JP2016529345A - Photocuring composition and encapsulated device comprising the same - Google Patents
Photocuring composition and encapsulated device comprising the same Download PDFInfo
- Publication number
- JP2016529345A JP2016529345A JP2016523615A JP2016523615A JP2016529345A JP 2016529345 A JP2016529345 A JP 2016529345A JP 2016523615 A JP2016523615 A JP 2016523615A JP 2016523615 A JP2016523615 A JP 2016523615A JP 2016529345 A JP2016529345 A JP 2016529345A
- Authority
- JP
- Japan
- Prior art keywords
- substituted
- group
- carbon atoms
- unsubstituted
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000000178 monomer Substances 0.000 claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 115
- 230000004888 barrier function Effects 0.000 claims description 93
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 229910052755 nonmetal Inorganic materials 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 150000001721 carbon Chemical class 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- HNQXCHVZYRDHJN-UHFFFAOYSA-N cyanosilicon Chemical compound [Si]C#N HNQXCHVZYRDHJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 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
- 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
- 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
- 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
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 125000002993 cycloalkylene group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 85
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- -1 biphenylyl group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GPIARXZSVWTOMD-UHFFFAOYSA-N 4-[chloro(dimethyl)silyl]butanenitrile Chemical compound C[Si](C)(Cl)CCCC#N GPIARXZSVWTOMD-UHFFFAOYSA-N 0.000 description 1
- UIFBMBZYGZSWQE-UHFFFAOYSA-N 4-[dichloro(methyl)silyl]butanenitrile Chemical compound C[Si](Cl)(Cl)CCCC#N UIFBMBZYGZSWQE-UHFFFAOYSA-N 0.000 description 1
- WJUVBJOJYPQIJA-UHFFFAOYSA-N 4-[dichloro(methyl)silyl]butanenitrile;4-[dichloro(phenyl)silyl]butanenitrile Chemical compound C[Si](Cl)(Cl)CCCC#N.N#CCCC[Si](Cl)(Cl)C1=CC=CC=C1 WJUVBJOJYPQIJA-UHFFFAOYSA-N 0.000 description 1
- NNDVJVQRHQFKNA-UHFFFAOYSA-N 4-[dichloro(phenyl)silyl]butanenitrile Chemical compound N#CCCC[Si](Cl)(Cl)C1=CC=CC=C1 NNDVJVQRHQFKNA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004622 benzoxazinyl group Chemical group O1NC(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005717 substituted cycloalkylene group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- NFYUPFDCZPKNQJ-UHFFFAOYSA-N tris(trimethylsilyl) trimethylsilyloxysilyl silicate Chemical compound C[Si](C)(C)O[SiH2]O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C NFYUPFDCZPKNQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
-
- 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
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本発明は、一般式１で表される（Ａ）シアノ基含有シリコン系光硬化モノマーおよび（Ｂ）開始剤を含む光硬化組成物およびこれを含む封止化された装置に関する。The present invention relates to a photocuring composition comprising (A) a cyano group-containing silicon-based photocuring monomer represented by general formula 1 and (B) an initiator, and an encapsulated apparatus comprising the photocuring composition.
Description
本発明は、光硬化組成物およびそれを含む封止化された装置に関するものである。 The present invention relates to a photocurable composition and a sealed device containing the same.
従来、モバイル用の小型の有機発光装置は、素子が蒸着された基板とその上を覆う基板との間の空間を、反応性のない不活性ガス（ｉｎｅｒｔ ｇａｓ）を充填剤として充填する方式が用いられていた。しかし、ＴＶ等の大型製品に開発が拡張するとともに、既存のように、基板の間を不活性ガス（ｉｎｅｒｔ ｇａｓ）で充填することになると、ガラス基板の重みによる撓みが生じ得る。また、外部からの衝撃によってパネル全体および有機発光素子が損傷（ｄａｍａｇｅ）し得る。 2. Description of the Related Art Conventionally, a small organic light emitting device for mobile has a method of filling a space between a substrate on which an element is deposited and a substrate covering the element with a non-reactive inert gas as a filler. It was used. However, when the development expands to a large product such as a TV and the space between the substrates is filled with an inert gas as in the existing case, the glass substrate may be bent due to the weight of the glass substrate. In addition, the entire panel and the organic light emitting device may be damaged by an external impact.
これと関連し、米国特許第７７６７４９８号明細書によると、約５層のアクリル系有機物と５層の無機物との反復的な真空蒸着コーティングによって、１０−６ｇ／ｍ２／ｄａｙ程度の水分透過防止特性を確保した。しかし、前記のように有機蒸着を重ねた場合、有機層が障壁特性の全くない有機材料として構成され、水分の浸透によってカソード（Ｃａｔｈｏｄ）層が腐食し発光現象が生じない不良により、信頼性が低くなる短所があった。また、蒸着層を１０層含む前記構造において、有機層の厚さが十分でない場合、無機層上に有機層が蒸着されるとともに、平滑性が劣る問題が生じる。また、障壁特性に優れた酸化アルミニウム単独でのみ用いる場合、層の厚さを厚くしても、蒸着時に発生したピンホール（ｐｉｎ−ｈｏｌｅ）がそのまま成長し、水分および酸素が透過し易くなる。その結果、無機層と有機層との間の付着力が低下し、水分遮断効果が劣る恐れがある。 In this connection, according to US Pat. No. 7,767,498, moisture permeation on the order of 10 −6 g / m 2 / day is achieved by repetitive vacuum deposition coating of about 5 layers of acrylic organic material and 5 layers of inorganic material. Preventing properties were ensured. However, when the organic vapor deposition is repeated as described above, the organic layer is configured as an organic material having no barrier property, and the cathode layer is corroded by moisture permeation and the light emission phenomenon does not occur, so that the reliability is improved. There was a downside. Moreover, in the said structure containing 10 vapor deposition layers, when the thickness of an organic layer is not enough, while an organic layer is vapor-deposited on an inorganic layer, the problem that smoothness is inferior arises. Further, when only aluminum oxide having excellent barrier properties is used alone, even if the thickness of the layer is increased, pin-holes generated during vapor deposition grow as they are, and moisture and oxygen are easily transmitted. As a result, the adhesion between the inorganic layer and the organic layer is reduced, and the moisture blocking effect may be inferior.
本発明の目的は、光硬化度および硬化後の無機障壁層に対する付着力が高く、且つ信頼性の高い装置用部材封止のための障壁層を具現できる光硬化組成物を提供することである。 An object of the present invention is to provide a photocuring composition that can realize a barrier layer for sealing a device member having high photocuring degree and high adhesion to an inorganic barrier layer after curing and having high reliability. .
本発明の別の目的は、環境に敏感な装置用部材封止のための障壁層を形成できる光硬化組成物を提供することである。 Another object of the present invention is to provide a photocurable composition capable of forming a barrier layer for sealing an environmentally sensitive device member.
本発明のまた別の目的は、前記光硬化組成物で形成された障壁層を含む封止化された装置を提供することである。 Another object of the present invention is to provide a sealed device comprising a barrier layer formed from the photocured composition.
本発明の光硬化組成物は、下記一般式１で表される（Ａ）シアノ基含有シリコン系光硬化モノマーおよび（Ｂ）開始剤を含んでもよい： The photocurable composition of the present invention may comprise (A) a cyano group-containing silicon-based photocurable monomer represented by the following general formula 1 and (B) an initiator:
（前記一般式１で、Ｒ１、Ｒ２、Ｒ３、Ｘ１、Ｘ２、Ｘ３、Ｙ１、Ｙ２は下記の詳細な説明で定義する通りである）。 (In the general formula 1, R 1 , R 2 , R 3, X 1 , X 2, X 3 , Y 1 , Y 2 are as defined in the detailed description below).
前記（Ａ）シアノ基含有シリコン系光硬化モノマーは、単独または２種以上で含まれてもよい。 The (A) cyano group-containing silicon-based photocurable monomer may be contained alone or in combination of two or more.
前記光硬化組成物は、モノ（メタ）アクリレート型の前記（Ａ）シアノ基含有シリコン系光硬化モノマーとジ（メタ）アクリレート型の前記（Ａ）シアノ基含有シリコン系光硬化モノマーとの混合物を含んでもよい。 The photocurable composition is a mixture of the mono (meth) acrylate type (A) cyano group-containing silicon photocurable monomer and the di (meth) acrylate type (A) cyano group-containing silicon photocurable monomer. May be included.
前記光硬化組成物は、（Ｃ）非シアノ系シリコン含有光硬化モノマー、（Ｄ）非シリコン系光硬化モノマー中の一つ以上をさらに含んでもよい。 The photo-curing composition may further include one or more of (C) a non-cyano silicon-containing photo-curing monomer and (D) a non-silicon-based photo-curing monomer.
本発明の有機発光素子封止用組成物は、前記光硬化組成物を含んでもよい。 The composition for sealing an organic light emitting device of the present invention may include the photocurable composition.
本発明の封止化された装置は、装置用部材と、前記装置用部材上に形成され、無機障壁層と有機障壁層とを含む障壁スタック（ｂａｒｒｉｅｒ ｓｔａｃｋ）と、を含み、前記有機障壁層は、前記光硬化組成物で形成されてもよい。 The sealed device of the present invention includes a device member and a barrier stack formed on the device member and including an inorganic barrier layer and an organic barrier layer, and the organic barrier layer May be formed of the photocurable composition.
本発明は、光硬化度および硬化後の無機障壁層に対する付着力が高く、且つ信頼性の高い障壁層を形成でき、装置用部材の封止用途として使用できる光硬化組成物を提供することができる。 The present invention provides a photocurable composition that can form a highly reliable barrier layer with high photocuring degree and adhesion to an inorganic barrier layer after curing, and can be used as a sealing member for apparatus members. it can.
（発明を実施するための最良の形態）
本明細書において「置換または非置換の」の「置換」は、本発明の官能基中の水素原子がハロゲン（Ｆ、Ｃｌ、ＢｒまたはＩ）、ヒドロキシ基、ニトロ基、イミノ基（＝ＮＨ、＝ＮＲ、Ｒは炭素数１以上、１０以下のアルキル基である）、アミノ基（−ＮＨ２、−ＮＨ（Ｒ’）、−Ｎ（Ｒ”）（Ｒ”’）、Ｒ’、Ｒ”、Ｒ”’は、それぞれ独立して炭素数１以上、１０以下のアルキル基である）、炭素数１以上、２０以下のアルキル基、炭素数６以上、２０以下のアリール基、炭素数３以上、１０以下のシクロアルキル基、炭素数３以上、２０以下のヘテロアリール基、炭素数２以上、３０以下のヘテロシクロアルキル基または炭素数７以上、２１以下のアリールアルキル基で置換されることを意味する。
(Best Mode for Carrying Out the Invention)
In the present specification, “substituted” of “substituted or unsubstituted” means that the hydrogen atom in the functional group of the present invention is a halogen (F, Cl, Br or I), a hydroxy group, a nitro group, an imino group (═NH, ═NR, R is an alkyl group having 1 to 10 carbon atoms), amino group (—NH 2 , —NH (R ′), —N (R ″) (R ″ ′), R ′, R ″) And R ″ ′ are each independently an alkyl group having 1 to 10 carbon atoms), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having 3 or more carbon atoms. Substituted with a cycloalkyl group having 10 or less carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or an arylalkyl group having 7 to 21 carbon atoms. means.
本明細書において「＊」は、元素間連結部位である。 In the present specification, “*” is an interelement connection site.
本明細書において「ヘテロ−」とは、別途の定義がない限り、一つの官能基内に、Ｎ、Ｏ、ＳおよびＰからなる群から選ばれるヘテロ原子を１個以上、３個以下含有し、残りは炭素であることを意味する。 In the present specification, unless otherwise defined, “hetero-” contains 1 or more and 3 or less heteroatoms selected from the group consisting of N, O, S and P in one functional group. , Meaning the rest is carbon.
本明細書において「アルキル（ａｌｋｙｌ)基」とは、別途の定義がない限り、線型の飽和（ｓａｔｕｒａｔｅｄ）脂肪族炭化水素基を意味する。 As used herein, the term “alkyl group” means a linear saturated aliphatic hydrocarbon group unless otherwise defined.
具体的に、アルキル基は、炭素数１以上、２０以下のアルキル基でもよい。より具体的に、アルキル基は、炭素数１以上、１０以下のアルキル基または炭素数１以上、６以下のアルキル基でもよい。例えば、炭素数１以上、４以下のアルキル基は、アルキル鎖に１個以上、４個以下の炭素原子が含まれることを意味し、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチルおよびｔ−ブチルからなる群から選ばれることを意味する。 Specifically, the alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 4 carbon atoms means that the alkyl chain contains 1 to 4 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec -Means selected from the group consisting of butyl and t-butyl.
アルキル基は、具体的な例を挙げると、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t−ブチル基、ペンチル基、ヘキシル基等を意味する。 An alkyl group means a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, etc., to give specific examples.
本明細書において「アリール（ａｒｙｌ）基」は、環状の置換基の全ての元素がｐ軌道を有しており、それらのｐ軌道が共役（ｃｏｎｊｕｇａｔｉｏｎ）を形成している置換基を意味し、モノサイクリック又は縮合環ポリサイクリック（すなわち、炭素原子の隣接した対を分けて持つ環）官能基を含む。 In the present specification, an “aryl group” means a substituent in which all elements of a cyclic substituent have p orbitals, and those p orbitals form a conjugation. Monocyclic or fused-ring polycyclic (ie, rings having adjacent pairs of carbon atoms separated) functional groups.
本明細書において「ヘテロアリール（ｈｅｔｅｒｏａｒｙｌ）基」は、アリール基内にＮ、Ｏ、ＳおよびＰからなる群から選ばれるヘテロ原子を１個以上、３個以下含有し、残りは炭素であることを意味する。前記ヘテロアリールが縮合環である場合は、それぞれの環ごとに前記ヘテロ原子を１個以上、３個以下含んでもよい。 In the present specification, a “heteroaryl group” contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P in the aryl group, and the remainder is carbon. Means. When the heteroaryl is a condensed ring, it may contain 1 to 3 heteroatoms for each ring.
具体的に、置換もしくは非置換のアリール基および／または置換もしくは非置換のヘテロアリール基は、置換もしくは非置換のフェニル基、置換もしくは非置換のナフチル基、置換もしくは非置換のアントラセニル基、置換もしくは非置換のフェナントリル基、置換もしくは非置換のナフタセニル基、置換もしくは非置換のピレニル基、置換もしくは非置換のバイフェニリル基、置換もしくは非置換のｐ−ターフェニル基、置換もしくは非置換のｍ−ターフェニル基、置換もしくは非置換のクリセニル基、置換もしくは非置換のトリフェニレニル基、置換もしくは非置換のフェリレニル基、置換もしくは非置換のインデニル基、置換もしくは非置換のフラニル基、置換もしくは非置換のチオフェニル基、置換もしくは非置換のピロリル基、置換もしくは非置換のピラゾリル基、置換もしくは非置換のイミダゾリル基、置換もしくは非置換のトリアゾリル基、置換もしくは非置換のオキサゾリル基、置換もしくは非置換のチアゾリル基、置換もしくは非置換のオキサジアゾリル基、置換もしくは非置換のチアジアゾリル基、置換もしくは非置換のピリジル基、置換もしくは非置換のピリミジニル基、置換もしくは非置換のピラジニル基、置換もしくは非置換のトリアジニル基、置換もしくは非置換のベンゾフラニル基、置換もしくは非置換のベンゾチオフェニル基、置換もしくは非置換のベンゾイミダゾリル基、置換もしくは非置換のインドリル基、置換もしくは非置換のキノリニル基、置換もしくは非置換のイソキノリニル基、置換もしくは非置換のキナゾリニル基、置換もしくは非置換のキノザリニル基、置換もしくは非置換のナフチリジニル基、置換もしくは非置換のベンゾオキサジニル基、置換もしくは非置換のベンゾチアジニル基、置換もしくは非置換のアクリジニル基、置換もしくは非置換のフェナジニル基、置換もしくは非置換のフェノチアジニル基、置換もしくは非置換のフェノキサジニル基、またはこれらの組合せでもよいが、これに制限されるのではない。 Specifically, a substituted or unsubstituted aryl group and / or a substituted or unsubstituted heteroaryl group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, substituted or unsubstituted Unsubstituted phenanthryl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted p-terphenyl group, substituted or unsubstituted m-terphenyl group A group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted ferrylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, A substituted or unsubstituted pyrrolyl group, Or an unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted Substituted thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted Benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or Substituted quinosalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, substituted Alternatively, it may be an unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, or a combination thereof, but is not limited thereto.
本発明において「（メタ）アクリレート」は、アクリレートおよび／またはメタクリレートを意味する。 In the present invention, “(meth) acrylate” means acrylate and / or methacrylate.
以下、本発明の一実施形態に係る光硬化組成物を説明する。 Hereinafter, the photocurable composition which concerns on one Embodiment of this invention is demonstrated.
本発明の一実施形態に係る光硬化組成物は、（Ａ）シアノ基（−ＣＮ）含有シリコン（ｓｉｌｉｃｏｎ）系光硬化モノマー（以下、（Ａ）光硬化モノマーとする）および（Ｂ）開始剤を含んでもよい。（Ａ）光硬化モノマーを含むことによって、光硬化組成物の光硬化度を高めることができ、封止用組成物として用いられ、硬化後の有機障壁層を形成する際の無機障壁層に対する付着力を高めることによって、装置用部材封止時の装置用部材の信頼性を高めることができる。 A photocurable composition according to an embodiment of the present invention includes (A) a cyano group (—CN) -containing silicon-based photocurable monomer (hereinafter referred to as (A) a photocurable monomer) and (B) an initiator. May be included. (A) By containing a photocuring monomer, the photocuring degree of the photocuring composition can be increased, and the photocuring composition is used as a sealing composition and attached to an inorganic barrier layer when forming a cured organic barrier layer. By increasing the adhesion, the reliability of the device member at the time of sealing the device member can be increased.
（Ａ）光硬化モノマーは、シアノ基、シリコン（ｓｉｌｉｃｏｎ）、および光硬化性官能基（例：（メタ）アクリレート基、ビニル基）を有し、例えば、ジ（メタ）アクリレート、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレートまたはヘキサ（メタ）アクリレート等の多官能（メタ）アクリレート、または単官能（メタ）アクリレートでもよい。 (A) The photocuring monomer has a cyano group, silicon, and a photocurable functional group (e.g., (meth) acrylate group, vinyl group), for example, di (meth) acrylate, tri (meth) Polyfunctional (meth) acrylates such as acrylate, tetra (meth) acrylate, penta (meth) acrylate or hexa (meth) acrylate, or monofunctional (meth) acrylate may be used.
一具体例において、（Ａ）光硬化モノマーは、下記式１で表すことができる： In one embodiment, (A) the photocuring monomer can be represented by the following formula 1:
（前記一般式１で、
Ｒ１およびＲ２はそれぞれ独立して、水素、置換または非置換の炭素数１以上、１０以下のアルキル基、置換または非置換の炭素数２以上、１０以下のヘテロアルキル基、置換または非置換の炭素数６以上、２０以下のアリール基、置換または非置換の炭素数４以上、２０以下のヘテロアリール基、置換または非置換の炭素数７以上、２１以下のアリールアルキル基、置換または非置換の炭素数１以上、１０以下のシリル基または下記一般式２であり、
(In the general formula 1,
R 1 and R 2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 10 carbon atoms, substituted or unsubstituted Aryl group having 6 or more and 20 or less carbon atoms, substituted or unsubstituted heteroaryl group having 4 or more and 20 or less carbon atoms, substituted or unsubstituted arylalkyl group having 7 or more and 21 or less carbon atoms, substituted or unsubstituted A silyl group having 1 to 10 carbon atoms, or the following general formula 2:
（前記一般式２で、＊は元素の連結部位で、Ｒ４は水素または炭素数１以上、５以下のアルキル基である）
Ｒ１およびＲ２中の少なくとも一つは、前記一般式２であり、
Ｒ３は、水素、水酸基、ハロゲン、−ＮＲ’Ｒ”（Ｒ’、Ｒ”はそれぞれ独立して水素、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、または置換もしくは非置換の炭素数７以上、２１以下のアリールアルキル基である）、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、置換もしくは非置換の炭素数７以上、２１以下のアリールアルキル基、または置換もしくは非置換の炭素数１以上、１０以下のシリル基であり、
Ｘ１、Ｘ２はそれぞれ独立して単結合または酸素であり、
Ｘ３、Ｙ１およびＹ２はそれぞれ独立して置換もしくは非置換の炭素数１以上、１０以下のアルキレン基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキレン基、置換もしくは非置換の炭素数６以上、２０以下のアリーレン基、置換もしくは非置換の炭素数７以上、２１以下のアリールアルキレン基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリーレン基、または置換もしくは非置換の炭素数３以上、１０以下のシクロアルキレン基である）。
(In the general formula 2, * is an element connecting site, and R 4 is hydrogen or an alkyl group having 1 to 5 carbon atoms)
At least one of R 1 and R 2 is the general formula 2,
R 3 represents hydrogen, a hydroxyl group, halogen, —NR′R ″ (R ′ and R ″ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted carbon; A heteroalkyl group having 2 or more and 10 or less, a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, a substituted or unsubstituted heteroaryl group having 4 or more and 20 or less carbon atoms, or a substituted or unsubstituted group An arylalkyl group having 7 to 21 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 10 carbon atoms, substituted or unsubstituted An unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 7 or more carbon atoms, 21 Arylalkyl group below, or a substituted or unsubstituted C 1 or more carbon atoms, is 10 or less of the silyl group,
X 1 and X 2 are each independently a single bond or oxygen,
X 3 , Y 1 and Y 2 are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, substituted or unsubstituted An arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkylene group having 7 to 21 carbon atoms, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, or a substituted or non-substituted group. A substituted cycloalkylene group having 3 to 10 carbon atoms).
例えば、Ｒ１、Ｒ２はそれぞれ独立して水素、炭素数１以上、９以下のアルキル基、または前記式２で、Ｒ１、Ｒ２中の一つ以上は前記一般式２でもよい。 For example, R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 9 carbon atoms, or one or more of R 1 and R 2 in the formula 2 may be the general formula 2.
例えば、Ｒ３は、炭素数１以上、６以下のアルキル基、または炭素数６以上、１０以下のアリール基でもよい。 For example, R 3 may be an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
例えば、Ｘ３、Ｙ１およびＹ２は、炭素数１以上、１０以下のアルキレン基、炭素数１以上、９以下のアルキレン基、炭素数１以上、８以下のアルキレン基、炭素数１以上、７以下のアルキレン基、炭素数１以上、６以下のアルキレン基、または炭素数１以上、５以下のアルキレン基でもよい。 For example, X 3 , Y 1 and Y 2 are each an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 9 carbon atoms, an alkylene group having 1 to 8 carbon atoms, an alkylene group having 1 to 8 carbon atoms, 1 or more carbon atoms, It may be an alkylene group having 7 or less carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 5 carbon atoms.
（Ａ）光硬化モノマーは、シアノ基含有シリコン化合物と光硬化官能基含有化合物とを反応させて製造してもよいが、これに制限されるのではない。 (A) The photocurable monomer may be produced by reacting a cyano group-containing silicon compound and a photocurable functional group-containing compound, but is not limited thereto.
（Ａ）光硬化モノマーは、単独または２種以上で混合し、光硬化組成物に含んでもよい。一実施形態において、光硬化組成物は、ジ（メタ）アクリレート型（Ａ）光硬化モノマー単独、あるいはモノ（メタ）アクリレート型（Ａ）光硬化モノマーとジ（メタ）アクリレート型（Ａ）光硬化モノマーとの混合物を含んでもよい。前記混合物中のモノ（メタ）アクリレート型（Ａ）光硬化モノマー：ジ（メタ）アクリレート型（Ａ）光硬化モノマーは、約１：０．５以上、１：２以下、具体的に、約１：０．５、約１：１、約１：１．５、または約１：２の重量比で含んでもよい。前記範囲で、光硬化組成物の光硬化度と無機障壁層に対する付着力を高め、装置用部材に使用する際の変色、透明度低下が生じず、信頼性を高めることができる。 (A) A photocuring monomer may be contained individually or in mixture of 2 or more types, and may be included in a photocuring composition. In one embodiment, the photocuring composition is a di (meth) acrylate type (A) photocuring monomer alone, or a mono (meth) acrylate type (A) photocuring monomer and di (meth) acrylate type (A) photocuring. Mixtures with monomers may also be included. The mono (meth) acrylate type (A) photocuring monomer: di (meth) acrylate type (A) photocuring monomer in the mixture is about 1: 0.5 or more, 1: 2 or less, specifically about 1 : 0.5, about 1: 1, about 1: 1.5, or about 1: 2. Within the above range, the photocuring degree of the photocuring composition and the adhesion to the inorganic barrier layer can be increased, and discoloration and transparency reduction when used for a device member do not occur, thereby improving the reliability.
（Ａ）光硬化モノマーは、固形分基準で、光硬化組成物中の約１重量％以上、９９重量％以下、例えば、約９０重量％以上、９９重量％以下で含んでもよく、具体的には、約９０重量％、９１重量％、９２重量％、９３重量％、９４重量％、９５重量％、９６重量％、９７重量％、９８重量％、または９９重量％であってもよく、または、約４０重量％以上、５５重量％以下で含んでもよく、具体的には、約４０重量％、４１重量％、４２重量％、４３重量％、４４重量％、４５重量％、４６重量％、４７重量％、４８重量％、４９重量％、５０重量％、５１重量％、５２重量％、５３重量％、５４重量％、または５５重量％であってもよい。前記範囲で、光硬化組成物の光硬化度が高く、硬化後の無機障壁層に対する付着力に優れるとともに、信頼性を高める効果が表れ得る。 (A) The photocuring monomer may be contained in an amount of about 1% by weight or more and 99% by weight or less in the photocuring composition, for example, about 90% by weight or more and 99% by weight or less based on the solid content. May be about 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% by weight, or About 40 wt% or more and 55 wt% or less, specifically about 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, It may be 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, or 55% by weight. In the said range, the photocuring degree of a photocurable composition is high, and while being excellent in the adhesive force with respect to the inorganic barrier layer after hardening, the effect which improves reliability can appear.
（Ｂ）開始剤は、（Ａ）光硬化モノマーの光硬化反応を開始するものであって、光硬化反応を行うことができる通常の光重合開始剤を制限なく含むことができる。例えば、（Ｂ）開始剤は、トリアジン系、アセトフェノン系、ベンゾフェノン系、チオキサントン系、ベンゾイン系、リン系、オキシム系またはこれらの混合物を含んでもよく、例えば、ジフェニル（２，４，６−トリメチルベンゾイル）ホスフィンオキシドでもよいが、これに制限されるのではない。 The (B) initiator is for initiating the photocuring reaction of the (A) photocuring monomer, and can contain an ordinary photopolymerization initiator capable of performing the photocuring reaction without limitation. For example, the initiator (B) may include triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or a mixture thereof, such as diphenyl (2,4,6-trimethylbenzoyl). ) Phosphine oxide may be used, but is not limited thereto.
（Ｂ）開始剤は、固形分基準で、光硬化組成物中の約１重量％以上、９９重量％以下、例えば、約１重量％以上、１０重量％以下で含んでもよく、具体的には、約１重量％、２重量％、３重量％、４重量％、５重量％、６重量％、７重量％、８重量％、９重量％、または１０重量％であってもよく、または、例えば、約１重量％以上、５重量％以下で含んでもよく、具体的には、約１重量％、２重量％、３重量％、４重量％、または５重量％であってもよい。前記範囲で、露光時の光重合が十分に起こり得、光重合後の残った未反応開始剤によって透過率が低下することを防ぐことができる。 (B) The initiator may be contained in an amount of about 1% by weight or more and 99% by weight or less, for example, about 1% by weight or more and 10% by weight or less in the photocurable composition based on the solid content. About 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, or For example, it may be included at about 1% by weight or more and 5% by weight or less, specifically about 1% by weight, 2% by weight, 3% by weight, 4% by weight, or 5% by weight. Within the above range, photopolymerization at the time of exposure can sufficiently occur, and it is possible to prevent the transmittance from being lowered by the unreacted initiator remaining after the photopolymerization.
一実施形態において、本発明の一実施形態に係る光硬化組成物は、固形分基準で、（Ａ）＋（Ｂ）中、（Ａ）光硬化モノマー約１重量％以上、９９重量％以下および（Ｂ）開始剤約１重量％以上、９９重量％以下を含んでもよい。前記範囲で、光硬化組成物の光硬化度が高く、硬化後の無機障壁層に対する付着力に優れるとともに、信頼性を高める効果が表れ得る。例えば、光硬化組成物は、固形分基準で、（Ａ）＋（Ｂ）中、（Ａ）光硬化モノマー約９０重量％以上、９９重量％以下および（Ｂ）開始剤約１重量％以上、１０重量％以下を含んでもよい。例えば、光硬化組成物は、モノ（メタ）アクリレート型（Ａ）光硬化モノマー約４０重量％以上、５５重量％以下、ジ（メタ）アクリレート型（Ａ）光硬化モノマー約４０重量％以上、５５重量％以下および（Ｂ）開始剤約１重量％以上、５重量％以下を含んでもよい。前記範囲で、光硬化組成物の光硬化度が高く、硬化後の無機障壁層に対する付着力に優れるとともに、信頼性を高める効果が表れ得る。 In one embodiment, the photo-curing composition according to one embodiment of the present invention comprises (A) + (B) (A) a photo-curing monomer of about 1 wt% or more, 99 wt% or less and (B) About 1 wt% or more and 99 wt% or less of the initiator may be included. In the said range, the photocuring degree of a photocurable composition is high, and while being excellent in the adhesive force with respect to the inorganic barrier layer after hardening, the effect which improves reliability can appear. For example, the photocuring composition comprises (A) + (B), based on solid content, in which (A) the photocuring monomer is about 90 wt% or more, 99 wt% or less, and (B) the initiator is about 1 wt% or more, It may contain up to 10% by weight. For example, the photo-curing composition has a mono (meth) acrylate type (A) photocuring monomer of about 40 wt% or more and 55 wt% or less, a di (meth) acrylate type (A) photocuring monomer of about 40 wt% or more, 55 It may contain about 1 wt% or less and (B) about 1 wt% or more and 5 wt% or less. In the said range, the photocuring degree of a photocurable composition is high, and while being excellent in the adhesive force with respect to the inorganic barrier layer after hardening, the effect which improves reliability can appear.
光硬化組成物は、溶剤を含まない無溶剤タイプであって、上述の（Ａ）光硬化モノマーと（Ｂ）開始剤とを混合して製造してもよい。 The photocurable composition is a solvent-free type that does not contain a solvent, and may be manufactured by mixing the above-described (A) photocurable monomer and (B) an initiator.
光硬化組成物は、光硬化度が約９０％以上、例えば、約９０％以上、９５％以下になり得る。前記範囲で、硬化後の硬化収縮応力が低く、シフトが発生しない層を具現することによって、封止用途として使用することができる。 The photocuring composition may have a photocuring degree of about 90% or more, for example, about 90% or more and 95% or less. By implementing a layer having a low curing shrinkage stress after curing within the above range and that does not cause a shift, it can be used as a sealing application.
光硬化組成物は、硬化後の無機障壁層に対する付着力が約２０ｋｇｆ以上になり得る。前記範囲で、外部から浸透する水分または酸素が障壁層の間を容易に浸透できずに信頼性不良が発生し得ない。無機障壁層は、下記で述べる無機障壁層（例：ＳｉＯｘ、ＳｉＮｘ、Ａｌ２Ｏ３）を含んでもよいが、これに制限されるのではない。例えば、無機障壁層に対する付着力は、約２０ｋｇｆ以上、１００ｋｇｆ以下になり得るものであり、例えば、約２５ｋｇｆ以上、１００ｋｇｆ以下になり得る。 The photocuring composition can have an adhesion to the inorganic barrier layer after curing of about 20 kgf or more. Within the above range, moisture or oxygen penetrating from the outside cannot easily penetrate between the barrier layers, and reliability cannot be generated. The inorganic barrier layer may include an inorganic barrier layer (eg, SiOx, SiNx, Al 2 O 3 ) described below, but is not limited thereto. For example, the adhesion force to the inorganic barrier layer can be about 20 kgf or more and 100 kgf or less, for example, about 25 kgf or more and 100 kgf or less.
一実施形態において、シリコン酸化物またはアルミニウム酸化物から形成された無機障壁層に対する付着力は、約２５ｋｇｆ以上、５５ｋｇｆ以下になり得る。他の一実施形態において、シリコン窒化物でなる無機障壁層に対する付着力は、約２５ｋｇｆ以上、４６ｋｇｆ以下になり得る。 In one embodiment, the adhesion to an inorganic barrier layer formed from silicon oxide or aluminum oxide can be about 25 kgf or more and 55 kgf or less. In another embodiment, the adhesion to the inorganic barrier layer made of silicon nitride may be about 25 kgf or more and 46 kgf or less.
装置用部材、特に、ディスプレイ部材は、周辺環境の気体または液体、例えば、大気中の酸素、水分および／または水蒸気の透過、ならびに電子製品に加工する際に用いられる化学物質の透過が原因で、分解や機能低下が生じ得る。そのため、装置用部材は、封止またはカプセル化される必要がある。このような装置用部材は、有機発光素子（ＯＬＥＤ）、照明装置、フレキシブル（ｆｌｅｘｉｂｌｅ）有機発光素子ディスプレイ、金属センサーパッド、マイクロディスクレーザー、電気変色装置、光変色装置、マイクロ電子機械システム、太陽電池、集積回路、電荷結合装置、発光重合体、発光ダイオード等を含んでもよいが、これに制限されるのではない。 Device members, particularly display members, are due to the permeation of gases or liquids in the surrounding environment, such as atmospheric oxygen, moisture and / or water vapor, and chemicals used in processing electronic products, Degradation and functional degradation can occur. Therefore, the device member needs to be sealed or encapsulated. Such device members include organic light emitting devices (OLEDs), lighting devices, flexible organic light emitting device displays, metal sensor pads, microdisk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells. May include, but is not limited to, integrated circuits, charge coupled devices, light emitting polymers, light emitting diodes, and the like.
光硬化組成物は、装置、特に、フレキシブル（ｆｌｅｘｉｂｌｅ）ディスプレイ装置の封止またはカプセル化用途として使用される有機障壁層を形成できる。 The photocurable composition can form an organic barrier layer used as a sealing or encapsulation application for devices, particularly flexible display devices.
光硬化組成物は、単独で有機発光素子封止用組成物として使用してもよく、有機発光素子封止用組成物に含んでもよく、または通常の添加剤と一緒に有機発光素子封止用組成物に含んでもよい。 The photocurable composition may be used alone as a composition for organic light emitting device sealing, may be included in the composition for organic light emitting device sealing, or for organic light emitting device sealing together with usual additives It may be included in the composition.
以下、本発明の別の実施例の光硬化組成物を説明する。 Hereinafter, the photocurable composition of another Example of this invention is demonstrated.
本発明の他の一実施形態に係る光硬化組成物は、（Ａ）光硬化モノマー、（Ｂ）開始剤、および（Ｃ）非シアノ系シリコン含有光硬化モノマー（以下、（Ｃ）光硬化モノマーとする）を含んでもよい。（Ｃ）光硬化モノマーをさらに含むことを除いては、前記の一実施形態に係る光硬化組成物と実質的に同一である。 A photocurable composition according to another embodiment of the present invention includes (A) a photocurable monomer, (B) an initiator, and (C) a non-cyano silicon-containing photocurable monomer (hereinafter referred to as (C) a photocurable monomer. May be included. (C) Except for further including a photo-curing monomer, it is substantially the same as the photo-curing composition according to the one embodiment.
（Ｃ）光硬化モノマーは、シアノ基を含有せず、シリコンと光硬化官能基（例えば、（メタ）アクリレート基、ビニル基等）を有するモノマーであって、光硬化組成物に含まれ、光硬化組成物の硬化後の信頼性を高めることができる。 (C) The photocuring monomer is a monomer having no cyano group and having silicon and a photocuring functional group (for example, (meth) acrylate group, vinyl group, etc.), and is contained in the photocuring composition. The reliability after hardening of a hardening composition can be improved.
一実施例において、（Ｃ）光硬化モノマーは、非シアノ系シロキサン光硬化モノマーであって、下記一般式３で表すことができる： In one embodiment, the (C) photocuring monomer is a non-cyano siloxane photocuring monomer, which can be represented by the following general formula 3.
（前記一般式３で、
Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５はそれぞれ独立して水素、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数１以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数２以上、２０以下のアルケニル基、置換もしくは非置換の炭素数２以上、２０以下のヘテロアルケニル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、置換もしくは非置換の炭素数１以上、１０以下のアルコキシ基、置換もしくは非置換の炭素数１以上、１０以下のシリル基、置換もしくは非置換の炭素数１以上、１０以下のシリルオキシ基、または下記一般式４であり、
(In the general formula 3,
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 1 or more carbon atoms, A heteroalkyl group of 10 or less, a substituted or unsubstituted carbon number of 2 or more, an alkenyl group of 20 or less, a substituted or unsubstituted carbon number of 2 or more, a heteroalkenyl group of 20 or less, a substituted or unsubstituted carbon number of 6 or more, 20 or less aryl groups, substituted or unsubstituted carbon atoms of 4 or more, 20 or less heteroaryl groups, substituted or unsubstituted carbon atoms of 1 or more and 10 or less, substituted or unsubstituted carbon atoms of 1 or more, 10 The following silyl group, a substituted or unsubstituted silyloxy group having 1 to 10 carbon atoms, or the following general formula 4,
(前記一般式４で、
＊は前記一般式３中のＳｉに対する連結部位で、
Ｒ４は、水素または炭素数１以上、５以下のアルキル基で、
Ｚは、単結合、置換もしくは非置換の炭素数１以上、１０以下のアルキレン基、置換もしくは非置換の炭素数１以上、１０以下のヘテロアルキレン基、置換もしくは非置換の炭素数２以上、２０以下のアルケニレン基、置換もしくは非置換の炭素数２以上、２０以下のヘテロアルケニレン基、置換もしくは非置換の炭素数６以上、２０以下のアリーレン基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリーレン基、または置換もしくは非置換の炭素数１以上、１０以下のアルコキシレン基である）
Ｒ１０、Ｒ１１、Ｒ１２中の少なくとも一つは前記一般式４で、
Ｒ１３、Ｒ１４、Ｒ１５中の少なくとも一つは前記一般式４である）。
(In the general formula 4,
* Is the linking site for Si in the general formula 3,
R 4 is hydrogen or an alkyl group having 1 to 5 carbon atoms,
Z is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 2 or more, 20 The following alkenylene groups, substituted or unsubstituted heteroalkenylene groups having 2 to 20 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted carbon atoms having 4 to 20 carbon atoms Or a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms)
At least one of R 10 , R 11 , and R 12 is the general formula 4,
At least one of R 13 , R 14 and R 15 is the general formula 4).
例えば、Ｒ１０、Ｒ１１、Ｒ１２は、炭素数１以上、５以下のアルキル基またはＺが炭素数１以上、５以下のアルキレン基である前記一般式４で、Ｒ１０、Ｒ１１、Ｒ１２中の一つ以上はＺが炭素数１以上、５以下のアルキレン基である前記式４であり、Ｒ１３、Ｒ１４、Ｒ１５は炭素数１以上、５以下のアルキル基またはＺが炭素数１以上、５以下のアルキレン基である前記式４であり、Ｒ１３、Ｒ１４、Ｒ１５中の一つ以上はＺが炭素数１以上、５以下のアルキレン基である前記一般式４である。 For example, R 10 , R 11 , and R 12 are each an alkyl group having 1 to 5 carbon atoms or Z is an alkylene group having 1 to 5 carbon atoms, and R 10 , R 11 , R 12 At least one of 12 is the formula 4 in which Z is an alkylene group having 1 to 5 carbon atoms, R 13 , R 14 and R 15 are alkyl groups having 1 to 5 carbon atoms or Z is carbon. In Formula 4, which is an alkylene group having a number of 1 or more and 5 or less, and one or more of R 13 , R 14 , and R 15 are represented by Formula 4 in which Z is an alkylene group having 1 to 5 carbon atoms. is there.
具体的に、（Ｃ）光硬化モノマーは、１，３−ビス（３−（メタ）アクリロキシプロピル）テトラメチルジシロキサン等を含む１，３−ビス（メタ）アクリロキシアルキル）テトラアルキルジシロキサン、１，３−ビス（３−（メタ）アクリロキシプロピル）テトラキス（トリメチルシロキシ）ジシロキサン等を含む１，３−ビス（メタ）アクリロキシアルキル）テトラキス（トリアルキルシロキシ）ジシロキサン等を含んでもよく、このとき、アルキルは炭素数１以上、５以下のアルキル基でもよい。 Specifically, (C) the photocuring monomer is 1,3-bis (meth) acryloxyalkyl) tetraalkyldisiloxane including 1,3-bis (3- (meth) acryloxypropyl) tetramethyldisiloxane 1,3-bis (3- (meth) acryloxypropyl) tetrakis (trimethylsiloxy) disiloxane and the like, including 1,3-bis (meth) acryloxyalkyl) tetrakis (trialkylsiloxy) disiloxane and the like In this case, the alkyl may be an alkyl group having 1 to 5 carbon atoms.
（Ｃ）光硬化モノマーは、固形分基準で、光硬化組成物中の約５重量％以上、８０重量％以下、例えば、約５重量％以上、５５重量％以下、約４０重量％以上、５５重量％以下、または約３５重量％以上、４５重量％以下で含んでもよく、具体的には、約３５重量％、３６重量％、３７重量％、３８重量％、３９重量％、４０重量％、４１重量％、４２重量％、４３重量％、４４重量％、４５重量％、４６重量％、４７重量％、４８重量％、４９重量％、５０重量％、５１重量％、５２重量％、５３重量％、５４重量％、または５５重量％であってもよい。前記範囲で、光硬化組成物の光硬化度および付着力がより向上するとともに、装置用部材の信頼性を良くすることができる。 (C) The photocuring monomer is about 5% by weight or more and 80% by weight or less in the photocuring composition, for example, about 5% by weight or more, 55% by weight or less, about 40% by weight or more, based on the solid content. Or about 35 wt% or more and 45 wt% or less, specifically about 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53% %, 54 wt%, or 55 wt%. Within the above range, the degree of photocuring and adhesion of the photocuring composition can be further improved, and the reliability of the device member can be improved.
一具体例において、光硬化組成物は、固形分基準で、（Ａ）＋（Ｂ）＋（Ｃ）中、（Ａ）光硬化モノマー約４０重量％以上、５５重量％以下、（Ｂ）開始剤約１重量％以上、５重量％以下、および（Ｃ）光硬化モノマー約４０重量％以上、５５重量％以下を含んでもよい。前記範囲で、光硬化組成物の光硬化度および付着力をより向上させながら、装置用部材の信頼性を高めることができる。 In one specific example, the photocuring composition is (A) + (B) + (C) based on the solid content, and (A) the photocuring monomer is about 40 wt% or more and 55 wt% or less, (B) start The composition may contain about 1 wt% or more and 5 wt% or less of the agent, and (C) about 40 wt% or more and 55 wt% or less of the photocuring monomer. In the said range, the reliability of the apparatus member can be improved, improving the photocuring degree and adhesive force of a photocurable composition more.
以下、本発明のさらなる他の実施形態に係る光硬化組成物を説明する。 Hereinafter, a photocurable composition according to still another embodiment of the present invention will be described.
本発明のさらなる他の実施形態に係る光硬化組成物は、（Ａ）光硬化モノマー、（Ｂ）開始剤および（Ｄ）非シリコン系光硬化モノマー（以下、（Ｄ）光硬化モノマーとする）を含んでもよい。（Ｄ）光硬化モノマーをさらに含むことを除いては、前記の一実施形態に係る光硬化組成物と実質的に同一である。 A photocurable composition according to still another embodiment of the present invention includes (A) a photocurable monomer, (B) an initiator, and (D) a non-silicon-based photocurable monomer (hereinafter referred to as (D) a photocurable monomer). May be included. (D) It is substantially the same as the photocurable composition according to the embodiment except that it further contains a photocurable monomer.
（Ｄ）光硬化モノマーは、シリコン（ｓｉｌｉｃｏｎ）を含有せず、光硬化官能基（例えば、（メタ）アクリレート基、ビニル基等）を有するモノマーであって、光硬化組成物に含まれ、光硬化組成物の硬化後の信頼性を高めることができる。 (D) The photo-curing monomer is a monomer that does not contain silicon and has a photo-curing functional group (for example, (meth) acrylate group, vinyl group, etc.), and is included in the photo-curing composition. The reliability after hardening of a hardening composition can be improved.
一実施例において、（Ｄ）光硬化モノマーは、多官能型（メタ）アクリレート系モノマーであって、炭素数２以上、２０以下のポリオールのジ（メタ）アクリレート、炭素数２以上、２０以下のポリオールのトリ（メタ）アクリレート、炭素数２以上、２０以下のポリオールのテトラ（メタ）アクリレート、炭素数２以上、２０以下のポリオールのペンタ（メタ）アクリレートまたは炭素数２以上、２０以下のポリオールのヘキサ（メタ）アクリレート中の一つ以上を含んでもよい。具体的に、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート中の一つ以上でもよいが、これに制限されるのではない。 In one embodiment, the (D) photocuring monomer is a polyfunctional (meth) acrylate monomer, and is a di (meth) acrylate of a polyol having 2 to 20 carbon atoms, having 2 to 20 carbon atoms. Tri (meth) acrylate of polyol, tetra (meth) acrylate of polyol having 2 to 20 carbon atoms, penta (meth) acrylate of polyol having 2 to 20 carbon atoms, or polyol having 2 to 20 carbon atoms One or more of hexa (meth) acrylates may be included. Specifically, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( One or more of (meth) acrylate and dipentaerythritol hexa (meth) acrylate may be used, but are not limited thereto.
（Ｄ）光硬化モノマーは、固形分基準で、光硬化組成物中の約５重量％以上、８０重量％以下、例えば、約５重量％以上、５５重量％以下、約４０重量％以上、５５重量％以下、または約５重量％以上、１５重量％以下で含んでもよく、具体的には、約５重量％、６重量％、７重量％、８重量％、９重量％、１０重量％、１１重量％、１２重量％、１３重量％、１４重量％、１５重量％、１６重量％、１７重量％、１８重量％、１９重量％、２０重量％、２１重量％、２２重量％、２３重量％、２４重量％、２５重量％、２６重量％、２７重量％、２８重量％、２９重量％、３０重量％、３１重量％、３２重量％、３３重量％、３４重量％、３５重量％、３６重量％、３７重量％、３８重量％、３９重量％、４０重量％、４１重量％、４２重量％、４３重量％、４４重量％、４５重量％、４６重量％、４７重量％、４８重量％、４９重量％、５０重量％、５１重量％、５２重量％、５３重量％、５４重量％または５５重量％であってもよい。前記範囲で、光硬化組成物の光硬化度および付着力を高め、硬化後の信頼性を高めることができる。 (D) The photocuring monomer is about 5 wt% or more and 80 wt% or less in the photocuring composition, for example, about 5 wt% or more, 55 wt% or less, about 40 wt% or more, based on the solid content. Or about 5 wt% or more and 15 wt% or less, specifically about 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% %, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42% %, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or It may be 55% by weight. In the said range, the photocuring degree and adhesive force of a photocurable composition can be improved, and the reliability after hardening can be improved.
一具体例において、光硬化組成物は、固形分基準で、（Ａ）＋（Ｂ）＋（Ｄ）中、（Ａ）光硬化モノマー約４０重量％以上、５５重量％以下、（Ｂ）開始剤約１重量％以上、５重量％以下、および（Ｄ）光硬化モノマー約４０重量％以上、５５重量％以下を含んでもよい。前記範囲で、光硬化組成物の光硬化度および付着力をより向上させながら、装置用部材の信頼性を高めることができる。 In one specific example, the photocurable composition is (A) + (B) + (D) based on the solid content, and (A) the photocuring monomer is about 40 wt% or more and 55 wt% or less, (B) start The composition may contain about 1 wt% or more and 5 wt% or less of the agent, and (D) about 40 wt% or more and 55 wt% or less of the photocuring monomer. In the said range, the reliability of the apparatus member can be improved, improving the photocuring degree and adhesive force of a photocurable composition more.
以下、本発明のその他の実施形態に係る光硬化組成物を説明する。 Hereinafter, photocurable compositions according to other embodiments of the present invention will be described.
本発明のその他の実施形態に係る光硬化組成物は、（Ａ）光硬化モノマー、（Ｂ）開始剤、（Ｃ）光硬化モノマーおよび（Ｄ）光硬化モノマーを含んでもよい。（Ｃ）光硬化モノマーおよび（Ｄ）光硬化モノマーをさらに含むことを除いては、前記の一実施例の光硬化組成物と実質的に同一である。 The photocurable composition according to another embodiment of the present invention may include (A) a photocurable monomer, (B) an initiator, (C) a photocurable monomer, and (D) a photocurable monomer. Except for further comprising (C) a photocuring monomer and (D) a photocuring monomer, it is substantially the same as the photocuring composition of the above-mentioned one example.
一実施形態において、光硬化組成物は、固形分基準で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）中、（Ａ）光硬化モノマー約４０重量％以上、５５重量％以下、（Ｂ）開始剤約１重量％以上、５重量％以下、（Ｃ）光硬化モノマー３５重量％以上、４５重量％以下、および（Ｄ）光硬化モノマー約５重量％以上、１５重量％以下を含んでもよい。前記範囲で、光硬化組成物の光硬化度および付着力を高め、硬化後の信頼性を改善できる。 In one embodiment, the photocuring composition is (A) + (B) + (C) + (D) in terms of solid content, wherein (A) the photocuring monomer is about 40 wt% or more, 55 wt% or less, (B) an initiator of about 1 wt% or more and 5 wt% or less, (C) a photocuring monomer of 35 wt% or more and 45 wt% or less, and (D) a photocuring monomer of about 5 wt% or more and 15 wt% or less. May be included. In the said range, the photocuring degree and adhesive force of a photocurable composition can be improved, and the reliability after hardening can be improved.
本発明の有機障壁層は、本発明の実施例の光硬化組成物で形成されてもよい。 The organic barrier layer of the present invention may be formed of the photocurable composition of the examples of the present invention.
有機障壁層は、本発明の実施形態に係る光硬化組成物を光硬化させて形成されてもよい。制限されるのではないが、光硬化組成物を約０.１μｍ以上、２０μｍ以下の厚さでコーティングし、約１０Ｊ／ｃｍ２以上、５００Ｊ／ｃｍ２以下で約１秒以上、５０秒以下の時間照射して硬化させてもよい。 The organic barrier layer may be formed by photocuring the photocurable composition according to the embodiment of the present invention. Although not limited, the photocurable composition is coated with a thickness of about 0.1 μm or more and 20 μm or less, and about 10 J / cm 2 or more and 500 J / cm 2 or less for about 1 second or more and 50 seconds or less. It may be cured by irradiation for a period of time.
有機障壁層は、無機障壁層に対する付着力が約２０ｋｇｆ以上、例えば、約２０ｋｇｆ以上、１００ｋｇｆ以下であり、例えば、約２５ｋｇｆ以上、１００ｋｇｆ以下になり得る。よって、有機障壁層は、下記無機障壁層と一緒に障壁スタックを形成して装置用部材の封止用途として用いてもよい。 The organic barrier layer has an adhesion force to the inorganic barrier layer of about 20 kgf or more, for example, about 20 kgf or more and 100 kgf or less, for example, about 25 kgf or more and 100 kgf or less. Therefore, the organic barrier layer may be used for sealing a device member by forming a barrier stack together with the following inorganic barrier layer.
無機障壁層は、光透過性に優れ、水分および／または酸素遮断性に優れた無機層であれば、特に制限されない。例えば、金属、非金属、金属もしくは非金属間の化合物、金属もしくは非金属間の合金、金属もしくは非金属の酸化物、金属もしくは非金属のフッ化物、金属もしくは非金属の窒化物、金属もしくは非金属の炭化物、金属もしくは非金属の酸窒化物、金属もしくは非金属のホウ素化物、金属もしくは非金属の酸ホウ素化物、金属もしくは非金属のシリサイド、またはこれらの混合物でもよい。前記金属または非金属は、シリコン（Ｓｉ）、アルミニウム（Ａｌ）、セレニウム（Ｓｅ）、亜鉛（Ｚｎ）、アンチモン（Ｓｂ）、インジウム（Ｉｎ）、ゲルマニウム（Ｇｅ）、スズ（Ｓｎ）、ビスマス（Ｂｉ）、遷移金属、ランタン族金属等でもよいが、これに制限されるのではない。具体的に、無機障壁層は、ＳｉＯｘ、ＳｉｚＮｘ、ＳｉＯｘＮｙ、ＺｎＳｅ、ＺｎＯ、Ｓｂ２Ｏ３、Ａｌ２Ｏ３、Ｉｎ２Ｏ３、ＳｎＯ２（前記で、ｘは１以上、５以下で、ｙは１以上、５以下で、ｚは１以上、５以下である）等でもよい。無機障壁層において、前記「金属」は、「非金属」で代替してもよい。 The inorganic barrier layer is not particularly limited as long as it is an inorganic layer that is excellent in light transmittance and excellent in moisture and / or oxygen barrier properties. For example, metal, nonmetal, compound between metal or nonmetal, metal or nonmetal alloy, metal or nonmetal oxide, metal or nonmetal fluoride, metal or nonmetal nitride, metal or nonmetal It may be a metal carbide, a metal or nonmetal oxynitride, a metal or nonmetal boride, a metal or nonmetal oxyboride, a metal or nonmetal silicide, or a mixture thereof. The metal or nonmetal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi). ), A transition metal, a lanthanum group metal or the like, but is not limited thereto. Specifically, the inorganic barrier layer includes SiO x , Si z N x , SiO x N y , ZnSe, ZnO, Sb 2 O 3 , Al 2 O 3 , In 2 O 3 , SnO 2 (wherein x is 1 Or more, 5 or less, y is 1 or more and 5 or less, and z is 1 or more and 5 or less. In the inorganic barrier layer, the “metal” may be replaced with “non-metal”.
本発明の障壁スタックは、本発明の実施形態に係る光硬化組成物で形成された有機障壁層および無機障壁層を含んでもよい。 The barrier stack of the present invention may include an organic barrier layer and an inorganic barrier layer formed of the photocurable composition according to the embodiment of the present invention.
無機障壁層は、有機障壁層と相違する無機層で形成し、有機障壁層の効果を補完することができる。 The inorganic barrier layer is formed of an inorganic layer different from the organic barrier layer, and can complement the effect of the organic barrier layer.
無機障壁層および有機障壁層は、真空プロセス、例えば、スパッタリング、化学気相蒸着、金属有機化学気相蒸着、プラズマ化学気相蒸着、蒸発、昇華、電子サイクロトロン共鳴−プラズマ強化化学気相蒸着、またはこれらの組合せで蒸着してもよい。 Inorganic barrier layers and organic barrier layers may be vacuum processes such as sputtering, chemical vapor deposition, metal organic chemical vapor deposition, plasma enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced chemical vapor deposition, or You may vapor-deposit by these combination.
障壁スタックは、前記有機障壁層と無機障壁層とを含むが、障壁スタックの数は制限されない。障壁スタックの組合せは、酸素、水分、水蒸気および／または化学物質に対する透過抵抗性のレベルによって変えることができる。 The barrier stack includes the organic barrier layer and the inorganic barrier layer, but the number of barrier stacks is not limited. The combination of barrier stacks can vary depending on the level of permeation resistance to oxygen, moisture, water vapor and / or chemicals.
障壁スタックにおいて、有機障壁層と無機障壁層は、交互に蒸着してもよい。これは上述の光硬化組成物が有する物性によって生成された有機障壁層の障壁層に対する効果のためである。これにより、有機障壁層と無機障壁層から発生するディスプレイ装置に対する効果を補完または強化できる。 In the barrier stack, the organic barrier layer and the inorganic barrier layer may be alternately deposited. This is because of the effect of the organic barrier layer generated by the physical properties of the above-described photocuring composition on the barrier layer. Thereby, the effect with respect to the display apparatus generated from an organic barrier layer and an inorganic barrier layer can be complemented or strengthened.
例えば、有機障壁層と無機障壁層は、それぞれ約２層以上交互に、全体約１０層以下、例えば、約７層以下（例：２〜７層）で蒸着されてもよく、例えば、無機障壁層−有機障壁層−無機障壁層−有機障壁層−無機障壁層−有機障壁層−無機障壁層の７層構造で形成されてもよい。 For example, the organic barrier layer and the inorganic barrier layer may be alternately deposited with about two or more layers alternately in a total of about 10 layers or less, for example, about 7 layers or less (for example, 2 to 7 layers). It may be formed of a seven-layer structure of layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer-organic barrier layer-inorganic barrier layer.
障壁スタックにおいて、有機障壁層一つの厚さは、約０.１μｍ以上、２０μｍ以下、例えば、約１μｍ以上、２０μｍ以下になり得るものであり、無機障壁層一つの厚さは、約５ｎｍ以上、５００ｎｍ以下、例えば、約５ｎｍ以上、２００ｎｍ以下になり得る。 In the barrier stack, the thickness of one organic barrier layer may be about 0.1 μm or more and 20 μm or less, for example, about 1 μm or more and 20 μm or less, and the thickness of one inorganic barrier layer is about 5 nm or more, It can be 500 nm or less, for example, about 5 nm or more and 200 nm or less.
障壁スタックは、薄膜封止剤であって、厚さは約５μｍ以下、例えば、約１.５μｍ以上、５μｍ以下になり得る。 The barrier stack is a thin film encapsulant and can have a thickness of about 5 μm or less, for example, about 1.5 μm or more and 5 μm or less.
本発明の封止化された装置は、装置用部材、および装置用部材上に形成され、有機障壁層および無機障壁層を含む障壁スタックを含み、前記有機障壁層は、本発明の実施形態に係る光硬化組成物で形成されてもよい。 The sealed device of the present invention includes a device member and a barrier stack formed on the device member and including an organic barrier layer and an inorganic barrier layer, wherein the organic barrier layer is an embodiment of the present invention. You may form with the photocuring composition which concerns.
装置用部材は、有機発光素子（ＯＬＥＤ）、照明装置、フレキシブル（ｆｌｅｘｉｂｌｅ）有機発光素子ディスプレイ、金属センサーパッド、マイクロディスクレーザー、電気変色装置、光変色装置、マイクロ電子機械システム、太陽電池、集積回路、電荷結合装置、発光重合体、発光ダイオード等を含んでもよいが、これに制限されるのではない。 Device members include organic light emitting devices (OLED), lighting devices, flexible organic light emitting device displays, metal sensor pads, microdisk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, solar cells, integrated circuits , Charge coupled devices, light emitting polymers, light emitting diodes, and the like, but are not limited thereto.
封止化された装置は、例えば、ディスプレイ装置、有機発光素子表示装置等でもよいが、これに制限されるのではない。 The sealed device may be, for example, a display device, an organic light emitting element display device, or the like, but is not limited thereto.
以下、図１を参考し、本発明の一実施形態に係る封止化された有機発光素子表示装置を説明する。図１は、本発明の一実施形態に係る封止化された有機発光素子表示装置の断面図である。 Hereinafter, a sealed organic light emitting device display device according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view of a sealed organic light emitting device display apparatus according to an embodiment of the present invention.
図１を参照すると、本発明の一実施形態に係る封止化された有機発光素子表示装置１００は、基板１０；基板１０上に形成された有機発光素子２０；および有機発光素子２０上に形成され、無機障壁層３１と有機障壁層３２とで構成される障壁スタック３０を含み、有機発光素子２０と無機障壁層３１は互いに接触し、有機障壁層３２は、本発明の一実施形態に係る光硬化組成物で形成されてもよい。 Referring to FIG. 1, a sealed organic light emitting device display device 100 according to an embodiment of the present invention is formed on a substrate 10; an organic light emitting device 20 formed on the substrate 10; and an organic light emitting device 20. The organic light emitting device 20 and the inorganic barrier layer 31 are in contact with each other, and the organic barrier layer 32 is in accordance with an embodiment of the present invention. You may form with a photocuring composition.
基板１０は、装置用部材が積層できる基板であれば、特に制限されない。例えば、透明ガラス、プラスチックシート、シリコンまたは金属基板等のような物質で構成されてもよい。 The board | substrate 10 will not be restrict | limited especially if the apparatus member can be laminated | stacked. For example, it may be made of a material such as transparent glass, plastic sheet, silicon or metal substrate.
有機発光素子２０は図１で図示されていないが、有機発光素子表示装置に通常用いられるもので、第１の電極、第２の電極、および第１の電極と第２の電極との間に形成された有機発光膜を含んでもよい。 The organic light emitting element 20 is not shown in FIG. 1, but is usually used in an organic light emitting element display device, and includes a first electrode, a second electrode, and a gap between the first electrode and the second electrode. The formed organic light emitting film may be included.
無機障壁層３１と有機障壁層３２の形成方法は、制限されないが、真空プロセス、例えば、スパッタリング、化学気相蒸着、プラズマ化学気相蒸着、蒸発、昇華、電子サイクロトロン共鳴−プラズマ強化化学気相蒸着、またはこれらの組合せで形成されてもよい。 The formation method of the inorganic barrier layer 31 and the organic barrier layer 32 is not limited, but a vacuum process such as sputtering, chemical vapor deposition, plasma chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced chemical vapor deposition. Or a combination thereof.
以下、図２を参考し、本発明の他の一実施形態に係る封止化された有機発光素子表示装置を説明する。図２は、本発明の他の一実施形態に係る封止化された有機発光素子表示装置の断面図である。 Hereinafter, a sealed organic light emitting device display device according to another embodiment of the present invention will be described with reference to FIG. FIG. 2 is a cross-sectional view of a sealed organic light emitting device display device according to another embodiment of the present invention.
図２を参照すると、本発明の別の実施例の封止化された有機発光素子表示装置２００は、基板１０；基板１０上に形成された有機発光素子２０；および有機発光素子２０上に形成され、無機障壁層３１と有機障壁層３２とで構成される障壁スタック３０を含み、有機発光素子２０と無機障壁層３１との間に空間４０が形成され、有機障壁層３２は、本発明の実施例の光硬化組成物で形成されてもよい。有機発光素子２０と無機障壁層３１とが互いに接触せず、空間４０が形成されたことを除いては前記の一実施形態に係る封止化された有機発光素子表示装置と実質的に同一である。 Referring to FIG. 2, a sealed organic light emitting device display device 200 according to another embodiment of the present invention includes a substrate 10; an organic light emitting device 20 formed on the substrate 10; and an organic light emitting device 20. Including a barrier stack 30 composed of an inorganic barrier layer 31 and an organic barrier layer 32, and a space 40 is formed between the organic light emitting device 20 and the inorganic barrier layer 31, and the organic barrier layer 32 is You may form with the photocuring composition of an Example. The organic light emitting device 20 and the inorganic barrier layer 31 are not in contact with each other and are substantially the same as the sealed organic light emitting device display device according to the embodiment except that the space 40 is formed. is there.
（発明を実施するための形態）
以下、本発明の好ましい実施形態により本発明の構成および作用をより詳しく説明する。但し、これは本発明の好ましい例示として提示するものであり、如何なる意味でもこれによって本発明が制限されると解釈してはならない。
(Mode for carrying out the invention)
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, this is presented as a preferred illustration of the present invention and should not be construed as limiting the invention in any way.
〔合成例１：シアノ基含有シリコン系光硬化モノマーの製造〕
２−ヒドロキシエチルメタクリレート（２−Ｈｙｄｒｏｘｙｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ）（Ｃ６Ｈ１０Ｏ３、ＴＣＩ社）１５０．０６ｇとトリエチルアミン（ｔｒｉｅｔｈｙｌａｍｉｎｅ）（Ｃ６Ｈ１５Ｎ、ＴＣＩ社）１１３．９０ｇ、メチレンクロライド（ｍｅｔｈｙｌｅｎｅｃｈｌｏｒｉｄｅ）（ＣＨ２Ｃｌ２、ＴＣＩ社）２００ｇを温度制御が可能なジャケット型反応器に入れて常温で３０分間撹拌した。その後、反応器を０℃で冷却した状態で、３−シアノプロピルメチルジクロロシラン（３−ｃｙａｎｏｐｒｏｐｙｌｍｅｔｈｙｌｄｉｃｈｌｏｒｏｓｉｌａｎｅ）（Ｃ５Ｈ９Ｃｌ２ＮＳｉ、Ｇｅｌｅｓｔ社）１００．００ｇを１時間にわたって徐々に反応器に滴下した。投入が終わると、反応器を常温に上昇した状態で、６時間撹拌した後、反応を終了した。反応器内の溶液をｐＨが中性になるまで水で中和し、次いで、減圧して乾燥させた後、下記式５の最終生成物を得た。得られた生成物をＮＭＲとＧＣとで最終構造を分析して確認した。
[Synthesis Example 1: Production of cyano group-containing silicon-based photocuring monomer]
150.06 g of 2-hydroxyethylmethacrylate (C 6 H 10 O 3 , TCI) and triethylamine (C 6 H 15 N, TCI) 113.90 g, methylene chloride (methylethylene chloride) 2 Cl 2, TCI Inc.) 200 g placed in a jacketed reactor whose temperature can be controlled was stirred for 30 minutes at room temperature. Then, with the reactor cooled at 0 ° C., 100.00 g of 3-cyanopropylmethyldichlorosilane (C 5 H 9 Cl 2 NSi, Gelest) was gradually dropped into the reactor over 1 hour. did. When the addition was completed, the reaction was completed after stirring for 6 hours while the reactor was raised to room temperature. The solution in the reactor was neutralized with water until the pH became neutral, and then dried under reduced pressure to obtain the final product of the following formula 5. The obtained product was confirmed by analyzing the final structure by NMR and GC.
〔合成例２:シアノ基含有シリコン系光硬化モノマー〕
３−シアノプロピルメチルジクロロシラン（３−ｃｙａｎｏｐｒｏｐｙｌｍｅｔｈｙｌｄｉｃｈｌｏｒｏｓｉｌａｎｅ）の代わりに３−シアノプロピルフェニルジクロロシラン（３−ｃｙａｎｏｐｒｏｐｙｌｐｈｅｎｙｌｄｉｃｈｌｏｒｏｓｉｌａｎｅ）（Ｃ１０Ｈ１１Ｃｌ２ＮＳｉ、Ｇｅｌｅｓｔ社）を用いたことを除いては、合成例１と同一の方法を実施して下記式６の最終生成物を得て、ＮＭＲとＧＣとで最終構造を分析して確認した。
[Synthesis Example 2: Cyano group-containing silicon-based photocuring monomer]
Synthesis example except that 3-cyanopropylphenyldichlorosilane (C 10 H 11 Cl 2 NSi, Gelest) was used instead of 3-cyanopropylmethyldichlorosilane (3-cyanopropylphenyldichlorosilane) The same method as 1 was performed to obtain the final product of the following formula 6, and the final structure was analyzed and confirmed by NMR and GC.
〔合成例３:シアノ基含有シリコン系光硬化モノマー〕
２−（ヒドロキシエチルメタクリレート（２−Ｈｙｄｒｏｘｙｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ）の代わりに、４−ヒドロキシブチルアクリレート（４−ｈｙｄｒｏｘｙｂｕｔｙｌａｃｒｙｌａｔｅ）（Ｃ７Ｈ１２Ｏ３、ＴＣＩ社）を用いたことを除いては、合成例１と同一の方法を実施して下記式７の最終生成物を得て、ＮＭＲとＧＣとで最終構造を分析して確認した。
[Synthesis Example 3: Cyano group-containing silicon-based photocuring monomer]
The same as Synthesis Example 1 except that 4-hydroxybutyl acrylate (C 7 H 12 O 3 , TCI) was used instead of 2- (hydroxyethyl methacrylate). The final product of the following formula 7 was obtained by carrying out the above method, and the final structure was analyzed and confirmed by NMR and GC.
〔合成例４：シアノ基含有シリコン系光硬化モノマー〕
２−ヒドロキシエチルメタクリレート（２−Ｈｙｄｒｏｘｙｅｔｈｙｌｍｅｔｈａｃｒｙｌａｔｅ）（Ｃ６Ｈ１０Ｏ３、ＴＣＩ社）７５．０３ｇとトリエチルアミン（ｔｒｉｅｔｈｙｌａｍｉｎｅ）（Ｃ６Ｈ１５Ｎ、ＴＣＩ社）５６．９５ｇ、メチレンクロライド（ｍｅｔｈｙｌｅｎｅｃｈｌｏｒｉｄｅ）（ＣＨ２Ｃｌ２、ＴＣＩ社）１００ｇを温度制御が可能なジャケット型反応器に入れて常温で３０分間撹拌した。その後、反応器を０℃で冷却した状態で、３−シアノプロピルジメチルクロロシラン（３−ｃｙａｎｏｐｒｏｐｙｌｄｉｍｅｔｈｙｌｃｈｌｏｒｏｓｉｌａｎｅ）（Ｃ６Ｈ１２ＣｌＮＳｉ、Ｇｅｌｅｓｔ社）１００．００ｇを１時間にわたって徐々に反応器に滴下した。投入が終わると、反応器を常温に上昇した状態で、６時間撹拌した後、反応を終了した。反応器内の有機溶液をｐＨが中性になるまで水で中和し、次いで、減圧して乾燥した後、下記式８の最終生成物を得て、得られた生成物をＮＭＲとＧＣとで最終構造を分析して確認した。
[Synthesis Example 4: Cyano group-containing silicon-based photocuring monomer]
2-Hydroxyethylmethacrylate (C 6 H 10 O 3 , TCI) 75.03 g and triethylamine (C 6 H 15 N, TCI) 56.95 g, methylene chloride (methylethylene chloride) 2 Cl 2, TCI Inc.) 100 g placed in a jacketed reactor capable temperature control was stirred for 30 minutes at room temperature. Thereafter, with the reactor cooled at 0 ° C., 100.00 g of 3-cyanopropyldimethylchlorosilane (C 6 H 12 ClNSi, Gelest) was gradually added dropwise to the reactor over 1 hour. When the addition was completed, the reaction was completed after stirring for 6 hours while the reactor was raised to room temperature. The organic solution in the reactor is neutralized with water until the pH becomes neutral, and then dried under reduced pressure to obtain the final product of the following formula 8. The obtained product is obtained by NMR and GC. The final structure was analyzed and confirmed.
（Ａ）シアノ基含有シリコン系光硬化モノマー：（Ａ−１）式５、（Ａ−２）式６、（Ａ−３）式７、（Ａ−４）式８
（Ｂ）開始剤：Ｄａｒｏｃｕｒ ＴＰＯ（ＢＡＳＦ社）
（Ｃ）非シアノ系シリコン含有光硬化モノマー：１，３−ビス（３−メタアクリロキシプロピル）テトラメチルジシロキサン
（Ｄ）非シリコン系光硬化モノマー：１，６−ヘキサンジオールジアクリレート
〔実施例１から１０、および比較例１から２〕
成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）を下記表２に記載されている含量（単位：重量部、固形分基準)で混合し、シェーカーを用いて３時間混合して光硬化組成物を製造した。
(A) Cyano group-containing silicon-based photocurable monomer: (A-1) Formula 5, (A-2) Formula 6, (A-3) Formula 7, and (A-4) Formula 8
(B) Initiator: Darocur TPO (BASF)
(C) Non-cyano silicon-containing photocuring monomer: 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane (D) Non-silicon photocuring monomer: 1,6-hexanediol diacrylate [Examples] 1 to 10 and Comparative Examples 1 to 2]
Ingredients (A), (B), (C), (D) were mixed in the content (unit: parts by weight, based on solid content) described in Table 2 below, mixed for 3 hours using a shaker, and light. A cured composition was produced.
実施例と比較例において、製造した光硬化組成物に対して下記の物性を評価し、その結果を下記表２に示した。 In Examples and Comparative Examples, the following physical properties were evaluated for the produced photocured compositions, and the results are shown in Table 2 below.
（１）光硬化度（％）：光硬化組成物に対してＦＴ−ＩＲ（ＮＩＣＯＬＥＴ４７００，Ｔｈｅｒｍｏ社）を用いて、１６３５ｃｍ−１付近（Ｃ＝Ｃ）および１７２０ｃｍ−１付近（Ｃ＝Ｏ）における吸収ピークの強度を測定した。ガラス基板上に組成物を厚さ５μｍで塗布し、１００Ｊ／ｃｍ２で１０秒間照射してＵＶ硬化して、２０ｃｍ×２０ｃｍ×５μｍ（横×縦×厚さ）の試片を得た。硬化したフィルムを取り出し、ＦＴ−ＩＲ（ＮＩＣＯＬＥＴ４７００，Ｔｈｅｒｍｏ社）を用いて１６３５ｃｍ−１付近（Ｃ＝Ｃ）および１７２０ｃｍ−１付近（Ｃ＝Ｏ）における吸収ピークの強度を測定した。光硬化度は下記数式１に従って計算した。 (1) Degree of photocuring (%): FT-IR (NICOLET4700, Thermo) was used for the photocuring composition at around 1635 cm −1 (C═C) and around 1720 cm −1 (C═O). The intensity of the absorption peak was measured. The composition was applied on a glass substrate at a thickness of 5 μm, irradiated with UV at 100 J / cm 2 for 10 seconds, and UV cured to obtain a test piece of 20 cm × 20 cm × 5 μm (width × length × thickness). The cured film was taken out, and the intensity of absorption peaks in the vicinity of 1635 cm −1 (C═C) and 1720 cm −1 (C═O) was measured using FT-IR (NICOLET 4700, Thermo). The photocuring degree was calculated according to the following formula 1.
（前記数式１において、
Ａは硬化したフィルムの１７２０ｃｍ−１付近における吸収ピークの強度に対する１６３５ｃｍ-１付近における吸収ピークの強度の比であり、
Ｂは組成物の１７２０ｃｍ−１付近における吸収ピークの強度に対する１６３５ｃｍ−１付近における吸収ピークの強度の比である）。
(In Equation 1 above,
A is the ratio of the intensity of the absorption peak near 1635 cm −1 to the intensity of the absorption peak near 1720 cm −1 of the cured film,
B is the ratio of the intensity of the absorption peak near 1635 cm −1 to the intensity of the absorption peak near 1720 cm −1 of the composition).
(２)付着力１（ｋｇｆ）：ガラスとガラスとの間の付着力を測定するための方法であり、ダイシェア強度（Ｄｉｅ ｓｈｅａｒ ｓｔｒｅｎｇｔｈ）を測定する方法と同じ方法で接着力を測定した。接着力測定器であるＤａｇｅ Ｓｅｒｉｅｓ ４０００ＰＸＹを用いて、２５℃で２００ｋｇｆの力で上部ガラスを側面から押して剥離する力を測定した。下部ガラスの大きさは２ｃｍ×２ｃｍ×１ｍｍ（横×縦×厚さ）とし、上部ガラスの大きさは１．５ｃｍ×１．５ｃｍ×１ｍｍ（横×縦×厚さ）で製作し、粘着層の厚さは５００μｍとした。 (2) Adhesive force 1 (kgf): This is a method for measuring the adhesive force between glasses, and the adhesive force was measured by the same method as the method of measuring die shear strength. Using a Dage Series 4000PXY, which is an adhesive force measuring device, the force to push the upper glass from the side with a force of 200 kgf at 25 ° C. was measured. The size of the lower glass is 2cm x 2cm x 1mm (width x length x thickness), and the size of the upper glass is 1.5cm x 1.5cm x 1mm (width x height x thickness) The thickness of was set to 500 μm.
(３)付着力２（ｋｇｆ）：シリコン窒化物とシリコン窒化物の付着力を測定するための方法であり、ダイシェア強度（Ｄｉｅ ｓｈｅａｒ ｓｔｒｅｎｇｔｈ）を測定する方法と同じ方法で接着力を測定した。接着力の測定器であるＤａｇｅ Ｓｅｒｉｅｓ ４０００ＰＸＹを用いて、２５℃で２００ｋｇｆの力で上部ガラスを側面から押して剥離する力を測定した。下部ガラスの大きさは２ｃｍ×２ｃｍ×１ｍｍ（横×縦×厚さ）とし、上部ガラスの大きさは１．５ｃｍ×１．５ｃｍ×１ｍｍ（横×縦×厚さ）で製作し、粘着層の厚さは５００μｍとした。粘着層が位置する下部ガラスと上部ガラスは共に、シリコン窒化物をコーティングした。 (3) Adhesive force 2 (kgf): This is a method for measuring the adhesive force between silicon nitride and silicon nitride, and the adhesive force was measured by the same method as the method of measuring die shear strength. Using a Dage Series 4000PXY, which is an adhesive force measuring device, the force to push the upper glass from the side with a force of 200 kgf at 25 ° C. was measured. The size of the lower glass is 2cm x 2cm x 1mm (width x length x thickness), and the size of the upper glass is 1.5cm x 1.5cm x 1mm (width x height x thickness) The thickness of was set to 500 μm. Both the lower glass and the upper glass where the adhesive layer is located were coated with silicon nitride.
(４)信頼性：信頼性評価用デバイスは、通常の方法で製造してもよい。基板上に素子を蒸着し、次いで無機障壁層を形成した。光硬化組成物をスピンコート、スリットコート等の方法を用いて１μｍ以上５μｍの厚さに塗布し、光を照射して有機障壁層を形成した。有機障壁層と無機障壁層は交互に、計３回蒸着した。用意したパッケージを８５℃、相対湿度８５％ＲＨの条件で静置して、顕微鏡を用いてパッケージ内部に変色が発生する時間を確認するために観察を行い、信頼性を判別した。下記表１のように変色発生時点を基準として、信頼性の点数を評価する。点数が高いほど、信頼性が高いことを意味する。 (4) Reliability: The reliability evaluation device may be manufactured by a normal method. An element was deposited on the substrate, and then an inorganic barrier layer was formed. The photocurable composition was applied to a thickness of 1 μm or more and 5 μm using a method such as spin coating or slit coating, and light was irradiated to form an organic barrier layer. The organic barrier layer and the inorganic barrier layer were alternately deposited three times in total. The prepared package was allowed to stand at 85 ° C. and a relative humidity of 85% RH, and was observed using a microscope to confirm the time when discoloration occurred inside the package, thereby determining the reliability. As shown in Table 1 below, the reliability score is evaluated based on the color change occurrence point. The higher the score, the higher the reliability.
前記表２に示したように、本発明に係る光硬化組成物は、光硬化度が高いだけでなく、硬化後のシリコン酸化物やシリコン窒化物等の無機障壁層に対する付着力が高く、素子パッケージで製作したときの過酷な条件においても信頼性が高かった。一方で、本発明に係るシアノ基含有シリコン系光硬化モノマーを含まない比較例１および比較例２の組成物は、光硬化度は高いものの、無機障壁層に対する付着力が低く、信頼性が低いため、本発明の効果を具現することはできなかった。 As shown in Table 2, the photocuring composition according to the present invention not only has a high degree of photocuring, but also has a high adhesion to an inorganic barrier layer such as silicon oxide and silicon nitride after curing, The reliability was high even under the harsh conditions when the package was manufactured. On the other hand, the compositions of Comparative Example 1 and Comparative Example 2 that do not contain the cyano group-containing silicon-based photocuring monomer according to the present invention have a high degree of photocuring, but have low adhesion to the inorganic barrier layer and low reliability. Therefore, the effect of the present invention could not be realized.
本発明は、前記実施例および図面によって限定されるものではなく、相違する多様な形態になってもよい。そのため、以上で記述した実施例と図面は、全ての面において例示的なものであり、限定的なものではないことを理解しなければならない。 The present invention is not limited to the above-described embodiments and drawings, and may take various forms. Therefore, it should be understood that the embodiments and drawings described above are illustrative in all aspects and not limiting.
Claims (15)
Ｒ１およびＲ２はそれぞれ独立して水素、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、置換もしくは非置換の炭素数７以上、２１以下のアリールアルキル基、置換もしくは非置換の炭素数１以上、１０以下のシリル基または下記一般式２であり、
Ｒ１およびＲ２中の少なくとも一つは前記一般式２であり、
Ｒ３は、水素、水酸基、ハロゲン、−ＮＲ’Ｒ”（Ｒ’、Ｒ”はそれぞれ独立して水素、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、または置換もしくは非置換の炭素数７以上、２１以下のアリールアルキル基である）、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、置換もしくは非置換の炭素数７以上、２１以下のアリールアルキル基、または置換もしくは非置換の炭素数１以上、１０以下のシリル基であり、
Ｘ１、Ｘ２はそれぞれ独立して、単結合または酸素であり、
Ｘ３、Ｙ１およびＹ２はそれぞれ独立して、置換もしくは非置換の炭素数１以上、１０以下のアルキレン基、置換もしくは非置換の炭素数２以上、１０以下のヘテロアルキレン基、置換もしくは非置換の炭素数６以上、２０以下のアリーレン基、置換もしくは非置換の炭素数７以上、２１以下のアリールアルキレン基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリーレン基、または置換もしくは非置換の炭素数３以上、１０以下のシクロアルキレン基である）。 A photocurable composition comprising (A) a cyano group-containing silicon-based photocurable monomer represented by the following general formula 1 and (B) an initiator:
R 1 and R 2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 10 carbon atoms, substituted or unsubstituted Aryl group having 6 or more and 20 or less carbon atoms, substituted or unsubstituted heteroaryl group having 4 or more and 20 or less carbon atoms, substituted or unsubstituted arylalkyl group having 7 or more and 21 or less carbon atoms, substituted or unsubstituted A silyl group having 1 to 10 carbon atoms or the following general formula 2;
At least one of R 1 and R 2 is the general formula 2,
R 3 represents hydrogen, a hydroxyl group, halogen, —NR′R ″ (R ′ and R ″ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted carbon; A heteroalkyl group having 2 or more and 10 or less, a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, a substituted or unsubstituted heteroaryl group having 4 or more and 20 or less carbon atoms, or a substituted or unsubstituted group An arylalkyl group having 7 to 21 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 10 carbon atoms, substituted or unsubstituted An unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 7 or more carbon atoms, 21 Arylalkyl group below, or a substituted or unsubstituted C 1 or more carbon atoms, is 10 or less of the silyl group,
X 1 and X 2 are each independently a single bond or oxygen,
X 3 , Y 1 and Y 2 are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, substituted or unsubstituted A substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted arylene group having 7 to 21 carbon atoms, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, An unsubstituted cycloalkylene group having 3 to 10 carbon atoms).
Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５はそれぞれ独立して水素、置換もしくは非置換の炭素数１以上、１０以下のアルキル基、置換もしくは非置換の炭素数１以上、１０以下のヘテロアルキル基、置換もしくは非置換の炭素数２以上、２０以下のアルケニル基、置換もしくは非置換の炭素数２以上、２０以下のヘテロアルケニル基、置換もしくは非置換の炭素数６以上、２０以下のアリール基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリール基、置換もしくは非置換の炭素数１以上、１０以下のアルコキシ基、置換もしくは非置換の炭素数１以上、１０以下のシリル基、置換もしくは非置換の炭素数１以上、１０以下のシリルオキシ基、または下記一般式４であり、
＊は前記一般式３中のＳｉに対する連結部位で、
Ｒ４は、水素または炭素数１以上、５以下のアルキル基で、
Ｚは、単結合、置換もしくは非置換の炭素数１以上、１０以下のアルキレン基、置換もしくは非置換の炭素数１以上、１０以下のヘテロアルキレン基、置換もしくは非置換の炭素数２以上、２０以下のアルケニレン基、置換もしくは非置換の炭素数２以上、２０以下のヘテロアルケニレン基、置換もしくは非置換の炭素数６以上、２０以下のアリーレン基、置換もしくは非置換の炭素数４以上、２０以下のヘテロアリーレン基、または置換もしくは非置換の炭素数１以上、１０以下のアルコキシレン基であり、
Ｒ１０、Ｒ１１、Ｒ１２中の少なくとも一つは前記一般式４で、
Ｒ１３、Ｒ１４、Ｒ１５中の少なくとも一つは前記一般式４である）。 The photocurable composition according to claim 4, wherein the (C) non-cyano silicon-containing photocuring monomer is represented by the following general formula 3.
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 1 or more carbon atoms, A heteroalkyl group of 10 or less, a substituted or unsubstituted carbon number of 2 or more, an alkenyl group of 20 or less, a substituted or unsubstituted carbon number of 2 or more, a heteroalkenyl group of 20 or less, a substituted or unsubstituted carbon number of 6 or more, 20 or less aryl groups, substituted or unsubstituted carbon atoms of 4 or more, 20 or less heteroaryl groups, substituted or unsubstituted carbon atoms of 1 or more and 10 or less, substituted or unsubstituted carbon atoms of 1 or more, 10 The following silyl group, a substituted or unsubstituted silyloxy group having 1 to 10 carbon atoms, or the following general formula 4,
* Is the linking site for Si in the general formula 3,
R 4 is hydrogen or an alkyl group having 1 to 5 carbon atoms,
Z is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 2 or more, 20 The following alkenylene groups, substituted or unsubstituted heteroalkenylene groups having 2 to 20 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted carbon atoms having 4 to 20 carbon atoms A heteroarylene group, or a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms,
At least one of R 10 , R 11 , and R 12 is the general formula 4,
At least one of R 13 , R 14 and R 15 is the general formula 4).
前記装置用部材上に形成され、無機障壁層と、請求項１〜１１のいずれか１項に記載の光硬化組成物で形成される有機障壁層とを含む障壁スタック（ｂａｒｒｉｅｒ ｓｔａｃｋ）を含む、封止化された装置。 A barrier stack formed on the device member and comprising an inorganic barrier layer and an organic barrier layer formed from the photocurable composition according to claim 1. a sealed device comprising a stack.
前記金属または非金属は、シリコン（Ｓｉ）、アルミニウム（Ａｌ）、セレニウム（Ｓｅ）、亜鉛（Ｚｎ）、アンチモン（Ｓｂ）、インジウム（Ｉｎ）、ゲルマニウム（Ｇｅ）、スズ（Ｓｎ）、ビスマス（Ｂｉ）、遷移金属、ランタン族金属中の一つ以上を含む、請求項１３に記載の封止化された装置。 The inorganic barrier layer is made of metal, nonmetal, compound of metal or nonmetal, metal or nonmetal alloy, metal or nonmetal oxide, metal or nonmetal fluoride, metal or nonmetal nitride. A metal or non-metal carbide, a metal or non-metal oxynitride, a metal or non-metal boride, a metal or non-metal oxyboride, a metal or non-metal silicide, or a mixture thereof,
The metal or nonmetal is silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi). 14) The encapsulated device of claim 13, comprising one or more of a transition metal, a lanthanum group metal.
The device member is a flexible organic light emitting device, organic light emitting device, lighting device, metal sensor pad, microdisk laser, electrochromic device, photochromic device, microelectromechanical system, solar cell, integrated circuit, charge coupling 14. The encapsulated device of claim 13, which is a device, a light emitting polymer, or a light emitting diode.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2013-0074954 | 2013-06-27 | ||
| KR20130074954 | 2013-06-27 | ||
| KR1020130157550A KR101696965B1 (en) | 2013-06-27 | 2013-12-17 | Photocurable composition and encapsulated apparatus comprising the same |
| KR10-2013-0157550 | 2013-12-17 | ||
| PCT/KR2013/011783 WO2014208849A1 (en) | 2013-06-27 | 2013-12-18 | Photocurable composition and encapsualted device including same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016529345A true JP2016529345A (en) | 2016-09-23 |
| JP6178920B2 JP6178920B2 (en) | 2017-08-09 |
Family
ID=52475307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016523615A Active JP6178920B2 (en) | 2013-06-27 | 2013-12-18 | Photocuring composition and encapsulated device comprising the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6178920B2 (en) |
| KR (1) | KR101696965B1 (en) |
| CN (1) | CN105143316B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015189977A (en) * | 2014-03-28 | 2015-11-02 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． | Composition for encapsulation of organic light emitting element, and organic light emitting display |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018124597A1 (en) * | 2016-12-27 | 2018-07-05 | 모멘티브퍼포먼스머티리얼스코리아 주식회사 | Encapsulation composition for organic electronic device, and encapsulation formed using same |
| CN109037460A (en) * | 2017-06-08 | 2018-12-18 | 上海和辉光电有限公司 | A kind of flexible substrate and preparation method thereof |
| CN108037628A (en) * | 2017-12-25 | 2018-05-15 | 兰州空间技术物理研究所 | Electrochomeric films that a kind of performance is stablized and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63179881A (en) * | 1987-01-19 | 1988-07-23 | Shin Etsu Chem Co Ltd | Organosilicon compound |
| JPH06180456A (en) * | 1992-10-14 | 1994-06-28 | Sekisui Finechem Co Ltd | Spacer for liquid crystal device and liquid crystal device using same |
| JP2000230021A (en) * | 1999-02-09 | 2000-08-22 | Toray Ind Inc | Monomer, and polymer and plastic molding produced therefrom |
| JP2011511100A (en) * | 2008-01-11 | 2011-04-07 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate containing the same, and liquid crystal display device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995252B (en) * | 2006-12-21 | 2010-05-12 | 大连轻工业学院 | Photocured cyanoacrylate adhesives |
| JP5292704B2 (en) | 2007-02-23 | 2013-09-18 | 横浜ゴム株式会社 | SEALING COMPOSITION FOR LIGHT EMITTING ELEMENT, CURED PRODUCT THEREOF, AND LIGHT EMITTING ELEMENT SEALING BODY |
| KR100987369B1 (en) * | 2008-02-04 | 2010-10-13 | 신재환 | Hybrid coating of and Manufacturing method of gas barrier film of high hardness by coating and film thereby |
| KR20100060143A (en) * | 2008-11-27 | 2010-06-07 | 주식회사 동진쎄미켐 | Photocurable silicon resin for sealing of electric device |
| JP5823277B2 (en) | 2011-12-12 | 2015-11-25 | 富士フイルム株式会社 | Barrier laminate, gas barrier film and device using the same |
-
2013
- 2013-12-17 KR KR1020130157550A patent/KR101696965B1/en active IP Right Grant
- 2013-12-18 JP JP2016523615A patent/JP6178920B2/en active Active
- 2013-12-18 CN CN201380075904.4A patent/CN105143316B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63179881A (en) * | 1987-01-19 | 1988-07-23 | Shin Etsu Chem Co Ltd | Organosilicon compound |
| JPH06180456A (en) * | 1992-10-14 | 1994-06-28 | Sekisui Finechem Co Ltd | Spacer for liquid crystal device and liquid crystal device using same |
| JP2000230021A (en) * | 1999-02-09 | 2000-08-22 | Toray Ind Inc | Monomer, and polymer and plastic molding produced therefrom |
| JP2011511100A (en) * | 2008-01-11 | 2011-04-07 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate containing the same, and liquid crystal display device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015189977A (en) * | 2014-03-28 | 2015-11-02 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． | Composition for encapsulation of organic light emitting element, and organic light emitting display |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105143316B (en) | 2018-03-02 |
| KR20150001581A (en) | 2015-01-06 |
| JP6178920B2 (en) | 2017-08-09 |
| CN105143316A (en) | 2015-12-09 |
| KR101696965B1 (en) | 2017-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6592005B2 (en) | Composition for sealing organic light emitting element and organic light emitting element display device manufactured using the same | |
| US9534069B2 (en) | Photocurable composition, barrier layer comprising same, and encapsulated device comprising same | |
| KR101534334B1 (en) | Photocurable composition and apparatus comprising a protective layer formed using the same | |
| EP2924085B1 (en) | Composition for encapsulation of organic light emitting diode and organic light emitting diode display manufactured using the same | |
| CN108137755B (en) | Composition for encapsulating organic light emitting element and organic light emitting element display device manufactured therefrom | |
| KR102008177B1 (en) | Composition for encapsulating organic light emitting device and organic light emitting display using prepared the same | |
| US11539025B2 (en) | Composition for organic light emitting diode encapsulation and organic light emitting diode display manufactured therefrom | |
| US10233350B2 (en) | Photocurable composition and enveloped device including same | |
| KR101611001B1 (en) | Composition for encapsulation, barrier layer comprising the same and encapsulated apparatus comprising the same | |
| JP2016509620A (en) | SEALING COMPOSITION, BARRIER LAYER CONTAINING THE SAME, AND SEALED DEVICE CONTAINING THE SAME | |
| JP6178920B2 (en) | Photocuring composition and encapsulated device comprising the same | |
| KR20160097168A (en) | Photocurable composition, barrier layer comprising the same and encapsulated apparatus comprising the same | |
| US10392459B2 (en) | Photocurable composition and device including barrier layer formed from composition | |
| KR20180102038A (en) | Photo-curable composition, organic protective layer comprising the same, and apparatus comprising the same | |
| EP2837642B1 (en) | Photocurable composition and encapsulated apparatus prepared using the same | |
| KR101726917B1 (en) | Composition for encapsulating organic light emitting diode and organic light emitting diode display apparatus prepared using the same | |
| KR20140004906A (en) | Photocurable composition and optical member comprising protective layer prepared from the same | |
| KR101574835B1 (en) | Photocurable composition, barrier layer comprising the same and encapsulated apparatus comprising the same | |
| KR20210082015A (en) | Composition for encapsulation, encapsulation layer comprising the same and encapsulated apparatus comprising the same | |
| KR20140004905A (en) | Photocurable composition, protective layer prepared from the same and optical member comprising the same | |
| JP2023001066A (en) | Composition for encapsulating organic light emitting element and organic luminous display device including organic layer manufactured thereby | |
| WO2014208849A1 (en) | Photocurable composition and encapsualted device including same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170310 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170314 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170525 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170704 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170714 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6178920 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |