WO2000010394A1 - Agents industriels, antibacteriens et antifongiques, algicides et inhibiteurs de bioadhesion contenant des isothiocyanates de phenyle - Google Patents

Agents industriels, antibacteriens et antifongiques, algicides et inhibiteurs de bioadhesion contenant des isothiocyanates de phenyle Download PDF

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Publication number
WO2000010394A1
WO2000010394A1 PCT/JP1999/004478 JP9904478W WO0010394A1 WO 2000010394 A1 WO2000010394 A1 WO 2000010394A1 JP 9904478 W JP9904478 W JP 9904478W WO 0010394 A1 WO0010394 A1 WO 0010394A1
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compound
formula
group
ome
carbon atoms
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PCT/JP1999/004478
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English (en)
Japanese (ja)
Inventor
Shinichi Igarashi
Taito Nishino
Yasuyuki Nakajima
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Nissan Chemical Industries, Ltd.
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Priority to AU53023/99A priority Critical patent/AU5302399A/en
Publication of WO2000010394A1 publication Critical patent/WO2000010394A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups

Definitions

  • the present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial and antifungal agents and algicides used in the production process of industrial products, and water for preventing harmful aquatic organisms such as shellfish from adhering. It relates to a biofouling inhibitor.
  • the use of industrial antibacterial and antifungal agents covers all uses other than the use of antibacterial and antifungal agents in the pharmaceutical and agrochemical fields, and the use of algicides includes the use of herbicides in the agrochemical field. It covers everything except the application. Background art
  • 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.
  • organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used. I have.
  • Anti-fouling agents can be found in underwater equipment such as fishing nets, ship bottoms, buoys, marine structures, condenser cooling water systems for thermal or nuclear power plants, heat exchanger cooling water intake channels for the chemical industry, It is used to prevent harmful aquatic organisms such as shellfish from attaching to underwater structures or reservoirs.
  • organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers, heavy metal coordination compounds, etc. are irritating and cause a problem in the Occupational Safety and Health Law, and the amount of drug used is large. It contains chemicals that are problematic from the viewpoint of environmental protection, releases formalin or halogens, and includes chemicals that may affect the human body and cause environmental pollution and chemicals that cause environmental pollution by heavy metals. Not all fungicides and algicides are composed solely of the preferred agents.
  • organotin compounds as biofouling inhibitors are effective in preventing the fouling of aquatic organisms, but are highly toxic. It has become.
  • Organtin Tin Antifouling Paints Control Act (11987) banned the use of organotin marine paints on ships less than 65 feet, and in the United Kingdom, the Food Environmental Protection Act (1998) 7 years) banned the use of antifouling agents containing triptyltin in ships less than 25 meters and in marine agriculture.
  • triptyl sulphoxide is classified as a Class 1 Specified Chemical Substance
  • triphenyltin compounds and triptyl tin compounds are classified as a Class 2 Specified Chemical Substance under the Act on the Regulation of Chemical Substances Examination and Manufacture. The use of fishing nets is prohibited.
  • the above-mentioned copper compounds widely used in antifouling paints for intake channels and ship bottoms contain copper, which is a heavy metal like tin compounds. Not a biofouling inhibitor.
  • a manufacturing method is disclosed.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, phenylisothiocyanates have high safety and exhibit a wide spectrum at a low dose from the viewpoint of preventing environmental pollution.
  • the present inventors have found that they are highly practical industrial antibacterial and antifungal agents, algicides and biofouling inhibitors, and completed the present invention.
  • the present invention provides a compound represented by the following general formula (1):
  • X, Y and Z each independently represent an alkyl group having 15 carbon atoms (the alkyl group may be optionally substituted by a fluorine atom);
  • An alkoxy group (the alkoxy group may be optionally substituted with a fluorine atom), an alkoxycarbonyl group having 2 to 6 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a hydroxyl group
  • G is an oxygen atom , Io atoms, sulfinyl groups, sulfonyl groups or N-R (R is a hydrogen atom, an alkyl group having 115 carbon atoms, an alkenyl group having 2-6 carbon atoms or an alkynyl group having 2-6 carbon atoms.
  • J and k each independently represent an integer of 0 to 5, j + k is always 5 or less,
  • the present invention relates to industrial antibacterial and antifungal agents, algicides and biofouling inhibitors characterized by containing phenylisothiocyanates represented by the following formula:
  • the phenylisothiocyanates of the present invention contain industrial antibacterial and antifungal agents, algicides and biofouling prevention. There is no description that it is effective as an agent.
  • n is normal, “i” is iso, and “s” is secondary.
  • C means cyclo
  • t means tertiary
  • neo means neo.
  • alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, c-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, and 2-pentyl , 3-pentyl, i-pentyl, neo-pentyl, t-pentyl, 1-methyl-c-propyl, 2-methyl-c-propyl, c-butyl, c-pentyl and the like.
  • alkoxy group having 1 to 5 carbon atoms examples include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy , 2-pentoxy, 3-pentoxy, i-pentoxy, neo-pentoxy, t-pentoxy, 1-methyl-c-propoxy, 2-methyl-c-propoxy, c-butoxy, c-pentoxy and the like.
  • alkoxycarbonyl group having 2 to 6 carbon atoms examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, s-butoxycarbonyl, and t-butoxycarbonyl.
  • N-pentoxycarbonyl 2-pentoxycarbonyl, 3-pentoxycarbonyl, i-pentoxycarponyl, neo-pentoxycarponyl, t-pentoxycarponyl, c-propoxyl-ponyl, 1-methyl-c-propoxyl Luponyl, 2-methyl-c-propoxycarbonyl, c-butoxycarbonyl, c-pentoxycarbonyl and the like.
  • Halogen atoms include fluorine, chlorine, bromine and iodine.
  • alkenyl group having 2 to 6 carbon atoms examples include 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-ethylvinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,2-dimethyl-1-propenyl, 1 , 2-Dimethyl-1-propenyl, 1-ethyl-1-1-propyl, 1-ethyl-2-propenyl, 1_methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butyl Phenyl, 1-i-propylvinyl, 2,4-pentyl genyl, 1-hexenyl, 2 W
  • Examples include 1-hexenyl, 3-hexenyl, 4-1-hexenyl, 5-hexenyl, 2,4-hexagenyl, 1-methyl-1-pentenyl and the like.
  • alkynyl group having 2 to 6 carbon atoms examples include ethynyl, 1-propynyl, 2-propiel, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 Examples include monohexynyl, 2-hexynyl, 3-hexynyl, 4-hexyl, and 5-hexynyl.
  • FIG. 1 shows the antifouling effect of Compound 1 (the surface of the test plate 120 days after the application of 35 mg of Compound 1 and immersion in the sea).
  • the industrial antibacterial agent, drag agent, algicide and biofouling inhibitor of the present invention may contain phenylisothiocyanates 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 Tables 1, 2 and 3 below. The compounds used are not limited to these.
  • Me methyl group
  • Et ethyl group
  • Pr-n normal propyl group
  • Pr-i isopropyl group
  • Bu-n normal butyl group
  • Pen-n normal pentyl group.
  • the ⁇ C00H ⁇ ⁇ ⁇ CF 3 HHH more preferred compounds include a compound shown below (hereinafter In the structural formula shown below, the bond position of NCS may be any of ortho, meta, and para. ).
  • the phenylisothiocyanates of the present invention are disclosed in Japanese Patent Application Laid-Open No. 4-210110, European Patent Application Publication No. 481,921, European Patent Application Publication No. It can be produced by a generally known method with reference to European Patent Publication No. 282425, German Patent Publication No. 3801395, and the like.
  • the phenylisothiocyanates used as the active ingredient in the present invention are solely When the industrial antibacterial agent, antifungal agent, algicide and biofouling inhibitor of the present invention are used, if necessary, other known industrial antibacterial and antifungal agents, algicidal agents may be used. An agent or a biofouling inhibitor can be further included and used as a mixture.
  • Aldehyde compounds such as glutaraldehyde
  • N-halogen compounds such as bromochlorodimethylhydantoin and trichloromouth isocyanuric acid
  • Guanide-based compounds such as poly (hexamethylene biguanide) hydrochloride; dimethyldithi, zinc rubamate, getylditi, zinc rubamate, dibutyruditi, zinc rubamate, zinc rubirmate, zinc bismuth, ethylene bisdiene Zinc thiocarbamate, Zinc propylene bisdithiocarbamate, Bis (dimethyldithiol rubamoyl) Ethylene bisdithiol rubbamate, Ethylene bis thiocyanate Manganese rubbamate, Dimethyl dithiate nickle rubinate Nickel, Dibutyl lutetite rubaminic acid Dithiocarbamate-based metal compounds such as nickel, dimethyldithiol copper rubamate, and dimethyldithiol rubamate iron;
  • Copper-based metal powders such as copper powder and copper-nickel alloy powder
  • Copper compounds such as cuprous oxide, cuprous thiocyanate (copper rhodan), basic copper carbonate, copper pyrophosphate, copper naphthenate, copper abietic acid, copper oxyquinoline;
  • Pyrithione metal compounds such as 2-pyridinethiol zinc oxide and 2-pyridinethiol copper salt;
  • 2- (4-thiazolyl) benzimidazole 2— (methoxycarponylamino) benzimidazole, methyl-11- ( ⁇ -cyanopentylcarbamoyl) 1-2-benzimidazole, 2-mercaptobenzimidazole zinc, Benzimidazole compounds such as 2-thiocyanomethylthiobenzimidazole;
  • 2-mercaptobenzothiazole 2- (thiocyanomethylthio) benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazol, 2-thiocyanoethylthio-14-chlorobenzoicazole, 2-thiocyanopropyl Benzothiazole compounds such as thio-5,7-dichlorobenzothiazole and 2-thiocyanomethylthio-1,4,5,6,7-tetrachlorobenzothiazole;
  • Ditolyl such as tetrafluoroisophthalonitrile, tetrachloroisophthalonitrile, 5-chloro-1,2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile System compound;
  • Quinone compounds such as 2,3-dichloro-1,4-naphthoquinone, 2-amino-1,3-chloro-1,4-naphthoquinone, 2,3-dicyanone 1,4-dithiaanthraquinone;
  • Maleimide compounds such as, 2,3-dichloro-N- (2 ', 4', 6'-trimethylphenyl) maleimide;
  • Thiocyanates such as carboxylate, arylisothiosinate, phenylisothionate, and benzylisothiocyanate
  • alkylphenol compounds such as caprylphenol and nonylphenol
  • tris (octylphenyl) phosphite, tris (nonylphenyl) Alkyl phenyl phosphite compounds such as phosphite, tris (dinonylphenyl) phosphite, and tris (mono- and di-mixed nonylphenyl) phosphite
  • Alkyl phenyl phosphite compounds such as tris (octyl phenyl) phosphate, tris (nonyl phenyl) phosphate, tris (dinonyl phenyl) phosphate, tris (mono, di-mixed nonyl phenyl) phosphate;
  • n a polysulfide compound such as octylchloromethyl disulfide; a boron compound such as pyridinetriphenylporan.
  • Bismuth compounds such as phenyl (bispyridyl) bismuth dichloride; and the phenylisothiocyanates used as the active ingredient in the present invention are composed of a single compound or a mixture of several kinds of phenylisothiocyanates. Is also good.
  • phenylisothiocyanates used as the active ingredient in the present invention may be added alone to the system for the use described above, or as a mixture comprising other active ingredients and, if necessary, a suitable carrier or solvent. Alternatively, it may be formulated as an aqueous emulsion or dispersion.
  • the formulation of the industrial antibacterial and antifungal agent, the algicide and the biofouling inhibitor of the present invention can be generally used in the field of industrial antibacterial and antifungal agent and the algicide as an active ingredient in the present invention.
  • the phenylisothiocyanates are mixed with suitable carriers and auxiliaries, such as surfactants, binders, stabilizers, etc., and mixed, and wettable powders, emulsions, sols (flowables) and It is used after being formulated into other appropriate dosage forms.
  • 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.
  • solid carriers include mineral powders such as lime ore, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphate lime, white limestone, slaked lime, silica sand, ammonium sulfate. , Urea, etc., or vegetable powders, for example, soybean powder, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like.
  • mineral powders such as lime ore, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphate lime, white limestone, slaked lime, silica sand, ammonium sulfate. , Urea, etc., or vegetable powders, for example, soybean powder, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers
  • liquid carriers examples include water, alcohols such as methyl alcohol, ethyl Aromatic hydrocarbons such as alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., for example, benzene, toluene, xylene, ethylbenzene, benzene, cumene, methylnaphthylene, and halogenated hydrocarbons , Such as chloroform, dichloromethane, ethylene dichloride, etc., ethers, such as ethyl ether, dioxane, tetrahydrofuran, etc., Ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters , For example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc., nit
  • surfactants are incorporated for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading, and the like.
  • examples of such a surfactant include the following, but are not limited thereto.
  • nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbin alkyl ester, and sorbitan alkyl ester.
  • anionic surfactant examples include alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfone and lauryl sulfate.
  • cationic surfactant examples include alkylamines (such as laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride).
  • amphoteric surfactants include carboxylic acid (bein-in type) sulfate. W 0
  • polyvinyl alcohol PVA
  • carboxymethyl cellulose CMC
  • gum arabic polyvinyl acetate
  • gelatin casein
  • sodium alginate sodium alginate
  • tragacanth gum guar gum
  • xanthan gum hydroxypropyl cellulose Thickeners and various auxiliaries
  • a suitable amount of a stabilizer such as an antioxidant or an ultraviolet absorber can be added.
  • the industrial antibacterial and antifungal agents and algicides of the present invention containing phenylisothiocyanates as an active ingredient can be used for the following applications.
  • Building materials building materials (building materials, civil engineering materials, etc.), antibacterial and antifungal and algicidal products for home appliances, household goods, sports equipment, etc .; protection of slime deposition on sugar cane and sugar beet sugar manufacturing equipment; Prevention of accumulation and accumulation of microorganisms in shear and scrubber systems and industrial freshwater supply systems; Preservation of sanitary conditions in food factories; Deodorization and sterilization of sewage treatment plants, human waste treatment plants, etc. when washing production facilities; Oil field cutting oil Prevention of microbial contamination and sedimentation in muddy water and secondary oil recovery processes; Prevention of bacterial and fungal growth in paper coatings and coatings; Prevention of microbial contamination in cosmetics and toiletry products; Algal growth on pools, etc. Control; Prevent microbial contamination of agricultural formulations, electrodeposition systems, diagnostic and pharmaceutical products, medical equipment, etc .; Prevent microbial accumulation in photographic processing.
  • the formulated industrial antibacterial and antifungal agents and algicides of the present invention can be obtained by diluting various preparations as they are or by diluting them with water or an appropriate organic solvent, and then preparing them in various industrial raw materials or products. To the surface of various industrial raw materials and products. Including the method of fogging or the method of immersing various industrial raw materials and products in the diluent of the industrial antibacterial and antifungal agent and the algicide of the present invention, and the like, It can be used by various methods according to the use of antibacterial and antifungal agents and algicides, but is not limited to any particular method.
  • Anti-biofouling agents containing phenylisothiocyanates as active ingredients include: fishing nets, ship bottoms, buoys and other submarine equipment, marine structures, condensers for thermal or nuclear power plants Shells such as blue mussels, fusippo, oysters, hide mouth mussels, hydra, selbra, sea squirts, mosquitoes, and evening reeds for underwater structures such as water intake channels for cooling water for heat exchangers in the chemical industry, facilities attached to dams, etc. It can also be used to prevent the adhesion of harmful aquatic organisms such as algae such as Aosa, Aonori and Shimidro.
  • Formulations of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are outlined in the field of application of biofouling inhibitors.
  • the phenylisothiocyanates used as active ingredients in the present invention are: It is prepared and used in the form of paints, solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions and the like, general recipes usually used can be adopted.
  • the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, an active ingredient, phenylisothiocyanate, is mixed with a film-forming agent to prepare a paint, and When applied to marine structures, cooling water intake pipes, or underwater structures, it is possible to prevent adherent propagation of underwater organisms.
  • an antifouling paint for example, an active ingredient, phenylisothiocyanate
  • oil varnish As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.
  • a solvent, a pigment, or the like may be used as necessary.
  • the concentration of the phenylisothiocyanate as an active ingredient has no upper limit as long as a coating film can be formed, but it is preferably 1 to 50% by weight, and more preferably 1 to 50% by weight based on the weight of the antifouling paint. It is blended at a ratio of 5 to 20% by weight.
  • the underwater biofouling inhibitor of the present invention is used in the form of a solution, for example, a solution in which phenylisothiocyanate, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared, and aquaculture fishing net, By applying it to a fixed fishing net or the like, it is possible to prevent the adhesion and propagation of aquatic organisms.
  • a solution for example, a solution in which phenylisothiocyanate, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared, and aquaculture fishing net, By applying it to a fixed fishing net or the like, it is possible to prevent the adhesion and propagation of aquatic organisms.
  • the coating film forming agent synthetic resin, artificial rubber, natural resin, etc. are used, and as the solvent, xylene, toluene, cumene, methylethyl ketone, methyl isobutyl ketone, acetate, etc. are
  • additives such as a plasticizer
  • concentration of the phenylisothiocyanate as an active ingredient there is no upper limit to the concentration of the phenylisothiocyanate as an active ingredient as long as a solution can be formed, but 1 to 50% by weight, preferably 5 to 50% by weight, based on the weight of the solution. It is blended at a rate of 30%.
  • a surfactant is usually added to a solution of phenylisothiocyanate as an active ingredient in accordance with a general method for preparing an emulsion.
  • a desired emulsion can be prepared, and there is no particular limitation on the type of surfactant used.
  • the prepared emulsion can be used by kneading it into raw materials such as aquaculture nets and fixed nets used in the ocean or water, for example, polymer resins and the like.
  • an emulsion When an emulsion is prepared, there is no upper limit to the concentration of the phenylisothiocyanate as an active ingredient as long as an emulsion can be formed, but it is 115% by weight, preferably 3% by weight, based on the weight of the emulsion. It is blended at a ratio of 30% by weight.
  • the above solution or emulsion of the present invention can also be used by adding to water, storage water, etc. in order to prevent adherent propagation of aquatic organisms in a cooling water intake pipe or a reservoir.
  • Formulation examples when the phenylisothiocyanates of the present invention are used as industrial antibacterial and antifungal agents and algicides are shown below.
  • the mixing ratio of active ingredients, the types of carriers and auxiliary agents, and the amounts added are as follows. It is not limited to these.
  • the above mixture was placed in a ball mill and pulverized and mixed for 12 hours to obtain a flooring agent containing 20% of the active ingredient.
  • VYHH (vinyl synthetic resin manufactured by UC C) 7
  • the antibacterial and antifungal activities of the phenylisothiocyanates of the present invention, the growth inhibitory activity against algae, and the anti-biological adhesion activity in water are described in Test Examples using Compounds 1 to 4, but the present invention is not limited thereto. It is not limited.
  • Compound 1 and compound 2 are commercially available and readily available.
  • Test Example 1 Evaluation of antibacterial and antifungal activities
  • a dilution series of the compound of the present invention (2000, 10000, 500, 2,500, 2000, 1250, 625, 313, 15 6, 78, 39, 20, 10, 5, 2.5, 1.25 mg / 1) were prepared.
  • Sensitivity Medium 1N (Nissui Pharmaceutical)
  • Potato Dextrose Agar Medium (Nissui Pharmaceutical)
  • the concentration of the compound of the present invention in the agar medium was 100, 500, 250, 125, 100, 62.5, 31.3, 15.6, 7.8, respectively.
  • the inoculated bacteria were cultured at 37 ° C for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured for 10 days on a potato dextrose agar medium (Nissui Pharmaceutical), each with 10 6 C FUZm.
  • One suspension was prepared.
  • the test bacterial suspension was streaked using a platinum loop on a drug-mixed agar plate, and cultured for 18 to 20 hours at 37 ⁇ 1 ° C for bacteria and 27 days for fungi at 27.
  • the development of each The lowest concentration was defined as the minimum inhibitory concentration (MIC).
  • Table 4 The results are shown in Table 4. However, the symbols in the table mean the following.
  • the logarithmic growth phase freshwater green alga (Serenasu Torumu Capri Korunutamu, Selenastrum capr icornutum) 1 0 medium containing a 5 m 1, respectively to dissolve a predetermined amount of a compound of the present invention, the concentration of each 5 of the present compounds in the medium
  • Samples of 00 ppb and 50 ppb were prepared and cultured at 23 ⁇ 1 for 24 hours under continuous lighting conditions.
  • the compound of the present invention was completely dissolved in 1 ml of acetone and applied uniformly in a 4 cm diameter zone drawn on a test plate.
  • a zone to which only acetone was applied was provided as a blank, and a zone to which 1.0 Omg and 0.5 mg of copper sulfate was applied as a comparative agent.
  • mussels (Mytilus edulis) having a shell length of about 2-2.5 cm were adhered to the perimeter of each zone using a piece of rubber as a spacer.
  • the prepared test plate was immersed in a water tank into which seawater flows, and allowed to stand in a dark place for 3 hours.
  • the anti-adhesion effect was determined by comparison with copper sulfate used as a comparative drug.
  • test plate vinyl chloride plate, 350 mm long ⁇ 60 mm wide. 0 mm was applied in a sample zone of 5 cm diameter drawn above. A sample zone to which only the above resin solution was applied was provided as a blank. After drying, the test plate was immersed at a depth of about 1 m below sea level at the Shizuoka- ⁇ Yomune fishing port.
  • the presence or absence of antifouling activity was determined by comparing the state of adherence of organisms in the sample zone to the blank, and by the number of days during which adhesion was inhibited.
  • the phenylisothiocyanates represented by the general formula (1) are highly safe, exhibit a wide spectrum with a low dose, and are used as industrial antibacterial agents, antifungal agents, algicides, and anti-biological adhesion agents. Useful as

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Abstract

L'invention porte sur des agents industriels antibactériens et antifongiques, sur des algicides et des inhibiteurs de bioadhésion contenant des isothiocanates de phényle représentées par la formule générale (1) dans laquelle X, Y et Z sont chacun, indépendamment, C1-C5 alkyl (qui peut être fluoré), C1-C5 alcoxy (qui peut être fluoré), C2-C6 alcoxycarbonyle, halogéno, nitro, hydroxyle ou carboxyle; G est un oxygène, soufre, sulfinyl, sulfonyl ou N-R (où R est un hydrogène, C1-C5 alkyle, C2-C6 alcényle ou C2-C6 alkynyle); j et k sont chacun, indépendamment, un entier compris entre 0 et 5, la somme de j et de k étant inférieure ou égale à 5; et 1 est un entier compris entre 0 et 4.
PCT/JP1999/004478 1998-08-25 1999-08-20 Agents industriels, antibacteriens et antifongiques, algicides et inhibiteurs de bioadhesion contenant des isothiocyanates de phenyle WO2000010394A1 (fr)

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JP23918898 1998-08-25
JP10/239188 1998-08-25
JP11/81766 1999-03-25
JP8176699 1999-03-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017031082A (ja) * 2015-07-30 2017-02-09 株式会社Ｐｒｄ 工業的抗菌防カビ方法
JP2020007283A (ja) * 2018-07-11 2020-01-16 株式会社Ｐｒｄ 工業的抗菌防カビ方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4849923A (fr) * 1971-10-25 1973-07-14
JPS5018626A (fr) * 1973-06-18 1975-02-27
JPS52122605A (en) * 1976-04-06 1977-10-15 Nihon Nohyaku Co Ltd Mildewcide and insecticide agent for woods
JPS63303904A (ja) * 1987-06-02 1988-12-12 Nippon Paint Co Ltd 水中有害生物防除剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4849923A (fr) * 1971-10-25 1973-07-14
JPS5018626A (fr) * 1973-06-18 1975-02-27
JPS52122605A (en) * 1976-04-06 1977-10-15 Nihon Nohyaku Co Ltd Mildewcide and insecticide agent for woods
JPS63303904A (ja) * 1987-06-02 1988-12-12 Nippon Paint Co Ltd 水中有害生物防除剤

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BATZINGER ROBERT P. ET AL.: "Antimutagenic Effects of 2(3)-tert-Betyl-4-hydroxyanisole and of Antimicrobial Agents", CANCER RES., vol. 38, no. 123, 1978, pages 4478 - 4485, XP002932467 *
ERIC J. LIEN ET AL.: "Structure-Activity Correlations for Antibacterial Agents on Gram-Positive and Gram-Negative Cells", J. MED. CHEM., vol. 11, no. 3, 1968, pages 430 - 441, XP002932466 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017031082A (ja) * 2015-07-30 2017-02-09 株式会社Ｐｒｄ 工業的抗菌防カビ方法
JP2020007283A (ja) * 2018-07-11 2020-01-16 株式会社Ｐｒｄ 工業的抗菌防カビ方法

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