CN1034667A - 防治牙垢的组合物 - Google Patents
防治牙垢的组合物 Download PDFInfo
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- CN1034667A CN1034667A CN88108695A CN88108695A CN1034667A CN 1034667 A CN1034667 A CN 1034667A CN 88108695 A CN88108695 A CN 88108695A CN 88108695 A CN88108695 A CN 88108695A CN 1034667 A CN1034667 A CN 1034667A
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- Prior art keywords
- hydrogen
- alkyl
- acid
- compositions
- salt
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 208000006558 Dental Calculus Diseases 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 230000002272 anti-calculus Effects 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229920001519 homopolymer Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 59
- -1 alkyl itaconate Chemical compound 0.000 claims description 45
- 150000003839 salts Chemical class 0.000 claims description 29
- 229910052783 alkali metal Inorganic materials 0.000 claims description 26
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims description 24
- 150000002431 hydrogen Chemical group 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 21
- 150000001340 alkali metals Chemical group 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 11
- 235000011180 diphosphates Nutrition 0.000 claims description 11
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 229940091249 fluoride supplement Drugs 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000606 toothpaste Substances 0.000 claims description 8
- 229940034610 toothpaste Drugs 0.000 claims description 8
- 229920000388 Polyphosphate Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 7
- 239000001205 polyphosphate Substances 0.000 claims description 7
- 235000011176 polyphosphates Nutrition 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 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 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 210000000214 mouth Anatomy 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229960004711 sodium monofluorophosphate Drugs 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 3
- 229940018557 citraconic acid Drugs 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 3
- 229960002799 stannous fluoride Drugs 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229960000414 sodium fluoride Drugs 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 150000002689 maleic acids Chemical class 0.000 claims 2
- AWJKGYJGKHDWDA-UHFFFAOYSA-N P(=O)(O)OP(=O)O.CCCC Chemical compound P(=O)(O)OP(=O)O.CCCC AWJKGYJGKHDWDA-UHFFFAOYSA-N 0.000 claims 1
- 229910001413 alkali metal ion Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- AQMNWCRSESPIJM-UHFFFAOYSA-M sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 claims 1
- 239000004634 thermosetting polymer Substances 0.000 claims 1
- 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 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 108090000790 Enzymes Proteins 0.000 description 11
- 102000004190 Enzymes Human genes 0.000 description 11
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 229940048084 pyrophosphate Drugs 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000001506 calcium phosphate Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 description 6
- 239000000551 dentifrice Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000011010 calcium phosphates Nutrition 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000600 sorbitol Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000011230 binding agent Substances 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 235000013355 food flavoring agent Nutrition 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 210000003296 saliva Anatomy 0.000 description 4
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 2
- 208000002064 Dental Plaque Diseases 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 2
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- 102000009609 Pyrophosphatases Human genes 0.000 description 2
- 108010009413 Pyrophosphatases Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004075 cariostatic agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 2
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 2
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
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- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
- A61K8/21—Fluorides; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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Abstract
本发明在此揭示用于抑制牙垢的口用组合物和
方法，所述组合物的特性由氟化物辕、牙磨剂和防牙
垢剂的存在而决定。防牙垢剂选自羧基单体的均聚
物和含有至少30％所述羧基单体的共聚物。
Description
本发明涉及含有防牙垢剂的口用组合物。
牙垢或牙石是钙化的牙斑，而牙斑是齿龈疾病的恶果。牙垢或牙石是齿龈边牙齿表面形成的沉积物。定形的牙垢中一部分是无机物，主要是磷酸钙，分布在类似骨质、牙釉质和牙质的羟磷灰石晶格结构里。牙垢中有机物包含唾液沉积、食物碎屑以及各种微生物。
人们一致认为，钙和正磷酸盐组成了已为熟知的羟磷灰石晶体物质，也就是牙垢，矿化的、附在牙齿上的坚硬组合物。晶态羟磷灰石的母体是非晶型磷酸钙，它在原子结构、颗粒形态学和化学计量学方面均与羟磷灰石不同。非晶型磷酸钙的X射线衍射图案显示出宽峰这个缺乏所有晶型物质，包括羟磷灰石在内所共有的长距离原子秩序性质的非晶型物质的特征。
线性分子脱水多磷酸盐，诸如，六偏磷酸盐、三聚磷酸盐、焦磷酸盐及类似物质，均是人们熟知的有效的钙、镁离子的抑制剂、阻止剂、多价螯合剂和/或螯合剂。人们还知道这些物质也是生物体外羟磷灰石形成的有效的抑制剂。人们也知道，在口腔和/或唾液中，这些多磷酸盐会被唾液酶，即磷酸酶有效地水解成为正磷酸盐，作为羟磷灰石形成的抑制剂，正磷酸盐无能为力。
研究表明，一化合物在生物体外防止羟磷灰石晶体生长的能力和其在生物体内防止钙化的能力之间存在着理想的相互关系，条件是这一化合物是稳定的，与唾液及其中放置成分不发生反应。
口用组合物特性在于氟化物源、牙磨剂和对唾液或唾液酶稳定的防牙垢剂。防牙垢剂选自C3-5单不饱和一元羧酸和二元羧酸的均聚物，选自至少含有30%wt.这种酸，尤其是丙烯酸的共聚物。本发明还通过应用这里所提供的口用组合物之一来介绍一种防牙垢的方法。这里所指的防牙垢剂在没有杀菌组合物的情况下有效。
此处提出并申请保护的口用组合物的特性在于氟化物源，牙齿摩擦或磨光剂、媒介物和防牙垢剂。防牙垢剂选自C3-5单不饱和一元羧酸和二羧酸的均聚物，选自含有至少30%（wt.）C3-5单不饱和一元羧酸或二元羧酸、其酸酐或这种酸的水溶性盐的共聚物。可以和一种或多种酸共聚的共聚用单体包括丙烯酸胺、丙烯酸烷基酯、衣康酸烷基酯、乙烯磺酸、丙烯酸羟烷基酯、丙烯酸烷氧烷基酯、低级烯基羧酸酯、苯乙烯磺酸、烯丙氧基羟基烷烃磺酸、丙烯酰氨基烷烃磺酸、磺基低级烷基丙烯酸酯、聚合乙烯醇、酸酐及其盐。上述防牙垢剂可以与包括其它防牙垢剂在内的其它添加剂联合使用。本发明还涉及通过将此处介绍并申请保护的口用组合物防牙垢用量应用于牙齿来防治牙垢的方法。
羧酸、酐及其盐的均聚物和共聚物的分子量在400-100，000之间，较好的是500-50，000。均聚物的分子量尤以500-50，000为佳。此处适宜的共聚物为无规则的非交联均聚物。分子量用凝胶渗透色谱法测定。本文申请保护的口腔组合物中防牙垢剂的用量约为0.01至10%（wt.），较可取的是0.1-5%。
多磷酸盐可以起到磨光或摩擦剂的作用，这一点将在后面介绍。这种多磷酸盐在没有唾液酶时对防止牙垢很有效，而当酶存在时，多磷酸盐会被水解为作为防牙垢剂无效的正磷酸盐。
氟化物离子源，或提供氟的化合物，依照本发明作为所述组合物的一个基本成分，是人们熟知的抗龋剂，在本发明的实践中也起这种抗龋剂的作用。这些化合物微溶于水或完全溶于水。它们的特性在于水中释放氟化物离子的能力和避免与该口腔制剂的其它化合物发生不需要的反应的能力。这些物质中有无机氟化物盐类如可溶性碱金属和碱土金属盐，例如氟化钠、氟化钾、氟化铵、氟化钙、氟化亚铜一类的铜氟化物、氟化锌、氟化钡、氟硅酸钠、氟硅酸铵、氟锆酸钠、一氟磷酸钠、单和双氟磷酸铝以及氟化焦磷酸钠钙。较为可取的是碱金属和锡的氟化物，诸如氟化物和氟化亚锡、一氟磷酸钠，及它们的混合物。
供氟化合物的量是在一定程度上取决于化合物类型、其溶解性和口用组合物类型，但必须是无毒性的量，通常约占组合物的0.005-3.0%。在洁牙剂组合物中，例如凝胶、乳膏、牙膏或牙粉，以米楹衔镏亓考疲苁头?0-3500ppm的氟离子的供氟化合物量被认为是满意的。任何适宜的最小用量均可采用，但比较可取的用量应为能释放约300-2，000ppm氟离子的量，更好的是能释放约800-1，500ppm氟离子的用量，以碱金属氟化物和氟化亚锡为例，该成分用量以该组合物重量为基准最高可达约2%（wt.），其中以约0.05%-1%为佳。若是一氟磷酸钠，用量约为0.1-3%，以约0.2-1%为佳。
在诸如漱口剂、锭剂和口香糖一类的口用组合物中，供氟化合物通常维持足以释放高达约500ppm，最好是约25-300ppm（wt.）氟离子的用量水平。一般，供氟化合物占0.005-1.0%（wt.）左右。
进行商品化制备适宜的口用组合物时所用的水最好是低离子含量并且没有有机杂质。本发明组合物的含水量为约2%-95%，以约20%-95%为佳。当以牙膏的形式存在时，含水量最好是约2%-45%，当为漱口剂时，含水量最好是约45%-95%。
牙膏中的液体媒介通常可含占制剂约10%-90%（wt.）的水和致湿物。甘油、丙二醇、山梨醇、聚丙二醇和/或聚乙二醇均为适宜的致湿物或载体。水、甘油和山梨醇的液态混合物也是很好的致湿物。清洁凝胶的折射率非常重要，故最好的使用量为：水约3-30%（wt.）、甘油0-80%（wt.）左右，山梨醇约20-80%（wt.）。
本发明某些期望的形式中，口用组合物可以是固态或面糊状，诸如牙粉、牙片、牙膏、凝胶或牙乳剂。这些固态或面糊状口用制剂的媒介物通常含有一磨光物质，例如，水不溶性偏磷酸钠、偏磷酸钾、磷酸三钙、磷酸钙二水合物、无水磷酸二钙、焦磷酸钙、正磷酸镁、磷酸三镁、碳酸钙、硅酸铝、硅酸锆、二氧化硅、膨润土、以及它们的混合物。其它适宜的磨光物质包括USP3，070，510中描述的、诸如蜜胺甲醛、苯酚甲醛和脲甲醛一类的颗粒热固（性）树脂，以及交联聚环氧化合物和聚酯。较理想的磨光物质包括最大粒度约5μ、平均粒度高达约1.1μ、表面积高达约50，000cm/gm的晶体硅石、以及硅胶或胶体硅石和复杂的无定杏碱金属硅铝酸盐。
使用清晰可见的凝胶时，胶体硅石和碱金属铝硅酸盐复合物磨光剂特别有用，因为它们的折射率接近于液体凝胶剂的折射率。
人们熟知此处所用的线性分子脱水多磷酸盐可作为摩擦牙齿添加剂，通常以全部或部分地被中和的水溶性碱金属或铵盐及其混合物的形式被使用。具有代表性的包括六偏磷酸钠、三聚磷酸钠、二酸二钠、一酸三钠和焦磷酸四钠、及类似物质。线性多磷酸盐对应于（Na PO3）n，其中n约为2-125。它们一般用在配制好的口用组合物里的用量约占0.1-7%（wt.），最好是1-5%（wt.）。
磨光物质或牙磨剂通常以大约10%-99%（wt.）的浓度用于固体或面糊状组合物中。对牙膏，最好是约10%-75%，对牙粉，则以约70%-99%为宜。
牙膏、乳剂和凝胶通常含有大约0.1-10，特别是大约0.5-5重量百分比的天然或合成的增稠剂或胶凝剂。适宜的增稠剂有合成水辉石、合成胶体镁、碱金属硅酸盐复合粘土，和中等分子量的羧乙烯系聚合物或聚丙烯酸。
本发明口用组合物可以含有各种根据需要而存在的普通口用成分，包括起泡剂、调味剂、增甜剂、粘合剂、着色剂、湿润剂及颜料。
较好的根据需要而存在成分是起泡剂。适宜的起泡剂应是相当稳定并且在较宽的pH值内能形成泡沫，这种起泡剂是无皂阴离子的、阳离子、两性离子及两性有机合成洗涤剂。这些类型的起泡剂在Agrlcola et al USP 3，959，458和Haefele USP3，937，807中有更全面的描述。
调味剂也可加入配制好的组合物里。适宜的调味剂包括冬青油、薄荷油、薄荷油（取自mentha）、黄樟油和丁子香油。能用的增甜剂有糖精、葡萄糖、果糖、aspartame、D-色氨酸、二氢查耳酮、acesulfame和环己烷氨基磺酸钠。组合物中调味剂用量一般为大约0.4%-2%（wt.）、增甜剂用量为大约0.1%-5%（wt.）。
粘合剂也可以与本发明的牙膏一起使用。这类粘合剂有，例如xanthan树脂、角叉菜（爱尔兰藓）、及中等分子量的羧基乙烯基聚合物或聚丙烯酸。这些粘合剂用量一般约为0.1%-1%。
该组合物另一个根据需要而存在的成分是湿润剂，它可以防止牙膏组合物在空气中变硬，在漱口剂里则可以使口腔感到湿润。某些湿润剂还能使漱口剂和牙膏组合物产生香甜感觉。该组合物中湿润剂，以纯湿润剂计，一般约占该组合物的0%-70%（wt.）以大约5%-55%为佳。
本发明所用的适宜湿润剂包括，诸如甘油、山梨糖醇、木糖醇和丙二醇一类的食用多元醇。山梨糖醇常常以70%溶液的形式使用。
此处的漱口剂也可以含大约0-30%，最好是5-25%的乙醇，来作为杀菌剂。
此处的组合物的pH值为6-10，以7-9较好，最好是用焦磷酸盐进行适当的平衡或通过添加碱性或酸性剂来得到上述pH值。
此处组合物使用常规混合技术制备。
此处提及的防牙垢剂选自C3-5单不饱和一元羧酸和二元羧酸的均聚物，选自由这些酸、酐及其盐与至少一种主要共聚用单体所形成的共聚物。共聚用单体选自丙烯酰胺、丙烯酸烷基酯、衣康酸烷基酯、乙烯基磺酸、羟烷基丙烯酸酯、烷氧基烷基丙烯酸酯、低级烯基羧酸酯、苯乙烯磺酸、烯丙氧基羟基烷烃磺酸、丙烯酰氨基烷烃磺酸、磺基低级烷基丙烯酸酯、聚合乙烯醇、酐及其盐。
这里所用的一般术语“丙烯酸盐（或酯）”也包括“甲基丙烯酸盐（或酯）”。
氟化物源，牙磨剂和选自水或水加湿润剂的媒介物与防牙垢剂一样，是本发明口用组合物的基本成分。
本发明的口用组合物可以是确实的液体形式，诸如漱口剂或漂清液。这种组合物的媒介物是典型的最好包含有湿润剂的水-醇混合物。通常，水与醇的重量比大约为1∶1-20∶1，较好的是约3∶1-10∶1，跟理想的则大约为4∶1-6∶1。在这种形式的制剂中，水醇混合物总量通常大约为制剂的70%-99.9%（wt.）。
上述的羧酸共聚物是羧酸、其盐及酐和至少一主要的能共聚的单体所形成的共聚物。该共聚物还可以包含高达约30%，最好是2-10%至少一种第二共聚单体，条件是这种单体对上述作为防牙垢剂的共聚物的性能确实无有害影响。
防牙垢羧酸共聚物含有至少30%（wt.）、最好含40-99%（wt.）以酸或酐或盐的形式存在的羧酸单体。主要共聚用单体用量不高于70%左右，以1-60%为佳。如果不用第二单体。主要的单体便与羧基单体形成共聚物。如果使用第二单体，可以替代一部分主要单体。
主要共聚用单体选自丙烯酰胺、烷基丙烯酸酯、烷基衣康酸酯、乙烯基磺酸、羟烷基丙烯酸酯、烷氧烷基丙烯酸酯、低级烷基羧酸酯、苯乙烯磺酸、烯丙氧基羟基烷烃磺酸、磺基低级烷基丙烯酸酯、聚合乙烯醇，及其酐和盐。
适宜的羧基单体选自C3-5单不饱和羧酸、酐及其盐，具有至少一个活性烯属双键和至少一个羧基，一元羧酸和二元羧酸比较理想。
举例来说，上述酸是丙烯酸、异丁烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、β-丙烯酰氧丙酸、山梨酸、α-氟山梨酸、肉桂酸、β-苯乙烯基丙烯酸、粘康酸、衣康酸、柠康酸、中康酸、戊烯二酸、阿康酸、α-苯基丙烯酸、2-苄基丙烯酸、2-环己基丙烯酸、当归酸、繖形酸（2，4-二羟基肉桂酸）、富马酸、马来酸和酐类。较为可取的羧酸选自丙烯酸、异丁烯酸、衣康酸、马来酸及其酐、柠康酸、和中康酸，特别是丙烯酸、异丁烯酸、衣康酸、马来酸和马来酸酐。丙烯酸和异丁烯酸最为理想。
作为主要共聚用单体的适宜的丙烯酰胺的通式如下：
其中R为氢或甲基，R1和R2分别选自氢、C1-12、最好是C1-8的烷基和取代烷基。较理想的是R1和R2均不是氢的取代丙烯酰胺。连接在烷基上的取代基包括烷基、芳基、羟基、羟烷基、羧酸及酮基。取代丙烯酰胺具体例子包括叔丁基丙烯酰胺、异丙基丙烯酰胺、异丁基丙烯酰胺、甲基丙烯酰胺、叔丁基甲基丙烯酰胺、2-（2，4，4-三甲基戊基）丙烯酰胺、2-（2-甲基-4-氧戊┍０贰Ⅳ腔谆０贰Ⅳ腔０贰?双丙酮丙烯酰胺和3-丙烯酰氨基-3-甲基丁酸。
作为主要的共聚用单体的烷基丙烯酸酯的分子式如下：
其中R是氢或甲基，R1选自C1-6烷基和取代烷基R2-Y，其中R2为C1-6烷基，Y是-SO3X、-C＜O＞R3或-CO2X，其中X为氢、碱金属、碱土金属，或铵，R3是C1-3烷基。最佳实例中的R1是未取代的C1-4烷基。适宜的单体型烷基丙烯酸酯和异丁烯酸酯包括：丙烯酸乙酯、异丁烯酸乙酯、磺基丙基丙烯酸酯和羧乙基丙烯酸酯。
作为主要共聚用单体的衣康酸烷基酯的分子式如下：
其中R2和R3分别代表氢、C1-12烷基和取代烷基，虽然R2或R3可以是氢，但R2和R3并不同时代表氢。R2和R3的取代基包括低级烷基、诸如苯基一类的芳基、及酮基，但在最佳实例中的R2和R3则分别选自非取代的低级C1-4烷基。最佳R2和R3基的具体例子包括：甲基、乙基、丙基、异丙基、丁基和它的异构形式、以及类似基团。此处最佳的是衣康酸二酯，具体例子有衣康酸二甲酯，衣康酸二乙酯和衣康酸二丁酯。
主要共聚用单体的乙烯基磺酸及其盐的结构式如下：
其中X选自氢、碱金属、碱土金属和铵基，以碱金属和铵基为佳。最佳乙烯基磺酸盐是上式中X为钠时的乙烯基磺酸钠。
主要共聚用单体羟烷基丙烯酸酯的结构式如下：
其中R是氢或C1-3低级烷基，以氢或甲基为佳;R1选自含有2-4、最好是2-3个碳原子的低级亚烷基;n为整数1-5。适宜的羟烷基丙烯酸酯的某些具体例子包括羟基丙基丙烯酸酯和羟基丙基甲基丙烯酸酯。
主要共聚用单体烷氧烷基丙烯酸酯的结构式如下：
其中R是氢或甲基，R1是含2至4、最好是2至3个碳原子的亚烷基，n是整数1至5，以1至3为佳，R2是含有1至10、以1至4个碳原子为佳的烷基。烷氧烷基丙烯酸酯单体的具体例子包括甲氧乙基丙烯酸酯，异丁烯酸2-乙氧基乙醇酯、和2-（2-乙氧基乙氧基）乙基丙烯酸酯。
乙烯基羧酸酯单体的结构式如下：
其中R是氢或含1至6个碳原子的低级烷基，以氢或C1-2烷基为佳，R1选自C1-12、以C1-8为佳的烷基。聚合乙烯基羧酸酯可以水解而含有如下结构的聚合乙烯醇重复链节：
其中R是氢或C1-6低级烷基，以氢或C1-2烷基为佳。水解的羧酸酯的R基对应于乙烯基羧酸酯上的R基。乙烯基羧酸酯的具体例子包括乙烯基乙酸酯，乙烯基丙烯酯和2-丙烯基乙酸酯。
主要共聚用单体苯乙烯磺酸及其盐的结构式如下：
其中R是氢或C1-6低级烷基，以氢为佳;X是氢、碱金属或碱土金属或铵，尤其是氢、铵或碱金属。特别适宜的磺酸是苯乙烯磺酸、该化合物中的R为氢并且-SO3基在苯环的3或4位上。苯乙烯磺酸的盐是水溶性的。苯乙烯磺酸的钠盐为易得商品。
主要共聚用单体烯丙氧基羟基烷烃磺酸及其盐的结构式如下：
其中R和R1均为氢或甲基，X选自氢、碱金属、碱土金属和铵基。最佳单体是3-烯丙氧基-2-羟基丙烷磺酸，钠盐。
主要共聚用单体、适宜的丙烯酰氨基烷烃磺酸及其盐具有以下通式结构：
其中R是氢或甲基;X选自氢、铵、碱金属或碱土金属，特别是氢、铵或碱金属;R1和R2分别选自氢和C1-4烷基。在最佳实例中，R是氢、R1和R2均为C1-3烷基。上式结构分子中的字母X代表氢或不影响聚合物水溶性的任何金属阳离子，诸如钠、钾及铵阳离子。另外，X也可以代表钙、镁和锂，因为它们对聚合物的溶解性没有任何不利影响。已经发现，特别适宜于本发明的丙烯酰氨基烷烃磺酸单体是具有如下结构式的2-丙烯酰氨基-2-甲基丙烷磺酸：
主要共聚用单体磺基烷基丙烯酸酯具有如下结构：
其中R1选自氢、甲基或下式基团
其中R2选自C1-12亚烷基，以C2-4亚烷基为佳;X选自氢、碱金属、碱土金属和铵，特别是氢、钠、钾、钙、镁和铵。磺基-SO3X最好是在R2基最后一个碳原子上。R2可以被取代或未被取代。R2取代基选自那些对共聚物防牙垢活性没有不利影响的取代基。较理想的是磺基烷基丙烯酸酯（或盐），其中包括2-磺基乙基异丁烯酸酯（或盐）、3-磺基丙基丙烯酸酯（或盐）、3-磺基丙基异丁烯酸酯（或盐）、双-（3-磺基丙基）衣康酸酯（或盐）。
如果需要，可以用常规方法制备这些单体，但它们是易得商品，因此可以买到。单体聚合形成的实际上是非交联无规聚合物，其分子量经一些反复试验来确定。较理想的共聚物产率约为共聚用单体的50%-99%（wt.）。
共聚物也要求溶于水。高溶解性不是必要的但合乎需要。防牙垢剂可以浓缩水溶液形式装在圆桶中进行船运。每100重量份该浓缩水溶液中含有大约20%-50%（wt.）的固体，要求溶解度达到每100重量份水至少含20重量份。
此处所指的单体聚合作用可以在一互溶剂中进行，比如在C1-6左右的低级链烷醇，或在水中进行，聚合作用需要一种在可接受的时间期限里足以产生所期望组合物的有效量的自由基引发剂。单体酸可如此使用或在聚合之前部分或全部被中和。
在温度为30-130℃左右、大气压或略微加压的条件下，反应在水这唯一的反应介质里可以方便地进行。以总的固体量为基准计，所形成的共聚物含量可以达到大约5%-50%（wt.），该溶液可以直接船运。
此处作为防牙垢剂的适宜的共聚物的平均分子量大约为400-100，000，较好的约为5，000-50，000，分子量用凝胶渗透色谱法定。通过KOH滴定测得所形成的共聚物的酸值大约为230-740，具有COOH基的单体单元的相应的重量百分率为30%-95%（wt.）。较理想的聚合物含有30%（wt.）以上的自由羧基和大约390-700左右的酸值。以下通过实例进一步描述和说明本发明范围内的最佳实施方案。这些实例只有详细说明的唯一目的，并不被认为是本发明的限制。在本发明的精神和范围内，它含有许多各种变化形式。
实例1
按照美国专利4，627，977实例1中描述的pH稳定器技术对磷酸钙沉淀进行分析研究。然后用Brnkman仪器600型系列的pH稳定器滴定分析氢氧化钠的消耗量来得出羟磷灰石（HAP）的生成速率。
在温度恒定在37℃的条件下，将氯化钙溶液、磷酸钠溶液和其它成分混合搅拌，然后将用来维持pH值恒定在7.40的氢氧化钠的量作为时间的函数连续记录下来。
将在37℃用水预饱和的氮气通过溶液以排除二氧化碳。在该系统中，可以确信沉淀和晶体生长发生在二个截然不同的阶段。第一阶段，对应于氢氧化钠首次消耗量，表示无定形磷酸钙的生成，其碱性低于羟磷灰石，而第二阶段，对应于氢氧化钠第二次消耗量，则代表羟磷灰石的晶体生长。
下面的表A列出了试验的结果，其中pH值为7.40，温度为37℃，钙离子和磷酸根离子的浓度均为3.2×10-3M，防牙垢剂的组成以重量为基准计：
表A
防牙垢剂 组合物 分子量 剂量 抑制晶体生长时间
无 - - 0 3
AA 100 9，000 25 3
AA 100 9，000 55 4
AA 100 9，000 70 17
AA∶MAA∶t-BuAm 60∶20∶20 10，000 10 3
AA∶MAA∶t-BuAm 60∶20∶20 10，000 25 4
AA∶MAA∶t-BuAm 60∶20∶20 10，000 55 58
AA∶MAA∶t-BuAm 60∶20∶20 10，000 60 135
AA∶MAA∶t-BuAm 60∶20∶20 10，000 70 600+
AA∶MAA∶t-BuAm 60∶20∶20 10，000 100 1200+
ME∶MAn 50∶50 - 25 3
ME∶MAn 50∶50 - 55 3
ME∶MAn 50∶50 - 70 4
ME∶MAn 50∶50 - 150 4
AA∶t-BuAm 80∶20 3，000 55 68
AA∶t-BuAm 80∶20 6，000 55 25
AA∶MAA∶t-BuAm 60∶20∶20 10，000 55 58
AA 100 9，000 55 4
AA 100 5，100 55 45
AA 100 11，000 55 5
AA 100 60，000 55 3
AA∶t-BuAm 90∶10 6，000 55 55
AA∶t-BuAm 80∶20 6，000 55 25
AA∶t-BuAm 60∶40 6，000 55 25
AA∶AMPS 80∶20 10，000 55 17
AA∶AMPS 51∶49 10，000 55 45
AA∶AMPS 10∶90 10，000 55 8
AA 100 6，000 55 22
AA 100 9，000 55 4
AA∶EA 80∶20 6，000 55 64
AA∶EoTgA 80∶20 6，000 55 60
AA∶MMA 80∶20 10，000 55 37
AA∶DMI 80∶20 10，000 55 45
AA∶DEI 70∶30 10，000 55 25
AA∶SSS 70∶30 5，000 55 18
AA∶HPA 63∶37 7，000 55 48
AA∶Am 45∶55 6，000 55 10
AA∶DmAm 60∶40 6，000 55 60
AA∶t-BuAm 60∶40 6，000 55 25
AA∶AMPS 51∶49 10，000 55 45
AA∶COPS 70∶30 10，000 55 15
AA∶SEM 80∶20 10，000 55 55
AA∶SPM 80∶20 10，000 55 47
AA∶MAA∶EMA 60∶20∶20 10，000 55 38
AA∶AMPS∶EMA 60∶20∶20 10，000 55 43
AA∶AMPS∶HPA 60∶10∶30 7，000 55 40
AA∶AMPS∶t-BuAm 60∶20∶20 10，000 55 55
AA∶MAA∶CHPM 60∶20∶20 6，000 55 40
AA∶MAA∶t-oAm 60∶30∶10 10，000 55 40
AA∶SSS∶SEM 60∶20∶20 10，000 55 13
AA∶AMPS∶Am 60∶20∶20 10，000 55 54
AA∶AMPS∶SSS 60∶30∶10 10，000 55 23
AA∶AMPS∶SSS 60∶30∶10 12，000 55 28
AA∶MAA∶Am∶CA 54∶21∶9∶16 10，000 55 47
MA 100 500 55 240
AA∶MA 30
AA∶VAc 80∶20 10，000 55 25
AA∶VOH 80∶20 10，000 55 14
AA∶VAc∶AMPS 50∶20∶30 10，000 55 17
AA∶VOH∶AMPS 50∶20∶30 10，000 55 12
AA∶MAA∶t-BuAm 60∶20∶20 40，000 55 87
AA∶MAA∶Am∶CA 54∶21∶9∶16 6，000 55 60
AA∶MAA∶Am∶CA 54∶21∶9∶16 10，000 55 47
AA∶MAA∶Am∶CA 54∶21∶9∶16 19，000 55 38
AA 100 6，000 55 22
AA 100 2，100 55 100
表A中的缩略词含义如下：
AA＝丙烯酸
ME∶MAn＝甲氧乙烯∶马来酸酐
t-Bo Am＝叔丁基丙烯酰胺
MAA＝异丁烯酸
HPA＝羟基丙基丙烯酸盐（或酯）
AMPS＝2-丙烯酰氨基-2-甲基丙烷磺酸
CA＝2-（2-乙氧乙氧基）乙基丙烯酸酯
Am＝丙烯酰胺
EA＝丙烯酸乙酯
Eo Tg A＝乙氧基三甘醇丙烯酸酯
MMA＝异丁烯酸甲酯
DMI＝衣康酸二甲酯
DEI＝衣康酸二乙酯
IA＝衣康酸
SSS＝苯乙烯磺酸钠
DMA＝丙烯酸二甲酯
COP＝3-烯丙氧基-3-羟基丙烷磺酸酯
SEM＝2-磺基乙基异丁烯酸酯
SPM＝3-磺基丙基异丁烯酸酯
EMA＝异丁烯酸乙酯
CHPM＝氯代羟基丙基异丁烯酸酯
t-OAm＝叔辛基丙烯酸胺
MA＝马来酸酐
AA∶MA＝丙烯酸∶马来酸酐
（Belclene 283，Ciba-Geigy 产品）
VAc＝乙酸乙烯酯
VOH＝乙烯醇
SPA＝3-磺基丙基异丙烯酸酯
SPI＝双-3-磺基丙基衣康酸酯
Me OEA＝甲氧乙基丙烯酸酯
上述实验用的甲氧乙烯和马来酸酐的共聚物为Gantrez S-97树脂。标注“晶体生长抑制时间”的栏目表示羟磷灰石的晶体生长状况。
表A结果一般表示在没有酶存在时3-5个碳原子的单不饱和一元羧酸和二元羧酸，特别是丙烯酸、马来酸和衣康酸的均聚物和共聚物的防牙垢功效。晶体生长抑制时间超过10分钟即可，但在最佳实施方案中，要大于一个半小时左右。当然，可以通过增加剂量来延长抑制时间。
实例Ⅱ
在pH＝7.20、含12.5ppm焦磷酸的、2.5×10-3M三（羟基甲基）氨基甲烷盐酸的缓冲溶液25ml里进行酶水解。先将本发明防牙垢剂的已知量（0-100ppm）加入焦磷酸溶液中，再加入无机焦磷酸酶，在25℃连续搅拌3小时。然后用标准比色法分析正磷酸盐。用防牙垢剂抑制酶水解可按照下式计算：
酶水解抑制率＝ (（磷酸盐）c-（磷酸盐）a)/(（磷酸盐）c)
其中（磷酸盐）c和（磷酸盐）a分别代表没有和有防牙垢剂存在的正磷酸盐浓度。
没有防牙垢剂的三份实验结果表明酶水解期间产生的正磷酸盐量占可得正磷酸盐的95%以上。酶存在下防牙垢剂功效请见下面表B所列结果：
表B
防牙垢剂 组合物 分子量 剂量 酶水解抑制率
无 - - 0 0
Me∶MAn 50∶50 - 5 0
MeOE∶MA 50∶50 - 15 9
MeOE∶MA 50∶50 - 20 60
MeOE∶MA 50∶50 - 25 70
MEOE∶MA 50∶50 - 100 92
AA∶MAA∶t-BuAm 60∶20∶20 10，000 10 70
AA∶MAA∶t-BuAm 60∶20∶20 10，000 25 76
AA∶MAA∶t-BuAm 60∶20∶20 40，000 10 67
AA∶MAA∶t-BuAm 60∶20∶20 40，000 15 81
AA∶MAA∶t-BuAm 60∶20∶20 40，000 25 98
AA∶HPA 63∶37 7，000 10 47
AA∶HPA 63∶37 7，000 15 82
AA∶AMPS 51∶49 10，000 15 31
AA∶SPA 80∶20 10，000 15 83
AA∶DEI 70∶30 10，000 15 86
AA∶IA 50∶50 10，000 15 88
AA∶SPM 80∶20 10，000 15 90
AA∶AMPS∶HPA 60∶10∶30 10，000 15 76
AA∶AMPS∶EMA 60∶20∶20 10，000 15 59
AA∶AMPS∶t-BuAm 60∶20∶20 10，000 15 70
AA∶MA - - 15 56
AA∶SEM 80∶20 10，000 15 81
AA∶SPI 80∶20 10，000 15 87
AA;EoTgA 80∶20 6，000 15 80
AA∶EA 80∶20 6，000 15 79
AA∶AMPS∶SSS 60∶20∶20 10，000 15 76
AA∶VAc 80∶20 10，000 15 85
AA∶VOH 80∶20 10，000 15 86
AA∶AMPS∶VoAc 50∶30∶20 10，000 15 81
AA∶AMPS∶VoOH 50∶30∶20 10，000 15 87
MA 100 500 25 68
MA 100 500 15 51
MA∶SSS - - 15 49
AA∶t-BuAm 80∶20 3，000 15 67
AA∶t-BuAm 80∶20 6，000 15 81
AA∶DMAm 60∶40 6，000 15 79
AA∶MeOEA 80∶20 6，000 15 90
AA∶AMPS∶MeOEA 60∶20∶20 10，000 15 86
AA∶SSS 70∶30 5，000 15 94
AA∶COPS 70∶30 10，000 15 90
AA 100 2，100 15 79
AA 100 60，000 15 89
IA 100 10，000 15 92
表B数据说明这些均聚物和共聚物具有抑制焦磷酸盐酶水解的功效。这些数据还表明本发明防牙垢剂比现有技术甲氧乙烯：马来酸酐树脂（Gantrez S-97）具备优越的性能。
表B中IA代表衣康酸，MA∶SSS代表被称为Versa TL-7的National Starch Corporation（国家淀粉公司）产品，该产品被认定是马来酸酐和苯乙烯磺酸钠的共聚物。其余缩略词含义同表A。
实例Ⅲ
用上述实例Ⅰ中的pH稳定器方法对试管中羟磷灰石的形成进行滴定分析。试验条件为：pH＝7.20，25℃，钙离子和磷酸盐离子浓度全都是3.85∶10-3M。在唾液酶，即焦磷酸酶，和防牙垢剂存在条件下的实验结果列于下表C：
表C
防牙垢剂 分子量 剂量 焦磷酸盐 焦磷酸酶 晶体生长
组合物 （ppm） 抑制时间
（分钟）
无 - - 无 无 12
无 - - 有 无 30
无 - - 有 有 11
MEMA 70，000 35 有 有 12
（50/50）
AA∶MAA∶t-BuAm 10，000 35 有 有 ＞400
（60∶20∶20）
表C结果表明焦磷酸盐可有效地延迟羟磷灰石（HAP）的形成。焦磷酸盐用量为25ppm。然而，在没有防牙垢剂聚合物的存在下，由于酶的作用焦磷酸盐的功效大幅度降低，因延迟HAP形成时间明显缩短。功效降低是因为P-O-P键的酶水解。上表说明，本发明聚合物组合物是有效的防牙垢剂，特别是在焦磷酸盐和唾液酶都存在的情况下，正如表A和表B中所表明的，其它共聚物在唾液酶和焦磷酸盐存在条件下作为HAP晶体生长抑制剂将是有效的。
Claims (17)
1、含下列物质的口用组合物：
(a)一有效量的氟化物辕；
(b)有效量的牙磨剂；
(c)0.01-10%(wt)的防牙垢剂，选自3-5个碳原子的单不饱和一元和二元羧酸、其盐和酐的均聚物，选自含有至少30%(wt)上述羧酸单体的共聚物以及这些防牙垢剂的混合物。
2、权利要求1的组合物，其中至少一种所述共聚物的共聚用单体选自丙烯酰胺、烷基丙烯酸酯、烷基衣康酸酯、乙烯基磺酸、羟烷基丙烯酸酯、烷氧烷基丙烯酸酯、低级烯基羧酸酯、苯乙烯磺酸、烯丙氧基羟基烷烃磺酸、丙烯酰氨基烷烃磺酸、膦酰基烷烃羧酸、磺基烷基丙烯酸酯、及其盐和酐，和这些共聚用单体的混合物。
3、权利要求2的组合物，其中所述氟化物源的量占所述口用组合物的0.005-3.0%（wt.），其中所述羧基单体占所述共聚物的40-90%，这里所述均聚物和共聚物的分子量大约为400-100，000。
4、权利要求3的组合物，其中所述共聚物含有60-10%至少一种所述共聚物单体，其中所述氟化物源的量约为0.05-1%，所述防牙垢剂的量为0.1-5%。
5、权利要求5的组合物，其中所述羧基单体选自丙烯酸、异丁烯酸、衣康酸、马来酸及其酐、柠康酸、中康酸、这些酸的盐、及其混合物;其中丙烯酰胺结构式如下：
其中R选自氢和甲基;R1和R2分别选自氢和1至12个碳原子的烷基;其中烷基丙烯酸酯结构式如下：
其中R选自氢和甲基，R1选自C1-6烷基和R1被定义为R2即C1-6烷基的取代烷基;Y选自SO3X、-COR3和-CO2X，其中X选自氢、碱金属、碱土金属及铵基;R3选自C1-3烷基;其中的烷基衣康酸酯结构式如下：
其中R2和R3分别选自氢和C1-4烷基，我们主张R2和R3不同时为氢，虽然R2或R3都可以是氢;其中的乙烯基磺酸及其盐的结构分子式如下：
其中X选自氢、碱金属、碱土金属及铵离子;其中的羟烷基丙烯酸酯分子式如下：
其中R选自氢和C1-3烷基，R1选自C2-4亚烷基，n为1-5;其中的烷氧烷基丙烯酸酯结构式如下：
其中R选自氢和甲基，R1选自C2-4亚烷基，R2选自C1-10烷基，n为1-5;其中的低级烯基羧酸酯的结构式如下：
其中R是氢或低级C1-6烷基，R1选自C1-12烷基;其中的乙烯醇结构式如下：
其中R是氢或低级C1-6烷基;其中的苯乙烯磺酸及其盐的分子式如下：
其中R选自氢和C1-6烷基，X选自氢、碱金属、碱土金属和铵离子;其中的烯丙氧基羟磺酸及其盐的结构式如下：
其中R和R1分别选自氢和甲基，X选自氢、碱金属，碱土金属和铵离子;其中的丙烯酰氨基烷烃磺酸及其盐的结构式如下：
其中R选自氢和甲基，R1和R2分别选自氢和C1-4烷基，X选自氢、碱金属、碱土金属和铵离子;其中的磺基烷基丙烯酸酯结构式如下：
其中R1选自氢、甲基、和如下结构式的基团：
其中R2选自C1-12亚烷基，X选自氢、碱金属、碱土金属和铵离子。
6、权利要求5的组合物，其中所述的丙烯酰胺;R1或R2不全是氢;其中所述的烷基丙烯酸酯，R1选自不饱和C1-4烷基;其中所述的烷基衣康酸酯，R2和R3分别选自不饱和C1-4烷基;其中所述的磺酸及其盐，X选自碱金属和铵离子;其中所述的羟烷基丙烯酸酯，R选自氢和甲基，R1选自C2-3亚烷基;其中所述的烷氧烷基丙烯酸酯，R1选自C2-3亚烷基，R2选自C1-4烷基;n为1-3;其中所述的苯乙烯磺酸及其盐，R是氢，X选自氢、铵和碱金属离子，所述-SO3X基团位于所述苯环的3或4位置上;其中所述的丙烯酰氨基烷烃磺酸及其盐，R为氢，R1和R2分别选自C1-3烷基;其中所述的磺基烷基丙烯酸酯，R2选自C2-4亚烷基，X选自氢、钠、钾、钙、镁和铵离子。
7、权利要求6的能有效地抑制牙垢生成的，pH为6-10的组合物，其中所述氟化物源用量足以提供大约50ppm到大约2，500ppm的氟化物离子;其中所述防牙垢剂用课?-1000ppm;其中所述牙磨剂的用量为10-70%;其中所述组合物还包括一口用媒介物。
8、权利要求7的组合物，其中所述磨擦剂为0.1-7%（wt.）的多磷酸盐，选自六偏磷酸碱金属盐、三聚磷酸碱金属盐、二碱金属二酸、三碱金属一酸、三聚磷酸碱金属盐、四碱金属焦磷酸盐、乙基乙烷二磷酸、及其混合物。
9、权利要求6的组合物，其中所述的防牙垢剂量为1-5%。所述的共聚防牙垢剂的分子量从2，000到20，000，所述的单不饱和羧酸选自丙烯酸、异丁烯酸、马来酸或其酐、衣康酸、以及它们的混合物。
10、权利要求9的组合物，其中所述的防牙垢剂选自下列共聚物：
（a）AA∶MAA∶t-Bu Am的60∶20∶20共聚物
（b）AA∶HPA的63∶37共聚物
（c）AA∶AMPS的51∶49共聚物
（d）100马来酸的均聚物
（e）100丙烯酸的均聚物
其中使用的缩略词含义如下：
AA＝丙烯酸
MAA＝异丁烯酸
HPS＝羟丙基丙烯酸酯
AMPS＝2-丙烯酰氨基-2-甲基丙烷磺酸
11、以牙膏形式存在的权利要求5的组合物，其中所述的氟化物源选自氟化钠、氟化亚锡、一氟磷酸钠、及其混合物;所述牙磨剂的用量为10-75%，所述牙磨剂选自硅石、水合铝、不溶性偏磷酸盐、热固性聚合树脂、及其混合物;所述口用煤介物的用量为10-90%（wt.）。
12、抑制牙垢形成的方法，其中包括将权利要求1所述的组合物施用于口腔。
13、抑制牙垢形成的方法，其中包括将权利要求3所述的组合物施用于口腔。
14、抑制牙垢形成的方法，其中包括将权利要求4所述的组合物施用于牙齿。
15、抑制牙垢形成的方法，其中包括将权利要求5所述的组合物施用于牙齿。
16、抑制牙垢形成的方法，其中包括将权利要求7所述的组合物施用于牙齿。
17、抑制牙垢形成的方法，其中包括将权利要求11所述的组合物施用于牙齿。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/135,803 US4842847A (en) | 1987-12-21 | 1987-12-21 | Dental calculus inhibiting compositions |
| US135,803 | 1987-12-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1034667A true CN1034667A (zh) | 1989-08-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88108695A Pending CN1034667A (zh) | 1987-12-21 | 1988-12-17 | 防治牙垢的组合物 |
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| US (1) | US4842847A (zh) |
| EP (1) | EP0321650A1 (zh) |
| JP (1) | JPH01172316A (zh) |
| KR (1) | KR890009366A (zh) |
| CN (1) | CN1034667A (zh) |
| AU (1) | AU2092988A (zh) |
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| US4272513A (en) * | 1980-01-31 | 1981-06-09 | Colgate-Palmolive Company | Stabilized oral composition |
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| EP0092929B2 (en) * | 1982-04-20 | 1991-05-02 | Beecham Group Plc | Oral hygiene compositions |
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| US4436721A (en) * | 1983-06-08 | 1984-03-13 | Colgate-Palmolive Company | Oral composition having mole ratio of tetra (methylene phosphonate) to alkali metal fluoride of at least 1.4:1 |
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-
1987
- 1987-12-21 US US07/135,803 patent/US4842847A/en not_active Expired - Fee Related
-
1988
- 1988-08-13 EP EP88113194A patent/EP0321650A1/en not_active Withdrawn
- 1988-08-15 ZA ZA886021A patent/ZA886021B/xx unknown
- 1988-08-15 AU AU20929/88A patent/AU2092988A/en not_active Abandoned
- 1988-08-22 JP JP63206498A patent/JPH01172316A/ja active Pending
- 1988-09-28 PT PT88612A patent/PT88612A/pt unknown
- 1988-10-07 KR KR1019880013073A patent/KR890009366A/ko not_active Application Discontinuation
- 1988-12-17 CN CN88108695A patent/CN1034667A/zh active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103200841A (zh) * | 2010-11-05 | 2013-07-10 | 宝洁公司 | 口腔护理施用装置 |
| CN103200841B (zh) * | 2010-11-05 | 2016-08-10 | 宝洁公司 | 口腔护理施用装置 |
| CN105358128A (zh) * | 2013-07-18 | 2016-02-24 | 狮王株式会社 | 口腔生物膜除去剂以及口腔用组合物 |
| CN105358128B (zh) * | 2013-07-18 | 2019-03-01 | 狮王株式会社 | 口腔生物膜除去剂以及口腔用组合物 |
| CN106413813A (zh) * | 2013-12-20 | 2017-02-15 | 高露洁-棕榄公司 | 口腔护理组合物和方法 |
| CN106413813B (zh) * | 2013-12-20 | 2020-11-03 | 高露洁-棕榄公司 | 口腔护理组合物和方法 |
| CN107847402A (zh) * | 2015-07-28 | 2018-03-27 | 宝洁公司 | 含有amps聚合物、共聚物或交联聚合物的口腔护理组合物 |
| CN111714410A (zh) * | 2019-12-27 | 2020-09-29 | 杭州薄尔道格科技有限公司 | 一种非磷酸体系的口腔护理组合物及其制备方法 |
| CN113045698A (zh) * | 2019-12-27 | 2021-06-29 | 黄石市森尔新型材料有限公司 | 一种两性离子聚合物及其制备方法、用途 |
| CN111714410B (zh) * | 2019-12-27 | 2024-01-05 | 杭州奥菲生物科技有限公司 | 一种非磷酸体系的口腔护理组合物及其制备方法 |
| CN113045698B (zh) * | 2019-12-27 | 2024-02-06 | 黄石市森尔新型材料有限公司 | 一种两性离子聚合物及其制备方法、用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| PT88612A (pt) | 1989-07-31 |
| ZA886021B (en) | 1989-07-26 |
| US4842847A (en) | 1989-06-27 |
| KR890009366A (ko) | 1989-08-01 |
| AU2092988A (en) | 1989-06-22 |
| EP0321650A1 (en) | 1989-06-28 |
| JPH01172316A (ja) | 1989-07-07 |
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