JP4164885B2 - Organic electroluminescent device and manufacturing method thereof - Google Patents
Organic electroluminescent device and manufacturing method thereof Download PDFInfo
- Publication number
- JP4164885B2 JP4164885B2 JP24496497A JP24496497A JP4164885B2 JP 4164885 B2 JP4164885 B2 JP 4164885B2 JP 24496497 A JP24496497 A JP 24496497A JP 24496497 A JP24496497 A JP 24496497A JP 4164885 B2 JP4164885 B2 JP 4164885B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- group
- organic electroluminescent
- meth
- polyfunctional
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000758 substrate Substances 0.000 claims description 111
- -1 mercapto compounds Chemical class 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 230000003746 surface roughness Effects 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000001033 ether group Chemical group 0.000 claims description 7
- 125000000101 thioether group Chemical group 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000010410 layer Substances 0.000 description 97
- 230000005525 hole transport Effects 0.000 description 32
- 239000000463 material Substances 0.000 description 32
- 230000032258 transport Effects 0.000 description 30
- 239000011521 glass Substances 0.000 description 23
- 238000002347 injection Methods 0.000 description 21
- 239000007924 injection Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000001771 vacuum deposition Methods 0.000 description 8
- 125000006839 xylylene group Chemical group 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005401 electroluminescence Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229940071127 thioglycolate Drugs 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 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 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 125000006617 triphenylamine group Chemical group 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical group OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000003513 tertiary aromatic amines Chemical group 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- SQWIEBKHVLRDRG-UHFFFAOYSA-N (2,6-dimethylphenyl)-diphenylphosphorylmethanone Chemical compound CC1=CC=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 SQWIEBKHVLRDRG-UHFFFAOYSA-N 0.000 description 1
- CHBDXRNMDNRJJC-UHFFFAOYSA-N 1,2,3-triphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CHBDXRNMDNRJJC-UHFFFAOYSA-N 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LHGFMZOQWYPJHE-UHFFFAOYSA-N 1-phenylphenanthridine-2,3-diamine Chemical class NC=1C(N)=CC2=NC=C3C=CC=CC3=C2C=1C1=CC=CC=C1 LHGFMZOQWYPJHE-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- SULWTXOWAFVWOY-PHEQNACWSA-N 2,3-bis[(E)-2-phenylethenyl]pyrazine Chemical class C=1C=CC=CC=1/C=C/C1=NC=CN=C1\C=C\C1=CC=CC=C1 SULWTXOWAFVWOY-PHEQNACWSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- FBHYXKSGCYPHCM-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]cyclohexyl]propan-2-yl]cyclohexyl]oxyethyl 2-methylprop-2-enoate Chemical compound C1CC(OCCOC(=O)C(=C)C)CCC1C(C)(C)C1CCC(OCCOC(=O)C(C)=C)CC1 FBHYXKSGCYPHCM-UHFFFAOYSA-N 0.000 description 1
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 1
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- NKIDFMYWMSBSRA-UHFFFAOYSA-N [4-(2-methylprop-2-enoyloxymethyl)cyclohexyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CCC(COC(=O)C(C)=C)CC1 NKIDFMYWMSBSRA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- VDQLDLGIMZTPQO-UHFFFAOYSA-N n-[4-(2,5-dimethylphenyl)phenyl]-4-methyl-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C(=CC=C(C)C=1)C)C1=CC=C(C)C=C1 VDQLDLGIMZTPQO-UHFFFAOYSA-N 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 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
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical class C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 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 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
Landscapes
- Electroluminescent Light Sources (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は有機電界発光素子及びその製造方法に関するものであり、詳しくは、有機化合物からなる発光層に電界をかけて光を放出する薄膜型発光素子の支持基板の改良に関するものである。
【０００２】
【従来の技術】
従来、薄膜型の電界発光（ＥＬ）素子としては、無機材料のII-IV 族化合物半導体であるＺｎＳ、ＣａＳ、ＳｒＳ等に、発光中心であるＭｎや希土類元素（Ｅｕ、Ｃｅ、Ｔｂ、Ｓｍ等）をドープしたものが一般的であるが、上記の無機材料から作製したＥＬ素子は、
(1) 交流駆動が必要とされる（一般に、５０〜１０００Ｈｚ）、
(2) 駆動電圧が高い（一般に２００Ｖ程度）、
(3) フルカラー化が困難であり、特に青色に問題がある、
(4) 周辺駆動回路のコストが高い、
といった問題点を有している。
【０００３】
しかし、近年、上記問題点を改良すべく、有機薄膜を用いたＥＬ素子の開発が行われるようになった。特に、発光効率を高めるために、電極からのキャリアー注入の効率向上を目的として電極の種類の最適化を行い、芳香族ジアミンから成る有機正孔輸送層と８−ヒドロキシキノリンのアルミニウム錯体から成る有機発光層とを設けた有機電界発光素子の開発（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５１巻，９１３頁，１９８７年）により、従来のアントラセン等の単結晶を用いた電界発光素子と比較して発光効率の大幅な改善がなされ、実用特性に近づいてきている。
【０００４】
また、上記の様な低分子材料を用いた電界発光素子の他にも、有機発光層の材料として、ポリ（ｐ−フェニレンビニレン）（Ｎａｔｕｒｅ，３４７巻，５３９頁，１９９０年他）、ポリ [２−メトキシ−５−（２−エチルヘキシルオキシ）−１，４−フェニレンビニレン] （Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５８巻，１９８２頁他）、ポリ（３−アルキルチオフェン）（Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，３０巻，Ｌ１９３８頁他）等の高分子材料を用いた電界発光素子の開発や、ポリビニルカルバゾール等の高分子に低分子の発光材料と電子移動材料を混合した素子（応用物理，６１巻，１０４４頁，１９９２年）の開発も行われている。
【０００５】
以上に示したような有機電界発光素子においては、通常、基板としてはガラスが用いられる。しかしながら、有機電界発光素子の重要な用途と目されているパソコンや携帯型端末の表示パネルにおいて、基板としてガラスを用いた場合、ガラスの低密度化と機械的強度の問題から、軽量化、薄型化に限界がある上に、生産性の向上の面でも、成形性、加工性の観点から問題がある。このため、プラスチックを基板として用いた有機電界発光素子の開発が強く望まれている。
【０００６】
【発明が解決しようとする課題】
しかしながら、従来のプラスチック基板には下記のような問題点があった。
【０００７】
(1) 有機電界発光素子に適した透明性と光学特性を満足し得ない。
(2) 耐熱性に劣る。
(3) 表面精度に劣る。
特に、光学的等方性に関しては、ガラス基板の複屈折Δｎ・ｄが１ｎｍ以下であるのに対し、プラスチック基板では１０ｎｍを超えているのが現状である。この複屈折性の問題は、何らかの延伸操作或いは材料の流動操作が樹脂に施される成型法を採用する場合において、これを解決するのは難しい。また、比較的厚い基板（例えば０．４ｍｍ以上）とする場合、熱可塑性樹脂の押し出しやベルト形成では成形が困難である。一方、熱硬化性樹脂を用いた場合には、成形に数時間を要し、生産性の面で問題がある。
【０００８】
本発明は上記従来の問題点を解決し、有機電界発光素子に適した透明性と光学特性を有し、耐熱性、表面精度に優れ、成形性も良好なプラスチック基板を用いて、軽量で機械的強度及び生産性に優れた有機電界発光素子及びその製造方法を提供することを目的とする。
【０００９】
【課題を解決するための手段】
本発明の有機電界発光素子は、基板の一方の板面上に、陽極、有機発光層及び陰極が積層された有機電界発光素子であって、該基板は光硬化性樹脂よりなり、かつ、基板の該一方の板面の表面粗さ（Ｒｚ）が１〜５０ｎｍであり、該光硬化性樹脂が下記一般式 [I]
【００１０】
【化５】
（上記 [I] 式中、Ｒ １ 及びＲ ２ は、それぞれ水素原子又はメチル基、Ｒ ３ 及びＲ ４ は、それぞれエーテル基及び／又はチオエーテル基を含んでいてもよい炭素数１〜６の炭化水素基、Ｘはハロゲン原子或いは炭素数１〜６のアルキル基又はアルコキシ基を示し、ｋは０〜４の整数を示す。）
で表される化合物及び下記一般式 [II]
【００１１】
【化６】
（上記 [II] 式中、Ｒ ５ 及びＲ ６ は、それぞれ水素原子又はメチル基を示し、ｍは１又は２、ｎは０又は１を示す。）
で表される化合物よりなる群から選ばれる少なくとも１種の分子内に２個以上の官能基を有する多官能（メタ）アクリレートを含有するモノマーを光重合させて得られることを特徴とする。
【００１２】
光硬化性樹脂製基板であれば、光硬化性液状モノマーを板状に賦形し該モノマーに活性エネルギー線を照射して重合硬化させることにより容易に基板を成形することができ、しかも、このような光硬化性樹脂製基板であれば、有機電界発光素子に適した透明性及び光学特性を有し、耐熱性や表面精度にも優れる。
【００１３】
なお、基板の積層面、即ち、陽極、有機発光層及び陰極が積層形成される面（以下「発光素子作製面」と称す。）の表面粗さ（Ｒｚ）を１〜５０ｎｍの範囲とすることで、素子の短絡を引き起こすことなく、基板に素子構成層を接着性良く形成することが可能となる。
【００１４】
本発明において、光硬化性樹脂は、分子内に２個以上の官能基を有する多官能（メタ）アクリレートを含有するモノマーを光重合させて得られるものであることが好ましく、この分子内に２個以上の官能基を有する多官能（メタ）アクリレートは、下記一般式[I]で 表される化合物及び下記一般式[II]で表される化合物よりなる群から選ばれる少なくとも１種のビス（メタ）アクリレートであることが好ましい。
【００１５】
【化７】
【００１６】
（上記[I]式中、Ｒ１及びＲ２は、それぞれ水素原子又はメチル基、Ｒ３及びＲ４ は、それぞれエーテル基及び／又はチオエーテル基を含んでいてもよい炭素数１〜６の炭化水素基、Ｘはハロゲン原子或いは炭素数１〜６のアルキル基又はアルコキシ基を示し、ｋは０〜４の整数を示す。）
【００１７】
【化８】
【００１８】
（上記[II]式中、Ｒ５及びＲ６は、それぞれ水素原子又はメチル基を示し、ｍは１又は２、ｎは０又は１を示す。）
本発明に係る光硬化性樹脂は、特に、分子内に２個以上の官能基を有する多官能（メタ）アクリレート及び分子内に２個以上の官能基を有する多官能メルカプト化合物を共重合させて得られるものであることが好ましい。
【００１９】
また、基板は、複屈折２０ｎｍ以下の光硬化性樹脂で構成されていることが好ましい。
【００２０】
このような本発明の有機電界発光素子は、基板上に、陽極、有機発光層及び陰極を積層して有機電界発光素子を製造する方法において、該基板として光硬化性樹脂よりなり、かつ、その少なくとも一方の板面の表面粗さ（Ｒｚ）が１〜５０ｎｍである基板を用い、該基板の該一方の板面に陽極、有機発光層及び陰極を積層することより製造される。
【００２１】
本発明において、基板は、好ましくは、分子内に２個以上の官能基を有する多官能（メタ）アクリレート及び分子内に２個以上の官能基を有する多官能メルカプト化合物を含む光硬化性液状モノマーを板状に賦形し、これに活性エネルギー線を照射して光重合硬化させることにより製造される。
【００２２】
【発明の実施の形態】
以下に、本発明の有機電界発光素子及びその製造方法について、図面を参照しながら説明する。
【００２３】
図１〜３は本発明の有機電界発光素子の構造例を示す模式的断面図であり、図中、１は基板、２は陽極、３は有機発光層、３ａは正孔輸送層、３ｂは電子輸送層、３ｃは正孔注入層、４は陰極、１０，１０Ａ，１０Ｂは有機電界発光素子である。
【００２４】
基板１は有機電界発光素子の支持体となるものであり、光学特性、耐熱性、表面精度、機械的強度、軽量性、ガスバリア性などの特性に優れていることが要求される。本発明においてはこれらの特性に優れたプラスチック基板として、光硬化性樹脂製基板を採用する。以下に本発明で用いている基板材料について説明する。
【００２５】
＜多官能（メタ）アクリレート＞
本発明に係る基板は、例えば多官能（メタ）アクリレートとして下記一般式[I]で示される含イオウビス（メタ）アクリレート及び下記一般式[II]で示される脂環骨格ビス（メタ）アクリレートよりなる群から選ばれる１種又は２種以上のビス（メタ）アクリレートを含んでなる光硬化性モノマー組成物を賦形し、これに活性エネルギー線を照射して光重合硬化させてなる光硬化性樹脂で構成される。
【００２６】
【化９】
【００２７】
【化１０】
【００２８】
上記一般式[I]及び[II]中の各記号は下記の意味を持つ。
Ｒ１及びＲ２：水素原子又はメチル基。Ｒ１，Ｒ２は同一であっても異なってもよい。
【００２９】
Ｒ３：エーテル基（エーテル結合：Ｃ−Ｏ−Ｃ）、チオエーテル基（チオエーテル結合：Ｃ−Ｓ−Ｃ）を含んでいてもよい炭素数１〜６の炭化水素基、好ましくは炭素数２〜４のアルキレン基
Ｒ４：エーテル基、チオエーテル基を含んでいてもよい炭素数１〜６の炭化水素基、好ましくは炭素数１〜３のアルキレン基
Ｘ：ハロゲン原子或いは炭素数１〜６のアルキル基又はアルコキシ基
ｋ：０〜４の整数
Ｒ５及びＲ６：水素原子又はメチル基。Ｒ５，Ｒ６は同一であっても異なっていてもよいｍ：１又は２
ｎ：０又は１
なお、上記「（メタ）アクリレートを含んでなる光硬化性モノマー組成物」の「含んでなる」とは、当該組成物が本発明の趣旨を損なわない範囲で、多官能（メタ）アクリレート以外の少量の補助成分を含んでもよいことを意味するものである。即ち、本発明で光硬化性モノマー組成物の主成分として特定する上記多官能（メタ）アクリレートと共重合可能な他の単量体等の補助成分を、例えば、後述の如く、光硬化性モノマー組成物１００重量部に対して３０重量部程度までの範囲で含んでいてもよいことを意味する。また、この組成物中の各成分は、成分間及び／又は成分内においてその複数種類を併用してもよい。
【００３０】
また、本明細書において、「（メタ）アクリレート」は、アクリレート及び／又はメタアクリレートを総称するものである。
【００３１】
前記一般式[I]で示される含イオウビス（メタ）アクリレート化合物の具体例としては、例えば、ｐ−ビス（β−メタクリロイルオキシエチルチオ）キシリレン（Ｒ１：メチル、Ｒ２：メチル、Ｒ３：エチレン、Ｒ４：メチレン、ｋ：０）、ｐ−ビス（β−アクリロイルオキシエチルチオ）キシリレン、ｍ−ビス（β−メタクリロイルオキシエチルチオ）キシリレン、ｍ−ビス（β−アクリロイルオキシエチルチオ）キシリレン、ｐ−ビス（β−メタクリロイルオキシエチルオキシエチルチオ）キシリレン、ｐ−ビス（β−メタクリロイルオキシエチルチオ）キシリレン、ｐ−ビス（β−メタクリロイルオキシエチルチオ）テトラブロムキシリレン、ｍ−ビス（β−メタクリロイルオキシエチルチオ）テトラクロロキシリレンなどが挙げられる。
【００３２】
これらの化合物は、例えば特開昭６２−１９５３５７号公報に示されている方法で合成することができる。
【００３３】
また、前記一般式[II]で示される脂環骨格ビス（メタ）アクリレート化合物の具体例としては、ビス（オキシメチル）トリシクロ［５．２．０２，６］デカン＝ジアクリレート、ビス（オキシメチル）トリシクロ［５．２．０２，６］デカン＝ジメタクリレート、ビス（オキシメチル）トリシクロ［５．２．０２，６］デカン＝アクリレートメタクリレート、及びこれらの混合物、ビス（オキシメチル）ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカン＝ジアクリレート、ビス（オキシメチル）ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカン＝ジメタクリレート、ビス（オキシメチル）ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカン＝アクリレートメタクリレート及びこれらの混合物が挙げられる。これらのトリシクロデカン化合物及びペンタシクロペンタデカン化合物は、群内又は群間で２種以上併用してもよい。
【００３４】
これらの化合物は、例えば特開昭６２−２２５５０８号公報に示されている方法で合成することができる。
【００３５】
前記一般式[I]及び[II]で表される多官能（メタ）アクリレートは、単独もしくは２種以上を併用して用いることができる。一般式[I]の化合物を単独で用いる場合、得られる基板の屈折率は、ナトリウムのＤ線（５８９．３ｍｍ）において室温で１．５５〜１．６５の比較的高い屈折率となる。一方、一般式[II]の化合物を単独で用いる場合は、１．４７〜１．５５という比較的低い屈折率となる。従って、一般式[I]及び[II]で表される化合物を各々１種以上併用することにより、１．４７〜１．６５の間で所望の屈折率を有する低複屈折樹脂基板を得ることができる。
【００３６】
＜補助成分＞
本発明に係る基板材料は、多官能（メタ）アクリレートを必須成分とする多官能（メタ）アクリレート含有光硬化性モノマー組成物を重合硬化させてなるものであり、この光硬化性モノマー組成物が少量の補助成分を含んでもよいことは前記したところである。
【００３７】
従って、本発明に係る樹脂基板は、その硬化前の光硬化性モノマー組成物１００重量部に対し３０重量部程度までの量でラジカル重合、付加重合可能な他の単量体を混合して上記多官能（メタ）アクリレートと共重合させて製造することも可能である。その際に用いる他の単量体としては、例えばメチル（メタ）アクリレート、フェニル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、メタクリロイルオキシメチルテトラシクロドデカン、メタクリロイルオキシメチルテトラシクロドデセン、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（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、２，２−ビス［４−（β−メタクリロイルオキシエトキシ）フェニル］プロパン、２，２’−ビス［４−（β−メタクリロイルオキシエトキシ）シクロヘキシル］プロパン、１，４−ビス（メタクリロイルオキシメチル）シクロヘキサン、トリメチロールプロパントリ（メタ）アクリレート等の（メタ）アクリレート化合物、スチレン、クロルスチレン、ジビニルベンゼン、α−メチルスチレン等の核及び／又は側鎖置換，非置換スチレンなどが挙げられるが、好ましくは、下記一般式[III]、[IV]及び[V]で示される分子内に２個以上の官能基（チオール基）を有する多官能メルカプト化合物よりなる群から選ばれる１種又は２種以上のメルカプト化合物が挙げられる。
【００３８】
【化１１】
【００３９】
【化１２】
【００４０】
【化１３】
【００４１】
なお、上記一般式[III]、[IV]及び[V]中の各記号は下記の意味を持つ。
【００４２】
Ｒ７：メチレン基又はエチレン基
Ｒ８：エーテル基、チオエーテル基を含んでいてもよい炭素数２〜１５の炭化水素基。好ましくは炭素数２〜６の炭化水素基
ａ：２〜６の整数
Ｒ：ＨＳ−（ＣＨ２−）ｂ（ＣＯ）−（ＯＣＨ２）ｄ−（ＣＨ２−）ｃ−
（ただしｂ，ｃは０〜２の整数、ｄは１〜４の整数）
Ｒ９：炭素数１〜３の炭化水素基
Ｒ１０：炭素数１〜３の炭化水素基
ｅ，ｆ：０又は１
ｇ：１又は２
上記一般式[III]で示されるメルカプト化合物は、２〜６価のチオグリコール酸エステル又はチオプロピオン酸エステルである。式[III]の化合物の具体例としては、例えばペンタエリスリトールテトラキス（β−チオプロピオネート）、ペンタエリスリトールテトラキス（チオグリコレート）、トリメチロールプロパントリス（β−チオプロピオネート）、トリメチロールプロパントリス（チオグリコレート）、ジエチレングリコールビス（β−チオプロピオネート）、ジエチレングリコールビス（チオグリコレート）、トリエチレングリコールビス（β−チオプロピオネート）、トリエチレングリコールビス（チオグリコレート）、ジペンタエリスリトールヘキサシス（β−チオプロピオネート）、ジペンタエリスリトールヘキサシス（チオグリコレート）などが挙げられる。
【００４３】
一般式[IV]で示される化合物は、Ｘ−ＳＨ基含有トリイソシアヌレートである。式[IV]の化合物の具体例としては、例えばトリス［２−（β−チオプロピオニルオキシ）エチル］イソシアヌレート、トリス（２−チオグリコニルオキシエチル）イソシアヌレート、トリス［２−（β−チオプロピオニルオキシエトキシ）エチル］イソシアヌレート、トリス（２−チオグリコニルオキシエトキシエチル）イソシアヌレート、トリス［３−（β−チオプロピオニルオキシ）プロピル］イソシアヌレート、トリス（３−チオグリコニルオキシプロピル）イソシアヌレートなどが挙げられる。
【００４４】
一般式[V]で示される化合物は、α，Ｘ−ＳＨ基含有化合物である。式[V]の化合物の具体例としては、例えばペンゼンジメルカプタン、キシリレンジメルカプタン、４，４’−ジメルカプトジフェニルスルフィドなどが挙げられる。
【００４５】
これらのメルカプト化合物を配合することにより、樹脂基板の製造に当り、チオール基のもつ連鎖移動剤としての作用が有効に発揮され、重合硬化をおだやかに均一に進行させ、得られる硬化樹脂の複屈折を低減することができる。また、これらのメルカプト化合物がビス（メタ）アクリレートにより形成される３次元網目構造に入り込み、得られる樹脂基板に適度な靱性が付与される。更に、分子内に２個以上のチオール基を有する、即ち多官能性のメルカプト化合物を用いることで、得られる硬化樹脂の耐熱性を大きく損なうことなく、複屈折、機械強度などを改善することができる。
【００４６】
本発明に係る基板材料として、前記多官能（メタ）アクリレートと上記メルカプト化合物を併用する場合、その組成割合は、多官能（メタ）アクリレート７０〜９９．９重量部に対して、メルカプト化合物０．１〜３０重量部とするのが好ましく、更に好ましくは多官能（メタ）アクリレート８０〜９９重量部に対して、メルカプト化合物１〜２０重量部の範囲である。メルカプト化合物の割合が少なすぎると硬化樹脂の複屈折改良効果が得られなくなり、逆に多すぎると硬化樹脂の耐熱性が低くなる。
【００４７】
なお、補助成分としては、上記メルカプト化合物の他、酸化防止剤、紫外線吸収剤、染顔料、充填剤などを用いることができる。
【００４８】
＜賦形・重合硬化＞
本発明に係る光硬化性モノマー組成物は賦形されて硬化される。その硬化は、紫外線等の活性エネルギー線によりラジカルを発生する光重合開始剤を添加する公知のラジカル重合により実施される。その際に用いる光重合開始剤としては、例えばベンゾフェノン、ベンゾイルメチルエーテル、ベンゾイルイソプロピルエーテル、ジエトキシアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２，６−ジメチルベンゾイルジフェニルホスフィンオキシド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド等が挙げられる。このうち、好ましい光重合開始剤は、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、ベンゾフェノンである。これらの光重合開始剤は２種以上を併用してもよい。
【００４９】
これら光重合開始剤の添加量は、モノマー１００重量部に対し０．０１〜１重量部、好ましくは０．０２〜０．３重量部である。光重合開始剤の添加量が多すぎると、重合が急激に進行し複屈折の増大をもたらすだけでなく色相も悪化する。また、少なすぎると光硬化性モノマー組成物を充分に硬化させることができなくなる。
【００５０】
照射する活性エネルギー線の量は、光重合開始剤がラジカルを発生する範囲であれば任意であるが、極端に少ない場合は重合が不完全となって硬化物の耐熱性、機械特性が十分に発現されず、逆に極端に過剰な場合には硬化物の黄変等の光による劣化を生じるので、モノマーの組成及び光重合開始剤の種類、量に合わせて２００〜４００ｎｍの紫外線を好ましくは０．１〜２００Ｊの範囲で照射する。使用するランプの具体例としては、メタルハライドランプ、高圧水銀灯ランプ等を挙げることができる。
【００５１】
なお、硬化をすみやかに完了させる目的で、熱重合を併用してもよい。すなわち光照射と同時に組成物並びに型全体を３０〜３００℃の範囲で加熱する。この場合は重合をよりよく完結するために熱重合開始剤を添加してもよいが、その過剰な使用は複屈折の増大と色相の悪化をもたらす。熱重合開始剤の具体例としてはベンゾイルパーオキシド、ジイソプロピルパーオキシカーボネート、ｔ−ブチルパーオキシ（２−エチルヘキサノエート）等が挙げられ、使用量はモノマー１００重量部に対して１重量部以下が好ましい。
【００５２】
本発明においては、光照射によるラジカル重合を行った後、硬化物を加熱することにより重合反応の完結及び重合時に発生する内部歪を低減することも可能である。この場合、加熱温度は、硬化物の組成やガラス転移温度に合わせて適宜選択されるが、過剰な加熱は硬化物の色相悪化をもたらすため、ガラス転移温度付近かそれ以下の温度が好ましい。
【００５３】
なお、賦形のための型としては、通常の場合、光学研磨されたガラス板及びスペーサーとしての所定の厚さのシリコン板を用いる。用いるガラス板の表面粗さは、得られる樹脂基板の表面粗さに影響を与えるので、樹脂基板に必要とされる表面粗さに応じてガラス板の表面粗さを制御する必要がある。一般に、表面粗さＲｚが１〜５０ｎｍの樹脂基板を得るには、型として用いるガラス板の表面粗さＲｚは０．２〜２０ｎｍであることが望ましい。樹脂基板の表面粗さに影響を与えるファクターとしては、上記のガラス板の表面粗さ以外に、紫外線照射量、光開始剤量などがあるので必要に応じて各パラメータを決定する。例えば、樹脂基板の表面粗さＲｚが５〜１０ｎｍのものを得るためには、ガラス板の表面粗さＲｚが１〜５ｎｍのものを用いて、このガラス板の上にスペーサとしてシリコン板を配置し、多官能（メタ）アクリレート及び補助成分を所定割合で混合して脱泡した光硬化性モノマー組成物を注液し、ガラス面より上下４０ｃｍ離隔した出力８０Ｗ／ｃｍのメタルハライドランプの間にて、１０分間紫外線を照射する。
【００５４】
＜樹脂基板の物性＞
有機電界発光素子用基板としての光学特性の面から、本発明に係る光硬化性樹脂製基板の光複屈折は２０ｎｍ以下であることが好ましい。
【００５５】
また、本発明に係る樹脂基板の厚みは、通常の場合、０．１〜５ｍｍ、好ましくは０．３〜１ｍｍである。
【００５６】
また、本発明に係る樹脂基板の発光素子作製面側の表面粗さは１０点平均粗さＲｚで１〜５０ｎｍ、好ましくは２〜２０ｎｍである。樹脂基板のＲｚが５０ｎｍより大きくなると、基板表面に作製される有機電界発光素子の電極間で短絡が起こりやすくなり基板としては適さない。また、Ｒｚが１ｎｍより小さいと、基板表面に形成される有機層と基板との接着力が小さくなり、その後の陰極金属層等の蒸着時の応力で有機層が剥がれやすくなり、やはり基板として適さなくなる。
【００５７】
なお、この樹脂基板のガスバリア性をより高める目的で、基板の少なくとも片面に緻密なシリコン酸化膜等を設けても良い。
【００５８】
次に、このような光硬化性樹脂製基板を用いた本発明の有機電界発光素子の構成層について説明する。
【００５９】
基板１上に形成された陽極２は、有機発光層３への正孔注入の役割を果たすものである。この陽極２は、通常、アルミニウム、金、銀、白金、ニッケル、パラジウム、白金等の金属、インジウム及び／又はスズの酸化物などの金属酸化物、ヨウ化銅などのハロゲン化金属、カーボンブラック、或いは、ポリ（３−メチルチオフェン）、ポリピロール、ポリアニリン等の導電性高分子など、好ましくは、インジウム・スズ酸化物により形成される。陽極２の形成は通常、スパッタリング法、真空蒸着法などにより行われることが多い。銀などの金属微粒子、ヨウ化銅などの微粒子、カーボンブラック、導電性の金属酸化物微粒子、導電性高分子微粉末などを用いる場合には、これを適当なバインダー樹脂溶液に分散し、基板１上に塗布することにより陽極２を形成することもできる。また、導電性高分子を用いる場合には、電解重合により直接基板１上に薄膜を形成するか、基板１上に導電性高分子を塗布することにより、陽極２を形成することもできる（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，６０巻，２７１１頁，１９９２年）。陽極２は異なる物質を積層して形成することも可能である。
【００６０】
陽極２の厚みは、透明性の要求の有無により異なる。透明性が必要とされる場合は、可視光の透過率を、通常、６０％以上、好ましくは８０％以上とすることが望ましく、この場合、厚みは、通常、５〜１０００ｎｍ、好ましくは１０〜５００ｎｍ程度である。陽極２が不透明でよい場合には、基板１と同一材料であってもよい。また、陽極２の上に異なる導電材料を積層することも可能である。
【００６１】
陽極２の上に形成される有機発光層３は、電界が与えられた電極間において、陽極２から注入された正孔と陰極４から注入された電子を効率よく輸送して再結合させ、かつ、再結合により効率よく発光する材料から形成される。通常、この有機発光層３は発光効率の向上のために、図２に示す様に、正孔輸送層３ａと電子輸送層３ｂに分割した機能分離型にすることが行われる（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５１巻，９１３頁，１９８７年）。
【００６２】
図２に示す機能分離型有機電界発光素子１０Ａにおいて、正孔輸送層３ａの材料としては、陽極２からの正孔注入効率が高く、かつ、注入された正孔を効率よく輸送することができる材料であることが必要である。そのためには、イオン化ポテンシャルが小さく、しかも正孔移動度が大きく、更に安定性に優れ、製造時や使用時にトラップとなる不純物が発生しにくいことが要求される。
【００６３】
このような正孔輸送材料としては、例えば、１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）シクロヘキサン等の３級芳香族アミンユニットを連結した芳香族ジアミン化合物（特開昭５９−１９４３９３号公報）、４，４’−ビス [Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ] ビフェニルで代表される２個以上の３級アミンを含み２個以上の縮合芳香族環が窒素原子に置換した芳香族アミン（特開平５−２３４６８１号公報）、トリフェニルベンゼンの誘導体でスターバースト構造を有する芳香族トリアミン（米国特許第４，９２３，７７４号）、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）ビフェニル−４，４’−ジアミン等の芳香族ジアミン（米国特許第４，７６４，６２５号）、α，α，α’，α’−テトラメチル−α，α’−ビス（４−ジ−ｐ−トリルアミノフェニル）−ｐ−キシレン（特開平３−２６９０８４号公報）、分子全体として立体的に非対称なトリフェニルアミン誘導体（特開平４−１２９２７１号公報）、ビレニル基に芳香族ジアミノ基が複数個置換した化合物（特開平４−１７５３９５号公報）、エチレン基で３級芳香族アミンユニットを連結した芳香族ジアミン（特開平４−２６４１８９号公報）、スチリル構造を有する芳香族ジアミン（特開平４−２９０８５１号公報）、チオフェン基で芳香族３級アミンユニットを連結したもの（特開平４−３０４４６６号公報）、スターバースト型芳香族トリアミン（特開平４−３０８６８８号公報）、ベンジルフェニル化合物（特開平４−３６４１５３号公報）、フルオレン基で３級アミンを連結したもの（特開平５−２５４７３号公報）、トリアミン化合物（特開平５−２３９４５５号公報）、ビスジピリジルアミノビフェニル（特開平５−３２０６３４号公報）、Ｎ，Ｎ，Ｎ−トリフェニルアミン誘導体（特開平６−１９７２号公報）、フェノキサジン構造を有する芳香族ジアミン（特開平７−１３８５６２号公報）、ジアミノフェニルフェナントリジン誘導体（特開平７−２５２４７４号公報）、ヒドラゾン化合物（特開平２−３１１５９１号公報）、シラザン化合物（米国特許第４，９５０，９５０号公報）、シラナミン誘導体（特開平６−４９０７９号公報）、ホスファミン誘導体（特開平６−２５６５９号公報）、キナクリドン化合物等が挙げられる。これらの化合物は、単独で用いてもよく、また、必要に応じて２種以上を混合して用いてもよい。
【００６４】
なお、上記の化合物以外に、正孔輸送層３ａの材料として、ポリビニルカルバゾールやポリシラン（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５９巻、２７６０頁，１９９１年）、ポリフォスファゼン（特開平５−３１０９４９号公報）、ポリアミド（特開平５−３１０９４９号公報）、ポリビニルトリフェニルアミン（特開平７−５３９５３号公報）、トリフェニルアミン骨格を有する高分子（特開平４−１３３０６５号公報）、トリフェニルアミン単位をメチレン基等で連結した高分子（Ｓｙｎｔｈｅｔｉｃ Ｍｅｔａｌｓ，５５−５７巻，４１６３頁，１９９３年）、芳香族アミンを含有するポリメタクリレート（Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｐｏｌｙｍ．Ｃｈｅｍ．Ｅｄ．，２１巻，９６９頁，１９８３年）等の高分子材料を用いることができる。
【００６５】
正孔輸送層３ａは、これらの正孔輸送材料を塗布法又は真空蒸着法により成膜することにより、前記陽極２上に積層形成される。
【００６６】
塗布法の場合は、正孔輸送材料の１種又は２種以上と、必要により正孔のトラップにならないバインダー樹脂や塗布性改良剤などの添加剤とを添加し、溶剤に溶解して塗布溶液を調製し、これをスピンコート法などの方法により陽極２上に塗布、乾燥して有機正孔輸送層３ａを形成する。この場合、バインダー樹脂としては、ポリカーボネート、ポリアリレート、ポリエステル等が挙げられる。バインダー樹脂の添加量が多いと正孔移動度を低下させるので、少ない方が望ましく、通常、５０重量％以下が好ましい。
【００６７】
一方、真空蒸着法の場合には、正孔輸送材料を真空容器内に設置されたルツボに入れ、真空容器内を適当な真空ポンプで１０−４Ｐａ程度にまで排気した後、ルツボを加熱して、正孔輸送材料を蒸発させ、ルツボに対向配置した基板１上の陽極２上に正孔輸送層３ａを形成する。
【００６８】
このようにして正孔輸送層３ａを形成する場合、更に、アクセプタとして、芳香族カルボン酸の金属錯体及び／又は金属塩（特開平４−３２０４８４号公報）、ベンゾフェノン誘導体及びチオベンゾフェノン誘導体（特開平５−２９５３６１号公報）、フラーレン類（特開平５−３３１４５８号公報）等を１０−３〜１０重量％の濃度でドープして、フリーキャリアとしての正孔を生成させることにより、低電圧駆動を可能にすることができる。
【００６９】
正孔輸送層３ａの膜厚は、通常、１０〜３００ｎｍ、好ましくは３０〜１００ｎｍである。このような膜厚の薄い正孔輸送層を一様に形成するためには、一般に真空蒸着法を採用するのが好適である。
【００７０】
また、正孔注入効率を更に向上させ、かつ、有機層全体の陽極２への付着力を改善する目的で、図３に示す如く、正孔輸送層３ａと陽極２との間に正孔注入層３ｃを形成することも行われている。正孔注入層３ｃに用いられる材料としては、イオン化ポテンシャルが低く、導電性が高く、更に陽極２上で熱的に安定な薄膜を形成し得る材料が望ましく、フタロシアニン化合物やポルフィリン化合物（特開昭５７−５１７８１号公報、特開昭６３−２９５６９５号公報）が用いられる。このような正孔注入層３ｃを介在させることで、初期の素子の駆動電圧が下がると同時に、素子を定電流で連続駆動した時の電圧上昇も抑制される効果が得られる。正孔注入層３ｃもまた、正孔輸送層３ａと同様にしてアクセプタをドープすることで導電性を向上させることが可能である。
【００７１】
正孔注入層３ｃの膜厚は、通常、２〜１００ｎｍ、好ましくは５〜５０ｎｍである。このような膜厚の薄い正孔注入層を一様に形成するためには、一般に真空蒸着法を採用するのが好適である。
【００７２】
正孔輸送層３ａの上に形成される電子輸送層３ｂは、電界が与えられた電極間において、陰極からの電子を効率よく正孔輸送層３ａの方向に輸送することができる化合物で構成される。
【００７３】
電子輸送層３ｂに用いられる電子輸送性化合物としては、陰極４からの電子注入効率が高く、かつ、注入された電子を効率よく輸送することができる化合物であることが必要である。そのためには、電子親和力が大きく、しかも電子移動度が大きく、更に安定性に優れ、製造時や使用時にトラップとなる不純物が発生しにくい化合物であることが要求される。
【００７４】
このような条件を満たす材料としては、テトラフェニルブタジエンなどの芳香族化合物（特開昭５７−５１７８１号公報）、８−ヒドロキシキノリンのアルミニウム錯体などの金属錯体（特開昭５９−１９４３９３号公報）、シクロペンタジエン誘導体（特開平２−２８９６７５号公報）、ペリノン誘導体（特開平２−２８９６７６号公報）、オキサジアゾール誘導体（特開平２−２１６７９１号公報）、ビススチリルベンゼン誘導体（特開平１−２４５０８７号公報、同２−２２２４８４号公報）、ペリレン誘導体（特開平２−１８９８９０号公報、同３−７９１号公報）、クマリン化合物（特開平２−１９１６９４号公報、同３−７９２号公報）、希土類錯体（特開平１−２５６５８４号公報）、ジスチリルピラジン誘導体（特開平２−２５２７９３号公報）、ｐ−フェニレン化合物（特開平３−３３１８３号公報）、チアジアゾロピリジン誘導体（特開平３−３７２９２号公報）、ピロロピリジン誘導体（特開平３−３７２９３号公報）、ナフチリジン誘導体（特開平３−２０３９８２号公報）などが挙げられる。
【００７５】
これらの化合物を用いた電子輸送層３ｂは、一般に、電子を輸送する役割と、正孔と電子の再結合の際に発光をもたらす役割とを同時に果たすことができる。
【００７６】
正孔輸送層３ａが発光機能を有する場合は、電子輸送層３ｂは電子を輸送する役割だけを果たす場合もある。
【００７７】
素子の発光効率を向上させるとともに発光色を変える目的で、例えば、８−ヒドロキシキノリンのアルミニウム錯体をホスト材料として、クマリン等のレーザ用蛍光色素をドープすること（Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，６５巻，３６１０頁，１９８９年）等も行われているが、本発明においても、上記の有機電子輸送性材料をホスト材料として各種の蛍光色素を１０−３〜１０モル％ドープすることにより、素子の発光特性をより一層向上させることができる。
【００７８】
電子輸送層３ｂの膜厚は、通常、１０〜２００ｎｍ、好ましくは３０〜１００ｎｍである。
【００７９】
電子輸送層も正孔輸送層と同様の方法で形成することができるが、通常は真空蒸着法が用いられる。
【００８０】
なお、図１に示すような機能分離を行わない単層型の有機発光層３としては、先に挙げたポリ（ｐ−フェニレンビニレン）（Ｎａｔｕｒｅ，３４７巻，５３９頁，１９９０年他）、ポリ [２−メトキシ−５−（２−エチルヘキシルオキシ）−１，４−フェニレンビニレン] （Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５８巻，１９８２頁，１９９１年他）、ポリ（３−アルキルチオフェン）（Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，３０巻，Ｌ１９３８頁，１９９１年他）等の高分子材料や、ポリビニルカルバゾール等の高分子に発光材料と電子移動材料を混合した系（応用物理，６１巻，１０４４頁，１９９２年）等が挙げられる。
【００８１】
陰極４は、有機発光層３に電子を注入する役割を果たす。陰極４として用いられる材料は、前記陽極２に使用される材料を用いることが可能であるが、効率よく電子注入を行うには、仕事関数の低い金属が好ましく、スズ、マグネシウム、インジウム、カルシウム、アルミニウム、銀等の適当な金属又はそれらの合金が好適である。陰極４の膜厚は、通常、陽極２と同程度である。
【００８２】
低仕事関数金属からなる陰極を保護する目的で、この陰極上に更に、仕事関数が高く大気に対して安定な金属層を積層することにより、素子の安定性を増すことができる。この目的のための金属層には、アルミニウム、銀、ニッケル、クロム、金、白金等の金属が用いられる。
【００８３】
なお、図１〜３は、本発明で採用される素子本体の一例を示すものであって、本発明は、図示のもの以外に、以下に示すような層構成の素子本体に適用することができる。
【００８４】
陽極／正孔輸送層／電子輸送層／界面層／陰極、
陽極／正孔輸送層／電子輸送層／他の電子輸送層／陰極、
陽極／正孔輸送層／電子輸送層／他の電子輸送層／界面層／陰極、
陽極／正孔注入層／正孔輸送層／電子輸送層／界面層／陰極、
陽極／正孔注入層／正孔輸送層／電子輸送層／他の電子輸送層／陰極
上記層構成で、界面層は陰極と有機層とのコンタクトを向上させるためのもので、芳香族ジアミン化合物（特開平６−２６７６５８号公報）、キナクリドン化合物（特開平６−３３００３１号公報）、ナフタセン誘導体（特開平６−３３００３２号公報）、有機シリコン化合物（特開平６−３２５８７１号公報）、有機リン化合物（特開平６−３２５８７２号公報）、Ｎ−フェニルカルバゾール骨格を有する化合物（特願平６−１９９５６２号）、Ｎ−ビニルカルバゾール重合体（特願平６−２００９４２号）等で構成された層が例示できる。界面層の膜厚は、通常、２〜１００ｎｍ、好ましくは５〜３０ｎｍである。界面層を設ける代わりに、有機発光層及び電子輸送層の陰極界面近傍に上記界面層の材料を５０重量％以上含む領域を設けてもよい。
【００８５】
また、他の電子輸送層は、有機電界発光素子の発光効率を更に向上させるために、電子輸送層の上にさらに積層形成されるものであり、この電子輸送層に用いられる化合物には、陰極からの電子注入が容易で、電子の輸送能力が更に大きいことが要求される。このような電子輸送性材料としては、オキサジアゾール誘導体（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５５巻，１４８９頁，１９８９年他）やそれらをポリメタクリル酸メチル（ＰＭＭＡ）等の樹脂に分散した系（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，６１巻，２７９３頁，１９９２年）、フェナントロリン誘導体（特開平５−３３１４５９号公報）、又は、ｎ型水素化非晶質炭化シリコン、ｎ型硫化亜鉛、ｎ型セレン化亜鉛等が挙げられる。この他の電子輸送層の膜厚は、通常、５〜２００ｎｍ、好ましくは１０〜１００ｎｍである。
【００８６】
本発明の有機電界発光素子は、単一の素子、アレイ状に配置された構造からなる素子、陽極と陰極がＸ−Ｙマトリックス状に配置された構造の素子のいずれにも適用することができる。
【００８７】
【実施例】
次に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。
【００８８】
実施例１
ｐ−ビス（β−メタクリロイルオキシエチルチオ）キシリレン９９重量部、ペンタエリスリトールテトラキス（β−チオプロピオネート）１重量部、光重合開始剤として２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド（ＢＡＳＦ社製「ルシリンＴＰＯ」）０．０５重量部、ベンゾフェノン０．０２重量部を均一に撹拌混合した後、脱泡して光硬化性モノマー組成物を得た。
【００８９】
一方、樹脂を賦形するための型として、光学研磨されたガラス板及びスペーサーとして厚さ１ｍｍのシリコン板を用い、上記光硬化性モノマー組成物を、この光学研磨ガラスの型に注液し、ガラス面より距離４０ｃｍの上下位置にある出力８０Ｗ／ｃｍのメタルハライドランプの間にて、１０分間紫外線を照射した。紫外線照射後離型し、１２０℃で１時間加熱して硬化物を得た。この硬化物をスライドガラス状（２５×７５ｍｍ）にカットし基板Ａとした。基板Ａの諸特性は表１に示す通りであった。なお、各特性の評価は以下の方法で行った。
【００９０】
（１）外観：目視により評価した。
（２）比重：幅及び長さ各５ｃｍ、厚さ１ｍｍの試験片の重量及び体積を測定することにより評価した。
（３）落球衝撃試験：幅及び長さ各５ｃｍ、厚さ１ｍｍの試験片に、１６ｇの鋼球を自然落下させることにより試験片が破損する最低の高さで評価した。
（４）曲げ弾性率：幅１ｃｍ、厚さ１ｍｍの板について支点間距離３ｃｍにてオートグラフを用いて２５℃で評価した。
（５）表面粗さＲｚ：触針式表面粗さ計（ランクテーラーホブソン社製タリステップ：触針の先端形状が０．２×０．２μｍ角）を用い十点平均粗さ（ＪＩＳＢ０６０１）で評価した。
（６）屈折率：アッベ屈折計（アタゴ社製）を用いて２５℃で評価した。
（７）複屈折：複屈折測定装置（オーク社製）を用いて２５℃で評価した。
（８）吸水率：６０℃で水中に１週間浸漬した時の飽和吸水率で評価した。
（９）ガラス転移温度：厚さ１ｍｍの試験片について５０ｇの加重でＴＭＡ（熱機械分析装置）を用いて評価した。
【００９１】
次に、この基板Ａ上にインジウム・スズ酸化物（ＩＴＯ）透明導電膜を１２０ｎｍ堆積（豊和産業社製：低温スパッタ成膜品：シート抵抗２０Ω）し、ＩＴＯ基板Ａとした。
【００９２】
このＩＴＯ基板Ａを用いて、図３に示す構造を有する有機電界発光素子を以下の方法で作製した。まず、ＩＴＯ基板Ａ上に堆積されたＩＴＯ透明導電膜を通常のフォトリソグラフィ技術と塩酸エッチングを用いて２ｍｍ幅のストライプにパターニングして陽極を形成した。
【００９３】
パターン形成したＩＴＯ基板を、アセトンによる超音波洗浄、純水による水洗、イソプロピルアルコールによる超音波洗浄の順で洗浄後、窒素ブローで乾燥させ、最後に紫外線オゾン洗浄を行って、真空蒸着装置内に設置した。装置の粗排気を油回転ポンプにより行った後、装置内の真空度が２×１０−６Ｔｏｒｒ（約２．７×１０−４Ｐａ）以下になるまで液体窒素トラップを備えた油拡散ポンプを用いて排気した。
【００９４】
上記装置内に配置されたモリブデンボートに入れた以下に示す銅フタロシアニン（Ｈ１）（結晶形はβ型）を加熱して蒸着を行った。蒸気は、真空度１．１×１０−６ｔｏｒｒ（約１．５×１０−４Ｐａ）、蒸着時間１分で行い、膜厚２０ｎｍの正孔注入層３ｃを形成した。
【００９５】
【化１４】
【００９６】
次に、上記装置内に配置されたセラミックるつぼに入れた、以下に示す４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビスフェノール（Ｈ２）をるつぼの周囲のタンタル線ヒーターで加熱して正孔注入層３ｃの上に積層した。この時のるつぼの温度は、２３０〜２４０℃の範囲で制御した。蒸着時の真空度８×１０−７Ｔｏｒｒ（約１．１×１０−４Ｐａ）、蒸着時間１分５０秒で膜厚６０ｎｍの正孔輸送層３ａを形成した。
【００９７】
【化１５】
【００９８】
引き続き、発光機能を有する電子輸送層３ｂの材料として、以下に示すアルミニウムの８−ヒドロキシキノリン錯体：Ａｌ（Ｃ９Ｈ６ＮＯ）３（Ｅ１）を上記正孔輸送層３ａの上に同様にして蒸着した。この時のるつぼの温度は３１０〜３２０℃の範囲で制御した。蒸着時の真空度は９×１０−７Ｔｏｒｒ（約１．２×１０−４Ｐａ）、蒸着時間は２分４０秒で、膜厚７５ｎｍの電子輸送層３ｂを形成した。
【００９９】
【化１６】
【０１００】
なお、正孔注入層３ｃ、正孔輸送層３ａ及び電子輸送層３ｂを真空蒸着する時の基板温度は室温に保持した。
【０１０１】
正孔注入層３ｃ、正孔輸送層３ａ及び電子輸送層３ｂを形成した基板を一度前記真空蒸着装置内より大気中に取り出して、陰極蒸着用のマスクとして２ｍｍ幅のストライプ状シャドーマスクを、陽極２のＩＴＯストライプと直交するように密着させて設け、別の真空蒸着装置内に設置して各有機層の蒸着時と同様にして装置内の真空度が２×１０−６Ｔｏｒｒ（約２．７×１０−４Ｐａ）以下になるまで排気した。続いて、陰極４として、マグネシウムと銀の合金電極を２元同時蒸着法によって膜厚１００ｎｍとなるように蒸着した。蒸着はモリブデンボートを用いて、真空度１×１０−５Ｔｏｒｒ（約１．３×１０−３Ｐａ）、蒸着時間３分１０秒で行った。また、マグネシウムと銀の原子比は１０：１．２とした。さらに続いて、装置の真空を破らないで、アルミニウムをモリブデンボートを用いて１００ｎｍの膜厚でマグネシウム・銀合金膜の上に積層して陰極４を完成させた。アルミニウム蒸着時の真空度は２．３×１０−５Ｔｏｒｒ（約３．１×１０−３Ｐａ）、蒸着時間は１分４０秒であった。以上のマグネシウム・銀合金とアルミニウムの２層型陰極の蒸着時の基板温度は室温に保持した。
【０１０２】
以上のようにして、２ｍｍ×２ｍｍのサイズの有機電界発光素子を得た。この素子を陰極蒸着装置から取り出した後、陽極２にプラス、陰極４にマイナスの直流電圧を印加して発光させ、発光特性を測定した。
【０１０３】
印加電圧を１〜１５Ｖの範囲で１Ｖステップで変化させた時の発光輝度の変化を図４に示した。また、１５Ｖを素子に印加した時の発光輝度、１５Ｖでの発光効率、及び、Ｌ／Ｊ（輝度−電流密度特性を直線で近似したときの傾きで、量子効率に対応した量）を表２に示した。
【０１０４】
実施例２
モノマー成分としてビス（オキシメチル）トリシクロ［５．２．１．０２．６］デカン＝ジメタクリレート９６重量部及びペンタエリスリトールテトラキス（β−チオプロピオネート）４重量部を用いたこと以外は実施例１と同様にして硬化物を得た。この硬化物をスライドガラス状にカットして基板Ｂとした。この基板Ｂの諸特性は表１に示す通りであった。
【０１０５】
次に、基板Ｂ上にＩＴＯ透明導電膜を実施例１と同様の低温スパッタ法で堆積し、ＩＴＯ基板Ｂとした。このＩＴＯ基板Ｂのシート抵抗値は２０Ωであった。
【０１０６】
更に、このＩＴＯ基板Ｂを用いて実施例１と同様にして図３に示す構造の有機電界発光素子を作製し、同様に発光特性を測定して結果を図４及び表２に示した。
【０１０７】
比較例１
コーニング社製７０５９ガラスをスライドガラス状にカットして基板Ｃとした。この基板Ｃの諸特性は表１に示す通りであった。
【０１０８】
次に、この基板Ｃ上にＩＴＯ透明導電膜を実施例１と同様の低温スパッタ法で堆積し、ＩＴＯ基板Ｃとした。このＩＴＯ基板Ｃのシート抵抗値は２０Ωであった。
【０１０９】
更に、このＩＴＯ基板Ｃを用いて実施例１と同様にして図３に示す構造の有機電界発光素子を作製し、同様に発光特性を測定して結果を図４及び表２に示した。
【０１１０】
比較例２
比較例１と同様にコーニング社製７０５９ガラスを基板とし、この基板上にＩＴＯ透明導電膜を電子ビーム蒸着法（ジオマテック社製）で堆積し、ＩＴＯ基板Ｄとした。このＩＴＯ基板Ｄのシート抵抗値は１５Ωであった。また、ＩＴＯ基板ＤのＸ線回折分析を行ったところ、低温スパッタ法による比較例１のＩＴＯ基板Ｃに比較して、２θ＝３０．６°付近のＩｎ２Ｏ３結晶の回折ピーク強度が大きく、結晶性が高いことが分かった。
【０１１１】
このＩＴＯ基板Ｄを用いて実施例１と同様にして図３に示す構造の有機電界発光素子を作製し、同様に発光特性を測定して結果を図４及び表２に示した。
【０１１２】
比較例３
光硬化性モノマー組成物を注入するガラスの型の表面を光学研磨をしなかったことを除いては実施例１と同様の方法で硬化物を得た。この硬化物をスライドガラス状にカットし基板Ｅとした。この基板Ｅの諸特性は表１に示す通りであった。
【０１１３】
次に、この基板Ｅ上にＩＴＯ透明導電膜を実施例１と同様の低温スパッタ法で堆積し、ＩＴＯ基板Ｅとした。このＩＴＯ基板Ｅのシート抵抗値は２０Ωであった。
【０１１４】
このＩＴＯ基板Ｅを用いて実施例１と同様にして図３に示す構造の有機電界発光素子を作製し、同様の方法で評価を行ったところ、５Ｖを印加した段階で素子が短絡破壊した。
【０１１５】
【表１】
【０１１６】
【表２】
【０１１７】
【発明の効果】
以上詳述した通り、本発明の有機電界発光素子及びその製造方法によれば、軽量で機械的強度が大きい、プラスチック基板を用いて、発光特性においても従来のガラス基板を用いた素子と比較し同等以上の特性を有する有機電界発光素子を高い生産性にて得ることができる。
【０１１８】
従って、本発明による有機電界発光素子は、フラットパネル・ディスプレイ（例えばＯＡコンピュータ用や壁掛けテレビ）や面発光体としての特徴を生かした光源（例えば、複写機の光源、演奏ディスプレイや計器類のバックライト光源）、表示板、標識灯への応用が期待され、その技術的価値は極めて大きい。
【図面の簡単な説明】
【図１】 本発明の有機電界発光素子の一実施例を示す模式的断面図である。
【図２】 本発明の有機電界発光素子の他の実施例を示す模式的断面図である。
【図３】 本発明の有機電界発光素子の別の実施例を示す模式的断面図である。
【図４】 実施例１，２及び比較例１，２における有機電界発光素子の発光輝度の印加電圧依存性を示すグラフである。
【符号の説明】
１ 基板
２ 陽極
３ 有機発光層
４ 陰極
３ａ 正孔輸送層
３ｂ 電子輸送層
３ｃ 正孔注入層
１０，１０Ａ，１０Ｂ 有機電界発光素子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic electroluminescent device and a method for manufacturing the same, and more particularly to an improvement in a support substrate of a thin film light emitting device that emits light by applying an electric field to a light emitting layer made of an organic compound.
[0002]
[Prior art]
Conventionally, as thin film type electroluminescent (EL) elements, ZnS, CaS, SrS, etc., which are inorganic material II-IV group compound semiconductors, Mn or rare earth elements (Eu, Ce, Tb, Sm, etc.) that are emission centers ) Is generally used, but an EL element made from the above inorganic material is
(1) AC drive is required (generally 50 to 1000 Hz),
(2) High drive voltage (generally around 200V),
(3) Full color is difficultTheThere is a problem with blue in particular,
(4) High cost of peripheral drive circuit,
Have the following problems.
[0003]
However, in recent years, an EL element using an organic thin film has been developed to improve the above problems. In particular, in order to improve luminous efficiency, the type of electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and an organic hole transport layer composed of aromatic diamine and an organic complex composed of 8-hydroxyquinoline aluminum complex. Development of an organic electroluminescent device provided with a light emitting layer (Appl. Phys. Lett., 51, 913, 1987) allows light emission efficiency compared to a conventional electroluminescent device using a single crystal such as anthracene. Has been greatly improved and is approaching practical characteristics.
[0004]
In addition to the electroluminescent device using the low molecular material as described above, as a material of the organic light emitting layer, poly (p-phenylene vinylene) (Nature, 347, 539, 1990, etc.), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., 58, 1982 et al.), Poly (3-alkylthiophene) (Jpn. J. Appl. Development of electroluminescent devices using polymer materials such as Phys, Vol. 30, L1938, etc., and devices in which low molecular light emitting materials and electron transfer materials are mixed with polymers such as polyvinyl carbazole (Applied Physics, Vol. 61) , Page 1044, 1992).
[0005]
In the organic electroluminescence device as described above, glass is usually used as the substrate. However, in the display panels of personal computers and portable terminals, which are regarded as important applications of organic electroluminescence devices, when glass is used as the substrate, the weight is reduced and the thickness is reduced due to low density of glass and mechanical strength. In addition, there is a problem in terms of formability and workability in terms of improving productivity. For this reason, development of an organic electroluminescent element using plastic as a substrate is strongly desired.
[0006]
[Problems to be solved by the invention]
However, the conventional plastic substrate has the following problems.
[0007]
(1) Transparency and optical properties suitable for organic electroluminescence devices cannot be satisfied.
(2) Inferior heat resistance.
(3) Inferior surface accuracy.
In particular, regarding the optical isotropy, the birefringence Δn · d of the glass substrate is 1 nm or less, whereas the plastic substrate exceeds 10 nm. This birefringence problem is difficult to solve in the case of employing a molding method in which some stretching operation or material flow operation is applied to the resin. In addition, when a relatively thick substrate (for example, 0.4 mm or more) is used, it is difficult to form by extrusion of thermoplastic resin or belt formation. On the other hand, when a thermosetting resin is used, molding takes several hours, and there is a problem in terms of productivity.
[0008]
The present invention solves the above-mentioned conventional problems, uses a plastic substrate having transparency and optical properties suitable for organic electroluminescent elements, excellent heat resistance, surface accuracy, and good moldability, and is lightweight and mechanical. An object of the present invention is to provide an organic electroluminescent device excellent in mechanical strength and productivity and a method for producing the same.
[0009]
[Means for Solving the Problems]
The organic electroluminescent device of the present invention is an organic electroluminescent device in which an anode, an organic light emitting layer and a cathode are laminated on one plate surface of the substrate, the substrate is made of a photocurable resin, and the substrate The surface roughness (Rz) of the one plate surface is 1 to 50 nmThe photocurable resin has the following general formula [I]
[0010]
[Chemical formula 5]
(the above [I] Where R 1 And R 2 Are each a hydrogen atom or a methyl group, R 3 And R 4 Are each a hydrocarbon group having 1 to 6 carbon atoms which may contain an ether group and / or a thioether group, X represents a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and k is 0 to 4 Indicates an integer. )
And the following general formula [II]
[0011]
[Chemical 6]
(the above [II] Where R 5 And R 6 Each represents a hydrogen atom or a methyl group, m represents 1 or 2, and n represents 0 or 1. )
It is obtained by photopolymerizing a monomer containing a polyfunctional (meth) acrylate having two or more functional groups in at least one molecule selected from the group consisting of compounds represented byIt is characterized by that.
0012]
If the substrate is a photocurable resin substrate, the substrate can be easily formed by shaping the photocurable liquid monomer into a plate shape, irradiating the monomer with active energy rays and polymerizing and curing the monomer. Such a photocurable resin substrate has transparency and optical characteristics suitable for an organic electroluminescent element, and is excellent in heat resistance and surface accuracy.
0013]
The surface roughness (Rz) of the laminated surface of the substrate, that is, the surface on which the anode, the organic light emitting layer, and the cathode are laminated (hereinafter referred to as “light emitting element fabrication surface”) is in the range of 1 to 50 nm. Thus, the element constituent layer can be formed on the substrate with good adhesion without causing a short circuit of the element.
0014]
In the present invention, the photocurable resin is preferably obtained by photopolymerizing a monomer containing a polyfunctional (meth) acrylate having two or more functional groups in the molecule. The polyfunctional (meth) acrylate having one or more functional groups is at least one bis (%) selected from the group consisting of a compound represented by the following general formula [I] and a compound represented by the following general formula [II]. A meth) acrylate is preferred.
0015]
[Chemical7]
0016]
(In the above formula [I], R1And R2Are each hydrogenatomOr methyl group, R3And R4 each represents an hydrocarbon group having 1 to 6 carbon atoms which may contain an ether group and / or a thioether group, X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and k is 0 Represents an integer of ~ 4. )
0017]
[Chemical8]
0018]
(In the above formula [II], R5And R6Are each hydrogenatomOr a methyl group, m is 1 or 2, and n is 0 or 1. )
In particular, the photocurable resin according to the present invention is obtained by copolymerizing a polyfunctional (meth) acrylate having two or more functional groups in the molecule and a polyfunctional mercapto compound having two or more functional groups in the molecule. It is preferable to be obtained.
0019]
The substrate is preferably made of a photocurable resin having a birefringence of 20 nm or less.
0020]
Such an organic electroluminescent element of the present invention is a method of producing an organic electroluminescent element by laminating an anode, an organic light emitting layer and a cathode on a substrate, and the substrate is made of a photocurable resin, and The substrate is manufactured by using a substrate having a surface roughness (Rz) of at least one plate surface of 1 to 50 nm and laminating an anode, an organic light emitting layer and a cathode on the one plate surface of the substrate.
0021]
In the present invention, the substrate is preferably a photocurable liquid monomer containing a polyfunctional (meth) acrylate having two or more functional groups in the molecule and a polyfunctional mercapto compound having two or more functional groups in the molecule. Is formed into a plate shape, and it is produced by irradiating it with an active energy ray and curing it by photopolymerization.
0022]
DETAILED DESCRIPTION OF THE INVENTION
Below, the organic electroluminescent element of this invention and its manufacturing method are demonstrated, referring drawings.
0023]
1 to 3 are schematic cross-sectional views showing structural examples of the organic electroluminescent device of the present invention, in which 1 is a substrate, 2 is an anode, 3 is an organic light emitting layer, 3a is a hole transport layer, and 3b is An electron transport layer, 3c is a hole injection layer, 4 is a cathode, 10, 10A, and 10B are organic electroluminescent elements.
0024]
The substrate 1 serves as a support for the organic electroluminescence device, and is required to have excellent characteristics such as optical characteristics, heat resistance, surface accuracy, mechanical strength, light weight, and gas barrier properties. In the present invention, a photocurable resin substrate is employed as the plastic substrate having excellent characteristics. The substrate material used in the present invention will be described below.
0025]
<Multifunctional (meth) acrylate>
The substrate according to the present invention comprises, for example, a sulfur-containing bis (meth) acrylate represented by the following general formula [I] as a polyfunctional (meth) acrylate and an alicyclic skeleton bis (meth) acrylate represented by the following general formula [II]. A photocurable resin obtained by shaping a photocurable monomer composition comprising one or more bis (meth) acrylates selected from the group, and irradiating the composition with an active energy ray to cause photopolymerization and curing. Consists of.
0026]
[Chemical9]
0027]
[Chemical10]
0028]
Each symbol in the general formulas [I] and [II] has the following meaning.
R1And R2: A hydrogen atom or a methyl group. R1, R2May be the same or different.
0029]
R3: An ether group (ether bond: C—O—C), a thioether group (thioether bond: C—S—C) which may contain a hydrocarbon group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms Alkylene group
R4: A C1-C6 hydrocarbon group which may contain an ether group or a thioether group, preferably a C1-C3 alkylene group
X: a halogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms
k: integer from 0 to 4
R5And R6: A hydrogen atom or a methyl group. R5, R6May be the same or different m: 1 or 2
n: 0 or 1
In addition, “comprising” of the “photocurable monomer composition comprising (meth) acrylate” means that the composition does not impair the gist of the present invention, and other than polyfunctional (meth) acrylate. It means that a small amount of auxiliary components may be included. That is, an auxiliary component such as another monomer copolymerizable with the polyfunctional (meth) acrylate specified as the main component of the photocurable monomer composition in the present invention, for example, a photocurable monomer as described later. It means that it may be contained in a range of up to about 30 parts by weight with respect to 100 parts by weight of the composition. Moreover, you may use multiple types of each component in this composition together between components and / or in a component.
0030]
In the present specification, “(meth) acrylate” is a generic term for acrylate and / or methacrylate.
0031]
Specific examples of the sulfur-containing bis (meth) acrylate compound represented by the general formula [I] include, for example, p-bis (β-methacryloyloxyethylthio) xylylene (R1: Methyl, R2: Methyl, R3: Ethylene, R4: Methylene, k: 0), p-bis (β-acryloyloxyethylthio) xylylene, m-bis (β-methacryloyloxyethylthio) xylylene, m-bis (β-acryloyloxyethylthio) xylylene, p-bis (Β-methacryloyloxyethyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthio) tetrabromoxylylene, m-bis (β-methacryloyloxyethyl) And thio) tetrachloroxylylene.
0032]
These compounds can be synthesized, for example, by the method disclosed in JP-A No. 62-195357.
0033]
Specific examples of the alicyclic skeleton bis (meth) acrylate compound represented by the general formula [II] include bis (oxymethyl) tricyclo [5.2.0].2,6Decane = diacrylate, bis (oxymethyl) tricyclo [5.2.0]2,6Decane = dimethacrylate, bis (oxymethyl) tricyclo [5.2.0]2,6Decane = acrylate methacrylate, and mixtures thereof, bis (oxymethyl) pentacyclo [6.5.1.1]3, 6. 02,7. 09,13] Pentadecane = diacrylate, bis (oxymethyl) pentacyclo [6.5.1.1]3, 6. 02,7. 09,13] Pentadecane = dimethacrylate, bis (oxymethyl) pentacyclo [6.5.1.1]3, 6. 02,7. 09,13And pentadecane = acrylate methacrylate and mixtures thereof. Two or more of these tricyclodecane compounds and pentacyclopentadecane compounds may be used in combination or within groups.
0034]
These compounds can be synthesized, for example, by the method disclosed in JP-A-62-225508.
0035]
The polyfunctional (meth) acrylates represented by the general formulas [I] and [II] can be used alone or in combination of two or more. When the compound of the general formula [I] is used alone, the obtained substrate has a relatively high refractive index of 1.55 to 1.65 at room temperature in the sodium D line (589.3 mm). On the other hand, when the compound of general formula [II] is used alone, it has a relatively low refractive index of 1.47 to 1.55. Therefore, a low birefringence resin substrate having a desired refractive index between 1.47 and 1.65 is obtained by using one or more compounds represented by general formulas [I] and [II]. Can do.
0036]
<Auxiliary component>
The substrate material according to the present invention is obtained by polymerizing and curing a polyfunctional (meth) acrylate-containing photocurable monomer composition containing a polyfunctional (meth) acrylate as an essential component. As described above, a small amount of auxiliary components may be included.
0037]
Therefore, the resin substrate according to the present invention is prepared by mixing other monomers capable of radical polymerization and addition polymerization in an amount of up to about 30 parts by weight with respect to 100 parts by weight of the photocurable monomer composition before curing. It can also be produced by copolymerizing with a polyfunctional (meth) acrylate. Examples of other monomers used in this case include methyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methacryloyloxymethyltetracyclododecane, methacryloyloxymethyltetracyclododecene, and ethylene. Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,2-bis [4- (β-methacryloyloxyethoxy) phenyl] propane, 2,2′- (Meth) acrylate compounds such as bis [4- (β-methacryloyloxyethoxy) cyclohexyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexane, trimethylolpropane tri (meth) acrylate, and styrene Nuclei such as styrene, chlorostyrene, divinylbenzene, α-methylstyrene, and / or side chain substituted and unsubstituted styrene, and the like, preferably represented by the following general formulas [III], [IV], and [V]: Two or more in a moleculeFunctional group (Thiol group)HaveMultifunctionalExamples thereof include one or more mercapto compounds selected from the group consisting of mercapto compounds.
0038]
[Chemical11]
0039]
[Chemical12]
0040]
[Chemical13]
0041]
The symbols in the general formulas [III], [IV], and [V] have the following meanings.
0042]
R7: Methylene group or ethylene group
R8: A hydrocarbon group having 2 to 15 carbon atoms which may contain an ether group or a thioether group. Preferably a hydrocarbon group having 2 to 6 carbon atoms
a: integer of 2-6
R: HS- (CH2−)b(CO)-(OCH2)d-(CH2−)c−
(Where b and c are integers from 0 to 2, d is an integer from 1 to 4)
R9: Hydrocarbon group having 1 to 3 carbon atoms
R10: Hydrocarbon group having 1 to 3 carbon atoms
e, f: 0 or 1
g: 1 or 2
The mercapto compound represented by the general formula [III] is a divalent to hexavalent thioglycolic acid ester or thiopropionic acid ester. Specific examples of the compound of formula [III] include, for example, pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-thiopropionate), trimethylolpropane. Tris (thioglycolate), diethylene glycol bis (β-thiopropionate), diethylene glycol bis (thioglycolate), triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycolate), di Examples include pentaerythritol hexacis (β-thiopropionate) and dipentaerythritol hexacis (thioglycolate).
0043]
The compound represented by the general formula [IV] is an X-SH group-containing triisocyanurate. Specific examples of the compound of the formula [IV] include, for example, tris [2- (β-thiopropionyloxy) ethyl] isocyanurate, tris (2-thioglyconyloxyethyl) isocyanurate, tris [2- (β-thio Propionyloxyethoxy) ethyl] isocyanurate, tris (2-thioglyconyloxyethoxyethyl) isocyanurate, tris [3- (β-thiopropionyloxy) propyl] isocyanurate, tris (3-thioglyconyloxypropyl) isocyanate Examples include nurate.
0044]
The compound represented by the general formula [V] is an α, X-SH group-containing compound. Specific examples of the compound of the formula [V] include benzene dimercaptan, xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, and the like.
0045]
By blending these mercapto compounds, in the production of resin substrates, the action as a chain transfer agent with a thiol group is effectively exerted, the polymerization and curing progresses gently and uniformly, and the birefringence of the resulting cured resin Can be reduced. Further, these mercapto compounds enter a three-dimensional network structure formed of bis (meth) acrylate, and appropriate toughness is imparted to the resulting resin substrate. Furthermore, by using a polyfunctional mercapto compound having two or more thiol groups in the molecule, it is possible to improve birefringence, mechanical strength, etc. without significantly impairing the heat resistance of the resulting cured resin. it can.
0046]
When the polyfunctional (meth) acrylate and the mercapto compound are used in combination as the substrate material according to the present invention, the composition ratio is 0.7 to 99.9 parts by weight of the polyfunctional (meth) acrylate. It is preferable to set it as 1-30 weight part, More preferably, it is the range of 1-20 weight part of mercapto compounds with respect to 80-99 weight part of polyfunctional (meth) acrylate. If the proportion of the mercapto compound is too small, the effect of improving the birefringence of the cured resin cannot be obtained.
0047]
In addition to the mercapto compound, antioxidants, ultraviolet absorbers, dyes and pigments, and the like can be used as auxiliary components.
0048]
<Shaping and polymerization curing>
The photocurable monomer composition according to the present invention is shaped and cured. The curing is performed by a known radical polymerization in which a photopolymerization initiator that generates radicals by active energy rays such as ultraviolet rays is added. Examples of the photopolymerization initiator used in this case include benzophenone, benzoylmethyl ether, benzoyl isopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethyl. Examples thereof include benzoyldiphenylphosphine oxide. Of these, preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone. Two or more of these photopolymerization initiators may be used in combination.
0049]
The addition amount of these photoinitiators is 0.01-1 weight part with respect to 100 weight part of monomers, Preferably it is 0.02-0.3 weight part. When the addition amount of the photopolymerization initiator is too large, the polymerization proceeds rapidly and not only causes an increase in birefringence but also deteriorates the hue. If the amount is too small, the photocurable monomer composition cannot be sufficiently cured.
0050]
The amount of active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals, but if it is extremely small, the polymerization is incomplete and the cured product has sufficient heat resistance and mechanical properties. If it is not expressed and, on the contrary, it is extremely excessive, it causes deterioration due to light such as yellowing of the cured product. Irradiation is in the range of 0.1 to 200J. Specific examples of the lamp used include a metal halide lamp, a high pressure mercury lamp, and the like.
0051]
For the purpose of promptly completing the curing, thermal polymerization may be used in combination. That is, the composition and the entire mold are heated in the range of 30 to 300 ° C. simultaneously with the light irradiation. In this case, a thermal polymerization initiator may be added for better completion of the polymerization, but excessive use thereof results in an increase in birefringence and a deterioration in hue. Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), and the amount used is 1 part by weight or less based on 100 parts by weight of the monomer. Is preferred.
0052]
In the present invention, after performing radical polymerization by light irradiation, the cured product can be heated to complete the polymerization reaction and reduce internal strain generated during the polymerization. In this case, the heating temperature is appropriately selected according to the composition of the cured product and the glass transition temperature. However, excessive heating causes the hue of the cured product to deteriorate, and therefore, a temperature around or below the glass transition temperature is preferable.
0053]
In addition, as a mold for shaping, an optically polished glass plate and a silicon plate having a predetermined thickness as a spacer are usually used. Since the surface roughness of the glass plate to be used affects the surface roughness of the resulting resin substrate, it is necessary to control the surface roughness of the glass plate in accordance with the surface roughness required for the resin substrate. Generally, the surface roughness Rz is1In order to obtain a resin substrate of ˜50 nm, it is desirable that the glass plate used as a mold has a surface roughness Rz of 0.2 to 20 nm. As factors that affect the surface roughness of the resin substrate, in addition to the surface roughness of the glass plate, there are an ultraviolet irradiation amount, a photoinitiator amount, and the like, so that each parameter is determined as necessary. For example, in order to obtain a resin substrate having a surface roughness Rz of 5 to 10 nm, a glass plate having a surface roughness Rz of 1 to 5 nm is used, and a silicon plate is disposed on the glass plate as a spacer. Then, a photocurable monomer composition obtained by mixing polyfunctional (meth) acrylate and auxiliary components at a predetermined ratio and defoaming was injected, and between the metal halide lamps with an output of 80 W / cm separated by 40 cm above and below the glass surface. Irradiate with UV for 10 minutes.
0054]
<Physical properties of resin substrate>
From the viewpoint of optical characteristics as a substrate for an organic electroluminescent element, the optical birefringence of the photocurable resin substrate according to the present invention is preferably 20 nm or less.
0055]
The thickness of the resin substrate according to the present invention is usually 0.1 to 5 mm, preferably 0.3 to 1 mm.
0056]
Further, the surface roughness of the resin substrate according to the present invention on the light emitting element production surface side is 1 to 50 nm, preferably 2 to 20 nm in terms of 10-point average roughness Rz. If the Rz of the resin substrate is larger than 50 nm, a short circuit is likely to occur between the electrodes of the organic electroluminescent element produced on the substrate surface, which is not suitable as a substrate. If Rz is less than 1 nm, the adhesion between the organic layer formed on the substrate surface and the substrate is reduced, and the organic layer is easily peeled off by the stress during the subsequent deposition of the cathode metal layer, etc., which is also suitable as a substrate. Disappear.
0057]
For the purpose of further improving the gas barrier property of the resin substrate, a dense silicon oxide film or the like may be provided on at least one surface of the substrate.
0058]
Next, the constituent layers of the organic electroluminescent element of the present invention using such a photocurable resin substrate will be described.
0059]
The anode 2 formed on the substrate 1 plays a role of hole injection into the organic light emitting layer 3. This anode 2 is usually made of metal such as aluminum, gold, silver, platinum, nickel, palladium, platinum, metal oxide such as oxide of indium and / or tin, metal halide such as copper iodide, carbon black, Alternatively, a conductive polymer such as poly (3-methylthiophene), polypyrrole, polyaniline, or the like, preferably made of indium tin oxide. In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. In the case of using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., these are dispersed in an appropriate binder resin solution and the substrate 1 is used. It is also possible to form the anode 2 by applying it on top. When a conductive polymer is used, the anode 2 can be formed by forming a thin film directly on the substrate 1 by electrolytic polymerization or by applying a conductive polymer on the substrate 1 (Appl). Phys. Lett., 60, 2711, 1992). The anode 2 can be formed by stacking different materials.
0060]
The thickness of the anode 2 varies depending on whether or not transparency is required. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 5 to 1000 nm, preferably 10 to 10%. It is about 500 nm. When the anode 2 may be opaque, the same material as the substrate 1 may be used. It is also possible to laminate different conductive materials on the anode 2.
0061]
The organic light emitting layer 3 formed on the anode 2 efficiently transports and recombines holes injected from the anode 2 and electrons injected from the cathode 4 between electrodes to which an electric field is applied, and It is formed from a material that emits light efficiently by recombination. Usually, the organic light emitting layer 3 is divided into a function separation type divided into a hole transport layer 3a and an electron transport layer 3b as shown in FIG. 2 in order to improve luminous efficiency (Appl. Phys. Lett., 51, 913, 1987).
0062]
In the function-separated organic electroluminescent device 10A shown in FIG. 2, as a material of the hole transport layer 3a, the hole injection efficiency from the anode 2 is high, and the injected holes can be efficiently transported. It must be a material. For this purpose, it is required that the ionization potential is low, the hole mobility is high, the stability is high, and impurities that become traps during production and use are hardly generated.
0063]
As such a hole transport material, for example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (Japanese Patent Laid-Open No. 59-86). No. 194393), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] containing two or more tertiary amines represented by biphenyl, and two or more condensed aromatic rings are nitrogen atoms Aromatic amines substituted with the above (Japanese Patent Laid-Open No. 5-234681), triphenylbenzene derivatives and aromatic triamines having a starburst structure (US Pat. No. 4,923,774), N, N′-diphenyl-N , N′-bis (3-methylphenyl) biphenyl-4,4′-diamine and other aromatic diamines (US Pat. No. 4,764,625), α, α, α ′, α′-tetramethyl -Α, α'-bis (4-di-p-tolylaminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084), a sterically asymmetric triphenylamine derivative as a whole molecule (Japanese Patent Laid-Open No. 4-129271) No. 1), a compound in which a biphenyl group is substituted with a plurality of aromatic diamino groups (Japanese Patent Laid-Open No. 4-175395), and an aromatic diamine in which a tertiary aromatic amine unit is linked with an ethylene group (Japanese Patent Laid-Open No. 4-264189) ), Aromatic diamines having a styryl structure (Japanese Patent Laid-Open No. 4-290851), those obtained by linking aromatic tertiary amine units with a thiophene group (Japanese Patent Laid-Open No. 4-304466), starburst aromatic triamines (specialty) Kaihei 4-308688), benzylphenyl compounds (JP-A-4-364153), tertiary amines with fluorene groups Conjugated compounds (JP-A-5-25473), triamine compounds (JP-A-5-239455), bisdipyridylaminobiphenyl (JP-A-5-320634), N, N, N-triphenylamine derivatives ( JP-A-6-1972), aromatic diamine having a phenoxazine structure (JP-A-7-138562), diaminophenylphenanthridine derivative (JP-A-7-252474), hydrazone compound (JP-A-2-2-1) 315991), silazane compounds (US Pat. No. 4,950,950), silanamine derivatives (JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), quinacridone compounds and the like. . These compounds may be used alone or in combination of two or more as required.
0064]
In addition to the above-mentioned compounds, polyvinyl carbazole, polysilane (Appl. Phys. Lett., 59, 2760, 1991), polyphosphazene (Japanese Patent Laid-Open No. Hei 5-310949) can be used as the material for the hole transport layer 3a. ), Polyamide (JP-A-5-310949), polyvinyltriphenylamine (JP-A-7-53953), a polymer having a triphenylamine skeleton (JP-A-4-133565), and a triphenylamine unit. Polymers linked by a methylene group (Synthetic Metals, 55-57, 4163, 1993), polymethacrylates containing aromatic amines (J. Polym. Sci., Polym. Chem. Ed., 21), 969 (1983), etc. Kill.
0065]
The hole transport layer 3a is laminated on the anode 2 by depositing these hole transport materials by a coating method or a vacuum deposition method.
0066]
In the case of the coating method, one or more hole transport materials and, if necessary, additives such as a binder resin and a coating property improving agent that do not trap holes are added and dissolved in a solvent to form a coating solution. Is coated on the anode 2 by a method such as spin coating and dried to form the organic hole transport layer 3a. In this case, examples of the binder resin include polycarbonate, polyarylate, and polyester. When the amount of the binder resin added is large, the hole mobility is lowered. Therefore, a smaller amount is desirable, and usually 50% by weight or less is preferable.
0067]
On the other hand, in the case of the vacuum evaporation method, the hole transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is set to 10-4After evacuating to about Pa, the crucible is heated to evaporate the hole transport material, and a hole transport layer 3a is formed on the anode 2 on the substrate 1 disposed opposite to the crucible.
0068]
In the case of forming the hole transport layer 3a in this way, further, as an acceptor, an aromatic carboxylic acid metal complex and / or metal salt (Japanese Patent Laid-Open No. 4-320484), a benzophenone derivative and a thiobenzophenone derivative (Japanese Patent Laid-Open No. 5-295361), fullerenes (JP-A-5-331458) and the like.-3Low voltage driving can be enabled by doping at a concentration of -10 wt% to generate holes as free carriers.
0069]
The thickness of the hole transport layer 3a is usually 10 to 300 nm, preferably 30 to 100 nm. In order to form such a thin hole transport layer uniformly, it is generally preferable to employ a vacuum deposition method.
0070]
Further, for the purpose of further improving the hole injection efficiency and improving the adhesion of the whole organic layer to the anode 2, the hole injection is performed between the hole transport layer 3 a and the anode 2 as shown in FIG. Formation of the layer 3c is also performed. The material used for the hole injection layer 3c is preferably a material having a low ionization potential, high conductivity, and capable of forming a thermally stable thin film on the anode 2, such as a phthalocyanine compound or a porphyrin compound (Japanese Patent Laid-Open No. 57-51781 and JP-A-63-295695) are used. By interposing such a hole injection layer 3c, the driving voltage of the initial element is lowered, and at the same time, an effect of suppressing the voltage increase when the element is continuously driven with a constant current can be obtained. The hole injection layer 3c can also be improved in conductivity by doping with an acceptor in the same manner as the hole transport layer 3a.
0071]
The film thickness of the hole injection layer 3c is usually 2 to 100 nm, preferably 5 to 50 nm. In order to form such a thin hole injection layer uniformly, it is generally preferable to employ a vacuum deposition method.
0072]
The electron transport layer 3b formed on the hole transport layer 3a is composed of a compound that can efficiently transport electrons from the cathode in the direction of the hole transport layer 3a between electrodes to which an electric field is applied. The
0073]
The electron transporting compound used for the electron transport layer 3b needs to be a compound that has high electron injection efficiency from the cathode 4 and can efficiently transport the injected electrons. For this purpose, it is required to be a compound that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate impurities that become traps during production and use.
0074]
Materials satisfying such conditions include aromatic compounds such as tetraphenylbutadiene (Japanese Patent Laid-Open No. 57-51781) and metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393). Cyclopentadiene derivatives (JP-A-2-289675), perinone derivatives (JP-A-2-289676), oxadiazole derivatives (JP-A-2-216791), bisstyrylbenzene derivatives (JP-A-1-245087). No. 2-22484), perylene derivatives (JP-A-2-189890, JP-A-3-791), coumarin compounds (JP-A-2-191694, JP-A-3-792), rare earths Complexes (Japanese Patent Laid-Open No. 1-256584), distyrylpyrazine derivatives (Japanese Patent Laid-Open No. 2-256854) 52793), p-phenylene compounds (JP-A-3-33183), thiadiazolopyridine derivatives (JP-A-3-37292), pyrrolopyridine derivatives (JP-A-3-37293), naphthyridine derivatives ( JP-A-3-203982).
0075]
In general, the electron transport layer 3b using these compounds can simultaneously play a role of transporting electrons and a role of causing light emission upon recombination of holes and electrons.
0076]
When the hole transport layer 3a has a light emitting function, the electron transport layer 3b may only play a role of transporting electrons.
0077]
For the purpose of improving the luminous efficiency of the device and changing the emission color, for example, doping a fluorescent dye for lasers such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys., Volume 65). , P. 3610 (1989)), and in the present invention, various fluorescent dyes are used in the present invention using the above organic electron transporting material as a host material.-3The light emission characteristics of the device can be further improved by doping at 10 mol% to 10 mol%.
0078]
The film thickness of the electron transport layer 3b is usually 10 to 200 nm, preferably 30 to 100 nm.
0079]
The electron transport layer can also be formed by the same method as the hole transport layer, but a vacuum deposition method is usually used.
0080]
As the single-layer type organic light emitting layer 3 that does not perform functional separation as shown in FIG. 1, poly (p-phenylene vinylene) (Nature, 347, 539, 1990, etc.), poly, [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., 58, 1982, 1991 et al.), Poly (3-alkylthiophene) (Jpn. Phys., J. Appl. Phys, 30, L 1938, 1991, etc.), or a system in which a light emitting material and an electron transfer material are mixed in a polymer such as polyvinyl carbazole (Applied Physics, 61, 1044, 1992).
0081]
The cathode 4 serves to inject electrons into the organic light emitting layer 3. The material used for the cathode 4 can be the material used for the anode 2, but a metal having a low work function is preferable for efficient electron injection, such as tin, magnesium, indium, calcium, Suitable metals such as aluminum and silver or their alloys are preferred. The film thickness of the cathode 4 is usually about the same as that of the anode 2.
0082]
In order to protect a cathode made of a low work function metal, the stability of the device can be increased by further laminating a metal layer having a high work function and stable to the atmosphere on the cathode. For the metal layer for this purpose, metals such as aluminum, silver, nickel, chromium, gold and platinum are used.
0083]
1 to 3 show an example of an element body employed in the present invention, and the present invention can be applied to an element body having a layer structure as shown below, in addition to the illustrated one. it can.
0084]
Anode / hole transport layer / electron transport layer / interface layer / cathode,
Anode / hole transport layer / electron transport layer / other electron transport layer / cathode,
Anode / hole transport layer / electron transport layer / other electron transport layer / interface layer / cathode,
Anode / hole injection layer / hole transport layer / electron transport layer / interface layer / cathode,
Anode / hole injection layer / hole transport layer / electron transport layer / other electron transport layer / cathode
In the above layer structure, the interface layer is for improving the contact between the cathode and the organic layer, and includes an aromatic diamine compound (JP-A-6-267658), a quinacridone compound (JP-A-6-330031), naphthacene. Derivatives (JP-A-6-330032), organosilicon compounds (JP-A-6-325871), organophosphorus compounds (JP-A-6-325872), compounds having an N-phenylcarbazole skeleton (Japanese Patent Application No. 6) -199562), an N-vinylcarbazole polymer (Japanese Patent Application No. 6-200942) and the like. The thickness of the interface layer is usually 2 to 100 nm, preferably 5 to 30 nm. Instead of providing the interface layer, a region containing 50% by weight or more of the material of the interface layer may be provided in the vicinity of the cathode interface between the organic light emitting layer and the electron transport layer.
0085]
The other electron transport layer is further laminated on the electron transport layer in order to further improve the light emission efficiency of the organic electroluminescent device. The compound used for this electron transport layer includes a cathode. Therefore, it is required that the electron injection is easy and the electron transport capacity is further increased. Examples of such electron transporting materials include oxadiazole derivatives (Appl. Phys. Lett., 55, 1489, 1989, etc.) and systems in which they are dispersed in a resin such as polymethyl methacrylate (PMMA) ( Appl. Phys. Lett., 61, 2793, 1992), phenanthroline derivative (Japanese Patent Laid-Open No. 5-33159), or n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type selenization. Zinc etc. are mentioned. The film thickness of the other electron transport layer is usually 5 to 200 nm, preferably 10 to 100 nm.
0086]
The organic electroluminescent element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and an element having a structure in which an anode and a cathode are arranged in an XY matrix. .
0087]
【Example】
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.
0088]
Example 1
99 parts by weight of p-bis (β-methacryloyloxyethylthio) xylylene, 1 part by weight of pentaerythritol tetrakis (β-thiopropionate), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF) as a photopolymerization initiator “Lucirin TPO” manufactured by 0.05) and 0.02 part by weight of benzophenone were uniformly stirred and mixed, and then defoamed to obtain a photocurable monomer composition.
0089]
On the other hand, as a mold for shaping the resin, using an optically polished glass plate and a 1 mm thick silicon plate as a spacer, the photocurable monomer composition was poured into this optically polished glass mold, Ultraviolet rays were irradiated for 10 minutes between metal halide lamps with an output of 80 W / cm at a vertical position of 40 cm from the glass surface. After the ultraviolet irradiation, the mold was released and heated at 120 ° C. for 1 hour to obtain a cured product. This cured product was cut into a glass slide (25 × 75 mm) to obtain a substrate A. Various characteristics of the substrate A were as shown in Table 1. Each characteristic was evaluated by the following method.
0090]
(1) Appearance: Evaluated visually.
(2) Specific gravity: Evaluated by measuring the weight and volume of a test piece having a width and a length of 5 cm each and a thickness of 1 mm.
(3) Falling ball impact test: Evaluation was performed at the lowest height at which a test piece was damaged by naturally dropping a 16 g steel ball onto a test piece having a width and length of 5 cm each and a thickness of 1 mm.
(4) Flexural modulus: Evaluation was performed at 25 ° C. using an autograph at a fulcrum distance of 3 cm for a plate having a width of 1 cm and a thickness of 1 mm.
(5) Surface roughness Rz: Ten-point average roughness (JISB0601) using a stylus type surface roughness meter (Taristep manufactured by Rank Taylor Hobson: tip shape of stylus is 0.2 × 0.2 μm square) evaluated.
(6) Refractive index: It evaluated at 25 degreeC using the Abbe refractometer (made by Atago Co., Ltd.).
(7) Birefringence: evaluated at 25 ° C. using a birefringence measuring apparatus (manufactured by Oak Co.).
(8) Water absorption rate: Evaluated by saturated water absorption rate when immersed in water at 60 ° C for 1 week.
(9) Glass transition temperature: A test piece having a thickness of 1 mm was evaluated using a TMA (thermomechanical analyzer) with a weight of 50 g.
0091]
Next, an indium tin oxide (ITO) transparent conductive film was deposited to 120 nm on this substrate A (Toyo Sangyo Co., Ltd .: low-temperature sputtered film product: sheet resistance 20Ω) to obtain an ITO substrate A.
0092]
Using this ITO substrate A, an organic electroluminescence device having the structure shown in FIG. 3 was produced by the following method. First, an ITO transparent conductive film deposited on the ITO substrate A was patterned into a stripe having a width of 2 mm using a normal photolithography technique and hydrochloric acid etching to form an anode.
0093]
The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, then dried with nitrogen blow, and finally with ultraviolet ozone cleaning. installed. After rough evacuation of the apparatus with an oil rotary pump, the degree of vacuum in the apparatus is 2 × 10-6Torr (about 2.7 × 10-4Pa) was evacuated using an oil diffusion pump equipped with a liquid nitrogen trap until it was below.
0094]
The following copper phthalocyanine (H1) (crystal form is β type) placed in a molybdenum boat placed in the above apparatus was heated for vapor deposition. Steam has a degree of vacuum of 1.1 × 10-6torr (about 1.5 × 10-4Pa), the deposition time was 1 minute, and a hole injection layer 3c having a thickness of 20 nm was formed.
0095]
[Chemical14]
0096]
Next, the following 4,4′-bis [N- (1-naphthyl) -N-phenylamino] bisphenol (H2) placed in a ceramic crucible arranged in the above apparatus was tantalum wire around the crucible. It heated with the heater and laminated | stacked on the positive hole injection layer 3c. At this time, the temperature of the crucible was controlled in the range of 230 to 240 ° C. Degree of vacuum during deposition 8 × 10-7Torr (approximately 1.1 × 10-4Pa), a hole transport layer 3a having a film thickness of 60 nm was formed at a deposition time of 1 minute 50 seconds.
0097]
[Chemical15]
0098]
Subsequently, as a material for the electron transport layer 3b having a light emitting function, the following aluminum 8-hydroxyquinoline complex: Al (C9H6NO)3(E1) was deposited in the same manner on the hole transport layer 3a. At this time, the temperature of the crucible was controlled in the range of 310 to 320 ° C. Degree of vacuum during deposition is 9 x 10-7Torr (about 1.2 × 10-4Pa), the deposition time was 2 minutes and 40 seconds, and an electron transport layer 3b having a film thickness of 75 nm was formed.
0099]
[Chemical16]
[0100]
In addition, the substrate temperature at the time of vacuum-depositing the hole injection layer 3c, the hole transport layer 3a, and the electron transport layer 3b was kept at room temperature.
[0101]
The substrate on which the hole injection layer 3c, the hole transport layer 3a and the electron transport layer 3b are formed is once taken out into the atmosphere from the vacuum deposition apparatus, and a 2 mm wide stripe shadow mask is used as a cathode deposition mask. 2 in close contact with the ITO stripe and installed in a separate vacuum deposition apparatus, and the degree of vacuum in the apparatus is 2 × 10 2 in the same manner as the deposition of each organic layer.-6Torr (about 2.7 × 10-4Pa) was exhausted to below. Subsequently, an alloy electrode of magnesium and silver was deposited as the cathode 4 so as to have a film thickness of 100 nm by a binary simultaneous deposition method. Deposition uses a molybdenum boat and a vacuum of 1 × 10-5Torr (approximately 1.3 × 10-3Pa), the deposition time was 3 minutes and 10 seconds. The atomic ratio of magnesium and silver was 10: 1.2. Subsequently, the cathode 4 was completed by laminating aluminum on the magnesium / silver alloy film with a film thickness of 100 nm using a molybdenum boat without breaking the vacuum of the apparatus. The degree of vacuum during aluminum deposition is 2.3 x 10-5Torr (about 3.1 × 10-3Pa), the deposition time was 1 minute 40 seconds. The substrate temperature at the time of vapor deposition of the above two-layer cathode of magnesium / silver alloy and aluminum was kept at room temperature.
[0102]
As described above, an organic electroluminescence device having a size of 2 mm × 2 mm was obtained. After the device was taken out from the cathode vapor deposition apparatus, a positive DC voltage was applied to the anode 2 and a negative DC voltage was applied to the cathode 4 to emit light, and the light emission characteristics were measured.
[0103]
FIG. 4 shows the change in light emission luminance when the applied voltage is changed in 1V steps in the range of 1 to 15V. Further, Table 2 shows the light emission luminance when 15 V is applied to the element, the light emission efficiency at 15 V, and L / J (the amount corresponding to the quantum efficiency by the slope when the luminance-current density characteristic is approximated by a straight line). It was shown to.
[0104]
Example 2
Bis (oxymethyl) tricyclo [5.2.1.0 as monomer component2.6A cured product was obtained in the same manner as in Example 1 except that 96 parts by weight of decane = dimethacrylate and 4 parts by weight of pentaerythritol tetrakis (β-thiopropionate) were used. This cured product was cut into a glass slide to obtain a substrate B. Various characteristics of the substrate B were as shown in Table 1.
[0105]
Next, an ITO transparent conductive film was deposited on the substrate B by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate B. The sheet resistance value of this ITO substrate B was 20Ω.
[0106]
Further, using this ITO substrate B, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission characteristics were measured in the same manner. The results are shown in FIG.
[0107]
Comparative Example 1
Corning 7059 glass was cut into a glass slide to form substrate C. Various characteristics of the substrate C were as shown in Table 1.
[0108]
Next, an ITO transparent conductive film was deposited on the substrate C by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate C. The sheet resistance value of the ITO substrate C was 20Ω.
[0109]
Further, using this ITO substrate C, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission characteristics were measured in the same manner. The results are shown in FIG.
[0110]
Comparative Example 2
In the same manner as in Comparative Example 1, 7059 glass manufactured by Corning was used as a substrate, and an ITO transparent conductive film was deposited on this substrate by an electron beam evaporation method (manufactured by Geomatech) to obtain an ITO substrate D. The sheet resistance value of the ITO substrate D was 15Ω. Further, when the X-ray diffraction analysis of the ITO substrate D was performed, the In substrate near 2θ = 30.6 ° was compared with the ITO substrate C of Comparative Example 1 by low-temperature sputtering.2O3It was found that the diffraction peak intensity of the crystal was large and the crystallinity was high.
[0111]
Using this ITO substrate D, an organic electroluminescence device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission characteristics were measured in the same manner. The results are shown in FIG.
[0112]
Comparative Example 3
A cured product was obtained in the same manner as in Example 1 except that the surface of the glass mold into which the photocurable monomer composition was injected was not optically polished. This cured product was cut into a glass slide to obtain a substrate E. Various characteristics of the substrate E were as shown in Table 1.
[0113]
Next, an ITO transparent conductive film was deposited on the substrate E by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate E. The sheet resistance value of the ITO substrate E was 20Ω.
[0114]
Using this ITO substrate E, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and evaluated in the same manner. When 5 V was applied, the device was short-circuited.
[0115]
[Table 1]
[0116]
[Table 2]
[0117]
【The invention's effect】
As described above in detail, according to the organic electroluminescent device and the manufacturing method thereof of the present invention, a light-weight and high mechanical strength plastic substrate is used, and the light emission characteristics are also compared with those using a conventional glass substrate. An organic electroluminescent device having the same or better characteristics can be obtained with high productivity.
[0118]
Therefore, the organic electroluminescent device according to the present invention is a light source (for example, a light source of a copying machine, a performance display, or a back of an instrument) utilizing characteristics of a flat panel display (for example, for OA computers or wall-mounted televisions) or a surface light emitter. It is expected to be applied to light sources), display boards, and sign lamps, and its technical value is extremely large.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of an organic electroluminescent element of the present invention.
FIG. 2 is a schematic cross-sectional view showing another embodiment of the organic electroluminescent element of the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the organic electroluminescent element of the present invention.
4 is a graph showing the applied voltage dependence of the light emission luminance of organic electroluminescent elements in Examples 1 and 2 and Comparative Examples 1 and 2. FIG.
[Explanation of symbols]
1 Substrate
2 Anode
3 Organic light emitting layer
4 Cathode
3a hole transport layer
3b Electron transport layer
3c hole injection layer
10, 10A, 10B Organic electroluminescent device
Claims (6)
で表される化合物及び下記一般式 [II]
で表される化合物よりなる群から選ばれる少なくとも１種の分子内に２個以上の官能基を有する多官能（メタ）アクリレートを含有するモノマーを光重合させて得られることを特徴とする有機電界発光素子。On one plate surface of the substrate, an anode, an organic electroluminescent device wherein an organic light-emitting layer and a cathode are stacked, the substrate is made of photocurable resin, and the surface of the one plate surface of the substrate roughness (Rz) Ri is 1~50nm der, photocurable resin is represented by the following general formula [I]
And the following general formula [II]
Organic THAT the photopolymerized monomers containing polyfunctional (meth) acrylate having at least one two or more functional groups in the molecule is selected from the group consisting of compounds represented characterized Rukoto obtained Electroluminescent device.
で表される化合物及び下記一般式 [II]
で表される化合物よりなる群から選ばれる少なくとも１種の分子内に２個以上の官能基を有する多官能（メタ）アクリレートを含有するモノマーを光重合させて得られる基板を用い、該基板の該一方の板面に陽極、有機発光層及び陰極を積層することを特徴とする有機電界発光素子の製造方法。In a method of manufacturing an organic electroluminescent element by laminating an anode, an organic light emitting layer and a cathode on a substrate, the substrate is made of a photocurable resin and has a surface roughness (Rz) of at least one plate surface. ) is Ri 1~50nm der, photocurable resin is represented by the following general formula [I]
And the following general formula [II]
At least one by photopolymerizing monomers containing polyfunctional (meth) acrylates having two or more functional groups in the molecule with a substrate that is obtained by, the substrate is selected from the group consisting of compounds represented by in A method for producing an organic electroluminescent device, comprising: laminating an anode, an organic light emitting layer, and a cathode on the one plate surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24496497A JP4164885B2 (en) | 1996-09-12 | 1997-09-10 | Organic electroluminescent device and manufacturing method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24205496 | 1996-09-12 | ||
| JP8-242054 | 1996-09-12 | ||
| JP24496497A JP4164885B2 (en) | 1996-09-12 | 1997-09-10 | Organic electroluminescent device and manufacturing method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008098225A Division JP2008218421A (en) | 1996-09-12 | 2008-04-04 | Organic electroluminescent element and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10144469A JPH10144469A (en) | 1998-05-29 |
| JP4164885B2 true JP4164885B2 (en) | 2008-10-15 |
Family
ID=26535585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24496497A Expired - Fee Related JP4164885B2 (en) | 1996-09-12 | 1997-09-10 | Organic electroluminescent device and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4164885B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008218421A (en) * | 1996-09-12 | 2008-09-18 | Mitsubishi Chemicals Corp | Organic electroluminescent element and its manufacturing method |
| WO2000072637A1 (en) * | 1998-03-09 | 2000-11-30 | Tdk Corporation | Organic el color display |
| US6406802B1 (en) | 1999-05-27 | 2002-06-18 | Tdk Corporation | Organic electroluminescent color display |
| JP4717198B2 (en) * | 1999-11-29 | 2011-07-06 | キヤノン株式会社 | Organic electroluminescence device |
| JP4531913B2 (en) * | 2000-03-08 | 2010-08-25 | 株式会社クレハ | Transparent electrode plate for organic EL element and organic EL element |
| JP2002063985A (en) * | 2000-08-22 | 2002-02-28 | Nec Corp | Organic electroluminescence element |
| JP2002289358A (en) * | 2001-03-23 | 2002-10-04 | Ricoh Co Ltd | Organic electroluminescence element |
| CN100572495C (en) * | 2002-03-09 | 2009-12-23 | Cdt牛津有限公司 | Polymerisable compound and the organic luminescent device that contains it |
| EP1478032A2 (en) | 2003-05-16 | 2004-11-17 | Kabushiki Kaisha Toyota Jidoshokki | Light emitting diode method for forming the same |
| TWI260945B (en) * | 2003-05-16 | 2006-08-21 | Toyota Ind Corp | Light-emitting apparatus and method for forming the same |
| GB0321781D0 (en) * | 2003-09-17 | 2003-10-15 | Toppan Printing Company Ltd | Electroluminescent device |
| JP5164369B2 (en) * | 2006-12-08 | 2013-03-21 | 日本合成化学工業株式会社 | Secondary battery |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60222241A (en) * | 1984-04-19 | 1985-11-06 | 住友ベークライト株式会社 | Transparent conductive film |
| JPS61287913A (en) * | 1985-06-17 | 1986-12-18 | Mitsubishi Petrochem Co Ltd | Resin for optical material |
| JP2983226B2 (en) * | 1989-05-08 | 1999-11-29 | 三菱化学株式会社 | Transparent resin material |
| JP2778988B2 (en) * | 1989-06-09 | 1998-07-23 | 三菱化学株式会社 | Manufacturing method of optical materials |
| JP3216197B2 (en) * | 1991-02-15 | 2001-10-09 | 東レ株式会社 | Plastic optical articles |
| JPH05182763A (en) * | 1992-01-07 | 1993-07-23 | Sekisui Chem Co Ltd | Manufacture of electroluminescent element using organic crystal |
| JPH05194672A (en) * | 1992-01-23 | 1993-08-03 | Mitsubishi Petrochem Co Ltd | High refractive index optical material |
| JPH05266979A (en) * | 1992-03-16 | 1993-10-15 | Toshiba Corp | Thin film type electroluminescence element |
| JP3028009B2 (en) * | 1992-04-13 | 2000-04-04 | セイコーエプソン株式会社 | Composition for high refractive index optical material and manufacturing method |
| JPH06170860A (en) * | 1992-12-09 | 1994-06-21 | Toray Ind Inc | Production of resin molded piece |
| JPH0741520A (en) * | 1993-07-28 | 1995-02-10 | Mitsubishi Chem Corp | Composition for polymerization and resin material |
| JP3614182B2 (en) * | 1993-11-04 | 2005-01-26 | 株式会社デンソー | Method for manufacturing electroluminescence element |
| JPH08199161A (en) * | 1995-01-26 | 1996-08-06 | Mitsubishi Chem Corp | Organic electroluminescence element |
-
1997
- 1997-09-10 JP JP24496497A patent/JP4164885B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10144469A (en) | 1998-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7203903B2 (en) | Sealant for organic electroluminescence display elements | |
| JPH10223367A (en) | Organic electric field luminescence element | |
| JP4164885B2 (en) | Organic electroluminescent device and manufacturing method thereof | |
| JP5506475B2 (en) | Method for manufacturing organic electroluminescent device | |
| JPH0753953A (en) | Organic electroluminescent element | |
| JPH10214682A (en) | Manufacturing device and manufacture of organic electroluminescent element | |
| JPH06267658A (en) | Organic el element | |
| JP2002056973A (en) | Organic electroluminescent element and photosensitive polymer | |
| JPH07312289A (en) | Organic electroluminescent element | |
| JP2017091695A (en) | Organic electroluminescent element, lighting system, surface light source, and display device | |
| JP2005235467A (en) | Organic el element | |
| JP2008218421A (en) | Organic electroluminescent element and its manufacturing method | |
| WO2022039019A1 (en) | Composition for electronic device sealing, method for forming electronic device sealing film, and electronic device sealing film | |
| JP4030608B2 (en) | Organic electroluminescent device and manufacturing method thereof | |
| JP3279014B2 (en) | Organic electroluminescent device | |
| JP2008021575A (en) | Organic electroluminescent element and manufacturing method of same | |
| JP5567407B2 (en) | Method for manufacturing organic electroluminescent device | |
| JP4088471B2 (en) | Organic light emitting device and method for manufacturing the same | |
| JP2009064882A (en) | Organic electric field light-emitting device and display device | |
| JP2005317440A (en) | Organic electroluminescent element, its manufacturing method and electronic apparatus | |
| JP4103531B2 (en) | Organic electroluminescence device | |
| JP3189376B2 (en) | Organic electroluminescent device | |
| KR20240009473A (en) | Composition for electronic device encapsulation, method of forming electronic device encapsulation film, and electronic device encapsulation film | |
| WO2024024836A1 (en) | Composition for encapsulating electronic device, electronic device encapsulation film, and method for forming electronic device encapsulation film | |
| WO2024024841A1 (en) | Composition for electronic device sealing, electronic device sealing film, and method for forming electronic device sealing film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060307 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060704 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080205 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080404 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20080507 |
|
| 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: 20080708 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080721 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110808 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110808 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110808 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110808 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120808 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120808 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120808 Year of fee payment: 4 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120808 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130808 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130808 Year of fee payment: 5 |
|
| 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 |
|
| LAPS | Cancellation because of no payment of annual fees |