JPH10306085A - Isothiazoleurea derivative and industrial antibacterial, antifungal and algicidal agent containing the same compound and biofouling-preventing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound comprising a specific isothiazoleurea derivative, having high safety, capable of developing broad spectrum at a low dose and useful as an industirial antibacterial, antifungal and algicidal agent, an agent, etc., for preventing adhesion of noxious organisms such as shellfishes. SOLUTION: This new isothiazoleuea derivative is represented by formula I [X and Y are each H, a (F-substituted)1-5C alkyl, a (F substituted)1-5C alkoxy or a halogen; R<1> is a 1-3C alkyl; R<2> is a 1-3C alkyl or a 1-3C alkoxy). The derivative has high safety and develops broad spectrum at a low dose and is useful as an agent for preventing adhesion of harmful aquatic lives such as shellfishes. The compound is obtained by condensing an aminoisothiazole compound represented by formula II with a carbamoyl halide represented by formula III (Hal is a halogen such as Cl or Br) in the presence of an acid acceptor such as an alkali metal hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to an antifungal agent and an algicide, an antibacterial and antifungal agent used in the production process of industrial products, an algicide, and an aquatic organism adhesion inhibitor for preventing harmful aquatic organisms from adhering to shellfish.

[0002]

BACKGROUND OF THE INVENTION Industrial antibacterial / antifungal agents and algaecides are used for eliminating various harmful effects due to growth and proliferation of bacteria, fungi and algae in various industrial products and facilities. Conventionally, as these industrial antibacterial / antifungal agents and algaecides, organic nitrogen compounds, organic nitrogen sulfur compounds,
Organic halogen compounds, nitrogen-containing aliphatic polymers, heavy metal coordination compounds and the like are used.

[0003] Anti-biofouling agents are used in underwater equipment such as fishing nets, ship bottoms, buoys, marine structures, condenser cooling water systems for thermal or nuclear power plants, and water intake channels for cooling heat exchangers in the chemical industry. , It is used to prevent harmful aquatic organisms such as shellfish from adhering to underwater structures or reservoirs. If these aquatic organisms adhere to the cultivation net, the mesh is clogged, and the growth of the cultivated fish is hindered with a decrease in the distribution of seawater, resulting in frequent occurrence of fish diseases.

The adhesion of these aquatic organisms to a ship causes an increase in fluid resistance, which results in a decrease in navigation speed, an increase in fuel consumption, and a loss in cost for cleaning the bottom of the ship and costs due to suspension of operation. . In marine facilities, marine and underwater structures, the increase in weight due to the attachment of aquatic organisms and the inconvenience of handling operations cause the adhesion to the intake channel to cause a decrease in thermal conductivity, and the intake channel becomes blocked, This causes problems such as reduced water intake.

Conventionally, in order to prevent the adhesion and propagation of organisms in seawater and freshwater, antifouling paints containing organotin compounds such as bistributyltin oxide and copper compounds such as copper sulfate and cuprous oxide have been used. There is. Further, no prior art similar to the isothiazole urea derivative of the present invention is known.

[0006]

The above-mentioned organic nitrogen compounds, organic nitrogen sulfur compounds, organic halogen compounds,
Nitrogen-containing aliphatic polymers and heavy metal coordination compounds release irritating drugs that are problematic under the Labor Safety Act, drugs that use a large amount of drugs, and that are problematic from the viewpoint of environmental protection, and release formalin or halogen to the human body. It contains chemicals that may cause environmental impact and environmental pollution, and chemicals that may cause environmental pollution by heavy metals, and it can be said that all industrial antibacterial / antifungal agents and algaecides are composed of only preferable agents. Absent.

Further, the above-mentioned organotin compound as a biofouling preventive agent is effective in preventing the adhesion of aquatic organisms, but is highly toxic, and in particular, the accumulation of fish and shellfish in the body is remarkable, and the environmental pollution is promoted at present. It is subject to regulation. For example, in the United States, the organic tin antifouling paint control law (198
7 years) bans the use of organotin marine paints on ships under 65 feet, and in the United Kingdom, the Food Environment Protection Act (1987) has made tributyltin-containing antifoulants for ships and marine agriculture under 25 meters. The use of is prohibited.

In Japan, the Chemical Substances Control Law (1990)
Accordingly, tributyltin oxide is designated as a first-class specified chemical substance, and triphenyltin compounds and tributyltin compounds are designated as a second-class specified chemical substances. Use of such substances for fishing nets is prohibited. Furthermore, measures have been taken to suppress the use of tributyltin-based ship bottom paint (Ministry of Transport Notification, 1990).

Although the above-mentioned copper compounds are widely used in antifouling paints for intake channels and ship bottoms, they contain copper, which is a heavy metal like tin compounds, and there is concern about future environmental pollution. However, it is not a preferable underwater biofouling control agent.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that isothiazole urea derivatives have a high safety and a wide spectrum with a low dose in view of prevention of environmental pollution. The present invention has been completed by discovering that it can be used as a highly practical industrial antibacterial / antifungal agent, algaecide, and biofouling preventive agent.

That is, the present invention provides a compound represented by the general formula (1):

[0012]

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(Wherein, X and Y each independently represent a hydrogen atom, an alkyl group having 1-5 carbon atoms,
R ¹ represents an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, an alkoxy group having 1 to 5 carbon atoms substituted by a fluorine atom, or a halogen atom; R ² is 1-carbon atom
3 represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms. The present invention relates to an industrial antibacterial / antifungal agent, an algicidal agent and an anti-biofouling agent, which comprises an isothiazole urea derivative represented by

Each substituent represented by the formula (1) will be specifically described. In the present specification, "n" is normal,
"I" means iso, "s" means secondary, "t" means tertiary, and "neo" means neo. 1 carbon atom
Examples of the -3 alkyl group include methyl, ethyl, n-propyl, i-propyl and cyclopropyl, and examples of the alkyl group having 1 to 5 carbon atoms include n-butyl, i-butyl, s-Butyl, t-butyl, n-pentyl, 2-
Pentyl, 3-pentyl, i-pentyl, neo-pentyl, t-
Pentyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and the like can be mentioned.

Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy and cyclopropoxy. As the alkoxy group having 1 to 5 carbon atoms, in addition to these, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, i-pentyloxy, neo-pentyloxy, t-pentyloxy,
1-methylcyclopropoxy, 2-methylcyclopropoxy, cyclobutoxy, cyclopentyloxy and the like can be mentioned.

The halogen atom includes fluorine, chlorine, bromine and iodine. Preferred compounds of the present invention include the following compounds. (I)

[0017]

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(In the formula, X and Y are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms.
5 is an alkoxy group, a C 1-5 alkyl group substituted with a fluorine atom, a C 1-5 alkoxy group substituted with a fluorine atom, or a halogen atom, and R ¹ is a C 1-3 Wherein R ² is 1-carbon atoms
3 represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms. ) An isothiazole urea derivative represented by the formula: (II)

[0019]

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Wherein X and Y each independently represent a hydrogen atom, an alkyl group having 1-5 carbon atoms,
R ¹ represents an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, an alkoxy group having 1 to 5 carbon atoms substituted by a fluorine atom, or a halogen atom; Wherein R ² is 1-carbon atoms
3 represents an alkyl group of 3 or an alkoxy group having 1 to 3 carbon atoms. ) An isothiazole urea derivative represented by the formula: (III)

[0021]

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(Wherein X and Y are each independently a hydrogen atom, an alkyl group having 1-5 carbon atoms,
5 is an alkoxy group, a C 1-5 alkyl group substituted with a fluorine atom, a C 1-5 alkoxy group substituted with a fluorine atom, or a halogen atom, and R ¹ is a C 1-3 Wherein R ² is 1-carbon atoms
3 represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms. ) An isothiazole urea derivative represented by the formula:

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial antibacterial and antifungal agent of the present invention,
The algicidal agent and the anti-biofouling agent may contain the isothiazole urea derivative represented by the general formula (1) as an active ingredient. The compound of the present invention and the industrial antibacterial of the present invention
The compounds contained in the active ingredients of the antifungal agent, the algicide and the biofouling inhibitor are listed in Table 1 below, but the isothiazole urea derivative of the present invention is not limited thereto.

However, the symbols in the table have the following meanings. Me: methyl group, Et: ethyl group, MeO: methoxy group, EtO: ethoxy group.

[0025]

[Table 1]

[0026]

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Table 1 ────────────────── XY R ¹ R ² ────────────────── HH Me Me HH Me OMe HH Et Me HH Et Et HH Et OMe HH Me OEt Me H Me Me Me H Me OMe Me H Et Me Me H Et Et Me H Et OMe Me H Me OEt Et H Me Me Et H Me OMe Et H Et Me Et H Et Et Et H Et OMe Et H Me OEt H Me Me Me H Me Me OMe H Me Et Me H Me Et Et H Me Et OMe H Me Me OEt Me Me Me Me Me Me Me OMe Me Me Et Me Me Me Et Et Me Me Et OMe Me Me Me OEt MeO H Me Me MeO H Me OMe MeO H Et Me MeO H Et Et MeO H Et OMe MeO H Me OEt H MeO Me Me H MeO Me OMe H MeO Et Me H MeO Et Et H MeO Et OMe H MeO Me OEt Me MeO Me Me Me MeO Me OMe Me MeO Et Me Me MeO Et Et Me MeO Et OMe Me MeO Me OEt MeO MeO Me Me MeO MeO Me OMe MeO MeO Et Me MeO MeO Et Et MeO MeO Et OMe MeO MeO Me OEt CF ₃ H Me Me CF ₃ H Me OMe CF ₃ H Et Me CF ₃ H Et Et CF ₃ H Et OMe CF ₃ H Me OEt H CF ₃ Me Me H CF ₃ Me OMe H CF ₃ Et Me H CF ₃ Et Et H CF ₃ Et OMe H CF ₃ Me OEt CF ₃ OH Me Me CF ₃ OH Me OMe CF ₃ OH Et Me CF ₃ OH Et Et CF ₃ OH Et OMe CF ₃ OH Me OEt H CF ₃ O Me Me H CF ₃ O Me OMe H CF ₃ O Et Me H CF ₃ O Et Et H CF ₃ O Et OMe H CF ₃ O Me OEt Cl H Me Me Cl H Me OMe Cl H Et Me Cl H Et Et Cl H Et OMe Cl H Me OEt H Cl Me Me H Cl Me OMe H Cl Et Me H Cl Et Et H Cl Et OMe H Cl Me OEt Cl Me Me Me Cl Me Me OMe Cl Me Et Me Cl Me Et Et Cl Me Et OMe Cl Me Me OEt Me Cl Me Me Me Cl Me OMe Me Cl Et Me Me Cl Et Et Me Cl Et OMe Me Cl Me OEt FH Me Me FH Me OMe FH Et Me FH Et Et FH Et OMe FH Me OEt Me F Me Me Me F Me OMe Me F Et Me Me F Et Et Me F Et OMe Me F Me OEt Cl Cl Me Me Cl Cl Me OMe Cl Cl Et Me Cl Cl Et Et Cl Cl Et OMe Cl Cl Me OEt Br H Me Me Br H Me OMe Br H Et Me Br H Et Et Br H Et OMe Br H Me OEt ────── ──────────── The isothiazole urea derivative of the present invention can be usually produced, for example, by the method of the following reaction formula.

However, in the following reaction formula, X, Y, R ¹ , R ²
Is the same as described above, and Hal represents a halogen atom such as a chlorine atom or a bromine atom.

[0029]

[Chemical 10]

Examples of the acid acceptor used for the condensation with carbamoyl halide include hydroxides, carbonates, bicarbonates, hydrides or alkaline earth metal hydroxides, carbonates and tertiary amines of alkali metals. , Pyridines, etc., but preferably potassium carbonate, sodium hydride, triethylamine, pyridine, etc. This reaction is preferably an aprotic polar solvent such as dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, acetone or methyl ethyl ketone, a halogenated hydrocarbon such as chloroform or m-dichlorobenzene,
Alternatively, a solvent such as an aromatic hydrocarbon such as benzene, toluene or xylene is used at an appropriate temperature, for example, -20 to 100.
Proceed by stirring for 0.5 to 24 hours at ° C.

The target compound obtained by the above method is purified as a pure product by means of recrystallization, column chromatography or the like with an appropriate solvent. The isothiazole urea derivative used as an active ingredient in the present invention may be used alone, and when the industrial antibacterial / antifungal agent, algaecide and biofouling preventive agent of the present invention are used, if necessary, other Known industrial antibacterial and antifungal agents, algicides or biofouling inhibitors, and can be used as a mixture.

The following are typical examples, but the present invention is not limited to these examples. Cuprous oxide, quaternary ammonium compound, allyl isothiocyanate, 2-amino-3-chloro-1,4-naphthoquinone, ethylene-bis-thiocyanate, 2-n-octyl-3-isothiazolone, glutaraldehyde, 5-chloro- 2-n-decyl-3-isothiazolone, 5-chloro-2,4-difluoro-6-
Methoxyisophthalonitrile, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 5
-Chloro-2-methyl-3-isothiazolone, 2,3-
Dichloro-1,4-naphthoquinone, diiodomethyl-p
-Tolyl sulfone, N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfamide, N- (3,4-dichlorophenyl) -N'-methylurea, N, N-dimethyl-N'-( 3,4-dichlorophenyl) urea, zinc dimethyldithiocarbamate, 2,6-dichloro-3,5-dicyano-4-phenylpyridine, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 4, 5-dichloro-2- (4
-Chlorobenzyl) -3-isothiazolone, 4,5-dichloro-2- (4-chlorophenyl) -3-isothiazolone, 4,5-dichloro-2-n-hexyl-3-isothiazolone, 4,5-dichloro-2 -N-octyl-3
-Isothiazolone, 1,2-dibromo-2,4-dicyanobutane, 2,2-dibromo-3-nitrilopropionamide, 2-thiocyanomethylthiobenzothiazole,
2- (4-thiazolyl) benzimidazole, thiabendazole, tetrafluoroisophthalonitrile, 2,
3,5,6-tetrachloro-4- (methylsulfonyl)
Pyridine, tetraphenylborane pyridine salt, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide,
Tetra-n-butyl thiuram disulfide, tetrachloroisophthalonitrile, tetrachlorophthalonitrile,
Cu-10% Ni solid solution alloy, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, 2,3,6-trichloro-4-propylsulfonylpyridine, N- (2,4,6-trichlorophenyl) maleimide, 4,5-trimethylene-2-methyl-3-isothiazolone, 2-pyridinethiol-1-
Zinc oxide salt, 2,3,3-triiodoallyl alcohol, N- (fluorodichloromethylthio) phthalimide, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, N-phenethyldichloromaleimide, 2-bromo-2-nitropropanediol, 5-
Bromo-5-nitro-1,3-dioxane, bromochlorodimethylhydantoin, N-benzyldichloromaleimide, 1,2-benzisothiazolin-3-one, 2-
(Methoxycarbonylamino) benzimidazole, 4
-Methyl-5-chloro-2-n-octyl-3-isothiazolone, 2-methylthio-4-tert-butylamino-6
-Cyclopropylamino-s-triazine, N-2-methyl-6-ethylphenyldichloromaleimide, 2-methyl-3-isothiazolone, methylene-bis-thiocyanate, 3-iodo-2-propynylbutylcarbamate, iodopropargyl Butyl carbamate.

Further, the isothiazole urea derivative used as the active ingredient in the present invention may be composed of a single compound or a mixture of several kinds of isothiazole urea derivatives. The isothiazole urea derivative used as the active ingredient in the present invention may be added alone to the above-mentioned use application system, or as a mixture of the active ingredient and a suitable carrier or solvent if necessary, or It may be formulated as an emulsion or dispersion.

Formulations of the industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention are summarized in the field of application of industrial antibacterial / antifungal agent and algicide. The isothiazole urea derivative to be used is mixed with a suitable carrier and auxiliary agent, for example, a surfactant, a binder, a stabilizer, and the like, and mixed, and then wettable powders, emulsions, sols (flowable agents) and others are mixed by a conventional method. It is used by formulating into a suitable dosage form.

In preparing these preparations, there is no upper limit of the concentration of the isothiazole urea derivative as an active ingredient as long as wettable powders, emulsions, solutions, sols and other suitable preparations can be prepared. Based on the weight of these formulations,
It is mixed in a proportion of 1-90% by weight, preferably 3-40% by weight. As the carrier that can be used, any solid or liquid carrier can be used as long as it is commonly used for industrial antibacterial / antifungal agents and algaecides, and it is not limited to a particular carrier.

Examples of solid carriers include mineral powders, such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphorous lime, white carbon, slaked lime, silica sand, ammonium sulfate, urea and the like, or Vegetable powders such as soybean flour, starch, crystalline cellulose and the like, alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like can be mentioned.

Examples of liquid carriers include water, alcohols such as methyl alcohol, ethyl alcohol, n-
Propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol and the like, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene,
Or halogenated hydrocarbons such as chloroform, dichloromethane, ethylene dichloride and the like, ethers such as ethyl ether, dioxane, tetrahydrofuran and the like, ketones such as acetone and methyl ethyl ketone,
Cyclohexanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate and the like, nitriles such as acetonitrile, propionitrile, acrylonitrile and the like, sulfoxides such as dimethyl sulfoxide and the like,
Alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, amines such as triethylamine, and aliphatic and alicyclic hydrocarbons such as n-hexane and cyclohexane, and industrial gasoline (petroleum ether). ,
Solvent naphtha) and petroleum fractions (paraffins, kerosene, light oil, etc.).

In the case of preparations such as emulsions, wettable powders and sols (flowables), emulsification, dispersion, solubilization, wetting, foaming,
A surfactant is added for the purpose of spreading or the like. Examples of such a surfactant include those shown below.
It is not limited only to these. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters and sorbitan alkyl esters.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulphates, polyoxyethylene alkyl sulphates, aryl sulphonates and lauryl sulphates. Examples of the cationic surfactant include alkylamines (such as laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride).

Examples of the amphoteric surfactant include carboxylic acid (betaine type) sulfuric acid ester and the like. In addition to these, polyvinyl alcohol (PVA),
Thickeners and various auxiliary agents such as carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, xanthan gum and hydroxypropyl cellulose can be blended.

Further, if necessary, a suitable amount of a stabilizer such as an antioxidant and an ultraviolet absorber can be added. The industrial antibacterial / antifungal agent and algicide of the present invention containing an isothiazole urea derivative as an active ingredient can be used for the following applications. Waterborne paints, adhesives, latex, emulsion products such as acrylics, starches, pigments, slurry products such as calcium carbonate, and growth control of bacteria, fungi and algae in joint cement; construction materials (building materials, civil engineering materials, etc.) Preservation of wood; Preservation of cutting oil; Prevention of mildew of surfactant; Prevention of sterilization and slime generation of cooling towers, pulp and paper mills in factory manufacturing facilities and building air conditioning, etc .; Spraying or dipping treatment on textile fabric and leather Antibacterial and antifungal treatment with; protection from attack by bacteria, fungi and algae that occur during the exposure of paint film, especially exterior paint film to wind and rain; vinyl chloride, polyurethane, polyethylene, polypropylene, silicone, modified Interior / exterior materials (houses, medical facilities), building materials (building building materials, etc.) made of resins such as silicone, nylon, and epoxy Antibacterial, antifungal and algicidal products for household materials, household goods, sports goods, etc .; protection of slime deposits on sugarcane and sugar beet sugar manufacturing equipment; air washers, scrubber systems and industrial fresh water supply systems Prevention of accumulation and accumulation of microorganisms in food processing; Maintenance of sanitary conditions in food factories, etc .; Deodorization and sterilization of manufacturing facilities, sewage treatment plants, human waste treatment plants, etc .; Microbial contamination in oilfield cutting oil, muddy water and secondary oil recovery processes Prevention of bacterial and fungal growth in paper coatings and coatings; prevention of microbial contamination of cosmetics and toiletry products; suppression of algal growth in pools, etc .; agricultural formulations, electrodeposition systems, diagnostics and pharmaceutical products. Prevention of microbial contamination of medical equipment, etc .; prevention of microbial accumulation in photographic processing.

Examples of the anti-fouling agent containing an isothiazole urea derivative as an active ingredient include fishing nets, ship bottoms,
Blue mussels for underwater facilities such as buoys and other underwater facilities, marine structures, condenser cooling water systems for thermal or nuclear power plants, water intake channels for cooling water for heat exchangers in the chemical industry, underwater structures such as auxiliary equipment for dams, etc. It can be used for the prevention of adhesion of harmful aquatic organisms such as shellfish such as barnacles, oysters, hydrops, hydra, serpra, ascidians, bryozoans and snails, and algae such as Ulva, Aonori and Shimizuro.

Next, synthesis examples of the isothiazole urea derivative are shown, but the compounds used in the present invention are not limited to these. Synthesis Example 1 (Synthesis of Compound 1)

[0044]

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3.42 g of 3-amino-5-methylisothiazole and 3.33 g of triethylamine were added to 100 ml of chloroform, and then 3.70 g of N-methyl-N-methoxycarbamoyl chloride dissolved in 30 ml of chloroform was added at 5 to 10 ° C. Was dropped. After heating under reflux for 2 hours, the mixture was allowed to cool to room temperature, and the reaction solution was washed twice with 50 ml of water and once with 50 ml of saturated saline.

After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained crude product was washed with an ether / n-hexane mixed solvent to give the title compound 5.1.
2 g was obtained. (Melting point: 165.0-167.0 ° C.) Formulation examples when the isothiazole urea derivative of the present invention is used as an industrial antibacterial / antifungal agent and an algicide are shown using compound 1. The type and amount of the carrier and the auxiliary agent are not limited to these.

[0047]

Table 2 Formulation Example 1 (emulsion) Ingredients% by weight Compound 15 5 Dimethyl sulfoxide 85 Methyl isobutyl ketone 5 Solpol 800A 5 (Emulsifier manufactured by Toho Chemical Co., Ltd.) # 100 The resulting emulsion was obtained.

[0048]

Formulation Example 2 (Wettable powder) Ingredient wt% Compound 1 20 Lauryl sulfate 7 Clay 73 ───── 100 The above ingredients were uniformly mixed and pulverized to obtain a wettable powder containing 20% of the active ingredient.

[0049]

Table 4 Formulation Example 3 (Floable agent) Ingredients% by weight Compound 1 20 Lauryl sulfate 2 Xanthan gum 2 Hydroxypropylcellulose 1 Distilled water 75 100 The above ingredients were put in a ball mill and pulverized and mixed for 12 hours, and the active ingredients were 20%. To obtain a flowable agent.

The formulated antibacterial / antifungal agents and algaecides of the present invention can be used in various industrial raw materials or products by diluting various formulations as they are or by diluting with water or a suitable organic solvent. In the method of adding or mixing in, the method of applying or spraying on the surface of various industrial raw materials and products, or the various industrial raw materials and products in the diluted solution of the industrial antibacterial and antifungal agent and the algicide of the present invention. It can be used by various methods according to the generally used industrial antibacterial / antifungal agents and algaecides, including the method of dipping, etc.,
It is not limited to any particular method.

The formulations of the industrial antibacterial / antifungal agents, algaecides and biofouling inhibitors of the present invention will be outlined in the field of application of biofouling inhibitors, and the isothiazole urea derivative used as an active ingredient in the present invention is , Paints, solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions and the like, general formulas usually used can be adopted.

When the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, an isothiazole urea derivative as an active ingredient is blended with a film-forming agent to prepare a paint, and the ship bottom is By applying to a marine structure, a water intake pipe for cooling, an underwater structure, or the like, it is possible to prevent the adhesion and propagation of aquatic organisms. As the film forming agent, oil varnish, synthetic resin, artificial rubber or the like is used.

Further, a solvent, a pigment or the like may be used if necessary. When a paint is prepared, the concentration of the isothiazole urea derivative, which is an active ingredient, has no upper limit as long as a coating film can be formed. It is blended in a ratio of weight%. Formulation examples using the underwater biofouling inhibitor of the present invention as an antifouling paint are shown using Compound 1, but are not limited thereto.

[0054]

Table 5 Formulation Example 4 Ingredients% by weight Compound 1 8 VYHH (vinyl synthetic resin, manufactured by UCC) 7 Rosin 7 Tricresyl phosphate 3 Talc 20 Barium sulfate 15 Petals 10 Xylene 20 Methyl isobutyl ketone 10 100

[0055]

[Table 6] Formulation Example 5 Ingredients% by weight Compound 1 5 CR-10 (chlorinated rubber resin, manufactured by Asahi Denka Co., Ltd.) 13 Zinc flower 20 Talc 20 Plasticizer 2 Stem 10 Xylene 30 100 Water of the present invention When the biofouling inhibitor is used in the form of a solution, for example, a solution in which an isothiazole urea derivative as an active ingredient is dissolved in a solvent together with a film-forming agent is prepared,
When applied to aquaculture nets, fixed fishing nets, etc., the adhesion and propagation of aquatic organisms can be prevented.

As the coating film forming agent, synthetic resin, artificial rubber, natural resin and the like are used, and as the solvent, xylene,
Toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are used. Furthermore, additives such as plasticizers may be used if necessary. When preparing a solution, the concentration of the active ingredient isothiazole urea derivative has no upper limit as long as the solution can be formed, but 1 to 50% by weight based on the weight of the solution,
Preferably, it is blended at a ratio of 5 to 30%.

Compound 1 is shown as a prescription example when the aquatic organism adhesion preventing agent of the present invention is used as an antifouling agent solution, but the invention is not limited thereto.

[0058]

Table 7 Formulation Example 6 Component Weight% Compound 1 15 Acrylic resin (50% xylene liquid) 50 Xylene 35 100

[0059]

Table 8 Formulation Example 7 Component Weight% Compound 1 10 Acrylic resin (50% xylene solution) 40 Ditertiary nonyl pentasulfide 5 Liquid paraffin 5 Xylene 40─────100 Prevention of biofouling in water of the present invention When the emulsion is used in the form of an emulsion, a surfactant is usually added to a solution of an isothiazole urea derivative as an active ingredient to prepare a desired emulsion according to a general method for preparing an emulsion. There is no particular limitation on the type of surfactant that can be used.

The prepared emulsion can be used by kneading it into raw materials such as aquaculture fishing nets and stationary nets used in the ocean or water, for example, polymer resins. When an emulsion is prepared, the concentration of the isothiazole urea derivative as an active ingredient has no upper limit as long as the emulsion can be formed, but 1 to 50% by weight, preferably 3 to 30% by weight based on the weight of the emulsion.
It is mixed in the ratio of.

The above solution or emulsion of the present invention can be used by adding it to water, water storage or the like in order to prevent the aquatic organisms from adhering and propagating in the cooling water intake pipe or the water reservoir.

[0062]

[Examples] The present invention will be described in more detail below with reference to Examples using Compound 1, but the present invention is not limited thereto. Example 1 (Evaluation of Growth Inhibitory Activity Against Freshwater Green Algae) Freshwater green alga in the logarithmic growth phase (Selenastrum capricornutum, Selena)
strum capricornutum ) In a medium containing 10 ⁵ cells / ml,
A fixed amount of the compound 1 of the present invention was dissolved, and a sample having a concentration of the compound of the present invention in the medium of 500 ppb was prepared.
The culture was allowed to stand still at 1 ° C. for 24 hours under continuous illumination.

After 72 hours, the proliferation rate was determined by measuring the number of cells using a hemocytometer. The growth inhibition rate is
It was calculated from the comparison with the untreated section. The results are shown in Table 2.

[0064]

[Table 9] Compound growth inhibition rate (%) 500 ppb ─────────────────────── 1 193 ─────────────────────── Implementation Example 2 (Evaluation of growth inhibitory activity against freshwater algae) A certain amount of the compound 1 of the present invention was dissolved in a medium containing 10 ⁵ cells / ml of freshwater algae in the logarithmic growth phase, and the concentration of the compound of the present invention in the medium was each adjusted. A sample of 500 ppb was prepared and the temperature was 20 ± 2 ° C. for freshwater diatoms, 23 ± 2 ° C. for other algae, and 10 hours under continuous lighting conditions for 24 hours.
Shaking culture at 0 rpm was performed.

After 72 and 168 hours, the proliferation rate was determined by measuring the total cell volume using a hemocytometer.
The growth inhibition rate was calculated by comparison with the untreated group. The results are shown in Table 3. However, the symbols in the table mean the following. A: Freshwater green algae ( Chlorella pyrenoid
osa ) B: Freshwater cyanobacteria ( Microcystis aer)
uginosa ) C: Freshwater diatoms ( Diatoma elongatu)
m )

[0066]

[Table 10] Example 3 (Evaluation of Biofouling Prevention Activity) 0.4 mg, 0.7 mg and 1.3 mg of Compound 1 were completely dissolved in about 1 ml of acetone, respectively, and placed in a 4 cm diameter zone drawn on a test paper. The sample solution was applied uniformly.

A zone coated only with acetone as a blank, 1.0 mg and 0.5 m of copper sulfate as a comparative agent
Zones were provided in which each g was applied. After drying, mussels having a shell length of about 2-2.5 cm were bonded to the outer periphery of each zone by using four rubber pieces as spacers. The prepared test plate was immersed in a water tank into which seawater was introduced, and allowed to stand in the dark for 3 hours. The test plate was lifted out of the water tank, and the attachment position and the number of the mussel thread were measured.

In comparison with copper sulfate used as a comparative drug,
The adhesion control effect (adhesion repellent activity) was determined. The evaluation method of the adhesion repellent activity is described by Kazuo Ina and Hideo Eto, "Searching method for adhesion repellent of marine marine organisms using mussels" (Chemistry and Biology, Vol. 28 (No. 2), pp. 132-138 (199)
0 years).

The results are shown in Table 4.

[0070]

[Table 11] Table 4 ─────────────────────── Active ingredient dose (mg) Judgment ────────────化合物 Compound 1 1.3 ++ 0.7 ++ 0.4 + Comparative drug (copper sulfate) 1.0 ++ 0.5 + blank − − ────────記号 The symbols in the table have the following meanings.

++: No adhesion is observed in the zone, and a strong repellent effect is recognized. +: Adhesion inside the zone is also observed, but most adhere outside the zone, and a repellent effect is observed. -: Adhered to the same extent inside and outside the zone, no repellent effect was observed.

[0072]

EFFECT OF THE INVENTION The isothiazole urea derivative represented by the general formula (1) is highly safe, exhibits a wide spectrum at a low dose, and is used for industrial antibacterial and antifungal agents, algicides and biofouling prevention. Useful as an agent.

Claims (16)

[Claims] 1. General formula (1): (Wherein X and Y each independently represent a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, or an alkyl group having 1-5 carbon atoms substituted with a fluorine atom) R ¹ is a C 1-5 alkoxy group or halogen atom substituted with a fluorine atom,
3 alkyl group, R ² represents an alkyl group or an alkoxy group having a carbon number of 1-3 of 1-3 carbon atoms. ) An isothiazole urea derivative represented by the formula: 2. General formula (2): (Wherein X and Y each independently represent a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, or an alkyl group having 1-5 carbon atoms substituted with a fluorine atom) R ¹ is a C 1-5 alkoxy group or halogen atom substituted with a fluorine atom,
3 alkyl group, R ² represents an alkyl group or an alkoxy group having a carbon number of 1-3 of 1-3 carbon atoms. ) Isothiazole urea derivative represented by. 3. A compound of the general formula (3): (In the formula, X and Y are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom. R ¹ is a C 1-5 alkoxy group or halogen atom substituted with a fluorine atom,
3 alkyl group, R ² represents an alkyl group or an alkoxy group having a carbon number of 1-3 of 1-3 carbon atoms. ) An isothiazole urea derivative represented by the formula: 4. A compound of the general formula (4): (In the formula, X and Y are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom. R ¹ is a C 1-5 alkoxy group or halogen atom substituted with a fluorine atom,
3 alkyl group, R ² represents an alkyl group or an alkoxy group having a carbon number of 1-3 of 1-3 carbon atoms. ) An isothiazole urea derivative represented by the formula: 5. An industrial antibacterial / antifungal agent comprising the compound according to claim 1. 6. An algaecide containing the compound according to claim 1. 7. An anti-biofouling agent comprising the compound according to claim 1. 8. An industrial antibacterial / antifungal agent comprising the compound according to claim 2. Description: 9. An algicide comprising the compound according to claim 2. Description: 10. A biofouling inhibitor comprising the compound according to claim 2. 11. An industrial antibacterial / antifungal agent comprising the compound according to claim 3. 12. An algicide comprising the compound according to claim 3. 13. A biofouling inhibitor comprising the compound according to claim 3. 14. An industrial antibacterial and antifungal agent containing the compound according to claim 4. Description: 15. An algaecide containing the compound according to claim 4. 16. An agent for preventing biofouling containing the compound according to claim 4.