and a fine particle portion was removed by a 0.710 mm sieve. The obtained granule contains 12.0% of F-155.

[0096]

Example 42 Granule Example Thiocyclam drug substance (85.3%) 87.92 parts, Aerosil R972 (hydrophobic synthetic silica, manufactured by Nippon Aerosil Co., Ltd.) 3.00 parts, Carplex # 100 4.
08 parts and 5.00 parts of powdered quick lime are mixed and crushed with a jet omizer 0101 type to give thiocyclam 75
% Premix was obtained. 49.0 parts of the granulated carrier obtained in Example 4 was charged into a Nauta mixer, and 27.6 parts of n-butyl maleate (first grade reagent) was added and mixed to moisten the surface of the particles. Then, 21.9 parts of premix of thiocyclam was added and mixed to coat the surface of the particles. Further, 1.5 parts of Surfynol 104S was added and mixed, and the surface of the particles was coated to obtain granules containing 16.4% of thiocyclam.

[0097]

[Example 43] Granule example Silafluofen drug substance (94.8%) 22.15 parts, Surfynol 420 5.00 parts, Solvesso 150
(Exxon Chemical Co., Ltd., aromatic high boiling solvent) 72.
Eighty-five parts were mixed and dissolved to obtain a premix containing 21% of silafluofene. Granulation carrier 6 of Example 7
30.0 parts of a premix of silafluofene was added to 7.0 parts for absorption. Furthermore, 3.0 parts of Surfynol 104S was added and mixed and coated to obtain 6.3% granules of silafluofene.

[0098]

[Example 44] Example of granules Bentazone drug substance 85 parts, Carplex # 80 5 parts,
5 parts of Surfynol 420 and 5 parts of talc were mixed and crushed by a jet omizer 0101 type to obtain a premix containing 85% of bentazone. Cork (0.
2 to 0.5 mm classification) 15.0 parts, serogen 5A 4.
0 parts, bentonite 2 20.0 parts, wood flour 32.8 parts,
The kneader was charged with 28.2 parts of bentazone premix and 0.2% solution of Newcol 291PG (powder part 10
The mixture was kneaded with 0 part to 80 parts) and extruded and granulated from a screen having an extruded particle size of 1.5 mm using a basket type granulator L-5 type. Drying was carried out at a hot air temperature of 70 ° C. using a fluidized bed dryer, a sieve having an opening diameter of 4.760 mm was forced, and a fine particle portion was removed by a 0.710 mm sieve. The obtained granule contains 24.0% of bentazone.

[0099]

[Example 45] Granule example Mefenacet drug substance 61.76 parts, Daimlon drug substance 2
6.47 parts, Rondax drug substance 2.95 parts, Carplex # 80 3.82 parts, Surfynol 104S 5
The parts were mixed and crushed with a jet omizer 0101 type to obtain a mixed premix of a raw material. Cork 20.0
Parts, 5.0 parts of serogen 5A, 20 parts of bentonite 2.
0 parts, 21.0 parts of coconut shell powder, and 34.0 parts of a mixed premix of the active ingredient were charged into a kneader, and Newcol 291P.
The mixture was kneaded with a 0.2% solution of G (80 parts to 100 parts of powder part), and was extruded and granulated from a screen having an extruded particle size of 1.5 mm using a basket type granulator L-5 type. Dry with a hot air temperature of 70 ° C. using a fluidized bed dryer, and force a sieve with an opening diameter of 4.760 mm to pass 0.710.
Fine particles were removed with a mm sieve. The obtained granules contained 21.0% mefenacet, 9.0% dimuron, and 1.0% bensulfuron methyl.

[0100]

[Example 46] Granule example Pyributicarb drug substance 48.0 parts, Daimlon drug substance 36.
0 parts, Rondax conformer 4.0 parts, Carplex # 8
0 parts of 7.0 and 5 parts of Surfynol 104S were mixed and pulverized by a jet omizer 0101 type to obtain a mixed premix of a raw material. Charge 15.0 parts of cork, 4.0 parts of serogen 5A, 20.0 parts of bentonite 2, 21.0 parts of wood flour, 15.0 parts of calcium carbonate, 25.0 parts of mixed premix of the drug substance into a kneader. , 0.2% liquid of Newcol 291PG (for 100 parts of powder,
60 parts) and kneaded, and extruded and granulated using a basket type granulator L-5 type from a screen having an extruded particle size of 1.5 mm. Dry at a hot air temperature of 70 ° C. using a fluidized bed dryer, and force a sieve having an opening diameter of 4.760 mm,
Fine particles were removed with a 0.710 mm sieve. The obtained granules were Pyributicarb 12.0% and Daimlon 9.0.
%, Bensulfuron-methyl 1.0%.

[0101]

Example 47 Granule Example 15.0 parts of cork, 4.0 parts of serogen 5A, 20.0 parts of bentonite 2, 33.0 parts of wood flour, 4.0 parts of Surfynol 104S were charged into a kneader, 120 parts of commercially available beam sol (suspension concentrate containing 20% tricyclazole, manufactured by Takeda Pharmaceutical Co., Ltd.) was added and kneaded.
It was extruded and granulated from a screen having an extrusion particle size of 1.5 mm. Dry at a hot air temperature of 70 ° C using a fluidized bed dryer,
Force the sieve with an opening diameter of 4.760 mm to 0.71
Fine particles were removed with a 0 mm sieve. The granules obtained contain 24% of tricyclazole.

[0102]

Example 48 Granules Example 1.4 parts of bensulfuron-methyl drug substance (92.9%) and 1.4 parts of calcium carbonate were crushed with a hammer mill to obtain a bensulfuron-methyl drug substance premix. Pyributycarb raw material (94.1%) 17.0 parts, Roca help (Mitsui Mining & Smelting Co., Ltd., pearlite powder) 4.0 parts and calcium carbonate 2.5 parts are mixed, and Jet omizer 10
Type 1 (manufactured by Seishin Enterprise Co., Ltd.) feed rate 2 kg /
The mixture was crushed under an air pressure of 6 kg / cm ² for hr to obtain a pyributicarb raw material premix. Bensulfuron methyl drug substance premix 2.8 parts, pyributicarb drug substance premix 23.5 parts, Demol EP powder (Kao Corporation, sodium salt of alkylene maleic acid copolymer) 3.30
Part, Pearlex NP (manufactured by Nippon Paper Industries Co., Ltd., sodium lignin sulfonate) 6.5 parts, polyvinylpyrrolidone K-30 (manufactured by Kyoto Wako Pure Chemical Industries, Ltd., reagent) 2.6 parts,
39 parts of foamed Shirasu PB03 (manufactured by Shirasu Co., Ltd., average particle size: 75 μm) and 15.8 parts of calcium carbonate were charged in a kneader (manufactured by Fuji Paudal Co., Ltd.), and after mixing, an appropriate amount of water was added and kneaded. . Extruder for kneading granulator EXK
-1 type (manufactured by Fuji Paudal Co., Ltd.) is extruded and granulated from a screen of 2.0 mm, and the granulated product is dried by a fluidized bed dryer (hot air temperature 100 ° C.) to be in a range of 1.5 to 3.0 mm. The granules were obtained by sieving. 93.5 parts of this granule was placed in a plastic bag, and 3.9 parts of Super Oil C (produced by Nippon Oil Co., Ltd., crude liquid paraffin) and Surfynol 465 (produced by Nissin Chemical Co., Ltd., ethylene oxide addition of acetylene diol). 50% premix (Surfinol 4)
65 and Carplex # 100 (Shionogi Pharmaceutical Co., Ltd.,
2.6 parts of a premix obtained by mixing and pulverizing amorphous silicon dioxide) in a ratio of 1: 1 was added and mixed, and the surface of the grain was weakly coated with Surfynol 465, and bensulfuron-methyl 1.
A granule containing 3% and 16% pyributycarb was obtained.

[0103]

[Example 49] Example of granules 36.0 parts of a pyrazolate drug substance (97.3%), 7.0 parts of Rocahelp and 7.0 parts of calcium carbonate were mixed, and a supply rate of 2 kg / h was supplied by a jet ohmicer 101 type.
The mixture was crushed at r and an air pressure of 6 kg / cm ² to obtain a pyrazolate raw material premix. Pyrazolate bulk premix 5
0 parts, Demol EP powder 3.30 parts, Pearlex NP 6.5 parts, glucose 2.6 parts and effervescent shirasu PB
31.1 parts of No. 03 was charged in a kneader, mixed and then kneaded by adding an appropriate amount of water. Extruding a kneaded product Granulator EXK-
Granulation was carried out by extruding from a 2.0 mm screen using a type 1 machine, the granulated product was dried with a fluidized bed dryer (hot air temperature 100 ° C.), and 1.5 to 3.0 mm sections were sieved to obtain granules. Put 93.5 parts of this granule in a plastic bag, and add Super Oil C
3.9 parts and 2.6 parts of 50% premix of Surfynol 465 (premix in which Surfynol 465 and Carplex # 100 were mixed and ground at a ratio of 1: 1) were added and mixed, and Surfynol was added to the surface of the particles. 465 was weakly coated to give granules containing 35% pyrazolate.

[0104]

[Example 50] Granule example Pyrazolate drug substance (96.2%) 26 parts, CH-900
Mix 6.0 parts of drug substance (96.7%), 7.2 parts of Lokahelp and 4.8 parts of calcium carbonate, and use Jet Ohmizer 101 type to feed at 2 kg / hr and air pressure at 6 kg.
/ Cm ² was crushed to obtain a raw material premix. 44.0 parts of this drug substance premix, 2.6 parts of the bensulfuron-methyl drug substance premix of Example 48, Sokalan C
P9 (manufactured by BASF, maleic acid-olefin copolymer sodium salt) 3.3 parts, Pearlex NP6.5
Part, 2.6 parts of glucose and 32. of effervescent Shirasu PB03.
Six parts were placed in a kneader, and after mixing, an appropriate amount of water was added and kneaded. The kneaded product is extruded and granulated by an extruding granulator EXK-1 type through a 2.0 mm screen, and the granulated product is dried by a fluidized bed drier (hot air temperature 100 ° C.) to give 1.5 to
Granules were obtained by screening 3.0 mm sections. This granule 91.
Take 6 parts in a plastic bag and add 3.8 parts of Super Oil C and 50 parts of 50% premix of Surfynol 465 (premix in which Surfynol 465 and Carplex # 100 are mixed and ground at a ratio of 1: 1). Mix and gently coat Surfynol 465 on the surface of the granules, 1.2% bensulfuron methyl, 25% pyrazolate, CH-9
A granule containing 5.8% of 00 was obtained.

[0105]

[Example 51] Example of granules 15.0 parts of cork (0.2 to 0.5 mm classification), 4.0 parts of serogen 7A, 40.0 parts of bentonite 1, 24.9 parts of wood flour, Example 41 F-155 Premix 1
4.1 parts were placed in a kneader, and Newcall 291PG
Was kneaded with a 0.2% liquid (80 parts to 100 parts of the powder part) and extruded and granulated from a screen having an extruded particle size of 1.5 mm using a basket type granulator L-5.
Dry with a fluidized-bed dryer at a hot air temperature of 70 ° C., and force a sieve with an opening diameter of 4.760 mm to pass 0.710 mm.
The fine particles were removed by sieving to obtain F-155 high content granules. 98.0 parts of the obtained granules were charged into a Nauta mixer, 2.0 parts of Surfynol 104S was added and mixed, and the surface of the granules was weakly coated with Surfynol 104S. The obtained granule contains 12.0% of F-155.

[0106]

Example 52 Granule Example 1 part of Megafac 110 and 4 of Carplex # 80
Parts are mixed, crushed with a hammer mill and Megafac 11
A 20% premix of 0 was obtained. F-obtained in Example 51
155 high content granules were coated with Megafac 110 premix in the same manner as in Example 51 and 1 part of F-155 was added.
A granule containing 2.0% was obtained.

[0107]

Example 53 Granule Example 2 parts of silicone oil KF6017 and 3 parts of carplex # 100 were mixed and ground with a hammer mill to obtain a 40% premix of silicone oil KF6017. Silicone oil KF60 as in Example 52
12% granules of F-155 coated with 17 premixes were obtained.

[0108]

Examples 54-55 Granules Example Instead of Surfynol 104S of Example 21, 20% premix of Megafac 110 of Example 52 or silicone oil KF6017 of Example 53, respectively.
Granules containing 12% of pyroquilon were obtained in exactly the same manner as in Example 21 except that 40% of premix was used.
The physical properties of the granules of Examples 21 to 55 are shown in Table 3.

[0109]

[Table 3] ────────────────────────────────── Example No. Apparent specific gravity Granularity (%) Suspension degree ( ml) Water surface floating rate (%) Spread distance (m) ────────────────────────────────── 21 0.27 99 0.08 7.2 5.3 22 22 0.27 99 0.05 8.3 5.2 23 237 7 97 0 5.9 4.9 24 24 0.29 97 0 1.3 5.0 25 25 0.29 96 0 2.2 4.7 26 0.32 95 0.10 2.8 4.9 27 0.28 95 0 2.5 4.3 28 288 99 0 2.9 4.0 29 0.33 96 0.12 3.4 4.2 30 0.28 95 0.12 2.3 4.2 31 0.25 99 0.08 7.5 4.7 32 0.25 99 0.05 6.3 5.3 33 0.25 99 0 5.2 5.0 34 0.27 99 0 1.1 4.9 35 35 0.27 99 0.06 1.2 4.8 36 0.34 99 0.04 4.3 4.7 37 0.37 100 0.01 5.1 4.1 38 0.35 100 0 3.8 4.0 39 0.38 99 0 0.1 4.8 40 40 0.36 99 0 1.0 4.8 41 0.28 100 0.02 10.5 5.0 42 423 33 98 0.13 0.8 4.4 43 438 97 0 1.6 4.9 44 0.35 100 0.15 13.8 4.7 45 0.28 100 0.03 21.4 4.8 46 0.33 100 0.08 8.5 5.2 47 47 0.36 100 0.23 10.2 4.1 48 0.38 100 0.01 4.0 5.1 49 0.45 100 0.02 3.8 4.6 50 0.48 100 0.02 4.2 4.8 51 0.28 99 0.05 8.3 5.4 52 0.28 99 0 23.5 4.6 53 0.28 100 0 19.2 4.5 542 0.27 99 0.03 8.3 4.6 55 0.27 100 0 9.6 4.5 ──────────────────────────────────

[0110]

[Comparative example]

[0111]

[Comparative Examples 1 to 8] Examples of granulation carrier According to the formulations shown in Table 4, the granulation carrier was obtained in exactly the same manner as in Example 1. The physical properties of the obtained granulated carrier are shown in Table 5.

[0112]

[Table 4] ──────────────────────────────────── Comparative Example No. 1 2 3 4 5 6 7 8 ──────────────────────────────────── Cork 10.0 5.0 15.0 15.0 Shirasu 50.0 30.0 70.0 70.0 Serogen 5A 4.0 4.0 4.0 4.0 1.0 5.0 Serogen WSA 1.0 1.0 4.0 Pa index # 2 10.0 Wood flour 51.0 41.0 44.0 Bentonite 1 40.0 40.0 40.0 40.0 Bentonite 2 20.0 20.0 25.0 20.0 Calcium carbonate 46.0 20.0 40.0 Vanilex N 5.0 5.0 ───────── ────────────────────────────

[0113]

[Table 5] ─────────────────────────────────── Comparative example number Apparent specific gravity Granularity (%) Suspended degree (ml) Water surface floating rate (%) ─────────────────────────────────── 1 0.63 99 0.65 ^* 14.5 2 0.60 98 0.80 ^* 9.2 3 0.53 96 0.23 3.2 4 0.59 94 0.60 ^* 1.0 5 0.21 99 0 88.0 6 0.20 92 0.65 11.2 7 0.23 96 0.60 8.2 8 0.25 94 0.70 4.8 ────────────── ────────────────────── *: Some grains sank without collapsing

[0114]

Comparative Examples 9 to 16 Granules Using the granulation carriers of Comparative Examples 1 to 8, granules containing 12% of pyroquilon were obtained by the same method as in Example 21. The physical properties of the obtained granules are shown in Table 6 below.

[0115]

[Comparative Examples 17 to 18] Examples of granules The granules granulated in Example 41 were classified into 4.760 mm or more (Comparative Example 17) and 0.710 mm or less (Comparative Example 18). The physical properties of these granules are shown in Table 6.

[0116]

[Table 6] ────────────────────────────────── Comparative example number Apparent specific gravity Granularity (%) Suspension degree ( ml) Surface floating rate (%) Spread distance (m) ────────────────────────────────── 9 0.74 99 2.80 ^* 2.1 − ^** 10 0.72 99 1.03 ^* 4.2 3.2 11 11 0.71 98 0.89 ^* 1.3 4.0 12 0.74 96 3.20 ^* 0.5 − ^** 13 0.28 99 0 91.0 5.0 14 14 0.24 95 1.55 8.3 3.2 15 0.28 98 1.35 5.2 3.3 163 0.31 96 1.50 3.5 2.8 17 17 0.25 3 0 38.5 3.3 18 0.38 2 0.85 12.3 3.7 ─────────────────────────────────── *: Some of the particles settled without collapsing **: Most of the particles settled

[0117]

[Test example]

[0118]

[Test Example 1] 50 of each of the granules obtained in Examples and Comparative Examples
g (however, 39 g only in the case of Example 48), Hycelon C200 (polyvinyl alcohol film, thickness 40
μm, manufactured by Nigo Film Co., Ltd. In the center of the paddy field, which was divided into 10x10m ridge sheets in one section, set up 6 chopsticks so that the diameter would be about 10cm, and keep the bag stationary. Drop the granules obtained in it. It was
After the sachets broke and the granules inside spread to the surface of the water, a stick was set up in the leeward blowing part. On the 4th day of the treatment, the diameter 10c was measured from the drop point, the blow-off part, and the three points on the opposite side of the blow-up.
Soil of m and 10 cm in depth was collected and frozen. Take out the frozen soil, slice a layer of 1 cm from the surface layer,
Each component present in the soil was analyzed, and the ratio of the amount of active ingredient present at the dropping point and the blow-off portion to the amount at the point on the opposite side of the blow-up was obtained. The results are shown in Table 7.

[0119]

[Table 7] ───────────────────────────────── Sample active ingredient Drop point Sweep section ─────── ─────────────────────────── Example 21 Pyroquilon 1.11 1.20 〃 22 〃 1.15 1.03 〃 23 〃 0 .97 1.12 〃 24 〃 0.95 0.98 〃 25 〃 1.04 1.20 〃 26 〃 1.13 1.02 〃 28 〃 0.93 1.22 〃 41 F-155 1.340 .98 〃 42 thiocyclam 0.98 0.89 〃 43 Silafluofen- ^* - ^* 〃 44 Bentazone 1.29 0.87 〃 45 Mefenacet 1.15 1.47 Dimeuron 0.87 1.62 Bensulfuron methyl 0.931 .03 〃 46 Pyributycarb 1.39 0.99 Da Muron 1.72 1.23 Bensulfuron Methyl 1.22 0.98 〃 47 Tricyclazole 1.25 0.88 〃 48 Bensulfuron Methyl 0.93 1.02 Pyributicarb 1.41 1.00 〃 51 F-155 1. 15 1.03 〃 52 〃 0.88 1.53 〃 53 〃 0.93 1.32 〃 54 Pyroquilon 1.15 1.28 〃 55 〃 0.95 1.31 Comparative Example 9 〃 38.45 1.03 〃 10 〃 20.52 0.75 〃 11 〃 17.22 0.82 〃 12 〃 32.45 0.98 〃 13 〃 1.02 18.25 〃 14 〃 7.43 0.91 〃 15 〃 5. 72 1.12 〃 16 〃 5.60 1.01 〃 17 F-155 0.87 4.85 〃 18 〃 8.25 1.32 ─────────────────── ── ───────────── *: Numerical or less detection limit any of the samples in the soil shows the proportion of the amount of active ingredient relative to the amount of active ingredient in the soil on the other side of Fukiyose.

As shown in Table 7, in each of the samples of Examples, the ratio of the amount of the active ingredient present at the dropping point and the blowing portion to the amount at the opposite side of the blowing portion is about 2
Although it was less than twice, in the sample of the comparative example, there was a point where the concentration of the active ingredient was considerably high at the dropping point or the blow-off part.

[0121]

[Test Example 2] The granules of Example 21 were placed in a box provided with a shaking outlet and subjected to a shaking treatment at a rate of 1 kg / 10a within a range of about 3 m from the ridge, and the granules spread over a wide water surface. did.
4kg / 10 of Koratop granules 5 (granules containing 5% of pyroquilon, manufactured by Sankyo Co., Ltd.) against blast
a The same effect was obtained when compared with the uniform spraying group.

[0122]

[Test Example 3] The granules of Example 42 were placed in a box with a shakeout port and subjected to a transfer treatment at a rate of 1 kg / 10a within a range of about 3 m from the ridge. It was exhibited. As for the effect against Kobunomeiga, 4 of padan granules (granules containing 4% cartap, manufactured by Takeda Pharmaceutical Co., Ltd.)
When compared to the kg / 10a uniform spraying group, the same effect was obtained.

[0123]

[Test Example 4] The granules of Example 46 were placed in a box with a shakeout port and subjected to a transfer treatment at a rate of 0.5 kg / 10a within a range of about 3 m from the ridge. It was expanded to. When the herbicidal effect was compared with 500 ml / 10a uniform spraying of Calshot Flowable (suspension concentrate containing 1% bensulfuron-methyl and 12% pyributycarb, Sankyo Co., Ltd.), the same effect was obtained. .

[0124]

[Test Example 5] 450 g of the granules of Example 49 were added to a paperboard carton (inside dimensions: 6 cm (W) x 9 cm (L) x 20 cm).
(H), the volume was 1080 cm ³ ), 5 circular openings having a diameter of 6 mm were attached to the upper portion, the container was attached with a resealable seal, and the lower portion was heat-sealed. The material composition of this paperboard carton is polyethylene (20
μm) / paper (250 g / m ² ) / copolymer resin of ethylene and methacrylic acid EMAA (20 μm) / aluminum foil (7 μm
m) / Polyester (12 μm) / Polyethylene (30
μm) is laminated. Peel off the resealable seal at the opening of the container and shake the two containers by hand to
The entire amount of granules was applied while going around the ridge of the paddy field. The granules were suspended and spread on the water surface, and then disintegrated and dispersed in water, and the active ingredient was dispersed in water. The herbicidal effect after 20 days was 3 kg / 1 of a commercially available sunbird granule (manufactured by Sankyo Co., Ltd., pyrazolate 10%).
The same effect was obtained when compared with the 0a uniform spraying group.

[0125]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a pesticide formulation which can be easily treated and does not harm the sprayer or the environment. It greatly contributes to the development of the industry.

The pesticide formulation using the granulation carrier of the present invention and the pesticide granules of the present invention have the following properties:
Most of the active ingredients are released into the water, and regardless of weather conditions, uneven distribution of the active ingredients hardly occurs, which is not a problem.

Further, since the active ingredient is released on the water surface and dispersed / dissolved in water, the adsorption by soil and the sedimentation on the soil surface are slow, and after the water is sufficiently dissolved and diffused in the water of the entire paddy field. Also, since it is adsorbed to the soil to form a treated layer, there is little concern about chemical damage and uneven efficacy in this sense as well.
From these facts, the obtained granules can produce good results even if they are not evenly sprayed like ordinary granules without causing chemical damage. And the like can be a suitable formulation for frame spraying.

[Brief description of drawings]

FIG. 1 shows a suspension tester.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Hirata 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Yasuhiro Tsujino Yasuhiro Yasu-machi, Yasu-gun, Shiga In-house (72) Inventor Masahiko Fujimoto 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Akiyoshi Kawagishi 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house

Claims (8)

[Claims] 1. A granulated carrier for agrochemicals, which contains expanded perlite, expanded shirasu, and / or cork and has the physical properties of (1) to (4) below, which floats on the water surface and disintegrates and disperses. (1) Apparent specific gravity of 0.10 to 0.40 (2) Grain size classification of 0.710 to 4.760 mm is 90% or more (3) Suspension degree after 3 minutes is 0.5 ml or less (4) After 2 hours Water surface floating rate is less than 30% 2. One or more plant powders selected from wood flour, sawdust, chaff powder, coconut shell powder, coffee bean powder, rice bran, bran, licorice powder and cellulose powder. The pesticide granulation carrier according to 1. 3. A structure containing a carrier selected from expanded perlite, expanded shirasu, and / or cork and an agrochemical active ingredient, and having the physical properties of (1) to (4) below, which floats on the water surface and disintegrates and disperses. Granulated pesticide granules. (1) Apparent specific gravity of 0.10 to 0.70 (2) Grain size classification of 0.710 to 4.760 mm is 90% or more (3) Suspension degree after 3 minutes is 0.5 ml or less (4) After 2 hours Water surface floating rate is less than 30% 4. One or more plant powders selected from wood flour, sawdust, chaff powder, coconut shell powder, coffee bean powder, rice bran, bran, licorice powder and cellulose powder are contained. The pesticide granule according to 3. 5. The pesticide granule according to claim 3, which has a spreading distance of 4 m or more 3 minutes after being put into water. 6. The water surface spreadability improver is characterized by blending one or more selected from acetylene-based surfactants, silicone-based surfactants and fluorine-based surfactants. The agricultural chemical granules according to 3 to 5. 7. A pesticide formulation for paddy rice transfer treatment, characterized by packaging the pesticide granules according to claim 3 in a box, a bag or a bottle with a transfer port. 8. A pesticide formulation for dumping in paddy fields, characterized in that the pesticide granules according to claims 3 to 6 are packaged in a water-soluble paper.