JP6246023B2 - Harmful microorganism eradication agent and harmful microorganism eradication method using the same - Google Patents
Harmful microorganism eradication agent and harmful microorganism eradication method using the same Download PDFInfo
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- 244000005700 microbiome Species 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 30
- 230000008029 eradication Effects 0.000 title claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 24
- 229940091173 hydantoin Drugs 0.000 claims description 19
- 150000003868 ammonium compounds Chemical class 0.000 claims description 17
- -1 Hydantoin compound Chemical class 0.000 claims description 15
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000007788 liquid Substances 0.000 description 29
- 230000000844 anti-bacterial effect Effects 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 9
- 241000233866 Fungi Species 0.000 description 8
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 150000001469 hydantoins Chemical class 0.000 description 4
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 4
- 238000003911 water pollution Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VSJRBQDMBFFHMC-UHFFFAOYSA-N 5-ethyl-5-methylimidazolidine-2,4-dione Chemical compound CCC1(C)NC(=O)NC1=O VSJRBQDMBFFHMC-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- PQRDTUFVDILINV-UHFFFAOYSA-N bcdmh Chemical compound CC1(C)N(Cl)C(=O)N(Br)C1=O PQRDTUFVDILINV-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002538 fungal effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229960005322 streptomycin Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SSSAHVJVVZSZQL-UHFFFAOYSA-N 1-bromo-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Br)C(=O)NC1=O SSSAHVJVVZSZQL-UHFFFAOYSA-N 0.000 description 1
- UWMJRBYGKZOPCC-UHFFFAOYSA-N 1-chloro-5,5-dimethylimidazolidine-2,4-dione Chemical group CC1(C)N(Cl)C(=O)NC1=O UWMJRBYGKZOPCC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- DPPLHBYXNCZPLR-UHFFFAOYSA-N imidazolidine-2,4-dione;hydrobromide Chemical compound Br.O=C1CNC(=O)N1 DPPLHBYXNCZPLR-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、水溶液中の有害微生物撲滅剤及び撲滅方法、特に製紙工程において使用される洗浄水や冷却水などの処理水又は白水に添加して、その中に含まれているスライム発生の原因となる有害微生物がスライムを形成することで発生する各種トラブルを抑制するための有害微生物撲滅剤及びそれを用いる有害微生物撲滅方法に関するものである。 The present invention adds harmful microorganism eradication agents and eradication methods in aqueous solutions, particularly treated water such as washing water and cooling water used in the papermaking process, or white water, and causes slime generation contained therein. The present invention relates to a harmful microorganism eradicating agent for suppressing various troubles caused by the formation of slime by harmful microorganisms and a method for eradicating harmful microorganisms using the same.
製紙工程で使用される洗浄水や冷却水などの被処理水には、原料の木材に由来するセルロース、リグニン、へミセルロース、多糖類などの有機物を栄養源として、多数の微生物が繁殖し、これらがパイプラインやピットの壁面に付着してスライムを形成する。そして、このスライムは、紙切れを引き起したり、紙の上に斑点を生じるため、生産効率の低下や製品の品質劣化の原因となっている。 In treated water such as washing water and cooling water used in the papermaking process, a large number of microorganisms are propagated using organic substances such as cellulose, lignin, hemicellulose, and polysaccharides derived from the raw wood as nutrients, These adhere to the wall of the pipeline or pit to form slime. And since this slime causes a piece of paper or a spot on the paper, it causes a reduction in production efficiency and product quality.
このようなスライム障害を防止するために、これまでに酸化剤とアンモニウム化合物とからなる多くのスライムコントロール剤や、これを用いるスライムコントロール方法が提案されている。例えば、アンモニウムイオンを含む冷却水中に、次亜塩素酸又はその塩１モルとヒダントイン又はその誘導体１〜２モルをあらかじめ混合して添加する冷却水系の運転方法（特許文献１参照）、塩素濃度に換算して０．１〜２．０％の次亜塩素酸ナトリウム又は次亜塩素酸カルシウムの希釈液と、濃度０．１〜６．０％のアミン源の希釈液とを同期的に計量して管路内に供給し、あらかじめ定められた比率で、上記管路内で連続的に混合して、その場で殺生物有効成分を製造しながら被処理液中へ連続的に注入する液体中の微生物の増殖を抑制する方法（特許文献２参照）、水中で、液状又はスラリー状の臭化ヒダントインと硫酸アンモニウムを混合して得られる循環水系におけるバイオフィルムの形成抑制剤を用いる方法（特許文献３参照）、次亜塩素酸ナトリウム希釈水と、無機系臭素化合物又は５，５−ジメチルヒダントインとを混合してスライムコントロール剤を製造し、１０秒以内に被処理水に添加するスライムコントロール剤の添加方法（特許文献４参照）、ブロモクロロジメチルヒダントインと水溶性セルロース誘導体とを混合したものに、硫酸アンモニウムを混合し、ただちに被処理水に添加する微生物の殺滅方法（特許文献５参照）、ブロモクロロジメチルヒダントインと多糖類高分子とを混合したものに、硫酸アンモニウムを混合し、ただちに被処理水に添加する微生物の殺滅方法（特許文献６参照）、次亜塩素酸ナトリウムと硫酸アンモニウムを組み合わせたもの（特許文献７参照）などが提案されている。 In order to prevent such slime failure, many slime control agents composed of an oxidizing agent and an ammonium compound and slime control methods using the same have been proposed. For example, in a cooling water containing ammonium ions, 1 mol of hypochlorous acid or a salt thereof and 1 to 2 mol of hydantoin or a derivative thereof are mixed and added in advance (see Patent Document 1). In conversion, 0.1 to 2.0% sodium hypochlorite or calcium hypochlorite diluted solution and 0.1 to 6.0% amine source diluted solution are weighed synchronously. In a liquid that is continuously injected into the liquid to be treated while producing biocidal active ingredients on the spot by continuously mixing in the pipe at a predetermined ratio. A method of suppressing the growth of microorganisms (see Patent Document 2), a method of using a biofilm formation inhibitor in a circulating water system obtained by mixing liquid or slurry hydantoin bromide and ammonium sulfate in water (Patent Document 3) reference A method for adding a slime control agent comprising mixing sodium hypochlorite-diluted water with an inorganic bromine compound or 5,5-dimethylhydantoin to produce a slime control agent and adding it to the water to be treated within 10 seconds ( Patent Document 4), a method of killing microorganisms (see Patent Document 5) in which ammonium sulfate is mixed with a mixture of bromochlorodimethylhydantoin and a water-soluble cellulose derivative, and immediately added to the water to be treated (see Patent Document 5), bromochlorodimethylhydantoin A method of killing microorganisms (see Patent Document 6), which is a mixture of a polymer and a polysaccharide polymer, mixed with ammonium sulfate and immediately added to the water to be treated (Patent Document 6) 7) is proposed.
しかしながら、アミン成分としてアンモニウム化合物を用いない場合は、これを用いた場合に比べ、殺菌力が低下し、スライムトラブルが発生するのを免れないが、このアンモニウム化合物は水質汚濁防止法により排水・貯蔵管理が必要な化合物であるため、作業環境によりその使用が制限される傾向にある。このため、アンモニウム化合物を使用しないでスライム障害を防止する方法として、例えば、次亜臭素酸及び／又はその水溶性塩とＮ−モノクロロ−５，５−ジアルキル置換ヒダントインを生成させることを特徴とする水系におけるスライムコントロール方法（特許文献８参照）や塩素化ヒダントインを特定量用いたバイオフィルムの除去のための方法（特許文献９参照）が提案されている。 However, when an ammonium compound is not used as an amine component, the bactericidal activity is reduced and slime troubles are unavoidable compared to the case where it is used, but this ammonium compound is drained and stored by the Water Pollution Control Law. Since it is a compound that needs to be managed, its use tends to be limited by the working environment. Therefore, as a method for preventing slime damage without using an ammonium compound, for example, hypobromous acid and / or a water-soluble salt thereof and N-monochloro-5,5-dialkyl-substituted hydantoin are produced. A slime control method in an aqueous system (see Patent Document 8) and a method for removing a biofilm using a specific amount of chlorinated hydantoin (see Patent Document 9) have been proposed.
前記特許文献８のスライムコントロール方法は用いるヒダントイン水溶液のｐＨは調整しているものの、ｐＨ７以上としている。また特許文献９のバイオフィルムの除去のための方法では単にハロゲン化ヒダントインを添加するか、ヒダントインおよびハロゲン化剤とを適切なモル比で別々に水システムを含むバイオフィルムに添加することによりバイオフィルムの除去を行なっているため、いずれもこれまでのアンモニウム化合物を用いるスライムコントロール剤に比べ殺菌効果の面で未だ満足できるものではなかった。 Although the pH of the hydantoin aqueous solution used in the slime control method of Patent Document 8 is adjusted, it is set to pH 7 or higher. In addition, in the method for removing a biofilm of Patent Document 9, a biofilm is obtained by simply adding a halogenated hydantoin or separately adding a hydantoin and a halogenating agent to a biofilm containing a water system at an appropriate molar ratio. Therefore, none of them was still satisfactory in terms of bactericidal effect as compared with the slime control agents using ammonium compounds so far.
本発明は、従来の次亜塩素酸塩とアンモニウム化合物とを有効成分とする有害微生物撲滅剤と同等の殺菌効果を有し、しかも水質汚濁防止法によりアンモニウム化合物の使用を制限される分野においても使用することが可能な有害微生物撲滅剤及びそれを用いた有害微生物撲滅方法を提供することを課題とする。 The present invention has a bactericidal effect equivalent to that of a conventional harmful microorganism eradicating agent containing hypochlorite and an ammonium compound as active ingredients, and is also used in fields where the use of ammonium compounds is restricted by the water pollution control method. It is an object of the present invention to provide a harmful microorganism eradication agent that can be used and a harmful microorganism eradication method using the same.
本発明者等は、上記の課題を解決するために鋭意検討した結果、次亜塩素酸塩や次亜臭素酸塩を含有する水溶液とヒダントイン含有水溶液とを特定の配合割合としたり、ｐＨ７以上のヒダントイン系化合物含有水溶液を用いる方法では、前記課題を解決することができないことに鑑み、ヒダントイン系化合物含有水溶液のｐＨを調整し、この水溶液と次亜ハロゲン酸塩を含有する水溶液とを混合した有害微生物撲滅剤のｐＨを６以上７未満とすることにより、従来のアンモニウム化合物を用いたスライムコントロール剤と同等の殺菌効果が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors made an aqueous solution containing hypochlorite or hypobromite and an aqueous solution containing hydantoin into a specific blending ratio or a pH of 7 or more. In view of the fact that the above-mentioned problem cannot be solved by the method using a hydantoin compound-containing aqueous solution, the pH of the hydantoin compound-containing aqueous solution is adjusted, and this aqueous solution and an aqueous solution containing a hypohalite are mixed. It has been found that by setting the pH of the microorganism eradicating agent to 6 or more and less than 7, a bactericidal effect equivalent to that of a conventional slime control agent using an ammonium compound can be obtained, and the present invention has been completed.
即ち、本発明は以下の有害微生物撲滅剤及び有害微生物撲滅方法を提供するものである。 That is, the present invention provides the following harmful microorganism eradication agent and harmful microorganism eradication method.
（１）（Ａ）次亜ハロゲン酸塩、（Ｂ）一般式で表されるヒダントイン系化合物（式中のＲ１、Ｒ２はそれぞれ独立して、炭素数１〜４の低級アルキル基、Ｘ及びＹは水素原子、塩素原子及び臭素原子から選ばれる少なくとも１種である）を含有し、かつ、アンモニウム化合物を含有しない水溶液からなる有害微生物撲滅剤であって、該有害微生物撲滅剤のｐＨが６以上７未満の範囲であり、該（Ａ）成分と該（Ｂ）成分との配合比がモル比として３：２〜５：１の範囲であることを特徴とする有害微生物撲滅剤。
（２）前記（Ａ）成分を含有する水溶液と、前記（Ｂ）成分を含有する水溶液とを混合したものである（１）に記載の有害微生物撲滅剤。 (2) The harmful microorganism eradication agent according to (1), wherein the aqueous solution containing the component (A) and the aqueous solution containing the component (B) are mixed.
（３）前記（Ａ）成分が次亜塩素酸ナトリウム及び／または次亜臭素酸ナトリウムである（１）または（２）に記載の有害微生物撲滅剤。 (3) The harmful microorganism eradication agent according to (1) or (2), wherein the component (A) is sodium hypochlorite and / or sodium hypobromite.
（４）（Ａ）次亜ハロゲン酸塩を含有する水溶液と、（Ｂ）一般式で表されるヒダントイン系化合物（式中のＲ１、Ｒ２はそれぞれ独立して、炭素数１〜４の低級アルキル基、Ｘ及びＹは水素原子、塩素原子及び臭素原子から選ばれる少なくとも１種である）を含有し、該（Ａ）成分と混合後のｐＨを６以上７未満の範囲になるように調整した水溶液とを混合後、水系に添加する殺菌方法であって、該（Ａ）成分を含有する水溶液と該（Ｂ）成分を含有する水溶液の双方にアンモニウム化合物を含有せず、かつ、該（Ａ）成分と該（Ｂ）成分の配合比がモル比として３：２〜５：１の割合で混合することを特徴とする殺菌方法。
本発明の有害微生物撲滅剤は、（Ａ）次亜ハロゲン酸塩、（Ｂ）ヒダントイン系化合物を含有し、かつ、アンモニウム化合物を含有しない水溶液からなるものであり、この有害微生物撲滅剤のｐＨが６以上７未満の範囲であり、該（Ａ）成分と該（Ｂ）成分との配合比がモル比として３：２〜５：１の範囲であるものである。 The harmful microorganism eradication agent of the present invention comprises an aqueous solution containing (A) a hypohalite and (B) a hydantoin compound and not containing an ammonium compound , and the pH of the harmful microorganism eradication agent is It is a range of 6 or more and less than 7, and the mixing ratio of the component (A) and the component (B) is in the range of 3: 2 to 5: 1 as a molar ratio .
本発明の有害微生物撲滅剤は、（Ａ）次亜ハロゲン酸塩を含有する水溶液からなる第一液と、（Ｂ）ヒダントイン系化合物を含有する水溶液からなる第二液のｐＨを調整し、この第一液と第二液とを混合した有害微生物撲滅剤のｐＨが６以上７未満の範囲であるものが好ましい。 The harmful microorganism eradication agent of the present invention adjusts the pH of (A) a first liquid comprising an aqueous solution containing a hypohalite and (B) a second liquid comprising an aqueous solution containing a hydantoin compound. What has the pH of the harmful microorganism eradication agent which mixed the 1st liquid and the 2nd liquid is the range of 6-6 is preferable.
前記（Ａ）次亜ハロゲン酸塩とは、次亜塩素酸、次亜臭素酸などのアルカリ金属（ナトリウム、カリウムなど）もしくはアルカリ土類金属（カルシウム、バリウムなど）塩のことであり、代表的な物として次亜塩素酸ナトリウム、次亜臭素酸ナトリウム、次亜塩素酸カリウム、次亜臭素酸カリウムおよび次亜塩素酸カルシウム等が挙げられる。
これらの中で特に次亜塩素酸ナトリウムや次亜臭素酸ナトリウムが好ましい。このものは、一般に１０〜２０質量％水溶液として市販されているので、これを工業用水又は水道水により所定の濃度に希釈して用いるのが有利であり、特に（Ｂ）成分として用いられるヒダントイン系化合物との反応性やその制御の容易さを考慮して有効塩素として０．０５〜２％程度に希釈するのがよい。
The (A) hypohalite is an alkali metal (sodium, potassium, etc.) or alkaline earth metal (calcium, barium, etc.) salt such as hypochlorous acid and hypobromite, and is representative. Examples of such substances include sodium hypochlorite, sodium hypobromite, potassium hypochlorite, potassium hypobromite and calcium hypochlorite.
Of these, sodium hypochlorite and sodium hypobromite are particularly preferable. Since this is generally marketed as a 10 to 20% by mass aqueous solution, it is advantageous to dilute it to a predetermined concentration with industrial water or tap water, and in particular it is a hydantoin system used as component (B). In consideration of the reactivity with the compound and the ease of control thereof, it is preferable to dilute to about 0.05 to 2% as effective chlorine.
前記（Ｂ）ヒダントイン系化合物とは、一般式
この化合物としては、式中のＲ１、Ｒ２がそれぞれメチル基、Ｘ、Ｙがそれぞれ水素原子である５，５−ジメチルヒダントインや、Ｒ１、Ｒ２がそれぞれメチル基、Ｘが塩素原子、Ｙが水素原子であるクロロジメチルヒダントイン、Ｒ１、Ｒ２がそれぞれメチル基、Ｘが臭素原子、Ｙが水素原子であるブロモジメチルヒダントイン、Ｒ１がメチル基、Ｒ２がエチル基、Ｘ、Ｙがそれぞれ水素原子である５メチル５エチルヒダントイン等が挙げられる。このヒダントイン系化合物は、微生物活性が失活するのを抑制する安定剤としての役割を果すと同時に、殺菌効果を高める作用を有する。
前記（Ｂ）成分を含有する水溶液を塩酸、硫酸、臭化水素、ヨウ化水素、硝酸、リン酸、酢酸、イソシアン酸、イソシアヌル酸、スルファミン酸などの酸性水溶液等を用いて第一液との混合後のｐＨを６以上７未満に調整することが重要である。従来からヒダントイン系化合物を用いる際には、水酸化ナトリウム、水酸化カリウムのような水酸化アルカリ金属の水溶液として用いられている。その際の水溶液のｐＨは７以上であり、次亜塩素酸ナトリウム等と混合後においてもそのｐＨは７以上とするように調整されており、このようなｐＨに調整することで安定な水溶液とすることができる。本発明では、（Ｂ）成分含有第二液のｐＨを７未満に調整し、かつ前記（Ａ）成分含有第一液との混合後のｐＨを６以上７未満とすることで従来よりもハロゲンをより活性化させることが可能となり、従来のアンモニウム化合物を用い、アンモニウムイオンから生成されるクロラミンを有効成分とする殺菌剤と同等の殺菌効果を得ることができる。
The (B) hydantoin compound is a general formula.
As this compound, R 1 and R 2 in the formula are each a methyl group, X and Y are each a hydrogen atom, 5,5-dimethylhydantoin, R 1 and R 2 are each a methyl group, X is a chlorine atom, Chlorodimethylhydantoin where Y is a hydrogen atom, R 1 and R 2 are each a methyl group, X is a bromine atom, Y is a bromodimethylhydantoin where Y is a hydrogen atom, R 1 is a methyl group, R 2 is an ethyl group, X, Y And 5-methyl-5-ethyl hydantoin, each of which is a hydrogen atom. This hydantoin compound plays a role as a stabilizer that suppresses the inactivation of microbial activity, and at the same time has an action of enhancing the bactericidal effect.
The aqueous solution containing the component (B) is mixed with the first solution using an acidic aqueous solution such as hydrochloric acid, sulfuric acid, hydrogen bromide, hydrogen iodide, nitric acid, phosphoric acid, acetic acid, isocyanic acid, isocyanuric acid, sulfamic acid, etc. It is important to adjust the pH after mixing to 6 or more and less than 7. Conventionally, when hydantoin compounds are used, they are used as an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The pH of the aqueous solution at that time is 7 or more, and the pH is adjusted to 7 or more even after mixing with sodium hypochlorite or the like. By adjusting to such pH, can do. In the present invention, the pH of the (B) component-containing second liquid is adjusted to less than 7, and the pH after mixing with the (A) component-containing first liquid is set to 6 or more and less than 7, so that Can be activated, and a bactericidal effect equivalent to a bactericidal agent containing chloramine produced from ammonium ions as an active ingredient can be obtained using a conventional ammonium compound.
前記（Ａ）成分と（Ｂ）成分との配合割合はモル比で１：２ないし５：１の範囲である。（Ａ）成分の配合割合がこの範囲より少ないと殺菌効果が得られにくくなり、この範囲を超えると使用量に見合う殺菌効果が得られにくくなるので好ましくない。特に好ましい配合割合は３：２ないし５：２である。 The blending ratio of the component (A) and the component (B) is in the range of 1: 2 to 5: 1 in molar ratio. When the blending ratio of the component (A) is less than this range, the bactericidal effect is difficult to obtain, and when it exceeds this range, the bactericidal effect commensurate with the amount used is difficult to obtain. A particularly preferable blending ratio is 3: 2 to 5: 2.
本発明の有害微生物撲滅剤を用いて、被処理水中の有害微生物を撲滅するには、第一液と第二液とを、第一液中の次亜塩素酸イオンと第二液中のヒダントイン系化合物のモル比が１：２ないし５：１になる割合で混合後、被処理水に添加するのが好ましい。 In order to eradicate harmful microorganisms in water to be treated using the harmful microorganism eradication agent of the present invention, the first liquid and the second liquid are mixed with hypochlorite ions in the first liquid and hydantoin in the second liquid. It is preferable to add to the water to be treated after mixing at a molar ratio of the system compound of 1: 2 to 5: 1.
この場合、第一液と第二液とは、ほぼ同じ濃度の水溶液として混合するのが普通であるが、所望に応じ第一液及び第二液の一方を高濃度水溶液とし、他方を希薄水溶液として、混合時に希薄水溶液中に高濃度水溶液を注入して、所要の濃度の第一液及び第二液を含む混合溶液とすることもできる。 In this case, the first liquid and the second liquid are usually mixed as an aqueous solution having substantially the same concentration. If desired, one of the first liquid and the second liquid is a high-concentration aqueous solution, and the other is a dilute aqueous solution. As described above, a high-concentration aqueous solution can be injected into a dilute aqueous solution at the time of mixing to obtain a mixed solution containing a first liquid and a second liquid having a required concentration.
本発明方法により、処理することができる被処理水としては、例えば、工業用水、工業用冷却水、工業用洗浄水、各種抄紙用工程水、製紙工程で生じる白水などが挙げられる。
白水は、水に再生パルプやバージンパルプなどのパルプ繊維、炭酸カルシウム、ホワイトカーボン、タルクなどの填料、硫酸バンド、サイズ剤、紙力剤、歩留り剤、凝結剤などの製紙用助剤を添加し、混合、撹拌したものである。
Examples of water to be treated that can be treated by the method of the present invention include industrial water, industrial cooling water, industrial washing water, various papermaking process water, and white water produced in the papermaking process.
For white water, pulp fibers such as recycled pulp and virgin pulp, fillers such as calcium carbonate, white carbon and talc, sulfuric acid bands, sizing agents, paper strength agents, retention agents, and coagulants are added to paper making aids. , Mixed and stirred.
本発明は、次亜ハロゲン酸塩と、特定のヒダントイン系化合物を含有しｐＨを６以上７未満の範囲に調整した水溶液を有害微生物撲滅剤として用いることにより、従来のアンモニウム化合物を用いたスライムコントロール剤と同等の殺菌効果を有し、しかも水質汚濁防止法により排水・貯蔵管理が必要な化合物を用いないため、作業環境を選ばず使用することができるという効果を有する。 The present invention provides a slime control using a conventional ammonium compound by using a hypohalite and an aqueous solution containing a specific hydantoin compound and having a pH adjusted in the range of 6 or more and less than 7 as a harmful microorganism eradicating agent. It has the same bactericidal effect as an agent and does not use a compound that requires drainage / storage management according to the Water Pollution Control Law, so that it can be used regardless of the working environment.
次に、実施例によって本発明を実施するための形態を説明する。
実施例１
Next, the form for implementing this invention by an Example is demonstrated.
Example 1
循環型調湿機を用いて、Ａ工場塗工原紙抄紙機より採取した白水［細菌数（ＣＦＵ）２．８×１０６，真菌数２４］５０ｍｌを３７℃に加温する。
別に、５℃に保持した工業用水中に１４質量％濃度の次亜塩素酸ナトリウム水溶液を加え、活性塩素量に換算して濃度２８００ｐｐｍの次亜塩素酸ナトリウム希釈水溶液を調製し、第一液とした。
次いで、次亜塩素酸ナトリウムの次亜塩素酸イオンに対し０．５モルとなるように５，５−ジメチルヒダントインを含有する水溶液を調製し第二液とした。この第二液に１Ｎ塩酸１６０μｌ／１００ｍｌを混合後、第一液と第二液とを混合し５秒間反応させｐＨ６．２の有害微生物撲滅剤を得た。この有害微生物撲滅剤を上記の白水中へ５，５−ジメチルヒダントインが６ｐｐｍとなる量を添加し、よく混合した。次いで５分経過後、白水の一部を採取し、常法により混釈平板培養を行い、発生したコロニー数から白水中の微生物数を計測した。なお、細菌数の計測培地としてはワックスマン寒天培地を、真菌数の計測培地としてはストレプトマイシンを加えたワックスマン寒天培地を使用した。
この結果を表１に示す。
実施例２
Using a circulation-type humidity controller, 50 ml of white water [bacterial count (CFU) 2.8 × 10 6 , fungal count 24] collected from the A-coated coated base paper machine is heated to 37 ° C.
Separately, a 14% strength by weight sodium hypochlorite aqueous solution is added to industrial water maintained at 5 ° C. to prepare a sodium hypochlorite diluted aqueous solution having a concentration of 2800 ppm in terms of the amount of active chlorine, did.
Next, an aqueous solution containing 5,5-dimethylhydantoin was prepared so as to be 0.5 mol with respect to hypochlorite ion of sodium hypochlorite, and used as the second liquid. After mixing 160 μl / 100 ml of 1N hydrochloric acid with this second liquid, the first liquid and the second liquid were mixed and reacted for 5 seconds to obtain a harmful microorganism eradication agent having a pH of 6.2. This harmful microorganism eradicating agent was added to the above white water in an amount such that 5,5-dimethylhydantoin was 6 ppm and mixed well. Then, after 5 minutes, a part of white water was collected and subjected to pour plate culture by a conventional method, and the number of microorganisms in white water was counted from the number of colonies generated. Waxman agar medium was used as the medium for measuring the number of bacteria, and Waxman agar medium supplemented with streptomycin was used as the medium for measuring the number of fungi.
The results are shown in Table 1.
Example 2
実施例１において、５，５−ジメチルヒダントインの代わりに、５メチル５エチルヒダントインを用いた以外は全て実施例１と同様にし、ｐＨ６．２の有害微生物撲滅剤とした。この時の白水中の微生物数及び真菌数を表１に示す。
比較例１
In Example 1, in place of 5,5-dimethylhydantoin, except that 5 methyl 5-ethylhydantoin was used, all was performed in the same manner as in Example 1 to obtain a harmful microorganism eradication agent of pH 6.2. The numbers of microorganisms and fungi in white water at this time are shown in Table 1.
Comparative Example 1
実施例１において、５，５−ジメチルヒダントインを用いず、次亜塩素酸ナトリウムの配合割合を６ｐｐｍとなるように白水に添加した以外は全て実施例１と同様にし、ｐＨ７．２の有害微生物撲滅剤とした。この時の白水中の微生物数及び真菌数を表１に示す。
比較例２
Example 1 eliminates harmful microorganisms having a pH of 7.2 in the same manner as in Example 1 except that 5,5-dimethylhydantoin is not used and sodium hypochlorite is added to white water so that the blending ratio is 6 ppm. An agent was used. The numbers of microorganisms and fungi in white water at this time are shown in Table 1.
Comparative Example 2
実施例１において、５，５−ジメチルヒダントインの代わりに１５％硫酸アンモニウムをアンモニウムイオンが次亜塩素酸イオンに対し０．５モルとなるようにした水溶液を用いた以外は全て実施例１と同様にし、ｐＨ７．２の有害微生物撲滅剤とした。この時の白水中の微生物数及び真菌数を表１に示す。
比較例３
In Example 1, instead of 5,5-dimethylhydantoin, all was carried out in the same manner as in Example 1 except that an aqueous solution in which 15% ammonium sulfate was used so that the ammonium ion was 0.5 mol with respect to hypochlorite ion was used. , To eliminate harmful microorganisms having a pH of 7.2. The numbers of microorganisms and fungi in white water at this time are shown in Table 1.
Comparative Example 3
実施例１において、次亜塩素酸ナトリウムの次亜塩素酸イオンに対し等モルとなるように５，５−ジメチルヒダントインを含有し、かつ、１Ｎ塩酸を混合しなかった以外は全て実施例１と同様にし、ｐＨ７．２の有害微生物撲滅剤とした。この時の白水の微生物数及び真菌数を表１に示す。
比較例４
In Example 1, all except that it contains 5,5-dimethylhydantoin so as to be equimolar to the hypochlorite ion of sodium hypochlorite and 1N hydrochloric acid was not mixed. In the same manner, a harmful microorganism eradication agent having a pH of 7.2 was obtained. Table 1 shows the number of microorganisms and fungi in white water at this time.
Comparative Example 4
実施例１において、第一液と第二液とを混合し５秒間反応させた後のｐＨを７．２になるよう１Ｎ塩酸の量を変更した以外は全て実施例１と同様にし、比較例４とした。この時の白水の微生物数及び真菌数を表１に示す。 In Example 1, the same procedure was followed as in Example 1, except that the amount of 1N hydrochloric acid was changed so that the pH after mixing the first solution and the second solution and reacting for 5 seconds was 7.2. It was set to 4. Table 1 shows the number of microorganisms and fungi in white water at this time.
循環型調湿機を用いて、Ｂ工場塗工原紙抄紙機より採取した白水［細菌数（ＣＦＵ）３．３×１０６，真菌数４８］５０ｍｌを３７℃に加温する。
別に、５℃に保持した工業用水中に１４質量％濃度の次亜塩素酸ナトリウム水溶液を加え、活性塩素量に換算して濃度２８００ｐｐｍの次亜塩素酸ナトリウム希釈水溶液を調製し、第一液とした。
次いで、次亜塩素酸ナトリウムの次亜塩素酸イオンに対し０．５モルとなるように５，５−ジメチルヒダントインを含有する水溶液を調製し第二液とした。この第二液に１Ｎ塩酸１６０μｌ／１００ｍｌを混合後、第一液と第二液とを混合し５秒間反応させｐＨ６．２の有害微生物撲滅剤を得た。この有害微生物撲滅剤を上記の白水中へ５，５−ジメチルヒダントインが６ｐｐｍとなる量を添加し、よく混合した。次いで５分経過後、白水の一部を採取し、常法により混釈平板培養を行い、発生したコロニー数から白水中の微生物数を計測した。なお、細菌数の計測培地としてはワックスマン寒天培地を、真菌数の計測培地としてはストレプトマイシンを加えたワックスマン寒天培地を使用した。
この結果を表２に示す。
実施例４、比較例５、６
Using a circulation-type humidity controller, 50 ml of white water [bacterial count (CFU) 3.3 × 10 6 , fungal count 48] collected from the base B coating base paper machine is heated to 37 ° C.
Separately, a 14% strength by weight sodium hypochlorite aqueous solution is added to industrial water maintained at 5 ° C. to prepare a sodium hypochlorite diluted aqueous solution having a concentration of 2800 ppm in terms of the amount of active chlorine, did.
Next, an aqueous solution containing 5,5-dimethylhydantoin was prepared so as to be 0.5 mol with respect to hypochlorite ion of sodium hypochlorite, and used as the second liquid. After mixing 160 μl / 100 ml of 1N hydrochloric acid with this second liquid, the first liquid and the second liquid were mixed and reacted for 5 seconds to obtain a harmful microorganism eradication agent having a pH of 6.2. This harmful microorganism eradicating agent was added to the above white water in an amount such that 5,5-dimethylhydantoin was 6 ppm and mixed well. Then, after 5 minutes, a part of white water was collected and subjected to pour plate culture by a conventional method, and the number of microorganisms in white water was counted from the number of colonies generated. Waxman agar medium was used as the medium for measuring the number of bacteria, and Waxman agar medium supplemented with streptomycin was used as the medium for measuring the number of fungi.
The results are shown in Table 2.
Example 4 and Comparative Examples 5 and 6
実施例３において、第一液と第二液とを混合し５秒間反応させた後のｐＨをそれぞれ、６．９、７．２、５．５になるよう１Ｎ塩酸の量を変更した以外は全て実施例３と同様にし、実施例４を得るとともに比較例５、６とした。この時の白水の微生物数及び真菌数を表２に示す。 In Example 3, except that the amount of 1N hydrochloric acid was changed so that the pH after mixing the first liquid and the second liquid and reacting for 5 seconds would be 6.9, 7.2, and 5.5, respectively. All were carried out similarly to Example 3, obtained Example 4, and set it as Comparative Examples 5 and 6. Table 2 shows the number of microorganisms and fungi in white water at this time.
表１の結果から、実施例１は従来のアンモニウム化合物を用いる比較例２と同等の殺菌効果及び殺かび効果が得られていることが分かる。また、ｐＨを７以上とする比較例４に比べ、ｐＨを６．２とする実施例１の有害微生物撲滅剤は殺菌効果で約１０倍、殺かび効果で約３倍優れた効果を示していることが分かる。
また、実施例２は、実施例１と比較してヒダントインの種類を変更したものであるが、実施例１と同等以上の殺菌効果及び殺かび効果が得られていることが分かる。
表２において、実施例３と比較例６の結果から、ｐＨ６を境に殺菌効果、防かび効果とも顕著な差異が見受けられることがわかる。また、これと同様に実施例４と比較例５の結果から、ｐＨ７を境に殺菌効果、防かび効果とも顕著な差異が見受けられることがわかる。
From the results in Table 1, it can be seen that Example 1 has the same bactericidal and fungicidal effects as Comparative Example 2 using a conventional ammonium compound. Moreover, compared with the comparative example 4 which makes pH 7 or more, the harmful microorganisms eradication agent of Example 1 which makes pH 6.2 shows about 10 times the bactericidal effect and about 3 times the fungicidal effect. I understand that.
Moreover, although Example 2 changes the kind of hydantoin compared with Example 1, it turns out that the bactericidal effect and fungicidal effect more than equivalent to Example 1 are acquired.
In Table 2, it can be seen from the results of Example 3 and Comparative Example 6 that there is a marked difference between the bactericidal effect and the fungicidal effect at pH 6. Similarly, from the results of Example 4 and Comparative Example 5, it can be seen that there is a marked difference between the bactericidal and antifungal effects at pH 7.
本発明の有害微生物撲滅剤及びこれを用いた有害微生物撲滅方法は、従来のアンモニウム化合物を用いる有害微生物撲滅剤と同等の殺菌効果を有することができるため、水質汚濁防止法により使用することが困難な環境でも有害微生物の発生を効率よく抑制でき、その結果高い品質の製品を得ることができる。そのため本発明の有害微生物撲滅剤及びこれを用いた有害微生物撲滅方法は、工業分野、特に紙の製造に極めて有効なものである。 The harmful microorganism eradication agent of the present invention and the harmful microorganism eradication method using the same can have a bactericidal effect equivalent to that of a conventional harmful microorganism eradicating agent using an ammonium compound, and thus are difficult to use by the water pollution prevention method. Generation of harmful microorganisms can be efficiently suppressed even in a difficult environment, and as a result, a high-quality product can be obtained. Therefore, the harmful microorganism eradication agent of the present invention and the harmful microorganism eradication method using the same are extremely effective in the industrial field, particularly in the production of paper.
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