JPWO2016152638A1 - 太陽電池用白色ポリエステルフィルム、これを用いた太陽電池裏面封止シートおよび太陽電池モジュール - Google Patents
太陽電池用白色ポリエステルフィルム、これを用いた太陽電池裏面封止シートおよび太陽電池モジュール Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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Abstract
Description
項1.
白色度が50以上、波長400〜800nmの範囲における平均反射率が50〜95%、酸価が1〜50eq/ton、厚みが30〜380μmである太陽電池用白色ポリエステルフィルムであって、
前記フィルムは、無機微粒子の含有量が10〜38質量%であるポリエステル樹脂層を少なくとも一方の最外層とした多層構造からなり、
前記ポリエステル樹脂層の表面における、突起高さに対する突起個数密度をプロットした突起分布の半値幅が200〜1000nmである、
ことを特徴とする太陽電池用白色ポリエステルフィルム。
項2.
前記ポリエステル樹脂層が、2種以上の無機微粒子を含有する層である、項1に記載の太陽電池用白色ポリエステルフィルム。
項3.
前記2種以上の無機微粒子のうち、少なくとも2種の無機微粒子の平均粒径の差が1.7μm以上である、項2に記載の太陽電池用白色ポリエステルフィルム。
項4.
前記ポリエステル樹脂層が、平均粒径が0.1μm〜1.7μmの無機微粒子I、平均粒径が1.8μm〜7.0μmの無機微粒子IIを含有し、無機微粒子Iと無機微粒子IIの平均粒径の差が1.7μm以上である、項1〜3のいずれかに記載の太陽電池用白色ポリエステルフィルム。
項5.
前記ポリエステル樹脂層が、ルチル型を主体とする二酸化チタンを少なくとも含む、項1〜4のいずれかに記載の太陽電池用白色ポリエステルフィルム。
項6.
前記ポリエステル樹脂層は硫酸バリウムを含まない、項1〜5のいずれかに記載の太陽電池用白色ポリエステルフィルム。
項7.
前記ポリエステル樹脂層の厚さは、前記無機微粒子IIの平均粒径よりも厚い、項4に記載の太陽電池用白色ポリエステルフィルム。
項8.
前記無機微粒子Iが、ルチル型を主体とする二酸化チタンである、項4に記載の太陽電池用白色ポリエステルフィルム。
項9
項1〜8のいずれかに記載の太陽電池用白色ポリエステルフィルムを用いたことを特徴とする太陽電池裏面封止シート。
項10.
項9に記載の太陽電池裏面封止シートと、太陽電池裏面封止シートに隣接する充填剤層と、充填剤層に埋設された太陽電池素子を備えることを特徴とする太陽電池モジュール。
本発明の太陽電池用白色ポリエステルフィルムに使用されるポリエステル樹脂とは、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸のごとき芳香族ジカルボン酸またはそのエステルと、エチレングリコール、ブチレングリコール、ジエチレングリコール、1,4−ブタンジオール、ネオペンチルグリコールのごときグリコールとを重縮合させて製造されるものであり、ホモポリマーであってもよく、第三成分を共重合したコポリマーであってもよい。
本発明の太陽電池用白色ポリエステルフィルムは、一方の最外層(太陽光に直接接する側であって、且つ、充填剤層と反対側)に、無機微粒子を10〜38質量%含有したポリエステル樹脂層(無機微粒子集中含有層)を有する。無機粒子集中含有層における無機微粒子の含有量は、10質量%以上35質量%以下が好ましく、11質量%以上30質量%以下がより好ましく、12質量%以上23質量%以下が更に好ましい。10質量%未満の場合、十分な白色度、転写痕隠蔽性が発現せず、38質量%を超える場合は凝集による異物の発生やフィルム品質、フィルム表面強度を低下させる懸念があるため好ましくない。
本発明の太陽電池用白色ポリエステルフィルムでは、上記無機微粒子集中含有層が少なくとも一方の最外層に配置される。このように太陽光に直接接する側の最外層に無機粒子を多く含む層を配置することにより、例えば上記フィルムをバックシートに用いたとき、フィルム自体、並びにバックシートを構成する内層の部材フィルム、シート及び接着層の紫外線などによる耐光性の劣化を効率的に防止できる。
本発明の太陽電池用白色ポリエステルフィルムは、前述したように上記無機微粒子集中含有層を最外層として含む2層以上の積層構成を有しており、上記無機微粒子集中含有層以外の層として、無機微粒子含有量の少ない他の層を含む。この他の層における無機微粒子の含有量は、上記無機微粒子集中含有層における無機微粒子の含有量より少なければよく、無機微粒子集中含有層における無機微粒子の含有量との差が10質量%以上であることが好ましい。具体的には、上記「無機微粒子含有量が少ない他の層」は、0.5質量%以上2質量%以下の無機微粒子を含有していることが好ましい。より好ましくは0.8質量%以上1.8質量%以下である。このように他の層に無機微粒子を少量含有させることによって、耐光性をより向上させることが可能となる。
本発明の太陽電池用白色ポリエステルフィルムは上記の層構成を有するが、易接着性、絶縁性、耐擦傷性などの各種機能が要求される場合、その表面がコーティングなどにより高分子樹脂の被覆層で被覆されてもよい。また、易滑性が要求される場合、上記被覆層に無機粒子および/または有機粒子が含まれてもよい。
本発明の太陽電池用白色ポリエステルフィルムの製造方法は、特に制限されるものではないが、各層形成用のポリエステルチップを別々の押出機に供給した後、溶融状態で積層して同一のダイから押し出す共押出法が好ましい。例えば、無機微粒子集中含有層を含む2層構成のフィルムを製造する場合、無機微粒子を多く含んだポリエステルチップ(無機微粒子集中含有層用樹脂チップ)と、これより無機微粒子の含有量が少ないポリエステルチップ(他の層用樹脂チップ)を別々の押出機に供給した後、溶融状態で積層して同一のダイから押し出せばよい。
本発明の太陽電池用白色ポリエステルフィルムの白色度は50以上であり、好ましくは60以上である。白色度が50未満では、隠蔽性が劣ったり、太陽電池モジュール加工時に目視でのフィルム確認が困難となり、加工効率が低下するおそれがある。
本発明の太陽電池用白色ポリエステルフィルムは、太陽電池裏面封止シートやフレキシブルな電子部材の貼合材の基材フィルム(ベースフィルム)として用いることができる。特に、本発明のフィルムは、高い環境耐久性が求められる太陽電池裏面封止シートのベースフィルムとして好適である。
本発明でいう太陽電池モジュールとは、太陽光、室内光などの入射光を取り込んで電気に変換するシステムをいい、上記太陽電池裏面封止シートと、太陽電池裏面封止シートに隣接する充填剤層と、充填剤層に埋設された太陽電池素子を備えることを特徴とする。
前述した方法により無機微粒子の平均粒径を算出した。
ポリエステルをフェノール/1,1,2,2−テトラクロロエタンの6/4(質量比)混合溶媒に溶解し、温度30℃にて固有粘度を測定した。微粒子含有のマスターバッチおよびフィルムの場合は、遠心分離により固形分を除いた後、固有粘度を測定した。
ポリエステル0.1gをメタノール2ml中に250℃で加熱分解させた後、ガスクロマトグラフィーにより定量した。
フィルムまたは原料ポリエステル樹脂の酸価は下記の方法により測定した。
フィルムまたは原料ポリエステル樹脂を粉砕し、70℃で24時間真空乾燥を行った後、天秤を用いて0.20g±0.0005gの範囲に秤量し、そのときの質量をW(g)とした。試験管にベンジルアルコール10mlと秤量した試料を加え、試験管を205℃に加熱したベンジルアルコール浴に浸し、ガラス棒で攪拌しながら試料を溶解させ、溶解時間を3分間、5分間、7分間としたときのサンプルをそれぞれA,B,Cとした。次いで、新たに試験管を用意し、ベンジルアルコールのみを入れ、同様の手順で処理し、溶解時間を3分間、5分間、7分間としたときのサンプルをそれぞれa,b,cとした。
予めファクター(NF)が分かっている0.04mol/Lの水酸化カリウム溶液(エタノール溶液)を用いて滴定した。指示薬であるフェノールレッドが黄緑色から淡紅色に変化したところを終点とし、水酸化カリウム溶液の滴定量を求めた。サンプルA,B,Cの滴定量をXA,XB,XC(ml)とし、サンプルa,b,cの滴定量をXa,Xb,Xc(ml)とした。
各溶解時間に対しての滴定量XA,XB,XCから、最小2乗法により、溶解時間0分での滴定量V(ml)を求めた。同様にXa,Xb,Xcから、溶解時間0分での滴定量V0(ml)を求めた。次いで、次式に従い酸価(eq/ton)を求めた。
酸価(eq/ton)=[(V−V0)×0.04×NF×1000]/W
フィルムの見かけ密度は、JIS K 7222「発泡プラスチックおよびゴム−見かけ密度の測定」に準拠して測定した。但し、表記を簡便にするために得られた見かけ密度の単位をg/cm3に換算した。
フィルムの白色度は、JIS L 1015−1981−B法により、日本電色工業社製のZ−1001DPを用いて測定した。
分光光度計(島津製作所社製、自記分光光度計「UV−3150」)に積分球を装着し、標準白色板(SphereOptics社製、白色標準板「ZRS−99−010−W」)の反射率を100%として校正し、分光反射率を測定した。測定は波長400〜800nmの領域で1nm刻みに行い、その平均値を求めた。測定に当たっては、無反射の黒台紙を試料フィルム背面に配し、A層側から光を当てて測定した。
耐光性を評価するため、アイスーパーUVテスター(岩崎電気社製、SUV−W151)を用い、フィルムの無機微粒子集中含有層側に63℃、50%RH、照射強度100mW/cm2で100時間の連続UV照射処理を行った。
耐加水分解性を評価するため、JIS C 60068−2−66で規格化されているHAST(Highly Accelerated temperature and humidity Stress Test)を行った。詳細には、試料フィルムを70mm×190mmにカットし、治具を用いて、各々が接触しない距離を保つように設置した。次にエスペック社製のEHS−221を用い、121℃、100%RH、0.03MPa、48時間処理を行った。
耐光性および耐加水分解性の評価は、破断伸度保持率で行った。詳細には前述した促進光劣化試験および促進加水分解試験それぞれの処理前後の破断伸度を、JIS C 2318−1997 5.3.31(引張強さおよび伸び率)に準拠して測定し、下記式に従い破断伸度保持率(%)を算出した。
破断伸度保持率(%)=[(処理後の破断伸度)×100]/(処理前の破断伸度)
促進光劣化試験後の伸度保持率が35%未満のものを×、35%以上、60%未満のものを○、60%以上のものを◎とした。
試料フィルムを40mm×40mmにカットし、X=94.19,Y=92.22,Z=110.58の標準白板を用いて、カラーb*値色差計(日本電色社製、ZE−2000)により、促進光劣化試験前後の試料フィルムのカラーb*値をJIS K 7105−1981 5.3.5(a)に準拠して測定した。下記式に従いカラーb*値の変化を求めた。
カラーb*値の変化=(促進光劣化試験後のカラーb*値)−(促進光劣化試験前のカラーb*値)
カラーb*値の変化が12より高いものを×、5〜12のものを○、5未満のものを◎とした。
試料フィルムを10mm×250mmにカットし、長辺を測定したい方向に合わせて、200mm間隔で印をつけ、5gの一定張力下で印の間隔Aを測った。続いて、試料フィルムを無荷重で150℃の雰囲気のオーブン中で30分間放置した後、オーブンから取り出して室温まで冷却した。その後、5gの一定張力下で印の間隔Bを求め、下記式により熱収縮率(%)を求めた。なお、上記熱収縮率は試料フィルムの幅方向に3等分した位置で測定し、3点の平均値を小数第3位の桁で四捨五入し、小数第2位の桁を丸めて得られたものである。
熱収縮率(%)=[(A−B)×100]/A
5cm×20cmに切り出した試料フィルムを、ポリエステル両面粘着テープAを用い、無機微粒子集中含有層側が外側となるように平板ガラスに全面接着した。試料フィルムの表面に幅24mmの粘着テープB(ニチバン社製、セロテープ(登録商標)を長さ35mmにわたって貼付して1分間放置した。この後、粘着テープBをガラス面に垂直な方向に一気に引き剥がして無機微粒子集中含有層側の表面を観察した。
フィルムを100mm×100mm、下記のEVAシートを70mm×90mmにそれぞれ切り出したものを用意し、フィルム/EVAシート/ガラスの構成で重ねて積層物を作製した。上記構成において、いずれのフィルムもB層がEVAシートに対向するように設置したが、実施例9のみ、A層の一方の面がEVAシートに対向するように設置した。このようにして得られた積層物の両面にエンボスシートを配し、後記するサンプル作製条件で上記積層物を加熱圧着し、フィルムへ凹凸が転写されたサンプルを作製した。
○:転写痕が見えない
△:転写痕がわずかに見える
×:転写痕が明瞭に見える
装置:真空ラミネーター(エヌ・ピー・シー社製、LM−30×30型)
エンボスシート:真空ラミネーター付属品(エヌ・ピー・シー社製、ガラスクロスシート)
加圧:1気圧
EVAシート:サンビック社製、ウルトラパール(登録商標)PV(0.4μm)
ラミネート工程:100℃(真空5分、真空加圧5分)
キュア工程:熱処理150℃(常圧45分)
前述した方法により、A層の突起分布の半値幅(nm)を測定した。
(1)PET樹脂ペレット(PET−I)の製造
エステル化反応缶を昇温し、200℃に到達した時点で、テレフタル酸86.4質量部およびエチレングリコール64.4質量部からなるスラリーを仕込み、攪拌しながら、触媒として三酸化アンチモンを0.017質量部およびトリエチルアミンを0.16質量部添加した。次いで、加圧昇温を行いてゲージ圧3.5kgf/cm2(343kPa)、240℃の条件で、加圧エステル化反応を行った。その後、エステル化反応缶内を常圧に戻し、酢酸マグネシウム四水和物0.071質量部、次いでリン酸トリメチル0.014質量部を添加した。さらに、15分かけて260℃に昇温し、リン酸トリメチル0.012質量部、次いで酢酸ナトリウム0.0036質量部を添加した。15分後、得られたエステル化反応生成物を重縮合反応缶に移送し、減圧下で260℃から280℃へ徐々に昇温し、285℃で重縮合反応を行った。
PET樹脂ペレットI(PET−I)を予め160℃で予備結晶化させた後、温度220℃の窒素雰囲気下で固相重合し、固有粘度0.71dl/g、酸価11eq/tonのPET樹脂ペレットII(PET−II)を得た。
(1)SiO2含有マスターバッチペレットI(SiO2 MB−I)の製造
上記PET樹脂ペレットIの製造の際に、平均粒径2.7μm(電子顕微鏡法により求めた値)のSiO2粒子をポリエステルに対して20,000ppmの割合で添加し、SiO2含有マスターバッチペレットI(SiO2 MB−I)を得た。上記ペレットIの固有粘度は0.62dl/g、酸価は17eq/tonであった。
上記のようにして得られたSiO2含有マスターバッチペレットI(SiO2 MB−I)を予め160℃で予備結晶化させた後、温度220℃の窒素雰囲気下で固相重合し、固有粘度0.71dl/g、酸価11eq/tonのSiO2含有マスターバッチペレットII(SiO2 MB−II)を得た。上記ペレットIIの固有粘度は0.71dl/g、酸価は11eq/tonであった。
上記PET樹脂ペレットIの製造の際に、平均粒径6.5μm(電子顕微鏡法により求めた値)のSiO2粒子をポリエステルに対して20,000ppmの割合で添加し、SiO2含有マスターバッチペレットを得た。このようにして得られたSiO2含有マスターバッチペレット予め160℃で予備結晶化させた後、温度220℃の窒素雰囲気下で固相重合し、表1に示すSiO2含有マスターバッチペレットIII(SiO2 MB−III)を得た。上記ペレットIIIの固有粘度および酸価も上記ペレットIIと同じであった。
上記PET樹脂ペレットIの製造の際に、平均粒径1.7μm(電子顕微鏡法により求めた値)のSiO2粒子をポリエステルに対して20,000ppmの割合で添加し、SiO2含有マスターバッチペレットを得た。このようにして得られたSiO2含有マスターバッチペレット予め160℃で予備結晶化させた後、温度220℃の窒素雰囲気下で固相重合し、表1に示すSiO2含有マスターバッチペレットIV(SiO2 MB−IV)を得た。上記ペレットIVの固有粘度および酸価も上記ペレットIIと同じであった。
(1)酸化チタン微粒子含有マスターバッチペレットI(TiO2 MB−I)の製造
原料として、予め120℃で8時間、10-3torr(約0.133Pa)下で乾燥したPET樹脂ペレットI(PET−I)50質量%に、平均粒径0.3μm(電子顕微鏡法により求めた値)のルチル型二酸化チタン50質量%を混合したものをベント式二軸押出機に供給して、混練りして脱気しながら275℃で押出し、ルチル型二酸化チタン微粒子含有マスターバッチペレットI(TiO2 MB−I)を得た。このペレットIの固有粘度は0.45dl/g、酸価は42.2eq/tonであった。
このようにして得られたペレットを用いて回転型真空重合装置で、0.5mmHgの減圧下、220℃で固相重合を行い、固有粘度0.71dl/g、酸価23.5eq/tonのマスターバッチペレットII(TiO2 MB−II)を得た。
原料として、予め120℃で8時間、10-3torr(約0.133Pa)下で乾燥したPET樹脂ペレットI(PET−I)90質量%に、平均粒径2.4μm(電子顕微鏡法により求めた値)のゼオライト10質量%を混合したものをベント式二軸押出機に供給して、混練りして脱気しながら275℃で押出し、得られたペレットを用いて回転型真空重合装置で、0.5mmHgの減圧下、220℃で固相重合を行い、固有粘度0.71dl/g、酸価23.5eq/tonのゼオライト含有マスターバッチペレット(ゼオライトMB)を得た。
下記実施例1〜9および比較例1〜6のフィルムを以下のようして製造した。これらフィルムの原料組成を上記表1にまとめて示す。
PET−IIを44質量%、TiO2 MB−IIを36質量%、SiO2 MB−IIを20質量%混合した微粒子集中含有層(A層)の原料と、PET−IIを97質量%、TiO2 MB−IIを3質量%混合した他の層(B層)の原料とをそれぞれ別々の押出機に投入し、285℃で混合した後、溶融し、続いてフィードブロックを用い、A層/B層となるように溶融状態で接合した。このとき、A層とB層の吐出量比率は、ギアポンプを用いて制御した。次いでT−ダイを用いて30℃に調節された冷却ドラム上に押出し、未延伸シートを作製した。
A層、B層の原料組成を表1のように変更した以外は、実施例1と同じ方法で太陽電池用白色ポリエステルフィルムロールを得た。
フィルムの総厚みを38μmに変更し、A層、B層の原料組成を表1のように変更した以外は、実施例1と同じ方法で太陽電池用白色ポリエステルフィルムロールを得た。
層構成をA層、B層、A層の順の積層構造に変更し、A層、B層の原料組成を表1のように変更した以外は、実施例1と同じ方法で太陽電池用白色ポリエステルフィルムロールを得た。
A層、B層の組成を表1のように変更した以外は、実施例1と同じ方法で太陽電池用白色ポリエステルフィルムロールを得た。
Claims (10)
- 白色度が50以上、波長400〜800nmの範囲における平均反射率が50〜95%、酸価が1〜50eq/ton、厚みが30〜380μmである太陽電池用白色ポリエステルフィルムであって、
前記フィルムは、無機微粒子の含有量が10〜38質量%であるポリエステル樹脂層を少なくとも一方の最外層とした多層構造からなり、
前記ポリエステル樹脂層の表面における、突起高さに対する突起個数密度をプロットした突起分布の半値幅が200〜1000nmであることを特徴とする太陽電池用白色ポリエステルフィルム。 - 前記ポリエステル樹脂層が、2種以上の無機微粒子を含有する層である請求項1に記載の太陽電池用白色ポリエステルフィルム。
- 前記2種以上の無機微粒子のうち、少なくとも2種の無機微粒子の平均粒径の差が1.7μm以上である請求項2に記載の太陽電池用白色ポリエステルフィルム。
- 前記ポリエステル樹脂層が、平均粒径が0.1μm〜1.7μmの無機微粒子I、および平均粒径が1.8μm〜7.0μmの無機微粒子IIを含有し、前記無機微粒子Iと前記無機微粒子IIの平均粒径の差が1.7μm以上である請求項1〜3のいずれかに記載の太陽電池用白色ポリエステルフィルム。
- 前記ポリエステル樹脂層が、ルチル型を主体とする二酸化チタンを少なくとも含む請求項1〜4のいずれかに記載の太陽電池用白色ポリエステルフィルム。
- 前記ポリエステル樹脂層は硫酸バリウムを含まない請求項1〜5のいずれかに記載の太陽電池用白色ポリエステルフィルム。
- 前記ポリエステル樹脂層の厚さは、前記無機微粒子IIの平均粒径よりも厚い請求項4に記載の太陽電池用白色ポリエステルフィルム。
- 前記無機微粒子Iが、ルチル型を主体とする二酸化チタンである請求項4に記載の太陽電池用白色ポリエステルフィルム。
- 請求項1〜8のいずれかに記載の太陽電池用白色ポリエステルフィルムを用いたことを特徴とする太陽電池裏面封止シート。
- 請求項9に記載の太陽電池裏面封止シートと、太陽電池裏面封止シートに隣接する充填剤層と、充填剤層に埋設された太陽電池素子を備えることを特徴とする太陽電池モジュール。
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