JP2020076103A - Hard surface detergent composition - Google Patents
Hard surface detergent composition Download PDFInfo
- Publication number
- JP2020076103A JP2020076103A JP2019203075A JP2019203075A JP2020076103A JP 2020076103 A JP2020076103 A JP 2020076103A JP 2019203075 A JP2019203075 A JP 2019203075A JP 2019203075 A JP2019203075 A JP 2019203075A JP 2020076103 A JP2020076103 A JP 2020076103A
- Authority
- JP
- Japan
- Prior art keywords
- component
- acid
- hard surface
- silver
- surface cleaning
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003599 detergent Substances 0.000 title abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229940100890 silver compound Drugs 0.000 claims abstract description 18
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 18
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002413 Polyhexanide Polymers 0.000 claims abstract description 16
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 55
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 45
- 229910052709 silver Inorganic materials 0.000 claims description 45
- 239000004332 silver Substances 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 20
- 150000001413 amino acids Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000003021 water soluble solvent Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229920001308 poly(aminoacid) Polymers 0.000 claims description 3
- IQRAGNMEYWPLKC-UHFFFAOYSA-N 1-(diaminomethylidene)-3-methylideneguanidine Chemical compound NC(=N)NC(=N)N=C IQRAGNMEYWPLKC-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 27
- 239000002253 acid Substances 0.000 abstract description 20
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 18
- 230000001954 sterilising effect Effects 0.000 abstract description 15
- -1 tiles Substances 0.000 description 51
- 108010039918 Polylysine Proteins 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 230000000249 desinfective effect Effects 0.000 description 15
- 125000000623 heterocyclic group Chemical group 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 9
- 239000003205 fragrance Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920000656 polylysine Polymers 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 235000007586 terpenes Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 235000001014 amino acid Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000015165 citric acid Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000008378 aryl ethers Chemical class 0.000 description 5
- 239000013068 control sample Substances 0.000 description 5
- 229940109239 creatinine Drugs 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 239000004472 Lysine Substances 0.000 description 4
- 239000004435 Oxo alcohol Substances 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 150000008365 aromatic ketones Chemical class 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 235000011087 fumaric acid Nutrition 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 210000002374 sebum Anatomy 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
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- 238000000746 purification Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 150000002473 indoazoles Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- DSQPRECRRGZSCV-UHFFFAOYSA-N penta-1,4-dien-3-yl(phenyl)silane Chemical compound C=CC([SiH2]c1ccccc1)C=C DSQPRECRRGZSCV-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- VYRLHRGPAOAVTO-UHFFFAOYSA-N penta-1,4-dien-3-ylsilane Chemical compound [SiH3]C(C=C)C=C VYRLHRGPAOAVTO-UHFFFAOYSA-N 0.000 description 1
- 238000010647 peptide synthesis reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
- 125000004495 thiazol-4-yl group Chemical group S1C=NC(=C1)* 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 1
- BNCOGDMUGQWFQE-UHFFFAOYSA-N tris(ethenyl)silicon Chemical compound C=C[Si](C=C)C=C BNCOGDMUGQWFQE-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、硬表面洗浄剤組成物に関する。 The present invention relates to a hard surface cleaning composition.
一般に、浴槽、浴室内の床、壁及び用具類等に使用されているプラスチック類、タイル、ステンレス、陶磁器、ガラス等の硬表面に付着する汚れとして、石鹸やボディーシャンプー等に含まれる脂肪酸と水道水中のカルシウム分等が結合して生成する脂肪酸金属塩（石鹸カス）や、タンパク質等の含窒素化合物、遊離脂肪酸、グリセライド類、脂肪酸金属塩（石鹸カス）等の有機物及び泥等の無機物の混合物である湯アカ汚れがある。 In general, fatty acids and water contained in soap and body shampoo, etc. as stains that adhere to hard surfaces such as plastics, tiles, stainless steel, ceramics, and glass that are generally used for bathtubs, floors in bathrooms, walls and equipment Mixtures of fatty acid metal salts (soap residue) formed by binding calcium components in water, nitrogen-containing compounds such as proteins, free fatty acids, glycerides, fatty acid metal salts (soap residue), and inorganic substances such as mud There is a hot red stain.
従来、浴室内の汚れを除去するための洗浄剤組成物として様々なものが提案されている。特許文献１には、非石鹸系アニオン界面活性剤を含む界面活性剤、グリコール系溶剤、アミノカルボン酸型キレート剤を含有し、ｐＨが１０超１２未満である浴室用液体洗浄剤組成物が開示されている。 Conventionally, various detergent compositions have been proposed for removing dirt in a bathroom. Patent Document 1 discloses a liquid detergent composition for a bathroom, which contains a surfactant containing a non-soap anionic surfactant, a glycol solvent, and an aminocarboxylic acid type chelating agent and has a pH of more than 10 and less than 12. Has been done.
生活者の衛生意識の高まりから、浴室用洗浄剤組成物には除菌力が求められる。特許文献２には、アニオン界面活性剤と、水溶性溶剤と、キレート剤と、ポリヘキサメチレンビグアニド系抗菌剤との組み合わせにより除菌力を付与した浴室用洗浄剤組成物が開示されている。
特許文献３〜５には、除菌剤としてポリリジンと銀を担持した無機化合物（銀ナノコロイド）を含む組成物が開示されている。
Due to an increase in hygiene awareness among consumers, the cleaning composition for bathrooms is required to have sterilizing power. Patent Document 2 discloses a bathroom cleaner composition having a disinfecting power imparted by a combination of an anionic surfactant, a water-soluble solvent, a chelating agent, and a polyhexamethylene biguanide antibacterial agent.
Patent Documents 3 to 5 disclose compositions containing polylysine and an inorganic compound (silver nanocolloid) carrying silver as a sterilizing agent.
しかし、洗浄力や使用時の泡立ちを良好にするためにアニオン界面活性剤を含有した浴室用洗浄剤組成物において、除菌力の付与のためにカチオン性高分子や無機系除菌剤を併用すると、アニオン界面活性剤との複合体の形成等により、特に高温保管後に、除菌力が低下する課題があった。また、弱アルカリ〜アルカリ液性では多くの硬表面において黄色ブドウ球菌に対する効果が低下する課題があった。 However, in a bathroom cleaning composition containing an anionic surfactant to improve detergency and foaming during use, a cationic polymer or an inorganic disinfectant is used together to impart disinfecting power. Then, due to the formation of a complex with an anionic surfactant and the like, there is a problem that the disinfecting power is lowered particularly after storage at high temperature. In addition, there is a problem that the effect against Staphylococcus aureus is deteriorated on many hard surfaces with weak alkali to alkaline liquid.
本発明は、洗浄力、除菌力及び液色安定性に優れた硬表面洗浄剤組成物を提供することを目的とする。 An object of the present invention is to provide a hard surface detergent composition which is excellent in detergency, disinfection ability and liquid color stability.
本発明は、以下の態様を有する。
〔１〕（Ａ）成分：アニオン界面活性剤、
（Ｂ）成分：銀化合物、ポリヘキサメチレンビグアニド及びその塩からなる群から選ばれる少なくとも１種、並びに
（Ｃ）成分：塩基性ポリアミノ酸及びその塩からなる群から選ばれる少なくとも１種、を含有し、
（前記（Ｂ）成分中の銀元素＋ポリヘキサメチレンビグアニド＋その塩）／前記（Ｃ）成分で表される質量比が０．０２５〜３．０であり、
２５℃におけるｐＨが９〜１２である、硬表面洗浄剤組成物。
〔２〕前記（Ｂ）成分が、ポリマー、アミノ酸、総炭素数３〜８で１〜２価のカルボン酸（但し、アミノ酸を除く）からなる群から選ばれる少なくとも１種と錯体化された銀、ポリヘキサメチレンビグアニド及びその塩からなる群から選ばれる少なくとも１種である、前記〔１〕の硬表面洗浄剤組成物。
〔３〕（Ｄ）成分：キレート剤をさらに含有する、前記〔１〕又は〔２〕の硬表面洗浄剤組成物。
〔４〕前記（Ｄ）成分が、エチレンジアミンテトラ酢酸又はその塩、及び、クエン酸又はその塩からなる群から選ばれる少なくとも１種を含有する前記〔３〕の硬表面洗浄剤組成物。
〔５〕前記（Ｂ）成分が、銀化合物を含み、
さらに、（Ｅ）成分：芳香族水溶性溶剤を含有する、前記〔１〕〜〔４〕のいずれかの硬表面洗浄剤組成物。
〔６〕前記（Ｂ）成分が、銀化合物を含み、
さらに、（Ｆ）成分：非イオン界面活性剤を含有する、前記〔１〕〜〔５〕のいずれかの硬表面洗浄剤組成物。
〔７〕前記（Ｂ）成分が銀化合物を含み、前記（Ｂ）成分中の銀元素／前記（Ｃ）成分で表される質量比が０．１〜１である、前記〔１〕〜〔６〕のいずれかの硬表面洗浄剤組成物。
〔８〕前記（Ｂ）成分がポリヘキサメチレンビグアニド又はその塩を含み、（前記（Ｂ）成分中のポリヘキサメチレンビグアニド＋その塩）／前記（Ｃ）成分で表される質量比が０．５〜３．０である、前記〔１〕〜〔７〕のいずれかの硬表面洗浄剤組成物。
The present invention has the following aspects.
[1] Component (A): anionic surfactant,
Component (B): at least one selected from the group consisting of silver compounds, polyhexamethylene biguanide and salts thereof, and component (C): at least one selected from the group consisting of basic polyamino acids and salts thereof. Then
(Silver element in the component (B) + polyhexamethylene biguanide + salt thereof) / the mass ratio represented by the component (C) is 0.025 to 3.0,
A hard surface cleaning composition having a pH of 9 to 12 at 25 ° C.
[2] Silver in which the component (B) is complexed with at least one selected from the group consisting of a polymer, an amino acid, and a monovalent to divalent carboxylic acid having 3 to 8 carbon atoms (excluding amino acids). The hard surface cleaning composition according to [1] above, which is at least one selected from the group consisting of polyhexamethylene biguanide and salts thereof.
[3] Component (D): The hard surface cleaning composition according to [1] or [2], which further contains a chelating agent.
[4] The hard surface cleaning composition according to [3], wherein the component (D) contains at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof and citric acid or a salt thereof.
[5] The component (B) contains a silver compound,
Further, the hard surface cleaning composition according to any one of the above [1] to [4], which further comprises (E) component: an aromatic water-soluble solvent.
[6] The component (B) contains a silver compound,
Further, the hard surface cleaning composition according to any one of the above [1] to [5], which further comprises (F) component: a nonionic surfactant.
[7] The component [B] contains a silver compound, and the mass ratio represented by the element silver in the component (B) / the component (C) is 0.1 to 1, wherein [1] to [1] 6) The hard surface cleaning composition according to any one of 6).
[8] The component (B) contains polyhexamethylene biguanide or a salt thereof, and the mass ratio represented by (polyhexamethylene biguanide in the component (B) + salt thereof) / component (C) is 0. The hard surface cleaning composition according to any one of [1] to [7], which is 5 to 3.0.
本発明の硬表面洗浄剤組成物は、洗浄力、除菌力及び液色安定性に優れる。 The hard surface cleaning composition of the present invention is excellent in detergency, disinfection and liquid color stability.
本発明の硬表面洗浄剤組成物は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を含有する。
本発明の硬表面洗浄剤組成物は、典型的には、水を含有する液状組成物である。
本発明の硬表面洗浄剤組成物は、（Ｄ）成分、（Ｅ）成分及び（Ｆ）成分から選ばれる少なくとも１種をさらに含有することが好ましい。
本発明の硬表面洗浄剤組成物は、必要に応じて、本発明の効果を損なわない範囲で、（Ａ）〜（Ｆ）成分以外の他の成分をさらに含有してもよい。
The hard surface cleaning composition of the present invention contains (A) component, (B) component and (C) component.
The hard surface cleaner composition of the present invention is typically a liquid composition containing water.
The hard surface cleaning composition of the present invention preferably further contains at least one selected from the component (D), the component (E) and the component (F).
The hard surface cleaning composition of the present invention may further contain components other than the components (A) to (F), if necessary, within a range that does not impair the effects of the present invention.
＜（Ａ）成分＞
（Ａ）成分は、アニオン界面活性剤である。
（Ａ）成分は、硬表面に付着した皮脂汚れやタンパク汚れ等に対して、効果的な洗浄力を発揮せしめるために使用する。
（Ａ）成分としては、アルキル（Ｃ１０〜Ｃ１４）ベンゼンスルホン酸塩、アルカン（Ｃ１０〜Ｃ２０）スルホン酸塩、硫酸アルキル（Ｃ１０〜Ｃ２０）塩、硫酸アルキル（Ｃ１０〜Ｃ２０）ポリオキシエチレン塩、α−オレフィン（Ｃ１０〜Ｃ１６）スルホン酸塩、アルキル（Ｃ１０〜Ｃ２０）フェノキシフェニルジスルホン酸塩、脂肪酸（Ｃ１０〜Ｃ２０）塩、α−スルホ脂肪酸（Ｃ１０〜Ｃ１８）塩、エーテルカルボン酸（Ｃ１０〜Ｃ２０）塩、リン酸アルキル（Ｃ１０〜Ｃ２０）塩、リン酸アルキル（Ｃ１０〜Ｃ２０）ポリオキシエチレン塩、ジアルキル（Ｃ８〜Ｃ２０）スルホコハク酸エステル塩、スルホコハク酸アルキル（Ｃ１０〜Ｃ２０）塩、アルケニル（Ｃ１０〜Ｃ２０）コハク酸塩、Ｎ−アシル（Ｃ１０〜Ｃ２０）アミノ酸塩、Ｎ−アシル（Ｃ１０〜Ｃ２０）メチルタウリン塩等が例示できる。「Ｃ」は炭素数を意味し、以下同様である。これらのアニオン界面活性剤は、１種を単独で、又は２種以上を組み合わせて使用することができる。
これらの中でも、洗浄力の点から、アルキルベンゼンスルホン酸塩及びα−オレフィンスルホン酸塩からなる群から選ばれる少なくとも１種が好ましい。
塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩、モノエタノールアミン塩、ジエタノールアミン塩等のアルカノールアミン塩等が挙げられる。なかでもナトリウム塩、カリウム塩等のアルカリ金属塩が好ましい。
<(A) component>
The component (A) is an anionic surfactant.
The component (A) is used in order to exert an effective detergency against sebum stains, protein stains and the like attached to the hard surface.
As the component (A), alkyl (C10-C14) benzene sulfonate, alkane (C10-C20) sulfonate, alkyl sulfate (C10-C20) salt, alkyl sulfate (C10-C20) polyoxyethylene salt, α -Olefin (C10-C16) sulfonate, alkyl (C10-C20) phenoxyphenyl disulfonate, fatty acid (C10-C20) salt, α-sulfo fatty acid (C10-C18) salt, ether carboxylic acid (C10-C20) Salt, alkyl phosphate (C10-C20) salt, alkyl phosphate (C10-C20) polyoxyethylene salt, dialkyl (C8-C20) sulfosuccinate ester salt, alkyl sulfosuccinate (C10-C20) salt, alkenyl (C10-C10) Examples thereof include C20) succinate, N-acyl (C10-C20) amino acid salt, and N-acyl (C10-C20) methyl taurine salt. “C” means the number of carbon atoms, and the same applies hereinafter. These anionic surfactants may be used alone or in combination of two or more.
Among these, at least one selected from the group consisting of alkylbenzene sulfonates and α-olefin sulfonates is preferable from the viewpoint of detergency.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Of these, alkali metal salts such as sodium salts and potassium salts are preferable.
＜（Ｂ）成分＞
（Ｂ）成分は、銀化合物、ポリヘキサメチレンビグアニド及びその塩からなる群から選ばれる少なくとも１種である。
（Ｂ）成分のうち、銀化合物としては、たとえば以下の（Ｂ１）成分、（Ｂ２）成分、及び（Ｂ３）成分が挙げられる。
<(B) component>
The component (B) is at least one selected from the group consisting of silver compounds, polyhexamethylene biguanide and salts thereof.
Among the component (B), examples of the silver compound include the following component (B1), component (B2), and component (B3).
（Ｂ１）成分は、ポリマー（以下、（ｂ１１）成分ということがある）と錯体化された銀である。
（Ｂ１）成分中の銀元素の含有量は、（Ｂ１）成分の総質量に対し、たとえば０．１〜６０質量％、あるいは０．５〜１５質量％、あるいは２０〜１００，０００ｐｐｍ、あるいは少なくとも２０ｐｐｍ、あるいは、２０〜４，０００ｐｐｍ、あるいは２０〜１，５００ｐｐｍ、あるいは３０〜７５ｐｐｍ、あるいは少なくとも５０ｐｐｍである。
The component (B1) is silver complexed with a polymer (hereinafter sometimes referred to as the component (b11)).
The content of the silver element in the component (B1) is, for example, 0.1 to 60% by mass, or 0.5 to 15% by mass, or 20 to 100,000 ppm, or at least the total mass of the component (B1). It is 20 ppm, or 20 to 4,000 ppm, or 20 to 1,500 ppm, or 30 to 75 ppm, or at least 50 ppm.
（Ｂ１）成分のポリマーとしては、下式（１）で表される単位Ａ、下式（２）で表される単位Ｂ、及び下式（３）で表される単位Ｃからなる群から選ばれる少なくとも１種のモノマー単位を含有するポリマーが挙げられる（但し、前記ポリマーの総質量に対し、前記単位Ｂの割合は９９．５質量％以下である。）。 The polymer as the component (B1) is selected from the group consisting of a unit A represented by the following formula (1), a unit B represented by the following formula (2), and a unit C represented by the following formula (3). Examples of the polymer include at least one monomer unit (provided that the proportion of the unit B is 99.5% by mass or less based on the total mass of the polymer).
式中、Ｘは、Ｎ、Ｏ及びＳからなる群から選択された少なくとも１種のヘテロ原子を有する不飽和又は芳香族複素環から選択され、
ｎは、０又は１であり、
Ｒ１は、Ｈ、ＣＨ３、及びＣＯ２Ｒ４から選択され、Ｒ４は、Ｈ、ＣＨ３、Ｃ２Ｈ５、及びＣ３〜Ｃ２４アルキル基から選択され、
Ｒ２は、Ｈ、ＣＨ３、Ｃ２Ｈ５、フェニル基、ＣＨ２ＣＯ２Ｒ５、及びＣＯ２Ｒ５から選択され、Ｒ５は、Ｈ、グリシジル基、（ＣＨ２ＣＨＲ１１Ｏ）ｍＨ、（ＣＨ２ＣＨＲ１１Ｏ）ｍ−ＣＯＣＨ２ＣＯＣＨ３、及びＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｑから選択され、Ｒ１１は、Ｈ、ＣＨ３、及びフェニル基から選択され、ｍは、１〜２０の整数であり、Ｑは、ＯＨ、ＳＯ３Ｚ、及びＸから選択され、Ｚは、Ｈ、Ｎａ、Ｋ、及びＮＨ４から選択され、但し、前記ポリマーに前記単位Ｂ及び前記単位Ｃが含有されていない場合、Ｒ２は−ＣＨ２ＣＯ２Ｒ５又は−ＣＯ２Ｒ５であり、Ｒ５はＣＨ２ＣＨ（ＯＨ）ＣＨ２Ｑであり、ＱはＸであり、
Ｒ３は、Ｈ、ＣＨ３、フェニル基、スルホン化フェニル基、フェノール基、アセテート基、ヒドロキシ基、フラグメントＯ−Ｒ１、−ＣＯ２Ｒ１２、及び−ＣＯＮＲ６Ｒ７から選択され、Ｒ１２は、Ｈ、ＣＨ３、Ｃ２Ｈ５、及びＣ３〜Ｃ２４アルキル基から選択され、Ｒ６及びＲ７は、それぞれ独立に、Ｈ、ＣＨ３、Ｃ２Ｈ５、Ｃ（ＣＨ３）２ＣＨ２ＳＯ３Ｚ、及びＣ３〜Ｃ８アルキル基から選択され、
Ｒ８及びＲ９は、それぞれ独立に、Ｈ、ＣＨ３、Ｃ２Ｈ５、及びＣ３〜Ｃ２４の直鎖又は分岐鎖アルキル基から選択され、
Ｒ１０は、Ｃ１〜Ｃ８アルキレン基、Ｃ２〜Ｃ８アルケニレン基、Ｃ６〜Ｃ１０不飽和非環式基、Ｃ６〜Ｃ１０環式基、Ｃ６〜Ｃ１０の芳香族基、オキシＣ２〜Ｃ４アルキレン基、及びポリ（オキシＣ２〜Ｃ４アルキレン）ｂ基から選択され、ｂは２〜２０の整数である。
Wherein X is selected from unsaturated or aromatic heterocycles having at least one heteroatom selected from the group consisting of N, O and S,
n is 0 or 1,
R 1 is selected from H, CH 3 , and CO 2 R 4 , R 4 is selected from H, CH 3 , C 2 H 5 , and C3-C24 alkyl groups,
R 2 is selected from H, CH 3 , C 2 H 5 , a phenyl group, CH 2 CO 2 R 5 and CO 2 R 5 , and R 5 is H, a glycidyl group, (CH 2 CHR 11 O) m. H, (CH 2 CHR 11 O ) m -COCH 2 COCH 3, and is selected from CH 2 CH (OH) CH 2 Q, R 11 is selected H, CH 3, and phenyl group, m is 1 Is an integer from 20 to 20, Q is selected from OH, SO 3 Z, and X, and Z is selected from H, Na, K, and NH 4 , provided that the unit B and the unit C are included in the polymer. Is not contained, R 2 is —CH 2 CO 2 R 5 or —CO 2 R 5 , R 5 is CH 2 CH (OH) CH 2 Q, Q is X, and
R 3 is, H, CH 3, a phenyl group, a sulfonated phenyl group, a phenol group, acetate group, hydroxy group, selected from a fragment O-R 1, -CO 2 R 12, and -CONR 6 R 7, R 12 is, H, CH 3, C 2 H 5, and C3~C24 selected from an alkyl group, R 6 and R 7 are each independently, H, CH 3, C 2 H 5, C (CH 3) 2 CH 2 SO 3 Z, and selected from C3 to C8 alkyl groups,
R 8 and R 9 are each independently selected from H, CH 3 , C 2 H 5 , and C3-C24 straight or branched chain alkyl groups,
R 10 is, C1 to C8 alkylene group, C2-C8 alkenylene group, C6-C10 unsaturated acyclic group, C6-C10 cyclic group, an aromatic group of C6-C10, oxy C2~C4 alkylene group, and poly (Oxy C2-C4 alkylene) selected from b groups, where b is an integer from 2-20.
本明細書及び特許請求の範囲において、「アルキル」には、直鎖、分枝鎖及び環式アルキル基が含まれる。「アルケニル」には、直鎖及び分枝鎖アルケニル基が含まれる。
不飽和又は芳香族複素環には、たとえば、不飽和結合を有する５員〜７員の複素環；Ｎ、Ｏ及びＳからなる群から選択された少なくとも１種のヘテロ原子を有する芳香族複素環；このような複素環の異性体及びこれらの組合せが含まれる。さらに、適切な複素環には、たとえば、一緒に縮合して、少なくとも１個のＮ、Ｏ又はＳ原子を有する、より大きな９員〜１４員の複素環を形成する５員〜７員の複素環；このような複素環の異性体及びこれらの組合せを含むことができる。
In the present specification and claims, “alkyl” includes straight chain, branched chain and cyclic alkyl groups. “Alkenyl” includes straight chain and branched chain alkenyl groups.
The unsaturated or aromatic heterocycle is, for example, a 5- to 7-membered heterocycle having an unsaturated bond; an aromatic heterocycle having at least one heteroatom selected from the group consisting of N, O and S. Includes such heterocyclic isomers and combinations thereof. Further, suitable heterocycles include, for example, 5- to 7-membered heterocycles which are fused together to form a larger 9- to 14-membered heterocycle having at least one N, O or S atom. Ring; can include such heterocyclic isomers and combinations thereof.
（Ｂ１）成分のポリマーは、複素環含有ポリマーを含むものであってよい。
複素環としては、イミダゾール、チオフェン、ピロール、オキサゾール、チアゾール及びそれらのそれぞれの異性体（たとえば、チアゾール−４−イル、チアゾール−３−イル及びチアゾール−２−イル）、テトラゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、アゾール、インダゾール、トリアゾール及びそれらのそれぞれの異性体（たとえば１，２，３−トリアゾール及び１，２，４−トリアゾール）、並びにイミダゾール１，２，３−トリアゾール−１，２，４−トリアゾールのようなこれらの組合せ、ベンゾトリアゾール、メチルベンゾトリアゾール、ベンゾチアゾール、メチルベンゾチアゾール、ベンズイミダゾール並にメチルベンズイミダゾールが挙げられる。
The polymer as the component (B1) may include a heterocycle-containing polymer.
Examples of the heterocycle include imidazole, thiophene, pyrrole, oxazole, thiazole and their respective isomers (for example, thiazol-4-yl, thiazol-3-yl and thiazol-2-yl), tetrazole, pyridine, pyridazine, pyrimidine. , Pyrazine, azoles, indazoles, triazoles and their respective isomers (eg 1,2,3-triazole and 1,2,4-triazole), and imidazole 1,2,3-triazole-1,2,4- These combinations such as triazoles, benzotriazoles, methylbenzotriazoles, benzothiazoles, methylbenzothiazoles, benzimidazoles as well as methylbenzimidazoles are mentioned.
複素環含有ポリマーとしては、たとえば、複素環含有モノマーに由来する単位を含有するポリマーが挙げられる。複素環含有モノマーとしては、たとえばビニルイミダゾールやビニルピリジンが挙げられる。
複素環含有ポリマーは、複素環含有モノマーに由来する単位のほかに、非複素環含有モノマーに由来する単位を含有していてもよい。
Examples of the heterocycle-containing polymer include a polymer containing a unit derived from a heterocycle-containing monomer. Examples of the heterocycle-containing monomer include vinylimidazole and vinylpyridine.
The heterocycle-containing polymer may contain units derived from a non-heterocycle-containing monomer in addition to the units derived from a heterocycle-containing monomer.
（Ｂ１）成分のポリマーは、典型的には、架橋剤に由来する単位を含む。
架橋剤に由来する単位の割合は、ポリマーの総質量に対し、０．５〜６０質量％が好ましく、２〜１０質量％がより好ましく、５〜８質量％がさらに好ましい。
架橋剤としては、通常使用されるものであればよく、たとえば、ジ−、トリ−、テトラ−及びより高級の多官能性エチレン性不飽和モノマーが挙げられる。より具体的には、トリビニルベンゼン；ジビニルトルエン；ジビニルピリジン；ジビニルナフタレン；ジビニルキシレン；エチレングリコールジアクリレート；トリメチロールプロパントリアクリレート；ジエチレングリコールジビニルエーテル；トリビニルシクロヘキサン；アリルメタクリレート（「ＡＬＭＡ」）；エチレングリコールジメタクリレート（「ＥＧＤＭＡ」）；ジエチレングリコールジメタクリレート（「ＤＥＧＤＭＡ」）；プロピレングリコールジメタクリレート；プロピレングリコールジアクリレート；トリメチロールプロパントリメタクリレート（「ＴＭＰＴＭＡ」）；ジビニルベンゼン（「ＤＶＢ」）；２，２−ジメチルプロパン−１，３−ジアクリレート；１，３−ブチレングリコールジアクリレート；１，３−ブチレングリコールジメタクリレート；１，４−ブタンジオールジアクリレート；ジエチレングリコールジアクリレート；ジエチレングリコールジメタクリレート；１，６−ヘキサンジオールジアクリレート；１，６−ヘキサンジオールジメタクリレート；トリプロピレングリコールジアクリレート；トリエチレングリコールジメタクリレート；テトラエチレングリコールジアクリレート；ポリエチレングリコール２００ジアクリレート；テトラエチレングリコールジメタクリレート；ポリエチレングリコールジメタクリレート；エトキシル化ビスフェノールＡジアクリレート；エトキシル化ビスフェノールＡジメタクリレート；ポリエチレングリコール６００ジメタクリレート；ポリ（ブタンジオール）ジアクリレート；ペンタエリスリトールトリアクリレート；トリメチロールプロパントリエトキシトリアクリレート；グリセリルプロポキシトリアクリレート；ペンタエリスリトールテトラアクリレート；ペンタエリスリトールテトラメタクリレート；ジペンタエリスリトールモノヒドロキシペンタアクリレート；ジビニルシラン；トリビニルシラン；ジメチルジビニルシラン；ジビニルメチルシラン；メチルトリビニルシラン；ジフェニルジビニルシラン；ジビニルフェニルシラン；トリビニルフェニルシラン；ジビニルメチルフェニルシラン；テトラビニルシラン；ジメチルビニルジシロキサン；ポリ（メチルビニルシロキサン）；ポリ（ビニルヒドロシロキサン）；ポリ（フェニルビニルシロキサン）及びこれらの２種以上の混合物が挙げられる。
The polymer as the component (B1) typically contains a unit derived from a crosslinking agent.
The proportion of the units derived from the crosslinking agent is preferably 0.5 to 60% by mass, more preferably 2 to 10% by mass, and further preferably 5 to 8% by mass, based on the total mass of the polymer.
The cross-linking agent may be any one commonly used, and examples thereof include di-, tri-, tetra- and higher polyfunctional ethylenically unsaturated monomers. More specifically, trivinylbenzene; divinyltoluene; divinylpyridine; divinylnaphthalene; divinylxylene; ethylene glycol diacrylate; trimethylolpropane triacrylate; diethylene glycol divinyl ether; trivinylcyclohexane; allyl methacrylate (“ALMA”); ethylene Glycol dimethacrylate (“EGDMA”); Diethylene glycol dimethacrylate (“DEGDMA”); Propylene glycol dimethacrylate; Propylene glycol diacrylate; Trimethylolpropane trimethacrylate (“TMPTMA”); Divinylbenzene (“DVB”); -Dimethylpropane-1,3-diacrylate; 1,3-butylene glycol diacrylate; 1,3-butylene glycol dimethacrylate; 1,4-butanediol diacrylate; diethylene glycol diacrylate; diethylene glycol dimethacrylate; 1,6- Hexanediol diacrylate; 1,6-hexanediol dimethacrylate; tripropylene glycol diacrylate; triethylene glycol dimethacrylate; tetraethylene glycol diacrylate; polyethylene glycol 200 diacrylate; tetraethylene glycol dimethacrylate; polyethylene glycol dimethacrylate; ethoxyl Bisphenol A diacrylate; ethoxylated bisphenol A dimethacrylate; polyethylene glycol 600 dimethacrylate; poly (butanediol) diacrylate; pentaerythritol triacrylate; trimethylolpropane triethoxy triacrylate; glyceryl propoxy triacrylate; pentaerythritol tetraacrylate; Pentaerythritol tetramethacrylate; dipentaerythritol monohydroxypentaacrylate; divinylsilane; trivinylsilane; dimethyldivinylsilane; divinylmethylsilane; methyltrivinylsilane; diphenyldivinylsilane; divinylphenylsilane; trivinylphenylsilane; divinylmethylphenylsilane; tetra Examples include vinylsilane; dimethylvinyldisiloxane; poly (methylvinylsiloxane); poly (vinylhydrosiloxane); poly (phenylvinylsiloxane) and mixtures of two or more thereof.
（Ｂ１）成分のポリマーは、典型的には、粒子状である。
ポリマーの平均粒子径は１〜２００ｎｍが好ましく、１〜５０ｎｍがより好ましく、１０ｎｍ未満がさらに好ましい。平均粒子径は、光散乱法により測定される数平均粒子径である。
ポリマーの分子量は、たとえば５００〜５０００である。
The polymer as the component (B1) is typically in the form of particles.
The average particle diameter of the polymer is preferably 1 to 200 nm, more preferably 1 to 50 nm, and even more preferably less than 10 nm. The average particle diameter is the number average particle diameter measured by the light scattering method.
The molecular weight of the polymer is, for example, 500 to 5000.
（Ｂ１）成分としては、ダウケミカル・ジャパン株式会社から提供されているＳＩＬＶＡＤＵＲ（登録商標）９００ Ａｎｔｉｍｉｃｒｏｂｉａｌ、ＳＩＬＶＡＤＵＲ（登録商標）９３０ Ａｎｔｉｍｉｃｒｏｂｉａｌ、ＳＩＬＶＡＤＵＲ（登録商標） ９３０ＦＬＥＸ Ａｎｔｉｍｉｃｒｏｂｉａｌ；Ｇｏｕｌｓｔｏｎ Ｔｅｃｈｎｏｌｏｇｉｅｓ，Ｉｎｃ．から提供されているＬｕｒｏｌ（登録商標）Ａｇ−１５００；松本油脂製薬株式会社から提供されているブリアンＢＧ−１（登録商標）等の市販品を使用することができる。ＳＩＬＶＡＤＵＲ ９３０ Ａｎｔｉｍｉｃｒｏｂｉａｌは、架橋剤に由来する単位の割合が１０質量％未満で、複素環含有モノマーとしてビニルイミダゾールを含み、平均粒子径が１０ｎｍ未満であるポリマーと錯体化された銀である。
（Ｂ１）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。
Examples of the component (B1) include SILVADUR (registered trademark) 900 Antimicrobial, SILVADUR (registered trademark) 930 Antimicrobial, and SILVADUR (registered trademark) 930 FLEXEXINOLOGIC. A commercially available product such as Lurol (registered trademark) Ag-1500 provided by K.K .; Brian BG-1 (registered trademark) provided by Matsumoto Yushi-Seiyaku Co., Ltd. can be used. SILVADUR 930 Antimicrobial is a silver complexed with a polymer having a proportion of units derived from a crosslinking agent of less than 10% by mass, containing vinylimidazole as a heterocycle-containing monomer, and having an average particle size of less than 10 nm.
As the component (B1), one type may be used alone, or two or more types may be used in combination.
（Ｂ２）成分は、アミノ酸（（ｂ２１）成分）、総炭素数が３〜８で１〜２価のカルボン酸（（ｂ２２）成分）及びイミダゾール誘導体（（ｂ２３）成分）からなる群から選ばれる少なくとも１種の化合物と錯体化された銀である。
（Ｂ２）成分としては、銀とアミノ酸（ヒスチジン、アルギニン、クレアチニン等）との錯体、銀とカルボン酸（ピルビン酸、グリコール酸、酢酸、酪酸、サリチル酸等）との錯体、銀とカルボン酸とアミノ酸との錯体、銀とイミダゾール誘導体（イミダゾリン等）との錯体等が挙げられる。これらの（Ｂ２）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。（Ｂ２）成分としては、株式会社Ｊ−ケミカル製ＣＦ−０１（クレアチニン及びフマル酸と銀との錯体）等の市販品を使用することができる。
中でも、（Ｂ２）成分としては、（ｂ２１）成分及び（ｂ２２）成分から選ばれる少なくとも１種と錯体化された銀が好ましい。
The component (B2) is selected from the group consisting of an amino acid (component (b21)), a carboxylic acid having a total carbon number of 3 to 8 and having a valence of 1 to 2 (component (b22)), and an imidazole derivative (component (b23)). It is silver complexed with at least one compound.
Examples of the component (B2) include a complex of silver and an amino acid (histidine, arginine, creatinine, etc.), a complex of silver and a carboxylic acid (pyruvic acid, glycolic acid, acetic acid, butyric acid, salicylic acid, etc.), a silver, a carboxylic acid and an amino acid. And a complex of silver with an imidazole derivative (such as imidazoline). These (B2) components can be used alone or in combination of two or more. As the component (B2), a commercially available product such as CF-01 (creatinine and a complex of fumaric acid and silver) manufactured by J-Chemical Co., Ltd. can be used.
Among them, as the component (B2), silver complexed with at least one selected from the component (b21) and the component (b22) is preferable.
（Ｂ３）成分は、銀の酸化物、塩化物、硝酸塩、硫酸塩あるいは銀そのものが粒子状の担体に担持されたものである。
担体の具体例としては、リン酸塩（リン酸ジルコニウム、リン酸カルシウム等）、金属酸化物（酸化ケイ素、酸化アルミニウム、酸化チタン、酸化亜鉛、酸化鉄、酸化ジリコニウム等）、無機化合物（ゼオライト、粘土鉱物、シリカゲル等）等が挙げられる。これらの担体は、１種を単独で、又は２種以上を組み合わせて使用することができる。担体としては、担持強度の点から、金属酸化物が好ましい。
（Ｂ３）成分としては、コロイド状アルミナシリカに酸化銀を担持させたものが好ましい。
（Ｂ３）成分の平均粒子径は、１〜５００ｎｍが好ましく、１〜１００ｎｍがより好ましい。平均粒子径は、光散乱法により測定される数平均粒子径である。平均粒子径が５００ｎｍ以下であれば、粒子の分散状態が安定なものになり、さらに１００ｎｍ以下であれば、粒子の分散状態がより安定なものとなる。また、平均粒子径が小さいほど、菌と分散粒子との接触が容易となる観点から除菌力に有利に作用する。
（Ｂ３）成分としては、触媒化成工業（株）製の、商品名「ＡＴＯＭＹ ＢＡＬＬ−Ｓ」、「ＡＴＯＭＹ ＢＡＬＬ−Ｌ」、「ＡＴＯＭＹ ＢＡＬＬ−ＵＡ」等の市販品を使用することができる。
（Ｂ３）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。
銀化合物としては、（Ｂ１）成分及び（Ｂ２）成分が好ましく、（ｂ１１）成分、（ｂ２１）成分及び（ｂ２２）成分からなる群から選ばれる少なくとも１種と錯体化された銀が好ましい。
The component (B3) is silver oxide, chloride, nitrate, sulfate or silver itself supported on a particulate carrier.
Specific examples of the carrier include phosphates (zirconium phosphate, calcium phosphate, etc.), metal oxides (silicon oxide, aluminum oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, etc.), inorganic compounds (zeolite, clay minerals). , Silica gel, etc.) and the like. These carriers can be used alone or in combination of two or more. As the carrier, a metal oxide is preferable from the viewpoint of supporting strength.
As the component (B3), colloidal alumina silica supported with silver oxide is preferable.
The average particle diameter of the component (B3) is preferably 1 to 500 nm, more preferably 1 to 100 nm. The average particle diameter is the number average particle diameter measured by the light scattering method. If the average particle diameter is 500 nm or less, the dispersed state of the particles will be stable, and if it is 100 nm or less, the dispersed state of the particles will be more stable. Further, the smaller the average particle size, the more advantageous the sterilizing power in terms of facilitating contact between the bacterium and the dispersed particles.
As the component (B3), commercially available products such as trade names "ATOMY BALL-S", "ATOMY BALL-L" and "ATOMY BALL-UA" manufactured by Catalysts & Chemicals Industry Co., Ltd. can be used.
As the component (B3), one type can be used alone, or two or more types can be used in combination.
As the silver compound, the component (B1) and the component (B2) are preferable, and silver complexed with at least one selected from the group consisting of the component (b11), the component (b21) and the component (b22) is preferable.
（Ｂ）成分のうち、ポリヘキサメチレンビグアニド及びその塩（以下、「（Ｂ４）成分」ともいう。）としては、たとえば、下記式（４）で表される化合物が挙げられる。 Among the component (B), examples of polyhexamethylene biguanide and salts thereof (hereinafter also referred to as “component (B4)”) include compounds represented by the following formula (4).
式中、ｙは、２〜１４の整数であり、好ましくは１０〜１４の整数、より好ましくは１１〜１３の整数、特に好ましくは１２である。
ＨＲは、有機酸又は無機酸であり、好ましくは塩酸、グルコン酸又は酢酸であり、特に好ましくは塩酸である。
ｘは、ＨＲの個数を示し、０〜５ｙの整数であり、好ましくは１〜５ｙの整数、より好ましくは２〜３ｙの整数、さらに好ましくはｙ〜２ｙの整数、特に好ましくはｙである。
（Ｂ４）成分としては、市販品を用いることができる。市販品の例として、前記式（４）中のｘ及びｙが１２であり、ＨＲが塩酸であるポリ（ヘキサメチレンビグアニド）塩酸塩である、ロンザジャパン社製の商品名Ｐｒｏｘｅｌ ＩＢ（登録商標）が挙げられる。
In the formula, y is an integer of 2 to 14, preferably an integer of 10 to 14, more preferably an integer of 11 to 13, and particularly preferably 12.
HR is an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid or acetic acid, and particularly preferably hydrochloric acid.
x represents the number of HR and is an integer of 0 to 5y, preferably an integer of 1 to 5y, more preferably an integer of 2 to 3y, still more preferably an integer of y to 2y, and particularly preferably y.
As the component (B4), a commercially available product can be used. As an example of a commercially available product, a product name Proxel IB (registered trademark) manufactured by Lonza Japan Co., Ltd., which is poly (hexamethylene biguanide) hydrochloride in which x and y in the formula (4) are 12 and HR is hydrochloric acid Is mentioned.
（Ｂ）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。
（Ｂ）成分としては、除菌力及び液色安定性の観点から、（Ｂ１）成分、（Ｂ２）成分及び（Ｂ４）成分からなる群から選ばれる少なくとも１種が好ましく、（ｂ１１）成分、（ｂ２１）成分及び（ｂ２２）成分からなる群から選ばれる少なくとも１種と錯体化された銀がより好ましく、（Ｂ１）成分がさらに好ましい。（ｂ２１）成分及び（ｂ２２）成分からなる群から選ばれる少なくとも１種と錯体化された銀としては、（ｂ２１）成分と銀との錯体、（ｂ２２）成分と銀との錯体が好ましく、クレアチニンと銀の錯体、フマル酸と銀の錯体がより好ましい。クレアチニンと銀との錯体及びフマル酸と銀との錯体の両者を含むことが特に好ましい。
As the component (B), one type can be used alone, or two or more types can be used in combination.
As the component (B), at least one selected from the group consisting of the component (B1), the component (B2) and the component (B4) is preferable from the viewpoints of sterilizing power and liquid color stability, and the component (b11), Silver complexed with at least one selected from the group consisting of component (b21) and component (b22) is more preferable, and component (B1) is still more preferable. The silver complexed with at least one selected from the group consisting of the component (b21) and the component (b22) is preferably a complex of the component (b21) and silver, a complex of the component (b22) and silver, and creatinine. And a silver complex, and a fumaric acid-silver complex are more preferable. It is particularly preferable to include both a complex of creatinine and silver and a complex of fumaric acid and silver.
＜（Ｃ）成分＞
（Ｃ）成分は、塩基性ポリアミノ酸及びその塩からなる群から選ばれる少なくとも１種である。
塩基性ポリアミノ酸とは、側鎖又は構成単位中にアミノ基等を有しており、水溶液にしたときに塩基性を示し、酸性下でカチオン性を示すものをいう。
塩基性ポリアミノ酸を構成するモノマー（アミノ酸）としては、リジン、ヒスチジン、アルギニン等が挙げられる。
塩基性ポリアミノ酸としては、抗菌効果の点から、ポリリジンが好ましい。ポリリジンは、必須アミノ酸であるＬ−リジンの重合体である。ポリリジンとしては、α−ポリリジンやε−ポリリジンが挙げられ、ε−ポリリジンが好ましい。
ε−ポリリジンは、Ｌ−リジンが直鎖状に結合したものである。ε−ポリリジンとしては、下記式（５）で表されるものが好ましい。
<(C) component>
The component (C) is at least one selected from the group consisting of basic polyamino acids and salts thereof.
The basic polyamino acid is a polyamino acid having an amino group or the like in a side chain or a structural unit, which shows basicity when made into an aqueous solution and exhibits cationicity under acidic conditions.
Examples of the monomer (amino acid) that constitutes the basic polyamino acid include lysine, histidine, and arginine.
From the viewpoint of antibacterial effect, polylysine is preferable as the basic polyamino acid. Polylysine is a polymer of L-lysine which is an essential amino acid. Examples of polylysine include α-polylysine and ε-polylysine, with ε-polylysine being preferred.
Epsilon-polylysine is a linear bond of L-lysine. As ε-polylysine, one represented by the following formula (5) is preferable.
ε−ポリリジンとしては、公知の何れの方法によって得られたものであってもよい。たとえば、特許第１２４５３６１号に記載のストレプトマイセス・アルプラス・サブスピーシーズ・リジノポリメラスを、グリセリン５質量％、酵母エキス０．５質量％、硫酸アンモニウム１質量％、リン酸水素二カリウム０．０８質量％、リン酸二水素カリウム０．１３６質量％、硫酸マグネシウム・７水和物０．０５質量％、硫酸亜鉛・７水和物０．００４質量％、硫酸鉄・７水和物０．０３質量％、ｐＨ６．８に調整した培地にて培養し、得られた培養物から分離・採取することによって得られたε−ポリリジンを用いることができる。また、ε−ポリリジンは、ペプチド合成に常用される固相法等を用いて、容易に合成することが可能であり、市販のペプチドシンセサイザー等によっても合成できる。さらに、ε−ポリリジンは、リジンのペプチドのアミノ酸配列をコードする遺伝子を利用する遺伝子工学的手法を用いて、微生物細胞、植物細胞、動物細胞において大量に生産することが可能である。ここで得られた粗合成ペプチドは、ゲル濾過、順相、逆相ＨＰＬＣ（高速液体クロマトグラフィー）、イオン交換カラム精製等、通常の蛋白質・ペプチドの精製に用いられる手段により、更に高純度化することが可能である。 The ε-polylysine may be one obtained by any known method. For example, Streptomyces alplus subspecies lysinopolymeras described in Japanese Patent No. 1245361 is used as glycerin 5% by mass, yeast extract 0.5% by mass, ammonium sulfate 1% by mass, dipotassium hydrogenphosphate 0.08% by mass. , Potassium dihydrogen phosphate 0.136% by mass, magnesium sulfate heptahydrate 0.05% by mass, zinc sulfate heptahydrate 0.004% by mass, iron sulfate heptahydrate 0.03% by mass , Ε-polylysine obtained by culturing in a medium adjusted to pH 6.8 and separating and collecting from the obtained culture can be used. Moreover, ε-polylysine can be easily synthesized by using a solid phase method or the like which is commonly used for peptide synthesis, and can also be synthesized by a commercially available peptide synthesizer or the like. Furthermore, ε-polylysine can be produced in large quantities in microbial cells, plant cells, and animal cells by using a genetic engineering technique that utilizes a gene encoding the amino acid sequence of a lysine peptide. The crude synthetic peptide obtained here is further highly purified by means commonly used for protein / peptide purification such as gel filtration, normal phase, reverse phase HPLC (high performance liquid chromatography), and ion exchange column purification. It is possible.
（Ｃ）成分の数平均分子量は、５００〜１００，０００が好ましく、１，０００〜５０，０００がより好ましく、２，０００〜２０，０００がさらに好ましい。
（Ｃ）成分の数平均分子量は、ゲルパーミエーションクロマトグラフィーにより測定された標準ポリスチレン換算の値である。
（Ｃ）成分として、市販品を用いることができる。市販品の例として、ε−ポリリジンであるチッソ社製ポリリジン（数平均分子量約４０００、２５％水溶液）が挙げられる。
（Ｃ）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。
The number average molecular weight of the component (C) is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000.
The number average molecular weight of the component (C) is a standard polystyrene conversion value measured by gel permeation chromatography.
As the component (C), a commercially available product can be used. An example of a commercially available product is poly-lysine manufactured by Chisso Corp. (number-average molecular weight of about 4000, 25% aqueous solution), which is ε-polylysine.
As the component (C), one type can be used alone, or two or more types can be used in combination.
＜（Ｄ）成分＞
（Ｄ）成分はキレート剤である。
（Ｄ）成分は、浴槽等の硬表面に付着した脂肪酸金属塩、皮脂・タンパク質汚れに対して優れた洗浄力を発揮し、微生物に対する除菌効果も発揮する。
（Ｄ）成分としては、通常使用されるものを使用でき、たとえば、有機カルボン酸類、アミノカルボン酸類、ホスホン酸類、ホスホノカルボン酸類、リン酸類等が挙げられる。有機カルボン酸類としては、酢酸、アジピン酸、モノクロル酢酸、シュウ酸、コハク酸、オキシジコハク酸、カルボキシメチルコハク酸、カルボキシメチルオキシコハク酸、ヒドロキシカルボン酸（グリコール酸、ジグリコール酸、乳酸、酒石酸、カルボキシメチル酒石酸、クエン酸、リンゴ酸、グルコン酸等）が挙げられる。アミノカルボン酸類としては、ニトリロトリ酢酸、イミノジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミノペンタ酢酸、Ｎ−ヒドロキシエチルエチレンジアミン酢酸、エチレンジアミンテトラプロピオン酢酸、トリエチレンテトラヘキサ酢酸、エチレングリコールジエーテルジアミンテトラ酢酸、ヒドロキシエチルイミノジ酢酸、シクロヘキサン−１，２−ジアミンテトラ酢酸等が挙げられる。ホスホン酸類としては、エタン−１，１−ジホスホン酸、エタン−１，１，２−トリホスホン酸、１−ヒドロキシエタン−１，１−ジホスホン酸及びその誘導体、１−ヒドロキシエタン−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、アミノトリメチレンホスホン酸等が挙げられる。ホスホノカルボン酸類としては、２−ノスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸等が挙げられる。リン酸類としては、オルソリン酸、ピロリン酸、トリポリリン酸、メタリン酸、ヘキサメタリン酸、フィチン酸等の縮合リン酸等が挙げられる。これらキレート剤は、酸の形で使用することも可能であるし、カリウム、ナトリウム等のアルカリ金属との塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミンとの塩等、塩基性物質との塩の形で使用することも可能である。これらのキレート剤は、１種を単独で、又は２種以上を組み合わせて使用することができる。
（Ｄ）成分としては、洗浄力の点から、エチレンジアミンテトラ酢酸又はその塩が好ましい。除菌力の点から、クエン酸又はその塩が好ましく、洗浄力と除菌力の点からエチレンジアミンテトラ酢酸又はその塩、クエン酸又はその塩を併用することがより好ましい。
が好ましい。
<(D) component>
The component (D) is a chelating agent.
The component (D) exerts an excellent detergency against fatty acid metal salts, sebum and protein stains adhered to a hard surface such as a bath, and also exerts a bactericidal effect against microorganisms.
As the component (D), those commonly used can be used, and examples thereof include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, and phosphoric acids. Organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, hydroxycarboxylic acid (glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxy Methyl tartaric acid, citric acid, malic acid, gluconic acid and the like). As aminocarboxylic acids, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, triethylenetetrahexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, hydroxyethylimino Diacetic acid, cyclohexane-1,2-diaminetetraacetic acid and the like can be mentioned. Examples of the phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1,2. -Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid and the like can be mentioned. Examples of the phosphonocarboxylic acids include 2-nosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid. Examples of phosphoric acids include condensed phosphoric acid such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, and phytic acid. These chelating agents can be used in the form of an acid, or a basic substance such as a salt with an alkali metal such as potassium or sodium or a salt with an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine. It is also possible to use it in the form of a salt with. These chelating agents can be used alone or in combination of two or more.
From the viewpoint of detergency, the component (D) is preferably ethylenediaminetetraacetic acid or a salt thereof. From the viewpoint of disinfecting power, citric acid or a salt thereof is preferable, and from the viewpoint of detergency and disinfecting power, ethylenediaminetetraacetic acid or a salt thereof, and citric acid or a salt thereof are more preferably used together.
Is preferred.
＜（Ｅ）成分＞
（Ｅ）成分は、芳香族水溶性溶剤である。水溶性溶剤とは、２５℃のイオン交換水１Ｌに３ｇ以上溶解する溶剤をいう。（Ｅ）成分は炭素数２〜３のアルキレングリコール単位を有する（ポリ）アルキレングリコールの芳香族エーテルが好ましい。（Ｂ）成分が銀化合物を含む場合、高温保管時における銀の析出を抑制できる。（Ｅ）成分の具体的な例としては、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル、平均分子量２００−１０００のポリエチレングリコールモノフェニルエーテル、エチレングリコールモノベンジルエーテル、ジエチレングリコールモノベンジルエーテル等が挙げられる。これらの中でも炭素数２のエチレングリコール単位を有する芳香族エーテルが好ましく、フェニル基を有する芳香族エーテルがより好ましく、ジエチレングリコールモノフェニルエーテルがさらに好ましい。これらの芳香族エーテルは、１種を単独で、又は２種以上を組み合わせて使用することができる。
<(E) component>
The component (E) is a water-soluble aromatic solvent. The water-soluble solvent is a solvent which dissolves 3 g or more in 1 L of ion-exchanged water at 25 ° C. The component (E) is preferably an aromatic ether of (poly) alkylene glycol having an alkylene glycol unit having 2 to 3 carbon atoms. When the component (B) contains a silver compound, precipitation of silver during storage at high temperature can be suppressed. Specific examples of the component (E) include ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of 200 to 1000, ethylene glycol monobenzyl ether, diethylene glycol mono. Benzyl ether and the like can be mentioned. Among these, aromatic ethers having an ethylene glycol unit having 2 carbon atoms are preferable, aromatic ethers having a phenyl group are more preferable, and diethylene glycol monophenyl ether is still more preferable. These aromatic ethers can be used alone or in combination of two or more.
＜（Ｆ）成分＞
（Ｆ）成分は、非イオン界面活性剤である。高温安定性を向上するために用いられる。（Ｆ）成分としては、高級アルコール、アルキルフェノール、高級脂肪酸又は高級アミン等にアルキレンオキシドを付加したポリオキシアルキレン型非イオン界面活性剤、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、脂肪酸アルカノールアミド、多価アルコール脂肪酸エステル又はそのアルキレンオキシド付加体、脂肪酸ポリグリセリンエステル、糖脂肪酸エステル、アルキル（又はアルケニル）アミンオキシド、アミドアミンオキシド、硬化ヒマシ油のアルキレンオキシド付加体、Ｎ−アルキルポリヒドロキシ脂肪酸アミド、アルキルグリコシド、アルキルポリグリコシド、グリセリルエーテル等が挙げられる。この中でも、高級アルコールにアルキレンオキシドを付加したポリオキシアルキレン型非イオン界面活性剤が好ましい。
アルキレンオキシドとしてはエチレンオキシド、プロピレンオキシドが挙げられ、エチレンオキシドが好ましい。アルキレンオキシドの平均付加モル数は３〜１５が好ましく、５〜１０がより好ましく、６〜８が特に好ましい。
高級アルコールのアルキル基の炭素数は８〜２０が好ましく、１０〜１５がより好ましい。
その中でも、オキソアルコールエトキシレート、ゲルベアルコールエトキシレート、天然アルコールエトキシレートが好ましく、オキソアルコールエトキシレート、ゲルベアルコールエトキシレートがより好ましい。
オキソアルコールエトキシレートではアルキル基の炭素数１０〜１５、エチレンオキシドの平均付加モル数が６〜１５のものが好ましい。具体的にはＢＡＳＦ社のＬｕｔｅｎｓｏｌＴＯシリーズが好ましい。
ゲルベアルコールエトキシレートではアルキル基の炭素数１０、エチレンオキシドの平均付加モル数が６〜１５のものが好ましい。具体的にはＢＡＳＦ社のＬｕｔｅｎｓｏｌＸＰシリーズが好ましい。
天然アルコールエトキシレートではアルキル基の炭素数１２〜１４、エチレンオキシドの平均付加モル数が６〜１５のものが好ましい。
（Ｆ）成分は、１種を単独で、又は２種以上を組み合わせて使用することができる。
（Ｆ）成分は、高温安定性の点から（Ｅ）成分との併用が好ましい。
<(F) component>
The component (F) is a nonionic surfactant. Used to improve high temperature stability. As the component (F), a polyoxyalkylene type nonionic surfactant obtained by adding an alkylene oxide to a higher alcohol, an alkylphenol, a higher fatty acid or a higher amine, a polyoxyethylene polyoxypropylene block copolymer, a fatty acid alkanolamide, a polyhydric alcohol Fatty acid ester or its alkylene oxide adduct, fatty acid polyglycerin ester, sugar fatty acid ester, alkyl (or alkenyl) amine oxide, amido amine oxide, alkylene oxide adduct of hydrogenated castor oil, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, alkyl Examples thereof include polyglycoside and glyceryl ether. Among these, polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxides to higher alcohols are preferable.
Examples of the alkylene oxide include ethylene oxide and propylene oxide, and ethylene oxide is preferable. The average addition mole number of alkylene oxide is preferably 3 to 15, more preferably 5 to 10, and particularly preferably 6 to 8.
8-20 are preferable and, as for carbon number of the alkyl group of higher alcohol, 10-15 are more preferable.
Among them, oxo alcohol ethoxylates, Guerbet alcohol ethoxylates and natural alcohol ethoxylates are preferable, and oxo alcohol ethoxylates and Guerbet alcohol ethoxylates are more preferable.
In the oxo alcohol ethoxylate, it is preferable that the alkyl group has 10 to 15 carbon atoms and the ethylene oxide has an average added mole number of 6 to 15. Specifically, the Lutensol TO series manufactured by BASF is preferable.
In the Guerbet alcohol ethoxylate, those having an alkyl group having 10 carbon atoms and an average number of moles of ethylene oxide added of 6 to 15 are preferable. Specifically, the Lutensol XP series manufactured by BASF is preferable.
In the natural alcohol ethoxylates, those having 12 to 14 carbon atoms in the alkyl group and 6 to 15 ethylene oxide on average are preferred.
As the component (F), one type can be used alone, or two or more types can be used in combination.
The component (F) is preferably used in combination with the component (E) from the viewpoint of high temperature stability.
＜他の成分＞
他の成分としては、たとえば、カチオン界面活性剤、両性界面活性剤、香料、ｐＨ調整剤、水溶性溶剤（（Ｅ）成分を除く）、色素、染料、増粘剤、粘度調整剤、表面改質剤、酸化防止剤、紫外線吸収剤、可溶化剤等が挙げられる。これら任意成分は、通常、洗浄剤に使用されるものならどのような物でもよく、特に限定されるものではない。
<Other ingredients>
Other components include, for example, cationic surfactants, amphoteric surfactants, fragrances, pH adjusters, water-soluble solvents (excluding component (E)), dyes, dyes, thickeners, viscosity modifiers, surface modifiers. Examples include denaturants, antioxidants, ultraviolet absorbers, solubilizers, and the like. These optional components are not particularly limited, as long as they are generally used in detergents.
カチオン界面活性剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルアンモニウム塩、ベンザルコニウム塩、ベンゼトニウム塩、ピリジニウム塩、イミダゾリニウム塩等が挙げられる。これらのカチオン性界面活性剤の対イオン（アニオン）としては、ハロゲンイオン等が挙げられる。 Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl ammonium salt, benzalkonium salt, benzethonium salt, pyridinium salt, imidazolinium salt and the like. Examples of the counter ion (anion) of these cationic surfactants include halogen ions.
両性界面活性剤としては、アルキルベタイン型、アルキルアミドベタイン型、イミダゾリン型、アルキルアミノスルホン型、アルキルアミノカルボン酸型、アルキルアミドカルボン酸型、アミドアミノ酸型、リン酸型両性界面活性剤等が挙げられる。なかでも、洗浄力の点から、アルキルアミノカルボン酸型が好ましい。 Examples of the amphoteric surfactant include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amideamino acid type and phosphoric acid type amphoteric surfactants. Be done. Of these, the alkylaminocarboxylic acid type is preferable from the viewpoint of detergency.
香料としては、特に限定するものではないが、たとえば、脂肪族炭化水素、テルペン炭化水素、芳香族炭化水素等の炭化水素類、脂肪族アルコール、テルペンアルコール、芳香族アルコール等のアルコール類、脂肪族エーテル、芳香族エーテル等のエーテル類、脂肪族オキサイド、テルペン類のオキサイド等のオキサイド類、脂肪族アルデヒド、テルペン系アルデヒド、水素化芳香族アルデヒド、チオアルデヒド、芳香族アルデヒド等のアルデヒド類、脂肪族ケトン、テルペンケトン、水素化芳香族ケトン、脂肪族環状ケトン、非ベンゼン系芳香族ケトン、芳香族ケトン等のケトン類、アセタール類、ケタール類、フェノール類、フェノールエーテル類、脂肪酸、テルペン系カルボン酸、水素化芳香族カルボン酸、芳香族カルボン酸等の酸類、酸アマイド類、脂肪族ラクトン、大環状ラクトン、テルペン系ラクトン、水素化芳香族ラクトン、芳香族ラクトン等のラクトン類、脂肪族エステル、フラン系カルボン酸エステル、脂肪族環状カルボン酸エステル、シクロヘキシルカルボン酸族エステル、テルペン系カルボン酸エステル、芳香族カルボン酸エステル等のエステル類、ニトロムスク類、ニトリル、アミン、ピリジン類、キノリン類、ピロール、インドール等の含窒素化合物等の、種々の合成香料及び植物からの天然香料が挙げられる。これらの香料は、１種を単独で、又は２種以上を組み合わせて使用することができ、通常、２種以上を組み合わせて使用する。 The fragrance is not particularly limited, but includes, for example, hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, and aliphatics. Ethers such as ethers and aromatic ethers, oxides such as aliphatic oxides and oxides of terpenes, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, and aliphatics Ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzene type aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids Acids such as hydrogenated aromatic carboxylic acid and aromatic carboxylic acid Lactones such as acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones and aromatic lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexylcarboxylic acids From various synthetic fragrances and plants such as group esters, esters such as terpene carboxylic acid esters, aromatic carboxylic acid esters, etc., nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, nitrogen-containing compounds such as indoles, etc. Natural fragrances. These fragrances may be used alone or in combination of two or more, and usually two or more kinds are used in combination.
ｐＨ調整剤としては、特に限定されないが、塩酸、硫酸等の無機酸、クエン酸、コハク酸、リンゴ酸、フマル酸、酒石酸、マロン酸、マレイン酸、ｐ−トルエンスルホン酸等の有機酸から選ばれる酸剤、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア及びその誘導体、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等から選ばれるアルカリ剤を用いることが好ましく、塩酸、硫酸、クエン酸から選ばれる酸剤、水酸化ナトリウム、水酸化カリウムから選ばれるアルカリ剤を用いることがより好ましい。これらのｐＨ調整剤は、１種を単独で、又は２種以上を組み合わせて使用することができる。 The pH adjuster is not particularly limited, but is selected from inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and p-toluenesulfonic acid. It is preferable to use an acid agent, an alkali agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc., and hydrochloric acid, sulfuric acid, citric acid. It is more preferable to use an acid agent selected from the above and an alkali agent selected from sodium hydroxide and potassium hydroxide. These pH adjusters can be used alone or in combination of two or more.
＜各成分の含有量＞
硬表面洗浄剤組成物において、（Ａ）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、０．１〜５．０質量％が好ましく、０．５〜３．０質量％がより好ましい。（Ａ）成分の含有量が前記範囲の下限値以上であれば、洗浄力がより優れ、前記範囲の上限値以下であれば、除菌力がより優れる。
<Content of each component>
In the hard surface cleaning composition, the content of the component (A) is preferably 0.1 to 5.0% by mass, and 0.5 to 3.0% by mass based on the total mass of the hard surface cleaning composition. % Is more preferable. When the content of the component (A) is at least the lower limit value of the above range, the detergency is more excellent, and when it is at most the upper limit value of the above range, the disinfecting power is more excellent.
（Ｂ）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、０．０００５〜０．１質量％が好ましく、０．００１〜０．０５質量％がより好ましく、０．００１〜０．０１質量％がさらに好ましい。（Ｂ）成分の含有量が前記範囲の下限値以上であれば、除菌力がより優れ、前記範囲の上限値以下であれば、液色安定性がより優れ、保存時に液色の黄変が生じにくい。
（Ｂ）成分が銀化合物を含む場合、銀化合物の含有量は、銀元素に換算した量を示すものとする。
The content of the component (B) is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.05% by mass, and 0.001 based on the total mass of the hard surface cleaning composition. Is more preferably 0.01% by mass. When the content of the component (B) is at least the lower limit value of the above range, the disinfecting power is more excellent, and when it is at most the upper limit value of the above range, the liquid color stability is more excellent and the liquid color turns yellow during storage. Is less likely to occur.
When the component (B) contains a silver compound, the content of the silver compound is the amount converted into elemental silver.
（（Ｂ）成分中の銀元素＋ポリヘキサメチレンビグアニド＋その塩）／（Ｃ）成分で表される質量比（以下、「Ｂ／Ｃ比」ともいう。）は、０．０２５〜３．０であり、０．０７５〜０．３が好ましい。Ｂ／Ｃ比が前記範囲の下限値以上であれば、硬表面洗浄剤組成物を高温下で保管した後でも良好な除菌力を得ることができる。Ｂ／Ｃ比が前記範囲の上限値以下であれば、良好な液色安定性を得ることができる。 (Silver element in component (B) + polyhexamethylene biguanide + salt thereof) / (C) mass ratio (hereinafter, also referred to as “B / C ratio”) is 0.025 to 3. It is 0, and 0.075 to 0.3 is preferable. When the B / C ratio is at least the lower limit value of the above range, good disinfecting power can be obtained even after the hard surface cleaning composition is stored at high temperature. When the B / C ratio is not more than the upper limit of the above range, good liquid color stability can be obtained.
（Ｂ）成分と（Ｃ）との合計量は、硬表面洗浄剤組成物の総質量に対して、０．００５〜０．０３質量％が好ましく、０．０１〜０．０２質量％がより好ましい。 The total amount of the component (B) and the component (C) is preferably 0.005 to 0.03% by mass, more preferably 0.01 to 0.02% by mass, based on the total mass of the hard surface cleaning composition. preferable.
（Ｂ）成分が銀化合物を含む場合、銀化合物の含有量は、（Ｂ）成分中の銀元素／（Ｃ）成分で表される質量比（以下、「Ａｇ／Ｃ比」ともいう。）が、０．１〜１となる量が好ましく、０．２〜０．６となる量がより好ましい。Ａｇ／Ｃ比が前記範囲の下限値以上であれば、除菌性能がより優れる。Ｂ／Ｃ比が前記範囲の上限値以下であれば、液色安定性がより優れる。 When the component (B) contains a silver compound, the content of the silver compound is the mass ratio represented by the silver element / (C) component in the component (B) (hereinafter, also referred to as “Ag / C ratio”). Is preferably 0.1 to 1, and more preferably 0.2 to 0.6. When the Ag / C ratio is at least the lower limit value of the above range, the disinfection performance is more excellent. When the B / C ratio is at most the upper limit value of the above range, the liquid color stability is more excellent.
（Ｂ）成分がポリヘキサメチレンビグアニド又はその塩を含む場合、（（Ｂ）成分中のポリヘキサメチレンビグアニド＋その塩）／（Ｃ）成分で表される質量比は、０．５〜３．０が好ましく、１．０〜２．０がより好ましい。質量比が上記下限値以上であれば、硬表面洗浄剤組成物を高温下で保管した後でも、良好な除菌力を得られやすい。質量比が上記上限値以下であれば、良好な液色安定性を得られやすい。 When the component (B) contains polyhexamethylene biguanide or a salt thereof, the mass ratio represented by (polyhexamethylene biguanide + salt thereof in the component (B)) / (C) component is 0.5 to 3. 0 is preferable and 1.0 to 2.0 is more preferable. When the mass ratio is at least the above lower limit value, it is easy to obtain good disinfecting power even after the hard surface cleaning composition is stored at high temperature. When the mass ratio is not more than the above upper limit value, good liquid color stability can be easily obtained.
（Ｂ）成分が（Ｂ１）成分を含む場合、（Ｂ１）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、銀元素濃度に換算して０．００１質量％以上が好ましい。（Ｂ１）成分の含有量（銀元素濃度換算）の上限は、たとえば０．００５質量％である。
（Ｂ）成分が（Ｂ２）成分を含む場合、（Ｂ２）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、銀元素濃度に換算して０．０００５質量％以上が好ましい。（Ｂ２）成分の含有量（銀元素濃度換算）の上限は、たとえば０．０２質量％である。
（Ｂ）成分が（Ｂ３）成分を含む場合、（Ｂ３）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、銀元素濃度に換算して０．００１質量％以上が好ましい。（Ｂ３）成分の含有量（銀元素濃度換算）の上限は、たとえば０．０１質量％である。
When the component (B) contains the component (B1), the content of the component (B1) is preferably 0.001 mass% or more in terms of silver element concentration, based on the total mass of the hard surface cleaning composition. .. The upper limit of the content (converted to the concentration of silver element) of the component (B1) is, for example, 0.005 mass%.
When the component (B) contains the component (B2), the content of the component (B2) is preferably 0.0005 mass% or more in terms of silver element concentration, based on the total mass of the hard surface cleaning composition. .. The upper limit of the content (converted to the concentration of silver element) of the component (B2) is, for example, 0.02 mass%.
When the component (B) contains the component (B3), the content of the component (B3) is preferably 0.001% by mass or more in terms of silver element concentration, based on the total mass of the hard surface cleaning composition. .. The upper limit of the content (converted to the concentration of silver element) of the component (B3) is, for example, 0.01% by mass.
（Ｂ）成分が（Ｂ４）成分を含む場合、（Ｂ４）成分の含有量は、（Ｂ）成分中の（Ｂ４）成分／（Ｃ）成分で表される質量比（以下、「Ｂ４／Ｃ比」ともいう。）が、０．５〜１０となる量が好ましく、１〜５となる量がより好ましい。Ｂ４／Ｃ比が前記範囲の下限値以上であれば、除菌性能がより優れる。Ｂ４／Ｃ比が前記範囲の上限値以下であれば、除菌性能がより優れる。 When the component (B) includes the component (B4), the content of the component (B4) is the mass ratio represented by the component (B4) / component (C) in the component (B) (hereinafter, “B4 / C”). It is also referred to as a "ratio"), preferably in an amount of 0.5 to 10 and more preferably in an amount of 1 to 5. When the B4 / C ratio is at least the lower limit value of the above range, the disinfection performance is more excellent. When the B4 / C ratio is not more than the upper limit value of the above range, the disinfection performance is more excellent.
（Ｃ）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、０．００１〜０．５質量％が好ましく、０．００５〜０．１質量％がより好ましく、０．０１〜０．０５質量％がさらに好ましい。（Ｃ）成分の含有量が前記範囲の下限値以上であれば、除菌力がより優れ、前記範囲の上限値以下であれば、高温保存後の香気劣化を抑制できる。 The content of the component (C) is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.1% by mass, and 0.01 to the total mass of the hard surface cleaning composition. Is more preferably 0.05% by mass. When the content of the component (C) is at least the lower limit value of the above range, the disinfecting power is more excellent, and when it is at most the upper limit value of the above range, aroma deterioration after high temperature storage can be suppressed.
（Ｄ）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、０．１〜１０．０質量部が好ましく、０．１〜５．０質量％がより好ましく、１．５〜３．０質量％がさらに好ましい。（Ｄ）成分の含有量が前記範囲内であれば、洗浄力と除菌力がより優れる。 The content of the component (D) is preferably 0.1 to 10.0 parts by mass, more preferably 0.1 to 5.0% by mass, and 1.5 with respect to the total mass of the hard surface cleaning composition. Is more preferably 3.0% by mass. When the content of the component (D) is within the above range, the detergency and the disinfecting power are more excellent.
（Ｅ）成分の含有量は、硬表面洗浄剤組成物の総質量に対して、０．０１〜１０質量％が好ましく、０．１〜１．０質量％がより好ましく、更に好ましくは０．２５〜０．７５質量％である。（Ｅ）成分の含有量が上記範囲内であると、高温安定性と除菌性能がより優れる。 The content of the component (E) is preferably 0.01 to 10% by mass, more preferably 0.1 to 1.0% by mass, and even more preferably 0.1% by mass based on the total mass of the hard surface cleaning composition. It is 25 to 0.75 mass%. When the content of the component (E) is within the above range, high temperature stability and sterilization performance are more excellent.
（Ｆ）成分の含有量は、硬表面洗浄剤洗浄剤の総質量に対して、０．０１〜２．０質量％が好ましく、０．１〜１．０質量％がより好ましく、更に好ましくは０．２５〜０．５質量％である。（Ｆ）成分の含有量が上記範囲内であると、高温安定性と除菌性能がより優れる。 The content of the component (F) is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and further preferably still more preferably 0.01 to 2.0% by mass, based on the total mass of the hard surface cleaning agent detergent. It is 0.25 to 0.5 mass%. When the content of the component (F) is within the above range, high temperature stability and sterilization performance are more excellent.
硬表面洗浄剤組成物の２５℃におけるｐＨは、９〜１２であり、１０〜１２が好ましい。ｐＨが前記範囲の下限値以上であれば、硬表面に対する洗浄力が優れる。ｐＨが前記範囲の上限値以下であれば、硬表面に対する洗浄力が優れる。
硬表面洗浄剤組成物のｐＨは、ＪＩＳ Ｚ８８０２：２０１１によって２５℃において測定した値である。
The pH of the hard surface cleaning composition at 25 ° C is 9 to 12, preferably 10 to 12. When the pH is at least the lower limit of the above range, the detergency for hard surfaces is excellent. When the pH is at or below the upper limit of the above range, the detergency for hard surfaces will be excellent.
The pH of the hard surface cleaning composition is a value measured at 25 ° C. according to JIS Z8802: 2011.
本発明の硬表面洗浄剤組成物は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、水、必要に応じて（Ｄ）成分、（Ｅ）成分、（Ｆ）成分、他の成分を混合し、必要に応じてｐＨ調整することにより調製できる。
硬表面洗浄剤組成物のｐＨは、ｐＨ調整剤等で調整できる。
The hard surface cleaning composition of the present invention comprises a component (A), a component (B), a component (C), water, and if necessary, a component (D), a component (E), a component (F) and other components. Can be prepared by mixing and adjusting the pH as necessary.
The pH of the hard surface cleaning composition can be adjusted with a pH adjusting agent or the like.
以上説明した本発明の硬表面洗浄剤組成物にあっては、（Ａ）成分、（Ｂ）成分、（Ｃ）成分を含有し、Ｂ／Ｃ比が０．０２５〜３．０であり、２５℃におけるｐＨが９〜１２であるので、洗浄力、除菌力及び液色安定性に優れる。 In the hard surface cleaner composition of the present invention described above, the component (A), the component (B) and the component (C) are contained, and the B / C ratio is 0.025 to 3.0, Since the pH at 25 ° C. is 9 to 12, it is excellent in detergency, disinfection and liquid color stability.
本発明の硬表面洗浄剤組成物を適用する硬表面の材質としては、プラスチック類、タイル、ステンレス、陶磁器、ガラス等が挙げられる。硬表面の具体例としては、浴室の浴槽、浴室内の床、壁及び用具類、蛇口や水栓、浴槽の蓋、浴室ドア、鏡、排水溝等が挙げられる。
本発明の硬表面洗浄剤組成物は、浴槽や浴室内の床や壁に付着した皮脂やタンパク汚れに対し高い洗浄力を有し、かつ黄色ブドウ球菌に対して高い除菌性能を有し、浴室用として好適である。
Examples of the hard surface material to which the hard surface cleaning composition of the present invention is applied include plastics, tiles, stainless steel, ceramics, glass and the like. Specific examples of hard surfaces include bath tubs, floors in bathrooms, walls and equipment, faucets and faucets, bath tub lids, bathroom doors, mirrors, drains and the like.
The hard surface cleaning composition of the present invention has high detergency against sebum and protein stains attached to floors and walls in bathtubs and bathrooms, and has high disinfection performance against Staphylococcus aureus, and bathroom It is suitable for use.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。本実施例において「％」は特に断りがない限り、純分の「質量％」を示す。本実施例において使用した原料は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In this example, "%" means "mass%" of pure content unless otherwise specified. The raw materials used in this example are as follows.
＜（Ａ）成分＞
Ａ−１：ＡＯＳ、Ｃ１４−αオレフィンスルホン酸ナトリウム、ライオン・スペシャリティ・ケミカルズ株式会社製、商品名「リポランＬＪ４４１」。
Ａ−２：ＬＡＳ、直鎖アルキル（Ｃ１２〜１４）ベンゼンスルホン酸ナトリウム、ライオン・スペシャリティ・ケミカルズ株式会社製、商品名「ライポンＰＳ−２３０」。
Ａ−３：ＡＥＳ、ポリオキシエチレン（２）ラウリル硫酸ナトリウム。新日本理化株式会社製、商品名「シノリンＳＰＥ−１２５０」。前記「ポリオキシエチレン（２）」の「（２）」はオキシエチレン基の平均繰り返し数を意味する。
Ａ−４：ＳＤＳ、ラウリル硫酸塩、ライオン・スペシャリティ・ケミカルズ株式会社製、商品名「サンノールＬＭ−１１３０」。
<(A) component>
A-1: AOS, C14-α sodium olefin sulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Liporan LJ441”.
A-2: LAS, straight chain alkyl (C12-14) sodium benzenesulfonate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon PS-230".
A-3: AES, polyoxyethylene (2) sodium lauryl sulfate. Product name “Sinoline SPE-1250” manufactured by Shin Nippon Rika Co., Ltd. "(2)" of the above "polyoxyethylene (2)" means the average number of repeating oxyethylene groups.
A-4: SDS, lauryl sulfate, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "SANNOL LM-1130".
＜（Ｂ）成分＞
Ｂ−１：ポリマーと錯体化された銀、ダウケミカル日本株式会社製 商品名「ＳＩＬＶＡＤＵＲ ９３０ Ａｎｔｉｍｉｃｒｏｂｉａｌ」 （銀元素濃度０．１％）。
Ｂ−２：カルボン酸及びクレアチニンと錯体化された銀、株式会社Ｊケミカル製 商品名「ＣＦ−０１」 （銀元素濃度２．５％）。
Ｂ−３：コロイド状アルミナシリカに酸化銀を担持させたナノコロイド、触媒化成社製 商品名「ＡＴＯＭＹＢＡＬＬ ＵＡ」（銀元素濃度＊０．０６８６％）。
Ｂ−４：ポリヘキサメチレンビグアニド塩酸塩、ロンザジャパン株式会社製 商品名「Ｐｒｏｘｅｌ ＩＢ」。
<(B) component>
B-1: Silver complexed with a polymer, trade name “SILVADUR 930 Antimicrobial” manufactured by Dow Chemical Japan Co., Ltd. (silver element concentration 0.1%).
B-2: Silver complexed with carboxylic acid and creatinine, trade name “CF-01” manufactured by J Chemical Co., Ltd. (concentration of silver element: 2.5%).
B-3: Nano colloid in which silver oxide is supported on colloidal alumina silica, trade name "ATOMYBALL UA" manufactured by Catalysts & Chemicals Corporation (silver element concentration * 0.0686%).
B-4: Polyhexamethylene biguanide hydrochloride, trade name “Proxel IB” manufactured by Lonza Japan Co., Ltd.
＊銀元素濃度の測定方法：
銀を含む（Ｂ）成分（ＡＴＯＭＹＢＡＬＬ ＵＡ等）の原液を硝酸（試薬特級、和光純薬工業）及び蒸留水で０．１Ｍ硝酸水溶液となるように希釈し、測定試料を作成した。一方、銀イオン標準溶液（１０００ｐｐｍ溶液、和光純薬工業）を測定試料と同様の操作で０．１Ｍ硝酸水溶液となるように希釈し、１ｐｐｍ及び０．０１ｐｐｍの標準溶液を作成した。そして、測定試料と標準試料の銀濃度を誘導結合プラズマ原子発光分析装置（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製「Ｏｐｔｉｍａ ５３００ＤＶ」）を用いて測定し、得られた測定試料の発光強度を、標準溶液を用いた検量線法により銀元素濃度に換算して定量値を得た。
* Method of measuring silver element concentration:
A stock solution of component (B) (ATOMYBALL UA, etc.) containing silver was diluted with nitric acid (special grade reagent, Wako Pure Chemical Industries, Ltd.) and distilled water to prepare a 0.1 M nitric acid aqueous solution to prepare a measurement sample. On the other hand, a silver ion standard solution (1000 ppm solution, Wako Pure Chemical Industries, Ltd.) was diluted in the same manner as the measurement sample to give a 0.1 M nitric acid aqueous solution to prepare standard solutions of 1 ppm and 0.01 ppm. Then, the silver concentrations of the measurement sample and the standard sample were measured using an inductively coupled plasma atomic emission spectrometer (“Optima 5300DV” manufactured by Perkin Elmer), and the emission intensity of the obtained measurement sample was calibrated using the standard solution. A quantitative value was obtained by converting the concentration of silver element by the linear method.
＜（Ｃ）成分＞
Ｃ−１：ポリリジン、ＪＮＣ株式会社製 商品名「ポリリジン」。
<(C) component>
C-1: Polylysine, product name “Polylysine” manufactured by JNC Corporation.
＜（Ｄ）成分＞
Ｄ−１：エチレンジアミン四酢酸二ナトリウム（ＥＤＴＡ２Ｎａ）、アクゾノーベル株式会社製 商品名「ディゾルビンＮＡ２」。
Ｄ−２：クエン酸、扶桑化学工業株式会社製 商品名「精製クエン酸（無水）」。
<(D) component>
D-1: Disodium ethylenediaminetetraacetate (EDTA2Na), trade name "Disorbin NA2" manufactured by Akzo Nobel.
D-2: Citric acid, manufactured by Fuso Chemical Industry Co., Ltd., trade name "Purified citric acid (anhydrous)".
＜（Ｅ）成分＞
Ｅ−１：ジエチレングリコールモノフェニルエーテル、日本乳化剤株式会社製 商品名「フェニルジグリコール」。
Ｅ−２：エチレングリコールモノフェニルエーテル、日本乳化剤株式会社製 商品名「フェニルグリコール」。
<(E) component>
E-1: Diethylene glycol monophenyl ether, trade name "Phenyldiglycol" manufactured by Nippon Emulsifier Co., Ltd.
E-2: Ethylene glycol monophenyl ether, trade name "Phenyl glycol" manufactured by Nippon Emulsifier Co., Ltd.
＜（Ｆ）成分＞
Ｆ−１：オキソアルコール（Ｃ１３、分岐１００％）エトキシレート［エチレンオキシドの平均付加モル数７］、ＢＡＳＦ社製、商品名「Ｌｕｔｅｎｓｏｌ ＴＯ−７」。
<(F) component>
F-1: Oxo alcohol (C13, branched 100%) ethoxylate [average number of added moles of ethylene oxide: 7], trade name "Lutensol TO-7" manufactured by BASF.
＜任意成分＞
ｐＨ調整剤：１Ｎ水酸化ナトリウム、１Ｎ塩酸、関東化学株式会社製。
水溶性溶剤：ジエチレングリコールモノブチルエーテル、日本乳化剤株式会社製、商品「ブチルジグリコール」。
色素Ａ：ダイレクトブルー８６、住友化学工業社製、商品名「Ｓｕｍｉｌｉｇｈｔ Ｓｕｐｒａ Ｔｕｒｑｕｉｓｅ Ｂｌｕｅ Ｇ ｃｏｎｃ」。
色素Ｂ：ファストグリーンＦＣＦ、癸巳化成株式会社製、商品名「緑色３号」。
香料：表１に示す香料組成物（香料Ａ、香料Ｂ）を使用した。
<Arbitrary ingredients>
pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid, manufactured by Kanto Chemical Co., Inc.
Water-soluble solvent: diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., product “Butyl diglycol”.
Dye A: Direct Blue 86, manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumilight Supra Turquise Blue G conc”.
Dye B: Fast Green FCF, manufactured by Rinka Kasei Co., Ltd., trade name "Green No. 3".
Fragrance: The fragrance composition (fragrance A, fragrance B) shown in Table 1 was used.
＜実施例１〜２５、比較例１〜６＞
表２、表３、表４に示す組成に従い、水に、（Ａ）〜（Ｆ）成分を添加し混合し、ｐＨ調整剤でｐＨを表中の値に調整した後、任意成分を添加して各例の硬表面洗浄剤組成物を得た。
表中、空欄の配合成分がある場合、その配合成分は配合されていない。表中、ｐＨ調整剤の含有量「適量」は、各例の硬表面洗浄剤組成物のｐＨを表中の値にするのに要した量である。表中、水の含有量「バランス」は、硬表面洗浄剤組成物に含まれる全配合成分の合計の配合量が１００％となるように加えられる残部を意味する。
各例の硬表面洗浄剤組成物について、洗浄力、除菌力、液色安定性、高温安定性を以下のように評価した。結果を表２、表３、表４に示す。
<Examples 1 to 25, Comparative Examples 1 to 6>
According to the compositions shown in Table 2, Table 3 and Table 4, components (A) to (F) were added to water and mixed, and after adjusting the pH to the value in the table with a pH adjuster, optional components were added. The hard surface cleaning composition of each example was obtained.
In the table, when there is a blank compounding ingredient, the compounding ingredient is not compounded. In the table, the “appropriate amount” of the content of the pH adjuster is the amount required to bring the pH of the hard surface cleaning composition of each example to the value in the table. In the table, the content “balance” of water means the balance added so that the total blending amount of all the blending components contained in the hard surface cleaning composition becomes 100%.
The hard surface cleaning composition of each example was evaluated for detergency, disinfecting power, liquid color stability, and high temperature stability as follows. The results are shown in Tables 2, 3 and 4.
（洗浄力の評価）
一般家庭の浴槽内側壁面に、ガラス繊維強化プラスチック（ＦＲＰ）製テストピース（２ｃｍ×１０ｃｍ）を固定した後、成人男性３名がそれぞれ３回入浴（１日につき１回の入浴を３日間繰り返し、その間、風呂水のみを入れ替え、浴槽は洗わずに使用）し、テストピースに汚れ（湯垢汚れ）を付着させた。
この汚れが付着したテストピースを充分乾燥させた後、このテストピースに対して、その全面が濡れるように各例の硬表面洗浄剤組成物を滴下し、３０秒間放置した後、水道水（１５℃）ですすぎ流した。テストピースを充分乾燥させ、５枚のテストピース表面の汚れの除去状態を目視、指触により、下記洗浄力の評価基準に従って評価した。下記評価基準において、◎及び○を合格とした。
［洗浄力の評価基準］
◎：汚れ落ちが非常に良好［５枚のテストピースのうち、５枚とも目視による汚れが観察されず、５枚ともテストピース全面につるつるとした指触が得られる］。
○：汚れ落ちが良好［５枚のテストピースのうち、１枚以上は目視による汚れが観察されず、かつ、テストピース全面につるつるとした指触が得られ、５枚のテストピースのうち、少なくとも１枚はテストピースにざらざらとした指触を感じる］。
△：ほとんど汚れが落ちない［５枚のテストピースのうち、５枚とも目視による汚れが観察され、５枚ともざらざらとした指触を感じるが、前記目視による汚れ及びざらざらとした指触は、洗浄前より軽減されている］。
×：全く汚れが落ちない［５枚のテストピースのうち、５枚とも目視による汚れが観察され、５枚ともざらざらとした指触を感じ、前記目視による汚れ及びざらざらとした指触は、洗浄前と変わらない］。
(Evaluation of detergency)
After fixing a test piece (2 cm x 10 cm) made of glass fiber reinforced plastic (FRP) to the inner wall surface of a bathtub of a general household, three adult males each bathed three times (one bath per day was repeated for three days, During that time, only the bath water was replaced, and the bathtub was used without washing), and stains (scale stains) were attached to the test pieces.
After sufficiently drying the test piece with the stain, the hard surface cleaning composition of each example was dripped onto the test piece so that the entire surface was wet, and after leaving it for 30 seconds, tap water (15 Rinse at ℃). The test pieces were sufficiently dried, and the state of removal of stains on the surfaces of the five test pieces was evaluated visually and by touch with a finger according to the following evaluation criteria for cleaning power. In the following evaluation criteria, ⊚ and ◯ were accepted.
[Evaluation criteria for detergency]
⊚: Very good stain removal [out of 5 test pieces, no visual stain was observed on all 5 pieces, and all 5 pieces provided a smooth finger touch on the entire surface of the test piece].
◯: Good stain removal [Out of 5 test pieces, no stain was visually observed, and smooth finger touch was obtained over the entire surface of the test pieces. At least one feels rough on the test piece].
Δ: Almost no stain was removed [Of the 5 test pieces, all 5 had visual stains and all 5 felt rough to the touch, but the visual stains and rough touch to Less than before cleaning].
X: No stain was removed [Of the 5 test pieces, all 5 were visually stained, and all 5 felt rough texture, and the above-mentioned stains and rough texture were washed. Same as before].
（除菌力の評価）
（１）対照試料の調製：
ポリオキシエチレンソルビタンモノオレアート（Ｔｗｅｅｎ８０、東京化成工業製）の、０．０５％水溶液を高圧蒸気滅菌して対照試料を調製した。
（２）試験用菌液の調製：
黄色ブドウ球菌をＴＳＡ（Ｔｒｉｐｔｉｃ Ｓｏｙ Ａｇａｒ）培地（Ｄｉｆｃｏ製）に接種し、３７℃、１８〜２０時間、前々培養した。次いで、この菌をＴＳＡ培地に接種して、３７℃、１８〜２０時間、前培養した後、滅菌した１／２ＮＢ（Ｎｕｔｒｉｅｎｔ Ｂｒｏｔｈ）培地（Ｄｉｆｃｏ製）を用い、１０６ＣＦＵ／ｍＬになるように調製した。
（３）不活性化剤の調製：
ポリペプトン、レシチン、ポリソルベートの混合物（ＬＰ希釈液ダイゴ（商品名）、日本製薬製）３０ｇを精製水１Ｌに加温溶解し、高圧蒸気滅菌して不活性化剤を調製した。
（４）試験管の滅菌：
試験管に対し、１８０℃、１時間にて乾熱滅菌を行った。
（５）除菌力測定：
評価試料（各例の硬表面洗浄剤組成物）及び対照試料を５０℃の環境で１ヶ月間保存した。
滅菌した試験管に、試験用菌液１ｍＬを添加し、続けて、５０℃の環境で１ヶ月間保存した評価試料又は対照試料９ｍＬを加え、撹拌後静置した。１０分静置後、撹拌してその中から１ｍＬ採取し、不活性化剤が９ｍＬ入った滅菌試験管に添加して撹拌したものを試験液−１とした。混釈培養法にて、試験液−１をＴＳＡ培地に塗布し、３７℃、にて４０時間培養後、菌数を求めた。対照試料のＬｏｇ菌数値から評価試料のＬｏｇ菌数値を差し引いたＬｏｇ菌数値を除菌活性値とし、下記の判定基準により判定した。下記評価基準において、◎◎、◎及び○を合格とした。
［除菌力の評価基準］
◎◎：除菌活性値が３．０以上。
◎：除菌活性値が２．５以上３．０未満。
○：除菌活性値が２．０以上２．５未満。
△：除菌活性値が１．５以上２．０未満。
×：除菌活性値が１．５未満。
(Evaluation of disinfecting power)
(1) Preparation of control sample:
A control sample was prepared by autoclaving a 0.05% aqueous solution of polyoxyethylene sorbitan monooleate (Tween 80, manufactured by Tokyo Chemical Industry Co., Ltd.).
(2) Preparation of test bacterial solution:
Staphylococcus aureus was inoculated into a TSA (Triptic Soy Agar) medium (manufactured by Difco), and pre-cultured at 37 ° C. for 18 to 20 hours. Then, this bacterium was inoculated into TSA medium, precultured at 37 ° C. for 18 to 20 hours, and then sterilized 1/2 NB (Nutrient Broth) medium (manufactured by Difco) was used to prepare 106 CFU / mL. did.
(3) Preparation of inactivating agent:
30 g of a mixture of polypeptone, lecithin and polysorbate (LP diluted solution Daigo (trade name), manufactured by Nippon Pharmaceutical Co., Ltd.) was dissolved in 1 L of purified water with heating and sterilized under high pressure to prepare an inactivating agent.
(4) Sterilization of test tubes:
The test tube was sterilized by dry heat at 180 ° C. for 1 hour.
(5) Measurement of disinfection power:
The evaluation sample (hard surface cleaning composition of each example) and the control sample were stored in an environment of 50 ° C. for one month.
To a sterilized test tube, 1 mL of the test bacterial solution was added, and subsequently, 9 mL of an evaluation sample or a control sample stored for 1 month in an environment of 50 ° C. was added, and the mixture was left standing after stirring. After standing for 10 minutes, stirring was performed to collect 1 mL of the mixture, and the deactivating agent was added to a sterile test tube containing 9 mL and stirred to prepare a test solution-1. The test solution-1 was applied to the TSA medium by the pour-in culture method and cultured at 37 ° C. for 40 hours, and then the number of bacteria was determined. The Log bacterium value obtained by subtracting the Log bacterium value of the evaluation sample from the Log bacterium value of the control sample was taken as the sterilization activity value, and judgment was made according to the following criteria. In the following evaluation criteria, ⊚, ⊚ and ∘ were passed.
[Evaluation criteria for disinfecting power]
⊚: The sterilization activity value is 3.0 or more.
A: The sterilization activity value is 2.5 or more and less than 3.0.
◯: Sterilizing activity value is 2.0 or more and less than 2.5.
B: The sterilization activity value is 1.5 or more and less than 2.0.
X: The sterilization activity value is less than 1.5.
（液色安定性の評価）
内側の材質がポリエチレン（ＰＥ）のプラスチック用パウチ袋に、各例の硬表面洗浄剤組成物を充填し、これらのパウチ袋を屋外（詳細：東京都江戸川区平井にあるライオン株式会社の５階建屋の屋上）で１週間（紫外線量として約４ＭＪ）、１ヶ月間（紫外線量として約１５ＭＪ）保存した後、内容液を無色透明のガラス瓶に移して、下記の判定基準により目視判定した。下記評価基準において、◎◎、◎及び○を合格とした。
［液色安定性の評価基準］
◎◎:１週間後も１ヶ月後も液変色はほとんど認められない。
◎：１週間後に液変色はほとんど認められず、１ヶ月後に液変色がわずかに認められる。
〇：１週間後に液変色がわずかに認められ、１ヶ月後にも液変色がわずかに認められる。
△：１週間後に液変色がわずかに認められ、１ヶ月後に明らかな液変色が認められる。
×：１週間後に明らかな液変色が認められる。
(Evaluation of liquid color stability)
A plastic pouch bag made of polyethylene (PE) is filled with the hard surface cleaning composition of each example, and these pouch bags are placed outdoors (details: Lion Corporation, 5th floor, Hirai, Edogawa-ku, Tokyo). After being stored on the roof of the building for 1 week (about 4 MJ in ultraviolet ray amount) and for 1 month (about 15 MJ in ultraviolet ray amount), the content liquid was transferred to a colorless transparent glass bottle and visually judged according to the following criteria. In the following evaluation criteria, ⊚, ⊚ and ∘ were passed.
[Evaluation criteria for liquid color stability]
⊚: Almost no liquid discoloration is observed after one week or one month.
A: Almost no liquid discoloration was observed after 1 week, and slight liquid discoloration was observed after 1 month.
◯: A slight liquid discoloration was observed after 1 week, and a slight liquid discoloration was observed even after 1 month.
Δ: A slight liquid discoloration was observed after 1 week, and a clear liquid discoloration was observed after 1 month.
X: Clear liquid discoloration is observed after 1 week.
（高温安定性の評価）
５０ｍＬガラス瓶（日電理化ガラス株式会社「ＳＶ−５０Ａ」に各例の硬表面洗浄剤組成物を５０ｇ充填し、フタをした後４０℃恒温室に４ヶ月間保存した。保存開始から１ヶ月後、２ヶ月後、３ヶ月後、４ヶ月後に、硬表面洗浄剤組成物の状態を目視判定した。下記評価基準において、◎◎、◎及び〇を合格とした。
［高温安定性の評価基準］
◎◎：４ヶ月後も析出物は認められなかった。
◎：３ヶ月後に析出物は認められず、４ヶ月後に析出物が認められた。
〇：２ヶ月後に析出物は認められず、３ヶ月後に析出物が認められた。
△：１ヶ月後に析出物は認められず、２ヶ月後に析出物が認められた。
×：１ヶ月後に析出物が認められた。
(Evaluation of high temperature stability)
A 50 mL glass bottle (Nichiden Rika Kagaku Co., Ltd. “SV-50A” was filled with 50 g of the hard surface cleaning composition of each example, covered with a lid, and stored in a thermostatic chamber at 40 ° C. for 4 months. One month after the start of storage, After 2 months, 3 months, and 4 months, the state of the hard surface cleaning composition was visually judged, and ⊚, ⊚ and ◯ were evaluated as acceptable in the following evaluation criteria.
[High temperature stability evaluation criteria]
A: No precipitate was observed even after 4 months.
⊚: No deposit was observed after 3 months, and a deposit was observed after 4 months.
◯: No deposit was observed after 2 months, and a deposit was observed after 3 months.
B: No deposit was observed after 1 month, and a deposit was observed after 2 months.
X: A deposit was observed after 1 month.
実施例１〜２５の硬表面洗浄剤組成物は、硬表面の洗浄力、除菌力、液色安定性に優れていた。
銀化合物を（Ｂ）成分として含み、（Ｅ）成分及び（Ｆ）成分の少なくとも一方を含む実施例１７〜２５は、高温安定性が「〇」〜「◎◎」であった。
（Ａ）成分を含有しない比較例１の硬表面洗浄剤組成物は、硬表面の洗浄力に劣っていた。
（Ｂ）成分又は（Ｃ）成分を含有しない比較例２〜３の硬表面洗浄剤組成物は、除菌力に劣っていた。
Ｂ／Ｃ比が０．０２５未満の比較例４の硬表面洗浄剤組成物は、除菌力に劣っていた。
Ｂ／Ｃ比が３．０超の比較例５の硬表面洗浄剤組成物は、液色安定性に劣っていた。
ｐＨが９未満の比較例６の硬表面洗浄剤組成物は、硬表面の洗浄力に劣っていた。
The hard surface cleaner compositions of Examples 1 to 25 were excellent in hard surface cleaning power, sterilization power, and liquid color stability.
Examples 17 to 25 containing the silver compound as the component (B) and at least one of the component (E) and the component (F) had high temperature stability of “◯” to “⊚⊚”.
The hard surface cleaning composition of Comparative Example 1 containing no component (A) was inferior in detergency for hard surfaces.
The hard surface cleaner compositions of Comparative Examples 2 and 3 which did not contain the component (B) or the component (C) were inferior in sterilizing power.
The hard surface cleaning composition of Comparative Example 4 having a B / C ratio of less than 0.025 was inferior in disinfecting power.
The hard surface cleaning composition of Comparative Example 5 having a B / C ratio of more than 3.0 was inferior in liquid color stability.
The hard surface cleaning composition of Comparative Example 6 having a pH of less than 9 was inferior in hard surface cleaning power.
Claims (6)
（Ｂ）成分：銀化合物、ポリヘキサメチレンビグアニド及びその塩からなる群から選ばれる少なくとも１種、並びに
（Ｃ）成分：塩基性ポリアミノ酸及びその塩からなる群から選ばれる少なくとも１種、を含有し、
（前記（Ｂ）成分中の銀元素＋ポリヘキサメチレンビグアニド＋その塩）／前記（Ｃ）成分で表される質量比が０．０２５〜３．０であり、
２５℃におけるｐＨが９〜１２である、硬表面洗浄剤組成物。 (A) component: anionic surfactant,
Component (B): at least one selected from the group consisting of silver compounds, polyhexamethylene biguanide and salts thereof, and component (C): at least one selected from the group consisting of basic polyamino acids and salts thereof. Then
(Silver element in the component (B) + polyhexamethylene biguanide + salt thereof) / the mass ratio represented by the component (C) is 0.025 to 3.0,
A hard surface cleaning composition having a pH of 9 to 12 at 25 ° C.
さらに、（Ｅ）成分：芳香族水溶性溶剤を含有する、請求項１〜４のいずれか一項に記載の硬表面洗浄剤組成物。 The component (B) contains a silver compound,
Furthermore, the hard surface cleaning composition according to any one of claims 1 to 4, further comprising (E) component: an aromatic water-soluble solvent.
さらに、（Ｆ）成分：非イオン界面活性剤を含有する、請求項１〜５のいずれか一項に記載の硬表面洗浄剤組成物。 The component (B) contains a silver compound,
Furthermore, (F) component: The hard surface cleaner composition as described in any one of Claims 1-5 containing a nonionic surfactant.
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| WO2003067311A1 (en) * | 2002-02-07 | 2003-08-14 | Ophtecs Corporation | Contact lens solution |
| US20050074467A1 (en) * | 2002-02-07 | 2005-04-07 | Masaaki Fujita | Contact lens solution |
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