KR20240106458A - Optical resin composition for wafer-level lenses and optical resin for wafer-level lenses using it - Google Patents
Optical resin composition for wafer-level lenses and optical resin for wafer-level lenses using it Download PDFInfo
- Publication number
- KR20240106458A KR20240106458A KR1020220189320A KR20220189320A KR20240106458A KR 20240106458 A KR20240106458 A KR 20240106458A KR 1020220189320 A KR1020220189320 A KR 1020220189320A KR 20220189320 A KR20220189320 A KR 20220189320A KR 20240106458 A KR20240106458 A KR 20240106458A
- Authority
- KR
- South Korea
- Prior art keywords
- diisocyanate
- isocyanatomethyl
- bis
- resin composition
- polythiol
- Prior art date
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- 230000003287 optical effect Effects 0.000 title claims abstract description 54
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims description 24
- 229920005989 resin Polymers 0.000 title claims description 24
- 229920006295 polythiol Polymers 0.000 claims description 43
- 239000012948 isocyanate Substances 0.000 claims description 39
- -1 diisocyanate compound Chemical class 0.000 claims description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims description 31
- 150000002513 isocyanates Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 claims description 4
- VBGAVNKWFCSKSE-UHFFFAOYSA-N 5-(2-isocyanatoethyl)-3-(isocyanatomethyl)-2-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C(CCN=C=O)C2C(CN=C=O)C(CCCN=C=O)C1C2 VBGAVNKWFCSKSE-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000006082 mold release agent Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 claims description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical group O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 claims description 2
- KVUYSIIZYQUVMT-UHFFFAOYSA-N 1,2-diisothiocyanatoethane Chemical compound S=C=NCCN=C=S KVUYSIIZYQUVMT-UHFFFAOYSA-N 0.000 claims description 2
- HACSMMPRDHJXQP-UHFFFAOYSA-N 1,3,5-tris(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CC(CN=C=O)CC(CN=C=O)C1 HACSMMPRDHJXQP-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- RRSISCMPUAGVJN-UHFFFAOYSA-N 1,4-diisothiocyanatobutane Chemical compound S=C=NCCCCN=C=S RRSISCMPUAGVJN-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- VZZPYUKWXDLMGI-UHFFFAOYSA-N 1,6-diisothiocyanatohexane Chemical compound S=C=NCCCCCCN=C=S VZZPYUKWXDLMGI-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- FELBNCXDZSNTIX-UHFFFAOYSA-N 1,8-diisocyanato-4-(isocyanatomethyl)-2,4,7-trimethyloctane Chemical compound O=C=NCC(C)CCC(C)(CN=C=O)CC(C)CN=C=O FELBNCXDZSNTIX-UHFFFAOYSA-N 0.000 claims description 2
- RHNNQENFSNOGAM-UHFFFAOYSA-N 1,8-diisocyanato-4-(isocyanatomethyl)octane Chemical compound O=C=NCCCCC(CN=C=O)CCCN=C=O RHNNQENFSNOGAM-UHFFFAOYSA-N 0.000 claims description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 claims description 2
- GHSZVIPKVOEXNX-UHFFFAOYSA-N 1,9-diisocyanatononane Chemical compound O=C=NCCCCCCCCCN=C=O GHSZVIPKVOEXNX-UHFFFAOYSA-N 0.000 claims description 2
- QLOQTKGUQKAAAB-UHFFFAOYSA-N 1-isocyanato-2-(2-isocyanatoethoxy)ethane Chemical compound O=C=NCCOCCN=C=O QLOQTKGUQKAAAB-UHFFFAOYSA-N 0.000 claims description 2
- XRPYTMSBOBTVIK-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)-3-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CCCN=C=O)C(CN=C=O)C1C2 XRPYTMSBOBTVIK-UHFFFAOYSA-N 0.000 claims description 2
- LEAAXJONQWQISB-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1C2C(CN=C=O)CC1C(CN=C=O)C2 LEAAXJONQWQISB-UHFFFAOYSA-N 0.000 claims description 2
- KPLNSCKRXRCEIQ-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)-3-[2-[3-sulfanyl-2-(2-sulfanylethylsulfanyl)propyl]sulfanylethylsulfanyl]propane-1-thiol Chemical compound SCCSC(CS)CSCCSCC(CS)SCCS KPLNSCKRXRCEIQ-UHFFFAOYSA-N 0.000 claims description 2
- OFPNMKVNQZZSIQ-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)-3-[2-sulfanyl-3-[3-sulfanyl-2-(2-sulfanylethylsulfanyl)propyl]sulfanylpropyl]sulfanylpropane-1-thiol Chemical compound SCCSC(CS)CSCC(S)CSCC(CS)SCCS OFPNMKVNQZZSIQ-UHFFFAOYSA-N 0.000 claims description 2
- NQLQMVQEQFIDQB-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)propane-1,3-dithiol Chemical compound SCCSC(CS)CS NQLQMVQEQFIDQB-UHFFFAOYSA-N 0.000 claims description 2
- WDZGTNIUZZMDIA-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.OCC(C)(CO)CO WDZGTNIUZZMDIA-UHFFFAOYSA-N 0.000 claims description 2
- QTEWPHJCEXIMRJ-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCC(SCCS)CSCCS QTEWPHJCEXIMRJ-UHFFFAOYSA-N 0.000 claims description 2
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 claims description 2
- ACBOBKJKSFYJML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylpropanoic acid Chemical compound CC(S)C(O)=O.CC(S)C(O)=O.CC(S)C(O)=O.CCC(CO)(CO)CO ACBOBKJKSFYJML-UHFFFAOYSA-N 0.000 claims description 2
- HJHZRZFONUPQAA-UHFFFAOYSA-N 2-isocyanato-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C(C)=C1 HJHZRZFONUPQAA-UHFFFAOYSA-N 0.000 claims description 2
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 claims description 2
- GNDOBZLRZOCGAS-UHFFFAOYSA-N 2-isocyanatoethyl 2,6-diisocyanatohexanoate Chemical compound O=C=NCCCCC(N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-UHFFFAOYSA-N 0.000 claims description 2
- XVSXUVBHGCOFHE-UHFFFAOYSA-N 2-isocyanatopropyl 2,6-diisocyanatohexanoate Chemical compound O=C=NC(C)COC(=O)C(N=C=O)CCCCN=C=O XVSXUVBHGCOFHE-UHFFFAOYSA-N 0.000 claims description 2
- CNSYSEMPKHDUHU-UHFFFAOYSA-N 3,5-bis(isocyanatomethyl)-2-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CN=C=O)C(CCCN=C=O)C1C2 CNSYSEMPKHDUHU-UHFFFAOYSA-N 0.000 claims description 2
- BXMHPINOHFKLMI-UHFFFAOYSA-N 3,5-bis(isocyanatomethyl)-3-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CCCN=C=O)(CN=C=O)CC1C2 BXMHPINOHFKLMI-UHFFFAOYSA-N 0.000 claims description 2
- FOLVZNOYNJFEBK-UHFFFAOYSA-N 3,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CN=C=O)CC1C2 FOLVZNOYNJFEBK-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 claims description 2
- JAVLMYDHCZNTMT-UHFFFAOYSA-N 5-(2-isocyanatoethyl)-2-(isocyanatomethyl)-2-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C2C(CCCN=C=O)(CN=C=O)CC1C(CCN=C=O)C2 JAVLMYDHCZNTMT-UHFFFAOYSA-N 0.000 claims description 2
- YGZKBWLEGAABPL-UHFFFAOYSA-N 5-(2-isocyanatoethyl)-3-(isocyanatomethyl)-3-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C(CCN=C=O)C2C(CCCN=C=O)(CN=C=O)CC1C2 YGZKBWLEGAABPL-UHFFFAOYSA-N 0.000 claims description 2
- QNNFODJDSHKLQL-UHFFFAOYSA-N 6,6-bis(hydroxymethyl)-1,11-diisocyanatoundeca-4,7-diene-5,7-diol Chemical compound O=C=NCCCC=C(O)C(CO)(CO)C(O)=CCCCN=C=O QNNFODJDSHKLQL-UHFFFAOYSA-N 0.000 claims description 2
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims description 2
- PEYZIFREGNMXEE-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1C(C)(C)C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1C(C)(C)C1CCCCC1 PEYZIFREGNMXEE-UHFFFAOYSA-N 0.000 claims description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 2
- OQSSNGKVNWXYOE-UHFFFAOYSA-N N=C=O.N=C=O.CCC(C)CC(C)(C)C Chemical compound N=C=O.N=C=O.CCC(C)CC(C)(C)C OQSSNGKVNWXYOE-UHFFFAOYSA-N 0.000 claims description 2
- MFWSSBVVMCUQFC-UHFFFAOYSA-N N=C=O.N=C=O.CCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCC(C)(C)C MFWSSBVVMCUQFC-UHFFFAOYSA-N 0.000 claims description 2
- KEGUGYDCYZRCFO-UHFFFAOYSA-N N=C=O.N=C=O.CS(C)(=O)=O Chemical compound N=C=O.N=C=O.CS(C)(=O)=O KEGUGYDCYZRCFO-UHFFFAOYSA-N 0.000 claims description 2
- XDUDBMDNVSGEQW-UHFFFAOYSA-N N=C=S.N=C=S.C1CCCCC1 Chemical compound N=C=S.N=C=S.C1CCCCC1 XDUDBMDNVSGEQW-UHFFFAOYSA-N 0.000 claims description 2
- DZYFUUQMKQBVBY-UHFFFAOYSA-N bis(2-isocyanatoethyl) carbonate Chemical compound O=C=NCCOC(=O)OCCN=C=O DZYFUUQMKQBVBY-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- DLTZIQGUEWGCCS-UHFFFAOYSA-N octahydro-2,5-bis(isocyanatomethyl)-4,7-methano-1h-indene Chemical compound C1C2CC(CN=C=O)C1C1C2CC(CN=C=O)C1 DLTZIQGUEWGCCS-UHFFFAOYSA-N 0.000 claims 2
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 claims 1
- GFRUDODCZTYECG-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)-2-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound C1C2C(CCCN=C=O)(CN=C=O)CC1C(CN=C=O)C2 GFRUDODCZTYECG-UHFFFAOYSA-N 0.000 claims 1
- LEPCJLRUTOSKJB-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 2-sulfanylpropanoic acid Chemical compound CC(S)C(O)=O.CC(S)C(O)=O.CC(S)C(O)=O.OCC(C)(CO)CO LEPCJLRUTOSKJB-UHFFFAOYSA-N 0.000 claims 1
- AJOSZJBREQTVHQ-UHFFFAOYSA-N 3,8-bis(isocyanatomethyl)tricyclo[5.2.1.02,6]decane Chemical compound C1C2C3C(CN=C=O)CCC3C1C(CN=C=O)C2 AJOSZJBREQTVHQ-UHFFFAOYSA-N 0.000 claims 1
- MREPGCSXKOVOII-UHFFFAOYSA-N 3,9-bis(isocyanatomethyl)tricyclo[5.2.1.02,6]decane Chemical compound C1C(CN=C=O)C2C3C(CN=C=O)CCC3C1C2 MREPGCSXKOVOII-UHFFFAOYSA-N 0.000 claims 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propyl mercaptan Natural products CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 description 48
- 238000003786 synthesis reaction Methods 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001723 curing Methods 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920002578 polythiourethane polymer Polymers 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 206010040925 Skin striae Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- HSFDFWROECINQQ-UHFFFAOYSA-N 1,3-diisothiocyanatopropane Chemical compound S=C=NCCCN=C=S HSFDFWROECINQQ-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- VSSFYDMUTATOHG-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)-3-[3-sulfanyl-2-(2-sulfanylethylsulfanyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCSC(CS)CSCC(CS)SCCS VSSFYDMUTATOHG-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- DAUUORKACOSESW-UHFFFAOYSA-N 2-[2-[2-(2-sulfanylethylsulfanyl)ethylsulfanyl]ethylsulfanylmethyl]propane-1,2,3-trithiol Chemical compound SCCSCCSCCSCC(S)(CS)CS DAUUORKACOSESW-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- VCVGLXGMPDRMRU-UHFFFAOYSA-N CC12CC(CC1(CCCN=C=O)N=C=O)C(C2)CN=C=O Chemical compound CC12CC(CC1(CCCN=C=O)N=C=O)C(C2)CN=C=O VCVGLXGMPDRMRU-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- OLYPWXRMOFUVGH-LURJTMIESA-N N(2)-methyl-L-lysine Chemical compound CN[C@H](C(O)=O)CCCCN OLYPWXRMOFUVGH-LURJTMIESA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VDKDFKRKAPXHBH-UHFFFAOYSA-N [3-(2-sulfanylpropanoyloxy)-2,2-bis(2-sulfanylpropanoyloxymethyl)propyl] 2-sulfanylpropanoate Chemical compound CC(S)C(=O)OCC(COC(=O)C(C)S)(COC(=O)C(C)S)COC(=O)C(C)S VDKDFKRKAPXHBH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- DGJUONISEWDPFO-UHFFFAOYSA-N dodecyl(triethyl)azanium Chemical class CCCCCCCCCCCC[N+](CC)(CC)CC DGJUONISEWDPFO-UHFFFAOYSA-N 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- VCAVAURZPNANDQ-UHFFFAOYSA-N ethyl-hexadecyl-dimethylazanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CC VCAVAURZPNANDQ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical class CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
본 발명은 웨이퍼레벨 렌즈용 광학 수지 조성물에 관한 것으로, 내열성이 높으면서도 굴절률, 투명성이 우수한 웨이퍼레벨 렌즈용 조성물에 관한 것이다. 특히, 본 발명은 웨이퍼레벨 렌즈의 제조에 요구되는 가공성 및 내열성, 광학적 특성이 우수한 수지 조성물에 관한 것이다.The present invention relates to an optical resin composition for wafer level lenses, and to a composition for wafer level lenses that has high heat resistance and excellent refractive index and transparency. In particular, the present invention relates to a resin composition having excellent processability, heat resistance, and optical properties required for manufacturing wafer-level lenses.
Description
본 발명은 웨이퍼레벨 렌즈용 광학 수지 조성물에 관한 것으로, 내열성이 높으면서도 굴절률, 투명성이 우수한 웨이퍼레벨 렌즈용 조성물에 관한 것이다. 특히, 본 발명은 웨이퍼레벨 렌즈의 제조에 요구되는 가공성 및 내열성, 광학적 특성이 우수한 수지 조성물에 관한 것이다.The present invention relates to an optical resin composition for wafer level lenses, and to a composition for wafer level lenses that has high heat resistance and excellent refractive index and transparency. In particular, the present invention relates to a resin composition having excellent processability, heat resistance, and optical properties required for manufacturing wafer-level lenses.
이소시아네이트와 폴리티올 화합물을 사용하여 제조한 광학수지는 투명성, 아베수 인장강도와 같은 광학적 특성이 우수하고, 유리에 비해 비중이 낮아 가볍고, 가공이 용이하여 광학수지 소재로 널리 사용되고 있다. 그러나 기존 우레탄계 광학 수지는 열변형 온도가 낮아 광학 수지를 캐스팅 후 렌즈 표 면에 하드-멀티 코팅 시 렌즈의 중심 변형이 발생하는 문제가 있고, 또 사우나 및 고온의 작업이 이루어지는 산업 현장 등에서 사용 시 고온에 노출되면 우레탄계 광 학수지의 열변형이 발생하여 멀티 코팅 층에 갈라짐이 유발하게 된다. 멀티 코팅 층이 갈라지게 되면 렌즈 표면에 뿌연 막을 형성하게 되어 광학 수지의 투명도가 급격히 낮아지게 되는 문제점이 있다.Optical resins manufactured using isocyanate and polythiol compounds have excellent optical properties such as transparency and Abbe number tensile strength, and are light and easy to process due to their low specific gravity compared to glass, so they are widely used as optical resin materials. However, the existing urethane-based optical resin has a low heat distortion temperature, so there is a problem of center deformation of the lens when hard-multi coating the surface of the lens after casting the optical resin. Also, when used in saunas or industrial sites where high-temperature work is performed, high temperatures occur. When exposed to urethane-based optical resin, thermal deformation occurs, causing cracking in the multi-coating layer. If the multi-coating layer is split, a hazy film is formed on the lens surface, causing a problem in that the transparency of the optical resin rapidly decreases.
종래 폴리우레탄 계열의 수지는 시력보정 렌즈 제작에 국한되어 몰드에 주입시 점도의 상승이 문제되어 가급적 점도가 없는 모노머 상태를 유지하고자 한다. 또한 경화시간이 길어 생산과정에 가급적 많은 몰드 주입과 경화가공을 진행해야 한다. Conventionally, polyurethane-based resins are limited to the production of vision correction lenses, and an increase in viscosity when injected into a mold is a problem, so it is attempted to maintain a monomer state with as little viscosity as possible. In addition, because the curing time is long, as much mold injection and curing as possible must be performed during the production process.
반면에 웨이퍼 레벨 렌즈는 웨이퍼 제조 공정을 이용하여 생산되는 웨이퍼 단위의 렌즈로서, 카메라 모듈 등에 사용된다. 일반적으로, 고정밀의 웨이퍼 레벨 렌즈는 마스터링(Mastering) 공정, 스탬핑(Stamping) 공정, 엠보싱(Embossing) 공정 및 다이싱(Dicing) 공정을 순차적으로 거치며 제작된다. 종래의 가스켓 및 필름 가스켓 몰드구조 방식의 가공 방법보다는 하부 몰드에 모노머 주입 후 상부 몰드로 스탬핑을 하는 방식으로 수지조성물의 흐름성이 낮은 고점도 물성을 요구하고 있다. 하지만 너무 높은 점도의 수지조성물은 스탬핑을 위한 흐름성 조정에는 용이하나, 수지조성물의 주입 시 기포형성 등의 문제점이 있다. On the other hand, wafer level lenses are wafer-level lenses produced using a wafer manufacturing process and are used in camera modules, etc. Generally, high-precision wafer-level lenses are manufactured by sequentially going through a mastering process, stamping process, embossing process, and dicing process. Rather than the conventional gasket and film gasket mold structure processing method, the method of injecting monomer into the lower mold and stamping with the upper mold requires high viscosity properties with low flowability of the resin composition. However, a resin composition with too high a viscosity is easy to adjust flowability for stamping, but has problems such as bubble formation when injecting the resin composition.
웨이퍼 레벨 렌즈의 제조에서는, 몰드 주입시 수지조성물의 점도가 2500 내지 5000 cps의 점도를 유지하는 것이 바람직하다. 이에 본 발명자는 수지조성물을 이소시아네이트 모노머와 폴리티올 모노머의 예비 중합체로 제조하여 점도를 높여 가공이 용이하도록 발명하였다.In the manufacture of wafer level lenses, it is desirable to maintain a viscosity of 2500 to 5000 cps of the resin composition during mold injection. Accordingly, the present inventor invented a resin composition made of a prepolymer of isocyanate monomer and polythiol monomer to increase viscosity and facilitate processing.
또한, 이 경우에, 수지조성물을 몰드에 주입하고, 30분이내의 경화시간을 통해 완성된 렌즈를 얻는 것이 바람직하다. 수지조성물은 온도에 따라 점도가 비례하여 지속적으로 증가하는 것이 아니라, 재료마다 상이한 특성에 의해 특정 온도까지는 오히려 점도가 떨어진다. 이후, 특정 온도보다 온도가 높아질 경우, 다시 점도가 증가하다가 굳어지는 특성을 갖는다. 따라서, 특정 온도에 도달하기 이전 상태에서 웨이퍼 레벨 렌즈 제조장치가 상부몰드를 이용하여 수지조성물에 압력을 가할 경우, 수지조성물의 유변특성(점도 및 용융강도계수)으로 인해 점도가 떨어짐으로서, 수지조성물이 상부몰드으로부터 흘러나오는 현상이 발생한다. 더욱이, 수지조성물이 상부몰드로부터 유출된 상태에서 렌즈용 액상 수지의 열경화가 진행되면, 렌즈의 중심부가 수축되어, 결과적으로, 렌즈와 상부몰드 사이에 빈 공간이 발생하는 문제가 발생한다. 이에 본 발명에서는 수지조성물을 몰드에 주입한 후 30분 이내에 경화시킴으로써 본 문제를 해결하였다.Also, in this case, it is preferable to inject the resin composition into the mold and obtain a completed lens through a curing time of less than 30 minutes. The viscosity of a resin composition does not continuously increase in proportion to temperature, but rather decreases in viscosity up to a certain temperature due to the different characteristics of each material. Afterwards, when the temperature rises above a certain temperature, the viscosity increases again and then hardens. Therefore, when the wafer level lens manufacturing device applies pressure to the resin composition using the upper mold before reaching a specific temperature, the viscosity decreases due to the rheological characteristics (viscosity and melt strength coefficient) of the resin composition. A phenomenon of flowing out from this upper mold occurs. Furthermore, if thermal curing of the liquid resin for a lens proceeds while the resin composition flows out from the upper mold, the center of the lens shrinks, resulting in the creation of an empty space between the lens and the upper mold. Accordingly, in the present invention, this problem was solved by curing the resin composition within 30 minutes after injecting it into the mold.
또한 기존 렌즈 가공의 중요 요소는 중합 불균형으로 인한 맥리현성을 억제하기 위해 모노머 배합부터 5 내지 10℃의 저온 공정이 요구되었으나, 이때 상기 온도에서는 수지조성물의 점도가 너무 높아 몰드 주입의 어려움이 있었으며, 기포제거가 어려워 별도의 감압처리가 중요 파라메터로 인식되었다.In addition, an important element of conventional lens processing is that a low-temperature process of 5 to 10°C is required from monomer mixing to suppress striae due to polymerization imbalance, but at this temperature, the viscosity of the resin composition is too high, making mold injection difficult. Because air bubbles were difficult to remove, separate pressure reduction treatment was recognized as an important parameter.
하지만 본 발명자는 수지조성물을 예비중합체로 제조하므로써 주입 전 20℃에서 2000 내지 5000 cp의 높은 점도를 유지하면서, 10℃ 부근의 저온보다는 20 내지 25℃의 조건에서 주입하여 짧은 경화시간으로 웨이퍼 레벨의 렌즈를 가공할 수 있다는 것을 확인하고, 본 발명을 완성하게 되었다.However, by manufacturing the resin composition as a prepolymer, the present inventor maintains a high viscosity of 2000 to 5000 cp at 20°C before injection, and injects under conditions of 20 to 25°C rather than at a low temperature around 10°C to achieve wafer-level curing with a short curing time. After confirming that lenses could be processed, the present invention was completed.
한편, 본 발명자들은 월등한 내열성을 가지기 위해서 예의 검토한 결과 후술하는 화학식(1)의 디이소시아네이토메틸 시클로헥산을 핵심 원료로 활용해서 여러가지 조건하에서 내열성을 연구한 결과 내열성이 130℃ 이상으로 우수하고, 굴절율도 1.59에서 1.65까지 조절이 가능하며 백화현상도 현저하게 제거되고, 황변현상도 나타나지 않는 웨이퍼레벨 렌즈용 폴리티오우레탄 조성물을 발명하게 되었다.Meanwhile, the present inventors studied the heat resistance under various conditions using diisocyanatomethyl cyclohexane of the formula (1) as a core raw material, as a result of careful examination to ensure superior heat resistance, and found that the heat resistance was excellent at over 130°C. In addition, a polythiourethane composition for wafer-level lenses was invented that can adjust the refractive index from 1.59 to 1.65, significantly eliminates whitening, and does not cause yellowing.
상기 과제를 해결하기 위하여, 본 발명의 한 양태로서, 본 발명은 디이소시아네이트 화합물과 폴리티올 화합물로 구성된 광학 수지 조성물로서, (1) 이소시아네이트의 작용기(NCO)와 폴리티올의 작용기(SH)의 몰비(NCO/SH의 몰비)가 1/8이하로 중합한 폴리티올 예비중합체, NCO/SH의 몰비가 8이상으로 중합한 디이소시아네이트 예비중합체를 포함하고; In order to solve the above problem, in one aspect of the present invention, the present invention is an optical resin composition composed of a diisocyanate compound and a polythiol compound, (1) the molar ratio of the functional group of isocyanate (NCO) and the functional group of polythiol (SH) It includes a polythiol prepolymer polymerized with a molar ratio of NCO/SH of 1/8 or less, and a diisocyanate prepolymer polymerized with a molar ratio of NCO/SH of 8 or more;
(2) 상기 디이소시아네이트 화합물의 하나로서, 하기 화학식 1:(2) As one of the above diisocyanate compounds, the following formula 1:
로 표시되는 메틸디이소시아네이트시클로헥산이 상기 디이소시아네이트 화합물의 총량에서 적어도 30%이상을 포함하면서;Methyl diisocyanate cyclohexane represented by contains at least 30% or more of the total amount of the diisocyanate compound;
(3) 상기 예비중합체 액상의 점도가 2,000~5000 cp인 것을 특징으로 하는, 웨이퍼레벨 광학 렌즈용 수지조성물을 제공한다.(3) A resin composition for a wafer-level optical lens is provided, wherein the prepolymer liquid phase has a viscosity of 2,000 to 5,000 cp.
본 발명의 다른 양태로서, 상기 메틸디이소시아네이트시클로헥산은 하기 화학식 2 또는 화학식 3의 화합물인 것을 특징으로 한다:In another aspect of the present invention, the methyl diisocyanate cyclohexane is characterized in that it is a compound of the following formula (2) or formula (3):
본 발명의 또 다른 양태로서, 상기 메틸디이소시아네이트시클로헥산을 제외한 다른 디이소시아네이트 화합물이 알킬렌 디이소시아네이트 화합물, 지환족 디이소시아네이트 화합물, 헤테로고리 디이소시아네이트 화합물 또는 황을 함유한 지방족 디이소시아 네이트 화합물인 것을 특징으로 한다. In another aspect of the present invention, the diisocyanate compounds other than the methyl diisocyanate cyclohexane are alkylene diisocyanate compounds, alicyclic diisocyanate compounds, heterocyclic diisocyanate compounds, or sulfur-containing aliphatic diisocyanate compounds. It is characterized by
본 발명의 또 다른 양태로서, 상기 광학 렌즈용 수지조성물 총 중량 중에 자외선 흡수제 0.001~10중량%, 이형제 0.0001~10 중량% 및 촉매제 0.001~10중량%를 추가로 포함할 수 있다. In another aspect of the present invention, the total weight of the resin composition for optical lenses may further include 0.001 to 10% by weight of an ultraviolet absorber, 0.0001 to 10% by weight of a mold release agent, and 0.001 to 10% by weight of a catalyst.
본 발명의 또 다른 양태로서, 본 발명은 As another aspect of the present invention, the present invention
(1) 이소시아네이트의 작용기(NCO)와 폴리티올의 작용기(SH)의 몰비(NCO/SH의 몰비)가 8이상의 범위의 과량의 이소시아네이트 화합물에 NCO/SH의 몰비가 1/8 이하의 범위의 소량의 폴리티올을 첨가하고 소정의 시간과 온도에서 얻어진 용액에 백탁이 발생하기 전에 중합반응을 완료하여 이소시아네이트 예비중합체를 제조하는 단계;(1) Excess isocyanate compound in which the molar ratio of isocyanate functional group (NCO) and polythiol functional group (SH) (NCO/SH molar ratio) is 8 or more, and a small amount of NCO/SH molar ratio is 1/8 or less. Preparing an isocyanate prepolymer by adding polythiol and completing the polymerization reaction before white turbidity occurs in the solution obtained at a predetermined time and temperature;
(2) NCO/SH의 몰비가 8이상의 과량의 폴리티올에 NCO/SH의 몰비가 1/8 이하의 범위의 소량의 이소시아네이트를 첨가하고 소정의 시간과 온도에서 얻어진 용액에 백탁이 발생하기 전에 중합반응을 완료하여 폴리티올 예비중합체를 제조하는 단계; 및 (2) Add a small amount of isocyanate with an NCO/SH molar ratio of 1/8 or less to excess polythiol with an NCO/SH molar ratio of 8 or more, and polymerize the resulting solution at a predetermined time and temperature before white turbidity occurs. Completing the reaction to prepare a polythiol prepolymer; and
(3) 상기에서 얻어진 이소시아네이트 예비중합체와 폴리티올 예비중합체를 혼합하는 단계;(3) mixing the isocyanate prepolymer and polythiol prepolymer obtained above;
를 포함하는, 제1항 내지 제5항 중 어느 한 항에 기재된 광학 수지 조성물을 이용한, 웨이퍼레벨용 광학 수지를 제조하는 방법을 제공한다.It provides a method of manufacturing an optical resin for wafer level using the optical resin composition according to any one of claims 1 to 5, including.
본 발명의 또 다른 양태로서, 본 발명은 상기 광학 수지를 제조하는 방법으로 제조된 웨이퍼레벨용 광학 수지를 제공한다.In another aspect of the present invention, the present invention provides an optical resin for wafer level manufactured by the method of manufacturing the optical resin.
본 발명의 수지조성물은 웨이퍼레벨 렌즈를 제조함에 있어 우수한 가공성을 위해 특정 점도를 유지할 필요성이 있으며, 웨이퍼레벨 렌즈의 광학적 특성을 위해 수축률을 감소시켜야 하므로 이소시아네이트 화합물과 폴리티올 화합물로 예비중합체를 제조하여 사용하는 것이 필요하다. 예비중합체는 이소시아네이트(NCO) 화합물의 작용기와 폴리티올(SH)의 작용기에서 NCO/SH의 작용기의 몰비가 0.1 내지 0.15의 범위 내에서 미리 중합하는 폴리티올 예비조성물, 8 내지 10의 범위 내에서 미리 중합하는 이소시아네이트 예비조성물이 바람직하고, 더욱 바람직하게는 이들의 몰비가 각각 0.125 내지 0.15, 8 내지 9의 범위이다. 또한, 상기 폴리 이소시아네이트 화합물에서, 화학식 (1)의 함유율은 30%이상이며, 바람직하게는 50% 이상, 더욱 바람직하게는 60% 이상을 함유하는 더욱 바람직하다. 한편, 본 발명에서는 상기의 이소시아네이트 예비중합체와 폴리티올 예비중합체를 중합시켜 광학용 수지를 제조하게 된다. 여기서 상기의 광학용 중합성 조성물을 120℃에서 30분 이내로 중합 가공하는 것이 바람직하다. 또한, 본 발명은 상기의 광학용 수지로 이루어진 광학 제품, 특히 렌즈에 관한 것이다.The resin composition of the present invention needs to maintain a certain viscosity for excellent processability in manufacturing wafer-level lenses, and shrinkage must be reduced for the optical properties of wafer-level lenses, so a prepolymer is prepared with an isocyanate compound and a polythiol compound. It is necessary to use The prepolymer is a polythiol precomposition in which the molar ratio of the functional group of the isocyanate (NCO) compound and the functional group of polythiol (SH) is in the range of 0.1 to 0.15, and the molar ratio of the functional group of NCO / SH is in the range of 8 to 10. A polymerizing isocyanate pre-composition is preferred, and more preferably, their molar ratio is in the range of 0.125 to 0.15 and 8 to 9, respectively. In addition, in the polyisocyanate compound, the content of the formula (1) is 30% or more, preferably 50% or more, and more preferably 60% or more. Meanwhile, in the present invention, an optical resin is manufactured by polymerizing the isocyanate prepolymer and the polythiol prepolymer. Here, it is preferable to polymerize the optical polymerizable composition at 120°C within 30 minutes. Additionally, the present invention relates to optical products, particularly lenses, made of the above optical resin.
본 발명에서, 메틸디이소시아네이트시클로헥산을 제외한 이소시아네이트 화합물로는 알킬렌 디이소시아네이트 화합물, 지환족 디이소시아네이트 화합물, 헤 테로고리 디이소시아네이트 화합물, 황을 함유한 지방족 디이소시아네이트 화합물 등을 사용할 수 있다.In the present invention, as the isocyanate compound excluding methyl diisocyanate cyclohexane, alkylene diisocyanate compounds, alicyclic diisocyanate compounds, heterocyclic diisocyanate compounds, sulfur-containing aliphatic diisocyanate compounds, etc. can be used.
알킬렌 디이소시아네이트 화합물에는, 예를 들어, 에틸렌디이소시아 네이트; 트리메틸렌디이소시아네이트; 테트라메틸렌디이소시아네이트; 1,6-헥사메 틸렌디이소시아네이트; 옥타메틸렌디이소시아네이트; 노나메틸렌디이소시아네이트; 2,2-디메틸펜탄디이소시아네이트; 2,2,4-트리메틸헥산디이소시아네이트; 데카메틸 렌디이소시아네이트; 부텐디이소시아네이트; 1,3-부타디엔-1,4-디이소시아네이트; 2,4,4-트리메틸헥사메틸렌디이소시아네이트; 1,6,11-운데칸트리이소시아네이트;Alkylene diisocyanate compounds include, for example, ethylene diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; octamethylene diisocyanate; nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexane diisocyanate; decamethyl lenediisocyanate; butene diisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecane triisocyanate;
1,3,6-헥사메틸렌트리이소시아네이트; 1,8-디이소시아네이토-4-이소시아네이토메틸 옥탄; 2,5,7-트리메틸-1,8-디이소시아네이토-5-이소시아네이토메틸옥탄; 비스(이소 시아네이토에틸)카보네이트; 비스(이소시아네이토에틸)에테르; 1,4-부틸렌글리콜디 프로필에테르-1,2-디이소시아네이트; 1,4-부틸렌글리콜디프로필에테르-1,3-디이소 시아네이트; 1,4-부틸렌글리콜디프로필에테르-1,4-디이소시아네이트; 1,4-부틸렌글 리콜디프로필에테르-2,3-디이소시아네이트; 1,4-부틸렌글리콜디프로필에테르- 2,4-디이소시아네이트; 메틸리신디이소시아네이트; 리신트리이소시아네이트; 2-이 소시아네이토에틸-2,6-디이소시아네이토헥사노에이트; 2-이소시아네이토프로필- 2,6-디이소시아네이토헥사노에이트; 메시틸렌트리이소시아네이트; 2,6-디(이소시아 네이토메틸)푸란 등이 있다.1,3,6-hexamethylene triisocyanate; 1,8-diisocyanato-4-isocyanatomethyl octane; 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane; Bis(isocyanatoethyl)carbonate; Bis(isocyanatoethyl)ether; 1,4-butylene glycol dipropyl ether-1,2-diisocyanate; 1,4-butylene glycol dipropyl ether-1,3-diisocyanate; 1,4-butylene glycol dipropyl ether-1,4-diisocyanate; 1,4-butylene glycol dipropyl ether-2,3-diisocyanate; 1,4-butylene glycol dipropyl ether-2,4-diisocyanate; methyl lysine diisocyanate; Lysine triisocyanate; 2-Isocyanatoethyl-2,6-diisocyanatohexanoate; 2-Isocyanatopropyl-2,6-diisocyanatohexanoate; Mesitylene triisocyanate; 2,6-di(isocynatomethyl)furan, etc.
지환족 디이소시아네이트 화합물에는, 예를 들어, 이소포론디이소시 아네이트; 디시클로헥실메탄디이소시아네이트; 3,8-비스(이소시아나토메틸)트리시 클로[5,2,1,0,6]데칸; 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,0,6]데칸; 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,0,6]데칸; 4,9-비스(이소시아나토메 틸)트리시클로[5,2,1,0,6]데칸; 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄; 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄; 비스(이소시아네이토메틸)시클로 헥산; 디시클로헥실메탄디이소시아네이트; 시클로헥산디이소시아네이트; 메틸시클 로헥산디이소시아네이트; 디시클로헥실디메틸메탄디이소시아네이트; 2,2'-디메틸디 시클로헥실메탄디이소시아네이트; 비스(4-이소시아네이토-n-부틸리덴)펜타에리트리 톨; 다이머산디이소시아네이트; 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-5-이소시아네이토메틸비시클로[2,2,1]-헵탄; 2-이소시아네이토메틸-3-(3-이소 시아네이토프로필)-6-이소시아네이토메틸비시클로[2,2,1]-헵탄; 2-이소시아네이토 메틸-2-(3-이소시아네이토프로필)-5-이소시아네이토메틸-비시클로[2,2,1]-헵탄; 2- 이소시아네이토메틸-2-(3-이소시아네이토프로필)-6-이소시아네이토메틸-비시클로 [2,2,1]-헵탄; 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-(2-이소시아네 이토에틸)-비시클로[2,2,1]-헵탄; 2-이소시아네이토메틸-3-(3-이소시아네이토프로 필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄; 2-이소시아네이토메틸-2-(3- 이소시아네이토프로필)-5-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄; 2-이소시 아네이토메틸-2-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2, 2,1]-헵탄; 1,3,5-트리스(이소시아네이토메틸)-시클로헥산; 디시클로헥실메탄-4,4- 디이소시아네이트(H12MDI) 등이 있다.Alicyclic diisocyanate compounds include, for example, isophorone diisocyanate; dicyclohexylmethane diisocyanate; 3,8-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 3,9-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 4,8-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 4,9-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane; 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane; Bis(isocyanatomethyl)cyclohexane; dicyclohexylmethane diisocyanate; cyclohexane diisocyanate; methylcyclohexanediisocyanate; dicyclohexyldimethylmethane diisocyanate; 2,2'-dimethyldicyclohexylmethane diisocyanate; Bis(4-isocyanato-n-butylidene)pentaerythritol; dimer acid diisocyanate; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo[2,2,1]-heptane; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethylbicyclo[2,2,1]-heptane; 2-Isocyanato methyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane; 2-Isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo [2,2,1]-heptane; 2-Isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-Isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-Isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-Isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2, 2,1]-heptane; 1,3,5-tris(isocyanatomethyl)-cyclohexane; Dicyclohexylmethane-4,4-diisocyanate (H12MDI), etc.
헤테로고리 디이소시아네이트 화합물에는, 예를 들어, 티오펜- 2,5-디이소시아네이트; 메틸 티오펜-2,5-디이소시아네이트; 1,4-디티안-2,5-디이소 시아네이트; 메틸 1,4-디티안-2,5-디이소시아네이트; 1,3-디티올란-4,5-디이소시아 네이트; 메틸 1,3-디티올란-4,5-디이소시아네이트; 메틸 1,3-디티올란-2-메틸-4,5- 디이소시아네이트; 에틸1,3-디티올란-2,2-디이소시아네이트; 테트라히드로티오펜- 2,5-디이소시아네이트; 메틸테트라히드로티오펜-2,5-디이소시아네이트; 에틸 테트 라히드로티오펜-2,5-디이소시아네이트; 메틸 테트라히드로티오펜-3,4-디이소시아네 이트; 1,2-디이소티오시아네이토에탄; 1,3-디이소티오시아네이토프로판; 1,4-디이 소티오시아네이토부탄; 1,6-디이소티오시아네이토헥산; p-페닐렌디이소프로필리덴 디이소티오시아네이트; 시클로헥산디이소티오시아네이트 등이 있다.Heterocyclic diisocyanate compounds include, for example, thiophene-2,5-diisocyanate; Methyl thiophene-2,5-diisocyanate; 1,4-dithiane-2,5-diisocyanate; Methyl 1,4-dithiane-2,5-diisocyanate; 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate; Ethyl 1,3-dithiolane-2,2-diisocyanate; Tetrahydrothiophene-2,5-diisocyanate; Methyltetrahydrothiophene-2,5-diisocyanate; ethyl tetrahydrothiophene-2,5-diisocyanate; methyl tetrahydrothiophene-3,4-diisocyanate; 1,2-diisothiocyanatoethane; 1,3-diisothiocyanatopropane; 1,4-Diisothiocyanatobutane; 1,6-diisothiocyanatohexane; p-phenylenediisopropylidene diisothiocyanate; Cyclohexane diisothiocyanate, etc.
황을 함유한 지방족 디이소시아네이트 화합물에는, 예를 들어, 4-이 소시아네이토-4'-이소티오시아네이토디페닐술피드; 2-이소시아네이토-2'-이소티오 시아네이토디에틸디술피드; 티오디에틸디이소시아네이트; 티오디프로필디이소시아 네이트; 티오디헥실디이소시아네이트; 디메틸술폰디이소시아네이트; 디티오디메틸 디이소시아네이트; 디티오디에틸디이소시아네이트; 디티오디프로필디이소시아네이 트; 디시클로헥실술퍼-4,4'-디이소시아네이트; 1-이소시아네이토메틸티아-2,3-비스 (2-이소시아네이토에틸티아)프로판 등이 있다.Sulfur-containing aliphatic diisocyanate compounds include, for example, 4-isocyanato-4'-isothiocyanatodiphenyl sulfide; 2-isocyanato-2'-isothiocyanatodiethyldisulfide; thiodiethyl diisocyanate; thiodipropyldiisocyanate; thiodihexyl diisocyanate; dimethylsulfone diisocyanate; dithiodimethyl diisocyanate; dithiodiethyl diisocyanate; Dithiodypropyl diisocyanate; Dicyclohexylsulfur-4,4'-diisocyanate; 1-isocyanatomethylthia-2,3-bis (2-isocyanatoethylthia)propane, etc.
상기 폴리티올 화합물은 분자 내에 황 원자를 적어도 하나 이상 가 지는 화합물이다. 바람직하게는, 2-(2-메르캅토에틸티오)프로판-1,3-디티올; 2,3- 비스(2-메르캅토에틸티오)프로판-1-티올; 2-(2,3-비스(2-메르캅토에틸티오)프로필 티오)에탄티올; 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판; 1,2-비스(2- (2-메르캅토에틸티오)-3-메르캅토프로필티오)-에탄; 비스(2-(2-메르캅토에틸티오)- 3-메르캅토프로필)술피드, 2-(2-메르캅토에틸티오)-3-{2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오}-프로판-1-티올; 2,2-비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르; 2-(2-메르캅토에틸티오)-3-(2-{2-[3-메 르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오}에틸티오)프로판-1-티올 중 1 종 혹은 2종 이상을 사용한다.The polythiol compound is a compound having at least one sulfur atom in the molecule. Preferably, 2-(2-mercaptoethylthio)propane-1,3-dithiol; 2,3-bis(2-mercaptoethylthio)propane-1-thiol; 2-(2,3-bis(2-mercaptoethylthio)propyl thio)ethanethiol; 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane; 1,2-bis(2- (2-mercaptoethylthio)-3-mercaptopropylthio)-ethane; Bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 2-(2-mercaptoethylthio)-3-{2-mercapto-3-[3-mercapto-2 -(2-mercaptoethylthio)-propylthio]propylthio}-propane-1-thiol; 2,2-bis-(3-mercapto-propionyloxymethyl)-butyl ester; 2-(2-mercaptoethylthio)-3-(2-{2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio}ethylthio)propane-1- One or two or more types of thiols are used.
또는 상기 폴리티올 화합물은 티올에스테르 화합물을 포함한다. 예를 들어, 티올에스테르 화합물은 한 분자 내에 티올기가 3개 존재하는 3가 티올에스테르 화합물로서 트리메틸올프로판 트리스(메르캅토프로피오네이트), 트리메틸올 에탄 트리스(메르캅토프로피오네이트), 글리세롤 트리스(메르캅토프로피오네이트), 트리메틸올클로로트리스(메르캅토프로피오네이트), 트리메틸올프로판 트리스(메르 캅토아세테이트), 트리메틸올에탄 트리스(메르캅토아세테이트) 등을 사용할 수 있 으며, 4가 이상의 티올에스테르화합물로서 펜타에리트리톨테트라키스(메르캅토프로 피오네이트)(PETMP), 펜타에리트리톨테트라키스(메르캅토아세테이트)(PETMA), 비스 펜타에리트리톨-에테르-헥사키스(메르캅토프로피오네이트)(BPEHMP), 비스펜타에리 트리톨-에테르-헥사키스(2-메르캅토아세테이트)(BPEHMA), 비스펜타에리트리톨헥사 (2-메르캅토아세테이트)(BPEMA), 비스트리메틸올프로판테트라키스(3-메르캅토프로 피오네이트)(BTMPMP), 비스트리메틸올프로판테트라키스(2-메르캅토아세테이 트)(BTMPMA) 등을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.Alternatively, the polythiol compound includes a thiol ester compound. For example, thiol ester compounds are trivalent thiol ester compounds with three thiol groups in one molecule, and include trimethylolpropane tris (mercaptopropionate), trimethylol ethane tris (mercaptopropionate), and glycerol tris ( Mercaptopropionate), trimethylolchlorotris(mercaptopropionate), trimethylolpropane tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), etc. can be used, and thiol esters of tetravalence or higher Compounds include pentaerythritol tetrakis (mercaptopropionate) (PETMP), pentaerythritol tetrakis (mercaptoacetate) (PETMA), and bis pentaerythritol-ether-hexakis (mercaptopropionate) ( BPEHMP), bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA), bispentaerythritol hexa (2-mercaptoacetate) (BPEMA), bistrimethylolpropanetetrakis (3-mer Captopropionate) (BTMPMP), bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA), etc. can be used alone or in a mixture of two or more.
상기 중합성 조성물은, 그 외에도 필요에 따라, 내부 이형제, 자외 선 흡수제, 중합개시제, 열안정제, 색상보정제, 사슬연장제, 가교제, 광안정제, 산 화방지제, 충전제, 근적외선 흡수제 등의 첨가제를 더 포함할 수 있다.In addition, the polymerizable composition may contain additives such as an internal mold release agent, ultraviolet absorber, polymerization initiator, heat stabilizer, color corrector, chain extender, crosslinker, light stabilizer, antioxidant, filler, near-infrared absorber, etc., if necessary. More may be included.
상기 내부 이형제로는, 퍼플루오르알킬기, 히드록시알킬기 또는 인 산에스테르기를 지닌 불소계 비이온계면활성제; 디메틸폴리실록산기, 히드록시알킬 기 또는 인산에스테르기를 가진 실리콘계 비이온계면활성제; 알킬제 4급암모늄염 즉, 트리메틸세틸 암모늄염, 트리메틸스테아릴, 디메틸에틸세틸 암모늄염, 트리에 틸도데실 암모늄염, 트리옥틸메틸 암모늄염, 디에틸시클로헥사도데실 암모늄염; 산 성 인산에스테르 중에서 선택된 성분이 단독으로 혹은 2종 이상 함께 사용될 수 있다.Examples of the internal release agent include a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphoric acid ester group; Silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphoric acid ester group; Alkyl quaternary ammonium salts, namely trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; Components selected from acid phosphate esters may be used alone or in combination of two or more.
상기 자외선 흡수제로는 벤조페논계, 벤조트리아졸계, 트리아진계, 살리실레이트계, 시아노아크릴레이트계, 옥사닐라이드계 등이 사용될 수 있다.As the ultraviolet absorber, benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, oxanilide-based, etc. may be used.
상기 중합개시제로는 아민계, 인계, 유기주석계, 유기구리계, 유기 갈륨, 유기지르코늄, 유기철계, 유기아연, 유기알루미늄, 유기비스무스계 등이 사 용될 수 있다. 상기 열안정제로는, 금속 지방산염계, 인계, 납계, 유기주석계 등을 1종 또는 2종 이상 혼합하여 사용가능하다.The polymerization initiator may be amine-based, phosphorus-based, organotin-based, organo-copper-based, organic gallium, organozirconium, organo-iron-based, organozinc, organoaluminium, organobismuth-based, etc. As the heat stabilizer, one type or a mixture of two or more types such as metal fatty acid salt-based, phosphorus-based, lead-based, organotin-based, etc. can be used.
또한, 본 발명에 따르면, 앞서 설명한 이소시아네이트 예비중합체와 폴리티올 예비중합체인 수지조성물로부터 얻은 폴리티오우레탄이 제공된다. 즉, 상기 폴리티오우레탄은 상기 중합성 조성물 내의 이 소시아네이트 조성물과 티올이 중합(및 경화)되어 제조될 수 있다. 상기 중합 반응 은 예비중합체의 SH기/NCO기의 몰비가 0.5 내지 1.5일 수 있고, 보다 바람직하게는 0.9 내지 1.1 이 되도록 반응시킬 수 있다.In addition, according to the present invention, polythiourethane obtained from a resin composition of the isocyanate prepolymer and polythiol prepolymer described above is provided. That is, the polythiourethane can be produced by polymerizing (and curing) the isocyanate composition and thiol in the polymerizable composition. The polymerization reaction may be carried out so that the molar ratio of SH groups/NCO groups of the prepolymer may be 0.5 to 1.5, and more preferably 0.9 to 1.1.
또한, 원하는 반응 속도로 조정하기 위해서, 반응 촉매를 적절하게 첨가할 수 있다. 바람직하게 사용되는 촉매로는, 예를 들면, 우레탄화 촉매로서, 디부틸주석디라우레이트, 디부틸주석디클로라이드, 디메틸주석디클로라이드, 테트 라메틸디아세톡시디스타녹산, 테트라에틸디아세톡시디스타녹산, 테트라프로필디아 세톡시디스타녹산, 테트라부틸디아세톡시디스타녹산 등의 주석 화합물이나 3급 아민 등의 아민 화합물을 사용할 수 있다. 이들은, 단독으로 사용하는 것도, 2종류이상을 병용하는 것도 가능하다. 촉매의 첨가량으로는, 조성물의 모노머 총중량에 대해서 0.001~1중량%의 범위에서 사용하는 것이 바람직하며, 더욱 바람직하게는 0.05~0.5중량%이다. 이 범위인 경우, 중합성은 물론 작업 시 가사시간(pot life)이나 얻어지는 수지의 투명성 등 광학적 특성에서 바람직하다.Additionally, in order to adjust the reaction rate to the desired level, a reaction catalyst may be added as appropriate. Catalysts preferably used include, for example, urethanization catalysts such as dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, tetramethyldiacetoxydistanoxane, and tetraethyldiacetoxydista. Tin compounds such as oxane, tetrapropyldiacetoxydistanoxane, and tetrabutyldiacetoxydistanoxane, or amine compounds such as tertiary amines can be used. These can be used individually or in combination of two or more types. The amount of catalyst added is preferably in the range of 0.001 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total weight of monomers in the composition. This range is desirable not only for polymerizability but also for optical properties such as pot life and transparency of the resulting resin.
본 발명의 조성물들을 중합에 의해 경화시킬 때에는, 용도에 따라서 여러 가지 성형법이 있을 수 있고 특별히 제한된 경화 방법은 없지만 대체적으로 열에 의한 경화를 주로 사용한다. 이것에 의해, 본 발명의 수지가 얻어진다. 본 발 명의 수지는 통상적인 방법인 몰드 주입 방식인 주형(注型)중합에 의해 얻어진다.When curing the compositions of the present invention by polymerization, there may be various molding methods depending on the use, and there is no particularly limited curing method, but curing by heat is generally used. As a result, the resin of the present invention is obtained. The resin of the present invention is obtained by cast polymerization, which is a conventional mold injection method.
또한, 본 발명의 광학렌즈용 수지 조성물은 렌즈의 초기색상을 보정을 위한 색상 보정제를 더 포함할 수 있다. 색상 보정제로는 유기염료, 유기안료, 무기안료 등이 사용될 수 있다. 이러한 유기염료등을 광학렌즈용 수지 조성물 1당 0.1~50,000ppm, 바람직하게는 0.5~10,000ppm 첨가함으로써 자외선 흡수제 첨가, 광 학 수지 및 모노머 등에 의하여 렌즈가 노란색을 띠는 것을 방지할 수 있다.Additionally, the resin composition for optical lenses of the present invention may further include a color corrector for correcting the initial color of the lens. Organic dyes, organic pigments, inorganic pigments, etc. may be used as color correctors. By adding 0.1 to 50,000 ppm, preferably 0.5 to 10,000 ppm, of such organic dyes per resin composition for optical lenses, it is possible to prevent the lenses from turning yellow due to the addition of ultraviolet absorbers, optical resins, monomers, etc.
본 발명의 광학렌즈용 수지 조성물은 통상적으로 사용되는 이형제 및 중합개시제를 더 포함할 수 있다. 이형제로는, 불소계 비이온계면활성제, 실리 콘계 비이온계면활성제, 알킬제 4급 암모늄염 들 중에서 선택된 성분이 단독으로 또는 2종 이상 혼합 사용될 수 있다. 바람직하게는 인산에스테르를 사용한다. 또한, 중합개시제로는 아민계 또는 주석계 화합물 등을 단독으로 또는 2종 이상 함 께 사용될 수 있다.The resin composition for optical lenses of the present invention may further include a commonly used mold release agent and a polymerization initiator. As a release agent, components selected from fluorine-based nonionic surfactants, silicone-based nonionic surfactants, and alkyl quaternary ammonium salts may be used alone or in combination of two or more types. Preferably, phosphoric acid ester is used. Additionally, as a polymerization initiator, amine-based or tin-based compounds may be used alone or in combination of two or more.
본 발명의 이소시아네이트 화합물과 폴리티올 화합물을 중합시켜 이소시아네이트 예비중합체와 폴리티올 예비중합체로 구성된 수지 조성물을 얻은 다음, 이를 열경화시켜 광학렌즈, 특히 웨이퍼 레벨 렌즈를 얻게 된다. 본 발명의 수지 조성물을 열경화시켜 렌즈를 제조하는 과정은 다음과 같다. 우선, 본 발명의 이소시아네이트 예비중합체는 과량의 이소시아네이트 화합물에 소량의 폴리티올을 첨가하고 감압교반을 4시간동안 진행한다. 반응기 내부를 질소로 치환한 후, 70 oC까지 1시간이내에 승온하고 이후 100~110 oC까지 승온하여 2시간 이상 교반한다. 이 때 70 oC까지 승온에 있어 1시간 이상의 시간이 소요되면 용액에 백탁이 발생하게 된다. 또한, 최종온도가 낮으면 예비중합체의 반응의 완료까지 오랜 시간이 소요되어 황변이 발생하게 되며, 최종온도가 높아도 황변이 발생하게 되므로 승온 속도와 최종온도에 유의하여 제조하여야 한다. 이 후 60 oC 이하로 냉각한 후 이형제 등 첨가제를 투입한 후 용액이 맑아지면 상온으로 냉각하여 이소시아네이트 예비중합체를 얻는다. 폴리티올 예비중합체는 과량의 이소시아네이트 및 소량이 폴리티올 대신 과량의 폴리티올 및 소량의 이소시아네이트를 사용한다는 차이점을 제외하고는 이소시아네이트 예비중합체와 같은 방법으로 실시하여 폴리티올 예비중합체를 얻는다.The isocyanate compound and the polythiol compound of the present invention are polymerized to obtain a resin composition composed of an isocyanate prepolymer and a polythiol prepolymer, which is then heat-cured to obtain an optical lens, particularly a wafer level lens. The process of manufacturing a lens by heat curing the resin composition of the present invention is as follows. First, the isocyanate prepolymer of the present invention is prepared by adding a small amount of polythiol to an excess of isocyanate compound and stirring under reduced pressure for 4 hours. After replacing the inside of the reactor with nitrogen, the temperature is raised to 70 o C within 1 hour, and then the temperature is raised to 100-110 o C and stirred for more than 2 hours. At this time, if it takes more than 1 hour to raise the temperature to 70 o C, white turbidity will occur in the solution. In addition, if the final temperature is low, it takes a long time to complete the reaction of the prepolymer, causing yellowing, and even if the final temperature is high, yellowing occurs, so the temperature increase rate and final temperature must be taken into consideration when manufacturing. After cooling to 60 o C or lower, additives such as release agents are added, and when the solution becomes clear, it is cooled to room temperature to obtain an isocyanate prepolymer. The polythiol prepolymer is obtained in the same manner as the isocyanate prepolymer, with the difference that an excess of polythiol and a small amount of isocyanate are used instead of an excess of isocyanate and a small amount of polythiol.
상기의 폴리이소시아네이트 예비중합체와 폴리티올 예비중합체로 구성된 수지조성물을 배합통 내에 투입한 후 내부 온도를 20~25 ℃로 유지한 채로 감압탈포를 실시하고 몰드에 주입한다. 이때 몰드는 바람직하게는, 하부에 고정된 유리몰드나 금속제 몰드에 주입하여 몰드 주입 후 상부몰드를 내려 주입된 수지가 몰드 내 고르게 퍼지도록 사용한다. 혼합물이 주입된 몰드를 상온에서 115~125 ℃에서 30분간 가열한 후 60~80℃로 천천히 냉각시켜 몰드로부터 수지를 이형시켜 광학렌즈를 얻는다. 이렇게 얻은 광학렌즈는 추가적으로 120~140℃의 온도에서 1시간 어닐링 처리할 수 있다.The resin composition consisting of the above-described polyisocyanate prepolymer and polythiol prepolymer is placed in a mixing tank, then degassed under reduced pressure while maintaining the internal temperature at 20-25°C, and then injected into the mold. At this time, the mold is preferably injected into a glass mold or metal mold fixed at the bottom, and after mold injection, the upper mold is lowered so that the injected resin is evenly spread within the mold. The mold into which the mixture is injected is heated at room temperature at 115-125°C for 30 minutes and then slowly cooled to 60-80°C to release the resin from the mold to obtain an optical lens. The optical lens obtained in this way can be additionally annealed at a temperature of 120 to 140°C for 1 hour.
또, 상기 방법으로 얻어진 광학렌즈에, 광학특성을 높이기 위하여 하드코팅 및 멀티코팅 처리를 할 수 있다. 하드코팅층의 형성은 에폭시기, 알콕시 기, 비닐기 등의 관능기를 가지는 적어도 하나의 실란화합물과 산화규산, 산화티탄, 산화안티몬, 산화주석, 산화텅스텐, 산화알루미늄 등의 적어도 하나 이 상의 금속산화물 콜로이드를 주성분으로 하는 코팅조성물을 함침 또는 스핀코팅법으로 광학렌즈 표면에 두께 0.5~10 로 코팅한 후, 가열 또는 자외선 경화하여 코팅 막을 완성한다.In addition, the optical lens obtained by the above method can be subjected to hard coating and multi-coating treatment to improve optical properties. Formation of the hard coating layer includes at least one silane compound having a functional group such as an epoxy group, an alkoxy group, or a vinyl group, and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, and aluminum oxide. The coating composition containing the main ingredient is coated on the surface of the optical lens to a thickness of 0.5 to 10 by impregnation or spin coating, and then heated or UV cured to complete the coating film.
멀티코팅층, 즉, 반사방지코팅 층은 산화규소, 불화마그네슘, 산화 알루미늄, 산화지르코늄, 산화티탄늄, 산화탄탈, 산화이트륨 등의 금속산화물을 진 공증착 또는 스퍼터링하는 방법에 의하여 형성할 수 있다. 가장 바람직하게는 렌즈의 양면 하드코팅막 위에 산화규소와 산화지르코늄 막을 3회 이상 반복 진공증착한 후 산화규소막을 마지막으로 진공 증착한다. 또, 필요에 따라 마지막에 수막(불소 수지)층을 두거나, 산화규소와 산화지르코늄막 사이에 ITO층을 둘 수도 있다.The multi-coating layer, that is, the anti-reflective coating layer, can be formed by vacuum deposition or sputtering of metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide, and yttrium oxide. Most preferably, silicon oxide and zirconium oxide films are repeatedly vacuum-deposited three or more times on the hard coating film on both sides of the lens, and then the silicon oxide film is vacuum-deposited last. Additionally, if necessary, a water film (fluororesin) layer may be placed at the end, or an ITO layer may be placed between the silicon oxide and zirconium oxide films.
본 발명의 광학렌즈용 수지 조성물은 플라스틱 렌즈에 한정되지 않고 다양한 광학제품에 이용될 수 있다.The resin composition for optical lenses of the present invention is not limited to plastic lenses and can be used in various optical products.
본 발명에 의해 제작된 광학렌즈가 플라스틱 렌즈로서의 적합한 물성을 갖는지 평가할 필요가 있으며, 각각의 물성치인 (1) 굴절율 및 아베수(υE), (2) 내열성 (Tg), (3) 황색도, (4) 맥리 및 백탁은 다음의 시험법에 의해 평가하였다.It is necessary to evaluate whether the optical lens produced by the present invention has suitable physical properties as a plastic lens, and the respective physical properties (1) refractive index and Abbe number (υE), (2) heat resistance (Tg), (3) yellowness, (4) Strain and white turbidity were evaluated by the following test method.
(1) 굴절율(nD20, nE20) 및 아베수(υE): ATAGO사의 DR-M4 모델인 ABBE 굴절계를 사용하여 589 nm (D파장), 546 nm (E파장)의 굴절율과 546 nm에서의 아베수를 20℃에서 측정했다.(1) Refractive index (nD 20 , nE 20 ) and Abbe number (υE): Using an ABBE refractometer, DR-M4 model from ATAGO, the refractive index of 589 nm (D wavelength), 546 nm (E wavelength) and 546 nm Abbe number was measured at 20°C.
(2) 내열성: SCINCO사의 DSC N-650 열분석기를 사용하여 시험편의 유리전이온도(Tg)를 측정하여 내열성으로 했다.(2) Heat resistance: The glass transition temperature (Tg) of the test piece was measured using SCINCO's DSC N-650 heat analyzer to determine heat resistance.
(3) 황색도: SHIMADZU사의 UV-2600 분광기를 사용하여 2 mm 시험편 의 Y.I값을 측정하여 황색도를 비교하였다.(3) Yellowness: The Y.I value of a 2 mm test piece was measured using SHIMADZU's UV-2600 spectrometer to compare the yellowness.
4) 맥리 및 백탁: 렌즈 100개를 육안으로 관찰하여 맥리 및 백화 현상의 발생 정도를 10개 이상: NG, 2개 이하: OK로 표기하였다.4) Stretching and whitening: 100 lenses were observed with the naked eye, and the degree of occurrence of striae and whitening was marked as NG for 10 or more lenses and OK for 2 or less lenses.
[합성예 1 내지 10, 비교예 1 내지 3] 이소시아네이트 예비중합체 합성[Synthesis Examples 1 to 10, Comparative Examples 1 to 3] Isocyanate prepolymer synthesis
이소시아네이트 화합물과 폴리티올 화합물을 표1에 표기한 내용대로 투입한 후 5 torr 이하의 조건에 4시간 동안 감압탈포를 실시하였다. 디부틸주석디클로라이드를 이소시아네이트 화합물과 폴리티올 화합물의 총 중량 대비 0.3wt%를 투입하고 30분 이내 70 oC까지 승온한 후, 다시 100 oC 승온하여 2시간 동안 교반하였다. 이후 60 oC로 냉각한 후 Zelec-UN (Stepan 사)를 총 중량 대비 0.12%를 첨가한 후 용액이 맑아질 때까지 교반하였다. 이후 상온으로 냉각하여 5 um 카트리지 필터를 통해 용액을 필터하여 이소시아네이트 예비중합체를 얻었다. 얻어진 예비중합체는 회전형 점도계를 통해 점도를 측정하였다.After the isocyanate compound and polythiol compound were added as indicated in Table 1, reduced pressure degassing was performed for 4 hours under conditions of 5 torr or less. Dibutyltin dichloride was added in an amount of 0.3 wt% based on the total weight of the isocyanate compound and polythiol compound, and the temperature was raised to 70 o C within 30 minutes, then the temperature was raised again to 100 o C and stirred for 2 hours. After cooling to 60 o C, 0.12% of the total weight of Zelec-UN (Stepan) was added and stirred until the solution became clear. After cooling to room temperature, the solution was filtered through a 5 um cartridge filter to obtain an isocyanate prepolymer. The viscosity of the obtained prepolymer was measured using a rotational viscometer.
비교예 1 내지 3을 통하여, SH/NCO가 0.15를 초과하게 되면 점도가 높아졌으며, 탈포 및 주입 등 가공이 어려웠다. 또한 SH/NCO가 0.1 이하일 경우 점도가 낮아서 예비중합체의 유동성이 증가하여 웨이퍼레벨 렌즈 가공 시 누액 등으로 렌즈 제조에 어려움이 있음을 확인하였다. Through Comparative Examples 1 to 3, when SH/NCO exceeded 0.15, the viscosity increased, and processing such as degassing and injection was difficult. In addition, it was confirmed that when SH/NCO is less than 0.1, the viscosity is low and the fluidity of the prepolymer increases, causing difficulties in manufacturing lenses due to leakage during wafer-level lens processing.
몰비SH/NCO
molar ratio
XDI: 크실릴렌디이소시아네이트MICH: 메틸디이소시아네이트시클로헥산XDI: Xylylene diisocyanate MICH: Methyl diisocyanate Cyclohexane
MICH: 메틸디이소시아네이트시클로헥산MICH: Methyl diisocyanatecyclohexane
NBDI: 노보난디이소시아네이트NBDI: Norbonane diisocyanate
BIC: 1,3-비스(이소시아네이토메틸)시클로헥산BIC: 1,3-bis(isocyanatomethyl)cyclohexane
BET: 비스(메르캅토메틸)-3,6,9-트리티아운데칸-1,11-디티올BET: Bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol
CET: 1,4-티티안-2,5-디메탄티올CET: 1,4-Titian-2,5-dimethanethiol
[합성예 11 내지 20, 비교예 4 내지 6] 폴리티올 예비중합체 합성[Synthesis Examples 11 to 20, Comparative Examples 4 to 6] Synthesis of polythiol prepolymer
이소시아네이트 화합물과 폴리티올 화합물을 표2에 표기한 내용대로 투입한 후 5 torr 이하의 조건에 4시간 동안 감압탈포를 실시하였다. 디부틸주석디클로라이드를 이소시아네이트 화합물과 폴리티올 화합물의 총 중량 대비 0.3wt%를 투입하고 30분 이내 70 oC까지 승온한 후, 다시 100 oC 승온하여 2시간 동안 교반하였다. 이후 60 oC로 냉각한 후 Zelec-UN (Stepan 사)를 총 중량 대비 0.12%를 첨가한 후 용액이 맑아질 때까지 교반하였다. 이후 상온으로 냉각하여 5 um 카트리지 필터를 통해 용액을 필터하여 폴리티올 예비중합체를 얻었다. 얻어진 예비중합체는 회전형 점도계를 통해 점도를 측정하였다.The isocyanate compound and polythiol compound were added as shown in Table 2, and then reduced pressure degassing was performed for 4 hours under conditions of 5 torr or less. Dibutyltin dichloride was added in an amount of 0.3 wt% based on the total weight of the isocyanate compound and polythiol compound, and the temperature was raised to 70 o C within 30 minutes, then the temperature was raised again to 100 o C and stirred for 2 hours. After cooling to 60 o C, 0.12% of the total weight of Zelec-UN (Stepan) was added and stirred until the solution became clear. After cooling to room temperature, the solution was filtered through a 5 um cartridge filter to obtain a polythiol prepolymer. The viscosity of the obtained prepolymer was measured using a rotational viscometer.
비교예 4 내지 6을 통하여, SH/NCO가 8 미만이거나 10을 초과하게 되면 예비중합체의 유동성이 증가하여 너무 낮아져서 원하는 웨이퍼레벨 렌즈 가공에 어려움이 있음을 확인하였다. Through Comparative Examples 4 to 6, it was confirmed that when SH/NCO is less than 8 or more than 10, the fluidity of the prepolymer increases and becomes too low, making it difficult to process the desired wafer-level lens.
몰비SH/NCO
molar ratio
[실시예 1 내지 10, 비교예 7 내지 10] 광학 수지 제조[Examples 1 to 10, Comparative Examples 7 to 10] Optical resin production
상기 합성예 1 내지 10에서 제조된 이소시아네이트 예비중합체와 상기 합성예 11 내지 20에서 제조된 폴리티올 예비중합체를 각각 [표3]에 표기한 바와 같이, 1:1의 함량으로 이들을 투입한다. 상온에서 감압교반하면서 20분동안 탈포 작업을 진행하여 수지조성물을 제조한다. 이 후 질소로 치환한 후 하판 몰드에 수지조성물을 시린지를 이용하여 투입하고 상판몰드로 서서히 용액을 덮는다. 이후 120 ± 5 oC로 승온하여 30분간 경화한 후 80 oC로 냉각하여 탈형하여 광학 수지를 얻었다.The isocyanate prepolymer prepared in Synthesis Examples 1 to 10 and the polythiol prepolymer prepared in Synthesis Examples 11 to 20 are added in a 1:1 ratio, as shown in [Table 3]. A resin composition is prepared by performing a degassing operation for 20 minutes while stirring under reduced pressure at room temperature. After replacing with nitrogen, the resin composition is added to the lower mold using a syringe and the solution is gradually covered with the upper mold. Afterwards, the temperature was raised to 120 ± 5 o C and cured for 30 minutes, then cooled to 80 o C and demolded to obtain an optical resin.
실시예 1 내지 10의 결과에서와 같이 수지조성물의 점도가 2000 cp 내지 5000 cp의 범위에서 웨이퍼레벨 렌즈의 가공성이 우수하였다. 또한, 실시예 1 내지 5와 7 내지 10의 결과와 같이 이소시아네이트 예비조성물에서 메틸디이소시아네이트시클로헥산의 비율 30% 이상 첨가 시 유리전이온도를 통하여 130 oC 이상의 우수한 내열성을 갖는 렌즈를 확보할 수 있었다. 또한 이소시아네이트 화합물의 종류 및 비율에 따라 다양한 굴절율의 제품을 얻을 수 있었으며, 얻어진 렌즈의 아베수 및 황색도 등의 광학적 물성이 우수하였다.As shown in the results of Examples 1 to 10, the processability of the wafer level lens was excellent when the viscosity of the resin composition was in the range of 2000 cp to 5000 cp. In addition, as shown in the results of Examples 1 to 5 and 7 to 10, when more than 30% of methyl diisocyanate cyclohexane was added to the isocyanate preliminary composition, a lens with excellent heat resistance of 130 o C or more was obtained through the glass transition temperature. . In addition, products with various refractive indices could be obtained depending on the type and ratio of the isocyanate compound, and the obtained lenses had excellent optical properties such as Abbe number and yellowness.
(υE20)Abesu
(υE20)
Claims (8)
(2) 상기 디이소시아네이트 화합물의 하나로서, 하기 화학식 1:
로 표시되는 메틸디이소시아네이트시클로헥산이 상기 디이소시아네이트 화합물의 총량에서 적어도 30%이상을 포함하면서;
(3) 상기 예비중합체 액상의 점도가 2,000~5000 cp인 것을 특징으로 하는, 웨이퍼레벨 광학 렌즈용 수지조성물.An optical resin composition composed of a diisocyanate compound and a polythiol compound, (1) polythiol polymerized so that the molar ratio (NCO/SH molar ratio) of the isocyanate functional group (NCO) and the polythiol functional group (SH) is 1/8 or less. A prepolymer, including a diisocyanate prepolymer polymerized to a molar ratio of NCO/SH of 8 or more;
(2) As one of the above diisocyanate compounds, the following formula 1:
Methyl diisocyanate cyclohexane represented by contains at least 30% or more of the total amount of the diisocyanate compound;
(3) A resin composition for a wafer-level optical lens, characterized in that the viscosity of the prepolymer liquid phase is 2,000 to 5000 cp.
The optical resin composition for wafer level according to claim 1, wherein the methyl diisocyanate cyclohexane is a compound of the following formula (2) or (3):
(2) NCO/SH의 몰비가 8이상의 과량의 폴리티올에 NCO/SH의 몰비가 1/8 이하의 범위의 소량의 이소시아네이트를 첨가하고 소정의 시간과 온도에서 얻어진 용액에 백탁이 발생하기 전에 중합반응을 완료하여 폴리티올 예비중합체를 제조하는 단계; 및
(3) 상기에서 얻어진 이소시아네이트 예비중합체와 폴리티올 예비중합체를 혼합하는 단계;
를 포함하는, 제1항 내지 제5항 중 어느 한 항에 기재된 광학 수지 조성물을 이용한, 웨이퍼레벨용 광학 수지를 제조하는 방법.(1) Excess isocyanate compound in which the molar ratio of isocyanate functional group (NCO) and polythiol functional group (SH) (NCO/SH molar ratio) is 8 or more, and a small amount of NCO/SH molar ratio is 1/8 or less. Preparing an isocyanate prepolymer by adding polythiol and completing the polymerization reaction before white turbidity occurs in the solution obtained at a predetermined time and temperature;
(2) Add a small amount of isocyanate with an NCO/SH molar ratio of 1/8 or less to excess polythiol with an NCO/SH molar ratio of 8 or more, and polymerize the resulting solution at a predetermined time and temperature before white turbidity occurs. Completing the reaction to prepare a polythiol prepolymer; and
(3) mixing the isocyanate prepolymer and polythiol prepolymer obtained above;
A method of producing an optical resin for wafer level using the optical resin composition according to any one of claims 1 to 5, comprising a.
An optical resin for wafer level manufactured by the method according to claim 7.
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