CN108886849B - Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element - Google Patents
Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element Download PDFInfo
- Publication number
- CN108886849B CN108886849B CN201780020277.2A CN201780020277A CN108886849B CN 108886849 B CN108886849 B CN 108886849B CN 201780020277 A CN201780020277 A CN 201780020277A CN 108886849 B CN108886849 B CN 108886849B
- Authority
- CN
- China
- Prior art keywords
- organic
- display element
- sealing agent
- sealant
- polymerizable compound
- 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.)
- Active
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000565 sealant Substances 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 oxetane compound Chemical class 0.000 claims description 104
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000010943 off-gassing Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 description 44
- 238000010438 heat treatment Methods 0.000 description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 16
- 229910010272 inorganic material Inorganic materials 0.000 description 15
- 239000011147 inorganic material Substances 0.000 description 15
- 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 15
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 238000010538 cationic polymerization reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- UCBQKJQXUPVHFJ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C1C=CC=C1 UCBQKJQXUPVHFJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000012024 dehydrating agents Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- NQEJEMZJOBCYOD-UHFFFAOYSA-N (4-methoxyphenyl)methyl-dimethyl-phenylazanium Chemical compound C1=CC(OC)=CC=C1C[N+](C)(C)C1=CC=CC=C1 NQEJEMZJOBCYOD-UHFFFAOYSA-N 0.000 description 1
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- VSHKLLPSERFSRJ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)pyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC2=CC=CC=C12 VSHKLLPSERFSRJ-UHFFFAOYSA-N 0.000 description 1
- OBSKXJSZGYXFFB-UHFFFAOYSA-N 1-benzylpyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC=C1 OBSKXJSZGYXFFB-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- RQJCIXUNHZZFMB-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxypropoxy)propane Chemical compound C=COCC(C)OCC(C)OC=C RQJCIXUNHZZFMB-UHFFFAOYSA-N 0.000 description 1
- FOWNZLLMQHBVQT-UHFFFAOYSA-N 1-ethenoxy-2-[2-(2-ethenoxypropoxy)propoxy]propane Chemical compound C=COCC(C)OCC(C)OCC(C)OC=C FOWNZLLMQHBVQT-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- MCBXLJCOMLRSQK-UHFFFAOYSA-N 2-(4-sulfanylphenoxy)ethanol Chemical compound OCCOC1=CC=C(S)C=C1 MCBXLJCOMLRSQK-UHFFFAOYSA-N 0.000 description 1
- IITAGOPHHFGANB-UHFFFAOYSA-N 2-(phenoxymethyl)oxetane Chemical compound C1COC1COC1=CC=CC=C1 IITAGOPHHFGANB-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- PNPLRTWSLDSFET-UHFFFAOYSA-N 2-naphthalen-1-yl-5-phenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C3=CC=CC=C3C=CC=2)O1 PNPLRTWSLDSFET-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 1
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-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
- GMXOYEFGMAXIIU-UHFFFAOYSA-N C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C Chemical compound C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C GMXOYEFGMAXIIU-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 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
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- MOOIXEMFUKBQLJ-UHFFFAOYSA-N [1-(ethenoxymethyl)cyclohexyl]methanol Chemical compound C=COCC1(CO)CCCCC1 MOOIXEMFUKBQLJ-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 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
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- HYVNJCOHGOONJK-UHFFFAOYSA-N dibenzyl-methyl-phenylazanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(C)CC1=CC=CC=C1 HYVNJCOHGOONJK-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ONRGBXGMVZEZLY-UHFFFAOYSA-N dimethyl-[(4-methylphenyl)methyl]-phenylazanium Chemical compound C1=CC(C)=CC=C1C[N+](C)(C)C1=CC=CC=C1 ONRGBXGMVZEZLY-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- PBHPFFDRTUWVIT-UHFFFAOYSA-N oxetan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCO1 PBHPFFDRTUWVIT-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 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
- HMKGBOLFVMRQRP-UHFFFAOYSA-N tribenzyl(phenyl)azanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 HMKGBOLFVMRQRP-UHFFFAOYSA-N 0.000 description 1
- GAMLUOSQYHLFCT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-3-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1(CC)COC1 GAMLUOSQYHLFCT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- ULNJZOIDTANZKR-UHFFFAOYSA-N tris[4-(4-acetylphenyl)sulfanylphenyl]sulfanium Chemical compound C1=CC(C(=O)C)=CC=C1SC1=CC=C([S+](C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=C1 ULNJZOIDTANZKR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Polyethers (AREA)
- Sealing Material Composition (AREA)
Abstract
The purpose of the present invention is to provide a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing properties, and can provide an organic EL display element having excellent reliability. Another object of the present invention is to provide a method for producing the sealant for organic EL display elements. The present invention is a sealing agent for an organic EL display element, which contains a polymerizable compound and a polymerization initiator, and which has a viscosity of 5 to 50 mPas at 25 ℃, a surface tension of 15 to 35mN/m at 25 ℃, and a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃, 50% RH.
Description
Technical Field
The present invention relates to a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing property, and can provide an organic EL display element having excellent reliability. The present invention also relates to a method for producing the sealing agent for an organic EL display element.
Background
An organic electroluminescence (organic EL) display element has a laminate structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected from one electrode into the organic light emitting material layer, and holes are injected from the other electrode into the organic light emitting material layer, whereby the electrons and the holes are combined in the organic light emitting material layer and light is emitted. Since the organic EL display element emits light in this manner, the organic EL display element has advantages of being excellent in visibility, being capable of being thinned, and being capable of dc low-voltage driving, as compared with a liquid crystal display element or the like that requires a backlight.
The organic light-emitting material layer and the electrode constituting the organic EL display device have a problem that their characteristics are easily deteriorated by moisture, oxygen, or the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to isolate the organic light emitting material layer and the electrode from the atmosphere to achieve a long life. Patent document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method. Here, the resin film has an effect of preventing the organic layer and the electrode from being pressed by internal stress of the silicon nitride film.
In the method of sealing with a silicon nitride film disclosed in patent document 1, the organic light emitting material layer may not be completely covered when the silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matter, occurrence of cracks due to internal stress, and the like. If the coverage based on the silicon nitride film is incomplete, moisture penetrates through the silicon nitride film and enters into the organic light emitting material layer.
As a method for preventing moisture from entering into the organic light emitting material layer, patent document 2 discloses a method of alternately depositing an inorganic material film and a resin film, and patent documents 3 and 4 disclose a method of forming a resin film on an inorganic material film.
As a method for forming a resin film, there is a method in which a sealant is applied to a substrate by an ink jet method and then cured. If a coating method based on such an ink jet method is used, a resin film can be uniformly formed at high speed. However, in the case where the sealant is made to have a low viscosity so as to be suitable for application by an ink-jet method, there are problems in that: the organic EL display device is not sufficiently prevented from being immersed in moisture due to outgassing or in a high-temperature and high-humidity environment, and the reliability of the obtained organic EL display device is deteriorated.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2000-223264
Patent document 2: japanese Kohyo publication No. 2005-522891
Patent document 3: japanese patent laid-open No. 2001-307873
Patent document 4: japanese patent laid-open No. 2008-149710
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing properties, and can provide an organic EL display element having excellent reliability. Another object of the present invention is to provide a method for producing the sealant for organic EL display elements.
Means for solving the problems
The present invention 1 is a sealing agent for an organic EL display element, which contains a polymerizable compound and a polymerization initiator, and which has a viscosity of 5 to 50mPa · s at 25 ℃, a surface tension of 15 to 35mN/m at 25 ℃, and a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃ and 50% rh.
The present invention 2 is a sealing agent for an organic EL display element, which is used for coating by an inkjet method, and which contains a polymerizable compound and a polymerization initiator, and which has a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃, 50% rh.
The present invention is described in detail below. The sealant for an organic EL display element of the present invention is referred to as "the sealant for an organic EL display element of the present invention" for the common matters of the sealant for an organic EL display element of the present invention and the sealant for an organic EL display element of the present invention 2.
The present inventors have further studied the case where the water content is in a specific range for a sealant for an organic EL display element having excellent ink-jet coatability. As a result, they found that: the present inventors have completed the present invention by obtaining a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing properties, and can obtain an organic EL display element having excellent reliability.
The sealing agent for an organic EL display element of the present invention can be applied by a non-heating type ink jet method or by a heating type ink jet method as an ink jet method.
In the present specification, the "non-heating type ink jet method" is a method of performing ink jet coating at a coating head temperature of less than 28 ℃, and the "heating type ink jet method" is a method of performing ink jet coating at a coating head temperature of 28 ℃ or higher.
The heating type ink jet method may use an ink jet coating head equipped with a heating mechanism. By mounting the heating mechanism on the inkjet application head, viscosity and surface tension can be reduced when the sealing agent for the organic EL display element is discharged.
Examples of the inkjet application head having the heating mechanism mounted thereon include KM1024 series manufactured by KONICA MINOLTA; SG1024 series manufactured by Fuji Film Dimatix, inc., and the like.
When the sealant for an organic EL display element of the present invention is used for the application by the heating inkjet method, the heating temperature of the application head is preferably in the range of 28 to 80 ℃. By setting the heating temperature of the coating head within this range, the viscosity of the sealant for an organic EL display element is prevented from increasing over time, and the discharge stability is further improved.
The lower limit of the viscosity of the sealant for an organic EL display element of the present invention 1 is 5mPa · s, and the upper limit of the viscosity is 50mPa · s. When the viscosity is within this range, the coating can be performed satisfactorily by an ink jet method.
In the present specification, the viscosity is a value measured at 25 ℃ and 100rpm using an E-type viscometer.
The viscosity of the sealing agent for an organic EL display element of the present invention when applied by the non-heating inkjet method has a preferred lower limit of 5mPa · s and a preferred upper limit of 20mpa · s. When the viscosity is in this range, the ink can be favorably applied by a non-heating type ink jet method. The viscosity of the sealant for an organic EL display element of the present invention when applied by the non-heating inkjet method is more preferably 8mPa · s at the lower limit, more preferably 169pa · s at the upper limit, still more preferably 10mPa · s at the lower limit, and still more preferably 13mpa · s at the upper limit.
On the other hand, the viscosity of the sealing agent for an organic EL display element of the present invention used for the application by the heating inkjet method has a preferred lower limit of 10mPa · s and a preferred upper limit of 50mpa · s. When the viscosity is in this range, the coating can be favorably performed by the heating inkjet method. The viscosity of the organic EL display element sealant of the present invention used for the application by the heating inkjet method has a more preferable lower limit of 20mPa · s and a more preferable upper limit of 40mpa · s.
The lower limit of the surface tension of the sealing agent for an organic EL display element of the present invention 1 is 15mN/m, and the upper limit is 35mN/m. When the surface tension is in this range, the coating can be favorably performed by an ink jet method. The surface tension preferably has a lower limit of 20mN/m, a preferred upper limit of 30mN/m, a more preferred lower limit of 22mN/m, and a more preferred upper limit of 28mN/m.
The surface tension of the sealing agent for an organic EL display element according to the present invention 2 has a preferred lower limit of 15mN/m and a preferred upper limit of 35mN/m. When the surface tension is in this range, the ink can be applied favorably by an ink jet method. The surface tension is more preferably 20mN/m in lower limit, more preferably 30mN/m in upper limit, still more preferably 22mN/m in lower limit, and still more preferably 28mN/m in upper limit.
The surface tension is a value measured by the Wilhelmy method at 25 ℃ using a dynamic wettability tester.
The sealant for organic EL display elements of the present invention has a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃ and 50% RH. By setting the water content to 1000ppm or less, the reliability of the obtained organic EL display element becomes excellent. The upper limit of the water content is preferably 800ppm, and more preferably 300ppm.
The water content is most preferably 0ppm.
The water content can be measured using a Karl Fischer apparatus under the conditions of an environment of 25 ℃ and 50% RH. The moisture content was measured with respect to the sealant which was left standing for 24 hours and within 30 minutes.
The viscosity, the surface tension and the water content can be set to the above ranges by selecting the species of the polymerizable compound, the polymerization initiator and other components optionally contained, which will be described later, and adjusting the content ratio. Further, by mixing the components of the sealing agent for an organic EL display element and then performing dehydration treatment, the water content can be easily set to 1000ppm or less.
The present invention also provides a method for producing a sealant for an organic EL display element, the method comprising: and a dehydration step in which the mixture containing the polymerizable compound and the polymerization initiator and/or the thermosetting agent is exposed to an environment of 10 to 100 ℃ and 0.1MPa or less for 15 minutes or longer.
The lower limit of the temperature in the dehydration step is preferably 20 ℃ and the upper limit thereof is preferably 80 ℃.
The dehydration step is preferably performed for 20 minutes or more.
In the method for producing the sealant for an organic EL display element of the present invention, other than the dehydration step, examples of the method for dehydrating the sealant for an organic EL display element include a method using a dehydrating agent.
Specific examples of the method of using the dehydrating agent include: a method of flowing a sealant for an organic EL display element into a column filled with a dehydrating agent at a flow rate of about 2.5 liters per hour; a method of adding a dehydrating agent to the organic EL display element sealing agent, stirring the mixture, standing the mixture for about 12 hours, and removing the dehydrating agent by filtration or the like.
Examples of the dehydrating agent include molecular sieves, alumina, calcium chloride, calcium oxide, magnesium perchlorate, anhydrous magnesium sulfate, phosphorus oxide (V), anhydrous potassium carbonate, silica gel, sodium hydroxide, anhydrous sodium sulfate, and zinc chloride. Among them, a molecular sieve is preferable because of its excellent drying ability.
The sealant for an organic EL display element of the present invention contains a polymerizable compound.
The polymerizable compound is preferably a compound containing 20 to 90 parts by weight of an oxygen atom in a molecule in a proportion of 30% or less based on 100 parts by weight of the entire polymerizable compound.
The present inventors have studied using, as a polymerizable compound, a compound having a high content of oxygen atoms in a molecule, such as a compound having a polyoxyalkylene skeleton in its main chain, for the purpose of making a sealant suitable for application by an ink jet method and making the sealant have a low viscosity. However, when a compound having a large content of oxygen atoms in the molecule is used, the following problems arise: when the obtained organic EL display device is exposed to a high-temperature and high-humidity environment, dark spots and the like are generated, and the reliability is liable to deteriorate. Thus, the present inventors have found, as a result of intensive studies: by using the compound having a content of oxygen atoms in the molecule of 30% or less as the polymerizable compound so as to have a specific content, it is possible to easily achieve both ink jet coatability and reliability of the obtained organic EL display element.
The compound having a content of oxygen atoms in the molecule of 30% or less preferably has a content of oxygen atoms in the molecule of 25% or less, more preferably 20% or less.
Further, the lower limit of the content of the compound having a content of oxygen atoms in the molecule of 30% or less in 100 parts by weight of the entire polymerizable compound is more preferably 30 parts by weight, and the upper limit is more preferably 70 parts by weight.
As the polymerizable compound, a radical polymerizable compound or a cation polymerizable compound can be used.
The radical polymerizable compound is preferably a (meth) acrylic compound.
The (meth) acrylic compound may be a monofunctional (meth) acrylic compound, may be a polyfunctional (meth) acrylic compound, or may be used in combination with the polyfunctional (meth) acrylic compound.
In the present specification, the "(meth) acrylic" refers to an acrylic or methacrylic, the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group.
The monofunctional (meth) acrylic compound preferably has a cationically polymerizable group from the viewpoint of low outgassing property and the like.
Examples of the cationically polymerizable group include a vinyl ether group, an epoxy group, an oxetane group, an allyl ether group, a vinyl group, and a hydroxyl group.
Specific examples of the monofunctional (meth) acrylic compound include 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl glycidyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, allyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. Among them, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate are preferable.
In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate.
When the polymerizable compound contains the monofunctional (meth) acrylic compound, the content of the monofunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is preferably 20 parts by weight at the lower limit, and is preferably 80 parts by weight at the upper limit. When the content of the monofunctional (meth) acrylic compound is in this range, the obtained sealant for an organic EL display element is more excellent in low outgassing property and the like. A more preferable lower limit of the content of the monofunctional (meth) acrylic compound is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.
From the viewpoint of ink-jet coatability, the polyfunctional (meth) acrylic compound preferably has a polyoxyalkylene skeleton in the main chain. Among these, when a compound having a large content of oxygen atoms in the molecule is used as described above, the reliability of the obtained organic EL display device is liable to deteriorate, and therefore, when a polyfunctional (meth) acrylic compound having a polyoxyalkylene skeleton in the main chain is used, it is preferable to adjust the content thereof. That is, the content of the polyfunctional (meth) acrylic compound having a polyoxyalkylene skeleton in the main chain is preferably adjusted so that the content of the compound having an oxygen atom content ratio in the molecule of 30% or less falls within the above range.
The polyoxyalkylene skeleton is preferably a skeleton in which oxyalkylene units are present in a row of 2 to 6.
Examples of the oxyalkylene unit constituting the polyoxyalkylene skeleton include an oxyethylene unit and an oxypropylene unit.
From the viewpoint of ink-jet coatability and the like, the polyfunctional (meth) acrylic compound is preferably a structure having a carbon chain with few branches, and more preferably a linear structure.
Specific examples of the polyfunctional (meth) acrylic compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like. Among them, tetraethylene glycol di (meth) acrylate is preferable.
When the polymerizable compound contains the polyfunctional (meth) acrylic compound, the lower limit of the content of the polyfunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is preferably 20 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the polyfunctional (meth) acrylic compound is in this range, the obtained sealing agent for an organic EL display element is more excellent in ink-jet coatability and the like. A more preferable lower limit and a more preferable upper limit of the content of the polyfunctional (meth) acrylic compound are 30 parts by weight and 60 parts by weight, respectively.
When the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound are used in combination, the content ratio of the monofunctional (meth) acrylic compound to the polyfunctional (meth) acrylic compound is preferably a monofunctional (meth) acrylic compound in terms of a weight ratio: multifunctional (meth) acrylic compounds = 7: 3 to 3: 7. By setting the content ratio of the monofunctional (meth) acrylic compound to the polyfunctional (meth) acrylic compound in this range, the obtained sealing agent for an organic EL display element can be more excellent in ink jet coatability and the like. The content ratio of the monofunctional (meth) acrylic compound to the polyfunctional (meth) acrylic compound is more preferably a monofunctional (meth) acrylic compound in terms of a weight ratio: multifunctional (meth) acrylic = 6: 4 to 4: 6.
Examples of the cationically polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.
Examples of the epoxy compound include bisphenol a type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol O type epoxy resins, 2' -diallylbisphenol a type epoxy resins, alicyclic epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol a type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, thioether type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, O-cresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenol novolac type epoxy resins, naphthol novolac type epoxy resins, glycidyl amine type epoxy resins, alkyl polyol type epoxy resins, rubber modified epoxy resins, glycidyl ester compounds, 1, 6-hexanediol diglycidyl ether, and the like. Among them, an alicyclic epoxy resin is preferable.
Examples of the commercially available products of the alicyclic epoxy resin include CELLOXIDE 2000, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 3000, and CELLOXIDE 8000 (all manufactured by Dailol corporation); sansocizer EPS (New Nippon chemical industry Co., ltd.), and the like.
Examples of the oxetane compound include allyloxybetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- ((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-3- ((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolak oxetane, 1, 4-bis (((3-ethyl-3-oxetan) methoxy) methyl) benzene, and the like.
Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1, 4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, and the like.
The sealing agent for an organic EL display element of the present invention contains a polymerization initiator.
As the polymerization initiator, a photo radical polymerization initiator, a thermal radical polymerization initiator, a photo cation polymerization initiator, and a thermal cation polymerization initiator can be suitably used depending on the kind of the polymerizable compound used, and the like.
Examples of the photo radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, benzil, and thioxanthone-based compounds.
Examples of commercially available products among the photo radical polymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE oxe01, and Lucirin TPO (both manufactured by BASF); benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo chemical industries Co., ltd.), and the like.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators formed from azo compounds, organic peroxides, and the like.
Examples of the azo compound include 2,2' -azobis (2, 4-dimethylvaleronitrile) and azobisisobutyronitrile.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
Examples of commercially available products among the thermal radical polymerization initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako pure chemical industries, ltd.).
The photo cation polymerization initiator is not particularly limited as long as it generates a protonic acid or a lewis acid by light irradiation, and may be an ionic photo acid type or a nonionic photo acid type.
Examples of the anionic moiety of the above-mentioned ionic photoacid generator type photocationic polymerization initiator include BF 4 - 、PF 6 - 、SbF 6 - Or (BX) 4 ) - (wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups).
Examples of the ionic photoacid generator type photo-cationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salts having the above-mentioned anionic moiety.
Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonium) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (2-hydroxyethoxy)) phenylsulfoxonium) phenyl) sulfide, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.
Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, and 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
Examples of the (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluorophosphate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, and (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (pentafluorophenyl) borate.
Examples of the nonionic photoacid-generating type photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide sulfonic acid salts.
Examples of commercially available products among the above-mentioned photo cation polymerization initiators include DTS-200 (manufactured by Green chemical Co., ltd.); UVI6990 and UVI6974 (both manufactured by Union Carbide Co., ltd.); SP-150 and SP-170 (both manufactured by ADEKA Co., ltd.); FC-508, FC-512 (both 3M); IRGACURE261, IRGACURE290 (both manufactured by BASF corporation); PI2074 (Rhodia).
As the above-mentioned thermal cationic polymerization initiator, there may be mentioned those having an anionic moiety represented by BF 4 - 、PF 6 - 、SbF 6 - Or (BX) 4 ) - (wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups), sulfonium salts, phosphonium salts, ammonium salts, and the like. Among them, sulfonium salts and ammonium salts are preferable.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
Examples of the phosphonium salts include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate and the like.
Examples of the above ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N-diethyl-N-benzylanilinium tetrafluoroborate, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, and the like.
Examples of commercially available products among the above thermal cationic polymerization initiators include San-Aid SI-60, san-Aid SI-80, san-Aid SI-B3A and San-Aid SI-B4 (all manufactured by Sanxin chemical industries Co., ltd.); CXC1612 and CXC1821 (both King Industries, ltd.), and the like.
The lower limit of the content of the polymerization initiator is preferably 0.01 part by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the polymerizable compound. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for an organic EL display element is more excellent in curability. By setting the content of the polymerization initiator to 10 parts by weight or less, the curing reaction of the obtained sealant for an organic EL display element is not excessively accelerated, the workability is more excellent, and the cured product can be more uniform. The lower limit of the content of the polymerization initiator is more preferably 0.05 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealing agent for an organic EL display element of the present invention may contain a sensitizer. The sensitizer has the effect of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for an organic EL display element of the present invention.
Examples of the sensitizer include thioxanthone compounds such as 2, 4-diethylthioxanthone; 2, 2-dimethoxy-1, 2-diphenylethan-1-one, benzophenone, 2, 4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4 '-bis (dimethylamino) benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide and the like.
The content of the sensitizer is preferably 0.01 part by weight or less, and more preferably 3 parts by weight or more, based on 100 parts by weight of the polymerizable compound. The sensitizing effect can be further exhibited by setting the content of the sensitizing agent to 0.01 part by weight or more. By setting the content of the sensitizer to 3 parts by weight or less, light can be transmitted to a deep portion without excessive absorption. A more preferable lower limit of the content of the sensitizer is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.
The sealing agent for an organic EL display element of the present invention may contain a silane coupling agent. The silane coupling agent has an effect of improving the adhesion of the sealant for an organic EL display element of the present invention to a substrate or the like.
Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used alone, or two or more of them may be used in combination.
The preferable lower limit of the content of the silane coupling agent is 0.1 part by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is in this range, the effect of improving the adhesion can be further enhanced while suppressing bleeding of the excess silane coupling agent. The lower limit of the content of the silane coupling agent is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealing agent for an organic EL display element of the present invention may further contain a surface modifier within a range not to impair the object of the present invention. By containing the surface modifier, the sealant for an organic EL display element of the present invention can be provided with flatness of a coating film.
Examples of the surface modifier include a surfactant and a leveling agent.
Examples of the surface modifier include silicone-based surface modifiers, fluorine-based surface modifiers, and the like.
Examples of commercially available products among the above surface modifiers include BYK-340, BYK-345 (both BYK-Chemie JAPAN Co.), surflon S-611 (AGC Seimi Chemical Co., ltd.).
The sealing agent for an organic EL display element of the present invention may contain a solvent for the purpose of adjusting viscosity or the like, but there is a concern that problems such as deterioration of the organic light emitting material layer or degassing occur due to the remaining solvent, and therefore, it is preferable that no solvent is contained or the content of the solvent is 0.05 wt% or less.
The sealing agent for an organic EL display element of the present invention may contain various known additives such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant, as required.
Examples of the method for producing the sealant for an organic EL display element of the present invention include a method of mixing a polymerizable compound, a polymerization initiator, and an additive such as a silane coupling agent, which is added as needed, using a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill.
The lower limit of the total light transmittance of the cured product of the sealing agent for an organic EL display element of the present invention at a wavelength of 380 to 800nm is preferably 80%. By setting the total light transmittance to 80% or more, the optical characteristics of the obtained organic EL display device become more excellent. A more preferred lower limit of the total light transmittance is 85%.
The total light transmittance can be measured using a spectrometer such as an AUTOMATIC HAZE matrix MODEL TC = III DPK (manufactured by tokyo electric color corporation).
Further, if the cured product used for the measurement of the total light transmittance is a photocurable sealing agent, the sealing agent can be irradiated with, for example, 3000mJ/cm by an LED lamp 2 365nm, or a thermosetting sealing agent, for example, at 80 deg.CHeated for 1 hour.
The sealant for an organic EL display element of the present invention preferably has a transmittance at 400nm of 85% or more in terms of an optical path length of 20 μm after irradiating a cured product with ultraviolet light for 100 hours. By setting the transmittance after 100 hours of ultraviolet irradiation to 85% or more, the transparency is increased, the loss of light emission is reduced, and the color reproducibility is further improved. The lower limit of the transmittance after 100 hours of the ultraviolet irradiation is more preferably 90%, and still more preferably 95%.
As the light source for irradiating the ultraviolet ray, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
Further, if the cured product used for the measurement of the transmittance after the irradiation with ultraviolet light for 100 hours is a photocurable sealing agent, the sealing agent can be irradiated with, for example, 3000mJ/cm by an LED lamp 2 365nm, or a thermosetting sealing agent, for example, by heating at 80 ℃ for 1 hour.
The sealant for an organic EL display element of the present invention preferably has a moisture permeability of 100g/m under a thickness condition of 100 μm measured by exposing a cured product to an environment of 85 ℃ and 85 RH for 24 hours in accordance with JIS Z0208 2 The following. By setting the above moisture permeability to 100g/m 2 Hereinafter, the effect of preventing the occurrence of dark spots due to the arrival of moisture at the organic light-emitting material layer becomes more excellent, and the reliability of the resulting organic EL display element becomes more excellent.
In addition, if the determination of the moisture permeability of the cured product is a photocurable sealant, can be used by using an LED lamp to the sealant irradiation of 3000mJ/cm 2 365nm, or a thermosetting sealing agent, for example, by heating at 80 ℃ for 1 hour.
Further, in the sealant for an organic EL display element of the present invention, when the cured product is exposed to an environment of 85 ℃ and 85% RH for 24 hours, the water content of the cured product is preferably less than 0.5%. When the water content of the cured product is less than 0.5%, the effect of preventing the organic light-emitting material layer from being deteriorated by the water in the cured product becomes more excellent, and the reliability of the obtained organic EL display element becomes more excellent. The upper limit of the water content of the cured product is more preferably 0.3%.
Examples of the method for measuring the water content include a method of obtaining the water content by the karl fischer method in accordance with JIS K7251, a method of obtaining the weight gain after water absorption in accordance with JIS K7209-2, and the like.
Further, if the cured product used for the measurement of the water content is a photocurable sealing agent, the sealing agent can be irradiated with, for example, 3000mJ/cm using an LED lamp 2 365nm, or a thermosetting sealing agent, for example, by heating at 80 ℃ for 1 hour.
The sealing agent for an organic EL display element of the present invention 1 can be suitably used for coating by an ink-jet method, and the sealing agent for an organic EL display element of the present invention 2 can be used for coating by an ink-jet method.
Examples of a method for producing an organic EL display element using the sealing agent for an organic EL display element of the present invention include a method comprising the following steps: a step of applying the sealant for an organic EL display element of the present invention to a substrate by an inkjet method; and curing the applied sealing agent for the organic EL display element by light irradiation and/or heating.
In the step of applying the sealant for an organic EL display element of the present invention to a substrate, the sealant for an organic EL display element of the present invention may be applied to the entire surface of the substrate or may be applied to a part of the substrate. The shape of the sealing portion of the sealing agent for an organic EL display element of the present invention formed by coating is not particularly limited as long as it is a shape capable of protecting a laminate having an organic light emitting material layer from an external gas, and may be a shape that completely covers the laminate, may be a pattern that is closed at the peripheral portion of the laminate, or may be a pattern that is a shape in which a part of an opening is provided at the peripheral portion of the laminate.
Curing the sealant for organic EL display element by light irradiationThe sealing agent for an organic EL display element of the present invention can be obtained by irradiating a light having a wavelength of 300 to 400nm and a cumulative light amount of 300 to 3000mJ/cm 2 Is well cured.
Examples of the light source used for irradiating the organic EL display element sealant of the present invention with light include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used alone, or two or more kinds may be used in combination.
These light sources can be appropriately selected according to the absorption wavelength of the photo-radical polymerization initiator or photo-cation polymerization initiator.
Examples of the means for irradiating the sealing agent for an organic EL display element of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time difference, and combined irradiation of simultaneous irradiation and sequential irradiation, and any irradiation means can be used.
The cured product obtained by the step of curing the sealing agent for an organic EL display element by light irradiation and/or heating may be further covered with an inorganic material film.
As the inorganic material constituting the inorganic material film, conventionally known inorganic materials can be used, and examples thereof include silicon nitride (SiN) x ) Silicon oxide (SiO) x ) And so on. The inorganic material film may be composed of 1 layer, or a plurality of layers may be laminated. The laminate may be covered with the inorganic material film and the resin film formed from the sealant for an organic EL display element of the present invention alternately and repeatedly.
The method of manufacturing the organic EL display device may include the steps of: a step of bonding the substrate coated with the sealant for an organic EL display element of the present invention (hereinafter, also referred to as "one substrate") to the other substrate.
The substrate (hereinafter, also referred to as "one substrate") to which the sealant for an organic EL display element of the present invention is applied may be a substrate on which a laminate having an organic light-emitting material layer is formed, or may be a substrate on which the laminate is not formed.
When the one substrate is a substrate on which the laminate is not formed, the sealant for an organic EL display element of the present invention may be applied to the one substrate so that the laminate can be protected from external air when the other substrate is bonded. That is, the entire surface of the portion to be the position of the laminate may be coated when the other substrate is bonded, or the sealant portion may be formed in a pattern that closes the shape in which the portion to be the position of the laminate is completely housed when the other substrate is bonded.
The step of curing the sealant for organic EL display elements by light irradiation and/or heating may be performed before the step of bonding the one substrate and the other substrate, or may be performed after the step of bonding the one substrate and the other substrate.
In the case where the step of curing the sealant for organic EL display elements by light irradiation and/or heating is performed before the step of bonding the one substrate and the other substrate, the pot life of the sealant for organic EL display elements of the present invention is preferably 1 minute or more from the time of light irradiation and/or heating until the curing reaction proceeds and bonding is not possible. By setting the usable time to 1 minute or more, curing does not progress excessively before the one base material and the other base material are bonded, and a higher adhesive strength can be obtained.
In the step of bonding the one substrate and the other substrate, a method of bonding the one substrate and the other substrate is not particularly limited, and bonding is preferably performed in a reduced pressure atmosphere.
The lower limit of the degree of vacuum in the reduced pressure atmosphere is preferably 0.01kPa, and the upper limit is preferably 10kPa. By setting the degree of vacuum in the reduced-pressure atmosphere to this range, it takes no longer time to reach a vacuum state from the viewpoint of airtightness of a vacuum apparatus and the capability of a vacuum pump, and bubbles in the sealant for an organic EL display element of the present invention when the one substrate and the other substrate are bonded can be removed more effectively.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing property, and can provide an organic EL display element having excellent reliability. Further, according to the present invention, a method for producing the sealant for organic EL display elements can be provided.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(examples 1 to 7 and comparative examples 1 to 4)
The materials were uniformly stirred and mixed at a stirring speed of 3000rpm using a homodispersion type stirring mixer (manufactured by Primix, "homo plastic L type") in accordance with the mixing ratio described in table 1, thereby producing each of the organic EL display element sealants of examples 1 to 7 and comparative examples 1 to 4. The sealing agents for organic EL display elements obtained in examples 1 to 5 and comparative examples 1 and 2 were stirred and mixed, and then subjected to a dehydration step of exposing the mixture to an atmosphere of 50 ℃ and 0.1MPa for 30 minutes.
The viscosities measured at 25 ℃ and 100rpm with an E-type VISCOMETER (manufactured by eastern industries, inc., "visible TV-22") and the surface tensions measured at 25 ℃ with a dynamic wettability tester (manufactured by RHESCA, inc., "WET-6100") for the respective sealants for organic EL display elements obtained in examples and comparative examples are shown in table 1.
Further, 10g of each of the organic EL display element sealants obtained in examples and comparative examples was charged into a Hi-Bessel container, and left to stand in a constant temperature and humidity apparatus at 25 ℃ and 50% rh for 24 hours, and then the water content of each of the organic EL display element sealants was measured at 25 ℃ and 50% rh using a karl fisher apparatus. BHB-160 (manufactured by Ningplasma vessels) was used as the Hi-Bessel vessel, and MKC-710S (manufactured by Kyoto electronics industries, ltd.) was used as the Karl Fischer apparatus. The water content was measured with respect to the sealant just after the sealant was taken out from the constant temperature and humidity apparatus (within 30 minutes) after standing for 24 hours. The results are shown in Table 1.
< evaluation >
The following evaluations were made for each of the organic EL display element sealants obtained in examples and comparative examples. The results are shown in Table 1.
In each of the evaluations of the ink ejection property, the wetting and diffusing property, and the reliability of the organic EL display element, IJH-30 (IJT corporation) was used as an ink jet coating head, and ink jet coating was performed without heating (head temperature 25 ℃).
(1) Ink-jet coatability
(1-1) ink jet ejectability
The respective organic EL display element sealants obtained in examples and comparative examples were applied to alkali-free glass (asahi glass, "AN 100") cleaned with alkali, using AN inkjet discharge apparatus (manufactured by microdot, "NanoPrinter 500"), at a drop volume of 30 picoliters. The case where the liquid droplets were normally ejected from the ink jet nozzles and landed on the substrate was marked as "o", and the case where the liquid droplets were not normally ejected was marked as "x", and the ink ejection performance was evaluated.
(1-2) wetting and diffusing Property
The respective organic EL display element sealants obtained in examples 1 to 7 and comparative examples 3 and 4 were applied to alkali-cleaned alkali-free glass (manufactured by asahi glass, "AN 100") at a rate of 5 m/sec and at a pitch of 500 μm in a drop amount of 30 picoliters using AN ink jet apparatus (manufactured by microsoft corporation, "NanoPrinter 500"). The diameter of the droplet on the alkali-free glass 10 minutes after the application was measured, and the wet diffusibility was evaluated by marking the case where the droplet diameter was 150 μm or more as "O", the case where the droplet diameter was 50 μm or more and less than 150 μm as "Δ", and the case where the droplet diameter was less than 50 μm as "X".
(2) Low degassing property
Gas chromatograph using headspace method (manufactured by JEOL Ltd.)And "JMS-Q1050 GC"), the degassing generated during heating of the cured products of the organic EL display element sealants obtained in examples 1 to 7 and comparative examples 3 and 4 was measured. Each organic EL display element was coated with 100mg of the sealant to a thickness of 300 μm by an applicator. Next, 3000mJ/cm was irradiated with an LED lamp 2 Curing the sealant with 365nm ultraviolet rays, filling the cured sealant into a vial for headspace, sealing the vial, heating at 100 ℃ for 30 minutes, and measuring the generated gas by headspace method.
The gas generated was evaluated for low outgassing, and the gas was rated as "O" when it was less than 300ppm, as "Δ" when it was 300ppm or more and less than 500ppm, and as "X" when it was 500ppm or more.
(3) Reliability of organic EL display element
(3-1) production of substrate having laminate comprising organic light-emitting Material layer
Is coated on a glass substrate (25 mm in length, 25mm in width and 0.7mm in thickness)
The thickness of (3) is such that an ITO electrode is formed into a film, and the film is used as a substrate. The substrate was ultrasonically cleaned with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, then cleaned with boiling isopropyl alcohol for 10 minutes, and further pretreated with a UV-ozone cleaner (NL-UV 253, manufactured by japan laser electronics).
Subsequently, the substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200mg of N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (. Alpha. -NPD) was charged into a bisque-fired crucible, and tris (8-hydroxyquinoline) aluminum (Alq) was charged into another bisque-fired crucible 3 ) 200mg, the pressure in the vacuum chamber was reduced to 1X 10 -4 Pa is up to. Thereafter, the crucible containing the alpha-NPD is heated to cause the alpha-NPD to react with the molten metal
Is deposited on a substrate at a deposition rate to form a film with a thickness of
The hole transport layer of (1). Then, will be charged with Alq 3 Is heated in a crucible to
The deposition rate of (2) is set to a film thickness
The organic light emitting material layer of (1). Thereafter, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum deposition apparatus, and 200mg of lithium fluoride was charged into a tungsten resistance heating boat in the vacuum deposition apparatus, and 1.0g of an aluminum wire was charged into another tungsten boat. Thereafter, the pressure in the evaporator of the vacuum evaporation apparatus was reduced to 2 × 10 -4 Pa, and fluorinating lithium with
Is deposited at a deposition rate of
Then, aluminum is added
At a rate of film formation of
The inside of the evaporator was returned to normal pressure by nitrogen gas, and the substrate on which the laminate having 10mm × 10mm organic light-emitting material layers was disposed was taken out.
(3-2) covering based on inorganic Material film A
A mask having an opening of 13mm × 13mm was provided so as to cover the entire laminate in the resulting substrate on which the laminate was disposed, and the inorganic material film a was formed by a plasma CVD method.
The plasma CVD method was performed under the following conditions: siH is used as the raw material gas 4 Gas and nitrogen at respective flow rates of SiH 4 The RF power was set to 10W (frequency: 2.45 GHz) and the chamber temperature was set to 1 sccm for gas 10sccm and nitrogen 200sccmThe pressure in the chamber was set at 0.9Torr at 00 ℃.
The thickness of the inorganic material film a formed is about 1 μm.
(3-3) formation of resin protective film
The obtained substrate was pattern-coated with each of the organic EL display element sealants obtained in examples 1 to 7 and comparative examples 3 and 4 using an inkjet discharge apparatus (manufactured by microdot, "NanoPrinter 500").
Thereafter, using an LED lamp, 3000mJ/cm was irradiated 2 Ultraviolet rays having a wavelength of 365nm, curing the sealing agent for the organic EL display element, thereby forming a resin protective film.
(3-4) covering based on inorganic Material film B
After the formation of the resin protective film, a mask having openings of 12mm × 12mm was provided so as to cover the entire resin protective film, and the inorganic material film B was formed by a plasma CVD method, thereby obtaining an organic EL display element.
The plasma CVD method is performed under the same conditions as the above-mentioned "(3-2) covering with the inorganic material film a".
The thickness of the inorganic material film B formed was about 1 μm.
(3-5) light-emitting State of organic EL display element
The organic EL display device thus obtained was exposed to an atmosphere of 85 ℃ and 85% humidity for 100 hours, and then a voltage of 3V was applied thereto, and the light emission state (presence or absence of dark spots and extinction around pixels) of the organic EL display device was visually observed. The display performance of the organic EL display element was evaluated by marking "o" for the case where light was uniformly emitted without dark spots or peripheral extinction, marking "Δ" for the case where a slight decrease in luminance was observed without dark spots or peripheral extinction, and marking "x" for the case where dark spots or peripheral extinction were observed.
[ Table 1]
In order to confirm the effect of the viscosity of the sealing agent for organic EL display elements on the ink-jet coatability in the non-heating type ink-jet method and the heating type ink-jet method, the following experiment was performed. The results are shown in Table 2.
(Experimental example 1)
The respective materials were uniformly stirred and mixed at a stirring speed of 3000rpm in a mixing ratio shown in table 2 using a homodispersion type stirring mixer (manufactured by Primix, "homo polymer L type"), and then subjected to a dehydration step of exposing the mixture to an atmosphere of 50 ℃ and 0.1MPa for 30 minutes, thereby producing a sealant for an organic EL display element.
The obtained sealing agent for organic EL display element was measured for viscosity at 25 ℃ and 100rpm using an E-type VISCOMETER (manufactured by eastern industries, ltd. "VISCOMETER TV-22") and for surface tension at 25 ℃ using a dynamic wettability tester (manufactured by RHESCA, manufactured by "WET-6100").
Further, 10g of the obtained sealing agent for organic EL display elements was charged into a Hi-Bessel container, allowed to stand in a constant temperature and humidity apparatus at 25 ℃ and 50% RH for 24 hours, and then the water content of the sealing agent for organic EL display elements was measured at 25 ℃ and 50% RH using a Karl Fischer apparatus. BHB-160 (manufactured by Ningplasma vessels) was used as the Hi-Bessel vessel, and MKC-710S (manufactured by Kyoto electronics industries, ltd.) was used as the Karl Fischer apparatus. The water content was measured with respect to the sealant just after the sealant was taken out from the constant temperature and humidity apparatus (within 30 minutes) after standing for 24 hours.
The obtained organic EL display element sealant was applied to alkali-cleaned alkali-free glass (manufactured by asahi glass, "AN 100") in a drop amount of 30 picoliters using AN ink jet apparatus (manufactured by microsoft corporation, "NanoPrinter 500"). The case where the liquid droplets were normally ejected from the ink jet nozzles and landed on the substrate was marked as "o", and the case where the liquid droplets were not normally ejected was marked as "x", and the ink ejection performance was evaluated. The ink jet coating head used was IJH-30 (IJT corporation), and the ink jet coating was performed without heating (the head temperature was 25 ℃).
(Experimental example 2)
The same sealant for organic EL display elements as the sealant produced in experimental example 1 was prepared.
Ink jet ejection performance was evaluated in the same manner as in experimental example 1, except that IJH-30 (IJT corporation) was used as an ink jet coating head, and ink jet coating was performed while heating (head temperature 60 ℃).
[ Table 2]
Industrial applicability
The present invention can provide a sealing agent for an organic EL display element, which can be easily applied by an ink jet method, has excellent low outgassing properties, and can provide an organic EL display element having excellent reliability. Further, according to the present invention, a method for producing the sealant for organic EL display elements can be provided.
Claims (6)
1. A sealing agent for an organic EL display element, characterized by containing a polymerizable compound, a polymerization initiator, and a silicone-based surface modifier or a fluorine-based surface modifier,
the polymerizable compound contains 20 to 90 parts by weight of an alicyclic epoxy resin and/or an oxetane compound having a content of oxygen atoms in a molecule of 30% or less based on 100 parts by weight of the whole polymerizable compound,
the organic EL display element sealing agent has a viscosity of 5 to 40 mPas at 25 ℃, a surface tension of 15 to 30mN/m at 25 ℃, and a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃ and 50% RH.
2. A sealing agent for an organic EL display element, which is used for coating by an ink-jet method,
the sealant for organic EL display elements contains a polymerizable compound, a polymerization initiator, and a silicone surface modifier or a fluorine surface modifier,
the polymerizable compound contains 20 to 90 parts by weight of an alicyclic epoxy resin and/or an oxetane compound having a content of oxygen atoms in a molecule of 30% or less based on 100 parts by weight of the entire polymerizable compound,
the organic EL display element sealing agent has a water content of 1000ppm or less at 25 ℃ after being left to stand for 24 hours in an environment of 25 ℃ and 50% RH.
3. The sealant for an organic EL display element according to claim 1 or 2, wherein the polymerizable compound contains 30 to 90 parts by weight of an alicyclic epoxy resin and/or an oxetane compound having a content of an oxygen atom in a molecule of 30% or less, based on 100 parts by weight of the entire polymerizable compound.
4. The sealant for an organic EL display element according to claim 1 or 2, wherein a content of the solvent is 0.05 wt% or less.
5. The sealant for an organic EL display element according to claim 4, which is free from a solvent.
6. A method for producing the sealant for an organic EL display element according to claim 1,2, 3,4 or 5,
the method comprises the following steps: and a dehydration step in which the mixture containing the polymerizable compound and the polymerization initiator and/or the thermosetting agent is exposed to an environment of 10 to 100 ℃ and 0.1MPa or less for 15 minutes or longer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110656273.1A CN113214604A (en) | 2016-10-19 | 2017-10-18 | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-205483 | 2016-10-19 | ||
| JP2016205483 | 2016-10-19 | ||
| PCT/JP2017/037656 WO2018074507A1 (en) | 2016-10-19 | 2017-10-18 | Organic el display element sealing agent, and method for producing organic el display element sealing agent |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110656273.1A Division CN113214604A (en) | 2016-10-19 | 2017-10-18 | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108886849A CN108886849A (en) | 2018-11-23 |
| CN108886849B true CN108886849B (en) | 2022-10-21 |
Family
ID=62018758
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110656273.1A Pending CN113214604A (en) | 2016-10-19 | 2017-10-18 | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element |
| CN201780020277.2A Active CN108886849B (en) | 2016-10-19 | 2017-10-18 | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110656273.1A Pending CN113214604A (en) | 2016-10-19 | 2017-10-18 | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element |
Country Status (4)
| Country | Link |
|---|---|
| JP (4) | JP6427283B2 (en) |
| KR (2) | KR102416054B1 (en) |
| CN (2) | CN113214604A (en) |
| WO (1) | WO2018074507A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7039391B2 (en) * | 2018-05-25 | 2022-03-22 | 三井化学株式会社 | Sealant for display element, sealant for organic EL element and its cured product |
| JP7153870B2 (en) * | 2018-05-31 | 2022-10-17 | パナソニックＩｐマネジメント株式会社 | Ultraviolet curable resin composition for encapsulating organic EL element, method for manufacturing organic EL light emitting device, and organic EL light emitting device |
| JP2019212399A (en) * | 2018-05-31 | 2019-12-12 | パナソニックＩｐマネジメント株式会社 | Uv-curable resin composition for sealing organic el element, method for manufacturing organic el light-emitting device, and organic el light-emitting device |
| JP7262038B2 (en) * | 2018-08-03 | 2023-04-21 | パナソニックＩｐマネジメント株式会社 | Ultraviolet curable resin composition for encapsulating organic EL element, method for manufacturing organic EL light emitting device, and organic EL light emitting device |
| CN111234606A (en) * | 2020-02-15 | 2020-06-05 | 苏州星烁纳米科技有限公司 | Packaging ink and light-emitting device |
| JPWO2021200668A1 (en) | 2020-03-31 | 2021-10-07 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008153076A1 (en) * | 2007-06-14 | 2008-12-18 | Sekisui Chemical Co., Ltd. | Optical adhesive for substrate bonding and optical adhesive cured body for substrate bonding |
| CN101416104A (en) * | 2006-03-29 | 2009-04-22 | 积水化学工业株式会社 | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
| CN102046690A (en) * | 2008-07-31 | 2011-05-04 | 大赛璐化学工业株式会社 | Optical semiconductor sealing resin composition and optical semiconductor device using same |
| WO2015129670A1 (en) * | 2014-02-27 | 2015-09-03 | 積水化学工業株式会社 | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3817081B2 (en) | 1999-01-29 | 2006-08-30 | パイオニア株式会社 | Manufacturing method of organic EL element |
| JP2001307873A (en) | 2000-04-21 | 2001-11-02 | Toppan Printing Co Ltd | Organic electroluminescence display element and its manufacturing method |
| US8808457B2 (en) | 2002-04-15 | 2014-08-19 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
| JP2004188903A (en) * | 2002-12-13 | 2004-07-08 | Konica Minolta Holdings Inc | Capping member, cleaning member, piping member, ink tank member, and uv hardening type inkjet recording device with these |
| JP2005302414A (en) * | 2004-04-08 | 2005-10-27 | Three Bond Co Ltd | Curing agent for two-part polyepoxy resin put under dehydration treatment and its utilization |
| JP2008153211A (en) | 2006-11-22 | 2008-07-03 | Fujifilm Corp | Barrier performance film substrate and its manufacturing method |
| JP2009102622A (en) * | 2007-10-03 | 2009-05-14 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing, and electronic component device |
| JP2010182634A (en) * | 2009-02-09 | 2010-08-19 | Seiko Epson Corp | Organic electroluminescent device |
| DE102009013710A1 (en) * | 2009-03-20 | 2010-09-23 | Merck Patent Gmbh | Polymers from blends with vinyl ether monomers |
| JP5356928B2 (en) * | 2009-06-17 | 2013-12-04 | 旭化成ケミカルズ株式会社 | Photosensitive resin composition, and photosensitive inkjet ink, photosensitive adhesive, photosensitive coating agent, and semiconductor encapsulant using the same |
| JP5849703B2 (en) * | 2009-11-19 | 2016-02-03 | コニカミノルタ株式会社 | Method for producing gas barrier film, method for producing organic photoelectric conversion element, and method for producing organic electroluminescence element |
| CN103459375B (en) * | 2011-04-07 | 2016-10-12 | 三菱化学株式会社 | Organic compound, charge transport materials, compositions, organic electroluminescent device, display device and illuminator containing this compound |
| JP5916220B2 (en) * | 2012-07-19 | 2016-05-11 | 日本化薬株式会社 | Energy ray curable resin composition and cured product thereof |
| US10559777B2 (en) * | 2012-07-19 | 2020-02-11 | Basf Coatings Gmbh | Radiation curable composition for water scavenging layer, and method of manufacturing the same |
| HUE056672T2 (en) * | 2012-12-14 | 2022-02-28 | Dexerials Corp | Method of producing image display device |
| KR20150091380A (en) * | 2013-02-14 | 2015-08-10 | 후지필름 가부시키가이샤 | Photosensitive resin composition for inkjet application, heat-treated substance, manufacturing method therefor, resin-pattern manufacturing method, liquid-crystal display, organic electroluminescent display, touch panel, manufacturing method therefor, and touch-panel display |
| KR101837259B1 (en) * | 2013-03-29 | 2018-03-09 | 후루카와 덴키 고교 가부시키가이샤 | Resin composition for element encapsulation for organic electronic devices, resin sheet for element encapsulation for organic electronic devices, organic electroluminescent element and image display device |
| JP6274639B2 (en) * | 2013-05-23 | 2018-02-07 | 日本化薬株式会社 | Energy ray curable resin composition and cured product thereof |
| WO2014192881A1 (en) * | 2013-05-31 | 2014-12-04 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material, liquid crystal display element and production method of sealing agent for liquid crystal display element |
| JP2015050143A (en) * | 2013-09-04 | 2015-03-16 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| WO2015064410A1 (en) * | 2013-10-30 | 2015-05-07 | 積水化学工業株式会社 | Sealing agent for organic el display elements |
| DE102013223451A1 (en) * | 2013-11-18 | 2015-05-21 | Tesa Se | Process for drying adhesives |
| KR102245326B1 (en) * | 2014-01-21 | 2021-04-27 | 세키스이가가쿠 고교가부시키가이샤 | Light/moisture-curable resin composition, adhesive for electronic components, and adhesive for display elements |
| KR20160111377A (en) * | 2014-01-23 | 2016-09-26 | 덴카 주식회사 | Resin composition |
| CN106062121B (en) * | 2014-05-02 | 2018-03-13 | 三井化学株式会社 | Sealing material and its solidfied material |
| KR20220098297A (en) * | 2014-05-20 | 2022-07-11 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for organic electroluminescence display element |
| KR20160011310A (en) * | 2014-07-21 | 2016-02-01 | 삼성디스플레이 주식회사 | Organic light emitting display apparatus and method for manufacturing the same |
| US9909022B2 (en) * | 2014-07-25 | 2018-03-06 | Kateeva, Inc. | Organic thin film ink compositions and methods |
| US10227498B2 (en) * | 2014-09-26 | 2019-03-12 | Lg Chem, Ltd. | UV-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby |
| JP2016104521A (en) * | 2014-12-01 | 2016-06-09 | セイコーエプソン株式会社 | Ink jet recording device, maintenance method of ink jet recording device, maintenance liquid, and liquid set |
| CN106459374B (en) * | 2015-02-13 | 2020-10-13 | 积水化学工业株式会社 | Sealing agent for organic electroluminescent display element |
-
2017
- 2017-10-18 KR KR1020187026418A patent/KR102416054B1/en active IP Right Grant
- 2017-10-18 CN CN202110656273.1A patent/CN113214604A/en active Pending
- 2017-10-18 CN CN201780020277.2A patent/CN108886849B/en active Active
- 2017-10-18 WO PCT/JP2017/037656 patent/WO2018074507A1/en active Application Filing
- 2017-10-18 KR KR1020227022052A patent/KR20220097552A/en not_active Application Discontinuation
- 2017-10-18 JP JP2017556252A patent/JP6427283B2/en active Active
-
2018
- 2018-10-12 JP JP2018193463A patent/JP6997062B2/en active Active
-
2021
- 2021-12-07 JP JP2021198477A patent/JP2022037060A/en active Pending
-
2023
- 2023-11-15 JP JP2023194285A patent/JP2024023308A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101416104A (en) * | 2006-03-29 | 2009-04-22 | 积水化学工业株式会社 | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
| WO2008153076A1 (en) * | 2007-06-14 | 2008-12-18 | Sekisui Chemical Co., Ltd. | Optical adhesive for substrate bonding and optical adhesive cured body for substrate bonding |
| CN102046690A (en) * | 2008-07-31 | 2011-05-04 | 大赛璐化学工业株式会社 | Optical semiconductor sealing resin composition and optical semiconductor device using same |
| WO2015129670A1 (en) * | 2014-02-27 | 2015-09-03 | 積水化学工業株式会社 | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113214604A (en) | 2021-08-06 |
| KR20190064530A (en) | 2019-06-10 |
| JPWO2018074507A1 (en) | 2018-10-18 |
| JP6997062B2 (en) | 2022-01-17 |
| WO2018074507A1 (en) | 2018-04-26 |
| KR20220097552A (en) | 2022-07-07 |
| KR102416054B1 (en) | 2022-07-01 |
| JP2022037060A (en) | 2022-03-08 |
| JP6427283B2 (en) | 2018-11-21 |
| CN108886849A (en) | 2018-11-23 |
| JP2019040872A (en) | 2019-03-14 |
| JP2024023308A (en) | 2024-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107109190B (en) | Sealing agent for electronic device and method for manufacturing electronic device | |
| CN108886849B (en) | Sealing agent for organic EL display element and method for producing sealing agent for organic EL display element | |
| CN109076661B (en) | Sealing agent for organic EL display element | |
| JP7457686B2 (en) | Encapsulant for organic EL display elements | |
| CN111567143B (en) | Electronic device sealing agent and organic EL display element sealing agent | |
| JP2022027778A (en) | Organic el display element sealing agent | |
| CN110731127B (en) | Sealing agent for organic EL display element | |
| CN111837457A (en) | Sealing agent for organic EL display element | |
| CN111480392B (en) | Electronic device sealing agent and organic EL display element sealing agent | |
| CN108781490B (en) | Sealing agent for organic EL display element | |
| CN110169201B (en) | Sealing agent for organic EL display element | |
| CN110603899B (en) | Sealing agent for organic EL display element | |
| CN112074957A (en) | Sealing agent for organic EL display element | |
| CN111937493A (en) | Sealing agent for organic EL display element and top emission type organic EL display element | |
| CN111972046A (en) | Sealing agent for organic EL display element | |
| CN112955488A (en) | Curable resin composition, cured product, and organic EL display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |