JP5617668B2 - ポリエステルフィルムおよびそれを用いた太陽電池バックシート、太陽電池 - Google Patents
ポリエステルフィルムおよびそれを用いた太陽電池バックシート、太陽電池 Download PDFInfo
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- JP5617668B2 JP5617668B2 JP2011019434A JP2011019434A JP5617668B2 JP 5617668 B2 JP5617668 B2 JP 5617668B2 JP 2011019434 A JP2011019434 A JP 2011019434A JP 2011019434 A JP2011019434 A JP 2011019434A JP 5617668 B2 JP5617668 B2 JP 5617668B2
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Description
また、ポリエチレンシートを用いたものは、比較的安価であるが、高温(100℃〜120℃)にさらされた時の耐熱性に難があった。
るポリエステルフィルム。
(1)示差走査熱量測定(DSC)の1stRUNで求められるポリエステルフィルムの結晶化度C1が20%以上38%以下であること。
(2)ラマンバンドスペクトル法における面配向係数Rが5.0以上10.0以下であること。
ただし、
R=(R(MD)+R(TD))/2
R(MD)=I(MD)/I(ND)
R(TD)=I(TD)/I(ND)。
また、I(ND)、I(MD)およびI(TD)は、それぞれ、レーザーラマン分光法において、1615cm−1のラマンバンドスペクトルの、フィルム平面方向に垂直な偏光配置での強度(I(ND))、フィルム平面の長手方向に平行な偏光配置での強度(I(MD))、およびフィルム平面の幅方向に平行な偏光配置での強度(I(TD))である。
また、本発明のポリエステルフィルムに含まれるP層は、ラマンバンドスペクトル法における面配向係数Rが5.0以上10.0以下であることが必要である。
ただし、R=(R(MD)+R(TD))/2であり、
R(MD)=I(MD)/I(ND)、
R(TD)=I(TD)/I(ND)。
また、I(ND)、I(MD)およびI(TD)は、それぞれ、レーザーラマン分光法において、1615cm−1のラマンバンドスペクトルの、フィルム平面方向に垂直な偏光配置での強度(I(ND))、フィルム平面の長手方向に平行な偏光配置での強度(I(MD))、およびフィルム平面の幅方向に平行な偏光配置での強度(I(TD))である。
fn=(n(TD)+n(MD))/2−n(ND)
次いで、fnが0.155以上0.180以下である場合は、下式を用いて、fnをRに換算することができる。
R=500×fn−76.5
ラマンバンドスペクトル法から求められる面配向係数Rと屈折率法から求められるfnは良い相関関係にあり、Rが高いほどfnも高くなることがわかっている。
なお、ポリエステル層のポリエステルの固有粘度を0.65以上とするには、1)溶融重合によって所定の溶融粘度になった時点で吐出、ストランド化、カッティングを行い、チップ化する方法と、2)目標より低めの固有粘度で一旦チップ化し、その後固相重合を行う方法などにより、固有粘度を0.7以上より好ましくは0.75以上、さらに好ましくは0.78以上とした樹脂を用いて、窒素雰囲気下、ポリエステルの融点+10℃以上融点+30℃以下、更には融点+15℃以上+25℃以下の温度範囲で押し出すことにより得ることができる。これらのうち、熱劣化を抑えられ、かつカルボン酸末端基数を低減できるという点で、ポリエステルの重合方法としては2)の目標より低めの固有粘度で一旦チップ化し、その後固相重合を行うのが好ましい。
ここでいう伸度保持率とは、ASTM−D882(1999)に基づいて測定されたものであって、処理前のフィルムの破断伸度E0、前記処理後の破断伸度をEとした時に、下記(1)式により求められる値である。
伸度保持率(%)=E/E0×100 (1)式
なお、測定にあたっては、試料を測定片の形状に切り出した後、処理を実施し、処理後のサンプルを測定した値である。このような範囲とすることでフィルムの耐湿熱性はより一層良好なものとなり、本発明のポリエステルフィルムを用いたバックシートの耐湿熱性を良好なものとすることができる。
ここでいう伸度保持率とは、ASTM−D882(1999)に基づいて測定されたものであって、処理前のバックシートの破断伸度E0’,温度125℃、湿度100%Rhの条件下72時間放置後の破断伸度をE1’としたときに、下記式(2’)により得られた値である。
伸度保持率(%)=E1’/E0’×100 (2’)
なお、E1’は試料を測定片の形状に切り出した後、温度125℃、湿度100%Rhの条件下72時間処理を施したものを用いて測定した値である。より好ましくは、上述の方法にて求められた伸度保持率が30%以上、更に好ましくは50%以上、特に好ましくは70%以上である。本発明のポリエステルフィルムを用いた太陽電池バックシートにおいて、伸度保持率が15%に満たないと、例えばバックシートを搭載した太陽電池を長期間使用した際に劣化が進行し、外部から何らかの衝撃が太陽電池に加わったとき(例えば、落石などが太陽電池に当たった場合など)に、バックシートが破断することがあるため好ましくない。本発明の太陽電池バックシートにおいて、伸度保持率を15%以上とすることによって、長期使用時の太陽電池の耐久性を高めることができる。
本発明に用いられるポリエステルを得る方法としては、常法による重合方法が採用できる。例えば、テレフタル酸等のジカルボン酸成分またはその誘導体と、エチレングリコール等のジオール成分とを周知の方法でエステル交換反応させることによって得ることができる。ここで、ジカルボン酸成分や、その他カルボン酸基を有する共重合成分については、カルボキシル基をエステル誘導体化したものを用いるのが、カルボキシル基末端量を低減でき、耐湿熱性をより高められるという点でより好ましい。
また、熱処理工程中では、必要に応じて幅方向あるいは長手方向に3〜12%の弛緩処理を施してもよい。続いて必要に応じて、他素材との密着性をさらに高めるためにコロナ放電処理などを行い、巻き取ることにより、本発明のポリエステルフィルムを得ることができる。
A.固有粘度IV
オルトクロロフェノール100mlに樹脂を溶解させ(溶液濃度C=1.2g/ml)、その溶液の25℃での粘度をオストワルド粘度計を用いて測定した。また、同様に溶媒の粘度を測定した。得られた溶液粘度、溶媒粘度を用いて、下記式(3)により、[η]を算出し、得られた値でもって固有粘度(IV)とした。
ηsp/C=[η]+K[η]2・C ・・・(3)
(ここで、ηsp=(溶液粘度/溶媒粘度)―1、Kはハギンス定数(0.343とする)である。)。
ポリエステル層(P層)の結晶化度C1を、JIS K7122(1987)に準じて、TA Instrument社製 Q100を、データ解析にはTA Instrument社製 “Universal Analysis 2000”を用いて、下記の要領にて、測定を実施した。
サンプルパンにサンプルを5mgずつ秤量し、昇温速度は10℃/minで樹脂を0℃から300℃まで加熱し、得られた示差走査熱量測定チャートにおいて、結晶融解ピークの熱量をJISK7122(1987)の「9.転移熱の求め方」に基づいて求めた。次に、求めた結晶融解ピークの熱量をポリエステル100%結晶化度の理論値を除算して、結晶化度(%)を求めた。ポリエステル100%結晶化度の結晶融解熱量は、ポリエチレンテレフタレートの場合、140.1(J/g)である。
ASTM−D882(1999)に基づいて、サンプルを1cm×20cmの大きさに切り出し、チャック間5cm、引っ張り速度300mm/minにて引っ張ったときの破断伸度を測定した。なお、サンプル数はn=5とし、また、フィルムの長手方向、幅方向のそれぞれについて測定した後、それらの平均値として求めた。
堀場製作所Jovin Yvon製T64000を用い、レーザー光源をArレーザー(514.5nm、レーザーパワー30mW)として、ポリエステル層(P層)にレーザーを照射し、1615cm−1のラマンバンドスペクトルの、P層厚みの中央でのピーク強度を求めた。レーザーの偏光がフィルム平面方向に垂直な偏光配置での強度(I(ND))、フィルム平面の長手方向に平行な偏光配置での強度(I(MD))、およびフィルム平面の幅方向に平行な偏光配置での強度(I(TD))を求め、次にI(MD)、I(TD)それぞれをI(ND)で除算することでフィルム長手方向と幅方向それぞれの配向係数R(MD)、R(TD)を求めた。さらにR(MD)、R(TD)の平均を求め、フィルム面方向の配向係数Rとした。
アッベ屈折率計を用いて面配向係数を測定する層をガラス面に密着させ、次いでナトリウムD線
を光源として、長手方向、幅方向、厚み方向の屈折率(n(TD)、n(MD)およびn(ND))を測定し、下記式より測定層の面配向係数fnを求めた。
・fn=(n(TD)+n(MD))/2−n(ND)。
試料を測定片の形状(1cm×20cm)に切り出した後、タバイエスペック(株)製プレッシャークッカーにて、温度125℃、相対湿度100%RHの条件下にて72時間処理を行い、その後上記C.項に従って破断伸度を測定した。なお、測定はn=5とし、また、フィルムの縦方向、横方向のそれぞれについて測定した後、その平均値を破断伸度E1とした。また、処理を行う前のフィルムについても上記C.項に従って破断伸度E0を測定し、得られた破断伸度E0,E1を用いて、次の(1)式により伸度保持率を算出した。
伸度保持率(%)=E1/E0×100 (1)式
バックシートの破断伸度は、上記と同様に処理前のバックシートの破断伸度E0’とし、温度125℃、相対湿度100%RHの条件下で72時間処理後の破断伸度E1’を求め、次の(2)式により伸度保持率を算出した。
伸度保持率(%)=E1’/E0’×100 (2)式
得られた伸度保持率について、以下のように判定した。
伸度保持率が70%以上の場合:S
伸度保持率が50%以上70%未満の場合:A
伸度保持率が30%以上50%未満の場合:B
伸度保持率が15%以上30%未満の場合:C
伸度保持率が15%未満の場合:D
S〜Cが良好であり、その中でもSが最も優れている。
ポリエステル樹脂サンプルを、JIS K7122(1987)に準じて、セイコー電子工業(株)製示差走査熱量測定装置”ロボットDSC−RDC220”を、データ解析にはディスクセッション”SSC/5200”を用いて、下記の要領にて、測定を実施した。
フィルムを、フィルム厚み方向がアルミニウム製試料ホルダー表面の法線となるように貼り付け、理学電機社製X線回折装置を用いてX線の入射角度を変えながら、X線の試料表面に対する入射角がθであるとき、検出器を入射角から2θの位置に配する2θ−θ連続スキャン(図2)にて反射法で回折ピークを測定したとき、2θが26°付近の回折ピークから下記式に従い結晶子サイズを算出した。
β=(βe2−βo2)1/2
K:0.9、λ:X線(CuKα線)の波長(0.15418nm)、βe:回折ピークの半値幅、βo:半値幅の補正値(0.12°)
・ポリエステル:
酸成分としてテレフタル酸を、ジオール成分としてエチレングリコールを用い、酸化ゲルマニウム(重合触媒)を得られるポリエステルペレットに対してゲルマニウム原子換算で300ppmとなるように添加し、重縮合反応を行い、固有粘度0.54、カルボキシル基末端基数13等量/tのポリエチレンテレフタレートペレットを得た。得られたポリエチレンテレフタレートを160℃で6時間乾燥、結晶化させたのち、220℃、真空度0.3Torr、8時間の固相重合を行い、固有粘度0.80、カルボキシル基末端基数12等量/tのポリエチレンテレフタレート(PET)を得た。
単軸押出機に、ポリエステルを180℃の温度で2時間真空乾燥した後、窒素雰囲気下で供給し、275℃の温度で溶融押出後80μmカットフィルターにより濾過を行った後に、Tダイ口金に導入し、表面温度20℃に保たれたドラム上に静電印加法で密着冷却固化させて未配向(未延伸)積層シートを得た。
製膜条件を表に記載のように変えた以外は実施例1と同様にして二軸延伸フィルムを得た。
多官能の酸成分として、トリメリット酸トリメチルを、酸成分に対して、表に記載の割合で共重合せしめた以外は、上述したポリエステル(PET)と同様の製法で、共重合PETを得た。
製膜条件を変えた以外は実施例1と同様にして二軸延伸フィルムを得た。
多官能の酸成分として、トリメリット酸トリメチルを、酸成分に対して、表に記載の割合で共重合せしめた以外は、上述したポリエステル(PET)と同様の製法で、共重合PETを得た。
2:透明充填剤
3:発電素子
4:透明基板
5:試料ホルダー
6:試料(フィルム)
7:検出器
Claims (6)
- 下記(1)および(2)の条件を満たすポリエチレンテレフタレート層(P層)を有するポリエステルフィルム。
(1)示差走査熱量測定(DSC)の1stRUNで求められるポリエステルフィルムの結晶化度C1が20%以上38%以下であること。
(2)ラマンバンドスペクトル法における面配向係数Rが5.0以上10.0以下であること。
ただし、
R=(R(MD)+R(TD))/2
R(MD)=I(MD)/I(ND)
R(TD)=I(TD)/I(ND)。
また、I(ND)、I(MD)およびI(TD)は、それぞれ、レーザーラマン分光法において、1615cm−1のラマンバンドスペクトルの、フィルム平面方向に垂直な偏光配置での強度(I(ND))、フィルム平面の長手方向に平行な偏光配置での強度(I(MD))、およびフィルム平面の幅方向に平行な偏光配置での強度(I(TD))である。 - P層におけるポリエチレンテレフタレートの(100)面結晶子サイズが4nm以下である請求項1に記載のポリエステルフィルム。
- P層の固有粘度(IV)が0.65以上かつカルボキシル基末端基数が20等量/t以下である請求項1または2に記載のポリエステルフィルム。
- P層が、多官能化合物成分が共重合されたポリエチレンテレフタレートを含有し、かつP層中の多官能化合物成分の含有量が、P層中の酸成分に対して、0.1mol%以上0.5mol%以下である請求項1〜3のいずれかに記載のポリエステルフィルム。
- 請求項1〜4のいずれかに記載のポリエステルフィルムを用いた太陽電池用バックシート。
- 請求項5に記載の太陽電池用バックシートを用いた太陽電池。
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| KR102022274B1 (ko) * | 2012-08-21 | 2019-09-18 | 도레이 카부시키가이샤 | 2축 배향 폴리에틸렌테레프탈레이트 필름 및 그 제조 방법 |
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| JP2014239125A (ja) * | 2013-06-07 | 2014-12-18 | 三菱樹脂株式会社 | 太陽電池裏面封止用ポリエステルフィルム |
| JP2014239128A (ja) * | 2013-06-07 | 2014-12-18 | 三菱樹脂株式会社 | 太陽電池裏面封止用ポリエステルフィルム |
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