JPWO2016098570A1 - 有機el素子、硬化性樹脂組成物、波長変換部の形成方法および有機el装置 - Google Patents
有機el素子、硬化性樹脂組成物、波長変換部の形成方法および有機el装置 Download PDFInfo
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- JPWO2016098570A1 JPWO2016098570A1 JP2016564767A JP2016564767A JPWO2016098570A1 JP WO2016098570 A1 JPWO2016098570 A1 JP WO2016098570A1 JP 2016564767 A JP2016564767 A JP 2016564767A JP 2016564767 A JP2016564767 A JP 2016564767A JP WO2016098570 A1 JPWO2016098570 A1 JP WO2016098570A1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002560 nitrile group Chemical group 0.000 description 1
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- BMVTVMIDGMNRRR-UHFFFAOYSA-N propyl 2-propoxyacetate Chemical compound CCCOCC(=O)OCCC BMVTVMIDGMNRRR-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 230000005469 synchrotron radiation Effects 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XRALRSQLQXKXKP-UHFFFAOYSA-N tris(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 XRALRSQLQXKXKP-UHFFFAOYSA-N 0.000 description 1
- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
前記波長変換部が、
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)上記(a1)以外の炭素数4〜20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物を用いて形成されたものであることを特徴とする有機EL素子に関する。
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)炭素数4〜20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物であって、
本発明の第1の態様の有機EL素子の前記波長変換部の形成に用いられることを特徴とする硬化性樹脂組成物に関する。
(1)本発明の第2の態様の硬化性樹脂組成物の塗膜を基材上に形成する工程、
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する工程、
(3)工程(2)で放射線を照射された塗膜を現像する工程、および
(4)工程(3)で現像された塗膜を露光する工程
を有することを特徴とする波長変換部の形成方法に関する。
<有機EL素子(1)>
図1は、本発明の第1実施形態の有機EL素子を概略的に示す断面図である。
<有機EL素子(2)>
図2は、本発明の第2実施形態の有機EL素子を概略的に示す断面図である。
したがって、有機EL素子200は、波長変換部材150から出射される赤色光、緑色光および青色光の光量を制御することにより、カラー画像を形成し、カラー表示を行うことが可能である。
青色拡散層151は、上述したように、成分である樹脂中に光散乱粒子となる透明粒子が分散されて構成されることが好ましい。
<硬化性樹脂組成物>
本発明の第3実施形態の硬化性樹脂組成物は、[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)炭素数4〜20の有機基を含む構成単位とを有する重合体(以下、[A]重合体または単に[A]成分とも言う。)、並びに、[B]量子ドット(以下、単に[B]成分とも言う。)を含有してなる硬化性の樹脂組成物である。
本発明の第3実施形態の硬化性樹脂組成物は、[A]重合体を含有する。
(i)同一の重合体分子中に構成単位(a1)および構成単位(a2)の両方を有しており、[A]重合体中に1種の重合体分子が存在する場合;
(ii)一の重合体分子中に構成単位(a1)を有し、それとは異なる重合体分子中に構成単位(a2)の両方を有しており、[A]重合体中に2種の重合体分子が存在する場合;
(iii)一の重合体分子中に構成単位(a1)および構成単位(a2)の両方を有し、それとは異なる重合体分子中に構成単位(a1)を有し、これらとはさらに異なる重合体分子中に構成単位(a2)を有しており、[A]重合体中に3種の重合体分子が存在する場合;
(iv)(i)〜(iii)に規定の重合体分子に加え、[A]重合体中にさらに別の1種または2種以上の重合体分子を含む場合等が挙げられる。
本発明の第3実施形態の硬化性樹脂組成物の必須の成分である[B]量子ドットは、半導体材料を用いて構成された半導体量子ドットであることが好ましい。そして、[B]量子ドットは、CdやPbを構成成分とせず、例えば、In(インジウム)やSi(珪素)等を構成成分として構成された、安全な材料からなる量子ドットであることが好ましい。
本発明の第3実施形態の硬化性樹脂組成物は、さらに[C]重合開始剤を含有することができる。本実施形態の[C]重合開始剤は、放射線に感応して重合性基を有する化合物の重合を開始しうる活性種を生じるものが好ましい。したがって、本実施形態の[C]重合開始剤は、感放射線性の重合開始剤、すなわち、感放射線性重合開始剤が好ましい。
本発明の第3実施形態の硬化性樹脂組成物は、さらに[D]重合性不飽和化合物を含有することができる。本発明の第3実施形態の硬化性樹脂組成物に含有される[D]重合性不飽和化合物は、重合性の不飽和構造を有する化合物である。本発明の第3実施形態の硬化性樹脂組成物が[D]重合性不飽和化合物を含有することで架橋反応性を高めることができる。そして、この硬化性樹脂組成物から形成される、本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部材の波長変換部である各波長変換層において、強度および基材との密着性を向上させることができる。その場合、[D]重合性不飽和化合物は、上述した[C]重合開始剤とともに用いられ、本発明の第3実施形態の硬化性樹脂組成物に含有されることが好ましい。
本発明の第3実施形態の硬化性樹脂組成物は、さらに、[E]安定剤を含有することができる。本発明の第3実施形態の硬化性樹脂組成物が、[A]成分や[B]成分等の必須の成分に加え、さらに[E]安定剤を含有することで、それを用いて得られる本発明の第1実施形態および第2実施形態の有機EL素子の波長変換部である各波長変換層において、光変換効率を向上させることできる。
これらのうち、特に下記式で示されるような芳香族を有するホスファイト系酸化防止剤あるいはホスフィン化合物が好ましい。
本発明の第3実施形態の硬化性樹脂組成物は、[A]成分および[B]量子ドットを必須の成分として含有するとともに、本発明の効果を損なわない限り、その他の任意成分を含有することができる。その他の任意成分としては、例えば、溶剤、硬化促進剤および熱酸発生剤等を挙げることができる。
本発明の第3実施形態の硬化性樹脂組成物は、[A]重合体および[B]量子ドットを均一に混合することによって調製される。また、含有させることが任意の[C]成分や[D]成分や[E]成分を含有させる場合、[A]成分および[B]成分とともに、必要に応じて[C]成分や[D]成分や[E]成分を均一に混合することによって調製される。
アルコール類として、例えば、ベンジルアルコール、ジアセトンアルコール等;
エーテル類として、例えば、テトラヒドロフランや、ジイソプロピルエーテル、ジn−ブチルエーテル、ジn−ペンチルエーテル、ジイソペンチルエーテル、ジn−ヘキシルエーテル等のジアルキルエーテル等;
ジエチレングリコールアルキルエーテル類として、例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル等;
エチレングリコールアルキルエーテルアセテート類として、例えば、メチルセロソルブアセテート、エチルセロソルブアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等;
プロピレングリコールモノアルキルエーテル類として、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等;
プロピレングリコールモノアルキルエーテルアセテート類として、例えば、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等;
プロピレングリコールモノアルキルエーテルプロピオネート類として、例えば、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、プロピレングリコールモノプロピルエーテルプロピオネート、プロピレングリコールモノブチルエーテルプロピオネート等;
ケトン類として、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2−ヘプタノン、4−ヒドロキシ−4−メチル−2−ペンタノン等;
エステル類として、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸i−プロピル、酢酸ブチル、2−ヒドロキシプロピオン酸エチル、2−ヒドロキシ−2−メチルプロピオン酸メチル、2−ヒドロキシ−2−メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、3−ヒドロキシプロピオン酸メチル、3−ヒドロキシプロピオン酸エチル、3−ヒドロキシプロピオン酸プロチル、3−ヒドロキシプロピオン酸ブチル、2−ヒドロキシ−3−メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸プロピル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸プロピル、エトキシ酢酸ブチル、プロポキシ酢酸メチル、プロポキシ酢酸エチル、プロポキシ酢酸プロピル、プロポキシ酢酸ブチル、ブトキシ酢酸メチル、ブトキシ酢酸エチル、ブトキシ酢酸プロピル、ブトキシ酢酸ブチル、2−メトキシプロピオン酸メチル、2−メトキシプロピオン酸エチル、2−メトキシプロピオン酸プロピル、2−メトキシプロピオン酸ブチル、2−エトキシプロピオン酸メチル、2−エトキシプロピオン酸エチル等がそれぞれ挙げられる。
<波長変換部の形成方法>
本発明の第4実施形態の波長変換部の形成方法によって得られる波長変換部は、例えば、図1および図2に示した本発明の第1実施形態の有機EL素子100および本発明の第2実施形態の有機EL素子200の波長変換部材50,150の波長変換部であり、具体的には、各波長変換層53R,53G,53Bとなる。
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する放射線照射工程。
(3)工程(2)で放射線を照射された塗膜を現像する現像工程。
(4)工程(3)で現像された塗膜を露光する硬化工程。
本発明の第4実施形態の波長変換部の形成方法の工程(1)である、塗膜形成工程では、図3に例示するように、本発明の第3実施形態の硬化性樹脂組成物の塗膜1を基材2上に形成する。
次いで、本発明の第4実施形態の波長変換部の形成方法の工程(2)である、放射線照射工程では、図4に例示するように、工程(1)で基材2上に形成された塗膜1の少なくとも一部に放射線4を照射する。このとき、塗膜1の一部にのみ、放射線4aを照射するには、例えば、所望の形状の形成に対応するパターンのフォトマスク3を介して行う。このフォトマスク3を用いることにより、照射された放射線4の一部がフォトマスクを透過し、その一部の放射線4aが、塗膜1に照射される。
次に、本発明の第4実施形態の波長変換部の形成方法の工程(3)である、現像工程では、図5に例示するように、放射線照射後の図4の塗膜1を現像して不要な部分を除去し、所定の形状にパターニングされた塗膜1aを得る。
次に、本発明の第4実施形態の波長変換部の形成方法の工程(4)である、硬化工程では、図5に例示されたパターニングされた塗膜1aを、露光装置を用いた露光によって硬化(ポスト露光ともいう)する。これにより、図6に例示するように、基材2上に形成された硬化膜5が得られる。硬化膜5は、上記の工程によって、所望の形状となるようにパターニングされたものとなる。
本実施例においては、上述した[A]重合体の例として、重合体(A−1)を用いた。以下に、重合体(A−1)の合成例を示す。
[重合体(A−1)の合成]
冷却管と攪拌機を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート150質量部を仕込んで窒素置換した。80℃に加熱して、同温度で、プロピレングリコールモノメチルエーテルアセテート50質量部、2−メタクリロイロキシエチルコハク酸30質量部、ベンジルメタクリレート10質量部、2−エチルヘキシルメタクリレート60質量部および2,2’−アゾビス(2,4−ジメチルバレロニトリル)6質量部の混合溶液を2時間かけて滴下し、この温度を保持して1時間重合した。その後、反応溶液の温度を90℃に昇温させ、さらに1時間重合することにより、重合体(A−1)を得た。重合体(A−1)は、重合体溶液(固形分濃度=33質量%)の状態で得られ、Mw=11000、Mn=6100、Mw/Mn=1.80であった。これを重合体(A−1)溶液とする。
本実施例で用いた量子ドットを次に示す。
量子ドットA:InP/ZnSコアシェル型量子ドット
[硬化性樹脂組成物(β−I)の調製]
重合体(A−1)溶液90質量部にメチルシクロヘキサン40質量部を加えて溶解させた後、量子ドットAを10質量部混合して均一な溶液を作製し、1,2−オクタンジオン−1−[4−(フェニルチオ)−2−(O−ベンゾイルオキシム)](BASFジャパン社製 イルガキュア(登録商標)OXE01)10質量部、1,9−ノナンジオールジアクリレート70質量部を混合し、硬化性樹脂組成物(β−I)を調製した。
[硬化性樹脂組成物(β−I)を用いた硬化膜の形成]
無アルカリガラス基板上に、実施例1で調製した硬化性樹脂組成物(β−I)をスピンナにより塗布した後、80℃のホットプレート上で2分間プレベークすることにより塗膜を形成した。
次に、得られたパターンに、高圧水銀ランプを用いて露光量10000J/m2として放射線照射を行い、所定の形状にパターニングされた硬化膜を形成した。
その結果、硬化性樹脂組成物(β−I)を用い、パターニングして形成された硬化膜のパターニング性は良好であった。
[蛍光特性の評価]
実施例2の形成方法による硬化膜について、さらに、絶対PL量子収率測定装置(C11347−01、浜松ホトニクス社)を用いて、25℃における蛍光量子収率を調べた。蛍光量子収率は38%であり、蛍光特性は良好と判断した。
したがって、実施例2の形成方法による硬化膜は量子ドットを含有する。そして、実施例2の形成方法による硬化膜は、有機EL素子に適用されて、その波長変換部材の波長変換部として、赤色波長変換層を構成することができ、有機EL素子の高輝度化を実現することができる。
2 基材
3 フォトマスク
4,4a 放射線
5 硬化膜
10 回路基板
11 基板
12 バッファ層
13 シリコン層
13s ソース
13d ドレイン
14 ゲート
15 選択用TFT
16 キャパシタ電極
17a コンタクトプラグ
18 第1平坦化膜
19 データライン
20 第2平坦化膜
30,130 有機EL素子アレイ
31,131 有機EL部
31a 画素電極
31b,131b 有機発光層
31c 共通電極
32 隔壁部
40 パッシベーション層
50,150 波長変換部材
51 基板
52R 赤色カラーフィルタ
52G 緑色カラーフィルタ
52B 青色カラーフィルタ
53R 赤色波長変換層
53G 緑色波長変換層
53B 青色波長変換層
54 ブラックマトリクス
100,200 有機EL素子
151 青色拡散層
Claims (8)
- 発光部と波長変換部とを有する有機EL素子であって、
前記波長変換部が、
[A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)上記(a1)以外の炭素数4〜20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物を用いて形成されたものであることを特徴とする有機EL素子。 - [B]量子ドットが、2族元素、11族元素、12族元素、13族元素、14族元素、15族元素および16族元素よりなる群から選ばれる少なくとも2種の元素を含む化合物からなることを特徴とする請求項1に記載の有機EL素子。
- [B]量子ドットが、Inを構成成分として含む化合物からなることを特徴とする請求項1または2に記載の有機EL素子。
- [B]量子ドットが、InP/ZnS化合物、CuInS2/ZnS化合物、AgInS2化合物、(ZnS/AgInS2)固溶体/ZnS化合物、ZnドープAgInS2化合物およびSi化合物よりなる群から選ばれる少なくとも1種であることを特徴とする請求項1〜3のいずれか1項に記載の有機EL素子。
- さらに、カラーフィルタを有することを特徴とする請求項1〜4のいずれか1項に記載の有機EL素子。
- [A]同一または異なる重合体分子中に、(a1)酸性基を含む構成単位と(a2)炭素数4〜20の有機基を含む構成単位とを有する重合体、および
[B]量子ドット
を含有する硬化性樹脂組成物であって、
請求項1〜5のいずれか1項に記載の有機EL素子の前記波長変換部の形成に用いられることを特徴とする硬化性樹脂組成物。 - 少なくとも青色の光を含んで発する光源部と波長変換部とを有する有機EL素子の該波長変換部を形成する波長変換部の形成方法であって、
(1)請求項6に記載の硬化性樹脂組成物の塗膜を基材上に形成する工程、
(2)工程(1)で形成した塗膜の少なくとも一部に放射線を照射する工程、
(3)工程(2)で放射線を照射された塗膜を現像する工程、および
(4)工程(3)で現像された塗膜を露光する工程
を有することを特徴とする波長変換部の形成方法。 - 請求項1〜5のいずれか1項に記載の有機EL素子を含んで構成され、画像表示に用いられることを特徴とする有機EL装置。
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