CN113387979A - Compound, photocurable composition, cured film, and organic EL element - Google Patents
Compound, photocurable composition, cured film, and organic EL element Download PDFInfo
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- CN113387979A CN113387979A CN202110255454.3A CN202110255454A CN113387979A CN 113387979 A CN113387979 A CN 113387979A CN 202110255454 A CN202110255454 A CN 202110255454A CN 113387979 A CN113387979 A CN 113387979A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims description 54
- 239000000758 substrate Substances 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 29
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 90
- 239000010410 layer Substances 0.000 description 39
- 239000002274 desiccant Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- -1 aluminum alkoxide Chemical class 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 239000000565 sealant Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BDKDHWOPFRTWPP-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)butan-1-ol Chemical compound C=CCOCC(CO)(CC)COCC=C BDKDHWOPFRTWPP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011796 hollow space material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000010409 thin film Substances 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
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- PNPLRTWSLDSFET-UHFFFAOYSA-N 2-naphthalen-1-yl-5-phenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C3=CC=CC=C3C=CC=2)O1 PNPLRTWSLDSFET-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 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
- 229910052744 lithium Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 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
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- LTBRWBUKPWVGFA-UHFFFAOYSA-N butan-1-olate;hafnium(4+) Chemical compound [Hf+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] LTBRWBUKPWVGFA-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- UCOXGMHKZNIXKW-UHFFFAOYSA-N butan-2-ylalumane Chemical compound C(C)(CC)[AlH2] UCOXGMHKZNIXKW-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- BFIMXCBKRLYJQO-UHFFFAOYSA-N ethanolate;hafnium(4+) Chemical compound [Hf+4].CC[O-].CC[O-].CC[O-].CC[O-] BFIMXCBKRLYJQO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- SEKCULWEIYBRLO-UHFFFAOYSA-N hafnium(4+);propan-1-olate Chemical compound [Hf+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] SEKCULWEIYBRLO-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OXOORKFAYAWPBJ-UHFFFAOYSA-N octan-1-olate zirconium(4+) Chemical compound CCCCCCCCO[Zr](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC OXOORKFAYAWPBJ-UHFFFAOYSA-N 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-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
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract
Disclosed is a compound represented by the following general formula (1). In the formula (1), M represents a titanium atom, a zirconium atom or a hafnium atom, R1、R2、R3And R4Represents an alkyl group which may be substituted with a group having a polymerizable unsaturated bond. However, R1、R2、R3And R4At least one of the above groups is an alkyl group substituted with a group having a polymerizable unsaturated bond.
Description
Technical Field
The present invention relates to a compound, a photocurable composition, a cured film, and an organic EL device.
Background
As a sealing technique of a light emitting portion of a top emission type organic EL element, a film sealing technique is known. The film sealing technique is a technique of alternately forming an inorganic film and an organic film on a light emitting section and sealing the light emitting section. By alternately laminating the sealing films thus obtained, it is possible to prevent moisture and the like from entering the light emitting section.
As a material for forming an organic film, for example, a composition containing a combination of a polyethylene glycol di (meth) acrylate monomer and pentaerythritol tetra (meth) acrylate is disclosed (see patent document 1).
Patent document 1: japanese Kokai publication Hei-2017-531049
In the composition described in patent document 1, the polymerizable monomer having a hydrophilic functional group contained in the composition tends to easily adsorb moisture, and therefore the organic film to be formed may contain moisture. When moisture contained in the organic film enters the light emitting section, the light emitting area of the organic EL element may be reduced or black spots may be generated.
From the viewpoint of preventing such a phenomenon, introduction of a water-capturing component into the composition has been studied. However, according to the studies of the present inventors, it was found that when an aluminum alkoxide is applied to these compositions as a representative water-capturing component, there may be caused a problem in storage stability as follows: the aluminum alkoxide has high reactivity (activity), and the composition undergoes changes in quality such as aggregation and cloudiness due to a small amount of water; the available time is short; and a curing reaction of the composition (polymerization reaction of the polymerizable monomer) during storage to increase the viscosity, and the composition cannot be applied.
Disclosure of Invention
Accordingly, a main object of the present invention is to provide a compound which, when applied to a composition containing a polymerizable monomer, can sufficiently remove moisture in the composition and can sufficiently maintain the storage stability of the composition.
One embodiment of the present invention provides a compound represented by the following general formula (1).
In the formula (1), M represents a titanium atom, a zirconium atom or a hafnium atom, R1、R2、R3And R4Each independently represents an alkyl group which may be substituted with a group having a polymerizable unsaturated bond. However, R1、R2、R3And R4At least one (1 or more) of (a) and (b) is an alkyl group substituted with a group having a polymerizable unsaturated bond.
According to such a compound, since it has water-capturing properties equivalent to those of aluminum alkoxides which are typical water-capturing components, it is possible to sufficiently remove water in a composition when it is applied to a composition containing a polymerizable monomer. Further, according to such a compound, since the activity of the polymerizable monomer to the polymerization reaction is more stable than the activity of the aluminum alkoxide which is representative of the water-capturing component, it is possible to prevent the composition from being deteriorated and to suppress an undesired polymerization reaction of the polymerizable monomer. Therefore, when the composition is applied to a composition containing a polymerizable monomer, the storage stability of the composition can be sufficiently maintained.
The above compound may be a compound for a water-capturing component. The present invention may also relate to the use (application) of the compound represented by the general formula (1) as a water-capturing component or the use (application) in the aspect of a water-capturing component for producing the compound represented by the general formula (1).
Another embodiment of the present invention provides a photocurable composition containing the above compound and a photocurable resin component. The photocurable resin component may contain a monomer having a (meth) acryloyl group and a photopolymerization initiator. Since such a photocurable composition contains the above compound, the moisture content is sufficiently reduced, and it can be preferably used for the production of an organic film to be described later. Further, such a photocurable composition has excellent storage stability.
Since the photocurable composition contains the compound, the photocurable composition or a cured product thereof can also be used as a drying agent. The present invention also relates to use (application) of a composition containing the above compound and a photocurable resin component or a cured product thereof as a drying agent or use (application) thereof for producing a drying agent.
Another embodiment of the present invention provides a cured film containing a cured product of the photocurable composition. In the cured film, the polymerizable unsaturated bond in the compound is polymerized with, for example, a polymerizable unsaturated bond in a monomer having a (meth) acryloyl group, and thus the compound can be sufficiently dispersed in the cured film. Therefore, the cured film can be a desiccant having excellent water-capturing properties.
Another embodiment of the present invention provides an organic EL device. The organic EL element includes: an element substrate; a sealing substrate arranged to face the element substrate; a sealant for sealing the outer peripheries of the element substrate and the sealing substrate; a light emitting section provided on the element substrate inside the sealing agent, and having a pair of electrodes arranged to face each other and an organic layer provided between the pair of electrodes; and alternately laminating sealing films which are provided so as to cover at least the surface of the light emitting section and are composed of an inorganic film and an organic film. In the alternately laminated sealing films, the innermost film and the outermost film are inorganic films with respect to the light emitting section. The organic film contains the photocurable composition or a cured product thereof. The organic film may be the above-described cured film.
According to the present invention, there is provided a compound which, when applied to a composition containing a polymerizable monomer, can sufficiently remove moisture in the composition and can sufficiently maintain the storage stability of the composition. Further, the present invention provides a photocurable composition containing such a compound. Further, the present invention provides a cured film and an organic EL device using the photocurable composition.
Drawings
Fig. 1 (a) is a schematic cross-sectional view showing an embodiment of an organic EL element, and fig. 1 (b) is a schematic cross-sectional view showing an embodiment of a light-emitting portion in the organic EL element.
Fig. 2 (a) and (b) are schematic cross-sectional views showing another embodiment of the organic EL element.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present specification, (meth) acrylate means acrylate or methacrylate corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl group.
[ Compound ]
The compound of one embodiment is a compound represented by the following general formula (1).
In the formula (1), M is an element of group 4 of the periodic Table of the elements, and represents a titanium atom, a zirconium atom or a hafnium atom. M is preferably a zirconium atom from the viewpoint of less coloration and less susceptibility to ultraviolet-induced deterioration.
In the formula (1), R1、R2、R3And R4Each independently represents an alkyl group which may be substituted with a group having a polymerizable unsaturated bond. The alkyl group which may be substituted with a group having a polymerizable unsaturated bond means an unsubstituted alkyl group and an alkyl group substituted with a group having a polymerizable unsaturated bond. The alkyl group substituted with a group having a polymerizable unsaturated bond means an alkyl group in which 1 or 2 or more hydrogen atoms of an arbitrary unsubstituted alkyl group are substituted with a group having a polymerizable unsaturated bond. From R1、R2、R3And R4The groups represented may be the same or different, respectively.
Examples of the unsubstituted alkyl group include linear, branched or cyclic alkyl groups, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and a hexadecyl group. The number of carbon atoms of the unsubstituted alkyl group may be 1 to 28 or 1 to 8.
The group having a polymerizable unsaturated bond may be a group having a C ═ C bond. Examples of the group having a C ═ C bond include a vinyl group, an allyl group, an allyloxy group, a (meth) acryloyl group, and an alkynyl group. The group having a polymerizable unsaturated bond is at least one selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, a (meth) acryloyl group and an alkynyl group, or an allyloxy group.
In the alkyl group substituted with a group having a polymerizable unsaturated bond, the number of substitution with a group having a polymerizable unsaturated bond may be 2 or more. Examples of the alkyl group substituted with a group having a polymerizable unsaturated bond include a group represented by the following formula (2-1), a group represented by the following formula (2-2), and-CH2-C-(CH2-OOC-CH＝CH2)3And the like. A group containing a polymerizable unsaturated bond from the viewpoint of low self-polymerizability and excellent storage stabilityThe substituted alkyl group may be a group represented by the following formula (2-1), a group represented by the following formula (2-2), or a group represented by the following formula (2-1).
In the formulae (2-1) and (2-2), a bond is represented.
R1、R2、R3And R4At least one of the above groups is an alkyl group substituted with a group having a polymerizable unsaturated bond. R1、R2、R3And R4Each of the alkyl groups may be substituted with a group having a polymerizable unsaturated bond. At this time, from R1、R2、R3And R4The groups represented may be the same or different, respectively, but are preferably the same.
The compound of the present embodiment may be a compound represented by the general formula (1) wherein M is a zirconium atom and R is1、R2、R3And R4Is a group represented by the formula (2-1).
The compound of the present embodiment has excellent water-capturing properties. The present inventors speculate that the reason is as follows. That is, when the compound is brought into contact with moisture, an alkoxy (alkoxy) group in the compound is substituted with a hydroxyl group derived from moisture, whereby the moisture is mixed into the compound.
[ Process for producing Compound ]
The compound of the present embodiment can be obtained, for example, by reacting a compound having a central atom of any of a titanium atom, a zirconium atom, or a hafnium atom with an alcohol corresponding to an alkyl group substituted with a group having a polymerizable unsaturated bond.
The compound having a central atom of any of a titanium atom, a zirconium atom or a hafnium atom may be a compound in which an alkoxy group (alkoxxy group) corresponding to the above-mentioned unsubstituted alkyl group is bonded to the central atom. Examples of the compound having a titanium atom include tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetraoctyloxytitanium, and forty dialkoxytitanium. Examples of the compound having a zirconium atom include tetraethoxyzirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, tetraoctyloxy zirconium, and forty dialkoxy zirconium. Examples of the compound having a hafnium atom include hafnium tetraethoxide, hafnium tetrapropoxide, hafnium tetrabutoxide, hafnium tetraoctyloxide, hafnium tetradialkoxide, and the like.
The compound having a central atom of any of a titanium atom, a zirconium atom or a hafnium atom may be used singly or in combination of two or more, but it is preferably used singly.
Examples of the alcohol corresponding to the alkyl group substituted with a group having a polymerizable unsaturated bond include an alcohol represented by the following formula (3-1), an alcohol represented by the following formula (3-2), pentaerythritol triacrylate, and the like. The alcohol corresponding to the alkyl group substituted with a group having a polymerizable unsaturated bond may be used alone or in combination of two or more.
In the compound represented by the general formula (1), the number of alkyl groups substituted with a group having a polymerizable unsaturated bond can be adjusted by adjusting the ratio of the compound having a central atom of any one of a titanium atom, a zirconium atom and a hafnium atom to the alcohol corresponding to the alkyl group substituted with a group having a polymerizable unsaturated bond when reacted. From R1、R2、R3And R4The compound represented by the general formula (1) each having an alkyl group substituted with a group having a polymerizable unsaturated bond can be obtained, for example, by reacting a compound having any central atom of a titanium atom, a zirconium atom or a hafnium atom with 4 equivalents or more of an alcohol corresponding to the alkyl group substituted with the group having a polymerizable unsaturated bond.
The reaction conditions can be appropriately selected depending on the raw material compound, raw material alcohol, and the like used. The reaction conditions can be adjusted, for example, in the absence or presence of a solvent at a reaction temperature of 0 ℃ to 150 ℃ for a reaction time of 0.5 to 48 hours. After the reaction, volatile components may be removed by distillation under reduced pressure.
[ Photocurable composition ]
The photocurable composition of an embodiment contains the above compound and a photocurable resin component. The photocurable resin component may contain a monomer having a (meth) acryloyl group and a photopolymerization initiator.
The monomer having a (meth) acryloyl group is not particularly limited as long as it is a monomer having a (meth) acryloyl group, and examples thereof include a monofunctional (meth) acrylate compound having one (meth) acryloyl group, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups, and the like. The photocurable composition of the present embodiment can form a cured product by polymerizing the polymerizable unsaturated bond in the compound and the polymerizable unsaturated bond in the (meth) acryloyl group in the monomer having a (meth) acryloyl group.
The monomer having a (meth) acryloyl group may contain a monomer having a siloxane skeleton and a (meth) acryloyl group in view of the property of having an organic layer of an organic EL element that is not easily dissolved. Examples of such monomers include methacrylic acid-modified silicone oil and the like. The methacrylic-modified silicone oil is a silicone oil in which a methacrylic acid (methacryloyl) group is introduced into one end/both ends of a siloxane skeleton. Examples of the both-terminal type methacrylic-modified silicone oil include silicones represented by the following general formula (4).
In the formula (4), R5Each independently represents an alkyl group having 1 to 4 carbon atoms. As R5Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. R5Preferably methyl.
In the formula (4), R6Each independently represents a 2-valent organic group. Examples of the organic group having a valence of 2 include a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms.
In the formula (4), n can be set so that the functional group equivalent (g/mol) is 100 to 1000, for example.
As the methacrylic acid-modified silicone oil, conventionally known silicone oils can be used, and commercially available ones can also be used as they are. Preferable commercially available products include, for example, X-22-164AS, X-22-164A, X-22-164B, X-22-2445, X-22-174ASX, and X-22-2404 (all product names Shin-Etsu Chemical Co., Ltd.).
The photopolymerization initiator is not particularly limited as long as it generates a chain-polymerizable radical by irradiation with an active energy ray. The active energy ray may be at least one selected from the group consisting of ultraviolet rays, electron beams, and visible rays, and may be ultraviolet rays. Examples of the photopolymerization initiator include a photo radical polymerization initiator. Here, the chain polymerizable radical means a radical which starts a polymerization reaction by reacting with a chain polymerizable functional group.
Examples of the photo radical polymerization initiator include benzoin ketals, α -hydroxyketones, α -aminoketones, oxime esters, phosphine oxides, triarylimidazole dimers, benzophenone compounds, quinone compounds, benzoin ethers, benzoin compounds, benzyl compounds, acridine compounds, N-phenylglycine, and coumarins.
The content of the photopolymerization initiator may be 0.1 to 10 parts by mass, 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass with respect to 100 parts by mass of the content of the (meth) acryloyl group-containing monomer.
The photocurable resin component may contain components other than the monomer having a (meth) acryloyl group and the photopolymerization initiator. Examples of the other component include a sensitizer for the purpose of improving curability and suppressing coloring of a cured product. The content of each component in the other components may be, for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the content of the monomer having a (meth) acryloyl group.
The content of the compound (the compound represented by the general formula (1)) may be 0.1 part by mass or more, 0.3 part by mass or more, 0.5 part by mass or more, or 1 part by mass or more, or may be 200 parts by mass or less, 100 parts by mass or less, 50 parts by mass or less, or 20 parts by mass or less, with respect to 100 parts by mass of the content of the photocurable resin component. When the content of the compound is 0.1 parts by mass or more per 100 parts by mass of the content of the photocurable resin component, the water trapping capacity tends to be sufficient. When the content of the compound is 200 parts by mass or less with respect to 100 parts by mass of the content of the photocurable resin component, the viscosity increase tends to be sufficiently controlled.
The photocurable composition may be an ink composition that can be applied. The photocurable composition can be suitably used in, for example, an inkjet coating method, a dispenser coating method, an ODF (One Drop Fill) method, a screen printing method, a spray coating method, a hot melt method, and the like. The photocurable composition is suitable for the production of an organic film, and thus may be an ink composition for inkjet coating. When the ink jet coating method is applied, the viscosity of the photocurable composition at 25 ℃ may be 0.01 to 30 mPas.
The photocurable composition can be cured (cured product is formed) by irradiation with an active energy ray. The conditions for irradiation with active energy rays can be appropriately adjusted depending on the constituent components of the photocurable composition. The active energy ray may be at least one selected from the group consisting of ultraviolet rays, electron beams, and visible rays, and may be ultraviolet rays.
[ cured film ]
The cured film of an embodiment contains a cured product of the photocurable composition. In the cured film of the present embodiment, the polymerizable unsaturated bond in the compound is polymerized with the polymerizable unsaturated bond in the monomer having a (meth) acryloyl group, and therefore the compound can be sufficiently dispersed in the cured film. Therefore, the cured film can be a desiccant having excellent water-capturing properties.
[ organic EL element and method for producing the same ]
Fig. 1 (a) is a schematic cross-sectional view showing an embodiment of an organic EL element, and fig. 1 (b) is a schematic cross-sectional view showing an embodiment of a light-emitting portion in the organic EL element. The organic EL element 100 shown in fig. 1 (a) includes: an element substrate 2; a sealing substrate 4 disposed to face the element substrate 2; a sealing agent 6 for sealing the outer peripheral portions of the element substrate 2 and the sealing substrate 4; a light emitting section 20 provided on the element substrate 2 inside the sealant 6; and alternately laminated sealing films 12 each composed of an inorganic film 8 and an organic film 10 and provided so as to cover at least the surface of the light emitting section 20. The light-emitting section 20 shown in fig. 1 (b) includes a pair of electrodes (an anode 22 and a cathode 24) disposed to face each other and an organic layer 26 provided between the pair of electrodes. In the alternately laminated sealing films 12, the innermost and outermost films are inorganic films 8 with respect to the light emitting part 20. The organic film 10 contains the above-described photocurable composition or a cured product thereof. The organic film 10 may be the above-described cured film.
The number of alternately laminated sealing films 12 composed of the inorganic film 8 and the organic film 10 is not particularly limited as long as the innermost film and the outermost film are inorganic films, and may be 3, 5, 7, or 9 or more layers. In addition, the alternately laminated sealing films 12 do not necessarily have to cover the entire surface of the element substrate 2 inside the sealing agent 6 as long as they cover the surface of the light emitting part 20.
The material constituting the inorganic film 8 is not particularly limited, and examples thereof include silicon compounds such as silicon nitride (SiN), silicon oxide (SiO), and silicon oxide containing nitrogen (SiON). The inorganic film 8 can be generally formed by Chemical Vapor Deposition (CVD) of a constituent material. The thickness of the inorganic film 8 may be, for example, 0.1 to 3 μm.
The organic film 10 can be generally formed by forming a coating film on the inorganic film 8 using the photocurable composition by an ink jet method, and irradiating the coating film with active energy rays to cure the photocurable composition. The active energy ray may be at least one selected from the group consisting of ultraviolet rays, electron beams, and visible rays, and may be ultraviolet rays. The thickness of the organic film 10 may be, for example, 0.1 to 10 μm.
By repeating such operations, the alternately laminated sealing films 12 can be obtained.
In the organic EL device 100 shown in fig. 1 (a), although a hollow space remains inside the sealing agent 6, the hollow space does not necessarily need to be present, and the entire or a part of the hollow space may be sealed with a sealing material or the like.
In the organic EL element 100, conventionally known elements can be applied to the elements other than the alternate lamination of the sealing films 12 (particularly, the organic films 10), and an example thereof will be briefly described below.
The element substrate 2 is formed of an insulating and light-transmitting rectangular glass substrate, and an anode 22 (electrode) is formed of ITO (Indium Tin Oxide) as a transparent conductive material on the element substrate 2. The anode 22 is formed by patterning an ITO film formed on the element substrate 2 by PVD (Physical Vapor Deposition) such as vacuum Vapor Deposition or sputtering, with a predetermined pattern shape by etching using a photoresist method. A part of the anode 22 as an electrode is drawn to an end of the element substrate 2 and connected to a drive circuit (not shown).
An organic layer 26, which is a thin film containing an organic light-emitting material, is laminated on the upper surface of the anode 22 by a PVD method such as a vacuum vapor deposition method or a resistance heating method. The organic layer 26 may be formed of a single layer or may be formed of a plurality of layers having different functions. The organic layer 26 may have a 4-layer structure in which a hole injection layer 26a, a hole transport layer 26b, a light-emitting layer 26c, and an electron transport layer 26d are stacked in this order from the anode 22 side, for example. The hole injection layer 26a is formed of, for example, copper phthalocyanine (CuPc) having a film thickness of several tens of nm. The hole transport layer 26b is made of, for example, bis [ N- (1-naphthyl) -N-phenyl ] having a film thickness of several tens of nm]Benzidine (. alpha. -NPD) formation. The light-emitting layer 26c is made of, for example, tris (8-hydroxyquinoline) aluminum (Alq) having a film thickness of several tens of nm3) And (4) forming. The electron transport layer 26d is formed of, for example, lithium fluoride (LiF) having a film thickness of several nm.
A cathode 24 (electrode) as a metal thin film is laminated on the upper surface of the organic layer 26 (electron transport layer 26d) by PVD such as vacuum vapor deposition. Examples of the material of the metal thin film include metal monomers having a small work function such as Al, Li, Mg, and In, and alloys having a small work function such as Al — Li and Mg — Ag. The cathode 24 is formed to have a film thickness of, for example, several tens nm to several hundreds nm (preferably, 50nm to 200 nm). A part of the cathode 24 is drawn out to an end of the element substrate 2 and connected to a drive circuit (not shown).
The sealing substrate 4 is disposed to face the element substrate 2 with the organic layer 26 interposed therebetween. The outer peripheral portions of the element substrate 2 and the sealing substrate 4 are sealed with a sealant 6. Examples of the sealing agent 6 include ultraviolet curable resins.
In the method of manufacturing an organic EL element according to one embodiment, a laminate in which a light-emitting section 20 having an organic layer 26 and the like is formed on an element substrate 2 is prepared. On the other hand, by the above method, the alternately laminated sealing films 12 composed of at least the inorganic film 8, the organic film 10, and the inorganic film 8 are formed at least on the light emitting section 20. Then, the sealant 6 is applied by a dispenser so as to surround the drying agent applied to the sealing substrate 4. These operations can be carried out in a glove box purged with nitrogen at a dew point of-76 ℃ or lower.
Next, the element substrate 2 on which the light emitting section 20 is mounted and the sealing substrate 4 are bonded to each other with the sealing film 12 and the sealing agent 6 alternately stacked therebetween. The organic EL element 100 of the present embodiment can be obtained by curing a drying agent and/or a sealing agent by irradiating ultraviolet rays and/or heating the obtained structure as necessary.
The embodiments of the present invention have been described above in detail, but the present invention is not limited to the above embodiments. For example, in the above-described embodiment, an organic EL element having an organic film made of a photocurable composition is exemplified, but the photocurable composition or a cured product (cured film) thereof itself functions as a desiccant, and therefore, the photocurable composition or the cured product (cured film) can be applied to a desiccant layer of an organic EL element having a desiccant layer. Fig. 2 (a) and (b) are schematic cross-sectional views showing another embodiment of the organic EL element. The organic EL element 200(300) shown in fig. 2 (a) and (b) includes: an element substrate 2; a sealing substrate 4 disposed to face the element substrate 2; a sealing agent 6 for sealing the outer peripheral portions of the element substrate 2 and the sealing substrate 4; a light emitting section 20 provided on the element substrate 2 inside the sealant 6; and a desiccant layer 14(16) which is provided around the light-emitting portion 20 inside the sealant 6 and contains the photocurable composition or a cured product thereof. The outer peripheral portions of the element substrate 2 and the sealing substrate 4 are sealed with the sealant 6, and an airtight space is formed around the light emitting portion 20 between the element substrate 2 and the sealing substrate 4.
The desiccant layer 14 in the organic EL element 200 shown in fig. 2 (a) fills an airtight space around the light-emitting section 20 inside the sealant 6. That is, the organic EL element 200 is a so-called filling and sealing structure organic EL element. However, the desiccant layer does not necessarily have to fill the entire airtight space in which the light emitting section 20 is provided. For example, as in the organic EL device 300 shown in fig. 2 (b), the desiccant layer 16 may be formed on the sealing substrate 4, and a hollow space may remain inside the sealant 6. That is, the organic EL element 300 is an organic EL element having a so-called hollow sealed structure. In this case, the thickness of the desiccant layer 16 may be, for example, 1 to 300 μm. The desiccant layer 16 can be formed by coating with a dispenser or the like.
In the organic EL elements 200 and 300, conventionally known elements can be applied to the elements other than the desiccant layers 14 and 16.
The application of the photocurable composition or the cured product (cured film) thereof is not limited to the organic EL element, and can be applied to, for example, a display device (quantum dot display) using quantum dots. More specifically, for example, in a color filter of a quantum dot display, the organic film (desiccant layer) can be used to cover the surface thereof.
Examples
The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[ Synthesis of Compound (Water trapping component) ] (example 1)
Into a flask, 21 parts by mass of trimethylolpropane diallyl ether (2, 2-bis (allyloxymethyl) -1-butanol, compound represented by the formula (3-1)) (trade name: neoallyl T-20, OSAKA SODA co., LTD.) and 10 parts by mass of zirconium tetrapropoxide (Tokyo Chemical Industry co., LTD.) were charged, and stirred at 25 ℃ for 1 hour. Then, the volatile matter and the like were distilled off under reduced pressure at 60 ℃ and 300Pa for 3 hours, and further under reduced pressure at 150 ℃ and 300Pa for 3 hours, whereby the compound of example 1 was obtained as a transparent adhesive. Since 4 equivalents of trimethylolpropane diallyl ether was reacted with zirconium tetrapropoxide, the compound of example 1 was presumed to be tetrakis (2, 2-bis (allyloxymethyl) -1-butoxy) zirconium, i.e. R in formula (1)1、R2、R3And R4All are 2, 2-bis (allyloxymethyl) -1-butyl zirconium compounds.
Comparative example 1
Into a flask, 28 parts by mass of trimethylolpropane diallyl ether (2, 2-bis (allyloxymethyl) -1-butanol) (trade name: neoallyl T-20, OSAKA SODA co., LTD.) and 10 parts by mass of sec-butyl aluminum (trade name: ADBD, Kawaken Fine Chemicals co., LTD.) were charged, and stirred at 25 ℃ for 1 hour. Then, the volatile components and the like were distilled off under reduced pressure at 60 ℃ and 300Pa for 3 hours, and further under reduced pressure at 150 ℃ and 300Pa for 3 hours, to obtain the compound of comparative example 1 as a transparent viscous body having a very high viscosity. Since 3 equivalents of trimethylolpropane diallyl ether was reacted with aluminum sec-butoxide, the compound of comparative example 1 was assumed to be tris (2, 2-bis (allyloxymethyl) -1-butoxy) aluminum.
[ Water Capacity test ]
The water trapping property test of the compound of example 1 was performed by charging the compound of example 1 into a monomer having a (meth) acryloyl group, and measuring the water content contained in the monomer having a (meth) acryloyl group before and after the charging by the karl fischer method. As the monomer having a (meth) acryloyl group, both-terminal methacrylic-modified silicone oil X-22-164 (trade name, Shin-Etsu Chemical Co., Ltd., viscosity at 25 ℃ C.: 10 mPas) was used. The measurement apparatus used was a trace moisture measurement apparatus (KF method moisture meter, trade name: CA-100, Nittoseiko Analyticch Co., Ltd.). The X-22-164 film was vacuum-degassed, and the water content was measured to find that the concentration was 136.8 ppm. Next, 10 parts by mass of the compound of example 1 was charged into 100 parts by mass of X-22-164, and the mixture was left at 25 ℃ for 1 hour. Then, X-22-164 containing the compound of example 1 was degassed under vacuum, and the water content was measured, whereby the water content was 0ppm (detection limit or less). This confirmed that the compound of example 1 was able to sufficiently remove moisture contained in the monomer having a (meth) acryloyl group.
[ storage stability test ]
The compounds shown in table 1, the (meth) acryloyl group-containing monomer, and the photopolymerization initiator were mixed at the contents (unit: parts by mass) shown in table 1 to prepare test compositions of test examples 1 to 4. In addition, "Irgacure 907" in Table 1 is 2- [4- (methylthio) benzoyl ] -2- (4-morpholinyl) propane (manufactured by BASF Co., Ltd., the same applies hereinafter). Each test composition was stored at 25 ℃ or 60 ℃ to visually confirm the presence or absence of deterioration in the test composition. The results are shown in Table 1. The viscosity at 25 ℃ of the test compositions of test examples 1 and 2, which were not deteriorated, was measured before and after storage. The results are shown in Table 1.
[ Table 1]
As shown in table 1, in test examples 3 and 4 using the compound of comparative example 1, the test composition was observed to be deteriorated after storage, whereas in test examples 1 and 2 using the compound of example 1, the test composition was not deteriorated after storage. Furthermore, the viscosity of the test examples 1 and 2 was hardly changed before and after the storage. From this, it was confirmed that the compound of example 1 can sufficiently maintain the storage stability of the test composition.
[ preparation of Photocurable composition ] (example 2)
Into a flask, 12 parts by mass of both-end type methacrylic modified silicone oil X-22-164AS (trade name, Shin-Etsu Chemical Co., Ltd., viscosity at 25 ℃ C.: 12 mPas), 1 part by mass of the compound of example 1 and 0.1 part by mass of Irgacure 907 were charged and stirred at 25 ℃ for 1 hour. Then, volatile components were distilled off at 100 ℃ for 1 hour to obtain a photocurable composition (ink composition) of example 2 as a transparent liquid. The photocurable composition of example 2 had a viscosity of 17.1mPa · s at 25 ℃.
[ study on coating Property and Water-capturing Properties ]
Organic EL devices for testing were prepared, and the coating properties and water-capturing properties of the photocurable composition were easily investigated by applying the photocurable composition of example 2 thereto.
(preparation of organic EL element)
ITO, a transparent conductive material, was formed on the element substrate by a sputtering method to have a film thickness of 140 nm. The ITO film was patterned in a predetermined pattern shape by etching by a photoresist method, and an anode was formed.
A hole injection layer was formed by forming copper phthalocyanine (CuPc) on the upper surface of the formed anode by a resistance heating method to a film thickness of 70nm, and bis [ N- (1-naphthyl) -N-phenyl ] was formed on the upper surface of the hole injection layer to a film thickness of 30nm]A hole transport layer was formed using benzidine (. alpha. -NPD), and tris (8-hydroxyquinoline) aluminum (Alq) was formed on the upper surface of the hole transport layer to a film thickness of 50nm3) Thereby forming a light emitting layer.
Lithium fluoride (LiF) was formed on the upper surface of the light-emitting layer to have a film thickness of 7nm to form an electron transporting layer, and aluminum was physically vapor-deposited on the surface of the electron transporting layer to have a film thickness of 150nm as a cathode. As described above, a laminate in which the anode, the organic layer (hole injection layer/hole transport layer/light-emitting layer/electron transport layer), and the cathode are sequentially laminated is formed on the element substrate.
Next, the photocurable composition of example 2 was applied to the center of the sealing substrate by ODF in a glove box purged with nitrogen gas having a dew point of-76 ℃ or lower, and cured by irradiation with ultraviolet rays, thereby forming an organic film containing a cured product of the photocurable composition of example 2. A sealant made of an ultraviolet curable resin is applied to the sealing substrate by a dispenser so as to surround the organic film.
Then, the element substrate and the sealing substrate are bonded with the laminate, the organic film, and the sealant facing inward. In this state, the outer peripheral portions of the sealing substrate and the sealing element substrate were sealed by ultraviolet irradiation and heating at 80 ℃.
(Change in luminous area ratio)
The obtained organic EL element was left to stand in a high-temperature and high-humidity environment at 85 ℃ and 85% RH for 1250 hours. It was found that the change in the light-emitting area ratio hardly changed before and after the test, the coating property of the photocurable composition of example 2 was excellent, and the formed organic film also had sufficient water-capturing property.
Description of the symbols
2-element substrate, 4-sealing substrate, 6-sealant, 8-inorganic film, 10-organic film, 12-alternately stacked sealing film, 14, 16-desiccant layer, 20-light emitting part, 22-anode, 24-cathode, 26-organic layer, 26 a-hole injection layer, 26 b-hole transport layer, 26 c-light emitting layer, 26 d-electron transport layer, 100, 200, 300-organic EL element.
Claims (5)
1. A compound represented by the following general formula (1),
in the formula (1), M represents a titanium atom, a zirconium atom or a hafnium atom, R1、R2、R3And R4Each independently represents an alkyl group which may be substituted with a group having a polymerizable unsaturated bond, provided that R1、R2、R3And R4At least one of the above groups is an alkyl group substituted with a group having a polymerizable unsaturated bond.
2. A photocurable composition comprising the compound according to claim 1 and a photocurable resin component.
3. The photocurable composition according to claim 2, wherein,
the photocurable resin component contains a monomer having a (meth) acryloyl group and a photopolymerization initiator.
4. A cured film comprising a cured product of the photocurable composition according to claim 2 or 3.
5. An organic EL element comprising:
an element substrate;
a sealing substrate arranged to face the element substrate;
a sealing agent sealing the outer peripheral portions of the element substrate and the sealing substrate;
a light emitting section provided on the element substrate inside the sealing agent, and having a pair of electrodes arranged to face each other and an organic layer provided between the pair of electrodes; and
alternately laminating sealing films each composed of an inorganic film and an organic film so as to cover at least the surface of the light emitting section,
in the alternately laminated sealing films, the innermost film and the outermost film are inorganic films with respect to the light emitting section,
the organic film contains the photocurable composition according to claim 2 or 3 or a cured product thereof.
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| JP2020-044219 | 2020-03-13 | ||
| JP2020044219A JP7312715B2 (en) | 2020-03-13 | 2020-03-13 | COMPOUND, PHOTOCURABLE COMPOSITION, CURED FILM AND ORGANIC EL DEVICE |
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| US5126205A (en) | 1990-05-09 | 1992-06-30 | The Perkin-Elmer Corporation | Powder of plastic and treated mineral |
| CA2431410A1 (en) * | 2000-12-15 | 2002-06-20 | Ucb, S.A. | Surface functionalization of pigments and/or dyes for radiation curable ink printing and coating applications |
| JPWO2012086334A1 (en) | 2010-12-22 | 2014-05-22 | Jsr株式会社 | Luminescent body and display device |
| EP2813540B1 (en) | 2012-02-08 | 2020-01-15 | LG Chem, Ltd. | Multilayered film and method for manufacturing same |
| CN102942841B (en) | 2012-05-30 | 2015-07-22 | 刘志钊 | Transparent thermal insulation coating material system for glass substrate |
| EP3186319A4 (en) | 2014-07-25 | 2018-04-18 | Kateeva, Inc. | Organic thin film ink compositions and methods |
| JP6165813B2 (en) | 2014-09-30 | 2017-07-19 | 富士フイルム株式会社 | Curable composition, cured film, organic EL display device, liquid crystal display device, and touch panel display device |
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