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TW201246572A - Protective sheet for solar cell, manufacturing method thereof, and solar cell module - Google Patents

Protective sheet for solar cell, manufacturing method thereof, and solar cell module Download PDF

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Publication number
TW201246572A
TW201246572A TW100137651A TW100137651A TW201246572A TW 201246572 A TW201246572 A TW 201246572A TW 100137651 A TW100137651 A TW 100137651A TW 100137651 A TW100137651 A TW 100137651A TW 201246572 A TW201246572 A TW 201246572A
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TW
Taiwan
Prior art keywords
layer
solar cell
protective sheet
substrate
resin
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TW100137651A
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Chinese (zh)
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TWI546976B (en
Inventor
Yasunari Takanashi
Naoki Taya
Marina Temchenko
David William Avison
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Lintec Corp
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Priority claimed from JP2010234071A external-priority patent/JP2012089632A/en
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of TW201246572A publication Critical patent/TW201246572A/en
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Publication of TWI546976B publication Critical patent/TWI546976B/en

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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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

The disclosed protective sheet (1) for solar cells is provided with a substrate (11) and a thermoplastic resin layer (12) laminated on at least one surface of the substrate (11). The thermoplastic resin layer (12) is provided with a first layer (121) which, laminated on the substrate (11), has as a main component a copolymer with at least one element of a group consisting of ethylene, (meth) acrylic acid, (meth) acrylic acid ester, glycidyl (meth)acrylate and vinyl acetate, and a second layer (122) which, laminated on the first layer (121), has an olefin resin as a main component. By means of this protective sheet (1) for solar cells, it is possible to achieve excellent adhesion between the substrate and the thermoplastic resin layer and to suppress warping occurring in the solar cell module.

Description

201246572 六、發明說明： 【發明所屬之技術領域】 本發明係關於當作太陽電池模組之表面保護薄板或背 面保護薄板用的太陽電池用保護薄板及其製造方法、以及 使用該太陽電池用保護薄板的太陽電池模組。 【先前技術】 將太陽的光能轉換為電能的太陽電池模組，有就因應 空氣污染、地球暖化等環保問題，能在不排放二氧化碳的 情况下可發電之潔淨能源備受矚目。 一般，太陽電池模組係由太陽電池單元（其係由結晶 矽、非晶石夕等構纟，並執行光電轉換）m陽電池單元 予以密封的電絕緣體所構成密封材（填充層）、積層於密封 材表面（受光面）上的表面保護薄板（前板）、以及積層於密 封材背面上的背面保護薄板(薄板)構成。為使太陽電池模 組能具有能承受可在室外與室内長期間使用的财候性與耐 久性’保護太陽電池單元與密封材免受風雨、濕氣、沙塵、 機械性衝擊等的傷害，，太陽電池模組内部保持呈阻 :外界空氣形成密閉狀態1而，對太陽電池用保護薄板 要求能承受長期間使用的耐濕性㈣候性。 “板 專利文獻i有揭示在薄膜其中一面上，依 機氧化物層、接著岸另勒7 有热 m #女塔^ 、、、可塑性樹脂層的太陽電池背面保 σ隻溥板。該太陽電妯發i Μ 「 皮面保護薄板係隔著熱可塑性樹脂# 被加熱壓接於密封材上。 曰層 磚膜係由諸如聚對苯二甲酸乙二 201246572 酯等樹脂構成，在該薄膜上真空蒸鍍著諸如氧化矽等並當 作無機氧化物層用。接著層係由順丁烯二酸酐改質聚乙烯 樹脂構成，熱可塑性樹脂層係由諸如聚丙烯等構成，而接 著層與熱可塑性樹脂層係利用多層共擠出積層法積層於具 無機氧化物層之薄膜（基材）上。 先行技術文獻 專利文獻 專利文獻1 :日本專利特開2008-270685號公報 【發明内容】 (發明所欲解決之課題） 的 因 組 然而’接著層係使用順丁烯二酸酐改質聚乙烯樹脂 專利文獻1之背板，因為接著層對基材的接著性偏低， 而會有基材與熱可塑性樹脂層間發生剝離、太陽電池模 内部有水蒸氣進入的問題。 再者’當將接著層與熱可塑性樹脂層施行多層共擠出 積層時，會有因積層後的冷卻而導致接著層及/或熱可塑性 樹脂層出現收縮、在輕的寬度方向或流動方向出現捲曲的 問題。若因背板的捲曲而導致太陽電池模組出現鍾曲，不 僅在太陽電池模組設置時會發生不良情況，尚會有太陽電 池模組遭受破損的可能性。201246572 VI. [Technical Field] The present invention relates to a solar cell protective sheet for use as a surface protection sheet or a back sheet for a solar cell module, a method for producing the same, and a solar cell protection Thin solar cell module. [Prior Art] A solar cell module that converts solar light energy into electric energy has attracted attention for environmentally friendly problems such as air pollution and global warming, and clean energy that can generate electricity without emitting carbon dioxide. In general, the solar cell module is composed of a solar cell unit (which is composed of a crystalline germanium, an amorphous stone, etc., and performs photoelectric conversion). The insulating material (filled layer) and the laminated layer are formed by an electrical insulator sealed by the m-yang battery unit. The surface protection sheet (front plate) on the surface of the sealing material (light receiving surface) and the back protective sheet (thin sheet) laminated on the back surface of the sealing material. In order to protect the solar cell unit and the sealing material from wind and rain, moisture, dust, mechanical shock, etc., in order to enable the solar cell module to withstand the financial and durability that can be used outdoors and indoors for a long period of time, The inside of the solar cell module is kept in a state of resistance: the outside air is in a sealed state 1 and the solar cell protective sheet is required to withstand the long-term use of moisture resistance (four). "Panel Patent Document i discloses that on the one side of the film, the solar oxide cell layer on the one side of the film, the heat-resistant m #女塔^, and the plastic resin layer on the one side of the film.妯发 i Μ "The leather protection sheet is heated and crimped to the sealing material via a thermoplastic resin #. The 曰 brick film is composed of a resin such as polyethylene terephthalate 201246572 ester, and the film is vacuumed. Evaporation such as yttrium oxide or the like is used as an inorganic oxide layer. The layer is then composed of a maleic anhydride-modified polyethylene resin, and the thermoplastic resin layer is composed of, for example, polypropylene, and the adhesive layer and thermoplasticity The resin layer is laminated on a film (substrate) having an inorganic oxide layer by a multilayer co-extrusion lamination method. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-270685 (Invention) The group to be solved, however, the following layer is used to modify the polyethylene resin of the maleic anhydride to the back sheet of Patent Document 1, because the adhesion of the adhesive layer to the substrate is low, and there is a substrate. There is a problem that peeling occurs between the thermoplastic resin layers and water vapor enters inside the solar cell mold. Further, when the adhesive layer and the thermoplastic resin layer are subjected to multilayer co-extrusion lamination, the subsequent layer may be caused by cooling after lamination. / or the thermoplastic resin layer shrinks, curling in the light width direction or the flow direction. If the solar cell module is bent due to the curl of the back sheet, not only the solar cell module will be installed. There is still the possibility that the solar cell module will be damaged.

本發明係有馨於此種實情而完成，目的在於提供：基 材與熱可塑性樹脂声問垃I p… 曰層間之接者性優異，且能抑制太陽電池 模、，且發生魅曲的太陽愈# 的太陽電池用保護薄板及其製造方法，以及 201246572 基材與熱可塑性樹脂層間之接著性優異、且能抑制勉曲的 太陽電池模組。 (解決課題之手段） 緣是，為達成上述目的，第丨，本發明所提供的太陽 電池用保護薄包括：基材、與在上述基材至少其中一 面上積層的熱可塑性樹脂層；其特徵在於：上述熱可塑性 樹脂層係包括第1層與第2^ ;該第1層係積層於上述基 材上，且以乙烯、與從（甲基）丙烯酸、（曱基）丙烯酸酯、（曱 基）丙烯酸環氧丙酯及醋酸乙烯酯所構成群組中選擇從至 少1種的共聚物為主成分；該第2層係積層於上述第1層 上’且以烯烴系樹脂為主成分。（發明1)。 上述發明（發明1)中，因為熱可塑性樹脂層的第i層 對基材之接著力較高’且第2層對太陽電池模組的密封材 之接著力較高，因而該太陽電池用保護薄板具有頗難發生 層間剝離的優點。χ，因為第】層的主成分在常溫下屬於 非晶質（非結晶），具有彈性，因而即便第2層在從加熱熔 融狀嘘進行冷卻時有出現收縮，仍可利用第1層而緩和其 收縮應力，藉此便縮小太陽電池用保護薄板的捲曲量。結 果可抑制因太陽電池用保護薄板的捲曲，而造成太陽電 池模組發生翹曲。 上述發明（發明1)中，上述第1層的上述共聚物中， 田作單體單元用之（甲基）丙烯酸、（甲基）丙烯酸酯、（曱基） 丙稀酸％氧丙酯及醋酸乙烯酯的合計含有量，較佳係 3·5〜15莫耳％。（發明2)。 201246572 "上述發明（發明卜2)中，上述第i層的上述共聚物中， 當作早體單7L用之（甲基）丙稀酸醋，較佳係從丙稀酸甲 醋、丙烯酸丁酷、丙烯酸1乙基己醋及甲基丙烯酸甲醋所 構成群組中選擇至少1種。（發明3)。 上述發明(發明卜3)中，上述第2層的上述稀烴系樹 脂，較佳係含有當作單體單元用的乙稀6〇〜1〇〇質量 明4)。 上述發明(發明卜4)中’較佳上述第2層的上述稀煙 糸樹脂係密度875〜92Gkg/m3，利用微分掃描熱量計所獲得 融解熱量ΔΗ係i00.0J/g以下。（發明5)。 上述發明（發明卜5)中，上述熱可塑性樹脂層較佳係 利用上述第1層盥上诫笸9 a w 边第2層進行共擠出塗佈而形成。（發 明6)。 上述發明（發明i，中，較佳上述基材的厚度係 〇 // m上述熱可塑性樹脂層的厚度係上述基材厚度的 倍（發月7)。藉由基材的厚度、與熱可塑性樹脂層 t厚度滿足該條件，便可使太陽電池用保護薄板的捲曲量 k為更小，結果可更有效地抑制因太陽電池用保護薄板捲 曲而造成太陽電池模組發生翹曲情形。 上述發明(發明卜7)中’較佳上述第1層的厚度盘上 述第2層的厚度之比率係1:913。（發明8)。 上述發明（發明〗〜 與構成太陽電池模㈣密封材^ 熱可塑性樹脂層係 保，，且的进封材相接著之層。（發明9)。 第2’本發明所提供的太陽電池用保護薄板之製造方 6 201246572 法，ι逅匕括基材、與在上述基材至少其中一面上積層的 熱可塑性樹脂層之太陽電池用保護薄;其特徵在於形成 包括第1層與第2層的上述熱可塑性樹脂層；該第j層係 由將以乙烯、與從（甲基）丙烯酸、（甲基）丙烯酸酯、（甲基） 丙烯酸環氧丙酯及醋酸乙烯酯所構成群組中選擇至少1種 的共聚物為主成分之第i樹脂組成物’以及以烯烴系樹脂 為主成分的第2樹脂組成物，依上述帛i樹脂組成物靠上 述基材側的方式，共擠出塗佈於上述基材至少其中一面 上，而積層於上述基材上的上述第丨樹脂組成物構成；該 第2層係由上述第！層上積層的上述第2樹脂組成物構 成。（發明10)。 第3，本發明所提供的太陽電池模組，包括：太陽電 池單元、將上述太陽電池單元予以密封的密封材、以及在 上述密封材上積層的保護薄板；其特徵在於：上述保護薄 板係由上述太陽電池用保護薄板（發明9)構成；上述保護 薄板係隔著上述熱可塑性樹脂層接著於上述密封材上。 明 11) 〇 (發明效果） 本發明的太陽電池用保護薄板係基材與熱可塑性樹脂 層間之接著性優異、且捲曲量小，因而可抑制太陽電池模 組發生翹曲。又，根據本發明的太陽電池用保護薄板之製 k方法，可獲得具有如上述優異效果的太陽電池用保護薄 板。又，本發明的太陽電池模組係基材與熱可塑性樹脂層 間之接著性優異，且能抑制因保護薄板捲曲而造成的翹曲。 201246572 【實施方式】 以下’針對本發明的實施形態進行說明。 〔太陽電池用保護薄板〕 如第1圖所示，本實施形態的太陽電池用保護薄板i， 係包括：基材11、以及在基材11其中一面（第1圖中的上 側面）所積層的熱可塑性樹脂層12 ^該太陽電池用保護薄 板1係當作太陽電池模組的表面保護薄板（前板）或背面保 護薄板（背板）使用。 基材11只要係具有電絕緣性，且熱可塑性樹脂層i 2 能積層便可，通常係使用以樹脂薄膜為主體者。 基材11所使用的樹脂薄膜，係選擇一般被使用為太陽 電池模組用背板之樹脂薄膜者。此種樹脂薄膜係可使用例 如由諸如：聚乙烯、聚丙烯等聚烯烴系樹脂；聚對苯二甲 酸乙二酯（PET)、聚萘二甲酸乙二酯等聚酯系樹脂；尼龍（商 品名）等聚醯胺系樹脂；聚碳酸酯系樹脂、無規聚苯乙烯、 間規聚苯乙烯(SPS)等聚苯乙烯系樹脂；聚丙烯腈系樹脂、 聚氯乙烯系樹脂、聚乙烯縮醛系樹脂、聚乙烯丁醛系樹脂、 氟系樹脂等樹脂所構成的薄膜或薄板。該等樹脂薄膜之 中，較佳係由聚酯系樹脂構成的薄膜、更佳係薄膜。 另外，上述樹脂薄膜視需要亦可含有諸如：顏料、紫 外線吸收劑、紫外線安定劑、難燃劑、可塑劑、抗靜電劑、 滑劑、抗黏合劑等各種添加劑。顏料係可例如：二氧化欽、 碳黑等。X，紫外線吸收劑係可例如：二苯基_系、苯并 8 201246572 三。坐系、草酸苯胺系、氰基丙稀酸醋系、三π井系等。 此處，當將本實施形態的太陽電池用保護薄板丨，使 用為太陽電池模組之背板的情況，樹脂薄膜較佳係含有使 可見光反射的顏料。又，當將本實施形態的太陽電池用保 護薄板1，使用為太陽電池模組之前板的情況，較佳係未 含有會使可見光穿透率降低的顏料，在耐候性提升之目的 下，更佳係含有線外線吸收劑。 在樹脂薄膜積層熱可塑性樹脂層12之一側的面上，為 提升與熱可塑性樹脂層12間之密接性，最好施行諸如：電 暈處理、電漿處理、底漆處理等表面處理。 基材11的厚度係根據對太陽電池模組所要求的電絕 緣性而適當設定。例如當基材u係樹脂薄膜的情況，其厚 度較佳係10〜300 // m。特別係與後述熱可塑性樹脂層12間 之關係’為更加降低太陽電池用保護薄板}的捲曲量，且 亦從電絕緣性與輕量化的觀點，基材u的厚度較佳係 5〇〜250 /zm、更佳係6〇~2〇〇#m、特佳係75〜15〇“爪。 β本實施形態的熱可塑性樹輯12係'為將太陽電池用 保遵溝板1接著於太陽電池模組的密封材者，本發明並不 僅偈限於此。 材11上積層 層122構成。 本實施形態的熱可塑性樹脂層12係由：在基 的第1層121、與在第1層121上積層的第2 第1層121係以乙稀、與從（甲基）丙稀酸、（甲基）丙 烯酸醋、（甲幻丙烯酸環氧丙酿及醋酸乙烯@旨所構成群組 中選擇至少1種的共聚物(以下稱「共聚物F」）為主成分， 9 201246572 而第2層122係以烯烴系樹脂為主成分。由上述材料構成 的第1層121係對基材U(特別係由樹脂薄膜構成的基材 11)、以及由PET薄膜構成的基材n之接著力較高。所以， 本實施形㈣太陽電池用保護薄板^為基材_孰可塑 性樹脂層12間之接著性優異。另-方面，以嫦烴系樹脂為 主成分的第2層122,利用烯烴系樹脂的優異熱熔接作用， 對太陽電池模組的密封材之接著力較冑。因為該等接著力 較高’因而本實施形態的太陽電池用保護薄板丄不易有層 間剝離情形，藉此可長期間保護太陽電池模組的内部。曰 再者，屬於第1層121之主成分的共聚物F，在常溫 下係屬於非晶質（非結晶）’具有彈性。所以以烯煙系樹 脂為主成分的第2 I 122 ’即便從加熱溶融狀態進行冷卻 時有發生收縮，仍可利用第1層⑶緩和該收縮應力。因 而’即便第^121與第2層⑵對基材u的形成係依共 擠出塗佈實施時’仍不易生成朝基㈣作用的應力，所以 太陽電池用保護薄板i的捲曲量變小。藉此，可抑制因太 陽電池用保護薄板i的捲曲而導致太陽電池模組發生麵曲 情況。具體而言，當將太陽電池用保護薄& i切取為 3〇〇miflX3〇〇ram正方形，並載置於水平平台上之時，若朝垂 直方向的捲曲量在2Gmm以下’便可抑制太陽電池模組的魅 曲，根據包括以上述丑聚铷p丸+上、、 ，、〜物F為主成分之第1層121的太 陽電池用保護薄板i，可將該捲曲量抑制在I以下。 屬於第1層121之主成分的共聚物F較佳係乙稀斑（甲 基）丙稀酸的共聚物、乙稀與（甲基）丙稀酸醋的共聚物、乙 201246572 烯與（甲基）丙烯酸環氧丙酯的共聚物、乙烯與（甲基）丙烯 酸及（甲基）丙烯酸環氧丙酯的共聚物、乙烯與（曱基）丙烯 酸及順丁烯二酸酐的共聚物、或乙烯與醋酸乙烯酯的共聚 物’更佳係乙烯與（曱基）丙烯酸酯的共聚物、或乙烯與醋 酸乙烯酯的共聚物。第i層121係可單獨使用該等共聚物 中之1種、或組合使用2種以上。另外，本說明書中所謂 「（曱基）丙烯酸酯」係指丙烯酸酯與甲基丙烯酸酯二者的 含意。其他類似用詞亦同。 (甲基）丙烯酸酯較佳係烷基碳數1〜i 8的（甲基）丙烯 酸烷基酯，可例如：（曱基）丙烯酸曱酯、（曱基）丙烯酸乙 酉曰、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、丙稀酸-2_ 乙基己醋等。該等之中’較佳係丙烯酸曱酯、丙烯酸丁酯、 丙烯酸-2-乙基己基及甲基丙烯酸曱酯，可單獨使用1種、 或組合使用2種以上。 上述共聚物F中’單體單元的（甲基）丙烯酸、（曱基） 丙烯酸醋、（曱基）丙烯酸環氧丙酯及醋酸乙烯酯之合計含 有里 車乂佳（卞3. 5〜15莫耳％、更佳係4 ~ 14莫耳％。即，乙 烯與（甲基）丙烯酸的共聚物中之（曱基）丙烯酸含有量、乙 烯與（甲基）丙烯酸酯的共聚物中之（曱基）丙烯酸酯含有 量、乙烯與（甲基）丙烯酸環氧丙酯的共聚物中之（甲基）丙 烯酸環氧丙酯含有量、乙烯與醋酸乙烯酯的共聚物中之醋 酸乙烯酯含有量’較佳係3. 5〜15莫耳％、更佳係4〜14莫耳 % ° 藉由（曱基）丙烯酸、（甲基）丙烯酸酯、（曱基）丙烯酸 11 201246572 環氧丙酯及醋酸乙烯酯的合計含有量在上述範圍内， 對基材11的高接著力與捲曲抑制效果便可更加明顯。另 外’當（甲基）丙烯酸、（甲基）丙烯酸酯、（甲基）丙歸酸環 氧丙酷、及醋酸乙烯酯的合計含有量未滿3. 5莫耳％時，會 有對基材11與第2層122的接著力偏低之情況，若達15 莫耳％以上時，無法獲得充分凝聚力，當太陽電池用保護薄 板1進行捲取時’會有發生捲取位移的可能性。 第1層121係只要含有以上述共聚物f為主成分便可， 具體而言，較佳係該共聚物F含有達60質量％以上、更佳 係含有達80質量％以上、特佳係含有達9〇質量％以上。第 1層121，當然亦可僅由共聚物f構成。 第2層122係以烯烴系樹脂為主成分。烯烴系樹脂係 可舉例如：超低密度聚乙烯（VLDPE，密度：88〇kg/m3以上、 且未滿91〇kg/m3)、低密度聚乙稀（LDpE，密度：9i〇kw 以上、且未滿915kg/m3)、中密度聚乙烯（MDpE，密度： 915kg/m以上、且未滿942kg/m3)、高密度聚乙烯⑽π， 密度：942kg/ra3以上）等聚乙烤樹脂、聚丙稀樹脂（pp)、聚 乙聚丙烯聚合物、烯烴系彈性體(τρ〇)、環烯烴樹脂等， 可單獨使用1種、或混合使用2種 。 再者’上述烯烴系樹脂之中，單體單元較佳係含有 烯60〜1〇〇質量％、 重。更佳70〜99. 5質量％的聚乙烯系樹脂。 聚乙烯系樹脂係加工適性優異， u旺馒兵且對太陽電池模組的密 材、特別係對由同樣屬# 7t 屬；乙烯糸的乙烯-醋酸乙烯酯共聚 構成的密封材，親和性古 + 性冋且接者性非常優異。甚至更 12 201246572 係從加熱熔融狀離- 〜、進仃令卻時的收縮率較小之超低密度聚 、：在度聚乙烯’最佳係超低密度聚乙烯。 晞,系樹脂較佳係密度為875〜92°kg/m3、更佳係 ^ g/m且利用微分掃描熱量計所獲得融解熱量△ H 較佳係 1 0 〇, 〇 j / p· w 下、更佳係95J/g以下。密度係根據 JIS K7112進行測b 依如上述’因為低密度或超低密度、且融解熱量低， P、°曰曰&低㈣㈣樹脂’在從加祕融狀態進行冷卻時 的收縮率亦非常小，因而本實施形態的太陽電池用保護薄 板1可成為捲曲量更小者。 另外，右烯烴系樹脂的密度未滿875kg/m3,第2層122 會發生黏疼’導致所捲取的太陽電池用保護薄1上發生 黏合貼附’造成在繞出的太陽電池用保護薄板1表面上出 現黏合貼附痕跡、或所捲取的太陽電池用保護薄板！無法 繞出之可能性。 …/ 第2層1 22係只要含有以烯烴系樹脂為主成分便可， 具體較佳係含有烯烴系樹脂達60質量％以上、更佳係含有 達80質量％以上、特佳係含有達9〇質量％以上。第2層I。 當然亦可僅由烯烴系樹脂構成。 第1層121的共聚物F及第2層122的烯烴系樹脂之 熔體流動速率（MFR)，較佳係卜20g/l〇min、$ & ^ 尺佳係 2〜lOg/lOmin。藉由二樹脂的MFR在上述範圍内， 乐 1層 121與第2層122便可利用共擠出塗佈形成。 第1層121與第2層122係除上述主成分的樹脂之外， 13 201246572 視需要尚可含有諸如：顏料、紫外繞 方卜線及收劑、t外線安定 劑 '難燃劑、可塑劑、抗靜電劑、滑 ^ 抗點合劑等各種 添加劑。 熱可塑性樹脂層12的厚度，較佳係基材 1/3〜2倍、更佳係〇·4〜倍、特佳係οι” 2倍^由 熱可塑性樹脂層12係由滿足上述條件的第…二Η 層122構成’太陽電池用保護薄板1的捲曲量便會變為更 小’結果可更有效地抑制因太陽電池用保護薄板^的捲 曲，而造成太陽電池模组發生翹曲情形。 此處，第丄層m的厚度、與第2層122的厚户比率， 較佳係1:9~7:3、更佳係1.5:8.5〜6.5:3.5、特;係2: ^卜藉由第…”的厚度與第…以的厚度比率 在上述範圍内，本實施形態的太陽電池用保護薄板^便巧 成為捲曲量更小者。 盘第1層121的厚度係在能發揮對基材11的所需接著性 與應力緩和性，且不致損及本發明效果之前提下，1餘並 無特別的限制。具體而言…層121的厚度較佳係 15〇 A m '更佳係10〜1〇〇 β m、特佳係15 75 α爪。 第2層122的厚度係在能發揮對密封材的所需接著 ,且不致損及本發明效果之前提下，其餘並無特別的限 具體而言，第2層122的厚度較佳係1〇〜2〇〇 " m、更 佳係15〜150# ^、特佳係25〜100# m。 另外’本實施形態的熱可塑性樹脂層12，係由第1層 **、第2層12 2構成’惟本發明並不僅倡限此，在不致 14 201246572 損及本發明效果之前提下，尚可包括其他層。例如亦可在 第1層121與第2層122之間設置第3層。 此處，如第2圖所示，在基材u未積層上述熱可塑性 樹脂層12之-側的面（第2圖中的下側面），較佳係設有氣 樹脂層13。依此藉由設置就樹脂層13，便可提升太陽電池 用保護薄板1的耐候性與耐藥性。另外，當基材u係由樹 脂薄膜構成的情況，該樹脂薄膜有積層著氟樹脂層13之一 側的面，為提升與氟樹脂層13間之密接性，較佳係施行諸 如電暈處理、電漿處理、底漆處理等表面處理。 氟樹脂層13係在屬於含氟之層的前提下’其餘並無特 別，限制，例如設有含貌樹脂的薄板（含氟樹脂薄板）、由 含氟樹脂的塗料施行塗佈而成的塗膜等構成。該等之中， =求太陽電池用保護薄板Μ輕量化，就從㈣脂層以 ，寻的觀點，較佳係由含I樹脂的塗料施行塗佈而成之塗膜。 含氟樹脂薄板係可使用例如將以諸如聚氟乙烯 )乙烯—氟氣乙婦（ECTFE)、或乙烯四氣乙稀⑽阳 :主成分的樹脂’加工為薄板狀者…VF為主成分的樹 ；Π^Ε· L ^ ?〇nt ^ 例2 Tedlar」（商品名）。以咖£為主成分的樹脂係可 如 Solvay Solexis 公司劁的「1 .The present invention has been completed in such a manner, and aims to provide a substrate and a thermoplastic resin, which are excellent in the connection between the layers, and which can suppress the solar cell mold and the sun that is enchanting. The solar cell protective sheet and the method for producing the same, and the solar cell module having excellent adhesion between the substrate and the thermoplastic resin layer and capable of suppressing distortion. (Means for Solving the Problem) In order to achieve the above object, a protective film for a solar cell according to the present invention includes: a substrate; and a thermoplastic resin layer laminated on at least one side of the substrate; The thermoplastic resin layer includes a first layer and a second layer; the first layer is laminated on the substrate, and is made of ethylene, (meth)acrylic acid, (meth)acrylic acid ester, or In the group consisting of glycidyl acrylate and vinyl acetate, at least one type of copolymer is selected as a main component; the second layer is laminated on the first layer' and an olefin resin is used as a main component. (Invention 1). In the above invention (Invention 1), since the adhesion of the i-th layer of the thermoplastic resin layer to the substrate is high and the adhesion of the second layer to the sealing material of the solar cell module is high, the solar cell protection is performed. The sheet has the advantage that it is difficult to cause interlayer peeling. χBecause the main component of the 】 layer is amorphous (non-crystalline) at normal temperature and has elasticity, even if the second layer shrinks when it is cooled from the heated fused crucible, it can be alleviated by the first layer. The shrinkage stress thereof reduces the amount of curling of the protective sheet for solar cells. As a result, the solar cell module is warped due to the curl of the protective sheet for the solar cell. In the above invention (Invention 1), among the copolymers of the first layer, (meth)acrylic acid, (meth)acrylic acid ester, (mercapto)acrylic acid oxypropylester and the like are used as a monomer unit. The total content of vinyl acetate is preferably from 3 to 5 mol%. (Invention 2). 201246572 "In the above invention (Invention 2), the above-mentioned copolymer of the i-th layer is used as the (meth)acrylic acid vinegar for the early single 7L, preferably from the methyl acetoacetate or the acrylic acid. At least one selected from the group consisting of Dingku, acrylic acid ethyl hexanoic acid and methyl methacrylate vinegar. (Invention 3). In the above invention (Invention 3), the above-mentioned dilute hydrocarbon resin of the second layer preferably contains ethylene 6 〇 1 当作 as a monomer unit. In the above invention (Invention 4), it is preferable that the above-mentioned thin layer of the above-mentioned dilute niobium resin has a density of 875 to 92 Gkg/m3, and the heat of fusion ΔΗ is i00.0 J/g or less obtained by a differential scanning calorimeter. (Invention 5). In the above invention (Invention 5), the thermoplastic resin layer is preferably formed by co-extrusion coating the second layer of the first layer of the upper layer 9 aw. (Claim 6). In the above invention (invention i, it is preferable that the thickness of the base material is 〇//m, and the thickness of the thermoplastic resin layer is a multiple of the thickness of the base material (moon 7). The thickness of the substrate, and the thermoplasticity When the thickness of the resin layer t satisfies the condition, the curl amount k of the protective sheet for a solar cell can be made smaller, and as a result, it is possible to more effectively suppress the warpage of the solar cell module caused by the curl of the protective sheet for a solar cell. (Invention 7) The ratio of the thickness of the second layer of the thickness plate of the first layer is preferably 1:913. (Invention 8) The invention (invention) ~ and the solar cell module (4) sealing material ^ heat The plastic resin layer is secured, and the sealing material is next to the layer. (Invention 9) The second invention of the present invention provides a solar cell protective sheet 6 201246572 method, including a substrate, and a protective film for a solar cell having a thermoplastic resin layer laminated on at least one of the substrates; characterized by forming the thermoplastic resin layer including the first layer and the second layer; the j-th layer is made of ethylene, With (meth) propyl An ith resin composition in which at least one type of copolymer is selected from the group consisting of an acid, a (meth) acrylate, a (meth) acrylate, a propyl acrylate, and a vinyl acetate, and an olefin resin The second resin composition of the main component is coextruded and applied to at least one surface of the substrate so that the 帛i resin composition is on the substrate side, and the ruthenium resin laminated on the substrate The second layer is composed of the second resin composition laminated on the first layer. (Invention 10). Third, the solar battery module provided by the present invention includes: a solar battery unit, a sealing material for sealing the solar battery unit and a protective sheet laminated on the sealing material; wherein the protective sheet is composed of the solar battery protective sheet (Invention 9); the protective sheet is separated by the heat The plastic resin layer is bonded to the above-mentioned sealing material. 11) The effect of the invention is excellent in the adhesion between the protective sheet substrate for a solar cell and the thermoplastic resin layer of the present invention. In addition, according to the method for producing a protective sheet for a solar cell of the present invention, a protective sheet for a solar cell having the above-described excellent effects can be obtained. The solar cell module-based substrate and the thermoplastic resin layer have excellent adhesion to each other, and can suppress warpage caused by curling of the protective sheet. 201246572 [Embodiment] Hereinafter, an embodiment of the present invention will be described. Protective Sheet According to Fig. 1, the solar cell protective sheet i of the present embodiment includes the substrate 11 and the thermoplasticity deposited on one side of the substrate 11 (the upper side in Fig. 1). Resin layer 12 The solar cell protective sheet 1 is used as a surface protective sheet (front sheet) or a back protective sheet (back sheet) of a solar cell module. The base material 11 may be electrically insulating, and the thermoplastic resin layer i 2 may be laminated, and a resin film is usually used as a main component. The resin film used for the substrate 11 is selected from those generally used as a resin film for a back sheet for a solar cell module. As such a resin film, for example, a polyolefin resin such as polyethylene or polypropylene; a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate; and nylon (commodity) can be used. Polyamide type resin, polycarbonate resin, random polystyrene, polystyrene resin such as syndiotactic polystyrene (SPS), polyacrylonitrile resin, polyvinyl chloride resin, polyethylene A film or sheet made of a resin such as an acetal resin, a polyvinyl butyral resin or a fluorine resin. Among these resin films, a film made of a polyester resin or a film which is more preferable is preferable. Further, the above resin film may contain various additives such as a pigment, an ultraviolet absorber, an ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a slip agent, and an anti-adhesive agent, as needed. The pigment system can be, for example, dioxins, carbon black or the like. X, the ultraviolet absorber may be, for example, diphenyl-based, benzo-8 201246572 III. Sit, oxalic acid aniline, cyanoacrylic acid vinegar, three π well system, and the like. Here, in the case where the solar cell protective sheet of the present embodiment is used as a back sheet of a solar cell module, the resin film preferably contains a pigment that reflects visible light. Further, when the solar cell protective sheet 1 of the present embodiment is used as a front panel of a solar cell module, it is preferable that the pigment for lowering the visible light transmittance is not contained, and the weather resistance is improved. The best system contains an external line absorbent. On the surface on one side of the resin film-laminated thermoplastic resin layer 12, in order to improve the adhesion to the thermoplastic resin layer 12, surface treatment such as corona treatment, plasma treatment, and primer treatment is preferably performed. The thickness of the substrate 11 is appropriately set in accordance with the electrical insulation required for the solar cell module. For example, in the case of a substrate u-based resin film, the thickness is preferably 10 to 300 // m. In particular, the relationship between the relationship between the thermoplastic resin layer 12 and the thermoplastic resin layer 12 described later is a reduction in the amount of curl of the solar cell protective sheet, and the thickness of the substrate u is preferably from 5 to 250 from the viewpoint of electrical insulation and weight reduction. /zm, more preferably 6〇~2〇〇#m, especially good 75~15〇“claw. β thermoplastic structure of this embodiment 12 series” is to use the solar cell with the Baoshougou board 1 followed by the sun In the sealing material of the battery module, the present invention is not limited thereto. The material 11 is formed of a laminate layer 122. The thermoplastic resin layer 12 of the present embodiment is composed of a first layer 121 and a first layer 121. The second layer 121 of the upper layer is selected from the group consisting of ethylene, and a group consisting of (meth)acrylic acid, (meth)acrylic acid vinegar, (methic acid acrylic acrylonitrile, and vinyl acetate@ At least one type of copolymer (hereinafter referred to as "copolymer F") is a main component, 9 201246572, and the second layer 122 is mainly composed of an olefin resin. The first layer 121 composed of the above materials is a pair of substrates U ( In particular, the substrate 11 made of a resin film and the substrate n made of a PET film have a high adhesion force. In the fourth embodiment, the protective layer of the solar cell is used as the substrate. The second layer 122 containing the hydrocarbon-based resin as the main component has excellent heat of the olefin resin. The welding action has a higher adhesion to the sealing material of the solar cell module. Because of the higher adhesion force, the solar cell protective sheet of the present embodiment is less prone to interlayer peeling, thereby protecting the solar cell for a long period of time. Further, the copolymer F belonging to the main component of the first layer 121 is amorphous (non-crystalline) at normal temperature. Therefore, the second component containing the olefin resin is the second component. I 122 'The shrinkage occurs even when cooling from the heated molten state, and the first layer (3) can be used to alleviate the shrinkage stress. Thus, even the formation of the substrate u by the 121st and the second layer (2) is coextruded. When the cloth is applied, it is difficult to generate a stress acting on the base (four), so that the amount of curling of the protective sheet for solar cells is small. Thereby, it is possible to suppress the surface of the solar cell module from being curled by the curl of the protective sheet for solar cells i. In particular, when the solar cell protection thin film & i is cut into 3〇〇miflX3〇〇ram squares and placed on a horizontal platform, if the amount of curl in the vertical direction is below 2Gmm, In the solar cell protective sheet i including the first layer 121 mainly composed of the above-mentioned ugly granules, the upper layer, and the upper portion F, the curl amount can be suppressed in the glare of the solar cell module. I. The copolymer F belonging to the main component of the first layer 121 is preferably a copolymer of ethylene (meth)acrylic acid, a copolymer of ethylene and (meth)acrylic acid vinegar, and B 201246572 olefin. Copolymer with (meth)acrylic acid propylene acrylate, copolymer of ethylene with (meth)acrylic acid and (meth)acrylic acid propyl acrylate, copolymerization of ethylene with (meth)acrylic acid and maleic anhydride The copolymer of ethylene or vinyl acetate is more preferably a copolymer of ethylene and (mercapto) acrylate or a copolymer of ethylene and vinyl acetate. The i-th layer 121 may be used alone or in combination of two or more. In the present specification, the term "(fluorenyl) acrylate" means both acrylate and methacrylate. Other similar terms are the same. The (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms, and may be, for example, (mercapto) decyl acrylate, (mercapto) acrylate, (methyl) Propyl acrylate, butyl (meth) acrylate, acrylic acid - 2 - ethyl hexanoic acid, and the like. Among these, it is preferably decyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and decyl methacrylate, and they may be used alone or in combination of two or more. The total of the monomeric units of the (meth)acrylic acid, (mercapto)acrylic acid vinegar, (meth)acrylic acid propyl acrylate and vinyl acetate in the above-mentioned copolymer F. % by mole, more preferably 4 to 14 mole %, that is, the amount of (mercapto)acrylic acid in the copolymer of ethylene and (meth)acrylic acid, and the copolymer of ethylene and (meth)acrylate ( The content of thiol) acrylate content, the content of glycidyl (meth) acrylate in the copolymer of ethylene and glycidyl (meth) acrylate, and the vinyl acetate content in the copolymer of ethylene and vinyl acetate The amount 'is preferably 3. 5 to 15 mol %, more preferably 4 to 14 mol % ° by (fluorenyl) acrylic acid, (meth) acrylate, (mercapto) acrylic acid 11 201246572 propylene acrylate When the total content of the vinyl acetate is within the above range, the high adhesion force and the curl suppressing effect on the substrate 11 can be more remarkable. Further, 'when (meth)acrylic acid, (meth)acrylic acid ester, (methyl) A total amount of acryl acrylate and vinyl acetate When the amount is less than 3.5 mol%, there is a case where the adhesion force to the substrate 11 and the second layer 122 is low, and if it is 15 mol% or more, sufficient cohesive force cannot be obtained, and the protective sheet for solar cells 1 When the coiling is performed, the coiling displacement may occur. The first layer 121 may contain the copolymer f as a main component, and specifically, the copolymer F preferably contains 60% by mass or more. More preferably, it is 80% by mass or more, and particularly preferably 9% by mass or more. The first layer 121 may of course be composed only of the copolymer f. The second layer 122 is mainly composed of an olefin resin. Examples of the olefin resin include ultra low density polyethylene (VLDPE, density: 88 〇 kg/m 3 or more, and less than 91 〇 kg/m 3 ), and low density polyethylene (LDpE, density: 9 i 〇 kw or more, And less than 915kg/m3), medium density polyethylene (MDpE, density: 915kg/m or more, and less than 942kg/m3), high-density polyethylene (10)π, density: 942kg/ra3 or more), such as poly-baked resin, polypropylene Dilute resin (pp), polyethylene-polypropylene polymer, olefin-based elastomer (τρ〇), cycloolefin resin, etc. Used alone or as a mixture thereof. In the above olefin-based resin, the monomer unit preferably contains 60 to 1% by mass of the olefin. More preferably, it is 70 to 99.5% by mass of a polyethylene resin. The polyethylene resin is excellent in processing suitability, and the adhesive material of the solar cell module is particularly suitable for the sealing material composed of the copolymer of the same genus #7t and ethylene-vinyl acetate. + Sexuality is very good. Even 12 201246572 is an ultra-low-density polyethylene that has a small shrinkage ratio when heated and melted--, and has a small shrinkage ratio.晞, the resin preferably has a density of 875~92°kg/m3, more preferably g/m, and the heat of fusion obtained by the differential scanning calorimeter ΔH is preferably 10 〇, 〇j / p·w More preferably, it is 95J/g or less. The density is measured according to JIS K7112. b. According to the above, because of low density or ultra-low density, and low heat of fusion, P, °曰曰 & low (four) (four) resin's shrinkage rate when cooling from the secret state is also very Therefore, the solar cell protective sheet 1 of the present embodiment can be made smaller in curl amount. In addition, the density of the right olefin resin is less than 875 kg/m3, and the second layer 122 may cause a sticky pain, which causes the adhesive to be attached to the protective film 1 of the solar cell to be wound up. 1 There are adhesion marks on the surface, or the protective sheet for solar cells that is taken up! Unable to circumvent the possibility. The second layer 1 22 is preferably composed of an olefin resin as a main component, and particularly preferably contains 60% by mass or more of the olefin resin, more preferably 80% by mass or more, and particularly preferably 9%. 〇% by mass or more. Layer 2 I. Of course, it may be composed only of an olefin resin. The melt flow rate (MFR) of the copolymer F of the first layer 121 and the olefin resin of the second layer 122 is preferably 20 g/l 〇 min, and the mass ratio is 2 to 10 g/lOmin. By the MFR of the two resins being within the above range, the Le 1 layer 121 and the second layer 122 can be formed by coextrusion coating. The first layer 121 and the second layer 122 are in addition to the resin of the above-mentioned main component, and 13 201246572 may contain, for example, a pigment, an ultraviolet wrapper and a collector, a t-stabilizer, a flame retardant, and a plasticizer. , antistatic agents, anti-spotting agents and other additives. The thickness of the thermoplastic resin layer 12 is preferably 1/3 to 2 times, more preferably 〇·4 倍, and 倍 倍 2 times. The thermoplastic resin layer 12 is made of the above-mentioned conditions. The second layer 122 constitutes 'the amount of curling of the protective sheet for solar cells 1 becomes smaller'. As a result, the curl of the solar cell protective sheet can be more effectively suppressed, and the solar cell module is warped. Here, the thickness of the second layer m and the ratio of the thickness of the second layer 122 are preferably 1:9 to 7:3, more preferably 1.5:8.5 to 6.5:3.5, and the system 2: In the above range, the thickness of the first ... and the thickness of the first layer are in the above range, and the protective sheet for a solar cell of the present embodiment is preferably a smaller amount of curl. The thickness of the first layer 121 of the disk is not particularly limited as long as it exhibits desired adhesion to the substrate 11 and stress relaxation, and does not impair the effects of the present invention. Specifically, the thickness of the layer 121 is preferably 15 〇 A m 'more preferably 10 to 1 〇〇 β m and more excellent 15 75 α claws. The thickness of the second layer 122 is raised before the desired sealing of the sealing material can be exerted, and the effect of the present invention is not impaired, and the rest is not particularly limited. Specifically, the thickness of the second layer 122 is preferably 1〇. ~2〇〇" m, better system 15~150# ^, especially good 25~100# m. Further, the thermoplastic resin layer 12 of the present embodiment is composed of the first layer ** and the second layer 12 2, but the present invention is not limited thereto, and it is not limited until 14 201246572 is used to impair the effects of the present invention. Other layers may be included. For example, a third layer may be provided between the first layer 121 and the second layer 122. Here, as shown in Fig. 2, the gas resin layer 13 is preferably provided on the surface (the lower side in Fig. 2) on the side of the substrate u on which the thermoplastic resin layer 12 is not laminated. By providing the resin layer 13 in this manner, the weather resistance and chemical resistance of the protective sheet for solar cells 1 can be improved. In addition, when the base material u is composed of a resin film, the resin film has a surface on one side of the fluororesin layer 13, and in order to improve adhesion to the fluororesin layer 13, it is preferable to perform corona treatment. Surface treatment such as plasma treatment and primer treatment. The fluororesin layer 13 is not particularly limited as long as it is a layer containing fluorine. For example, a thin plate containing a resin (a fluorine-containing resin sheet) and a coating material coated with a fluorine-containing resin are applied. Membrane and the like. Among these, = the solar cell protective sheet is lighter, and it is preferably a coating film coated with a coating containing an I resin from the viewpoint of the (four) lipid layer. The fluororesin sheet can be processed, for example, by using a resin such as polyvinyl fluoride (ethylene fluoride), ethylene oxide (ECTFE), or ethylene tetraethylene (10) cation: a main component, as a thin component. Tree; Π^Ε· L ^ ?〇nt ^ Example 2 Tedlar" (trade name). The resin based on the coffee can be as "1" by Solvay Solexis.

為士 Α』袈的HalarJ(商品名）。以ETFE 名）成分的樹脂係可例如旭確子公司製的％_」（商品 當氟樹脂層13係含氟樹脂薄板的情況，隔著接著層將 樹脂層13積層於基材11上。接著層係由對基材U與含 15 201246572 樹脂薄板具有接著性的接著劑構成。該接著劑係可使用 例如：丙稀酸系接著劑、聚胺甲酸乙酿系接著劑、'二 接者劑、聚醋系接著劑、聚醋聚胺甲酸乙㈣ 不 該等接著劑係可單獨使用1種、亦可組合使用2種：上 另-方面，當氟樹脂層13係由具含氟樹脂之塗料 塗佈而成的塗膜之情況，通常並未隔著接著層，而是將a 有含氟樹脂之塗料直接塗佈於基材"上，藉此將: 13積層於基材u上。 μ曰摩 含有含氟樹脂之塗料係在能溶解於溶劑中、或分散於 水中’並可施行塗佈的前提下，其餘並無特別的限定。、 塗料中所含的含氟樹脂，係在不致損及本發明效果， 且含有氟的樹脂之前提下，其餘並無特別的限定，通常係 使用能溶解於塗料的溶劑（有機溶劑或水）中，並可進行交 聯者。含氟樹脂較佳係使用具有硬化性官能基的銳稀煙樹 脂。該氟烯烴樹脂係可舉例如：由四氟乙烯（TFE)、異丁烯、 偏氟乙稀⑽）、經丁基乙料、及由其他單體構成的共聚 物’或者由TFE、VdF、經丁基乙稀㈣、及其他單體構成的 共聚物。 氟烯烴樹脂的具體例，係可舉例如：旭硝子公司製的 「LUMIFL0N」（商品名）、CENTRAL Guss 公司製的「cefral COAT」（商品名）、DIC公司製的「FLU0NATE」（商品名）等 以三氟氣乙稀（CTFE)為主成分的高分子類；大金工業公司 製的「ZEFFLE」（商品名）等以四氟乙烯（TFE)為主成分的高 分子類等等。該等之中，就從耐候性與顏料分散性等觀點， 201246572 較佳係以CTFE為主成分的高分子、及以TFE為主成分的高 分子，更佳係「LUMIFL0N」與「ZEFFLE 。 「LUMIFL0N」係含有以、與數種特定烧基乙稀越 (VE)或經烧基乙軸主要構成單位的非結晶性樹脂。諸 如此種「LUMIFL0N」具有經烧基乙稀喊單體單元的樹脂， 因為溶劑可溶性、交聯反應性、基材密接性、顏料分散性、 硬度及柔軟性均優異，因而屬較佳。 ZEFFLE」係TFE與有機溶劑可溶性烴烯烴的共聚物， 其中，就從溶劑可溶性、交聯反應性、基材密接性及顏料 分散性均優異的觀點，較佳係含有具有高反應性經基之煙 稀烴者。 形成塗料中所含有之含氟樹脂的含氟單體，係可例 如·· CTFE、貌乙烯（VF)、VdF、氣化乙稀鍵等。 再者，形成塗料中所含有之含氟樹脂且可共聚合的單 體，係可例如：醋酸乙烯酯、丙酸乙烯醋、丁酸丁醋、異 丁酸乙烯S曰、=甲基乙酸乙烯酯、己酸乙烯酯、特十碳酸 :烯::、月桂酸乙烯酯、硬脂酸乙烯醋、帛己基緩酸乙稀 酉曰及本甲酸乙稀醋等叛酸的乙稀基酷類；甲基乙稀驗、乙 基乙稀喊：丁基乙烯越及環己基乙烯喊等烷基乙稀驗類。 塗料係除上述含I樹脂之外，尚可含有諸如交聯劑、 硬化觸媒、溶劑等’視需要亦可含有諸如顏料、填充劑等 無機化合物。 塗料中所含的溶劑，在不致損及本發明效果之前提 下，其餘並無特別的限定’例如最好使用含有從甲乙酮 201246572 (MEK)、垓己酮、丙_、曱基異丁酮（MIBK)、甲苯、二甲笨、 曱醇、異丙醇、乙醇、庚烷、醋酸乙酯、醋酸異丙酯、醋 酸正丁醋或正丁醇中選擇任1種或2種以上之有機溶劑的 溶劑。 塗料中所含的顏料或填充劑，在不致損及本發明效果 之前提下，其餘並無特別的限^，可使用例如：二氧化欽、 碳黑、花顏料、雲母、聚酿胺粉末、氣㈣、氧㈣、氧 化紹、二氧化石夕、紫外線吸收劑、防腐劑、乾燥劑等。具 體而言，顏料與填充劑係為能賦予耐久性，最好使用經氧 化石夕處理過的金紅石型二氧化欽之E. L du P〇nt de Nemours and Company 公司製的「了卜pure Rl〇5」（商品名）' 及利用二甲基聚石夕氧的表面處理而修飾二氧化石夕表面經基HalarJ (trade name) for the 士 Α 袈. The resin of the component of the ETFE name can be, for example, %_" manufactured by Asahi Co., Ltd. (When the fluororesin layer 13 is a fluororesin sheet, the resin layer 13 is laminated on the substrate 11 via the adhesive layer. The layer is composed of an adhesive having a bonding property to the substrate U and a resin sheet containing 15 201246572. The adhesive may be, for example, an acrylic adhesive, a polyurethane adhesive, or a second adhesive. , a vinegar-based adhesive, and a polyester urethane (IV). These adhesives may be used singly or in combination of two types: in the other aspect, when the fluororesin layer 13 is made of a fluorine-containing resin. In the case of a coating film coated with a coating material, a coating material having a fluorine-containing resin is usually applied directly to the substrate without interposing the layer, thereby: laminating 13 on the substrate u μ 曰 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有Lifting the resin without damaging the effects of the present invention and containing fluorine, the rest It is not particularly limited, and it is usually used in a solvent (organic solvent or water) which can be dissolved in a coating material, and can be crosslinked. The fluorine-containing resin is preferably a sharp-smoke resin having a hardening functional group. The resin may, for example, be a copolymer of tetrafluoroethylene (TFE), isobutylene, vinylidene fluoride (10), butyl b, and other monomers' or TFE, VdF, butyl ethene (4), and copolymers composed of other monomers. Specific examples of the fluoroolefin resin include "LUMIFL0N" (trade name) manufactured by Asahi Glass Co., Ltd., "cefral COAT" (product name) manufactured by CENTRAL Guss Co., Ltd., and "FLU0NATE" (trade name) manufactured by DIC Corporation. A polymer containing trifluoroethylene (CTFE) as a main component; a polymer such as "ZEFFLE" (trade name) manufactured by Daikin Industries Co., Ltd., which contains tetrafluoroethylene (TFE) as a main component. Among these, from the viewpoints of weather resistance and pigment dispersibility, 201246572 is preferably a polymer containing CTFE as a main component and a polymer containing TFE as a main component, and more preferably "LUMIFL0N" and "ZEFFLE." LUMIFL0N" is a non-crystalline resin containing a main constituent unit of a plurality of specific alkyl group (VE) or a burnt-based ethyl group. Such a "LUMIFL0N" resin having a monomer unit which is exemplified by the alkyl group is preferred because it is excellent in solvent solubility, crosslinking reactivity, substrate adhesion, pigment dispersibility, hardness and flexibility. ZEFFLE is a copolymer of TFE and an organic solvent-soluble hydrocarbon olefin. Among them, from the viewpoints of excellent solvent solubility, crosslinking reactivity, substrate adhesion, and pigment dispersibility, it is preferred to contain a highly reactive base. Soda fisher. The fluorine-containing monomer which forms the fluorine-containing resin contained in the coating material may, for example, be CTFE, vinyl acetate (VF), VdF or vaporized ethylene bond. Further, a monomer which forms a fluorine-containing resin contained in the coating material and which can be copolymerized may be, for example, vinyl acetate, vinyl vinegar propionate, butyric acid butyrate, ethylene isobutyrate, and ethylene vinyl acetate. Ester, vinyl hexanoate, tetracarbonate: alkene::, vinyl laurate, vinyl vinegar stearate, hexyl sulphuric acid sulphuric acid and ethyl formate sulphuric acid, etc.; Methyl ethene test, ethyl ethene shout: butyl vinyl and cyclohexyl vinyl shunt and other alkyl ethene test. The coating material may contain, in addition to the above-mentioned I-containing resin, such as a crosslinking agent, a curing catalyst, a solvent, etc., and may contain an inorganic compound such as a pigment or a filler as needed. The solvent contained in the coating is not limited until the effect of the present invention is impaired, and the rest is not particularly limited. For example, it is preferred to use from methyl ethyl ketone 201246572 (MEK), hexanone, propylene, decyl isobutyl ketone ( One or two or more organic solvents selected from MIBK), toluene, dimethyl benzene, decyl alcohol, isopropanol, ethanol, heptane, ethyl acetate, isopropyl acetate, n-butyl acetate or n-butanol Solvent. The pigment or filler contained in the coating is not limited until the effect of the present invention is impaired, and the rest is not particularly limited. For example, dioxins, carbon black, flower pigment, mica, polyamine powder, Gas (4), oxygen (4), oxidized Shao, cerium oxide, ultraviolet absorber, preservative, desiccant, etc. Specifically, the pigment and the filler are capable of imparting durability, and it is preferable to use the rutile-type dioxin treated by Oxide-based E. L du P〇nt de Nemours and Company. Rl〇5" (trade name)' and modification of the surface of the sulphur dioxide by the surface treatment of dimethyl polychlorite

的疏水性二氧化石夕之Cab〇t公司製的「donas 72〇 (商品名）。 J /含I樹脂的塗膜係為能提升耐候性與耐到傷性，較佳 係利用交㈣施行硬I交聯㈣在*致損及本發明效果 之前提下’其餘並無特料限定，最好使用金屬螯合類、 矽烷類、異氰酸酯類或三聚氰胺類。 田版6又太％電池用保 4溥板1係在室外長期間使用的 月儿就從耐候性的觀 點，交聯劑較佳係脂肪族異氰酸酯類。 塗料中所含有的硬化觸媒係在 ‘ 钍不致抬及本發明效果之 刖提下，其餘並無特別的限定， w , j例如為促進含氟樹脂與 異氰S文酯間之交聯的二丁基二月桂酸錫等。 塗料的組成係在不致損及本發 又禾之則提下，其餘 18 201246572 並無特別的限定，例人# 月緬 f s齓树脂、顏料、交聯劑、溶劑 及觸媒進行混合而調製。 、，，成比係▲將塗料全體設為100 質里/。時’含氟樹脂含有 3〜80質量%、更佳係25〜50 顏料含有率較佳係、5〜60質量％、更佳係1〇〜3 〇 ’合劑3有率較佳係2〇~8〇質量％、更佳係25,質量％。 塗料塗佈於基材i i上的方法係可使用公知方法，利用 例如.棒塗法、刀塗法、輥塗佈法、刮刀塗佈模頭塗 佈法、凹版塗佈法等’只要塗佈成所獲得氟樹脂層Μ能成 為所需厚度便可。 在基材11上所塗佈㈣料乾燥溫度係只要不致損及 本發明效果的溫度便可，就從降低對基材u之影響的觀 點’較佳係5 0〜13 0 °C範圍。 ★氟樹脂層13的厚度係經考慮耐候性、耐藥性、輕量化 等因素之後才叹定，較佳係5〜5〇 “ m '更佳係…加“爪。 此處，氟樹脂層13係可由熱可塑性材料構成，此情 況，可非施行塗料塗佈，而是利用擠出塗佈法形成。該氣 樹脂層13係可直接擠出塗佈於基材u上，亦可在與基材 U之間介設為提高與基材u間之接著力的其他層。例如 苐3圖所示，亦可在氟樹脂層13與基材u之間介設第2 熱可塑性樹脂層14。此情況，較佳係對基材u，共擠出塗 佈形成第2熱可塑性樹脂層14與氟樹脂層13。 由熱可塑性材料構成的氟樹脂層13，係可例如：乙稀 -四氟乙烯系共聚物、乙烯-三氟氯乙烯系共聚物、乙烯_ 四氟乙烯-六就丙烯系共聚物、四氟乙烯—全氟（烷基乙烯醚） 19 201246572 系共聚物、四氟乙烯-六氟丙烯系共聚物、四氟乙烯_全氟 (烷基乙烯醚）-六氟丙烯系共聚物等、或以該等的改質聚合 物為主成分者。該等樹脂係可單獨使用]種、或混合使用 2種以上。由熱可塑性材料構成的氟樹脂層丨3係具有高耐 候性的優點。上述樹脂之中，就從與基材丨丨或第2熱可塑 性樹脂層14間之密接性的觀點，較佳係etfe。 第2熱可塑性樹脂層14係可舉例如：低密度聚乙烯 (LDPE，密度：910kg/m3以上、且未滿915kg/m3)、中密度 聚乙烯（MDPE，密度：915kg/m3以上、且未滿942kg/m3) ' 高密度聚乙烯（HDPE，密度：942kg/m3以上）等的聚乙烯； 聚丙烯（PP)、烯烴系彈性體（TP〇)、環烯烴系樹脂、乙烯_ 醋酸乙烯醋共聚物（EVA)、乙烯-醋酸乙烯醋—順丁烯二酸野 共聚物、乙烯-(甲基）丙烯酸共聚物、乙烯_(甲基）丙烯酸 酯-順丁烯二酸酐共聚物等，該等之中，較佳係聚乙烯等聚 烯烴系樹脂、更佳係乙烯-曱基丙烯酸環氧丙酯共聚物（EGA) 及乙烯-醋酸乙烯酯-順丁烯二酸酐共聚物。該等樹脂係可 單獨使用1種、或混合使用2種以上。因為上述樹脂具有 s月b基且具有極性，因而對基材11 (特別係由樹脂薄膜構 成的基材11，以及由PET薄膜構成的基材u)之接著力較 高。上述樹脂之中，更佳係對由含有官能基之氟樹脂構成 的H樹知層1 3、及由PET專構成的基材η二者之接著性 均良好的EGA。 第2熱可塑性樹脂層14的厚度，係在對基材^能發 揮所需接著性’且不致損及本發明效果之前提下，其餘並 20 201246572 無特別的限制。具體^ 較佳係2~100㈣ '更估言’第2熱可塑性樹脂層14的厚度 再者，在基材u 5〜π”、特佳係1〇〜5〇”。 禾積層上述熱可塑性樹脂層1 2之一 側的面’亦可如第4 設置蒸鍍層15，亦可如1不在基材11與氣樹脂層13之間 屬薄板Π，更可在^ 圖所示隔著接著層16積層金 L鍍層15或金屬薄板17的表面（第4 J —5圖中的下側面）設置上述氟樹脂層13。依此，藉 置ϋ層15或金屬薄17 ’便可提升太陽電池用保 濩溥板1的防濕性與耐候性。 田土材11係由樹脂薄膜構成的情況，該樹脂薄 膜有積層著蒸鍍層15或接著層16之一侧的面，為提升盘 蒸鑛層15或接著層16間之密接性，最好係施行諸如電晕 處理：電衆處理、底漆處理等表面處理。 〃、鍍層15係由諸如：金屬或半金屬、或金屬或半金屬 的軋化物、虱化物、矽化物等無機材料構成，藉由由該材 料構成’便可對基材11(太陽電池用保護薄板1)賦予防濕 性（水蒸氣阻障性）與耐候性。 ’ 形成蒸鍍層15的蒸鍍方法，係可使用例如：電漿化學 =相沉積法、熱化學氣相沉積法、光化學氣相沉積法等化 學氣相法、或真空蒸鍍法、賤鍵法、離子蒸鐘法等物理氣 冲法該等方法之中，在考慮操作性、層厚控制性的情況 下’最好為濺鍍法。 成為該蒸鍍層15之原料的金屬，係可例如：鋁（A1)、 鎂（Mg)、鈣（Ca)、鉀（κ)、錫（Sn)、鈉（Na)、鈦（Ti)、鉛（pb)、 21 201246572 錯⑹、紀⑺等。半金屬係可例如：石夕⑻)、侧⑻等。 該4金屬或半金屬的氧化物、氮化物、氮氧化物，係可例 如：氧化鋁、氧化錫、氧化 „ 化紹等。 氧切1切、氮氧切、氮氧 蒸鍍層1 5係可僅由—猫—, …機材料構成，亦可由複數種 :機材料構成。當蒸㈣15係由複數種無機材料構= 層，：為依序蒸鑛由各無機材料所構成層的 層，料為複數種無機材料同時施行蒸鑛的蒸鑛層。 —洛㈣15的厚度係經考慮水蒸氣阻障性之後才適· =，依照所使用的無機材料種類與蒸鍍密度“ 10~l〇〇nm. ㈣度I佳係更佳係 可二：二，17亦是與上述蒸鍵…樣的， 了對基材11(太陽電池用保護薄 阻障性）與耐候性。金屬 “水蒸氣 前提下⑫ 的材料係在具有該功能的 二/、餘並無特別的限制’可例如：紹 鋁合金等等金屬。 金屬薄板1 7的厚度係在不 下，其餘並無特別的限定，就從=及本發明效果的前提 強度較強、水蒸氣阻障性較巧 發生頻度較低、機械 5，。㈣、更佳係!5〇二 ！量化等觀點’較佳係 接著層16係由對基材u 接著劑構成。構成接著層16的接著屬二板17具有接著㈣ 酸系接著劑、聚胺甲酸乙s旨系接二“糸可使用例如：丙稀 者Μ、環氧系接著劑、聚 22 201246572 酯系接著劑、聚酯聚胺甲酸乙酯系接著劑等。豸等接著劑 係可單獨使用1種、亦可組合使用2種以上。 接著層16的厚度係在不致損及本發明效果的前提 下，其餘並無特別的限定，通常較佳係卜2〇 # m、更佳係 3〜1 0以m 〇 另外，以上實施形態係例示在基材丨丨其中一面上積層 著熱可塑性樹脂層丨2之太陽電池用保護薄板丨，惟本發明 的太陽電池用保護薄板並不僅侷限於此，亦可在基材丨丨的 另一面（上述其中一面背後側的面）上積層著熱可塑性樹脂 層0 (太陽電池用保護薄板之製造方法） 在製造本實施形態的太陽電池用保護薄板丨（其中一例 係第1圖所示太陽電池用保護薄板叫，較佳係將構成上 述熱可塑性樹脂層12之第1層12ι的第i樹脂組成物、構 成第2層12 2的第2樹脂組成物’依第j樹脂組成物靠基 材11側的方式，共擠出塗佈於基材丨丨至少其中一面上， 而开y成由在基材11上所積層第1層121、與在第1層I。 上所積層第2層121構成的熱可塑性樹脂層丨2。根據此種 共擠出塗佈&，可依高生產性且廉價地製造线電池用保 護薄板1。又’因為不需要另外設置為對太陽電池模組的 密封材接著太陽電池用保護薄板丨用之接著劑層，因而可 防止因該接著劑的分解等而造成經時劣化情形。 具體而言’使用T型模頭製膜機等，將上述第1樹脂 組成物與第2樹脂組成物分別施行熔融、混練，一邊使基 23 201246572 材π依一定濃度移動，一邊在該基材u其中一面上，將 熔融的第1樹脂組成物與第2樹脂組成物施行共擠出塗佈 而積層，而在基材11上形成由第1層121與第2層122構 成的熱可塑性樹脂層1 2，便獲得太陽電池用保護薄板i。 另外，如第2圖〜第5圖所示，當在基材丨丨上形成其 他層的情況，只要在基材丨i未形成該其他層之—側的面 上，形成熱可塑性樹脂層12便可。 將形成熱可塑性樹脂層1 2的第i與第2樹脂組成物予 以炼融之溫度’係、設定為不會有因炫融樹脂組成物的溫度 (熱）而導致基材U出現變形的程度，較佳係8〇~35〇1 : 更佳係150〜300°C。 再者’形成熱可塑性樹脂層12的第）與第2樹脂組成 物從T型模頭製膜機中的吐出量，係配合目標之熱可塑性 樹脂層12的第1層121與第2層m厚度、以及基材u 的移動速度而適當調整。 基材11係例如利用滚輪對滾輪方式依—定速度朝 邊方向移動（搬送），該移動速声仫财人， 助迷度係配合形成熱可塑性樹 層12的第1及第2樹脂材料，從I % 寸攸i型杈碩製膜機中的吐 量而適當調整。 ^ 114 + 上’從τ型模頭製膜機共擠出塗佈著“W樹脂細 與第2樹脂組成物而積層，债可尤|u 隹基材11上牢固地招 熱可塑性樹脂層12 ,俾可依高生產 μ 座性製造太陽電池用 溥板1。 24 201246572 〔太陽電池模組〕 第6圖所示係本發明一實施形態的太陽電池模組之概 略剖視圖。本實施形態的太陽電池模組1 〇係由複數太陽電 池單元2、密封材（填充層）3、玻璃板4、及太陽電池用保 護薄板1構成。該等複數太陽電池單元2係由屬於光電轉 換元件的結晶矽、非晶矽等所構成。該密封材（填充層）3 係由將該等太陽電池單元2予以密封的電絕緣體構成。該 玻璃板4係積層於密封材3的表面（第6圖中的上側面） 上。該太陽電池用保護薄板1係積層於密封材3的背面（第 6圖中的下側面）上’且當作背面保護薄板（背板）用。 另外，太陽電池用保護薄板1係依熱可塑性樹脂層12 的第2層122靠密封材3側的方式，積層於密封材3上， 利用該熱可塑性樹脂層 12提高對密封材3的接著力。又"Donas 72" (trade name) manufactured by Cab〇t Co., Ltd. of the hydrophobic dioxide. The coating film of J / I resin is used to improve weather resistance and resistance to damage, and it is better to use it. Hard I cross-linking (4) is provided before the *damage and the effect of the present invention. 'There are no special restrictions, and it is preferable to use metal chelate, decane, isocyanate or melamine. 4 The slab 1 is used for the long period of outdoor use. From the viewpoint of weather resistance, the crosslinking agent is preferably an aliphatic isocyanate. The curing catalyst contained in the coating is not affected by the effect of the present invention.刖 , , , , , , , , w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w And the other is raised, the remaining 18 201246572 is not particularly limited, the example of the people #月 f 齓 齓 resin, pigment, cross-linking agent, solvent and catalyst mixed to prepare.,,, the ratio of ▲ will paint all Set to 100% /. When 'fluorinated resin contains 3 to 80% by mass, more The ratio of the pigment content of 25 to 50 is preferably 5 to 60% by mass, more preferably 1 to 3 〇. The ratio of the mixture 3 is preferably 2 〇 to 8 〇 by mass, more preferably 25, and % by mass. The method of applying to the substrate ii can be carried out by a known method, for example, by a bar coating method, a knife coating method, a roll coating method, a knife coating die coating method, a gravure coating method, etc. The fluororesin layer can be obtained to have a desired thickness. The drying temperature of the (four) material applied to the substrate 11 can be reduced from the viewpoint of reducing the influence on the substrate u as long as the temperature of the effect of the present invention is not impaired. 'The preferred range is 50 to 13 ° ° °. ★ The thickness of the fluororesin layer 13 is determined by considering the weather resistance, drug resistance, weight reduction and other factors, preferably 5 to 5 〇 "m ' more Preferably, the fluororesin layer 13 may be composed of a thermoplastic material, and in this case, it may be formed by extrusion coating instead of coating, and the gas resin layer 13 may be directly extruded. It may be applied to the substrate u or may be interposed between the substrate U and another layer to increase the adhesion between the substrate u and the substrate u. It is also possible to interpose the second thermoplastic resin layer 14 between the fluororesin layer 13 and the substrate u. In this case, it is preferable to form the second thermoplastic resin layer 14 by co-extrusion coating on the substrate u. Fluororesin layer 13. The fluororesin layer 13 composed of a thermoplastic material may be, for example, an ethylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, or an ethylene-tetrafluoroethylene-hexa-propylene system. Copolymer, tetrafluoroethylene-perfluoro(alkyl vinyl ether) 19 201246572 copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene_perfluoro(alkyl vinyl ether)-hexafluoropropylene copolymer The resin or the like may be used as a main component, and these resins may be used singly or in combination of two or more. The fluororesin layer 丨3 composed of a thermoplastic material has an advantage of high weather resistance. Among the above resins, from the viewpoint of adhesion to the substrate crucible or the second thermoplastic resin layer 14, it is preferable to use it. The second thermoplastic resin layer 14 is, for example, low density polyethylene (LDPE, density: 910 kg/m3 or more and less than 915 kg/m3), medium density polyethylene (MDPE, density: 915 kg/m3 or more, and not 942kg/m3) 'High density polyethylene (HDPE, density: 942kg/m3 or more), polyethylene, polypropylene (PP), olefin-based elastomer (TP〇), cycloolefin resin, ethylene _ vinyl acetate vinegar Copolymer (EVA), ethylene-vinyl acetate vinegar-maleic acid field copolymer, ethylene-(meth)acrylic acid copolymer, ethylene_(meth)acrylate-maleic anhydride copolymer, etc. Among them, a polyolefin resin such as polyethylene, more preferably an ethylene-mercaptoacrylic acid propylene acrylate copolymer (EGA) or an ethylene-vinyl acetate-maleic anhydride copolymer is preferable. These resins may be used alone or in combination of two or more. Since the above resin has a s-month b-base and has a polarity, the adhesion to the substrate 11 (particularly, the substrate 11 composed of the resin film and the substrate u composed of the PET film) is high. Among the above resins, an EGA having good adhesion to both the H-tree layer 13 composed of a functional group-containing fluororesin and the substrate η composed of PET is more preferable. The thickness of the second thermoplastic resin layer 14 is raised before the substrate can be subjected to the desired adhesion, and the effect of the present invention is not impaired, and the rest 20 201246572 is not particularly limited. Specifically, it is preferably 2 to 100 (4). [More] The thickness of the second thermoplastic resin layer 14 is further in the case of the substrate u 5 to π" and the special system 1 to 5 〇". The surface of the one side of the thermoplastic resin layer 12 may be provided with the vapor deposition layer 15 as in the fourth embodiment, or may be a thin plate between the substrate 11 and the gas resin layer 13, and may be The fluororesin layer 13 is provided on the surface of the gold-plated layer 15 or the metal thin plate 17 (the lower side in the fourth J-5) in which the adhesive layer 16 is laminated. Accordingly, the moisture resistance and weather resistance of the solar cell protective sheet 1 can be improved by the use of the tantalum layer 15 or the thin metal sheet 17'. When the field material 11 is composed of a resin film, the resin film has a surface on which one side of the vapor deposition layer 15 or the subsequent layer 16 is laminated, and it is preferable to carry out the adhesion between the vapor deposition layer 15 or the adhesion layer 16 of the disk. Such as corona treatment: electric treatment, primer treatment and other surface treatment. The ruthenium and the plating layer 15 are composed of an inorganic material such as a metal or a semimetal, or a rolled metal, a bismuth compound or a bismuth compound of a metal or a semimetal, and the substrate 11 can be protected by the material. The sheet 1) imparts moisture resistance (water vapor barrier property) and weather resistance. The vapor deposition method for forming the vapor deposition layer 15 may be, for example, a chemical vapor phase method such as a plasma chemical method, a phase deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method, or a vacuum vapor deposition method or a ruthenium bond. Among the methods, such as the method and the ion-steaming method, it is preferable to use a sputtering method in consideration of operability and layer thickness controllability. The metal which is a raw material of the vapor deposition layer 15 may be, for example, aluminum (A1), magnesium (Mg), calcium (Ca), potassium (κ), tin (Sn), sodium (Na), titanium (Ti), or lead. (pb), 21 201246572 Wrong (6), Ji (7), etc. The semimetal system can be, for example, Shi Xi (8), side (8), and the like. The oxide, nitride or oxynitride of the metal or semimetal may be, for example, alumina, tin oxide, oxidized, or the like. Oxygen cut 1 cut, oxynitride, nitrogen oxide vapor deposition layer 15 It consists only of -cat-, machine material, or a plurality of kinds: machine material. When steaming (four) 15 series consists of a plurality of inorganic materials = layer, it is a layer of layers of each inorganic material. The steaming layer of steamed ore is simultaneously applied to a plurality of inorganic materials. The thickness of Luo (4) 15 is determined by considering the water vapor barrier property, according to the type of inorganic material used and the vapor deposition density "10~l〇〇 Nm. (four) degree I better system can be two: two, 17 is also the same as the above steaming, for the substrate 11 (solar battery protection thin barrier) and weather resistance. The metal "water vapor under the premise of 12 materials in the second / / there is no special limit" can be, for example, Shao aluminum alloy and other metals. The thickness of the metal sheet 17 is not inferior, the rest is not special Qualified, from the = and the effect of the invention is stronger, the water vapor barrier is less frequent, the machine is 5, (4), better system! 5 〇 2! Quantitative view, etc. The 16th layer is composed of the substrate u and the subsequent agent. The second plate 17 constituting the adhesive layer 16 has a (4) acid-based adhesive, and the polyurethane is used to connect the second layer. For example, a propylene ring or a ring can be used. Oxygen-based adhesive, poly 22 201246572 ester-based adhesive, polyester polyurethane-based adhesive, and the like. The adhesive may be used singly or in combination of two or more. The thickness of the layer 16 is not particularly limited as long as the effect of the present invention is not impaired, and it is generally preferred that the thickness of the layer 16 is preferably 2 m, more preferably 3 to 10 0 m, and the above embodiment is A protective sheet for a solar cell in which a thermoplastic resin layer 2 is laminated on one surface of a substrate, but the protective sheet for a solar cell of the present invention is not limited thereto, and may be on the other side of the substrate. (The method of manufacturing a solar cell protective sheet) is formed on the surface of the back surface of the one surface (the method for producing a solar cell protective sheet). The solar cell protective sheet of the present embodiment is manufactured (an example of which is a solar cell shown in Fig. 1). It is preferable to use a protective sheet, and it is preferable to form the i-th resin composition constituting the first layer 12 of the thermoplastic resin layer 12 and the second resin composition constituting the second layer 12 2 by the substrate of the j-th resin composition. The 11-side method is co-extruded and applied on at least one side of the substrate ,, and the y is formed by laminating the first layer 121 on the substrate 11 and the second layer on the first layer I. 121 is a thermoplastic resin layer 。2. Such a co-extrusion coating & can manufacture the protective sheet for wire batteries 1 with high productivity and at low cost. Moreover, since it is not necessary to separately provide a sealing material for the solar cell module and then a protective sheet for the solar cell. In the case of the adhesive layer, it is possible to prevent deterioration over time due to decomposition of the adhesive, etc. Specifically, the first resin composition and the second resin composition are respectively formed by using a T-die film forming machine or the like. By melting and kneading, while the base 23 201246572 material π is moved at a constant concentration, the molten first resin composition and the second resin composition are coextruded and laminated on one surface of the substrate u. On the substrate 11, a thermoplastic resin layer 12 composed of the first layer 121 and the second layer 122 is formed, and a solar cell protective sheet i is obtained. Further, as shown in Figs. 2 to 5, In the case where another layer is formed on the substrate, the thermoplastic resin layer 12 may be formed on the side of the substrate 丨i on the side where the other layer is not formed. The i-th and the thermoplastic resin layer 12 are formed. The second resin composition is smelted The degree is set so as not to cause deformation of the substrate U due to the temperature (heat) of the composition of the molten resin, and is preferably 8 〇 to 35 〇 1 : more preferably 150 to 300 ° C. The amount of discharge from the "form of the thermoplastic resin layer 12" and the second resin composition from the T-die film forming machine is the thickness of the first layer 121 and the second layer m of the thermoplastic resin layer 12 to be targeted. And the movement speed of the substrate u is appropriately adjusted. The base material 11 is moved (transported) in the direction of the side by a roller, for example, by a roller, and the moving speed is used to match the first and second resin materials forming the thermoplastic tree layer 12. Adjust appropriately from the amount of spit in the I % inch 攸i type 杈 制 film machine. ^ 114 + upper 'co-extruded and coated with the second resin composition from the τ-type die-making machine to laminate the layer, the bond can be used to securely coat the plastic resin layer 12 on the substrate 11俾 俾 生产 生产 制造 制造 制造 2012 2012 2012 2012 2012 2012 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳The battery module 1 is composed of a plurality of solar battery cells 2, a sealing material (filler layer) 3, a glass plate 4, and a protective sheet for solar cells 1. The plurality of solar battery cells 2 are composed of crystallizations belonging to photoelectric conversion elements. The sealing material (filling layer) 3 is composed of an electrical insulator that seals the solar battery cells 2. The glass plate 4 is laminated on the surface of the sealing material 3 (Fig. 6 The solar cell protective sheet 1 is laminated on the back surface (the lower side in FIG. 6) of the sealing material 3 and used as a back protective sheet (back sheet). 1 is based on the thermoplastic resin layer 12 The second layer 122 is laminated on the sealing material 3 so as to be on the side of the sealing material 3, and the adhesion of the sealing material 3 is improved by the thermoplastic resin layer 12.

或太陽電池模組1 0遭受破損。Or the solar cell module 10 is damaged.

脂’特別係就從對諸如氧等的阻氣性高 系树脂，較佳係例如就熱 主成分所例示的烯烴系樹 氣性高、交聯容易、取得 25 201246572 谷易度等觀點，較佳杳乙烯_醋酸乙烯酯共聚物（EVA)。若 密封材3的材料係烯烴系樹脂，則在與以烯烴系樹脂為主 成分的熱可塑性樹脂層12之第2層122間之親和性會變 大，俾使在與熱可塑性樹脂層12及密封材3間之接著力變 為更南。 製造上述太陽電池模組丨〇的方法並無特別的限定例 如利用構成密封材3的2片薄板呈三明治狀夾置太陽電池 單几2’在該薄板其中一露出面上設置太陽電池用保護薄 板1，並在另一露出面上設置玻璃板4，再將該等依真空狀 態一邊加熱一邊施行壓合而呈一體化，藉此便可製造太陽 電池拉組1 0。此時，太陽電池用保護薄板1係利用熱可塑 性樹月曰層1 2與密封材3間之熱熔接而接合於密封材3上。 另外，如第7圖所示，亦可取代玻璃板4，改為將太 陽電池用保護薄板1使用為表面保護薄板（前板）。此情 況，若太陽電池單元係使用可撓性基板，便可獲得具有可 撓性的太陽電池模組。依此，藉由將太陽電池模組呈可撓 化，便可利用滾輪對滾輪進行大量生產。又，因為具有可 撓性的太陽電池模組亦可貼合於具有弓形狀、拋物線狀壁 面的物體，因而可設置於諸如圓頂狀建築物、高速道路隔 音牆等處。 以上所5兒明的實施形態係為使本發明的理解較為容易 而記載’並非為限定本發明而記載。it，上述實施形態所 揭示的各要件’均涵蓋在隸屬本發明技術範疇内的所有變 更設計與均等物之涵義。 26 201246572 實施例 以下，利用實施例等針對本發明進行更具體說明，惟 本發明範圍並不僅侷限於該等實施例等。 〔實施例1〕 對基材的PET薄膜（T0RAY公司製，Lumirror xl〇s， 厚度125//m)其中一面施行電暈處理（輸出2〇〇〇幻。利用τ 型模頭製膜機（擠筒溫度：23 0〜28(TC，Τ型模頭溫度：3〇〇 c )，將乙烯-丙烯酸丁酯共聚物（ARKEMa公司製，商品名： LOTRYL 17BA07 ’丙烯酸丁酯含有量：4. 2莫耳％，以下稱 「共聚物A」）、與低密度聚乙烯系樹脂（T〇s〇h公司製，商 品名：LUMITAC 43-1，密度905kg/m3)，分別依厚度成為 25 與75/zm的方式’且共聚物A靠基材側的方式，對 上述PET薄膜的電暈處理面施行直接共擠出塗佈，而形成 由第1層（共聚物A)與第2層（低密度聚乙烯系樹脂）構成 的熱可塑性樹脂層，便獲得第1圖所示構造的太陽電池用 保護薄板。 〔實施例2〕 除將共聚物A變更為乙烯-丙烯酸丁酯共聚物（ARKEMA 公司製’商品名：LOTRYL 30BA02，丙烯酸丁酯含有量：8.6 莫耳％ ’以下稱「共聚物B」）之外，其餘均施行與實施例1 同樣的操作，獲得第1圖所示構造的太陽電池用保護薄板。 〔實施例3〕 除將共聚物A變更為乙烯-丙烯酸甲酯共聚物（ARKEMA 公司製，商品名：LOTRYL 28MA07，丙烯酸曱酯含有量：11.2 27 201246572 莫耳％)之外，其餘均施行與實施例1同樣的操作，獲得第 1圖所示構造的太陽電池用保護薄板。 〔實施例4〕 除將共聚物A變更為乙晞-甲基丙烯酸共聚物（三井· 杜邦高分子化學公司製，Nucrel N1 525 ’甲基丙烯酸含有 量：5. 4莫耳％)之外，其餘均施行與實施例1同樣的操作， 獲得第1圖所示構造的太陽電池用保護薄板。 〔實施例5〕 除將共聚物A變更為乙烯-醋酸乙烯酯共聚物（Tosoh 公司製，ULTRATHENE 750，醋酸乙烯酯含有量：13. 3莫耳 %)之外，其餘均施行與實施例1同樣的操作，獲得第1圖 所示構造的太陽電池用保護薄板。 〔實施例6〕 在基材的PET薄膜（帝人杜邦薄膜公司製，帝特龍sl， 厚度125/zm)其中一面上，將氟樹脂（旭硝子公司製的The grease is particularly suitable for a gas barrier high-resin such as oxygen, and preferably, for example, the olefins which are exemplified by the hot main component are high in gas, easy to crosslink, and have a viewpoint of 25 201246572. Jiayi ethylene-vinyl acetate copolymer (EVA). When the material of the sealing material 3 is an olefin-based resin, the affinity between the second layer 122 and the second layer 122 of the thermoplastic resin layer 12 containing the olefin-based resin as a main component is increased, and the thermoplastic resin layer 12 and the thermoplastic resin layer 12 are formed. The adhesion between the sealing members 3 becomes more south. The method for manufacturing the above-described solar cell module is not particularly limited. For example, two solar panels constituting the sealing material 3 are sandwiched between the solar cells, and a solar cell protective sheet is provided on one of the exposed surfaces of the thin plate. 1. The glass plate 4 is placed on the other exposed surface, and the glass cells are assembled by pressing and heating in a vacuum state, whereby the solar cell pull group 10 can be manufactured. At this time, the solar cell protective sheet 1 is joined to the sealing material 3 by heat fusion between the thermoplastic plastic tree layer 12 and the sealing member 3. Further, as shown in Fig. 7, instead of the glass plate 4, the protective sheet 1 for solar cells can be used as a surface protective sheet (front plate). In this case, if the solar cell unit uses a flexible substrate, a flexible solar cell module can be obtained. Accordingly, by flexing the solar cell module, the roller can be mass-produced by the roller. Further, since the flexible solar cell module can be attached to an object having a bow shape or a parabolic wall surface, it can be disposed, for example, in a dome-shaped building, a highway partition wall or the like. The embodiments described above are intended to facilitate the understanding of the present invention and are not intended to limit the present invention. It is to be understood that all of the elements of the present invention are intended to cover all modifications and equivalents within the scope of the invention. [Embodiment] The present invention will be described more specifically by way of examples and the like, but the scope of the invention is not limited to the embodiments and the like. [Example 1] A PET film (manufactured by Tory Co., Ltd., Lumirror xl〇s, thickness: 125/m) was subjected to corona treatment on one side (output 2 illusion. Using a τ type die forming machine ( Extrusion temperature: 23 0~28 (TC, Τ type die temperature: 3〇〇c), ethylene-butyl acrylate copolymer (ARKEMa company, trade name: LOTRYL 17BA07 'butyl acrylate content: 4. 2 mol%, hereinafter referred to as "copolymer A"), and low-density polyethylene resin (trade name: LUMITAC 43-1, density: 905 kg/m3, manufactured by T〇s〇h Co., Ltd.), respectively, with a thickness of 25 In the manner of 75/zm' and the copolymer A is on the substrate side, direct co-extrusion coating is applied to the corona-treated side of the PET film to form the first layer (copolymer A) and the second layer ( A thermoplastic sheet for a solar cell having the structure shown in Fig. 1 was obtained as a thermoplastic resin layer composed of a low-density polyethylene resin. [Example 2] A copolymer A was changed to an ethylene-butyl acrylate copolymer (ARKEMA). Company's name: LOTRYL 30BA02, butyl acrylate content: 8.6 mol% 'hereafter The same operation as in Example 1 was carried out except that the copolymer B") was used to obtain a protective sheet for a solar cell having the structure shown in Fig. 1. [Example 3] In addition to changing the copolymer A to ethylene-methyl acrylate The solar cell of the structure shown in Fig. 1 was obtained by the same operation as in Example 1 except that the copolymer (trade name: LOTRYL 28MA07, decyl acrylate content: 11.2 27 201246572 mol%) was used. The protective sheet was used. [Example 4] The copolymer A was changed to an acetamidine-methacrylic acid copolymer (manufactured by Mitsui & DuPont Polymer Chemical Co., Ltd., Nucrel N1 525 'methacrylic acid content: 5. 4 mol% The same operation as in Example 1 was carried out, and a protective sheet for a solar cell having the structure shown in Fig. 1 was obtained. [Example 5] Except that the copolymer A was changed to an ethylene-vinyl acetate copolymer (Tosoh) The same operation as in Example 1 was carried out except that the company's product, ULTRATHENE 750, vinyl acetate content: 13.3 mol%), and the protective sheet for solar cells having the structure shown in Fig. 1 was obtained. 6〕 A fluororesin (made by Asahi Glass Co., Ltd.) on one side of a PET film (manufactured by Teijin DuPont Film Co., Ltd., Ditron Sol, thickness 125/zm)

Lumifron LF-200、與 Sumika Bayer Urethane 公司製的 SUMIDUR 3300、以及杜邦公司製Ti-Pure R105，依1〇〇質 量份：10質量份：3 0質量份比率進行混合者）利用邁耶塗 佈機施行塗佈’經依130°C施行1分鐘乾燥，形成厚度丨5 μ ^ 的氟樹脂層，便製得氟塗佈處理pET薄膜。然後，對所獲 得氟塗佈處理PET薄膜的非氟塗佈面施行電暈處理（輸出 2000W)。 利用T型模頭製膜機（擠筒溫度：230〜280 °C，T型模 頭溫度.300C)，將共聚物β、與乙烯—丙烯酸丁酯共聚物 28 201246572Lumifron LF-200, SUMIDUR 3300 manufactured by Sumika Bayer Urethane Co., Ltd., and Ti-Pure R105 manufactured by DuPont Co., Ltd., mixed according to 1 part by mass: 10 parts by mass: 30 parts by mass) The coating was subjected to drying at 130 ° C for 1 minute to form a fluororesin layer having a thickness of μ 5 μ ^ to prepare a fluorine-coated pET film. Then, the non-fluorine coated surface of the obtained fluorine-coated PET film was subjected to corona treatment (output: 2000 W). Using a T-die film forming machine (squeezing barrel temperature: 230 to 280 ° C, T-die temperature: 300 C), copolymer β, and ethylene-butyl acrylate copolymer 28 201246572

(ARKEMA公司製’商品名：l〇TRyl 35BA40，丙烯酸丁酯含 有量：10.5莫耳以下稱「共聚物c」），依質量比6: 4(共聚物B :共聚物⑺的摻合物、以及含氧化鈦15質量％ 的低密度聚乙烯系樹脂（T〇s〇h公司製，商品名：LUMITAC 43-1 ’密度905kg/m3) ’分別依厚度成為25#m與75#m的 方式施行共擠出塗佈。此時，依共聚物B與共聚物c的摻 合樹脂靠基材側的方式’對上述氟塗佈處理pET薄膜的電(ARKEMA company's product name: l〇TRyl 35BA40, butyl acrylate content: 10.5 mol hereinafter referred to as "copolymer c"), according to a mass ratio of 6: 4 (copolymer B: copolymer (7) blend, And a low-density polyethylene resin (manufactured by T〇s〇h Co., Ltd., trade name: LUMITAC 43-1 'density 905kg/m3) containing titanium oxide 15% by mass, respectively, in a manner of 25#m and 75#m depending on the thickness Co-extrusion coating is carried out. At this time, the fluorine-coated pET film is electrically treated in such a manner that the blended resin of the copolymer B and the copolymer c is on the substrate side.

暈處理面施行直接共擠出塗佈，而形成由第1層（共聚物B 與共聚物C的摻合樹脂）及第2層（低密度聚乙烯系樹脂） 構成的熱可塑性樹脂層’便獲得第2圖所示構造的太陽電 池用保護薄板。 〔實施例7〕 將具攪拌機的聚合鍋中施行脫氣，並再該聚合鍋中注 入1H-十三氟己烷soo.ogu—二氯氟丙烷 (和光化學公司製：HCFC-225)75.0g 、及 3’3’4’4’5’5’6’6’6-九氟-卜己烯1492。更擠人六氣丙院 157.3g、四氟乙烯49.2g、及乙烯16g，然後使聚合鋼溫 度升溫至66°C。 接者，添加屬於聚合起始劑的三甲基乙酿基過氧化第 三丁基0_564g’使開始進行聚合。為在聚合中能使壓力保 持一定’便使四I乙稀/乙歸混合單體氣體（混合比：54/46) 連續地^聚合W。又，連續地流人u莫耳％的 3’3’4,4,5,5,6,6,6-九氟〜1_已稀、〇25 莫耳％的衣康酸Direct-coextrusion coating is applied to the halo-treated surface to form a thermoplastic resin layer composed of the first layer (the blended resin of the copolymer B and the copolymer C) and the second layer (the low-density polyethylene resin). A protective sheet for a solar cell having the structure shown in Fig. 2 was obtained. [Example 7] Degassing was carried out in a polymerization vessel equipped with a stirrer, and 1H-trifluoropropane soo.ogu-dichlorofluoropropane (manufactured by Photochemical Co., Ltd.: HCFC-225) 75.0 g was injected into the polymerization pot. And 3'3'4'4'5'5'6'6'6-nonafluoro-buhexene 1492. More crowded six gas cylinders 157.3g, tetrafluoroethylene 49.2g, and ethylene 16g, and then the temperature of the polymer steel was raised to 66 °C. Next, a trimethylethyl ketone peroxide tributyl 0-564g' which is a polymerization initiator was added to start polymerization. In order to maintain a certain pressure in the polymerization, the tetra-ethylene/ethylidene mixed monomer gas (mixing ratio: 54/46) was continuously polymerized. Further, it continuously flows 3'3'4,4,5,5,6,6,6-non-fluorine~1_diluted, 〇25 mol% of itaconic acid

及含有1質量％的1， 鼠-1，1，2，2，3-五氟丙烧之四 29 201246572 氟乙烯/乙烯混合單體氣體（混合比：54/46)。然後，在裝 填混合單體氣體7〇g的時點便停止聚合，將聚合鍋溫度冷 钾至室溫，同時施行迫淨直到常壓。使所獲得樹脂依i 2〇 °C進行24小時乾燥，便獲得目標之氟樹脂（乙烯四氟乙烯 (ETFE)樹脂；稱「氟樹脂1」）。 在所獲得氟樹脂1中’依氧化鈦成為20質量％的方式 添加ETFE的顏料母料（大田精化工業公司製，H_51〇〇)並混 練，獲得白色氟樹脂（稱「氟樹脂2」）。 對PET薄膜（帝人杜邦薄膜公司製，帝特龍SL厚度 125# m)的雙面施行電暈處理（輸出2〇〇〇w)。然後，利用τ 型杈頭製膜機（擠筒溫度：200。(：，T型模頭溫度：3〇(TC )， 將上述所獲得氟樹脂2、與乙烯-甲基丙烯酸環氧丙酯共聚 物（ARKEMA公司製，商品名：L0TADER Αχ884〇，曱基丙烯 酸環氧丙酯含有量：8.0莫耳％)，分別依厚度成為25"m， 且乙烯-甲基丙烯酸環氧丙酯共聚物靠基材側的方式，對上 述PET薄膜其中一面施行直接共擠出塗佈，而形成熱可塑 性樹脂層與氟樹脂層。 再者，對上述PET薄膜另一面，與實施例2同樣的施 行共擠出塗佈，形成由第1層（共聚物B)與第2層（低密度 聚乙烯系樹脂）所構成熱可塑性樹脂層，便獲得第3圖所示 構造的太陽電池用保護薄板。 〔實施例8〕 除將共聚物A變更為乙烯-甲基丙烯酸環氧丙酯共聚 物（ARKEMA公司製’ LOTADER AX8840，甲基丙烯酸環氧丙 201246572 酉曰含有量.8.0莫耳％)之外，其餘均施行與實施例1同樣 的插作’獲得第1圖所示構造的太陽電池用保護薄板。 〔比較例1〕 對依與實施例1同樣獲得的PET薄膜之電暈處理面， 將低密度聚乙稀（T〇s〇h公司製，商品名：LUMITAC 434， 密度905kg/m3)依厚度成為75μ m方式施行直接擠出塗佈， 而形成熱可塑性樹脂層，便獲得太陽電池用保護薄板。 〔試驗例1〕<接著性評價> 根據日本工業規格：JIS K6854-3 : 1999「接著劑-剝 離接著強度試驗方法-第3部：τ形剝離」所規定方法，評 價實施例與比較例所獲得太陽電池用保護薄板的接著性。 具體係如下述。 將實施例與比較例所獲得太陽電池用保護薄板裁剪為 25nunx200mm，而製作試驗片。依能獲得該試驗片中的基材 與熱可塑性樹脂層能剝離方式，分別固定於萬能拉伸試驗 機上下的扣件，於溫度23t：、濕度5〇%RH條件下，依剝離 速度300mm/inin速度剝離試驗片，將此時的負荷視為接著 力（初期：N/25mm)並測定（測定中，依基材與熱可塑性樹脂 層的張開角度成為180度方式固定）。結果如表1所示。 再者’將上述式驗片投入高壓蒸煮試驗 cooker test : 12rc，濕度 l〇〇%RH，24 小時）後，與上述 同樣的測定接著力（耐久後：N/25min)。結果如表1所示。 〔試驗例2〕<捲曲量測定> 將實施例或比較例所獲得太陽電池用保護薄板切取為 31 201246572 3〇〇mmx3〇〇mm正方形，放置於水平平台上，測定從四角落 的平台面距捲曲頂部的垂直距離（mm)。計算所獲得4個地 方的各距離平均值，將其視為「捲曲量（mm)」。結果如表 1所示。 [表1 ] 接著力（N/25mm〉 捲曲量 (mm) 初期 耐久後 實施例1 >25 >25 21.3 實施例2 >25 >25 15.3 實施例3 >25 >25 18. 7 實施例4 >25 >25 20, 8 實施例5 >25 >25 13.6 實施例6 >25 >25 8.3 實施例7 >25 >25 14.6 實施例8 >25 >25 21. 〇 比較例1 14.8 3.1 24.1 由表1中得知，實施例的太陽電池用保護薄板係 基材（PET薄膜）與熱可塑性樹脂層間之接著力較高，且捲 曲量較小。 〔實施例9〕 對基材的PET薄膜（T0RAY公司製，Lumirr〇r xl〇s， 厚度125em)其中一面施行電暈處理（輸出2〇〇〇w)。利用τ 型模頭製膜機（擠筒溫度：230〜280°C，Τ型模頭溫度：300 °c)，將乙烯-丙烯酸丁酯共聚物（ARKEMA公司製，商品名： LOTRYL 30BA02，丙烯酸丁酯含有量：8 6莫耳％ ;共聚物 B)、與密度880kg/m3的聚乙烯系樹脂（住友化學公司製， 品名：EKELEN CX4002)，分別依厚度成為25/^與75//m 32 201246572 的方式’且共聚物B靠基材侧的方式，對上述pa薄膜的 電暈處理面施行直接共擠出塗佈，而形成由第1層（丘聚物 B)與第2層（密度880kg/m3的聚乙烯系樹脂）構成之熱可塑 性樹脂層，便獲得第1圖所示構造的太陽電池用保護薄板。 〔實施例10〕 除將構成第2層的聚乙浠系樹脂，變更為密度890 kg/m3 的聚乙烯系樹脂（Prime Polymer公司製，商品名：ev〇lUE S P 9 0 0 1 0 0 )之外’其餘均施行與實施例9同樣的操作，獲得 第1圖所示構造的太陽電池用保護薄板。 〔實施例11〕 除將構成第2層的聚乙烯系樹脂，變更為密度9〇〇kg/m3 的聚乙烯系樹脂（Tosoh公司製，商品名：LUMITAC 22-6) 之外’其餘均施行與實施例9同樣的操作，獲得第1圖所 示構造的太陽電池用保護薄板。 〔實施例12〕 除將構成第2層的聚乙浠系樹脂，變更為密度91 〇kg/m3 的聚乙烯系樹脂（T〇s〇h公司製，商品名：LUMITAC 54-1) 之外，其餘均施行與實施例9同樣的操作，獲得第丨圖所 示構造的太陽電池用保護薄板。 〔實施例13〕 除將構成第2層的聚乙烯系樹脂’變更為由密度 890Kg/m3的聚丙烯樹脂（Prime p〇lymer公司製，商品名： Prime P〇lypro F-744NP)50 質量份、與密度 9〇5kg/m3 的聚 乙烯系樹脂（T〇s〇h公司製，商品名：UMITAC 43_1)5〇質 33 201246572 里伤的摻合物（摻合樹脂密度：之外其餘均施 灯與實施例9同樣的操作，獲得第i圖所示構造的太陽電 池用保護薄板。 〔實施例14〕 除將構成第1層的共聚物B，變更為乙烯-丙烯酸曱酯 共聚物（ARKEMA公司製，商品名：L〇mL 2謝〇7，丙稀酸 曱西曰3有里1 1 . 2莫耳％ )之外，其餘均施行與實施例1 〇 同樣的操作，獲得第丨圖所示構造的太陽電池用保護薄板。 〔實施例15〕 除將構成第1層的共聚物B，變更為乙烯-甲基丙烯酸 共聚物（三井•杜邦高分子化學公司製，Nucrel N1525，甲 基丙稀酸含有量：5.4莫耳％)之外，其餘均施行與實施例 10同樣的操作’獲得第1圖所示構造的太陽電池用保護薄 板。 〔實施例16〕 除將構成第1層的共聚物B，變更為乙烯-醋酸乙烯酯 共聚物（Tosoh公司製，ULTRATHENE 750，醋酸乙烯酯含有 量.13. 3莫耳％)之外，其餘均施行與實施例1〇同樣的操 作，獲得第1圖所示構造的太陽電池用保護薄板。 〔實施例17〕 除將構成第1層的共聚物B，變更為共聚物B、與乙烯 -丙烯酸丁酯共聚物（ARKEMA公司製，商品名：L0TRYL 35BA40 ’丙烯酸丁酯含有量：10. 5莫耳％ ;共聚物C)，依 質量比6: 4(共聚物B:共聚物C)的摻合物之外，其餘均 34 201246572 施行與實施例ίο同樣的操作’獲得第丨圖所示構造的太陽 電池用保護薄板。 〔實施例18〕 除將構成第2層的聚乙烯系樹脂，變更為密度9丨〇kg/m3 的聚乙稀系樹脂（Tosoh公司製’商品名：lumitaC 54-1)， 且將第1層厚度變更為10/ζπι，並將第2層厚度變更為 90 # m之外’其餘均施行與實施例9同樣的操作，獲得第1 圖所不構造的太陽電池用保護薄板。 〔實施例1 9〕 將構成第2層的聚乙烯系樹脂，變更為密度91〇kg/m3 的聚乙烯系樹脂（Tosoh公司製，商品名：lumitaC 54-1)， 且將第1層厚度變更為50//m，並將第2層厚度變更為 50 # m之外’其餘均施行與實施例9同樣的操作，獲得第i 圖所不構造的太陽電池用保護薄板。 〔實施例20〕 除將構成第2層的聚乙烯系樹脂，變更為密度91 〇Kg/m3 的聚乙烯系樹脂（Tosoh公司製’商品名：LUMITAC 54-1)， 且將第1層厚度變更為70μπι’並將第2層厚度變更為 30 // m之外’其餘均施行與實施例9同樣的操作，獲得第i 圖所示構造的太陽電池用保護薄板。 〔實施例21〕 除將基材的PET薄膜，變更為厚度50/Z m的pET薄膜 (T0RAY 公司製，Lumirror X10S，厚度 50/im)，且將第 1 層厚度變更為5νιη’並將第2層厚度變更為i5//m之外， 35 201246572 ’獲得第1圖所示構造 其餘均施行與實施例12同樣的操作 的太陽電池用保護薄板。 〔實施例22〕 (T0RAY 公司製 ’ Lumirror Xl〇s， 除將基材輯τ薄膜’變更為厚度ι〇〇"“”ετ薄膜 層厚度變更為50#m’並將第2層犀厗料, 早度變更為50#m之外， 其餘均施行與實施例12阁婵Μ 4。a j Z H樣的刼作，獲得第1圖所示構造 的太陽電池用保護薄板 〔實施例23〕 除將基材的PET薄膜’變更為厚度25〇Am的m薄膜 (帝人杜邦薄膜公司製’ MeHnex s，厚度25{)"m)，且將 第1層厚度變更為75/zm，並將第2層厚度變更為225 //m 之外，其餘均施行與實施例12同樣的操作，獲得第丨圖所 示構造的太陽電池用保護薄板。 〔實施例24〕 將具揽拌機的聚合鍋中施行脫氣，並再該聚合鍋中注 入1H-十三II己烷3〇〇 〇g、13_二氣—五氟丙烷 (和光化學公司製：HCFC-225)75.0g 、及 3, 3’4, 4’5, 5’6, 6, 6-九氟-1-己烯1.49g。更擠入六氟丙烷 157.3g、四氟乙烯49.2g、及乙烯1.6g，並使聚合鍋溫度 升溫至66°C。 接著，添加屬於聚合起始劑的三甲基乙醯基過氧化第 三丁基0. 564g ’使開始進行聚合。為在聚合中能使壓力保 持一定’便使四氟乙烯/乙烯混合單體氣體（混合比：54/46) 36 201246572 連續地流入聚合鍋中。又，連續地流入κ 〇莫耳％的 3,3’4,4,5’5’6,6,6-九氟_卜己烯、〇.25莫耳％的衣康酸 針、及含有i質量二氯]，12,2,3 —五氟丙院之四 氟乙烯/乙烯混合單體氣體（混合比：54/46)。然後在裝 填混合單體氣冑7Gg的時點便停止聚合，將聚合㈣度冷 卻至室溫’同時施行返淨直到常壓。使所獲得樹脂依12〇 °C進行24小時乾燥，便獲得目標之氟樹脂(乙浠四氟乙烯 (ETFE)樹脂；稱「氟樹脂丨」）。 在所獲仔氟樹脂1中’依氧化鈦成為2〇質量%的方式 添加ETFE的顏料母料（大田精化工業公司製，h_5i〇〇)並混 練’獲得白色氟樹脂（稱「氟樹脂2」）。 對PET薄膜（帝人杜邦薄膜公司製，帝㈣sl厚度 125/zm)的雙面施行電暈處理（輸出2〇〇〇幻。然後，利用τ 型模頭製膜機(擠筒溫度：200t，τ型模頭溫度：3〇〇t)， 將上述所獲;^氟樹脂2、與乙稀_甲基丙稀酸環氧丙醋共聚 物（ARKEMA公司製，商品名：L_ER Αχ8刚，甲基丙婦 酸環氧丙醋含有量：8.0莫耳％)，分別依厚度成為25口， 且乙稀f &丙烯酸j哀氧丙西旨共聚物靠基材側的方式，對上 述PET薄膜其中一面施行直接共擠出塗佈，而形成熱可塑 性樹脂層與氟樹脂層。 再者，對上述PET薄膜另一面，與實施例9同樣的施 行共擠出塗佈，形成由第1層（乙烯—丙烯酸丁酯共聚物B) 與第2層（密度880kg/m3的聚乙烯系樹脂）所構成熱可塑性 樹脂層，便獲得第3圖所示構造的太陽電池用保護薄板。 37 201246572 〔實施例25〕 在基材的PET薄膜（帝人杜邦薄膜公司製，帝特龍SL， 厚度125"m)其中一面上’將氟樹脂（旭硝子公司製的And containing 1% by mass of 1, rat-1,1,2,2,3-pentafluoropropanone 4 29 201246572 Vinyl fluoride/ethylene mixed monomer gas (mixing ratio: 54/46). Then, the polymerization was stopped at the time of charging the mixed monomer gas of 7 〇g, and the temperature of the polymerization pot was cooled to room temperature while being forced to a normal pressure. The obtained resin was dried at i 2 ° C for 24 hours to obtain a target fluororesin (ethylene tetrafluoroethylene (ETFE) resin; "fluoro resin 1"). In the obtained fluororesin 1 , a pigment masterbatch (H_51 制, manufactured by Daejeon Seika Co., Ltd.) of ETFE was added to the fluororesin 1 in an amount of 20% by mass of titanium oxide, and kneaded to obtain a white fluororesin (referred to as "fluororesin 2"). . Corona treatment (output 2 〇〇〇 w) was performed on both sides of a PET film (manufactured by Teijin DuPont Film Co., Ltd., Titron SL thickness 125# m). Then, using a τ type boring machine (extrusion temperature: 200. (:, T-die temperature: 3 〇 (TC), the above obtained fluororesin 2, and ethylene-glycidyl methacrylate) Copolymer (manufactured by ARKEMA, trade name: L0TADER Αχ 884 〇, propylene glycol methacrylate content: 8.0 mol%), respectively, according to thickness 25 " m, and ethylene-methacrylic acid butyl acrylate copolymer The thermoplastic resin layer and the fluororesin layer were formed by direct co-extrusion coating on one side of the PET film on the side of the substrate. Further, the same operation as in Example 2 was carried out on the other side of the PET film. By extrusion coating, a thermoplastic resin layer composed of a first layer (copolymer B) and a second layer (low density polyethylene resin) was formed, and a protective sheet for a solar cell having the structure shown in Fig. 3 was obtained. Example 8] Except that the copolymer A was changed to an ethylene-glycidyl methacrylate copolymer ("LOTADER AX8840, methacrylic acid propylene glycol 201246572 酉曰 content. 8.0 mol%, manufactured by ARKEMA Co., Ltd.), The rest are the same as in the first embodiment. 'The protective sheet for solar cells having the structure shown in Fig. 1 was obtained. [Comparative Example 1] The corona-treated surface of the PET film obtained in the same manner as in Example 1 was low-density polyethylene (T〇s〇h company) Product name: LUMITAC 434, density 905 kg/m3) Direct extrusion coating was applied to a thickness of 75 μm to form a thermoplastic resin layer, and a protective sheet for a solar cell was obtained. [Test Example 1] < Evaluation> According to the method specified in Japanese Industrial Standard: JIS K6854-3: 1999 "Adhesive - Peeling Strength Test Method - Part 3: τ-shaped peeling", the protective sheets for solar cells obtained in the examples and comparative examples were evaluated. Specifically, the following is the following: The protective sheet for solar cells obtained in the examples and the comparative examples was cut into 25 nun x 200 mm to prepare a test piece, and the peeling manner of the substrate and the thermoplastic resin layer in the test piece was obtained. The fasteners fixed on the upper and lower sides of the universal tensile testing machine are peeled off at a peeling speed of 300 mm/inin at a temperature of 23 t: and a humidity of 5 〇 % RH, and the load at this time is regarded as an adhesion force. In the initial stage: N/25 mm) and measured (in the measurement, the opening angle of the base material and the thermoplastic resin layer was fixed to 180 degrees). The results are shown in Table 1. Further, the above test piece was put into a high pressure cooking test. After the cooker test: 12 rc, humidity l〇〇% RH, 24 hours), the adhesion was measured in the same manner as above (after durability: N/25 min). The results are shown in Table 1. [Test Example 2] <Measurement of curl amount > The protective sheet for solar cells obtained in the examples or the comparative examples was cut into 31 201246572 3〇〇mmx3〇〇mm squares, placed on a horizontal platform, and the vertical distance (mm) from the top surface of the four corners to the curled top was measured. . The average value of each distance obtained in the four places was calculated and regarded as "curl amount (mm)". The results are shown in Table 1. [Table 1] Next force (N/25 mm) Curl amount (mm) After initial durability Example 1 > 25 > 25 21.3 Example 2 > 25 > 25 15.3 Example 3 > 25 > 25 18. 7 Embodiment 4 > 25 > 25 20, 8 Embodiment 5 > 25 > 25 13.6 Embodiment 6 > 25 > 25 8.3 Embodiment 7 > 25 > 25 14.6 Example 8 > 25 &gt 25: 〇 Comparative Example 1 14.8 3.1 24.1 It is understood from Table 1 that the adhesion between the protective sheet substrate for a solar cell (PET film) and the thermoplastic resin layer of the examples is high, and the amount of curl is small. [Example 9] One side of a PET film (manufactured by Tory Co., Ltd., Lumirr〇r xl〇s, thickness: 125 cm) was subjected to corona treatment (output 2 〇〇〇 w). A τ type die forming machine was used ( Extrusion temperature: 230~280°C, Τ-type die temperature: 300 °c), ethylene-butyl acrylate copolymer (manufactured by ARKEMA, trade name: LOTRYL 30BA02, butyl acrylate content: 8 6 m %; copolymer B), polyethylene resin with a density of 880 kg/m3 (manufactured by Sumitomo Chemical Co., Ltd., product name: EKELEN CX4002), respectively, 25/^ and 75//m 32 depending on the thickness In the method of 201246572, and the copolymer B is on the side of the substrate, direct co-extrusion coating is applied to the corona-treated surface of the pa film to form a first layer (juniture B) and a second layer (density). A protective sheet for a solar cell having the structure shown in Fig. 1 was obtained as the thermoplastic resin layer of the 880 kg/m3 polyethylene resin. [Example 10] The polyethylene bismuth resin constituting the second layer was changed. The same operation as in Example 9 was carried out except for a polyethylene resin having a density of 890 kg/m 3 (manufactured by Prime Polymer Co., Ltd., trade name: ev〇lUE SP 9 0 0 1 0 0), and FIG. 1 was obtained. [Example 11] The polyethylene resin constituting the second layer was changed to a polyethylene resin having a density of 9 〇〇kg/m3 (manufactured by Tosoh Corporation, trade name: LUMITAC 22). -6) The same operation as in Example 9 was carried out except that the protective sheet for a solar cell having the structure shown in Fig. 1 was obtained. [Example 12] The polyethyl fluorene resin constituting the second layer was changed. It is a polyethylene resin with a density of 91 〇kg/m3 (manufactured by T〇s〇h Co., Ltd. Name: addition LUMITAC 54-1), the rest were performed the same operation as in Example 9, to obtain the configuration shown in FIG Shu of the protective sheet for solar cells. [Example 13] The polyethylene resin constituting the second layer was changed to 50 parts by mass of a polypropylene resin (manufactured by Prime P〇lymer Co., Ltd., trade name: Prime P〇lypro F-744NP) having a density of 890 kg/m3. Polyethylene resin with a density of 9〇5kg/m3 (manufactured by T〇s〇h Co., Ltd., trade name: UMITAC 43_1) 5 〇 33 33 201246572 Injury blend (mixed resin density: all other applications) The lamp was subjected to the same operation as in Example 9 to obtain a protective sheet for a solar cell having the structure shown in Fig. i. [Example 14] The copolymer B of the first layer was changed to an ethylene-acrylic acid acrylate copolymer (ARKEMA). The company's system, the trade name: L〇mL 2 〇 〇 7, 丙 曱 曰 曰 有 有 有 有 有 有 有 有 有 有 有 有 1 1 1 1 1 1 1 1 1 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 [Example 15] The copolymer B of the first layer was changed to an ethylene-methacrylic acid copolymer (manufactured by Mitsui & DuPont Polymer Chemical Co., Ltd., Nucrel N1525, methyl group). Except for the content of acrylic acid: 5.4 mol%) [Example 16] The protective sheet for a solar cell having the structure shown in Fig. 1 was obtained. [Example 16] The copolymer B constituting the first layer was changed to an ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, ULTRATHENE 750). The same operation as in Example 1 was carried out except that the vinyl acetate content was 13.3 mol%, and the protective sheet for a solar cell having the structure shown in Fig. 1 was obtained. [Example 17] Copolymer B constituting the first layer was changed to copolymer B and ethylene-butyl acrylate copolymer (manufactured by ARKEMA, trade name: L0TRYL 35BA40 'butyl acrylate content: 10.5 mol%; copolymer C In the same manner as in the example ίο, except for the blend of the mass ratio of 6:4 (copolymer B: copolymer C), the protective sheet for solar cells having the structure shown in Fig. 1 was obtained. [Example 18] The polyethylene resin constituting the second layer was changed to a polyethylene resin having a density of 9 丨〇 kg/m 3 (trade name: lumita C 54-1 manufactured by Tosoh Co., Ltd.), and Change the thickness of 1 layer to 10/ζπι, and change the thickness of the second layer to 90. The same operation as in Example 9 was carried out, and the protective sheet for solar cells not structured in Fig. 1 was obtained. [Example 1 9] The polyethylene resin constituting the second layer was changed to density. 91 〇 kg/m3 of polyethylene resin (trade name: lumita C 54-1, manufactured by Tosoh Co., Ltd.), and the thickness of the first layer was changed to 50 / / m, and the thickness of the second layer was changed to 50 # m. The rest of the operation was carried out in the same manner as in Example 9 to obtain a protective sheet for a solar cell which was not constructed in the first embodiment. [Example 20] The polyethylene resin constituting the second layer was changed to a polyethylene resin having a density of 91 〇Kg/m3 (trade name: LUMITAC 54-1, manufactured by Tosoh Corporation), and the thickness of the first layer was changed. The same operation as in Example 9 was carried out except that the thickness of the second layer was changed to 70 μm and the thickness of the second layer was changed to 30 // m. The protective sheet for a solar cell having the structure shown in Fig. i was obtained. [Example 21] A PET film of a base material was changed to a pET film (Lumirror X10S, thickness 50/im, manufactured by Toray Co., Ltd.) having a thickness of 50/Z m, and the thickness of the first layer was changed to 5 νηη' The thickness of the two layers was changed to i5//m, and the protective sheet for solar cells, which was subjected to the same operation as in Example 12, was obtained in the configuration shown in Fig. 1 . [Example 22] (Lumirror Xl〇s manufactured by T0RAY Co., Ltd., except that the base film τ film was changed to the thickness ι〇〇" "" ετ film layer thickness was changed to 50 #m' and the second layer of rhinoceros The material was changed to 50#m in the morning, and the rest of the work was carried out in the same manner as in Example 12, aj ZH-like, and the protective sheet for solar cells having the structure shown in Fig. 1 was obtained (Example 23). The PET film of the substrate was changed to an m film having a thickness of 25 〇Am (manufactured by Teijin DuPont Film Co., Ltd., MeHnex s, thickness 25{) "m), and the thickness of the first layer was changed to 75/zm, and The same operation as in Example 12 was carried out except that the thickness of the two layers was changed to 225 //m, and the protective sheet for solar cells having the structure shown in Fig. 1 was obtained. [Example 24] Degassing was carried out in a polymerization pot equipped with a mixer, and then 1H-tride-II hexane 3 〇〇〇g, 13_di-pentafluoropropane was injected into the polymerization pot (and photochemical company) System: HCFC-225) 75.0g, and 3, 3'4, 4'5, 5'6, 6, 6-nonafluoro-1-hexene 1.49g. Further, 157.3 g of hexafluoropropane, 49.2 g of tetrafluoroethylene, and 1.6 g of ethylene were extruded, and the temperature of the polymerization vessel was raised to 66 °C. Next, the trimethylethenyl peroxybutyl butyl group 0. 564 g' which is a polymerization initiator was added to start polymerization. In order to maintain the pressure in the polymerization, the tetrafluoroethylene/ethylene mixed monomer gas (mixing ratio: 54/46) 36 201246572 was continuously flowed into the polymerization vessel. Further, it continuously flows into the 3,3'4,4,5'5'6,6,6-nonafluoro-bhexene, 〇.25 mol% itaconic acid needle of κ 〇 mol%, and contains i quality dichloro], 12, 2, 3 - pentafluoropropyl tetrafluoroethylene / ethylene mixed monomer gas (mixing ratio: 54/46). Then, the polymerization was stopped at the time of loading 7 gg of the mixed monomer gas, and the polymerization (four degrees) was cooled to room temperature while returning to normal pressure. The obtained resin was dried at 12 ° C for 24 hours to obtain a target fluororesin (ethrenetetrafluoroethylene (ETFE) resin; "fluororesin"). In the obtained fluororesin 1 , a pigment masterbatch of ETFE (manufactured by Daejeon Seika Co., Ltd., h_5i〇〇) was added in a manner of 2% by mass of titanium oxide, and kneaded to obtain a white fluororesin (referred to as "fluororesin 2". "). Double-sided corona treatment of PET film (manufactured by Teijin DuPont Film Co., Ltd., Emperor (4) sl thickness 125/zm) (output 2 illusion. Then, using τ-type die-cutting machine (squeezing cylinder temperature: 200t, τ Type die temperature: 3〇〇t), obtained from the above; ^ fluororesin 2, and ethylene _ methyl acrylate acid propylene vinegar copolymer (ARKEMA company, trade name: L_ER Αχ 8 just, methyl The content of propylene glycol acid propylene vinegar: 8.0 mol%), respectively, according to the thickness of 25 mouths, and ethylene f & acrylic acid j oxime oxime copolymer on the substrate side, the above PET film The thermoplastic resin layer and the fluororesin layer were formed by direct co-extrusion coating. Further, on the other side of the PET film, co-extrusion coating was carried out in the same manner as in Example 9 to form a first layer (ethylene). - A butyl acrylate copolymer B) and a thermoplastic resin layer composed of a second layer (polyethylene resin having a density of 880 kg/m3) to obtain a protective sheet for a solar cell having the structure shown in Fig. 3. 37 201246572 [Examples] 25] PET film on the substrate (made by Teijin DuPont Film Co., Ltd., Tetelon SL, thick 125 " m) on one side of 'the fluororesin (manufactured by Asahi Glass Co.

Lumifron LF-200、盥 q1iit1 ,· uQ D mika Bayer Urethane 公司製的 SUMIDUR 3300、以及杜邦公司製ri〇5 ,依i〇〇質 量份：10質量份：30質量份比率進行混合者)利用邁耶塗 佈機施行塗佈，經依13Gt施行U鐘乾燥，形成厚度15" 的氟樹脂層，便製得氟塗佈處理m薄膜。錢，對所獲 得氟塗佈處理PET薄膜的非翁务 辱膜的非氟塗佈面施行電暈處理（輸出 2000W)。 在上述PET薄膜的電量虚^ 一 町电箪處理面上，依與實施例10同樣 的施行共擠出塗佈，而形成由第] 取田弟1層（乙烯_丙烯酸丁酯共 聚物Β)與第2層（密度890kg/m3的 s丨们心乙烯系樹脂）所構成熱 可塑性樹脂層’便獲得第2圖所 厅不構造的太陽電池用保護 薄板。 〔實施例26〕 除將構成第2層的聚乙嫌系椒 歸糸樹知’變更為密度890kg/m3 的聚乙烯系樹脂（prime P〇1 公 A习製，商品名：EV0LUE SP90 01 00)1 00質量份、與氧化鈦丨 3質量份的混合物之外， 其餘均施行與實施例1〇同樣的操 '作’獲得第1圖所示構造 的太陽電池用保護薄板。 〔比較例2〕 對基材的PET薄膜（T0RAY公司制 ^ J Lumi rror XI OS > 厚度125/zin)其中一面施行電暈處Lumifron LF-200, 盥q1iit1, uQ D SUMIDUR 3300 manufactured by Mika Bayer Urethane Co., Ltd., and ri〇5 manufactured by DuPont Co., Ltd., based on i〇〇 mass parts: 10 parts by mass: 30 parts by mass) The coating machine was applied and dried by a U-clock at 13 Gt to form a fluororesin layer having a thickness of 15 ", and a fluorine-coated m film was obtained. For the money, the non-fluorine coated surface of the non-woven film of the fluorine-coated PET film was subjected to corona treatment (output 2000 W). In the same manner as in Example 10, the co-extrusion coating was carried out in the same manner as in Example 10 on the surface of the PET film of the PET film, and the first layer (the ethylene butyl acrylate copolymer Β) was formed. The thermoplastic resin layer constituting the second layer (having a density of 890 kg/m 3 of the vinyl resin) is obtained as a protective sheet for a solar cell which is not structured in the second embodiment. [Example 26] A polyethylene resin having a density of 890 kg/m3 was changed to a polyethylene resin (primary P 〇 1 A A, product name: EV0LUE SP90 01 00) The solar cell protective sheet having the structure shown in Fig. 1 was obtained by the same operation as in Example 1 except that a mixture of 100 parts by mass and 3 parts by mass of titanium oxide was used. [Comparative Example 2] A corona sheet was applied to one side of a PET film (manufactured by T0RAY Co., Ltd., J Lumi rror XI OS > thickness 125/zin)

& Η輸出2000W)。利用T 38 201246572 型模頭製膜機（擠筒溫度：230〜280°C，T型模頭溫度：3〇〇 °C ) ’將密度918kg/m3的聚乙烯系樹脂（曰本聚乙烯公司 製，商品名：NOVATEC LC615Y) ’依厚度成為i〇〇"m的方 式’對上述PET薄膜的電暈處理面施行擠出塗佈而形成單 層的熱可塑性樹脂層，便獲得太陽電池用保護薄板。 〔比較例3〕 對基材的PET薄膜（T0RAY公司製，Lumirror Xl〇S， 厚度125ym)其中一面施行電暈處理（輸出2〇〇〇w)。利用T 型椒頭製膜機（擠筒溫度：230〜280°C，T型模頭溫度：300 °C )，將乙烯-丙烯酸丁酯共聚物b(ARKEMA公司製，商品 名：LOTRYL 30BA02，丙烯酸丁酯含有量：8· 6莫耳。/。），依 厚度成為100 # m的方式，對上述PET薄膜的電暈處理面施 行擠出塗佈而形成單層的熱可塑性樹脂層，便獲得太陽電 池用保護薄板。 〔試驗例3〕<融解熱量測定> 針對實施例9〜26與比較例2〜3中構成熱可塑性樹脂層 的稀煙糸樹月曰’使用微分掃描熱量計（Ta instruments公 司製，型號：Q 2 0 0 〇 )，依下述條件施行熱量變化測定，並 擷取數據。 •樣品調整條件 從-40°C依升溫速度2(TC/分施行加熱至25(TC。 •測定條件 依25 0°C保持5分鐘後’依降溫速度2(TC /分施行冷卻 至-4 0’並測定熱量變化。 39 201246572 從所獲得數據，計算出因固體化而出現的尖峰面積， 將其視為「融解熱量△H(J/g)」。結果如表2所示。 〔試驗例4〕<密度測定> 針對實施例9〜26與比較例2〜3十構成熱可塑性樹脂層 的烯烴系樹脂，根據JIS K7112施行密度（kg/m3)測定。另 外’當測定2種以上樹脂的摻合物時’係針對經利用雙螺 桿混練機（東洋精機製作所公司製，製品名：實驗塑膠撞擊 研磨機）依21 0。(：施行混練，並利用水槽施行急冷後，再度 加工為顆粒狀物實施測定。結果如表2所示。 〔試驗例5〕<黏合貼附評價> 將實施例9〜26與比較例2〜3所製得太陽電池用保護薄 板，在直徑3吋、寬35〇mm的紙管上捲取i〇〇m，便製得評 價樣品。將該評價樣品在4(rc環境下保管i週後依下述 基準評價再度施行繞出時的狀況。結果如表2所示。 〇：無阻力、可繞出。 △:雖可繞出，但有部分性出現黏合貼附情形，在薄板表 面上殘留黏合貼附的痕跡。 X :部分性或全體性中王目針人μ 出現黏s貼附，無法進行繞出。 〔試驗例6〕<接著性評價> 實施例9〜26與比較例21斛搐巧丄b J z d所獲侍太陽電池用保護薄板 的接著性’依照試驗例1所 ㈣1所錢方法進行評價。結果如表 2所示。 〔試驗例7〕<捲曲量測定> 實施例9 ~ 2 6與比較例2 ~ 3 所獲得 太陽電池用保護薄板 40 201246572 的接著性，依照試驗例2所記載方法進行測定、計算。結 果如表2所示。 [表2 ]& Η output 2000W). Using T 38 201246572 die-making machine (squeeze temperature: 230~280°C, T-die temperature: 3〇〇°C) 'Polyester resin with a density of 918kg/m3 (Sakamoto Polyethylene Co., Ltd.) Product name: NOVATEC LC615Y) 'The method of forming the corona-treated surface of the PET film by extrusion coating to form a single-layer thermoplastic resin layer to obtain a solar cell Protect the sheet. [Comparative Example 3] One side of a PET film (manufactured by Toray Co., Ltd., Lumirror Xl〇S, thickness: 125 μm) was subjected to corona treatment (output 2 〇〇〇 w). Using a T-type pepper head film forming machine (squeezing barrel temperature: 230 to 280 ° C, T-die temperature: 300 ° C), ethylene-butyl acrylate copolymer b (manufactured by ARKEMA, trade name: LOTRYL 30BA02, The content of butyl acrylate is 8.6 mol/m., and the corona-treated surface of the PET film is extrusion-coated to form a single-layer thermoplastic resin layer in such a manner that the thickness is 100 #m. Obtain a protective sheet for solar cells. [Test Example 3] <Measurement of heat of fusion> The use of a differential scanning calorimeter (manufactured by Ta Instruments Co., Ltd.) for the thermoplastic resin layer of the thermoplastic resin layer of Examples 9 to 26 and Comparative Examples 2 to 3 was used. :Q 2 0 0 〇), the heat change measurement was performed according to the following conditions, and data was taken. • The sample adjustment conditions are from -40 ° C according to the heating rate 2 (TC / min heating to 25 (TC. • After the measurement conditions are maintained at 25 ° C for 5 minutes) - according to the cooling rate 2 (TC / min cooling to -4 0' and measure the change in heat. 39 201246572 From the obtained data, the peak area due to solidification was calculated and regarded as "melting heat △H (J/g)". The results are shown in Table 2. Example 4] <Measurement of Density> The olefin-based resin constituting the thermoplastic resin layer of Examples 9 to 26 and Comparative Examples 2 to 3 was measured in accordance with JIS K7112 density (kg/m3). The blend of the above resins is based on the use of a twin-screw kneading machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: experimental plastic impact grinding machine) according to 21 0. (: Performing mixing and re-cooling using a water tank, re-processing The measurement was carried out for the pellets. The results are shown in Table 2. [Test Example 5] <Adhesive adhesion evaluation> The protective sheets for solar cells obtained in Examples 9 to 26 and Comparative Examples 2 to 3 were in diameter. 3〇〇, 35〇mm paper tube is taken up i〇〇m, it will be evaluated The evaluation sample was stored in a 4 (rc environment) for one week, and the condition at the time of winding out again was evaluated according to the following criteria. The results are shown in Table 2. 〇: no resistance, no wraparound. △: Although it can be wound Out, but there is a partial adhesion and adhesion, leaving traces of adhesion and adhesion on the surface of the thin plate. X: Partial or all-in-one, Wangmu needle person μ appears sticky s attach, can not be circumvented. 6] <Adhesive evaluation> The adhesion of the protective sheets for solar cells obtained in Examples 9 to 26 and Comparative Example 21 was compared with the method of the test method 1 (4). As shown in Table 2 [Test Example 7] <Measurement of Curl Amount> The adhesion of the solar cell protective sheet 40 201246572 obtained in Examples 9 to 26 and Comparative Examples 2 to 3 was in accordance with the method described in Test Example 2. The measurement and calculation were carried out. The results are shown in Table 2. [Table 2]

融解熱量 △ H(J/g) 密度 (kg/m3) 接著力（N/25m) 捲曲量 (mm) 黏合貼附 初期 耐久後 實施例9 50 880 >25 >25 6.3 〇 實施例10 80 890 >25 >25 8.3 〇 實施例11 88 900 >25 >25 13.5 〇 實施例12 95 910 >25 >25 17, 3 〇 實施例13 87 898 >25 >25 12.4 〇 實施例14 80 890 >25 >25 11.1 〇 實施例15 80 890 >25 >25 13.9 〇 實施例16 80 890 >25 >25 9.0 〇 實施例17 80 890 >25 >25 7.0 〇 實縮例18 95 910 >25 >25 19.7 〇 實施例19 95 910 >25 >25 13.1 〇 實施例20 95 910 >25 >25 10.9 〇 實施例21 95 910 >26 >25 18.8 〇 實施例22 95 910 >25 >25 16.9 〇 實施例23 95 910 >25 >25 14.8 〇 實施例24 50 880 >25 >25 8.3 〇 實施例25 80 890 >25 >25 8.3 〇 實施例26 80 890 >25 >25 8.3 〇 比較例2 108 918 9.8 4.4 36.4 〇 比較例3 — — >25 >25 8.8 X 由表2中得知，實施例9〜26的太陽電池用保護薄板係 在與基材（PET薄膜）及熱可塑性樹脂層間之接著力較高， 且捲曲量較小，更沒有黏合貼附的問題。 產業上之可利用性 本發明的太陽電池用保護薄板係頗適用為例如太陽電 41 201246572 池模組的背板。 【圖式簡單說明】 第1圖係本發明一實施形態的太陽電池用保護薄板之 概略剖視圖》 第2圖係本發明另一實施形態的太陽電池用保鹱薄板 之概略剖視圖。 第3圖係本發明另一實施形態的太陽電池用保|蔓薄板 之概略剖視圖。 第4圖係本發明另一實施形態的太陽電池用保護薄板 之概略剖視圖。 第5圖係本發明另一實施形態的太陽電池用保護薄板 之概略剖視圖。 第6圖係本發明一實施形態的太陽電池模組之概略剖 視圖。 第7圖係本發明另一實施形態的太陽電池模組之概略 剖視圖。 【主要元件符號說明】 1 太陽電池用保護薄板 2 太陽電池單元 3 密封材 4 玻璃板 10 太陽電池模組 42 201246572 11 基材 12 熱可塑性樹脂層 13 氣樹脂層 14 第2熱可塑性樹脂層 15 蒸鍵層 16 接著層 17 金屬薄板 121 第1層 122 第2層 43Heat of fusion △ H (J / g) Density (kg / m3) Next force (N / 25m) Curl amount (mm) After the initial adhesion of the adhesive attaching Example 9 50 880 > 25 > 25 6.3 〇 Example 10 80 890 > 25 > 25 8.3 〇 Example 11 88 900 > 25 > 25 13.5 〇 Example 12 95 910 > 25 > 25 17, 3 〇 Example 13 87 898 > 25 > 25 12.4 〇 Example 14 80 890 > 25 > 25 11.1 〇 Example 15 80 890 > 25 > 25 13.9 〇 Example 16 80 890 > 25 > 25 9.0 〇 Example 17 80 890 > 25 > 7.0 Compaction 18 95 910 > 25 > 25 19.7 〇 Example 19 95 910 > 25 > 25 13.1 〇 Example 20 95 910 > 25 > 25 10.9 〇 Example 21 95 910 >>25 18.8 〇Example 22 95 910 >25 >25 16.9 〇Example 23 95 910 >25 >25 14.8 〇Example 24 50 880 >25 >25 8.3 〇Example 25 80 890 &gt ;25 >25 8.3 〇Example 26 80 890 >25 >25 8.3 〇Comparative Example 2 108 918 9.8 4.4 36.4 〇Comparative Example 3 — — >25 >25 8.8 X It is known from Table 2 that implementation Example 9 to 26 for solar cells The protective sheet has a high adhesion force with the substrate (PET film) and the thermoplastic resin layer, and the amount of curl is small, and there is no problem of adhesion and adhesion. Industrial Applicability The protective sheet for a solar cell of the present invention is suitably used as, for example, a back sheet of a solar cell 41 201246572 pool module. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of a protective sheet for a solar cell according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a protective sheet for a solar cell according to another embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing a protective sheet for a solar cell according to another embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing a protective sheet for a solar cell according to another embodiment of the present invention. Fig. 5 is a schematic cross-sectional view showing a protective sheet for a solar cell according to another embodiment of the present invention. Fig. 6 is a schematic cross-sectional view showing a solar battery module according to an embodiment of the present invention. Fig. 7 is a schematic cross-sectional view showing a solar battery module according to another embodiment of the present invention. [Description of main components] 1 Solar cell protection sheet 2 Solar cell unit 3 Sealing material 4 Glass plate 10 Solar cell module 42 201246572 11 Substrate 12 Thermoplastic resin layer 13 Gas resin layer 14 Second thermoplastic resin layer 15 Steaming Key layer 16 next layer 17 metal thin plate 121 first layer 122 second layer 43

Claims (1)

201246572 七、申請專利範圍： 1. 種太陽電池用保護薄板，包括：基材、與在上述 基材至少其中一面上積層的熱可塑性樹脂層； 其特徵在於： 上述熱可塑性樹脂層係包括第丨層與第2層；該第工 層係積層於上述基材上，且以乙烯、與從（甲基）丙烯酸、（曱 基）丙烯酸酯、（甲基）丙烯酸環氧丙酯及醋酸乙烯酯所構成 群組中選擇從至少1種的共聚物為主成分；該第2層係積 層於上述第1層上，且以烯烴系樹脂為主成分。 2. 如申請專利範圍第i項之太陽電池用保護薄板，其 中’上述第1層的上述共聚物中，當作單體單元用之（曱基） 丙烯酸 '(甲基）丙烯酸酯、（曱基）丙烯酸環氧丙酯及醋酸 乙烯醋的合計含有量，係3. 丨5莫耳〇/〇。 3·如申請專利範圍第1項之太陽電池用保護薄板，其 中’上述第1層的上述共聚物中，當作單體單元用之（甲基） 丙烯酸酯，係從丙烯酸曱酯、丙烯酸丁酯、丙烯酸_2_乙基 己醋及甲基丙烯酸曱酯所構成群組中選擇至少1種。 4. 如申請專利範圍第1項之太陽電池用保護薄板，其 中’上述第2層的上述烯烴系樹脂係含有當作單體單元用 的乙烯60〜1 〇〇質量％。 5. 如申請專利範圍第1項之太陽電池用保護薄板，其 中’上述第2層的上述烯烴系樹脂係密度875~92〇kg/m3， 利用微分掃描熱量計所獲得融解熱量△ Η係丨〇 〇. 〇 J/g以 下。 44 201246572 6’如申明專利範圍第1項之太陽電池用保護薄板，其 、/上述熱可塑性樹脂層係利用上述第1層與上述第2層 進行共擠出塗佈而形成。 7’如申叫專利範圍第1項之太陽電池用保護薄板，其 中，上述基材的厚度係50〜250 ym; 上述熱可塑性樹脂層的厚度係上述基材厚度的1/3~2 倍。 8·如申明專利範圍帛1項之太陽電池用保護薄板，其 中上述第1層的厚度與上述第2層的厚度之比率係 9~7 : 3 。 9·如申明專利範圍第i至8項中任一項之太陽電池用 呆U板其中’上述熱可塑性樹脂層係與構成太陽電池 模組的密封材相接著之層。 10. -種太陽電池用保護薄板之製造方法，製造包括基 材與在上述基材至少其中—面上積層的熱可塑性樹脂層 之太陽電池用保護薄板； 其特徵在於： 形成包括第i層與第2層的上述熱可塑性樹脂層；該 第1層係由將以乙稀、與從（甲基）丙稀酸、（甲基）丙稀酸 醋、（甲基）㈣酸環氧㈣及醋酸乙烯8旨所構成群組中選 擇至）1種的共聚物為主成分之第i樹脂組成物，以及以 烯烴系樹脂為主成分的帛2樹脂組成物，依上述第i樹脂 組成物靠上述基材側的方式，共擠出塗佈於上述基材至少 其中-面1，而積層於上述基材上的上述第（樹脂組成物 45 201246572 構成；該第2層係由上述第1 成物構成。 層上積層的上述第 2樹脂组 11.—種太陽電池模組，包右 太陽電池單元予以密封的密封材 層的保護薄板； 包括.太陽電池單元 π、將上述 以及在上述密封材上積 其特徵在於： 上述保護薄板係由申請專利範圍第9項之太陽電池用 保護薄板構成； 上述保護薄板係隔著上述熱可塑性樹脂層接著於上述 密封材上。 46201246572 VII. Patent application scope: 1. A protective sheet for a solar cell, comprising: a substrate; and a thermoplastic resin layer laminated on at least one side of the substrate; wherein: the thermoplastic resin layer comprises a third layer a layer and a second layer; the layer is laminated on the substrate, and is made of ethylene, and (meth)acrylic acid, (meth)acrylic acid ester, glycidyl (meth)acrylate, and vinyl acetate. Among the constituent groups, at least one type of copolymer is selected as a main component, and the second layer is laminated on the first layer, and an olefin resin is used as a main component. 2. The protective sheet for solar cells according to item i of the patent application, wherein the above-mentioned copolymer of the first layer is used as a monomer unit ((mercapto)acrylic acid '(meth)acrylate, (曱The total content of glycidyl acrylate and vinyl acetate vinegar is 3. 丨5 mole 〇 / 〇. 3. The protective sheet for a solar cell according to the first aspect of the invention, wherein the (meth) acrylate used as a monomer unit in the copolymer of the first layer is a decyl acrylate or butyl acrylate. At least one selected from the group consisting of ester, acrylic acid 2-ethylhexanacetate and decyl methacrylate. 4. The solar cell protective sheet according to the first aspect of the invention, wherein the olefin-based resin of the second layer contains 60 to 1% by mass of ethylene as a monomer unit. 5. The protective sheet for a solar cell according to the first aspect of the patent application, wherein the olefin resin of the second layer is density 875 to 92 〇 kg/m 3 , and the heat of fusion is obtained by a differential scanning calorimeter. 〇〇. 〇J/g or less. In the solar cell protective sheet according to the first aspect of the invention, the thermoplastic resin layer is formed by co-extrusion coating of the first layer and the second layer. The solar cell protective sheet according to the first aspect of the invention, wherein the substrate has a thickness of 50 to 250 μm; and the thermoplastic resin layer has a thickness of 1/3 to 2 times the thickness of the substrate. 8. The solar cell protective sheet according to claim 1, wherein the ratio of the thickness of the first layer to the thickness of the second layer is 9 to 7:3. 9. The solar cell for use in a solar cell according to any one of claims 1 to 8, wherein the thermoplastic resin layer is a layer adjacent to a sealing material constituting the solar cell module. 10. A method for producing a protective sheet for a solar cell, comprising: a protective sheet for a solar cell comprising a substrate and a thermoplastic resin layer laminated on at least a surface of the substrate; wherein: forming an ith layer and a second layer of the thermoplastic resin layer; the first layer is made of ethylene, and (meth)acrylic acid, (meth)acrylic acid vinegar, (meth) (tetra) acid epoxy (four) and The i-th resin composition containing the copolymer of one type selected from the group consisting of vinyl acetate 8 and the quinone resin composition containing the olefin-based resin as a main component, and the ith resin composition based on the ith resin composition The substrate side is coextruded and applied to at least the surface of the substrate, and the first layer (resin composition 45 201246572 is laminated on the substrate; the second layer is formed by the first layer The second resin group 11 layered on the layer, the solar cell module, the protective sheet of the sealing material layer sealed by the right solar cell unit; the solar cell unit π, the above and the sealing material Accumulate Characterized in that: the protective sheet is comprised of the patent scope of the solar cell of item 9 with a protective sheet; and the protective sheet via the thermoplastic resin-based layer is then on the sealing member 46.
TW100137651A 2010-10-18 2011-10-18 A protective sheet for a solar cell and a method for manufacturing the same, and a solar cell module TWI546976B (en)

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