JP4780275B2 - Organic EL element sealing material - Google Patents
Organic EL element sealing material Download PDFInfo
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- JP4780275B2 JP4780275B2 JP2004257853A JP2004257853A JP4780275B2 JP 4780275 B2 JP4780275 B2 JP 4780275B2 JP 2004257853 A JP2004257853 A JP 2004257853A JP 2004257853 A JP2004257853 A JP 2004257853A JP 4780275 B2 JP4780275 B2 JP 4780275B2
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- 239000003566 sealing material Substances 0.000 title claims description 31
- 239000011521 glass Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 29
- 239000010408 film Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 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 8
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- -1 chlorine ions Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003230 hygroscopic agent Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-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
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000945 filler Substances 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
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical class O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000011282 treatment Methods 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
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
Description
本発明は、電界の印加によって高輝度で発光する有機ＥＬ素子用の有機ＥＬ素子封止材組成物に関し、さらに詳しくは湿分もしくは水分から有機ＥＬ素子を保護するための有機ＥＬ素子封止材組成物に関する。 The present invention relates to an organic EL element sealing material composition for an organic EL element that emits light with high luminance by application of an electric field, and more specifically, an organic EL element sealing material for protecting an organic EL element from moisture or moisture. Relates to the composition.
有機ＥＬ素子は多結晶の半導体デバイスであり、低電圧で高輝度の発光を得られるため液晶のバックライトなどに使用され、また、自発光性の薄型平面表示デバイスとして期待されている。しかしながら、有機ＥＬ素子は水分に極めて弱く、金属電極と有機物ＥＬ層との界面が水分の影響ではく離してしまったり、金属が酸化して高抵抗化してしまったり、有機物自体が水分によって変質してしまったりし、このようなことから発光しなくなったり輝度が低下してしまったりという欠点がある。 An organic EL element is a polycrystalline semiconductor device and can be used for a backlight of a liquid crystal because it can emit light with high luminance at a low voltage, and is also expected as a self-luminous thin flat display device. However, the organic EL element is extremely sensitive to moisture, and the interface between the metal electrode and the organic EL layer is separated by the influence of moisture, the metal is oxidized to increase resistance, or the organic matter itself is altered by moisture. For this reason, there is a disadvantage that the light is not emitted and the luminance is lowered.
このような課題を解消するために、有機ＥＬ素子をアクリル樹脂でモールドする方法（特許文献１）、有機ＥＬ素子を気密ケース内にＰ２Ｏ５とともに入れて外気から遮断する方法（特許文献２）、有機ＥＬ素子上に金属の酸化物等の保護膜を設けた後にガラス板等を用いて気密にする方法（特許文献３）、有機ＥＬ素子上にプラズマ重合膜及び光硬化型樹脂層を設ける方法（特許文献４）、有機ＥＬ素子をフッ素化炭素からなる不活性液体中に保持する方法（特許文献５）、有機ＥＬ素子上に高分子保護膜を設けた後シリコーンオイル中に保持する方法（特許文献６）、有機ＥＬ素子上に設けられた無機酸化物等の保護膜の上にさらにポリビニルアルコールを塗布したガラス板をエポキシ樹脂で接着する方法（特許文献７）、有機ＥＬ素子を流動パラフィンやシリコーンオイル中に封じ込める方法（特許文献８）等が提案されている。また、近年では封止樹脂中に吸湿剤を添加してこれを有機ＥＬ素子上に積層して水分による影響から有機ＥＬ層を守る方法が提案されている。
しかしながら、上記従来の有機ＥＬ層の封止方法はいずれも満足できるものではなく、例えば、吸湿剤とともに気密構造に素子を封じ込めるだけでは、ダークスポットの発生、成長を抑制出来ず、また、フッ素化炭素やシリコーンオイル中に保持する方法は液体を注入する工程を経ることにより封止工程が煩雑になるだけでなく、ダークスポットの増加も完全には防げず、むしろ液体が陰極と有機層の界面に侵入して陰極のはく離を促進する問題もある。吸湿剤が樹脂に添加された場合も、吸湿により樹脂自体が膨潤し剥離等を生じてしまうことがあった。この他にも、有機ＥＬ素子への水分による悪影響を排除するため、封止層とは別に光硬化性エポキシ樹脂に酸化バリウムや酸化カルシウムなどの金属酸化物からなる吸湿剤を添加して防湿層を別途設けることも提案されている（特許文献９）。
一方、特許文献１０には、紫外線硬化型樹脂を用いてガラス基板上にＥＬ層を形成し、ＥＬ層全面を覆うように樹脂組成物を積層し非透水性ガラス基板を貼り合わせたものが開発された。しかし、特許文献１０に記載されている樹脂組成物は該樹脂に含まれる有機溶剤や紫外線による素子の劣化の問題、硬化時の応力歪みによる有機層からの陰極のはく離の問題、紫外線が届かない所で未硬化が発生する問題があり、実用性にやや劣る面があった。
また、エポキシ樹脂は成分に含まれるアミン由来の色（主に黄色、褐色）により、透明度（透過率）が低く、特許文献１０に記載されたような有機ＥＬ発光側に用いることが出来なかった。また、透明性に優れるエポキシ樹脂は一般に硬化条件が厳しく、硬化物が固いためにはく離を起こす心配があり実用されていない。さらに、アミン系硬化剤で硬化させた場合、硬化時に発生するアミン系ガスによる影響で保護膜のピンホールから有機ＥＬ素子を腐食させる問題もあった。 Moreover, the epoxy resin has low transparency (transmittance) due to the amine-derived color (mainly yellow, brown) contained in the components, and could not be used on the organic EL light emitting side as described in Patent Document 10. . In addition, epoxy resins having excellent transparency are generally not used practically because the curing conditions are severe and the cured product is hard and may cause peeling. Further, when cured with an amine-based curing agent, there is also a problem that the organic EL element is corroded from the pinhole of the protective film due to the influence of the amine-based gas generated at the time of curing.
このように有機ＥＬ素子のダークスポットによる劣化が十分に改善されず、発光特性が不安定なことは、液晶ディスプレイのバックライト等の光源としては重大な欠陥となり、また、フラットパネル・ディスプレイなどの表示素子としても望ましくない。本発明は上記従来技術の課題を解決し、有機ＥＬ素子に悪影響を及ぼすことなく、効果的な封止を行うことにより、ダークスポットの発生・成長を確実に抑制して、長期間にわたって安定な発光特性を維持することが出来る有機ＥＬ素子封止用の硬化性樹脂性組成物である有機ＥＬ素子封止材を得ることを目的とする。 The deterioration of organic EL elements due to dark spots is not sufficiently improved and the light emission characteristics are unstable, which is a serious defect for light sources such as backlights of liquid crystal displays. It is not desirable as a display element. The present invention solves the above-described problems of the prior art and effectively suppresses the occurrence and growth of dark spots by performing effective sealing without adversely affecting the organic EL element, and is stable over a long period of time. It aims at obtaining the organic EL element sealing material which is a curable resin composition for organic EL element sealing which can maintain a luminescent property.
上記の課題を解決するため本発明は、ガラスもしくはフィルム基板１上に透明電極２、正孔輸送層３、有機物ＥＬ層４及び背面電極５からなる有機ＥＬ層を形成し、有機ＥＬ素子封止材層７を積層して非透水性ガラスもしくはフィルム６と貼り合わせることにより得られる有機ＥＬ素子に使用することができる有機ＥＬ素子封止材であり、該有機ＥＬ素子封止材が、
（Ａ）分子中にグリシジル基を有する化合物：１００重量部
（Ｂ）酸無水物硬化剤：５０〜１５０重量部
を主成分とする有機ＥＬ素子封止材を見いだした。
In order to solve the above problems, the present invention forms an organic EL layer composed of a transparent electrode 2, a hole transport layer 3, an organic EL layer 4 and a back electrode 5 on a glass or film substrate 1, and seals the organic EL element. It is an organic EL element sealing material that can be used for an organic EL element obtained by laminating the material layer 7 and laminating it with the water-impermeable glass or film 6, and the organic EL element sealing material is
(A) Compound having glycidyl group in molecule: 100 parts by weight (B) Acid anhydride curing agent: An organic EL device sealing material having 50 to 150 parts by weight as a main component was found.
以下、本発明を詳細に説明する。まず、本発明で得られる有機ＥＬ素子は図１に示すようにガラスまたはフィルム基板１上にＩＴＯ等の透明電極２、正孔輸送層３、有機物ＥＬ層４及び背面電極５がこの順に積層される。また、ガラスまたはフィルム基板１上には、耐湿性を有した有機ＥＬ素子封止材層７を介しガラスや金属等の非透水性ガラスまたはフィルム基板６が固着される。 Hereinafter, the present invention will be described in detail. First, as shown in FIG. 1, the organic EL element obtained by the present invention is formed by laminating a transparent electrode 2 such as ITO, a hole transport layer 3, an organic EL layer 4 and a back electrode 5 in this order on a glass or film substrate 1. The On the glass or film substrate 1, a water-impermeable glass such as glass or metal or a film substrate 6 is fixed via an organic EL element sealing material layer 7 having moisture resistance.
さらに詳述すると、このような構成の有機ＥＬ素子は次のようにして製造される。まず、ガラスまたはフィルム基板１上に透明電極２を約０．１μｍの厚みで成膜する。透明電極２の成膜に際しては、真空蒸着及びスパッタ等による方法がある。ただし、真空蒸着による成膜は、結晶粒が成長して膜表面の平滑度を低下させることがあり、薄膜ＥＬに適用する場合には絶縁破壊や不均一発光の原因を作ることがあるため、注意を要する。一方、スパッタによる成膜は表面の平滑性がよく、その上に薄膜デバイスを積層する場合に好ましい結果が得られる。続いて、透明電極２の上部に正孔輸送層３及び有機物ＥＬ層４を０．０５μｍの厚みで順次成膜する。また有機物ＥＬ層４の上部に背面電極５を０．１〜０．３μｍの厚みで成膜する。 More specifically, the organic EL element having such a configuration is manufactured as follows. First, the transparent electrode 2 is formed on the glass or film substrate 1 with a thickness of about 0.1 μm. In forming the transparent electrode 2, there are methods such as vacuum deposition and sputtering. However, film formation by vacuum deposition may cause crystal grains to grow and reduce the smoothness of the film surface, and when applied to a thin film EL, it may cause dielectric breakdown and uneven light emission, Need attention. On the other hand, film formation by sputtering has good surface smoothness, and preferable results are obtained when a thin film device is laminated thereon. Subsequently, the hole transport layer 3 and the organic EL layer 4 are sequentially formed on the transparent electrode 2 with a thickness of 0.05 μm. Further, the back electrode 5 is formed in a thickness of 0.1 to 0.3 μm on the organic EL layer 4.
これらの素子の成膜を終えた後、ガラスまたはフィルム基板１の上部に有機ＥＬ素子封止材を約０．１ｍｍの厚みで滴下し、この有機ＥＬ素子封止材の上から非透水性ガラスまたはフィルム基板６を密着させる。有機ＥＬ素子封止材の詳細は後述する。非透水性ガラスまたはフィルム基板６の密着を終えた後、常温で養生または低温での加熱促進により有機ＥＬ素子封止材を硬化させて有機ＥＬ素子封止材層７を形成する。これにより、非透水性ガラス基板６は有機ＥＬ素子封止材層７を介してガラスまたはフィルム基板１に固着される。なお、上記の加熱促進硬化を行う場合は有機ＥＬ素子にダメージを与えないよう１００℃以下で行うことが望ましい。また、有機ＥＬ素子封止材可使時間は作業性を考慮し室温で１２０分以上であることが望ましい。 After the film formation of these elements is completed, an organic EL element sealing material is dropped on the glass or film substrate 1 to a thickness of about 0.1 mm, and the water-impermeable glass is formed on the organic EL element sealing material. Alternatively, the film substrate 6 is brought into close contact. Details of the organic EL element sealing material will be described later. After the adhesion of the water-impermeable glass or the film substrate 6 is completed, the organic EL element sealing material layer 7 is formed by curing the organic EL element sealing material at room temperature or by promoting heating at a low temperature. Thereby, the water-impermeable glass substrate 6 is fixed to the glass or film substrate 1 through the organic EL element sealing material layer 7. In addition, when performing said heat-accelerated hardening, it is desirable to carry out at 100 degrees C or less so that an organic EL element may not be damaged. In addition, the usable time of the organic EL element sealing material is preferably 120 minutes or more at room temperature in consideration of workability.
本発明において有機ＥＬ素子封止材層７に求められる物性は、透湿度が６０℃、９５％で３０ｇ／ｍ２×２４ｈｒ以下（厚み１５０μｍ）、光透過率９１％以上（４５０ｎｍ、５０μｍ）、ガラス同士のはく離接着力が１．５ＭＰａ以上及び比較的低温で硬化することが望まれる。これらの要求項目を満たすものとして、（Ａ）分子中にグリシジル基を有する化合物１００重量部、（Ｂ）酸無水物硬化剤５０〜１５０重量部、からなるエポキシ樹脂組成物であることが必要である。 The physical properties required for the organic EL element sealing material layer 7 in the present invention are: moisture permeability is 60 ° C., 95%, 30 g / m 2 × 24 hr or less (thickness 150 μm), light transmittance 91% or more (450 nm, 50 μm), It is desired that the peel adhesion between the glasses is 1.5 MPa or more and that the glass is cured at a relatively low temperature. In order to satisfy these requirements, it is necessary that the epoxy resin composition comprises (A) 100 parts by weight of a compound having a glycidyl group in the molecule and (B) 50 to 150 parts by weight of an acid anhydride curing agent. is there.
本発明の有機ＥＬ素子封止材組成物において（Ａ）分子中にグリシジル基を有する化合物は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水素化ビスフェノール型エポキシ樹脂などがあげられるが、有機ＥＬ素子用に使用するためには塩素イオン含有量の少ないもの、具体的には加水分解性塩素が５００ｐｐｍ以下であるものが好ましく、また、含有水分量が８００ｐｐｍ以下（さらに好ましくは６００ｐｐｍ以下）であることが望ましい。（Ａ）成分の具体例としては含有する塩素イオン濃度が少ないエピクロンＥＸＡ−８３５ＬＶ（大日本インキ工業株式会社製）が好ましく使用できる。 また、（Ａ）成分の粘度は１０００〜１０００００ｃＰ範囲であることが好ましい。粘度が１０００００ｃＰを越えると（Ｂ）成分との混合性、貼合せ時に問題が生じる。 Examples of the compound having a glycidyl group in the molecule (A) in the organic EL device sealing material composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, and the like. In order to use for EL devices, those having a low chloride ion content, specifically those having a hydrolyzable chlorine content of 500 ppm or less are preferable, and the water content is 800 ppm or less (more preferably 600 ppm or less). It is desirable to be. As a specific example of the component (A), Epicron EXA-835LV (manufactured by Dainippon Ink Industries, Ltd.) having a low concentration of chlorine ions can be preferably used. Moreover, it is preferable that the viscosity of (A) component is 1000-100000 cP range. When the viscosity exceeds 100,000 cP, problems arise with mixing with (B) component and bonding.
上記（Ａ）成分は水分が少ない方が好ましい。工業材料として水分を含んでいるもを使用する場合、例えば加熱・撹拌・脱泡（真空引き）が同時に行える装置を用いて、６０℃〜１００℃で数時間程度加熱撹拌脱泡を行ないうことで含有する水分量を低減させることが可能である。例えば８０℃で１時間程度加熱撹拌脱泡を行うことでの含有水分量を８００ｐｐｍ以下することが可能である。 The component (A) preferably has less moisture. When using water that contains water as an industrial material, for example, using a device that can perform heating, stirring, and defoaming (evacuation) at the same time, heating and stirring and defoaming at 60 ° C to 100 ° C for several hours It is possible to reduce the amount of water contained. For example, the water content can be reduced to 800 ppm or less by heating and defoaming at 80 ° C. for about 1 hour.
本発明に用いられる（Ｂ）酸無水物硬化剤としては、従来から公知のものが使用可能である。酸無水物硬化剤としては液状で、二重結合を含まない水素化されたタイプの脂環式酸無水物が好ましい。例えば、メチルヘキサヒドロ無水フタル酸、水素化メチルナジック酸無水物が挙げられる。また、固体でもヘキサヒドロ無水フタル酸を溶解し使用することも可能である。その他、特に高い透過率を期待しないのであれば、メチルテトラヒドロ無水フタル酸、メチルナジック酸無水物等を使用することもできる。酸無水物は単独もしくは複数の混合でも使用可能である。（Ｂ）成分の配合量は（Ａ）成分１００重量部に対して５０〜１５０重量部添加する。 As the (B) acid anhydride curing agent used in the present invention, conventionally known ones can be used. As the acid anhydride curing agent, a hydrogenated type alicyclic acid anhydride which is liquid and does not contain a double bond is preferable. For example, methyl hexahydrophthalic anhydride and hydrogenated methyl nadic acid anhydride can be mentioned. Moreover, it is also possible to dissolve and use hexahydrophthalic anhydride even in a solid state. In addition, if a particularly high transmittance is not expected, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, or the like can be used. The acid anhydride can be used alone or in combination. Component (B) is added in an amount of 50 to 150 parts by weight per 100 parts by weight of component (A).
さらに本発明の有機ＥＬ素子封止材組成物は（Ｃ）硬化促進剤を添加することができる。硬化促進剤としては４級アンモニウム塩、４級スルホニウム塩、ＤＢＵ脂肪酸塩、各種金属塩、イミダゾール、３級アミン等が挙げられる。例えば、４級アンモニウム塩としてはテトラメチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、４級スルホニウム塩としてはテトラフェニルホスホニウムブロマイド、テトラブチルホスホニウムブロマイド、ＤＢＵ脂肪酸塩としてはＤＢＵの２−エチルヘキサン酸塩等、金属塩としてはオクチル酸亜鉛、オクチル酸スズ等、イミダゾールとしては１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール等、三級アミンとしてはトリス（ジメチルアミノメチルフェノール、ベンジルジメチルアミン等が挙げられる。（Ａ）成分１００重量部に対して０〜１０重量部添加する。（Ｃ）成分の添加により有機ＥＬ素子封止材組成物の硬化温度を所望の温度にすることができる。有機ＥＬ素子封止材組成物に（Ｃ）成分は（Ｂ）成分である酸無水物硬化剤とあらかじめ混合し（Ａ）成分と混合することにより、硬化させることができる。 Furthermore, the organic EL element sealing material composition of this invention can add (C) hardening accelerator. Examples of the curing accelerator include quaternary ammonium salts, quaternary sulfonium salts, DBU fatty acid salts, various metal salts, imidazole, and tertiary amines. For example, tetramethylammonium bromide, tetrabutylammonium bromide as quaternary ammonium salt, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide as quaternary sulfonium salt, DBU 2-ethylhexanoate as DBU fatty acid salt, etc. Zinc octylate and tin octylate as salts, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole and the like as imidazole, and tris ( Examples thereof include dimethylaminomethylphenol, benzyldimethylamine, etc. (A) 0 to 10 parts by weight is added to 100 parts by weight of component (C) The curing temperature of the organic EL device sealing material composition is increased by adding component (C). To the desired temperature Rukoto can. (C) component organic EL element sealing material composition by mixing (B) pre-mixed with the acid anhydride curing agent as the component (A) component, can be cured.
（Ｂ）（Ｃ）成分は加熱、撹拌、脱泡（真空引き）などの工程処理を行なうことにより含有水分量を減少させることができる。これらの成分はその種類により水分量が大きく異なるため一概に規定できないが、例えば８０℃で２時間程度加熱撹拌脱泡を行うことで１０００ｐｐｍ以下の水分量にすることが可能である。 The component (B) and component (C) can reduce the water content by carrying out process treatments such as heating, stirring and defoaming (evacuation). These components cannot be defined unconditionally because the amount of water varies greatly depending on the type, but for example, the amount of water can be reduced to 1000 ppm or less by heating and stirring and defoaming at 80 ° C. for about 2 hours.
本発明に使用できる（Ｄ）成分のカップリング剤としては、シランカップリング剤やチタネート系カップリング剤、アルミネート系カップリング剤、ジルコネート系カップリング剤、およびこれらを混合したものが使用できるが、エポキシシラン系カップリング剤とアルミネート系カップリング剤を１：１〜２０：１（重量比）の割合で混合したものがより好ましい。カップリング剤の効果としては接着性の向上や粘度の低減がある。カップリング剤の配合量は（Ａ）成分１００重量部に対して０〜３０重量部加えることが好ましい。 As the coupling agent of component (D) that can be used in the present invention, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, and a mixture thereof can be used. More preferably, an epoxysilane coupling agent and an aluminate coupling agent are mixed at a ratio of 1: 1 to 20: 1 (weight ratio). As an effect of the coupling agent, there is an improvement in adhesion and a reduction in viscosity. The blending amount of the coupling agent is preferably 0 to 30 parts by weight per 100 parts by weight of component (A).
本発明には、さらに本発明の目的を達成可能な限り、その他の成分、例えばよう変剤、保存安定剤、可塑剤、反応性希釈剤、充填材、粘度調製剤等を添加することも可能であるが、それらの添加成分中の水分や不純物に注意する必要がある。 As long as the object of the present invention can be achieved, other components such as a modifier, a storage stabilizer, a plasticizer, a reactive diluent, a filler, a viscosity adjuster, etc. can be added to the present invention. However, it is necessary to pay attention to moisture and impurities in those added components.
上記のとおりベース層と非透水ガラスまたはフィルム基板層の接着に本発明の有機ＥＬ素子封止材組成物を使用し固着封止することにより、有機ＥＬ素子の劣化の進行を大幅に抑制することができ、長寿命化、有機ＥＬ発光側にエポキシ樹脂層があっても高輝度化を図ることができる。また、紫外線硬化型の接着剤組成物で問題となる紫外線の届かない箇所の未硬化や、大きな硬化収縮もないため、得られる有機ＥＬ素子は安定した性能を発揮する。本発明の有機ＥＬ素子封止材は二液性エポキシ樹脂として配合でき、常温で硬化させ、低温加熱により硬化促進させることができ、比較的低温の促進で十分に性能が安定する。 As described above, by using the organic EL element sealing material composition of the present invention for adhesion between the base layer and the non-permeable glass or film substrate layer, the deterioration of the organic EL element is greatly suppressed. Thus, the lifetime can be increased and the luminance can be increased even if the organic EL light emitting side has an epoxy resin layer. In addition, since there is no uncured portion where ultraviolet rays do not reach, which is a problem in the ultraviolet curable adhesive composition, and large shrinkage due to curing, the obtained organic EL device exhibits stable performance. The organic EL device sealing material of the present invention can be blended as a two-component epoxy resin, cured at room temperature, and cured by low temperature heating, and the performance is sufficiently stabilized by promoting relatively low temperatures.
以下実施例にて本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
表１に示す通り有機ＥＬ素子封止材用の各硬化性樹脂を調製し各種評価を行った。その結果を表２に記載する。なお、使用した各成分はエピクロンＥＸＡ−８３５ＬＶ：ビスフェノールＡ型及びＦ型混合エポキシ樹脂低塩素型（大日本インキ化学工業株式会社製）、エピコート８２８：ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製）、エピコート８０７：ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン株式会社製）、リカシッドＭＨ−７００：メチルヘキサヒドロ無水フタル酸（新日本理化株式会社社製）、リカシッドＴＨ：テトラヒドロ無水フタル酸（新日本理化株式会社社製）、リカシッドＨＨ：ヘキサヒドロ無水フタル酸（新日本理化株式会社社製）、１Ｂ２ＭＺ：１−ベンジル−２−メチルイミダゾール、Ｋ−６１Ｂ：トリス（ジメチルアミノメチル）フェノール・トリ（２−エチルヘキソエート）（エアープロダクツジャパン株式会社社製）、トーマイド２９６：ポリアミドアミン（富士化成工業株式会社製）、サンマイドＡ−１００イミダゾール変性アミン（三和化学工業株式会社製）、アンカミンＺ：芳香族ポリアミン（エアプロダクトジャパン株式会社製）、アンカミン２２６４：脂環式ポリアミン（エアプロダクトジャパン株式会社製）、アンカミン１７８４：脂肪族ポリアミン（エアプロダクトジャパン株式会社製）、ＫＢＭ−４０３：シランカップリング剤（信越化学工業株式会社社製）である。 As shown in Table 1, each curable resin for an organic EL device sealing material was prepared and subjected to various evaluations. The results are listed in Table 2. In addition, each component used is Epicron EXA-835LV: Bisphenol A type and F type mixed epoxy resin low chlorine type (manufactured by Dainippon Ink Chemical Co., Ltd.), Epicoat 828: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.) ), Epicoat 807: Bisphenol F-type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.), Ricacid MH-700: Methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.), Ricacid TH: Tetrahydrophthalic anhydride (Shin Nihon) Manufactured by Rika Co., Ltd.), Ricacid HH: hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.), 1B2MZ: 1-benzyl-2-methylimidazole, K-61B: tris (dimethylaminomethyl) phenol tri (2 -Ethylhexoate) -Products Japan Co., Ltd.), Tomide 296: Polyamidoamine (Fuji Kasei Kogyo Co., Ltd.), Sunmide A-100 Imidazole-modified amine (Sanwa Chemical Co., Ltd.), Ancamine Z: Aromatic polyamine (Air Product Japan) Ancamine 2264: Alicyclic polyamine (produced by Air Product Japan), Ancamine 1784: Aliphatic polyamine (produced by Air Product Japan), KBM-403: Silane coupling agent (Shin-Etsu Chemical Co., Ltd.) Company-made).
（Ａ）成分の分子中にグリシジル基を有する化合物を８０℃で２時間加熱、撹拌、脱泡を行い、水分量を８００ｐｐｍ以下に調整した。（Ｂ）成分の酸無水物硬化剤は、常温で脱泡、攪拌を３０分行い水分量を１２００ｐｐｍ以下に調整した。なお、調整後の各成分は窒素雰囲気中で乾燥剤とともに保管した。 The compound having a glycidyl group in the molecule of component (A) was heated at 80 ° C. for 2 hours, stirred and degassed to adjust the water content to 800 ppm or less. The acid anhydride curing agent (B) was defoamed at room temperature and stirred for 30 minutes to adjust the water content to 1200 ppm or less. In addition, each component after adjustment was stored with a desiccant in a nitrogen atmosphere.
評価１：透湿度測定
各硬化性樹脂を厚み１５０μｍのシート状に加工し硬化させ（硬化条件：表１参照）、６０℃×９５％の条件で透湿度を測定した。（使用機器：Ｌ８０−５０００型水蒸気透過度計／ＬＹＳＳＹ社製）表中単位はｇ／ｍ２ｘ２４ｈである。
評価２：アウトガス測定
フッ素樹脂コートした板の上に各硬化性樹脂を約２０ｍｇ計量し所定の硬化条件で硬化させ、ダブルショットパイロライザーおよびガスクロマトグラフ／質量分析計（ＧＣ／ＭＳ）を用いたダイナミックヘッドスペース法で１２０℃×１５分加熱した際に発生するアウトガス量を測定した。表中単位はｐｐｍである。
評価３：透過率測定
パネル用ガラス基板を２５ｍｍ×５０ｍｍにカットし、ガラス片が十字状になるように中央に樹脂を挟み（５０μｍ）所定の硬化条件で硬化させた。これを分光高度計で４００ｎｍの透過性を測定し、硬化性樹脂を塗布しないガラスのみのものをブランクとして、透過率を測定した。表中単位は％である。
評価４：パネル信頼性試験（ダークスポット評価）
ガラス基板上にスパッタリングにより透明電極を０．１μｍの厚みで成膜した。続いて、透明電極の上部に正孔輸送層及び有機物ＥＬ層を０．０５μｍの厚みで順次成膜した。また有機物ＥＬ層の上部に背面電極を０．２μｍの厚みで成膜する。これらの素子の成膜を終えた後、ガラス基板１の上部に各硬化性樹脂をＥＬ素子材として約０．１ｍｍの厚みで滴下し、この硬化性樹脂の上から非透水性ガラス基板を密着させた（硬化条件：表１参照）。このようにして有機ＥＬパネルを作製し、連続点灯で６０℃、９０％の環境でダークスポットの成長を観察した。１０００時間経過後の直径１００μｍ以上のダークスポットが発生したものはＤ、２０００時間経過後に直径１００μｍ以上のダークスポットが発生したものはＣ、同様に３０００時間はＢ、４０００時間経過しても直径１００μｍ以上のダークスポットが発生していないものはＡとした。これらの結果を表２に示した。
Evaluation 1: Measurement of moisture permeability Each curable resin was processed into a sheet having a thickness of 150 µm and cured (curing conditions: see Table 1), and the moisture permeability was measured at 60 ° C x 95%. (Equipment used: L80-5000 type water vapor permeability meter / manufactured by LYSSY) The unit in the table is g / m 2 × 24h.
Evaluation 2: Outgas measurement About 20 mg of each curable resin is weighed on a fluororesin-coated plate and cured under predetermined curing conditions, and dynamic using a double shot pyrolyzer and a gas chromatograph / mass spectrometer (GC / MS) The amount of outgas generated when heated at 120 ° C. for 15 minutes by the headspace method was measured. The unit in the table is ppm.
Evaluation 3: Transmittance measurement A glass substrate for panels was cut into 25 mm x 50 mm, and a resin was sandwiched in the center (50 µm) so that the glass piece had a cross shape, and cured under predetermined curing conditions. This was measured for transmittance at 400 nm with a spectrophotometer, and the transmittance was measured using only a glass without a curable resin as a blank. The unit in the table is%.
Evaluation 4: Panel reliability test (dark spot evaluation)
A transparent electrode having a thickness of 0.1 μm was formed on a glass substrate by sputtering. Subsequently, a hole transport layer and an organic EL layer were sequentially formed on the transparent electrode in a thickness of 0.05 μm. A back electrode is formed to a thickness of 0.2 μm on top of the organic EL layer. After film formation of these elements is completed, each curable resin is dropped as an EL element material on the glass substrate 1 with a thickness of about 0.1 mm, and a non-permeable glass substrate is adhered onto the curable resin. (Curing conditions: see Table 1). In this way, an organic EL panel was produced, and the growth of dark spots was observed in an environment of 60 ° C. and 90% with continuous lighting. D is a dark spot with a diameter of 100 μm or more after 1000 hours, C is a dark spot with a diameter of 100 μm or more after 2000 hours, and B is 3000 μ for 3000 hours. The case where the above dark spots were not generated was A. These results are shown in Table 2.
本発明は有機ＥＬ素子封止材料として好適に使用できる。 The present invention can be suitably used as an organic EL device sealing material.
１ガラス基板
２透明電極
３正孔輸送層
４有機物ＥＬ層
５背面電極
６非透水性ガラス基板
７有機ＥＬ素子封止材
1 glass substrate 2 transparent electrode 3 hole transport layer 4 organic EL layer 5 back electrode 6 water-impermeable glass substrate 7 organic EL element sealing material
Claims (2)
（Ａ）成分 水分が８００ｐｐｍ以下の分子中にグリシジル基を有する化合物：１００重量部
（Ｂ）成分 水分除去工程直後の水分が１２００ｐｐｍ以下のメチルヘキサヒドロ無水フタル酸：５０〜１５０重量部
（Ｃ）成分 硬化促進剤：０．１〜１０重量部 An organic EL layer composed of a transparent electrode 2, a hole transport layer 3, an organic EL layer 4 and a back electrode 5 is formed on a glass or film substrate 1, and the transparent electrode 2 and the hole transport layer are formed by an organic EL element sealing material 7. 3, an organic EL sealing material used in an organic EL element that bonds the substrate 1 and the water-impermeable glass or film 6 so as to cover the laminate of the organic EL layer 4 and the back electrode 5, (C) The organic EL element sealing material which consists of components.
(A) Component Compound having a glycidyl group in a molecule having a water content of 800 ppm or less: 100 parts by weight (B) Methylhexahydrophthalic anhydride having a water content of 1200 ppm or less immediately after the component water removal step : 50 to 150 parts by weight (C) Ingredient Curing accelerator: 0.1 to 10 parts by weight
The organic EL element sealing material according to claim 1, wherein a coupling agent is further added as a component (D) to the organic EL element sealing material.
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| JP4909581B2 (en) * | 2005-01-20 | 2012-04-04 | 三井化学株式会社 | Organic EL element sealing method |
| JP2007326915A (en) * | 2006-06-06 | 2007-12-20 | Nitto Denko Corp | Epoxy resin sheet for forming optical member |
| JP2008059868A (en) * | 2006-08-30 | 2008-03-13 | Seiko Epson Corp | Organic electroluminescent device, its manufacturing method, and electronic apparatus |
| WO2010035502A1 (en) * | 2008-09-29 | 2010-04-01 | 三井化学株式会社 | Sealant, sealing member and organic el device |
| KR102121724B1 (en) | 2009-08-05 | 2020-06-11 | 아지노모토 가부시키가이샤 | Film |
| JP5237507B1 (en) | 2011-06-23 | 2013-07-17 | 三井化学株式会社 | Surface sealant for optical semiconductor, method for producing organic EL device using the same, organic EL device, and organic EL display panel |
| WO2013118509A1 (en) * | 2012-02-10 | 2013-08-15 | 三井化学株式会社 | Surface sealing agent for organic el element, organic el device using same, and manufacturing method for same |
| JP6129154B2 (en) | 2012-02-24 | 2017-05-17 | 三井化学株式会社 | Optical device surface sealing composition, optical device surface sealing sheet, display, and display manufacturing method |
| KR102085332B1 (en) | 2012-07-26 | 2020-03-05 | 덴카 주식회사 | Resin composition |
| JP5435520B1 (en) | 2013-03-29 | 2014-03-05 | 古河電気工業株式会社 | Resin composition for sealing element for organic electronic device, resin sheet for sealing element for organic electronic device, organic electroluminescence element, and image display device |
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| JPH01167359A (en) * | 1987-12-24 | 1989-07-03 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
| JP2763388B2 (en) * | 1990-07-24 | 1998-06-11 | 三菱電機株式会社 | Crystallization prevention method |
| JPH11224771A (en) * | 1998-02-05 | 1999-08-17 | Matsushita Electric Ind Co Ltd | Organic electroluminescence element |
| JP3695226B2 (en) * | 1999-06-17 | 2005-09-14 | 住友金属鉱山株式会社 | One-part thermosetting resin composition |
| JP4475711B2 (en) * | 1999-12-09 | 2010-06-09 | ユニチカ株式会社 | Polyimide precursor solution |
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| JP4057278B2 (en) * | 2001-11-02 | 2008-03-05 | セイコーエプソン株式会社 | ORGANIC ELECTROLUMINESCENT DEVICE, ITS MANUFACTURING METHOD, AND ELECTRONIC DEVICE |
| JP2003165826A (en) * | 2001-11-30 | 2003-06-10 | Mitsui Chemicals Inc | Paste resin composition for connecting circuit and method for using the same |
| AU2003211875B2 (en) * | 2002-01-25 | 2008-05-08 | Sumitomo Bakelite Co., Ltd. | Transparent composite composition |
| JP4106953B2 (en) * | 2002-04-10 | 2008-06-25 | 凸版印刷株式会社 | Organic EL device |
| JP2004119317A (en) * | 2002-09-27 | 2004-04-15 | Toshiba Corp | Organic electroluminescent display device |
| JP2004168945A (en) * | 2002-11-21 | 2004-06-17 | Sumitomo Bakelite Co Ltd | Transparent composite composition |
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