JPS6221341B2 - - Google Patents
Info
- Publication number
- JPS6221341B2 JPS6221341B2 JP56205100A JP20510081A JPS6221341B2 JP S6221341 B2 JPS6221341 B2 JP S6221341B2 JP 56205100 A JP56205100 A JP 56205100A JP 20510081 A JP20510081 A JP 20510081A JP S6221341 B2 JPS6221341 B2 JP S6221341B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- product
- reaction
- fluorine
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 11
- -1 perfluorocarboxylic acid halide Chemical class 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 6
- 125000005843 halogen group Chemical group 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 47
- 238000010521 absorption reaction Methods 0.000 description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 150000001733 carboxylic acid esters Chemical class 0.000 description 27
- 239000007788 liquid Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000178 monomer Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- 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 19
- 238000000862 absorption spectrum Methods 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 238000000921 elemental analysis Methods 0.000 description 16
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 16
- 230000000379 polymerizing effect Effects 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 150000001793 charged compounds Chemical class 0.000 description 14
- 238000004949 mass spectrometry Methods 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- 239000000805 composite resin Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 208000002925 dental caries Diseases 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 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 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000005548 dental material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 241000194017 Streptococcus Species 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KIZCNUWGIVQQBK-UHFFFAOYSA-N (2-hydroxy-4-methylphenyl)-phenylmethanone Chemical compound OC1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 KIZCNUWGIVQQBK-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 description 1
- KLAVPNKIYBZAOK-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(Cl)=O)C(F)(F)F KLAVPNKIYBZAOK-UHFFFAOYSA-N 0.000 description 1
- BCLQALQSEBVVAD-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoyl fluoride Chemical compound FC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F BCLQALQSEBVVAD-UHFFFAOYSA-N 0.000 description 1
- AFTBJQDQENGCPC-UHFFFAOYSA-N 2,5-ditert-butyl-4-methylphenol Chemical compound CC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C AFTBJQDQENGCPC-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002316 cosmetic surgery Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000004262 dental pulp cavity Anatomy 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Dental Preparations (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規化合物である含弗素不飽和カルボ
ン酸エステルおよびその製造方法に関する。また
本発明は該含弗素不飽和カルボン酸エステルを少
くとも１成分とする歯科用充填剤組成物を提供す
る。
現在、虫歯を治療した後の修復用充填材料とし
てアマルガム、セメント以外に多官能性アクリル
（又はメタクリル）誘導体と無機フイラーを主成
分とする複合材料（以下コンポジツトレジンとい
う）が使われている。又、小窩裂溝などの充填剤
としても同様な多官能性アクリル（又はメタクリ
ル）誘導体を主成分とする合成樹脂材料（以下シ
ーラントという）が用いられている。
コンボジツトレジンやシーラント等の充填剤は
従来の修復材料や充填剤に比べ多くの利点を有し
ているが、吸水性が高いために充填物と歯質の隙
間に水が入り易く、水と一緒に虫歯の原因となる
ストレプトコツカスミユータンスが侵入して二次
う食を起こし易いという欠点を有している。これ
は充填剤の主成分である多官能性アクリル（又は
メタクリル）誘導体が親水性である事に起因して
いる。
本発明では二次う食予防を目的として、撥水性
を有する歯科用モノマーを開発すべく、長年研究
を続けてきた。その結果、次式で示される新規物
質が著しい撥水性を示し、歯科用充填剤組成物と
しても有用であることを見い出し、本発明を完成
させるに至つた。
即ち、本発明は新規物質に関するもので、一般
式
（但し、R1はＨ又はCH3、R2は−CH2−、
The present invention relates to a new compound, a fluorine-containing unsaturated carboxylic acid ester, and a method for producing the same. The present invention also provides a dental filler composition containing the fluorine-containing unsaturated carboxylic acid ester as at least one component. Currently, in addition to amalgam and cement, composite materials (hereinafter referred to as composite resins) whose main components are polyfunctional acrylic (or methacrylic) derivatives and inorganic fillers are used as filling materials for restorations after cavities have been treated. Furthermore, a similar synthetic resin material (hereinafter referred to as a sealant) whose main component is a polyfunctional acrylic (or methacrylic) derivative is also used as a filler for pits and fissures. Filling materials such as composite resins and sealants have many advantages over conventional restorative materials and filling materials. It also has the disadvantage of being susceptible to the invasion of Streptococcus smutans, which causes cavities, and secondary caries. This is due to the fact that the polyfunctional acrylic (or methacrylic) derivative, which is the main component of the filler, is hydrophilic. In the present invention, we have continued research for many years to develop a water-repellent dental monomer for the purpose of preventing secondary caries. As a result, they discovered that a new substance represented by the following formula exhibits remarkable water repellency and is useful as a dental filling composition, leading to the completion of the present invention. That is, the present invention relates to a new substance, which has the general formula (However, R 1 is H or CH 3 , R 2 is -CH 2 -,
【式】R′2 はCH2、[Formula] R′ 2 is CH 2 ,
【式】【formula】
【式】であり、R3は[Formula], and R 3 is
【式】または[expression] or
【式】であり、 Ｙは[Formula], Y is
【式】ｌ又は０又は１、ｎは０又は１で
ある。）で示される含弗素不飽和カルボン酸エス
テルである。この化合物は常温、常圧で無色透明
な液体であり、ベンゼン、エーテル、クロロホル
ム、酢酸エチル、アルコールなど通常の有機溶媒
に可溶であるが水には不溶である。また、その沸
点は非常に高く２〜３mmHgの減圧下でも100℃以
上の加熱を必要とする。
また本発明の含弗素不飽和カルボン酸エステル
は以下(a)〜(d)のような方法で分析を行ない確認す
ることが出来る。
(a) 赤外吸収スペクトル（I.R.）
一般にメタクリル酸エステル（あるいはアク
リル酸エステル）において、カルボニル基の吸
収は1720cm-1に、二重結合による吸収は1640cm
-1に観察される。一方、フルオロアルキル基に
隣接したカルボニル基の吸収は1780cm-1付近に
観察される。又、Ｃ−Ｆの伸縮による吸収は、
1400〜1100cm-1に現われる事が分つている。
本発明の前記一般式で示される含弗素不飽和
カルボン酸エステルをI.R.分析すると、メタク
リル酸エステル又はアクリル酸エステルのカル
ボニル基の吸収が1720cm-1に、フルオロアルキ
ル基に隣接したカルボニル基の吸収が1780cm-1
に、二重結合に基づく吸収が1640cm-1にそれぞ
れ表われる。またＣ−Ｆの伸縮による吸収が
1400〜1100cm-1に現われる。更にまたベンゼン
環を結合して有する含弗素不飽和カルボン酸エ
ステルにあつては該ベンゼン環に基づく吸収が
1495cm-1に表われる。
従つてI.R.分析によつてカルボン酸エステル
に基づくカルボニル基、フルオロアルキル基、
フルオロアルキル基に基づくカルボニル基、二
重結合及びベンゼン環の有無についての確認が
出来る。
(b) カーボン13核磁気共鳴スペクトル
1Hならびに 19Fをデカツプリングした 13C
核磁気共鳴スペクトルにおいて、環境の異なる
炭素はそれぞれ一本のピークを示す。この化学
シフトを調べる事によつて生成物を同定するこ
とが出来る。本発明の化合物についての具体的
な同定については後述する実施例で述べるが、
本発明の化合物が何であるかはカーボン13核磁
気共鳴スペクトルでほゞ完全に確認することが
出来る。
(c) 質量スペクトル
通常の質量スペクトル法においては、試料を
電子衝撃してイオンを作るのであるが、含弗素
化合物の場合、この方法によると枝分かれや転
位反応が起き、しかも分子イオンM+が観察さ
れない事が多い。そこで本発明においては比較
的マイルドな条件下でイオン化する方法として
フイールドイオン−質量スペクトル法を用い
た。
この方法により、分子イオンピークM+を確
認することができる。このデーターとカーボン
13核磁気共鳴スペクトル、赤外吸収スペクト
ル、元素分析等の結果を併せて分子量および分
子構造を確認出来る。
(d) 元素分析
含弗素不飽和カルボン酸エステルのほゞ確実
な同定は、前記カーボン13核磁気共鳴スペクト
ルで判明するが、該化合物におけるＨ、Ｃ、Ｆ
各元素の理論計算値と実際に得られる化合物と
の各元素分解結果を比較することにより更に明
確な同定が可能となる。
以上(a)〜(d)に述べたような分析手段で本発明の
含弗素不飽和カルボン酸エステルを同定すること
が出来る。
本発明の含弗素不飽和カルボン酸エステルは前
記したように新規物質であり、ポリマーの一般的
な原料として広く利用できる。また分子内に２つ
のメタクリル基（又はアクリル基）を有するため
架橋剤としても利用できる。さらに上記単量体を
重合して得られるポリマーは側鎖に撥水性を示す
パーフルオロアルキル基を有するため従来の炭化
水素系ポリマーに比べ高い撥水性を示すポリマー
となる。また、この新規物質は後述する実施例に
示すように極端に低い屈折率を示すため、他の単
量体に添加して共重合する事によつて屈折率を調
整することが出来る。
本発明の含弗素不飽和カルボン酸エステルの製
造方法は特に限定されず如何なる方法で製造して
もよい。一般に好適に採用しうる代表的な製造方
法を挙げると次のような方法である。
()(1) 一般式
（但し、R1はＨ又はCH3、R2はCH2、
[Formula] l or 0 or 1, n is 0 or 1. ) is a fluorine-containing unsaturated carboxylic acid ester. This compound is a colorless and transparent liquid at room temperature and pressure, and is soluble in common organic solvents such as benzene, ether, chloroform, ethyl acetate, and alcohol, but insoluble in water. In addition, its boiling point is extremely high and requires heating to 100°C or higher even under reduced pressure of 2 to 3 mmHg. Further, the fluorine-containing unsaturated carboxylic acid ester of the present invention can be analyzed and confirmed by the following methods (a) to (d). (a) Infrared absorption spectrum (IR) Generally, in methacrylic esters (or acrylic esters), the carbonyl group absorbs at 1720 cm -1 and the double bond absorbs at 1640 cm
-1 observed. On the other hand, the absorption of the carbonyl group adjacent to the fluoroalkyl group is observed around 1780 cm -1 . In addition, absorption due to expansion and contraction of C-F is
It is known that it appears between 1400 and 1100 cm -1 . IR analysis of the fluorine-containing unsaturated carboxylic acid ester represented by the above general formula of the present invention shows that the absorption of the carbonyl group of the methacrylic ester or acrylic ester is 1720 cm -1 , and the absorption of the carbonyl group adjacent to the fluoroalkyl group is 1720 cm -1. 1780cm -1
In addition, absorption based on double bonds appears at 1640 cm -1 . Also, absorption due to expansion and contraction of C-F
Appears between 1400 and 1100 cm -1 . Furthermore, in the case of a fluorine-containing unsaturated carboxylic acid ester having a benzene ring bonded to it, the absorption based on the benzene ring is
It appears at 1495cm -1 . Therefore, by IR analysis, carbonyl groups, fluoroalkyl groups, and
The presence or absence of carbonyl groups, double bonds, and benzene rings based on fluoroalkyl groups can be confirmed. (b) Carbon 13 nuclear magnetic resonance spectrum 13 C decoupled with 1 H and 19 F
In a nuclear magnetic resonance spectrum, each carbon in a different environment exhibits a single peak. By examining this chemical shift, the product can be identified. Specific identification of the compounds of the present invention will be described in the Examples below.
The identity of the compound of the present invention can be almost completely confirmed by carbon-13 nuclear magnetic resonance spectrum. (c) Mass spectrum In normal mass spectrometry, ions are created by bombarding the sample with electrons, but in the case of fluorine-containing compounds, branching and rearrangement reactions occur using this method, and molecular ions M + are observed. There are many cases where it is not done. Therefore, in the present invention, field ion-mass spectrometry was used as a method for ionization under relatively mild conditions. By this method, the molecular ion peak M + can be confirmed. This data and carbon
13Molecular weight and molecular structure can be confirmed by combining the results of nuclear magnetic resonance spectra, infrared absorption spectra, elemental analysis, etc. (d) Elemental analysis The fluorine-containing unsaturated carboxylic acid ester can be identified with certainty using the carbon-13 nuclear magnetic resonance spectrum, but H, C, and F in the compound can be confirmed with certainty.
By comparing the theoretically calculated values of each element and the results of decomposition of each element with the actually obtained compound, more clear identification becomes possible. The fluorine-containing unsaturated carboxylic acid ester of the present invention can be identified by the analytical means described in (a) to (d) above. As mentioned above, the fluorine-containing unsaturated carboxylic acid ester of the present invention is a new substance and can be widely used as a general raw material for polymers. Furthermore, since it has two methacrylic groups (or acrylic groups) in its molecule, it can also be used as a crosslinking agent. Furthermore, since the polymer obtained by polymerizing the above monomer has a perfluoroalkyl group exhibiting water repellency in the side chain, the polymer exhibits higher water repellency than conventional hydrocarbon polymers. Furthermore, since this new substance exhibits an extremely low refractive index as shown in the Examples below, the refractive index can be adjusted by adding it to other monomers and copolymerizing it. The method for producing the fluorine-containing unsaturated carboxylic acid ester of the present invention is not particularly limited and may be produced by any method. Typical manufacturing methods that can generally be suitably employed include the following methods. ()(1) General formula (However, R 1 is H or CH 3 , R 2 is CH 2 ,
【式】 R′2はCH2、[Formula] R′ 2 is CH 2 ,
【式】又は[Formula] or
【式】であり、Ｙは[Formula], and Y is
【式】
ｌは０又は１である。）と
(2) 一般式
CF3CF2COX又は
[Formula] l is 0 or 1. ) and (2) General formula CF 3 CF 2 COX or
【式】
（ただし、Ｘはハロゲンで好ましくは弗素又は塩
素、ｎは０又は１である。）
で示される化合物を反応させることにより、前記
一般式で示される含弗素不飽和エステルを製造す
ることが出来る。
上記反応にあたり原料化合物はどのような順序
で混合して反応を行なつてもよい。また一段階で
これらの原料成分化合物をすべて混合して反応を
行なうこともできるし、数段階に分けてこれらの
原料成分化合物を混合する方法で反応を行なうこ
ともできる。
前記製造法に於ける反応条件は特に限定されな
いが、通常は溶媒の存在下に実施するのが一般的
である。該溶媒としては、原料と反応しない無水
の極性非水溶媒が特に制限なく使用される。該極
性非水溶媒の代表的なものを例示すると、エーテ
ル、テトラヒドロフラン、ジオキサン、モノグラ
イム、ジグライム、トリグライム、テトラグライ
ム等のエーテル系溶媒；ジメチルスルホキシド、
スルホラン等のオキソサルフア系溶媒；アセトニ
トリル、プロピオニトリル、ベンゾニトリル等の
ニトリル系溶媒；ジメチルホルムアミド、ジエチ
ルホルムアミド、ジメチルアセトアミド、Ｎ−メ
チルピロリドン、ヘキサメチルホスホルアミド等
のアミド系溶媒等が好適に使用される。また、分
子内にベンゼン環を持つ含弗素不飽和カルボン酸
エステルを製造する場合はベンゼン溶媒を使用す
ることが出来る。尚、使用する原料成分化合物と
溶媒とを混合する方法及び混合順序は特に制限さ
れない。
前記製造方法に於ける反応温度は特に限定され
るものではないが、通常−78℃以上乃至100℃以
下の温度範囲から選択するのが望ましい。該100
℃を越える高い温度においても反応は進行する
が、原料または生成物の重合などが起こつたり、
副反応が起つたりする傾向があるので通常は採用
しない方がよい。従つて目的物の収率の面から反
応は好ましくは、−78〜100℃の間の温度から選択
し、更に好ましくは、−78〜50℃の間の温度範囲
の中から選択するのが好ましい。
前記製造法に於ける反応は通常原料成分化合物
および溶媒を仕込んだ状態での反応温度における
自然圧下で行なうのが便利であるが必要に応じて
更に加圧又は減圧した状態で行なつても良い。
尚、反応の雰囲気は特に限定されないが一般には
不活性ガスで置換した方が好ましい結果を与える
ことが多い。
前記製造法に於ける反応時間は用いる原料成分
化合物溶媒の種類、反応温度等によつて異なり一
概に限定出来るものではないが、一般には数分か
ら数日の範囲で選択すれば好ましく、必要に応じ
て数分から数時間程度の反応時間にするように他
の条件を選ぶのが好適である。
前記製造法に於ける反応容器の材質は反応に関
与しない腐食に耐える材質であれば特に限定され
ないがガラス、ステンレス等の金属、テフロン等
が一般に好適に使用される。尚、CF3CF2COXは
沸点が低いので反応する際には耐圧容器を用いる
のが好ましい。
前記製造法の実施に際して反応熱の均一な分散
および原料成分化合物の均一な分散等のために反
応系を撹拌する手段はしばしば好適な手段として
採用されうる。
前記製造法に於ける方法により製造した含弗素
不飽和カルボン酸エステルを反応容器内の混合物
から分離する方法は特に限定されず公知の方法が
採用出来るが通常の蒸留等の操作では沸点が高く
しかも100℃以上の温度では一部重合が始まるた
め、非常に困難である場合が多い。
そこで、このような場合は次のような操作で分
離すればよい。例えば一旦大量の水と四塩化炭
素、クロロホルム、塩化メチレン、１・１・２−
トリクロロ−１・２・２−トリフルオロエタンな
どの含ハロゲン溶媒との混合物を加えて含弗素不
飽和カルボン酸エステルを溶媒抽出する方法が好
ましい。また前記反応で生成するハロゲン化水
素、パーフルオロカルボン酸及び未反応原料のパ
ーフルオロ酸ハライドは水に溶けるので、弱アル
カリ水溶液（例えばNaHCO3、Na2CO3等）で中
和してモノマーから分離できる。これらを分離し
た後溶媒を減圧下、100℃以下の温度で留去させ
て、含弗素不飽和カルボン酸エステルを得るのが
よい。
()(i) 一般式
（但し、R1はＨ又はCH3、R2はCH2、[Formula] (wherein, X is a halogen, preferably fluorine or chlorine, and n is 0 or 1) to produce a fluorine-containing unsaturated ester represented by the general formula above. I can do it. In the above reaction, the raw materials may be mixed in any order and the reaction may be carried out. Further, the reaction can be carried out by mixing all of these raw material component compounds in one step, or the reaction can be carried out by mixing these raw material component compounds in several stages. Although the reaction conditions in the above production method are not particularly limited, it is generally carried out in the presence of a solvent. As the solvent, an anhydrous polar non-aqueous solvent that does not react with the raw materials can be used without particular limitation. Representative examples of the polar nonaqueous solvent include ether solvents such as ether, tetrahydrofuran, dioxane, monoglyme, diglyme, triglyme, and tetraglyme; dimethyl sulfoxide;
Oxosulfur solvents such as sulfolane; nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoramide are preferably used. be done. Furthermore, when producing a fluorine-containing unsaturated carboxylic acid ester having a benzene ring in the molecule, a benzene solvent can be used. Note that the method and order of mixing the raw material component compounds and the solvent used are not particularly limited. The reaction temperature in the above production method is not particularly limited, but it is generally desirable to select it from a temperature range of -78°C or higher to 100°C or lower. 100
Although the reaction proceeds even at high temperatures exceeding ℃, polymerization of raw materials or products may occur, or
Since it tends to cause side reactions, it is usually better not to use it. Therefore, from the viewpoint of yield of the target product, the reaction temperature is preferably selected from a temperature range of -78 to 100°C, more preferably from a temperature range of -78 to 50°C. . The reaction in the above production method is usually conveniently carried out under natural pressure at the reaction temperature with the raw material components and solvent charged, but it may be carried out under increased or reduced pressure if necessary. .
Incidentally, the reaction atmosphere is not particularly limited, but in general, substitution with an inert gas often gives preferable results. The reaction time in the above production method varies depending on the raw material components, the type of solvent used, the reaction temperature, etc., and cannot be absolutely limited, but it is generally preferable to select it within the range of several minutes to several days, and the reaction time may be changed as necessary. It is preferable to select other conditions such that the reaction time is on the order of several minutes to several hours. The material of the reaction vessel in the above manufacturing method is not particularly limited as long as it is not involved in the reaction and is resistant to corrosion, but glass, metals such as stainless steel, Teflon, etc. are generally suitably used. In addition, since CF 3 CF 2 COX has a low boiling point, it is preferable to use a pressure-resistant container when reacting. When carrying out the above production method, means for stirring the reaction system can often be employed as a suitable means for uniformly dispersing the reaction heat and uniformly dispersing the raw material component compounds. The method for separating the fluorine-containing unsaturated carboxylic acid ester produced by the above production method from the mixture in the reaction vessel is not particularly limited and any known method can be used, but it is difficult to separate the fluorine-containing unsaturated carboxylic acid ester produced by the above production method from the mixture in the reaction vessel. At temperatures above 100°C, some polymerization begins, which is often extremely difficult. Therefore, in such a case, you can separate it by the following operation. For example, once a large amount of water and carbon tetrachloride, chloroform, methylene chloride, 1, 1, 2-
A method of solvent extraction of the fluorine-containing unsaturated carboxylic acid ester by adding a mixture with a halogen-containing solvent such as trichloro-1,2,2-trifluoroethane is preferred. In addition, the hydrogen halide, perfluorocarboxylic acid, and perfluoro acid halide that are unreacted raw materials produced in the above reaction are soluble in water, so they can be neutralized with a weak alkaline aqueous solution (e.g., NaHCO 3 , Na 2 CO 3 , etc.) to remove the monomers. Can be separated. After separating these, the solvent is preferably distilled off under reduced pressure at a temperature of 100° C. or lower to obtain a fluorine-containing unsaturated carboxylic acid ester. ()(i) General formula (However, R 1 is H or CH 3 , R 2 is CH 2 ,
【式】R′2は CH2、[Formula] R′ 2 is CH 2 ,
【式】又は[Formula] or
【式】であり、Ｙは[Formula], and Y is
【式】 ｌは０又は１である） で示される化合物と (ii)【formula】 l is 0 or 1) With the compound shown by (ii)
【式】とを、３級アミンの存在す
る無水極性非水溶媒中で反応させることにより、
含弗素不飽和カルボン酸エステルを製造する方法
が採用される。
上記（）の製造法の反応にあたり原料化合物
はどのような順序で混合して反応を行なつてもよ
いが、By reacting [Formula] in an anhydrous polar nonaqueous solvent in the presence of a tertiary amine,
A method for producing a fluorine-containing unsaturated carboxylic acid ester is employed. In the reaction of the above production method (), the raw materials may be mixed in any order and the reaction may be carried out,
【式】は沸点が−28℃と低いた
め、好ましくは上記(i)式の化合物と３級アミン、
無水極性非水溶媒系の混合物に[Formula] has a low boiling point of -28°C, so it is preferable to combine the compound of formula (i) above with a tertiary amine,
For mixtures of anhydrous polar non-aqueous solvent systems
【式】
を導入するのが好ましい。
上記（）の製造法に於ける反応温度は特に限
定されるものではないが、通常−78℃以上乃至
100℃以下の温度範囲から選択するのが望まし
い。100℃を越える高い温度においても反応は進
行するが、原料または生成物の重合などが起つた
り、副反応が起つたりする傾向があるので特別の
場合を除き採用しない方が好ましい。従つて目的
物の収率の面から反応は好ましくは−78〜100℃
の間の温度から選択し、更に好ましくは−78〜50
℃の間の温度範囲の中から選択するのが好まし
い。
前記（）の製造法に於ける反応は通常、原料
成分化合物および溶媒を仕込んだ状態での反応温
度に於ける自然圧下で行なうのが便利であるが必
要に応じて更に加圧又は減圧した状態で行なうこ
とも出来る。尚、反応の雰囲気は特に限定されな
いが、一般には不活性ガスで置換した方が好まし
い結果を与えることが多い。
前記（）の製造法に於ける反応時間は用いる
原料成分化合物、溶媒の種類、反応温度等によつ
て異なり一概に限定できるものではないが一般に
は数分から数日の範囲で選択すれば好ましく、必
要に応じて数分から数時間程度の反応時間にする
ように他の条件を選ぶのが好適である。
前記（）の製造法に於ける反応溶器の材質は
反応に関与しない腐食に耐える材質であれば特に
限定されないが、ガラス、ステンレス等の金属、
テフロン等が一般に好適に使用される。前記原料
のIt is preferable to introduce [Formula]. The reaction temperature in the above manufacturing method () is not particularly limited, but is usually -78°C or higher.
It is desirable to select from a temperature range of 100℃ or less. Although the reaction proceeds even at high temperatures exceeding 100°C, it tends to cause polymerization of raw materials or products or side reactions, so it is preferable not to use this method except in special cases. Therefore, from the viewpoint of yield of the target product, the reaction temperature is preferably -78 to 100°C.
Select from a temperature between, more preferably -78 to 50
Preferably, the temperature range is between 0.degree. The reaction in the production method described in () above is usually conveniently carried out under natural pressure at the reaction temperature with the raw material components and solvent charged, but if necessary, the reaction may be carried out under further increased or reduced pressure. You can also do it with Incidentally, the reaction atmosphere is not particularly limited, but in general, substitution with an inert gas often gives preferable results. The reaction time in the production method of () above varies depending on the raw material components used, the type of solvent, the reaction temperature, etc., and cannot be absolutely limited, but it is generally preferable to select it within the range of several minutes to several days. It is preferable to select other conditions so that the reaction time ranges from several minutes to several hours, if necessary. The material of the reaction vessel in the above manufacturing method is not particularly limited as long as it is not involved in the reaction and is resistant to corrosion, but metals such as glass, stainless steel, etc.
Teflon and the like are generally preferred. of said raw materials
【式】は沸点が低いため、さらに好ま
しくは耐圧製容器を用いることが好ましい。
前記（）の製造法の実施に際して反応熱の均
一な分散および原料成分化合物の均一な分散等の
ために反応系を撹拌する手段は、しばしば好適な
手段として採用されうる。
また前記（）の製造法により製造した含弗素
不飽和カルボン酸エステルを反応容器内の混合物
から分離するには前記（）の製造法に於ける分
離方法と同様に操作すればよい。
次に本発明の新規物質である含弗素不飽和カル
ボン酸エステルの利用方法について以下説明す
る。
本発明の含弗素不飽和カルボン酸エステルは、
前記したように不飽和結合を有するので重合体又
は共重合体用の単量体、架橋剤等として広く利用
される。例えば歯科用充填剤組成分には好適に使
用される。該含弗素不飽和カルボン酸エステルを
歯科用充填剤組成物に用いる場合につき以下説明
する。歯科用充填剤組成物は重合可能な単量体と
無機充填剤とを混合したペースト状物又はこれら
を硬化させたもの等一般にコンポジツトレジンと
称されるものに或いは重合可能な単量体よりなる
液状物又はこの重合体等一般にシーラントと称さ
れるものに、重合可能な単量体として使用され
る。
現在、医歯用材料、特に歯科用材料のうち修復
用充填材料としてビスフエノールＡジグリシジル
メタクリレート（以下〔Bis−GMA〕という）と
無機フイラーを主成分とする材料（以下「Bis−
GMA系コンポジツトレジン」という）が開発さ
れており、また小窩裂溝などの充填材料として
Bis−GMAを主成分とする有機材料（以下「Bis
−GMA系シーラント」という）も使われてい
る。
しかし、これらのBis−GMA系の充填材料は吸
水率が高いために、歯質と充填材料との間に水が
入りやすく、そのために水と一緒に虫歯の原因と
なるストレプトコツカスミユータンスが入つて二
次う食の原因となり易い。また、Bis−GMAの屈
折率は1.55と高い値を示すため、コンポジツトレ
ジンの原料として用いる無機フイラーに対しても
屈折率の低い無機物（例えば無定形シリカ）は、
混合時に透明感が出ないのでフイラーとして用い
ることが出来ないという欠点を有している。しか
るに前記Bis−GMA系コンポジツトレジンならび
にBis−GMAに代えて本発明の含弗素不飽和カル
ボン酸エステルを用いることによつて上記の欠陥
を解決することができる。
本発明の新規物質は低粘度、低屈折率ならびに
撥水性にすぐれた特性を有する。また実用に際し
ては、コンポジツトレジンに用いる場合、無機質
フイラー、コンポジツトレジンを重合せしめるた
めの触媒、該触媒と反応して遊離基を生成する促
進剤等と混合して用いられるのが一般的である。
また該無機質フイラーとしては石英粉末、ガラス
粉末、ガラスビーズ、酸化アルミニウムならびに
無定形シリカ等を用いればよい。更にまた該無機
質フイラーは複合レジン重量の50〜90重量％を占
めるのが好ましい。また無機質フイラーを予めカ
ツプリング剤、例えばγ−メタクリロキシプロピ
ルトリメトキシシラン、ビニルトリエトキシシラ
ン等により処理しておけば無機質フイラーとレジ
ン組成物との結合が強くなり、医歯用材料として
の物理的性質が更に向上するので好ましい。又、
前記触媒として代表的なものを挙げれば、過酸化
ベンゾイル、過酸化２・４−ジクロロベンゾイ
ル、過酸化４−クロロベンゾイル、過酸化ラウロ
イル等が好適に使用される。これらの触媒は一般
にレジン組成物100重量部に対し0.1〜2.0重量部
の割合で使用される。更にまた促進剤として代表
的なものは、Ｎ・Ｎ−ジメチル−Ｐ−トルイジ
ン、Ｎ・Ｎ−ビス−（２−ヒドロキシエチル）−４
−メチルアニリン、Ｎ・Ｎ−ビス−（２−ヒドロ
キシエチル）−３・５−ジメチルアニリン、Ｎ・
Ｎ−ビス−（２−ヒドロキシエチル）−３・４−ジ
メチルアニリン等が好適に使用される。
これらの促進剤は一般にレジン組成物100重量
部に対し、0.1〜2.0重量部の割合で使用すればよ
い。更にレジン組成物の保存性を高めるために
は、ベンゾフエノン系化合物、例えば２−ヒドロ
キシ−４−メチルベンゾフエノン等の紫外線吸収
剤をレジン組成物100重量部に対し、0.5〜2.0重
量部あるいは一般にラリーラジカル連鎖反応停止
剤と呼ばれる安定剤、例えばＰ−メトキシフエノ
ール、２・５−ジ−tertブチル−４−メチルフエ
ノール等を該レジン組成物促進剤からなるペース
ト状物（ペーストＡ）と無機質フイラーレジン組
成物触媒からなるペースト状物（ペーストＢ）を
予め準備しておき、医師が使用する際、これらの
二つのペーストを混合するだけでレジン組成物は
重合を開始するため非常に便利である。
本発明の新規物質をシーラントに用いる場合、
大量の無機質フイラーは混合して用いないが、そ
の他触媒、促進剤、紫外線吸収剤等については、
コンポジツトレジンと同様である。
医師が使用する際同様に２液を混合してレジン
組成物が重合を開始する方法を用いる。
尚、本発明のレジン組成物は医歯用として例え
ば整形外科及び形成外科分野に於けるボーンセメ
ント人工骨、或いは歯科保存、補綴分野に於ける
歯冠修復材料、支台歯材料、合着材料、充填材
料、裏装剤、根管充填剤等に使用する事ができ
る。
以下実施例により本発明を具体的に説明する。
尚、実施例中、モノマーの粘度、コンポジツトレ
ジンならびにシーラントの調製および硬化方法、
硬化後のサンプルの物性値（吸水率、歯ブラシ摩
耗深さ、圧縮強度、屈折率）の測定は、以下の方
法に従つた。
(イ) サンプルの調製および硬化方法
(a) 先ず、γ−メタクリロキシプロピルトリメ
トキシシランによつて表面処理された非晶質
シリカと本発明の新規物質を一成分とするビ
ニルモノマーを所定の割合でメノウ乳鉢に入
れ均一なペーストとなるまで十分混練した。
次いで該ペーストを二等分し、一方のペース
トにはさらに重合促進剤を加え十分混合し
た。（これをペーストＡとする）。また他方の
ペーストには有機過酸化物触媒を加え十分混
合した。（これをペーストＢとする）。次にペ
ーストＡ及びペーストＢの等量を約30秒間混
練し、型枠に充填し硬化させた。
(b) 本発明の新規物質を一成分とするビニルモ
ノマーを二等分し、一方の液には重合促進剤
を加え十分混合した。（これを液Ａとする）。
また他方のモノマー液には有機過酸化物触媒
を加え十分混合した。（これを液Ｂとする）。
次に液Ａ及び液Ｂの等量を約30秒間混練
し、型枠に充填し硬化させた。
(ロ) 吸水率
ペーストＡとペーストＢ（あるいは液Ａと液
Ｂ）を混合して、室温で30分重合させた後、37
℃で45時間真空乾燥を行なつた。次に乾燥重量
を測つた後、37℃の温水に浸漬した各日数毎に
重量変化を測定した。そのサンプルの形状は10
mm×10mm×1.5mmの立方体である。
(ハ) 圧縮強度
ペーストＡとペーストＢ（あるいは液Ａと液
Ｂ）を混合して室温で30分間重合させた後、37
℃水中24時間浸漬したものを試験片とした。そ
の大きさ、形状は直径６mm、高さ12mmの円柱状
のものである。試験片を試験機（東洋ボードウ
イン製UTM−5T）に装着し、クロスヘツドス
ピード10mm／minで圧縮強度を測定した。
(ニ) 歯ブラシ摩耗深さ
ペーストＡとペーストＢ（あるいは液Ａと液
Ｂ）を混合して室温で30分間重合させた後、37
℃水中で24時間浸漬したものを試験片とした。
その大きさ、形状は1.5×10×10mmの板状のも
のである。試験片と荷重400ｇで歯ブラシで
1500ｍ摩耗した後摩耗深さを求めた。尚、摩耗
深さは摩耗重量を複合レジン（あるいはポリマ
ー）の密度で除して求めた。
(ホ) 粘度測定
東京計器製のＥ形粘度計を使用して含弗素不
飽和カルボン酸エステルの粘度を求めた。測定
は21℃の恒温室で行なつた。
(ヘ) 屈折率
含弗素不飽和カルボン酸エステルの屈折率な
らびに有機過酸化物触媒を加えた含弗素不飽和
カルボン酸エステルを100℃で加熱重合して得
られる重合体の屈折率をアツベの屈折計で測定
した。
また実施例で用いた原料の略語は表１に示す
通りである。Since [Formula] has a low boiling point, it is more preferable to use a pressure-resistant container. When carrying out the production method described in () above, means for stirring the reaction system for uniform dispersion of reaction heat and uniform dispersion of raw material component compounds can often be employed as a suitable means. Further, in order to separate the fluorine-containing unsaturated carboxylic acid ester produced by the above production method () from the mixture in the reaction vessel, the same operation as in the above production method may be used. Next, a method of utilizing the fluorine-containing unsaturated carboxylic acid ester, which is a novel substance of the present invention, will be explained below. The fluorine-containing unsaturated carboxylic acid ester of the present invention is
As mentioned above, since it has unsaturated bonds, it is widely used as a monomer, crosslinking agent, etc. for polymers or copolymers. For example, it is suitably used in dental filler compositions. The use of the fluorine-containing unsaturated carboxylic acid ester in a dental filler composition will be explained below. Dental filler compositions are generally referred to as composite resins, such as paste-like mixtures of polymerizable monomers and inorganic fillers, or cured materials, or are made from polymerizable monomers. This liquid material or its polymer is used as a polymerizable monomer in what is generally called a sealant. Currently, among medical and dental materials, especially dental materials, materials whose main components are bisphenol A diglycidyl methacrylate (hereinafter referred to as [Bis-GMA]) and inorganic filler (hereinafter referred to as ``Bis-GMA'') are used as filling materials for restorations.
GMA-based composite resin) has been developed and is also used as a filling material for pits and fissures.
Bis-GMA-based organic material (hereinafter referred to as “Bis
-GMA sealants) are also used. However, because these Bis-GMA filling materials have a high water absorption rate, water tends to enter between the tooth structure and the filling material, and this causes streptococcus cumutans, which causes tooth decay, to enter along with the water. It can easily become trapped and cause secondary caries. In addition, since the refractive index of Bis-GMA is as high as 1.55, inorganic substances with a low refractive index (such as amorphous silica) are suitable for inorganic fillers used as raw materials for composite resins.
It has the disadvantage that it cannot be used as a filler because it does not give a transparent feel when mixed. However, the above defects can be solved by using the Bis-GMA composite resin and the fluorine-containing unsaturated carboxylic acid ester of the present invention in place of Bis-GMA. The novel substance of the present invention has excellent properties such as low viscosity, low refractive index, and water repellency. In addition, in practical use, when used in composite resins, it is generally mixed with an inorganic filler, a catalyst for polymerizing the composite resin, and a promoter that reacts with the catalyst to generate free radicals. be.
Further, as the inorganic filler, quartz powder, glass powder, glass beads, aluminum oxide, amorphous silica, etc. may be used. Furthermore, the inorganic filler preferably accounts for 50 to 90% by weight of the composite resin. Furthermore, if the inorganic filler is previously treated with a coupling agent such as γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, etc., the bond between the inorganic filler and the resin composition will be strengthened, making it suitable for physical use as a medical and dental material. This is preferable because the properties are further improved. or,
Typical examples of the catalyst that are preferably used include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, and lauroyl peroxide. These catalysts are generally used in a proportion of 0.1 to 2.0 parts by weight per 100 parts by weight of the resin composition. Furthermore, typical accelerators include N.N-dimethyl-P-toluidine and N.N-bis-(2-hydroxyethyl)-4.
-Methylaniline, N.N-bis-(2-hydroxyethyl)-3.5-dimethylaniline, N.
N-bis-(2-hydroxyethyl)-3,4-dimethylaniline and the like are preferably used. These accelerators may generally be used in an amount of 0.1 to 2.0 parts by weight per 100 parts by weight of the resin composition. Furthermore, in order to improve the storage stability of the resin composition, a benzophenone compound, for example, an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, may be added in an amount of 0.5 to 2.0 parts by weight or generally based on 100 parts by weight of the resin composition. A stabilizer called a rally radical chain reaction terminator, such as P-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, etc., is added to the resin composition, a paste consisting of a promoter (paste A), and an inorganic filler. A paste-like substance (paste B) consisting of a resin composition catalyst is prepared in advance, and when used by a doctor, the resin composition starts polymerization simply by mixing these two pastes, which is very convenient. . When using the novel substance of the present invention in a sealant,
Large amounts of inorganic fillers are not mixed together, but other catalysts, accelerators, ultraviolet absorbers, etc.
Same as composite resin. When used by a doctor, the same method is used in which the two liquids are mixed and the resin composition starts polymerizing. The resin composition of the present invention can be used for medical purposes, such as bone cement artificial bones in the orthopedics and plastic surgery fields, or crown restoration materials, abutment materials, and bonding materials in the dental preservation and prosthetics fields. It can be used as filling material, lining agent, root canal filling agent, etc. The present invention will be specifically explained below using Examples.
In addition, in the examples, the viscosity of the monomer, the preparation and curing method of the composite resin and sealant,
Physical property values (water absorption, toothbrush wear depth, compressive strength, refractive index) of the sample after curing were measured according to the following method. (b) Sample preparation and curing method (a) First, amorphous silica surface-treated with γ-methacryloxypropyltrimethoxysilane and a vinyl monomer containing the novel substance of the present invention as one component are mixed in a predetermined ratio. The mixture was placed in an agate mortar and thoroughly kneaded until it became a uniform paste.
The paste was then divided into two equal parts, and a polymerization accelerator was further added to one of the pastes and thoroughly mixed. (This is called paste A). Further, an organic peroxide catalyst was added to the other paste and thoroughly mixed. (This is called paste B). Next, equal amounts of paste A and paste B were kneaded for about 30 seconds, filled into a mold, and hardened. (b) A vinyl monomer containing the novel substance of the present invention as one component was divided into two equal parts, and a polymerization accelerator was added to one of the liquids and thoroughly mixed. (This is called liquid A).
Further, an organic peroxide catalyst was added to the other monomer liquid and thoroughly mixed. (This is called liquid B). Next, equal amounts of liquid A and liquid B were kneaded for about 30 seconds, filled into a mold, and cured. (b) Water absorption rate After mixing paste A and paste B (or liquid A and liquid B) and polymerizing them at room temperature for 30 minutes,
Vacuum drying was performed at ℃ for 45 hours. Next, after measuring the dry weight, changes in weight were measured for each number of days of immersion in hot water at 37°C. The sample shape is 10
It is a cube measuring mm x 10 mm x 1.5 mm. (c) Compressive strength After mixing paste A and paste B (or liquid A and liquid B) and polymerizing for 30 minutes at room temperature, 37
A test piece was prepared by immersing it in water at ℃ for 24 hours. Its size and shape are cylindrical with a diameter of 6 mm and a height of 12 mm. The test piece was mounted on a testing machine (UTM-5T manufactured by Toyo Baudouin), and the compressive strength was measured at a crosshead speed of 10 mm/min. (d) Toothbrush wear depth After mixing paste A and paste B (or liquid A and liquid B) and polymerizing for 30 minutes at room temperature, 37
A test piece was prepared by immersing it in ℃ water for 24 hours.
Its size and shape are plate-like, 1.5 x 10 x 10 mm. Using a toothbrush with a test piece and a load of 400g.
The wear depth was determined after 1500m of wear. Note that the wear depth was determined by dividing the wear weight by the density of the composite resin (or polymer). (e) Viscosity measurement The viscosity of the fluorine-containing unsaturated carboxylic acid ester was determined using an E-type viscometer manufactured by Tokyo Keiki. Measurements were performed in a constant temperature room at 21°C. (f) Refractive index The refractive index of the fluorine-containing unsaturated carboxylic acid ester and the refractive index of the polymer obtained by heating and polymerizing the fluorine-containing unsaturated carboxylic acid ester added with an organic peroxide catalyst at 100°C are defined as Atsube's refraction index. Measured with a meter. Further, the abbreviations of raw materials used in the examples are as shown in Table 1.
【表】【table】
【表】
実施例 １
100mlのステンレス製オートクレーブに第１表
に示す構造式のbisGMA1.84ｇとベンゼン30mlを
入れて充分撹拌混合した後ドライアイス−メタノ
ール溶液で冷却した。次にあらかじめ−78℃に冷
却した100mlの耐圧ガラス容器に貯蔵しておいた
パーフルオロプロピオン酸フルオリド（沸点−28
℃）10mlを銅パイプを通じてオートクレーブ内に
導入した。その後一夜撹拌を続けたのちオートク
レーブ容器の内容物を分液ロートに移し大量の水
を加えると、水層が弱酸性を示した。そこで炭酸
水素ナトリウム水溶液で水層を中和した後ベンゼ
ン層のみを取り出し、ベンゼンを蒸発した後目的
物を得た。収率は79％であつた。得られた反応生
成物の赤外吸収スペクトルによれば、3500cm-1付
近のOH基に基因する吸収が消失し1780cm-1にパ
ーフルオロアルキル基に結合したカルボン酸エス
テルによる吸収、1400〜1100cm-1にＣ−Ｆ結合に
よる吸収が現われた。
またメタクリル基のカルボン酸エステルによる
吸収が1720cm-1、二重結合による吸収が1640cm
-1、ベンゼン環による吸収は1495cm-1に観察され
た。
次に生成物の13C核磁気共鳴スペクトルを用い
て同定を行なつた。結果は下記の通りである。[Table] Example 1 1.84 g of bisGMA having the structural formula shown in Table 1 and 30 ml of benzene were placed in a 100 ml stainless steel autoclave, stirred and mixed thoroughly, and then cooled with a dry ice-methanol solution. Next, perfluoropropionic acid fluoride (boiling point -28
℃) was introduced into the autoclave through a copper pipe. After stirring overnight, the contents of the autoclave were transferred to a separatory funnel and a large amount of water was added, and the aqueous layer showed weak acidity. Therefore, after neutralizing the aqueous layer with an aqueous sodium hydrogen carbonate solution, only the benzene layer was taken out, and after evaporating the benzene, the desired product was obtained. The yield was 79%. According to the infrared absorption spectrum of the obtained reaction product, the absorption based on the OH group disappeared around 3500 cm -1 , the absorption due to the carboxylic acid ester bonded to the perfluoroalkyl group disappeared at 1780 cm -1 , and the absorption due to the carboxylic acid ester bonded to the perfluoroalkyl group appeared at 1400 to 1100 cm -1. Absorption due to C-F bond appeared in 1 . Also, absorption due to carboxylic acid ester of methacrylic group is 1720 cm -1 and absorption due to double bond is 1640 cm
-1 , absorption by the benzene ring was observed at 1495 cm -1 . Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results are as follows.
【表】
更にまた生成物の質量分析スペクトルにより
ｍ／ｅ＝804の分子イオンピークが観察された。
更にまた生成物の元素分析の結果を以下に示
す。[Table] Furthermore, a molecular ion peak of m/e=804 was observed in the mass spectrometry spectrum of the product. Furthermore, the results of elemental analysis of the product are shown below.
【表】
これらの分析結果より反応生成物は
であることが確認出来た。この生成物と該生成物
を重合開始剤としてラウロイルパーオキサイド
を用いて100℃、10時間加熱重合を行なつて得ら
れるポリマーの屈折率はそれぞれ1.480ならびに
1.499であつた。
実施例 ２
100mlのステンレス製オートクレーブに
bisGMA16.7ｇ、トリエチルアミン１ｇ、アセト
ニトリル50mlを入れて充分撹拌混合した後、ドラ
イアイス−メタノール溶液で冷却した。次にあら
かじめ−78℃に冷却した100ml用耐圧ガラス容器
に貯蔵しておいたヘキサフルオロプロピレンオキ
サイド（以下HFPOと呼ぶ）35mlを次第に室温に
戻しながら銅パイプを通じてオートクレーブ内に
導入した。導入後オートクレーブを徐々に室温に
戻し一夜撹拌放置した。圧力は一旦５Kg／cm2まで
上昇するが、その後徐々に減圧して行き最終的に
2.7Kg／cm2で安定した。ガス成分は赤外吸収スペ
クトルにより1890cm-1に酸フルオリドの吸収を持
つ事からHFPOの異性化反応によつて生じたプロ
ピオン酸フルオリドだと考えられる。次に反応ガ
スを抜いた後、反応物を分液ロートに移し大量の
水および１・１・２−トリクロロ−１・２・２−
トリフルオロエタン溶媒（CClF2CCl2F）を加え
た。ここで未反応のbisGMAならびに溶媒のアセ
トニトリルは水層に移る。水層は強酸性を示すの
で炭酸水素ナトリウム水溶液で中和した後、１・
１・２−トリクロロ−１・２・２−トリフルオロ
エタン層を採り出し、溶媒を蒸発させて目的生成
物を得た。収率は75％であつた。得られた生成物
は実施例１とまつたく同様な赤外吸収スペクトル
を示した。又、13C核磁気共鳴スペクトル、質量
分析スペクトルについても実施例１と同様な結果
を示した。元素分析の結果は
Ｃ：52.15、Ｈ：4.39、Ｆ：11.76
となつた。これらの分析結果より反応生成物は実
施例１と同じ化合物である事が分つた。又、この
生成物ならびにこの生成物を実施例１と同様な方
法で重合したポリマーの屈折率はそれぞれ1.480
ならびに1.499であつた。
実施例 ３
100mlの三つ口フラスコにbisGMA11.9ｇとベ
ンゼン25mlを入れて充分撹拌しながら、HFPOの
２量体
（CF3CF2CF2OCF（CF3）COF）20.7ｇを滴
下した。滴下後、約５時間撹拌を行なつた。次に
反応液から２mmHgの減圧下50℃で原料酸フルオ
リドとベンゼンを除去した。残つた生成物を分液
ロートに移し水と１・１・２−トリクロロ−１・
２・２−トリフルオロエタン溶媒を加えた。ここ
で未反応のbisGMA、生成した弗化水素ならびに
パーフルオロカルボン酸は水層に移る。水層は強
酸性を示すのでNaHCO3水溶液で中和した。その
後１・１・２−トリクロロ−１・２・２−トリフ
ルオロエタン層を採り出し、溶媒を蒸発させて粘
稠な液体を得た。この反応の収率は98％であつ
た。この生成物の赤外吸収スペクトルは実施例１
と同様な吸収を示した。次に生成物の13C核磁気
共鳴スペクトルを用いて同定を行なつた。結果は
次の通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that this is the case. This product and lauroyl peroxide using this product as a polymerization initiator The refractive index of the polymer obtained by heating polymerization at 100℃ for 10 hours using
It was 1.499. Example 2 In a 100ml stainless steel autoclave
After adding 16.7 g of bisGMA, 1 g of triethylamine, and 50 ml of acetonitrile and thoroughly stirring and mixing, the mixture was cooled with a dry ice-methanol solution. Next, 35 ml of hexafluoropropylene oxide (hereinafter referred to as HFPO), which had been previously cooled to -78°C and stored in a 100 ml pressure-resistant glass container, was introduced into the autoclave through a copper pipe while being gradually returned to room temperature. After the introduction, the autoclave was gradually returned to room temperature and left stirring overnight. The pressure once rises to 5Kg/ cm2 , but then gradually decreases and finally
It stabilized at 2.7Kg/ cm2 . The gas component is thought to be propionic acid fluoride produced by the isomerization reaction of HFPO, as the infrared absorption spectrum shows an absorption of acid fluoride at 1890 cm -1 . Next, after removing the reaction gas, the reaction product was transferred to a separating funnel, and a large amount of water and 1,1,2-trichloro-1,2,2-
Trifluoroethane solvent ( CClF2CCl2F ) was added. Here, unreacted bisGMA and the solvent acetonitrile move to the aqueous layer. The aqueous layer is strongly acidic, so after neutralizing it with an aqueous sodium hydrogen carbonate solution, 1.
The 1,2-trichloro-1,2,2-trifluoroethane layer was taken out and the solvent was evaporated to obtain the desired product. The yield was 75%. The obtained product showed an infrared absorption spectrum very similar to that of Example 1. Furthermore, the same results as in Example 1 were also shown in the 13 C nuclear magnetic resonance spectrum and mass spectrometry spectrum. The results of elemental analysis were C: 52.15, H: 4.39, and F: 11.76. These analysis results revealed that the reaction product was the same compound as in Example 1. The refractive index of this product and the polymer obtained by polymerizing this product in the same manner as in Example 1 are each 1.480.
and 1.499. Example 3 11.9 g of bisGMA and 25 ml of benzene were placed in a 100 ml three-necked flask, and 20.7 g of HFPO dimer (CF 3 CF 2 CF 2 OCF (CF 3 )COF) was added dropwise while stirring thoroughly. After the dropwise addition, stirring was continued for about 5 hours. Next, the raw acid fluoride and benzene were removed from the reaction solution at 50° C. under a reduced pressure of 2 mmHg. Transfer the remaining product to a separating funnel and mix with water and 1,1,2-trichloro-1.
2,2-trifluoroethane solvent was added. Here, unreacted bisGMA, generated hydrogen fluoride, and perfluorocarboxylic acid move to the aqueous layer. Since the aqueous layer was strongly acidic, it was neutralized with an aqueous NaHCO 3 solution. Thereafter, the 1,1,2-trichloro-1,2,2-trifluoroethane layer was taken out, and the solvent was evaporated to obtain a viscous liquid. The yield of this reaction was 98%. The infrared absorption spectrum of this product is shown in Example 1.
showed similar absorption. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as follows.
【表】
また生成物の質量分析スペクトルによりｍ／ｅ
＝169（C3F7）、1136（分子イオンピーク）が観
察された。
更にまた生成物の元素分析の結果は以下に示す
通りであつた。[Table] Also, based on the mass spectrometry spectrum of the product, m/e
= 169 (C 3 F 7 ), 1136 (molecular ion peak) was observed. Furthermore, the results of elemental analysis of the product were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびにこの生成物を実施例１
と同様な方法で重合したポリマーの屈折率はそれ
ぞれ1.459、1.478であつた。
実施例 ４
100mlの三つ口フラスコにbisGMA10.0ｇ、ト
リエチルアミン7.3ｇとベンゼン25mlを入れて充
分撹拌しながらヘキサフルオロプロピレンオキサ
イドの２量体の酸クロライド（CF3CF2CF2OCF
（CF3）COCl）25.0ｇを滴下した。滴下後一夜撹
拌を行なつた。次に反応液から２mmHgの減圧下
50℃で原料酸クロライドとベンゼンを除去した。
ここで残つた反応液に大量の水と１・１・２−ト
リクロロ−１・２・２−トリフルオロエタンを加
えることによつて、トリエチルアミンの塩酸塩は
水層に移り、目的の生成物のみが１・１・２−ト
リクロロ−１・２・２−トリフルオロエタン層に
溶解する。そこで１・１・２−トリクロロ−１・
２・２−トリフルオロエタン層を分液ろう斗を用
いて取り出し、溶媒を蒸発させて目的の生成物を
得た。この反応の収率は89％であつた。得られた
生成物は実施例３とまつたく同様な赤外吸収スペ
クトルを示した。又、13C核磁気共鳴スペクト
ル、質量スペクトルについても実施例３と同様な
結果を示した。元素分析の結果は
Ｃ：43.50 Ｈ：3.10 Ｆ：18.36
となつた。これらの分析結果より、反応生成物は
実施例３と同じ化合物である事が分つた。
又、この生成物ならびにこの生成物を実施例１
と同様な方法で重合したポリマーの屈折率はそれ
ぞれ1.459、1.478であつた。
実施例 ５
bisGMAとHFPOの３量体との反応を実施例３
と同様な方法で行なつた。収率は90％であつた。
生成物の赤外吸収スペクトルは実施例１と同様
な吸収を示した。次に生成物の13C核磁気共鳴ス
ペクトルを用いて同定を行なつた。その結果は次
に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Also, this product as well as this product in Example 1
The refractive index of polymers polymerized in the same manner as 1.459 and 1.478, respectively. Example 4 Put 10.0 g of bisGMA, 7.3 g of triethylamine, and 25 ml of benzene into a 100 ml three-necked flask, and while stirring thoroughly, add dimeric acid chloride of hexafluoropropylene oxide (CF 3 CF 2 CF 2 OCF
(CF 3 )COCl) 25.0 g was added dropwise. After the addition, stirring was continued overnight. Next, under a reduced pressure of 2 mmHg from the reaction solution.
Raw material acid chloride and benzene were removed at 50°C.
By adding a large amount of water and 1,1,2-trichloro-1,2,2-trifluoroethane to the remaining reaction solution, triethylamine hydrochloride is transferred to the aqueous layer, and only the desired product is produced. is dissolved in the 1,1,2-trichloro-1,2,2-trifluoroethane layer. Therefore, 1,1,2-trichloro-1,
The 2,2-trifluoroethane layer was removed using a separatory funnel and the solvent was evaporated to yield the desired product. The yield of this reaction was 89%. The obtained product showed an infrared absorption spectrum very similar to that of Example 3. Furthermore, the same results as in Example 3 were also shown in the 13 C nuclear magnetic resonance spectrum and mass spectrum. The results of elemental analysis were: C: 43.50 H: 3.10 F: 18.36. These analysis results revealed that the reaction product was the same compound as in Example 3. Also, this product as well as this product in Example 1
The refractive index of polymers polymerized in the same manner as 1.459 and 1.478, respectively. Example 5 Example 3 shows the reaction between bisGMA and HFPO trimer.
It was done in a similar way. The yield was 90%. The infrared absorption spectrum of the product showed the same absorption as in Example 1. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また質量分析スペクトルによりｍ／ｅ＝169
（C3F7）、1468（分子イオンピーク）が観察され
た。
更にまた元素分析の結果は以下に示す通りであ
つた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 ), 1468 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびにこの生成物を実施例１
と同様な方法で重合したポリマーの屈折率はそれ
ぞれ1.428、1.449であつた。
実施例 ６
表１に示した構造式を持つメタクリル酸誘導体
（エポキシエステル3002M）とHFPOの反応を行
なつた。この際、触媒としてトリエチルアミンを
用い、実施例２と同様な方法で行なつた。収率は
74％であつた。
生成物の赤外吸収スペクトルは、実施例１と同
様な吸収を示した。次に生成物の13C核磁気共鳴
スペクトルを用いて同定を行なつた。
その結果は次に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Also, this product as well as this product in Example 1
The refractive index of polymers polymerized in the same manner as 1.428 and 1.449, respectively. Example 6 A methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 was reacted with HFPO. At this time, the same method as in Example 2 was conducted using triethylamine as a catalyst. The yield is
It was 74%. The infrared absorption spectrum of the product showed absorption similar to that of Example 1. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また質量分析スペクトルによりｍ／ｅ＝946の
分子イオンピークが観察された。
更にまた元素分析の結果は以下に示す通りであ
つた。[Table] Furthermore, a molecular ion peak of m/e=946 was observed in the mass spectrometry spectrum. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびに生成物を実施例１と同
様な方法で重合したポリマーの屈折率はそれぞれ
1.467、1.484であつた。
実施例 ７
表１に示した構造式を持つメタクリル酸誘導体
（エポキシエステル3002M）とHFPOの２量体の
反応を実施例３と同様な方法で行なつた。収率は
54％であつた。生成物の赤外吸収スペクトルは実
施例１と同様な吸収を示した。次に生成物の13C
核磁気共鳴スペクトルを用いて同定を行なつた。
その結果は次に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are as follows:
It was 1.467 and 1.484. Example 7 A reaction between a methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 and a dimer of HFPO was carried out in the same manner as in Example 3. The yield is
It was 54%. The infrared absorption spectrum of the product showed the same absorption as in Example 1. Then the product 13 C
Identification was made using nuclear magnetic resonance spectroscopy.
The results were as shown below.
【表】
また質量分析スペクトルによりｍ／ｅ＝169
（C3F7）1278（分子イオンピーク）が観察され
た。
更にまた元素分析の結果は以下に示す通りであ
つた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 ) 1278 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびに生成物を実施例１と同
様な方法で重合したポリマーの屈折率はそれぞれ
1.456、1.475であつた。
実施例 ８
表１に示した構造式を持つメタクリル酸誘導体
（エポキシエステル3002M）とHFPOの３量体の
反応を実施例３と同様な方法で行なつた。収率は
82％であつた。生成物の赤外吸収スペクトルは実
施例１と同様な吸収を示した。次に生成物の13C
核磁気共鳴スペクトルを用いて同定を行なつた。
その結果は次に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are as follows:
It was 1.456 and 1.475. Example 8 A reaction between a methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 and a trimer of HFPO was carried out in the same manner as in Example 3. The yield is
It was 82%. The infrared absorption spectrum of the product showed the same absorption as in Example 1. Then the product 13 C
Identification was made using nuclear magnetic resonance spectroscopy.
The results were as shown below.
【表】
また質量分析スペクトルによりｍ／ｅ＝169
（C3F7）1610（分子イオンピーク）が観察され
た。
更にまた元素分析の結果は以下に示す通りであ
つた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 ) 1610 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。又、この生成物ならび
に生成物を実施例１と同様な方法で重合したポリ
マーの屈折率はそれぞれ1.395、1.414であつた。
実施例 ９
表１に示した構造式を持つメタクリル酸誘導体
（エポキシエステル40EM）とHFPOの反応を行な
つた。この際、触媒としてトリエチルアミンを用
い実施例２と同様な方法で行なつた。収率は68％
であつた。
生成物の赤外吸収スペクトルは、ベンゼン環に
よる吸収（1495cm-1）が無い点以外は実施例１と
同様な吸収を示した。次に生成物の13C核磁気共
鳴スペクトルを用いて同定を行なつた。その結果
は次に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that The refractive index of this product and a polymer obtained by polymerizing the product in the same manner as in Example 1 were 1.395 and 1.414, respectively. Example 9 A methacrylic acid derivative (epoxy ester 40EM) having the structural formula shown in Table 1 was reacted with HFPO. At this time, the same method as in Example 2 was conducted using triethylamine as a catalyst. Yield is 68%
It was hot. The infrared absorption spectrum of the product showed the same absorption as in Example 1 except that there was no absorption due to the benzene ring (1495 cm -1 ). Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量分析スペクトルによりｍ／ｅ＝638
（分子イオンピーク）が観察された。更にまた元
素分析の結果は以下に示す通りであつた。[Table] Also, according to the mass spectrometry spectrum, m/e = 638
(molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。又、この生成物ならび
に生成物を実施例１と同様な方法で重合したポリ
マーの屈折率はそれぞれ1.415、1.437であつた。
実施例 10
表１に示した構造式を持つメタクリル酸誘導体
（エポキエステル40EM）とHFPOの２量体の反応
を実施例３と同様な方法で行なつた。収率は76％
であつた。
生成物の赤外吸収スペクトルは、実施例９と同
様な吸収を示した。次に、生成物の13C核磁気共
鳴スペクトルを用いて同定を行なつた。その結果
は次に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that The refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 were 1.415 and 1.437, respectively. Example 10 A reaction between a methacrylic acid derivative (epoxyester 40EM) having the structural formula shown in Table 1 and a dimer of HFPO was carried out in the same manner as in Example 3. Yield is 76%
It was hot. The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量スペクトルによりｍ／ｅ＝169
（C3F7）970（分子イオンピーク）が観察され
た。更にまた元素分析の結果は以下に示す通りで
あつた。[Table] Also, according to the mass spectrum, m/e = 169
(C 3 F 7 )970 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。又、この生成物ならび
に生成物を実施例１と同様な方法で重合したポリ
マーの屈折率はそれぞれ1.377、1.404であつた。
実施例 11
表１に示した構造式を持つメタクリル酸誘導体
（エポキシエステル40EM）とHFPOの３量体の反
応を実施例３と同様な方法で行なつた。収率は65
％であつた。
生成物の赤外吸収スペクトルは実施例９と同様
な吸収を示した。次に生成物の13C核磁気共鳴ス
ペクトルを用いて同定を行なつた。その結果は次
に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that The refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 were 1.377 and 1.404, respectively. Example 11 A reaction between a methacrylic acid derivative (epoxy ester 40EM) having the structural formula shown in Table 1 and a trimer of HFPO was carried out in the same manner as in Example 3. Yield is 65
It was %. The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量分析スペクトルによりｍ／ｅ＝169
（C3F7）、1302（分子イオンピーク）が観察され
た。更にまた元素分析の結果は以下に示す通りで
あつた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 ), 1302 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。又、この生成物ならび
に生成物の実施例１と同様な方法で重合したポリ
マーの屈折率はそれぞれ1.365、1.381であつた。
実施例 12
表１に示した構造式を持つアクリル酸誘導体
（エポキシエステル70PA）とHFPOの反応を行な
つた。この際、触媒としてトリエチルアミンを用
い実施例２と同様な方法で行なつた。収率は68％
であつた。
生成物の赤外吸収スペクトルは実施例９と同様
な吸収を示した。次に生成物の13C核磁気共鳴ス
ペクトルを用いて同定を行なつた。その結果は次
に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that The refractive index of this product and the polymer polymerized in the same manner as in Example 1 were 1.365 and 1.381, respectively. Example 12 An acrylic acid derivative (epoxy ester 70PA) having the structural formula shown in Table 1 was reacted with HFPO. At this time, the same method as in Example 2 was conducted using triethylamine as a catalyst. Yield is 68%
It was hot. The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量分析スペクトルによりｍ／ｅ＝624
の分子イオンピークが観察された。更にまた元素
分析の結果は以下に示す通りであつた。[Table] Also, according to the mass spectrometry spectrum, m/e = 624
A molecular ion peak of was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびに生成物を実施例１と同
様な方法で重合したポリマーの屈折率はそれぞれ
1.405、1.427であつた。
実施例 13
表１に示した構造式を持つアクリル酸誘導体
（エポキシエステル70PA）とHFPOの２量体の反
応を実施例３と同様な方法で行なつた。収率は96
％であつた。
生成物の赤外吸収スペクトルは実施例９と同様
な吸収を示した。次に生成物の13C核磁気共鳴ス
ペクトルを用いて同定を行なつた。その結果は次
に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are as follows:
It was 1.405 and 1.427. Example 13 A reaction between an acrylic acid derivative (epoxy ester 70PA) having the structural formula shown in Table 1 and a dimer of HFPO was carried out in the same manner as in Example 3. Yield is 96
It was %. The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量分析スペクトルによりｍ／ｅ＝169
（C3F7）956（分子イオンピーク）が観察され
た。更にまた元素分析の結果は以下に示す通りで
あつた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 )956 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびに生成物を実施例１と同
様な方法で重合したポリマーの屈折率はそれぞれ
1.375、1.394であつた。
実施例 14
表１に示した構造を持つアクリル酸誘導体（エ
ポキシエステル70PA）とHFPO3量体の反応を実
施例３と同様な方法で行なつた。収率は80.0％で
あつた。
生成物の赤外吸収スペクトルは実施例９と同様
な吸収を示した。次に生成物の13C核磁気共鳴ス
ペクトルを用いて同定を行なつた。その結果は次
に示す通りであつた。[Table] From these analysis results, the reaction products are It was confirmed that Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are as follows:
It was 1.375 and 1.394. Example 14 A reaction between an acrylic acid derivative (epoxy ester 70PA) having the structure shown in Table 1 and HFPO trimer was carried out in the same manner as in Example 3. The yield was 80.0%. The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 13 C nuclear magnetic resonance spectrum. The results were as shown below.
【表】
また、質量分析スペクトルによりｍ／ｅ＝169
（C3F7）1288（分子イオンピーク）が観察され
た。更にまた元素分析の結果は以下に示す通りで
あつた。[Table] Also, according to the mass spectrometry spectrum, m/e = 169
(C 3 F 7 ) 1288 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.
【表】
これらの分析結果より反応生成物は
であることが確認された。
又、この生成物ならびに生成物を実施例１と同
様な方法で重合したポリマーの屈折率はそれぞれ
1.351、1.369であつた。
実施例 15
0.3μのシリカ粒子をγ−メタクリロキシプロ
ピルトリメトキシシランで表面処理したものをフ
イラーとして用い、ビニルモノマーとして
BisGMA、BisGMAとHFPOの２量体を応応させ
たもの（以下Ｆ−bisGMAと言う）、そして希釈
用モノマーとしてトリエチレングリコールジメタ
クリレート（以下TEGDMAと言う）を用い、上
記シリカ粒子と配合し充分練和することによりペ
ースト状の複合修復材を得た。この際、複合修復
材のシリカ粒子の充填量は73.6wt％でペーストの
粘度は操作上適正であつた。次にペーストを二等
分にして一方には重合促進剤としてＮ・Ｎ−ジメ
チル−Ｐ−トルイジンを、もう一方には重合開始
剤として過酸化ベンゾイルを各々ビニルモノマー
に対してそれぞれ1wt％添加しペーストＡ（前
者）及びペーストＢ（後者）を調製した。
上記のペーストＡとペーストＢを等量取り30秒
間室温で練和し硬化させたものについて吸水率を
測定した。尚、硬化した試料は、37℃で45時間真
空乾燥した。次に乾燥重量を測定した後、37℃温
水中に浸漬して１日後および２日後に重量増加を
測定した。その結果を表２に示した。[Table] From these analysis results, the reaction products are It was confirmed that Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are as follows:
It was 1.351 and 1.369. Example 15 Silica particles of 0.3 μm were surface-treated with γ-methacryloxypropyltrimethoxysilane and used as a filler, and as a vinyl monomer.
BisGMA, a reaction product of a dimer of BisGMA and HFPO (hereinafter referred to as F-bisGMA), and triethylene glycol dimethacrylate (hereinafter referred to as TEGDMA) as a diluent monomer were mixed with the above silica particles and kneaded thoroughly. A paste-like composite restorative material was obtained by mixing. At this time, the filling amount of silica particles in the composite restorative material was 73.6 wt%, and the viscosity of the paste was appropriate for operation. Next, the paste was divided into two halves, and to one side, N.N-dimethyl-P-toluidine was added as a polymerization accelerator, and to the other side, 1wt% of benzoyl peroxide was added as a polymerization initiator, based on the vinyl monomer. Paste A (former) and paste B (latter) were prepared. Equal amounts of Paste A and Paste B were mixed together at room temperature for 30 seconds and cured, and the water absorption was measured. The cured sample was vacuum dried at 37°C for 45 hours. Next, after measuring the dry weight, the weight increase was measured one day and two days after immersion in 37°C warm water. The results are shown in Table 2.
【表】
実施例 16
ビニルモノマーとしてbisGMA、Ｆ−bisGMA
および希釈用モノマーとしてTEGDMAを用い、
これらを混合して液体修復材を得た。次に液を二
等分して、一方には重合促進剤としてＮ・Ｎ−ジ
メチル−Ｐ−トルイジンを、もう一方には重合開
始剤として過酸化ベンゾイルを各々ビニルモノマ
ーに対して1wt％添加し、液Ａ（前者）及び液Ｂ
（後者）を調製した。上記の液Ａと液Ｂを等量取
り30秒間室温で練和し硬化させたものについて吸
水率を測定した。測定法は実施例15と同様であ
る。
上記試作品の吸水率の変化は表３に示した。[Table] Example 16 BisGMA and F-bisGMA as vinyl monomers
and using TEGDMA as a diluting monomer,
These were mixed to obtain a liquid restorative material. Next, the liquid was divided into two parts, and to one side, N.N-dimethyl-P-toluidine was added as a polymerization accelerator, and to the other side, 1wt% of benzoyl peroxide was added as a polymerization initiator, based on the vinyl monomer. , liquid A (former) and liquid B
(the latter) was prepared. Equal amounts of the above liquids A and B were kneaded at room temperature for 30 seconds and cured, and the water absorption rate was measured. The measurement method is the same as in Example 15. Table 3 shows the changes in water absorption of the above prototypes.
【表】
実施例 17
実施例16と同様な方法で液状の修復材を調製し
た。ビニルモノマー成分の混合割合は表４に示し
た通りである。液状の修復材を実施例15と同様な
操作で硬化させ、圧縮強度を測定した。
その結果を表４に示す。[Table] Example 17 A liquid restorative material was prepared in the same manner as in Example 16. The mixing proportions of the vinyl monomer components are shown in Table 4. The liquid repair material was cured in the same manner as in Example 15, and the compressive strength was measured. The results are shown in Table 4.
【表】
実施例 18
実施例15と同様な方法で液状の修復材を調製し
た。ビニルモノマー成分の混合割合は表５に示し
た通りである。液状の修復材をそれぞれ実施例15
と同様な操作で硬化させ、ハブラシ摩耗深さを調
べた。その結果を表５に示す。[Table] Example 18 A liquid restorative material was prepared in the same manner as in Example 15. The mixing proportions of the vinyl monomer components are shown in Table 5. Example 15 of each liquid restorative material
It was cured in the same manner as above, and the depth of toothbrush wear was examined. The results are shown in Table 5.
【表】
実施例 19
実施例３で合成した弗素系モノマーとbisGMA
ならびに希釈用モノマーであるTEGMAを表６に
示すような割合で混合し、その混合物の粘度を測
定した。その結果を表６に示す。[Table] Example 19 Fluorine-based monomer synthesized in Example 3 and bisGMA
In addition, TEGMA, which is a diluting monomer, was mixed in the proportions shown in Table 6, and the viscosity of the mixture was measured. The results are shown in Table 6.
【表】【table】
Claims (1)
【式】【式】R′2 はCH2、【式】【式】又は 【式】R3は 【式】又は 【式】であり、Ｙは【式】ｌは０又は １、ｎは０又は１である。）で示される含弗素不
飽和カルボン酸エステル。 ２ 一般式CF3CF2COX（但しＸはハロゲン原子
である）又は
【式】（但しｎ は０又は１、Ｘはハロゲン原子である）で示され
るパーフルオロカルボン酸ハライドと、一般式 （但しR1はＨ又はCH3、R2はCH2、
【式】又は【式】 R′2はCH2、【式】【式】又は 【式】であり、Ｙは 【式】ｌは０又は１、ｎは０又は１である） で示される不飽和カルボン酸エステルとを反応さ
せることを特徴とする含弗素不飽和カルボン酸エ
ステルの製法。 ３ 有機溶媒中、３級アミンの存在下で 【式】と一般式 （但しR1はＨ又はCH3、R2はCH2、
【式】【式】R′2 はCH2、【式】【式】又は 【式】Ｙは【式】ｌは０ 又は１）で示される不飽和カルボン酸エステルと
を反応させることを特徴とする含弗素不飽和カル
ボン酸エステルの製法。 ４ 一般式 （但しR1はＨ又はCH3、R2はCH2、【式】又 は【式】R′2はCH2、 【式】【式】又は 【式】であり、R3は 【式】又は 【式】であり、Ｙは【式】ｌは０又は １、ｎは０又は１である。）で示される含弗素不
飽和カルボン酸エステルを少なくとも１成分とす
る歯科用充填剤組成物。[Claims] 1. General formula (However, R 1 is H or CH 3 , R 2 is CH 2 ,
[Formula] [Formula] R′ 2 is CH 2 , [Formula] [Formula] or [Formula] R 3 is [Formula] or [Formula], Y is [Formula] l is 0 or 1, n is 0 Or 1. ) A fluorine-containing unsaturated carboxylic acid ester. 2. A perfluorocarboxylic acid halide represented by the general formula CF 3 CF 2 COX (where X is a halogen atom) or [Formula] (where n is 0 or 1 and X is a halogen atom) and a general formula (However, R 1 is H or CH 3 , R 2 is CH 2 ,
[Formula] or [Formula] R′ 2 is CH 2 , [Formula] [Formula] or [Formula], Y is [Formula] l is 0 or 1, n is 0 or 1) A method for producing a fluorine-containing unsaturated carboxylic acid ester, which comprises reacting a fluorine-containing unsaturated carboxylic acid ester with a saturated carboxylic acid ester. 3 In an organic solvent, in the presence of a tertiary amine, [formula] and general formula (However, R 1 is H or CH 3 , R 2 is CH 2 ,
[Formula] [Formula] R′ 2 is CH 2 , [Formula] [Formula] or [Formula] Y is [Formula] l is 0 or 1 A method for producing a fluorine-containing unsaturated carboxylic acid ester. 4 General formula (However, R 1 is H or CH 3 , R 2 is CH 2 , [Formula] or [Formula] R′ 2 is CH 2 , [Formula] [Formula] or [Formula], R 3 is [Formula] or A dental filling composition comprising at least one component of a fluorine-containing unsaturated carboxylic acid ester represented by the following formula: where Y is [formula] l is 0 or 1 and n is 0 or 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56205100A JPS58105943A (en) | 1981-12-21 | 1981-12-21 | Fluoride-containing unsaturated carboxylic acid ester and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56205100A JPS58105943A (en) | 1981-12-21 | 1981-12-21 | Fluoride-containing unsaturated carboxylic acid ester and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58105943A JPS58105943A (en) | 1983-06-24 |
| JPS6221341B2 true JPS6221341B2 (en) | 1987-05-12 |
Family
ID=16501411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56205100A Granted JPS58105943A (en) | 1981-12-21 | 1981-12-21 | Fluoride-containing unsaturated carboxylic acid ester and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58105943A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011409A (en) * | 1983-06-30 | 1985-01-21 | Mitsubishi Rayon Co Ltd | Dental material |
| JPS62153257A (en) * | 1985-12-26 | 1987-07-08 | Tokuyama Soda Co Ltd | Production of perfluoromonoester carboxylic acid chloride |
| JPH01182306A (en) * | 1988-01-12 | 1989-07-20 | Asahi Glass Co Ltd | Active energy ray curing composition |
| CN102060702B (en) * | 2010-10-28 | 2013-12-25 | 华南理工大学 | Visible light curing fluorine-containing dental resin monomer/composite material and preparation method thereof |
| JP6423002B2 (en) * | 2014-12-12 | 2018-11-14 | 富士フイルム株式会社 | Polymer, composition, optical film, and liquid crystal display device |
-
1981
- 1981-12-21 JP JP56205100A patent/JPS58105943A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58105943A (en) | 1983-06-24 |
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