JP2012518691A - 白色塗布ポリエステルフィルム及びその製造方法ならびにソーラーモジュールにおけるバックカバーとしてのその使用 - Google Patents
白色塗布ポリエステルフィルム及びその製造方法ならびにソーラーモジュールにおけるバックカバーとしてのその使用 Download PDFInfo
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- JP2012518691A JP2012518691A JP2011550461A JP2011550461A JP2012518691A JP 2012518691 A JP2012518691 A JP 2012518691A JP 2011550461 A JP2011550461 A JP 2011550461A JP 2011550461 A JP2011550461 A JP 2011550461A JP 2012518691 A JP2012518691 A JP 2012518691A
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- film
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- film according
- polyester film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
Abstract
Description
・機械的な影響から脆いソーラーセルを保護する。
・ソーラーセルの保護および湿気からの電気的短絡を防ぐ。
・電気部品との接続を防ぐ。
・ソーラーセルを埋込むための透明ポリマー材。最も汎用的に使用される材料としてはフィルム形状のエチレン−ビニルアセテート(エチレン−酢酸ビニル、EVA)である。EVAは比較的高温で溶融し、適当な添加剤により架橋し、屋外環境に極めて優れた耐性を有する。EVAの種類およびその中に存在させる添加剤によって、架橋プロセスは異なる架橋時間を必要とする。その違いはいわゆる「標準硬化型」と「急速硬化型」として区別されている。
・原則的に透明または着色されたバックカバー。代表的にはポリマーフィルム又は積層ポリマーフィルム(例えばフッ素化ポリマーフィルムやポリエステルフィルム)が使用される。白色不透明バックカバーは、ソーラーセル間を通過する太陽光がバックカバーの上面で反射し、ソーラーモジュールの効率を増大させるため有利である。
本発明のフィルムとEVAフィルムとから成る積層体を85℃で85%の空気の相対湿度に1000時間保存した後に剥離するために必要な応力を保存開始時のそれと比較して50%以上であることを意味する。
本発明の非透明性白色ポリエステルフィルムは、少なくとも片面に、1)ポリウレタン及び2)架橋剤から成るEVA接着塗布層を有する。本発明において好ましいポリウレタン及び架橋剤を以下に記載する。
本発明の塗布組成物が塗布されるポリエステルフィルムは、単層であっても、ベース層(B)と外層(A)から成る2層であっても、ベース層(B)と2つの外層(A’、C)から成る3層であってもよい。ポリエステルフィルムが多層構造の場合、外層(AA’、C)の厚さは0.1〜10μm、好ましくは0.2〜5μmである。ベース層の厚さは、フィルムの総厚さから外層の厚さを差し引いて算出される。
塗布ポリエステルフィルムを切り、長さ300mm、幅25mmの細長い切片を2つ用意した。長さ50mm、幅25mmのEVAフィルム切片(厚さ0.5mm)を上記の2つの塗布ポリエステルフィルム切片の間に、それぞれの塗布面がEVAフィルムに接する向きで挟んだ。ポリエステルフィルムとEVAは、続いてヒートシール装置(TP−701−B、(テスター)産業社製、日本)によって積層した。使用したEVAの種類によって以下のシール条件を採用した。
高温高湿下でのPET/EVA/PET積層体の長期安定性を評価するため、25mm幅の試験試料を上記の方法で作成し、IEC61215の規格に基づき、温度85℃、相対湿度85%に調節されたキャビネット(Hiflex(登録商標)FX210C、楠本化成社エタック事業部製、日本)中で1000時間保存した。
25cm×25cmのガラスプレート(Krystal Klear(登録商標)、厚さ3mm、AFG社製、米国)をイソプロパノールによって洗浄する。次いで、同じ大きさのEVAフィルムをガラスプレート上に配置し、更に試験用PETフィルムを塗膜面がEVAフィルム面に接するように配置する。得られた複合体を、先ず、脱気可能な加熱キャビネットに入れ、150℃の温度で100mbarの減圧下で約2分間加熱する。更に5分間加熱後、複合体を取り出し、ホットプレス(10t、Gonno社製、日本)で積層した。使用したEVAにより、以下の条件を採用した。
・照射光強度:0.35W/cm2、340nm(キセノンランプ、ホウ化ケイ素から成るフィルター使用)
・照射サイクル:102分間乾燥状態、18分間脱イオン水をスプレー状態
・ブラックパネル温度:63℃
塗膜の硬度はナノインデント法により測定した。この方法は、基材にかかわりなく塗膜の硬度を測定できる方法である。「TS70 TriboScope(登録商標)」ナノインデント装置(Hysitron社製、米国)を、原子間力顕微鏡(SPM−9500J2、島津製作所社製、日本)と連結した「Berkovich」チップと共に使用した。測定は室温、50%相対湿度の帯湿空気中で行われた。チップの浸入深さは10nmに調整した。
片面に塗膜を有する15cm×14cmのフィルム試料2つを、温度と湿度が40℃/80%相対湿度に調節されたキャビネットに2時間保存した。次いで、2つの試料を、塗膜面と塗膜を有さない面とが接するように重ね、上記の環境下、キャビネット内で10kgの重量の圧力(48g/cm2に対応)を20時間負荷した。試料は、引張試験機(Autograph AG−1島津製作所社製、日本)を使用し、ピンと張った0.1mm厚のスチールワイヤーを使用して500mm/分の速度で引張り、重ねられた2つのフィルム試料を互いに分離した。必要とされる平均力(g)を力−距離線図より決定した。平均力が低いほど、塗布フィルムの耐ブロッキング性が良好である(平均力が50g未満が良好である)。
塗膜の性状は目視により評価した。
「Lamda 12」型分光計(標準照光器D65、10°標準観測器、Perkin Elmer社製、米国)を使用し、ASTM−D 1925−70に準じて測定した。測定された色値座標X、Y、Zを使用し、下記式に基づいて黄変指数YIを算出した。
光透明は、ASTM−D1003に準じ測定した。
白色度はBergerの方法により、「ELREPHO(登録商標)」(Zeiss社製(ドイツ))電気的反射光度計(標準照度C(2°通常観測))を使用して測定した。白色度は、W=RY+3RZ−3RXの式に基づき算出した。
標準粘度SV(DCA)はDIN53726に従い、ジクロル酢酸中25℃で測定した。固有粘度(IV)は、標準粘度と以下の式を使用して算出した。
フィルムの収縮率はDIN 40634に準じ、150℃で、滞留時間15分として測定した。
表面粗度Raの算術平均は、DIN4762に準じて測定した(カットオフ値:0.25mm)。
グロス値はDIN 67530に準じて測定した。反射率を、フィルム表面の光学的特性として測定した。ASTM−D 523−78及びISO 2813を基準とし、入射角を20°とした。所定の入射角で試料の平坦な表面に光線を照射すると、反射および/または散乱が起こる。光電検知器に当った光が電気的な比率変数として表示される。得られた無次元値は入射角と共に表示される。
溶融ポリエステルの原料としてM67を使用した以外は実施例1と同様の方法でフィルムを製造した。フィルムは実施例1と同様に塗布を行い、特性付けを行った。得られた塗布フィルムは、低光線透過度、高白色度、高グロス、湿度と熱の影響に曝されても非常に良好なEVAヘの接着性を有していた。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下においても剥離することなく耐えることが出来た。
溶融ポリエステルの原料として70重量%のM67と30重量%のM80を使用した以外は実施例1と同様の方法でフィルムを製造した。フィルムは実施例1と同様に塗布を行い、特性付けを行った。得られた塗布フィルムは、低光線透過度、高白色度、高グロス、湿度と熱の影響に曝されても非常に良好なEVAヘの接着性を有していた。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下においても剥離することなく耐えることが出来た。
実施例1で製造されたフィルムを280℃で溶融し、ストランドに成形し、水中で急冷し、ペレットに加工した。得られたペレットをベースフィルムを製造するための原料ポリエステルとして50重量%添加した。フィルムは実施例1と同様に塗布を行い、特性付けを行った。得られた塗布フィルムは、実施例1におけるフィルムと類似の性質を示した。フィルムの黄変度は再生品を使用しているにもかかわらず、実施例1のフィルムと比較してそれほど上昇しなかった。
表3に示す組成の塗布組成物分散体を5重量を使用して、実施例1と類似の方法でフィルムを製造し、塗布を行った。続いて、得られた塗布フィルムを上記の方法で特性付けした。同様に、得られた塗布フィルムは、低光線透過度、高白色度、高グロス、湿度と熱の影響に曝されても非常に良好なEVAヘの接着性を有していた。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下においても剥離することなく耐えることが出来た。
塗布を行わなかった以外は実施例1と同様の方法でポリエステルフィルムを製造した。得られた未塗布フィルムを上記の方法で特性付けした。85℃で85%の空気の相対湿度に1000時間保存した後のEVAヘの接着性は不十分であった。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下において剥離した。
塗布を行わなかった以外は実施例2と同様の方法でポリエステルフィルムを製造した。得られた未塗布フィルムを上記の方法で特性付けした。85℃で85%の空気の相対湿度に1000時間保存した後のEVAヘの接着性は不十分であった。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下において剥離した。
比較例1で製造されたフィルムを280℃で溶融し、ストランドに成形し、水中で急冷し、ペレットに加工した。得られたペレットをベースフィルムを製造するための原料ポリエステルとして50重量%添加した。得られた未塗布フィルムを上記の方法で特性付けした。85℃で85%の空気の相対湿度に1000時間保存した後のEVAヘの接着性は不十分であった。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下において剥離した。
表3に示す組成の塗布組成物分散体を5重量を使用して、実施例1と類似の方法でフィルムを製造し、塗布を行った。続いて、得られた塗布フィルムを上記の方法で特性付けした。85℃で85%の空気の相対湿度に1000時間保存した後のEVAヘの接着性は不十分であった。フィルムをEVA/ガラスに積層した積層体は、20000時間の人工天候下において剥離した。
Claims (15)
- 少なくとも片面に塗布層を有し、塗布層が少なくとも1種のポリウレタンと少なくとも1種の架橋剤とから成る白色塗布ポリエステルフィルム。
- (1)光線透過率が40%未満、好ましくは35%未満、更に好ましくは30%未満;(2)Berger白色度が70を超える、好ましくは75を超える、更に好ましくは80を超える;(3)塗布面の20°で測定したグロスが5を超える、好ましくは10を超える、更に好ましくは20を超える;(4)150℃で15分以内の長手方向および横方向の収縮率が2.5%未満、好ましくは2.0%未満、更に好ましくは1.5%未満;(5)請求項1に記載のフィルムとEVAフィルムとから成る積層体(塗布面がEVAに接する)を180°の角度で剥離するために必要な応力として表される塗布層面のEVAに対する接着力が50N/15mmを超え、好ましくは70N/15mmを超え;(6)請求項1に記載のフィルムとEVAフィルムとから成る積層体(塗布面がEVAに接する)を85℃で85%の空気の相対湿度に1000時間保存した後に剥離するために必要な応力を保存開始時のそれと比較して表される高温多湿下での塗膜の長期安定性が、50%以上である;(7)ナノインデント法による塗膜の機械的硬度が0.2GPaを超え、好ましくは0.25GPaを超え、更に好ましくは0.3GPaを超え;(8)請求項1に記載のフィルムとEVAフィルムと(塗布面がEVAに接する)ガラスとから成る積層体が、ISO4892に従い、キセノン耐候試験装置を使用した20000時間の促進耐候試験において層間剥離に絶えられる;(9)フィルム中のポリエステルのSV値が700を超え、好ましくは650を超え;(10)フィルムの塗布面の表面粗度Raが20nmを超え、好ましくは25nmを超え、更に好ましくは30nmを超え;(11)黄変度が80未満、好ましくは70未満である、(1)〜(11)の特性を1つ以上満足する請求項1に記載の白色塗布ポリエステルフィルム。
- ポリウレタンが、少なくとも1つのポリヒドロキシ化合物と少なくとも1つのポリイソシアネートとの反応によって得られる請求項1又は2に記載の白色塗布ポリエステルフィルム。
- ポリヒドロキシ化合物がポリエステルポリオール、ポリカーボネートポリオール及びポリオキシアルキレンポリオールから選択される請求項3に記載の白色塗布ポリエステルフィルム。
- 架橋剤が、架橋反応を行う反応性基を有する水混和性または水分散性化合物である請求項1に記載の白色塗布ポリエステルフィルム。
- 架橋剤が、オキサゾリン基、カルボジイミド基、エポキシ基、イソシアネート基またはメラミン基の少なくとも1つを有するポリマーである請求項5に記載の白色塗布ポリエステルフィルム。
- 架橋剤が、オキサゾリン基またはカルボジイミド基を含むポリマーである請求項6に記載の白色塗布ポリエステルフィルム。
- オキサゾリン基を含むポリマーが、a)以下の構造式(I)〜(III)に示されるオキサゾリン誘導体とb)少なくとも1つの他の共重合モノマーとの付加反応により形成される高分子である請求項7に記載の白色塗布ポリエステルフィルム。
- 共重合モノマーが、メタクリル酸エステル類、不飽和カルボン酸類、不飽和ニトリル類、不飽和アミド類、ビニルエステル類、ビニルエーテル類、α−オレフィン類、ハロゲン化α,β−不飽和化合物類およびα,β−不飽和芳香族化合物類から選択される1種以上である請求項8に記載の白色塗布ポリエステルフィルム。
- 塗布層が、更に、ポリエステル類、アクリレート類、メタクリレート類、ポリビニルピロリドンおよびアルコキシシランの縮合物から選択される1種以上のポリマーを含む請求項1に記載の白色塗布ポリエステルフィルム。
- 塗布層が、更に、耐ブロッキング剤、界面活性剤、帯電防止剤、酸化防止剤および泡調整剤から選択される1種以上を含む請求項1に記載の白色塗布ポリエステルフィルム。
- ポリエステルフィルム上の乾燥塗布層の厚さが5〜500nm、好ましくは10〜250nmである請求項1に記載の白色塗布ポリエステルフィルム。
- 請求項1に記載の白色塗布ポリエステルフィルムの製造方法であって、当該製造方法は、スロットダイを介して冷却ロール上に白色粒子および/または空胞発生粒子を含有する1つ以上のポリエステル溶融体を押出し又は共押出しする工程と、形成されたフィルム前駆体を引取る工程と、フィルム前駆体を同時または逐次二軸延伸してフィルムを得る工程と、得られたフィルムを熱固定し巻取る工程とから成り、更に塗布分散体または塗布組成物をインライン法でフィルムに塗布する工程を有し、当該塗布工程は同時二軸延伸前か逐次二軸延伸における横方向延伸の前に行われ、塗布分散体または塗布組成物が少なくとも1種のポリウレタンと少なくとも1種の架橋剤とから成ることを特徴とするフィルムの製造方法。
- 請求項1に記載のフィルムのソーラーモジュールのバックカバー又はソーラーモジュールのバックカバー用積層体としての使用。
- 請求項1に記載のフィルムから成るソーラーモジュール。
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US (1) | US9206295B2 (ja) |
EP (1) | EP2398849B1 (ja) |
JP (1) | JP5686745B2 (ja) |
KR (1) | KR20110118170A (ja) |
CN (1) | CN102325831B (ja) |
DE (1) | DE102009009791A1 (ja) |
PL (1) | PL2398849T3 (ja) |
WO (1) | WO2010094443A1 (ja) |
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- 2010-02-15 JP JP2011550461A patent/JP5686745B2/ja not_active Expired - Fee Related
- 2010-02-15 WO PCT/EP2010/000912 patent/WO2010094443A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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JP5686745B2 (ja) | 2015-03-18 |
KR20110118170A (ko) | 2011-10-28 |
EP2398849B1 (en) | 2017-11-08 |
US20100215902A1 (en) | 2010-08-26 |
CN102325831A (zh) | 2012-01-18 |
EP2398849A1 (en) | 2011-12-28 |
DE102009009791A1 (de) | 2010-08-26 |
US9206295B2 (en) | 2015-12-08 |
PL2398849T3 (pl) | 2019-01-31 |
CN102325831B (zh) | 2014-05-07 |
WO2010094443A1 (en) | 2010-08-26 |
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