WO2016068415A1 - Photocurable composition, organic protective layer comprising same, and device comprising same - Google Patents
Photocurable composition, organic protective layer comprising same, and device comprising same Download PDFInfo
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- WO2016068415A1 WO2016068415A1 PCT/KR2015/003617 KR2015003617W WO2016068415A1 WO 2016068415 A1 WO2016068415 A1 WO 2016068415A1 KR 2015003617 W KR2015003617 W KR 2015003617W WO 2016068415 A1 WO2016068415 A1 WO 2016068415A1
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- acrylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000011241 protective layer Substances 0.000 title claims description 93
- 239000000178 monomer Substances 0.000 claims abstract description 94
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 125
- -1 2-phenyl 2- (phenylthio) ethyl group Chemical group 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 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 8
- 239000008393 encapsulating agent Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005577 anthracene group Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001616 biphenylenes Chemical group 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000002987 phenanthrenes Chemical group 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 229910001512 metal fluoride Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 150000003918 triazines Chemical class 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229910052755 nonmetal Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002843 nonmetals Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RHOOUTWPJJQGSK-UHFFFAOYSA-N 2-phenylsulfanylethyl prop-2-enoate Chemical group C=CC(=O)OCCSC1=CC=CC=C1 RHOOUTWPJJQGSK-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KQMPMWGWJLNKPC-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C KQMPMWGWJLNKPC-UHFFFAOYSA-N 0.000 description 2
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 2
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 2
- ZIFLDVXQTMSDJE-UHFFFAOYSA-N 3-[[dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]silyl]oxy-dimethylsilyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)CCCOC(=O)C(C)=C ZIFLDVXQTMSDJE-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- FJKOQFIGFHTRRW-UHFFFAOYSA-N (2-methoxy-3-methylphenyl)-(3-methylphenyl)methanone Chemical compound COC1=C(C)C=CC=C1C(=O)C1=CC=CC(C)=C1 FJKOQFIGFHTRRW-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 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 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- UFUXVJFOILLERS-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(C)CO UFUXVJFOILLERS-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- 125000003070 2-(2-chlorophenyl)ethyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DQMOHZLFVGYNAN-UHFFFAOYSA-N 2-(2-phenylethenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2C=CC=CC=2)=N1 DQMOHZLFVGYNAN-UHFFFAOYSA-N 0.000 description 1
- 125000000301 2-(3-chlorophenyl)ethyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- MPNIGZBDAMWHSX-UHFFFAOYSA-N 2-(4-methylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(C)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MPNIGZBDAMWHSX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- AAXRSWGYLGOFQP-UHFFFAOYSA-N 2-butoxy-1-(2-butoxyphenyl)ethanone Chemical compound CCCCOCC(=O)C1=CC=CC=C1OCCCC AAXRSWGYLGOFQP-UHFFFAOYSA-N 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- MRDMGGOYEBRLPD-UHFFFAOYSA-N 2-ethoxy-1-(2-ethoxyphenyl)ethanone Chemical compound CCOCC(=O)C1=CC=CC=C1OCC MRDMGGOYEBRLPD-UHFFFAOYSA-N 0.000 description 1
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- BCVXHSPFUWZLGQ-UHFFFAOYSA-N mecn acetonitrile Chemical compound CC#N.CC#N BCVXHSPFUWZLGQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GRXOWOKLKIZFNP-UHFFFAOYSA-N undecane-1,1-diol Chemical compound CCCCCCCCCCC(O)O GRXOWOKLKIZFNP-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
Definitions
- the present invention relates to a photocurable composition, an organic protective layer comprising the same, and a device comprising the same.
- Organic electroluminescent devices used in an optical display device are susceptible to deterioration or deterioration of properties under the influence of an environment such as moisture or gas.
- the interface between the metal field and the organic light emitting layer may be peeled off by the influence of moisture, or may be highly resistant to oxidation of the metal, and the organic material itself may be altered by moisture or oxygen, or may be caused by outgass generated from outside or inside. Oxidation of the organic material and the electrode material may occur to deteriorate the light emission characteristics of the organic EL device. Therefore, the organic electroluminescent device should be encapsulated with a composition for encapsulation that protects it from moisture or oxygen.
- the organic electroluminescent element is encapsulated in a multilayer structure in which an inorganic protective layer and an organic protective layer are formed.
- the inorganic protective layer is formed by deposition by plasma, in which the organic protective layer may be etched by the plasma. Such etching may damage the encapsulation function of the organic protective layer, and thus, the organic light emitting diode may have poor luminous properties and may have low reliability.
- the problem to be solved by the present invention is to provide a photocurable composition that can implement an organic protective layer with high plasma resistance.
- Another problem to be solved by the present invention is to provide a photocurable composition capable of realizing an organic protective layer having a significantly low moisture permeability and oxygen permeability.
- Another problem to be solved by the present invention is to provide a photocurable composition that can implement an organic protective layer that can protect the device from the influence of the environment, including water and gas to give the device over time reliability.
- Another object of the present invention is to provide an encapsulated device comprising a cured product of the photocurable composition of the present invention.
- the photocurable composition which is a consistent point of the present invention, has a POC parameter value of about 0.1 or more and about 0.35 or less, and may include a photocurable monomer having an aromatic hydrocarbon group and a photopolymerization initiator.
- Pc n is the number of aromatic rings of each monomer
- Oc n is the number of O atoms and S atoms of each monomer
- Wr n is the weight% of each monomer in the total monomers
- Mw n is the weight average molecular weight of the monomers.
- An encapsulated device includes a device member and a protective layer formed on the device member, the protective layer including an inorganic protective layer and an organic protective layer, wherein the organic protective layer comprises the spectacle. It may include a cured product of the composition.
- the photocurable composition of the present invention exhibits high plasma resistance.
- composition of the present invention can implement an organic protective layer that can protect the device from the effects of the environment, including water and gas to give the device over time reliability.
- Encapsulated devices containing cured products of the compositions of the present invention exhibit high plasma resistance, low moisture vapor transmission rate and oxygen permeability.
- FIG. 1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.
- FIG. 2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.
- (meth) acryl may mean acryl and / or methacryl.
- Hetero as used herein means that the carbon atom is substituted with any one selected from the group consisting of N, O, S and P.
- plasma resistance may be determined according to the etching rate when the cured product of the photocurable composition is plasma treated, and the lower the etching rate, the better the plasma resistance.
- the photocurable composition according to the embodiments of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, and a photocurable monomer having an aromatic hydrocarbon group as a photocurable monomer and a photocurable monomer having no aromatic hydrocarbon group. It may include one or more of.
- the photocurable composition according to an embodiment of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, and may include a photocurable monomer and a photopolymerization initiator having an aromatic hydrocarbon group.
- the photocurable composition according to an embodiment of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, a photocurable monomer having an aromatic hydrocarbon group, a photocurable monomer having no aromatic hydrocarbon group, and It may include a photopolymerization initiator.
- Pc n is the number of aromatic rings of each monomer
- Oc n is the number of O atoms and S atoms of each monomer
- Wr n is the weight percent of each monomer in the total monomers
- Mw n represents the molecular weight of the monomer.
- the POC parameter is a value obtained by subtracting the content of O and S atoms from the aromatic ring content in the photocurable monomer and dividing it by the composition average molecular weight.
- the POC parameter value may be about 0.100 or more and about 0.350 or less. .
- the plasma etch rate may be increased to damage the organic layer, thereby lowering the reliability of the device.
- the POC parameter value is greater than about 0.350, the POC parameter may not be suitable for the process due to the viscosity increase.
- the POC parameter value may be, for example, about 0.100 or more and about 0.230 or less, about 0.100 or more and about 0.190 or less, and about 0.108 or more and about 0.187 or less.
- Pc n represents the number of aromatic rings in each monomer.
- the number of the aromatic rings means the number of monocycles contained in the monomer, and in the case of a condensed ring, it means the number of condensed monocycles.
- Pc n is 2 since two monocyclic benzene rings are condensed
- Pc n is 3 when the monomer includes one anthracene group or a phenanthrene group.
- Oc n does not include the number of "O atoms and S atoms" of each monomer and the number of "O" contained in the acrylate.
- Oc n is 0 when the monomer is dodecanediol dimethacrylate and Oc n is 1 when the monomer is phenylthioethyl acrylate.
- the photocurable monomer having an aromatic hydrocarbon group Pc n is 1 or more, Pc n may be 1 or more and 5 or less, in one embodiment Pc n is 1 or more, Pc n is 2 or more, Pc n is 3 or more Can be; Pc n may be 2 or more and 5 or less, Pc n may be 1 or more and 4 or less, and Pc n may be 1 or more and 3 or less.
- the plasma etch rate is lowered so that the organic layer is not damaged and thus the reliability of the device can be improved, and at the same time, an advantageous process can be achieved.
- the photocurable monomer which has the said aromatic hydrocarbon group and / or the photocurable monomer which does not have an aromatic hydrocarbon group means the photocurable monomer which can harden-react with a photoinitiator.
- the photocurable monomer may be a non-silicone monomer that does not include silicon (Si), and may be, for example, a monomer including only an element selected from C, H, O, N, or S, but is not limited thereto.
- the photocurable monomer may be synthesized by a conventional synthetic method, or may be used by purchasing a commercially available product.
- the photocurable monomer having an aromatic hydrocarbon group may be used alone or in combination of one or more, and may be a polycyclic aromatic group including a monocyclic or condensed ring form, a hydrocarbon group including two or more aromatic monocyclic rings, or two or more.
- the heteroatom-containing hydrocarbon group containing an aromatic monocyclic ring for example, it may include one or more of substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group.
- substituted or unsubstituted phenyl group substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted triphenylmethyl group, substituted or unsubstituted terphenyl group , Substituted or unsubstituted quarterphenyl group, substituted or unsubstituted anthracene group, substituted or unsubstituted phenanthrene group, substituted or unsubstituted fluorene group and substituted or unsubstituted triphenylene group, substituted or unsubstituted tetra Phenylene group, substituted or unsubstituted 2-phenyl-2- (phenylthio) ethyl group, substituted or unsubstituted 3-phenyl-2- (phenylthio) ethyl group, substituted
- the aromatic hydrocarbon group may include a structure in which two or more rings are adjacent to each other, for example, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted triphenylmethyl group, and a 2-phenyl-2- (phenylthio) ethyl group. And the like, but are not limited thereto.
- the monomer having an aromatic hydrocarbon group may include 1 to 20, specifically 1 to 5, substituted or unsubstituted vinyl or (meth) acryl groups.
- the photocurable monomer having an aromatic hydrocarbon group is 2-phenylphenoxyethyl (meth) acrylate, 3-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, 3-ethylphenoxy (meth) acrylate, 4-ethylphenoxy ( Meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, 2,2'-phenylphenoxyethyldi (meth) acrylate, 2-phenylphenoxypropyl (Meth) acrylate, 3-phenylphenoxypropyl (meth) acrylate, 4-phenylphen
- the photocurable monomers having the aromatic hydrocarbon group of the present invention are di (meth) acryl whose mono (meth) acrylates mentioned above have the same central moiety, but in which the acrylate is further substituted at the terminal in a symmetrical form. Rates, tri (meth) acrylates, tetra (meth) acrylate forms.
- the (meth) acrylate referred to in the present invention is not limited to one example, and the present invention further includes all acrylates in the structural isomer relationship.
- the present invention is 1,2-phenylenedi (meth) acrylate, 1,3-phenylenedi (meth) acrylic. Includes all rates.
- the monomer having an aromatic hydrocarbon group satisfies Pc n -Oc n ⁇ 1, and ii) when two or more monomers having an aromatic hydrocarbon group are used.
- the mixture preferably satisfies ⁇ (Pc n -Oc n ) ⁇ 1. .
- the monomer having an aromatic hydrocarbon group may be included in an amount of about 5 wt% to about 50 wt%, specifically about 10 wt% to about 45 wt%, and about 30 wt% to about 50 wt%, based on the total weight of the photocurable monomer. It may be excellent in plasma resistance within the above range.
- the weight average molecular weight of the photocurable monomer having an aromatic hydrocarbon group may be 100.00g / mol or more 1000.00g / mol or less, 100.00g / mol or more 300.00g / mol or less, 130.00g / mol or more 700.00g / mol or less, 150.00 g / mol or more and 600.00 g / mol or less. Within the above range can be advantageously advantageous effect.
- the photocurable monomer not having an aromatic hydrocarbon group does not include an aromatic hydrocarbon group, and may include 1 to 20, specifically 1 to 5, substituted or unsubstituted vinyl or (meth) acryl groups, and may include one or more species. It can also be mixed.
- (meth) acrylate monomers having no aromatic hydrocarbon groups include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, dodecyl (meth) acrylic Unsaturated carboxylic acid esters including (meth) acrylic acid esters such as acrylate and cyclohexyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Saturated or unsaturated carboxylic acid vinyl esters
- the photocurable monomer not having an aromatic hydrocarbon group may be a (meth) acrylate monomer having no aromatic hydrocarbon group, and specifically, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl silyl group , Mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate and the like having a substituted or unsubstituted cycloalkyl group.
- the (meth) acrylate monomer having no aromatic hydrocarbon group is a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group or Di (meth) acrylates having a substituted or unsubstituted C1 to C20 alkyl group, tri (meth) acrylates having a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 alkyl group, Tetra (meth) acrylate having a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 alkyl group, or a mixture thereof.
- the (meth) acrylate monomer not having an aromatic hydrocarbon group is a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group or a substituted Or a di (meth) acrylate having an unsubstituted C1 to C20 alkyl group.
- mono (meth) acrylate having a substituted or unsubstituted C 1 to C 20 alkyl group is decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate , Arachidyl (meth) acrylate or a mixture thereof, but is not limited thereto.
- Di (meth) acrylates having a substituted or unsubstituted C1 to C20 alkyl group include octanediol di (meth) acrylate, nonanedioldi (meth) acrylate, decanedioldi (meth) acrylate, and undecanedioldi ( Meth) acrylate, dodecanediol di (meth) acrylate or mixtures thereof, but is not limited thereto.
- the photocurable monomer having no aromatic hydrocarbon group may be included in an amount of about 30 wt% to about 95 wt%, specifically about 50 wt% to about 70 wt%, based on the total weight of the photocurable monomer included in the composition of the present invention.
- the weight average molecular weight of the photocurable monomer having no aromatic hydrocarbon group may be about 100.00 g / mol or more and about 500.00 g / mol or less, about 100.00 g / mol or more and about 300.00 g / mol or less and about 130.00 g / or more than about 400.00 g / mol. Within the above range can be more advantageously effected fairly.
- the photocurable monomer having an aromatic hydrocarbon group in the photocurable monomer and about 50 of the photocurable monomer having no aromatic hydrocarbon group in the photocurable monomer It may be a photocurable composition comprising from about 95% by weight.
- the photocurable monomer having an aromatic hydrocarbon group in the photocurable monomer and about 50 of the photocurable monomer having no aromatic hydrocarbon group in the photocurable monomer It may be a photocurable composition comprising from about 70% by weight.
- the viscosity of the photocurable composition within the above range may be suitable for forming the encapsulation layer of the organic electroluminescent device.
- the photopolymerization initiator includes without limitation any conventional photopolymerization initiator capable of carrying out the photocurable reaction.
- the photopolymerization initiator may include a triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime or mixtures thereof.
- Triazine initiators include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxy Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 -B
- acetophenone-based initiators examples include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methyl propiophenone, pt-butyl trichloro acetophenone and pt-butyl Dichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propan-1-one , 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -butan-1-one, mixtures thereof.
- benzophenone initiators benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-dichloro Benzophenone, 3,3'-dimethyl-2-methoxy benzophenone or mixtures thereof.
- Thioxanthone initiators include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chloro thioke Santon or mixtures thereof.
- the benzoin-based initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or mixtures thereof.
- the phosphorus initiator may be bisbenzoylphenyl phosphine oxide, benzoyldiphenyl phosphine oxide or mixtures thereof.
- oximes examples include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.
- the photopolymerization initiator may be included in about 0.1 parts by weight to about 20 parts by weight based on 100 parts by weight of the total photocurable monomer and the photopolymerization initiator in the photocurable composition. Within this range, photopolymerization can sufficiently occur during exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization. Specifically about 0.5 to about 10 parts by weight, more specifically about 1 to about 8 parts by weight.
- the photopolymerization initiator may be included in about 0.1% to about 5% by weight, specifically about 0.1% to about 4% by weight, based on solids in the photocurable composition. Within this range, photopolymerization can take place sufficiently and the transmittance can be prevented from being lowered due to the remaining unreacted initiator.
- photoacid generators or photopolymerization initiators such as carbazole, diketones, sulfonium, iodonium, diazo, and biimidazole may be used.
- the photocurable composition according to another embodiment of the present invention may further include an antioxidant.
- Antioxidants can improve the thermal stability of the encapsulation layer.
- the antioxidant may include, but is not limited to, one or more selected from the group consisting of phenolic, quinone, amine and phosphite based.
- antioxidants include tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, tris (2,4-di-tert-butylphenyl) phosphite, and the like. Can be mentioned.
- the antioxidant may be included in about 0.01 parts by weight to about 3 parts by weight, specifically 0.01 parts by weight to about 1 part by weight, based on 100 parts by weight of the total photocurable monomer and the photopolymerization initiator in the photocurable composition. Within this range, excellent thermal stability can be exhibited.
- the photocurable composition may be cured by irradiating ultraviolet light at about 10 to about 500 mW / cm 2 for about 1 second to about 100 seconds, but is not limited thereto.
- the photocurable composition may have an etching rate of 12% or less, specifically about 0% to about 10%, more specifically about 0% to about 8.0%, by the plasma after curing. It is excellent in plasma resistance after curing in the above range can implement a reliable organic protective layer.
- the etch rate may be expressed by calculating the following Equation 2 by measuring the thickness (T1) of the organic protective layer after the plasma treatment by forming a curing layer by depositing and curing the photocurable composition to a specific thickness (T0). have.
- Plasma Etch Rate (%) ⁇ (T0-T1) / T0 ⁇ ⁇ 100
- the etching rate may be applied to the photocurable composition by spraying on a silicon wafer and irradiated with UV at 100 J / cm 2 for 10 seconds to form a specimen having a thickness of 5 ⁇ m.
- the plasma etch rate can be calculated by Equation 2 by measuring the thickness T0 of the organic protective layer before performing dry etching and the thickness T1 of the organic protective layer after performing.
- the photocurable composition of the present invention is a flexible organic electroluminescent device, organic electroluminescent device, lighting device, metal sensor pad, microdisk laser, electrochromic device, photochromic device, microelectromechanical system, solar cell, integrated circuit, charge coupling Device, a light-curing composition for the encapsulant of the light emitting polymer.
- the photocurable composition according to an embodiment of the present invention may be a photocurable composition for a display encapsulant selected from an organic light emitting diode (OLED), a light emitting diode (LED), an OLED, or an LED light.
- OLED organic light emitting diode
- LED light emitting diode
- LED light an LED light
- the photocurable composition according to the embodiments of the present invention may be used as an encapsulant of an organic electroluminescent device.
- the organic electroluminescent device may be damaged by a surrounding environment, such as liquid or gas, specifically moisture or oxygen, or may be damaged or characterized by chemicals used in the manufacturing process of a device including the organic electroluminescent device.
- a surrounding environment such as liquid or gas, specifically moisture or oxygen
- it can be used as an encapsulant for forming an organic protective layer which blocks the organic electroluminescent element from the surrounding environment.
- the photocurable composition according to embodiments of the present invention may be used for forming an organic protective layer formed on an organic electroluminescent device, or an organic protective layer formed on an inorganic protective layer formed on an organic electroluminescent device.
- the organic protective layer may be formed using a method such as deposition, inkjet, but is not limited thereto.
- the photocurable composition according to the embodiments of the present invention can be used as an encapsulant for a device member.
- the member for the device is damaged by the surrounding environment, for example, liquid or gas, specifically moisture or oxygen, or damaged by chemicals used in the manufacturing process of the device including the organic electroluminescent element or deteriorated in characteristics. It can be used as an encapsulant to form an organic protective layer which blocks the device member from the surrounding environment in order to prevent it from becoming.
- the device member may be, for example, a flexible organic electroluminescent device, an organic electroluminescent device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, an electric charge. Coupling devices, light emitting polymers, light emitting diodes, and the like.
- An encapsulated device includes a device member and a protective layer formed on the device member, the protective layer includes an inorganic protective layer and an organic protective layer, and the organic protective layer is It may be formed of the photocurable composition of the embodiments of the invention.
- FIG. 1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.
- the encapsulated device 100 of the present embodiment is formed on the substrate 10, the device member 20 formed on the substrate 10, and the device member 20, and the inorganic protective layer 31 and the organic protective layer ( Including a composite protective layer 30 comprising a 32, the inorganic protective layer 31 is formed in contact with the device member 20, the organic protective layer 32 is a photocuring of embodiments of the present invention It can be formed into a composition.
- the device member may be a flexible organic electroluminescent device, an organic electroluminescent device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, a charge coupling device, Light emitting polymers and the like, but is not limited thereto.
- the device member may be one of an organic light emitting diode (OLED), a light emitting diode (LED), an OLED lighting device, and an LED lighting device.
- the substrate 10 is not particularly limited, and for example, a transparent glass, a plastic film, a silicon or a metal substrate can be used.
- the device member 20 may be, for example, an organic electroluminescent device, and includes an organic light emitting layer formed between the first electrode, the second electrode, and the first electrode and the second electrode, and the organic light emitting layer includes a hole injection layer and a hole.
- the transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be sequentially stacked, but is not limited thereto.
- the composite protective layer 30 includes an inorganic protective layer 31 and an organic protective layer 32.
- the inorganic protective layer 31 and the organic protective layer 32 have different components constituting the layers, respectively. It can act as the sealing material of a member.
- the inorganic protective layer 31 is different from the organic protective layer 32 and a component, and may complement the effect of the organic protective layer 32.
- the inorganic protective layer 31 may be formed of an inorganic material having excellent light transmittance and excellent moisture and / or oxygen barrier properties.
- the inorganic protective layer 31 may be a metal, a nonmetal, an intermetallic compound or alloy, a nonmetal intermetallic compound or alloy, an oxide of a metal or nonmetal, a fluoride of a metal or a nonmetal, a nitride of a metal or a nonmetal, a carbide of a metal or a nonmetal.
- Metals or nonmetals include silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transitions Metal, lanthanide metal, and the like, but is not limited thereto.
- the inorganic protective layer is AlOx, In 2 O 3 , including silicon oxide (SiOx), silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe, ZnO, Sb 2 O 3 , Al 2 O 3 , and the like.
- SiOx silicon oxide
- SiNx silicon nitride
- SiOxNy silicon oxygen nitride
- ZnSe ZnO
- Sb 2 O 3 Al 2 O 3
- SnO 2 may be.
- x and y are each 1-5.
- the inorganic protective layer 31 may be deposited through a plasma process, a vacuum process, for example, sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and a combination thereof.
- the thickness of the inorganic protective layer 31 is not particularly limited, but may be about 100-2000.
- the organic protective layer 32 may be formed by deposition, inkjet, screen printing, spin coating, blade coating, curing alone or a combination of the photocurable compositions of the embodiments of the present invention.
- the photocurable composition may be coated to a thickness of about 1 ⁇ m to about 50 ⁇ m, and cured by irradiation at about 10 to about 500 mW / cm 2 for about 1 second to about 100 seconds.
- the organic protective layer and the inorganic protective layer may be alternately deposited in three or more layers.
- the smoothing property of the inorganic protective layer can be ensured, and defects of the inorganic protective layer can be prevented from propagating to another inorganic protective layer.
- the inorganic protective layer deposited between two or more organic protective layers may complement or enhance the sealing effect on the device.
- the composite protective layer 30 alternately includes the inorganic protective layer 31 and the organic protective layer 32, but the total number of the inorganic protective layer 31 and the organic protective layer 32 is not limited.
- the total number of inorganic protective layer 31 and organic protective layer 32 may vary depending on the level of permeation resistance to oxygen and / or moisture and / or water vapor and / or chemicals.
- the total number of the inorganic protective layer 31 and the organic protective layer 32 may be 10 layers or less, for example, 2 to 7 layers, and specifically, an inorganic protective layer / organic protective layer / inorganic protective layer. It may be formed of seven layers in the order of / organic protective layer / inorganic protective layer / organic protective layer / inorganic protective layer.
- the encapsulated device may have an outgas generation amount of about 2000 ppm or less. Within this range, the life of the device member can be increased to increase the reliability, specifically, about 10 ppm to about 1000 ppm.
- FIG. 2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.
- an encapsulated device 200 of another embodiment of the present invention is formed on a substrate 10, a device member 20 formed on the substrate 10, and a device protective member 20 and an inorganic protective layer.
- the composite protective layer 30 including the 31 and the organic protective layer 32, the inorganic protective layer 31 encapsulates the internal space 40 in which the barrier member 20 is accommodated, and the organic protective layer ( 32) may be formed from the photocurable compositions of embodiments of the invention. Except that the inorganic protective layer 31 is not in contact with the device member 20, the description thereof is omitted because it is substantially the same as the organic light emitting display device of an embodiment of the present invention described above.
- Pc n is the number of aromatic rings of each monomer
- Oc n is the number of O atoms and S atoms of each monomer
- Wr n is the weight% of each monomer in the total monomers
- Mw n is the weight average molecular weight of the monomers.
- a photocurable composition was prepared in the same manner as in Example 1, except that each component type and content were used as described in Table 1 below, and POC parameter values were calculated and described in Tables 1 and 2.
- Plasma etch rate (%): Apply the photocurable compositions of Examples and Comparative Examples on a silicon wafer with a spray and irradiate UV at 100 J / cm 2 for 10 seconds to cure the specimen having a thickness of 5 ⁇ m. Prepared. The prepared specimens were dry-etched with argon gas for 1 minute under ICP power 2500 W, RE power 300 W, DC bias 200 V, Ar flow 50 sccm, and pressure 10 mtorr using an ICP dry etcher (Plasma lab system 133, Oxford instruments). Plasma etch rate was calculated by the following formula by measuring the thickness (T0) of the organic protective layer before dry etching and the thickness (T1) of the organic protective layer after the implementation, the results are shown in Table 1 and Table 2.
- Plasma Etch Rate (%) ⁇ (T0-T1) / T0 ⁇ ⁇ 100
- the plasma etching rate is very low in the case of the POC parameter value in the embodiment of the present invention it can be seen that the plasma resistance is remarkably excellent.
- the etching rate is higher than that in the example.
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Abstract
The present invention relates to a photocurable composition having a POC parameter value of at least about 0.1 and at most about 0.35 and comprising a photocurable monomer having an aromatic hydrocarbon group and a photopolymerization initiator.
Description
본 발명은 광경화 조성물, 이를 포함하는 유기보호층, 및 이를 포함하는 장치에 관한 것이다.The present invention relates to a photocurable composition, an organic protective layer comprising the same, and a device comprising the same.
광학 표시 장치에 사용되는 유기 전계 발광 소자는 수분 또는 기체와 같은 환경의 영향을 받아 특성의 열화 또는 변질의 문제가 발생하기 쉽다. 구체적으로 수분의 영향을 받아 금속 전계와 유기 발광층의 계면이 박리되거나, 금속의 산화로 고저항화 될 수 있고, 유기물 자체가 수분 또는 산소에 의하여 변질되거나, 외부 또는 내부에서 발생하는 아웃가스에 의하여 유기재료, 전극재료의 산화가 발생하여 유기 전계 발광 소자의 발광 특성이 저하될 수 있다. 따라서 유기 전계 발광 소자는 수분 또는 산소로부터 이를 보호하는 봉지용 조성물에 의하여 봉지되어야 한다.Organic electroluminescent devices used in an optical display device are susceptible to deterioration or deterioration of properties under the influence of an environment such as moisture or gas. Specifically, the interface between the metal field and the organic light emitting layer may be peeled off by the influence of moisture, or may be highly resistant to oxidation of the metal, and the organic material itself may be altered by moisture or oxygen, or may be caused by outgass generated from outside or inside. Oxidation of the organic material and the electrode material may occur to deteriorate the light emission characteristics of the organic EL device. Therefore, the organic electroluminescent device should be encapsulated with a composition for encapsulation that protects it from moisture or oxygen.
유기 전계 발광 소자는 무기 보호층과 유기 보호층이 형성된 다층 구조로 봉지화되고 있다. 무기 보호층은 플라즈마에 의한 증착으로 형성되는데, 이때 플라즈마에 의해 유기 보호층이 식각될 수 있다. 이러한 식각은 유기 보호층의 봉지 기능에 손상을 줄 수 있고, 이로 인해 유기발광소자는 발광 특성이 떨어지고, 신뢰성이 떨어질 수 있다.The organic electroluminescent element is encapsulated in a multilayer structure in which an inorganic protective layer and an organic protective layer are formed. The inorganic protective layer is formed by deposition by plasma, in which the organic protective layer may be etched by the plasma. Such etching may damage the encapsulation function of the organic protective layer, and thus, the organic light emitting diode may have poor luminous properties and may have low reliability.
본 발명의 배경기술은 한국공개특허 제2011-0071039호에 개시되어 있다.Background art of the present invention is disclosed in Korea Patent Publication No. 2011-0071039.
본 발명이 해결하고자 하는 과제는 내플라즈마성이 높은 유기 보호층을 구현할 수 있는 광경화 조성물을 제공하는 것이다.The problem to be solved by the present invention is to provide a photocurable composition that can implement an organic protective layer with high plasma resistance.
본 발명이 해결하고자 하는 다른 과제는 수분 투습률 및 산소 투과도가 현저하게 낮은 유기 보호층을 구현할 수 있는 광경화 조성물을 제공하는 것이다.Another problem to be solved by the present invention is to provide a photocurable composition capable of realizing an organic protective layer having a significantly low moisture permeability and oxygen permeability.
본 발명이 해결하고자 하는 또다른 과제는 장치를 수분 및 가스를 포함하는 환경의 영향으로부터 보호하여 장치에 경시 신뢰성을 부여할 수 있는 유기 보호층을 구현할 수 있는 광경화 조성물을 제공하는 것이다.Another problem to be solved by the present invention is to provide a photocurable composition that can implement an organic protective layer that can protect the device from the influence of the environment, including water and gas to give the device over time reliability.
본 발명이 해결하고자 또 다른 과제는 본 발명의 광경화 조성물의 경화물을을 포함하는 봉지화된 장치를 제공하는 것이다. Another object of the present invention is to provide an encapsulated device comprising a cured product of the photocurable composition of the present invention.
본 발명의 일관점인 광경화 조성물은 하기 식 1으로 표시되는 POC 파라미터 값이 약 0.1 이상 약 0.35이하이고, 방향족 탄화수소기를 갖는 광경화성 모노머 및 광중합 개시제를 포함할 수 있다.The photocurable composition, which is a consistent point of the present invention, has a POC parameter value of about 0.1 or more and about 0.35 or less, and may include a photocurable monomer having an aromatic hydrocarbon group and a photopolymerization initiator.
<식 1><Equation 1>
상기 식에서, Pcn은 각 모노머의 방향족 고리의 개수, Ocn은 각 모노머의 O원자 및 S원자의 개수, Wrn은 총 모노머 중 각 모노머의 중량%, Mwn는 모노머의 중량평균분자량을 나타낸다.Wherein Pc n is the number of aromatic rings of each monomer, Oc n is the number of O atoms and S atoms of each monomer, Wr n is the weight% of each monomer in the total monomers, and Mw n is the weight average molecular weight of the monomers. .
본 발명의 다른 관점인 봉지화된 장치는 장치용 부재, 및 상기 장치용 부재 위에 형성된 보호층을 포함하고, 상기 보호층은 무기보호층 및 유기보호층을 포함하고, 상기 유기보호층은 상기 광경화 조성물의 경화물을 포함할 수 있다.An encapsulated device according to another aspect of the present invention includes a device member and a protective layer formed on the device member, the protective layer including an inorganic protective layer and an organic protective layer, wherein the organic protective layer comprises the spectacle. It may include a cured product of the composition.
본 발명의 광경화 조성물은 높은 내플라즈마성을 나타낸다. The photocurable composition of the present invention exhibits high plasma resistance.
본 발명의 조성물은 장치를 수분 및 가스를 포함하는 환경의 영향으로부터 보호하여 장치에 경시 신뢰성을 부여할 수 있는 유기 보호층을 구현할 수 있다. The composition of the present invention can implement an organic protective layer that can protect the device from the effects of the environment, including water and gas to give the device over time reliability.
본 발명의 조성물의 경화물을 함유하는 봉지화된 장치는 높은 내플라즈마성, 낮은 수분 투습률 및 산소 투과도를 나타낸다.Encapsulated devices containing cured products of the compositions of the present invention exhibit high plasma resistance, low moisture vapor transmission rate and oxygen permeability.
도 1은 본 발명 일실시예의 봉지화된 장치의 단면도이다.1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention.
도 2는 본 발명 다른 실시예의 봉지화된 장치의 단면도이다.2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.
이하, 첨부한 도면들을 참조하여, 본 출원의 구체예들을 보다 상세하게 설명하고자 한다. 그러나 본 출원에 개시된 기술은 여기서 설명되는 구체예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 단지, 여기서 소개되는 구체예들은 개시된 내용이 철저하고 완전해질 수 있도록 그리고 당업자에게 본 출원의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다. 도면에서 각 구성요소를 명확하게 표현하기 위하여 구성요소의 폭이나 두께 등의 크기를 다소 확대하여 나타내었다. 또한, 설명의 편의를 위하여 구성요소의 일부만을 도시하기도 하였으나, 당업자라면 구성요소의 나머지 부분에 대하여도 용이하게 파악할 수 있을 것이다. 또한, 해당 분야에서 통상의 지식을 가진 자라면 본 출원의 기술적 사상을 벗어나지 않는 범위 내에서 본 출원의 사상을 다양한 다른 형태로 구현할 수 있을 것이다.Hereinafter, exemplary embodiments of the present application will be described in detail with reference to the accompanying drawings. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. It is merely to be understood that the embodiments introduced herein are provided so that the disclosure can be made thorough and complete, and that the spirit of the present application can be fully conveyed to those skilled in the art. In order to clearly express each component in the drawings, the size, such as the width or thickness of the component, is shown to be somewhat enlarged. In addition, although only a part of the components are shown for convenience of description, those skilled in the art will be able to easily understand the rest of the components. In addition, one of ordinary skill in the art may implement the spirit of the present application in various other forms without departing from the technical spirit of the present application.
본 명세서에서 "상부"와 "하부"는 도면을 기준으로 정의한 것으로서, 시 관점에 따라 "상부"가 "하부"로 "하부"가 "상부"로 변경될 수 있고, "위(on)" 또는 "상(on)"으로 지칭되는 것은 바로 위뿐만 아니라 중간에 다른 구조를 개재한 경우도 포함할 수 있다. 반면, "직접 위(directly on)" 또는 "바로 위"로 지칭되는 것은 중간에 다른 구조를 개재하지 않은 것을 나타낸다.In the present specification, "upper" and "lower" are defined based on the drawings, and according to a viewpoint, "upper" may be changed to "lower" and "lower" to "upper", and "on" or What is referred to as “on” may include not only the above but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly on" indicates that there is no intervening structure in between.
본 명세서에서 "(메트)아크릴"은 아크릴(acryl) 및/또는 메타크릴(methacryl)을 의미할 수 있다. As used herein, "(meth) acryl" may mean acryl and / or methacryl.
본 명세서에서 "치환된"은 별도의 정의가 없는 한, 본 발명의 작용기 중 하나 이상의 수소 원자가 할로겐 (F, Cl, Br 또는 I), 히드록시기, 니트로기, 이미노기(=NH, =NR, R은 탄소수 1-10의 알킬기이다), 아미디노기, 히드라진 또는 히드라존기, 카르복시기, 탄소수 1-20의 알킬기, 탄소수 6-30의 아릴기, 탄소수 3-30의 헤테로아릴기, 탄소수 2-30의 헤테로시클로알킬기, 탄소수 3-20의 시클로알킬기로 치환되는 것을 의미할 수 있다.As used herein, unless otherwise defined, "substituted" means that one or more hydrogen atoms of the functional groups of the present invention are halogen (F, Cl, Br or I), hydroxy group, nitro group, imino group (= NH, = NR, R Is an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine or hydrazone group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and a 2 to 30 carbon group It may mean substituted with a heterocycloalkyl group and a cycloalkyl group having 3-20 carbon atoms.
본 명세서에서 "헤테로"는 탄소 원자가 N, O, S 및 P로 이루어진 군에서 선택되는 어느 하나의 원자로 치환된 것을 의미한다."Hetero" as used herein means that the carbon atom is substituted with any one selected from the group consisting of N, O, S and P.
본 명세서에서 "내플라즈마성"은 광경화 조성물의 경화물이 플라즈마 처리 되었을 때, 식각(etch)되는 식각률에 따라 판단할 수 있으며, 식각률이 낮을 수록 내플라즈마성이 우수한 것으로 정의한다.In the present specification, "plasma resistance" may be determined according to the etching rate when the cured product of the photocurable composition is plasma treated, and the lower the etching rate, the better the plasma resistance.
본 발명의 실시예들에 따른 광경화 조성물은 하기 식 1으로 표시되는 POC 파라미터 값이 약 0.100 이상 약 0.350 이하이고, 광경화성 모노머로서 방향족 탄화수소기를 갖는 광경화성 모노머 및 방향족 탄화수소기를 가지지 않는 광경화성 모노머 중 하나 이상을 포함할 수 있다.The photocurable composition according to the embodiments of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, and a photocurable monomer having an aromatic hydrocarbon group as a photocurable monomer and a photocurable monomer having no aromatic hydrocarbon group. It may include one or more of.
본 발명의 일 실시예에 따른 광경화 조성물은 하기 식 1으로 표시되는 POC 파라미터 값이 약 0.100 이상 약 0.350 이하이고, 방향족 탄화수소기를 갖는 광경화성 모노머 및 광중합 개시제를 포함할 수 있다.The photocurable composition according to an embodiment of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, and may include a photocurable monomer and a photopolymerization initiator having an aromatic hydrocarbon group.
또한, 본 발명의 일 실시예에 따른 광경화 조성물은 하기 식 1으로 표시되는 POC 파라미터 값이 약 0.100 이상 약 0.350 이하이고, 방향족 탄화수소기를 갖는 광경화성 모노머, 방향족 탄화수소기를 가지지 않는 광경화성 모노머, 및 광중합 개시제를 포함할 수 있다.In addition, the photocurable composition according to an embodiment of the present invention has a POC parameter value of about 0.100 or more and about 0.350 or less, a photocurable monomer having an aromatic hydrocarbon group, a photocurable monomer having no aromatic hydrocarbon group, and It may include a photopolymerization initiator.
<식 1><Equation 1>
상기 식에서, Pcn은 각 모노머의 방향족 고리의 개수, Ocn은 각 모노머의 O원자 및 S원자의 개수, Wrn은 총 모노머 중 각 모노머의 중량%, Mwn는 모노머의 분자량을 나타낸다.In the above formula, Pc n is the number of aromatic rings of each monomer, Oc n is the number of O atoms and S atoms of each monomer, Wr n is the weight percent of each monomer in the total monomers, Mw n represents the molecular weight of the monomer.
상기 POC 파라미터(phenyl oxygen parameter)는 광경화성 모노머 내의 방향족 고리 함량에서 O, S 원자의 함량을 제외한 것을 계산하여 이를 조성물 평균 분자량으로 나눈 값으로, 상기 POC 파라미터 값은 약 0.100 이상 약 0.350 이하일 수 있다. 상기 POC 파라미터 값을 만족하는 광경화성 모노머를 사용함으로써, 유기 전계 발광 소자 또는 유기 전계 발광 소자 상에 형성된 무기 보호층 상에 유기 보호층을 형성할 때에 플라즈마 처리에 의해 유기 보호층이 손상되는 플라즈마 식각률이 현저하게 낮아 내플라즈마성이 높은 유기 보호층을 제공할 수 있다.The POC parameter is a value obtained by subtracting the content of O and S atoms from the aromatic ring content in the photocurable monomer and dividing it by the composition average molecular weight. The POC parameter value may be about 0.100 or more and about 0.350 or less. . By using a photocurable monomer that satisfies the POC parameter value, the plasma etching rate at which the organic protective layer is damaged by plasma treatment when the organic protective layer is formed on the organic electroluminescent device or the inorganic protective layer formed on the organic electroluminescent device. This remarkably low level can provide an organic protective layer with high plasma resistance.
더욱이, POC 파라미터 값이 약 0.100미만인 경우에는 플라즈마 식각율이 높아져 유기막이 손상되어 소자의 신뢰성이 저하될 수 있으며, 약 0.350 이상인 경우에는 점도 상승으로 인하여 공정에 적합하지 않을 수 있다. Furthermore, when the POC parameter value is less than about 0.100, the plasma etch rate may be increased to damage the organic layer, thereby lowering the reliability of the device. When the POC parameter value is greater than about 0.350, the POC parameter may not be suitable for the process due to the viscosity increase.
상기 POC 파라미터 값은 예를 들어 약 0.100 이상 약 0.230이하일 수 있으며, 약 0.100 이상 약 0.190이하 일 수 있으며, 약 0.108 이상 약 0.187 이하 일 수 있다. The POC parameter value may be, for example, about 0.100 or more and about 0.230 or less, about 0.100 or more and about 0.190 or less, and about 0.108 or more and about 0.187 or less.
상기 Pcn은 각 모노머의 방향족 고리의 개수를 나타낸다. 상기 방향족 고리의 개수는 모노머에 포함되는 단일환의 개수를 의미하며, 축합환인 경우 축합된 각 단일환의 개수를 의미한다. 예를 들어, 모노머가 하나의 나프틸기를 포함하는 경우 단일환인 벤젠고리 2개가 축합된 것이므로 Pcn은 2이며, 모노머가 하나의 안트라센기 또는 페난트렌기를 포함하는 경우 Pcn은 3이다.Pc n represents the number of aromatic rings in each monomer. The number of the aromatic rings means the number of monocycles contained in the monomer, and in the case of a condensed ring, it means the number of condensed monocycles. For example, when the monomer contains one naphthyl group, Pc n is 2 since two monocyclic benzene rings are condensed, and Pc n is 3 when the monomer includes one anthracene group or a phenanthrene group.
상기 Ocn은 각 모노머의 "O 원자 및 S원자의 개수"이나, 아크릴레이트에 포함된 "O"의 개수는 포함하지 않는다. 예를 들어, 모노머가 도데칸디올 디메타아크릴레이트인 경우 Ocn은 0이며, 모노머가 페닐티오에틸 아크릴레이트인경우 Ocn은 1 이다.Oc n does not include the number of "O atoms and S atoms" of each monomer and the number of "O" contained in the acrylate. For example, Oc n is 0 when the monomer is dodecanediol dimethacrylate and Oc n is 1 when the monomer is phenylthioethyl acrylate.
상기 Wrn은 총 모노머 중 각 모노머의 중량%로 예를 들어, 조성물에 사용된 모노머가 도데칸디올 디메타아크릴레이트 60 kg 및 페닐티오에틸아크릴레이트 40 kg로 혼재되어 있다면, 도데칸디올 디메타아크릴레이트의 Wrn은 (60/100) X100= 60 이며, 페닐티오에틸아크릴레이트의 Wrn은 (40/100)X100= 40이다. Wr n is the weight percentage of each monomer in the total monomers. For example, if the monomers used in the composition are mixed with 60 kg of dodecanediol dimethacrylate and 40 kg of phenylthioethylacrylate, dodecanediol dimetha Wr n of acrylate is (60/100) X 100 = 60, and Wr n of phenylthioethyl acrylate is (40/100) X 100 = 40.
본 발명에서, 방향족 탄화수소기를 갖는 광경화성 모노머는 Pcn 이 1 이상이며, Pcn 이 1 이상 5 이하 일 수 있고, 일 예에서 Pcn 이 1 이상, Pcn이 2 이상, Pcn이 3 이상 일 수 있으며; Pcn이 2 이상 5 이하일 수 있고, Pcn 이 1 이상 4 이하일 수 있고, Pcn 이 1 이상 3 이하일 수 있다. 상기 범위 내에서, 플라즈마 식각율이 낮아져 유기막이 손상되지 않아 소자의 신뢰성이 향상될 수 있는 동시에 공정상 유리한 효과를 나타낼 수 있다.In the present invention, the photocurable monomer having an aromatic hydrocarbon group Pc n is 1 or more, Pc n may be 1 or more and 5 or less, in one embodiment Pc n is 1 or more, Pc n is 2 or more, Pc n is 3 or more Can be; Pc n may be 2 or more and 5 or less, Pc n may be 1 or more and 4 or less, and Pc n may be 1 or more and 3 or less. Within this range, the plasma etch rate is lowered so that the organic layer is not damaged and thus the reliability of the device can be improved, and at the same time, an advantageous process can be achieved.
상기 방향족 탄화수소기를 갖는 광경화성 모노머 및/또는 방향족 탄화수소기를 갖지 않는 광경화성 모노머는 광중합 개시제에 의해 경화 반응할 수 있는 광경화성 모노머를 의미한다. 상기 광경화성 모노머는 실리콘(Si)을 포함하지 않는 비-실리콘계 모노머를 사용할 수 있으며, 예를 들어 C, H, O, N 또는 S에서 선택되는 원소 만으로 이루어진 모노머일 수 있으나 이에 한정되지 않는다. 광경화성 모노머는 통상의 합성방법으로 합성하여 사용하거나 상업적으로 판매하는 제품을 구입하여 사용할 수 있다. The photocurable monomer which has the said aromatic hydrocarbon group and / or the photocurable monomer which does not have an aromatic hydrocarbon group means the photocurable monomer which can harden-react with a photoinitiator. The photocurable monomer may be a non-silicone monomer that does not include silicon (Si), and may be, for example, a monomer including only an element selected from C, H, O, N, or S, but is not limited thereto. The photocurable monomer may be synthesized by a conventional synthetic method, or may be used by purchasing a commercially available product.
상기 방향족 탄화수소기를 갖는 광경화 모노머는 1종 또는 1종이상 혼합하여 사용할 수 있으며, 단일환 또는 축합환 형태를 포함하는 다환의 방향족기, 2개 이상의 방향족 단일환을 포함하는 탄화수소기 또는 2개 이상의 방향족 단일환을 포함하는 헤테로원자 함유 탄화수소기로서, 예를 들면 치환 또는 비치환된 C6 내지 C30의 아릴기, 치환 또는 비치환된 C7 내지 C30의 아릴알킬기 중 하나 이상을 포함할 수 있다. 구체적으로 치환 또는 비치환된 페닐기, 치환 또는 비치환된 비페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 비페닐렌기, 치환 또는 비치환된 트리페닐메틸기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 쿼터페닐기, 치환 또는 비치환된 안트라센기, 치환 또는 비치환된 페난트렌기, 치환 또는 비치환된 플루오렌기 및 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 테트라페닐렌기, 치환 또는 비치환된 2-페닐-2-(페닐티오)에틸기, 치환 또는 비치환된 3-페닐-2-(페닐티오)에틸기, 치환 또는 비치환된 2,2-디페닐프로판기, 치환 또는 비치환된 디페닐메탄기, 치환 또는 비치환된 비페닐옥시기, 치환 또는 비치환된 터페닐옥시기, 치환 또는 비치환된 쿼터페닐옥시기, 치환 또는 비치환된 퀸퀴페닐옥시기 및 이들의 구조적 이성질체 중 하나 이상일 수 있다. 구체적으로, 상기 방향족 탄화수소기는 2 이상의 고리가 인접한 구조를 포함할 수 있으며, 예를 들어 치환 또는 비치환된 비페닐기, 치환 또는 비치환된 트리페닐메틸기, 2-페닐-2-(페닐티오)에틸기 등를 포함할 수 있으나 이에 한정되지 않는다.The photocurable monomer having an aromatic hydrocarbon group may be used alone or in combination of one or more, and may be a polycyclic aromatic group including a monocyclic or condensed ring form, a hydrocarbon group including two or more aromatic monocyclic rings, or two or more. As the heteroatom-containing hydrocarbon group containing an aromatic monocyclic ring, for example, it may include one or more of substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group. Specifically substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted triphenylmethyl group, substituted or unsubstituted terphenyl group , Substituted or unsubstituted quarterphenyl group, substituted or unsubstituted anthracene group, substituted or unsubstituted phenanthrene group, substituted or unsubstituted fluorene group and substituted or unsubstituted triphenylene group, substituted or unsubstituted tetra Phenylene group, substituted or unsubstituted 2-phenyl-2- (phenylthio) ethyl group, substituted or unsubstituted 3-phenyl-2- (phenylthio) ethyl group, substituted or unsubstituted 2,2-diphenylpropane group , Substituted or unsubstituted diphenylmethane group, substituted or unsubstituted biphenyloxy group, substituted or unsubstituted terphenyloxy group, substituted or unsubstituted quarterphenyloxy group, substituted or unsubstituted quinquiphenyloxy group And their structural reason One of the body may be at least. Specifically, the aromatic hydrocarbon group may include a structure in which two or more rings are adjacent to each other, for example, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted triphenylmethyl group, and a 2-phenyl-2- (phenylthio) ethyl group. And the like, but are not limited thereto.
상기 방향족 탄화수소기를 갖는 모노머는 치환 또는 비치환된 비닐기 또는 (메트)아크릴기를 1 내지 20개, 구체적으로 1 내지 5개 포함할 수 있다.The monomer having an aromatic hydrocarbon group may include 1 to 20, specifically 1 to 5, substituted or unsubstituted vinyl or (meth) acryl groups.
구체적으로, 상기 방향족 탄화수소기를 갖는 광경화성 모노머는 2-페닐페녹시에틸(메트)아크릴레이트, 3-페닐페녹시에틸(메트)아크릴레이트, 4-페닐페녹시에틸(메트)아크릴레이트, 페녹시에틸(메트)아크릴레이트, 페닐(메트)아크릴레이트, 페녹시(메트)아크릴레이트, 2-에틸페녹시(메트)아크릴레이트, 3-에틸페녹시(메트)아크릴레이트, 4-에틸페녹시(메트)아크릴레이트, 벤질(메트)아크릴레이트, 페닐에틸 (메트)아크릴레이트, 페닐프로필(메트)아크릴레이트, 2,2'-페닐페녹시에틸디(메트)아크릴레이트, 2-페닐페녹시프로필(메트)아크릴레이트, 3-페닐페녹시프로필(메트)아크릴레이트, 4-페닐페녹시프로필(메트)아크릴레이트, 2,2'-페닐페녹시프로필디(메트)아크릴레이트, 2-페닐페녹시부틸(메트)아크릴레이트, 2,2'-페닐페녹시부틸디(메트)아크릴레이트, 4-페닐부틸(메트)아크릴레이트, 2-페닐부틸(메트)아크릴레이트, 3-페닐부틸(메트)아크릴레이트, 2-(2-메틸페닐)에틸(메트)아크릴레이트, 2-(3-메틸페닐)에틸(메트)아크릴레이트, 2-(4-메틸페닐)에틸(메트)아크릴레이트, 2-(4-프로필페닐)에틸 (메트)아크릴레이트, 2-(4-(1-메틸에틸)페닐)에틸(메트)아크릴레이트, 2-(4-메톡시페닐)에틸 (메트)아크릴레이트, 2-(4-사이클로헥실페닐)에틸 (메트)아크릴레이트, 2-(2-클로로페닐)에틸(메트)아크릴레이트, 2-(3-클로로페닐)에틸(메트)아크릴레이트, 2-(4-클로로페닐)에틸(메트)아크릴레이트, 2-(4-브로모페닐)에틸(메트)아크릴레이트, 2-(3-페닐페닐)에틸(메트)아크릴레이트, 2-페닐-2-(페닐티오)에틸(메트)아크릴레이트, 2-(트리페닐메틸옥시)에틸(메트)아크릴레이트, 4-(트리페닐메틸옥시)부틸(메트)아크릴레이트, 3-(비페닐-2-일옥시)부틸(메트)아크릴레이트, 2-(비페닐-2-일옥시)부틸(메트)아크릴레이트, 4-(비페닐-2-일옥시)프로필(메트)아크릴레이트, 3-(비페닐-2-일옥시)프로필(메트)아크릴레이트, 2-(비페닐-2-일옥시)프로필(메트)아크릴레이트, 4-(비페닐-2-일옥시)에틸(메트)아크릴레이트, 3-(비페닐-2-일옥시)에틸(메트)아크릴레이트, 2-(4-벤질페닐)에틸(메트)아크릴레이트, 1-나프틸(메트)아크릴레이트, 2-나프틸(메트)아크릴레이트, 1,4-페닐렌디(메트)아크릴레이트, 비스페놀-에이디(메트)아크릴레이트, 에톡시레이티드비스페놀-에이디(메트)아크릴레이트, 비스페놀에프디(메트)아크릴레이트, 에톡시레이티드비스페놀에프디(메트)아크릴레이트, 4-큐밀페녹시에틸아크릴레이트, 에톡시레이티드비스페닐플루오렌디아크릴레이트 , 및 이들의 구조적 이성질체, 또는 이들의 혼합물을 포함할 수 있으나,이들로 한정되는 것은 아니다. 또한, 본 발명의 상기 방향족 탄화수소기를 갖는 광경화성 모노머는 위에서 언급된 모노(메트)아크릴레이트와 중심 모이어티가 동일하나 대칭형태로 아크릴레이트가 말단에 추가 치환된 형태인 이들의 디(메트)아크릴레이트, 이들의 트리(메트)아크릴레이트, 테트라(메트)아크릴레이트 형태를 포함한다. Specifically, the photocurable monomer having an aromatic hydrocarbon group is 2-phenylphenoxyethyl (meth) acrylate, 3-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, 3-ethylphenoxy (meth) acrylate, 4-ethylphenoxy ( Meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenylpropyl (meth) acrylate, 2,2'-phenylphenoxyethyldi (meth) acrylate, 2-phenylphenoxypropyl (Meth) acrylate, 3-phenylphenoxypropyl (meth) acrylate, 4-phenylphenoxypropyl (meth) acrylate, 2,2'-phenylphenoxypropyldi (meth) acrylate, 2-phenylphenoxy Cibutyl (meth) acrylate, 2,2'-phenylphenoxybutyldi (meth) acrylate, 4-pe Butyl (meth) acrylate, 2-phenylbutyl (meth) acrylate, 3-phenylbutyl (meth) acrylate, 2- (2-methylphenyl) ethyl (meth) acrylate, 2- (3-methylphenyl) ethyl ( Meth) acrylate, 2- (4-methylphenyl) ethyl (meth) acrylate, 2- (4-propylphenyl) ethyl (meth) acrylate, 2- (4- (1-methylethyl) phenyl) ethyl (meth ) Acrylate, 2- (4-methoxyphenyl) ethyl (meth) acrylate, 2- (4-cyclohexylphenyl) ethyl (meth) acrylate, 2- (2-chlorophenyl) ethyl (meth) acrylate , 2- (3-chlorophenyl) ethyl (meth) acrylate, 2- (4-chlorophenyl) ethyl (meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 2- ( 3-phenylphenyl) ethyl (meth) acrylate, 2-phenyl-2- (phenylthio) ethyl (meth) acrylate, 2- (triphenylmethyloxy) ethyl (meth) acrylate, 4- (triphenylmethyl Oxy) butyl (meth) acrylate, 3- (biphenyl-2-yloxy) moiety (Meth) acrylate, 2- (biphenyl-2-yloxy) butyl (meth) acrylate, 4- (biphenyl-2-yloxy) propyl (meth) acrylate, 3- (biphenyl-2- Yloxy) propyl (meth) acrylate, 2- (biphenyl-2-yloxy) propyl (meth) acrylate, 4- (biphenyl-2-yloxy) ethyl (meth) acrylate, 3- (non Phenyl-2-yloxy) ethyl (meth) acrylate, 2- (4-benzylphenyl) ethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1 , 4-phenylenedi (meth) acrylate, bisphenol-edi (meth) acrylate, ethoxylated bisphenol-edi (meth) acrylate, bisphenol Fdi (meth) acrylate, ethoxylated bisphenol Fdi (meth) Acrylate, 4-cumylphenoxyethylacrylate, ethoxylatedbisphenylfluorenediacrylate, and structural isomers thereof, or mixtures thereof. However, it not limited to these. In addition, the photocurable monomers having the aromatic hydrocarbon group of the present invention are di (meth) acryl whose mono (meth) acrylates mentioned above have the same central moiety, but in which the acrylate is further substituted at the terminal in a symmetrical form. Rates, tri (meth) acrylates, tetra (meth) acrylate forms.
또한, 본 발명에서 언급된 (메트)아크릴레이트는 일 예에 해당할 뿐 이로 한정되는 것은 아니며, 더욱이 본 발명은 구조 이성질체 관계에 있는 아크릴레이트를 모두 포함한다. 예를 들어, 본 발명의 일예로 1,4-페닐렌디(메트)아크릴레이트만 언급되어 있더라도, 본 발명은 1,2-페닐렌디(메트)아크릴레이트, 1,3-페닐렌디(메트)아크릴레이트를 모두 포함한다.In addition, the (meth) acrylate referred to in the present invention is not limited to one example, and the present invention further includes all acrylates in the structural isomer relationship. For example, although only 1,4-phenylenedi (meth) acrylate is mentioned as an example of the present invention, the present invention is 1,2-phenylenedi (meth) acrylate, 1,3-phenylenedi (meth) acrylic. Includes all rates.
다만, 본 발명에서, i) 방향족 탄화수소기를 갖는 모노머가 1종만 사용될 경우 방향족 탄화수소기를 갖는 모노머는 Pcn-Ocn≥1을 만족하며, ii) 방향족 탄화수소기를 갖는 모노머를 2종 이상 사용할 경우 이들의 혼합물은 ∑(Pcn-Ocn)≥1을 만족하는 것이 바람직하다. . However, in the present invention, i) when only one monomer having an aromatic hydrocarbon group is used, the monomer having an aromatic hydrocarbon group satisfies Pc n -Oc n ≥ 1, and ii) when two or more monomers having an aromatic hydrocarbon group are used. The mixture preferably satisfies Σ (Pc n -Oc n ) ≧ 1. .
상기 방향족 탄화수소기를 갖는 모노머는 광경화성 모노머 총 중량에 대하여 약 5 중량% 내지 약 50 중량%, 구체적으로 약 10 중량% 내지 약 45 중량%, 약 30 중량% 내지 약 50 중량%로 포함될 수 있다. 상기 범위 내에서 내플라즈마성이 우수할 수 있다.The monomer having an aromatic hydrocarbon group may be included in an amount of about 5 wt% to about 50 wt%, specifically about 10 wt% to about 45 wt%, and about 30 wt% to about 50 wt%, based on the total weight of the photocurable monomer. It may be excellent in plasma resistance within the above range.
본 발명에서, 상기 방향족 탄화수소기를 갖는 광경화성 모노머의 중량평균분자량은 100.00g/mol 이상 1000.00g/mol이하 일 수 있으며, 100.00g/mol 이상 300.00g/mol이하, 130.00g/mol 이상 700.00g/mol이하, 150.00g/mol 이상 600.00g/mol이하 일 수 있다. 상기 범위 내에서 공정적으로 유리한 효과를 나타낼 수 있다.In the present invention, the weight average molecular weight of the photocurable monomer having an aromatic hydrocarbon group may be 100.00g / mol or more 1000.00g / mol or less, 100.00g / mol or more 300.00g / mol or less, 130.00g / mol or more 700.00g / mol or less, 150.00 g / mol or more and 600.00 g / mol or less. Within the above range can be advantageously advantageous effect.
상기 방향족 탄화수소기를 가지지 않는 광경화성 모노머는 방향족 탄화수소기를 포함하지 않으며, 치환 또는 비치환된 비닐기 또는 (메트)아크릴기를 1 내지 20개, 구체적으로 1 내지 5개 포함할 수 있으며, 1종 이상을 혼합하여 사용할 수 도 있다.The photocurable monomer not having an aromatic hydrocarbon group does not include an aromatic hydrocarbon group, and may include 1 to 20, specifically 1 to 5, substituted or unsubstituted vinyl or (meth) acryl groups, and may include one or more species. It can also be mixed.
구체적으로 방향족 탄화수소기를 가지지 않는 (메트)아크릴레이트 모노머는 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 부틸 (메트)아크릴레이트, 2-히드록시에틸 (메트)아크릴레이트, 2-히드록시부틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 노닐 (메트)아크릴레이트, 데카닐 (메트)아크릴레이트, 운데카닐 (메트)아크릴레이트, 도데실 (메트)아크릴레이트, 시클로헥실 (메트)아크릴레이트 등의 (메트)아크릴산 에스테르를 포함하는 불포화 카르본산 에스테르; 2-아미노에틸 (메트)아크릴레이트, 2-디메틸아미노에틸 (메트)아크릴레이트 등의 불포화 카르본산 아미노 알킬 에스테르; 비닐 아세테이트 등의 포화 또는 불포화 카르본산 비닐 에스테르; (메트)아크릴로니트릴 등의 시안화 비닐 화합물; (메트)아크릴아미드 등의 불포화 아미드 화합물; 에틸렌 글리콜 디(메트)아크릴레이트, 트리에틸렌글리콜 디(메트)아크릴레이트, 트리메틸올프로판 트리(메트)아크릴레이트, 1,4-부탄디올 디(메트)아크릴레이트, 1,6-헥산디올 디(메트)아크릴레이트, 옥탄디올 디(메트)아크릴레이트, 노난디올 디(메트)아크릴레이트, 데칸디올 디(메트)아크릴레이트, 운데칸디올 디(메트)아크릴레이트, 도데칸디올 디(메트)아크릴레이트, 네오펜틸글리콜 디(메트)아크릴레이트, 펜타에리트리톨 디(메트)아크릴레이트, 펜타에리트리톨 트리(메트)아크릴레이트, 펜타에리트리톨 테트라(메트)아크릴레이트, 디펜타에리트리톨 디(메트)아크릴레이트, 디펜타에리트리톨 트리(메트)아크릴레이트, 디펜타에리트리톨 테트라(메트)아크릴레이트, 디펜타에리트리톨 펜타(메트)아크릴레이트, 디펜타에리트리톨 헥사(메트)아크릴레이트 또는 이들의 혼합물을 포함할 수 있으나, 이에 한정되지 않는다Specifically (meth) acrylate monomers having no aromatic hydrocarbon groups include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, dodecyl (meth) acrylic Unsaturated carboxylic acid esters including (meth) acrylic acid esters such as acrylate and cyclohexyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Saturated or unsaturated carboxylic acid vinyl esters such as vinyl acetate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth ) Acrylate, octanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, undecanediol di (meth) acrylate, dodecanediol di (meth) acrylate Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylic Latent, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Agent or may comprise a mixture thereof, but are not limited to,
상기 방향족 탄화수소기를 가지지 않는 광경화성 모노머는 방향족 탄화수소기를 가지지 않는 (메트)아크릴레이트 모노머일 수 있으며, 구체적으로 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C1 내지 C20의 알킬 실릴기, 치환 또는 비치환된 시클로알킬기 등을 갖는 모노(메트)아크릴레이트, 디(메트)아크릴레이트, 트리(메트)아크릴레이트, 테트라(메트)아크릴레이트 등일 수 있다.The photocurable monomer not having an aromatic hydrocarbon group may be a (meth) acrylate monomer having no aromatic hydrocarbon group, and specifically, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl silyl group , Mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate and the like having a substituted or unsubstituted cycloalkyl group.
본 발명의 일예에서, 상기 방향족 탄화수소기를 가지지 않는 (메트)아크릴레이트 모노머는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 모노(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 디(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 트리(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 테트라(메트)아크릴레이트 또는 이들의 혼합물일 수 있다.In one embodiment of the invention, the (meth) acrylate monomer having no aromatic hydrocarbon group is a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group or Di (meth) acrylates having a substituted or unsubstituted C1 to C20 alkyl group, tri (meth) acrylates having a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 alkyl group, Tetra (meth) acrylate having a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 alkyl group, or a mixture thereof.
본 발명의 일예에서는 상기 방향족 탄화수소기를 가지지 않는 (메트)아크릴레이트 모노머는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 모노(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 디(메트)아크릴레이트일 수 있다. 구체적으로, 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 모노(메트)아크릴레이트는 데실(메트)아크릴레이트, 운데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 트리데실(메트)아크릴레이트, 테트라데실(메트)아크릴레이트, 펜타데실(메트)아크릴레이트, 헥사데실 (메트)아크릴레이트, 헵타데실(메트)아크릴레이트, 옥타데실(메트)아크릴레이트, 노나데실(메트)아크릴레이트, 아라키딜(메트)아크릴레이트 또는 이들의 혼합물일 수 있으나 이에 한정되지 않는다. 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 디(메트)아크릴레이트는 옥탄디올디(메트)아크릴레이트, 노난디올디(메트)아크릴레이트, 데칸디올디(메트)아크릴레이트, 운데칸디올디(메트)아크릴레이트, 도데칸디올디(메트)아크릴레이트 또는 이들의 혼합물일 수 있으나, 이에 한정되지 않는다.In one embodiment of the present invention, the (meth) acrylate monomer not having an aromatic hydrocarbon group is a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group or a substituted Or a di (meth) acrylate having an unsubstituted C1 to C20 alkyl group. Specifically, mono (meth) acrylate having a substituted or unsubstituted C 1 to C 20 alkyl group is decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate , Arachidyl (meth) acrylate or a mixture thereof, but is not limited thereto. Di (meth) acrylates having a substituted or unsubstituted C1 to C20 alkyl group include octanediol di (meth) acrylate, nonanedioldi (meth) acrylate, decanedioldi (meth) acrylate, and undecanedioldi ( Meth) acrylate, dodecanediol di (meth) acrylate or mixtures thereof, but is not limited thereto.
상기 방향족 탄화수소기를 가지지 않는 광경화성 모노머는 본 발명의 조성물에 포함된 광경화성 모노머 총 중량에 대하여 약 30 중량% 내지 약 95 중량%, 구체적으로 약 50 중량% 내지 약 70 중량%로 포함될 수 있다. The photocurable monomer having no aromatic hydrocarbon group may be included in an amount of about 30 wt% to about 95 wt%, specifically about 50 wt% to about 70 wt%, based on the total weight of the photocurable monomer included in the composition of the present invention.
본 발명에서, 방향족 탄화수소기를 가지지 않는 광경화성 모노머의 중량평균 분자량은 약 100.00 g/mol이상 약 500.00g/mol이하 일 수 있으며, 약 100.00g/mol 이상 약 300.00g/mol이하, 약 130.00g/mol 이상 약 400.00g/mol이하 일 수 있다. 상기 범위 내에서 공정적으로 보다 유리한 효과를 나타낼 수 있다.In the present invention, the weight average molecular weight of the photocurable monomer having no aromatic hydrocarbon group may be about 100.00 g / mol or more and about 500.00 g / mol or less, about 100.00 g / mol or more and about 300.00 g / mol or less and about 130.00 g / or more than about 400.00 g / mol. Within the above range can be more advantageously effected fairly.
본 발명의 일 예에서, 상기 광경화성 모노머 중 방향족 탄화수소기를 갖는 광경화성 모노머를 약 5중량% 내지 약 50중량%로 포함하고, 상기 광경화성 모노머 중 상기 방향족 탄화수소기를 가지지 않는 광경화성 모노머를 약 50 중량% 내지 약 95 중량%로 포함하는 광경화 조성물일 수 있다.In one embodiment of the present invention, about 5% to about 50% by weight of the photocurable monomer having an aromatic hydrocarbon group in the photocurable monomer, and about 50 of the photocurable monomer having no aromatic hydrocarbon group in the photocurable monomer It may be a photocurable composition comprising from about 95% by weight.
본 발명의 일 예에서, 상기 광경화성 모노머 중 방향족 탄화수소기를 갖는 광경화성 모노머를 약 30 중량% 내지 약 50 중량%로 포함하고, 상기 광경화성 모노머 중 상기 방향족 탄화수소기를 가지지 않는 광경화성 모노머를 약 50 중량% 내지 약 70 중량%로 포함하는 광경화 조성물일 수 있다.In one embodiment of the present invention, about 30% to about 50% by weight of the photocurable monomer having an aromatic hydrocarbon group in the photocurable monomer, and about 50 of the photocurable monomer having no aromatic hydrocarbon group in the photocurable monomer It may be a photocurable composition comprising from about 70% by weight.
상기 범위 내에서 광경화 조성물의 점도가 유기 전계 발광 소자의 봉지층 형성에 적절할 수 있다.The viscosity of the photocurable composition within the above range may be suitable for forming the encapsulation layer of the organic electroluminescent device.
상기 광중합 개시제는 광경화성 반응을 수행할 수 있는 통상의 광중합 개시제를 제한 없이 포함한다. 예를 들어, 광중합 개시제는 트리아진계, 아세토페논계, 벤조페논계, 티오크산톤계, 벤조인계, 인계, 옥심계 또는 이들의 혼합물을 포함할 수 있다.The photopolymerization initiator includes without limitation any conventional photopolymerization initiator capable of carrying out the photocurable reaction. For example, the photopolymerization initiator may include a triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime or mixtures thereof.
트리아진계 개시제로는 2,4,6-트리클로로-s-트리아진, 2-페닐-4,6-비스(트리클로로 메틸)-s-트리아진, 2-(3',4'-디메톡시 스티릴)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-(4'-메톡시 나프틸)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-(p-메톡시 페닐)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-비페닐-4,6-비스(트리클로로 메틸)-s-트리아진, 비스(트리클로로 메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-(4-메톡시 나프토-1-일)-4,6-비스(트리클로로 메틸)-s-트리아진, 2,4-트리클로로 메틸(피페로닐)-6-트리아진, 2,4-(트리클로로 메틸(4'-메톡시 스티릴)-6-트리아진 또는 이들의 혼합물일 수 있다.Triazine initiators include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxy Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 -Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho-1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro Methyl (piperonyl) -6-triazine, 2,4- (trichloro methyl (4'-methoxy styryl) -6-triazine, or mixtures thereof.
아세토페논계 개시제로는, 2,2'-디에톡시 아세토페논, 2,2'-디부톡시 아세토페논, 2-히드록시-2-메틸 프로피오페논, p-t-부틸 트리클로로 아세토페논, p-t-부틸 디클로로 아세토페논, 4-클로로 아세토페논, 2,2'-디클로로-4-페녹시 아세토페논, 2-메틸-1-(4-(메틸티오)페닐)-2-모폴리노 프로판-1-온, 2-벤질-2-디메틸 아미노-1-(4-모폴리노 페닐)-부탄-1-온, 이들의 혼합물일 수 있다.Examples of the acetophenone-based initiators include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methyl propiophenone, pt-butyl trichloro acetophenone and pt-butyl Dichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propan-1-one , 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -butan-1-one, mixtures thereof.
벤조페논계 개시제로는 벤조페논, 벤조일 안식향산, 벤조일 안식향산 메틸, 4-페닐 벤조페논, 히드록시 벤조페논, 아크릴화 벤조페논, 4,4'-비스(디메틸 아미노)벤조페논, 4,4'-디클로로 벤조페논, 3,3'-디메틸-2-메톡시 벤조페논 또는 이들의 혼합물일 수 있다. As the benzophenone initiators, benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-dichloro Benzophenone, 3,3'-dimethyl-2-methoxy benzophenone or mixtures thereof.
티오크산톤계 개시제로는 티오크산톤, 2-메틸 티오크산톤, 이소프로필 티오크산톤, 2,4-디에틸 티오크산톤, 2,4-디이소프로필 티오크산톤, 2-클로로 티오크산톤 또는 이들의 혼합물일 수 있다.Thioxanthone initiators include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chloro thioke Santon or mixtures thereof.
벤조인계 개시제로는 벤조인, 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 이소프로필 에테르, 벤조인 이소부틸 에테르, 벤질 디메틸 케탈 또는 이들의 혼합물일 수 있다.The benzoin-based initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or mixtures thereof.
인계 개시제로는 비스벤조일페닐 포스핀옥시드, 벤조일디페닐 포스핀옥시드 또는 이들의 혼합물이 될 수 있다.The phosphorus initiator may be bisbenzoylphenyl phosphine oxide, benzoyldiphenyl phosphine oxide or mixtures thereof.
옥심계로는 2-(o-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온 및 1-(o-아세틸옥심)-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄온, 또는 이들의 혼합물일 수 있다.Examples of oximes include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.
상기 광중합 개시제는 광경화 조성물 중 광경화성 모노머와 광중합 개시제의 합계 100중량부에 대하여 약 0.1중량부 내지 약 20중량부로 포함될 수 있다. 상기 범위 내에서, 노광시 광중합이 충분히 일어날 수 있고, 광중합 후 남은 미반응 개시제로 인하여 투과율이 저하되는 것을 막을 수 있다. 구체적으로 약 0.5 내지 약 10중량부, 보다 구체적으로 약 1 내지 약 8중량부로 포함될 수 있다. 또한, 상기 광중합 개시제는 상기 광경화 조성물 중 고형분 기준으로 약 0.1중량% 내지 약 5중량%, 구체적으로 약 0.1중량% 내지 약 4중량%로 포함될 수 있다. 상기 범위에서, 광중합이 충분히 일어날 수 있고, 남은 미반응 개시제로 인해 투과율이 저하되는 것을 막을 수 있다.The photopolymerization initiator may be included in about 0.1 parts by weight to about 20 parts by weight based on 100 parts by weight of the total photocurable monomer and the photopolymerization initiator in the photocurable composition. Within this range, photopolymerization can sufficiently occur during exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization. Specifically about 0.5 to about 10 parts by weight, more specifically about 1 to about 8 parts by weight. In addition, the photopolymerization initiator may be included in about 0.1% to about 5% by weight, specifically about 0.1% to about 4% by weight, based on solids in the photocurable composition. Within this range, photopolymerization can take place sufficiently and the transmittance can be prevented from being lowered due to the remaining unreacted initiator.
또한, 상기 광중합 개시제 대신에, 카바졸계, 디케톤류, 술포늄계, 요오드늄계, 디아조계, 비이미다졸계 등의 광산 발생제 또는 광중합 개시제를 사용할 수도 있다.Instead of the photopolymerization initiator, photoacid generators or photopolymerization initiators such as carbazole, diketones, sulfonium, iodonium, diazo, and biimidazole may be used.
본 발명 다른 실시예에 따른 광경화 조성물은 산화 방지제를 더 포함할 수 있다.The photocurable composition according to another embodiment of the present invention may further include an antioxidant.
산화 방지제는 봉지층의 열적 안정성을 향상시킬 수 있다. 산화 방지제는 페놀계, 퀴논계, 아민계 및 포스파이트계로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있지만, 이들에 제한되는 것은 아니다. 예를 들면, 산화 방지제는 테트라키스[메틸렌(3,5-디-t-부틸-4-히드록시히드로신나메이트)]메탄, 트리스(2,4-디-터트-부틸페닐)포스파이트 등을 들 수 있다.Antioxidants can improve the thermal stability of the encapsulation layer. The antioxidant may include, but is not limited to, one or more selected from the group consisting of phenolic, quinone, amine and phosphite based. For example, antioxidants include tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, tris (2,4-di-tert-butylphenyl) phosphite, and the like. Can be mentioned.
산화 방지제는 상기 광경화 조성물 중 광경화성 모노머와 광중합 개시제의 합계 100중량부에 대하여 약 0.01중량부 내지 약 3중량부, 구체적으로는 0.01중량부 내지 약 1중량부로 포함될 수 있다. 상기 범위에서, 우수한 열 안정성을 나타낼 수 있다.The antioxidant may be included in about 0.01 parts by weight to about 3 parts by weight, specifically 0.01 parts by weight to about 1 part by weight, based on 100 parts by weight of the total photocurable monomer and the photopolymerization initiator in the photocurable composition. Within this range, excellent thermal stability can be exhibited.
상기 광경화 조성물은 자외선을 약 10 내지 약 500mW/㎠에서 약 1초 내지 약 100초 동안 조사하여 경화할 수 있으나, 이에 한정되지 않는다.The photocurable composition may be cured by irradiating ultraviolet light at about 10 to about 500 mW / cm 2 for about 1 second to about 100 seconds, but is not limited thereto.
상기 광경화 조성물은 경화 후 플라즈마에 의한 식각률이 12% 이하, 구체적으로 약 0% 내지 약 10%, 보다 구체적으로 약 0% 내지 약 8.0%일 수 있다. 상기 범위에서 경화 후 내플라즈마성이 우수하여 신뢰성 있는 유기 보호층을 구현할 수 있다.The photocurable composition may have an etching rate of 12% or less, specifically about 0% to about 10%, more specifically about 0% to about 8.0%, by the plasma after curing. It is excellent in plasma resistance after curing in the above range can implement a reliable organic protective layer.
상기 식각률은 광경화 조성물을 특정 두께(T0)로 증착하여 경화시켜 유기 보호층을 형성하고, 여기에 플라즈마 처리한 후의 유기 보호층의 두께(T1)을 측정하여 하기 식 2에 의하여 계산하여 나타낼 수 있다.The etch rate may be expressed by calculating the following Equation 2 by measuring the thickness (T1) of the organic protective layer after the plasma treatment by forming a curing layer by depositing and curing the photocurable composition to a specific thickness (T0). have.
<식 2><Equation 2>
플라즈마 식각률(%) = { (T0 - T1) / T0 } × 100Plasma Etch Rate (%) = {(T0-T1) / T0} × 100
상기 식각률은 예를 들어 실리콘 웨이퍼 위에 상기 광경화 조성물을 스프레이로 도포하고 자외선을 100J/㎠로 10초 동안 조사하여 경화시킨 도막 두께 5㎛의 시편을 형성한다. ICP dry etcher(Plasma lab system 133, Oxford instruments사)를 사용하여 ICP power 2500W, RF power 300W, DC bias 200V, Ar flow 50 sccm, 압력 10mtorr 조건에서 아르곤 가스를 1분간 드라이 에칭한다. 플라즈마 식각률은 드라이 에칭 실시 전의 유기 보호층의 두께(T0)와 실시 후의 유기 보호층의 두께(T1)를 측정하여 상기 식 2에 의하여 계산할 수 있다.For example, the etching rate may be applied to the photocurable composition by spraying on a silicon wafer and irradiated with UV at 100 J / cm 2 for 10 seconds to form a specimen having a thickness of 5 μm. Dry etch argon gas for 1 minute under ICP power 2500W, RF power 300W, DC bias 200V, Ar flow 50 sccm and pressure 10mtorr using ICP dry etcher (Plasma lab system 133, Oxford instruments). The plasma etch rate can be calculated by Equation 2 by measuring the thickness T0 of the organic protective layer before performing dry etching and the thickness T1 of the organic protective layer after performing.
본 발명의 광경화 조성물은 플렉서블 유기 전계 발광 소자, 유기 전계 발광 소자, 조명 장치, 금속 센서 패드, 마이크로디스크 레이저, 전기변색 장치, 광변색 장치, 마이크로전자기계 시스템, 태양전지, 집적 회로, 전하 결합 장치, 발광 중합체 의 봉지제용 광경화 조성물일 수 있다.The photocurable composition of the present invention is a flexible organic electroluminescent device, organic electroluminescent device, lighting device, metal sensor pad, microdisk laser, electrochromic device, photochromic device, microelectromechanical system, solar cell, integrated circuit, charge coupling Device, a light-curing composition for the encapsulant of the light emitting polymer.
본 발명의 일 실시예에 따른 광경화 조성물은 유기 전계 발광소자(organic lighting emitting diode, OLED), LED(light emitting diode), OLED 또는 LED 조명 중 선택된 디스플레이 봉지제용인 광경화 조성물일 수 있다. The photocurable composition according to an embodiment of the present invention may be a photocurable composition for a display encapsulant selected from an organic light emitting diode (OLED), a light emitting diode (LED), an OLED, or an LED light.
본 발명 실시예들에 따른 광경화 조성물은 유기 전계 발광 소자의 봉지재로서 사용될 수 있다. 구체적으로, 유기 전계 발광 소자가 주변 환경, 예를 들어 액체 또는 기체, 구체적으로 수분 또는 산소에 의하여 손상되거나, 유기 전계 발광 소자를 포함하는 장치의 제조 공정에서 사용되는 화학물질에 의하여 손상되거나 특성이 열화되는 것을 방지하기 위하여 유기 전계 발광 소자를 주변 환경으로부터 차단시키는 유기 보호층을 형성하는 봉지재로서 사용될 수 있다. The photocurable composition according to the embodiments of the present invention may be used as an encapsulant of an organic electroluminescent device. Specifically, the organic electroluminescent device may be damaged by a surrounding environment, such as liquid or gas, specifically moisture or oxygen, or may be damaged or characterized by chemicals used in the manufacturing process of a device including the organic electroluminescent device. In order to prevent deterioration, it can be used as an encapsulant for forming an organic protective layer which blocks the organic electroluminescent element from the surrounding environment.
본 발명 실시예들에 따른 광경화 조성물은 유기 전계 발광 소자 상에 형성되는 유기 보호층, 또는 유기 전계 발광 소자 상에 형성된 무기 보호층 상에 형성되는 유기 보호층을 형성하는 용도로 사용될 수 있다. 상기 유기 보호층은 증착, 잉크젯 등의 방법 을 사용하여 형성될 수 있으나 이에 한정되지 않는다.The photocurable composition according to embodiments of the present invention may be used for forming an organic protective layer formed on an organic electroluminescent device, or an organic protective layer formed on an inorganic protective layer formed on an organic electroluminescent device. The organic protective layer may be formed using a method such as deposition, inkjet, but is not limited thereto.
본 발명 실시예들에 따른 광경화 조성물은 장치용 부재의 봉지재로서 사용될 수 있다. 구체적으로, 장치용 부재가 주변 환경, 예를 들어 액체 또는 기체, 구체적으로 수분 또는 산소에 의하여 손상되거나, 유기 전계 발광 소자를 포함하는 장치의 제조 공정에서 사용되는 화학물질에 의하여 손상되거나 특성이 열화되는 것을 방지하기 위하여 장치용 부재를 주변 환경으로부터 차단시키는 유기 보호층을 형성하는 봉지재로서 사용될 수 있다. 상기 장치용 부재는 예를 들어 플렉서블 유기 전계 발광 소자, 유기 전계 발광 소자, 조명 장치, 금속 센서 패드, 마이크로디스크 레이저, 전기변색 장치, 광변색 장치, 마이크로전자기계 시스템, 태양전지, 집적 회로, 전하 결합 장치, 발광 중합체, 발광 다이오드 등일 수 있으나 이에 한정되지 않는다.The photocurable composition according to the embodiments of the present invention can be used as an encapsulant for a device member. Specifically, the member for the device is damaged by the surrounding environment, for example, liquid or gas, specifically moisture or oxygen, or damaged by chemicals used in the manufacturing process of the device including the organic electroluminescent element or deteriorated in characteristics. It can be used as an encapsulant to form an organic protective layer which blocks the device member from the surrounding environment in order to prevent it from becoming. The device member may be, for example, a flexible organic electroluminescent device, an organic electroluminescent device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, an electric charge. Coupling devices, light emitting polymers, light emitting diodes, and the like.
본 발명 일실시예에 따른 봉지화된 장치는 장치용 부재, 및 상기 장치용 부재 위에 형성된 보호층을 포함하고, 상기 보호층은 무기보호층 및 유기보호층을 포함하고, 상기 유기보호층은 본 발명 실시예들의 광경화 조성물로 형성될 수 있다.An encapsulated device according to an embodiment of the present invention includes a device member and a protective layer formed on the device member, the protective layer includes an inorganic protective layer and an organic protective layer, and the organic protective layer is It may be formed of the photocurable composition of the embodiments of the invention.
이하, 도 1을 참조하여 본 발명 일실시예의 봉지화된 장치를 설명한다. Hereinafter, an encapsulated device according to an embodiment of the present invention will be described with reference to FIG. 1.
도 1은 본 발명 일실시예의 봉지화된 장치의 단면도이다. 본 실시예의 봉지화된 장치(100)는 기판(10), 기판(10) 위에 형성된 장치용 부재(20), 및 장치용 부재 (20) 위에 형성되고 무기보호층(31)과 유기보호층(32)을 포함하는 복합보호층(30)을 포함하고, 무기보호층(31)은 장치용 부재(20)와 접촉하는 상태로 형성되고, 유기보호층(32)은 본 발명 실시예들의 광경화 조성물로 형성될 수 있다.1 is a cross-sectional view of an encapsulated device of one embodiment of the present invention. The encapsulated device 100 of the present embodiment is formed on the substrate 10, the device member 20 formed on the substrate 10, and the device member 20, and the inorganic protective layer 31 and the organic protective layer ( Including a composite protective layer 30 comprising a 32, the inorganic protective layer 31 is formed in contact with the device member 20, the organic protective layer 32 is a photocuring of embodiments of the present invention It can be formed into a composition.
상기 장치용 부재는 플렉서블 유기 전계 발광 소자, 유기 전계 발광 소자, 조명 장치, 금속 센서 패드, 마이크로디스크 레이저, 전기변색 장치, 광변색 장치, 마이크로전자기계 시스템, 태양전지, 집적 회로, 전하 결합 장치, 발광 중합체 등일 수 있으나 이에 한정되지 않는다. 본 발명의 일예에서, 장치용 부재는 유기 전계 발광 소자(OLED), LED(light emitting diode), OLED 조명 장치, LED 조명장치중 하나 일 수 있다. The device member may be a flexible organic electroluminescent device, an organic electroluminescent device, a lighting device, a metal sensor pad, a microdisk laser, an electrochromic device, a photochromic device, a microelectromechanical system, a solar cell, an integrated circuit, a charge coupling device, Light emitting polymers and the like, but is not limited thereto. In one embodiment of the present invention, the device member may be one of an organic light emitting diode (OLED), a light emitting diode (LED), an OLED lighting device, and an LED lighting device.
기판(10)은 특별히 제한되지 않으며, 예를 들면, 투명 유리, 플라스틱 필름, 실리콘 또는 금속 기판 등을 사용할 수 있다..The substrate 10 is not particularly limited, and for example, a transparent glass, a plastic film, a silicon or a metal substrate can be used.
장치용 부재(20)는 예를 들어 유기 전계 발광 소자일 수 있으며, 제1전극, 제2전극, 제1전극과 제2전극 사이에 형성된 유기발광층을 포함하고, 유기발광층은 홀 주입층, 홀 수송층, 발광층, 전자 수송층, 전자 주입층이 순차적으로 적층된 것일 수 있지만, 이에 제한되지 않는다.The device member 20 may be, for example, an organic electroluminescent device, and includes an organic light emitting layer formed between the first electrode, the second electrode, and the first electrode and the second electrode, and the organic light emitting layer includes a hole injection layer and a hole. The transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be sequentially stacked, but is not limited thereto.
복합보호층(30)은 무기보호층(31)과 유기보호층(32)을 포함하고, 무기보호층(31)과 유기보호층(32)은 층을 구성하는 성분이 상이하여 각각이 장치용 부재의 봉지재로서 작용할 수 있다.The composite protective layer 30 includes an inorganic protective layer 31 and an organic protective layer 32. The inorganic protective layer 31 and the organic protective layer 32 have different components constituting the layers, respectively. It can act as the sealing material of a member.
무기보호층(31)은 유기보호층(32)과 성분이 상이하며, 유기보호층(32)의 효과를 보완할 수 있다. 무기보호층(31)은 광투과성이 우수하고, 수분 및/또는 산소 차단성이 우수한 무기 소재로 형성될 수 있다. 예를 들면, 무기보호층(31)은 금속, 비금속, 금속간 화합물 또는 합금, 비금속간 화합물 또는 합금, 금속 또는 비금속의 산화물, 금속 또는 비금속의 불화물, 금속 또는 비금속의 질화물, 금속 또는 비금속의 탄화물, 금속 또는 비금속의 산소질화물, 금속 또는 비금속의 붕소화물, 금속 또는 비금속의 산소붕소화물, 금속 또는 비금속의 실리사이드, 또는 이들의 혼합물일 수 있다. 금속 또는 비금속은 실리콘(Si), 알루미늄(Al), 셀레늄(Se), 아연(Zn), 안티몬(Sb), 인듐(In), 게르마늄(Ge), 주석(Sn), 비스무트(Bi), 전이금속, 란탄족 금속 등이 될 수 있지만, 이에 제한되지 않는다. 구체적으로, 무기보호층은 실리콘 산화물(SiOx), 실리콘 질화물(SiNx), 실리콘 산소 질화물(SiOxNy), ZnSe, ZnO, Sb2O3, Al2O3 등을 포함하는 AlOx, In2O3, SnO2일 수 있다. 상기에서 x, y는 각각 1~5이다.The inorganic protective layer 31 is different from the organic protective layer 32 and a component, and may complement the effect of the organic protective layer 32. The inorganic protective layer 31 may be formed of an inorganic material having excellent light transmittance and excellent moisture and / or oxygen barrier properties. For example, the inorganic protective layer 31 may be a metal, a nonmetal, an intermetallic compound or alloy, a nonmetal intermetallic compound or alloy, an oxide of a metal or nonmetal, a fluoride of a metal or a nonmetal, a nitride of a metal or a nonmetal, a carbide of a metal or a nonmetal. , Oxygen nitrides of metals or nonmetals, borides of metals or nonmetals, oxygen borides of metals or nonmetals, silicides of metals or nonmetals, or mixtures thereof. Metals or nonmetals include silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transitions Metal, lanthanide metal, and the like, but is not limited thereto. Specifically, the inorganic protective layer is AlOx, In 2 O 3 , including silicon oxide (SiOx), silicon nitride (SiNx), silicon oxygen nitride (SiOxNy), ZnSe, ZnO, Sb 2 O 3 , Al 2 O 3 , and the like. SnO 2 may be. In the above, x and y are each 1-5.
무기보호층(31)은 플라즈마 공정, 진공 공정, 예를 들면 스퍼터링, 화학기상증착, 플라즈마화학기상증착, 증발, 승화, 전자사이클로트론공명-플라즈마증기증착 및 이들의 조합을 통하여 증착될 수 있다.The inorganic protective layer 31 may be deposited through a plasma process, a vacuum process, for example, sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma vapor deposition, and a combination thereof.
무기보호층(31)의 두께는 특별히 한정되지 않지만, 약 100-2000탔 수 있다.The thickness of the inorganic protective layer 31 is not particularly limited, but may be about 100-2000.
유기보호층(32)은 본 발명 실시예들의 광경화 조성물의 증착, 잉크젯, 스크린 인쇄, 스핀 코팅, 블레이드 코팅, 경화 단독 또는 이들의 조합에 의해 형성될 수 있다. 예를 들면, 광경화 조성물을 약 1㎛ 내지 약 50㎛ 두께로 코팅하고, 약 10 내지 약 500mW/㎠에서 약 1초 내지 약 100초 동안 조사하여 경화시킬 수 있다.The organic protective layer 32 may be formed by deposition, inkjet, screen printing, spin coating, blade coating, curing alone or a combination of the photocurable compositions of the embodiments of the present invention. For example, the photocurable composition may be coated to a thickness of about 1 μm to about 50 μm, and cured by irradiation at about 10 to about 500 mW / cm 2 for about 1 second to about 100 seconds.
도 1에서 도시되지 않았지만, 유기보호층과 무기보호층은 3층 이상 교대로 증착될 수 있다. 유기보호층이 2 이상의 무기보호층 사이에 증착되는 경우 무기보호층의 평활화 특성을 확보하고, 무기보호층의 결함이 또 다른 무기보호층으로 전파되는 것을 막을 수 있다. 또한 2 이상의 유기보호층 사이에 증착되는 무기보호층은 장치에 대한 봉지 효과를 보완 또는 강화할 수 있다.Although not shown in FIG. 1, the organic protective layer and the inorganic protective layer may be alternately deposited in three or more layers. When the organic protective layer is deposited between two or more inorganic protective layers, the smoothing property of the inorganic protective layer can be ensured, and defects of the inorganic protective layer can be prevented from propagating to another inorganic protective layer. In addition, the inorganic protective layer deposited between two or more organic protective layers may complement or enhance the sealing effect on the device.
복합보호층(30)은 무기보호층(31)과 유기보호층(32)을 교대로 포함하되, 무기보호층(31)과 유기보호층(32)의 총 개수는 제한되지 않는다. 무기보호층(31)과 유기보호층(32)의 총 개수는 산소 및/또는 수분 및/또는 수증기 및/또는 화학 물질에 대한 투과 저항성의 수준에 따라 변경할 수 있다. 예를 들면, 무기보호층(31)과 유기보호층(32)의 총 개수는 10층 이하, 예를 들면 2 내지 7층이 될 수 있고, 구체적으로 무기보호층/유기보호층/무기보호층/유기보호층/무기보호층/유기보호층/무기보호층의 순서로 7층으로 형성될 수 있다.The composite protective layer 30 alternately includes the inorganic protective layer 31 and the organic protective layer 32, but the total number of the inorganic protective layer 31 and the organic protective layer 32 is not limited. The total number of inorganic protective layer 31 and organic protective layer 32 may vary depending on the level of permeation resistance to oxygen and / or moisture and / or water vapor and / or chemicals. For example, the total number of the inorganic protective layer 31 and the organic protective layer 32 may be 10 layers or less, for example, 2 to 7 layers, and specifically, an inorganic protective layer / organic protective layer / inorganic protective layer. It may be formed of seven layers in the order of / organic protective layer / inorganic protective layer / organic protective layer / inorganic protective layer.
상기 봉지화된 장치는 아웃가스 발생량이 약 2000ppm 이하일 수 있다. 상기 범위 내에서, 장치용 부재의 수명이 길어져 신뢰성이 높아질 수 있으며, 구체적으로는 약 10ppm 내지 약 1000ppm일 수 있다.The encapsulated device may have an outgas generation amount of about 2000 ppm or less. Within this range, the life of the device member can be increased to increase the reliability, specifically, about 10 ppm to about 1000 ppm.
이하, 도 2를 참조하여 본 발명 다른 실시예의 봉지화된 장치를 설명한다. 도 2는 본 발명 다른 실시예의 봉지화된 장치의 단면도이다.Hereinafter, an encapsulated device according to another embodiment of the present invention will be described with reference to FIG. 2. 2 is a cross-sectional view of an encapsulated device of another embodiment of the present invention.
도 2를 참조하면, 본 발명 다른 실시예의 봉지화된 장치 (200)는 기판(10), 기판(10) 위에 형성된 장치용 부재(20), 및 장치용 부재(20) 위에 형성되고 무기보호층(31)과 유기보호층(32)을 포함하는 복합보호층(30)을 포함하고, 무기보호층(31)은 장지용 부재(20)가 수용된 내부 공간(40)을 봉지하고, 유기보호층(32)은 본 발명 실시예들의 광경화 조성물로 형성될 수 있다. 무기보호층(31)이 장치용 부재(20)와 접촉하지 않은 점을 제외하고는 상술한 본 발명 일 실시예의 유기발광소자 표시장치와 실질적으로 동일하므로 기술을 생략한다.Referring to FIG. 2, an encapsulated device 200 of another embodiment of the present invention is formed on a substrate 10, a device member 20 formed on the substrate 10, and a device protective member 20 and an inorganic protective layer. The composite protective layer 30 including the 31 and the organic protective layer 32, the inorganic protective layer 31 encapsulates the internal space 40 in which the barrier member 20 is accommodated, and the organic protective layer ( 32) may be formed from the photocurable compositions of embodiments of the invention. Except that the inorganic protective layer 31 is not in contact with the device member 20, the description thereof is omitted because it is substantially the same as the organic light emitting display device of an embodiment of the present invention described above.
이하, 실시예, 비교예 및 시험예를 들어 본 발명의 구성 및 효과를 보다 구체적으로 설명한다. 그러나 이들 실시예, 비교예 및 시험예는 본 발명에 대한 이해를 돕기 위해 예시의 목적으로만 제공된 것일 뿐 본 발명의 범주 및 범위가 하기 실시예, 비교예 및 시험예에 의해 제한되는 것은 아니다.Hereinafter, the structure and effect of the present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However, these examples, comparative examples and test examples are provided only for the purpose of illustration to help the understanding of the present invention, and the scope and scope of the present invention is not limited by the following examples, comparative examples and test examples.
제조예 1Preparation Example 1
냉각관과 교반기를 구비한 3000㎖ 반응기에 디클로로메탄(dichloromethane, 시그마알드리치사) 300㎖를 넣고, 4-히드록시부틸아크릴레이트(4-hydroxibutyl acrylate, 신나까무라사) 200g과 트리에틸아민 168g을 넣고, 플라스크 내 온도를 0℃로 내린 후 p-톨루엔설포닐클로라이드(p-toluene sulfonyl chloride, 시그마알드리치사) 278g을 디클로로메탄 500㎖에 녹인 용액을 2시간 동안 적하하며 교반하였다. 추가로 5시간 교반 후 잔류 용매를 증류로 제거하였다. 얻어진 화합물 300g을 아세토니트릴(acetonitrile, 시그마알드리치사) 1000㎖에 넣고 포타슘카보네이트(potassium carbonate, Aldrich사) 220g과 2-페닐페놀(2-phenylphonol, 시그마알드리치사) 141g을 추가하고 80℃에서 교반하였다. 잔류 용매와 반응 잔류물을 제거하여, 하기 화학식 1의 화합물(분자량 296.36)을 HPLC 순도 93%로 얻었다. Into a 3000 ml reactor equipped with a cooling tube and a stirrer, 300 ml of dichloromethane (Sigma Aldrich Co., Ltd.), 200 g of 4-hydroxyxiacrylate (Sinka Kamura) and 168 g of triethylamine were added. After lowering the temperature in the flask to 0 ° C., a solution of 278 g of p-toluene sulfonyl chloride (Sigma-Aldrich Co., Ltd.) in 500 ml of dichloromethane was added dropwise for 2 hours and stirred. After further stirring for 5 hours, the residual solvent was removed by distillation. 300 g of the obtained compound was added to 1000 ml of acetonitrile (acetonitrile) and 220 g of potassium carbonate (Aldrich) and 141 g of 2-phenylphenol (2-phenylphonol, Sigma Aldrich) were added and stirred at 80 ° C. . The residual solvent and the reaction residue were removed to obtain a compound of formula 1 (molecular weight 296.36) with an HPLC purity of 93%.
<화학식 1><Formula 1>
제조예 2Preparation Example 2
냉각관과 교반기를 구비한 1000㎖ 반응기에 디클로로메탄(dichloromethane, 시그마알드리치사) 200㎖를 넣고, 벤젠티올(benzene thiol, Aldrich 사) 100g과 스티렌옥사이드(styrene oxide, 시그마알드리치사) 109g을 넣고, 플라스크 내 온도를 0℃로 내린 후 아연 퍼클로레이트(zinc perchlorate, 시그마알드리치사) 4g을 넣은 후 8시간 교반 후 잔류 용매를 증류로 제거하였다. 얻어진 화합물 150g을 디클로로메탄 500㎖에 넣고 트리에틸아민(triethylamine, 대정화금) 70g과 0℃에서 교반하면서 아크릴로일클로라이드(acryloyl chloride, TCI사) 65g을 2시간 동안 적하하며 교반하였다. 추가로 5시간 교반 후 잔류 용매와 반응 잔류물을 제거하여, 하기 화학식 2의 화합물(분자량 284.37)을 HPLC 순도 94%로 얻었다.Into a 1000 ml reactor equipped with a cooling tube and a stirrer, 200 ml of dichloromethane (Sigma Aldrich), 100 g of benzene thiol (Aldrich) and 109 g of styrene oxide (Sigma Aldrich) were added. The temperature in the flask was lowered to 0 ° C., 4 g of zinc perchlorate (Sigma Aldrich, Inc.) was added thereto, followed by stirring for 8 hours, and residual solvent was removed by distillation. 150 g of the obtained compound was added to 500 ml of dichloromethane, and 65 g of acryloyl chloride (TCI) was added dropwise for 2 hours while stirring at 70 ° C. with triethylamine (triethylamine). After stirring for an additional 5 hours, the residual solvent and the reaction residue were removed, thereby obtaining a compound of the following Chemical Formula 2 (molecular weight 284.37) with an HPLC purity of 94%.
<화학식 2><Formula 2>
제조예 3Preparation Example 3
냉각관과 교반기를 구비한 2000㎖ 플라스크에 디클로로메탄(dichloromethane, 시그마알드리치사) 600㎖을 채우고 히드록시에틸메타아크릴레이트(hydroxyethyl methacrylate, Aldrich사) 58.8g과 트리에틸아민(triethylamine, 시그마알드리치사 ) 52.2g을 0℃에서 교반하면서 트리페닐클로로메탄(triphenyl chloromethane, 시그마알드리치사, 제품명 trityl chloride) 100g을 천천히 첨가하였다. 온도를 25℃으로 올린 후 4시간 교반하였다. 디클로로메탄을 감압 증류하여 제거한 후 실리카겔 칼럼을 통해 하기 화학식 3의 화합물을 124g을 HPLC 순도 97%로 얻었다.Fill a 2000 ml flask equipped with a cooling tube and a stirrer with 600 ml of dichloromethane (Sigma Aldrich), 58.8 g of hydroxyethyl methacrylate (Aldrich) and triethylamine (Sigma Aldrich) While stirring 52.2 g at 0 ° C., 100 g of triphenyl chloromethane (Sigma Aldrich, product name trityl chloride) was slowly added. The temperature was raised to 25 ° C. and stirred for 4 hours. Dichloromethane was distilled off under reduced pressure, and then 124 g of the compound of Formula 3 was obtained by HPLC purity 97% through a silica gel column.
<화학식 3><Formula 3>
제조예 4Preparation Example 4
냉각관과 교반기를 구비한 2000㎖ 플라스크에 아세토니트릴(acetonitrile, 시그마알드리치사) 800㎖을 채우고 포타슘카보네이트(potassium carbonate, Aldrich사) 180g과 아크릴산 108g을 0℃에서 교반하면서 4,4'-비스(클로로메틸) 비페닐(4,4'-bis(chloromethyl) biphenyl, TCI사) 150g을 천천히 첨가하였다. 온도를 70℃으로 올린 후 12시간 교반하였다. 아세토니트릴을 감압 증류하여 제거한 후 실리카겔 칼럼을 통해 하기 화학식 4의 화합물을 177g 를 HPLC 순도 97%로 얻었다.800 ml of acetonitrile (Sigma-Aldrich) was charged into a 2000 ml flask equipped with a cooling tube and a stirrer, and 180 g of potassium carbonate (Aldrich) and 108 g of acrylic acid were stirred at 0 ° C. to 4,4′-bis ( 150 g of chloromethyl) biphenyl (4,4'-bis (chloromethyl) biphenyl, TCI) was slowly added. The temperature was raised to 70 ° C. and stirred for 12 hours. After acetonitrile was distilled off under reduced pressure, 177 g of a compound of the following Chemical Formula 4 was obtained through a silica gel column with an HPLC purity of 97%.
<화학식 4><Formula 4>
하기 실시예 및 비교예에서 사용된 성분은 다음과 같다.The components used in the following Examples and Comparative Examples are as follows.
(A)광경화성 모노머: (A) Photocurable Monomer:
(a1) 도데칸디올 디메타아크릴레이트(dodecandiol dimethacrylate, Satomer사)(a1) dodecandiol dimethacrylate (Satomer)
(a2) 트리메틸올프로판 트리아크릴레이트(trimethylolpropane triacrylate, BASF사)(a2) trimethylolpropane triacrylate (BASF)
(a3) 1,3-비스(3-메타크릴록시프로필) 테트라메틸 디실록산 (1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, SIB1402.0, Gelest사)(a3) 1,3-bis (3-methacryloxypropyl) tetramethyl disiloxane (1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane, SIB1402.0, Gelest Corporation)
(a4) 2-페닐페녹시에틸 아크릴레이트(2-phenylphenoxyethyl acrylate, FA-301A, Hitachi chemical사)(a4) 2-phenylphenoxyethyl acrylate (2-phenylphenoxyethyl acrylate, FA-301A, Hitachi Chemical Co., Ltd.)
(a5) 제조예 1의 방향족 탄화수소기를 갖는 모노머(a5) Monomer having an aromatic hydrocarbon group of Preparation Example 1
(a6) 제조예 2의 방향족 탄화수소기를 갖는 모노머(a6) Monomer having an aromatic hydrocarbon group of Preparation Example 2
(a7) 제조예 3의 방향족 탄화수소기를 갖는 모노머(a7) Monomer having an aromatic hydrocarbon group of Preparation Example 3
(a8) 페닐티오에틸 아크릴레이트(phenylthioethyl acrylate, KOREMUL-PT-011, 한농화성사)(a8) Phenylthioethyl acrylate (KOREMUL-PT-011, Hannongsung Co., Ltd.)
(a9) 제조예 4의 방향족 탄화수소기를 갖는 모노머(a9) Monomer having an aromatic hydrocarbon group of Preparation Example 4
(B) 광개시제: 인계 개시제(Darocur TPO, BASF사)(B) Photoinitiator: Phosphorus initiator (Darocur TPO, BASF Corporation)
실시예 1Example 1
(a1) 65중량부, (a4) 35중량부 및 (B) 5중량부를 125㎖ 갈색 폴리프로필렌 병에 넣고, 쉐이커를 이용하여 3시간 동안 교반하여 실시예 1의 광경화 조성물을 제조하였으며, 하기 식에 따라 POC 파라미터 값을 계산하여 표 1에 기재하였다.(a1) 65 parts by weight, (a4) 35 parts by weight and (B) 5 parts by weight were placed in a 125 ml brown polypropylene bottle, and stirred for 3 hours using a shaker to prepare the photocurable composition of Example 1 The POC parameter values were calculated according to the formulas and are shown in Table 1.
상기 식에서, Pcn은 각 모노머의 방향족 고리의 개수, Ocn은 각 모노머의 O원자 및 S원자의 개수, Wrn은 총 모노머 중 각 모노머의 중량%, Mwn는 모노머의 중량평균분자량을 나타낸다.Wherein Pc n is the number of aromatic rings of each monomer, Oc n is the number of O atoms and S atoms of each monomer, Wr n is the weight% of each monomer in the total monomers, and Mw n is the weight average molecular weight of the monomers. .
실시예 2~11 및 비교예 1~3Examples 2-11 and Comparative Examples 1-3
각 성분의 종류 및 함량을 하기 표 1에 기재된 바와 같이 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화 조성물을 제조하였으며, POC 파라미터 값을 계산하여 표 1 및 표 2에 기재하였다.A photocurable composition was prepared in the same manner as in Example 1, except that each component type and content were used as described in Table 1 below, and POC parameter values were calculated and described in Tables 1 and 2.
물성 평가Property evaluation
(1) 플라즈마 식각률(%): 실리콘 웨이퍼 위에 상기 실시예 및 비교예의 광경화 조성물을 스프레이로 도포하고 자외선을 100J/㎠로 10초 동안 조사하여 경화시켜 형성한 유기보호층 두께 5㎛의 시편을 제조하였다. 제조된 시편을 ICP dry etcher(Plasma lab system 133, Oxford instruments사)를 사용하여 ICP power 2500W, RE power 300W, DC bias 200V, Ar flow 50 sccm, 압력 10mtorr 조건에서 아르곤 가스를 1분간 드라이 에칭하였다. 플라즈마 식각률은 드라이 에칭 실시 전의 유기 보호층의 두께(T0)와 실시 후의 유기 보호층의 두께(T1)를 측정하여 하기 식에 의하여 계산하였으며, 하기 표 1 및 표 2에 결과를 나타내었다.(1) Plasma etch rate (%): Apply the photocurable compositions of Examples and Comparative Examples on a silicon wafer with a spray and irradiate UV at 100 J / cm 2 for 10 seconds to cure the specimen having a thickness of 5 μm. Prepared. The prepared specimens were dry-etched with argon gas for 1 minute under ICP power 2500 W, RE power 300 W, DC bias 200 V, Ar flow 50 sccm, and pressure 10 mtorr using an ICP dry etcher (Plasma lab system 133, Oxford instruments). Plasma etch rate was calculated by the following formula by measuring the thickness (T0) of the organic protective layer before dry etching and the thickness (T1) of the organic protective layer after the implementation, the results are shown in Table 1 and Table 2.
플라즈마 식각률(%) = { (T0 - T1) / T0 } × 100Plasma Etch Rate (%) = {(T0-T1) / T0} × 100
표 1
Table 1
| 실시예 | ||||||||||||
| (단위:중량부) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| (A) | (a1) | 60 | 65 | 68 | 60 | 65 | 67 | 60 | 50 | 60 | 70 | 60 |
| (a2) | - | - | - | - | - | - | - | - | - | - | - | |
| (a3) | - | - | - | - | - | - | - | - | - | - | - | |
| (a4) | 40 | 35 | 32 | - | - | - | - | 30 | 20 | 20 | 20 | |
| (a5) | - | - | - | 40 | 35 | 33 | - | - | - | - | ||
| (a6) | - | - | - | - | - | - | 40 | - | - | - | - | |
| (a7) | - | - | - | - | - | - | - | 20 | 20 | 10 | - | |
| (a8) | - | - | - | - | - | - | - | - | - | - | - | |
| (a9) | - | - | - | - | - | - | - | - | - | - | 20 | |
| (B) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| POC 파라미터 | 0.129 | 0.111 | 0.101 | 0.124 | 0.108 | 0.102 | 0.124 | 0.216 | 0.181 | 0.122 | 0.187 | |
| 플라즈마식각률(%) | 6.1 | 6.5 | 8.2 | 6.8 | 7.0 | 7.9 | 7.2 | 4.2 | 4.5 | 6.9 | 6.64 | |
| Example | ||||||||||||
| (Unit: weight part) | One | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| (A) | (a1) | 60 | 65 | 68 | 60 | 65 | 67 | 60 | 50 | 60 | 70 | 60 |
| (a2) | - | - | - | - | - | - | - | - | - | - | - | |
| (a3) | - | - | - | - | - | - | - | - | - | - | - | |
| (a4) | 40 | 35 | 32 | - | - | - | - | 30 | 20 | 20 | 20 | |
| (a5) | - | - | - | 40 | 35 | 33 | - | - | - | - | ||
| (a6) | - | - | - | - | - | - | 40 | - | - | - | - | |
| (a7) | - | - | - | - | - | - | - | 20 | 20 | 10 | - | |
| (a8) | - | - | - | - | - | - | - | - | - | - | - | |
| (a9) | - | - | - | - | - | - | - | - | - | - | 20 | |
| (B) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| POC parameter | 0.129 | 0.111 | 0.101 | 0.124 | 0.108 | 0.102 | 0.124 | 0.216 | 0.181 | 0.122 | 0.187 | |
| Plasma Etch Rate (%) | 6.1 | 6.5 | 8.2 | 6.8 | 7.0 | 7.9 | 7.2 | 4.2 | 4.5 | 6.9 | 6.64 | |
표 2
TABLE 2
| 비교예 | ||||
| (단위: 중량부) | 1 | 2 | 3 | |
| (A) | (a1) | 95 | 50 | 65 |
| (a2) | 5 | - | - | |
| (a3) | - | 30 | - | |
| (a4) | - | 20 | - | |
| (a5) | - | - | - | |
| (a6) | - | - | - | |
| (a7) | - | - | - | |
| (a8) | - | - | 35 | |
| (a9) | - | - | - | |
| (B) | 5 | 5 | 5 | |
| POC 파라미터 | 0 | -0.02951 | 0 | |
| 플라즈마 식각률(%) | 16.4 | 15.8 | 12.2 | |
| Comparative example | ||||
| (Unit: parts by weight) | One | 2 | 3 | |
| (A) | (a1) | 95 | 50 | 65 |
| (a2) | 5 | - | - | |
| (a3) | - | 30 | - | |
| (a4) | - | 20 | - | |
| (a5) | - | - | - | |
| (a6) | - | - | - | |
| (a7) | - | - | - | |
| (a8) | - | - | 35 | |
| (a9) | - | - | - | |
| (B) | 5 | 5 | 5 | |
| POC parameter | 0 | -0.02951 | 0 | |
| Plasma Etch Rate (%) | 16.4 | 15.8 | 12.2 | |
상기 표 1 및 표 2의 결과에서, POC 파라미터 값이 본 발명 범위 내인 실시예의 경우 플라즈마 식각률이 매우 낮아 내플라즈마성이 현저하게 우수한 점을 알 수 있다. 반면, POC 파라미터 값이 본 발명의 범위를 벗어나는 비교예의 경우 실시예에 비해 식각률이 높게 나타난다.In the results of Table 1 and Table 2, the plasma etching rate is very low in the case of the POC parameter value in the embodiment of the present invention it can be seen that the plasma resistance is remarkably excellent. On the other hand, in the case of the comparative example in which the POC parameter value is outside the scope of the present invention, the etching rate is higher than that in the example.
Claims (14)
- 하기 식 1로 표시되는 POC 파라미터 값이 약 0.1 이상 약 0.35이하이고, 방향족 탄화수소기를 갖는 광경화성 모노머 및 광중합 개시제를 포함하는 광경화 조성물:A photocurable composition comprising a photocurable monomer having a POC parameter value represented by the following formula 1 and a photocurable monomer having an aromatic hydrocarbon group and a photopolymerization initiator:<식 1><Equation 1>
상기 식에서, Pcn은 각 모노머의 방향족 고리의 개수, Ocn은 각 모노머의 O원자 및 S원자의 개수, Wrn은 총 모노머 중 각 모노머의 중량%, Mwn는 모노머의 중량평균분자량을 나타낸다.Wherein Pc n is the number of aromatic rings of each monomer, Oc n is the number of O atoms and S atoms of each monomer, Wr n is the weight% of each monomer in the total monomers, and Mw n is the weight average molecular weight of the monomers. . - 제1항에 있어서,The method of claim 1,방향족 탄화수소기를 가지지 않는 (메타)아크릴레이트계 모노머를 더 포함하는 광경화 조성물.The photocurable composition further containing the (meth) acrylate type monomer which does not have an aromatic hydrocarbon group.
- 제1항에 있어서, The method of claim 1,방향족 탄화수소기를 갖는 광경화성 모노머의 Pcn은 약 1 이상인 약 5 이하인 광경화 조성물.Pc n of the photocurable monomer which has an aromatic hydrocarbon group is about 5 or less which is about 1 or more.
- 제2항에 있어서, The method of claim 2,상기 방향족 탄화수소기를 갖는 모노머 및 방향족 탄화수소기를 가지지 않는 (메타)아크릴계 모노머의 중량평균분자량은 약 100.00 내지 약 500.00g/mol인 광경화 조성물. The weight average molecular weight of the monomer having an aromatic hydrocarbon group and the (meth) acrylic monomer having no aromatic hydrocarbon group is about 100.00 to about 500.00 g / mol.
- 제1항에 있어서,The method of claim 1,상기 방향족 탄화수소기는 치환 또는 비치환된 페닐기, 치환 또는 비치환된 비페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 비페닐렌기, 치환 또는 비치환된 트리페닐메틸기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 안트라센기, 치환 또는 비치환된 페난트렌기, 치환 또는 비치환된 플루오렌기 및 치환 또는 비치환된 트리페닐렌기, 치환 또는 비치환된 테트라페닐렌기, 2-페닐-2-(페닐티오)에틸기, 3-페닐-2-(페닐티오)에틸기 2,2-디페닐프로판기, 디페닐메틸기, 치환 또는 비치환된 비페닐옥시기, 치환 또는 비치환된 터페닐옥시기, 치환 또는 비치환된 쿼터페닐옥시기, 치환 또는 비치환된 퀸퀴페닐옥시기 및 이들의 구조적 이성질체 중에서 선택되는 1종 이상인 광경화 조성물.The aromatic hydrocarbon group is substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenylene group, substituted or unsubstituted triphenylmethyl group, substituted or unsubstituted Terphenyl group, substituted or unsubstituted anthracene group, substituted or unsubstituted phenanthrene group, substituted or unsubstituted fluorene group and substituted or unsubstituted triphenylene group, substituted or unsubstituted tetraphenylene group, 2-phenyl 2- (phenylthio) ethyl group, 3-phenyl-2- (phenylthio) ethyl group 2,2-diphenylpropane group, diphenylmethyl group, substituted or unsubstituted biphenyloxy group, substituted or unsubstituted terphenyl At least one photocurable composition selected from an oxy group, a substituted or unsubstituted quarterphenyloxy group, a substituted or unsubstituted quinquiphenyloxy group, and structural isomers thereof.
- 제2항에 있어서,The method of claim 2,상기 방향족 탄화수소기를 가지지 않는 (메타)아크릴레이트계 모노머는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 모노(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 디(메트)아크릴레이트, 치환 또는 비치환된 C1 내지 C20의 알킬렌기 또는 치환 또는 비치환된 C1 내지 C20의 알킬기를 갖는 트리(메트)아크릴레이트 중 하나 이상을 포함하는 광경화 조성물.The (meth) acrylate monomer having no aromatic hydrocarbon group may be a mono (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted group. At least one of a di (meth) acrylate having an alkyl group of C1 to C20, a substituted or unsubstituted C1 to C20 alkylene group or a tri (meth) acrylate having a substituted or unsubstituted C1 to C20 alkyl group Photocuring composition.
- 제2항에 있어서,The method of claim 2,상기 광경화성 모노머 중 방향족 탄화수소기를 갖는 모노머를 5중량% 내지 50중량%로 포함하고, 상기 광경화성 모노머 중 상기 방향족 탄화수소기를 가지지 않는 (메타)아크릴레이트계 모노머를 약 50중량% 내지 약 95중량%로 포함하는 광경화 조성물.5 wt% to 50 wt% of the monomer having an aromatic hydrocarbon group in the photocurable monomer, and about 50 wt% to about 95 wt% of the (meth) acrylate monomer having no aromatic hydrocarbon group in the photocurable monomer. Photocuring composition comprising a.
- 제1항에 있어서,The method of claim 1,상기 POC 파라미터값은 약 0.100 이상 약 0.230이하인 광경화조성물.Wherein said POC parameter value is greater than or equal to about 0.100 and less than or equal to about 0.230.
- 제1항에 있어서,The method of claim 1,상기 방향족 탄화수소기를 갖는 광경화성 모노머는 C, H, O, N 또는 S에서 선택되는 원소 만으로 이루어지는 광경화 조성물.The photocurable monomer which has the said aromatic hydrocarbon group consists only of elements chosen from C, H, O, N, or S.
- 제1항에 있어서,The method of claim 1,상기 광중합 개시제는 트리아진계, 아세토페논계, 벤조페논계, 티오크산톤계, 벤조인계, 인계, 옥심계 중에서 선택되는 1종 이상인 광경화 조성물.The photoinitiator is at least one selected from triazines, acetophenones, benzophenones, thioxanthones, benzoin, phosphorus and oxime.
- 제1항에 있어서,The method of claim 1,광경화 조성물은 유기 전계 발광소자(organic lighting emitting diode, OLED), LED(light emitting diode), OLED 또는 LED 조명 중 선택된 디스플레이 봉지제용인 광경화 조성물. The photocurable composition is a photocurable composition for a display encapsulant selected from organic light emitting diodes (OLEDs), light emitting diodes (LEDs), OLEDs or LED lights.
- 장치용 부재, 및 상기 장치용 부재 위에 형성된 복합보호층을 포함하고,A device for the device, and a composite protective layer formed on the device for the device,상기 복합보호층은 무기보호층 및 유기보호층을 포함하고,The composite protective layer includes an inorganic protective layer and an organic protective layer,상기 유기보호층은 제1항 내지 제11항 중 어느 한 항의 광경화 조성물의 경화물을 포함하는 봉지화된 장치.The organic protective layer is encapsulated device comprising a cured product of the photocurable composition of any one of claims 1 to 11.
- 제12항에 있어서,The method of claim 12,상기 무기보호층은 금속, 금속 산화물, 금속 불화물, 금속 질화물, 금속 산질화물, 금속 붕소화물, 금속 산붕소화물, 금속 실리사이드에서 선택되는 1종 이상을 포함하고,The inorganic protective layer includes at least one selected from metals, metal oxides, metal fluorides, metal nitrides, metal oxynitrides, metal borides, metal oxyborides, and metal silicides,상기 금속은 실리콘(Si), 알루미늄(Al), 셀레늄(Se), 아연(Zn), 안티몬(Sb), 인듐(In), 게르마늄(Ge), 주석(Sn), 비스무트(Bi), 전이금속, 란탄족 금속 중에서 선택되는 1종 이상을 포함하는 장치.The metal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metal And at least one member selected from lanthanide metals.
- 제12항에 있어서,The method of claim 12,상기 장치용 부재는 플렉서블 유기 전계 발광소자, 유기 전계 발광 소자(OLED), LED(light emitting diode), OLED 조명 장치, LED 조명장치 중 하나 이상을 포함하는 장치.The device member includes one or more of a flexible organic electroluminescent device, an organic electroluminescent device (OLED), a light emitting diode (LED), an OLED lighting device, and an LED lighting device.
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| KR1020150050476A KR20160049953A (en) | 2014-10-28 | 2015-04-09 | Photo-curable composition, organic protective layer comprising the same, and apparatus comprising the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200143442A (en) | 2018-04-16 | 2020-12-23 | 덴카 주식회사 | Encapsulant for organic electroluminescent display devices |
| US20230287221A1 (en) * | 2021-04-02 | 2023-09-14 | Solus Advanced Materials Co., Ltd. | Composition for encapsulating organic light emitting diodes and organic light emitting display device comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013232317A (en) * | 2012-04-27 | 2013-11-14 | Konica Minolta Inc | Organic electronic device |
| US20140027739A1 (en) * | 2010-10-25 | 2014-01-30 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Multilayered Protective Layer, Organic Opto-Electric Device and Method of Manufacturing the Same |
| KR101402355B1 (en) * | 2014-01-16 | 2014-06-02 | (주)휴넷플러스 | Organic electronic device and fabricating method thereof |
| KR20140076423A (en) * | 2012-12-12 | 2014-06-20 | 제일모직주식회사 | Composition for encapsulation, barrier layer comprising the same, barrier stack comprising the same, encapsulated apparatus comprising the same, and method for encapsulating the apparatus |
| JP2014193970A (en) * | 2013-03-29 | 2014-10-09 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition and cured product of the same |
-
2015
- 2015-04-10 WO PCT/KR2015/003617 patent/WO2016068415A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140027739A1 (en) * | 2010-10-25 | 2014-01-30 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Multilayered Protective Layer, Organic Opto-Electric Device and Method of Manufacturing the Same |
| JP2013232317A (en) * | 2012-04-27 | 2013-11-14 | Konica Minolta Inc | Organic electronic device |
| KR20140076423A (en) * | 2012-12-12 | 2014-06-20 | 제일모직주식회사 | Composition for encapsulation, barrier layer comprising the same, barrier stack comprising the same, encapsulated apparatus comprising the same, and method for encapsulating the apparatus |
| JP2014193970A (en) * | 2013-03-29 | 2014-10-09 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition and cured product of the same |
| KR101402355B1 (en) * | 2014-01-16 | 2014-06-02 | (주)휴넷플러스 | Organic electronic device and fabricating method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200143442A (en) | 2018-04-16 | 2020-12-23 | 덴카 주식회사 | Encapsulant for organic electroluminescent display devices |
| US20230287221A1 (en) * | 2021-04-02 | 2023-09-14 | Solus Advanced Materials Co., Ltd. | Composition for encapsulating organic light emitting diodes and organic light emitting display device comprising the same |
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