JP7430326B2 - Dental adhesive composition and dental adhesive composition package - Google Patents
Dental adhesive composition and dental adhesive composition package Download PDFInfo
- Publication number
- JP7430326B2 JP7430326B2 JP2020093552A JP2020093552A JP7430326B2 JP 7430326 B2 JP7430326 B2 JP 7430326B2 JP 2020093552 A JP2020093552 A JP 2020093552A JP 2020093552 A JP2020093552 A JP 2020093552A JP 7430326 B2 JP7430326 B2 JP 7430326B2
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- Prior art keywords
- adhesive composition
- mass
- parts
- dental adhesive
- peroxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 135
- 239000003479 dental cement Substances 0.000 title claims description 46
- 230000001070 adhesive effect Effects 0.000 claims description 121
- 239000000853 adhesive Substances 0.000 claims description 119
- 239000000178 monomer Substances 0.000 claims description 88
- 239000000463 material Substances 0.000 claims description 67
- -1 iron arene Chemical class 0.000 claims description 66
- 238000011049 filling Methods 0.000 claims description 61
- 230000002378 acidificating effect Effects 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 150000002978 peroxides Chemical class 0.000 claims description 28
- 239000005749 Copper compound Substances 0.000 claims description 24
- 150000001880 copper compounds Chemical class 0.000 claims description 24
- 150000001451 organic peroxides Chemical class 0.000 claims description 24
- 150000004982 aromatic amines Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000002736 metal compounds Chemical class 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 4
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000003860 storage Methods 0.000 description 27
- 238000001723 curing Methods 0.000 description 22
- 239000003999 initiator Substances 0.000 description 16
- 239000000945 filler Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 5
- 150000001768 cations Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000805 composite resin Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- MMLSWLZTJDJYJH-UHFFFAOYSA-N calcium;propan-2-olate Chemical compound [Ca+2].CC(C)[O-].CC(C)[O-] MMLSWLZTJDJYJH-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- UFKUWSBTKLUIIZ-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu+2].CC(=O)CC(C)=O UFKUWSBTKLUIIZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- AJUXDFHPVZQOGF-UHFFFAOYSA-N n,n-dimethyl-1-naphthylamine Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1 AJUXDFHPVZQOGF-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- MHHDXUNFNAZUGB-UHFFFAOYSA-N oxidovanadium(2+) Chemical compound [V+2]=O MHHDXUNFNAZUGB-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- IMQBFRAZTGRJBA-VOTSOKGWSA-N (E)-4-oxo-4-(2,3,4,5,6-pentamethylphenyl)but-2-enoic acid Chemical compound CC1=C(C)C(C)=C(C(=O)\C=C\C(O)=O)C(C)=C1C IMQBFRAZTGRJBA-VOTSOKGWSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- PHECBGBJCLDCMF-UHFFFAOYSA-L copper;1,10-phenanthroline;dichloride Chemical compound Cl[Cu]Cl.C1=CN=C2C3=NC=CC=C3C=CC2=C1 PHECBGBJCLDCMF-UHFFFAOYSA-L 0.000 description 1
- FQHSBEXCSPGVGY-UHFFFAOYSA-L copper;2-butoxycarbonylbenzoate Chemical compound [Cu+2].CCCCOC(=O)C1=CC=CC=C1C([O-])=O.CCCCOC(=O)C1=CC=CC=C1C([O-])=O FQHSBEXCSPGVGY-UHFFFAOYSA-L 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- CHPMNDHAIUIBSK-UHFFFAOYSA-J copper;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Cu+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O CHPMNDHAIUIBSK-UHFFFAOYSA-J 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 239000011642 cupric gluconate Substances 0.000 description 1
- 235000019856 cupric gluconate Nutrition 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HSUSKWQWIPIFEB-UHFFFAOYSA-L dichlorocopper;propane-1,3-diamine Chemical compound Cl[Cu]Cl.NCCCN.NCCCN HSUSKWQWIPIFEB-UHFFFAOYSA-L 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- DGMJZELBSFOPHH-KVTDHHQDSA-N mannite hexanitrate Chemical compound [O-][N+](=O)OC[C@@H](O[N+]([O-])=O)[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)CO[N+]([O-])=O DGMJZELBSFOPHH-KVTDHHQDSA-N 0.000 description 1
- 229950003934 mannite hexanitrate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- NBFRQCOZERNGEX-UHFFFAOYSA-N n,n,3,5-tetramethylaniline Chemical group CN(C)C1=CC(C)=CC(C)=C1 NBFRQCOZERNGEX-UHFFFAOYSA-N 0.000 description 1
- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
- HKJNHYJTVPWVGV-UHFFFAOYSA-N n,n-diethyl-4-methylaniline Chemical compound CCN(CC)C1=CC=C(C)C=C1 HKJNHYJTVPWVGV-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical class OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- XTXFUQOLBKQKJU-UHFFFAOYSA-N tert-butylperoxy(trimethyl)silane Chemical compound CC(C)(C)OO[Si](C)(C)C XTXFUQOLBKQKJU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Dental Preparations (AREA)
Description
本発明は、充填材料を歯質に接着するための歯科用接着性組成物及び歯科用接着性組成物包装体に関する。 The present invention relates to a dental adhesive composition and a dental adhesive composition package for adhering a filling material to tooth structure.
齲蝕等により損傷を受けた歯牙の修復には、コンポジットレジンと呼ばれる硬化性の充填材料が用いられている。このような充填材料は、歯牙を構成する歯質に対する接着性がほとんど無い。このため、充填材料は、通常、接着材を介して歯質に接着される。一般的な接着材は、高い接着力を得るために、修復対象となる歯牙に塗布された接着材層上に充填された充填材料を硬化させる前に接着材層を予め或る程度硬化させる必要がある。 A hardening filling material called composite resin is used to repair teeth damaged by caries or the like. Such filling materials have almost no adhesion to the tooth structure that constitutes the tooth. For this reason, the filling material is usually bonded to the tooth structure via an adhesive. In order to obtain high adhesive strength with general adhesives, it is necessary to harden the adhesive layer to some extent before hardening the filling material filled on the adhesive layer applied to the tooth to be restored. There is.
コンポジットレジンのような充填材料を歯質に接着するための接着材としては、一般に光照射によって硬化可能な光重合型のボンディング材が使用されることが多く(例えば、特許文献1参照。)、このような光硬化型接着材を使用する場合には、接着材塗布後、充填材充填する前に患者口腔内に光照射器を挿入して数秒から数十秒間光照射して接着材層の硬化を行う必要がある。 As an adhesive for bonding a filling material such as a composite resin to a tooth, a photopolymerizable bonding material that can be cured by light irradiation is often used (see, for example, Patent Document 1). When using such a light-curing adhesive, after applying the adhesive and before filling the patient's mouth, insert a light irradiator into the patient's oral cavity and irradiate it with light for several seconds to several tens of seconds to harden the adhesive layer. It is necessary to perform curing.
ところが、患者によっては上記操作を負担と感じる場合があり、さらに、上記操作中に塗布面を患者の唾液や血液などで汚染させてしまう危険性もある。このような理由から、光照射作業を要さない化学重合型接着材に対する要望もあり、化学重合型のボンディング材も開発されている。 However, some patients may find the above operations burdensome, and furthermore, there is a risk that the application surface may be contaminated with the patient's saliva or blood during the above operations. For these reasons, there is a demand for chemically polymerized adhesives that do not require light irradiation, and chemically polymerized bonding materials have also been developed.
たとえば特許文献2には、「互いに分包された第1剤および第2剤を有し、(A)酸性基含有重合性単量体、(B)硫黄原子含有重合性単量体、(C)シランカップリング剤、(D)ボレート化合物、および、(E)水からなる5成分を少なくとも含み、前記第1剤には、前記5成分のうち、前記(A)酸性基含有重合性単量体および前記(B)硫黄原子含有重合性単量体のみが含まれ、前記第2剤には、前記5成分のうち、前記(C)シランカップリング剤、前記(D)ボレート化合物および前記(E)水のみが含まれることを特徴とする2液型歯科用接着性組成物」からなるボンディング材が記載されている。 For example, Patent Document 2 states, "It has a first agent and a second agent separated from each other, (A) an acidic group-containing polymerizable monomer, (B) a sulfur atom-containing polymerizable monomer, (C ) A silane coupling agent, (D) a borate compound, and (E) water. Among the five components, the second agent contains only the silane coupling agent (C), the borate compound (D), and the (B) sulfur atom-containing polymerizable monomer. E) A two-component dental adhesive composition characterized in that it contains only water.''
また、特許文献3には、特定の修復材専用の1液型の接着材(前処理剤)が開示されている。すなわち、特許文献3には、「(A)a)酸性基含有ラジカル重合性単量体、b)第4周期の遷移金属化合物、及びc)水を含み、且つアミン化合物を含んでいない前処理剤と、(B)d)酸性基を有さないラジカル重合性単量体、e)有機過酸化物、f)光重合開始剤、及びg)シリカ系無機フィラーからなり、該g)シリカ系無機フィラーの含有量がd)酸性基を有さないラジカル重合性単量体100質量部に対して30~900質量部であり、且つアリールボレート化合物を含んでいない充填修復材とからなることを特徴とする歯科用充填修復キット」が記載されている。 Further, Patent Document 3 discloses a one-component adhesive (pretreatment agent) dedicated to a specific restorative material. That is, Patent Document 3 describes "(A) a pretreatment containing a) an acidic group-containing radically polymerizable monomer, b) a fourth period transition metal compound, and c) water and not containing an amine compound". (B) d) a radically polymerizable monomer having no acidic group, e) an organic peroxide, f) a photopolymerization initiator, and g) a silica-based inorganic filler; The content of the inorganic filler is d) 30 to 900 parts by mass based on 100 parts by mass of the radically polymerizable monomer having no acidic group, and the filling repair material does not contain an arylborate compound. ``Dental filling restoration kit with special features'' is described.
特許文献2に開示されるボンディング材は、2液型歯科用接着性組成物からなるものであり、第1剤と第2剤とを治療中に混合する必要があるため、手間及び時間がかかり、操作性の観点からは必ずしも満足のゆくものではない。 The bonding material disclosed in Patent Document 2 is composed of a two-component dental adhesive composition, and the first part and the second part need to be mixed during treatment, which takes time and effort. However, it is not necessarily satisfactory from the viewpoint of operability.
一方、特許文献3に開示される前処理剤は、ボンディング材に相当するものであり、1液型であるため操作性の点では改善がなされているものの、その接着対象は、特定の組成を有する充填修復材に限定されている。 On the other hand, the pretreatment agent disclosed in Patent Document 3 corresponds to a bonding material, and although it is a one-component type and has improved operability, the adhesive target is a bonding material with a specific composition. Limited to filling and restorative materials with
上記の事情に鑑み、本発明の目的は、汎用的な充填材料に適用可能な歯科用接着性組成物であって、充填材料の充填前の段階での光照射による硬化が不要な1液型の歯科用接着性組成物及び歯科用接着性組成物包装体を提供することにある。 In view of the above circumstances, the object of the present invention is to provide a one-component dental adhesive composition that can be applied to general-purpose filling materials, and which does not require curing by light irradiation before filling the filling material. An object of the present invention is to provide a dental adhesive composition and a dental adhesive composition package.
上記目的を達成するため、汎用的な充填材料である光硬化型の充填材料に着目し、当該充填材料に適用可能で且つ充填材料の充填前の段階での光照射による硬化が不要な1液型の歯科用接着性組成物を開発すべく鋭意検討を行った。具体的には、殆どの光硬化型の充填材料には芳香族アミン化合物が配合されているという事実に鑑み、充填材料に含有される芳香族アミン化合物を利用して1液型の化学重合型歯科用接着性組成物とすることを着想し、検討を行った。その結果、芳香族アミン化合物を利用した化学重合開始剤系のみでは十分な硬度を得ることが困難であったものの、特定の光重合開始剤を更に配合して、充填材料硬化時に照射される光の透過光(充填材料層を透過した光)を利用した光重合が起こるようにした場合には、高強度の(歯科用接着性組成物の硬化体からなる)接着層が得られ、高い接着力が得られることを見出し、本発明を完成するに至った。 In order to achieve the above objectives, we focused on a photo-curable filling material, which is a general-purpose filling material, and developed a one-liquid product that is applicable to the filling material and does not require curing by light irradiation before filling. We conducted extensive research to develop a type of dental adhesive composition. Specifically, in light of the fact that most photocurable filling materials contain aromatic amine compounds, we are developing a one-component chemical polymerization method that utilizes aromatic amine compounds contained in filling materials. We came up with the idea of creating a dental adhesive composition and conducted a study. As a result, although it was difficult to obtain sufficient hardness only with a chemical polymerization initiator system that uses aromatic amine compounds, we found that by adding a specific photopolymerization initiator, the light irradiated when the filling material hardens If photopolymerization is caused using transmitted light (light transmitted through the filling material layer), a high-strength adhesive layer (consisting of the cured product of the dental adhesive composition) can be obtained, resulting in high adhesion. The inventors discovered that the present invention was able to obtain sufficient power and completed the present invention.
すなわち、本発明の第一の形態は、芳香族アミンを含有する光硬化型の充填材料を歯質に接着するための1液型の歯科用接着性組成物であって、
1質量部~40質量部の(a1)酸性基含有重合性単量体、を含む100質量部の(A)重合性単量体と、0.05質量部~2質量部の(B)二価の銅化合物と、0.1質量部~10質量部の(c1)有機過酸化物を含む(C)過酸化物と、0.1質量部~10質量部の(D)鉄アレーン錯体と、1質量部~50質量部の(E)水と、10質量部~300質量部の(F)有機溶媒と、を含有し、かつ“(B)二価の銅化合物及び(C)過酸化物との反応によって(A)重合性単量体の重合を開始させる還元剤”を含有しない歯科用接着性組成物である。
That is, the first aspect of the present invention is a one-component dental adhesive composition for adhering a photocurable filling material containing an aromatic amine to tooth structure,
100 parts by mass of (A) polymerizable monomer, including 1 part by mass to 40 parts by mass of (a1) acidic group-containing polymerizable monomer, and 0.05 parts by mass to 2 parts by mass of (B) a (C) peroxide containing 0.1 parts by mass to 10 parts by mass of (c1) organic peroxide, and 0.1 parts by mass to 10 parts by mass of (D) an iron arene complex; , 1 part by mass to 50 parts by mass of (E) water, 10 parts by mass to 300 parts by mass of (F) organic solvent, and "(B) divalent copper compound and (C) peroxide. This is a dental adhesive composition that does not contain a reducing agent that initiates polymerization of (A) the polymerizable monomer by reaction with a substance.
本発明の第一の形態である上記接着性組成物(以下、「本発明の接着性組成物」ともいう。)においては、上記(D)鉄アレーン錯体が、下記式(1) In the adhesive composition of the first embodiment of the present invention (hereinafter also referred to as "adhesive composition of the present invention"), the iron arene complex (D) has the following formula (1):
{式中、ベンゼン環を構成する6個の炭素原子に夫々結合する6個のRは、夫々独立に水素原子又は置換基を有していても良い1価の炭化水素基であり、1価の炭化水素基であるRが複数隣接する場合、相互に隣接するRは互いに結合して前記ベンゼン環と共に縮合芳香族炭化水素環を形成してもよく、X-は、ハロゲン化物イオン、スルホン酸イオン、BF4
-、PF6
-、AsF6
-、SbF6
-、B(C6F5)4
-、又はGa(C6F5)4
-から選ばれるアニオンである。}
で表される鉄アレーン錯体であることが好ましい。
{In the formula, the 6 R's each bonded to the 6 carbon atoms constituting the benzene ring are each independently a hydrogen atom or a monovalent hydrocarbon group which may have a substituent; When a plurality of R's which are hydrocarbon groups are adjacent to each other, the adjacent R's may be bonded to each other to form a condensed aromatic hydrocarbon ring together with the benzene ring, and X - represents a halide ion, a sulfonic acid ion, BF 4 - , PF 6 - , AsF 6 - , SbF 6 - , B(C 6 F 5 ) 4 - , or Ga(C 6 F 5 ) 4 - . }
An iron arene complex represented by is preferable.
また、前記本発明の接着性組成物においては、前記(a1)酸性基含有重合性単量体1molに対して0.01mol~1molの(G)多価金属化合物を更に含有するか、又は10質量部~30質量部の平均一次粒子径が1nm~20nmのヒュームドシリカを更に含有することが好ましく、更に前記(c1)有機過酸化物がパーオキシエステル類を含むことが好ましい。 In addition, the adhesive composition of the present invention further contains 0.01 mol to 1 mol of (G) a polyvalent metal compound per 1 mol of the acidic group-containing polymerizable monomer (a1), or It is preferable to further contain fumed silica having an average primary particle diameter of 1 nm to 20 nm in an amount of 30 parts by weight, and it is further preferable that the organic peroxide (c1) contains peroxy esters.
また、前記本発明の接着性組成物は、α-ジケトンを更に含有する前記光硬化型の充填材料を歯質に接着するための1液型の歯科用接着性組成物であることが好ましい。 Further, the adhesive composition of the present invention is preferably a one-component dental adhesive composition for adhering the photocurable filling material further containing α-diketone to tooth structure.
本発明の第二の形態は、前記本発明の接着性組成物と、当該歯科用接着性組成物を収容する単一の遮光性容器と、を具備する歯科用接着性組成物包装体である。 A second aspect of the present invention is a dental adhesive composition package comprising the adhesive composition of the present invention and a single light-shielding container containing the dental adhesive composition. .
本発明の第三の形態は、前記本発明の接着性組成物と、芳香族アミンを含有する光硬化型の充填材料と、の組み合わせからなる歯牙修復用キットである。 A third aspect of the present invention is a tooth repair kit comprising a combination of the adhesive composition of the present invention and a photocurable filling material containing an aromatic amine.
本発明の歯科用接着性組成物を用いることにより、汎用的な充填材料である芳香族アミンを含有する光硬化型の充填材料を用いて歯牙の修復を行うに際し、患者への負担を少なくしつつ、簡便な操作で確実な修復を行うことが可能となる。すなわち、本発明の歯科用接着性組成物を歯牙に使用した後、充填材料の充填前の段階での光照射器を用いた光硬化作業が不要となるので、従来の光硬化型歯科用接着性組成物を用いた場合と比べて患者への負担が少なく、且つ光照射作業時における塗布面の汚染を防止することができる。さらに、本発明の歯科用接着性組成物1液の状態で安定に保存できるため、2剤に分けて保管する必要がなく、治療時における混合作業を省略することができる。 By using the dental adhesive composition of the present invention, it is possible to reduce the burden on patients when performing tooth restoration using a light-curable filling material containing an aromatic amine, which is a general-purpose filling material. At the same time, it is possible to perform reliable repairs with simple operations. That is, after the dental adhesive composition of the present invention is used on a tooth, there is no need for a light curing operation using a light irradiator before filling with the filling material, so that it is not necessary to perform a light curing operation using a light irradiator. Compared to the case of using a sexual composition, the burden on the patient is less, and contamination of the applied surface during light irradiation work can be prevented. Furthermore, since the dental adhesive composition of the present invention can be stably stored as one liquid, there is no need to store it separately in two parts, and mixing work during treatment can be omitted.
また、上記したように、本発明の歯科用接着性組成物は、1液型の構成において高い保存安定性が得られるため、予め調製された歯科用接着性組成物を単一の遮光性容器に充填した接着性組成物包装体を商品形態とすることができる。 Furthermore, as described above, the dental adhesive composition of the present invention has high storage stability in a one-component configuration, so the dental adhesive composition prepared in advance can be stored in a single light-shielding container. The adhesive composition package filled with the adhesive composition can be made into a commercial product.
以下、本発明の実施するための形態について詳細に説明する。なお、以下の説明において、「X~Y」との数値範囲にはX及びYが含まれるものとし、つまり「X~Y」は「X以上Y以下を意味するものとする。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. In the following description, the numerical range "X to Y" includes X and Y, that is, "X to Y" means "more than or equal to X and less than or equal to Y."
<全体構成>
本発明の一実施形態に係る歯科用接着性組成物(以下、単に接着性組成物と呼称することもある。)は、齲蝕等により損傷を受けた歯牙を修復するために利用可能である。より詳細に、接着性組成物は、歯牙の損傷部に充填される歯科用充填材料(以下、単に充填材料と呼称する。)を、当該損傷部の表面を構成する歯質に接着するために利用可能である。
<Overall configuration>
A dental adhesive composition (hereinafter sometimes simply referred to as an adhesive composition) according to an embodiment of the present invention can be used to repair teeth damaged by caries or the like. More specifically, the adhesive composition is used to bond a dental filling material (hereinafter simply referred to as a filling material) that is filled into a damaged area of a tooth to the tooth structure that constitutes the surface of the damaged area. Available.
多くの一般的な光硬化型の充填材料には、光重合開始剤としてα-ジケトンが含まれ、重合促進剤として芳香族アミンが含まれる。本実施形態に係る接着性組成物を適用可能な接着性組成物は、特殊な構成の充填材料ではなく、このような一般的な光硬化型の充填材料に広く適用可能である。 Many common photocurable filler materials contain α-diketones as photoinitiators and aromatic amines as polymerization accelerators. The adhesive composition to which the adhesive composition according to the present embodiment can be applied is not a filling material with a special configuration, but can be widely applied to such general photocurable filling materials.
本実施形態に係る接着性組成物は、1液型として構成され、1質量部~40質量部の(a1)酸性基含有重合性単量体、を含む100質量部の(A)重合性単量体と、0.05質量部~2質量部の(B)二価の銅化合物と、0.1質量部~10質量部の(c1)有機過酸化物を含む(C)過酸化物と、0.1質量部~10質量部の(D)鉄アレーン錯体と、1質量部~50質量部の(E)水と、10質量部~300質量部の(F)有機溶媒と、を含有し、(B)二価の銅化合物及び(C)過酸化物との反応によって(A)重合性単量体の重合を開始させる還元剤を含有しない。 The adhesive composition according to the present embodiment is configured as a one-component type, and contains 100 parts by mass of (A) polymerizable monomer containing 1 to 40 parts by mass of (a1) acidic group-containing polymerizable monomer. 0.05 parts by mass to 2 parts by mass of (B) a divalent copper compound, and 0.1 parts by mass to 10 parts by mass of (c1) an organic peroxide. , 0.1 parts by mass to 10 parts by mass of (D) an iron arene complex, 1 part by mass to 50 parts by mass of (E) water, and 10 parts by mass to 300 parts by mass of (F) an organic solvent. However, it does not contain a reducing agent that initiates the polymerization of (A) the polymerizable monomer by reaction with (B) the divalent copper compound and (C) the peroxide.
上記(B)二価の銅化合物と上記(C)過酸化物は、使用時において光硬化型の充填材料から拡散等によって供給される芳香族アミンと共に化学重合開始剤を構成するものであり、上記接着性組成物が塗布された歯牙表面(塗布面)上に上記光硬化型の充填材料が配置されると重合硬化が始まるので、充填材料の充填前の段階での光照射を行う必要はない。一方で、本実施形態に係る接着性組成物自体は、還元剤として機能する芳香族アミンを含めて「(B)二価の銅化合物及び(C)過酸化物との反応によって(A)重合性単量体の重合を開始させる還元剤」を含有しないため、全ての成分が混合された状態で保管されても、(A)重合性単量体の化学重合型の硬化が開始することなく、長期間にわたって一定の品質が保持される。つまり、この接着性組成物は、1液型の構成において長期間の高い保存安定性が得られる。 The above (B) divalent copper compound and the above (C) peroxide constitute a chemical polymerization initiator together with an aromatic amine supplied by diffusion etc. from a photocurable filling material during use, When the photocurable filling material is placed on the tooth surface (applied surface) coated with the adhesive composition, polymerization and curing will begin, so there is no need to irradiate the filling material with light before filling. do not have. On the other hand, the adhesive composition itself according to the present embodiment, including the aromatic amine that functions as a reducing agent, undergoes (A) polymerization by reaction with (B) a divalent copper compound and (C) a peroxide. Because it does not contain a "reducing agent that initiates polymerization of polymerizable monomers," even if all components are stored in a mixed state, (A) chemical polymerization type curing of polymerizable monomers will not begin. , constant quality is maintained over a long period of time. In other words, this adhesive composition exhibits high storage stability over a long period of time in a one-component composition.
さらに、前記(D)鉄アレーン錯体は、前記(C)過酸化物として含まれる(c1)有機過酸化物の作用によって少量の光によっても十分な硬化を起こすことができる高活性光重合開始剤として機能するようになり、充填された光硬化型の充填材料を硬化させる際の光、より詳しくは充填材料層を透過した透過光によって光重合型の硬化を実現し、前記化学重合型の硬化を補完して接着性組成物を充分に硬化させることで、高い接着強度の接着層を形成することができる。したがって、このような歯科用接着性組成物では、充填材料の充填前の段階での光照射が不要な1液型の構成を実現することができる。 Furthermore, the iron arene complex (D) is a highly active photopolymerization initiator that can cause sufficient curing even with a small amount of light due to the action of the organic peroxide (c1) contained as the peroxide (C). The photopolymerization type curing is realized by the light used to cure the filled photocurable filling material, more specifically, the transmitted light transmitted through the filling material layer, and the chemical polymerization type curing is achieved. By complementing the above and sufficiently curing the adhesive composition, an adhesive layer with high adhesive strength can be formed. Therefore, such a dental adhesive composition can realize a one-component composition that does not require light irradiation before filling with the filling material.
このような作用機構を、図面を用いて説明すると、図1に示されるように、本実施形態に係る接着性組成物が塗布された歯牙の凹状の損傷部に、接着性組成物を硬化させることなく充填材料が充填される。歯牙の損傷部に接着性組成物を介して充填材料が充填された状態を模式的に示す部分断面図である図1に示す状態では、未硬化の接着性組成物と未硬化の充填材料とが直接接触している。 To explain such an action mechanism using drawings, as shown in FIG. 1, the adhesive composition according to the present embodiment is applied to the concave damaged part of the tooth, and the adhesive composition is hardened. The filling material is filled without any problems. In the state shown in FIG. 1, which is a partial cross-sectional view schematically showing a state in which a damaged part of a tooth is filled with a filling material via an adhesive composition, an uncured adhesive composition and an uncured filling material are mixed together. are in direct contact.
図2A,2Bは、図1に示す状態における接着性組成物と充填材料との間の界面付近を模式的に示す部分断面図である。充填材料が接着性組成物に接触すると、図2Aに示すように充填材料に重合促進剤として含まれる芳香族アミンが接着性組成物に供給される。接着性組成物に供給される芳香族アミンは還元性を有する。 2A and 2B are partial cross-sectional views schematically showing the vicinity of the interface between the adhesive composition and the filler material in the state shown in FIG. 1. FIG. When the filler material contacts the adhesive composition, the aromatic amine contained in the filler material as a polymerization accelerator is supplied to the adhesive composition as shown in FIG. 2A. The aromatic amine supplied to the adhesive composition has reducing properties.
このため、接着性組成物では、(C)過酸化物を酸化剤とし、芳香族アミンを還元剤とする酸化還元反応が発生する。つまり、この接着性組成物では、芳香族アミンが(C)過酸化物とともに重合開始剤(レドックス開始剤)として機能する。これにより、接着性組成物では、(A)重合性単量体の化学重合型の硬化が進行する。 Therefore, in the adhesive composition, an oxidation-reduction reaction occurs in which the peroxide (C) is used as an oxidizing agent and the aromatic amine is used as a reducing agent. That is, in this adhesive composition, the aromatic amine functions as a polymerization initiator (redox initiator) together with (C) peroxide. As a result, in the adhesive composition, chemical polymerization type curing of the polymerizable monomer (A) progresses.
また、図1に示す状態から充填材料の硬化のために光照射が行われると、図2Bに示すように、充填材料を透過した照射光の一部が接着性組成物に入射する。これにより、接着性組成物では、(D)鉄アレーン錯体と(c1)有機過酸化物とによって構成される光重合開始剤の作用によって(A)重合性単量体の光重合型の硬化が進行する。 Further, when light irradiation is performed to cure the filling material from the state shown in FIG. 1, a part of the irradiation light that has passed through the filling material enters the adhesive composition, as shown in FIG. 2B. As a result, in the adhesive composition, the photopolymerization type curing of the (A) polymerizable monomer is effected by the action of the photopolymerization initiator composed of (D) the iron arene complex and (c1) the organic peroxide. proceed.
このように、本実施形態に係る接着性組成物では、(A)重合性単量体の化学重合型の硬化と光重合型の硬化とを同時に進行させることができる。したがって、この接着性組成物では、(A)重合性単量体を迅速かつ充分に硬化させることができるため、患者への負担を抑えつつ高い接着強度の接着層が得られる。 In this way, in the adhesive composition according to the present embodiment, chemical polymerization type curing and photopolymerization type curing of the polymerizable monomer (A) can proceed simultaneously. Therefore, in this adhesive composition, since the polymerizable monomer (A) can be cured quickly and sufficiently, an adhesive layer with high adhesive strength can be obtained while suppressing the burden on the patient.
<詳細構成>
[(A)重合性単量体]
本実施形態に係る接着性組成物は、必須成分として重合性単量体(モノマー)、すなわち分子内に少なくとも1つの重合性不飽和基を有する化合物を含む。重合性不飽和基としては、(メタ)アクリロイル基、(メタ)アクリロキシ基(メタ)アクリロイルアミノ基、(メタ)アクリロイルチオ基等の(メタ)アクリロイル系基、ビニル基、アリル基、スチリル基等のラジカル重合性基を挙げることができるが、重合性及び生体への安全性の観点から特に(メタ)アクリロキシ基を有する(メタ)アクリル酸エステル系のラジカル重合性単量体を使用することが好適である。モノマー成分は1種類のモノマーのみからなっていても複数種類のモノマーの混合物からなっていても良い。
<Detailed configuration>
[(A) Polymerizable monomer]
The adhesive composition according to the present embodiment contains a polymerizable monomer (monomer), that is, a compound having at least one polymerizable unsaturated group in the molecule, as an essential component. Examples of polymerizable unsaturated groups include (meth)acryloyl groups, (meth)acryloyl groups, (meth)acryloxy groups, (meth)acryloylamino groups, (meth)acryloylthio groups, vinyl groups, allyl groups, styryl groups, etc. However, from the viewpoint of polymerizability and safety to living organisms, it is particularly preferable to use (meth)acrylic acid ester-based radically polymerizable monomers having a (meth)acryloxy group. suitable. The monomer component may consist of only one type of monomer or a mixture of multiple types of monomers.
本実施形態に係る接着性組成物におけるモノマーは、歯質脱灰性を有するようにするために(a1)酸性基含有重合性単量体(酸性モノマー)を含む必要がある。また、(a2)酸性基非含有重合性単量体(以下、「非酸性モノマー」ともいう。)を含むことが好ましい。以下に、酸性モノマー及び非酸性モノマーについて詳しく説明する。 The monomer in the adhesive composition according to this embodiment needs to contain (a1) an acidic group-containing polymerizable monomer (acidic monomer) in order to have tooth demineralizing properties. Moreover, it is preferable to include (a2) a polymerizable monomer containing no acidic group (hereinafter also referred to as "non-acidic monomer"). Acidic monomers and non-acidic monomers will be explained in detail below.
(a1)酸性基含有重合性単量体(酸性モノマー)
酸性モノマーとは、分子内に、カルボキシル基(-COOH)、スルホ基(-SO3H)、ホスフィニコ基{=P(=O)OH}、ホスホノ基{-P(=O)(OH)2}、酸無水物基{-C(=O)-O-C(=O)-}、酸ハロゲン化物基{-C(=O)X、但しXはハロゲン原子を表す。}等の酸性基を有する重合性単量体であり、歯質、卑金属材料及び金属酸化物材料に対する接着性を高める機能を有する。酸性モノマーは、水を含む場合の水に対する安定性が高く、歯面のスメアー層の溶解や歯牙脱灰を緩やかに実施できると言う理由から酸性基としてカルボキシル基(-COOH)、酸無水物基{-C(=O)-O-C(=O)-}、ホスフィニコ基{=P(=O)OH}及びホスホノ基{-P(=O)(OH)2}からなる群より選ばれる少なくとも1種の基を有する重合性単量体からなることが好ましい。効果の観点から、酸性モノマーは、リン酸二水素モノエステル系{基:-O-P(=O)(OH)2}を有する。}、リン酸水素ジエステル系{基:(-O-)2P(=O)OHを有する。}又はカルボン酸系(基:-COOHを有する。)、の(メタ)アクリレートであることが特に好ましい。
(a1) Acidic group-containing polymerizable monomer (acidic monomer)
Acidic monomers include carboxyl group (-COOH), sulfo group (-SO 3 H), phosphinico group {=P(=O)OH}, phosphono group {-P(=O)(OH) 2 in the molecule. }, acid anhydride group {-C(=O)-OC(=O)-}, acid halide group {-C(=O)X, where X represents a halogen atom. It is a polymerizable monomer having an acidic group such as }, and has the function of increasing adhesiveness to teeth, base metal materials, and metal oxide materials. Acidic monomers have high stability against water when they contain water, and are capable of dissolving the smear layer on the tooth surface and gently demineralizing teeth. selected from the group consisting of {-C(=O)-OC(=O)-}, phosphinico group {=P(=O)OH} and phosphono group {-P(=O)(OH) 2 } It is preferable to consist of a polymerizable monomer having at least one type of group. From the point of view of effectiveness, the acidic monomer has a dihydrogen phosphate monoester system {group: -OP(=O)(OH) 2 }. }, hydrogen phosphate diester system {having group: (-O-) 2 P(=O)OH. } or carboxylic acid type (having group: -COOH), (meth)acrylates are particularly preferred.
好適に使用できる酸性モノマーを具体的に例示すれは、リン酸二水素モノエステル系及びリン酸水素ジエステル系のもとして、2-(メタ)アクリロキシエチルジハイドロジェンホスフェート、ビス[2-(メタ)アクリロキシエチル]ハイドロジェンホスフェート、2-(メタ)アクリロキシエチルフェニルハイドロジェンホスフェート、6-(メタ)アクリロキシヘキシルジハイドロジェンホスフェート、6-(メタ)アクリロキシヘキシルフェニルハイドロジェンホスフェート、10-(メタ)アクリロキシデシルジハイドロジェンホスフェート、1,3-ジ(メタ)アクリロイルプロパン-2-ジハイドロジェンホスフェート、1,3-ジ(メタ)アクリロイルプロパン-2-フェニルハイドロジェンホスフェート、ビス[5-{2-(メタ)アクリロキシエトキシカルボニル}ヘプチル]ハイドロジェンホスフェート等を、カルボン酸系のものとして、アクリル酸、メタクリル酸、4-(メタ)アクリロキシエチルトリメリット酸、11-(メタ)アクリロキシ1,1-ウンデカンジカルボン酸、1,4-ジ(メタ)アクリロキシピロメリット酸、2-(メタ)アクリロキシエチルマレイン酸、2-(メタ)アクリロキシエチルフタル酸、2-(メタ)アクリロキシエチルヘキサヒドロフタル酸等を挙げることができる。 Specific examples of acidic monomers that can be suitably used include 2-(meth)acryloxyethyl dihydrogen phosphate, bis[2-(meth) ) acryloxyethyl] hydrogen phosphate, 2-(meth)acryloxyethylphenyl hydrogen phosphate, 6-(meth)acryloxyhexyl dihydrogen phosphate, 6-(meth)acryloxyhexylphenyl hydrogen phosphate, 10- (meth)acryloxydecyl dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-phenylhydrogen phosphate, bis[5 -{2-(meth)acryloxyethoxycarbonyl}heptyl] hydrogen phosphate, etc., as carboxylic acid type, acrylic acid, methacrylic acid, 4-(meth)acryloxyethyl trimellitic acid, 11-(meth) Acryloxy 1,1-undecanedicarboxylic acid, 1,4-di(meth)acryloxypyromellitic acid, 2-(meth)acryloxyethylmaleic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth) Examples include acryloxyethylhexahydrophthalic acid.
また、本実施形態に係る接着性組成物においては、(A)重合性単量体を100質量部としたとき、(a1)酸性基含有重合性単量体の配合割合を1質量部~40質量部とし、5質量部~30質量部とすることが好ましく、10質量部~20質量部とすることがより好ましい。これにより、接着性組成物では、歯質に対する十分な接着強度、及び高い接着耐久性が得られやすくなる。 Furthermore, in the adhesive composition according to the present embodiment, when (A) the polymerizable monomer is 100 parts by mass, the blending ratio of (a1) the acidic group-containing polymerizable monomer is 1 part by mass to 40 parts by mass. It is preferably 5 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 20 parts by mass. As a result, the adhesive composition tends to have sufficient adhesive strength and high adhesive durability to the tooth.
(a2)酸性基非含有重合性単量体(非酸性モノマー)
非酸性モノマーは、接着層の構成成分となるばかりでなく、多官能重合性の非酸性モノマーによってコンポジットレジン等のラジカル重合性単量体を含む歯科材料との接着性を高めると共に接着層内に架橋構造を導入して強度を高め、延いては耐久接着性をより高める機能を有する。非酸性モノマーは、酸性モノマー以外のモノマーであれば特に限定されず、従来の歯科用接着性組成物で使用される非酸性モノマーが特に制限なく使用できる。
(a2) Acidic group-free polymerizable monomer (non-acidic monomer)
The non-acidic monomer not only serves as a constituent component of the adhesive layer, but also increases the adhesion with dental materials containing radically polymerizable monomers such as composite resin by using the polyfunctional polymerizable non-acidic monomer. It has the function of introducing a crosslinked structure to increase strength and, in turn, further enhance durable adhesiveness. The non-acidic monomer is not particularly limited as long as it is a monomer other than acidic monomers, and non-acidic monomers used in conventional dental adhesive compositions can be used without particular limitation.
好適に使用できる非酸性モノマーを例示すれば、メチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、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、2,2-ビス(メタクリロイルオキシポリエトキシフェニル)プロパン、2-ヒドロキシエチルメタクリレート、2,2,4-トリメチルヘキサメチレンビス(2-カルバモイルオキシエチル)ジメタクリレート、1,10-デカンジオールジ(メタ)アクリレート等を挙げことができる。 Examples of non-acidic monomers that can be suitably used include methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. Acrylate, 2,2-bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(methacryloyloxypolyethoxyphenyl)propane, 2-hydroxyethyl methacrylate, 2,2,4 -trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate, 1,10-decanediol di(meth)acrylate, and the like.
非酸性モノマーは、1種類のみを用いてもよく、2種類以上を組み合わせて用いてもよい。非酸性モノマー含有量は、酸性モノマーの含有量の残部であり、酸性モノマーの含有量に応じて自動的に決定される。 Only one type of non-acidic monomer may be used, or two or more types may be used in combination. The non-acidic monomer content is the remainder of the acidic monomer content and is automatically determined depending on the acidic monomer content.
[(B)二価の銅化合物]
(B)二価の銅化合物は、(C)過酸化物と充填材料に含まれる芳香族アミンとのレドックス反応を促進する作用を有する。別言すれば、前記3成分で構成されるレドックス型の化学重合開始剤の一成分である。したがって、接着性組成物では、(B)二価の銅化合物を必須の構成要素として含むことにより、化学重合型の硬化が促進されるため、充分な硬化が得られやすくなる。
[(B) Divalent copper compound]
(B) The divalent copper compound has the effect of promoting the redox reaction between the (C) peroxide and the aromatic amine contained in the filling material. In other words, it is one component of a redox type chemical polymerization initiator composed of the three components mentioned above. Therefore, in the adhesive composition, by including the divalent copper compound (B) as an essential component, chemical polymerization type curing is promoted, so that sufficient curing is easily obtained.
(B)二価の銅化合物は、水和物であっても無水物であってもよい。好適に使用できる二価の銅化合物を例示すれば、塩化銅(II)、硫酸銅(II)五水和物、硝酸銅(II)、トリフルオロメタン硫酸銅(II)、酢酸銅(II)一水和物、アセチルアセトン銅(II)、ナフテン酸銅(II)、サリチル酸銅(II)、安息香酸銅(II)、メタクリル酸銅(II)、フタル酸ブチル銅(II)、グルコン酸銅(II)、ジクロロ(1,10-フェナントロリン)銅(II)、エチレンジアミン四酢酸銅(II)二ナトリウム四水和物、ジメチルジチオカルバミン酸銅(II)、ジエチルチオカルバミン酸銅(II)、ヘキサフルオロアセチルアセトナト銅(II)、ビス(1,3-プロパンジアミン)銅(II)ジクロリド、ビス(8-キノリノラト)銅(II)、等を挙げることができる。これら二価の銅化合物は1種類のみを用いてもよく、2種類以上を組み合わせて用いてもよい。 (B) The divalent copper compound may be a hydrate or an anhydride. Examples of divalent copper compounds that can be suitably used include copper(II) chloride, copper(II) sulfate pentahydrate, copper(II) nitrate, copper(II) trifluoromethane sulfate, and copper(II) acetate. Hydrate, copper(II) acetylacetone, copper(II) naphthenate, copper(II) salicylate, copper(II) benzoate, copper(II) methacrylate, copper(II) butyl phthalate, copper(II) gluconate ), dichloro(1,10-phenanthroline) copper(II), ethylenediaminetetraacetic acid copper(II) disodium tetrahydrate, dimethyldithiocarbamate copper(II), diethylthiocarbamate copper(II), hexafluoroacetylacetate Examples include natocopper(II), bis(1,3-propanediamine)copper(II) dichloride, bis(8-quinolinolato)copper(II), and the like. These divalent copper compounds may be used alone or in combination of two or more.
(B)二価の銅化合物の配合割合は、(A)重合性単量体100質量部に対して、0.05質量部~2質量部とし、0.1質量部~1質量部とすることが好ましい。配合割合が0.05質量部以上では、特に高い接着性が得られる。配合割合が2質量部以下では、優れた保存安定性が得られやすくなる。 (B) The blending ratio of the divalent copper compound is 0.05 parts by mass to 2 parts by mass, and 0.1 parts by mass to 1 part by mass, based on 100 parts by mass of (A) polymerizable monomer. It is preferable. Particularly high adhesiveness can be obtained when the blending ratio is 0.05 parts by mass or more. When the blending ratio is 2 parts by mass or less, excellent storage stability is likely to be obtained.
[(C)過酸化物]
本実施形態に係る接着性組成物に含まれる過酸化物(C)は、(c1)有機過酸化物を含む必要がある。また、当該過酸化物(C)は、必要に応じ、(c2)無機過酸化物を更に含んでいてもよい。(c1)有機過酸化物及び/又は(c2)無機過酸化物は前記3成分得構成されるレドックス型の化学重合開始剤の酸化剤成分として機能し、(c1)有機過酸化物は、(D)鉄アレーン錯体との組み合わせにより光重合開始剤として機能する。
[(C) Peroxide]
The peroxide (C) contained in the adhesive composition according to this embodiment needs to contain (c1) an organic peroxide. Moreover, the peroxide (C) may further contain (c2) an inorganic peroxide, if necessary. (c1) organic peroxide and/or (c2) inorganic peroxide function as an oxidizing agent component of a redox type chemical polymerization initiator composed of the three components, D) Functions as a photopolymerization initiator in combination with an iron arene complex.
(c1)有機過酸化物
有機過酸化物の配合割合は、(A)重合性単量体100質量部に対して、0.1質量部~10質量部とし、0.5質量部~5質量部とすることが好ましい。この範囲を満足することにより、高い重合活性と、高い保存安定性を発揮することができる。有機過酸化物としては公知の化合物が制限なく使用できるが、代表的には、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリールパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネートを挙げることができる。上記の有機過酸化物の具体例としては、次のようなものが挙げられる。
(c1) Organic peroxide The blending ratio of the organic peroxide is 0.1 parts by mass to 10 parts by mass, and 0.5 parts by mass to 5 parts by mass, based on 100 parts by mass of (A) polymerizable monomer. It is preferable to set it as part. By satisfying this range, high polymerization activity and high storage stability can be exhibited. As the organic peroxide, any known compound can be used without restriction, but typically ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate are used. can be mentioned. Specific examples of the above organic peroxides include the following.
ケトンパーオキサイド類としては、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、アセチルアセトンパーオキサイド等が挙げられる。 Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
パーオキシケタール類としては、1,1-ビス(t-ヘキシルパーオキシ)3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ヘキシルパーオキシ)シクロヘキサン、1,1-ビス(t-ブチルパーオキシ)3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロドデカン、2,2-ビス(t-ブチルパーオキシ)ブタン、n-ブチル 4,4-ビス(t-ブチルパーオキシ)バレレート、2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパンが挙げられる。 Peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t- butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 2,2-bis(t- butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.
ハイドロパーオキサイド類としては、P-メンタンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、t-ヘキシルハイドロパーオキサイド、t-ブチルハイドロパーオキサイドが挙げられる。ジアルキルパーオキサイドとしては、α,α-ビス(t-ブチルパーオキシ)ジイソプロピルベンゼン、ジクミルパーオキサイド、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン、t-ブチルクミルパーオキサイド、ジ-t-ブチルパーオキサイド、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキシン-3等が挙げられる。 Hydroperoxides include P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl Examples include hydroperoxide. Examples of dialkyl peroxides include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumylbenzene. Examples include luperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, and the like.
ジアシルパーオキサイド類としては、イソブチリルパーオキサイド、2,4-ジクロロベンゾイルパーオキサイド、3,5,5-トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアリルパーオキサイド、スクシニックアシッドパーオキサイド、m-トルオイルベンゾイルパーオキサイド、ベンゾイルパーオキサイド等が挙げられる。 Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and succinic acid peroxide. oxide, m-toluoylbenzoyl peroxide, benzoyl peroxide and the like.
パーオキシジカーボネート類としては、ジ-n-プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、ジ-2-エトキシエチルパーオキシジカーボネート、ジー2-エチルヘキシルパーオキシジカーボネート、ジ-2-メトキシブチルパーオキシジカーボネート、ジ(3-メチル-3-メトキシブチル)パーオキシジカーボネート等が挙げられる。 Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and di-2-ethoxyethyl peroxydicarbonate. Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutyl)peroxydicarbonate.
パーオキシエステル類としては、α,α-ビス(ネオデカノイルパーオキシ)ジイソプロピルベンゼン、クミルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、1-シクロヘキシル-1-メチルエチルパーオキシネオデカノエート、t-ヘキシルパーオキシネオデカノエート、t-ブチルパーオキシネオデカノエート、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、2,5-ジメチル-2,5-ビス(2-エチルヘキサノイルパーオキシ)ヘキサン、1-シクロヘキシル-1-メチルエチルパーオキシ-2-エチルヘキサノエート、t-ヘキシルパーオキシ2-エチルヘキサノエート、t-ブチルパーオキシ2-エチルヘキサノエート、t-ブチルパーオキシイソブチレート、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシマレイックアシッド、t-ブチルパーオキシ3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート、2,5-ジメチル-2,5-ビス(m-トルオイルパーオキシ)ヘキサン、t-ブチルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシ2-エチルヘキシルモノカーボネート、t-ヘキシルパーオキシベンゾエート、2,5-ジメチル-2,5-ビス(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシアセテート、t-ブチルパーオキシ-m-トルオイルベンゾエート、t-ブチルパーオキシベンゾエート、ビス(t-ブチルパーオキシ)イソフタレート等が挙げられる。 Peroxy esters include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1 , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl mono carbonate, t-butyl peroxymaleic acid, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis(m-tol) oil peroxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane , t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, and the like.
なお、これら以外にもt-ブチルトリメチルシリルパーオキサイド、3,3’,4,4’-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン等が好適に使用できる。(c1)有機過酸化物としては、これら有機過酸化物を、1種類のみを用いてもよく、2種以上を組み合わせて使用してもよいが、保存安定性の点からパーオキシエステル類を使用するのが特に好ましい。 In addition to these, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. can be suitably used. (c1) As the organic peroxide, these organic peroxides may be used alone or in combination of two or more types, but from the viewpoint of storage stability, peroxyesters are used. Particularly preferred is the use of
(c2)無機過酸化物
)無機過酸化物としては公知の化合物が制限なく使用できるが、代表的には、過炭酸塩、ペルオキソ二硫酸化合物、過リン酸塩、過酸化カルシウム、過酸化マグネシウムを挙げることができる。中でも、水分を多く含む環境下での重合活性の高さの観点から、ペルオキソ二硫酸化合物が好ましい。具体的には、アンモニウム塩、ナトリウム塩、カリウム塩などのペルオキソ二硫酸化合物などが挙げられ、特に、水溶性が高いことからペルオキソ二硫酸ナトリウムやペルオキソ二硫酸アンモニウムが好ましく、入手の容易性も考慮するとペルオキソ二硫酸ナトリウムが最適である。これら無機過酸化物は、単独で又は2種以上を混合して用いてもかまわない。
(c2) Inorganic peroxide) Known compounds can be used without restriction as inorganic peroxides, but typically percarbonates, peroxodisulfate compounds, perphosphates, calcium peroxide, magnesium peroxide can be mentioned. Among these, peroxodisulfuric acid compounds are preferred from the viewpoint of high polymerization activity in an environment containing a large amount of water. Specifically, peroxodisulfate compounds such as ammonium salts, sodium salts, and potassium salts are mentioned, and sodium peroxodisulfate and ammonium peroxodisulfate are particularly preferred because of their high water solubility, and considering their ease of availability. Sodium peroxodisulfate is most suitable. These inorganic peroxides may be used alone or in combination of two or more.
本実施形態に係る接着性組成物が(c2)無機過酸化物を含む場合における、当該無機過酸化物の配合量は、通常(A)重合性単量体100質量部に対して通常0.01質量部~5質量部であり、好ましくは0.05質量部~2質量部である。 When the adhesive composition according to the present embodiment contains (c2) an inorganic peroxide, the amount of the inorganic peroxide is usually 0. The amount is 0.01 parts by mass to 5 parts by mass, preferably 0.05 parts by mass to 2 parts by mass.
[(D)鉄アレーン錯体]
(D)鉄アレーン錯体は、前記(c1)有機過酸化物と共に光重合開始剤を構成する。すなわち、(D)鉄アレーン錯体は、光照射によって光を吸収し、鉄原子上の配位子が、(c1)有機過酸化物と交換することで該有機化酸化物が活性化され、重合開始種が発生する。
[(D) Iron arene complex]
(D) The iron arene complex constitutes a photopolymerization initiator together with the organic peroxide (c1). That is, (D) iron arene complex absorbs light by light irradiation, and the ligand on the iron atom is exchanged with (c1) organic peroxide, thereby activating the organic peroxide and polymerizing it. A starting species occurs.
(D)鉄アレーン錯体は、光を吸収し、配位子が交換するものであれば公知の鉄アレーン錯体が特に制限無く利用できるが、配位子交換能が高く、前記(c1)有機過酸化物と併用したときの光重合活性が高いと言う理由から、下記一般式(1)で示される鉄アレーン錯体を使用することが好ましい。このような鉄アレーン錯体を用いることにより光重合型の硬化が促進され、延いては接着強度が向上する。 As the iron arene complex (D), any known iron arene complex can be used without particular limitation as long as it absorbs light and exchanges ligands. It is preferable to use an iron arene complex represented by the following general formula (1) because it has high photopolymerization activity when used in combination with an oxide. By using such an iron arene complex, photopolymerizable curing is promoted and adhesive strength is improved.
上記一般式(1)式中において、ベンゼン環を構成する6個の炭素原子に夫々結合する6個のRは、夫々独立に水素原子又は置換基を有していても良い1価の炭化水素基を表す。なお、ベンゼン環に1価の炭化水素基であるRが複数隣接して結合する場合、相互に隣接するRは互いに結合して前記ベンゼン環と共に縮合芳香族炭化水素環を形成してもよい。また、上記式中のアニオンを表すX-は、ハロゲン化物イオン、スルホン酸イオン、BF4 -、PF6 -、AsF6 -、SbF6 -、B(C6F5)4 -、又はGa(C6F5)4 -である。 In the above general formula (1), the six R's each bonded to the six carbon atoms constituting the benzene ring are each independently a hydrogen atom or a monovalent hydrocarbon which may have a substituent. represents a group. In addition, when a plurality of monovalent hydrocarbon groups R are bonded adjacent to a benzene ring, the mutually adjacent R may be bonded to each other to form a condensed aromatic hydrocarbon ring together with the benzene ring. Furthermore, X − representing an anion in the above formula is a halide ion, sulfonate ion, BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , B(C 6 F 5 ) 4 − , or Ga( C 6 F 5 ) 4 - .
前記Rが、互い結合して縮環構造を形成しない場合の1価の炭化水素基としては、炭素数1~20、特に炭素数1~8のアルキル基、炭素数3~20、特に炭素数1~8のシクロアルキル基、炭素数2~20、特に炭素数2~8のアルケニル基、炭素数2~20、特に炭素数2~8のアルキニル基、芳香環を構成する炭素数が6~18、特に6~14のアリール基等を挙げる事ができる。これら基のうち、好適な基を具体的に例示すれば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、イソプロピル基、イソブチル基、1-メチルプロピル基、2-エチルヘキシル基等のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基;ビニル基、2-メチルビニル基、ブタジエン-1-イル基、ブタジエン-2-イル基、シクロヘキセン-3-イル基等のアルケニル基;エチニル基、プロピン-1-イル基、1-ブチン-1-イル基等のアルキニル基;フェニル基、ナフタレン-1-イル基、ナフタレン-2-イル基、アントラセン-9-イル基等のアリール基を挙げることができる。 When the R's do not combine with each other to form a condensed ring structure, the monovalent hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms, especially 1 to 8 carbon atoms, and an alkyl group having 3 to 20 carbon atoms, especially 1 to 8 carbon atoms. Cycloalkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 20 carbon atoms, especially 2 to 8 carbon atoms, alkynyl group having 2 to 20 carbon atoms, especially 2 to 8 carbon atoms, 6 to 8 carbon atoms constituting an aromatic ring. Examples include 18, especially 6 to 14 aryl groups. Among these groups, specific examples of suitable groups include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, isopropyl group, isobutyl group, 1-methylpropyl group, 2-ethylhexyl group. Alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; Vinyl group, 2-methylvinyl group, butadien-1-yl group, butadien-2-yl group, cyclohexene-3- alkenyl groups such as yl group; alkynyl groups such as ethynyl group, propyn-1-yl group, 1-butyn-1-yl group; phenyl group, naphthalen-1-yl group, naphthalen-2-yl group, anthracene-9 Examples include aryl groups such as -yl group.
なお、上記1価の炭化水素基及び相互に隣接するRは互いに結合して前記ベンゼン環と共に縮合芳香族炭化水素環を形成する場合における縮合環は、置換基を有していても良い。好適な置換基としては、メトキシ基、エトキシ基等のアルコキシ基;アセチル基;プロピオニル基等のアシル基;アセトキシ基、プロピオニルオキシ基等のアシルオキシ基;フッ素原子、塩素原子等のハロゲン原子;等を挙げることができる。また、置換基を有する場合の置換基の数は、1~6であり、特に1又は2であることが好ましい。 In addition, when the monovalent hydrocarbon group and the mutually adjacent R's are bonded to each other to form a condensed aromatic hydrocarbon ring together with the benzene ring, the condensed ring may have a substituent. Suitable substituents include alkoxy groups such as methoxy and ethoxy groups; acetyl groups; acyl groups such as propionyl groups; acyloxy groups such as acetoxy and propionyloxy groups; halogen atoms such as fluorine atoms and chlorine atoms; can be mentioned. Further, the number of substituents in the case of having substituents is 1 to 6, and particularly preferably 1 or 2.
また、重合性単量体中への溶解度の観点から、上記式(1)中のX-は、BF4 -、PF6 -、AsF6 -、SbF6 -、B(C6F5)4 -、又はGa(C6F5)4 -であることが好ましい。 Furthermore, from the viewpoint of solubility in the polymerizable monomer, X in the above formula (1) is BF 4 - , PF 6 - , AsF 6 - , SbF 6 - , B(C 6 F 5 ) 4 - or Ga(C 6 F 5 ) 4 - is preferable.
以下に、特に好適に使用される(D)鉄アレーン錯体を示す。 The iron arene complexes (D) that are particularly preferably used are shown below.
上記に示す通り、カチオン部としては、(η6-ベンゼン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-トルエン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-クメン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-アントラセン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-ナフタレン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-フェナントレン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオン、(η6-ピレン)(η5-シクロペンタジエン-1-イル)鉄(II)」カチオンであることが好ましい。 As shown above, the cation moiety includes (η 6 -benzene)(η 5 -cyclopentadien-1-yl)iron(II) cation, (η 6 -toluene)(η 5 -cyclopentadien-1-yl) ) Iron (II) cation, (η 6 -cumene) (η 5 -cyclopentadien-1-yl) iron (II) cation, (η 6 -anthracene) (η 5 -cyclopentadien-1-yl) iron (II)" cation, (η 6 -naphthalene)(η 5 -cyclopentadien-1-yl)iron(II)" cation, (η 6 -phenanthrene)(η 5 -cyclopentadien-1-yl)iron(II) )" cation, and (η 6 -pyrene)(η 5 -cyclopentadien-1-yl)iron(II)" cation are preferred.
これらの中でも(c1)有機過酸化物と共存してもより安定に保存でき、硬化後の着色も少ないと言う理由から、下記式で示される(η6-クメン)(η5-シクロペンタジエン-1-イル)鉄(II)ヘキサフルオロフォスフェートを使用することが最も好ましい。 Among these, (c1) (η 6 -cumene) (η 5 -cyclopentadiene- Most preferably, iron(II) hexafluorophosphate is used.
(D)鉄アレーン錯体の配合量は、(A)重合性単量体100質量部に対して0.1~10質量部とし、より好ましくは0.5~8質量部とすることが好ましい。この範囲を満足することにより、高い重合活性、接着性を発揮することができる。また、これら鉄アレーン錯体は2種以上のものを併用しても良い。 The amount of the iron arene complex (D) to be blended is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the polymerizable monomer (A). By satisfying this range, high polymerization activity and adhesive properties can be exhibited. Moreover, two or more types of these iron arene complexes may be used in combination.
[(E)水]
(E)水としては、貯蔵安定性、生体適合性及び接着性の観点で有害な不純物を実質的に含まない事が好ましく、例としては脱イオン水、蒸留水等が利用できる。(E)水の配合割合は、(A)重合性単量体100質量部に対して、1質量部~50質量部とし、2質量部~30質量部とすることが好ましく、5質量部~20質量部とすることが特に好ましい。
[(E) Water]
(E) Water is preferably substantially free of harmful impurities from the viewpoints of storage stability, biocompatibility, and adhesiveness, and examples of water that can be used include deionized water and distilled water. (E) The mixing ratio of water is 1 part by mass to 50 parts by mass, preferably 2 parts to 30 parts by mass, and 5 parts by mass to 100 parts by mass of (A) polymerizable monomer. It is particularly preferable to use 20 parts by mass.
[(F)有機溶媒]
(F)有機溶媒としては、公知の有機溶媒であればいずれも制限無く用いることができるが、通常は、沸点が100℃未満の揮発性の高い有機溶媒を用いることが好ましい。(F)有機溶媒の配合割合は、(A)重合性単量体100質量部に対して、10質量部~300質量部とし、30質量部~200質量部とすることが好ましい。
[(F) Organic solvent]
(F) As the organic solvent, any known organic solvent can be used without restriction, but it is usually preferable to use a highly volatile organic solvent with a boiling point of less than 100°C. The blending ratio of the organic solvent (F) is 10 parts by mass to 300 parts by mass, preferably 30 parts by mass to 200 parts by mass, based on 100 parts by mass of the polymerizable monomer (A).
具体的に、(F)有機溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール等のアルコール類;アセトン、メチルエチルケトン等のケトン類;エチルエーテル、1,4-ジオキサン、テトラヒドロフラン等のエーテル類;酢酸エチル、蟻酸エチル等のエステル類;トルエン、キシレン、ベンゼン等の芳香族系溶媒;ペンタン、ヘキサン、ヘプタン、オクタン等のハイドロカーボン系溶媒;塩化メチレン、クロロホルム、1,2-ジクロロエタン等の塩素系溶媒;トリフルオロエタノール等のフッ素系溶媒等が挙げられる。これらの中でも、溶解性及び保存安定性等の理由で、アセトン、エタノール、イソプロピルアルコール等が特に好ましく使用される。(F)有機溶媒としては、1種又は2種以上の有機溶媒を組み合わせて使用することもできる。 Specifically, (F) organic solvents include, for example, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, 1,4-dioxane, and tetrahydrofuran; Esters such as ethyl acetate and ethyl formate; Aromatic solvents such as toluene, xylene, and benzene; Hydrocarbon solvents such as pentane, hexane, heptane, and octane; Chlorine solvents such as methylene chloride, chloroform, and 1,2-dichloroethane Solvent: Examples include fluorine-based solvents such as trifluoroethanol. Among these, acetone, ethanol, isopropyl alcohol and the like are particularly preferably used for reasons such as solubility and storage stability. (F) As the organic solvent, one type or a combination of two or more types of organic solvents can be used.
[還元剤]
本実施形態に係る接着性組成物は、“(B)二価の銅化合物及び(C)過酸化物との反応によって(A)重合性単量体の重合を開始させる還元剤”を含有しない。このような還元剤を含む場合には、1液型としたときに十分な保存安定性を得ることができない。なお、ここで「含まない」とは積極的に配合しないという意味であり、前記した各必須成分が還元剤となる物質を不純物や微量添加剤として含む等の理由により、不可避的に混入することは許容される。但し、この場合においても還元剤の(総)含有量は(A)重合性単量体100質量部に対して、0.1質量部以下である必要があり、0.01質量部以下、特に0.001質量部以下とすることが好ましい。
[Reducing agent]
The adhesive composition according to the present embodiment does not contain "a reducing agent that initiates polymerization of (A) polymerizable monomer by reaction with (B) divalent copper compound and (C) peroxide". . If such a reducing agent is included, sufficient storage stability cannot be obtained when a one-component product is used. Note that "does not contain" here means that it is not actively blended, and does not mean that each of the above-mentioned essential components is unavoidably mixed due to reasons such as containing substances that act as reducing agents as impurities or trace additives. is allowed. However, even in this case, the (total) content of the reducing agent needs to be 0.1 parts by mass or less, especially 0.01 parts by mass or less, based on 100 parts by mass of the (A) polymerizable monomer. The amount is preferably 0.001 parts by mass or less.
本実施形態に係る接着性組成物に含まれない上記還元剤としては、4-ジメチルアミノ安息香酸エチル、N,N-ジメチル-p-トルイジン等の芳香族アミン化合物;テトラフェニルホウ素のトリエタノールアミン塩等のアリールボレート化合物;p-トルエンスルフィン酸ナトリウム等のスルフィン酸化合物;ベンゾイルチオ尿素等のチオ尿素化合物;ビス(マルトラート)オキソバナジウム(IV)等の(B)二価の銅化合物及び(D)鉄アレーン錯体以外の第4周期遷移金属化合物等を挙げることができる。 Examples of the reducing agent not included in the adhesive composition according to the present embodiment include aromatic amine compounds such as ethyl 4-dimethylaminobenzoate and N,N-dimethyl-p-toluidine; triethanolamine of tetraphenylboron; Arylborate compounds such as salts; sulfinic acid compounds such as sodium p-toluenesulfinate; thiourea compounds such as benzoylthiourea; (B) divalent copper compounds such as bis(maltolate)oxovanadium (IV); ) Examples include fourth period transition metal compounds other than iron arene complexes.
[その他の成分]
本実施形態に係る接着性組成物は、必要に応じて、上記の成分以外の各種添加剤などの成分を含んでいてもよい。添加剤としては、例えば、(G)前記(D)以外の光重合開始剤(その他光重合開始剤)、(H)多価金属化合物、(I)フィラー、着色剤、ヒドロキノン、ヒ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の重合禁止剤などが挙げられる。
[Other ingredients]
The adhesive composition according to the present embodiment may contain components such as various additives other than the above-mentioned components, as necessary. Examples of additives include (G) a photopolymerization initiator other than the above (D) (other photoinitiators), (H) a polyvalent metal compound, (I) a filler, a colorant, hydroquinone, hydroquinone monomethyl ether, Examples include polymerization inhibitors such as dibutylhydroxytoluene.
(G)その他の光重合開始剤
前記(D)以外のその他の光重合開始剤としては、例えば、カンファーキノンなどのα-ジケトン類、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイドなどのアシルホスフィンオキサイド類、ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイドなどのビスアシルフォスフィンオキサイド類等が挙げられる。
(G) Other photopolymerization initiators Examples of photopolymerization initiators other than the above (D) include α-diketones such as camphorquinone, and acylphosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. and bisacylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.
ただし、還元剤として酸化剤と反応する芳香族アミン類、アリールボレート化合物類等は保存安定性の観点から含まない。 However, aromatic amines, arylborate compounds, etc. that react with oxidizing agents as reducing agents are not included from the viewpoint of storage stability.
(H)多価金属化合物
接着性組成物では、(H)多価金属化合物を配合するのが、接着性及び保存安定性の観点から好ましい。(H)多価金属化合物が(a1)酸性基含有重合性単量体と架橋することによって、より高い接着強度の接着層が得られる。また、接着性組成物では、(H)多価金属化合物を予め(a1)酸性基含有重合性単量体と架橋させることで、保管時に(a1)酸性基含有重合性単量体と(B)二価の銅化合物との架橋が生じにくくなる。したがって、接着性組成物では、(a1)酸性基含有重合性単量体と(B)二価の銅化合物との架橋により生成される銅化合物の析出が抑えられる。これにより、この接着性組成物では、保管時における銅化合物の析出による接着強度の低下を抑制することができる。(H)多価金属化合物の配合割合は、(a1)酸性基含有重合性単量体1molに対して、0.01mol~1molとすることが好ましい。
(H) Polyvalent Metal Compound In the adhesive composition, it is preferable to incorporate (H) a polyvalent metal compound from the viewpoint of adhesiveness and storage stability. By crosslinking the polyvalent metal compound (H) with the acidic group-containing polymerizable monomer (a1), an adhesive layer with higher adhesive strength can be obtained. In addition, in the adhesive composition, by crosslinking (H) the polyvalent metal compound with (a1) the acidic group-containing polymerizable monomer in advance, the (a1) acidic group-containing polymerizable monomer and (B ) Crosslinking with divalent copper compounds is less likely to occur. Therefore, in the adhesive composition, precipitation of the copper compound produced by crosslinking between (a1) the acidic group-containing polymerizable monomer and (B) the divalent copper compound is suppressed. Thereby, this adhesive composition can suppress a decrease in adhesive strength due to precipitation of copper compounds during storage. The blending ratio of the polyvalent metal compound (H) is preferably 0.01 mol to 1 mol per mol of the acidic group-containing polymerizable monomer (a1).
(H)多価金属化合物としては、第4周期の遷移金属以外の、(a1)酸性基含有重合性単量体と架橋可能な2価以上の金属化合物のことであり、代表的なものを例示すれば、カルシウム、ストロンチウム、バリウム、アルミニウム、ランタン、ランタノイド等の金属化合物である。(B)二価の銅化合物及び(D)鉄アレーン錯体以外の第4周期の遷移金属は、(C)過酸化物と酸化還元反応が生じる可能性があるため含まない。また、(H)多価金属化合物は、多価金属アルコキシド、多価金属フッ化物、多価金属炭酸塩、多価金属水酸化物、多価金属水素化物、及びアルキル多価金属から選択される少なくとも1種類の化合物である。 (H) The polyvalent metal compound refers to a divalent or higher valent metal compound that can crosslink with (a1) the acidic group-containing polymerizable monomer, other than the fourth period transition metal. Examples include metal compounds such as calcium, strontium, barium, aluminum, lanthanum, and lanthanoids. Transition metals of the fourth period other than (B) divalent copper compounds and (D) iron arene complexes are not included because they may undergo redox reactions with (C) peroxides. (H) The polyvalent metal compound is selected from polyvalent metal alkoxides, polyvalent metal fluorides, polyvalent metal carbonates, polyvalent metal hydroxides, polyvalent metal hydrides, and alkyl polyvalent metals. At least one type of compound.
(H)多価金属化合物としては、保存安定性が高く、より接着強度に優れることから、上記の中でも特に多価金属アルコキシドが含まれること好ましい。 (H) As the polyvalent metal compound, it is particularly preferable to include a polyvalent metal alkoxide among the above because it has high storage stability and excellent adhesive strength.
多価金属アルコキシドにおける有機基としては、特に制限はなく、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ペンチル、ヘキシル、シクロヘキシル、ヘプチル、2-エチルヘキシル、オクチル等が挙げられ、中でも、炭素数4以下のアルキル基が好ましい。 The organic group in the polyvalent metal alkoxide is not particularly limited and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, octyl, etc. Among them, carbon An alkyl group having a number of 4 or less is preferable.
多価金属アルコキシドの具体的な化合物としては、例えば、マグネシウムジエトキシド、カルシウムジイソプロポキシド、バリウムジイソプロポキシド、アルミニウムトリエトキシド、アルミニウムトリイソプロポキシド、ランタントリイソプロポキシド、ジルコニウムテトライソプロポキシド等が挙げられ、前記多価金属フッ化物の具体的な化合物としては、例えば、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化アルミニウム、フッ化ジルコニウム等が挙げられ、前記多価金属炭酸塩の具体的な化合物としては、例えば、炭酸カルシウム、炭酸バリウム、炭酸アルミニウム、炭酸ジルコニウム等が挙げられ、前記多価金属水素化物の具体的な化合物としては、例えば、水素化カルシウム、水素化アルミニウム、水素化ジルコニウム等が挙げられ、前記アルキル多価金属の具体的な化合物としては、例えば、ジエチルマグネシウム、トリメチルアルミニウム等が挙げられる。 Specific compounds of polyvalent metal alkoxides include, for example, magnesium diethoxide, calcium diisopropoxide, barium diisopropoxide, aluminum triethoxide, aluminum triisopropoxide, lanthanum triisopropoxide, and zirconium tetra. Specific compounds of the polyvalent metal fluoride include magnesium fluoride, calcium fluoride, barium fluoride, aluminum fluoride, zirconium fluoride, etc. Specific compounds of the polyvalent metal carbonate include, for example, calcium carbonate, barium carbonate, aluminum carbonate, zirconium carbonate, etc. Specific compounds of the polyvalent metal hydride include, for example, calcium hydride, Examples include aluminum hydride and zirconium hydride. Specific examples of the alkyl polyvalent metal include diethylmagnesium, trimethylaluminum, and the like.
上記のアルキル多価金属におけるアルキル基としては、特に制限はなく、例えば、炭素数1~20のアルキル基が挙げられる。 The alkyl group in the above-mentioned alkyl polyvalent metal is not particularly limited, and includes, for example, an alkyl group having 1 to 20 carbon atoms.
なお、上記の多価金属化合物は、1種単独で用いてもよく、2種以上を併用してもよい。 In addition, the above-mentioned polyvalent metal compounds may be used alone or in combination of two or more.
また、(B)多価金属化合物を構成する金属元素としては、第4周期の遷移金属以外であれば、特に制限はなく、周期律表の第2族~第13族の金属元素が挙げられるが、接着性、保存安定性に優れることから、中でも、カルシウムが特に好ましい。 Furthermore, the metal elements constituting the polyvalent metal compound (B) are not particularly limited as long as they are other than transition metals in period 4, and include metal elements in groups 2 to 13 of the periodic table. Among them, calcium is particularly preferred because it has excellent adhesive properties and storage stability.
(I)フィラー
(I)フィラーは、接着性組成物を硬化して得られる接着層における機械的強度や操作性を向上させるために配合される。(I)フィラーとしては、特に制限はなく、公知の無機フィラー、有機フィラー、無機-有機複合フィラーを用いることができる。
(I) Filler (I) Filler is blended to improve the mechanical strength and operability of the adhesive layer obtained by curing the adhesive composition. The filler (I) is not particularly limited, and known inorganic fillers, organic fillers, and inorganic-organic composite fillers can be used.
接着性組成物は、無機フィラーとしてヒュームドシリカを含むことが好ましい。これにより、硬化後に高い接着強度の接着層が得られる。ヒュームドシリカの平均一次粒子径は1nm~20nmであることが好ましい。このように、接着性組成物では、平均一次粒子径が小さいヒュームドシリカを用いることにより、添加量を多くしてもヒュームドシリカが沈降しにくくなる。したがって、接着性組成物では、ヒュームドシリカの添加量を多くすることによって、更に接着強度の高い接着層を形成することが可能となる。ヒュームドシリカの配合割合は、(A)重合性単量体100質量部に対して、10質量部~30質量部とすることが好ましい。 Preferably, the adhesive composition contains fumed silica as an inorganic filler. This provides an adhesive layer with high adhesive strength after curing. The average primary particle diameter of fumed silica is preferably 1 nm to 20 nm. Thus, in the adhesive composition, by using fumed silica having a small average primary particle diameter, the fumed silica becomes difficult to settle even if the amount added is increased. Therefore, in the adhesive composition, by increasing the amount of fumed silica added, it becomes possible to form an adhesive layer with even higher adhesive strength. The blending ratio of fumed silica is preferably 10 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A).
この他、接着性組成物は、有機フィラーとして、例えば、ポリメチル(メタ)アクリレート、ポリエチル(メタ)アクリレート、メチル(メタ)アクリレート・エチル(メタ)アクリレート共重合体、メチル(メタ)アクリレート・ブチル(メタ)アクリレート共重合体、メチル(メタ)アクリレート・スチレン共重合体等の非架橋性ポリマー、又は、メチル(メタ)アクリレート・エチレングリコールジ(メタ)アクリレート共重合体、メチル(メタ)アクリレート・トリエチレングリコールジ(メタ)アクリレート共重合体、(メタ)アクリル酸メチルとブタジエン系単量体との共重合体等の(メタ)アクリレート重合体などを含んでいてもよい。 In addition, the adhesive composition may contain organic fillers such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, methyl (meth)acrylate/ethyl (meth)acrylate copolymer, methyl (meth)acrylate/butyl ( Non-crosslinkable polymers such as meth)acrylate copolymer, methyl(meth)acrylate/styrene copolymer, or methyl(meth)acrylate/ethylene glycol di(meth)acrylate copolymer, methyl(meth)acrylate/tri It may also contain (meth)acrylate polymers such as ethylene glycol di(meth)acrylate copolymers and copolymers of methyl (meth)acrylate and butadiene monomers.
無機フィラーとしては、例えば、石英、無定形シリカ、シリカジルコニア、クレー、酸化アルミニウム、タルク、雲母、カオリン、ガラス、硫酸バリウム、酸化ジルコニウム、酸化チタン、窒化ケイ素、窒化アルミニウム、窒化チタン、炭化ケイ素、炭化ホウ素、炭酸カルシウム、ヒドロキシアパタイト、リン酸カルシウム等が挙げられる。 Examples of inorganic fillers include quartz, amorphous silica, silica zirconia, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon carbide, Examples include boron carbide, calcium carbonate, hydroxyapatite, calcium phosphate, and the like.
更に、これら無機フィラーは、表面処理することが好ましい。これにより、重合性単量体とのなじみをよくし、機械的強度や耐水性を向上させることが容易になる。表面処理の方法は公知の方法で行えばよく、表面処理剤としては、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、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリアセトキシシラン、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-メタクリロイルオキシプロピルトリス(β-メトキシエトキシ)シラン、γ-クロロプロピルトリメトキシシラン、γ-クロロプロピルメチルジメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、ヘキサメチルジシラザン等が好適に用いられる。 Furthermore, these inorganic fillers are preferably surface-treated. This improves compatibility with the polymerizable monomer and makes it easy to improve mechanical strength and water resistance. The surface treatment may be performed by a known method, and examples of the surface treatment agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris(β-methoxyethoxy)silane, γ-chloropropyltrimethoxysilane, γ -Chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-amino Propyltrimethoxysilane, hexamethyldisilazane, etc. are preferably used.
(I)フィラーとしては、上記で挙げた物質を、単独で使用してもよく、2種類以上を組み合わせて使用してもよい。 As the filler (I), the substances listed above may be used alone or in combination of two or more.
[適用対象物となる充填材料]
本実施形態に係る接着性組成物は、前記したように接着対象物となる光硬化型充填材料中に含まれる芳香族アミンを利用して硬化する。汎用的な光硬化型充填材料は、通常、芳香族アミンを含有しているため、本実施形態に係る接着性組成物は、汎用的な光硬化型充填材料に対して適用可能なものとなっている。なお、このような光硬化型充填材料は、通常、重合性単量体成及び光重合触媒を必須成分として含み、更に、光重合開始剤の成分等として芳香族アミンを含んでいる。例えば、市販されている光硬化型のコンポジットレジンの多くがこのような充填材に該当し、本実施形態に係る接着性組成物は、このような光硬化型充填材料に対して使用でき、前記したような効果を発揮する。
[Applicable filling material]
As described above, the adhesive composition according to this embodiment is cured using the aromatic amine contained in the photocurable filler material to be bonded. Since general-purpose photocurable filling materials usually contain aromatic amines, the adhesive composition according to the present embodiment can be applied to general-purpose photocurable filling materials. ing. Note that such a photocurable filling material usually contains a polymerizable monomer and a photopolymerization catalyst as essential components, and further contains an aromatic amine as a component of a photopolymerization initiator. For example, many commercially available photocurable composite resins correspond to such fillers, and the adhesive composition according to the present embodiment can be used for such photocurable fillers, and the adhesive composition according to the present embodiment can be used for such photocurable fillers. It exerts a similar effect.
なお、前記光硬化型充填材料中に含まれる重合性単量体成分としては、組成が若干異なる点を除いて含有される具体的な重合性単量体は前記(A)重合性単量体と同様である。また、光硬化型充填材料中に含まれる芳香族アミンとしては、芳香族第三級アミンとしては、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-ジメチル-m-トルイジン、N,N-ジヒドロキシエチル-p-トルイジン、N,N-ジメチル-3,5-キシリジン等のトルイジン系芳香族第三級アミン類;N,N-ジメチルアニリン、N,N-ジエチルアニリン、N,N-ジ-n-ブチルアニリン、N,N-ジベンジルアニリン、p-ブロモ-N,N-ジメチルアニリン、m-クロロ-N,N-ジメチルアニリン、N,N-ジヒドロキシエチルアニリン等のアニリン系芳香族第三級アミン類;p-ジメチルアミノベンズアルデヒド、p-ジメチルアミノアセトフェノン、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エステル、p-ジメチルアミノ安息香酸アミルエステル、N,N-ジメチルアンスラニリックアシッドメチルエステル等の芳香族環にカルボニル基が結合した芳香族第三級アミン類;、p-ジメチルアミノフェネチルアルコール、p-ジメチルアミノスチルベン、4-ジメチルアミノピリジン、N,N-ジメチル-α-ナフチルアミン、N,N-ジメチル-α-ナフチルアミン等を挙げることができる。 As for the polymerizable monomer component contained in the photocurable filling material, the specific polymerizable monomers contained are the above (A) polymerizable monomers, except that the composition is slightly different. It is similar to Further, as aromatic amines contained in the photocurable filling material, examples of aromatic tertiary amines include N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N- Toluidine aromatic tertiary amines such as dimethyl-m-toluidine, N,N-dihydroxyethyl-p-toluidine, N,N-dimethyl-3,5-xylidine; N,N-dimethylaniline, N,N -diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, N,N-dihydroxy Aniline aromatic tertiary amines such as ethylaniline; p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester , Aromatic tertiary amines in which a carbonyl group is bonded to an aromatic ring such as N,N-dimethylanthranilic acid methyl ester; p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, 4-dimethylaminopyridine , N,N-dimethyl-α-naphthylamine, N,N-dimethyl-α-naphthylamine, and the like.
また、光硬化型充填材料中に含まれる芳香族アミンの量は特に制限されず、芳香族アミンを光重合開始剤の成分として含む光硬化型充填材料に通常含まれる量と特に変わる点は無く、通常は、重合性単量体成分100質量部に対して、0.01~10質量部の範囲である。 Further, the amount of aromatic amine contained in the photocurable filling material is not particularly limited, and there is no particular difference from the amount normally contained in a photocurable filling material containing aromatic amine as a component of the photopolymerization initiator. , usually in the range of 0.01 to 10 parts by weight per 100 parts by weight of the polymerizable monomer component.
本実施形態に係る接着性組成物を適用する充填材料は、光重合開始剤としてα-ジケトンを更に含有していることが好ましい。α-ジケトンは、本実施形態に係る接着性組成物に含まれる(D)鉄アレーン錯体と光の吸収波長が若干ずれている。このため、α-ジケトンを含有する充填材料では、照射光のうち(D)鉄アレーン錯体の吸収波長の光がα-ジケトンに吸収されずに透過されやすくなる。これにより、接着性組成物では、光重合型の硬化が促進される。 The filling material to which the adhesive composition according to the present embodiment is applied preferably further contains α-diketone as a photopolymerization initiator. The light absorption wavelength of α-diketone is slightly different from that of the iron arene complex (D) contained in the adhesive composition according to the present embodiment. Therefore, in a filling material containing α-diketone, among the irradiated light, light having the absorption wavelength of the iron arene complex (D) is easily transmitted without being absorbed by the α-diketone. This promotes photopolymerizable curing of the adhesive composition.
[歯科用接着性組成物包装体]
本実施形態に係る歯科用接着性組成物包装体(以下、単に接着性組成物包装体と呼称する。)は、本実施形態に係る接着性組成物包装体の商品形態であり、歯科用接着性組成物と、当該歯科用接着性組成物を収容する単一の遮光性容器と、を有する。上記のとおり、歯科用接着性組成物は、1液型の構成において高い保存安定性が得られる。このため、予め調製された当該歯科用接着性組成物を単一の遮光容器に充填した接着性組成物包装体を商品形態とすることができる。
[Dental adhesive composition package]
The dental adhesive composition package according to the present embodiment (hereinafter simply referred to as adhesive composition package) is a product form of the adhesive composition package according to the present embodiment, and is a dental adhesive composition package according to the present embodiment. and a single light-shielding container containing the dental adhesive composition. As mentioned above, the dental adhesive composition has high storage stability in a one-component composition. Therefore, an adhesive composition package in which a single light-shielding container is filled with the dental adhesive composition prepared in advance can be made into a commercial product.
このような接着性組成物包装体は、必要に応じて箱詰め等の二次的な包装を行った上で、流通過程を製造場所から歯科医院等の最終的なユーザーサイドまで輸送され、使用時まで保管しても内部の歯科用接着性組成物を安定に保つことができる。接着性組成物包装体に用いる遮光容器としては、歯科用接着性組成物に含まれる光重合開始剤を活性化する光を遮蔽できるものであれば特に限定されないが、使用感、気密性の観点から、ポリエチレン、ポリプロピレン、ポリビニルアルコール、エチレン-ビニルアルコール共重合体等の合成樹脂で形成された容器であることが好ましい。 Such adhesive composition packages are transported through the distribution process from the manufacturing site to the final user site, such as a dental clinic, after performing secondary packaging such as boxing as necessary. The dental adhesive composition inside can be kept stable even if stored for up to 20 days. The light-shielding container used for the adhesive composition package is not particularly limited as long as it can block light that activates the photopolymerization initiator contained in the dental adhesive composition, but from the viewpoint of usability and airtightness. Therefore, the container is preferably made of a synthetic resin such as polyethylene, polypropylene, polyvinyl alcohol, or ethylene-vinyl alcohol copolymer.
以下に本発明を、実施例を挙げて説明するが、本発明はこれらの例に何ら限定されるものでは無い。 The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.
1.物質の略称
まず、以下に、実施例及び比較例において使用した物質の略称について説明する。
1. Abbreviations of Substances First, the abbreviations of substances used in Examples and Comparative Examples will be explained below.
1-1.(A)重合性単量体
・(a1)酸性基含有重合性単量体
MDP:10-メタクリルオキシデシルジハイドロジェンホスフェート
SPM:2-メタクリロイルオキシエチルジハイドロジェンホスフェート及びビス(2-メタクリロイルオキシエチル)ハイドロジェンホスフェートをモル比1:1の割合で混合した混合物
・(a2)酸性基非含有重合性単量体
BisGMA:2.2’ ―ビス[4―(2―ヒドロキシ―3―メタクリルオキシプロポキシ)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
HEMA:2―ヒドロキシエチルメタクリレート。
1-1. (A) Polymerizable monomer (a1) Acidic group-containing polymerizable monomer MDP: 10-methacryloxydecyl dihydrogen phosphate SPM: 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl ) A mixture of hydrogen phosphate at a molar ratio of 1:1 ・(a2) Acidic group-free polymerizable monomer BisGMA: 2.2'-bis[4-(2-hydroxy-3-methacryloxypropoxy) ) phenyl]propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate.
1-2.(B)二価の銅化合物
CuA:酢酸銅(II)一水和物
CuAA:アセチルアセトン銅(II)。
1-2. (B) Divalent copper compound CuA: Copper (II) acetate monohydrate CuAA: Copper (II) acetylacetone.
1-3.(C)過酸化物
・(c1)有機過酸化物
BPT:t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート
BPB:t-ブチルパーオキシベンゾエート
BPE:t-ブチルパーオキシ-2-エチルヘキシルモノカーボネート
TMBHP:1,1,3,3-テトラメチルブチルハイドロパーオキサイド
・(c2)無機過酸化物
NPS;ペルオキソ二硫酸ナトリウム。
1-3. (C) Peroxide ・(c1) Organic peroxide BPT: t-butylperoxy-3,5,5-trimethylhexanoate BPB: t-butylperoxybenzoate BPE: t-butylperoxy-2- Ethylhexyl monocarbonate TMBHP: 1,1,3,3-tetramethylbutyl hydroperoxide (c2) Inorganic peroxide NPS: Sodium peroxodisulfate.
1-4.(D)鉄アレーン錯体
CFeP:(η6-クメン)(η5-シクロペンタジエン-1-イル)鉄(II)ヘキサフルオロフォスフェート。CFePの構造を以下に示す。
1-4. (D) Iron arene complex CFeP: (η 6 -cumene) (η 5 -cyclopentadien-1-yl) iron(II) hexafluorophosphate. The structure of CFeP is shown below.
1-4.(G)その他の光重合開始剤
CQ:カンファーキノン。
1-4. (G) Other photopolymerization initiators CQ: Camphorquinone.
1-5.(H)多価金属化合物
AlPO:アルミニウムトリイソプロポキシド
CaPO:カルシウムジイソプロポキシド。
1-5. (H) Polyvalent metal compound AlPO: aluminum triisopropoxide CaPO: calcium diisopropoxide.
1-5.(I)フィラー
・ヒュームドシリカ
DM-30:平均一次粒子径7nm、表面処理剤:ジメチルジクロロシラン(株式会杜トクヤマ製)
DM-20:平均一次粒子径12nm、表面処理剤:ジメチルジクロロシラン(株式会杜トクヤマ製)。
1-5. (I) Filler - Fumed silica DM-30: average primary particle diameter 7 nm, surface treatment agent: dimethyldichlorosilane (manufactured by Mori Tokuyama Co., Ltd.)
DM-20: average primary particle diameter 12 nm, surface treatment agent: dimethyldichlorosilane (manufactured by Mori Tokuyama Co., Ltd.).
1-5.上記以外の成分
BMOV:オキソバナジウム(IV)ビス(マルトラート)
DMBE:4-ジメチルアミノ安息香酸エチル
BHT:ジブチルヒドロキシトルエン。
1-5. Ingredients other than the above BMOV: Oxovanadium (IV) bis(maltrate)
DMBE: Ethyl 4-dimethylaminobenzoate BHT: Dibutylhydroxytoluene.
<実施例1~24、比較例1~9>
(接着性組成物の作製)
実施例1~24及び比較例1~9に係る接着性組成物を作製した。各接着性組成物の成分及び配合割合は、下記の表1及び2に示すとおりである。表1には実施例1~24について示し、表2には比較例1~9について示している。なお、下記の表1及び2における括弧内の数値は、(A)重合性単量体100質量部に対する各成分の質量部を示している。
<Examples 1 to 24, Comparative Examples 1 to 9>
(Preparation of adhesive composition)
Adhesive compositions according to Examples 1 to 24 and Comparative Examples 1 to 9 were prepared. The components and blending ratios of each adhesive composition are as shown in Tables 1 and 2 below. Table 1 shows Examples 1 to 24, and Table 2 shows Comparative Examples 1 to 9. The numerical values in parentheses in Tables 1 and 2 below indicate parts by mass of each component based on 100 parts by mass of the polymerizable monomer (A).
次に、得られた接着性組成物を以下に示す「接着強度評価」に従い接着性を評価した。
また、以下に示す「長期保管後の外観評価」に従い保存安定性を評価した。
Next, the adhesiveness of the obtained adhesive composition was evaluated according to the "adhesive strength evaluation" shown below.
In addition, storage stability was evaluated according to "Appearance evaluation after long-term storage" shown below.
(接着強度評価)
抜去した牛前歯を、注水下、耐水研磨紙P600で研磨し、象質平面を削り出した被着体を準備した。
(Adhesive strength evaluation)
The extracted bovine front tooth was polished with water-resistant abrasive paper P600 under water injection to prepare an adherend in which the dentin plane was shaved.
その後、被着体の研磨面に、直径3mmの穴を開けた両面テープを貼り付けた。続いて、研磨面のうち両面テープの穴から露出している接着面に各実施例、及び各比較例の接着性組成物をそれぞれマイクロブラシで塗布し、接着面に塗布された接着性組成物を5秒間エアブローすることにより乾燥させた。 Thereafter, double-sided tape with a hole of 3 mm in diameter was attached to the polished surface of the adherend. Subsequently, the adhesive compositions of each example and each comparative example were applied with a microbrush to the adhesive surface exposed through the holes of the double-sided tape on the polished surface, and the adhesive composition applied to the adhesive surface was was dried by air blowing for 5 seconds.
直径8mmの穴が設けられた厚み0.5mmのパラフィンワックスを、パラフィンワックスの穴と、両面テープの穴とが同心円となるように接着性組成物が塗布された接着面に貼り付けて模擬窩洞を作製した。この模擬窩洞に歯科用コンポジットレジン(エステライトΣクイック、トクヤマデンタル社製)を充填してポリエステルフィルムで軽く圧接した後、可視光線照射器(エリパーLED光重合器、3M ESPE社製)を用い、光照射10秒による光硬化を行った。その後、あらかじめ研磨したSUS304製丸棒(直径8mm、高さ18mm)をレジンセメント(ビスタイトII、トクヤマデンタル社製)で接着した。最後に、37℃の水中にて24時間浸漬することで接着強度測定用のサンプルを得た。なお、使用したコンポジットレジン(エステライトΣクイック)は、カンファーキノン及び芳香族アミン化合物を含む光重合性の組成物である。 A simulated cavity was created by pasting 0.5 mm thick paraffin wax with a hole of 8 mm in diameter onto the adhesive surface coated with the adhesive composition so that the hole in the paraffin wax and the hole in the double-sided tape were concentric. was created. This simulated cavity was filled with a dental composite resin (Esterite ΣQuick, manufactured by Tokuyama Dental Co., Ltd.) and lightly pressed with a polyester film. Photocuring was performed by irradiating light for 10 seconds. Thereafter, a previously polished SUS304 round bar (diameter 8 mm, height 18 mm) was adhered with resin cement (Vistite II, manufactured by Tokuyama Dental Co., Ltd.). Finally, a sample for adhesive strength measurement was obtained by immersing it in water at 37° C. for 24 hours. The composite resin (Esterite ΣQuick) used is a photopolymerizable composition containing camphorquinone and an aromatic amine compound.
これら接着強度測定用のサンプルについて、島津製作所製オートグラフ(クロスヘッドスピード2mm/分)を用いて引張接着強度を測定した。各実施例及び比較例について、4個のサンプルの測定値を平均し、測定結果とした。 The tensile adhesive strength of these samples for adhesive strength measurement was measured using an Autograph manufactured by Shimadzu Corporation (crosshead speed: 2 mm/min). For each Example and Comparative Example, the measured values of four samples were averaged to obtain the measurement results.
接着面に対して調製直後の接着性組成物を塗布することにより得られたサンプル(初期の接着強度測定用サンプル)の接着強度(初期の接着強度)の測定結果、接着面に対して調製後に更に50℃の恒温槽中で3週間保管した後の接着性組成物を塗布することにより得られたサンプル(保管後の接着強度接着強度測定用サンプル)の接着強度(保管後の接着強度)の測定結果を下記の表3及び4に示す。 Measurement results of the adhesive strength (initial adhesive strength) of the sample (sample for initial adhesive strength measurement) obtained by applying the adhesive composition immediately after preparation to the adhesive surface, Furthermore, the adhesive strength (adhesive strength after storage) of the sample obtained by applying the adhesive composition after storage in a constant temperature bath at 50°C for 3 weeks (sample for measuring adhesive strength after storage) The measurement results are shown in Tables 3 and 4 below.
なお、後述する長期保管後の外観評価においてゲル化していた場合は、接着面への接着性組成物の塗布が困難となったため、長期保管後接着強度の評価は省略した。 Note that if gelation was found in the appearance evaluation after long-term storage, which will be described later, it became difficult to apply the adhesive composition to the adhesive surface, so evaluation of adhesive strength after long-term storage was omitted.
(長期保管後の外観評価)
表1及び2に示す各実施例及び各比較例の接着性組成物を調製した後に容器内に密封し、更に50℃の恒温槽中で3週間保管した。続いて、恒温槽から取り出した接着性組成物の外観を目視観察し、保管前後における変化の有無やゲル化などの変性について評価した。結果を下記の表3及び表4に示す。
(Appearance evaluation after long-term storage)
After the adhesive compositions of each Example and each Comparative Example shown in Tables 1 and 2 were prepared, they were sealed in a container and further stored in a constant temperature bath at 50° C. for 3 weeks. Subsequently, the appearance of the adhesive composition taken out from the thermostatic bath was visually observed, and the presence or absence of changes before and after storage and deterioration such as gelation were evaluated. The results are shown in Tables 3 and 4 below.
(表3,4に示す評価結果ついて)
表3に示す実施例1~24は1液型基本歯科用接着性組成物を用いたものである。いずれの場合においても、接着試験結果は初期、保管後共に良好であった。また、保管後の外観変化においても大きな変化は確認されなかった。
(Regarding the evaluation results shown in Tables 3 and 4)
Examples 1 to 24 shown in Table 3 used a one-component basic dental adhesive composition. In either case, the adhesion test results were good both initially and after storage. Furthermore, no major changes in appearance were observed after storage.
一方、表4に示す比較例1~5の接着性組成物はそれぞれ(a1)酸性基含有重合性単量体、(B)二価の銅化合物、(c1)有機過酸化物、(D)鉄アレーン錯体、(E)水を含まないため、十分な接着強度は得られなかったと考えられる。また、比較例6及び7は(B)二価の銅化合物または、(D)鉄アレーン錯体の添加量が少ないため、添加の効果が十分に生じず、良好な接着強度は得られなかったと考えられる。 On the other hand, the adhesive compositions of Comparative Examples 1 to 5 shown in Table 4 each contained (a1) an acidic group-containing polymerizable monomer, (B) a divalent copper compound, (c1) an organic peroxide, and (D) It is thought that sufficient adhesive strength could not be obtained because the iron arene complex (E) did not contain water. In addition, in Comparative Examples 6 and 7, since the amount of (B) divalent copper compound or (D) iron arene complex added was small, the effect of addition was not sufficiently produced, and it is thought that good adhesive strength could not be obtained. It will be done.
比較例8は過酸化物と酸化還元反応する芳香族アミンが含まれるため、保管後ゲル化が生じた。また、初期接着評価においても、光重合開始剤として機能する、(D)鉄アレーン錯体を含まず、(G)その他の光重合開始剤のみであるため、十分な接着強度は得られなかったと考えられる。比較例9は過酸化物と酸化還元反応する第4周期の遷移金属化合物が含まれるため、保存安定性が悪く、接着性組成物調製中にゲル化が生じたため、接着評価を実施できなかった。 Comparative Example 8 contained an aromatic amine that undergoes a redox reaction with peroxide, so gelation occurred after storage. In addition, in the initial adhesion evaluation, it was thought that sufficient adhesive strength could not be obtained because (D) iron arene complex, which functions as a photopolymerization initiator, was not included, and only (G) other photopolymerization initiators were used. It will be done. Comparative Example 9 contained a fourth period transition metal compound that undergoes a redox reaction with peroxide, so it had poor storage stability and gelation occurred during the preparation of the adhesive composition, so it was not possible to conduct an adhesion evaluation. .
Claims (8)
1質量部~40質量部の(a1)酸性基含有重合性単量体、を含む100質量部の(A)重合性単量体と、
0.05質量部~2質量部の(B)二価の銅化合物と、
0.1質量部~10質量部の(c1)有機過酸化物を含む(C)過酸化物と、
0.1質量部~10質量部の(D)鉄アレーン錯体と、
1質量部~50質量部の(E)水と、
10質量部~300質量部の(F)有機溶媒と、
を含有し、かつ
“(B)二価の銅化合物及び(C)過酸化物との反応によって(A)重合性単量体の重合を開始させる還元剤”を含有しない、
歯科用接着性組成物。 A one-component dental adhesive composition for adhering a photocurable filling material containing an aromatic amine to tooth structure,
100 parts by mass of (A) polymerizable monomer, including 1 part by mass to 40 parts by mass of (a1) acidic group-containing polymerizable monomer;
0.05 parts by mass to 2 parts by mass of (B) a divalent copper compound;
(C) peroxide containing 0.1 parts by mass to 10 parts by mass of (c1) organic peroxide;
0.1 parts by mass to 10 parts by mass of (D) iron arene complex,
1 part by mass to 50 parts by mass of (E) water;
10 parts by mass to 300 parts by mass of (F) organic solvent,
and does not contain "a reducing agent that initiates polymerization of (A) polymerizable monomer by reaction with (B) divalent copper compound and (C) peroxide",
Dental adhesive composition.
で表される鉄アレーン錯体である、請求項1に記載の歯科用接着性組成物。 The iron arene complex (D) has the following formula (1)
The dental adhesive composition according to claim 1, which is an iron arene complex represented by:
請求項1又は2に記載の歯科用接着性組成物。 Further containing 0.01 mol to 1 mol of (H) a polyvalent metal compound per 1 mol of the acidic group-containing polymerizable monomer (a1);
The dental adhesive composition according to claim 1 or 2.
Priority Applications (1)
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JP2012126666A (en) | 2010-12-14 | 2012-07-05 | Tokuyama Dental Corp | Adhesive composition for dental use |
WO2019131094A1 (en) | 2017-12-26 | 2019-07-04 | 株式会社トクヤマデンタル | Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method for storing adhesive composition |
JP2020515641A (en) | 2017-04-03 | 2020-05-28 | ゼスト、アイピー、ホールディングス、リミテッド、ライアビリティー、カンパニーZest Ip Holdings,Llc | Dental cement composition and method of use |
JP2020138911A (en) | 2019-02-27 | 2020-09-03 | 株式会社トクヤマデンタル | Dental adhesive composition and dental adhesive composition package |
JP2021130611A (en) | 2020-02-18 | 2021-09-09 | 株式会社トクヤマデンタル | Dental adhesive composition and dental adhesive composition package |
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JP2012126666A (en) | 2010-12-14 | 2012-07-05 | Tokuyama Dental Corp | Adhesive composition for dental use |
JP2020515641A (en) | 2017-04-03 | 2020-05-28 | ゼスト、アイピー、ホールディングス、リミテッド、ライアビリティー、カンパニーZest Ip Holdings,Llc | Dental cement composition and method of use |
WO2019131094A1 (en) | 2017-12-26 | 2019-07-04 | 株式会社トクヤマデンタル | Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method for storing adhesive composition |
JP2020138911A (en) | 2019-02-27 | 2020-09-03 | 株式会社トクヤマデンタル | Dental adhesive composition and dental adhesive composition package |
JP2021130611A (en) | 2020-02-18 | 2021-09-09 | 株式会社トクヤマデンタル | Dental adhesive composition and dental adhesive composition package |
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