JP5706411B2 - Quinomethionate formulation with reduced phytotoxicity - Google Patents

Description

  The present invention has a cumulative 50% particle diameter of active ingredient particles (hereinafter referred to as “medium diameter” as required) of 3 to 8 μm, 25% particle diameter of 1 μm or more and 75% particle diameter of 10 μm or less, preferably 6-methylquinoxaline-2,3-dithiocarbonate for crops (hereinafter referred to as necessary) by setting the median diameter to 4-7 μm, 25% particle size to 2 μm or more and 75% particle size to 8.5 μm or less. The present invention relates to an aqueous suspension preparation technology that reduces the phytotoxicity caused by the “quinomethionate”.

Quinomethionate is used as an agricultural disease control agent that exhibits a high effect on powdery mildew in various crops, or a pest control agent that exhibits a high effect on pests such as mites and whiteflies that are difficult to control pests. Quinomethionate is a solid of yellow crystals at room temperature, and is generally put into practical use as a wettable powder containing 10 to 50% of quinomethionate.
As described above, quinomethionate has an excellent medicinal effect as a disease control agent or a pest control agent. However, when quinomethionate is sprayed on the foliage of crops, it has the property of causing phytotoxicity to crops, so the target crops that are actually used are limited to crops that are unlikely to cause phytotoxicity. Use at a low concentration within the specified range at high temperatures, not to be used for seedlings or soft seedlings immediately after planting, and to avoid use in the flowering and new leaf development periods for trees. There is a problem in that it is necessary to limit the time and concentration of use, and the performance in terms of the effects inherent to the drug cannot be fully utilized.

  An object of the present invention is to provide a quinomethionate preparation and a production technique in which an aqueous suspension preparation containing quinomethionate as an active ingredient has reduced phytotoxicity to crops while maintaining or improving conventional effects.

  As a result of diligent studies to overcome the above problems, the present inventors have found that phytotoxicity is caused by quinomethionate having a fine particle size, and further includes mineral fine powder in the preparation, such as a wettable powder. It was found that strong phytotoxicity was shown in the preparation.

The present invention contains quinomethionate as an active ingredient, the median diameter of the active ingredient particles is 3 to 8 μm, the 25% particle diameter of the active ingredient particles is 1 μm or more, and the 75% particle diameter of the active ingredient particles is 10 μm. The present invention relates to an aqueous suspension preparation characterized by being free of mineral fine powder.
Preferably, the median diameter of quinomethionate is 4-7 μm.
More preferably, the 25% particle size of quinomethionate is 2 μm or more, and the 75% particle size of quinomethionate is 8.5 μm or less.
It has been found that the aqueous suspension preparation of the present invention can achieve the above-mentioned problems, and has reached the present invention.

  The inventors of the present invention have found that quinomethionates are widely distributed in the conventional quinomethionate wettable powders from coarse particles to fine particles. This is because it is difficult to control the particle size distribution of quinomethionate, which is an active ingredient in the preparation, in the dry pulverization method used for the preparation of a wettable powder preparation. In the case of a conventional quinomethionate wettable powder produced by a dry pulverization method, it is difficult to actually measure the particle size of the quinomethionate, but it is generally considered to be 0.5 to 15 μm.

In the present invention, the particle size can be controlled by using a wet pulverizer, particularly a bead mill, and the particle size distribution of the quinomethionate which is an active ingredient is adjusted as compared with the dry pulverization method.
Normally, when the particle size of the drug substance is reduced, the drug effect is enhanced, but even if the advantages of the drug effect increase are taken into consideration, the drug damage caused by the drug substance is extremely likely to occur. In addition, when the particle size of the drug substance is increased, it is difficult for phytotoxicity to occur, but the pharmacological effect is greatly reduced.
However, the inventors of the present invention include conventional quinomethionate preparations that have a fine particle size that causes phytotoxicity by adjusting the particle size distribution of quinomethionate to an aqueous suspension preparation that does not contain mineral fine powder. It was found that the phytotoxicity of quinomethionate can be significantly suppressed while maintaining or improving the medicinal properties of quinomethionate compared to the wettable powder.

  As far as the present inventors know, such an effect is an excellent effect observed only in the quinomethionate preparation. It has been found that the aqueous suspension preparation of the present invention can achieve the above problems due to this excellent effect.

The aqueous suspension preparation of the present invention has significantly reduced phytotoxicity to crops compared to conventional quinomethiomate preparations. Therefore, the aqueous suspension preparation of the present invention is likely to cause phytotoxicity, so that it can be applied at crops and times that cannot be applied by conventional preparations.
Furthermore, the conventional quinomethiomate formulation had to be used at a low dose for the purpose of avoiding phytotoxicity, but the aqueous suspension formulation of the present invention can be applied at a high dose, thereby sustaining the effect. The period can be extended and the number of spraying can be reduced. From the above, labor saving is expected in cultivating crops.

  Hereinafter, the present invention will be described in detail.

In the aqueous suspension preparation of the present invention, quinomethionate is contained, for example, at a concentration of 0.1 to 70 mass%, preferably 10 to 50 mass%, based on the mass of the agricultural chemical aqueous suspension formulation.
The quinomethionate used in the aqueous suspension formulation of the present invention has a median diameter of 3-8 μm, preferably 4-7 μm.
Further, the quinomethionate used in the aqueous suspension preparation of the present invention has a 25% particle size of 1 μm or more, preferably 2 μm or more, and 10 μm or less, preferably 8.5 μm or less, 75%. It has a particle size.

The term “median diameter (cumulative 50% particle diameter)” used in the present specification means that when the cumulative value from the smaller particle size to the larger particle size distribution on the volume basis indicates 50%. It represents the particle size (ie median diameter).
The term “25% particle size” used in the present specification represents a particle size when the cumulative value from the smaller particle size to the larger particle size distribution on the volume basis shows 25%.
The term “75% particle size” used in this specification represents a particle size when the cumulative value from the smaller particle size to the larger particle size distribution on the volume basis shows 75%.
In the aqueous suspension preparation of the present invention, as a method for measuring the particle size distribution of quinomethionate, a measurement method using a laser diffraction method can be used. For example, using a laser analysis type particle size distribution measuring device SALD-2200 (manufactured by Shimadzu Corporation), measurement is performed under the condition of a refractive index of 1.95-0.05i, and the volume diameter of the particles is obtained.

  The quinomethionate used in the aqueous suspension preparation of the present invention is a known compound. As the quinomethionate becomes finer, the cohesive force / adhesive force becomes higher. Therefore, it is difficult to obtain the desired particle size distribution from the quinomethionate or the quinomethionate wettable powder obtained by dry pulverization. Accordingly, the median diameter of quinomethionate is 3-8 μm, the 25% particle diameter is 1 μm or more, and the 75% particle diameter is 10 μm or less, preferably the median diameter is 4-7 μm, the 25% particle diameter is 2 μm or more, and 75 Examples of a method for adjusting the% particle diameter to 8.5 μm or less include a wet pulverization method in which a slurry in which quinomethionate is suspended is pulverized by stirring at high speed together with fine glass beads, zirconia beads and the like. However, the present invention is not limited to these methods.

More specifically, one embodiment of the fine particle formation is as follows. First, quinomethionate is pulverized to a median diameter of 30 μm or less, preferably 20 μm or less using a dry pulverizer such as a hammer mill, and a predetermined amount of the fine particles and a surfactant are used. Then, the dispersion medium is sufficiently mixed and wet-dispersed, and then pulverized to a target particle size by a wet pulverizer such as a bead mill. In order to suspend and suspend the finely pulverized particles obtained in the dispersion medium for a long time, it is desirable to add an appropriate amount of a thickener. Furthermore, an antifoamer, a preservative, etc. can also be added as needed.
These conditions can be easily examined and set by those skilled in the art.

  In the aqueous suspension preparation of the present invention, quinomethionate exists in a suspended state in a dispersion medium. The dispersion medium used is mainly water. The amount of the dispersion medium used is 20 to 98% by mass, preferably 40 to 80% by mass, based on the mass of the aqueous suspension preparation of the present invention.

The aqueous suspension preparation of the present invention contains a surfactant to suspend quinomethionate in the dispersion medium.
Examples of the surfactant that can be used in the aqueous suspension preparation of the present invention include sulfonate anionic surfactants and styrenated phenol surfactants.
The sulfonate anionic surfactant, preferably, mono- or dialkyl (C ₁ -C ₄₎ Na naphthalene sulfonate, K or NH ₄ salts, Na naphthalene sulfonate formalin condensates, K or NH ₄ salt, monoalkyl ( C ₁ -C ₄₎ those selected Na naphthalene sulfonate formalin condensates, K or NH ₄ salts, Na polystyrene sulfonate, K or NH ₄ salt, and Na lignin sulphonate, from the group consisting of K or Ca salt, Is appropriate.
The styrenated phenol surfactant is preferably polyoxyethylene (10-18 mol) tristyryl phenyl ether, polyoxyethylene (10-18 mol) tristyryl phenyl ether sulfate Na, K, NH ₄ or triethanol. Amine salts, or Na, K, NH ₄ or triethanolamine salts of tristyryl phenyl ether phosphate.
These surfactants are usually 0.1 to 15% by mass, preferably 1 to 10% by mass, based on the mass of the aqueous suspension preparation of the present invention, from the viewpoint of economy and storage stability. Used in.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.

In the aqueous suspension preparation of the present invention, various surfactants other than those described above, for example, nonionic surfactants and anionic surfactants may be used in combination as necessary. These surfactants are also used in the aqueous suspension preparation of the present invention in the same amount as the above-mentioned surfactant.
Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene resin acid or resin acid ester thereof, polyoxyethylene castor oil, polyoxyethylene mono- or dialkyl ether, polyoxyethylene alkanediol, polyoxyethylene Ethylene sorbitan alkylate, sorbitan or sucrose alkylate, polyoxyethylene dialkyl diphenyl ether, polyoxyethylene alkylphenyl ether formalin condensate, polyoxyethylene styrenated or benzylated phenyl ether formalin condensate, polyoxyethylene polyoxypropylene block polymer or Examples thereof include polydimethylsiloxane surfactants.
Examples of such anionic surfactants include alkyl sulfates or sulfonates, α-olefin sulfonates, alkylbenzene sulfonates, dialkyl sulfosuccinates, alkyl succinic acid half ester sulfonates, polyoxyethylene alkyl ether sulfates or phosphates, polyoxyethylenes. Examples thereof include Na, K, NH ₄ or mono-triethanolamine salts such as alkylphenyl ether sulfate or phosphate, polyoxyethylene polyoxypropylene block polymer sulfate or phosphate, or dialkyldiphenyl ether sulfonate.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.

Thickeners that can be used in the aqueous suspension formulations of the present invention include heteropolysaccharides produced by plants or microorganisms such as guar gum, locust bean gum, xanthan gum or its isopropyl alcohol derivative, welan gum or lambzan gum having thixotropic viscosity characteristics. Natural thickeners such as saccharide, gum arabic, gum tragacanth, carrageenan, sodium alginate or pectin, or polyacrylate, polymethacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methacrylate, methyl or ethyl cellulose, carboxymethyl or ethyl cellulose, Examples include synthetic or semi-synthetic thickeners such as hydroxymethyl or ethyl cellulose or starch derivatives. These thickeners can be used singly or as a mixture of two or more.
The thickener is usually in an amount of 0.05 to 10% by mass, preferably 0.1 to 3% by mass, based on the mass of the aqueous suspension preparation of the present invention, from the viewpoint of economy and storage stability. Used in.

  In the aqueous suspension preparation of the present invention, an antifoaming agent, an antifreezing agent, a preservative, a sedimentation inhibitor, a crystal growth inhibitor, a pH adjuster, an antioxidant, etc. are conventionally used as an agrochemical aqueous solution for convenience. If it is used for a suspension formulation, it can be used without being specifically limited.

  Examples of the antifoaming agent that can be used in the aqueous suspension preparation of the present invention include silicone oil, silicone emulsion, fatty acid, silica, or polyoxyethylene polyoxypropylene block polymer. These antifoaming agents can be used singly or as a mixture of two or more. The antifoaming agent is usually used in an amount of 0.05 to 2% by mass, preferably 0.1 to 0.5% by mass based on the mass of the aqueous suspension preparation of the present invention.

  Examples of the antifreezing agent that can be used in the aqueous suspension preparation of the present invention include lower alcohols (such as methanol and ethanol), ethylene glycol, propylene glycol, diethylene glycol, glycerin, and inorganic salts. These antifreeze agents can be used singly or as a mixture of two or more. The antifreeze agent is usually used in an amount of 1 to 10% by mass, preferably 3 to 8% by mass, based on the mass of the aqueous suspension preparation of the present invention.

  Examples of the preservative that can be used in the aqueous suspension preparation of the present invention include benzoate, sorbate, dehydroacetate, parabens, thiabendazole, isothiazoline compounds, thiazole, thiazolone, bronopol, and pyridine compounds. Examples of the commercial products include Biocide 800A, Proxel GX-L, BDN, Sun Eyebac 300K, Sun Aisol 200, Biotac, Bioace, and Biohope. These preservatives can be used individually by 1 type or in mixture of 2 or more types. The preservative is usually used in an amount of 0.05 to 1% by mass, preferably 0.05 to 0.5% by mass, based on the mass of the aqueous suspension preparation of the present invention.

  Examples of the crystal growth inhibitor that can be used in the aqueous suspension preparation of the present invention include polysaccharides such as starch, alginic acid, mannose or galactose, polyvinylpyrrolidone, white carbon, ester gum, or petroleum resin. . These crystal growth inhibitors can be used singly or as a mixture of two or more. The crystal growth inhibitor is usually used in an amount of 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the mass of the aqueous suspension preparation of the present invention.

  Examples of the antioxidant that can be used in the aqueous suspension preparation of the present invention include a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, and a phosphate-based antioxidant. . These antioxidants can be used individually by 1 type or in mixture of 2 or more types. The antioxidant is usually used in an amount of 0.05 to 2% by mass, preferably 0.1 to 1% by mass, based on the mass of the aqueous suspension preparation of the present invention.

The aqueous suspension formulation of the present invention does not contain mineral fines. Mineral fine powders are included in wettable pesticide formulations to increase the amount added to the powder raw material for easy handling. Specific examples of mineral fine powders include pyrophyllite clay, kaolin clay, meteorite clay, talc, calcium carbonate, diatomaceous earth, acid clay, and attapulgous clay.
Even if the particle size of the quinomethionate is a desired value, when the mineral fine powder is contained in the aqueous suspension preparation, the effect of the conventional quinomethionate preparation is reduced as in the aqueous suspension preparation of the present invention. It is not possible to make an agrochemical formulation that reduces or protects crops while maintaining or improving it. In other words, the aqueous suspension preparation of the present invention has an effect that exceeds the conventional quinomethionate preparation (used practically as a wettable powder containing mineral fine powder).

Below, the specific manufacturing method of the quinomethionate formulation as an agricultural disease control agent or pest control agent of this invention is described. However, the method for producing the aqueous suspension preparation of the present invention is not limited to the following.
First, a premix A containing quinomethionate and a premix B containing a thickener are prepared in advance, and the aqueous suspension preparation of the present invention can be obtained by mixing them. Premix A is, for example, a mixture of quinomethionate pulverized in advance with a hammer mill or jet mill to a median diameter of 30 μm or less, preferably 20 μm or less, lignin sulfonate Na, antifoaming agent and other additives, and water. The mixture is sufficiently stirred and then pulverized to a predetermined particle size using a wet pulverizer. Premix B consists of, for example, a thickener 0.1 to 5%, an antifreezing agent 5 to 50%, a preservative 0.1 to 5%, other additives, and water as a general composition. It is desirable to disperse and dissolve. The mixing ratio of the premix A and the premix B is generally mixed at a ratio of 50 to 90% to 50 to 10%. In these premixes, other additives (precipitation inhibitor, crystal growth inhibitor, pH adjuster, antioxidant, etc.) may be appropriately mixed as necessary.

  The aqueous agricultural chemical suspension thus obtained usually contains 5 to 50% by mass of quinomethionate having a median diameter of 3 to 8 μm, and has a viscosity of 200 to 5000 mPa · s, preferably 400 to 1000 mPa. S, adjusted to pH 4 to 9, and can be stably maintained without causing particle size growth, sedimentation separation, caking and gelation in a normal long-term stability test at -5 to 40 ° C. In addition, the production of the aqueous agricultural chemical suspension preparation of the present invention is not necessarily limited to the above procedure, but the supply state of quinomethionate, the content ratio in the aqueous agricultural suspension preparation, a mixing device, a surfactant, a thickener, etc. It can be appropriately changed depending on the type and content thereof, and the range is obvious to those skilled in the art.

  The method for using the aqueous suspension preparation of the present invention is not particularly limited. Usually, a diluted solution obtained by diluting in a predetermined amount of water is sprayed on the crop. The dilution rate is not particularly limited, but is usually 10 to 10,000 times, preferably about 100 to 3000 times.

By using the aqueous suspension preparation of the present invention, it is possible to reduce phytotoxicity to crops while maintaining the same effect as a conventional quinomethionate-containing drug. Although the example of the crop which can apply the aqueous suspension formulation of this invention is shown below, it is not necessarily limited to this.
Examples of crops to which the aqueous suspension preparation of the present invention can be applied include crop fruit trees, such as avocado, apricot, fig, yokan, ume, unshu mandarin orange, outo, oysters, kabo, kiwifruit, plums, western none, mandarin orange, dekopon , None, summer orange, nectarine, hassaku, papaya, loquat, grape, grape, mango, peach, yuzu, apple, lemon, etc .;
Cereals such as barley, wheat, paddy rice, corn, pigeons, rye, upland rice;
Potatoes, such as potatoes, potatoes, potatoes, potatoes, etc .;
Vegetables such as red bean paste, strawberry, kidney bean, pea bean, okra, turnip, pumpkin, cabbage, cucumber, burdock, pigtails, sardine, watermelon, celery, broad bean, daikon, daizu, onion, tensai, togarashi , Tomatoes, tomatoes, eggplants, garlic, carrots, green onions, hakusai, parsley, bell peppers, spotted rice, melon, lettuce, etc .;
Special crops such as sugar cane, turf, tobacco, tea, rapeseed, pop, etc .;
Flowers, for example, hydrangea, carnation, gerbera, gazania, peony, snapdragon, calendula, salvia, perennial gypsophila, sweet pea, statice, saintpaulia, dahlia, timothy, delphenium, eustoma, verbena, sunflower, rose, begonia, petunia, poinsettia , Lilac, apple, rosemary, etc .;
List trees, such as red snapper, maple, sardine, wig, drill, keyaki, sakura, cypress, azalea, camellia, noodles, agaric, yanagi Can do.

The quinomethionate formulation of the present invention can be mixed or used in combination with one or more fungicides, insecticides, acaricides, repellents, synergists, or plant growth regulators. The mixture thus obtained has a broad activity spectrum.
Although the example of the bactericidal agent (general name) which can be mixed or used together with the quinomethionate formulation of this invention is shown below, the bactericidal agent which can be mixed or used together is not necessarily limited to this.
Bactericides that can be mixed or used in combination with the quinomethionate formulation of the present invention include copper bactericides such as cupric hydroxide, basic copper sulfate, basic copper oxychloride, Organic copper (oxine-copper), DBEDC (complex of bis (ethylenediamine) copper-bis- (dodecylbenzenesulfonic acid)), copper nonylphenol sulfonate, etc .;
Inorganic bactericides such as calcium carbonate, sulfur, calcium polysulfide, silver, sodium hydrogen carbonate, sodium hypochlorite , Potassium hydrogen carbonate, zinc sulfate, etc .;
Organic sulfur agents such as mancozeb, maneb, ambam, ziram, thiram, polycarbamate, propineb, thiadiazin, etc. ;
Organophosphorus agents such as iprobenfos, edifenphos, tolclofos-methyl, fosetyl and the like;
Melanin synthesis inhibitors such as fthalide, tricyclazole, pyroquilon, carpropamid, diclocymet, fenoxanil and the like;
Benzimidazoles, such as thiophanate-methyl, benomyl, thiabendazole, dietofencarb, etc .;
Dicarboximide agents such as iprodione, procymidone and the like;
Acid amide agents, such as mepronil, flutolanil, boscalid, furametpyr, thifluzamide, metalaxyl, oxadixyl, etc .;
Sterol biosynthesis inhibitors such as prochloraz, pefurazoate, fenarimol, triadimefon, bitertanol, fenbuconazole, difenoconazole, ipconazole, ipconazole Imibenconazole, propiconazole, tebuconazole, triflumizole, triforine, microbutanil, oxpoconazole fumarate, tetraco Tetraconazole, simeconazole, hexaconazole, cyproconazole, bromuconazole, carbendazim, fluconazole furconazole), hymexazol (hymexazol), fluquinconazole (fluquinconazole), metconazole (metconazole), triticonazole (triticonazole) or the like;
Strobilurins such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, famoxadone, fluoxastrobin , Pyraclostrobin, picoxystrobin, orysastrobin, etc .;
Anilinopyrimidine-based agents such as pyrimethanil, mepanipyrim, cyprodinil and the like;
Synthetic antibacterial agents such as tecloftalam, oxolinic acid and the like;
Antibacterial fungicides such as kasugamycin, validamycin (-A), mildiomycin, blasticidin S, streptomycin, oxytetracycline, polyoxin Complex (polyoxins), polyoxin D zinc salt (polyoxorim), etc .;
Natural product-derived fungicides, such as extract from mushroom, etc .;
Soil fungicides such as methyl bromide, chloropicrin, metam-ammonium, flusulfamide, hydroxyioxazole, echlomezole, dazomet (Dazomet), chloroneb, etc .;
Other fungicides include, for example, probenazole, acibenzolar-S-methyl, isoprothiolane, ferimzone, diclomezine, pencicuron, fluoroimide, captan ( captan), chlorothalonil, dithianon, diflumetorim, triazine (also known as anilazine), fluazinam, iminoctadine triacetate, iminoctadine albesilate, iminoctadine albesilate Propamocarb, cyazofamid, fenhexamid, tiadinil, amisulbrom, benthiazole, fosetyl aluminum (fo setyl-AL, zineb, penthiopyrad, zoxamid, fluopicolide, fluopyrum, cymoxanil, metalaxyl-M, dimethomorph, fluoxoyl fuldioxonil, ethaboxam, benchthiavalicarb-isopropyl, cyflufenamid, pyribencarb, ametoctrazine, mandipropamid, fluanid, ichlopet , Diclomezine, polyoxin-B, dodine, metam-sodium, 1,3-dichloropropene (DD) (1,3-dichloropropene) ), Methyl isothiocyanate ( methylisothiocyanate, fenamidone, flumetover, iprovalicarb, metasulfocarb, oxycarboxin, pebulate, pyrazophos, pyrifenox, quintozen (Quintozene), spiroxamine, tecloftalam, tolylfluanid, triadimenol, vinclozolin and the like can be exemplified.

Next, examples of insecticides and acaricides (generic names) that can be mixed or used in combination with the quinomethionate preparation of the present invention are shown below. However, insecticides and acaricides that can be mixed or used in combination are not necessarily limited thereto. is not.
Insecticides that can be mixed or used in combination with the quinomethionate formulations of the present invention include organophosphorus agents such as acephate, chlorpyrifos, diazinon, dichlorvos, dimeton-S-methyl (dimeton-S). -methyl), dimethoate, dimethylvinphos, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos , Methidathion, naled, oxydeprofos, phenthoate, phenthoate, phosalone, pirimiphos-methyl, pyridafenthion, profenofos, prothiofos Prothiofos, propaphos, pyraclofos, salithion, sulprofos, thiometon, tetrachlorvinfos, trichlorphon, vamidothion, etc .;
Carbamates such as alanycarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbofuran, carbosulfan, ethiofencarb, fenobucarb, furothiocarb (Furathiocarb), isoprocarb, mesomyl, metolcarb, pirimicarb, propoxur, thiodicarb, etc .;
Organochlorine agents such as aldrin, chlordane, DDT (p, p'-DDT), endosulfan, lindane, etc .;
Pyrethroids such as acrinathrin, allethrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, ethen Ethofenprox, fenpropathrin, fenvalerate, flucythrinate, flufenprox, fluvalpronate, furamethrin, halofenprox, halfenprox, Imiprothrin, permethrin, phenothrin, prallethrin, pyrethrin, resmethrin, silafluofen, teflutri Tefluthrin, tralomethrin, transfluthrin, etc .;
Neonicotinoid agents, such as acetamiprid, clothianidin, dinotefran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, etc .;
Insect growth regulators such as phenylbenzoyl urea agents, such as chlorfluazuron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, Teflubenzuron, triflumuron, buprofezin, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, cyromazine, etc .;
Juvenile hormone agents, such as diofenolan, phenoxycarb, hydroprene, methoprene, pyriproxyfen, etc .;
Insecticidal substances produced by microorganisms such as abamectin, emamectin-benzoate, ivermectin, lepimectin, milbemectin, nemadectin, nikkomycin , Spinetram, spinosad, BT agent, etc .;
Insecticides derived from natural products, such as anabasine, azadiractin, deguelin, decanoyloctanoylglycerol (decanoyloctanoylglycerol), hydroxypropylstarch, soy lecithin ), Nicotine, nornicotine, oreic acid sodium salt, machine oil (petroleum oil), propylene glycol monolaurate (propylene glycol monolaurate), rapeseed oil ( rape oil), rotenone, etc .;
Other insecticides include, for example, acetoprole, bensultap, cartap, thiocyclam, chlorantraniliprore, chlorfenapyr, diafenthiuron, Cyantraniliprole, ethiprole, fipronil, flonicamid, flubenziamid, hydramethylnon, indoxacarb, metaflumizone, metaaldehyde (Metaldehyde), nicotin sulfate, pymetrozine, pyridalyl, pyrifluquinazon, spirotetramat, tolfenpyrad, triazame Toza (triazamate) and the like.

  Examples of acaricides that can be mixed or used in combination with the quinomethionate preparation of the present invention include, for example, acequinocyl, amitraz, azocyclotin, benzomate (also known as benzoximate), bifenazate, and binapacryl. (Binapacryl), bromopropylate (phenobromolate), clofentezine, cyenopyrafen, cyflumetofen, cyhexatin (cyhexatin hydroxide), dicofol , Dienochlor, ethoxazole, fenazaflor, fenazaquin, fenbutatin oxide, phenothiocarb, fenpyroximate , Fluacrypyrim, hexythiazox, pyrimidifen, polynactins, propargite, pyridaben, spirodiclofen, spiromesifen, tebufen ) And tetradifon.

Examples of nematicides that can be mixed or used in combination with the quinomethionate preparation of the present invention include, for example, aluminum phosphide, benclothiaz, cadusafos, ethoprophos, fosthiazate, imimiafos ), Levamisol hydrochloride, mesulfenfos, metam-ammonium, methyl isothiocyanate, moranteltartarate, oxamyl and the like.
Examples of poisonous baits that can be mixed or used in combination with the quinomethionate preparation of the present invention include, for example, chlorophacinone, coumatetralyl, diphacin (also known as diphacinone), sodium fluoroacetate (sodium fluoracetate) , Warfarin and the like.

Next, examples of repellents and synergists that can be mixed or used in combination with the quinomethionate preparation of the present invention and compounds (generic names) having plant growth regulating activity are shown below. It is not limited to.
Examples of repellents that can be mixed or used together with the quinomethionate preparation of the present invention include, for example, capsaicin, caran-3,4-diol, citronellal, deet, dimethyl Phthalate (dimethyl phthalate), hinokitiol, limonene, linalool, menthol, menthone, naphthalene, naphthalene, thiram, etc .;
As a synergist, for example, methylenedioxynaphthalene, naphthyl propynyl ether, nitrobenzyl thiocyanate, octachlorodipropyl ether, pentynyl phthalimide ( pentynyl phthalimide, phenyl salioxon, piperonyl butoxide, safrole, sesamex, sesamin, sulfoxide, triphenyl phosphate, verbutin Etc.

  Examples of the compound having a plant growth regulating action that can be mixed or used together with the quinomethionate preparation of the present invention include 1-naphthylacetamid, 4-CPA (4-CPA), 6-benzylaminopurine (6 -benzylaminopurine, butralin, calcium chloride, calcium formate, calcium peroxide, calcium sulfate, chlormequat chloride, choline ), Cyanamide, cyclanilide, daminozide, decyl alcohol, dichlorprop, ethephon, ethychlozate, flurprimidol, forchlor Forenor (forclorfenuron), gibberellin (Gibberellic acid), indolebutyric acid, maleic hydrazide potassium salt, mefenpyr, mepiquat chloride, oxine sulfate, 8-hydroxyquinoline sulfate , Paclobutrazol, paraffin, calcium prohexadione-calcium, prohydrojasmon, thidiazuron, trinexapac-ethyl, uniconazole P -P) and wax.

EXAMPLES Next, an Example is given and this invention is demonstrated still in detail. However, the scope of the present invention is not limited to the following examples, and the production method, the surfactant used in the production, and the like can be freely changed without departing from the spirit of the present invention.
Formulation method of various preparations <Example 1>
A quinomethionate (purity 99%, 21 g), previously pulverized to a median diameter of 20 μm by a hammer mill, was obtained from lignin sulfonate Na (3 g), silicone emulsion (antifoam E20) (0.2 g), and water (55.8 g). Was added to the resulting aqueous surfactant solution and mixed for 1 hour at a speed of 400 rpm using a three-one motor (FBL1200 type, manufactured by Shinto Kagaku Co., Ltd.). This mixed solution is put together with glass beads (1 mm hard glass, 75% filled) into Dynomill (MULTI LAB type, manufactured by Shinmaru Enterprises) until the median diameter reaches 5.0 μm under the condition of disk rotation speed of 3200 rpm. Premix A-1 (72 g) was obtained by high-speed grinding for 1 minute. At this time, wet pulverization was carried out while taking care that the temperature of the mixed solution was always 30 ° C. or lower.
Preparation of the thickening solution includes xanthan gum (1.25%), 1,2-benzisothiazolin-3-one (0.5%), propylene glycol (15%), A solution consisting of water (83.25%) was mixed for 1 hour at a speed of 600 rpm using a three-one motor (FBL 1200 type) at room temperature. The obtained mixed liquid was allowed to stand at room temperature for 12 hours or more, and a sufficiently swollen thickening substance was used as premix B-1.
After adding 18 g of premix B-1 to premix A-1 (72 g), it was mixed for 1 hour at a speed of 400 rpm using a three-one motor (FBL 1200 type), and 20% quinomethionate (median diameter 4.63 μm). 90 g of quinomethionate agrochemical suspension containing 25% particle size 2.42 μm and 75% particle size 8.18 μm).

<Example 2>
Quinomethionate (purity 99%, 42 g), which was previously ground to a median diameter of 20 μm with a hammer mill, was converted to alkyl naphthalene sulfonate formalin condensate (6 g), silicone emulsion (antifoam E20) (0.4 g), water (111 .6 g), and mixed for 1 hour at a speed of 400 rpm using a three-one motor (FBL1200 type). This mixed solution is put into a batch-type ready mill (RMB-08 type, manufactured by IMEX) together with glass beads (1 mm hard glass, 40% filled), and the median diameter becomes 5.0 μm under the condition of disk rotation speed 2000 rpm. The mixture was pulverized at high speed for 5 minutes to obtain premix A-2 (144 g). At this time, wet pulverization was carried out while taking care that the temperature of the mixed solution was always 30 ° C. or lower.
Preparation of the thickening solution includes xanthan gum (1.25%), 1,2-benzisothiazolin-3-one (0.5%), propylene glycol (15%), A solution consisting of water (83.25%) was mixed for 1 hour at a speed of 600 rpm using a three-one motor (FBL 1200 type) at room temperature. The obtained mixed liquid was allowed to stand at room temperature for 12 hours or more, and a sufficiently swollen thickening substance was used as premix B-2.
After adding 36 g of premix B-2 to premix A-2 (144 g), it was mixed for 1 hour at a speed of 400 rpm using a three-one motor (FBL 1200 type), and quinomethionate 20% (median diameter 5.09 μm) 180 g of quinomethionate agrochemical suspension containing 25% particle size 2.90 μm, 75% particle size 8.08 μm).

According to the same method as in Example 1 except that high-speed grinding is performed for 10 minutes in the step of obtaining the preparation 1 of the preparation 1 of comparative agent 1 (quinomethionate aqueous suspension preparation of quinomethionate) , quinomethionate 20% (medium) 90 g of a quinomethionate pesticide aqueous suspension preparation containing 0.98 μm in diameter, 0.66 μm in 25% particle size, 1.54 μm in 75% particle size) was prepared.
Comparative agent 2 (quinomethionate wettable powder)
A commercially available wettable powder containing 25% quinomethionate was used. This formulation was produced by a dry milling system and contained mineral fines.

上記結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、検討した全ての作物の幼苗に対して薬害を示さなかった。一方、比較剤１、比較剤２は供試植物全てに薬害を示した。Test Example Next, a test example will be given to explain the effectiveness of the present invention in detail.
Test Example 1 Medicinal damage test for seedlings of various crops The chemical solution of a predetermined concentration shown in Table 1 was sprayed on the whole stems and leaves of potted plant seedlings using a spray gun (1 concentration 3 repetitions). After spraying, it was kept in a glass greenhouse. Ten days after the treatment, the following levels of phytotoxicity (-: no phytotoxicity, +: phytotoxicity) and their symptoms were objectively investigated. The results are shown in Table 1.
Table 1

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 did not show any phytotoxicity to all the crop seedlings examined. On the other hand, the comparative agent 1 and the comparative agent 2 showed phytotoxicity to all the test plants.

Test Example 2 Test of preventive effect against cucumber powdery mildew 5 ml of a predetermined concentration of the chemical solution shown in Table 2 was sprayed per cup using a spray gun over the entire cucumber stem and leaf of the 1.5-stage potted plant (one concentration 3 repetitions). After spraying, the cucumber was kept in a glass greenhouse, and after 24 hours, the cucumber leaf surface was spray-inoculated with a cucumber powdery mildew spore suspension (1 × 10 ⁵ cells / ml). Cucumbers after inoculation were kept in a glass greenhouse, and an objective survey was conducted 9 days after the inoculation based on the following disease severity. Based on the results, the disease severity and control value were calculated from the following equations. The results are shown in Table 2.

上記の結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、キュウリうどんこ病に対して高い効果を示し、その効果は比較剤２と同等であった。No disease (onset index: 0), disease area is less than 6.25% of leaf area (same as above: 1), disease area is between 6.25% and less than 12.5% of leaf area (same: 2), disease area Is 12.5% to less than 25% of the leaf area (same: 3), the diseased area is 25% to less than 50% of the leaf area (same: 4), and the diseased area is 50% or more of the leaf area (same: 5)
Disease severity = {Σ (morbidity index × number of diseased leaves by degree) × 100} ÷ (5 × number of leaves studied)
Control value = 100− (Severity of treated area ÷ Severity of untreated section × 100)
Table 2

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 showed a high effect on cucumber powdery mildew, and the effect was equivalent to that of Comparative Agent 2.

Test Example 3 Residual effect test for cucumber powdery mildew 5 ml per cup of the prescribed concentration of the chemical solution shown in Table 3 was sprayed on the entire cucumber stem and leaves of the pot planted 1.5 leaf stage (1 concentration 3 repetitions) . After spraying, the cucumber was kept in a glass greenhouse, and after 7 days or 14 days of treatment, the cucumber leaf surface was spray-inoculated with a cucumber powdery mildew spore suspension (1 × 10 ⁵ cells / ml). Cucumbers after inoculation were kept in a glass greenhouse, and an objective survey was conducted 9 days after the inoculation based on the following disease severity. Based on the results, the disease severity and control value were calculated from the following equations. The results are shown in Table 3.

上記の結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、キュウリうどんこ病に対して処理１４日後まで残効性を示し、その効果は比較剤２と同等であった。No disease (onset index: 0), disease area is less than 6.25% of leaf area (same as above: 1), disease area is between 6.25% and less than 12.5% of leaf area (same: 2), disease area Is 12.5% to less than 25% of the leaf area (same: 3), the diseased area is 25% to less than 50% of the leaf area (same: 4), and the diseased area is 50% or more of the leaf area (same: 5)
Disease severity = {Σ (morbidity index × number of diseased leaves by degree) × 100} ÷ (5 × number of leaves studied)
Control value = 100− (Severity of treated area ÷ Severity of untreated section × 100)
Table 3

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 showed residual effect until 14 days after treatment against cucumber powdery mildew, and the effect was equivalent to that of Comparative Agent 2. there were.

上記の結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、タバココナジラミに対して高い効果を示し、その効果は比較剤２と同等であった。Test Example 4 Insecticidal test for tobacco whitefly A 400 ml capacity polyethylene cup filled with water was capped with a hole (diameter: about 10 mm) in the center. Insert the absorbent cotton of about 1cm in width and about 14cm in length so that it is immersed in the water in the cup through the hole of the lid, and put the absorbent cotton of about 8cm square on it and the water in the cup is always replenished to the upper absorbent cotton. I did it. In this way, the leaf made from the leaf-planted bean leaf of the pot planting initial leaf stage that was laid for about 24 hours in the greenhouse where tobacco whitefly was generated in advance on the absorbent cotton in which the water in the cup was constantly replenished -Six discs (diameter 20 mm) were placed. About 7 days later, after confirming that eye spots were formed on tobacco whitefly eggs, this cup was placed in an acrylic cylinder having a height of 45 cm and a diameter of 12 cm, and a chemical solution having a predetermined concentration shown in Table 4 was placed on an air brush. Used and sprayed 1.35 ml per cup (1 concentration, 1 repetition). After spraying, it was kept in a constant temperature room at 25 ° C. Seven days after the treatment, the state of larvae was observed under the binocicular, divided into survival and death, and the larval mortality (%) was calculated based on the observation results. The results are shown in Table 4.
Table 4

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 showed a high effect on tobacco whitefly, and the effect was equivalent to that of Comparative Agent 2.

上記の結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、ナミハダニに対して高い効果を示し、その効果は比較剤２と同等であった。Test Example 5 An insecticidal test against a spider mite A 400 ml-capacity polyethylene cup filled with water was capped with a hole (diameter: about 10 mm) in the center. Insert the absorbent cotton of about 1cm in width and about 14cm in length so that it is immersed in the water in the cup through the hole of the lid, and put the absorbent cotton of about 8cm square on it so that the water in the cup is always replenished to the upper absorbent cotton I made it. In this way, six leaf discs (diameter 20 mm) made from kidney bean primary leaves were placed on the cotton wool that had been constantly replenished with water in the cup, and four female adults of the spider mite were inoculated on the leaf discs. did. This cup was placed in an acrylic cylinder having a height of 45 cm and a diameter of 12 cm, and a chemical solution having a predetermined concentration shown in Table 5 was sprayed with 1.35 ml per cup using an air brush (one concentration, one repetition). After spraying, it was kept in a constant temperature room at 25 ° C. Three days after the treatment, the mortality and agonism of adult worms were investigated under a binocular, and the mite killing rate (%) was calculated by dying of the worms. The results are shown in Table 5.
Table 5

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 showed a high effect against the spider mite, and the effect was equivalent to that of Comparative Agent 2.

上記の結果から分かるように、実施例１において製造された本発明の水性懸濁製剤は、チャノホコリダニに対して高い効果を示し、その効果は比較剤２と同等であった。Test Example 6. Test for killing larvae against mite dust mites A 400 ml capacity polyethylene cup filled with water was capped with a hole (diameter: about 10 mm) in the center. Insert the absorbent cotton of about 1cm in width and about 14cm in length so that it is immersed in the water in the cup through the hole of the lid, and put the absorbent cotton of about 8cm square on it so that the water in the cup is always replenished to the upper absorbent cotton I made it. In this way, six leaf discs (diameter 20 mm) made from kidney bean primary leaves were placed on the absorbent cotton that had been constantly replenished with water in the cup, and adult larvae of mushroom dust mites were infested on the leaf discs. Inoculated with a small piece of leaf. The cup was placed in an acrylic cylinder having a height of 45 cm and a diameter of 12 cm, and a chemical solution having a predetermined concentration shown in Table 6 was sprayed with 1.35 ml per cup using an air brush (one concentration, one repetition). After spraying, it was kept in a constant temperature room at 25 ° C. Six days after the treatment, the number of adult larvae surviving under the binocicular was investigated, and the control rate was calculated by the following formula with the ratio of no treatment. The results are shown in Table 6.
Control rate = {1− (adult larvae in treated area ÷ adult larvae in untreated area)} × 100
Table 6

As can be seen from the above results, the aqueous suspension preparation of the present invention produced in Example 1 showed a high effect on the dust mite, and the effect was equivalent to that of Comparative Agent 2.

  Compared with the conventional quinomethiomate preparation, the aqueous suspension preparation of the present invention has greatly reduced phytotoxicity to crops. Moreover, the aqueous suspension preparation of the present invention showed almost the same effect as the conventional quinomethiomate preparation.

上記結果から分かるように、実施例１において製造された本発明の水性懸濁製剤に、比較剤２に含まれる鉱物質微粉を同質量加用した場合には薬害が生じ、鉱物質微粉を加用しなかった場合は薬害が生じなかった。
比較剤２、すなわち、鉱物質微粉を含む従来のキノメチオネート水和剤は薬害を示した。
脱塩水においては、鉱物質微粉を含むと含まないとに関らず、薬害は生じなかった。従って、鉱物質微粉自体のみにより薬害が生じるわけではないことがわかる。
以上より、鉱物質微粉を含むキノメチオネート製剤により薬害が引き起こされることが示された。また、本発明の水性懸濁製剤によれば、そのような薬害を格段に抑えることができることが示された。Test Example 7 Medicinal damage test for cucumber seedlings when mineral fine powder is added to the aqueous suspension preparation of the present invention produced in Example 1 The chemical solution of a predetermined concentration shown in Table 7 is applied to the whole stems and leaves of seedlings of pot-planted crops. Was sprayed using a spray gun to such an extent that the drug solution was dripped (1 concentration 3 repetitions). After spraying, it was kept in a glass greenhouse. Ten days after the treatment, the following levels of phytotoxicity (-: no phytotoxicity, +: phytotoxicity) and their symptoms were objectively investigated. The results are shown in Table 7.
Table 7

As can be seen from the above results, when the same amount of mineral fine powder contained in Comparative Agent 2 is added to the aqueous suspension preparation of the present invention produced in Example 1, phytotoxicity occurs, and the mineral fine powder is added. When not used, no phytotoxicity occurred.
Comparative agent 2, ie, a conventional quinomethionate wettable powder containing mineral fine powder, showed phytotoxicity.
In the desalted water, no phytotoxicity occurred regardless of whether or not it contained mineral fine powder. Therefore, it turns out that a phytotoxicity does not arise only by mineral matter fine powder itself.
From the above, it was shown that phytotoxicity was caused by the quinomethionate preparation containing mineral fine powder. Moreover, according to the aqueous suspension formulation of this invention, it was shown that such a phytotoxicity can be suppressed markedly.

Claims (3)

  6-methylquinoxaline-2,3-dithiocarbonate as an active ingredient, the median diameter of the active ingredient particles is 3 to 8 μm, the 25% particle size of the active ingredient particles is 1 μm or more, and the active ingredient particles An aqueous suspension preparation characterized by having a 75% particle size of 10 μm or less and containing no mineral fine powder.   The aqueous suspension formulation according to claim 1, wherein the median diameter of the active ingredient particles is 4 to 7 µm.   The aqueous suspension preparation according to claim 2, wherein the 25% particle diameter of the active ingredient particles is 2 µm or more and the 75% particle diameter of the active ingredient particles is 8.5 µm or less.