KR101356387B1 - Transparent Optical Hybrid Material - Google Patents
Transparent Optical Hybrid Material Download PDFInfo
- Publication number
- KR101356387B1 KR101356387B1 KR1020110079318A KR20110079318A KR101356387B1 KR 101356387 B1 KR101356387 B1 KR 101356387B1 KR 1020110079318 A KR1020110079318 A KR 1020110079318A KR 20110079318 A KR20110079318 A KR 20110079318A KR 101356387 B1 KR101356387 B1 KR 101356387B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- resin composition
- thiol
- curable resin
- hybrid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000003287 optical effect Effects 0.000 title claims abstract description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 45
- 150000003573 thiols Chemical class 0.000 claims abstract description 35
- 239000011342 resin composition Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 18
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006596 Alder-ene reaction Methods 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 150000004703 alkoxides Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- -1 acryl group Chemical group 0.000 claims description 25
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 23
- 238000006482 condensation reaction Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 8
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000010936 titanium Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- UKSWSALBYQIBJN-UHFFFAOYSA-N dihydroxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](O)(O)CC(C)C UKSWSALBYQIBJN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- RXJXDPDHNAYULH-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-4-morpholin-4-yl-1-phenylbutan-1-one Chemical compound C=1C=CC=CC=1CC(C(=O)C=1C=CC=CC=1)(N(C)C)CCN1CCOCC1 RXJXDPDHNAYULH-UHFFFAOYSA-N 0.000 claims description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 claims description 2
- IZXRSZNHUSJWIQ-UHFFFAOYSA-N 2-methylpropan-2-ol;titanium Chemical compound [Ti].CC(C)(C)O.CC(C)(C)O.CC(C)(C)O.CC(C)(C)O IZXRSZNHUSJWIQ-UHFFFAOYSA-N 0.000 claims description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 229920000180 alkyd Chemical group 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical group CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004678 hydrides Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 125000005641 methacryl group Chemical group 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 229910052715 tantalum Chemical group 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- PKLMYPSYVKAPOX-UHFFFAOYSA-N tetra(propan-2-yloxy)germane Chemical compound CC(C)O[Ge](OC(C)C)(OC(C)C)OC(C)C PKLMYPSYVKAPOX-UHFFFAOYSA-N 0.000 claims description 2
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 claims 1
- ROYRUMBLNWJMGV-UHFFFAOYSA-N 10-trimethoxysilyldecane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCCCCCS ROYRUMBLNWJMGV-UHFFFAOYSA-N 0.000 claims 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- DUVRJGHTIVORLW-UHFFFAOYSA-N [diethoxy(methyl)silyl]methanethiol Chemical compound CCO[Si](C)(CS)OCC DUVRJGHTIVORLW-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229960005235 piperonyl butoxide Drugs 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 238000002834 transmittance Methods 0.000 abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 31
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 229910000077 silane Inorganic materials 0.000 description 13
- 238000003980 solgel method Methods 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000016 photochemical curing Methods 0.000 description 10
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 9
- 229910001863 barium hydroxide Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 239000012258 stirred mixture Substances 0.000 description 8
- 238000002207 thermal evaporation Methods 0.000 description 8
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
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- VHJRQDUWYYJDBE-UHFFFAOYSA-N 11-trimethoxysilylundecane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCS VHJRQDUWYYJDBE-UHFFFAOYSA-N 0.000 description 1
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- PBYDIWCXDGMNRO-UHFFFAOYSA-N 3-trimethoxysilylpropyl but-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=CC PBYDIWCXDGMNRO-UHFFFAOYSA-N 0.000 description 1
- HGEKXQRHZRDGKO-UHFFFAOYSA-N 3-tripropoxysilylpropyl prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C=C HGEKXQRHZRDGKO-UHFFFAOYSA-N 0.000 description 1
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- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000239366 Euphausiacea Species 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- PVLBXNICXUCXTA-UHFFFAOYSA-N [2-hydroxy-3-(3-triethoxysilylpropylamino)propyl] prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCNCC(O)COC(=O)C=C PVLBXNICXUCXTA-UHFFFAOYSA-N 0.000 description 1
- LTKACMBVEOKTGC-UHFFFAOYSA-N [2-hydroxy-3-(3-trimethoxysilylpropylamino)propyl] prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCNCC(O)COC(=O)C=C LTKACMBVEOKTGC-UHFFFAOYSA-N 0.000 description 1
- RNFUJUQPEUUTEZ-UHFFFAOYSA-N [2-hydroxy-3-(3-tripropoxysilylpropylamino)propyl] prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCNCC(O)COC(=O)C=C RNFUJUQPEUUTEZ-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Abstract
본 발명은 티올 올리고실록산 하이브리드, 비닐 올리고실록산 하이브리드 또는 비닐기를 최소 2개 이상 포함하는 유기화합물, 및 광개시제 또는 열개시제를 포함하는 경화성 수지 조성물 및 이로부터 제조된 광학용 투명 하이브리드에 관한 것이다. 이러한 수지는 자외선 조사 또는 열을 가함으로써, 비닐기를 최소 2개 이상 포함하는 유기화합물 또는 올리고실록산과 광개시제 또는 열개시제 하에 티올-엔 반응을 통해 경화되어 광소자, 광학 렌즈, 디스플레이, LED 등의 다양한 종류의 광학용 재료로 응용될 수 있다.
본 발명에 따른 티올-엔 반응을 통한 광학용 투명 하이브리드 재료는 탁월한 투광도, 내광성 및 내열성을 나타내고 광학용 응용에 적합한 굴절률과 경도를 가지며 성형 시 수축률이 적어 광소자, 광학 렌즈, 디스플레이, LED 등의 광학용 응용에 사용할 수 있는 이상적인 재료이다.
The present invention relates to a thiol oligosiloxane hybrid, a vinyl oligosiloxane hybrid or an organic compound including at least two or more vinyl groups, and a curable resin composition comprising a photoinitiator or a thermal initiator and an optically transparent hybrid prepared therefrom. Such resins are cured through thiol-ene reaction under an organic or oligosiloxane containing at least two vinyl groups and a photoinitiator or a thermal initiator by irradiation with ultraviolet rays or by heating, thereby providing a variety of optical devices, optical lenses, displays, and LEDs. It can be applied to a kind of optical material.
The optical transparent hybrid material through the thiol-ene reaction according to the present invention exhibits excellent light transmittance, light resistance and heat resistance, has refractive index and hardness suitable for optical applications, and has a low shrinkage rate during molding, such as an optical device, an optical lens, a display, and an LED. It is an ideal material for use in optical applications.
Description
본 발명은 티올 올리고실록산 하이브리드를 합성하고, 합성된 수지를 비닐기를 포함하는 유기화합물과 함께 광개시제 또는 열개시제 하에 티올-엔 반응을 통해 경화함으로써, 광소자, 렌즈, 디스플레이, LED 등에 응용될 수 있는 광학용 재료로 매우 유용하게 응용될 수 있는 광학용 투명 하이브리드 재료의 제조방법에 관한 것이다.The present invention can be applied to optical devices, lenses, displays, LEDs, and the like by synthesizing a thiol oligosiloxane hybrid and curing the synthesized resin through a thiol-ene reaction under a photoinitiator or a thermal initiator with an organic compound including a vinyl group. The present invention relates to a method for producing an optically transparent hybrid material which can be very usefully applied as an optical material.
광경화를 통한, 광학 재료의 제조는 각종 광학 렌즈, 유리를 대체하고, 디스플레이, 전기통신 시스템 및 의료/분석 장치 등의 캐스트 또는 코팅 제품에 많이 응용되고 있다. The manufacture of optical materials through photocuring replaces various optical lenses, glass, and is widely applied to cast or coated products such as displays, telecommunication systems and medical / analytical devices.
특히, 유기/무기 하이브리드는 유기 금속알콕사이드르 물과 촉매에 의해 가수분해, 축합반응을 거쳐 용액을 제조한 후 경화시키는 방법인 솔-젤법을 통해 제조되어 왔다. 미국특허 제 6,436,613호(특허문헌1) 에는 이러한 솔-젤법을 통하여 제조된 유기/무기 하이브리드를 광소자에 적용시키는 방법을 개시하고 있다. 그러나 상기 방법으로 제조된 유기/무기 하이브리드는 저온에서 경화가 충분히 일어나지 않으므로 재료 내부에 실라놀기가 남게 된다. 이러한 잔류 실라놀기는 현재 광통신에서 사용되고 있는 근적외선 영역인 1310, 1550nm의 파장을 흡수하므로 전송 손실이 크다는 문제가 있다. 또한 장시간 사용시 재료 내부의 실라놀기가 대기중의 수분을 흡착하여 소자의 성능을 저하시킬 수 있는 위험이 있다. In particular, organic / inorganic hybrids have been prepared through the sol-gel process, which is a method of preparing a solution through hydrolysis and condensation reaction with an organometallic alkoxide water and a catalyst and then curing. U.S. Patent No. 6,436,613 (Patent Document 1) discloses a method of applying an organic / inorganic hybrid produced by such a sol-gel method to an optical device. However, the organic / inorganic hybrid prepared by the above method does not sufficiently cure at low temperature, so silanol groups remain inside the material. Such residual silanol groups absorb a wavelength of 1310 and 1550 nm, which are the near infrared region currently used in optical communication, and thus have a problem in that transmission loss is large. In addition, there is a risk that the silanol groups inside the material may adsorb moisture in the air and degrade the performance of the device when used for a long time.
상기 문제점에 대한 해결방법으로 대한민국 등록특허 제 10-0614976호(특허문헌2) 에서는 비가수 솔-젤법을 통해 유기/무기 하이브리드를 제조하고 이를 개시제를 사용하여 광 또는 열경화하여 광학용 재료로 응용하는 방법을 개시하고 있다. 상기 방법은 유기/무기 하이브리드의 외부에 관능성 유기그룹으로 주로 에폭시, 아크릴 계의 유기 관능기를 갖는 올리고실록산을 사용한다. 이는 안정되며 균일한 무기 망목 구조가 솔-젤법으로 형성됨으로써, 열적으로 안정되고 광학특성이 우수한 재료를 제조할 수 있다. 그러나, 상기의 광경화를 위하여서는 산소의 접촉을 막아야 하는 추가적인 공정이 필요하다. 또한 일반적인 자유 라디칼 중합에 의한 시스템은 미경화 상태로부터 경화된 상태로 변환될 때, 밀도가 급격하게 증가하기 때문에 경화 후 수축이 야기될 수 있다. 이러한 수축은 렌즈와 같은 광학 소재의 제조에 필요한 것들과 같은 정밀 성형 작업에서 문제점을 일으킬 수 있다. 수축은 이러한 광학 소재에 잔류 응력을 생성할 수 있으며, 크랙 및 다양한 광학적 결함으로 이어질 수 있다.As a solution to the problem, Korean Patent No. 10-0614976 (Patent Document 2) manufactures an organic / inorganic hybrid through a non-aqueous sol-gel method and applies it as an optical material by light or thermal curing using an initiator. A method of doing this is disclosed. The method uses oligosiloxanes having organic functional groups, mainly epoxy and acrylic, as functional organic groups outside of organic / inorganic hybrids. Since a stable and uniform inorganic mesh structure is formed by the sol-gel method, it is possible to produce a material that is thermally stable and has excellent optical characteristics. However, the above-mentioned photocuring requires an additional process to prevent the contact of oxygen. In addition, a system by general free radical polymerization may cause shrinkage after curing because of the sharp increase in density when converted from an uncured state to a cured state. Such shrinkage can cause problems in precision molding operations such as those required for the manufacture of optical materials such as lenses. Shrinkage can create residual stresses in these optical materials and can lead to cracks and various optical defects.
본 발명자는 비가수 솔-젤법으로 합성하여 제조되는 실록산 수지에 대해 많은 연구를 거듭하여 대한민국 등록특허 제 10-0929547(특허문헌3) 및 공개특허 제 10-2010-00133689(특허문헌4)를 개시한 바가 있으며, 이를 토대로 삼아 본 발명을 완성하였다.MEANS TO SOLVE THE PROBLEM This inventor repeated many researches about the siloxane resin synthesize | combined by a non-aqueous sol-gel method, and discloses Republic of Korea Patent No. 10-0929547 (Patent Document 3) and Publication No. 10-2010-00133689 (Patent Document 4). There is one bar, and based on this, the present invention has been completed.
따라서, 본 발명은 상술한 종래 기술의 문제점을 해결하기 위하여 티올 올리고실록산 하이브리드와, 비닐 올리고실록산 하이브리드 또는 최소 2개의 비닐기를 갖는 유기화합물을 광개시제 또는 열개시제 하에 티올-엔 반응을 통해 경화시킴으로써 다양한 광학용 재료로 응용될 수 있는 광학용 투명 하이브리드 재료를 제공한다. 비가수 솔-젤법을 통해 제조된 티올 올리고실록산 하이브리드는 치밀한 무기 망목구조를 형성하고 매우 투명하며, 축합도가 매우 높은 치밀한 구조를 갖는다. 본 발명은 상기 티올 올리고실록산 하이브리드를 이용해, 티올-엔 반응을 통해 광학 재료를 제조함으로써, 광투과율, 내광성, 내열성, 굴절률, 및 기계적 강도가 우수하고 성형 시 거의 수축이 없는 우수한 광학용 투명 하이브리드 재료를 제공하는데 목적이 있다.Therefore, the present invention is to solve the above-mentioned problems of the prior art by curing a thiol oligosiloxane hybrid, a vinyl oligosiloxane hybrid or an organic compound having at least two vinyl groups through a thiol-ene reaction under a photoinitiator or a thermal initiator. Provided are an optically transparent hybrid material that can be applied as a material for the purpose. The thiol oligosiloxane hybrid prepared by the non-aqueous sol-gel method forms a dense inorganic network structure, is very transparent, and has a dense structure having a very high condensation degree. The present invention uses the thiol oligosiloxane hybrid to prepare an optical material through a thiol-ene reaction, thereby providing excellent optical transmittance, light resistance, heat resistance, refractive index, and mechanical strength, and excellent optically transparent hybrid material having almost no shrinkage during molding. The purpose is to provide.
상기 목적을 달성하기 위하여 본 발명의 일 양태는 One aspect of the present invention to achieve the above object is
(1) 티올기를 포함하는 유기알콕시실란(Ⅰ) 단독 또는 상기 유기알콕시실란(Ⅰ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조된 티올 올리고실록산 하이브리드,(1) a thiol oligosiloxane hybrid prepared by non-aqueous condensation reaction of an organoalkoxysilane (I) containing a thiol group alone or a mixture of the organoalkoxysilane (I) and a metal alkoxide with an organosilanediol,
(2) 비닐기를 포함하는 유기알콕시실란(Ⅱ) 단독 또는 상기 유기알콕시실란(Ⅱ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조되는 비닐 올리고실록산 하이브리드; 또는 비닐기를 최소 2개 이상 포함하는 유기화합물; 및(2) a vinyl oligosiloxane hybrid prepared by non-aqueous condensation reaction of an organoalkoxysilane (II) containing a vinyl group alone or a mixture of the organoalkoxysilane (II) and a metal alkoxide with an organosilanediol; Or an organic compound containing at least two vinyl groups; And
(3) 광 또는 열 개시제 를 포함하는 경화성 수지 조성물을 제공한다.(3) It provides curable resin composition containing a photo or thermal initiator.
본 발명의 또 다른 일 양태는Another aspect of the invention
(1) 티올기를 포함하는 유기알콕시실란(Ⅰ) 단독 또는 상기 유기알콕시실란(Ⅰ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조된 티올 올리고실록산 하이브리드,(1) a thiol oligosiloxane hybrid prepared by non-aqueous condensation reaction of an organoalkoxysilane (I) containing a thiol group alone or a mixture of the organoalkoxysilane (I) and a metal alkoxide with an organosilanediol,
(2) 비닐기를 포함하는 유기알콕시실란(Ⅱ) 단독 또는 상기 유기알콕시실란(Ⅱ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조되는 비닐 올리고실록산 하이브리드; 및(2) a vinyl oligosiloxane hybrid prepared by non-aqueous condensation reaction of an organoalkoxysilane (II) containing a vinyl group alone or a mixture of the organoalkoxysilane (II) and a metal alkoxide with an organosilanediol; And
(3) 광 또는 열 개시제 를 포함하는 경화성 수지 조성물을 제공한다.(3) It provides curable resin composition containing a photo or thermal initiator.
또한, 본 발명의 가장 바람직한 일 양태는In addition, the most preferred aspect of the present invention
(1) 티올기를 포함하는 유기알콕시실란(Ⅰ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조된 티올 올리고실록산 하이브리드,(1) a thiol oligosiloxane hybrid prepared by a nonaqueous condensation reaction of an organoalkoxysilane (I) containing a thiol group with a metal alkoxide and an organosilanediol;
(2) 비닐기를 포함하는 유기알콕시실란(Ⅱ)과 금속알콕사이드의 혼합물과, 유기실란디올과의 비가수 축합반응에 의해 제조되는 비닐 올리고실록산 하이브리드, 및(2) a vinyl oligosiloxane hybrid prepared by a nonaqueous condensation reaction of a mixture of an organoalkoxysilane (II) containing a vinyl group with a metal alkoxide, and an organosilanediol, and
(3) 광 또는 열 개시제 를 포함하는 경화성 수지 조성물을 제공하는 것이다.(3) It provides curable resin composition containing a light or a thermal initiator.
본 발명에 따른 광학용 투명 하이브리드 재료를 위한 티올 올리고실록산 하이브리드는 솔-젤법을 통하여 합성되며, 특히 본 발명에 따른 티올기를 포함하는 유기알콕시실란 단독 또는 티올기를 포함하는 유기알콕시실란과 금속 알콕사이드의 혼합물과, 유기실란디올의 비가수 축합반응은 하기 반응식에 도시한 바와 같이 비가수 솔-젤법으로 물의 첨가 없이 축합반응에 의해 제조된다.Thiol oligosiloxane hybrids for optically transparent hybrid materials according to the present invention are synthesized through the sol-gel method, in particular organoalkoxysilanes comprising a thiol group according to the present invention or mixtures of organoalkoxysilanes containing a thiol group and a metal alkoxide And, the non-aqueous condensation reaction of the organosilanediol is prepared by the condensation reaction without addition of water by the non-aqueous sol-gel method as shown in the following scheme.
비가수 솔-젤법과 전통적인 방식의 가수 솔-젤법의 가장 기본적인 차이점은 물의 사용여부에 있다. 가수 솔-젤법은 2종 물질간의 반응 속도의 차이에 의해 복합 산화물의 형성이 어려워 전구체의 선택에 제약이 따른다. 또한 예를 들면 고온의 열처리 공정이 필요하고, 재료 내에 존재하게 되는 미 반응 수산화기들에 의해 재료의 안정성이 떨어지는 문제점 등 물을 사용하므로 필연적으로 발생하게 되는 한계가 있다. 하지만 비가수 솔-젤법을 이용하면 복합산화물뿐만 아니라 다양한 전구체를 이용하여 티올 올리고실록산 하이브리드를 형성할 수 있고 가수 솔-젤법의 단점도 극복할 수 있다. The most basic difference between the non-single sol-gel method and the traditional method of singer sol-gel method is the use of water. Hydrophilic sol-gel method is difficult to form a complex oxide due to the difference in the reaction rate between the two materials, there is a restriction in the selection of the precursor. In addition, a high temperature heat treatment process is required, and there is a limitation that inevitably occurs because water is used, such as a problem that the stability of the material is deteriorated by unreacted hydroxyl groups present in the material. However, the non-aqueous sol-gel method can be used to form thiol oligosiloxane hybrids using various precursors as well as composite oxides, and can overcome the disadvantages of the hydrosol-gel method.
(여기서, M 은 Metal, R, R'은 각각 티올기를 포함하지 않은 유기기, R"는 티올기를 포함하는 유기기)(Wherein M is a metal, R and R 'are each an organic group not containing a thiol group, and R' 'is an organic group including a thiol group)
상기의 반응식에서 알 수 있듯이 출발 물질인 유기실란디올의 수산화기와 다른 단량체인 티올기를 포함하는 유기알콕시실란 단독 또는 티올기를 포함하는 유기알콕시실란과 금속 알콕사이드의 혼합물의 알콕시기와 비가수 축합반응을 하여 무기 망목구조를 형성하며 무기 망목구조의 주변에는 티올기를 포함하는 R"과 같은 유기기가 수식된 티올 올리고실록산 하이브리드를 형성하게 된다.As can be seen from the above reaction scheme, an inorganic alkoxy group and a non-aqueous condensation reaction of an organoalkoxysilane containing a thiol group which is a monomer different from the hydroxyl group of an organosilanediol as a starting material or a mixture of an organoalkoxysilane containing a thiol group and a metal alkoxide are carried out. It forms a network structure and forms a thiol oligosiloxane hybrid in which an organic group such as R ″ including a thiol group is modified around the inorganic network structure.
비가수 솔-젤법을 이용하여 티올 올리고실록산 하이브리드를 합성할 경우 유기 실란 모노머는 수산화기가 수식된 수산화 유기 실란과 유기 실란의 비가수 축합반응을 통하여 티올 올리고실록산 하이브리드가 형성되므로 반응 온도를 낮추고 솔-젤법을 촉진하기 위해 바람직하게는 촉매가 투입될 수 있다. 사용 가능한 촉매로는 수산화바륨, 수산화스트론튬 등과 같은 수산화 금속이 사용될 수 있다. 촉매의 투입양은 특별히 제한되지 않으며 모노머의 0.0001~10 mol%로 첨가하는 것으로 충분하다. 상기 반응은 상온에서 6~72시간 정도 교반하는 것으로 충분하며 반응속도를 촉진하고 완전한 비가수 축합반응의 진행을 위하여 0~100℃ 바람직하게는 40 내지 80℃에서 1 내지 10시간 동안 비가수 축합반응을 유도하여 무기 망목 구조를 형성할 수 있다.When the thiol oligosiloxane hybrid is synthesized using the non-aqueous sol-gel method, the organic silane monomer is formed by the non-aqueous condensation reaction of the hydroxyl group-modified organic silane with the organic silane. A catalyst may be preferably added to facilitate the gel process. As a usable catalyst, metal hydroxides such as barium hydroxide, strontium hydroxide and the like can be used. The amount of catalyst to be added is not particularly limited and it is sufficient to add 0.0001-10 mol% of the monomer. The reaction is sufficient to stir at about 6 to 72 hours at room temperature, and to promote the reaction rate and to proceed with a complete non-aqueous condensation reaction, the non-aqueous condensation reaction is performed at 0 to 100 ° C. and preferably 40 to 80 ° C. for 1 to 10 hours. It can be induced to form an inorganic mesh structure.
또한 비가수 축합반응을 통해 제조된 티올 올리고실록산 하이브리드 내에는 부산물인 알코올이 존재하게 되는데 이는 대기압 및 감압 하에서 0℃~120℃바람직하게는 -0.1MPa, 40 내지 80℃의 조건에서 10분 내지 1시간 수행하거나, 비가수 축합반응 시, 질소를 지속적으로 불어넣어서, 발생되는 알코올을 반응과 동시에 배기시킬 수도 있다.In addition, by-product alcohol is present in the thiol oligosiloxane hybrid prepared through the non-aqueous condensation reaction, which is 0 to 120 ° C. under atmospheric pressure and reduced pressure, preferably -0.1 MPa and 10 to 1 minute at 40 to 80 ° C. In a non-aqueous condensation reaction for a long time, nitrogen may be continuously blown to exhaust the generated alcohol simultaneously with the reaction.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
상기 티올기를 포함하는 유기알콕시실란은 작용기가 치환 또는 비치환된 유기사슬 및 알콕시기가 결합된 실란화합물로서 하기 화학식 3 또는 화학식3의 화합물 또는 이의 혼합물로부터 선택하여 사용할 수 있다.The organoalkoxysilane including the thiol group may be selected and used from the compound represented by the following Chemical Formula 3 or Chemical Formula 3 or a mixture thereof as a silane compound having a substituted or unsubstituted organic chain and an alkoxy group.
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[상기 화학식 3,4에서 R1은 각각, 티올기를 포함하는, C1~C20의 알킬, C3~C8의 사이클로알킬, C3~C8의 사이클로알킬로 치환된 C1~C20의 알킬, C2~C20의 알케닐, C2~C20의 알키닐, 및 C6~C20의 아릴로부터 선택되고, 상기 R1은 모두 티올기를 포함하는 1종 이상의 작용기를 가질 수 있으며; R2은 각각 직쇄 또는 분지쇄 C1~C7의 알킬이다.][In the above formula R 1 is 3,4, each comprising, a thiol group, C 1 ~ C 20 alkyl, C 3 ~ C 8 cycloalkyl, a C 1 ~ C 20 cycloalkyl substituted by a C 3 ~ C 8 Alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, and C 6 to C 20 aryl, wherein R 1 may all have one or more functional groups including thiol groups ; R 2 is straight or branched alkyl of C 1 to C 7 , respectively.]
보다 구체적으로는 머캅토메틸메틸다이에톡시실란(Mercaptomethyl methydiethoxysilane), 3-머캅토프로필메틸다이메톡시실란(3-Mercaptopropyl methyldimethoxysilane), 3-머캅토프로필트리에톡시실란(3-Mercaptopropyl triethoxysilane), 3-머캅토프로필트리메톡시실란(3-Mercaptopropyl trimethoxysialne), 및 11-머캅토운데실트리메톡시실란(11-Mercaptoundecyl trimethoxysilane) 또는 이들의 혼합물로부터 선택하여 사용할 수 있으나 반드시 이에 한정하는 것은 아니다.More specifically, mercaptomethyl methydiethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-Mercaptopropyl trimethoxysialne, and 11-Mercaptoundecyl trimethoxysilane or mixtures thereof may be selected and used, but not necessarily limited thereto.
상기 유기실란디올은 작용기가 치환 또는 비치환된 유기사슬 및 2개의 수산화기가 결합된 실란화합물로 하기 화학식 5의 화합물 또는 이의 혼합물로부터 선택하여 사용할 수 있다.The organosilanediol may be selected from a compound represented by the following Formula 5 or a mixture thereof as a silane compound in which a functional group has a substituted or unsubstituted organic chain and two hydroxyl groups bonded thereto.
[화학식 5][Chemical Formula 5]
[상기 화학식 5에서 R3및 R4는 독립적으로 C1~C20의 알킬, C3~C8의 사이클로알킬, C3~C8의 사이클로알킬로 치환된 C1~C20의 알킬, C2~C20의 알케닐, C2~C20의 알키닐, C6~C20의 아릴로부터 선택되고, 상기 R3및 R4은 아크릴기, 메타크릴기, 알릴기, 할로겐기, 아미노기, 머캡토기, 에테르기, 에스테르기, C1~C20의 알콕시기, 술폰기, 니트로기, 하이드록시기, 하이드라이드기, 사이클로부텐기, 카르보닐기, 카르복실기, 알키드기, 우레탄기, 비닐기, 니트릴기 및 에폭시기로부터 선택되는 1종 이상의 작용기를 가질 수 있으며; n은 단위체의 개수이고 단위체의 종류는 1개 이상이 될 수 있으며, n은 1이상의 정수이며, 바람직하게 n은 1내지 100000의 정수이다.][In Formula 5, R 3 and R 4 are independently C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 6 to C 20 aryl, wherein R 3 and R 4 are an acryl group, methacryl group, allyl group, halogen group, amino group, Mercapto group, ether group, ester group, C 1 -C 20 alkoxy group, sulfone group, nitro group, hydroxy group, hydride group, cyclobutene group, carbonyl group, carboxyl group, alkyd group, urethane group, vinyl group, nitrile May have one or more functional groups selected from groups and epoxy groups; n is the number of units and the number of units may be one or more, n is an integer of 1 or more, preferably n is an integer of 1 to 100000.]
구체적인 화합물로는 다이페닐실란디올, 다이아이소부틸실란디올, 실란올 터미네이티드 폴리다이메틸실록산, 실란올 터미네이티드 다이페닐실록산-다이메틸실록산 코폴리머, 실란올 터미네이티드 폴리다이페닐실록산, 실란올 터미네이티드 폴리다이페닐실록산, 및 실란올 터미네이티드 폴리트리플루오로프로필메틸실록산 또는 이의 혼합물을 예로 들 수 있으나 반드시 이에 한정하는 것은 아니다.Specific compounds include diphenylsilanediol, diisobutylsilanediol, silanol terminated polydimethylsiloxane, silanol terminated diphenylsiloxane-dimethylsiloxane copolymer, silanol terminated polydiphenylsiloxane, Silanol terminated polydiphenylsiloxanes, and silanol terminated polytrifluoropropylmethylsiloxanes or mixtures thereof are exemplified, but are not necessarily limited thereto.
상기 금속 알콕사이드는 알콕시기가 결합된 금속화합물로서 하기 화학식 4의 화합물 또는 이의 혼합물로부터 선택하여 사용할 수 있다.The metal alkoxide may be selected from a compound represented by the following formula (4) or a mixture thereof as a metal compound having an alkoxy group bonded thereto.
[화학식 6][Chemical Formula 6]
[상기 화학식 6에서 M은 금속으로부터 선택되고, n은 M의 원자가이며, 상기 R5은 직쇄 또는 분지쇄 C1~C7의 알킬이다.][In Formula 6, M is selected from a metal, n is a valence of M, and R 5 is an alkyl of straight or branched C 1 to C 7. ]
상기 화학식 6에서 n은 1 내지 5, 보다 좋게는 3 내지 5이고, M은 구체적으로 원자가 3 내지 5의 금속으로서 알루미늄, 게르마늄, 티타늄, 지르코늄, 및 탄탈럼(Tantalum)을 예로 들 수 있다. In Chemical Formula 6, n is 1 to 5, more preferably 3 to 5, and M may specifically include aluminum, germanium, titanium, zirconium, and tantalum as metals having 3 to 5 atoms.
상기 화학식 6의 구체적인 화합물로는 알루미늄에톡사이드, 탄탈럼에톡사이드, 게르마늄에톡사이드, 티타늄에톡사이드, 지르코니움에톡사이드, 지르코늄프로폭사이드, 티타늄프로폭사이드, 알루미늄아이소프로폭사이드, 게르마늄아이소프로폭사이드, 티타늄아이소프로폭사이드, 지르코늄아이소프로폭사이드, 알루미늄트리부톡사이드, 탄탈럼부톡사이드, 알루미늄 t-부톡사이드, 티타늄부톡사이드, 티타늄 t-부톡사이드, 지르코늄부톡사이드, 및 지르코늄 t-부톡사이드 또는 이의 혼합물을 예로 들 수 있으나 반드시 이에 한정하는 것은 아니다.Specific compounds of the formula 6 include aluminum ethoxide, tantalum ethoxide, germanium ethoxide, titanium ethoxide, zirconium ethoxide, zirconium propoxide, titanium propoxide, aluminum isopropoxide Side, germanium isopropoxide, titanium isopropoxide, zirconium isopropoxide, aluminum tributoxide, tantalum butoxide, aluminum t-butoxide, titanium butoxide, titanium t-butoxide, zirconium butoxide, And zirconium t-butoxide or mixtures thereof, but is not necessarily limited thereto.
본 발명에 있어서 티올기를 포함하는 유기알콕시실란과 유효량의 금속 알콕사이드의 혼합물과 유기실란디올의 비가수 축합반응을 통해 합성된 티올 올리고실록산 하이브리드에 있어서 굴절률을 높이고 높은 축합도를 위한 금속 알콕사이드의 첨가량은 상기 유기알콕시실란(Ⅰ) 100 mol에 대해 1~80 mol만큼 첨가하는 것이 바람직하며 더욱 바람직한 것은 20~70mol이다. 이 양이 너무 많으면 굴절률은 증가하지만 투과율이 저하되는 경향이 있고 양이 너무 적으면 굴절률을 증가효과가 충분치 않다.In the present invention, in the thiol oligosiloxane hybrid synthesized through the non-aqueous condensation reaction of a mixture of an organoalkoxysilane containing a thiol, an effective amount of a metal alkoxide and an organosilanediol, the addition amount of the metal alkoxide for increasing the refractive index and the degree of condensation is It is preferable to add 1-80 mol with respect to 100 mol of said organoalkoxysilanes (I), More preferably, it is 20-70 mol. If the amount is too large, the refractive index increases but the transmittance tends to decrease. If the amount is too small, the effect of increasing the refractive index is insufficient.
상기 금속 알콕사이드는 유기알콕시실란(Ⅰ)에 비하여 유기실란디올과의 반응 속도가 빨라서 보다 균질한 수지 조성물을 제조하기 위하여 금속 알콕사이드의 반응 속도를 유기알콕시실란과 유사하게 조절할 필요가 있다. 본 발명에서는 금속 알콕사이드 첨가 시 금속 알콕사이드의 반응을 조절하기 위하여 금속 킬레이트제를 더 첨가하는 것이 바람직하다. 금속 킬레이트제로는 아세틸아세톤 등의 β-디케토네이트 화합물, 또는 아크릴산, 메타크릴산 등 불포화 탄화수소기를 가지는 유기산을 사용하는 것이 바람직하다. 유기알콕시실란에 비하여 상대적으로 반응성이 큰 금속 알콕사이드를 안정화시키기 위하여, 금속 킬레이트제를 첨가하면 금속 알콕사이드의 알콕시기와 치환되어 금속 킬레이트제-금속알콕사이드 착화합물이 형성된다. 금속알콕사이드의 일부 알콕사이드기가 금속 킬레이트제로 치환되도록 첨가량을 조절하는 것이 바람직하며, 구체적으로는 금속알콕사이드의 알콕사이드에 대하여 0.2 내지 0.5 당량으로 부가하는 것이 좋다. 즉, 금속 킬레이트제를 상기 범위로 첨가하여야 반응계 내에서 적절한 반응속도로 유기실란디올과 반응하여 무기 망목 구조 내에 금속 성분이 균일하게 분산될 수 있게 된다.Since the metal alkoxide has a faster reaction rate with organoalkoxydiol than the organoalkoxysilane (I), it is necessary to control the reaction rate of the metal alkoxide similarly to the organoalkoxysilane in order to prepare a more homogeneous resin composition. In the present invention, it is preferable to further add a metal chelating agent in order to control the reaction of the metal alkoxide when the metal alkoxide is added. As the metal chelating agent, it is preferable to use β-diketonate compounds such as acetylacetone or organic acids having unsaturated hydrocarbon groups such as acrylic acid and methacrylic acid. In order to stabilize the metal alkoxide which is relatively reactive compared to the organoalkoxysilane, the addition of the metal chelating agent substitutes the alkoxy group of the metal alkoxide to form the metal chelating agent-metal alkoxide complex. It is preferable to adjust the addition amount so that some alkoxide groups of the metal alkoxide are substituted with the metal chelating agent, and specifically, it is preferable to add 0.2 to 0.5 equivalents with respect to the alkoxide of the metal alkoxide. That is, the metal chelating agent must be added in the above range to react with the organosilanediol at an appropriate reaction rate in the reaction system so that the metal component can be uniformly dispersed in the inorganic mesh structure.
본 발명에서 제조된 티올 올리고실록산 하이브리드를 함유하는 수지는 비닐 올리고실록산 하이브리드 또는 비닐기를 최소 2개 이상 포함하는 유기화합물과 자외선 조사 또는 열을 가함으로써, 광 또는 열 개시제 하에 티올-엔 반응을 통해 경화되어 광학용 응용에 사용될 수 있다. The resin containing the thiol oligosiloxane hybrid prepared in the present invention is cured through a thiol-ene reaction under a light or thermal initiator by applying UV irradiation or heat with an organic compound including at least two vinyl oligosiloxane hybrids or vinyl groups. Can be used in optical applications.
다음으로 비닐 올리고실록산 하이브리드에 대하여 설명한다.Next, the vinyl oligosiloxane hybrid will be described.
상기 비닐 올리고실록산 하이브리드는 하기 화학식 1, 2의 비닐기를 포함하는 유기알콕시실란(Ⅱ)과 유기실란디올의 축합반응을 통하여 제조된 비닐 올리고실록산 하이브리드가 사용될 수 있다.The vinyl oligosiloxane hybrid may be a vinyl oligosiloxane hybrid prepared through a condensation reaction of an organoalkoxysilane (II) containing an vinyl group of Formulas 1 and 2 with an organosilanediol.
상기 유기알콕시실란(Ⅱ)은 하기 화학식 1,2의 중 어느 하나 또는 둘의 혼합물을 포함한다.The organoalkoxysilane (II) includes any one or a mixture of two of the following Chemical Formulas 1,2.
[화학식 1][Formula 1]
[화학식 2](2)
상기 화학식 1, 2에서 R6은 각각, 모두 비닐기를 포함하는, C1~C20의 알킬, C3~C8의 사이클로알킬, C3~C8의 사이클로알킬로 치환된 C1~C20의 알킬, C2~C20의 알케닐, C2~C20의 알키닐, 및 C6~C20의 아릴로부터 선택되고, 상기 R6은 각각, 모두 비닐기를 포함하고 있는, 아크릴기, 메타크릴기, 알릴기, 및 비닐기로부터 선택되는 1종 이상의 작용기를 가질 수 있으며; R7은 직쇄 또는 분지쇄의 C1~C7의 알킬이다.The general formula (1), in 2 R 6 are each including, both a vinyl group, C 1 ~ C 20 alkyl, C 3 ~ C 8 cycloalkyl, a C 1 ~ C 20 substituted cycloalkyl of C 3 ~ C 8 Is selected from alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and C 6 -C 20 aryl, and each of R 6 includes a vinyl group, an acrylic group, meta May have one or more functional groups selected from krill, allyl, and vinyl groups; R 7 is straight or branched C 1 -C 7 alkyl.
보다 구체적으로는 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리프로폭시실란, 아릴트리메톡시실란, 아릴트리에톡시실란, N-(3-아크릴옥시-2-하이드록시프로필)-3-아미노프로필트리에톡시실란, N-(3-아크릴옥시-2-하이드록시프로필)-3-아미노프로필트리메톡시실란, N-(3-아크릴옥시-2-하이드록시프로필)-3-아미노프로필트리프로폭시실란, 3-(메트)아크릴옥시프로필트리메톡시실란, 3-(메트)아크릴옥시프로필트리에톡시실란, 3-(메트)아크릴옥시프로필트리프로폭시실란, 및 스티릴에틸트리메톡시실란에서 선택된 하나 또는 둘 이상의 혼합물을 포함하는 경화성 수지 조성물. 또는 이들의 혼합물로부터 선택하여 사용할 수 있으나 반드시 이에 한정하는 것은 아니다. More specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, aryltrimethoxysilane, aryltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3 -Aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-amino Propyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, and styrylethyl tree Curable resin composition comprising one or more mixtures selected from methoxysilane. Or a mixture thereof, but is not limited thereto.
본 발명에서 비닐 올리고실록산 하이브리드에 포함되는 유기실란디올은 앞서 언급한 화학식 5의 화학물 또는 이의 혼합물이며, 구체적인 화합물로는 다이페닐실란디올, 다이아이소부틸실란디올, 실란올 터미네이티드 폴리다이메틸실록산, 실란올 터미네이티드 다이페닐실록산-다이메틸실록산 코폴리머, 실란올 터미네이티드 폴리다이페닐실록산, 실란올 터미네이티드 폴리다이페닐실록산, 및 실란올 터미네이티드 폴리트리플루오로프로필메틸실록산 또는 이의 혼합물을 예로 들 수 있으나 반드시 이에 한정하는 것은 아니다.In the present invention, the organosilanediol included in the vinyl oligosiloxane hybrid is a chemical compound of Chemical Formula 5 or a mixture thereof, and specific compounds include diphenylsilanediol, diisobutylsilanediol, and silanol-terminated polydimethyl. Siloxane, Silanol Terminated Diphenylsiloxane-Dimethylsiloxane Copolymer, Silanol Terminated Polydiphenylsiloxane, Silanol Terminated Polydiphenylsiloxane, and Silanol Terminated Polytrifluoropropylmethylsiloxane Or a mixture thereof, but is not necessarily limited thereto.
또한 비닐 올리고실록산 하이브리드의 제조 시, 혼합할 수 있는 금속 알콕사이드는 알콕시기가 결합된 금속화합물로서 앞서 언급된 화학식 6의 화합물 또는 이의 혼합물로부터 선택하여 사용할 수 있다. 상기 금속 알콕사이드는 상기 유기알콜시실란(Ⅱ) 100 mol에 대해 1~80 mol 만큼 첨가하는 것이 바람직하며 더욱 바람직한 것은 20~70mol이다. 이 양이 너무 많으면 굴절률은 증가하지만 투과율이 저하되는 경향이 있고 양이 너무 적으면 굴절률을 증가효과가 충분치 않다.In addition, in the preparation of the vinyl oligosiloxane hybrid, the metal alkoxide that can be mixed may be selected and used from the above-described compound of formula 6 or a mixture thereof as the metal compound to which the alkoxy group is bound. The metal alkoxide is preferably added in an amount of 1 to 80 mol, more preferably 20 to 70 mol, based on 100 mol of the organoalkoxysilane (II). If the amount is too large, the refractive index increases but the transmittance tends to decrease. If the amount is too small, the effect of increasing the refractive index is insufficient.
상기 유기화합물은 비닐기를 최소 2개 이상 포함한다. 구체적인 화합물로는 비닐기를 최소 2개 이상 포함하는 1,3-부타타이엔, 1,4-펜타다이엔, 1,5-헥사다이엔, 1,6-헵타다이엔, 1,7-옥타다이엔, 1,6-헥산다이올다이아크릴레이트 또는 이의 혼합물을 예로 들 수 있으나 반드시 이에 한정하는 것은 아니다.The organic compound contains at least two vinyl groups. Specific compounds include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadie containing at least two vinyl groups. Examples include, but are not limited to, 1,6-hexanediol diacrylate or mixtures thereof.
본 발명에 따른 티올기를 포함한 올리고실록산 하이브리드는 비닐기를 포함하는 올리고실록산 하이브리드 또는 비닐기를 최소 2개 이상 포함하는 유기화합물과의 티올 반응을 통해 경화되어, 광학용 투명 하이브리드 재료로 제조되어, 탁월한 내광성, 내열성, 투광도 및 굴절률을 나타내고 광학재료에 적합한 경도를 갖는다. 티올-엔 반응은 젤화 지연으로 인하여 반응 동안 더 작은 응력을 유도할 수 있는 반응으로, 이를 하이브리드 재료의 경화에 적용시킴으로써, 재료의 성형 시 수축률이 적어 광소자, 광학 렌즈, 디스플레이, LED 등의 광학용 응용에 사용될 수 있는 이상적인 재료를 제조할 수 있다.The oligosiloxane hybrid including a thiol group according to the present invention is cured through a thiol reaction with an oligosiloxane hybrid including a vinyl group or an organic compound including at least two or more vinyl groups, and is made of an optically transparent hybrid material, thereby providing excellent light resistance, It exhibits heat resistance, light transmittance and refractive index and has a hardness suitable for optical materials. The thiol-ene reaction is a reaction that can induce smaller stresses during the reaction due to the gelation delay. The thiol-ene reaction is applied to the curing of the hybrid material, so that the shrinkage rate during the molding of the material is low. It is possible to produce ideal materials that can be used in applications.
또한 광 또는 열 개시제 하에 광 또는 열을 가해줌으로써, 티올-엔 반응을 통해 경화될 수 있는 상기 티올 및 비닐 올리고실록산 하이브리드는 티올 또는 비닐기를 갖는 모노머를 첨가하거나 다른 종류의 관능기를 갖는 모노머를 혼합하여 최종 광학용 투명 하이브리드 재료의 밀도, 자유 부피, 기판과의 접착력, 굴절률 등을 조절할 수 있다. 상기 경화는 통상적으로 사용되는 광개시제 또는 열개시제 하에서 티올-엔 반응을 통해 이루어 질 수 있다. In addition, the thiol and vinyl oligosiloxane hybrid, which may be cured through a thiol-ene reaction by applying light or heat under a photo or thermal initiator, may be added by adding a monomer having a thiol or vinyl group or by mixing a monomer having a different functional group. The density, free volume, adhesion to the substrate, refractive index and the like of the final optically transparent hybrid material can be adjusted. The curing can be done through thiol-ene reaction under commonly used photoinitiators or thermal initiators.
사용 가능한 광개시제로는 1-하이드록시-2-메틸-1-페닐프로판-1온(다로큐어(Darocure) 1173), 2-메틸-1-[4-(메틸티오페닐)-2-모폴리노프로판온](다로큐어 907), 1-하이드록시 시클로헥실 페닐 케톤(이가큐어(Irgacure) 184), 벤조인, 벤조인 메틸 에테르, 벤조인 이소프로필 에테르, 벤조인 부틸 에테르, 벤질, 벤조페논, 2-하이드록시-2-메틸 프로피오페논, 2,2-디에톡시 아세토페논, 2-클로로티오크산톤, 안트라센 또는 3,3,4,4-테트라-(t-부틸퍼옥시 카보닐)벤조페논, 2,2-디메톡시-2-페닐-아세토페논, 2-벤질-2-디메틸아미노-4-모르폴리노부티로페논(이가큐어 369)와 같은 개시제가 사용되어질 수 있으며, 열경화제로는 2,5-비스-(3급-부틸-퍼옥시)-2,5-디메틸헥산, 3급-부틸퍼옥시-2-에틸-헥사노에이트, 벤조일 퍼옥사이드, 메틸 에틸케톤 퍼옥사이드, 2,2-아조-비스-이소부틸로니트릴 또는 2,2-아조-비스-(2,4-디메틸발레로니트릴), t-부틸 페록시 벤조네이트, 1-메틸이미다졸과 같은 개시제를 사용하여 열경화시킬 수 있지만 상기 물질로 한정되는 것은 아니다.Photoinitiators that can be used include 1-hydroxy-2-methyl-1-phenylpropane-1one (Darocure 1173), 2-methyl-1- [4- (methylthiophenyl) -2-morpholino Propane] (Darocure 907), 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184), benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl, benzophenone, 2-hydroxy-2-methyl propiophenone, 2,2-diethoxy acetophenone, 2-chlorothioxanthone, anthracene or 3,3,4,4-tetra- (t-butylperoxy carbonyl) benzo Initiators such as phenone, 2,2-dimethoxy-2-phenyl-acetophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone (Igacure 369) can be used, and as a thermosetting agent Is 2,5-bis- (tert-butyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethyl-hexanoate, benzoyl peroxide, methyl ethyl ketone peroxide, 2 , 2-azo-bis-isobutylonitrile Or thermally curable using initiators such as 2,2-azo-bis- (2,4-dimethylvaleronitrile), t-butyl peroxy benzoate, 1-methylimidazole, but are not limited to these materials It is not.
또한 본 발명의 경화성 수지 조성물은In addition, the curable resin composition of the present invention
(a) 티올 올리고실록산 하이브리드 9.00~89.99 중량%(a) 9.00 to 89.99 wt% thiol oligosiloxane hybrid
(b) 비닐 올리고실록산 하이브리드 또는 비닐기를 최소 2개 이상 포함하는 유기화합물 10.00~90.00 중량%, 및(b) 10.00 to 90.00% by weight of an organic compound containing at least two vinyl oligosiloxane hybrids or vinyl groups, and
(c) 광개시제 또는 열개시제 0.01~10.00 중량% 인 것이 좋다.(c) The amount of photoinitiator or thermal initiator is preferably 0.01 to 10.00% by weight.
티올 올리고실록산 하이브리드의 투입량은 9.00~89.99 중량%인 것이 바람직하다 9 중량% 미만이면 티올기의 함량이 부족하여 미경화되며, 89.99 중량% 이상이면 비닐기의 함량이 상대적으로 부족하여 미경화된다The amount of the thiol oligosiloxane hybrid is preferably 9.00 to 89.99% by weight. If the content is less than 9% by weight, the content of the thiol group is insufficient and uncured.
상기 비닐 올리고실록산 하이브리드 또는 비닐기를 최소 2개 이상 포함하는 유기화합물의 투입량은 10.00~90.00 중량%인 것이 바람직하다 10.00 중량% 미만이면 비닐기의 함량이 부족하여 미경화되며, 90.00 중량% 이상이면 티올기의 함량이 상대적으로 부족하여 미경화된다.The amount of the vinyl oligosiloxane hybrid or the organic compound including at least two vinyl groups is preferably 10.00 to 90.00% by weight. If the amount is less than 10.00% by weight, the amount of vinyl groups is insufficient to be uncured, and at least 90.00% by weight of thiol Uncured due to the relatively low content of groups.
상기 개시제의 투입량은 특별한 한정을 요하지는 아니하며, 상기 반응물의 총량 대비 0.01∼10 중량%를 첨가하는 것이 바람직하다. 0.01 중량% 미만이면 반응이 진행되나, 효과적으로 일어나지 못하므로 성능의 구현이 어렵고, 10 중량% 를 초과하면 특성의 저하는 없지만 경제적인 측면에서 불리하다. The amount of the initiator is not particularly limited, and it is preferable to add 0.01 to 10% by weight based on the total amount of the reactants. If it is less than 0.01% by weight, the reaction proceeds, but it does not occur effectively, so it is difficult to implement performance.
본 발명에 따른 경화성 수지 조성물의 합성 시 또는 제조 후에 점도를 제어하고 수지의 안정성을 부가하기 위해 본 발명의 효과에 영향을 주지 않는 범위 내에서 용매를 더 첨가할 수 있다. 또한 이는 용액의 점도를 낮추어, 스핀 코팅, 딥 코팅 등의 박막 필름을 형성시킬 경우의 코팅성을 증가시킬 수 있다. 사용 가능한 용매로는 특별히 제한을 두지 않지만 바람직하게는 헥산, 헵탄 등의 지방족 탄화수소 용매 또는 벤젠, 톨루엔, 자일렌 등의 방향족 탄화수소 용매 또는 메틸 이소부틸 케톤, 1-메틸-2-피롤리디논, 시클로헥산온, 아세톤 등의 케톤계 용매 또는 테트라히드로퓨란, 이소프로필 에테르, 프로필렌 글리콜 프로필 에테르 등의 에테르계 용매 또는 에틸 아세테이트, 부틸 아세테이트, 프로필렌 글리콜 메틸 에테르 아세테이트 등의 아세테이트계 용매 또는 이소프로필 알코올, 부틸 알코올 등의 알코올계 용매 또는 디메틸아세트아미드, 디메틸포름아미드 등의 아미드계 용매 또는 실리콘계 용매 또는 이들의 혼합물이 사용될 수 있다.In order to control the viscosity and add stability of the resin during or after synthesis of the curable resin composition according to the present invention, a solvent may be further added within a range that does not affect the effect of the present invention. In addition, this can lower the viscosity of the solution, thereby increasing the coating property when forming a thin film, such as spin coating, dip coating. The solvent that can be used is not particularly limited but is preferably an aliphatic hydrocarbon solvent such as hexane or heptane or an aromatic hydrocarbon solvent such as benzene, toluene or xylene or methyl isobutyl ketone, 1-methyl-2-pyrrolidinone or cyclo Ketone solvents such as hexanone and acetone or ether solvents such as tetrahydrofuran, isopropyl ether and propylene glycol propyl ether or acetate solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate or isopropyl alcohol and butyl Alcohol solvents such as alcohols or amide solvents such as dimethylacetamide and dimethylformamide or silicone solvents or mixtures thereof may be used.
본 발명에 따른 티올-엔 반응 경화를 통한 광학용 투명 하이브리드 재료는 필요에 따라서 불활성 충전제, 보강성 및 비보강성 충전제, 살균제, 항료, 유동학적 첨가제, 부식억제제, 산화 억제제, 광 안정화제, 난연제, 전기적 특성에 영향을 미치는 제제, 분산제, 용매, 결합제, 안료, 염료, 가소화제, 유기 중합체, 열 안정화제, 산화물 또는 질화물의 나노입자, 방염제 및 내열제로부터 선택되는 1종 이상의 추가 첨가제를 더 포함할 수 있다. 추가 첨가제는 티올 및 비닐 올리고실록산 하이브리드의 100 중량%에 대하여 0.0001 내지 30 중량%의 비로 포함한다. 상기 추가 첨가제는 공지의 것을 사용하거나, 공지의 방법에 의해 제조하여 사용할 수 있으며, 예를 들면, 석영 가루, 규조토, 점토, 초크, 리소폰, 카본 블랙, 그라파이트, 금속 산화물, 금속 탄산염, 황산염, 카보실산의 금속염, 금속 분진, 유리섬유, 합성 섬유, 중합체 분말, 염료, 안료 등을 포함할 수 있다. Optically transparent hybrid materials through thiol-ene reaction hardening according to the present invention are inert fillers, reinforcing and non-reinforcing fillers, fungicides, paints, rheological additives, corrosion inhibitors, oxidation inhibitors, light stabilizers, flame retardants, Further comprises one or more additional additives selected from agents, dispersants, solvents, binders, pigments, dyes, plasticizers, organic polymers, heat stabilizers, nanoparticles of oxides or nitrides, flame retardants and heat resistant agents that affect electrical properties can do. Further additives comprise a ratio of 0.0001 to 30% by weight relative to 100% by weight of the thiol and vinyl oligosiloxane hybrid. The additional additives may be known or used by known methods, for example, quartz powder, diatomaceous earth, clay, chalk, lithopone, carbon black, graphite, metal oxides, metal carbonates, sulfates, Metal salts of carbolic acid, metal dust, glass fibers, synthetic fibers, polymer powders, dyes, pigments and the like.
본 발명에 따른 티올-엔 반응을 통한 광학용 투명 하이브리드 재료는 탁월한 투광도, 내광성 및 내열성을 나타내고 광학용 응용에 적합한 굴절률과 경도를 가지며, 티올-엔 반응을 통한 경화가 이루어지기 때문에, 성형 시 수축률이 적어 광소자, 광학 렌즈, 디스플레이, LED 등의 광학용 응용에 사용할 수 있는 이상적인 재료이다.The optically transparent hybrid material through the thiol-ene reaction according to the present invention exhibits excellent light transmittance, light resistance and heat resistance, has a refractive index and hardness suitable for optical applications, and is cured through the thiol-ene reaction, so that shrinkage in forming This makes it an ideal material for use in optical applications such as optical devices, optical lenses, displays, and LEDs.
본 발명을 다음의 실시예 및 비교예에 의하여 설명하고자 한다. 그러나 이들이 본 발명의 기술적 범위를 한정하는 것은 아니다. The invention is illustrated by the following examples and comparative examples. However, these do not limit the technical scope of the present invention.
<실시예 1>≪ Example 1 >
3-머캅토프로필트리메톡시실란과 다이페닐실란디올을 2:3 몰비로 하여 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 티올기와 페닐기가 수식된 투명한 티올 올리고실록산 하이브리드(Resin A)를 수득하였다.3-mercaptopropyltrimethoxysilane and diphenylsilanediol were added to a two-neck flask in a 2: 3 molar ratio, and then, as a catalyst, 0.1 mol of barium hydroxide was added to 100 mol of silane as a catalyst for 4 hours at 80 ° C. During the reaction, nitrogen gas was continuously blown to remove methanol remaining in the resin, thereby exhausting the methanol generated during the reaction. After the reaction was completed, a transparent thiol oligosiloxane hybrid (Resin A) in which a thiol group and a phenyl group were modified was obtained.
그리고 비닐트리메톡시실란(Vinyl tri-methoxysilane)과 다이페닐실란디올(Di-phenylsilane-diol)을 2:3 몰비로 하여 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 비닐기와 페닐기가 수식된 투명한 비닐 올리고실록산 하이브리드(Resin B)을 수득하였다.Then, vinyl trimethoxysilane and di-phenylsilane-diol were added in a two-neck flask in a 2: 3 molar ratio, and then barium hydroxide was used as a catalyst to 100 mol of silane. Nitrogen gas was continuously blown in order to remove methanol remaining in the resin while adding 0.1 mol and reacting at 80 ° C. for 4 hours to exhaust the methanol generated during the reaction. After the reaction was completed, a transparent vinyl oligosiloxane hybrid (Resin B) in which a vinyl group and a phenyl group were modified was obtained.
Resin A와 Resin B를 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐 아세토페논을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin E) 100mol에 대하여 0.1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Resin A and Resin B were stirred in a 1: 1 equivalent ratio, and 2,2-dimethoxy-2-phenyl acetophenone as a photoinitiator was added 0.1 mol to 100 mol of a thiol oligosiloxane hybrid (Resin E) contained in the mixture. Then, it was stirred for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<실시예 2><Example 2>
3-머캅토프로필트리메톡시실란(3-Mercaptopropyl tri-methoxysilane)과 티타늄이소프로폭사이드(Titanium iso-propoxide), 아세틸아세톤(Acetylacetone) 및 다이페닐실란디올(Di-phenylsilane-diol)을 1.2:0.8:0.8:3 몰비로 준비한다. 먼저, 상기의 몰비로 각각 3-머캅토프로필트리메톡시실란과 티타늄이소프로폭사이드를 혼합한 후, 아세틸아세톤을 넣고 20분 간 혼합하여, 충분히 킬레이팅을 한다. 그리고 다이페닐실란디올을 상기의 혼합 용액과 함께 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 티올기와 페닐기가 수식되어 있으며, 티타늄을 포함하는 투명한 티올 올리고실록산 하이브리드(Resin C)를 수득하였다.3-mercaptopropyl trimethoxysilane, titanium iso-propoxide, acetylacetone and di-phenylsilane-diol were 1.2: Prepare at 0.8: 0.8: 3 molar ratio. First, 3-mercaptopropyltrimethoxysilane and titanium isopropoxide are mixed at the above-mentioned molar ratios, and then acetylacetone is added and mixed for 20 minutes to sufficiently chelate. After diphenylsilanediol was added to the two-neck flask together with the mixed solution, methanol was added to the mol of barium hydroxide with respect to 100 mol of silane as a catalyst. The methanol remaining in the resin was reacted at 80 ° C. for 4 hours. Nitrogen gas was continuously blown in order to remove, exhausting the methanol generated during the reaction. After the reaction was completed, a thiol group and a phenyl group were modified, and a transparent thiol oligosiloxane hybrid (Resin C) containing titanium was obtained.
비닐메톡시실란(Vinylmethoxysilane)과 티타늄이소프로폭사이드(Titanium iso-propoxide), 아세틸아세톤(Acetylacetone) 및 다이페닐실란디올(Di-phenylsilane-diol)을 1.2:0.8:0.8:3 몰비로 준비한다. 먼저, 상기의 몰비로 각각 비닐메톡시실란과 티타늄이소프로폭사이드를 혼합한 후, 아세틸아세톤을 넣고 20분 간 혼합하여, 충분히 킬레이팅을 한다. 그리고 다이페닐실란디올을 상기의 혼합 용액과 함께 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 비닐기와 페닐기가 수식되어 있으며, 티타늄을 포함하는 투명한 비닐 올리고실록산 하이브리드(Resin D)를 수득하였다.Vinylmethoxysilane, titanium iso-propoxide, acetylacetone and di-phenylsilane-diol are prepared in a molar ratio of 1.2: 0.8: 0.8: 3. First, vinylmethoxysilane and titanium isopropoxide are mixed at the above molar ratios, and then acetylacetone is added and mixed for 20 minutes to sufficiently chelate. After diphenylsilanediol was added to the two-neck flask together with the mixed solution, methanol was added to the mol of barium hydroxide with respect to 100 mol of silane as a catalyst. The methanol remaining in the resin was reacted at 80 ° C. for 4 hours. Nitrogen gas was continuously blown in order to remove, exhausting the methanol generated during the reaction. After the reaction was completed, a vinyl vinyl group and a phenyl group were modified, and a transparent vinyl oligosiloxane hybrid (Resin D) including titanium was obtained.
Resin C와 Resin D을 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐 아세토페논(2, 2-dimethoxy-2-phenyl- acetophenone)을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin C) 100mol 에 대하여 1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하여 투과율 및 열안정성 측정용 시편을 제작하였다. 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Thiol oligosiloxane containing Resin C and Resin D in a 1: 1 equivalent ratio and containing 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2-phenylacetophenone) as a photoinitiator in the mixture. 1 mol was added to 100 mol of hybrid (Resin C), followed by stirring for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, a heat treatment was performed at 150 ° C. for 2 hours in a vacuum state to prepare specimens for measuring transmittance and thermal stability. In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<실시예 3><Example 3>
3-머캅토프로필트리메톡시실란(3-Mercaptopropyl tri-methoxysilane)과 지르코늄이소프로폭사이드(Zirconium iso-propoxide), 아세틸아세톤(Acetylacetone) 및 다이페닐실란디올(Di-phenylsilane-diol)을 1.2:0.8:0.8:3 몰비로 준비한다. 먼저, 상기의 몰비로 각각 3-머캅토프로필트리메톡시실란과 지르코늄이소프로폭사이드를 혼합한 후, 아세틸아세톤을 넣고 20분 간 혼합하여, 충분히 킬레이팅을 한다. 그리고 다이페닐실란디올을 상기의 혼합 용액과 함께 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 티올기와 페닐기가 수식되어 있으며, 지르코늄을 포함하는 투명한 티올 올리고실록산 하이브리드(Resin E)를 수득하였다.3-mercaptopropyl trimethoxysilane, zirconium iso-propoxide, acetylacetone and di-phenylsilane-diol were 1.2: Prepare at 0.8: 0.8: 3 molar ratio. First, 3-mercaptopropyl trimethoxysilane and zirconium isopropoxide are mixed at the above-mentioned molar ratios, and then acetylacetone is added and mixed for 20 minutes to sufficiently chelate. After diphenylsilanediol was added to the two-neck flask together with the mixed solution, methanol was added to the mol of barium hydroxide with respect to 100 mol of silane as a catalyst. The methanol remaining in the resin was reacted at 80 ° C. for 4 hours. Nitrogen gas was continuously blown in order to remove, exhausting the methanol generated during the reaction. After the reaction was completed, a thiol group and a phenyl group were modified, and a transparent thiol oligosiloxane hybrid including zirconium (Resin E) was obtained.
비닐메톡시실란(Vinylmethoxysilane)과 지르코늄이소프로폭사이드(Zirconium iso-propoxide), 아세틸아세톤(Acetylacetone) 및 다이페닐실란디올(Di-phenylsilane-diol)을 1.2:0.8:0.8:3 몰비로 준비한다. 먼저, 상기의 몰비로 각각 비닐메톡시실란과 지르코늄이소프로폭사이드를 혼합한 후, 아세틸아세톤을 넣고 20분 간 혼합하여, 충분히 킬레이팅을 한다. 그리고 다이페닐실란디올을 상기의 혼합 용액과 함께 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 비닐기와 페닐기가 수식되어 있으며, 지르코늄을 포함하는 투명한 비닐 올리고실록산 하이브리드(Resin F)를 수득하였다.Vinylmethoxysilane, zirconium iso-propoxide, Acetylacetone and Di-phenylsilane-diol are prepared in a molar ratio of 1.2: 0.8: 0.8: 3. First, vinylmethoxysilane and zirconium isopropoxide are mixed at the above molar ratios, and then acetylacetone is added and mixed for 20 minutes to sufficiently chelate. After diphenylsilanediol was added to the two-neck flask together with the mixed solution, methanol was added to the mol of barium hydroxide with respect to 100 mol of silane as a catalyst. The methanol remaining in the resin was reacted at 80 ° C. for 4 hours. Nitrogen gas was continuously blown in order to remove, exhausting the methanol generated during the reaction. After the reaction was completed, a vinyl vinyl group and a phenyl group were modified, and a transparent vinyl oligosiloxane hybrid (Resin F) including zirconium was obtained.
Resin E와 Resin F을 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐 아세토페논(2, 2-dimethoxy-2-phenyl- acetophenone)을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin E) 100mol 에 대하여 1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하여 투과율 및 열안정성 측정용 시편을 제작하였다. 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Thiol oligosiloxane containing 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2-phenyl-acetophenone) as a photoinitiator in a 1: 1 equivalent ratio and Resin E and Resin F were stirred. 1 mol was added to 100 mol of hybrid (Resin E), followed by stirring for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, a heat treatment was performed at 150 ° C. for 2 hours in a vacuum state to prepare specimens for measuring transmittance and thermal stability. In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<실시예 4><Example 4>
Resin A와 1,7-옥타다이엔을 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐아세토페논을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin A) 100mol에 대하여 0.1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Resin A and 1,7-octadiene were stirred in a 1: 1 equivalent ratio and 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator was added to 100 mol of a thiol oligosiloxane hybrid (Resin A) in the mixture. 0.1 mol was added and then stirred for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<실시예 5><Example 5>
Resin C와 1,7-옥타다이엔을 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐아세토페논을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin C) 100mol에 대하여 0.1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Resin C and 1,7-octadiene were stirred in a 1: 1 equivalent ratio and 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator was added to 100 mol of a thiol oligosiloxane hybrid (Resin C) in the mixture. 0.1 mol was added and then stirred for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<실시예 6><Example 6>
Resin E와 1,7-옥타다이엔을 1:1당량비로 교반하였고 광개시제로 2,2-다이메톡시-2-페닐아세토페논을 상기 혼합물 중 함유된 티올 올리고실록산 하이브리드(Resin E) 100mol에 대하여 0.1mol을 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.Resin E and 1,7-octadiene were stirred in a 1: 1 equivalent ratio and 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator was added to 100 mol of a thiol oligosiloxane hybrid (Resin E) in the mixture. 0.1 mol was added and then stirred for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<비교예 1>≪ Comparative Example 1 &
3-메타크릴록시트리메톡시실란(Methacryloxypropyl-tri-methoxysilane)과 다이페닐실란디올을 2:3 몰비로 하여 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 메타크릴레이트기와 페닐기가 수식된 투명한 메타크릴레이트 올리고실록산(Resin E)을 수득하였다. 광개시제로 2,2-다이메톡시-2-페닐아세토페논을 상기 메타크릴레이트 올리고실록산(Resin E) 당량 대비 1mol%를 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.3-Methylacryloxypropyl-tri-methoxysilane and diphenylsilanediol were added to a two-neck flask in a 2: 3 molar ratio, and then, as a catalyst, 0.1 mol of barium hydroxide was added to 100 mol of silane. Nitrogen gas was continuously blown in order to remove methanol remaining in the resin while adding and reacting at 80 ° C. for 4 hours to exhaust the methanol generated during the reaction. After the reaction was completed, a transparent methacrylate oligosiloxane (Resin E) in which the methacrylate group and the phenyl group were modified was obtained. 2,2-dimethoxy-2-phenylacetophenone was added as a photoinitiator to 1 mol% of the methacrylate oligosiloxane (Resin E) equivalents, followed by stirring for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
<비교예 2>Comparative Example 2
2-(3,4-에폭시시클로헥실)에틸트리메톡시실란(ECTMS; 2-(3,4-Epoxycyclohexyl)ethyl-tri-methoxysilane)과 다이페닐실란디올을 1:1 몰비로 하여 100ml 플라스크(two neck flask)에 넣은 후 촉매로 수산화바륨을 실란 100mol에 대하여 0.1mol을 첨가하여 80℃에서 4시간 동안 반응시키면서 수지 내에 잔존하는 메탄올을 제거하기 위해 질소 가스를 지속적으로 불어넣어주어, 반응 시 발생된 메탄올을 배기시켰다. 반응이 완료된 후 지환식 에폭시기와 페닐기가 수식된 투명한 지환식 에폭시 올리고실록산(Resin H)을 수득하였다. 광개시제로 아릴 설포니움 헥사플로로안티모니움 솔트를 상기 지환식 에폭시 올리고실록산(Resin H)의 4 중량%를 첨가한 후, 3시간 동안 교반했다. 이러한 혼합물을 유리로 만들어진 1mm 두께를 지닌 형틀에 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하였다. 그리고 150℃, 진공 상태에서 2시간 동안 열처리를 진행하였다 (투과율 및 열안정성 측정용 샘플). 또한, 교반된 혼합물을 PGMEA(propylene glycol monomethyl ether acetate)과 중량비로 1:1로 희석한 후, ITO(Indium Thin Oxide)가 증착된 유리 기판에 스핀 코팅을 이용해 막질을 형성한 뒤, 제작된 시료를 넣어 3분간 UV(365nm) 광을 일반 대기 상태에서 조사하여 광경화하였다. 상기 광경화 후 150℃, 진공상태에서 2시간 동안 열처리를 실시하였다. 형성된 막질 위에 열증착법과 쉐도우 마스트를 사용해 금전극을 35nm 증착하여 유전상수 및 누설 전류 측정용 시편을 제작하였다.100 ml flask containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS; 2- (3,4-Epoxycyclohexyl) ethyl-tri-methoxysilane) and diphenylsilanediol in a 1: 1 molar ratio (two neck flask) and added 0.1 mol of barium hydroxide to 100 mol of silane as a catalyst and continuously blow nitrogen gas to remove methanol remaining in the resin while reacting for 4 hours at 80 ° C. Methanol was evacuated. After the reaction was completed, a transparent alicyclic epoxy oligosiloxane (Resin H) obtained by modifying an alicyclic epoxy group and a phenyl group was obtained. As photoinitiator, aryl sulfonium hexafluoro antimony salt was added to 4 wt% of the alicyclic epoxy oligosiloxane (Resin H), followed by stirring for 3 hours. The mixture was placed in a 1 mm thick mold made of glass and irradiated with UV (365 nm) light under normal atmosphere for 3 minutes. Then, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state (a sample for measuring transmittance and thermal stability). In addition, the stirred mixture was diluted 1: 1 with PGMEA (propylene glycol monomethyl ether acetate) in a weight ratio, and then a film was formed by spin coating on a glass substrate on which ITO (Indium Thin Oxide) was deposited. 3 minutes was irradiated with UV (365 nm) light in a general atmospheric condition and photocured. After photocuring, heat treatment was performed at 150 ° C. for 2 hours in a vacuum state. 35 nm of gold electrodes were deposited on the formed film using thermal deposition and a shadow mast to prepare specimens for measuring dielectric constant and leakage current.
상기 실시예 및 비교예에서 얻어진 시편의 물성을 아래와 같은 방법으로 평가하여 그 결과를 표 1 내지 표 4에 나타내었다. The physical properties of the specimens obtained in Examples and Comparative Examples were evaluated by the following method, and the results are shown in Tables 1 to 4.
[축합도][Condensation degree]
Bruker사의 핵자기공명 분광기를 사용하여 측정하였고 측정된 데이터로부터 다음 식을 이용해 축합도를 계산하였다. It was measured using a Bruker nuclear magnetic resonance spectrometer, and from the measured data, the degree of condensation was calculated using the following equation.
D0, D1, D2, T0, T1, T2, 및 T3 는 다음 그림에서 나타낸 것과 같다.D 0 , D 1 , D 2 , T 0 , T 1 , T 2 , and T 3 are shown in the following figure.
여기서 R'는 유기 관능기이고 R은 페닐기이다. D종은 솔-젤 반응을 통해 실록산 결합 (≡Si-O-Si≡)을 형성할 수 있는 관능기가 2가지인 경우를 뜻하며, D1는 그 중 한 개가, D2는 두 개 모두 결합을 형성하였을 때를 의미한다. D0는 실록산 결합이 이루어지지 않은 상태를 뜻한다. 마찬가지로, T종은 반응 관능기가 3가지임을 뜻하며, T0는 실록산 결합이 이루어지지 않은 상태를 나타내며, T1, T2, T3는 각각 실록산 결합이 한 개, 두 개, 세 개가 형성되었을 때를 의미한다.R 'is an organic functional group and R is a phenyl group. Type D means two functional groups capable of forming siloxane bonds (≡Si-O-Si≡) through sol-gel reaction, where D 1 is one of them and D 2 is both It means when formed. D 0 means no siloxane bond. Similarly, T species means three reactive functional groups, T 0 indicates no siloxane bond, and T 1 , T 2 , and T 3 each represent one, two, or three siloxane bonds. Means.
[투과율][Transmittance]
Shimadzu Corporation의 UV/Vis/NIR 스펙트럼 분석기 UV-3101PC를 사용하여 450nm 파장에서 측정하였다.Measurements were made at 450 nm wavelength using a UV / Vis / NIR spectrum analyzer UV-3101PC from Shimadzu Corporation.
[굴절률][Refractive index]
633nm 파장에서 프리즘 커플러(Prism coupler)를 이용해 측정하였다.Measurement was performed using a prism coupler at a wavelength of 633 nm.
[유전상수][Genetic constant]
HP 사의 HP4194A를 사용하여 얻은 커패시턴스-프리퀀시(C-f) 곡선을 이용해 1MHz에서의 유전율을 측정하였다.The permittivity at 1 MHz was measured using a capacitance-frequency (C-f) curve obtained using HP4194A from HP.
[누설전류][Leakage current]
Keithley 사의 keithley237을 사용하여 얻은 전류-전압(I-V)곡선을 이용해 1MV/cm에서의 누설전류를 측정하였다.The leakage current at 1 MV / cm was measured using the current-voltage (I-V) curve obtained using Keithley 237 from Keithley.
[열안정성][Thermal stability]
TA instrument 사의 TGA(thermogravimatric analysis)를 사용하여 측정하고, 상온에서 800℃까지 질소 분위기 하에서 가열하였을 때, 샘플의 중량이 5% 감소되는 시점의 온도를 나타낸다.Measured using a TGA (thermogravimatric analysis) of TA instrument, and shows the temperature at which the weight of the sample is reduced by 5% when heated from room temperature to 800 ℃ in a nitrogen atmosphere.
<표 1> 유기 올리고실록산(Resin)의 축합도.TABLE 1 Condensation degree of organic oligosiloxane (Resin).
<표 2> 광학용 투명 하이브리드 재료의 굴절률 및 투과율Table 2 Refractive and Transmittance of Optically Transparent Hybrid Materials
<표 3> 광학용 투명 하이브리드 재료의 열안정성Table 3 Thermal Stability of Transparent Hybrid Materials for Optics
<표 4> 광학용 투명 하이브리드 재료의 유전상수와 누설 전류Table 4 Dielectric Constant and Leakage Current of Optically Transparent Hybrid Materials
표 1은 합성된 유기 올리고실록산의 축합도를 나타내고 있고, 표 2는 실시예 및 비교예에서 제조된 샘플에 굴절률과 투과율을 나타내고 있으며, 표 3은 실시예 및 비교예에서 제조된 샘플을 질소 분위기 하에서 상온에서 800℃까지 5℃/min의 승온 속도로 가열하였을 때, 샘플의 중량이 5% 감소되는 시점의 온도를 나타낸다. Table 1 shows the degree of condensation of the synthesized organic oligosiloxane, Table 2 shows the refractive index and transmittance in the samples prepared in Examples and Comparative Examples, Table 3 is a nitrogen atmosphere for the samples prepared in Examples and Comparative Examples When heated from room temperature to 800 ° C. at a rate of 5 ° C./min, the temperature at which the weight of the sample is reduced by 5% is shown.
그리고 표 4는 실시예 및 비교예에서 제조된 샘플의 유전상수와 누설 전류를 나타낸다. 티올-엔 반응을 통해 형성된 광학용 투명 하이브리드 재료의 유전상수는 일반적인 자유 라디칼 또는 양이온 중합에 의한 재료들에 비하여, 약 1정도 높은 값을 갖는 것을 알 수 있다. 또한 비교예 1~6이 비교예1~2보다 누설전류 특성이 현저하게 개선되었음을 보였다.And Table 4 shows the dielectric constant and leakage current of the samples prepared in Examples and Comparative Examples. It can be seen that the dielectric constant of the optically transparent hybrid material formed through the thiol-ene reaction has a value about 1 higher than that of general free radical or cationic polymerization materials. In addition, Comparative Examples 1 to 6 showed that the leakage current characteristics were significantly improved than Comparative Examples 1 to 2.
따라서 상기 실시예의 결과로부터 본 발명에 따른 티올-엔 반응 경화를 통한 광학용 투명 하이브리드 재료는 우수한 내광성 및 내열성뿐만 아니라 광학용 응용에 적합한 투광도, 굴절률, 유전상수, 및 누설전류 특성을 갖기 때문에 광소자, 광학용 렌즈, 디스플레이, LED 등의 다양한 광학용 응용으로 사용될 수 있다.Therefore, the optical transparent hybrid material through the thiol-ene reaction hardening according to the present invention from the results of the above embodiment has not only excellent light resistance and heat resistance but also light transmittance, refractive index, dielectric constant, and leakage current characteristics suitable for optical applications. It can be used in various optical applications such as optical lenses, displays, LEDs, and the like.
Claims (20)
(2) 비닐기를 최소 2개 이상 포함하는 유기화합물 및
(3) 광 또는 열 개시제
를 포함하며, 상기 비닐기를 최소 2개 이상 포함하는 유기화합물은 1,3-부타다이엔, 1,4-펜타다이엔, 1,5-헥사다이엔, 1,6-헵타다이엔, 1,7-옥타다이엔 및 1,6-헥산다이올다이아크릴레이트로에서 선택된 하나 또는 둘 이상의 혼합물인 경화성 수지 조성물. (1) a thiol oligosiloxane hybrid prepared by non-aqueous condensation reaction of an organoalkoxysilane (I) containing a thiol group alone or a mixture of the organoalkoxysilane (I) and a metal alkoxide with an organosilanediol,
(2) an organic compound containing at least two vinyl groups and
(3) photo or thermal initiators
Including, wherein the organic compound containing at least two or more vinyl groups are 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1, Curable resin composition which is one or two or more mixtures selected from 7-octadiene and 1,6-hexanedioldiacrylate.
상기 유기알콕시실란(Ⅰ)은 하기 화학식 3과 화학식 4의 화합물 또는 이의 혼합물로부터 선택되는 경화성 수지 조성물.
[화학식 3]
[화학식 4]
[상기 화학식 3,4에서 R1은 각각, 티올기를 포함하는, C1~C20의 알킬, C3~C8의 사이클로알킬, C3~C8의 사이클로알킬로 치환된 C1~C20의 알킬, C2~C20의 알케닐, C2~C20의 알키닐, 및 C6~C20의 아릴로부터 선택되고, 상기 R1은 모두 티올기를 포함하는 1종 이상의 작용기를 가질 수 있으며; R2은 각각 직쇄 또는 분지쇄 C1~C7의 알킬이다.]The method of claim 1,
The organoalkoxysilane (I) is a curable resin composition selected from compounds of the following Chemical Formulas 3 and 4 or mixtures thereof.
(3)
[Chemical Formula 4]
[In the above formula R 1 is 3,4, each comprising, a thiol group, C 1 ~ C 20 alkyl, C 3 ~ C 8 cycloalkyl, a C 1 ~ C 20 cycloalkyl substituted by a C 3 ~ C 8 Alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, and C 6 to C 20 aryl, wherein R 1 may all have one or more functional groups including thiol groups ; R 2 is straight or branched alkyl of C 1 to C 7 , respectively.]
상기 유기알콕시실란(Ⅰ)은 머캅토메틸메틸다이에톡시실란, 3-머캅토프로필메틸다이메톡시실란, 3-머캅토프로필트리에톡시실란, 3-머캅토프로필트리메톡시실란 및 11-머캅토운데실트리메톡시실란에서 선택된 하나 또는 둘 이상의 혼합물을 포함하는 경화성 수지 조성물.5. The method of claim 4,
The organoalkoxysilane (I) includes mercaptomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 11- Curable resin composition containing one or two or more mixtures selected from mercaptodecyl trimethoxysilane.
상기 유기실란디올은 하기 화학식 5의 화합물 또는 이를 포함하는 혼합물로부터 선택되는 경화성 수지 조성물.
[화학식 5]
[상기 화학식 5에서 R3및 R4는 독립적으로 C1~C20의 알킬, C3~C8의 사이클로알킬, C3~C8의 사이클로알킬로 치환된 C1~C20의 알킬, C2~C20의 알케닐, C2~C20의 알키닐, C6~C20의 아릴로부터 선택되고, 상기 R3및 R4은 아크릴기, 메타크릴기, 알릴기, 할로겐기, 아미노기, 머캡토기, 에테르기, 에스테르기, C1~C20의 알콕시기, 술폰기, 니트로기, 하이드록시기, 하이드라이드기, 사이클로부텐기, 카르보닐기, 카르복실기, 알키드기, 우레탄기, 비닐기, 니트릴기 및 에폭시기로부터 선택되는 1종 이상의 작용기를 가질 수 있으며, n은 1내지 100000의 정수이다.]The method of claim 1,
The organosilanediol is curable resin composition selected from the compound of Formula 5 or a mixture comprising the same.
[Chemical Formula 5]
[In Formula 5, R 3 and R 4 are independently C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 6 to C 20 aryl, wherein R 3 and R 4 are an acryl group, methacryl group, allyl group, halogen group, amino group, Mercapto group, ether group, ester group, C 1 -C 20 alkoxy group, sulfone group, nitro group, hydroxy group, hydride group, cyclobutene group, carbonyl group, carboxyl group, alkyd group, urethane group, vinyl group, nitrile And at least one functional group selected from a group and an epoxy group, n is an integer from 1 to 100000.]
상기 유기 실란디올은 다이페닐실란디올, 다이아이소부틸실란디올, 실란올 터미네이티드 폴리다이메틸실록산, 실란올 터미네이티드 다이페닐실록산-다이메틸실록산 코폴리머, 실란올 터미네이티드 폴리다이페닐실록산, 실란올 터미네이티드 폴리다이페닐실록산, 및 실란올 터미네이티드 폴리트리플루오로프로필메틸실록산에서 선택된 하나 또는 둘 이상의 혼합물을 포함하는 경화성 수지 조성물. The method according to claim 6,
The organosilanediol is diphenylsilanediol, diisobutylsilanediol, silanol terminated polydimethylsiloxane, silanol terminated diphenylsiloxane-dimethylsiloxane copolymer, silanol terminated polydiphenylsiloxane Curable resin composition comprising one or more mixtures selected from silanol terminated polydiphenylsiloxane, and silanol terminated polytrifluoropropylmethylsiloxane.
상기 금속 알콕사이드는 하기 화학식 6의 화합물 또는 이의 혼합물로부터 선택되는 경화성 수지 조성물.
[화학식 6]
상기 화학식 6에서 M은 알루미늄, 게르마늄, 티타늄, 지르코늄 및 탄탈럼으로부터 선택되고 n은 M의 원자가이며, 상기 R5은 직쇄 또는 분지쇄의 C1~C7의 알킬이다. The method of claim 1,
The metal alkoxide is curable resin composition selected from the compound of Formula 6 or a mixture thereof.
[Chemical Formula 6]
In Formula 6, M is selected from aluminum, germanium, titanium, zirconium, and tantalum, n is the valence of M, and R 5 is linear or branched C 1 -C 7 alkyl.
상기 금속알콕사이드는 알루미늄에톡사이드, 탄탈럼에톡사이드, 게르마늄에톡사이드, 티타늄에톡사이드, 지르코니움에톡사이드, 지르코늄프로폭사이드, 티타늄프로폭사이드, 알루미늄아이소프로폭사이드, 게르마늄아이소프로폭사이드, 티타늄아이소프로폭사이드, 지르코늄아이소프로폭사이드, 알루미늄트리부톡사이드, 탄탈럼부톡사이드, 알루미늄 t-부톡사이드, 티타늄부톡사이드, 티타늄 t-부톡사이드, 지르코늄부톡사이드, 및 지르코늄 t-부톡사이드에서 선택된 하나 또는 둘 이상의 혼합물을 포함하는 경화성 수지 조성물. The method of claim 8,
The metal alkoxide is aluminum ethoxide, tantalum ethoxide, germanium ethoxide, titanium ethoxide, zirconium ethoxide, zirconium propoxide, titanium propoxide, aluminum isopropoxide, germanium iso Propoxide, titanium isopropoxide, zirconium isopropoxide, aluminum tributoxide, tantalum butoxide, aluminum t-butoxide, titanium butoxide, titanium t-butoxide, zirconium butoxide, and zirconium t- Curable resin composition comprising one or more mixtures selected from butoxide.
상기 금속 알콕사이드는 상기 유기알콕시실란(Ⅰ) 100 mol에 대해 1~80 mol 사용되는 경화성 수지 조성물.The method of claim 1,
The said metal alkoxide is curable resin composition used 1-80 mol with respect to 100 mol of said organoalkoxysilanes (I).
상기 유기알콕시실란(Ⅰ)과 금속 알콕사이드의 혼합물은 금속 킬레이트제를 더 함유하는 경화성 수지 조성물.The method of claim 1,
Curable resin composition in which the mixture of the said organoalkoxysilane (I) and a metal alkoxide further contains a metal chelating agent.
상기 금속 킬레이트제는 금속 알콕사이드의 알콕사이드에 대하여 0.2 내지 0.5 당량으로 함유되는 경화성 수지 조성물.12. The method of claim 11,
Curable resin composition containing the said metal chelating agent in 0.2-0.5 equivalent with respect to the alkoxide of a metal alkoxide.
상기 금속 킬레이트제는 β-디케토네이트 화합물 또는 불포화 탄화수소기를 가지는 유기산으로부터 선택되는 경화성 수지 조성물.12. The method of claim 11,
The said metal chelating agent is curable resin composition chosen from the organic acid which has a (beta) -diketonate compound or an unsaturated hydrocarbon group.
상기 비가수 축합반응은 수산화금속 촉매 하에 이루어지는 것을 포함하는 경화성 수지 조성물.The method of claim 1,
Curable resin composition comprising the non-aqueous condensation reaction is carried out under a metal hydroxide catalyst.
상기 광 또는 열 개시제는 광개시제로 1-하이드록시-2-메틸-1-페닐프로판-1온(다로큐어(Darocure) 1173), 2-메틸-1-[4-(메틸티오페닐)-2-모폴리노프로판온](다로큐어 907), 1-하이드록시 시클로헥실 페닐 케톤(이가큐어(Irgacure) 184), 벤조인, 벤조인 메틸 에테르, 벤조인 이소프로필 에테르, 벤조인 부틸 에테르, 벤질, 벤조페논, 2-하이드록시-2-메틸 프로피오페논, 2,2-디에톡시 아세토페논, 2-클로로티오크산톤, 안트라센 또는 3,3,4,4-테트라-(t-부틸퍼옥시 카보닐)벤조페논, 2,2-디메톡시-2-페닐-아세토페논, 및 2-벤질-2-디메틸아미노-4-모르폴리노부티로페논(이가큐어 369)로부터 선택된 하나 또는 둘 이상의 혼합물이며, 열경화제로는 2,5-비스-(3급-부틸-퍼옥시)-2,5-디메틸헥산, 3급-부틸퍼옥시-2-에틸-헥사노에이트, 벤조일 퍼옥사이드, 메틸 에틸케톤 퍼옥사이드, 2,2-아조-비스-이소부틸로니트릴 또는 2,2-아조-비스-(2,4-디메틸발레로니트릴), t-부틸 페록시 벤조네이트, 및 1-메틸이미다졸에서 선택된 하나 또는 둘 이상의 혼합물을 포함하는 경화성 수지 조성물. The method of claim 1,
The photo or thermal initiator is a photoinitiator 1-hydroxy-2-methyl-1-phenylpropane-1one (Darocure 1173), 2-methyl-1- [4- (methylthiophenyl) -2- Morpholinopropanone] (Darocure 907), 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184), benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl, Benzophenone, 2-hydroxy-2-methyl propiophenone, 2,2-diethoxy acetophenone, 2-chlorothioxanthone, anthracene or 3,3,4,4-tetra- (t-butylperoxy carbo One) or a mixture of two or more selected from benzophenone, 2,2-dimethoxy-2-phenyl-acetophenone, and 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone (Igacure 369) As the thermosetting agent, 2,5-bis- (tert-butyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethyl-hexanoate, benzoyl peroxide, methyl ethyl ketone Peroxide, 2,2-azo- One or more mixtures selected from sus-isobutylonitrile or 2,2-azo-bis- (2,4-dimethylvaleronitrile), t-butyl peroxy benzoate, and 1-methylimidazole Curable resin composition.
(a) 티올 올리고실록산 하이브리드 9.00~89.99 중량%
(b) 비닐기를 최소 2개 이상 포함하는 유기화합물 10.00~90.00 중량%, 및
(c) 광개시제 또는 열개시제 0.01~10.00 중량%
인 경화성 수지 조성물. The method of claim 1, wherein the curable resin composition
(a) 9.00 to 89.99 wt% thiol oligosiloxane hybrid
(b) 10.00 to 90.00 weight percent of an organic compound containing at least two vinyl groups, and
(c) 0.01-10.00 wt% of photoinitiator or thermal initiator
Phosphorus curable resin composition.
상기 경화성 수지 조성물은 불활성 충전제, 보강성 및 비보강성 충전제, 살균제, 항료, 유동학적 첨가제, 부식억제제, 산화 억제제, 광 안정화제, 난연제, 전기적 특성에 영향을 미치는 제제, 분산제, 용매, 결합제, 안료, 염료, 가소화제, 유기 중합체, 열 안정화제, 산화물 또는 질화물의 나노입자, 방염제 및 내열제로부터 선택되는 하나 또는 둘 이상의 첨가제를 티올 올리고실록산 하이브리드 100 중량부에 대하여 0.0001 ~ 30 중량부를 함유하는 경화성 수지 조성물.The method of claim 1,
The curable resin compositions include inert fillers, reinforcing and non-reinforcing fillers, fungicides, paints, rheological additives, corrosion inhibitors, oxidation inhibitors, light stabilizers, flame retardants, agents affecting electrical properties, dispersants, solvents, binders, pigments. Curable containing 0.0001 to 30 parts by weight of one or two or more additives selected from dyes, plasticizers, organic polymers, heat stabilizers, nanoparticles of oxides or nitrides, flame retardants and heat resistant agents based on 100 parts by weight of a thiol oligosiloxane hybrid Resin composition.
상기 광학용 투명 하이브리드를 광학재료로 하는 광학소자.20. The method of claim 19,
An optical element comprising the optical transparent hybrid as an optical material.
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