WO2013027389A1 - シート状エポキシ樹脂組成物、及びこれを含む封止用シート - Google Patents
シート状エポキシ樹脂組成物、及びこれを含む封止用シート Download PDFInfo
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- WO2013027389A1 WO2013027389A1 PCT/JP2012/005230 JP2012005230W WO2013027389A1 WO 2013027389 A1 WO2013027389 A1 WO 2013027389A1 JP 2012005230 W JP2012005230 W JP 2012005230W WO 2013027389 A1 WO2013027389 A1 WO 2013027389A1
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- WIPO (PCT)
- Prior art keywords
- sheet
- epoxy resin
- resin composition
- organic
- component
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 303
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 303
- 239000000203 mixture Substances 0.000 title claims abstract description 245
- 238000007789 sealing Methods 0.000 title claims description 80
- 238000003860 storage Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims description 62
- 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 claims description 39
- 239000004593 Epoxy Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 22
- 125000003700 epoxy group Chemical group 0.000 claims description 22
- 229930185605 Bisphenol Natural products 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 abstract description 16
- 230000003287 optical effect Effects 0.000 abstract description 10
- 238000010348 incorporation Methods 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- 238000001723 curing Methods 0.000 description 45
- 239000000463 material Substances 0.000 description 29
- 239000011521 glass Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 21
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- 239000011248 coating agent Substances 0.000 description 17
- 230000035699 permeability Effects 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 15
- 239000002585 base Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- -1 imidazole compound Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 C(*c1ccc(*c(cc2)ccc2OCC2OC2)cc1)C1OC1 Chemical compound C(*c1ccc(*c(cc2)ccc2OCC2OC2)cc1)C1OC1 0.000 description 1
- SQUNKLNGFIILTR-UHFFFAOYSA-N C1(CCCCC1)CO[Si](OC)(OC)CC Chemical compound C1(CCCCC1)CO[Si](OC)(OC)CC SQUNKLNGFIILTR-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 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 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JBYYGVMOBTYNOM-UHFFFAOYSA-N trimethoxy-[3-(4-methylpiperazin-1-yl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCN1CCN(C)CC1 JBYYGVMOBTYNOM-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a sheet-like epoxy resin composition, a sealing sheet containing the same, and the like.
- the present invention relates to a sheet-like epoxy resin composition and a sealing sheet suitable for optical devices such as organic EL displays.
- organic EL elements are expected to be applied to lighting devices and next-generation displays because of their low power consumption, high viewing angle, and excellent polarization characteristics.
- the organic EL element has a problem that it is easily degraded by moisture and oxygen in the atmosphere. Therefore, the organic EL element is used after being sealed with a sealing member, but a sealing material for producing a sealing member with lower moisture permeability is desired.
- a composition containing an epoxy resin containing a fluorene skeleton, a curing agent, a curing accelerator, a coupling agent and the like has been proposed (for example, see Patent Document 1).
- the cured product of the epoxy resin composition containing a fluorene skeleton has high moisture resistance, and can effectively suppress deterioration of the organic EL element.
- a sealing sheet obtained from a composition containing a low molecular weight epoxy resin, a high molecular weight epoxy resin, a latent imidazole compound and a silane coupling agent has also been proposed (see, for example, Patent Documents 2 and 3).
- the device can be sealed (surface-sealed) simply by thermocompression-transferring the epoxy resin composition to the device and transferring the epoxy resin.
- JP-A-2005-41925 JP 2006-179318 A Japanese Patent Application Laid-Open No. 2007-112956
- the present invention has been made in view of such circumstances, and it is difficult for air to enter particularly the central portion of the sheet during thermocompression bonding, the cured product is highly transparent, and has excellent adhesion to optical elements and the like. It aims at providing a sheet-like resin composition.
- the inventors of the present invention have a sheet-like epoxy resin composition in which the storage elastic modulus at 50 ° C. and the storage elastic modulus at 80 ° C. satisfy a predetermined relationship, so It has been found that air can be prevented from entering between the epoxy resin composition and the element. Furthermore, by setting the storage elastic modulus at 80 ° C. of the sheet-like epoxy resin composition to a specific range, even if bubbles are generated in the sheet-like epoxy resin composition, the aggregation of the bubbles can be suppressed, and the sheet and element It has been found that the transparency reduction at the interface and the interface peeling can be suppressed.
- the sheet-like epoxy resin composition in which the storage elastic modulus G ′ (80) satisfies the relationship of G ′ (50) / G ′ (80) ⁇ 11 and G ′ (80) is 2500 to 5 ⁇ 10 5 Pa object.
- the epoxy resin oligomer of the component (A) contains, in one molecule, a bisphenol F-type repeating structural unit in which X in the general formula (1) is a methylene group, and X in the general formula (1). Includes a bisphenol A-type repeating structural unit in which isopropylidene group is included, and the number of the bisphenol A-type repeating structural unit (A) and the number of the bisphenol F-type repeating structural units (F ), The number (F) of bisfer F-type repeating structural units contained in one molecule of the oligomer is 50% or more, and the sheet-like epoxy resin composition according to [8].
- the manufacturing method of a sheet-like epoxy resin composition which has the process of apply
- a sealing sheet comprising a layer made of the sheet-like epoxy resin composition according to any one of [1] to [9].
- the sealing sheet according to [11] having a protective film on at least one surface of the layer made of the sheet-like epoxy resin composition.
- An organic EL element surface sealing material comprising the sealing sheet according to [11] or [12].
- thermocompression bonding between the element or the like and the sheet-like epoxy resin composition air hardly enters these interfaces. Moreover, even if air gets in to some extent or bubbles are generated inside, these hardly aggregate.
- the sheet-like epoxy resin composition of the present invention contains at least (A) a high molecular weight epoxy resin and (B) a curing accelerator. In the sheet-like epoxy resin composition, if necessary, (C) a low molecular weight epoxy resin, (D) an epoxy group or a silane coupling agent having a functional group capable of reacting with an epoxy group, (E) a solvent, and Other ingredients are included.
- the sheet-like epoxy resin composition of the present invention is preferably thermosetting.
- the curing accelerator of the thermosetting composition is less likely to be decomposed during curing as compared with the curing accelerator of the photocurable composition. In addition, the decomposition product of the thermosetting curing accelerator hardly degrades the optical element, and the transparency of the cured product of the composition is hardly impaired.
- the storage elastic modulus G ′ (50) at 50 ° C. and the storage elastic modulus G ′ (80) at 80 ° C. are G ′ (50) / G ′ (80) ⁇ 11.
- the sheet-like epoxy resin composition preferably satisfies G ′ (50) / G ′ (80) ⁇ 8, and preferably satisfies G ′ (50) / G ′ (80) ⁇ 5.
- thermocompression bonding of the sheet-like epoxy resin composition is performed according to the following procedure. 1) A sheet-like epoxy resin composition is thermocompression bonded to a heat-bonded material heated to 50 to 100 ° C. 2) Hold these at a temperature of 80 ° C. to 100 ° C. for a certain time to completely cure the sheet-like epoxy resin composition.
- the sheet-like epoxy resin composition is brought into contact with the heat-bonded material in order from the end side during thermocompression bonding. Therefore, the temperature of the sheet-like epoxy resin composition gradually increases. Generally, the temperature of the sheet-like epoxy resin composition at the initial stage of thermocompression bonding is about 50 ° C., and the temperature of the sheet-like epoxy resin composition at the end of thermocompression bonding is about 80 ° C. 1) If the storage elastic modulus of the sheet-like epoxy resin composition is greatly reduced during thermocompression bonding, the sheet-like epoxy resin composition becomes excessively soft. And it becomes easy for air to enter between a to-be-heat-bonded material and a sheet-like epoxy resin composition.
- the storage elastic modulus of the sheet-like epoxy resin composition changes during thermocompression bonding of the sheet-like epoxy resin composition, that is, from the start of thermocompression bonding (50 ° C) to the end of thermocompression bonding (80 ° C). It is hard to do. Therefore, it is difficult for air to enter the interface between the sheet-shaped epoxy resin composition and the heat-bonded material, and it is difficult for air bubbles to be generated at the interface between the sheet-shaped epoxy resin composition and the heat-bonded material.
- the content ratio (mass%) of (A) high molecular weight epoxy resin is increased with respect to all components of the sheet-like epoxy resin composition.
- a method for increasing the content ratio of the high-viscosity epoxy resin is provided.
- the high molecular weight epoxy resin has less temperature dependence of the storage elastic modulus than the low molecular weight resin component. Therefore, when the content ratio of the (A) high molecular weight epoxy resin with respect to all the components of the epoxy resin composition increases, the value of G ′ (50) / G ′ (80) decreases.
- the storage elastic modulus G ′ (80) at 80 ° C. of the sheet-like epoxy resin composition of the present invention is 2500 to 5 ⁇ 10 5 Pa, preferably 5 ⁇ 10 3 to 2 ⁇ 10 5 Pa.
- the low molecular weight component or the solvent volatilizes due to heating during thermocompression bonding, and bubbles may be generated in the sheet-like epoxy resin composition.
- the storage elastic modulus G ′ (80) at a relatively high temperature (80 ° C.) is 2500 Pa or higher; that is, since the bubbles are relatively high, the generated bubbles are difficult to move in the composition and the bubbles are difficult to aggregate.
- a method for increasing the storage elastic modulus G ′ (80) at 80 ° C. there is a method for increasing the content ratio (% by mass) of a resin having a small epoxy equivalent to all components of the sheet-like epoxy resin composition.
- the content ratio of the resin having a small epoxy equivalent is increased, the crosslinking density in the sheet-like epoxy resin composition is increased, and the storage elastic modulus at 80 ° C. is increased.
- the storage elastic moduli G ′ (50) and G ′ (80) are measured with a rheometer on a sheet-like epoxy resin composition having a film thickness of 250 to 300 ⁇ m, a measurement frequency: 1 Hz, a heating rate: 4 ° C./min, and a measurement temperature. Range: Value measured at 40 to 150 ° C.
- a rheometer is a rheometer manufactured by Haake (RS150 type).
- the (A) high molecular weight epoxy resin referred to in the present invention is an epoxy resin having a weight average molecular weight of 2 ⁇ 10 3 to 1 ⁇ 10 5 , and the weight average molecular weight is preferably 3 ⁇ 10 3 to 8 ⁇ 10 4 , more preferably 4 ⁇ 10 3 to 6 ⁇ 10 4 .
- the weight average molecular weight is measured under the following conditions by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- an epoxy resin having a weight average molecular weight within the above range has a high viscosity. Therefore, when (A) high molecular weight epoxy resin is contained in the sheet-like epoxy resin composition, the shape stability of the sheet is increased. Further, (A) the high molecular weight epoxy resin has a relatively low temperature dependency of the storage elastic modulus. Therefore, when the sheet-like epoxy resin composition contains a predetermined amount or more of (A) a high molecular weight epoxy resin, the aforementioned G ′ (50) / G ′ (80) becomes a desired range.
- the epoxy equivalent of the high molecular weight epoxy resin is preferably 500 to 1 ⁇ 10 4 g / eq, and preferably 600 to 9000 g / eq in consideration of the crosslink density of the sheet-like epoxy resin composition. Is more preferable.
- the high molecular weight epoxy resin is preferably a resin containing a bisphenol skeleton in the main chain from the viewpoint of reducing the moisture permeability of the sheet.
- a resin containing bisphenol and epichlorohydrin as monomer components is preferable, and an oligomer thereof is more preferable.
- all of the monomer components constituting the high molecular weight epoxy resin may be bisphenol and epichlorohydrin; some of the monomer components constituting the epoxy resin are other than bisphenol or epichlorohydrin It may be a component (comonomer component).
- the comonomer component include dihydric or higher polyhydric alcohols (for example, divalent phenol and glycol).
- Preferred examples of the high molecular weight epoxy resin include a resin having a repeating structural unit represented by the following general formula (1).
- X represents a single bond, a methylene group, an isopropylidene group, —S— or —SO 2 —.
- the structural unit in which X is a methylene group is a bisphenol F type structural unit; the structural unit in which X is an isopropylidene group is a bisphenol A type structural unit.
- n is the repeating number of the structural unit represented by the general formula (1), and is an integer of 2 or more.
- P is the number of substitutions of the substituent R 1 and is an integer of 0 to 4. From the viewpoint of heat resistance and low moisture permeability, P is preferably 0.
- Each R 1 is independently an alkyl group having 1 to 5 carbon atoms, preferably a methyl group.
- the oligomer which is a high molecular weight epoxy resin includes a “bisphenol F-type repeating structural unit” in which X in the general formula (1) is a methylene group, and X in the general formula (1) is an isopropylidene group. It is preferable that both of certain “bisphenol A-type repeating structural units” are included.
- the oligomer contains a bisphenol A-type repeating structural unit, the viscosity of the sheet-like epoxy resin composition increases.
- the oligomer contains a bisphenol F-type repeating structural unit, the steric hindrance of the oligomer is reduced. Therefore, a plurality of phenylene groups are easily oriented, and the moisture permeability of the cured product of the sheet-like epoxy resin composition is lowered.
- the ratio of the number (F) of “F-type repeating structural units”; ⁇ (F / (A + F)) ⁇ 100 ⁇ is preferably 50% or more, and more preferably 55% or more. If many “bisphenol F-type repeating structural units” are contained, the moisture permeability of the cured product of the sheet-like epoxy resin composition will be sufficiently low.
- the content of the (A) high molecular weight epoxy resin is 100 to 2000 with respect to a total of 100 parts by mass of the later-described (B) curing accelerator, (C) the low molecular weight epoxy resin, and (D) the silane coupling agent.
- the amount is preferably part by mass, more preferably 210 to 2000 parts by mass, and still more preferably 250 to 1200 parts by mass.
- the above-described G ′ (50) / G ′ (80) is in a desired range.
- the content ratio of the (A) high molecular weight epoxy resin is too high, the fluidity of the composition at the time of thermocompression bonding to the heat-bonded material is lowered. Therefore, a gap is easily generated between the heat-bonded material and the sheet-like epoxy resin composition.
- the content ratio of the (A) high molecular weight epoxy resin is too low, the shape-retaining property of the sheet-like epoxy resin composition is lowered, and the moisture resistance of the cured product is also lowered.
- the content of (A) the high molecular weight epoxy resin is based on 100 parts by mass of the (C) low molecular weight epoxy resin. 100 to 1500 parts by mass, and more preferably 120 to 1200 parts by mass.
- (A) When the said content ratio of a high molecular weight epoxy resin is 1500 mass parts or less, the fluidity
- the content ratio of the (A) high molecular weight epoxy resin is 100 parts by mass or more, the shape stability of the sheet-like epoxy resin composition is likely to increase. Furthermore, the moisture permeability of the cured product is sufficiently low.
- the curing accelerator contained in the sheet-like epoxy resin composition of the present invention has a function of starting the curing of the epoxy resin and promoting the curing.
- the curing accelerator include imidazole compounds and amine compounds.
- imidazole compounds include 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole and the like; examples of amine compounds include trisdimethylaminomethylphenol and the like.
- the curing accelerator may be a Lewis base compound.
- the curing accelerator is preferably a thermosetting curing accelerator. Thermosetting curing accelerators are unlikely to degrade optical elements and the like. Furthermore, it is difficult to generate a decomposition product at the time of curing, which may impair the transparency of the cured product.
- the curing accelerator preferably has a melting point of 50 ° C. or lower.
- a hardening accelerator is a solid state at the time of thermocompression bonding, it is not fully disperse
- the melting point of the curing accelerator is more preferably 50 ° C. or lower, and further preferably 45 ° C. or lower.
- Examples of the (B) curing accelerator having a melting point of 50 ° C. or lower include 1,2-dimethylimidazole, trisdimethylaminomethylphenol, 2-ethyl-4-methylimidazole and the like.
- the molecular weight of the curing accelerator is preferably 80 to 800, more preferably 100 to 500, and still more preferably 120 to 250.
- the molecular weight of the curing accelerator is less than 80, the volatility becomes high, and air bubbles may be generated in the sheet-like epoxy resin composition during thermocompression bonding of the sheet-like epoxy resin composition.
- the molecular weight is over 800, the fluidity of the sheet-like epoxy resin composition may be reduced when the sheet-like epoxy resin composition is thermocompression-bonded, and further curing in the sheet-like epoxy resin composition. The diffusibility of the accelerator is lowered, and it becomes difficult to obtain sufficient curability.
- the content of (B) curing accelerator is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) high molecular weight epoxy resin and (C) low molecular weight epoxy resin described later. Is preferably 0.3 to 8 parts by mass, and more preferably 0.5 to 6 parts by mass.
- (B) The storage stability of a sheet-like epoxy resin composition increases that the said content of a hardening accelerator is 10 mass parts or less.
- hardenability of a sheet-like epoxy resin composition increases that the said content of (B) hardening accelerator is 0.3 mass part or more.
- the sheet-like epoxy resin composition preferably contains (C) a low molecular weight epoxy resin.
- the low molecular weight epoxy resin is an epoxy resin having a weight average molecular weight of 100 to 1200, and the weight average molecular weight is preferably 200 to 1100. The weight average molecular weight is measured in the same manner as described above. When the weight average molecular weight is in the above range (C), the fluidity of the sheet-like epoxy resin composition is sufficiently enhanced when the sheet-like epoxy resin composition is thermocompression-bonded, and the sheet-like epoxy resin composition for the heat-bonded material. Adhesion of objects is sufficiently enhanced.
- the epoxy equivalent of the low molecular weight epoxy resin is preferably 80 to 300 g / eq, and more preferably 100 to 200 g / eq.
- (C) low molecular weight epoxy resin having an epoxy equivalent in the above range is included, the amount of hydrogen bonds in the sheet-like epoxy resin composition increases, and a storage elastic modulus G ′ (80) at 80 ° C. is desired. It becomes the range.
- the low molecular weight epoxy resin is preferably a phenol type epoxy resin, more preferably a divalent or higher valent phenol type epoxy compound, or an oligomer containing a phenol derivative and epichlorohydrin as monomer components. preferable.
- Examples of the bivalent or higher phenol type epoxy compound include a bisphenol type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, and the like.
- Examples of the bisphenol type epoxy compound include a compound represented by the general formula (2).
- X, R 1 and p in the following general formula (2) may be the same as X, R 1 and P in the general formula (1).
- oligomeric phenol derivatives containing a phenol derivative and epichlorohydrin as monomer components include bisphenol, hydrogenated bisphenol, phenol novolak, cresol novolak, and the like.
- the low molecular weight epoxy resin include a bisphenol type epoxy compound or an oligomer having bisphenol and epichlorohydrin as monomer components.
- the low molecular weight epoxy resin is more preferably an oligomer having a repeating number n of 2 to 4 in the general formula (1). Such an oligomer has a high affinity with (A) a high molecular weight epoxy resin.
- the repeating structural unit contained in (C) the low molecular weight epoxy resin may be the same as or different from the repeating structural unit contained in the (A) high molecular weight epoxy resin.
- the content of the low molecular weight epoxy resin is 1 to 100 parts by mass with respect to 100 parts by mass in total of (A) high molecular weight epoxy resin, (B) curing accelerator, and (D) silane coupling agent. Preferably, the amount is 5 to 50 parts by mass.
- the content ratio of the low molecular weight epoxy resin is within the above range, the fluidity of the composition during thermocompression bonding of the sheet-like epoxy resin composition is sufficiently enhanced. Furthermore, the sheet-like epoxy resin composition is sufficiently cured.
- the sheet-like epoxy resin composition of the present invention includes 1) a silane coupling agent having an epoxy group, or 2) a reaction with an epoxy group. Silane coupling agents with possible functional groups may be included. Reacting with an epoxy group means an addition reaction with an epoxy group. For example, when a silane coupling agent is contained in the sheet-shaped epoxy resin composition for sealing an organic EL element, the adhesion between the sheet-shaped epoxy resin composition and the substrate of the organic EL element is enhanced.
- the silane coupling agent having an epoxy group or having a functional group capable of reacting with the epoxy group reacts with the epoxy resin in the sheet-like epoxy resin composition. Therefore, it is also preferable from the viewpoint that the low molecular weight component hardly remains in the cured product of the sheet-like epoxy composition.
- a silane coupling agent having an epoxy group is a silane coupling agent having an epoxy group such as a glycidyl group. Examples thereof include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane and the like.
- Functional groups capable of reacting with epoxy groups include amino groups such as primary amino groups and secondary amino groups; carboxyl groups and the like, and groups that can be converted into functional groups capable of reacting with epoxy groups (for example, Methacryloyl group, isocyanate group, etc.).
- silane coupling agent having a functional group capable of reacting with such an epoxy group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- ( 1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane or 3- (4-methylpiperazino) propyltrimethoxysilane, trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, And ⁇ -isocyanatopropyl
- the sheet-like epoxy resin composition may contain other silane coupling agents in addition to the silane coupling agent.
- silane coupling agents include vinyltriacetoxysilane and vinyltrimethoxysilane.
- One of these silane coupling agents may be included, or two or more thereof may be included.
- the molecular weight of the silane coupling agent is preferably 80 to 800. When the molecular weight of the silane coupling agent exceeds 800, the fluidity at the time of thermocompression bonding the sheet-like epoxy resin composition is not sufficient, and the adhesion may be lowered.
- the content of the silane coupling agent is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the sheet-like epoxy resin composition. More preferably, it is 3 to 10 parts by mass.
- the sheet-like epoxy resin composition of the present invention may contain a solvent for uniformly mixing the components (A) to (D).
- the solvent particularly has a function of uniformly dispersing or dissolving the high molecular weight epoxy resin.
- the solvent can be various organic solvents.
- Examples include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, Ethers such as propylene glycol or dialkyl ether; aprotic polar solvents such as N-methylpyrrolidone, dimethylimidazolidinone and dimethylformaldehyde; esters such as ethyl acetate and butyl acetate are included.
- a ketone solvent a solvent having a keto group
- methyl ethyl ketone is preferable from the viewpoint of easily dissolving a high molecular weight epoxy resin.
- the sheet-like epoxy resin composition of the present invention further includes optional components such as other resin components, fillers, modifiers, and stabilizers, as long as the effects of the invention are not significantly impaired. Also good.
- other resin components include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine series
- oligomers, silicon oligomers, polysulfide oligomers and the like may contain only 1 type and may contain multiple types.
- filler examples include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles. Multiple types of fillers may be included.
- modifiers include polymerization initiation aids, anti-aging agents, leveling agents, wettability improvers, surfactants, plasticizers, and the like. You may use these in combination of multiple types.
- stabilizer include ultraviolet absorbers, preservatives, and antibacterial agents. A plurality of modifiers may be included.
- the curing rate of the sheet-like epoxy resin composition of the present invention is preferably higher to some extent. This is to improve workability when bonding to the heat-bonded material. “Cure quickly” means, for example, curing within 120 minutes under heating conditions (80 to 100 ° C.).
- Whether the sheet-like epoxy resin composition is cured can be determined by checking with a finger whether the sheet-like epoxy resin composition is cured on a hot plate and gelled. Whether the sheet-like epoxy resin composition is cured is also determined from the conversion rate of the epoxy group.
- the conversion rate of the epoxy group can be determined from the reduction rate of the epoxy group in the IR spectrum by measuring the IR spectrum of the sheet-like epoxy resin composition before the curing reaction and after the curing reaction.
- the curability of the sheet-like epoxy resin composition can be controlled by adjusting the amount of the curing accelerator.
- the sheet-like epoxy resin composition of the present invention is produced by any method as long as the effects of the present invention are not impaired. For example, 1) a step of preparing components (A) to (E), 2) a step of dissolving components (A) to (D) in component (E) and mixing at 30 ° C. or lower, and 3) a substrate
- a sheet-like epoxy resin composition is obtained by the process of apply
- the components (A) to (E) may be mixed at one time, or after the component (A) is dissolved and mixed in the component (E), other components may be added and mixed.
- the mixing method include a method of charging these components into a flask and stirring, a method of kneading with three rolls, and the like.
- the viscosity at 25 ° C. of the mixture obtained in the step 2) is preferably 0.01 to 100 Pa ⁇ s.
- the viscosity is a value measured at 25 ° C. with an E-type viscometer (RC-500 manufactured by Toki Sangyo). The viscosity of the mixture is adjusted by the amount of the component (E).
- the coating method in step 3) is not particularly limited, and may be, for example, a method using screen printing, a dispenser, various coating rolls, or the like. Moreover, there is no restriction
- the coating thickness of the mixture is appropriately selected according to the film thickness of the target sheet-like epoxy resin composition, and for example, the film thickness of the dried sheet-like epoxy resin composition is, for example, 1 to 100 ⁇ m. Set.
- the drying temperature and drying time in the step 4) are such that (A) the high molecular weight epoxy resin and (C) the low molecular weight epoxy resin contained in the sheet resin composition are not cured, and (E) the solvent is used.
- the temperature and time can be dried and removed until the desired amount is reached.
- the drying temperature is, for example, 20 to 70 ° C.
- the drying time is, for example, about 10 minutes to 3 hours.
- an inert gas atmosphere such as a nitrogen atmosphere at 30 to 60 ° C. for about 10 minutes and then vacuum dry for about 2 hours.
- the drying method is not particularly limited, and examples thereof include hot air drying and vacuum drying.
- the sealing sheet of the present invention is a sheet containing the above-mentioned sheet-like epoxy resin composition.
- the above-mentioned sheet-like epoxy resin composition formed on the base film and the base film.
- a protective film formed on the sheet-like epoxy resin composition as necessary.
- the water content of the layer made of the sheet-like epoxy resin composition of the present invention is preferably 0.1% by mass or less, and 0.06% by mass or less from the viewpoint of suppressing the influence of moisture on the material to be sealed. It is more preferable that In particular, organic EL elements are easily degraded by moisture. Therefore, when sealing an organic EL element with the sheet
- the moisture content of the sealing sheet can be reduced, for example, by heating and drying the sealing sheet under vacuum.
- the moisture content of the sealing sheet of the present invention is measured, for example, by weighing about 0.1 g of a sample piece of the sheet, heating to 150 ° C. with a Karl Fischer moisture meter, and measuring the amount of water generated at that time. Can be obtained (solid vaporization method).
- the thickness of the layer formed of the sheet-like epoxy resin composition of the present invention is, for example, 1 to 100 ⁇ m, preferably 10 to 30 ⁇ m, more preferably 20 to 30 ⁇ m, although it depends on the type of the material to be sealed. .
- the layer made of the sheet-like epoxy resin composition of the present invention preferably has appropriate fluidity at the thermocompression bonding temperature.
- a sheet fluidized by heating is used to smoothly fill the unevenness of the element surface and eliminate the gap.
- the fluidity during thermocompression bonding is determined by the melting point.
- the melting point is a temperature at which fluidity is exhibited when a layer made of the sheet-like epoxy resin composition is heated, and is preferably 30 to 100 ° C.
- the melting point is a temperature at which the sheet (thickness: 100 ⁇ m) is pressed onto a glass plate placed on a hot plate and the sheet starts to melt.
- the melting point is less than 30 ° C.
- the thermal transfer (thermocompression bonding) or thermosetting and sealing the fluidity of the layer made of the sheet-like epoxy resin composition is too high, and dripping is likely to occur. It may be difficult to manage the film thickness of the film.
- the melting point exceeds 100 ° C.
- workability at the time of thermal transfer is deteriorated. For this reason, a gap is easily formed between the sealing sheet and the material to be sealed, or the material to be sealed (for example, an organic EL element) is adversely affected by heating.
- the melting point is 30 to 100 ° C., it is possible to suppress the formation of a gap between the layer made of the sheet-like epoxy resin composition and the element, and to obtain good adhesion.
- the sealing sheet may include a layer made of the sheet-like epoxy resin composition of the present invention, a base film, and a protective film.
- the base film and the protective film include known release films, preferably films having moisture barrier properties or gas barrier properties, and more preferably polyethylene terephthalate.
- the thickness of the base film or the protective film is, for example, about 50 ⁇ m, although it depends on the film material, from the viewpoint of following the sealing material such as an organic EL element.
- the sealing sheet of the present invention may further include a gas barrier layer as necessary.
- the gas barrier layer may be a layer that suppresses permeation of moisture or gas that deteriorates the organic EL element, such as moisture in the outside air, into the organic EL panel.
- Such a gas barrier layer may be disposed anywhere as long as the surface is not in contact with the organic EL element, but is preferably disposed between the base film and the layer made of the sheet-like epoxy resin composition of the present invention.
- the material constituting the gas barrier layer is not particularly limited. Examples of materials constituting the gas barrier layer include Al, Cr, Ni, Cu, Zn, Si, Fe, Ti, Ag, Au, and Co; oxides of these metals; nitrides of these metals; oxynitrides of these metals Etc. are included.
- the gas barrier layer may be made of one kind of metal or may be made of two or more kinds of metals.
- the gas barrier layer may be made of a resin.
- the gas barrier layer of the encapsulating sheet used for encapsulating the bottom emission type organic EL element is preferably a layer having a high light reflectance, for example, a layer made of Al, Cu or the like.
- the gas barrier layer of the sealing sheet used for sealing the top emission type organic EL element is preferably a layer having a high light transmittance, for example, a layer made of polyethylene terephthalate (PET), polycarbonate (PC) or the like. It can be.
- the thickness of the gas barrier layer may be about 100 to 3000 ⁇ m.
- a sealing sheet having a gas barrier layer can be produced by forming a gas barrier layer on a substrate film and then forming a layer made of the sheet-like epoxy resin composition of the present invention.
- the formation method of the gas barrier layer is not particularly limited, and the dry process includes various PVD methods such as vacuum deposition, sputtering, and ion plating, and the CVD method such as plasma CVD.
- the wet process includes a plating method. , Coating methods and the like are included.
- a protective film is further laminated on the layer made of the sheet-shaped resin composition.
- Lamination is preferably performed at about 60 ° C. using a laminator, for example.
- the thickness of the protective film is, for example, about 20 ⁇ m.
- FIG. 1 is a view showing a preferred example of the configuration of the sealing sheet.
- the sealing sheet 10 includes a base film 12, a layer 16 made of a sheet-like epoxy resin composition formed on the base film 12, and a sheet-like epoxy resin composition. And a protective film 18 disposed on the layer 16.
- such a sealing sheet 10 is formed by disposing the exposed layer 16 of the sheet-like epoxy resin composition after peeling off the protective film 18 so as to be in contact with the display substrate on which the organic EL element is disposed. Can be used.
- the sealing sheet of the present invention is preferably stored together with a desiccant such as silica gel in order to keep the moisture content below a certain level.
- a desiccant such as silica gel
- sealing sheet of the present invention is used as a sealing member by curing.
- the object to be sealed is not particularly limited, for example, an optical device is preferable.
- the optical device include an organic EL display including an organic EL panel, an organic EL illumination, a liquid crystal display, and an LED.
- the sealing sheet of the present invention is particularly preferably used as a sealing member for an organic EL panel.
- the sealing member is required to have transparency.
- the sealing member is required to have particularly low moisture permeability.
- the sealing sheet when the sealing sheet is subjected to thermocompression bonding, air hardly enters and air bubbles are less likely to aggregate. Therefore, it is excellent in transparency after thermosetting, and also excellent in adhesion to the organic EL element and low moisture permeability. Therefore, it is particularly effective as a sealing member for organic EL panels.
- the sheet-like epoxy resin composition of this invention can provide the sealing member of the organic EL panel of a top emission structure especially in an organic EL panel.
- the moisture permeability of the cured product of the sheet-like epoxy resin composition of the present invention is preferably 60 (g / m 2 ⁇ 24 h) or less, and more preferably 30 (g / m 2 ⁇ 24 h) or less.
- the moisture permeability is determined by measuring a cured product of a 100 ⁇ m sheet-shaped epoxy resin composition under the conditions of 60 ° C. and 90% RH according to JISZ0208.
- cured material of the sheet-like epoxy resin composition of this invention and a to-be-sealed material is 300 gf / 15mm or more.
- the adhesive force between the cured product and the material to be sealed is measured by the following method.
- a sheet-like epoxy resin composition (thickness: about 15 ⁇ m) is formed by coating and drying on the aluminum foil side of a film (product name: Alpet) obtained by bonding aluminum foil and PET.
- the surface of the sheet-like epoxy resin composition was placed on a glass substrate (JIS R3202 compliant glass, 100 mm ⁇ 25 mm ⁇ 2 mm) using a roll laminator (MCK Corporation, MRK-650Y type) at a speed of 0.
- Thermocompression bonding is performed under the conditions of 3 m / min, air cylinder pressure 0.2 MPa, and roller temperature 90 ° C. up and down heating.
- This laminate is heated in an oven at 80 ° C. for 30 minutes to cure the sheet-like epoxy resin composition.
- the laminate is cut into a width of 15 mm, and the 90 ° peel strength between the glass substrate and the sheet-like epoxy resin composition is measured with a peel tester (device name: STOROGRAPE ES, range 50 mm / min). .
- the 90 degree peeling strength is defined as the adhesive strength.
- cured material of the sheet-like epoxy resin composition of this invention is 80 degreeC or more.
- the Tg of the cured product is determined from the inflection point by measuring the linear expansion coefficient under the condition of a temperature increase rate of 5 ° C./min using TMA (TMA / SS6000 manufactured by Seiko Instruments Inc.).
- content of the solvent with respect to the resin composition whole component of the sheet-like epoxy resin composition of this invention is 50000 mass ppm or less, Preferably it is 30000 mass ppm or less.
- a solvent may affect a to-be-sealed material.
- the amount of solvent in the sheet-shaped resin composition is measured using, for example, an IR absorption spectrum measuring apparatus (FT / IR-4100 manufactured by JASCO Corporation). The method for measuring the amount of solvent will be described by taking as an example the case of containing methyl ethyl ketone (MEK) as the solvent.
- MEK methyl ethyl ketone
- a standard sample (sheet-like epoxy resin composition) whose amount of solvent is quantified in advance by gas chromatography / mass spectrometry (GC-MS) is prepared, and IR absorption spectrum measurement is performed on this standard sample.
- C C absorption peak (about 1609cm -1)
- calculates the strength ratio of the C O absorption peak of MEK (for approximately 1710 cm -1).
- C C absorption peak (about 1609cm -1) (about 1710 cm -1 ) Is calculated.
- the ratio of the peak intensity ratio of the measurement sample to the peak intensity ratio of the standard sample is obtained, and the amount of solvent contained in the measurement sample is calculated.
- the organic EL panel includes a substrate (display substrate) on which an organic EL element is disposed; a counter substrate paired with the display substrate; a seal interposed between the display substrate and the counter substrate and sealing the organic EL element Member.
- the sealing member filled in the space formed between the organic EL element and the sealing substrate is referred to as a surface sealing type organic EL panel.
- the sheet-like epoxy resin composition of the present invention is particularly suitable for producing a surface sealing type sealing member of an organic EL panel having a top emission structure.
- FIG. 2 is a cross-sectional view schematically showing a surface-sealing type organic EL panel having a top emission structure.
- the organic EL panel 20 includes a display substrate 22, an organic EL element 24, and a counter substrate (transparent substrate) 26 stacked in this order.
- a sealing member 28 is filled between the substrate 26 and the substrate.
- the seal member 28 in FIG. 2 is a cured product of the above-described sheet-like epoxy resin composition of the present invention.
- the display substrate 22 and the counter substrate 26 are usually glass substrates or resin films, and at least one of the display substrate 22 and the counter substrate 26 (here, the counter substrate 26) is a transparent glass substrate or a transparent resin film. is there.
- transparent resin films include aromatic polyester resins such as polyethylene terephthalate.
- the organic EL element 24 has a cathode reflective electrode layer 30 (made of aluminum, silver, etc.), an organic EL layer 32, and an anode transparent electrode layer 34 (made of ITO, IZO, etc.) laminated from the display substrate 22 side.
- the cathode reflective electrode layer 30, the organic EL layer 32, and the anode transparent electrode layer 34 may be formed by vacuum deposition, sputtering, or the like.
- the organic EL panel using the cured product of the sheet-like epoxy resin composition of the present invention as a sealing member is produced by an arbitrary method.
- the organic EL panel 20 is manufactured by thermally bonding the sheet-like epoxy resin composition of the present invention to a display substrate; Specifically, 1) a step of obtaining a laminate of the display substrate 22 on which the organic EL element 24 is disposed, the sheet-like epoxy resin composition of the present invention, and the counter substrate (transparent substrate) 26, and 2) the obtained laminate. It is manufactured through a step of thermocompression-bonding the sheet of the body, and 3) a step of curing the thermocompression-bonded sheet. Each step may be performed according to a known method.
- step 1) after placing (or transferring) the sheet-like epoxy resin composition on the display substrate 22 on which the organic EL element 24 is arranged; the display substrate 22 on which the sheet is placed (or transferred).
- a laminated body may be obtained by superposing a pair of opposing substrates (transparent substrates) 26 on the substrate (method (i)).
- the other protective film is peeled off and transferred.
- the sheet-like epoxy resin composition having no protective film may be directly placed on the organic EL element by a roll laminator or the like.
- the sheet is subjected to thermocompression bonding, for example, at 50 to 110 ° C. using a vacuum laminator device, so that the organic EL element and the sheet are thermocompression bonded, and the display substrate 22 and the counter substrate 26 are bonded.
- thermocompression bonding for example, at 50 to 110 ° C. using a vacuum laminator device, so that the organic EL element and the sheet are thermocompression bonded, and the display substrate 22 and the counter substrate 26 are bonded.
- the organic EL element side is preferably heated to 50 to 110 ° C. in advance, and the organic EL element and the sheet-like epoxy resin composition are bonded together.
- step 3 the sheet is completely cured at a curing temperature of 80 to 100 ° C., for example.
- Heat curing is preferably performed at a temperature of 80 to 100 ° C. for about 0.1 to 2 hours.
- the temperature at the time of heat-curing shall be 100 degrees C or less in order not to give a damage to an organic EL element.
- Silane coupling agent KBM-403 (3-glycidoxypropyltrimethoxysilane molecular weight 236) (manufactured by Shin-Etsu Chemical Co., Ltd.)
- Example 1 0.35 parts by mass of jER1001, 0.3 part by mass of jER1010, and 0.35 parts by mass of jER154 were added to the flask, and 2 parts by mass of methyl ethyl ketone was added thereto, followed by stirring and dissolving at room temperature. To this solution, 0.04 parts by weight of KBM-403 and 0.06 parts by weight of 1,2-DMZ were added and stirred at room temperature to prepare an epoxy resin composition varnish.
- the prepared varnish was applied on a PET film (Purex A53, Teijin DuPont Films, Inc., 38 ⁇ m), which had been subjected to mold release using a coating machine, so that the dry thickness was about 20 ⁇ m. And dried for 2 hours to obtain a solid sheet-like epoxy resin composition at room temperature (about 25 ° C.). Furthermore, a PET film (Purex A31 manufactured by Teijin DuPont Films, Ltd.) subjected to release treatment as a protective film was thermocompression bonded onto the sheet-like epoxy resin composition to obtain a sealing sheet. In addition, a protective film is peeled off suitably and the sheet-like epoxy resin composition surface is exposed and used.
- Examples 2 to 9 and Comparative Examples 1 to 5 Sealing in which a varnish of an epoxy resin composition was prepared in the same manner as in Example 1 with a composition ratio (mass ratio) as shown in Table 1, coated and dried to form a sheet-like epoxy resin composition A sheet was obtained.
- Adhesive strength The above varnish was applied to the aluminum surface of a film (trade name Alpet; manufactured by Panac Co., Ltd.) obtained by laminating an aluminum foil having a thickness of 30 ⁇ m and a PET film having a thickness of 12 ⁇ m using an applicator. This is kept in an inert oven (30 ° C.) for 10 minutes, and then kept in a vacuum oven (40 ° C.) for 2 hours, and the MEK in the varnish coating film is removed by drying to form a sheet-like epoxy resin composition. A test sheet having a layer formed thereon was obtained.
- a film (trade name Alpet; manufactured by Panac Co., Ltd.) obtained by laminating an aluminum foil having a thickness of 30 ⁇ m and a PET film having a thickness of 12 ⁇ m using an applicator. This is kept in an inert oven (30 ° C.) for 10 minutes, and then kept in a vacuum oven (40 ° C.) for 2 hours, and the MEK in the varnish coating film is
- the surface of the sheet-like epoxy resin composition of this test sheet was thermocompression-bonded (roller temperature: heated up and down 90 ° C., air cylinder) to a glass substrate with a thickness of 2 mm using a roll laminator (MCK, MRK-650Y type). (Pressure 0.2 MPa, feed rate 0.3 m / min), and then heated in an oven at 80 ° C. for 30 minutes to cure the sheet-like epoxy resin composition. Subsequently, the test sheet portion was cut with a cutter to obtain a strip-shaped test piece having a width of 15 mm.
- the base film was peeled and removed from the cured product of the sheet-shaped epoxy resin composition to obtain a cured film of the sheet-shaped epoxy resin composition.
- the coating was carried out so that the film-like cured product had a thickness of 25 to 30 ⁇ m.
- the moisture permeability of the film-like cured product was measured in accordance with JIS Z0208 under a temperature and humidity condition of 60 ° C. and 90% RH. For the moisture permeability, the thickness of the film-like cured product was measured, and the value converted to 100 ⁇ m thickness was determined as the average value of three samples. In Comparative Examples 3 to 5, the moisture permeability was not evaluated.
- the curability (curing rate) of the sheet-like epoxy resin composition was calculated from the four states of IR absorption spectra. In the calculation, the state (i) was set to a curing rate of 0%, and the state (iv) was set to a curing rate of 100%.
- the oxolane ring decreases with the heat curing reaction of the epoxy resin. Therefore, the specific intensity of the characteristic absorption of the oxolane ring (about 910 cm ⁇ 1 ) was calculated with the characteristic absorption of the benzene ring (about 1609 cm ⁇ 1 ) as the internal standard in (i) to (iv).
- a slide glass (6 cm ⁇ 6 cm) was placed on a hot plate heated to 90 ° C.
- the protective film on one side of the sealing sheet was peeled off, and the sheet-like epoxy resin composition was bonded to the slide glass in order from the end side using a stick roller.
- three slide glasses were prepared by thermocompression bonding the sheet-like epoxy resin composition, and stored in a vacuum oven at 90 ° C. under ⁇ 100 kPa (gauge pressure) for 2 minutes.
- the foamed state after storage was visually observed from the glass substrate side.
- the ratio of the peeled area of the sheet-like epoxy resin composition to the area of the slide glass was determined.
- the evaluation of foaming property is that the adhesiveness is good, the case where the ratio is less than 5%, ⁇ , the case where the ratio is 5% or more and less than 30%, and the case where the ratio is 30% or more. It was.
- the dried sealing sheet is cut into a strip-shaped test piece having a length of about 40 mm and a width of about 5 mm, and the test piece is 180 degrees in a state where the sheet-like epoxy resin composition is in close contact with the heated glass plate on the hot plate. It gradually peels in the direction.
- This operation is started at a preset temperature of 35 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a new strip-shaped test piece is prepared and repeated, and the adhesive peelability of the sheet-like epoxy resin composition becomes the greatest at the time of peeling.
- the temperature was taken as the melting point. In Comparative Examples 3 to 5, the melting point was not measured.
- the sheet-like epoxy resin composition of Example 7 had a G '(80) value of 2500 or more, but was 10,000 or less. For this reason, it is considered that bubbles generated inside during the thermocompression bonding slightly aggregated and foaming occurred in the outer peripheral portion.
- the value of G ′ (80) was 10,000 or less, and G ′ (50) / G ′ (80) was larger than 8, so the sheet-like resin composition was heated.
- the pressure bonding it is considered that a part of air bubbles entered between the sheet-like epoxy resin composition and the slide glass, and some of these bubbles aggregated, so that partial foaming occurred.
- Example 3 when Example 3 is compared with Comparative Example 1 or Example 9 is compared with Comparative Example 1, the value of G ′ (50) / G ′ (80) is increased by increasing the amount of high molecular weight epoxy resin. Is suggested to decrease.
- Example 9 when Example 9 is compared with Example 1, it is suggested that the value of G ′ (80) increases by increasing the amount of epoxy resin having a small epoxy equivalent.
- the sheet-like epoxy resin composition of the present invention is less likely to enter air between the sheet-like epoxy resin composition and the device during thermocompression bonding, and is excellent in transparency of the cured product and adhesion to the device. For this reason, it can be preferably used as a sealing material in other devices such as an organic EL display and a liquid crystal display.
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Abstract
Description
[2]前記(B)硬化促進剤は、融点が50℃以下である、[1]に記載のシート状エポキシ樹脂組成物。
[3](C)重量平均分子量が100~1200のエポキシ樹脂をさらに含む、[1]または[2]に記載のシート状エポキシ樹脂組成物。
[4]前記(A)成分と前記(C)成分との合計100質量部に対する、前記(B)成分の量が0.1~10質量部である、[3]に記載のシート状エポキシ樹脂組成物。
[5]前記(C)成分のエポキシ当量が80~300g/eqである、[3]または[4]に記載のシート状エポキシ樹脂組成物。
[7]前記(A)成分の重量平均分子量が、3×103~8×104である、[1]~[6]のいずれか一項に記載のシート状エポキシ樹脂組成物。
Xは、単結合、メチレン基、イソプロピリデン基、-S-または-SO2-を表わし、
R1は、それぞれ独立して炭素数が1~5のアルキル基を表わし、
nは、2以上の繰り返し数を表わし、
Pは、0~4の整数を表わす。〕
[11]前記[1]~[9]のいずれか一項に記載のシート状エポキシ樹脂組成物からなる層を含む、封止用シート。
[12]前記シート状エポキシ樹脂組成物からなる層の少なくとも一方の面に、保護フィルムを有する、[11]に記載の封止用シート。
[13]前記[11]または[12]に記載の封止用シートを含む、有機EL素子面封止材。
[14]含水分量が0.1質量%以下である、前記[11]~[13]のいずれか一項に記載の封止用シート。
[17]前記シート状エポキシ樹脂組成物を、50~110℃に加熱した前記有機EL素子に熱圧着することを特徴とする、[16]に記載の有機ELパネルの製造方法。
[18]前記[15]に記載の有機ELパネルを具備する有機ELディスプレイ。
[19]前記[15]に記載の有機ELパネルを具備する有機EL照明。
本発明のシート状エポキシ樹脂組成物には、(A)高分子量のエポキシ樹脂と、(B)硬化促進剤とが少なくとも含まれる。シート状エポキシ樹脂組成物には、必要に応じて、(C)低分子量のエポキシ樹脂、(D)エポキシ基またはエポキシ基と反応可能な官能基を有するシランカップリング剤、(E)溶剤、及びその他の成分が含まれる。また本発明のシート状エポキシ樹脂組成物は熱硬化性であることが好ましい。熱硬化性組成物の硬化促進剤は、光硬化性組成物の硬化促進剤と比較して、硬化時に分解しにくい。また、熱硬化性の硬化促進剤の分解物は、光学素子を劣化させ難く、組成物の硬化物の透明性も損ない難い。
本発明でいう(A)高分子量のエポキシ樹脂とは、重量平均分子量が2×103~1×105であるエポキシ樹脂であり、重量平均分子量は好ましくは3×103~8×104、さらに好ましくは4×103~6×104である。上記重量平均分子量は、ポリスチレンを標準物質とするゲルパーミエーションクロマトグラフィー(GPC)により下記条件で測定する。
装置:SHODEX製、GPC-101
展開溶媒:テトラヒドロフラン
標準ポリスチレン:VARIAN製PS-1(分子量580~7,500,000)、VARIAN製PS-2(分子量580~377,400)
本発明のシート状エポキシ樹脂組成物に含まれる硬化促進剤は、エポキシ樹脂の硬化を開始させるとともに、硬化を促進させる機能を有する。硬化促進剤の例には、イミダゾール化合物やアミン化合物が含まれる。イミダゾール化合物の例には、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾールなどが含まれ;アミン化合物の例には、トリスジメチルアミノメチルフェノールなどが含まれる。(B)硬化促進剤はルイス塩基化合物であってもよい。硬化促進剤は、熱硬化性の硬化促進剤であることが好ましい。熱硬化性の硬化促進剤は、光学素子などを劣化させ難い。さらに、組成物の硬化物の透明性を損なう恐れがある分解物を硬化時に発生しにくい。
シート状エポキシ樹脂組成物には、(C)低分子量のエポキシ樹脂が含まれることが好ましい。(C)低分子量のエポキシ樹脂とは、重量平均分子量が100~1200であるエポキシ樹脂であり、重量平均分子量は好ましくは200~1100である。重量平均分子量は、前述と同様に測定する。重量平均分子量が上記範囲である(C)と、シート状エポキシ樹脂組成物を熱圧着する際の、シート状エポキシ樹脂組成物の流動性が十分に高まり、被熱圧着材に対するシート状エポキシ樹脂組成物の密着性が十分に高まる。
なお、(C)低分子量のエポキシ樹脂に含まれる繰り返し構造単位は、(A)高分子量のエポキシ樹脂に含まれる繰り返し構造単位と同じであってもよく、異なってもよい。
本発明のシート状エポキシ樹脂組成物には、1)エポキシ基を有するシランカップリング剤、または2)エポキシ基と反応可能な官能基を有するシランカップリング剤が含まれてもよい。エポキシ基と反応するとは、エポキシ基と付加反応すること等をいう。例えば、有機EL素子封止用のシート状エポキシ樹脂組成物にシランカップリング剤が含まれると、シート状エポキシ樹脂組成物と有機EL素子の基板との密着性が高まる。
本発明のシート状エポキシ樹脂組成物には、前述の(A)~(D)成分を均一に混合するための溶剤が含まれてもよい。溶剤は、特に高分子量のエポキシ樹脂を均一に分散または溶解させる機能を有する。溶剤は、各種有機溶剤でありうる。その例には、トルエン、キシレン等の芳香族溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤;エーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコ-ルモノアルキルエーテル、エチレングリコ-ルジアルキルエーテル、プロピレングリコールまたはジアルキルエーテル等のエーテル類;N-メチルピロリドン、ジメチルイミダゾリジノン、ジメチルフォルムアルデヒド等の非プロトン性極性溶剤;酢酸エチル、酢酸ブチル等のエステル類等が含まれる。特に、高分子量のエポキシ樹脂を溶解し易い点から、メチルエチルケトン等のケトン系溶剤(ケト基を有する溶剤)であることが好ましい。
本発明のシート状エポキシ樹脂組成物は、発明の効果を大きくは損なわない範囲で、その他樹脂成分、充填剤、改質剤、安定剤などの任意成分がさらに含まれてもよい。他の樹脂成分の例には、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン-ブタジエン-スチレンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコン系オリゴマー、ポリスルフィド系オリゴマー等がある。これらは1種のみが含まれてもよく、複数種が含まれてもよい。
本発明のシート状エポキシ樹脂組成物の硬化速度は、ある程度高いほうが好ましい。被熱圧着材と接着する際の作業性を高めるためである。速やかに硬化できるとは、例えば、加熱条件下(80~100℃)において、120分以内に硬化することをいう。
本発明のシート状エポキシ樹脂組成物は、本発明の効果を損なわない限り、任意の方法で製造される。例えば、1)(A)~(E)成分を準備する工程と、2)(A)~(D)成分を(E)成分に溶解させて30℃以下で混合する工程と、3)基材上に当該混合物をシート状に塗布する工程と、4)シート状に塗布された混合物を乾燥する工程によって、シート状エポキシ樹脂組成物が得られる。
本発明の封止用シートは、上述のシート状エポキシ樹脂組成物を含むシートであり、例えば基材フィルムと、該基材フィルム上に形成された、上述のシート状エポキシ樹脂組成物と、必要に応じて該シート状エポキシ樹脂組成物上に形成される保護フィルムが含まれる。
本発明の封止用シートは、硬化させることによりシール部材として用いられる。シールされる対象は特に限定されないが、例えば光デバイスが好ましい。光デバイスの例には、有機ELパネルを具備する有機ELディスプレイ、有機EL照明、液晶ディスプレイ、LEDなどが含まれる。
硬化物と被封止材との接着力は以下の方法で測定される。
アルミ箔とPETとを貼り合せたフィルム(製品名:アルペット)のアルミ箔側に、シート状エポキシ樹脂組成物(厚み約15μm)を塗工・乾燥で形成する。さらにシート状エポキシ樹脂組成物の表面を、ガラス基板(JIS R3202準拠ガラス、100mm×25mm×2mm)に、ロールラミネーター(エム・シー・ケー社製、MRK-650Y型)を用いて、速度0.3m/min、エアーシリンダー加圧圧力0.2MPa、ローラー温度90℃上下加熱の条件で熱圧着する。この積層体を、オーブンにて80℃で30分間加熱し、シート状エポキシ樹脂組成物を硬化させる。その後、積層体を幅15mmに切断し、ガラス基板とシート状エポキシ樹脂組成物との90度はく離強度を、剥離試験機(装置名:STOROGRAPH E-S、レンジ50mm/min、)にて測定する。本発明では、この90度はく離強度を、上記接着力とする。
予め、ガスクロマトグラフィ/質量分析法(GC-MS)にて溶剤量を定量した標準サンプル(シート状エポキシ樹脂組成物)を準備し、この標準サンプルに対してIR吸収スペクトル測定を行う。標準サンプルのIR吸収スペクトルから、エポキシ樹脂のC=C吸収ピーク(約1609cm-1)に対する、MEKのC=O吸収ピーク(約1710cm-1)の強度比を算出する。続いて、測定サンプル(シート状エポキシ樹脂組成物)に対してIR吸収スペクトル測定を行い、エポキシ樹脂のC=C吸収ピーク(約1609cm-1)に対するMEKのC=O吸収ピーク(約1710cm-1)の強度比を算出する。標準サンプルのピーク強度比に対する、測定サンプルのピーク強度比の割合を求め、測定サンプル中に含まれる溶剤量を算出する。
具体的には、1)有機EL素子24が配置された表示基板22、本発明のシート状エポキシ樹脂組成物、および対向基板(透明基板)26の積層体を得る工程、2)得られた積層体の前記シートを熱圧着させる工程、3)熱圧着させた前記シートを硬化させる工程、を経て製造される。各工程は、公知の方法に準じて行えばよい。
<ビスフェノールA型エポキシ樹脂>
jER1001(三菱化学社製):重量平均分子量2322、エポキシ当量500g/eq
jER1010(三菱化学社製):重量平均分子量38312、エポキシ当量5000g/eq
<ビスフェノールF型エポキシ樹脂>
jER4004(三菱化学社製):重量平均分子量5872、エポキシ当量880g/eq
jER4005(三菱化学社製):重量平均分子量7582、エポキシ当量1070g/eq
jER4010(三菱化学社製):重量平均分子量39102、エポキシ当量4400g/eq
<ビスフェノールA/ビスフェノールF型エポキシ樹脂>
jER4275(三菱化学社製):重量平均分子量58287、エポキシ当量9200g/eq、(一分子内のビスフェノールF型構造単位の個数):(一分子内のビスフェノールA型構造単位の個数)=75:25
<フェノキシ型エポキシ樹脂>
jER1256(三菱化学社製):重量平均分子量58688、エポキシ当量8500g/eq
YP-70(新日鐵化学社製):重量平均分子量60000、エポキシ当量12100g/eq
1,2-DMZ(1,2-ジメチルイミダゾール、融点37~39℃、分子量96)(四国化成社製)
2PZ-CNS-PW(1-シアノエチル-2-フェニルイミダゾリウムトリメリテイト、融点175~183℃)(四国化成工業社製)
2MAOK-PW(2,4-ジアミノ-6-[2’-メチルイミダゾリン-(1’)]-エチル-s-トリアジンイソシアヌル酸付加物(50℃で固体、分解温度260℃)(四国化成工業社製)
SP170(アデカオプトマーSP-170(光カチオン重合開始剤))(4,4-ビス{ジ(β-ヒドロキシエトキシ)フェニルスルフォニル}フェニルスルフィド-ビス-ヘキサフルオロアンチモネート、融点25℃以下)(旭電化社製)
<ビスフェノールA型/ビスフェノールF型エポキシ樹脂>
EXA835-LV(大日本インキ化学工業社製):重量平均分子量350、エポキシ当量170g/eq
<ビスフェノールF型エポキシ樹脂>
YL983U(三菱化学社製):重量平均分子量398、エポキシ当量170g/eq
jER807(三菱化学社製):重量平均分子量229、エポキシ当量175g/eq
<フェノールノボラック型エポキシ樹脂>
jER152(三菱化学社製):重量平均分子量416、エポキシ当量178g/eq
jER154(三菱化学社製):重量平均分子量1028、エポキシ当量180g/eq
KBM-403(3-グリシドキシプロピルトリメトキシシラン 分子量236)(信越化学工業社製)
MEK(メチルエチルケトン)
フラスコに、0.35質量部のjER1001と、0.3質量部のjER1010と、0.35質量部のjER154とを挿入し、これに2質量部のメチルエチルケトンを加え、室温で攪拌溶解した。この溶液に0.04質量部のKBM-403と、0.06質量部の1,2-DMZとを添加して室温で攪拌し、エポキシ樹脂組成物のワニスを調製した。
表1に示されるような組成比率(質量比)で、エポキシ樹脂組成物のワニスを、実施例1と同様に調製し、塗工・乾燥してシート状エポキシ樹脂組成物が形成された封止用シートを得た。
実施例1~9および比較例1、2のシート状エポキシ樹脂組成物の各々について、接着強度、硬化物の透湿度、硬化性、発泡性、シート状エポキシ樹脂組成物の塗工性、硬化物の透明性、シート状エポキシ組成物のポットライフ、溶融点、50℃における貯蔵弾性率G’(50)、80℃における貯蔵弾性率G’(80)を以下の方法で評価した。その結果を表1及び表2に示す。また、図3のグラフに、実施例1~9、及び比較例1~5で得られたシート状エポキシ樹脂組成物の、50℃における貯蔵弾性率G’(50)及び80℃における貯蔵弾性率G’(80)の比G’(50)/G’(80)と、G’(80)との関係を示す。
厚み30μmのアルミ箔と厚み12μmPETフィルムとをラミネートしたフィルム(商品名アルペット;パナック株式会社製)のアルミ面に、アプリケーターを用いて前述のワニスを塗工した。これを、イナートオーブン(30℃)中で10分間保持し、続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物の層が形成された試験シートを得た。
この試験シートのシート状エポキシ樹脂組成物の面を、厚み2mmのガラス基板にロールラミネーター(エム・シー・ケー社製、MRK-650Y型)で熱圧着(ローラー温度:上下90℃加熱、エアーシリンダー圧力0.2MPa、送り速度0.3m/min)した後、オーブンで80℃30分間加熱してシート状エポキシ樹脂組成物を硬化させた。
続いて、試験シート部をカッターで切断し、幅15mmの短冊状試験片とした。試験シートがガラス基板から剥離するときの90度はく離強度を、剥離試験機(東洋精機製作所社製、装置名:STOROGRAPH E-S、はく離速度50mm/min)で測定した。なお、比較例3~5については、評価を行わなかった。
基材フィルム(A53(帝人デュポンフィルム株式会社製)厚み38μm)に、前述のワニスをアプリケーターで塗工した。このフィルムをイナートオーブン(30℃)中で、10分間保持した。続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物の層が形成された封止シートを得た。この封止シートを、オーブンで80℃30分間加熱し、シート状エポキシ樹脂組成物を硬化させた。その後、基材フィルムを、シート状エポキシ樹脂組成物の硬化物から剥離除去し、シート状エポキシ樹脂組成物のフィルム状硬化物を得た。なお、当該フィルム状硬化物の厚みが、25~30μmとなるように塗工を行った。
また、フィルム状硬化物の透湿度は、JIS Z0208に準じ、温湿度条件60℃90%RHで測定した。透湿度は、フィルム状硬化物の厚みを計測し、100μm厚みに換算した値を、3枚の試料の平均値として求めた。なお、比較例3~5については、透湿度の評価を行わなかった。
基材フィルム(A53(帝人デュポンフィルム株式会社製)厚み38μm)に、前述のワニスをアプリケーターで塗工した。このフィルムをイナートオーブン(30℃)中で、10分間保持した。続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物の層が形成された封止シート得た。その後、シート状エポキシ樹脂組成物の層を、ホットプレート上で45℃前後に加熱したNaCl板に熱圧着、室温に冷却した後、基材フィルムを剥がし、NaCl板上に転写した。転写された上面に別のNaCl板を被せ、IR吸収スペクトル測定用のサンプルとした。この際、2枚のNaCl板間のスペーサーとして、厚み11μmのアルミ箔を使用した。
IR吸収スペクトル測定装置として、日本分光社製 FT/IR-4100を用い、下記の4状態のシート状エポキシ樹脂組成物について、測定を行った。
(i)NaCl板で挟みこんだ直後のシート状エポキシ樹脂組成物
(ii)オーブンで80℃30分加熱した後のシート状エポキシ樹脂組成物
(iii)(ii)終了後、さらにオーブンで80℃30分加熱した後のシート状エポキシ樹脂組成物
(iv)(iii)終了後、さらにオーブンで150℃2時間加熱した後のシート状エポキシ樹脂組成物
エポキシ樹脂の加熱硬化反応に伴って、オキソラン環が減少する。そこで、(i)~(iv)における、ベンゼン環の特性吸収(約1609cm-1)を内部標準とした、オキソラン環の特性吸収(約910cm-1)の比強度を算出した。その後、(i)から(iv)までの比強度の変化量に対する、(i)から(ii)までの比強度比の変化量の割合、及び(i)から(iv)までの比強度の変化量に対する、(i)から(iii)までの比強度の変化量の割合を算出し、これらを(ii)及び(iii)の状態における硬化率とした。なお、比較例3~5については、硬化性の評価を行わなかった。
スライドガラス(6cm×6cm)を、90℃に加熱したホットプレート上に配置した。前記封止用シートの片面の保護フィルムを剥離し、スティックローラーを用いて、シート状エポキシ樹脂組成物を端部側から順にスライドガラスに貼り合わせた。同様に、シート状エポキシ樹脂組成物を熱圧着したスライドガラスを3枚作製し、90℃の真空オーブン中、-100kPa(ゲージ圧)下で2分間保管した。この保管後の発泡状態を、ガラス基板側から目視観察した。スライドガラスの面積に対する、シート状エポキシ樹脂組成物の剥離面積の比率を求めた。
発泡性評価は、密着性が良好であり、上記比率が5%未満であるものを○、上記比率が5%以上30%未満であるものを△、上記比率が30%以上であるものを×とした。
基材フィルム(A53(帝人デュポンフィルム株式会社製)厚み38μm)に、前述のワニスを、乾燥後の厚みが約20μmになるように、アプリケーターで塗工した。このフィルムをイナートオーブン(30℃)中で、10分間保持した。続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物からなる層を形成した。
得られたシート状エポキシ樹脂組成物を目視で観察し、ハジキがないものを○、ハジキがあるものを×とした(塗工性評価)。
基材フィルム(A53(帝人デュポンフィルム株式会社製)厚み38μm)に、前述のワニスを、乾燥後の厚みが約20μmになるように、アプリケーターで塗工した。このフィルムをイナートオーブン(30℃)中で、10分間保持した。続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物からなる層を形成した。
このシート状エポキシ樹脂組成物の面を、厚み2mmのガラス基板にロールラミネーター(エム・シー・ケー社製、MRK-650Y型)で熱圧着(ローラー温度:上下90℃加熱、エアーシリンダー圧力0.2MPa、送り速度0.3m/min)した。得られたガラス基板とシート状エポキシ樹脂組成物との積層体を目視で観察し、積層体に濁りがないものを○、積層体に濁りがあるものを×とした(透明性評価)。
塗工性及び透明性の評価と同様に、基材フィルム上にシート状エポキシ樹脂組成物の層を形成した。得られたシートを、常温常圧下で10時間保存した。その後、スライドガラス(6cm×6cm)を、60℃に加熱したホットプレート上に配置した。このスライドガラスと上記シートのシート状エポキシ樹脂層側とを重ね合わせ、スティックローラーで、シート状エポキシ樹脂組成物の端部から貼り合わせた。
シート状エポキシ樹脂組成物をガラス基板上に転写できたものを○、転写できなかったものを×とした。
基材フィルム(A53(帝人デュポンフィルム株式会社製)厚み38μm)に、前述のワニスを、乾燥後厚みが約15μmとなるようにアプリケーターで塗工した。このフィルムをイナートオーブン(30℃)中で、10分間保持し、続いて真空オーブン(40℃)中で2時間保持し、ワニス塗工膜中のMEKを乾燥除去してシート状エポキシ樹脂組成物の層が形成された封止シートを得た。乾燥後の封止シートを長さ約40mm、幅約5mmの短冊状試験片に切り出し、ホットプレート上において、加熱されたガラス板にシート状エポキシ樹脂組成物を密着した状態で試験片を180度方向へ徐々に剥離していく。この操作を、ホットプレートの設定温度35℃から始め、設定温度を1℃上げる毎に短冊状試験片を新たに用意して繰り返し、剥離時にシート状エポキシ樹脂組成物の粘着剥離性が最も大きくなる温度を溶融点とした。なお、比較例3~5については、溶融点の測定を行わなかった。
封止シート上のシート状エポキシ樹脂組成物をホットプレート45℃で複数層を熱圧着で積層し、膜厚250~300μmに調整し、Haake社製レオメーター(RS150型)を用い、測定周波数:1Hz、昇温速度:4℃/分、測定温度範囲:40~150℃で測定を行い、50℃における貯蔵弾性率G’(50)、及び80℃における貯蔵弾性率G’(80)の値を得た。
また比較例2~5は、G’(80)の値が2500以下であり、さらにG’(50)/G’(80)が11を大幅に超える。そのため、シート状樹脂組成物をスライドガラスに熱圧着する間に、シート状樹脂組成物を熱圧着する際に、シート状エポキシ樹脂組成物とスライドガラスとの間に空気が多量に入り込み、さらにこれらの気泡が凝集したため、全体に発泡が生じたと考えられる。
12 基材フィルム
16 シート状エポキシ樹脂組成物からなる層
18 保護フィルム
20 有機ELパネル
22 表示基板
24 有機EL素子
26 対向基板(透明基板)
28 シール部材
30 カソード反射電極層
32 有機EL層
34 アノード透明電極層
Claims (19)
- (A)重量平均分子量が2×103~1×105であるエポキシ樹脂と、
(B)硬化促進剤と、を含み、50℃における貯蔵弾性率G’(50)と80℃における貯蔵弾性率G’(80)がG’(50)/G’(80)<11の関係を満たし、かつG’(80)が2500~5×105Paである、シート状エポキシ樹脂組成物。 - 前記(B)硬化促進剤は、融点が50℃以下である、請求項1に記載のシート状エポキシ樹脂組成物。
- (C)重量平均分子量が100~1200のエポキシ樹脂をさらに含む、請求項1に記載のシート状エポキシ樹脂組成物。
- 前記(A)成分と前記(C)成分との合計100質量部に対する、前記(B)成分の量が0.1~10質量部である、請求項3に記載のシート状エポキシ樹脂組成物。
- 前記(C)成分のエポキシ当量が80~300g/eqである、請求項3に記載のシート状エポキシ樹脂組成物。
- (D)エポキシ基、またはエポキシ基と反応可能な官能基を有するシランカップリング剤をさらに含み、
前記(B)成分、(C)成分、及び(D)成分の合計100質量部に対して、前記(A)成分を100~2000質量部含有する、請求項3に記載のシート状エポキシ樹脂組成物。 - 前記(A)成分の重量平均分子量が、3×103~8×104である、請求項1に記載のシート状エポキシ樹脂組成物。
- 前記(A)成分のエポキシ樹脂のオリゴマーは、一分子中に、前記一般式(1)におけるXがメチレン基であるビスフェノールF型の繰り返し構造単位、及び前記一般式(1)におけるXがイソプロピリデン基であるビスフェノールA型の繰り返し構造単位を含み、
前記オリゴマー一分子中に含まれる前記ビスフェノールA型の繰り返し構造単位の個数(A)及び前記ビスフェノールF型の繰り返し構造単位の個数(F)の総数に対する、前記オリゴマー一分子中に含まれるビスフェールF型の繰り返し構造単位の個数(F)の割合が、50%以上である、請求項8に記載のシート状エポキシ樹脂組成物。 - 請求項1~9のいずれか一項に記載のシート状エポキシ樹脂組成物の製造方法であって、
基材上に、前記(A)成分及び前記(B)成分を含有する組成物を塗布する工程と、
前記組成物を乾燥させる工程とを有する、シート状エポキシ樹脂組成物の製造方法。 - 請求項1~9のいずれか一項に記載のシート状エポキシ樹脂組成物からなる層を含む、封止用シート。
- 前記シート状エポキシ樹脂組成物からなる層の少なくとも一方の面に、保護フィルムを有する、請求項11に記載の封止用シート。
- 請求項11に記載の有機EL素子を面封止するための封止用シート。
- 含水分量が0.1質量%以下である、請求項11に記載の封止用シート。
- 表示基板と、
前記表示基板と対になる対向基板と、
前記表示基板上に配置された有機EL素子と、
前記表示基板と前記対向基板との間に介在し、前記有機EL素子を封止するシール部材と、を含む有機ELパネルであって、
前記シール部材は、請求項1~9のいずれか一項に記載のシート状エポキシ樹脂組成物の硬化物である、有機ELパネル。 - 請求項1~9のいずれか一項に記載のシート状エポキシ樹脂組成物を、有機EL素子に熱圧着する工程と、
前記熱圧着した前記シート状エポキシ樹脂組成物を硬化させる工程と、を含む、有機ELパネルの製造方法。 - 前記シート状エポキシ樹脂組成物を、50~110℃に加熱して前記有機EL素子に熱圧着することを特徴とする、請求項16に記載の有機ELパネルの製造方法。
- 請求項15に記載の有機ELパネルを具備する有機ELディスプレイ。
- 請求項15に記載の有機ELパネルを具備する有機EL照明。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013187394A1 (ja) * | 2012-06-15 | 2013-12-19 | 古河電気工業株式会社 | 有機エレクトロルミネッセンス素子封止用樹脂組成物、有機エレクトロルミネッセンス素子用封止フィルム、有機エレクトロルミネッセンス素子用ガスバリアフィルムおよびこれを用いた有機エレクトロルミネッセンス素子 |
JP2015096571A (ja) * | 2013-11-15 | 2015-05-21 | 日東電工株式会社 | 光硬化性樹脂組成物およびそれを用いてなる光硬化性樹脂組成物製シート |
WO2015087807A1 (ja) * | 2013-12-11 | 2015-06-18 | 積水化学工業株式会社 | 有機エレクトロルミネッセンス表示素子封止用硬化性樹脂組成物、有機エレクトロルミネッセンス表示素子封止用硬化性樹脂シート、及び、有機エレクトロルミネッセンス表示素子 |
JP2015137333A (ja) * | 2014-01-23 | 2015-07-30 | 三井化学株式会社 | シート状封止材、及びこれを含む封止用シート |
WO2015178469A1 (ja) * | 2014-05-23 | 2015-11-26 | 味の素株式会社 | 封止体の製造方法 |
JPWO2015098875A1 (ja) * | 2013-12-24 | 2017-03-23 | 株式会社ブリヂストン | 接着シート、その製造方法及び積層体 |
JP2017060927A (ja) * | 2015-09-25 | 2017-03-30 | 味の素株式会社 | 樹脂シートの製造方法 |
JP2017098263A (ja) * | 2017-01-11 | 2017-06-01 | 日本化薬株式会社 | エネルギー線硬化型樹脂組成物及びその硬化物 |
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JP6724900B2 (ja) * | 2015-03-20 | 2020-07-15 | 味の素株式会社 | 封止体の製造方法 |
JP7327402B2 (ja) * | 2018-08-03 | 2023-08-16 | 三菱ケミカル株式会社 | 積層体及びエポキシ樹脂シートの製造方法 |
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- 2012-08-21 KR KR1020147003505A patent/KR20140048252A/ko not_active Application Discontinuation
- 2012-08-21 CN CN201280040160.8A patent/CN103732658A/zh active Pending
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Cited By (11)
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WO2013187394A1 (ja) * | 2012-06-15 | 2013-12-19 | 古河電気工業株式会社 | 有機エレクトロルミネッセンス素子封止用樹脂組成物、有機エレクトロルミネッセンス素子用封止フィルム、有機エレクトロルミネッセンス素子用ガスバリアフィルムおよびこれを用いた有機エレクトロルミネッセンス素子 |
JP2014002875A (ja) * | 2012-06-15 | 2014-01-09 | Furukawa Electric Co Ltd:The | 有機エレクトロルミネッセンス素子封止用樹脂組成物、有機エレクトロルミネッセンス素子用封止フィルム、有機エレクトロルミネッセンス素子用ガスバリアフィルムおよびこれを用いた有機エレクトロルミネッセンス素子 |
US9913324B2 (en) | 2012-06-15 | 2018-03-06 | Furukawa Electric Co., Ltd. | Resin composition for sealing organic electroluminescent element, sealing film for organic electroluminescent element, gas-barrier film for organic electroluminescent element, and organic electroluminescent element using these films |
JP2015096571A (ja) * | 2013-11-15 | 2015-05-21 | 日東電工株式会社 | 光硬化性樹脂組成物およびそれを用いてなる光硬化性樹脂組成物製シート |
WO2015087807A1 (ja) * | 2013-12-11 | 2015-06-18 | 積水化学工業株式会社 | 有機エレクトロルミネッセンス表示素子封止用硬化性樹脂組成物、有機エレクトロルミネッセンス表示素子封止用硬化性樹脂シート、及び、有機エレクトロルミネッセンス表示素子 |
JPWO2015098875A1 (ja) * | 2013-12-24 | 2017-03-23 | 株式会社ブリヂストン | 接着シート、その製造方法及び積層体 |
JP2015137333A (ja) * | 2014-01-23 | 2015-07-30 | 三井化学株式会社 | シート状封止材、及びこれを含む封止用シート |
WO2015178469A1 (ja) * | 2014-05-23 | 2015-11-26 | 味の素株式会社 | 封止体の製造方法 |
JPWO2015178469A1 (ja) * | 2014-05-23 | 2017-04-20 | 味の素株式会社 | 封止体の製造方法 |
JP2017060927A (ja) * | 2015-09-25 | 2017-03-30 | 味の素株式会社 | 樹脂シートの製造方法 |
JP2017098263A (ja) * | 2017-01-11 | 2017-06-01 | 日本化薬株式会社 | エネルギー線硬化型樹脂組成物及びその硬化物 |
Also Published As
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JPWO2013027389A1 (ja) | 2015-03-05 |
CN103732658A (zh) | 2014-04-16 |
TW201311755A (zh) | 2013-03-16 |
KR20140048252A (ko) | 2014-04-23 |
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