JPS61258802A - Photopolymerizable composition - Google Patents
Photopolymerizable compositionInfo
- Publication number
- JPS61258802A JPS61258802A JP9954585A JP9954585A JPS61258802A JP S61258802 A JPS61258802 A JP S61258802A JP 9954585 A JP9954585 A JP 9954585A JP 9954585 A JP9954585 A JP 9954585A JP S61258802 A JPS61258802 A JP S61258802A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- photopolymerizable composition
- photopolymerization initiator
- composition
- diketone
- 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 39
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229930006711 bornane-2,3-dione Natural products 0.000 claims abstract description 5
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229940103494 thiosalicylic acid Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 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 abstract description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract 1
- 239000000383 hazardous chemical Substances 0.000 abstract 1
- 231100000206 health hazard Toxicity 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 16
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- -1 vinyl compound Chemical class 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical group CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- RSFDFESMVAIVKO-UHFFFAOYSA-N 3-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S)=C1 RSFDFESMVAIVKO-UHFFFAOYSA-N 0.000 description 2
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000002131 composite material Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ORXSLDYRYTVAPC-UHFFFAOYSA-N 2-(4-sulfanylphenyl)acetic acid Chemical compound OC(=O)CC1=CC=C(S)C=C1 ORXSLDYRYTVAPC-UHFFFAOYSA-N 0.000 description 1
- NEJQFNAWNQKPHV-UHFFFAOYSA-N 2-(4-sulfanylphenyl)butanoic acid Chemical compound CCC(C(O)=O)C1=CC=C(S)C=C1 NEJQFNAWNQKPHV-UHFFFAOYSA-N 0.000 description 1
- HLWUKJUOPQJDOL-UHFFFAOYSA-N 2-(4-sulfanylphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC=C(S)C=C1 HLWUKJUOPQJDOL-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WOPYHBAMCZOYMJ-UHFFFAOYSA-N 2-phenyl-6-sulfanylbenzoic acid Chemical compound OC(=O)C1=C(S)C=CC=C1C1=CC=CC=C1 WOPYHBAMCZOYMJ-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- KCTZYAAHUYSVON-UHFFFAOYSA-N 4-(sulfanylmethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CS)C=C1 KCTZYAAHUYSVON-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000003479 dental cement Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000006286 dichlorobenzyl group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 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
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000068 pit and fissure sealant Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FAIDIRVMPHBRLT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(O)CO FAIDIRVMPHBRLT-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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、メルカプトカルボン酸とα−ジケトンを光開
始剤とするビニル化合物の光重合性組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photopolymerizable composition of a vinyl compound using mercaptocarboxylic acid and α-diketone as photoinitiators.
光重合は、印刷版材、複写用感光剤、プリント配線、I
C、シャドーマスクなどの精密加工用の画像形成、さら
に塗料、印刷インキ、接着剤など多方面で利用されてい
る。Photopolymerization can be used for printing plate materials, photosensitive agents for copying, printed wiring, I
It is used in a wide range of applications, including image formation for precision processing such as C, shadow masks, and paints, printing inks, and adhesives.
光重合は歯科領域においても利用され、例えば、光重合
性物質は歯牙充填材(コンポジットレジン等)、歯牙封
止材及び歯科用接着剤の製造、う蝕予防填塞材、歯冠部
及び義歯の製造等に供されている。Photopolymerization is also used in the dental field; for example, photopolymerizable substances are used in the production of tooth filling materials (composite resins, etc.), tooth sealants and dental adhesives, caries prevention filling materials, dental crowns and dentures. Provided for manufacturing, etc.
従来、上述のように利用される光重合性組成物としては
、例えば、特公昭54−10986号には、次のような
組成を有する、可視光または紫外線の照射により硬化し
得る光重合性組成物が記載されている。すなわち、この
光重合性組成物は感光剤/還元剤を光開始剤として、(
a)下記一般式%式%)
であり、R3−R4は同一であるかまたは相異してよく
、水素または炭化水素基であり、nはゼロまたは1であ
り、基Aは同一であるかまたは相異してよく炭化水素基
または置換炭化水素基であり、そして両方の基Aが直接
接合もしくは二価の炭化水素基を介して一緒に結合して
いても、あるいは両方の基Aが一緒になって縮合芳香族
環系を形成してもよく、nが1かつXが>CRIR2で
あるときおよびnがゼロであるときに基Aは芳香族基ま
たは置換芳香族基である。)で表わされる少なくとも1
種の感光剤と(b)下記一般式
%式%
(ここに、単位Rは同一であるか、または相異しでよく
、水素、炭化水素基、置換炭化水素基、または2個の単
位RがNと共に環系を形成している基であり、3個の単
位Rが同時に置換炭化水素基でなく、そしてNは芳香族
基に対して直接に結合していない)で表わされる少なく
とも1種の還元剤とを含む感光性触媒と重合性エチレン
系不飽和物質とからなる。上記の中で特に好ましい感光
剤の具体例としては、ビアセチル、ベンジル、ベンゾフ
ェノン及びカンフオルキノン(樟脳キノン)等が挙げら
れており、還元剤としてはトリメチルアミン、トリプロ
ピルアミン、ジメチルアミン、 )プロピ
ルアミン、N、N’−ジメチルアニリン、N−メチルジ
フェニルアミン、エチレンジアミン、ヘキサメチレンジ
アミン、ジメチルアミノエチルメタクリレート及びピペ
リジン等が記載されている。これらの光開始剤を使用し
た材料は光照射によって迅速に硬化するものの、硬化物
は著しく着色(多くは黄色)しかつ太陽光及び水中での
色調経時変化が大きく、さらに強度物性が低い水準のも
のしか得られない欠点を有していた。Conventionally, as the photopolymerizable compositions used as mentioned above, for example, Japanese Patent Publication No. 10986/1986 describes a photopolymerizable composition that can be cured by irradiation with visible light or ultraviolet light and has the following composition. things are listed. That is, this photopolymerizable composition uses a photosensitizer/reducing agent as a photoinitiator, and (
a) The following general formula % formula %), R3-R4 may be the same or different, are hydrogen or hydrocarbon groups, n is zero or 1, and the groups A are the same or or are distinctly hydrocarbon groups or substituted hydrocarbon groups, and both groups A are bonded together through a direct bond or a divalent hydrocarbon group, or even if both groups A are together may form a fused aromatic ring system, and the group A is an aromatic or substituted aromatic group when n is 1 and X is >CRIR2 and when n is zero. ) at least 1
and (b) the following general formula % formula % (wherein the units R may be the same or different and are hydrogen, a hydrocarbon group, a substituted hydrocarbon group, or two units R is a group forming a ring system with N, the three units R are not substituted hydrocarbon groups at the same time, and N is not directly bonded to an aromatic group). It consists of a photosensitive catalyst containing a reducing agent and a polymerizable ethylenically unsaturated substance. Among the above, particularly preferred photosensitizers include biacetyl, benzyl, benzophenone, and camphorquinone, and reducing agents include trimethylamine, tripropylamine, dimethylamine, )propylamine, N , N'-dimethylaniline, N-methyldiphenylamine, ethylenediamine, hexamethylenediamine, dimethylaminoethyl methacrylate and piperidine. Although materials using these photoinitiators are rapidly cured by light irradiation, the cured products are markedly colored (often yellow) and change significantly in color over time in sunlight and water, and have low physical strength and physical properties. It had the disadvantage that only one product could be obtained.
本発明の目的は、上記従来技術の問題点を解決し、着色
及び色調経時変化がなく、且つ機械的特性に優れた製品
を与える光重合性組成物を提供することにある。An object of the present invention is to provide a photopolymerizable composition that solves the problems of the prior art described above and provides a product that is free from coloration and color change over time and has excellent mechanical properties.
本発明の光重合性組成物は、ビニルモノマーと光重合開
始剤とからなる光重合性組成物において、光重合開始剤
として、メルカプトカルボン酸とα−ジケトンとを組合
せ用いることを特徴とする。The photopolymerizable composition of the present invention is a photopolymerizable composition comprising a vinyl monomer and a photopolymerization initiator, and is characterized by using a combination of mercaptocarboxylic acid and α-diketone as the photopolymerization initiator.
本発明の組成物を形成するビニル糸上ツマ−は、単官能
性のビニル化合物であってもよく、また多官能性のビニ
ル化合物であってもよい。単官能性のビニル化合物の例
としては、スチレン、アクリロニトリル、酢酸ビニル、
メチルアクリレートおよびメタクリレート、エチルアク
リレートおよびメタクリレート、ブチルアクリレートお
よびメタクリレート、ヒドロキシエチルアクリレートお
よびメタクリレート、メトキシエチルアクリレートおよ
びメタクリレート、グリシジルアクリレートおよびメタ
クリレート、メタクリロキシエチルトリメリット酸およ
びその酸無水物等が挙げられる。The vinyl yarn thread forming the composition of the present invention may be a monofunctional vinyl compound or a polyfunctional vinyl compound. Examples of monofunctional vinyl compounds include styrene, acrylonitrile, vinyl acetate,
Examples include methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, hydroxyethyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, glycidyl acrylate and methacrylate, methacryloxyethyl trimellitic acid and its acid anhydride, and the like.
また、多官能性のビニル化合物の例としては、下記一般
式
%式%
(式中、R6は水素原子またはメチル基、pは1〜20
の整数である。)で示されるエチレングリコールジアク
リレートおよびメタクリレート、ジエチレングリコール
ジアクリレートおよびメタクリレート、トリエチレング
リコールジアクリレートおよびメタクリレート、ポリエ
チレングリコールジアクリレートおよびメタクリレート
類、1゜4−ブタンジオールジアクリレートおよびメタ
クリレート、1.3−ブタンジオールジアクリレートお
よびメタクリレート、1.6−ヘキサンジオールジアク
リレートおよびメタクリレート、グリセリンジアクリレ
ートおよびメタクリレート、ならびに下記一般式
(式中、R7は水素原子またはメチル基、pは1〜20
の整数である。)で示されるビスフェノールAジグリシ
ジルアクリレートおよびメタクリレート類、ウレタンジ
アクリレートおよびメタクリレート類、トリメチロール
プロパントリアクリレートおよびメタクリレート、ペン
タエリスリトールテトラアクリレートおよびメタクリレ
ート、ビスフェノールAジアクリレートおよびメタクリ
レート等が挙げられる。これらのアクリレートおよびメ
タクリレート類は、その1種を使用しても、2種以上を
組合せて用いてもよい。In addition, as an example of a polyfunctional vinyl compound, the following general formula % formula % (in the formula, R6 is a hydrogen atom or a methyl group, p is 1 to 20
is an integer. ) Ethylene glycol diacrylate and methacrylate, diethylene glycol diacrylate and methacrylate, triethylene glycol diacrylate and methacrylate, polyethylene glycol diacrylate and methacrylates, 1゜4-butanediol diacrylate and methacrylate, 1,3-butanediol diacrylate and methacrylate, 1,6-hexanediol diacrylate and methacrylate, glycerin diacrylate and methacrylate, and the following general formula (wherein R7 is a hydrogen atom or a methyl group, p is 1 to 20
is an integer. ), bisphenol A diglycidyl acrylate and methacrylates, urethane diacrylate and methacrylates, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, bisphenol A diacrylate and methacrylate, and the like. These acrylates and methacrylates may be used alone or in combination of two or more.
本発明の光重合開始剤として使用されるメルカプトカル
ボン酸は好ましくは、下記の一般式(式中、R8及びR
2は、直接結合、炭素数1〜5のアルキレン基またはフ
ェニレン基を示し、R2はニトロ基、水酸基、アミノ基
またはハロゲンを示す。)で表わされる化合物であり、
具体例としては、o−、m−およびp−メルカプト安息
香酸、o−、m−およびp−メルカプトフェニル酢酸、
o−、m−およびp−メルカプトフェニルプロピオン酸
、o−、m−およびp−メルカプトフェニル酪酸、メル
カプトビフェニルカルボン酸、o−、m−およびp−メ
ルカプトメチル安息香酸、0−ニトロ−p−メルカプト
安息香酸、0−ヒドロキシ−p−メルカプト安息香酸、
0−アミノ−p−メルカプト安息香酸、0−りoo−p
−メルカプト安息香酸等が挙げられる。特に好ましいメ
ルカプトカルボン酸としては、O−メルカプト安息香酸
(チオサリチル酸)、m−メルカプト安息香酸及びp−
メルカプト安息香酸等をあげることができる。The mercaptocarboxylic acid used as the photopolymerization initiator of the present invention preferably has the following general formula (where R8 and R
2 represents a direct bond, an alkylene group having 1 to 5 carbon atoms, or a phenylene group, and R2 represents a nitro group, a hydroxyl group, an amino group, or a halogen. ) is a compound represented by
Specific examples include o-, m- and p-mercaptobenzoic acid, o-, m- and p-mercaptophenylacetic acid,
o-, m- and p-mercaptophenylpropionic acid, o-, m- and p-mercaptophenylbutyric acid, mercaptobiphenylcarboxylic acid, o-, m- and p-mercaptomethylbenzoic acid, O-nitro-p-mercapto Benzoic acid, 0-hydroxy-p-mercaptobenzoic acid,
0-amino-p-mercaptobenzoic acid, 0-oo-p
-mercaptobenzoic acid and the like. Particularly preferred mercaptocarboxylic acids include O-mercaptobenzoic acid (thiosalicylic acid), m-mercaptobenzoic acid and p-mercaptobenzoic acid.
Examples include mercaptobenzoic acid.
α−ジケトンは、格別限定されるものではなくすべて適
用できるが、カンファーキノン、ベンジル、アセチルベ
ンゾイル、アセナフテンキノンα−ナフチル、ジクロロ
ベンジル、ビアセチル、β−ナフチル、ベンゾイン、α
−ナフトインおよびβ−ナフトインが好ましい。中でも
、カンファーキノンは最も好ましい。α-diketones are not particularly limited and all can be used, but camphorquinone, benzyl, acetylbenzoyl, acenaphthenequinone α-naphthyl, dichlorobenzyl, biacetyl, β-naphthyl, benzoin, α-diketone, etc.
-naphthoin and β-naphthoin are preferred. Among them, camphorquinone is most preferred.
上記光重合開始剤は前述のビニル系モノマーに対して1
0−5重量%〜30重量%の量、好ましくは10−3重
量%〜15重景%、特に好ましくは10−1〜5重量%
の量で添加する。なお、α−ジケトンの配合量はメルカ
プトカルボン酸に対して10−5重量%〜102重量%
、好ましくは10−3重量%〜50重量%、特に好まし
くはto−’重量%〜20重量%の範囲である。これら
の配合量は光重合硬化物の着色及び色調経時変化がなく
、さらに機械的強度の高い組成物を得る上で好適である
。The above photopolymerization initiator is 1% relative to the above vinyl monomer.
Amounts from 0-5% to 30% by weight, preferably from 10-3% to 15% by weight, particularly preferably from 10-1 to 5% by weight
Add in the amount of The amount of α-diketone is 10-5% to 102% by weight based on mercaptocarboxylic acid.
, preferably in the range from 10-3% to 50% by weight, particularly preferably from to-'% to 20% by weight. These blending amounts are suitable for obtaining a composition that does not cause coloration or color change over time of the photopolymerized cured product and has high mechanical strength.
本発明の組成物においては、必要に応じてさらにフィラ
ーが上述の成分に加えられる。かかるフィラー成分とし
ては、周期律第r、n、m、rv。In the composition of the present invention, a filler is further added to the above-mentioned components as necessary. Such filler components include periodic law numbers r, n, m, and rv.
V族、遷移金属およびそれらの酸化物、水酸化物、塩化
物、硫酸塩、亜硫酸塩、炭酸塩、リン酸塩、ケイ酸塩お
よびこれらの混合物、複合塩等が挙げられるが、中でも
二酸化ケイ素、石英粉末、酸化アルミニウム、硫酸バリ
ウム、酸化チタン、タルク、ガラス粉末、ガラスピーズ
、ガラス繊維、バリウム塩、鉛塩を含有するガラスフィ
ラー、シリカゲル、コロイダルシリカ、炭素繊維、ジル
コニウム酸化物、スズ酸化物、その他のセラミックス粉
末等が好ましい。なお、上記フィラーは、未処環フィラ
ー、シランカップリング剤等による表面処理フィラー及
びポリマーで複合化して粉砕した有機複合フィラーのい
ずれであっても適用できる。Examples include V group metals, transition metals, and their oxides, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates, and mixtures and composite salts thereof, among which silicon dioxide , quartz powder, aluminum oxide, barium sulfate, titanium oxide, talc, glass powder, glass beads, glass fiber, barium salt, glass filler containing lead salt, silica gel, colloidal silica, carbon fiber, zirconium oxide, tin oxide , other ceramic powders, etc. are preferred. The above-mentioned filler may be any of an untreated ring filler, a surface-treated filler using a silane coupling agent, and an organic composite filler composited with a polymer and pulverized.
上記フィラーの配合量は、光重合硬化物の使用目的に応
じて適宜変えられるが、例えば、歯科材料用充填材とし
て用いる場合には、前述のビニル系モノマーに対して、
1〜103重量%、好ましくは10〜9.5X10”重
量%、特に好ましくは20〜9.0X102重量%の範
囲で配合されて、ペースト状の組成物として用いられる
。The blending amount of the filler can be changed as appropriate depending on the purpose of use of the photopolymerized cured product, but for example, when used as a filling material for dental materials,
It is blended in a range of 1 to 103% by weight, preferably 10 to 9.5×10”% by weight, particularly preferably 20 to 9.0×102% by weight, and used as a paste composition.
さらに、本発明の組成物には、必要に応じて着色剤、重
合禁止剤(例えば、ハイドロキノン、メトキシベンゾフ
ェノン、メチルフェノール、ハイドロキノンモノメチル
エーテル等)、酸化安定剤、紫外線吸収剤(例えば、ペ
ンヅフェノン等)、顔料(例えば、酸化鉄、酸化チタン
等)、染料などを配合することもできる。Furthermore, the composition of the present invention may optionally contain a colorant, a polymerization inhibitor (e.g., hydroquinone, methoxybenzophenone, methylphenol, hydroquinone monomethyl ether, etc.), an oxidation stabilizer, and an ultraviolet absorber (e.g., penduphenone, etc.). , pigments (for example, iron oxide, titanium oxide, etc.), dyes, etc. can also be blended.
本発明に係る光重合性組成物においては、可視光線領域
で硬化し得る光重合開始剤を使用しているため、従来の
紫外線による光重合の欠点である人体に対する有害性、
硬化性能(深度)が劣る及び設備投資が高価である等の
問題点をすべて解決したものであり、また、光硬化して
得られる硬化物は、従来方法では得られなかった優れた
色調安定性および外観性能と高い機械的性質を有する。Since the photopolymerizable composition of the present invention uses a photopolymerization initiator that can be cured in the visible light range, it is not harmful to the human body, which is a drawback of conventional photopolymerization using ultraviolet light.
This method solves all problems such as poor curing performance (depth) and high equipment investment, and the cured product obtained by photocuring has excellent color stability that could not be obtained with conventional methods. and has good appearance performance and high mechanical properties.
次に、実施例により、本発明をさらに詳細に説明するが
、本発明はかかる実施例に限定されるものではない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.
実施例1〜3.比較例1〜2
からなるモノマー混合物を、下面がシールされたテフロ
ン筒(内径4mm、高さ20mm)に上液面がテフロン
筒上面と一致するまで注ぎ入れた。次に、3M社の可視
光照射器(商品名: 0PTILUX)の光線照射面と
上記液面との距離が1m1I+になるように配置して3
0秒間可視光線を照射した。その後、注入上ツマー混合
物をテフロン筒からはずし、未重合部分を除いて、得ら
れた重合硬化物の“厚み”を測定した。Examples 1-3. A monomer mixture consisting of Comparative Examples 1 and 2 was poured into a Teflon cylinder (inner diameter 4 mm, height 20 mm) whose bottom surface was sealed until the upper liquid level coincided with the top surface of the Teflon cylinder. Next, the distance between the light irradiation surface of the 3M company's visible light irradiator (product name: 0PTILUX) and the above liquid level was 1 m1I+.
Visible light was irradiated for 0 seconds. Thereafter, the injection mixture was removed from the Teflon tube, the unpolymerized portion was removed, and the "thickness" of the resulting polymerized and cured product was measured.
第1表に光開始剤の種類、量及び前述の“厚み測定結果
を示す。Table 1 shows the type and amount of the photoinitiator and the results of the thickness measurement described above.
第1表から明らかなように、本発明による組成物は比較
例の公知組成物に比べて、優れた光硬化性能を有するこ
とが判る。また、本発明による光硬化重合体の外観は、
着色がほとんどなく、比較例よりも著しくきれいであっ
た。As is clear from Table 1, it can be seen that the composition according to the present invention has superior photocuring performance compared to the known composition of the comparative example. Moreover, the appearance of the photocurable polymer according to the present invention is as follows:
There was almost no coloration, and it was much cleaner than the comparative example.
からなる七ツマ−・フィラー混合物(ペースト)を下面
がシールされたテフロン筒(内径4ml11、高さ20
1)に上ペースト面が、テフロン筒上面と一敗するまで
つめ込んだ。次に、3M社の可視光照射器(商品名:
0PTILLIχ)の光線照射面と上記ペースト面との
距離が1++mになるように配置して、30秒間、可視
光線を照射した。その後、注入ペーストをテフロン筒か
らはずし、未重合部分を除いて、得られた重合硬化物の
“厚み”を測定した。A Teflon tube (inner diameter 4 ml, height 20
1) was packed until the upper paste surface was completely flush with the top surface of the Teflon tube. Next, 3M's visible light irradiator (product name:
Visible light was irradiated for 30 seconds with the paste surface placed such that the distance between the light irradiated surface of the 0PTILLIx and the paste surface was 1++ m. Thereafter, the injection paste was removed from the Teflon tube, the unpolymerized portion was removed, and the "thickness" of the resulting polymerized and cured product was measured.
第2表に光開始剤の種類、量及び前述の“厚み”測定結
果を示す。Table 2 shows the type and amount of photoinitiator and the results of the above-mentioned "thickness" measurement.
第2表
第2表から明らかなようにフィラーが追加された場合に
おいても、本発明による組成物は、比較例の公知組成物
に比べて、優れた光硬化性能を有することが判る。また
、本発明による光硬化重合体の外観は、着色がほとんど
なく、比較例よりも著しくきれいであった。As is clear from Table 2, even when a filler is added, the composition according to the present invention has superior photocuring performance compared to the known composition of the comparative example. In addition, the appearance of the photocurable polymer according to the present invention had almost no coloration and was significantly cleaner than that of the comparative example.
比較例5
実施例1及び4に相当する混合物をそれぞれ前記テフロ
ン筒に注入後、テフロン筒上面をアルミはくで覆って、
可視光線が注入混合物に到達できない状態にした後、注
入混合物上面と光線照射面との距離が1mmになるよう
に配置して3分間可視光線を照射したが重合は起らなか
った。Comparative Example 5 After injecting the mixtures corresponding to Examples 1 and 4 into the Teflon cylinder, the top surface of the Teflon cylinder was covered with aluminum foil,
After making it impossible for visible light to reach the injection mixture, the mixture was placed so that the distance between the top surface of the injection mixture and the light irradiation surface was 1 mm, and visible light was irradiated for 3 minutes, but no polymerization occurred.
比較例6
実施例1及び4に相当する混合物をそれぞれ前記テフロ
ン筒に注入後、テフロン筒上面をアルミはくで覆って、
可視光線が注入混合物に到達できない状態にした後、3
分間60℃に加熱したが、重合は起らなかった。Comparative Example 6 After injecting the mixtures corresponding to Examples 1 and 4 into the Teflon cylinder, the top surface of the Teflon cylinder was covered with aluminum foil,
After making visible light unable to reach the injection mixture, 3
Although heated to 60° C. for minutes, no polymerization occurred.
実施例7〜9.比較例7〜9
からなるモノマー・フィラー混合物(ペースト)を実施
例4と同様に操作して60秒間可視光線を照射した後、
得られた光重合硬化物を切断して4X6mmの円筒状試
片を作製し、その圧縮強度、太陽光による1週間曝露試
験後の色調変化及び60℃水中での1週間浸漬試験後の
色調変化を測定した。Examples 7-9. A monomer filler mixture (paste) consisting of Comparative Examples 7 to 9 was operated in the same manner as in Example 4 and irradiated with visible light for 60 seconds,
The obtained photopolymerized cured product was cut into 4 x 6 mm cylindrical specimens, and their compressive strength, color change after a one-week exposure test to sunlight, and color tone change after a one-week immersion test in 60°C water were measured. was measured.
第3表に光開始剤の種類、量及び前述の測定結果を示す
。Table 3 shows the type and amount of the photoinitiator and the above measurement results.
以下余白
第3表から明らかなように本発明による組成物は比較例
の公知組成物に比べて、優れた機械的物性を有し、しか
も色調安定性が極めて高いことが判る。As is clear from Table 3 below, it can be seen that the compositions according to the present invention have superior mechanical properties and extremely high color stability compared to the known compositions of comparative examples.
Claims (5)
合性組成物において、光重合開始剤がメルカプトカルボ
ン酸とα−ジケトンとの組合せであることを特徴とする
光重合性組成物。(1) A photopolymerizable composition comprising a vinyl monomer and a photopolymerization initiator, wherein the photopolymerization initiator is a combination of mercaptocarboxylic acid and α-diketone.
フィラーを含んでなる特許請求の範囲第1項記載の光重
合性組成物。(2) The photopolymerizable composition according to claim 1, further comprising a filler in addition to the vinyl monomer and the photopolymerization initiator.
のアルキレン基またはフェニレン基を示し、R_3はニ
トロ基、水酸基、アミノ基またはハロゲンを示す。)で
表わされる化合物である特許請求の範囲第1項または第
2項記載の光重合性組成物。(3) Mercaptocarboxylic acid has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 are direct bonds, carbon numbers 1 to 5
represents an alkylene group or a phenylene group, and R_3 represents a nitro group, a hydroxyl group, an amino group or a halogen. ) The photopolymerizable composition according to claim 1 or 2, which is a compound represented by:
の範囲第1項または第2項記載の光重合性組成物。(4) The photopolymerizable composition according to claim 1 or 2, wherein the α-diketone is camphorquinone.
香酸(チオサリチル酸)、メタ−メルカプト安息香酸ま
たはパラ−メルカプト安息香酸である特許請求の範囲第
1項または第2項記載の光重合性組成物。(5) The photopolymerizable composition according to claim 1 or 2, wherein the mercaptocarboxylic acid is ortho-mercaptobenzoic acid (thiosalicylic acid), meta-mercaptobenzoic acid, or para-mercaptobenzoic acid.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9954585A JPS61258802A (en) | 1985-05-13 | 1985-05-13 | Photopolymerizable composition |
US06/765,925 US4777190A (en) | 1985-05-13 | 1985-08-15 | Photopolymerizable composition based on a vinyl compound, a sulfur-containing compound and an α-diketone |
AU57192/86A AU594336B2 (en) | 1985-05-13 | 1986-05-06 | Photopolymerisable composition |
CA000508595A CA1282541C (en) | 1985-05-13 | 1986-05-07 | Photopolymerizable composition |
DE8686106431T DE3680711D1 (en) | 1985-05-13 | 1986-05-12 | PHOTOPOLYMERIZABLE COMPOSITION. |
EP86106431A EP0201903B1 (en) | 1985-05-13 | 1986-05-12 | Photopolymerizable composition |
US07/227,606 US5047442A (en) | 1985-05-13 | 1988-08-02 | Photopolymerizable composition based on a vinyl compound, a sulfur-containing compound and an alpha-diketone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9954585A JPS61258802A (en) | 1985-05-13 | 1985-05-13 | Photopolymerizable composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61258802A true JPS61258802A (en) | 1986-11-17 |
Family
ID=14250149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9954585A Pending JPS61258802A (en) | 1985-05-13 | 1985-05-13 | Photopolymerizable composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61258802A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5275917A (en) * | 1991-07-09 | 1994-01-04 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US5514521A (en) * | 1990-08-22 | 1996-05-07 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US6025112A (en) * | 1996-02-09 | 2000-02-15 | Brother Kogyo Kabushiki Kaisha | Photocurable composition and photosensitive capsules |
US6171759B1 (en) | 1992-05-14 | 2001-01-09 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US6242149B1 (en) | 1997-12-22 | 2001-06-05 | Brother Kogyo Kabushiki Kaisha | Fast-curing photosensitive composition and recording sheet |
-
1985
- 1985-05-13 JP JP9954585A patent/JPS61258802A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5514521A (en) * | 1990-08-22 | 1996-05-07 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US5275917A (en) * | 1991-07-09 | 1994-01-04 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US6171759B1 (en) | 1992-05-14 | 2001-01-09 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
US6025112A (en) * | 1996-02-09 | 2000-02-15 | Brother Kogyo Kabushiki Kaisha | Photocurable composition and photosensitive capsules |
US6242149B1 (en) | 1997-12-22 | 2001-06-05 | Brother Kogyo Kabushiki Kaisha | Fast-curing photosensitive composition and recording sheet |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0968459B1 (en) | Ternary photoinitiator system for curing of epoxy resins | |
AU744316B2 (en) | Ternary photoinitiator system for curing of epoxy/polyol resin compositions | |
US4923905A (en) | Light curable dental composition | |
CA1076296A (en) | Photo-polymerizable dental restorative and tooth coating composition comprising an oligomeric resin, an acrylate monomer, an organic peroxide and a photosensitizer | |
US4439380A (en) | Photopolymerizable composition, especially for dental purposes | |
US4372836A (en) | Light curable acrylic dental composition with calcium fluoride pigment | |
JPH0653647B2 (en) | Dental restoration composition | |
JPH024705A (en) | Titanate initiator for a photosetting composition | |
EP0047097B1 (en) | Visible light curable dental compositions | |
US4534839A (en) | Process for the photopolymerization of vinyl compounds and photopolymerizable materials | |
US4777190A (en) | Photopolymerizable composition based on a vinyl compound, a sulfur-containing compound and an α-diketone | |
JPH03111402A (en) | Near-infrared polymerization initiator | |
US4843110A (en) | Light curing compositions for dental restoration | |
CA1117685A (en) | One paste polymeric dental restorative composition | |
US4771084A (en) | Light curing compositions for dental restoration | |
JPS61258802A (en) | Photopolymerizable composition | |
JPS63316709A (en) | Photo-setting dental composition | |
JPS61258803A (en) | Photopolymerizable composition | |
JPH0521121B2 (en) | ||
US5583164A (en) | Dental compositions comprising bifunctional or polyfunctional acrylic-acid esters or methacrylic-acid esters | |
JPS6261906A (en) | Photopolymerizable composition for dental restoration | |
JPS6218403A (en) | Photopolymerizable composition | |
JP3506564B2 (en) | Dental photopolymerizable composition | |
JPH02155904A (en) | Photopolymerizable composition | |
JPH04261406A (en) | Near infrared photopolymerization initiator |