JP3119878B2 - Jumbo preparations containing pesticides and their production - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a jumbo formulation for casting containing pesticides that effectively controls various weeds, insect pests and plant diseases in vast wetlands such as paddy fields, ponds, and swamps. . More specifically, the present invention relates to a jumbo preparation in which pesticides contained therein are uniformly distributed over a large area when applied to paddy water.

The present invention also relates to a method for producing a jumbo formulation. Briefly, the method of manufacturing this formulation involves placing a bulk porous carrier insoluble in water or an organic solvent in a water-soluble film bag and mixing the active pesticide, surfactant, solvent, and a liquid pesticide mixture of auxiliaries. Absorbing into a bag and heat sealing the bag.

When this formulation is thrown into a paddy rice field or irrigation gate without using a special pesticide applicator, the active ingredient of the pesticide is slowly released over a large area, and is uniformly distributed. It is characterized by its distribution.

BACKGROUND ART The progress of urbanization and industrialization has rapidly transformed modern agriculture into a labor-saving type. Although most farm operations in rice cultivation are becoming more mechanized, pesticides are still often sprayed by farmers. Such work in wetlands is extremely demanding due to the difficulty of walking in mud and exposes farmers to the risk of poisoning pesticides often. In addition, in the Far Eastern countries, including South Korea, aerial spraying of pesticides is available on only a few large farms because of the labor-intensive agricultural work in these countries. Thus, pesticides must be hand-sprayed on rice fields until fully mechanized agricultural work is widespread. In order to effectively control weeds, insects and diseases in large areas such as rice fields, ponds, and swamps, labor-saving pesticide formulations such as fumes and their methods of spraying are commonly used in greenhouses. Development has been long awaited.

Several types of solutions, such as suspension formulations, emulsion concentrates and emulsifiable concentrates, have been developed to reduce the labor and dangers of distributing pesticides in rice fields. However, these preparations have not been used successfully in vast rice fields due to defects such as contact harm to the rice by the sprayed liquid pesticides and inconvenient spraying methods in the rice fields. Therefore, they are used only in limited areas such as narrow rice fields. For these reasons, so-called jumbo preparations are being eagerly developed in Japan and Korea.

Jumbo preparations have different physical and chemical properties from conventional preparations, even when throwing out several to tens of packs per 10a (earl). This is because the active ingredient from the preparation must be evenly dispersed in all of the sprayed rice fields.
Jumbo formulations are much larger than conventional granular or tablet formulations, and are therefore commonly referred to as "jumbo formulations". Currently, a variety of jumbo formulations of different shapes, sizes, and mechanisms of action are being pursued and developed.

A good jumbo formulation must be economical to manufacture and have properties such that when dispersed in a paddy field, the active ingredients are dispersed evenly over a large area. Moreover, their properties must not be such that they deteriorate or disappear even during prolonged storage.

To date, several types of jumbo formulations have been developed. One is a gas generation type. Formulations of this type are in tablet form, usually weighing several grams to tens of grams. This formulation is rapidly broken down into fine particles by vigorous evolution of carbon dioxide gas when in contact with water, and at the same time these particles are dispersed far away.
However, this type of formulation can cause severe phytotoxicity to the rice due to excessive residual activity of the active ingredient at the point of treatment. Because formulations of this type contain some acid or base, pesticides that are easily degraded by chemical reactions (eg, hydrolysis) cannot be prepared as the above formulations and are therefore chemically stable. Only pesticides will be prepared as jumbo formulations. In addition, these formulations tend to lose their gas generating capacity by reaction with water that penetrates during storage. The manufacturing costs of these formulations are considerably higher than conventional formulations.

Another method for producing jumbo formulations is to directly emulsify the desired emulsifying formulation or oily suspension of the pesticide or to absorb them into a water-soluble or substantially water-insoluble carrier, Known are those which are characterized by being placed in capsules or water-soluble bags and then sealing them. However, when a water-soluble bag of a formulation containing a water-insoluble carrier is dissolved in water, the active ingredient of the pesticide is not completely released into the water and often accumulates on the soil surface of rice fields. Therefore, this formulation can not evenly distribute the active ingredients of pesticides, harm the rice around the treated point, and the effect of pesticides,
It is considerably reduced from the place where it applied. In the case of a formulation comprising a water-soluble carrier, when the liquid pesticidal mixture of the formulation is emulsified, the aqueous carrier solution is easily incorporated into the emulsion particles, so that the specific gravity of the emulsion particles is greater than 1. As a result, most of the emulsion particles containing the active ingredient settle on the soil surface, resulting in non-uniform distribution over a vast area, thus damaging the rice at or near the point where the formulation was applied, and reducing the effects of pesticides. It becomes smaller than the place where it was applied.

A variety of jumbo formulations other than the above are also known, but due to their respective disadvantages, they cannot be widely applied to many pesticides and have little practical significance.

Therefore, development of a jumbo preparation which is highly dispersible in water and can be easily produced at low cost has been desired.

DISCLOSURE OF THE INVENTION In order to overcome the problems of the above-mentioned jumbo preparations, the present inventors have energetically studied these preparations.
As a result, we have created a jumbo formulation with excellent physical and chemical properties that can exert the maximum pesticide effect. These formulations are prepared by absorbing a self-emulsifying or easily dispersed liquid pesticidal mixture into a solid, water-non-disintegrating, porous carrier contained in a water-soluble film bag.

Accordingly, one of the objects of the present invention is a liquid pesticide mixture,
It is an object of the present invention to provide a jumbo preparation including a porous carrier that does not disintegrate with water and a water-soluble film bag.

Another object of the present invention is to provide a method for producing a jumbo formulation.

These manufacturing methods include packing water-insoluble particulate matter into a porous bag whose outer surface is laminated with a water-soluble film, absorbing the liquid pesticide mixture into the bag, and sealing the bag; Alternatively, pack a porous bag with water-insoluble particulate matter, seal the bag, insert the sealed bag into a water-soluble bag, absorb the liquid pesticide mixture and seal it; or A block-type porous carrier is prepared by bonding the particulate matter with an adhesive, the porous carrier is inserted into a water-soluble bag, the liquid pesticide mixture is absorbed, the bag is sealed, and the bag is re-aluminized. Inserting into the outer cylinder and sealing it.

BEST MODE FOR CARRYING OUT THE INVENTION The carrier 1 used as an absorbent material for the liquid pesticide mixture of the present invention comprises a powdery or granular substance substantially insoluble in water or an organic solvent in a porous bag. It is a porous pack packed tightly. These powdery or granular materials have few micropores inside, 0.1mm
It is of the above diameter. These substances include inorganic or organic substances. Examples include inorganic minerals such as sea sand, hollow fine particles, calcium carbonate, dolomite, calcined granular bentonite, zeolite, kaolin, talc (talc), and wax wax (waxite); polyethylene, polypropylene, polyvinyl chloride, etc. And organic materials such as sawdust, rice husk, granular charcoal, and grains. Any of the above exemplified materials can be used depending on the kind of the pesticide. Generally, sea sand, calcium carbonate, dolomite, phyllite, talc, hollow fine particles [for example, Microcells SL made in Australia, Scotchlite made in the United States (Sco
tchlite), Japanese-made Shirasu balloon (Shirasu baloo)
n)], as well as polyvinyl chloride are suitable for use. The most preferred carrier materials are sea sand, hollow particulates, calcium carbonate, dolomite, phyllite, and talc, which have a smooth surface, low absorption capacity for organic liquids, and high for water and organic solvents. Has affinity,
This is because it has excellent degradability in the natural world and has high environmental safety.

After packing and sealing one of the carrier materials as tightly as possible in the porous bag, the pack is inserted into a water-soluble bag. A water-soluble bag containing a porous pack is used as an absorbent for a liquid pesticide mixture. The carrier material can also be packed directly into a water soluble bag, the interior of which is laminated with a porous bag. The pore size distribution and total pore volume of the porous pack can be maintained by tightly packing the carrier material. 2 to adjust bulk density
Bags may contain more than one different carrier material.

Carrier 2 used as an absorbent material in the present invention
Is a porous block with an average pore size of 20-100 μm in diameter. This block-shaped carrier 2
It has a compressive strength of 4 kg / cm ² or more and should not be damaged during the manufacturing and forming process of the porous block.
Bound inorganic minerals and porous natural materials that are insoluble in water and organic solvents can be used as porous blocks. Generally, calcium carbonate, talc, calcined granular bentonite, phyllite, dolomite, hollow particulates, and sea sand are suitable for use, all of which are urea,
Bonded using vinyl or phenolic resin adhesive. Most preferred are sea sand, calcium carbonate, talc, dolomite, and dolomite, given their affinity for water and organic solvents, natural degradability, and environmental safety, each mixed with hollow particulates. I do.

Carrier 2 can be prepared by combining sea sand, calcium carbonate, and hollow particulates individually or in combination with hollow particulates by the force of a urea, vinyl, or phenolic resin adhesive, and then curing them. . In the case of sea sand- or calcium carbonate-hollow particulate blocks, the bulk density of the carrier block can be controlled by adjusting the proportion of sea sand or calcium carbonate to be mixed from 30 to 70%. Therefore, the jumbo preparation can be suspended in water or settled in water. Urea, vinyl, or phenolic resin adhesive is added at a rate of 3 to 20% during the manufacture of the porous block of carrier 2.

The weight of the carrier ranges from 2.5 to 99% of the total weight of the jumbo formulation.

If the porous pack (carrier 1) or the porous block (carrier 2) used in the present invention is too light, it is difficult to throw them far. On the other hand, if it is too heavy, it will sink into the soil, resulting in incomplete release of contained liquid pesticides. Therefore, it is necessary to adjust the bulk density and size of the jumbo formulation according to the application and the condition of the farm to which it is applied. When the soil is soft, such as during the period immediately before or immediately after rice planting, the bulk density of the formulation is controlled by using a mixture of sea sand and hollow particulates as a porous carrier in the formulation so that it does not sink into the soil. Must be lowered.

Conversely, when the rice is actively growing on the farm, a high bulk density of the formulation is required to pass through the rice cover (canopy). In addition, jumbo formulations containing a highly water-soluble active ingredient must be of low bulk density, thereby allowing the formulation to float in water and the active ingredient to be well dispersed.

The porous bag used for the carrier 1 has a myriad of pores having an average pore size of 50 μm or more in diameter, and its air permeability is
10 m ³ / m ² / min or more. Tensile strength of porous bag,
Burst strength, and tear strength, as well as cut resistance, are suitably adjusted to prevent tearing or bursting during the manufacturing process or use of the formulation. Those made of natural or synthetic fibers such as nonwovens, gauze, heat-sealable filter papers, and adhesively-sealable filter papers can all be used as materials for making porous bags. In practice, there is no limitation on the porous bag materials as long as they are not soluble in water and organic solvents. However, heat-sealable filter paper for tea bags is the most suitable material for this purpose because it is very inexpensive, readily available, and highly degradable in nature. Heat seal, tea bag, paper (He
atseal Teabag Paper: grade reference number 474601, manufactured by Crompton, UK) is a good example of such a material.

After the liquid pesticide mixture is absorbed by the porous carrier, the carrier is placed in a water-soluble film bag
). The water-soluble bag is then sealed so that the liquid pesticide mixture does not leak or penetrate into adjacent formulations. 25-75μm thick with polyvinyl alcohol, water-soluble cellulose or water-soluble dextrin
Can be used for a water-soluble bag. More than 50% of the film must dissolve in water in a temperature range of 10 to 40 ° C. within 10 minutes and the film must be heat-sealable. Examples of such materials include Monosol 7030, 8533 and 8534 (registered trademark: Chris-Craft, USA).
Industrial Products [Chris-Craft Indus
trial Products, Inc.]), and S-400 and C-
There is 200AX type high theron [HI-SELON] (Japan). The rate of dissolution of the water-soluble bag in water does not significantly affect the efficacy of the jumbo formulation. Thus, any water-soluble bag can be used for this purpose, even if it dissolves relatively slowly in water.
It is preferable to use a water-soluble bag whose inner surface is laminated with a heat sealable porous bag. The sealing portion of the porous bag is covered with a water-soluble bag, and the end of the porous bag is adhered only to the sealing portion so that no portion of the porous bag is exposed to the outside. It is more preferable that it is separated from the water-soluble bag.

Any pesticide can be used in the present invention, such as herbicides, insecticides, and fungicides, provided that they are highly soluble in liquid or organic solvents at room temperature.

The herbicides applicable to the present invention include N-butoxymethyl-2-chloro-2 ', 6'-diethyl-acetanilide (butachlor), 2-chloro-2',
6'-diethyl-N- (2-propoxyethyl) acetanilide (pretilachlor), 2-
Chloro-N- (3-methoxy-2-thienyl) methyl-
2 ', 6'-diethylacetanilide (NSK-850), (S
-(Α, α-dimethylbenzyl) piperidine-1-carbothioate (dimepiperate), S
-(4-chlorobenzyl) N, N-diethylthiocarbamate (benthiocarb), S-ethylazepan-1-carbothioate (molinate [molina
te]), S-benzyl N-ethyl-N- (1,2-dimethylpropyl) thiocarbamate (esprocarb [esprav]
ocarb]), 2,3-dihydro-3,3-dimethyl-5-benzofuranyl-ethanesulfonate (benfresate [be
nfuresate]), 5- (4,6-dimethoxypyrimidine-2
-Yl-carbamoylsulfamoyl) -1-methylpyrazole-4- = carboxylic acid (pyrazosulfuron ethyl), 4-nitrophenyl-2,
4,6-trichlorophenyl ether (chlornitrofen), 5- (2,4-dichlorophenoxy) -2-nitroanisole (chloromethoxyphen [ch
lomethoxyfen]), methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (bifenox [Bi
fenox]), 1,1,1-= trifluoro-2'-methyl-
4 '-(phenylsulfonyl) methanesulfoneanilide (perfluidone), 2- [4-
(2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] -acetophenone (pyrazoxyfen), S-2-methylpiperidinocarbonyl-methyl O, O-dipropylphosphorodithioate (Piperophos), 4,6-dichloro-2
Phenylpyrimidine (fenchlori)
^{m]), N 2 - (} 1,2- dimethyl - propyl) N ⁴ - ethyl -
6-methylthio-1,3,5-triazine-2,4-diamine (dimethametryn), 4- (4-chloro-O-tolyloxy) butyric acid (MCPB), 5-te
rt-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,5-oxadiazole- = 2 (3H)
-One (oxadiazon) and the like.
Insecticides applicable to the present invention include O, O-diethyl-
O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate (diazino
n]), O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (chloropyrifos [chloro
pyrifos]), 2-sec-butylphenylmethyl carbamate (BPMC), dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate (monocrotophos), O, O-diethyl O-4 -Nitrophenyl phosphorothioate (parathione
n]), O-ethyl-O-2-isopropoxycarbonylphenylisopropylphosphoramide thioate (isofenphos), 2,3-dihydro-2,2-
Dimethylbenzofuran-7-yl (dibutylaminothio) = methyl carbamate (carbosulfan [carbos
ulfan]), (RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) = cyclopropanecarboxylate (cycloprothrin), 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (ethofenprox), ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) = Amino-thio] -N-isopropyl-β-alaninate (benfuracarb), O, O-dimethyl O-3,5,6-
Trichloro-2-pyridyl phosphorothioate (chlorpyrifos-methyl) and the like. Fungicides applicable to the present invention include S-benzyl O, O-di-isopropyl phosphorothioate (IBP),
1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinoline-
4-one (pyroquilon), 3-allyloxy-1,2-benz [d] isothiazole-1,1-dioxide (probenazole), di-isopropyl-1,3-dithiolan-2-ylidene Malonate (isoprothiolane) and the like. In addition to the pesticides shown above, any pesticides that are liquid or highly soluble in organic solvents at room temperature can be used in the present invention.

One of the active ingredients of the pesticide, alone or in combination with other active ingredients, can be incorporated into the jumbo formulation of the present invention. The active ingredient in the formulation is from 0.01 to 98 of the total weight
% Range.

Organic solvents having a boiling point of 60 ° C. or higher and a specific gravity of less than 1 can be preferably used for the jumbo preparation of the present invention.

In addition, the specific gravity of the liquid pesticide mixture depends on the organic solvent used. Considering that the specific gravity of the active ingredient is usually greater than 1, it is preferable to use a low specific gravity organic solvent to produce a highly concentrated liquid pesticide. Examples of the solvent include xylene, liquid paraffins, cyclohexanone, cyclohexane, cyclohexanol, methylnaphthalene, Solvesso 100, Solvesso 1
50, Solvesso 200, N-methylpyrrolidone, N-butylpyrrolidone, diethylbenzene, triethylbenzene, ketones (eg, methyl ethyl ketone), polyalkyl glycols, and alcohols (eg, methanol). Although non-polar organic solvents are used as the primary solvent, water-soluble solvents can also be used as co-solvents for the active ingredients of the pesticide.

Various surfactants can be added to the liquid pesticide mixture as emulsifiers, solubilizers or dispersants to give the pesticides good emulsifying and dispersing properties. For this purpose, both nonionic and anionic surfactants can be used. Examples of nonionic surfactants include:
Polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylestyryl aryl ethers, polyoxyethylene polyoxypropylene bulk (block) polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid Esters, polyoxyethylene glycerin fatty acid esters, acetylene glycols, and acetylene alcohols. Examples of anionic surfactants are calcium alkyl benzene sulfonates, sodium alkyl sulfosuccinates, and sodium poly (ethylene glycol) alkyl aryl ether sulfates. In addition to the above surfactants, the surfactants used in the jumbo preparation of the present invention are not particularly limited as long as they can be used as emulsified concentrates or diffusible oils. The surfactant added to the liquid pesticide mixture ranges from 5 to 15% of the total weight, more preferably 10%.

Thickeners such as ethyl cellulose can be added to control the viscosity of the liquid pesticide mixture. Degradation or stabilizers such as epichlorohydrin, soybean oil, phosphoric acid, etc. can also be added to the liquid pesticide mixture to stabilize the physical and chemical properties of the jumbo formulation during long-term storage. , They must not affect the dispersibility of the pesticidal mixture in water. When a jumbo formulation is applied to paddy water, almost all active ingredients must be released from the jumbo formulation within one day. Specifically, more than 90% of liquid insecticides and fungicides and more than 95% of herbicides need to be released within about 24 hours each. Therefore,
It is necessary to adjust the specific gravity of the pesticide mixture in the range of 0.80 to 0.995 and the viscosity according to the pore size of the carrier used.

The jumbo formulations of the present invention are manufactured to weigh 5 to 200 grams per piece, depending on their throw distance and subsequent sedimentation in rice fields. The number of jumbo formulations to be treated will depend on the dispersibility in water of the active ingredients contained in the formulation. 5 to 200 formulations can be applied to the 10a paddy field, but preferably 5 to 50 are applied.

To prevent the liquid pesticide mixture from leaking out of the formulation during storage and from contaminating the human body with the leaked pesticide, the liquid pesticidal mixture is absorbed to 80 to 90% of the total pore volume of the porous carrier.

Although the production process of the jumbo preparation of the present invention is not particularly limited, the present preparation is usually prepared as in the following three examples.

First, (1) two heated seals, tea bags,
A filter paper is inserted between two water-soluble films and their three sides are heat-sealed using an impulse sealer to make a bag. (2) Pack sea sand in the bag.
(3) Add the liquid pesticide mixture to the bag filled with sea sand and heat seal the open portion of the bag.
(4) Put the resulting jumbo preparation in an aluminum outer cylinder,
Seal for storage.

Second, (1) the carrier 1 is prepared by packing the granular material in a heat-sealed tea bag / filter paper bag and sealing. (2) Put the carrier 1 in a water-soluble bag. (3) Add the liquid pesticide mixture to carrier 1 and then heat seal the open portion of the water soluble bag using an impulse sealer. (4) Put the resulting jumbo preparation in an aluminum outer cylinder and seal for storage.

Third, (1) the granular material is mixed with a phenolic resin adhesive, then shaped and cured to prepare a block-shaped porous carrier 2. (2) Put the carrier 2 in a water-soluble bag. (3) Add the liquid pesticide mixture to the carrier 2 and heat seal the open portion of the bag using an impulse sealer. (4) Put the resulting jumbo preparation in an aluminum outer cylinder and seal for storage.

When the jumbo preparations prepared as described above are used for rice fields, they contain a liquid pesticide mixture having a specific gravity of less than 1, but they may be suspended in paddy water or paddy fields depending on the bulk density of the preparation. It will settle on the soil.
As the water soluble bag dissolves in the water, the liquid pesticide mixture is slowly released from the porous carrier to or near the water surface. At the same time, the liquid pesticide mixture is emulsified, diffused and dispersed over a large area so that the active ingredient is evenly distributed in the treated paddy within 24 hours. If the pesticides are highly water-soluble, their dispersibility can be increased by suspending the jumbo formulations so that they are exposed to air. Conversely, if the pesticides are hardly soluble in water and their emulsification stability is very high, the jumbo formulation will settle, thereby preventing the effects of wind from accumulating pesticides in specific locations. Can be prevented. Further, if the jumbo formulation contains a highly volatile, non-viscous petroleum solvent dispersible oil in its oil mixture, the dispersible oil from the formulation will be released rapidly and the water surface will be in the form of a thin film. Is diffused along.

The active ingredient of the jumbo formulation of the present invention is easily dispersed,
Since it is evenly distributed in the water, its effect is hardly diminished unless the surface of the treated paddy water is completely covered with rice stalks, mosses, or aqueous weeds such as duckweed.

The greatest effect can be obtained when 5 to 50 jumbo preparations of the present invention are applied to the paddy field of 10a. The number of applications of the formulation of the invention can of course be adjusted.

When the jumbo formulations of the invention are applied to paddy fields, they float in the water of the paddy field or settle on the soil of the paddy field. As the water-soluble bag dissolves in the water, the liquid pesticide mixture from the porous carrier is slowly released to or near the surface of the water. Since the jumbo preparation of the present invention contains a nonpolar solvent and a surfactant having high self-emulsifiability and dispersibility, the active ingredient is
It will be widely distributed within 24 hours and their concentration will be evenly distributed. Even under conditions such as gusts, these active ingredients are homogeneously dispersed and exert their full effect without any harm to the rice. In addition, since the jumbo formulation of the present invention contains only a liquid pesticide mixture, a porous carrier, and a water-soluble bag, they are manufactured by a simple formulation method using inexpensive materials.

The present invention will be described with reference to the following detailed examples. These examples are provided for illustrative purposes only and are not intended to limit the invention unless otherwise noted. In the examples, "parts" and "%" represent parts by weight and% by weight, respectively. Example 1 Two pieces of filter paper for a tea bag (heat-seal tea bag: grade reference number 474601, manufactured by Crompton, UK; air permeability) 100 m ³ / m ² / min) with two water-soluble films [Type 7030 or Type 8534 Monosol (registered trademark);
Chris-Craft Industrial Products Co., Ltd.], exposing any part of the filter paper to the outside, using three sides of the filter paper with an impulse sealer so that the end of the filter paper is in the center of the seal part. A bag (hereinafter, referred to as a "water-soluble film-filter paper bag") was formed by heat sealing so as not to cause such a problem. Further, the filter paper for a tea bag and the water-soluble film were separately heat-sealed to produce respective bags (hereinafter, referred to as “filter paper bag” and “water-soluble bag”, respectively). These bags were used in preparing the following jumbo formulations.

Example 2 A filter paper bag was filled with 14.4 grams of sea sand and 9.6 grams of Microcells SL350® and sealed. The resulting porous pack was used for preparing the following jumbo formulations.

Example 3 After mixing sea sand and Microcells SL350 in a ratio of 47:47, a phenol resin (resole type) was added to this mixture.
They were added at a mixing ratio of 9:94. The extruding can have carrier mixture is formed into a rod shape having a diameter of 2.7 cm ^2, 0.99
Cured by drying at 2O 0 C for 2 hours and cutting into appropriately sized pieces. The resulting carrier (hereinafter referred to as "porous block") was used for preparing the following jumbo formulations.

Example 4 6.6 parts of pyrazosulfuron ethyl (purity 99.0%)
It was dissolved in 72.8 parts of molinate (purity 98.0%). To this mixture is added, with stirring, 400.6 parts of xylene (industrial grade) and 120 parts of an emulsifier (a mixture of polyoxyethylene alkyl phenyl ether, polyoxyethylene special alkyl phosphonate, calcium dodecyl benzene sulfonate and anti-decomposition agent). , Active ingredient 4
An emulsifiable formulation of molinate-pyrazosulfuron-ethyl containing 7.0% and having a specific gravity of 0.970 was made. The liquid pesticide mixture was used in Examples 5, 6, 7, 8 and 15.

Example 5 Sea sand was ground with a mortar and pestle, sieved, washed with water and dried to prepare sea sand having a particle size of 0.3 to 0.5 mm. 57 g of the sea sand was tightly packed into a water-soluble film-filter paper bag. 11.3 g of emulsifying formulation of molinate-pyrazosulfuron-ethyl was added to the bag and the bag was heat sealed to produce a jumbo formulation with 7.78% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 6 Sea sand was ground with a mortar and pestle, sieved, washed with water and dried to prepare sea sand having a particle size of 0.3 to 0.5 mm. 57 g of the sea sand was densely packed in a filter paper bag, and the bag was heat-sealed to form a porous pack. The resulting porous pack was placed in a 7030 Monosol® water-soluble bag. 11.3 g of an emulsifying formulation of molinate-pyrazosulfuron-ethyl was added to the bag and the bag was heat sealed to give a jumbo formulation of 7.78% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 7 The porous pack of Example 2 was placed in a 7030 Monosol® water-soluble bag. 11.3 g of emulsifying formulation of molinate-pyrazosulfuron-ethyl was added to the bag and the bag was heat sealed to produce a jumbo formulation with 7.78% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 8 57 g of calcium carbonate having a particle size of 0.3 to 0.5 mm was tightly packed in a water-soluble film-filter paper bag. 11.3 g of the emulsifying formulation of molinate-pyrazosulfuron-ethyl was added to the bag and the bag was heat sealed to make a jumbo formulation with 7.78% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 9 15.2 g of sea sand with a particle size of 0.3 to 0.5 mm and 10.1 g of Microcells SL350 were tightly packed in a water-soluble film-filter paper bag. 12.3 g of Lonestar® emulsifying formulation (12% active ingredient; specific gravity 0.92; Hang-Nong Agrochemical Co., Korea) was added to the bag, the bag was heat sealed, 3.9
A jumbo formulation was made with the active ingredients in%. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 10 556 parts of butachlor (87% purity), 100 parts of an emulsifier (a mixture of polyoxyethylene nonylphenyl ether and calcium dodecylbenzenesulfonate), and
344 parts of xylene (industrial grade) were added with stirring to form an emulsifying butachlor emulsifying formulation. 0.3
91 g of sea sand with a particle size of 0.5 mm to 0.5 mm were tightly packed in a water-soluble film-filter paper bag. 18.6 g of an emulsifiable formulation of butachlor was added to the bag and the bag was heat sealed to give a jumbo formulation with 8.21% active ingredient.
The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 11 395.4 parts of diazinon (96.1% purity), 100 parts of an emulsifier (mixture of polyoxyethylene nonylphenyl ether, polyoxyethylene castor oil ether and calcium dodecylbenzenesulfonate), 20 parts of epichlorohydrin, and 484.6 parts of Xylene (industrial grade) was added with stirring to make an emulsifiable formulation of diazinon with a specific gravity of 0.970. 68 g of sea sand with a particle size of 0.3 to 0.5 mm was tightly packed in a water-soluble film-filter paper bag. 13.5 g of an emulsifiable formulation of diazinon was added to the bag and the bag was heat sealed to give a jumbo formulation with 6.3% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 12 231.2 parts of diazinon (96.4% purity), 228.6 parts of BP
MC (purity 97.5%), 100 parts of an emulsifier (a mixture of polyoxyethylene nonylphenyl ether, polyoxyethylene castor oil ether, and calcium dodecylbenzenesulfonate), and 440.2 parts of xylene (industrial grade) are added with stirring. An emulsifying preparation of diazinon-BPMC having a specific gravity of 0.970 was prepared. Particle size
68 g of 0.3 to 0.5 mm sea sand was tightly packed in a water-soluble film-filter paper bag. 13.5 g of the emulsifying formulation of diazinon-BPMC was added to the bag and the bag was heat sealed to a jumbo formulation with 7.38% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 13 42 parts of Etofenprox (96.9% purity), 40 parts of an emulsifier (polyoxyethylene nonylphenyl ether,
A mixture of polyoxyethylene castor oil ether and calcium dodecylbenzenesulfonate), 460 parts of diisopropyl phthalate, and 458 parts of xylene (industrial grade) were added with stirring to form an etofenprox diffusion oil. 50 g of sea sand with a particle size of 0.3 to 0.5 mm was tightly packed in a water-soluble film-filter paper bag. 10 g of etofenprox diffusion oil was added to the bag and the bag was heat sealed to give a jumbo formulation with 6.67% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 14 112.6 parts of hexaconazole (88.8% purity) were dissolved in 500 parts of cyclohexanone (industrial grade). 100 parts of an emulsifier (a mixture of polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phosphonate and calcium dodecylbenzene sulfonate) and 287.4 parts of xylene (industrial grade) are added to this mixture with stirring, and hexaconazole is added. An emulsifiable formulation was made. 68 g of sea sand with a particle size of 0.3 to 0.5 mm was tightly packed in a water-soluble film-filter paper bag. 20g
Hexaconazole emulsifying formulation of the above is added to the bag,
The bag was heat sealed to give a jumbo formulation with 1.67% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

Example 15 22.1 g of a porous block was placed in a 7030 Monosol® water-soluble bag. 11.3 g of an emulsifying formulation of molinate-pyrazosulfuron-ethyl was added to the bag and the bag was heat sealed to give a jumbo formulation of 7.78% active ingredient. The jumbo formulation was placed in an aluminum barrel, which was then heat sealed.

The distribution of the active ingredient after applying the jumbo preparation of the present invention to a paddy field and the effect thereof will be described in detail with reference to the following detailed test examples.

Test Example 1: Distribution of Active Ingredients After Applying Herbicide Molinate-Pyrazosulfuron-Ethyl Jumbo Preparation to Paddy Field and Their Weed Inhibiting Effect Rice seedlings were transplanted to a 13 mx 15.3 m paddy field. This paddy field has a diameter
A 1 cm and 1.2 m long PVC pipe was driven into and divided into 2 mx 2 m. Immediately after transplanting rice seedlings, rice millet (Echinochloa cr
us-galli Beauv.), Erogaris Kuroguwa
i Ohwi), Cyperus serotinus Rott
b.), seeds of squid (Sagittaria trifolia L.) were planted in the center of each fraction. Ten days after transplanting the rice seedlings, the water level in the experimental paddy field was adjusted to about 6 cm. Six julin preparations of the molinate-pyrazosulfuron-ethyl of Example 7 were cast as evenly as possible. Twenty-four hours after treatment, 5 ml of water was sampled from the center of each fraction. Molinate concentration in the sample was measured using high performance liquid chromatography. The effects of the treated jumbo preparation on the control of phytotoxicity and weeds on rice were visually evaluated 30 days after the treatment.

FIG. 1 shows the distribution of the active ingredient in the paddy field 24 hours after the treatment.

Paddy water spontaneously decreased at a rate of up to 2-3 cm per day, and the active ingredient was relatively uniformly distributed, despite the wind blowing continuously upwards in FIG. .

Average molinate concentration in paddy field 24 hours after treatment
At 1.23 ppm, the coefficient of variation was 23.4%. Molinate from the jumbo formulation was more evenly distributed in water than from conventional granules with a coefficient of variation of 25-30%.

Jumbo preparations, and in the fractionation of
No phytotoxicity to the rice was observed except that only one row of rice showed 50, 60, and 30% growth inhibition, respectively. The present jumbo formulation completely suppressed four different weed species planted in paddy fields.

Test Example 2: Distribution of active ingredient after treatment of diazinon / jumbo preparation in paddy field In the growing season of rice, a 13m x 15.3m rice field was 1cm in diameter
And a 1.2m long PVC pipe was driven into it and divided into 2m x 2m. After adjusting the water level of the experimental paddy field to about 6 cm, Example 11
Of the diazinon jumbo preparations of the above were thrown as evenly as possible. 24 m after processing, 5 m from the center of each fraction
l of water was sampled. The diazinon concentration in the sample was measured using high performance liquid chromatography.

FIG. 2 shows the distribution of the active ingredient in the paddy field 24 hours after the treatment.

The active ingredient diazinon was relatively uniformly distributed.
The average concentration of diazinon in paddy water 24 hours after treatment is 0.
At 61 ppm, the coefficient of variation was 28.5%. The coefficient of variation was comparable to that of conventional granules. From these results, an excellent control effect on insect damage is expected.

As mentioned above, the jumbo formulation of the present invention can be applied to rice fields simply by throwing 5 to 50 pieces per 10a without using a special pesticide applicator. This jumbo formulation can save a great deal of labor and reduce the risk of poisoning by pesticides when distributing pesticides. Therefore, this jumbo preparation containing pesticides for throwing,
Conventional formulations can be successfully replaced while having excellent control effects on weeds, insect damage and plant diseases.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Lin He Kyun 305-333, Republic of Korea, Taejong, Yusong-ku, Eo-dong-99, 99 Hanbit apartment 138-805 (56) References JP-A-63-45201 (JP) JP-A-60-202801 (JP, A) JP-A-5-97604 (JP, A) JP-A-5-246802 (JP, A) JP-A-5-339106 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A01N 25/34 A01N 25/08 A01N 25/12 101

Claims (18)

(57) [Claims] 1. A jumbo preparation comprising a water-absorbable porous carrier that has absorbed a liquid pesticide mixture and sealed with a film that is insoluble in water and soluble in an organic solvent. (1) An organic or inorganic porous carrier A sealed porous bag tightly packed with powdered or granular material, or (2) a porous carrier in which the granular material is bonded by an adhesive, and is insoluble in water and organic solvents and does not disintegrate. A jumbo preparation, characterized in that: 2. The organic or inorganic powdery or granular substance of (1) is an inorganic substance of sea sand, hollow fine particles, calcium carbonate, dolomite, phyllite, talc, kaolin, calcined granular bentonite, and zeolite; 2. The jumbo of claim 1, wherein the jumbo is composed of one or more of powdered or granular polymers of polyethylene, polypropylene, and polyvinyl chloride; or, sawdust, hulls, granular charcoal, and cereal organic substances. Formulation. 3. The jumbo preparation according to claim 1, wherein the organic or inorganic powdery or granular substance (1) has an average diameter of more than 100 μm. 4. The organic or inorganic powdery or granular substance (1) is an inorganic substance of sea sand, hollow fine particles, calcium carbonate, dolomite, phyllite or talc.
Or the jumbo preparation according to 3. 5. The jumbo preparation according to claim 1, wherein the granular substance (2) comprises at least one of sea sand, calcium carbonate, talc, phyllite, dolomite, and hollow fine particles. 6. The porous carrier in the form of block (2) which is insoluble in water and an organic solvent and which does not collapse is a mixture of sea sand / hollow fine particles, a mixture of calcium carbonate / hollow fine particles, a mixture of talc / hollow fine particles, and a phyllite-hollow mixture. The jumbo preparation according to claim 1, which is obtained by binding a fine particle mixture or a dolomite-hollow fine particle mixture. 7. The jumbo preparation according to claim 1, wherein the porous bag of (1) is a nonwoven fabric, a gauze or a heat-sealable teabag / filter paper made of natural or synthetic fibers. 8. The jumbo preparation according to claim 1, wherein the porous bag of (1) has an innumerable number of pores having an average pore size larger than 50 μm in diameter. 9. The jumbo preparation according to claim 1, wherein the porous bag of (1) is made of a heat-sealable tea bag / filter paper. 10. The jumbo preparation according to claim 1, wherein the film bag insoluble in an organic solvent and soluble in water is mainly made of polyvinyl alcohol, water-soluble cellulose, or water-soluble dextrin. 11. The jumbo preparation according to claim 1, wherein the film bag insoluble in an organic solvent and soluble in water has a thickness of 25 to 75 μm. 12. The jumbo preparation according to claim 1, wherein the liquid pesticide mixture contains an active ingredient of a pesticide, an organic solvent, a surfactant and an auxiliary. 13. The jumbo preparation according to claim 1, wherein the active ingredient of the pesticide is either liquid at room temperature or highly soluble in organic solvents. 14. The jumbo preparation according to claim 1, wherein the liquid pesticide mixture has a specific gravity of 0.800 to 0.995. 15. The jumbo preparation according to claim 12, wherein the pesticide active ingredient in the jumbo preparation is in the range of 0.01 to 98% of the total weight. 16. The liquid pesticide mixture is absorbed by a water-soluble film bag-sealed insoluble carrier in water and an organic solvent which does not collapse, and the bag is heat-sealed. A method for producing a jumbo preparation comprising: (1) A sealed porous bag tightly packed with organic or inorganic powder or granular material, or (2) A block in which the granular material is bonded by an adhesive and is insoluble in water and organic solvents and does not disintegrate. Shaped object 17. The method according to claim 16, wherein the porous carrier of (1) is prepared by packing a powdery or granular substance into a porous bag whose outer surface is laminated with a water-soluble film. The manufacturing method as described. 18. The porous carrier of (2), which is obtained by mixing a granular substance with an adhesive, molding and curing the same, and which is insoluble in water and an organic solvent and does not disintegrate. 16. The production method according to 16.