JP4533618B2 - Disinfectant cleaning composition - Google Patents
Disinfectant cleaning composition Download PDFInfo
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- JP4533618B2 JP4533618B2 JP2003394080A JP2003394080A JP4533618B2 JP 4533618 B2 JP4533618 B2 JP 4533618B2 JP 2003394080 A JP2003394080 A JP 2003394080A JP 2003394080 A JP2003394080 A JP 2003394080A JP 4533618 B2 JP4533618 B2 JP 4533618B2
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- Prior art keywords
- acid
- aqueous solution
- persulfate
- sterilization
- weight
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 66
- 238000004140 cleaning Methods 0.000 title claims description 18
- 239000000645 desinfectant Substances 0.000 title description 11
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 148
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 81
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 57
- 239000007864 aqueous solution Substances 0.000 claims description 55
- 230000001954 sterilising effect Effects 0.000 claims description 54
- 238000004659 sterilization and disinfection Methods 0.000 claims description 46
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 39
- 239000003599 detergent Substances 0.000 claims description 27
- 150000007524 organic acids Chemical class 0.000 claims description 18
- 230000000249 desinfective effect Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000012736 aqueous medium Substances 0.000 claims description 12
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 9
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000004967 organic peroxy acids Chemical class 0.000 description 68
- 238000000034 method Methods 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 25
- 230000000694 effects Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 235000019645 odor Nutrition 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- ADKBGLXGTKOWIU-UHFFFAOYSA-N butanediperoxoic acid Chemical compound OOC(=O)CCC(=O)OO ADKBGLXGTKOWIU-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012459 cleaning agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 238000010790 dilution Methods 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 3
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- 239000008272 agar Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- -1 persulfate compound Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000032368 Device malfunction Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
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- 230000036783 anaphylactic response Effects 0.000 description 1
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- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
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- 210000004369 blood Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000000385 dialysis solution Substances 0.000 description 1
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
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- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、除菌洗浄剤組成物に関する。更に詳しくは、本発明は、人工透析装置、内視鏡等医療機器、水処理装置、食品製造装置等の除菌に有用に使用できる水溶性有機過酸系の除菌洗浄剤組成物に関する。 The present invention relates to a disinfecting detergent composition. More specifically, the present invention relates to a water-soluble organic peracid-based disinfectant cleaning composition that can be usefully used for disinfecting medical devices such as an artificial dialysis apparatus and an endoscope, a water treatment apparatus, and a food production apparatus.
人工透析装置、内視鏡等の医療機器は、間接的あるいは直接的に患者との接触がある。そのため、患者への細菌やウイルス感染の防止、機器の正常運転状態を保持するための細菌、真菌、ウイルス等の除去状態、細菌増殖あるいは機器誤動作の原因なる異物付着のない状態に保持される必要がある。例えば、人工透析装置を、その使用過程において血液等の体液や透析液由来物が付着して汚染された状態のまま放置すると、細菌やウイルスを患者へ感染させたり、異種蛋白質によるアナフィラキシー等を発生させたり、細菌増殖によるエンドトキシンの発生により患者を発熱させたりする等の原因となる場合がある。かかる原因を除外するため、使用後の装置への汚染付着物の洗浄除去と除菌（殺菌）を目的とした除菌洗浄の実施が必須である。 Medical devices such as an artificial dialysis machine and an endoscope have contact with a patient indirectly or directly. Therefore, it is necessary to prevent bacteria and virus infection to patients, remove bacteria, fungi, viruses, etc. to maintain the normal operation state of the device, and maintain a state free from foreign substances that cause bacterial growth or device malfunction. There is. For example, if an artificial dialysis machine is left in a state where it is contaminated with body fluids such as blood or dialysate in the course of its use, it infects patients with bacteria or viruses, or anaphylaxis due to foreign proteins occurs. Or cause the patient to fever due to endotoxin generation due to bacterial growth. In order to exclude such causes, it is essential to carry out sterilization washing for the purpose of washing and removing contaminant deposits on the apparatus after use and sterilization (sterilization).
従来から、この除菌洗浄を目的に次亜塩素酸ナトリウムのような塩素系化合物を含有する塩素系洗浄剤、グルタルアルデヒドのようなアルデヒド系洗浄剤が使用されている。しかしこれら洗浄剤は、人体に対する安全性の問題、金属からなる装置部材に対する腐食性の問題、更には環境への悪影響が懸念される。そのため、近年に至って有機過酸、とりわけ過酢酸を主成分とする除菌剤あるいは殺菌剤が使用されるようになってきた。過酢酸は、酢酸と過酸化水素および水からなる平衡過酢酸溶液として得ることができ、その製造方法については、例えば、特許第２５２３０８５号（特許文献１）、特許第２８７１１２４号（特許文献２）、特許第３０４６６２８号（特許文献３）、特許第２５９９２０４号（特許文献４）等で公開されている。また、医療機器用の除菌洗浄に用いられる過酢酸は、一般的に上記方法によって製造された平衡過酢酸溶液であり、その使用方法についても、例えば特開２０００−５１３５０号公報（特許文献５）、特開２００１−７２９９６号公報（特許文献６）等で公開されている。 Conventionally, a chlorine-based cleaning agent containing a chlorine-based compound such as sodium hypochlorite and an aldehyde-based cleaning agent such as glutaraldehyde have been used for the purpose of this sterilization cleaning. However, these cleaning agents are concerned with safety problems for the human body, corrosive problems with metal equipment members, and adverse environmental effects. Therefore, in recent years, disinfectants and bactericides mainly composed of organic peracids, especially peracetic acid, have been used. Peracetic acid can be obtained as an equilibrium peracetic acid solution comprising acetic acid, hydrogen peroxide, and water. For example, Japanese Patent No. 2523085 (Patent Document 1) and Patent No. 2871124 (Patent Document 2) can be used for the production method. Patent No. 3046628 (Patent Document 3), Patent No. 2599204 (Patent Document 4) and the like. In addition, peracetic acid used for sterilization and washing for medical devices is an equilibrium peracetic acid solution generally produced by the above-described method. ), And JP-A-2001-72996 (Patent Document 6).
また、平衡過酢酸溶液は、鉄、銅等の金属不純物が混入すると速やかに分解することが知られており、この分解を防止する目的にピロリン酸、ピロリン酸ナトリウム等のポリリン酸塩、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリメチルホスホン酸またはその塩、ジピコリン酸、２，６−ピリジンジカルボン酸、ジエチレントリアミン五酢酸塩等の安定剤が該溶液中に添加されている。また、過酢酸の合成における平衡化反応は緩慢であるために、平衡化反応を促進する触媒として硫酸、リン酸等の強鉱酸を共存させると有効なことも知られている。 In addition, it is known that the equilibrium peracetic acid solution is rapidly decomposed when metal impurities such as iron and copper are mixed. For the purpose of preventing this decomposition, polyphosphates such as pyrophosphoric acid and sodium pyrophosphate, 1- Stabilizers such as hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylphosphonic acid or salts thereof, dipicolinic acid, 2,6-pyridinedicarboxylic acid, diethylenetriaminepentaacetic acid salt are added to the solution. Moreover, since the equilibration reaction in the synthesis of peracetic acid is slow, it is known that it is effective to coexist strong mineral acids such as sulfuric acid and phosphoric acid as a catalyst for promoting the equilibration reaction.
また、過酢酸以外の無臭の有機過酸を作る方法として、特開昭５３−８１６１９号公報（特許文献７）には過グルタル酸水溶液を作る方法、特開平８−６７６６７号公報（特許文献８）には、過グルタル酸、過コハク酸、過アジピン酸から混合有機過酸混合物を作る方法等が既に公開されている。 Moreover, as a method for producing an odorless organic peracid other than peracetic acid, JP-A-53-81619 (Patent Document 7) discloses a method for preparing an aqueous solution of perglutaric acid, JP-A-8-67667 (Patent Document 8). ), A method for making a mixed organic peracid mixture from perglutaric acid, persuccinic acid and peradipic acid has already been disclosed.
上記製法にて合成された有機過酸水溶液を除菌洗浄剤として使用する場合を想定すると、以下のような、なお改良すべき多くの欠点を有する。 Assuming that the organic peracid aqueous solution synthesized by the above-mentioned production method is used as a disinfecting detergent, it has many drawbacks to be improved as follows.
例えば、過酢酸水溶液は、有機過酸水溶液の中でも除菌（殺菌）効力及び製品の経時保存安定性に優れているため多用されている。しかし、過酢酸水溶液は、過酸化水素を含有しており、過酢酸の割合を上げるには、過酸化水素の割合を増やす必要がある。ところが、過酢酸水溶液を輸送あるいは保管時における取扱いが容易となる非劇物扱い（過酸化水素含有量６％以下）の製品形態品とするには、過酸化水素の割合を減らす必要があるため、相対的に過酢酸濃度が低くなる。過酢酸濃度の低い水溶液を、除菌洗浄工程に適用する際に希釈液で高倍率に希釈すると、除菌効果の発揮が不充分になる。 For example, peracetic acid aqueous solutions are frequently used among organic peracid aqueous solutions because of their excellent disinfection (sterilization) efficacy and storage stability of products over time. However, the peracetic acid aqueous solution contains hydrogen peroxide, and it is necessary to increase the proportion of hydrogen peroxide in order to increase the proportion of peracetic acid. However, it is necessary to reduce the proportion of hydrogen peroxide in order to make a peracetic acid aqueous solution product product that is easy to handle during transport or storage and is handled as a non- deleterious substance (hydrogen peroxide content of 6% or less). Relatively low peracetic acid concentration. If an aqueous solution having a low peracetic acid concentration is applied to the sterilization washing step with a diluting solution at a high magnification, the sterilization effect is insufficiently exhibited.
高倍率の希釈条件においても除菌効果を充分に発揮させる方法として、酢酸濃度比率を大きくすることで過酢酸濃度を高める方法がある。しかし、この方法では、遊離の酢酸濃度も必然的に高くなり、水溶液からの不快な酢酸臭気の発生が益々強くなる。 There is a method of increasing the peracetic acid concentration by increasing the acetic acid concentration ratio as a method of sufficiently exerting the sterilization effect even under high-magnification dilution conditions. However, this method inevitably increases the concentration of free acetic acid, and the generation of an unpleasant acetic acid odor from the aqueous solution becomes more and more intense.
すなわち、これらの問題は、過酢酸生成反応が、下記式に示すように酢酸と過酸化水素濃度に依存する平衡反応であり、平衡状態における生成過酢酸濃度を高めるためには溶液中の酢酸（ＣＨ3ＣＯＯＨ）あるいは過酸化水素（Ｈ2Ｏ2）の濃度を高める必要があることに由来している。つまり、毒物及び劇物取締法にて規定される劇物の適用を受けない濃度で過酸化水素を使用すると、生成する過酢酸濃度にも限界があること、過酸化水素を増加させないで、酢酸濃度を増加させると、過酢酸濃度は増加するが、必然的に遊離酢酸濃度も増加し、臭気が発生することになる。 That is, these problems are equilibrium reactions in which the peracetic acid production reaction depends on the concentration of acetic acid and hydrogen peroxide as shown in the following formula. In order to increase the concentration of peracetic acid produced in the equilibrium state, acetic acid ( This is because the concentration of CH 3 COOH) or hydrogen peroxide (H 2 O 2 ) needs to be increased. In other words, if hydrogen peroxide is used at a concentration that does not apply to the deleterious substances prescribed by the Poisonous and Deleterious Substances Control Law, there is a limit to the concentration of peracetic acid that is produced. Increasing the concentration increases the peracetic acid concentration, but inevitably also increases the free acetic acid concentration, resulting in odor.
また、酢酸臭気問題を改良する別手段として、酢酸以外の有機酸を活用する方法が考えられる。例えば、特開昭５３−８１６１９号公報（特許文献９）で開示されている過グルタル酸、特開平８−６７６６７号公報（特許文献１０）で開示されている過グルタル酸、過コハク酸および過アジピン酸よりなる混合有機過酸、特開平１０−１０１６４２号公報（特許文献１１）で開示されている６−アミノ−ｎ−過カプロン酸を始めとする過アミノカルボン酸のような無臭の有機過酸を活用する方法も提案されている。 Further, as another means for improving the acetic acid odor problem, a method using an organic acid other than acetic acid can be considered. For example, perglutaric acid disclosed in Japanese Patent Laid-Open No. 53-81619 (Patent Document 9), perglutaric acid, persuccinic acid and peroxygen disclosed in Japanese Patent Laid-Open No. 8-67667 (Patent Document 10). A mixed organic peracid composed of adipic acid, and an odorless organic peroxycarboxylic acid such as 6-amino-n-percaproic acid disclosed in JP-A-10-101642 (Patent Document 11). A method of utilizing an acid has also been proposed.
これら手法によれば酢酸臭気問題は回避できるものの、目的とする主効果である除菌効果が過酢酸より大幅に劣り、実用性を満足するものでなかった。すなわち、従来の過酢酸を始めとする有機過酸系除菌洗浄剤は、除菌力と臭気問題の両立性が悪く、特に過酸化水素含有量に関連する非劇物扱い条件を前提した場合はその傾向が強く、両立性は改良すべき検討課題であった。また、高い除菌効果を発揮する洗浄剤の開発は、除菌効果を発揮する必要薬剤濃度の低減が可能となり、結果的には除菌処理コスト低減に結びつくことであり、従来からの継続的改良検討課題であった。 According to these methods, the acetic acid odor problem can be avoided, but the sterilization effect, which is the intended main effect, is significantly inferior to peracetic acid, and the practicality is not satisfied. In other words, organic peracid-based disinfectant cleaners such as conventional peracetic acid have poor compatibility between sterilization power and odor problems, especially when premised on non-deleterious handling conditions related to hydrogen peroxide content The tendency was strong, and compatibility was an issue to be improved. In addition, the development of detergents that exhibit high sterilization effects can reduce the concentration of necessary chemicals that exhibit sterilization effects, resulting in lower sterilization treatment costs. It was an improvement study subject.
本発明者等は、上記した検討課題に対する対応策を鋭意検討した結果、有機過酸水性溶液中に過硫酸塩を混合溶解させることによって有機過酸の除菌洗浄力を意外にも向上できること、また更にその混合溶解液に非アミノ系ホスホン酸と共存させることによって溶解状態の過硫酸塩および有機過酸の保存経時安定性を大幅に向上できることを見出し、本発明を完成するに至った。 As a result of earnestly examining the countermeasures against the above-mentioned examination problems, the present inventors can surprisingly improve the disinfecting detergency of organic peracid by dissolving persulfate in the organic peracid aqueous solution, Furthermore, the coexistence of the mixed solution with non-amino phosphonic acid has greatly found that the storage aging stability of dissolved persulfate and organic peracid can be greatly improved, and the present invention has been completed.
かくして本発明によれば、有効成分として、少なくとも過酢酸と過硫酸塩とを含む水性溶液からなる除菌洗浄剤組成物であって、
前記除菌洗浄剤組成物が、１液型の水性溶液であって、かつ水性媒体中に、過酸化水素を３．５〜６重量％の割合で、過硫酸水素カリウムを０．２〜５重量％の割合でかつ硫酸水素カリウムと硫酸カリウムとの３重塩の形態で、酢酸を５〜３０重量％の割合で、１−ヒドロキシエチリデン−１，１−ジホスホン酸又はその塩を０．０５〜１重量％の割合で添加して得られた水性溶液である除菌洗浄剤組成物が提供される。
Thus, according to the present invention, a disinfecting detergent composition comprising an aqueous solution containing at least peracetic acid and persulfate as active ingredients,
The sterilizing detergent composition is a one-component aqueous solution, and hydrogen peroxide is added in an amount of 3.5 to 6% by weight and potassium hydrogen persulfate is added in an amount of 0.2 to 5 in an aqueous medium. in the form of weight% ratio a and triple salt of potassium hydrogen sulfate and potassium sulfate, at a rate of acetic acid from 5 to 30 wt%, of 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof 0. Disinfecting detergent composition which is an aqueous solution obtained by adding at a ratio of 05 to 1% by weight is provided.
本発明の除菌洗浄剤組成物は、有機過酸と過硫酸塩を水性溶液中で併用することで、それら単独の効果より相乗的に向上した除菌効果を発揮する。この除菌効果の相乗的向上作用機構は、明確ではないが、過硫酸塩により有機過酸の酸化力が一段と強化されること、及び有機過酸と過硫酸塩との何らかの相互作用に基づくと考えられる。 The sterilization detergent composition of the present invention exhibits a sterilization effect that is synergistically improved from the effects of the single agent by using an organic peracid and a persulfate in combination in an aqueous solution. The mechanism of synergistic improvement of the sterilization effect is not clear, but it is based on the fact that persulfate further enhances the oxidizing power of organic peracid and some interaction between organic peracid and persulfate. Conceivable.
更に、非アミノ系ホスホン酸を共存させることで、有機過酸と過硫酸塩の除菌効果を水性溶液中で安定させることができ、長期保存可能な除菌洗浄剤組成物を提供することができる。 Furthermore, by coexisting non-amino phosphonic acid, the disinfecting effect of organic peracid and persulfate can be stabilized in an aqueous solution, and a disinfecting detergent composition that can be stored for a long time is provided. it can.
なお、従来公知の過酸化水素と有機酸（例えば、酢酸）から有機過酸を作製する際に触媒としての硫酸を共存させても、過硫酸塩は生成されないことを確認している。また、本発明において発揮される過硫酸塩様の使用効果も発揮されないことも確認している。すなわち、本発明の除菌洗浄剤組成物の保有する効果は、前もって合成された過硫酸塩の使用によってはじめて発現したものであり、従来の公知技術から容易に類推されるものではない。 It has been confirmed that a persulfate is not produced even when sulfuric acid is used as a catalyst in the production of an organic peracid from a conventionally known hydrogen peroxide and an organic acid (for example, acetic acid). It has also been confirmed that the persulfate-like use effect exhibited in the present invention is not exhibited. That is, the effect possessed by the sterilizing detergent composition of the present invention is first manifested by the use of a pre-synthesized persulfate, and is not easily inferred from conventional known techniques.
本発明の除菌洗浄剤組成物は、有機過酸と過硫酸塩を少なくとも有効成分量含み、必要に応じて更に非アミノ系ホスホン酸又はその塩を有効成分量含み、特定のｐＨ範囲を有する水性溶液からなる。 The disinfectant cleaning composition of the present invention contains an organic peracid and a persulfate at least as effective ingredients, and further contains a non-amino phosphonic acid or a salt thereof as necessary, and has a specific pH range. Consists of an aqueous solution.
まず、本発明に使用できる有機過酸としては、特に限定されず、当該分野で公知のものをいずれも使用できる。具体的には、過ギ酸、過酢酸、過プロピオン酸、過コハク酸、過グルタル酸等の過アルキル酸、過β−アラニン、過４−アミノ酪酸、過５−アミノ吉草酸、過６−アミノ−ｎ−カプロン酸等の過アミノカルボン酸が挙げられる。これら有機過酸は、単独でも、２種以上組み合わせて使用してもよい。 First, the organic peracid that can be used in the present invention is not particularly limited, and any organic peracid known in the art can be used. Specifically, peralkyl acids such as performic acid, peracetic acid, perpropionic acid, persuccinic acid, perglutaric acid, per-β-alanine, per-4-aminobutyric acid, per-5-aminovaleric acid, per-6-amino Peraminocarboxylic acids such as -n-caproic acid. These organic peracids may be used alone or in combination of two or more.
水性溶液中の有機過酸の有効成分量は、０．１重量％以上であることが好ましく、０．４〜６重量％の範囲であることがより好ましく、１〜４重量％の範囲であることが更に好ましい。０．１重量％より少ない場合、除菌効果が不充分であるので好ましくない。 The amount of the active component of the organic peracid in the aqueous solution is preferably 0.1% by weight or more, more preferably in the range of 0.4 to 6% by weight, and in the range of 1 to 4% by weight. More preferably. When the amount is less than 0.1% by weight, the sterilization effect is insufficient, which is not preferable.
有機過酸は、通常水性溶液中で有機過酸に相応する有機酸と過酸化水素との共存下で、安定に存在する。ここで、水性溶液中の有機過酸、有機酸及び過酸化水素の重量比率は、特に限定されず、一般的な比率が適用できるが、通常は、（有機過酸＋有機酸）／過酸化水素の重量比率で０．１〜１５の範囲のものであり、０．５〜１０の範囲のものが好ましく、特に好ましくは１〜５の範囲のものである。この重量比率が０．１より小さい場合および１５より大きい場合のいずれにおいても生成有機過酸の含有比率が小さくなるので好ましくない。なお、過酸化水素の水性溶液に対する割合は６重量％以下であることが好ましい。６重量％以下とすることによって、水性溶液を非劇物として取り扱うことができるので、保管及び輸送時の取り扱い性を向上できる。有機酸の重量比率は、含有させる有機過酸の重量比率によって決定される。 The organic peracid is usually present stably in an aqueous solution in the presence of an organic acid corresponding to the organic peracid and hydrogen peroxide. Here, the weight ratio of the organic peracid, the organic acid and the hydrogen peroxide in the aqueous solution is not particularly limited, and a general ratio can be applied, but usually (organic peracid + organic acid) / peroxidation. The weight ratio of hydrogen is in the range of 0.1 to 15, preferably in the range of 0.5 to 10, particularly preferably in the range of 1 to 5. In both cases where the weight ratio is less than 0.1 and greater than 15, the content ratio of the generated organic peracid is small, which is not preferable. The ratio of hydrogen peroxide to the aqueous solution is preferably 6% by weight or less. By setting the amount to 6% by weight or less, the aqueous solution can be handled as a non-deleterious substance, so that the handleability during storage and transportation can be improved. The weight ratio of the organic acid is determined by the weight ratio of the organic peracid to be contained.
上記有機過酸の内、過酢酸、過プロピオン酸、過コハク酸、過グルタル酸が好ましい。これら好適な有機過酸中、高い除菌力の保有を目的とする場合は、過酢酸単独または過酢酸と、過プロピオン酸、過コハク酸、過グルタル酸等の他の有機過酸との混合有機過酸を使用することが好ましい。臭気低減を目的とする場合は、過コハク酸、過グルタル酸を選定することが好ましい。 Of the organic peracids, peracetic acid, perpropionic acid, persuccinic acid, and perglutaric acid are preferred. In these suitable organic peracids, when high sterilization power is to be maintained, peracetic acid alone or a mixture of peracetic acid and other organic peracids such as perpropionic acid, persuccinic acid, perglutaric acid, etc. It is preferred to use organic peracids. For the purpose of reducing odor, it is preferable to select persuccinic acid or perglutaric acid.
但し、過コハク酸を使用する場合、コハク酸の室温（約２５℃）における水溶解度が約６重量％であるから、水性溶液中のコハク酸と過コハク酸の合計量を６重量％以下とすることが好ましい。 However, when using persuccinic acid, the water solubility of succinic acid at room temperature (about 25 ° C.) is about 6% by weight, so the total amount of succinic acid and persuccinic acid in the aqueous solution is 6% by weight or less. It is preferable to do.
次に、本発明における過硫酸塩は、水性溶液中の有機過酸の共存によって安定して存在すると共に、それ自体も除菌機能を有する。本発明に使用できる過硫酸塩とは、過硫酸水素カリウム、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等が挙げられる。この中では過硫酸水素カリウムが最も好適である。その理由は、過硫酸水素カリウムは、他の過硫酸塩に比べて、水溶解度が高く、組成物配合時の過酢酸量として測定した場合の過酸量の増加率が他の過硫酸塩より著しく高いためである。過硫酸水素カリウムは、無臭の酸性系酸化剤であり、衣料洗濯用漂白剤、入れ歯洗浄剤等の成分の一つとして使用されているが、本発明のような有機過酸の水溶液に配合溶解して使う使用法については、知られていない。 Next, the persulfate in the present invention stably exists due to the coexistence of an organic peracid in an aqueous solution, and has a sterilizing function itself. Examples of the persulfate that can be used in the present invention include potassium hydrogen persulfate, potassium persulfate, ammonium persulfate, and sodium persulfate. Of these, potassium hydrogen persulfate is most preferred. The reason for this is that potassium hydrogen persulfate has a higher water solubility than other persulfates, and the rate of increase in the amount of peracid when measured as the amount of peracetic acid when blended with the composition is higher than that of other persulfates. This is because it is extremely high. Potassium hydrogen persulfate is an odorless acidic oxidizer, and it is used as one of the components of clothes laundry bleach, denture cleaning agents, etc., but it is formulated and dissolved in an aqueous solution of organic peracid as in the present invention. It is not known how to use it.
水性溶液中の過硫酸塩の有効成分量は、０．１〜１０重量％の範囲であることが好ましく、０．５〜６重量％の範囲であることがより好ましい。０．１重量％より少ない場合、過硫酸塩配合により得られる除菌機能の向上効果が不充分であり、１０重量％より多い場合、水性溶液の酸化能力（活性酸素量）の経時による変化保持率（安定性）が低下する傾向が大きくなり、経済的でないので好ましくない。 The amount of the persulfate active ingredient in the aqueous solution is preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 0.5 to 6% by weight. When the amount is less than 0.1% by weight, the effect of improving the sterilization function obtained by the persulfate compound is insufficient. When the amount is more than 10% by weight, the oxidation capacity (active oxygen amount) of the aqueous solution is changed over time. The rate (stability) tends to decrease, which is not preferable because it is not economical.
なお、過硫酸カリウム、過硫酸ナトリウムのように過硫酸塩によっては、水溶解度が小さいため、上記配合量範囲で使用は溶解性に劣るものもある。このような過硫酸塩を使用する場合は、完全溶解が可能となる濃度範囲で使用することが好ましい。 Some persulfates, such as potassium persulfate and sodium persulfate, have low water solubility, so use may be inferior in the above-mentioned blending amount range. When such a persulfate is used, it is preferably used in a concentration range that allows complete dissolution.
ここで、水性溶液中の有機過酸と過硫酸塩の配合割合（モル比）は、９５／５〜５／９５の範囲であることが好ましい。さらに好ましい配合割合は、９０／１０〜２０／８０の範囲であり、この範囲内では、特に優れた除菌洗浄効果を有する。なお、有機過酸のモル比は、過酢酸換算値を意味する。 Here, the blending ratio (molar ratio) of the organic peracid and persulfate in the aqueous solution is preferably in the range of 95/5 to 5/95. A more preferable blending ratio is in a range of 90/10 to 20/80, and in this range, a particularly excellent sterilization cleaning effect is obtained. In addition, the molar ratio of organic peracid means a peracetic acid conversion value.
次に、本発明における非アミノ系ホスホン酸は、有機過酸及び過硫酸塩の安定剤としての機能を有する。具体的な非アミノ系ホスホン酸としては、１−ヒドロキシエチリデン−１，１−ジホスホン酸（ＨＥＤＰ）、ホスホノブタントリカルボン酸またはその塩が挙げられ、特に１−ヒドロキシエチリデン−１，１−ジホスホン酸またはその塩が好ましい。非アミノ系ホスホン酸の有効成分量は、該酸の種類によっても異なるが、０．０１〜２重量％の範囲であることが好ましく、０．０５〜１重量％の範囲であることがより好ましい。０．０１重量％より少ない場合、有機過酸及び過硫酸塩を安定に存在させるという機能が不充分であり、２重量％より多い場合、配合量に見合う効果を得ることが困難であるので好ましくない。更に、ピロリン酸、ピロリン酸ナトリウム等のポリリン酸塩も上記非アミノ系ホスホン酸と併用してもよい。 Next, the non-amino phosphonic acid in the present invention functions as a stabilizer for organic peracids and persulfates. Specific examples of the non-amino phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), phosphonobutanetricarboxylic acid or a salt thereof, and particularly 1-hydroxyethylidene-1,1-diphosphonic acid. Or its salt is preferable. The amount of the active ingredient of the non-amino phosphonic acid varies depending on the kind of the acid, but is preferably in the range of 0.01 to 2% by weight, and more preferably in the range of 0.05 to 1% by weight. . When the amount is less than 0.01% by weight, the function of stably presenting the organic peracid and persulfate is insufficient, and when the amount is more than 2% by weight, it is difficult to obtain an effect commensurate with the blending amount. Absent. Furthermore, polyphosphates such as pyrophosphate and sodium pyrophosphate may be used in combination with the non-amino phosphonic acid.
次に、本発明の水性溶液を構成する水性媒体としては、水単独、水溶性の有機溶媒（例えば、アルコール）と水との混合溶媒が挙げられる。 Next, examples of the aqueous medium constituting the aqueous solution of the present invention include water alone and a mixed solvent of water-soluble organic solvent (for example, alcohol) and water.
本発明の除菌洗浄剤組成物である水性溶液は、２５℃におけるｐＨが２．５〜０．３の範囲であることが好ましい。この範囲内であれば、水性溶液の安定性、言い換えれば有機過酸及び過硫酸塩の経時保存安定性の低下を抑制することができる。更に、ｐＨが低い場合、水性溶液中の有機過酸生成反応が促進されるため、所望濃度の有機過酸を早期に得ることができるという利点がある。具体的には、１．５〜０．５の範囲であることがより好ましい。ｐＨが０．３より小さい場合、除菌洗浄の対象物（特に金属部品を含む装置）の腐食が進みやすくなったり、原液を希釈した場合における有機過酸平衡反応が速すぎて使用時までに分解してしまい、かえって有機過酸の濃度が低下したりすることがあり、２．５より大きい場合、平衡反応によって生成される有機過酸濃度が低下するので好ましくない。 The aqueous solution that is the sterilizing detergent composition of the present invention preferably has a pH at 25 ° C. in the range of 2.5 to 0.3. Within this range, the stability of the aqueous solution, in other words, the deterioration of the storage stability with time of the organic peracid and persulfate can be suppressed. Further, when the pH is low, the organic peracid production reaction in the aqueous solution is promoted, so that there is an advantage that an organic peracid having a desired concentration can be obtained at an early stage. Specifically, the range of 1.5 to 0.5 is more preferable. If the pH is less than 0.3, the object of sterilization washing (especially equipment containing metal parts) is likely to corrode, or the organic peracid equilibrium reaction when the stock solution is diluted is too fast before use. In some cases, the concentration of the organic peracid may be lowered, and the concentration of the organic peracid may be decreased. If the concentration is larger than 2.5, the concentration of the organic peracid generated by the equilibrium reaction is undesirably decreased.
本発明の除菌洗浄剤組成物は、１液型、２液型、３液型のいずれの形態でもよく、粉末状の過硫酸塩と有機過酸及び非アミノ系ホスホン酸とを同時又は別々に含む溶液との形態であってもよい。２液型の場合、有機過酸、過硫酸塩及び非アミノ系ホスホン酸の組み合わせは特に限定されない。 The disinfectant cleaning composition of the present invention may be in any one of a one-component type, a two-component type, and a three-component type. A powdered persulfate, an organic peracid, and a non-amino phosphonic acid may be used simultaneously or separately. It may be in the form of a solution contained in In the case of the two-pack type, the combination of organic peracid, persulfate and non-amino phosphonic acid is not particularly limited.
本発明の除菌洗浄剤組成物は、有機過酸に過硫酸塩及び非アミノ系ホスホン酸を使用時又は予め水性媒体に溶解することで水性溶液の形態として得られる。 The disinfectant cleaning composition of the present invention is obtained in the form of an aqueous solution by using a persulfate and a non-amino phosphonic acid in an organic peracid, or by dissolving in advance in an aqueous medium.
除菌洗浄剤組成物の製造に使用される有機過酸は、有機過酸として市販されているものをいずれも使用することができる。これ以外に、有機過酸に相応する有機酸と過酸化水素とを混合することで、上記平衡反応により得られた有機過酸を使用してもよい。有機酸及び過酸化水素は、通常水溶液の形態で入手可能である。入手可能な有機酸の水溶液の濃度は、有機酸の種類に応じて異なる。一方、過酸化水素の水溶液の濃度は、通常３５〜６０重量％である。 Any organic peracid that is commercially available as an organic peracid can be used for the production of the disinfecting detergent composition. In addition to this, an organic peracid obtained by the above equilibrium reaction may be used by mixing an organic acid corresponding to the organic peracid and hydrogen peroxide. Organic acids and hydrogen peroxide are usually available in the form of aqueous solutions. The concentration of the aqueous solution of the organic acid that can be obtained varies depending on the type of the organic acid. On the other hand, the concentration of the aqueous solution of hydrogen peroxide is usually 35 to 60% by weight.
なお、有機過酸は、水性媒体に溶解することでそれを放出しうる化合物由来の有機過酸でもよい。このような化合物として過酢酸を発生する化合物を例示すれば、過炭酸ナトリウムあるいは過ホウ酸ナトリウムと、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアセチルエチレンジアミン（ＴＡＥＤ）のようなポリアシル化アミンあるいはグルコースペンタアセテートのような多価アルコールの酢酸エステル類との固形形態混合物等が挙げられる。これら化合物は、通常アルカリ性の水溶液中で過酢酸を発生させるものであり、生成した過酢酸は比較的短時間で酢酸に変化するため、これら化合物を使用する場合は、除菌洗浄組成物の調製後、速やか（室温放置で少なくとも１２時間以内）に除菌洗浄処理に供することが好ましい。 The organic peracid may be an organic peracid derived from a compound that can be dissolved in an aqueous medium to release it. Examples of such compounds that generate peracetic acid include sodium percarbonate or sodium perborate and polyacylated amines such as N, N, N ′, N′-tetraacetylethylenediamine (TAED) or glucose. And solid form mixtures with polyhydric alcohol acetates such as pentaacetate. These compounds usually generate peracetic acid in an alkaline aqueous solution, and the generated peracetic acid changes to acetic acid in a relatively short time. Therefore, when these compounds are used, preparation of a disinfecting cleaning composition is required. After that, it is preferable to use the sterilization washing treatment promptly (within at least 12 hours at room temperature).
過硫酸塩は、通常粉末形態であり、直接水性媒体に溶解しても、予め水溶液として水性媒体と混合してもよい。特に、過硫酸水素カリウムは、一般的にはカロ酸とも呼ばれる範疇のものであり、単体物を使用することができる。但し、単体物は、安定性が悪く取り扱い性に劣るため、過硫酸水素カリウム・硫酸カリウム・硫酸水素カリウムからなる３重塩の形態の粉末品を使用することが好ましい。このような３重塩は、Ｏｘｏｎｅ（デュポン社製）、Ｃａｒｏａｔ（デグサ社製）等の商品名で市販されているものを使用できる。 The persulfate is usually in a powder form, and may be directly dissolved in an aqueous medium or may be mixed in advance with an aqueous medium as an aqueous solution. In particular, potassium hydrogen persulfate belongs to a category generally called caroic acid, and a simple substance can be used. However, since the single substance has poor stability and poor handling, it is preferable to use a powder product in the form of a triple salt composed of potassium hydrogen persulfate, potassium sulfate, and potassium hydrogen sulfate. As such triple salts, those commercially available under trade names such as Oxone (manufactured by DuPont) and Caroat (manufactured by Degussa) can be used.
非アミノ系ホスホン酸は、その形態に応じて、直接水性媒体に溶解しても、予め水溶液として水性媒体と混合してもよい。 Depending on the form, the non-amino phosphonic acid may be directly dissolved in an aqueous medium or may be mixed with an aqueous medium in advance as an aqueous solution.
ここで、市販品を使用せず、有機過酸を新たに合成する方法としては、有機酸と過酸化水素を含む水溶液を、任意に安定剤（例えば、ＨＥＤＰ）及び反応触媒（例えば、リン酸）の存在下、保温状態で規定時間以上保持する方法が挙げられる。保持時間（反応時間）は、反応が完結しうる（平衡反応状態となる）時間であることが好ましく、反応触媒の有無、原料濃度によっても異なるが、例えば、２５℃では１２８時間、４５℃では２８時間、１００℃では１時間以内である。すなわち、反応温度と必要反応時間は、一般的にはアレニウスの式と呼ばれる反応速度定数Ｋと温度Ｔの関係式“Ｋ＝Ａｅｘｐ（−Ｅ／ＲＴ）”（式中、Ｋ＝反応速度定数、Ａ＝定数、Ｅ＝活性化エネルギー、Ｒ＝気体定数、Ｔ＝絶対温度を示す。）によって関係付けられ、反応温度の上昇とともに必要反応時間は短くなる、例えば反応温度が１０℃上昇すると必要反応時間は約１／２となる関係にある。 Here, as a method for newly synthesizing an organic peracid without using a commercially available product, an aqueous solution containing an organic acid and hydrogen peroxide is optionally used as a stabilizer (for example, HEDP) and a reaction catalyst (for example, phosphoric acid). ) In the presence of heat, and a method of holding for a specified time or longer. The holding time (reaction time) is preferably a time during which the reaction can be completed (becomes an equilibrium reaction state), and varies depending on the presence or absence of the reaction catalyst and the raw material concentration. For example, at 25 ° C., 128 hours, and at 45 ° C. It is within 1 hour at 28 ° C. and 100 ° C. That is, the reaction temperature and the required reaction time are expressed by a relational expression “K = Aexp (−E / RT)” (where K = reaction rate constant, generally called Arrhenius equation). A = constant, E = activation energy, R = gas constant, T = absolute temperature), and the required reaction time becomes shorter as the reaction temperature increases. The time is about ½.
有機過酸と過硫酸塩を混合する方法としては、（１）有機過酸を合成する前の有機酸と過酸化水素を含む混合水性溶液に過硫酸塩を溶解し、次いで有機過酸を合成する方法、（２）既に合成した有機過酸含有水性溶液（有機過酸と有機過酸に相応する有機酸と過酸化水素を含有する）に過硫酸塩を配合溶解する方法、（３）除菌洗浄剤組成物として使用する直前の有機過酸含有水性溶液に過硫酸塩を溶解する方法が挙げられる。更に、除菌洗浄剤組成物を希釈して使用する場合には、有機過酸含有水性溶液を所定倍数まで希釈した後、希釈液に過硫酸塩を溶解する方法も挙げられる。 As a method of mixing organic peracid and persulfate, (1) dissolving persulfate in mixed aqueous solution containing organic acid and hydrogen peroxide before synthesizing organic peracid, then synthesizing organic peracid (2) A method of mixing and dissolving a persulfate in an organic peracid-containing aqueous solution (containing an organic peracid and an organic acid corresponding to the organic peracid and hydrogen peroxide), (3) The method of melt | dissolving a persulfate in the organic peracid containing aqueous solution just before using as a microbe cleaning composition is mentioned. Furthermore, when diluting the sterilizing detergent composition, a method of dissolving the persulfate in the diluted solution after diluting the organic peracid-containing aqueous solution to a predetermined multiple is also included.
特に、本発明の発明者等は、水性溶液中で溶解状態の過硫酸塩を長期に安定に存在させるためには、有機酸、過酸化水素と有機過酸及び非アミノ系ホスホン酸と共存させ、水性溶液のｐＨ範囲を適正範囲に調製することによって実現できることを見出した。言い換えると、本発明の発明者等は、市場に製品として流通させ得るレベルにまで安定性が向上した過硫酸塩を含む１液型の除菌洗浄剤組成物を提供できることを見出している。よって、本発明は、実用的見地から見ても意義がある。 In particular, the inventors of the present invention have made an organic acid, hydrogen peroxide, an organic peracid, and a non-amino phosphonic acid coexist in order for the persulfate dissolved in an aqueous solution to exist stably for a long period of time. It has been found that this can be realized by adjusting the pH range of the aqueous solution to an appropriate range. In other words, the inventors of the present invention have found that it is possible to provide a one-part sterilization detergent composition containing a persulfate that has improved stability to a level that can be distributed as a product on the market. Therefore, the present invention is significant from a practical viewpoint.
好ましい１液型の除菌洗浄剤組成物は、過硫酸水素カリウムを０．２〜５重量％、有機過酸を０．４〜６重量％（過酢酸換算値）、１−ヒドロキシエチリデン−１，１−ジホスホン酸又はその塩を０．０５〜１重量％含み、２５℃で１．５〜０．５のｐＨを有する除菌洗浄剤組成物である。 A preferred one-part sterilizing detergent composition is 0.2-5 wt% potassium hydrogen sulfate, 0.4-6 wt% organic peracid (peracetic acid equivalent value), 1-hydroxyethylidene-1 , 1-diphosphonic acid or a salt thereof, and a sterilizing detergent composition having a pH of 1.5 to 0.5 at 25 ° C.
また、より好ましい１液型の除菌洗浄剤組成物は、水性媒体に、過酸化水素を３．５〜６重量％の割合で、過硫酸水素カリウムを０．２〜５重量％の割合でかつ硫酸水素カリウムと硫酸カリウムとの３重塩の形態で、酢酸を５〜３０重量％の割合で、１−ヒドロキシエチリデン−１，１−ジホスホン酸又はその塩を０．０５〜１重量％の割合で添加して得られた水性溶液である。 A more preferred one-part sterilizing detergent composition is an aqueous medium containing hydrogen peroxide in a proportion of 3.5 to 6% by weight and potassium hydrogen sulfate in a proportion of 0.2 to 5% by weight. And in the form of a triple salt of potassium hydrogen sulfate and potassium sulfate, acetic acid in a proportion of 5 to 30% by weight, 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof in an amount of 0.05 to 1% by weight. It is an aqueous solution obtained by adding in proportions.
上記より好ましい除菌洗浄剤組成物は、過酢酸ベースの除菌洗浄剤組成物であるが、公知の組成物と比較し酢酸臭気の増加もなく、明らかに高い除菌力を保有し、高希釈倍率液にて除菌洗浄工程に適用しても充分に除菌効果を発揮する。 A more preferable sterilization detergent composition is a peracetic acid-based sterilization detergent composition, but does not increase the acetic acid odor compared to known compositions, clearly possesses a high sterilization power, and has a high Even if it is applied to the sterilization washing step with a dilution ratio solution, it exhibits a sufficient sterilization effect.
本発明の除菌洗浄剤組成物は、そのまま除菌洗浄に使用してもよいが、一般的にはそれを処理原液として、使用時に水にて希釈した液（水希釈液）をもって使用される。希釈倍率は、有機過酸濃度、該組成物の使用方法、対象の除菌物や汚染状態により適宜選択できるが、通常１０〜３００倍程度である。 The disinfectant cleaning composition of the present invention may be used as it is for disinfecting and cleaning, but generally it is used as a processing stock solution with a solution diluted with water at the time of use (water diluted solution). . The dilution rate can be appropriately selected depending on the concentration of organic peracid, the method of using the composition, the target sterilized product and the contamination state, but is usually about 10 to 300 times.
除菌洗浄剤組成物は、除菌及び洗浄が必要な対象物であれば特に限定されないが、人工透析装置あるいは内視鏡等の医療機器、水処理装置、食品製造装置等の除菌洗浄に使用することができる。 The sterilization detergent composition is not particularly limited as long as it is an object that needs to be sterilized and cleaned, but is suitable for sterilization cleaning of medical devices such as an artificial dialysis apparatus or an endoscope, a water treatment apparatus, and a food production apparatus. Can be used.
除菌洗浄する方法は、基本的に除菌洗浄すべき材料表面に除菌洗浄剤を動的あるいは静的な状態でその効果が発揮するに必要な時間接触させることによって実施できる。例えば、人工透析装置などのように液流回路を有する装置の除菌洗浄は、その液流回路中に除菌洗浄剤を規定時間流す方法（シングルパス方式）あるいは充填放置する方法（貯留方式）あるいはこれらの方法を組み合わせた方法で実施できる。また、本発明の除菌洗浄剤組成物を人工透析装置の除菌洗浄に適用した場合、装置内表面の除菌、透析工程で使用される透析液に由来し回路内に形成される炭酸カルシウムスケールの除去に優れた効果を発揮する。 The method of disinfecting and cleaning can be basically carried out by bringing the disinfecting cleaning agent into contact with the surface of the material to be disinfected and cleaned for a time necessary to exert its effect in a dynamic or static state. For example, sterilization washing of a device having a liquid flow circuit such as an artificial dialysis device is performed by a method of flowing a sterilization detergent in the liquid flow circuit for a specified time (single pass method) or a method of leaving it filled (storage method). Or it can implement by the method of combining these methods. In addition, when the sterilization detergent composition of the present invention is applied to sterilization washing of an artificial dialysis machine, the calcium carbonate formed in the circuit is derived from the dialysis solution used in the sterilization and dialysis process of the inner surface of the machine. Excellent effect in removing scale.
また、水処理装置の例としては、処理水貯槽表面あるいは逆浸透膜をはじめとする濾過膜の除菌洗浄に好適にできる。例えば、逆浸透膜により洗浄水を得る濾過膜装置（ＲＯ膜装置）において、最近多用されている芳香族ポリアミド系ＲＯ膜の除菌洗浄にも好適に使用できる。 Moreover, as an example of a water treatment apparatus, it can be suitable for the disinfection washing | cleaning of the filtration membrane including the treated water storage tank surface or a reverse osmosis membrane. For example, in a filtration membrane device (RO membrane device) that obtains washing water using a reverse osmosis membrane, it can be suitably used for disinfecting and washing aromatic polyamide RO membranes that are frequently used recently.
特にＲＯ膜の除菌洗浄を行う場合、ＲＯ膜は多くの場合鉄分を含む錆を共存付着している場合が多く、このような錆の共存ＲＯ膜に除菌処理を実施すると、膜物性の低下（脱塩率の低下）、除菌効果の低下等悪影響の出る場合がある。この悪影響を回避させる方法として、除錆処理を実施した後本発明の除菌洗浄剤組成物で処理することが好ましい。かかる目的に好適に使用できる除錆組成物としては、蓚酸、クエン酸等の有機酸をはじめとする公知の除錆処理剤が使用できるが、特に以下の除錆組成物で処理した後、本発明の除菌洗浄剤組成物で処理する方法が、ＲＯ膜物性低下の回避、錆をはじめとする付着物の除去、除菌効果の付与等で優れた効果を発揮し好ましい。 In particular, when RO membranes are sterilized and washed, RO membranes often have rust containing iron in many cases. When sterilization treatment is performed on such rust-existing RO membranes, There may be adverse effects such as reduction (decrease in desalination rate) and sterilization effect. As a method for avoiding this adverse effect, it is preferable to treat with the disinfectant cleaning composition of the present invention after carrying out the rust removal treatment. As the rust removal composition that can be suitably used for such purposes, known rust removal treatment agents including organic acids such as oxalic acid and citric acid can be used. The method of treating with the disinfectant cleaning composition of the invention is preferable because it exhibits excellent effects in avoiding deterioration of the physical properties of the RO membrane, removing deposits including rust, and providing a disinfecting effect.
すなわち、除錆組成物としては、塩基性化合物、水溶性の金属キレート剤と二酸化チオ尿素ととからなる水溶性組成物であり、その組成物と水性媒体との溶液がアルカリ性（例えば８以上）である組成物が挙げられる。塩基性化合物としては、苛性アルカリ及び苛性アルカリと弱酸との水溶性塩が挙げられ、水溶性の金属キレート剤としては、アミノカルボン酸系化合物を含むキレート剤が挙げられる。より具体的な除錆組成物としては、水性媒体に溶解され、得られた溶液中、苛性アルカリ及び苛性アルカリと弱酸との水溶性塩から選択される塩基性化合物を０．００１〜３０重量％、アミノカルボン酸系化合物からなる水溶性の金属キレート剤を０．０１〜３０重量％、二酸化チオ尿素を０．０１〜３０重量％含み、溶液調製直後において８以上のｐＨを有する組成物が挙げられる。 That is, the derusting composition is a water-soluble composition comprising a basic compound, a water-soluble metal chelating agent and thiourea dioxide, and the solution of the composition and the aqueous medium is alkaline (for example, 8 or more). The composition which is is mentioned. Examples of the basic compound include caustic alkali and water-soluble salts of caustic alkali and weak acid, and examples of the water-soluble metal chelating agent include chelating agents containing aminocarboxylic acid compounds. As a more specific rust removal composition, 0.001 to 30% by weight of a basic compound selected from caustic and a water-soluble salt of caustic and weak acid is dissolved in an aqueous medium. And a composition containing 0.01 to 30% by weight of a water-soluble metal chelating agent comprising an aminocarboxylic acid compound and 0.01 to 30% by weight of thiourea dioxide, and having a pH of 8 or more immediately after the preparation of the solution. It is done.
以下に、本発明の実施例および比較例をもって本発明を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 with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited thereto.
以下の実施例及び比較例において、過酢酸（ＰＡＡ）濃度及びＨ2Ｏ2濃度は、以下の方法により測定した。 In the following examples and comparative examples, peracetic acid (PAA) concentration and H 2 O 2 concentration were measured by the following methods.
まず、所定量の原料成分を混合溶解した配合液を作製し、配合液を１００℃にて５時間煮沸処理（還流状態）した後、室温まで冷却する。冷却後の配合液のＰＡＡとＨ2Ｏ2濃度を表１に記載の方法によって測定した。なお、配合液の１００℃×５時間の加熱処理は、ＰＡＡの合成を促進すること及び合成されたＰＡＡの経時安定性を評価するために実施した（１００℃での試験は、２５℃での約１８０倍の加速試験に相当する）。なお、表１に記載の方法は、特開平６−１３００５１号公報記載の方法に準拠した方法であり、この方法をヨードメトリー２段滴定法と呼ぶことにする。また、過硫酸塩の濃度は、過酢酸の濃度に含まれている。 First, a blended solution in which a predetermined amount of raw material components are mixed and dissolved is prepared, and the blended solution is boiled (refluxed) at 100 ° C. for 5 hours and then cooled to room temperature. The PAA and H 2 O 2 concentrations of the mixed solution after cooling were measured by the method described in Table 1. The heat treatment of the blended solution at 100 ° C. for 5 hours was carried out in order to promote the synthesis of PAA and to evaluate the temporal stability of the synthesized PAA (the test at 100 ° C. was performed at 25 ° C. This corresponds to an acceleration test of about 180 times). The method described in Table 1 is a method based on the method described in JP-A-6-130051, and this method will be referred to as iodometric two-step titration method. The concentration of persulfate is included in the concentration of peracetic acid.
また、配合液のｐＨは、ガラス電極法により測定した値である。 Moreover, pH of a compounding liquid is the value measured by the glass electrode method.
実施例１〜３及び比較例１〜３：過硫酸水素カリウムの有無による過酢酸水溶液の特性評価
表２に記載の割合で以下の原料を混合して配合液を得た。
・酢酸：９０重量％水溶液
・過酸化水素：３５重量％水溶液
・ピロリン酸：１００％固形品
・１−ヒドロキシエチリデン−１，１−ジホスホン酸（略号ＨＥＤＰとする)：６０重量％水溶液
・過硫酸水素カリウム（略号ＫＭＰＳとする）：４３重量％含有粉末（２ＫＨＳＯ5・ＫＨＳＯ4・Ｋ2ＳＯ4の混合品）、デュポン社製Ｏｘｏｎｅ
Examples 1-3 and Comparative Examples 1-3: Characteristic evaluation of peracetic acid aqueous solution with or without potassium hydrogen persulfate The following raw materials were mixed at the ratio shown in Table 2 to obtain a blended solution.
Acetic acid: 90% by weight aqueous solution Hydrogen peroxide: 35% by weight aqueous solution Pyrophosphate: 100% solid product 1-hydroxyethylidene-1,1-diphosphonic acid (abbreviated as HEDP): 60% by weight aqueous solution Persulfuric acid Potassium hydride (abbreviated as KMPS): 43 wt% powder (mixture of 2KHSO 5 · KHSO 4 · K 2 SO 4 ), Oxone manufactured by DuPont
・純水：イオン交換水（略号ＤＩＷとする）
得られた配合液のＰＡＡとＨ2Ｏ2濃度及びｐＨを表２に示す。また、比較例１〜３のそれぞれのＰＡＡに対する実施例１〜３のＰＡＡの増加率を合わせて表２に示す。更に、酢酸配合量に対するＰＡＡ濃度の変化を図１に示す。図１中、×はＫＭＰＳを使用しない例（比較例１〜３）を、□はＫＭＰＳを１．９４重量％含む例（実施例１、２−１、３）を、■はＫＭＰＳを３．８８重量％含む例（実施例２−２）を意味する。
・ Pure water: ion-exchanged water (abbreviated as DIW)
Table 2 shows the PAA, H 2 O 2 concentration and pH of the resulting blended solution. In addition, Table 2 shows the increase rates of the PAAs of Examples 1 to 3 with respect to the respective PAAs of Comparative Examples 1 to 3. Furthermore, the change of the PAA concentration with respect to the acetic acid content is shown in FIG. In FIG. 1, x indicates an example in which KMPS is not used (Comparative Examples 1 to 3), □ indicates an example (Examples 1, 2 and 3) containing 1.94% by weight of KMPS, and ■ indicates KMPS in an amount of 3. This means an example (Example 2-2) containing 88% by weight.
表２及び図１から明らかなように、ＫＭＰＳを含む実施例１〜３のＰＡＡ濃度は、ＫＭＰＳを含まない比較例１〜３のそれより明らかに増加していることが判る。また、この結果は酢酸あるいは過酸化水素を増量しなくても、ＫＭＰＳを添加するだけで過酢酸濃度を増加できることを示唆するものと言える。 As is apparent from Table 2 and FIG. 1, it can be seen that the PAA concentrations of Examples 1 to 3 containing KMPS are clearly increased from those of Comparative Examples 1 to 3 not containing KMPS. Moreover, it can be said that this result suggests that the peracetic acid concentration can be increased only by adding KMPS without increasing the amount of acetic acid or hydrogen peroxide.
実施例４〜２１及び比較例４〜２１：過硫酸水素カリウムを配合した混合有機過酸水溶液の特性評価
実施例１〜３で使用したものに加え、下記有機酸
プロピオン酸（関東化学社製鹿特級グレード）
コハク酸（関東化学社製鹿特級グレード）
グルタル酸（関東化学社製試薬）
クエン酸（扶桑化学工業社製無水品）
を使用した。表３に示す割合で原料を混合して配合液を得た。得られた配合液の１００℃にて３時間加熱処理後のＰＡＡとＨ2Ｏ2濃度及びｐＨを表３に示す。また、実施例４〜２１において、ＫＭＰＳを添加しないこと以外は同一の比較例４〜２１に対するＰＡＡ増加率を表３に示す。
Examples 4 to 21 and Comparative Examples 4 to 21: Characteristic evaluation of mixed organic peracid aqueous solution blended with potassium hydrogen persulfate In addition to those used in Examples 1 to 3, the following organic acid propionic acid (deer manufactured by Kanto Chemical Co., Inc.) Special grade)
Succinic acid (special grade by Kanto Chemical Co., Ltd.)
Glutaric acid (Kanto Chemical Co., Ltd. reagent)
Citric acid (anhydrous manufactured by Fuso Chemical Industries)
It was used. The raw materials were mixed at the ratio shown in Table 3 to obtain a blended solution. Table 3 shows the concentrations of PAA, H 2 O 2 and pH after heat treatment at 100 ° C. for 3 hours. Moreover, in Examples 4-21, the PAA increase rate with respect to the same comparative examples 4-21 is shown in Table 3 except not adding KMPS.
表３から、いずれの実施例においてもＫＭＰＳを添加することで、ＰＡＡ濃度が増加していることがわかる。更に、酢酸以外の有機酸を含む場合であっても、ＫＭＰＳの添加によりＰＡＡ濃度が増加することがわかる。 From Table 3, it can be seen that the PAA concentration is increased by adding KMPS in any of the Examples. Furthermore, even when organic acids other than acetic acid are included, it can be seen that the PAA concentration is increased by the addition of KMPS.
また、実施例１４〜１６と他の実施例を比較すると、プロピオン酸、コハク酸、グルタル酸の方がクエン酸よりＰＡＡ濃度の増加割合が大きいことがわかる。 In addition, comparing Examples 14 to 16 with other examples, it can be seen that propionic acid, succinic acid, and glutaric acid have a higher PAA concentration increase rate than citric acid.
なお、酢酸とコハク酸及びグルタル酸とを含む実施例の配合液は、酢酸及び酢酸とプロピオン酸を含む実施例の配合液に比べて、刺激臭が少なかった。よって、コハク酸及びグルタル酸を使用することで、含有有機過酸含有量が高く、かつ低臭気型の除菌洗浄剤組成物を提供することができる。 In addition, the liquid mixture of the Example containing an acetic acid, a succinic acid, and glutaric acid had few irritating odors compared with the liquid mixture of the Example containing an acetic acid and an acetic acid, and propionic acid. Therefore, by using succinic acid and glutaric acid, it is possible to provide a disinfectant cleaning composition having a high content of organic peracid and a low odor type.
実施例２２〜２６及び比較例２２〜２３：各種過硫酸塩の配合効果比較
過酸化水素を１８重量％、酢酸９重量％、ＨＥＤＰを０．４８重量％、過硫酸塩又は硫酸水素塩をＸ重量％とし、ＤＩＷにより全量を１００重量％となるように配合液を調製した。使用した過硫酸塩又は硫酸水素塩を下記する。
硫酸水素カリウム（関東化学社製試薬特級、略号ＫＨＳ）
過硫酸水素カリウム（デュポン社製Ｏｘｏｎｅ、過硫酸水素カリウム４３％含有、略号ＫＭＰＳ）
過硫酸カリウム（関東化学社製試薬特級、略号ＫＰＳ）、
過硫酸アンモニウム（関東化学社製試薬特級、略号ＡＰＳ）。
Examples 22 to 26 and Comparative Examples 22 to 23: Comparison of blending effects of
Potassium hydrogen sulfate (special grade reagent manufactured by Kanto Chemical Co., abbreviation KHS)
Potassium hydrogen persulfate (Oxone manufactured by DuPont, containing 43% potassium hydrogen persulfate, abbreviation KMPS)
Potassium persulfate (special grade reagent manufactured by Kanto Chemical Co., abbreviation KPS),
Ammonium persulfate (special grade reagent manufactured by Kanto Chemical Co., abbreviation APS).
得られた配合液のＰＡＡとＨ2Ｏ2濃度及びｐＨを、過硫酸塩又は硫酸水素塩の配合量Ｘ重量％とあわせて表４に示す。また、比較例２３及び実施例２２〜２６のＰＡＡ濃度の比較例２２に対する増加量も表４に示す。 Table 4 shows the PAA, H 2 O 2 concentration and pH of the obtained blended liquid, together with the blending amount X weight% of persulfate or hydrogen sulfate. Table 4 also shows the amount of increase in the PAA concentration of Comparative Example 23 and Examples 22 to 26 with respect to Comparative Example 22.
比較例２２及び２３と実施例２２〜２６から、ＰＡＡ濃度は過硫酸塩を使用することで増加することがわかる。実施例２５と２６から、ＫＭＰＳを使用することで、ＰＡＡ濃度が特に増加することがわかる。 From Comparative Examples 22 and 23 and Examples 22-26, it can be seen that the PAA concentration increases with the use of persulfate. Examples 25 and 26 show that the use of KMPS increases the PAA concentration particularly.
実施例２７及び比較例２４〜３０：ＫＭＰＳの保存安定性に他の配合成分が及ぼす影響に関する検討
表５に記載の割合で以下の原料を混合して配合液を得た。得られた配合液のＰＡＡとＨ2Ｏ2濃度及びｐＨを、配合直後と、１００℃で３時間後と１００℃で６時間後の熱処理後のそれぞれについて測定し、結果を表５に示す。
Example 27 and Comparative Examples 24 to 30: Study on the effect of other compounding components on the storage stability of KMPS The following raw materials were mixed at the ratio shown in Table 5 to obtain a compounded solution. The PAA, H 2 O 2 concentration and pH of the resulting blended solution were measured immediately after blending, after 3 hours at 100 ° C., and after 6 hours after heat treatment at 100 ° C., and the results are shown in Table 5.
ＫＭＰＳの水溶液中での安定性は、熱処理後におけるＰＡＡ量の比較をもって判定することができる。すなわち、表５から、ＫＭＰＳの安定性は、ＨＥＤＰの非共存系では著しく劣り（比較例２４、２５、２７）、ＨＥＤＰの共存によって向上する（比較例２６、２８）。しかし、これら比較例は、実施例２７のＰＡＡ量より低い。すなわち、ＫＭＰＳは、実施例２７のＨＥＤＰ、酢酸、過酸化水素のいずれもが共存する系に存在させることによって、その保存安定性が最も高くなることがわかる。 The stability of KMPS in an aqueous solution can be determined by comparing the amount of PAA after heat treatment. That is, from Table 5, the stability of KMPS is remarkably inferior in the non-coexisting system of HEDP (Comparative Examples 24, 25, 27), and is improved by the coexistence of HEDP (Comparative Examples 26, 28). However, these comparative examples are lower than the PAA amount of Example 27. That is, it can be seen that KMPS has the highest storage stability when it is present in a system in which all of HEDP, acetic acid, and hydrogen peroxide in Example 27 coexist.
実施例２８〜３３及び比較例３１〜３６：組成物の殺菌効力試験
１）実験方法
（ａ）供試検体
実施例６、実施例４、実施例１８の組成物および比較用として比較例４、比較例６、比較例１８、比較例２６（いずれも１００℃にて３時間加熱品）の組成物
Examples 28-33 and Comparative Examples 31-36: Bactericidal efficacy test of composition 1) Experimental method (a) Test specimens Compositions of Examples 6, 4 and 18 and Comparative Example 4 for comparison Compositions of Comparative Example 6, Comparative Example 18, and Comparative Example 26 (all heated at 100 ° C. for 3 hours)
（ｂ）特性評価方法
ｉ）試験菌
Escherichia coli IFO3972（大腸菌）
Staphylococcus aureus IFO13276（黄色ブドウ球菌）
ｉｉ）試験菌液の調製
試験菌をＳＣＤ寒天培地で３５℃、２４時間培養する。更にその１白金耳を新しいＳＣＤ寒天培地に移植し、３５℃、２４時間培養する。この前培養菌を滅菌生理食塩水に懸濁し、約１０8個／ｍｌに調製したものを試験菌液とした。
(B) Characteristic evaluation method i) Test bacteria
Escherichia coli IFO3972 (Escherichia coli)
Staphylococcus aureus IFO13276 (Staphylococcus aureus)
ii) Preparation of test bacterial solution Test bacteria are cultured on an SCD agar medium at 35 ° C. for 24 hours. Furthermore, the 1 platinum ear is transplanted to a new SCD agar medium and cultured at 35 ° C. for 24 hours. This preculture was suspended in sterilized physiological saline and prepared at about 10 8 cells / ml as a test bacterial solution.
ｉｉｉ）検体希釈液の調製
各検体を１００、３００、１０００、３０００、６０００、１００００倍となるように滅菌精製水にて希釈し、各希釈液２０ｍｌを滅菌バイアル瓶に取り、３０℃高温水槽で保温した。
iii) Preparation of specimen dilution liquid Each specimen is diluted with sterilized purified water so that it becomes 100, 300, 1000, 3000, 6000, and 10000 times. Keep warm.
ｉｖ）試験操作
滅菌バイアル瓶の各希釈検体液に試験菌１％量（０．２ｍｌ）接種した後、１０分後にその１ｍｌを採取し、ＴＧＣ培地ＩＩ（予備試験より殺菌作用を中和する効果を確認）９ｍｌに移し、この液の生菌数をＳＣＤＬＰ寒天培地混釈法により測定した。結果を表６に示す。
iv) Test procedure After inoculating each diluted specimen solution in a sterile vial with 1% test bacteria (0.2 ml), 1 ml is collected 10 minutes later, and TGC medium II (effect of neutralizing bactericidal action from preliminary test) The number of viable bacteria in this liquid was measured by the SCDLP agar medium pour method. The results are shown in Table 6.
表６の結果から明らかなように、実施例２８〜３３の組成物の方が、対応する比較例の組成物より、希釈倍率の増加に伴う殺菌力の低下度合は少なく、優れた殺菌効力を発揮すると言える。また、実施例６と４の過酢酸含有組成物である実施例２８、２９、３１及び３２は、実施例１８の非過酢酸含有組成物である実施例３０及び３３より優れた殺菌効力を発揮すると言える。 As is clear from the results in Table 6, the compositions of Examples 28 to 33 are less in the degree of sterilization power reduction due to the increase in the dilution ratio than the compositions of the corresponding comparative examples, and have excellent sterilization efficacy. It can be said that it demonstrates. In addition, Examples 28, 29, 31 and 32, which are peracetic acid-containing compositions of Examples 6 and 4, exhibit superior bactericidal efficacy than Examples 30 and 33, which are non-peracetic acid-containing compositions of Example 18. I can say that.
また、表６の結果を作図し、実施例６と４および比較例６と４ならび比較例２６の組成物について、実質的生菌がいない状態であると評価される生菌数Log値が１以下となるＰＡＡ濃度（含有過酸量の過酢酸換算値）を求めた結果を表７に示す。また、実施例６と４の組成物が含有する過酸量について、比較例６と４の組成を参照しその発生元である過酢酸とＫＭＰＳにその由来分を分け、その混合モル比を計算した結果を合わせて表７に示す。 In addition, the results of Table 6 are plotted, and the composition of Examples 6 and 4 and Comparative Examples 6 and 4 and Comparative Example 26 has a viable cell count Log value of 1 which is evaluated as having substantially no viable bacteria. Table 7 shows the results obtained for the following PAA concentration (peracetic acid equivalent value of the amount of peracid contained). In addition, with respect to the amount of peracid contained in the compositions of Examples 6 and 4, with reference to the compositions of Comparative Examples 6 and 4, the origin was divided into peracetic acid and KMPS, and the mixing molar ratio was calculated. The results are shown in Table 7.
表７の結果を組成物中ＰＡＡ含有量由来元成分比率（過酢酸／ＫＭＰＳ混合モル比）と生菌数Log値１以下となるＰＡＡ濃度の関係図を図２に示す。図中記号□はEscherichia coli、IFO3972に対する関係を、記号ＸはStaphylococcus aureus、IFO13276に対する関係を示す。また、ＫＭＰＳ／ＰＡＡ＝０／１００と１００／０を結ぶ線（細点線）は、左記成分混合比の変動に対し特性が直線的に変化する、すなわち相乗効果のない特性変化に示す場合の関係を示す。図２から明らかなように、本発明の実施例の組成物においてＫＭＰＳ／ＰＡＡ混合比の変動に対し実質的殺菌状態を示す必要薬剤濃度変化（太鎖線および太実線）は下に凹型となる特性変化を示している、すなわちＫＭＰＳとＰＡＡの混合によって殺菌効果特性は相乗的に向上していることがわかる。 FIG. 2 shows the relationship between the results of Table 7 and the PAA content origin component ratio (peracetic acid / KMPS mixed molar ratio) in the composition and the PAA concentration at which the viable cell count Log value is 1 or less. In the figure, the symbol □ represents the relationship to Escherichia coli and IFO3972, and the symbol X represents the relationship to Staphylococcus aureus and IFO13276. Further, the line connecting KMPS / PAA = 0/100 and 100/0 (thin dotted line) is a relationship in which the characteristic changes linearly with respect to the fluctuation of the left component mixture ratio, that is, the characteristic change without synergistic effect is shown. Indicates. As is clear from FIG. 2, in the composition of the example of the present invention, the necessary drug concentration change (thick chain line and thick solid line) showing a substantial bactericidal state with respect to the variation of the KMPS / PAA mixing ratio is a characteristic in which the bottom is concave. It can be seen that the bactericidal effect characteristics are synergistically improved by mixing KMPS and PAA.
Claims (5)
前記除菌洗浄剤組成物が、１液型の水性溶液であって、かつ水性媒体中に、過酸化水素を３．５〜６重量％の割合で、過硫酸水素カリウムを０．２〜５重量％の割合でかつ硫酸水素カリウムと硫酸カリウムとの３重塩の形態で、酢酸を５〜３０重量％の割合で、１−ヒドロキシエチリデン−１，１−ジホスホン酸又はその塩を０．０５〜１重量％の割合で添加して得られた水性溶液である除菌洗浄剤組成物。 As an active ingredient, a disinfecting detergent composition comprising an aqueous solution containing at least peracetic acid and persulfate,
The sterilizing detergent composition is a one-component aqueous solution, and hydrogen peroxide is added in an amount of 3.5 to 6% by weight and potassium hydrogen persulfate is added in an amount of 0.2 to 5 in an aqueous medium. in the form of weight% ratio a and triple salt of potassium hydrogen sulfate and potassium sulfate, at a rate of acetic acid from 5 to 30 wt%, of 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof 0. A disinfecting detergent composition which is an aqueous solution obtained by adding at a ratio of 05 to 1% by weight.
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