JP6119258B2 - 易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート - Google Patents
易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート Download PDFInfo
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- JP6119258B2 JP6119258B2 JP2013005375A JP2013005375A JP6119258B2 JP 6119258 B2 JP6119258 B2 JP 6119258B2 JP 2013005375 A JP2013005375 A JP 2013005375A JP 2013005375 A JP2013005375 A JP 2013005375A JP 6119258 B2 JP6119258 B2 JP 6119258B2
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Classifications
-
- 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
- H01L31/049—Protective back sheets
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
また、太陽電池は屋外で使用されるため、使用する部材には高い耐久性、耐候性、耐光性などが要求される。特に、前記バックシートは、長期に渡る太陽光の暴露、昼夜の温度変動、風圧や施工時の力学的変形にかかる応力に耐え、水分、酸素、窒素酸化物、硫黄酸化物等の汚染物質の浸入を阻止し、発電素子を保護することが求められる。
このような材料としては、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、四フッ化エチレン・六フッ化プロピレン共重合体、エチレン・四フッ化エチレン共重合体等のフッ素系樹脂シートや金属箔等が組み合わされて、用いられることが多い。しかしながら、フッ素系樹脂シートは高価であると同時に発電モジュールの長期高圧課電での耐久性の観点からは十分とは言えず、改良技術として様々な構成体が提案されている。
そこで近年、バックシートとして、ポリプロピレンフィルムやポリエチレンテレフタレートフィルム(以下PETフィルムと称す)等の汎用のプラスチックシートを利用する検討がなされている。しかしながら、汎用のプラスチックシートは、耐光性あるいは封止樹脂として標準的に用いられるEVAとの接着性に問題があるため、プラスチックシート自体に無機粒子を添加して耐光性を高めたり、プラスチックシートとEVAとの間に易接着層を設けて接着性を高めたりする検討がなされている。(特許文献1〜4)
しかしながら、特許文献1〜4に記載の方法では、EVAとの接着性が不十分であり、満足する性能に達しているとはいえない。加えて、EVAとの接着性を上げるには、易接着剤組成物として、ガラス転移温度の低いバインダー樹脂を用いるのが好ましいが、このようなバインダー樹脂は、逆に、耐ブロッキング性が悪化してしまう。一方、発電効率のアップ、耐侯性および耐光性等の性能付与を目的に、易接着剤組成物に顔料を含ませる検討が行われている。しかしながら、従来の易接着剤組成物では、顔料を含んだ場合に、EVAとの接着性が極端に低下し、更には、易接着剤としての貯蔵安定性にも課題が生じる。また、バックシートの基材としてPETフィルム等の加水分解を受けやすいプラスチックシートを使用する場合においては、易接着剤にも加水分解を抑制する耐加水分解性が要求される。そこで、これらの課題を解決する易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシートの開発が望まれている。
従って、本発明の目的は、市販されている多様なPETフィルムにコーティングを施すことでEVAとの接着性、耐ブロッキング性、更には耐加水分解性を付与できる易接着剤組成物を提供することである。
これらの樹脂としては、例えば、アクリルポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリオレフィン系ポリオール、ポリカーボネートポリオール、ウレタンポリオール、及び、フッ素系ポリオールからなる群から選ばれる1種以上の樹脂等が挙げられる。
硬化剤は、ポリイソシアネート化合物(C)のみでもある程度の性能が発現するが、ポリイソシアネート化合物と後述するエポキシ化合物とを積極的に併用することより、硬化塗膜により高度な耐加水分解性を付与することが出来る。
このような脂肪酸としては、例えば、花王(株)製「ルナック」シリーズ、「NAA−312」日油(株)製などが挙げられる。
本発明に用いる脂肪酸エステルを得る為の2価のアルコールとしては、例えば、エチレングリコール、1,2−プロピレングリコール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、ジエチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ネオペンチルグリコール等の脂肪族ジオール類;ビスフェノールA、ビスフェノールS、ビスフェノールF等のビスフェノール類、ビスフェノールAのポリアルキレンオキサイド付加物、ビスフェノールSのポリアルキレンオキサイド付加物、ビスフェノールFのポリアルキレンオキサイド付加物等のビスフェノールのアルキレンオキサイド付加物等のビスフェノール誘導体類等の芳香族のジオール類;シクロヘキサンジメタノール等の脂環族のジオール類等が挙げられる。
本発明に用いる脂肪酸エステルを得る為の3価以上のアルコールとしては、例えば、グリセリン、トリメチロ−ルエタン、トリメチロ−ルプロパン、ソルビト−ル、1,2,3,6−ヘキサンテトロ−ル、1,4−ソルビタン、ペンタエリスリト−ル、ジペンタエリスリト−ル、2−メチルプロパントリオ−ル、1,3,5−トリヒドロキシベンゼン、トリス(2−ヒドロキシエチル)イソシアヌレ−ト等が挙げられる。
本発明で用いる脂肪酸エステルを得る為の製造装置および製造方法についても、従来公知な方法を利用することができる。このような脂肪酸エステルとしては、例えば、新日本理化(株)製「ラウリン酸メチルエステル」、味の素ファインテクノ(株)製「アジスパー PN−411」などが挙げられる。
これらの中でも、フッ素化ポリオレフィン樹脂、表面処理したポリオレフィン樹脂類等が好ましい。
通常、太陽電池モジュールの封止樹脂として用いられるEVAは、酢酸ビニル含有量が10〜40重量%であるものを用い、太陽電池モジュールの耐熱性、物理的強度を確保するために、熱あるいは光などによりEVAを架橋している。
アリルシアヌレート、トリアリルイソシアヌレート、フタル酸ジアリル、イソフタル酸ジアリル、マレイン酸ジアリル等が配合されている。
測定装置;東ソー株式会社製 HLC−8220
検出器;RI(示差屈折計)
測定条件;カラム温度 40℃ 溶媒 テトラヒドロフラン
また、本発明に用いる水酸基を含有する樹脂(A)のガラス転移温度は、下記の条件により求めた。
測定方法;DSC(示差走査熱量分析)法
下記の表1、及び表2に示す通り、水酸基を含有する樹脂(A)、水酸基を含有する樹脂(B)、ポリイソシアネート化合物(C)、エポキシ化合物を用いて、主剤成分と硬化剤成分との二液型の、本発明及び従来の易接着剤組成物を調製した。
(EVAとの接着性評価サンプルの作製方法)
前記易接着層を設けた塗工物を幅50mm、長さ100mmに裁断したもの2枚、およびEVAシート(サンビック(株)製)を幅50mm、長さ100mmに裁断したもの1枚を用意した。
EVAとの接着性は、前記易接着性の評価用サンプルを、引張試験機((株)エー・アンド・ディー製テンシロン試験機)の上下のクリップに未接着部分のバックシートを挟み、オートグラフによるT型剥離法を用い、幅10mmのクロスヘッド速度200mm/分における剥離強度を測定した。ここで、表1及び表2記載の単位は「N/10mm」である。
バックシート2枚を易接着層面が向かい合わない方向、すなわち易接着層/基材層/易接着層/基材層の順序で重ね合わせ、5kgf/cm2の荷重をかけた状態で、40℃、24時間放置した。その後、室温に戻し、荷重をはずした状態で、下記の評価基準に基づいて評価した。
○;基材層への裏移り跡無し
△;基材層への裏移り跡あるが、裏移り無し
×;基材層への裏移り有り
材:E5001(東洋紡(株)製 PET)/X10S(東レ(株)製 耐候PET)
乾燥塗布量:6g/m2
・エリーテルUE−3210:ポリエステル樹脂(ユニチカ株式会社)固形分:100%、Tg:45℃、水酸基価:4mgKOH/g、数平均分子量:20,000
・エリーテルUE−3660:ポリエステル樹脂(ユニチカ株式会社)固形分:100%、Tg:60℃、水酸基価:4mgKOH/g、数平均分子量:20,000
・アクリディック57−451:水酸基含有アクリル樹脂(DIC株式会社)、固形分:55%、Tg:65℃、水酸基価:20
・アクトコール D−400:PPGジオール(三井化学株式会社)固形分:100%、水酸基価:280 数平均分子量:400
・アクトコール D−1000:PPGジオール(三井化学株式会社)固形分:100%、水酸基価:110 数平均分子量:1,000
・アクトコール D−2000:PPGジオール(三井化学株式会社)固形分:100%、水酸基価:55 数平均分子量:2,000
・PEG 1000:PEGジオール(日油株式会社)固形分:100%、水酸基価:115 数平均分子量:1,000
・P−1020:MPD系ポリエステルポリオール(クラレ株式会社)固形分:100%、水酸基価:110 数平均分子量:1,000
・プラクセル 220EB:ポリカプロラクトンジオール(ダイセル株式会社)固形分:100%、水酸基価:56 数平均分子量:2,200
・DURANOL T−5651:ポリカーボネートジオール(旭化成ケミカルズ株式会社)、固形分:100% 数平均分子量:1000 水酸基価:100〜120
・JR−403 テイカ(株)製 ルチル型酸化チタン、平均粒経0.25μm 表面処理Al、Si
・エピクロン860:ビスフェノールA型エポキシ樹脂(DIC株式会社) 固形分:100%、エポキシ当量:240
・スミジュールN3300:HDI系イソシアヌレート型ポリイソシアネート(住化バイエルウレタン株式会社)固形分:100%、NCO%:22%
・デュラネート TSE−100;旭化成(株)製 無黄変型ポリイソシアネート、固形分:100%、NCO%13
Claims (11)
- 水酸基価が1〜200mgKOH/g、数平均分子量が5,000〜50,000以下の水酸基を含有するアクリル樹脂(A)と数平均分子量が200〜5,000未満のポリエーテルポリオール(B)とポリイソシアネート化合物(C)を含有することを特徴とする易接着剤組成物。
- 水酸基を含有するアクリル樹脂(A)の数平均分子量が5,000以上で50,000以下、ガラス転移温度が20℃〜110℃以下である請求項1に記載の易接着剤組成物。
- 前記ポリエーテルポリオール(B)の水酸基価が40〜500である請求項1又は2のいずれか1つに記載の易接着剤組成物。
- 前記水酸基を含有するアクリル樹脂(A)と前記ポリエーテルポリオール(B)との数平均分子量の差が1000以上である請求項1〜3のいずれか1つに記載の易接着剤組成物。
- 前記水酸基を含有するアクリル樹脂(A)100部に対して、前記ポリエーテルポリオール(B)を1〜50部含有することを特徴とする請求項1〜4のいずれか1つに記載の易接着剤組成物。
- 前記ポリエーテルポリオール(B)がポリエチレングリコールジオール及びポリプロピレンジオールからなる群から選ばれる1種以上であることを特徴とする請求項1〜5のいずれか1つに記載の易接着剤組成物。
- 更に、エポキシ化合物を含有することを特徴とする1〜6のいずれか1つに記載の易接着剤組成物。
- 請求項1〜7のいずれか1つに記載の易接着剤組成物の硬化皮膜がポリエステル樹脂フィルム上に積層された積層ポリエステル樹脂フィルム。
- 請求項8に記載の積層ポリエステル樹脂フィルムを少なくとも含む、多層構造の太陽電池バックシート。
- 請求項9に記載の太陽電池バックシートと、封止材とを含む太陽電池モジュール。
- 前記封止材がエチレン−酢酸ビニル共重合体を含有する組成物である請求項10記載の太陽電池モジュール。
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