EP0059194A4 - Zinc-containing glass composition. - Google Patents
Zinc-containing glass composition.Info
- Publication number
- EP0059194A4 EP0059194A4 EP19810902360 EP81902360A EP0059194A4 EP 0059194 A4 EP0059194 A4 EP 0059194A4 EP 19810902360 EP19810902360 EP 19810902360 EP 81902360 A EP81902360 A EP 81902360A EP 0059194 A4 EP0059194 A4 EP 0059194A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- glass
- oxide
- accordance
- paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000011521 glass Substances 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 12
- 229910052725 zinc Inorganic materials 0.000 title abstract description 12
- 239000011701 zinc Substances 0.000 title abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 11
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 9
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910011255 B2O3 Inorganic materials 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 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 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 20
- 229910052788 barium Inorganic materials 0.000 description 19
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011350 dental composite resin Substances 0.000 description 4
- 235000019589 hardness Nutrition 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 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
- 239000004568 cement Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 239000003479 dental cement Substances 0.000 description 2
- 238000005816 glass manufacturing process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 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 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000004489 deciduous teeth Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- 229940102838 methylmethacrylate Drugs 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000000068 pit and fissure sealant Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/17—Particle size
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/78—Pigments
-
- 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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/807—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
Definitions
- This invention relates to zinc-containing glass compositions and to dental filling compositions containing such glass composition in the form of finely divided fi ller .
- Gold and other metallic-looking restorations are used for molars and teeth which are not immediately open to view when the wearer opens his mouth or smiles.
- anterior teeth For anterior teeth, however, current practice is to use materials closer in appearance to natural teeth.
- These are known colloquially as porcelain or plastic fillings. They are composite materials characterized by containing usually predominantly inorganic materials, normally finely divided powders inert to the oral environment bound together with polymeric matarial .
- the inorganic materials are frequently finely-ground fused oxides, particularly glasses, or crystalline quartz, while the polymer moiety is commonly a polyacrylate .
- These composite systems are available, for example, as pastes which are polymerized in situ, after having been activated, e.g. by adding a catalyst to initiate a polymerization reaction, just before being placed in the prepared tooth.
- Fi llings and restorations of this kind can be made to look much l ike natural teeth.
- the color of the restoration can be adjusted to a shade quite close to that of a patient's natural teeth by tinting with pigments.
- the translucency or pearlescence of the natural tooth can also be approximated through adjustment of the relative refractive indices of the materials used in the restoration.
- color and refractive indices are well matched, it is possible to obtain a restoration that is barely perceptible to the glance.
- the attainment of good color and overall appearance is very difficult to achieve in practice. This is particularly true when one desires also to optiimize other features of a good restoration, particularly radiopacity.
- a filling or other restoration it is highly desirable for a filling or other restoration to be radiopaque, for it is by X-ray examination that a dentist determines whether or not a filling remains sound. From radiographs a dentist determines the condition ⁇ f a filling, e.g. whether it has cracked, or whether decay is occurring at the interface between the tooth and the filling. Fillings and restorations which are made of metal are readily observable in X-rays. Fillings of the porcelain/plastic art are not observable by X-rays unless they have radiopaque materials therein.
- radiopaque agents are elements of high atomic number (i.e. the "heavy elements" of the periodic table); it is unfortunate, however, that most of these elements ar either radioactive or toxic, such as thorium or lead. Barium is toxic also, but in certain medical uses it is present in a form so highly insoluble that the body is unable to metabolize enough of it to become intoxicated.
- barium glasses have been used as components of dental restorations, on the hypothesis that barium ions within the structure of a glassy matrix will not be available to oral fluids (sal iva, beverages , etc.) and will not, therefore, pose a problem of toxicity.
- Examples of the use of barium glass in dental restorations can be found in U.S. Patents 3,801 ,344; 3,808,170; 3,826,778; 3,911,581 ; 3,959,212; 3,975,203 and 4,032,504.
- the barium glasses are not as stable as had originally been hoped, and they have not, therefore, found favor in the art on account of the risk they pose of poisoning the patient (see, e.g. U.S.
- Patent 3,971,754 A further problem encountered with the barium glasses is that of matching refractive indices to that of the other components of the restoration. For example, it would be desirable to use components with refractive indices in the range of about 1.5 to 1.6 (so as to closely match the refractive index of commonly used organic binders) but most barium glasses with refractive indices in this range are unsuitable for dental use according to U.S. Patent 4,032,504. It is difficult, therefore, to prepare restorations containing barium glass which present an unobtrusive appearance when used for anterior surface repair. An additional problem of the barium glasses is their alkalinity.
- bariuim glasses show alkalinity values of pH 9 or greater, whereas a pH of 7 is preferred.
- Highly alkaline fillers appear to degrade the sildxane coating resulting from etching of the prepared tooth cavity and also cause rapid decomposition of any peroxide catalyst present in the dental restorative composition during storage.
- Recent efforts in the field of dental restoration materials have resulted in the use of fillers other than barium-containing compounds as an X-ray detectable component.
- U.S. Patent 3,371,754 describes the use of certain oxides or carbonates, particularly those of lanthanum, strontium, tantalum and, less usefully, hafnium. These salts are mixed with glass-making components at the time the glass is made, yielding a lanthanum, strontium, tantalum or hafnium glass which possesses a measure of radiopacity.
- 3,973,972 and 4,017,454 describe glass ceramics which possess both a low coefficient of thermal expansion (an advantage in dental fillings) and a useful degree of radiopacity, by virtue of a high content of rare earth elements, particularly lanthanum.
- the rare earth elements absorb X-rays in the wavelength range of 0.2 - 0.3A, a range commonly available from dental X-ray machines.
- the cost and problems with availability of these rare earth fillers make them generally unsuitable for commercial use.
- organic halide e.g. an alkyl iodide
- plastic materials e.g. acrylata polymers
- molded articles e.g. U.S. Patent 3,715,331.
- the articles molded from such compositions lack the strength of restorations made from glass or ceramic materials.
- U.S. Patent 4,250,277 describes a glass composition used for crosslinking polycarboxylic acid cement, wherein the glass contains zinc oxide and a large amount of boric oxide, in addition to other ingredients. This glass, however, is too water soluble to be useful in dental restorative compositions and prosthetic devices.
- U.S. Patent 4,215,033 describes a composite dental material containing a glass which in one embodiment is described as single phase.
- this patent does not appear to recognize that a single phase glass containing zinc oxide can be made radiopaque.
- the single phase glass composition described in this patent is very difficult to make.
- such glass does not contain any aluminum fluoride. Disclosure of Invention
- a novel glass and a dental filling composition comprising polymeri zable resin binder and a finely divided inorganic glass filler.
- which is X-ray opaque and single phase, wherein said X-ray opaque inorganic glass filler consists essentially of, in percent by weight:
- Al uminum oxide 0 to 10% Al uminum fluoride At least 2% Al kal i metal oxide 0 to 3% or alkaline earth metal oxide wherein the combined weight of aluminum oxide and aluminum fluoride is at least about 10%, and wherein said glass exhibits an "X-ray absorption characteristic" of at least 1/16 inch (0.16 cm).
- glasses containing high levels of zinc can be prepared which possess physical characteristics (e.g. refractive index, pH, coefficient of expansion) making them especially suitable for use in dental restorati ve compositions.
- these glasses have been found to be radiopaque and to be capable of being made into dental composites which have greater radiopacity than those made with barium, the best Scnown radiopacifying agent used heretofore. This is quite surprising, considering barium has an atomic number of 56, iodine an atomic number of 33, the la ⁇ thanides having atomic numbers of 57 to 71, and zinc having an atomic number of only 30.
- the new zinc glasses with refractive indices in the desired range for dentai restorative compositions.
- the new glasses can be prepared at a pH close to 7. This is a highly desirable feature in regard to the preparation of high quality dental composites.
- the stability of the dental composite is significantly enhanced. Improved color stability, and reliable setting characteristics after the activated camp ⁇ si te is emplaced in the tooth being repaired.
- the new glasses are significantly better than the barium glasses of the prior art in this regard.
- Barium is an alkaline earth element in the periodic system, and, therefore, more electropositive than zinc, which is a transition element.
- the higher pHs characteristic of the barium glasses cause decomposition of the peroxide catalysts normally used in these formulations and thus greatly reduce storage stability.
- a significant advantage of the new glasses, which is an improvement over any known heretofore, is that they contain an element, namely, zinc, that has been in regular dental use for many years Zinc oxide-containing ointments have long been used in medicine as safe and mild antibacterial agents and zinc oxide has long been used as a component in dental cements or adhesives.
- the new single phase glasses used in this invention have the following composition in percent by weight:
- the alkali metal oxide o alkaline earth metal oxide may be, for example, sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, or the like, or combinations thereof, so long as the combined weight of such oxides does not exceed about 3% of the glass, thus maintaining the pH of the glass in the desired range of about 6.5 to 8.
- a preferred embodiment of the new glass for use in de ⁇ tai restoratives intended for anterior applications has the following composition:
- Aluminum oxide 1 to 3% Aluminum fluoride 17 to 19% wherein the combined weight of aluminum oxide and aluminum fluoride is not greater than about 20%, and wherein the glass exhibits an X-ray absorption characteristic of at least 3/32 inch (0.24 cm).
- the compositions given above are written in terms of the salts (e.g. oxides and fluorides) which are used in preparing the melt from which the glass is obtained upon cooling. This is a common practice in the glass- marking art. There is, of course, no oxide, fluoride, or other simple salt in the resultant glass. Glasses used in this invention all possess a useful degree of radiopacity.
- the refractive index of the glass may be varied, depending upon the particular amount of each ingredient present. It is preferred that the refractive index of the glass filler be substantially the same as that of the binder resin when the glass is used in a dentai filling composition, i.e. within about 0.05, whan the composition is used in anterior appl ications.
- the binder resin comprises the well known BIS-GMA
- the refractive index for the glass filler is preferbaly 1.555 + 0.05. Matching of the refractive indices of the glass filler and the binder resin is. less important when the composition is intended for posterior dental applications.
- BIS-GiMA resin is diluted with another acrylic resin (e.g.
- the resultant resin mixture may have a refractive index of 1.545, for example. Consequently, far such an application it may be preferred to use a glass composition having a refractive index of 1.545 if close matching of the resin and filler is desired.
- a dental fill ing composition which is light curable it is important to obtain a close match of the refractive indices of the polymerizabl e resin and the glass filler so that complete and rapid cure of the resin will be achieved when it is exposed to the activating light.
- the composition is intended for use elsewhere in the body (i.e. where esthetics are not a factor) and where the composition is not light curable, there is no need to attempt matching the refractive index of the glass to the refractive index of the binder resin.
- Radiopacity which reflects the materials's ability to attenuate X-rays, is conveniently measured by comparing the X-ray film image density values of a disc of the cured composite of a standard thickness, e.g. 0.040 inch (0.1 cm), with corresponding values of a known standard Film image density measurements are made with a suitable densitometer, such as a Macbeth Transmission Densito meter, Model TO 504, with visible light filter (manufactured by Macbeth Div. of Kollmorgan Corp., Newburgh, 'N.Y.).
- a suitable densitometer such as a Macbeth Transmission Densito meter, Model TO 504
- visible light filter manufactured by Macbeth Div. of Kollmorgan Corp., Newburgh, 'N.Y.
- a convenient standard is a stepped aluminum wedge, for example, a ten step wedge having a thickness of 1/32 inch (0.08 cm) at the thinnest step increasing to 5/16 inch (O.8 cm) at the thickest step.
- a ten step wedge having a thickness of 1/32 inch (0.08 cm) at the thinnest step increasing to 5/16 inch (O.8 cm) at the thickest step.
- a proper level of radiopacity wi ll permit one skilled in the art to differentiate between the restoration and primary and recurrent caries in the tooth structure, and will also visualize defects in the restoration itself.
- the glasses of this invention when tested in this manner give values of 1/16 inch (0.16 cm) at 26% ZnO; 3/32 - 1/8 inch (0.24 - 0.32 cm) at 26.5 - 28% ZnO.
- Typical barium glasses of the prior art, tested under identical conditions give values of 1/16 - 3/32 inch (0.16 - 0.24 cm).
- the typical "plastic" or “porcelain” filling materials containing quartz or borosilicate filler) common in contemporary dental practive give values of zero.
- a silver amalgam gives a values of > 5/16 inch (0.3 cm). It will be understood, of course, that these values are completely empirical. Using different wedges and experimental apparatus, the actual numbers one gets may be different.
- useful glasses exhibit an X-ray absorption characteristic of at least 1/16 inch (0.16 cm).
- the glass powder is then prepared for incorporating into an organic binder matrix by treating the surface with a si lane compound.
- a si lane compound This is a well-known technique for rendering relatively polar materials, such as siliceous powders, more compatible with relatively non-polar materials, such as organic polymers.
- the zinc glass is then mixed into a dentai paste.
- the paste may be formed of any of the polymeri zable resin systems useful in dentistry.
- Especially useful resin systems comprise free-radically polymerizable materials such as the polyfunctional acrylata systems.
- Particularly useful in the system is 3IS-GMA, a well- known material which is the reaction product of bisphenol- A and glycidyl methacryl ate, widely used in dentistry.
- Other commonly used resin binders include polyurethanes, methyl methacryl ate, and isobutyl methacrylate.
- the zinc glass may be used alone or it may be blended with other suitable materials, such as inert glass powders, when mixed into the binder - depending, for example, on the degree of radiopacity desired in the final composite.
- the paste may also be mixed into the paste, such as pigments for making the restoration match the patient's natural tooth color, and reagents like hydroquinone monomethyl ether, as an inhibitor of premature polymerization of the binder.
- the paste is activated by mixing into it the appropriate amount of catalyst, such as benzoyl peroxide.
- the dental restorative composition may be in the form of two pastes (one paste containing filler, resin binder and catalyst while the other contains filler, resin binder and accelerator), or a liquid resin and powdered filler system, or a paste- liquid resin, or any other desired form.
- the mixed composition is promptly em p l a c ed in the tooth, hardeni n g in the manner characteristic of the resin binder and catalyst system being used.
- the composite becomes grossly rigid in about 5 minutes and may be finely ground and polished, to give the finished restoration, in about 10 minutes.
- the condition of the restoration and the adjacent tooth structures can be determined by diagnostic dental X-rays.
- Curable compositions which contain the novel glass and which are useful in other applications may be prepared in similar fashion using polymerizable resin binders.
- Silica 47 gms
- zinc oxide 25 gms
- baric oxide 8 gms
- aluminum oxide (1 gm)
- aluminum fluoride 18 gms
- the mixture is heated in a muffle furnace at 1450oF. (788oC.) until the powder has become a transparent mel t.
- the molten glass is then removed from the crucible through a small hole in the crucible wall, by tilting the crucible and allowing a thin stream of glass to flow through, giving a filament of glass of about 1/32 inch (0.08 cm) diameter. This filament is quenched rapidly in cold water, to give a completely clear glass (as opposed to being opalescent). Mere air cooling of the glass is not sufficiently rapid to prevent phase separation.
- the clear glass is then ground, e.g. in a ball mill, to a mean particle size range of 0.5 - 15 ⁇ m.
- Example 2 Gamma-methacryloxy-propyltrimethoxy silane (2 gms) is mixed with glacial acetic acid (0.033 gms) and water (44.4 gms) in a plastic beaker. Glass powder (100 gms for example, from Example 1) is added to the mixture, and the system is stirred for 1.5 hours at room temperature. The glass slurry is dried, by warming it at 140oF. (50 C.) for 24 hours, followed by heating it in an oven for 2.5 hours at 240oF. (115o C).
- Example 3 Two pastes, A and B, are prepared, having the following compositions: Ingredient Paste A Paste B
- Tinuvin P a UV absorber .16
- the pastes are prepared as follows : For each paste, A and B, two preliminary mixes are made. The glass (from Example 2) and the pigments are mixed thoroughly to give an evenly colored powder. This mix is the same for each paste. The resins, accelerator, UV absorbers and inhibitor are mixed to give the mix for paste A. The resins, catalyst, UV absorber, and inhibitor are mixed to give the mix for paste B. After the two mixes, glass and resin based respectively, have been prepared, the procedure for preparing each paste, A and B, is the same .
- Each resin mix is added to a vessel and then the respective glass mix is added.
- the two mixes are first roughly blended together, such as by shaking, and are then thoroughly mixed preferably by prolonged mechanical mixing.
- Pastes A and B are the precursors to the dental restorations made from the materials of this invention.
- Pastes A and B are kept separate until immediately before the appropriate repair is made in a tooth which has been prepared to receive it. They are then mixed together thoroughly and promptly emplaced in the manner well-known in dental art.
- Example 4 Using the procedure of Example 3, two pastas, A and B, are prepared having the following compositions:
- the two pastes when mixed together, form a very useful dental restorative composition.
- Example 5 The glass filler of Example 1 was ball milled to a mean particle size of 4.5 microns and silane treated according to the method described in Example 2.
- a light- curable paste was prepared having the following compositions.
- the paste is prepared as follows: The milled and treated filler (from Example 2), Aerosil R-972 (col loidal silica, commercially available from DeGussa Corporation, average particle diameter of 16 millimicrons, surface area of 110 square meters/ gram) and the pigments are blended to give an evenly colored powder.
- the resins, inhibitor, accelerator and photoinitiator are mixed in a dark area in a vessel excluding light.
- the filler blend is then added to the mixing vessel containing the resin mix.
- the filler, resins and other components are then thoroughly mixed by prolonged mechanical mixing, with the entire operation carried out in the absence of light.
- Test samples are prepared by packing the paste into an open-ended Teflon mold with a cylindrical cavity. The loaded mold is then placed between 2 pieces of clear polyester film (each 25 microns thick) . Test samples of prescribed thickness are then irradiated for a period of exposure necessary to polymerize or cure the resin in the paste. Barcol hardness measurements are made on the top and bottom of the test sample to determine the extent of polymerization. The following Barcol hardnesses are determined on cured test samples using two different sample thicknesses.
- Standard, commercially available dentai restorative composites typically have Barcol hardness values of 70 - 75 after 24 hours cure.
- the filler loading levels of 33% attained with the zinc glass must also be considered to be extraordinary.
- Conventional radiopaque barium glass permits maximum filler loadings of 73 - 30% when using similar particle size distributions.
- Example 6 The glass filler of Example 1 was ball milled to a mean particle size of 1.8 microns and silane treated according to the method described in Example 2.
- a light-curable pasta having the following composition was prepared using the procedure of Example 5:
- Example 7 The glass filler of Example 1 was ball mil led to a mean particle size of 4.5 - 5.0 microns.
- Radiopaque impression pastes containing the ingredients listed below, were prepared by mixing the ingredients in a conventional Ross brand mixer:
- compositions containing 30 - 40% filler are of low viscosity, while compositions containing 80 - 90% filler have a putty consistency.
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Abstract
Novel glass composition and a dental filling composition for making dental restorations. More particularly, the invention provides a radiopaque dental filling material. Specifically, the dental filling material contains a zinc-containing glass as the component imparting opacity to X-rays.
Description
Description
Zinc-Containing Glass Composition
Technical Fi el d
This invention relates to zinc-containing glass compositions and to dental filling compositions containing such glass composition in the form of finely divided fi ller .
Background Art
A variety of substances has been used over the years to repair damaged teeth. The best known currently include silver amalgams, which are frequently first encountered at an early age as a filling for small cavities, even in deciduous teeth. Gold alloys are a particularly valuable filling material, used frequently when a tooth has been considerably damaged, such as after several cavities have occurred and a lot of tooth must be restored. Frequently, for example, several smaller extending cavities, e.g. in the occlusal surface, will be combined and a restoration made with a single gold inlay or onlay. The gold alloys have gained an excellent reputation for strength, reliability and long life in service. However, both the gold alloys, and the other metals, such as the stainless steels, which have been technically successful in dental reconstructions and crowns, do not impart a natural tooth appearance.
Gold and other metallic-looking restorations are used for molars and teeth which are not immediately open to view when the wearer opens his mouth or smiles. For anterior teeth, however, current practice is to use materials closer in appearance to natural teeth. These are known colloquially as porcelain or plastic fillings. They are composite materials characterized by containing usually predominantly inorganic materials, normally finely divided powders inert to the oral environment
bound together with polymeric matarial . The inorganic materials are frequently finely-ground fused oxides, particularly glasses, or crystalline quartz, while the polymer moiety is commonly a polyacrylate . These composite systems are available, for example, as pastes which are polymerized in situ, after having been activated, e.g. by adding a catalyst to initiate a polymerization reaction, just before being placed in the prepared tooth.
Fi llings and restorations of this kind can be made to look much l ike natural teeth. In particular, the color of the restoration can be adjusted to a shade quite close to that of a patient's natural teeth by tinting with pigments. In addition, the translucency or pearlescence of the natural tooth can also be approximated through adjustment of the relative refractive indices of the materials used in the restoration. When color and refractive indices are well matched, it is possible to obtain a restoration that is barely perceptible to the glance. However, the attainment of good color and overall appearance is very difficult to achieve in practice. This is particularly true when one desires also to optiimize other features of a good restoration, particularly radiopacity.
It is highly desirable for a filling or other restoration to be radiopaque, for it is by X-ray examination that a dentist determines whether or not a filling remains sound. From radiographs a dentist determines the condition αf a filling, e.g. whether it has cracked, or whether decay is occurring at the interface between the tooth and the filling. Fillings and restorations which are made of metal are readily observable in X-rays. Fillings of the porcelain/plastic art are not observable by X-rays unless they have radiopaque materials therein.
Currently, dental filling materials are rendered radiopaque by incorporating barium into the inorganic powder moiety of the filling material. The most effective radiopaque agents are elements of high atomic number (i.e. the "heavy elements" of the periodic table); it is unfortunate, however, that most of these elements ar either radioactive or toxic, such as thorium or lead.
Barium is toxic also, but in certain medical uses it is present in a form so highly insoluble that the body is unable to metabolize enough of it to become intoxicated. In dental applications barium glasses have been used as components of dental restorations, on the hypothesis that barium ions within the structure of a glassy matrix will not be available to oral fluids (sal iva, beverages , etc.) and will not, therefore, pose a problem of toxicity. Examples of the use of barium glass in dental restorations can be found in U.S. Patents 3,801 ,344; 3,808,170; 3,826,778; 3,911,581 ; 3,959,212; 3,975,203 and 4,032,504. Unfortunately, in practice, the barium glasses are not as stable as had originally been hoped, and they have not, therefore, found favor in the art on account of the risk they pose of poisoning the patient (see, e.g. U.S. Patent 3,971,754). A further problem encountered with the barium glasses is that of matching refractive indices to that of the other components of the restoration. For example, it would be desirable to use components with refractive indices in the range of about 1.5 to 1.6 (so as to closely match the refractive index of commonly used organic binders) but most barium glasses with refractive indices in this range are unsuitable for dental use according to U.S. Patent 4,032,504. It is difficult, therefore, to prepare restorations containing barium glass which present an unobtrusive appearance when used for anterior surface repair. An additional problem of the barium glasses is their alkalinity. Typically, bariuim glasses show alkalinity values of pH 9 or greater, whereas a pH of 7 is preferred. Highly alkaline fillers appear to degrade the sildxane coating resulting from etching of the prepared tooth cavity and also cause rapid decomposition of any peroxide catalyst present in the dental restorative composition during storage. Recent efforts in the field of dental restoration materials have resulted in the use of fillers other than barium-containing compounds as an X-ray detectable component. For example, U.S. Patent 3,371,754 describes the use of certain oxides or carbonates, particularly
those of lanthanum, strontium, tantalum and, less usefully, hafnium. These salts are mixed with glass-making components at the time the glass is made, yielding a lanthanum, strontium, tantalum or hafnium glass which possesses a measure of radiopacity. U.S. Patents
3,973,972 and 4,017,454 describe glass ceramics which possess both a low coefficient of thermal expansion (an advantage in dental fillings) and a useful degree of radiopacity, by virtue of a high content of rare earth elements, particularly lanthanum. The rare earth elements absorb X-rays in the wavelength range of 0.2 - 0.3A, a range commonly available from dental X-ray machines. However, the cost and problems with availability of these rare earth fillers make them generally unsuitable for commercial use.
In another approach to preparing radiopaque composites for dental use, organic halide (e.g. an alkyl iodide) has been incorporated into plastic materials (e.g. acrylata polymers), from which molded articles are made (e.g. U.S. Patent 3,715,331). However, the articles molded from such compositions lack the strength of restorations made from glass or ceramic materials.
U.S. Patent 4,250,277 describes a glass composition used for crosslinking polycarboxylic acid cement, wherein the glass contains zinc oxide and a large amount of boric oxide, in addition to other ingredients. This glass, however, is too water soluble to be useful in dental restorative compositions and prosthetic devices.
U.S. Patent 4,215,033 describes a composite dental material containing a glass which in one embodiment is described as single phase. However, this patent does not appear to recognize that a single phase glass containing zinc oxide can be made radiopaque. Also, the single phase glass composition described in this patent is very difficult to make. Furthermore, such glass does not contain any aluminum fluoride.
Disclosure of Invention
In accordance with the present invention there is provided a novel glass and a dental filling composition comprising polymeri zable resin binder and a finely divided inorganic glass filler. which is X-ray opaque and single phase, wherein said X-ray opaque inorganic glass filler consists essentially of, in percent by weight:
Zinc oxide 20 to 35%
Silica 45 to 65% Boric oxide 3 to 15%
Al uminum oxide 0 to 10% Al uminum fluoride At least 2% Al kal i metal oxide 0 to 3% or alkaline earth metal oxide wherein the combined weight of aluminum oxide and aluminum fluoride is at least about 10%, and wherein said glass exhibits an "X-ray absorption characteristic" of at least 1/16 inch (0.16 cm).
Best Mode for Carrying Out the Invention
It has been discovered that glasses containing high levels of zinc can be prepared which possess physical characteristics (e.g. refractive index, pH, coefficient of expansion) making them especially suitable for use in dental restorati ve compositions. Moreover, these glasses have been found to be radiopaque and to be capable of being made into dental composites which have greater radiopacity than those made with barium, the best Scnown radiopacifying agent used heretofore. This is quite surprising, considering barium has an atomic number of 56, iodine an atomic number of 33, the
laπthanides having atomic numbers of 57 to 71, and zinc having an atomic number of only 30. Moreover, it has been found possible to make the new zinc glasses with refractive indices in the desired range for dentai restorative compositions. In addition, the new glasses can be prepared at a pH close to 7. This is a highly desirable feature in regard to the preparation of high quality dental composites. In particular, when the glass is near neutral in pH (i.e. 5.5 to 3), the stability of the dental composite is significantly enhanced. Improved color stability, and reliable setting characteristics after the activated campαsi te is emplaced in the tooth being repaired. The new glasses are significantly better than the barium glasses of the prior art in this regard.
It is believed that the problems encountered with the barium glasses are contributed to by the relative alkalinity of these materials. Barium is an alkaline earth element in the periodic system, and, therefore, more electropositive than zinc, which is a transition element. The higher pHs characteristic of the barium glasses cause decomposition of the peroxide catalysts normally used in these formulations and thus greatly reduce storage stability. A significant advantage of the new glasses, which is an improvement over any known heretofore, is that they contain an element, namely, zinc, that has been in regular dental use for many years Zinc oxide-containing ointments have long been used in medicine as safe and mild antibacterial agents and zinc oxide has long been used as a component in dental cements or adhesives. These latter agents are used for cementing prostheses, onlays, bridges, crowns, and the like, to the teeth. In this use they have proved safe and effective over many years. In other words, zinc compounds have a long history of being safe to use in the oral cavity, and are thus vastly preferable to use compared with those of unknown safety or known toxicity,
such as compounds of barium.
The new single phase glasses used in this invention have the following composition in percent by weight:
Zinc oxide (ZnO) 20 to 35% Silica (SiO2) 45 to 65%
Boric oxide (B2O3) 3 to 15% A luminum oxide (Al 2O3) 0 to 10% Aluminum fluori de (AlF3) At least 2% Alkali metal oxide 0 to 3% or alkaline earth metal oxide wherein the combined weight of aluminum oxide and aluminum fluoride is at least about 10%, and wherein the glass exhibits an "X-ray absorption characteristic" of at least 1/16 inch (0.15 cm). The alkali metal oxide o alkaline earth metal oxide may be, for example, sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, or the like, or combinations thereof, so long as the combined weight of such oxides does not exceed about 3% of the glass, thus maintaining the pH of the glass in the desired range of about 6.5 to 8. Of course, as will be recognized by those skilled in the art, various other ingredients may also be present in minor amounts so long as the resulting glass exhibits the desired X-ray opacity and the desired pH . However, it is highly preferred to avoid the inclusion of toxic metals such as lead, cadmium, mercury, arsenic, etc.
A preferred embodiment of the new glass for use in deπtai restoratives intended for anterior applications has the following composition:
Zinc oxide 25 to 28%
Silica 46 to 48%
Boric oxide 6 to 9%
Aluminum oxide 1 to 3% Aluminum fluoride 17 to 19%
wherein the combined weight of aluminum oxide and aluminum fluoride is not greater than about 20%, and wherein the glass exhibits an X-ray absorption characteristic of at least 3/32 inch (0.24 cm). The compositions given above are written in terms of the salts (e.g. oxides and fluorides) which are used in preparing the melt from which the glass is obtained upon cooling. This is a common practice in the glass- marking art. There is, of course, no oxide, fluoride, or other simple salt in the resultant glass. Glasses used in this invention all possess a useful degree of radiopacity.
The refractive index of the glass may be varied, depending upon the particular amount of each ingredient present. It is preferred that the refractive index of the glass filler be substantially the same as that of the binder resin when the glass is used in a dentai filling composition, i.e. within about 0.05, whan the composition is used in anterior appl ications. When the binder resin comprises the well known BIS-GMA, the refractive index for the glass filler is preferbaly 1.555 + 0.05. Matching of the refractive indices of the glass filler and the binder resin is. less important when the composition is intended for posterior dental applications. When BIS-GiMA resin is diluted with another acrylic resin (e.g. triethyleneglycol dimethacrylate) to facilitate higher filler loadings to make a composition having particular use for posterior filling applications, the resultant resin mixture may have a refractive index of 1.545, for example. Consequently, far such an application it may be preferred to use a glass composition having a refractive index of 1.545 if close matching of the resin and filler is desired. When it is desired to prepare a dental fill ing composition which is light curable it is important to obtain a close match of the refractive indices of the polymerizabl e resin and the
glass filler so that complete and rapid cure of the resin will be achieved when it is exposed to the activating light. Of course, when the composition is intended for use elsewhere in the body (i.e. where esthetics are not a factor) and where the composition is not light curable, there is no need to attempt matching the refractive index of the glass to the refractive index of the binder resin.
Radiopacity, which reflects the materials's ability to attenuate X-rays, is conveniently measured by comparing the X-ray film image density values of a disc of the cured composite of a standard thickness, e.g. 0.040 inch (0.1 cm), with corresponding values of a known standard Film image density measurements are made with a suitable densitometer, such as a Macbeth Transmission Densito meter, Model TO 504, with visible light filter (manufactured by Macbeth Div. of Kollmorgan Corp., Newburgh, 'N.Y.). A convenient standard is a stepped aluminum wedge, for example, a ten step wedge having a thickness of 1/32 inch (0.08 cm) at the thinnest step increasing to 5/16 inch (O.8 cm) at the thickest step. One empirically determines the X-ray film image density values corresponding to steps on the wedge, which indicate degrees of X-ray beam attenuation which provide, in actual practice, proper differentia tion between a composite restoration and the surrounding tooth structure. A proper level of radiopacity wi ll permit one skilled in the art to differentiate between the restoration and primary and recurrent caries in the tooth structure, and will also visualize defects in the restoration itself. By way of illustration, using a wedge, the glasses of this invention when tested in this manner give values of 1/16 inch (0.16 cm) at 26% ZnO; 3/32 - 1/8 inch (0.24 - 0.32 cm) at 26.5 - 28% ZnO. Typical barium glasses of the prior art, tested under identical conditions give values of 1/16 - 3/32 inch (0.16 - 0.24 cm). The typical "plastic" or "porcelain" filling materials (containing quartz or borosilicate filler) common in contemporary dental
practive give values of zero. A silver amalgam gives a values of > 5/16 inch (0.3 cm). It will be understood, of course, that these values are completely empirical. Using different wedges and experimental apparatus, the actual numbers one gets may be different. For the purposes of this invention, useful glasses exhibit an X-ray absorption characteristic of at least 1/16 inch (0.16 cm).
Insofar as the preparation of the zinc glass is concerned, standard techniques well-known in the glass- making art are used. See, for example, The Handbook of Glass Manufacture, Fay and Tooley. Volume I (1974) . After the melt has cooled, the glass is comminuted to a size that passes through a 325-mesh standard sieve (44 microns). For grinding the glass into smaller sizes a ball mill is used, and grinding aids such as ammonium carbonate or alcohols may be present in an amount of approximately 0.5% based on the weight of the glass.
When making dental composite restorative, the glass powder is then prepared for incorporating into an organic binder matrix by treating the surface with a si lane compound. This is a well-known technique for rendering relatively polar materials, such as siliceous powders, more compatible with relatively non-polar materials, such as organic polymers. The zinc glass is then mixed into a dentai paste.
The paste may be formed of any of the polymeri zable resin systems useful in dentistry. Especially useful resin systems comprise free-radically polymerizable materials such as the polyfunctional acrylata systems. Particularly useful in the system is 3IS-GMA, a well- known material which is the reaction product of bisphenol- A and glycidyl methacryl ate, widely used in dentistry. Other commonly used resin binders include polyurethanes, methyl methacryl ate, and isobutyl methacrylate. The zinc glass may be used alone or it may be blended with other suitable materials, such as inert glass powders, when mixed into the binder - depending, for example, on the degree of radiopacity desired in the
final composite. Along with the glass, other materials may also be mixed into the paste, such as pigments for making the restoration match the patient's natural tooth color, and reagents like hydroquinone monomethyl ether, as an inhibitor of premature polymerization of the binder. Immediately before use, and after the dentist has prepared the tooth for receiving the restoration, the paste is activated by mixing into it the appropriate amount of catalyst, such as benzoyl peroxide. For example, the dental restorative composition may be in the form of two pastes (one paste containing filler, resin binder and catalyst while the other contains filler, resin binder and accelerator), or a liquid resin and powdered filler system, or a paste- liquid resin, or any other desired form. The mixed composition is promptly em p l a c ed in the tooth, hardeni n g in the manner characteristic of the resin binder and catalyst system being used. For example, using the well-known BIS-GMA/benzoyl peroxide system, the composite becomes grossly rigid in about 5 minutes and may be finely ground and polished, to give the finished restoration, in about 10 minutes. At any time after emplacement, but more particularly after significant time has elapsed, such as many months or years afterwards, the condition of the restoration and the adjacent tooth structures can be determined by diagnostic dental X-rays.
Curable compositions which contain the novel glass and which are useful in other applications (e.g. medical and dental prostheses, pit and fissure sealants, hard tissue cements) may be prepared in similar fashion using polymerizable resin binders.
The invention is further illustrated by means of the following representative examples wherein the term "parts" refers to parts by wei gh t u n l es s o th erw i s e i ndi ca ted .
Example 1
Silica (47 gms), zinc oxide (25 gms) , baric oxide (8 gms), aluminum oxide (1 gm) and aluminum fluoride (18 gms) are thoroughly mixed, as fine powders, in a silica-lined crucible. The mixture is heated in a muffle furnace at 1450ºF. (788ºC.) until the powder has become a transparent mel t.
The molten glass is then removed from the crucible through a small hole in the crucible wall, by tilting the crucible and allowing a thin stream of glass to flow through, giving a filament of glass of about 1/32 inch (0.08 cm) diameter. This filament is quenched rapidly in cold water, to give a completely clear glass (as opposed to being opalescent). Mere air cooling of the glass is not sufficiently rapid to prevent phase separation.
The clear glass is then ground, e.g. in a ball mill, to a mean particle size range of 0.5 - 15 μm.
Example 2 Gamma-methacryloxy-propyltrimethoxy silane (2 gms) is mixed with glacial acetic acid (0.033 gms) and water (44.4 gms) in a plastic beaker. Glass powder (100 gms for example, from Example 1) is added to the mixture, and the system is stirred for 1.5 hours at room temperature. The glass slurry is dried, by warming it at 140ºF. (50 C.) for 24 hours, followed by heating it in an oven for 2.5 hours at 240ºF. (115º C).
Example 3 Two pastes, A and B, are prepared, having the following compositions: Ingredient Paste A Paste B
3IS-GMA resin 14.48 gm 14.67 gm
Triethylene glycol dimethacryl atas 4.67 4.63 Silaπe-treated filler 30.0 30.0 ( from Exaraple 2) Beπzoyl peroxide .21
Dihydroxyethyl p-toluidine
Inqredient Paste A Paste B
"Tinuvin P", a UV absorber .16
Phenylsalicylate glycidyl .14 16 methacryl ate adduct, a UV absorber
Butylated hydroxytoluene - - - - .16
Bisphenol A - - - - .14
Pigments-titanium dioxide and .17 .17 iron oxides - yellow raw sienna, burnt umber), ottalume
TOTAL 100.00 gm 100.00 gm The pastes are prepared as follows : For each paste, A and B, two preliminary mixes are made. The glass (from Example 2) and the pigments are mixed thoroughly to give an evenly colored powder. This mix is the same for each paste. The resins, accelerator, UV absorbers and inhibitor are mixed to give the mix for paste A. The resins, catalyst, UV absorber, and inhibitor are mixed to give the mix for paste B. After the two mixes, glass and resin based respectively, have been prepared, the procedure for preparing each paste, A and B, is the same .
Each resin mix is added to a vessel and then the respective glass mix is added. The two mixes are first roughly blended together, such as by shaking, and are then thoroughly mixed preferably by prolonged mechanical mixing.
The resultant homogeneous pastes, A and B, are the precursors to the dental restorations made from the materials of this invention. Pastes A and B are kept separate until immediately before the appropriate repair is made in a tooth which has been prepared to receive it. They are then mixed together thoroughly and promptly emplaced in the manner well-known in dental art.
Example 4 Using the procedure of Example 3, two pastas, A and B, are prepared having the following compositions:
The two pastes, when mixed together, form a very useful dental restorative composition.
Example 5 The glass filler of Example 1 was ball milled to a mean particle size of 4.5 microns and silane treated according to the method described in Example 2. A light- curable paste was prepared having the following compositions.
The paste is prepared as follows: The milled and treated filler (from Example 2), Aerosil R-972 (col loidal silica, commercially available from DeGussa Corporation, average particle diameter of 16 millimicrons, surface area of 110 square meters/ gram) and the pigments are blended to give an evenly colored powder. The resins, inhibitor, accelerator and photoinitiator are mixed in a dark area in a vessel excluding light. The filler blend is then added to the mixing vessel containing the resin mix. The filler, resins and other components are then thoroughly mixed by prolonged mechanical mixing, with the entire operation carried out in the absence of light.
A commercially available "KULZER TRANSLUX" irradiation device with a light guiding rod is used to cure the paste. Test samples are prepared by packing the paste into an open-ended Teflon mold with a cylindrical cavity. The loaded mold is then placed between 2 pieces of clear polyester film (each 25 microns thick) . Test samples of prescribed thickness are then irradiated for a period of exposure necessary to polymerize or cure the resin in the paste. Barcol hardness measurements are made on the top and bottom of the test sample to determine the extent of polymerization. The following Barcol hardnesses are determined on cured test samples using two different sample thicknesses.
Barcol hardness values in excess of 30 are considered outstanding. Standard, commercially available dentai restorative composites typically have Barcol hardness values of 70 - 75 after 24 hours cure.
The filler loading levels of 33% attained with the zinc glass must also be considered to be extraordinary. Conventional radiopaque barium glass permits maximum filler loadings of 73 - 30% when using similar particle size distributions.
Example 6 The glass filler of Example 1 was ball milled to a mean particle size of 1.8 microns and silane treated according to the method described in Example 2. A light-curable pasta having the following composition was prepared using the procedure of Example 5:
Barcol hardnesses were determined on 2 mm thick test samples of composition cured at two different exposure times:
Example 7 The glass filler of Example 1 was ball mil led to a mean particle size of 4.5 - 5.0 microns. Radiopaque impression pastes , containing the ingredients listed below, were prepared by mixing the ingredients in a conventional Ross brand mixer:
The concentration of the filler may be varied, as desired, to produce compositions having various viscosities. Compositions containing 30 - 40% filler are of low viscosity, while compositions containing 80 - 90% filler have a putty consistency.
Claims
Claims
1. A single phase glass composition consisting essen tially of, in percent by weight: Zinc oxide 20 to 35% Silica 45 to 03% Boric oxide 3 to 15% Aluminum oxide 0 to 10% Aluminum fluoride At least 2% Alkali metal oxide or 0 to 5% alkaline earth metal oxide
A dentai filling composition comprising a poly merizable resin binder and a finely divided inorganic glass filler which is X-ray opaque and single phase, wherein said glass filler has the composition of claim 1.
A composition in accordance with claim 2, wherein said binder comprises a free-radically polymerizable resin.
4. A composition in accordance with claim 3, wherein said polymerizable resin binder comprises BIS-GMA 5. A composition in accordance with claim 2, wherein the index of refraction of said glass filler and said resin are substantially the same. 6. A composition in accordance with claim 2, wherein said composition is in the form of two pastes, the first said paste comprising polymerizabl e resin binder, inorganic glass filler, and a catalyst,
and the second said paste comprising polymerizable resin binder, inorganic glass filler, and an accelerator.
7. A composition in accordance with claim 6, wherein said filler represents at least about 70% by weight of each said paste.
8. A composition in accordance with claim 6, wherein said binder in each said paste comprises BIS-GMA. 9. A composition in accordance with claim 4, wherein said glass filler consists essentially of, in percent by weight :
Zinc oxide 25 to 23%
Silica 46 to 43%
Boric oxide 6 to 9%
Aluminum oxide 1 to 3 %
Aluminum fluoride 1 7 to 1 9% wherein the combined weight of aluminum oxide and aluminum fluoride is not greater than about 20%.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US18491680A | 1980-09-08 | 1980-09-08 | |
US184916 | 1994-01-24 |
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EP0059194A1 EP0059194A1 (en) | 1982-09-08 |
EP0059194A4 true EP0059194A4 (en) | 1984-03-27 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19810902360 Ceased EP0059194A4 (en) | 1980-09-08 | 1981-08-18 | Zinc-containing glass composition. |
Country Status (6)
Country | Link |
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EP (1) | EP0059194A4 (en) |
JP (1) | JPS57501376A (en) |
AU (1) | AU550056B2 (en) |
CA (1) | CA1157892A (en) |
IT (1) | IT1142743B (en) |
WO (1) | WO1982000827A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4503169A (en) * | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
GB2264711A (en) * | 1992-03-06 | 1993-09-08 | British Tech Group | Glass-polyalkenoate cements |
PL3218317T3 (en) | 2014-11-13 | 2019-03-29 | Gerresheimer Glas Gmbh | Glass forming machine particle filter, a plunger unit, a blow head, a blow head support and a glass forming machine adapted to or comprising said filter |
FR3116823B1 (en) * | 2020-11-30 | 2023-03-24 | Commissariat Energie Atomique | Thermal insulation coating based on a PREceramic Polymer to improve the performance of heat engines |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3826778A (en) * | 1970-02-17 | 1974-07-30 | Owens Illinois Inc | Tooth filling and facing compositions comprising a radiopaque glass and method of making the same |
US3911581A (en) * | 1970-02-17 | 1975-10-14 | Owens Illinois Inc | Tooth filling and facing composition comprising a radiopaque glass and method of using the same |
US3715331A (en) * | 1970-05-01 | 1973-02-06 | Coe Labor | Monomer soluble x-ray opaque methacrylate particles |
US3882080A (en) * | 1971-01-15 | 1975-05-06 | Espe Pharm Praep | Self-hardening compound, particularly for dental-medical application |
US4028325A (en) * | 1972-08-09 | 1977-06-07 | King Alan G | Composite dental material and method of preparing same |
GB1450157A (en) * | 1973-03-06 | 1976-09-22 | Colgate Palmolive Co | Dental powder cement and filling material |
US4017454A (en) * | 1973-09-21 | 1977-04-12 | Jenaer Glaswerk Schott & Gen. | Glass ceramic as filler in polymerizable dental filling compositions |
AT339523B (en) * | 1973-09-21 | 1977-10-25 | Jenaer Glaswerk Schott & Gen | CERAMIC GLASS FOR FULL DENTALS |
US3971754A (en) * | 1973-12-10 | 1976-07-27 | Pennwalt Corporation | X-ray opaque, enamel-matching dental filling composition |
US4050947A (en) * | 1976-03-17 | 1977-09-27 | Bullseye Glass Co. | Process for opalizing glass |
US4215033A (en) * | 1978-09-08 | 1980-07-29 | American Dental Association Health Foundation | Composite dental material |
US4250277A (en) * | 1980-01-07 | 1981-02-10 | International Standard Electric Corporation | Glass composition for water setting ion-polymer cements |
-
1981
- 1981-08-18 WO PCT/US1981/001104 patent/WO1982000827A1/en not_active Application Discontinuation
- 1981-08-18 AU AU75348/81A patent/AU550056B2/en not_active Ceased
- 1981-08-18 EP EP19810902360 patent/EP0059194A4/en not_active Ceased
- 1981-08-18 JP JP56502852A patent/JPS57501376A/ja active Pending
- 1981-09-04 CA CA000385221A patent/CA1157892A/en not_active Expired
- 1981-09-07 IT IT49244/81A patent/IT1142743B/en active
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No relevant documents have been disclosed * |
Also Published As
Publication number | Publication date |
---|---|
IT8149244A0 (en) | 1981-09-07 |
AU550056B2 (en) | 1986-02-27 |
AU7534881A (en) | 1982-04-05 |
JPS57501376A (en) | 1982-08-05 |
IT1142743B (en) | 1986-10-15 |
WO1982000827A1 (en) | 1982-03-18 |
CA1157892A (en) | 1983-11-29 |
EP0059194A1 (en) | 1982-09-08 |
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