WO1995031899A1

WO1995031899A1 - Pesticide composition, pesticidal preparation, and production process

Info

Publication number: WO1995031899A1
Application number: PCT/JP1995/000986
Authority: WO
Inventors: Kouichi Nakamichi; Shougo Izumi; Hiroyuki Yasuura
Original assignee: Nippon Shinyaku Co., Ltd.
Priority date: 1994-05-24
Filing date: 1995-05-23
Publication date: 1995-11-30

Abstract

A waterborne pesticide composition which has a configuration entirely different from that of conventional waterborne pesticide compositions. It contains a macromolecular compound such as a cellulose derivative as the principal ingredient, further contains at least a pesticidally active ingredient and an expansion aid such as talc, is in the form of an expanded molding with a reticular cross section, and has an apparent density of 1 g/cm3 or less. It has a high buoyancy and is well developable on the water surface.

Description

Specification

Agrochemical compositions, formulations and manufacturing technology

The present invention relates to a pesticidal composition. More specifically, the present invention relates to a water-suspension type pesticide composition having an apparent density of 1 g / cm ³ or less (preferably less than 1 g / cm ³ ), which is composed of an expanded molded article having a net-like cross section.

Here, the “expanded molded body” refers to an object that expands due to heating, a change in pressure, a chemical change, or the like, and as a result has a hole therein. “Water-suspension type pesticide composition” refers to a composition capable of releasing a pesticide active ingredient by floating in water or on the surface of water.

Background technology

There are various pesticide compositions depending on the kind of pesticide active ingredient, the place of application, the purpose of use, and the like. One of them is a water-suspension type pesticide composition. Unlike the sedimentation-type pesticide composition, the water-suspension-type pesticide composition is excellent in water surface spreadability because the pesticide composition itself and the pesticide active ingredient that spreads therefrom are hardly adsorbed to the soil. Further, in the pesticidal composition floating on the water surface, the pesticidal active ingredient can be released into the air as a gas depending on the kind of the pesticide active ingredient.

At present, water-suspended pesticide compositions include those in which a pesticide active ingredient is held on a carrier such as pumice, vermiculite, or synthetic resin (Japanese Patent Publication No. 44-8600, Japanese Patent Publication No. 48-1180, JP-A-55-139308, JP-A-63-99327, JP-A-5-155703, etc.), and oily substances obtained by dissolving a pesticidal active ingredient together with a solvent or a surfactant (JP-A-5-78207). No.), pesticide activity Containing a water-soluble polymer film containing a composition containing a water-soluble solid acid and an inorganic floating substance, a carbonate component, and a water-soluble polymer (JP-A-5-139906). There is known a material coated with a water-soluble substance and a water-soluble substance and wrapped in a sheet (Japanese Patent Laid-Open No. 5-194104). Each of these compositions obtains floating ability by a substance that imparts some floating properties.

On the other hand, the multi-screw extruder is one of the screw-type kneading extruders that have completely different performance and applications from the single-screw extruder. Because the entanglements interfere with each other and can generate physically high energy, it is possible to apply treatments that cannot be achieved with a single-screw extruder. Multiaxial extruders have developed mainly in the food and plastic fields, and are widely used in the processing of food (cereals, proteins, animal meat, fish meat, etc.) and in the injection molding of plastics. Recently, its use in the pharmaceutical field has also been reported (PCT W092 / 18106, PCT W094 / 08568, PCT W095 / 05809, etc.).

In the food field, there is a technique for obtaining an expanded molded article using a multiaxial extruder (Japanese Patent Application Laid-Open Nos. 5-284926, 5-192083, 5-23125, and 1). -252267, JP-A-61-9253, etc.). However, none of these technologies are technologies that solve problems specific to the food field (such as texture improvement) and are not technologies that can be transferred to the agrochemical field.

Disclosure of the invention

The main object of the present invention is completely different from the conventional water-floating pesticide composition. An object of the present invention is to provide a water-suspension type pesticide composition in a form. That is, it is an object of the present invention to provide a water-suspension type pesticide composition which does not acquire the buoyancy by a substance such as a carrier or oil, but is substantially obtained by a large number of fine voids of the composition itself.

As a result of various studies, the present inventors have found a water-suspendable agricultural chemical composition that can achieve the above object, and have completed the present invention.

The water-suspension type pesticide composition according to the present invention (hereinafter, referred to as “the present composition J”) contains a polymer compound as a main component, and further contains at least a pesticide active ingredient and a leavening aid. And an apparent density of 1 g / cm ³ or less consisting of a swollen molded body having a net-like cross section * S> o

Here, “subject” means that the component has the highest content among all the components.

Hereinafter, the composition of the present invention will be described in detail.

The present invention composition can be apparent density float in the water or the water from being less 1 g / cm ^s. However, those having an apparent density of less than 1 g / cm ³ are preferable. This is because the pesticide composition floating on the water surface is superior in water spreadability, and can be a composition capable of releasing a pesticide active ingredient into the air as a gas.

Since the composition of the present invention has a net-like cross section, it has a large number of fine pores independently closed inside.

Examples of the polymer compound according to the present invention include cellulose derivatives, starch derivatives, polyacrylic acid derivatives, polyvinyl derivatives, proteins, and rubbers. Some of these are hydrophilic Some are hydrophobic, but any can be used in the present invention. In the present invention, a cellulose derivative is preferred.

Examples of the hydrophilic polymer compound according to the present invention include the following.

1. Cellulose derivatives

Methylcellulose, hydroxypropyl cellulose, hydroxypropylmethylcellulose, hydroxypropyl cellulose, carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose.

2. Starch derivatives

Pregelatinized starch, pregelatinized amino starch, carboxyethyl starch, carboxymethyl starch, oxidized starch, pullulan 0

3. Polyacrylic acid derivative

Alkaline salts of polyacrylic acid, alkaline salts of polymethacrylic acid,

4. Boli Bull derivative

Polyvinyl pyrrolidone, polyvinyl alcohol.

5. Proteins

Gelatin, collagen, casein, albumin, gluten.

6. Rubbers

Gum arabic, tragacanth, carrageenan.

Examples of the hydrophobic polymer compound according to the present invention include the following.

1. Cellulose derivatives Ethylcellulose, hydroxypropyl mouth propyl methylcellulose acetate, succinate, hydroxypropylmethylcellulose phthalate, carboxymethylethylcellulose, cellulose acetate fluorate. 2. Boriataryl acid derivative

Methacrylic acid copolymer, aminoalkyl methacrylate copolymer.

The above-mentioned hydrophilic and hydrophobic polymer compounds may contain two or more kinds, and may contain a mixture of a hydrophilic polymer compound and a hydrophobic polymer compound. In any case, the object of the present invention can be sufficiently achieved.

The hydrophilic polymer compound according to the present invention forms a gel when contacted with water and can exhibit adhesiveness. Therefore, when the proportion of such a hydrophilic polymer compound is increased, it is possible to prevent a certain degree of deviation, outflow and scattering due to wind and rain. In addition, pesticide active ingredients can be effectively released at the plant origin of the applicable plant. Furthermore, the composition of the present invention directly adheres to pests, and can effectively control and kill. Such an effect due to adhesion is an effect that has not been observed in conventional agricultural chemical compositions.

The hydrophobic polymer compound according to the present invention can contribute to suppression of disintegration or dissolution of the composition in water. Therefore, if the ratio of the hydrophobic high molecular compound is increased, a long-time floating can be secured. In addition, the release of the pesticidal active ingredient can be delayed, and the efficacy of the pesticidal active ingredient can be maintained for a long time.

The composition ratio of the polymer compound is as follows: polymer compound, other constituent components, purpose Although it depends on the composition of the present invention, it is suitably 25 to 94% (w / w), preferably 40 to 80% (w / w), and more preferably 50 to 70% (w / w). is there. A composition having a composition ratio of less than 25% (W / W) may have the form of the composition of the present invention depending on other components, but may not have sufficient adhesive and sustained release properties.

The leavening aid is an additive for providing a large number of independently closed fine uniform holes inside the composition of the present invention. It is considered that this expansion aid gives the raw material an effect similar to the zeolite action when the composition of the present invention is produced by a multiaxial extruder described later. Without this expansion aid, the composition of the present invention cannot be obtained by a multiaxial extruder. Therefore, the leavening aid is a very important component for the present invention.

Examples of the leavening aid which can be used in the present invention include talc, dried aluminum hydroxide gel, synthetic aluminum gateate, hydrogen phosphate, calcium carbonate, precipitated calcium carbonate, calcium hydrogen carbonate and the like. it can. These leavening aids may contain two or more kinds. Even if two or more kinds are contained, the purpose as a leavening aid can be achieved.

The composition ratio of the leavening aid varies depending on the leavening aid, other constituent components, the intended composition of the present invention, etc., but is suitably 5 to 40¾i (w / w), preferably 10 to 30% (w / w). w / w), more preferably 15 to 20% (w / w). A composition having a composition ratio of less than 5% (w / w) may not have sufficiently fine and uniform pores, and a composition having a composition ratio of greater than 40 (w / w) may have the shape of the composition of the present invention. May not. The pesticidal active ingredient that can be used in the present invention is not particularly limited, and examples thereof include the following.

1. herbicide

Oxaziazone, pyrazolate, mefunaset, bretilachlor, benzozone, pilophos, dimelone, bilazosulfronethyl, nabloalide, bensulfuronmethyl, simetrin, falachlor, metrachlor, Atrazine, cyanadine, trifluralin.

2. Insecticides

Diazinon, cyclobrotrin, bensultap, etofen block, dimethate, bubrofedin, MEP, MICP, MPMC, ethiofencalp, benfracarb, acephate.

3. Fungicide

Probenazole, IBP, EDDP, isobrothiolane, mebronil, penciclone, thiophanate methyl, hexaconazole, flyside, vitelenol, triflumibul, tricyclazole, josetyl, and voridamycin.

These pesticidal active ingredients may contain two or more kinds.

The composition ratio of the pesticidal active ingredient varies depending on the pesticidal active ingredient, other constituents, the intended composition of the present invention, and the like, but is suitably 0.01 to 45% (w / w), preferably 0.1 to 30% (w / w). w / w). More preferably, it is 1 to 20% (w / w). When the composition ratio is less than 0.01% (w / w), the effect of the pesticide active ingredient may not be exhibited, and when the composition ratio is more than 45% (w / w), the composition of the present invention has no deformation. There are cases. It has an apparent density of 1 g / cm ³ or less (preferably made of a swollen molded body having a cross-section that is blended with the above-mentioned polymer compound, pesticidal active ingredient and swelling aid, and in addition to fat and Z or a surfactant). Is less than 1 g / cm ³ ).

By blending fats and oils, it is possible to mainly improve water repellency and water surface spreadability, and it is possible to smoothly produce the composition of the present invention using a multiaxial extruder described later (like a fluidizer). Effect). By adding a surfactant, the water surface spreadability can be mainly improved. The fats and oils also have a function of suppressing the release of the pesticidal active ingredient from the pesticide composition. Therefore, fats and oils can be added when sustained release is desired.The fats and oils which can be used in the present invention may be any of vegetable fats and oils, animal fats and oils, fatty oils, solid oils and the like. Can be mentioned

O 0

1. High fatty acids

Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, araquinic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid.

2. High fatty acid ester derivatives

Esters such as the glycerin, ethylene glycol, propylene glycol, sorbitol, and polyethylene glycol of the high fatty acids listed above. Glycerides of saturated fatty acids obtained from animals and plants, and mixtures thereof, and hardened fats and oils of glycerides derived from animals and plants. Glycerides of unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, and ricinoleic acid, and mixtures thereof. 3. High alcohol

Pentadecanol, hexadenicol, cetyl alcohol, hebutadecanol, stearyl alcohol, nonadenicol, eicosanorl, wool alcohol, cholesterol.

4. High alcohol derivative

Cholesteryl palmitate, plant sterol palmitate. Examples of the surfactant that can be used in the present invention include nonionic, anionic, and cationic surfactants that are commonly used in agricultural chemical formulations. Specifically, for example, polyoxyethylene Alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene hexitane fatty acid ester, polyalkylene glycol alkyl ether, alkyl benzene sulfonate, lignin sulfonate, naphthyl methane sulfonate And alkyl sulfosuccinates.

Either one of these fats and oils and surfactants may be blended, or both may be blended. In addition, each may contain two or more kinds. Either of them can fulfill the above purpose as a fat or oil and a surfactant.

The composition ratio of the whole fat and oil and the surfactant varies depending on the fat and oil, the surfactant, other components, the intended composition of the present invention, etc., but is preferably 0.1 to 20% (w / w). Preferably it is 0.5 to 10% (w / w), more preferably 1 to 5% (w / w). When this composition ratio is larger than 20% (w / w), the composition of the present invention may not have a form.

In addition, it also contains pesticide release modifiers and plasticizers. The composition of the present invention also includes an expanded molded article having a cross-section having a net density of 1 g / cm ^s or less (preferably less than lg / cm ^s ).

Here, the term "pesticide release regulator" refers to a substance capable of controlling the release rate of the pesticidally active component from the composition of the present invention. Examples of the pesticide release modifier that can be used in the present invention include the above-mentioned oils and fats, the above-mentioned hydrophobic high molecular compound, the above-mentioned hydrophilic high molecular compound, and low-substituted hydroxybu mouth building having a swelling action upon contact with water. Disintegrants such as cellulose and microcrystal cellulose can be exemplified. Fats and oils and hydrophobic high molecular weight compounds can suppress the release of active agricultural chemicals, and hydrophilic high molecular weight compounds and disintegrants can enhance the release of active agricultural chemicals. Up to about 45¾i (w / w).

Examples of the plasticizer that can be used in the present invention include polyethylene glycol, propylene glycol, glycerin, and triethyl citrate. These plasticizers may contain two or more kinds. Even if two or more kinds are contained, the purpose as a plasticizer can be achieved.

In the composition of the present invention, for example, all components (polymer compound, pesticidal active ingredient, leavening aid, and other components) and water are collectively processed by a multiaxial extruder (hereinafter simply referred to as “extruder”). It can be manufactured by doing so.

Here, Γbatch processing j ”means that all components and water are substantially simultaneously subjected to the processing possessed by the extruder, such as shearing, mixing, kneading, compression, and extrusion. The main part of the extruder is mainly composed of a barrel called a barrel, a die corresponding to the exit, and a screw mounted with various screw elements. There are usually multiple barrels through which the screw passes. The screw elements include trapezoidal screw elements, trapezoidal cut screw elements, trapezoidal reverse cuts, ball screw elements, and kneading paddles (also known as kneading discs). It can be done arbitrarily. The components sent into the barrel move inside the barrel by a screw, and are subjected to processing such as shearing and mixing by a screw element such as a kneading paddle in the barrel, and the die pores are removed. Extruded from. Normally, each barrel and die can be independently temperature controlled.

In the present invention, an ester having basic characteristics such as a transport function of a high-moisture / high-oil content raw material, a mixing function, a shearing function, a compressing function, a crushing function, and a heating function, which is generally used in the food field, the plastic field, and the like. If it is the first one, it can be used as it is. The composition of the present invention can be sufficiently obtained by using a biaxial extruder having two screws.

In addition, there are various types of extruders, such as a non-interlocking counter-rotating or co-rotating extruder and a complete or partially interlocking counter-rotating or co-rotating extruder. In the present invention, it is preferable to use a completely interlocking type co-rotating extruder, and particularly preferably a fully interlocking type co-rotating twin-screw extruder having a kneading paddle (kneading disk) on the shaft. Batch processing in the extruder does not necessarily have to take place in all barrels and die of the extruder. is there

"·,

The composition of the present invention can be obtained by performing batch processing in and after the barrel.

As a method of batch treatment in an extruder, ① All the components (high molecular compounds, pesticide active ingredients, expansion aids, and other components) are mixed in advance with water and supplied through the main feed hole of the extruder. B) Method of batch treatment, ② Method of mixing all components in advance, supplying this through the main supply hole of the extruder, supplying water through the auxiliary supply hole, and performing batch processing, ③ Component Among them, "Some components" are mixed in advance and supplied from the main supply hole of the container, and "The remaining components J and water are supplied from the auxiliary supply holes and processed collectively. Method, one of the “components” is supplied from the main supply hole of the extruder, and the remaining components are supplied from the auxiliary supply hole, and water is supplied from the auxiliary supply hole to collectively treat the components. Can be. Of these methods, (2) and (3) are preferred. Here, the main supply hole is the most basic supply hole capable of supplying the raw material into the barrel, and the auxiliary supply hole is used to supply water, additives, etc. additionally into the barrel. Supply holes other than the main supply holes. In the above item (2), if necessary, any constituent component and water or water can be further supplied from the trapping supply hole. In the above item (2), if necessary, an arbitrary component can be further supplied from the auxiliary supply hole. In the above ③, for example, the polymer compound and the pesticide active ingredient Some components may be referred to as “swelling aids”, water and other components may be referred to as “the remaining components”. In any case, the composition of the present invention can be obtained. It is preferable to include the high molecular compound in "some components". The “remaining components” can be supplied as a mixture from one auxiliary supply hole, or individual components or a mixture of arbitrary components can be supplied from a plurality of auxiliary supply holes. In any case, the composition of the present invention can be obtained. A part of the “several components” supplied from the main supply hole may be included in the “remaining components” and supplied from the auxiliary supply hole.

In (1) above, the “component of r-D” is preferably a polymer compound. The `` remaining components '' can be supplied as a mixture from one auxiliary supply hole, or individual components or a mixture of arbitrary components can be supplied from multiple auxiliary supply holes. it can. In any case, the composition of the present invention can be obtained. In addition, a part of “one component” supplied from the main supply hole may be included in “r remaining components” and supplied from the auxiliary supply hole.

Premixing of each component can be performed manually by a machine such as an Eder mixer, a V mixer, a double cone mixer, a cubic mixer, a Ripon mixer, or the like.

The supply of each component and water into the barrel can be performed manually or by a raw material feeder generally provided in the extruder to be used, but with a device capable of supplying the components at a constant speed. If there is, there is no particular limitation. Such devices include, for example, a screw feeder, a table feeder, and a belt-conveyor metering system. Supply machine, electromagnetic feeder, etc. can be used.

The amount of each component to be charged into the extruder can be appropriately set within the range of each component ratio described above.

The amount of water used varies depending on the components, the type and type of extruder, the processing conditions, the intended composition of the present invention, etc., but is added in the range of 5 to 20% (w / w) for all the components. be able to. If it is less than 5% (w / w), poor expansion may occur, or the frictional resistance in the barrel may increase, resulting in an excessive load and no discharge. If it exceeds 20% (w / w), poor expansion may occur.

The water mentioned here includes not only water but also isotonic water such as physiological saline, neutral or acidic or basic buffer, or ammonia water.

The processing conditions of the extruder will be described.

The temperature of the barrel and die of the extruder can be appropriately set according to the constituent components, the model and type of the extruder, the intended composition of the present invention, and the like. Specifically, 70 to 150, but can be set preferably to 100 to 120 ^e C. Although the composition of the present invention can be obtained even when the temperature is set to a higher value at 150, if the temperature is set too high, the pesticidal active ingredient may be decomposed. If the temperature is lower than 70, the composition of the present invention may not be obtained.

The screw rotation speed (processing speed) can be set within the allowable range of the extruder used. An extruder with a longer barrel length can increase the rotation speed. This is because the longer the barrel length, the higher the processing capacity such as mixing and shearing. In particular 50 rpm or more is suitable, and 50 to 300 rpm is preferred.

Discharge pressure, 10-1501 (8 111 ² is suitably, 30~120kg / cm ^a virtuous preferable.

The shape and combination of the screw elements that can be used in the present invention can be selected without any particular limitation. However, it is preferable to use at least one pair of a kneading paddle (kneading disc) having strong kneading action and shearing action.

The discharge die can be appropriately changed depending on the intended composition of the present invention. Specifically, there can be mentioned those in which the diameter of the pores of the discharge die is 0.5 to 5 hidden.

It is considered that the expansion caused by the extruder is caused by a sudden return of the mixture of all the components under appropriate heat and high pressure in the barrel to normal pressure by being pushed out of the die. It is. At that time, since the water present in the mixture is also vaporized at the same time, it is considered that the water vapor also plays a role in the expansion phenomenon by the extruder.

Hereinafter, the pesticide formulation according to the present invention (hereinafter referred to as “formulation j of the present invention”) will be described in detail: The formulation of the present invention can be produced by formulating the composition of the present invention by a conventional method. The following methods can be used.

All the constituent components batch-processed by the extruder become the composition of the present invention and are continuously extruded from the pores of the die. This can be cut to a desired length by a suitable cutting machine, for example, a roller type crusher, a cutter mill, a pin mill, or the like. This cut one is The preparation of the present invention in a granular form can be obtained as it is. Further, the composition of the present invention extruded from the pong holes of the die is, for example, rotated by a rotary cutter (for example, a rotary cutter for KEXN-30, manufactured by Kurimoto Iron Works) provided at the tip of the die. By cutting into pieces, a granular preparation of the present invention can be directly obtained without any special abduction operation.

By compressing and molding the cut granular composition of the present invention, a tablet-form preparation of the present invention can be obtained. Also, the granules or tablets can be packaged with a hydrophilic polymer film that dissolves quickly in water. This packaged product is also the preparation of the present invention.

As more preferable preparations of the present invention, those in which the surface of the above-mentioned preparation of the present invention is further coated with a fat or oil and / or a surfactant can be mentioned. By coating the above-mentioned preparation of the present invention with oil and Z or a surfactant, water surface spreadability can be obtained or enhanced.

The types and constitutional ratios of the fats and oils and surfactants that can be used in the present invention are the same as described above.

The above-mentioned coating is performed by dissolving or dispersing a fat or oil and / or a surfactant in a suitable solvent such as water or an organic solvent (e.g., ethanol), and spraying the formulation of the present invention, or a fat or oil and / or a surfactant. It can be carried out by a method of simply mixing powder or liquid. These can be performed by, for example, a fluidized bed granulation coating apparatus, a rotary drum type coating apparatus, a ribbon type or V type mixer, or the like.

The invention's effect

The composition of the present invention (the preparation of the present invention) can have adhesiveness. In addition, the composition of the present invention (the preparation of the present invention) can have a high floating force and a high water surface spreading power, and can also be a sustained-release preparation.

The composition of the present invention (the preparation of the present invention) can be produced by an extruder in a simple, large-scale, and basically continuous manner. Therefore, the method for producing the composition of the present invention (the preparation of the present invention) is excellent in practicality and industrial properties.

Best form for carrying out the invention

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples. The following barrel numbers are assigned in ascending order from the barrel on the sample supply side (entrance side).

Example 1

A mixture of 12 g of mefenacet, 45 g of talc, 43 g of hydroxypropyl pill cellulose, and 20 Og of ethylcellulose is mixed with a diameter of 32 mm0, an effective L / D of 20, and a screw pattern of 16 P. , 12P, 9.6P, 8P, 30deg, 8t x 3 pieces' 30deg (reverse) screw, 2 mra 0 x 1-hole twin-screw extruder equipped with a 1-hole die (KE XN- 30S- 20 ; Kurimoto Iron Works, same hereafter) was injected into the main supply hole from the hopper at a rate of 30 g per minute. The processing temperature was set to 100 ° C for each barrel and die, and the screw speed was set to 80 rpm while adding purified water at a rate of 2 m1 per minute from the auxiliary supply hole. The treatment was performed at a dipping speed to obtain the composition of the present invention. The apparent density of such a composition was 0.21 g / cm ³ .

Example 2

Mefenaset 12 g, Talc 36 g, Hydroxib mouth Pilsell 100 g of loin, 140 g of ethylcellulose and 12 g of stearic acid were mixed and treated under the same conditions as in Example 1 to obtain a composition of the present invention. The apparent density of such a composition was 0.26 g / cm ^s .

Example 3

The present invention was prepared by mixing 12 g of mefenacet, 36 g of talc, 180 g of Pircellulose with hydroxy mouth, and 72 g of sodium boriaacrylate and treating them under the same conditions as in Example 1. A composition was obtained. The apparent density of the composition was 0.4 g / cra ³ .

Example 4

15 g of dimechate, 36 g of dried aluminum hydroxide gel, 100 g of hydrmethyl cellulose, 50 g of sodium polyboacrylate, 50 g of gelatin, 50 g of ethyl cellulose mixing, another setting each barrel and die 1 2 0 ^e C, to obtain the composition of the present invention performs processing under the same conditions as in example 1. The apparent density of such a composition was 0.32 g / cm ³ .

Example 5

A mixture of 12 g of mefenacet, 30 g of talc, 100 g of hydroxypropyl pilcellulose, 68 g of ethylcellulose, and 90 g of microcrystalline cellulose was mixed with the same mixture as in Example 1. A twin-screw extruder equipped with a ridge and a die was charged into the main feed hole from the hopper at a rate of 30 g / min. The processing temperature was set at 90 for each barrel and die section, and the screw rotation was performed while adding a 50% (w / w) aqueous solution of propylene glycol from the auxiliary supply hole at a rate of 2 ml per minute. The composition was processed at an extrusion speed of 100 rpm to obtain the composition of the present invention. The apparent density of such a composition was 0.61 g / cm ³ .

Example 6

A mixture of 12 g of methnaset, 36 g of talc, 126 g of pilcellulose with hydroxyb mouth, and 126 g of ethylcellulose was treated under the same conditions as in Example 1 to obtain the composition of the present invention. Obtained. The apparent density of such a composition was 0.44 g / cm ^s . The composition of the present invention was crushed into a range of 100 to 100 // using a roll granulator (GRN-1041: manufactured by Nippon Granulator Co., Ltd .; 0 g was placed in a fluidized bed coating apparatus, and a solution prepared by dissolving 2 g of stearate and 2 g of polyethoxyethylene alkyl phenyl ether in 50 ml of a mixture of methylene chloride and ethanol was sprayed onto the apparatus. The preparation of the present invention coated with fats and oils was obtained.

Example 7

3 g of Etofen Blocks, 57 g of calcium carbonate, 120 g of hydroxypropyl methylcellulose, and 120 g of pillmethylcellulose phthalate hydrochloride were mixed, and the mixture was mixed with the same screw and 1 screw as in Example 1. The hopper was fed into the main feed hole at a rate of 30 g per minute into a twin-screw extruder equipped with a 5-hole die. The processing temperature was set to 100 ° C for each barrel and die section, and a 30% aqueous solution of triethyl citrate (w / w) was added from the auxiliary supply hole at a rate of 2 ml per minute. Processing was performed at an extrusion speed of 100 rpm at a screw rotation speed to obtain the composition of the present invention. The apparent density of such a composition was 0.43 g / cm ³ .

Test example 1 Floatability test The composition of the present invention obtained in Examples 1 and 2 was cut into a length of 2 cm, and this was put into a glass beaker of 500 m1 containing 400 m1 of water, and then was added at room temperature. Buoyancy was measured over time.

The measurement of buoyancy is measured using a micro load transducer (UL-10GR:

(Shinkoh Minebea) was used, an attachment for fixing the sample was attached to the sample, and the sample was mounted. Then, the force required to submerge the sample in water was measured electrically.

The water in the beaker during the test was taken out of the lower layer every day at 20 Om1, and 200 ml of fresh water was added for the test.

As a result, as shown in FIG. 1, it was observed that the compositions of the present invention obtained in Examples 1 and 2 floated immediately after the introduction of the test solution, and also floated 10 days after the test.

Test example 2 Water surface spreadability test

Pour about 12 L (liter) of water into a plastic container 20 cm wide and 2 m long so that the water depth is about 3 cm. 1 g of the composition of the present invention obtained in Examples 2 and 6 was charged from the center of the container, and the water surface spreadability of the composition of the present invention was measured.

The evaluation of the expandability was performed by measuring the spread width of the sample expanded in the major axis direction at 10 seconds, 30 seconds, and 60 seconds after the composition of the present invention was charged. The results are shown in Table 1.

table 1

(Unit: cm) As shown in Table 1, the composition of the present invention started developing immediately after spraying, and had good water surface deployability. Test example 3 Composition bias test

The soil was packed in a 1 mx 1 m container, and paddy rice seedlings were transplanted every 15 cm from the end, and harbored at a water depth of about 3 cm. 5 g of each of the compositions of the present invention of Examples 3 and 4 as granules and plastic beads having a particle size of about 1.0 mm were added from the center of the container. After that, let it stand for 1 hour, and then change the wind speed (0, 2, 4, 6 m / s) for 10 minutes as shown in Fig. 2: We observed the movement of the drug floating on the surface of the water when the air was blown (offset phenomenon). The results are shown in Table 2.

Table 2 No deviation at all) f No deviation

： About half the bias

: Almost)

As shown in Table 2, the composition of the present invention floated on the water surface after being charged in water, and thereafter, the composition was prevented from shifting due to adhesion to the particles or to the seedlings, thereby maintaining a substantially uniform spread state.

Test Example 4 Release Test According to the Japanese Pharmacopoeia Dissolution Test Method 2 (paddle method), a dissolution test of each invention composition was performed under the conditions of 900 ml of water and a paddle rotation speed of 50 rpm. Quantification was performed by high performance liquid chromatography.

The sample was a granular product of the composition of the present invention obtained in Examples 1, 2, and 5.

¾: Used 0 As a result, as shown in FIG. 3, the composition of the present invention could give an arbitrary release rate by changing the amount of the pesticide release modifier added.

Brief description of drawings

Figure 1 shows the buoyancy measurement results.

The horizontal axis represents time (say), and the vertical axis represents buoyancy (mg). 1-1 represents the buoyancy of the composition of the present invention obtained in Example 1, and 1 □ 1 represents the buoyancy of the composition of the present invention obtained in Example 2.

FIG. 2 shows a schematic diagram of the experimental method of Test Example 3.

Y indicates the permanent rice seedling for transplantation, and → indicates the direction of the blast.

Figure 3 shows the dissolution test results.

The horizontal axis is the elution time (time), and the vertical axis is the elution rate of mefnaset.

) Represents each. 1-1 shows the elution curve of the composition of the present invention obtained in Example 1, 1 shows the elution curve of the composition of the present invention obtained in Example 2, and 1 shows the elution curve of the composition of Example 5. The elution curve of the obtained composition of the present invention is represented by <

Claims

The scope of the claims

1. It contains a polymer compound as a main component and at least an agricultural chemical active ingredient and a swelling aid, and has an apparent density of 1 g / cm ³ or less made of a swelled molded body having a net-like cross section. Pesticide composition.

2. Polymer compound apparent density of 1 g / cm ^s following agrochemical composition comprising bulky formed body according to claim 1 wherein the hydrophilic polymer compound.

3. The agricultural chemical composition having an apparent density of 1 g / cm ³ or less, comprising the expanded molded article according to claim 1, wherein the polymer compound is a hydrophobic polymer compound.

4. The bulky molded article according to claim 1, wherein the polymer compound is selected from the group consisting of a cellulose derivative, a starch derivative, a polyacrylic acid derivative, a polyvinyl derivative, a protein, and a rubber. An agricultural chemical composition having a density of lg / cra ³ or less.

5. A pesticidal composition having an apparent density of 1 g / ciii ³ or less, comprising the expanded molded article according to claim 1, further comprising an oil and fat and a surfactant.

6. Further pesticide modified release剂and or apparent density comprised of bulky formed of claims 1 to 5, wherein it contains a plasticizer is 1 g / cm ^s following agrochemical composition.

7. A pesticidal composition obtained by coating the pesticidal composition according to claim 1 with fats and oils and Z or a surfactant.

8. The method for producing an agricultural chemical composition according to any one of claims 1 to 6, wherein all components and water are collectively processed by a multiaxial extruder.

9. A pesticide formulation derived from the pesticide composition according to claims 1 to 7.