WO1982004259A1 - Fluorine containing dental materials - Google Patents
Fluorine containing dental materials Download PDFInfo
- Publication number
- WO1982004259A1 WO1982004259A1 PCT/US1982/000695 US8200695W WO8204259A1 WO 1982004259 A1 WO1982004259 A1 WO 1982004259A1 US 8200695 W US8200695 W US 8200695W WO 8204259 A1 WO8204259 A1 WO 8204259A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dental
- group
- substituted
- lewis base
- amine
- Prior art date
Links
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims description 26
- 239000011737 fluorine Substances 0.000 title claims description 26
- 239000005548 dental material Substances 0.000 title description 10
- 239000000463 material Substances 0.000 claims abstract description 75
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 208000002925 dental caries Diseases 0.000 claims abstract description 10
- 239000000068 pit and fissure sealant Substances 0.000 claims abstract description 9
- 230000007505 plaque formation Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000002879 Lewis base Substances 0.000 claims description 50
- 239000011350 dental composite resin Substances 0.000 claims description 36
- 150000007527 lewis bases Chemical class 0.000 claims description 35
- 239000002841 Lewis acid Substances 0.000 claims description 34
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 29
- -1 carboxyl amine Chemical class 0.000 claims description 29
- 150000007517 lewis acids Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 125000001931 aliphatic group Chemical group 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 229920006395 saturated elastomer Polymers 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 17
- 229910015900 BF3 Inorganic materials 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 150000003512 tertiary amines Chemical class 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000805 composite resin Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003335 secondary amines Chemical class 0.000 claims description 9
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical group CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 229940086542 triethylamine Drugs 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000000248 cariostatic effect Effects 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229920003180 amino resin Polymers 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003673 urethanes Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 6
- 239000002253 acid Substances 0.000 claims 3
- 150000007513 acids Chemical class 0.000 claims 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims 2
- 239000002952 polymeric resin Substances 0.000 claims 2
- 229920003002 synthetic resin Polymers 0.000 claims 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 125000004103 aminoalkyl group Chemical group 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000011797 cavity material Substances 0.000 claims 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical group CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
- 238000011049 filling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 239000003469 silicate cement Substances 0.000 description 9
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 8
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- VDMLVOIDGSOUTA-UHFFFAOYSA-N 2-(4-methylanilino)ethane-1,1-diol Chemical compound CC1=CC=C(NCC(O)O)C=C1 VDMLVOIDGSOUTA-UHFFFAOYSA-N 0.000 description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003479 dental cement Substances 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
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- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RGXCTRIQQODGIZ-UHFFFAOYSA-O isodesmosine Chemical compound OC(=O)C(N)CCCC[N+]1=CC(CCC(N)C(O)=O)=CC(CCC(N)C(O)=O)=C1CCCC(N)C(O)=O RGXCTRIQQODGIZ-UHFFFAOYSA-O 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- HAOYOWVFKDKJMI-UHFFFAOYSA-N 2-(2-methylpropyl)pent-2-enoic acid Chemical compound CCC=C(C(O)=O)CC(C)C HAOYOWVFKDKJMI-UHFFFAOYSA-N 0.000 description 1
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- VEOIOMOZIIRJHV-UHFFFAOYSA-N 2-ethoxyhexyl prop-2-enoate Chemical compound CCCCC(OCC)COC(=O)C=C VEOIOMOZIIRJHV-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
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- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical class CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- ZFMZSZMUFWRAOG-UHFFFAOYSA-N 3-methoxy-n-methylaniline Chemical compound CNC1=CC=CC(OC)=C1 ZFMZSZMUFWRAOG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
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- 229910021620 Indium(III) fluoride Inorganic materials 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
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- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
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- 210000004513 dentition Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MVJMLDCCPRMJFY-UHFFFAOYSA-N ethanol;3-methylaniline Chemical compound CCO.CCO.CC1=CC=CC(N)=C1 MVJMLDCCPRMJFY-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical class CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- WXXZSFJVAMRMPV-UHFFFAOYSA-K gallium(iii) fluoride Chemical compound F[Ga](F)F WXXZSFJVAMRMPV-UHFFFAOYSA-K 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical class O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012948 isocyanate Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GDHRQDYGUDOEIZ-UHFFFAOYSA-N n,n,2-trimethylpropan-1-amine Chemical compound CC(C)CN(C)C GDHRQDYGUDOEIZ-UHFFFAOYSA-N 0.000 description 1
- QEFRGRRBNLTXGD-UHFFFAOYSA-N n,n,n',n'-tetrakis(2-methylpropyl)octane-1,8-diamine Chemical compound CC(C)CN(CC(C)C)CCCCCCCCN(CC(C)C)CC(C)C QEFRGRRBNLTXGD-UHFFFAOYSA-N 0.000 description 1
- GCDQTHZYCHESCJ-UHFFFAOYSA-N n,n,n',n'-tetraphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1N(C=1C=CC=CC=1)CCN(C=1C=CC=CC=1)C1=CC=CC=C1 GCDQTHZYCHESCJ-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- DBIJGSRXWPQTLH-UHFFFAOYSA-N n-butyloctan-1-amine Chemical compound CCCCCCCCNCCCC DBIJGSRXWPQTLH-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- AASABFUMCBTXRL-UHFFFAOYSA-N n-ethyl-4-methylaniline Chemical compound CCNC1=CC=C(C)C=C1 AASABFUMCBTXRL-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000007406 plaque accumulation Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/69—Medicaments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/889—Polycarboxylate cements; Glass ionomer cements
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
Definitions
- fluorine-containing additives that have been tried in dental restorations consist of inorganic fluoride salts, organic bases such as a ine hydrofluoride, fluorocarbons and fluoride-containing ion- exchange resins. These attempts to find suitable fluorine-containing additives which are both dispersed in dental restorative material and
- Silicate cements have demonstrated cariostatic release of fluoride; however, the strictly rapid surface release of fluoride from the cement, the dissolution of the cement in oral fluids, and the low tensile strengths of the cements are major disadvantages.
- a controlled, slow fluoride releasing additive comprising a Lewis base and a fluorine-containing Lewis acid which is therapeutic in preventing secondary caries and reducing plaque formation.
- This additive is incorporated into polymeric dental restorative material and is capable of migrating from the interior to the surface of said material without dissolution thereof and with consequent release of flouride.
- Lewis acid compounds containing covalently bound fluorine can be reacted with Lewis base compounds to produce addition compounds which are mixed with dental restorative materials and release fluoride ion.
- the flouride is released at a controlled rate . * by diffusion of the Lewis acid within said dental material with sub ⁇ sequent hydrolysis upon contact with water.
- the fluorine-containing Lewis acid - Lewis base addition compounds of the present invention can be added to dental restorative materials, denture base materials, orthodontic elastics, plastic dental materials, and dental resins. Alternatively, the addition compounds can be incorporated into the polymer matrix as part of the monomer resin constituents.
- the Lewis base compounds are dispersible or soluble within the dental restorative material; the Lewis acid compound must be mobile within the restorative material and capable of migrating to the surface of said material to release fluoride ion by dissociation with water at a controlled rate; and the resulting Lewis acid - Lewis base addition compound and its hydrolysis products must be non-toxic.
- the Lewis acid compounds used in this invention may be any covalently bound fluorine-containing compound with a vacant electron orbital which can be used to form a covalent bond with the electron pair of a base, yet which retains its mobility within the dental restorative material.
- fluorine-containing Lewis acid compounds are aluminum trifluoride, boron trifluoride, gallium trifluoride, titanium tetrafluoride and indium trifluoride. We have found that boron tri- . 5 fluoride works well in accordance with the present invention; thus it is the preferred fluorine-containing Lewis acid compound.
- Lewis base compounds in accordance with the present invention may be any compound having an available pair of electrons, either unshared
- the Lewis base compounds in accordance with this invention are primary amines having the formula h R-,), secondary amines having the formula HN(R,) 2 , tertiary amines having the formula N(R-.) 3 , ethers having the formula R- j OR,, esters having the
- R- j COOR- ketones having the formula R,C0R, , alcohols having the formula R-,0H, mercaptans, thioethers and thioesters, wherein R, is a hydroxyl, a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group, wherein the carbon chain length of these aliphatic
- 20 ⁇ groups is limited to the number of carbon atoms which produce a compound which is dispersible or soluble within a dental restorative material.
- a preferred chain length of the aliphatic group is from about 1 to about 18 carbon atoms. We have found that aliphatic chains containing from about 1 to about 12 carbon atoms operate most successfully in accordance 25 with this invention, and are thus most preferred.
- Lewis base compounds in accordance with the present invention are: butylamine, octylamine, dodecylamine, aniline, isobutyl amine, isooctylamine, isopropylamine, glycine, alanine, valine,
- 35 isobutylamine, ethylisooctyl mine, butylisopropyl mine, N-methyl- aniline, N-methyl-3-methoxyaniline, tri ethylamine, triethylamine, trioctylamine, tridodecylamine, dimethyloctyl mine, dibutyldodecyl ⁇ amine, triisobutylamine, triisoctylamine, triisopropylamine, dimethylisobutylamine, dibutylisoctylamine, tributeneamine, tri- ethanolamine, triisopropanolamine, triphenyl mine, methyldiphenyl- amine, octyldiphenylamine, pyridine, dimethylether, dibutylether, didodecylether, methylethylether, d iso:butylether, disopropylether, methylisobutylether,
- Additional Lewis base compounds in accordance with the present invention are a inoalkyls.
- the preferred Lewis base compounds in accordance with this invention are diamines having the formula:
- R- is a substituted or unsubstituted aromatic group, a hydroxyl group, hydrogen, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group having from about 1 to about 12 carbon atoms, and n is an integer having from about 1 to about 9 carbon atoms.
- the chain length of the alkylene group is limited to the number of carbon atoms which produce a compound which is dispersible or soluble within a dental restorative material. We have found that compounds having alkylene chains containing from about 1 to about 9 carbon atoms are preferred in accordance with this invention.
- Examples of diamines in accordance with the present invention are: N,N,N * ,N--tetramethylethylenediamine, N,N,N * ,N l --tetraoctylbutylene- diamine, N,N,N' ,N'-tetraisobutyloctylenediamine, N,N,N' ,N'-tetra- phenylethylenediamine, and N,N-dihydroxy-N' ,N'-diphenylethylene- dia ine.
- the preferred compound of the present invention is N,N,N'N'- tetramethylethylenediamine.
- the Lewis base components can be monomer resin constituents capable of becoming incorporated into the backbone, side chain, or crosslink of the polymeric dental material.
- monomer resin constituents include compounds having the formula: CH 2 * -C-R 3 R 2
- R « is hydrogen, or a cyano, or a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl; and R- is an esterified carboxyl, a primary amine, a secondary amine, a tertiary amine, a carboxyl amine as illustrated by acrylamide (ChLCHCONI- ), or an amine- containing ester having the formula:
- R. is a primary amine, a secondary amine, or a tertiary amine
- n is an integer representing from about 1 to about 18 and preferably from about 1 to 9 carbon atoms.
- monomer resin constituents in accordance with the present invention are: acrylic and methacrylic esters such as methylacry ate, ethylacrylate, propyl- acrylate, butylacrylate, 2-ethoxyhexylacrylate, methylmethacrylate, ethylmethacrylate, propyl ethacrylate, butylmethacrylate, lauryl- methacrylate, stearyl ethacrylate, ethylisobutylacrylate, butylene- dimethacrylate, and trimethylolpropane trimethacrylate; acrylonitrile; trimethylaminostyrene; polya ides such as acrylamide and ethacryl- a ide; polycyclamide constituents such as 1,4
- the fluorine-containing Lewis acid - Lewis base compounds are added to restorative dental mate ⁇ rials or are incorporated into polymer-based dental restorative materials as constituent resin components. In either case, the content of the fluorine-containing compound within the dental material should
- compositions containing up to about 50 wt % of the fluorine- containing Lewis acid - Lewis base addition compound do not adversely affect the physical properties of the dental materials and operate effectively in a controlled, slow-fluoride release composite.
- compositions having from about 0.5 to about 50 wt % of the fluorine- containing compounds are preferred in this invention. Concentrations as low as 0.05% wt flouride compounds can be effective in preventive dentistry.
- a more preferred range of compositions is from about 0.5 to about 25 wt % of the fluorine-containing compound.
- the most preferred compositions in accordance with this invention contain from about 0.5 to about 1.5 wt % of the fluorine-containing addition compounds. It should be noted, however, that the various dental materials used in accordance with thts invention will exhibit different physical characteristics when their respective formulations are modified, so that the quantity of the fluoride-containing compounds of this invention must be evaluated with each formulation.
- the dental restorative materials used in accordance with this invention include resin cements, dental prosthetic devices, denture base resins, cavity liners, composite resins, pit and fissure sealants, resin adhesives, repair materials, relining and rebasi ⁇ g dental mate ⁇ rials, orthodontic resins, orthodontic elastics, plastic orthodontic brackets, or any other such material used in restorative dental opera ⁇ tions.
- Presently employed dental restorative materials are fabricated from polymer-based materials, metals, ceramics, or combinations (composite) thereof.
- polymer-based materials in accordance with this invention include acrylic and methacrylic polymers, vinyl acrylic polymers, cyanoacrylates, polystyrene, polycarbonate, epoxy resins, nylons, vinyl styrenes, unsaturated polyesters, polyurethane, polyvinyl cetate-ethylene, silicones, polyvinylchlor de, copolymer formulations using these polymers, or modifications thereof which prove useful as dental materials.
- dental composites in accordance with this invention include glass ionom ⁇ r cements, acrylic composite restorative filling materials, Bis-GMA resin composites, acrylic restorative tooth liners, and urethane dimethacrylate composites.
- dental restorative materials in accordance with the present invention include restorative composite resins, cavity liners, adhesives, pit and fissure sealants, orthodontic resins, and denture base materials.
- the most preferred dental restorative materials are cavity liners, adhesives, sealants and denture base materials.
- Example 1 The following example describes the preparation and chemical characterization of the fluorine-containing Lewis acid - Lewis base compounds of the present invention and their use in dental restorative materials.
- DEAEMA diethyla inoethylmethacrylate
- the product prepared accordingly was determined to be the 1:1 adduct of DEAEMA and boron trifluoride (DEAEMA-BF 3 ) on the basis of infrared spectroscopy, thermogravimetric analysis, nuclear magnetic resonance spectroscopy and elemental analysis.
- DEAEMA-BF 3 boron trifluoride
- This material (DEAEMA-BF 3 ) was used in combination with other ethacrylate monomers to prepare a formulation suitable for composite restorative liner preparations according to the formulation below:
- the above material is polymerized by mixing 5 parts with 1 part of saturated (9%) benzoyl peroxide solution in dimethylphthalate. 0.1 gm samples of hardened material were stored in 10 ml of distilled water. The - fluoride content was measured periodically with an ion-specific elec ⁇ trode, and significant levels of fluoride were still being released after more than three months.
- the fluoride leach (ppm/day) was determined based upon a 0.01 gm application of the composite in contact with 0.1 ml of water.
- identical tests were run of films of a silico phosphate cement (Fluorothin) and a silicate cement (MQ). The results indicate that the experimental composite liner maintained a detectable release of fluoride over a longer period of time than the silicate cements, even though the silicate cements release larger amounts of fluoride during the initial part of the leach.
- Example 2 The following example describes an alternate method of preparing the fluorine-containing Lewis acid - Lewis base compounds of the present invention.
- a quantity of 37 gm of diethylaminoethylmethacrylate (DEAEMA) are placed in a three-neck round-bottom flask. Gaseous oxygen is bubbled in for one-half hour. After the oxygen flow is shut off, 26 gm of boron trifluoride methanol complex is placed in a dropping funnel. The funnel is mounted on top of the round-bottom flask in an ice water bath. The temperature is cooled to about 10° C. The boron trifluoride methanol is added dropwise while the mixture is stirred. Temperature is maintained between 15 - 25° C.
- DEAEMA diethylaminoethylmethacrylate
- Example 3 The following example describes the preparation and physical properties of a dental adhesive in accordance with this invention.
- the DEAEMA-BF 3 compound was prepared as in Example 1. This mate ⁇ rial was used in combination with other methacrylate monomers to pre- - pare a formulation suitable for orthodontic adhesive preparations. Equal amounts of solutions A and B, described below, are mixed together to form the desired adhesive:
- Cured discs of material measuring .015 to 0.050 inches thick and 1.5 inches in diameter were immersed in 50 ml portions of distilled water.
- the fluoride concentration of the exposed water was determined at measured intervals using a fluoride-specific ion electrode. After each determination, the water was discarded and replaced with an additional portion of distilled water. Rates of release have been determined to be 2 to 5 micrograms of fluoride per square centimeter per day. The samples thus studied have fluoride available for release for over one year.
- Example 4 The DEAEMA-BF- 3 adduct is prepared according to Example 1, and is used in combination with other methacrylate monomers to prepare a formulation suitable -for denture-base preparations according to the following composition:
- the liquid resin portion of a powder or liquid denture-base material is formulated by mixing 1 part of a solution con ⁇ taining 4 parts DEAEMA-BF 3 and 5 parts methyl ethacrylate containing 2% di ethyl-para-toluidine and 2 parts commercial denture-base powder (polymethylmethacrylate) to form test specimens and acrylic dental devices.
- the DEAEMA-BF 3 addition compound can be prepared according to Example 1 and used in combination with other methacrylate monomers to prepare a formulation suitable for pit and fissure sealant preparations according to the following composition: Equal amounts of solution A and solution B as described below can be mixed together to form a chemically cured pit and fissure sealant:
- Example 6 The DEAEMA-BF 3 addition compound was prepared as shown in Example 1 and used in combination with other methacrylate monomers to prepare a formulation suitable for composite restorative liner prepara- tions according to the following composition:
- the above material is polymerized by mixing 5 parts with 1 part of saturated 9% benzoyl peroxide solution in dimethylphthalate.
- 0.1 gm " samples of hardened material were stored in 10 ml of distilled water.
- the fluoride content was measured periodically with an ion-specific electrode and significant levels of fluoride were still being released after more than three months.
- identical tests were run of films of fluorothin, a silica phosphate cement, and MQ, a silicate cement. Results indicate that the experimental composite films . maintained a detectable release of fluoride over a longer period of time than the fluorothin and MQ films, even though the silica phosphate and silicate cements released larger amounts of fluoride during the initial part of the leach.
- Example 7 A quantity 15 gm N,N,N' ,N'-tetramethylethylenediam ne (TMED) are placed in a three-neck round-bottom flask. The flask is set into an ice bath to moderate reaction temperature. A vacuum is drawn on the reaction flask and gaseous boron trifluoride is bubbled at such a rate that the temperature does not exceed 35° C. The rate of bubbling is increased when the temperature begins to fall. The reaction is
- OMPI _ continued until the temperature no longer increases on increased boron trifluoride addition. This takes about one hour when the reaction product is collected and then purified by distillation using a molecular still.
- the resulting addition compound is used in combination with methacrylate monomers to prepare a formulation suitable for composite resin filling materials according to the formulation below:
- Example 8 The DEAEMA-BF 3 compound was prepared as shown in Example 1. This compound was then added to an experimental formulation of a composite restorative liner as shown below:
- Example 9 A composite restorative liner was prepared as shown in Example 6. Analysis of leaching of the fluorine-containing Lewis acid - Lewis base addition compound indicates that the boron content of the restorative liner leaching solution is much less than it should be if all the available boron is leached.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Birds (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dental Preparations (AREA)
Abstract
The composition is particularly adapted for use in the field of dentistry as a composite filling material, cavity liner, adhesive, orthodontic resin, pit and fissure sealant, and denture base material wherein the fluoride is released to prevent secondary caries and reduce plaque formation.
Description
FLUORINE-CONTAINING DENTAL MATERIALS
Background of the Invention
5 It is established that dental silicate cements containing fluoride are therapeutic in preventing secondary caries and reducing plaque formation. Present acrylic denture base material, restorative materials and adhesives have been shown to be sites of bacterial and plaque accumulation, which can be a precursor of irritation to soft 10 tissues and caries attack on remaining natural dentition. The release of fluoride ion from .these dental restorative materials occurs either by surface release, or by dissolution of the fluorine-containing additives or the dental restorative material itself with consequent migration of fluoride ions into the underlying tooth structure. 15 Various fluorine-containing additives that have been tried in dental restorations consist of inorganic fluoride salts, organic bases such as a ine hydrofluoride, fluorocarbons and fluoride-containing ion- exchange resins. These attempts to find suitable fluorine-containing additives which are both dispersed in dental restorative material and
20 capable of reducing tooth caries through controlled long-term fluoride release have failed. Silicate cements have demonstrated cariostatic release of fluoride; however, the strictly rapid surface release of fluoride from the cement, the dissolution of the cement in oral fluids, and the low tensile strengths of the cements are major disadvantages.
25 Alternatively, the fluoride incorporated into insoluble resin materials has been considered to be virtually incapable of leaking out, and thus *■ to be ineffective as a cariostatic agent. Studies by Forsten and Paunio s (Scandinavian Journal of Dental Research (1972) 80, 515-519) comparing fluoride release by silicate cements and composite resins have shown
30 that the overall release of fluoride from the two materials was comparable; however, the manner in which the fluoride was released from
the composite was not controlled. Heretofore it was difficult to obtain controlled, effective cariostatic and plaque-reducing fluoride release from virtually insoluble materials such as acrylic denture base materials, adhesives and composite resins, and the like.
Summary of the Invention In accordance with the present invention, we have discovered a controlled, slow fluoride releasing additive comprising a Lewis base and a fluorine-containing Lewis acid which is therapeutic in preventing secondary caries and reducing plaque formation. This additive is incorporated into polymeric dental restorative material and is capable of migrating from the interior to the surface of said material without dissolution thereof and with consequent release of flouride.
Detailed Description of the Invention
We have now found that Lewis acid compounds containing covalently bound fluorine can be reacted with Lewis base compounds to produce addition compounds which are mixed with dental restorative materials and release fluoride ion. The flouride is released at a controlled rate . * by diffusion of the Lewis acid within said dental material with sub¬ sequent hydrolysis upon contact with water. The fluorine-containing Lewis acid - Lewis base addition compounds of the present invention can be added to dental restorative materials, denture base materials, orthodontic elastics, plastic dental materials, and dental resins. Alternatively, the addition compounds can be incorporated into the polymer matrix as part of the monomer resin constituents. The principal requirements of these compounds are that the Lewis base compounds are dispersible or soluble within the dental restorative material; the Lewis acid compound must be mobile within the restorative material and capable of migrating to the surface of said material to release fluoride ion by dissociation with water at a controlled rate; and the resulting Lewis acid - Lewis base addition compound and its hydrolysis products must be non-toxic.
The Lewis acid compounds used in this invention may be any covalently bound fluorine-containing compound with a vacant electron orbital which can be used to form a covalent bond with the electron pair
of a base, yet which retains its mobility within the dental restorative material. Examples of fluorine-containing Lewis acid compounds are aluminum trifluoride, boron trifluoride, gallium trifluoride, titanium tetrafluoride and indium trifluoride. We have found that boron tri- . 5 fluoride works well in accordance with the present invention; thus it is the preferred fluorine-containing Lewis acid compound.
Lewis base compounds in accordance with the present invention may be any compound having an available pair of electrons, either unshared
10 or in a π-electron orbital, which is dispersible or soluble within the dental restorative material. The Lewis base compounds in accordance with this invention are primary amines having the formula h R-,), secondary amines having the formula HN(R,)2, tertiary amines having the formula N(R-.)3, ethers having the formula R-jOR,, esters having the
15 formula R-jCOOR-, , ketones having the formula R,C0R, , alcohols having the formula R-,0H, mercaptans, thioethers and thioesters, wherein R, is a hydroxyl, a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group, wherein the carbon chain length of these aliphatic
20 ■ groups is limited to the number of carbon atoms which produce a compound which is dispersible or soluble within a dental restorative material. A preferred chain length of the aliphatic group is from about 1 to about 18 carbon atoms. We have found that aliphatic chains containing from about 1 to about 12 carbon atoms operate most successfully in accordance 25 with this invention, and are thus most preferred.
Examples of Lewis base compounds in accordance with the present invention are: butylamine, octylamine, dodecylamine, aniline, isobutyl amine, isooctylamine, isopropylamine, glycine, alanine, valine,
30 hydroxylamine, tryptophan, aspartic acid, n-amino-1-butene, n-amino-2- octene, ethanolamine, octanolamine, dodecanolamine, 3-methoxyan line, dimethylamine, dibutyla ine, dioctylamine, didodecylamine, methyl- ethylamine, methylbutylamine, butyloctylamine, octyldodecylamine, methylhydroxylamine, butylethanolamine, octyldodecanolamine, methyl-
35 isobutylamine, ethylisooctyl mine, butylisopropyl mine, N-methyl- aniline, N-methyl-3-methoxyaniline, tri ethylamine, triethylamine, trioctylamine, tridodecylamine, dimethyloctyl mine, dibutyldodecyl¬ amine, triisobutylamine, triisoctylamine, triisopropylamine,
dimethylisobutylamine, dibutylisoctylamine, tributeneamine, tri- ethanolamine, triisopropanolamine, triphenyl mine, methyldiphenyl- amine, octyldiphenylamine, pyridine, dimethylether, dibutylether, didodecylether, methylethylether, d iso:butylether, disopropylether, methylisobutylether, butylisoctylether, octyl sododecylether, diphenylether and ethyl acetate. A preferred Lewis base compound in accordance with this invention is triethylamine.
Additional Lewis base compounds in accordance with the present invention are a inoalkyls. The preferred Lewis base compounds in accordance with this invention are diamines having the formula:
* wherein R-, is a substituted or unsubstituted aromatic group, a hydroxyl group, hydrogen, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group having from about 1 to about 12 carbon atoms, and n is an integer having from about 1 to about 9 carbon atoms. The chain length of the alkylene group is limited to the number of carbon atoms which produce a compound which is dispersible or soluble within a dental restorative material. We have found that compounds having alkylene chains containing from about 1 to about 9 carbon atoms are preferred in accordance with this invention. Examples of diamines in accordance with the present invention are: N,N,N*,N--tetramethylethylenediamine, N,N,N*,Nl--tetraoctylbutylene- diamine, N,N,N' ,N'-tetraisobutyloctylenediamine, N,N,N' ,N'-tetra- phenylethylenediamine, and N,N-dihydroxy-N' ,N'-diphenylethylene- dia ine. The preferred compound of the present invention is N,N,N'N'- tetramethylethylenediamine.
In an alternative embodiment of this invention, the Lewis base components can be monomer resin constituents capable of becoming incorporated into the backbone, side chain, or crosslink of the polymeric dental material. In accordance with this invention, examples of monomer resin constituents include compounds having the formula:
CH2 *-C-R3 R2
wherein R« is hydrogen, or a cyano, or a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl; and R- is an esterified carboxyl, a primary amine, a secondary amine, a tertiary amine, a carboxyl amine as illustrated by acrylamide (ChLCHCONI- ), or an amine- containing ester having the formula:
wherein R. is a primary amine, a secondary amine, or a tertiary amine, and n is an integer representing from about 1 to about 18 and preferably from about 1 to 9 carbon atoms. Examples of monomer resin constituents in accordance with the present invention are: acrylic and methacrylic esters such as methylacry ate, ethylacrylate, propyl- acrylate, butylacrylate, 2-ethoxyhexylacrylate, methylmethacrylate, ethylmethacrylate, propyl ethacrylate, butylmethacrylate, lauryl- methacrylate, stearyl ethacrylate, ethylisobutylacrylate, butylene- dimethacrylate, and trimethylolpropane trimethacrylate; acrylonitrile; trimethylaminostyrene; polya ides such as acrylamide and ethacryl- a ide; polycyclamide constituents such as 1,4-cyclohexane bis (methylamine); amino resins such as carbamide, melamine, thiocarbamide, aniline, dicyanodia ide, toluenesulfonamide, benzoguanamine, ethylene urea; urethanes, epoxies, polyesters, polycarbonates, and isocyanate derivatives such as toluene diisocyanate and diphenyl methane diiso- cyanate. A preferred Lewis base monomer resin component of this invention is diethylaminoethylmethacrylate (DEAEMA).
In accordance with the present invention, the fluorine-containing Lewis acid - Lewis base compounds are added to restorative dental mate¬ rials or are incorporated into polymer-based dental restorative materials as constituent resin components. In either case, the content of the fluorine-containing compound within the dental material should
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be limited so as not to interfere with the physical properties of the material. In addition, the content of the fluorine-containing com¬ pound should be high enough to effectively release fluoride ion and reduce tooth caries in a controlled sustained manner over a long period of time. Compositions containing up to about 50 wt % of the fluorine- containing Lewis acid - Lewis base addition compound, do not adversely affect the physical properties of the dental materials and operate effectively in a controlled, slow-fluoride release composite. Thus, compositions having from about 0.5 to about 50 wt % of the fluorine- containing compounds are preferred in this invention. Concentrations as low as 0.05% wt flouride compounds can be effective in preventive dentistry. A more preferred range of compositions is from about 0.5 to about 25 wt % of the fluorine-containing compound. The most preferred compositions in accordance with this invention contain from about 0.5 to about 1.5 wt % of the fluorine-containing addition compounds. It should be noted, however, that the various dental materials used in accordance with thts invention will exhibit different physical characteristics when their respective formulations are modified, so that the quantity of the fluoride-containing compounds of this invention must be evaluated with each formulation.
The dental restorative materials used in accordance with this invention include resin cements, dental prosthetic devices, denture base resins, cavity liners, composite resins, pit and fissure sealants, resin adhesives, repair materials, relining and rebasiπg dental mate¬ rials, orthodontic resins, orthodontic elastics, plastic orthodontic brackets, or any other such material used in restorative dental opera¬ tions. Presently employed dental restorative materials are fabricated from polymer-based materials, metals, ceramics, or combinations (composite) thereof. Examples of polymer-based materials in accordance with this invention include acrylic and methacrylic polymers, vinyl acrylic polymers, cyanoacrylates, polystyrene, polycarbonate, epoxy resins, nylons, vinyl styrenes, unsaturated polyesters, polyurethane, polyvinyl cetate-ethylene, silicones, polyvinylchlor de, copolymer formulations using these polymers, or modifications thereof which prove useful as dental materials. Examples of dental composites in accordance with this invention include glass ionomεr cements, acrylic
composite restorative filling materials, Bis-GMA resin composites, acrylic restorative tooth liners, and urethane dimethacrylate composites. A discussion of dental restorative materials and their composition, application, and properties can be found in Restorative Dental Materials, by Robert G. Craig, published by the C.V. Mosby Publishing Company, 1980, incorporated herein by reference. Preferred dental restorative materials in accordance with the present invention include restorative composite resins, cavity liners, adhesives, pit and fissure sealants, orthodontic resins, and denture base materials. The most preferred dental restorative materials are cavity liners, adhesives, sealants and denture base materials.
The following examples describe certain representative embodi¬ ments of this invention as set forth above. They are to be illustrative only and are not intended to limit the scope of the invention.
Example 1 The following example describes the preparation and chemical characterization of the fluorine-containing Lewis acid - Lewis base compounds of the present invention and their use in dental restorative materials.
A quantity of 25 g diethyla inoethylmethacrylate (DEAEMA) are placed in a three-neck round-bottom flask. The flask is set into an ice bath to moderate reaction temperature. A vacuum is drawn on the reaction flask and gaseous boron trifluoride is bubbled into the DEAEMA at such a rate that the temperature does not exceed 35° C. The rate of bubbling is increased when the temperature begins to fall. The reaction is continued until the temperature no longer increases on increased boron trifluoride addition. This takes about one hour, when the reac¬ tion product is collected and then purified by distillation using a • molecular still. The product prepared accordingly was determined to be the 1:1 adduct of DEAEMA and boron trifluoride (DEAEMA-BF3) on the basis of infrared spectroscopy, thermogravimetric analysis, nuclear magnetic resonance spectroscopy and elemental analysis. The corresponding structure is shown below:
This material (DEAEMA-BF3) was used in combination with other ethacrylate monomers to prepare a formulation suitable for composite restorative liner preparations according to the formulation below:
35 parts Bis-GMA (reaction product of methacrylic acid and the diglycidyl ether of bisphenol A)
30 parts ethyleneglycoldi ethacryl te
30 parts trimethylolpropanetrimethacrylate
5 parts DEAEMA-BF3 1 part dihydroxyethyl-para-tolylamine
. The above material is polymerized by mixing 5 parts with 1 part of saturated (9%) benzoyl peroxide solution in dimethylphthalate. 0.1 gm samples of hardened material were stored in 10 ml of distilled water.The - fluoride content was measured periodically with an ion-specific elec¬ trode, and significant levels of fluoride were still being released after more than three months.
Additionally, the fluoride leach (ppm/day) was determined based upon a 0.01 gm application of the composite in contact with 0.1 ml of water. For comparison, identical tests were run of films of a silico phosphate cement (Fluorothin) and a silicate cement (MQ). The results indicate that the experimental composite liner maintained a detectable release of fluoride over a longer period of time than the silicate cements, even though the silicate cements release larger amounts of fluoride during the initial part of the leach.
Example 2 The following example describes an alternate method of preparing the fluorine-containing Lewis acid - Lewis base compounds of the present invention.
A quantity of 37 gm of diethylaminoethylmethacrylate (DEAEMA) are placed in a three-neck round-bottom flask. Gaseous oxygen is bubbled in for one-half hour. After the oxygen flow is shut off, 26 gm of boron trifluoride methanol complex is placed in a dropping funnel. The funnel is mounted on top of the round-bottom flask in an ice water bath. The temperature is cooled to about 10° C. The boron trifluoride methanol is added dropwise while the mixture is stirred. Temperature is maintained between 15 - 25° C. by adjustment of addition of the boron trifluoride methanol material. Complete addition requires 20 to 30 minutes. Next, the oxygen flow is resumed to bubble off methanol and unreacted mate¬ rials. After four hours material is collected and weighed. The yield is 49 gm.
Example 3 The following example describes the preparation and physical properties of a dental adhesive in accordance with this invention.
The DEAEMA-BF3 compound was prepared as in Example 1. This mate¬ rial was used in combination with other methacrylate monomers to pre- - pare a formulation suitable for orthodontic adhesive preparations. Equal amounts of solutions A and B, described below, are mixed together to form the desired adhesive:
Solution A
14 parts DEAEMA-BF3
28 parts diethyleneglycoldimethacrylate
29 parts Bis-GMA
27 parts fumed silica
2 parts dihydroxyethyl-para-tolylamine
Solution B
42 parts diethyleneglycoldimethacrylate
29 3is-GMA
27 parts fumed silica
1 part benzoyl peroxide
"BUREAIT
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Fluoride Release
Cured discs of material measuring .015 to 0.050 inches thick and 1.5 inches in diameter were immersed in 50 ml portions of distilled water. The fluoride concentration of the exposed water was determined at measured intervals using a fluoride-specific ion electrode. After each determination, the water was discarded and replaced with an additional portion of distilled water. Rates of release have been determined to be 2 to 5 micrograms of fluoride per square centimeter per day. The samples thus studied have fluoride available for release for over one year.
Example 4 The DEAEMA-BF-3 adduct is prepared according to Example 1, and is used in combination with other methacrylate monomers to prepare a formulation suitable -for denture-base preparations according to the following composition: The liquid resin portion of a powder or liquid denture-base material is formulated by mixing 1 part of a solution con¬ taining 4 parts DEAEMA-BF3 and 5 parts methyl ethacrylate containing 2% di ethyl-para-toluidine and 2 parts commercial denture-base powder (polymethylmethacrylate) to form test specimens and acrylic dental devices.
Example 5
The DEAEMA-BF3 addition compound can be prepared according to Example 1 and used in combination with other methacrylate monomers to prepare a formulation suitable for pit and fissure sealant preparations according to the following composition: Equal amounts of solution A and solution B as described below can be mixed together to form a chemically cured pit and fissure sealant:
Solution A 20 parts DEAEMA-BF3 40 parts diethyleneglycoldimethacrylate 40 parts Bis-GMA 2 parts dihydroxyethyl-para-tolylamine
"BUREALT
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Sol ution B
60 parts diethyleneglycoldimethacrylate 40 parts Bis-GMA 1 part benzoyl peroxide
Example 6 The DEAEMA-BF3 addition compound was prepared as shown in Example 1 and used in combination with other methacrylate monomers to prepare a formulation suitable for composite restorative liner prepara- tions according to the following composition:
35 parts Bis-GMA
30 parts ethyleneglycoldimethacrylate 30 parts trimethylolpropanetrimethacrylate 2.5 parts DEAEMA-BF3
1 part dihydroxyethyl-para-tolylamine
The above material is polymerized by mixing 5 parts with 1 part of saturated 9% benzoyl peroxide solution in dimethylphthalate. 0.1 gm " samples of hardened material were stored in 10 ml of distilled water. The fluoride content was measured periodically with an ion-specific electrode and significant levels of fluoride were still being released after more than three months. For comparison, identical tests were run of films of fluorothin, a silica phosphate cement, and MQ, a silicate cement. Results indicate that the experimental composite films . maintained a detectable release of fluoride over a longer period of time than the fluorothin and MQ films, even though the silica phosphate and silicate cements released larger amounts of fluoride during the initial part of the leach.
Example 7 A quantity 15 gm N,N,N' ,N'-tetramethylethylenediam ne (TMED) are placed in a three-neck round-bottom flask. The flask is set into an ice bath to moderate reaction temperature. A vacuum is drawn on the reaction flask and gaseous boron trifluoride is bubbled at such a rate that the temperature does not exceed 35° C. The rate of bubbling is increased when the temperature begins to fall. The reaction is
- U EA L
OMPI _
continued until the temperature no longer increases on increased boron trifluoride addition. This takes about one hour when the reaction product is collected and then purified by distillation using a molecular still.
The resulting addition compound is used in combination with methacrylate monomers to prepare a formulation suitable for composite resin filling materials according to the formulation below:
13 parts Bis-GMA
3 parts trimethylolpropanetrimethacrylate
3 parts ethyleneglycoldimethacrylate
.01 parts 2,6-di-t-butyl-p-cresol
.2 parts N,N, diethanol-m-tolylamine 1 part per asorb MA
17 parts Calcium silicate
.04 parts Tilan-ium dioxide
60 parts Barium silicate
3 parts TMED BF3
Example 8 The DEAEMA-BF3 compound was prepared as shown in Example 1. This compound was then added to an experimental formulation of a composite restorative liner as shown below:
35 parts Bis-GMA
30 parts ethyleneglycoldimethacrylate 30 parts trimethylolpropanetrimethacrylate 5 parts DEAEMA-BF3 0.84 pphr N,N-diethanol-p-tolylamine 0.05 pphr 2,6 di-t-butyl-p-cresol 2.5 pphr benzophenone
Results of tests show that the thermal and ultraviolet color stability of these liners are good, as is their compatibility with silicate cements and composite resins.
- υREACT
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Example 9 A composite restorative liner was prepared as shown in Example 6. Analysis of leaching of the fluorine-containing Lewis acid - Lewis base addition compound indicates that the boron content of the restorative liner leaching solution is much less than it should be if all the available boron is leached.
Leach % Total Sol'n Avail. Exp. Boron % of Solution Fluoride Fluoride Avail. in Leach Boron (% Adduct) Content Leached Boron* S Sooll''nn Avail.
(5%) 12 μg 22.5 40 μg 7.4 μg 18.5% (2.5%) 8.4 μg 32 29 μg 2.6 μg 8.8%*
*Based upon measured fluoride content in leach solution.
•* To measure the fluoride-releasing characteristics of cured experimental restorative liners, 0.1 gm films of 9 to 13 mils thickness were soaked for an extended period in 10 mis water. Fluoride ion concentrations were measured periodically, using an ion-specific electrode.
Claims
1. A dental composite comprising a dental restorative material and a controlled fluoride release compound wherein said controlled fluoride release compound comprises a Lewis base and a fluorine- containing Lewis acid.
2. The dental composite of claim 1 wherein the fluorine-con¬ taining Lewis acid component is mobile within said composite.
3. The dental composite of claim 2 wherein the Lewis base is dispersible or soluble within the dental composite.
4. The dental composite of claim 2 wherein the Lewis base is selected from the group consisting of amines, ethers and esters, acids, ketones, and alcohols, mercaptans, thioethers and thioesters.
5. The dental composite of claim 2 wherein the Lewis base is an amine represented by the formula: -
R R
wherein R and R, are hydrogen, a hydroxyl, a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.
6. The dental composite of claim 5 wherein the chain length of the aliphatic group is from about 1 to about 12 carbon atoms.
7. The dental composite of claim 6 wherein the Lewis base is triethylamine and the Lewis acid is boron trifluoride.
8. The dental composite of claim 5 wherein R, is an a inoalkyl represented by the formula:
"BU EA
wherein R is a substituted or unsubstituted aromatic group, a hydroxyl group, hydrogen, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group, and R2 is an alkylene.
9. The dental composite of claim 8 wherein the carbon chain length of the aliphatic group is from about 1 to about 12 carbon atoms and the alkylene from about 1 to about 9 carbon atoms.
10. The dental composite of claim 8 wherein the Lewis base is a diamine represented by the formula:
11. The dental composite of claim 10 wherein the aliphatic groups have a chain length of from about 1 to about 12 carbon atoms and n is an integer having from about 1 to about 9 carbon atoms.
12. The dental composite of claim 11 wherein the Lewis base is N,N,N' jN'-tetramethylethylenediamine and the Lewis acid is boron tri¬ fluoride.
13. The dental composite of claim 1, 2, 3, 4, 5, 8, or 10 wherein the controlled fluoride release compound comprises from about 0.05 to about 50% of said dental restorative material.
IJUREAT/"
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-
14. The dental composite of claim 1, 2, 3, 4, 5, 8, or 10 wherein the controlled fluoride release compound comprises from about 0.5 to about 25% of said dental restorative material.
15. The dental composite of claim 1, 2, 3, 4, 5, 8, or 10 wherein the controlled fluoride release compound comprises from about 0.5 to about 1.5% of said dental restorative material.
16. The dental composite of claim 2 wherein the dental restora- tive material is selected from the group consisting of restorative composite resins, cavity liners, resin adhesives, pit and fissure sealants, denture base resins, orthodontic resins, orthodontic elastics and plastic orthodontic brackets.
17. A dental composite comprising a polymeric dental restora¬ tive material and a controlled fluoride release compound wherein said controlled fluoride release compound comprises a Lewis base and a fluorine-containing Lewis acid, wherein the Lewis base is a constituent resin component of the polymeric dental restorative material.
18. The dental composite of claim 17 wherein the fluorine- containing Lewis acid is mobile within said dental composite.
19. The dental composite of claim 18 wherein the Lewis base constituent resin component can be incorporated into the backbone, side chain, or crosslink of the polymeric dental restorative material.
20. The dental composite of claim 19 wherein the Lewis base constituent resin component has the formula:
CH2=C-R3
R2
wherein R2 is hydrogen, or a cyano group, or a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl; and R~ is an esterified
-fclJ E cr
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carboxyl group, a primary amine, a secondary amine, a tertiary amine, a carboxyl amine, or an amine-containing ester having the formula:
5 °tCHΛR4
wherein R. is a primary amine, secondary amine, or tertiary amine, and n is an integer.
0 21. The dental composite of claim 20 wherein n is an integer having from about 1 to about 9 carbon atoms.
22. The dental composite of claim 20 wherein the amine is a 5 tertiary amine of the formula:
N—R
\R
Q . wherein R is a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.
23. The dental composite of claim 22 wherein the aliphatic tj group has from about 1 to about 9 carbon atoms.
24. The dental composite of claim 19 wherein the Lewis base is selected from the group consisting of acrylic and methacrylic esters, polya ides, polycyclamides, amino resins, and acrylic and methacrylic Q acids, urethanes, epoxies, polyesters and polycarbonates.
25. The dental composite of claim 20 wherein the constituent resin component is dimethylaminoethylmethacrylate and the Lewis acid is boron trifluoride.
26. The dental composite of claim 17, 19, 20, or 24 wherein the controlled fluoride release compound comprises from about 0.05 to about 50% of said restorative material. liU E lT
OMPI
27. The dental composite of claim 17, 19, 20, or 24 wherein the controlled fluoride release compound comprises from about 0.5 to about 25% of said restorative material.
28. . The dental composite of claim 17, 19, 20, or 24 wherein the controlled fluoride release compound comprises from about 0.5 to about 1.5% of said restorative material.
29. The dental composite of claim 19 wherein the dental restorative material is selected from the group consisting of restora¬ tive composite resins, cavity liners, resin adhesives, pit and fissure sealants, denture base materials, orthodontic resins, orthodontic elastics and plastic orthodontic brackets.
30. A method of reducing dental caries and plaque formation by treating teeth with a dental composite comprising a dental restorative material and a controlled fluoride release compound wherein said controlled fluoride release compound comprises a Lewis base and a fluorine-containing Lewis acid, said release compound being present in ' an amount effective to reduce plaque formation and prevent tooth caries.
31. The method of claim 30 wherein the fluorine-containing Lewis acid component is mobile within said composite.
32. The method of claim 30 wherein the Lewis base is dispersible or soluble within the dental composite.
33. The method of claim 32 wherein the Lewis base is selected from the group consisting of amines, ethers and esters.
34. The method of claim 32 wherein the Lewis base is an amine represented by the formula:
- lJREA r OMPI
wherein R and R^ are hydrogen, a hydroxyl, a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group wherein the carbon chain length.of the aliphatic group is limited such that the compound is soluble within a dental restorative material.
35. The method of claim 34 wherein the chain length of the aliphatic group is from about 1 to about 12 carbon atoms.
36. The method of claim 35 wherein the Lewis base is triethyl- amine and the Lewis acid is boron trifluoride.
37. The method of claim 34 wherein R, is an aminoalkyl represented by the formula:
wherein R is a substituted or unsubstituted aromatic group, a • hydroxyl group, or a hydrogen, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group, and R« is an al ylene.
38. The method of claim 37 wherein the carbon chain length of the aliphatic group is from about 1 to about 12 carbon atoms and the alkylene from about 1 to about 9 carbon atoms.
39. The method of claim 37 wherein the diamine is represented by the formula:
wherein R is a substituted or unsubstituted aromatic group, a hydroxyl group, a hydrogen, or a linear or branched, saturated or unsat¬ urated, substituted or unsubstituted aliphatic group, and n is an
integer representing an alkylene chain length which produces a compound that is dispersible or soluble within a dental restorative material.
40. The method of claim 39 wherein the aliphatic groups have a chain length of from about 1 to about 12 carbon atoms and n is an integer having from about 1 to about 9 carbon atoms.
41. The method of claim 40 wherein the Lewis base is N,N,N',N'- tetraethylenediamine and the Lewis acid is boron trifluoride.
42. The method of claim 30, 31, 32, 33 34, or 39 wherein the controlled fluoride release compound comprises from about 0.05 to about 50% of said dental restorative material.
43. The method of claim 30, 31, 32, 33, 34, or 39 wherein the controlled fluoride release compound comprises from about 0.5 to about 25% of said dental restorative material.
44. The method of claim 30, 31 32, 33, 34, or 39 wherein the - controlled fluoride release compound comprises from about 0.5 to about
1.5% of said dental restorative material.
45. The method of claim 32 wherein the dental restorative material is selected from the group consisting of restorative composite resins, cavity liners, resin adhesives,. pit and fissure sealants, den¬ ture base materials, orthodontic resins, orthodontic elastics and plas¬ tic orthodontic brackets.
46. A method of reducing dental caries and plaque formation by treating teeth with a dental composite comprising a polymeric dental restorative material and a controlled fluoride release compound wherein said controlled fluoride release compound comprises a Lewis base and a fluorine-containing Lewis acid, wherein the Lewis base is a constituent resin component of the polymeric dental restorative material, said release compound being present in an amount effective to reduce plaque formation and prevent tooth caries.
47. The method of claim 46 wherein the fluorine-containing Lewis acid is mobile within said dental composite.
48. The method of claim 47 wherein the Lewis base constituent resin component can be incorporated into the backbone, side chain, or crosslink of the polymeric dental restorative material.
49. The method of claim 48 wherein the Lewis base constituent resin component has the formula: '
CH2=C-R3 R2
wherein R2 is hydrogen, or a cyano group, or a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl; and R is an esterified carboxyl group, a primary amine, secondary amine, tertiary amine, carboxyl amine, or an amine-containing ester having the formula: ■
wherein R^ is a primary amine, secondary amine, or tertiary amine, and n is an integer.
50. The method of claim 49 wherein n is an integer having from about 1 to about 9 carbon atoms.
51. The method of claim 49 wherein the amine is a tertiary amine of the formula:
-gU EAZT OMPI
^
wherein R is a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.
52. The method of claim 51 wherein the aliphatic group has from about 1 to about 9 carbon atoms.
53. The method of claim 48 wherein the Lewis base is selected from the group consisting of acrylic and methacrylic esters, poly- amides, polycyclamides, amino resins, and acrylic and methacrylic acids, urethanes, epoxies, polyesters and polycarbonates.
54. The method of claim 52 wherein the constituent resin component is dimethylaminoethylmethacrylate and the Lewis acid is boron trifluoride.
55. The method- of claim 46, 48, 49, or 53 wherein the con¬ trolled fluoride release compound comprises from about 0.05 to about 50% of said restorative material. -
56. The method of claim 46, 48, 49, or 53 wherein the controlled fluoride release compound comprises from about 0.5 to about 25% of said restorative material.
57. The method of claim 46, 48, 49, or 53 wherein the controlled fluoride release compound comprises from about 0.5 to about 1.5% of said restorative material.
58. The method of claim 48 wherein the dental restorative ate- rial is selected from the group consisting of restorative composite resins, adhesives, cavity liners, pit and fissure sealants, denture base materials, orthodontic resins, orthodontic elastics and plastic orthodontic brackets.
59. A cariostatic and plaque-reducing compound comprising a Lewis base and a fluorine-containing Lewis acid, wherein the Lewis base is selected from the group consisting of amines, ethers, esters, acids, ketones and alcohols.
60. The compound of claim 59 wherein the Lewis base is an amine represented by the formula:
R
/ N—R,
\
wherein R and R, are hydrogen, a hydroxyl, a substituted or unsubstituted aromatic group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.
61. The compound of claim 60 wherein the chain length of the aliphatic group is from about 1 to about 12 carbon atoms.
62. The compound of claim 59 wherein the Lewis base is triethyla ine and the Lewis acid i's boron trifluoride.
63. The compound of claim 60 wherein R-, is an a inoalkyl represented by the formula:
wherein R is a substituted or unsubstituted aromatic group, a hydroxyl group, a hydrogen, or a linear or branched, saturated or unsat¬ urated, substituted or unsubstituted aliphatic group, and R2 is an alkylene.
64. The compound of claim 63 wherein the carbon chain length of the aliphatic group is from about 1 to about 12 carbon atoms, and the carbon atom chain length of the alkylene is from about 1 to about 9 carbon atoms.
-fcUREAiT
OMPI
65. The compound of claim 63 wherein the the Lewis base is a diamine represented by the formula:
66. The compound of claim 65 wherein the Lewis base is N,N,N', N1- tetramethylethylenediamine and the Lewis acid is boron trifluoride.
67. A cariostatic and plaque-reducing compound comprising a Lewis base and a fluorine-containing Lewis acid, wherein the Lewis base is a constituent resin component of a polymeric resin.
" 68. The compound of claim 67 wherein the fluorine-containing Lewis acid is mobile within said polymeric resin.
69. The compound of claim 67 wherein the Lewis base constituent resin component has the formula:
wherein R2 is hydrogen, or a cyano group, or a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl; and R3 is an esterified carboxyl group, a primary amine, a secondary amine, a tertiary amine, a carboxyl amine, or an amine-containing ester having the formula:
70. The compound of claim 69 wherein the amine is a tertiary amine having the formula:
/ R
N—R R
wherein R is a substituted or unsubstituted phenyl group, or a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.
71. The compound of claim 70 wherein the constituent resin component is diethylaminoethylmethacrylate and the Lewis acid is boron trifluoride.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82902043T ATE36646T1 (en) | 1981-06-01 | 1982-05-20 | FLUORINE CONTAINING DENTAL MATERIALS. |
DE8282902043T DE3278929D1 (en) | 1981-06-01 | 1982-05-20 | Fluorine containing dental materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26912981A | 1981-06-01 | 1981-06-01 | |
US269129810601 | 1981-06-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1982004259A1 true WO1982004259A1 (en) | 1982-12-09 |
Family
ID=23025920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1982/000695 WO1982004259A1 (en) | 1981-06-01 | 1982-05-20 | Fluorine containing dental materials |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0079940B1 (en) |
CA (1) | CA1203484A (en) |
DE (1) | DE3278929D1 (en) |
WO (1) | WO1982004259A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0363095A2 (en) * | 1988-10-03 | 1990-04-11 | Minnesota Mining And Manufacturing Company | Organic fluoride sources |
FR2680098A1 (en) * | 1991-08-06 | 1993-02-12 | Bergersen Earl Olaf | PROCESS FOR INJECTION MOLDING OF SLOW RELEASE FLUORANE AND APPARATUS FOR HUMAN DENTITION RELATING THERETO. |
WO1997018791A1 (en) * | 1995-11-17 | 1997-05-29 | Minnesota Mining And Manufacturing Company | Use of metallofluorocomplexes for dental compositions |
WO1997018792A1 (en) * | 1995-11-17 | 1997-05-29 | Minnesota Mining And Manufacturing Company | Fluoride-releasing compositions |
WO1998046197A1 (en) * | 1997-04-11 | 1998-10-22 | Minnesota Mining And Manufacturing Company | Dental compositions with improved handling capabilities |
EP3243499A1 (en) * | 2008-10-15 | 2017-11-15 | 3M Innovative Properties Co. | Dental compositions with fluorescent pigment |
CN116196222A (en) * | 2023-02-28 | 2023-06-02 | 上海沐良医疗器械有限公司 | Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW414713B (en) | 1994-05-12 | 2000-12-11 | Dentsply Gmbh | Fluoride releasing liquid dental primer product and method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2824083A (en) * | 1955-12-27 | 1958-02-18 | Shell Dev | Compositions containing bf3 complexes and their use as curing agents for polyepoxides |
US2980733A (en) * | 1954-07-12 | 1961-04-18 | Frank J Sowa | Coordination complexes of urea and boron trifluoride and methods of producing the same |
US3159470A (en) * | 1961-07-21 | 1964-12-01 | Gulf Research Development Co | Thermally stabilized liquid hydrocarbon fuels |
US3327016A (en) * | 1964-07-09 | 1967-06-20 | Epoxylite Corp | Epoxide compositions cured with 1, 4-bis (aminomethyl) cyclohexane |
-
1982
- 1982-05-20 EP EP82902043A patent/EP0079940B1/en not_active Expired
- 1982-05-20 WO PCT/US1982/000695 patent/WO1982004259A1/en active IP Right Grant
- 1982-05-20 DE DE8282902043T patent/DE3278929D1/en not_active Expired
- 1982-06-01 CA CA000404186A patent/CA1203484A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2980733A (en) * | 1954-07-12 | 1961-04-18 | Frank J Sowa | Coordination complexes of urea and boron trifluoride and methods of producing the same |
US2824083A (en) * | 1955-12-27 | 1958-02-18 | Shell Dev | Compositions containing bf3 complexes and their use as curing agents for polyepoxides |
US3159470A (en) * | 1961-07-21 | 1964-12-01 | Gulf Research Development Co | Thermally stabilized liquid hydrocarbon fuels |
US3327016A (en) * | 1964-07-09 | 1967-06-20 | Epoxylite Corp | Epoxide compositions cured with 1, 4-bis (aminomethyl) cyclohexane |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0363095A2 (en) * | 1988-10-03 | 1990-04-11 | Minnesota Mining And Manufacturing Company | Organic fluoride sources |
EP0363095A3 (en) * | 1988-10-03 | 1991-07-31 | Minnesota Mining And Manufacturing Company | Organic fluoride sources |
CN1034550C (en) * | 1988-10-03 | 1997-04-16 | 明尼苏达州采矿制造公司 | Organic fluoride sources |
FR2680098A1 (en) * | 1991-08-06 | 1993-02-12 | Bergersen Earl Olaf | PROCESS FOR INJECTION MOLDING OF SLOW RELEASE FLUORANE AND APPARATUS FOR HUMAN DENTITION RELATING THERETO. |
WO1997018791A1 (en) * | 1995-11-17 | 1997-05-29 | Minnesota Mining And Manufacturing Company | Use of metallofluorocomplexes for dental compositions |
WO1997018792A1 (en) * | 1995-11-17 | 1997-05-29 | Minnesota Mining And Manufacturing Company | Fluoride-releasing compositions |
JP2000500484A (en) * | 1995-11-17 | 2000-01-18 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Use of metal fluoro complexes in dental compositions |
US6391286B1 (en) | 1995-11-17 | 2002-05-21 | 3M Innovative Properties Company | Use of metallofluorocomplexes for dental compositions |
JP2008050369A (en) * | 1995-11-17 | 2008-03-06 | 3M Co | Dental composition |
WO1998046197A1 (en) * | 1997-04-11 | 1998-10-22 | Minnesota Mining And Manufacturing Company | Dental compositions with improved handling capabilities |
EP3243499A1 (en) * | 2008-10-15 | 2017-11-15 | 3M Innovative Properties Co. | Dental compositions with fluorescent pigment |
CN116196222A (en) * | 2023-02-28 | 2023-06-02 | 上海沐良医疗器械有限公司 | Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance |
Also Published As
Publication number | Publication date |
---|---|
CA1203484A (en) | 1986-04-22 |
EP0079940A4 (en) | 1985-07-01 |
EP0079940A1 (en) | 1983-06-01 |
EP0079940B1 (en) | 1988-08-24 |
DE3278929D1 (en) | 1988-09-29 |
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