JP4630623B2 - Agricultural / horticultural fungicide composition - Google Patents

Description

  The present invention shows a synergistic effect as well as an additive effect of each agricultural and horticultural fungicide by mixing an iminooxymethylpyridine compound and an agricultural and horticultural fungicide other than the iminooxymethylpyridine compound. The present invention relates to an agricultural and horticultural fungicide composition.

Patent Document 1 discloses an iminooxymethylpyridine compound represented by the above formula (I), which is one active ingredient of the agricultural and horticultural fungicide composition of the present invention. These compounds are safe for rice, wheat, vegetables, fruit trees and the like, and exhibit an excellent bactericidal effect per se.
Japanese Patent No. 3472245

  On the other hand, in recent years, problems related to environmental pollution caused by pesticides have been taken up, and it is desired to develop drugs that reliably control diseases by reducing the dose of drugs to the extent possible, reducing the impact on the environment as much as possible. .

  The present invention enhances the bactericidal effect of the iminooxymethylpyridine compound represented by the formula (I) and expands the target range of effective diseases, thereby reducing the amount of the compound used and high for useful plants. An object of the present invention is to provide an agricultural and horticultural fungicide composition having effectiveness and safety.

（式中、Ｘはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６ハロアルキル基又はＣ_１〜Ｃ_６ハロアルコキシ基を表し、Ｙはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシ基を表し、ｌは０、１／２又は１を表しｍ及びｎは各々独立に０又は１から４の整数を表し、Ｒ^１はＣ_１〜Ｃ_６アルキル基を表し、Ｒ^２は水素原子、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６ハロアルキル基を表し、Ｈ−Ａは酸性物質を表す。）にて示されるイミノオキシメチルピリジン化合物と、植物病害に対して殺菌活性を有するイミノオキシメチルピリジン化合物以外の化合物から選択される１種または２種以上の農園芸用殺菌剤とを混合した農園芸用殺菌剤組成物を提供するものである。 In order to solve these problems, the present inventors have conducted extensive research on mixing iminooxymethylpyridine compounds represented by the formula (I) and active ingredients of many agricultural chemicals. By mixing with an agricultural and horticultural fungicide other than the iminooxymethylpyridine compound, the iminooxymethylpyridine compound represented by the formula (I) alone cannot produce a sufficient effect, and can be used for many diseases. On the other hand, it was found that a very high bactericidal effect was obtained, and the present invention was completed. That is, the present invention relates to the general formula (I)

(Wherein, X represents a halogen _atom, C 1 -C ₆ alkyl _group, C 1 -C ₆ alkoxy _group, C 1 -C ₆ haloalkyl group or a _C 1 -C ₆ haloalkoxy group, Y is a halogen atom, C _{1 to} C ₆ alkyl group or C _{1 to} C ₆ alkoxy group, l represents 0, 1/2 or 1, m and n each independently represents 0 or an integer of 1 to 4, and R ¹ represents C ₁ It represents -C ₆ alkyl group, ^{R 2} represents a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ haloalkyl group, imino oxymethyl pyridine H-a indicated by the representative of the acidic substance.) Provided is an agricultural and horticultural fungicide composition obtained by mixing a compound and one or more agricultural and horticultural fungicides selected from compounds other than iminooxymethylpyridine compounds having fungicidal activity against plant diseases. Is.

で表されるものから選ばれたものである。なお、表１における化合物番号は以下の記載において参照される。 The iminooxymethylpyridine compound used for this invention is a compound shown by the said general formula (I), and can also use 1 type or 2 types or more thereof. Preferred specific examples of the iminooxymethylpyridine compound represented by the general formula (I) are shown in Table 1. These exemplary compounds have the general formula

Is selected from those represented by In addition, the compound number in Table 1 is referred in the following description.

  Agricultural and horticultural fungicides other than the iminooxymethylpyridine compound used in the present invention are known as described in the Pesticide Manual, 13th edition 2003 (published by The British Crop Protection Council) and the like. It is a disinfectant.

  Although the example of the compound which has bactericidal activity with respect to the plant disease used by mixing with an iminooxymethylpyridine compound is given to the following, this invention is not limited to these. That is, inorganic copper compounds such as basic copper sulfate, anhydrous copper sulfate, cupric hydroxide, basic copper chloride and the like, organic copper compounds such as organic copper and copper nonylphenol sulfonate, inorganic sulfur compounds such as sulfur and total sulfur Organic sulfur compounds such as organic sulfur, such as dineb, manneb, propineb, thiadiazine, thiuram, polycarbamate, etc., anilinopyrimidine compounds such as cyprodinyl, pyrimethanil, mepanipyrim, phenylpyrrole compounds such as fludioxonil, etc. For example, chlorothalonil, captan, triazine, fluazinam, sulfenic acid, fusalide, etc., hydrogen carbonate salt agents, eg, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., organophosphorus compounds such as EDDP, fosetyl, torquelophosmethyl, IBP, etc., benzimidazole Compounds such as carbendazim, thiophanate methyl, thiabendazole, benomyl, fuberidazole, etc., dicarboximide compounds such as iprodione, procymidone, vinclozoline, etc., azole compounds such as fenbuconazole, cimeconazole, diclobutrazole, tritico Nazole, ipconazole, fluconazole, microbutanyl, penconazole, viteltanol, bromconazole, oxpoconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriazole, hexaconazole , Imibenconazole, metconazole, propiconazole, cypconazole, tebuconazole, tetraconazo , Triazimenol, imidazole compounds such as triflumizole, prochloraz, imazalyl, pefrazoate, piperazine compounds such as triphorin, morpholine compounds such as fenpropimorph, tridemorph, fenpropidin, etc. Pyrimidine compounds such as ethylimole, dimethylimole, etc., guanidine compounds such as iminotadine acetate, iminoctagine albecylate, guazatine, acid amide compounds such as oxycarboxin, benzoanilide compounds such as mepronil, dichromedin, flutolanil, Acylalanine compounds such as pencyclonfuramethpyr and tifluzamide, such as oxadixyl, metalaxyl, methoxyacrylate compounds such as Cistrobin, cresoxime methyl, metminostrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, orissastrobin, etc., quinoxaline compounds such as quinomethionate, hydroxyanilide compounds such as phenhexamide, cyanoacetamide compounds such as Simoxanyl, etc., cyanoimidazole compounds, such as cyazofamide, etc. Tricyclazole, diflumetrim, phenazine oxide, isoproti Orchids, oxolinic acid, acibenzolar -S- methyl, quinoxyfen.

  The plant diseases having excellent efficacy of the composition of the present invention include filamentous fungal diseases, bacterial diseases, and viral diseases. Specifically, the fungal fungi include Pseudoperonospora bacteria such as cucumber leaves. Pseudoperonospora cubensis, Venturia spp., For example, Venturia inaequalis, Erysiphe spp., For example, Erysiphyrium spp. Pyricularia oryzae, Botrytis spp., For example, cucumber gray mold (Botrytis c) inerea, Rhizoctonia, for example, Rhizoctonia solani, Cladosporium, for example, Tomato leaf fungus (Cladosporum fulvum), Coltosporium, Coltotrichum r Colletotrichum fragaliae, Puccinia genus bacteria such as wheat red rust fungus (Puccinia recondita), Septoria genus bacteria such as Septoria nocrum Cucumber sclerotia (Sclerotinia sclerotio) um), Pythium spp., for example, Phythium debaryanum Hesse, Geeumannomyces spp., for example, Gaeumanomyces graminis, and Bactrum horde Bacteria such as Burkholderia plantarii, Pseudomonas spp., Such as Pseudomonas syringae pv. Lachrymons, Ralstonia spp., Ralstonia spp. Xanthomonas bacteria (Xant Omonas), for example, citrus canker (Xanthomonas citiri), Erwinia (Erwinia) bacteria, e.g., Chinese cabbage soft rot (Erwinia carotovora), and the like. Examples of viral diseases include tobacco mosaic virus and cucumber mosaic virus, but the bactericidal spectrum should not be limited to these.

  The mixing ratio of the iminooxymethylpyridine compound, which is the active ingredient of the composition of the present invention, and the agricultural and horticultural fungicide other than the iminooxymethylpyridine compound can be varied within a relatively wide range. The agricultural and horticultural fungicide other than the iminooxymethylpyridine compound is 0.01 to 1000 parts by weight, preferably 0.1 to 100 parts by weight, based on 1 part by weight of the compound.

  When the composition of the present invention is used as an agricultural and horticultural fungicide, it is usually mixed with a solid carrier, a liquid carrier or a gaseous carrier, and if necessary, a surfactant or other formulation adjuvant is added to obtain an oil agent. , Emulsion, wettable powder, granule, powder, aerosol, liquid, suspension, foam, microcapsule, seed coating, ULV (cold mist, warm mist), paste and the like. These preparations contain 0.1 to 99.9%, preferably 0.2 to 80% by weight of the total amount of active ingredients.

  These preparations can be produced by known methods. Such methods include, for example, the active compound as a developing agent, i.e. a solid carrier, a liquid carrier, a gaseous carrier, optionally a surfactant, a sticking agent, a dispersing agent, a stabilizer, a foam-forming agent or the like or mixtures thereof. Can be carried out by mixing with When water is used as a developing agent, for example, organic solvents can also be used as auxiliary solvents.

  Examples of solid carriers include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fusami clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon, Examples thereof include fine powders or granular materials such as calcium carbonate, hydrated silica, and chemical fertilizers (for example, ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride).

  Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), fat Group hydrocarbons (eg, n-hexane, cyclohexanone, kerosene, kerosene), esters (eg, ethyl acetate, butyl acetate), nitriles (eg, acetonitrile, isobutyronitrile), ethers (eg, dioxane, Diisopropyl ether), acid amides (for example, dimethylformamide, dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane, trichloroethylene, carbon tetrachloride) and the like.

  Examples of the gaseous carrier, that is, the propellant, include chlorofluorocarbon gas, butane gas, and carbon dioxide gas.

  Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like. Can be given.

  Examples of the fixing agent and the dispersing agent include casein, gelatin, polysaccharides (for example, starch powder, gum arabic, cellulose derivatives, alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinyl). Examples of the stabilizer include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-). Butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants or fatty acids or esters thereof.

  The formulated fungicidal composition of the present invention is applied as it is or diluted with water or the like to a plant, water surface or soil. Further, it can be used in combination with other fungicides, insecticides, herbicides, fertilizers, soil conditioners and the like.

  The application amount of the fungicidal composition of the present invention is the mixing ratio of the compound represented by the formula (I) which is an active ingredient compound and the agricultural and horticultural disease control agent other than the compound represented by the formula (I), weather conditions, Although it varies depending on the preparation form, application time, application method, application place, disease to be controlled, target crop, etc., it is usually 1 to 1000 g, preferably 10 to 250 g as an active ingredient compound amount per hectare. When emulsions, wettable powders, suspensions, liquids, etc. are diluted with water and applied, the applied concentration is 1-1000 ppm, preferably 10-250 ppm, and granules, powders, etc. are usually not diluted. Apply as is.

  The composition of the present invention exhibits a synergistic effect on various plant diseases, and has an extremely high bactericidal effect against many diseases even at a low dose, in which a sufficient effect cannot be obtained by the compound represented by formula (I) alone. Since the effect can be obtained, it is excellent as an agricultural and horticultural fungicide.

  Formulation examples and test examples are shown below to describe the present invention in more detail. However, the compounds, additives, and blending ratios in the formulation examples are not limited to these. In addition,% which shows the usage-amount of a formulation example is weight% unless there is particular notice.

(Formulation example 1)
10 parts of compound 1, 0.3 part of agricultural and horticultural fungicide tricyclazole, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 25 parts of bentonite and 61.7 parts of kaolin clay are mixed and mixed with water. In addition, after kneading well, granulation and drying are performed to obtain granules containing 10.3% active ingredient.

(Formulation example 2)
3 parts of compound 5, 0.1 part of agricultural and horticultural fungicide tricyclazole, 85.7 parts of kaolin clay and 11.2 parts of talc are thoroughly pulverized and mixed to obtain a powder of 3.1% active ingredient.

(Formulation example 3)
30 parts of Compound 1, 0.9 part of agricultural and horticultural fungicide mepanipyrim, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 63.1 parts of water are mixed and wet milled until the particle size is 5 microns or less. Thus, a suspension of 30.9% active ingredient is obtained.

(Formulation example 4)
9 parts of compound 1, 0.3 part of agricultural and horticultural fungicide tricyclazole, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 85.7 parts of synthetic silicon hydroxide were thoroughly pulverized and mixed to obtain an active ingredient 9.3 % Wettable powder is obtained.

(Formulation example 5)
9 parts of compound 5, 3 parts of agricultural and horticultural fungicide fusaride, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 83 parts of synthetic silicon hydroxide were thoroughly pulverized and mixed to obtain a wettable powder containing 12% active ingredient. obtain.

(Formulation Example 6)
30 parts of compound 1, 7.5 parts of agricultural and horticultural fungicide iminotadine albesylate, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 57.5 parts of synthetic silicon hydroxide are mixed and mixed well. A 42.5% wettable powder is obtained.

(Formulation Example 8)
30 parts of compound 5, 0.3 part of agricultural and horticultural fungicide azoxystrobin, 14 parts of polyoxyethylene stilphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 49.7 parts of xylene are mixed well and are the active ingredients. A 30.3% emulsion is obtained.

  Next, test examples show that the composition of the present invention is useful as a bactericidal agent.

  The excellent bactericidal effect of the agricultural and horticultural fungicide composition of the present invention is also apparent from the following test examples. That is, the individual active compounds show a certain bactericidal effect, but their combination shows a bactericidal effect that is greater than the sum of the bactericidal effects of the individual active compounds, and a synergistic effect is seen.

The expected bactericidal effect of the combination of individual active compounds can be determined from the Colby formula (calculation of synergistic and antagonistic combinations of herbicides: Calculating Synthetic Responses of Herbide Combination, 15, 20-22 pages, 1967). The calculation formula of Colby is shown below.
(Equation 1)
E = X + Y−X × Y / 100
X represents the bactericidal effect (control value) expressed as a percentage of the untreated control when the compound was used at a concentration of m ppm, and Y was untreated when the agricultural and horticultural fungicide was used at a concentration of n ppm. It represents the bactericidal effect (control value) expressed as a percentage of the control, and E is expressed as the percentage of the untreated control when the compound is used in a concentration of m ppm and the agricultural and horticultural fungicide mixed at a concentration of n ppm. Represents the bactericidal effect (control value).

  When the bactericidal effect of the agricultural and horticultural fungicide composition of the present invention is greater than the calculated value (E) obtained from the Colby formula, the bactericidal effect of this combination exhibits a synergistic effect. Next, the fact that the bactericidal effect of the agricultural and horticultural fungicide composition of the present invention shows a synergistic effect will be specifically described with reference to test examples.

(Wheat powdery mildew control effect test)
Nine wheat seeds (variety: Norin 61) were sown in a square bowl made of PVC with a side of 9 cm, grown for 8 days in a greenhouse, and prepared according to Formulation Example 3 and Formulation Example 8. The horticultural fungicide composition, the compound, and the agricultural and horticultural fungicide were diluted with water so as to be an active ingredient having a predetermined concentration, and 10 ml was sprayed per pot. After air drying, spores of wheat powdery mildew (Erysiphe graminis) were inoculated and placed in a 20-25 ° C. greenhouse. 10 days after the inoculation, each diseased area of the first leaf was indexed according to the following criteria. Based on the obtained index value, the degree of damage was obtained by Equation 2, and the control value (%) was obtained by Equation 3. It was. Table 2 shows the control value (%) of the experimental value obtained by the test and the control value (%) of the calculated value obtained from the calculation formula of Colby.

Disease index 0: No disease
1: Disease area less than 5%
2: Disease area of 5% or more and less than 10%
3: 10% or more and less than 25% disease area
4: Disease area of 25% or more

(Equation 2)
Damage level (%) = (Σ (index × number of leaves)) / (number of leaves surveyed × 4) × 100

(Equation 3)
Control value (%) = (1−Damage level of treated area / Damage level of untreated area) × 100

(Rice prevention test for rice blast)
About 15 seeds of rice seed (variety: Aichi Asahi) were sown in 7 cm diameter clay pots and grown in a greenhouse for 2 to 3 weeks. The agricultural and horticultural fungicide composition of the present invention prepared according to Formulation Example 4 and Formulation Example 5 and the compound and the agricultural and horticultural fungicide become an active ingredient with a predetermined concentration on rice seedlings in which the fourth leaf is completely developed. The mixture was diluted with water and sprayed at 10 ml per bowl. After air-drying, a conidial spore suspension of Pyricularia oryzae was spray-inoculated and immediately placed in a humid chamber at 25 ° C. for 24 hours. Then, it moved to the greenhouse, and the number of lesions on the 4th leaf was investigated 5 days after the inoculation. Table 3 shows the control value (%) of the experimental value obtained by the test and the control value (%) of the calculated value obtained from the calculation formula of Colby.

(Equation 4)
Control value (%) = (1−number of lesions in treated area / number of lesions in untreated area) × 100

(Cucumber powdery mildew control effect test)
Ten cucumber seeds (variety: Sagamihanjiro) were sown in a square bowl made of PVC with a side of 9 cm, grown in a greenhouse for 7 days, and cucumber seedlings with cotyledons were used as test plants. The agricultural and horticultural fungicide composition, compound and agricultural and horticultural fungicide of the present invention prepared according to Formulation Example 3, Formulation Example 6 and Formulation Example 8 were diluted with water so as to become active ingredients of a predetermined concentration, 10 ml per bowl was sprayed. After air-drying, inoculate by shaking the cucumber powdery mildew fungus (Sphaerotheca fuliginea) or its resistant conidia and keep it in a greenhouse at 20 ° C. Based on the obtained index value, the degree of damage was obtained from Equation 2, and the control value (%) was obtained from Equation 3. Tables 4 and 5 show the control value (%) of the experimental value obtained by the test and the control value (%) of the calculated value obtained from the calculation formula of Colby.

Disease index 0: No disease
1: Disease area less than 5% of leaf area
2: Disease area of 5% or more and less than 33.3% of leaf area
3: Onset area of 33.3% to less than 66.6% of leaf area
4: Disease area of 66.6% or more of leaf area, or fallen leaves

(Cucumber downy mildew control effect test)
Ten cucumber seeds (variety: Sagamihanjiro) were sown in a square bowl made of PVC with a side of 9 cm, grown in a greenhouse for 7 days, and cucumber seedlings with cotyledons were used as test plants. The agricultural and horticultural fungicide composition, compound and agricultural and horticultural fungicide of the present invention prepared according to Formulation Example 7 and Formulation Example 8 were diluted with water so as to become an active ingredient of a predetermined concentration, and each 10 ml per pot Sprayed. After air-drying, a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis) or its resistant bacteria was spray-inoculated and immediately placed in a humid chamber at 20 ° C. for 24 hours. After that, it was transferred to a greenhouse, and after 7 days, the degree of disease of each cotyledon was investigated according to the following criteria of disease index, and based on the obtained index value, the degree of damage was calculated by Equation 2, and the control value by Equation 3 ( %). Tables 6 and 7 show the control value (%) of the experimental value obtained by the test and the control value (%) of the calculated value obtained from the calculation formula of Colby.

Disease index 0: No disease
1: Disease area less than 5% of leaf area
2: Disease area of 5% or more and less than 33.3% of leaf area
3: Onset area of 33.3% to less than 66.6% of leaf area
4: Disease area of 66.6% or more of leaf area, or fallen leaves

As is clear from these results, the composition of the present invention is synergistically higher than expected by the Colby formula even at low doses where the compound of formula (I) alone does not provide a sufficient effect. High effect.

Claims (3)

Agricultural and horticultural sterilization in which iminooxymethylpyridine compound represented by the following chemical formula 3 is mixed with one or more agricultural and horticultural fungicides selected from mepanipyrim, azoxystrobin, and iminoctadine arbesylate Agent composition.

Agricultural and horticultural sterilization in which iminooxymethylpyridine compound represented by the following chemical formula 5 is mixed with one or more agricultural and horticultural fungicides selected from mepanipyrim, azoxystrobin and iminoctadine arbesylate Agent composition.

Agricultural and horticultural sterilization in which iminooxymethylpyridine compound represented by the following chemical formula 6 is mixed with one or more agricultural and horticultural fungicides selected from mepanipyrim, azoxystrobin, and iminoctadine arbesylate Agent composition.