JPH0154323B2 - - Google Patents
Info
- Publication number
- JPH0154323B2 JPH0154323B2 JP56115418A JP11541881A JPH0154323B2 JP H0154323 B2 JPH0154323 B2 JP H0154323B2 JP 56115418 A JP56115418 A JP 56115418A JP 11541881 A JP11541881 A JP 11541881A JP H0154323 B2 JPH0154323 B2 JP H0154323B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- polymer
- plaque
- weight
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 91
- 239000000203 mixture Substances 0.000 claims description 53
- -1 poly(arylene ether sulfone Chemical class 0.000 claims description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 22
- 229910005965 SO 2 Inorganic materials 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 12
- 239000003349 gelling agent Substances 0.000 claims description 12
- 239000003906 humectant Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 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 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 230000000675 anti-caries Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 41
- 229920002492 poly(sulfone) Polymers 0.000 description 26
- 238000006277 sulfonation reaction Methods 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000009472 formulation Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 19
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 19
- 230000004888 barrier function Effects 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000000499 gel Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000012754 barrier agent Substances 0.000 description 14
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 14
- 210000003298 dental enamel Anatomy 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000003751 zinc Chemical class 0.000 description 11
- 238000000502 dialysis Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 7
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 6
- 150000003460 sulfonic acids Chemical class 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 235000003599 food sweetener Nutrition 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 239000003765 sweetening agent Substances 0.000 description 5
- 239000000606 toothpaste Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920003295 Radel® Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 238000000338 in vitro Methods 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002324 mouth wash Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920001992 poloxamer 407 Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 150000008054 sulfonate salts Chemical class 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 208000002064 Dental Plaque Diseases 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229940034610 toothpaste Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002415 Pluronic P-123 Polymers 0.000 description 2
- 229920002065 Pluronic® P 105 Polymers 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000005838 aromatic sulfonation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000015218 chewing gum Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000551 dentifrice Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229940051866 mouthwash Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SIHSSUWJKIEVGQ-UHFFFAOYSA-N 14-methyl-1-(14-methylpentadecoxy)pentadecane Chemical compound CC(C)CCCCCCCCCCCCCOCCCCCCCCCCCCCC(C)C SIHSSUWJKIEVGQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CKPHTUFEGVEMOQ-UHFFFAOYSA-N C(C)[S](CC)CC Chemical compound C(C)[S](CC)CC CKPHTUFEGVEMOQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 208000019428 Ligament disease Diseases 0.000 description 1
- 229920003091 Methocel⢠Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002057 Pluronic® P 103 Polymers 0.000 description 1
- 229920002059 Pluronic® P 104 Polymers 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004695 VICTREX⢠PEEK Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- CHNUOJQWGUIOLD-NFZZJPOKSA-N epalrestat Chemical compound C=1C=CC=CC=1\C=C(/C)\C=C1/SC(=S)N(CC(O)=O)C1=O CHNUOJQWGUIOLD-NFZZJPOKSA-N 0.000 description 1
- 229950010170 epalrestat Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 208000007565 gingivitis Diseases 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 210000002379 periodontal ligament Anatomy 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
- 230000007505 plaque formation Effects 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229960003191 potassium methylparaben Drugs 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 229940048098 sodium sarcosinate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 108010050327 trypticase-soy broth Proteins 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Description
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The present invention relates to oral hygiene compositions and methods of using such compositions to prevent bacterial adhesion to teeth. More specifically, the present invention includes:
This invention relates to certain sulfonated polymeric materials that have been found to be useful in inhibiting the adhesion of oral microorganisms to teeth. Prevention of plaque buildup on teeth is a highly desirable outcome. Plaque occurs when caries-causing bacteria aggregate in colonies on the tooth surface and form aggressive deposits thereon. The presence of plaque on teeth is believed to be a precursor to the development of gingivitis, caries and periodontal ligament disease. Many attempts have been made to control the effects of caries-causing bacteria and plaque, which have produced treatments such as fluoride, the use of dental floss, and brushing, which typically either counteracts the secondary effects of plaque on the teeth and gums, or the teeth and surrounding tissues are directed toward the removal of plaque that has already formed and adhered. However, such treatments are not completely effective and must undergo periodic auxiliary treatment by a dental professional. To date, there are no commercially viable home treatments for preventing plaque formation or attachment to teeth. Certain poly(arylene ether sulfones)
A number of polymeric hydrophilic sulfonic acid and sulfonate derivatives have been synthesized and found to prevent plaque deposition on human teeth. These hydrophilic polymer sulfonates have excellent film-forming properties and are therefore applied to the teeth from various toothpaste formulations, mouthwashes, or other oral hygiene procedures. The sulfonate polymers of the present invention are anionic in nature and substantially compatible with water or water/organic solvent excipients, primarily due to the relatively high degree of sulfonation achieved during the preparation of these derivatives. Soluble. Although the mechanism of action of hydrophilic polymer films in retarding plaque deposition cannot be known with absolute certainty, anionically charged polymer films deposited on teeth can reduce plaque deposition. It is presumed that this affects the mutual repulsion between the negatively charged microorganisms in the oral fluid that causes the outbreak and the negatively charged polymer film. For example, when powdered human tooth enamel is dispersed in an aqueous medium containing a polymeric sulfonate, a substantially negative surface charge is imparted to the enamel particles, as determined by zeta potential measurements. be done. The sulfonated poly(arylene ether sulfone) polymers of the present invention are particularly effective as components of toothpastes and other oral hygiene preparations in reducing plaque buildup on teeth. According to one preferred embodiment of the invention, the zinc salt of the sulfonated poly(arylene ether sulfone) polymer exhibits a As determined by Accordingly, the present invention provides a dental treatment comprising a zinc salt of a sulfonated poly(arylene ether sulfone) polymer and a pharmaceutically acceptable oral hygiene release system compatible therewith, as more fully defined hereinafter. A highly substantive oral hygiene formulation for reducing plaque buildup on teeth is also provided. In still other preferred embodiments, the present invention provides water, at least about 5% by weight of a humectant selected from the group consisting of glycerol and sorbitol, and at least about 16% by weight of a block copolymer of polyoxypropylene and polyoxyethylene. a gelling agent selected from the group consisting of: wherein the polyoxypropylene component has a molecular weight in the range of about 3000 to about 4000, and the polyoxyethylene comprises about 25 to about 80 mole percent of the copolymer; and from about 0.5 to about 10% by weight of the sulfonated poly(arylene ether sulfone) described herein.
Provided is an oral hygiene composition that suppresses the adhesion of dental plaque to teeth, which comprises a dental plaque barrier agent that is a polymer.
Thus, of all the dentifrice vehicle systems tested, only these gels have a combination of high plaque barrier activity, high substance content and excellent aesthetic quality. Desirable aesthetic properties of the gel of the present invention can be defined as a translucent gel with clarity, absence of haze, and adhesive properties that do not allow the gel to be absorbed or dissolved into toothbrush bristles. In contrast, poor aesthetic properties include gel separation, active ingredient precipitation, and gel cloudiness. Plaque barrier agents are present in these formulations from about 0.5 to about
Present in effective concentrations in the range of 10% by weight. A more preferred range is about 2 to about 8% by weight, with about 5% by weight
is currently the most preferred concentration. Certain commercially available polyoxypropylene/polyoxyethylene block copolymer gelling agents within the above definition include Pluronic F-127, Pluronic F-108, Pluronic P-103, Pluronic P-104. , Pluronic P-105, and Pluronic P-123. Effective gelling agent concentrations are generally about 16-22% by weight. Examples of the benefits of the preferred non-abrasive gel formulations of the present invention include high levels of plaque barrier activity and substance in a clear, uniform, aesthetically pleasing formulation that is acceptable for use as an oral hygiene product. It is gender. Additionally, anti-cavity compounds such as sodium fluoride can be incorporated into these compositions so that they can be used as a primary dentifrice in oral health prevention programs. The hydrophilic, polymeric, anionic sulfonate salts useful for plaque control in accordance with the present invention are obtained by aromatically sulfonating a poly(arylene ether sulfone) polymer and then converting the sulfonic acid derivative of the polymer into They are prepared by conversion to alkali metal salts of Group A, metal salts of certain polyvalent metals of Groups A, B, and A, and ammonium or amine salts. The repeating units of the sulfonated poly(arylene ether sulfone) polymers of the present invention include structure (A), (-(Ar 1 -SO 2 -Ar 2 -O)-) (A) and structure (B), (-( Ar 1 âSO 2 âAr 2 âOâAr 3 âO)â) (B) Here, Ar 1 and Ar 2 are each
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(a) 次ã®å埩åäœã®æ§é ãæãããååéçŽ
35000ã®ããŠããªã³ã»ã«ãŒãã€ã瀟ïŒUnion
Carbide Corp.ïŒããå
¥æã§ãããUdel
PolysulfoneïŒP1700åãŸãã¯å»ççšMG11ïŒ
(b) ICIã¢ã¡ãªã«ç€Ÿããå
¥æã§ãããVictrex
PolyethersulfoneãççŽ100PïŒ200PïŒ
300PïŒ
(c) 次ã®å埩æ§é ãæãããšèããããããŠããª
ã³ã»ã«ãŒãã€ã瀟ããå
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ã¹ã«ãã³åããŠæ¬çºæã®ã¹ã«ãã³åããªããŒã
çæã§ããä»ã®ããªïŒã¢ãªãŒã¬ã³ãšãŒãã«ã¹ã«ã
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ïŒïŒããã³ïŒïŒãšããŠè¡šãããããããŠãã
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ïŒâAr5âSO2âAr6ââïŒo ïŒïŒ
ïŒâAr5âSO2âAr6ââAr7ââïŒo ïŒïŒ
(1) âAr5âSO2âAr6âOMâ²â
ïŒâAr5âSO2âAr6ââïŒoïŒMâ²X
(2) âAr5âSO2âAr6âïŒMâ²OâAr7â
OMâ²â
ïŒâAr5âSO2âAr6ââAr7ââïŒoïŒ2Mâ²X
ããã§ãã¯ããã²ã³ã§ããïŒMâ²ã¯ïŒäŸ¡ã®é
å±ãããšãã°ããããªãŠã ãŸãã¯ã«ãªãŠã ã§ã
ãïŒAr5ããã³Ar6ã¯ãåã
[Formula], where Y is lower alkylene of 1 to 5 carbon atoms, lower alkylidine of 2 to 5 carbon atoms, selected from O, S and SO 2 ; subscript c is an integer selected from 0, 1 and 2; the sum of C in each of repeating units (A) and (B) in said repeating unit the average quotient divided by the number of aromatic groups is at least about 0.2; and M is lithium, sodium, potassium, calcium, magnesium, zinc, aluminum, hydrogen, ammonium,
and a substituted ammonium ion derived from a pharmaceutically acceptable organic amine. In general, metal and ammonium salts are preferred over the free sulfonic acid form of the polymer due to their higher water solubility and lower acidity, which makes them advantageous as plaque control barriers in oral hygiene formulations. Zinc salts are particularly preferred. The polymers utilized for conversion into sulfonate salts are either commercially available or synthesized by known methods described in the literature. Representative examples of commercial poly(arylene ether sulfone) polymers that can be sulfonated to hydrophilic, anionic sulfonates of the present invention are: (a) having a repeating unit structure of:
35,000, Union Carbide
Udel, available from Carbide Corp.
Polysulfone, P1700 type or medical MG11: (b) Victrex, available from ICI America, Inc.
Polyethersulfone, grade 100P, 200P,
300P: (c) Radel, available from Union Carbide, believed to have the following repeating structure:
Polysufone: Generalized structures for other poly(arylene ether sulfone polymers) that can be sulfonated to produce the sulfonated polymers of the present invention are represented as formulas () and (), and their synthesis methods are as follows: Shown by the reaction formula: (-Ar 5 -SO 2 -Ar 6 -O-) o () (-Ar 5 -SO 2 -Ar 6 -O-Ar 7 -O-) o () (1) X- Ar 5 âSO 2 âAr 6 âOMâ²â (âAr 5 âSO 2 âAr 6 âOâ) o +Mâ²X (2) XâAr 5 âSO 2 âAr 6 âX+Mâ²OâAr 7 â
OMâ²â (âAr 5 âSO 2 âAr 6 âOâAr 7 âOâ) o +2Mâ²X where X is a halogen; Mâ² is a monovalent metal, such as sodium or potassium. ;Ar 5 and Ar 6 are each
ãåŒããformulaã
ãåŒãããã³[expression] and
ãåŒãããéžã°ãããã ãAr6ã¯
âAr8âSO2âAr8âããã³âAr8âSO2âAr8â
SO2âAr8âããéžã°ããïŒãŸãã¯ïŒä»¥äžã®éé
åäœãããªãããšãã§ããåèšééåäœã«ãããŠ
åAr8ã¯[Formula], where Ar 6 is âAr 8 âSO 2 âAr 8 â and âAr 8 âSO 2 âAr 8 â
It can consist of one or more interval units selected from SO 2 âAr 8 â, in which each Ar 8 is
ãåŒããformulaã
ãåŒãããã³[expression] and
ãåŒãã
ãå¥ã
ã«éžã°ããA7ã¯Ar8ããã³
chosen separately from [formula], A 7 is Ar 8 and
ãåŒãããéžã°ããããã§ïŒ¹
ã¯ïŒãïŒççŽ ååã®äœçŽã¢ã«ãã¬ã³ãïŒãïŒççŽ
ååã®äœçŽã¢ã«ããªãžã³[Formula], where Y is lower alkylene of 1 to 5 carbon atoms, lower alkylidine of 2 to 5 carbon atoms
ãåŒããformulaã
ãåŒãïŒïŒ³ããã³SO2ãã
éžã°ããã
æ§é ïŒïŒã®ããªããŒã¯ãT.E.AttwoodïŒ
etalïŒPolymerïŒVol.18ïŒ354â374ïŒ1977ïŒã«èš
èŒãããäžè¬æ³ïŒäžã®åå¿åŒ(1)äžã«èŠçŽããïŒã«
ããåæã§ãããæ§é ïŒïŒã®ããªããŒã¯ãããš
ãã°ãR.N.JohnsonïŒet alïŒJ.Polymer
ScienceïŒPart âïŒïŒVolume ïŒïŒ2375â
2398ïŒ1967ïŒã«æ瀺ãããããã«ããã¹ïŒããã¢
ãªãŒã«ïŒã¹ã«ãã³ãšè³éŠæãžãªãŒã«ã®ïŒäŸ¡ã®éå±
å¡©ãšã®åå¿ã«ãã補é ããããæ¬çºæã®çµæç©ã
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å床ãäœããã€æ°Žã®è±å¡©çšèãšããŠé©åœãªæ°Žæº¶æ§
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ãªæç®ããã³ç¹èš±ã«èšèŒãããŠããïŒA.Noshay
ããã³L.M.RobesonïŒJ.Applied Polymer
ScienceïŒ20ïŒ1885â1903ïŒ1976ïŒïŒC.L.BrousseïŒ
et al.ïŒDesalinationïŒ18ïŒ137â153ïŒ1976ïŒïŒã
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50000ã®ç¯å²ã§ããã[Formula] selected from O, S and SO 2 . The polymer of structure () is TEAttwood,
etal, Polymer, Vol. 18, 354-374 (1977) (summarized in reaction formula (1) above). Polymers of structure () are, for example, RNJohnson, et al, J. Polymer
Science, Part A-1, Volume 5, 2375-
2398 (1967), by the reaction of a bis(haloaryl)sulfone with a monovalent metal salt of an aromatic diol. Poly(arylene ether sulfone) polymers suitable for use in the compositions and methods of the present invention are determined according to the above definitions of aromatic polymer structure () and (), the nature of the aromatic groups, the orientation of the bonds on the aromatic rings, and It can be synthesized by changing the spacing of sulfone (SO 2 ), ether (O), and other bonding groups. The sulfonation of poly(arylene ether sulfone) polymers, such as Udel Polysulfone, to water-soluble sulfonated polymers with a low degree of sulfonation and suitable as membranes for water desalination is described in the following literature and patents: Present: A.Noshay
and LM Robeson, J. Applied Polymer
Science, 20 , 1885-1903 (1976); CLBrousse,
et al., Desalination, 18 , 137-153 (1976); and U.S. Patent No. 3709841 (issued January 9, 1973), U.S. Pat. (Published April 1, 1975). These sulfonated polysulfones differ from the derivatives of the invention in that they are substantially water-insoluble due to their relatively low degree of sulfonation and therefore cannot be used in oral hygiene applications. As discussed below, the poly(arylene ether sulfone) sulfonates of the present invention, as a result of the high degree of sulfonation, can be dissolved in water and a mixed solvent of water and an organic solvent miscible therewith (generally at least 1% w/w). It is substantially soluble and hydrophilic.
As discussed in more detail below, the degree of sulfonation (D.
S.) also has a significant effect on the degree of plaque adhesion. As used herein, DS is the average number of sulfonic acid groups or groups per repeating unit of the polymer structure. The preferred sulfonating agent for producing the sulfonated polymer barrier of the present invention is anhydrous sulfur trioxide, triethyl sulfur trioxide phosphate (TEP).
complex, and chlorosulfonic acid. Due to the high reactivity of trioxide ions and their potential dehydration properties, sulfonation reactions using sulfur trioxide are difficult due to cross-linking between polymer chains through sulfone formation.
Sometimes it is possible to form dispersions of highly insoluble polymers. In these cases, it is preferred to moderate the sulfonation reaction using a complex of sulfur trioxide with triethyl phosphate (TEP), which reduces or essentially eliminates the formation of crosslinking by-products [AFTurbak. Ind.Eng.Chem.ïŒProd.RïŒ
D, 1 , 275 (1962); U.S. Pat. No. 3,072,619 (1963)
January 8, 1965); AFTurbak and A. Noshay, U.S. Pat. No. 3,206,492 (September 14, 1965); NH
Canter, U.S. Pat. No. 3,642,728 (February 15, 1972)
); A. Noshay and LM Robeson, J. Applied
See Polymer Science, 20 , 1885 (1976)]. Although the sulfonation activity increases with increasing the molar ratio of sulfur trioxide in the complex with TEP, 2:1, 3:1 and 4 A molar ratio of :1 is preferred. If it is difficult to carry out the sulfonation under mild conditions using the complex, sulfonation using sulfur trioxide (alone) or chlorosulfonic acid is more effective. Sulfonation can be carried out in solvents such as methylene oxide, 1,2-dichloroethane, and chloroform. This is because they are generally good solvents for the starting aromatic polymer, but poor solvents for the sulfonated polymer, allowing the sulfonated polymer to precipitate directly from the reaction medium and be filtered. If the product is soluble in the reaction medium and does not precipitate, the sulfonated polymer can be isolated by removing the solvent and converted to a well-discrete solid by trituration or slurrying with a suitable non-solvent. Can be done. Three types of reactions between the sulfonating agent and the polymer were experimented: (1) addition of the sulfonating agent to the polymer, (2) addition of the polymer to the sulfonating agent, and (3) addition of the sulfonating agent to the reaction medium. and simultaneous addition of polymers.
Methods (1) and (3) are preferred. This is because the addition of polymer to the sulfonating agent (method 2) results in a non-uniform product, likely due to the presence of a large excess of sulfonating agent during the initial stages of the reaction. The most preferred sulfonation method is that of method (3), which involves simultaneous addition of the reactants. These conditions give a more homogeneous sulfonated product, and the product precipitates directly from the reaction as a finely divided solid, thereby eliminating encapsulation of the solvent by the sulfonated polymer, residual acid, and complexing agents (e.g., phosphoric acid). triethyl) and unreacted polymer. Temperature control of the sulfonation reaction using sulfur trioxide and its complex with TEP is not very critical. An acceptable result is â20
It ranges from â to +40â. Sulfonation is generally at ambient room temperature. This is because the exotherm of sulfonation is very mild and rarely generates temperatures above 35°C. Typical impurities in sulfonated polymers are small amounts of unreacted polymer entrapped in the solid polymer, excess amounts of sulfonating agent (as sulfuric acid), and residual trimethyl phosphate. Substantial purification involves converting the polymeric sulfonic acid derivative to its non-solvent,
For example, by slurrying in halocarbon. Free sulfuric acid is difficult to remove because it is highly complexed with the polymer product. Diethyl ether is an exceptionally good complexing agent for sulfuric acid and effectively removes this contaminant when freshly isolated solids are slurried in ether. Other additives effective in removing sulfuric acid are hydrocarbon blends with diethyl ether and other oxygenated solvents such as ethyl acetate and acetone. Sulfuric acid, if not removed, will cause contamination of the metal salts produced by neutralization or ion-exchange reactions with the polymeric sulfonic acid intermediate, and when producing the polymeric sulfonic acid salts, significant inorganic substances such as sodium sulfate may be present. produces salt. Although efficient purification of polymeric sulfonic acid derivatives is not always possible, it has been found that additional purification converts the sulfonic acid groups into various salts of their monovalent and divalent metal atoms. For example, neutralizing an ethanolic solution of the DS 1.8 sulfonic acid of Udel polysulfone with an alcoholic solution of sodium hydroxide results in the precipitation of sodium sulfonate in higher purity. Much of the encapsulated triethyl phosphate and processing solvent is removed to the liquor during precipitation of the product. A preferred method of purification of sulfonated polymers (free acids and salts), especially the highly water-soluble forms, is in a membrane tube or hollow fiber dialysis unit with a molecular weight cut off well below that of the polymer. , by dialysis of their aqueous solutions. Dialysis removes all low molecular weight impurities, triethyl phosphate and inorganic salts. High purity polymers are isolated as solids by lyophilization or spray drying of dialyzed polymer solutions. Examples of acceptable metal salts of the polymeric sulfonic acid derivatives of the polymeric poly(arylene ether sulfone) polymers according to the invention are potassium, lithium, sodium, calcium, magnesium, zinc, and aluminum salts. Zinc salts are particularly preferred since they exhibit a higher presence in human tooth enamel (after repeated washing with water) than alkali metal salts. Other acceptable salt forms of the polymer are ammonium salts prepared from ammonia or pharmaceutically acceptable organic amines. Alkali metal salts of sulfonated polymers are conveniently prepared by neutralizing an aqueous or alcoholic solution of the sulfonic acid derivative of the polymer to the potentiometric endpoint with a solution of an alkali metal hydroxide. Salt perfusion, solvent stripping,
or by lyophilization, depending on the type of solvent used and whether or not the salt precipitates directly from the solvent medium. Alternatively, sulfonate salts can be prepared by adding at least a stoichiometric amount of an alkali metal hydroxide, carbonate, acetate, chloride, nitrate, or sulfate to a sulfonic acid derivative. Salts can be directly precipitated or isolated by solvent stripping. Purification of sulfonate salts by dialysis is the preferred method for more highly water-soluble salts. Polyvalent metal salts of sulfonated polymers, such as calcium, magnesium, bad lead, and aluminum salts, can be prepared by methods similar to those described above. In another method, salts of polyvalent metals can be prepared by ion exchange reactions between polyvalent metals and polymeric free sulfonic acids or alkali metal sulfonate derivatives. The aforementioned neutralization reactions and other salt formation reactions are essentially ion exchange reactions, as typically represented by the following reaction equation, where P represents a polymer chain: -SO3H +M + n /n âSO 3 â (M +n /n) + H + âSO 3 Na + Zn +2 /2 â SO 3 â (Zn +2 /2) + Na + The ammonium salt of the sulfonic acid polymer is ammonia or primary, They can be prepared by direct addition of secondary or tertiary amines. Although the sulfonic acids of the polymers of the present invention are highly effective in reducing plaque deposition during in vitro testing, these sulfonic acid polymers are too highly acidic and must be properly buffered. are not tolerated in the oral environment. Various salts of polymeric sulfonic acids are preferred due to their high solubility in aqueous media and low acidity. These salts, when tested in vitro, exhibit reductions in plaque deposition approximately equivalent to that exhibited by the corresponding free acids. The in vitro testing procedure used in the present invention begins by growing dental plaque in small bottles containing sterile trypticase medium supplemented with scrolls. Typically, 10 bottles are individually filled with freshly collected human plaque samples from 10 subjects.
Inoculate with 0.5ml. In the control series, a pre-sterilized glass slide or an extracted human tooth is placed in each bottle. In a test series, a tooth or glass slide is pretreated with a 1% solution of the test compound (dissolved in water or other excipients), a thin film of the compound is deposited on the surface, allowed to dry, and Place the slide or tooth into the growth medium. The bottles are incubated for 2 days at 37°C under anaerobic conditions. Remove the tooth or glass slide, air dry, and stain with 0.15% FD&C #3 red dye to reveal accumulated plaque deposits. Teeth or glass slides are scored for plaque density on a scale of 0-5 versus control.
Plaque barrier activity is reported as the average percent plaque reduction compared to appropriate controls for 10 subjects. The test method used to assess substantivity is relatively simple to perform, is compatible with multicomponent gel formulations according to the invention, and includes modifications to the plaque barrier activity test described above; And as summarized below: Test A 1 A clean glass slide is coated on both sides with the test formulation. Apply a thin film using a toothbrush. 2 Place the coated glass slide into a bottle of previously inoculated plaque medium. 3. Cultivate anaerobically at 37°C for 48-72 hours. 4 Remove plaque deposits on the glass slide using FD&
Dye by immersing in a 0.15% solution of C Red #3 for 1 minute. 5. Plaque deposits on glass slides by comparing the amount of deposits on untreated control slides with the amount of deposits on treated slides.
evaluate. The adhesion is reported as "inhibition rate of plaque adhesion to glass slides." Test B Follow the method of Test A, but with the following changes. After coating the slides as with the test formulation, wash for 5 seconds (2.5 seconds/side) with cold running (1.6/min) tap water. Test C The above test method was applied to the side of the glass for 10 seconds (5 seconds/
Side) Change by washing. Test D The above test method was applied to the side of the glass for 20 seconds (10 seconds/
Side) Change by washing. Test E The method of Test A is modified as follows: 1. Coat both sides of a clean glass slide with the test formulation. Use a toothbrush to form a thin film. 2. Rinse glass slides with cold running tap water until all test formulations have been washed away (visual observation). 3 Place the glass slide into the pre-inoculated jar of plaque medium. 4 Continue as in Test A. Attempts have been made to establish the presence of sulfonated polymers (arylene ether sulfones) using preferred in vitro test procedures, but they are difficult to consistently use with multicomponent gel formulations such as the preferred formulations of the present invention. It is. This procedure is based on the measurement of the zeta potential of powdered human tooth enamel in contact with an aqueous solution of a polymeric zinc sulfonate compound.
This microelectrophoretic technique consists of measuring adsorption isotherms by measuring the zeta potential of tooth enamel in the presence of increasing concentrations of polymeric zinc sulfonate. All solutions are
Prepared in 0.0200M sodium chloride. Udel
When polysulfone DS 1.8 zinc sulfonate was so tested, the adsorption isotherm obtained showed that the surface potential of the tooth enamel particles became increasingly negative with increasing concentration of zinc. Approximately -40mV
A plaque value of was reached, indicating that the enamel surface is saturated with polymer anions. In the absence of the polymeric zinc salt, the zeta potential of tooth enamel was approximately -10 mV. These experimental techniques established that polymer anions are indeed adsorbed onto the enamel surface. In the presence of the polymeric sulfonate, the powdered enamel was briefly contacted with a 0.1% w/v solution of the polymeric sulfonate, and then, after measuring the initial charge on the enamel, a large volume of 0.0200 mol. There were successive washes with sodium chloride and the zeta potential was measured after each wash. It has been discovered that the degree of sulfonation of poly(arylene ether sulfone) polymers has a significant effect on plaque reduction and that a certain minimum DS is required for the development of adequate barrier activity. The DS can be varied at will by adjusting the sulfonated zinc conditions, eg, the molar ratio of sulfonating agent to polymer. The nature of the aromatic polymer repeat unit governs the maximum DS that can be achieved. Linking groups attached to aromatic rings in the polymer chain structure, such as ethers, sulfones, and various organic groups (see, e.g., the definition of Y above), can have a deactivating or activating effect on aromatic sulfonation. You can have it. Electronic and steric effects determined the location of sulfonation as well as the ease of sulfonation. These mechanistic considerations can be found in popular organic texts, such as RTMorrison and
RNBoyd, âOrganic Chemistryâ 3rd edition,
Allyn and Bacon, Inc., Boston, 1973. In poly(arylene ether sulfone) polymers, the ether bond activates sulfonation at the available ortho position of the adjacent aromatic ring; in contrast, the sulfone group activates the aromatic ring to which it is attached for aromatic sulfonation. become inactive. For example, A. Noshay and L.M.
Robeson (supra) established that the sulfonation of Udel Polysulfone actually occurs only in the ortho position of the bisphenol A moiety with respect to the ether oxygen atom, an example of which is: The degree of sulfonation (DS) of poly(arylene ether sulfone) derivatives can be determined by several methods: (a) NMR analysis, (b) elemental analysis for the sulfur to carbon ratio, or (c ) Direct titration of sulfonic acids with standard sodium hydroxide. The NMR method is probably a more accurate method because it does not tend to be interfered with by other impurities like acidity or elemental analysis. Acidity assays for DS agree well with those determined by NMR when the sulfonic acid polymer is carefully washed to remove entrained sulfuric acid and dried well, and in this regard the method of the sulfonation reaction can be determined. It is often the most convenient assay method to monitor. Good correlations between calculated values for metal salts and measured values determined by atomic absorption are obtained for polymers carefully purified by dialysis. The acidity measurement method for DS determination involves adding an accurately weighed 2 g sample (±0.1 mg) of the sulfonic acid polymer, dissolved in approximately 10 volumes of water, alcohol, or other solvent, to a standardized sodium hydroxide solution. and titration to the end of the potentiometric dropping point. The acidity A of the sample is milliequivalent/g (meq/g)
It is expressed as Using the acidity value A and the formula weight R of the non-sulfonated repeat units in the polymer, DS
is calculated from the following equation: A = (ml of titrant) (normality) / weight of sample (g) DS = (R) (A) / 1000-80A Relating polymer structure to plaque barrier activity A concept related to DS that is sometimes so useful when attaching is the average number of sulfonic acid groups or sulfonic acid groups per aromatic group in the repeating unit. This is simply DS (determined by the procedure described above) divided by the number of aromatic groups in the repeating unit, i.e. DS/Ar
It is. For example, Udel in DS2.0
Polysulfone sodium sulfonate has a D of 0.5 due to the presence of four aromatic groups in each repeating unit.
It can be expressed as indicating S./Ar. Sulfonates of poly(arylene ether sulfone) polymers, e.g. Udel
The plaque barrier activities of the sulfonate salts of Polysulfone, Vitrex ⢠Polyethersulfone, and Radel Polysulfone are shown in Table 1, and these achieve a certain minimum degree of sulfonation to obtain satisfactory plaque barrier activity. proves that this is necessary. Generally, sulfonated poly(arylene ether sulfone) polymers with high plaque barrier activity are obtained only when the average number of sulfonate groups per aromatic group within the polymer (DS/Ar) is at least about 0.2. . In addition to being insoluble in water, non-sulfonated polymer intermediates do not exhibit any plaque barrier activity. Effective plaque barrier activity (plaque reduction of at least 40% or more is seen only when the hydrophilicity of the polymer is increased by the introduction of sulfonic acid or sulfonate functional groups. In the compositions of the invention Although the molecular weight of the polymer used is not considered a critical factor, generally the polymer has a weight average molecular weight within a wide range of from about 5,000 to about 200,000. Preferred molecular weights are from about 20,000 to about
The range is 50000.
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ããäžèŽãããTable: Example 1 Udel Polysulfone Sulfonic Acid, DS 1.8 A 12 volume resin flask was equipped with a mechanical stirrer, thermometer, two addition funnels, and a nitrogen inlet adapter. The flask was charged with 3000 ml of methylene chloride dried over molecular sieves. In one side of the dropping funnel, add 664 g in 3000 ml of dry methylene chloride.
(1.50 mol) of Udel Polysulfone (type P1700, medical grade, MG11; Union Carbide) was supplied. In the other dropping funnel, add 360 g (4.50 moles) to the cooled solution of 205 g (1.125 moles) of triethyl phosphate dissolved in 3000 ml of dry methylene chloride.
The sulfonating agent was prepared by the controlled addition of anhydrous liquid sulfur trioxide. While stirring the methylene chloride solvent in a resin flask, the solution of the polymer and the solution of the sulfonating agent were mixed at an ambient temperature varying from 23°C to 32°C.
They were added simultaneously over a period of 1-2 hours. After the addition was complete, the resulting suspension of white solid was stirred for an additional 1-2 hours at ambient temperature. The product was vacuum filtered through a fritted glass funnel and mechanically slurried.
of methylene chloride and passed each time.
A final slurry wash in colorless diethyl ether brightened the product. After air drying at room temperature,
The yield of sulfonic acid derivatives of Udel Polysulfone is
It was 1043g. The degree of sulfonation (DS) determined by acidity dropping point or NMR analysis was 1.8. Example 2 Udel Polysulfone Sulfonic Acid Sodium Salt, DS 1.8 A stirred solution of 1030 g of the sulfonic acid derivative prepared according to Example 1 in 5150 ml of 95% ethanol is added with vigorous stirring to 2N
of sodium hydroxide (in ethanol) was slowly added to bring the neutralization end point (PH8 to 9). The suspension of the sodium sulfonate derivative was stirred for an additional hour, filtered with suction, washed on a funnel with 95% ethanol, and subsequently washed by mechanical slurry in 2000 ml of 95% ethanol. The solid was dried at room temperature to remove most of the solvent and then air-dried to near constant weight in a high draft oven at 60°C.
The yield of sodium sulfonate derivative of Udel Polysulfone, DS1.8, was 1041 g. Example 3 Udel Polysulfone Zinc Sulfonate, DS 1.8 A stirred solution of 133.0 g of Udel Polysulfone sodium sulfonate derivative DS 1.8, prepared as in Example 2, in 1200 ml of water is heated to dissolve the polymer. , cooled to room temperature, and centrifuged the solution to remove approximately 4% of highly insoluble solids. An aliquot of the total centrifuge containing about 26.3 g of sodium sulfonate solids was diluted to about 500 ml with water. 10.5 in 20ml water
A solution of an aliquot of 1.5 g of zinc chloride was added and the resulting thick solution, pH 6.2, was dialyzed in a membrane tube (6000-8000 molecular weight cutoff) surrounded by distilled water. Removal of water from the dialyzed polymer solution, pH 6.5, by lyophilization yielded 25.4 g of purified
Udel Polysulfone Zinc Sulfonate, DS1.8,
was obtained as a fluffy white solid. In an alternative method, a solution of sodium sulfonate derivative in water was prepared and centrifuged after addition of zinc chloride to obtain a clear solution of zinc sulfate. Further purification, especially on a large scale, is possible using a Tri-Ex-1 hollow fiber dialysis machine (Extracorporeal Medical Specialties, Inc.).
Inc.)], in which the polymer solution was passed twice through the dialyzer at 100-200 ml/min and distilled water was passed in countercurrent at about 500-600 ml/min. Lyophilization of the dialyzed polymer solution yields the purified zinc salt of the polymer. Zinc salts in polymers are highly hygroscopic, with 42%
and 75% relative humidity for approximately 24 hours, absorbed significant water (35-40% weight increase). To stabilize the moisture content of the total supply of polymers for clinical studies, the zinc sulfonate obtained by lyophilization was stored at ambient laboratory conditions (temperatures of approximately 20-25 °C and temperatures between approximately 40-70% (relative humidity) to achieve maximum moisture uptake over several days to a substantially constant weight. Using this procedure, an 8 Kg lot of zinc salt was equilibrated to 21.5% water by weight, as determined by thermogravimetry. Table 2 shows the assay values for zinc salt of this lot of polymers.
and when corrected for moisture, 1.8
Very good agreement with the theoretical values for anhydrous zinc salts with DS.
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ãããå€æŽãè¡ãããšãã§ããã[Table] Middle Example 4 Udel Polysulfone Zinc Sulfonate, DS1.8
By ion exchange of sulfonic acid derivatives A solution of 5.0 g of Udel Polysulfone sulfonic acid derivative (acidity of 16.6 meq) in 100 ml of water was prepared and after addition of 2.25 g (33.0 meq) of zinc chloride,
Ion exchange was allowed to proceed at room temperature overnight. The solution was purified by passing through a 0.8 micron membrane filter and the solution was dialyzed in a dialysis membrane in water. The hydrochloric acid by-product produced in the ion exchange reaction was removed to the extent of 94% by dialysis within 1 hour, as determined by sodium hydroxide titration of the surrounding water (PH 2.7). After allowing dialysis to proceed for several days and removing water under reduced pressure from the purified polymer solution, 3.7 g of
An absorbent wet zinc sulfate derivative of Udel Polysulfone was obtained. Analysis: Zinc, 7.08%; Sodium,
0.026%; absorption at 274 nm, 31.9; sulfate and triethyl phosphate were not detected. Example 5 Udel Polysulfone Sodium Sulfonate,
DS0.7 A solution of 2.2 g (5.0 mmol) of polysulfone in 20 ml of dry methylene chloride and a solution of 0.33 ml (0.58 g, 4.98 mmol) of chlorosulfonic acid in 20 ml of methylene chloride are added to a 40 ml portion of a reaction flask. Added simultaneously to methylene chloride with vigorous stirring. Addition time is 21 minutes, and temperature is 24â
was maintained constant. The pink solution containing some rubbery precipitate was stirred for a further hour and 100 ml
diluted with diethyl ether. This clear solution phase was decanted from the gum. When crushed with additional water, the rubber turns into a white solid, which is collected and
Dry with ether and dry to obtain 2.5 g of polysulfone sulfonic acid. 2.4925 of this sulfonic acid
The DS was determined to be 0.7 by titrating 6.9 ml of 0.495 N sodium hydroxide solution in 1:1 tetrahydrofuran-water to the end of neutralization. Removing the solvent from the neutralized solution results in
2.3 g of sodium sulfonate derivative of polysulfone was obtained. Example 6 Sodium poly(phenylene ether sulfone) sulfonate, DS 0.6 2.32 g (100 mmol) poly(p-phenylene ether sulfone) in 40 ml dry methylene,
100p type (ICI) solution for 21 minutes at 24-25
1.6 g in 80 ml methylene chloride at °C
(20.0 mmol) of liquid sulfur trioxide was added to a stirred solution. After an additional 20 minutes of reaction, the reaction mixture was diluted with 20 ml of diethyl ether and a white solid was collected. The solid was slurried in 150 ml of methylene chloride, filtered and washed with methylene chloride and ether. The yield of sulfonic acid derivative was 2.8 g. A sample of 2.511 g of sulfonic acid derivative in methanol-water was neutralized with 8.0 ml of 0.641N sodium hydroxide and the degree of sulfonation (DS) was established to be 0.6. Removal of the solvent from the neutralized solution yielded 2.5 g of the polymeric sodium sulfonate derivative. Example 7 Radel Polysulfone Sodium Sulfonate,
DS1.3 4.0 g (0.01 mol) in 40 ml dry methylene chloride
into a stirred suspension of Radel Polysulfone,
2.4 g dissolved in 20 ml methylene chloride containing 1.37 g (7.5 mmol) triethyl phosphate
(0.03 mol) of liquid sulfur trioxide,
Added over 12 minutes at 26°C. This suspension
It was added for an additional 70 minutes at 24-26°C and left at room temperature for 3 days. The solid was filtered, washed with methylene chloride and diethyl ether, and dried to yield 3.6 g.
A sulfonic acid derivative of the polymer was obtained. The sodium salt was prepared by neutralizing a stirred suspension of 3.5507 g of sulfonic acid derivative in 10 ml of methanol with standardized sodium hydroxide solution. A solid suspension of the sodium salt was recovered by solvent stripping, the residue was dissolved in 1:1 tetrahydrofuran-water, filtered from some solid (0.5 g) believed to be the sulfate salt, and the solvent was removed. Thereupon, 2.3 g of fine pale yellow colored solid was obtained. The DS corrected for the amount of free sulfuric acid in the sulfonic acid polymer recovered as the sulfate salt was 1.3. The DS determined by NMR analysis was 1.6. The plaque barrier oral compositions of the present invention are comprised of conventional pharmaceutically acceptable oral hygiene formulations (compatible with said plaque barrier agent) containing an effective amount of a plaque barrier agent as defined herein. ). Such formulations can be used, for example, as mouthwashes, rinses, cleaning solutions,
Non-abrasive toothpastes, tooth cleansers, coated tooth silks and interdental irritation coatings, chewing gums, lozenges, respiratory fresheners, foams and sprays. Plaque barrier agents generally contain approximately
It could be present in effective concentrations ranging from 0.05% to as high as 30% by weight, or up to the limits of compatibility with the vehicle. However, no benefit will be obtained from concentrations above about 20% by weight.
The preferred concentration range for plaque barrier agents in the formulations of the present invention is from about 0.5 to about 10% by weight. A more preferred range is about 2 to about 8% by weight, with about 5%
is currently the most preferred range in a non-abrasive gel vehicle. The pH of these plaque preparations is PH5.0-10.0, preferably PH5.0-8.0, more preferably about PH6.0-7.5. A PH lower than 5.0 is undesirable as enamel demineralization can increase. Suitable conventional pharmaceutically acceptable vehicles that can be used with plaque barrier agents to prepare the barrier compositions of the present invention include water, ethanol; humectants such as propylene glycol, glycerol and sorbitol; Cellulose derivatives, e.g.
Methocel, carboxycellulose (CMC TMF)
Klucel HF, polyoxypropylene/polyoxyethylene block copolymer, e.g. Pluronic F-127, Pluronic F
-108, Pluronik P-103, Pluronik P-
104, Pluronic P-105, and Pluronic P-123, colloidal aluminosilicate complexes such as Veegum, and myucoprotein thickeners such as Carbopol.
Gelling agents such as 934; gelling stabilizers such as silicon dioxide, such as Cab-O-SilM5 and polyvinylpyrrolidone; sweeteners such as sodium saccharin; preservatives such as citric acid, sodium benzoate, cetylpyridinium chloride, Potassium sorbate, methylparaben and ethylparaben; detergents such as sodium lauryl sulfate, sodium cocomoglyceride sulfonate, sodium sarcosinate and polyoxyethylene isohexadecyl ether (Arlasolve200) and approved colorants and flavors. can. The following specific examples illustrate example plaque barrier compositions. Example A Mouthwash Solution Barrier 0.5-2.0% w/w Glycerol (humectant) 6.0 Pluronic F-108 1.0 Sodium Saccharin (sweetener) 0.3 Deionized water Sufficient Flavoring 1.0 100.0 Example B Mouthwash Solution plaque barrier agent 0.5-3.0% w/w Ethanol, USP 15.0 Pluronic F-108 (foaming agent) 2.0 Glycerol (humectant) 10.0 Sorbitol (humectant) 10.0 Sodium saccharin (sweetener) 0.2 Deionized water Sufficient quantity Flavoring 0.2 100.0 Example C Abrasive toothpaste gel plaque barrier agent 2.0-10.0% w/w Humid silica (abrasive agent) 55.0 Sodium lauryl sulfate (cleaning agent) 1.5 Glycerol (humectant) 10.0 Carboxymethyl cellulose (gelling agent)
2.0 Sodium saccharin (sweetener) 0.2 Sorbitol (humectant) 10.0 Flavor 1.0 Deionized water Sufficient amount Preservative 0.05 100.0 Example D Chewing gum plaque barrier 1.0-11.0% w/w Gum base 21.3 Sugar 48.5-58.5 Corn syrup (Baume45) 18.2 Flavoring 1.0 100.0 Example E Non-abrasive gel toothpaste plaque barrier agent 0.05-30.0% w/w Sorbistat (preservative) 0.15 Deionized water Adequate amount Silicon dioxide ( 1.0 Pluronic F-127 (gelling agent) 20.0 Sodium Saccharin 0.2 Flavoring 1.5 100.0 Example F The following formulation incorporates a presently preferred non-abrasive gel composition containing a barrier agent according to the present invention. Illustrate. Ingredients %w/w Distilled water Sufficient amount Sodium saccharin (sweetener) 0.20 Sodium benzoate (preservative) 0.30 FD & Blue #1 0.27 (0.1% aqueous solution) D&C Yellow #10 0.50 (0.5% aqueous solution) Gel Glycerol (humectant) 20.00 Cab-O-SilM5 (silicon dioxide) 1.00 Plaque barrier agent 5.00 (dry basis) Flavoring agent 0.80 100.0 Details of the preparation of all of the above formulations are in this field Although well known in the art, the procedures suggested for the preparation of the gel formulation of this example are described for completeness. In a first container, mix water, sodium, saccharin, and sodium benzoate. The container is then placed in an ice bath. When the temperature reaches 6°C, add the gelling agent and gently mix the contents until the gelling agent dissolves. The solution is then heated to 70°C. Add glycerin to the second container. Then Cab-
Sprinkle in O-SilM5 while mixing. The plaque barrier agent is then added and mixing continued until a smooth paste is formed. The paste is then heated to a temperature of 70° C. while mixing in a water bath. Add the first container to the second container and blend together while maintaining a temperature of 70° C. until the batch is homogeneous. Flavors are then added, all mixing stopped and the formulation allowed to settle for approximately 1 hour. Air bubbles can be removed if necessary and refrigerated overnight. Although any pharmaceutically acceptable gelling agent that is compatible with the plaque barrier agent can be used, the currently preferred gelling agent is Pluronic F-127. These compositions are preferably used 1 to 3 times daily according to a daily oral hygiene program to prevent plaque buildup on the teeth. Of course, changes may be made without departing from the spirit or scope of the invention.
Claims (1)
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èŒã®çµæç©ã§ãã€ãŠãããã«æã«ãªãšã¹ããåç©
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æç©ã[Claims] 1. An amount effective to prevent plaque from adhering to teeth.
Structure (A), --(Ar 1 --SO 2 --Ar 2 --O) -- (A) and structure (B) --(Ar 1 --SO 2 --Ar 2 --O-Ar 3 --O) -- (B) Here Ar 1 is and Ar 2 is or Ar 2 is Ar 4 âSO 2 âAr 4 and âAr 4 â
It can be composed of one or more interval units selected from SO 2 âAr 4 âSO 2 âAr 4 , and each Ar 4 in the interval unit is and Ar 3 is selected from Ar 4 and [Formula], where Y is selected from lower alkylene of 1 to 5 carbon atoms, lower alkylidine of 2 to 5 carbon atoms, O, S and SO 2 ,; the subscript c is an integer selected from 0, 1 and 2, obtained by dividing the sum of C's in each of repeating units (A) and (B) by the number of aromatic groups in said repeating unit. and M is an ion of lithium, sodium, potassium, calcium, magnesium, zinc, aluminum, hydrogen, ammonium, and substituted ammonium derived from a pharmaceutically acceptable organic amine. selected from the group consisting of a sulfonated poly(arylene ether sulfone) polymer having repeating units selected from the group consisting of; and a pharmaceutically acceptable oral hygiene excipient compatible with said polymer. An oral hygiene composition characterized by: 2. The composition according to claim 1, wherein M is a metal selected from the group consisting of potassium, lithium, sodium, calcium, magnesium, zinc and aluminum. 3. The composition according to claim 2, wherein the metal is zinc. 4. A composition according to claim 1, 2 or 3, wherein said quotient ranges from about 0.2 to 0.5. 5. The composition of any of claims 1-4, wherein the sulfonated polymer comprises from about 0.5% to about 10% by weight of the composition, and wherein the composition comprises water, at least about 5% by weight of the composition. % by weight of a humectant selected from the group consisting of glycerol and sorbitol;
about at least about 16% by weight of a gelling agent selected from the group consisting of block copolymers of polyoxypropylene and polyoxyethylene, wherein said polyoxypropylene component has a polyoxypropylene component of about 3000 to about
4000, and the polyoxyethylene comprises about 25 to about 80 mole percent of the copolymer.
The composition that makes up the composition. 6. The composition of claim 5, wherein the sulfonated polymer comprises about 2% to about 8% by weight.
composition present in an amount of 7. The composition of claim 5 or 6, wherein the amount of gelling agent is about 16 to about 22% by weight.
composition in an amount of 8. A method for preventing plaque from adhering to teeth, which comprises periodically applying the composition according to any one of claims 1 to 7 to teeth. 9. The method according to claim 8, comprising:
A method of applying the composition from about 1 to about 3 times per day. 10. The composition according to any one of claims 1 to 7, further comprising an anti-caries sulfide. 11. The composition according to claim 10, wherein the fluoride is sodium fluoride.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17234780A | 1980-07-25 | 1980-07-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5756417A JPS5756417A (en) | 1982-04-05 |
JPH0154323B2 true JPH0154323B2 (en) | 1989-11-17 |
Family
ID=22627328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56115418A Granted JPS5756417A (en) | 1980-07-25 | 1981-07-24 | Sulfonated poly(arylene ether sulfone) polymer as tooth dirt inhibitor |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS5756417A (en) |
CA (1) | CA1167382A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2147947A1 (en) | 2001-11-29 | 2010-01-27 | Ube Industries, Ltd. | Process for preparing an aromatic polyether sulfone blockcopolymer |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4413106A (en) * | 1982-12-27 | 1983-11-01 | Albany International Corp. | Heterogeneous sulfonation process for difficultly sulfonatable poly(ether sulfone) |
US4666708A (en) * | 1984-01-27 | 1987-05-19 | Oral Research Laboratories, Inc. | Dental rinse |
GB8605817D0 (en) * | 1986-03-10 | 1986-04-16 | Ici Plc | Membrane |
EP3381479A1 (en) * | 2017-03-29 | 2018-10-03 | ARTOSS GmbH | Carrier composition for bone substitute materials |
-
1981
- 1981-06-22 CA CA000380356A patent/CA1167382A/en not_active Expired
- 1981-07-24 JP JP56115418A patent/JPS5756417A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2147947A1 (en) | 2001-11-29 | 2010-01-27 | Ube Industries, Ltd. | Process for preparing an aromatic polyether sulfone blockcopolymer |
Also Published As
Publication number | Publication date |
---|---|
JPS5756417A (en) | 1982-04-05 |
CA1167382A (en) | 1984-05-15 |
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