TW201018707A - Sealing material and solar cell module prepared therefrom - Google Patents

Sealing material and solar cell module prepared therefrom Download PDF

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Publication number
TW201018707A
TW201018707A TW098119230A TW98119230A TW201018707A TW 201018707 A TW201018707 A TW 201018707A TW 098119230 A TW098119230 A TW 098119230A TW 98119230 A TW98119230 A TW 98119230A TW 201018707 A TW201018707 A TW 201018707A
Authority
TW
Taiwan
Prior art keywords
group
component
polymer
sealing material
functional group
Prior art date
Application number
TW098119230A
Other languages
Chinese (zh)
Inventor
Takeo Nakamura
Toshiyuki Hayakawa
Teruo Aoyama
Takuya Sano
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW201018707A publication Critical patent/TW201018707A/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Sealing Material Composition (AREA)

Abstract

Provided is a sealing material having, as constituent components, (i) polypropylene, (ii) hydrogenated diene-based polymer and (iii) a polymer (a functional-group-containing polymer) which is different from said component (ii) and has at least one type of functional group. The material includes 1 to 100 parts by mass of component (iii) with respect to 100 parts by mass in total comprising 0 to 60 parts by mass of component (i) and 40 to 100 parts by mass of component (ii).

Description

201018707 六、發明說明： 【發明所屬之技術領域】 本發明有關封閉材料以及使用該封閉材料之太陽電池 模組。更詳言之’示有關可易於形成模組且透明性、耐熱 性、接著性等優異之封閉材料。 【先前技術】 Φ 太陽電池於近年來使用作爲乾淨的能源而備受矚目， 雖已變成亦可利用於一般住宅，但迄今仍尙未到充分普及 。其主要理由舉例爲太陽電池仍舊昂貴。至於其原因舉例 如下。太陽電池本身之發電效率並不充分，爲獲得所需電 力，不得不使模組增大。又，模組製造之生產性低。 太陽電池模組一般係將矽、鎵·砷、銅-銦-硒等隻太陽 電池元件以上部透明保護材及下部基板保護材予以保護， 以封閉材固定太陽電池元件及保護材，經封裝化者。爲此 # 作爲太陽電池元件封閉材料要求有透明性、耐熱性、與玻 璃或金屬等之上下各保護材之接著性良好。 目前，作爲太陽電池模組用太陽電池元件封閉材料， 由柔軟性、透明性等觀點觀之，使用有乙酸乙烯酯含量高 的乙烯•乙酸乙烯酯共聚物。此元件由於耐熱性、接著性 不足，因此有必要倂用有機過氧化物或矽烷偶合劑等予以 交聯。因此，太陽電池模組之製造，有必要經歷製作調配 有該等添加劑之乙烯•乙酸乙烯酯共聚物之薄片，層合數 分鐘至十數分鐘暫時接著成太陽電池元件之步驟，以及於 -5- 201018707 烘箱內於使有機過氧化物分解之高溫下持續數十分鐘至1 小時之正式接著步驟之耗費時間之步驟。又，於薄片製造 階段，由於有必要於不使有機過氧化物分解之低溫度成形 ，故押出成形速度無法變大。如上述，太陽電池模組之製 造耗費勞力及時間，使其製造成本上升成爲原因之一。 [專利文獻1]特公平2-4070 9號公報 【發明內容】 本發明係鑑於上述習知技術所具有之問題點而完成者 ，作爲其課題，係提供—種並無必要藉有機過氧化物之交 聯’因此可顯著改善太陽電池模組之生產效率，而且具有 作爲太陽電池元件封閉材料之優異特性之替代材料。 本發明人等爲達成上述課題經積極硏究之結果，發現 藉由以下所示之封閉材料可達成上述課題，因而完成本發 明。亦即，依據本發明，提供以下所示之封閉材料。 Π]—種封閉材料，其特徵爲以（i)成分：聚丙烯， (ii)成分：氫化二烯系聚合物，及（iii)成分：具有選 自下述官能基群X之至少一種官能基之聚合物且爲與上述 (Π)成分不同之聚合物（含有官能基之聚合物）作爲構 成成分’且相對於上述（i)成分〇〜6〇質量份，上述（π ) 成分40〜1〇〇質量份（合計量ι〇〇質量份），含有1〜1〇〇質量 份之上述（iii )成分， [官能基X]:羧基、酸酐基、環氧基、（甲基）丙烯 釀基、胺基、院氧基矽烷基、羥基、異氰酸酯基及噁唑啉 -6- 201018707 基。 [2] 如上述[1]記載之封閉材料，其中上述（ii)成分爲 含有下述聚合物嵌段A及下述聚合物嵌段B之聚合物，且爲 構成上述（ii)成分之下述共軛二烯化合物單位之雙鍵之 至少80%經氫化之氫化二烯系聚合物， [聚合物嵌段A]:含有50質量％以上之芳香族乙烯基化 合物單位之聚合物嵌段， [聚合物嵌段B]:含有50質量％以上之共軛二烯化合物 單位’且其1,2 -鍵含量及3,4 -鍵含量之合計在3〇〜90%範圍 內之聚合物嵌段。 [3] 如上述[1]或[2]記載之封閉材料，其中上述（η) 成分爲具有選自下列官能基群X之至少一種官能基之氫化 二烯系化合物（含有官能基之氫化二烯系聚合物）， [官能基群X]:羧基、酸酐基、環氧基、（甲基）丙 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸酯基及噁唑 β 啉基。 [4]如上述[1]~[3]中任一項記載之封閉材料，其中上 述（ίΠ )成分爲具有選自下列官能基群父之至少一種官能 基之含官能基之烯烴系聚合物， 基、環氧基、（甲基）丙 經基、異氰酸酯基及噁唑 [官能基群X]:羧基、酸野 烯醯基、胺基、烷氧基矽烷基、 琳基。 中上述（iii )成分 甲基丙烯酸縮水甘 [5]如上述[4]記載之封閉材料，其 爲含有酸肝基之丙嫌系聚合物或乙稀. 201018707 油酯共聚物。 [6] —種封閉材料薄片，其特徵爲使用上述π]〜[5]中 任一項記載之封閉材料。 [7] 如上述[6]記載之封閉材料薄片，其中於宜一·面上 層合有熱可塑性樹脂及/或金屬。 [8] 如上述[1]〜[5]中任一項記載之封閉材料，其中上 述封閉材料係作爲太陽電池之封閉材料使用。 [9] 如上述[6]或[7]記載之封閉材料薄片，其中上述封 閉材料薄片係作爲太陽電池之封閉材料使用。 [10] —種太陽電池模組’其特徵係使用上述[6]或[7] 記載之封閉材料薄片。 本發明之兀件封閉材料之透明性、耐熱性優異，且即 使不使用有機過氧化物或矽烷偶合劑等，亦可顯示與玻璃 或金屬等之上下各保護材之優異接著性。 【實施方式】 以下對本發明實施之最佳形態加以說明，但本發明並 不限定於以下實施形態，應理解在不脫離本發明主旨之範 圍內’基於本技藝者通常之知識，對以下實施形態加以適 胃_更、改良者亦屬於本發明之範圍。 [1 ]封閉材料： 本發明之封閉材料係以下列作爲構成成分：（i )成 分·聚丙烯，（ii)成分：氫化二烯系聚合物，及（m) -8- 201018707 成分·具有特定官能基之聚合物（含有官能基之聚合物） ’且相對於上述（i )成分0〜60質量份，上述（Η )成分 4 0〜100質量份（合計量ι〇〇質量份），含有ι〜1〇〇質量份之 上述（iii )成分。以下對每構成成分加以說明。 [1-1]聚丙烯（（i)成分） 本發明之封閉材料含有聚丙烯（以下，有時表示爲Γ ® (i)成分」）作爲構成成分。藉由以（i)成分作爲構成 成分有提高耐熱性及成形加工性之傾向。 本發明中使用之聚丙烯亦可爲均聚丙烯、嵌段聚丙烯 、無規聚丙烯、丙烯· 烯烴共聚物、丙烯•乙烯共聚 物、丙烯•丁烯共聚物、丙烯.乙烯•丁烯共聚物等。 (i)成分之分子量或分子量分布並無特別限制。因 此’只要在可實質成形加工範圍內適當選擇即可。由此等 觀點而言’重量平均分子量較好爲丨萬以上，更好爲4萬以 ® 上’最好爲8萬以上。又，此處所謂「重量平均分子量」 意指使用六氟異丙醇作爲溶劑，以凝膠滲透層析儀（GPC )測定之換算爲聚甲基丙烯酸甲酯之重量平均分子量。 關於（i )成分之熔點亦無特別限制，但較好爲1 20 °C 以上’更好爲140 °C以上。又，本說明書中，顯示（〇成 分之熔點時’表示藉由示差掃描熱量計（DSC)所測定之 値。 (i)成分可藉由已知之聚丙烯製造法製造。具體而 言可舉例爲自由基聚合、觸煤聚合法等。 -9- 201018707 (ί)成分之含量，相對於（i)成分與（π)成分之 合計100質量份’有必要成爲0〜60質量份，較好成爲5〜60 質量份。若不存在（i )成分，則有耐熱性或成形加工性 變差之傾向。若超過60質量份，則由於氫化二烯系聚合物 ((ii)成分）之量減少故而變硬而使太陽電池元件封閉 性變差。 [1-2]氫化二烯系聚合物（（Η)成分） 本發明之封閉材料除了聚丙烯（（i)成分）以外， 又含有氫化二烯聚合物（以下有時表示爲「（ii)成分」 )作爲構成成分。藉由以（ii)成分作爲構成成分而成爲 柔軟使封閉性優異。本發明使用之氫化二烯系聚合物（（ Π)成分）較好含有源自芳香族二烯化合物之重複單位以 及源自共範一儲系化合物之重複單位。 至於（Π)成分之「芳香族二烯化合物」，可舉例爲 例如苯乙嫌、第三丁基苯乙烯、α -甲基苯乙烯、對-甲基 苯乙烯、對-乙基苯乙烯、二乙烯基苯、丨丨―二苯基苯乙烯 、乙嫌基萘、乙燦基蒽、ΝΝ·二乙基-對-胺基乙基苯乙烯 及乙嫌基n比陡等。本發明中由成爲原料之單體獲取容易性 、聚合性觀點觀之’較好爲以含有源自苯乙烯或第三丁基 苯乙烯之重複單位之共軛二烯聚合物作爲基礎聚合物。 (ii)成分之「共軛二烯化合物」可舉爲例如13-丁 一烯、異戊間一烯、2,3 -二甲基_1，3-丁二烯、丨，3 -戊二烯 、2-甲基-1，3-辛二嫌、13_己二烯、丨，3•環己二烯、4,5_二 201018707 乙基-1，3-辛二烯、3-丁基-1，3-辛二烯、月桂烯（myreene )及氯丁二烯等。本發明中，就成爲原料之單體獲取容易 性、聚合性之觀點而言’以含有源自1,3-丁二烯或異戊間 二烯之重複單位之共軛二烯系聚合物較佳。 芳香族二烯化合物：共軛二烯化合物之質量比較好爲 3:97〜60:40’當質量比超過60:4〇時，（ii)成分之玻璃轉 移點過高’變較硬化而有封閉性變差之傾向。 • 至於（ϋ)成分之含有聚合物嵌段A、聚合物嵌段B之 聚合物可舉例爲例如（A)-(B)、[(A)-(B)]X-Y、（A)-(B)-(A) 、[(A)-(B)-(A)]X-Y、（a)-(B)-(A)-(B)、（B)-(A)-(B)-(A)、 [(A)-(B)-(A)-(B)]X-Y 、 （Α)-(Β)-(Α)·(Β)-(Α)及[(A)-(B)- (八卜⑼卜…:^-丫^⑼^众…-丫等構造結合而成之嵌段共聚 物。 (其中’ （A)表示聚合物嵌段a，（B)表示聚合物嵌段 B ’ X表示2以上之整數，γ表示偶合劑殘基）。 ® 又’含有如上述之兩種以上嵌段之嵌段共聚物可爲芳 香族乙烯基化合物或共軛二烯化合物之含有率於嵌段中連 續變化之錐型（taper )，或亦可爲無規型。另外，使聚合 物嵌段偶合之「偶合劑」可舉例爲例如甲基二氯矽烷、甲 基三氯矽烷、丁基三氯矽烷、四氯矽烷、二溴乙烷、四氯 錫、丁基三氯錫、四氯鍺、雙（三氯矽烷基）乙烷等鹵素 化合物；環氧化大豆油等環氧化合物；己二酸二乙酯、己 二酸二甲酯、對苯二甲酸二甲酯、對苯二甲酸二乙酯等羰 基化合物、二乙烯基苯等聚乙烯化合物；聚異氰酸酯等。 -11 - 201018707 (ϋ)成分爲使共軛二烯化合物單位之雙鍵之至少 80%經氫化而成之聚合物。氫化率之上限並沒有特別限制 ，但就獲得耐熱候性或耐熱性優異之材料之觀點而言，以 上述雙鍵之90%以上經氫化而成之聚合物較佳，更好爲 9 5 %以上經氫化而成之聚合物。 (ii)成分亦可爲導入選自官能基群X之至少一種官 能基之聚合物。導入官能基有使與玻璃或金屬等上下之各 保護材之接著性提高之傾向。 [官能基群X]:羧基、酸酐基、環氧基、（甲基）丙 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸酯基及噁唑 啉基。 (Π)成分以具有平均〇_〇1〜100(個/1分子）上述官 能基之聚合物較佳，更好爲具有平均0.1〜10 (個/1分子） 之聚合物。官能基數未達0.01 (個/1分子）時會有與玻璃 或金屬等上下各保護材之接著性下降之f頃向。另一方面， 官能基數超過1 00 (個/1分子）時，有所謂成形加工性下 降而產生缺陷之情況。 (ii )成分之分子量並沒有特別限制，但重量平均分 子量較好爲3萬~200萬，更好爲4萬〜100萬，且最好爲5萬 〜50萬。重量平均分子量未達3萬時，會有太陽電池元件封 閉材料之強度或尺寸安定性下降造成缺陷之傾向而較不佳 。另一方面，當重量平均分子量超過200萬時，（ii)成分 之熔融黏度過高，有使太陽電池元件封閉材料之加工性或 生產性下降造成缺陷之傾向故而不佳。另外，此處所謂的 -12- 201018707 「重量平均分子量」意指以凝膠滲透層析（GPC )測定換 算成聚苯乙烯之重量平均分子量者。 (ii)成分可以下列（a) ~(e)之任一製法所述之方 法製造。 製法（a): 製法（a)爲使共軛二烯化合物單獨，或使共軛二烯 φ 化合物及芳香族乙烯基化合物在有機鹼金屬化合物存在下 進行嵌段共聚合，且使該共聚物氫化而得之方法。又，亦 可任意對所得氫化二烯系聚合物，於溶液中或於押出機等 之混練機中反應選自由下列通式（1)表示之含有（甲基 )丙烯醯基之化合物、以下列通式（2)表示之含有環氧 基之化合物及馬來酸酐所組成群組之至少一種。 【化1】 Ο R1201018707 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a sealing material and a solar cell module using the same. More specifically, it relates to a sealing material which is easy to form a module and which is excellent in transparency, heat resistance, adhesion, and the like. [Prior Art] Φ Solar cells have attracted attention as a clean energy source in recent years. Although they have become available for general housing, they have not yet been fully popularized. The main reason for this is that solar cells are still expensive. An example of the reason is as follows. The power generation efficiency of the solar cell itself is not sufficient, and the module has to be increased in order to obtain the required power. Moreover, the module manufacturing is low in productivity. The solar cell module generally protects the transparent protective material and the lower substrate protective material of the solar cell element, such as germanium, gallium, arsenic, copper-indium-selenium, etc., and fixes the solar cell component and the protective material with the sealing material, and is packaged. By. For this reason, as a solar cell element sealing material, transparency, heat resistance, and adhesion to various protective materials such as glass or metal are required. At present, as a solar cell element sealing material for a solar cell module, an ethylene/vinyl acetate copolymer having a high vinyl acetate content is used from the viewpoints of flexibility and transparency. Since this element is insufficient in heat resistance and adhesion, it is necessary to crosslink it with an organic peroxide or a decane coupling agent. Therefore, in the manufacture of a solar cell module, it is necessary to undergo a step of preparing a sheet of an ethylene-vinyl acetate copolymer prepared with the additives, and laminating for a few minutes to ten minutes to temporarily form a solar cell element, and at -5 - 201018707 A time-consuming step in the oven that lasts for a period of tens of minutes to an hour at a high temperature at which the organic peroxide is decomposed. Further, in the sheet production stage, since it is necessary to form at a low temperature without decomposing the organic peroxide, the extrusion forming speed cannot be increased. As described above, the manufacturing of the solar cell module requires labor and time, and the manufacturing cost thereof is one of the causes. [Patent Document 1] Japanese Patent Publication No. 2-4070 No. 9 (Invention) The present invention has been made in view of the problems of the above-described conventional techniques, and as a subject thereof, it is not necessary to use organic peroxides. The cross-linking' thus significantly improves the production efficiency of solar cell modules, and has an excellent material as a sealing material for solar cell components. The present inventors have found that the above problems can be attained by the following sealing materials in order to achieve the above-mentioned problems, and thus the present invention has been completed. That is, according to the present invention, the sealing material shown below is provided.封闭] a kind of sealing material characterized by (i) component: polypropylene, (ii) component: hydrogenated diene polymer, and (iii) component: at least one functional group selected from the following functional group X The polymer of the base is a polymer (a polymer containing a functional group) different from the above (Π) component as a constituent component' and the above (π) component 40~ with respect to the above component (i) 1 part by mass (total amount ι by mass) containing 1 to 1 part by mass of the above component (iii), [functional group X]: carboxyl group, acid anhydride group, epoxy group, (meth) propylene Stiff base, amine, oxiranyl, hydroxy, isocyanate and oxazoline-6- 201018707. [2] The sealing material according to the above [1], wherein the component (ii) is a polymer containing the polymer block A and the polymer block B described below, and is composed of the component (ii) a hydrogenated hydrogenated diene polymer of at least 80% of the double bonds of the conjugated diene compound unit, [Polymer block A]: a polymer block containing 50% by mass or more of the aromatic vinyl compound unit, [Polymer block B]: a polymer embedded in a range of from 3 Å to 90% inclusive of a conjugated diene compound unit of 50% by mass or more and a 1,2-bond content and a 3,4-bond content segment. [3] The sealing material according to the above [1] or [2] wherein the (η) component is a hydrogenated diene compound having at least one functional group selected from the following functional group X (hydrogenated difunctional group) Elefinic polymer), [functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, a (meth)acrylinyl group, an amine group, an alkoxyalkyl group, a hydroxyl group, an isocyanate group, and an oxazole β-phenyl group. [4] The sealing material according to any one of the above [1], wherein the (Π) component is a functional group-containing olefin polymer having at least one functional group selected from the group of the following functional groups. , a group, an epoxy group, a (meth)propyl group, an isocyanate group, and an oxazole [functional group X]: a carboxyl group, an acid olefin group, an amine group, an alkoxyalkyl group, a linyl group. The above-mentioned (iii) component is condensed with methacrylic acid [5]. The sealing material according to the above [4], which is a sodium silicate polymer containing an acid liver group or ethylene. 201018707 Oil ester copolymer. [6] A sealing material sheet characterized by using the sealing material according to any one of the above π] to [5]. [7] The sheet of the sealing material according to the above [6], wherein a thermoplastic resin and/or a metal is laminated on the surface of the Yiyi. [8] The sealing material according to any one of [1] to [5] wherein the sealing material is used as a sealing material for a solar cell. [9] The sheet of the sealing material according to the above [6] or [7] wherein the sheet of the sealing material is used as a sealing material for a solar cell. [10] A solar battery module is characterized in that the sealing material sheet described in the above [6] or [7] is used. The component sealing material of the present invention is excellent in transparency and heat resistance, and exhibits excellent adhesion to each of the protective materials such as glass or metal, even without using an organic peroxide or a decane coupling agent. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is not limited to the following embodiments, and it is to be understood that the following embodiments are based on the knowledge of those skilled in the art without departing from the scope of the invention. It is also within the scope of the invention to apply the stomach to the stomach. [1] Closure material: The sealing material of the present invention is composed of the following components: (i) component·polypropylene, (ii) component: hydrogenated diene polymer, and (m) -8- 201018707 component·specific The functional group polymer (polymer containing a functional group) is contained in an amount of from 0 to 60 parts by mass based on the above (i) component, and the above (Η) component is from 40 to 100 parts by mass (total amount of ι by mass). 1 to 5 parts by mass of the above component (iii). Each constituent component will be described below. [1-1] Polypropylene ((i) component) The sealing material of the present invention contains polypropylene (hereinafter sometimes referred to as Γ® (i) component) as a constituent component. The component (i) has a tendency to improve heat resistance and moldability by using the component (i) as a constituent component. The polypropylene used in the present invention may also be a homopolypropylene, a block polypropylene, a random polypropylene, a propylene/olefin copolymer, a propylene/ethylene copolymer, a propylene/butene copolymer, a propylene, ethylene, butene copolymer. Things and so on. The molecular weight or molecular weight distribution of the component (i) is not particularly limited. Therefore, it suffices that it can be appropriately selected within the range in which it can be substantially formed. From such a viewpoint, the weight average molecular weight is preferably 10,000 or more, more preferably 40,000 or more, and preferably 80,000 or more. Here, the "weight average molecular weight" herein means a weight average molecular weight converted to polymethyl methacrylate by a gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. The melting point of the component (i) is not particularly limited, but is preferably 1 20 ° C or more and more preferably 140 ° C or more. Further, in the present specification, it is shown that (in the case of the melting point of the bismuth component, 'the enthalpy measured by the differential scanning calorimeter (DSC). (i) The component can be produced by a known polypropylene production method. Specifically, it can be exemplified as The radical polymerization, the coal-contacting polymerization method, etc. -9- 201018707 (ί) The content of the component is preferably 0 to 60 parts by mass with respect to 100 parts by mass of the total of the (i) component and the (π) component. 5 to 60 parts by mass. If the component (i) is not present, heat resistance or moldability tends to be deteriorated. When it exceeds 60 parts by mass, the amount of the hydrogenated diene polymer (component (ii)) is decreased. Therefore, the sealing property of the solar cell element is deteriorated. [1-2] Hydrogenated diene polymer ((Η) component) The sealing material of the present invention contains hydrogenation in addition to polypropylene ((i) component). The olefin polymer (hereinafter sometimes referred to as "(ii) component") is a constituent component. The component (ii) is used as a constituent component to be soft and excellent in sealing property. The hydrogenated diene polymer used in the present invention (( Π) component) preferably contains aromatic diene compound The repeating unit of the substance and the repeating unit derived from the compound of the common-type reservoir. As the "aromatic diene compound" of the (Π) component, for example, styrene-butadiene, tert-butylstyrene, α-methyl group can be exemplified. Styrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, anthracene-diphenylstyrene, ethyl cyanophthalene, ethyl ruthenium, ruthenium diethyl-p-amine The ratio of the ethyl styrene and the sulphur group n is steep, etc. In the present invention, it is preferable to obtain a monomer which is a raw material, and it is preferable to contain a styrene-derived or a tert-butyl styrene. The conjugated diene polymer of the repeating unit is used as the base polymer. The "conjugated diene compound" of the component (ii) may, for example, be 13-butene, isoamyl, or 2,3-dimethyl. 1,3-butadiene, anthracene, 3-pentadiene, 2-methyl-1,3-octanediene, 13-hexadiene, anthracene, 3•cyclohexadiene, 4,5_two 201018707 Ethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myreene, chloroprene, etc. In the present invention, the monomer is easily obtained as a raw material, Polymerization The conjugated diene polymer containing a repeating unit derived from 1,3-butadiene or isoprene is preferred. The aromatic diene compound: the conjugated diene compound preferably has a mass of 3: 97~60:40' When the mass ratio exceeds 60:4〇, the (ii) component has a tendency that the glass transition point is too high to become harder and the sealing property is deteriorated. The polymer of the segment A and the polymer block B can be exemplified by, for example, (A)-(B), [(A)-(B)]XY, (A)-(B)-(A), [(A) -(B)-(A)]XY, (a)-(B)-(A)-(B), (B)-(A)-(B)-(A), [(A)-(B )-(A)-(B)]XY, (Α)-(Β)-(Α)·(Β)-(Α) and [(A)-(B)-(八卜(9)卜...:^-丫^(9)^众...-丫 The structure of the block copolymer is combined. (wherein (A) represents the polymer block a, (B) represents the polymer block B ′ X represents an integer of 2 or more, and γ represents a coupling agent residue). And a block copolymer containing two or more blocks as described above may be a taper in which the content of the aromatic vinyl compound or the conjugated diene compound continuously changes in the block, or may be Non-standard. Further, the "coupling agent" for coupling the polymer block may, for example, be methyl dichlorodecane, methyl trichlorodecane, butyl trichlorodecane, tetrachlorodecane, dibromoethane, tetrachlorotin or butyl. Halogen compounds such as trichlorotin, tetrachlorophosphonium, bis(trichlorodecanealkyl)ethane; epoxy compounds such as epoxidized soybean oil; diethyl adipate, dimethyl adipate, and dimethyl terephthalate a carbonyl compound such as an ester or diethyl terephthalate; a polyvinyl compound such as divinylbenzene; a polyisocyanate or the like. -11 - 201018707 The (ϋ) component is a polymer obtained by hydrogenating at least 80% of the double bonds of the conjugated diene compound unit. The upper limit of the hydrogenation rate is not particularly limited, but from the viewpoint of obtaining a material excellent in heat resistance or heat resistance, a polymer obtained by hydrogenating 90% or more of the above double bonds is more preferable, more preferably 95%. The above polymer obtained by hydrogenation. The component (ii) may also be a polymer which is introduced into at least one functional group selected from the functional group X. The introduction of the functional group tends to improve the adhesion to the respective protective materials such as glass or metal. [Functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, a (meth) propylene group, an amine group, an alkoxyalkyl group, a hydroxyl group, an isocyanate group, and an oxazoline group. The (Π) component is preferably a polymer having an average of 〇_〇1 to 100 (one/1 molecule) of the above functional groups, more preferably a polymer having an average of 0.1 to 10 (pieces per molecule). When the number of functional groups is less than 0.01 (one molecule per molecule), the adhesion to the upper and lower protective materials such as glass or metal may decrease. On the other hand, when the number of functional groups exceeds 100 (one molecule), there is a case where the moldability is lowered to cause defects. The molecular weight of the component (ii) is not particularly limited, but the weight average molecular weight is preferably from 30,000 to 2,000,000, more preferably from 40,000 to 1,000,000, and most preferably from 50,000 to 500,000. When the weight average molecular weight is less than 30,000, there is a tendency that the strength or dimensional stability of the solar cell element sealing material is lowered to cause defects, which is not preferable. On the other hand, when the weight average molecular weight exceeds 2,000,000, the melt viscosity of the component (ii) is too high, which tends to cause defects in the processability or productivity of the solar cell element sealing material. Further, the term "weight average molecular weight" as used herein means -12-201018707 means the weight average molecular weight converted to polystyrene by gel permeation chromatography (GPC). The component (ii) can be produced by the method described in any one of the following methods (a) to (e). Process (a): Process (a) is a block copolymerization of a conjugated diene compound alone or a conjugated diene φ compound and an aromatic vinyl compound in the presence of an organic alkali metal compound, and the copolymer is copolymerized The method of hydrogenation. Further, the obtained hydrogenated diene polymer may be optionally reacted in a solution or a kneader such as an extruder to select a compound containing a (meth)acryl oxime group represented by the following formula (1), and the following The compound represented by the formula (2) represents at least one of a group consisting of an epoxy group-containing compound and maleic anhydride. 【化1】 Ο R1

⑴(1)

Γ II I X1--R1-C-C=CH2 [通式（1)中，R1爲氫原子或甲基，R1爲單鍵或亦可含雜 原子之碳數1~20之烴基，X1爲烷氧基矽烷基、羥基、胺基 、羧基、環氧基、異氰酸酯基或噁唑啉基，q在胺基時表 示1~3之整數，於其他官能基之情況表示1]。 【化2】Γ II I X1--R1-CC=CH2 [In the formula (1), R1 is a hydrogen atom or a methyl group, R1 is a single bond or a hydrocarbon group having a carbon number of 1 to 20 which may also contain a hetero atom, and X1 is an alkoxy group. The alkyl group, the hydroxyl group, the amine group, the carboxyl group, the epoxy group, the isocyanate group or the oxazoline group, q represents an integer of 1 to 3 in the case of an amine group, and represents 1 in the case of other functional groups. [Chemical 2]

Ο -13- 1 201018707 [通式（2)中’ R3表示碳數2〜18之烯基，R4表示羯氧基、 亞甲氧基或伸苯氧基]。 由製法（a)獲得之聚合物可舉例爲例如（馬來酸酐 改質）苯乙烯·乙烯•丁烯-苯乙烯嵌段共聚物、（馬來酸 酐改質）苯乙烯-乙烯•丙烯-苯乙烯嵌段共聚物、（馬來 酸酐改質）苯乙烯-乙烯•丁烯•丙烯-苯乙烯嵌段共聚物 、環氧基改質之苯乙烯-乙烯•丁烯-苯乙烯嵌段共聚物、 環氧基改質之苯乙烯-乙烯•丙烯-苯乙烯嵌段共聚物、瓌 β 氧基改質之苯乙烯-乙烯•丁烯•丙烯-苯乙烯嵌段共聚物 等。其中，（馬來酸酐改質）苯乙烯-乙烯•丁烯-苯乙烯 嵌段共聚物等之表示係指苯乙烯-乙烯•丁烯-苯乙烯嵌段 共聚物及馬來酸酐改質之苯乙烯-乙烯•丁烯-苯乙烯嵌段 共聚物二者。 製法（b): 製法（b)爲使共軛二烯化合物單獨，或使共軛二烯 β 化合物及芳香族乙烯基化合物在以下列通式（3)或（4) 表示之具有胺基之有機鹼金屬化合物存在下經嵌段共聚合 後，使該共聚物氫化之方法。Ο -13- 1 201018707 [In the formula (2), R3 represents an alkenyl group having 2 to 18 carbon atoms, and R4 represents a decyloxy group, a methyleneoxy group or a phenoxy group. The polymer obtained by the process (a) can be exemplified by, for example, (maleic anhydride modified) styrene·ethylene·butylene-styrene block copolymer, (maleic anhydride modified) styrene-ethylene/propylene-benzene. Ethylene block copolymer, (maleic anhydride modified) styrene-ethylene/butene/propylene-styrene block copolymer, epoxy modified styrene-ethylene/butylene-styrene block copolymer An epoxy-modified styrene-ethylene/propylene-styrene block copolymer, an 瓌β-oxygen-modified styrene-ethylene/butene/propylene-styrene block copolymer, and the like. Among them, (maleic anhydride modified) styrene-ethylene•butylene-styrene block copolymer, etc. means styrene-ethylene•butylene-styrene block copolymer and maleic anhydride modified benzene Both ethylene-ethylene•butylene-styrene block copolymers. Process (b): Process (b) is a method in which the conjugated diene compound is used alone or the conjugated diene β compound and the aromatic vinyl compound have an amine group represented by the following formula (3) or (4) A method of hydrogenating the copolymer after block copolymerization in the presence of an organic alkali metal compound.

-14- 201018707 [通式（3)中’ R5及R6二者均表示碳數3~18之二焼基砂院 基，或任一者爲前述之三烷基矽烷基’另一者爲碳數1〜20 之院基、碳數6~20之芳基、碳數7〜20之芳烷基或碳數 1〜100之有機矽烷氧基’ R7表示碳數之伸院基或亞院 基]。 【化4】 R8 R8-14- 201018707 [In the general formula (3), both R5 and R6 represent a carbon number of 3 to 18 decyl sand-based, or either of the aforementioned trialkyl decyl groups, and the other is carbon. a number of bases of 1 to 20, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organodecyloxy group having a carbon number of 1 to 100 'R7" ]. [化4] R8 R8

.Si (4).Si (4)

N-R7-U 、Si [通式（4)中，R7表示碳數1~20之伸烷基或亞烷基’ R8表 示碳數1〜20之烷基、碳數6〜20之芳基、碳數7~20之芳烷基 或碳數1~100之有機矽烷氧基]。 ❿ 上述以通式（3)或（4)表示之有機鹼金屬化合物可 舉例爲例如3-鋰離子-1-[N,N-雙（三甲基矽烷基）]胺基丙 烷、2-鋰離子-1-[N，N-雙（三甲基矽烷基）]胺基乙烷、3- 鋰離子-2,2·二甲基-1-[N，N-雙（三甲基矽烷基）]胺基丙烷 、2,2,5,5-四甲基-1-( 3-鋰離子丙基）-1-氮雜-2,5-二矽環 戊烷、2，2,5,5-四甲基-1-(3-鋰離子-2,2-二甲基-丙基）- 1-氮雜-2,5-二矽環戊烷、2,2,5,5-四甲基-1- (2-鋰離子乙 基）-1-氮雜-2,5-二矽環戊烷、3-鋰離子-1-[1<[-(第三丁 基-二甲基矽烷基）-N-三甲基矽烷基]胺基丙烷、3-鋰離 子-1-(N_甲基-N_三甲基矽烷基）胺基丙烷及3_鋰離子_卜 -15- 201018707 (N-乙基-N-三甲基矽烷基）胺基丙烷等。 製法（c): 製法（c)爲使共軛二烯單獨，或使共軛二烯及芳香 族乙烯基化合物與以下列通式（5)或（6)表示之具有胺 基之不飽和單體，在有機鹼金屬化合物存在下進行嵌段共 聚合後，使該聚合物氫化之方法。 【化5】 HC=CH2N-R7-U, Si [In the formula (4), R7 represents an alkylene group or an alkylene group having 1 to 20 carbon atoms. R8 represents an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. An aralkyl group having 7 to 20 carbon atoms or an organic decyloxy group having 1 to 100 carbon atoms. ❿ The above organic alkali metal compound represented by the formula (3) or (4) can be exemplified by, for example, 3-lithium ion-1-[N,N-bis(trimethyldecyl)aminopropane, 2-lithium Ion-1-[N,N-bis(trimethyldecyl)]aminoethane, 3-lithium ion-2,2·dimethyl-1-[N,N-bis(trimethyldecyl) )]aminopropane, 2,2,5,5-tetramethyl-1-(3-lithium propyl)-1-aza-2,5-dioxancyclopentane, 2,2,5, 5-tetramethyl-1-(3-lithium ion-2,2-dimethyl-propyl)-1-oxa-2,5-dioxancyclopentane, 2,2,5,5-tetra Methyl-1-(2-lithium ethethyl)-1-aza-2,5-dioxancyclopentane, 3-lithium ion-1-[1<[-(t-butyl-dimethyl矽alkyl)-N-trimethyldecyl]aminopropane, 3-lithium ion-1-(N-methyl-N-trimethyldecyl)aminopropane and 3_lithium ion_b-15- 201018707 (N-ethyl-N-trimethyldecyl)aminopropane and the like. Process (c): Process (c) is an unsaturated single having a conjugated diene alone or a conjugated diene and an aromatic vinyl compound and having an amine group represented by the following formula (5) or (6) A method in which the polymer is hydrogenated after block copolymerization in the presence of an organic alkali metal compound. [Chemical 5] HC=CH2

[通式（5 )中，R9及R1q二者均表示碳數3~18之三烷基矽 烷基，或任一者表示上述三烷基矽烷基，另一者表示碳數 1~20之烷基、碳數6~20之芳基、碳數7~20之芳烷基或碳數 1〜100之有機矽烷氧基，η表示1〜3之整數]。 【化6】 HC=CH2[In the formula (5), both R9 and R1q represent a trialkylsulfanyl group having 3 to 18 carbon atoms, or either of the above represents a trialkyldecanealkyl group, and the other represents an alkyl group having 1 to 20 carbon atoms. The group, the aryl group having 6 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms or the organodecyloxy group having 1 to 100 carbon atoms, and η represents an integer of 1 to 3]. [Chemical 6] HC=CH2

201018707 [通式（6)中，R9及Rio二者均表示碳數3~18之三烷基矽 院基’或任一者表示上述三烷基矽烷基，另一者表示碳數 1〜20之院基、碳數6〜20之芳基、碳數7〜2〇之芳烷基或碳數 1~1〇〇之有機矽烷氧基，Rn表示碳數卜2〇之伸烷基或亞烷 基，η表示1〜3之整數]。 以上述通式（5)或（6)表示之不飽和單體可舉例爲 例如對- [Ν，Ν-雙（三甲基矽烷基）胺基]苯乙烯、對-[Ν，Ν_ ® 雙（三甲基矽烷基）胺基甲基]苯乙烯、對-{2-[Ν，Ν-雙（ 三甲基矽烷基）胺基]乙基}苯乙烯、間-[Ν，Ν-雙（三甲基 矽烷基）胺基]苯乙烯、對-(Ν-甲基-Ν-三甲基矽烷基胺基 )苯乙烯及對-(Ν-甲基-Ν-三甲基矽烷基胺基甲基）苯乙 烯等。 製法（d): 製法（d)爲使共軛二烯化合物單獨，或使共軛二烯 Φ 化合物及芳香族乙烯基化合物在有機鹼金屬化合物存在下 經嵌段共聚合，且於所得共聚物之活性點與以下述通式（ 7)表示之烷氧基矽烷化合物反應後’使該聚合物氫化之 方法。 R12(4-m-n)Si(〇R，3)mR14n :⑺ [通式（7)中，R12表示碳數1~2〇之烷基、碳數6~20之芳 基、碳數7~2〇之芳烷基或碳數1~1〇〇之有機矽烷基。R12爲 -17- 201018707 複數之情況，各R12可爲相同之官能基，或亦可爲不同之 官能基。R13表示碳數1~20之烷基、碳數6~20之芳基或碳 數7~20之芳烷基。OR13爲複數之情況，各OR13可爲相同之 官能基或亦可爲不同之官能基。R1 4表示具有含N原子之極 性基之取代基。R14爲複數之情況，各R14可爲相同之官能 基或亦可爲不同之官能基。另外，各R14爲獨立之取代基 ，亦可形成環狀構造。m及η表示1〜3之整數。但，m與η之 和爲1〜4之整數]。 φ 以上述通式（7)表示之烷氧基矽烷化合物可舉例爲 例如Ν-Ν-雙（三甲基矽烷基）胺基丙基三甲氧基矽烷、Ν-Ν·雙（三甲基矽烷基）胺基丙基三乙氧基矽烷、Ν-Ν-雙（ 三甲基矽烷基）胺基丙基二甲基乙氧基矽烷、Ν-Ν-雙（三 甲基矽烷基）胺基丙基二甲基甲氧基矽烷、Ν-Ν-雙（三甲 基矽烷基）胺基丙基甲基二乙氧基矽烷、Ν-Ν-雙（三甲基 矽烷基）胺基丙基甲基二甲氧基矽烷、Ν，Ν-雙（三甲基矽 烷基）胺基乙基三甲氧基矽烷、Ν-Ν-雙（三甲基矽烷基） 0 胺基乙基三乙氧基矽烷、Ν-Ν-雙（三甲基矽烷基）胺基乙 基二甲基乙氧基矽烷、Ν，Ν-雙（三甲基矽烷基）胺基乙基 二甲基甲氧基矽烷、Ν，Ν·雙（三甲基矽烷基）胺基乙基甲 基二乙氧基矽烷、Ν,Ν·雙（三甲基矽烷基）胺基乙基甲基 二甲氧基矽烷、Ν-甲基-Ν-三甲基矽烷基胺基丙基三甲氧 基矽烷， Ν -甲基-Ν -二甲基矽院基胺基丙基三乙氧基砂院、Ν· 甲基-Ν -三甲基砂垸基胺基丙基二甲基乙氧基矽院、Ν -甲 -18- 201018707 基-N-三甲基矽烷基胺基丙基二甲基甲氧基矽烷、N-甲基-N-三甲基矽烷基胺基丙基甲基二乙氧基矽烷、N-甲基-N-三甲基矽烷基胺基丙基甲基二甲氧基矽烷、N，N-二甲基胺 基丙基三甲氧基矽烷、N，N-二甲基胺基丙基三乙氧基矽烷 、N，N-二甲基胺基丙基二甲基乙氧基矽烷、N，N-二甲基胺 基丙基二甲基甲氧基矽烷、N，N-二甲基胺基丙基甲基二乙 氧基矽烷、N，N-二甲基胺基丙基甲基二甲氧基矽烷、 # N-(l,3-二甲基亞丁基）-3-(三乙氧基矽烷基）-1-丙胺、N-(l-甲基亞乙基）-3-(三乙氧基矽烷基）-1-丙 胺、N-亞乙基-3-(三乙氧基矽烷基）-1-丙胺、N- ( 1-甲 基亞丙基）-3-(三乙氧基矽烷基）-1-丙胺、N-(4-N,N-二甲基胺基亞苄基）-3-(三乙氧基矽烷基）-l-丙胺、N- (l，3-二甲基亞丁基）-3-(三甲氧基矽烷基）-l-丙胺、 N-(l-甲基亞乙基）-3-(三甲氧基矽烷基）-1-丙胺、N-亞乙基-3-(三甲氧基矽烷基）-1-丙胺、N- ( 1-甲基亞丙 • 基）-3-(三甲氧基矽烷基）-1-丙胺、 N-(4-N，N-二甲基胺基亞苄基）-3-(三甲氧基矽烷基 )-1-丙胺、N-(l，3二甲基亞苄基）-3-(甲基二甲氧基矽 烷基）-1-丙胺、N-( 1-甲基亞乙基）-3-(甲基二甲氧基 矽烷基）-1-丙胺、N-亞乙基-3-(甲基二甲氧基矽烷基）-1-丙胺、N- ( 1-甲基亞丙基）-3-(甲基二甲氧基矽烷基 )-1-丙胺、N- (4-N，N-二甲基胺基亞苄基）-3-(甲基二 甲氧基矽烷基）-1-丙胺、N- ( 1，3二甲基亞丁基）-3-(甲 基二乙氧基矽烷基）-1-丙胺、N-(l -甲基亞乙基）-3-( -19- 201018707 甲基二乙氧基矽烷基）-1·丙胺、N-亞乙基-3-(甲基二乙 氧基矽烷基）·1-丙胺、N- ( i-甲基亞丙基）_3·(甲基二 乙氧基矽烷基）-1·丙胺、 N-(4-N,N -二甲基胺基亞卞基）-3-(甲基二乙氧基砂 烷基）-卜丙胺、N- ( 1，3二甲基亞丁基）-3-(二甲基甲氧 基矽烷基）-1-丙胺、Ν-(1·甲基亞乙基）-3-(二甲基甲 氧基矽烷基）·卜丙胺、N-亞乙基-3-(二甲基甲氧基矽烷 基）-1-丙胺、N-(l -甲基亞丙基）-3-(二甲基甲氧基矽 烷基）-1-丙胺、N-(4-N，N-二甲基胺基亞苄基）-3-(二 甲基甲氧基矽烷基）-1-丙胺、Ν·(1，3二甲基亞丁基）-3-(二甲基乙氧基矽烷基）-1-丙胺、N-(l-甲基亞乙基）-3-(二甲基乙氧基矽烷基）-1-丙胺、Ν-亞乙基-3·(二甲 基乙氧基矽烷基）-1-丙胺、Ν- ( 1-甲基亞丙基）-3·(二 甲基乙氧基矽烷基）-1-丙胺、Ν-( 4-Ν，Ν-二甲基胺基亞芣 基）-3-(二甲基乙氧基矽烷基）-1-丙胺等。 製法（e): 製法（e)爲使共軛二烯化合物單獨，或使共軛二烯 化合物及芳香族乙烯基化合物在有機鹼金屬化合物存在下 進行嵌段共聚合，且於所得共聚物之活性點與環氧化合物 或酮化合物或除上述通式（3)〜（7)外之含氮化合物反 應成爲聚合物後，使該聚合物氫化之方法。 至於「環氧化合物」可舉例爲環氧乙烷、環氧丙烷等 ’ 「酮化合物」可舉例爲丙酮、二苯甲酮等，除上述通式 -20- 201018707 (3) ~(7)外之含氮化合物可舉例爲以下列通式（8)表 示之含氮化合物等。 R15R16C = N-R17 : (8) [通式（8)中，R15及R16各表示相同或不同之氫原子、碳 數1~20之烷基、碳數6〜20之芳基、碳數7~20之芳烷基或碳 Φ 數1〜100之有機矽烷基，R17爲氫原子、碳數3~18之三烷基 矽烷基、碳數卜20之烷基、碳數6~20之芳基、碳數7〜20之 芳烷基或碳數1~1 〇〇之有機矽烷基]。 以上述通式（8 )表示之含氮化合物可舉例爲例如N-亞苄基甲基胺、N-亞苄基乙基胺、N-亞苄基丁基胺及N-亞 苄基苯胺等。 [1-3]含官能基之聚合物（（iii)成分）： • 本發明之封閉材料除聚丙烯（（i)成分）、氫化二 烯系聚合物（（ii)成分）以外，亦含有含官能基之聚合 物（以下，有時記爲「（ iii )成分」）作爲構成成分。藉 由混合（iii)成分，可提升與太陽電池元件或玻璃等上下 各保護材之接著性。 本說明書中所謂的「含官能基之聚合物」意指具有選 自下列官能基群X之至少一種官能基之聚合物，且與上述 (ii)成分不同之聚合物。亦即，可使用於作爲基本骨架 之聚合物（以下有時記爲「基礎聚合物」）中導入上述官 -21 - 201018707 能基之聚合物作爲（in)成分。藉由導入該等反應性官能 基，使與太陽電池元件或玻璃等上下各保護材之接著爲可 能。 [官能基群X]··羧基、酸酐基、環氧基、（甲基）丙 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸酯基及噁唑 啉基。 至於本發明之含有官能基之聚合物可使用含官能基之 烯烴系聚合物。本發明書中所謂的「含官能基之烯烴系聚 合物」意指以烯烴系聚合物作爲基礎聚合物，於該基礎聚 合物中導入上述官能基而成之聚合物。 成爲（iii)成分之基礎聚合物之「烯烴系聚合物」爲 含有源自烯烴化合物（亦即乙烯及/或α-烯烴）之重複單 位之聚合物。具體而言，可舉例爲使一種或兩種以上之乙 烯及/或α-烯烴聚合獲得之聚合物。對該聚合法並沒有特 別限制，可使用例如藉由過去習知之聚合法（例如，高壓 法、低壓法等）等聚合獲得之聚合物。但，（iii)成分之 基礎聚合物亦可爲含有源自烯烴化合物以外之化合物之重 複單位者。 至於「α -烯烴」可舉例爲例如丙烯（以下記爲「丙 烯」）、1-丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、3-甲 基-1-戊烯、4-甲基-1-戊烯、3-乙基-1-戊烯、1-辛烯、1- 癸烯、1-十一碳烯等碳數3~12之α-烯烴。 烯烴系聚合物可舉例爲例如聚乙烯系樹脂、聚丙烯系 樹脂、聚丁烯樹脂、甲基戊烯樹脂等。該等中可單獨使用 -22- 201018707 一種亦可組合兩種以上 例如低密度聚乙烯、中 低密度聚乙烯、乙烯· 。「聚丙烯系樹脂」可 、無規聚丙烯、丙烯· 物、丙烯•丁烯共聚物 等聚烯烴中以使用聚乙: • ( iii)成分爲於上 基群X之至少一種官能； 法可舉例爲使烯烴化合 方法。例如，藉由使乙 得導入羧基之聚合物， 獲得導入酸酐基之聚合 )表示之含有（甲基） 導入（甲基）丙烯醯基 • 式（2)表示之含有環！ 環氧基之聚合物。又， 可藉由接枝聚合等進行 (ίΠ)成分之具體 共聚物、藉由Na、Zn、 丙烯酸共聚物之羧基一 烯·（甲基）丙烯酸酯 丙烯醯基共聚物、乙烯 聚物、乙烯•異氰酸乙 使用。「聚乙烯系樹脂」可舉例爲 密度聚乙烯、高密度聚乙烯、線性 丙烯共聚物、乙烯•辛烯共聚物等 舉例爲例如均聚丙烯、嵌段聚丙烯 α-烯烴共聚物、丙烯•乙烯共聚 、丙烯•乙烯•丁烯共聚物等。該 稀系樹脂或聚丙烯系樹脂較佳。 述基礎聚合物中導入選自上述官能 S之聚合物。導入上述官能基之方 物與具有該官能基之單體共聚合之 烯與（甲基）丙烯酸共聚合，可獲 藉由使乙烯與馬來酸酐共聚合，可 物，藉由使乙烯與以上述通式（1 丙烯醯基之化合物共聚合，可獲得 之聚合物，藉由使乙烯與以上述通 R基之化合物共聚合，可獲得導入 官能基之導入並不限於共聚合，亦 〇 例可舉例爲乙烯·（甲基）丙烯酸 Mg等金屬離子使乙烯·（甲基） 部份中和而成之陰離子聚合物、乙 共聚物之皂化物、乙烯·（甲基） •(甲基）丙烯酸酯•馬來酸酐共 烯酯共聚物、馬來酸酐改質之聚乙 -23- 201018707 烯、馬來酸酐改質之聚丙烯、馬來酸酐改質之乙烯•丙烯 共聚物、乙烯•甲基丙基酸縮水甘油酯共聚物、環氧基改 質之乙烯•丙烯共聚物、羥基改質之聚乙烯•羥基改質之 乙烯•丙烯共聚物等。 上述聚合物中，以與太陽電池元件或玻璃等上下各保 護材之接著性優異之具有酸酐之聚合物較佳，更好爲與（ ϋ)成分更具相溶性之含有酸酐基之聚丙烯或乙烯•甲基 丙烯酸縮水甘油酯共聚物。 (Hi )成分在使所得封閉材料之機械特性與成形加工 性之均衡良好之範圍內，亦可使用導入上述官能基之聚合 物。具體而言，較好爲具有平均〇·〇ι~ι，〇〇〇 (個/1分子） 之上述官能基之聚合物，更好爲具有平均0.1〜500 (個/1分 子）之聚合物。官能基數平均未達0.01 (個/1分子）時會 有無法獲得與太陽電池元件或玻璃、金屬之上下各保護材 之接著性之傾向。另一方面’當官能基數超過1，000 (個n 分子）時，有組成物之流動性降低使成形性顯著下降而造 成缺陷之傾向。 (iii )成分之分子量並沒有特別限制’但較好重量平 均分子量爲0.1萬~2 00萬，更好爲〇·5萬~150萬’最好爲0.5 萬〜1〇〇萬。重量平均分子量未達0.1萬時’有太陽電池封 閉材之強度下降之傾向。另一方面’重量平均分子量超過 200萬時，有組成物之流動性降低使成形加工性降低而造 成缺陷之傾向。再者，此處所謂的「重量平均分子量」意 指藉由凝膠滲透層析儀（GPC)測定換算成聚苯乙烯之重 201018707 量平均分子量者。 (iii)成分之含量相對於（i)成分及（ii)成分之合 計量爲100質量份，有必要成爲〇.1~40質量份，較好爲 0.5〜30質量份。未達0.1質量份時，含有官能基之聚合物量 少，有與玻璃或金屬等上下各保護材之接著性下降之傾向 。當超過40質量份時，含有官能基之聚合物量變得過剩， 而有成形加工性降低之情況。 [1-4]其他添加物： 本發明之封閉材料只要不損及其物性，則可添加（i )成分、（Π)成分及（iii)成分以外之次要添加物。次 要添加物可舉例爲例如抗氧化劑、紫外線吸收劑、有機過 氧化物、矽烷偶合劑、各種塡充劑、滑動劑、可塑劑、抗 著色劑、著色劑、抗菌劑、核形成劑、抗靜電劑等。 有機過氧化物可舉例爲例如苯甲醯基過氧化物、2,4-• 二氯苯甲醯基過氧化物、第三丁基過氧乙酸酯、第三丁基 過氧苯甲酸酯、二枯基過氧化物、2,5-二甲基-2,5-二（第 三丁基過氧基）己烷、二-第三丁基過氧化物、2,5·二甲 基-2,5-二（第三丁基過氧基）-3-己炔。尤其，可更佳地 使用二枯基過氧化物、2,5-二甲基-2,5-二（第三丁基過氧 基）己烷、二-第三丁基過氧化物、2,5-二甲基-2,5-二（第 三丁基過氧基）-3 -己炔等之一種或兩種以上。 有機過氧化物之使用量過少時會有接枝化反應之轉化 變不充分之情況，過多時由於會使聚烯烴中之游離自由基 -25- 201018707 部位變得過多，而有進行所謂的過氧化物交聯之虞，因此 相對於1〇〇質量份之（i)成分，較好爲0.01〜5質量份，更 好爲0.02~2質量份。 矽烷偶合劑舉例爲具有乙烯基、環氧基、苯乙烯基、 甲基丙烯醯氧基、丙烯醯氧基、胺基、脲基、氯丙基、锍 基、亞磺醯基、異氰酸酯機、烷基、芳基作爲官能基之習 知矽烷化合物。其中，使用有機過氧化物進行接枝反應時 ，較好爲具有乙烯基、甲基丙烯醯氧基作爲官能基之矽烷 化合物較佳。該等矽烷偶合劑相對於1 00重量份之聚合物 較好爲0.01〜5重量份，更好爲0.02〜2重量份。 抗氧化劑可舉例爲例如磷系安定劑、受阻酚系抗氧化 劑、環氧系安定劑及離子系安定劑等。紫外線吸收劑可舉 例爲二苯甲酮系、苯并三唑系、三嗪系、水楊酸酯系等。 至於矽烷偶合劑可舉例爲具有如乙烯基、丙烯醯氧基、甲 基丙烯醯氧基等不飽和基、胺基、環氧基等同時具有如烷 氧基之可水解基之化合物。至於各種塡充材可舉例爲氧化 矽、雲母等。至於滑動劑可舉例爲脂肪酸醯胺等。 [2]封閉材料薄片：201018707 [In the general formula (6), both R9 and Rio represent a trialkyl fluorenyl group having a carbon number of 3 to 18 or any of the above represents a trialkyldecyl group, and the other represents a carbon number of 1 to 20 a hospital base, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 2 carbon atoms or an organic decyloxy group having 1 to 1 carbon number, and Rn represents an alkyl group or a subunit of carbon number An alkyl group, η represents an integer of 1 to 3]. The unsaturated monomer represented by the above formula (5) or (6) can be exemplified by, for example, p-[Ν, Ν-bis(trimethyldecyl)amino]styrene, p-[Ν,Ν_ ® double (trimethyldecyl)aminomethyl]styrene, p-{2-[indene, bis-bis(trimethyldecyl)amino]ethyl}styrene, m-[Ν,Ν-double (trimethyldecyl)amino]styrene, p-(Ν-methyl-hydrazine-trimethyldecylalkylamino)styrene and p-(Ν-methyl-oxime-trimethyldecylamine Methyl) styrene and the like. Process (d): Process (d) is a block copolymerization of a conjugated diene compound alone or a conjugated diene Φ compound and an aromatic vinyl compound in the presence of an organic alkali metal compound, and the resulting copolymer A method of hydrogenating the polymer after reacting with an alkoxydecane compound represented by the following formula (7). R12(4-mn)Si(〇R,3)mR14n :(7) [In the formula (7), R12 represents an alkyl group having 1 to 2 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 to 2 An aralkyl group or an organic decyl group having a carbon number of 1 to 1 Å. Where R12 is -17- 201018707, each R12 may be the same functional group or may be a different functional group. R13 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. In the case where OR13 is plural, each OR13 may be the same functional group or may be a different functional group. R1 4 represents a substituent having a polar group containing an N atom. In the case where R14 is plural, each R14 may be the same functional group or may be a different functional group. Further, each R14 is an independent substituent and may have a cyclic structure. m and η represent an integer of 1 to 3. However, the sum of m and η is an integer of 1 to 4]. φ The alkoxydecane compound represented by the above formula (7) can be exemplified by, for example, anthracene-fluorene-bis(trimethyldecyl)aminopropyltrimethoxydecane, anthracene-bis-trimethyldecane. Aminopropyltriethoxydecane, anthracene-fluorene-bis(trimethyldecyl)aminopropyldimethylethoxydecane, anthracene-fluorene-bis(trimethyldecyl)amino group Propyl dimethyl methoxy decane, Ν-Ν-bis(trimethyldecyl)aminopropylmethyldiethoxy decane, Ν-Ν-bis(trimethyldecyl)aminopropyl Methyldimethoxydecane, hydrazine, hydrazine-bis(trimethyldecyl)aminoethyltrimethoxydecane, fluorene-fluorene-bis(trimethyldecyl) 0 aminoethyltriethoxy矽, Ν-Ν-bis(trimethyldecyl)aminoethyl dimethyl ethoxy decane, hydrazine, hydrazine-bis(trimethyldecyl)aminoethyl methoxy decane, Ν, Ν bis (trimethyl decyl) aminoethyl diethoxy decane, hydrazine, hydrazine bis (trimethyl decyl) aminoethyl dimethoxy decane, hydrazine - Methyl-indole-trimethyldecylaminopropyltrimethoxydecane Ν-Methyl-indole-dimethyl ketone-based propyl triethoxy sand, Ν·methyl-Ν-trimethylsalyl propyl dimethyl ethoxy oxime, Ν-甲-18- 201018707 --N-trimethyldecylaminopropyl dimethyl methoxy decane, N-methyl-N-trimethyl decylaminopropyl propyl methyl diethoxy Decane, N-methyl-N-trimethyldecylaminopropylpropyldimethoxydecane, N,N-dimethylaminopropyltrimethoxydecane, N,N-dimethylamine Propyl triethoxy decane, N,N-dimethylaminopropyl dimethyl ethoxy decane, N,N-dimethylaminopropyl dimethyl methoxy decane, N, N -dimethylaminopropylmethyldiethoxydecane, N,N-dimethylaminopropylmethyldimethoxydecane, #N-(l,3-dimethylbutylene)- 3-(triethoxydecyl)-1-propylamine, N-(1-methylethylidene)-3-(triethoxydecyl)-1-propylamine, N-ethylene-3- (triethoxydecyl)-1-propylamine, N-(1-methylpropylene)-3-(triethoxydecyl)-1-propylamine, N-(4-N,N-di Methylaminobenzylidene)-3-(triethoxydecyl)-l- Amine, N-(l,3-dimethylbutylene)-3-(trimethoxydecyl)-l-propylamine, N-(1-methylethylidene)-3-(trimethoxydecylalkyl) )-1-propylamine, N-ethylidene-3-(trimethoxydecyl)-1-propylamine, N-(1-methylpropenylene)-3-(trimethoxydecyl)-1 -propylamine, N-(4-N,N-dimethylaminobenzylidene)-3-(trimethoxydecyl)-1-propylamine, N-(l,3dimethylbenzylidene)- 3-(methyldimethoxydecyl)-1-propylamine, N-(1-methylethylidene)-3-(methyldimethoxydecyl)-1-propylamine, N-Asian 3-(methyldimethoxydecyl)-1-propylamine, N-(1-methylpropylene)-3-(methyldimethoxydecyl)-1-propylamine, N- (4-N,N-Dimethylaminobenzylidene)-3-(methyldimethoxydecyl)-1-propylamine, N-(1,3-dimethylbutylene)-3-( Methyldiethoxydecyl)-1-propylamine, N-(1-methylethylidene)-3-(-19- 201018707 methyldiethoxydecyl)-1·propylamine, N-Asia Ethyl-3-(methyldiethoxydecyl)-1-propylamine, N-(i-methylpropylene)_3·(methyldiethoxydecyl)-1·propylamine, N-(4-N,N-dimethylaminobenzylidene)-3-(methyldiethoxysulphyl)-propylamine, N-(1,3-dimethylbutylene)-3 -(dimethylmethoxydecyl)-1-propylamine, Ν-(1·methylethylidene)-3-(dimethylmethoxydecyl)dipropylamine, N-ethylidene- 3-(Dimethylmethoxydecyl)-1-propylamine, N-(1-methylpropylene)-3-(dimethylmethoxydecyl)-1-propylamine, N-(4 -N,N-dimethylaminobenzylidene)-3-(dimethylmethoxydecyl)-1-propylamine, Ν·(1,3 dimethylbutylene)-3-(dimethyl Ethyl ethoxyalkyl)-1-propylamine, N-(1-methylethylidene)-3-(dimethylethoxydecyl)-1-propylamine, oxime-ethylene-3·( Dimethylethoxydecyl)-1-propylamine, Ν-(1-methylpropylene)-3·(dimethylethoxydecyl)-1-propylamine, Ν-(4-Ν, Ν-Dimethylaminoindenyl)-3-(dimethylethoxyindolyl)-1-propanamine and the like. Process (e): Process (e) is a block copolymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound in the presence of an organic alkali metal compound, and the resulting copolymer A method in which an active point is reacted with an epoxy compound or a ketone compound or a nitrogen-containing compound other than the above formulas (3) to (7) to form a polymer, and then the polymer is hydrogenated. Examples of the "epoxy compound" include ethylene oxide, propylene oxide, and the like. The "ketone compound" can be exemplified by acetone, benzophenone, etc., except for the above formula -20- 201018707 (3) to (7). The nitrogen-containing compound can be exemplified by a nitrogen-containing compound represented by the following formula (8). R15R16C = N-R17 : (8) [In the formula (8), R15 and R16 each represent the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 ~20 aralkyl or carbon Φ number 1~100 organic decyl group, R17 is a hydrogen atom, a carbon number of 3 to 18 trialkyl fluorenyl group, a carbon number of 20 alkyl group, a carbon number of 6 to 20 An aralkyl group having 7 to 20 carbon atoms or an organic decyl group having 1 to 1 carbon atoms. The nitrogen-containing compound represented by the above formula (8) can be exemplified by, for example, N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, and N-benzylidene aniline. . [1-3] Functional group-containing polymer ((iii) component): • The sealing material of the present invention contains, in addition to polypropylene ((i) component) and hydrogenated diene polymer (component (ii)), The functional group-containing polymer (hereinafter sometimes referred to as "(iii) component") is used as a constituent component. By mixing the component (iii), the adhesion to the upper and lower protective materials such as solar cell elements or glass can be improved. The "functional group-containing polymer" as used herein means a polymer having a polymer selected from at least one functional group of the following functional group X and different from the above component (ii). In other words, a polymer which is used as a base skeleton (hereinafter sometimes referred to as "base polymer") can be introduced as a (in) component of the polymer of the above-mentioned -21 - 201018707. By introducing the reactive functional groups, it is possible to connect the upper and lower protective materials such as solar cell elements or glass. [Functional group X]··carboxyl group, acid anhydride group, epoxy group, (meth) propylene group, amine group, alkoxyalkyl group, hydroxyl group, isocyanate group and oxazoline group. As the functional group-containing polymer of the present invention, a functional group-containing olefin-based polymer can be used. The "functional group-containing olefin-based polymer" as used in the present invention means a polymer obtained by introducing an olefin-based polymer as a base polymer and introducing the above functional group into the base polymer. The "olefin-based polymer" which is a base polymer of the component (iii) is a polymer containing a repeating unit derived from an olefin compound (i.e., ethylene and/or an α-olefin). Specifically, a polymer obtained by polymerizing one or two or more kinds of ethylene and/or an α-olefin can be exemplified. The polymerization method is not particularly limited, and for example, a polymer obtained by polymerization such as a conventional polymerization method (e.g., high pressure method, low pressure method, etc.) may be used. However, the base polymer of the component (iii) may also be a repeating unit containing a compound other than the olefin compound. As the "α-olefin", for example, propylene (hereinafter referred to as "propylene"), 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl- can be exemplified. 1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, 1-undecene, etc. Olefins. The olefin-based polymer may, for example, be a polyethylene resin, a polypropylene resin, a polybutene resin, a methylpentene resin or the like. These can be used alone -22- 201018707 One can also combine two or more kinds such as low density polyethylene, medium low density polyethylene, ethylene ·. "Polypropylene resin", polyolefins such as atactic polypropylene, propylene, propylene, butene copolymer, etc., using polyethylene: • (iii) is at least one functional group of the upper group X; An example is a method of combining olefins. For example, a polymer obtained by introducing a carboxyl group into a polymer to obtain an acid anhydride group is introduced, and a (meth)-introduced (meth)acryl-yl group is introduced (including a ring represented by the formula (2)! A polymer of epoxy groups. Further, a specific copolymer of a component by graft polymerization or the like, a carboxy-alkylene (meth)acrylate propylene-based copolymer of Na, Zn, or an acrylic copolymer, a vinyl polymer, and ethylene can be used. • Use of isocyanic acid. The "polyethylene-based resin" can be exemplified by density polyethylene, high-density polyethylene, linear propylene copolymer, ethylene octene copolymer, etc., for example, homopolypropylene, block polypropylene α-olefin copolymer, propylene/ethylene Copolymer, propylene, ethylene, butene copolymer, etc. The rare resin or the polypropylene resin is preferred. A polymer selected from the above functional group S is introduced into the base polymer. The copolymer of the above-mentioned functional group and the monomer copolymerized with the monomer having the functional group and (meth)acrylic acid can be obtained by copolymerizing ethylene with maleic anhydride, by using ethylene and The polymer of the above formula (1 propylene fluorenyl group) can be obtained by copolymerizing ethylene with a compound having the above R group, and introduction of the introduced functional group is not limited to copolymerization, and examples thereof are also exemplified. For example, an anionic polymer obtained by neutralizing an ethylene (methyl) moiety with a metal ion such as ethylene (meth)acrylic acid, a saponified product of ethylene copolymer, or ethylene (meth) • (methyl) Acrylate•Maleic anhydride coenol copolymer, maleic anhydride modified polyethylene-23- 201018707 olefin, maleic anhydride modified polypropylene, maleic anhydride modified ethylene/propylene copolymer, ethylene•A Glycidyl methacrylate copolymer, epoxy-modified ethylene/propylene copolymer, hydroxy-modified polyethylene, hydroxy-modified ethylene/propylene copolymer, etc. Among the above polymers, with solar cell components Or glass, etc. The acid anhydride-containing polymer excellent in the adhesion property of each of the protective materials is more preferably an acid anhydride group-containing polypropylene or ethylene/glycidyl methacrylate copolymer which is more compatible with the (ϋ) component. (Hi) In the range in which the mechanical properties of the obtained sealing material and the moldability are well balanced, a polymer into which the above functional group is introduced may be used. Specifically, it is preferably an average 〇·〇ι~ι, 〇〇〇 The polymer of the above functional group (one/1 molecule) is more preferably an polymer having an average of 0.1 to 500 (one/1 molecule). When the average number of functional groups is less than 0.01 (one/1 molecule), it may not be obtained. On the other hand, when the number of functional groups exceeds 1,000 (n molecules), the fluidity of the composition is lowered to cause a significant decrease in formability. The tendency of the defect. (iii) The molecular weight of the component is not particularly limited 'but the preferred weight average molecular weight is 0.1 million to 200,000, more preferably 5 50,000 to 1.5 million', preferably 0.5 million to 1 million. The weight average molecular weight is less than 0 "110,000" has a tendency to decrease the strength of the solar cell sealing material. On the other hand, when the weight average molecular weight exceeds 2 million, the fluidity of the composition is lowered to lower the formability and cause defects. The term "weight average molecular weight" means the amount of the average molecular weight converted to polystyrene by the gel permeation chromatography (GPC). (iii) The content of the component relative to the (i) component and (ii) The total amount of the components is 100 parts by mass, and it is necessary to be 1 to 40 parts by mass, preferably 0.5 to 30 parts by mass. When the amount is less than 0.1 part by mass, the amount of the polymer containing a functional group is small, and there is a glass or When the amount is more than 40 parts by mass, the amount of the polymer containing a functional group becomes excessive, and the moldability may be lowered. [1-4] Other Additives: As long as the sealing material of the present invention does not impair its physical properties, a secondary additive other than the component (i), the component (b), and the component (iii) may be added. The secondary additive can be exemplified by, for example, an antioxidant, an ultraviolet absorber, an organic peroxide, a decane coupling agent, various chelating agents, a slip agent, a plasticizer, an anti-coloring agent, a coloring agent, an antibacterial agent, a nucleating agent, and an anti-drug. Electrostatic agent, etc. The organic peroxide can be exemplified by, for example, benzammonium peroxide, 2,4-•dichlorobenzhydryl peroxide, tert-butylperoxyacetate, and tert-butylperoxybenzoic acid. Ester, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-tert-butyl peroxide, 2,5·dimethyl Base-2,5-di(t-butylperoxy)-3-hexyne. In particular, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-tert-butyl peroxide, 2 can be more preferably used. One or more of 5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne and the like. When the amount of the organic peroxide used is too small, the conversion of the grafting reaction may be insufficient. When the amount of the free radical-25-201018707 in the polyolefin is too large, the so-called excessive The amount of the (i) component is preferably from 0.01 to 5 parts by mass, more preferably from 0.02 to 2 parts by mass, per part by mass of the component (i). The decane coupling agent is exemplified by having a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amine group, a urea group, a chloropropyl group, a decyl group, a sulfinyl group, an isocyanate machine, A conventional decane compound having an alkyl group or an aryl group as a functional group. Among them, when a graft reaction is carried out using an organic peroxide, a decane compound having a vinyl group or a methacryloxy group as a functional group is preferred. The decane coupling agent is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, per 100 parts by weight of the polymer. The antioxidant may, for example, be a phosphorus-based stabilizer, a hindered phenol-based antioxidant, an epoxy-based stabilizer, or an ion-based stabilizer. The ultraviolet absorber may, for example, be a benzophenone type, a benzotriazole type, a triazine type or a salicylate type. The decane coupling agent can be exemplified by a compound having an unsaturated group such as a vinyl group, a propylene methoxy group, a methacryloxy group, an amine group, an epoxy group or the like and having a hydrolyzable group such as an alkoxy group. As the various cerium materials, cerium oxide, mica, and the like can be exemplified. As the slip agent, a fatty acid decylamine or the like can be exemplified. [2] Closed material sheet:

本發明之封閉材料薄片可藉由使上述構成成分經熔融 混合成形爲薄片而相當容易地製造。混合、成形方法或裝 置並沒有特別限制，但以押出機或班伯里混練機等之混合 、押出T模嘴成形或以砑光成形而成形爲薄片於工業上較 有利而較佳。此時之熔融混合成形溫度較好在150〜250 °C 201018707 之範圍。 如上述獲得之封閉材料薄片上亦可層合保護材。保護 材可層合於封閉材料薄片之單面上。至於保護材可例示爲 金屬、熱可塑性樹脂。保護材可重疊封閉材料薄片後壓著 、共押出成形層合。又，亦可藉由將保護材蒸鍍於封閉材 料薄片上而層合。 可作爲保護材使用之金屬可爲任一種金屬，但以銘較 Φ 佳。該等亦可藉由蒸鍍層合於由封閉材料薄片或熱可塑性 樹脂所構成之保護材上。又，亦可使用氧化矽、氧化鋁替 代金屬。 可作爲保護材使用之熱可塑性樹脂可爲任何熱可塑性 樹脂，但與薄片相同’可使用例如聚乙烯系樹脂、聚丙烯 系樹脂、環狀聚烯烴系樹脂、氟系樹脂、聚苯乙烯系樹脂 、丙烯腈·苯乙烯共聚物（AS樹脂）、丙烯腈-丁二烯-苯 乙烯共聚物（ABS樹脂）、聚氯化乙烯系樹脂、氟系樹脂 ® 、聚（甲基）丙烯酸系樹脂、聚碳酸酯系樹脂、聚對苯二 甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂、各種尼龍 等聚醯胺系樹脂、聚醯亞胺系樹脂、聚醯胺醯亞胺系樹脂 、聚芳基苯二甲酸系樹脂、矽氧系樹脂、聚碾系樹脂、聚 苯硫醚系樹脂、聚醚碾系樹脂、聚胺基甲酸酯系樹脂、縮 醛系樹脂、纖維素系樹脂、其他各種樹脂之薄膜或薄片。 本發明中以聚對苯二甲酸乙二酯、聚偏氟乙烯較佳。 如上述之層合/未經層合保護材之本發明封閉材料薄 片可使用於太陽電池模組中。 -27- 201018707 [實施例] 以下利用實施例更具體說明本發明之封閉材料。但’ 該等實施例不過是顯示本發明之一部份實施型態者。據此 ，本發明不應解釋爲限制於該等實施形態。又’實施例、 比較例中之份及％若未特別說明則爲質量基準。The sealing material sheet of the present invention can be produced relatively easily by melt-mixing the above-mentioned constituent components into a sheet. The mixing, molding method or apparatus is not particularly limited, but it is industrially advantageous to use a mixture of an extruder or a Banbury mixer or the like, or to form a T-die or to form a sheet by calendering. The melt mixing forming temperature at this time is preferably in the range of 150 to 250 ° C 201018707. The protective material may also be laminated on the sheet of the sealing material obtained as described above. The protective material can be laminated to one side of the sheet of the closure material. As the protective material, a metal or a thermoplastic resin can be exemplified. The protective material may be laminated with a sheet of the sealing material and pressed together to form a laminate. Further, it may be laminated by depositing a protective material on the sealing material sheet. The metal that can be used as a protective material can be any metal, but it is better than Φ. These may also be laminated to a protective material composed of a sheet of sealing material or a thermoplastic resin by vapor deposition. Further, iridium oxide or aluminum oxide may be used instead of the metal. The thermoplastic resin which can be used as the protective material may be any thermoplastic resin, but may be the same as the sheet. For example, a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, a fluorine resin, or a polystyrene resin may be used. , acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polychlorinated vinyl resin, fluorine resin®, poly(meth)acrylic resin, Polyester resin such as polycarbonate resin, polyethylene terephthalate or polyethylene naphthalate, polyamine resin such as nylon, polyimide resin, polyamidimide Resin, polyaryl phthalic acid resin, oxime resin, poly pulverized resin, polyphenylene sulfide resin, polyether mill resin, polyurethane resin, acetal resin, fiber A film or sheet of a resin or other various resins. In the present invention, polyethylene terephthalate or polyvinylidene fluoride is preferred. The closure material sheet of the present invention, such as the laminated/unlaminated protective material described above, can be used in a solar cell module. -27- 201018707 [Examples] Hereinafter, the sealing material of the present invention will be more specifically described by way of examples. However, the embodiments are merely illustrative of some of the embodiments of the present invention. Accordingly, the invention should not be construed as being limited to the embodiments. Further, the parts and % in the examples and comparative examples are based on mass unless otherwise specified.

[1] ( Π)成分之合成及評價： Q 在說明本發明之封閉材料之前，先合成作爲其原料之 (ii)成分[含有官能基之氫化二烯系聚合物]。其合成方 法以合成例表示。又，以下列方法測定、評價（ii )成分 之物性値。 (1)乙烯鍵含量（1，2-鍵含量及3,4-鍵含量）： 使用紅外線分析法，由漢普敦（Hampton )法計算出 〇 (2)結合之苯乙烯含量： 使用四氯化碳作爲溶劑，由270MHz、h-NMR光譜計 算出。 (3 )重量平均分子量： 使用凝膠滲透層析儀（GPC，商品名：HLC-8120，東 曹公司製造），求得換算成聚苯乙烯之重量平均分子量。 -28- 201018707 (4 ) MFR (熔融流動速率）： 以JIS K7210所述之方法爲準，在23(rc，2i2N荷重 之條件下測定。 (5) 官能基含重（個/聚合物）： 所謂「官能基含量」意指聚合物中之官能基之比例， φ 且可以下式（9)表示。 官能基含量=官能基（個）/聚合物（一分子鏈） ：（9) 該官能基含量係以Analy. Chem. 564(1 952)所述之胺 滴定法爲準予以定量。亦即，（ii )成分經純化後，溶解 於有機溶劑中’且使用甲基紫作爲指示劑，滴加 HC104/CH3C00H至溶液顔色由紫變成水色爲止，由該滴加 • 量計算出官能基含量。 (6) 共軛二烯之氫化率： 使用四氯化碳作爲溶劑，由270MHz、W-HMR光譜計 算出。 (合成例l/ii·1之合成） 於經氮氣置換之內容積5 0升之反應容器中添加環己院 (25kg)、四氫呋喃（750g)及苯乙烯（500g) ’且自50 -29- 201018707 °C進行絕熱聚合。反應結束後，使溫度成爲20 °C且添加 1，3· 丁二烯（ 4,250g)，再進行絕熱聚合。30分鐘後’添 加苯乙烯（25 0g)，再進行聚合。 聚合結束後，以〇.4MPa-錶壓之壓力供給氫氣，攪拌 2 0分鐘，與作爲活性陰離子而生成之聚合物末端鋰反應’ 成爲氫化鋰。使反應溶液成爲90°C，且使用以二茂鈦二氯 化物做爲主體之觸媒進行氫化反應。氫吸收結束之時點， 使反應溶液恢復至常溫、常壓且自反應容器洩出。接著在 攪拌下將反應溶液注入水中，且藉由蒸氣汽提去除溶劑， 獲得構造爲A-B-A型之氫化二烯系聚合物（以下稱爲「ii-1 j ) ° 測定ii-Ι之分子特性，聚丁二烯嵌段（聚合物嵌段B ) 之乙烯鍵含量爲79%，氫化前聚合物之鍵結苯乙烯含量爲 15質量％，重量平均分子量爲11萬，MFR爲24g/10分鐘， 氫化率爲97%。結果列於表1。 201018707 [表u ii-1 ii-2 ii-3 苯乙烯 (質量％) 15 15 15 丁二烯 (質量％) 85 85 85 B嵌段之乙烯鍵含量 (%) 79 78 78 構造 A-B-A A-B-A A-B-A 雷量平均分子量 (xlO4) 11 13 12 氫化率 (%) 97 97 98 MFR (g/1吩鐘） 24 22 17 官能基有無 無 有 有 官能基_ - 胺基 胺基，院氧 基砂烷基 官能基量 (個/聚合物) 0.98 0.84 改質劑種類 - (a) ⑻ (眇2,2,5,5-四甲基小(3-鋰離子丙基)-1-氮雜-2,5-二矽烷環戊烷 (b):N,N-雙(三甲基矽院基)胺基丙基甲基二乙氧基砂院 (合成例2/ii-2之合成） 除於經氮氣置換之內容積50升反應容器中添加 2,2,5,5-四甲基-1- ( 3-鋰離子丙基）-1-氮雜-2,5-二矽烷環 戊烷（14.5 kg )以外，餘如上述合成例1般，獲得構造爲 A-B-A型之含官能基之氫化二烯聚合物（以下稱爲「ii-2」 )° 測定ii-2之分子特性’發現聚丁二烯嵌段（聚合物嵌 段B)之乙烯鍵含量爲78%’氫化前聚合物之鍵結苯乙烯 含量爲15質量％ ’重量平均分子量舄13萬，MFR爲22 g/10 分鐘，官能基含量爲〇.98個/聚合物，氫化率爲97%。結果 列於表1。 31 - 201018707 (合成例3/ii-3之合成） 除於經氮氣置換之內容積50升反應容器中添加N，N_雙 (三甲基砂烷基）胺基丙基甲基二乙氧基砂烷21.3g以外 ，餘如上述合成例1般’獲得構造爲A-B·A型之含官能基之 氫化二烯聚合物（以下稱爲「Η·3」）° 測定Π-3之分子特性’發現聚丁二烯嵌段（聚合物嵌 段B)之乙烯鍵含量爲78%’氫化前聚合物之鍵結苯乙烯 含量爲15質量％，重量平均分子量爲12萬，MFR爲17 g/10 分鐘，官能基含量爲0.84個/聚合物，氫化率爲98%。結果 列於表1。 [2]太陽電池封閉材料之製造： (實施例1 ) 將20質量份之作爲（i)成分之聚丙烯、80質量份之 作爲（Π)成分之以上述[1]合成之「ii-Ι」及10質量份之 作爲（iii)成分（馬來酸酐改質之聚丙烯，三洋化成工業 公司製造’商品名：Umaxl〇i〇 )分別以真空乾燥機使水 分充分減少後’經混合，且使用直徑40mm之押出機（池 貝公司製造），在23 0 °C下混練片粒化。使用τ模嘴押出成 形機使所得片粒在23 °C下成爲厚度〇.5mm之薄片，獲得實 施例1之太陽電池元件封閉材料。其評價結果列於表2。 -32- 201018707 【s】 κη ο r < ο 良好 不良 〇\ VO 寸 〇 ο 良好1 不良 比較例 m g ο <N 00 良好 良好 〇 (N § ο 00 1良好1 良好 ο ί-Η g 落 不良 良好 Os ο in 寸 ο (N rs Os 良好 Γ-· oo Ο s CN Ο 1—Η m Os 良好 CN 卜 沄 ο ι〇 a\ 良好 良好 Ο s Ο 艺 良好 CS ΟΝ 實施例 ο δ ο m On 良好 U-) Ο 寸 ο 良好 __1 fN QO m § ο ON 良好 00 00 (N § ο m Os 良好 冢 § ο m On i 担 2 ί Κ 鬆 矽烷偶合劑 全光透過率(％) 接著性(對玻璃） if 艋吝 蕊2 魆X Sg S 2 硬度(SHORE-A) /—N I :έ r~s :三 m m 鹚 :三 ΐ S u 特性 (棚IKIM<43N3AldcmdAlod-M-[nu9oawng躯)遐r嵌··【^1gs】 il^mdd^im^nnnsi^in^liifii^lHSS^^00SUH^<s§ffl^nnn®W^I^^K«fr · §s0i^蓉啦骹浓褰 υΛΡ>_^«貂_<ra-NM^I 嗽：【Φ链(ε-π)】 鬆啦嵌恢繫：！^_^糊貂_釦^尿鉅1撇：【汆隻3)】 -33- 201018707 (實施例2~7，比較例1~5 ) 除將（i)成分、（ii)成分、（iii)成分之種類及量 改變成表2所記載以外，餘如實施例1般，獲得實施例2〜6 、比較例1~5之太陽電池元件封閉材料。結果列於表2。 (實施例8 ) 將4 0質量份之作爲（i)成分之聚丙烯、60質量份之 作爲（Π)成分之於上述Π]合成之「ii-2」及5質量份之作 爲（iii)成分（乙烯•甲基丙烯酸縮水甘油酯，商品名： BONDFAST CG5004，住友化學工業公司製造）分別以真 空乾燥機使水分充分減少後，添加有機過氧化物（二枯基 過氧化物，商品名：BARKMILL D，日本油脂製造）、矽 烷偶合劑（乙烯基三甲氧基矽烷，商品名：KBM1003，信 越化學工業公司製造）並經混合，且使用直徑45mm之二 軸押出機（池貝公司製造），在200 °C下混練而顆粒化。 使用T模嘴押出成形機使所得顆粒在230 °C下成爲厚度 0.5mm之薄片，獲得實施例1之太陽電池元件封閉材料。其 評價結果列於表2。 (實施例9 ) 除將（i)成分、（ii)成分、（iii)成分之種類及量 改變成如表2中所列以外，餘如實施例8同樣，獲得實施例 9之太陽電池封閉材料。結果列於表2。 再者，實施例1〜9、比較例1〜5中係使用下列作爲（i -34- 201018707 )成分、（ii)成分及（ΠΠ成分。 [(i )成分]:聚丙烯（商品名：BC6C ’日本 POLYPROPYLENE公司製造） [(ii-Ι)成分]:於上述Π]合成之「ii·1」 [(ii-2)成分]:於上述Π]合成之「Π-2」 [(ii-3)成分]:於上述[1]合成之「ϋ-3」 [(iii )成分]:馬來酸酐改質之聚丙烯（商品名： φ Umax 1010，三洋化成工業公司製造， [3]太陽電池元件封閉材料之評價： 以下述方法測定、評價太陽電池元件封閉材料之物性 値。結果列於表2。 (η全光透過率： 本說明書中，全光透過率表示以JIS_K7105 (光線透 • 過率及全光線反射率）爲準測定之値。該全光透過率係使 用曰本電色工業製造之濁度計（商品名：「NDH 2 000」） 測定。 (2 )接著性（對玻璃）： 以5mm厚之透明玻璃板夾住〇.5mm厚之薄片樣品，在 溫度調整爲20(TC之壓製機上壓製成薄片厚度〇·3 mm，製備 層合體。使該層合體冷卻後，以手剝離玻璃與薄片樣品之 間，觀察該剝離狀況，以下列二階段評價。 -35- 201018707 良好：接著性良好，不良：接著性不良 (3 ) 60度傾斜試驗（l〇〇°CxlOO小時） 以5mm厚之透明玻璃板夾住〇.5mm厚之薄片樣品，在 溫度調整爲200°C之壓製機上壓製成薄片厚度〇.3mm，製備 層合體。使該層合體冷卻後，在100 °C下傾斜60度，観察 薄片熔融且觀察是否未自玻璃偏移直至100小時爲止，以 下列兩階段評價。 _ 良好：沒有偏移，不良；有偏移 (4)硬度（蕭氏（SHORE) -A) 以JIS K625 3爲準測定作爲柔軟度之指標。 [評價結果]:[1] Synthesis and evaluation of (Π) component: Q Before describing the sealing material of the present invention, (ii) component [hydrogenated diene polymer containing a functional group] as a raw material is synthesized. The synthesis method is represented by a synthesis example. Further, the physical properties of the component (ii) were measured and evaluated by the following methods. (1) Content of vinyl bond (1,2-bond content and 3,4-bond content): The styrene content of ruthenium (2) combined by the Hampton method was calculated by infrared spectroscopy: tetrachloroethylene was used. Carbon was used as a solvent and calculated from a 270 MHz, h-NMR spectrum. (3) Weight average molecular weight: A weight average molecular weight converted into polystyrene was determined using a gel permeation chromatography (GPC, trade name: HLC-8120, manufactured by Tosoh Corporation). -28- 201018707 (4) MFR (melt flow rate): It is determined by the method described in JIS K7210 under the condition of 23 (rc, 2i2N load). (5) Functional group weight (unit/polymer): The "functional group content" means the ratio of the functional group in the polymer, φ and can be represented by the following formula (9): functional group content = functional group (unit) / polymer (one molecular chain): (9) the functional group The base content is quantified by the amine titration method described in Analy. Chem. 564 (1 952), that is, the component (ii) is purified, dissolved in an organic solvent, and methyl violet is used as an indicator. HC104/CH3C00H was added dropwise until the color of the solution changed from purple to water, and the functional group content was calculated from the amount of addition. (6) Hydrogenation ratio of conjugated diene: Using carbon tetrachloride as a solvent, 270 MHz, W- The HMR spectrum was calculated. (Synthesis Example 1/ii·1 synthesis) Cyclohexylamine (25 kg), tetrahydrofuran (750 g) and styrene (500 g) were added to a reaction vessel containing 50 liters of internal volume substituted with nitrogen. Adiabatic polymerization from 50 -29 to 201018707 ° C. After the reaction is completed, the temperature is made 20 ° C and added 1,3· Butadiene (4,250g), and then adiabatic polymerization. After 30 minutes, 'styrene (25 0g) was added and polymerization was further carried out. After the end of the polymerization, hydrogen was supplied at a pressure of MPa4 MPa-gauge, and stirred. 20 minutes, reacting with the terminal lithium of the polymer formed as the living anion to become lithium hydride. The reaction solution was brought to 90 ° C, and hydrogenation reaction was carried out using a catalyst mainly composed of titanocene dichloride. At the end of the reaction, the reaction solution is returned to normal temperature, normal pressure and discharged from the reaction vessel. Then, the reaction solution is poured into water under stirring, and the solvent is removed by steam stripping to obtain a hydrogenated diene polymerization structure of the ABA type. (hereinafter referred to as "ii-1 j ) ° Determine the molecular characteristics of ii-Ι, the polybutadiene block (polymer block B) has a vinyl bond content of 79%, and the polymer is bonded to the styrene before hydrogenation. The content was 15% by mass, the weight average molecular weight was 110,000, the MFR was 24 g/10 min, and the hydrogenation rate was 97%. The results are shown in Table 1. 201018707 [Table u ii-1 ii-2 ii-3 Styrene (% by mass) 15 15 15 Butadiene (% by mass) 85 85 85 Block B Key content (%) 79 78 78 Structure ABA ABA ABA Thunder average molecular weight (xlO4) 11 13 12 Hydrogenation rate (%) 97 97 98 MFR (g/1 knives) 24 22 17 Functional group with or without functional groups _ - Amino amine group, alkoxyalkyl functional group amount (unit / polymer) 0.98 0.84 Modifier type - (a) (8) (眇2,2,5,5-tetramethyl small (3-lithium) Ionic propyl)-1-aza-2,5-dioxane cyclopentane (b): N,N-bis(trimethylindenyl)aminopropylmethyldiethoxylate (synthesis) Synthesis of Example 2/ii-2) In addition to the addition of 2,2,5,5-tetramethyl-1-(3-lithium propyl)-1-aza in a 50 liter reaction vessel filled with nitrogen In addition to the above-mentioned Synthesis Example 1, except for the use of -2,5-dioxanecyclopentane (14.5 kg), a hydrogenated diene polymer having a functional group of the ABA type (hereinafter referred to as "ii-2") was obtained. Determination of the molecular characteristics of ii-2 'The polybutadiene block (polymer block B) was found to have a vinyl bond content of 78%'. The polymerized prepolymer had a bonded styrene content of 15% by mass. 'Weight average molecular weight 舄13 Million, MFR is 22 g/10 min, and the functional group content is 〇98/polymer. The hydrogenation rate was 97%. The results are shown in Table 1. 31 - 201018707 (Synthesis of Synthesis Example 3/ii-3) In addition to N,N-bis(trimethylsilyl)aminopropylmethyldiethoxylate in a 50 liter reaction vessel filled with nitrogen The hydrogenated diene polymer having a functional group of AB·A type (hereinafter referred to as "Η·3") was obtained as in the above Synthesis Example 1 except for 21.3 g of the base sand. 'The polybutadiene block (polymer block B) was found to have a vinyl bond content of 78%. The polymer before hydrogenation had a bonded styrene content of 15% by mass, a weight average molecular weight of 120,000, and an MFR of 17 g/ At 10 minutes, the functional group content was 0.84 / polymer, and the hydrogenation rate was 98%. The results are shown in Table 1. [2] Manufacture of the solar cell sealing material: (Example 1) 20 parts by mass of the polypropylene as the component (i) and 80 parts by mass of the component (Π) are synthesized by the above [1]. And 10 parts by mass of the component (iii) (maleic anhydride-modified polypropylene, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Umaxl〇i〇), respectively, was sufficiently reduced by a vacuum dryer to be mixed, and The granulation was carried out at 23 ° C using a 40 mm diameter extruder (manufactured by Chiba Corporation). The obtained pellets were formed into a sheet having a thickness of 〇5 mm at 23 ° C using a τ nozzle extrusion molding machine to obtain a solar cell element sealing material of Example 1. The evaluation results are shown in Table 2. -32- 201018707 [s] κη ο r < ο Good bad 〇 \ VO 〇 good 1 bad comparative example mg ο <N 00 Good good 〇 (N § ο 00 1 good 1 good ο ί-Η g Bad good Os ο in inch ο (N rs Os good Γ-· oo Ο s CN Ο 1—Η m Os Good CN Bu 沄 ι〇a\ Good good Ο Ο 艺 Good good CS 实施 Example ο δ ο m On Good U-) Ο inch ο good __1 fN QO m § ο ON Good 00 00 (N § ο m Os good 冢 § m om m ii 担 矽 矽 偶 偶 全 全 全 全 全 全 全 全 全 全 全 全 全For glass) if 艋吝 2 2 魆X Sg S 2 Hardness (SHORE-A) /—NI :έ r~s : three mm 鹚: three ΐ S u characteristics (shed IKIM<43N3AldcmdAlod-M-[nu9oawng body)遐r embedded··[^1gs] il^mdd^im^nnnsi^in^liifii^lHSS^^00SUH^<s§ffl^nnn®W^I^^K«fr · §s0i^蓉骹骹υΛΡ>_^«貂_<ra-NM^I 嗽: [Φ chain (ε-π)] 松啦嵌系::^_^糊_ buckle ^ urine giant 1 撇: [汆 only 3)] -33- 201018707 (Examples 2 to 7, Comparative Examples 1 to 5) except for the types of components (i), (ii), and (iii) The solar cell element sealing materials of Examples 2 to 6 and Comparative Examples 1 to 5 were obtained as in Example 1 except that the amounts were changed as shown in Table 2. The results are shown in Table 2. (Example 8) 40 mass The component (i) component of the polypropylene, 60 parts by mass of the (Π) component of the above-mentioned Π] synthesized "ii-2" and 5 parts by mass of the component (iii) (ethylene methacrylic acid glycidol Ester, trade name: BONDFAST CG5004, manufactured by Sumitomo Chemical Industries Co., Ltd.) After the water is sufficiently reduced by a vacuum dryer, an organic peroxide (dicumyl peroxide, trade name: BARKMILL D, manufactured by Nippon Oil Co., Ltd.), decane is added. A coupling agent (vinyl trimethoxy decane, trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and granulated by kneading at 200 ° C using a two-axis extruder (manufactured by Chiba Corporation) having a diameter of 45 mm. The solar cell element sealing material of Example 1 was obtained by using a T-die extrusion molding machine to obtain a sheet having a thickness of 0.5 mm at 230 °C. The evaluation results are shown in Table 2. (Example 9) The solar cell of Example 9 was obtained in the same manner as in Example 8 except that the kind and amount of the component (i), the component (ii), and the component (iii) were changed as listed in Table 2. material. The results are shown in Table 2. Further, in Examples 1 to 9 and Comparative Examples 1 to 5, the following (i-34-201018707) component, (ii) component, and (ΠΠ component. [(i) component]: polypropylene (trade name: BC6C 'Manufactured by Japan POLYPROPYLENE Co., Ltd.' [(ii-Ι) component]: "ii·1" [(ii-2) component] synthesized in the above Π]: "Π-2" synthesized in the above Π] [(ii -3) Ingredients: "ϋ-3" [(iii) component synthesized in the above [1]: Maleic anhydride modified polypropylene (trade name: φ Umax 1010, manufactured by Sanyo Chemical Industries, Ltd., [3] Evaluation of solar cell element sealing material: The physical properties of the solar cell element sealing material were measured and evaluated by the following method. The results are shown in Table 2. (η total light transmittance: In this specification, the total light transmittance is expressed by JIS_K7105 (light transmission) • The over-rate and the total light reflectance are measured. The all-light transmittance is measured using a turbidity meter (trade name: “NDH 2 000”) manufactured by Sakamoto Electric Co., Ltd. (2) Adhesiveness ( For the glass): A 5 mm thick sheet sample was clamped with a 5 mm thick transparent glass plate and pressed into a sheet thickness at a temperature of 20 (TC press). After the laminate was cooled, the laminate was peeled between the glass and the sheet sample by hand, and the peeling condition was observed and evaluated in the following two stages. -35 - 201018707 Good: Good adhesion, poor: Poorness of the next (3) 60 degree tilt test (l〇〇°Cx100 hours) The 5 mm thick sheet sample was clamped with a 5 mm thick transparent glass plate and pressed into a sheet thickness on a press machine adjusted to a temperature of 200 °C.层. 3 mm, a laminate was prepared. After the laminate was cooled, it was tilted at 100 ° C for 60 degrees, and the sheet was melted and observed to be not offset from the glass until 100 hours, and evaluated in the following two stages. _ Good: No Offset, poor; offset (4) hardness (Shore -A) Measured as an indicator of softness based on JIS K625 3. [Evaluation results]:

自表2可瞭解實施例1〜9之太陽電池元件封閉材料任一 例均具備全光透過率、對玻璃之接著性、60度傾斜試驗及 D 硬度均衡之良好特性， 相對於此，缺少（iii )成分之比較例1之太陽電池元 件封閉材料對玻璃之接著性不足。另外，含過量（i)成 分之比較例2及3之太陽電池元件封閉材料之全光透過率低 。再者，缺少（i)成分之比較例4及5之太陽電池元件封 閉材料在60度傾斜試驗時產生偏移。且硬度亦不足。 [產業上利用之可能性] -36- 201018707 本發明之封閉材料及太陽電池模組係用於製造太陽電 池。It can be understood from Table 2 that any of the solar cell element sealing materials of Examples 1 to 9 has good characteristics of total light transmittance, adhesion to glass, 60 degree tilt test, and D hardness balance, and is lacking (iii). The solar cell element sealing material of Comparative Example 1 was insufficient in adhesion to glass. Further, the solar cell element sealing materials of Comparative Examples 2 and 3 containing an excessive amount of the (i) component had a low total light transmittance. Further, the solar cell element sealing materials of Comparative Examples 4 and 5 lacking the component (i) were offset at the 60-degree tilt test. And the hardness is not enough. [Possibility of Industrial Utilization] -36- 201018707 The sealing material and solar cell module of the present invention are used for manufacturing a solar cell.

-37--37-

Claims (1)

201018707 七、申請專利範圍： 1·—種封閉材料，其特徵爲以（i)成分：聚丙烯，（ ii)成分：氫化二烯系聚合物，及（iii)成分：具有選自 下述官能基群X之至少一種官能基之聚合物且爲與上述（ Π)成分不同之聚合物（含有官能基之聚合物）作爲構成 成分， 且相對於上述（i)成分〇~60質量份，上述（ii)成分 40~100質量份（合計量1〇〇質量份），含有ι〜1〇〇質量份之 上述（iii )成分， [官能基群X]:羧基、酸酐基、環氧基、（甲基）丙 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸酯基及噁唑 啉基。 2,如申請專利範圍第1項之封閉材料，其中上述（ii) 成分爲含有下述聚合物嵌段A及下述聚合物嵌段b之聚合物 ，且爲構成上述（ii)成分之下述共範二嫌化合物單位之 雙鍵之至少80%經氫化之氫化二烯系聚合物， [聚合物嵌段A]:含有50質量％以上之芳香族乙烯基化 合物單位之聚合物嵌段， [聚合物嵌段B]:含有50質量％以上之共範二儲化合物 單位，且其1,2-鍵含量及3,4-鍵含量之合計在3〇~9〇%範圍 內之聚合物嵌段。 3 ·如申請專利範圍第1項之封閉材料，其中上述（^ ) 成分爲具有選自下述官能基群X之至少一種官能基之氫化 二嫌系聚合物（含有官能基之氫化二稀系聚合物）， 201018707 [官能基群X]:羧基、酸酐基、環氧基、（ 嫌醯基、胺基、烷氧基矽烷基、羥基、異氯酸醋 啉基。 4. 如申請專利範圍第2項之封閉材料，其中』 成分爲具有選自下述官能基群X之至少—種胃會g 二嫌系聚合物（含有官能基之氫化二烯系聚合物 [官能基群X]:羧基、酸酐基、環氧基、（ • 烯醯基、胺基、烷氧基矽烷基、羥基、異氣酸醋 啉基。 5. 如申請專利範圍第i項之封閉材料，其φ )成分爲具有選自下述官能基群X之至少_種胃 官能基之烯烴系聚合物， [官能基群X]:羧基、酸酐基、環氧基、（ 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸醋 啉基。 ® 6.如申請專利範圍第2項之封閉材料，其中 )成分爲具有選自下述官能基群X之至少—種官 官能基之烯烴系聚合物， [官能基群X]:羧基、酸酐基、環氧基、（ 嫌醯基、胺基、院氧基砂院基、經基、異氰酸醋 啉基。 7.如申請專利範圍第3項之封閉材料，其中 )成分爲具有選自下述官能基群X之至少一種官 官能基之烯烴系聚合物， 甲基）丙 基及噁唑 :述（ii ) 基之氫化 )， 甲基）丙 基及噁唑 上述（iii 能基之含 甲基）丙 基及噁唑 上述（iii 能基之含 甲基）丙 基及噁唑 上述（iii 能基之含 -39- 201018707 [官能基群χ]:羧基、酸酐基、環氧基、（甲基）丙 稀醯基、胺基、院氧基砂院基、經基、異氰酸醋基及嚼哩 啉基。 8. 如申請專利範圍第4項之封閉材料，其中上述（iH )成分爲具有選自下列官能基群X之至少一種官能基之含 官能基之烯烴系聚合物， [官能基群X]:羧基、酸酐基、環氧基、（甲基）丙 烯醯基、胺基、烷氧基矽烷基、羥基、異氰酸酯基及噁唑 _ 啉基。 9. 如申請專利範圍第5項之封閉材料，其中上述（in )成分爲含有酸酐基之丙嫌系聚合物或乙嫌•甲基丙嫌酸 縮水甘油酯共聚物。 10. 如申請專利範圍第6項之封閉材料，其中上述（Hi )成分爲含有酸Sf基之丙烯系聚合物或乙嫌•甲基丙嫌酸 縮水甘油酯共聚物。 11. 如申請專利範圍第7項之封閉材料，其中上述（in 0 )成分爲含有酸酐基之丙嫌系聚合物或乙嫌•甲基丙嫌酸 縮水甘油酯共聚物。 12. 如申請專利範圍第8項之封閉材料，其中上述（iH )成分爲含有酸軒基之丙稀系聚合物或乙燒•甲基丙嫌酸 縮水甘油酯共聚物。 13. —種封閉材料薄片，其特徵爲使用申請專利範圍 第1〜1 2項中任一項之封閉材料。 ί4.如申請專利範圍第13項之封閉材料薄片，其中於 -40- 201018707 其一面上層合有熱可塑性樹脂及/或金屬。 15. 如申請專利範圍第1~12項中任一項之封閉材料， 其中上述封閉材料係作爲太陽電池之封閉材料使用。 16. 如申請專利範圍第13項之封閉材料薄片，其中上 述封閉材料薄片係作爲太陽電池之封閉材料使用。 I7·如申請專利範圍第14項之封閉材料薄片，其中上 述封閉材料薄片係作爲太陽電池之封閉材料使用。 ® IS.—種太陽電池模組，其特徵係使用申請專利範圍 第I3項之封閉材料薄片。 19_ 一種太陽電池模組，其特徵係使用申請專利範圍 第I4項之封閉材料薄片_。201018707 VII. Patent application scope: 1. A kind of sealing material characterized by (i) component: polypropylene, (ii) component: hydrogenated diene polymer, and (iii) component: having the following functional groups a polymer having at least one functional group of the group X and a polymer (a polymer containing a functional group) different from the above (Π) component as a constituent component, and 〇~60 parts by mass based on the above component (i), (ii) 40 to 100 parts by mass of the component (1 part by mass in total), containing ι to 1 part by mass of the above component (iii), [functional group X]: carboxyl group, acid anhydride group, epoxy group, (Meth) acrylonitrile, an amine group, an alkoxyalkyl group, a hydroxyl group, an isocyanate group, and an oxazoline group. 2. The sealing material according to claim 1, wherein the component (ii) is a polymer comprising the polymer block A and the polymer block b described below, and is composed of the component (ii) below. a hydrogenated diene polymer which is hydrogenated at least 80% of the double bond of the compound unit, [polymer block A]: a polymer block containing 50% by mass or more of the aromatic vinyl compound unit, [Polymer block B]: a polymer containing 50% by mass or more of a common dibasic compound unit and having a total of 1,2-bond content and 3,4-bond content in the range of 3〇 to 9〇% Block. 3. The sealing material according to claim 1, wherein the (^) component is a hydrogenated divalent polymer having at least one functional group selected from the following functional group X (hydrogenated dilute system containing a functional group) Polymer), 201018707 [Functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, (anthracene group, an amine group, an alkoxyalkyl group, a hydroxyl group, an isocyanate group.) 4. The sealing material of the second aspect, wherein the component is at least one selected from the group consisting of the following functional groups X: a dihydrogen polymer (functional group-containing hydrogenated diene polymer [functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, (• an olefin group, an amine group, an alkoxyalkyl group, a hydroxyl group, an isophthalic acid hydroxy group. 5. The sealing material of the item i of claim patent φ) An olefin-based polymer having at least one gastric functional group selected from the following functional group X, [functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, an (methenyl group, an amine group, an alkoxy group)矽alkyl, hydroxy, isocyanatoyl. ® 6. Closure material as claimed in item 2 , wherein the component is an olefin-based polymer having at least a genus functional group selected from the group of functional groups X below, [functional group X]: a carboxyl group, an acid anhydride group, an epoxy group, (an anthracene group, an amine group) The oxidizing agent base, the thiol group, and the isocyanatoyl group. 7. The sealing material according to claim 3, wherein the component is at least one functional group having a functional group X selected from the group consisting of Olefin-based polymer, methyl)propyl and oxazole: hydrogenation of (ii) group, methyl)propyl and oxazole, above (iii, methyl group-containing methyl) propyl and oxazole, above (iii) The methyl group-containing propyl group and the oxazole are as described above. (iii. The energy group contains -39- 201018707 [functional group]: carboxyl group, acid anhydride group, epoxy group, (meth) acrylonitrile group, amine group The oxidized sand base, the warp group, the isocyanate group and the chelate porphyrin group. 8. The sealing material according to claim 4, wherein the (iH) component has a functional group X selected from the group consisting of Functional group-containing olefin-based polymer of at least one functional group, [functional group X]: carboxyl group, acid anhydride group, epoxy group, (methyl group) A propylene group, an amine group, an alkoxyalkyl group, a hydroxyl group, an isocyanate group, and an oxazol group. 9. The sealing material according to claim 5, wherein the (in) component is an acid anhydride group-containing A polymer or a propylene glycol methacrylate copolymer. 10. The sealing material of claim 6 wherein the (Hi) component is a propylene-based polymer containing an acid Sf group or • a methyl propylene succinic acid glycidyl ester copolymer. 11. A sealing material according to claim 7 wherein the above (in 0 ) component is an acid anhydride-based propylene polymer or a susceptor. Acid glycidyl ester copolymer. 12. The sealing material of claim 8 wherein the (iH) component is an acrylic polymer containing an acid group or an ethylene methacrylate copolymer. A closure material sheet characterized by using the sealing material according to any one of claims 1 to 12. Ί4. A sheet of sealing material according to claim 13 wherein a thermoplastic resin and/or metal is laminated on one side of the layer from -40 to 201018707. 15. The closure material of any one of claims 1 to 12, wherein the closure material is used as a sealing material for a solar cell. 16. A sheet of closure material according to claim 13 wherein said sheet of closure material is used as a closure material for a solar cell. I7. The closure material sheet of claim 14, wherein the closure material sheet is used as a sealing material for a solar cell. ® IS.—A solar cell module characterized by the use of a sheet of sealing material in the scope of claim I. 19_ A solar cell module characterized by the use of a sheet of sealing material _ in the scope of claim I. -41 - 201018707 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無-41 - 201018707 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201018707 五、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201018707 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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