JP2002338403A - Agrochemical preparation having water surface-floating property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agrochemical preparation not crushed even by gripping by a hand for performing an agricultural work in a good efficiency and easily, and also scattering in a good efficiency after putting it in and spraying. SOLUTION: This agrochemical preparation has a shape-maintaining property and self scattering water surface-floating property. More concretely, as for the shape-maintaining property, it is preferable to have >=80% in using 2,000 μm sieve in a porcelain ball mill method. Such agrochemical preparation having such shape-maintaining property, self-dispersing property and water surface- floating property simultaneously is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dosage form of a chemical substance. More particularly, it relates to the dosage form of a pesticide formulation, especially granules.

[0002]

2. Description of the Related Art Agrochemicals such as herbicides, insecticides, fungicides, and agricultural fertilizers are used in various dosage forms such as granules.

[0003] Granules are mainly produced by producing empty granules containing no active ingredient and then impregnating the granules with the active ingredient,
And a method of preparing a mixture composition of a carrier, a surfactant, an active ingredient and water, and then extruding the composition, granulating the composition simultaneously or separately, and then drying the composition.

In recent years, attention has been paid to pesticide preparations that can be sprayed simply by throwing them from the ridge without entering a paddy field, in consideration of the ease of operation or safety when spraying.
There must be no local soil residues and good diffusibility of the pesticidal active ingredient in water. Various pesticide formulations have been studied to meet these requirements. For example, Japanese Unexamined Patent Publication No. Sho 60-142901 discloses a pesticide granule having diffusibility. However, since this granule has a large specific gravity and sinks in water after being sprayed, concentration of the pesticide is inevitable.

[0005] Japanese Patent Application Laid-Open No. Hei 7-233002 discloses pesticide particles and tablets of a water surface moving disintegrating dispersion type. But,
The granules have little shape retention and must be used after being packaged in a water-soluble film such as PVA.
If wrapped in a water-soluble film, if the farm worker grasps it with wet hands, the film will dissolve and the granules frequently disintegrate before being administered and sprayed by hand, Not very suitable for manual dosing / spraying.

[0006] JP-A-9-295903 discloses a pesticide granule composition having excellent water surface spreadability. However, Japanese Patent Application Laid-Open
In 295903, it is described that disintegration dispersibility was achieved by including sodium polyacrylate having a molecular weight of 500,000 to 6,000,000. When the content is high, the disintegration dispersibility is considered to be extremely poor.

[0007] Conventional pesticide preparations having diffusibility in water are insufficiently dispersed or, even if dispersion is sufficiently achieved, are produced only with such strength that the grains are crushed when grasped by hand. Various granules having a high strength have also been developed, but since they are too small to be gripped by hand, they usually need to be manufactured as packs packed with a water-soluble film. However, in view of production cost and efficiency, development of more excellent pesticide formulations has been demanded.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a method for delivering a medicine, for example, for agricultural work, in which the medicine is gripped by hand and / or sprinkled with a machine without being packed with a water-soluble film. It is an object of the present invention to provide a granule capable of uniformly introducing a target drug to a target place.

[0009]

The above objects have been achieved by the self-diffusing water-floating pesticide formulation having shape retention properties of the present invention.

[0010] In one embodiment, the equivalent sphere diameter of the pesticide formulation of the present invention is greater than 5 mm. In another embodiment, the equivalent sphere diameter of the pesticide formulation is 10 mm or more. Preferably, the equivalent sphere diameter of the pesticide preparation of the present invention may be 13 mm or more, more preferably 15 mm or more. Examples of the shape of the pesticide formulation of the present invention include a columnar shape, a football shape, or a shape therebetween (for example, a formulation obtained by rounding corners by lightly mixing a granulated product in a columnar shape before drying). Usually, these preparations are columnar granules having a diameter of 5 mm or more and a length of 10 mm or more, more preferably 5 to 10 mm in diameter and 10 to 30 mm in length.

In another embodiment, in the pesticidal formulation of the present invention, the ratio of the content of the pesticidal active ingredient to the total weight of the formulation is higher than 30%. Preferably, the ratio of the content of the pesticidal active ingredient to the total weight of the formulation may be higher than 50%, more preferably 60% or more, 70% or more, 80% or more. As described above, according to the present invention, a pesticide formulation containing more than 30% of a pesticide active ingredient while maintaining shape retention and maintaining self-diffusion is achieved. By spraying the pesticide formulation, it has become possible to spray the same pesticide efficiently and easily for farmers as before.

In another embodiment, the weight of a pesticide formulation of the present invention per grain may be 0.1 g or more. This weight is preferably 0.5 g or more per grain, 1.0 g or more.
g or more, 1.5 g or more, 2 g or more, 3 g or more. Particularly preferably, this weight may be between 0.5 and 1 g.

[0013] In another embodiment, the pesticide formulation of the present invention may have an index of 80% or more in shape retention by a porcelain ball mill method. Preferably, the shape retention of the pesticide preparation of the present invention is 90% by a shape retention index by a porcelain ball mill method.
That is all. However, in consideration of diffusibility in water, the upper limit is preferably 95% or less. Therefore, in another embodiment, the shape retainer is made by porcelain ball milling.
When a 00 μm sieve is used, it can be 80% or more and 95% or less.

In another embodiment, the agrochemical formulation of the present invention may contain a water-soluble carrier and a film-forming substance.

[0015] In one embodiment, the water-soluble carrier may be present at from 5 to 95% based on the total weight of the formulation. In another embodiment, the film forming material may be present at 0.1 to 10% based on the total weight of the formulation.

In another embodiment, the water-soluble carrier is one selected from the group consisting of potassium chloride, ammonium sulfate, sodium chloride, urea and sucrose.
It may include the above.

[0017] In another embodiment, the film forming material can include one or more selected from the group consisting of xanthan gum, sodium alginate, sodium polyacrylate and gum arabic.

In another embodiment, the pesticidal preparation of the present invention may contain a floating agent. Preferably, the density of the buoyancy-imparting agent may be less than 0.5, more preferably less than 0.3.

In another embodiment, in the pesticidal formulation of the present invention, the above-mentioned buoyancy-imparting agent is 1 to 9% based on the total weight of the formulation.
It may be present in a 5% ratio.

In a further embodiment, the buoyancy-imparting agent may be a glass micro hollow sphere.

[0021] In one embodiment, the pesticide formulation of the present invention may contain a disintegration promoter. Preferably, the molecular weight of the disintegration accelerator may be less than 10,000. More preferably, the molecular weight of the disintegration accelerator can be 1000 or less.

In another embodiment, the disintegration accelerator may be present in a ratio of 1 to 15% based on the total weight of the formulation.
In one embodiment, the disintegration promoter can include one or more selected from the group consisting of dextrin, croscarmellose sodium, water-soluble gelatin, sodium carboxymethylcellulose, cellulose ether and hydroxypropylmethylcellulose.

In another embodiment, the disintegration accelerator may be a dextrin having a molecular weight of less than 10,000.

In another embodiment, the pesticide formulation of the present invention may contain a surfactant having a dispersant function. Preferably, the surfactant with dispersant function may be present in a ratio of 5 to 30% based on the total weight of the formulation.

In another embodiment, the surfactant having a dispersant function comprises at least one selected from the group consisting of alkylaryl sulfonate formalin polycondensate, lignin sulfonate and polyacrylate. obtain.

In another embodiment, the pesticide preparation of the present invention may contain a surfactant having a large surface tension lowering ability.

In another embodiment, the surfactant having a large surface tension lowering ability is used in an amount of 0.1 to 0.1% based on the total weight of the preparation.
It may be present in a ratio of 10%.

In another embodiment, the surfactant having a large surface tension lowering ability may include at least one selected from the group consisting of an acetylene glycol-based surfactant and a dioctyl sulfosuccinate salt.

In a preferred embodiment, the pesticidal formulation of the present invention comprises metminostrobin as the pesticidal active ingredient.

The specific gravity of the agricultural chemical preparation of the present invention may be any specific gravity as long as the characteristics of the present invention are maintained. In one embodiment, the specific gravity of the agricultural chemical preparation of the present invention is from 0.4 to 0.4.
1.5. Also, in other embodiments,
The specific gravity of the pesticide preparation of the present invention may be in the range of 0.5 to 1.0.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The terms used in the present invention have the same definitions as those commonly used in the art, unless otherwise specified, as follows.

The term "shape retention" refers to the strength or firmness of the particles so that the shape of the particles is maintained to the extent that they are not crushed by the hand of a farm worker during administration. Here, "maintaining the shape" means that the shape does not need to be completely maintained and the grains are not substantially broken. For example, even if some deformation occurs when grasped by hand, if the granules are not broken by the time the medicine is administered by hand and reaches the paddy field, it can be evaluated as having shape retention. In this specification, shape retention can be evaluated using an index measured by a porcelain ball mill method. For example, when the granule of the present invention uses a 2000 μm sieve in a porcelain ball mill method, the shape retention index is preferably 80%, more preferably 90% or more. However, in consideration of the diffusibility in water, the upper limit is preferably 95% or less. Particularly preferably, it can be 80% to 95%.

Here, in the porcelain ball mill method, a predetermined amount (eg, 100 g in the case of the shape retention property measurement in the present specification) of a sieve having a predetermined size (for example, 2000 μm or 8000 μm) is measured, Put in a pot (in the case of shape retention measurement in this specification, inner diameter about 100 mm x inner depth about 100 mm), and make a porcelain ball (in the case of shape retention measurement in this specification, diameter 30 ± 2 mm, weight 35 ± 5 g) A predetermined number (3 in the case of the shape retention measurement herein),
Rotate for a predetermined time (15 minutes in the case of shape retention measurement in the present specification) (75 ± 1 rotation per minute in the case of shape retention measurement in the present specification).

Next, the sample in the ball mill was
Or transfer to 8000 μm sieve. Fit this sieve into a receiver and cover it. Next, shake lightly for 3 minutes while shaking horizontally. Thereafter, the lid and the sieve are removed, the receiver is tilted little by little, and the sample in the receiver is collected with a brush, and weighed to the order of 0.01 g using a direct reading scale. When no sample remains on the sieve, the measurement is completed. If the sample remains on the sieve, fit the sieve into the receiver again, cover and sieve for another minute. When the passing amount is less than 0.05 g, the measurement is terminated. When the passing amount is 0.05 g or more, the passing amount is 0.0 g
Repeat sieving for another 1 minute until less than 5 g. Weigh the sample in the receiver and add the total throughput. The sieve fraction (W (g)) is measured, and the number obtained by subtracting the proportion of this fraction from the total from 100% is defined as the "shape retention" in this specification. Here, this passage is generally an index of hardness. This is represented by the following equation.

Shape retention (%) = 100−W / 100 × 100 After the surface of the 8000 μm sieve is rubbed, the cracked material is mixed as a sieve, so that the test is conducted with a 2000 μm sieve. Both are used as an index of shape retention. For details of such shape retention measurement, refer to page 212 in “Actual State of the Latest Granulation Technology (Comprehensive Technical Data Book)” (edited by Kanagawa Business Development Center, published by Kanagawa Business Development Center Publishing Division). That.

When the preparation of the present invention is produced by extrusion granulation, the formability of the preparation of the present invention can be evaluated. The formability can be evaluated by referring to the amount of current of the motor of the extruder and the occurrence of squeak. In the present invention, the formability is measured by using a screw type extruder (DG-L1 made by Fuji Paudal) equipped with a 1.0 mm diameter screen, in which the inverter frequency of the motor is 20 Hz and the rotation speed of the shaft is 32 rpm.
Evaluation is made based on the amount of current and the squeak noise when extruded under the conditions of m. In this case, the preferable formability means that the current amount of the motor is stable at an average of 1.6 to 2.0 amps,
This refers to cases where there is little or no squeak. When the amount of current exceeds 2.4 amps on average, it is not preferable for granulation because of high load operation.

"Self-diffusion" refers to the properties of a preparation, and when the preparation is administered or spread, the active ingredient of the preparation can be administered without any external additional measures after administration. (For example, the pesticidal active ingredient) refers to the property of being diffused over a certain area or more. It is preferable that the active ingredient is uniformly diffused within a predetermined time (for example, within 30 minutes) over the whole rice field.

The term "water-floating property" refers to the property of a preparation, and refers to the property of floating on a water surface of a rice field or the like when the preparation is administered or sprayed. In this case, a part of the preparation may be out of the water surface, and all of the preparation is submerged without coming out, but may be still floating in the water. In addition, even if the drug once sinks after being administered, if it subsequently floats, it can be said that it has water surface floatability.

There are various ways to express the size of a formulation. For example, refer to Chapter 2, pages 31 to 33, "Basic of powder engineering" (Nikkan Kogyo Shimbun), edited by the Basic Editing Committee of Powder Engineering. If the particles are spherical, the size can be uniquely specified by expressing them in diameter; otherwise, the minor axis, major axis, thickness (or height) of the formulation
The triaxial average diameter, the triaxial harmonic average diameter, and the triaxial geometric average diameter can be calculated based on the (representative diameter). In addition, the circle equivalent diameter can be calculated based on the area of the projection view of the particle. In this case, the average circle equivalent diameter obtained by projecting from various directions can be used as the diameter. In this case, the diameter is approximated to the actual surface area of the particle. Similarly, the equivalent sphere diameter can be calculated based on the volume of the particles.

Further, the width or length in a certain direction is measured,
This may be a constant direction diameter. This is Green
It is called n diameter or Feret diameter. The diameter that equally divides the area in a certain direction is called a constant direction area equal diameter, which is referred to as Martin.
Called diameter.

In the present specification, in consideration of the simplicity of the measurement, the diameter of the preparation is usually represented by the equivalent sphere diameter.

"Agrochemical active ingredient" refers to a substance having an activity as a pesticide. Here, pesticides include herbicides,
Insecticides, fungicides and the like. The pesticidal active ingredient contained in the preparation of the present invention can be any one as long as it is generally used as a pesticide. The pesticidal active ingredients can be used alone or in combination of two or more.

Exemplary pesticidal active ingredients used in the formulations of the present invention include the following.

[Herbicides] Pyrazolate, Daimulon, Bromobutide, Mefenacet, MCP, MCPB, Triclopyr, Naproanilide, CNP, Clomethoxynil, Bifenox, MCC, Pyributicarb, DCP
A, napropamide, diphenamide, pyropizamide, ashram, DCMU, linuron, methyldimuron, tebuthiuron, bensulfuronmethyl, simazine, atrazine, simethrin, amethrin, promethrin, dimetamethrin, metribuzin, bentazone, oxadiazon, pyrazolate, benzophenaglip, benzophenaplit
Vialaphos, alloxydim, imazosulfuron, azimsulfuron, pyrazosulfuron-ethyl, sinosulfuron.

[Insecticide / Acaricide] Diazinon, fenthion, isoxathion, pyridafenthion, fenitrothion, dimethoate, PMP, dimethylvinphos, acephate, DEP, NAC, MTMC, MIP
C, PHC, MPMC, XMC, BPMC, bendiocarb, pirimicarb, mesomil, oxamyl, thiodicarb, cypermethrin, cartap hydrochloride, thiocyclam, bensultap, pyriproxyfen, phenoxycarb, methoprene, diflubenzuron, teflubenzuron, chlorfluazuron , Buprofezin, Hexythiazox, Pyridabene, Clofenthedine, Nitenpyram.

[Disinfectant] Probenazole, isoprothiolane, pyroquilon, flutranil, methinostrobin, ziram, thiuram, captan, TPN, fusalide, tolclofosmethyl, fosetyl, thiophanatemethyl, benomyl, carbentazole, thiaventhazole, dietofencarb, iprodione, Vinclozolin, Procymidone, Fluorimide, Oxycarboxin, Mepronil, Flutranil, Pencyclon, Metalaxyl, Oxazixyl, Triadimefon, Hexaconazole, Triforin, Blasticidin S, Kasugamycin, Polyoxin, Validamycin A, Mildiomycin, PCNB, Hydroxyisoxazole , Dazomet, Dimethylimole, Diclomedin, Triazine, Ferimzone, Trisik Tetrazole, but like oxolinic are exemplified, preferably a strobilurin compound such as metominostrobin.

The pesticide preparations of the present invention include, for example, acaricides (eg, chlorbenzilate), plant growth regulators (eg, paclobutrazol), nematicides (eg, benomyl), Synergists (eg, piperonyl butoxide, etc.), attractants (eg, eugenol, etc.), repellents (eg,
Creosote, etc.), pigments (eg, Food Blue No. 1, etc.),
Fertilizers (eg, urea, etc.) can also be mixed if desired.

The pesticidal active ingredient is contained in the preparation at an arbitrary content, but is preferably 30% or more, more preferably 50% or more.
% Or more than 50%, more preferably 70% or more.
%, 80% or more, or more.

[0049] The "water-soluble carrier" refers to a water-soluble carrier, and is used for the purpose of increasing the amount of a preparation and the like. Examples of the water-soluble carrier in the present invention include, but are not limited to, potassium chloride, ammonium sulfate, sodium chloride, urea, and sucrose. The water-soluble carrier preferably has good granulation properties and low deliquescence. In one embodiment, in the formulation of the present invention, the water-soluble carrier is present at 5-95% by weight before formulation. More preferably, the water-soluble carrier is present in an amount of 5% to 50% based on the weight before formulation.
%, 5% to 30%, 5 to 20%.

The term "film-forming substance" refers to a water-soluble polymer which dissolves in water at a rate lower than that of a water-soluble carrier and, when poured into water, swells and contains water and dissolves after forming a film. Say. By utilizing the difference in dissolution rate using a combination of a water-soluble carrier having a high water dissolution rate and a film-forming substance having a low water dissolution rate, most of the disintegrated products of the preparation of the present invention have a specific gravity of 1 or less. Therefore, the disintegration material floats on the surface of the water without sinking directly below the formulation,
Or float in the water. Film-forming substances include, but are not limited to, xanthan gum, sodium alginate, sodium polyacrylate, gum arabic, and the like. Preferably, xanthan gum is used. Exemplary xanthan gum has a molecular weight of about 10
100,000 and the viscosity of a 1% aqueous solution is 1,000 mPa · s
(60 rpm, 25 ° C. aqueous solution), but is not limited thereto. As the sodium polyacrylate used as the film-forming substance, a highly polymerized product (preferably, a molecular weight of 1,000,000 to 6,000,000) is preferable. 1
In one embodiment, the film forming material may be present at 0.1 to 10% based on the total weight of the formulation. Preferably,
The film-forming substance is 0.1 to 5 parts by weight based on the weight before formulation.
%, 0. Present at 1-3%, 0.1-2%.

The “floatability-imparting agent” refers to the result that, when contained in a formulation, the formulation has a density lower than the density of water (1.0 g / cm ³ ) in order to impart water surface floatability. A substance that brings. Preferably, the floating agent is
Having a density of less than 1.0 g / cm ³ , more preferably a density of less than 0.5 g / cm ³ , even more preferably 0.3
having a density of less than g / cm ^3. The density of the buoyancy-imparting agent may fluctuate in relation to the density of other ingredients, especially the active ingredient of the agrochemical, which is the main drug, and if the other ingredients impart sufficient buoyancy to the formulation, the The agent may not be contained. Examples of the buoyancy imparting agent include glass micro hollow spheres. In one embodiment, the floating agent of the present invention is present in a ratio of 1 to 95% based on the total weight of the formulation. Preferably, the floating agent is present in a ratio of 1 to 50%, 1 to 30%, 1 to 20% based on the total weight of the formulation. The floating agent used in the present invention has, in another embodiment, a density of 0.24 to 0.30 g / cm ³ . In this case, in one embodiment of the present invention, the content of 15% causes the whole preparation to float.

In the present invention, the combination of a water-soluble carrier and a film-forming substance and a buoyancy-imparting agent are present at the same time. Since it does not occur, efficient diffusion of the pesticidal active ingredient is performed efficiently.
Such a combination has not been performed in a conventional pesticide formulation, and it is a surprising effect that it has not been previously predicted that administration is easy and that effective diffusion of the pesticidal active ingredient has been achieved. .

The term "disintegration accelerator" refers to a substance having the property of swelling and then dissolving when exposed to a solvent such as water. By including a disintegration accelerator in the preparation, a solvent such as water further penetrates into the swelled and dissolved place, thereby promoting disintegration. Since a general water-soluble binder usually dissolves after swelling, it seems to have the same properties, but those having a low molecular weight, high water solubility, and a low aqueous solution viscosity should be called a disintegration accelerator ( For example, Keiichi Sato (K. Sato) "Development technology of water-soluble polymer" (Research and Development)
ent ofWater Soluble Polym
er), published by CMC (1996), "(3) Disintegrant", pp. 3-4).

The disintegration accelerator used in the present invention preferably has a molecular weight of less than 10,000, more preferably has a molecular weight of 5,000 or less, further preferably has a molecular weight of 3000 or less, and still more preferably has a molecular weight of 1000 or less. , 500 or less, 300 or less are used.

The disintegration promoter used in the present specification is not limited to the following, but those having a water solubility of 10% or more can be used. The disintegration promoter used herein is not limited to the following, but the viscosity of the aqueous solution is 5 or less.
% Aqueous solution using a B-type viscometer. 1 using 2
When rotating for 30 minutes (rotor rotation speed is 30 rpm,
And the temperature of the aqueous solution is 20 ° C.)
-The following can be used:

The disintegration accelerator used in the present invention includes dextrin, croscarmellose sodium,
Examples include, but are not limited to, water-soluble gelatin, sodium carboxymethylcellulose, cellulose ether and hydroxypropylmethylcellulose. It has not been heretofore known that gelatin and croscarmellose sodium promote the disintegration of pesticide preparations or wettable powders, and this is the first finding in the present invention.

The term "surfactant" means that when it is dissolved in a solvent such as water, it quickly spreads on the surface of the solvent and remarkably reduces the surface tension, and at the same time, adsorbs on the interface with another liquid or solid, A substance that significantly lowers interfacial tension. Surfactants herein are defined as surfactants having additional properties from another perspective, as follows.

"Surfactant having dispersant function"
A surfactant having the function of dispersing solid fine particles in a liquid. By including a surfactant having a dispersant function, the property that the pesticidal active ingredient is rapidly dispersed when the preparation is disintegrated is enhanced.

Examples of the surfactant having a dispersant function include:
Examples include, but are not limited to, alkylaryl sulfonates, formalin polycondensates, lignin sulfonates, polyacrylates, and the like. Examples of the alkylaryl sulfonate formalin polycondensate include sodium alkylnaphthalene sulfonate formalin polycondensate and sodium alkylbenzene sulfonate formalin condensate. Examples of the lignin sulfonate include sodium lignin sulfonate and calcium lignin sulfonate. Examples of the polyacrylate include sodium polyacrylate, calcium polyacrylate, and ammonium polyacrylate. The polyacrylate preferably has a molecular weight of less than 2,000,000, more preferably less than 500,000. As a surfactant having a dispersant function, one or more selected from the group consisting of alkylaryl sulfonate formalin polycondensate, lignin sulfonate and polyacrylate are used alone or in combination of the present invention. It can be included in the formulation. The optimal combination may vary depending on the formulation of the formulation.

In one embodiment of the present invention, the surfactant having a dispersant function may include only an alkylaryl sulfonate formalin polycondensate. In another embodiment, a polyacrylic acid salt having a molecular weight of less than 2,000,000, more preferably less than 500,000, can be contained in addition to the alkylaryl sulfonate formalin polycondensate. Further, in another embodiment,
In addition to these two surfactants having a dispersant function,
Lignin sulfonate may be contained. Further, in order to improve the disintegration property, the granulation property, etc., preferably, sodium α-olefin sulfonate may be contained.

The term "surfactant having a large surface tension lowering ability" refers to a surfactant having a function of remarkably lowering the surface tension when dissolved in water or the like. The surfactant having a large surface tension lowering ability in the present invention usually has a surface tension of 25 ° C.
Has a function of lowering the surface tension to 60 dyne / cm or less, preferably to 50 dyne / cm or less, in the case of a 0.01% aqueous solution of By incorporating a surfactant having a large surface tension lowering ability into the preparation, the effect of rapidly spreading the pesticidal active ingredient and the like on the water surface when the preparation is disintegrated is enhanced. As a result, the collapsed object spreads to run on the water surface. As a surfactant having a large surface tension lowering ability,
Examples include acetylene glycol-based surfactants and dioctyl sulfosuccinate salts. As the acetylene glycol-based surfactant, acetylene diol, Part 5
0% ethylene glycol solution and the like.

The pesticide preparation of the present invention can be administered or dispersed by adding a combination of a water-soluble carrier such as potassium chloride and a film-forming substance such as xanthan gum, and a floating agent, so that the pesticide preparation is dissolved in water. It has been achieved that the pesticidal active ingredient is spread without sinking and without floating. By using a substance having a binder function such as xanthan gum as a film-forming substance, it has been achieved that the pesticide preparation of the present invention is given a certain shape retention. This is because conventional agricultural chemical formulations (for example, JP-A-7-233002, JP-A-9-29590)
3 and JP-A-60-142901) are unexpected and unexpected effects which were neither achieved nor suggested.

As described above, the details of the present invention have been described in various forms. However, specific embodiments and examples in the present specification are merely examples, and the scope of the present invention is not limited to the examples. It is understood that the invention is in no way limited to the specific embodiments or examples.

[0064]

EXAMPLES (Example 1: Formulation Examples) (Preparation of Premix) Before preparing various preparation examples, a 66% premix as shown in the following table was prepared.

[0065]

Table 1 Preparation of 66% premix First, prepare the actual charge amounts described in the table, and supermix each component using a super mixer (manufactured by Kawada Seisakusho, SMJ-20, capacity 20 L).
Mixed in. First, raw materials other than sodium polyacrylate (liquid) were charged and mixed for 5 minutes. Next, sodium polyacrylate, which is a liquid material, was added dropwise, and mixing was continued for another minute. Thereafter, the mixture was taken out.

Next, using this premix, various blending examples were prepared with the blending as shown in the following table.

[0067]

[Table 2] (Merging / granulation method) Solid substance (other than a 50% ethylene glycol solution of acetylenic diol) using a kneader (KDHJ-3 manufactured by Fuji Electric Industries (currently Fuji Paudal)) (composition example) In 2, the ammonium sulfate was dissolved in water before use) was mixed for 30 seconds, and then a 50% ethylene glycol solution of acetylene diol was added dropwise.

Water was added (in Formulation Example 2 after the ammonium sulfate was dissolved in the water) in an appropriate amount for granulation, and after about 10 minutes of kneading, was taken out. Granulation was performed to a diameter of 10 mm using a granulator (Pelleter) (manufactured by Fuji Electric Industries (currently Fuji Paudal), EXDS-60).
Using a safety oven (SPA-100, manufactured by Tabai Espec Corp.), shelves were dried at 55 ° C. for about 4 hours.

Comparative Example 1 A compounding example was prepared in which potassium chloride or xanthan gum in Example 1 was replaced with clay. The mixing ratio is shown in Table 3 below.

[0070]

[Table 3] Refining and granulation were performed in the same manner as in Example 1.

(Comparative Example 2: Conventional Formulation) For comparison with the conventional formula, Table 2 (Comparative Example 4) and Table 2 of Example 1 of JP-A-7-233002 were used in the case of using metominostropine and the main drug. 4 (Comparative Example 3) and JP-A-9-29
It was prepared based on the formulation example described in Example 3 of 5903 (Comparative Example 5). The specific prescription is as shown in Table 4 below.

[0072]

[Table 4] (Merging / granulation method) In the kneading step, the actual charged amounts of the respective components were put into a mortar, and water was gradually added to combine them so as to be in a state suitable for granulation. Granulation and shelf drying were performed in the same manner as in Example 1.

Example 2 Evaluation of Active Ingredient Amount, Dispersion State, etc. of Each Preparation The active ingredient content ratio, weight per one grain, size, and dispersion state were evaluated for each of the above Formulation Examples and Comparative Examples.

Regarding the dimensions, the particle size is determined by the basics of powder engineering, Editorial Board, “Basics of Powder Engineering” (Nikkan Kogyo Shimbun), No. 2
Chapters, pages 31-33, and were evaluated as described herein above.

The diffusivity in water was evaluated by observing the diffusivity in a bat as shown in FIG. First,
Water of 31 kg (water depth 5 cm) was put into the vat.
Next, in FIG. 1, one grain (1.10 ±
0.06 g). 1 hour, 2 hours, 3
At time, 6 hours, 10 hours, and 24 hours, at each of the measurement points (1) to (5) in FIG. 1, a sample was sampled from a depth of 2.5 cm to measure the concentration.

The diffusivity is expressed by the following equation: diffusivity (%) = (effective component concentration at each sampling point)
/ (Concentration of active ingredient when the entire amount of preparation is uniformly diffused) x 1
00 was calculated. The results for each value are described below.

[0077]

[Table 5] Table 6 below shows the particle size on various scales for each preparation example. Calculation of each particle size was performed according to the description of the powder engineering (supra).

[0078]

[Table 6] The details of the results of the diffusivity test are shown below. The diffusivity at each sampling point was shown for each elapsed time, and the coefficient of variation at each sampling point was calculated. The coefficient of variation was calculated according to the following equation: coefficient of variation (%) = 100 × standard deviation / average value.

In Comparative Examples 3 and 4, granulation was impossible, so that a diffusivity test could not be performed.

[0080]

Table 7 (Formulation Example 1, also shown in FIG. 2)

[0081]

Table 8 (Formulation Example 2, also shown in FIG. 3)

[0082]

Table 9 (Formulation Example 3, also shown in FIG. 4)

[0083]

Table 10 (Comparative Example 1, also shown in FIG. 5)

[0084]

Table 11 (Comparative Example 2, also shown in FIG. 6)

[0085]

Table 12 (Comparative Example 5, also shown in FIG. 7) The relationship between each preparation example, time and coefficient of variation is shown (Table 1).
3). In particular, it can be seen that there is a remarkable difference between the compounding examples and the comparative examples in the early stage of the introduction.

[0086]

Table 13 (Each preparation example, summary of time and coefficient of variation, also shown in FIG. 8) It can be said that the preparation of the present invention is not inferior to Olibrite (registered trademark) 1 kg granules. It is considered that the reason why the coefficient of variation in 24 hours is reduced in any of the preparation examples is that the active substance is dissolved and diffused. However, in the field, the area covered by the 1.1 g of the preparation tested this time is more than five times that of the current test. Can not expect much. Therefore, in the diffusion evaluation in this test format, it is considered that the diffusibility up to 2 to 3 hours after introduction is significant. In view of this point, when the above results are evaluated, it is understood that the diffusivity of the present invention is much better than the conventional formulation.

Example 3 Evaluation of Shape Retention The shape retention of the above preparation examples was evaluated by a porcelain ball mill method. 80
100 g of a sieve residue of 100 μm is weighed, and the
A ball 3 mm in diameter, about 30 ± 2 mm in diameter, and about 35 ± 5 g in weight, placed in a porcelain pot for ball mill having a diameter of about 100 mm × 100 mm.
The individual was put and rotated for 15 minutes (75 ± 1 rotation per minute).

The sample in the ball mill is transferred to a sieve having a size of 8000 μm or 2000 μm, and the sieve is set in a receiver and covered. Next, shake lightly for 3 minutes while shaking horizontally. Thereafter, the lid and the sieve are removed, the receiver is tilted little by little, and the sample in the receiver is collected with a brush, and weighed to the order of 0.01 g using a direct reading scale. When no sample remains on the sieve, the measurement is completed. If the sample remains on the sieve, fit the sieve into the receiver again, cover and sieve for another minute. When the passing amount is less than 0.05 g, the measurement is terminated. When the passing amount is 0.05 g or more, the passing amount is 0.
Repeat sieving for another 1 minute until less than 05 g. Weigh the sample in the receiver and add the total throughput. This was used as a predetermined sieve for measurement.

The number obtained by subtracting this amount from 100% was defined as the “shape retention” in this specification. 8000
In the case of a sieve of μm, after the surface of the grain was rubbed, cracked materials were mixed as a sieve, so that a sieve of 2000 μm was also tested. Therefore, in the present specification, as an index of shape retention, in addition to the residue of the 8000 μm sieve, the residue of the 2000 μm sieve may be used. The following table shows the results.

[0090]

[Table 14]

[0091]

According to the present invention, there is provided a pesticide preparation which is not easily crushed even when grasped by hand, and which is efficiently diffused after being applied and dispersed. As a result, the agricultural work can be performed efficiently and easily. Is now available. The present pesticide formulation can be put into a paddy field or the like by hand throwing or using a commercially available spraying machine, even if it is not packed with a water-soluble film. Especially in hand throwing, for example,
It can be easily inserted up to a distance of about 10m.

[Brief description of the drawings]

FIG. 1 is a bat used for a water diffusion test. Numbers 1 to 5 in the figure indicate sampling points.

FIG. 2 is a graph showing the results of a diffusion test of Formulation Example 1.

FIG. 3 is a graph showing the results of a diffusivity test of Formulation Example 2.

FIG. 4 is a graph showing the results of a diffusivity test of Formulation Example 3.

FIG. 5 is a graph showing the results of a diffusion test of Comparative Example 1.

FIG. 6 is a graph showing the results of a diffusivity test of Comparative Example 2.

FIG. 7 is a graph showing the results of a diffusivity test of Comparative Example 5.

FIG. 8 is a graph showing a summary of the results of a diffusivity test of each Preparation Example.

Claims (30)

[Claims] 1. A self-diffusing water-floating pesticide having shape retention properties. 2. The pesticide preparation according to claim 1, wherein the equivalent spherical diameter of the pesticide preparation is larger than 5 mm. 3. The pesticide preparation according to claim 1, wherein the equivalent sphere diameter of the pesticide preparation is 10 mm or more. 4. The method according to claim 1, wherein the ratio of the content of the pesticidal active ingredient to the total weight of the preparation is higher than 30%.
The pesticide preparation according to the above item. 5. The pesticidal preparation according to claim 1, wherein the weight per one grain is 0.1 g or more. 6. The pesticide preparation according to claim 1, wherein the shape retention property is 80% or more when a 2000 μm sieve is used by a porcelain ball mill method. 7. The method according to claim 7, wherein the shape retainer is made by a porcelain ball mill method.
80% or more and 95% when using a 000 μm sieve
The agricultural chemical formulation according to any one of claims 1 to 5, which is: 8. The pesticide formulation according to claim 1, which comprises a water-soluble carrier and a film-forming substance. 9. The method according to claim 1, wherein the water-soluble carrier is 5% based on the total weight of the preparation.
9. The pesticide formulation of claim 8, wherein the formulation is present at ~ 95%. 10. The pesticide formulation according to claim 8, wherein the film-forming substance is present at 0.1 to 10% based on the total weight of the formulation. 11. The water-soluble carrier comprises one or more selected from the group consisting of potassium chloride, ammonium sulfate, sodium chloride, urea and sucrose.
0. The agricultural chemical preparation according to any one of 0. 12. The agrochemical formulation according to claim 7, wherein the film-forming substance comprises one or more selected from the group consisting of xanthan gum, sodium alginate, sodium polyacrylate and gum arabic. 13. The method according to claim 1, further comprising a buoyancy-imparting agent.
13. The pesticide preparation according to any one of 12 above. 14. The pesticide preparation according to claim 13, wherein the density of the floating agent is less than 0.3. 15. The pesticidal preparation according to claim 13, wherein the buoyancy-imparting agent is present in a ratio of 1 to 95% based on the total weight of the preparation. 16. The agrochemical preparation according to claim 13, wherein the buoyancy imparting agent is a glass micro hollow sphere. 17. The method according to claim 1, further comprising a disintegration accelerator.
7. The pesticide preparation according to any one of 6. 18. The disintegration accelerator has a molecular weight of 10,000.
18. The pesticide formulation of claim 17, wherein the formulation is less than. 19. The pesticide preparation according to claim 17, wherein the disintegration promoter has a molecular weight of 1,000 or less. 20. The agrochemical formulation according to claim 17, wherein the disintegration promoter is present in a ratio of 1 to 15% relative to the total weight of the formulation. 21. The method according to claim 17, wherein the disintegration accelerator comprises at least one selected from the group consisting of dextrin, croscarmellose sodium, water-soluble gelatin, sodium carboxymethylcellulose, cellulose ether and hydroxypropylmethylcellulose. Or the pesticide formulation according to item 1. 22. The agricultural chemical preparation according to claim 21, wherein the disintegration promoter is dextrin having a molecular weight of less than 10,000. 23. The agrochemical preparation according to claim 1, further comprising a surfactant having a dispersant function. 24. The pesticide formulation according to claim 23, wherein the surfactant having a dispersant function is present in a ratio of 5 to 30% based on the total weight of the formulation. 25. The surfactant having a dispersant function, comprising at least one selected from the group consisting of alkylaryl sulfonate formalin polycondensate, lignin sulfonate and polyacrylate. Or the pesticide formulation according to 24. 26. The agricultural chemical preparation according to any one of claims 1 to 25, comprising a surfactant having a large surface tension lowering ability. 27. The pesticide preparation according to claim 26, wherein the surfactant having a large surface tension reducing ability is present in a ratio of 0.1 to 10% based on the total weight of the preparation. 28. The method according to claim 26, wherein the surfactant having a large surface tension lowering ability includes at least one selected from the group consisting of an acetylene glycol-based surfactant and a dioctyl sulfosuccinate salt. Pesticide formulation. 29. The pesticide preparation according to any one of claims 1 to 28, wherein the pesticidal active ingredient is metominostrobin. 30. The specific gravity of the pesticide formulation is from 0.4 to 1.5.
The agricultural chemical formulation according to any one of claims 1 to 29, which is within the range of.