JP2005019269A - Organic el element and resin composition for pasting together organic el element - Google Patents
Organic el element and resin composition for pasting together organic el element Download PDFInfo
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- JP2005019269A JP2005019269A JP2003183956A JP2003183956A JP2005019269A JP 2005019269 A JP2005019269 A JP 2005019269A JP 2003183956 A JP2003183956 A JP 2003183956A JP 2003183956 A JP2003183956 A JP 2003183956A JP 2005019269 A JP2005019269 A JP 2005019269A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 230000005525 hole transport Effects 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
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- 238000010030 laminating Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 abstract description 4
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- 239000003822 epoxy resin Substances 0.000 description 14
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- 238000005259 measurement Methods 0.000 description 5
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
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- OSVSGGXCQRQNTE-UHFFFAOYSA-N 1-n,1-n',1-n"-trimethylhexane-1,1,1-triamine Chemical compound CCCCCC(NC)(NC)NC OSVSGGXCQRQNTE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical class NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
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- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QAZHYRJYZIMJJI-UHFFFAOYSA-N n-ethylpiperazin-1-amine Chemical compound CCNN1CCNCC1 QAZHYRJYZIMJJI-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
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Abstract
Description
【０００１】
【発明の属する技術分野】
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、およびその貼合せ用樹脂組成物に関する。
【０００２】
【従来の技術】
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ることができ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うなどの現象が起き、このようなことから発光しなくなったり輝度が低下するなどの欠点がある。
【０００３】
このような欠点を解消するために、アクリル樹脂でモールドする方法（特開平３−３７９９１号公報）、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（特開平３−２６１０９１号公報）、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（特開平４−２１２２８４号公報）、プラズマ重合膜及び光硬化型樹脂層を設ける方法（特開平５−３６４７５号公報）、フッ素化炭素からなる不活性液体中に保持する方法（特開平４−３６３８９０号公報他）、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（特開平５−３６７４７５号公報）、無機酸化物等の保護膜の上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（特開平５−８９９５９号公報）、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（特開平５−１２９０８０号公報）等が提案されている。
【０００４】
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。
【０００５】
【発明が解決しようとする課題】
そこで、特開平５−１８２７５９号公報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、この公報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、樹脂の透明度が低く、有機ＥＬ発光側に使用しにくいという問題があり、実用的できるものではなかった。
【０００６】
従来の封止用接着剤としてアクリル樹脂は硬化時に素子に及ぼすダメージが大きく、また特に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、特開平５−１８２７５９号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。
【０００７】
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、ファクシミリ、複写機、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。
【０００８】
本発明は上記従来技術の問題点を解決し、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・成長を確実に制御して、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、また、それに使用される貼合わせ用樹脂組成物を得ることを目的とする。
【０００９】
【課題を解決するための手段】
上記の問題を解決するため本発明は、ガラス基板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、硬化性樹脂７を積層して非透水性ガラス６と貼り合わせる有機ＥＬ素子において、前記硬化性樹脂７が（Ａ）分子中にグリシジル基を有する化合物、（Ｂ）変性脂環式ポリアミン、または、変性脂肪族ポリアミンからなることを特徴とする有機ＥＬ素子と、前記有機ＥＬ素子に使用される硬化性樹脂組成物を提供するものである。
【００１０】
以下、本発明を詳細に説明する。まず、本発明の有機ＥＬ素子は図１に示すようにガラス基板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。またガラス基板１上には、耐湿性を有した硬化性樹脂層７を介しガラスや金属等の非透水性ガラス基板６が固着される。
【００１１】
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、ガラス基板１上に透明電極２を０ ．１μｍの厚みで成膜する。透明電極２の成膜の方法は真空蒸着及びスパッタ等による方法が挙げられる。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。
【００１２】
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。
【００１３】
これらの素子の成膜を終えた後、ガラス基板１の上部に硬化性樹脂を約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６を密着させる。硬化性樹脂の詳細は後述する。
【００１４】
非透水性ガラス基板６の密着を終えた後、常温で養生または常温より少し加熱した温度での加熱促進により硬化性樹脂を硬化させて硬化性樹脂層７を形成する。これにより、非透水性ガラス基板６は硬化性樹脂層７を介してガラス基板１に固着される。
【００１５】
本発明で使用することのできる硬化性樹脂７の性能は、４００ｎｍ以上で９０％以上の光透過率であること、透湿度が６０℃、９５％で１００ｇ／ｍ２×２４ｈ以下であること（厚み１５０μｍ）、硬化物から発生するアウトガスが２０ｐｐｍ以下であること（１２０℃×１５ｍｉｎ抽出）、ガラス同士のはく離接着力が５ｋｇｆ／ｃｍ２ 以上であること、水分量が２０００ｐｐｍ以下であること、５０℃〜７０℃程度の比較的低温で硬化が可能であることが要求される。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、（Ｂ）変性脂環式ポリアミン、および／または、変性脂肪族ポリアミンからなるエポキシ樹脂組成物であることが判明した。
【００１６】
上記有機ＥＬ層と非透水ガラス基板層の接着に本発明の硬化性樹脂組成物を使用し固着封止する事により、有機ＥＬ素子の劣化の進行を大幅に制御することができ、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。本発明の二液性エポキシ樹脂は常温で硬化させ、比較的低温での加熱により硬化促進させることができる。
【００１７】
本発明の二液性エポキシ樹脂において（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）が好ましく使用される。
【００１８】
また、（Ａ）成分の粘度は１０００〜２００００ｃＰが好ましい。粘度が２００００ｃＰを越えると後述する（Ｂ）と混合する際に気泡が混入しやすく、また貼り合わせ時の抵抗が大きく膜厚が安定しない。また、１０００ｃＰより低いと塗布後の樹脂が流れ出し、貼り合わせることができない。
【００１９】
本発明の（Ｂ）成分は変性脂環式ポリアミン、および／または、変性脂肪族ポリアミンである。（Ａ）成分を硬化させるための硬化剤はアミン系が公知であるが前記した各要求項目を満たすものは変性脂環式ポリアミン、または、変性脂肪族ポリアミンまたはその混合物である。脂環式ポリアミンの例は、メンセンジアミン、イソホロンジアミン、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、メタキシリレンジアミンの水添物、Ｎ−エチルアミノピペラジンなどであり、脂肪族ポリアミンの例は、ジエチレントリアミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、アミノエチルエタノールアミン、トリ（メチルアミノ）ヘキサン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、メチルイミノビスプロピルアミンなどである。これらの変性物としてはエポキシアダクト反応物、マンニッヒ反応物、シアノエチル化物、マイケル反応物、ケチミン化物、チオ尿素付加物などのが挙げられる。
【００２０】
商業的に入手が容易な変性脂環式ポリアミンとして「アンカミン１６１８」（ＡＣＩ ＪＡＰＡＮ販売）アンカミン２０７４、１８８２（エアプロダクツ社製）、等が挙げられる。商業的に入手が容易な変性脂肪族ポリアミンとして「カサミド２２２１」（ＡＣＩ ＪＡＰＡＮ販売）、「ラッカマイドＷＨ１０８Ｓ（大日本インキ化学工業（株）、アデカハードナーＥＨ２２０、ＥＨ−２７０Ｂ（旭電化工業（株）製）、バーサミンＩ−３７６、Ｃ−３０（ヘンケル白水社製）などが挙げられる。
【００２１】
また、（Ａ）成分を硬化させる硬化剤として（Ｂ）成分以外にポリアミドアミンを添加すると接着強度を向上させることができる。しかし、ポリアミドアミンの添加量が多いと光透過率が低下するので好ましくない。適切な添加量として（Ａ）成分１００重量部に対し２５重量部までである。
【００２２】
本発明にはその他の成分の他に保存安定剤、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、着色やアウトガス等の特性が極端に低下しない程度とする。
【発明の実施の形態】
【実施例】
【００２３】
表１の通り各硬化性樹脂を調製し、各種評価を行った。なお、使用した各成分はエピクロンＥＸＡ８３５ＬＶ：ビスフェノールＡ型，ビスフェノール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Ｆ型エポキシ樹脂（ジャパンエポキシレジン株式会社製）、トーマイド２９６：ポリアミノアミド（富士化成工業株式会社製）、ダイトクラールＣ−２２００Ａ：変性脂環式ポリアミン（大都産業株式会社製）、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（ＢＴＲジャパン株式会社製）、ダイトクラールＸ−５２７３Ｃ：変性脂肪族ポリアミン（大都産業株式会社製）である。
【００２４】
評価１：透過率測定
パネル用ガラス基板に各硬化性樹脂を挟み（１００μｍ）所定の硬化時間で硬化させ測定用試験片を作成した。初期の状態で、４００ｎｍでの透過率を測定した。また、この試験片を８０℃×５００時間に放置し同じように透過率を測定した。何も塗布しないガラス基板の透過率と比較して透過率を計算し９０％以上を○とし、９０％未満を×とした。
【００２５】
評価２：透湿度測定
各硬化性樹脂を厚さ１５０μｍに所定の硬化条件で硬化させ、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）
【００２６】
評価３：アウトガス測定
フッ素コートした板の上に各硬化性樹脂を約２０ｍｇ滴下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。
【００２７】
評価４：接着力測定
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（１００μｍ）所定の硬化時間で硬化させ、上下にはく離した。この時はく離速度は５０ｍｍ／ｍｉｎとして、あらかじめ測定した接着剤塗布面積で最大荷重を除して接着力とした。
【００２８】
評価５：パネル信頼性試験−輝度劣化評価−
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。このようにしてパネルを作製し、初期の輝度を測定し、連続点灯で６０℃、９０％の環境で輝度を測定し初期の輝度に対する相対値で比較した。
【００２９】
評価６：パネル信頼性試験−ダークスポット評価−
同様に各硬化性樹脂で貼り合わせしたパネルを作成し、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発生がない場合は○、ある場合は×とした。
【００３０】
評価７：水分量試験−カールフィッシャー微量水分計−
表１の配合のとおり調製した各試料に酸化バリウム（ＩＩ）（株式会社高純度化学研究所 純度９９％以上 ｐｏｗｄｅｒ）を５ｗｔ％添加し減圧脱泡攪拌を１時間行った。その後５μｍのフィルターで濾過し、各試料を規定量混合しカールフィッシャー微量水分計にて水分量を測定した。
【００３１】
【表１】
実施例１、２は透過率を始めほぼ全ての基準をクリアーした。実施例３〜６は脂環式ポリアミン＋ポリアミド、脂肪族ポリアミン＋ポリアミドの組み合わせを試験したが、それぞれ単独の結果より総合的に優れた結果であった。脂環式、脂肪族にそれぞれポリアミドを添加することにより接着力を向上させることができた。この結果より脂環式ポリアミンとポリアミドアミン、脂肪族ポリアミンとポリアミドアミンもしくは脂環式ポリアミンと脂肪族ポリアミンとポリアミドアミンの組み合わせであれば有機ＥＬ素子貼合わせ用の樹脂組成物として使用することが可能であることがわかる。比較例１〜３は使用している硬化剤の色が濃く、透過率が低くなってしまうため適さない。比較例４は水分量が多く信頼性が劣り、耐久試験後の輝度が低く、ダークスポットの成長が大きい。
【発明の効果】
【００３３】
従来の硬化性樹脂は光透過率と低アウトガス性の優れたものは硬化させるのに８０℃以上の加熱が必要であったり、更にガラスへの接着力も低く、結果的に有機ＥＬ素子の延命を実現できなかった。逆に低透湿性、低アウトガス、高接着力、常温硬化性に優れるものは透過率が低く主に黄色もしくは褐色となってしまう。更に硬化時は無色でも長時間の放置で次第に変色（黄変）してしまい、有機ＥＬ素子の輝度を著しく低下させてしまい、実用できるものはなかった。しかし、本発明は有機ＥＬ素子の劣化の進行を大幅に制御するとこができ、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。
【００３４】
【図面の簡単な説明】
【図１】本発明の有機ＥＬ素子の一実施例を示す断面図
【符号の説明】
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硬化性樹脂[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic EL element that emits light with high luminance when an electric field is applied, and a resin composition for bonding the organic EL element.
[0002]
[Prior art]
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, organic EL elements are 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. Phenomena such as losing occur, and there are drawbacks such as no longer emitting light and lowering brightness.
[0003]
In order to eliminate such disadvantages, a method of molding with an acrylic resin (Japanese Patent Laid-Open No. 3-37991), a method of putting together with P 2 O 5 in an airtight case and blocking from the outside air (Japanese Patent Laid-Open No. 3-261910) ), A method of providing a protective film such as a metal oxide and then airtight using a glass plate or the like (Japanese Patent Laid-Open No. 4-212284), a method of providing a plasma polymerized film and a photocurable resin layer (Japanese Patent Laid-Open No. Hei 5). No. 36475), a method of holding in an inert liquid made of fluorinated carbon (Japanese Patent Laid-Open No. 4-363890 et al.), A method of holding in a silicone oil after providing a polymer protective film (Japanese Patent Laid-Open No. Hei 5- No. 367475), a method of bonding a glass plate coated with polyvinyl alcohol on a protective film such as an inorganic oxide with an epoxy resin (Japanese Patent Laid-Open No. 5-89959), And a method of confining in emissions and silicone oil (JP-A-5-129080) have been proposed.
[0004]
However, none of the above-mentioned conventional organic EL layer sealing methods are satisfactory. For example, it is not possible to suppress the generation and growth of dark spots only by enclosing the element in an airtight structure together with a hygroscopic agent. The method of holding in carbon and silicone oil not only complicates the sealing process by injecting the liquid, but also does not completely prevent the increase of dark spots, but rather the liquid is at the interface between the cathode and the organic layer. There is also a problem that it penetrates into the cathode and promotes peeling of the cathode.
[0005]
[Problems to be solved by the invention]
Therefore, in JP-A-5-182759, an ultraviolet curable resin is used to form an EL layer on a glass substrate, a resin composition is laminated so as to cover the entire surface of the EL layer, and a non-permeable glass substrate is bonded. Was developed. However, the resin composition described in this publication has a problem of deterioration of the device due to an organic solvent and ultraviolet rays contained in the resin, a problem of peeling of the cathode from the organic layer due to stress strain during curing, and a place where ultraviolet rays do not reach. In this case, there is a problem that uncured resin is generated, and the transparency of the resin is low and it is difficult to use on the organic EL light emitting side.
[0006]
Acrylic resin as a conventional sealing adhesive has a large damage to the device during curing, and especially epoxy resin has low transparency (transmittance) due to amine-derived color (mainly yellow, brown) contained in the component, It could not be used on the organic EL emission side as described in JP-A-5-182759. 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.
[0007]
Such deterioration of the organic EL element due to dark spots is not sufficiently improved and the light emission characteristics are unstable, which is a serious defect as a light source for facsimiles, copiers, liquid crystal display backlights, etc. It is not desirable as a display element such as a panel display.
[0008]
The present invention solves the above-mentioned problems of the prior art, and by performing effective sealing without adversely affecting the device, the generation and growth of dark spots can be reliably controlled, and stable light emission over a long period of time. It aims at obtaining the organic EL element which can maintain a characteristic, and the resin composition for bonding used for it.
[0009]
[Means for Solving the Problems]
In order to solve the above problems, the present invention forms an organic EL layer comprising a transparent electrode 2, a hole transport layer 3, an organic EL layer 4 and a back electrode 5 on a glass substrate 1, and laminates a curable resin 7. In the organic EL device bonded to the water-impermeable glass 6, the curable resin 7 is made of (A) a compound having a glycidyl group in the molecule, (B) a modified alicyclic polyamine, or a modified aliphatic polyamine. The organic EL element characterized by these, and the curable resin composition used for the said organic EL element are provided.
[0010]
Hereinafter, the present invention will be described in detail. First, as shown in FIG. 1, in the organic EL device of the present invention, a transparent electrode 2 such as ITO, a hole transport layer 3, an organic EL layer 4 and a back electrode 5 are laminated on a glass substrate 1 in this order. On the glass substrate 1, a non-permeable glass substrate 6 such as glass or metal is fixed through a curable resin layer 7 having moisture resistance.
[0011]
The organic EL element having such a configuration is manufactured as follows. First, the transparent electrode 2 is placed on the glass substrate 1 with 0. The film is formed with a thickness of 1 μm. Examples of the method for forming the transparent electrode 2 include vacuum evaporation 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.
[0012]
Subsequently, the hole transport layer 3 and the organic EL layer 4 are placed on the transparent electrode 2 on the top of the transparent electrode 2. Films are sequentially formed with a thickness of 05 μm. Further, a back electrode 5 is placed on the organic EL layer 4 at a distance of 0. 1 to 0. The film is formed with a thickness of 3 μm.
[0013]
After the film formation of these elements is completed, a curable resin is added to the upper portion of the glass substrate 1 by about 0. It is dripped at a thickness of 1 mm, and the water-impermeable glass substrate 6 is brought into close contact with the curable resin. Details of the curable resin will be described later.
[0014]
After the adhesion of the water-impermeable glass substrate 6 is finished, the curable resin is cured by curing at room temperature or by heating at a temperature slightly heated from room temperature to form the curable resin layer 7. Thereby, the water-impermeable glass substrate 6 is fixed to the glass substrate 1 through the curable resin layer 7.
[0015]
The performance of the curable resin 7 that can be used in the present invention is that the light transmittance is not less than 90% at 400 nm or more, and the moisture permeability is not more than 100 g / m 2 × 24 h at 60 ° C. and 95% ( 150 μm in thickness), outgas generated from the cured product is 20 ppm or less (extracted at 120 ° C. × 15 min), peel-off adhesion between glasses is 5 kgf / cm 2 or more, water content is 2000 ppm or less, 50 It is required to be able to be cured at a relatively low temperature of about 0 to 70 ° C. It has been found that an epoxy resin composition comprising (A) a compound having a glycidyl group in the molecule, (B) a modified alicyclic polyamine, and / or a modified aliphatic polyamine satisfies these requirements.
[0016]
By using the curable resin composition of the present invention for adhesion between the organic EL layer and the non-water-permeable glass substrate layer, the deterioration of the organic EL element can be greatly controlled and the life can be extended. Even if there is an epoxy resin layer on the organic EL light emitting side, high luminance can be achieved. 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 two-part epoxy resin of the present invention can be cured at room temperature and accelerated by heating at a relatively low temperature.
[0017]
In the two-part epoxy resin of the present invention, examples of the compound (A) having a glycidyl group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, etc. For use, those having a low chloride ion content, specifically those having hydrolyzable chlorine of 500 ppm or less are preferred. As a specific example of the component (A), Epicron EXA-835LV (manufactured by Dainippon Ink & Chemicals, Inc.) having a low chlorine ion concentration is preferably used.
[0018]
The viscosity of the component (A) is preferably 1000 to 20000 cP. When the viscosity exceeds 20000 cP, bubbles are easily mixed when mixed with (B) described later, and the resistance at the time of bonding is large and the film thickness is not stable. On the other hand, if it is lower than 1000 cP, the resin after application flows out and cannot be bonded.
[0019]
The component (B) of the present invention is a modified alicyclic polyamine and / or a modified aliphatic polyamine. As the curing agent for curing the component (A), amine-based curing agents are known, but those satisfying the above-mentioned requirements are modified alicyclic polyamines, modified aliphatic polyamines or mixtures thereof. Examples of alicyclic polyamines are mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, hydrogenated metaxylylenediamine, N-ethylaminopiperazine, and the like. Examples are diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, tri (methylamino) hexane, dimethylaminopropylamine, diethylaminopropylamine And methyliminobispropylamine. These modified products include epoxy adduct reactants, Mannich reactants, cyanoethylated products, Michael reactants, ketimineated products, thiourea adducts, and the like.
[0020]
Examples of modified alicyclic polyamines that are easily commercially available include “Ancamine 1618” (sold by ACI JAPAN) Ancamine 2074, 1882 (manufactured by Air Products), and the like. "Casamide 2221" (sold by ACI JAPAN), "Rakkamide WH108S (Dainippon Ink Chemical Co., Ltd.), Adeka Hardener EH220, EH-270B (Asahi Denka Kogyo Co., Ltd.) as commercially available modified aliphatic polyamines ), Versamine I-376, C-30 (manufactured by Henkel Hakusui Co., Ltd.), and the like.
[0021]
Further, when a polyamidoamine is added as a curing agent for curing the component (A) in addition to the component (B), the adhesive strength can be improved. However, if the amount of polyamidoamine added is large, the light transmittance decreases, which is not preferable. Appropriate addition amount is up to 25 parts by weight per 100 parts by weight of component (A).
[0022]
It is possible to add a storage stabilizer, a plasticizer, a reactive diluent, a filler, a viscosity adjuster, etc. in addition to the other components in the present invention, but the properties such as coloring and outgassing do not extremely decrease. To the extent.
DETAILED DESCRIPTION OF THE INVENTION
【Example】
[0023]
Each curable resin was prepared as shown in Table 1 and subjected to various evaluations. In addition, each component used is Epicron EXA835LV: Bisphenol A type, bisphenol F type mixed epoxy resin low chlorine type (Dainippon Ink Chemical Co., Ltd.), Epicoat 828: Bis A type epoxy resin (Japan Epoxy Resin Co., Ltd.) Epicoat 807: Bis-F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.), Tomide 296: Polyaminoamide (manufactured by Fuji Kasei Kogyo Co., Ltd.), Daitokural C-2200A: Modified alicyclic polyamine (manufactured by Daito Sangyo Co., Ltd.) , Sanmide A-100: Imidazole-modified amine (manufactured by Sanwa Chemical Industry Co., Ltd.), Ancamine Z: Aromatic polyamine (manufactured by BTR Japan Co., Ltd.), Daitokural X-5273C: Modified aliphatic polyamine (manufactured by Daito Sangyo Co., Ltd.) It is.
[0024]
Evaluation 1: Each curable resin was sandwiched between glass substrates for a transmittance measurement panel (100 μm) and cured for a predetermined curing time to prepare a test specimen for measurement. In the initial state, the transmittance at 400 nm was measured. Further, this test piece was left at 80 ° C. for 500 hours, and the transmittance was measured in the same manner. The transmittance was calculated by comparing with the transmittance of a glass substrate to which nothing was applied, and 90% or more was evaluated as ◯, and less than 90% was evaluated as ×.
[0025]
Evaluation 2: Measurement of moisture permeability Each curable resin was cured to a thickness of 150 µm under predetermined curing conditions, and the moisture permeability was measured under conditions of 60 ° C x 95%. (Equipment used: L80-5000 type water vapor permeability meter / manufactured by LYSSY)
[0026]
Evaluation 3: Outgas measurement Dynamic head using a double shot pyrolyzer and a gas chromatograph / mass spectrometer (GC / MS) by dropping about 20 mg of each curable resin on a fluorine-coated plate and curing it under predetermined curing conditions. The amount of outgas generated when heated at 120 ° C. for 15 minutes by the space method was measured.
[0027]
Evaluation 4: A glass substrate for an adhesive force measurement panel was cut into 25 mm × 50 mm, and a resin was sandwiched in the center (100 μm) so that the glass piece had a cross shape (100 μm), cured for a predetermined curing time, and peeled up and down. At this time, the peeling speed was 50 mm / min, and the maximum load was divided by the adhesive application area measured in advance to obtain the adhesive strength.
[0028]
Evaluation 5: Panel reliability test -Brightness degradation evaluation-
A transparent electrode is formed on a glass substrate by sputtering. A film having a thickness of 1 μm was formed. Subsequently, a hole transport layer and an organic EL layer are formed on the top of the transparent electrode. Films were sequentially formed with a thickness of 05 μm. In addition, a back electrode is formed on the top of the organic EL layer. The film is formed with a thickness of 2 μm. After the film formation of these elements is completed, each curable resin is placed on the upper portion of the glass substrate 1 by about 0. It was dripped at a thickness of 1 mm and a water-impermeable glass substrate was adhered onto the curable resin. In this way, a panel was prepared, the initial luminance was measured, the luminance was measured in an environment of 60 ° C. and 90% with continuous lighting, and the relative value was compared with the initial luminance.
[0029]
Evaluation 6: Panel reliability test-Dark spot evaluation-
Similarly, panels bonded with each curable resin were prepared, and the growth of dark spots was observed in an environment of 60 ° C. and 90% with continuous lighting. When there was no dark spot having a diameter of 100 μm or more after 1000 hours, it was marked with ◯, and when it was, it was marked with x.
[0030]
Evaluation 7: Moisture content test-Karl Fischer trace moisture meter-
To each sample prepared as shown in Table 1, 5 wt% of barium (II) oxide (High Purity Chemical Laboratory, Inc., purity 99% or more powder) was added, and vacuum degassing and stirring were performed for 1 hour. Thereafter, the mixture was filtered through a 5 μm filter, each sample was mixed in a specified amount, and the moisture content was measured with a Karl Fischer micro moisture meter.
[0031]
[Table 1]
In Examples 1 and 2, almost all the standards including transmittance were cleared. In Examples 3 to 6, the combination of alicyclic polyamine + polyamide and aliphatic polyamine + polyamide was tested, and the results were comprehensively superior to the results of the single compounds. Adhesive strength could be improved by adding polyamide to the alicyclic and aliphatic groups. From this result, any combination of alicyclic polyamine and polyamidoamine, aliphatic polyamine and polyamidoamine, or alicyclic polyamine, aliphatic polyamine and polyamidoamine can be used as a resin composition for laminating organic EL devices. It can be seen that it is. Comparative Examples 1 to 3 are not suitable because the color of the curing agent used is dark and the transmittance is low. Comparative Example 4 has a large amount of moisture, is inferior in reliability, has low luminance after the durability test, and has a large dark spot growth.
【The invention's effect】
[0033]
Conventional curable resins with excellent light transmittance and low outgassing require heating at 80 ° C. or higher to cure, and also have low adhesion to glass, resulting in longer life of organic EL devices. It could not be realized. On the other hand, those having low moisture permeability, low outgas, high adhesive strength, and room temperature curability have low transmittance and are mainly yellow or brown. Further, even when it is colorless, even when it is colorless, it is gradually discolored (yellowing) after being left for a long time, and the luminance of the organic EL element is remarkably lowered, and there is nothing practically usable. However, the present invention can greatly control the progress of the deterioration of the organic EL element, and it is possible to increase the lifetime and increase the brightness even when an epoxy resin layer is provided on the organic EL light emitting side.
[0034]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an embodiment of an organic EL device of the present invention.
1 glass substrate 2 transparent electrode 3 hole transport layer 4 organic EL layer 5 back electrode 6 water-impermeable glass substrate 7 curable resin
Claims (2)
（Ａ）分子中にグリシジル基を有する化合物
（Ｂ）変性脂環式ポリアミン、および／または、変性脂肪族ポリアミン
であることを特徴とする有機ＥＬ素子。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 substrate 1, and a curable resin 7 is laminated and bonded to the water-impermeable glass 6 In the device, the curable resin 7 is (A) a compound having a glycidyl group in the molecule (B) a modified alicyclic polyamine and / or a modified aliphatic polyamine.
（Ａ）分子中にグリシジル基を有する化合物
（Ｂ）変性脂環式ポリアミン、および／または、変性脂肪族ポリアミン
であることを特徴とする有機ＥＬ素子貼合わせ用樹脂組成物。By forming an organic EL layer comprising a transparent electrode 2, a hole transport layer 3, an organic EL layer 4, and a back electrode 5 on a glass substrate 1, laminating a curable resin 7 and bonding it to a water-impermeable glass 6. It is a curable resin that can be used in the obtained organic EL device, and the composition is (A) a compound having a glycidyl group in the molecule (B) a modified alicyclic polyamine and / or a modified aliphatic polyamine. A resin composition for laminating organic EL elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003183956A JP2005019269A (en) | 2003-06-27 | 2003-06-27 | Organic el element and resin composition for pasting together organic el element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003183956A JP2005019269A (en) | 2003-06-27 | 2003-06-27 | Organic el element and resin composition for pasting together organic el element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005019269A true JP2005019269A (en) | 2005-01-20 |
Family
ID=34183868
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003183956A Pending JP2005019269A (en) | 2003-06-27 | 2003-06-27 | Organic el element and resin composition for pasting together organic el element |
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| Country | Link |
|---|---|
| JP (1) | JP2005019269A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462651B2 (en) | 2005-04-04 | 2008-12-09 | National Starch And Chemical Investment Holding Corporation | Radiation-curable desiccant-filled adhesive/sealant |
| WO2011105141A1 (en) * | 2010-02-23 | 2011-09-01 | コニカミノルタホールディングス株式会社 | Organic electroluminescent component and method of manufacturing same |
| US8828500B2 (en) | 2008-11-28 | 2014-09-09 | Three Bond Co., Ltd. | Photocurable resin composition for sealing organic EL device |
| US8941301B2 (en) | 2007-06-28 | 2015-01-27 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and method for fabricating light-emitting element |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136098A (en) * | 1992-10-22 | 1994-05-17 | Fuji Xerox Co Ltd | Epoxy rein composition for electronic part |
| WO2000046317A1 (en) * | 1999-02-08 | 2000-08-10 | The Yokohama Rubber Co., Ltd. | Resin compositions |
| JP2001267065A (en) * | 2000-03-22 | 2001-09-28 | Casio Comput Co Ltd | Electroluminescence element |
| JP2002145996A (en) * | 2000-11-10 | 2002-05-22 | Mitsubishi Electric Corp | Thermosetting resin composition and insulated coil using the same |
| JP2002164165A (en) * | 2000-09-12 | 2002-06-07 | Toray Ind Inc | Organic electroluminescent element and its manufacturing method |
| JP2002367771A (en) * | 2001-06-05 | 2002-12-20 | Toray Ind Inc | Organic electroluminescent element |
-
2003
- 2003-06-27 JP JP2003183956A patent/JP2005019269A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136098A (en) * | 1992-10-22 | 1994-05-17 | Fuji Xerox Co Ltd | Epoxy rein composition for electronic part |
| WO2000046317A1 (en) * | 1999-02-08 | 2000-08-10 | The Yokohama Rubber Co., Ltd. | Resin compositions |
| JP2001267065A (en) * | 2000-03-22 | 2001-09-28 | Casio Comput Co Ltd | Electroluminescence element |
| JP2002164165A (en) * | 2000-09-12 | 2002-06-07 | Toray Ind Inc | Organic electroluminescent element and its manufacturing method |
| JP2002145996A (en) * | 2000-11-10 | 2002-05-22 | Mitsubishi Electric Corp | Thermosetting resin composition and insulated coil using the same |
| JP2002367771A (en) * | 2001-06-05 | 2002-12-20 | Toray Ind Inc | Organic electroluminescent element |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462651B2 (en) | 2005-04-04 | 2008-12-09 | National Starch And Chemical Investment Holding Corporation | Radiation-curable desiccant-filled adhesive/sealant |
| US8941301B2 (en) | 2007-06-28 | 2015-01-27 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and method for fabricating light-emitting element |
| US8828500B2 (en) | 2008-11-28 | 2014-09-09 | Three Bond Co., Ltd. | Photocurable resin composition for sealing organic EL device |
| WO2011105141A1 (en) * | 2010-02-23 | 2011-09-01 | コニカミノルタホールディングス株式会社 | Organic electroluminescent component and method of manufacturing same |
| JPWO2011105141A1 (en) * | 2010-02-23 | 2013-06-20 | コニカミノルタ株式会社 | Organic electroluminescence device and method for manufacturing the same |
| JP5960047B2 (en) * | 2010-02-23 | 2016-08-02 | コニカミノルタ株式会社 | Organic electroluminescence device and method for manufacturing the same |
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