WO2003075659A1

WO2003075659A1 - Sulfonamide derivative-containing agricultural and horticultural compositions

Info

Publication number: WO2003075659A1
Application number: PCT/JP2003/002545
Authority: WO
Inventors: Masaharu Nakayama; Yukio Okada
Original assignee: Sumitomo Chemical Takeda Agro Company, Limited
Priority date: 2002-03-13
Filing date: 2003-03-05
Publication date: 2003-09-18
Also published as: AR038965A1; AU2003212646A1

Abstract

The present invention provides an agricultural and horticultural composition comprising a sulfonamide derivative which is safe because of its low effect on humans and animals, natural enemies and environment and which has an excellent controlling ability also against drug-resistant microorganisms; which comprises a compound represented by Formula (I): wherein each of A1 and B1 is independently optionally substituted phenyl group, X1 is a chemical bond, Z1 is (1) a C?1-6#191 alkyl group optionally substituted by 1 to 3 C?1-4#191 alkoxy, (2) a C?3-6#191 cycloalkyl group or (3) an allyl group or a salt thereof and a certain surfactant ingredient.

Description

DESCRIPTION

SULFONAMIDE DERIVATIVE-CONTAINING AGRICULTURAL AND HORTICULTURAL COMPOSITIONS

Technical Field

The present invention relates to a combination composition comprising a sulfona ide derivative or a salt thereof useful as an agricultural and horticultural microbicidal agent.

Background Art

A large number of compounds having a microbicidal activity have been synthesized and employed as agricultural and horticultural microbicidal agents for the purpose of the stable supply of agricultural products. It is well known, however, that repetitive administration of only limited types of such compounds resulted in the problematic development of microorganisms which are resistant to such compounds. In addition, increasing demands for safe chemicals and environmental protection encourage the^' development of safer agricultural and horticultural microbicidal agents. Accordingly, an investigation has been made to search for a novel compound having a microbicidal activity. An attention is paid also to biological or chemical characteristics of a sulfomamide derivative and a large number of the analogous compounds have been synthesized to date. However, most of such compounds are synthetic intermediates, pharmaceuticals, compounds synthesized just for investigating chemical reactions, or reagents. The sulfonamide derivatives reported in connection with microbicidal agents are those disclosed in Japanese Patent Laid-open Publication No.Sβl- 286366, Japanese Patent Laid-open Publication No. S62-190104, Japanese Patent Laid-open Publication No . S63-239264, Japanese Patent Laid-open Publication No . S63-238006, Japanese Patent Laid-open Publication No. S63-307851, Japanese Patent Laid-open Publication No. Hl-156952, Japanese Patent Laid-open Publication No.2001-26506 (Japanese Patent Application No .2000-132869) , J.Med. Chem. 1983, 26, 1741, DE19725447, USP 4906650 and the like.

Nevertheless, a combination composition comprising a sulfonamide derivative, which is safe because of its low effect on humans and animals, natural enemies and environment and which has an excellent controlling ability also against drug-resistant microorganisms, has not been developed yet.

Disclosure of Invention We made an effort in searching for an agricultural and horticultural microbicidal agent having an excellent microbicidal activity in order to solve the problems described above, and finally found out that a compound represented by Formula (I) :

(I)

wherein A¹ is a phenyl group which may be optionally substituted by 1 to 3 substituents selected from the group consisting of C_x_₄ alkyl group, C_x_₄ haloalkyl group, C-,^ alkoxy group, C_x_₄ haloalkoxy group, C₁__i alkylthio group, Cj_₄ haloalkylthio group, halogen, cyano and nitro; X¹ is a chemical bond; B¹ is a phenyl group which may be optionally substituted by 1 to 5 substituents selected from the group consisting of (1) a C_x_₄ alkyl group optionally substituted by 1 to 3 halogens, (2) a C_x_₄ alkoxy group, (3) a C_x_₄ alkylthio group, (4) a thiocarba oyl group, (5) a halogen atom, (6) a cyano group and (7) a nitro group; Z¹ is (1) a C^ alkyl group optionally substituted by 1 to 3 C_1-4 alkoxy groups, (2) a C₃_₆ cycloalkyl group or (3) an allyl group (hereinafter referred to as Compound (I) ) or a salt thereof, especially Compounds No.l to 9 listed below or a salt thereof, unexpectedly exhibits an extremely potent microbicidal activity but has a low toxicity to humans and animals, fish and natural enemies.

In addition, we also found out that a combination of a Compound (I) or a salt thereof and at least one surfactant ingredient selected from the group consisting of compounds represented by Formulae (II), (III), (IV) and (V) or salts thereof brought a synergistic effect to the microbicidal activity. Based on these findings, we further studied intensively and finally completed the present invention.

Thus, the present invention provides: (1) an agricultural and horticultural composition comprising a Compound (I) or a salt thereof and at least one surfactant ingredient selected from the group consisting of a compound represented by Formula (II) :

Y⁺ • X^" (II) wherein Y⁺ is a metal ion or an ion represented by Formula:

wherein at least one of RI, R2 and R3 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, and the others may be same or different and each is selected from the group consisting of methyl group, ethyl group and groups represented by Formulae:

wherein nl is 1 to 5, and R4 is a methyl group or an ethyl group, and the counterion X^" is an anionic group derived from at least one anionic oligomer or polymer having a mean molecular weight of 300 to 20,000 which is selected from the following 1), 2), 3) and 4):

1) a polymer whose essential constituent monomer is one or more monomer selected from the group consisting of unsaturated carboxylic acids and their derivatives; 2) a polymer whose essential constituent monomer is styrenesulfonic acid; 3) a formalin condensate of a sulfonated polycyclic aromatic compound which may be optionally substituted by a hydrocarbon group;

4) a formalin condensate of a C₁_₄ alkylsulfonated polycyclic aromatic compound which may be optionally substituted by a hydrocarbon group; or halogen anion, or a salt thereof; a compound represented by Formula (III) :

wherein n2 is 1 to 18, and R5 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, or a salt thereof; a compound represented by Formula (IV) :

wherein n3 is 1 to 18, ml is 1 to 18, and R6 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, or a salt thereof; and a compound represented by Formula (V)

wherein n4 is 1 to 18, m2 is 1 to 18, and R7 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, or a salt thereof;

(2) the agricultural and horticultural composition according to the above-mentioned (1) , which is used for applying in combination with other pesticidal active ingredients; (3) the agricultural and horticultural composition according to the above-mentioned (1) , which contains other pesticidal active ingredients;

(4) the agricultural and horticultural composition according to the above-mentioned (1) , which contains other surfactant ingredients;

(5) a agricultural and horticultural composition, wherein a composition comprising a compound represented by Formula (I) or a salt thereof and a composition comprising at least one of compounds represented by Formulae (II) to (V) or a salt thereof are combined just before the use and then applied; (6) the agricultural and horticultural composition according to the above-mentioned (5) , which is applied in combination with other pesticidal active ingredients;

(7) the agricultural and horticultural composition according to any one of the above-mentioned (1) to (6) , wherein a compound represented by Formula (I) is at least one selected from the group consisting of

4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.l) ,

2' 4 ' -dinitro-N-ethyl-p-toluenesulfonanilide (Compound

No 2) , 2' 4 ' -dicyano-N-ethyl-p-toluenesulfonanilide (Compound No 3),

4 ' -chloro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.4),

4 ' -fluoro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide

(Compound No.5),

4 ' -cyano-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide

(Compound No.6) , 4 ' -chloro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide

(Compound No .7 ) ,

2 ' , 4 ' -dinitro-N-isopropyl-p-toluenesulfonanilide (Compound

No.8) and

4 ' -nitro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide (Compound No.9) or a salt thereof; (8) the agricultural and horticultural composition according to any one of the above-mentioned (1) to (7), wherein a compound represented by Formulae (II), (III), (IV) or (V) is at least one selected from the group consisting of polynaphthylmethanesulfonate of dialkyldimethylammonium, didecyldimethylammonium chloride, distearyldimethylammonium chloride, condensate of sodium naphthalenesulfonate, polyoxyethylene fatty acid ester, polyoxyethylene monolaurate, polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine and polyoxyethylene oleylstearylamine;

(9) a method of using a composition comprising a compound represented by Formula (I) or a salt thereof and a composition comprising at least one of compounds represented by Formulae (II) to (V) or a salt thereof as being combined just before the use as an agricultural and horticultural microbicidal agent; and the like.

Best Mode for Carrying Out the Invention A Compound (I) and a salt thereof are known and described, for example, in WO00/65913, and by a method described therein they can be produced.

Representative Compounds (I) employed in the present invention include the Compounds No.l to 9 described above, that is: 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.l);

2 ' , 4 ' -dinitro-N-ethyl-p-toluenesulfonanilide (Compound No.2); 2 ' , 4 ' -dicyano-N-ethyl-p-toluenesulfonanilide

(Compound No.3);

4 ' -chloro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.4);

4 ' -fluoro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.5);

4 ' -cyano-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.6);

4 ' -chloro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide (Compound No.7); 2 ' , 4 ' -dinitro-N-isopropyl-p-toluenesulfonanilide

(Compound No.8); and

4 ' -nitro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide (Compound No.9) .

A salt of a Compound (I) may be any pesticide chemically acceptable salt. For example, if a Compound (I) is basic, a salt thereof may be a salt with an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, or with an organic acid such as formic acid, acetic acid, propionic acid, tartaric acid, malic acid, citric acid, benzoic acid and p-toluenesulfonic acid, and if a Compound (I) is acid, a salt thereof may be a salt with an alkaline metal such as sodium and potassium, an alkaline earth metal such as calcium and magnesium, ammonia or amine. Any of Compounds (I) or salts thereof can be employed alone or in combination of two or more thereof.

Compounds (II) to (V) and salts thereof are also known as surfactant ingredients, and commercially available. For example, a Compound (II) includes an ionic surfactant such as an alkylamine salt and a quaternary ammonium salt; polynaphthylmethanesulfonate of dialkyldimethylammonium [e.g., a ingredient of NEEDS™ (TM represents trade mark) ; manufactured by KAO] , didecyldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride and the like, an ionic surfactant such as a formalin condensate, for example, of a naphthalenesulfonate; a condensate of sodium naphthalenesulfonate and the like.

A Compound (III) includes, for example, a nonionic surfactant such as a polyoxyethylene fatty acid ester [e.g., a ingredient of NEEDS™; manufactured by KAO] ; polyoxyethylene monolaurate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and the like.

A Compound (IV) includes, for example, a nonionic surfactant such as an alkoxylated aliphatic amine and polyoxyethylene alkylamine; polyoxyethylene laurylamine, polyoxethylene stearylamine, polyoxyethylene oleylstearylamine and the like.

A Compound (V) includes, for example, an anionic surfactant such as a polyoxyethylene fatty acid amide; alkylalkanol amide and the like. Any of these surfactant ingredients can be employed alone or in combination of two or more thereof.

An example of agricultural and horticultural compositions of the present invention may be a composition comprising one or more of Compounds (I) and salts thereof and one or more selected from the group of consisting of Compounds (II), Compounds (III), Compounds (IV) and Compounds (V) and salts thereof (hereinafter sometimes referred to as Composition A) , which can be employed in the form of a conventional pesticidal composition as a microbicidal composition by a method known per se. Another example of agricultural and horticultural compositions of the present invention may be a composition used by combining a composition comprising a Compound (I) or a salt thereof (hereinafter sometimes referred to as Composition A') and a composition comprising Compounds (II) to (V) or a salt thereof just before the use and then applying

(hereinafter sometimes referred to as Composition A"). Any of Compositions A to A" is used by combining one or more

(preferably 1 to 4) of Compounds (I) or salts thereof as active ingredients with one or more (preferably 1 to 5) of surfactant ingredients selected from the group consisting of Compounds (II), Compounds (III), Compounds (IV) and

Compounds (V) and salts thereof for enhancing the microbicidal effect, and can be mixed with or dispersed in a suitable liquid carrier or mixed with or adsorbed on a suitable solid carrier depending on the purpose of use, whereby being formulated as any of dosage forms such as emulsifiable concentrate, oil, aqueous suspension, emulsion, liquid, ULV formulation, wettable agent, powder, DL (driftless) powder, granule, fine-granule, fine-granule F, flowable formulation, dry-flowable formulation, tablet, JUMBO-for ulation, spray, ointment, paste, foam, aerosol, microcapsule, dressing agent for seed, fumigant, and stick formulation for irrigating plant body. Any of these formulations may be combined, if necessary, with other surfactant ingredients, suspending agent, spreading agent, penetrating agent, wetting agent, dispersant, thickening agent, stabilizer, binder, fluidizing aid, solidification inhibitor, coagulant, antioxidant, floating agent, antifoaming agent, anti-freezing agent, preservative, dehydrating agent, UV absorbing agent, UV scattering agent, colorant, suspension stabilizer and the like, and may be produced by mixing a Compound (I) or a salt thereof and a surfactant ingredient together with a liquid carrier or a solid carrier homogeneously in accordance with a method known per se, if necessary, also together with the various additives listed above as well as other pesticidal active ingredients .

More specifically, an emulsion may be produced by, for example, mixing and dissolving a Compound (I) or a salt thereof together with a surfactant ingredient, an organic solvent and the like homogeneously. A granule formulation or granular wettable formulation may be produced by, for example, mixing a Compound (I) or a salt thereof together with a surfactant ingredient, a dispersant (other surfactant ingredient) , a binder, a bulking agent (or a solid carrier) and the like homogeneously and then granulating the mixture. A powder formulation (such as DL powder formulation) may be produced by, for example, mixing and grinding a Compound (I) or a salt thereof together with a surfactant ingredient, a bulking agent (or a solid carrier) and the like homogeneously. A flowable formulation may be produced by, for example, mixing and dispersing a Compound (I) or a salt thereof together with a surfactant ingredient, a dispersant and the like using a stirrer and then wet-grinding the mixture using DYNO-MILL or the like. A JUMBO-formulation may be produced by, for example, mixing and granulating a Compound (I) or a salt thereof together with a surfactant ingredient, a dispersant (other surfactant ingredient) , a binder, a floating agent, a bulking agent (or a solid carrier) and the like homogeneously.

A JUMBO-formulation, a granule, a granular wettable or a wettable agent may be wrapped in 20 to 200 g portions with a water-soluble film for the purpose of convenience of the application. Such a water-soluble film may be made of polyvinyl alcohol, carboxymethyl cellulose, starch, gelatin, polyvinyl pyrrolidone, polyacrylic acid or a salt thereof, Pullulan (Trade name: Starch-based polysaccharides) , PAOGEN (Trade name: Thermoplastic water-soluble polymer) or the like .

Preferable examples of a liquid carrier (solvent) to be used include water; alcohol such as methanol, ethanol, propanol, isopropanol, ethylene glycol, etc.; ketone such as acetone, methyl ethyl ketone, etc.; ether such as 1,4- dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.; aliphatic hydrocarbon such as kerosene, paraffin oil, fuel oil, machine oil, edible oil, etc.; aromatic hydrocarbon such as benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, etc.; acid amide such as N,N- dimethylformamide, N,N-dimethylacetamide, etc.; ester such as ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.; and nitrile such as acetonitrile, propionitrile, etc., one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Preferable examples of a solid carrier (diluent, bulking agent) include vegetable powder such as soybean powder, tobacco powder, wheat flour, wood powder, etc.; clay such as kaolin, bentonite, acid terra alba, etc.; talc such as talcum powder, agalmatolite powder, etc.; silica- based mineral powder such as kieselguhr, mica powder, etc.; calcium carbonate, alumina, sulfur powder, activated carbon, etc., one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate. Examples of an ointment base include polyethylene glycol; pectin; polyhydric alcohol ester of higher fatty acid. such as monostearic acid glycerin ester, etc.; a cellulose derivative such as methyl cellulose, etc.; sodium alginate; bentonite; higher alcohol; polyhydric alcohol such as glycerin, etc.; Vaseline; white Vaseline; liquid paraffin; lard; various vegetable oils; lanolin; dehydrated lanolin; hardened oil; resin; etc., one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio with or without various other surfactants listed below as appropriate. Examples of a surfactant to be used as an emulsifying agent, a spreading agent, a penetrating agent, a wetting agent or a dispersant as desired include soap; nonionic surfactants such as polyoxyethylene alkyl ether (NEWKALGEN D1504™, NOIGEN ET65™, NOIGEN ET83™, NOIGEN ET157™ and the like) , polyoxyethylene alkylphenyl ether, polyoxyethylene nonylphenyl ether (NONIPOL 20™, NONIPOL 100™ and the like) , polyoxyethylene alkylallyl ether [e.g., NOIGEN EA142™, NOIGEN EA92™; DAIICHI KOGYO SEIYAKU, NONAL™; TOHOKAGAKU] , polyethylene glycol ether [e.g., NONIPOL 85™, NONIPOL 100™, NONIPOL 160™; SANYO KASEI] , polyhydric alcohol ester [e.g., Tween 20™, Tween 80™; Kao] , polyoxyethylene polyoxypropylene ether, polyoxyethylene distylene-derivatized phenyl ether (NOIGEN EA 87™, NOIGEN EA 177™ and the like), polyoxyethylene alkyl ester (IONET MO20™, IONET MO600™ and the like), sorbitan fatty acid ester (RHEODOL SP-S10™, RHEODOL TW- S20™ and the like) , polyoxyethylene sorbitan fatty acid ester, block copolymers of ethylene oxide and propylene oxide (NEWPOL PE64™) , higher fatty acid alkanolamide, alkylmaleic acid copolymer (DEMOL EP™ and the like), etc.; cationic surfactants such as alkylamine salts,- quaternary ammonium salts, etc.; polymer compounds such as alkyl sulfate [e.g., EMAL 10™, EMAL 40™; Kao] , alkyl sulfonate [e.g., NEOGEN™, NEOGEN T™: DAIICHI KOGYO SEIYAKU, NEOPELEX; Kao] , naphthalenesulfonic acid polycondensate metal salts, formalin condensates of naphthalenesulfonate (NEWKALGEN FS4™ and the like), alkyl naphthalenesulfonate (SORPOL 5115™ and the like) , metal lignosulfonate, alkylallyl sulfonate, alkylallyl sulfonate sulfate, etc.; anionic surfactants such as polynaphtyl methanesulfonate, polystyrenesulfonic acid sodium salt, polycarboxylic acid metal salts, polyoxyethylene distyrylphenyl ether sulfate ammonium, higher alcohol sulfonate, higher alcohol ether sulfonate, dialkyl sulfosuccinate (NEWKALGEN EP70P™ and the like) , higher fatty acid alkaline metal salts, and the like. Any salt may .be used as far as the performance of a surfactant is not affected adversely, including sodium salts, potassium salts, ammonium salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts, triisopropanlamine salts, other tertiary amine salts such as dialkyldimethylammonium salts and the like.

Examples of a surfactant to be used as a microbicidal effect enhancer include sorbitan fatty acid ester (sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate and the like) and polyoxyethylene sorbitan fatty acid ester (polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate and the like) as well as Compounds (II) to (V) described above.

Examples of a stabilizer include compounds having an epoxy group, antioxidants [e.g., dibutylhydroxytoluene (BHT) , butylhydroxyanisole (BHA) , tetrakis [3- (3, 5-di-tert- butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Irganox 1010) , DL-tocopherol, propyl gallate, erythorbic acid, sodium erythorbate, isporpyl citrate and the like], phosphoric acid, PAP auxiliary agent (isopropyl acid phosphate) , cyclodextrin (TOYODERIN P) , tall oil fatty acid (HARTALL fatty acid) and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a binder include dextrin, alpha-starch, polyvinyl alcohol, gum arabic, sodium alginate, polyvinyl pyrrolidone, glucose, sucrose, mannitol, sorbitol and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate. Examples of a fluidizing aid include PAP auxiliary agents (e.g., isopropyl acid phosphate), talc and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a solidification inhibitor include white carbon, kieselguhr, magnesium stearate, aluminium oxide, titanium dioxide and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a coagulant include liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, isobutylene polymers (e.g., IP solvent) and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of an antioxidant include dibutylhydroxytoluene, 4, 4-thiobis-6-tert-butyl-3- methylphenol, butylhydroxyanisole, p-octylphenol, mono (or di or tri) (a-methylbenzyl) phenol, 2, 6-di-tert-butyl-4- methylphenol, tetrakis [3- (3, 5-di-tert-butyl-4- hydroxyphenyl) propionyloxymethyl]methane and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

A floating agent is used especially in the production of a JUMBO-formulation, and is preferably a powder base having a specific gravity of 1 or less (preferably 1 to 0.5). Such a powder base preferably has the particle size of 600 μm or less, preferably 600 μm to 10 μm and includes an inorganic substance obtained by sintering a naturally occurring glass material to form one or several independent air bubbles therein, such as perlite made of perlite rock or obsidian, SHIRASU BALLOON (trade name) made of Shirasu sand, vermiculite made of HIRUISHI stone (leech stone) , and PHYLLITE (trade name) which is aluminosilicate-based and microporous and obtained by the similar sintering process. Such a powder base also includes an organic substance, which is solid at the ambient temperature and generally referred as waxy material, for example, higher fatty acid such as stearic acid and palmitic acid, higher alcohol such as stearyl alcohol, and paraffin wax. Such waxy material is water-repellent and poorly water-permeable and thereby tends to retain pesticidal active ingredients therein for a prolonged time to prevent the dispersion in water.

Therefore such waxy material is used preferably as a mixture with the microporous glass material described above,

Examples of an antifoaming agent include silicon- based antifoaming agents (for example, antifoam E20) and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate .

Examples of an anti-freezing agent include ethylene glycol, diethylene glycol, polyethylene glycol, glycerin and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a preservative include butylparaben, potassium sorbate and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a dehydrating agent include anhydrous plaster, silica gel powder and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of an UV absorbing agent include 2-(2'- hydroxy-5 ' -methylphenyl) benzotriazole, 2-ethoxy-2- methyloxalic acid bisanilide, dimethyl succinate-1- (2- hydroxyethyl) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine polycondensate and the like, one or more (preferably 1 to

3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of an UV scattering agent include titanium dioxide and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a colorant include cyanine green G, Erio green B400 and the- like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

Examples of a suspension stabilizer include polyvinyl alcohol (GOHSENOL GH17 and the like) , clay mineral (KUNIPIA F, VEEGUM R and the like), silicon dioxide (AEROSIL COK 84 and the like) and the like, one or more (preferably 1 to 3) of which may be used alone or as a mixture in a suitable ratio as appropriate.

A Composition A can comprise, in addition to a Compound (I) or a salt thereof, a insecticide, an acaricide, a nematocide, a herbicide, a plant hormone, a plant growth regulator, a bactericide, a synergistic agent, an attractant, a repellent, a dye, a fertilizer and the like and be used as appropriate. In addition, an agricultural and horticultural composition in the form of a conventional pesticidal composition, which comprises ingredients other than a Compound (I) or a salt thereof, (hereinafter referred to as Composition B) may be applied in combination with Composition A, A' or A".

Thus, the present invention includes agricultural and horticultural microbicidal agents comprising other pesticidal active ingredients and the like in addition to a Compound (I) or a salt thereof. The other pesticidal active ingredients and the like may be contained in a single preparation together with any of Compositions A to A". Alternatively, they may be formulated into a separate preparation from Compositions A to A" and then mixed with any of Compositions A to A" just before the use, or may be applied individually.

Representative insecticides, acaricides and nematocides to be used as such other pesticidal active ingredients and the like are as follows: EPN, acephate, isoxathion, isofenphos, isoprocarb, etrimfos, oxydeprofos, quinalphos, cadusafos, chlorethoxyfos, chlorpyrifos, chlorpyrifos-methyl, chlorofenvinphos, salithion, cyanophos, disulfoton, dimethoate, sulprofos, diazinon, thiometon, tetrachlorvinphos, tebupirimfos, trichlorphon, naled, vamidothion, pyraclophos, pyridafenthion, pirimiphos-methyl, fenitrothion, fenthion, phenthoate, fosthiazate, butathiofos, prothiofos, propaphos, profenofos, phosalone, fosthiazate, malathion, methidathion, metolcarb, monocrotophos, BPMC, XMC, alanycarb, ethiofencarb, carbaryl, carbosulfan, carbofuran, xylylcarb, cloethocarb, thiodicarb, triazamate, pirimicarb, fenoxycarb, fenothiocarb, furathiocarb, propoxur, bendiocarb, benfuracarb, methomyl, acrinathrin, imiprothrin, ethofenprox, cycloprothrin, sigma-cypermethrin, cyhalothrin, cyfluthrin, cypermethrin, silafluofen, tefluthrin, deltamethrin, tralomethrin, fenvalerate, fenpropathrin, flucythrinate, fluvalinate, flufenoprox, fluproxyfen, flumethrin, prallethrin, beta- cyfluthrin, benfluthrin, permethrin, acetamiprid, imidacloprid, cartap, thiocyclam, nitenpyram, clotianidine, tefuranidine, AKD-1022, thiomethoxam, bensultap, avermectin, emamectin-benzoate, clofentezine, chlorfluazuron, cyromazine, diafenthiuron, dienochlor, dichlorvos, dif.lubenzuron, spynosyn, sulfluramid, teflubenzuron, tebufenozide, tebufenpyrad, hydroprene, vaniliprole, pymetrozine, pyridaben, pyriproxyfen, pyrimidifen, fipronil, fenazaquin, fenpyroximate, fluazuron, flucycloxuron, flufenoxuron, buprofezin, hexaflumuron, hexythiazox, milbemycin, metoxadiazone, lufenuron, levamisol, chlorphenapyr, NC-184, etoxazole, IBP, ampropylfos, edifenphos, chlorthiophos, tolclofos-methyl, acequinocyl (3-dodecyl-l, 4-dihydro-l, 4-dioxo-2-naphthyl acetate) , acetoprole ( (RS) -1- [5-amino-l- (2, 6-dichloro- , α, ~ trifluoro-p-tolyl) -4- (methylsulfinyl) pyrazol-3-yl] ethanone) , bistrifluron (1- [2-chloro-3, 5-bis (trifluoromethyl) phenyl] - 3- (2, 6-difluorobenzoyl) urea) , cybutryne (N2-tert-butyl-N4- cyclopropyl-6-methylthio-l, 3, 5-triazine-2, 4-diamine) , dinotefuran ( (RS) -l-methyl-2-nitro-3- (tetrahydro-3- furylmethyl) guanidine) , ethiprole (5-amino-l- (2, 6-dichloro- α, α, -trifluoro-p-tolyl) -4-ethylsulfinylpyrazole-3- carbonitrile) , fluacrypyrim (NA-83,methyl (E)-2-{ -[2- isopropoxy-6- (trifluoromethyl) pyrimidin-4-yloxy] -o-tolyl}- 3-methoxyacrylate) , flunicoamid (IKI-220) , indoxacarb (methyl (S) -N- [7-chloro-2, 3, 4a, 5-tetrahydro-4a-

(methoxycarbonyl) indeno [1, 2-e] [1, 3, 4] oxadiazin-2- ylcarbonyl] -4 '- (trifluoromethoxy carbanilate or methyl (S)- 7-chloro-2, 3, 4a, 5 -tetrahydro-2 - [methoxycarbonyl (4- trifluoromethoxyphenyl) carbamoyl] indeno [1, 2-e] [1,3,4] oxadiazine -4a-carboxylate) ) , spinosad (mixture of 50-95% of (2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR) -2- (6-deoxy-2, 3, 4- tri-O-methyl-α-L-mannopyranosyloxy) -13- (4-dimethylamino- 2,3,4, 6-tetradeoxy-β-D-erythropyranosyloxy) -9-ethyl- 2, 3, 3a, 5a, 5b, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16a, 16b-hexadecahydro- 14-methyl-lH-8-oxacyclododeca [b] as-indacene -7,15-dione and 50-5% (2S,3aR,5aS,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy - 2,3,4-tri -O-methyl-α-L-mannopyranosyloxy) 13- (4- dimethylamino -2,3,4, 6-tetradeoxy-β-D-erythropyranosyloxy) -9-ethyl -2, 3, 3a, 5a, 5b, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16a, 16b - hexadecahydro-4, 14 -dimethyl-lH-8-oxacyclododeca [b] as- indacene-7, 15-dione) , spirodiclofen (3- (2, 4- dichlorophenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl 2, 2- di ethylbutyrate) .

Representative insecticides which can be used as such other pesticidal active ingredients and the like are as follows :

Fosetyl, ipconazole, imazalil, imibenconazole, etaconazole, epoxiconazole, cyproconazole, diniconazole, difenoconazole, tetraconazole, tebuconazole, triadimenol, triadimefon, triticonazole, triforine, bitertanol, viniconazole, fenarimol, fenbuconazole, fluotrimazole, furconazole-cis, flusilazole, flutriafol, bromuconazole, propiconazole, hexaconazole, pefurazoate, penconazole, myclobutanil, metconazole, cabendazin, debacarb, prothiocarb, benomyl, maneb, TPN, isoprothiolane, iprodione, iminoctadine-albesil, iminoctadine-triacetate, ethirimol, etridiazole, oxadixyl, oxycarboxin, oxolinic acid, ofurace, kasugamycin, carboxin, captan, clozylacon, chlobenthiazone, cyprodinil, cyprofuram, diethofencarb, dichlofluanid, diclomezine, diclocymet, zineb, dimethirimol, dimethomorph, dimefluazole, thiabendazole, thiophanate-methyl, thifluzamide, tecloftalam, triazoxide, triclamide, tricyclazole, tridemorph, triflumizole, validamycin A, hymexazol, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, ferimzone, fenpiclonil, fenpropidin, fenpropimorph, fthalide, furametpyr, furalaxyl, fluazinam, furcarbanil, fluquinconazole, fludioxonil, flusulfamide, flutolanil, butiobate, prochloraz, procymidone, probenazole, benalaxyl, benodanil, pencycuron, myclozolin, metalaxyl, metsulfovax, ethfuroxam, mepanipyrim, mepronil, kresoxim-methyl, azoxystrobin, SSF- 126, carpropamid, benthiavalicarb (KIF230, isopropyl [(S)- 1- [ (R) -1- (6-fluorobenzothiazol-2-yl) ethylcarbamoyl] -2- methylpropyl] carbamate) , bethoxazin (3-benzo [b] thien-2-yl- 5, 6-dihydro-l, 4, 2-oxathiazine 4-oxide), BJL994, carbendazim, cyflufenamid (NF-149) , epoxiconazole ( (2RS, 3SR) -1- [3- (2- chlorophenyl) -2, 3-epoxy-2- (4-fluorophenyl) propyl] -1H-1, 2, 4- triazole) , ethaboxam ( (RS) -N- (α-cyano-2-thenyl) -4-ethyl-2- (ethylamino) -1, 3-thiazole-5-carboxamide) , fenamidone ( (S) - l-anilino-4-methyl -2-methylthio-4-phenylimidazolin-5-one) , fenpropimorph, flusilazole, fuberidazole, iprovalicarb (isopropyl 2-methyl-1- [ (1-p-tolylethyl) carbamoyl] - (S) - propylcarbamate) , metrafenone, nicobifen, picoxystrobin (methyl (E) -3-methoxy-2- {2- [6- (trifluoromethyl) -2- pyridyloxymethyl] phenyl} acrylate) , pyraclostrobin (methyl N-{2- [1- (4-chlorophenyl) -lH-pyrazol-3-yloxymethyl] phenyl }- (N-methoxy) carbamate) , simeconazole ((RS)-2-(4- fluorophenyl) -1- (1H-1, 2, 4-triazol-l-yl) -3- (trimethylsilyl) propan-2-ol) , spiroxamine (8-tert-butyl- 1, 4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine) , tiadinil, trifloxystrobin (methyl (E) -methoxyirαino- { (E) - - [l-( , α, α-trifluoro-m-tolyl) ethylideneaminooxy] -o- tolyl } acetate) , zoxamide ( (RS) -3, 5-dichloro-N- (3-chloro-l- ethyl-l-methyl-2-oxopropyl) -p-toluamide) . Representative herbicides, plant hormones and plant growth regulators which can be used as such other pesticidal active ingredients and the like are as follows: amicarbazone (4-amino-N-tert-butyl-4, 5-dihydro -3- isopropyl-5-oxo-lH-l, 2, 4-triazole-l-carboxamide) , beflubutamid (N-benzyl-2- (α, α, α, -tetrafluoro-m- tolyloxy) butyramide) , benzobicyclon (3- (2-chloro-4- mesylbenzoyl) -2-phenylthiobicyclo [3.2.1] oct-2-en-4-one) , cinidon-ethyl (ethyl 2-chloro-3- [2-chloro-5- (cyclohex-1- ene-1, 2-dicarboximido) phenyl] acrylate), dimethenamid-P ( (S) -2-chloro-N- (2, 4-dimethyl-3-thienyl) -N- (2-methoxy-l- methylethyl) acetamide) , epocholeone (22, 23-epoxy-6-oxo-7- oxa-6 (7a) -homo-5α-stigmastane-2α, 3α-diyl dipropionate) , fluazolate (isopropyl 5- [4-bromo-l-methyl-5- (trifluoromethyl) pyrazol-3-yl] -2-chloro-4-fluorobenzoate) , flucarbazone (4, 5-dihydro-3-methoxy-4-methyl-5-oxo-N- [2- (trifluoromethoxy) phenylsulfonyl] -1H-1, 2, 4-triazole-l- carboxamide) , flufenacet (4 ' -fluoro-N-isopropyl-2- [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yloxy] acetanilide) , flufenpyr (2-chloro-5- [1, 6-dihydro-5-methyl-6-oxo-4- (trifluoromethyl) pyridazin-1-yl] -4-fluorophenoxyacetic acid), foramsulfuron (1- (4, 6-dimethoxypyrimidin-2-yl) -3- [2- (dimethylcarbamoyl) -5-formamidophenylsulfonyl] urea) , imazapic ( (RS) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin- 2-yl) -5-methylnicotinic acid), iodosulfuron (4-iodo-2- [3- (4-methoxy-6-methyl-l, 3, 5-triazin-2- yl) ureidosulfonyl]benzoic acid), isoxachlortole (4-chloro- 2-mesylphenyl 5-cyclopropyl-l, 2-oxazol-4-yl ketone), isoxadifen (4, 5-dihydro-5, 5-diphenyl-l, 2-oxazole-3- carboxylic acid), mesosulfuron (2- [ (4, 6-dimethoxypyrimidin- 2-ylcarbamoyl) sulfamoyl] - - (methanesulfonamido) -p-toluic acid), mesotrione (2- (4-mesyl-2-nitrobenzoyl) cyclohexane- 1,3-dione), penoxsulam (3- (2, 2-difluoroethoxy) -N- (5, 8- dimethoxy [1, 2, 4] triazolo [1, 5-c] pyrimidin-2-yl) -α, α, α- trifluorotoluene-2-sulfonamide) , picolinafen (4 ' -fluoro-6- (α, , α-trifluoro-m-tolyloxy) pyridine-2-carboxanilide) , profluazol (1,2' -dichloro-4 ' -fluoro-5 ' - [ (6S, 7aR) -6-fluoro- 2, 3, 5,6,7 , 7a-hexahydro-l, 3-dioxo-lH-pyrrolo [1, 2-c] imidazol- 2-yl]methanesulfonanilide) , profoxydim (2-{ (EZ) -1- [ (2RS) -2- (4-chlorophenoxy) propoxyimino] butyl }-3-hydroxy-5- (thian-3- yl) cyclohex-2-en-l-one) , propoxycarbazone (methyl 2- (4, 5- dihydro-4-methyl-5-oxo-3-propoxy-lH-l, 2, 4-triazol-l- yl) carboxa idosulfonylbenzoate) , pyraclonil (1- (3-chloro- 4,5,6, 7-tetrahydropyrazolo [1, 5-a] pyridin-2-yl) -5- [methyl (prop-2-ynyl) amino] pyrazole-4-carbonitrile) , pyribenzoxim (benzophenone 0- [2, 6-bis (4, 6- dimethoxypyrimidin-2-yloxy) benzoyl] oxime) , pyridafol (6- chloro-3-phenylpyridazin-4-ol) , pyriftalid (CGA279233) , tepraloxydim ( (EZ)- (RS)-2-{l-[ (2E)-3- chloroallyloxyimino] propyl } -3-hydroxy-5-perhydropyran-4- ylcyclohex-2-en-l-one) , trifloxysulfuron (CGA292230) .

Among "other pesticidal active ingredients and the like" listed above, bactericidal active ingredients and insecticidal active ingredients are preferred especially. The bactericidal active compounds described above include preferably carbendazim, epoxiconazole, fenpropimorph, flusilazole, fuberidazole, picoxystrobin, pyraclostrobin and trifloxystrobin as a soil treatment agent and a seed treatment agent for wheat; epoxiconazole, flusilazole, picoxystrobin, pyraclostorobin and trifloxystrobin as a spray for stem and leaf of wheat; BJL994, iprovalicarb, picoxystrobin, pyraclostrobin, trifloxystrobin and benthiavalicarb as a spray for stem and leaf of fruits and vegetables; and carpropamid, diclocymet and BAS-520F as a box treatment agent for rice and the like. The insecticidal active ingredients described above are preferably TI-435 (clotianidine; iso name now being in application), nitenpyram and the like.

Thus the embodiments of a composition of the present invention include:

[1] an agricultural and horticultural composition which comprises a Compound (I) and at least one selected fr.o the group consisting of Compound (II), Compound (III), Compound (IV) and Compound (V) ; [2] an agricultural and horticultural composition which comprises at least one selected from Compounds No.l to 9 described above or a salt thereof and at least one selected from the group consisting of Compound (II), Compound (III), Compound (IV) and Compound (V) ; [3] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide and at least one or more selected from the group consisting of Compound (II) , Compound (III) , Compound (IV) and Compound (V) ; [4] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide, dialkyldimethylammonium polynaphtylmethanesulfonate and polyoxyethylene fatty acid ester;

[5] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide, alkoxylated aliphatic amine and polyoxyethylene monolaurate;

[6] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide, didecyldimethylammonium chloride, sodium naphthalenesulfonate condensate and polyoxyethylene monolaurate;

[7] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide, distearyldimethylammonium chloride, sodium naphthalenesulfonate condensate and polyoxyethylene monolaurate;

[8] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide and polyoxyethylene laurylamine;

[9] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide and polyoxyethylene oleylamine;

[10] an agricultural and horticultural composition which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide and polyoxyethylene oleylstearyl amine;

[11] an agricultural and horticultural microbicidal agent according to any one of the above-mentioned [1] to [10] which further comprises a bactericidal ingredient as another pesticidal active ingredient;

[12] an agricultural and horticultural microbicidal agent according to any one of the above-mentioned [1] to [10] which further comprises an insecticidal ingredient as another pesticidal active ingredient; [13] an agricultural and horticultural microbicidal agent according to the above-mentioned [11] wherein the bactericidal ingredient is one or more selected from the group consisting of epoxiconazole, flusilazole, azoxystrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, metalaxyl and iprovalicarb; and,

[14] an agricultural and horticultural microbicidal agent according to the above-mentioned [11] wherein the bactericidal ingredient is one or more selected from the group consisting of TI-435 (clotianidine; iso name now being in application) and nitenpyram.

More preferred embodiments of the compositions comprising other surfactant ingredients are as follows: (i) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof, dialkyldimethylammonium polynaphtylmethanesulfonate and polyoxyethylene fatty acid ester,

(ii) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof, didecyldimethylammonium chloride, sodium naphthalenesulfonate condensate and polyoxyethylene monolaurate, (iii) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof and polyoxyethylene oleylstearylamine,

(iv) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof and polyoxyethylene oleylamine,

(v) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof and polyoxyethylene stearylamine,

(vi) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof and polyoxyethylene laurylamine, (vii) An agricultural and horticultural microbicidal agent which comprises 4 ' -chloro-N-ethyl-2 ' -nitro-p- toluenesulfonanilide or a salt thereof, polyoxyethylene monolaurate and alkoxylated aliphatic amine.

According to the present invention, when a Compound

(I) described above or a salt thereof is combined with at least one ingredient selected from the group consisting of Compound (II), Compound (III), Compound (IV) and Compound (V) , a synergistically enhanced microbicidal effect which is higher than the effect of the Compound (I) used alone is obtained. A microbicidal agent comprising a Compound (I) or a salt thereof in combination with one or more surfactant ingredients selected from the group consisting of Compounds (II) to (V) exerts excellent effects, for example, (1) the bactericidal effect may be enhanced as compared with the application of the drug alone, (2) the bactericidal effect is immediately given, (3) a broader bactericidal spectrum and a more prolonged sustained effect are induced as compared with conventional bactericidal agents, (4) the dose can be decreased as compared with the application of the drug alone and (5) a more reliable controlling effect on various harmful organisms can be expected as compared with the application of individual drug against the individual harmful organism. Examples of diseases which can be controlled by a composition of the present invention or a combination of said composition with other pesticidal active ingredients include diseases in rice such as rice blast (Pyricularia oryzae) , brown spot {Helminthosporium oryzae, Cochliobolus ' miyabeanus) , Bakanae disease (Gibberella fujikuroi) , damping-off {Rhizopus oryzae) , sheath blight {Rhizoctonia ■ solani) and the like; diseases in oats such as crown rust {Puccinia coronata) and the like; diseases in barley such as powdery mildew (Erysiphe graminis) , scald {Phynchsporium secalis) , leaf spot {Cochliobolus sativus) , stripe

{Helminthosporium gramineum, Pyrenophora gramineum) , net blotch (Pyrenophra teres) , net smut (Tilletia caries), loose smut {Ustilago nuda) and the like; diseases in wheat such as powdery mildew {Erysiphe graminis) , glume blotch (Leptosphaeria nodorum, Septoria nodorum) , stripe rust

{Puccinia striiformis) , brown microparticle microorganism {Typhula incarnata) , eye spot {Pseudocercosporella herpotrichoides) , red snow blight (Calonectria graminicola, Fusariu nivale) , stem rust {Puccinia granminis) , black microparticle microorganism {Typhula ishikariensis) , scab ^■ {Gibberella zeae) , red rust (Puccinia recondita, Puccinia triticina) , stripe (Helminthosporium gramineum), net smut {Tilletia caries), leaf blight {Septoria tritici) , loose smut (Ustilago tritici) and the like; diseases in maize such as damping-off {Pythium debaryanum) ; diseases in rye such as red snow blight ( Fusarium nivale) ; diseases in potato such as late blight { Phytophthora infestans) ; diseases in tobacco such as downy mildew ( Εeronospora tabacina) , late blight { Phytophthora parasi tica var) , white scab { Cercospora nicotianae) , mosaic ( tobaaco mosaic virus) and the like; diseases in sugar beat such as leaf spot { Cercospora beticola) , damping-off ( Pythium debaryanum, Rhizoctonia solani) , take all { Pythium aphanidermatum) and the like; diseases in paprika such as gray mold (Botrytis cinerea) ; diseases in kidney bean such as gray mold {Botrytis cinerea) , sclerotium rot { Scletotinia sclerotiorum) , southern blight { Corticium rolfsii ) and the like; diseases in broad bean such as powdery mildew { Erysiphe polygoni , Sphaerotheca fuliginae) , rust ( Uromyces fabae, Uromyces phaseoli) , gray mold (Botrytis cinerea) and the like; diseases in peanut such as leaf blotch (Mycosphaerella arachidicola) and the like; diseases in cabbage such as damping-off (Rhizoctonia solani) ; diseases in cucumber such as powdery mildew { Sphaerotheca fuliginea) , fusarium wilt ( Fusarium oxysporum) , vine blight

(Mycosphaerela melonis) , downy mildew { Pseudoperonospora cubensis) , gray mold (Botrytis cinerea) , sclerotium rot ( Scletorinia sclerotiorum) , anthracnose ( Colletotri chum lagenarium) , damping-off { Fusarium oxysporum, Pythium aphanidermatum , Rhizoctonia solani) , mosaic (Cucumber mosaic virus) and the like; diseases in Brassica campestris such as black sooty disease {Alternaria brassicicola) , club root ( Plasmodiophora brassicae) and the like; diseases in celery such as leaf blight ( Septoria apii) ; diseases in radish such as yellows ( Fusarium oxysporum) ; diseases in tomato such as wilt disease { Fusarium oxysporum) , late blight ( Phytophthora infestans) , ring spot (Al ternaria solani) , gray mold {Botrytis cinerea) , gray late blight { Phytophthora capsici ) , black spot {Alternaria toma to) and the like; diseases in egg plants such as brown rot

{ Phytophthora capsici ) , half wilt disease { Verticilium albo-a trum) and the like; diseases in Chinese cabbage such as black spot (Alternaria japonica ) , club root ( Plasmodiophora brassicae) and the like; diseases in green pepper such as late blight ( Phytophthora capsici) , gray mold (Botrytis cinerea) and the like; diseases in lettuce such as gray mold (Botrytis cinerea) ; diseases in citrus fruits such as black spot (Diaporthe citri) ; diseases in pear such as scab ( Venturis nashicola ) , black spot (Alternaria kikuchiana) , red scab disease { Gymno sporangium haraeanum) and the like; diseases in grapes such as downy mildew ( Plasmopara vi ticola) , gray mold (Botrytis cinerea ) , anthracnose {Elsinoe ampelina) and the like; diseases in peach such as rugose^' ( Taphrina deformans) , shot hole (Mycosphaerella cerasella) and the like; diseases in apple such as powdery mildew { Podosphaera leucotria) , scab ( Cladsporium carpophilum) , gray mold (Botrytis cinerea ) , scab ( Venturis inaequalis) , red scab ( Gymnosporangium yamadae) , white root rot (Rosellinia nectrix) , leaf spot defoliation disease {Alternaia mali) and the like; as well as diseases in cereals, fruits and vegetables such as rape, sunflower, carrot, red pepper, strawberry, melon, kiwi fruit, onion, leek, sweet potato, fig, plum, asparagus, persimmon, soybean, azuki bean, watermelon, garland chrysanthemum, spinach, tea leaf and the like. Especially, the higher activity is observed against the diseases caused by the microorganism of Pyricularia, Cochliobolus , Curvularia , Pyrenophora , Al ternaria , Phytophthora , Erysiphe, Puccinia genera or genera closely related thereto, and such diseases include, for example, blast, brown spot and brown rice disease in rice, leaf spot disease, stripe, net blotch and powdery mildew in barley, stripe, leaf spot disease, red rust disease and powdery mildew in wheat, brown spot in maize, summer late blight and late blight in potato, black sooty disease in Brassica campestris, ring spot and black spot in tomato, black spot in Chinese cabbage, black spot in pear, leaf spot defoliation disease in apple and the like.

A combination composition of a Composition A or a Composition B and other pesticidal active ingredients has a microbicidal activitiy and a low toxicity, and as the result, can be used as a safe and excellent microbicidal agent.

A composition of the present invention can be used in a manner similar to that of a conventional microbicidal agent, and can exert, as a result, a more excellent effect than a conventional microbicidal agent. For example, it can be used by nursery box treatment, spray onto stems and leaves of a plant, application to water in paddy field, seed treatment or soil treatment, direct application onto stems of a fruit tree and the like. The dose may vary widely depending on the season, site and method of the application, and is generally 0.3 to 3,000 g, preferably 50 to 1,000 g of an active ingredient (Compound (I) or a salt thereof) per a hector. When a combination composition of the present invention is a wettable agent, it may be used after being diluted at a final concentration of the active ingredient within the range from 0.1 to 1,000 ppm, preferably 10 to 500 ppm. The amount of a Compound (I) or a salt thereof contained in the composition of the present invention is usually about 0.1 to 80% by weight, preferably about 1 to 20% by weight of the total amount of the formulation. Specifically, if the formulation is emulsion, liquid, a wettable agent (for example, a granule wettable agent) , aqueous suspension or microemulsion, it is usually about 1 to 80% by weight, preferably about 1 to 20% by weight. If the formulation is oil or powder, it is usually about 0.1 to 50% by weight, preferably about 1 to 20% by weight. If the formulation is granule, tablet or JUMBO formulation, it is usually about 5 to 50% by weight, preferably about 1 to 20% by weight. The amount of the other pesticidal active ingredients (e.g., insecticide, acaricide, herbicide and/or microbicidal agent) incorporated into the combination composition of the present invention ranges usually from about 1 to 80% by weight, preferably about 1 to 20% by weight of the total amount of the formulation. The amount of additives other than the above-described pesticidal active ingredients contained in the composition of the present invention may vary depending on the type and amount of the pesticidal active ingredient or the dosage form of the formulation, and it is usually 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. More specifically, it is preferable that, on the basis of the total amount of the composition, a surfactant in an amount of 1 to 50% by weight, preferably about 1 to 20% by weight, a fluidizing aid in an amount of about 1 to 20% by weight, and a carrier in an amount of about 1 to 90% by weight, preferably about 1 to 70% by weight are usually added. Specifically, when a liquid formulation is produced, it is preferable that a surfactant in an amount of about 1 to 20% by weight, preferably 1 to 10% by weight and water in an amount of 20 to 90% by weight are added. An emulsion, wettable agent (for example, granule wettable agent) or the like is applied preferably after being diluted with water appropriately (for example about 100 to 5000-fold dilution) .

The present invention is further described in detail in the following Formulation Examples and Experiments, which are not intended to restrict the present invention. Unless otherwise specified, "part" means a part by weight.

Formulation Example 1

10.5 Parts of Compound No.l, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal , hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU)', 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI

KOGYO SEIYAKU) , 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI) , 0.5 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (31.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI) , 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (31 parts) to obtain a homogeneous flowable formulation.

Formulation Example 2

21 Parts of Compound No.l, 5 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO) , 2 parts of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA- 177, DAIICHI KOGYO SEIYAKU), 2 parts of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 1 part of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (27.9 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 10 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (26 parts) to obtain a homogeneous flowable formulation. Formulation Example 3

21 Parts of Compound No.l, 5 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 1.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 2 parts of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU), 2 parts of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 1 part of rosin glycerin ester

(SORPOL 7518, TOHO KAGAKU KOGYO) and water (26.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 10 parts of polyoxyethylene oleylstearylamine (NEWKALGEN D-3615T, TAKEMOTO YUSHI) and water (30 parts) to obtain a homogeneous flowable formulation.

Formulation Example 4 21 Parts of Compound No.l, 10 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate .(KUNIPIA F KUNIMINE KOGYO) , 0.75 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU), 2 parts of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU) , 2 parts of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 1 part of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (22.05 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 10 parts of polyoxyethylene oleylstearylamine (NEWKALGEN D-3615T, TAKEMOTO YUSHI), 10 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (20 parts) to obtain a homogeneous flowable formulation.

Formulation Example 5

10.5 Parts of Compound No.l, 10 parts of epoxiconazole, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.3 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.5 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (31.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (21 parts) to obtain a homogeneous flowable formulation.

Formulation Example 6 10.5 Parts of Compound No.l, 10 parts of epoxiconazole, 5 parts of pyraclostrobin, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA- 177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.3 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU

KOGYO) and water (26.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (21 parts) to obtain a homogeneous flowable formulation.

Formulation Example 7

10.5 Parts of Compound No.l, 10 parts of flusilazole, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA- 177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.3 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU

KOGYO) and water (31.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (21 parts) to obtain a homogeneous flowable formulation.

Formulation Example 8 10.5 Parts of Compound No.l, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO .SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.5 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (31.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 9 parts of dialkyldimethylammonium polynaphthylmethanesulfonate, 22 parts of polyoxyethylene fatty acid ester and 19 parts of water to obtain a homogeneous flowable formulation.

Formulation Example 9

(SORPOL 7518, TOHO KAGAKU KOGYO) and water (26.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 10 parts of polyoxyethylene stearylamine (NEWKALGEN D-3212, TAKEMOTO YUSHI) and water

(30 parts) to obtain a homogeneous flowable formulation.

Formulation Example 10

10.5 parts of Compound No. 1, 10 parts of iprovalicarb, 4 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.5 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.3 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and water (31.4 parts) were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalene sulfonate condensate (NEWGALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethyl ammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and water (21 parts) to obtain a homogeneous flowable formulation.

Formulation Example 11

20.5 Parts of Compound No.l, 10 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO) , 2 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 2 parts of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU) , 2 parts of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 1 part of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and 61.4 parts of water were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension (flowable formulation) .

Formulation Example 12

10.6 Parts of TF-991, 5 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion

(ANTIFOAM E20, KAO), 0.5 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.3 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.5 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and 20.8 parts of water were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 15 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and 41 parts of water to obtain a homogeneous flowable formulation.

Formulation Example 13

10.6 Parts of TF-991, 5 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.5 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO), 0.3 parts of sodium carboxymethyl cellulose (CELLOGEN 7A, DAIICHI KOGYO SEIYAKU) , 1 part of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA-177, DAIICHI KOGYO SEIYAKU), 1 part of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 0.5 parts of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and 20.8 parts of water were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension, to which was added a mixture of 2 parts of sodium naphthalenesulfonate condensate (NEWKALGEN PS-P, TAKEMOTO YUSHI), 2 parts of didecylmethylammonium chloride (CATIOGEN DDM, DAIICHI KOGYO SEIYAKU) , 12 parts of polyoxyethylene monolaurate (EMANON 1112, KAO) and 44 parts of water to obtain a homogeneous flowable formulation.

Formulation Example 14

10.6 Parts of TF-991, 10 parts of ethylene glycol, 0.1 parts of butylparaben, 0.2 parts of silicone emulsion (ANTIFOAM E20, KAO), 0.8 parts of colloidal hydrated aluminium silicate (KUNIPIA F KUNIMINE KOGYO) , 2 parts of polyoxyalkylene allylphenyl ether sulfate salt (NOIGEN EA- 177, DAIICHI KOGYO SEIYAKU), 2 parts of polyoxyalkylene distyrylphenyl ether (NEWKALGEN FS-7, TAKEMOTO YUSHI), 1 part of rosin glycerin ester (SORPOL 7518, TOHO KAGAKU KOGYO) and 73.3 parts of water were mixed and subjected to wet grinding by DYNO-MILL KDL (SHINMARU ENTERPRISE) to form homogeneous suspension (flowable formulation) .

In the following Experiment 1, Experiment 2 and Experiment 6, a bactericide was evaluated by measuring a lesion area rate (percentage) and converting it into a controlling value. The controlling value was calculated by the following equation.

% Controlling value = {l-(% lesion area in treatment group/% lesion area in non-treatment group) } x 100

In the case of a negative value, the % controlling value was regarded as zero. An estimated controlling value of a mixture of active ingredients was determined using Colby's formula [R.S.Colby, Weeds 15, 20-22 (1967)] and compared with an actual controlling value. Colby's Formula: E=x+y-xy/100 wherein E represents the estimated controlling value (synergistic effect) when a mixture of the active ingredient A and the active ingredient B is used at the concentrations of a and b, x represents the controlling value when _r the active ingredient A was used at the concentration of a, and y represents the controlling value when the active ingredient B was used at the concentration of b. When a controlling value obtained in an experiment exceeded the estimated value E, then a synergistic effect was exerted. The controlling value of 0 means that the lesion area rate in the test plant is similar to that in the untreated control plant. The controlling value of 100 means that the test plant dose not suffer from the disease. In the following Experiment 3 and Experiment 4, a bactericidal agent was evaluated by measuring the length of a mycelium and converting it into an inhibition rate. The inhibition rate was calculated by the following equation.

Inhibition rate (%) = (1- (Mycelium length in treatment group/Mycelium length in non-treatment group) ) x 100

Then an estimated inhibition rate of a mixture of active ingredients was determined using Colby's formula described above, and compared with an actual inhibition rate.

Experiment 1

Controlling effect on wheat red rust ( Pussinia recondita) A flowable formulation of the test Compound No.l (designated by the No. of the compounds described above)

(shown in Formulation Example 11 described above) , the test surfactants AD-1 (18% dialkyldimethylammonium polynaphthylmethanesulfonate, 44% polyoxyethylene fatty acid ester, 20% isopropyl alcohol and 18% water, etc) , AD-2 (4.5% didecyldimethylammonium chloride, 4.5% sodium naphthalenesulfonate condensate, 22% polyoxyethylene (10) monolaurate, 69% water, etc) and AD-3 (100% polyoxyethylene (15) oleylstearylamine) shown in the following Table 1 were used individually or in any combination thereof, and diluted with water at predetermined concentrations of the active ingredient (ppm) and predetermined dilution ratios (times) in order to prepare application liquids. To a wheat plant (species: NORIN No.4) cultured for 1 week in a greenhouse, 10 ml/pot of the application liquid was sprayed. After allowing the drug liquid to be dried in the air, the test plant was inoculated with 2 ml/pot of a suspension, which was prepared by suspending spores of Pussinia recondita (1 mg/ml) in ion exchange water containing 0.025% Tween 20 (NAKARAI KAGAKU), by spraying. After the inoculation followed by allowing the test plant to stand in a humid chamber at 22°C for 18 hours, it was cultured in a greenhouse for 6 days. The lesion area rate of the treated leaf was examined and the results are represented using the controlling value described above. The results are shown in Table 1.

The Compound No.l exhibited a higher controlling effect when combined with the surfactants AD-1, AD-2 and AD-3 than the effect of individual use, showing a synergistic effect of the combination. Table 1

Compound ConcentratSurfactant Dilution Lesion Controlling E ion of ratio of area rate value

Compound surfactant (%)

(ppm) (times)

Compound

No.l 8 - - 73 0 -

40 - - 77 0 -

200 - - 55 25 -

1000 - - 30 59 -

- - AD-1 4000 47 36 -

- - 2000 21 72 -

- - AD-2 2000 43 41 -

- - AD-3 4000 25 66 -

- - 2000 14 81 -

Compound

No.l 8 AD-1 4000 28 61 36

40 4000 14 81 36

200 4000 13 82 52

1000 4000 14 81 74

Compound

No.l 8 AD-1 2000 11 86 72

40 2000 11 86 72

200 2000 7 91 79

Compound •

No.l 40 AD-2 2000 35 52 41

200 2000 20 73 56

1000 2000 11 85 76

Compound

No.l 8 AD-3 4000 20 73 66

40 4000 15 80 66

200 4000 11 85 75

1000 4000 8 89 86

Compound

No.l 40 AD-3 2000 11 86 81

200 2000 8 89 86

Non- treatment control group 73 Experiment 2

Controlling effect on barley powdery mildew {Erysiphe graminis)

A flowable formulation of the test Compound No.l (designated by the No. of the compounds described above)

(shown in Formulation Example 11 described above), the test surfactants AD-1 (18% dialkyldimethylammonium polynaphthylmethanesulfonate, 44% polyoxyethylene fatty acid ester, 20% isopropyl alcohol and 18% water, etc) and AD-3 (100% polyoxyethylene (15) oleylstearylamine) shown in the following Table 2 were used individually or in any combination thereof, and diluted with water at predetermined concentrations of the active ingredient (ppm) and predetermined dilution ratios (times) in order to prepare application liquids. To a barley plant (species: SIGAHYATSUISHI No.5) cultured for 1 week in a greenhouse, 10 ml/pot of the application liquid was sprayed. After allowing the drug liquid to be dried in the air, the test plant was inoculated with spores of Erysiphe graminis by airborne infection from leaves of a barely powdery mildew- infected sporing barley. After the inoculation, the test plant was allowed to stand in a thermostat chamber at 22°C under a 12-hour/day lighting cycle and cultured for 5 days. The lesion area rate of the treated leaf was examined and the results are represented using the controlling value described above. The results are shown in Table 2.

The Compound No.l exhibited a higher controlling effect when combined with the surfactants AD-1 and AD-3 than the effect of individual use, showing a synergistic effect of the combination.

Table 2

Compound Concentrat- Surfactant Dilution Lesion Controlling E ion of ratio of area rate value

Compound surfactant (%) (ppm) (times)

Compound

No.l 8 - 97 2 -

40 - 97 2 -

200 - 63 35 -

1000 - 60 38 -

AD-1 4000 53 45 -

2000 37 62 -

AD-3 4000 53 45 -

2000 47 52 —

Compound

No.l 8 AD-1 4000 47 52 46

40 4000 30 69 46 200 4000 27 72 64 1000 4000 23 76 66

Compound

No.l 8 AD-1 2000 27 72 63

40 2000 17 83 63 200 2000 17 83 75 1000 2000 17 83 76

Compound

No .1 8 AD-3 2000 37 62 53

40 2000 40 59 53

Non- treatment control group - - - ' 97

Experiment 3 In vitro antibacterial effect on potato late blight (Phytophthora infestans)

A solution of the test Compound No.l (designated by the No. of the compounds described above) in dimethylformamide (final concentration: 0.1 to 0.5% by volume) and the test surfactant AD-1 (18% dialkyldimethylammonium polynaphthylmethanesulfonate, 44% polyoxyethylene fatty acid ester, 20% isopropyl alcohol and 18% water, etc) were used individually or in combination, and diluted with a liquid medium (V8 juice liquid medium) at predetermined concentrations of the active ingredients (ppm and % by volume) .

The strain M2 (hybrid type A2, metalaxyl sensitive) , strain Nl (hybrid type Al, metalaxyl resistant) and strain Q2 (hybrid type Al, metalaxyl resistant) of Phytophthora infestans were contributed from Masayuki Akino in Department of Agriculture of Hokkaido University and used in this experiment. Each strain was subjected to subculture (20°C, passage at 2-week interval) on a V8 juice medium plate. A zoosporangium suspension of Phytophthora infestans was prepared by pouring the V8 juice liquid medium onto the culture plate which had been incubated for 2 weeks after inoculation, scraping the surface gently using a painting brush to separate the zoosporangia and then filtering them through a double-layered gauze. The test compound and the test surfactant were used individually or in combination and then mixed with the zoosporangium suspension in the wells of a 96-well microplate at a predetermined density, which was then incubated at 20°C for 4 days. Subsequently, an inverted microscope was employed for observation. In Experiment 3, an antibacterial effect was evaluated as one of the following four degrees, i.e., A: the germination of the zoosporangia is inhibited completely, B: part of the zoosporangia undergoes the germination, but the mycelium elongation is inhibited potently, C: part of the zoosporangia undergoes the germination, and the mycelium elongation is inhibited mildly, D: the zoosporangia undergoes the germination, and the mycelium elongation is not inhibited. The results are shown in Table 3 to 5.

The Compound No.l exhibited a higher antibacterial activity when combined with the surfactant AD-1 than the effect of individual use, showing an evident synergistic effect of the combination.

Table 3

Table 4

Table 5

Experiment 4

In vitro antibacterial activity

In vitro antibacterial activities against apple canker { Valsa mali) , cucumber stem rot ( Fusarium oxysporum) , citrus black spot (Diaporte ci tri ) , gourd anthracnose { Colletotrichum lagenarium) and potato late blight { Phytophthora infestans) were examined.

A solution of the test Compound No.l (designated by the No. of the compounds described above) in dimethylformamide (final concentration: 0.1 to 0.5% by volume) and the test surfactant AD-1 (18% dialkyldimethylammonium polynaphthylmethanesulfonate, 44% polyoxyethylene fatty acid ester, 20% isopropyl alcohol and 18% water, etc) were used individually or in combination, and dispensed into petri dishes at predetermined concentrations (ppm and %) to prepare V8 juice medium plates.

The microorganisms to be tested were incubated for 2 weeks in PSA medium (potato sucrose agar medium) plates or V8 juice medium plates, from which microorganism flora discs were punched out using a cork borer (inside diameter of 9 mm) . Each flora disc was placed on a V8 juice medium plate prepared at a predetermined concentration of the active ingredient. Subsequently, the incubation was continued at 25°C for 3 to 12 days. The plate was inspected by measuring the length of the flora growing on the plate. The results are shown, in Table 6.

The Compound No.l exhibited a higher antibacterial activity when combined with the surfactant AD-1 than the effect of individual use, showing an evident synergistic effect of the combination. Table 6

Experiment 5

In vitro antibacterial effect

In vitro antibacterial activities on potato late blight { Phytophthora infestans) strain M2 (hybrid type A2, metalaxyl sensitive) , strain Nl (hybrid type Al, metalaxyl resistant) and strain Q2 (hybrid type Al, metalaxyl resistant) were examined.

The microorganisms to be tested were incubated for 2 weeks in V8 juice medium plates, from which microorganism flora discs were punched out using a cork borer (inside diameter of 9 mm) . Each flora disc was placed on a V8 juice medium plate prepared at a predetermined concentration of the active ingredient. Subsequently, the incubation was continued at 20°C for 3 to 12 days. The plate was inspected by measuring the length of the flora growing on the plate. The results are shown in Table 7. The Compound No.l exhibited a higher antibacterial activity when combined with the surfactant AD-1 than the effect of individual use, showing an evident synergistic effect of the combination.

Table 7

Experiment 6

Controlling effect on rice brown spot (H. oryzae) A flowable formulation of the test Compound No.l

(designated by the No. of the compounds described above) (shown in Formulation Example 11 described above), the test surfactants AD-1 (18% dialkyldimethylammonium polynaphthylmethanesulfonate, 44% polyoxyethylene fatty acid ester, 20% isopropyl alcohol and 18% water, etc) and AD-2 (4.5% didecyldimethylammonium chloride, 4.5% sodium naphthalenesulfonate condensate, 22% polyoxyethylene (10) monolaurate, 69% water, etc) shown in the following Table 8 were used individually or in any combination thereof, and diluted with water at predetermined concentrations of the active ingredients (ppm) and predetermined dilution ratios (times) in order to prepare application liquids. To a rice plant (species: ASAHI No.4) cultured for 2 weeks in a greenhouse, 10 ml/pot of the application liquid was sprayed. After allowing the drug liquid to be dried in the air, the test plant was inoculated with a spore suspension (5 x 10⁴ cells/ml) of H. oryzae by spraying at 2 ml/pot in an inoculation box at 28°C in a greenhouse. After the inoculation, the plant was allowed to stand as it was in the inoculation box, and cultured for 4 days. The lesion area rate of the treated leaf was examined and the results are represented using the controlling value described above, The results are shown in Table 8.

The Compound No.l exhibited a higher controlling effect when combined with the surfactants AD-1 and AD-2 than the effect of individual use, showing a synergistic effect of the combination. Table 8

Compound Concentrat Surfact- Dilution Lesion area Controlling E ion of ant ratio of rate (%) value

Compound surfactant .

(ppm) (times)

Compound No .1 50 _ _ 8.0 27

100 - - 5.0 55 -

- _ AD-1 4000 6.5 41 -

- - 2000 5.0 55 -

- - AD-2 2000 15 0 -

Compound No .1 50 AD-1 2000 1.0 91 67

Compound No .1 50 AD-2 2000 2.0 82 27

Non-treatment control group - - 11 - - Experiment 7

Controlling effect on wheat red rust ( Pussinia recondi ta ) The flowable formulations of the test Compound No.l (designated by the No. of the compounds described above)

SCI, SC2 and SC3 (shown in Formulation Example 12, 13 and . 14 described above) and the blank formulations WSC1 and WSC2 which were similar to the flowable formulations SCI and SC2 except for containing no test Compound No.l were used. They were diluted with water at a predetermined concentration of the active components (ppm) and a predetermined dilution ratio (times) to prepare application liquids. To a wheat plant (species: NORIN No.4) cultured for 1 week in a greenhouse, 10 ml/pot of the application liquid was sprayed. After allowing the drug liquid to be dried in the air, the test plant was inoculated with 2 ml/pot of a suspension, which was prepared by suspending spores of Pussinia recondi ta (1 mg/ml) in ion exchange water containing 0.025% Tween 20 (NAKARAI KAGAKU), by spraying. After the inoculation followed by allowing the test plant to stand in a humid chamber at 22°C for 18 hours, it was cultured for 6 days in a greenhouse. The lesion area rate of the treated leaf was examined and the results are represented by using the controlling value described above. The results are shown in Table 8. The Compound No.l exhibited a higher controlling effect when combined with the surfactant components contained in SCI and SC2 but not in SC3 than ^• the effect of individual use, showing a synergistic effect of the combination. Table 9

Compound ConcentraFormul Dilution Lesion Controlling E tion of ation ratio of area rate value

Compound type Formulation (%)

(ppm) (times)

- - wsci 1000 50 36 —

- - WSC2 1000 60 23 -

Compound No .1 100 SCI 1000 20 74 49

Compound No .1 100 SC2 1000 25 68 38

Compound No .1 100 SC3 ^• 1000 63 20 _

Non-treatment control group - - l i

Experiment 8

In vitro antibacterial effect on potato late blight { Phytophthora infestans)

A solution of the test Compound No.l (designated by the No. of the compounds described above) in dimethylformamide (final concentration: 0.1 to 0.5% by volume) and the test surfactant AD-4 (100% polyoxyethylene (15) oleylstearylamine) were used individually or in combination, and diluted with a liquid medium (V8 juice liquid medium) at predetermined concentrations of the active components (ppm and % by volume) .

The strain M2 (hybrid type A2, metalaxyl sensitive) and strain Q2 (hybrid type Al, metalaxyl resistant) of Phytophthora infestans were contributed from Masayuki Akino in Department of Agriculture of Hokkaido University and used in this experiment. Each strain was subjected to subculture (20°C, passage at 2-week interval) on a V8 juice medium plate. A zoosporangium suspension of Phytophthora infestans was prepared by pouring the V8 juice liquid medium onto the culture plate which had been incubated for 2 weeks after inoculation, scraping the surface gently using a painting brush to separate the zoosporangia and then filtering them through a double-layered gauze. The test compound and the test surfactants were • used individually or in combination and then mixed with the zoosporangium suspension in the wells of a 96-well microplate at a predetermined density, which was then incubated at 20°C for 5 days. Subsequently, an inverted microscope was used for observation. In Experiment 8, an antibacterial effect was evaluated as one of the following four degrees, i.e., A: the germination of the zoosporangia is inhibited completely, B: part of the zoosporangia undergoes the germination, but the mycelium elongation is inhibited potently, C: part of the zoosporangia undergoes the germination, and the mycelium elongation is inhibited mildly, D: the zoosporangia undergoes the germination, and the mycelium elongation is not inhibited. The results are shown in Table 10 and 11.

The Compound No.l exhibited a higher antibacterial activity when combined with the surfactant AD-4 than the effect of individual use, showing an evident synergistic effect of the combination. Table 10

Table 11

Industrial Applicability

As described above, a composition which comprises a Compound (I) or a salt thereof, especially Compounds No.l to 9 or salts thereof, and at least one selected from the group consisting of Compound (II), Compound (III), Compound (IV) and Compound (V) of the present invention and said composition used in combination with other pesticidal ingredients are sulfonamide derivative compositions having a microbicidal activity, each of which is safe because of its low effect on humans and animals,^' natural enemies and environment and has an excellent controlling ability also against drug-resistant microorganisms, and therefore they are useful as excellent agricultural microbicidal agents. They exhibit marked controlling effect especially against blast, brown spot and brown rice disease in rice, leaf spot disease, stripe, net blotch and powdery mildew in barley, stripe, leaf spot disease, red rust disease and powdery mildew in wheat, brown spot in maize, summer late blight and late blight in potato, black soot disease in Brassica campestris, ring spot and black rot in tomato, black rot in Chinese cabbage, black rot in pear, leaf spot defoliation disease in apple and the like.

Claims

CLAIMS 1. An agricultural and horticultural composition comprising a compound represented by Formula (I) :

(I)

wherein A¹ is a phenyl group which may be optionally substituted by 1 to 3 substituents selected from the group consisting of C_x_₄ alkyl group, C_x_₄ haloalkyl group, C_1-4 alkoxy group, C_{1 1} haloalkoxy group, C_1-4 alkylthio group, C₁_₄ haloalkylthio group, halogen, cyano and nitro; X¹ is a chemical bond; B¹ is a phenyl group which may be optionally substituted by 1 to 5 substituents selected from the group consisting of (1) a C^ alkyl group optionally substituted by 1 to 3 halogens, (2) a C_x_₄ alkoxy group, (3) a C_x_₄ alkylthio group, (4) a thiocarbamoyl group, (5) a halogen atom, (6) a cyano group and (7) a nitro group; Z¹ is (1) a C-_L-.₆ alkyl group optionally substituted by 1 to 3 C-^ alkoxy groups, (2) a C₃_₆ cycloalkyl group or (3) an allyl group;, or a salt thereof and at least one surfactant ingredient selected from the group consisting of a compound represented by Formula (II) :

Y^{+ •} X^~ (II) wherein Y⁺ is a metal ion or an ion represented by Formula: R1- :_N: -R3 R2^{' ^}R4

wherein at least one of Rl, R2 and R3 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, and the others may be same or different and each of them is selected from the group consisting of methyl group, ethyl group and groups represented by Formulae:

1) a polymer whose essential constituent monomer is one or more monomer selected from the group consisting of unsaturated carboxylic acids and their derivatives; 2) a polymer whose essential constituent monomer is styrenesulfonic acid;

3) a formalin condensate of a sulfonated polycyclic aromatic compound which may be optionally substituted by a hydrocarbon group; 4) a formalin condensate of a C_x_₄ alkylsulfonated polycyclic aromatic compound which may be optionally substituted by a hydrocarbon group; or halogen anion, or a salt thereof; a compound represented by Formula (III) :

wherein n3 is 1 to 18, ml is 1 to 18, and R6 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, or a salt thereof; and a compound represented by Formula (V) :

wherein n4 is 1 to 18, m2 is 1 to 18, and R7 is a straight or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, or a salt thereof.

2. The agricultural and horticultural composition according to Claim 1, which is used for applying in combination with other pesticidal active ingredients.

3. The agricultural and horticultural composition according to Claim 1, which contains other pesticidal active ingredients. .

4. The agricultural and horticultural composition according to Claim 1, which contains other surfactant ingredients .

5. A agricultural and horticultural composition, wherein a composition comprising a compound represented by Formula (I) or a salt thereof and a composition comprising at least one of compounds represented by Formulae (II) to (V) or a salt thereof are combined just before the use and then applied.

6. The agricultural and horticultural composition according to Claim 5, which is applied in combination with other pesticidal active ingredients.

7. The agricultural and horticultural composition according to any one of Claims 1 to 6, wherein a compound represented by Formula (I) is at least one selected from the group consisting of 4 ' -chloro-N-ethyl-2 ' -nitro-p-toluenesulfonanilide

(Compound No.l),

2 ' , 4 ' -dinitro-N-ethyl-p-toluenesulfonanilide ^' (Compound No.2),

2 ' , 4 ' -dicyano-N-ethyl-p-toluenesulfonanilide (Compound No.3) ,

4 ' -chloro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.4),

4 ' -fluoro-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide (Compound No.5), 4 ' -cyano-N-isopropyl-2 ' -nitro-p-toluenesulfonanilide ( Compound No . 6 ) ,

4 ' -chloro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide (Compound No.7),

2 ' , 4 ' -dinitro-N-isopropyl-p-toluenesulfonanilide (Compound No.8) and

4 ' -nitro-N-isopropyl-2 ' -cyano-p-toluenesulfonanilide (Compound No.9) or a salt thereof.

8. The agricultural and horticultural composition according to any one of Claims 1 to 7, wherein a compound represented by Formulae (II), (III), (IV) or (V) is at least one selected from the group consisting of polynaphthylmethanesulfonate of dialkyldimethylammonium, didecyldimethylammonium chloride, distearyldimethylammonium chloride, condensate of sodium naphthalenesulfonate, polyoxyethylene fatty acid ester, polyoxyethylene monolaurate, polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine and polyoxyethylene oleylstearylamine .

9. A method for using a composition comprising a compound represented by Formula (I) or a salt thereof and a composition comprising at least one of compounds represented by Formulae (II) to (V) or a salt thereof as being combined just before the use as an agricultural and horticultural microbicidal agent.