JPS62275103A - Photopolymerizable composition - Google Patents
Photopolymerizable compositionInfo
- Publication number
- JPS62275103A JPS62275103A JP29078086A JP29078086A JPS62275103A JP S62275103 A JPS62275103 A JP S62275103A JP 29078086 A JP29078086 A JP 29078086A JP 29078086 A JP29078086 A JP 29078086A JP S62275103 A JPS62275103 A JP S62275103A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- composition according
- group
- azobis
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- -1 azo compound Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 7
- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 claims description 6
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 6
- LBCCPKFTHIBIKU-UHFFFAOYSA-N 3,4-Heptanedione Chemical compound CCCC(=O)C(=O)CC LBCCPKFTHIBIKU-UHFFFAOYSA-N 0.000 claims description 4
- XYZAPOXYXNIBEU-UHFFFAOYSA-N octane-4,5-dione Chemical compound CCCC(=O)C(=O)CCC XYZAPOXYXNIBEU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 3
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 claims 1
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 8
- 239000005548 dental material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000306 component Substances 0.000 abstract 2
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 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 6
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- FJPGAMCQJNLTJC-UHFFFAOYSA-N 2,3-Heptanedione Chemical compound CCCCC(=O)C(C)=O FJPGAMCQJNLTJC-UHFFFAOYSA-N 0.000 description 2
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 2
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- YKYIFUROKBDHCY-ONEGZZNKSA-N (e)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one Chemical group CCO\C=C\C(=O)C(F)(F)F YKYIFUROKBDHCY-ONEGZZNKSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- QNGBRPMOFJSFMF-UHFFFAOYSA-N 1-(4-sulfanylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(S)C=C1 QNGBRPMOFJSFMF-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- VYNQWGXTLZDYFX-UHFFFAOYSA-N 1-benzoylperoxyhexyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(CCCCC)OOC(=O)C1=CC=CC=C1 VYNQWGXTLZDYFX-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JZDHUYKBYNFYAB-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(C)C JZDHUYKBYNFYAB-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- ZKHZEAOYIJBZBM-UHFFFAOYSA-N 2-ethoxyethanethiol Chemical compound CCOCCS ZKHZEAOYIJBZBM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- OVTQTPRJINYNIY-UHFFFAOYSA-N 3-butyl-1h-benzimidazole-2-thione Chemical compound C1=CC=C2NC(=S)N(CCCC)C2=C1 OVTQTPRJINYNIY-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- LPODPMFRVWIGSD-UHFFFAOYSA-N [2-hydroxy-3-[2-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]butoxy]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(CC)COCC(O)COC(=O)C(C)=C LPODPMFRVWIGSD-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- JSWTUBJPNIKZJF-UHFFFAOYSA-N bis(1-phenylethyl)diazene Chemical compound C=1C=CC=CC=1C(C)N=NC(C)C1=CC=CC=C1 JSWTUBJPNIKZJF-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- WRZXKWFJEFFURH-UHFFFAOYSA-N dodecaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO WRZXKWFJEFFURH-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- JNNNAJIAXISWGB-UHFFFAOYSA-N icosane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCCC(O)O JNNNAJIAXISWGB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- BJHIKXHVCXFQLS-OTWZMJIISA-N keto-L-sorbose Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-OTWZMJIISA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- XERJXXOWNJXINE-UHFFFAOYSA-N n-[[tert-butyl(formyl)amino]hydrazinylidene]formamide Chemical compound CC(C)(C)N(C=O)NN=NC=O XERJXXOWNJXINE-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- PJEPOHXMGDEIMR-UHFFFAOYSA-N octane-3,5-dione Chemical compound CCCC(=O)CC(=O)CC PJEPOHXMGDEIMR-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 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
- 239000003973 paint Substances 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester 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
- 229920002223 polystyrene Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は光重合性組成物に関するものであり、とくに、
可視光線の照射により速やかに硬化し、歯科用材料、印
刷版、プリント基板、フォトレジスト材、光硬化型粘土
、がん具や美術工芸品の材料等に利用できる光重合性組
成物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photopolymerizable composition, and in particular,
The present invention relates to a photopolymerizable composition that rapidly hardens upon irradiation with visible light and can be used for dental materials, printing plates, printed circuit boards, photoresist materials, photocurable clay, materials for toys, arts and crafts, etc.
樹脂組成物を光を用いて重合硬化させる技術は、いつで
も重合させたい時に組成物に元を照射することによって
重合させることができるため、操作方法やプロセスのレ
イアウトが自由にとれるという点で非常に便利な技術で
ある。この光を用いた硬化技術どしては、従来、Ｘ線、
γ線、紫外線や可視光線を用いた技術が考案されていた
。一般に光線のエネルギーは短波長の光はど強く、エネ
ルギーの強い光を用いるほど技術的には簡単に組成物を
反応させ、重合硬化できるが、反面、波長の短い光はど
安全面で問題があり、光を発生させる装置の価格も高価
なものとなってしまう。そのため、工業的に大きな規模
の装置では紫外線を利用した光硬化型組成物も非常に有
用ではあるが、例えば歯科用光てん剤を患者の口腔内で
重合硬化させたり、粘土細工のように少量の組成物を机
上で適当な形状にして光硬化させたりするような小規模
なケースでは、可視光線硬化型の方が光発生装置の価格
から考えても人体に対する安全性からもより望ましいと
考えられる。The technology of polymerizing and curing resin compositions using light allows polymerization to be carried out by irradiating the composition with a source whenever desired, so it is extremely useful in that it allows for flexible operation methods and process layouts. It's a convenient technology. Conventional curing technologies using this light include X-rays,
Technologies using gamma rays, ultraviolet rays, and visible light were devised. In general, light with short wavelengths is strong, and technically speaking, the stronger the energy, the easier it is to react and polymerize the composition, but on the other hand, light with shorter wavelengths poses safety problems. However, the cost of the device that generates the light becomes expensive. For this reason, photocurable compositions using ultraviolet rays are very useful in large-scale industrial equipment, but for example, photocurable compositions that use ultraviolet rays may be used to polymerize and cure dental photonics in the patient's mouth, or in small quantities such as in clay work. In small-scale cases where a composition is shaped into an appropriate shape on a desk and photocured, visible light curing is considered more desirable in terms of the cost of the light generator and safety for the human body. It will be done.
可視光線番こよる光重合法は、従来より種々研究されて
２す、いくつかの提案がなされている。たとえば、重合
開始触媒に関してはケトン類光増感剤とアミン類、ホス
フィン類または有機スルフィン類との組み合せ〔特開昭
４８−４９８７５号、特開昭５４−１０９８６号、特開
昭５５−８３７０６号、特開昭６０−２６００２号、特
開昭６０−７１６０２号〕、ケトン類光増感剤と有機過
酸化物との組み合せ〔特開昭５５−１０２号、特開昭６
０−３２８０１号〕、ケトン類光増感剤と有機過酸化物
および有機アミンの三成分系の組み合せ〔特開昭５７−
２０３００７号〕、可視光線に吸収をもつ光還元性色素
化合物と三級アミンの組み合せ〔特開昭５７−４０５０
６号、特開昭５７−１５１６３９号、特開昭５７−１２
８７０２号〕、ケトン類光増感と有機過慮物およびアル
デヒド類の三成分系の組み合せ〔特開昭６０−１４９６
０３号〕、ケトン類光増感剤とチオール化合物との組み
合せ〔特開昭６０−１９７６０９号〕等がある。また、
アゾ化合物を用いる重合法は、熱分解か紫外線照射によ
る重合法〔西ドイツ特許公開公報第２１３００７０号、
特開昭５５−１６０８３号〕が知られている。Photopolymerization methods that rely on visible light have been extensively studied and several proposals have been made. For example, regarding polymerization initiation catalysts, combinations of ketone photosensitizers and amines, phosphines, or organic sulfins [JP-A-48-49875, JP-A-54-10986, JP-A-55-83706] , JP-A-60-26002, JP-A-60-71602], combination of ketone photosensitizer and organic peroxide [JP-A-55-102, JP-A-6
No. 0-32801], a three-component combination of a ketone photosensitizer, an organic peroxide, and an organic amine [JP-A-57-
No. 203007], a combination of a photoreducible dye compound that absorbs visible light and a tertiary amine [JP-A-57-4050]
No. 6, JP-A-57-151639, JP-A-57-12
No. 8702], a combination of ketone photosensitization and a three-component system of organic substances and aldehydes [JP-A-60-1496]
No. 03], a combination of a ketone photosensitizer and a thiol compound [JP-A-60-197609], and the like. Also,
The polymerization method using an azo compound is a polymerization method using thermal decomposition or ultraviolet irradiation [West German Patent Publication No. 2130070,
JP-A-55-16083] is known.
しかし、従来の技術では重合速度が不十分であったり、
また、重合速度が充分であっても、光重合性組成物の保
存安定性や、硬化物の色安定性が不良であるという問題
点がある。特に美術工芸品材料や歯科材料のように硬化
物の厚みがあり、色調の安定性を必要とする目的に使用
するには、実用性に乏しかった。However, with conventional technology, the polymerization rate is insufficient,
Further, even if the polymerization rate is sufficient, there is a problem that the storage stability of the photopolymerizable composition and the color stability of the cured product are poor. In particular, the cured material is thick, such as arts and crafts materials and dental materials, and is not practical for use in purposes that require stability of color tone.
本発明の目的は、前記問題点を解決することにある。す
なわち、本発明の目的は、可視光線に充分良好な感度を
示し、硬化物の色安定性も良好で、かつ、保存安定性に
優れた光重合性組成物を提供することである。An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a photopolymerizable composition that exhibits sufficiently good sensitivity to visible light, has good color stability of a cured product, and has excellent storage stability.
上記の本発明の目的は、（ａ）エチレン性二重結イ〕を
少なくとも１個有する付加重合可能な化介物および（ｂ
）α−ジケトンとアゾ化合物とからなる光開始剤とから
構成された、可視光線を照射することにより重合可能な
組成物により達成される。The object of the present invention is to provide (a) an addition-polymerizable compound having at least one ethylenic double bond and (b)
) This is achieved by a composition which is polymerizable by irradiation with visible light and is composed of an α-diketone and a photoinitiator consisting of an azo compound.
本発明は、とくに光開始剤成分としてアゾ化合物を用い
ることを特徴とするが、かかるアゾ化合物としては、一
般式
％式％
〔式中、ＡおよびＡ′はそれぞれニトリル基または炭素
数１−２０の炭化水素基を表わし、Ａ（！：Ａ’は同一
でもよく、また、異なっていてもよい。Ｂ１Ｂ’、Ｄお
よびＤ′はそれぞれ炭素数１−２０の炭化水素基を表わ
し、Ｂ、Ｂ’、ＤおよびＤ′は同一であっても異なって
いてもよく、また、ＢとＤおよび／またはＢ′とＤ′が
結合し、環状構造を形成していてもよい。また、Ａ、
Ａ’、Ｂ、＋３’、ＤおよびＤ′は炭素数１−４のアル
コキシ基、炭素数２−５のアルコキシカルボニル基、炭
素″ａ２−５のアミド基またはアミン基を含んでいても
よい（炭素数には、ＣＯＯ−１−ＣＯＮＨ２の炭素を含
む）。〕で表わされる化合物が用いられる。
゛
これらのアゾ化合物には、たとえば、２２’−アゾビス
イソブチロニトリル、２２′−アゾビスイソプロピロニ
トリル、１．１’−アゾビス（シクロヘキサン−１−カ
ルボニトリル）、２２’−アゾビス（ｚ４−ジメチルバ
レロニトリル）、２２’−７：／’ビス（４−メトーｐ
シー２４−ジメチルバレロニトリル）、１．１’−アゾ
ビス（１−フェニルエタン）、アゾビス−ジフェニルメ
タン、 ２２／−アゾビス（メチルイソブチレート）
、２２’−アゾビス（２−アミジノプロパン）ジクロ１
１ド、２２’−アゾビス（２−アミジノプロパン）ジア
セテート、２−ｔ−７−ｙ−ルアシー２−シアノプロパ
ｙ、２−を一ブチ、シアノ”−１−シアノシクロヘキサ
ン、２−ｔ−ブチルアゾ−２−シアンブタン、ｔ−ブチ
ルアゾホルムアミド、２２′−アゾビス（インブチロア
ミド）ジヒドレート、２．２’−アゾビス〔２−メチル
−Ｎ−（２−ヒドロキシエチル）プロピオンアミド〕、
２．２′−アゾビス（２−メチル−Ｎ−（１，１−ビス
（ヒドロキシメチル）エチル〕）プロピオンアミド、２
，２′−アゾビス（２−メチル−Ｎ −［１゜１−ビス
（ヒドロキシメチル）−２−ヒドロキシエチル］）プロ
ピオンアミド等が含まれる。これらの中でも、１．１’
−アゾビス（フクロヘキサン−１−カルボニトリル）、
２．２−アゾビス（メチルイソブチレート）、２，２′
−アゾビス（２，４−ジメチルバレロニトリル等が特に
好ましい。これらの灯
アゾ化合物は重合性単量体に・し、０．５〜１０重量％
の範囲で使用される。The present invention is particularly characterized by using an azo compound as a photoinitiator component, and such an azo compound has the general formula % [wherein A and A' are each a nitrile group or a carbon number of 1 to 20]. represents a hydrocarbon group, A(!: A' may be the same or different. B1B', D and D' each represent a hydrocarbon group having 1 to 20 carbon atoms, B, B ', D and D' may be the same or different, and B and D and/or B' and D' may be bonded to form a cyclic structure.Also, A,
A', B, +3', D and D' may contain an alkoxy group having 1-4 carbon atoms, an alkoxycarbonyl group having 2-5 carbon atoms, an amide group or amine group having 2-5 carbon atoms ( The number of carbon atoms includes carbon of COO-1-CONH2).] A compound represented by the following formula is used.
゛These azo compounds include, for example, 22'-azobisisobutyronitrile, 22'-azobisisopropylonitrile, 1.1'-azobis(cyclohexane-1-carbonitrile), 22'-azobis(z4 -dimethylvaleronitrile), 22'-7:/'bis(4-methop
24-dimethylvaleronitrile), 1,1'-azobis(1-phenylethane), azobis-diphenylmethane, 22/-azobis(methylisobutyrate)
, 22'-azobis(2-amidinopropane) dichloro 1
1-do, 22'-azobis(2-amidinopropane) diacetate, 2-t-7-y-ruacy2-cyanopropane, 2-monobuty, cyano''-1-cyanocyclohexane, 2-t-butylazo- 2-cyanbutane, t-butylazoformamide, 22'-azobis(inbutyroamide) dihydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
2.2'-Azobis(2-methyl-N-(1,1-bis(hydroxymethyl)ethyl))propionamide, 2
, 2'-azobis(2-methyl-N-[1°1-bis(hydroxymethyl)-2-hydroxyethyl])propionamide, and the like. Among these, 1.1'
-Azobis(fuclohexane-1-carbonitrile),
2.2-azobis(methylisobutyrate), 2,2'
-Azobis(2,4-dimethylvaleronitrile and the like are particularly preferred.These light azo compounds are converted into polymerizable monomers and are used in an amount of 0.5 to 10% by weight.
used within the range.
本発明に使用できるα−ジケトンとしては、一般式
％式％
〔式中、Ｘは炭素数１−２０の脂肪族炭化水素基を表わ
し、２個のＸは同一であっても異なっていてもよく、ま
た２例のＸどうしが互いに結合し、環状構造を形成して
いてもよい。〕で表わされる化合物である。これらの化
合物の中には、たとえば、ジアセチル、２３−ペンタン
ジオン、７３−９るいは３．４−ヘキサンジオン、２３
あるいは３． 、ｉ −ヘプタンジオン、２３−１３．
４−ちるいはｄ、５−オクタンジオンのような鎖状のα
−ジケトン化合物、カンファーキノン（１，７，７−１
リッチルビシクロ−［２２１］へブタン−２，３−ジオ
ン）やビシクロ〔２２，ｌ ）ヘプタン−２３−ジオン
のようなＵＮｍ式α−ジケトン化合物が含まれる。これ
らの中でも、カンファーキノン、ジアセチル、′１３−
ペンタンジオン、２３−．？）るいは、３．４−ヘキサ
ンジオン、２３−６るいは、３．４−ヘプタンジオン、
２３−１３．４−あるいは４，５−オクタンジオン等が
特に好ましい。これらの化合物は、重合性単量体に対し
、０．１〜５重惜チの範囲で使用される。The α-diketone that can be used in the present invention has the general formula % [wherein, X represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and two X's may be the same or different]. Alternatively, two Xs may be bonded to each other to form a cyclic structure. ] This is a compound represented by Among these compounds are, for example, diacetyl, 23-pentanedione, 73-9 or 3,4-hexanedione, 23
Or 3. , i-heptanedione, 23-13.
4-thiol is d, chain α such as 5-octanedione
-diketone compound, camphorquinone (1,7,7-1
Included are UNm formula α-diketone compounds such as lytylbicyclo-[221]heptane-2,3-dione) and bicyclo[22,l)heptane-23-dione. Among these, camphorquinone, diacetyl, '13-
Pentanedione, 23-. ? ) or 3,4-hexanedione, 23-6 or 3,4-heptanedione,
Particularly preferred are 23-13.4- or 4,5-octanedione. These compounds are used in an amount of 0.1 to 5 times the amount of the polymerizable monomer.
次に本発明では、硬化速度をさらに速くするために、前
述の開始剤成分にメルカプト基を有する化合物および／
または、有機過酸化物をさらに加えることができる。メ
ルカプト基を有する化合物としては、１−オクタデカン
チオール、１−ドデカンチオール、シクロヘキシルメル
カプタン、２−メルカプトエタノール、２−エトキシエ
タンチオール、２−メルカプト−酢酸などの非置換なら
びに置換アルキルメルカプタン；チオフェノール、ナフ
タレン−２−チオール、ベンジルチオール、チオサリチ
ル酸、４−メルカプトアセトフェノンなどの非置換なら
びに置換芳香族メルカプタン：２−メルカプトチアゾリ
ン、２−メルカプトピリジン、２−メルカプトキノン、
２−メルカプトイミダゾール、２−メルカプトベンズチ
アゾール、２−メルカプトベンズチアゾール、２−メル
カプトベンズイミダゾール、２−メルカプト−１−ブチ
ルベンズイミダゾールなどが挙げられる。また有機過酸
化物としては、ジアシルパーオキシド類や、パーオキシ
エステル類が挙げられ、特に過酸化ベンゾイル、ｔ−ブ
チルパーベンゾエート、ジ−ｔ−ブチルパーオキシイソ
７タレート、２５−ジメチル−２５−ジ（ベンゾイルパ
ーオキシ）ヘキサンなどの安息香酸の誘導体と考えられ
る過酸化物が好適である。これらの成分は、重合性単量
体に対し、０．０１〜２．０重量％の範囲で使用される
。Next, in the present invention, in order to further increase the curing speed, the above-mentioned initiator component contains a compound having a mercapto group and/or
Alternatively, additional organic peroxides can be added. Examples of compounds having a mercapto group include unsubstituted and substituted alkyl mercaptans such as 1-octadecanethiol, 1-dodecanethiol, cyclohexylmercaptan, 2-mercaptoethanol, 2-ethoxyethanethiol, and 2-mercapto-acetic acid; thiophenol and naphthalene. - Unsubstituted and substituted aromatic mercaptans such as 2-thiol, benzylthiol, thiosalicylic acid, 4-mercaptoacetophenone: 2-mercaptothiazoline, 2-mercaptopyridine, 2-mercaptoquinone,
Examples include 2-mercaptoimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 2-mercapto-1-butylbenzimidazole, and the like. Examples of organic peroxides include diacyl peroxides and peroxy esters, particularly benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxyiso7thalet, 25-dimethyl-25- Peroxides considered to be derivatives of benzoic acid, such as di(benzoylperoxy)hexane, are preferred. These components are used in an amount of 0.01 to 2.0% by weight based on the polymerizable monomer.
本発明において使用されるエチレン性二重結合を少なく
とも１個有する付加重合可能な化合物としては、α−シ
アンアクリル酸、（メタ）アクリル酸、ウレタン（メタ
）アクリル酸、クロトン酸、桂皮酸、ソルビン酸、マレ
イン酸、イタコン酸すどの１価又は２価アルコールとの
エステル類さらに、Ｎ−インブチルアクリルアミドのよ
うな（メタ）アクリルアミド類、酢酸ビニルなどのよう
なカルボン酸のビニルエステル類、ブチルビニルエーテ
ルのようなビニルエーテル類、Ｎ−ビニルピロリドンの
ようなモノ−Ｎ−ビニル化合物、スチレン誘導体などが
挙げられるが特に下記のような一官能性、多官能性の（
メタ）アクリル酸エステル類およびウレタン（メタ）ア
クリル酸エステル類が好適である。Examples of addition-polymerizable compounds having at least one ethylenic double bond used in the present invention include α-cyanoacrylic acid, (meth)acrylic acid, urethane (meth)acrylic acid, crotonic acid, cinnamic acid, and sorbin. Acids, esters with monohydric or dihydric alcohols such as maleic acid and itaconic acid, as well as (meth)acrylamides such as N-butylacrylamide, vinyl esters of carboxylic acids such as vinyl acetate, and butyl vinyl ether. Examples include vinyl ethers such as N-vinylpyrrolidone, mono-N-vinyl compounds such as N-vinylpyrrolidone, and styrene derivatives.
Preferred are meth)acrylic esters and urethane (meth)acrylic esters.
（１）−官能性
（メタ）アクリル酸メチル、（メタ）アクリル酸ｎ−も
しくはｉ−プロピル、（メタ）アクリル酸ｎ−１ｉ−も
しくはｔ−ブチル、２−ヒドロキシエチル（メタコアク
リレートなど。(1)-Functional methyl (meth)acrylate, n- or i-propyl (meth)acrylate, n-1i- or t-butyl (meth)acrylate, 2-hydroxyethyl (methacrylate, etc.).
（ｉｉ） 二官能性
〔ここでｎは、３〜２０の整数Ｒは水素またはメチル基
を表わす〕
で示される化合物。例えば、プロパンジオール、ブタン
ジオール、ヘキサンジオール、オクタンジオール、ノナ
ンジオール、デカンジオール、エイコサンジオールなど
のジ（メタ）アクリレート類、〔ここでｎは１〜１４の
整数Ｒは水素またはメチル基を表わす。〕
で示される化合物。例えば、エチレングリコール、ジエ
チレングリコール、トリエチレン／Ｉ）コール、テトラ
エチレングリコール、ドデカエチレングリコール、テト
ラテカエチレングリコール、プロピレングリコール、ジ
プロピレングリコール、テトラデ力グロビレングリコー
ルなどのジ（メタ）アクリレート類の池、グリセリンジ
（メタ）アクリレート、２，２−ビス〔ｐ−（γ−メタ
クリロキ／−Ｓ−ヒドロキシグロボキ／）フェニルプロ
パン（Ｂｉｇ −ＧＭＡ ）、ビスフェノールＡジメタ
クリレート、ネオペンチルグリコールジ（メタ）アクリ
レート、２，２−ジ（４−メタクリロキシポリエトキシ
フェニル）プロパン（１分子中にエトキシ基２〜１０）
、１．２−ビス（３−メタクリロキシ−２−ヒドロキシ
プロポキシ）ブタンなど。(ii) A compound having a difunctional property [where n is an integer R of 3 to 20 and represents hydrogen or a methyl group]. For example, di(meth)acrylates such as propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol, eicosanediol, [where n is an integer of 1 to 14 and R represents hydrogen or a methyl group] . ] A compound represented by For example, di(meth)acrylates such as ethylene glycol, diethylene glycol, triethylene/I)col, tetraethylene glycol, dodecaethylene glycol, tetratecaethylene glycol, propylene glycol, dipropylene glycol, and tetradeglobylene glycol; Glycerin di(meth)acrylate, 2,2-bis[p-(γ-methacryloki/-S-hydroxygloboki/)phenylpropane (Big-GMA), bisphenol A dimethacrylate, neopentyl glycol di(meth)acrylate, 2,2-di(4-methacryloxypolyethoxyphenyl)propane (2 to 10 ethoxy groups in 1 molecule)
, 1,2-bis(3-methacryloxy-2-hydroxypropoxy)butane and the like.
（ｉｉｉ） 三官能性以上
トリメチロールプロパントリ（メタ）アジリレート、ペ
ンタエリスリトールテトラ（メタ）アクリレートなど。(iii) trifunctional or higher functional trimethylolpropane tri(meth)azilylate, pentaerythritol tetra(meth)acrylate, etc.
Ｇｖ） ウレタン（メタ）アクリレート系ヒドロキシ
ル基を有する（メタ）アクリレート単量体２モルとジイ
ソシアネート１モルの反応生成物、両末端ＮＣＯのウレ
タンプレポリマーとヒドロキシル基を有する（メタ）ア
クリレート単量体の反応生成物などが挙げられ、かかる
反応生放物の構造は、次式に示すものが挙げられる。Gv) A reaction product of 2 moles of a urethane (meth)acrylate monomer (meth)acrylate having a hydroxyl group and 1 mole of diisocyanate, a urethane prepolymer with NCO at both ends and a (meth)acrylate monomer having a hydroxyl group. Examples include reaction products, and examples of the structure of such reaction products include those shown in the following formula.
。 。 。 （り
！ＩＩＩ １
〔ここでＲ１は水素またはメチル基、Ｒ２はアルキレン
基、Ｒａは有機残基である。）具体的なものとして特公
昭５１−３６９６０号に記載されている２、 ２．４−
トリメチルへキサメチレンジイソシアネートとメタクリ
ル酸オキシプロピルとの反応生成物、特公昭５５−３３
６８７号に記載されている両末端インシアネートのウレ
タンプレポリマーとメタクリル酸−２−オキシエチルと
の反応生成物が挙げられる。まｆｃ％開昭５６−１５２
４０８号に開示されているような四官能性のモノマーも
用いられる。. . . (Ri!III 1 [Here, R1 is hydrogen or a methyl group, R2 is an alkylene group, and Ra is an organic residue.) Specific examples include 2 and 2.4 described in Japanese Patent Publication No. 51-36960. −
Reaction product of trimethylhexamethylene diisocyanate and oxypropyl methacrylate, Japanese Patent Publication No. 55-33
687, a reaction product of a urethane prepolymer having incyanate at both terminals and 2-oxyethyl methacrylate. Mafc% Kaisho 56-152
Tetrafunctional monomers such as those disclosed in No. 408 may also be used.
本発明の組成物には、上述の重合性単量体および光重合
開始剤の他に、目的に応じて各種の充填剤が加えられて
もよい。この充填剤は有機物であっても、無機物であっ
てもよく、有機物としては、ポリ（メタ）アクリル酸メ
チル、ポリ（メタ）アクリル酸エチル、ポリエステル、
ポリエチレン、ポリプロピレン、ナイロン、ポリスチレ
ン、ポリアミド、ホハール、ビニロン、セルロース、テ
ンプンなどの他に、後述の無機充填剤をポリマーで被覆
した材料であってもよい。また無機物としては、二酸化
ケイ素、アルミナ、各種ガラス類、セラミックス類、珪
藻土、メルク、カオリン、モンモリロナイト等の粘土鉱
物、活性白土、合成ゼオライト、マイカ、フッ化カルシ
ウム、リン酸カルシウム、硫酸バリウム、二酸化ジルコ
ニウム、ケイ酸アルミニウム、ケイ酸ジルコニウム、ケ
イ酸カルシウム、炭酸マグネシウム、炭酸カルシウム、
石こう、二酸化チタンなど酸よシなる粉末状、繊維状、
薄片状のものであシ、目的に応じてその最大粒子径が１
００μ以下のものが用いられるが、粒子の小さいものと
しては数ｎｍの微粒子状のものも用いられる。また無機
充填剤を使用することによシ、複合材料の強度の向上を
目的とする場合は表面処理をして用いることが望ましい
。表面処理剤としてはγ−メタクリロキシプロピルトリ
メトキシシラン、ビニルトリクロロシラン、ビニルトリ
エトキシシラン、ビニルトリメトキシシラン、ビニルト
リアセトキシシランおよびビニルトリ（メトキシエトキ
シ）シラン等の有機ケイ素化合物が用いられ、７ラン化
は、通常の方法によシ行なわれる。これらの充填剤は、
重合性単量体に対し、０．１〜８倍重量を使用すること
が好ましい。In addition to the above-mentioned polymerizable monomer and photopolymerization initiator, various fillers may be added to the composition of the present invention depending on the purpose. This filler may be organic or inorganic. Examples of organic materials include methyl poly(meth)acrylate, ethyl poly(meth)acrylate, polyester,
In addition to polyethylene, polypropylene, nylon, polystyrene, polyamide, hohar, vinylon, cellulose, starch, etc., materials in which an inorganic filler described below is coated with a polymer may also be used. Examples of inorganic substances include silicon dioxide, alumina, various glasses, ceramics, diatomaceous earth, clay minerals such as Merck, kaolin, and montmorillonite, activated clay, synthetic zeolite, mica, calcium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, and silicon dioxide. aluminum acid, zirconium silicate, calcium silicate, magnesium carbonate, calcium carbonate,
Gypsum, titanium dioxide, and other acid-repellent powders, fibers,
It is flaky, and depending on the purpose, the maximum particle size may be 1.
Although particles of 00 μm or less are used, fine particles of several nanometers are also used as small particles. In addition, if the purpose is to improve the strength of the composite material by using an inorganic filler, it is desirable to perform surface treatment. Organosilicon compounds such as γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane and vinyltri(methoxyethoxy)silane are used as surface treatment agents. The conversion is carried out in a conventional manner. These fillers are
It is preferable to use 0.1 to 8 times the weight of the polymerizable monomer.
また本発明の組成物には、所望によシ、重合禁止剤、着
色剤、紫外線吸収剤等を添加することができる。Further, optional additives, polymerization inhibitors, colorants, ultraviolet absorbers, etc. can be added to the composition of the present invention.
前述のように、本発明の光重合性組成物は、可視光線の
照射によシ、速やかに硬化し、組成物の保存安定性も良
好でかつ、硬化物の色安定性も良好であるという特徴を
有するため、歯科用材料、光硬化型の塗料、印刷版、プ
リント基板作製、フォトレジスト材、光硬化型粘土、が
ん具や美術工芸品の材料等に利用できる。As mentioned above, the photopolymerizable composition of the present invention cures rapidly upon irradiation with visible light, has good storage stability, and has good color stability of the cured product. Because of these characteristics, it can be used for dental materials, photo-curing paints, printing plates, printed circuit board production, photoresist materials, photo-curing clays, materials for toys and arts and crafts, etc.
実施例１
トリエチレングリコールジメタクリレート５０重責部と
２，２−ビス〔ｐ−（γ−メタクリルオキシーβ−ヒド
ロキシプロポキク）フェニル〕プロパン５０１Ｌ量部を
混合し、組成物を作成した。ガラス製サンプル管（外径
１０ ｗａ 、高さ３０Ｈ１ガラス肉厚約０．８ ｍ
）に前記組成物４００ｒｑ、カンファーキノン４ＴＩ＃
ｇ、２．２−アゾビスイソブチロニトリル８岬を入れて
混合し、完全に溶解させた。Example 1 A composition was prepared by mixing 50 parts of triethylene glycol dimethacrylate and 501 L parts of 2,2-bis[p-(γ-methacryloxy-β-hydroxypropoxy)phenyl]propane. Glass sample tube (outer diameter 10 wa, height 30H1, glass wall thickness approx. 0.8 m)
) with 400 rq of the above composition, camphorquinone 4TI#
8 g of 2.2-azobisisobutyronitrile were added and mixed to completely dissolve.
歯科用可視光線照射器（Ｋｕｌｚｅｒ綴、Ｔｒａｎｓｌ
ｕｘ ）のハンドピースの先端チップをはずし、この円
筒状部分を垂直上方に向けて固定しその円筒の底まで前
記サンプル管を入れ、サンプル管の中央部に熱電対をセ
ットしてから光を照射し重合熱による温度上昇をモニタ
ーして温度が最高値を示した時間第１表に記載し九九増
感剤とアゾ化合物を用いて、実施例１と全く同様の条件
下で硬化時間を測定した。第１表に結果を示す。Dental visible light irradiator (Kulzer, Transl
Remove the tip of the handpiece (ux), fix this cylindrical part vertically upward, insert the sample tube to the bottom of the cylinder, set the thermocouple in the center of the sample tube, and then irradiate it with light. The temperature increase due to polymerization heat was monitored and the time at which the temperature reached its maximum value was listed in Table 1. Using a multiplication factor sensitizer and an azo compound, the curing time was measured under exactly the same conditions as in Example 1. did. Table 1 shows the results.
比較例１〜７ 第２表に記載した光増感剤と促進剤を用いて。Comparative examples 1 to 7 Using the photosensitizers and accelerators listed in Table 2.
実施例１と全く同様の条件下で硬化時間を測定し念。第
２表に結果を示す。The curing time was measured under exactly the same conditions as in Example 1. Table 2 shows the results.
以下余白
実施例５〜７
第３表に記載した３成分系光開始剤を用いて実施例１と
全く同様の条件下で硬化時間全測定した。Margin Examples 5 to 7 The entire curing time was measured under exactly the same conditions as in Example 1 using the three-component photoinitiator listed in Table 3.
結果を第３表に示す。The results are shown in Table 3.
第 ３ 表
実施例８〜中
トリエチレングリコールジメタクリレート１゜重量部、
２．２−ビス（ｐ−（ｒ−メタクリルオキシ−β−ヒド
ロキシプロポキシ）フェニル〕プロパン１０重量部、１
．１’−アゾビス（シクロヘキサン−１−カルボニトリ
ル）マタは２．２′−アゾビス（メチルイソブチレート
）０．２１Ｅ’ｉ部、カンファーキノン０．２重量部を
良く混合して液状組成物を得た。この組成物にざらにシ
ラン処理を施した粉末シリカ８０３ｉｉ部を混合して練
り合ぜ、ペースト状組成物を作製した。この組成物を歯
科用に汎用されている光硬化型レジン用答器（黒色ポリ
プロピレン製内径９瓢φＸ５０ｍ、肉厚１ｍ＋のシリン
ジ）に４ｆずつ充填し、保存安定性試験を行なつ穴。４
５℃恒温槽に容器ごと入れ経時的に硬化の有無を調べた
。結果を第４表に示した。Table 3 Example 8 - Medium triethylene glycol dimethacrylate 1° part by weight,
2.2-bis(p-(r-methacryloxy-β-hydroxypropoxy)phenyl)propane 10 parts by weight, 1
．． 1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(methylisobutyrate) 0.21 E'i part and camphorquinone 0.2 part by weight were thoroughly mixed to obtain a liquid composition. Ta. This composition was mixed with 803ii parts of powdered silica that had been roughly silane treated and kneaded to prepare a paste composition. This composition was filled into a photocurable resin container (black polypropylene syringe with an inner diameter of 9 mm x 50 m and a wall thickness of 1 m+) commonly used in dentistry, and filled with 4 f holes to perform a storage stability test. 4
The entire container was placed in a thermostat at 5° C., and the presence or absence of curing was examined over time. The results are shown in Table 4.
ま比、上記の液状組成物に可視光ｍを照射して。Then, the above liquid composition was irradiated with visible light m.
該組成物を硬化させ、厚さ１瓢、直径２０１ｍの円板を
作製した。この円板を紫外線照射機（スガ試験機社製、
サンテスト型）を用い、紫外ｆｌｌｔ−所定時間照射し
て円板の色の変化を肉眼で観察した。The composition was cured to produce a disk with a thickness of 1 gourd and a diameter of 201 m. This disc was heated using an ultraviolet irradiation machine (manufactured by Suga Test Instruments Co., Ltd.).
The disc was irradiated with ultraviolet light for a predetermined period of time using a Suntest model), and the change in color of the disc was observed with the naked eye.
結果を第４表に示した。The results are shown in Table 4.
比較例８〜１０
実施例８の液状組成物において、１．１′−アゾビス（
フクロヘキサン−１−カルボニトリル）の代りに過酸化
ベンゾイル０．２３１ｊ−ｉ部、ミヒラーケトン０．２
車量部、まｆｃはｐ−ジメチルアミノベンズアルデヒド
０．２重量部を加え、さらにこの組成物に実施例８と同
様の粉末シリカを同量加えてぺ一ヌト状組成物を作りそ
れぞれ保存安定性を調べ念。Comparative Examples 8 to 10 In the liquid composition of Example 8, 1.1′-azobis(
0.231 parts of benzoyl peroxide, 0.2 parts of Michler's ketone instead of (fuclohexane-1-carbonitrile)
0.2 parts by weight of p-dimethylaminobenzaldehyde was added to the weight part and fc, and the same amount of powdered silica as in Example 8 was added to this composition to make a sticky composition, and the storage stability of each was determined. Please check it out.
結果を第４表に示した。The results are shown in Table 4.
また、実施例８の液状組成物ＶＣおいて、１．１′−ア
ゾビス（シクロヘキサン−１−カルボニトリル）の代ｆ
ｉＫ過酸化ベンゾイル、ミヒラーケトン″！たはｐ−ア
ミノベンズアルデヒドを加えた組成物について実施例８
と同様にして円板の色の変化を調べた。結果を第４表に
示した。In addition, in the liquid composition VC of Example 8, the substitute f for 1,1'-azobis(cyclohexane-1-carbonitrile)
Example 8 for compositions containing iK benzoyl peroxide, Michler's ketone''! or p-aminobenzaldehyde
Changes in the color of the discs were investigated in the same manner. The results are shown in Table 4.
以下余白
上記から明らかなように１重合促進剤が過酸化ベンゾイ
ルでは組成物の保存安定性が悪く、ミヒラーケトンでは
硬化物の色調安定性が悪かつ食。As is clear from the above, when the polymerization accelerator is benzoyl peroxide, the storage stability of the composition is poor, and when Michler's ketone is used, the color stability of the cured product is poor and it is edible.
本発明の組成物では、保存安定性および色調安定性が良
好であった。The composition of the present invention had good storage stability and color stability.
実施例１０
２．２−ジ（４−メタクリロキシポリエトキシフェニル
）プロパン（１分子中にエトキシ基平均４個）３０重量
部、１．６−ヘキサンジオールジアクリレート４０重量
部、トリメチａ−ルプロパントリアクリレート３０ｒＸ
量部、カンファーキノンｏ、ｓｍｔｔ部、２．２’−ア
ゾビスイソブチロニトリル２友Ｉｋ部を混合し２．均一
に溶解さぜた組成物を調製しｔｏこの組成物４０重量部
に、粉末状の炭酸マグネシウム６０重′ｆｉｔ部を混合
して練和（７粘土状の組成物を調製（、た。−万、顕微
鏡Ｒ１のスライドグラス３枚を合せて三角柱型の型を作
り、この型の甲に上述の粘土状組成物ｆ隙間のないよう
に詰め１両端をガラス片でふざい〕ど後、この型を直射
日光にさらした。三角柱のそれぞれの餌か全て直接口光
に当るように、約１０分おきに型を置く角度を変え、全
部の面に光を当て終えてから、型を外して硬化物をとシ
出した。光を当てる前は濃い黄色の不透明なペーストで
あったものが、硬化物では淡黄色ないしは淡い乳白色の
透明感のある固体となってお９１紙やすυを用いて稜や
角の尖ったところを削り取ったのち交鎖として使用でき
る成形物が得られた。Example 10 30 parts by weight of 2.2-di(4-methacryloxypolyethoxyphenyl)propane (average of 4 ethoxy groups in 1 molecule), 40 parts by weight of 1.6-hexanediol diacrylate, trimethylalpropane Triacrylate 30rX
1 part, camphorquinone O, smtt part, and 2.2'-azobisisobutyronitrile 2 part Ik were mixed.2. A uniformly dissolved composition was prepared, and 40 parts by weight of this composition was mixed with 60 parts by weight of powdered magnesium carbonate and kneaded (7) to prepare a clay-like composition. 1.Make a triangular prism-shaped mold by combining three glass slides from Microscope R1, and fill the back of this mold with the above-mentioned clay-like composition so that there are no gaps. The mold was exposed to direct sunlight.The angle at which the mold was placed was changed every 10 minutes so that all of the baits in the triangular prisms were exposed to the light, and after all sides were exposed to light, the mold was removed. The cured product was removed.Before exposure to light, it was a deep yellow opaque paste, but after the cured product it became a pale yellow or pale milky white transparent solid. After cutting off the sharp edges and corners, a molded product that can be used as a crosslink was obtained.
実施例１Ｉ
Ｕ−４７）ｆＡ＊４０重量部、トリプロピレングリコー
ルジアクリレート４０重量部、アクリル酸イソブチル２
０重量部、２，３−ペンタンジオン２重量部、２．２’
−アゾビスイソブチロニトリル２重量部、メトキシヒド
ロキシベンゾフェノン１ｌＨ１部を混合］−１均一な溶
液としたのち、この溶液２５１ｆ量部に粉砕石英粉７５
重量部を混合し、練和することにより粘土状のペースト
を得た。このペーストを透明な薄いスチロール製の型（
７備Ｘ１８ｃｒｎＸ０、８ ｏｎ ）に入れ、表面に黒
の油性塗料で文字を書いた透明なフィルムを密着させ、
まず表面より直射日光に２分間さらした。透明なフィル
ムの上から組成物に触れ、硬化していることを確認した
のち、透明なフィルムの上から、文字の部分を刃物を使
ってえぐシ取シ、取シきれないところは小型のドリルを
使って仕上げを行ったのち、再度表面に太陽光線を約１
０分間あて、さらに裏面にも光線を１０分間あてた。硬
化物を型よりとり出した後、紙やナシで、角とりを行い
表札とした。Example 1I U-47) fA*40 parts by weight, tripropylene glycol diacrylate 40 parts by weight, isobutyl acrylate 2
0 parts by weight, 2 parts by weight of 2,3-pentanedione, 2.2'
- Mix 2 parts by weight of azobisisobutyronitrile and 1 part by weight of methoxyhydroxybenzophenone]-1 After making a homogeneous solution, add 75 parts of crushed quartz powder to 251 parts of this solution.
A clay-like paste was obtained by mixing parts by weight and kneading. Pour this paste into a transparent thin styrofoam mold (
7bi x 18 crn
First, the surface was exposed to direct sunlight for 2 minutes. After touching the composition from above the transparent film and confirming that it has hardened, use a knife to remove the letters from above the transparent film, and use a small drill to remove the parts that cannot be removed. After completing the finish using
The light was applied for 0 minutes, and the back side was also exposed to the light for 10 minutes. After the cured product was removed from the mold, the corners were trimmed using paper or pears to form a nameplate.
？Ｈ３
＊ ＣＨ２＝Ｃ−Ｃｏ−０
！
？Ｈ３
０−ＱＣ−Ｃ＝ＣＨ２
さＨ２
♂−ＱＣ−Ｃ＝ＣＨ２
実施例１２
２．２−ジ（４−メタクリロキシポリエトキシフル
エニ・）プロパン（１分子中にエトキシ基平均２．６１
固）３０薫童部、トリエチレングリコールジメタクリレ
ート７０１１部、カンファーキノン１ｍ１ｆｆｆｉ、
１．１’−アゾビス（シクロヘキサン−１−カルボニ
トリル）２重量部を混合し、均一に溶解し几液状組成物
を調製した。? H3*CH2=C-Co-0! ? H3 0-QC-C=CH2 SaH2 ♂-QC-C=CH2 Example 12 2.2-di(4-methacryloxypolyethoxyflueni.)propane (average of 2.61 ethoxy groups in one molecule)
solid) 30 parts of Kundo, 7011 parts of triethylene glycol dimethacrylate, 1ml of camphorquinone, 1ffi,
2 parts by weight of 1.1'-azobis(cyclohexane-1-carbonitrile) were mixed and uniformly dissolved to prepare a liquid composition.
抜去したヒト大臼歯咬合面のｌトか裂溝を小型ドリル（
ＱＣ社、ダイヤモンドポイントＦ、Ｇ、８１８ ）を用
いて拡大清掃し、その裂溝に４０％リン酸水溶液で４０
秒間酸処理を行った。水洗、乾燥した後に、上記組成物
を注射筒と注射針を用いて、気泡が入らないように該裂
溝に注入した。爾科用の可視光線照射器（クラレ社、ク
イックライ岬）を用いて１２０秒間光を照射して１組成
物を硬化させ次のちビンセットを用いて組成物ｆはがそ
うとしたが、硬化物によく＠着しておシ外すことができ
なかった。A small drill (
QC Co., Ltd., Diamond Point F, G, 818) was used to enlarge and clean the fissure, and the fissure was filled with 40% phosphoric acid aqueous solution for 40 minutes.
Acid treatment was performed for seconds. After washing with water and drying, the above composition was injected into the fissure using a syringe and needle, taking care not to introduce air bubbles. I tried to cure Composition 1 by irradiating it with light for 120 seconds using a visible light irradiator (Kuraray Co., Ltd., Quickly Misaki), and then tried to peel off Composition F using a bottle set, but it did not harden. It often got stuck on things and I couldn't take it off.
Claims (8)
る付加重合可能な化合物および（ｂ）α−ジケトンとア
ゾ化合物とからなる光開始剤とから構成された、可視光
線を照射することにより重合可能な組成物。(1) By irradiating with visible light, the compound is composed of (a) an addition-polymerizable compound having at least one ethylenic double bond and (b) a photoinitiator consisting of an α-diketone and an azo compound. Polymerizable composition.
数１−２０の炭化水素基を表わし、ＡとＡ′は同一でも
よくまたは異なつていてもよい。 Ｂ、Ｂ′、ＤおよびＤ′はそれぞれ炭素数１−２０の炭
化水素基を表わし、Ｂ、Ｂ′、ＤおよびＤ′は、同一で
あつても異なつていてもよく、また、ＢとＤおよび／ま
たはＢ′とＤ′が結合し、環状構造を形成していてもよ
い。また、Ａ、Ａ′、Ｂ、Ｂ′、ＤおよびＤ′は炭素数
１−４のアルコキシ基、炭素数２−５のアルコキシカル
ボニル基、炭素数２−５のアミド基またはアミノ基を含
んでいてもよい。〕で表わされる化合物である特許請求
の範囲第１項記載の組成物。(2) Azo compounds have general formulas ▲ mathematical formulas, chemical formulas, tables, etc. It may also be different or different. B, B', D and D' each represent a hydrocarbon group having 1 to 20 carbon atoms, and B, B', D and D' may be the same or different; D and/or B' and D' may be combined to form a cyclic structure. Furthermore, A, A', B, B', D and D' include an alkoxy group having 1-4 carbon atoms, an alkoxycarbonyl group having 2-5 carbon atoms, an amide group or an amino group having 2-5 carbon atoms. You can stay there. ] The composition according to claim 1, which is a compound represented by:
サン−１−カルボニトリル）、２，２′−アゾビス（メ
チルイソブチレート）、２，２′−アゾビス（２，４−
ジメチルバレロニトリル）である特許請求の範囲第２項
記載の組成物。(3) The azo compound is 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(methylisobutyrate), 2,2'-azobis(2,4-
The composition according to claim 2, which is dimethylvaleronitrile).
し、２個のＸは同一であつても異なつていてもよく、ま
た２個のＸどうしが互いに結合し、環状構造を形成して
いてもよい。〕 で表わされる化合物である特許請求の範囲第１項記載の
組成物。(4) α-diketone has the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and two or two Xs may be bonded to each other to form a cyclic structure. ] The composition according to claim 1, which is a compound represented by:
、２，３−ペンタンジオン、２，３あるいは３，４−ヘ
キサンジオン、２，３−あるいは３，４−ヘプタンジオ
ン、２，３−、３，４−あるいは４，５−オクタンジオ
ンである特許請求の範囲第４項記載の組成物。(5) α-diketone is camphorquinone, diacetyl, 2,3-pentanedione, 2,3- or 3,4-hexanedione, 2,3- or 3,4-heptanedione, 2,3-, 3, The composition according to claim 4, which is 4- or 4,5-octanedione.
がさらに加えられてなる特許請求の範囲第１項記載の組
成物。(6) The composition according to claim 1, further comprising a compound having a mercapto group as a photoinitiator component.
れてなる特許請求の範囲第１項記載の組成物。(7) The composition according to claim 1, further comprising an organic peroxide as a photoinitiator component.
載の組成物。(8) The composition according to claim 1, which contains a filler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-19115 | 1986-01-29 | ||
| JP1911586 | 1986-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62275103A true JPS62275103A (en) | 1987-11-30 |
Family
ID=11990475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29078086A Pending JPS62275103A (en) | 1986-01-29 | 1986-12-05 | Photopolymerizable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62275103A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01232025A (en) * | 1988-03-14 | 1989-09-18 | Mitsui Eng & Shipbuild Co Ltd | Optical shaping method |
| EP0742001A2 (en) * | 1995-05-11 | 1996-11-13 | JENERIC/PENTRON Incorporated | Colour stable dental restorative materials |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62132904A (en) * | 1985-12-06 | 1987-06-16 | Tokuyama Soda Co Ltd | Catalytic composition for photopolymerization |
-
1986
- 1986-12-05 JP JP29078086A patent/JPS62275103A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62132904A (en) * | 1985-12-06 | 1987-06-16 | Tokuyama Soda Co Ltd | Catalytic composition for photopolymerization |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01232025A (en) * | 1988-03-14 | 1989-09-18 | Mitsui Eng & Shipbuild Co Ltd | Optical shaping method |
| JPH0698686B2 (en) * | 1988-03-14 | 1994-12-07 | 三井造船株式会社 | Optical modeling method |
| EP0742001A2 (en) * | 1995-05-11 | 1996-11-13 | JENERIC/PENTRON Incorporated | Colour stable dental restorative materials |
| EP0742001A3 (en) * | 1995-05-11 | 1997-03-19 | Jeneric Pentron Inc | Colour stable dental restorative materials |
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