JP6441132B2 - Dental photopolymerizable composition - Google Patents
Dental photopolymerizable composition Download PDFInfo
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- JP6441132B2 JP6441132B2 JP2015049991A JP2015049991A JP6441132B2 JP 6441132 B2 JP6441132 B2 JP 6441132B2 JP 2015049991 A JP2015049991 A JP 2015049991A JP 2015049991 A JP2015049991 A JP 2015049991A JP 6441132 B2 JP6441132 B2 JP 6441132B2
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- JP
- Japan
- Prior art keywords
- photopolymerizable composition
- compound
- group
- dental
- dental photopolymerizable
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 86
- -1 amine compound Chemical class 0.000 claims description 118
- 239000000178 monomer Substances 0.000 claims description 60
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000945 filler Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 claims description 7
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 5
- 239000011350 dental composite resin Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 description 33
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
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- 238000005452 bending Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
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- 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 4
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- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
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- 208000002925 dental caries Diseases 0.000 description 4
- 239000003479 dental cement Substances 0.000 description 4
- 239000005548 dental material Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 4
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 3
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 3
- 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007824 aliphatic compounds Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
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- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 2
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 2
- CGGPPTKPILLONI-UHFFFAOYSA-N (4-methyl-4-propan-2-ylcyclohexa-1,5-dien-1-yl)-phenyliodanium Chemical compound C1=CC(C(C)C)(C)CC=C1[I+]C1=CC=CC=C1 CGGPPTKPILLONI-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical group CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 2
- WJKHYAJKIXYSHS-UHFFFAOYSA-N 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(Cl)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 WJKHYAJKIXYSHS-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 2
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 150000001634 bornane-2,3-dione derivatives Chemical class 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
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- ISGXOWLMGOPVPB-UHFFFAOYSA-N n,n-dibenzylaniline Chemical compound C=1C=CC=CC=1CN(C=1C=CC=CC=1)CC1=CC=CC=C1 ISGXOWLMGOPVPB-UHFFFAOYSA-N 0.000 description 2
- HKJNHYJTVPWVGV-UHFFFAOYSA-N n,n-diethyl-4-methylaniline Chemical compound CCN(CC)C1=CC=C(C)C=C1 HKJNHYJTVPWVGV-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 2
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- BOEOXRHGXOIKKE-UHFFFAOYSA-N (3-methyl-5-phenylhept-4-en-3-yl)benzene Chemical compound C=1C=CC=CC=1C(CC)=CC(C)(CC)C1=CC=CC=C1 BOEOXRHGXOIKKE-UHFFFAOYSA-N 0.000 description 1
- ISZVHXPSMYZEJC-UHFFFAOYSA-N (3-methyl-5-phenylhept-5-en-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)CC(=CC)C1=CC=CC=C1 ISZVHXPSMYZEJC-UHFFFAOYSA-N 0.000 description 1
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- JZDQKBZKFIWSNW-UHFFFAOYSA-N (4-methoxyphenyl)-phenyliodanium Chemical compound C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 JZDQKBZKFIWSNW-UHFFFAOYSA-N 0.000 description 1
- MHMPFHGJSJOKIV-UHFFFAOYSA-N (4-phenoxyphenyl)-phenyliodanium Chemical compound C=1C=C([I+]C=2C=CC=CC=2)C=CC=1OC1=CC=CC=C1 MHMPFHGJSJOKIV-UHFFFAOYSA-N 0.000 description 1
- RGXLDQDGZYZGEE-UHFFFAOYSA-N (4-tert-butylphenyl)-phenyliodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=CC=C1 RGXLDQDGZYZGEE-UHFFFAOYSA-N 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
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- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
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- MFGSQXUNSUJWPZ-UHFFFAOYSA-N 1,7,7-trimethyl-2,3-dioxobicyclo[2.2.1]heptane-4-carboxylic acid Chemical compound C1CC2(C(O)=O)C(=O)C(=O)C1(C)C2(C)C MFGSQXUNSUJWPZ-UHFFFAOYSA-N 0.000 description 1
- QUDNWFSGYBTWLF-UHFFFAOYSA-N 1,7,7-trimethyl-2,3-dioxobicyclo[2.2.1]heptane-4-sulfonic acid Chemical compound C1CC2(S(O)(=O)=O)C(=O)C(=O)C1(C)C2(C)C QUDNWFSGYBTWLF-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QZKVUSSYPPWURQ-UHFFFAOYSA-N 1-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C QZKVUSSYPPWURQ-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- URJAUSYMVIZTHC-UHFFFAOYSA-N 2,4,6-tris(tribromomethyl)-1,3,5-triazine Chemical compound BrC(Br)(Br)C1=NC(C(Br)(Br)Br)=NC(C(Br)(Br)Br)=N1 URJAUSYMVIZTHC-UHFFFAOYSA-N 0.000 description 1
- JJPKWNXRUDKBQT-UHFFFAOYSA-N 2,4-bis(trichloromethyl)-6-[2-(3,4,5-trimethoxyphenyl)ethenyl]-1,3,5-triazine Chemical compound COC1=C(OC)C(OC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 JJPKWNXRUDKBQT-UHFFFAOYSA-N 0.000 description 1
- DQMOHZLFVGYNAN-UHFFFAOYSA-N 2-(2-phenylethenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2C=CC=CC=2)=N1 DQMOHZLFVGYNAN-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、歯科治療に用いられる歯科用光重合性組成物に関し、特に、大きな窩洞に対して好適に用いることができる歯科用光重合性組成物に関する。 The present invention relates to a dental photopolymerizable composition used for dental treatment, and particularly to a dental photopolymerizable composition that can be suitably used for a large cavity.
齲蝕等により欠損を生じた歯質の修復において、充填用コンポジットレジンと呼ばれる、主に（メタ）アクリレート系のラジカル重合性単量体と金属酸化物等の無機フィラーとを主成分とする修復材料のペーストを欠損部に充填、歯牙の形状を付与した後に重合、硬化させる手法が主流である。欠損部では、ペースト充填前に、齲蝕等の病巣部を取り除くため、欠損部周部を削り出し、窩洞を形成する処置が行われる。 In restoration of dental material that has been damaged due to caries, etc., a restoration material mainly composed of a (meth) acrylate radical polymerizable monomer and an inorganic filler such as a metal oxide, called a composite resin for filling. The mainstream is a method of filling the defective portion with a paste and polymerizing and curing the tooth shape. In the defect portion, before filling the paste, in order to remove a lesion portion such as a caries, a treatment for cutting out the periphery of the defect portion and forming a cavity is performed.
歯科分野における重合方法としては、光重合と化学重合とに大別される。前記ラジカル重合性単量体と光重合開始剤とを用いた光重合型の修復材料は、光を遮断しておけば重合反応が進むことはほとんどないため、全ての成分を１ペーストの状態で製造、保管しておくことができ、化学重合型の修復材料を用いる場合に必要な使用時における混合・練和作業が必要なく、また、可使時間が長いなどの利点を有する。そのため、近年では、光重合型の歯科用修復材料が主流である。以下では、このような光重合型の修復材料を歯科用光重合性組成物と呼ぶ。 Polymerization methods in the dental field are roughly classified into photopolymerization and chemical polymerization. Since the photopolymerization type repair material using the radical polymerizable monomer and the photopolymerization initiator hardly undergoes the polymerization reaction if the light is blocked, all the components are in one paste state. It can be manufactured and stored, and there are advantages such as no need for mixing and kneading work at the time of use, which is necessary when using a chemical polymerization type restoration material, and a long pot life. Therefore, in recent years, photopolymerization type dental restoration materials have become mainstream. Hereinafter, such a photopolymerization type restorative material is referred to as a dental photopolymerizable composition.
歯科治療分野においては、生体への為害性のため紫外線領域に活性を有する光重合開始剤の使用が困難であることから、可視光領域の光（活性光）に活性を有する光重合開始剤が使用される。このような光重合開始剤としては、光を吸収しそれ自身が分解して重合活性種を生成するα−ジケトン化合物が広く用いられている。
前記歯科用光重合性組成物は、患者の口腔内に充填した後、光照射を行って重合、硬化される。そのため、重合のための光（活性光）の照射時間を長く取ると、操作に時間がかかるだけではなく、患者にも多大な負担を強いるという問題があり、光照射時間の短縮が要望されている。また、光照射後の前記歯科用光重合性組成物の重合硬化体の機械的強度が低いと、割れや欠けといった欠損に加え、摩耗により治療時の形状が損なわれる問題が生じる。
In the field of dental treatment, it is difficult to use a photopolymerization initiator having activity in the ultraviolet region because of its harmfulness to the living body. Therefore, a photopolymerization initiator having activity in light (active light) in the visible light region is used. used. As such a photopolymerization initiator, α-diketone compounds that absorb light and decompose themselves to generate polymerization active species are widely used.
The dental photopolymerizable composition is polymerized and cured by filling with light in the patient's oral cavity. Therefore, if the irradiation time of the light for polymerization (active light) is made long, there is a problem that not only the operation takes time but also a heavy burden is imposed on the patient, and there is a demand for shortening the light irradiation time. Yes. Moreover, when the mechanical strength of the cured polymer of the dental photopolymerizable composition after light irradiation is low, there arises a problem that the shape at the time of treatment is impaired due to wear in addition to defects such as cracks and chips.
こうしたことから、前記α−ジケトン化合物に対して、増感剤としてのアミン化合物を組み合わせることで重合時間を短縮化させるものや、トリアジン化合物やヨードニウム塩等の光酸発生剤を組み合わせることで機械的強度を付与するものが提案されている（例えば、特許文献１、２参照）。これらの中でも、前記α−ジケトン化合物に対して、前記アミン化合物とトリアジン化合物とを組み合わせた高速重合系の光重合開始剤組成を用いると、前記ラジカル重合性単量体の重合時間を短縮させるとともに、その重合硬化体に優れた機械的強度を付与することができる（特許文献１参照）。 For these reasons, the α-diketone compound is mechanically combined with a photoacid generator such as a triazine compound or an iodonium salt that shortens the polymerization time by combining an amine compound as a sensitizer. The thing which provides intensity | strength is proposed (for example, refer patent document 1, 2). Among these, when using a photopolymerization initiator composition of a high-speed polymerization system in which the amine compound and the triazine compound are combined with the α-diketone compound, the polymerization time of the radical polymerizable monomer is shortened. The polymer cured product can be provided with excellent mechanical strength (see Patent Document 1).
しかしながら、前記ラジカル重合性単量体は、重合時に収縮するため収縮時の応力（収縮応力）が前記窩洞と前記重合硬化体との界面に集中することがあり、前記高速重合系の光重合開始剤組成を用いると、重合反応による急激な収縮応力が前記界面に働くことで、前記窩洞と前記重合硬化体との間にギャップ（隙間）が生じ易くなる。この問題は、大きな窩洞に前記歯科用光重合性組成物を一度に充填して重合を行う場合に特に顕在化し易く、前記ギャップが生じると、前記重合硬化体の前記窩洞からの脱落や２次齲蝕の原因となる。 However, since the radical polymerizable monomer contracts during polymerization, stress during contraction (contraction stress) may concentrate on the interface between the cavity and the polymerized cured body, and photopolymerization of the high-speed polymerization system starts. When an agent composition is used, a rapid contraction stress due to a polymerization reaction acts on the interface, so that a gap (gap) is easily generated between the cavity and the polymerized cured body. This problem is particularly obvious when polymerization is performed by filling the dental cavity with the dental photopolymerizable composition at one time. When the gap occurs, the polymerized cured product may fall off from the cavity, or may be secondary. Causes caries.
ところで、患者の口腔内を検査するデンタルライトや治療室内の室内灯等の環境光に基づく意図しない重合を防ぐため、重合コントロール成分として重合禁止剤が配合されることがある。
しかしながら、前記環境光に対する安定性を得るために前記重合禁止剤の配合量を増やしていくと、前記窩洞内の深い位置における重合が不十分となることがある。
そのため、大きな窩洞に対しては、窩洞深部で比較的高い硬化性が得られる重合コントロール成分として、α−メチルスチレン二量体のようなα−アルキルスチレン化合物を配合する歯科用光重合性組成物が提案されている（特許文献３）。
By the way, a polymerization inhibitor may be blended as a polymerization control component in order to prevent unintentional polymerization based on environmental light such as dental light for examining the oral cavity of a patient or indoor light in a treatment room.
However, if the blending amount of the polymerization inhibitor is increased in order to obtain stability against the ambient light, polymerization at a deep position in the cavity may be insufficient.
Therefore, for large cavities, a dental photopolymerizable composition containing an α-alkylstyrene compound such as α-methylstyrene dimer as a polymerization control component capable of obtaining relatively high curability in the deep cavity. Has been proposed (Patent Document 3).
しかしながら、前記α−アルキルスチレン化合物を配合する歯科用光重合性組成物では、深い硬化深度が得られるものの、前記高速重合系の光重合開始剤組成を配合したときの前記ギャップに対する影響や、得られる重合硬化体の強度については未知であり、むしろ前記α−アルキルスチレン化合物が重合コントロール成分としてポリマーの重合度（平均分子量）の調節に用いられる添加剤であることから、前記高速重合系の光重合開始剤組成を用いる場合には、単にそのメリットが失われ、硬化体の強度不足に陥ることが懸念される。
したがって、窩洞適合性として、大きな窩洞に対しても前記窩洞と前記重合硬化体との間にギャップが生じにくく、また、優れた機械的強度を有する重合硬化体を得ることが可能な歯科用光重合性組成物としては、何ら存在しないのが現状である。
However, in the dental photopolymerizable composition containing the α-alkylstyrene compound, although a deep depth of cure is obtained, the effect on the gap when the photopolymerization initiator composition of the high-speed polymerization system is added, and The strength of the polymerized cured product is unknown. Rather, the α-alkylstyrene compound is an additive used to control the degree of polymerization (average molecular weight) of the polymer as a polymerization control component. When the polymerization initiator composition is used, there is a concern that the merit is simply lost and the strength of the cured product is insufficient.
Therefore, as a cavity compatibility, a dental light capable of obtaining a polymerized cured body having an excellent mechanical strength, with a gap between the cavity and the polymerized cured body hardly generated even for a large cavity. The present condition is that there is no polymerizable composition.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、大きな窩洞に対しても優れた窩洞適合性及び機械的強度を兼備する重合硬化体を得ることが可能な歯科用光重合性組成物を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a dental photopolymerizable composition capable of obtaining a polymerized cured body having excellent cavity compatibility and mechanical strength even for a large cavity.
大きな窩洞に対しても優れた窩洞適合性及び機械的強度を兼備するものが存在しない現状から、本発明者らは、試行錯誤を繰返しつつ検討を進めていた。
こうした検討の中、歯科用光重合性組成物に対して、単にα−アルキルスチレン化合物を配合しても、予め懸念されていた通り、機械的強度が得られない結果が得られたものの、更に検討を進めるうち、前記α−ジケトン化合物、前記アミン化合物及び前記光酸発生剤の組み合わせによる系では、予想に反し、優れた窩洞適合性及び機械的強度を兼備する前記重合硬化体が得られることの知見を得た。
The present inventors have been proceeding with examinations through repeated trial and error from the current situation that there is no excellent cavity compatibility and mechanical strength even for a large cavity.
In such examination, even if the α-alkylstyrene compound was simply added to the dental photopolymerizable composition, the mechanical strength could not be obtained as previously feared. While proceeding with the study, in the system based on the combination of the α-diketone compound, the amine compound and the photoacid generator, the polymer cured product having excellent cavity compatibility and mechanical strength is obtained contrary to expectations. I got the knowledge.
本発明は、前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ （Ａ）ラジカル重合性単量体と、（Ｂ）α−ジケトン化合物と、（Ｃ）アミン化合物と、（Ｄ）光酸発生剤と、（Ｅ）α−アルキルスチレン化合物と、を含んでなる歯科用光重合性組成物であって、前記（Ａ）ラジカル重合性単量体１００質量部に対する前記（Ｅ）α−アルキルスチレン化合物の配合量が０．１質量部〜０．５質量部であり、直径６ｍｍ、深さ２ｍｍの模擬窩洞の内部に前記歯科用光重合性組成物を充填した後に、前記模擬窩洞の上方から光照射して前記歯科用光重合性組成物を重合硬化させたとき、前記歯科用光重合性組成物の前記重合硬化によって生じる重合収縮応力が最大値に至るまでの時間である最大応力到達時間が４８秒以上である、ことを特徴とする歯科用光重合性組成物。
＜２＞ （Ｅ）α−アルキルスチレン化合物が、α−メチルスチレンダイマーである前記＜１＞に記載の歯科用光重合性組成物。
＜３＞ （Ｄ）光酸発生剤が、トリハロメチル基により置換されたｓ−トリアジン化合物及びジアリールヨードニウム塩化合物の少なくともいずれかである前記＜１＞から＜２＞のいずれかに記載の歯科用光重合性組成物。
＜４＞ （Ｃ）アミン化合物が、脂肪族第３級アミン化合物と芳香族第３級アミン化合物とを含有する前記＜１＞から＜３＞のいずれかに記載の歯科用光重合性組成物。
＜５＞ 更に、（Ｆ）充填材を含む前記＜１＞から＜４＞のいずれかに記載の歯科用光重合性組成物。
＜６＞ ３ｍｍ〜６ｍｍの深さを有する窩洞を充填修復する歯科用コンポジットレジンとして用いられる前記＜１＞から＜５＞のいずれかに記載の歯科用光重合性組成物。
The present invention is based on the above knowledge, and means for solving the above problems are as follows. That is,
<1> (A) a radically polymerizable monomer, (B) an α-diketone compound, (C) an amine compound, (D) a photoacid generator, and (E) an α-alkylstyrene compound. a dental photopolymerizable composition comprising Nde containing, (a) the amount of the relative radical-polymerizable monomer 100 parts by (E) alpha-alkylstyrene compound 0.1 part by mass to 0.5 After filling the dental photopolymerizable composition into a simulated cavity having a diameter of 6 mm and a depth of 2 mm, the dental photopolymerizable composition is polymerized by irradiating light from above the simulated cavity. When cured, the dental photopolymerizable composition has a maximum stress arrival time which is a time until the polymerization shrinkage stress generated by the polymerization and curing reaches a maximum value of 48 seconds or more . Photopolymerizable composition.
<2> The dental photopolymerizable composition according to <1>, wherein the (E) α-alkylstyrene compound is an α-methylstyrene dimer .
< 3 > (D) The dental agent according to any one of <1> to < 2 >, wherein the photoacid generator is at least one of an s-triazine compound substituted with a trihalomethyl group and a diaryliodonium salt compound. Photopolymerizable composition.
< 4 > (C) The dental photopolymerizable composition according to any one of <1> to < 3 >, wherein the amine compound contains an aliphatic tertiary amine compound and an aromatic tertiary amine compound. .
< 5 > The dental photopolymerizable composition according to any one of <1> to < 4 >, further comprising (F) a filler.
< 6 > The dental photopolymerizable composition according to any one of <1> to < 5 >, which is used as a dental composite resin for filling and repairing a cavity having a depth of 3 mm to 6 mm.
本発明によれば、従来技術における前記諸問題を解決することができ、大きな窩洞に対しても優れた窩洞適合性及び機械的強度を兼備する重合硬化体を得ることが可能な歯科用光重合性組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the dental photopolymerization which can solve the said various problems in a prior art, and can obtain the polymeric hardening body which has the outstanding cavity compatibility and mechanical strength also with respect to a large cavity. Sex compositions can be provided.
（歯科用光重合性組成物）
本発明の歯科用光重合性組成物は、少なくとも（Ａ）ラジカル重合性単量体と、（Ｂ）α−ジケトン化合物と、（Ｃ）アミン化合物と、（Ｄ）光酸発生剤と、（Ｅ）α−アルキルスチレン化合物と、を含み、必要に応じて、その他の成分を含む。
(Dental photopolymerizable composition)
The dental photopolymerizable composition of the present invention comprises at least (A) a radical polymerizable monomer, (B) an α-diketone compound, (C) an amine compound, (D) a photoacid generator, E) an α-alkylstyrene compound, and optionally other components.
＜（Ａ）ラジカル重合性単量体＞
前記（Ａ）ラジカル重合性単量体は、（Ｂ）α−ジケトン化合物、（Ｃ）アミン化合物、及び（Ｄ）光酸発生剤を重合開始成分として光の照射により重合硬化する成分である。
前記（Ａ）ラジカル重合性単量体としては、特に制限はなく、目的に応じて適宜選択されるが、酸性基（スルホン酸基、カルボキシル基、リン酸残基等）を有さない（メタ）アクリレート系の重合性単量体が、硬化速度や硬化体の機械的物性、耐水性、耐着色性等の観点から好適に用いられ、特に、複数の重合性官能基を有する、多官能の（メタ）アクリレート系重合性単量体が好ましい。
前記多官能の（メタ）アクリレート系重合性単量体としては、特に制限はなく、目的に応じて適宜選択されるが、水に対する溶解度が５質量％以下の非水溶性化合物が好ましい。
前記非水溶性化合物としては、例えば、以下に詳述する、下記（Ｉ）二官能重合性単量体、（ＩＩ）三官能重合性単量体、（ＩＩＩ）四官能重合性単量体が挙げられる。
<(A) Radical polymerizable monomer>
The (A) radical polymerizable monomer is a component that is polymerized and cured by light irradiation using (B) an α-diketone compound, (C) an amine compound, and (D) a photoacid generator as a polymerization initiation component.
The (A) radical polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but does not have an acidic group (such as a sulfonic acid group, a carboxyl group, or a phosphoric acid residue) (meta ) An acrylate-based polymerizable monomer is preferably used from the viewpoints of curing speed, mechanical properties of the cured product, water resistance, color resistance, and the like. In particular, a polyfunctional monomer having a plurality of polymerizable functional groups. A (meth) acrylate polymerizable monomer is preferred.
There is no restriction | limiting in particular as said polyfunctional (meth) acrylate type | system | group polymerizable monomer, Although it selects suitably according to the objective, The water-insoluble compound whose solubility with respect to water is 5 mass% or less is preferable.
Examples of the water-insoluble compound include the following (I) bifunctional polymerizable monomer, (II) trifunctional polymerizable monomer, and (III) tetrafunctional polymerizable monomer described in detail below. Can be mentioned.
（Ｉ）二官能重合性単量体
前記（Ｉ）二官能重合性単量体としては、（ｉ）芳香族化合物系のものと、（ｉｉ）脂肪族化合物系のものが挙げられる。
(I) Bifunctional polymerizable monomer Examples of the (I) bifunctional polymerizable monomer include (i) aromatic compound-based monomers and (ii) aliphatic compound-based monomers.
（ｉ）芳香族化合物系のもの
前記（ｉ）芳香族化合物系のものとしては、例えば、２，２−ビス（メタクリロイルオキシフェニル）プロパン、２，２−ビス［４−（３−メタクリロイルオキシ）−２−ヒドロキシプロポキシフェニル］プロパン（「ｂｉｓ−ＧＭＡ」）、２，２−ビス（４−メタクリロイルオキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン（「Ｄ−２．６Ｅ」）、２，２−ビス（４−メタクリロイルオキシジエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシテトラエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシペンタエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシジプロポキシフェニル）プロパン、２（４−メタクリロイルオキシジエトキシフェニル）−２（４−メタクリロイルオキシトリエトキシフェニル）プロパン、２（４−メタクリロイルオキシジプロポキシフェニル）−２−（４−メタクリロイルオキシトリエトキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシプロポキシフェニル）プロパン、２，２−ビス（４−メタクリロイルオキシイソプロポキシフェニル）プロパン及びこれらのメタクリレートに対応するアクリレート；２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート等のメタクリレート又はこれらメタクリレートに対応するアクリレート等の水酸基を有するビニルモノマーと、ジイソシアネートメチルベンゼン、４，４’−ジフェニルメタンジイソシアネート等の芳香族基を有するジイソシアネート化合物との付加体から得られるジアダクトなどが挙げられる。
(I) Aromatic compound type As the above (i) aromatic compound type, for example, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane ("bis-GMA"), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane ("D-2 .6E "), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) ) Propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) pro Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having a hydroxyl group such as acrylate corresponding to these methacrylates, and diisocyanate methylbenzene Emissions, etc. diadduct obtained from adducts of a diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate.
（ｉｉ）脂肪族化合物系のもの
前記（ｉｉ）脂肪族化合物系のものとしては、例えば、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート（「３Ｇ」）、テトラエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート及びこれらのメタクリレートに対応するアクリレート；２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート等のメタクリレート又はこれらのメタクリレートに対応するアクリレート等の水酸基を有するビニルモノマーと、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）等のジイソシアネート化合物との付加体から得られるジアダクト；１，２−ビス（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）エチルなどが挙げられる。
(Ii) Aliphatic compound-based (ii) Aliphatic compound-based compounds include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (“3G”), tetraethylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxy Vinylates having hydroxyl groups such as methacrylates such as propyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates 1,2-bis (3-methacryloyloxy), a diadduct obtained from an adduct of a monomer and a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 2-hydroxypropoxy) ethyl and the like.
（ＩＩ）三官能重合性単量体
前記（ＩＩ）三官能重合性単量体としては、例えば、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールメタントリメタクリレート等のメタクリレート及びこれらメタクリレートに対応するアクリレートなどが挙げられる。
(II) Trifunctional polymerizable monomer Examples of the (II) trifunctional polymerizable monomer include trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate. Examples thereof include methacrylates and acrylates corresponding to these methacrylates.
（ＩＩＩ）四官能重合性単量体
前記（ＩＩＩ）四官能重合性単量体としては、例えば、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールテトラアクリレート；ジイソシアネートメチルベンゼン、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）、４，４−ジフェニルメタンジイソシアネート、トリレン−２，４−ジイソシアネート等のジイソシアネート化合物とグリシドールジメタクリレートとの付加体から得られるジアダクトなどが挙げられる。
(III) Tetrafunctional polymerizable monomer Examples of the (III) tetrafunctional polymerizable monomer include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene. Examples thereof include a diadduct obtained from an adduct of a diisocyanate compound such as diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate and glycidol dimethacrylate.
前記多官能の（メタ）アクリレート系重合性単量体としては、１種単独で用いてもよく２種以上を併用してもよい。
更に、必要に応じて、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ヒドロキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、グリシジルメタクリレート等のメタクリレート及びこれらメタクリレートに対応するアクリレート等の単官能の（メタ）アクリレート系単量体と併用してもよい。
前記歯科用光重合性組成物では、良好な硬化体物性（機械的強度、非溶出性など）を得る観点から、前記多官能の（メタ）アクリレート系単量体以外の単量体の配合量が、前記（Ａ）ラジカル重合性単量体の全量中、３０質量％以下であることが好ましく、１０質量％以下がより好ましく、５質量％以下が特に好ましい。
As the polyfunctional (meth) acrylate polymerizable monomer, one kind may be used alone, or two or more kinds may be used in combination.
Furthermore, if necessary, for example, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. You may use together with a mer.
In the dental photopolymerizable composition, from the viewpoint of obtaining good cured product properties (mechanical strength, non-eluting property, etc.), the amount of monomers other than the polyfunctional (meth) acrylate monomer However, the total amount of the (A) radical polymerizable monomer is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
＜（Ｂ）α−ジケトン化合物＞
前記α−ジケトン化合物は、前記（Ａ）ラジカル重合性単量体の重合開始成分として配合される。
前記α−ジケトン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、カンファーキノン、カンファーキノンカルボン酸、カンファーキノンスルホン酸等のカンファーキノン類；ジアセチル、アセチルベンゾイル、２，３−ペンタジオン、２，３−オクタジオン、９，１０−フェナンスレンキノン、アセナフテンキノンなどを挙げることができる。これらの中でも、可視光領域に極大吸収波長を有する前記カンファーキノン類が好ましく、前記カンファーキノンが特に好ましい。
なお、これらは１種単独で用いてもよく２種以上を併用してもよい。
<(B) α-diketone compound>
The α-diketone compound is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said alpha-diketone compound, According to the objective, it can select suitably, For example, camphor quinones, such as camphor quinone, camphor quinone carboxylic acid, camphor quinone sulfonic acid; diacetyl, acetyl benzoyl, 2 , 3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, acenaphthenequinone, and the like. Among these, the camphorquinones having a maximum absorption wavelength in the visible light region are preferable, and the camphorquinone is particularly preferable.
In addition, these may be used individually by 1 type and may use 2 or more types together.
前記α−ジケトン化合物の配合量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記（Ａ）ラジカル重合性単量体１００質量部に対して、０．０１質量部〜１０質量部が好ましく、０．０３質量部〜５質量部がより好ましい。
前記配合量が０．０１質量部未満であると、前記（Ａ）ラジカル重合性単量体の重合が不十分となり、１０質量部を超えると環境光安定性が低下することがある。
The blending amount of the α-diketone compound is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.01 parts by mass with respect to 100 parts by mass of the (A) radical polymerizable monomer. 10 mass parts is preferable, and 0.03 mass parts to 5 mass parts is more preferable.
When the blending amount is less than 0.01 parts by mass, the polymerization of the radically polymerizable monomer (A) becomes insufficient, and when it exceeds 10 parts by mass, the ambient light stability may be lowered.
＜（Ｃ）アミン化合物＞
前記（Ｃ）アミン化合物は、前記（Ａ）ラジカル重合性単量体の重合開始成分として配合される。
前記（Ｃ）アミン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、第１級アミン化合物、第２級アミン化合物及び第３級アミン化合物のいずれも用いることができるが、これらの中でも、臭気等の観点から前記第３級アミン化合物が好ましい。
また、前記（Ｃ）アミン化合物としては、特に制限はなく、窒素原子に１つ以上の芳香族基が直接結合したアミン化合物（以下、「芳香族アミン化合物」とも呼ぶ）、窒素原子に結合している有機基が、全て脂肪族基（但し、置換基を有していてもよい）である化合物（以下、「脂肪族アミン化合物」とも呼ぶ）のいずれも用いることができる。
<(C) Amine compound>
The (C) amine compound is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said (C) amine compound, Although it can select suitably according to the objective, Any of a primary amine compound, a secondary amine compound, and a tertiary amine compound can be used. Among these, the tertiary amine compound is preferable from the viewpoint of odor and the like.
The amine compound (C) is not particularly limited, and is an amine compound in which one or more aromatic groups are directly bonded to the nitrogen atom (hereinafter also referred to as “aromatic amine compound”), or bonded to the nitrogen atom. Any compound (hereinafter also referred to as “aliphatic amine compound”) in which all organic groups are aliphatic groups (however, they may have a substituent) can be used.
前記芳香族アミン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アニリン、トルイジン等の芳香族第１級アミン化合物；Ｎ−メチルアニリン、Ｎ−メチル−ｐ−トルイジン等の芳香族第２級アミン化合物；Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジベンジルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジエチル−ｐ−トルイジン、Ｎ，Ｎ−ジ（β−ヒドロキシエチル）−ｐ−トルイジン、ｐ−ジメチルアミノ安息香酸、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸アミル等の第３級アミン化合物を挙げることができる。これらの中でも、歯科用として使用することを考慮すると、臭気等の点から前記第３級芳香族アミン化合物が好ましく、更に、高い重合活性を示し、環境光に対する安定性と照射光による短時間での重合硬化性を維持し、かつ、高い硬化体物性を発現させることが可能な点で、下記一般式（１）で表される芳香族第３級アミン化合物が特に好ましい。 There is no restriction | limiting in particular as said aromatic amine compound, According to the objective, it can select suitably, For example, aromatic primary amine compounds, such as aniline and toluidine; N-methylaniline, N-methyl-p- Aromatic secondary amine compounds such as toluidine; N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N- There may be mentioned tertiary amine compounds such as di (β-hydroxyethyl) -p-toluidine, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate and amyl p-dimethylaminobenzoate. Among these, the tertiary aromatic amine compound is preferable from the viewpoint of odor, etc. in consideration of use as a dental product, and further exhibits high polymerization activity, stability to ambient light, and a short time due to irradiation light. The aromatic tertiary amine compound represented by the following general formula (1) is particularly preferable in that it can maintain the polymerization curability of the polymer and can exhibit high cured product properties.
前記一般式（１）中、Ｒ１〜Ｒ３で示されるアルキル基としては、炭素数１〜６のものが好ましく、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｎ−ヘキシル基などを挙げることができる。また、これらアルキル基としては、置換基を有している置換アルキル基であってもよく、このような置換アルキル基としては、フロロメチル基、２−フロロエチル基等のハロゲン置換アルキル基；２−ヒドロキシエチル基等の水酸基置換アルキル基などを挙げることができる。 In the general formula (1), the alkyl group represented by R 1 to R 3 is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -A butyl group, n-hexyl group, etc. can be mentioned. These alkyl groups may be substituted alkyl groups having a substituent. Examples of such substituted alkyl groups include halogen-substituted alkyl groups such as a fluoromethyl group and a 2-fluoroethyl group; 2-hydroxy Examples thereof include a hydroxyl group-substituted alkyl group such as an ethyl group.
前記一般式（１）中、Ｒ３で示されるアリール基、アルケニル基、アルコキシ基及びアルキルオキシカルボニル基としては、置換基を有するものであってよい。
前記アリール基としては、フェニル基、ｐ−メトキシフェニル基、ｐ−メチルチオフェニル基、ｐ−クロロフェニル基、４−ビフェニリル基等の炭素数６〜１２のものを挙げることができる。前記アルケニル基としては、ビニル基、アリル基、２−フェニルエテニル基等の炭素数２〜１２のものを挙げることができる。前記アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基等の炭素数１〜１０のものを挙げることができる。また、前記アルキルオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、アミルオキシカルボニル基、イソアミルオキシカルボニル基等のアルキルオキシ基部分の炭素数が１〜１０のものを挙げることができる。
In the general formula (1), the aryl group, alkenyl group, alkoxy group and alkyloxycarbonyl group represented by R 3 may have a substituent.
As said aryl group, C6-C12 things, such as a phenyl group, p-methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, can be mentioned. Examples of the alkenyl group include those having 2 to 12 carbon atoms such as vinyl group, allyl group, and 2-phenylethenyl group. As said alkoxy group, C1-C10 things, such as a methoxy group, an ethoxy group, a butoxy group, can be mentioned. Examples of the alkyloxycarbonyl group include those having 1 to 10 carbon atoms in the alkyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, and isoamyloxycarbonyl group. it can.
前記一般式（１）中、Ｒ１及びＲ２としては、炭素数１〜３の非置換のアルキル基（例えば、メチル基、エチル基、ｎ−プロピル基）、２−ヒドロキシエチル基が特に好ましい。
また、ｎ＝１の場合は、Ｒ３の結合位置がパラ位であることが好ましく、中でもＲ３がアルキルオキシカルボニル基であることが好ましい。一方、ｎが２〜３の場合には、結合位置は、オルト位及びパラ位の少なくともいずれかであることが好ましい。特に、複数のＲ３がオルト位及びパラ位に結合していることによって、硬化体の太陽光安定性を向上させることができる。
In the general formula (1), R 1 and R 2 are particularly preferably an unsubstituted alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group) or a 2-hydroxyethyl group. .
In addition, when n = 1, the bonding position of R 3 is preferably the para position, and it is particularly preferable that R 3 is an alkyloxycarbonyl group. On the other hand, when n is 2 to 3, the bonding position is preferably at least one of the ortho position and the para position. In particular, the solar stability of the cured product can be improved by bonding a plurality of R 3 to the ortho and para positions.
前記一般式（１）表される第３級芳香族アミン化合物を具体的に例示すると、Ｒ３がパラ位に結合したアルキルオキシカルボニル基である化合物として、ｐ−ジメチルアミノ安息香酸メチル、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸プロピル、ｐ−ジメチルアミノ安息香酸アミル、ｐ−ジメチルアミノ安息香酸イソアミル、ｐ−ジエチルアミノ安息香酸エチル、ｐ−ジエチルアミノ安息香酸プロピルなどが挙げられる。
また、この他の芳香族アミン化合物を具体的に例示すると、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジベンジルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジエチル−ｐ−トルイジン、Ｎ，Ｎ−ジ（β−ヒドロキシエチル）−ｐ−トルイジン、Ｎ，Ｎ，２，４，６−ペンタメチルアニリン、Ｎ，Ｎ，２，４−テトラメチルアニリン、Ｎ，Ｎ−ジエチル−２，４，６−トリメチルアニリンなどが挙げられる。
なお、前記芳香族アミン化合物としては、１種単独で用いてもよく２種以上を併用してもよい。
Specifically, the tertiary aromatic amine compound represented by the general formula (1) is specifically exemplified as a compound in which R 3 is an alkyloxycarbonyl group bonded to the para-position, methyl p-dimethylaminobenzoate, p- Examples include ethyl dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate, and the like.
Specific examples of the other aromatic amine compounds include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine. N, N-di (β-hydroxyethyl) -p-toluidine, N, N, 2,4,6-pentamethylaniline, N, N, 2,4-tetramethylaniline, N, N-diethyl-2 , 4,6-trimethylaniline and the like.
In addition, as said aromatic amine compound, it may be used individually by 1 type and may use 2 or more types together.
前記脂肪族アミン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、２−エチルヘキシルアミン、ｎ−ブチルアミン、ｎ−ヘキシルアミン、ｎ−オクチルアミン等の脂肪族第１級アミン化合物；ジエチルアミン、ジブチルアミン、ジアリルアミン、ジイソプロピルアミン、ジ−２−エチルヘキシルアミン、ジ−ｎ−オクチルアミン等の脂肪族第２級アミン化合物；トリエチルアミン、トリエタノールアミン、トリブチルアミン、トリアリルアミン、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート等の脂肪族第３級アミン化合物を挙げることができ、これらの中でも、窒素原子に結合している３つの飽和脂肪族基のうち、２つ以上が電子吸引性基を置換基として有している前記脂肪族第３級アミン化合物は、より高い重合活性を得ることができ、さらに優れた保存安定性を得ることができる。このような脂肪族第３級アミンとしては、例えば、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン等の電子吸引性基置換飽和脂肪族基数が２つのもの、及びトリエタノールアミン、トリ（イソプロパノール）アミン等の電子吸引性基置換飽和脂肪族基数が３つであるものが挙げられる。
なお、前記脂肪族アミン化合物としては、１種単独で用いてもよく２種以上を併用してもよい。
There is no restriction | limiting in particular as said aliphatic amine compound, According to the objective, it can select suitably, Aliphatic primary amines, such as 2-ethylhexylamine, n-butylamine, n-hexylamine, n-octylamine, etc. Compound: Aliphatic secondary amine compound such as diethylamine, dibutylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, di-n-octylamine; triethylamine, triethanolamine, tributylamine, triallylamine, N, N -Aliphatic tertiary amine compounds such as dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate, and among these, two of the three saturated aliphatic groups bonded to the nitrogen atom The above has an electron-withdrawing group as a substituent. The aliphatic tertiary amine compound can achieve a higher polymerization activity, it is possible to obtain a more excellent storage stability. Examples of such aliphatic tertiary amines include those having two electron-withdrawing group-substituted saturated aliphatic groups such as N-methyldiethanolamine and N-ethyldiethanolamine, and triethanolamine and tri (isopropanol) amine. In which the number of electron-withdrawing group-substituted saturated aliphatic groups is 3.
In addition, as said aliphatic amine compound, it may be used individually by 1 type and may use 2 or more types together.
これら（Ｃ）アミン化合物としては、いずれを用いてもよいが、前記芳香族アミン化合物と前記脂肪族アミン化合物とを含有することが好ましい。これらを併用すると、前記芳香族アミン化合物のみを配合した場合よりも、前記重合硬化体が太陽光等の紫外光に暴露されたときの変色を抑えることができ、また、前記脂肪族アミン化合物のみを配合した場合よりも、硬化速度を向上させることができる。
これらの中でも、前記一般式（１）で表される芳香族第３級アミン化合物と、前記ラジカル重合性官能基を有する脂肪族第３級アミン化合物との併用が特に好ましい。
Any of these (C) amine compounds may be used, but it is preferable to contain the aromatic amine compound and the aliphatic amine compound. When these are used in combination, it is possible to suppress discoloration when the polymerized cured product is exposed to ultraviolet light such as sunlight, compared to the case where only the aromatic amine compound is blended, and only the aliphatic amine compound. The curing rate can be improved as compared with the case of blending.
Among these, the combined use of the aromatic tertiary amine compound represented by the general formula (1) and the aliphatic tertiary amine compound having the radical polymerizable functional group is particularly preferable.
前記（Ｃ）アミン化合物の配合量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記（Ａ）ラジカル重合性単量体１００質量部に対して、０．０１質量部〜１０質量部が好ましく、０．０２質量部〜５質量部がより好ましい。
また、前記芳香族アミン化合物と前記脂肪族アミン化合物とを併用する場合、これらの配合比としては、質量比で、前記芳香族アミン化合物：前記脂肪族アミン化合物＝１：９９〜９９：１が好ましく、３：９７〜９７：３がより好ましい。
There is no restriction | limiting in particular as a compounding quantity of the said (C) amine compound, Although it can select suitably according to the objective, 0.01 mass with respect to 100 mass parts of said (A) radically polymerizable monomers. Part-10 mass parts is preferable, and 0.02 mass part-5 mass parts is more preferable.
Moreover, when using together the said aromatic amine compound and the said aliphatic amine compound, as these compounding ratios, the said aromatic amine compound: the said aliphatic amine compound = 1: 99-99: 1 is a mass ratio. Preferably, 3:97 to 97: 3 is more preferable.
更に、必要に応じて、公知の他の重合開始剤を用いることができる。前記他の重合開始剤成分としては、過酸化ベンゾイル、クメンハイドロパーオキサイド等の有機過酸化物類；酸化バナジウム（ＩＶ）アセチルアセトナート、ビス（マルトラート）オキソバナジウム（ＩＶ）等の＋ＩＶ価又は＋Ｖ価のバナジウム化合物類；テトラフェニルホウ素ナトリウム、テトラフェニルホウ素トリエタノールアミン塩、テトラフェニルホウ素ジメチル−ｐ−トルイジン塩、テトラキス（ｐ−フルオロフェニル）ホウ素ナトリウム、ブチルトリ（ｐ−フルオロフェニル）ホウ素ナトリウム等のアリールボレート化合物類；３，３’−カルボニルビス（７−ジエチルアミノ）クマリン、７−ヒドロキシ−４−メチル−クマリン等のクマリン系色素類；ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、ビス（２，６−ジメトキシベンソイル）−２，４，４−トリメチルペンチルホスフィンオキサイド等のアシルホスフィンオキサイド類；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル等のベンゾインアルキルエーテル類；２，４−ジエトキシチオキサンソン、２−クロロチオキサンソン、メチルチオキサンソン等のチオキサンソン誘導体；ベンゾフェノン、ｐ，ｐ’−ジメチルアミノベンゾフェノン、ｐ，ｐ’−メトキシベンゾフェノン等のベンゾフェノン誘導体類などが挙げられる。
なお、前記他の重合開始剤としては、１種単独で用いてもよく２種以上を併用してもよい。
Furthermore, other known polymerization initiators can be used as necessary. Examples of the other polymerization initiator components include organic peroxides such as benzoyl peroxide and cumene hydroperoxide; + IV value or + V such as vanadium (IV) acetylacetonate, bis (maltolate) oxovanadium (IV), etc. Valent vanadium compounds; tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) boron sodium, butyltri (p-fluorophenyl) boron sodium, etc. Aryl borate compounds; coumarin-based dyes such as 3,3′-carbonylbis (7-diethylamino) coumarin, 7-hydroxy-4-methyl-coumarin; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxa B , Acylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; Examples include thioxanthone derivatives such as 4-diethoxythioxanthone, 2-chlorothioxanthone, and methylthioxanthone; benzophenone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, and p, p′-methoxybenzophenone. .
In addition, as said other polymerization initiator, 1 type may be used individually and 2 or more types may be used together.
＜（Ｄ）光酸発生剤＞
前記（Ｄ）光酸発生剤は、前記（Ａ）ラジカル重合性単量体の重合開始成分として配合される。
前記（Ｄ）光酸発生剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、トリアジン化合物、アリールヨードニウム塩等が挙げられる。
<(D) Photoacid generator>
The (D) photoacid generator is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said (D) photo-acid generator, According to the objective, it can select suitably, For example, a triazine compound, an aryl iodonium salt, etc. are mentioned.
前記トリアジン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、トリクロロメチル基、トリブロモメチル基等のトリハロメチル基を少なくとも一つ有するｓ−トリアジン化合物が挙げられる。
前記トリハロメチル基により置換されたｓ−トリアジン化合物としては、例えば、下記一般式（２）で表される化合物が挙げられる。
There is no restriction | limiting in particular as said triazine compound, According to the objective, it can select suitably, For example, the s-triazine compound which has at least one trihalomethyl group, such as a trichloromethyl group and a tribromomethyl group, is mentioned.
Examples of the s-triazine compound substituted with the trihalomethyl group include compounds represented by the following general formula (2).
前記一般式（２）のＸで示されるハロゲン原子としては、塩素、臭素、ヨウ素のいずれでもよいが、塩素が一般的であり、従って、トリアジン環に結合した置換基（ＣＸ３）としては、トリクロロメチル基が一般的である。 The halogen atom represented by X in the general formula (2) may be any of chlorine, bromine and iodine, but chlorine is generally used. Therefore, as the substituent (CX 3 ) bonded to the triazine ring, A trichloromethyl group is common.
前記一般式（２）において、Ｒ４及びＲ５の少なくともいずれかが、前記トリアジン環と共役可能な不飽和結合を有する有機基である場合、前記歯科用光重合性組成物の保存安定性を特に優れたものとすることができる。他方、Ｒ４及びＲ５の少なくともいずれかが、ハロゲン置換アルキル基である方がより良好な重合活性を得られ易く、共にハロゲン置換アルキル基であると特に重合活性が良好である。 In the general formula (2), when at least one of R 4 and R 5 is an organic group having an unsaturated bond that can be conjugated to the triazine ring, the storage stability of the dental photopolymerizable composition is improved. It can be made particularly excellent. On the other hand, it is easier to obtain better polymerization activity when at least one of R 4 and R 5 is a halogen-substituted alkyl group, and when both are halogen-substituted alkyl groups, the polymerization activity is particularly good.
前記一般式（２）中、Ｒ４及びＲ５で示される前記トリアジン環と共役可能な不飽和結合により結合した有機基としては、特に制限はなく、目的に応じて適宜選択することができるが、炭素数が２〜３０の有機基が好ましく、炭素数が２〜１４の有機基が特に好ましい。
このような有機基を具体的に例示すると、フェニル基、メトキシフェニル基、ｐ−メチルチオフェニル基、ｐ−クロロフェニル基、４−ビフェニリル基、ナフチル基、４−メトキシ−１−ナフチル基等の炭素数６〜１４のアリール基；ビニル基、２−フェニルエテニル基、２−（置換フェニル）エテニル基等の炭素数２〜１４のアルケニル基等が挙げられる。なお、前記置換フェニル基の有する置換基としては、メチル基、エチル基、プロピル基等の炭素数１〜６のアルキル基；メトキシ基、エトキシ基、プロポキシ基等の炭素数１〜６のアルコキシ基；メチルチオ基、エチルチオ基、プロピルチオ基等の炭素数１〜６のアルキルチオ基；フェニル基；ハロゲン原子などが挙げられる。
In the general formula (2), the organic group bonded by an unsaturated bond that can be conjugated with the triazine ring represented by R 4 and R 5 is not particularly limited and may be appropriately selected depending on the purpose. An organic group having 2 to 30 carbon atoms is preferable, and an organic group having 2 to 14 carbon atoms is particularly preferable.
Specific examples of such an organic group include carbon number such as phenyl group, methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, naphthyl group, 4-methoxy-1-naphthyl group, etc. C6-C14 alkenyl groups, such as a 6-14 aryl group; a vinyl group, 2-phenylethenyl group, 2- (substituted phenyl) ethenyl group, etc. are mentioned. In addition, as a substituent which the said substituted phenyl group has, C1-C6 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group An alkylthio group having 1 to 6 carbon atoms such as a methylthio group, an ethylthio group and a propylthio group; a phenyl group; a halogen atom and the like.
また、前記一般式（２）中、Ｒ４及びＲ５で示されるアルキル基及びアルコキシ基は、置換基を有するものであってもよい。
前記アルキル基としては、炭素数１〜１０のものが好ましく、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｎ−ヘキシル基等の非置換のアルキル基；トリクロロメチル基、トリブロモメチル基、α，α，β−トリクロロエチル基等のハロゲン置換アルキル基などが挙げられる。
前記アルコキシ基としては、炭素数１〜１０のものが好ましく、例えば、メトキシ基、エトキシ基、ブトキシ基等の非置換のアルコキシ基；２−｛Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノ｝エトキシ基、２−｛Ｎ−ヒドロキシエチル−Ｎ−エチルアミノ｝エトキシ基、２−｛Ｎ−ヒドロキシエチル−Ｎ−メチルアミノ｝エトキシ基、２−｛Ｎ，Ｎ−ジアリルアミノ｝エトキシ基等のアミノ基により置換されたアルコキシ基などが挙げられる。
In the general formula (2), the alkyl group and alkoxy group represented by R 4 and R 5 may have a substituent.
As said alkyl group, a C1-C10 thing is preferable, For example, unsubstituted alkyl groups, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group A halogen-substituted alkyl group such as a trichloromethyl group, a tribromomethyl group, and an α, α, β-trichloroethyl group;
The alkoxy group is preferably one having 1 to 10 carbon atoms, for example, an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group; 2- {N, N-bis (2-hydroxyethyl) amino} Amino such as ethoxy group, 2- {N-hydroxyethyl-N-ethylamino} ethoxy group, 2- {N-hydroxyethyl-N-methylamino} ethoxy group, 2- {N, N-diallylamino} ethoxy group And an alkoxy group substituted by a group.
前記一般式（２）で表される、前記トリハロメチル基を有するｓ−トリアジン化合物を具体的に例示すると、２，４，６−トリス（トリクロロメチル）−ｓ−トリアジン（「ＴＣＴ」）、２，４，６−トリス（トリブロモメチル）−ｓ−トリアジン、２−メチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−メチル−４，６−ビス（トリブロモメチル）−ｓ−トリアジン、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−メチルチオフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−クロロフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（２，４−ジクロロフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−ブロモフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−トリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−ｎ−プロピル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（α，α，β−トリクロロエチル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−スチリル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−（ｐ−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−（ｏ−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−（ｐ−ブトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−（３，４−ジメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−（３，４，５−トリメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（１−ナフチル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−ビフェニリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−｛Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノ｝エトキシ］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−｛Ｎ−ヒドロキシエチル−Ｎ−エチルアミノ｝エトキシ］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−｛Ｎ−ヒドロキシエチル−Ｎ−メチルアミノ｝エトキシ］−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−［２−｛Ｎ，Ｎ−ジアリルアミノ｝エトキシ］−４，６−ビス（トリクロロメチル）−ｓ−トリアジンなどが挙げられる。 Specific examples of the s-triazine compound having the trihalomethyl group represented by the general formula (2) include 2,4,6-tris (trichloromethyl) -s-triazine (“TCT”), 2 , 4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s -Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthio) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4- Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (Trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (o-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) eth L] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6- Bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N -Hide Roxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl)- Examples include s-triazine.
前記例示中、特に好ましいトリアジン化合物としては、重合活性の点で２，４，６−トリス（トリクロロメチル）−ｓ−トリアジンであり、また、保存安定性の点で、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−クロロフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、及び２−（４−ビフェニリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジンである。
なお、これらトリアジン化合物は、１種単独で用いてもよく２種以上を併用してもよい。
Among the above examples, a particularly preferred triazine compound is 2,4,6-tris (trichloromethyl) -s-triazine in terms of polymerization activity, and 2-phenyl-4,6 in terms of storage stability. -Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis (trichloromethyl) ) -S-triazine.
In addition, these triazine compounds may be used individually by 1 type, and may use 2 or more types together.
前記アリールヨードニウム塩としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、ジフェニルヨードニウム、ビス（ｐ−クロロフェニル）ヨードニウム、ジトリルヨードニウム、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウム、ｐ−イソプロピルフェニル−ｐ−メチルフェニルヨードニウム、ビス（ｍ−ニトロフェニル）ヨードニウム、ｐ−ｔｅｒｔ−ブチルフェニルフェニルヨードニウム、ｐ−メトキシフェニルフェニルヨードニウム、ビス（ｐ−メトキシフェニル）ヨードニウム、ｐ−オクチルオキシフェニルフェニルヨードニウム、ｐ−フェノキシフェニルフェニルヨードニウム、ビス（ｐ−ドデシルフェニル）ヨードニウム等のカチオンと、クロリド、ブロミド、ｐ−トルエンスルホナート、トリフルオロメタンスルホナート、テトラフルオロボレート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレート、ヘキサフルオロフォスフェート、ヘキサフルオロアルセナート、ヘキサフルオロアンチモネート等のアニオンからなるジアリールヨードニウム塩化合物が好ましい。 The aryliodonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) Iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyl Cations such as oxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, bis (p-dodecylphenyl) iodonium, chloride, bromide, p-toluenesulfonate, tri Le Oro methanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis pentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate, diaryliodonium salt compounds composed of anions such as hexafluoroantimonate are preferred.
これらの中でも、前記（Ａ）ラジカル重合性単量体に対する溶解性の点から、ｐ−トルエンスルホナート、トリフルオロメタンスルホナート、テトラフルオロボレート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレート、ヘキサフルオロフォスフェート、ヘキサフルオロアルセナート、ヘキサフルオロアンチモネートをアニオンとして有する化合物が好ましく、また、アニオンの求核性が低く、重合速度が速い点から、ヘキサフルオロアンチモネート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレートをアニオンとして有する化合物がより好ましく、更に、アニオンに由来する毒性がより低いことから、テトラキスペンタフルオロフェニルボレートが特に好ましい。
なお、これらアリールヨードニウム塩としては、１種単独で用いてもよく２種以上を併用してもよい。
Among these, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluoro from the viewpoint of solubility in the (A) radical polymerizable monomer. Compounds having phosphate, hexafluoroarsenate and hexafluoroantimonate as anions are preferred, and hexafluoroantimonate, tetrakispentafluorophenylborate, tetrakispenta are from the viewpoint of low anion nucleophilicity and high polymerization rate. A compound having fluorophenyl gallate as an anion is more preferable, and tetrakispentafluorophenyl borate is particularly preferable because toxicity derived from the anion is lower. Arbitrariness.
In addition, as these aryl iodonium salts, you may use individually by 1 type and may use 2 or more types together.
前記（Ｄ）光酸発生剤の配合量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記（Ａ）ラジカル重合性単量体１００質量部に対して、０．００１質量部〜１０質量部が好ましく、０．０５質量部〜５質量部がより好ましい。 There is no restriction | limiting in particular as a compounding quantity of the said (D) photo-acid generator, Although it can select suitably according to the objective, It is 0.00 with respect to 100 mass parts of said (A) radically polymerizable monomers. 001 mass part-10 mass parts are preferable, and 0.05 mass part-5 mass parts are more preferable.
＜（Ｅ）α−アルキルスチレン化合物＞
前記（Ｅ）α−アルキルスチレン化合物は、大きな窩洞に対しても優れた窩洞適合性及び機械的強度を兼備する重合硬化体を得る目的で配合される。
前記（Ｅ）α−アルキルスチレン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、２−フェニル−1−プロペン（α−メチルスチレン）、２，４−ジフェニル−４−メチル−１−ペンテン（α−メチルスチレンダイマー）、３，５−ジフェニル−５−メチル−２−へプテン、１，３−ジフェニル−１−ブテン、２，４−ジフェニル−４−メチル−２−ペンテン、３，５−ジフェニル−５−メチル−３−へプテン、１，１−ジフェニルエチレン等が挙げられる。これらの中で、特に本発明の効果が得られやすく、また、入手の容易さから、２，４−ジフェニル−４−メチル−１−ペンテン（α−メチルスチレンダイマー）が好適である。
<(E) α-alkylstyrene compound>
The (E) α-alkylstyrene compound is blended for the purpose of obtaining a polymerized cured product having excellent cavity compatibility and mechanical strength even for a large cavity.
The (E) α-alkylstyrene compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-phenyl-1-propene (α-methylstyrene), 2,4-diphenyl- 4-methyl-1-pentene (α-methylstyrene dimer), 3,5-diphenyl-5-methyl-2-heptene, 1,3-diphenyl-1-butene, 2,4-diphenyl-4-methyl- 2-pentene, 3,5-diphenyl-5-methyl-3-heptene, 1,1-diphenylethylene and the like can be mentioned. Among these, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable because the effects of the present invention are particularly easily obtained and it is easily available.
前記（Ｅ）α−アルキルスチレン化合物の配合量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記（Ａ）ラジカル重合性単量体１００質量部に対して、０．０１質量部〜１質量部が好ましく、０．１質量部〜０．５質量部がより好ましい。
前記配合量が０．０１質量部未満であると、前記（Ａ）ラジカル重合性単量体の重合速度を律速して収縮応力を十分に緩和させることができないことがあり、１質量部を超えると、前記重合硬化体の機械的強度が低下することがある。
There is no restriction | limiting in particular as a compounding quantity of the said (E) alpha-alkyl styrene compound, Although it can select suitably according to the objective, It is 0 with respect to 100 mass parts of said (A) radically polymerizable monomers. 0.01 parts by mass to 1 part by mass is preferable, and 0.1 parts by mass to 0.5 parts by mass is more preferable.
When the blending amount is less than 0.01 parts by mass, the polymerization rate of the radically polymerizable monomer (A) may be limited and the shrinkage stress may not be sufficiently relaxed. In some cases, the mechanical strength of the polymerized cured product may decrease.
＜その他の成分＞
前記その他の成分としては、本発明の効果を妨げない限り、特に制限はなく、目的に応じて適宜選択することができ、例えば、歯科用修復材料の配合成分として公知の（Ｆ）充填材（フィラー）、（Ｇ）重合禁止剤等を挙げることができる。
<Other ingredients>
The other components are not particularly limited as long as the effects of the present invention are not hindered, and can be appropriately selected depending on the purpose. For example, the filler (F) known as a compounding component of a dental restoration material ( Filler), (G) polymerization inhibitor, and the like.
−（Ｆ）充填材−
前記（Ｆ）充填材は、前記歯科用光重合性組成物の重合硬化体に機械的強度を付与し、重合収縮や熱膨張を低減させる目的で配合される。
前記（Ｆ）充填材としては、特に制限はなく、目的に応じて適宜選択することができ、公知の無機充填材、有機充填材を用いることができるが、中でも、前記無機充填材が好ましい。
-(F) Filler-
The filler (F) is blended for the purpose of imparting mechanical strength to the polymerized cured product of the dental photopolymerizable composition and reducing polymerization shrinkage and thermal expansion.
There is no restriction | limiting in particular as said (F) filler, According to the objective, it can select suitably, A well-known inorganic filler and an organic filler can be used, Above all, the said inorganic filler is preferable.
前記無機充填材の材料としては、特に制限はなく、石英、シリカ、アルミナ、シリカチタニア、シリカジルコニア、ランタンガラス、バリウムガラス、ストロンチウムガラス等の金属酸化物類を挙げることができる。また、必要に応じて、ケイ酸塩ガラス、フルオロアルミノシリケートガラス等の歯科用の無機充填材として公知のカチオン溶出性の無機充填材を配合してもよい。 The material for the inorganic filler is not particularly limited, and examples thereof include metal oxides such as quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Moreover, you may mix | blend a well-known cation elution inorganic filler as dental inorganic fillers, such as silicate glass and fluoroaluminosilicate glass, as needed.
また、これら無機充填材に前記（Ａ）ラジカル重合性単量体を添加し、ペースト状とした後、重合硬化させ、これを粉砕して得られる粒状の有機−無機複合充填材を用いてもよい。 Alternatively, the above-mentioned inorganic filler (A) may be added with the radical polymerizable monomer (A) to form a paste, and then polymerized and cured, and then pulverized to obtain a granular organic-inorganic composite filler. Good.
これら（Ｆ）充填材の粒径としては、特に制限はなく、一般的に歯科用材料として使用されている０．０１μｍ〜１００μｍ（好ましくは０．０１μｍ〜５μｍ）の平均粒径の充填材を用いることができる。中でも、球状の前記無機充填材を用いると、得られる硬化体の表面滑沢性を向上させることができる。
また、前記（Ｆ）充填材の屈折率としても、特に制限はなく、一般的な歯科用材料として使用される無機充填材の屈折率である、１．４〜１．７の範囲の屈折率を有する充填材を用いることができる。
The particle size of these (F) fillers is not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm (preferably 0.01 μm to 5 μm) that are generally used as dental materials are used. Can be used. Among these, when the spherical inorganic filler is used, the surface smoothness of the obtained cured product can be improved.
Moreover, there is no restriction | limiting in particular also as the refractive index of the said (F) filler, The refractive index of the range of 1.4-1.7 which is the refractive index of the inorganic filler used as a general dental material. A filler having can be used.
前記無機充填材としては、前記（Ａ）ラジカル重合性単量体とのなじみを向上させ、また、機械的強度や耐水性を向上させる観点から、シランカップリング剤に代表される表面処理剤で表面処理されることが好ましい。
前記表面処理の方法としては、公知の方法を挙げることができ、また、前記シランカップリング剤としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロイルオキシプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、ヘキサメチルジシラザンなどを挙げることができる。
なお、前記（Ｆ）充填材としては、１種単独で用いてもよく２種以上を併用してもよい。
The inorganic filler is a surface treatment agent typified by a silane coupling agent from the viewpoint of improving familiarity with the (A) radical polymerizable monomer and improving mechanical strength and water resistance. A surface treatment is preferred.
Examples of the surface treatment method include known methods, and examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, Vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane, etc. Can be mentioned.
In addition, as said (F) filler, it may be used individually by 1 type and may use 2 or more types together.
前記（Ｆ）充填材の配合量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記（Ａ）ラジカル重合性単量体と混合させたときの粘度（操作性）や硬化体の機械的物性を考慮して、前記（Ａ）ラジカル重合性単量体１００質量部に対して５０質量部〜１，５００質量部が好ましく、７０質量部〜１，０００質量部がより好ましい。 The blending amount of the filler (F) is not particularly limited and may be appropriately selected depending on the intended purpose. Viscosity (operability) when mixed with the (A) radical polymerizable monomer. In consideration of the mechanical properties of the cured product and the cured product, 50 parts by weight to 1,500 parts by weight is preferable with respect to 100 parts by weight of the radically polymerizable monomer (A). More preferred.
−（Ｇ）重合禁止剤−
前記（Ｇ）重合禁止剤は、保存安定性を得る目的で配合される。
前記（Ｇ）重合禁止剤としては、特に制限はなく、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ジブチルヒドロキシトルエンなどを挙げることができる。
-(G) Polymerization inhibitor-
The (G) polymerization inhibitor is blended for the purpose of obtaining storage stability.
There is no restriction | limiting in particular as said (G) polymerization inhibitor, For example, hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene etc. can be mentioned.
また、前記その他の成分として、歯牙の色調に合わせる目的で顔料、蛍光顔料、染料、紫外線に対する変色防止目的で紫外線吸収剤を配合してもよいし、歯科用コンポジットレジン用途として公知の添加剤を配合してもよい。 In addition, as the other components, pigments, fluorescent pigments, dyes for the purpose of matching the color tone of the teeth, ultraviolet absorbers for the purpose of preventing discoloration against ultraviolet rays may be blended, and additives known for use in dental composite resins. You may mix | blend.
＜用途＞
前記歯科用光重合性組成物は、大きな窩洞に対する優れた窩洞適合性及び機械的強度を兼備する重合硬化体が得られる。したがって、前記歯科用光重合性組成物としては、大きな窩洞向けの充填修復材として、３ｍｍ〜６ｍｍの深さを有する窩洞を充填修復する歯科用コンポジットレジン用途に好適である。また、こうした用途で用いる場合、前記歯科用光重合性組成物を前記窩洞内に一度に充填し光照射して重合硬化操作を完了させることができる。
<Application>
The dental photopolymerizable composition provides a polymerized cured product having excellent cavity compatibility with a large cavity and mechanical strength. Therefore, the dental photopolymerizable composition is suitable as a dental restoration resin for filling and repairing cavities having a depth of 3 mm to 6 mm as a filling and restoration material for large cavities. Further, when used in such applications, the dental photopolymerizable composition can be filled into the cavity at a time and irradiated with light to complete the polymerization and curing operation.
以下、本発明を具体的に説明するために、実施例、比較例を挙げて説明するが、本発明の技術的思想は、これらにより何ら制限されるものではない。 Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the technical idea of the present invention is not limited by these.
（各成分並びにその略称及び略号）
＜（Ａ）ラジカル重合性単量体＞
ｂｉｓ−ＧＭＡ：２，２−ビス［４−（３−メタクリロイルオキシ−２−ヒドロキシプロピルオキシ）フェニル］プロパン
３Ｇ：トリエチレングリコールジメタクリレート
＜（Ｂ）α−ジケトン化合物＞
ＣＱ：カンファーキノン
＜（Ｃ）アミン化合物＞
ＤＭＢＥ：Ｎ，Ｎ−ジメチルアミノ−ｐ−安息香酸エチル
ＭＤＥＯＡ：Ｎ−メチルジエタノールアミン
＜（Ｄ）光酸発生剤＞
ＩＰＤＰＩ：ｐ−イソプロピルフェニル−ｐ−メチルフェニルヨードニウムテトラキスペンタフルオロフェニルボレート
ＴＣＴ：２，４，６−トリス（トリクロロメチル）−ｓ−トリアジン
＜（Ｅ）α−アルキルスチレン化合物＞
ＭＳＤ：α−メチルスチレンダイマー
ＭＳ：α−メチルスチレン
＜（Ｆ）充填材＞
Ｆ−１：球状シリカ−ジルコニアのγ−メタクリロイルオキシプロピルトリメトキシシラン表面処理物であり、平均粒径が０．２μｍであるもの
Ｆ−２：前記球状シリカ−ジルコニア（Ｆ−１）をｂｉｓ−ＧＭＡ／３Ｇ＝６０／４０の重合性単量体に分散して重合硬化後、粉砕したものであり、また、平均粒径が３０μｍであるもの
Ｆ−３：球状シリカ−ジルコニアのγ−メタクリロイルオキシプロピルトリメトキシシラン表面処理物であり、平均粒径が０．４μｍであるもの
Ｆ−４：球状シリカ−ジルコニアのγ−メタクリロイルオキシプロピルトリメトキシシラン表面処理物であり、平均粒径が０．０８μｍであるもの
＜（Ｇ）重合禁止剤＞
ＨＱＭＥ：ヒドロキノンモノメチルエーテル
(Each component and its abbreviations and abbreviations)
<(A) Radical polymerizable monomer>
bis-GMA: 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane 3G: triethylene glycol dimethacrylate <(B) α-diketone compound>
CQ: camphorquinone <(C) amine compound>
DMBE: N, N-dimethylamino-p-ethylbenzoate MDEOA: N-methyldiethanolamine <(D) Photoacid generator>
IPDPI: p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate TCT: 2,4,6-tris (trichloromethyl) -s-triazine <(E) α-alkylstyrene compound>
MSD: α-methylstyrene dimer MS: α-methylstyrene <(F) filler>
F-1: Spherical silica-zirconia surface-treated product of γ-methacryloyloxypropyltrimethoxysilane having an average particle size of 0.2 μm F-2: Bis- of the spherical silica-zirconia (F-1) GMA / 3G = 60/40 dispersed in a polymerizable monomer, polymerized and cured, and then pulverized, and average particle size is 30 μm F-3: γ-methacryloyloxy of spherical silica-zirconia F-4: Spherical silica-zirconia γ-methacryloyloxypropyltrimethoxysilane surface-treated product with an average particle size of 0.08 μm <(G) Polymerization inhibitor>
HQME: Hydroquinone monomethyl ether
（実施例１）
前記（Ａ）ラジカル重合性単量体として、ｂｉｓ−ＧＭＡ（６０質量部）と、３Ｇ（４０質量部）とを混合して、前記（Ａ）ラジカル重合性単量体の混合物を調製した。
次いで、前記混合物１００質量部に対し、前記（Ｂ）α−ジケトン化合物としてＣＱを０．３質量部、前記（Ｃ）アミン化合物としてＤＭＢＥを０．４５質量部、前記（Ｄ）光酸発生剤としてＩＰＤＰＩを０．７５質量部、前記（Ｅ）α−アルキルスチレン化合物としてＭＳＤを０．３質量部、前記（Ｇ）重合禁止剤としてＨＱＭＥを０．１５質量部それぞれ加え、これらが均一になるまで混合した。
次いで、乳鉢に、前記（Ｆ）充填材としてＦ−１、Ｆ−２を質量比６０：４０（＝Ｆ−１：Ｆ−２）の配合比で４５０質量部計りとり、前記均一混合物１００質量部を赤色光下にて徐々に加えていき、暗所にて十分に混練し均一な硬化性ペーストとした。
次いで、減圧下脱泡して、このペーストから気泡を除去し、実施例１に係る歯科用光重合性組成物を製造した。
Example 1
As the (A) radical polymerizable monomer, bis-GMA (60 parts by mass) and 3G (40 parts by mass) were mixed to prepare a mixture of the (A) radical polymerizable monomer.
Next, 0.3 parts by mass of CQ as the (B) α-diketone compound, 0.45 parts by mass of DMBE as the (C) amine compound, and (D) the photoacid generator with respect to 100 parts by mass of the mixture. As a result, 0.75 parts by mass of IPDPI, 0.3 parts by mass of MSD as the (E) α-alkylstyrene compound, and 0.15 parts by mass of HQME as the (G) polymerization inhibitor were added, and these became uniform. Until mixed.
Next, in a mortar, 450 parts by mass of F-1 and F-2 as the filler (F) with a mass ratio of 60:40 (= F-1: F-2) are weighed, and the homogeneous mixture is 100 masses. The portion was gradually added under red light and sufficiently kneaded in a dark place to obtain a uniform curable paste.
Subsequently, defoaming was performed under reduced pressure to remove bubbles from the paste, and a dental photopolymerizable composition according to Example 1 was produced.
（実施例２，４，６〜１２及び参考例１，２）
前記（Ｃ）アミン化合物、前記（Ｄ）光酸発生剤、及び（Ｅ）α−アルキルスチレン化合物の種類、配合量を後掲表１に示す種類と配合量に変更したこと以外、実施例１と同様にして、実施例２，４，６〜１２及び参考例１，２に係る各歯科用光重合性組成物を製造した。
(Examples 2 , 4, 6-12 and Reference Examples 1, 2 )
Example 1 except that the types and blending amounts of the (C) amine compound, the (D) photoacid generator, and the (E) α-alkylstyrene compound were changed to the types and blending amounts shown in Table 1 below. Similarly, each dental photopolymerizable composition according to Examples 2 , 4, 6 to 12 and Reference Examples 1 and 2 was produced.
（比較例１〜４）
前記（Ｃ）アミン化合物、前記（Ｄ）光酸発生剤、及び（Ｅ）α−アルキルスチレン化合物の少なくともいずれかを配合せず、これらを後掲表１に示す種類と配合量で配合したこと以外、実施例１と同様にして、比較例１〜４に係る各歯科用光重合性組成物を製造した。
(Comparative Examples 1-4)
Other than not blending at least one of the (C) amine compound, the (D) photoacid generator, and the (E) α-alkylstyrene compound, and blending them in the types and amounts shown in Table 1 below. Each dental photopolymerizable composition according to Comparative Examples 1 to 4 was produced in the same manner as in Example 1.
（特性評価）
＜重合収縮応力評価試験＞
重合収縮応力試験は、参考文献（根元ら 歯科材料・器械 Ｖｏｌ．１１ Ｎｏ．４ ６９７−７０２（１９９２））に記載の試験方法を参照して実施した。収縮応力測定装置の本体及び制御部として万能試験機（島津製作所製、オートグラフＡＧ５０００Ｄ）を用いた。開放型の窩洞試料部とし、模擬窩洞の大きさは、直径６ｍｍ、深さ２ｍｍとした。窩洞内部に歯科用接着材（ワンナップボンドＦプラス、トクヤマデンタル製）を塗布し１０秒放置後、可視光線照射器（トクソーパワーライト、株式会社トクヤマ製）で１０秒間光照射した。試験ごとに模擬窩洞に実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る各歯科用光重合性組成物を充填し、可視光線照射器（トクソーパワーライト、株式会社トクヤマ製）を用いて模擬窩洞上方から１０秒間光照射し、重合硬化させた。
前記光照射開始後、重合硬化によって生じる収縮応力を３分間測定し、その最大値を前記重合収縮応力の「最大応力」とした。また、前記光照射開始後、前記重合収縮応力が前記最大応力に至るまでの時間を「最大応力到達時間」として測定した。
実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る各歯科用光重合性組成物の「最大応力」、「最大応力到達時間」を後掲表１に示す。
(Characteristic evaluation)
<Evaluation test for polymerization shrinkage stress>
The polymerization shrinkage stress test was performed with reference to a test method described in a reference (Nemoto et al., Dental Materials and Instruments, Vol. 11 No. 4 697-702 (1992)). A universal testing machine (manufactured by Shimadzu Corp., Autograph AG5000D) was used as the main body and control unit of the shrinkage stress measuring device. The open cavity sample portion was used, and the size of the simulated cavity was 6 mm in diameter and 2 mm in depth. A dental adhesive (One Nap Bond F Plus, manufactured by Tokuyama Dental Co., Ltd.) was applied to the inside of the cavity and left for 10 seconds, and then irradiated with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for 10 seconds. For each test, the simulated cavity was filled with each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4, and a visible light irradiator (TOXOH). Power light, manufactured by Tokuyama Co., Ltd.) was used for light irradiation for 10 seconds from above the simulated cavity and polymerized and cured.
After the start of the light irradiation, the shrinkage stress caused by polymerization and curing was measured for 3 minutes, and the maximum value was defined as the “maximum stress” of the polymerization shrinkage stress. Further, the time until the polymerization shrinkage stress reaches the maximum stress after the start of the light irradiation was measured as “maximum stress arrival time”.
Table 1 shows “maximum stress” and “maximum stress arrival time” of each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4. Show.
＜窩洞適合性評価試験＞
牛を屠殺し、屠殺後２４時間以内に抜去した牛前歯の唇側の面を＃６００の耐水研磨紙で研磨した。
次いで、その研磨面に歯科用接着材（ボンドフォースＩＩ、トクヤマデンタル社製）を塗布し、１０秒間放置後、圧縮空気により乾燥させ、可視光線照射器（トクソーパワーライト、株式会社トクヤマ製）を用いて１０秒間光照射した。
次いで、歯科用接着材で処理した面に厚さ２ｍｍのφ８ｍｍの孔が形成されたワックスシートを張り付け、孔部に歯科用コンポジットレジン（パルフィークエステライト、トクヤマデンタル社製）を充填し、ポリプロピレンで圧接して、可視光線照射器（トクソーパワーライト、株式会社トクヤマ製）を用いて３０秒間光照射し、重合硬化させた。
次いで、注水下、ダイヤモンドバーを用いて、前記ワックスシートの前記孔部から露出する前記コンポジットレジン硬化体の上面側から前記コンポジットレジン硬化体の下に位置する前記歯にかけて掘削加工を行い、前記コンポジットレジン硬化体内に直径４ｍｍ、深さ４ｍｍの模擬窩洞を形成した。なお、前記模擬窩洞の形成に際し、前記掘削加工は、前記コンポジットレジン硬化体（厚さ２ｍｍ）に貫通孔を形成した後、前記歯の象牙質が露出する深さ（深さ２ｍｍ）まで行い、前記模擬窩洞の深さが４ｍｍとなるように行っている。
次いで、前記模擬窩洞内を前記研磨面に対する処理と同様に前記歯科用接着材で処理した後、試験ごとに前記模擬窩洞内に実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る各歯科用光重合性組成物を充填し、前記可視光線照射器を用いて１０秒間光照射し、重合硬化させ、窩洞適合性評価試験の各試験片を作製した。
次いで、前記試験片を３７℃の水中に２４時間浸漬した後、ダイヤモンドカッターを用いて、前記模擬窩洞の中央部分を窩底面に対して垂直に切断し、その切断面を＃１５００の耐水研磨紙及び＃３０００の耐水研磨紙で用いて研磨した。
前記試験片の研磨面をレーザー顕微鏡で観察し、前記模擬窩洞を構成する前記歯（深さ２ｍｍ）と重合硬化体との界面にギャップ（隙間）が存在するかを観察した。その観察結果に対し、前記切断面において前記界面を示す、前記模擬窩洞を構成する前記歯と重合硬化体との「境界線の長さ」に対する、ギャップが観察される位置における全ての前記模擬窩洞（前記歯で構成される部分）の長さを足し合わせた「ギャップ長さ」の比（「ギャップ長さ」／「境界線の長さ」の比）をとり、その比が０．１以上０．３未満であるものに対して○、０．３以上０．５未満であるものに対して△、０．５以上であるものに対して×の評価をそれぞれ行った。
<Cavity compatibility test>
The cows were slaughtered, and the lip side surface of the cow's front teeth removed within 24 hours after slaughtering was polished with # 600 water-resistant abrasive paper.
Next, a dental adhesive (Bond Force II, manufactured by Tokuyama Dental Co., Ltd.) was applied to the polished surface, left standing for 10 seconds, dried with compressed air, and a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). For 10 seconds.
Next, a wax sheet with a 2 mm-thick φ8 mm hole formed is attached to the surface treated with the dental adhesive, and the hole is filled with a dental composite resin (Palfique Estelite, manufactured by Tokuyama Dental Co., Ltd.). And irradiated with light for 30 seconds using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.) for polymerization and curing.
Next, under water injection, using a diamond bar, excavation is performed from the upper surface side of the composite resin cured body exposed from the hole of the wax sheet to the teeth positioned under the composite resin cured body, and the composite A simulated cavity having a diameter of 4 mm and a depth of 4 mm was formed in the cured resin body. In the formation of the simulated cavity, the excavation is performed up to a depth (depth 2 mm) where the dentin of the teeth is exposed after a through hole is formed in the cured composite resin (thickness 2 mm), The simulated cavity has a depth of 4 mm.
Next, after the inside of the simulated cavity was treated with the dental adhesive in the same manner as the treatment on the polished surface , Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 were placed in the simulated cavity for each test. And each dental photopolymerizable composition according to Comparative Examples 1 to 4 was filled, irradiated with light for 10 seconds using the visible light irradiator, polymerized and cured, and each test piece of the cavity compatibility evaluation test was produced. .
Next, after immersing the test piece in water at 37 ° C. for 24 hours, a diamond cutter was used to cut the central portion of the simulated cavity perpendicular to the bottom of the cavity, and the cut surface was # 1500 water-resistant abrasive paper And polished with # 3000 water-resistant abrasive paper.
The polished surface of the test piece was observed with a laser microscope, and it was observed whether a gap (gap) was present at the interface between the teeth (depth 2 mm) constituting the simulated cavity and the polymer cured body. With respect to the observation result, all the simulated cavities at the positions where gaps are observed with respect to the “boundary length” between the teeth constituting the simulated cavities and the polymerized cured body, which show the interface at the cut surface. Take the ratio of the “gap length” (the ratio of “gap length” / “boundary length”), which is the sum of the lengths of the (parts composed of the teeth), and the ratio is 0.1 or more An evaluation of “◯” was given for those less than 0.3, “Δ” was given for those of 0.3 or more and less than 0.5, and “x” was given for those of 0.5 or more.
＜曲げ強度試験＞
ステンレス製型枠に充填器を用いて実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る歯科用光重合性組成物を１つずつ充填し、ポリプロピレンで圧接して前記各歯科用光重合性組成物それぞれの試験試料を調製した。
次いで、前記各試験試料に対して、可視光線照射器（トクソーパワーライト、トクヤマ社製）を用いて、一方の面に３０秒間×３回、前記各試験試料の全体に光が当たるように場所を変えつつ、光源をポリプロピレンに密着させて光照射を行なった。
次いで、反対の面についても同様に光照射を行って前記各試験試料を硬化させた後、これを＃８００の耐水研磨紙を用いて、２×２×２５ｍｍの角柱状に形状を整えることで、実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る歯科用光重合性組成物の各試験片を得た。
前記各試験片を試験機（島津製作所製、オートグラフＡＧ５０００Ｄ）に装着し、支点間距離２０ｍｍ、クロスヘッドスピード１ｍｍ／分の条件で３点曲げ破壊強度を測定した。
前記破壊強度は、以下に示す式により、曲げ強さσＢとして算出した。
なお、前記試験片は、実施例１，２，４，６〜１２、参考例１，２及び比較例１〜４に係る歯科用光重合性組成物ごとに５個作製し、算出した曲げ強さσＢの５個の平均値を前記各歯科用光重合性組成物の曲げ強さ（ＭＰａ）とした。これら歯科用光重合性組成物の曲げ強さを後掲表１に示す。
<Bending strength test>
Each of the dental photopolymerizable compositions according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4 was filled into a stainless steel mold using a filling device, and polypropylene. Test samples of the respective dental photopolymerizable compositions were prepared by pressure welding.
Next, with respect to each test sample, using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.), light is applied to the entire test sample for 30 seconds × 3 times on one surface. While changing the place, the light source was brought into close contact with the polypropylene to perform light irradiation.
Next, the opposite surface was similarly irradiated with light to cure each of the test samples, and then this was shaped into a 2 × 2 × 25 mm prismatic shape using # 800 water-resistant abrasive paper. Each specimen of the dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4 was obtained.
Each test piece was mounted on a testing machine (manufactured by Shimadzu Corporation, Autograph AG5000D), and the three-point bending fracture strength was measured under the conditions of a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min.
The breaking strength was calculated as the bending strength σ B by the following formula.
In addition, the said test piece produced 5 pieces for every dental photopolymerizable composition which concerns on Example 1 , 2, 4 , 6-12, Reference Examples 1 and 2, and Comparative Examples 1-4 , and calculated bending strength. The average value of the five pieces of thickness σ B was taken as the bending strength (MPa) of each dental photopolymerizable composition. The bending strength of these dental photopolymerizable compositions is shown in Table 1 below.
前掲表１に示すように、実施例１，２，４，６〜１２及び参考例１，２に係る各歯科用光重合性組成物は、窩洞適合性評価が△以上で、かつ、曲げ強度が７５ＭＰａ以上であり、良好な窩洞適合性及び機械的強度を両立させることができている。
これに対し、比較例１〜４に係る各歯科用光重合性組成物は、窩洞適合性評価が△以上で、かつ、曲げ強度が７５ＭＰａ以上のものがなく、窩洞適合性及び機械的強度を両立させることができていない。
As shown in Table 1 above, each of the dental photopolymerizable compositions according to Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 has a cavity compatibility evaluation of Δ or more and bending strength. Is 75 MPa or more, and both good cavity compatibility and mechanical strength can be achieved.
On the other hand, each dental photopolymerizable composition according to Comparative Examples 1 to 4 has a cavity compatibility evaluation of Δ or more and a bending strength of 75 MPa or more, and has cavity compatibility and mechanical strength. It is not possible to achieve both.
即ち、実施例１に係る歯科用光重合性組成物に対し、前記（Ｄ）光酸発生剤及び前記（Ｅ）アルキルスチレンを配合しない比較例１に係る歯科用光重合性組成物では、最大応力到達時間が短時間であり、前記重合硬化体と前記模擬窩洞との界面において、急激に重合収縮応力が働き、多くのギャップを発生させたと考えられる。また、前記（Ｄ）光酸発生剤を配合しないことで、前記（Ｂ）α−ジケトン化合物及び前記（Ｃ）アミン化合物によるラジカル発生量が抑えられ、前記（Ａ）ラジカル重合性単量体の重合硬化体に十分な機械的強度を付与することができなかったものと考えられる。 That is, with respect to the dental photopolymerizable composition according to Example 1, the dental photopolymerizable composition according to Comparative Example 1 in which the (D) photoacid generator and the (E) alkylstyrene are not blended is the maximum. The stress arrival time is short, and it is considered that a large amount of gap was generated due to a rapid polymerization shrinkage stress acting at the interface between the polymerized cured body and the simulated cavity. In addition, by not blending the (D) photoacid generator, the amount of radicals generated by the (B) α-diketone compound and the (C) amine compound can be suppressed, and the (A) radical polymerizable monomer can be reduced. It is considered that sufficient mechanical strength could not be imparted to the polymerized cured product.
また、前記（Ｄ）光酸発生剤を配合せず、前記（Ｅ）α−アルキルスチレン化合物のみを配合した比較例２に係る歯科用光重合性組成物では、これら双方を配合しない比較例１に係る歯科用光重合性組成物よりも僅かに窩洞適合性が向上するものの、機械的強度が更に低下する結果となっている。このことは、前記（Ｄ）光酸発生剤を配合しないことで、前記（Ｂ）α−ジケトン化合物及び前記（Ｃ）アミン化合物によるラジカル発生量が抑えられたことに加え、単に前記（Ｅ）α−アルキルスチレン化合物だけを配合しても、前記（Ａ）ラジカル重合性単量体の重合度を低下させるように働くことを意味する。 Further, in the dental photopolymerizable composition according to Comparative Example 2 in which the (D) photoacid generator was not blended and only the (E) α-alkylstyrene compound was blended, Comparative Example 1 in which both of these were not blended. Although the cavity compatibility is slightly improved as compared with the dental photopolymerizable composition according to the present invention, the mechanical strength is further reduced. This is because, by not blending the (D) photoacid generator, the amount of radicals generated by the (B) α-diketone compound and the (C) amine compound is suppressed, and the (E) It means that even if only the α-alkylstyrene compound is blended, it functions to lower the degree of polymerization of the (A) radical polymerizable monomer.
また、実施例６に係る歯科用光重合性組成物に対し、前記（Ｅ）α−アルキルスチレン化合物を配合しない比較例３に係る歯科用光重合性組成物では、最大応力到達時間が極めて短時間であり、前記（Ｄ）光酸発生剤により、光照射開始直後から大量のラジカルが発生し続け、前記（Ａ）ラジカル重合性単量体の重合反応が急激かつ十分に進むことで、優れた機械的強度が得られるものの、その反面、前記重合硬化体と前記模擬窩洞との界面において、より急激に重合収縮応力が働き、多くのギャップを発生させたと考えられる。
この傾向は、同様の関係である、実施例１２に係る歯科用光重合性組成物と比較例４に係る歯科用光重合性組成物との比較を通じて、前記（Ｄ）光酸発生剤の種類を変更しても変わらないことが確認される。
Further, in the dental photopolymerizable composition according to Comparative Example 3 in which the (E) α-alkylstyrene compound is not added to the dental photopolymerizable composition according to Example 6, the maximum stress arrival time is extremely short. It is time, the (D) photoacid generator continues to generate a large amount of radicals immediately after the start of light irradiation, and the polymerization reaction of the (A) radical polymerizable monomer proceeds rapidly and sufficiently. However, on the other hand, it is considered that the polymerization shrinkage stress acted more rapidly at the interface between the polymerized cured body and the simulated cavity and many gaps were generated.
This tendency is similar, and through comparison between the dental photopolymerizable composition according to Example 12 and the dental photopolymerizable composition according to Comparative Example 4, the type of the (D) photoacid generator It is confirmed that even if it is changed, it does not change.
したがって、実施例１，２，４，６〜１２及び参考例１，２に係る各歯科用光重合性組成物と比較例１〜４に係る各歯科用光重合性組成物の比較から、前記（Ｄ）光酸発生剤及び前記（Ｅ）アルキルスチレンが、前記（Ａ）ラジカル重合性単量体を緩やかな速度で重合させ、延いては、急激な重合収縮応力によりギャップが発生することを抑制させることができると考えられる。また、前記（Ａ）ラジカル重合性単量体の重合反応自体は、光照射を継続することで十分進み、前記重合硬化体に優れた機械的強度を付与することができると考えられる。このことは、前記（Ｄ）光酸発生剤により前記（Ｂ）α−ジケトン化合物及び前記（Ｃ）アミン化合物から発生するラジカル種のうち、幾らかが前記（Ｅ）α−アルキルスチレン化合物に移動することで前記（Ａ）ラジカル重合性単量体の重合反応の律速要因となり、前記（Ｅ）α−アルキルスチレン化合物に移動した前記ラジカル種は、時間の経過とともに前記（Ａ）ラジカル重合性単量体の重合反応に供されるためと考えられる。 Therefore, from comparison between each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 and each dental photopolymerizable composition according to Comparative Examples 1 to 4, (D) The photoacid generator and the (E) alkyl styrene polymerize the (A) radical polymerizable monomer at a moderate rate, and as a result, a gap is generated due to a rapid polymerization shrinkage stress. It is thought that it can be suppressed. In addition, it is considered that the polymerization reaction itself of the (A) radical polymerizable monomer proceeds sufficiently by continuing the light irradiation, and can impart excellent mechanical strength to the polymerized cured product. This means that some of the radical species generated from the (B) α-diketone compound and the (C) amine compound by the (D) photoacid generator migrate to the (E) α-alkylstyrene compound. As a result, the radical species that has become a rate-determining factor for the polymerization reaction of the (A) radical polymerizable monomer, and has moved to the (E) α-alkylstyrene compound, the radical polymerizable monomer (A) This is considered to be used for the polymerization reaction of the monomer.
特に、前記（Ａ）ラジカル重合性単量体（１００質量部）に対する前記（Ｅ）α−アルキルスチレン化合物の配合割合である（Ｅ）／（Ａ）が、質量比で０．１〜０．５の範囲内である実施例１，２，４に係る各歯科用光重合性組成物では、範囲外である参考例１，２に係る各歯科用光重合性組成物よりも、優れた窩洞適合性及び機械的強度が得られている。 Particularly, (E) / (A), which is a blending ratio of the (E) α-alkylstyrene compound to the (A) radical polymerizable monomer (100 parts by mass), is 0.1 to 0.00 by mass ratio. The dental photopolymerizable compositions according to Examples 1, 2, and 4 within the range of 5 are superior to the dental photopolymerizable compositions according to Reference Examples 1 and 2 that are outside the range. Compatibility and mechanical strength are obtained.
また、前記（Ｃ）アミン化合物として、芳香族第３級アミン化合物と脂肪族第３級アミン化合物とを併用する実施例６〜８に係る各歯科用光重合性組成物では、前記芳香族アミン化合物単独の実施例１，２及び参考例１に係る各歯科用光重合性組成物よりも、最大応力到達時間が長く優れた窩洞適合性を示すとともに、より優れた機械的強度が得られている。
なお、実施例６に係る歯科用光重合性組成物に対し、前記（Ｆ）充填材の配合量を少なくした実施例９に係る歯科用光重合性組成物では、機械的強度の低下が確認されるものの、前記（Ｆ）充填材の種類を実施例１０に係る歯科用光重合性組成物で用いた球状のものに変更することで、機械的強度の改善が期待できる。
Moreover, in each dental photopolymerizable composition which concerns on Examples 6-8 which uses together an aromatic tertiary amine compound and an aliphatic tertiary amine compound as said (C) amine compound, in said aromatic amine Compared to each of the dental photopolymerizable compositions according to Examples 1 and 2 and Reference Example 1 where the compound alone is used, the maximum stress arrival time is long and excellent cavity compatibility is obtained, and more excellent mechanical strength is obtained. Yes.
In addition, with respect to the dental photopolymerizable composition according to Example 6, in the dental photopolymerizable composition according to Example 9 in which the blending amount of the filler (F) was reduced, a decrease in mechanical strength was confirmed. However, the mechanical strength can be improved by changing the type of the filler (F) to the spherical one used in the dental photopolymerizable composition according to Example 10.
また、前記（Ｅ）α−アルキルスチレン化合物として、α−アルキルスチレンダイマーを配合する実施例６に係る歯科用光重合性組成物では、α−アルキルスチレンを配合する実施例１１に係る歯科用光重合性組成物よりも、最大応力到達時間が長く優れた窩洞適合性を示すとともに、より優れた機械的強度が得られている。 Further, in the dental photopolymerizable composition according to Example 6 in which an α-alkylstyrene dimer is blended as the (E) α-alkylstyrene compound, the dental light according to Example 11 in which α-alkylstyrene is blended. The maximum stress arrival time is longer than that of the polymerizable composition, and excellent cavity compatibility is exhibited, and superior mechanical strength is obtained.
また、前記（Ｄ）光酸発生剤として、ジアリールヨードニウム塩化合物を配合する実施例６に係る歯科用光重合性組成物では、ｓ−トリアジン化合物を配合する実施例１２に係る歯科用光重合性組成物よりも、最大応力到達時間が長く優れた窩洞適合性を示すとともに、より優れた機械的強度が得られている。 Moreover, in the dental photopolymerizable composition according to Example 6 in which a diaryliodonium salt compound is blended as the photoacid generator (D), the dental photopolymerizability according to Example 12 in which an s-triazine compound is blended. The maximum stress arrival time is longer than that of the composition, and excellent cavity compatibility is exhibited, and superior mechanical strength is obtained.
Claims (6)
前記（Ａ）ラジカル重合性単量体１００質量部に対する前記（Ｅ）α−アルキルスチレン化合物の配合量が０．１質量部〜０．５質量部であり、
直径６ｍｍ、深さ２ｍｍの模擬窩洞の内部に前記歯科用光重合性組成物を充填した後に、前記模擬窩洞の上方から光照射して前記歯科用光重合性組成物を重合硬化させたとき、前記歯科用光重合性組成物の前記重合硬化によって生じる重合収縮応力が最大値に至るまでの時間である最大応力到達時間が４８秒以上である、ことを特徴とする歯科用光重合性組成物。 (A) a radical polymerizable monomer, comprising Nde containing and (B) alpha-diketone compound, and (C) an amine compound, and (D) photoacid generator, and a (E) alpha-alkylstyrene compounds A dental photopolymerizable composition comprising:
The blending amount of the (E) α-alkylstyrene compound with respect to 100 parts by mass of the (A) radical polymerizable monomer is 0.1 parts by mass to 0.5 parts by mass,
When the dental photopolymerizable composition is filled into the inside of a simulated cavity having a diameter of 6 mm and a depth of 2 mm, and then the dental photopolymerizable composition is polymerized and cured by irradiation with light from above the simulated cavity, The dental photopolymerizable composition having a maximum stress arrival time of 48 seconds or more, which is a time until the polymerization shrinkage stress generated by the polymerization and curing of the dental photopolymerizable composition reaches a maximum value . .
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