KR102510805B1 - Photo curable resin composition for 3D printing comprising biomass-derived 1,5-pentamethylenediisocyanate-isocyanurate acrylate - Google Patents
Photo curable resin composition for 3D printing comprising biomass-derived 1,5-pentamethylenediisocyanate-isocyanurate acrylate Download PDFInfo
- Publication number
- KR102510805B1 KR102510805B1 KR1020200186400A KR20200186400A KR102510805B1 KR 102510805 B1 KR102510805 B1 KR 102510805B1 KR 1020200186400 A KR1020200186400 A KR 1020200186400A KR 20200186400 A KR20200186400 A KR 20200186400A KR 102510805 B1 KR102510805 B1 KR 102510805B1
- Authority
- KR
- South Korea
- Prior art keywords
- acrylate
- methacrylate
- isocyanurate
- pentamethylene diisocyanate
- diacrylate
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 239000002028 Biomass Substances 0.000 title claims abstract description 22
- 238000010146 3D printing Methods 0.000 title abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 29
- -1 nonylphenol acrylate Ethyl acrylate Chemical compound 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- 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 claims description 20
- 239000003365 glass fiber Substances 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 11
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 9
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 8
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 4
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 claims description 4
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 claims description 4
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 4
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- DABQKEQFLJIRHU-UHFFFAOYSA-N 2-Propenoic acid, 2-methyl-, 3,3,5-trimethylcyclohexyl ester Chemical compound CC1CC(OC(=O)C(C)=C)CC(C)(C)C1 DABQKEQFLJIRHU-UHFFFAOYSA-N 0.000 claims description 4
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 4
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 4
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 4
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 4
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 4
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 4
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 claims description 4
- KSXJRXNHRYSLLC-UHFFFAOYSA-N 9H-fluorene prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.C1=CC=C2CC3=CC=CC=C3C2=C1 KSXJRXNHRYSLLC-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 claims description 4
- MNHBRBJOBAXMLL-UHFFFAOYSA-N OC(C=CCC(CC=CC(O)=O)(CC1)C2C1C1CC2CC1)=O Chemical compound OC(C=CCC(CC=CC(O)=O)(CC1)C2C1C1CC2CC1)=O MNHBRBJOBAXMLL-UHFFFAOYSA-N 0.000 claims description 4
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- GSJNBCZKEUYYLK-UHFFFAOYSA-N [phenoxy(phenyl)methyl] prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)OC1=CC=CC=C1 GSJNBCZKEUYYLK-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 4
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 4
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 4
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 4
- NGYRYRBDIPYKTL-UHFFFAOYSA-N icosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C=C NGYRYRBDIPYKTL-UHFFFAOYSA-N 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 4
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 4
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 4
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 4
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 4
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 4
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 claims description 4
- WPDBAIRIXJBWDB-UHFFFAOYSA-N propan-2-one;1-propan-2-ylthioxanthen-9-one Chemical compound CC(C)=O.S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C WPDBAIRIXJBWDB-UHFFFAOYSA-N 0.000 claims description 4
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 4
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 claims description 4
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 claims description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
- CSNNRKSTBPAVND-UHFFFAOYSA-N CC1N(CCOC1CC(C)=O)C=1SC=C(C=1)C Chemical compound CC1N(CCOC1CC(C)=O)C=1SC=C(C=1)C CSNNRKSTBPAVND-UHFFFAOYSA-N 0.000 claims description 3
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 claims description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000001723 curing Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000582 polyisocyanurate Polymers 0.000 description 4
- 239000011495 polyisocyanurate Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
- C08F22/22—Esters containing nitrogen
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- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
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- C08K7/04—Fibres or whiskers inorganic
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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Abstract
본 발명은 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물에 관한 것으로, 보다 상세하게는, 바이오매스 유래 1,5-펜타메틸렌디아민을 1,5-펜타메틸렌디이소시아네이트로 전환시킨 후, 상기 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 합성하고, 상기 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트를 부가하여 라디칼 경화가 가능하여 SLA나 DLP 기반의 3D프린팅에 적용이 가능한 내열성과 현상성이 우수한 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물에 관한 것이다.The present invention relates to a 3D photocurable resin composition comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound, and more particularly, to a biomass-derived 1,5-pentamethylenediamine After conversion to 1,5-pentamethylene diisocyanate, the 1,5-pentamethylene diisocyanate is trimerized in the presence of a trimerization catalyst to synthesize 1,5-pentamethylene diisocyanate-isocyanurate, 1,5-pentamethylene diisocyanate-isocyanurate is a bio product with excellent heat resistance and developability that can be applied to SLA or DLP-based 3D printing by adding an acrylate having a hydroxyl group to the terminal isocyanate group to enable radical curing. It relates to a 3D photocurable resin composition comprising a mass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound.
Description
본 발명은 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물에 관한 것으로, 보다 상세하게는, 바이오매스 유래 1,5-펜타메틸렌디아민을 1,5-펜타메틸렌디이소시아네이트로 전환시킨 후, 상기 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 합성하고, 상기 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가하여 라디칼 경화가 가능하여 SLA나 DLP 기반의 3D프린팅에 적용이 가능한 내열성과 현상성이 우수한 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물에 관한 것이다.The present invention relates to a 3D photocurable resin composition comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound, and more particularly, to a biomass-derived 1,5-pentamethylenediamine After conversion to 1,5-pentamethylene diisocyanate, the 1,5-pentamethylene diisocyanate is trimerized in the presence of a trimerization catalyst to synthesize 1,5-pentamethylene diisocyanate-isocyanurate, Radical curing is possible by adding acrylate or methacrylate having a hydroxyl group to the terminal isocyanate group of 1,5-pentamethylene diisocyanate-isocyanurate. Heat resistance and development that can be applied to SLA or DLP-based 3D printing It relates to a 3D photocurable resin composition comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound having excellent properties.
일반적으로, 3D 프린팅 방식은 FDM(Fused Deposition Medeling), SLA(Stereo Lithography Apparatus), SLS(Selective Laser Sintering), DLP(Digital Light Processing) 방식으로 구분된다.In general, 3D printing methods are classified into Fused Deposition Medeling (FDM), Stereo Lithography Apparatus (SLA), Selective Laser Sintering (SLS), and Digital Light Processing (DLP) methods.
상기 FDM(Fused Deposition Medeling) 방식은 열가소성 플라스틱(PLA, ABS, Ultem 등)을 노즐 안에서 녹여 적층하면서 제품을 프린팅하는 것으로, 이 방식은 주로 항공 우주, 자동차, 건축과 다양한 부품에 활용이 되고 있으며, 최근에는 의료 산업으로 많이 개발되고 있는 추세이며, 광개시제가 필요 없기 때문에 상대적으로 강도가 높은 장점이 있고, 또한 고가의 레이저가 필요 없어 장비가 상대적으로 저렴하고, 가공비용이 싸기 때문에 주로 맞춤형 소량 생산이나 프로토 타입을 만들 때 유리한 장점이 있다.The FDM (Fused Deposition Medeling) method prints products while melting and stacking thermoplastic plastics (PLA, ABS, Ultem, etc.) in a nozzle. This method is mainly used for aerospace, automobiles, construction and various parts, Recently, it has been developed a lot for the medical industry, and it has the advantage of relatively high strength because it does not require a photoinitiator, and also because it does not require an expensive laser, the equipment is relatively cheap, and the processing cost is cheap, so it is mainly used for customized small-volume production or There are advantages to prototyping.
그러나, 상기 FDM(Fused Deposition Medeling) 방식은 열에 의해 녹았던 열가소성 플라스틱이 식으면서 변형 및 수축이 발생하여 정밀한 구조와 우수한 현상성이 요구되는 제품을 3D 프린팅하기에는 불가능한 문제점이 있다.However, the Fused Deposition Medeling (FDM) method has a problem in that it is impossible to 3D print a product that requires a precise structure and excellent developability because deformation and contraction occur while the thermoplastic melted by heat cools.
한편, 상기 SLA(Stereo Lithography Apparatus), DLP(Digital Light Processing) 방식은 액상의 광경화성 수지에 빛을 조사하여 경화시켜 조형물을 제작하는 것으로서, 자외선 또는 빛을 이용한 경화방식을 이용하기 때문에 기구적 움직임(Z축)이 최소이고 형상 제작시 실패율이 낮아 3D 프린팅 방식에서 FDM 방식을 보완하여 많이 사용되고 있다.On the other hand, the SLA (Stereo Lithography Apparatus) and DLP (Digital Light Processing) methods produce a sculpture by irradiating light to a liquid photocurable resin and curing it. Since a curing method using ultraviolet light or light is used, mechanical movement (Z-axis) is minimal and the failure rate is low during shape production, so it is widely used as a complement to the FDM method in the 3D printing method.
상기 SLA 또는 DLP 방식의 3D 프린터는 아크릴, 우레탄, 에폭시 중 하나 이상을 포함하는 광경화성 고분자(photopolymer) 수지에 빛(가시광선)을 조사하여 3차원 형상의 플라스틱 조형물을 제작하는 것이다.The SLA or DLP 3D printer produces a three-dimensional plastic sculpture by irradiating light (visible light) to a photopolymer resin containing at least one of acrylic, urethane, and epoxy.
즉, CAD 시스템으로 모델링한 3차원 형상을 0.05∼0.1mm 두께의 다수의 층으로 분할한 후, 이들 각 층을 슬라이스 데이터(slice data)로 변경하고, 이를 사용하여 광경화성 수지에 빛을 조사하면서 한층 또 한층 차례로 경화시 키면서 적층함으로써 조형물을 완성하는 방식으로 각종 형태의 정밀한 제품을 제조하고 있으며, 현재 상기 광경화 방식 3D 프린터에 이용되는 광경화 조성물이 매우 다양하게 개발되고 있다.That is, after dividing the three-dimensional shape modeled by the CAD system into a plurality of layers with a thickness of 0.05 to 0.1 mm, each of these layers is converted into slice data, and using this, while irradiating light on the photocurable resin, Precise products of various shapes are manufactured in a way to complete a sculpture by laminating while curing one layer after another, and photocuring compositions used in the photocuring 3D printer are currently being developed in a variety of ways.
종래 개발된 3D 프린팅용 광경화 수지 조성물을 살펴 보면, 한국공개특허 특2003-0009435(공개일자 2003년01년29일)에 삼차원 프린터에서 입체물을 형성시키는 화학 조성물로서, 성분이 비수성 유기 단량체 화합물을 포함하며, 상기 화합물이 알코올, 에스테르, 에테르, 실란, 비닐 단량체, 아크릴 단량체 또는 메타크릴레이트 단량체 중 하나 이상을 포함하되, 상기 아크릴 단량체가 트리(프로필렌 글리콜) 디아크릴레이트, 에틸렌 글리콜 페닐 에테르 아크릴레이트 또는 1,6 헥산디올 디아크릴레이트중 하나 이상을 포함하거나, 상기 메타크릴 단량체가 1,3 부틸렌 글리콜 디메타크릴레이트, 네오펜틸 글리콜 디메타크릴레이트, 부틸메타크릴레이트, 1,6 헥산디올 디메타크릴레이트 또는 디(프로필렌 글리콜) 알릴 에테르 메타크릴레이트중 하나 이상을 포함함을 특징으로 하는 삼차원 프린터용 광경화 조성물이 공지되어 있다.Looking at the conventionally developed photocurable resin composition for 3D printing, Korean Patent Publication No. 2003-0009435 (published on the 29th of January 2003) is a chemical composition for forming a three-dimensional object in a three-dimensional printer, and the component is a non-aqueous organic monomer compound wherein the compound includes one or more of alcohol, ester, ether, silane, vinyl monomer, acrylic monomer or methacrylate monomer, wherein the acrylic monomer is tri(propylene glycol) diacrylate, ethylene glycol phenyl ether acrylic 1,6 hexanediol diacrylate or at least one of 1,6 hexanediol diacrylate, or the methacrylic monomer is 1,3 butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate, 1,6 hexane A photocurable composition for a three-dimensional printer is known, characterized in that it contains at least one of diol dimethacrylate and di(propylene glycol) allyl ether methacrylate.
또한, 한국공개특허 10-2012-0055242(공개일자 2012년05월31일)에는 광경화형 수지 조성물 100 중량부에 대하여, 아크릴계 화합물 50~80 중량부, 실세스퀴옥산 10~50 중량부, 광경화성 이형제 0.5~5 중량부 및 자외선 개시제 1~5 중량부를 포함하고, 상기 아크릴계 화합물은 단관능성 모노머, 이관능성 모노머, 삼관능성 모노머, 다관능성 모노머 및 이들의 혼합물로 구성된 군에서 선택되며, 상기 실세스퀴옥산은 아크릴레이트 또는 메타크릴레이트 기를 가지는 실세스퀴옥산 및 이들 의 혼합물로 구성된 군에서 선택되는 것을 특징으로 하는 광경화형 수지 조성물이 공지되어 있다.In addition, Korean Patent Publication No. 10-2012-0055242 (published on May 31, 2012) discloses 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, and 100 parts by weight of a photocurable resin composition. 0.5 to 5 parts by weight of a chemical release agent and 1 to 5 parts by weight of an ultraviolet initiator, and the acrylic compound is selected from the group consisting of monofunctional monomers, difunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof, A photocurable resin composition is known in which sesquioxane is selected from the group consisting of silsesquioxane having an acrylate or methacrylate group and mixtures thereof.
또한, 한국공개특허 10-2012-0137258(공개일자 2012년12월20일)에는 아크릴수지 기판 등의 기판에 대한 습윤 전개성이 우수한 광경화성 잉크젯 잉크이며, 기판으로의 밀착성이 우수한 표면 발액성 경화막을 형성할 수 있는 광경화성 잉크젯 잉크로서, 유기용매(A), 히드록시기를 갖는 2관능 이하의 (메타)아크릴레이트(B), 우레탄(메타)아크릴레이트(C), 계면활성제(D) 및 광중합 개시제(E)를 함유하고, 상기 우레탄(메타)아크릴레이트(C)가 화학식(2)로 표시되는 광경화성 잉크젯 잉크가 공지되어 있다.In addition, Korean Patent Publication No. 10-2012-0137258 (published on December 20, 2012) is a photocurable inkjet ink with excellent wet spreadability for substrates such as acrylic resin substrates, and a surface liquid repellent curing with excellent adhesion to substrates As a photocurable inkjet ink capable of forming a film, an organic solvent (A), a hydroxyl group having a bifunctional (meth)acrylate (B), a urethane (meth)acrylate (C), a surfactant (D), and photopolymerization A photocurable inkjet ink containing an initiator (E) and wherein the urethane (meth)acrylate (C) is represented by formula (2) is known.
(화학식(2)에서, R1, R2 및 R3은 각각 독립적으로 탄소수 1 내지 20인 2가의 유기기이며, R4 및 R5는 각각 독립적으로 수소 또는 탄소수 1 내지 6의 알킬이며, m 및 n은 각각 독립적으로 1 내지 3의 정수이다.)(In Formula (2), R1, R2 and R3 are each independently a divalent organic group having 1 to 20 carbon atoms, R4 and R5 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and m and n are each independently is an integer from 1 to 3.)
또한, 한국공개특허 10-2016-0058595(공개일자 2016년05월25일)에는 피에조 헤드를 이용한 자외선 경화형 잉크젯 방식을 적용하여 3차원 연성 조형물을 형성하기 위한 컬러 잉크 조성물에 있어서, 아크릴레이트계 올리고머 13 내지 30 중량%; 아크릴레이트계 단관능 및 다관능 모노머 60 내지 80중량%; 안료 0.1 내지 2.0중량%; 광개시제 4 내지 12 중량%; 및 레벨링제 및 안정제를 포함하는 첨가제 1 내지 5 중량%를 포함하는 3차원 연성 조형물 형성용 잉크 조성물이 공지된 바 있다.In addition, Korean Patent Publication No. 10-2016-0058595 (published on May 25, 2016) discloses an acrylate-based oligomer in a color ink composition for forming a three-dimensional flexible object by applying an ultraviolet curable inkjet method using a piezo head. 13 to 30% by weight; 60 to 80% by weight of acrylate-based monofunctional and multifunctional monomers; 0.1 to 2.0% by weight of a pigment; 4 to 12% by weight of a photoinitiator; And an ink composition for forming a three-dimensional flexible object containing 1 to 5% by weight of an additive including a leveling agent and a stabilizer is known.
그러나, 상기한 3D프린팅용 광경화 수지조성물들은 경화메카니즘이 아크릴레이트 또는 메타크릴레이트 이중결합의 광경화에 의한 라디칼 연쇄중합반응으로 경화되기 때문에 이로 인하여 현상성(미세선폭 구현)과 수축률이 불량한 심각한 문제가 있었다.However, since the curing mechanism of the photocurable resin compositions for 3D printing is cured by a radical chain polymerization reaction by photocuring of acrylate or methacrylate double bonds, this causes serious problems such as poor developability (realization of fine line width) and poor shrinkage. There was a problem.
상기한 문제점들을 개선하기 위하여, 본 출원인은 한국등록특허 10-1838520(등록일자 2018년03월08일)에서 하기 [화학식 1]로 표시되는 지환족 에폭시 화합물의 하나의 에폭시 고리에 친수성기를 갖는 아크릴계 모노머를 부가반응시켜 하나의 에폭시 고리가 개환되어 아크릴기 또는 메타크릴기가 부가된 형태를 가지므로 에폭시기에 의한 양이온경화 및 아크릴기 또는 메타크릴기에 의한 자외선경화 메커니즘을 동시에 가지는 신규한 지환족 에폭시 아크릴계 화합물과, 아크릴 모노머와, 글리시딜에테르와, 옥세탄 화합물과, 광개시제 및 양이온개시제를 포함하여 조성되는 것을 특징으로 하는 현상성과 수축률이 우수한 3D프린팅용 수지 조성물을 출원하여 특허받은 바 있다.In order to improve the above problems, the applicant of the Korean Patent Registration No. 10-1838520 (registration date March 8, 2018) has an acrylic type having a hydrophilic group on one epoxy ring of an alicyclic epoxy compound represented by the following [Chemical Formula 1] A novel alicyclic epoxy acrylic compound having a cationic curing mechanism by an epoxy group and an ultraviolet curing mechanism by an acrylic or methacrylic group at the same time as it has a form in which an acrylic or methacrylic group is added by ring-opening one epoxy ring by addition reaction of a monomer. And, an acrylic monomer, glycidyl ether, an oxetane compound, a photoinitiator and a cationic initiator, characterized in that it is composed of a resin composition for 3D printing with excellent developability and shrinkage.
[화학식 2][Formula 2]
그러나, 상기 지환족 에폭시 아크릴계 화합물을 포함하는 3D프린팅용 수지 조성물은 에폭시기에 의한 양이온경화가 아크릴계 화합물의 라디칼경화보다 경화속도가 늦은 단점이 있었을 뿐만 아니라, 고가의 양이온 개시제를 사용하는 문제점이 있었다.However, the resin composition for 3D printing containing the cycloaliphatic epoxy-acrylic compound has disadvantages in that cationic curing by an epoxy group has a slower curing rate than radical curing of the acrylic compound, and also has a problem of using an expensive cationic initiator.
한편, 상기 3D프린팅용 광경화 수지 조성물들은 3D 프린트 인출 공정에 적용할 수 있는 빠른 경화와 적절히 낮은 점도를 갖고 있어야 하므로 전형적으로 올리고머와 반응성 희석제를 사용하여야 한다.On the other hand, since the photocurable resin compositions for 3D printing should have fast curing and appropriately low viscosity applicable to the 3D print extraction process, oligomers and reactive diluents should typically be used.
그러나, 상기 3D프린팅용 광경화 수지 조성물들은 빠른 경화 특성을 나타내면서 적정한 수준의 반응성 희석제를 첨가하여 비교적 낮은 점도로 조절해야 하며, 상기한반응성 희석제는 저분자량의 반응성 모노머로써 경화중에 휘발 성분을 방출하며, 수축율이 높아 치수 안정성을 낮추는 현상을 야기한다는 결점이 있었으며, 낮은 자외선 광량에서 높은 경도를 나타내지 못하는 단점이 있었으며, 특히, 3D 프린트의 레이저에서 방출하는 자외선에서 충분히 경화되지 못하는 경우 또는 광중합형 올리고머와 반응성 희석제의 조성비가 불균일한 경우에는 낮은 모듈러스(Modulus) 값을 가지게 되어 강도 또는 경도 물성이 저하되는 문제점이 있었다.However, the photocurable resin composition for 3D printing exhibits fast curing characteristics and needs to be adjusted to a relatively low viscosity by adding an appropriate level of reactive diluent. The reactive diluent is a low molecular weight reactive monomer and releases volatile components during curing. , there was a drawback that the shrinkage rate was high, which caused a phenomenon of lowering dimensional stability, and there was a disadvantage that it did not show high hardness at a low amount of ultraviolet light. When the composition ratio of the reactive diluent is non-uniform, it has a low modulus value, resulting in a decrease in strength or hardness properties.
뿐만 아니라, 상기와 같이 점도가 낮게 조절하려면 분자량이 커야 하는데 분자량이 큰 물질은 고점도의 성질을 띄고 있기 때문에 잉크 재료 선정에 있어 한계가 있으며, 특히, 성형품의 특성이 높은 강도를 가지게 하는데는 한계가 있었으므로 상기한 문제점을 해결하기 위하여 우레탄아크릴레이트를 사용한 광경화 조성물이 개발되었다.In addition, in order to control the viscosity to a low level as described above, the molecular weight must be high, but since a substance with a high molecular weight has a high viscosity, there is a limit in the selection of ink materials, and in particular, there is a limit in making the characteristics of molded products have high strength. Since there was, a photocurable composition using urethane acrylate was developed to solve the above problems.
즉, 한국공개특허 10-2017-0010299(공개일자 2017년01월26일)에 2개 이상의 이소시아네이트기를 갖는 폴리이소시아네이트, 분자 내에 하이드록시기를 갖고 1개 이상의 아크릴기를 포함하는 아크릴레이트, 축중합 촉매 및 라디칼 중합 방지제를 반응시켜 제조되는, 하기 화학식 1로 표시되는 우레탄 아크릴레이트 올리고머가 개발되었다.That is, in Korea Patent Publication No. 10-2017-0010299 (published on January 26, 2017), a polyisocyanate having two or more isocyanate groups, an acrylate having a hydroxyl group in a molecule and including one or more acryl groups, a polycondensation catalyst, and A urethane acrylate oligomer represented by the following formula (1) prepared by reacting a radical polymerization inhibitor has been developed.
[화학식 1][Formula 1]
(상기 식에서, B 및 P는 각각 독립적으로 하이드록시기를 포함하는 폴리올이고, I는 3개 이상의 아크릴기를 포함하는 (메타)아크릴레이트이고, M은 하이드록시기를 포함하는 (메타)아크릴레이트이고, n은 1 내지 3의 정수이고, p는 1 내지 4의 정수이고, 그리고 q는 1 내지 4의 정수이다.)(Wherein, B and P are each independently a polyol containing a hydroxyl group, I is a (meth)acrylate containing three or more acryl groups, M is a (meth)acrylate containing a hydroxyl group, and n is an integer from 1 to 3, p is an integer from 1 to 4, and q is an integer from 1 to 4.)
또한, 한국공개특허 10-2020-0143046(공개일자 2020년12월23일)에 단관능 우레탄 아크릴레이트 모노머(a); 단관능 알킬 아크릴레이트 모노머(b); 및 광 개시제(c)를 포함하고, 상기 단관능 우레탄 아크릴레이트 모노머(a)는 C3-5 고리형 알킬기를 갖는 것인, 잉크젯 3D 프린팅용 광경화성 조성물이 공지되어 있다.In addition, a monofunctional urethane acrylate monomer (a) in Korean Patent Publication No. 10-2020-0143046 (published on December 23, 2020); Monofunctional alkyl acrylate monomer (b); and a photoinitiator (c), wherein the monofunctional urethane acrylate monomer (a) has a C3-5 cyclic alkyl group, and a photocurable composition for inkjet 3D printing is known.
그러나, 상기 한국공개특허 10-2017-0010299 및 한국공개특허 10-2020-0143046는 저점도 단관능 또는 다관능 우레탄 아크릴레이트 올리고머를 사용하고 있으나, 모두 올리고머의 분자량이 크지 않고, 희석제로서 부틸아크릴레이트 또는 히드록시시클로헥실페닐케톤(hydroxycyclohexylketone) 등을 사용하므로 상기 특허들은 단지 탄성을 부여하는 목적 외에는 종래 3D 프린팅용 광경화성 조성물과 같은 문제점이 있었다.However, Korean Patent Publication No. 10-2017-0010299 and Korean Patent Publication No. 10-2020-0143046 use low-viscosity monofunctional or multifunctional urethane acrylate oligomers, but both oligomers do not have a large molecular weight, and butyl acrylate as a diluent Alternatively, since hydroxycyclohexylketone is used, the above patents have the same problems as conventional photocurable compositions for 3D printing except for the purpose of imparting elasticity.
다른 한편,폴리이소시아누레이트 구조 구성요소를 갖는 중합체는 기본적으로 그의 우수한 열적 안정성 및 내화학성이 공지되어 있다. 특히 지방족 이소시아네이트를 기재로 하는 폴리이소시아누레이트 함량을 갖는 폴리우레탄 페인트는 추가적으로 매우 우수한 내열성 및 내후성을 갖는다.On the other hand, polymers with polyisocyanurate structural components are basically known for their excellent thermal stability and chemical resistance. Polyurethane paints with a polyisocyanurate content, especially based on aliphatic isocyanates, additionally have very good heat and weather resistance.
상기한 폴리이소시아누레이트의 특성을 응용하여, 최근에는 한국등록특허 10-1969223(등록일자 2019년04월09일)에 이소포론 디이소시아네이트 및 2-(터트-뷰틸아미노)에틸 메타크릴레이트가 반응한 올리고머; 및 이소포론 디이소시아네이트 삼량체 및 2-(터트-뷰틸아미노)에틸 메타크릴레이트가 반응한 모노머;를 포함하는 UV경화형 조성물이 개발되었다.Applying the above characteristics of polyisocyanurate, recently, isophorone diisocyanate and 2-(tert-butylamino)ethyl methacrylate reacted in Korea Patent Registration 10-1969223 (registration date April 9, 2019) one oligomer; and a monomer in which isophorone diisocyanate trimer and 2-(tert-butylamino)ethyl methacrylate reacted; a UV curable composition comprising a was developed.
그러나, 한국등록특허 10-1969223의 UV경화형 조성물중 상기 이소포론 디이소시아네이트 삼량체는 완전한 삼량화가 어렵기 때문에 이소포론 디이소시아네이트 및 2-(터트-뷰틸아미노)에틸 메타크릴레이트가 반응한 올리고머를 별도로 사용하여야 하고 점도조절이 어려워 코팅용 또는 필름형성용으로만 사용될 수 있는 문제점이 있었다.However, since complete trimerization of the isophorone diisocyanate trimer in the UV-curable composition of Korean Patent No. 10-1969223 is difficult, isophorone diisocyanate and 2-(tert-butylamino)ethyl methacrylate reacted oligomers are separately separated. It had to be used and it was difficult to control the viscosity, so there was a problem that it could be used only for coating or film formation.
이에 본 출원인들은 폴리이소시아누레이트의 특성을 응용하면서 경화속도가 빠르고, 내열성과 현상성이 우수한 3D프린팅용 광경화 수지 조성물을 연구한 결과, 본 발명을 완성하게 되었다.Accordingly, the present applicants have completed the present invention as a result of studying a photocurable resin composition for 3D printing that has a fast curing speed, excellent heat resistance and developability while applying the characteristics of polyisocyanurate.
본 발명은 상기 종래 문제점들을 해결하기 위하여, 바이오매스 유래 1,5-펜타메틸렌디아민을 1,5-펜타메틸렌디이소시아네이트로 전환시킨 후, 상기 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 합성하고, 상기 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가하여 라디칼 경화가 가능하여 SLA나 DLP 기반의 3D프린팅에 적용이 가능한 내열성과 현상성이 우수한 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물을 제공하는 것을 해결하고자 하는 과제로 한다.In order to solve the above conventional problems, the present invention converts biomass-derived 1,5-pentamethylenediamine into 1,5-pentamethylenediisocyanate, and then converts the 1,5-pentamethylenediisocyanate in the presence of a trimerization catalyst. 1,5-pentamethylene diisocyanate-isocyanurate was synthesized by trimerization, and an acrylate or methacrylate having a hydroxyl group at the terminal isocyanate group of the 1,5-pentamethylene diisocyanate-isocyanurate was prepared. 3D photocuring containing biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound with excellent heat resistance and developability that can be radically cured by addition and can be applied to SLA or DLP-based 3D printing The problem to be solved is to provide a resin composition.
본 발명은 상기 과제를 해결하기 위한 것으로, 바이오매스 유래 1,5-펜타메틸렌디아민으로부터 제조된 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 제조된 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가한 하기 [화학식 1]로 표시되는 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물과; 광개시제;를 포함하여 조성되는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물을 과제의 해결수단으로 한다.The present invention is to solve the above problems, and 1,5-pentamethylene diisocyanate prepared from biomass-derived 1,5-pentamethylene diisocyanate is trimerized in the presence of a trimerization catalyst. A 1,5-pentamethylenediisocyanate-isocyanurate-acrylate compound represented by the following [Formula 1] obtained by adding an acrylate or methacrylate having a hydroxyl group to the terminal isocyanate group of isocyanate-isocyanurate; ; A 3D photocurable resin composition comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound containing a photoinitiator as a solution to the problem.
[화학식 1][Formula 1]
[상기 화학식 1에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트중의 아크릴레이트 또는 메타크릴레이트 잔기이다.][In
상기 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트는 다음 화학식에서 열거된 2-하이드록시에틸아크릴레이트, 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필아크릴레이트, 2-하이드록시프로필메타크릴레이트, 3-하이드록시프로필아크릴레이트, 3-하이드록시프로필메타크릴레이트로부터 선택되는 것을 과제의 해결수단으로 한다.The hydroxyl group-containing acrylate or methacrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate listed in the following formula What is selected from a rate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate is used as a solution to the problem.
상기 3D 광경화수지 조성물은 길이 100㎛~3mm의 grained glass fiber. chopped glass fiber, chopped glass matte로부터 선택되는 1종 이상의 글라스 화이버(GF)를 포함하여 조성되는 것을 과제의 해결수단으로 한다.The 3D photocurable resin composition is a grained glass fiber having a length of 100 μm to 3 mm. As a solution to the problem, a composition including at least one glass fiber (GF) selected from chopped glass fiber and chopped glass matte is used.
상기 3D 광경화수지 조성물은 하이드록시에틸아크릴레이트, 하이드록시프로필아크릴레이트, 에틸헥실아크릴레이트, 싸이클릭트리메틸올프로판아크릴레이트, 벤질아크릴레이트, 페놀아크릴레이트, 테트라하이드로푸르푸릴아크릴레이트, 노닐페놀아크릴레이트, 에톡시에틸아크릴레이트, 페녹시벤질아크릴레이트, 이소옥틸아크릴레이트, 이소데실아크릴레이트, 라우릴아크릴레이트, 테트라데실아크릴레이트, 쎄틸아크릴레이트, 스테아릴아크릴레이트, 아이코실아크릴레이트, 비헤닐아크릴레이트, 3,3,5-트리메틸싸이클로헥실아크릴레이트, 카프로락톤아크릴레이트, 2-카르복시에틸아크릴레이트, 비스페놀A아크릴레이트, 비스페놀A디아크릴레이트, (옥타하이드로-4,7-메타노-1H-인덴디일)비스(메틸렌)디아크릴레이트, 디프로필렌글리콜디아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 헥산디올디아크릴레이트, 부탄디올디아크릴레이트, 비스페놀플루오렌디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 하이드록시피발릭네오펜틸글리콜디아크릴레이트, 1,9-노난디올디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 글리세린트리아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리아크릴레이트, 디트리메틸올프로판테트라아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 메톡시PEG메타크릴레이트, 벤질메타크릴레이트, 페녹시에틸메타크릴레이트, 테트라하이드로푸르푸릴메타크릴레이트, 이소데실메타크릴레이트, 라우릴메타크릴레이트, 테트라데실메타크릴레이트, 세틸메타크릴레이트, 스테아릴메타크릴레이트, 3,3,5-트리메틸싸이클로헥실메타크릴레이트, 비스페놀A디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 네오펜틸글리콜디아크릴레이트, 네오펜틸글리콜디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 글리세롤트리메타크릴레이트 중에서 1종 이상 선택되는 아크릴 모노머를 포함하여 조성되는 것을 과제의 해결수단으로 한다.The 3D photocurable resin composition is hydroxyethyl acrylate, hydroxypropyl acrylate, ethylhexyl acrylate, cyclic trimethylolpropane acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonylphenol acrylate Ethyl acrylate, ethoxyethyl acrylate, phenoxybenzyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, bihenyl Acrylate, 3,3,5-trimethylcyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, bisphenol A diacrylate, (octahydro-4,7-methano-1H -indendiyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate, Neopentyl glycol diacrylate, hydroxypivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, trimethylol Propane triacrylate, glycerin triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methyl ToxyPEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, Aryl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycoldi Acrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyester As a solution to the problem, a composition containing at least one acrylic monomer selected from ethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate is used.
상기 광개시제는 페닐비스(2,4,6-트리메틸벤조일), 벤질디메틸케탈, 하이드록시싸이클로헥실페닐케톤, 하이드록시디메틸아세토페논, 메틸-[4-메틸티오페닐]-2-모르폴린프로파논, 2,4-디에틸티옥산톤, 이소프로필티옥산톤프로파논, 에틸-4-디메틸아미노벤조에이트, 벤조페논, 4-페닐벤조페논, 2,4,6-트리메틸벤조일-디페닐포스핀, 메틸벤조일포르메이트 중에서 선택되는 것을 과제의 해결수단으로 한다.The photoinitiator is phenylbis(2,4,6-trimethylbenzoyl), benzyldimethylketal, hydroxycyclohexylphenylketone, hydroxydimethylacetophenone, methyl-[4-methylthiophenyl]-2-morpholinepropanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine, A solution selected from methyl benzoyl formate is used as a solution to the problem.
본 발명의 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물은, 바이오매스 유래 1,5-펜타메틸렌디아민을 1,5-펜타메틸렌디이소시아네이트로 전환시킨 후, 상기 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 합성하고, 상기 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가하여 라디칼 경화가 가능하여 SLA나 DLP 기반의 3D프린팅에 적용이 가능한 내열성과 현상성이 우수한 효과가 있다.The 3D photocurable resin composition comprising the biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention is obtained by converting biomass-derived 1,5-pentamethylenediamine to 1,5-pentamethylene After conversion to diisocyanate, the 1,5-pentamethylene diisocyanate is trimerized in the presence of a trimerization catalyst to synthesize 1,5-pentamethylene diisocyanate-isocyanurate, and the 1,5-pentamethylene diisocyanate is synthesized. Radical curing is possible by adding an acrylate or methacrylate having a hydroxyl group to the terminal isocyanate group of isocyanate-isocyanurate, and thus has excellent heat resistance and developability applicable to SLA or DLP-based 3D printing.
도 1은 본 발명의 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물의 FT-IR 그래프
도 2는 본 발명의 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물의 NMR 데이터
도 3은 본 발명의 GF를 함유한 3D 광경화 조성물의 경화 후 횡단면 현미경 사진
도 4는 본 발명의 GF를 함유한 3D 광경화 조성물의 경화 후 종단면 현미경 사진
도 5는 본 발명의 3D 광경화 조성물의 경화 후 인쇄해상도 현미경 사진1 is a FT-IR graph of the 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention
Figure 2 is NMR data of the 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention
Figure 3 is a cross-sectional micrograph after curing of the 3D photocurable composition containing the GF of the present invention
Figure 4 is a longitudinal cross-sectional micrograph after curing of the 3D photocurable composition containing the GF of the present invention
5 is a print resolution micrograph after curing of the 3D photocurable composition of the present invention
본 발명은, 바이오매스 유래 1,5-펜타메틸렌디아민으로부터 제조된 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 제조된 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가한 하기 [화학식 1]로 표시되는 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물과; 광개시제;를 포함하여 조성되는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물을 기술구성의 특징으로 한다.The present invention relates to 1,5-pentamethylene diisocyanate-isocyanurate prepared by trimerizing 1,5-pentamethylene diisocyanate prepared from biomass-derived 1,5-pentamethylene diisocyanate in the presence of a trimerization catalyst. 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound represented by the following [Formula 1] obtained by adding an acrylate or methacrylate having a hydroxyl group to a terminal isocyanate group; A 3D photocurable resin composition comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound comprising a photoinitiator is characterized by a technical configuration.
[화학식 1][Formula 1]
[상기 화학식 1에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트중의 아크릴레이트 또는 매타크릴레이트 잔기이다.][In
상기 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트는 다음 화학식에서 열거된 2-하이드록시에틸아크릴레이트, 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필아크릴레이트, 2-하이드록시프로필메타크릴레이트, 3-하이드록시프로필아크릴레이트, 3-하이드록시프로필메타크릴레이트로부터 선택되는 것을 기술구성의 특징으로 한다.The hydroxyl group-containing acrylate or methacrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate listed in the following formula The technical composition is characterized by being selected from lactate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate.
상기 3D 광경화수지 조성물은 길이 100㎛~3mm의 grained glass fiber. chopped glass fiber, chopped glass matte로부터 선택되는 1종 이상의 글라스 화이버(GF)를 포함하여 조성되는 것을 기술구성의 특징으로 한다.The 3D photocurable resin composition is a grained glass fiber having a length of 100 μm to 3 mm. It is characterized by a technical configuration that is composed of at least one glass fiber (GF) selected from chopped glass fiber and chopped glass matte.
상기 3D 광경화수지 조성물은 하이드록시에틸아크릴레이트, 하이드록시프로필아크릴레이트, 에틸헥실아크릴레이트, 싸이클릭트리메틸올프로판아크릴레이트, 벤질아크릴레이트, 페놀아크릴레이트, 테트라하이드로푸르푸릴아크릴레이트, 노닐페놀아크릴레이트, 에톡시에틸아크릴레이트, 페녹시벤질아크릴레이트, 이소옥틸아크릴레이트, 이소데실아크릴레이트, 라우릴아크릴레이트, 테트라데실아크릴레이트, 쎄틸아크릴레이트, 스테아릴아크릴레이트, 아이코실아크릴레이트, 비헤닐아크릴레이트, 3,3,5-트리메틸싸이클로헥실아크릴레이트, 카프로락톤아크릴레이트, 2-카르복시에틸아크릴레이트, 비스페놀A아크릴레이트, 비스페놀A디아크릴레이트, (옥타하이드로-4,7-메타노-1H-인덴디일)비스(메틸렌)디아크릴레이트, 디프로필렌글리콜디아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 헥산디올디아크릴레이트, 부탄디올디아크릴레이트, 비스페놀플루오렌디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 하이드록시피발릭네오펜틸글리콜디아크릴레이트, 1,9-노난디올디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 글리세린트리아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리아크릴레이트, 디트리메틸올프로판테트라아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 메톡시PEG메타크릴레이트, 벤질메타크릴레이트, 페녹시에틸메타크릴레이트, 테트라하이드로푸르푸릴메타크릴레이트, 이소데실메타크릴레이트, 라우릴메타크릴레이트, 테트라데실메타크릴레이트, 세틸메타크릴레이트, 스테아릴메타크릴레이트, 3,3,5-트리메틸싸이클로헥실메타크릴레이트, 비스페놀A디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 네오펜틸글리콜디아크릴레이트, 네오펜틸글리콜디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 글리세롤트리메타크릴레이트 중에서 1종 이상 선택되는 아크릴 모노머를 포함하여 조성되는 것을 기술구성의 특징으로 한다.The 3D photocurable resin composition is hydroxyethyl acrylate, hydroxypropyl acrylate, ethylhexyl acrylate, cyclic trimethylolpropane acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonylphenol acrylate Ethyl acrylate, ethoxyethyl acrylate, phenoxybenzyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, bihenyl Acrylate, 3,3,5-trimethylcyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, bisphenol A diacrylate, (octahydro-4,7-methano-1H -indendiyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate, Neopentyl glycol diacrylate, hydroxypivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, trimethylol Propane triacrylate, glycerin triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methyl ToxyPEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, Aryl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycoldi Acrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyester It is characterized in that it is composed of an acrylic monomer selected from ethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.
상기 광개시제는 페닐비스(2,4,6-트리메틸벤조일), 벤질디메틸케탈, 하이드록시싸이클로헥실페닐케톤, 하이드록시디메틸아세토페논, 메틸-[4-메틸티오페닐]-2-모르폴린프로파논, 2,4-디에틸티옥산톤, 이소프로필티옥산톤프로파논, 에틸-4-디메틸아미노벤조에이트, 벤조페논, 4-페닐벤조페논, 2,4,6-트리메틸벤조일-디페닐포스핀, 메틸벤조일포르메이트 중에서 선택되는 것을 기술구성의 특징으로 한다.The photoinitiator is phenylbis(2,4,6-trimethylbenzoyl), benzyldimethylketal, hydroxycyclohexylphenylketone, hydroxydimethylacetophenone, methyl-[4-methylthiophenyl]-2-morpholinepropanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine, The selection among methylbenzoylformates characterizes the technical composition.
이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예 및/또는 도면을 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예 및/또는 도면에 한정되지 않는다.Hereinafter, examples and/or drawings of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments and/or drawings described herein.
먼저, 본 발명의 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물은, 바이오매스 유래 1,5-펜타메틸렌디아민으로부터 제조된 1,5-펜타메틸렌디이소시아네이트를 삼량화 촉매 존재하에 삼량화시켜 제조된 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 부가한 하기 [화학식 1]로 표시되는 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물과; 광개시제;를 포함하여 조성된다.First, the 3D photocurable resin composition comprising the biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention contains 1,5-pentamethylenediamine prepared from biomass-derived 1,5-pentamethylenediamine. The following [ 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound represented by Formula 1]; It is composed including; photoinitiator.
[화학식 1][Formula 1]
[상기 화학식 1에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트중의 아크릴레이트 또는 매타크릴레이트 잔기이다.][In
우선, 일반적으로 지방족 디이소시아네이트 또는 다환식 지방족 디이소시아네이트를 삼량화 촉매에 의하여 합성된 다음 화학식으로 표시되는 폴리이소시아네이트-이소시아누레이트 화합물은 우레탄의 경화제로서 사용하면, 내후성, 유연성, 경화성, 건조성이 우수하다는 것은 주지의 사실이다.First, in general, aliphatic diisocyanate or polycyclic aliphatic diisocyanate is synthesized by a trimerization catalyst, and then the polyisocyanate-isocyanurate compound represented by the formula is used as a curing agent for urethane, which has excellent weather resistance, flexibility, curability, and drying properties. It is a well-known fact that this is excellent.
[화학식 1][Formula 1]
[식중, R1, R2 및 R3은 탄소수 2 내지 12의 알킬렌기이다][Wherein, R1, R2 and R3 are alkylene groups having 2 to 12 carbon atoms]
특히, 상기와 같이, 이소시아누레이트기를 함유하는 이소시아누레이트형 폴리이소시아네이트는 뛰어난 코팅 물성, 예컨대, 내후성을 갖는 것으로 알려져 있으며, 코팅의 건조성 및 가교성이 우수하고, 낮은 점도, 폴리올과의 상용성 및 저극성 용매 내에서의 용해성을 가지므로 폴리이소시아네이트보다 더 안정하기 때문에 디이소시아네이트를 삼량화하여 사용한다.In particular, as described above, isocyanurate-type polyisocyanates containing an isocyanurate group are known to have excellent coating properties, such as weather resistance, excellent drying properties and crosslinking properties of coatings, low viscosity, and polyol and Diisocyanate is trimerized and used because it is more stable than polyisocyanate due to its compatibility and solubility in low-polarity solvents.
그러나, 상기 이소시아누레이트기를 함유하는 이소시아누레이트형 폴리이소시아네이트들은 높은 OH 기 함량을 갖는 결합제의 분야에서 비상용성 때문에 뷰렛 구조를 함유하는 가교제의 사용에 의존하여야 하고, 특히, HDI 이소시아누레이트형 폴리이소시아네이트는 낮은 반응성 NCO 기 함량을 가지며, 높은 점도를 가지는 문제가 있어서 여러 코팅분야에는 사용할 수 있으나, 낮은 점도로 사용되어야 하는 3D 프린팅 분야에 사용은 어려움이 있었다.However, isocyanurate-type polyisocyanates containing the isocyanurate group have to rely on the use of a crosslinking agent containing a biuret structure because of incompatibility in the field of a binder having a high OH group content, in particular, HDI isocyanurate Late-type polyisocyanate has a low reactive NCO group content and has a high viscosity, so it can be used in various coating fields, but it is difficult to use in the 3D printing field where it must be used with a low viscosity.
다만, 1,5-펜타메틸렌디이소시아네이트는 높은 OH 기 함량의 결합제에 대한 개선된 상용성이 알려진 바 있어, 1,5-펜타메틸렌디이소시아네이트로부터 출발하는 이소시아누레이트형 폴리이소시아네이트의 상용성을 기반으로 본 발명의 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 3D 광경화수지 조성물로 사용하는 것을 목표로 한다.However, since 1,5-pentamethylene diisocyanate has been known to have improved compatibility with binders having a high OH group content, the compatibility of isocyanurate-type polyisocyanates starting from 1,5-pentamethylene diisocyanate has been improved. It aims to use the 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention as a 3D photocurable resin composition.
여기서, 상기 1,5-펜타메틸렌디이소시아네이트는 WO 2008/015134 A1에 바이오패스 유래 라이신을 발효하여 펜탄-1,5-디아민(PDA)으로 전환시키고 이를 상기 1,5-펜타메틸렌디이소시아네이트를 제조하는 방법이 공지되어 있다.Here, the 1,5-pentamethylene diisocyanate is converted into pentane-1,5-diamine (PDA) by fermenting biopass-derived lysine in WO 2008/015134 A1 to prepare the 1,5-pentamethylene diisocyanate. How to do this is known.
이를 이용하여, [1단계로서] 바이오매스 유래 1,5-펜타메틸렌디아민으로부터 제조된 1,5-펜타메틸렌디이소시아네이트를 다음 [반응식 1]과 같이, 삼량화 촉매 하에 삼량화시켜 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 제조한다.Using this, [as a first step] 1,5-pentamethylene diisocyanate prepared from biomass-derived 1,5-pentamethylene diisocyanate is trimerized under a trimerization catalyst as shown in [Scheme 1] to obtain 1,5-pentamethylene diisocyanate. Pentamethylene diisocyanate-isocyanurate is prepared.
[반응식 1][Scheme 1]
이때, 상기 삼량체화 촉매로는 이소시아누레이트 형성 반응에 대해 비교적 활성 및 안정성이 우수한 4차 암모늄 화합물 또는 그의 유기 약산 염이 사용되고 있으나, 이들 삼량체화 촉매들중 제조 및 정제가 단순한 트리알킬히드록시알킬암모늄염, 예를 들면 N,N,N-트리메틸-N-2-히드록시프로필암모늄 p-3차-부틸벤조에이트, 특히 N,N,N-트리메틸-N-2-히드록시프로필암모늄 2-에틸헥사노에이트인 삼량체화 촉매중의 음이온 유기산염의 분자량이 큰 삼량체화 촉매가 사용되고 있다.At this time, as the trimerization catalyst, a quaternary ammonium compound or an organic weak acid salt thereof having relatively excellent activity and stability for the isocyanurate formation reaction is used, but among these trimerization catalysts, trialkylhydroxy, which is simple to prepare and purify, is used. Alkylammonium salts, for example N,N,N-trimethyl-N-2-hydroxypropylammonium p-tert-butylbenzoate, especially N,N,N-trimethyl-N-2-hydroxypropylammonium 2- A trimerization catalyst having a large molecular weight of an anionic organic acid salt in the trimerization catalyst, which is ethyl hexanoate, is used.
그러나, 상기 촉매들은 삼량체화 촉매중의 음이온 유기산염이 벤조에이트 또는 헥사노에이트로서 분자량이 커서 상대적으로 촉매활성이 만족스럽지 못한데, 그 이유는 반응메카니즘상 유기산염의 사슬길이가 길고 이에 따른 분자량이 커서 이소시아네이트와 4급 암모늄염의 접촉이 원활하지 못한데서 기인하기 때문인데, 즉, 유기산염의 사슬길이가 길고 이에 따른 분자량이 긴 것 대신에, 유기산염의 사슬길이가 짧고 이에 따른 분자량이 작은 것을 사용하면, 동일 중량의 촉매를 사용했을 경우, 상대적으로 분자량이 낮은 촉매의 몰함량이 더 높기 때문에 이소시아네이트와 4급 암모늄염의 접촉이 원활하여 활성이 증대된다.However, these catalysts have relatively unsatisfactory catalytic activity because the anionic organic acid salt in the trimerization catalyst has a large molecular weight as benzoate or hexanoate. This is because the contact between the isocyanate and the quaternary ammonium salt is not smooth, that is, if an organic acid salt having a short chain length and a small molecular weight is used instead of a long organic acid salt having a long chain length and a correspondingly long molecular weight, the same When a heavy catalyst is used, since the molar content of the catalyst having a relatively low molecular weight is higher, the contact between the isocyanate and the quaternary ammonium salt is smooth and the activity is increased.
따라서, 본 발명에서는 상기 삼량화 촉매로서 유기산염의 사슬길이가 상대적으로 짧고 분자량이 낮은 N,N-트리메틸-N-2-하이드록시프로필암모늄 2,2-다이메틸프로파네이트의 부틸셀로솔브 용액 또는 N,N,N-트리메틸-N-2-하이드록시프로필암모늄 2,2-다이메틸부타노에이트의 부틸셀로솔브 용액을 사용하여 촉매활성을 향상시키도록 한다.Therefore, in the present invention, as the trimerization catalyst, a butyl cellosolve solution of N,N-trimethyl-N-2-
다음 [2단계]로서, 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트를 다음 [반응식 2]과 같이 부가하여 하기 [화학식 1]로 표시되는 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 합성한다.As the next [step 2], an acrylate or methacrylate having a hydroxyl group is added to the terminal isocyanate group of 1,5-pentamethylene diisocyanate-isocyanurate as shown in [Scheme 2] below [Formula 1] A 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound represented by is synthesized.
[반응식 2][Scheme 2]
[상기 반응식 2에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트중의 아크릴레이트 또는 매타크릴레이트 잔기이다.][In
이때, 상기 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트는 다음 화학식에서 열거된 2-하이드록시에틸아크릴레이트, 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필아크릴레이트, 2-하이드록시프로필메타크릴레이트, 3-하이드록시프로필아크릴레이트, 3-하이드록시프로필메타크릴레이트로부터 선택될 수 있다.At this time, the acrylate or methacrylate having a hydroxyl group is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl listed in the following formula methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate.
특히, 상기 반응에서, 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트는 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 말단 이소시아네이트기에 다음과 같이 부가반응하여 우레탄(-NH-CO-O-)을 형성하면 기계적 물성이 우수한 경화물을 얻을 수 있다.In particular, in the above reaction, acrylate or methacrylate having a hydroxyl group is added to the terminal isocyanate group of 1,5-pentamethylene diisocyanate-isocyanurate as follows to form urethane (-NH-CO-O- ), a cured product having excellent mechanical properties can be obtained.
[상기식에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트중의 아크릴레이트 또는 매타크릴레이트 잔기이다.][Wherein R is an acrylate or methacrylate residue in an acrylate or methacrylate having a hydroxyl group.]
즉, 상기 아크릴레이트의 부가반응으로부터 형성된 우레탄(-NH-CO-O-) 작용기는 자유 라디칼 경화 반응에서 비닐기 또는 아크릴레이트기와 반응하여 경화 후 연질의 기계적 물성을 제공할 수 있다.That is, the urethane (-NH-CO-O-) functional group formed from the addition reaction of the acrylate may react with a vinyl group or an acrylate group in a free radical curing reaction to provide soft mechanical properties after curing.
이때, 상기 3D 광경화수지 조성물은 하이드록시에틸아크릴레이트, 하이드록시프로필아크릴레이트, 에틸헥실아크릴레이트, 싸이클릭트리메틸올프로판아크릴레이트, 벤질아크릴레이트, 페놀아크릴레이트, 테트라하이드로푸르푸릴아크릴레이트, 노닐페놀아크릴레이트, 에톡시에틸아크릴레이트, 페녹시벤질아크릴레이트, 이소옥틸아크릴레이트, 이소데실아크릴레이트, 라우릴아크릴레이트, 테트라데실아크릴레이트, 쎄틸아크릴레이트, 스테아릴아크릴레이트, 아이코실아크릴레이트, 비헤닐아크릴레이트, 3,3,5-트리메틸싸이클로헥실아크릴레이트, 카프로락톤아크릴레이트, 2-카르복시에틸아크릴레이트, 비스페놀A아크릴레이트, 비스페놀A디아크릴레이트, (옥타하이드로-4,7-메타노-1H-인덴디일)비스(메틸렌)디아크릴레이트, 디프로필렌글리콜디아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 헥산디올디아크릴레이트, 부탄디올디아크릴레이트, 비스페놀플루오렌디아크릴레이트, 네오펜틸글리콜디아크릴레이트, 하이드록시피발릭네오펜틸글리콜디아크릴레이트, 1,9-노난디올디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 글리세린트리아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리아크릴레이트, 디트리메틸올프로판테트라아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 메톡시PEG메타크릴레이트, 벤질메타크릴레이트, 페녹시에틸메타크릴레이트, 테트라하이드로푸르푸릴메타크릴레이트, 이소데실메타크릴레이트, 라우릴메타크릴레이트, 테트라데실메타크릴레이트, 세틸메타크릴레이트, 스테아릴메타크릴레이트, 3,3,5-트리메틸싸이클로헥실메타크릴레이트, 비스페놀A디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 네오펜틸글리콜디아크릴레이트, 네오펜틸글리콜디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 글리세롤트리메타크릴레이트 중에서 1종 이상 선택되는 아크릴 모노머를 포함하여 점도를 조절하거나 물성을 보완할 수 있다.At this time, the 3D photocurable resin composition is hydroxyethyl acrylate, hydroxypropyl acrylate, ethylhexyl acrylate, cyclic trimethylolpropane acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl Phenol acrylate, ethoxyethyl acrylate, phenoxybenzyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, Bihenyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, bisphenol A diacrylate, (octahydro-4,7-methano -1H-indendiyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate rate, neopentyl glycol diacrylate, hydroxypivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, Trimethylolpropane triacrylate, glycerin triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate , methoxyPEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate , stearyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl Glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Viscosity may be adjusted or physical properties may be supplemented by including at least one acrylic monomer selected from polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.
또한, 상기 광개시제는 페닐비스(2,4,6-트리메틸벤조일), 벤질디메틸케탈, 하이드록시싸이클로헥실페닐케톤, 하이드록시디메틸아세토페논, 메틸-[4-메틸티오페닐]-2-모르폴린프로파논, 2,4-디에틸티옥산톤, 이소프로필티옥산톤프로파논, 에틸-4-디메틸아미노벤조에이트, 벤조페논, 4-페닐벤조페논, 2,4,6-트리메틸벤조일-디페닐포스핀, 메틸벤조일포르메이트 중에서 선택될 수 있다.In addition, the photoinitiator is phenylbis (2,4,6-trimethylbenzoyl), benzyldimethylketal, hydroxycyclohexylphenylketone, hydroxydimethylacetophenone, methyl-[4-methylthiophenyl] -2-morpholine pro Panone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphos It may be selected from pin, methyl benzoyl formate.
한편, 상기 3D 광경화수지 조성물은 길이 100㎛~3mm의 grained glass fiber. chopped glass fiber, chopped glass matte로부터 선택되는 1종 이상의 글라스 화이버(GF)를 포함하여 조성되는 보강재료를 포함할 수도 있다.On the other hand, the 3D photocurable resin composition is a grained glass fiber having a length of 100 μm to 3 mm. A reinforcing material composed of at least one glass fiber (GF) selected from chopped glass fiber and chopped glass matte may be included.
뿐만 아니라, 본 발명에 따른 3D 광경화수지 조성물은 방향족 화합물을 포함하는 2관능성 에폭시 (메타)아크릴레이트를 추가로 더 포함할 수 있다.In addition, the 3D photocurable resin composition according to the present invention may further include a bifunctional epoxy (meth)acrylate containing an aromatic compound.
여기서, 상기 방향족 화합물은 비스페놀A, 노블락, 나프탈렌, 및 플루오렌으로 이루어진 그룹 중에서 선택된 하나 이상의 방향족 화합물로부터 유도된 것을 포함한다.Here, the aromatic compound includes one derived from at least one aromatic compound selected from the group consisting of bisphenol A, noblock, naphthalene, and fluorene.
특히, 본 발명에 따른 방향족 화합물을 포함하는 2 관능성 에폭시 (메타)아크릴레이트는 비스페놀A와 에피클로로히드린(epichlorohydrin)을 수산화나트륨 촉매하에서 합성하여 제조한 비스페놀A형 에폭시, 예컨대 YD-128(국도화학, 대한민국), KER-828(금호피엔씨, 대한민국), EPR-174(헥시온코리아, 대한민국) 등의 에폭시를 염기성 촉매와 중합금지제를 사용하여 아크릴산과 부가반응시켜 제조할 수 있다.In particular, the difunctional epoxy (meth)acrylate containing an aromatic compound according to the present invention is a bisphenol A type epoxy prepared by synthesizing bisphenol A and epichlorohydrin under a sodium hydroxide catalyst, such as YD-128 ( Kukdo Chemical, Korea), KER-828 (Kumho P&C, Korea), EPR-174 (Hexion Korea, Korea), etc. can be prepared by addition reaction with acrylic acid using a basic catalyst and a polymerization inhibitor.
여기서, 상기 비스페놀 A 대신 다핵체인 노블락수지, 나프탈렌, 플루오렌 등을 사용하여 고굴절율의 올리고머수지로서 변성체의 아크릴산 에스테르 등으로 사용할 수 있다.Here, polynuclear noblock resin, naphthalene, fluorene, etc. can be used instead of the bisphenol A as a high refractive index oligomer resin, which can be used as a modified acrylic acid ester.
한편, 상기 2 관능성 에폭시 (메타)아크릴레이트는 구조상 경도가 높고, 극성기를 지니고 있으므로 접착력이 좋은 특성이 있고, 이러한 것들은 시중에서 판매되는 상품으로 사용할 수 있다.On the other hand, the difunctional epoxy (meth)acrylate has high structural hardness and has a polar group, so it has good adhesive properties, and these can be used as commercially available products.
[1단계] 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트 제조[Step 1] Preparation of 1,5-pentamethylene diisocyanate-isocyanurate
교반기, 콘덴서, 질소 유입구, 서머커플이 장착된 2 liter flask에 99.89g의 PDI를 넣은 후 교반하면서 70℃까지 가열하였다. 원하는 온도에 도달한 후 이소시아누레이트화 촉매로서 N,N,N-트리메틸-N-2-하이드록시프로필 암모늄 2,2-다이메틸프로파네이트의 12.5% 부틸셀로솔브 용액을 분할 첨가하였다. 이 촉매용액을 총량으로 0.1g(PDI 투입량에 대하여)을 첨가한 바, 반응기내의 온도가 80℃까지 상승하였다. 반응기내의 온도를 70℃~80℃로 유지하면서, 반응의 진행도를 굴절율(n25D)로 확인하면서 반응을 계속시켰다. 반응 혼합물의 굴절율이 1.4670에 도달한 시점에서, 촉매의 실효제로서 모노클로로초산의 6.8% 자이렌용액 0.01g을 반응기내에 첨가하여 반응을 종결시켰다. 반응 혼합물을 실온으로 냉각시킨 후, 반응혼합물 중 과량의 PDI를 박막증발기에서 증류에 의해 분리시켰다. 반응혼합물을 증류하여 맑고 매우 연한색의 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트를 얻었다. 얻어진 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트의 특징은 Viscocity 2300mPa.s/25℃, Hazen color 22, NCO content 22.2% 이었다, After putting 99.89 g of PDI in a 2 liter flask equipped with a stirrer, condenser, nitrogen inlet, and thermocouple, it was heated to 70 °C while stirring. After reaching the desired temperature, a 12.5% butylcellosolve solution of N,N,N-trimethyl-N-2-
[2단계] 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물 제조[Step 2] Preparation of 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound
플라스크에 [실시예 1]에서 얻은 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트 42.4g과 2-HEMA(2-Hydroxyethyl methacrylate) 57.2g을 메틸에틸케톤에 점도를 조정하여 녹인 후, 이 용액을 상온에서 30분동안 교반하여 본 발명의 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 제조하였다.After dissolving 42.4 g of 1,5-pentamethylene diisocyanate-isocyanurate and 57.2 g of 2-HEMA (2-Hydroxyethyl methacrylate) obtained in [Example 1] in a flask by adjusting the viscosity in methyl ethyl ketone, this solution was stirred at room temperature for 30 minutes to prepare the 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound of the present invention.
상기 제조된 화합물은 [도 1]의 FT-IR 그래프 및 [도 2]의 13C-NMR 를 동해 확인할 수 있다.The prepared compound can be confirmed by FT-IR graph of [FIG. 1] and 13 C-NMR of [FIG. 2].
3D 광경화수지 조성물의 제조Preparation of 3D photocurable resin composition
[실시예 2]에서 얻은 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물에 이르가큐어 광개시제 및 chopped glass fiber를 혼합하여 3D 광경화수지 조성물의 제조하고 열변형온도, 굽힘강도, 쇼어경도, 수축률을 다음 [표 1]에, 인쇄해상도를 [도 3]에 나타내었다.A 3D photocurable resin composition was prepared by mixing the 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound obtained in [Example 2] with an Irgacure photoinitiator and chopped glass fibers, and the heat deflection temperature and bending strength , Shore hardness, and shrinkage are shown in [Table 1], and the printing resolution is shown in [Figure 3].
상기 [표 1]에 나타난 바와 같이, 본 발명의 3D 광경화조성물은 열변형온도, 굽힘강도, 쇼어경도, 수축률에 있어서 우수한 것을 확인할 수 있으며, 인쇄해상도의 경우에도 [도 5에 나타난 바와 같이, 선폭이 18~20㎛ 수준으로 형상성이 우수한 것을 확인할 수 있다.As shown in [Table 1], it can be confirmed that the 3D photocurable composition of the present invention is excellent in heat distortion temperature, bending strength, shore hardness, and shrinkage, and even in the case of printing resolution [as shown in FIG. 5, It can be seen that the formability is excellent at a line width of 18 to 20 μm.
이상의 설명은 본 발명의 기술사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예 및/또는 도면들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예 및/또는 도면에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is only illustrative of the technical idea of the present invention, and various modifications and variations can be made to those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments and / or drawings disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain, and the scope of the technical idea of the present invention is not limited by these embodiments and / or drawings. . The protection scope of the present invention should be construed according to the claims below, and all technical ideas within the equivalent range should be construed as being included in the scope of the present invention.
Claims (5)
[화학식 1]
[상기 화학식 1에서 R은 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트 잔기이다.]
상기 하이드록실기를 가지는 아크릴레이트 또는 메타크릴레이트는 다음 화학식에서 열거된 2-하이드록시에틸아크릴레이트, 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필아크릴레이트, 2-하이드록시프로필메타크릴레이트, 3-하이드록시프로필아크릴레이트, 3-하이드록시프로필메타크릴레이트로부터 선택되는 것을 특징으로 하는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물
1,5-pentamethylene diisocyanate prepared by trimerization of 1,5-pentamethylene diisocyanate prepared from biomass-derived 1,5-pentamethylene diisocyanate in the presence of a trimerization catalyst is hydroxylated at the terminal isocyanate group of isocyanurate. a 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound represented by the following [Formula 1] to which an acrylate or methacrylate having a hydroxyl group is added; A photoinitiator; is composed including,
[Formula 1]
[In Formula 1, R is an acrylate or methacrylate residue having a hydroxyl group.]
The hydroxyl group-containing acrylate or methacrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate listed in the following formula 3D spectacle comprising a biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound selected from hydroxypropyl acrylate, 3-hydroxypropyl acrylate and 3-hydroxypropyl methacrylate fire resin composition
상기 3D 광경화수지 조성물은 길이 100㎛~3mm의 grained glass fiber. chopped glass fiber, chopped glass matte로부터 선택되는 1종 이상의 글라스 화이버(GF)를 포함하여 조성되는 것을 특징으로 하는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물
According to claim 1,
The 3D photocurable resin composition is a grained glass fiber having a length of 100 μm to 3 mm. A biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound comprising at least one glass fiber (GF) selected from chopped glass fiber and chopped glass matte 3D photocurable resin composition
상기 3D 광경화수지 조성물은 하이드록시에틸아크릴레이트, 하이드록시프로필아크릴레이트, 에틸헥실아크릴레이트, 싸이클릭트리메틸올프로판아크릴레이트, 벤질아크릴레이트, 페놀아크릴레이트, 테트라하이드로푸르푸릴아크릴레이트, 노닐페놀아크릴레이트, 에톡시에틸아크릴레이트, 페녹시벤질아크릴레이트, 이소옥틸아크릴레이트, 이소데실아크릴레이트, 라우릴아크릴레이트, 테트라데실아크릴레이트, 쎄틸아크릴레이트, 스테아릴아크릴레이트, 아이코실아크릴레이트, 비헤닐아크릴레이트, 3,3,5-트리메틸싸이클로헥실아크릴레이트, 카프로락톤아크릴레이트, 2-카르복시에틸아크릴레이트, 비스페놀A아크릴레이트, 비스페놀A디아크릴레이트, (옥타하이드로-4,7-메타노-1H-인덴디일)비스(메틸렌)디아크릴레이트, 디프로필렌글리콜디아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 프로필렌글리콜디아크릴레이트, 헥산디올디아크릴레이트, 부탄디올디아크릴레이트, 비스페놀플루오렌디아크릴레이트, 하이드록시피발릭네오펜틸글리콜디아크릴레이트, 1,9-노난디올디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 트리메틸올프로판트리아크릴레이트, 글리세린트리아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리아크릴레이트, 디트리메틸올프로판테트라아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 벤질메타크릴레이트, 페녹시에틸메타크릴레이트, 테트라하이드로푸르푸릴메타크릴레이트, 이소데실메타크릴레이트, 라우릴메타크릴레이트, 테트라데실메타크릴레이트, 세틸메타크릴레이트, 스테아릴메타크릴레이트, 3,3,5-트리메틸싸이클로헥실메타크릴레이트, 비스페놀A디메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 1,4-부탄디올디메타크릴레이트, 네오펜틸글리콜디아크릴레이트, 네오펜틸글리콜디메타크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 폴리프로필렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 글리세롤트리메타크릴레이트 중에서 1종 이상 선택되는 아크릴 모노머를 포함하여 조성되는 것을 특징으로 하는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물
According to claim 1,
The 3D photocurable resin composition is hydroxyethyl acrylate, hydroxypropyl acrylate, ethylhexyl acrylate, cyclic trimethylolpropane acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonylphenol acrylate Ethyl acrylate, ethoxyethyl acrylate, phenoxybenzyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, bihenyl Acrylate, 3,3,5-trimethylcyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, bisphenol A diacrylate, (octahydro-4,7-methano-1H -indendiyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate, Hydroxypivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, glycerin tri Acrylates, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, benzyl methacrylate, phenoxyethyl Methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5-trimethylcyclohexyl Methacrylate, bisphenol A dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol di Methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, Biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound comprising at least one acrylic monomer selected from trimethylene propane trimethacrylate and glycerol trimethacrylate 3D photocurable resin composition comprising
상기 광개시제는 페닐비스(2,4,6-트리메틸벤조일), 벤질디메틸케탈, 하이드록시싸이클로헥실페닐케톤, 하이드록시디메틸아세토페논, 메틸-[4-메틸티오페닐]-2-모르폴린프로파논, 2,4-디에틸티옥산톤, 이소프로필티옥산톤프로파논, 에틸-4-디메틸아미노벤조에이트, 벤조페논, 4-페닐벤조페논, 2,4,6-트리메틸벤조일-디페닐포스핀, 메틸벤조일포르메이트 중에서 선택되는 것을 특징으로 하는 바이오매스 유래 1,5-펜타메틸렌디이소시아네이트-이소시아누레이트-아크릴레이트화합물을 포함하는 3D 광경화수지 조성물According to claim 1,
The photoinitiator is phenylbis(2,4,6-trimethylbenzoyl), benzyldimethylketal, hydroxycyclohexylphenylketone, hydroxydimethylacetophenone, methyl-[4-methylthiophenyl]-2-morpholinepropanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine, 3D photocurable resin composition comprising biomass-derived 1,5-pentamethylene diisocyanate-isocyanurate-acrylate compound selected from methylbenzoylformate
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| JP5927783B2 (en) | 2011-06-10 | 2016-06-01 | Jnc株式会社 | Photo-curable inkjet ink |
| CN105658694A (en) * | 2013-10-21 | 2016-06-08 | 三井化学株式会社 | Polymerizable composition for optical material and optical material |
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| KR20170010299A (en) | 2015-07-15 | 2017-01-26 | 주식회사 루벤틱스 | Low viscosity oligomer, and resin composition for stereolithography apparatus 3D printing comprising the same |
| KR101838520B1 (en) | 2016-09-07 | 2018-03-14 | 애경화학 주식회사 | Curable resin composition for 3D printing with good developing properties and contraction percentage comprising cycloaliphatic epoxy acrylic compound having cation curing and UV curing mechanizm |
| KR101969223B1 (en) | 2017-08-31 | 2019-04-15 | 전자부품연구원 | UV-curable composition and coating film using the same |
| KR102672896B1 (en) | 2019-06-14 | 2024-06-05 | 주식회사 엘지화학 | Light curable composition for inkjet 3d printing |
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| JP2006039179A (en) * | 2004-07-27 | 2006-02-09 | Mitsubishi Paper Mills Ltd | Photosensitive composition and photosensitive lithographic printing plate |
| JP2007264497A (en) | 2006-03-29 | 2007-10-11 | Mitsubishi Paper Mills Ltd | Photosensitive lithographic printing plate and development processing method using the same |
| KR101822151B1 (en) | 2017-06-28 | 2018-01-25 | 비즈텍코리아 주식회사 | Photocurable polysiloxane composition for 3D printing and dental model comprising the same |
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