TW201242054A - Adhesive composition for laminating sheet and back protective sheet for solar cell - Google Patents

Adhesive composition for laminating sheet and back protective sheet for solar cell Download PDF

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Publication number
TW201242054A
TW201242054A TW101104895A TW101104895A TW201242054A TW 201242054 A TW201242054 A TW 201242054A TW 101104895 A TW101104895 A TW 101104895A TW 101104895 A TW101104895 A TW 101104895A TW 201242054 A TW201242054 A TW 201242054A
Authority
TW
Taiwan
Prior art keywords
sheet
film
adhesive
adhesive composition
acid
Prior art date
Application number
TW101104895A
Other languages
Chinese (zh)
Other versions
TWI548104B (en
Inventor
Akira Saito
Satoshi Maeda
Mitsuo Umezawa
Takeshi Yoshikawa
Original Assignee
Toyo Ink Sc Holdings Co Ltd
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Publication date
Application filed by Toyo Ink Sc Holdings Co Ltd filed Critical Toyo Ink Sc Holdings Co Ltd
Publication of TW201242054A publication Critical patent/TW201242054A/en
Application granted granted Critical
Publication of TWI548104B publication Critical patent/TWI548104B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S20/00—Supporting structures for PV modules
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

An adhesive composition for fabricating a back protective sheet of solar cell is provided. The adhesive composition provides high adhesion between various sheet-like portions, especially between layers including surface treatment layer of plastic film, and the high adhesion can be maintained even when the adhesive composition is exposed to an environment of high temperature and high humidity. The adhesive composition for a laminating sheet of this invention includes an acrylic polyol (A) and a polyisocyanate (B), wherein a number average molecular weight of the acrylic polyol (A) is 10,000 to 100,000m, a hydroxyl value is l to 100 mgKOH/g, and a glass transition temperature (Tg) is more than -40 DEG C and no more than 10 DEG C. Further, an equivalent ratio NCO/OH of a hydroxyl group from the acrylic polyol (A) and an isocyanate group from the polyisocyanate (B) is 0.1 to 3.

Description

201242054 . -rx v/z- / 1 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種積層片用接著劑組成物及太陽電 池用背面保護片。 【先前技術】 近年來，以面向室外產業用途的例如屏障材料、屋頂 材料、太陽電池面板材料、窗戶材料、室外地板材料、昭 明保護材料:汽車部件、招牌、標籤料所使用的多層㈠复 合）膜等為·Τ的多層（複合）積層體得到實用化 層體可藉由對金屬系原材料或塑膠系原材料 ^ (層壓）而獲得。金屬系原材料可列舉鋁或鋼、鋼板等‘ 屬笛、金屬板、金屬蒸鍍膜等。塑膠系原材料可列丙 稀、聚氣乙稀、聚酿、IL樹脂、丙烯酸系樹脂等之塑膠膜、 塑膠片、塑膠板，於表面形成有二氧切蒸㈣等益機、 化物層的歸料。金衫原材料或__㈣4& 中所使用的接著劑於先前已知有聚環氧系 ς 基曱酸酯系接著劑。 w及|妝 於專利文獻1中記載了-種太陽電池背面 材，其包含以聚胺基曱酸酯系接著劑將至少2声、 貼合而成的積層體。更詳細而言，記載曰以上基材 且含有具㈣水解性之接著劑的聚胺基甲g ' 條件！：在作為利用加壓蒸汽之促進評 度濕度未飽和蒸汽應力測試（HAST)室中&於、/皿 atm下保存168小時後的層壓強度至少為 4 ,pif 201242054 上；條件2 :在作為利用加壓蒸汽之促進評價裝置的HAST 室中，於105 C、ι·〇5 atm下保持168小時後，並不產生 伴隨著脫層（delamination)的基材間的隆起。具體而古， 提出了分別相對於多元醇A〜多元醇F這6種類型的多元 醇而組合有交聯劑的多種聚胺基曱酸酯系接著劑（參 利文獻1之申請專利範圍第2項〜第11項）。 ^ -於專利文獻2中記载了一種太陽電池模組用後片，其 =含以2烯酸系接著劑將至少2個基材貼合而成的積二 體。更洋細而言，提出了一種丙烯酸系接著劑作為具: 水解性n緣性、及水分轉性之丙烯酸接著劑 述丙烯酸系接著劑含有使含有通式⑴所表示之 】 體成分聚合而成的丙稀酸系聚合物（參照專利2之 晴專利範圍第2項）。 CHfC^KO-OZ (I) 之烴^式中’ Rl表示氫原子或？基，Z表示碳數為4〜25 專利i於成為優先權之基礎的先前申請後所公開的 文獻3、專利文獻4中_了 一㈣合 其他膠膜之未經處理之面與 [先前技術文獻] [專利文獻] 5 201242054 . • * va* t [專利文獻1]國際公開2007_148754號 [專利文獻2]日本專利特開2〇〇9 24636〇號公報 [專利文獻3]日本專利特開2G111G5819號公報 [專利文獻4]日本專利特開2〇11111519號公報 為了在至外的嚴酷條件下經過長時間地穩定地維 重要的是接著強度即使隨時間經過亦穩定。於最近， 本灯，發如專利文獻3或翻文獻*所示那樣可將 之聚，等的塑膠之未經處理之面與其他基材【 者的接著劑。由於未進行表面處 =之縮短化，因此可降低成本。然而，於其另一方面步 :自先刖所運用的表面處理技術’對於使接著劑組 成物本來雜驗-步提高、且㈣ # 特性的接著劑組成物的需求亦變高。吏憂異之接者 【發明内容】 梦尽^=是#於上述背景而成的，其目的在於提供一種 劑組成物以及太陽電池用背面保護片，所述 劑組成物於各種片狀部件間、特別於是包含 ΐ膝膜表面處理層的層間顯示出高的接著力，即使暴露於 亦可維持高的接著力，適於製造太陽電 幹果等人為了解決上述課題而進行了銳意研究， 以下所示之積層片用接著劑組成物而解決 上述錁碭，從而完成本發明。 亦即’本發明之積層片用接著劑組成物包括丙稀酸多 201242054 f 元醇（Λ)與聚異氰酸酯（B)，所述丙烯酸多元醇（A) 之數量平均分子量為ι〇,000〜⑻0 ’且經值為1 mgKOH/g〜10〇mgKOH/g’另外玻璃轉移溫度（Tg)超過 •4〇°C且為10。(：以下’源自所述丙烯酸多元醇（A)之羥基 與源自所述聚異氰酸酯（B )之異氰酸酯基之當量比 NCO/OH 為 0.1 〜3。 所述聚異氰酸酯（B)之較佳例可列舉包含由脂環族 二異氰酸酯或脂肪族二異氰酸酯所衍生之聚異氰酸自旨之例 子0 上述態樣之積層片用接著劑組成物於包含2層以上片 狀部件的太陽電池用背面保護片之製造中使用，適用於如 下之用途中：形成用以將所述片狀部件彼此接合的接著劑 層的至少一部分。 本發明之太1¼電池用背面保護片包含：由上述態樣之 積層片用接著劑組成物而形成的接著劑層；介隔所^接著 劑層而積層的至少2層以上的片狀部件。 [發明的效果] 片用=本發明可提供如下的❹效果：可提供-種積層 2= 且ίΓ以及太陽電池用背面保護片，所述積層 2接^組成物於各刻狀部件間、 膜表面處理層的層間顯示出高 、31^ 高濕度環境下亦可維持高的，即使暴露於高溫 背面保護片。 旳接耆力，適於製造太陽電池用 【實施方式】 201242054 以下對本發明之實施形態加以詳細說明。另外，只要 符合本發明的宗旨，其他實施形態亦可屬於本發明之範 疇。而且，於本說明書中，「任意之數A〜任意之數B」的 5己载是表示數A及大於數A之範圍，且為數B及小於數B 的範圍。而且’於本說明書及申請專利範圍中所記載之「（曱 基）丙稀醯」之記載包含換稱為「丙烯酿」之化合物及換稱 為甲基丙埽醯」之化合物的任意者。而且’於「（甲基) 丙烯基」及「（甲基)丙烯酸酯」中亦同樣地定義。 <丙稀酸多元醇（A) > 丙烯酸多元醇（A)可較佳地使用含有羥基之單（甲基) 丙^酸酯單體與不含羥基之單（曱基）丙烯酸酯單體之共聚 物。含有羥基之單（甲基)丙烯酸酯單體是於丨分子中含有1 ，（甲基)丙烯醯基與丨個以上羥基之單體。較佳例可列舉 兀醇與（甲基）丙烯酸之反應而所得之單（甲基）丙烯 -欠酯單體、ε_己内酯改質（甲基)丙烯酸系單體等。 =丙烯酸多元醇（Α)之數量平均分子量為同種程度， =提高接著力之方面考慮，與單（？基)叫_旨單體之 無關之部分、亦即經由醋鍵而與（甲基)丙稀酸部分鍵 =之部分（烷基或烯基等部分。以下稱為「側鏈部分」）之 ^數較佳的是1〜17，更佳的是卜9，進—步更佳的是】 述側鏈部分於共聚後形成丙烯酸多元醇（A)之側 况。f (甲基)丙稀酸酿單體之所述側鏈部分之碳數一般情 '^是1〜3〇左右，但如果丙烯酸多元醇（a)之數量平 句分子量為同等程度，則所述側鏈部分越短，丙烯酸多元 201242054. -τι /pif 醇（A)之主鏈越相對性變長。其結果，硬化後之接著層 ' 的機械性質（具體而言為伸長率）提高，接著力提高。曰 由2元醇所知之單（甲基）丙稀酸醋單體例如可列舉（甲 基^丙烯酸羥基乙酯、（甲基）丙烯酸羥基丙酯、丨，4_丁二 醇單（甲基)丙烯酸醋、（聚)乙二醇單(曱基)丙稀酸醋等。 一另外，如（甲基）丙烯酸_2,3-二羥基丙酯等這樣的由3 元以上之醇而所得之單（曱基）丙烯酸酯單體亦可用作含有 罗工基之卓（曱基)丙婦酸g旨單體。 不含羥基之單（曱基）丙烯酸酯單體可適宜選擇自先前 以來所公知之自由基聚合性單體而使用。適宜的例子例如 可列舉以（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲 基）丙烯酸第三丁酯、（曱基）丙烯酸_2_乙基己酯、（甲基）丙 7酸正辛酯、（甲基)丙烯酸月桂基酯、（甲基)丙酸十三烷基 知（甲基)丙稀酸硬脂基酯等（曱基)丙烯酸烧基酯單體為代 表之長鏈（甲基)丙烯酸系單體、及丙烯腈等。 另外，除了上述含有羥基之（曱基）丙烯酸酯單體與不 含羥基之單（曱基）丙烯酸酯單體之外，還可以共聚其;^單 體，例如.（曱基）丙稀酸、馬來酸、馬來酸酐等含有竣基 之單體或其酸酐，或者苯乙烯等乙烯系單體等。另外，含 有經基之（曱基)丙烯酸酯單體、不含經基之單（曱基)丙稀酸 S曰單體可分別獨立地使用1種化合物，亦可將2種以上化 - 合物組合使用。關於使用其他單體之情形亦同樣。 於本發明中，丙烯酸多元醇（A)之數量平均分子量 必須為10,000〜100,000。進一步而言，較佳的是10 000 201242054. 70,000 ’ 更佳的是 25,〇〇〇〜50 000。 ，用本發明之積層片用接著劑 =，)將2個《上片狀部件積層：為： 電f用背面保護片例如可經過如下之步驟而獲得。 择部件之接合面塗佈接著_成物而使其乾 燥。其-人’將其他片狀部件重邁於 〜_之魏下财 之步驟，進行接著劑層之硬化而===為「老化」 於元醇^數量平均分子量不足ig，_之情 ^〖老化步驟剛之接著劑層之凝聚力不足之， 且存在老化步驟前之接著力變小之虞。在工業性^ 了時^繞為触之狀態的積層體在通常情況 =201242054. -rx v/z- / 1 6. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition for a laminated sheet and a back protective sheet for a solar battery. [Prior Art] In recent years, multi-layer (1) composites used for outdoor industrial applications such as barrier materials, roofing materials, solar panel materials, window materials, outdoor flooring materials, and Zhaoming protective materials: automotive parts, signboards, and label materials. A multilayer (composite) laminate having a film or the like can be obtained by laminating a metal-based raw material or a plastic-based raw material. Examples of the metal-based raw material include aluminum, steel, steel, and the like, which are flutes, metal plates, metal deposition films, and the like. Plastic raw materials can be listed as plastic film, plastic sheet, plastic sheet, such as acryl, polystyrene, poly brewing, IL resin, acrylic resin, etc., and the surface of the product is formed by dioxane steaming (four) and the like. material. The enamel raw material or the adhesive used in __(4)4& is previously known as a polyepoxy decyl phthalate-based adhesive. w and _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ More specifically, the above-mentioned base material is described and contains a polyamine-based g' condition having a (4) hydrolyzable adhesive agent! : at a laminate strength of at least 4, pif 201242054 after 168 hours of storage in a humidity-saturated vapor stress test (HAST) chamber using pressurized steam, at /, atm; condition 2: In the HAST chamber using the pressurized steam promotion evaluation device, after 168 hours at 105 C and ι·5 atm, no bulging between the substrates accompanying delamination occurred. Specifically, various polyamine phthalate-based adhesives in which a cross-linking agent is combined with respect to the six types of polyols of polyol A to polyol F, respectively, have been proposed (the patent application scope of reference 1) 2 items - 11 items). ^ - Patent Document 2 describes a rear sheet for a solar cell module, which comprises a product comprising a combination of at least two substrates bonded by a 2-olefinic binder. More specifically, an acrylic adhesive has been proposed as an acrylic adhesive having a hydrolyzable n-bond property and a water-transfer property. The acrylic adhesive contains a polymer component represented by the formula (1). Acrylic acid polymer (refer to Patent No. 2 of Patent No. 2). CHfC^KO-OZ (I) is a hydrocarbon in the formula where R is a hydrogen atom or ? Base, Z represents a carbon number of 4 to 25, and the unprocessed surface of the other film is disclosed in the document 3, Patent Document 4, which is the basis of the prior application. [Patent Document] [Patent Document] 5 201242054. • * va* t [Patent Document 1] International Publication No. 2007-148754 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. In order to stably maintain the stability over a long period of time under severe conditions to the outside, it is important that the subsequent strength is stable even with time. Recently, the lamp can be gathered as shown in Patent Document 3 or the document *, and the untreated side of the plastic and other substrates can be used as an adhesive. Since the shortening of the surface is not performed, the cost can be reduced. However, in another aspect, the surface treatment technique used by the prior art has become higher for the adhesive composition, and the demand for the (4) adhesive composition is also increased.吏 之 【 【 【 【 【 【 【 【 【 = = = = = = = = = 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于In particular, the layer containing the ruthenium surface treatment layer exhibits a high adhesion force, and even if it is exposed to a high adhesion force, it is suitable for the manufacture of solar electric dried fruit and the like. In order to solve the above problems, the following research has been conducted. The laminated sheet is shown to solve the above flaws with an adhesive composition, thereby completing the present invention. That is, the adhesive composition for a laminated sheet of the present invention comprises a polyacrylic acid 201242054 f-alcohol (Λ) and a polyisocyanate (B), and the number average molecular weight of the acrylic polyol (A) is ι〇, 000~ (8) 0 ' and the pass value is 1 mgKOH/g to 10 〇 mgKOH/g', and the glass transition temperature (Tg) exceeds • 4 〇 ° C and is 10. (The following 'equivalent ratio NCO/OH derived from the hydroxyl group derived from the acrylic polyol (A) to the isocyanate group derived from the polyisocyanate (B) is 0.1 to 3. The polyisocyanate (B) is preferred. Examples of the polyisocyanate derived from an alicyclic diisocyanate or an aliphatic diisocyanate are exemplified. The adhesive composition for a laminate sheet of the above aspect is used for a solar cell comprising two or more sheet members. The use of a back protective sheet for use in the manufacture of at least a portion of an adhesive layer for bonding the sheet members to each other. The back protective sheet for a battery of the present invention comprises: The adhesive layer formed of the adhesive composition of the laminated sheet; at least two or more sheet-like members laminated with the adhesive layer. [Effects of the Invention] The present invention provides the following effect : It is possible to provide a laminate 2 = and 背面 and a back protective sheet for solar cells. The laminate 2 is formed between the sculpt members and the surface of the film surface treatment layer, and is also high in the environment of 31 ^ high humidity. Kewei High, even when exposed to a high-temperature back protective sheet. Suitable for manufacturing solar cells. [Embodiment] 201242054 Hereinafter, embodiments of the present invention will be described in detail. Further, other embodiments are also provided as long as the gist of the present invention is met. Further, in the present specification, the five-loads of "arbitrary number A to any number B" are ranges indicating the number A and the number A, and are in the range of the number B and less than the number B. Further, the description of "(曱基)丙丙" as described in the specification and the scope of the patent application includes any of the compounds referred to as "acrylic brewing" and the compound referred to as methylpropionamidine. Further, '(meth)acryloyl group) and "(meth) acrylate" are also defined in the same manner. <Acrylic polyol (A) > Acrylic polyol (A) can be preferably used. a copolymer of a mono(meth) acrylate monomer of a hydroxy group and a mono(indenyl) acrylate monomer having no hydroxyl group. A mono(meth) acrylate monomer having a hydroxyl group is contained in a ruthenium molecule. , (meth) acrylonitrile and A monomer having more than one hydroxyl group. Preferred examples thereof include a mono(meth)acryl-under ester monomer obtained by reacting decyl alcohol with (meth)acrylic acid, and ε_caprolactone modified (meth)acrylic acid. Monomer, etc. = The number average molecular weight of the acrylic polyol (Α) is the same degree, = the improvement of the adhesion force, and the part of the single (? base) called the monomer, that is, via the vinegar bond The portion of the (meth)acrylic acid moiety bond (the moiety such as an alkyl group or an alkenyl group, hereinafter referred to as a "side chain moiety") is preferably 1 to 17, more preferably a ruthenium, and - Preferably, the side chain portion forms a side of the acrylic polyol (A) after copolymerization. The carbon number of the side chain portion of the f (meth) acrylic acid monomer is generally '^ 1~3〇 or so, but if the molecular weight of the acrylic polyol (a) is the same, the shorter the side chain portion, the more the main chain of the acrylic polyol 201242054. -τι /pif alcohol (A) lengthen. As a result, the mechanical properties (specifically, elongation) of the adhesive layer 'after curing are improved, and the force is increased. Examples of the mono(meth)acrylic acid vinegar monomer known from the divalent alcohols include (hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydrazine, 4-butanediol alone (A) Acrylic vinegar, (poly)ethylene glycol mono(indenyl) acrylate vinegar, etc. In addition, such as (meth)acrylic acid 2,3-dihydroxypropyl ester and the like The obtained mono(indenyl) acrylate monomer can also be used as a monomer containing a ruthenium-based sulfonate. The hydroxy-free mono(indenyl) acrylate monomer can be suitably selected from A radically polymerizable monomer which has been conventionally known has been used, and suitable examples thereof include n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. Mercapto)Acrylic acid 2-ethylhexyl ester, (meth)propionic acid 7-octyl ester, (meth)acrylic acid lauryl ester, (meth)propionic acid tridecyl (meth)acrylic acid a long-chain (meth)acrylic monomer represented by a (mercapto)acrylic acid alkyl ester monomer such as stearyl ester, acrylonitrile or the like. The (meth) acrylate monomer may be copolymerized with a hydroxyl group-free mono(indenyl) acrylate monomer; a monomer such as (mercapto)acrylic acid, maleic acid, a monomer containing a mercapto group such as maleic anhydride or an anhydride thereof, or a vinyl monomer such as styrene, etc. Further, it contains a mercapto (mercapto) acrylate monomer, and does not contain a mercapto mono(indenyl) propyl group. The dilute acid S曰 monomer may be used singly or in combination of two or more kinds of compounds. The same applies to the case of using other monomers. In the present invention, the acrylic polyol (A) is used. The number average molecular weight must be 10,000 to 100,000. Further, it is preferably 10 000 201242054. 70,000 ' More preferably 25, 〇〇〇 ~ 50 000. With the laminate of the present invention, the adhesive will be used, Two "layers of the upper sheet-like component: for: The back protective sheet for electric f can be obtained, for example, by the following steps. The joint surface of the selected part is coated and then dried to dry. Its-people's re-take the other sheet-like parts to the step of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The cohesive force of the adhesive layer immediately after the aging step is insufficient, and the adhesive force before the aging step becomes small. In the case of industriality, the layered body in the state of being touched is in the normal case =

=方Γ進行老化。若老化步驟前之接著力二1 於正在進行老化時捲繞容易散開，並不適於 J 而且，若不足_()〇，則存在老化 f ^。 傾向’伴隨於此而存在耐濕熱性變低、產生==之 而且，若丙烯酸多元醇之數量平均分曰，。 100,000，則存在接著劑之黏度變高，於塗佈性方面過 題，對片狀部件之濕潤性降低之傾向，t f生問 驟前之接著力變小之虞。雖然初始接老化步 化前相比而言變大，但存在由於其後 教2老 緩降低，祕過3_小時後低於使用下限^虞以驗而緩 另外，本發明中之數量平均分子量 > 析儀（GPC)而求出’進行聚苯乙稀換算^值。 201242054., / pit 言，本發明t之數量平均分子量是表示藉由後述之實例中 所記載之測定方法而求出之值。而且，關於玻璃轉移溫度、 NCO/OH φ量比’亦jg]樣地表示藉纟彳歧之實财所記載 之方法而求出之值。 丙烯酸多7L醇（A)之羥值由含有羥基之單（甲基）丙烯 酸酯單體之含量而決定，於本發明中羥值為i mgK〇H/g〜 100 mgKOH/g，較佳的是 1 mgK〇H/g〜5〇 mgK〇H/g，更 佳的是 1 mgKOH/g〜15 mgKOH/g。若不足 1 mgK〇H/g， 則存在與異氰酸酯硬化劑之交聯降低之傾向，且存在耐濕 熱性降低之虞。而且，若超過100 mgKOH/g，則存在雖然 可表現出老化前之接著力，但於老化後交聯密度變高之傾 向，且存在無法表現出充分之接著力，於其後之耐濕熱性 试驗中接著力進一步降低之虞。 而且，於本發明中，丙烯酸多元醇（A)之玻璃轉移 點（Tg)由於後述之理由而為超過_4crc且為1(rc以下， 更佳的是超過-25°c且為10〇c以下。 <聚異氰酸酯（B) > 聚異氰酸酯（B)例如為由周知之二異氰酸酯所衍生 之化合物，可無限制地利用公知之化合物。例如可列舉： 由2,4-曱笨二異氰酸酯（別名：2,4_TDI)、2,6_甲笨二異氣 酸醋（別名：2,6-TDI)、二甲苯二異氰酸酯（別名：XDI)、 二笨基甲烷二異氰酸酯（別名：MDI)、異佛爾_二異氰酸 酉曰1，5-萘一異鼠酸醋、六亞曱基二異氰酸醋（別名：hdi )、 雙(4·異氰酸酯環己基）甲烷、或氫化二苯基甲烷二異氰酸 201242054 4102/pif 氰;生之化合物’亦即所述二異氰酸_之 絲體、讀甲基狀加合物體、縮二脲型、 ^ 酿殘基之預聚物（由二異氰酸s旨與多元醇所得之低= 物）、具有異級喊基之脲二_體、脲基甲酸醋體/。 些化合物之複合物、絲段錢_。料級自旨 可早獨使用早-之化合物或者將2種以上組合使用。 自交聯後之硬化塗膜之黏彈性之觀點:， 醋⑻較佳的是使用由脂環族二異_^或脂肪2 異氰賴崎生之聚異級§旨^更詳纟袖言，、I 酸醋可列舉異佛_二異氰_、甲基_2,6_環己垸二[異 酸醋等。而且，脂肪族二異氰酸s旨可列舉六亞甲^二里， 酸醋、五亞甲基二異氰酸g旨等。而且可列舉：作為前述^ 脂環族二魏_及簡族二錢酸自旨化合物之衍 二異氰酸i旨之IU旨體、三經甲基丙燒加合物體、縮二腺型、 具有異氰酸S旨殘基之預聚物（由二異級g|與多元 之低聚合物）、具有異驗g旨殘基之脲二酮體、脲基甲 體、或該些之複合物等。 而且，於重視硬化速度快慢之情形時，較佳的是使用 如二曱苯二異氰酸自旨（別名：XDI)這樣的雖然具有芳香 環’但於NCO與料社間具有狀基的錢酸醋。若 硬化速度快，則於可縮短老化時間之方面而言較佳。 而且’聚異氰咖（B)巾之異級g旨錢度較佳的 是5 Wt%〜3G Wt%。聚異氰_旨⑻中之異氰酸醋基濃 度設為5 wt%〜30 wt%之範圍。另外，聚異氰酸酯（B) 12 201242054. ΤίνΛώ，pif 中之異減S旨基濃度可藉由滴定法而求出 。滴定藉由正丁 二胺/+鹽酸滴定法㈣行評價。具體而言 ，使試樣溶解於乾 、’、甲笨中後添加過剩之二正丁基胺(dibutylamine)溶液而 使’、反應藉由鹽酸而反滴定剩餘之二正丁基胺，將滴定 曲線上之反曲點作為終點，根據直至終點之滴定量而算出 異氰酸酯基含有率。 叩异出 、f異减_⑻之使用量可由源自丙烯酸多元醇（A) 基與源自聚異氰酸自旨（B)之異氰酸之NCo/〇h 虽罝比而決定，將Nc〇/〇h當量比設 NCO/OH當量比A、隹又住的疋 舍旦kh制田步更佳的是1.5〜3。NC 0/0H *里比HX下之數學式⑴而求出。 NCO/OH比=聚異酸醋必黨晉 值）X (nc〇%/(42x 里（重讀）x (56_ 量））數學式⑴ 多元醇量（固形物重 本發明者等人查明：藉由滿足以下 得令人驚言牙之優異特性的積 有條件，了獲 查明藉由滿足如下之所有條件，可提供勿。亦即， (所述接著劑組成物於各種片 /、接者劑組成物 膠膜之表面處理層之層間顯別是於包含塑 池用背面保護片）：使用上述之於製造太陽電 平均分子量'/、有（ι)特定範圍之數量 轉移溫度（Tg)的丙烯酸多元醇，）“範圍之玻璃 自丙晞酸多it醇（A)之麵其盘、“進一步將（iv)源 之匕基與源自聚異氰酸酉旨⑻之異 201242054f τ Λ V/X-> f 氰酸酯基之f纽NCG/qH設絲㈣ 下，對其理由加以說明。 與積層表面未經處理之塑膠膜之情形招比而言， 層以電暈放電等對表面進行處理的歸膜之情，要灰 製造步驟增加部分之附加價值。於接著力中，要求盘積芦 表面未經處理之塑膠膜之情形相比而言更高的接著力'。、θ 若丙烯酸多元醇之Tg過低，則老化前之接著劑層之 硬化尚不充分’因此由接著劑組成物所形成之接著劑^柔 軟。而且4於其柔軟程度而可於片狀部件間表現出^種 程度的接者力。然❿，於老化後，即使接著劑層充分硬化， 亦由於作為原料之丙烯酸多元醇之Tg低而存在接著劑層 之凝聚力不足變賴’變得難以確保大的接著力之傾向: 另外’若將積層體長時間地置於高温高濕度下，則存在如 下之傾向·由於接著劑層之凝聚力不足的原因而造成接著 力緩緩降低。 另一方面，若丙烯酸多元醇之Tg過高，則存在對基 材之濕潤性不足賴向。雜老化後之接著力與老化前相 比而言多少有所變大，但交聯後之硬化接著劑層過於變 硬，因此存在老化步驟後之接著力惡化之傾向。 β於本發明中，進行研究而得知獲得上述優異效果之理 由是由t:將丙烯酸多元醇之Tg設為並不過低且不過高 之溫度範圍（具體而言為超過_4(rc且為1(rc以下），於其 基礎上進一步設為特定之羥值、特定之NCO/OH當量比、 及特定之數量平均分子量之範圍’藉此而協同地激發分子 201242054.ΤίνΛώ，pif ，動級別的丙烯酸多元醇之運動的活躍程度，從而使對接 者對象之测性與!㈣性提高。_是進行研究而得知藉 由將NC〇/〇H當量比控制為〇·卜3之範圍、特別是卜3 之辄圍’可f現適度之㈣度之平衡且於老 出高的接著力。而且，令人驚祕發购纽老化^亦員: ，出南的接者力。另外發現：於老化步驟後，於置於高溫 尚濕度下之後亦可維持高的接著力。 於使用金n、金屬板、或金屬蒸鑛膜等為基材之 形時，自使接著強度提高之觀點考慮，較㈣是本發明之 積層片用接著劑組成物含有矽烷偶合劑。 石^偶合劑並非較於以下者，例如可列舉乙稀基三 (β-甲乳基乙氧基)魏、乙縣乙氧基魏、及乙稀基三 :氧基魏等乙烯基魏類，基)丙烯崎基丙基 氧基魏、⑽基)丙烯醯氧基丙基三乙氧基魏、及γ_(甲 f丙婦醯氧基丙基二甲氧基甲基魏等（甲基）丙_氧 ^夕=類’^(3,4-環氧環己基）乙基三甲氧基魏、阳，4_ 環，環己基)甲基三甲氧基魏、p_(3,4環氧環己基)乙基三 乙氧基矽烷、β-(3,4-環氧環己基)甲基三乙氧基矽烷、γ'缩 料油氧基祕三甲氧基魏、及γ_縮水甘油氧基丙基三 乙乳基魏等環氧基魏類；Ν_Ρ(胺基乙基 甲氧基魏、Ν·β(胺基乙基)γ_胺基丙基三乙氧基残: =(胺基乙基)γ·胺基丙基甲基二乙氧基石夕石夕烧、γ胺基丙 基二乙氧基石夕院、γ-胺基丙基三甲氧基石找、Ν苯基个胺 基丙基三甲氧基魏、及Ν·笨基个胺基丙基三乙氧基魏 201242054 41627pif 等胺基矽烷類；以及γ-巯基丙基三甲氧基矽烷、及γ_毓基 丙基三乙氧基矽烷等含硫矽烷類等。該些化合物可分別單 獨使用或者將2種以上任意組合而使用。 石夕炫偶合劑之添加量相對於丙烯酸多元醇（A ) 1 〇〇 重量份而言較佳的是〇」重量份〜5重量份，更佳的是J 重量份〜3重量份。若不足〇〗重量份，則由於添加矽烷 偶合劑而帶來之對金屬箔之接著強度提高的效果差；即使 添加超過5重量份，亦存在未發現其以上之性能提高之情 況。 本發明之積層片用接著劑組成物可為於使用時將主齊 與硬化劑純齡的所謂2液混合型接著劑，亦可為預失 將主劑與硬化修以混合的丨㈣接著劑。而且，丙婦駿 多元醇（A)或聚異氰酸醋（B)亦可各自獨立地使用多種。 另外，上述以外的其他主劑或硬化劑亦可各自獨立地使用 種或多種。通常情況下，蝴包括丙烯酸多元醇（A)、 二=劑，溶劑、其他添加劑’硬化劑包括聚異氰 酉文酉曰（B)、有機溶劑、其他添加劑。 内，：添加劑，可於在不脫離本發明之主旨之範圍 劑、均化劑、碟系：黏d反應促進 屬減活劑、阻4 ==紫外線穩定劑、金 添加劑。j』化小有機顏料、無機顏料等各種 於使用金屬層（金屬箔、金 情形時，為了使太称屬板專）作為片狀部件之 %積㈢片用接著劑組成物之金屬密 16 201242054 ~Τ 1 ,pif 接性提向，可添加構酸系化合物，例如鱗酸、偏鱗酸、焦 ' 磷酸、亞磷酸或該些酸之酯等。 - 而且，本發明之接著劑組成物除了作為用以製造太陽 電池用背面保護片之接著劑而較佳地使用以外，亦可作為 太電池積層片用增黏塗層劑而使用。於此情形時，較佳 的是放入防結塊劑。= square aging. If the adhesion force before the aging step is 2, the winding is easily spread when aging is occurring, and it is not suitable for J. If _() is insufficient, there is aging f ^. There is a tendency that the heat and humidity resistance is lowered and the yield is ==, and the number of the acrylic polyols is evenly distributed. When the viscosity is 100,000, the adhesiveness of the adhesive becomes high, and the coating property is insufficient, and the wettability of the sheet member is lowered, and the adhesive force before the tf is reduced. Although it is larger than before the initial aging step, there is a decrease in the amount of the aging step, and it is lower than the lower limit of use after 3 hours, and the number average molecular weight in the present invention is further reduced. > The analyzer (GPC) was used to determine the value of the polystyrene conversion. 201242054., /pit The numerical average molecular weight of t of the present invention is a value obtained by a measurement method described in the examples described later. Further, the glass transition temperature and the NCO/OH φ amount ratio 'also referred to as 'jg' indicate the value obtained by the method described in the real money. The hydroxyl value of the poly(7L) alcohol (A) is determined by the content of the mono(meth)acrylate monomer having a hydroxyl group, and in the present invention, the hydroxyl value is i mgK〇H/g to 100 mgKOH/g, preferably It is 1 mgK〇H/g~5〇mgK〇H/g, more preferably 1 mgKOH/g~15 mgKOH/g. If it is less than 1 mgK〇H/g, the crosslinking with the isocyanate curing agent tends to decrease, and the heat and humidity resistance is lowered. In addition, when it exceeds 100 mgKOH/g, although the adhesive force before aging may be exhibited, the crosslinking density tends to become high after aging, and it may not be able to exhibit sufficient adhesive force, and thereafter it is resistant to moist heat. In the test, the force was further reduced. Further, in the present invention, the glass transition point (Tg) of the acrylic polyol (A) is more than _4crc and is 1 (rc or less, more preferably more than -25 °c and 10 〇c) for the reason described later. <Polyisocyanate (B) > The polyisocyanate (B) is, for example, a compound derived from a well-known diisocyanate, and a known compound can be used without limitation. For example, 2,4-indole diisocyanate can be cited. (alias: 2,4_TDI), 2,6_A stupid acid vinegar (alias: 2,6-TDI), xylene diisocyanate (alias: XDI), diphenylmethane diisocyanate (alias: MDI) , Iverine _ diisocyanate 1,5-naphthalene-iso citrate, hexamethylene diisocyanate (alias: hdi), bis (4 · isocyanate cyclohexyl) methane, or hydrogenation Phenyl methane diisocyanate 201242054 4102/pif cyanide; raw compound', that is, the diisocyanate, the read methyl form adduct, the biuret type, the prepolymerization of the distillate residue (lower than that obtained from diisocyanate s with polyol), urea dimer with heterogeneous sulfonic acid, ureido formic acid /. Compound, silk segment money _. Material grade can be used as early as possible alone or in combination of two or more. Self-crosslinking hardened coating film viscoelastic point of view:, vinegar (8) is preferred to use From the alicyclic two different _^ or fat 2 isocyanide Laisaki's poly-level § purpose ^ more detailed 纟 sleeve words, I vinegar can be listed as different _ _ diisocyan _, methyl _2, 6 _ Cyclohexanide [isoacid vinegar, etc. Further, the aliphatic diisocyanate s can be exemplified by hexamethylene ketone, acid vinegar, pentamethylene diisocyanate g, etc. ^ Cycloaliphatic diwei _ and succinyl dinic acid derived from the compound diisocyanate IU constitutive, tri-methyl propyl acrylate adduct, dimeric gland, with isocyanic acid a prepolymer of a residue (a low polymer composed of a di-equivalent g| and a multi-element), a uretdione having a heterologous residue, a urea-based body, or a composite thereof, etc. When it is important to emphasize the rate of hardening, it is preferred to use a vinegar having an aromatic ring, but having a group between the NCO and the material, such as diphenylbenzene diisocyanate (alias: XDI). Hardening speed It is preferable in terms of shortening the aging time. Moreover, the heterogeneous g of the polyisocyanurated coffee (B) towel is preferably 5 Wt% to 3 G Wt%. Polyisocyanate (8) The isocyanate group concentration is set in the range of 5 wt% to 30 wt%. Further, the polyisocyanate (B) 12 201242054. ΤίνΛώ, the difference in the pif base concentration can be determined by titration. It is evaluated by n-butylene diamine/+ hydrochloric acid titration method (IV). Specifically, the sample is dissolved in dry, ', and the solution is added, and the excess dibutylamine solution is added to make the reaction. The remaining di-n-butylamine was back-titrated with hydrochloric acid, and the inflection point on the titration curve was used as an end point, and the isocyanate group content was calculated from the titration to the end point. The amount of 叩 出 、 f ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The Nc〇/〇h equivalent ratio is preferably 1.5 to 3 in which the NCO/OH equivalent ratio A and the 疋 旦 旦 kh kh field step are better. NC 0/0H * is calculated by the mathematical formula (1) under HX. NCO/OH ratio = polyisoacid vinegar must be party value) X (nc〇% / (42x (reread) x (56_ quantity)) Mathematical formula (1) The amount of polyol (solid matter weight inventors and others identified: By satisfying the following conditions for the excellent characteristics of the surprising tooth, it has been found that by satisfying all of the following conditions, it can be provided. That is, (the adhesive composition is in various sheets/connections) The composition of the surface treatment layer of the composition film is mainly for the back surface protective sheet containing the plastic pool): using the above-mentioned average molecular weight for manufacturing solar energy '/, having a specific range of (ι) transfer temperature (Tg) Acrylic polyol,) "Scope of glass from the surface of propionate poly-alcohol (A), "further (iv) source of thiol and polyisocyanate derived from (8) different 201242054f τ Λ V/X-> f cyanate-based f-NCG/qH wire (4), the reason is explained. Compared with the untreated plastic film on the laminated surface, the layer is corona discharge, etc. The filming of the surface is treated with the added value of the ash manufacturing step. In the subsequent force, the disk is required. A higher adhesion force in the case of an untreated plastic film on the surface of the reed. θ If the Tg of the acrylic polyol is too low, the hardening of the adhesive layer before aging is not sufficient 'so it consists of an adhesive The adhesive formed by the object is soft, and 4 can exhibit a degree of contact between the sheet members in terms of its softness. Then, after the aging, even if the adhesive layer is sufficiently hardened, it is also used as a raw material. When the Tg of the acrylic polyol is low and the cohesive force of the adhesive layer is insufficient, it becomes difficult to ensure a large adhesive force: In addition, if the laminate is placed under high temperature and high humidity for a long period of time, the following tendency tends to occur. - The adhesion force is gradually lowered due to insufficient cohesive force of the adhesive layer. On the other hand, if the Tg of the acrylic polyol is too high, the wettability to the substrate is insufficient. It is somewhat larger than before, but the hardened adhesive layer after crosslinking is too hard, so there is a tendency that the adhesion force after the aging step is deteriorated. In the present invention, research is known. The reason for the above excellent effect is that t: the Tg of the acrylic polyol is not too low but not too high (specifically, it exceeds _4 (rc and is 1 (rc or less), and further based thereon Setting a specific hydroxyl value, a specific NCO/OH equivalent ratio, and a range of a specific number average molecular weight' thereby synergistically exciting the activity of the molecule 201242054.ΤίνΛώ, pif, the dynamic level of the acrylic polyol, thereby The testability of the docker object is improved. (4) The research is carried out and it is known that by controlling the NC〇/〇H equivalent ratio to the range of 〇·卜3, in particular, The balance of the moderate (four) degree and the high strength of the old. And, the shocking purchase of New Year aging ^ also:: The success of the South. It has also been found that after the aging step, a high adhesion can be maintained after being placed at a high temperature and humidity. When the gold n, the metal plate, or the metallized film or the like is used as the base material, it is preferable that the adhesive composition for a laminated sheet of the present invention contains a decane coupling agent from the viewpoint of improving the adhesion strength. The stone coupling agent is not the same as the following, and examples thereof include ethylene tris(β-methyllacyl ethoxy) Wei, ethyl ethoxy wei, and ethylene triyl oxy wei. , a) acrylonitrile propyloxy Wei, (10) based propylene methoxy propyl triethoxy wei, and γ _ (methyl propyl methoxy methoxy dimethoxymethyl Wei et al (methyl ) _ _ oxygen ^ Xi = class '^ (3,4-epoxycyclohexyl) ethyl trimethoxy Wei, cation, 4_ ring, cyclohexyl) methyl trimethoxy Wei, p_ (3, 4 epoxy ring Hexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane, γ'reduced oleyloxytrimethoxywei, and γ-glycidoxy Propyl triethyl lactyl-Wei- ortho-epoxide Wei; Ν_Ρ (aminoethyl methoxy-wei, Ν·β (aminoethyl) γ-aminopropyl triethoxy residue: = (amino group Ethyl) γ-aminopropylmethyldiethoxy sulphur, gamma-aminopropyldiethoxy sylvestre, γ-aminopropyltrimethoxylate, phenylphenylaminopropyl Trimethoxy-Wei, and hydrazine-stupyl-aminopropyltriethoxy-201242054 41627pif and other amino decanes; and γ- a thiol-containing decane such as propyl trimethoxy decane or γ-mercaptopropyl triethoxy decane, etc. These compounds may be used singly or in combination of two or more kinds. The amount of addition is preferably 〇" parts by weight to 5 parts by weight, more preferably J parts by weight to 3% by weight, based on 1 part by weight of the acrylic polyol (A). The effect of improving the adhesion strength of the metal foil due to the addition of the decane coupling agent is inferior; even if it is added in an amount exceeding 5 parts by weight, the above performance improvement is not observed. The adhesive composition for a laminated sheet of the present invention may be used. In order to use the so-called two-liquid mixed type adhesive which is the age of the master and the curing agent at the time of use, it is also possible to use a ruthenium (tetra) adhesive which mixes the main agent with the hardening treatment. Moreover, the propyl group (100) Alternatively, the polyisocyanuric acid vinegar (B) may be used independently of each other. Further, other main agents or curing agents other than the above may be used independently of the species or a plurality of types. In general, the butterfly includes an acrylic polyol (A). , two = agent, solvent, and The additive 'hardener includes polyisocyanine (B), organic solvent, and other additives. Internal: additive, which can be used in the range of the agent, the homogenizer, and the dish without sticking to the gist of the present invention: sticky d reaction It is a deactivating agent, a resistance 4 == UV stabilizer, a gold additive, a small organic pigment, an inorganic pigment, etc., which are used as a sheet in the use of a metal layer (in the case of metal foil or gold, in order to make the board too special) % of the component (3) The metal bond of the adhesive composition of the sheet 16 201242054 ~ Τ 1 , pif directional lift, can add acid-based compounds, such as scalylic acid, squaric acid, pyrophosphoric acid, phosphorous acid or In addition, the adhesive composition of the present invention can be preferably used as a tackifying coating agent for a battery laminate sheet, in addition to being preferably used as an adhesive for producing a back surface protective sheet for a solar cell. And use. In this case, it is preferred to incorporate an anti-caking agent.

另外，可於不脫離本發明之主旨之範圍内無限制地調 配作為接著劑用途而公知之添加劑。例如可使用反應促進 劑。具體而言可列舉二乙酸二丁基錫、二月桂酸二丁基錫、 二月桂酸二辛基錫、二馬來酸二丁基錫等金屬系觸媒；H 二氮雜-雙環(5,4,0)十一碳烯-7、1，5-二氮雜雙環(4,3,0)壬烯 5 6 —丁基胺基-1，8-一氮雜雙環(5,4,〇)十一碳稀_7等三級 fee，如二乙醇胺這樣的反應性三級胺等。反應促進劑可使 用1種或將2種以上併用使用。 另外，為了使層壓外觀提高，亦可於主劑中調配公知 之均化劑或消泡劑。 併均化劑例如可列舉聚醚改質聚二甲基矽氧烷、聚酯改 質Ϊ二甲基石夕氧烧、芳烧基改質聚甲基烧基石夕氧烧、聚醋 改質含羥基聚二甲基矽氧烷、聚醚酯改質含羥基聚二甲基 矽，烷、丙烯酸系共聚物、甲基丙烯醯基系共聚物、聚醚 改質聚甲基烧基石夕氧烧、丙烯酸院基醋共聚物、甲基丙稀 魏基共聚物、Μ脂、或該些之混合物等公知之均化 劑。 4泡劑可列舉矽酮樹脂、矽酮溶液、烷基乙烯基醚與 17 201242054 . Hioz /pif 丙烯酸烷基酯與曱基丙烯酸烷基酯之共聚物、或該此之甲 合物等公知之消泡劑。於添加均化劑、消泡劑之情形時此 各自獨立地可使用1種化合物亦可將2種以上化合^ ’立 地組合而使用。 〜 而且，作為本發明中所使用之公知的添加劑，為 - ^抑制由於太陽等之紫外賴造紅接著崎時間經過 之買化、由於太陽熱等熱所造成之接著劑隨時間經過之黃 化:可於主劑中調配公知之磷系或酚系之抗氧化劑、紫= 線穩定劑、金屬減活劑。該些添加劑可單獨使用，亦可將 2種以上任意組合而使用。本發明中所使用之磷系戋酚系 之抗氧化劑、紫外線穩定劑、金屬減活劑相對於丙婦酸多 元醇（A)之固形物1〇〇重量份而言較佳的是〇仍重量份 〜I重量份之範圍，更佳的是〇]重量份叫重量份。若添 加置不足G.G5重量’則存在無法獲得充分之黃化抑制效果 之虞；若多於5重量份，則存在使接著劑之接著力大程度 地惡化之虞。 作為硬化劑，除了上述聚異氰酸酯（B)以外，可以 在不阻礙本發明之效果的範_任意地包含周知之射琳 化口物（例如2,5-二曱基、或2,2_(14_伸丁基)_ ^(2））或轉化合物（例如間笨二甲酸二紐、 矣二酸二醯肼、或己二酸二醯肼）等。 匕本發明中所使用之溶劑，例如可列舉乙酸乙醋、乙酸 丁酯、乙酸賽珞蘇等酿類；丙酮、丁_、里美 異丁基_、環己酮等_ ;四氫料、二員；$ 18 201242054., / pit 苯:二f苯等芳香族煙類；二氯曱烧、1，2_二氯乙烧等鹵 代烴類；二甲基亞颯、二甲基磺醯胺等。所使用的溶劑可 使用1種溶劑，亦可將2種以上任意組合而使用。 本發明之接著劑之不揮發成份（固形物）較佳的是1〇 wt%〜50 Wt%之範圍。本接著劑可使用如上述所例示之溶 劑而進行固形物之調整。 其次，對製造使用本發明之積層片用接著劑組成物而 成的太陽電池用背面保護片之方法、及太陽電池用背面保 護片之-例加以說明。另外，太陽電池用背面保護片之製 造方法或構成並不限定於以下之例，可根據目的或需要而 採用各種各樣之製造方法或構成。 作為太陽電池模組，單純的太陽電池模植具有在作為 太陽電池元件之太陽電池單元的兩個面順次積層有填充劑Further, additives known as adhesives can be used without limitation, without departing from the gist of the present invention. For example, a reaction accelerator can be used. Specific examples thereof include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; H-diaza-bicyclo(5,4,0) ten Monocarbene-7,1,5-diazabicyclo(4,3,0)nonene 5 6-butylamino-1,8-azabicyclo (5,4,fluorene) eleven carbon Three grades such as _7, such as reactive tertiary amines such as diethanolamine. One type of the reaction accelerator or two or more types may be used in combination. Further, in order to improve the appearance of the laminate, a known leveling agent or antifoaming agent may be formulated in the main component. The homogenizing agent may, for example, be a polyether modified polydimethyl siloxane, a polyester modified dimethyl dimethyl oxyhydrogen, an aromatic alkyl modified polymethyl ketone, and a polyacetal. Hydroxy-containing polydimethyl siloxane, polyether ester modified hydroxy-containing polydimethyl hydrazine, alkane, acrylic copolymer, methacryl fluorenyl copolymer, polyether modified polymethyl ketone A known homogenizing agent such as a burned, acrylic acid based vinegar copolymer, a methyl propylene Wei based copolymer, a blush, or a mixture thereof. Examples of the foaming agent include an anthrone resin, an anthrone solution, an alkyl vinyl ether, and 17 201242054. A copolymer of a Hioz/pif alkyl acrylate and an alkyl methacrylate, or a compound thereof, etc., is known. Defoamer. In the case of adding a leveling agent or an antifoaming agent, one type of compound may be used independently, and two or more types of compounds may be used in combination. Further, as a known additive used in the present invention, it is - - inhibits the yellowing of the adhesive which is caused by the heat of the sun or the like due to the heat of the sun or the like; A known phosphorus-based or phenol-based antioxidant, a violet-line stabilizer, and a metal deactivator can be blended in the main component. These additives may be used singly or in combination of two or more kinds. The phosphorus-based phenol-based antioxidant, the ultraviolet stabilizer, and the metal deactivator used in the present invention are preferably one by weight based on 1 part by weight of the solid content of the bupropion polyol (A). The parts are in the range of 〜1 parts by weight, more preferably 〇] parts by weight. If the weight is less than G.G5 by weight, there is a possibility that a sufficient yellowing suppression effect cannot be obtained. If it is more than 5 parts by weight, the adhesion of the adhesive is greatly deteriorated. As the curing agent, in addition to the above polyisocyanate (B), a well-known cylindrical mouthpiece (for example, 2,5-dimercapto, or 2,2_(14) may be optionally contained in a form which does not inhibit the effects of the present invention. _ butyl butyl) _ ^ (2)) or a trans-compound (such as bis-dicarboxylic acid di-n-dicarboxylate, diterpene azelaic acid, or diammonium adipate) and the like. The solvent to be used in the present invention may, for example, be a kind of acetic acid such as ethyl acetate, butyl acetate or ceramide acetate; acetone, butyl ketone, lysyl butyl ketone, cyclohexanone, etc.; tetrahydrogen, two Member; $ 18 201242054., / pit benzene: aromatic flakes such as di-f-benzene; halogenated hydrocarbons such as dichlorohydrazine and 1,2-dichloroethane; dimethyl hydrazine, dimethyl sulfonium Amines, etc. The solvent to be used may be one type of solvent, or two or more types may be used in combination. The nonvolatile matter (solid content) of the adhesive of the present invention is preferably in the range of from 1% by weight to 50% by weight. The present adhesive can be adjusted by using a solvent as exemplified above. Next, a method of producing a back protective sheet for a solar cell using the adhesive composition for a laminated sheet of the present invention, and a back protective sheet for a solar cell will be described. Further, the manufacturing method or configuration of the back surface protective sheet for a solar cell is not limited to the following examples, and various manufacturing methods or configurations may be employed depending on the purpose or necessity. As a solar cell module, a simple solar cell module has a filler layered on both sides of a solar cell unit as a solar cell element.

Hill。玻璃板之透明性、耐候性、耐擦傷 性優〃 α此現在亦—般用作太陽之 然而，於無需透明性之非受光面側，自成本或=加 工性之方面考慮，由各公司開發玻璃::二生力 取代玻璃板。 料片）’该些背面保護片正在 太陽電池用背面保護片存在有積層有如下者之太陽雷 屬氧化物或非金屬氧化物之聚醋膜等上設有金 膜、純等金屬箱、附有屬層之塑膠 各片狀部件間可使用本發明之積二 pif 201242054 構成之太陽電池用背面保護片可藉由該多岸 …構而賦予各種性能，如可藉由使用聚_而 ，，藉由使用氟系膜而賦予耐候性，使用料而 ^ 氣阻障性。至於使用何種太陽電池时 洛 使用太陽電池模組之產品、用途而適宜選可根據 塑膠膜例如可列舉料苯二曱酸乙二酿 聚醋系樹脂膜，聚乙糊脂膜:聚丙；I Μ月曰膜，ΛΚ乳乙烯系樹脂膜，聚碳酸醋系樹脂臈 备、 =膜;聚(甲基)丙烯酸系樹脂膜，聚 偏； 乙稀、聚氟三氟乙稀、聚乙烯四敗乙烯 】-鼠 等氟=:=_共—二聚: 系塗些體並塗佈丙稀酸系、I 丙稀酸系樹脂等而出=層聚偏二敦乙稀或 ^紙倾著劑層等制多個增膠:== 物理性處理，理、火焰處理等 理，於膜表行改質的化學性處 的褪光加工等等。〜 使其成為所謂之褶皺狀態 組成物適用於表面=$亦可將本發明之積層片用接著劑 處理之原材料中。 ’列舉料或銅箱。作為所蒸鍍之金屬氧化物 20 201242054. /pif 或非金屬無機氧化物例如可使用矽、鋁、鎂、詞、钟、錫、 鈉、硼、鈦、鉛、锆、釔等之氧化物 該些中較佳的是為了滿足作為太陽電池模組而使用時 之耐候性、水蒸氣透過性、電氣絕緣性、機械特性、封裝 作業性等性能，積層有對溫度具有耐受性之聚對笨二甲酸 乙二S旨、聚對苯二甲酸萘二酯等聚酯系樹脂膜、聚碳酸鳴 系樹脂膜而成的太陽電池用背面保護片；為了防止太陽電 池單元由於水之影響而造成的輸出降低，較佳的是積層有 具有水蒸氣阻障性之蒸鍍有金屬氧化物或非金屬無機氧化 物之塑膠膜或紹箔等金屬箔而成的太陽電池用背面保護 片；為了防止由於光劣化所產生之外觀不良；較佳的是積 層有耐候性良好之氟系樹脂膜而成的太陽電池用背面保 片。 /而且，太陽電池用背面保護片為了保護太陽電池模組 免於電壓施加所造成之破損，根據太陽電池單元之發Hill. The transparency, weather resistance, and scratch resistance of the glass plate are excellent. This is also used as a sun. However, it is developed by various companies in terms of cost or workability in the non-light-receiving side where transparency is not required. Glass:: Two raw forces replace the glass plate. "The back sheet" is provided with a gold film, a pure metal case, etc., in the back surface protective sheet for solar cells, which is laminated with a solar ray oxide or a non-metal oxide polymer film of the following. The back surface protective sheet for a solar cell which can be formed by using the two layers of pif 201242054 of the present invention between the various sheet-like members of the plastic layer can be imparted with various properties by using the multi-span structure, for example, by using poly- By using a fluorine-based film to impart weather resistance, a material is used and gas barrier properties are obtained. As for the type of solar cell to be used, it is suitable to use the product and use of the solar cell module. According to the plastic film, for example, the phthalic acid acetylated resin film can be exemplified, and the polyacetamide film: polypropylene; Μ月曰膜, ΛΚ 乙烯 vinyl resin film, polycarbonate 臈 resin preparation, = film; poly (meth) acryl resin film, poly-bias; ethylene, polyfluorotrifluoroethylene, polyethylene Ethylene]-rat and other fluorine=:=_co-dimerization: Apply these bodies and apply acrylic acid, I acrylic acid resin, etc. = layered polydiethylene or dipper Multiple layers of glue for layering: == physical treatment, rationality, flame treatment, etc., matte processing in the chemical modification of the film surface. ~ It is made into a so-called pleated state. The composition is applied to the surface of the raw material of the present invention which can be treated with an adhesive. 'List materials or copper boxes. As the vapor-deposited metal oxide 20 201242054. /pif or a non-metallic inorganic oxide, for example, an oxide of lanthanum, aluminum, magnesium, word, bell, tin, sodium, boron, titanium, lead, zirconium, hafnium or the like can be used. In order to satisfy the properties such as weather resistance, water vapor permeability, electrical insulation, mechanical properties, and packaging workability when used as a solar cell module, it is preferable to have a temperature-resistant pair. A back surface protective sheet for a solar cell obtained by using a polyester resin film such as a polyethylene terephthalate or a polyethylene carbonate resin film; in order to prevent the solar cell from being affected by water The output is lowered, and it is preferable to laminate a back surface protective sheet for a solar cell which has a water vapor barrier metal film deposited with a metal oxide or a non-metal inorganic oxide or a metal foil such as a foil; The appearance of photodegradation is poor, and it is preferable to use a back surface protective sheet for a solar cell in which a fluorine-based resin film having good weather resistance is laminated. / Moreover, the solar cell rear protection sheet protects the solar cell module from damage caused by voltage application, according to the solar cell unit.

電今里，多採用藉由要求部分放電電壓為700 V或1000 V j文性的f氣絕緣性或者包含發泡層而使部分放電電壓 提问之構成。作為使部分放電電壓提高的方法的電氣絕緣 =依存於膜或發泡層之厚度因此存在膜紐泡層成為 ΐ膜之傾向。於最近’多採用使用100 μιη〜300 μιη左右 者之構成。 Η μ 層之形成例如是藉由缺角輪塗佈機（comma 膣耸夕I?式貼合機將接著劑組成物塗佈在其中-個塑膠 、 部件之單面上，使溶劑揮發後，與另一個層壓In today's electricity, the composition of the partial discharge voltage is often used by requiring f-gas insulation with a partial discharge voltage of 700 V or 1000 Vj or a foamed layer. As a method of improving the partial discharge voltage, electrical insulation = depending on the thickness of the film or the foam layer, there is a tendency that the film bubble layer becomes a ruthenium film. In the recent past, the use of 100 μιη to 300 μιη was adopted. The formation of the Η μ layer is carried out, for example, by applying a binder composition to a single surface of one of the plastics and the parts by a comma coater (comma I I ? , , , , , Laminated with another

S 21 201242054. -TL\J^ /jjif 基材貼合，於常溫或加溫下使其硬化而獲得。或者可萨由 如下方式而製造：於任意-個片狀部件上塗佈接著劑^成 物而進行加熱硬化，形成接著劑層，形成接著劑層彳 1’，塗 佈其他之片狀部件形成用塗液，藉由熱或活性能4線而形 成其他片狀部件。作為將接著劑組成物塗佈於片狀部件2 之裝置，可列舉缺角輪塗佈機、乾式貼合機、刀輥塗佈機、 模塗機、輥塗機、棒式塗佈機、凹版輕式塗佈機、反向輕 塗機、刮刀塗佈機（blade coater·)、凹板印刷塗佈機、微型 凹板塗佈機等。於層壓基材表面所塗佈之接著劑量以乾燥 換算計而言，較佳的是〇.1 g/m2〜50 g/m2左右。更佳的是 lg/m2〜50g/m2左右。作為層壓基材，可根據用途而以任 意數選擇任意基材’於設為3層以上之多層構成時，可於 各層之貼合之全部或一部分中使用本發明之接著劑紐成 物0 作為片狀部件形成用塗液，可列舉可於塑膠膜之形成 3用的聚自旨系樹脂溶液、聚乙晞系樹脂溶液、聚丙稀系 知^月曰溶液、聚氣乙烯系樹脂溶液、聚碳酸酯系樹脂溶液、 聚碾系樹脂溶液、聚（甲基)丙稀酸系樹脂溶液、氣系樹脂 溶液等作為較佳例。 可考慮作為太陽電池用背面保護片而要求的性能、價 格、生產性等，選擇各種製造方法或者進一步將該些方法 加以組合。 一 《實例》 以下，藉由實例對本發明加以更詳細之說明，但以下 22 201242054. 之實例並不對本發狀權力_作任何關。另外，實例 中之各評價依照下述方法而進行。另外，於實例中，份表 示重量份，％表示wt% ’經值表示mgK〇H/g。數量平均分 子Ϊ、玻璃轉移溫度、羥值可藉由如下方式而求出。 &lt;數量平均分子量&gt; 數量平均分子量之測定使用東#公司製造之G p C (凝 膠渗透層析儀）「HPC-8020」，管柱使用sh〇dexkf_806l 2根、KF-804L 1根、KF-802 1根，溶劑使用四氫呋喃。 數量平均分子量可藉由標準聚苯乙烯換算而求出。 〈玻璃轉移溫度（Tg) &gt; 玻璃轉移溫度（Tg)之測定可使用精工電子股份有限 公司製造之DSC「RDC220」而進行。於鋁鍋中量取約丨〇 mg 之藉由下述手法而合成之聚碳酸酯胺基曱酸酯多元醇A-1 〜聚碳酸酯胺基曱酸酯多元醇A-21溶液乾燥而成之試 樣，裝置於DSC裝置中而以液氮冷卻至_1〇〇。〇後，根據以 10°C/min進行升溫而所得之DSC圖而求出玻璃轉移溫度。 &lt;羥值&gt; 羥值可藉由如下方式而求出：將約2 g之試樣溶解於 約10 ml之吡啶中之後’加入預先調整之乙酸酐/吡啶之體 積比為15/85的混合溶液5 m卜放置20小時。其後，加入 水1 ml與乙醇l〇ml，藉由〇·1 N之氫氧化鉀（乙醇溶液） 進行滴定而求出。指示劑使用酚酞。 &lt;丙烯酸多元醇（A)之製造&gt; (合成例1)於具有泠凝器、氮氣導入管、滴液漏斗、 23 &amp; 201242054. /plf 及溫度計之4 口燒瓶中裴入乙酸乙醋100重量份，升溫至 8〇 f。繼而藉由滴液漏斗以2小時滴加將丙烯酸丁酯42 7 重量份胃、甲基丙烯酸乙酯51〇重量份、丙烯酸_2_羥基乙酯 1.8重里份、及偶氮雙異丁基腈2 〇重量份預先混合而成之 單體液體。其後使其反應H、時，其次加人偶氮雙異丁基 腈0.2重里份使其反應1小時，進行如上之步驟直至單體 之轉化率成為98%以上，然後加以冷卻。繼而，加入乙酸 乙醋而獲得固形物為50%之溶液。 (合成例2〜合成例21)藉由聚合起始劑偶氣雙異 丁基腈之添加量而調節分子量，除此以外與合成例丨同樣 地進行而獲得表1中所示之合成例2〜合成例21之丙烤酸 多元醇。另外’關於合成例17 ’是於專利文獻2中作為合 成例1而表示之組成的丙烯酸多元醇。另外’表1中之簡 稱如下所述。 bA :丙烯酸丁酯、EMA :甲基丙烯酸乙酯、EA :丙 稀酸乙酿、St:苯乙烯、CHMA:甲基丙烯酸環己酯、2EHA: 丙稀酸_2-乙基己酯、HEA :丙辨酸-2_經基乙酯、4HBA : 丙烯酸難基丁酯、HEMA:甲基丙烯酸羥基乙酯 24 201242054. H1UZ, /pif [表1] 單體組成 數量平 岣分子 量 Tg (°C) 羥值 (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA HEMA A-1 47.2 51.0 1.8 10000 5 8.6 A-2 47.2 51.0 1.8 35000 5 8.6 A-3 47.2 51.0 1.8 60000 5 8.6 A-4 56.2 42.0 1.8 35000 -5 8.6 A-5 60.7 37.5 1.8 35000 -15 8.6 A-6 71.2 27.0 1.8 35000 -25 8.6 A-7 47.0 50.0 3.0 35000 -5 14.5 A-8 47.6 51.5 0.9 35000 -5 4.3 A-9 47.3 52.3 0.4 35000 -5 2.1 A-10 47.6 51.5 0.9 35000 -5 4.3 A-11 4U.3 50.0 10.7 35000 -5 51.6 A-12 iy.u 45.0 16.0 35000 -5 77.4 A-13 48.3 40.6 10.0 1.1 35000 -5 4.3 A-14 44.7 53.5 1.8 35000 10 8.6 _ A-15 38.0 60.2 1.8 35000 5 8.6 A-16 4人〇 51.0 2.0 35000 5 8.6 A-17 70.0 10.0 10.0 10.0 25000 55 48.3 A-18 47.6 51.5 0.9 6000 -5 4.3 A-19 47.6 51.5 0.9 150000 -5 43 ~~ A.-20 4.1 0.9 35000 -50 A-21 35.0 42.0 23.0 35000 -5 lioo~~~ &lt;接著劑組成物之調配例&gt; (實例1〜實例17、比較例1〜比較例6 )相對於以 固形物換算計而言為1〇〇重量份之作為主劑的丙烯酸多元 醇（A)’以表2中所示之調配比而調配作為硬化劑之聚異 氰酸酯（B)，且調配作為添加劑之含有縮水甘油基之矽俨 偶合劑（「KBM-403」信越化學公司製造）3 〇重量份、^ 二月桂酸二辛基錫（「NEOSTANNU-810」、日東化成公勹 製。造）O.G1重量份，進-步以乙酸乙g旨將固形物調二 a 25 201242054. -Ti /pif [表2] 丙婦酸多元31 -(A) 聚異氰酸酯（B) 數量平均 分子量 Tg (°〇 經值 (mgKOH/g) 種類 NCO/OH 比 調配比 實例1 A-1 10000 5 8.6 硬化劑A 2.0 10.2 實例2 A-2 35000 5 8.6 硬化劑A 2.0 10.2 實例3 A-3 60000 5 8.6 硬化劑A 2.0 10.2 實例4 A-4 35000 -5 8.6 硬化劑A 3.0 15.3 實例5 A-5 35000 •15 8.6 硬化劑A 3.0 15.3 實例6 A-6 35000 -25 8.6 硬化劑B 3.0 10.1 實例7 A-7 35000 -5 14.5 硬化劑B 3.0 17.0 實例8 A-8 35000 -5 4.3 硬化劑B 3.0 5.0 實例9 A-9 35000 -5 2.1 硬化劑B 3.0 2.5 實例10 A-10 35000 -5 4.3 硬化劑B 1.2 2.0 實例11 A-10 35000 -5 4.3 硬化劑C 3.0 8.0 實例12 A-11 35000 -5 51.6 硬化劑C 1.2 38.6 實例13 A-12 35000 -5 77.4 硬化劑C 0.5 24.1 實例14 A-13 35000 -5 4.3 硬化劑C 3.0 8.0 實例15 A-14 35000 10 8.6 硬化劑A 2.0 10.2 ^&quot;例 16 A-15 35000 5 8.6 硬化劑A 2.0 10.2 實例17 A-16 35000 5 8.6 硬化劑A 2,0 10.2 比較例1 A-17 25000 55 48.3 硬化劑D 0.5 8.0 比較例2 A-18 6000 -5 4.3 硬化劑A 3.0 7.7 比較例3 A-19 150000 -5 4.3 硬化劑A 3.0 7.7 比較例4 A-20 35000 -50 4.3 硬化劑A 3.0 7.7 比較例5 A-21 35000 -5 110.0 硬化劑A 0.5 32.7 比較例6 5k 1 A-8 35000 -5 4.3 硬化劑A 12.0 30.7 w 100重量份(不揮發成份）而言，調配01^-403 (石夕坑偶合劑）3·0重量份。 (Α) 100重量份(不揮發成份）而言，調配υ_810〇.〇ι重量份作為反應促進劑。 質物，化劑A : TakenateEM60N (三井化學公司製造、六亞甲基二異氰酸酯之ΤΜΡ加合物改 (三井化學公司製造、六亞甲基二異氣酸醋之腺基甲酸醋改質物） 硬化劑C ··異佛爾_二異氰酸_之異氰尿酸醋改質物） 其〜 g化劑D · SumidurN3200 (Sumika Bayer Urethane製造、六亞甲基二異⑽醋之縮二脲改質 &lt;積層膜1之製作例&gt; 使用實例1〜貫例17、及比較例1〜比較例6之各接 著劑組成物，以乾燥塗佈量成為4 g/m2〜5 g/m2之量而藉 由乾式貼合機將接著劑組成物塗佈於聚酯膜[東麗公司製 26 201242054.f Ηΐυζ,/pif 造、Lumirror X-10S、厚度為5〇 μιη]之電暈處理面。繼而， 使溶劑揮發後，層壓於另丨牧聚酯膜[東麗公司製造、 Lumirror X-l0S、厚度為5〇卿]之電暈處理面上。其後， 於40°C下進行3天之硬化處理（老化），由此使接著劑硬 化而製作積層膜1。 &lt;積層膜2之製作例&gt; 使用實例1〜實例4、及比較例1〜比較例3之接著劑 組成物，依照前述積層膜丨之製作法，製作成為[電暈處理 聚酯膜/接著劑層/鋁箔]之構成的積層膜2。 &lt;積層膜3之製作例&gt; 使用實例1〜實例4、及比較例比較例3之接著劑 組成物，依照前述積層膜丨之製作法，製作以二氧化矽蒸 鍍聚酯膜之热鍍層與接著劑層相接之方式而成為[電暈處 理tg曰膜/接著劑層/一氧化石夕蒸鑛聚醋膜]之構成的積層膜 於表2、表3中表示實例1〜實例17、比較例1〜比較 例6中之主劑與硬化劑之組合，以及積層膜i之初始接著 力與於85°C、濕度85%之環境下暴露1000小時、2〇〇〇小 時、及3000小時後之接著力。 而且:於表4、表5中表示使用實例1〜實例4、比較 例。1〜比㈣3之積層膜2、積層膜3之初始接著力與於 85°C、濕度85%之環境下暴露1000小時、2000小時、及 3〇00小時後 =接著力。以下對具體之評價方法加以說明。 &lt;老化前、老化後之接著力試驗&gt;S 21 201242054. -TL\J^ /jjif The substrate is bonded and obtained by hardening it at normal temperature or under heating. Alternatively, Kosa can be produced by applying an adhesive agent to any of the sheet-like members and heat-hardening to form an adhesive layer to form an adhesive layer 彳1', and coating other sheet-like members to form With the coating liquid, other sheet-like members are formed by heat or active energy. Examples of the apparatus for applying the adhesive composition to the sheet member 2 include a knurling wheel coater, a dry laminator, a knife roll coater, a die coater, a roll coater, and a bar coater. Gravure light coater, reverse light coater, blade coater, gravure coater, micro gravure coater, and the like. The amount of the coating applied to the surface of the laminated substrate is preferably from about 1 g/m2 to about 50 g/m2 in terms of dryness. More preferably, it is about lg/m2 to 50g/m2. As the laminated base material, any one of the base materials can be selected in any number depending on the application. When the multilayer structure is three or more layers, the adhesive of the present invention can be used in all or a part of the bonding of the respective layers. Examples of the coating liquid for forming a sheet-like member include a polyether-based resin solution for forming a plastic film, a polyethylene-based resin solution, a polypropylene-based solution, a gas-polymerized vinyl resin solution, and A polycarbonate resin solution, a poly-type resin solution, a poly(meth)acrylic resin solution, a gas-based resin solution, or the like is preferable. The performance, price, productivity, and the like required as a back protective sheet for a solar cell can be considered, and various manufacturing methods can be selected or further combined. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the following examples of 22 201242054. do not make any reference to the present invention. Further, each evaluation in the examples was carried out in accordance with the following method. Further, in the examples, parts represent parts by weight, and % means wt% 'the value indicates mgK 〇 H / g. The number average molecular weight, glass transition temperature, and hydroxyl value can be obtained by the following methods. &lt;Quantum average molecular weight&gt; The number average molecular weight was measured by Gp C (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation, and two columns of sh〇dexkf_806l and one KF-804L were used for the column. One KF-802, the solvent used tetrahydrofuran. The number average molecular weight can be determined by standard polystyrene conversion. <Glass Transfer Temperature (Tg) &gt; Measurement of the glass transition temperature (Tg) can be carried out using DSC "RDC220" manufactured by Seiko Instruments Inc. Approximately 丨〇mg of the polycarbonate amino phthalate polyol A-1~polycarbonate phthalate polyol A-21 solution synthesized by the following method is dried in an aluminum pan. The sample was placed in a DSC unit and cooled to -1 Torr with liquid nitrogen. After the enthalpy, the glass transition temperature was determined from the DSC chart obtained by heating at 10 ° C / min. &lt;Hydroxyl value&gt; The hydroxyl value can be determined by dissolving about 2 g of the sample in about 10 ml of pyridine after adding 'pre-adjusted acetic anhydride/pyridine to a volume ratio of 15/85. The mixed solution was placed at 5 m for 20 hours. Thereafter, 1 ml of water and 1 ml of ethanol were added, and the solution was titrated by potassium hydroxide (ethanol solution) of 〇·1 N. The indicator uses phenolphthalein. &lt;Production of Acrylic Polyol (A)&gt; (Synthesis Example 1) Ethyl acetate was poured into a 4-necked flask equipped with a condenser, a nitrogen introduction tube, a dropping funnel, 23 & 201242054. /plf and a thermometer. 100 parts by weight, heated to 8 〇f. Then, 42 parts by weight of butyl acrylate, 51 parts by weight of ethyl methacrylate, 1.8 parts by weight of 2-hydroxyethyl acrylate, and azobisisobutylnitrile were added dropwise by a dropping funnel over 2 hours. 2 parts by weight of pre-mixed monomer liquid. Thereafter, H was reacted, and then 0.2 parts by weight of azobisisobutylcarbonitrile was added thereto to carry out a reaction for 1 hour, and the above steps were carried out until the conversion of the monomer became 98% or more, followed by cooling. Then, ethyl acetate was added to obtain a solution having a solid content of 50%. (Synthesis Example 2 to Synthesis Example 21) The synthesis example 2 shown in Table 1 was obtained in the same manner as in the synthesis example except that the molecular weight was adjusted by the addition amount of the polymerization initiator bis-isobutyl butyl nitrile. ~ Synthesis of a propanolic acid polyol of Example 21. Further, the "synthesis example 17" is an acrylic polyol having a composition shown in Synthesis Example 1 in Patent Document 2. Further, the abbreviation in Table 1 is as follows. bA: butyl acrylate, EMA: ethyl methacrylate, EA: acrylic acid, St: styrene, CHMA: cyclohexyl methacrylate, 2EHA: -2-ethylhexyl acrylate, HEA :Acidic acid-2_ylaminoethyl, 4HBA: butyl acrylate, HEMA: hydroxyethyl methacrylate 24 201242054. H1UZ, /pif [Table 1] Number of monomer components Flat molecular weight Tg (°C Hydroxyl value (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA HEMA A-1 47.2 51.0 1.8 10000 5 8.6 A-2 47.2 51.0 1.8 35000 5 8.6 A-3 47.2 51.0 1.8 60000 5 8.6 A-4 56.2 42.0 1.8 35000 -5 8.6 A-5 60.7 37.5 1.8 35000 -15 8.6 A-6 71.2 27.0 1.8 35000 -25 8.6 A-7 47.0 50.0 3.0 35000 -5 14.5 A-8 47.6 51.5 0.9 35000 -5 4.3 A-9 47.3 52.3 0.4 35000 -5 2.1 A-10 47.6 51.5 0.9 35000 -5 4.3 A-11 4U.3 50.0 10.7 35000 -5 51.6 A-12 iy.u 45.0 16.0 35000 -5 77.4 A-13 48.3 40.6 10.0 1.1 35000 -5 4.3 A -14 44.7 53.5 1.8 35000 10 8.6 _ A-15 38.0 60.2 1.8 35000 5 8.6 A-16 4 people 〇 51.0 2.0 350 00 5 8.6 A-17 70.0 10.0 10.0 10.0 25000 55 48.3 A-18 47.6 51.5 0.9 6000 -5 4.3 A-19 47.6 51.5 0.9 150000 -5 43 ~~ A.-20 4.1 0.9 35000 -50 A-21 35.0 42.0 23.0 35000 -5 lioo~~~ &lt;Example of formulation of adhesive composition&gt; (Examples 1 to 17 and Comparative Examples 1 to 6) are 1 part by weight in terms of solid content The acrylic polyol (A) of the main component was formulated with the polyisocyanate (B) as a curing agent in the compounding ratio shown in Table 2, and the glycidyl group-containing oxime coupling agent as an additive was formulated ("KBM-403" "Manufactured by Shin-Etsu Chemical Co., Ltd." 3 parts by weight, ^ dioctyltin dilaurate ("NEOSTANNU-810", Nitto Chemical Co., Ltd.). O.G1 parts by weight, further step by step with acetic acid to adjust the solid matter to a 25 201242054. -Ti /pif [Table 2] propylene fosic acid 31 - (A) polyisocyanate (B) number average molecular weight Tg (° 〇 value (mgKOH/g) type NCO/OH ratio formulation ratio Example 1 A-1 10000 5 8.6 Hardener A 2.0 10.2 Example 2 A-2 35000 5 8.6 Hardener A 2.0 10.2 Example 3 A-3 60000 5 8.6 Hardener A 2.0 10.2 Example 4 A-4 35000 -5 8.6 Hardener A 3.0 15.3 Example 5 A-5 35000 • 15 8.6 Hardener A 3.0 15.3 Example 6 A-6 35000 -25 8.6 Hardener B 3.0 10.1 Example 7 A-7 35000 -5 14.5 Hardener B 3.0 17.0 Example 8 A-8 35000 -5 4.3 Hardener B 3.0 5.0 Example 9 A-9 35000 -5 2.1 Hardener B 3.0 2.5 Example 10 A-10 35000 -5 4.3 Hardener B 1.2 2.0 Example 11 A-10 35000 -5 4.3 Hardener C 3.0 8.0 Example 12 A-11 35000 -5 51.6 Hardener C 1.2 38.6 Example 13 A-12 35000 -5 77.4 Hardener C 0.5 24.1 Example 14 A -13 35000 -5 4.3 Hardener C 3.0 8.0 Example 15 A-14 35000 10 8.6 Hardener A 2.0 10.2 ^&quot;Example 16 A-15 35000 5 8.6 Hardener A 2.0 10.2 Example 17 A-16 35000 5 8.6 Hardener A 2,0 10.2 Comparative Example 1 A-17 25000 55 48.3 Hardener D 0.5 8.0 Comparative Example 2 A-18 6000 -5 4.3 Hardener A 3.0 7.7 Comparative Example 3 A-19 150000 -5 4.3 Hardener A 3.0 7.7 Comparative Example 4 A-20 35000 -50 4.3 Hardener A 3.0 7.7 Comparative Example 5 A-21 35000 -5 110.0 Hardener A 0.5 32.7 Comparative Example 6 5k 1 A-8 35000 -5 4.3 Hardener A 12.0 30.7 w 100 For the parts by weight (non-volatile content), 1.0^-403 (Shi Xikeng coupling agent) was added in an amount of 3.0 parts by weight. (Α) For 100 parts by weight (nonvolatile matter), υ_810〇.〇 parts by weight is formulated as a reaction accelerator. Qualitative, chemical agent A : TakenateEM60N (manufactured by Mitsui Chemicals Co., Ltd., hexamethylene diisocyanate ruthenium adduct modification (manufactured by Mitsui Chemicals Co., Ltd., hexamethylene diiso- succinic acid glutamic acid modified vinegar modified substance) hardener C ······································································································ Production Example of Laminated Film 1 Using the respective adhesive compositions of Examples 1 to 17, and Comparative Examples 1 to 6, the amount of dry coating was 4 g/m 2 to 5 g/m 2 . The adhesive composition was applied to a corona-treated surface of a polyester film [26 201242054.f Ηΐυζ, /pif, Lumirror X-10S, thickness 5 〇μηη] manufactured by Toray Industries Co., Ltd. by a dry laminator. After volatilizing the solvent, it was laminated on a corona-treated surface of a polyester film (manufactured by Toray Industries, Lumirror X-l0S, thickness 5 〇), and then dried at 40 ° C for 3 days. After the curing treatment (aging), the adhesive is cured to form the laminated film 1. <Production Example of the laminated film 2> Example 1~ In the adhesive composition of Example 4 and Comparative Example 1 to Comparative Example 3, a laminated film 2 having a structure of [corona treated polyester film/adhesive layer/aluminum foil] was produced in accordance with the method for producing a laminated film. Production Example of Laminated Film 3 Using the adhesive compositions of Examples 1 to 4 and Comparative Example 3, a hot-dip coating of a polyester film deposited with ruthenium dioxide was produced in accordance with the method for producing a laminated film. The laminated film which is formed by the contact of the adhesive layer to form a corona-treated tg film/adhesive layer/one oxidized stone polyvaporation film is shown in Table 2 and Table 3 in Examples 1 to 17. The combination of the main component and the curing agent in Comparative Example 1 to Comparative Example 6, and the initial adhesion force of the laminated film i and exposure in an environment of 85 ° C and a humidity of 85% for 1,000 hours, 2 hours, and 3000 The adhesion force after the hour is shown. Further, in Tables 4 and 5, the use examples 1 to 4 and the comparative examples are shown. The initial adhesion force of the laminated film 2 and the laminated film 3 of 1 to 4 (4) 3 is at 85 ° C and humidity 85. Exposure to 1000 hours, 2000 hours, and after 30,000 hours in the environment of % = adhesion. The following specific evaluation methods Explain. &lt;Adhesion test before aging and after aging&gt;

27 S 201242054 i * v/A / pif 將老化前及老化後之所述積層膜卜積層膜2、積層膜 3分別切斷為2〇〇mmxl5 mm之大小，於25。〇、濕度65% 之裱境下靜置6小時後，依據ASTM-D1876-61之試驗法 而使用拉伸試驗機，於25。(：、濕度65%之環境下，以負載 速度為300 mm/min而進行τ型剝離試驗。以5個試片的 平均值表示PET膜/PET膜間、PET膜/鋁箔間、pET膜/ 二氧化矽蒸鍍聚酯膜間之剝離強度（Nyq5 mm寬）。 &lt;耐濕熱性試驗後之接著力試驗&gt; 將老化後之所述積層體分別切斷為200 mmxl5 mm之 大小’於85°C、濕度85%之環境下靜置looo小時、2〇〇〇 小時、3000小時。其後，於25¾、濕度65%之環境下靜 置6小時後，依據ASTM-D1876-61之試驗法而使用拉伸 試驗機’於25°C、濕度65%之環境下，以負載速度為3〇〇 mm/min而進行T型剥離試驗。以5個試片的平均值表示 PET膜/PET膜間、PET膜/紹箱間、PET膜/二氧化矽蒸鑛 聚酯膜間之剝離強度（N/15 mm 寬）。 &lt;評價基準&gt; [老化前之接著力試驗] ◎於實用上優異：3N/15mm以上 〇實用區域：2 N/15 mm〜3 N/15 mm △實用下限：1 N/15 mm 〜2 N/15 mm X不能實用··不足1 N/15 mm [老化後之試驗、耐濕熱性試驗後之接著力試驗] ◎於實用上優異：5N/15mm以上 28 201242054f -τ x \j^ / pir 〇實用區域：4 N/15 mm〜5 N/15 mm • △實用下限：2 N/15 mm〜4 N/15 mm * x不能實用：不足2 N/15 mm [表3] 接著力 耐濕熱性試驗 老化前後之接著強度 (N/15mm) 85°C、濕度85%之隨時間經過後之接著強度（N/15mm) 老化前 於40°C下老化3天後 1000小時後 2000小時後 3000小時後 實例1 2.2 〇 4.3 〇 4.2 〇 3.8 △ 3.5 △ 實例2 3.4 ◎ 5.6 ◎ 5.4 ◎ 5.2 ◎ 5.2 ◎ 實例3 2.7 〇 5.4 ◎ 5.7 ◎ 5.1 ◎ 5.2 ◎ 實例4 3.5 ◎ 5.1 ◎ 5.2 ◎ 4.8 〇 4.4 〇 實例5 3.2 ◎ 4.2 〇 4.1 〇 3.9 Δ 3.3 Δ 實例6 4.0 ◎ 4.0 〇 3.9 △ 3.7 Δ 3.1 △ 實例7 4.1 ◎ 5.2 ◎ 5.2 ◎ 5.3 ◎ 5.1 Ί ◎ 實例8 3.4 ◎ 5.1 ◎ 4.9 〇 4.3 Ο 3.7 △ 實例9 3.2 ◎ 4.8 〇 4.3 〇 4.2 〇 3.3 △ 實例10 3.3 ◎ 4.9 〇 5.2 ◎ 4.4 〇 3.5 Δ 實例11 3.5 ◎ 5.3 ◎ 5.4 ◎ 5.4 ◎ 5.1 ◎ 實例12 3.8 ◎ 5.1 ◎ 5.2 ◎ 4.4 〇 4.0 〇 實例13 3.6 ◎ 5.0 ◎ 4.8 〇 4.2 〇 3.9 △ 實例14 3.5 ◎ 5.3 ◎ 5.8 ◎ 5.3 ◎ 5.2 ◎ 實例15 3.3 ◎ 5.8 ◎ 5.8 ◎ 5.6 ◎ 5.5 ◎ 實例16 4.0 ◎ 5.7 ◎ 5.9 @ 5.7 ◎ 5.4 ◎ 實例17 3.2 ◎ 5.5 ◎ 5.3 @ 5.Ϊ ◎ 5.0 @ 比較例1 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X 比較例2 0.4 X 3.5 △ 3.4 Δ 2.6 △ 1.8 X 比較例3 1.2 Δ 2.8 Δ 2.2 Δ 2.1 △ 1.5 X 比較例4 2.2 〇 2.2 Δ 1.7 X 1.2 X 0.3 X 比較例5 3.1 ◎ 2.3 Δ 3.3 Δ 2.1 Δ 1.8 X 比較例6 於調製接著劑時產生凝膠物，因此未實施塗佈 s 29 201242054 41627pif [表4] 鋁$/錄虛扭夕帟結眩 接荖力 耐濕熱性試驗 老化前後之接著強度 (N/15mm) 85°C、85%RH之隨時間經過後之接著強度（N/15 111111) 老化前 於40°c下老化3天後 1000小時後 2000小時後 3000小時後 實例1 2.3 〇 4.8 〇 4.5 〇 4.2 〇 3.5 Δ 實例2 2.6 〇 5.4 ◎ 5.3 ◎ 5.1 ◎ 4.8 〇 實例3 2.8 〇 5.1 ◎ 4.9 〇 4.3 〇 4.2 〇 實例4 2.1 〇 4.3 〇 4.5 〇 4.3 〇 4.1 〇 比較例1 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X 比較例2 0.9 X 2.7 Δ 2.4 △ 2.3 Δ 1.8 X 比較例3 0.5 X 2.5 Δ 3.1 △ 2.9 Δ 2.2 Δ [表5]27 S 201242054 i * v/A / pif The laminated film 2 and the laminated film 3 before and after aging are respectively cut into a size of 2 mm x 15 mm, at 25. After standing for 6 hours under a helium and humidity of 65%, a tensile tester was used according to the test method of ASTM-D1876-61, at 25. (:, in a humidity of 65%, the τ-type peeling test was carried out at a load speed of 300 mm/min. The average value of the five test pieces was between PET film/PET film, PET film/aluminum foil, pET film/ Peel strength between the ruthenium dioxide vapor-deposited polyester film (Nyq 5 mm width). &lt;Adhesion test after moisture and heat resistance test&gt; The laminate after aging was cut to a size of 200 mm x 15 mm. After standing at 85 ° C and 85% humidity, the looo hour, 2 hrs, and 3000 hours were allowed to stand. Thereafter, after standing for 6 hours in an environment of 253⁄4 and humidity of 65%, the test was performed according to ASTM-D1876-61. The T-peel test was carried out using a tensile tester at 25 ° C and a humidity of 65% at a load speed of 3 〇〇 mm/min. The average value of the five test pieces was expressed as PET film/PET. Peel strength (N/15 mm width) between film, PET film/sand box, PET film/cerium oxide vaporized polyester film. &lt;Evaluation criteria&gt; [Adhesion test before aging] ◎In practical Excellent: 3N/15mm or more 〇 Practical area: 2 N/15 mm~3 N/15 mm △ Practical lower limit: 1 N/15 mm ~2 N/15 mm X is not practical · Less than 1 N/15 mm [Old Subsequent test, adhesion test after moisture and heat resistance test] ◎ Excellent in practical use: 5N/15mm or more 28 201242054f -τ x \j^ / pir 〇 Practical area: 4 N/15 mm~5 N/15 mm • △ Practical lower limit: 2 N/15 mm~4 N/15 mm * x not practical: less than 2 N/15 mm [Table 3] Next, the strength of the heat and humidity resistance test before and after aging (N/15mm) 85°C, 85% humidity after the passage of time after the strength (N / 15mm) before aging at 40 ° C after 3 days after 1000 hours after 2000 hours after 3000 hours after Example 1 2.2 〇 4.3 〇 4.2 〇 3.8 △ 3.5 △ Example 2 3.4 ◎ 5.6 ◎ 5.4 ◎ 5.2 ◎ 5.2 ◎ Example 3 2.7 〇 5.4 ◎ 5.7 ◎ 5.1 ◎ 5.2 ◎ Example 4 3.5 ◎ 5.1 ◎ 5.2 ◎ 4.8 〇 4.4 〇 Example 5 3.2 ◎ 4.2 〇 4.1 〇 3.9 Δ 3.3 Δ Example 6 4.0 ◎ 4.0 〇 3.9 △ 3.7 Δ 3.1 △ Example 7 4.1 ◎ 5.2 ◎ 5.2 ◎ 5.3 ◎ 5.1 Ί ◎ Example 8 3.4 ◎ 5.1 ◎ 4.9 〇 4.3 Ο 3.7 △ Example 9 3.2 ◎ 4.8 〇 4.3 〇 4.2 〇 3.3 △ Example 10 3.3 ◎ 4.9 〇5.2 ◎ 4.4 〇3.5 Δ Example 11 3.5 ◎ 5.3 ◎ 5.4 ◎ 5.4 ◎ 5.1 ◎ Example 12 3.8 ◎ 5.1 ◎ 5.2 ◎ 4.4 〇 4.0 〇 Example 13 3.6 ◎ 5.0 ◎ 4.8 〇 4.2 〇 3.9 △ Example 14 3.5 ◎ 5.3 ◎ 5.8 ◎ 5.3 ◎ 5.2 ◎ Example 15 3.3 ◎ 5.8 ◎ 5.8 ◎ 5.6 ◎ 5.5 ◎ Example 16 4.0 ◎ 5.7 ◎ 5.9 @ 5.7 ◎ 5.4 ◎ Example 17 3.2 ◎ 5.5 ◎ 5.3 @ 5.Ϊ ◎ 5.0 @ Comparative Example 1 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X Comparative Example 2 0.4 X 3.5 △ 3.4 Δ 2.6 △ 1.8 X Comparative Example 3 1.2 Δ 2.8 Δ 2.2 Δ 2.1 Δ 1.5 X Comparative Example 4 2.2 〇 2.2 Δ 1.7 X 1.2 X 0.3 X Comparative Example 5 3.1 ◎ 2.3 Δ 3.3 Δ 2.1 Δ 1.8 X Comparative Example 6 Gel was produced when the adhesive was prepared Material, therefore not applied s 29 201242054 41627pif [Table 4] Aluminum $ / Recording 扭 帟 帟 眩 荖 耐 耐 耐 耐 耐 耐 耐 耐 ( ( ( ( 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 Subsequent strength after time lapse (N/15 111111) aging at 40 ° C for 3 days before aging, 1000 hours after 2000 hours after 3000 hours after Example 1 2.3 〇 4.8 〇 4.5 〇 4.2 〇 3.5 Δ Example 2 2.6 〇 5.4 ◎ 5.3 ◎ 5.1 ◎ 4.8 〇 Example 3 2.8 〇 5.1 ◎ 4.9 〇 4.3 4.2 〇 Example 4 2.1 〇 4.3 〇 4.5 〇 4.3 〇 4.1 〇 Comparative Example 1 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X Comparative Example 2 0.9 X 2.7 Δ 2.4 Δ 2.3 Δ 1.8 X Comparative Example 3 0.5 X 2.5 Δ 3.1 △ 2.9 Δ 2.2 Δ [Table 5]

二氧化矽蒸鍍聚酯膜/經處理之聚8|膜 接著力 耐濕熱性試驗 老Ί 匕前後之接著強度 (N/15mm) 85°C、85%RH之隨時間經過後之接著強度（N/15mm) 老化 月，J 於40°C下老 化3天後 1000小時後 2000小時後 3000小B车祛 實例1 2.1 〇 4.5 〇 4.3 〇 3.9 △ 3.5 △ 實例2 〇 5.3 ◎ 5.2 ◎ 4.8 〇 4.3 〇 實例3 2.2 〇 5.1 ◎ 5.1 ◎ 4.6 〇 3,7 △ 實例4 2.6 〇 5.2 ◎ 4.3 〇 4.1 〇 4.2 〇 比較例1 0.6 X 3.1 Δ 2.5 Δ 1.9 X 0.9 X 比較例2 0,1 X 2.8 「△ 2.2 Δ 1.7 Δ 1.5 Λ 比較例3 0.〇 2.4 Δ 2.1 Δ 2.1 Δ 1.7 X 如表3所示可知：實例之接著劑組成物於之老化前、 老化後之接著力以及耐濕熱性試驗後之接著力優異，可經 長時間地維持接著強度。因此’該些實例之接著劑組成^ 之面向室外用途的長期耐濕熱性優異。 而且’於JIS C 8917 (結晶系太陽電池模組 驗方法及耐久試驗方法）中，將於85。〇、濕度850/、而° 1000小時規定為耐濕性試驗Β_2，已知為特別1心= 30 201242054 /pif 丨=中’表現出於超過1000小時，經過3000 長時間後亦可維持接著強度之特性，可以說本發明 之接者劑組成物具有充分之長期耐濕熱性。 太陽電池用背面保護片於此種長期耐濕熱試驗中保持 ^刀的層·者強度（層壓強度），於片材層間並不產生脫 ^因此可有助於太陽電池元件之保護、發電效率之維持， 步可有助於太陽電池之壽命延長。太陽電池之壽命延 ^與太陽電池系統之普及相關，自確保化石燃料以外之能 里的觀點考慮，亦有助於環境保護。 本發明之接著敝成物可作為面向賴物等室外產業 用途之多層積層材料（屏障材料、外·料、屋頂材料、 太陽電池面板材料（太陽電池用背面保護片、太陽電池表 ，保護片）、窗戶材料、室外地板材料、證明保護材料、汽 車部件等）用接著劑而提供強的接著強度。而且，可抑制 於室外暴糾由於搞等所造叙接著強度料間經過而 降低，可經長時間地維持強的接著強度。 。比較例1是丙烯酸多元醇⑷之玻璃轉移溫度為 55 C ’高於5G°C之例子。評價之結果是獲得基本上沒有對 基材之制性’初始之接著力小，於耐濕熱輯驗中接著 力降低之Μ要。 比較例2是丙烯酸多元醇（Α)之數量平均分子量為 MOO mG，GGG之例子。可知評價之結果是老化步驟 前之接著劑之凝聚力不足，老化步驟前之接著力小。於工 業性生產之㈣時’捲繞她狀之狀態騎層體使捲芯為 31 201242054 =垂直料_行老化。若老化轉狀接著力小 於老化時捲繞容易散開，並不適於工業性生產。 、 比較例3是丙烯酸多元醇⑷之數量平均分子 於卿，刪之例子。可知評價之結果是對PET ；‘濶性不足，無法於老化前獲得充分之接著力。與仏 樣的是於老化的過程中捲繞容易朗，並不適於 ^ 產。而且，由於耐濕熱性試驗而造成接著力緩緩 降低，且接著力本來就低，因此獲得於3〇〇〇小低 用下限之結果。 _、牙 比較例4是丙烯酸多元醇⑷之玻璃轉移溫度為 ’低於-40〇C之例子。可知評價之結果是即使於表面 3 = 形時，甚至連3⑽5 _)左右之接著 比車又例5是丙稀酸多元醇（A)之〇H值為11〇，大於 0^之例子。可知評價之結果是獲得交聯變過剩從而成為 非Μ找硬化_，接著性差的結果。 比車乂例6是聚異氰酸酯（Β)之調配量為NCO/OH=12 2子。可知評價之結果是於塗佈之前進行與丙騎多元 &quot;Α) ^反應，產生凝膠物，因此無法進行塗佈。 片拇本申=案主張以於2〇U年3月31號向曰本智慧財產 巧申印之日本專利申請案第2〇11-〇78188號為基礎的 奢權該專利申請案所揭露之内容系完整結合於本說明 書中。 [產業上之可利用性] 32 201242054 ，pif 同月ir 月之積f片用接著劑組成物是用以接合同-或不 ==ΐΓ成物即使暴露於高溫纖環境下亦可 之多…因此’作為面向建築物等室外產業用途 ^積層材料（屏障材料、外麟料、屋頂材料、 太陽電池㈣面保護片、太陽電池表面保 ;』、田 室外地板材料、照明保護材料、汽車部 接著劑而言適宜。可經長日相輯日相經過地維 =者強度’因此特別適於強烈要求環境耐受性之用途、 陽電池用背面保制之形成。而且，亦適於太陽電 =面保護片之形成。而且’本發明之積層片用接著劑 組成物於特別是於包含歸膜之表面處理層的層間顯示出 ί的接著力，亦可触地勒於表面未域理之職料（亦 包合表面未經處理之塑膠膜）中。 【圖式簡單說明】 益。 ”*、 【主要元件符號說明】 益 # »»、二 矽 矽 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 聚酯 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 N/15mm) aging month, J after aging at 40 °C for 3 days, after 1000 hours, after 2000 hours, 3000 small B rut example 1 2.1 〇4.5 〇4.3 〇3.9 △ 3.5 △ Example 2 〇5.3 ◎ 5.2 ◎ 4.8 〇 4.3 〇Example 3 2.2 〇5.1 ◎ 5.1 ◎ 4.6 〇3,7 △ Example 4 2.6 〇5.2 ◎ 4.3 〇4.1 〇4.2 〇Comparative Example 1 0.6 X 3.1 Δ 2.5 Δ 1.9 X 0.9 X Comparative Example 2 0,1 X 2.8 "△ 2.2 Δ 1.7 Δ 1.5 Λ Comparative Example 3 0. 〇 2.4 Δ 2.1 Δ 2.1 Δ 1.7 X As shown in Table 3, it can be seen that the example of the adhesive composition before aging, the post-aging adhesion and the heat and humidity resistance test Then, the force is excellent, and the strength can be maintained for a long period of time. Therefore, the adhesive composition of these examples is excellent in long-term heat and humidity resistance for outdoor use. Moreover, 'JIS C 8917 (Crystal System Solar Cell Module Test Method and In the endurance test method), it will be 85. 〇, humidity 850 /, and ° 1000 The time is specified as the moisture resistance test Β_2, which is known as the special 1 heart = 30 201242054 / pif 丨 = medium 'expressed for more than 1000 hours, after 3,000 hours can maintain the strength of the subsequent strength, it can be said that the invention The composition of the agent has sufficient long-term heat and humidity resistance. The back surface protective sheet for solar cells maintains the layer strength (lamination strength) of the blade during such long-term heat and humidity resistance test, so that no peeling occurs between the sheet layers. It can help protect solar cell components and maintain power generation efficiency, which can help extend the life of solar cells. The life cycle of solar cells is related to the popularity of solar cell systems, and the viewpoint of ensuring the ability of fossil fuels It is also considered to contribute to environmental protection. The subsequent composition of the present invention can be used as a multi-layer laminate material for outdoor industrial applications such as a barrier material (barrier material, exterior material, roofing material, solar cell panel material (back protection for solar cells) Sheets, solar cell meters, protective sheets), window materials, outdoor flooring materials, proof protective materials, automotive parts, etc.) provide strong bonding with adhesives In addition, it can be suppressed from the outdoor storm due to the reduction of the strength between the materials, and the strength can be maintained for a long time. Comparative Example 1 is the glass transition temperature of the acrylic polyol (4) is 55. An example in which C ' is higher than 5 G ° C. The result of the evaluation is that substantially no basis for the substrate is obtained, and the initial adhesive force is small, and the subsequent force is lowered in the heat and humidity resistance test. Comparative Example 2 is an example in which the number average molecular weight of the acrylic polyol (Α) is MOO mG, GGG. It can be seen that the result of the evaluation is that the cohesive force of the adhesive before the aging step is insufficient, and the adhesion force before the aging step is small. In the industrial production (four) when the state of winding her shape, riding the layer body to make the core is 31 201242054 = vertical material _ line aging. If the aging transition is less than the aging, the winding is easily spread, which is not suitable for industrial production. Comparative Example 3 is an example of the number average molecular weight of the acrylic polyol (4). It can be seen that the result of the evaluation is that PET is insufficient; it is not sufficient to obtain sufficient adhesion before aging. It is easy to wind up during the aging process, and it is not suitable for production. Further, since the adhesion was gradually lowered due to the heat and humidity resistance test, and the force was originally low, the result was obtained at the lower limit of 3 〇〇〇. _, teeth Comparative Example 4 is an example in which the glass transition temperature of the acrylic polyol (4) was ' below -40 〇C. It can be seen that the result of the evaluation is that even when the surface 3 = shape, even 3 (10) 5 _) is followed by the example of the vehicle, and the enthalpy H value of the acrylic polyol (A) is 11 〇, which is larger than 0 。 . It can be seen that the result of the evaluation is that the cross-linking becomes excessive and the non-cracking hardening_ is obtained, and the result is poor. The compounding amount of polyisocyanate (Β) is NCO/OH=12 2 than that of the car. It was found that the result of the evaluation was that a reaction was carried out with a C. singularity before the coating to produce a gel, and thus coating was impossible. The invention of the patent application is based on the Japanese patent application No. 2〇11-7878, which is based on the Japanese patent application No. 2〇-78188, which was filed on March 31, 2002. The content is fully integrated into this specification. [Industrial Applicability] 32 201242054 , pif The same month ir month of the product of the f-substrate composition is used to accept the contract - or not = = the composition can be even exposed to high-temperature fiber environment ... so 'As a building for outdoor industries such as buildings, laminated materials (barrier materials, outer materials, roofing materials, solar cell (four) surface protection sheets, solar cell surface protection;", outdoor floor materials, lighting protection materials, automotive parts Appropriate. It can be used for long-term phase-matching of the phase of the earth's dimension = strength, so it is particularly suitable for applications that strongly demand environmental resistance, and the formation of the back side of the anode battery. Moreover, it is also suitable for solar power = surface protection. The formation of the sheet. Moreover, the adhesive composition for the laminated sheet of the present invention exhibits an adhesive force between the layers including the surface-treated layer of the film-removing layer, and can also touch the surface untreated material ( Also included in the untreated plastic film). [Simple description of the diagram] Benefits. ”*, [Main component symbol description] 益# »»,

33 S33 S

Claims (1)

201242054f ~Γ 1 / pi 丄 七、申請專利範圍： 1 · 一種積層片用接者劑組成物，包括丙稀酸多元醇 (A)與聚異氰酸酯（B)， 所述丙烯酸多元醇（A)之數量平均分子量為1〇,〇〇〇 〜100,000 ’ 且髮值為 1 mgK〇H/g〜1〇〇 rngKOH/g ’ 另外玻 璃轉移溫度（Tg)超過_40°C且為1〇ΐ以下， 源自所述丙烯酸多元醇（Α)之羥基與源自所述聚異 氰酸酯（Β)之異氰酸醋基之當量比NCO/OH為〇,1〜3。 2·如申請專利範圍第1項所述之積層片用接著劑組成 物，其中， 所述聚異氰酸酯（Β)包含由脂環族二異氰酸酯或脂 肪族二異氰酸酯衍生的聚異氰酸酷。 3.如申請專利範圍第1項或第2項所述之積層片用接 著劑組成物，其中， 其於包含2層以上片狀部件的太陽電池用背面保 之製造中使用， 人如下之用途中：形成用以將所述片狀部件彼此接 &amp;的接者劑層的至少一部分。 4_ —種太陽電池用背面保護片，其包含： 居二=請專利_第1項至第3射任—項所述之積 ^而積声^1組成物所形成的接著劑層；介隔所述接著劑 層而積層的至少2層以上的片狀部件。 34 201242054. -Μυώ /pif 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： 〇 五、 本案若有化學式時，請揭示最能顯示發明特徵 的化學式： 無〇 § 3 201242054 .一層， 修正日期:1〇1年6月15曰 爲第ΐίΐ 104895號中文說明書無劃線修正本 發明專利說明書 (本說明書格式、順序，請勿任意更動，※記號部分請勿填寫） ※申請案號 ※申請日十,.&gt;‘/? m?c分類 一、發明名稱：（中文/英文） c〇v ] 積層片用接著劑組成物及太陽電池用背面保護片201242054f ~ Γ 1 / pi 丄 VII, the scope of application for patents: 1 · A laminate composition for a laminate, comprising an acrylic polyol (A) and a polyisocyanate (B), the acrylic polyol (A) The number average molecular weight is 1 〇, 〇〇〇~100,000 ' and the value is 1 mgK〇H/g~1〇〇rngKOH/g ' In addition, the glass transition temperature (Tg) exceeds _40 ° C and is less than 1 ,. The equivalent ratio NCO/OH of the hydroxyl group derived from the acrylic polyol (Α) to the isocyanate group derived from the polyisocyanate is 〇1 to 3. The adhesive composition for laminated sheets according to claim 1, wherein the polyisocyanate comprises polyisocyanate derived from an alicyclic diisocyanate or an aliphatic diisocyanate. 3. The adhesive composition for a laminated sheet according to the first or second aspect of the invention, which is used in the manufacture of a back surface of a solar cell comprising two or more sheet members, the use of the following Medium: forming at least a portion of a connector layer for joining the sheet members to each other. 4_—a back protective sheet for a solar cell, comprising: an adhesive layer formed by the composition of the second and third shots of the first to third shots; At least two or more sheet-like members laminated with the adhesive layer. 34 201242054. -Μυώ /pif IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇§§ 201242054. One layer, date of revision: January 1st, 1st, 1st For the Chinese manual of ΐίΐ 104895, the patent specification of this invention is not slashed. (The format and order of this manual should not be changed at any time. Please do not fill in the ※ part of the symbol.) ※Application number ※Application date ten,.&gt;'/? m ?c classification one, invention name: (Chinese / English) c〇v ] laminate with adhesive composition and solar cell back protection sheet ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL 二、 中文發明摘要： 提供一種接著劑組成物，其於各種片狀部件間、特別 是於包含塑膠膜表面處理層之層間顯示出高的接著力，即 使暴露於高溫高濕度環境下亦可維持高的接著力，適於製 造太陽電池用背面保護片。本發明之積層片用接著劑組成 物包括丙烯酸多元醇（A)與聚異氰酸酯（b)，丙婦酸多 元醇（A)之數量平均分子量為1〇,〇〇〇〜10〇,〇〇〇，且經值 為1 mgKOH/g〜l〇〇mgKOH/g，另外玻璃轉移溫度（Tg) 超過-40 C且為l〇°C以下。另外，源自丙烯酸多元醇（a) 之羥基與源自聚異氰酸酯（B)之異氰酸酯基之當量比 NCO/OH 為 0.1 〜3。 三、 英文發明摘要： An adhesive composition for fabricating a back 201242054 ϋΊοϋ4895號中文說明書無劃線修正本 修正日期αοι年6月15日 六、發明說明： 【發明所屬之技術領域】 本發明是有關於/種積層片用接著劑組成物及太陽電 池用背面保護片。 【先前技術】 近年來，以面向室外產業用途的例如屏障材料、屋頂 材料、太陽電池面板材料、窗戶材料、室外地板材料、照 明保護材料、汽車部件、招牌、標籤等中所使用的多層（複 合）膜等為首的多層（複合）積層體得到實用化。多層積 層體可藉由對金屬系原材料或塑膠系原材料等進行積層 (層壓）而獲得。金屬系原材料可列舉鋁或銅、鋼板等金 屬箱、金屬板、金屬蒸锻膜等。塑膠系原材料可列舉聚丙 烯、聚氣乙烯、聚酯、氟樹脂、丙烯酸系樹脂等之塑膠膜、 塑膠片、塑膠板’於表面形成有二氧化石夕蒸鍍膜等無機氧 化物層的塑膠膜等。金屬系原材料或塑膠李屌 : 中所使用的接著劑於先前已知有聚環氧系== 基甲酸醋系接著劑。 $專散獻i中記載了-種太陽電池背面密封用片 材，其包含以聚胺基甲酸酯系接著劑將至少2 = 。更詳細而言’記载了滿足:下條二、 二St:之接著劑的聚胺基甲酸峨 二未加壓蒸汽之促進評價裂置的高加速溫 應力測試(_室中，於_ 下保存⑽小時後的層壓強度至少為iN/i5_ 201242054 -— ^— i 爲第-麵號中文說鴨無劃線修正本 修正日期⑽年6月15曰 上；條件2 :在作為利用加壓蒸汽之促進評價裝置的謹丁 室中’於105°C、1.05 atm下保持168小時後，並不產生 伴隨著脫層（delamination)的基材間的隆起。具體而古， 提出了分別相對於多元醇A〜多元醇17這6種類'型的多5元 醇而組合有交聯劑的多種聚胺基甲酸醋系接著劑（參照專 利文獻1之申睛專利範圍第2項〜第11項）。 於專利文獻2中記載了一種太陽電池模組用後片，其 〇 包含'丙烯酸緖著縣至少2個基材貼合*成的積層 體。更詳細而言，提出了一種丙烯酸系接著劑作為具有耐 水解性、耐絕緣性、及水分阻障性之丙烯酸系接著劑，所 述丙烯酸系接著劑含有使含有通式（1)所表示之單體的單 體成分聚合而成的丙烯酸系聚合物（參照專利文獻2之申 請專利範圍第2項）。 C^^CCR^-CO-OZ (I) ) 於式中，R1表示氫原子或甲基，z表示碳數為4〜25 之烴基。 另外’至於成為優先權之基礎的先前申請後所公開的 專利文獻’於專利文獻3、專利文獻4中記载了一種適合 如下用途之接著劑組成物：於對塑膠膜之未經處理之面與 其他基材進行接著之片材中使用。 [先前技術文獻] [專利文獻] 5 201242054 ~Γ 1 \JL·. / ^/AJL 1 修正曰期:1〇1年6月15日 爲第1011〇4895號中文說明書無畫!)線修正本 [專利文獻1]國際公開2007-148754號 [專利文獻2]曰本專利特開2〇〇9_246360號公報 [專利文獻3]曰本專利特開2〇11_1〇5819號公報 [專利文獻4]日本專利特開n519號公報 ^為了在室外的嚴酷條件下經過長時間地穩定地維持接 著力，重要的是接著強度即使隨時間經過亦穩定。於最近， 盛行開發如專利文獻3或專利文獻4所示那樣可將未進行 表面處理之聚酯膜等的塑膠之未經處理之面與其他基材良 好地接著的接著劑。由於未進行表面處理而可實現製造步 驟之縮短化，因此可降低成本。然而，於其另一方面而言， 亦運用了自先别所運用的表面處理技術，對於使接著劑組 成物本來雜能進-步提高、且朗地具有紐異之接著 特性的接著劑組成物的需求亦變高。 【發明内容】 本發明是黎於上述背景而成的，其目的在於提供一種 積層片用接著劑組成物以及太陽電池用背面保護片，所迷 積層片用接著劑組成物於各種片狀部件間、特別於是包含 表面處理層的層間顯示出高的接著力，即使暴露於 尚溫高濕度環境下村轉高的接著力，適於製造太陽 池用背面保護片。 本發明者等人為了解決上述課題而進行了銳意研究， 結，發現可藉由町所示之積層y用接著触成物而解決 上述課題，從而完成本發明。 、 亦即’本發明之積層片用接著劑組成物包括丙烯酸多 201242054 _____ 修正日期:101年6月15日 爲第101104895號中文說明書無劃線修正本 元醇（A)與聚異氰酸酯（B)，所述丙烯酸多元醇（a) 之數量平均分子量為10,000〜100,000，且經值為1 mgKOH/g〜100mgKOH/g，另外玻璃轉移溫度（Tg)超過 -40°C且為10°C以下，源自所述丙烯酸多元醇（A)之羥基 與源自所述聚異乱酸醋（B )之異氰酸醋基之當量比 NCO/OH 為 0.1 〜3。 所述聚異氰酸酯（B)之較佳例可列舉包含由脂環族ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL II. SUMMARY OF THE INVENTION: An adhesive composition is provided which exhibits high adhesion between various sheet members, particularly layers comprising a plastic film surface treatment layer. It can maintain a high adhesion even when exposed to high temperature and high humidity, and is suitable for manufacturing a back protective sheet for solar cells. The adhesive composition for a laminated sheet of the present invention comprises an acrylic polyol (A) and a polyisocyanate (b), and the number average molecular weight of the bupropion polyol (A) is 1 〇, 〇〇〇 10 〇, 〇〇〇 And the pass value is 1 mgKOH/g~l〇〇mgKOH/g, and the glass transition temperature (Tg) exceeds -40 C and is below 10 °C. Further, the equivalent ratio NCO/OH of the hydroxyl group derived from the acrylic polyol (a) to the isocyanate group derived from the polyisocyanate (B) is 0.1 to 3. III. Abstract of English invention: An adhesive composition for fabricating a back 201242054 ϋΊοϋ4895 Chinese manual without scribe correction. Amendment date αοι年6月15日. Description of the invention: [Technical field of invention] The present invention relates to The adhesive composition for the laminated sheet and the back protective sheet for solar cells. [Prior Art] In recent years, multi-layer (composite) used in outdoor industry applications such as barrier materials, roofing materials, solar panel materials, window materials, outdoor flooring materials, lighting protection materials, automobile parts, signs, labels, and the like A multilayer (composite) laminate body such as a film is put into practical use. The multilayered laminate can be obtained by laminating (laminating) a metal-based raw material or a plastic-based raw material. Examples of the metal-based raw material include a metal case such as aluminum, copper, or steel plate, a metal plate, and a metal forged film. Plastic materials include polypropylene, polyethylene, polyester, fluororesin, acrylic resin, plastic film, plastic sheet, plastic sheet, and plastic film with an inorganic oxide layer such as a dioxide oxide film deposited on the surface. Wait. Metal-based raw materials or plastics: The adhesive used in the prior art is known as a polyepoxy-based == carboxylic acid vinegar-based adhesive. A special sheet for solar cell back sealing, which contains at least 2 = a polyurethane-based adhesive, is described in the Japanese Patent Publication No. In more detail, the high accelerated temperature stress test for the evaluation of the cracking is evaluated in the _ room, which is satisfied by the evaluation of the following two: two St. (10) The lamination strength after hours is at least iN/i5_ 201242054 - - ^ - i is the first - face number Chinese said duck without scribe correction this correction date (10) June 15 ;; condition 2: in the use of pressurized steam In the chamber of the evaluation device, after holding for 168 hours at 105 ° C and 1.05 atm, there is no ridge between the substrates accompanying delamination. Specifically, it is proposed to be relatively different from each other. A variety of polyamino carboxylic acid vinegar-based adhesives in which a cross-linking agent is used as a mixture of a plurality of 5-alcohols of the alcohol type A to the polyhydric alcohol 17 (refer to Patent Application No. 2 to Item 11 of Patent Document 1) Patent Document 2 describes a rear sheet for a solar cell module, and the crucible includes a laminate in which at least two substrates of the acrylic acid in the prefecture are bonded. In more detail, an acrylic adhesive is proposed. As a hydrolysis resistance, insulation resistance, and moisture barrier An acryl-based adhesive containing an acrylic polymer obtained by polymerizing a monomer component containing a monomer represented by the general formula (1) (refer to Patent Application No. 2 of Patent Document 2) C^^CCR^-CO-OZ (I) In the formula, R1 represents a hydrogen atom or a methyl group, and z represents a hydrocarbon group having a carbon number of 4 to 25. Further, in the patent documents disclosed in the prior application, which is the basis of the priority, Patent Document 3 and Patent Document 4 disclose an adhesive composition suitable for the following applications: on the untreated side of the plastic film. Used in subsequent sheets with other substrates. [Prior technical literature] [Patent Document] 5 201242054 ~Γ 1 \JL·. / ^/AJL 1 Revision period: June 15th, 1st, June 15th, No. 1011〇4895 Chinese manual no picture!) Line correction [Patent Document 1] International Publication No. 2007-148754 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Patent Publication No. n519. In order to stably maintain the adhesion force over a long period of time under severe outdoor conditions, it is important that the subsequent strength is stabilized even with time. Recently, an adhesive which can be used to adhere the untreated surface of a plastic film such as a polyester film which has not been subjected to surface treatment to another substrate as disclosed in Patent Document 3 or Patent Document 4 has been actively developed. Since the surface-treatment is not performed, the manufacturing steps can be shortened, so that the cost can be reduced. However, on the other hand, the surface treatment technology used in the prior art is also used, and the composition of the adhesive which allows the adhesive composition to be further improved and has the same characteristics as the adhesive properties of the adhesive composition. The demand for goods has also increased. SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and an object of the invention is to provide an adhesive composition for a laminated sheet and a back protective sheet for a solar cell, wherein the laminated sheet is composed of an adhesive composition between various sheet members. In particular, the layer containing the surface treatment layer exhibits a high adhesion force, and is suitable for the solar cell back surface protection sheet even when exposed to a high temperature and humidity environment. The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have found that the above problems can be solved by using the laminate y shown in the town with the succeeding touch, thereby completing the present invention. That is, the adhesive composition for the laminated sheet of the present invention includes acrylic acid 201242054 _____ Revision date: June 15, 101 is the Chinese specification No. 101104895. The original alcohol (A) and polyisocyanate (B) are not underlined. The acrylic polyol (a) has a number average molecular weight of 10,000 to 100,000, and a pass value of 1 mgKOH/g to 100 mgKOH/g, and a glass transition temperature (Tg) of more than -40 ° C and 10 ° C or less. The equivalent ratio NCO/OH of the hydroxyl group derived from the acrylic polyol (A) to the isocyanate group derived from the polyisoan acid vinegar (B) is 0.1 to 3. Preferred examples of the polyisocyanate (B) include alicyclic groups 二異氰酸酯或脂肪族二異氰酸酯所衍生之聚異氰酸酯之例 子0 上述態樣之積層片用接著劑組成物於包含2層以上片 狀部件的太陽電池用背面保護片之製造中使用，適用於如 下之用途中：形成用以將所述片狀部件彼此接合的接著劑 層的至少一部分。 本發明之太陽電池用背面保護片包含：由上述態樣之 2片用接著劑組成物而形成的接著劑層；介隔所述接著 蜊層而積層的至少2層以上的片狀部件。 [發明的效果] 片用^本發明可提供如下的優異絲：可提供-種積層 組成物以及太陽電池用背面保護片，所述積層 膜表面處理層的層間顯：特別是於包含塑膠 亦可_高的接著力，適於製造太陽電池用 【實施方式】 7 201242054 I 1 V·/知 / 先/ϋ 爲第101104895號中文說明書無劃線修正本修正曰期:1〇1年6月丨5曰 以下對本發明之實施形態加以詳細說明。另外，只要 付合本發明的宗旨’其他實施形態亦可屬於本發明之範 疇。而且，於本說明書中，「任意之數A〜任意之數B」的 記載是表示數A及大於數A之範圍，且為數B及小於數B 的範圍。而且，於本說明書及申請專利範圍中所記載之「（甲 基)丙烯S&amp;」之記載包含換稱為「丙稀醯」之化合物及換稱 為「曱基丙稀酿」之化合物的任意者。而且，於「（曱基） 丙烯基」及「（甲基）丙烯酸酯」中亦同樣地定義。 &lt;丙烯酸多元醇（A) &gt; 丙烯酸多元醇（A)可較佳地使用含有經基之單（甲基） 丙烯酸酯單體與不含羥基之單（甲基）丙烯酸酯單體之共聚 物。含有羥基之單（甲基)丙烯酸酯單體是於1分子中含有1 ，（甲基)丙烯醯基與i個以上羥基之單體。較佳例可列舉 ，由2元醇與（甲基）丙烯酸之反應而所得之單（甲基）丙浠 峻酉旨單體、ε_己内酉旨改質（曱基)丙烯酸系單體等。 ^丙烯酸多元醇⑷之數量平均分子量為同種程度， =提高接著力之方面考慮，與單（甲基)丙稀酸醋單體之 二’無關之部分、亦即經由醋鍵而與（甲基)丙稀酸部分鍵 或烯基等部分。以下稱為「側鏈部分」)之 、疋〜17，更佳的是1〜9，進一步更佳的是1 '所述側鏈部分於共聚後形成丙烯酸多元醇⑷之側 况甲〜基)丙烯_單體之所述側鏈部分之碳數一般情 均八、3〇々左右，但如果丙稀酸多元醇（Α)之數量平 -刀里為同等程度’則所述側鏈部分越短，丙稀酸多元 201242054 ‘ w I f a I l 修正日期·_101年6月15日 爲第101104895號中文說明書無劃線修正本 鏈越相對性變長。其結果，硬化後之接著層 的機，質言為伸長率）提高，接著力提高。 2元醇所得之單（曱基)丙稀酸醋單體例如可列舉（甲 二，、H祕乙顆 '(曱基)丙烯酸經基丙醋、1,4丁二 醇早（甲基)丙稀軸、（聚)乙二醇單(曱基)丙烯酸醋等。 …另外:如（曱基）丙缔酸_2,3_二經基丙醋等這樣的由3 〇 〇 ^上^醇而所彳代單（曱基)丙稀酸δΐ單體亦可用作含有 經基之单（曱基)丙稀酸酯單體。 不3 &amp;基之單（甲基)丙稀酸g旨單體可適宜選擇自先前 、“所A知之自由基聚合性單體而使用。適宜的例子 I列舉以（曱基)丙晞酸正丁醋、（甲基)丙稀酸異丁醋、（甲 丙烯酸第三丁醋、(甲基)丙烯酸-2-乙基己酉旨、(甲基)丙 3酸正辛醋、（甲基)丙稀酸月桂基S旨、（甲基)丙稀酸十三烧 =、（甲基)丙烯酸硬脂基醋等（甲基)丙烯酸烧基醋單體為 代表之長鏈（曱基)丙烯酸系單體、及丙烯腈等。 另外，除了上述含有經基之（甲基)丙稀酸醋單體斑不 &quot;羥基之單（甲基)丙婦酸酯單體之外，ϋ可以共聚其他單 體⑽例如·（甲基)丙烯酸、馬來酸、馬來酸肝等含有羧基 之單體或其酸酐，或者苯乙埽等乙烯系單體等。另外，含 有，基之（甲基)丙烯酸醋單體、不含錄之單（甲基)丙稀酸 醋早體可分別獨立地使们種化合物，亦可將2種以上化 合物組合使用。關於使用其他單體之情形亦同樣。 於本發明中，丙烯酸多元醇（Α)之數量平均分子量 必須為10，_〜100,_。進一步而言，較佳的是1〇，_ 9 201242054 ~Γ ί KJ ^ / yjki A 修正曰期:1〇1年6月15日 爲第1011(Η895號中文說明書無劃線修正本 〜70,000’更佳的是 25,00〇〜5〇,〇〇〇。 使用本發明之積層片轉著劑組成物（以下亦稱為「接 著劑組成物」）將2個以上片狀部件積層而成的積層片、例 如太陽電池用背面保護片例如可經過如下之步驟而獲得。 於其中-個片狀部件之接合面塗佈接著劑組成物而使其乾 燥。其次’將其他片狀部件重4於接著劑層上，藉由於俄 〜6〇°C之環境下保存2日〜1星期左右之被稱為「老化」 之步驟，進行接著劑層之硬化而獲得積層片。 ，於丙烯酸多元醇之數量平均分子量^足1〇,_之情 形時’存在老化步驟前之接著劑層之凝聚力不足之傾向， 且存在老化步驟前之接著力變小之虞。在工業性生產 形時，捲繞為輥狀之狀態的積層體在通常情況下使捲 上下垂直方向而進行老化。若老化步驟前之接著力小 於正在進行老化時捲繞容易散開，並不適於工業性生產i ，則存在老化步驟後之凝聚力不足之 、°，伴隨於此而存在耐濕熱性變低、產生脫層等之虞。 而且，若丙烯酸多元醇之數量平均分、 ’則存在接著劑之黏度變高’於塗佈性方面產：二 子片狀部件之制性降低之傾向，其結果存在老化+ 化初始接著力由於老化而與ί 化⑴相比“變大，但存在由於其後之耐㉙ 緩降低，於經過3000小時後低於使用下限虞;驗而緩 另外，本發明中之數量平均分子量是藉由1 析儀（GPC)而求出，進行聚苯乙烯換算之值。更^體; 10 201242054A 修正曰期:101年6月15日 爲第lill〇4895號中文說明書無劃線 «本發明中之數量平均分子量是表示藉由後述之實例中 所記載之贼方法而求H而且，_玻雜移溫度、 NCO/OH當量比’亦同樣地表示藉由後述之實例中所記載 之方法而求出之值。 丙烯酸多7L醇（A)之經值由含有經基之單（曱基)丙烯 酸醋單體之含量㈣定，於本發明性值為i mgK〇H/g〜 100 mgKOH/g ’ 較佳的是 i mgK〇H/g〜5〇 mgK⑽g，更 〇 佳的是 1 mgKOH/g〜15 mgKOH/g。若不足 i mgK〇H/g， 則存在與異氰酸酯硬化劑之交聯降低之傾向，且存在耐濕 熱性降低之虞。而且，若超過l00mgKOH/g，則存在雖然 可表現出老化前之接著力，但於老化後交聯密度變高之傾 向’且存在無法表現出充分之接著力，於其後之耐濕熱性 試驗中接著力進一步降低之虞。 而且，於本發明中，丙烯酸多元醇（A)之玻璃轉移 點（Tg)由於後述之理由而為超過-4〇°C且為1〇乞以下， 更佳的是超過-25°C且為l〇°C以下。 D &lt;聚異氰酸酯（B) &gt; 聚異氰酸酯（B)例如為由周知之二異氰酸酯所衍生 之化合物，可無限制地利用公知之化合物。例如可列舉： 由2,4-甲苯二異氰酸酯（別名：2,4-TDI)、2,6-曱苯二異氰 酸酯（別名：2,6-TDl)、二曱笨二異氰酸酯（別名：XDI)、 二苯基甲烧二異氰酸醋（別名：MDI)、異佛爾_二異氰酸 酯、1,5-萘二異氰酸酯、六亞甲基二異氰酸酯（別名：HDI)、 雙(4-異氰酸酯環己基）曱烧、或氫化二苯基甲烷二異氰酸 201242054 X / Λ. Λ. 爲第101104895號中文說明書無劃線修正本 疋日期:⑼年6月15日 酯等二異氰酸酯所衍生之化合物，亦即所 異氰酸酯體、三羥曱基丙烷加合物體、縮二^異氣酸酷之 氰酸酯殘基之預聚物（由二異氰酸酯與多元型、具有異 合物）、具有異氰酸酯殘基之脲二酮體、脲^所之低聚 該些化合狀複合*、絲段聽_u旨體、或 可單獨使用單-之化合物或者將2種以上組合^酸醋（B) 自交聯後之硬化塗膜之黏彈性之觀點考^^ s紅 醋（B)較佳的是使用由脂環族二異氮酸酉旨:或 異氰酸醋而衍生之聚異氰酸酯。更詳細而言，脂二於一Ί 氰酸醋可列舉異佛爾酮二異氰酸醋、曱基 氰酸酯等。而且，脂肪族二異氰酸酯可列舉六亞甲美一 ^ 氰酸酯、五亞曱基二異氰酸酯等。而且可列舉：作述 之脂環族二異氰酸酯及脂肪族二異氰酸酯化合物之衍生物 的二異氰酸酯之異氰酸酯體、三羥曱基丙烷加合物體、縮 ^脲型、具有異氰酸S旨殘基之預聚物（由二異氰酸醋與多 元醇所得之低聚合物）、具有異氰酸酯殘基之脲二酮體、脲 基曱酸酯體、或該些之複合物等。 而且，於重視硬化速度快慢之情形時，較佳的是使用 如二甲笨二異氰酸酯（別名：XDI)這樣的雖然具有芳香 環，但於NCO與芳香環之間具有伸烷基的異氰酸酯。若 硬化速度快，則於可縮短老化時間之方面而言較佳。 而且，聚異氰酸酯（B)中之異氰酸酯基濃度較佳的 是5 wt%〜30 wt%。聚異氰酸酯（B)中之異氰酸酯基濃 度設為5 wt%〜30 wt%之範圍。另外，聚異氰酸酯 201242054 修正曰期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 中之異亂酸醋基濃度可藉由滴定法而求出。滴定藉由正丁 基胺/鹽酸滴定法而進行評價。具體而言，使試樣溶解於乾 燥甲本中後’添加過剩之二正丁基胺(dibutylamine)溶液而 使其反應，藉由鹽酸而反滴定剩餘之二正丁基胺，將滴定 曲線上之反曲點作為終點，根據直至終點之滴定量而算出 異象i酸醋基含有率。 Ο Ο 聚異氰酸酯（B)之使用量可由源自丙烯酸多元醇（A) 之羥基與源自聚異氰酸酯（B)之異氰酸酯基之nc〇/〇h 當量比而決定，將NCO/OH當量比設為〇1〜3。更佳的是 NCO/OH當量比為1〜3,進一步更佳的是丨5〜3qNC〇/〇h 當量比可使用以下之數學式（1)而求出。 NCO/OH比=聚異氰酸g旨必需量（重量份）χ (56i/〇h 值）x (NC〇%/(42xl00)) x (刚 量））數學式（1) 本發明者等人查明：藉由滿足以下之所 異特性的積層片用接著劑組成物。亦即： 查月藉由滿足如下之所有條件，可提供—種接 (所述接著聽成物於各種片狀部件間、 ^ 膠膜之表面處理層之層間顯示出高的 夬疋；J 濕度環境下亦可維持高的接著力 池用背面保護片）：使用上述之具 二太險電 平均分子量、（ii)特定範圍之雜 ^㈣之數量 轉移溫度㈤的丙_多鱗d1) t範圍之玻璃 自丙_多元醇⑷之雜與源自聚異驗 13 201242054 X / JL. 1 修正日期:101年6月15日 設定為前述之特定範圍。以 爲第1011〇4895號中文說明書無劃線修正本 氰酸酯基之當量比Ν(：〇/〇ΐί 下，對其理由加以說明。 ”積θ表面未喊理之塑軸之^ r電晕放電等對表面進行處理的塑膠膜之情：;，π 製造步驟增加部分之附加價值。於接著力中: 表面未經處理之塑膠膜之情形相比 ：積曰 若丙稀酸多元醇之Tg過低，則老化前二 硬化尚不充分，因此由接著劑組成物所形成之接^ 軟。而且，由於其柔軟程度而可於片狀部件^ 而，於老化後’即使接著劑層充分硬化， 亦由於作為原料之_酸多元醇之Tg低而存在接著劑層 之凝聚力不足變明顯’變得難以確保大的接著力之傾向。曰 另外’若將積層體長時間地置於高溫高濕度下，則存在如 下t傾向.由於縣㈣之凝聚力不足的原“造成接著 力緩緩降低。 另一方面，若丙烯酸多元醇之Tg過高，則存在對基 材之，潤性不足的傾向。雖然老化後之接著力與老化前相 比而言多少有所變大’但交聯後之硬化接著劑層過於變 硬，因此存在老化步驟後之接著力惡化之傾向。 於本發明中，進行研究而得知獲得上述優異效果之理 由是由於：將_酸多元醇之Tg設為並不過低且不過高 之溫度範圍（具體而言為超過_4(rc且為10t:以下），於其 基礎上進一步設為特定之羥值、特定之NCO/OH當量比、 及特疋之數1平均分子量之範圍，藉此而協同地激發分子 修正日期:1〇1年6月15日Example of Polyisocyanate Derived from Diisocyanate or Aliphatic Diisocyanate The laminate for a laminate of the above aspect is used in the production of a back protective sheet for solar cells comprising two or more sheet members, and is suitable for use in the following In use: forming at least a portion of an adhesive layer for joining the sheet members to each other. The back surface protective sheet for a solar cell of the present invention comprises: an adhesive layer formed of two adhesive compositions of the above-described aspect; and at least two or more sheet members laminated with the subsequent tantalum layer. [Effects of the Invention] The present invention provides the following excellent yarns: a laminated composition and a back protective sheet for a solar cell, wherein the interlayer of the laminated film surface treatment layer is particularly useful for containing plastic _High adhesion force, suitable for manufacturing solar cells [Embodiment] 7 201242054 I 1 V·/知/先/ϋ For the 101101895 Chinese manual, no slash correction, this revision period: 1〇1年六丨The embodiments of the present invention will be described in detail below. Further, other embodiments may be included in the scope of the present invention as long as it is the subject of the present invention. Further, in the present specification, the description of "arbitrary number A to any number B" means a range of the number A and the number A, and is a range of the number B and the number B. Further, the description of "(meth)acrylic S&amp;" as described in the specification and the patent application includes any compound which is referred to as "acrylic" and a compound which is referred to as "mercaptopropene". By. Further, it is similarly defined in "(indenyl) propylene group" and "(meth) acrylate". &lt;Acrylic Polyol (A) &gt; The acrylic polyol (A) can preferably be copolymerized with a mono(meth)acrylate monomer containing a trans group and a mono(meth)acrylate monomer having no hydroxyl group. Things. The mono(meth)acrylate monomer having a hydroxyl group is a monomer having 1, (meth)acryloyl group and i or more hydroxyl groups in one molecule. Preferable examples thereof include a mono(methyl)propene-based monomer obtained by a reaction of a divalent alcohol and (meth)acrylic acid, and an ε-caprolactam-modified (fluorenyl)acrylic monomer. Wait. ^The number average molecular weight of the acrylic polyol (4) is the same degree, and the part of the mono(meth)acrylic acid vine monomer is not related to the increase of the bonding force, that is, via the vinegar bond and (methyl) a part of an acrylic acid bond or an alkenyl group. Hereinafter, it is referred to as "side chain portion"), 疋~17, more preferably 1 to 9, and even more preferably 1' said side chain portion forms a side of the acrylic polyol (4) after copolymerization. The carbon number of the side chain portion of the propylene-monomer is generally about eight or three, but if the amount of the acrylic polyol (Α) is equal to the same degree in the knife, the more the side chain portion is. Short, acrylic acid diversity 201242054 ' w I fa I l Revision date · June 15, 15th is the 101104895 Chinese manual without a slash correction The longer the relative length of the chain. As a result, the machine of the adhesive layer after hardening is improved in elongation, and the force is increased. The mono(indenyl)acrylic acid vinegar monomer obtained by the dihydric alcohol can be exemplified by (A, H, H, E, thiophene acrylate, 1,4 butanediol, early (methyl). Acrylic axis, (poly)ethylene glycol mono(indenyl)acrylic acid vinegar, etc. ...in addition: such as (mercapto) propionate 2,3_di-propyl acetoacetate, etc. by 3 〇〇 ^ on ^ Alcohol and deuterated mono(indenyl) acrylate δ oxime monomer can also be used as a mono(indenyl) acrylate monomer containing a trans group. Not 3 &amp; mono mono(methyl) acrylate The g-type monomer can be suitably selected from the above-mentioned "radical polymerizable monomer", and a suitable example I is exemplified by (mercapto) propionate n-butyl vinegar, (meth) acrylic acid isobutyl vinegar ((3rd butyl ketone methacrylate, 2-ethylhexyl methacrylate), (methyl) propyl triacetate, octyl vinegar, (methyl) acrylate, lauryl S, (methyl) A long-chain (fluorenyl) acrylic monomer represented by a (meth)acrylic acid sulfonic acid acetal monomer such as benzoic acid triglyceride = (meth)acrylic acid stearyl vinegar, and acrylonitrile. The above-mentioned (meth)acrylic acid vinegar monomer containing no warp group is not &quot; In addition to the mono(meth)propionate monomer of hydroxy group, hydrazine may copolymerize other monomer (10) such as (meth)acrylic acid, maleic acid, maleic acid, etc., a carboxyl group-containing monomer or an anhydride thereof, or a vinyl monomer such as phenethyl hydrazine, etc. Further, the base (meth)acrylic acid vinegar monomer and the unreported mono (meth)acrylic acid vinegar precursor can be independently used as a compound. Two or more kinds of compounds may be used in combination. The same applies to the case of using other monomers. In the present invention, the number average molecular weight of the acrylic polyol (Α) must be 10, _~100, _. Further, preferably It is 1〇, _ 9 201242054 ~Γ ί KJ ^ / yjki A Correction period: 1〇1年15月15日第1011(Η895号 Chinese manual no-line correction this ~70,000' is better 25, 00〇~5〇,〇〇〇. A laminated sheet obtained by laminating two or more sheet-like members, such as a solar cell, using the laminated sheet transfer agent composition of the present invention (hereinafter also referred to as "adhesive composition") The back protective sheet can be obtained, for example, by the following steps. Among them, a sheet member The bonding surface is coated with the adhesive composition and dried. Secondly, the other sheet-like members are heavy on the adhesive layer, and are stored in the environment of Russia ~ 6 ° ° C for 2 days to 1 week or so. For the step of "aging", the adhesive layer is hardened to obtain a laminated sheet. When the number average molecular weight of the acrylic polyol is 1 〇, _, there is a tendency that the cohesive force of the adhesive layer before the aging step is insufficient. And the adhesive force before the aging step becomes smaller. In the industrial production form, the laminated body wound in a roll shape is normally aged in the vertical direction of the roll. If the aging step is followed by When the force is less than the aging, the winding is easily spread, and it is not suitable for industrial production, and the cohesive force after the aging step is insufficient, and the heat and humidity resistance is lowered, and delamination is caused. Further, if the number of acrylic polyols is evenly divided, 'the viscosity of the adhesive becomes high' is produced in terms of coating properties: the productivity of the two-sheet member is lowered, and as a result, there is an aging + initial adhesion due to aging. However, it is larger than the oxime (1), but it is lower than the lower limit of use after 3000 hours due to the subsequent decrease in resistance to 29; in addition, the number average molecular weight in the present invention is analyzed by 1 Calculated by instrument (GPC), the value of polystyrene conversion is more. 10 201242054A Revision period: June 15, 2011 is the number of the Chinese version of the no. The molecular weight is represented by the thief method described in the example described later, and the value of the _glass miscibility temperature and the NCO/OH equivalent ratio 'is similarly expressed by the method described in the examples described later. The value of the poly(7L) alcohol (A) is determined by the content of the mono(indenyl)acrylic acid acetal monomer containing the trans group (IV), and the intrinsic value is i mgK〇H/g~100 mgKOH/g'. Is mg mg〇H/g~5〇mgK(10)g, more It is 1 mgKOH/g to 15 mgKOH/g. If it is less than i mgK〇H/g, the crosslinking with the isocyanate curing agent tends to decrease, and the heat and humidity resistance is lowered. Moreover, if it exceeds 100 mgKOH/g In addition, there is a tendency that the crosslinking strength before aging is high, but the crosslinking density becomes high after aging, and there is a possibility that a sufficient adhesive force cannot be exhibited, and the subsequent force is further lowered in the subsequent moist heat resistance test. Further, in the present invention, the glass transition point (Tg) of the acrylic polyol (A) is more than -4 〇 ° C and is not more than 1 ,, more preferably more than -25 ° C, for the reason described later. It is below 10 ° C. D &lt; Polyisocyanate (B) &gt; The polyisocyanate (B) is, for example, a compound derived from a known diisocyanate, and a known compound can be used without limitation. For example, 4-toluene diisocyanate (alias: 2,4-TDI), 2,6-nonyl diisocyanate (alias: 2,6-TDl), diterpene diisocyanate (alias: XDI), diphenyl carbaryl Isocyanic acid vinegar (alias: MDI), isophor _ diisocyanate, 1,5-naphthalene diisocyanate Ester, hexamethylene diisocyanate (alias: HDI), bis(4-isocyanate cyclohexyl) oxime, or hydrogenated diphenylmethane diisocyanate 201242054 X / Λ. Λ. No description for the Chinese manual No. 101104895 Line correction date: (9) June 15th, the compound derived from diisocyanate such as ester, that is, the isocyanate, trihydrocarbyl propane adduct, and the cyanate residue a prepolymer (from a diisocyanate to a polybasic, having a complex), a uretdione having an isocyanate residue, an oligomerization of the urea, a compounding compound*, a wire segment, or a The viewpoint of the viscoelasticity of the hardened coating film after self-crosslinking using a single-form compound or a combination of two or more kinds of acid vinegar (B) is preferably used as the alicyclic group (B). Isoindoline: A polyisocyanate derived from isocyanate. More specifically, the lipid is used in the form of isophorone diisocyanate, decyl cyanate or the like. Further, examples of the aliphatic diisocyanate include hexamethylene methacrylate, pentadecyl diisocyanate, and the like. Further, examples thereof include a diisocyanate isocyanate, a trihydrocarbyl propane adduct, a uret-type, and a residue having an isocyanate of the derivative of the alicyclic diisocyanate and the aliphatic diisocyanate compound. a prepolymer (lower polymer obtained from diisocyanate and a polyol), a uretdione having an isocyanate residue, a urea phthalate body, or a composite thereof. Further, in the case where the rate of hardening is emphasized, it is preferred to use an isocyanate having an aromatic ring, such as dimethyl diisocyanate (alias: XDI), having an alkyl group between the NCO and the aromatic ring. If the hardening speed is fast, it is preferable in terms of shortening the aging time. Further, the isocyanate group concentration in the polyisocyanate (B) is preferably from 5 wt% to 30 wt%. The isocyanate group concentration in the polyisocyanate (B) is set in the range of 5 wt% to 30 wt%. In addition, the polyisocyanate 201242054 revised period: June 15th, 1st, 1st, 1st, 10th, 10th, Chinese, No. 101104895, the inconsistency of the acid-free vinegar base can be determined by titration. The titration was evaluated by n-butylamine/hydrochloric acid titration. Specifically, after the sample is dissolved in the dried nail, the excess dibutylamine solution is added and reacted, and the remaining di-n-butylamine is back-titrated by hydrochloric acid, and the titration curve is The inflection point is used as the end point, and the content of the vision i acid vine group is calculated based on the titration to the end point. Ο 聚 The amount of polyisocyanate (B) used can be determined by the ratio of the hydroxyl group derived from the acrylic polyol (A) to the nc〇/〇h equivalent ratio of the isocyanate group derived from the polyisocyanate (B), and the NCO/OH equivalent ratio is set. For 〇1~3. More preferably, the NCO/OH equivalent ratio is 1 to 3, and more preferably, the 丨5 to 3qNC〇/〇h equivalent ratio can be obtained by the following mathematical formula (1). NCO/OH ratio = polyisocyanate g required amount (parts by weight) χ (56i / 〇h value) x (NC〇% / (42xl00)) x (rigid)) Mathematical formula (1) The present inventors, etc. It has been found that an adhesive composition for a laminate sheet which satisfies the following characteristics is obtained. That is to say: by checking all the following conditions, it is possible to provide a kind of connection (the subsequent listening to the object between the various sheet parts, ^ the surface of the surface treatment layer of the film shows a high enthalpy; J humidity In the environment, it is also possible to maintain a high backing force pool back protection sheet): using the above-mentioned two-scale electric weight average molecular weight, (ii) a specific range of miscellaneous ^ (four) quantity transfer temperature (f) of the C-multi-scale d1) t range The glass from the C-polyol (4) miscellaneous and derived from the polygraph 13 201242054 X / JL. 1 Revision date: June 15, 101 set to the aforementioned specific range. It is assumed that the Chinese manual No. 1011〇4895 has no slash correction of the equivalent ratio Ν(:〇/〇ΐί of the present cyanate group, and the reason is explained.) The product of the θ surface is not called the plastic shaft ^ r corona The plastic film treated by discharge, etc.:;, π The added value of the manufacturing step is added. In the adhesion force: Compared with the case of the untreated plastic film: the accumulation of the Tg of the acrylic polyol If it is too low, the second hardening before aging is not sufficient, so that the adhesive formed by the adhesive composition is soft, and because of its softness, it can be applied to the sheet member, and after aging, even if the adhesive layer is sufficiently hardened In addition, since the Tg of the acid polyol as a raw material is low and the cohesive force of the adhesive layer is insufficient, it becomes difficult to ensure a large adhesion force. 曰In addition, if the laminate is placed in a high temperature and high humidity for a long time. In the following, there is a tendency that the cohesive force of the county (four) is insufficient to cause a decrease in the adhesion. On the other hand, if the Tg of the acrylic polyol is too high, the substrate tends to be insufficient in wettability. although The adhesion force after aging is somewhat larger than before aging. However, the hardened adhesive layer after crosslinking is too hard, so there is a tendency that the adhesion force after the aging step is deteriorated. In the present invention, research is conducted. The reason for obtaining the above excellent effect is that the Tg of the _acid polyol is not too low but not too high (specifically, it exceeds _4 (rc and is 10t: or less), on the basis of Further, the range of the specific hydroxyl value, the specific NCO/OH equivalent ratio, and the characteristic number 1 average molecular weight is further set, thereby synergistically exciting the molecular correction date: June 15, 2011 2012420542 爲第1^104895號中文說明書無劃線修正本 運動級別的丙烯酸多元醇之運動的活躍程度，從而使對接 著對象之關性與綱性提高。特別是進行研究而得知藉 由將NCO/OH當量比控制為αι〜3之範圍、特別是卜3 ==現適度之交聯度之平衡且於老化步驟後顯示 出南㈣者力。而且’令人驚訐地發現即使於老化前亦表 現出南的接著力。另外發現：於老化步驟後，於置於高溫 高濕度下之後亦可維持高的接著力。 於使用金屬謂、金屬板、或金屬蒸鍍膜等為基材之情 形時，自使接著強度提高之觀點考慮，較佳的是本發明之 積層片用接著劑組成物含有石夕燒偶合劑。 f烧偶合劑並非限定於以下者，例如可列舉乙稀基三 (β^甲氧基乙氧基)魏、乙稀基乙氧基石夕烧、及乙稀基三 甲氧基魏等乙烯基⑧絲；γ_(甲基)丙烯醯氧基丙基三甲 氧基矽烷、γ:(甲基)丙烯醯氧基丙基三乙氧基矽烷、及ρ(甲 基）丙烯醯氧基丙基二甲氧基甲基魏等（甲基）丙烯醯氧 ^矽，類；ρ-(3,4-環氧環己基）乙基三甲氧基矽炫、ρ_(34_ 環，環己基）甲基三甲氧基矽烧、β_(3,4_環氧環己基）乙基三 乙氧基矽烷、β-(3,4-環氧環己基）甲基三乙氧基矽烷、γ_縮 水，油氧基丙基三甲氧基矽烷、及γ_縮水甘油氧基丙基三 乙氧基矽烷等環氧基矽烷類；Ν_β_(胺基乙基)_γ_胺基丙基 三曱氧基矽烷、Ν-Ρ-(胺基乙基)_γ_胺基丙基三乙氧基矽 烷、N-p-(胺基乙基)_γ_胺基丙基曱基二乙氧基矽烷、丫_胺基 丙基二乙氧基矽烷、γ_胺基丙基三甲氧基矽烷、Ν_苯基_丫_ 胺基丙基三甲氧基矽烷、及Ν•苯基_γ•胺基丙基三乙氧基矽 15 201242054 修正日期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 烷等胺基矽烷類；以及γ_巯基丙基三曱氧基矽烷、及丫_巯 基丙基二乙氧基石夕烧等含硫石夕烧類等。該些化合物可分別 單獨使用或者將2種以上任意組合而使用。 矽烷偶合劑之添加量相對於丙烯酸多元醇（Α) 1〇〇 重^份而δ較佳的是G1重量份〜5重量份，更佳的是i 重量伤〜3重里伤。若不足〇1重量份，則由於添加矽烷 偶cr劑而γ來之對金屬之接著強度提高的效果差；即使 添加超過5重量份’亦存在未魏其以上之性能提高之情 况。 盘；^ j日月之積層片祕著劑組成物可為於使用時將主劑 ΓΐΓΓ以混合的所謂2液混合型接著劑，亦可為預先 多元二硬，加以混合的1液型接著劑。而且，丙烯酸 ，(Α)或聚異氰酸S|(B)亦可各自獨立地使用多種。 -種或ΐϊ以外：其他主劑或硬化劑亦可I自獨立地使用 石夕燒。2情況下，主劑包括丙稀酸Κ醇（Α)、 酸醋⑻、有_卜^^劑，硬化舰括聚異氮 内，： = ==在不脫離本發明之主旨之範圍 劑、均化劑、鱗“=調配增黏劑、反應促進 屬減活劑、阻_、塑化化劑、紫外線穩定劑、金 添加劑。 有機顏料、無機顏料等各種 於使用金屬層（金屬箔、 情形時’為了使本發明之軸作為片狀部件之 、增片用接者劑組成物之金屬密 201242054 α λ- mm t ^ X 修正日期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 接性提高，可添加磷酸系化合物，例如磷酸' 偏磷酸、焦 磷酸、亞磷酸或該些酸之酯等。 而且，本發明之接著劑組成物除了作為用以製造太陽 電t用月面保護片之接著劑而較佳地使用以外，亦可作為 太％電池積層片用增黏塗層劑而使用。於此情形時，較佳 的是放入防結塊劑。 〇 〇 另外，可於不脫離本發明之主旨之範圍内無限制地調 配作為接著劑用途而公知之添加劑。例如可使用反應促進 劑。具體而言可列舉二乙酸二丁基錫、二月桂酸二丁基錫、 桂酸二辛基錫、二馬來酸二丁基錫等金屬系觸媒；1，8-^亂雜-雙環[…]十一碳稀―7、氮雜雙環旧力]壬稀 、6·—了基胺基_18_二氮雜雙環[5 4 〇]十一碳烯等三級 ，如二乙醇胺這樣的反應性三級胺等。反應促進劑可 用1種或將2種以上併用使用。 另外，為了使層壓外觀提高，亦可於主劑中調配公知 之均化劑或消泡劑。 m例如可列舉賴改質聚二曱基魏境、聚醋改 改質=3氧燒、芳烧基改質聚甲基絲錢燒、聚酉旨 石夕基來二甲基矽氧烷、聚醚酯改質含羥基聚二甲美 改ΐΐ甲系共聚物'甲基丙稀醯基系共聚物、聚二 酸燒基匕、丙稀酸烧基si共聚物、甲基丙稀 劑。a^、聚物、卵磷脂、或該些之混合物等公知之均化 消泡劑可列舉矽_樹脂 、石夕酮溶液、烧基己埽義喊與 17 201242054 _ ..........i 修正日期謂年6月15日 爲第101104895號中文說明書無劃線修正本 〜十〇月ί5日 丙稀酸絲酯與f基丙舰絲§|之共㈣ 合物等公知之消_。於添加均化劑 之混 =;::使一物亦可將2種二:意 :，由於太陽熱等熱所造成之 化，可於主劑中調配公知之磷系或酚 、:過之頁 線穩定劑、金屬減活劑。該些添加 訓：紫外 2種以上任意組合而使用。本發明中所亦可將 之抗氧化劑、紫外線穩定劑、金屬減活 ^ (A) 100 〇；〇^S- 5重置份之範圍，更佳的是〇1重量份〜 重里知 加量不足0.05重量份，則存在盔法_ 置知。若添 果之虞;若多於5重量份，則; 度地惡化之虞。 子在使接讀之接著力大程 作為硬化劑，除了上述聚異氮酸酿 在不阻礙本發日狀效果的範_ 卜^可以 化合物（例如2,5_二甲基_2+料、之射琳 雙(2-噁唑啉））或醯肼化合物（例如間笨二離伸丁基)_ 癸二酸二醯肼、或己二酸二醯肼）等。—-欠二醯肼、 本發明中所使用之溶劑，例如可列m 丁酷、乙酸賽路蘇等醋類；丙納、丁嗣、里、乙酸 異丁基_、環己酮等酮類·’四氫咳喃、二贼二類甲f 18 201242054 «aw mm I ^ a a. ^ 爲第觀嶋號中文說鴨無劃線修正本 修正日獅丨年6月15臼 苯=甲苯等芳香族煙類；二氣曱烧、U-二氯乙烧等南 代煙類，一曱基亞石風、二甲基礦酿胺等。所使用的溶劑可 使用1種溶劑，亦可將2種以上任意組合而使用。 本毛明之接著劑之不揮發成份（固形物）較佳的是1〇 Wt%〜5〇 Wt%之範圍。本接著劑可使用如上述所例示之溶 劑而進行固形物之調整。 ο 、其-人’對製造使用本發明之積層片用接著劑組成物而 $的太陽電池用#面保護片之方法、及太陽電池用背面保 ί = = 2說明。另外，太陽電池用背面保護片之製 1方，或構成並不限定於以下之例，可根據目的或需要而 採用各種各樣之製造方法或構成。 太陽3太：電池模組，單純的太陽電池模組具有在作為 ，= 陽電池單元的兩個面順次積層有填充劑 板的構成形態。玻璃板之透明性、耐候性、耐擦傷 Ο =片、’it現在亦一般用作太陽電池模組之受光面側的 Π 無需透明性之非受光面侧，自成本或安 慮，由各公司開發玻璃板以外之太 以下稱為背面輪)，該些背面保 2陽電池用背面賴片存在有積層有如下者之太 ，用背面保護片：聚_等_膜、於聚_等上 I ^ ^ ^ ^ ^ « 膜鋁/白·#金屬泊、附有氮化石夕層之塑 各片狀部件間可使用本發明之積層片用接著= 19 201242054 爲第101HM895號中文說明書無劃線修正本 修正曰期:101年6月15 臼 行接合。多層構成之太陽電池用背面保護片可藉由該多屉 結構而賦予各種性能。例如可藉由使用聚酯膜而賦予絕^ 性，藉由使用氟系膜而賦予耐候性，使用鋁箔而職予水摹 氣阻障性。至於使用何種太陽電池用背面保護片，可根摅 使用太陽電池模組之產品、用途而適宜選擇。 K 塑膠膜例如可列舉聚對笨二曱酸乙二酯、聚對笨二 酸萘二S旨等之聚g旨系樹賴，聚乙_樹脂膜，聚 樹脂膜’聚氣乙烯系樹脂膜，聚碳_旨系樹脂膜㈣ 樹脂膜，聚（曱基)丙烯酸系樹脂膜，聚敦乙稀、聚偏二翁 乙f 2氯三氟乙烯、聚乙烯四氟乙烯、聚四氟乙烯二 等之氟系樹脂膜等。 鼠丙婦，、♦物 李塗些塑膠膜作為支撐體並塗佈丙稀酸系、氟 ^甲酸㈣接著劑料積層多個上__喊之;；= 成易宜g:;對表面進行如下處理而製 理，於膜表面_彳^/制表面進行改質的化學性處 的褪光加I等。，、田凹凸’使其成為所謂之權皺狀態 成物適用:表面處理之積層片用接著劑組 屬白刊舉料或銅。作為所蒸鍍之金屬氧化物 20 201242054 _____ __1 爲第101104895號中文說明書無劃線修正本 修正日期:101年6月丨5日 或非金屬無機氧化物例如可使 納、硼、鈦、鉛、锆、釔等之氧二鋁、鎂、鈣、鉀、錫、 之：中滿電池模組而使用時 作，等=積層有=溫度具有耐受 〇 膜萘二顆等聚I系樹脂膜、聚竣酸酯 糸树月曰膜而成的太陽電池用背面保護片 = 池單元由於水之影響而造成的輸出降低，較佳的是積2 具有水蒸氣阻障性之蒸鍛有金 層有 ? ΐΤΓίΓ丄'而成的太陽電池用背面保護 化所產生之外觀不良;較佳的是積 ^有」、!·生良好之氟系樹脂膜而成的太陽電池用背 片。 向且2012420542 For the Chinese manual No. 1^104895, the activity level of the exercise-grade acrylic polyol is corrected without the underline, so that the relevance and the nature of the docking object are improved. In particular, it was found that the NCO/OH equivalent ratio was controlled to be in the range of αι to 3, in particular, the balance of the degree of crosslinking of the current level of 3 == and the south (four) force was exhibited after the aging step. Moreover, it was surprisingly found that even before aging, the south's adhesion was exhibited. It has also been found that after the aging step, a high adhesion can be maintained after being placed under high temperature and high humidity. In the case where a metal, a metal plate, or a metal vapor-deposited film is used as the substrate, it is preferable that the adhesive composition for a laminated sheet of the present invention contains a sulphur-burning coupler from the viewpoint of improving the adhesion strength. The f-coupling agent is not limited to the following, and examples thereof include vinyl 3 (β methoxyethoxy) Wei, ethylene ethoxy oxy-stone, and vinyl 8 such as ethylene trimethoxy Wei. Silk; γ-(methyl) propylene methoxy propyl trimethoxy decane, γ: (meth) propylene methoxy propyl triethoxy decane, and ρ (methyl) propylene methoxy propyl dimethyl Oxymethylmethyl and the like (methyl) propylene oxime, ph-(3,4-epoxycyclohexyl)ethyltrimethoxy fluorene, ρ_(34_cyclo,cyclohexyl)methyltrimethoxy Base calcined, β_(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane, γ-shrink, oleyloxy Ethyl trimethoxy decane, and epoxy decanes such as γ-glycidoxypropyl triethoxy decane; Ν_β_(aminoethyl)_γ-aminopropyltrimethoxy decane, Ν-Ρ -(Aminoethyl)_γ-aminopropyltriethoxydecane, Np-(aminoethyl)_γ-aminopropylmercaptodiethoxydecane, 丫-aminopropyldiethoxy Baseline, γ-aminopropyltrimethoxydecane, Ν_phenyl_丫_aminopropyl three Oxydecane, and phenyl phenyl γ-aminopropyl triethoxy hydrazine 15 201242054 Revision date: June 15, 2011 is the 101101895 Chinese manual without a slash correction of the amino decane such as the alkane And γ-mercaptopropyltrimethoxy decane, and sulfonium-containing sulphur-like smoldering such as 丫_mercaptopropyldiethoxy zeshi. These compounds may be used singly or in combination of two or more kinds. The amount of the decane coupling agent to be added is preferably 1 part by weight to 5% by weight based on the weight ratio of the acrylic polyol (Α), and more preferably the weight of the weight is 〜3 weight loss. When the amount is less than 1 part by weight, the effect of γ on the adhesion strength of the metal is inferior due to the addition of the decane-coupled cr agent, and even if the addition exceeds 5 parts by weight, there is a case where the performance is not improved. The composition of the layered tablet of the sun and the moon may be a so-called two-liquid mixed type adhesive which mixes the main agent during use, or may be a one-component type adhesive which is mixed in advance and multi-hardened. . Further, acrylic acid, (Α) or polyisocyanic acid S|(B) may be used independently of each other. - Other than species or sputum: Other main agents or hardeners may also be used independently from Shi Xi. In the case of 2, the main agent includes sterol oxime (Α), vinegar (8), _ _ _ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Homogenizer, scale "= blending tackifier, reaction promotion is a deactivator, resistance _, plasticizer, UV stabilizer, gold additive. Organic pigments, inorganic pigments, etc. in various metal layers (metal foil, case) When the shaft of the present invention is used as a sheet member, the metal seal of the composition of the splicer is used. 201242054 α λ- mm t ^ X Revision date: June 15, 2011 is the Chinese manual No. 101104895 There is no scribe line correction, and a phosphate compound such as phosphoric acid 'phosphoric acid, pyrophosphoric acid, phosphorous acid or an ester of these acids, etc. can be added. Moreover, the adhesive composition of the present invention is used for manufacturing solar power. It is preferably used as a tackifying coating agent for a solar cell laminate sheet. It is preferably used as an anti-caking agent in the case of using an adhesive for a lunar surface protective sheet. In addition, without departing from the gist of the present invention A known additive is used as an adhesive for the purpose of the adhesive. For example, a reaction accelerator can be used, and specific examples thereof include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin laurate, and dimaleic acid. a metal-based catalyst such as butyltin; 1,8-^-hetero-bicyclic [...] eleven carbon thinner -7, azabicyclopropene] 壬,6·-ylamino _18_diazabicyclo[ 5 4 〇] a three-stage such as undecene, a reactive tertiary amine such as diethanolamine, etc. The reaction accelerator may be used alone or in combination of two or more. In addition, in order to improve the appearance of the laminate, A well-known leveling agent or defoaming agent is blended in the main agent. For example, a modified polydifluorenyl group, a polyacetate modified medium = 3 oxygen burned, an aromatic burned base modified polymethyl silk burned,酉 酉 石 石 石 来 二 二 、 、 、 、 、 、 、 、 、 、 、 、 、 、 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 聚醚 ' ' Dilute acid-based i copolymer, methyl propylene agent, a ^, a polymer, lecithin, or a mixture of these, such as known homogenization defoaming agents can be cited 矽Resin, lithene ketone solution, burning base has been shouted with 17 201242054 _ ..........i Amendment date is June 15th is the 101101895 Chinese manual no line correction this ~ 十〇 On the 5th of the month, the acrylic acid ester and the f-based propyl ship §| the total (four) compound and other known _. Add the homogenizing agent mixed =;:: one thing can also be two kinds of two: meaning: Due to the heat caused by the heat of the sun, a known phosphorus-based or phenol, a sheet-line stabilizer, or a metal deactivator can be blended in the main agent. These additions are used in combination of two or more kinds of ultraviolet rays. In the present invention, the antioxidant, the ultraviolet stabilizer, the metal may be deactivated (A) 100 〇; the range of the 重置^S-5 replacement portion, more preferably 〇1 part by weight 0.05 parts by weight, there is a helmet method _ know. If the result is more than 5 parts by weight, then it will deteriorate. In order to make the subsequent force of the reading as a hardening agent, in addition to the above-mentioned polyisocyanic acid, the compound can be compounded (for example, 2,5-dimethyl_2+ material, which does not hinder the daily effect of the hair. The cedar bis(2-oxazoline) or hydrazine compound (for example, bismuth dibutyl butyl) _ azelaic acid dioxime or diammonium adipate). --Under hydrazine, the solvent used in the present invention, for example, vinegar such as butyl acetonide or celecoxib acetate; ketones such as propane, butyl sulfonium, lye, isobutyl acetate, and cyclohexanone · 'Tetrahydrogen cough, two thieves, second class A, f 18 201242054 «aw mm I ^ a a. ^ For the first nickname Chinese said that ducks are not underlined to correct this amendment, the day of the lion, June 15 臼 benzene = toluene, etc. Aromatic cigarettes; second-generation smoldering, U-dichloroethane-sintering and other southern-generation smog, one-base kiya stone, dimethyl ore and amine. The solvent to be used may be one type of solvent, or two or more types may be used in combination. The non-volatile component (solid content) of the adhesive of the present invention is preferably in the range of 1 〇 Wt% 〜 5 〇 Wt%. The present adhesive can be adjusted by using a solvent as exemplified above. ο, the person-person's method for manufacturing the solar cell using the #layer protective sheet using the adhesive composition for laminated sheets of the present invention, and the solar cell back surface = = 2. In addition, the configuration of the back surface protective sheet for a solar cell is not limited to the following examples, and various manufacturing methods or configurations can be employed depending on the purpose or necessity. Sun 3: Battery module, a simple solar cell module has a configuration in which a filler plate is sequentially laminated on both surfaces of a positive and a negative battery unit. The transparency, weather resistance, and scratch resistance of the glass plate = sheet, 'it is now also generally used as the light-receiving side of the solar cell module. The non-light-receiving side without transparency is required, and the cost is from the company. The development of glass plates other than the following is called the back wheel), the backside of the 2 positive battery for the backside of the sheet has a layer of the following is too much, with the back protective sheet: poly _ _ film, on the poly _, etc. ^ ^ ^ ^ ^ « Membrane aluminum/white·# metal mooring, plastic sheet with nitriding layer, can be used between the various sheet-like parts of the invention. Then, the laminated sheet of the present invention can be used = 19 201242054 This revision period: June 15, 101. The multi-layered back surface protective sheet for a solar cell can impart various properties by the multi-drawer structure. For example, it is possible to impart durability by using a polyester film, impart weather resistance by using a fluorine-based film, and use an aluminum foil to impart water vapor barrier properties. As for the type of back surface protection sheet for solar cells, it is suitable to use the product and use of the solar cell module. The K plastic film may, for example, be a poly(ethylene terephthalate) or a poly(p-dibenzoic acid naphthalene), or a poly(ethylene resin film) or a poly resin film 'polyethylene vinyl resin film. , Polycarbonate_Resin film (4) Resin film, poly(fluorenyl) acrylic resin film, Polydene, Polyprene, F 2 chlorotrifluoroethylene, Polytetrafluoroethylene, Polytetrafluoroethylene A fluorine-based resin film or the like. Rats and women, ♦ material Li coated some plastic film as a support and coated with acrylic acid, fluorine ^ formic acid (four) adhesive material layer on a number of __ shouting;; = Cheng Yiyi g:; The treatment is carried out as follows, and the surface of the film is modified to have a chemical modification at the surface of the film. , ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, As the vapor deposited metal oxide 20 201242054 _____ __1 is the 101104895 Chinese manual without a slash correction. Amendment date: June, 丨 5, or non-metallic inorganic oxides such as nano, boron, titanium, lead, Oxygen-aluminum, magnesium, calcium, potassium, tin, etc. of zirconium, hafnium, etc.: when used in a full battery module, etc., etc. = layered = temperature has a poly-type I resin film that is resistant to two layers of phthalocyanine, Back surface protective sheet for solar cell made of polyphthalate eucalyptus eucalyptus film = output reduction of pool unit due to water influence, preferably product 2 steam-forged gold layer with water vapor barrier property The solar cell made of ΐΤΓ Γ丄 Γ丄 外观 外观 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To 保護片為了保護太陽電池模組 免^於《施加所造成之破損，根據域電池單元之發 電谷錄賴由要求部分放電電壓為 V或1_ V j受性的電氣絕緣性或者包含發泡層*使部分放電電壓 提南之構成。作為使部分放電t壓提高的方法的電氣絕緣 性，依存於膜或發泡層之厚度，@此存在膜或發泡層成為 壓膜之傾向。於最近，多採用使用⑽㈣〜獅叫左右 者之構成。 接著劑層之形成例如是藉由缺角輪塗佈機（c〇mma coater)或乾式貼合機將接著劑組成物塗佈在其中 一個塑膠 膜等之片狀部件之單面上，使溶贿發後，與另一個層壓 21 201242054 • Λ , ^Λ,Λ. ΐ 修正曰期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 基材貼合，於常溫或加溫下使其硬化而獲得。或者可藉由 如下方式而製造：於任意-個片狀部件上塗佈接著劑組成 物而進行加熱硬化，形成接著劑層後，塗佈其他之片狀部 件形成用塗液，藉由熱或活性能量線而形成其他片狀部 件。作為將接著劑組成物塗佈於片狀部件上之裝置，可列 舉缺角輪塗佈機、乾式貼合機、刀輕塗佈機、模塗機、輕 塗機、棒式塗佈機、凹版輥式塗佈機、反向輥塗機、到刀 ^機（blade coater)、凹板印刷塗佈機、微型凹板塗佈機 f壓基材表面所塗佈之接著劑量以乾燥換算計而 2 —的是Μ W〜50咖2左右。更佳的是W〜 ，層壓基材’可_用途而以任意數選擇 ^思基材，於設為3層以上之多層構成時，可於各声之 &amp;之全部或-部分中使用本發明之接著劑組成物。曰、 中使部件形成用塗液，可列舉可於塑膠膜之形成 :Γ:卿旨溶液、聚乙烯系樹脂溶液、聚丙烯系 树W液、聚氣乙烯系樹脂溶液、聚糸 聚颯系樹脂溶液、聚（甲某）丙烯舻会I -曰糸树月曰〉谷液、 溶液等作為較佳例）版系樹脂溶液、氟系樹脂 可考慮作為太陽電池用背面保護 2以=性等，選擇各種製造方法或者進-步將該= 《實例》 以下，藉由實例對本發明加以更 之實例並不對本發明之權力範圍作任何限7另月外但冗 22 201242054 爲第101104895號中文說明書無劃線修正本 修正日期:丨〇丨年6月〗5日 中之各評價依照下述方法而進行。另外，於實例中，份表 示重量份，％表示wt%，羥值表示mgK〇H/g。數量平均分 子量、玻璃轉移溫度、羥值可藉由如下方式而求出。 &lt;數量平均分子量&gt; 數量平均分子量之測定使用東曹公司製造之GPC (凝 膠滲透層析儀）「HPC-8020」，管柱使用SHODEXKF-806L 2根、KF-804L 1根、KF-802 1根，溶劑使用四氫呋喃。 〇 數量平均分子量可藉由標準聚苯乙烯換算而求出。 &lt;玻璃轉移溫度（Tg) &gt; 玻璃轉移溫度（Tg)之測定可使用精工電子股份有限 公司製造之DSC「RDC220」而進行。於鋁銷中量取約mg 之藉由下述手法而合成之丙稀酸多元醇〜丙烯酸多元 醇A-21溶液乾燥而成之試樣，裝置於Dsc裝置中而以液 氮冷卻至-100C後，根據以10°C/min進行升溫而所得之 DSC圖而求出玻璃轉移溫度。 3 &lt;羥值&gt; 羥值可藉由如下方式而求出：將約2 g之試樣溶解於 約10 ml之吡啶中之後，加入預先製備之乙酸酐/π比啶之體 積比為15/85的混合溶液5 ml ’放置20小時。盆後，加入 水1 ml與乙醇1〇 m卜藉由〇.1 N之氫氧化鉀（乙醇溶液） 進行滴定而求出。指示劑使用盼酞。 &lt;丙烯酸多元醇（A)之製造&gt; (合成例1)於具有冷凝器、氮氣導入管、滴液漏斗、 及溫度計之4 口燒瓶中裝入乙酸乙酯100重量份，升溫至 23 201242054 修正曰期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 斗以2小時滴力口將丙稀酸丁㈣.7 丨份、及偶氮雙異丁基腈2:ί量 單體液體。其後使⑽小時，ί=:;= 腈0·2重量份使其反應i小時’進行如上之步驟直至單體 之轉化率成為98%以上，然後加以冷卻。繼而，加入乙酸 乙酯而獲得固形物為50%之溶液。 (合成例2〜合成例21)藉由聚合起始劑偶氮雙異 丁基腈之添加量而調節分子量’除此以外與合成例1同樣 地進行而獲得表1中所示之合成例2〜合成例21之丙烯酸 多元醇。另外，關於合成例17 ’是於專利文獻2中作為合 成例1而表示之組成的丙烯酸多元醇。另外，表1中之簡 稱如下所述。 BA :丙烯酸丁酯、EMA :曱基丙烯酸乙醋、EA :丙 烯酸乙酯、St:苯乙烯、CHMA:甲基丙烯酸環己酯、2EHA: ^酸-2上基己5旨、HEA :丙雜_2_減乙_、侧A : _gM-_TSI、HEMA:甲基丙稀酸經基乙醋 24 201242054 爲第101104895號中文說明書無畫臟修正本 修正臼期:101年6月15曰 [表1] 單體組成 數量平 均分手 量 Tg (°C) 經值 (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA HEMA A-1 47.2 51.0 1.8 10000 5 8.6 A-2 47.2 51.0 1.8 35000 5 8,6 A-3 47.2 51.0 1.8 60000 5 8.6 A-4 56.2 42.0 1.8 35000 -5 8.6 A-5 60.7 37.5 1.8 35000 -15 8.6 A-6 71.2 27.0 1.8 35000 -25 8.6 A-7 47.0 50.0 3.0 35000 -5 14.5 A-8 47.6 51.5 0.9 35000 -5 4.3 A-9 47.3 52.3 0.4 35000 -5 2.1 A-10 47.6 51.5 0.9 35000 -5 4.3 ~ A-11 40.3 50.0 10.7 35000 -5 51.6 A-12 39.0 45.0 16.0 35000 -5 ΊΊΑ A-13 48.3 40.6 10.0 1.1 35000 -5 4.3 A-14 44.7 53.5 1.8 35000 10 8.6 ~~' A-15 38.0 60.2 1.8 35000 5 8.6 A-16 47.0 51.0 2.0 35000 5 8.6 A-17 70.0 10.0 10.0 10.0 25000 55 483 A-18 47.6 51.5 0.9 6000 -5 4 3 ' A-19 47.6 51.5 0.9 150000 -5 4 3~ A-20 95.0 4.1 0.9 35000 -50 4 3 ^ A-21 35.0 42.0 23.0 35000 -5 Γϊα〇~^ &lt;接著劑組成物之調配例&gt; (實例1〜實例17、比較例1〜比較例6)相對於以 Ο 固形物換算計而言為1〇〇重量份之作為主劑的丙烯酸多元 醇（A)，以表2中所示之調配比而調配作為硬化劑之聚異 氰酸酯（B)’且調配作為添加劑之含有縮水甘油基之石夕燒 偶合劑（「KBM-403」信越化學公司製造）3 〇重量份、= 二月桂酸二辛基錫（「NEOSTANNU-810」、日東化成公司 製造）0.01重量份，進一步以乙酸乙酯將固形物調整為 25 201242054 爲第101104895號中文說明書無劃線修正本 修正日期:101年6月15日 [表2] 希酸多元酵 -(A) 聚異氰酸酯（B) 數量平均 分子量 Tg (°〇 經值 (mgKOH/g) 種類 NCO/OH 比 調配比 實例1 A-1 10000 5 8.6 硬化劑A 2.0 10.2 實例2 A-2 35000 5 8.6 硬化劑A 2.0 10.2 實例3 A-3 60000 5 8.6 硬化劑A 2.0 10.2 實例4 A-4 35000 -5 8.6 硬化劑A 3.0 15.3 實例5 A-5 35000 -15 8.6 硬化劑A 3.0 15.3 實例6 A-6 35000 -25 8.6 硬化劑B 3.0 10.1 實例7 A-7 35000 —1 — -5 14.5 硬化劑B 3.0 17.0 實例8 A-8 35000 -5〜 4.3 硬化劑B 3.0 5.0 實例9 A-9 35000 -5 2.1 硬化劑B 3.0 2.5 實例10 A-10 35000 -5 4.3 硬化劑B 1.2 2.0 實例11 A-10 35000 -5 4.3 硬化劑C 3.0 8.0 實例12 A-11 35000 -5 51.6 硬化劑c 1.2 38.6 實例13 A-12 35000 -5 77.4 硬化劑C 0.5 24.1 實例14 A-13 35000 -5〜 4.3 硬化劑C 3.0 8.0 實例15 A-14 35000 10 8,6 硬化劑A 2.0 10.2 實例16 A-15 35000 「5 8.6 硬化劑A 2.0 10.2 實例17 A-16 35000 5 8.6 硬化劑A 2.0 10.2 比較例1 A-17 25000 55 48.3 硬化劑D 0.5 8.0 比較例2 A-18 6000 -5 4.3 硬化劑A 3.0 7.7 比較例3 A-19 150000 -5 4.3 硬化劑A 3.0 Ί·Ί 比較例4 A-20 35000 -50 4.3 硬化劑A 3.0 7.7 比較例5 A-21 35000 -5 110.0 硬化劑A 0.5 ^1 32.7 比較例6 A-8 35000 -5 4.3 硬化劑A 12.0 30.7 *1調配比=主劑：硬化劑（固形物比） *2相對於（A) 100重量份(不揮發成份）而言，調配(矽烷偶合劑）3.0重量份。 *3相對於（A) 100重量份(不揮發成份）而言，調配仏⑽⑽丨重量份作為反應促進劑。 ^4硬化劑A : Takenate D-160N (三井化學公司製造、六亞甲基二異氰酸酯之TMP加合物改 質物） ΐϋ! 2: lakfnateD-178N (三井化學公司製造、六亞甲基二異氰酸醋之腺基甲酸醋改質物） 硬化劑C 異佛爾酮二異氪酸酯之異氰尿酸酯改質物 =匕劑D . SumidurN3200 (Sumika Bayer Urethane製造、六亞甲基二異氰酸酯之縮二脲改質 物） &lt;積層膜1之製作例&gt; 使用實例1〜實例17、及比較例1〜比較例6之各接 著劑組成物，以乾燥塗佈量成為4 g/m2〜5 g/m2之量而藉 由乾式貼合機將接著劑組成物塗佈於聚酯膜[東麗公司製 26 201242054 修正曰期:1〇1年6月15日 爲第101104895號中文說明書無劃線修正本 造、Luminm X-10S、厚度為5〇 μιη]之電暈處理面。繼而， 使溶劑揮發後，層壓於另i枚聚酯膜[東麗公司製造、 Lumirror X-10S、厚度為50 μιη]之電暈處理面上。其後， 於4〇t下進行3天之硬化處j里（老化），由此使接著劑 化而製作積層膜1。 &lt;積層膜2之製作例&gt; 使用實例1〜實例4、及比較例！〜比較例3之接著劑 0 組成物，依照前述積層膜1之製作法，製作成為[電暈處理 聚酯膜/接著劑層/鋁箔]之構成的積層膜2。 &lt;積層膜3之製作例&gt; 使用實例1〜實例4、及比較例1〜比較例3之接著劑 組成物，依照丽述積層膜丨之製作法，製作以二氧化矽蒸 鍍聚醋膜之蒸鑛層與接著劑層相接之方式而成為[電晕^ 理聚醋膜/接著劑層/二氧化石夕蒸鏟聚醋膜]之構成的積層犋 3 ° 、 於表2、表3中表示實例1〜實例17、比較例1〜比較 〇 例6中之主劑與硬化劑之組合，以及積層膜1之初始接著 力與於85°C、濕度85%之環境下暴露1000小時、2_小 時、及3000小時後之接著力。 ‘而且’於表4、表5中表示使用實例1〜實例4、比較 例。1〜比較例3之積層膜2、積層膜3之初始接著力與於 85c、濕度85%之環境下暴露1〇〇〇小時、2〇〇〇小時 '及 3000小時後^接著力。以下對具體之評價方法加以說明。 〈老化前、老化狀接著力試驗〉 27 201242054 修正日期:101年6月丨5日 爲第1011048%號中文說明書無劃線修正本 將老化減老化後之所述積層膜1、積層膜2、積層棋 3分別切斷為200 mmx15 _之大小，於坑、渴度 之環境下靜置6小日後，依據ASTM_m876_6i :試驗法 而使用拉伸試驗機，於机、濕度65%之環境下，以負栽 速度為300 mm/min而進行τ型剝離試驗。以5個試 平均絲示PET膜/PET膜間、PET膨郎間、ρΕτ膜/ 二乳化矽蒸鍍聚酯膜間之剝離強度（N/15mm寬）。 &lt;耐濕熱性試驗後之接著力試驗&gt; 將老化後之所述積層體分別切斷為2〇〇 mmxl5 mm之 大小，於85。〇、濕度85%之環境下靜置1〇〇〇小時、2〇〇〇 小時、3000小時。其後，於坑、濕度65%之環境下靜 置6小時後’依據ASTM_D1876_61之試驗法而使用拉伸 試驗機’於25t、濕度65%之環境下，以負载速度為· mm/min而進行τ型剝離試驗。以5個試片的平均值表示 PET膜/PET膜間、PET膜/紹箔間、PET膜/二氧化石夕蒸鍍 聚酯膜間之剝離強度（N/15 mm 寬）。 &lt;評價基準&gt; [老化前之接著力試驗] ◎於實用上優異：3 N/15 mm以上 〇實用區域：2 N/15 mm〜3 N/15 mm △實用下限：1 N/15 mm〜2 N/15 mm x不能實用：不足1 N/15 mm [老化後之減驗、财濕熱性試驗後之接著力試驗] ◎於實用上優異：5 N/15 mm以上 28 201242054 爲第101104895號中文說明書無劃線修正本修正曰期:101年ό月15曰 〇實用區域：4 N/15 mm〜5 N/15 mm △實用下限：2N/15 mm 〜4 N/15 mm x不能實用：不足2 N/15 mmIn order to protect the solar cell module from damage caused by the application, the protective film according to the power generation of the domain battery unit is required to have a partial discharge voltage of V or 1_V j to be electrically insulated or to contain a foamed layer* The partial discharge voltage is made up. The electrical insulation of the method for increasing the partial discharge t pressure depends on the thickness of the film or the foam layer, and there is a tendency that the film or the foam layer becomes a film. Recently, the use of (10) (four) ~ lions around the composition is used. The formation of the layer is carried out, for example, by applying a composition of the adhesive to one side of a sheet member such as a plastic film by a chamfer coater or a dry laminator to dissolve After bribery, laminate with another 21 201242054 • Λ , ^Λ, Λ. 曰 Correction period: January 1st, 1st, June 15th, No. 101104895 Chinese manual without sizing correction of the substrate, at room temperature Or obtained by hardening it under heating. Alternatively, it can be produced by applying an adhesive composition to any of the sheet-like members and heat-hardening to form an adhesive layer, and then applying other coating materials for forming a sheet-like member by heat or The active energy rays form other sheet-like members. Examples of the apparatus for applying the adhesive composition to the sheet member include a knurling wheel coater, a dry laminator, a knife coater, a die coater, a light coater, and a bar coater. The gravure roll coater, the reverse roll coater, the blade coater, the gravure coater, and the micro gravure coater f are applied to the surface of the substrate to be dried. And 2 - is Μ W ~ 50 coffee 2 or so. More preferably, W~, the laminated base material can be selected by any number of substrates, and when it is composed of three or more layers, it can be used in all or part of each sound &amp; The adhesive composition of the present invention. Examples of the coating liquid for forming a component of a crucible or a medium include a plastic film, a polyethylene resin solution, a polypropylene resin W liquid, a polystyrene resin solution, and a polyfluorene polymerization system. A resin solution, a poly(A) propylene oxime I, a eucalyptus, a gluten solution, a solution, etc., as a preferred example) a plate-type resin solution or a fluorine-based resin can be considered as a back surface protection for solar cells 2 </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; There is no slash correction. The date of this revision: each of the evaluations on the 5th of June of the following year is carried out according to the following method. Further, in the examples, parts represent parts by weight, % means wt%, and hydroxyl number means mgK〇H/g. The number average molecular weight, the glass transition temperature, and the hydroxyl value can be obtained by the following methods. &lt;Quantum average molecular weight&gt; The number average molecular weight was measured by GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation, and two columns of SHODEXKF-806L, KF-804L, and KF- were used for the column. 802 1 and the solvent used tetrahydrofuran.数量 The number average molecular weight can be determined by standard polystyrene conversion. &lt;Glass transfer temperature (Tg) &gt; Measurement of the glass transition temperature (Tg) can be carried out using DSC "RDC220" manufactured by Seiko Instruments Inc. A sample of about 100 mg of an acrylic polyol-acrylic polyol A-21 solution synthesized by the following method was weighed in an aluminum pin, and was placed in a Dsc apparatus and cooled to -100 C with liquid nitrogen. Thereafter, the glass transition temperature was determined from the DSC chart obtained by heating at 10 ° C/min. 3 &lt;Hydroxyl value&gt; The hydroxyl value can be determined by dissolving about 2 g of the sample in about 10 ml of pyridine, and adding a previously prepared volume ratio of acetic anhydride/π-pyridine to 15 /85 mixed solution 5 ml 'Place for 20 hours. After the pot, 1 ml of water and 1 〇 m of ethanol were added and titrated by potassium hydroxide (ethanol solution) of N1 N to obtain. The indicator is used in the hope. &lt;Production of Acrylic Polyol (A)&gt; (Synthesis Example 1) 100 parts by weight of ethyl acetate was placed in a 4-necked flask equipped with a condenser, a nitrogen gas introduction tube, a dropping funnel, and a thermometer, and the temperature was raised to 23 201242054 Amendment period: 1st, 1st, 1st, June 15th, the Chinese manual No. 101104895, no underline correction, the bucket will be butyl bis(4).7 丨, and azobisisobutyronitrile 2 in 2 hours. : ί quantity of monomer liquid. Thereafter, (10) hours, ί = :; = nitric acid 0. 2 parts by weight was allowed to react for 1 hour. The above steps were carried out until the monomer conversion became 98% or more, and then cooled. Then, ethyl acetate was added to obtain a solution in which the solid content was 50%. (Synthesis Example 2 to Synthesis Example 21) The synthesis example 2 shown in Table 1 was obtained in the same manner as in Synthesis Example 1 except that the molecular weight was adjusted by the addition amount of the polymerization initiator azobisisobutyl nitrile. ~Acrylic polyol of Synthesis Example 21. Further, the synthesis example 17' is an acrylic polyol having a composition shown in Synthesis Example 1 in Patent Document 2. In addition, the abbreviation in Table 1 is as follows. BA: butyl acrylate, EMA: ethyl methacrylate, EA: ethyl acrylate, St: styrene, CHMA: cyclohexyl methacrylate, 2EHA: ^acid-2 on the base 5, HEA: propylene _2_减乙_, Side A: _gM-_TSI, HEMA: Methyl acrylate acid base vinegar 24 201242054 is the 101104895 Chinese manual No picture dirty correction This revision period: June, June 15 曰 [Table 1] monomer composition number average breaking amount Tg (°C) value (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA HEMA A-1 47.2 51.0 1.8 10000 5 8.6 A-2 47.2 51.0 1.8 35000 5 8,6 A-3 47.2 51.0 1.8 60000 5 8.6 A-4 56.2 42.0 1.8 35000 -5 8.6 A-5 60.7 37.5 1.8 35000 -15 8.6 A-6 71.2 27.0 1.8 35000 -25 8.6 A-7 47.0 50.0 3.0 35000 -5 14.5 A -8 47.6 51.5 0.9 35000 -5 4.3 A-9 47.3 52.3 0.4 35000 -5 2.1 A-10 47.6 51.5 0.9 35000 -5 4.3 ~ A-11 40.3 50.0 10.7 35000 -5 51.6 A-12 39.0 45.0 16.0 35000 -5 ΊΊΑ A-13 48.3 40.6 10.0 1.1 35000 -5 4.3 A-14 44.7 53.5 1.8 35000 10 8.6 ~~' A-15 38.0 60.2 1.8 35000 5 8.6 A-16 47.0 51.0 2.0 35000 5 8.6 A-17 70.0 10.0 10.0 10.0 25000 55 483 A-18 47.6 51.5 0.9 6000 -5 4 3 ' A-19 47.6 51.5 0.9 150000 -5 4 3~ A-20 95.0 4.1 0.9 35000 -50 4 3 ^ A-21 35.0 42.0 23.0 35000 -5 Γϊα〇~^ &lt;Example of formulation of adhesive composition&gt; (Example 1 to Example 17, Comparative Example 1 to Comparative Example 6) The acrylic polyol (A) as a main component in terms of 固 solid content is prepared by blending the polyisocyanate (B) as a curing agent with the compounding ratio shown in Table 2, and blending as Glycidyl-containing sulphur coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by weight, = dioctyltin dilaurate ("NEOSTANNU-810", manufactured by Nitto Chemical Co., Ltd.) 0.01 weight The solid content is further adjusted to 25 by ethyl acetate. 201224054 is the Chinese manual of 101104895. There is no underline correction. This revision date: June 15, 101 [Table 2] Polyacids of polyacids - (A) Polyisocyanate (B) ) number average molecular weight Tg (°〇 Mean value (mgKOH/g) Type NCO/OH ratio formulation ratio Example 1 A-1 10000 5 8.6 Hardener A 2.0 10.2 Example 2 A-2 35000 5 8.6 Hardener A 2.0 10.2 Example 3 A-3 60000 5 8.6 Hardener A 2.0 10.2 Example 4 A-4 35000 -5 8.6 Hardener A 3.0 15.3 Example 5 A-5 35000 -15 8.6 Hardener A 3.0 15.3 Example 6 A-6 35000 -25 8.6 Hardener B 3.0 10.1 Example 7 A-7 35000 —1 — -5 14.5 Hardener B 3.0 17.0 Example 8 A-8 35000 -5~ 4.3 Hardener B 3.0 5.0 Example 9 A-9 35000 -5 2.1 Hardener B 3.0 2.5 Example 10 A-10 35000 -5 4.3 Hardener B 1.2 2.0 Example 11 A-10 35000 -5 4.3 Hardener C 3.0 8.0 Example 12 A-11 35000 -5 51.6 Hardener c 1.2 38.6 Example 13 A-12 35000 -5 77.4 Hardener C 0.5 24.1 Example 14 A -13 35000 -5~ 4.3 Hardener C 3.0 8.0 Example 15 A-14 35000 10 8,6 Hardener A 2.0 10.2 Example 16 A-15 35000 "5 8.6 Hardener A 2.0 10.2 Example 17 A-16 35000 5 8.6 Hardening Agent A 2.0 10.2 Comparative Example 1 A-17 25000 55 48.3 Hardener D 0.5 8.0 Comparative Example 2 A-18 6000 -5 4.3 Hardener A 3.0 7.7 Comparative Example 3 A-19 150000 -5 4.3 Hardener A 3.0 Ί·Ί Comparative Example 4 A-20 35000 -50 4.3 Hardener A 3.0 7.7 Comparative Example 5 A-21 35000 -5 110.0 Hardener A 0.5 ^1 32.7 Comparative Example 6 A-8 35000 -5 4.3 Hardener A 12.0 30.7 *1 compounding ratio = main agent: hardener (solid content ratio) *2 3.0 parts by weight of a (decane coupling agent) to (A) 100 parts by weight (nonvolatile matter). *3 With respect to (A) 100 parts by weight (nonvolatile matter), 仏(10)(10)丨 parts by weight are formulated as a reaction accelerator. ^4 Hardener A : Takenate D-160N (manufactured by Mitsui Chemicals, TMP adduct of hexamethylene diisocyanate) ΐϋ! 2: lakfnateD-178N (manufactured by Mitsui Chemicals, hexamethylene diisocyanide) Acidic vinegar glycolic acid vinegar modified) Hardener C Isophorone diisodecanoate isocyanurate modification = bismuth D. Sumidur N3200 (manufactured by Sumika Bayer Urethane, hexamethylene diisocyanate [Diurea modified product) &lt;Production example of laminated film 1&gt; The adhesive compositions of Examples 1 to 17 and Comparative Examples 1 to 6 were used, and the dry coating amount was 4 g/m2 to 5 g. /m2, the adhesive composition is applied to the polyester film by a dry laminator [26, 2012, 420, 2014, 2014, revised period: 1〇1, June 15 is the 101104895 Chinese manual without line Correct the corona treatment surface of this product, Luminm X-10S, thickness 5〇μιη]. Then, after evaporating the solvent, it was laminated on a corona-treated surface of another polyester film [manufactured by Toray Industries, Lumirror X-10S, thickness: 50 μm]. Thereafter, the hardened portion was aged for 3 days at 4 Torr, and the film was laminated to form a laminated film 1. &lt;Production Example of Laminated Film 2&gt; Examples 1 to 4 and Comparative Examples were used! ~Binder of Comparative Example 3 0 The composition film 2 was formed into a laminated film 2 of a structure of [corona treated polyester film/adhesive layer/aluminum foil] in accordance with the method for producing the laminated film 1. &lt;Preparation Example of Laminated Film 3&gt; Using the adhesive compositions of Examples 1 to 4 and Comparative Examples 1 to 3, a ruthenium-doped vapor-deposited vinegar was prepared in accordance with the production method of the laminated film 丽The vaporized layer of the film is connected to the adhesive layer to form a laminated layer of θ 3 ° [corona ^ 聚 膜 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Table 3 shows the combination of the main agent and the hardener in Examples 1 to 17, Comparative Example 1 to Comparative Example 6, and the initial adhesion force of the laminated film 1 and exposure to 1000 in an environment of 85 ° C and a humidity of 85%. Hours after 2 hours, 2 hours, and 3000 hours. ‘and’ shows the use of Examples 1 to 4 and Comparative Examples in Tables 4 and 5. The initial adhesion of the laminated film 2 and the laminated film 3 of 1 to Comparative Example 3 was exposed to an environment of 85 ° and a humidity of 85% for 1 hour, 2 hours, and 3000 hours later. The specific evaluation method will be described below. <Before aging, aging-like force test> 27 201242054 Revision date: June, 2011, 丨5, is the 1011048% Chinese manual, no slash correction, the aging and aging of the laminated film 1, laminated film 2 The layered chess 3 is cut to a size of 200 mmx15 _, and after standing for 6 hours in a pit and thirst environment, a tensile tester is used according to the ASTM_m876_6i: test method, in an environment of 65% humidity and humidity. The τ-type peeling test was carried out at a load rate of 300 mm/min. The peel strength (N/15 mm width) between the PET film/PET film, the PET film, the ρΕτ film, and the second emulsified polyester film was shown by five test average filaments. &lt;Adhesion test after moisture heat resistance test&gt; The laminate after aging was cut to a size of 2 mm x 15 mm, respectively. Allow to stand for 1 hour, 2 hours, and 3000 hours in an environment of 85% humidity. Thereafter, after standing for 6 hours in a pit and a humidity of 65%, the test was carried out according to the test method of ASTM_D1876_61 using a tensile tester at 25 t and a humidity of 65% at a load speed of mm/min. τ type peel test. The peeling strength (N/15 mm width) between the PET film/PET film, the PET film/sand foil, the PET film/the dioxide dioxide vapor-deposited polyester film was indicated by the average value of the five test pieces. &lt;Evaluation Criteria&gt; [Adhesion test before aging] ◎ Excellent in practical use: 3 N/15 mm or more 〇 Practical area: 2 N/15 mm to 3 N/15 mm △ Practical lower limit: 1 N/15 mm ~2 N/15 mm x is not practical: less than 1 N/15 mm [After the aging test, the adhesion test after the heat and humidity test] ◎ Excellent in practical use: 5 N/15 mm or more 28 201242054 is the 101104895 No. Chinese manual without slash correction This revision period: 101 years, 15 months, practical area: 4 N/15 mm~5 N/15 mm △ Practical lower limit: 2N/15 mm ~4 N/15 mm x is not practical : Less than 2 N/15 mm [表3] 接著力 耐濕熱性試驗 老化前後之接著強度 (N/15mm) 85°C、濕度85%之隨時間經過後之接著強度（N/15mm) 老化前 於40°C下老化3天後 1000小時後 2000小時後 3000小時後 實例1 2.2 〇 4.3 〇 4.2 〇 3.8 Δ 3.5 Λ 實例2 3.4 ◎ 5.6 ◎ 5.4 ◎ 5.2 ◎ 5.2 ◎ 實例3 2.7 〇 5.4 ◎ 5.7 ◎ 5.1 ◎ 5.2 ◎ 實例4 3.5 ◎ 5.1 ◎ 5.2 ◎ 4.8 〇 4.4 〇 實例5 3.2 ◎ 4.2 〇 4.1 〇 3.9 Δ 3.3 Δ 實例6 4.0 ◎ 4.0 〇 3.9 Δ 3.7 Δ 3.1 Δ 實例7 4.1 ◎ 5.2 ◎ 5.2 ◎ 5.3 ◎ 5.1 ◎ 實例8 3.4 ◎ 5.1 ◎ 4.9 〇 4.3 〇 3.7 Δ 實例9 3.2 ◎ 4.8 〇 4.3 〇 4.2 〇 3.3 Δ 實例10 3.3 ◎ 4.9 〇 5.2 ◎ 4.4 〇 3.5 Δ 實例11' 3.5 ◎ 5.3 ◎ 5.4 ◎ 5.4 ◎ 5.1 ◎ 實例12 3.8 ◎ 5.1 ◎ 5.2 ◎ 4.4 〇 4.0 0 實例13 3.6 ◎ 5.0 ◎ 4.8 〇 4.2 〇 3.9 Δ 實例14 3.5 ◎ 5.3 ◎ 5.8 ◎ 5.3 ◎ 5.2 ◎ 實例15 3.3 ◎ 5.8 ◎ 5.8 ◎ 5.6 ◎ 5.5 ◎ 實例16 4.0 ◎ 5.7 ◎ 5.9 ◎ 5.7 ◎ 5.4 ◎ 實例Π 3.2 ◎ 5.5 ◎ 5.3 ◎ 5.1 ◎ 5.0 ◎ 比較例1 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X 比較例2 0.4 X 3.5 Δ 3.4 Δ 2.6 Δ 1.8 X 比較例3 1.2 Δ 2.8 Δ 2.2 Δ 2.1 △ 1 1.5 X 比較例4 2.2 〇 2.2 △ 1.7 X 1.2 X 0.3 X 比較例5 3.1 ◎ 2.3 Δ 3.3 △ 2.1 △ 1.8 X 比較例6 於調製接著劑時產生凝膠物，因此未實施塗佈 29 201242054 爲第liu〇4895號中文麵書無劃線修正本 修正曰期:1〇1年6月15曰 [表4] 鋁箔/經處理之聚酯膜______ 接著力 财濕、熱性試驗_____ 老化前後之接著強度 (N/15mm) 85Ϊ、85%RH之隨時間經過後之接著 -強度（N/15 mm) 老化前 於40°c下老化3天後 1000小時後 2000小時後 3000 時後 實例1 2.3 0 4.8 〇 4.5 〇 4.2 〇 3.5 ] Δ 實例2 2.6 〇 5.4 ◎ 5.3 ◎ 5.1 ◎ 4.8 〇 實例3 2.8 〇 5.1 ◎ 4.9 〇 4.3 〇 4.2 〇 實例4 2.1 〇 4.3 〇 4.5 〇 4.3 〇 4.1 〇 比較例1 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X 比較例2 0.9 X 2.7 Δ 2.4 Δ 2.3 Δ 1.8 X 比較例3 0.5 X 2.5 Δ 3.1 Δ 2.9 Δ 2.2 Δ [表5] 二氧化矽蒸鍍聚酯膜/經處理之聚酯膜 接著力 耐濕熱性試驗 老4 匕前後之接著強度 (N/15mm) 85°C、85%RH之隨時間經過後之接著強度（N/15mm) 老化 前 於40°C下老化3天後 1000小時後 2000小時後 3000小時後 實例1 2.1 〇 4.5 〇 4.3 〇 3.9 Δ 3.5 Λ 實例2 2.3 〇 5.3 ◎ 5.2 ◎ 4.8 〇 —--- 4,3 〇 實例3 2.2 〇 5.1 ◎ 5.1 ◎ 4.6 0 ~-—-— 3 7 A 實例4 2.6 〇 5.2 ~1 ◎ 4.3 〇 4.1 〇 —--^--- 4.2 ζλ 比較例1 0,6 X 3.1 Δ 2,5 Δ 1.9 ----- 〇 9 比較例2 0.7 X 2.8 Δ 2.2 Δ 1.7 Δ '----.— 1 S —---- 比較例3 0.8 X 2.4 Δ 2.1 Δ 2.1 △ HZ 如表3所示可知：實例之接著劑組成物於之老化前、 老化後之接著力以及耐濕熱性試驗後之接著力優異，可辨 長時間地維持接著強度。因此，該些實例之接著南 1纟 之面向室外用途的長期耐濕熱性優異。 ~/ 而且，於HS C 8917 (結晶系太陽電池模組之严 驗方法及耐久試驗方法）中，將於85〇c、濕度85〇/衣兄成 1000小時規定為耐濕性試驗B-2,已知為牿别„ 0下耐久 J敬酷之試驗 30 修正日期:1〇1年6月15日[Table 3] Next, the strength (N/15 mm) before and after aging of the heat and humidity resistance test was 85 ° C, the humidity was 85%, and the subsequent strength (N/15 mm) after aging was aged at 40 ° C for 3 days before aging. After 1000 hours and 2000 hours after 3000 hours, Example 1 2.2 〇 4.3 〇 4.2 〇 3.8 Δ 3.5 Λ Example 2 3.4 ◎ 5.6 ◎ 5.4 ◎ 5.2 ◎ 5.2 ◎ Example 3 2.7 〇 5.4 ◎ 5.7 ◎ 5.1 ◎ 5.2 ◎ Example 4 3.5 ◎ 5.1 ◎ 5.2 ◎ 4.8 〇 4.4 〇 Example 5 3.2 ◎ 4.2 〇 4.1 〇 3.9 Δ 3.3 Δ Example 6 4.0 ◎ 4.0 〇 3.9 Δ 3.7 Δ 3.1 Δ Example 7 4.1 ◎ 5.2 ◎ 5.2 ◎ 5.3 ◎ 5.1 ◎ Example 8 3.4 ◎ 5.1 ◎ 4.9 〇 4.3 〇 3.7 Δ Example 9 3.2 ◎ 4.8 〇 4.3 〇 4.2 〇 3.3 Δ Example 10 3.3 ◎ 4.9 〇 5.2 ◎ 4.4 〇 3.5 Δ Example 11' 3.5 ◎ 5.3 ◎ 5.4 ◎ 5.4 ◎ 5.1 ◎ Example 12 3.8 ◎ 5.1 ◎ 5.2 ◎ 4.4 〇 4.0 0 Example 13 3.6 ◎ 5.0 ◎ 4.8 〇 4.2 〇 3.9 Δ Example 14 3.5 ◎ 5.3 ◎ 5.8 ◎ 5.3 ◎ 5.2 ◎ Example 15 3.3 ◎ 5.8 ◎ 5.8 ◎ 5.6 ◎ 5.5 ◎ Example 16 4.0 ◎ 5.7 ◎ 5.9 ◎ 5.7 ◎ 5.4 ◎ Real Example 3.2 ◎ 5.5 ◎ 5.3 ◎ 5.1 ◎ 5.0 ◎ Comparative Example 1 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X Comparative Example 2 0.4 X 3.5 Δ 3.4 Δ 2.6 Δ 1.8 X Comparative Example 3 1.2 Δ 2.8 Δ 2.2 Δ 2.1 Δ 1 1.5 X Comparative Example 4 2.2 〇 2.2 △ 1.7 X 1.2 X 0.3 X Comparative Example 5 3.1 ◎ 2.3 Δ 3.3 Δ 2.1 Δ 1.8 X Comparative Example 6 A gel was generated when the adhesive was prepared, so that no coating was performed 29 201242054 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Then the strength (N/15mm) 85Ϊ, 85% RH after the passage of time-strength (N/15 mm) before aging at 40 °c for 3 days, after 1000 hours, after 2000 hours after 3000 hours after example 1 2.3 0 4.8 〇4.5 〇4.2 〇3.5 ] Δ Example 2 2.6 〇5.4 ◎ 5.3 ◎ 5.1 ◎ 4.8 〇 Example 3 2.8 〇 5.1 ◎ 4.9 〇 4.3 〇 4.2 〇 Example 4 2.1 〇 4.3 〇 4.5 〇 4.3 〇 4.1 〇 Comparative Example 1 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X Comparative Example 2 0.9 X 2.7 Δ 2.4 Δ 2.3 Δ 1.8 X Comparative Example 3 0.5 X 2.5 Δ 3.1 Δ 2.9 Δ 2.2 Δ [Table 5] Antimony sulphide vapor-deposited polyester film/treated polyester film, adhesion heat and humidity resistance test, 4 匕 before and after strength (N/15mm) 85°C , 85% RH after the passage of time after the strength (N / 15mm) before aging at 40 ° C after 3 days after 1000 hours after 2000 hours after 3000 hours after Example 1 2.1 〇 4.5 〇 4.3 〇 3.9 Δ 3.5 Λ Example 2 2.3 〇5.3 ◎ 5.2 ◎ 4.8 〇—--- 4,3 〇 Example 3 2.2 〇5.1 ◎ 5.1 ◎ 4.6 0 ~---- 3 7 A Example 4 2.6 〇5.2 ~1 ◎ 4.3 〇4.1 〇—-- ^--- 4.2 ζλ Comparative Example 1 0,6 X 3.1 Δ 2,5 Δ 1.9 ----- 〇9 Comparative Example 2 0.7 X 2.8 Δ 2.2 Δ 1.7 Δ '-----. — 1 S —-- -- Comparative Example 3 0.8 X 2.4 Δ 2.1 Δ 2.1 △ HZ As shown in Table 3, it can be seen that the adhesive composition of the example is excellent in the adhesion force before aging, after the aging, and after the heat and humidity resistance test, and can be distinguished. The strength is maintained in time. Therefore, these examples are excellent in long-term heat and humidity resistance for outdoor use. ~/ Moreover, in HS C 8917 (the method of rigorous solar cell module and the endurance test method), the moisture resistance test B-2 will be specified at 85 ° C, humidity 85 〇 / clothing brother 1000 hours. , known as screening „ 0 durability J test of cool 30 correction date: 1 June 1 201242054 爲第101104895號中文說明書無劃線修正本 方法。於本只例中，表現出於超過小時，經過扣⑻ 小¥之長^•間後亦可維持接著強度之特性，可以說本發明 之接著劑組成物具有充分之長期耐濕熱性。 太陽電池用背面保護片於此種長期耐濕熱試驗中保持 充分的層間接著強度（層壓強度），於片材層間並不產生脫 層’因此可有助於太陽電池元件之保護、發電效率之維持， 進-步可有祕域電池之壽命延長。太陽電池之壽命延 ，與太陽電池系統之普及相關，自確保化石㈣以外之能 量的觀點考慮，亦有助於環境保護。 本發明之接著劑組成物可作為面向建築物等室外產業 用，之多層積層材料（屏障材料、外牆材料、屋頂材料了 太％，池面板材料（太陽電池用背面保護片、太陽電池表 ，保護^ )、窗戶材料、室外地板材料、照明保護材料、汽 用接著劑而提供強的接著強度。而且，可抑制 ^至4時由於水解等所造成之接著強度隨時間經過而 降低’可經長時間地維持強的接著強度。 价比。疋丙烯酸多㈣（A)之玻璃轉移溫度為 ’ 1 5G°C之例子。評價之結果是獲得基本上沒有對 初始之接著力小’於嘯性試驗中接著 6議比1例2是丙烯酸多元醇（A)之數量平均分子量為 k㈣^ 1G，_之例子。可知評價之結果是老化步驟 則 舞1之凝聚力不足，老化步驟前之接著力小。於工 業產之f月幵/日守，捲繞為輕狀之狀態的積層體使捲芯為 201242054 爲第ώΐ〇4895號Φ嫌卿麵難縣 紙醜ΚΠ年6月即 上下垂直方向而進行老化。若老化步驟前之接著力小，則 於老化時捲繞容易散開，並不適於工業性生產。 比較例3疋丙烯酸多元醇（a)之數量平均分子量為 150,000，大於loo ooo之例子。可知評價之結果是對ρΕτ 膜之濕潤性不足，無法於老化前獲得充分之接著力。與比 較例2同樣的是於老化的過程中捲繞容易散開，並不適於 工業性生產二而且，由於耐濕熱性試驗而造成接著力緩緩 降低’且接著力本來就低，因此獲得於3〇〇〇小時後低於實 用下限之結果。 。比較例4是丙烯酸多元醇（A)之玻璃轉移溫度為 -50C，低於-40C之例子。可知評價之結果是即使於表面 處理聚醋膜之情形時，甚至連3⑽5 mm)左右之接著 力也無法表現出。 比較例5是丙稀酸多元醇（A)之OH值為11〇,大於 削之例子。可知評價之結果是獲得交聯變過剩從而成為 非常硬的硬化塗膜，接著性差的結果。 比較例6是聚異氰酸酯（b)之調配量為nc〇/〇h=12 之例子。可知評價之結果是於塗佈之前進行與丙烯酸多元 醇（A)之反應，產生凝膠物，因此無法進行塗佈。 曰本申=案主張以於2〇11年3月31號向日本智慧財產 局提出申請之日本專利申請案第2〇11-〇78188號為基礎的 優先權。亥專利申請案所揭露之内容系完整結合於本說明 書中。 [產業上之可利用性] 32 201242054 •--— ' I---1 爲第101104895號中文說明書無劃線修正本 修正日期:1〇1年6月15日 本發明之積層片用接著劑組成物是用以接合同 同原材料之被黏著體者，例如可於塑系 原材料之多層積層體之接合中適宜地使用。當上、^二 塑膠系原材料彼此、金屬系原材料彼此之接合。本發明之 積層片用接著劑組成物即使暴露於高溫高濕度環境下亦可 維持高的接著力。因此，作為面向建築物等室外產業用途 之多層積層材料（屏障材料、外牆材料、屋頂材料、太陽 心 電池面板材料（太陽電池用背面保護片、太陽電池表面保 濩片）、窗戶材料、室外地板材料、照明保護材料、汽車部 件等）用接著劑而言適宜。可經長時間地隨時間經過地維 持接著強度，因此特別適於強烈要求環境耐受性之用途、 例如太陽電池用背面保護片之形成。而且，亦適於太陽電 池用表面保護片之形成。而且，本發明之積層片用接著劑 組成物於特別是於包含塑膠膜之表面處理層的層間顯示出 高的接著力，亦可適宜地適用於表面未經處理之原材料（亦 &amp; 包含表面未經處理之塑膠膜）中。 【圖式簡單說明】 無。 【主要元件符號說明】 益。 33 201242054 .一層， 修正日期:1〇1年6月15曰 爲第ΐίΐ 104895號中文說明書無劃線修正本 發明專利說明書 (本說明書格式、順序，請勿任意更動，※記號部分請勿填寫） ※申請案號 ※申請日十,.&gt;‘/? m?c分類 一、發明名稱：（中文/英文） c〇v ] 積層片用接著劑組成物及太陽電池用背面保護片201242054 For the Chinese manual No. 101104895, this method is not slashed. In the present example, the performance of the adhesive strength of the present invention can be maintained for more than an hour, and the adhesive composition of the present invention can maintain the strength of the adhesive strength after the length of the buckle (8). The solar cell back protective sheet maintains sufficient interlayer adhesion strength (laminate strength) in such long-term moisture resistance test, and does not cause delamination between the sheet layers, thus contributing to solar cell element protection and power generation efficiency. Maintenance, step-by-step can extend the life of the battery. The longevity of solar cells is related to the popularity of solar cell systems, and it also contributes to environmental protection from the viewpoint of ensuring energy other than fossils (4). The adhesive composition of the present invention can be used as a multi-layered material for building materials and other outdoor industries (barrier material, exterior wall material, roofing material, too much, pool panel material (back panel for solar cell, solar cell watch, Protection ^ ), window material, outdoor flooring material, lighting protection material, vapor adhesive to provide strong bonding strength. Moreover, it can suppress the decrease of the subsequent strength due to hydrolysis, etc., over time. Maintain strong bonding strength for a long time. Price ratio. 疋Acrylic acid (4) (A) The glass transition temperature is '15G °C. The result of the evaluation is that there is basically no small initial force to the whistling In the test, 6 cases are compared with 1 case. The number average molecular weight of the acrylic polyol (A) is k(tetra)^1G, _. It can be seen that the result of the evaluation is that the aging step is insufficient for the cohesive force of the dance 1, and the adhesion force before the aging step is small. In the industrial production of the 幵 幵 / 日 守 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The aging is performed in the vertical direction. If the adhesion force before the aging step is small, the winding is easily spread at the time of aging, and is not suitable for industrial production. Comparative Example 3 疋 The acrylic polyol (a) has a number average molecular weight of 150,000, which is larger than As an example of loo ooo, it was found that the wetness of the ρΕτ film was insufficient, and sufficient adhesion could not be obtained before aging. The same as in Comparative Example 2, the winding was easily spread during aging, and it was not suitable for industrial use. In the second production, the adhesion was gradually lowered due to the heat and humidity resistance test, and the force was originally low, so that the result was lower than the practical lower limit after 3 hours. Comparative Example 4 is an acrylic polyol (A) The glass transition temperature is -50 C, which is lower than -40 C. It can be seen that the result of the evaluation is that even in the case of surface treatment of the polyester film, even an adhesion of about 3 (10) 5 mm) cannot be exhibited. Comparative Example 5 is an example in which the OH value of the acrylic polyol (A) was 11 Å, which was larger than that of the cut. As a result of the evaluation, it was found that the cross-linking became excessive and it became a very hard cured coating film, which was a result of poor adhesion. Comparative Example 6 is an example in which the amount of the polyisocyanate (b) blended is nc〇/〇h=12. As a result of the evaluation, it was found that the reaction with the acrylic polyol (A) was carried out before the coating to produce a gel, and thus coating was impossible. The priority of the Japanese Patent Application No. 2〇11-〇78188, filed on March 31, 2011 to the Japanese Intellectual Property Office. The contents disclosed in the Hai patent application are fully incorporated in this specification. [Industrial Applicability] 32 201242054 •--- ' I---1 is the 101101895 Chinese manual without a slash correction. Amendment date: June 1st, 1st, 15th Japan's invention of laminated sheets with an adhesive composition The object is used to bond the same material to the adherend of the raw material, for example, it can be suitably used in the joining of the multi-layer laminate of the plastic raw material. When the upper and lower plastic materials are joined to each other, the metal-based raw materials are joined to each other. The adhesive composition for a laminated sheet of the present invention can maintain a high adhesion even when exposed to a high temperature and high humidity environment. Therefore, it is a multi-layer laminated material for use in outdoor industries such as buildings (barrier materials, exterior wall materials, roofing materials, solar cell panel materials (back protection sheets for solar cells, solar cell surface protection sheets), window materials, outdoor Flooring materials, lighting protection materials, automotive parts, etc.) are suitable for use as an adhesive. The bonding strength can be maintained over a long period of time, and therefore it is particularly suitable for applications in which environmental resistance is strongly required, for example, formation of a back surface protective sheet for solar cells. Moreover, it is also suitable for the formation of a surface protection sheet for a solar cell. Further, the adhesive sheet composition for laminated sheets of the present invention exhibits a high adhesion force between the layers particularly including the surface treatment layer of the plastic film, and can be suitably applied to the surface untreated raw material (also &amp; Untreated plastic film). [Simple description of the diagram] None. [Main component symbol description] Benefit. 33 201242054 . One floor, date of revision: January 1st, 1st, June 15th is the first ΐ ΐ 104895 Chinese manual without slash correction of the patent specification of this invention (the format, order of this manual, please do not change anything, please do not fill in the ※ part) ※Application No. ※Application date ten,.&gt;'/? m?c classification I. Invention name: (Chinese/English) c〇v ] Adhesive composition for laminated sheets and back protective sheet for solar cells ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL 二、 中文發明摘要： 提供一種接著劑組成物，其於各種片狀部件間、特別 是於包含塑膠膜表面處理層之層間顯示出高的接著力，即 使暴露於高溫高濕度環境下亦可維持高的接著力，適於製 造太陽電池用背面保護片。本發明之積層片用接著劑組成 物包括丙烯酸多元醇（A)與聚異氰酸酯（b)，丙婦酸多 元醇（A)之數量平均分子量為1〇,〇〇〇〜10〇,〇〇〇，且經值 為1 mgKOH/g〜l〇〇mgKOH/g，另外玻璃轉移溫度（Tg) 超過-40 C且為l〇°C以下。另外，源自丙烯酸多元醇（a) 之羥基與源自聚異氰酸酯（B)之異氰酸酯基之當量比 NCO/OH 為 0.1 〜3。 三、 英文發明摘要： An adhesive composition for fabricating a back 201242054 I Λ \J^ / Μ. X 爲第丨01104895號中文說明書無劃線修正本修正曰期:101年6月15曰 protective sheet of solar cell is provided. The adhesive composition provides high adhesion between various sheet-like portions, especially between layers including surface treatment layer of plastic film, and the high adhesion can be maintained even when the adhesive composition is exposed to an environment of high temperature and high humidity. The adhesive composition for a laminating sheet of this invention includes an acrylic polyol (A) and a polyisocyanate (B), wherein a number average molecular weight of the acrylic polyol (A) is 10,000 to 100,000m, a hydroxyl value is 1 to 100 mgKOH/g, and a glass transition temperature (Tg) is more than -40°C and no more than 10°C. Further, an equivalent ratio NCO/OH of a hydroxyl group from the acrylic polyol (A) and an isocyanate group from the polyisocyanate (B) is 0.1 to 3. 201242054ι 爲第101104895號中文說明書無劃線修正本 修正日期:1〇1年6月15曰 七、申請專利範圍： 1. 一種積層片用接著劑組成物，包括丙烯酸多元醇 (A)與聚異氰酸酯（B)， 所述丙烯酸多元醇（A)之數量平均分子量為10,000 〜100,000，且羥值為1 mgK〇H/g〜1〇〇 mgK〇H/g，另外玻 璃轉移溫度（Tg)超過-4〇°C且為10°c以下， ^源自所述丙烯酸多元醇（A)之羥基與源自所述聚異 氰酸酯（B)之異氰酸酯基之當量比Nc〇/〇h為。 2. 如申請專利範圍第丨項所述之積層片雜著劍組成 所返眾呉氰酸 .呉氰酸酿驭脂 J 田月旨環族 肪族二異氰酸酯衍生的聚異氰酸酯。 著劑==範圍第1項或第2項所述之_用接 之製層以上片狀部件的太陽電池用背面保護片 用於如下之用途中：形成用r 合的接著劑層的至少—部分。、將所述片狀部件彼此接 4. -種太陽電池”面保護片， 由如申請專利範圍第1項至第3 jg、匕3 . 層片用接著劑組成物所形成_^ 項所述之積 層而積層的至少2層以上的片狀部件9，；丨隔所述接著劑 34 201242054x 爲第1^1104895號中文說明書無劃線修正本修正日期:101年6月15曰 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。 五、 本案若有化學式時，請揭示最能顯示發明特徵 的化學式： 〇 無。ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL II. SUMMARY OF THE INVENTION: An adhesive composition is provided which exhibits high adhesion between various sheet members, particularly layers comprising a plastic film surface treatment layer. It can maintain a high adhesion even when exposed to high temperature and high humidity, and is suitable for manufacturing a back protective sheet for solar cells. The adhesive composition for a laminated sheet of the present invention comprises an acrylic polyol (A) and a polyisocyanate (b), and the number average molecular weight of the bupropion polyol (A) is 1 〇, 〇〇〇 10 〇, 〇〇〇 And the pass value is 1 mgKOH/g~l〇〇mgKOH/g, and the glass transition temperature (Tg) exceeds -40 C and is below 10 °C. Further, the equivalent ratio NCO/OH of the hydroxyl group derived from the acrylic polyol (a) to the isocyanate group derived from the polyisocyanate (B) is 0.1 to 3. III. Abstract of English invention: An adhesive composition for fabricating a back 201242054 I Λ \J^ / Μ. X is the Chinese manual of No. 01104895. There is no slash correction. This revision period: June 15, 2010 曰 protective sheet of solar cell The adhesive composition provides high adhesion between various sheet-like portions, especially between layers including surface treatment layer of plastic film, and the high adhesion can be maintained even when the adhesive composition is exposed to an environment of high temperature and high humidity The adhesive composition for a laminating sheet of the invention includes an acrylic polyol (A) and a polyisocyanate (B), wherein a number average molecular weight of the acrylic polyol (A) is 10,000 to 100,000 m, a hydroxyl value is 1 to 100 mgKOH/g, and a glass transition temperature (Tg) is more than -40°C and no more than 10°C. Further, an equivalent ratio NCO/OH of a hydroxyl group from the acrylic polyol (A) and an isocyanate Group from the polyisoc Yanate (B) is 0.1 to 3. 201242054ι is the 101101895 Chinese manual without a slash correction. Amendment date: June 1st, 1st, 1st, 1st, and the scope of application: 1. A laminate for the laminate, including An acrylic polyol (A) and a polyisocyanate (B) having a number average molecular weight of 10,000 to 100,000 and a hydroxyl value of 1 mgK〇H/g to 1〇〇mgK〇H/g, Further, the glass transition temperature (Tg) exceeds -4 ° C and is 10 ° C or less, ^ is derived from the equivalent ratio of the hydroxyl group of the acrylic polyol (A) to the isocyanate group derived from the polyisocyanate (B) Nc 〇/〇h is. 2. As described in the scope of the patent application, the laminated piece of the mixed sword is composed of the cyanuric acid. The cyanuric acid is made from the aliphatic diisocyanate-derived polyisocyanate. The back protective sheet for solar cells of the above-mentioned sheet or the above-mentioned sheet-like member is used in the following applications: at least one of the layers of the adhesive layer formed with r is formed. section. And the sheet-like members are connected to each other. - a solar cell "face protection sheet, as described in claims 1 to 3 jg, 匕 3. The layer is formed of an adhesive composition. At least two or more laminar members 9 laminated in layers; the interlayer adhesive 34 201242054x is No. 1104895 Chinese specification without a slash correction. Amendment date: June 15, 2004, designated representative Figure·· (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.
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JP2012214805A (en) 2012-11-08
KR20140022811A (en) 2014-02-25
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CN103534325A (en) 2014-01-22
JP5003849B1 (en) 2012-08-15

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