JPH11209205A - Industrial antibacterial and antifungal agent, algicidal agent and anti-biofouling agent containing n-pyridylanilines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial antibacterial and antifungal agent with high practicality and high safety, capable of manifesting a wide spectrum of effect with a small amount of dosage in the viewpoint of environmental pollution by making the agent include specific pyridylanilines. SOLUTION: This industrial antibacterial and antifungal agent contains (A) N-pyridylanilines of the formula [A is H or chlorine; B is H, a 1-5C alkyl, a 2-6C alkenyl or the like; X and Y is nitro, a halogen or the like; Z is H, a 1-5C alkoxy or the like; (j) and (k) are each 0-3 with the proviso that (j)+(k)<=3] and (B) optionally, other well-known industrial antibacterial and antifungal agents. The antibacterial and antifungal agent is obtained by compounding and mixing a suitable carrier and an auxiliary substance, e.g. a surfactant, a binder and a stabilizer therewith, and used by forming the compounded and mixed materials into a proper dosage form of a water- dispersible powder, an emulsion, a sol agent (a floable agent) or the like. Preferably, the component A is included in a proportion of 1-90 wt.% based on the amount of the preparation when the preparation is prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial agent for industrial products.
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 and antifungal agents and algicides are used to eliminate various adverse effects of the growth and growth of bacteria, fungi and algae on various industrial products and facilities. Conventionally, as these industrial antibacterial and antifungal agents and algicides, 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 underwater 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.

[0004] The adhesion of these aquatic organisms to ships causes an increase in fluid resistance, which results in a decrease in navigation speed, an increase in fuel consumption, a cost for cleaning the bottom of the ship, and a loss of 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, Problems such as a decrease in water intake will occur.

Conventionally, in order to prevent the adhesion and propagation of these 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. I have. JP-A-57-1
JP-A-26475 and JP-A-57-126476 disclose an N-pyridylaniline compound, a method for producing the compound, and its use as an agricultural and horticultural fungicide, insecticide, and acaricide.

Also, fluazinam (trade name: Froncide), which is the patented compound, has been developed and commercialized as an agricultural fungicide. However, there is no description of the use of the compounds described in this publication as industrial antibacterial and antifungal agents, algicides and biofouling inhibitors.

[0007]

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 is possible to say that industrial antibacterial and antifungal agents and algicides as a whole consist only of the preferred chemicals, including chemicals that are likely to be affected by environmental impact and environmental pollution and chemicals that are likely to be environmentally polluted by heavy metals. Absent.

Although the above-mentioned organotin compounds as biofouling inhibitors are effective in preventing the fouling of aquatic organisms, they are highly toxic and cause significant accumulation of fish and shellfish in the body. It is subject to regulation. For example, in the United States, the Organotin Antifouling Paint Control Law (198
7 years) banned the use of organotin marine paints on ships up to 65 feet, and in the United Kingdom, the Food Environmental Protection Act (1987) allowed tributyltin-containing antifouling agents to be applied to ships up to 25 meters and marine farming. 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 curb the use of tributyltin-based ship bottom paints (Notification of the Ministry of Transport, 1990).

[0010] The above-mentioned copper compounds are widely used in antifouling paints for intake channels and ship bottoms, but contain copper which is a heavy metal like tin compounds. However, it is not a preferable underwater biofouling control agent.
The compounds used in the present invention are not described in the above-mentioned regulation law, and the publication discloses that N-pyridylanilines are effective as industrial antibacterial and antifungal agents, algicides and biofouling inhibitors. Nothing is described.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, N-pyridylanilines have been found to be highly safe and to be widely used at a low dose in view of the prevention of environmental pollution. The present invention was found to be a highly practical industrial antibacterial and antifungal agent, an algicide, and a biofouling inhibitor that exhibit a spectrum, and completed the present invention.

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

[0013]

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Wherein A represents a hydrogen atom or a chlorine atom,
B is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms or 1 carbon atom; X and Y each independently represent a nitro group, a trifluoromethyl group or a halogen atom, and Z represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 5 carbon atoms. Where j
And k each independently represent 0, 1, 2 or 3, j
+ K always represents 3 or less. The present invention relates to an industrial antibacterial and antifungal agent, an algicide and a biofouling inhibitor, characterized by containing an N-pyridylaniline represented by the formula (1).

Each substituent represented by the formula (1) will be specifically described. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 1-pentyl, 2-pentyl, Pentyl, i-pentyl, neo-pentyl, t-pentyl, cyclopropyl, 1-methylcyclopropyl, 2-
Methylcyclopropyl, cyclobutyl, cyclopentyl and the like can be mentioned.

The alkenyl group having 2 to 6 carbon atoms includes ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl- 1-propenyl, 1-methyl-2-propenyl, 2-methyl-2
-Propenyl, 1-ethyl-2-vinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,2-dimethyl
1-Propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl
1-Propenyl, 1-ethyl-2-propenyl, 1-methyl-1-
Butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 1-i-propylvinyl, 2,4-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,
5-hexenyl, 2,4-hexadienyl, 1-methyl-1-pentenyl and the like.

The alkynyl group having 2 to 6 carbon atoms includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, -Pentynyl, 1-hexynyl, 2-
Hexinyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like can be mentioned. Examples of the alkylcarbonyl group having 2 to 6 carbon atoms include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-
Butylcarbonyl, i-butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, 1-pentylcarbonyl,
2-pentylcarbonyl, 3-pentylcarbonyl, i-pentylcarbonyl, neo-pentylcarbonyl, t-pentylcarbonyl, cyclopropylcarbonyl, 1-methylcyclopropylcarbonyl, 2-methylcyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, etc. Is mentioned.

Examples of the alkylsulfonyl group having 1 to 5 carbon atoms include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl,
t-butylsulfonyl, 1-pentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, i-pentylsulfonyl, neo-pentylsulfonyl, t-pentylsulfonyl, cyclopropylsulfonyl, 1-methylcyclopropylsulfonyl, 2-methylcyclo Propylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl and the like.

The halogen atom includes fluorine, chlorine, bromine and iodine. Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy,
i-propoxy, n-butoxy, i-butoxy, s-butoxy,
t-butoxy, pentyloxy and the like.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial antibacterial and antifungal agent of the present invention,
The algicide and the biofouling inhibitor may contain the N-pyridylaniline represented by the general formula (1) as an active ingredient. Preferred compounds contained in the active ingredients of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are listed in Table 1 below, but the compounds used in the present invention are not limited to these. Not something.

However, the symbols in the table have the following meanings. Me: methyl group, MeCO: acetyl group, MeSO ₂ :
Methanesulfonyl group, OMe: methoxy group, OEt: ethoxy group.

Table 1

[0023]

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[0024]

[Table 1] {Substituent AB on benzene ring} {2 3 (Z) 4 5 6} ────────────── HH NO ₂ H CF ₃ H NO ₂ HH NO ₂ H NO ₂ H CF ₃ HH NO ₂ H NO ₂ H NO ₂ HH NO ₂ H Cl H NO ₂ HH NO ₂ H NO ₂ H Cl HH NO ₂ Cl CF ₃ H NO ₂ HH NO ₂ OMe CF ₃ H NO ₂ Cl H NO ₂ H CF ₃ H NO ₂ Cl H NO ₂ H NO ₂ H CF ₃ Cl H NO ₂ H NO ₂ H NO ₂ Cl H NO ₂ H Cl H NO ₂ Cl H NO ₂ H NO ₂ H Cl Cl H NO ₂ Cl CF ₃ H NO ₂ Cl H NO ₂ OMe CF ₃ H NO ₂ Cl H NO ₂ OEt CF ₃ H NO ₂ Cl Me NO ₂ Cl CF ₃ H NO ₂ Cl CH ₂ = CHCH ₂ NO ₂ Cl CF ₃ H NO ₂ Cl CH≡CCH ₂ NO ₂ Cl CF ₃ H NO ₂ Cl MeCO NO ₂ Cl CF ₃ H NO ₂ Cl MeSO ₂ NO ₂ Cl CF ₃ H NO ₂ ────────────────────────────────────

The N-pyridylanilines of the present invention are disclosed in JP-A-57-126475 and JP-A-57-12264.
Usually, for example, the following (a), (b)
Alternatively, it can be produced by the method (c). However, Z ¹ , Z ² and Z ³ in the following reaction formula are the same as those in the general formula (1).
Is included.

(A) when Z ¹ is a hydrogen atom or a halogen atom;

[0027]

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In the above reaction formula, A, X, Y, j and k
Is the same as described above, Hal is a halogen atom such as a chlorine atom or a fluorine atom, and Z ¹ is a hydrogen atom or a halogen atom. Acid acceptors used in this reaction include, for example, alkali metal hydroxides, carbonates, bicarbonates,
Examples thereof include hydroxides and carbonates of hydrides or alkaline earth metals, and preferred are potassium hydroxide and sodium hydride.

The above reaction is preferably carried out in an aprotic polar solvent such as dimethylformamide, dimethylsulfoxide, sulfolane, tetrahydrofuran, dioxane or the like at a suitable temperature, for example, -50 to 100 ° C. for 0.5 to 2 hours.
Perform by stirring for 4 hours. (B) when Z ³ is an alkoxy group;

[0030]

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In the above reaction formula, Z ² represents a halogen atom such as a chlorine atom and a bromine atom, and A, X, Y, j and k
Is the same as described above, and Z ³ represents an alkoxy group. The acid acceptor used in this reaction is the same as that which can be used in the method (a), and frequently used solvents include alcohols such as methanol and ethanol in addition to the aprotic polar solvent described above. Carbon tetrachloride, chloroform, m-
And halogenated hydrocarbons such as dichlorobenzene.

[0032] The reaction temperature is generally -30 ° C to 150 ° C, and the reaction time is 0.5 to 24 hours. (C) B is an alkyl group, an alkenyl group, an alkynyl group,
In the case of an alkylcarbonyl group or an alkylsulfonyl group;

[0033]

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In the above reaction, B represents an alkyl group, an alkenyl group, an alkynyl group, an alkylcarbonyl group or an alkylsulfonyl group, and A, X, Y, Z, j and k
Is the same as described above, and Hal represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. Examples of the acid acceptor used in this reaction include tertiary amines, pyridines and the like in addition to those described in the above method (a), and preferably sodium hydride for alkylation, alkenylation and alkynylation. However, triethylamine or pyridine are also suitable.

The above reaction is carried out by using carbon tetrachloride, chloroform,
The reaction is performed in a solvent such as a halogenated hydrocarbon such as m-dichlorobenzene or an aromatic hydrocarbon such as benzene, toluene and xylene. The reaction temperature is generally −30 ° C.
１５０150 ° C., and the reaction time is 0.5-24 hours.

The target compound obtained by the methods (a), (b) and (c) is purified as a pure product by recrystallization or column chromatography using an appropriate solvent. The N-pyridyl anilines used as the active ingredient in the present invention may be used alone, or when using the industrial antibacterial / antifungal agent of the present invention, an algicide and a biofouling inhibitor, if necessary, Other known industrial antibacterial and antifungal agents, algicides or biofouling inhibitors can be further contained and used as a mixture.

Representative examples are listed below, but the present invention is not limited to these. 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
-Tolylsulfone, 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-butylthiuram 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 N-pyridylanilines used as the active ingredient in the present invention may be composed of a single compound or a mixture of several kinds of N-pyridylanilines. N- used as an active ingredient in the present invention
The pyridylanilines may be added alone to the system of use described above, or may be formulated as a mixture of the active ingredients and, if necessary, a suitable carrier or solvent, or as an aqueous emulsion or dispersion. You may.

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 N-pyridylaniline 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 powder, emulsion, sol (flowable agent) and It is used after being formulated into other appropriate dosage forms.

In preparing these preparations, there is no upper limit to the concentration of N-pyridylaniline 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 blended in a proportion of 1-90% by weight, preferably 3-40% by weight. As a carrier that can be used, any solid or liquid can be used as long as it is commonly used for industrial antibacterial and antifungal agents and algicides, and it is not limited to a specific one.

Examples of solid carriers include mineral powders, such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphate lime, white carbon, slaked lime, silica sand, ammonium sulfate, urea and the like, or Vegetable powders such as soybean flour, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers, highly dispersible silicic acids, 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, ethylene glycol monoethyl ether and the like; amines such as triethylamine and the like; aliphatic and alicyclic hydrocarbons such as n-hexane and cyclohexane; ,
Solvent naphtha) and petroleum fractions (paraffins, kerosene, light oil, etc.).

In the case of preparations such as emulsions, wettable powders and sols (flowable preparations), emulsification, dispersion, solubilization, wetting, foaming,
A surfactant is added for the purpose of spreading or the like. Such surfactants include those shown below,
It is not limited only to these.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester and sorbitan alkyl ester.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate and lauryl sulfate.

Examples of the cationic surfactant include alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride and the like).

Examples of the amphoteric surfactant include carboxylic acid (betaine type) sulfate and the like. In addition, in addition to these, polyvinyl alcohol (PVA),
Thickeners such as carboxymethylcellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth, guar gum, xanthan gum and hydroxypropylcellulose, and various adjuvants 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 and antifungal agents and algicides containing N-pyridylanilines as an active ingredient of the present invention 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 fungi of surfactants; Sterilization and prevention of slime formation in cooling towers, pulp and paper mills in factory manufacturing equipment and building air conditioning, etc .; By spraying or dipping on textiles and leather Antibacterial / antifungal treatment; bacteria and bacteria that are generated while the paint film, especially exterior paint film, is exposed to the elements
Protection from fungal and algae attacks; vinyl chloride, polyurethane, polyethylene, polypropylene, silicone,
Interior / exterior materials (for housing and medical facilities) and building materials (building materials,
Antibacterial, antifungal and algicidal products for household and household goods, sports goods, etc .; protection of slime deposits on sugarcane and sugar beet production 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 N-pyridylanilines as an active ingredient include: fishing nets, ship bottoms, buoys and other underwater facilities, marine structures, thermal power plants and condenser cooling water systems of nuclear power plants. Mussels, barnacles, oysters, hydromussels, to underwater structures such as water intake channels for cooling water of heat exchangers in the chemical industry, auxiliary equipment for dams, etc.
It can be used to prevent the adhesion of harmful aquatic organisms such as shellfish such as hydra, serpula, sea squirt, bryozoan and snail, and algae such as Aosa, Aonori and Shiomidoro.

Formulation examples when the N-pyridylanilines of the present invention are used as industrial antibacterial and antifungal agents and algicides are shown using Compounds 1 and 2. The type and the amount of addition are not limited to these. (Compounds 1 and 2 are disclosed in
It was synthesized by the methods described in JP-A-126475 and JP-A-57-126476. )

[0052]

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[0053]

Table 2 Formulation Example 1 (Emulsion) Ingredient% by weight Compound 15 5 Dimethyl sulfoxide 85 Methyl isobutyl ketone 5 Solpol 800A 5 (Emulsifier manufactured by Toho Chemical Co., Ltd.) # 100 The above were mixed and dissolved to obtain an emulsion containing 5% of the active ingredient.

[0054]

Table 3 Formulation Example 2 (Wettable powder) Ingredient% by weight Compound 2 20 Lauryl sulfate 7 Clay 73 # 100 The above is uniform The wettable powder containing 20% of the active ingredient was obtained.

[0055]

Table 4 Formulation Example 3 (Floable agent) Ingredient weight% Compound 1 20 Lauryl sulfate 2 Xanthan gum 2 Hydroxypropylcellulose 1 Distilled water 75 # 100 The above was put in a ball mill and ground and mixed for 12 hours to obtain a flowable agent containing 20% of the active ingredient.

The industrialized antibacterial and antifungal agents and algicides of the present invention, which have been formulated, can be obtained by mixing various preparations as they are or by diluting them with water or an appropriate organic solvent, in various industrial raw materials or in products. 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. Including a method of immersion, etc., can be used by various methods according to the use of industrial antibacterial and antifungal agents and algicides that have been generally performed so far,
It is not limited to any particular method.

The formulation of the industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention is outlined in the field of application of biofouling inhibitors. N-pyridylanilines used as active ingredients in the present invention Is used after being prepared in the form of a paint, a solution, an emulsion or 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 N-pyridylaniline as an active ingredient is blended with a film-forming agent to prepare a paint, and By applying to the bottom of a ship, an offshore structure, a cooling water intake pipe, an underwater structure, or the like, the adhesion and propagation of underwater organisms can be prevented. As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.

Further, a solvent, a pigment or the like may be used if necessary. When preparing a paint, the concentration of the active ingredient N-pyridylaniline has no upper limit as long as a coating film can be formed.
It is blended at a ratio of 1 to 50% by weight, preferably 5 to 20% by weight. Formulation examples in the case of using the underwater biofouling inhibitor of the present invention as an antifouling paint are shown using Compounds 1 and 2,
It is not limited to these.

[0060]

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} １００ 100

[0061]

Table 6 Formulation Example 5 Ingredients% by weight Compound 2 5 CR-10 (chlorinated rubber resin, manufactured by Asahi Denka Co., Ltd.) 13 Zinc flower 20 Talc 20 Plasticizer 2 Red handle 10 Xylene 30 100 pieces When the underwater biofouling inhibitor of the present invention is used in the form of a solution, for example, a solution in which N-pyridylaniline as an active ingredient is dissolved in a solvent together with a film-forming agent is prepared, and aquaculture fishing nets, stationary fishing nets, and the like are prepared. By applying the composition to the water, the adhesion and propagation of aquatic organisms can be prevented.

As the 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. Further, if necessary, an additive such as a plasticizer may be used. When a solution is prepared, the concentration of the active ingredient, N-pyridylaniline, has no upper limit as long as the solution can be formed, but 1 to 50% by weight, preferably 5 to 30% by weight of the solution. It is blended in a ratio.

Formulation examples in the case of using the underwater anti-biofouling agent of the present invention as an antifouling agent solution are shown using compounds 1 and 2, but are not limited thereto.

[0064]

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

[0065]

Table 8 Formulation Example 7 Ingredients% by weight Compound 2 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 added to a solution of N-pyridylaniline as an active ingredient to prepare a desired emulsion according to a general method for preparing an emulsion. The type of surfactant used is not particularly limited.

The prepared emulsion can be used by kneading it into raw materials such as aquaculture nets and stationary nets used in the ocean or water, for example, polymer resins and the like. When an emulsion is prepared, the concentration of the active ingredient, N-pyridylaniline, 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. In the proportion of

The above-mentioned solution or emulsion of the present invention can be used by adding it to service water, water storage, or the like in order to prevent adherent propagation of aquatic organisms in a cooling water intake pipe or a reservoir.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically and in detail with reference to Examples using Compounds 1 and 2 and Compounds 3 to 5, but the present invention is not limited thereto.
(Compounds 3 to 5 were synthesized by the methods described in JP-A-57-126475 and JP-A-57-126476.)

[0069]

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Example 1 (Evaluation of antibacterial and antifungal activities) Bacillus subtilis ( Bacillus subtilis ) was tested in 125 ml of bouillon agar medium with 6.6 ml of the test bacterium and Trichophyton mentagrophytes.
phytes ) was added to 31.3 ml of the test bacterium to 125 ml of Sabouraud agar medium, and the mixture was stirred with care so as not to cause foaming, and was uniformly poured on a plate to solidify. Next, a certain amount of the compound of the present invention was weighed and diluted with acetone to a predetermined concentration. A sample containing the prepared compound of the present invention at a fixed concentration was impregnated into a paper disk, spread on filter paper, air-dried, and equally spaced on a plate on which each test bacterium was flown. Bacillus subtilis (Bacillus sub
tilis ) was incubated at 37 ° C. for 1 day and Trichophyton mentagrophytes was incubated at 28 ° C. for 3 days in an incubator, and the diameter of each inhibition circle was measured to evaluate the activity. Table 2 shows the results when a sample having a concentration of 100 ppm was used. However, the symbols in the table mean the following.

[0071] A: Bacillus subtilis (Bacillus sub
tilis ) B: Trichophyt
on mentagrophytes ) +: Blocking circle (A; 10 to 13 mm, B; 10 to 20 m)
m) is observed. -: No blocking circle is observed.

[0072]

Table 9 Table 2 ────────────────────────── compounds judgment No. AB {1 ++ 2 ++ 3 +++ 4 ++-5 ++++} Example 2 (Evaluation of antibacterial and antifungal activities) The compound of the present invention was diluted with dimethyl sulfoxide in a dilution series (20,000, 10,000, 5000, 2500, 1
250, 626, 313, 156, 78, 39 mg /
l) was prepared. This is used as a susceptibility medium for bacteria.
N (Nissui Pharmaceutical Co., Ltd.), and for fungi, 0.5 m per 9.5 ml of potato dextrose agar medium (Nissui Pharmaceutical Co., Ltd.)
1 was added and mixed, and the mixture was poured into a petri dish to obtain a solidified flat plate. The concentration of the compound of the present invention in the agar medium is 1000, 50, respectively.
0, 250, 125, 62.5, 31.3, 15.6,
7.8, 3.9, 2.0 mg / l. The inoculated bacteria were cultured at 37 ° C. for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical). The fungi were cultured on a potato dextrose agar medium (Nissui Pharmaceutical) for 10 days, and then 10 ⁶ C
A FU / ml suspension was prepared. The test bacterial suspension was streaked onto a drug-mixed agar plate using a platinum loop and incubated at 37 ± 1 ° C. for 18-20 hours for bacteria and 27 ° C. for fungi.
For 7 days, and the concentration at which no growth was observed was defined as the minimum growth inhibitory concentration (MIC). The results are shown in Tables 3 and 4. However, the symbols in the table mean the following.

[0073] A: Bacillus subtilis (Bacillus sub
tilis ) B: Trichophyt
on mentagrophytes) C: Staphylococcus aureus (Staphylococcus
aureus ) D: Escherichia coli E: Pseudomonas aeru
ginosa ) F: Aspergillus niger G: Penicillium funiclosum
culosum ) H: Candida albicans

[0074]

Table 3 Table 3 MIC measurement results for bacteria (mg / l)細菌 Compound test bacteria No. ACDE───────────────────────────────────1 <2.0 <2.0 31. 3 31.3 2 <2.0 3.9 31.3 31.3 ──────────────────────────────── ───

[0075]

Table 4 MIC measurement results for fungi (mg / l) Compound test fungus No. FGBH───────────────────────────────────13.9 <2.015.6 <2.0 2 3.9 3.9 <2.0 15.6 ──────────────────────────────── ─── Example 3 (Evaluation of antibacterial and antifungal activities) The compound of the present invention was diluted with dimethyl sulfoxide in a dilution series (20,000, 10,000, 5000, 2500, 1
250, 626, 313, 156, 78, 39 mg /
l) was prepared. This is used as a susceptibility medium for bacteria.
N (Nissui Pharmaceutical Co., Ltd.), and for fungi, 0.5 m per 9.5 ml of potato dextrose agar medium (Nissui Pharmaceutical Co., Ltd.)
1 was added and mixed, and the mixture was poured into a petri dish to obtain a solidified flat plate. The concentration of the compound of the present invention in the agar medium is 1000, 50, respectively.
0, 250, 125, 62.5, 31.3, 15.6,
7.8, 3.9, 2.0 mg / l. The inoculated bacteria were cultured at 37 ° C. for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical). Moreover, fungi after 10 days of culture in potato dextrose agar medium (Nissui Pharmaceutical), respectively 10 ⁶
A suspension of CFU / ml was prepared. The test bacterial suspension was streaked using a platinum loop on a drug-mixed agar plate, for 18-20 hours at 37 ± 1 ° C. for bacteria and 27-27 for fungi.
After culturing at 7 ° C. for 7 days, the concentration at which no growth was observed was defined as the minimum growth inhibitory concentration (MIC). The results are shown in Tables 5 and 6. However, the symbols in the table mean the following.

[0076] I: Micrococcus lutea (Micrococcu
s lutea ) J: Corynebacteria aquaticum
acterium aquaticum ) K: Alcaligenes faec
alis) L: Salmonella cheh Fi-time Liu beam (Salmonella typ
hymurium ) M: Chetomium globosum N: Rhizopus oryzae O: Rodotorula rubra P: Saccharomyces
cervisiaes )

[0077]

Table 5 Table 5 MIC measurement results for bacteria (mg / l)細菌 Compound test bacteria No. IJKL───────────────────────────────────1 <2.0 <2.0 <2 .0> 500───────────────────────────────────

[0078]

Table 13 Table 6 MIC measurement results for fungi (mg / l) Compound test fungus No. MNOP───────────────────────────────────1 <2.0> 500 <2.0 > 500 ─────────────────────────────────── Example 4 (Evaluation of bactericidal efficacy against Legionella bacteria) Was prepared by using dimethyl sulfoxide for 20
A solution having a concentration of 00 mg / l was prepared, and 1 ml of the sample solution was diluted with 19 ml of sterilized tap water to prepare a solution having a concentration of 100 mg / l. The sample solution 20 containing the compound of the present invention
ml in test bacteria solution [Legionella pneumophila (Legion
ella pneumophila ), 3.1 × 10 ⁸ cells / ml]
ml. The cells were contacted at 30 ° C. for 24 hours, and the viable cell count after the action was measured. The results are shown in Table 7.

[0079]

Table 7 Table II Compound No. Viable bacteria count / ml after 24 hours １ 1 <10 2 <10 Control (sterile tap water) 1.2 × 10 ⁶ ────────────────────────── Example 5 (Evaluation of growth inhibitory activity against freshwater green algae) Freshwater green algae ( Selenastrum ) in logarithmic growth phase capricornutu
m ) A certain amount of the compound of the present invention was dissolved in a medium containing 10 ⁵ cells / ml, and a sample containing 500 ppb and 50 ppb of the compound of the present invention in the medium was prepared.
The culture was allowed to stand still at 1 ° C. for 24 hours under continuous lighting conditions.

After 72 hours, the proliferation rate was determined by measuring the number of cells using a blood cell counter. The growth inhibition rate is
It was calculated from the comparison with the untreated section. The results are shown in Table 8.

[0081]

[Table 15] Compound growth inhibition rate (%) 500 ppb 50 ppb {185 30 280 323 390 64 473 636 5 86 32} ─────────────────── Example 6 (Evaluation of growth inhibitory activity against seawater diatom) Seawater diatom ( Nitzschia closterium ) 1 in logarithmic growth phase
0 to ⁵ medium containing / ml, respectively were dissolved amount of a compound of the present invention, the concentration of the compound of the present invention in the medium, each 500
ppb, prepare a sample that is 50 ppb, 23 ± 1 ° C.
The culture was allowed to stand still under continuous lighting conditions for 24 hours.

After 72 hours, the cells were collected by centrifugation, and the cells were crushed by adding methanol to extract chlorophyll. The amount of chlorophyll was measured from the absorbance using a spectrophotometer to determine the growth rate. The growth inhibition rate was calculated from the comparison with the untreated group. The results are shown in Table 9.

[0083]

Table 9: Compound growth inhibition rate (%) 500ppb 50ppb {1 100 96 2 100 97 3 100 96 4 100 33 5 86 37} ７ Example 7 (Evaluation of anti-biofouling activity) 2.9 mg and 1.5 mg of compound 1 were completely dissolved in about 1 ml of acetone, respectively. Diameter 4 drawn on test paper
Each sample solution was uniformly applied in a zone of cm.

A zone to which only acetone was applied as a blank, and 1.0 mg and 0.5 m
g was applied to each zone. 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 adjusted test plate was immersed in a water tank into which seawater flows, and allowed to stand in a dark place 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 10.

[0087]

[Table 17] Table 10 ──────────────────────── Active ingredient dose (mg) Judgment ───────────化合物 Compound 1 2.9 ++ 1.5 ++ Comparative drug (copper sulfate) 1.0 ++ 0.5 + blank − − ──────────記号 The symbols in the table have the following meanings.

++: Does not adhere to the zone at all, and a strong repellent effect is observed. +: Adhesion inside the zone is also observed, but most adhere outside the zone, and a repellent effect is observed. -: Attached to the same degree inside and outside the zone, and no repellent effect is observed.

[0089]

Industrial Applicability The N-pyridylanilines represented by the general formula (1) are highly safe, exhibit a wide spectrum at a low dose, and are used as industrial antibacterial and antifungal agents, algicides and biofouling. Useful as an inhibitor.

Claims (6)

[Claims] 1. A compound represented by the general formula (1): (In the formula, A represents a hydrogen atom or a chlorine atom, B represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and 2 to 6 carbon atoms.
An alkenyl group, an alkynyl group having 2 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms or an alkylsulfonyl group having 1 to 5 carbon atoms, X and Y each independently represent a nitro group, a trifluoro group. Z represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 5 carbon atoms. However, j and k each independently represent 0, 1, 2 or 3, and j + k always represents 3 or less. An antibacterial and antifungal agent for industrial use, comprising an N-pyridylaniline represented by the formula (1): 2. An industrial antibacterial / antifungal agent comprising the N-pyridylaniline according to claim 1, wherein B is a hydrogen atom. 3. An algicide comprising the N-pyridylaniline according to claim 1. 4. An algicide comprising the N-pyridylaniline according to claim 2. 5. An anti-biofouling agent comprising the N-pyridylaniline of claim 1. 6. A biofouling inhibitor comprising the N-pyridylaniline according to claim 2.