JP5762621B2 - 光電子デバイスおよびそれらのための被膜、ならびにそれらの作製および使用方法 - Google Patents
光電子デバイスおよびそれらのための被膜、ならびにそれらの作製および使用方法 Download PDFInfo
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- JP5762621B2 JP5762621B2 JP2014502824A JP2014502824A JP5762621B2 JP 5762621 B2 JP5762621 B2 JP 5762621B2 JP 2014502824 A JP2014502824 A JP 2014502824A JP 2014502824 A JP2014502824 A JP 2014502824A JP 5762621 B2 JP5762621 B2 JP 5762621B2
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Images
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Description
耐破壊性の比較
耐破壊性の1つの尺度は、図1に示す通りに、ポリマーフィルムを封止材フィルム上に支持し、ポンチで衝撃を与えることである。よって、4ポンド(1.8kg)の重錘を、平坦な0.19インチ(0.48cm)の正方形のスチール製ポンチの上に様々な高さから落下させた。不合格とは、ポリマーフィルム中の破損として定義される。5ミル(127μm)厚のフィルムをStevens Urethaneによって供給される14ミル(355.6μm)厚のポリウレタンの封止材フィルム上で支持した。ETFEポリマー(3M Companyから市販される)、PCフィルム(SABIC Innovative Plastics IP B.V.から市販されるLexan*8050フィルム)、およびPETフィルム(DuPont−Teijenから市販される)のフィルムに力を加え、それを表1に示す。その結果により、同等の厚さでPCおよびPETはETFEより大きい貫通力に耐えることができることが示される。
切断試験結果
耐切断性の尺度は、米国保険業者安全試験所のUL1703、24節によって提供されており、該規格では、図2に概略的に示すように、加重した炭素鋼製の刃がポリマーフィルムを横切って引かれる。荷重は刃先で測定される。フィルムを、ポリ(エチレン−co−酢酸ビニル)(EVA)またはポリウレタンの封止材フィルムに真空ラミネートして、モジュールをシミュレートした。比較のために、柔軟なUni−Solar Photovoltaic Laminateの一部分も試験した。フィルムが切断されたかどうかを決定するために、該領域に、95%エタノール1ミリリットル(mL)中にフルオレセイン染料1ミリグラム(mg)を含む溶液を塗布し、そのまま乾燥した。過剰なフルオレセインを流水によって除去し、該領域を365ナノメートル(nm)のブラックライト下で調べた。少しでも溶液がフィルムを通って浸透していれば、フルオレセインが封止材中に拡散することになり、強い蛍光ゾーンとなる。結果を表2に示す。
UV安定性
PCおよびPETなどのポリマーの耐候性を向上させるいくつかの方法が存在する。例えば、紫外線吸収剤(UVA)を含有する被膜を施すことができる。しかし、UVAそれ自体が光劣化を受けやすいので、所望される20年を超す耐候性を実現するのは困難である。透明被膜の寿命は、最終的にはUV吸収剤の寿命および母材の安定性によって決定される。あるものは、物理的性質の折り合いをつける前に、被膜に許される最大の厚さおよび最大のUVA配合量によって制限されることが多い。
ベンゾトリアゾールのUV吸収剤を有する塗布液
7グラム(g)のElvacite2041PMMA、79gの1−メトキシ−2−プロパノール、14gのジアセトンアルコール、0.85gのTinuvin384、0.43gのTinuvin328、0.22gのCyasorb5411、および2滴のBYK331界面活性剤を含有する塗布液を調製した。よって、該液は、固形分に基づいて、総重量の7%のPMMA、および10%のTinuvin384、5%のTinuvin328、ならびに2.5%のCyasorb5411を含有する。この液を、フローコーティングによって、7ミル(177.8μm)のポリカーボネートフィルム、幅10インチ(25.4cm)および長さ15インチ(38.1cm)の上に塗布し、溶媒を50℃で10分間フラッシュ蒸発させ、被覆フィルムを100℃で1時間焼成した。フィルムの上部5インチ(12.7cm)を廃棄した。
ジベンゾイルレゾルシノールおよびジフェニルトリアジンのUV吸収剤を有する塗布液
14gのElvacite2041PMMA、158gの1−メトキシ−2−プロパノール、28gのジアセトンアルコール、1.7gの4,6−ジベンゾイルレゾルシノール(DBR)、0.85gのAdeka LA−46、0.43gのTinvuin1577、および4滴のBYK331界面活性剤を含有する塗布液を調製した。よって、該液は、固形分に基づいて、総重量の7%のPMMAおよび10%のDBR、5%のLA−46、ならびに2.5%のTinuvin1577を含有する。この液を、フローコーティングによって、7ミル(177.8μm)のポリカーボネートフィルム、幅10インチ(25.4cm)および長さ15インチ(38.1cm)の上に塗布し、溶媒を50℃で10分間フラッシュ蒸発させ、被覆フィルムを100℃で1時間焼成した。フィルムの上部5インチ(12.7cm)を廃棄した。
封止したセルの耐候試験
CIGS太陽電池(Global Solar Energy、ツーソン、アリゾナ)の実装は、以下の積み上げたラミネート物から構成される:バックシート/封止材/太陽電池/封止材/上部シート。ラミネート構造物を、150℃に設定した小型の真空ラミネーター内に入れる。積み上げたものを、真空下で5分間ラミネーターに入れる。脱気ステップの間、部材はおよそ90℃に達する。5分後に、ラミネート上に圧力をかけ、部材を11分間保温する。ラミネート加工ステップの後、部材を取り出し、ラミネート加工を完了する。
共押出PCフィルム
第2の保護方法は、比較的高い配合量のUV吸収剤を含有するポリマーの共押出キャップ層を使用することである。高度に安定化させたPCの薄層とそれより厚いPC基材との共押出は、十分に確立した技術である。現在の市販品は、2から5ミル(50.8から127μm)のキャップ層に、ベンゾトリアゾールまたはシアノアクリレート型のUV吸収剤を、5〜10%の配合量で使用している。これらの吸収剤はあまり光安定性ではなく、屋外で7年から10年経つうちにかなり早く侵食されることとなる。
高RPA含有率のRPA−PC層を基材とするRPAラミネートの耐候試験
およそ7ミル(177.8μm)厚の熱可塑性ポリウレタンフィルム(Bayer製)を接着剤として使用して、90:10(重量に基づく)のRPA:PCブロックコポリマーの5ミル(127μm)厚の押出フィルムを、Melinex725PETフィルム(DuPont−Teijin製)上に真空ラミネートした。試料の背面を黒色に塗った。実施例6の条件を使用して、試料を促進耐候試験にかけた。1平方メートル当たり49メガジュール(MJ/m2)の暴露(340nmで測定)の後、該フィルムは完全に透明で、折り曲げたときに延性であった。ラミネートされていないフィルムは、4MJ/m2の暴露(340nmで測定)の後、黄変し、脆性となった。レゾルシノールポリアリレートは、フィルタ処理キセノンアーク耐候試験から評価して、3μm/年以下の侵食率を有するとPolymer Preprints48(1)、643〜644、(2007)に報告されている。
水分バリア
米国特許第7,015,640号に記載される方法を使用して、実施例5に記述した被膜を前側に施したポリマーの裏側に、5つのゾーンの傾斜バリア被膜を施した。
共押出PCを使用する封止
多結晶シリコン光起電力セルを、実施例7の実験5および実験8の共押出フィルムを前面に、EVA封止材、および1/8インチ(0.32センチメートル(cm))厚のBPAポリカーボネートシートを裏面に使用して真空封止した。
20:80(重量に基づく)のRPA:PCコポリマーとUV吸収剤とを含むキャップ層を有する共押出(「Coex」)PCフィルム
RPA−PCブロックコポリマーをポリカーボネート基材と共押出しして、フィルムまたはシートを作製することができることが留意される。しかし、ブロックコポリマーのRPA含有率が、ブロックコポリマーの総重量に基づいて50wt%以上であるときは、該コポリマーは、通常のBPAポリカーボネート基材と非相溶性であるので、共押出プロセスのためにRPA−PCコポリマー層とBPA−PC基材層との間に連結層が必要とされる。ブロックコポリマーのRPA含有率が、ブロックコポリマーの総重量に基づいて40wt%以下であるときは、ブロックコポリマーはBPA−PCと相溶性があり、連結層を用いずに(例えば、RPA−PCブロックコポリマー層と基材との間に接着層がなくてもよい)BPA−PC基材層と直接共押出しすることができる。上で述べたように、UV吸収剤(1つまたは複数)を耐候層組成に添加して、層の耐UV性をさらに強化することができる。層は、3から10ミル(76.2から254μm)の厚さのRPA−PCブロックコポリマー、および5から20ミル(127μmから508μm)の厚さの基材(例えば、ポリカーボネート)を有することができる。最も具体的には、4から5ミル(101.6μmから127μm)のRPA−PCブロックコポリマー、および5ミルから15ミル(127μmから381μm)の基材(例えば、ポリカーボネート)である。
Br-PCは、BPA-PC50wt%とTBBPA-BPAコポリマー50wt%とのブレンドであり、TBBPA:BPAの比率は、重量に基づいて25:75である。
ERは侵食率である。
SRは収縮率である。
のトリアジンを含むことができ、ならびに/あるいは(xix)R1、R2、およびR3=Hであってもよく、ならびに/あるいは(xx)R4は、C6H13であってもよく、ならびに/あるいは(xxi)R4は、CH2CH2OOCC7H15であってもよく、ならびに/あるいは(xxii)耐候保護層は、下式
Claims (17)
- 透明な熱可塑性基材であって、芳香族ポリカーボネートおよびポリエステル、ならびに前述の材料の少なくとも1つを含む組み合わせから選択される材料を含む熱可塑性基材と、
耐候保護層であって、
a)レゾルシノールポリアリレート、及び又は
b)レゾルシノールポリアリレートとポリカーボネートとを含むブロックコポリマー、及び又は
c)ポリカーボネートおよび5wt%以上のUV吸収剤を含み、及び
フィルタ処理したキセノンアークへの暴露から評価して、330nmで0.15A/年以下のUV吸光度損失率を有し、および/またはフィルタ処理したキセノンアークへの暴露から評価して、1年当たり5μm以下の侵食率を有する耐候保護層と、
を含む、被覆された構成要素と、
前記被覆された構成要素上の光電子デバイスであって、発光ダイオードおよび光起電力セルから選択される光電子デバイスと、
を含むことを特徴とする光電子デバイス組立体。 - 請求項1に記載の組立体であって、前記耐候保護層が、ポリカーボネートとレゾルシノールポリアリレートとを含むブロックコポリマーを含むことを特徴とする組立体。
- 請求項1に記載の組立体であって、前記熱可塑性基材は、ビスフェノールAポリカーボネートホモポリマーとポリカーボネートコポリマーとを含む透明な熱可塑性基材であって、前記ポリカーボネートコポリマーが、テトラブロモビスフェノールAカーボネートとBPAカーボネートとのコポリマー、2−フェニル−3,3−ビス(4−ヒドロキシフェニル)フタルイミジンカーボネートとBPAカーボネートとのコポリマー、4,4’−(1−フェニルエチリデン)ビフェノールカーボネートとBPAカーボネートとのコポリマー、4,4’−(1−メチルエチリデン)ビス[2,6−ジメチル−フェノール]カーボネートとBPAカーボネートとのコポリマー、および前述の少なくとも1つを含む組み合わせから選択される材料を含み、
前記耐候保護層は、
a)レゾルシノールポリアリレートとポリカーボネートとを含む前記ブロックコポリマー、ならびに/または
b)前記ポリカーボネートおよび5wt%以上のUV吸収剤
を含むことを特徴とする光電子デバイス組立体。 - 請求項1〜3のいずれかに記載の組立体であって、前記耐候保護層が、4,6−ジベンゾイルレゾルシノール、シリル化された4,6−ジベンゾイルレゾルシノール、2,4−ジフェニル−6−(2’−ヒドロキシ−4’アルコキシフェニル)−1,3,5−トリアジン、および前述の少なくとも1つを含む組み合わせから選択されるUV吸収剤を含むことを特徴とする組立体。
- 請求項5に記載の組立体であって、R1、R2およびR3=Hであることを特徴とする組立体。
- 請求項5または6に記載の組立体であって、R4=C6H13であることを特徴とする組立体。
- 請求項5または6に記載の組立体であって、R4=CH2CH2OOCC7H15であることを特徴とする組立体。
- 請求項3〜5のいずれかに記載の組立体であって、前記耐候保護層が、レゾルシノールポリアリレートとポリカーボネートとを含むブロックコポリマーを含み、前記ブロックコポリマーが、80wt%以上のレゾルシノールポリアリレートブロック含有率を有し、追加的なUV吸収剤を有していないことを特徴とする組立体。
- 請求項3〜8のいずれかに記載の組立体であって、前記耐候保護層が、レゾルシノールポリアリレートとポリカーボネートとを含むブロックコポリマーを含み、前記ブロックコポリマーが、40wt%以下のレゾルシノールポリアリレートブロック含有率を有することを特徴とする組立体。
- 請求項1〜10のいずれかに記載の組立体であって、前記耐候保護層が、シリコーン、ポリ(メタ)アクリレート、ポリカーボネートから選択される少なくとも1つを含む母材をさらに含むことを特徴とする組立体。
- 請求項1〜11のいずれかに記載の組立体であって、前記耐候保護層が、複数のレンズ、マイクロレンズ、線状プリズム、プリズム、角錐、レンズ状構造、および前述の少なくとも1つを含む組み合わせから選択される工学的表面テクスチャを有することを特徴とする組立体。
- 請求項1〜12のいずれかに記載の組立体であって、前記透明な熱可塑性基材および前記耐候保護層が共押出しされることを特徴とする組立体。
- 請求項1〜13のいずれかに記載の組立体であって、組成物中に実質的に有機である少なくとも1つのゾーンと、組成物中に実質的に無機である少なくとも1つのゾーンとを含むバリア被膜層、および/又は平坦化層を含み、
前記平坦化層が、エポキシ系樹脂、アクリル系樹脂、UV硬化アクリル−コロイドシリカ被膜層、シリコーン樹脂、および前述の少なくとも1つを含む組み合わせから選択されることを特徴とする組立体。 - 請求項14に記載の組立体であって、前記平坦化層を含み、前記平坦化層が1nmから100μmの厚さを有することを特徴とする組立体。
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