JP3433157B2 - High concentration pesticide solid formulation - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a suspension containing a high concentration pesticide active ingredient by blending a polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in a molecule. A high concentration pesticide solid preparation obtained by wet pulverizing a liquid (slurry) and kneading and granulating the obtained suspension, a method for producing and using the same, and a high concentration pesticide solid preparation containing a water-soluble film Alternatively, the present invention relates to a pesticide formulation for paddy field packaging in a sheet and a method for using the same.

[0002]

2. Description of the Related Art Conventionally, pesticides have been formulated into various dosage forms, such as powders, wettable powders, emulsions and granules, and sprayed on the surface of water, soil and plants for convenience of use.

Conventionally, the solid pesticide raw materials have been conventionally pulverized mainly by dry pulverization using a jet mill or a hammer mill.
Recently, since the number of extremely poorly soluble active ingredients has increased,
More frequent pulverization has been required. However, conventional dry crushing cannot cope with such fine crushing, and therefore, wet crushing using an attritor, a bead mill or the like has been widely used recently.

In recent years, as agrochemical dosage forms, powdered dosage forms and dosage forms containing organic solvents tend to be shunned due to environmental concerns and growing health awareness of farmers. In addition, for example, as laboratories are aging, part-time workers are increasing, and women's labor is increasing, labor-saving pesticide spraying is required.

[0005] From the above, a so-called 1 which can be applied without dusting, a flowable agent for paddy fields which can be treated without using a machine, and an active ingredient content in granules to reduce the amount of application as a preparation. Dosage forms such as kilo granules and granular wettable powders with less dusting have been widely used.

However, 1 kg granules and hydratable granules are
Since the content of the active ingredient is higher than that of the conventional so-called 3 kg granule, especially when the active ingredient is wet-milled, it is necessary to pulverize the suspension containing the high-concentration active ingredient when granulating. There is a drawback that the amount of kneading water becomes too large and granulation becomes impossible.

Furthermore, recently, a solid formulation of a pesticide is divided into water-soluble films, and the package is a lightweight labor-saving pesticide formulation that can be treated by throwing it from a ridge or the like without entering a paddy field (that is, , Agricultural chemicals for throwing in paddy fields) have been proposed (JP-A-3-173802) and commercialized, and these are also called jumbo agents or pack agents.

[0008] Such a paddy field throwing formulation is, for example, one in which a large effervescent tablet is directly thrown into the paddy field (JP-A-6-107503), and a small effervescent tablet is used as a package of a water-soluble film. To the paddy field (Japanese Patent Laid-Open No. 5-339106), a water-soluble carrier such as potassium chloride granulated with a water-soluble film-forming polymer, and an agrochemical active ingredient contained in the water-soluble film. What is used as a sachet, which is thrown into a paddy field (Japanese Patent Laid-Open No. 5-78207), and a pesticide solid formulation which is prepared so as to float and spread on the water surface is sachet-packaged into a water-soluble film and thrown into a paddy field ( JP 6-3
No. 36403) and an oil preparation having water spreading properties are packed in a water-soluble container and thrown into a paddy field (Japanese Patent Laid-Open No. 5-339103).

These pesticide formulations for paddy field dumping have the first purpose of saving labor and energy, and for this purpose, the amount of formulation to be dropped per unit area and the number of thrown doses should be kept as high as possible. It is necessary to reduce. In addition, in particular, the above-mentioned agricultural chemical formulation for dumping in paddy fields has a process of packaging in small sachets, so the production cost tends to be high, and in order to reduce the cost, make a high content formulation and treat it in a unit area. It is necessary to keep the absolute dosage of the formulation as low as possible and the number of sachets thrown in as low as possible. For this reason, it is necessary to wet-grind the suspension as high as possible, but wet-grinding using a conventionally known surfactant has never been able to grind a satisfactory content. That is, when a surfactant that has been conventionally used for wet pulverization of a suspension is used for wet pulverization of a suspension containing a high concentration of pesticidal active ingredient as it is, the suspension aggregates and non-uniformity occurs. There is a concern that the discharge rate of the suspension from the crusher may be lowered, the production efficiency may be reduced, the quality of the slurry may not be stable, and the viscosity of the suspension may be increased, which may cause crushing. Therefore, it has been desired to develop a method capable of wet-milling a suspension as high as possible without adversely affecting the quality of the preparation.

On the other hand, since these formulations for throwing in paddy fields are applied locally, unless the active ingredient diffuses promptly from the spot where they are thrown, phytotoxicity and uneven efficacy tend to occur due to non-uniformity of the active ingredient. In some cases, defects such as the influence of residual active ingredients on subsequent crops are likely to occur. Therefore, it is necessary that the pesticide formulation for dumping in paddy fields is a formulation that floats on water, and an appropriate water surface extender is added to the formulation to spread the formulation from the dropping point as soon as possible. However, the water surface spreader compounded for this purpose is easily affected by the surfactant used for other purposes, and depending on the type of the surfactant used, the spreadability on the water surface of the preparation may deteriorate. Many. Therefore, it is necessary to select a surfactant that does not cause such spread inhibition as much as possible.

[0011]

In view of the above-mentioned circumstances, the present inventors have been able to wet pulverize a pesticide active ingredient having a concentration as high as possible in a suspended state, and in particular, pesticides for paddy field throwing. In the case of manufacturing a preparation, the inventors have made earnest studies for a grinding aid that does not adversely affect the spreadability of the preparation on the water surface when thrown into a paddy field. As a result, a polyalkylene glycol-type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule should be blended (preferably in a small amount).
The suspension containing a high concentration of pesticide active ingredient can be pulverized with low viscosity without gelation, and it is contained in the pesticide formulation for paddy field thrown into by kneading and granulating the obtained pulverized suspension. The present invention has been completed by finding that the pesticide formulation for dumping in paddy fields does not have an adverse effect on the water surface spreader to be used and exhibits a good spreadability.

[0012]

According to the present invention, a polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in a molecule is blended to contain a high concentration of pesticide active ingredient. Wet milling of the suspension, high-concentration pesticide solid preparation obtained by kneading and granulating the obtained suspension, polyalkylene glycol type non-polymer containing ethylene glycol and propylene glycol in a block form in the molecule A high-concentration agricultural chemical solid preparation is produced by wet-pulverizing a suspension containing an ionic surfactant and containing a high-concentration agricultural chemical active ingredient, and kneading and granulating the resulting suspension. Method, pesticide formulation for paddy field in which the high-concentration pesticide solid formulation is packaged in a water-soluble film or sheet, the high-concentration pesticide solid formulation from the ridge to the paddy field How to use the above-mentioned high concentration pesticide solid formulation with the inflow of irrigation water from the mouth of the paddy field, and how to use the above pesticide formulation for paddy field with the inflow of irrigation water from the mouth of the paddy field And a method of throwing the pesticide formulation for paddy field injection into the paddy field from the ridge.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, "a polyalkylene glycol type nonionic surfactant containing a block of ethylene glycol and propylene glycol in a molecule" is, for example, a higher alcohol, an alkylphenol, a fatty acid or a higher fat. Ethylene oxide (hereinafter referred to as EO) in a hydroxyl group, a carboxyl group, an amino group or an amide group possessed by a group amine or a fatty acid amide in the molecule.
And propylene oxide (hereinafter referred to as PO) are added to the polyalkylene glycol type nonionic surfactant to contain them in a block form.
The terminal hydroxyl group to which is added may remain the hydroxyl group,
Suitable alcohol (the alcohol may be, for example, a straight chain or branched chain unsaturated or saturated aliphatic alcohol having 1 to 18 carbon atoms, and preferably 6 to 1 carbon atoms.
Two straight or branched chain saturated aliphatic alcohols or oleyl alcohols. And an organic acid (the organic acid has, for example, 1 carbon atom).
It may be a straight or branched chain unsaturated or saturated fatty acid having 18 to 18 carbon atoms, and is preferably a straight chain or branched chain saturated fatty acid having 6 to 12 carbon atoms or oleic acid. Or an inorganic acid (the inorganic acid may be, for example, sulfuric acid or phosphoric acid). When forming an ether or an ester, when there are a plurality of terminal hydroxyl groups, each hydroxyl group may optionally form an ether bond or an ester bond. Also, for example, as in the following compounds (1) and (2), a surfactant having a form in which polyalkylene glycol is sandwiched and EO or PO is added in a block form at both ends is also used in the molecule of the present invention. It is included in a polyalkylene glycol type nonionic surfactant containing a block of glycol and propylene glycol.

The "polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule" of the present invention preferably has the following formula:

[0015]

[Chemical 3] [Wherein R ¹ represents a hydrogen atom, a higher alcohol residue, an alkylphenol residue, an arylphenol residue, a fatty acid residue, a higher aliphatic amine residue or a fatty acid amide residue, and x 1, x 2, x 3 and x 4 Each independently 4 or more 9
Represents an integer of 00 or less, and y1, y2, y3 and y4 are each independently an integer of 16 or more and 130 or less (preferably 16 or less).
It is an integer not less than 70 and not more than 70. ) Is shown. ] The compound (1)-(4) represented by this.

In the present invention, the higher alcohol residue is
A linear or branched alcohol residue having 4 to 18 carbon atoms, which may be, for example, a butyl alcohol residue, a hexyl alcohol residue, an ethylhexyl alcohol residue, a lauryl alcohol residue or an oleyl alcohol residue, Is an ethylhexyl alcohol residue or a lauryl alcohol residue.

In the present invention, the alkylphenol residue is a phenol residue to which the same or different 1 to 3 linear or branched alkyl groups having 3 to 9 carbon atoms are bonded, for example, tributylphenol residue. Group, an ethylhexylphenol residue or a nonylphenol residue, preferably a nonylphenol residue.

In the present invention, the arylphenol residue is a straight-chain or branched-chain alkyl group to which 1 to 3 styryl groups are bonded and which is the same or different and has 1 or 2 carbon atoms of 1 to 4 Is a phenol residue which may be bonded, and may be, for example, a monostyrylphenol residue, a distyrylphenol residue, a tristyrylphenol residue or a distyrylcresol residue, and preferably a tristyrylphenol residue. is there.

In the present invention, the fatty acid residue is a saturated or unsaturated fatty acid residue having 2 to 18 carbon atoms, such as acetic acid residue, butyric acid residue, lauric acid residue or oleic acid residue. It is possible and is preferably a lauric acid residue.

In the present invention, the higher aliphatic amine residue is a saturated or unsaturated aliphatic amine residue having 4 to 18 carbon atoms, for example, hexylamine residue, ethylhexylamine residue, laurylamine residue. It may be a group or an oleylamine residue, preferably a laurinamine residue or an oleylamine residue.

In the present invention, the fatty acid amide residue is a saturated or unsaturated fatty acid amide residue having 4 to 18 carbon atoms, for example, butyric acid amide residue, lauric acid amide residue or oleic acid amide residue. And is preferably a lauric acid amide residue.

Generally, the above compounds (1) and (2) are
Those in which R ¹ is a hydrogen atom are nonionic surfactants called Pluronic type, and compounds (3) and (4) are nonionic surfactants called Tetronic type. The relationships between the compounds (1) and (2) and the compounds (3) and (4) are such that the addition positions of EO and PO are reversed. These compounds are surfactants that are commonly used as auxiliary agents for agricultural chemicals, and have characteristics such as low toxicity, less phytotoxicity, less environmental impact, and less influence of hard water and pH. is doing.

In compounds (1) and (2), R
¹ is preferably a hydrogen atom.

The polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule used in the present invention is
More preferably, the polyalkylene glycol type nonionic surfactant has a propylene glycol moiety (PO addition moiety) having a molecular weight of 2000 to 4000, and an ethylene glycol moiety (EO) relative to the molecular weight of the propylene glycol moiety (PO addition moiety). The ratio of the molecular weight of (addition portion) is 0.
It is a polyalkylene glycol-type nonionic surfactant having an amount of 05 to 10 times, and even more preferably, the polyalkylene glycol-type nonionic surfactant has a propylene glycol moiety having a molecular weight of 2500 to 3500 and a propylene glycol moiety The ratio of the molecular weight of the ethylene glycol portion to the molecular weight is 0.1 to 4 times, and R
^The above compound (1) wherein ¹ is a hydrogen atom, and particularly preferably, the propylene glycol moiety has a molecular weight of 2700 to 3
200, and the ratio of the molecular weight of the ethylene glycol portion to the molecular weight of the propylene glycol portion is 0.2 to
It is the above compound (1) which is 1 time and R ¹ is a hydrogen atom.

The above-mentioned molecular weight may represent not only the molecular weight of one molecule but also the average molecular weight of a plurality of molecules.

When the above-mentioned surfactant is added to a suspension containing a pesticidal active ingredient, the viscosity of the suspension does not increase even if the concentration of the pesticidal active ingredient increases, and as shown below. Wet pulverization can be performed with a high-concentration suspension, and the obtained suspension can be kneaded and granulated to produce a high-content granule. Even if these surfactants are mixed with the granules that float and spread on the water surface, they do not hinder the action of the water surface spreader that is used at the same time. It can be blended in a pesticide formulation for paddy field throwing into a permeable film.

The amount of the polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule used in the present invention varies depending on the combination of the agrochemical active ingredient and the surfactant. In the suspension to be wet-milled, usually in a small amount,
It is preferably 0.005 to 10% by mass, more preferably 0.01 to 3% by mass, and even more preferably
0.05 to 2% by mass, and particularly preferably 0.08 to
1% by mass, most preferably 0.1 to 0.5% by mass
Is. It should be noted that even if it is more than 10% by mass, the effect of the present invention can be obtained, but it is not preferable in consideration of economy.

In the present invention, the nonionic surfactant is suspended in water together with the active ingredient of the agricultural chemicals and, if necessary, a grinding aid such as a dispersant and a wetting agent.
Grinding can be carried out in the same manner as in ordinary wet grinding.

The wet pulverizer used for such wet pulverization is a pulverizer generally used for wet pulverization of agricultural chemicals, and for example, an attrition mill such as an attritor;
It may be a vertical or horizontal bead mill such as an apex mill, a dyno mill, a sand mill; a hammer mill such as a wet atomizer; or a colloid mill, preferably an attrition mill or a bead mill.

The pesticidal active ingredient used in the present invention is generally used as a pesticide, and is not particularly limited as long as the drug substance is a solid at room temperature. For example, usual insecticides, fungicides, herbicides or It may be a plant regulator (preferably a fungicide or a herbicide, more preferably a herbicide),
It is preferably one that does not have extremely poor stability in water, one that does not have high solubility in water, or one that has a melting point higher than 30 ° C.

The insecticide used in the present invention is, for example, trichlorfon, monocrotophos, acephate, carbofuran, bensultap, buprofezin, metolcarb, propoxure, imidacloprid, acetamiprid, milbemectin, carbaryl, chlorfluazuron, dimethylvinphos or pyrimidifen. Can be
Preferred are buprofezin, imidacloprid, acetamiprid, milbemectin or pyrimidifen.

The bactericide used in the present invention is, for example, fusaride, iprodione, probenazole, isoprothiolane, tricyclazole, pyroquilon, carpropamide, olibrite, azoxystrobin and 7-fluoro-1,2,5,6-tetrahydro-. 4H-pyrrolo [3.2.1-i. j] blasting agents such as quinolin-4-one; diclomedine, flutolanil, mepronil, thifluzamide, flametopyr, 2- (4-fluorophenyl)
-1- (1H-1,2,4-triazol-1-yl)
A scouring agent such as -3-trimethylsilylpropan-2-ol and peniculone; or teclophthalam, benomyl, metalaxyl, maneb, zineb, thiadiazine, thiuram, polycarbamate, captan, TP
It may be other fungicides such as N, thiophanate methyl, vinclozolin, fluazinam, PCNB, triazine, chlorothalonil and carboxin, preferably fusaride, probenazole, isoprothiolane, carpropamide, olibrite, azoxystrobin, diclomedine, Flutolanil, thifluzamide, flametopyr or teclophthalam.

The herbicides used in the present invention include, for example, pyrazolate, benzophenap, pyrazoxifene, pyributycarb, bromobutide, mefenacet,
Bensulfuron-methyl, chlornitrophen, clomethoxyphene, dimuron, bifenox, naproanilide, oxadiazone, oxadiargyl, bentazone, dimepiperate, dithiopyr, imazosulfuron,
Quinoclamin, MCPA, 2,4-D, MCPB, quinclorac, pyrazosulfuron-ethyl, pentoxazone, tenilchlor, cumyluron, cinosulfuron, cimetrin, cyhalofop-butyl, etobenzanide, casfenthrol, ethoxysulfuron, azimsulfuron, cyclosulfamuron, indanofan. , Pyriminobac-methyl, oxadichromefone, 4- (2-chlorophenyl) -N-cyclohexyl-4,5-dihydro-N-ethyl-5-oxo-1H-tetrazole-1
-Carboxamide (NBA061), benzobicyclone (SB500), methyl N- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] carbamate and methyl N- [4- (benzoxazole-
Paddy field herbicides such as 2-ylmethoxy) -2-methylphenyl] carbamate; or herbicides for field or non-arable land such as trifluralin, linuron, diuron, metribuzin, promethrin, simazine, pendimethalin, aixonil, alachlor and bromacil. And preferably pyrazolate, benzophenap, pyrazoxifene, pyributycarb, bromobutide, mefenacet, bensulfuron-methyl, dimuron, oxadiaargyl, imazosulfuron, pyrazosulfuron-
Ethyl, pentoxazone, cafenstrol, ethoxysulfuron, azimsulfuron, indanophane, oxadichromefone, NBA061 or benzobicyclone.

The plant regulator used in the present invention may be, for example, inabenfide, paclobutrazol or uniconazole.

In the present invention, "wet grinding of high-concentration suspension" is wet grinding of a suspension having a concentration of an agrochemical active ingredient that exceeds the limit of the concentration that can be pulverized using a normal surfactant. .

The concentration of the pesticidal active ingredient to be wet-milled in the suspension varies depending on, for example, the physical properties of the pesticidal active ingredient and the presence and type of a grinding aid such as a dispersant or a wetting agent.
Usually, it is 30 to 80% by mass, and the higher the higher the efficiency. The wet pulverization of the present invention can pulverize a suspension having a concentration higher than 80% by mass depending on the combination of the pesticide active ingredient and the nonionic surfactant used.
It is possible to grind a suspension in which the pesticidal active ingredient is 85% by mass, in which case the pesticidal active ingredient is of course 30%.
It is also possible to grind a suspension which is -80% by weight. The concentration of the pesticide active ingredient that can be wet-milled in the suspension varies depending on the type of the pesticide active ingredient.For example, when pyrazolate is used as the pesticide active ingredient, in the conventional method, the pesticide content in the suspension is At most 60-65%, at most 50% when using diclomedine and at most 45% when using pyrimidifen,
The maximum concentration in the suspension of the pesticidal active ingredient that can be wet-milled according to the present invention is 85% in the case of pyrazolate, 70% in the case of diclomedine, and 65% in the case of pyrimidifen, as described later. .

In the present invention, it is necessary to select and use a dispersant that does not interfere with other components as the dispersant used during wet pulverization. Examples of the dispersant used during wet milling include lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate condensate, maleic acid and styrene sulfonate. Salts of condensates with acids, salts of carboxylic acid condensates such as acrylic acid and maleic acid, polyacrylic acid salts, salts of acrylic acid and maleic acid copolymers, salts of maleic anhydride and methyl vinyl ether copolymers, Alkylbenzene sulfonates, dialkyl sulfosuccinates, salts of lauryl sulphates, polyoxyethylene alkylaryl ether sulphates such as polyoxyethylene alkylaryl ether sulphates of nonionic surfactants with normal ethylene oxide, polyoxyethylene alkylaryl ether phosphates Such as normal Phosphoric acid esters of nonionic surfactants having lenoxide, and anionic surfactants such as salts obtained by neutralizing these sulfuric acid esters and phosphoric acid esters with appropriate cations; or phosphorus such as sodium tripolyphosphate and sodium hexametaphosphate It may be an acid salt and in many cases is preferably an anionic surfactant. The surfactants used in these dispersants are often effective as wetting agents. Further, in the present invention, an appropriate nonionic, cationic or amphoteric surfactant can be used as a dispersant during wet grinding.

The above-mentioned dispersant or the amount of the above-mentioned dispersant and the wetting agent to be compounded is usually 0.01 to 0.01 in the suspension during wet grinding.
It is 30% by mass, preferably 0.03 to 10% by mass, and more preferably 0.1 to 5% by mass.

As described below, when the high-concentration pesticide solid preparation of the present invention is subjected to so-called frame spraying or water mouth treatment, and when the pesticide formulation for paddy field injection of the present invention is water mouth treatment or throw-in treatment, the pesticide preparation is the rice paddy field. Therefore, it is necessary to spread the granules to the surface of the water by the force of the water surface spreader to exert their effect on the entire paddy field, but if a large amount of the above dispersant is used, , The water surface extender and the above dispersant may sometimes compete with each other. Therefore, as the dispersant used in the present invention, it is necessary to select and use a surfactant that does not compete with the water surface spreader and the like.

In the high-concentration pesticide solid preparation of the present invention, other auxiliary agents, liquid active ingredients and the like can be added, if necessary, during wet grinding of the pesticide active ingredient. It is necessary to select and use a component that does not interfere with the above.

The suspension obtained by wet-milling the solid pesticide active ingredient thus obtained is, for example, a suitable extender, binder,
Mix with disintegrating / dispersing agent, wetting agent, granulating property improving agent, stabilizer, potency enhancer, phytotoxicity reducing agent, floating agent, water surface spreading agent, and other dry active pulverized pesticide active ingredient, and if necessary, It is possible to carry out wet granulation by adding water and kneading, and using an appropriate kneading granulator which is usually used for granulation of pesticides. However, these extenders, binders, disintegrating / dispersing agents, wetting agents, granulating agents, stabilizers, potency enhancers, phytotoxicity reducing agents, suspending agents and other agrochemical active ingredients should not interfere with each other. Other pesticide active ingredients pulverized by dry method that need to be selected and used, when the pesticide active ingredient is extremely unstable to water and cannot be wet pulverized, such as when dry pulverizing for any reason, It is also possible to mix the dry pulverized product with other auxiliaries, and knead and granulate with the above suspension.

The extender used in the present invention is not particularly limited as long as it is generally used as a pesticide carrier, and for example, fine mineral powder such as clay, calcium carbonate, diatomaceous earth, amorphous silicon dioxide, talc and bentonite. ; Starch, wood flour, sawdust, coffee bean powder, tab powder, cellulose powder, microcrystalline cellulose, rice husk powder, rice bran, bran and coconut shell powder, and other plant powders; urea, potassium chloride, ammonium sulfate, and water soluble such as glauber's salt Inorganic compound; or a water-soluble saccharide such as sugar, lactose and glucose, and is preferably fine mineral powder or vegetable powder.

The blending amount of the extender used varies depending on the type and amount of other auxiliaries, but is usually 0.1 to 80% by mass in the high concentration pesticide solid formulation, and preferably 1 to 5
It is 0 mass%.

The high-concentration pesticide solid preparation of the present invention may contain a binder in order to impart hardness to the preparation when the powder raw material is granulated to prepare the high-concentration pesticide solid preparation. The binder used is preferably a high-concentration pesticide solid preparation that disintegrates in water, or it depends on whether it is preferable that it does not disintegrate, but when disintegration is preferred, for example, a relatively low molecular weight, dextrin, Polyvinylpyrrolidone, polyacrylic acid salt or carboxymethylcellulose salt, polyvinyl alcohol with relatively low molecular weight and low saponification rate, ligninsulfonic acid salt, water-soluble polymer substance such as gum arabic, or montmorillonite mineral substance such as bentonite It may be a fine powder, preferably a low molecular weight dextrin, a low molecular weight salt of carboxymethyl cellulose, a salt of lignin sulfonic acid or bentonite, and when it is preferable not to disintegrate, for example, starch;
Water-soluble starch, dextrin, pregelatinized starch, and various other starch derivatives; or relatively high-molecular weight polyvinylpyrrolidone, polyacrylic acid salt, carboxymethylcellulose salt or polyvinyl alcohol, preferably water-soluble starch , Dextrin, pregelatinized starch or other starch derivatives.

The amount of the binder used varies depending on the formulation composition, the granulation method, the size of the particles, etc., but is usually 0.1 to 30% by mass in the high-concentration pesticide solid preparation, and is preferably Is 0.5 to 20 mass%.

The high-concentration pesticide solid preparation of the present invention may contain a disintegrating / dispersing agent for disintegrating the particles in water and suspending / dispersing the active ingredient in water. The disintegrating / dispersing agent used is often, preferably, an anionic surfactant. The disintegrating / dispersing agents used may be common and these disintegrating / dispersing agents are often also useful as wetting agents. The disintegrating / dispersing agent and the wetting agent are not limited to these, and nonionic, cationic or zwitterionic surfactants may be used as appropriate. Also, starch,
Carboxymethyl cellulose, carboxymethylated starch and salts thereof, cross-linked polyvinylpyrrolidone, microcrystalline cellulose, superabsorbent resin and the like having a property of absorbing water and expanding can be used as a disintegrant.

The amount of the disintegrating / dispersing agent, the disintegrating agent or the wetting agent to be added is usually 0.01 to 0.01 in the high concentration pesticide solid preparation.
It is 30% by mass, preferably 0.03 to 20% by mass, and more preferably 0.05 to 10% by mass.

In the present invention, a granulating property improver can be used to improve the granulating property of the high concentration pesticide solid preparation. The granulation improver used may have a viscosity that imparts plasticity to the surfactant or composition generally used as a granulation improver in pesticide granules, for example, polyoxyethylene alkylaryl. ether,
Nonionic surfactants such as polyoxyethylene alkyl esters, polyoxyethylene aryl aryl ethers; sodium salts of dialkyl sulfosuccinates,
Anionic surfactants such as sodium salts of alkylbenzene sulfonic acids; mineral fines such as bentonite;
Dextrin, starch derivative such as pregelatinized starch; natural gum such as gum arabic; cellulose derivative such as sodium salt of carboxymethyl cellulose; or water-soluble synthetic polymer such as sodium salt of polyvinyl alcohol or polyacrylic acid It is possible and is preferably an anionic surfactant or bentonite.

The amount of the granulating property improver to be used varies depending on the type of the granulating property improver and the type and amount of other auxiliaries, but it is usually 0.01 to 30 in the high concentration pesticide solid preparation.
%, Preferably 0.05 to 20% by mass, and more preferably 0.1 to 10% by mass.

The high-concentration pesticide solid preparation of the present invention may contain a stabilizer, if necessary, in order to stabilize the active ingredient of the pesticide or the physical properties in the high-concentration pesticide solid preparation. The stabilizer used may be, for example, a pH adjuster, an antioxidant, a light stabilizer and a solid acid activity or solid base activity remover.

The amount of the stabilizer to be used is usually 0.001 to 5% by mass, preferably 0.01 to 2% by mass in the high concentration pesticide solid preparation.

The high-concentration pesticide solid preparation of the present invention may contain a potency enhancer such as piperonyl butoxide, if necessary, in order to maximize the potency of the pesticide active ingredient. . Further, the high-concentration pesticide solid preparation of the present invention may contain a phytotoxicity-reducing agent, if necessary. As these potency enhancers and phytotoxicity reducing agents, appropriate ones can be selected and used according to the active ingredient of the agricultural chemical.

The compounding amount of the potency enhancer or phytotoxicity reducing agent used varies depending on the kind and amount of the agrochemical active ingredient, but is usually 0.1 to 10 times the amount of the agrochemical active ingredient,
The amount is preferably 0.5 to 5 times.

The high-concentration pesticide solid preparation of the present invention is formed as it is or into a paddy field throwing preparation, and the pesticide preparation is uniformly treated in the entire paddy field, for example, by the frame treatment, water spout treatment and throwing treatment described below. When processing locally without
A water surface floating agent can be contained in order to float and spread the solid preparation on the water surface and to spread the pesticide active ingredient throughout the paddy field. Water floating agents used include, for example, mineral substances such as expanded shirasu, expanded perlite, expanded pumice and calcined vermiculite; plant substances such as cork, wood flour and cellulose; expanded synthetic resins such as expanded polystyrene; Synthetic resin powder; hollow plastic (eg Matsumoto Microsphere F30E); synthetic resin granules; or mixtures thereof, preferably cork, wood flour, expanded shirasu, expanded pumice, calcined vermiculite. , Foamed perlite, foamed synthetic resin, synthetic resin powder or plastic hollow body.

The amount of the surface floating agent to be used depends on, for example, the type and formulation of the surface floating agent and the particle size of the solid preparation, but may be an amount sufficient to float the high concentration pesticide solid preparation on the water surface. Ordinarily, it is 0.01 to 90 mass% in a high concentration pesticide solid preparation, and preferably 0.1 to 90 mass%.
70% by mass, more preferably 0.5 to 60% by mass
Is.

The high-concentration pesticide solid preparation of the present invention may contain a water surface spreader to improve the spread of the high-concentration pesticide solid preparation on the water surface. Examples of the water surface extender used include (co) carboxylic acids such as acrylic acid and maleic acid.
Polycarboxylic acid type polysoap such as polymer salt, carboxylic acid such as acrylic acid, maleic acid and the like, copolymerized with styrenesulfonic acid, vinyl group and the like, sodium salt, potassium salt, polymer salt such as ammonium salt; olein Soaps such as sodium acidate and potassium stearate; sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, perfluoroalkylcarboxylic acid salts, salts of α-olefinsulfonic acid, salts of α-sulfofatty acid, oleyl Other anionic surfactants such as salts of methyl tauride; alkylene oxas such as polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters. Nonionic surfactants of the type to which an id is added; various nonionic surfactants such as silicone-based surfactants and acetylene-based surfactants; these nonionic surfactants are esters of phosphoric acid or sulfuric acid, and in some cases, Surfactants obtained by neutralizing them with a suitable alkali; Surfactants containing a fluorine atom in the molecular structure;
Liquid paraffin, naphthenic and aromatic high boiling solvents, low viscosity polybutene, mineral oils such as machine oils; silicone oils; various vegetable oils; resins such as pine resin; camphor white oil; α-pinene; camphor; , Naphthalene, and preferably sodium dialkylsulfosuccinate, a salt of α-olefin sulfonic acid, a salt of α-sulfofatty acid, a salt of oleylmethyl tauride, a silicone surfactant, an acetylene surfactant, a molecule. It is a surfactant having a fluorine atom in the structure or a liquid paraffin, a naphthene-based or aromatic high-boiling solvent.

Among these, acetylene type surfactants,
Silicone-based surfactants and surfactants containing a fluorine atom in the molecular structure are particularly good as water surface extenders, but when these water surface extenders are used together with ordinary surfactants, water surface extenders are Since the malleability is often reduced, it is desirable to mix the surfactant as little as possible. However, the polyalkylene glycol-type nonionic surfactants (particularly pluronic and tetronic surfactants) containing ethylene glycol and propylene glycol in a block form in the molecule of the present invention can be used as these water surface spreading agents. On the other hand, it has a characteristic that it does not have an adverse effect.

The amount of the water surface spreader used is, for example, the type and content of the pesticide active ingredient, the type of the water surface spreader and its addition method, and the formulation and dosage form of the other ingredients. It is usually 0.01 to 10% by mass in a high-concentration pesticide solid preparation, preferably 0.1
˜5% by mass, more preferably 0.2 to 3% by mass.

The high-concentration pesticide solid preparation of the present invention can be prepared by the following method.

The high-concentration pesticide solid preparation of the present invention comprises a high-concentration suspension of the pesticidal active ingredient wet-ground by the method described above.
It can be obtained by kneading and granulating with other auxiliaries. The granulator used may be, for example, a lateral-pressing, pre-pressing or basket-type extruding granulator, a mixing granulator, a tumbling granulator, a fluidized bed granulator and a spray dryer, among the components In the case of containing foamed Shirasu or foamed perlite, if these are strongly pressed, the balloon may be crushed and the buoyancy may be reduced.Also, in the case of containing cork, if this is strongly pressed, the buoyancy will be reduced. Therefore, a granulator that does not apply strong pressure or shearing force is preferable.

The wet granules thus obtained are subjected to, for example, drying, sizing and sieving steps to obtain the desired granules.

With respect to the particle size of the obtained granules, in the case of the granulation method, if the particles are too large, it becomes difficult to dry the granules, and especially when the high-concentration pesticide solid preparation of the present invention is water-floating granules, The agent is easily affected by wind on the surface of the water, and when it is a hydratable granule, if the particle is too large, the dispersion of the active ingredient of the pesticide will be delayed, and if the particle is too fine, it will be easy to divide into small pieces. Is 0.1 to 5 mm, and preferably 0.3 to 3 mm, because it deteriorates or dusting occurs during use.
And more preferably 0.5 to 2 mm. The shape of the particles is not particularly limited, and may be, for example, a columnar shape, a spherical shape, or an amorphous shape.

The apparent specific gravity of the high-concentration pesticide solid preparation of the present invention is usually from the viewpoint of ease of handling, productivity and floatability on the water surface when the high-concentration pesticide solid preparation is a water-floating granule. , 0.15 to 0.50, and preferably 0.
20 to 0.45, and more preferably 0.25 to 0.
40.

In the case of using a liquid pesticide active ingredient, a liquid pesticide active ingredient or a low melting point pesticide active ingredient, the high-concentration pesticide solid preparation of the present invention may be dissolved in a solvent or an emulsifier if necessary. The concentrated premix can be prepared and absorbed by the granules obtained by the above-mentioned method to be manufactured. The concentrated premix can contain, for example, a water surface extender, a stabilizer, an emulsifier, a dispersant, a wetting agent, and a solvent, if necessary. Further, the agrochemical active ingredient, together with other auxiliaries, for example, amorphous synthetic silica, diatomaceous earth, calcium silicate, a highly oil-absorbing carrier such as a highly oil-absorbent resin and highly oil-absorbent dextrin, or absorb the agrochemical effective. If a solid solution is formed with a resin, chemical substance or other solid agricultural chemical active ingredient which is compatible with the components, and this is pulverized, it can be handled in the same manner as a solid agricultural chemical active ingredient. Furthermore, the high-concentration pesticide solid preparation of the present invention is a solid pesticide active ingredient, and when using a liquid pesticide active ingredient, a liquid pesticide active ingredient or a low-melting pesticide active ingredient at the same time, a solid pesticide active ingredient. Ingredients and other active ingredients of agricultural chemicals are crushed together to prepare a so-called suspoemulsion, which is mixed and kneaded with other raw materials in the same manner as the suspension of the above-mentioned solid raw material, and produced by granulation. It is possible to

When the high-concentration pesticide solid preparation of the present invention is produced by the absorption method, the previously prepared particle nuclei are charged into the above-mentioned stirring mixer, and the liquid or liquefied pesticide active ingredient or its concentrated liquid is stirred. A general method is to add a premix for absorption. The premix can contain, for example, a water surface extender, a solvent, an emulsifier, and a stabilizer, if necessary.

The high-concentration pesticide solid preparation of the present invention may optionally contain a solvent in order to dilute the liquid drug substance or to liquefy the low melting point drug substance. The solvent used has a dissolving power for the drug substance, does not affect the stability of the drug substance, has a high boiling point and low toxicity, and has low flammability,
For example, high-boiling point solvents such as paraffinic, aromatic and naphthenic; fatty acids, phthalic acid, adipic acid and the like obtained from various animal and vegetable oils such as oleic acid, maleic acid, fumaric acid and coconut oil used as plasticizers. It may be an ester such as phosphoric acid; a vegetable oil such as coconut oil and rapeseed oil; or an animal oil such as whale oil and sardine oil. In general, many pesticide active substances have a specific gravity of 1 or more. In such a case, it is desirable to use a solvent having a specific gravity of less than 1 and a low viscosity in order to keep the emulsified particles in water as long as possible and diffuse them widely in the paddy field. In this sense, the solvent used is preferably liquid paraffin or low molecular weight polybutene.

The amount of the solvent used varies depending on the kind and physical properties of the pesticide active ingredient, but is preferably as small as possible unless it affects the stability and physical properties of the solid preparation over time.
Normally, 1 part of pesticide active ingredient to be dissolved is 0.
It is 1 to 50 parts, and preferably 0.2 to 10 parts.

The high-concentration pesticide solid preparation of the present invention may contain an emulsifier for emulsifying the pesticide active ingredient in water, and such an emulsifier may be selected in the same manner as the emulsifier of the emulsion is selected. It can be selected and used according to the kind and physical properties of the components and the solvent. Unlike ordinary emulsifiers, the emulsifier used does not artificially stir when the solid pesticide solid preparation is used, and therefore, it is preferable that the emulsifier be as self-emulsifying as possible and be finely emulsified.

The amount of the emulsifier used is usually 0.01 to 1 with respect to 1 part of a liquid to be emulsified, which is composed of a liquid pesticide active ingredient or a pesticide active ingredient diluted or dissolved in a solvent.
It is 0 part, and preferably 0.03 to 3 parts.

When the high-concentration pesticide solid preparation of the present invention is produced by the coating method, the granules prepared in advance are charged into a stirring mixer, and if necessary, a liquid binder is added to the surface of the granules. After moistening, a concentrated premix of the agrochemical active ingredient is added and further mixed by stirring to coat the surface of the grain core with the agrochemical active ingredient. The stirring mixer used may be, for example, a Nauta mixer, a ribbon blender, a rotary blender or a V-type mixer, and is preferably a low speed mixer with less crushing of particles.

In the case of producing a water surface spreadable granule by a coating method or an absorption method, the effect of the water surface spreader can be more effectively exhibited when it is present in the outermost layer. Therefore,
It is desirable that the water surface extender is added last after coating or absorbing the pesticide active ingredient and other auxiliaries. As described above, when the high-concentration pesticide solid preparation of the present invention is produced by using the granulation method, the coating method and the absorption method, the necessary steps among the steps such as granulation, coating and absorption are performed at once. Also, if necessary, it may be divided into two or more stages,
For example, a part of the pesticide active ingredient is kneaded and granulated to obtain a floating granule, which may be coated with the rest of the pesticide active ingredient, on the surface of the floating granule prepared by the granulation method, The water surface spreader may be coated or absorbed, and the coating method and the absorption method may be applied to the same preparation.

The high-concentration pesticide solid preparation of the present invention can be used as follows.

The high-concentration pesticide solid preparation of the present invention is, for example,
It may be a granule, a granular wettable powder or a fine granule, and is preferably a granule or a granular wettable powder.

When the high-concentration pesticide solid preparation of the present invention is used as a pesticide for paddy fields, the high-concentration pesticide solid preparation of the present invention is:
When it is a granule, it can be uniformly sprayed into the paddy field like a general granule or from the ridge without entering the paddy field, without using a machine or using a spraying machine. In addition, the high-concentration pesticide solid preparation of the present invention is suitable for water treatment from the ridge to the paddy field (frame treatment), or from the water mouth of the paddy field to the irrigation water (water mouth treatment). It can be used as a sachet in a film, and the obtained sachet is thrown into a paddy field from a ridge (throwing treatment) to spray pesticides without using a uniform spraying machine. Further, the high-concentration agrochemical solid preparation of the present invention, when it is a granular wettable powder, the granular wettable powder is diluted with a small amount of water at the time of use to prepare a suspension, which is the same as the flowable agent. To
For example, pesticides can be sprayed by uniformly spraying into a paddy field, frame treatment, water mouth treatment, and air spraying with a helicopter or the like.

Even when the high-concentration pesticide solid preparation of the present invention is used as a pesticide other than for paddy fields, when the high-concentration pesticide solid preparation of the present invention is a granule, the granule is the same as a general granule. It can be used as a granule for labor-saving spraying with a high concentration and a small amount that can be uniformly sprayed. Further, the high-concentration agrochemical solid preparation of the present invention, when it is a granular wettable powder, the granular wettable powder is diluted with water at the time of use to prepare a suspension, similar to the flowable agent, For example, pesticides can be sprayed by uniform spraying on soil or foliage and air spraying with a helicopter or the like.

The water-soluble film when the high-concentration pesticide solid preparation of the present invention is used as a package of a preparation for injection treatment is a film which dissolves or disperses in water and has spreadability, The raw material of the water-soluble film may be, for example, polyvinyl alcohol or a derivative thereof, pullulan film or polyethylene oxide or a derivative thereof, expansive water-soluble paper is preferable, and more preferably, a film made of polyvinyl alcohol or a derivative thereof. Alternatively, it is a sheet (hereinafter abbreviated as PVA film).

The PVA film has a degree of polymerization of 500 to 20.
00, a polyvinyl alcohol having a saponification degree of 80 to 98% in the form of a film or sheet together with a small amount of a plasticizer and a stabilizer, and a small amount of a carboxylic acid and a sulfonic acid in a polymer. A film or sheet containing a copolymer such as

The water-soluble film is required to have high mechanical strength and cold resistance and be water-soluble. In that sense, the degree of polymerization of polyvinyl alcohol as a raw material is too high,
If the saponification degree is too high, it becomes difficult to dissolve in cold water, which is not preferable. Although the thickness of the water-soluble film depends on the film strength and the dissolution time, it is usually 20 to 80 μm, and preferably 30 to 50 μm.

Although the edges of the water-soluble film may be sealed with glue, there is a problem in workability, and the glued portion may be difficult to dissolve. In this respect, a material that can be heat-sealed is preferable.

The weight of the sachet for throwing into the paddy field is usually 10 to 200 g per pack, preferably 20 to 100 g, and more preferably 25 to 100 g.
It is 60 g. With such a weight, even a child, a woman, or an elderly person can easily throw the packet at a target point within 15 m. If the sachet is heavier than this, it will be difficult to throw it into a large area and it will be difficult to process it in a large area, and if the sachet is less than this, the sachet will reach the target point under the influence of the wind. Becomes difficult.

The water-floating pesticide solid preparation of the present invention spreads over a wide range on the water surface and also spreads the pesticide active ingredient over a wide range. Therefore, it is not necessary to forcibly throw a paddy field of a normal size into a ridge. It is enough to throw it on the surface of the water a few meters from the shore.

The number of sachets to be thrown into the paddy field is
If it is too large, it will take labor to throw it, labor will not be saved, and it will be economically disadvantageous, while if it is too small, the spread of the water-borne floating pesticide solid preparation may be insufficient, and usually 10 a paddy field , 1 to 30, preferably 2 to 20
It is an individual.

The outer packaging of the sachet for throwing into the paddy field is, for example, paper, resin, a bag or box or bottle made of metal, wood, etc., which is obtained by laminating aluminum foil or vapor-depositing aluminum or silica on these. And preferably a bag made of paper, resin, or a laminate of aluminum foil and aluminum or silica vapor-deposited thereon.

The water-floating pesticide solid preparation of the present invention can be used in the form of a granular wettable powder or a granule for uniform dispersion, or in the case of a frame treatment or a water spout treatment not divided into a water-soluble film. The same bag, box or bottle as the one used for packaging.

The water-floating pesticide solid preparation of the present invention is stable with respect to moisture absorption over time from the viewpoint of physical properties, and therefore it is necessary to pay more attention to moisture absorption as compared with the preparation containing a foaming agent. However, since the water-soluble film is broken when exposed to water, it is desirable to use an exterior that is appropriately waterproofed.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these. The following parts mean parts by mass.

[0087]

【Example】

[0088]

Test Example 1 Pyrazolate Slurry Grinding Experiment According to the formulations shown in Table 1 below, a pyrazolate drug substance, Surfynol TGE, NE291PG, and Pluronic P1 were used.
03 and water were mixed to form a pyrazolate slurry. 3 /
3 kg of the above slurry was added into the attritor MA1NS-X type (manufactured by Mitsui Mining Co., Ltd.) bestle filled with 17 kg of 16-inch steel balls, and the mixture was crushed at 200 rpm for 1 hour. After the pulverization was completed, the slurry was discharged from the attritor and the weight of the slurry that could be taken out by natural discharge was measured to obtain the yield relative to the charged amount, which was defined as the discharge rate. In addition, the dispersion state of the obtained slurry is indicated by a symbol, that in which it is completely dispersed is indicated by ◯, that in which some agglomerates are observed is indicated by Δ, and those in which agglomerates are formed and which are difficult to stir are indicated by x. The results are shown in Table 1.

[0089]

[Table 1] Formulation, viscosity and discharge rate of pyrazolate slurry ―――――――――――――――――――――――――――――――――――― Experiment Pyrazola Surfino NE29 Pluronic Water Emission Rate Slurry No. ¹⁾ Lu TGE ²⁾ 1PG ³⁾ Ku P103 ⁴⁾ (%) Dispersion state ――――――――――――――――――――― ――――――――――――――――― 1 70.0% 0.5% 0 0.4% 29.1% 98 ○ 2 70.0% 0.5% 0 0.8% 28.7% 96 ○ 3 75.0% 0.5% 0 0.8% 23.7 % 95 ○ 4 80.0% 0.5% 0 0.8% 18.7% 96 ○ 5 85.0% 0.5% 0 0.8% 13.7% 95 ○ − − − − − − − − − − − − − − − − − − 6 (Comparison) 65.0 % (Low concentration) 0.5% 0.4% 0 34.1% 97 ○ 7 (Comparison) 70.0% 0.5% 0.4% 0 29.1% 88 △ 8 (Comparison) 70.0% 0.5% 0 0 29.5% 84 △ 9 (Comparison) 75.0% 0.5 % 0.4% 0 24.1% 86 △ 10 (Comparison) 80.0% 0.5% 0.4% 0 19.1% 85 × ―――――――――――――――――――――――――― ―――――――――― ¹⁾ Pyrazolate 93.2%, moisture 6% ²⁾ Nissin Chemical Co., Ltd., surfactant mixture ³⁾ Nippon Emulsifier Co., Ltd., sodium salt of diethylhexyl sulfosuccinate 70 % ⁴⁾ BASF's pluronic type surfactant, PO part having a molecular weight of 3100, EO part having a molecular weight of 1850 containing 70-75% pyrazolate obtained in Experiment Nos. 1 to 5 in which Pluronic P103 was blended. The slurry was completely dispersed and the discharge amount was high. Particularly in Experiment No. 5, a high concentration slurry of 85% could be pulverized.

On the other hand, the slurry containing 70% of pyrazolate obtained in Experiment No. 8 from which Pluronic P103 was removed had a low discharge rate, and the quality of the slurry was not stable as the number of batches for grinding was increased.

Also, instead of Pluronic P103, N
Slurries containing 70% or more of pyrazolate obtained in Experiment Nos. 7, 9 and 10 in which E291PG was blended were observed to have some or considerable agglomeration, the discharge rate was low, and as the number of milling batches increased, The quality of the slurry was not stable. In addition, the slurry obtained from Experiment No. 10 was not sufficiently kneaded with the powder carrier during granulation, and the white kneader was noticeable in the kneaded product. In addition, it is the concentration containing 65% of pyrazolate at most (Experiment No. 6) and the pyrazolate concentration of 70% when the slurry wet-milled by blending NE291PG instead of Pluronic P103 is completely dispersed and shows a high discharge amount. When set to%,
The dispersion state and discharge amount of the slurry were inferior (Experiment No. 7).

[0092]

[Test Example 2] Pyrazolate slurry grinding experiment Pyrazolate drug substance (70.0%), Surfynol TG
E (0.5%), a surfactant (0.4%) selected from Table 2 below, and water (29.1%) were mixed to prepare a pyrazolate slurry. 3/16 inch steel ball 17
3 kg of the above slurry was added into the attritor MA1NS-X type (manufactured by Mitsui Mining Co., Ltd.) bestle filled with kg, and crushed at 200 rpm for 1 hour. After crushing,
The slurry was discharged from the attritor, and the weight of the slurry that could be taken out by natural discharge was measured to obtain the yield relative to the charged amount, which was defined as the discharge rate. In addition, the viscosity of the obtained slurry is B
It was measured by a viscometer. The results are shown in Table 2.

[0093]

[Table 2]   Viscosity and discharge rate of surfactant and pyrazolate slurry containing it ――――――――――――――――――――――――――――――――――――       Surfactant Experiment viscosity discharge rate No.Compound name Molecular weight of EO part Molecular weight of PO part (mPa ・ S) (%) ―――――――――――――――――――――――――――――――――――― (Pluronic type) 1 Pluronic L35 950 950 60 90 2 Pluronic L42 430 1200 53 92 3 Epan 450 1200 1200 48 93 4 Pluronic L63 850 1800 49 92 5 Epan 710 220 2000 44 94 6 Epan 720 500 2000 45 94 7 Epan 740 1333 2000 40 94 8 Epan 750 2000 2000 45 94 9 Epan 785 11333 2000 52 93 10 Pluronic P84 1900 2300 43 95 11 Pluronic P85 2300 2300 46 95 12 Pluronic L92 950 2700 42 96 13 Epan u102 775 3100 47 96 14 Epan u103 1330 3100 41 98 15 Epan u105 3100 3100 43 95 16 Epan u108 12400 3100 56 94 17 Pluronic 17R2 550 1600 50 92 18 Pluronic 17R4 1050 1600 48 93 19 Pluronic 25R2 800 2300 48 94 20 Pluronic 31 R1 350 2900 48 93 (Tetronic type) 21 Tetronic 701 400 3200 47 93 22 Tetronic 704 2300 3200 42 95 23 Tetronic 901 500 4200 49 93 24 Tetronic 904 2500 4200 59 94 25 Tetronic 908 20 800 4200 63 93 26 Tetronic 90R4 2840 4400 63 92 27 Tetronic 150R1 800 7200 51 92 − − − − − − − − − − − − − − − − − − 28 No additive--260 84 ――――――――――――――――――――――――――――――――――――     Note) Pluronic and Tetronic are trade names of BASF.         Epan is a trade name of Dai-ichi Kogyo Co., Ltd.

As is clear from Table 2, the slurry containing the surfactant of the present invention had a lower viscosity and a better discharge rate as compared with the case of no addition.

[0095]

Example 1 1 kg granules Calfin 600 (manufactured by Adachi Lime Industry Co., Ltd., calcium carbonate powder, 48.2 parts) prepared by using a slurry which was prepared by blending Pluronic P103 and wet-milled, bentonite powder (Toyojun Hotaka) Mark, 22.0 parts), Amycol No. 1 (Nippon Kagaku KK, dextrin, 3.0 parts) and serogen 5A
(Daiichi Kogyo Seiyaku Co., Ltd., sodium salt of carboxymethyl cellulose, 0.5 part) are mixed in a kneader,
Then, the slurry (29.0 parts) described in Test Example 1 as Experiment No. 1 and toxanone GR31A (5.0
Parts) and kneaded, and granulated using an extrusion granulator EXK1 type (manufactured by Fuji Paudal Co., Ltd., 0.9 mm screen). It dried at 105 degreeC using the fluidized bed dryer, and sieved to 1.0-0.5 mm division, and prepared the base particle. The obtained base particles (95.08 parts) were charged into a Nauta mixer, and pretilachlor raw material (96.0%, 4.92) was added.
Part) was added and mixed, and absorbed by the base particles to obtain 1 kg granule. This granule is a so-called 1 kg granule containing pyrazolate 18% and pretilachlor 4.5% and applying 1 kg per 10 a to a paddy field.

[0096]

[Comparative Example 1] 1 kg granules produced by using a slurry which was wet-milled without blending Pluronic P103 In Example 1, the slurry used was 31.2 parts of the slurry described as Experiment No. 6 in Test Example 1. 1 kg of granules was tried to be obtained in the same manner as in Example 1 except for changing the above. However, when the slurry was added to the powder part mixture and kneaded, the granulated product extruded from the screen was
Adhering to each other resulted in a large lump, which did not flow in the fluidized bed dryer, and a satisfactory granule could not be obtained. This means that the amount of granules calculated from the amount of pyrazolate required per 10a becomes larger than 1 kg, and 1 kg of pyrazolate granules cannot be produced.

[0097]

Example 2 Pesticide formulation cork powder for paddy field production (0.2 to 0.5 mm classification, 13.36) produced using a slurry which was wet-milled by blending Pluronic P103.
Part), bentonite powder (6.0 parts), serogen 5A
(8.0 parts), Surfynol 104S (3.0 parts) and tamol PP (manufactured by BASF, sodium salt of condensate of phenolsulfonic acid, 3.0 parts) were mixed in a kneader, and then Test Example 1 Slurry (84.5 parts) described in Experiment No. 4, Toxanone GR31A (5.0
Part) and kneading water (small amount) were added and kneaded, and the mixture was extruded and granulated from a 1.2 mm screen using Twin Dome Gran (extrusion granulator manufactured by Fuji Paudal Co., Ltd.).
The obtained granulated product was dried at 70 ° C. with a fluidized bed drier and sized with a sieve of 2 mm and 0.5 mm to obtain a granule.
The obtained granule was a water-spreading floating granule containing 63% of pyrazolate. The obtained granules were treated with Hycelon C-
200 (manufactured by Nigo Film Co., Ltd., PVA film, thickness 40 μm) was packaged in 30 g portions to obtain the target agricultural chemical formulation for dumping. This formulation is a pesticide formulation for paddy field treatment that treats 10 packs per 10a.

[0098]

[Comparative Example 2] In Example 2 of a pesticide formulation for throwing in paddy, which was produced by using a slurry which was wet-milled without compounding Pluronic P103, the slurry used was replaced with the slurry described as Experiment No. 6 in Test Example 1. In order to obtain granules having a pyrazolate content of 63%,
4 parts were required, and the amount of kneading water was too much, and it was difficult to granulate. Therefore, it was not possible to obtain the target agricultural chemical formulation for dumping.

The content of granules which can be obtained by using the slurry was limited to 47.3%. In this case, to obtain the same amount of active ingredient as in Example 2, it was necessary to treat 400 g of this granule per 10a. Compared with the pesticide formulation for paddy field injection of Example 2 which has the same active ingredient as 300 g, the pesticide formulation for paddy field implantation of this example is easy to carry in terms of economical efficiency such as raw material cost, packaging cost and freight charge. It is also disadvantageous in terms of labor and other uses.

[0100]

[Example 3] Granular wettable powder Nipseal NA (manufactured by Nippon Silica Co., Ltd., amorphous silica, 5.0 parts) produced by using a slurry wet-milled by blending Pluronic P103, Pearlex NP (Japan) Paper Manufacturing Co., Ltd., sodium lignin sulfonate, 10.0 parts),
Neogen powder (Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzene sulfonate, 2.0 parts) and dried potato starch (Matsutani Chemical Co., Ltd., 18.42 parts) were mixed, and Experiment No. 5 was added to Test Example 1. Slurry described as (7
(9.53 parts) and kneading water (a small amount) were added and kneaded. Next, a basket type granulator (Kikusui Seisakusho Co., Ltd., L
-5 type) was used to granulate with a 0.7 mm screen and then dried in a blow dryer set at 70 ° C.
The obtained granules were sized with a sieve of 1 mm to 0.3 mm to obtain a granular wettable powder containing 63% of pyrazolate. This agent can be used in the same manner as a flowable agent by diluting 300 g per 10 a with a small amount of water.

[0101]

Comparative Example 3 In the granular wettable powder Example 3 in which the slurry was wet-milled without blending Pluronic P103, the slurry used in Example 3 was changed to the slurry described as Experiment No. 6 in Test Example 1. However, the amount of kneading water was too much, and the maximum limit was to obtain a granular wettable powder having an active ingredient content of 52.5%, and the target granular wettable powder could not be obtained.

To obtain the same amount of active ingredient as in Example 3 using the above-mentioned granular wettable powder, 10 parts of this granule 360 was used.
It was necessary to process g. Compared with the granular wettable powder of Example 3 having the same active ingredient as 300 g, the granular wettable powder of this example is disadvantageous in terms of economy and convenience in use.

[0103]

Example 4 Granular wettable powder manufactured by using a slurry wet-milled with Epan u103 (99.0%, 70.7 parts), Demol EP (Kao Corporation, carboxylic acid) System polysoap, 1.
5 parts), Hitenol 12 (Daiichi Kogyo Seiyaku Co., Ltd.,
Sulfonate ammonium salt of polyoxyethylene alkyl ether, 0.15 part), Epan u103 (0.8
Part) and water (26.85 parts) were mixed and wet-ground under the same conditions as in Test Example 1 to obtain a slurry containing 70% of dichromedine. Nipseal NA (10.0 parts), kaolin (6.85 parts), vanilex N (8.0 parts) and neogen powder (2.0 parts) were mixed in a speed kneader, and the slurry obtained earlier was mixed. (100.0 parts) was added and mixed, and granulated. The obtained granulated product was dried in a blow dryer at 70 ° C., and then 0.2 to 0.7 mm sections were sieved to obtain a granular wettable powder containing 70% of diclomedine. The present granular wettable powder can be diluted with a small amount of water and used as a mongale agent for aerial application.

[0104]

[Comparative Example 4] Granular wettable powder which was attempted to be produced by using a slurry which was wet-milled without blending Epan-u103 In the wet-milling of Example 4, the mixture except Epan-u103 was wet-milled in the same manner as in Example 4. However, the viscosity of the slurry containing 70% diclomedine increased, and it was impossible to grind it. Therefore, the target granular wettable powder could not be obtained.

In order to wet-mill the mixture except for Epan u103, it is necessary to reduce the amount of the Monguard drug substance to 50.5 parts and the amount of water to 47.85 parts as compared with Example 4. Yes, the concentration of grindable diclomedine was limited to 50%. Granulation was carried out in the same manner as in Example 4 using the 50% slurry of diclomedine to give diclomedine 3
A granular wettable powder containing 5% was obtained. Table 3 shows a composition comparison between Example 4 and Comparative Example 4. "-" In the table means that no component was added.

[0106]

[Table 3]   Granular wettable powder composition ――――――――――――――――――――――――――――――――――――                 Ingredients Content in Example 4 Content in Comparative Example 4 ―――――――――――――――――――――――――――――――――――― Mongard product in slurry 70.7 parts 50.5 parts         (Diclomedine content in slurry) (70.0%) (50.0%)                 Demol EP 1.5 parts 1.5 parts                 Hitenol 12 0.15 parts 0.15 parts                 Epan U103 0.8 part −                 Water 26.85 parts 47.85 parts ―――――――――――――――――――――――――――――――――――― In a granular wettable powder The above slurry 100.0 parts 70.0 parts           (Diclomedine content in wettable powder) (70.0%) (35.0%)                 Nipseal NA 10.0 parts 10.0 parts                 Kaolin 6.85 parts 43.49 parts                 Vanillex N 8.0 parts 8.0 parts                 Neogen powder 2.0 parts 2.0 parts ――――――――――――――――――――――――――――――――――――

[0107]

[Example 5] Granular wettable powder manufactured by using a slurry which was mixed with Epan-u102 and wet-milled (99.5%, 65.33 parts), Epan-u102 (1.0 parts), New Call 291PG
(Nippon Emulsifier Co., Ltd., sodium salt of dialkyl sulfosuccinate, 0.8 parts) and water (32.87 parts)
And mixed with Dynomill KDL type (600 ml continuous vessel, 480 ml of glass beads with a diameter of 1 mm,
Rotation speed 3000 rpm, supply speed 200 ml / min)
Was wet pulverized to obtain a slurry containing 65% of pyrimidiphene. Nipseal NA (18.0 parts), Tamol PP (8.0 parts), Neogen powder (2.0
Part), Amycol No. 1 (3.0 parts) and kaolin (7.03 parts) were mixed in a kneader, then the resulting slurry (92.31 parts) was added and kneaded, and an extrusion granulator EXD1 type (0.7 mm) was used. Granulated using a screen) and dried in a fluidized bed dryer (airflow temperature 70 ° C.) to 0.2
The ~ 0.8 mm section was sieved to obtain a granular wettable powder containing pyrimidifen 60%. This granular wettable powder can be diluted with water and used as a spray for acaricide.

[0108]

[Comparative Example 5] Granular wettable powder which was attempted to be produced by using a slurry which was wet-milled without blending Epan-u102 In the wet-milling of Example 5, the mixture except Epan-u102 was wet-milled in the same manner as in Example 5. Attempts were made, but the viscosity of the slurry containing 65% pyrimidiphen increased, and it was impossible to grind. Therefore, the target granular wettable powder could not be obtained.

In order to wet-mill the mixture except for Epan u102, it is necessary to reduce the amount of the pyrimidiphen drug substance to 45.23 parts and the amount of water to 53.97 parts as compared with Example 5. And the concentration of millable pyrimidifen was limited to 45%. Using this pyrimidiphene 45% slurry, granulation was performed in the same manner as in Example 5 to obtain a granular wettable powder containing pyrimidiphene 35%.
Table 4 shows a composition comparison between Example 5 and Comparative Example 5. "-" In the table means that no component was added.

[0110]

[Table 4]   Granular wettable powder composition ――――――――――――――――――――――――――――――――――――                 Ingredients Content in Example 5 Content in Comparative Example 5 ―――――――――――――――――――――――――――――――――――― Pyrimidiphen drug substance in slurry 65.33 parts 45.23 parts       (Pyrimidiphen content in slurry) (65.0%) (45.0%)                 Epan U102 1.00 copy-                 Newcol 291PG 0.80 copy 0.80 copy                 Water 32.87 parts 53.97 parts ―――――――――――――――――――――――――――――――――――― Granular wettable powder The above slurry 92.31 parts 77.8 parts         (Pyrimidiphen content in wettable powder) (60.0%) (35.0%)                 Nipseal NA 18.0 part 18.0 part                 Tamor PP 8.0 part 8.0 part                 Neogen powder 2.0 parts 2.0 parts                 Amicol No. 1 3.0 parts 3.0 parts                 Kaolin 7.03 parts 33.19 parts ――――――――――――――――――――――――――――――――――――

[0111]

Industrial Applicability According to the present invention, it has become possible to produce a solid preparation containing a high concentration of a solid pesticidal active ingredient finely pulverized by wet pulverization. As a result, the weight of the pesticide formulation can be reduced, and labor and cost can be reduced in terms of production and transportation. In terms of distribution and use, it is easy to handle and contributes greatly to the development of agriculture.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI A01N 43/56 A01N 43/56 C 43/58 43/58 B (72) Inventor Hiroshi Sahi 1041 Yasu, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Co., Ltd. (56) Reference JP-A-3-163005 (JP, A) JP-A-8-40809 (JP, A) JP-A-5-17303 (JP, A) JP-A-6-48902 (JP , A) JP-A-3-146126 (JP, A) JP-A-5-310516 (JP, A) JP-A-4-297403 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB) Name) A01N 25/00 A01N 25/08-25/14 A01N 25/30

Claims (17)

(57) [Claims] 1. A suspension containing a high-concentration pesticide active ingredient is wet-milled by blending a polyalkylene glycol-type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule, Knead and granulate the obtained suspension (however, the wet grinding and
Except when freeze-drying is performed during kneading and granulation. ) High-concentration pesticide solid preparation obtained by. 2. A polyalkylene glycol type nonionic surfactant is represented by the following formula: [Wherein R ¹ represents a hydrogen atom, a higher alcohol residue, an alkylphenol residue, an arylphenol residue, a fatty acid residue, a higher aliphatic amine residue or a fatty acid amide residue, and x 1, x 2, x 3 and x 4 Each independently 4 or more 9
An integer of 00 or less and y1, y2, y3 and y4 each independently represent an integer of 16 or more and 130 or less. ] The high-concentration agricultural chemical solid preparation according to claim 1, which is one or more nonionic surfactants selected from the group consisting of compounds (1) to (4) represented by the following formula. 3. The highly concentrated agricultural chemical solid preparation according to claim 2, wherein R ¹ is a hydrogen atom. 4. A polyalkylene glycol type nonionic surfactant is represented by the following formula: [In the formula, x1 and x2 each independently represent an integer of 4 or more and 900 or less, and y1 represents an integer of 16 or more and 70 or less. ] The high-concentration agrochemical solid formulation of Claim 1 which is a nonionic surfactant which consists of a compound represented by these. 5. The propylene glycol portion of the polyalkylene glycol type nonionic surfactant has a molecular weight of 2000.
The high-concentration pesticide solid preparation according to any one of claims 1 to 4, wherein the ratio of the molecular weight of the ethylene glycol portion to the molecular weight of the propylene glycol portion is 0.05 to 10 times. 6. The propylene glycol portion of the polyalkylene glycol type nonionic surfactant has a molecular weight of 2500.
The high-concentration agrochemical solid formulation according to any one of claims 1 to 4, wherein the ratio of the molecular weight of the ethylene glycol portion to the molecular weight of the propylene glycol portion is 0.1 to 4 times. 7. The propylene glycol portion of the polyalkylene glycol type nonionic surfactant has a molecular weight of 2700.
The high-concentration agrochemical solid formulation according to any one of claims 1 to 4, wherein the ratio of the molecular weight of the ethylene glycol moiety to the molecular weight of the propylene glycol moiety is 0.2 to 1 times. 8. The high-concentration pesticide solid preparation according to any one of claims 1 to 7, which comprises a water surface floating agent. 9. The high-concentration pesticide according to claim 8, wherein the surface floating agent is cork, wood powder, foamed shirasu, foamed pumice stone, calcined vermiculite, foamed perlite, foamed synthetic resin, synthetic resin powder or a plastic hollow body. Solid formulation. 10. A water surface extender is contained in any one of claims 1 to 9.
The high concentration pesticide solid preparation according to any one of 1. 11. The high-concentration pesticide solid preparation according to claim 10, wherein the water surface spreader is an acetylene-based surfactant, a silicon-based surfactant or a fluorine-based surfactant. 12. A suspension containing a high-concentration agrochemical active ingredient is wet-milled by blending a polyalkylene glycol-type nonionic surfactant containing ethylene glycol and propylene glycol in a block form in the molecule, The obtained suspension is kneaded and granulated (however, the wet pulverization and the
Excludes freeze-drying during kneading and granulation. ) , The method for producing the high-concentration agrochemical solid preparation according to any one of claims 1 to 11. 13. A pesticide formulation for throwing into a paddy field, which comprises the high concentration pesticide solid formulation according to any one of claims 1 to 11 packaged in a water-soluble film or sheet. 14. A method of use, wherein the high-concentration pesticide solid preparation according to any one of claims 1 to 11 is transferred from a ridge to a paddy field. 15. A method of use, wherein the high-concentration pesticide solid preparation according to any one of claims 1 to 11 is treated together with inflow of irrigation water from the mouth of a paddy field. 16. A method of using, wherein the pesticide formulation for paddy field injection according to claim 13 is poured along with the inflow of irrigation water from the mouth of a paddy field. 17. A method of using, wherein the pesticide formulation for paddy field injection according to claim 13 is injected into a paddy field from a ridge.