JP2004167218A - 消臭剤組成物 - Google Patents
消臭剤組成物 Download PDFInfo
- Publication number
- JP2004167218A JP2004167218A JP2003351216A JP2003351216A JP2004167218A JP 2004167218 A JP2004167218 A JP 2004167218A JP 2003351216 A JP2003351216 A JP 2003351216A JP 2003351216 A JP2003351216 A JP 2003351216A JP 2004167218 A JP2004167218 A JP 2004167218A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- deodorant composition
- ethyl
- acetate
- acid
- 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
- 239000002781 deodorant agent Substances 0.000 title claims abstract description 274
- 239000000203 mixture Substances 0.000 title claims abstract description 240
- 238000006243 chemical reaction Methods 0.000 claims abstract description 133
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 109
- 150000001413 amino acids Chemical class 0.000 claims abstract description 73
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 104
- 235000001014 amino acid Nutrition 0.000 claims description 73
- 239000000419 plant extract Substances 0.000 claims description 35
- 239000004480 active ingredient Substances 0.000 claims description 20
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 235000008206 alpha-amino acids Nutrition 0.000 claims description 5
- 230000001747 exhibiting effect Effects 0.000 claims description 5
- 150000001371 alpha-amino acids Chemical class 0.000 claims description 3
- -1 polyphenol compound Chemical class 0.000 abstract description 219
- 230000001877 deodorizing effect Effects 0.000 abstract description 70
- 238000000034 method Methods 0.000 abstract description 30
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 108
- 229940024606 amino acid Drugs 0.000 description 67
- 239000003921 oil Substances 0.000 description 58
- 235000019198 oils Nutrition 0.000 description 58
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 53
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 51
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 44
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 39
- 229940022663 acetate Drugs 0.000 description 38
- 238000003756 stirring Methods 0.000 description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 32
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 32
- 235000019645 odor Nutrition 0.000 description 32
- 239000000049 pigment Substances 0.000 description 31
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 26
- 238000001914 filtration Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- 150000001299 aldehydes Chemical class 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
- 150000001241 acetals Chemical class 0.000 description 21
- 230000000694 effects Effects 0.000 description 21
- 239000000284 extract Substances 0.000 description 20
- 229940074391 gallic acid Drugs 0.000 description 20
- 235000004515 gallic acid Nutrition 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000004332 deodorization Methods 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 19
- 229930182470 glycoside Natural products 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 18
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 16
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 description 16
- 235000017550 sodium carbonate Nutrition 0.000 description 16
- 229940073490 sodium glutamate Drugs 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 15
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 15
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 15
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 15
- 229940074393 chlorogenic acid Drugs 0.000 description 15
- 235000001368 chlorogenic acid Nutrition 0.000 description 15
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 15
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 229940088598 enzyme Drugs 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 150000004665 fatty acids Chemical class 0.000 description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 14
- 239000003205 fragrance Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 235000013923 monosodium glutamate Nutrition 0.000 description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 14
- 241000196324 Embryophyta Species 0.000 description 13
- 239000004471 Glycine Substances 0.000 description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 13
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 12
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 210000002700 urine Anatomy 0.000 description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 11
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 11
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 11
- 239000000796 flavoring agent Substances 0.000 description 11
- 235000019634 flavors Nutrition 0.000 description 11
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 10
- INAXVXBDKKUCGI-UHFFFAOYSA-N 4-hydroxy-2,5-dimethylfuran-3-one Chemical compound CC1OC(C)=C(O)C1=O INAXVXBDKKUCGI-UHFFFAOYSA-N 0.000 description 10
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 10
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 10
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 10
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 10
- UNYNVICDCJHOPO-UHFFFAOYSA-N sotolone Chemical compound CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 description 10
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 10
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 9
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 9
- WRYLYDPHFGVWKC-UHFFFAOYSA-N 4-terpineol Chemical compound CC(C)C1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 9
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 235000007586 terpenes Nutrition 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- BAVONGHXFVOKBV-UHFFFAOYSA-N Carveol Chemical compound CC(=C)C1CC=C(C)C(O)C1 BAVONGHXFVOKBV-UHFFFAOYSA-N 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 8
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 description 8
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 8
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 8
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 8
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 8
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 7
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 235000002566 Capsicum Nutrition 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 7
- 241000533293 Sesbania emerus Species 0.000 description 7
- 244000269722 Thea sinensis Species 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 7
- 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 7
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- 150000002989 phenols Chemical class 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 6
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- JXZABYGWFNGNLB-UHFFFAOYSA-N 4-methoxybenzene-1,2-diol Chemical compound COC1=CC=C(O)C(O)=C1 JXZABYGWFNGNLB-UHFFFAOYSA-N 0.000 description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 6
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- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 6
- 235000009754 Vitis X bourquina Nutrition 0.000 description 6
- 235000012333 Vitis X labruscana Nutrition 0.000 description 6
- 240000006365 Vitis vinifera Species 0.000 description 6
- 235000014787 Vitis vinifera Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 6
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 description 6
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- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 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
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- SDTYFWAQLSIEBH-UHFFFAOYSA-N undec-3-ene Chemical compound CCCCCCCC=CCC SDTYFWAQLSIEBH-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 241001478887 unidentified soil bacteria Species 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- 239000001799 vanilla spp. oleoresin Substances 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 229940078465 vanillyl butyl ether Drugs 0.000 description 1
- DCSCXTJOXBUFGB-UHFFFAOYSA-N verbenone Natural products CC1=CC(=O)C2C(C)(C)C1C2 DCSCXTJOXBUFGB-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- SGEWCQFRYRRZDC-VPRICQMDSA-N vitexin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(O)C2=C1OC(C=1C=CC(O)=CC=1)=CC2=O SGEWCQFRYRRZDC-VPRICQMDSA-N 0.000 description 1
- PZKISQRTNNHUGF-UHFFFAOYSA-N vitexine Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=CC(O)=CC=1)=CC2=O PZKISQRTNNHUGF-UHFFFAOYSA-N 0.000 description 1
- 239000001529 viverra civetta schreber and viverra zibeth a schreber absolute Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000009637 wintergreen oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- BURBOJZOZGMMQF-UHFFFAOYSA-N xanthoxylol Natural products C1=C(O)C(OC)=CC=C1C1C(COC2C=3C=C4OCOC4=CC=3)C2CO1 BURBOJZOZGMMQF-UHFFFAOYSA-N 0.000 description 1
- 229940062776 zinc aspartate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical class F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229940077935 zinc phosphate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- POEVDIARYKIEGF-CEOVSRFSSA-L zinc;(2s)-2-aminobutanedioate;hydron Chemical compound [Zn+2].[O-]C(=O)[C@@H](N)CC(O)=O.[O-]C(=O)[C@@H](N)CC(O)=O POEVDIARYKIEGF-CEOVSRFSSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- GAMIYQSIKAOVTG-UHFFFAOYSA-L zinc;2-aminopentanedioate Chemical compound [Zn+2].[O-]C(=O)C(N)CCC([O-])=O GAMIYQSIKAOVTG-UHFFFAOYSA-L 0.000 description 1
- OJYLAHXKWMRDGS-UHFFFAOYSA-N zingerone Chemical compound COC1=CC(CCC(C)=O)=CC=C1O OJYLAHXKWMRDGS-UHFFFAOYSA-N 0.000 description 1
- HZRFVTRTTXBHSE-AYJHFOLZSA-N α-cedrene epoxide Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C1(C)OC1C2 HZRFVTRTTXBHSE-AYJHFOLZSA-N 0.000 description 1
- USDOQCCMRDNVAH-KKUMJFAQSA-N β-cadinene Chemical compound C1C=C(C)C[C@H]2[C@H](C(C)C)CC=C(C)[C@@H]21 USDOQCCMRDNVAH-KKUMJFAQSA-N 0.000 description 1
- FUQAYSQLAOJBBC-PAPYEOQZSA-N β-caryophyllene alcohol Chemical compound C1C[C@](C2)(C)CCC[C@]2(O)[C@H]2CC(C)(C)[C@@H]21 FUQAYSQLAOJBBC-PAPYEOQZSA-N 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
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Abstract
【解決手段】特定のポリフェノール化合物、又は、特定のポリフェノール化合物とアミノ酸をアルカリ性の溶媒中、酸素分子共存下で、反応時のpH値が6.5以上で反応して得られた有色の化合物を消臭剤組成物の有効成分とする。
Description
さらに詳しくは口臭、体臭、冷蔵庫内での臭い、生ゴミ臭、下駄箱臭、ヒトや動物の体臭、ヒト・動物の糞尿の臭いなど日常の生活において感じられる臭い、工場内あるいは工業廃液中の悪臭などを消去あるいは軽減するために使用される新規な消臭剤組成物に関する。
それら悪臭を消去あるいは軽減するために使用される消臭剤について多数の報告がある。
例えば、多種類のポリフェノール混合物を含む植物抽出液を消臭剤とする報告がある(例えば、特許文献1参照)。これら消臭剤は、消臭効果が十分とはいえない。一方、植物抽出液とフェノールオキシダーゼとを構成成分とする消臭剤組成物も公知であり(例えば、特許文献2、特許文献3を参照)、これらの消臭剤は消臭効果が優れているものの、調製方法がやや複雑であるという問題点が残されている。
さらに、一度消臭剤組成物を調製すれば、長い時間が経過しても消臭能が維持されれば、それだけ有利であるから、消臭能が維持される消臭剤組成物が望まれていた。また、含窒素化合物、含硫黄化合物、低級脂肪酸などの各種悪臭成分に対して優れた消臭効果を有する消臭剤組成物が期待されていた。
なお、特定のポリフェノールの消臭効果をNH4OH溶液中あるいはNaHCO3溶液中で確認した報告があるが(非特許文献1参照)、そこには例示されたポリフェノールを原料として新たな消臭剤を得る考えは無い。
一方、カフェー酸エステルとアミノ酸とを反応させると有色の化合物が調製できたことが報告されているが(非特許文献2を参照)、その化合物が消臭機能を有することを示唆する記載はない。
しかもその消臭剤組成物を長い時間保存しても、その消臭剤組成物の消臭効果が長く維持されることを見出し、さらに研究を重ね、遂に本発明に到達した。
(1)ポリフェノールを、アルカリ性を示す溶媒中、酸素分子共存下、反応時のpH値が6.5以上で反応させて得られる有色の化合物を有効成分として含有することを特徴とする消臭剤組成物、
(2)反応中の酸素分子供給量が1mg/L以上であることを特徴とする上記消臭剤組成物、
(3)反応時の温度が0〜60℃であることを特徴とする上記消臭剤組成物、
(4)さらに金属イオンを添加して反応させることを特徴とする上記消臭剤組成物、
(5)ポリフェノールがo−ジフェノール構造を有するポリフェノールである上記消臭剤組成物、
(6)ポリフェノールがヒドロキノンである上記消臭剤組成物、
(7)ポリフェノールの代わりに実質的にアミノ酸を含まない植物抽出物を用いる上記消臭剤組成物、
(8)さらにアミノ酸を添加して反応させることを特徴とする(1)〜(4)記載の消臭剤組成物、
(9)さらにアミノ酸を添加して反応させることを特徴とする(5)〜(7)記載の消臭剤組成物、
(10)アミノ酸がα−アミノ酸である(8)または(9)記載の消臭剤組成物、
(11)ポリフェノールとアミノ酸との代わりにポリフェノールとアミノ酸を含む植物抽出物および/または植物体を用いる(8)記載の消臭剤組成物、
に関するものである。
まず本発明の消臭剤組成物を調製する原料であるポリフェノールについて説明する。本発明で使用されるポリフェノールとは、同一ベンゼン環に二個あるいは二個以上の水酸基が水素原子と置換されている化合物を意味し、その配糖体もポリフェノールとして含む。本発明で使用されるポリフェノールは、所期の目的を達成できるポリフェノールである限りとくに限定されない。その中でも、ヒドロキノンおよびo−ジフェノール構造を有するポリフェノールが好ましい。なお、o−ジフェノール構造とはベンゼン環に直接水酸基が置換されており、しかもその水酸基が隣接しているときの構造を意味する。
これらのポリフェノールは、それぞれ単独で用いてもよいし、2種以上混合して用いても良い。
また、上記ポリフェノールは、公知の方法により調製できるが、市販品を購入してもよい。また、合成により調製してもよい。さらには、植物から調製した高濃度ポリフェノール画分を使用することもできる。
なお、ポリフェノール化合物と、アミノ酸を実質的に含まないポリフェノール含有植物抽出物とを併用してもよい。
本発明で使用されるアミノ酸は、本発明の所期の効果をもたらすアミノ酸である限り、とくに限定されないのであるが、アミノ酸の中でもα−アミノ酸がとくに好ましい。ここで、α−アミノ酸とは一つのアミノ基と一つのカルボキシル基とが一つの同じ炭素原子に結合しているアミノ酸をいう。α−アミノ酸の例としては、例えば、グリシン、アラニン、バリン、ロイシン、イソロイシン、グルタミン酸、アスパラギン酸、グルタミン、アスパラギン、セリン、スレオニン、リジン、ヒドロキシリジン、アルギニン、ヒスチジン、シスチン、メチオニン、フェニルアラニン、チロシン、トリプトファン、プロリン、4−ヒドロキシプロリン、システイン、テアニン、アミノ酸塩(グルタミン酸ナトリウム、アスパラギン酸ナトリウム)等が挙げられる。
これらアミノ酸は市販品を購入することにより容易に入手できる。また、これらアミノ酸をそれぞれ単独で用いてもよいし、2種以上混合して用いても良い。さらには、アミノ酸を含有する植物抽出物を使用することもできる。
また、本発明で消臭剤組成物を得る際には、アミノ酸の代わりに、実質的にポリフェノールを含まずアミノ酸を含む植物抽出物を使用することができる。ここでいう実質的にポリフェノールを含まずアミノ酸を含む植物抽出物は公知の方法を用いて調製することができるが、市販品を購入してもよい。なお、アミノ酸と、ポリフェノールを実質的に含まないアミノ酸含有植物抽出物とを併用してもよい。
アルカリ性を示す溶媒は、公知のものであり、代表的にはアルカリ性物質を水などの溶媒に溶解させたアルカリ性物質含有溶媒である。
アルカリ性物質としては、とくに限定されないのであるが、具体的には、炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、炭酸アンモニウム、炭酸グアニジン等の炭酸塩;もしくは炭酸水素塩;ホウ酸カリウム、ホウ酸ナトリウム等のホウ酸塩;珪酸カリウム、1号珪酸ナトリウム、2号珪酸ナトリウム、3号珪酸ナトリウム、オルト珪酸ナトリウム、メタ珪酸ナトリウム等の珪酸塩;リン酸1水素ナトリウム、亜硫酸ナトリウム、水酸化ナトリウム、水酸化カルシウム、水酸化カリウム、水酸化マグネシウム、水酸化アンモニウム、ピロリン酸ナトリウム、ピロリン酸カリウムなどが挙げられる。
上記溶媒は通常アルカリ性を示し、反応前はアルカリ性であるが、消臭剤組成物の出発物質など、溶媒中に共存させる物質およびその添加量によっては弱酸性を示すときがある。すなわち、反応前の溶媒は必ずアルカリ性であり、かつ上記消臭剤組成物を得る際、反応開始後の反応系の溶媒のpHが6.5以上となると好ましい結果が得られる。とくに反応中のpH7〜13とすることが好ましく、さらにはpH8〜13とすることが好ましい。反応中の反応系内のpHが6.5を下回ると、好ましい消臭効果を有する消臭剤組成物をもたらすことができず、逆に、あまりにも高いpH(pH14付近)とすると、消臭剤組成物を取り扱う際に注意が必要であり、不都合である。
その場合、反応液中への酸素供給量が1mg/L以上であれば、効率よく消臭剤組成物を得ることができる。この酸素供給量を達成させるには、例えば、酸素ガス、空気あるいはそれらの混合物を、反応系内に積極的に吹き込む(バブリングさせる)ことで達成することができるが、酸素ガスあるいは空気が常に接触できる反応条件下で反応液を攪拌することによっても達成することができる。
本発明では、ポリフェノールは短時間で反応するのであるが、実用的な点からでは、数分(2分)〜24時間程度、反応させることにより消臭剤組成物を調製することができる。とくに10分〜9時間程度反応させるのが好ましく、更に好ましくは10分〜7時間反応させるのが良い。
上記消臭剤組成物を調製する反応に際しては、とくに加圧する必要はないが、加圧してもよい。
好ましい金属イオンは、銅イオン、亜鉛イオン、カルシウムイオン、マグネシウムイオン、銀イオン、スズイオン、アルミニウムイオン、マンガンイオンが挙げられる。
金属イオンを放出する化合物の例として、以下のものを挙げることができる。例えば、塩化銅、フッ化銅、硫酸銅、硝酸銅、水酸化銅、クエン酸銅、グルコン酸銅、アスパラギン酸銅、グルタミン酸銅、銅クロロフィリンナトリウム、銅クロロフィル等の銅化合物; 塩化亜鉛、フッ化亜鉛、硫酸亜鉛、硝酸亜鉛、水酸化亜鉛、クエン酸亜鉛、グルコン酸亜鉛、アスパラギン酸亜鉛、グルタミン酸亜鉛、リン酸亜鉛、乳酸亜鉛等の亜鉛化合物; 塩化カルシウム、水酸化カルシウム、クエン酸カルシウム、グルコン酸カルシウム、L−グルタミン酸カルシウム、炭酸カルシウム、乳酸カルシウム、パントテン酸カルシウム、ピロリン酸二水素カルシウム、プロピオン酸カルシウム、硫酸カルシウム、リン酸三カルシウム、リン酸一水素カルシウム、リン酸二水素カルシウム、エチレンジアミン四酢酸カルシウム二ナトリウム等のカルシウム化合物; 塩化マグネシウム、硫酸マグネシウム、水酸化マグネシウム、L−グルタミン酸マグネシウム、酸化マグネシウム、炭酸マグネシウム等のマグネシウム化合物; 酸化銀等の銀化合物; 塩化スズ、酢酸スズ、フッ化スズ等のスズ化合物; 塩化アルミニウム、水酸化アルミニウム、酢酸アルミニウム、ホウ酸アルミニウム、リン酸アルミニウム、硫酸アルミニウム等のアルミニウム化合物; 過マンガン酸カリウム等の過マンガン酸塩、硫酸マンガン等のマンガン化合物などがあげられる。また二酸化チタン等のチタン化合物も使用することができる。
金属イオンの添加量としては、反応の状況により異なるが、反応液中の金属イオンの濃度が0.00001mM〜100mMとなるように添加することが好ましく、より好ましくは0.00005mM〜10mMであり、さらに好ましくは0.1mM〜5mMである。
本発明の消臭剤組成物は、ポリフェノールとアミノ酸を含む植物抽出物、つまり、植物の葉、茎、根、(果)実などから選ばれる少なくとも1つの部位からの抽出物を、アルカリ性を示す溶媒に添加し、反応中の反応液をpH6.5以上に調製して、酸素供給量1mg/L以上、反応温度0℃〜溶剤リフラックス温度、反応時間数分〜24時間で処理することによっても得ることができる。この場合のアルカリ性物質、溶媒の例としては、上記したものがあげられ、反応条件などは前記と同様に操作することにより得られる。なお、ポリフェノールとアミノ酸との代わりに、ポリフェノールとアミノ酸とを含む植物抽出物を使用した場合、さらに、実質的にアミノ酸を含まないポリフェノール含有植物抽出物、実質的にポリフェノールを含まないアミノ酸含有植物抽出物、ポリフェノール、アミノ酸から選ばれる少なくとも1種を併用してもよい。また、植物抽出物の例は以下に示してある。
具体的には、本発明の消臭剤組成物は、本発明のポリフェノールとアミノ酸を含む植物体、つまり、植物の葉、茎、根、(果)実などから選ばれる少なくとも1つの部位を、アルカリ性を示す溶媒に添加し、反応中の反応液をpH6.5以上に調製して、酸素供給量1mg/L以上、反応温度0℃〜溶剤リフラックス温度、反応時間数分〜24時間で処理することによっても得ることができる。この場合のアルカリ性物質、溶媒の例としては、上記したものがあげられ、反応条件などは前記と同様に操作することにより得られる。植物体は、下記植物抽出物で例示された植物を使用することができる。
なお、ポリフェノールとアミノ酸との代わりに、ポリフェノールとアミノ酸とを含む植物体を使用した場合、さらに、実質的にアミノ酸を含まないポリフェノール含有植物抽出物、実質的にポリフェノールを含まないアミノ酸含有植物抽出物、ポリフェノールおよびアミノ酸を含む植物抽出物、ポリフェノール、アミノ酸から選ばれる少なくとも1種を併用してもよい。
例えば、ポリフェノール酸化酵素を共存させてもよく、好ましい酵素としては、カテコールオキシダーゼ、ポリフェノールオキシダーゼ、チロシナーゼ、ラッカーゼ、ペルオキシダーゼなどが挙げられる。酵素の添加量はとくに限定されないが、消臭剤の基質であるポリフェノール100mg当たり、酵素活性が100単位以上となる量で添加することが好ましい。なお、ここでいう酵素活性の単位とは、(L)−ドーパ(L−DOPA)を基質として、pH6.5、温度25℃の条件下、1分間反応させた場合にOD265nmでの吸光値を0.001増加させたときを1単位と定義する。
例えば、クロロゲン酸の例をとって説明すれば、反応開始時では淡黄色である反応液は、時間の経過と共に茶色となり、やがてはこげ茶色となる。ケルセチンの場合には、反応開始時では淡いピンク色である反応液は、時間の経過と共に赤味を増し、やがては深いワインレッド色となる。没食子酸の場合には、反応開始時では淡黄色である反応液は、時間の経過と共に緑色がかり、やがては濃緑色となる。ピロカテコールの場合には、反応開始時では淡いピンク色である反応液は、時間の経過と共に茶色となり、やがてはこげ茶色となる。
多くのポリフェノール、あるいはポリフェノールとアミノ酸との反応については、反応開始時では反応液は淡い色を有するが、反応時間が経過すると共に反応液の色が次第に濃くなり、ついには濃い色となる傾向にある。反応液の色が濃くなる時間は、ポリフェノールの種類、ポリフェノールとアミノ酸との組合せ、反応条件により異なるが、およそ反応開始後数分程度であるが、開始後20分程度や30分程度のときがある。
得られた消臭剤組成物中の有色化合物の分子量、すなわち消臭剤組成物中の消臭有効成分の分子量は、反応前の出発物質であるポリフェノールの分子量、あるいは、ポリフェノールとアミノ酸との分子量の和を超え、かつ10000以下である。
この分子量は次の方法により測定した。すなわち、上記各種の方法で調製された消臭剤組成物を遠心分離処理により濃縮し、この濃縮物が一定の細孔を有するろ過膜を通過するか、あるいはろ過膜上に残るか知り、ろ過膜上に濃縮物が残るろ過膜の細孔から、対応する分子量を求めた。ここで用いるろ過膜は市販品を用いればよい。
本発明での消臭有効成分は出発物質と酸素分子とが反応した出発物質の酸化物でもよいのであるから、消臭有効成分の分子量を上記のように表現した。
ここで、液体の好ましい例として、水、含水アルコール、低級アルコール(メタノール、エタノール、ブタノール、プロパノールなど)、ポリオール系有機溶媒(エチレングリコール、プロピレングリコールなど)、ベンジルアルコール、グリセロール、モノグリセリド、ジグリセリド、動植物油、精油などが挙げられる。
好ましい固体として、デキストリン、シクロデキストリン、ブドウ糖、乳糖、澱粉等の糖類; プラスチック粒子や発泡プラスチック等のプラスチック担体; シリカゲル粒子、珪藻土、活性白土、バーミキュライト、アルミナ、ゼオライト、パーライト、粘土鉱物、素焼き、セラミックス、金属、ガラス、活性炭などの無機物粒子; 吸水性ポリマー; そば殻、糠殻、おがくず、これらの焼成物等の天然系担体; 繊維、繊維塊、繊維束、不織布、編物、繊維製品、パルプ、紙、紙製品(ダンボール、ハニカム等)などの繊維系担体; クラウンエーテル、クリプタント、シクロファン、カリックスアレン等の合成分子: など多孔性を有する担体が挙げられる。ここでの「多孔性を有する」とは、担体自身が多孔性である場合と、担体間に無数の空隙を有する場合との双方を含む。
本発明の消臭剤組成物を担体に担持させる方法として、消臭剤組成物を溶液の状態とし、担体に塗布、含浸、噴霧等の手段により付着させ、次いで乾燥(例えば、60℃で12時間、風乾)する方法を例としてあげることが出来る。
本発明の消臭剤組成物は、担持させる以外に、ゼラチン、アラビアガム、アルギン酸ソーダ、エチルセルロース等のセルロース誘導体、ポリビニルアルコール、ビニルメチルエーテル−無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体、ポリエチレン、ポリスチレン、パラフィンワックス等を用い、公知の方法でカプセル化して使用しても良い。
溶液中の溶存酸素の量をできるだけ除去する方法としては公知の方法を使用すればよいのであり、具体的には溶液を減圧状況下に保存する方法、脱気処理を施す方法、窒素ガスやアルゴンガスにて置換する方法やそれらガス雰囲気下にて処理する方法などが挙げられる。
潮解性、高吸湿性を有する化合物の例としては、空気中の水分によって潮解性を示す、又は、空気中の水分を強く吸収する性質を示す塩類、アルカリ類などが用いられ、特に潮解性または高吸湿性を有する塩類が実用的である。
具体的には、例えば、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、塩化マグネシウムアンモニウム、塩化マグネシウムナトリウム、塩化マグネシウムカリウム、塩化マンガン、塩化マンガンカリウム、塩化アンチモン、塩化コバルトアンチモン、塩化亜鉛、塩化鉄、塩化ビスマス、塩化ベリリウム、臭化カルシウム、臭化亜鉛、臭化銅、臭化鉄、臭化コバルト、臭化カドミウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化マグネシウム、ヨウ化カルシウム、ヨウ化鉄、ヨウ化ニッケル、亜硝酸ナトリウム、亜硝酸カリウム、亜硝酸マグネシウム、硝酸アンモニウム、硝酸リチウム、硝酸ナトリウム、硝酸カルシウム、硝酸ベリリウム、硝酸マグネシウム、硝酸マンガン、硝酸セリウム、硝酸セリウムアンモニウム、硝酸鉄、硝酸銅、塩素酸リチウム、塩素酸カルシウム、塩素酸マグネシウム、塩素酸亜鉛、塩素酸カドミウム、塩素酸コバルト、塩素酸銅、炭酸カリウム、硫酸リチウム、硫酸亜鉛アンモニウム、硫酸アンチモン、硫酸鉄、硫酸カドミウムアンモニウム、チオ硫酸アンモニウム、リン酸カリウム、亜リン酸アンモニウム、亜リン酸カリウム、亜リン酸ヒドラジウム、次亜リン酸ナトリウム、次亜リン酸カリウム、過マンガン酸ナトリウム、過マンガン酸カルシウム、過マンガン酸ストロンチウム、過マンガン酸マグネシウム、過マンガン酸亜鉛、水酸化ナトリウム、水酸化カリウム等が挙げられる。これらは、1種で使用することもでき、また2種以上を併用してもよい。
これら潮解性、高吸湿性を有する化合物の共存最適量は、化合物の種類や適用する環境、用途によって大きく異なるため一概には決められないが、消臭剤組成物に対して0.1〜10倍重量を例としてあげることができる。
これらを単独あるいは2種以上を組み合わせて本発明の消臭剤組成物に配合することができ、特徴のある消臭剤を調製することができる。とくに抗菌剤を消臭剤組成物に配合すると消臭効果が相乗的に増加するので、これに他の配合剤を併用して配合剤の機能を引き出し、より特徴のある消臭剤を調製することが可能となる。上記配合剤の配合量は所期の目的を達成できる量であれば、とくに限定されない。
抗酸化剤としては、ブチルヒドロキシトルエン、ブチルヒドロキシアニソール、クエン酸、ビオフラボ酸、グルタチオン、セレン、リコペン、ビタミンA、ビタミンE、ビタミンC等の他、ピロロピロール誘導体や各種植物からの抽出物から得られる遊離基スカベンジャー(free radical scavengers)、スーパーオキサイドディスムターゼやグルタチオンペルオキシダーゼなどの抗酸化特性を有する酵素などが知られている。
上記カーボヒドラーゼ (例えば、デキストラナーゼやムタナーゼ)は、5員環構造及び6員環構造の炭水化物鎖を分解することが可能であるあらゆる酵素 (すなわち、International Union of Biochemistry and Molecular Biology(以下、IUBMBという)に基づいた酵素分類番号E.C.3.2(グリコシダーゼ)のもとに分類される酵素)を含む。デキストラナーゼは、デキストランのα-1,6-グリコシド結合を分解するα-1,6-グルカナーゼ (1,6-α-D-グルカン 6グルカノヒドロラーゼとしても知られる)である。ムタナーゼは、ムタンにおけるα-1、3-グリコシド結合を分解するα-1、3-グルカナーゼ (α-1、3-グルカノヒドロラーゼとしても知られる)である。
香料の配合量は、採用されるポリフェノールやアミノ酸、消臭剤組成物の適用対象、使用方法などにより変動するが、通常消臭剤組成物に対して重量で0.001〜500倍とすることが好ましい。
本発明の用いられるフレーバーとしては、エステル類、アルコール類、アルデヒド類、ケトン類、アセタール類、フェノール類、エーテル類、ラクトン類、フラン類、炭化水素類、酸類などの合成香料、および、天然香料などが挙げられる。
フェノール類としては、例えば、オイゲノール、イソオイゲノール、2−メトキシ−4−ビニルフェノール、チモール、カルバクロール、グアヤコールおよびチャビコールなどが好ましく挙げられる。
ラクトン類としては、例えば、γ−又はδ−デカラクトン、γ−ヘプタラクトン、γ−ノナラクトン、γ−又はδ−ヘキサラクトン、γ−又はδ−オクタラクトン、γ−又はδ−ウンデカラクトン、δ−ドデカラクトン、δ−2−デセノラクトン、メチルラクトン、5−ヒドロキシ−8−ウンデセン酸δ−ラクトン、ジャスミンラクトン、メンタラクトン、ジヒドロクマリン、オクタヒドロクマリンおよび6−メチルクマリンなどが好ましい例として挙げられる。
炭化水素類としては、例えば、α−又はβ−ビザボレン、β−カリオフィレン、p−サイメン、テルピネン、テルピノーレン、カジネン、ファルネセン、リモネン、オシメン、ミルセン、α−又はβ−ピネン、1,3,5−ウンデカトリエンおよびバレンセンなどが好ましい例として挙げられる。
本発明で用いられる合成ムスク類は、ムスク香或いはムスク類似香を有する有機化合物であれば特に限定されることはなく10−オキサヘキサデカノリド、11−オキサヘキサデカノリド、12−オキサヘキサデカノリド、アンブレットリド、アンブレトン、エギザルトリド、エギザルトン、ガラクソリド、シクロヘキサデカノリド、シクロペンタデカノリド、シクロペンタデカノン、シベトン、セルボリド、セレストリド、トナリド、ファントリド、ペンタリド、ホルミルエチルテトラメチルテトラリン、ムスコン、ベルサリドなどが例示される。
ノエート、メチルトランス−2−ヘキセノエート、メチルトランス−3−ヘキセノエート、メチルノナノエート、メチルハイドロキシヘキサノエート、メチルバレレート、メチルフェニルアセテート、メチルフェニルグリシデート、メチルブチレート、メチルヘプタノエート、メチルヘプチンカーボネート、メチルペラルゴネート、メチルベンゾエート、メチルミリステート、メチルラウレート、メチルラクテート、ラバンジュリルアセテート、リナリルアセテート、リナリルイソバレレート、リナリルイソブチレート、リナリルオクタノエート、リナリルシンナメート、リナリルブチレート、リナリルプロピオネート、リナリルヘキサノエート、リナリルベンゾエート、リナリルホーメート、ローザムスク、ローズフェノン、ロジニルアセテート、ロジニルイソブチレート、ロジニルフェニルアセテート、ロジニルブチレート、ロジニルプロピオネート、ロジニルホーメート、1,3−ジメチル−3−ブテニルイソブチレート、1−アセトキシ−2−sec−ブチルー1−ビニルシクロヘキサン、1−シクロヘキセ−1−エンイソプロピルセテート、2,4−ジメチル−3−シクロヘキシルメチルアセテート、2,4−ヘキサジエニルイソブチレート、2−メチル−2−メチルペンチルバレレート、2−メチルブチルアセテート、2−メチルブチルイソバレレート、3−オクチルアセテート、3−フェニルプロピルイソバレレート、3−フェニルプロピルイソブチレート、3−フェニルプロピルプロピオネート、3−メチルペンチルアンゲレート、4−メチルベンジルアセテート、5−メチル−3−ブチルテトラヒドロピラン−4−イルアセテート、6,10−ジメチル−5,9−ウンデカトリエン−2−イルアセテート、9−デセン−1−イルプロピオネート、E.G.ジアセテート、E.G.モノブチルエーテルアセテート、L−カルビルプロピオネート、L−ペリリルアセテート、L−ボルニルプロピオネート、L−メンチルイソバレレート、L−メンチルフェニルアセテート、P.G.ジブチレート、P.G.ジプロピオネート、p−クレジルカプリレート、p−クレジルサリシレート、α−アミルシンナミルアセテート、アセチルバニリン、アニシルプロピオネート、アニシルホーメート、イソブチル2−フランプロピオネート、イソブチルアンゲレート、イソブチルクロトネート、エチルアクリレート、エチルシトロネリルオキサレート、エチルステアレート、エチルチグレート、エチルデカジエノエート、エチルデヒドロシクロゲラネート、エチルドデカノエート、エチルトランス−2−ヘキサノエート、エチルトランス−3−ヘキサノエート、エチルノナノエート、エチルパルミテート、エチルバレレート、エチルピルベート、オイゲニルホーメート、オキシオクタリンホーメート、ネロリジルアセテート、ノナンジオール−1,3−ジアセテート、フェニルグリコールジアセテート、プソイドリナリルアセテート、ブチル10−ウンデセノエート、ブチルステアレート、ブチルホーメート、ブチルラクテート、フルフリルバレレート、プロピル2−フランアクリレートが例示され、更に好ましくは1−エチニルシクロヘキシルアセテート、1−オクテン−3−イルアセテート、2−エチルヘキシルアセテート、2−フェノキシエチルイソブチレート、2−フェノキシエチルプロピオネート、3,5,5−トリメチルヘキシルアセテート、3,7−ジメチルオクタニルアセテート、3−フェニルプロピルアセテート、9−デセン−1−イルアセテート、L−メンチルアセテート、L−メンチルプロピオネート、o−tert−ブチルシクロヘキシルアセテート、p−tert−ブチルシクロヘキシルアセテート、p−クレジルアセテート、p−クレジルイソブチレート、p−クレジルフェニルアセテート、アセチルイソオイゲノール、アセチルオイゲノール、アニシルアセテート、アフェルマート、アミルアセテート、アミルカプリレート、アミルカプロエート、アミルサリシレート、アミルバレレート、アミルブチレート、アミルホーメート、アリル2−エチルブチレート、アリルアミルグリコレート、アリルイソバレレート、アリルオクタノエート、アリルカプリレート、アリルカプロエート、アリルシクロヘキシルアセテート、アリルシクロヘキシルオキシアセテート、アリルシクロヘキシルブチレート、アリルシクロヘキシルプロピオネート、アリルシンナメート、アリルフェノキシアセテート、アリルブチレート、アリルプロピオネート、アリルヘプタノエート、アリルベンゾエート、アルデヒド C−16(ストロベリー)、アルデヒド C−19(パイナップル)、アルデヒド C−20(ラズベリー)、イソアミルアセテート、イソアミルアンゲレート、イソアミルイソバレレート、イソアミルイソブチレート、イソアミルウンデシレネート、イソアミルオクタノエート、イソアミルサリシレート、イソアミルシンナメート、イソアミルデカノエート、イソアミルドデカノエート、イソアミルブチレート、イソアミルプロピオネート、イソアミルヘキサノエート、イソアミルヘプチンカーボネート、イソアミルベンゾエート、イソアミルホーメート、イソアミルレブリネート、イソオイゲニルフェニルアセテート、イソジヒドロラバンジュリルアセテート、イソブチルアセテート、イソブチルイソバレレート、イソブチルイソブチレート、イソブチルサリシレート、イソブチルシンナメート、イソブチルバレレート、イソブチルフェニルアセテート、イソブチルブチレート、イソブチルプロピオネート、イソブチルヘキサノエート、イソブチルベンゾエート、イソプレギルアセテート、イソプロピルアセテート、イソプロピルイソバレレート、イソプロピルイソブチレート、イソプロピルシンナメート、イソプロピルデカノエート、イソプロピルフェニルアセテート、イソプロピルブチレート、イソプロピルヘキサノエート、イソプロピルベンゾエート、イソプロピルミリステート、イソボルニルアセテート、イソボルニルプロピオネート、エチル2−tert−ブチルシクロヘキシルカーボネート、エチル2−エチルヘキサノエート、エチル2−オクテノエート、エチル2−デセノエート、エチル2−フロエート、エチル2−ヘキシルアセトアセテート、エチル2−ベンジルアセトアセテート、エチル2−メチルバレレート、エチル2−メチルブチレート、エチル3,5,5−トリメチルヘキサノエート、エチル3−ハイドロキシブチレート、エチル3−ハイドロキシヘキサノエート、エチル3−ヒドロキシ−3−フェニルプロピオネート、エチル3−フェニルグリシデート、エチル3−フェニルプロピオネート、エチルo−メトキシベンゾエート、エチルp−アニセート、エチルアセテート、エチルアセトアセテート、エチルイソバレレート、エチルイソブチレート、エチルオクチンカーボネート、エチルオレエート、エチルカプリネート、エチルカプリレート、エチルカプロエート、エチルクロトネート、エチルゲラネート、エチルサフラネート、エチルサリシレート、エチルシクロゲラニエート、エチルシンナメート、エチルバレレート、エチルフェニルアセテート、エチルブチレート、エチルプロピオネート、エチルヘプタノエート、エチルヘプチンカーボネート、エチルペラルゴネート、エチルベンゾエート、エチルホーメート、エチルミリステート、エチルメチルp−トリルグリシデート、エチルメチルフェニルグリシデート、エチルラウレート、エチルラクテート、エチルリナリルアセテート、エチルレブリネート、エチレンドデカンジオエート、エチレンブラッシレート、オイゲニルフェニルアセテート、オクチルアセテート、オクチルイソバレレート、オクチルイソブチレート、オクチルオクタノエート、オクチルブチレート、オクチルヘプタノエート、オクチルホーメート、オシメニルアセテート、カリオフィレンアセテート、カリオフィレンホーメート、カルビルアセテート、グアィアックアセテート、クミニルアセテート、ゲラニルアセテート、ゲラニルイソバレレート、ゲラニルイソブチレート、ゲラニルチグレート、ゲラニルフェニルアセテート、ゲラニルブチレート、ゲラニルプロピオネート、ゲラニルヘキサノエート、ゲラニルベンゾエート、ゲラニルホーメート、コニフェラン、サンタリルアセテート、ジエチルアジペート、ジエチルスクシネート、ジエチルセバケート、ジエチルタータレート、ジエチルフタレート、ジエチルマロネート、シクロヘキシルアセテート、シクロヘキシルイソバレレート、シクロヘキシルエチルアセテート、シクロヘキシルクロトネート、シクロヘキシルブチレート、シス−3−ヘキセニル2−メチルブチレート、シス−3−ヘキセニルアセテ−ト、シス−3−ヘキセニルアンゲレート、シス−3−ヘキセニルイソバレレート、シス−3−ヘキセニルイソブチレート、シス−3−ヘキセニルカプロエート、シス−3−ヘキセニルサリシレート、シス−3−ヘキセニルチグレート、シス−3−ヘキセニルバレレート、シス−3−ヘキセニルフェニルアセテート、シス−3−ヘキセニルブチレート、シス−3−ヘキセニルプロピオネート、シス−3−ヘキセニルベンゾエート、シス−3−ヘキセニルホーメート、シス−3−ヘキセニルラクテート、シトリルアセテート、シトロネリルアセテート、シトロネリルイソバレレート、シトロネリルイソブチレート、シトロネリルチグレート、シトロネリルフェニルアセテート、シトロネリルブチレート、シトロネリルプロピオネート、シトロネリルヘキサノエート、シトロネリルホーメート、ジヒドロカルビルアセテート、ジヒドロクミニルアセテート、ジヒドロターピニルアセテート、ジヒドロミルセニルアセテート、ジメチルスクシネート、ジメチルフェニルエチルカルビニルアセテート、ジメチルフタレート、ジメチルベンジルカルビニルアセテート、ジメチルベンジルカルビニルイソブチレート、ジメチルベンジルカルビニルブチレート、ジメチルベンジルカルビニルプロピオネート、ジャスマール、シンナミルアセテート、シンナミルイソバレレート、シンナミルイソブチレート、シンナミルシンナメート、シンナミルチグレート、シンナミルブチレート、シンナミルプロピオネート、シンナミルベンゾエート、シンナミルホーメート、スチラリルアセテート、スチラリルイソブチレート、スチラリルプロピオネート、セドリルアセテート、セドリルホーメート、ターピニルアセテート、ターピニルイソバレレート、ターピニルイソブチレート、ターピニルブチレート、ターピニルプロピオネート、ターピニルホーメート、デカハイドロ−β−ナフチルホーメート、デシルアセテート、テトラハイドロフルフリルブチレート、テトラヒドロゲラニルアセテート、テトラヒドロフルフリルアセテート、テトラヒドロムギルアセテート、テトラヒドロリナリルアセテート、ドデシルアセテート、トランス−2−ヘキセニルアセテート、トランス−2−ヘキセニルブチレート、トランス−2−ヘキセニルプロピオネート、トランス−2−ヘキセニルヘキサノエート、トランス−デカハイドロ−β−ナフチルアセテート、トランス−デカハイドロ−β−ナフチルイソブチレート、トリアセチン、トリエチルシトレート、トリシクロデシルアセテート、トリシクロデセニルアセテート、トリシクロデセニルイソブチレート、トリシクロデセニルプロピオネート、ネリルアセテート、ネリルイソブチレート、ネリルブチレート、ネリルプロピオネート、ネリルホーメート、ノニルアセテート、ノピルアセテート、ハイドロトロピックアセテート、フェニルエチル2−メチルブチレート、フェニルエチルアセテート、フェニルエチルアンゲレート、フェニルエチルイソバレレート、フェニルエチルイソブチレート、フェニルエチルカプリレート、フェニルエチルサリシレート、フェニルエチルシンナメート、フェニルエチルチグレート、フェニルエチルノナノエート、フェニルエチルバレレート、フェニルエチルピバレート、フェニルエチルフェニルアセテート、フェニルエチルブチレート、フェニルエチルプロピオネート、フェニルエチルベンゾエート、フェニルエチルホーメート、フェニルエチルメタアクリレート、フェニルエチルメチルエチルカルビニルアセテート、フェニルサリシレート、フェンキルアセテート、ブチルアセテー
ト、ブチルアンゲレート、ブチルイソバレレート、ブチルイソブチレート、ブチルオクタノエート、ブチルサリシレート、ブチルデカノエート、ブチルドデカノエート、ブチルバレレート、ブチルフェニルアセテート、ブチルブチリルラクテート、ブチルブチレート、ブチルプロピオネート、ブチルヘキサノエート、ブチルレブリネート、フルフリルアセテート、プレニルアセテート、プレニルアンゲレート、プレニルベンゾエート、プロピルアセテート、プロピルイソバレレート、プロピルイソブチレート、プロピルオクタノエート、プロピルシンナメート、プロピルトランス−2,シス−4−デカジエノエート、プロピルフェニルアセテート、プロピルブチレート、プロピルプロピオネート、プロピルヘキサノエート、プロピルヘプタノエート、プロピルベンゾエート、プロピルホーメート、ヘキシル2−メチルブチレート、ヘキシルアセテート、ヘキシルイソバレレート、ヘキシルイソブチレート、ヘキシルオクタノエート、ヘキシルサリシレート、ヘキシルチグレート、ヘキシルフェニルアセテート、ヘキシルブチレート、ヘキシルプロピオネート、ヘキシルヘキサノエート、ヘキシルベンゾエート、ヘキシルホーメート、ベチコールアセテート、ベチベリルアセテート、ヘプチルアセテート、ヘプチルオクタノエート、ヘプチルブチレート、ヘプチルヘキサノエート、ヘリオトロピルアセテート、ベンジル2−メチルブチレート、ベンジルアセテート、ベンジルイソバレレート、ベンジルイソブチレート、ベンジルカプリレート、ベンジルサリシレート、ベンジルシンナメート、ベンジルチグレート、ベンジルドデカノエート、ベンジルバレレート、ベンジルフェニルアセテート、ベンジルブチレート、ベンジルプロピオネート、ベンジルヘキサノエート、ベンジルベンゾエート、ベンジルホーメート、ペンチルサリシレート、マイラルディルアセテート、ミルセニルアセテート、ミルテニルアセテート、メチル1−メチル−3−シクロヘキセンカルボキシレート、メチル2−ノネノエート、メチル2−フロエート、メチル2−メチルブチレート、メチル3−ノネノエート、メチル9−ウンデセノエート、メチルo−メトキシベンゾエート、メチルアセテート、メチルアトラレート、メチルアニセート、メチルアンゲレート、メチルイソバレレート、メチルイソブチレート、メチルイソヘキサノエート、メチルオクタノエート、メチルオクチンカーボネート、メチルオレエート、メチルカプリネート、メチルカプリレート、メチルカプロエート、メチルゲラネート、メチルサリシレート、メチルシクロオクチルカーボネート、メチルシクロゲラネート、メチルシクロペンチリデンアセテート、メチルジヒドロジャスモネート、メチルジャスモネート、メチルシンナメート、メチルデカノエート、メチルデシンカーボネート、メチルテトラデカノエート、メチルドデカノエート、メチルトランス−2−ヘキセノエート、メチルトランス−3−ヘキセノエート、メチルノナノエート、メチルハイドロキシヘキサノエート、メチルバレレート、メチルフェニルアセテート、メチルフェニルグリシデート、メチルブチレート、メチルヘプタノエート、メチルヘプチンカーボネート、メチルペラルゴネート、メチルベンゾエート、メチルミリステート、メチルラウレート、メチルラクテート、ラバンジュリルアセテート、リナリルアセテート、リナリルイソバレレート、リナリルイソブチレート、リナリルオクタノエート、リナリルシンナメート、リナリルブチレート、リナリルプロピオネート、リナリルヘキサノエート、リナリルベンゾエート、リナリルホーメート、ローザムスク、ローズフェノン、ロジニルアセテート、ロジニルイソブチレート、ロジニルフェニルアセテート、ロジニルブチレート、ロジニルプロピオネート、ロジニルホーメートが例示される。
デュピカール(Dupical,Quest);4−(Tricyclo[5.2.1.02,6]decylidene−8)butanal、
ジャスマール(Jasmal);3−Pentyltetrahydropyran−4−yl acetateアフェルマート(Aphermate,IFF);α,3,3−Trimethylcyclohexanemethyl formate、
フロラロゾン(Floralozon,IFF);p−Ethyl−α,α−dimethylhydrocinnamaldehyde、
シクロガルバネート(Cyclogalbanate,Dragoco);Allyl cyclohexyloxy acetate、
エストラゴール(Estragol,);Methyl chavicol、
ルボフィックス(Rhubofix,Firmenich);Spiro[1,4−methanonaphthalene−2(1H),2′−oxirane],3,4,4a,5,8,8a,−hexahydro−3′,7−dimethyl(1),Spiro[1,4−methanonaphthalene−(2H),2′−Oxiran],3,4,4a,5,8,8a−hexahydro−3′,6−dimethyl(2)の異性体の混合体、
トリプラール(Triplal,IFF);Dimethyl tetrahydrobenzaldehyde、
コアボン(Koavone,IFF);4−Methylene−3,5,6,6−tetramethyl−2−heptanone、
リメトール(Limetol);2,2,6−Trimethyl−6−vinyl tetrahydropyran、
アンブロキサン;Ambroxan(Henkel)、
ダマスコン;α−Damascone,β−Damascone,γ−Damascone,δ−Damascone、
ダマセノン;α−Damascenone,β−Damascenone,γ−Damascenone、
イオノン;α−Ionone,β−Ionone,γ−Ionone、
メチルイオノン;α−n−Methylionone,β−n−Methylionone,γ−n−Methylionone,α−iso−Methylionone,β−iso−Methylionone,γ−iso−Methylionone、
サンダル;Bacdanol(IFF);2−Ethyl−4−(2,2,3−trimethyl−3−cyclopenten−1−yl)−2−buten−1−olBrahamanol(Dragoco);2−Methyl−4−(2,2,3−trimethyl−3−cyclopenten−1−yl)butanolMadranol(Dragoco);β−2,2,3−Tetramethyl−3−cyclopentenyl−2−butenolSandalore(Givaudan);3−Methyl−5−(2,2,3−trimethylcyclopent−3−en−1−yl)−pentan−2−ol3,3−Dimethyl−5−(2,2,3−trimethylcyclopenten−1−yl)−pent−4−en−2−ol,Methyl sadeflor(TPC)、Sandeol(MS)など、
ムスク;Cashmeran(IFF),Galaxolide(IFF),Tonalide(PFW)、Phantolide,Versalide,Exaltolide,Exaltone,Oxalide,12−Oxahexadecanolide,Ethylenebrassylate,Celestolide(IFF),Traseolide(Quest),Ethylenedodecanedioate,5−Cyclohexadecen−1−oneなど、
イソ−E−スーパー;Iso−E−Super(IFF)、
7−Acetyl−1,2,3,4,5,6,7,8−octahydro−1,1,6,7−tetramethyl−naphthalene、
チンベロール;Timberol(Dragoco)、
1−(2,2,6−Trimethylcyclohexan−1−yl)−hexan−3−ol、
イロン;α−Irone,β−Ironeγ−Irone、
α−ダイナスコン;α−Dynascone(Firmenich)、
1−(5,5−Dimethyl cyclohexen−1−yl)−4−penten−1−one。
これらは市販のものを使用することもできる。また単品は、合成品を使用してもよいし、植物などの天然起源から導入してもよい。精油、レジノイド、バルサム、アブソリュート、コンクリート、チンキなどは、公知の方法で調製することもできる。
具体的には、口臭、体臭、冷蔵庫内での臭い、ヒト・動物・鳥の糞尿の臭い、体臭、生ゴミの臭いなど日常の生活において感じられる臭い、工場内あるいは工業廃液中の悪臭など様々な臭気を消去あるいは軽減するのに有効である。
また、本発明の消臭剤組成物は、メチルメルカプタン、硫化水素、ジメチルスルフィドなどの含硫黄化合物; アンモニア、尿素、インドール、スカトール、アミン類などの含窒素化合物; 酪酸などの低級脂肪酸などの消臭効果に優れている。その中でも、本発明の消臭剤組成物は、とくにメチルメルカプタン、硫化水素、ジメチルスルフィドなどの含硫黄化合物の消臭効果に優れている。
実施例1 消臭剤組成物の調製
表1記載のポリフェノール1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む攪拌器内に加え、空気が自由に流通でき、反応液表面が空気と充分に接触できる条件にて、25℃で、攪拌、又は攪拌後静置し、消臭剤組成物を得た。攪拌・静置時間は表1に示す。
50mLのバイアル瓶に実施例1の消臭剤組成物2mL、メチルメルカプタンナトリウムの15%水溶液(東京化成工業株式会社)4uLを順次入れ、パラフィルムで蓋をして、25℃にて攪拌する。10分後、バイアル瓶内のヘッドスペースガス50mLをガス検知管(ガステック株式会社製)に通して、ガス内に残存する悪臭成分である含イオウ化合物の濃度を測定し、下式に従って消臭率を算出した。その結果を表1に示す。
消臭率(%) = 100 × {1 − (A/B)}
なお、上記式中、Aは測定された悪臭成分濃度を示し、Bはコントロールでの測定された悪臭成分濃度を示す。
コントロールは、実施例1の消臭剤組成物2mLを加える代わりに、0.05M Na2CO3溶液(pH 11.2)2mLを加えた。
表中の時間は、消臭剤組成物を調製するために攪拌を開始してから、消臭剤組成物を調製し終わるまでの経過時間を示す。1時間、2時間、および、3時間は、消臭剤組成物を調製するときの攪拌時間を示す。4時間以降の消臭剤組成物は、3時間攪拌した後に、静置している。以下の表においても、表18以外は同様である。
比較例1 モノフェノールを用いた消臭剤組成物の調製
表1記載のポリフェノールの代わりに、表2記載のモノフェノールを用いること以外は、実施例1と同様な操作を行い、消臭剤組成物を得た。
比較例2 モノフェノールを用いた消臭剤組成物のメチルメルカプタンに対する消臭効果
実施例1の消臭剤組成物2mLの代わりに、比較例1記載の消臭剤組成物2mLを用いること以外は、実施例2と同様な操作を行い、比較例1の消臭剤組成物の消臭効果を測定し、消臭率を算出した。その結果を表2に示す。
実施例3 消臭剤組成物の調製
0.05M Na2CO3溶液(pH 11.2)50mLを加えた攪拌器内に、クロロゲン酸1mmolを添加し、空気が自由に流通でき、反応液表面が空気と充分に接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、黄土色の粉末化消臭剤組成物460mgを得た。
実施例4 メチルメルカプタンに対する消臭効果
実施例1の消臭剤組成物2mLの代わりに、実施例3の消臭剤組成物20mgを水2mLで溶解させたものを用いること以外は、実施例2と同様な操作を行い、実施例3の消臭剤組成物の消臭効果を測定した。その結果、消臭率は100%であった。
真空ポンプで吸引しながら超音波処理して溶存酸素を除去した0.05M Na2CO3溶液(pH 11.2)50mLを含む攪拌器内にクロロゲン酸1mmolを添加し、窒素ガス雰囲気下、25℃で、攪拌、又は攪拌後静置し、消臭剤組成物を得た。また、静置しているときも窒素ガス雰囲気下とした。攪拌・静置時間は表3に示す。この消臭剤組成物は黄色であった。
比較例4 メチルメルカプタンに対する消臭効果
実施例1の消臭剤組成物2mLの代わりに、比較例3記載の消臭剤組成物2mLを用いること以外は、実施例2と同様な操作を行い、比較例3の消臭剤組成物の消臭効果を測定し、消臭率を算出した。その結果を表3に示す。
実施例5 消臭剤組成物の調製
表4記載のポリフェノール1mmolとグリシン1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃にて、攪拌、又は攪拌後静置し、消臭剤組成物を得た。攪拌・静置時間は表5に示す。
得られた消臭剤組成物(3日目の結果)の示す色調は表4の通りであった。
実施例1の消臭剤組成物2mLの代わりに、実施例5記載の消臭剤組成物2mLを用いること以外は、実施例2と同様な操作を行い、実施例5の消臭剤組成物の消臭効果を測定し、消臭率を算出した。その結果を表5に示す。
表4記載のポリフェノール1mmolの代わりに、表6記載のモノフェノール1mmolを用いること以外は、実施例5と同様な操作を行い、消臭剤組成物を得た。
得られた消臭剤組成物の示す色調(3日目の結果)は表6の通りであった。
表6
実施例1の消臭剤組成物2mLの代わりに比較例5記載の消臭剤組成物2mLを用いること以外は、実施例2と同様な操作を行い、比較例5の消臭剤組成物の消臭効果を測定した。
その結果を表7に示した。
クロロゲン酸1mmolと表8記載のアミノ酸1mmolを用いる以外は、実施例5と同様な方法により、消臭剤組成物を得た。
得られた消臭剤組成物の示す色調は表8の通りであった。併せて、反応液のpH、消臭素材由来の臭い対する評価を記載した。
表8
実施例8 メチルメルカプタンに対する消臭効果
実施例7の消臭剤組成物2mL用いること以外は、実施例2と同様な操作を行い、実施例7の消臭剤組成物の消臭率を測定した。その結果を表9に示した。
表9
クロロゲン酸1mmolとグリシン1mmolを反応容器に入れ、0.05M Na2CO3溶液(pH11.2)50mLを添加した。空気と接触できる条件にて、25℃、3時間攪拌した。次いで凍結乾燥し、濃緑色の粉末化消臭剤組成物を535mg得た。
実施例10 メチルメルカプタンに対する消臭効果
実施例1の消臭剤組成物の代わりに、実施例9の粉末化消臭剤組成物28mg用い、蒸留水2mLをさらに添加する以外は実施例2と同様な操作を行い、消臭率を測定した。
その結果、消臭率は100%であった。
反応器内に0.05M Na2CO3溶液(pH11.2)50mLを入れ、表10記載の植物抽出物(ポリフェノールとアミノ酸を含有している抽出物)をポリフェノール含量が1mmolとなるように添加した。空気と接触できる条件にて、25℃で、攪拌、又は攪拌後静置し、消臭剤組成物を得た。攪拌・静置時間は表10に示す。
緑茶抽出物:ポリフェノール含量 30重量%
リンゴ抽出物:ポリフェノール含量 60重量%
ローズマリー抽出物:ポリフェノール含量 50重量%
ペパーミント抽出物:ポリフェノール含量 32重量%
スペアミント抽出物:ポリフェノール含量 33重量%
ブドウ果皮抽出物:ポリフェノール含量 90重量%
ブドウ種子抽出物:ポリフェノール含量 40重量%
上記ポリフェノール含量は、コーヒー生豆抽出物、リンゴ抽出物、ローズマリー抽出物、ペパーミント抽出物、スペアミント抽出物ではクロロゲン酸換算で算出した。緑茶抽出物はカテキン換算で算出した。ブドウ果皮抽出物、ブドウ種子抽出物はメーカー表示にしたがった。
コーヒー生豆に対して10倍質量の水を加えて、90〜95℃で2時間攪拌抽出する。ろ過後、ろ過液を減圧下で溶剤を留去することによりコーヒー生豆抽出物を得た(対コーヒー生豆収率約16.8%)。
緑茶抽出物:
緑茶に対して20倍質量の水を加えて90〜95℃で2時間攪拌抽出する。ろ過後、ろ過液を減圧下で溶剤を留去することにより緑茶抽出物を得た(対緑茶収率約25.7%)。
リンゴ抽出物:ニッカウイスキー株式会社製
ローズマリー抽出物:
乾燥ローズマリーに対して20倍質量の30%含水エタノール溶液を加えて、45〜50℃で2時間攪拌抽出する。ろ過後、ろ過液を減圧下で溶剤を留去することによりローズマリー抽出物を得た(対乾燥ローズマリー収率約15.4%)。
ペパーミント抽出物:
水蒸気蒸留処理によりオイル分を除去した後の乾燥ペパーミントに対して10倍質量の水を加えて、90〜95℃で2時間攪拌抽出する。ろ過後、ろ過液を減圧下で溶剤を留去することによりペパーミント抽出物を得た(対乾燥ペパーミント収率約17.8%)。
スペアミント抽出物:
水蒸気蒸留処理によりオイル分を除去した後の乾燥スペアミントに対して10倍質量の水を加えて、90〜95℃で2時間攪拌抽出する。ろ過後、ろ過液を減圧下で溶剤を留去することによりスペアミント抽出物を得た(対乾燥スペアミント収率約15.8%)。
ブドウ果皮抽出物:ポリフェノリックス社製
ブドウ種子抽出物:ポリフェノリックス社製
リンゴ(品種ふじ)果皮乾燥物をミルで粉砕し、粉末化し、リンゴパウダーを得た。そのパウダー80gに、50mM炭酸ナトリウム溶液800mLを加えて、空気と接触できる状態で、40℃、3時間激しく攪拌した(反応溶液のpHは7.6)。反応液を濾過後、濾過液を減圧乾燥し、消臭剤組成物パウダー81.6g(対果皮乾燥物102%)を得た。
実施例14
緑茶の乾燥茶葉80gに、50mM炭酸ナトリウム溶液1600mLを加えて、空気と接触できる状態で、30℃、1時間激しく攪拌した(反応溶液のpHは8.7)。反応液を濾過後、濾過液を凍結乾燥し、消臭剤組成物パウダー51.8g(対乾燥茶葉64%)を得た。
水蒸気蒸留処理によりオイル部を取り除いたシソ葉・茎の乾燥物100gをミルで破砕した。50mM炭酸ナトリウム溶液(pH11.2)を20倍質量加え、空気と接触できる状態で、25℃、3時間激しく攪拌抽出した(反応液のpHは8.5)。反応液をろ過後、ろ過液を凍結乾燥し、消臭剤組成物パウダー25.8gを得た(対シソ乾燥物収率25.8%)。
実施例16
コーヒー生豆100gに50mM炭酸ナトリウム溶液(pH11.2)を10倍質量加え、空気と接触できる状態で、15℃、3時間激しく攪拌抽出した(反応液のpHは7.8)。反応液をろ過後、ろ過液を凍結乾燥し、消臭剤組成物パウダー17.3gを得た(対コーヒー生豆収率17.3%)。
ブドウ果皮乾燥物100gに50mM炭酸ナトリウム溶液(pH11.2)を10倍質量加え、空気と接触できる状態で、15℃、3時間激しく攪拌抽出した(反応液のpHは7.3)。反応液をろ過後、ろ過液を凍結乾燥し、消臭剤組成物パウダー15.4gを得た(対ブドウ果皮乾燥物収率15.4%)。
実施例18
実施例1の消臭剤組成物の代わりに、実施例13〜実施例17で得られた消臭剤組成物パウダー40mgをそれぞれ水2mLに溶解したものを用いる以外は、実施例2と同様な操作を行い、消臭率を測定した。その結果を表11に示す。
反応器中で、没食子酸1mmol、グルタミン酸ナトリウム1mmol、表12に記載の各種濃度のNa2CO3水溶液あるいは、表13に記載の各種濃度のNaOH水溶液50mLを混合し、室温下、空気が接触できる条件で、攪拌、又は攪拌後静置し、消臭剤組成物を調整した。攪拌・静置時間は表12、表13に示す。
上記消臭剤組成物を用い、実施例2と同様な操作を行い、消臭率を測定した。なお、実施例2の式のBにあたるコントロールは、消臭剤組成物の代わりに、表12、表13に記載された各種濃度のアルカリ性溶媒を加えた。
その結果を表12、表13に示す。
いずれのアルカリ溶媒においても、反応中の反応液のpHが7以上で調製した消臭剤組成物は、優れた消臭効果を発揮し、反応中の反応液のpHが6以下で調製した消臭剤組成物は、消臭率は低かった。
クロロゲン酸1mmolとグリシン1mmolを、下記のアルカリ溶媒、アルカリ緩衝溶媒、中性緩衝溶媒50mLを入れた反応器内に添加し、25℃にて、攪拌、または攪拌・静置した後、消臭剤組成物を得た。攪拌・静置時間は表14に示す。
(B) 0.05M NaHCO3/Na2CO3 溶液(pH9.1)
(C) 0.05M NaHCO3/Na2CO3 溶液(pH10.0)
(D)0.05M Na2CO3 溶液(pH11.2)
(E)0.05M Na2HPO4/NaH2PO4溶液(pH 6.5)
実施例21 メチルメルカプタンに対する消臭効果
実施例20の消臭剤組成物を用い、実施例2と同様な操作を行い、実施例20の消臭効果を測定した。なお、実施例2の式のBにあたるコントロールは、消臭剤組成物の代わりに、(A)〜(E)の溶媒を加えた。
その結果を表14に示した。
(A)は、0.05M NaHCO3溶液(pH 8.3)、
(B)は、0.05M NaHCO3/Na2CO3溶液(pH 9.1)、
(C)は、0.05M NaHCO3/Na2CO3溶液(pH 10.0)、
(D)は、0.05M Na2CO3溶液(pH 11.2)
(E)は、0.05M Na2HPO4/NaH2PO4溶液(pH 6.5)
を使用して調製した消臭剤組成物を示す。
一方、反応中の反応液のpHが6.5であっても、反応前の溶媒がアルカリ性であり、かつ、クロロゲン酸とグリシンを添加し反応させた結果pH6.5になった場合には、消臭効果が認められ消臭剤組成物が生成された。
実施例19、20、21より、消臭剤組成物の生成には、アルカリ性溶媒の種類、濃度、反応前のアルカリ性溶媒のpHに依存するのではなく、pH7.0以上のアルカリ性溶媒を用いて、反応中の反応液のpHを6.5以上とすることが重要な要因であることが示唆された。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを0.05M 炭酸ナトリウム溶液(pH11.2)100mLを含む反応器内に加え、常に空気を供給しながら、表15に記載の各温度で攪拌し、経時的に反応液中の溶存酸素濃度の測定した。また、没食子酸とグルタミン酸ナトリウムを添加せずに、0.05M 炭酸ナトリウム溶液(pH11.2)100mLについても、同様の方法で経時的に反応液中の溶存酸素濃度の測定をした。その結果を表15に示す。
なお、反応液中の溶存酸素濃度の測定には、23.4℃と42.4℃時では、溶存酸素測定装置(東亜電気株式会社製、酸素電極:OE−2102)を用いて測定し、また、60℃、80℃、沸騰水中の測定には、溶存酸素測定用ポナールキット−DO(同仁化学研究所製)を用いて測定した。
また、各温度の攪拌3時間のものについて、実施例2と同様に、消臭活性試験を行った。その結果を表16に示す。
以上の結果から、沸騰温度で反応させた場合の溶存酸素量(0.5mg/L)では、消臭有効成分の生成効率がかなり低下することが示唆された。
タンニン酸1mmolとグルタミン酸ナトリウム1mmolを0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
没食子酸1mmolとグリシン1mmolを0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
得られた各消臭剤組成物2gを、3,000rpmで1時間遠心膜ろ過した。遠心膜ろ過は、分子量3000で分離させるろ過膜と分子量10000で分離させるろ過膜の2種類のろ過膜を使用した。分子量3000で分離させるろ過では、ろ過液に分子量3000以下が分離し、ろ過残に分子量3000より大きいものが分離される。分子量10000で分離させるろ過では、ろ過液に分子量10000以下が分離し、ろ過残に分子量10000より大きいものが分離される。
その結果を表17に示す。
分子量3000分離用ろ過膜:
Centricon(登録商標) YM−3(Millipore社製、分子量3000カット用)
分子量10000分離用ろ過膜:
Centricon(登録商標) YM−10(Millipore社製、分子量10000カット用)
タンニン酸とグルタミン酸ナトリウム由来の消臭剤組成物、没食子酸とグリシン由来の消臭剤組成物ともに同様の結果であった。すなわち、分子量3000カット用の遠心ろ過器ではろ過液、ろ過残液ともに強い消臭活性が認められたが、分子量10000カット用の遠心ろ過器では、ろ過液に強い消臭活性が認められるが、ろ過残液には消臭効果は全く認められなかった。この結果から、消臭剤組成物中の有効成分の分子量は10000以下であることが示唆された。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、表18に記載の各温度、各時間で攪拌し続けた。経時的に反応液2mLを採取し、実施例2に従って消臭活性を測定した。
結果を表18に示す。
反応(攪拌)温度と消臭活性の関係では、反応温度の上昇に伴い消臭活性は低下することが明らかになった。特に70℃以上の高温度では、攪拌時間が長時間であると消臭活性は低下した。従って、消臭有効成分生成効率が高い反応温度は、60℃までの範囲である。
反応(攪拌)時間については、7時間程度が好ましい。また、反応温度が80℃では消臭率100%を保っている3時間までが消臭有効成分の生成に適している。
反応器中で、クロロゲン酸1mmol、グルタミン酸ナトリウム1mmol、50mM Na2CO3水溶液50mL、表19に記載の各種金属塩0.25mmolを混合し、室温下、空気と接触できる条件で、攪拌、又は攪拌後静置し、消臭剤組成物を調整した。攪拌・静置時間は表19に示す。また、表中の無添加は、金属塩を添加しないで調製した消臭剤組成物である。
上記消臭剤組成物を用い、実施例2と同様な操作を行い、消臭率を測定した。その結果を表19に示す。
色調は、反応(攪拌)開始3日後と48日後に観察した結果である。
金属イオンを添加した場合は、コントロール(金属塩無添加)と比較して消臭活性の持続性が認められた。また、MgCl2、ZnCl2、MnSO4を添加した消臭剤組成物は、色調の安定性に対しても優れた効果を示した。
実施例26 金属イオン添加濃度の影響
反応器中で、クロロゲン酸1mmol、グルタミン酸ナトリウム1mmol、50mM Na2CO3水溶液45mL、表20に記載の各種濃度のMgCl2水溶液を5mL混合し、室温下、空気が接触できる条件で、攪拌、又は攪拌後静置し、消臭剤組成物を調整した。
攪拌・静置時間は表20に示す。また、表中の無添加は、MgCl2水溶液を添加しないで調製した消臭剤組成物である。
上記消臭剤組成物を用い、実施例2と同様な操作を行い、消臭率を測定した。その結果を表20に示す。
0.0005mMのMgCl2水溶液を添加した場合でも、13日後、47日後の消臭率は無添加区の場合よりもいずれも高く、MgCl2添加により活性の持続性が高まっていた。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを、0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し消臭剤組成物パウダーを得た。本パウダーを水に溶解し、消臭剤組成物溶液を得た。
消臭剤組成物の濃度が10.00mg/mlの消臭剤組成物溶液を調製し、その消臭剤組成物溶液について、メチルメルカプタン、アンモニア、イソ吉草酸に対する消臭効果の試験を行った。
実施例2と同様な方法で行った。
アンモニアに対する消臭試験
50mLのバイアル瓶に消臭剤組成物を2mL入れ、そこに2.8%アンモニア水を5μL添加し、パラフィルムで蓋をして、25℃、10分間攪拌する。バイアル瓶内のヘッドスペースガス50mLをガス検知管(ガステック(株))に通して、ガス内に残存する悪臭成分の濃度を測定し、実施例2で示した式に従って消臭率を算出した。
イソ吉草酸に対する消臭試験
50mLのバイアル瓶に消臭剤組成物を2mL入れ、そこにイソ吉草酸40μLを添加し、パラフィルムで蓋をして、25℃、10分間攪拌する。バイアル瓶内のヘッドスペースガス50mLをガス検知管(ガステック(株))に通して、ガス内に残存する悪臭成分の濃度を測定し、実施例2で示した式に従って消臭率を算出した。
このことから、本発明の消臭剤組成物はメチルメルカプタン、アンモニア、イソ吉草酸について優れた消臭効果をもたらすことが分かり、アルカリ性を示す悪臭成分に対しても優れた消臭効果をもたらすことができる汎用的な消臭剤組成物であることが分かった。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを、0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し消臭剤組成物パウダーを得た。本パウダーを水に溶解し、表21に示す各濃度の消臭剤組成物溶液を得た。
各濃度の消臭剤組成物溶液について、メチルメルカプタンに対する消臭効果の試験を行った。
メチルメルカプタンに対する消臭試験
実施例2と同様な方法で行った。
その結果を表21に示す。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを、0.05M 炭酸ナトリウム溶液(pH11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し消臭剤組成物パウダーを得た。本パウダーを水に溶解し、表22に示す各濃度の消臭剤組成物溶液を得た。
各濃度の消臭剤組成物溶液について、イソ吉草酸に対する消臭効果の試験を行った。
イソ吉草酸に対する消臭試験
50mLのバイアル瓶に消臭剤組成物を2mL入れ、そこにイソ吉草酸40μLを添加し、パラフィルムで蓋をして、25℃、10分間攪拌する。バイアル瓶内のヘッドスペースガス50mLをガス検知管(ガステック(株))に通して、ガス内に残存する悪臭成分の濃度を測定し、実施例2で示した式に従って消臭率を算出した。
その結果を表22に示す。
没食子酸20mmol、グルタミン酸ナトリウム20mmol、50mM 炭酸ナトリウム水溶液1000mLを混合し、室温下、空気と接触できる状態で、3時間攪拌後、反応液を凍結乾燥によって乾燥濃縮した。乾燥物を磨砕して、消臭剤組成物パウダー9.6gを得た。
紙おむつ(ライフリー尿とりパットスーパー:ユニチャーム製)の尿吸収体の約1/2(10g)を500mL用紙コップに取り、上から上記消臭剤組成物パウダー0.5gを添加した。ヒト尿100mLを加え、コップの口をサランラップ(商品名)とアルミ箔の2重構造で蓋をし、34℃で、3時間、6時間、24時間静置した後の臭いに対する官能評価をパネル4名にて行った。評価方法は、以下の項目について点数評価で行い、評価結果は、4名のパネルの平均値とした。
なお、消臭剤組成物パウダーを添加しないものをブランクとした。結果を図1と図2に示す。
尿臭の消臭効果;
1: 尿の臭いがほとんどしない
2: 尿の臭いが僅かにする
3: 尿の臭いが若干する
4: 尿の臭いが少しする
5: 尿の臭いがかなりする
6: 尿の臭いが強い
全体的な臭気強度(尿臭、紙オムツ尿吸収体自身の臭いなど系全体の臭気強度);
0: 無臭
1: やっとかすかに感じる
2: 楽に感じる
3: 明らかに感じる
4: 強く感じる
5: 耐えられないほど強く感じる
没食子酸20mmol、50mM 炭酸ナトリウム水溶液1000mLを混合し、室温下、空気と接触できる状態で、3時間攪拌後、反応液を凍結乾燥によって乾燥濃縮した。乾燥物を磨砕して、消臭剤組成物パウダー5.8gを得た。
紙オムツへの応用方法、官能評価方法は実施例30と同じ方法で行った。結果を図1と図2に示す。
図1および図2から、本発明の消臭剤組成物を添加した紙オムツは、24時間静置したものにおいても、3時間の評価点と変わらず、顕著に尿臭の発生を抑制するとともに、系全体の臭気強度も弱く、強い消臭効果が得られた。
没食子酸1mmolとグルタミン酸ナトリウム1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃で、3時間攪拌した。次いで、反応液を凍結乾燥し、静置し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法により洗口液を得た。
ニンニク4gと水1Lからニンニク抽出液を調製した。得られたニンニク抽出液10mLを50mL容量瓶内に注入し、さらに上記洗口液1mLを加えて混合した。引き続き、34℃で3分間振とうした。得られた混合物に対し、専門パネル5名により下記評価基準に従い官能評価した。結果は、5名の評価値の平均値とした。その結果を表24に示す。
評価基準値
1点) ニンニク臭を全く感じない
2点) ニンニク臭を僅かに感じる
3点) ニンニク臭を幾分感じる
4点) ニンニク臭を明確に感じる
5点) ニンニク臭を強く感じる
6点) ニンニク臭を強烈に感じる
実施例33 練り歯磨き剤
タンニン酸1mmolとグリシン1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて25℃、3時間攪拌した。次いで、反応液を減圧下で乾固し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法により練り歯磨き剤を得た。
消臭剤組成物を練り歯磨き剤に使用した場合の口臭除去効果を評価するために、下記の方法を採用した。
被験者は水で口をよく濯いだ後に、メチルメルカプタンナトリウム50ppmの溶液10mLを口に含み、1分後にその溶液を吐き出した。直ちに呼気を5Lのプラスチックバッグに捕集した。
引き続き、上記調製した練り歯磨き剤を用いて2分間歯磨きした。直ちに、呼気を5Lのプラスチックバッグに捕集した。
歯磨きした後のプラスチック製バッグ内の呼気について、歯磨きする前のプラスチック製バッグ内の呼気と比較しながら、4名のパネルが下記評価基準に基づき官能評価した。結果は、4名の評価値の平均値とし、表26に示す。
1点) メチルメルカプタンを全く感じない
2点) メチルメルカプタンを僅かに感じる
3点) メチルメルカプタンを幾分感じる
4点) メチルメルカプタンを明確に感じる
5点) メチルメルカプタンを強く感じる
6点) メチルメルカプタンを強烈に感じる
コントロール(2)は、本発明品を添加せずに調製した練り歯磨き剤を使用した場合を示す。
反応器内に0.05M Na2CO3溶液(pH11.2)50mLを入れ、ペパーミント抽出物をポリフェノール含量がクロロゲン酸換算で1mmolとなるように添加した。空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法により直径約6mmのタブレットを得た。
表27 タブレットの組成
消臭剤組成物をタブレットに配合した場合の口臭除去効果を評価するために下記の方法を採用した。
被験者は水で口をよく濯いだ後、メチルメルカプタンナトリウム50ppmの溶液10mLを口に含み、1分後にその溶液を吐き出した。直ちに、呼気を5Lのプラスチック製バッグに捕集した。
引き続き、被験者は上記で調製したタブレットを10分間食した。直ちに、呼気を5Lのプラスチック製バッグに捕集した。
タブレットを食した後のプラスチック製バッグに捕集した呼気について、タブレットを食する前のプラスチック製バッグに捕集した呼気と比較しながら、4名のパネルが、練り
歯磨き剤の項と同じ評価基準により官能評価した。結果は、4名の評価値の平均値とし、表28に示す。
実施例35 チューインガム
反応器内に0.05M Na2CO3溶液(pH11.2)50mLを入れ、ブドウ果皮抽出物をポリフェノール含量がカテキン換算で1mmolとなるように添加した。空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法によりチューインガムを得た。
上記消臭剤組成物入りチューインガムを使用した場合の口臭除去効果を評価するために下記の方法を採用した。
被験者は水で口をよく濯いだ後、メチルメルカプタンナトリウム50ppmの溶液10mLを口に含み、1分後にその溶液を吐き出した。直ちに呼気を5Lのプラスチックバッグに捕集した。
引き続き、被験者はチューインガムを10分間噛み続けた。10分後、即座に呼気を5Lのプラスチックバッグに捕集した。
チューインガムを噛み続けた後のプラスチック製バッグに捕集した呼気について、チューインガムを噛む前のプラスチック製バッグに捕集した呼気と比較しながら、4名のパネルが、練り歯磨きの項と同じ評価基準により官能評価した。結果は、4名の評価値の平均値とし、表30に示す。
実施例36 制汗剤
クロロゲン酸1mmolとグリシン1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。下記処方の成分の所定量を加熱して均一な高粘度の溶液を得た。ついで、この溶液を型内に流し込み、冷却して、消臭剤組成物含有制汗剤スティックを得た。
0.25%酪酸水溶液5mL中に上記制汗剤ステイックの削り出し片2gを加え、室温で混合した。10分後に、専門パネル5名によって下記評価基準により当該混合物の官能評価を行った。結果は、5名の評価値の平均値とし、表32に示す。
なお、比較のために消臭剤組成物を含まない制汗剤ステイックを用いて、上記と同様な方法により官能評価した。
評価基準値
1点) 酪酸臭を全く感じない
2点) 酪酸臭を僅かに感じる
3点) 酪酸臭を幾分感じる
4点) 酪酸臭を明確に感じる
5点) 酪酸臭を強く感じる
6点) 酪酸臭を強烈に感じる
実施例37 粉末洗剤
没食子酸1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法により粉末洗剤を得た。
表33 粉末洗剤の組成
丸1日着用した靴下のうちの片方を、上記調製された消臭剤組成物入り粉末洗剤(0.5重量%)を含む水に浸し、室温下5分間洗浄し、濯いだ。また、残りの片方については本発明の消臭剤組成物を添加せずに調製した粉末洗剤(0.5重量%)を含む水に浸し、同時に室温下5分間洗浄し、濯いだ(コントロール)。この靴下を5名の専門パネルによって下記評価基準に従い官能評価した。結果は、5名の評価値の平均値とし、表34に示す。
評価基準値
1点) 特有のむれ臭を全く感じない
2点) 特有のむれ臭を僅かに感じる
3点) 特有のむれ臭を幾分感じる
4点) 特有のむれ臭を明確に感じる
5点) 特有のむれ臭を強く感じる
6点) 特有のむれ臭を強烈に感じる
没食子酸1mmolとグルタミン酸ナトリウム1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。下記処方の成分を混合し、常法によりシャンプーを得た。
表35 シャンプーの組成
消臭剤組成物含有シャンプーを用いたパーマ臭消去効果を評価するため下記の方法を採用した。
試験用のカモジ1.8gをパーマ処理第1液(チオグリコール酸6%水溶液をアンモニア水でpH9.3に調整したもの)50mLに30分間浸す。付着した第1液を紙でふき取った後、100mLの水で洗浄した後、パーマ処理第2液(臭素酸カリウム5%水溶液)50mLに20分間浸す。付着した第2液を紙でふき取った後、このカモジを、上記で調製されたシャンプー(1重量%)を含む水1000mL中に5分間浸す。付着したシャンプー含有水を紙でふき取った後、水100mLで水洗し、付着する水を紙でふき取った。このカモジを4名のパネルが下記のような評価基準に従い官能評価した。結果は、4名の評価値の平均値とし、表36に示す。
1点) パーマ臭を全く感じない
2点) パーマ臭を僅かに感じる
3点) パーマ臭を幾分感じる
4点) パーマ臭を明確に感じる
5点) パーマ臭を強く感じる
6点) パーマ臭を強烈に感じる
クロロゲン酸1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。
消臭試験
100mLのバイアル瓶に成人男子の尿10mL、上記の消臭剤組成物20mgを入れ、パラフィルム(American National Can社製)で栓をし、25℃で10分間振とうした。また、100mLのバイアル瓶に成人男子の尿10mL、上記の消臭剤組成物20mg、ラベンダーフレグランス(高砂香料工業株式会社製)10μLを入れ、パラフィルムで栓をし、25℃で10分間振とうした。
そのバイアル瓶内について、パネル7名によりの下記評価基準に従って官能評価を行った。結果は、7名の評価値の平均値とし、表37に示す。
なお、比較として、尿のみの検体、尿にラベンダーフレグランス(高砂香料工業株式会社製)を10μL添加した検体についても試験した。
官能評価基準
1点) マルオーダを全く感じない
2点) マルオーダを僅かに感じる
3点) マルオーダをややはっきりと感じる
4点) マルオーダをはっきりと感じる
5点) マルオーダを強く感じる
6点) マルオーダを強烈に感じる
タンニン酸1mmolとグルタミン酸ナトリウム1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。
消臭試験
100mL用のバイアル瓶に、生理臭マルオーダ10mL、上記の消臭剤組成物50mgを入れパラフィルムで栓をする。25℃で10分間振とうした後、パネル7名により下記の評価基準に従って官能評価を行った。結果は、7名の評価値の平均値とし、表38に示す。
なお、比較のため、マルオーダのみで振とうし、官能評価を行った。
官能評価基準
1点) マルオーダを全く感じない
2点) マルオーダを僅かに感じる
3点) マルオーダをややはっきりと感じる
4点) マルオーダをはっきりと感じる
5点) マルオーダを強く感じ
6点) マルオーダを強烈に感じる
クロロゲン酸1mmolとグルタミン酸ナトリウム1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
消臭試験
100mL用のバイアル瓶に、家畜の糞尿から分離した液10mL、上記の消臭剤組成物1mLを入れ、パラフィルムで栓をする。25℃で10分間振とうした後、パネル7名により下記の評価基準に従って官能評価を行った。結果は、7名の評価値の平均値とし、表39に示す。
なお、対照には、家畜の糞尿分離液のみで培養した検体を使用した。
官能評価基準
1点) 糞尿臭を全く感じない
2点) 糞尿臭を僅かに感じる
3点) 糞尿臭はややはっきりと感じる
4点) 糞尿臭をはっきりと感じる
5点) 糞尿臭を強く感じる
6点) 糞尿臭を強烈に感じる
反応器内に0.05M Na2CO3溶液(pH11.2)50mLを入れ、緑茶抽出物をポリフェノール含量がカテキン換算で1mmolとなるように添加した。空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
消臭試験
水5Lに、上記で調製された消臭剤組成物5mLを加えてよくかき混ぜ、その混合液内に鰯を調理した後の鍋を漬け込む。室温下、10分間経過した後に鍋を取り出し、消臭剤組成物含有液を水で洗い流した。ついで、この鍋表面の臭いの有無およびその程度を専門パネル5名によって下記評価基準に基づき官能評価した。結果は、5名の評価値の平均値とし、表40に示す。
評価基準値
1点) 魚臭を全く感じない
2点) 魚臭を僅かに感じる
3点) 魚臭を幾分感じる
4点) 魚臭を明確に感じる
5点) 魚臭を強く感じる
6点) 魚臭を強烈に感じる
実施例43 生ゴミに対する消臭効果
タンニン酸1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
消臭試験
野菜くず、魚くず、肉片等からなる所謂生ゴミ1kgを蓋付きポリバケツに入れ、上記で調製した消臭剤組成物を水で10倍に希釈した水溶液50mLを噴霧し、蓋をした。対照として同様の生ゴミ1kgに対して水50mLを噴霧した。室温で3日間静置した後、パネル5名により所定の官能評価基準に従い官能評価を行った。結果は、5名の評価値の平均値とし、表41に示す。
官能評価基準
1点) 生ゴミ臭は全く認められない
2点) 僅かに生ゴミ臭が認められる
3点) 若干生ゴミ臭が認められる
4点) 生ゴミ臭がはっきりと認められる
5点) 生ゴミ臭が強く認められる
6点) 非常に強烈に生ゴミ臭が認められる
反応器内に0.05M Na2CO3溶液(pH11.2)50mLを入れ、リンゴ果皮抽出物をポリフェノール含量がクロロゲン酸換算で1mmolとなるように添加した。空気と接触できる条件にて、25℃、3時間攪拌した。次いで、反応液を凍結乾燥し、消臭剤組成物のパウダーを得た。
消臭試験
パネル5名に各々本発明品2gを便器内の水たまり部分に撒いてもらい、その後排泄してもらった。排泄後、トイレ内の臭気を官能評価基準に従い官能評価を行った。その結果を表42に示す。
官能評価基準
1点) 排泄物臭は全く認められない
2点) 僅かに排泄物臭が認められる
3点) 若干排泄物臭が認められる
4点) 排泄物臭がはっきりと認められる
通常と同程度に排泄物臭が強く認められる
没食子酸1mmolとグリシン1mmolを0.05M Na2CO3溶液(pH 11.2)50mLを含む反応器内に加え、空気と接触できる条件にて、25℃、3時間攪拌した後、静置し、消臭剤組成物を得た。
消臭試験
4L用無臭袋に空気4Lをエアーポンプを用いて封入し、そこへ各悪臭ガス(アンモニア、トリメチルアミン、硫化水素、メチルメルカプタン)を注射器にて注入しガス濃度を調製する。この袋をエアーポンプ付き密閉循環系の試験装置にセットし約1000mL/分の空気量にてエアーポンプを稼動させる。上記消臭剤組成物1mLを脱脂綿(0.2g)に担持させエアーポンプ吐き出し側にセットする。稼動後2時間して、系内の悪臭ガスの残存量を、専用のガス検知管(ガステック株式会社)を用いて測定し、以下の式に従い消臭率を算出した。
比較例として、上記消臭剤組成物を担持させた脱脂綿の代わりに、没食子酸20mMの水溶液1mLを脱脂綿に染み込ませたものをエアーポンプ吐き出し側にセットし、同様に試験し、消臭率を算出した。
Claims (11)
- ポリフェノールを、アルカリ性を示す溶媒中、酸素分子共存下、反応時のpH値が6.5以上で反応させて得られる有色の化合物を有効成分として含有することを特徴とする消臭剤組成物。
- 反応中の酸素分子供給量が1mg/L以上であることを特徴とする請求項1記載の消臭剤組成物。
- 反応時の温度が0〜60℃であることを特徴とする請求項1記載の消臭剤組成物。
- さらに金属イオンを添加して反応させることを特徴とする請求項1記載の消臭剤組成物。
- ポリフェノールがo−ジフェノール構造を有するポリフェノールである請求項1記載の消臭剤組成物。
- ポリフェノールがヒドロキノンである請求項1記載の消臭剤組成物。
- ポリフェノールの代わりに実質的にアミノ酸を含まない植物抽出物を用いる請求項1記載の消臭剤組成物。
- さらにアミノ酸を添加して反応させることを特徴とする請求項1〜4から選ばれる1項記載の消臭剤組成物。
- さらにアミノ酸を添加して反応させることを特徴とする請求項5〜7から選ばれる1項記載の消臭剤組成物。
- アミノ酸がα−アミノ酸である請求項8または9記載の消臭剤組成物。
- ポリフェノールとアミノ酸との代わりにポリフェノールとアミノ酸とを含む植物抽出物および/または植物体を用いる請求項8記載の消臭剤組成物。
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US12/252,558 US8778320B2 (en) | 2002-10-28 | 2008-10-16 | Deodorant composition |
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- 2003-10-28 WO PCT/JP2003/013794 patent/WO2004037303A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
---|---|
US20140271522A1 (en) | 2014-09-18 |
US20090087401A1 (en) | 2009-04-02 |
EP1561476A1 (en) | 2005-08-10 |
AU2003275719A1 (en) | 2004-05-13 |
JP3947149B2 (ja) | 2007-07-18 |
WO2004037303A1 (ja) | 2004-05-06 |
US9358191B2 (en) | 2016-06-07 |
EP1561476B1 (en) | 2014-02-12 |
US8778320B2 (en) | 2014-07-15 |
US20060165622A1 (en) | 2006-07-27 |
EP1561476A4 (en) | 2006-09-06 |
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