CN104822361A - 含磷酸锌的组合物 - Google Patents
含磷酸锌的组合物 Download PDFInfo
- Publication number
- CN104822361A CN104822361A CN201280077527.3A CN201280077527A CN104822361A CN 104822361 A CN104822361 A CN 104822361A CN 201280077527 A CN201280077527 A CN 201280077527A CN 104822361 A CN104822361 A CN 104822361A
- Authority
- CN
- China
- Prior art keywords
- dentifrice
- zinc
- collutory
- phosphate
- zinc phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 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 title claims abstract description 64
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 63
- 239000000551 dentifrice Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- 210000003298 dental enamel Anatomy 0.000 claims description 54
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 150000001413 amino acids Chemical class 0.000 claims description 25
- 235000021317 phosphate Nutrition 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 210000000214 mouth Anatomy 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 239000004475 Arginine Substances 0.000 claims description 18
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 11
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 11
- 230000000844 anti-bacterial effect Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 7
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 7
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 7
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 7
- 235000019800 disodium phosphate Nutrition 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- 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 claims description 5
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 5
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000230 xanthan gum Substances 0.000 claims description 4
- 235000010493 xanthan gum Nutrition 0.000 claims description 4
- 229920001285 xanthan gum Polymers 0.000 claims description 4
- 229940082509 xanthan gum Drugs 0.000 claims description 4
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 235000010241 potassium sorbate Nutrition 0.000 claims description 3
- 239000004302 potassium sorbate Substances 0.000 claims description 3
- 229940069338 potassium sorbate Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002324 mouth wash Substances 0.000 abstract description 3
- 229940051866 mouthwash Drugs 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 description 43
- -1 calcium ion.Usually Chemical class 0.000 description 38
- 229910052725 zinc Inorganic materials 0.000 description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 26
- 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 24
- 239000011746 zinc citrate Substances 0.000 description 24
- 235000006076 zinc citrate Nutrition 0.000 description 24
- 229940068475 zinc citrate Drugs 0.000 description 24
- 229940024606 amino acid Drugs 0.000 description 22
- 235000001014 amino acid Nutrition 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229940091249 fluoride supplement Drugs 0.000 description 18
- 239000011575 calcium Substances 0.000 description 17
- 235000009697 arginine Nutrition 0.000 description 16
- 229960003121 arginine Drugs 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 15
- 239000006072 paste Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 239000000606 toothpaste Substances 0.000 description 11
- 229940034610 toothpaste Drugs 0.000 description 11
- 208000002925 dental caries Diseases 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 239000003945 anionic surfactant Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 8
- 208000002064 Dental Plaque Diseases 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 235000011180 diphosphates Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 6
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229920006318 anionic polymer Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000011775 sodium fluoride Substances 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- 229960000414 sodium fluoride Drugs 0.000 description 5
- 229960003500 triclosan Drugs 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 4
- 208000006558 Dental Calculus Diseases 0.000 description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 4
- 239000004472 Lysine Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- INVGWHRKADIJHF-UHFFFAOYSA-N Sanguinarin Chemical compound C1=C2OCOC2=CC2=C3[N+](C)=CC4=C(OCO5)C5=CC=C4C3=CC=C21 INVGWHRKADIJHF-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005115 demineralization Methods 0.000 description 4
- 230000002328 demineralizing effect Effects 0.000 description 4
- 210000004268 dentin Anatomy 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229960003646 lysine Drugs 0.000 description 4
- 235000018977 lysine Nutrition 0.000 description 4
- 230000007406 plaque accumulation Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 235000010356 sorbitol Nutrition 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000010418 carrageenan Nutrition 0.000 description 3
- 229920001525 carrageenan Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 208000007565 gingivitis Diseases 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
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- 230000001976 improved effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- 150000002978 peroxides Chemical class 0.000 description 3
- OXHXATNDTXVKAU-UHFFFAOYSA-N phosphoric acid zinc Chemical group [Zn].OP(O)(O)=O OXHXATNDTXVKAU-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
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- 229960004711 sodium monofluorophosphate Drugs 0.000 description 3
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 3
- 229960002799 stannous fluoride Drugs 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 2
- ZIRURAJAJIQZFG-UHFFFAOYSA-N 1-aminopropane-1-sulfonic acid Chemical compound CCC(N)S(O)(=O)=O ZIRURAJAJIQZFG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 description 2
- ANAAMBRRWOGKGU-UHFFFAOYSA-M 4-ethyl-1-tetradecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+]1=CC=C(CC)C=C1 ANAAMBRRWOGKGU-UHFFFAOYSA-M 0.000 description 2
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- FCEXWTOTHXCQCQ-UHFFFAOYSA-N Ethoxydihydrosanguinarine Natural products C12=CC=C3OCOC3=C2C(OCC)N(C)C(C2=C3)=C1C=CC2=CC1=C3OCO1 FCEXWTOTHXCQCQ-UHFFFAOYSA-N 0.000 description 2
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- RHGKLRLOHDJJDR-BYPYZUCNSA-N L-citrulline Chemical compound NC(=O)NCCC[C@H]([NH3+])C([O-])=O RHGKLRLOHDJJDR-BYPYZUCNSA-N 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
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Abstract
本发明提供了口腔护理组合物,例如洁齿剂或漱口剂,其包含磷酸锌,其中所述磷酸锌作为预形成的盐添加到洁齿剂或漱口剂中;以及制造和使用该组合物的方法。
Description
背景
牙侵蚀包括由于非细菌性来源的酸侵蚀对牙齿结构的去矿化和损害。侵蚀初始发现在釉质,且如果未经检查,可在牙质下面发展。牙侵蚀可通过酸性食品和饮料、暴露在氯化游泳池水和胃酸回流导致或加重。牙釉质为带负电荷的表面,其天然趋向于吸引正电荷离子,例如氢和钙离子,同时排斥负电荷离子例如氟化物离子。取决于周围唾液的相对pH,牙釉质将失去或获得正电荷离子,例如钙离子。通常,唾液具有7.2-7.4的pH。当pH降低且氢离子浓度变得相对高时,氢离子将替换釉质内的钙离子,形成磷酸氢(磷酸),其损害釉质并产生多孔的、海绵状粗糙表面。如果唾液在延长期限保持酸性,则可能不发生再矿化,且牙齿将继续失去矿物质,导致牙齿变弱并最终失去结构。
需要改进的产品用于处理和减少侵蚀。
重金属离子,例如锌,对酸侵蚀有抗性。在电化学序列中,锌排在氢上面,使得酸性溶液中的金属锌反应释放氢气,因为锌进入溶液形成二价阳离子Zn2+。已经显示锌在牙斑和龋齿研究中具有抗菌性质。
可溶性锌盐,例如柠檬酸锌,已经用于洁齿剂组合物,但是具有几个缺点。在溶液中的锌离子给予了一种不愉快、涩的口感,因此,提供了有效水平的锌以及具有可接受的感官性质的制剂已经难以获得。此外,游离的锌离子可与氟化物离子反应产生氟化锌,其为不溶的并且因此减少了锌和氟化物两者的可用性。最终,锌离子将与阴离子表面活性剂例如月桂基硫酸钠反应,因此干扰发泡和清洁。
磷酸锌(Zn3(PO4)2)是不溶于水的,但是可溶于酸性或碱性溶液,例如,无机酸、乙酸、氨或碱金属氢氧化物的溶液。参见例如Merck Index,(2001)第13版1812页,专刊号10205。部分因为其在本领域被视为通用的惰性材料,通常用于牙科粘合剂,例如用于镶补、齿冠、牙桥和正牙的粘合,旨在使其在口腔内保持多年。磷酸锌牙科粘合剂通常通过将氧化锌和氧化镁粉末与主要包含磷酸、水和缓冲剂的液体混合来制备,如此通过与磷酸的反应在原位形成包含磷酸锌的粘合剂。
概述
目前已发现当磷酸锌放入制剂中时,例如,在酸性或碱性pH下,其可在使用时溶解充分以将有效浓度的锌离子提供至釉质,从而防御侵蚀,减少细菌拓殖和生物膜发展,并为牙齿提供增强的光泽。在一些实施方案中,制剂包含氨基酸,例如碱性氨基酸,例如精氨酸或赖氨酸,其可使制剂具有碱性pH。还发现制剂中的磷酸锌与第二磷酸盐源提高磷酸盐沉积。这完全出乎预料,考虑到磷酸锌差的溶解度,且现有技术认为在口腔条件下其基本是惰性的,正如它在牙可粘合剂中的广泛使用所证明。同时,包含磷酸锌的制剂未显示与常规锌基口腔护理产品(其使用更可溶的锌盐)相关的差的味道和口感、差的氟离子递送和差的起泡和清洁。
因此,本发明提供了包含磷酸锌的口腔护理组合物,例如洁齿剂。在一些实施方案中,磷酸锌作为预形成的盐添加到洁齿剂中。在一个实施方案中,组合物还包含氨基酸,例如,碱性氨基酸。组合物可任选地还包含氟化物源和或附加的磷酸盐源。组合物可在常规的洁齿剂或漱口剂基质内配制,所述基质例如包含研磨剂例如二氧化硅研磨剂、表面活性剂、发泡剂、维生素、聚合物、酶、保湿剂、增稠剂、抗菌剂、防腐剂、矫味剂、着色剂和/或它们的组合。例如,在一个实施方案中,本发明提供了在二氧化硅研磨剂洁齿剂基质内包含大约2%磷酸锌、大约5%精氨酸、大约5%碱性磷酸盐和大约1450ppm氟化物洁齿剂。
本发明还提供了使用本发明的组合物减少和抑制釉质酸侵蚀、清洁牙齿、减少细菌产生的生物膜和牙斑、减少牙龈炎、抑制牙齿腐烂和形成牙洞、和减少牙质过敏的方法,其包含用本发明的组合物刷牙。
本发明的其它应用领域由下文提供的详述变得显而易见。应理解详述和具体实例虽然表明了本发明的优选实施方案,但旨在仅用于说明,且不旨在限制本发明的范围。
详述
优选实施方案的以下描述在性质上仅为示例性的,且绝不旨在限制本发明、它的应用或用途。
如本文所用,术语“预形成的盐”,当用于指磷酸锌时,是指所述磷酸锌不是在洁齿剂或漱口剂内例如通过磷酸和锌盐的反应原位形成。
因此,本发明在第一实施方案中提供间歇使用的口腔护理组合物,例如每天使用,例如,以包含磷酸锌的洁齿剂或漱口剂的形式(组合物1),例如,
1.1. 组合物1的形式为在洁齿剂基质内包含磷酸锌的洁齿剂,例如,其中磷酸锌在洁齿剂基质内以有效量存在,例如,0.5-4重量%的量,例如约1-3重量%。
1.2. 组合物1.1,其中所述洁齿剂基质包含研磨剂,例如,有效量的二氧化硅研磨剂,例如,10-30%,例如约20%。
1.3. 组合物1的形式为包含磷酸锌的漱口剂,例如,量为0.005-0.05重量%,例如,约0.01-0.03重量%,在漱口剂基质内。
1.4. 任一种前述组合物,其进一步包含有效量的氟化物离子源,例如提供500-3000ppm的氟化物。
1.5. 任一种前述组合物,其还包含有效量的氟化物,其中氟化物为选自以下的盐:氟化亚锡、氟化钠、氟化钾、单氟磷酸钠、氟硅酸钠、氟硅酸铵、氟化胺(例如,N'-十八烷基三亚甲基二胺-N,N,N'-三(2-乙醇)-二氢氟化物)、氟化铵、氟化钛、六氟硫酸盐和它们的组合。
1.6. 任一种前述组合物,其包含氨基酸,所述氨基酸的量足以提高磷酸锌的溶解度,例如总组合物重量的约0.5重量%-约20重量%,总组合物重量的约0.5重量%-约10重量%,例如在洁齿剂的情况下,为总组合物重量的约1.5重量%、约3.75重量%、约5重量%或约7.5重量%,或例如在漱口剂的情况下,为约0.5-2重量%,例如约1%。
1.7. 任一种前述组合物,其包含碱性氨基酸,例如,精氨酸或赖氨酸或它们的组合,例如l-精氨酸,例如有效量,例如与磷酸锌组合的有效量,以减少侵蚀、牙质过敏和/或牙斑累积,例如,在洁齿剂情况下为总组合物重量的约1-10%的量,或在漱口剂情况下,例如约0.5-2重量%,例如约1%。
1.8. 任一种前述组合物,其包含碱性氨基酸,例如精氨酸,所述碱性氨基酸的量足以将制剂的pH提高至大于pH 8,例如pH 8.5-10。
1.9. 任一种前述组合物,其还包含附加的锌离子源,例如,选自柠檬酸锌、硫酸锌、硅酸锌、乳酸锌、氧化锌和它们的组合;例如在一个实施方案中,包含1%磷酸锌和1%柠檬酸锌的洁齿剂。
1.10.
任一种前述组合物,其包含有效量的一种或多种碱性磷酸盐,例如,钠、钾或钙盐,例如选自碱性二元磷酸盐和碱性焦磷酸盐,例如,选自以下的碱性磷酸盐:磷酸氢二钠、磷酸氢二钾、二水合磷酸二钙、焦磷酸钙、焦磷酸四钠、焦磷酸四钾、三磷酸钠和这些的任意两个或更多的混合物,例如量为组合物重量的1-20%,例如2-8%,例如大约5%。
1.11.
任一种前述组合物,其包含缓冲剂,例如磷酸钠缓冲剂(例如,磷酸二氢钠和磷酸二钠)。
1.12.
任一种前述组合物,其包含保湿剂,例如选自甘油、山梨糖醇、丙二醇、聚乙二醇、木糖醇和它们的混合物,例如包含至少20%,例如20-40%,例如25-35%的甘油。
1.13.
任一种前述组合物,其包含一种或多种表面活性剂,例如选自阴离子、阳离子、两性离子和非离子表面活性剂,和它们的混合物,例如,包含阴离子表面活性剂,例如选自以下的表面活性剂:月桂基硫酸钠、月桂基醚硫酸钠和它们的混合物,例如量为约0.3%-约4.5重量%,例如1-2%的月桂基硫酸钠(SLS);和/或两性离子表面活性剂,例如甜菜碱表面活性剂,例如椰油酰胺丙基甜菜碱,例如量为约0.1%-约4.5重量%,例如0.5-2%的椰油酰胺丙基甜菜碱。
1.14.
任一种前述组合物,其进一步包含粘度改变量的一种或多种多糖胶,例如黄原胶或角叉胶、二氧化硅增稠剂和它们的组合。
1.15.
任一种前述组合物,其包含胶条或片。
1.16.
任一种前述组合物,其进一步包含矫味剂、香料和/或着色剂。
1.17.
任一种前述组合物,其包含有效量的一种或多种抗菌剂,例如包含选自以下的抗菌剂:卤化二苯醚(例如三氯生)、药草提取物和精油(例如,迷迭香提取物、茶提取物、木兰提取物、百里酚、薄荷醇、桉叶油醇、香叶醇、香芹酚、柠檬醛、日柏酚、儿茶酚、水杨酸甲酯、表焙儿茶素没食子酸盐、表焙儿茶素、没食子酸、miswak提取物、沙棘提取物)、双胍杀菌剂(例如,氯己定、阿立西定或奥替尼啶)、季铵化合物(例如,十六烷基氯化吡啶鎓(CPC)、苯扎氯铵、十四烷基氯化吡啶鎓(TPC)、N-十四烷基-4-乙基氯化吡啶鎓(TDEPC))、酚类杀菌剂、海克替啶、奥替尼啶、血根碱、聚维酮碘、地莫匹醇、5-正辛酰-3'-三氟甲基苯基水杨酰胺(salifluor)、金属离子(例如锌盐例如柠檬酸锌、亚锡盐、铜盐、铁盐)、血根碱、蜂胶和产氧剂(例如,过氧化氢、缓冲的过氧硼酸钠或过氧碳酸钠)、邻苯二甲酸和它的盐、单过氧邻苯二甲酸(monoperthalic acid)和它的盐和酯、硬脂酸抗坏血酸酯、油酰肌氨酸、烷基硫酸酯、磺基琥珀酸二辛酯、水杨酰苯胺、溴化度米芬、地莫匹醇、辛哌醇和其它哌啶基衍生物、盐酸制剂、亚氯酸盐;和前述任一项的混合物;例如,包含三氯生或十六烷基氯化吡啶鎓。
1.18.
任一种前述组合物,其包含抗菌有效量的三氯生,例如0.1-0.5%,例如约0.3%。
1.19.
任一种前述组合物,其进一步包含增白剂,例如选自过氧化物、金属亚氯酸盐、过硼酸盐、过碳酸盐、过氧酸、次氯酸盐,和它们的组合。
1.20.
任一种前述组合物,其进一步包含过氧化氢或过氧化氢源,例如过氧化脲或过氧化物盐或复合物(例如,例如过氧磷酸盐、过氧碳酸盐、过硼酸盐、过氧硅酸盐或过硫酸盐;例如过氧磷酸钙、过硼酸钠、过氧碳酸钠、过氧磷酸钠和过硫酸钾);
1.21. 任一种前述组合物,其进一步包含干扰或阻止细菌附着的剂,例如solbrol或壳聚糖。
1.22.
任一种前述组合物,其进一步包含钙和磷酸盐的源,选自(i)钙-玻璃复合物,例如,磷硅酸钠钙,和(ii)钙-蛋白质复合物,例如,酪蛋白磷酸肽-无定形磷酸钙
1.23. 任一种前述组合物,其进一步包含可溶性钙盐,例如选自硫酸钙、氯化钙、硝酸钙、乙酸钙、乳酸钙和它们的组合。
1.24.
任一种前述组合物,其进一步包含生理或口腔可接受的钾盐,例如,硝酸钾或氯化钾,其量有效减少牙质敏感。
1.25.
任一种前述组合物,其进一步包含阴离子聚合物,例如,合成的阴离子聚合多羧酸盐,例如,其中阴离子聚合物选自马来酸酐或酸与另一种可聚合的乙烯属不饱和单体的1:4-4:1的共聚物;例如,其中所述阴离子聚合物为甲基乙烯醚/马来酸酐(PVM/MA)共聚物,其平均分子量(M.W.)为约30,000-约1,000,000,例如约300,000-约800,000,例如,其中阴离子聚合物为组合物重量的约1-5%,例如约2%。
1.26.
任一种前述组合物,其进一步包含口气清新剂、香料或矫味剂。
1.27.
任一种前述组合物,其中所述组合物的pH为酸性或碱性,例如,pH 4-pH 5.5或pH
8-pH 10。
1.28.
任一种前述组合物,其为洁齿剂,其中所述组合物在二氧化硅研磨剂洁齿剂基质中包含
1-3%,例如约2%的磷酸锌;
2-8%,例如大约5%的L-精氨酸(游离碱);
2-8%,例如,大约5%的碱性磷酸盐,例如选自磷酸氢二钠、磷酸氢二钾、二水合磷酸二钙、焦磷酸钙、焦磷酸四钠、焦磷酸四钾、三聚磷酸钠和这些之中任意两个或更多的混合物。
700-2000ppm,例如大约1450ppm的氟化物,例如0.3-0.4%,例如大约0.32%的氟化钠。
1.29.
任一种前述组合物,其为漱口剂,其中所述组合物包含
5-10%,例如约7.5%的甘油;
3-7%,例如约5.5%的山梨糖醇;
5-10%,例如约7%的丙二醇;
0-0.1% TSPP;
0.01-1%甜味剂,例如,约0.02%糖精;
0.01-1%,例如,约0.05%柠檬酸;
0-0.1%黄原胶;
0.005-0.05%,例如,约0.028%磷酸锌;
0-0.01%十六烷基氯化吡啶鎓;
0.01-0.1%,例如,约0.05%山梨酸钾;
0.05-1%,例如,约0.1-0.2%矫味剂;
0.1-2%,例如,约1%椰油酰胺丙基甜菜碱;
水(任选地与任何附加的成分一起)组成余量,例如,约70-85%,例如约80%的水。
1.30.
任一种前述组合物,其包含与以下实施例1或实施例4中试验制剂基本相同的成分。
1.31.
任一种前述组合物,其例如以刷拭有效施用在口腔,以(i)减少牙齿的过敏,(ii)减少牙斑积聚,(iii)减少或抑制去矿化和促进牙齿的再矿化,(iv)抑制口腔内微生物生物膜形成,(v)减少或抑制牙龈炎,(vi)促进口腔内溃疡或创口的愈合,(vii)减少产酸菌的水平,(viii)提高非生龋和/或非牙斑形成细菌的相对水平,(ix)减少或抑制龋齿的形成,(x)减少、修复或抑制釉质的预-龋损伤,例如,通过定量的光诱导荧光色谱(QLF)或电学龋齿测量(ECM)检测,(xi)处理、减轻或减少口干,(xii)清洁牙齿和口腔,(xiii)减少侵蚀,(xiv)使牙齿变白;和/或(xv)促进全身健康,包括心血管健康,例如通过减少经由口腔组织的全身感染的可能性。
1.32.
通过将任意前述组合物所述的成分组合获得或可获得的组合物。
本发明还提供了磷酸锌在口腔护理组合物(例如洁齿剂)的制造中的用途,和提高釉质中锌水平的方法。在一些实施方案中,磷酸锌作为预形成的盐添加到洁齿剂中。
本发明还提供了使用本发明的组合物的方法,来提高釉质中的锌水平和处理、减少或控制釉质侵蚀的发生,其包含将如上所述的组合物,例如组合物1及其后的任一种,施用到牙齿,例如通过刷拭。在各种实施方案中,本发明提供(i)减少牙齿的过敏,(ii)减少牙斑积聚,(iii)减少或抑制去矿化和促进牙齿的再矿化,(iv)抑制口腔内微生物生物膜形成,(v)减少或抑制牙龈炎,(vi)促进口腔内溃疡或创口的愈合,(vii)减少产酸菌的水平,(viii)提高非生龋和/或非牙斑形成细菌的相对水平,(ix)减少或抑制龋齿的形成,(x)减少、修复或抑制釉质的预-龋损伤,例如,通过定量的光诱导荧光色谱(QLF)或电学龋齿测量(ECM)检测,(xi)处理、减轻或减少口干,(xii)清洁牙齿和口腔,(xiii)减少侵蚀,(xiv)使牙齿变白;(xv)减少牙垢积累,和/或(xvi)促进全身健康,包括心血管健康,例如通过减少经由口腔组织的全身感染的可能性,其包括将如上所述的组合物1及其后的任一种施用到有需要的人的口腔内,例如,通过每天用组合物1及其后的任一种一次或多次刷牙。本发明还提供了组合物1及其后的组合物在任何这些方法中的用途。
活化剂:本发明的组合物可包含不同的试剂,其对于保护和提高釉质和牙齿结构的强度和完整性,和/或减少细菌和相关的牙齿腐烂和/或牙龈疾病有活性。本文使用的活性成分的有效浓度取决于特定的剂和使用的递送体系。应理解,牙膏在使用时例如通常与水稀释,而漱口液通常不会。因此,牙膏中活性成分的有效浓度通常比漱口液所需的高,为5-15倍。浓度也取决于所选的确切的盐或聚合物。例如,当提供盐形式的活化剂时,反离子将影响盐的重量,使得,如果反离子较重,按重量计需要更多的盐以在最终产物中提供相同浓度的活性离子。当存在精氨酸时,其存在水平可为,例如约0.1-约20重量%(表示为游离碱的重量),例如对于消费者牙膏来说,为约1-约10重量%,或对于专业的或处方处理产品来说,为约7-约20重量%。当存在氟化物时,其存在水平可为,例如约25-约25,000ppm,例如对于消费者牙膏来说,约750-约2,000ppm,或对于专业的或处方处理产品来说,约2,000-约25,000ppm。抗菌剂水平将类似地变化,用于牙膏的水平例如大于用于漱口液,为约5-约15倍。例如,三氯生牙膏可包含约0.3重量%的三氯生。
氟化物离子源:口腔护理组合物还可包括一种或多种氟化物离子源,例如,可溶的氟化物盐。可使用多种产生氟化物离子的材料作为本发明组合物中可溶氟化物的来源。适合的产生氟化物离子的材料的实例见美国专利号3,535,421,Briner等人;美国专利号4,885,155,Parran,Jr.等人和美国专利号3,678,154,Widder等人。代表性的氟化物离子源包括但不限于氟化亚锡、氟化钠、氟化钾、单氟磷酸钠、氟硅酸钠、氟硅酸铵、氟化胺、氟化铵和它们的组合。在某些实施方案中,氟化物离子源包括氟化亚锡、氟化钠、单氟磷酸钠以及它们的混合物。在某些实施方案中,本发明的口腔护理组合物还可包含氟化物离子或提供氟的成分的来源,其量足以供应约25ppm-约25,000ppm的氟化物离子,通常至少约500ppm,例如,约500-约2000ppm,例如,约1000-约1600ppm,例如约1450ppm。氟化物的适当水平取决于具体的应用。一般消费者使用的牙膏通常具有约1000-约1500ppm,儿童牙膏稍微少一些。专业应用的洁齿剂或涂层可具有多达约5,000,乃至约25,000ppm的氟化物。按组合物重量计,在一个实施方案中,氟化物离子源可在约0.01重量%-约10重量%的水平下加入到本发明的组合物中;和在另一个实施方案中,约0.03重量%-约5重量%;在另一个实施方案中,约0.1重量%-约1重量%。提供适当水平的氟化物离子的氟化物盐的重量基于所述盐中反离子的重量将明显改变。
氨基酸:在一些实施方案中,本发明的组合物包含氨基酸。在具体实施方案中,氨基酸可为碱性氨基酸。“碱性氨基酸”是指天然存在的碱性氨基酸,例如精氨酸、赖氨酸和组氨酸,以及在分子中具有羧基和氨基的任何碱性氨基酸,其为水溶性的并提供约为7或更大的pH的水溶液。因此,碱性氨基酸包括但不限于精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸、它们的盐或它们的组合。在一个具体实施方案中,碱性氨基酸选自精氨酸、瓜氨酸和鸟氨酸。在某些实施方案中,碱性氨基酸为精氨酸,例如l-精氨酸或它们的盐。在其它实施方案中,氨基酸为季铵化的,即,氨基为另外被取代以形成季铵部分,其可形成具有羧基的内盐,例如甜菜碱(N,N,N-三甲基甘氨酸)。
在各种实施方案中,氨基酸存在的量为总组合物重量的约0.5重量%-约20重量%,总组合物重量的约0.5重量%-约10重量%,例如在洁齿剂的情况下,为总组合物重量的约1.5重量%,约3.75重量%,约5重量%,或约7.5重量%,或例如在漱口剂的情况下,为约0.5-2重量%,例如约1%。
研磨剂:本发明的组合物,例如组合物1及其后的组合物,包括二氧化硅研磨剂,并且可包含其它的研磨剂,例如,磷酸钙研磨剂,例如磷酸三钙(Ca3(PO4)2)、羟磷灰石(Ca10(PO4)6(OH)2)或二水合磷酸二钙(CaHPO4•2H2O,本文有时也称作DiCal)或焦磷酸钙;碳酸钙研磨剂;或研磨剂例如偏磷酸钠、偏磷酸钾、硅酸铝、煅烧氧化铝、膨润土或其它的硅质材料,或它们的组合。
本文可使用的其它二氧化硅研磨磨光材料,以及其它的研磨剂,通常具有约0.1-约30微米,约5-约15微米的平均粒度。二氧化硅研磨剂可来自沉淀的二氧化硅或二氧化硅凝胶,例如美国专利号3,538,230,Pader等人和美国专利号3,862,307,Digiulio描述的二氧化硅干凝胶。具体的二氧化硅干凝胶由W. R.
Grace & Co.,Davison Chemical
Division以商品名Syloid®销售。沉淀的二氧化硅材料包括J.M.Huber
Corp.以商标Zeodent®销售的那些,包括携带Zeodent
115和119标记的二氧化硅。这些二氧化硅研磨剂在Wason的美国专利号4,340,583中描述。在某些实施方案中,本发明的口腔护理组合物实践中可使用的研磨材料包括二氧化硅凝胶和沉淀的无定形二氧化硅,其具有小于约100cc/100g二氧化硅和约45cc/100g-约70cc/100g二氧化硅的油吸收值。使用ASTA擦除方法D281测定油吸收值。在某些实施方案中,二氧化硅为胶态微粒,其具有约3微米-约12微米,和约5-约10微米的平均粒度。在本发明的实践中可特别使用的低油吸收二氧化硅研磨剂由W. R.
Grace & Co.,Baltimore,Md.21203的Davison Chemical
Division以商标Sylodent XWA®销售。Sylodent 650XWA®,其为由胶态二氧化硅颗粒组成的二氧化硅水凝胶,具有29重量%的水含量,平均为约7-约10微米直径,且小于约70cc/100g二氧化硅的油吸收为本发明实践可用的低油吸收二氧化硅研磨剂的实例。
发泡剂:当刷拭口腔时,本发明的口腔护理组合物也可包括提高产生的泡沫量的剂。提高泡沫量的剂的说明性实例包括但不限于聚氧乙烯和某些聚合物,包括但不限于藻酸盐聚合物。聚氧乙烯可提高泡沫的量和本发明的口腔护理载体组分产生的泡沫厚度。聚氧乙烯也通常称为聚乙二醇(“PEG”)或聚环氧乙烷。适合于本发明的聚氧乙烯具有约200,000-约7,000,000的分子量。在一个实施方案中,分子量为约600,000-约2,000,000,和在另一个实施方案中,为约800,000-约1,000,000。Polyox®为Union Carbide生产的高分子量聚氧乙烯的商标。聚氧乙烯存在的量可为本发明的口腔护理组合物的口腔护理载体组分的约1%-约90%,在一个实施方案中,为约5%-约50%,和在另一个实施方案中约10%-约20重量%。当存在时,口腔护理组合物中的发泡剂的量(即,单次剂量)为约0.01-约0.9重量%,约0.05-约0.5重量%,和在另一个实施方案中,约0.1-约0.2重量%。
表面活性剂:可用于本发明的组合物可包含阴离子表面活性剂,例如:
i. 高级脂肪酸甘油单酯单硫酸盐的水溶性盐,例如氢化椰油脂肪酸的单硫酸甘油单酯的钠盐,例如N-甲基N-椰油酰牛磺酸钠,椰油酸单甘油酯硫酸钠,
ii. 高级烷基硫酸盐,例如月桂基硫酸钠,
iii. 例如式CH3(CH2)mCH2(OCH2CH2)nOSO3X的高级烷基醚硫酸盐,其中m为6-16,例如,10,n为1-6,例如2、3或4,和X为Na或K,例如月桂醚-2硫酸钠(CH3(CH2)10CH2(OCH2CH2)2OSO3Na)。
iv. 高级烷基芳基磺酸盐例如十二烷基苯磺酸钠(月桂基苯磺酸钠)
v. 高级烷基磺基乙酸盐,例如月桂基磺基乙酸钠(十二烷基磺基乙酸钠),1,2二羟基丙烷磺酸盐的高级脂肪酸酯,磺基月桂酸盐(N-2-乙基月桂酸钾磺基乙酰胺)和月桂基肌氨酸钠。
“高级烷基”是指,例如C6-30烷基。在具体实施方案中,阴离子表面活性剂选自月桂基硫酸钠和月桂基醚硫酸钠。阴离子表面活性剂存在的有效量可为,例如,>制剂的0.01重量%,但是不是对口腔组织有刺激性的浓度,例如<10%,和为取决于具体的制剂和具体的表面活性剂的最优浓度。例如,漱口剂的使用浓度通常为用于牙膏的约十分之一。在一个实施方案中,存在于牙膏中的阴离子表面活性剂为约0.3%-约4.5重量%,例如约1.5%。本发明的组合物可任选地包含表面活性剂的混合物,例如,包含阴离子表面活性剂和其它表面活性剂(其可为阴离子的、阳离子的、两性离子的或非离子的)。通常,表面活性剂为在宽pH范围内相当稳定的那些。表面活性剂更完整地描述于例如美国专利号3,959,458,Agricola等人;美国专利号3,937,807,Haefele;和美国专利号4,051,234,Gieske等人。在某些实施方案中,本文可使用的阴离子表面活性剂包括烷基硫酸盐的水溶性盐(在烷基中具有约10-约18个碳原子)和具有约10-约18个碳原子的脂肪酸的磺酸单甘油酯的水溶性盐。月桂基硫酸钠、月桂酰肌氨酸钠和椰油甘油单酯磺酸钠为该类型的阴离子表面活性剂的实例。在一个具体实施方案中,本发明的组合物,例如组合物1及其后的组合物,包含月桂基硫酸钠。
可存在于本发明的组合物中的表面活性剂或相容的表面活性剂的混合物以总组合物的重量计可为约0.1%-约5.0%,在另一个实施方案中,约0.3%-约3.0%,和在另一个实施方案中,约0.5%-约2.0%。
牙垢控制剂:在本发明的各种实施方案中,组合物包含抗牙石(牙垢控制)剂。适合的抗牙石剂包括而不限于磷酸盐和多磷酸盐(例如焦磷酸盐)、聚氨基丙磺酸(AMPS)、六偏磷酸盐、柠檬酸锌三水合物、多肽、聚烯烃磺酸盐、聚烯烃磷酸盐、二磷酸盐。本发明因此可包含除了磷酸锌以外的磷酸盐。在具体实施方案中,这些盐为碱性磷酸盐,即,碱金属氢氧化物或碱土金属氢氧化物的盐,例如,钠、钾或钙盐。本文所用的“磷酸盐”包括口腔可接受的单和多磷酸盐,例如,P1-6磷酸盐,例如单体分子磷酸盐例如一元、二元或三元磷酸盐;二聚磷酸盐例如焦磷酸盐;和多聚磷酸盐,例如,六偏磷酸钠。在具体实例中,所选的磷酸盐选自碱性二元磷酸盐和碱性焦磷酸盐,例如,选自磷酸氢二钠、磷酸氢二钾、二水合磷酸二钙、焦磷酸钙、焦磷酸四钠、焦磷酸四钾、三聚磷酸钠和这些中的任意两个或更多个的混合物。在具体实施方案中,例如组合物包含以下的混合物:焦磷酸四钠(Na4P2O7)、焦磷酸钙(Ca2P2O7)和磷酸氢二钠(Na2HPO4),例如,量为大约3-4%的磷酸氢二钠和大约0.2-1%的每种所述焦磷酸盐。在另一个实施方案中,组合物包含焦磷酸四钠(TSPP)和三聚磷酸钠(STPP)(Na5P3O10)的混合物,例如比例为约1-2%的TSPP和约7%-约10%的STPP。提供有效量的这些磷酸盐来减少釉质侵蚀、帮助清洁牙齿和/或减少牙齿上的牙垢累积,例如量为2-20%,例如,大约5-15%,按组合物的重量计。
矫味剂:本发明的口腔护理组合物还可包括矫味剂。用于本发明的实践的矫味剂包括但不限于精油以及不同的矫味醛、酯、醇和类似的材料。精油的实例包括以下的油:留兰香、胡椒薄荷、冬青、黄樟、丁香、鼠尾草、桉树、马郁兰、肉桂、柠檬、酸橙、葡萄柚和橙。也可使用薄荷醇、香芹酮和茴香脑这些化学品。某些实施方案使用胡椒薄荷薄荷油和留兰香油。矫味剂可在约0.1-约5重量%的浓度下结合到口腔组合物,例如约0.5-约1.5重量%。
聚合物:本发明的口腔护理组合物还可包括其它的聚合物以调节制剂粘度或提高其它成分的溶解度。这些其它的聚合物包括聚乙二醇、多糖(例如,纤维素衍生物例如羧甲基纤维素,或多糖胶例如黄原胶或角叉胶)。酸性聚合物,例如聚丙烯酸酯凝胶,可按它们的游离酸形式或部分或完全中和的水溶性碱金属(例如,钾和钠)或铵盐的形式提供。
可存在二氧化硅增稠剂,其在水性介质中形成聚合结构或凝胶。应注意这些二氧化硅增稠剂为物理和功能上不同于也存在于组合物中的颗粒二氧化硅研磨剂,因为该二氧化硅增稠剂非常精细分散并提供极少或无研磨作用。其它的增稠剂为羧乙烯基聚合物、角叉胶、羟乙基纤维素,和纤维素醚的水溶性盐(例如羧甲基纤维素钠和羧甲基羟乙基纤维素钠)。还可结合天然胶例如刺梧桐胶、***胶和黄芪胶。胶态硅酸镁铝还可用作增稠组合物的组分来进一步提高组合物的质地。在某些实施方案中,以总组合物重量的约0.5%-约5.0%的量使用增稠剂。
本发明的组合物可包括阴离子聚合物,例如量为约0.05-约5%。已知这些剂通常用于用的洁齿剂,虽然不针对该特定应用,但可用于本发明的这些剂公开于美国专利号5,188,821和5,192,531;并包括合成的阴离子聚合多碳酸酯,例如马来酸酐或酸与另一种可聚合乙烯属不饱和单体的1:4-4:1共聚物,优选具有约30,000-约1,000,000分子量(M.W.)的甲基乙烯基醚/马来酸酐,最优选约300,000-约800,000。这些共聚物可得自例如Gantrez.,例如AN
139(M.W.500,000)、AN
119(M.W.250,000),和优选S-97药用级(M.W.700,000),可由ISP
Technologies, Inc.,Bound Brook,N.J.08805获得。当存在时,增强剂存在的量为约0.05-约3重量%。其它的有效聚合物包括以下那些,例如:马来酸酐与丙烯酸乙酯、甲基丙烯酸羟乙酯、N-乙烯基-2-吡咯烷酮或乙烯的1:1共聚物,后者可得自例如Monsanto EMA No. 1103,M.W.10,000和EMA级别61,和丙烯酸与甲基丙烯酸甲酯或甲基丙烯酸羟乙酯、丙烯酸甲酯或丙烯酸乙酯、异丁基乙烯基醚或N-乙烯基-2-吡咯烷酮的1:1共聚物。通常适合的是,含有活化碳-碳烯属双键和至少一个羧基的聚合烯属或乙烯属不饱和羧酸,即,含有在聚合中易于起作用的烯属双键的酸,因为它存在于单体分子中或者在相对于羧基的α-β位或作为末端亚甲基基团的一部分。这些酸的说明为丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、β-酰基氧基丙酸、山梨酸、α-氯代山梨酸、肉桂酸、β-苯乙基丙烯酸、粘康酸、衣康酸、柠康酸、中康酸、戊烯二酸、乌头酸、α-苯基丙烯酸、2-苄基丙烯酸、2-环己丙烯酸、当归酸、伞形酸、富马酸、马来酸和酐。其它的不同烯属单体可与这些羧酸单体(包括乙酸乙烯酯、氯乙烯、马来酸二甲酯等)共聚。为了水溶性,共聚物包含足够羧酸盐基团。另一类型的聚合剂包括含有经取代的丙烯酰胺的均聚物和/或不饱和磺酸的均聚物和它们的盐的组合物,特别地,其中聚合物基于选自丙烯酰胺基烷基磺酸的不饱和磺酸,例如具有约1,000-约2,000,000分子量的2-丙烯酰胺2甲基丙磺酸,描述于美国专利号4,842,847,1989年6月27日,Zahid。聚合剂的另一个有用的类别包括聚氨基酸,其含有阴离子表面活性氨基酸部分,例如天冬氨酸、谷氨酸和磷丝氨酸,例如美国专利号4,866,161,Sikes等人所公开。
水:口腔组合物可包含显著水平的水。市售口腔组合物制剂所用的水应去离子并不含有机杂质。组合物中水的量包括添加的游离水,加上与其它材料一起引入的量。
保湿剂:在口腔组合物的某些实施方案中,也期望加入保湿剂以阻止组合物暴露于空气时硬化。某些保湿剂还可给予期望的甜度或风味至洁齿剂组合物。适合的保湿剂包括食用多元醇,例如甘油、山梨糖醇、木糖醇、丙二醇以及其它的多元醇和这些保湿剂的混合物。在本发明的一个实施方案中,主要的保湿剂为甘油,其存在水平可大于25%,例如25-35%,约30%,连同5%或更少的其它保湿剂。
其它的任选成分:除了以上所述的组分,本发明的实施方案可包含许多任选的洁齿剂成分,其中的一些如下所述。任选的成分包括例如但不限于粘合剂,起泡剂,矫味剂,增甜剂,其它的抗牙斑试剂,研磨剂和着色剂。这些和其它任选组分进一步描述于美国专利号5,004,597,Majeti;美国专利号3,959,458,Agricola等人;和美国专利号3,937,807,Haefele,所有通过引用结合入本文。
如通篇所用,范围用作描述每个和所有在该范围内的值的简写。在该范围内的任何值可选作该范围的端点。另外,本文引用的所有参考文献在此通过引用以其全部并入。在本公开中的定义和引用的参考文献的定义冲突的情况下,以本公开为准。
除非另有说明,本文或说明书中其它地方表示的所有百分数和量应理解为是指按重量计的百分数。给定的量基于材料的有效重量。
实施例
实施例
1
制备包含2%磷酸锌,与5%精氨酸组合、1450ppm氟离子和磷酸盐的洁齿剂。该洁齿剂具有9.13的pH,与相对高的精氨酸含量一致。根据以下制剂(成分按组合物的重量计)还制备了包含2%柠檬酸锌、1%柠檬酸锌、1%柠檬酸锌+1%磷酸锌、无锌或无精氨酸的洁齿剂:
实施例
2
包含2%磷酸锌,连同精氨酸和氟化物的实施例1的洁齿剂,与对照的包含1%柠檬酸锌的洁齿剂相比,对酸试验显示了优异的功效。
体外方法用于测定实施例1的制剂原型的釉质防护活性。釉质基底(N=6/8个/细胞)通过将牛的门牙嵌入基于甲基丙烯酸酯的树脂中来制备,并用600和1200磨砂碳化物纸连续磨光。注意不要穿透牙质层,同时将釉质磨光为镜面光洁度。在测试之前,所有釉质基底用5%的柠檬酸预腐蚀30秒。每个基底的半侧用耐酸胶带覆盖以保护该表面作为对照表面。用于评价产品的模式,根据T-C-C-C-C-T
(T=产品处理,C=酸检验)的每日顺序,交替进行1-分钟产品处理与2-分钟酸曝露时间。用由NaOH调节至pH=3.8的1%的柠檬酸水溶液(无缓冲)进行酸试验。所有的釉质基底保存在37℃的无菌人造唾液溶液中,而不经历处理或试验。该方法总共进行五天,在结束时,用显微硬度分析来量化损失的釉质的量,损失的釉质由在受保护和暴露的表面上每个釉质基底上的腐蚀导致。计算硬度的百分数改变。未经处理,使用去离子水代替测试洁齿剂,硬度的百分数改变非常高,接近80%,取决于具体的基底,实验之间有轻微的变化。
在设计用以研究对早期釉质溶解的处理的保护效果的这种体外pH-循环模型中,包含2%磷酸锌的制剂有效对抗去矿化,在重复的酸试验后,仅有24.3%的硬度减少,与对于1%柠檬酸锌制剂可见的26.3%的硬度减少相比,其更低。单独的实验显示在制剂中柠檬酸锌的量由1%增加至2%不会提高对抗酸试验的功效。最大效果已在1%获得。因此,磷酸锌制剂在该试验中的有效性优于使用柠檬酸锌制剂可获得的最大效果,或至少与其一样好,考虑到在本领域中相信磷酸锌在口腔内是相对惰性的,该结果为令人意外的。
进行其它实验以评价有和没有精氨酸的含磷酸锌(ZnP)制剂,和包含1%磷酸锌和柠檬酸锌的制剂。包含氟化钠和硝酸钾的市售釉质保护牙膏(市售1)作为正对照包括在内。(NB:对每组实验使用由不同的人牙齿制备的配制品,因此在实验组之间可能有一些变化):
表2
未处理 | ZnP | ZnP + 柠檬酸锌 | ZnP + Arg | 市售1 | |
硬度减少% | 67.56 | 34.13 | 44.19 | 31.26 | 32.96 |
在该系列实验中,磷酸锌与精氨酸至少与正对照组一样好,和意外地,显著好于磷酸锌和柠檬酸锌的组合。
实施例
3
化学分析电子光谱法(ESCA,也称为x射线光电子能谱或XPS)为用于获得关于固体材料表面化学信息的表面分析技术。材料表征方法利用x射线束激发固体样品,导致光电子发射。这些光电子的能量分析提供了关于样品表面的元素和化学键信息两者。光电子的相对低的动能为ESCA带来约30Å的取样深度。ESCA用于分析在如前述实施例所述制备和处理的经磨光和腐蚀的釉质基底上使用测试洁齿剂-对照洁齿剂前后釉质中的矿物质含量,证实了锌递送至釉质表面,且所述锌甚至在酸试验之后保留在表面上,以及证实了氟化物的有效递送。
用不同的Zn/精氨酸/磷酸盐抗侵蚀膏处理的实施例1的釉质样品的ESCA数据显示在表3(以下)中,阐述了所检测的元素和它们相应的原子浓度。在每个磨光、腐蚀和处理步骤后分析所有样品。为简单起见,对于磨光和腐蚀表面仅呈现所有样品的平均组成。在所有情况下,每个样品分析三至四个单独的区域。对于经处理的样品,呈现单独区域的组成以及每个样品的平均组成。
检测在来自表面组织的经磨光和腐蚀的样品上的C和N。由釉质中的羟磷灰石(HAP)检测Ca和P,釉质表面有典型的P/Ca比率。腐蚀表面的平均P/Ca比率比磨光表面的P/Ca比率稍低,表明在腐蚀之后发生表面磷酸盐相对于Ca的减少。磨光面检测到低水平的Zn,其被腐蚀去除。对于磨光和腐蚀的两种表面,也检测到低水平的氟离子。也观察到低水平的Na。总的来说,磨光和腐蚀釉质表面的组成对于牛牙釉质来说是典型的。
在来自表面组织的所有经处理的样品表面上,检测C和N。所有样品的C水平比腐蚀表面更高,由于剩余组织的存在,很可能是来自糊膏。经处理的样品的N水平也相对于腐蚀表面更高。
也检测了样品表面上的Ca和P,其来自釉质中的HAP。经处理的样品的P/Ca比率比腐蚀表面更高,表明相对于Ca过量的磷酸盐。对于所有样品,Na浓度也显著大于腐蚀釉质的Na浓度。在经处理的样品上更高的磷酸盐和Na水平表示,来自糊膏的Na磷酸盐已经沉积在釉质表面。由于来自糊膏的残余二氧化硅,在经处理的釉质上也检测到少量的Si。
对于用包含柠檬酸锌或磷酸锌的糊膏处理过的釉质样品,在表面上观察到升高的锌水平。对于先前的研究,Zn/Ca比率提供了对比釉质表面上锌吸收的最佳方法。用磷酸锌糊膏处理的釉质的Zn/Ca比率大于柠檬酸锌糊膏的那些。这表明磷酸锌糊膏比柠檬酸锌产品在釉质上沉积了更多锌。在摩尔基准上,磷酸锌比同样重量的柠檬酸锌包含更多锌。这可说明在用磷酸锌糊膏处理的釉质上检出更多的锌,但是在任何情况下都应清楚的是,磷酸锌有效将锌递送至釉质表面。总的说来,在当前研究中,观察到样品的Zn/Ca比率约为先前报道的pH循环研究的釉质样品的两倍。
ESCA锌的峰位置可提供釉质表面上锌的化学态的信息。对于所有用含锌糊膏处理的样品,锌的峰位置相同。这表示所有样品上存在的锌呈相似的化学形式。此外,锌糊膏处理的样品的锌峰位置与在磨光釉质表面上背景锌的那些相同。釉质中固有存在的背景锌可能是锌HAP的形式。因此,该数据表明经处理的釉质上的锌还可为锌HAP的形式。
在所有经糊膏处理的釉质样品的表面上检测氟化物形式的F。样品之间相对的氟化物吸收也最好使用F/Ca比率测定。该数据表明用1%和2%柠檬酸锌糊膏处理的釉质具有相似的F/Ca比率,表示相似的F吸收。用无精氨酸的柠檬酸锌和Zn3(PO4)2糊膏处理的釉质显示了比其它样品稍低的F/Ca比率。然而,后两个处理的较低的氟化物吸收在这类研究的正常变化范围内。
ESCA结果表明,用含柠檬酸锌或磷酸锌的糊膏处理的釉质会发生锌沉积。含磷酸锌的糊膏比起柠檬酸锌糊膏,锌沉积更大。该数据也表示锌可按锌-HAP的形式存在于表面上。对于所有经糊膏处理的样品,也观察到升高水平的氟化物。
分析的详细结果表示在表3(以下)中。
如该数据显示,使用磷酸锌制剂递送到釉质的锌(平均0.58)实际高于使用任何柠檬酸锌制剂的锌递送。考虑到锌在控制侵蚀和减少细菌性生物膜沉积的有益作用,锌可能通过形成锌-羟磷灰石材料结合进入釉质是有利的。用磷酸锌制剂的氟化物递送也在可接受的范围内,与对照组相比显示显著的氟化物沉积,与包含柠檬酸锌没有精氨酸的制剂相似。
实施例
4
虽然磷酸锌不溶于水,但发现其溶于酸性溶液。包含例如2%乳酸(大约pH 2.4),或甚至低至0.05%柠檬酸(大约pH4),具有0.01-0.03%磷酸锌的制剂未显示出沉淀。发现磷酸锌的溶解度可在包含氨基酸和/或甜菜碱表面活性剂的制剂中提高。稳定的漱口剂制剂如下提供:
成分 | 重量 % |
山梨糖醇 | 5.5 |
甘油 | 7.5 |
丙二醇 | 7 |
糖精钠 | 0.02 |
柠檬酸(无水) | 0.05 |
磷酸锌 | 0.028 |
矫味剂/染料 | 0.12 |
山梨酸钾 | 0.05 |
椰油酰胺丙基甜菜碱 | 1 |
水 | 足量 |
总和 | 100 |
Claims (30)
1.包含磷酸锌的洁齿剂,其中所述磷酸锌作为预形成的盐添加到所述洁齿剂中。
2.权利要求1的洁齿剂,其中磷酸锌的量为0.05-5重量%。
3.权利要求1或2的洁齿剂,其中所述洁齿剂基质包含研磨剂。
4.上述权利要求中任一项的洁齿剂,其中磷酸锌的量为0.1-4重量%。
5.上述权利要求中任一项的洁齿剂,其包含一种或多种保湿剂和一种或多种表面活性剂。
6.上述权利要求中任一项的洁齿剂,其进一步包含有效量的氟化物离子源。
7.上述权利要求中任一项的洁齿剂,其进一步包含游离形式或口腔可接受盐的形式的碱性氨基酸。
8.上述权利要求中任一项的洁齿剂,其进一步包含有效量的一种或多种碱性磷酸盐。
9.上述权利要求中任一项的洁齿剂,其进一步包含有效量的一种或多种抗菌剂。
10.上述权利要求中任一项的洁齿剂,其进一步包含增白剂。
11.上述权利要求中任一项的洁齿剂,其进一步包含除磷酸锌之外的一种或多种锌离子源。
12.上述权利要求中任一项的洁齿剂,其中所述组合物的pH为酸性。
13.上述权利要求中任一项的洁齿剂,其中所述组合物的pH为碱性。
14.上述权利要求中任一项的洁齿剂,其在二氧化硅研磨剂洁齿剂基质内包含
1-3%的磷酸锌;
1-8%的精氨酸;
2-8%的碱性磷酸盐,其选自磷酸氢二钠、磷酸氢二钾、二水合磷酸二钙、焦磷酸四钠、焦磷酸四钾、焦磷酸钙、三聚磷酸钠和这些中任意两个或更多个的混合物;
700-2000ppm的氟化物。
15.包含磷酸锌的漱口剂,其中所述磷酸锌作为预形成的盐添加到所述漱口剂中。
16.权利要求15的漱口剂,其中磷酸锌的量为0.5-4重量%。
17.权利要求15或16的漱口剂,其中磷酸锌的量为0.005-4重量%。
18.前述权利要求的权利要求15-17中任一项的漱口剂,其进一步包含有效量的氟化物离子源。
19.权利要求15-18中任一项的漱口剂,其进一步包含游离形式或口腔可接受盐的形式的碱性氨基酸。
20.权利要求15-19中任一项的漱口剂,且进一步包含有效量的一种或多种碱性磷酸盐。
21.权利要求15-20中任一项的漱口剂,其进一步包含有效量的一种或多种抗菌剂。
22.权利要求15-21中任一项的漱口剂,其进一步包含增白剂。
23.权利要求15-22中任一项的漱口剂,其进一步包含除磷酸锌之外的一种或多种锌离子源。
24.权利要求15-23中任一项的漱口剂,其中所述组合物的pH为酸性。
25.权利要求15-24中任一项的漱口剂,其中所述组合物的pH为碱性。
26.权利要求15-25中任一项的漱口剂,其在二氧化硅研磨剂洁齿剂基质内包含
0.1-2%的磷酸锌;
0.1-3%的精氨酸;
2-8%的碱性磷酸盐,其选自磷酸氢二钠、磷酸氢二钾、二水合磷酸二钙、焦磷酸四钠、焦磷酸四钾、焦磷酸钙、三聚磷酸钠和这些中任意两个或更多个的混合物;
700-2000ppm的氟化物。
27.权利要求15-25中任一项的漱口剂,其中所述组合物包含
5-10%的甘油;
3-7%的山梨糖醇;
5-10%的丙二醇;
0-0.1%的TSPP;
0.01-1%的甜味剂;
0.01-1%的柠檬酸;
0-0.1%的黄原胶;
0.005-0.05%的磷酸锌;
0-0.01%的十六烷基氯化吡啶鎓;
0.01-0.1%的山梨酸钾;
0.05-1%的矫味剂;和
0.1-2%的椰油酰胺丙基甜菜碱。
28.磷酸锌在洁齿剂或漱口剂制造中的用途,其中所述磷酸锌以预形成的盐添加到所述洁齿剂或漱口剂中。
29.处理或减少牙釉质侵蚀的方法,其包含将权利要求1-27中任一项的组合物施用于有需要的受试者的口腔。
30.权利要求1-27中任一项的组合物,其用于处理或减少牙釉质侵蚀。
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