NO158991B - POLYMERIZABLE DENTAL MASS AND PROCEDURE FOR PREPARING THIS. - Google Patents
POLYMERIZABLE DENTAL MASS AND PROCEDURE FOR PREPARING THIS. Download PDFInfo
- Publication number
- NO158991B NO158991B NO811448A NO811448A NO158991B NO 158991 B NO158991 B NO 158991B NO 811448 A NO811448 A NO 811448A NO 811448 A NO811448 A NO 811448A NO 158991 B NO158991 B NO 158991B
- Authority
- NO
- Norway
- Prior art keywords
- weight
- monomer
- reducing agent
- parts
- copper ions
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 36
- 239000003638 chemical reducing agent Substances 0.000 claims description 34
- -1 peroxy compound Chemical class 0.000 claims description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 29
- 229910001431 copper ion Inorganic materials 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 210000003074 dental pulp Anatomy 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229940124024 weight reducing agent Drugs 0.000 claims 10
- 239000013585 weight reducing agent Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 12
- 150000002978 peroxides Chemical class 0.000 description 11
- 239000005749 Copper compound Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 150000001880 copper compounds Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000011521 glass Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 210000000214 mouth Anatomy 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229960001748 allylthiourea Drugs 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 150000003585 thioureas Chemical class 0.000 description 3
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 2
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 2
- UCGFRIAOVLXVKL-UHFFFAOYSA-N benzylthiourea Chemical compound NC(=S)NCC1=CC=CC=C1 UCGFRIAOVLXVKL-UHFFFAOYSA-N 0.000 description 2
- GMEGXJPUFRVCPX-UHFFFAOYSA-N butylthiourea Chemical compound CCCCNC(N)=S GMEGXJPUFRVCPX-UHFFFAOYSA-N 0.000 description 2
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000551 dentifrice Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- POXAIQSXNOEQGM-UHFFFAOYSA-N propan-2-ylthiourea Chemical compound CC(C)NC(N)=S POXAIQSXNOEQGM-UHFFFAOYSA-N 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KAGLPYRXTCQWHU-UHFFFAOYSA-N (2,4-dimethylphenyl)thiourea Chemical compound CC1=CC=C(NC(N)=S)C(C)=C1 KAGLPYRXTCQWHU-UHFFFAOYSA-N 0.000 description 1
- HXCHZMHFZXNFIX-UHFFFAOYSA-N (2-methoxyphenyl)thiourea Chemical compound COC1=CC=CC=C1NC(N)=S HXCHZMHFZXNFIX-UHFFFAOYSA-N 0.000 description 1
- BHJYKFUCQNISJA-UHFFFAOYSA-N (3-hydroxyphenyl)thiourea Chemical compound NC(=S)NC1=CC=CC(O)=C1 BHJYKFUCQNISJA-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- OLTJYOMEFRRCKA-UHFFFAOYSA-N 1,1,3-triphenylthiourea Chemical compound C=1C=CC=CC=1N(C=1C=CC=CC=1)C(=S)NC1=CC=CC=C1 OLTJYOMEFRRCKA-UHFFFAOYSA-N 0.000 description 1
- OVRQXQSDQWOJIL-UHFFFAOYSA-N 1,1-dibutylthiourea Chemical compound CCCCN(C(N)=S)CCCC OVRQXQSDQWOJIL-UHFFFAOYSA-N 0.000 description 1
- QADMBPYDNAHONY-UHFFFAOYSA-N 1,1-diethyl-3-prop-2-enylthiourea Chemical compound CCN(CC)C(=S)NCC=C QADMBPYDNAHONY-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- UKOJOHPYEVWPNN-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-methylthiourea Chemical compound CNC(=S)NC1=CC=C(Cl)C=C1 UKOJOHPYEVWPNN-UHFFFAOYSA-N 0.000 description 1
- WGTSYSMCCBVJNF-UHFFFAOYSA-N 1-(4-ethenylphenyl)-3-methylthiourea Chemical compound CNC(=S)NC1=CC=C(C=C)C=C1 WGTSYSMCCBVJNF-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XZETWBTXPADGDR-UHFFFAOYSA-N 3-methyl-1,1-diphenylthiourea Chemical compound C=1C=CC=CC=1N(C(=S)NC)C1=CC=CC=C1 XZETWBTXPADGDR-UHFFFAOYSA-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
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DQGASIACJAQOCL-UHFFFAOYSA-N C(=C)=C(CO)O Chemical group C(=C)=C(CO)O DQGASIACJAQOCL-UHFFFAOYSA-N 0.000 description 1
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical group CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 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 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VAVFWTOVXLDJFG-UHFFFAOYSA-N n-(butylcarbamothioyl)butanamide Chemical compound CCCCNC(=S)NC(=O)CCC VAVFWTOVXLDJFG-UHFFFAOYSA-N 0.000 description 1
- JLMHZVYLAQPMOZ-UHFFFAOYSA-N noxytiolin Chemical compound CNC(=S)NCO JLMHZVYLAQPMOZ-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 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
- QAKUNEDFMJPMGO-UHFFFAOYSA-N octylthiourea Chemical compound CCCCCCCCNC(N)=S QAKUNEDFMJPMGO-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical class CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
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Description
Oppfinnelsen angår generelt polymeriserbare dentalmasser, og spesielt slike som er istand hurtig til å herde under dannelse av et polymerisatprodukt med en forholdsvis høyere mengde av uoppløselig komponent. The invention generally relates to polymerizable dental masses, and in particular those which are able to harden quickly while forming a polymer product with a relatively higher amount of insoluble component.
Polymeriserbare dentalmasser basert på bruk av methacrylatmonomerer, f.eks. reaksjonsproduktet av bis-glycidyletheren av bisfenol A og methacrylsyre (herefter be-tegnet som BIS-GMA) ,■ er vanlig anvendt som fyllinger, grop-forseglingsmidler og rissforseglingsmidler og kan med fordel anvendes for en lang rekke forskjellige tannreparasjons-metoder. Slike masser omfatter typisk én eller flere methacrylatmonomerer og minst én komponent av et fritt radikal-frigjørende (redox) polymerisasjonssystem for monomeren eller monomerene. Monomerblandingen som fremstilles på denne måte, omfatter som regel en katalysator av peroxydtypen (oxydasjonsmiddel) som senere bringes i kontakt med reduksjonsmidlet kort tid før anvendelsen for tannreparasjonen. Når oxydasjonsmidlet kommer i kontakt med reduksjonsmidlene, Polymerizable dental masses based on the use of methacrylate monomers, e.g. the reaction product of the bis-glycidyl ether of bisphenol A and methacrylic acid (hereinafter referred to as BIS-GMA) is commonly used as fillings, pit sealants and rice sealants and can be advantageously used for a wide range of different tooth repair methods. Such masses typically comprise one or more methacrylate monomers and at least one component of a free radical-releasing (redox) polymerization system for the monomer or monomers. The monomer mixture produced in this way usually comprises a catalyst of the peroxide type (oxidizing agent) which is later brought into contact with the reducing agent shortly before use for the tooth repair. When the oxidizing agent comes into contact with the reducing agents,
som regel i form av pastaer for enkelhets skyld, finner polymerisasjon sted som fører til at det dannes et polymerisat med de fysikalske egenskaper som er nødvendige for å opp-rettholde en god strukturmessig helhet i munnhulen, f.eks. usually in the form of pastes for the sake of simplicity, polymerization takes place which leads to the formation of a polymer with the physical properties necessary to maintain a good structural integrity in the oral cavity, e.g.
høy trykkfasthet, høy grad av uoppløselige komponenter etc. Den sistnevnte betingelse er sterkt ønsket for å nedsette high compressive strength, high degree of insoluble components etc. The latter condition is strongly desired to reduce
en utluting av vitale bestanddeler og derav følgende ned-brytning av polymerisatet til et minimum. a leaching of vital constituents and consequent degradation of the polymer to a minimum.
En hurtig og fullstendig herding er således sterkt ønskede formål. En økning i katalysatorkonsentrasjonen for-bedrer i noen grad herdehastigheten, men en overensstemmende forbedring i herdegraden blir ikke nødvendigvis oppnådd. Det er i virkeligheten ofte tilfellet at store katalysatorkon-sentrasjoner hemmer herdegraden og fører således til en forholdsvis større prosentuell andel av oppløselige og utlut-bare komponenter i sluttpolymerisatet. Dessuten øker store mengder av peroxydkatalysatoren muligheten for en forpoly-merisasjon av methacrylatmonomer, dvs. før kontakten med reduksjonsmidlet, hvorved det ofte er nødvendig.å anvende tilsetningsmidler, som regel, i uvanlig store mengder for å utøve en stabiliserende eller polymerisasjonshemmende virk-ning. Slike hemmende virkninger gir seg imidlertid uunngåelig i en viss grad til kjenne under kontakten mellom monomer, oxydasjonsmiddel og reduksjonsmiddel, hvorved herdehastigheten senkes og uunngåelig også herdegraden. A rapid and complete curing is thus a highly desired objective. An increase in the catalyst concentration improves the cure rate to some extent, but a corresponding improvement in the degree of cure is not necessarily achieved. In reality, it is often the case that large catalyst concentrations inhibit the degree of curing and thus lead to a relatively larger percentage of soluble and leachable components in the final polymer. In addition, large quantities of the peroxide catalyst increase the possibility of a pre-polymerisation of methacrylate monomer, i.e. before contact with the reducing agent, whereby it is often necessary to use additives, as a rule, in unusually large quantities to exert a stabilizing or polymerization-inhibiting effect. Such inhibitory effects, however, inevitably make themselves felt to a certain extent during the contact between monomer, oxidizing agent and reducing agent, whereby the curing speed is lowered and inevitably also the degree of curing.
Det er et hovedformål ved oppfinnelsen å tilveiebringe polymeriserbare dentalmasser for hvilke de ovennevnte og beslektede ulemper er blitt fjernet eller i det minste re-dusert i sterk grad. It is a main purpose of the invention to provide polymerizable dental masses for which the above-mentioned and related disadvantages have been removed or at least reduced to a great extent.
Det er også et formål ved oppfinnelsen å tilveiebringe polymeriserbare dentalmasser som er istand til å utsettes for en hurtig herdehastighet under dannelse av et polymerisat med en forholdsvis høy mengde av uoppløselig komponent. It is also an object of the invention to provide polymerizable dental masses which are capable of being subjected to a rapid curing rate while forming a polymer with a relatively high amount of insoluble component.
Det er dessuten et formål ved oppfinnelsen å tilveiebringe en slik masse som har god strukturmessig stabilitet under de betingelser som foreligger i menneskets munnhule. It is also an object of the invention to provide such a mass which has good structural stability under the conditions that exist in the human oral cavity.
Det er også et formål ved oppfinnelsen å tilveiebringe en slik masse som ikke krever bruk av høyere katalysator-konsentrasjoner for å oppnå en effektiv herdehastighet og It is also an object of the invention to provide such a mass which does not require the use of higher catalyst concentrations in order to achieve an effective curing speed and
-grad. -degree.
Det er ytterligere et formål ved oppfinnelsen å tilveiebringe slike masser som har de ovenfor beskrevne gunstige egenskaper til tross for at de ikke inneholder fyllstoffer og/eller koplingskomponenter etc. It is a further object of the invention to provide such masses which have the above-described favorable properties despite the fact that they do not contain fillers and/or coupling components etc.
Det er et videre formål ved oppfinnelsen å tilveiebringe slike masser hvori, i overensstemmelse med en spesielt foretrukken utførelsesform av oppfinnelsen, monomerens stabilitet i nærvær av en peroxydkatalysator blir sterkt forbedret . It is a further object of the invention to provide such masses in which, in accordance with a particularly preferred embodiment of the invention, the stability of the monomer in the presence of a peroxide catalyst is greatly improved.
Det er et ytterligere formål ved oppfinnelsen å tilveiebringe en fremgangsmåte for fremstilling av slike dentalmasser av høy kvalitet. It is a further object of the invention to provide a method for the production of such dental masses of high quality.
De ovenfor beskrevne og beslektede formål oppnås ifølge oppfinnelsen sem mer generelt angår en polymeriserbar dentalmasse , idet dentalmassen har forbedret herdehastighet og inneholder minst ett monomert methacrylat med 2-4 polymeriserbare dobbeltbindinger, 0-400 vektdeler organisk, partikkelformig fyllstoff, 0-5 vektdeler silankoplingsmiddel, 0,5-5 vektdeler av en polymerisasjons.katalysator som omfatter en organisk peroxyforbindelse og som danner frie radikaler, og et reduksjonsmiddel, hvorved samtlige vektdeler er basert på monomeren, og idet preparatet består av en oxydasjonsblanding og en reduksjonsblanding som foreligger adskilt anordnet, eller i blanding med hverandre når polymerisasjonen skal finne sted, og den polymeriserbare dentalmasse er særpreget ved at den inneholder 0,5-5 vektdeler reduksjonsmiddel, The above-described and related purposes are achieved according to the invention, which more generally concerns a polymerizable dental mass, the dental mass having improved curing speed and containing at least one monomeric methacrylate with 2-4 polymerizable double bonds, 0-400 parts by weight of organic, particulate filler, 0-5 parts by weight of silane coupling agent, 0.5-5 parts by weight of a polymerization catalyst which comprises an organic peroxy compound and which forms free radicals, and a reducing agent, whereby all parts by weight are based on the monomer, and the preparation consists of an oxidation mixture and a reduction mixture which is arranged separately, or mixed with each other when polymerization is to take place, and the polymerizable dental pulp is characterized by the fact that it contains 0.5-5 parts by weight of reducing agent,
basert på monomeren, idet mengden av reduksjonsmiddel ikke utgjør over 40 vekt% av den samlede mengde av peroxyforbindelse og reduksjonsmiddel, og at dessuten som akselerasjonsmiddel toverdige kobberioner er tilstede i en for aktiveringen av katalysatoren virksom konsentrasjon av 5-100 ppm, basert på monomeren, eventuelt sammen med opp til 50 vekt% énverdige kobberioner, basert på vekten av de toverdige kobberioner, opp til en samlet konsentrasjon av kobberioner av 100 ppm, basert på monomeren. based on the monomer, as the amount of reducing agent does not amount to more than 40% by weight of the total amount of peroxy compound and reducing agent, and that, in addition, as an accelerator, divalent copper ions are present in a concentration effective for the activation of the catalyst of 5-100 ppm, based on the monomer, optionally together with up to 50% by weight of monovalent copper ions, based on the weight of the divalent copper ions, up to a total concentration of copper ions of 100 ppm, based on the monomer.
Oppfinnelsen angår også en fremgangsmåte for fremstilling av en polymeriserbar dentalmasse med forbedret herdehastighet, hvor et monomert methacrylat med 2-4 polymeriserbare dobbeltbindinger, 0-400 vektdeler uorganisk, partikkelformig fyllstoff,0-5 vektdeler silankoplingsmiddel, 0,5-5 vektdeler -av en polymerisasjonskatalysator som omfatter en organisk peroxyforbindelse og som .danner frie radikaler, og et reduksjonsmiddel for peroxyforbindelseTi,, idet de angitte vektdeler .•alle ©a: .basert .på monomeren.., Iblandes med hverandre, idet reMcsJiOB^jUa-iiid&ngsæn Jboldes «a&sflcilLt fra oxydasjons-ibl-andlingein .'inntil det tifåsipurikt når polymer isa jon er ønsket, og fremgangsmcLten er særpreget ved at det tilsettes 0,5-5 vektdeler, basert på 100 vektdeler av monomeren, av reduksjonsmidlet, idet reduksjonsmidlet ikke tilsettes i en mengde over 40 vekt% av den samlede mengde av peroxyforbindelse og reduksjonsmiddel, og dessuten at det som akselerasjonsmiddel tilsettes toverdige kobberioner i en for aktivering av katalysatoren virksom konsentrasjon av 5-100 ppm, basert på monomeren, eventuelt sammen med opp til 5 0 ve'kt% énverdige kobberioner, basert på vekten av de toverdige kobberioner, The invention also relates to a method for the production of a polymerizable dental compound with improved curing speed, where a monomeric methacrylate with 2-4 polymerizable double bonds, 0-400 parts by weight of inorganic, particulate filler, 0-5 parts by weight of silane coupling agent, 0.5-5 parts by weight of a polymerization catalyst which comprises an organic peroxy compound and which .forms free radicals, and a reducing agent for peroxy compound Ti,, in that the stated parts by weight are all ©a: .based .on the monomer.., are mixed with each other, as the reMcsJiOB^jUa-iiid&ngsæn Jboldes a&sflcilLt from an oxidation reaction until it becomes pure when polymer ion is desired, and the process is characterized by the addition of 0.5-5 parts by weight, based on 100 parts by weight of the monomer, of the reducing agent, as the reducing agent is not added in a amount over 40% by weight of the total amount of peroxy compound and reducing agent, and furthermore that divalent copper is added as an accelerator ions in a concentration effective for activating the catalyst of 5-100 ppm, based on the monomer, possibly together with up to 50% by weight of monovalent copper ions, based on the weight of the divalent copper ions,
opp til en samlet kobberionkonsentrasjon i dentalmassen up to a total copper ion concentration in the dental pulp
av 100 ppm, basert på monomeren. of 100 ppm, based on the monomer.
Toverdige kobberioner tilveiebringes enklest i form Divalent copper ions are most easily provided in form
av kobbersalter med organiske og uorganiske syrer. Spesielt foretrukne materialer for anvendelse ifølge oppfinnelsen omfatter toverdig kobberacetat, toverdig kobberacetylacetonat, toverdig kobberklorid eller toverdig kobbersulfat. Forbind-elsene kan anvendes alene eller i blanding med to eller flere av hverandre. Dessuten kan enverdige kobberioner være tilstede sammen med de ovennevnte selv om de toverdige kobber-forbindelser i alminnelighet har vist seg å være mer effektive hva gjelder å oppnå både en høy herdegrad og høy herdehastighet. Det er derfor spesielt foretrukket ifølge oppfinnelsen at toverdige kobberioner (Cu<++>) utgjør minst 50% av den samlede mengde anvendte kobberioner. Imidlertid gir, som nærmere beskrevet senere, bruk av enverdige kobbersalter en betydelig forbedring sammenlignet med forsøk hvori ingen kobberioner inngår. Hvorvidt dette skyldes nærværet av toverdige kobberioner som uunngåelig er tilstede i tilgjengelige enverdige kobbersalter, eller de enverdige kobberioner eller kombinasjonen av disse, er ikke blitt entydig fastlagt. of copper salts with organic and inorganic acids. Particularly preferred materials for use according to the invention include divalent copper acetate, divalent copper acetylacetonate, divalent copper chloride or divalent copper sulfate. The compounds can be used alone or in a mixture with two or more of each other. Also, monovalent copper ions may be present together with the above although the divalent copper compounds have generally been found to be more effective in achieving both a high degree of cure and a high rate of cure. It is therefore particularly preferred according to the invention that divalent copper ions (Cu<++>) make up at least 50% of the total amount of copper ions used. However, as described in more detail later, the use of monovalent copper salts provides a significant improvement compared to experiments in which no copper ions are included. Whether this is due to the presence of divalent copper ions which are unavoidably present in available monovalent copper salts, or the monovalent copper ions or the combination thereof, has not been unequivocally determined.
Mengden av kobberioner som er tilstede i monomerblandingen, er meget liten og varierer fra 5 til The amount of copper ions present in the monomer mixture is very small and varies from 5 to
100 ppm, fortrinnsvis fra 8 til 50 ppm, basert på den samlede monomermengde. Uttrykt på annen måte er mengden av kobberioner i det minste den mengde som er nødvendig for å gi effektive katalysatoraktiverende/eller akselererende virkninger. Betegnelsen "samlet monomermengde" som her anvendt betegner den samlede monomermengde som vil være tilstede på det tidspunkt polymerisasjonen i virkeligheten finner sted. I overensstemmelse med en foretrukken utførelsesform innarbeides 100 ppm, preferably from 8 to 50 ppm, based on the total monomer amount. In other words, the amount of copper ions is at least the amount necessary to provide effective catalyst activating/or accelerating effects. The term "total amount of monomer" as used here denotes the total amount of monomer that will be present at the time the polymerization actually takes place. In accordance with a preferred embodiment is incorporated
således peroxydkatalysatoren, monomeren og eventuelt fyllstoff i en første pastablanding som betegnes som "oxydasjonsmiddel"-pastaen, og reduksjonsmidlet for peroxydkatalysatoren innarbeides i en annen "reduksjonsmiddel"-pasta som fortrinnsvis omfatter de samme komponenter som den første pasta, bortsett fra peroxydkatalysatoren. Pastaene blandes kort tid før den tannpleiemessige anvendelse, hvorefter poly-merisas jonen igangsettes. Kobberionene kan tilsettes til én eller begge av pastablandingene, og det er mest foretrukket at de er tilstede i oxydasjonsmiddelblandingen. I ethvert tilfelle refererer kobberionkonsentrasjonen ifølge denne ut-førelsesform seg til den samlede monomermengde som er tilstede både i oxydasjonsmiddelpastaen og i reduksjonsmiddel-pastaen. Konsentrasjonen av kobberioner varierer fra 0,02 til 0,4% av peroxydforbindelsen, basert på katalysatoren. thus the peroxide catalyst, the monomer and any filler in a first paste mixture which is referred to as the "oxidizing agent" paste, and the reducing agent for the peroxide catalyst is incorporated into another "reducing agent" paste which preferably comprises the same components as the first paste, except for the peroxide catalyst. The pastes are mixed shortly before dental care use, after which the polymerization is initiated. The copper ions may be added to one or both of the paste mixtures, and it is most preferred that they are present in the oxidizing agent mixture. In any case, the copper ion concentration according to this embodiment refers to the total amount of monomer present both in the oxidizing agent paste and in the reducing agent paste. The concentration of copper ions varies from 0.02 to 0.4% of the peroxide compound, based on the catalyst.
Det foretrekkes i alminnelighet å tilsette kobberforbindelsen til det flytende monomersystem (uten fyllstoff) som er beregnet for anvendelse som oxydasjonsmiddelpasta. It is generally preferred to add the copper compound to the liquid monomer system (without filler) intended for use as an oxidizer paste.
Kobberforbindelsen kan tilsettes til blandingen ved å fordele denne i den normalt flytende komponent av monomer eller monomerer. Den nødvendige dispersjon kan oppnås ved å tilsette kobberforbindelsen til monomeren i form av en oppløsning i et oppløsningsmiddel som fortrinnsvis utgjøres av et polart organisk oppløsningsmiddel med lavt kokepunkt, som ether eller en lavere alkanol, f.eks. methanol. Da oppløsningsmidlet bare tjener som en bærer for kobberforbindelsen, er det mest ønsket at det har høy flyktighet slik at mesteparten av eller hele mengden av oppløsningsmiddel i alminnelighet fjernes under påfølgende håndteringer, f.eks. ved blanding etc. Den anvendte mengde oppløsningsmiddel er ganske lav slik at det fås 80 ppm Cu<++>, og når bare en 1%-ig oppløsning i methanol anvendes, vil oppløsningsmiddelvolumet bare utgjøre 12,5% av monomervolumet og 2,5% av en egnet pasta, basert på vekt. Kobberforbindelsen kan alternativt adsorberes på fyllstoffkomponenten, f.eks. siliciumdioxyd, dersom et slikt materiale anvendes, for å blandes med monomer-komponenten eller -komponentene. The copper compound can be added to the mixture by distributing it in the normally liquid component of monomer or monomers. The necessary dispersion can be achieved by adding the copper compound to the monomer in the form of a solution in a solvent which is preferably a polar organic solvent with a low boiling point, such as ether or a lower alkanol, e.g. methanol. Since the solvent serves only as a carrier for the copper compound, it is most desirable that it has high volatility so that most or all of the solvent is generally removed during subsequent handling, e.g. by mixing etc. The amount of solvent used is quite low so that 80 ppm Cu<++> is obtained, and when only a 1% solution in methanol is used, the solvent volume will only amount to 12.5% of the monomer volume and 2.5 % of a suitable paste, based on weight. The copper compound can alternatively be adsorbed on the filler component, e.g. silicon dioxide, if such a material is used, to be mixed with the monomer component or components.
Foruten kobberforbindelsen inneholder de foretrukne blandinger ifølge oppfinnelsen de følgende komponenter: In addition to the copper compound, the preferred mixtures according to the invention contain the following components:
Methacrylatmonomeren velges fra materialer The methacrylate monomer is selected from materials
som har 2-4 polymeriserbare dobbelt- which have 2-4 polymerizable double-
bindinger pr. molekyl for at det herdede materiale skal tverrbindes og således bli bedre egnet for anvendelse i munnhulen. De mest foretrukne monomerer er slike som har 2 polymeriserbare dobbeltbindinger pr. molekyl. Egnede egenskaper for slike monomerer omfatter lav polymerisasjons-krymping, lav varmeutvikling under polymerisasjon, lav vann-adsorpsjon og evne til å herde hurtig og fullstendig i munnen. Det er også ønsket at monomerene har lav flyktighet og ikke er irriterende overfor tannmargen. bindings per molecule so that the hardened material is cross-linked and thus becomes better suited for use in the oral cavity. The most preferred monomers are those that have 2 polymerizable double bonds per molecule. Suitable properties for such monomers include low polymerization shrinkage, low heat development during polymerization, low water adsorption and the ability to harden quickly and completely in the mouth. It is also desired that the monomers have low volatility and are not irritating to the dental pulp.
Methacrylatmonomerer som er spesielt anvendbare ifølge oppfinnelsen, er slike som kan representeres ved de følgende generelle formler: Methacrylate monomers which are particularly useful according to the invention are those which can be represented by the following general formulas:
hvor M betegner methacryloyloxy, dvs. CH2=C(CH^)C00-, where M denotes methacryloyloxy, i.e. CH2=C(CH^)C00-,
M<1> betegner methacryloyloxy eller hydroxyl, A betegner alkylen med 1-3 carbonatomer, som methylen, propylen, isopropylen, hydroxyalkylen med 1-3 carbonatomer, som hydroxy-methylen, 2-hydroxypropylen(eller acetoxyalkylen med 3-5 carbonatomer i alkylengruppen, som 2-acetoxypropylen eller 3-acetoxyamylen etc, n betegner 1-4, fortrinnsvis 1 eller 2, m betegner 2 eller 3, og p betegner 1 eller 2, med det forbehold at summen av m og p er 4, R betegner hydrogen, methyl, ethyl eller -A-M hvori A og M er som beskrevet ovenfor, Ar betegner fenylen, f.eks. o-fenylen, m-fenylen eller p-fenylen, alkylsubstituert fenylen, f.eks. tolylen eller 5-t-butyl-m-fenylen;eller en cycloalifatisk gruppe med 6-10 carbonatomer, som 1,3-cyclohexylen, B betegner M<1> denotes methacryloyloxy or hydroxyl, A denotes alkylene with 1-3 carbon atoms, such as methylene, propylene, isopropylene, hydroxyalkylene with 1-3 carbon atoms, such as hydroxy-methylene, 2-hydroxypropylene (or acetoxyalkylene with 3-5 carbon atoms in the alkylene group , such as 2-acetoxypropylene or 3-acetoxyamylene etc, n denotes 1-4, preferably 1 or 2, m denotes 2 or 3, and p denotes 1 or 2, with the proviso that the sum of m and p is 4, R denotes hydrogen , methyl, ethyl or -A-M where A and M are as described above, Ar denotes phenylene, eg o-phenylene, m-phenylene or p-phenylene, alkyl substituted phenylene, eg tolylene or 5-t-butyl -m-phenylene; or a cycloaliphatic group with 6-10 carbon atoms, such as 1,3-cyclohexylene, B denotes
hvori R^ og R,, uavhengig av hverandre betegner in which R^ and R,, independently of each other denote
hydrogen, alkyl, f.eks. C^-C^-alkyl, eller substituert alkyl, og R' betegner alkylen med 2-12 carbonatomer, som ethylen hydrogen, alkyl, e.g. C₁-C₁-alkyl, or substituted alkyl, and R' denotes the alkylene of 2-12 carbon atoms, such as ethylene
2 2 2 2 2 2 2 2
eller dodecylen etc, eller -R (O-R ) OR— hvori R betegner alkylen med 2 eller 3 carbonatomer, som ethylen, propylen or dodecylene etc, or -R (O-R ) OR— in which R denotes alkylene with 2 or 3 carbon atoms, such as ethylene, propylene
3 3
eller isopropylen og x er fra 0 til 5, og R betegner fenylen, tolylen, methylen-bis-fenylen eller alkylen med 2-12 carbonatomer. or isopropylene and x is from 0 to 5, and R denotes phenylene, tolylene, methylene-bis-phenylene or alkylene with 2-12 carbon atoms.
Monomerer med de ovenstående formler er velkjente og Monomers with the above formulas are well known and
i alminnelighet tilgjengelige i handelen. De kan også lett freivistilles ved hjelp av vanlige syntesemetoder, f .eks. ved å reagere en fenolisk forbindelse, som difenolsyre, flor-glucinol eller bisfenol A med glycidylmethacrylat i nærvær av forskjellige tertiære aminer eller ved å reagere methacrylsyre med en epoxydholdig forbindelse, som diglycidyletheren av en bisfenol. Enkelte av disse monomerer fremstilles også ved å reagere egnede alkoholer med methacrylsyre, metha-crylylklorid eller methacrylsyreanhydrid. Eksempler på monomerer med disse formeler, omfatter: generally available commercially. They can also be easily released using common synthesis methods, e.g. by reacting a phenolic compound, such as diphenolic acid, fluoroglucinol or bisphenol A with glycidyl methacrylate in the presence of various tertiary amines or by reacting methacrylic acid with an epoxy-containing compound, such as the diglycidyl ether of a bisphenol. Some of these monomers are also produced by reacting suitable alcohols with methacrylic acid, methacrylyl chloride or methacrylic anhydride. Examples of monomers with these formulas include:
Monomerer med formlene I, II, III og IV er foretrukne ifølge oppfinnelsen. Blant disse monomerer er monomerene I, Monomers of the formulas I, II, III and IV are preferred according to the invention. Among these monomers are the monomers I,
II og III spesielt foretrukne, og monomerene IV anvendes oftere i blanding med én eller flere av monomerene I, II og III. II and III are particularly preferred, and the monomers IV are more often used in a mixture with one or more of the monomers I, II and III.
Andre methacrylatmonomerer som kan anvendes ifølge oppfinnelsen, omfatter slike som har de følgende formeler, hvori M og Ar har samme betydning som beskrevet ovenfor: Other methacrylate monomers that can be used according to the invention include those that have the following formulas, in which M and Ar have the same meaning as described above:
(MR 4 OAr)„C(CH-)0 hvori R 4 betegner isopropylen, (MR 4 OAr)„C(CH-)0 in which R 4 denotes isopropylene,
5 5 5 5 5 5
(MR OAr). og (MR 0)-Ar hvori R betegner 2-hydroxy-propylen, MA R M hvori R 6 betegner hydroxycyclopentyl eller hydroxycyclohexyl og A 2-hydroxyethylen, og M2R 8 hvori R<8 >betegner (MR OAr). and (MR 0)-Ar in which R denotes 2-hydroxy-propylene, MA R M in which R 6 denotes hydroxycyclopentyl or hydroxycyclohexyl and A 2-hydroxyethylene, and M2R 8 in which R<8 > denotes
Detaljer angående fremstillingen av en lang rekke av disse monomerer finnes i US patentskrifter 3066112, 3721644, 3730947, 3770881 og 3774305. En tertiær eutektisk monomerblanding som også kan anvendes ifølge oppfinnelsen, er beskrevet i US patentskrift 3539526. Details regarding the production of a large number of these monomers can be found in US patent documents 3066112, 3721644, 3730947, 3770881 and 3774305. A tertiary eutectic monomer mixture that can also be used according to the invention is described in US patent document 3539526.
Det vil forstås at blandinger av to eller flere egnede methacrylatmonomerer kan anvendes ifølge oppfinnelsen. Av-hengig av valget av monomerer er i virkeligheten blandinger ofte sterkt ønskede for å optimalisere egenskapene for det erholdte tannpleiemiddel. Det foretrekkes således at monomeren eller monomerblandingen har en viskositet av 100-10000 centipoise, bestemt med et Brookfield-viskosimeter ved 20 omdreininger pr. minutt ved værelsetemperatur. It will be understood that mixtures of two or more suitable methacrylate monomers can be used according to the invention. Depending on the choice of monomers, in reality, mixtures are often highly desired to optimize the properties of the resulting dentifrice. It is thus preferred that the monomer or monomer mixture has a viscosity of 100-10,000 centipoise, determined with a Brookfield viscometer at 20 revolutions per minute. minute at room temperature.
Det uorganiske, partikkelformige fyllstoff som anvendes i blandingen ifølge oppfinnelsen, omfatter smeltet siliciumdioxyd, kvarts, krystallinsk siliciumdioxyd, amorft siliciumdioxyd, sodaglassperler, glasstaver, keramiske oxyder, par-tikkelf ormig silikatglass, radioopake glass (barium- og strontiumglass) og syntetiske mineraler, som 3-eucryptitt (LiAlSiO^) idet det sistnevnte har en negativ varmeut-videlseskoeffisient. Det er også mulig å anvende findelte materialer og pulverformig hydroxylapatitt selv om materialer som reagerer med silankoplingsmidler, er foretrukne. Også kolloidale siliciumdioxydkvaliteter eller siliciumdioxydkvaliteter med en partikkelstørrelse under l^,um og belagt med en polymer er tilgjengelige som fyllstoff. The inorganic, particulate filler used in the mixture according to the invention comprises fused silicon dioxide, quartz, crystalline silicon dioxide, amorphous silicon dioxide, soda glass beads, glass rods, ceramic oxides, particulate silicate glass, radio-opaque glass (barium and strontium glass) and synthetic minerals, which 3-eucryptite (LiAlSiO^), the latter having a negative coefficient of thermal expansion. It is also possible to use finely divided materials and powdered hydroxylapatite, although materials which react with silane coupling agents are preferred. Also, colloidal silicon dioxide grades or silicon dioxide grades with a particle size below 1 µm and coated with a polymer are available as fillers.
Små mengder pigmenter for å gi midlet en farve som passer til de forskjellige nyanser for tennene, kan anvendes. Egnede pigmenter omfatter jernoxydsort, kadmiumgult eller kadmiumoransje, fluorescerende sinkoxyder eller titandioxyd etc. Fyllstoffpartiklene vil i alminnelighet ha en diameter under 50^um, fortrinnsvis under 30^um. Det vil forstås at fyllstoffet er en valgfri bestanddel og at blandinger som ikke inneholder fyllstoff, anvendes når tannpleiemidlet er beregnet for anvendelse som belegg, kantforseglingsmiddel for amalgamgjenoppbygning eller klebemiddel. Small amounts of pigments can be used to give the agent a color that matches the different shades of the teeth. Suitable pigments include iron oxide black, cadmium yellow or cadmium orange, fluorescent zinc oxides or titanium dioxide etc. The filler particles will generally have a diameter below 50 µm, preferably below 30 µm. It will be understood that the filler is an optional component and that mixtures that do not contain filler are used when the dentifrice is intended for use as a coating, edge sealer for amalgam reconstruction or adhesive.
Silankoplingsmidlene eller låsemidlene er materialer som inneholder minst én polymeriserbar dobbeltbinding for reaksjon med methacrylatmonomerene. Eksempler på egnede koplingsmidler er vinyltriklorsilan, tris (acetoxy)-vinyl-silan, 1-N(vinylbenzylaminoethyl)-aminopropyltrimethoxy-silan-3 eller 3-methacryloxypropyltrimethoxysilan. Det sistnevnte materiale foretrekkes for anvendelse sammen med methacrylatmonomerer på grunn av likheten mellom dobbelt-bindingenes reaktivitet. The silane coupling agents or locking agents are materials that contain at least one polymerizable double bond for reaction with the methacrylate monomers. Examples of suitable coupling agents are vinyltrichlorosilane, tris (acetoxy)-vinyl-silane, 1-N(vinylbenzylaminoethyl)-aminopropyltrimethoxy-silane-3 or 3-methacryloxypropyltrimethoxysilane. The latter material is preferred for use with methacrylate monomers due to the similarity of the reactivity of the double bonds.
Peroxydkatalysatorer som kan anvendes ifølge oppfinnelsen og som er istand til å igangsette polymerisasjon av metha-crylatmonomeren eller -monomerene, er velkjente innen tek-nikken for en slik anvendelse og omfatter vanlige peroxyd-og dessuten hydroperoxydforbindelser, som cumenhydroperoxyd, p-methanhydroperoxyd, diisopropylbenzenhydroperoxyd eller t-butylhydroperoxyder. Peroxide catalysts which can be used according to the invention and which are able to initiate polymerization of the methacrylate monomer or monomers are well known in the art for such use and include common peroxide and also hydroperoxide compounds, such as cumene hydroperoxide, p-methane hydroperoxide, diisopropylbenzene hydroperoxide or t-butyl hydroperoxides.
Hydroperoxydene er de foretrukne representanter for organiske peroxydpolymerisasjonskatalysatorer, og cumenhydroperoxyd (CHP) er spesielt foretrukket. Om ønsket kan peroxydstabilisatorer, som ascorbinsyre eller maleinsyre The hydroperoxides are the preferred representatives of organic peroxide polymerization catalysts, and cumene hydroperoxide (CHP) is particularly preferred. If desired, peroxide stabilizers, such as ascorbic acid or maleic acid, can be used
etc., anvendes i små mengder. etc., are used in small quantities.
Reduksjonsmidler som kan anvendes ifølge oppfinnelsen, omfatter generelt et hvilket som helst materiale som er istand til å reagere med peroxydforbindelsen under dannelse av polymerisasjonsigangsettende, frie radikalgrupper, som er velkjent innen denne teknikk. Spesielt anvendbare ifølge oppfinnelsen er et substituert thiourinstoff med formelen Reducing agents that can be used in accordance with the invention generally include any material capable of reacting with the peroxide compound to form polymerization-initiating free radical groups, which are well known in the art. Particularly useful according to the invention is a substituted thiourea with the formula
hvori X er H eller Y, og Y er alkyl med 1-8 carbonatomer, wherein X is H or Y, and Y is alkyl of 1-8 carbon atoms,
som methyl, butyl eller octyl, cycloalkyl med 5 eller 6 carbonatomer, som cyclopentyl eller cyclohexyl, klor-, hydroxy- eller mercaptosubstituert alkyl med 1-8 carbonatomer, som klorethyl, mercaptoethyl, hydroxymethyl eller kloroctyl, alkenyl med 3-4 carbonatomer, som allyl eller methallyl, such as methyl, butyl or octyl, cycloalkyl of 5 or 6 carbon atoms, such as cyclopentyl or cyclohexyl, chloro-, hydroxy- or mercapto-substituted alkyl of 1-8 carbon atoms, such as chloroethyl, mercaptoethyl, hydroxymethyl or chlorooctyl, alkenyl of 3-4 carbon atoms, such as allyl or methallyl,
aryl med 6-8 carbonatomer, som fenyl eller xylyl, eller klor-, hydroxy-, methoxy- eller sulfonylsubstituert fenyl, som klor-fenyl, fenylsulfonyl, hydroxyfenyl eller methoxyfenyl, aryl of 6-8 carbon atoms, such as phenyl or xylyl, or chloro-, hydroxy-, methoxy- or sulfonyl substituted phenyl, such as chlorophenyl, phenylsulfonyl, hydroxyphenyl or methoxyphenyl,
acyl med 2-8 carbonatomer, som acetyl, butyryl eller octanoyl, klor- eller methoxysubstituert acyl, som kloracetyl, klor-benzoyl, klortoluoyl eller methoxybenzoyl, aralkyl med 7-8 carbonatomer, som benzyl, eller klor- eller methylsubstituert aralyl, som methoxybenzyl, og Z er NH,,, NHX eller NX,,. Eksempler på forbindelser som kan anvendes ifølge oppfinnelsen, er methylthiourea, isopropylthiourea, butylthiourea, octylthiourea, benzylthiourea, acetylthiourea, allylthiourea, 1,1,3-trifenylthiourea, 1,1,3-trimethylthiourea, 2,4-xylylthiourea, p-tolysulfonylthiourea, l-octyl-3-fenylthiourea, o-methoxyfenylthiourea, m-hydroxyfenylthiourea, 1,1-diallylthiourea, i,3-diallylthiourea, 2-methallyl-thiourea, o-methoxybenzylthipurea, 1-(hydroxymethyl)-3-methylthiourea, 1,1-dibutylthiourea, 1,3-dibutylthiourea, 1-(p-klorfenyl)-3-methylthiourea, 1 butyl-3-butyrylthio-urea, l-acetyl-3-fenylthiourea, 1 méthyl-3-(p-vinylfenyl) thiourea, 1-methy1-3-0-tolylthiourea, l-methyl-3-pentyl- acyl with 2-8 carbon atoms, such as acetyl, butyryl or octanoyl, chloro- or methoxy-substituted acyl, such as chloroacetyl, chlorobenzoyl, chlorotoluene or methoxybenzoyl, aralkyl with 7-8 carbon atoms, such as benzyl, or chloro- or methyl-substituted arallyl, such as methoxybenzyl , and Z is NH,,, NHX or NX,,. Examples of compounds that can be used according to the invention are methylthiourea, isopropylthiourea, butylthiourea, octylthiourea, benzylthiourea, acetylthiourea, allylthiourea, 1,1,3-triphenylthiourea, 1,1,3-trimethylthiourea, 2,4-xylylthiourea, p-tolysulfonylthiourea, l-octyl-3-phenylthiourea, o-methoxyphenylthiourea, m-hydroxyphenylthiourea, 1,1-diallylthiourea, i,3-diallylthiourea, 2-methallylthiourea, o-methoxybenzylthipurea, 1-(hydroxymethyl)-3-methylthiourea, 1, 1-dibutylthiourea, 1,3-dibutylthiourea, 1-(p-chlorophenyl)-3-methylthiourea, 1-butyl-3-butyrylthio-urea, l-acetyl-3-phenylthiourea, 1-methyl-3-(p-vinylphenyl)thiourea , 1-methyl-3-0-tolylthiourea, l-methyl-3-pentyl-
thiourea, 3-methyl-l, 1-difenylthiourea eller 1-acetyl 3-(2 metacptoethyl) thiourea . Selv ara hvilke som helst av de ovennevnte thiorureaer kan anvendes ifølge oppfinnelsen, er de monosubstituerte thioureaer foretrukne, dvs. slike som har den ovennevnte formel hvori X er H og Z er NH2. thiourea, 3-methyl-1,1-diphenylthiourea or 1-acetyl 3-(2-metacptoethyl)thiourea. Although any of the above-mentioned thioureas can be used according to the invention, the monosubstituted thioureas are preferred, i.e. those having the above-mentioned formula in which X is H and Z is NH 2 .
Spesielt foretrukne er fenylthiourea, acetylthioureau og allylthiourea. Blandingen inneholder fortrinnsvis 0,5-1,0 vekt% reduksjonsmiddel. Particularly preferred are phenylthiourea, acetylthiourea and allylthiourea. The mixture preferably contains 0.5-1.0% by weight of reducing agent.
Oppfinnelsen er nærmere beskrevet ved hjelp av de nedenstående eksempler. The invention is described in more detail using the examples below.
Eksempler 1- 14 Examples 1-14
Reduksjonsmiddelpastaer som er ugjennomtrengbare for radiostråler og med de følgende sammensetninger, fremstilles: Reducing agent pastes that are impervious to radio rays and with the following compositions are produced:
Oxydasjonsmiddelpastaer som er ugjennomtrengbare for radiostråler og med de følgende sammensetninger, fremstilles: Oxidizing agent pastes that are impervious to radio rays and with the following compositions are produced:
Både oxydasjonsmiddel- og reduksjonsmiddelpastaer blandes i et vektforhold av 1:1 som antydet i de nedenstående eksempler. Herdetider er angitt i minutter og omfatter den tid som er nødvendig for blanding, dvs. ca. 30 sekunder. Opp-høret av herdereaksjonen bestemmes ved at materialet ikke lenger kan trykkes inn med en spatel. Dette kan også gjøres ved å måle prosenten av polymerisat som er uoppløselig i methanol efter at herdereaksjonen er avsluttet. Prøver av den polymerdannende masse tas med visse tidsmellomrom under herdereaksjonen. Opphøret av denne antydes ved det tidspunkt ved hvilket den prosentuelle mengde av uoppløselige materialer holder seg i det vesentlige konstant. Resultatene kan oppsummeres som følger: Both oxidizing agent and reducing agent pastes are mixed in a weight ratio of 1:1 as indicated in the examples below. Curing times are stated in minutes and include the time required for mixing, i.e. approx. 30 seconds. The end of the hardening reaction is determined by the fact that the material can no longer be pressed in with a spatula. This can also be done by measuring the percentage of polymer that is insoluble in methanol after the curing reaction has ended. Samples of the polymer-forming mass are taken at certain intervals during the curing reaction. The cessation of this is indicated at the time at which the percentage amount of insoluble materials remains essentially constant. The results can be summarized as follows:
I elthvert av forsøkene utføres herdingen i luft, dvs. i In each of the experiments, the curing is carried out in air, i.e. i
en åpen beholder. En øket konsentrasjon av Cu gir en hurtigere herding. an open container. An increased concentration of Cu results in faster hardening.
Sammenlignet med eksemplene 7 og 14 hvori kobber-akselieratoren ikke ble anvendt, fastslår forsøksdataene en tydelig forbedring i herdehastigheten for midler ifølge oppfinnelsen. Compared to Examples 7 and 14 in which the copper accelerator was not used, the experimental data establish a clear improvement in the cure rate of compositions according to the invention.
Lignende kombinasjoner (1:1) av reduksjonsmiddelpasta B med I og J gir sammenlignbare resultater. Similar combinations (1:1) of reducing agent paste B with I and J give comparable results.
Eksempler 15- 17 Examples 15-17
Fremgangsmåten ifølge de ovenstående eksempler gjentas, men ved anvendelse av en monomerblanding av "Nupol" og HMDMA (vektforhold 71:29) i hver av oxydasjonsmiddelblandingen og reduksjonsmiddelblandingen. The procedure according to the above examples is repeated, but using a monomer mixture of "Nupol" and HMDMA (weight ratio 71:29) in each of the oxidizing agent mixture and the reducing agent mixture.
Fyllstoff sløyfes fullstendig i hvert av eksemplene. Kobberioner tilveiebringes ved hjelp av de følgende forbindelser: Filler is omitted completely in each of the examples. Copper ions are provided by the following compounds:
I hvert tilfelle fås forbedret herdehastighet sammenlignet med identiske kontrollforsøksblandinger uten kobberforbindelsen. In each case, improved cure rate is obtained compared to identical control test mixtures without the copper compound.
Eksempler 18- 20 Examples 18-20
Fremgangsmåten ifølge eksemplene 15-17 gjentas, men med de følgende materialer som akseleratorer: The procedure according to examples 15-17 is repeated, but with the following materials as accelerators:
Resultatene er lignende resultatene ifølge de foregående eksempler. The results are similar to the results according to the previous examples.
Eksempler 21- 34 Examples 21-34
Hver av eksemplene 1-14 gjentas, men med den forskjell at det toverdige kobberacetat adsorberes på fyllstoffet og derefter tilsettes til monomerblandingen. En lignende forbedring av herdehastigheten fås sammenlignet med kontrollfor-søk hvor kobberforbindelsen ikke ble anvendt. Each of the examples 1-14 is repeated, but with the difference that the divalent copper acetate is adsorbed on the filler and then added to the monomer mixture. A similar improvement in the curing rate is obtained compared to control experiments where the copper compound was not used.
Eksempler 35- 37 Examples 35-37
De følgende reduksjonsmiddelholdige og oxydasjonsmiddelholdige blandinger fremstilles: The following mixtures containing reducing agents and oxidizing agents are produced:
Reduksjonsmiddelholdige bland- inger Oxydasjonsmiddelholdig blanding- N Containing reducing agents mixtures Mixture containing oxidizing agent- N
Den oxydasjonsmiddelholdige pasta blir på en ren plast-plate blandet med hver av de tre reduksjonsmiddelholdige pastaer i et forhold 1:1. Herdetidene for hver av de tre blandinger bestemmes ved den tid som er nødvendig for at det blandede materiale skal bli motstandsdyktig mot inntrykning ved hjelp av en plastspatel. Resultatene kan oppsummeres som følger: The oxidizing agent-containing paste is mixed on a clean plastic plate with each of the three reducing agent-containing pastes in a 1:1 ratio. The curing times for each of the three mixtures are determined by the time required for the mixed material to become resistant to indentation using a plastic spatula. The results can be summarized as follows:
For hvert av de ovenstående forsøk utføres herdingen i luft. (Kortere herdetider vil fås under glass eller i en fordypning som er dekket av en grunnmassestrimmel.) Det er klart at når konsentrasjonen av Cu<++> økes, fås kortere herdetid. For each of the above tests, curing is carried out in air. (Shorter curing times will be obtained under glass or in a recess covered by a base material strip.) It is clear that when the concentration of Cu<++> is increased, shorter curing times are obtained.
Lignende resultater fås når de ovenstående eksempler gjentas, men ved innenfor de ovenfor angitte områder å anvende de følgende peroxydkatalysatorer og reduserende forbindelser: peroxydkatalysatorer - p-methanhydroperoxyd, diisopropylbenzenhydroperoxyd eller t-butylhydroperoxyd, og reduksjonsmidler - allylthiourea, fenylthiourea eller 3-allyl-l, 1-diethylthiourea. Similar results are obtained when the above examples are repeated, but by using within the ranges indicated above the following peroxide catalysts and reducing compounds: peroxide catalysts - p-methane hydroperoxyd, diisopropylbenzene hydroperoxyd or t-butyl hydroperoxyd, and reducing agents - allylthiourea, phenylthiourea or 3-allyl-1, 1-diethylthiourea.
Claims (4)
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DE3928987A1 (en) * | 1989-09-01 | 1991-03-28 | Siegfried Reiss | METHOD AND SHAPE FORM FOR PRODUCING SHAPINGS FOR THE DENTAL AREA |
DE4339399A1 (en) * | 1993-11-18 | 1995-05-24 | Thera Ges Fuer Patente | Dental inserts prodn. for use with composite filling materials. |
US20070100019A1 (en) * | 2005-08-02 | 2007-05-03 | Fuming Sun | Catalyst system for dental compositions |
DE102005039590B4 (en) * | 2005-08-19 | 2008-05-21 | Heraeus Kulzer Gmbh | Polymerizable dental composition with a 2-component initiator system |
EP1849449A1 (en) | 2006-04-26 | 2007-10-31 | 3M Innovative Properties Company | Filler containing composition and process for production and use thereof |
EP2142163B1 (en) * | 2007-04-25 | 2015-11-04 | DENTSPLY International Inc. | Self-adhesive dental cement |
JP5388482B2 (en) * | 2008-06-04 | 2014-01-15 | クラレノリタケデンタル株式会社 | Dental curable composition |
JP2009292761A (en) * | 2008-06-04 | 2009-12-17 | Kuraray Medical Inc | Curable composition for dental use |
CN102702405B (en) * | 2012-07-05 | 2014-04-09 | 东营市诺尔化工有限责任公司 | Method for preparing ultralow-residue water absorbing resins |
JP6112887B2 (en) * | 2013-02-05 | 2017-04-12 | 株式会社トクヤマデンタル | Dental curable composition |
JP6086797B2 (en) * | 2013-04-25 | 2017-03-01 | クラレノリタケデンタル株式会社 | Dental polymerizable composition |
RU2683315C2 (en) | 2014-07-10 | 2019-03-28 | 3М Инновейтив Пропертиз Компани | Two-component self-adhesive dental composition, process of production and use thereof |
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AU2018394851B2 (en) | 2017-12-26 | 2021-03-11 | Tokuyama Dental Corporation | Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method of storing adhesive composition |
EP3808324A1 (en) * | 2019-09-26 | 2021-04-21 | Shofu Inc. | Curable composition containing transition metal adsorbent |
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GB1177879A (en) * | 1967-09-04 | 1970-01-14 | Sumitomo Chemical Co | Catalyst System and process for the Polymerisation of Vinyl Compounds |
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JPS51131197A (en) * | 1975-05-08 | 1976-11-15 | Sankin Ind Co | Uniiliquid type dental cement |
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ZA812567B (en) | 1982-11-24 |
NZ196864A (en) | 1984-04-27 |
AU6991181A (en) | 1981-11-05 |
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SE8102634L (en) | 1981-10-30 |
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FR2481114B1 (en) | 1984-11-30 |
ES8206560A1 (en) | 1982-08-16 |
SE450547B (en) | 1987-07-06 |
JPS56169609A (en) | 1981-12-26 |
IE810958L (en) | 1981-10-29 |
GB2075035B (en) | 1984-07-25 |
ATA187781A (en) | 1984-03-15 |
ES501695A0 (en) | 1982-08-16 |
PH17044A (en) | 1984-05-17 |
DE3116132A1 (en) | 1982-02-04 |
DK189781A (en) | 1981-10-30 |
CA1223696A (en) | 1987-06-30 |
MX156002A (en) | 1988-06-14 |
BR8102607A (en) | 1982-01-19 |
AT376125B (en) | 1984-10-10 |
BE888599A (en) | 1981-08-17 |
GB8321611D0 (en) | 1983-09-14 |
CH649465A5 (en) | 1985-05-31 |
AU554532B2 (en) | 1986-08-28 |
NO158991C (en) | 1988-11-23 |
NO811448L (en) | 1981-10-30 |
GB2075035A (en) | 1981-11-11 |
FR2481114A1 (en) | 1981-10-30 |
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