WO2012093608A1 - Algicidal/microbicidal agent and algicidal/microbicidal method - Google Patents

Algicidal/microbicidal agent and algicidal/microbicidal method Download PDF

Info

Publication number
WO2012093608A1
WO2012093608A1 PCT/JP2011/080039 JP2011080039W WO2012093608A1 WO 2012093608 A1 WO2012093608 A1 WO 2012093608A1 JP 2011080039 W JP2011080039 W JP 2011080039W WO 2012093608 A1 WO2012093608 A1 WO 2012093608A1
Authority
WO
WIPO (PCT)
Prior art keywords
chloro
dichloro
group
formula
compounds
Prior art date
Application number
PCT/JP2011/080039
Other languages
French (fr)
Japanese (ja)
Inventor
祐二 市村
英俊 妻木
勝久 磯貝
Original Assignee
ケイ・アイ化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ケイ・アイ化成株式会社 filed Critical ケイ・アイ化成株式会社
Priority to CN201180064265.2A priority Critical patent/CN103298340B/en
Priority to KR20137016670A priority patent/KR20130141624A/en
Publication of WO2012093608A1 publication Critical patent/WO2012093608A1/en

Links

Classifications

    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to an algicide / bactericidal agent.
  • the algicidal / bactericidal agent of the present invention is used to suppress the growth and proliferation of algae and general bacteria generated in aqueous systems.
  • the water system is not limited to this, but circulating cooling water such as cooling towers, various industrial water, waste water, ponds, lakes, reservoir spillways, fountains, and sunlight (in environments such as building exteriors) It also refers to water systems that come into contact with the atmosphere.
  • triazine-based algicides such as amethrin, simethrin, promethrin and the like are used because of their high efficacy as algicides. Handbook "(1998 edition Japan Plant Protection Association edition) ⁇ .
  • these triazine-based algicides have low solubility in water, and it is necessary to add a large amount of an organic solvent for formulation. When added to an aqueous system, the organic solvent in the formulation is a nutrient for general bacteria. There were problems such as becoming a source. In addition, these triazine-based algicides have problems in terms of safety such as toxicity and carcinogenicity.
  • bactericides for suppressing the growth and proliferation of general bacteria include isothiazolone compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1, An organic bromine-based compound represented by 3-diol is used (Patent Document 1 and Patent Document 2).
  • isothiazolone compounds have strong toxicity, skin irritation and mucous membrane irritation and are inconvenient to handle, and organic bromine compounds have the disadvantage that they have a relatively strong effect on general bacteria but a weak algaecidal effect. .
  • N-chlorosulfamic acid or N, N-dichlorosulfamic acid or a salt thereof formed by adding sulfamic acid or a salt thereof to this hypochlorite is bound chlorine, and hypochlorous acid It is known that its bactericidal effect is inferior to free chlorine such as. Bonded chlorine is less likely to cause problems such as corrosion of piping and equipment in the system at high concentrations, although its oxidizing power is reduced compared to free chlorine.
  • the algicidal effect of halogen-based oxidizing agents such as hypochlorous acid is lower than that of triazine-based algicidal agents such as amethrin described above, and bound N-chlorosulfamic acid is the same.
  • halogen-based oxidizing agents such as hypochlorous acid
  • triazine-based algicidal agents such as amethrin described above
  • bound N-chlorosulfamic acid is the same.
  • a high concentration is required, and as a result, there is a problem that the risk of causing corrosion of piping and equipment in the system is increased.
  • currently used drugs have various drawbacks in terms of solubility in water, cost, handleability, safety and the like, and are not always satisfactory.
  • N-chloro-2-pyrrolidinone which is one of the algicidal / bactericidal components of the present invention, is used as a disinfectant / bleaching agent in combination with N-chloro-5-methyl-2-oxazolidinone in Patent Document 4.
  • Patent Document 4 There is a report, but there is no description about the algicidal effect.
  • methods for blending 2-pyrrolidinone with sulfamic acid or hydantoin as N-hydrogen compounds for the purpose of stabilizing hypochlorous acid have been reported in Patent Document 5 and Patent Document 6, but 2-pyrrolidinone is only used.
  • N-hydrogen compounds such as these are formulated for the purpose of stabilizing hypochlorous acid, and have not been evaluated as bonded N-chloro compounds or N, N′-dichloro compounds shown in the present invention. There is no mention of the algaecidal effect.
  • Patent Document 7 reports a microorganism control method using dimethylhydantoin in combination with free halogen and N-hydrogen compounds, and there is a description of 2-pyrrolidinone as one of N-hydrogen compounds. Has not been evaluated, and there is no mention of the algicidal effect.
  • An object of the present invention is to provide an algicidal agent and an algicidal / bactericidal agent that are excellent in solubility in water, low in cost, and excellent in handleability.
  • the subject of the present invention also provides a method for controlling algae and / or bacteria in an aqueous system in contact with a metal member where corrosion is not desired.
  • the present invention provides: (1) an algicidal agent containing N-chloro-2-pyrrolidinone, (2) The algicidal agent according to (1), which is a water-soluble liquid preparation further comprising water or a mixed solution of water and a water-soluble organic solvent, (3) Formula (I):
  • X represents a methylene group, a secondary amino group or an N-chloro group
  • R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam, N-chloro- ⁇ -hepta.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-pyrrolidinone, N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam N-chloro- ⁇ -heptalactam, N-chloro-2-imidazolidinone, N, N′-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N′-dichloro -Algae / sterilization method according to (6), characterized in that it is at least one selected from tetrahydro-2-pyrimidinone, (8) Use of N-chloro-2-pyrrolidinone to kill algae, (9) Algae killing method using N-chloro-2-pyrrol
  • Algae method (where "algae control is desired” refers to, for example, an aqueous system), (10) Use of N-chloro-2-pyrrolidinone for the production of an algicide (11) Method for producing an algicide using N-chloro-2-pyrrolidinone; specifically, N-chloro-2 -A method for producing an algicide, comprising a step of blending pyrrolidinone (the method may further comprise a step of blending other components as appropriate), (12) One kind selected from cyclic N-chloro compounds represented by formula (I) (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds for algaecidal / sterilizing Use of the above compounds, (13) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam, N-chloro- ⁇ -hepta
  • a target for which control of algae and / or bacteria is desired refers to, for example, an aqueous system
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam, N-chloro- ⁇ -hepta.
  • Method for producing algicide / bactericidal agent specifically, a method for producing algicide / bactericidal agent, comprising the step of blending the compound (this method may further comprise a step of blending other components as appropriate) it can),
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam, N-chloro- ⁇ -hepta.
  • algicidal / bactericidal agent refers to “algicidal and / or bactericidal agent”.
  • the “algaecidal / sterilizing method” refers to “a method of controlling algae and / or bacteria”.
  • Algae-killing refers to “controlling algae and / or bacteria”.
  • algae control refers to, for example, suppression or prevention of algae growth or proliferation.
  • control of algae and / or bacteria refers to suppression or inhibition of growth or proliferation of algae and / or bacteria, for example.
  • an algicide / disinfectant composition that has excellent solubility in water, exhibits excellent algicidal and bactericidal effects, and is low in cost and easy to handle, It can be handled as a liquid formulation, has excellent solubility in water, is stable in aqueous solution, and exhibits excellent algicidal and bactericidal effects, even though effective chlorine is a combined N-chloro or N, N'-dichloro compound. Furthermore, the present inventors have found an algicidal / bactericidal composition having low corrosive properties and excellent handleability, and has reached the present invention.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) can be handled as an aqueous solution because it dissolves in water at an arbitrary ratio. It has also been found that the aqueous solution is stable and maintains an effective chlorine concentration.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is a hypothetical compound in water such as the corresponding N-hydrogen cyclic amide compound and sodium hypochlorite. Another advantage is that it can be prepared as a stable aqueous solution at a low cost by mixing with a compound that generates chloric acid.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is extremely low in corrosiveness and corrodes equipment and piping even when used at a high concentration. It is also an advantage that the risk of falling is low.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is preferably N-chloro-2-pyrrolidinone, N-chloro-2-piperidone, N-chloro- ⁇ -caprolactam, N-chloro- ⁇ -heptalactam, N-chloro-2-imidazolidinone, N, N′-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N One or more selected from '-dichloro-tetrahydro-2-pyrimidinone.
  • algicidal agent and “algicidal / bactericidal agent” each contain at least a predetermined active ingredient and may contain other ingredients, or an algaecidal compound or composition, In addition, it refers to a compound or composition for algicidal and / or sterilizing.
  • Examples of the above-mentioned other components include media such as diluents and excipients for formulation, and other active ingredients.
  • Other components can be selected from known components as long as the stability is not impaired.
  • the algicidal agent and algicidal / bactericidal agent of the present invention may be formulated into an arbitrary form.
  • the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is dissolved in water or a mixed solution of water and a water-soluble organic solvent. And water-soluble liquid preparations.
  • water-soluble organic solvents include organic acids such as lactic acid, formic acid, acetic acid and citric acid, ketones such as acetone, alcohols such as ethanol, glycols such as ethylene glycol, glycol ethers such as diethylene glycol monomethyl ether, diethyl carbonate And esters such as tetrahydrofuran, ethers such as tetrahydrofuran, cyclic amides, and chain amides such as dimethylformamide.
  • organic acids such as lactic acid, formic acid, acetic acid and citric acid
  • ketones such as acetone
  • alcohols such as ethanol
  • glycols such as ethylene glycol
  • glycol ethers such as diethylene glycol monomethyl ether
  • diethyl carbonate And esters such as tetrahydrofuran, ethers such as tetrahydrofuran, cyclic amides, and chain amides such as dimethylformamide.
  • bactericidal active ingredient can be added to the algicidal / bactericidal agent of the present invention within a range not impairing the stability.
  • organic bromonitro compounds such as 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol, and 5-chloro-2-methyl-4-isothiazoline.
  • Isothiazolone compounds such as -3-one and 2-methyl-4-isothiazolin-3-one
  • dithiocarbamate compounds such as dimethyldithiocarbamate
  • thiazole compounds such as sodium 2-mercaptobenzothiazole, 1,2-bis (bromo Acetoxy) -ethane, 1,4-bis- (bromoacetoxy) -2-butene, N-bromoacetamide and other organic bromoacetates or amides
  • Bactericides such as quaternary ammonium salts and algae And the like control component.
  • a cationic surfactant, an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant can also be blended.
  • scale inhibitors such as polymers containing acrylic acid and maleic acid, organic phosphonic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, zinc salts, polymerization Corrosion inhibitors such as phosphates, organic phosphonic acids, azole compounds, and molybdates can also be added.
  • the effective chlorine concentration of the algicidal / bactericidal composition of the present invention and hypochlorous acid is determined by diethyl-p-phenylenediammonium (DPD) colorimetric method, DPD-ammonium iron (II) sulfate titration method (JIS K 0101). ) Etc., and simple analysis kits are also commercially available.
  • the effective chlorine concentration measurement in the present invention was performed using a DPD-ammonium iron (II) sulfate titration method and an effective chlorine counter CL-300 (iodine coulometric titration method) manufactured by Hiranuma Sangyo Co., Ltd.
  • the amount of the algicidal / bactericidal agent of the present invention to be added to the aqueous system varies depending on the scale of the aqueous system, the quality of the target aqueous system, the degree of contamination, the frequency of addition, etc. Is preferably 0.1 to 50 mg / L as the residual chlorine concentration in the water.
  • the residual chlorine concentration is lower than 0.1 mg / L, the effect of the present invention cannot be expected substantially.
  • the residual chlorine concentration is higher than 50 mg / L, it is not preferable in terms of economy.
  • the residual chlorine concentration here means all effective chlorine concentrations remaining in water.
  • the present invention also relates to a method for inhibiting the growth and / or proliferation of algae and / or bacteria in the aqueous system by adding the above-mentioned compound represented by formula (I) into the aqueous system.
  • This method is particularly suitable for the control of algae and / or bacteria in aqueous systems in contact with metal parts where corrosion is not desired.
  • the algicide / bactericides of the present invention are less corrosive to iron and copper even at high concentrations.
  • the compound represented by formula (I) is 0.2 to 10 mg / L as a residual chlorine concentration (Cl 2 equivalent), Preferably, it is added to the aqueous system so as to be 2.5 to 5.0 mg / L.
  • metal members that do not require corrosion include metal pipes and equipment that come into contact with water systems.
  • the metal include iron, copper, and stainless steel.
  • the residual chlorine concentration (in terms of Cl 2 ) can be measured by the above-described method for measuring effective chlorine concentration.
  • Example 1 In Example 1, 6.8 g of 2-pyrrolidinone [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to 100 g of chloroform [reagent, manufactured by Kanto Chemical Co., Ltd.], and trichloroisocyanuric acid [reagent, Tokyo Chemical Industry ( Co., Ltd.] 9.3 g of koji was added over 40 minutes. The resulting white slurry was filtered with suction after stirring for 6 hours. The filtrate was concentrated on a rotary evaporator and then ice-cooled to obtain 9.4 g of white crystals of N-chloro-2-pyrrolidinone (yield 98.4%, physical properties are shown below).
  • Example 2 7.6 g of 2-piperidone [reagent, manufactured by Kanto Chemical Co., Ltd.] ⁇ and 42.8 g of waterpox were mixed, and 4.6 g of acetic acid [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to the aqueous solution.
  • Sodium hypochlorite solution with an effective chlorine concentration of 12% [effective chlorine concentration of 12%, manufactured by Yayoi Sangyo Co., Ltd.] 5.0 45.0 g was added, and an N-chloro-2-piperidone aqueous solution with an effective chlorine concentration of 5.4% 100 g of koji was prepared.
  • the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
  • Example 3 7.9 g of ⁇ -caprolactam [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to 100 g of chloroform, and 8.1 g of trichloroisocyanuric acid was added over 90 minutes under ice cooling. The resulting white slurry was filtered with suction after stirring for 6 hours, and the filtrate was concentrated by a rotary evaporator to obtain 10.1 g of a slightly yellow transparent oil of N-chloro- ⁇ -caprolactam (yield 97.9%, physical properties are as follows). To show).
  • Example 4 8.6 g of ⁇ -heptalactam [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 31.8 g of water tank instead of 2-piperidone of Example 2, and 10.0 g of ⁇ -butyrolactone was added. Except for the above, the same operation as in Example 2 was carried out to obtain 100 g of an aqueous N-chloro- ⁇ -heptalactam solution having an effective chlorine concentration of 5.4%. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
  • II DPD-iron ammonium sulfate
  • Example 5 tetrahydro-2-pyrimidinone [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] 5.0 g-2 was added dichloromethane [reagent, manufactured by Kanto Chemical Co., Ltd.] 40.0 g, and trichloroisocyanuric acid. 8. 5 g of koji was added over 30 minutes. The resulting white slurry was stirred and filtered for 8 hours, and the filtrate was concentrated with a rotary evaporator and then ice-cooled to obtain 8.1 g of white crystals of N, N'-dichloro-tetrahydro-2-pyrimidinone (yield 96. 2%, physical properties are shown below).
  • Example 6 5.6 g of white crystals of N-chloro-tetrahydro-2-pyrimidinone were obtained by performing the same operation while reducing the chlorinating agent trichloroisocyanuric acid in Example 5 to 3.9 g (yield 83). 2%, physical properties are shown below).
  • Example 7 6.5 g of ethylene urea [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] was dispersed in 40 g of ethyl acetate [reagent, manufactured by Kanto Chemical Co., Inc.] to form a suspension. Dimethylhydantoin 15.5g was added over 1 hour. The resulting white slurry was filtered after stirring for 8 hours, and the filtrate was concentrated with a rotary evaporator. The precipitated white crystals were filtered and dried to obtain 3.5 g of N, N′-dichloro-2-imidazolidinone (yield) 30.1%, physical properties are shown below).
  • Comparative Example 1 11.9 g of water syrup, 15.6 g of 48% by weight sodium hydroxide aqueous solution, 12.0 g of sulfamic acid cocoon, 60.0 g of sodium hypochlorite solution with an effective chlorine concentration of 12%, and 0.5 g of benzotriazole
  • an algicidal / bactericidal agent containing N-chlorosulfamic acid and N, N-dichlorosulfamic acid was prepared.
  • the effective chlorine concentration of this algicide / bactericidal agent was 7.2%.
  • the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
  • Comparative Example 3 only a sodium hypochlorite solution having an effective chlorine concentration of 12% was used. In this solution, the chlorine form was detected as free in the DPD-iron (II) ammonium sulfate titration method.
  • Test example 1 Algae killing test (green algae and cyanobacteria) Using the green alga Chlorella vulgaris C-135 (hereinafter referred to as chlorella) and the cyanobacteria Microcystis aeruginosa Lemmermann NIES-44 (hereinafter referred to as microkitis), the algicidal effect of the algicidal and bactericidal agents of Examples and Comparative Examples Evaluated. Chlorella uses a pre-cultured solution in MDM medium with an absorbance of O.D. D.
  • N-chloro and N, N′-dichloro compounds of the present invention showed a high algicidal effect against microkistis, which is a cyanobacteria that constitutes the blue sea urchin and is a biological indicator. It was.
  • Test Example 2 Bactericidal power test Cooling water from a cooling tower for air conditioning in Sakai Hospital was used as test water. Table 3 shows the quality of the cooling water.
  • each of this cooling water was dispensed into an L-shaped test tube, and each algicidal / bactericidal agent prepared in Examples and Comparative Examples was added so as to have a predetermined concentration as an effective chlorine concentration to evaluate the efficacy.
  • the test conditions were carried out by shaking culture in a constant temperature bath at 30 ° C., and measuring the number of general bacteria in the test water 1 hour and 6 hours after the addition of the drug. The results are shown in Table 4. The amount of drug added in Table 4 is shown as effective chlorine concentration.
  • the N-chloro and N, N′-dichloro compounds of the present invention showed a very excellent bactericidal effect at a low concentration.
  • the N-chloro compound of sulfamic acid shown in Comparative Example 1 has a very weak bactericidal effect, and after 1 hour of addition, it shows only a weaker effect than sodium hypochlorite, which is the free chlorine of Comparative Example 3. Even after the time, the addition of a low concentration showed almost no effect.
  • 1-chloro-5,5-dimethylhydantoin of Comparative Example 2 also showed a certain bactericidal effect when added at a high concentration, but the effect was only low compared with the algicidal / bactericidal agent of the present invention. This also indicates that the N-chloro and N, N'-dichloro compounds of the present invention exhibit a bactericidal effect quickly even at low concentrations, even though they are bound N-chloro compounds.
  • Test Example 3 Metal Corrosiveness Stainless steel SUS304 (single side # 400 polished finish, 2.5 ⁇ 15 ⁇ 50 mm), iron (SS-400, 2.3 ⁇ 15 ⁇ 30 mm) and copper (C122OP) in a glass container with a lid , 2.0 ⁇ 20 ⁇ 50 mm), a predetermined amount of clean water (Iwata City Shizuoka City water) is measured to a position where a gas phase portion and a solution immersion portion can be formed. 3.
  • the algicidal and bactericidal agents of Comparative Examples 1 and 3 were added so that the effective chlorine concentration was 2.5 mg / L and 5 mg / L, and the degree of corrosion of the test piece was observed at 30 ° C.
  • the test solution is changed once a week, and after 8 weeks, the test piece is taken out, and the degree of corrosion (gmd; g / m 2 ⁇ day) is obtained.
  • the degree of corrosion of each algicide / bactericide was evaluated according to the criteria shown in Table 6 below with respect to the degree of corrosion in the non-agent-added section (only clean water). The results are shown in Table 7 in combination with symbols.

Abstract

This invention relates to an algicide of excellent water solubility, low cost and excellent handling that is characterized in containing N-chloro-2-pyrrolidinone, as well as to an algicidal/microbicidal agent characterized in containing one or more compounds selected from cyclic N-chloro compounds and N,N'-dichloro compounds represented by formula (1). (1) (In the formula, X represents a methylene group, secondary amino group, or N-chloro group, and R represents a C2-5 alkylene group, provided that when X is an N-chloro group, R is a C2-3 alkylene group.)

Description

殺藻・殺菌剤及び殺藻・殺菌方法Algae killing agent and alga killing method
　本発明は、殺藻・殺菌剤に関する。本発明の殺藻・殺菌剤は水系において発生する藻類及び一般細菌の生育及び増殖を抑制するために用いられる。水系とは、これに限定されるものではないが、クーリングタワー等の循環冷却水、各種工業用水、廃水、池、湖沼、貯水池放水路、噴水及び（建築物外壁などの環境で）太陽光があたり且つ大気と接する水系等を指す。 The present invention relates to an algicide / bactericidal agent. The algicidal / bactericidal agent of the present invention is used to suppress the growth and proliferation of algae and general bacteria generated in aqueous systems. The water system is not limited to this, but circulating cooling water such as cooling towers, various industrial water, waste water, ponds, lakes, reservoir spillways, fountains, and sunlight (in environments such as building exteriors) It also refers to water systems that come into contact with the atmosphere.
　上記の水系や施設では、しばしば藻類の繁殖により、異臭の発生や外観の悪化などの他に、配管の詰まり、クーリングタワーの循環式冷却水系統においては熱交換効率の低下、散水板の閉塞などにより冷却塔が機能しなくなるなど様々な問題を引き起こす要因となっている。また、富栄養化の進んだ湖沼や用水池、内湾や入江のような閉鎖性の強い水系においては、しばしばアオコが大量発生し、これにより外観を損なうだけでなく、特異な臭気や、湖沼に生息する魚介類のへい死を招くなど甚大な被害をもたらす要因となっている。 In the above water systems and facilities, often due to the growth of algae, the generation of off-flavors and deterioration of the appearance, clogging of piping, reduction of heat exchange efficiency in the circulating cooling water system of the cooling tower, clogging of water spray plates, etc. It causes various problems such as the cooling tower not functioning. Also, in highly closed water systems such as eutrophied lakes and irrigation ponds, inner bays and bays, a large amount of blue sea bream is often generated, which not only impairs the appearance, but also causes unusual odors and lakes. It is a factor that causes enormous damage, such as causing the death of inhabited seafood.
　このような藻類及び一般細菌の生育及び増殖を抑制するための薬剤として、殺藻剤としては、アメトリン、シメトリン、プロメトリン等のトリアジン系殺藻剤が効果の高さから用いられている｛「農薬ハンドブック」（1998年版 社団法人 日本植物防疫協会 編）｝。しかしこれらトリアジン系殺藻剤は、水に対する溶解性が低く、製剤化の際には多量の有機溶剤を配合する必要があり、水系に添加した際には製剤中の有機溶剤が一般細菌の栄養源となってしまうなどの問題があった。また、これらトリアジン系殺藻剤は毒性や発ガン性が指摘されるなど安全性の面でも課題を有している。一方、一般細菌の生育及び増殖を抑制するための殺菌剤としては、5－クロロ－2－メチル－4－イソチアゾリン－3－オンなどのイソチアゾロン系化合物や2－ブロモ－2－ニトロプロパン－1，3－ジオールに代表される有機臭素系化合物が用いられている（特許文献１および特許文献２）。しかし、イソチアゾロン系化合物は、毒性、皮膚刺激性、粘膜刺激性が強く取り扱い等が不便であり、有機臭素系化合物は、一般細菌に対する効果は比較的強いものの殺藻効果が弱いという欠点があった。このため、殺藻効果と殺菌効果の両効果を得るためには、少なくとも２種以上の成分を組み合わせる必要があり、製剤化の面では薬剤が高価となり、各成分を水系に別々に添加する場合でも、薬剤添加のためのポンプや薬液タンクなどの経費が必要になるなどの他に作業が繁雑となる課題を有している。 As drugs for suppressing the growth and proliferation of such algae and general bacteria, triazine-based algicides such as amethrin, simethrin, promethrin and the like are used because of their high efficacy as algicides. Handbook "(1998 edition Japan Plant Protection Association edition)}. However, these triazine-based algicides have low solubility in water, and it is necessary to add a large amount of an organic solvent for formulation. When added to an aqueous system, the organic solvent in the formulation is a nutrient for general bacteria. There were problems such as becoming a source. In addition, these triazine-based algicides have problems in terms of safety such as toxicity and carcinogenicity. On the other hand, bactericides for suppressing the growth and proliferation of general bacteria include isothiazolone compounds such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1, An organic bromine-based compound represented by 3-diol is used (Patent Document 1 and Patent Document 2). However, isothiazolone compounds have strong toxicity, skin irritation and mucous membrane irritation and are inconvenient to handle, and organic bromine compounds have the disadvantage that they have a relatively strong effect on general bacteria but a weak algaecidal effect. . For this reason, in order to obtain both the algicidal effect and the bactericidal effect, it is necessary to combine at least two kinds of components, and in terms of formulation, the drug becomes expensive, and each component is added to the aqueous system separately. However, in addition to the expense of pumps and chemical tanks for adding chemicals, there is a problem that the work becomes complicated.
　近年では、水の供給の逼迫、価格の上昇に伴い、水の循環再利用が進み、殺菌・殺藻剤の必要性が益々高まっている反面、経費削減を目的としてこれら薬剤の低コスト化も望まれている。このことを受けて、安価な次亜塩素酸ナトリウムなどの塩素系酸化剤、アゾール系化合物及びスルファミン酸若しくはその塩を含有する殺菌殺藻剤が報告されている（特許文献３）。しかし、この次亜塩素酸塩にスルファミン酸又はその塩を添加して形成されるN－クロロスルファミン酸若しくはN，N－ジクロロスルファミン酸又はこれらの塩は、結合型塩素であり、次亜塩素酸などの遊離塩素と比較するとその殺菌効果は劣ることが知られている。また、結合型塩素は、酸化力が遊離塩素に比べて低減されるものの、高濃度では系内配管・設備の腐食などの問題を引き起こす可能性が高い。一般に次亜塩素酸などハロゲン系酸化剤の殺藻効果は、前述のアメトリンなどのトリアジン系殺藻剤に比べて低く、結合型のN－クロロスルファミン酸なども同様である。このため、殺藻効果を得るためには高濃度の添加が必要となり、結果として系内配管・設備の腐食を引き起こす危険性が高まるなどの課題があった。このように、現在使用される薬剤は、水に対する溶解性、コスト、取り扱い性、安全性等の面において様々な欠点を有しており、必ずしも満足できるものではなかった。 In recent years, with the tightening of water supply and rising prices, the circulation and reuse of water has progressed and the need for bactericides and algicides has increased. On the other hand, the cost of these drugs has been reduced to reduce costs. It is desired. In response to this, a bactericidal algicidal agent containing an inexpensive chlorine-based oxidizing agent such as sodium hypochlorite, an azole-based compound, and sulfamic acid or a salt thereof has been reported (Patent Document 3). However, N-chlorosulfamic acid or N, N-dichlorosulfamic acid or a salt thereof formed by adding sulfamic acid or a salt thereof to this hypochlorite is bound chlorine, and hypochlorous acid It is known that its bactericidal effect is inferior to free chlorine such as. Bonded chlorine is less likely to cause problems such as corrosion of piping and equipment in the system at high concentrations, although its oxidizing power is reduced compared to free chlorine. In general, the algicidal effect of halogen-based oxidizing agents such as hypochlorous acid is lower than that of triazine-based algicidal agents such as amethrin described above, and bound N-chlorosulfamic acid is the same. For this reason, in order to obtain the algicidal effect, a high concentration is required, and as a result, there is a problem that the risk of causing corrosion of piping and equipment in the system is increased. As described above, currently used drugs have various drawbacks in terms of solubility in water, cost, handleability, safety and the like, and are not always satisfactory.
　なお、本発明の殺藻・殺菌剤成分の一つであるN－クロロ－２－ピロリジノンは、特許文献４にN－クロロ－５－メチル－2－オキサゾリジノンなどと併せて消毒・漂白剤としての報告があるが、殺藻効果についての記載はない。また、次亜塩素酸の安定化を目的にN－水素化合物類としてスルファミン酸やヒダントインなどと共に２－ピロリジノンを配合する方法が特許文献５や特許文献６に報告されているが、あくまでも２－ピロリジノンなどのN－水素化合物類は次亜塩素酸の安定化を目的として配合されており、本発明に示す結合型のN－クロロ化合物或いはN，N’－ジクロロ化合物としての評価はなされておらず、殺藻効果についての言及もない。さらに、特許文献７では、遊離ハロゲンとN－水素化合物類としてジメチルヒダントインを併用する微生物防除方法が報告されており、N－水素化合物類の一つとして２－ピロリジノンの記載はあるが、実施例としての評価はされておらず、殺藻効果についての言及もない。 In addition, N-chloro-2-pyrrolidinone, which is one of the algicidal / bactericidal components of the present invention, is used as a disinfectant / bleaching agent in combination with N-chloro-5-methyl-2-oxazolidinone in Patent Document 4. There is a report, but there is no description about the algicidal effect. Further, methods for blending 2-pyrrolidinone with sulfamic acid or hydantoin as N-hydrogen compounds for the purpose of stabilizing hypochlorous acid have been reported in Patent Document 5 and Patent Document 6, but 2-pyrrolidinone is only used. N-hydrogen compounds such as these are formulated for the purpose of stabilizing hypochlorous acid, and have not been evaluated as bonded N-chloro compounds or N, N′-dichloro compounds shown in the present invention. There is no mention of the algaecidal effect. Further, Patent Document 7 reports a microorganism control method using dimethylhydantoin in combination with free halogen and N-hydrogen compounds, and there is a description of 2-pyrrolidinone as one of N-hydrogen compounds. Has not been evaluated, and there is no mention of the algicidal effect.
特公昭５３－１１８５２７号公報Japanese Patent Publication No.53-118527 特公昭５５－７３６０３号公報Japanese Patent Publication No.55-73603 特許第４４７０１２１号Patent No. 4470121 米国特許第３５９１６０１号US Pat. No. 3,591,601 米国特許第３７４９６７２号U.S. Pat. No. 3,749,672 特開２００２－３６３０１６号公報JP 2002-363016 A 米国特許第５５６５１０９号US Pat. No. 5,565,109
　本発明の課題は、水への溶解性に優れる、低コストで取り扱い性に優れた殺藻剤及び殺藻・殺菌剤を提供することにある。 
　本発明の課題はまた、腐食が望まれない金属部材と接触している水系中において藻類及び／又は細菌類を防除するための方法を提供する。 An object of the present invention is to provide an algicidal agent and an algicidal / bactericidal agent that are excellent in solubility in water, low in cost, and excellent in handleability.
The subject of the present invention also provides a method for controlling algae and / or bacteria in an aqueous system in contact with a metal member where corrosion is not desired.
　本発明を概説すれば、本発明は、
（１）Ｎ－クロロ－２－ピロリジノンを含有することを特徴とする殺藻剤、
（２）水又は水と水溶性有機溶剤の混合溶液を更に含む、水溶性の液体製剤であることを特徴とする（１）記載の殺藻剤、
（３）式（Ｉ）：
Figure JPOXMLDOC01-appb-C000007
 In summary, the present invention provides:
(1) an algicidal agent containing N-chloro-2-pyrrolidinone,
(2) The algicidal agent according to (1), which is a water-soluble liquid preparation further comprising water or a mixed solution of water and a water-soluble organic solvent,
(3) Formula (I):
Figure JPOXMLDOC01-appb-C000007
（式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上を含有することを特徴とする殺藻・殺菌剤、
（４）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（３）記載の殺藻・殺菌剤、
（５）水又は水と水溶性有機溶剤の混合溶液を更に含む、水溶性の液体製剤であることを特徴とする（３）又は（４）記載の殺藻・殺菌剤、
（６）腐食が望まれない金属部材と接触している水系中に、式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上を含有する殺藻・殺菌剤を、残留塩素濃度（Ｃｌ２換算）として０．２～１０ｍｇ／Ｌとなるように添加する殺藻・殺菌方法、
（７）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピロリジノン、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（６）記載の殺藻・殺菌方法、
（８）殺藻するためのＮ－クロロ－２－ピロリジノンの使用、
（９）Ｎ－クロロ－２－ピロリジノンを用いる殺藻方法；具体的には、藻類に、又は、藻類の防除が望まれる対象に、Ｎ－クロロ－２－ピロリジノンを付与する工程を含む、殺藻方法（ここで「藻類の防除が望まれる対象」とは、たとえば水系を指す）、
（１０）殺藻剤の製造のためのＮ－クロロ－２－ピロリジノンの使用
（１１）Ｎ－クロロ－２－ピロリジノンを使用する殺藻剤の製造方法；具体的には、Ｎ－クロロ－２－ピロリジノンを配合する工程を含む、殺藻剤の製造方法（当該方法は、適宜、他の成分を配合する工程を更に含むことができる）、
（１２）殺藻・殺菌するための式（Ｉ）で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物の使用、
（１３）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（１２）記載の使用、
（１４）式（Ｉ）で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物を用いる殺藻・殺菌方法；具体的には、藻類及び／又は細菌類に、又は、藻類及び／又は細菌類の防除が望まれる対象に、当該化合物を付与する工程を含む、殺藻・殺菌方法（ここで「藻類及び／又は細菌類の防除が望まれる対象」とは、たとえば水系を指す）、
（１５）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（１４）記載の殺藻・殺菌方法、
（１６）殺藻・殺菌剤の製造のための式（Ｉ）で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物の使用、
（１７）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（１６）記載の使用、
（１８）式（Ｉ）で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物を使用する、殺藻・殺菌剤の製造方法；具体的には、当該化合物を配合する工程を含む、殺藻・殺菌剤の製造方法（当該方法は、適宜、他の成分を配合する工程を更に含むことができる）、
（１９）式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする（１８）記載の製造方法、
に関する。 (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
Containing at least one selected from the group consisting of cyclic N-chloro compounds (excluding N-chloro-2-pyrrolidinone) and N, N′-dichloro compounds ,
(4) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-hepta. Selected from lactam, N-chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone (1) The algae / bactericidal agent according to (3),
(5) The algicidal / bactericidal agent according to (3) or (4), which is a water-soluble liquid preparation further comprising water or a mixed solution of water and a water-soluble organic solvent,
(6) One or more selected from the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is contained in an aqueous system in contact with a metal member where corrosion is not desired. Algaecidal / bactericidal method, adding residual chlorine concentration (Cl 2 equivalent) to 0.2 to 10 mg / L,
(7) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-pyrrolidinone, N-chloro-2-piperidone, N-chloro-ε-caprolactam N-chloro-ω-heptalactam, N-chloro-2-imidazolidinone, N, N′-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N′-dichloro -Algae / sterilization method according to (6), characterized in that it is at least one selected from tetrahydro-2-pyrimidinone,
(8) Use of N-chloro-2-pyrrolidinone to kill algae,
(9) Algae killing method using N-chloro-2-pyrrolidinone; specifically, including a step of imparting N-chloro-2-pyrrolidinone to algae or to a subject for which algae control is desired. Algae method (where "algae control is desired" refers to, for example, an aqueous system),
(10) Use of N-chloro-2-pyrrolidinone for the production of an algicide (11) Method for producing an algicide using N-chloro-2-pyrrolidinone; specifically, N-chloro-2 -A method for producing an algicide, comprising a step of blending pyrrolidinone (the method may further comprise a step of blending other components as appropriate),
(12) One kind selected from cyclic N-chloro compounds represented by formula (I) (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds for algaecidal / sterilizing Use of the above compounds,
(13) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-hepta. Selected from lactam, N-chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone The use according to (12), characterized in that it is one or more
(14) Algicidal using one or more compounds selected from cyclic N-chloro compounds represented by formula (I) (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds A sterilization method; specifically, an algicide / sterilization method comprising a step of applying the compound to algae and / or bacteria or to a subject for which control of algae and / or bacteria is desired. "A target for which control of algae and / or bacteria is desired" refers to, for example, an aqueous system)
(15) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-hepta. Selected from lactam, N-chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone (1) The algaecidal / sterilizing method according to (14),
(16) A cyclic N-chloro compound represented by formula (I) (excluding N-chloro-2-pyrrolidinone) or an N, N′-dichloro compound for the production of an algicidal / bactericidal agent Use of one or more compounds,
(17) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-hepta. Selected from lactam, N-chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone The use according to (16), characterized in that it is one or more of
(18) One or more compounds selected from cyclic N-chloro compounds represented by formula (I) (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds are used. Method for producing algicide / bactericidal agent; specifically, a method for producing algicide / bactericidal agent, comprising the step of blending the compound (this method may further comprise a step of blending other components as appropriate) it can),
(19) The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-hepta. Selected from lactam, N-chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone (1) The production method according to (18),
About.
　なお本発明において「殺藻・殺菌剤」とは、「殺藻剤及び／又は殺菌剤」を指す。「殺藻・殺菌方法」とは、「藻類及び／又は細菌類を防除する方法」を指す。「殺藻・殺菌する」とは、「藻類及び／又は細菌類を防除する」ことを指す。 In the present invention, the term “algicidal / bactericidal agent” refers to “algicidal and / or bactericidal agent”. The “algaecidal / sterilizing method” refers to “a method of controlling algae and / or bacteria”. “Algae-killing” refers to “controlling algae and / or bacteria”.
　本発明において、「藻類の防除」とは、たとえば藻類の生育又は増殖の抑制又は阻止を指す。 In the present invention, “algae control” refers to, for example, suppression or prevention of algae growth or proliferation.
　本発明において、「藻類及び／又は細菌類の防除」とは、たとえば藻類及び／又は細菌類の生育又は増殖の抑制又は阻止を指す。 In the present invention, “control of algae and / or bacteria” refers to suppression or inhibition of growth or proliferation of algae and / or bacteria, for example.
　本発明者は、水への溶解性に優れ、優れた殺藻効果と殺菌効果とを発揮し、低コストで取り扱い性に優れた殺藻・殺菌剤組成物を鋭意研究した結果、水溶性の液体製剤として取り扱え、水への溶解性に優れ、水溶液中において安定で、有効塩素が結合型のN－クロロ又はN，N’－ジクロロ化合物でありながら、優れた殺藻効果と殺菌効果を示し、尚且つ腐食性の低い、取り扱い性に優れた殺藻・殺菌剤組成物を見出し、本発明に至った。 As a result of earnest research on an algicide / disinfectant composition that has excellent solubility in water, exhibits excellent algicidal and bactericidal effects, and is low in cost and easy to handle, It can be handled as a liquid formulation, has excellent solubility in water, is stable in aqueous solution, and exhibits excellent algicidal and bactericidal effects, even though effective chlorine is a combined N-chloro or N, N'-dichloro compound. Furthermore, the present inventors have found an algicidal / bactericidal composition having low corrosive properties and excellent handleability, and has reached the present invention.
　本明細書は本願の優先権の基礎である日本国特許出願2011-002059号の明細書および／または図面に記載される内容を包含する。 This specification includes the contents described in the specification and / or drawings of Japanese Patent Application No. 2011-002059 which is the basis of the priority of the present application.
　本発明の式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物は、水への溶解性に優れ、高い殺藻効果と殺菌効果を示すことを見出した。 It has been found that the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is excellent in solubility in water and exhibits high algicidal and bactericidal effects.
　また、式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物は、水に任意の割合で溶解するため、水溶液として取り扱うことができ、当水溶液は、長期に渡り有効塩素濃度を維持する安定な水溶液であることも見出した。 In addition, the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) can be handled as an aqueous solution because it dissolves in water at an arbitrary ratio. It has also been found that the aqueous solution is stable and maintains an effective chlorine concentration.
　加えて、本発明の式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物は、対応するＮ－水素環状アミド化合物と次亜塩素酸ナトリウムなどの水中で次亜塩素酸を発生させる化合物との混合により安価に且つ簡単に安定な水溶液として調製出来ることも利点の一つである。 In addition, the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is a hypothetical compound in water such as the corresponding N-hydrogen cyclic amide compound and sodium hypochlorite. Another advantage is that it can be prepared as a stable aqueous solution at a low cost by mixing with a compound that generates chloric acid.
　さらには、本発明の式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物は、腐食性が極めて低く、高濃度での使用においても設備、配管を腐食してしまう危険性が低いことも利点である。 Furthermore, the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is extremely low in corrosiveness and corrodes equipment and piping even when used at a high concentration. It is also an advantage that the risk of falling is low.
　以下、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described.
　本発明において式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物は、好ましくは、Ｎ－クロロ－２－ピロリジノン、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上である。 In the present invention, the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is preferably N-chloro-2-pyrrolidinone, N-chloro-2-piperidone, N-chloro- ε-caprolactam, N-chloro-ω-heptalactam, N-chloro-2-imidazolidinone, N, N′-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N One or more selected from '-dichloro-tetrahydro-2-pyrimidinone.
　本発明において、「殺藻剤」及び「殺藻・殺菌剤」という用語は、それぞれ、所定の有効成分を少なくとも含み、他の成分が配合されていてもよい殺藻用の化合物又は組成物、並びに、殺藻及び／又は殺菌用の化合物又は組成物を指す。 In the present invention, the terms “algicidal agent” and “algicidal / bactericidal agent” each contain at least a predetermined active ingredient and may contain other ingredients, or an algaecidal compound or composition, In addition, it refers to a compound or composition for algicidal and / or sterilizing.
　上記の他の成分としては、製剤化のための希釈剤、賦形剤等の媒体や、他の有効成分が挙げられる。他の成分は安定性を損なわない範囲内で公知の成分から選択することができる。 Examples of the above-mentioned other components include media such as diluents and excipients for formulation, and other active ingredients. Other components can be selected from known components as long as the stability is not impaired.
　本発明の殺藻剤及び殺藻・殺菌剤は任意の形態に製剤化されたものであってよい。好ましい製剤化の形態として、本発明の式（Ｉ）で表される環状のN－クロロ化合物又はN，N’－ジクロロ化合物を、水あるいは水と水溶性有機溶剤の混合溶液に溶解して形成された、水溶性の液体製剤が挙げられる。水溶性有機溶剤としては、乳酸、蟻酸、酢酸、クエン酸等の有機酸類、アセトン等のケトン類、エタノール等のアルコール類、エチレングリコール等のグリコール類、ジエチレングリコールモノメチルエーテル等のグリコールエーテル類、ジエチルカーボネート等のエステル類、テトラヒドロフラン等のエーテル類、環状アミド類、ジメチルホルムアミド等の鎖状アミド類等が挙げられる。 The algicidal agent and algicidal / bactericidal agent of the present invention may be formulated into an arbitrary form. As a preferred formulation, the cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) of the present invention is dissolved in water or a mixed solution of water and a water-soluble organic solvent. And water-soluble liquid preparations. Examples of water-soluble organic solvents include organic acids such as lactic acid, formic acid, acetic acid and citric acid, ketones such as acetone, alcohols such as ethanol, glycols such as ethylene glycol, glycol ethers such as diethylene glycol monomethyl ether, diethyl carbonate And esters such as tetrahydrofuran, ethers such as tetrahydrofuran, cyclic amides, and chain amides such as dimethylformamide.
　さらに、本発明の殺藻・殺菌剤へは、安定性を損なわない範囲内で、公知の殺菌有効成分を配合することが出来る。これらの具体例としては、２，２－ジブロモ－２－ニトロエタノールや２－ブロモ－2－ニトロプロパン－１，３－ジオールなどの有機ブロモニトロ系化合物、５－クロロ－２－メチル－４－イソチアゾリン－３－オンや２－メチル－４－イソチアゾリン－３－オンなどのイソチアゾロン系化合物、ジメチルジチオカーバメートなどのジチオカーバメート化合物、２－メルカプトベンゾチアゾールナトリウムなどのチアゾール系化合物、１，２－ビス（ブロモアセトキシ）－エタン、１，４－ビス－（ブロモアセトキシ）－２－ブテンやＮ－ブロモアセトアミドなどの有機ブロム酢酸エステル又はアミド類、塩化ジデシルジメチルアンモニウム、塩化ベンザルコニウム、ビス型ピリジニウム塩などの第四級アンモニウム塩などの殺菌剤成分や藻類防除剤成分が挙げられる。また、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤又は両性界面活性剤の配合も可能である。 Furthermore, a known bactericidal active ingredient can be added to the algicidal / bactericidal agent of the present invention within a range not impairing the stability. Specific examples thereof include organic bromonitro compounds such as 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol, and 5-chloro-2-methyl-4-isothiazoline. Isothiazolone compounds such as -3-one and 2-methyl-4-isothiazolin-3-one, dithiocarbamate compounds such as dimethyldithiocarbamate, thiazole compounds such as sodium 2-mercaptobenzothiazole, 1,2-bis (bromo Acetoxy) -ethane, 1,4-bis- (bromoacetoxy) -2-butene, N-bromoacetamide and other organic bromoacetates or amides, didecyldimethylammonium chloride, benzalkonium chloride, bis-type pyridinium salts, etc. Bactericides such as quaternary ammonium salts and algae And the like control component. Further, a cationic surfactant, an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant can also be blended.
　クーリングタワーなどの工業用循環冷却水用途では、さらにアクリル酸やマレイン酸などを含む重合体や２－ホスホノブタン－１，２，４－トリカルボン酸などの有機ホスホン酸等のスケール抑制剤、亜鉛塩、重合リン酸塩、有機ホスホン酸、アゾール化合物、モリブテン酸塩などの腐食抑制剤の配合も可能である。 For industrial circulating cooling water applications such as cooling towers, scale inhibitors such as polymers containing acrylic acid and maleic acid, organic phosphonic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, zinc salts, polymerization Corrosion inhibitors such as phosphates, organic phosphonic acids, azole compounds, and molybdates can also be added.
　なお、本発明の殺藻・殺菌剤組成物及び次亜塩素酸の有効塩素濃度は、ジエチル－ｐ－フェニレンジアンモニウム（ＤＰＤ）比色法、ＤＰＤ－硫酸アンモニウム鉄（ＩＩ）滴定法（ＪＩＳ　Ｋ　０１０１）などの方法で測定でき、簡易な分析キットも市販されている。本発明での有効塩素濃度測定には、ＤＰＤ－硫酸アンモニウム鉄（ＩＩ）滴定法と平沼産業社製の有効塩素カウンタ　ＣＬ－３００（ヨウ素電量滴定法）を用いて行った。 The effective chlorine concentration of the algicidal / bactericidal composition of the present invention and hypochlorous acid is determined by diethyl-p-phenylenediammonium (DPD) colorimetric method, DPD-ammonium iron (II) sulfate titration method (JIS K 0101). ) Etc., and simple analysis kits are also commercially available. The effective chlorine concentration measurement in the present invention was performed using a DPD-ammonium iron (II) sulfate titration method and an effective chlorine counter CL-300 (iodine coulometric titration method) manufactured by Hiranuma Sangyo Co., Ltd.
　本発明の殺藻・殺菌剤の該水系への添加量は、該水系の規模、対象とする水系の水質、汚染の程度、添加頻度等により異なるために一律に決められるものではないが、通常は該水系の水において残留塩素濃度として０．１～５０ｍｇ／Ｌとするのが望ましい。残留塩素濃度として０．１ｍｇ／Ｌより低い場合には、実質的に本発明の効果が期待できず、また５０ｍｇ／Ｌより多い場合は、経済性の面で好ましくない。なお、ここでいう残留塩素濃度とは、水中に残留する全ての有効塩素濃度を意味する。 The amount of the algicidal / bactericidal agent of the present invention to be added to the aqueous system varies depending on the scale of the aqueous system, the quality of the target aqueous system, the degree of contamination, the frequency of addition, etc. Is preferably 0.1 to 50 mg / L as the residual chlorine concentration in the water. When the residual chlorine concentration is lower than 0.1 mg / L, the effect of the present invention cannot be expected substantially. When the residual chlorine concentration is higher than 50 mg / L, it is not preferable in terms of economy. The residual chlorine concentration here means all effective chlorine concentrations remaining in water.
　本発明はまた、式（Ｉ）で表される上記の化合物を、水系中に添加し、該水系中での藻類及び／又は細菌類の生育及び／又は増殖を抑制する方法に関する。この方法は特に、腐食が望まれない金属部材と接触している水系における藻類及び／又は細菌類の防除に適した方法である。驚くべきことに、従来公知のＮ－クロロ化合物系殺藻・殺菌剤と比較して、本発明の殺藻・殺菌剤は高濃度でも鉄や銅への腐食性が低い。金属部材の腐食を抑制しつつ藻類及び／又は細菌類を防除するためには、式（Ｉ）で表される化合物を、残留塩素濃度（Ｃｌ２換算）として０．２～１０ｍｇ／Ｌ、より好ましくは２．５～５．０ｍｇ／Ｌとなるように水系中に添加することが好ましい。腐食が望まれない金属部材としては、水系に接触する金属製の配管や設備が挙げられる。金属としては鉄、銅、ステンレス鋼等が挙げられる。残留塩素濃度（Ｃｌ２換算）は上述の有効塩素濃度の測定方法により測定することができる。 The present invention also relates to a method for inhibiting the growth and / or proliferation of algae and / or bacteria in the aqueous system by adding the above-mentioned compound represented by formula (I) into the aqueous system. This method is particularly suitable for the control of algae and / or bacteria in aqueous systems in contact with metal parts where corrosion is not desired. Surprisingly, as compared with conventionally known N-chloro compound-based algicide / bactericides, the algicide / bactericides of the present invention are less corrosive to iron and copper even at high concentrations. In order to control algae and / or bacteria while suppressing corrosion of metal members, the compound represented by formula (I) is 0.2 to 10 mg / L as a residual chlorine concentration (Cl 2 equivalent), Preferably, it is added to the aqueous system so as to be 2.5 to 5.0 mg / L. Examples of metal members that do not require corrosion include metal pipes and equipment that come into contact with water systems. Examples of the metal include iron, copper, and stainless steel. The residual chlorine concentration (in terms of Cl 2 ) can be measured by the above-described method for measuring effective chlorine concentration.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
　実施例１では、クロロホルム［試薬、関東化学（株）製］ １００ｇ に２－ピロリジノン［試薬、関東化学（株）製］ ６．８ｇ を加え、室温下、トリクロロイソシアヌル酸［試薬、東京化成工業（株）製］ ９．３ｇ を４０分かけて投入した。生じた白色スラリーを６時間攪拌後に吸引濾過した。この濾液をロータリーエバポレーターで濃縮後に氷冷してN－クロロ－２－ピロリジノンの白色結晶 ９．４ｇ を得た（収率９８．４％、物性を下記に示す）。 In Example 1, 6.8 g of 2-pyrrolidinone [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to 100 g of chloroform [reagent, manufactured by Kanto Chemical Co., Ltd.], and trichloroisocyanuric acid [reagent, Tokyo Chemical Industry ( Co., Ltd.] 9.3 g of koji was added over 40 minutes. The resulting white slurry was filtered with suction after stirring for 6 hours. The filtrate was concentrated on a rotary evaporator and then ice-cooled to obtain 9.4 g of white crystals of N-chloro-2-pyrrolidinone (yield 98.4%, physical properties are shown below).
１Ｈ－ＮＭＲ（ＣＤＣｌ３、δ）：
２．２８（ｍ、４Ｈ）、４．２１（ｔ、２Ｈ）
ＩＲ（ＫＢｒ、ｃｍ－1）：
２９６８、１７０８、１３８５、１２５４、１１３５、８２０
　このN－クロロ－２－ピロリジノンの白色結晶９．４ｇに酢酸 ４．６ｇ 、水 ８６．０ｇ を加えて、有効塩素濃度５．５％のN－クロロ－２－ピロリジノン水溶液 １００ｇを調製した。なお、この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 1 H-NMR (CDCl 3 , δ):
2.28 (m, 4H), 4.21 (t, 2H)
IR (KBr, cm -1 ):
2968, 1708, 1385, 1254, 1135, 820
To 9.4 g of the white crystals of N-chloro-2-pyrrolidinone, 4.6 g of acetic acid and 86.0 g of water were added to prepare 100 g of an aqueous N-chloro-2-pyrrolidinone solution having an effective chlorine concentration of 5.5%. In this aqueous solution, the chlorine form was detected as a bound type in the DPD-iron ammonium sulfate (II) titration method.
　実施例２では、２－ピペリドン［試薬、関東化学（株）製］ ７．６ｇと水 ４２．８ｇとを混合し、酢酸［試薬、関東化学（株）製］ ４．６ｇを加えた水溶液に有効塩素濃度１２％の次亜塩素酸ナトリウム溶液［有効塩素濃度１２％、やよい産業（株）製］ ４５．０ｇを添加して、有効塩素濃度 ５．４％のN－クロロ－２－ピペリドン水溶液 １００ｇ を調製した。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 In Example 2, 7.6 g of 2-piperidone [reagent, manufactured by Kanto Chemical Co., Ltd.] と and 42.8 g of waterpox were mixed, and 4.6 g of acetic acid [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to the aqueous solution. Sodium hypochlorite solution with an effective chlorine concentration of 12% [effective chlorine concentration of 12%, manufactured by Yayoi Sangyo Co., Ltd.] ５．０ 45.0 g was added, and an N-chloro-2-piperidone aqueous solution with an effective chlorine concentration of 5.4% 100 g of koji was prepared. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　実施例３では、クロロホルム１００ｇ にε－カプロラクタム［試薬、関東化学（株）製］ ７．９ｇ を加え、氷冷下、トリクロロイソシアヌル酸 ８．１ｇ を９０分かけて投入した。生じた白色スラリーを６時間攪拌後に吸引濾過し、濾液をロータリーエバポレーターで濃縮しN－クロロ－ε－カプロラクタムの微黄色透明のオイル １０．１ｇ を得た（収率９７．９％、物性を下記に示す）。 In Example 3, 7.9 g of ε-caprolactam [reagent, manufactured by Kanto Chemical Co., Ltd.] was added to 100 g of chloroform, and 8.1 g of trichloroisocyanuric acid was added over 90 minutes under ice cooling. The resulting white slurry was filtered with suction after stirring for 6 hours, and the filtrate was concentrated by a rotary evaporator to obtain 10.1 g of a slightly yellow transparent oil of N-chloro-ε-caprolactam (yield 97.9%, physical properties are as follows). To show).
１Ｈ－ＮＭＲ（ＣＤＣｌ３、δ）：
１．７８（ｂｒ．ｓ、６Ｈ）、２．４５（ｄ、２Ｈ）、３．２１（ｔ、２Ｈ）
ＩＲ（ＮａＣｌ、ｃｍ－1）：
２９３３、２８５８、１６７２、１４５２、１１９１、９８０
　このN－クロロ－ε－カプロラクタムの微黄色透明オイル１０．１ｇにγ－ブチロラクトン［試薬、関東化学（株）製］１０．０ｇ 、酢酸 ４．１ｇ 、水 ７５．８ｇ を加えて、有効塩素濃度４．７％のN－クロロ－ε－カプロラクタム水溶液 １００ｇ を調製した。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 1 H-NMR (CDCl 3 , δ):
1.78 (br.s, 6H), 2.45 (d, 2H), 3.21 (t, 2H)
IR (NaCl, cm −1 ):
2933, 2858, 1672, 1452, 1191, 980
10.0 g of γ-butyrolactone [reagent, manufactured by Kanto Chemical Co., Ltd.], 4.1 g of acetic acid, and 75.8 g of water were added to 10.1 g of this slightly yellow transparent oil of N-chloro-ε-caprolactam to obtain an effective chlorine concentration. 100 g of a 4.7% aqueous solution of N-chloro-ε-caprolactam was prepared. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　実施例４では、実施例２の２－ピペリドンの代わりにω－ヘプタラクタム［試薬、東京化成工業（株）製］８．６ｇ を水 ３１．８ｇ に溶かし、γ－ブチロラクトン １０．０ｇを加えた以外は、実施例２と同様の操作を行い、有効塩素濃度５．４％のＮ－クロロ－ω－ヘプタラクタム水溶液１００ｇを得た。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 In Example 4, 8.6 g of ω-heptalactam [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] was dissolved in 31.8 g of water tank instead of 2-piperidone of Example 2, and 10.0 g of γ-butyrolactone was added. Except for the above, the same operation as in Example 2 was carried out to obtain 100 g of an aqueous N-chloro-ω-heptalactam solution having an effective chlorine concentration of 5.4%. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　実施例５では、テトラヒドロ－２－ピリミジノン［試薬、東京化成工業（株）製］ ５．０ｇ にジクロロメタン［試薬、関東化学（株）製］ ４０．０ｇ を加え、室温下、トリクロロイソシアヌル酸 ８．５ｇ を３０分かけて投入した。生じた白色スラリーを８時間攪拌後に吸引濾過し、濾液をロータリーエバポレーターで濃縮後に氷冷してN，N’－ジクロロ－テトラヒドロ－２－ピリミジノンの白色結晶 ８．１ｇ を得た（収率９６．２％、物性を下記に示す）。 In Example 5, tetrahydro-2-pyrimidinone [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] 5.0 g－２ was added dichloromethane [reagent, manufactured by Kanto Chemical Co., Ltd.] 40.0 g, and trichloroisocyanuric acid． 8. 5 g of koji was added over 30 minutes. The resulting white slurry was stirred and filtered for 8 hours, and the filtrate was concentrated with a rotary evaporator and then ice-cooled to obtain 8.1 g of white crystals of N, N'-dichloro-tetrahydro-2-pyrimidinone (yield 96. 2%, physical properties are shown below).
１Ｈ－ＮＭＲ（ＣＤＣｌ３、δ）：
１．９８（ｍ、４Ｈ）、２．９８（ｔ、２Ｈ）
ＩＲ（ＫＢｒ、ｃｍ－1）：
２９６６、２８８７、１６９７、１４７５、１２７７、１１７２
　このN，N’－ジクロロ－テトラヒドロ－２－ピリミジノンの白色結晶８．１ｇにγ－ブチロラクトン２０．０ｇ 、酢酸 ５．７ｇ、水 ６６．２ｇ を加えて、有効塩素濃度６．８％のN，N’－ジクロロ－テトラヒドロ－２－ピリミジノン水溶液 １００ｇ を調製した。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。なお、実施例５で得られた結晶および水溶液の保管に当たっては、直射日光を避けるため遮光容器に保管した。 1 H-NMR (CDCl 3 , δ):
1.98 (m, 4H), 2.98 (t, 2H)
IR (KBr, cm -1 ):
2966, 2887, 1697, 1475, 1277, 1172
By adding 20.0 g of γ-butyrolactone, 5.7 g of acetic acid and 66.2 g of water to 8.1 g of the white crystals of N, N′-dichloro-tetrahydro-2-pyrimidinone, N, having an effective chlorine concentration of 6.8%, 100 g of an aqueous solution of N′-dichloro-tetrahydro-2-pyrimidinone was prepared. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method. In addition, when storing the crystals and the aqueous solution obtained in Example 5, they were stored in a light shielding container in order to avoid direct sunlight.
　実施例６では、実施例５における塩素化剤のトリクロロイソシアヌル酸を３．９ｇに減らして同様の操作を行いＮ－クロロ－テトラヒドロ－２－ピリミジノンの白色結晶５．６ｇを得た（収率８３．２％、物性を下記に示す）。 In Example 6, 5.6 g of white crystals of N-chloro-tetrahydro-2-pyrimidinone were obtained by performing the same operation while reducing the chlorinating agent trichloroisocyanuric acid in Example 5 to 3.9 g (yield 83). 2%, physical properties are shown below).
ＩＲ（ＫＢｒ、ｃｍ－1）：
３３６７、２８８７、１６７６、１４９０、１２７８、１１７２、７２４
　このＮ－クロロ－テトラヒドロ－２－ピリミジノンの白色結晶５．６ｇにγ－ブチロラクトン２０．０ｇ、水７４．４ｇを加えて有効塩素濃度３．０％のＮ－クロロ－テトラヒドロ－２－ピリミジノン水溶液１００ｇを調製した。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 IR (KBr, cm -1 ):
3367, 2887, 1676, 1490, 1278, 1172, 724
To 5.6 g of the white crystals of N-chloro-tetrahydro-2-pyrimidinone, 20.0 g of γ-butyrolactone and 74.4 g of water were added, and 100 g of an aqueous N-chloro-tetrahydro-2-pyrimidinone solution having an effective chlorine concentration of 3.0%. Was prepared. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　実施例７では、エチレン尿素［試薬、東京化成工業(株)製］ ６．５ｇを酢酸エチル［試薬、関東化学（株）製］４０ｇに分散して懸濁液とし、これに室温下、ジクロロジメチルヒダントイン１５．５ｇを1時間かけて投入した。生じた白色スラリーを８時間攪拌後に濾過して濾液をロータリーエバポレーターで濃縮し、析出した白色結晶をろ過乾燥してN，N’－ジクロロ－２－イミダゾリジノン３．５ｇを得た（収率３０．１％、物性を下記に示す）。 In Example 7, 6.5 g of ethylene urea [reagent, manufactured by Tokyo Chemical Industry Co., Ltd.] was dispersed in 40 g of ethyl acetate [reagent, manufactured by Kanto Chemical Co., Inc.] to form a suspension. Dimethylhydantoin 15.5g was added over 1 hour. The resulting white slurry was filtered after stirring for 8 hours, and the filtrate was concentrated with a rotary evaporator. The precipitated white crystals were filtered and dried to obtain 3.5 g of N, N′-dichloro-2-imidazolidinone (yield) 30.1%, physical properties are shown below).
ＩＲ（ＫＢｒ、ｃｍ－1）：
３２３０、１７３６、１７１５、１４４０、１３８０、１２１４、１０５４
　このN，N’－ジクロロ－２－イミダゾリジノンの白色結晶３．５ｇにγ－ブチロラクトン２０．０ｇ、水７６．５ｇを加えて有効塩素濃度３．２％のN，N’－ジクロロ－２－イミダゾリジノンの水溶液 １００ｇ を調製した。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 IR (KBr, cm -1 ):
3230, 1736, 1715, 1440, 1380, 1214, 1054
23.5 g of γ-butyrolactone and 76.5 g of water were added to 3.5 g of this white crystal of N, N′-dichloro-2-imidazolidinone to add N, N′-dichloro-2 having an effective chlorine concentration of 3.2%. -100 g of an aqueous solution of imidazolidinone was prepared. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　実施例１～７の化合物の構造は次式の通りである：
Figure JPOXMLDOC01-appb-C000008
 The structures of the compounds of Examples 1-7 are as follows:
Figure JPOXMLDOC01-appb-C000008
　比較例１では、水 １１．９ｇ、４８重量％の水酸化ナトリウム水溶液１５．６ｇ、スルファミン酸 １２．０ｇ、有効塩素濃度１２％の次亜塩素酸ナトリウム溶液 ６０．０ｇ及びベンゾトリアゾール ０．５ｇ を混合してN－クロロスルファミン酸及びN、N－ジクロロスルファミン酸を含有する殺藻・殺菌剤を調製した。この殺藻・殺菌剤の有効塩素濃度は７．２％であった。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 In Comparative Example 1, 11.9 g of water syrup, 15.6 g of 48% by weight sodium hydroxide aqueous solution, 12.0 g of sulfamic acid cocoon, 60.0 g of sodium hypochlorite solution with an effective chlorine concentration of 12%, and 0.5 g of benzotriazole By mixing, an algicidal / bactericidal agent containing N-chlorosulfamic acid and N, N-dichlorosulfamic acid was prepared. The effective chlorine concentration of this algicide / bactericidal agent was 7.2%. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　比較例２では、５，５－ジメチルヒダントイン［試薬、関東化学（株）製］１３．２ｇを水３６．８ｇとγ－ブチロラクトン２０．０ｇに溶解し、有効塩素濃度１２％の次亜塩素酸ナトリウム溶液３０．０ｇを加えて１－クロロ－５，５－ジメチルヒダントインを調製した。この殺藻・殺菌剤の有効塩素濃度は、３．６％であった。この水溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は結合型として検出された。 In Comparative Example 2, 13.2 g of 5,5-dimethylhydantoin [reagent, manufactured by Kanto Chemical Co., Ltd.] was dissolved in 36.8 g of water and 20.0 g of γ-butyrolactone, and hypochlorous acid having an effective chlorine concentration of 12%. 30.0 g of sodium solution was added to prepare 1-chloro-5,5-dimethylhydantoin. The effective chlorine concentration of this algicidal / bactericidal agent was 3.6%. In this aqueous solution, the chlorine form was detected as bound in the DPD-iron ammonium sulfate (II) titration method.
　比較例３では、有効塩素濃度が１２％の次亜塩素酸ナトリウム溶液のみを用いた。この溶液は、ＤＰＤ－硫酸アンモニウム鉄（II）滴定法において、塩素形態は遊離型として検出された。 In Comparative Example 3, only a sodium hypochlorite solution having an effective chlorine concentration of 12% was used. In this solution, the chlorine form was detected as free in the DPD-iron (II) ammonium sulfate titration method.
試験例１　殺藻試験（緑藻と藍藻）
　緑藻類としてＣｈｌｏｒｅｌｌａ　ｖｕｌｇａｒｉｓ　Ｃ－１３５（以下、クロレラという）を、藍藻類としてＭｉｃｒｏｃｙｓｔｉｓ　ａｅｒｕｇｉｎｏｓａ　Ｌｅｍｍｅｒｍａｎｎ　ＮＩＥＳ－４４（以下、ミクロキスティスという）を用いて、実施例及び比較例の殺藻・殺菌剤の殺藻効果を評価した。クロレラは、ＭＤＭ培地による前培養液を吸光度Ｏ．Ｄ．４２０での値が０．５になるように蒸留水で希釈し、これにＨＥＰＥＳ（Ｎ－２－ヒドロキシエチルピペラジン－Ｎ’－２－エタンスルホン酸）を５０ｍＭになるように投入して溶解させ、苛性ソーダにてｐＨを８．５に調整した。ミクロキスティスは、ＣＢ培地による前培養液を吸光度Ｏ．Ｄ．４４０での値が０．５になるように蒸留水で希釈し、Ｂｉｃｉｎｅ（Ｎ，Ｎ－ビス（２－ヒドロキシエチル）グリシン）を１００ｍＭになるように投入して溶解させ、苛性ソーダにてｐＨを９．０に調整した。これらを試験液とし、各１０ｍｌをＬ字型試験管に分注し、光照射型振盪－恒温水槽に設置した。実施例及び比較例の殺藻・殺菌剤を有効塩素濃度として所定濃度になるようにそれぞれ添加し、３０℃、１０ＫＬｘ（明：１２ｈ、暗：１２ｈ）の条件で振盪培養し、１日おきに目視観察し、３日間観察を行った。殺藻・殺菌剤の殺藻効果は表１に記載の判定基準にて評価し、試験結果を表２に示す。
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
 Test example 1 Algae killing test (green algae and cyanobacteria)
Using the green alga Chlorella vulgaris C-135 (hereinafter referred to as chlorella) and the cyanobacteria Microcystis aeruginosa Lemmermann NIES-44 (hereinafter referred to as microkitis), the algicidal effect of the algicidal and bactericidal agents of Examples and Comparative Examples Evaluated. Chlorella uses a pre-cultured solution in MDM medium with an absorbance of O.D. D. Dilute with distilled water so that the value at 420 is 0.5, and add HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid) to 50 mM to dissolve it. The pH was adjusted to 8.5 with caustic soda. Microcystis uses a CB medium pre-cultured solution with an absorbance of O.D. D. Dilute with distilled water so that the value at 440 is 0.5, add Bicine (N, N-bis (2-hydroxyethyl) glycine) to 100 mM and dissolve, and adjust the pH with caustic soda. Adjusted to 9.0. These were used as test solutions, and 10 ml of each was dispensed into L-shaped test tubes and placed in a light irradiation type shaking-constant water bath. The algicidal and bactericidal agents of Examples and Comparative Examples were respectively added so as to have a predetermined concentration as an effective chlorine concentration, and cultured under shaking at 30 ° C. and 10 KLx (light: 12 h, dark: 12 h) every other day. Visual observation was performed and observation was performed for 3 days. The algicidal effect of the algicidal / bactericidal agent is evaluated according to the criteria shown in Table 1, and the test results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
　表２の結果より、緑藻類であるクロレラや藍藻類のミクロキスティスに対して本発明のN－クロロ化合物及びN，N’－ジクロロ化合物（実施例１～７）は、他のN－クロロ化合物（比較例１、２）や遊離塩素（次亜塩素酸ナトリウム溶液、比較例３）と比較して、低濃度で高い殺藻効果を示した。特にアオコを構成する藍藻類であり、生物指標であるミクロキスティスに対して、本発明のN－クロロ及びN，N’－ジクロロ化合物が高い殺藻効果を示したことは非常に興味深い結果であった。 From the results shown in Table 2, the N-chloro compound and N, N′-dichloro compound of the present invention (Examples 1 to 7) were compared with other N-chloro compounds (Examples 1 to 7) against the green algae chlorella and cyanobacteria microkistis. Compared with Comparative Examples 1 and 2) and free chlorine (sodium hypochlorite solution, Comparative Example 3), it showed a high algicidal effect at a low concentration. In particular, it was a very interesting result that the N-chloro and N, N′-dichloro compounds of the present invention showed a high algicidal effect against microkistis, which is a cyanobacteria that constitutes the blue sea urchin and is a biological indicator. It was.
試験例２　殺菌力試験
　試験水として、某病院空調用冷却塔の冷却水を用いた。冷却水の水質を表３に示す。 Test Example 2 Bactericidal power test Cooling water from a cooling tower for air conditioning in Sakai Hospital was used as test water. Table 3 shows the quality of the cooling water.
　この冷却水をＬ字型試験管に１０ｍｌずつ分注し、実施例及び比較例で調製した各殺藻・殺菌剤を有効塩素濃度として所定濃度となるように添加して効力評価を行った。試験条件は、３０℃の恒温槽中で振盪培養し、薬剤添加1時間後及び６時間後の試験水中の一般細菌数を測定して行った。結果を表４に示す。表４中の薬剤添加量は有効塩素濃度で示した。
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
 10 ml each of this cooling water was dispensed into an L-shaped test tube, and each algicidal / bactericidal agent prepared in Examples and Comparative Examples was added so as to have a predetermined concentration as an effective chlorine concentration to evaluate the efficacy. The test conditions were carried out by shaking culture in a constant temperature bath at 30 ° C., and measuring the number of general bacteria in the test water 1 hour and 6 hours after the addition of the drug. The results are shown in Table 4. The amount of drug added in Table 4 is shown as effective chlorine concentration.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
　表４の結果より、本発明のN－クロロ及びN，N’－ジクロロ化合物は、低濃度で非常に優れた殺菌効果を示した。比較例１に示すスルファミン酸のN－クロロ化合物は、その殺菌効果は非常に弱く、添加1時間後では、比較例３の遊離塩素である次亜塩素酸ナトリウムよりも弱い効果しか示さず、６時間後でも低濃度の添加では殆ど効果を示さない結果であった。また、比較例２の１－クロロ－５，５－ジメチルヒダントインも高濃度添加ではある程度の殺菌効果を示すが、その効果は本発明の殺藻・殺菌剤と比較すると低い効果しか示さなかった。このことからも、本発明のN－クロロ及びN，N’－ジクロロ化合物は、結合型のN－クロロ化合物でありながら、低濃度でも速やかに殺菌効果を発揮することが示された。 From the results shown in Table 4, the N-chloro and N, N′-dichloro compounds of the present invention showed a very excellent bactericidal effect at a low concentration. The N-chloro compound of sulfamic acid shown in Comparative Example 1 has a very weak bactericidal effect, and after 1 hour of addition, it shows only a weaker effect than sodium hypochlorite, which is the free chlorine of Comparative Example 3. Even after the time, the addition of a low concentration showed almost no effect. Further, 1-chloro-5,5-dimethylhydantoin of Comparative Example 2 also showed a certain bactericidal effect when added at a high concentration, but the effect was only low compared with the algicidal / bactericidal agent of the present invention. This also indicates that the N-chloro and N, N'-dichloro compounds of the present invention exhibit a bactericidal effect quickly even at low concentrations, even though they are bound N-chloro compounds.
試験例３　金属腐食性
　蓋付きガラス製容器中にステンレス鋼ＳＵＳ３０４（片面＃４００研磨仕上、２．５×１５×５０ｍｍ）、鉄（ＳＳ－４００、２．３×１５×３０ｍｍ）及び銅（Ｃ１２２ＯＰ、２．０×２０×５０ｍｍ）の試験片を立て掛け、気相部と溶液浸積部とが形成できる位置にまで上水（静岡県磐田市市水）を所定量計り込み、実施例１及び３、比較例１及び３の殺藻・殺菌剤を有効塩素濃度として２．５ｍｇ／Ｌ及び５ｍｇ／Ｌとなるように添加し、３０℃下で試験片の腐食の程度を観察した。試験液は１週間に一度交換し、８週間後に試験片を取り出し、腐食度（ｇｍｄ；ｇ／ｍ２・ｄａｙ）を求め下表５のA～Eの判定基準による評価結果と、外観観察にて薬剤未添加区（上水のみ）での腐食程度に対して各殺藻・殺菌剤の腐食の程度を下表６の判定基準により評価した。結果を組み合わせた記号にて表７に示した。
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
 Test Example 3 Metal Corrosiveness Stainless steel SUS304 (single side # 400 polished finish, 2.5 × 15 × 50 mm), iron (SS-400, 2.3 × 15 × 30 mm) and copper (C122OP) in a glass container with a lid , 2.0 × 20 × 50 mm), a predetermined amount of clean water (Iwata City Shizuoka City water) is measured to a position where a gas phase portion and a solution immersion portion can be formed. 3. The algicidal and bactericidal agents of Comparative Examples 1 and 3 were added so that the effective chlorine concentration was 2.5 mg / L and 5 mg / L, and the degree of corrosion of the test piece was observed at 30 ° C. The test solution is changed once a week, and after 8 weeks, the test piece is taken out, and the degree of corrosion (gmd; g / m 2 · day) is obtained. The degree of corrosion of each algicide / bactericide was evaluated according to the criteria shown in Table 6 below with respect to the degree of corrosion in the non-agent-added section (only clean water). The results are shown in Table 7 in combination with symbols.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
　表７の結果より、本発明のN－クロロ及びN，N’－ジクロロ化合物は、比較例３の遊離塩素はもとより、比較例１のスルファミン酸のN－クロロ化合物と比較しても、鉄や銅への腐食性が低く、実用濃度では、上水（磐田市市水）での腐食程度と殆ど差がみられない結果であった。 From the results shown in Table 7, the N-chloro and N, N′-dichloro compounds of the present invention were found to be iron or iron in comparison with the free chlorine of Comparative Example 3 as well as the N-chloro compound of sulfamic acid of Comparative Example 1. The corrosiveness to copper was low, and the practical concentration showed almost no difference from the degree of corrosion in tap water (Iwata city water).
　本明細書で引用した全ての刊行物、特許および特許出願をそのまま参考として本明細書にとり入れるものとする。 All publications, patents and patent applications cited in this specification shall be incorporated into the present specification as they are.

Claims (19)

  1. 　Ｎ－クロロ－２－ピロリジノンを含有することを特徴とする殺藻剤。 An algicidal agent containing N-chloro-2-pyrrolidinone.
  2. 　水又は水と水溶性有機溶剤の混合溶液を更に含む、水溶性の液体製剤であることを特徴とする請求項１記載の殺藻剤。 The algicidal agent according to claim 1, which is a water-soluble liquid preparation further comprising water or a mixed solution of water and a water-soluble organic solvent.
  3. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上を含有することを特徴とする殺藻・殺菌剤。     Formula (I):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    Containing at least one selected from the group consisting of cyclic N-chloro compounds (excluding N-chloro-2-pyrrolidinone) and N, N′-dichloro compounds .
  4. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項３記載の殺藻・殺菌剤。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-heptalactam, N One selected from -chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone The algicide / bactericidal agent according to claim 3, which is as described above.
  5. 　水又は水と水溶性有機溶剤の混合溶液を更に含む、水溶性の液体製剤であることを特徴とする請求項３又は４記載の殺藻・殺菌剤。 The algicidal / bactericidal agent according to claim 3 or 4, which is a water-soluble liquid preparation further comprising water or a mixed solution of water and a water-soluble organic solvent.
  6. 　腐食が望まれない金属部材と接触している水系中に、式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000002
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上を含有する殺藻・殺菌剤を、残留塩素濃度（Ｃｌ２換算）として０．２～１０ｍｇ／Ｌとなるように添加する殺藻・殺菌方法。     In an aqueous system in contact with a metal member where corrosion is not desired, the formula (I):
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    An algicidal / bactericidal agent containing one or more selected from cyclic N-chloro compounds or N, N′-dichloro compounds represented by the formula: 0.2 to 10 mg / L as a residual chlorine concentration (Cl 2 conversion) Algae killing and sterilization method to be added.
  7. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピロリジノン、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項６記載の殺藻・殺菌方法。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-pyrrolidinone, N-chloro-2-piperidone, N-chloro-ε-caprolactam, N— Chloro-ω-heptalactam, N-chloro-2-imidazolidinone, N, N′-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N′-dichloro-tetrahydro- The algicidal / sterilizing method according to claim 6, wherein the method is one or more selected from 2-pyrimidinone.
  8. 　殺藻するためのＮ－クロロ－２－ピロリジノンの使用。 Use of N-chloro-2-pyrrolidinone to kill algae.
  9. 　Ｎ－クロロ－２－ピロリジノンを用いる殺藻方法。 Algae killing method using N-chloro-2-pyrrolidinone.
  10. 　殺藻剤の製造のためのＮ－クロロ－２－ピロリジノンの使用。 Use of N-chloro-2-pyrrolidinone for the production of algicide.
  11. 　Ｎ－クロロ－２－ピロリジノンを使用する殺藻剤の製造方法。 A method for producing an algicide using N-chloro-2-pyrrolidinone.
  12. 　殺藻・殺菌するための式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000003
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物の使用。     Formula (I) for algaecidal / sterilizing:
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    Use of one or more compounds selected from cyclic N-chloro compounds represented by the above (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds.
  13. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項１２記載の使用。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-heptalactam, N One selected from -chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone Use according to claim 12, characterized by the above.
  14. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000004
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物を用いる殺藻・殺菌方法。     Formula (I):
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    An algicidal / sterilizing method using at least one compound selected from the group consisting of cyclic N-chloro compounds (excluding N-chloro-2-pyrrolidinone) and N, N′-dichloro compounds.
  15. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項１４記載の殺藻・殺菌方法。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-heptalactam, N One selected from -chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone It is the above, The algicide / sterilization method of Claim 14 characterized by the above-mentioned.
  16. 　殺藻・殺菌剤の製造のための
    　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000005
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物の使用。     Formula (I) for the production of algaecides and fungicides:
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    Use of one or more compounds selected from cyclic N-chloro compounds represented by the above (excluding N-chloro-2-pyrrolidinone) or N, N′-dichloro compounds.
  17. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項１６記載の使用。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-heptalactam, N One selected from -chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone Use according to claim 16, characterized by the above.
  18. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000006
     （式中のＸはメチレン基、二級アミノ基又はＮ－クロロ基を表し、Ｒは炭素原子数が２～５のアルキレン基を示す。但し、ＸがＮ－クロロ基のときＲは炭素原子数が２～３のアルキレン基である。）
    で表される環状のＮ－クロロ化合物（但し、Ｎ－クロロ－２－ピロリジノンを除く）又はＮ，Ｎ’－ジクロロ化合物から選ばれる１種以上の化合物を使用する、殺藻・殺菌剤の製造方法。     Formula (I):
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, X represents a methylene group, a secondary amino group or an N-chloro group, R represents an alkylene group having 2 to 5 carbon atoms, provided that when X is an N-chloro group, R represents a carbon atom. It is an alkylene group having 2 to 3 numbers.)
    Or a fungicide using at least one compound selected from the group consisting of cyclic N-chloro compounds (excluding N-chloro-2-pyrrolidinone) and N, N′-dichloro compounds Method.
  19. 　式（Ｉ）で表される環状のＮ－クロロ化合物又はＮ，Ｎ’－ジクロロ化合物が、Ｎ－クロロ－２－ピペリドン、Ｎ－クロロ－ε－カプロラクタム、Ｎ－クロロ－ω－ヘプタラクタム、Ｎ－クロロ－２－イミダゾリジノン、Ｎ，Ｎ’－ジクロロ－２－イミダゾリジノン、Ｎ－クロロ－テトラヒドロ－２－ピリミジノン、及びＮ，Ｎ’－ジクロロ－テトラヒドロ－２－ピリミジノンから選ばれる１種以上であることを特徴とする請求項１８記載の製造方法。 The cyclic N-chloro compound or N, N′-dichloro compound represented by the formula (I) is N-chloro-2-piperidone, N-chloro-ε-caprolactam, N-chloro-ω-heptalactam, N One selected from -chloro-2-imidazolidinone, N, N'-dichloro-2-imidazolidinone, N-chloro-tetrahydro-2-pyrimidinone, and N, N'-dichloro-tetrahydro-2-pyrimidinone The manufacturing method according to claim 18, which is as described above.
PCT/JP2011/080039 2011-01-07 2011-12-26 Algicidal/microbicidal agent and algicidal/microbicidal method WO2012093608A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180064265.2A CN103298340B (en) 2011-01-07 2011-12-26 Kill algae-bactericide and kill algae-method for disinfection
KR20137016670A KR20130141624A (en) 2011-01-07 2011-12-26 Algicidal/microbicidal agent and algicidal/microbicidal method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011002059A JP5643117B2 (en) 2011-01-07 2011-01-07 Algae killing agent and alga killing method
JP2011-002059 2011-01-07

Publications (1)

Publication Number Publication Date
WO2012093608A1 true WO2012093608A1 (en) 2012-07-12

Family

ID=46457467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/080039 WO2012093608A1 (en) 2011-01-07 2011-12-26 Algicidal/microbicidal agent and algicidal/microbicidal method

Country Status (5)

Country Link
JP (1) JP5643117B2 (en)
KR (1) KR20130141624A (en)
CN (1) CN103298340B (en)
TW (1) TW201309198A (en)
WO (1) WO2012093608A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104336070A (en) * 2014-10-20 2015-02-11 山东华亚环保科技有限公司 Disinfection and algae killing agent for oil field water delivery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3591601A (en) * 1967-10-30 1971-07-06 Dow Chemical Co N-chloro or bromo-2-oxazolidinones
US3749672A (en) * 1971-04-19 1973-07-31 Du Pont Stabilized solutions of n-halo compounds
JPS63101498A (en) * 1986-10-17 1988-05-06 ライオン株式会社 Bleaching detergent composition
WO1996011882A1 (en) * 1994-10-14 1996-04-25 Lonza Inc. Hydantoin-enhanced halogen efficacy in pulp and paper applications
JP2002363016A (en) * 2001-05-31 2002-12-18 Hakuto Co Ltd Microorganism-controlling agent
JP2003261517A (en) * 2002-03-11 2003-09-19 K I Chemical Industry Co Ltd New dibromonitro compound and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB868876A (en) * 1958-05-05 1961-05-25 Montedison Spa A method of preparing compounds containing the groupingí¬nclí¬coí¬nclí¬ in a ring
US3850920A (en) * 1967-10-30 1974-11-26 Dow Chemical Co N-halo-3-morpholinone
US4492619A (en) * 1984-02-01 1985-01-08 Phan Xuan T Photochemical process for preparing alkoxy substituted compounds
US4681948A (en) * 1986-03-31 1987-07-21 Ppg Industries, Inc. N,N'dihalo-2-imidazolidinones

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3591601A (en) * 1967-10-30 1971-07-06 Dow Chemical Co N-chloro or bromo-2-oxazolidinones
US3749672A (en) * 1971-04-19 1973-07-31 Du Pont Stabilized solutions of n-halo compounds
JPS63101498A (en) * 1986-10-17 1988-05-06 ライオン株式会社 Bleaching detergent composition
WO1996011882A1 (en) * 1994-10-14 1996-04-25 Lonza Inc. Hydantoin-enhanced halogen efficacy in pulp and paper applications
JP2002363016A (en) * 2001-05-31 2002-12-18 Hakuto Co Ltd Microorganism-controlling agent
JP2003261517A (en) * 2002-03-11 2003-09-19 K I Chemical Industry Co Ltd New dibromonitro compound and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104336070A (en) * 2014-10-20 2015-02-11 山东华亚环保科技有限公司 Disinfection and algae killing agent for oil field water delivery

Also Published As

Publication number Publication date
JP5643117B2 (en) 2014-12-17
CN103298340A (en) 2013-09-11
CN103298340B (en) 2016-03-30
KR20130141624A (en) 2013-12-26
TW201309198A (en) 2013-03-01
JP2012144451A (en) 2012-08-02

Similar Documents

Publication Publication Date Title
US5057612A (en) N,n'-dihaloimidazolidin-4-ones
US5126057A (en) Disinfecting with N,N'-dihaloimidazolidin-4-ones
AU2001258644B2 (en) Treatment of circulating water systems
JPS62230770A (en) N, n'-dihalo-2-imidazolidinone
AU2001258644A1 (en) Treatment of circulating water systems
JP2003146817A (en) Antimicrobial algicidal agent composition, method for killing microbe and alga in water system and method for producing antimicrobial algicidal agent composition
KR960013330B1 (en) Method for the control of biofouling in recirculating water systems
JP5643117B2 (en) Algae killing agent and alga killing method
JP3814085B2 (en) Algae control agent and algae control method
JP4475920B2 (en) Microbial control agent and microorganism control method
US10793586B2 (en) Quaternary ammonium etidronates
JPS60204704A (en) Synergistic composition containing hydroxypropyl methane sulfonate and use
JP4748773B2 (en) Disinfectant algicide having ability to prevent discoloration and discoloration prevention method
JP2006232687A (en) Biofilm formation inhibitor in circulating water system and method of inhibiting formation of biofilm
JP3916216B2 (en) Novel dibromonitroalcohol derivatives and their uses
JP4297473B2 (en) Antibacterial and algae agent and method
US20150045223A1 (en) Biocidal compositions and their use in the control of microorganisms in aqueous and water containing systems
JP4296565B2 (en) Hydantoin-containing composition and use thereof
US20220024865A1 (en) Cluster compounds and methods of making the same
WO2023118170A1 (en) Antimicrobial system and method
JP5211274B2 (en) Triazine preparation and aqueous preparation thereof
JP2002161007A (en) Algicide
CN103945698A (en) Antimicrobial composition of ortho phenylphenol and silver
JPH10139603A (en) Industrial antimicrobial
Williams et al. A New Solid Isothiazolone Biocide For Industrial Water Treatment

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180064265.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11855042

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20137016670

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1301003799

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11855042

Country of ref document: EP

Kind code of ref document: A1