TWI522122B - 牙齒美白方法、視覺可接受標記及所使用之組成物 - Google Patents
牙齒美白方法、視覺可接受標記及所使用之組成物 Download PDFInfo
- Publication number
- TWI522122B TWI522122B TW102146813A TW102146813A TWI522122B TW I522122 B TWI522122 B TW I522122B TW 102146813 A TW102146813 A TW 102146813A TW 102146813 A TW102146813 A TW 102146813A TW I522122 B TWI522122 B TW I522122B
- Authority
- TW
- Taiwan
- Prior art keywords
- zinc
- precipitate
- amino acid
- composition
- complex
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 32
- 230000002087 whitening effect Effects 0.000 title claims description 10
- 239000011701 zinc Substances 0.000 claims description 79
- 229910052725 zinc Inorganic materials 0.000 claims description 64
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 239000002244 precipitate Substances 0.000 claims description 33
- -1 zinc amino acid halide Chemical class 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 238000010790 dilution Methods 0.000 claims description 15
- 239000012895 dilution Substances 0.000 claims description 15
- 210000000214 mouth Anatomy 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 230000008901 benefit Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 208000002925 dental caries Diseases 0.000 claims description 3
- 201000002170 dentin sensitivity Diseases 0.000 claims description 2
- 208000007565 gingivitis Diseases 0.000 claims description 2
- 230000007407 health benefit Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UJNPHNKJSKIVTE-SCGRZTRASA-L zinc;(2s)-2-amino-5-(diaminomethylideneamino)pentanoate Chemical compound [Zn+2].[O-]C(=O)[C@@H](N)CCCNC(N)=N.[O-]C(=O)[C@@H](N)CCCNC(N)=N UJNPHNKJSKIVTE-SCGRZTRASA-L 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 229940024606 amino acid Drugs 0.000 description 61
- 235000001014 amino acid Nutrition 0.000 description 59
- 150000001413 amino acids Chemical class 0.000 description 36
- 239000000606 toothpaste Substances 0.000 description 31
- 229940034610 toothpaste Drugs 0.000 description 30
- 239000000499 gel Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- 210000004268 dentin Anatomy 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000011282 treatment Methods 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 230000001680 brushing effect Effects 0.000 description 12
- 150000004820 halides Chemical class 0.000 description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229960003646 lysine Drugs 0.000 description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000004472 Lysine Substances 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 239000004475 Arginine Substances 0.000 description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 5
- 229960003121 arginine Drugs 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229960002449 glycine Drugs 0.000 description 3
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 210000005239 tubule Anatomy 0.000 description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960005261 aspartic acid Drugs 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000012470 diluted sample Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 229940041672 oral gel Drugs 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229960004295 valine Drugs 0.000 description 2
- 239000004474 valine Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- QDRLNOULQCBRJN-JEDNCBNOSA-N (2s)-2-amino-4-methylpentanoic acid;zinc Chemical compound [Zn].CC(C)C[C@H](N)C(O)=O QDRLNOULQCBRJN-JEDNCBNOSA-N 0.000 description 1
- BLCJBICVQSYOIF-UHFFFAOYSA-N 2,2-diaminobutanoic acid Chemical compound CCC(N)(N)C(O)=O BLCJBICVQSYOIF-UHFFFAOYSA-N 0.000 description 1
- SKWCZPYWFRTSDD-UHFFFAOYSA-N 2,3-bis(azaniumyl)propanoate;chloride Chemical compound Cl.NCC(N)C(O)=O SKWCZPYWFRTSDD-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical group Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 1
- 108010011485 Aspartame Proteins 0.000 description 1
- 241000189524 Baccharis halimifolia Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- RHGKLRLOHDJJDR-BYPYZUCNSA-N L-citrulline Chemical compound NC(=O)NCCC[C@H]([NH3+])C([O-])=O RHGKLRLOHDJJDR-BYPYZUCNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- RHGKLRLOHDJJDR-UHFFFAOYSA-N Ndelta-carbamoyl-DL-ornithine Natural products OC(=O)C(N)CCCNC(N)=O RHGKLRLOHDJJDR-UHFFFAOYSA-N 0.000 description 1
- GHGVHHVOANIDQA-UHFFFAOYSA-L O.[OH-].[Cl-].[Zn++] Chemical compound O.[OH-].[Cl-].[Zn++] GHGVHHVOANIDQA-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- BOHQCUKFMRYRDY-UHFFFAOYSA-M [N-]=C=O.[Cl-].[Zn+2] Chemical compound [N-]=C=O.[Cl-].[Zn+2] BOHQCUKFMRYRDY-UHFFFAOYSA-M 0.000 description 1
- DTHZWUDUWBPDQI-UHFFFAOYSA-N [Zn].ClO Chemical compound [Zn].ClO DTHZWUDUWBPDQI-UHFFFAOYSA-N 0.000 description 1
- QVLSUSDHNOLZMO-UHFFFAOYSA-N [Zn].ClOCl Chemical compound [Zn].ClOCl QVLSUSDHNOLZMO-UHFFFAOYSA-N 0.000 description 1
- HFFROHHGHGDACO-JEDNCBNOSA-N [Zn].NCCCC[C@H](N)C(Cl)=O Chemical group [Zn].NCCCC[C@H](N)C(Cl)=O HFFROHHGHGDACO-JEDNCBNOSA-N 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- IAOZJIPTCAWIRG-QWRGUYRKSA-N aspartame Chemical compound OC(=O)C[C@H](N)C(=O)N[C@H](C(=O)OC)CC1=CC=CC=C1 IAOZJIPTCAWIRG-QWRGUYRKSA-N 0.000 description 1
- 235000010357 aspartame Nutrition 0.000 description 1
- 239000000605 aspartame Substances 0.000 description 1
- 229960003438 aspartame Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000013477 citrulline Nutrition 0.000 description 1
- 229960002173 citrulline Drugs 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 229960002743 glutamine Drugs 0.000 description 1
- 229960001269 glycine hydrochloride Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 235000011649 selenium Nutrition 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000008521 threonine Nutrition 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
- 229960004799 tryptophan Drugs 0.000 description 1
- 229960004441 tyrosine Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 229940068475 zinc citrate Drugs 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
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/45—Colour indicators, e.g. pH- or Redox indicators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/58—Metal complex; Coordination compounds
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Cosmetics (AREA)
Description
本發明說明牙齒清潔方法,其包含投予包含鋅胺基酸鹵化物錯合物之組成物至口腔;及保留組成物在口腔中足夠形成沉澱物的時間。
對美白牙齒的口腔保健產品仍有需求。常使用漂白材料(諸如過氧化物)美白牙齒,但是過氧化物難以足以提供好的美白效果之濃度調配及運送。亦使用白色顏料,諸如氧化鋅,但是此等不可溶之顏料亦難以調配及運送。
亦對方便於消費者的經改善之產品及方法仍有需求,以鼓勵使用者以較長的刷牙時間刷他們的牙齒。建議孩童應以至少45-60秒及成人應以至少90至120秒刷他們的牙齒。大部分的人,尤其是孩童以不足以獲得最大效益的期間刷他們的牙齒,而且難以準確地評估必要的刷牙時間。已知包含著色薄膜斷片的牙膏或在適當的刷動時會釋出顏料的包膠物,但是該等顏料對牙齒沒有特別的效益。
驚訝地發現雖然鋅胺基酸鹵化物錯合物在濃縮的水溶液中為可溶的、無色的且穩定的,甚至在中性pH下,但是鋅胺基酸鹵化物錯合物在更稀釋的溶液中分解,以提供相對不可溶的含鋅沉澱物,例如氧化鋅沉澱物。此動態令人驚訝,因為當溶液變得更稀釋時,人們可能預期離子錯合物維持在溶液中。此沉澱可有用地標記已經過的最短刷牙期間,而且沉澱提供白色的含鋅沉澱物經控制沉積在牙齒上。
本發明因此在一個具體實例中提供(i)標出刷牙的時間量;及/或(ii)美白牙齒之方法,其包含以包含鋅胺基酸鹵化物錯合物之牙膏在水的存在下刷牙,直到鋅胺基酸鹵化物錯合物提供來自牙膏及水的鋅沉澱物。該方法包含以含有鋅胺基酸鹵化物錯合物之牙膏刷牙,直到鋅胺基酸鹵化物錯合物分解以提供白色的含鋅沉澱物為止。時間就孩童而言可為例如30至120秒,例如45-60秒,或就成人而言可為90-120秒。
例如,在一個具體實例中,牙膏為透明凝膠。在刷一段期間之後,例如至少30秒,鋅胺基酸鹵化物錯合物分裂,且透明的凝膠牙膏因沉澱物而瞬間成為白色及不透明的,向使用者發出的標記使她或他以適當的期間刷牙。
在一個特定的具體實例中,鋅-胺基酸錯合物為鋅-離胺酸-氯化物錯合物,例如以ZLC命名之新穎錯合物,其可從氧化鋅與離胺酸鹽酸鹽之混合物形成。ZLC具有化學結構[Zn(C6H14N2O2)2Cl]+Cl-,且可以陽離子性陽離子([Zn(C6H14N2O2)2Cl]+)與氯化物陰離子之溶液存在,或可為固體鹽,例如晶體,視需要呈單-或二水合物形式。
本發明的更多可應用領域將從下文提供的詳細說明而變得顯而易見。應瞭解詳細說明及特定的實施例雖然指出本發明較佳的具體實例,但是意欲以例證為目的,並不意欲限制本發明的範圍。
以下較佳的具體實例之說明在本質上僅為範例而已,並不意欲以任何方式限制本發明,其應用或用途。
本發明因此在特定的具體實例中提供清潔及/或美白牙齒之方法(方法1),其包含以包含鋅-胺基酸-鹵化物錯合物之牙膏在水的存在下刷牙,直到錯合物崩解為止,其中因此形成的白色沉澱物提供標記給適當刷牙的使用者,及/或提供牙齒美白效益,例如
1.1.方法1,其中在錯合物崩解之前的刷牙時間就孩童使用的牙膏而言係介於30與180秒之間,例如約45-60秒,及就成人使用的牙膏而言為約90-120秒。
1.2.方法1,其中在錯合物中的胺基酸係選自呈游離或口腔可接受之酸加成鹽形式(例如,鹽酸鹽形式)的離胺酸和精胺酸。
1.3.前述方法中之任一者,其中在錯合物中的鹵化物係選自氯化物、氟化物、溴化物及其混合物,例如氯化物。
1.4.前述方法中之任一者,其中在錯合物中的Zn:胺基酸之莫耳比係從3:1至1:5,例如約1:2,及Zn:鹵化物之莫耳比係從3:1至1:3,例如約1:2。
1.5.前述方法中之任一者,其中鋅係以牙膏重量的0.05至10%之量存在,視需要為至少牙膏重量的0.1,至少0.2,至少0.3,至少0.4,至少0.5,至少1,至少2,至少3,或至少4到至多10%,例如約1-3%,例如約牙膏重量的2-2.7%。
1.6.前述方法中之任一者,,其中胺基酸係以牙膏重量的0.05至30%之量存在,視需要為至少牙膏重量的0.1,至少0.2,至少0.3,至少0.4,至少0.5,至少1,至少2,至少3,至少4,至少5,至少10,至少15,至少20到至多30%,例如約1-10%。
1.7.前述方法中之任一者,其中牙膏包含2:1至1:4的鋅對胺基酸之莫耳比,視需要為1:1至1:4,1:2至1:4,1:3至1:4,2:1至1:3,2:1至1:2,或2:1至1:1,例如約1:2或1:3。
1.8.前述方法中之任一者,其中鋅胺基酸錯合物為鋅離胺酸氯化物錯合物(例如,(ZnLys2Cl)+Cl-或(ZnLys3)2+Cl2)或鋅精胺酸氯化物錯合物。
1.9.前述方法中之任一者,其中鋅胺基酸錯合物為鋅離胺酸氯化物錯合物,例如ZLC,例如具有化學結構[Zn(C6H14N2O2)2Cl]+Cl-之鋅離胺酸氯化物錯合物,其呈陽離子性陽離子(例如,[Zn(C6H14N2O2)2Cl]+)及氯化物陰離子之溶液,或固體鹽形式,例如晶體形式,視需要為單-或二水合物形式。
1.10.前述方法中之任一者,其中牙膏係呈透明凝膠形式,其在稀釋時提供氧化鋅沉澱物。
1.11.前述方法中之任一者,其中鋅-胺基酸-鹵化物錯合物係以有效量存在於牙膏中,例如對應於0.1-3重量%之鋅,例如約0.2-1重量%之鋅的量於牙膏中。
1.12.前述方法中之任一者,其額外提供選自下列的口腔保健效益:降低或抑制琺瑯質的酸侵蝕、清潔牙齒、減少細菌產生的生物膜和牙菌斑、降低牙齦炎、抑制蛀牙和齲齒的形成及/或降低牙質過敏性。
1.13.前述方法中之任一者,其中牙膏係呈透明凝膠形式,其中鋅-胺基酸-鹵化物錯合物為具有化學結構[Zn(C6H14N2O2)2Cl]+Cl-之鋅-離胺酸-氯化物錯合物,以對應於0.1-2重量%,例如約0.5重量%之鋅的量存在於牙膏中,且進一步包含例如45-65%之量(例如,約50-60%)的保濕劑,例如山梨醇、丙二醇及其混合物,例如0.1-2%之量的增稠劑,例如纖維素衍生物,例如選自羧甲基纖維素(CMC)、三甲基纖維素(TMC)及其混合物,甜味劑及/或調味劑,及水,例如其中牙膏為口腔用凝膠,其包含:
本發明亦提供鋅胺基酸鹵化物錯合物在根據前述方法1中之任一者及以下等等中的方法之用途,或在製造前述方法1中之任一者及以下等等中使用的牙膏之用途。
鋅、胺基酸與鹵化物在水性介質中的組合形成陽離子錯合物-鹵化物鹽。鋅胺基酸鹵化物為從鋅的鹵化物酸加成鹽(例如,氯化鋅)及胺基酸,或從胺基酸的鹵化物酸加成鹽(例如,離胺酸鹽酸鹽)及鋅離子來源(例如,氧化鋅或TBZC),及/或從氫鹵酸、胺基酸與鋅離子來源之全部三種的組合所形成之水溶性錯合物。
與胺基酸氫鹵酸鹽或與胺基酸加上氫鹵酸組合的鋅離子來
源可為有效提供Zn++離子之任何來源,例如氧化鋅、氯化鋅、四鹼式氯化鋅、碳酸鋅、硝酸鋅、檸檬酸鋅和磷酸鋅。氧化鋅為不溶於水中的白色粉末。四鹼式氯化鋅(TBZC)或氯化鋅氫氧化物單水合物為具有式Zn5(OH)8Cl2.H2O之鋅羥基化合物,亦稱為鹼式氯化鋅、羥基氯化鋅或氧氯化鋅。其為不溶於水中的無色結晶固體。發現該兩種材料在胺基酸的存在下可溶於水中且提供鋅離子來源,同時限制可用的陰離子,因為過量的陰離子可干擾錯合物的形成。
胺基酸來源可為任何胺基酸。胺基酸的實例包括但不限於常
見的天然胺基酸,例如:離胺酸、精胺酸、組胺酸、甘胺酸、絲胺酸、蘇胺酸、天冬醯胺、麩醯胺酸、半胱胺酸、硒代半胱胺酸、脯胺酸、丙胺酸、纈胺酸、異亮胺酸、亮胺酸、甲硫胺酸、苯基丙胺酸、酪胺酸、色胺酸、天冬胺酸和麩胺酸。
在一些具體實例中,胺基酸為鹼性胺基酸。以「鹼性胺基酸」
意指天然生成之鹼性胺基酸,諸如精胺酸、離胺酸和組胺酸,以及在分子中具有羧基和胺基的任何鹼性胺基酸,其為水溶性且提供具有約7或更大的pH之水溶液。據此,鹼性胺基酸包括但不限於精胺酸、離胺酸、瓜胺酸、鳥胺基、肌酸、組胺酸、二胺基丁酸、二胺基丙酸、其鹽或其組合。在特定的具體實例中,胺基酸為離胺酸。在其他的具體實例中,胺基酸為精胺酸。然而,中性胺基酸(諸如甘胺酸)及甚至酸性胺基酸(諸如天冬胺酸)亦能夠與強酸(諸如氫鹵酸)形成鹽。在一些具體實例中,胺基酸為中性或酸性胺基酸,例如甘胺酸。
鹵化物來源可為一部分的鋅來源,諸如氯化鋅或四鹼式氯化
鋅。鹵化物來源可為一部分的胺基酸,諸如胺基酸氫鹵酸鹽。鹵化物來源亦可為氫鹵酸。鹵化物可為氯化物、溴化物或碘化物,最典型為氯化物。
胺基酸及氫鹵酸(例如,HCl、HBr或HI)的酸加成鹽在本文有時稱為胺基酸氫鹵酸鹽。因此,胺基酸氫鹵酸鹽的一個實例為離胺酸鹽酸鹽。另一實例為甘胺酸鹽酸鹽。
在特定的具體實例中,在用於上述方法的組成物中的鋅胺基酸鹵化物量為組成物重量的0.05至40%。在特定的具體實例中,前驅物(例
如,氧化鋅和胺基酸氫鹵酸鹽)的存在量使得組合成鋅胺基酸鹵化物時,鋅胺基酸鹵化物可以組成物重量的0.05至40%之量存在。在該等具體實例中之任一者中,鋅胺基酸鹵化物之量可以所欲目的而改變,諸如作為抗細菌劑或作為止汗劑。在其他的具體實例中,鋅胺基酸鹵化物係以組成物重量的0.05至40%之量存在,視需要為至少組成物重量的0.1,至少0.2,至少0.3,至少0.4,至少0.5,至少1,至少2,至少3,或至少4到至多40%,或視需要為組成物重量的0.1到至多30%,至多20%,至多10%,至多5%,至多4%,至多3%,至多2%,或至多1%。
當鋅胺基酸鹵化物係從前驅物材料形成時,則前驅物材料較
佳地以產生所欲鋅胺基酸鹵化物大約必要的莫耳比使用,雖然過量的一種或另一種材料可能為特定的調配物中所希望的,例如以對抗其他的調配物成分來平衡pH,提供額外的抗細菌鋅或提供胺基酸緩衝液。然而,較佳地使鹵化物的量受到限制,因為限制鹵化物的水平有點鼓勵鋅與胺基酸之間的交互作用。例如,在生產鋅離胺酸氯化物(ZnLys3Cl2)的一個具體實例中,在前驅物材料中的元素之莫耳比可包括約1莫耳當量Zn2+:3莫耳當量Lys:2莫耳當量Cl-。
在一些具體實例中,在本發明使用的牙膏中之鋅的總量為牙
膏重量的0.05至3%。在其他的具體實例中,鋅的總量為至少牙膏重量的0.1,至少0.2,至少0.3,至少0.4,至少0.5,或至少1到至多2.5或3%。
在其他的具體實例中,在牙膏中之鋅的總量為少於組成物重量的5,少於4,少於3,少於2,或少於1至0.05%。
在特定的具體實例中,在用於本發明的方法之牙膏中的鋅對
胺基酸之莫耳比為至少2:1。在其他的具體實例中,莫耳比為至少1:1,至少1:2,至少1:3,至少1:4,2:1至1:4,1:1至1:4,1:2至1:4,1:3至1:4,2:1至1:3,2:1至1:2,2:1至1:1,或1:3。預期鋅在大於1:4會完全溶解。
在特定的具體實例中,鋅胺基酸鹵化物為具有式[Zn(C6H14N2O2)2Cl]+Cl-之鋅-離胺酸錯合物(在本文有時稱為「ZLC」)。
在特定的具體實例中,鋅胺基酸鹵化物具有式ZnAA3Hal2,其中Zn為二價鋅離子,AA為胺基酸殘基,及Hal為鹵化物離子。
本發明的一些具體實例提供牙齒清潔之方法,其包含投予包
含鋅胺基酸鹵化物錯合物之組成物至口腔;及保留組成物在口腔中足以形成沉澱物的時間。在一些具體實例中,沉澱物提供標記給使用者。在一些具體實例中,標記為視覺可接受標記。在一些具體實例中,標記表明組成物已使用了適當的時間。
在一些具體實例中,組成物係在口腔中30秒之後形成沉澱
物。在一些具體實例中,組成物係在口腔中90秒之後形成沉澱物。在一些具體實例中,組成物係在口腔中120秒之後形成沉澱物。
以本文之方法使用的組成物及調配物係參考彼之成分予以
說明,如本技藝中常用的方式。如熟諳此項技術者所明白,成分可在一些事例中互相反應,所以最終調配物的真實組成與所列示之成份可能不完全對應。因此,應瞭解本發明延伸至所列示之成分組合的產物。
如在所有方面所使用的範圍被用作為說明在該範圍內的各
個和每個值的簡略表達方式。可選擇在範圍內的任何值作為範圍的邊界。
另外,將本文所引述之所有參考文獻以其全文特此併入以供參考。在本發明中的定義與引述之參考文獻的定義衝突的情況中,則以本發明的揭示內容為準。
在本文及本說明書中的任何地方所表達之所有的百分比及
量應瞭解係指重量百分比,除非另有其他指定。所給定之量係以材料的活性重量為基準。
形成ZLC之通用反應係如下:ZnO+2(離胺酸.HCl)-›[Zn(離胺酸)2Cl]Cl.2H2O(ZLC)
2:1之莫耳比的ZnO:離胺酸.HCl懸浮液係在室溫下攪拌約12小時而製得。將混合物離心。將1毫升上清液轉移至NMR管中。接著將NMR管放入以乙醇填充之密閉的試管中,使晶體生長。在一週之後形成許多無色立方晶體。ZLC晶體之晶體結構係以單晶體X-射線繞射法測定。此結構的關鍵參數為:晶體系統:單斜晶系,空間群:P 21。單位晶胞尺寸:a=
5.2751(8)Å,b=17.055(3)Å,c=11.4072(18)Å。α=90°,β=94.064(2)°,γ=90°。在此錯合物中,Zn陽離子係以兩個具有來自NH2基團的兩個N原子及來自羧酸基團的兩個O原子之離胺酸配體在赤道面上配位。其顯現扭曲的四方錐體幾何形,具有以Cl原子佔據的頂點位置。此新穎結構產生正陽離子部分,其與Cl陰離子組合而形成離子鹽。
按實驗室比例放大純ZLC粉末的合成:將2莫耳離胺酸HCl在室溫下以攪拌溶解在1000毫升DI水中,將1莫耳固體ZnO以攪拌緩慢添加至離胺酸HCl溶液中且在RT下繼續攪拌隔夜(約12小時)。將懸浮溶液在高速下離心15分鐘。將上清液緩慢倒入EtOH中。立即形成沉澱物。需要約5-8毫升EtOH得到1公克粉末。將具有粉末的EtOH溶劑過濾,且獲得灰白色粉末。將粉末放入50℃烘箱中乾燥且獲得88%產率之產物。PXRD確認與ZLC晶體相比之ZLC粉末的純度。
調配具有ZLC作為活性成分的口腔用凝膠牙膏且與含有ZnCl2、ZnO和NaF之其他調配物相比。僅ZLC調配物顯示與目前含有NaF之凝膠相可競爭的澄清度。ZLC凝膠相的沉澱性質亦以水解反應研究進行調查,提供以下證據:當以含有ZLC活性物之牙膏刷牙時,在刷牙期間所形成之不可溶粒子可穿透至牙質小管中且阻斷小管,使消費者得到抗敏感效果及標記。
將含有NaF(對照物)、ZLC、ZnCl2和ZnO作為活性成分的4個500.0公克凝膠相批組以表1中所示之成分調配。比較具有不同活性物之樣品的澄清度,且以稀釋評估ZLC凝膠相的沉澱特性。以ICP所獲得在ZLC溶液中的鋅離子濃度為25300ppm,以此得到在溶液中約17重量%之ZLC活性物。在以下批組中的鋅離子濃度全部皆以0.5%(w/w)之鋅水平製得。
使用Lambda 25 UV/VIS光譜計(PerkinElmer)獲得所有樣品
的吸光率資訊,以比較在不同活性物之間的凝膠相澄清度。吸光率為通過物質時經吸收之光量的對數度量。因為在凝膠中的粒子吸收光,所以在溶液中存在的粒子越多,則以凝膠吸收的光越多。因此,低數值的凝膠吸光率表示較高的澄清度。吸光率係使用去離子(DI)水作為空白溶液在610奈米波長之光源下校正。ZnO不溶解且懸浮在凝膠相中,得到高吸光率。儘管ZnCl2可溶於水中,但是含有ZnCl2之凝膠相出現混濁。僅以ZLC調配之凝膠相形成均勻的溶液且顯示與以NaF調配之凝膠相可競爭的澄清度。將所有樣品的吸光率及pH顯示於表2中。
稀釋實驗:將所有原始凝膠相批組稀釋成2倍、4倍、8倍、
16倍和32倍。當ZnCl2凝膠及ZnO凝膠進一步稀釋時,則吸光率下降,而在進一步稀釋之ZLC凝膠溶液中的吸光率增加。此觀察確認當ZLC凝膠以水稀釋時形成沉澱物。2倍、4倍、8倍、16倍和32倍稀釋之ZLC凝膠的pH分別為7.71、7.91、8.03、8.12和8.14。
上述凝膠可單獨使用(較佳的目的為提供標記給適當的刷牙
時間之使用者)或用在具有凝膠相及研磨膏相之牙膏中。ZLC為牙膏調配物之凝膠相中的活性成分。與以ZnCl2和ZnO調配之凝膠相批組相比,僅以ZLC作為活性物的調配物顯示與市售產品中所使用者(NaF作為活性成分)可競爭的澄清度及pH。稀釋實驗顯示僅ZLC凝膠相可從在稀釋時的透明凝膠形成不可溶之沉澱物。在使用此類型的牙膏之後,以稀釋形成的不可溶
之沉澱物加速在牙質小管中形成「堵塞物」,其美白牙齒且在消費者使用期間提供白色沉澱物標記。
製備ZLC的各種稀釋液,以評估其產生可見的沉澱物及/或凝絮之效力,其可運送至牙齒表面(牙質及/或琺瑯質)上以得到美白效益。
ZLC之純淨溶液係藉由以下方式製備:1)將0.5莫耳ZnO粉末與1莫耳離胺酸HCl在1公升水中於室溫下反應約2小時,及2)經由離心收集上清液,接著使用0.45微米薄膜過濾。純淨溶液具有2.39重量%之鋅濃度及約7.03之pH。
稀釋實驗係藉由將純淨溶液與去離子水混合來進行。將純淨溶液稀釋2倍、4倍、6倍、7倍、8倍、10倍、12倍、16倍、20倍、24倍、28x和32倍,其分別對應於1.20重量%、0.598重量%、0.398重量%、0.341重量%、0.299重量%、0.239重量%、0.199重量%、0.149重量%、0.120重量%、0.0996重量%、0.0854重量%、0.0747重量%之初始鋅濃度。將稀釋之樣品保持在37℃且監測發生凝絮/沉澱之速率。具有0.149%和0.199%之初始鋅濃度的稀釋液能夠在儲備溶液與水混合時之時間點起30分鐘之內產生一些可見的凝絮。從混合起1小時在具有介於0.0854%與0.239%之間的初始鋅濃度的稀釋液中觀察到可見的凝絮。在混合之後1又半小時在具有介於0.0747%與0.239%之間的初始鋅濃度的稀釋液中觀察到可見的凝絮。在混合之後2小時,具有0.299%之初始鋅濃度的額外樣品亦顯示凝絮的存在。在總計19小時之後,在所有樣品中皆觀察到凝絮,除了具有1.20%之初始鋅濃度的樣品以外,且以具有介於0.0747%與0.239%之間的初始鋅濃度的樣品顯出最多沉澱物。
最終稀釋之樣品的pH值適合於口腔保健應用。分別具有0.0747重量%、0.0854重量%、0.0996重量%、0.120重量%、0.149重量%、0.199重量%和0.239重量%之初始鋅濃度的樣品分別具有7.99、8.13、8.11、7.97、7.99、6.80和6.70之pH值。該等pH值完全在5.5至10之範圍內,其限定適合於口腔保健調配物之範圍。
鋅主要以氧化鋅形式存在於沉澱物中。離胺酸係以其完整組份及/或以雜質存在於沉澱物中。
共焦影像證明ZLC在可形成可見的沉澱之條件下在牙質表面上產生沉積物的效力。以肉眼檢查時,沉積物賦予牙質表面白色。
沉積/閉塞檢定係使用人類牙質切片及實施例3的純淨溶液進行。牙質切片的製備係藉由將人類牙齒切成約800微米厚度的薄牙質片,指定一試驗面,將此試驗面使用約600粒度之砂紙磨砂,將該試驗面使用Buehler拋光布和5微米Buehler氧化鋁拋光,將該牙質片在1%(重量)之檸檬酸溶液中酸浸漬約20秒,將該牙質片聲波化10分鐘且將該牙質片貯存在磷酸鹽緩衝之食鹽水(PBS,pH 7.4,Gibco目錄號:10010)中。
將用於處理的純淨溶液以水稀釋16倍,得到約0.149重量%之初始鋅濃度的處理溶液。將牙質片插入37℃之處理溶液中1小時。接著將處理之牙質片從處理溶液取出且沖洗4次,每次以1毫升PBS。接著將牙質片使用以紙為主的棉紙乾燥及在XYZ與XYZ兩種模式的共焦顯微鏡下檢查。接著以相同的方式進行處理。
可經由共焦影像觀察到漸進式沉積和閉塞。第一次處理導致明顯的沉積。第二次處理導致表面完全覆蓋,包括阻塞幾乎所有的小管開口。表面沉積物的厚度可為10微米或更厚。在第三次處理之後,觀察到表面完全覆蓋且小管開口完全阻塞。表面沉積物的厚度可為25微米或更厚。
共焦影像證明ZLC在未觀察到可見的沉澱之條件下在牙質表面上產生沉積物的效力。
將按照實施例4之程序所製得的新牙質片以具有0.0747重量%之初始鋅濃度的ZLC稀釋液重複處理。每次處理包含32毫升稀釋之溶液(來自實施例3的1毫升純淨溶液及31毫升去離子水)且在37℃下持續10分鐘,在此期間,以肉眼未觀察到沉澱。在每次處理之後在共焦顯微鏡下檢查牙質片。在連續4次處理之後,觀察到顯著的表面沉積。在連續12次處理之後,觀察到表面完全覆蓋,未留下小管開口存在的標記。
因此,表面沉積可在不產生可見的沉澱之稀釋比及處理持續期間二者而論的條件下出現。結果,美白效益可在比從實施例3和4直接推論結果更寬的稀釋比範圍及更短的處理時間達成。
分光光度分析證實ZLC處理的美白效力。在第三次處理之後,將實施例4之牙質片乾燥且在SpectroshadeTM分光光度計(Handy Dental Type 71,3000)下檢查。檢查包括經處理之牙質區域,而不包括琺瑯質邊緣,且接著處理數據。CIELAB色彩讀值為L*=86.6,a*=-1.7,及b*=1.5。以類似方式製備而未經處理之牙質片得到L*=72.5,a*=-1.9,及b*=10.3之讀值。通常瞭解的是以下的定義:L*=0意指黑色及L*=100表示擴散白,負的a*值表示綠色,而正值表示品紅色,及負的b*值表示藍色,而正值表示黃色。可得出結論為ZLC處理提高牙質表面的整體白度及降低黃度。
雖然本發明已以關於特定的實施例說明,包括目前進行本發明的較佳模式,但是那些熟諳此項技術者將察知有許多上述系統和技術的變化及交換。應瞭解可利用其他的具體實例,且可進行結構與功能修改而不違背本發明的範圍。因此,本發明的範圍應以所附申請專利範圍中所提出而廣泛地解釋。
Claims (14)
- 一種鋅胺基酸鹵化物錯合物在製造用於清潔牙齒的組成物之用途,其中將該組成物投予口腔及在口腔中保留足以形成沉澱物的時間。
- 根據請求項1之用途,其中該沉澱物提供標記給使用者。
- 根據請求項2之用途,其中該標記為視覺可接受標記。
- 根據請求項2或3之用途,其中該標記表明組成物已使用了適當的時間。
- 根據請求項1之用途,其中將該組成物稀釋至在口腔中30秒之後足以形成沉澱物的程度。
- 根據請求項1之用途,其中將該組成物稀釋至在口腔中90秒之後足以形成沉澱物的程度。
- 根據請求項1之用途,其中將該組成物稀釋至在口腔中120秒之後足以形成沉澱物的程度。
- 根據請求項1之用途,其中該沉澱物為白色沉澱物,及其中該沉澱物提供牙齒美白效益。
- 根據請求項1之用途,其中該鋅胺基酸鹵化物錯合物為鋅離胺酸氯化物錯合物或鋅精胺酸氯化物錯合物。
- 根據請求項1之用途,其中該鋅胺基酸鹵化物錯合物為具有化學結構[Zn(C6H14N2O2)2Cl]+ Cl-之鋅離胺酸氯化物錯合物。
- 根據請求項1之用途,其中該組成物係呈透明凝膠形式,其在稀釋時提供氧化鋅沉澱物。
- 根據請求項1之用途,其額外提供選自下列的口腔保健效益:降低或抑制琺瑯質的酸侵蝕、清潔牙齒、減少細菌產生的生物膜和牙菌斑、降低牙齦炎、抑制蛀牙和齲齒的形成及/或降低牙質過敏性。
- 根據請求項1之用途,其為美白牙齒之方法。
- 根據請求項1之用途,其為經特定期間清潔牙齒之方法。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2012/070534 WO2014098828A1 (en) | 2012-12-19 | 2012-12-19 | Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201436814A TW201436814A (zh) | 2014-10-01 |
| TWI522122B true TWI522122B (zh) | 2016-02-21 |
Family
ID=47501524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102146813A TWI522122B (zh) | 2012-12-19 | 2013-12-18 | 牙齒美白方法、視覺可接受標記及所使用之組成物 |
Country Status (9)
| Country | Link |
|---|---|
| US (4) | US9572756B2 (zh) |
| EP (1) | EP2934445B1 (zh) |
| CN (1) | CN104853728B (zh) |
| AR (1) | AR094207A1 (zh) |
| AU (1) | AU2012397269B2 (zh) |
| BR (1) | BR112015014444B1 (zh) |
| MX (1) | MX353167B (zh) |
| TW (1) | TWI522122B (zh) |
| WO (1) | WO2014098828A1 (zh) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX352357B (es) | 2012-12-19 | 2017-11-22 | Colgate Palmolive Co | Productos para el cuidado oral que contienen un complejo de zinc tetrabásico-aminoácido-halogenuro. |
| CA2892468C (en) | 2012-12-19 | 2019-10-08 | Colgate-Palmolive Company | Oral care products comprising tetrabasic zinc chloride and trimethylglycine |
| AU2012397270B9 (en) | 2012-12-19 | 2015-08-13 | Colgate-Palmolive Company | Oral care products comprising zinc oxide and trimethylglycine |
| RU2627840C2 (ru) | 2012-12-19 | 2017-08-14 | Колгейт-Палмолив Компани | Антиперспирантные продукты с содержанием белка и антиперспирантных солей |
| BR112015014502B1 (pt) * | 2012-12-19 | 2019-04-09 | Colgate-Palmolive Company | Composição para cuidado oral compreendendo um complexo haleto de aminoácido-zinco e usos da mesma |
| JP5968558B2 (ja) | 2012-12-19 | 2016-08-10 | コルゲート・パーモリブ・カンパニーColgate−Palmolive Company | 亜鉛リジン錯体 |
| US9675823B2 (en) | 2012-12-19 | 2017-06-13 | Colgate-Palmolive Company | Two component compositions containing zinc amino acid halide complexes and cysteine |
| CN104853721B (zh) | 2012-12-19 | 2017-10-27 | 高露洁-棕榄公司 | 锌精氨酸/赖氨酸卤化物 |
| AU2012397263B2 (en) | 2012-12-19 | 2015-09-24 | Colgate-Palmolive Company | Zinc amino acid halide mouthwashes |
| RU2638791C2 (ru) | 2012-12-19 | 2017-12-15 | Колгейт-Палмолив Компани | Композиция с галогенидными предшественниками аминокислоты/триметилглицина цинка |
| US9763865B2 (en) * | 2012-12-19 | 2017-09-19 | Colgate-Palmolive Company | Oral gel comprising zinc-amino acid complex |
| WO2014098828A1 (en) | 2012-12-19 | 2014-06-26 | Colgate-Palmolive Company | Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides |
| US9504858B2 (en) | 2012-12-19 | 2016-11-29 | Colgate-Palmolive Company | Zinc amino acid halide complex with cysteine |
| US9750670B2 (en) | 2012-12-19 | 2017-09-05 | Colgate-Palmolive Company | Zinc amino acid complex with cysteine |
| US10188112B2 (en) | 2012-12-19 | 2019-01-29 | Colgate-Palmolive Company | Personal cleansing compositions containing zinc amino acid/trimethylglycine halide |
| US9498421B2 (en) | 2012-12-19 | 2016-11-22 | Colgate-Palmolive Company | Two component compositions containing tetrabasic zinc-amino acid halide complexes and cysteine |
| WO2015195124A1 (en) | 2014-06-18 | 2015-12-23 | Colgate-Palmolive Company | Dentifrice comprising zinc - amino acid complex and phosphates |
| EP3157935B1 (en) | 2014-06-18 | 2018-08-15 | Colgate-Palmolive Company | Synthesis of zinc-lysine complex from zinc chloride |
| CN106459094B (zh) | 2014-06-18 | 2019-07-16 | 高露洁-棕榄公司 | 锌-赖氨酸络合物的低pH合成 |
| RU2717682C2 (ru) * | 2014-08-08 | 2020-03-25 | Колгейт-Палмолив Компани | Удаление и предупреждение окрашивания зубов |
| CN107072895A (zh) * | 2014-10-23 | 2017-08-18 | 高露洁-棕榄公司 | 包含锌化合物和过氧化物化合物的口腔护理组合物 |
| AU2017442633C1 (en) * | 2017-12-13 | 2021-12-23 | Colgate-Palmolive Company | Dentifrice comprising zinc - amino acid complex |
| WO2020047395A1 (en) | 2018-08-30 | 2020-03-05 | University Of Washington | Compositions and methods for dental care |
| US11091502B2 (en) | 2018-12-21 | 2021-08-17 | Colgate-Palmolive Company | Methods for synthesizing zinc-lysine-chloride complex |
| EP3897864A1 (en) | 2018-12-21 | 2021-10-27 | Colgate-Palmolive Company | Zinc-arginine-halide complex |
| US11229591B2 (en) | 2018-12-21 | 2022-01-25 | Colgate-Palmolive Company | Methods for synthesizing zinc-lysine-chloride complex |
| US11117906B2 (en) | 2018-12-21 | 2021-09-14 | Colgate-Palmolive Company | Methods for synthesizing zinc-lysine-chloride complex |
| WO2022083996A1 (en) | 2020-10-22 | 2022-04-28 | Unilever Ip Holdings B.V. | An oral care composition for whitening benefits |
Family Cites Families (103)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE735096C (de) | 1940-12-09 | 1943-05-06 | Ig Farbenindustrie Ag | Verfahren zur Herstellung von Sulfonsaeuren |
| US2527686A (en) | 1945-12-26 | 1950-10-31 | Max H Sandberg | Mouthwash |
| US2503280A (en) | 1947-10-24 | 1950-04-11 | Du Pont | Azo catalysts in preparation of sulfonic acids |
| US2507088A (en) | 1948-01-08 | 1950-05-09 | Du Pont | Sulfoxidation process |
| US2893918A (en) | 1957-04-24 | 1959-07-07 | Harold A Abramson | Deodorant composition |
| FR1247957A (fr) | 1958-09-28 | 1960-12-09 | Ajinomoto Kk | Procédé de séparation continue d'aminoacides racémiques |
| US3320174A (en) | 1964-04-20 | 1967-05-16 | Colgate Palmolive Co | Detergent composition |
| US3372188A (en) | 1965-03-12 | 1968-03-05 | Union Oil Co | Sulfoxidation process in the presence of sulfur trioxide |
| US3538230A (en) | 1966-12-05 | 1970-11-03 | Lever Brothers Ltd | Oral compositions containing silica xerogels as cleaning and polishing agents |
| US3678154A (en) | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
| US3535421A (en) | 1968-07-11 | 1970-10-20 | Procter & Gamble | Oral compositions for calculus retardation |
| US3741911A (en) | 1970-12-21 | 1973-06-26 | Hart Chemical Ltd | Phosphate-free detergent composition |
| US3959458A (en) | 1973-02-09 | 1976-05-25 | The Procter & Gamble Company | Oral compositions for calculus retardation |
| US3937807A (en) | 1973-03-06 | 1976-02-10 | The Procter & Gamble Company | Oral compositions for plaque, caries, and calculus retardation with reduced staining tendencies |
| US3862307A (en) | 1973-04-09 | 1975-01-21 | Procter & Gamble | Dentifrices containing a cationic therapeutic agent and improved silica abrasive |
| US3941818A (en) | 1973-08-20 | 1976-03-02 | Zinpro Corporation | 1:1 Zinc methionine complexes |
| US4021569A (en) * | 1973-08-20 | 1977-05-03 | Zinpro Corporation | Method of nutritional supplementation for zinc and methionine by ingesting 1:1 zinc methionine complexes |
| US4051234A (en) | 1975-06-06 | 1977-09-27 | The Procter & Gamble Company | Oral compositions for plaque, caries, and calculus retardation with reduced staining tendencies |
| US4021459A (en) * | 1975-08-14 | 1977-05-03 | Schering Corporation | Process for the preparation of 21-halogeno-21-desoxy-17α-acyloxy 20-keto-pregnenes |
| US4340583A (en) | 1979-05-23 | 1982-07-20 | J. M. Huber Corporation | High fluoride compatibility dentifrice abrasives and compositions |
| US4339432A (en) | 1979-06-20 | 1982-07-13 | Lever Brothers Company | Oral mouthwash containing zinc and glycine |
| CA1139229A (en) * | 1979-06-20 | 1983-01-11 | Thomas W. Ritchey | Zinc salt with glycine in oral composition |
| US4316824A (en) | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
| JPS57158724A (en) | 1981-03-26 | 1982-09-30 | Shiseido Co Ltd | Antimicrobial composition |
| US4565693A (en) | 1981-11-09 | 1986-01-21 | Colgate-Palmolive Company | Deodorant composition |
| US4487757A (en) | 1981-12-28 | 1984-12-11 | Colgate-Palmolive Company | Dispensing container of toothpaste which effervesces during toothbrushing |
| IL64700A0 (en) | 1982-01-01 | 1982-03-31 | Binderman Itzhak | Dental care compositions |
| US4885155A (en) | 1982-06-22 | 1989-12-05 | The Procter & Gamble Company | Anticalculus compositions using pyrophosphate salt |
| DE3238118A1 (de) | 1982-10-14 | 1984-04-19 | Verla-Pharm, Arzneimittelfabrik Apotheker H.J. v. Ehrlich GmbH & Co KG, 8132 Tutzing | Verfahren zur herstellung von komplexverbindungen aus aminodicarbonsaeuren, zweiwertigen metallionen und halogenidionen |
| US4687663B1 (en) | 1983-03-01 | 1997-10-07 | Chesebrough Ponds Usa Co | Dental preparation article and method for storage and delivery thereof |
| US4684528A (en) | 1984-06-11 | 1987-08-04 | Godfrey Science & Design, Inc. | Flavor of zinc supplements for oral use |
| US4599152A (en) | 1985-05-24 | 1986-07-08 | Albion Laboratories | Pure amino acid chelates |
| US5192531A (en) | 1988-12-29 | 1993-03-09 | Colgate-Palmolive Company | Antibacterial antiplaque oral composition |
| US5188821A (en) | 1987-01-30 | 1993-02-23 | Colgate-Palmolive Company | Antibacterial antiplaque oral composition mouthwash or liquid dentifrice |
| US4866161A (en) | 1987-08-24 | 1989-09-12 | University Of South Alabama | Inhibition of tartar deposition by polyanionic/hydrophobic peptides and derivatives thereof which have a clustered block copolymer structure |
| US5004597A (en) | 1987-09-14 | 1991-04-02 | The Procter & Gamble Company | Oral compositions comprising stannous flouride and stannous gluconate |
| US4842847A (en) | 1987-12-21 | 1989-06-27 | The B. F. Goodrich Company | Dental calculus inhibiting compositions |
| US5061815A (en) * | 1988-07-06 | 1991-10-29 | Zinpro Corporation | Metal lysine complexes and method for producing metal lysine complexes |
| US5156845A (en) | 1990-05-04 | 1992-10-20 | Colgate-Palmolive Company | Dry mouth lozenge |
| GB2243775A (en) | 1990-05-09 | 1991-11-13 | Unilever Plc | Oral compositions |
| JPH0578243A (ja) | 1990-12-11 | 1993-03-30 | Shiseido Co Ltd | 鎮痒剤及び鎮痒組成物 |
| GB9107833D0 (en) | 1991-04-12 | 1991-05-29 | Unilever Plc | Treatment of periodontitis |
| US5643559A (en) | 1991-10-30 | 1997-07-01 | Colgate-Palmolive Company | Deodorant compositions comprising inhibitors of odor-producing axillary bacterial exoenzymes |
| US5330748A (en) * | 1993-05-19 | 1994-07-19 | Church & Dwight Co., Inc. | Dentifrices containing zinc oxide particles |
| US5504055A (en) | 1994-03-15 | 1996-04-02 | J.H. Biotech, Inc. | Metal amino acid chelate |
| US5707679A (en) | 1994-09-30 | 1998-01-13 | Kemin Industries, Inc. | Metal propionates for use as animal feed supplements |
| EP1203575B1 (en) * | 1995-05-03 | 2010-09-01 | Unilever N.V. | Clear gel-type dentrifices |
| US5714447A (en) | 1996-01-24 | 1998-02-03 | Church & Dwight Co., Inc. | Deodorant soap or detergent composition containing a zinc compound and a polyamine |
| US5698724A (en) | 1996-04-30 | 1997-12-16 | Zinpro Corporation | Amino acid metal complexes using hydrolyzed protein as the amino acid source and methods re same |
| AU4428397A (en) | 1996-09-20 | 1998-04-14 | Warner-Lambert Company | Oral compositions containing a zinc compound |
| GB9622659D0 (en) | 1996-10-31 | 1997-01-08 | Unilever Plc | Hair treatment composition |
| US5897891A (en) | 1996-11-18 | 1999-04-27 | Godfrey; John C. | Flavorful zinc compositions for oral use incorporating copper |
| FI106923B (fi) | 1997-01-03 | 2001-05-15 | Cultor Ltd Finnsugar Bioproduc | Trimetyyliglysiinin käyttö kehon limakalvojen hygieniaan ja hoitoon tarkoitetuissa valmisteissa |
| US5993784A (en) | 1997-07-24 | 1999-11-30 | Whitehill Oral Technologies | Low foaming therapeutic toothpastes with improved cleaning and abrasion performance |
| DK176196B1 (da) | 1997-10-07 | 2007-01-08 | Ejvind Jersie Pedersen | Mundhygejnepræparat til behandling af halitosis samt anvendelse af et chelat omfattende en metaliondel og en aminosyredel som en komponent i præparatet |
| JP2002517411A (ja) | 1998-06-09 | 2002-06-18 | ウイリアム ジェイ エンブロ | 表皮刺激及び感染の治療のための方法並びに組成物 |
| US6558710B1 (en) | 1999-06-14 | 2003-05-06 | Helen Rebecca Godfrey | Topical zinc compositions and methods of use |
| US6685920B2 (en) | 1999-11-12 | 2004-02-03 | The Procter & Gamble Company | Method of protecting teeth against erosion |
| US7164035B2 (en) | 2000-01-07 | 2007-01-16 | Newsome David A | Zinc-monocysteine complex and method of using zinc-cysteine complexes |
| JP3490950B2 (ja) | 2000-03-15 | 2004-01-26 | 三洋電機株式会社 | 2シリンダ型2段圧縮式ロータリーコンプレッサ |
| DE10160933B4 (de) | 2001-12-12 | 2018-06-21 | Evonik Degussa Gmbh | Zubereitungen mit desodorierender Wirkung, enthaltend das Zinksalz der Ricinolsäure und mindestens eine aminofunktionelle Aminosäure |
| US6670494B1 (en) | 2001-12-17 | 2003-12-30 | J H Brotech, Inc. | Method for preparation of metal organic acid chelates |
| US20040033916A1 (en) | 2002-06-28 | 2004-02-19 | Kuzmin Vladimir Semenovich | Disinfecting composition |
| JP2004175790A (ja) * | 2002-11-12 | 2004-06-24 | Arita Junichi | α−グルコシダーゼ阻害作用を有する亜鉛含有物 |
| US7022351B2 (en) | 2003-01-14 | 2006-04-04 | Zinpro Corporation | Composition for supplementing animals with solutions of essential metal amino acid complexes |
| US20040198998A1 (en) | 2003-04-04 | 2004-10-07 | Marian Holerca | Glycine-free antiperspirant salts with betaine for enhanced cosmetic products |
| US7270806B2 (en) | 2004-07-27 | 2007-09-18 | Coty S.A. | Liquid stick antiperspirant |
| US7700079B2 (en) | 2005-09-26 | 2010-04-20 | Jamie Collins Doss | Therapeutic soap product with UV protection |
| CA2631254A1 (en) | 2005-11-29 | 2007-06-07 | The Procter & Gamble Company | Dentifrice composition comprising binder system comprising hydrophilic clay material |
| CN100366539C (zh) | 2006-05-25 | 2008-02-06 | 黄逸强 | 一种微量元素添加剂碱式氯化锌的制备方法 |
| DE102006040302A1 (de) | 2006-08-29 | 2008-03-20 | Henkel Kgaa | Antitranspirant- und Deodorant-Zusammensetzungen mit verbesserter Pflegewirkung |
| EP1935395B1 (en) | 2006-12-20 | 2013-06-05 | Unilever PLC | Oral composition |
| US8247398B2 (en) | 2007-02-17 | 2012-08-21 | Ssv Therapeutics, Inc. | Zinc complexes of natural amino acids for treating elevated copper caused toxicities |
| JP2009084201A (ja) | 2007-09-28 | 2009-04-23 | Riken Koryo Kogyo Kk | パーマネントウェーブ剤用消臭処理剤並びにこれを含有するパーマネントウェーブ剤 |
| EP2052978B1 (de) | 2007-10-26 | 2012-08-15 | MultiTec GmbH & Co. KG | Anzeigevorrichtung mit Datenerfassungseinrichtung und entsprechendes Verfahren |
| CN101925346A (zh) * | 2008-02-08 | 2010-12-22 | 高露洁-棕榄公司 | 口腔护理产品及其使用和制造方法 |
| US20110229536A1 (en) | 2008-05-12 | 2011-09-22 | Tagra Biotechnologies Ltd. | Compositions for topical application comprising microencapsulated colorants |
| US20100021573A1 (en) | 2008-07-22 | 2010-01-28 | Michael J Gonzalez | Compositions and methods for the prevention of cardiovascular disease |
| JP2010132639A (ja) | 2008-11-10 | 2010-06-17 | Nikko Chemical Co Ltd | Dna損傷抑制剤及びマトリックスメタロプロテアーゼ−1産生抑制剤 |
| RU2540520C2 (ru) | 2009-06-24 | 2015-02-10 | Чарльз Н.С. СОПАРКАР | Композиции и способы улучшения медикаментозной терапии средствами, зависящими от ионов металлов |
| CN101606639B (zh) | 2009-07-20 | 2012-07-25 | 曹江山 | 一种保育猪浓缩饲料 |
| RU2491912C1 (ru) | 2009-09-30 | 2013-09-10 | Колгейт-Палмолив Компани | Композиция антиперспиранта/дезодоранта |
| RU2523900C2 (ru) | 2009-10-29 | 2014-07-27 | Колгейт-Палмолив Компани | Средство для чистки зубов, содержащее фторид двухвалентного олова и цитрат цинка и небольшие количества воды |
| AR079890A1 (es) | 2010-01-13 | 2012-02-29 | Colgate Palmolive Co | Estabilizacion de peliculas de oxido de zinc en composiciones bucales |
| US8652495B2 (en) | 2010-03-31 | 2014-02-18 | Colgate-Palmolive Company | Oral care composition |
| CN103156073B (zh) | 2011-12-13 | 2015-02-18 | 北京东方联鸣科技发展有限公司 | 奶牛产后营养补充剂 |
| CN103535536A (zh) | 2012-07-15 | 2014-01-29 | 新沂市佳威饲料有限公司 | 一种哺乳母猪饲料的配制方法 |
| US9763865B2 (en) * | 2012-12-19 | 2017-09-19 | Colgate-Palmolive Company | Oral gel comprising zinc-amino acid complex |
| MX352357B (es) * | 2012-12-19 | 2017-11-22 | Colgate Palmolive Co | Productos para el cuidado oral que contienen un complejo de zinc tetrabásico-aminoácido-halogenuro. |
| WO2014204439A1 (en) | 2013-06-18 | 2014-12-24 | Colgate-Palmolive Company | Zinc amino acid halide complex with cysteine |
| WO2014098828A1 (en) | 2012-12-19 | 2014-06-26 | Colgate-Palmolive Company | Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides |
| BR112015014502B1 (pt) | 2012-12-19 | 2019-04-09 | Colgate-Palmolive Company | Composição para cuidado oral compreendendo um complexo haleto de aminoácido-zinco e usos da mesma |
| IN2015DN04211A (zh) | 2012-12-19 | 2015-10-16 | Colgate Palmolive Co | |
| RU2638791C2 (ru) | 2012-12-19 | 2017-12-15 | Колгейт-Палмолив Компани | Композиция с галогенидными предшественниками аминокислоты/триметилглицина цинка |
| US10494589B2 (en) | 2012-12-19 | 2019-12-03 | Colgate-Palmolive Company | Method for indicating time for washing or indicating delivery of antibacterial agent |
| AU2012397263B2 (en) | 2012-12-19 | 2015-09-24 | Colgate-Palmolive Company | Zinc amino acid halide mouthwashes |
| CN104853721B (zh) | 2012-12-19 | 2017-10-27 | 高露洁-棕榄公司 | 锌精氨酸/赖氨酸卤化物 |
| AU2012397270B9 (en) | 2012-12-19 | 2015-08-13 | Colgate-Palmolive Company | Oral care products comprising zinc oxide and trimethylglycine |
| JP5968558B2 (ja) | 2012-12-19 | 2016-08-10 | コルゲート・パーモリブ・カンパニーColgate−Palmolive Company | 亜鉛リジン錯体 |
| RU2627840C2 (ru) | 2012-12-19 | 2017-08-14 | Колгейт-Палмолив Компани | Антиперспирантные продукты с содержанием белка и антиперспирантных солей |
| WO2014098821A1 (en) | 2012-12-19 | 2014-06-26 | Colgate-Palmolive Company | Method for indicating time for washing or indicating delivery of antibacterial agent |
| WO2015195124A1 (en) * | 2014-06-18 | 2015-12-23 | Colgate-Palmolive Company | Dentifrice comprising zinc - amino acid complex and phosphates |
| US9913784B2 (en) * | 2015-12-22 | 2018-03-13 | Colgate-Palmolive Company | Oral care compositions comprising zinc amino acid halides |
-
2012
- 2012-12-19 WO PCT/US2012/070534 patent/WO2014098828A1/en not_active Ceased
- 2012-12-19 EP EP12809996.7A patent/EP2934445B1/en active Active
- 2012-12-19 AU AU2012397269A patent/AU2012397269B2/en not_active Ceased
- 2012-12-19 CN CN201280077901.XA patent/CN104853728B/zh not_active Expired - Fee Related
- 2012-12-19 US US14/653,300 patent/US9572756B2/en active Active
- 2012-12-19 MX MX2015007786A patent/MX353167B/es active IP Right Grant
- 2012-12-19 BR BR112015014444-6A patent/BR112015014444B1/pt not_active IP Right Cessation
-
2013
- 2013-12-18 TW TW102146813A patent/TWI522122B/zh not_active IP Right Cessation
- 2013-12-19 AR ARP130104941A patent/AR094207A1/es unknown
-
2017
- 2017-01-20 US US15/411,144 patent/US9993407B2/en active Active
-
2018
- 2018-05-14 US US15/978,549 patent/US10610475B2/en active Active
-
2020
- 2020-02-24 US US16/798,492 patent/US11197811B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US9572756B2 (en) | 2017-02-21 |
| EP2934445A1 (en) | 2015-10-28 |
| US10610475B2 (en) | 2020-04-07 |
| AU2012397269B2 (en) | 2015-10-29 |
| US20150335552A1 (en) | 2015-11-26 |
| EP2934445B1 (en) | 2017-10-04 |
| US9993407B2 (en) | 2018-06-12 |
| MX2015007786A (es) | 2015-08-20 |
| CN104853728A (zh) | 2015-08-19 |
| US20170128339A1 (en) | 2017-05-11 |
| MX353167B (es) | 2017-12-20 |
| WO2014098828A1 (en) | 2014-06-26 |
| US11197811B2 (en) | 2021-12-14 |
| BR112015014444B1 (pt) | 2019-10-01 |
| CN104853728B (zh) | 2018-07-24 |
| AU2012397269A1 (en) | 2015-06-18 |
| AR094207A1 (es) | 2015-07-15 |
| US20200206115A1 (en) | 2020-07-02 |
| TW201436814A (zh) | 2014-10-01 |
| BR112015014444A2 (pt) | 2017-07-11 |
| US20180256468A1 (en) | 2018-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI522122B (zh) | 牙齒美白方法、視覺可接受標記及所使用之組成物 | |
| TWI522120B (zh) | 包含鋅-胺基酸複合物的口腔用凝膠 | |
| TWI555536B (zh) | 包含鋅胺基酸鹵化物之口腔保健組成物 | |
| TWI555534B (zh) | 含四鹼基鋅-胺基酸-鹵化物複合物之口腔保健產品 | |
| EP2934447B1 (en) | Zinc amino acid halide mouthwashes | |
| TWI499433B (zh) | 鋅胺基酸鹵化物錯合物與半胱胺酸 | |
| AU2014398198B2 (en) | Low pH synthesis of zinc-lysine complex | |
| CN108289804A (zh) | 用于细菌聚集的金属氨基酸络合物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |