TW201244940A - Laminated sheet and solar cell using the same - Google Patents
Laminated sheet and solar cell using the same Download PDFInfo
- Publication number
- TW201244940A TW201244940A TW101110959A TW101110959A TW201244940A TW 201244940 A TW201244940 A TW 201244940A TW 101110959 A TW101110959 A TW 101110959A TW 101110959 A TW101110959 A TW 101110959A TW 201244940 A TW201244940 A TW 201244940A
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- mass
- laminated sheet
- resin
- sheet
- Prior art date
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- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 32
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 32
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 31
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 31
- 239000010419 fine particle Substances 0.000 claims description 56
- 239000000470 constituent Substances 0.000 claims description 12
- 239000004417 polycarbonate Substances 0.000 abstract description 50
- 229920000515 polycarbonate Polymers 0.000 abstract description 19
- 239000010954 inorganic particle Substances 0.000 abstract description 11
- 239000002075 main ingredient Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 236
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 53
- 229920005989 resin Polymers 0.000 description 48
- 239000011347 resin Substances 0.000 description 48
- 239000004594 Masterbatch (MB) Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 45
- -1 polyethylene Polymers 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002245 particle Substances 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
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- 238000005259 measurement Methods 0.000 description 14
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- 238000012360 testing method Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
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- 238000010438 heat treatment Methods 0.000 description 7
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
201244940 六、發明說明: 【發明所屬之技術領域】 於機械特性、抗紫夕卜線 :系積層片。尤其是關於一種聚碳㈣系積層 =當使用:為太陽能電池用背板’又’係關於使用了該 溥膜的太陽能電池用背板或太陽能電池。 λ 【先前技術】 近年來,作為半永久性且無公害之下—代能量源 以屬綠色能源的太陽光發電受到矚目,太陽能電各 速地普及。 -般的太陽能電池之代表構成係如第1圖所示 陽能電池係以EVA(伸乙基·乙烯乙酸8旨共聚物)等之透明 的封閉齊"將發電元件3封閉之物上,貼合玻璃等之透 明基板4、與稱為背板i的樹脂薄片而構成。太陽光通 過透明基板4而導入於太陽能電池内。導入太陽能電池 内的太陽光,被發電元件3所吸收,被吸收的光能量, 變換成為電能量。以連接於發電元件3的引線(第ι圖未 不出)操取經變換的電能量,並使用於各種電氣機器。在 此,背板1係指相對於太陽,被設置於較發電元件3更 背面側’與發電元件3無直接接觸之薄片構件之意。就 该太陽能電池之系統或各構件,雖有各種之提案,不過 就^板丨,主要係使用聚乙烯系或聚g旨系、氟系之樹脂 製薄膜(參照專利文獻1至3)。 —方面,聚碳酸酯系樹脂因機械特性、熱特性、抗 濕熱性、抗熱性、透明性、成形性優異,故被廣泛使用 -4- 201244940 於汽車 是為了 途,尤 所致色 因 外線所 對聚碳 又,為 討將含 色聚碳 性,而 先行技 棚、看板等之屋外材料、光碟、成形材料等。 適^聚妷酸酯系樹脂於太陽能電池背板般之用 其疋屋外長期間使用之用途’有必要抑制 調變化或強度_伸度之劣化。 、卜線 此,吾人開始研討各種用以抑制因聚碳酸酯之紫 致色調變化或強度伸度之劣化。例如,吾人研討 酸,^樹脂添加無機微粒(專利文獻4)之技術。 了提南聚碳酸酯系樹脂之紫外線耐性,吾人亦研 有紫外線吸收劑之丙烯酸樹脂層積層於透明或白 ISs知U曰層(專利文獻5、6、7),或為了提高密接 積層PBT樹脂層(專利文獻8)等之技術。 術文獻 專利文獻 專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 專利文獻6 專利文獻7 專利文獻8 【發明内容 S本特開平hjhom號公報 a本特開平號公報 曰本特開2006-270025號公報 曰本特開2007-191499號公報 曰本特開2006-343445號公報 曰本特開平1 1 -58627號公報 曰本特開平11 - 3 3 4 0 17號公報 曰本特開2009-141345號公報 [發明欲解決課題] 但是’纟先前之聚碳酸酯系薄[欲提供太陽能電 池背板所要求之向抗紫外線性則有困難。 201244940 因此,本發明之課題係提供一 其具有亦可適用於太陽能電池背::酸醋系薄片, 外線性(強度_伸度劣 2械特性,且抗紫 [解決課題之手段] 色調變化之抑制)優異者。 上述課題,本發明採用以下之構成。亦即, ’其係具有將聚碳酸s旨系樹脂作為主要 構成成4之層(P1層)’及將丙職系樹脂作為主要構成 成分,且無機微粒含有_ ―為i質量%以上 以下之層(P2層)的積層片, 貝里/〇 其中,P1層之層厚度TU P2層之層厚度T2之比 T1/T2滿足下述式(I)。 (Wa2+ 18)/9.5^ T1/T2(I) [發明之效果] 根據本發明,可提供一種聚碳酸酯系樹脂薄片,其 相較於先前聚碳酸酯系樹脂薄片,抗紫外線性優異。Ζ 等聚碳酸酯系樹脂薄片,除了太陽能電池用背板之外, 在以液晶顯示器用反射板、汽車用材料、建築材料為妒, 重視抗濕熱性、相對於紫外線之耐性般之用途可適當使 用。尤其是藉由使用此等聚碳酸酯系樹脂薄片,而可提 供具有高耐久性的太陽能電池背板及使用其之太陽能電 池。 【實施方式】 一種積層片’其係具有將聚碳酸酯系樹脂作為主要 構成成分之層(Ρ1層),及將丙烯酸系樹脂作為主要構成 成分,且無機微粒含有率Wa2為1質量%以上20質量% 以下之層(P2層)的積層片, -6- 201244940 其中,pi層之層厚度口與!^層之層厚度丁 2 T1/T2,滿足下述式(j)。 比 (Wa2+ 18)/9.5^ T1/T2(I) /藉由完全滿足上述要件’而可提供一種包含聚碳妒 酯糸樹脂的積層片,該聚碳酸酯樹脂具有可適用於太^ 月匕电池为板等之用途的機械特性,同時具有歷經長期 之抗濕熱性、抗紫外線性。此外,在此所指的主要構: 成分,係表示在P1層中,構成層之樹脂成分中6〇質息 %以上為聚碳酸酯系樹脂之意,更佳為7〇質量%以上里 進-步較佳為8。質量%以上…將聚碳酸醋系。樹脂作 為主要構成成分之層有二層以上之層之情形濃产差土 8%以下魏作相同之層(該值係將相鄰之鄰 :± ,準之相對濃度之值)。在此,有二層以上微粒濃度為: 3之層之情形,則將微粒濃度最少之層設為p 1層。又’ 在P2層,係表示構成層之樹脂成分中6〇質量以上為 :稀酸系樹脂,更佳為70質量%以上、進—步較。佳為8〇 質量%以上。又,在將丙稀酸系樹脂作為主要構成成分 之層有-層以上之層之情形’濃度差±8%以下係視為相 同之層。在此,有二層以上之微粒濃度為不同之層之情 升將微粒濃度最多之層視作p 2層。 進-步’較佳是例示將本發明之積層片,製成例如 後述般’⑴包含P1層/P2層之二層構成、(u)包含?1層 /P2層/……/P2層之多層積層構成、層/P2層/盆他 層、(W)其他層/P1層/?2層、P1層/其他層/p2層等在 構成本發明之積層片之?1層與P2層中,自—表面側使 201244940 取初之層成為P i層,自另一表面側使最初之層成為p2 層之構成(以下’ s亥等構成稱為非對稱之構成。此外,其 他層由複數之層構成亦無妨)之情形,可製成耐捲曲性優 異的積層片:就其理由,在下述詳細說明。 通常,為了使聚碳酸酯系樹脂高功能化,或有在聚 碳酸酯系樹脂添加無機微粒,不過在此時,係使用在一 次製作含有高濃度微粒的母料後,予以稀釋之方法。但 了匕因在母料製作時承受熱過程,故會產生聚碳酸醋系 才S之劣化又,無機微粒因原來就具有吸附水,故含 有無機微粒之聚碳酸酯系樹脂可促進水解反應。在組合 該二種現象之結果’則使抗濕熱性降低。又聚碳酸酯 系樹脂原本對於紫夕卜娩4 Ρ 糸卜線就易於黃變’即使添加微粒予以 白色化,亦完全無法抑制。 方面在本發明之積層片,係藉由積層在Ρ2層使 丙烯酸系樹脂作為Φ亜m Λ、上、a Θ主要構成成分,且無機微粒含有率 i質量%以上2〇質量%以下之層(ρ2層”而可賦 予因應無機微粒之種類的特性(例如光反射性、白色性) :積方面,藉由積層含有無機微粒的丙烯酸樹 脂層’薄片雖傾向於易於破裂,不過藉由使ρι層之層厚 度^與P2層之層厚度T2之比丁1/?2滿足下述式⑴, 可提供可適用於太陽能電池背板用等的機械特性。 (Wa2+ 18)/9.5^ Tl/T2(l) 兹就本發明,例舉具體例如下,同時詳細說明。 2明之積層片之ρι層之主要構成成分的聚碳酸 :::知’係指將二羥二芳基化合物與光氣、或二笨基 石反I酯等之碳酸酯反應所得之聚合物。 -8 - 201244940 在本电明之積層#,以使用於聚碳酸g旨系樹脂之二 經二芳基化合物之例而言,可例舉2,2雙(4_經苯基)丙烧 (通稱雙盼A)、雙(心經笨基)甲院、U1-雙(4_經苯‘基)乙 烷、2,2-雙(4-羧苯基)丁貌、2,2_雙(4_經苯基)辛烧、雙… 經苯基)苯基甲烧、2,2-雙(4·羥苯基-3-甲基苯基)丙烷、 1,1-雙(4-經-3-二級丁基苯基)丙烷、2,2_雙(4_經_3漠苯 基)丙院、2,2-雙(4_經_3u臭苯基)丙烧、2,2_雙(心羥 -3,5-二氣苯基)丙烷等之雙(羥芳基)烷系化合物;1 1雙 (4-經苯基)環戊烧、^-雙(4_經苯基)環己院等之雙㈤芳 基)環烧系化合物、4, _二經二苯驗、4,4,二經基 -3,3 -二曱基二苯醚等之二羥二芳基醚系化合物;4,4, -二羥二苯硫化物等之二羥二芳基硫化物系化合物; 4,4’ -二羥二苯亞砜、4,4’ _二羥基_3,3,·二甲基二苯亞 颯等之二羥二芳亞砜系化合物;4,4,_二羥二苯砜、4,4, -二經基-3’3’ -二甲基二苯礙等之二經二芳基石風系化合 物等為例子,但非限定於該等。又,該等可單獨使用, 依照需要使用複數種亦無妨。 又,本發明之聚碳酸醋系樹脂,除了上述二羥二芳 基化合物’亦可使用具有3個以上酚性羥基的化合物。其 例可例舉根皮三酚(phloroglucin)、4,6-二甲基_2 4 6-= (4-經苯基)-庚稀、2,4,6_二曱基_2,4,6_三_(4_^苯基)_: 烧、1,3,5-三-(4-經苯基)-苯、U山三-(4_經苯基)乙烧 及2,2-雙[4,4-(4’4,.二經二苯基)_環己基]_丙烧等。 在此,本發明之積層片中,為P1層之主要構成成分 的聚碳酸酯系樹脂,由抗熱性、抗濕熱性之觀點,以作 201244940 為二經二芳基化合物之2,2-雙(4-經笨基)丙燒(通稱雙盼 A)為主要成分之聚碳酸酯系樹脂較佳。此外,在此所說 主要成分,係指在使用於聚碳酸酯系樹脂之全二羥二芳 基化a物中,較佳為8 〇莫耳%以上、再佳為9 〇莫耳%以 上、更佳為95莫耳%以上。進一步為?1層之主要構成成 分之聚碳酸酯系樹脂,由更加提高抗熱性、抗濕熱性的 觀點,均以作為二羥二芳基化合物之2,2_雙(4_羥苯基)丙 院(通稱雙盼A)為主要成分之聚碳酸酯系樹脂更佳。 在本發明之積層片’聚碳酸酯系樹脂之分子量較佳 為數量平均分子量(Mn)l〇〇〇〇以上50000以下。更佳為 1 2000以上40000以下、再佳為ι5〇〇〇以上3〇〇〇〇以下。 在本發明之積層片’聚碳酸酯系樹脂之玻璃轉移溫 度Tg ,以兩者為抗濕熱性或抗熱性變高,在使用作為太 陽能電池背板之情形,由在將發電電池組與封閉材料— 起封閉之步驟之積層片之封閉步驟之形態保持性之觀點 為較佳。201244940 VI. Description of the invention: [Technical field to which the invention pertains] Mechanical properties, anti-purple wire: a laminated sheet. In particular, it relates to a polycarbon (tetra) layered layer = when used: a back sheet for a solar cell, and a solar cell back sheet or solar cell using the tantalum film. λ [Prior Art] In recent years, as a semi-permanent and pollution-free energy source, solar power generation, which is a green energy source, has attracted attention, and solar power has spread rapidly. The representative structure of the solar cell is as shown in Fig. 1, in which the solar cell is sealed with a transparent sealing device such as EVA (equivalent ethylene/ethylene acetate 8 copolymer), and the power generating element 3 is closed. The transparent substrate 4 such as glass is bonded to a resin sheet called a back sheet i. The sunlight is introduced into the solar cell through the transparent substrate 4. The sunlight introduced into the solar cell is absorbed by the power generating element 3, and the absorbed light energy is converted into electric energy. The converted electric energy is manipulated by a lead wire connected to the power generating element 3 (not shown), and is used for various electric machines. Here, the back sheet 1 means a sheet member which is disposed on the back side of the power generating element 3 and has no direct contact with the power generating element 3 with respect to the sun. There are various proposals for the system or the components of the solar cell. However, it is mainly a polyethylene-based or poly-g-based resin-based film (see Patent Documents 1 to 3). In view of the fact that the polycarbonate resin is excellent in mechanical properties, thermal properties, moisture resistance, heat resistance, transparency, and formability, it is widely used. -4- 201244940 is used in the automobile, especially because of the external line. For the polycarbon, in order to discuss the color-containing polycarbonity, the exterior materials such as the technical shed and the kanban, optical discs, and molding materials are used. The use of a suitable polyphthalate-based resin for a solar cell backsheet is used for the purpose of the outer length of the squatter. It is necessary to suppress the change of the change or the deterioration of the strength _ elongation. In this way, we have begun to study various kinds of properties to suppress the deterioration of the color tone or the elongation of the strength due to the purple color of the polycarbonate. For example, we have studied the technique of adding an inorganic fine particle to the resin (Patent Document 4). The UV resistance of the Tynan polycarbonate resin, we have also developed an acrylic resin laminate with a UV absorber in a transparent or white ISs layer (Patent Documents 5, 6, and 7), or to improve the adhesion of the PBT resin. A technique such as a layer (Patent Document 8). Patent Document Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 8 [Summary of the Invention S This is an open-opening hjhom bulletin a special open flat bulletin 曰本特开 2006- Japanese Patent Publication No. 270025, No. 2007-191499, JP-A-2006-343445, 曰本特开平1 1 -58627号 曰本特开平11 - 3 3 4 0 17号 曰本特开2009- Japanese Patent Publication No. 141345 [The problem to be solved by the invention] However, the previous polycarbonate is thin. [The ultraviolet light resistance required for providing a solar battery back sheet is difficult. 201244940 Therefore, the subject of the present invention is to provide a solar cell back:: vinegar-based sheet, external linearity (strength_extension 2 mechanical characteristics, and anti-purple [solution to the subject] color change) Suppress) excellent. In the above problem, the present invention adopts the following constitution. In other words, 'there is a layer in which a polycarbonate s-based resin is mainly composed of 4 (P1 layer)' and a C-based resin is used as a main constituent component, and the inorganic fine particles contain _- of i mass% or more. The layered sheet of the layer (P2 layer), the ratio T1/T2 of the layer thickness T2 of the layer thickness TU P2 of the layer P1 of the P1 layer satisfies the following formula (I). (Wa2+ 18)/9.5^ T1/T2 (I) [Effect of the Invention] According to the present invention, it is possible to provide a polycarbonate resin sheet which is excellent in ultraviolet resistance as compared with the conventional polycarbonate resin sheet. In addition to the backsheet for a solar cell, the polycarbonate resin sheet is suitable for use in a liquid crystal display reflector, an automobile material, or a building material, and is excellent in moisture resistance and resistance to ultraviolet rays. use. In particular, by using such polycarbonate-based resin sheets, a solar battery back sheet having high durability and a solar battery using the same can be provided. [Embodiment] A laminated sheet having a layer containing a polycarbonate resin as a main component (a layer of ruthenium) and an acrylic resin as a main component, and having an inorganic fine particle content Wa2 of 1% by mass or more and 20% Layer of the layer below the mass% (P2 layer), -6- 201244940 where the layer thickness of the pi layer is! The layer thickness of the layer is 2 T1/T2, which satisfies the following formula (j). Ratio (Wa2+ 18) / 9.5 ^ T1/T2 (I) / by fully satisfying the above requirements ', a laminated sheet comprising a polycarboester oxime resin which is suitable for use in Taiyue The battery is a mechanical property for use in a board or the like, and has a long-term resistance to moist heat and ultraviolet rays. In addition, the main component: the component referred to herein means that in the P1 layer, the resin component of the constituent layer has a mass ratio of 6 以上 or more of polycarbonate resin, and more preferably 7% by mass or more. - The step is preferably 8. More than % by mass... will be polycarbonate. When the resin is used as the main constituent layer, the layer having two or more layers is rich in the difference of 8% or less, and the same layer (the value is adjacent to: ±, the relative concentration of the standard). Here, in the case where there are two or more layers of the particles having a concentration of 3: the layer having the smallest particle concentration is referred to as the p 1 layer. Further, in the P2 layer, the resin component of the constituent layer is 6 〇 or more by mass: a dilute acid resin, more preferably 70% by mass or more, and further. Good for 8〇 quality% or more. In the case where the layer containing the acrylic resin as the main constituent component has a layer of -layer or more, the concentration difference of ±8% or less is regarded as the same layer. Here, if the concentration of the particles having two or more layers is different, the layer having the highest concentration of the particles is regarded as the p 2 layer. The step-by-step is preferably exemplified by the fact that the laminated sheet of the present invention is formed into a two-layer structure including (1) P1 layer/P2 layer and (u) as described later. 1 layer/P2 layer/.../P2 layer multi-layer laminate structure, layer/P2 layer/pot layer, (W) other layer/P1 layer/?2 layer, P1 layer/other layer/p2 layer, etc. The invention of the laminate? In the first layer and the P2 layer, the original layer of 201244940 is made into the P i layer from the surface side, and the first layer is formed into the p2 layer from the other surface side (hereinafter, the structure of 'Shai and the like is called an asymmetric structure. Further, in the case where the other layer is composed of a plurality of layers, it is possible to form a laminated sheet excellent in curl resistance: the reason for this will be described in detail below. Usually, in order to increase the functionality of the polycarbonate resin, or to add inorganic fine particles to the polycarbonate resin, in this case, a method of preparing a masterbatch containing a high concentration of fine particles once and then diluting it is used. However, since the heat treatment is carried out during the production of the master batch, the polycarbonate is degraded, and the inorganic fine particles have adsorbed water. Therefore, the polycarbonate resin containing inorganic fine particles can promote the hydrolysis reaction. In combination with the results of the two phenomena, the heat and humidity resistance is lowered. Further, the polycarbonate resin was originally liable to yellowing when it was delivered to the purple buds. 4 Even if the particles were whitened, it could not be suppressed at all. In the layered sheet of the present invention, the acrylic resin is used as a main component of Φ亜m Λ, upper and a Θ in the Ρ2 layer, and the inorganic fine particle content is i% by mass or more and 2% by mass or less. Ρ2 layer" can impart properties (for example, light reflectivity and whiteness) in response to the type of inorganic fine particles: in terms of product, the acrylic resin layer containing the inorganic fine particles is apt to be easily broken, but by making the ρ layer The ratio of the layer thickness ^ to the layer thickness T2 of the P2 layer is 1/?2, which satisfies the following formula (1), and can provide mechanical properties applicable to solar battery back sheets, etc. (Wa2+ 18)/9.5^ Tl/T2 ( l) For the purpose of the present invention, for example, the following is a detailed description. 2. The polycarbonate of the main constituent of the layer of the layered layer of the layered layer::: knowing means the dihydroxydiaryl compound and phosgene, or A polymer obtained by reacting a carbonate of a second stupid base anti-I ester, etc. -8 - 201244940 In the case of the laminate of the present invention, an example of a di-diaryl compound used for a polycarbonate resin is exemplified. Take 2, 2 pairs (4_ phenyl) propane (known as double hope A), double ( Stupid base), U1-double (4_ benzene'-yl) ethane, 2,2-bis(4-carboxyphenyl) butyl, 2,2 bis (4-phenyl) octyl , double... phenyl) phenyl ketone, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-terido-3-butylbenzene) Base) propane, 2,2_double (4_ via_3 lyophilyl) propyl, 2,2-bis (4_ _3u odor phenyl) propane, 2,2 bis (cardiohydroxy-3) a bis(hydroxyaryl)alkane compound such as 5-diphenylphenylpropane; 1 bis(4-phenylene)cyclopentane, ^-bis(4-phenylene)cyclohexanthes, etc. a bis(penta)aryl)cycloalkyl compound, a dihydroxydiaryl ether compound such as 4, _di-diphenyl, 4,4, di-mercapto-3,3-didecyldiphenyl ether; a dihydroxydiaryl sulfide compound such as 4,-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3,-dimethyldi a dihydroxydiaryl sulfoxide compound such as benzodiazepine; 4,4,-dihydroxydiphenyl sulfone, 4,4,-di-based-3'3'-dimethyldiphenyl The aryl stone-based compound or the like is exemplified, but is not limited thereto. Further, these may be used alone, depending on Further, in the polycarbonate-based resin of the present invention, a compound having three or more phenolic hydroxyl groups may be used in addition to the above-mentioned dihydroxydiaryl compound. Examples thereof include radix trisphenol. (phloroglucin), 4,6-dimethyl-2 4 6-= (4-phenylene)-glycol, 2,4,6-dimercapto-2,4,6_tri-(4_^benzene Base)_: calcined, 1,3,5-tris-(4-phenyl)-benzene, U-san--(4-phenylene)-b-butyl and 2,2-bis[4,4-(4) '4,. di-diphenyl) _cyclohexyl] _ propyl burning and the like. Here, in the laminated sheet of the present invention, the polycarbonate resin which is a main constituent component of the P1 layer is made of 2,2-double as a di-diaryl compound as 201244940 from the viewpoint of heat resistance and moist heat resistance. A polycarbonate-based resin in which (4-pyro-based)-propane-burning (commonly referred to as "double-looking A") is a main component is preferable. In addition, the main component herein means a total dihydroxydiarylated a used in a polycarbonate resin, preferably 8 〇 mol% or more, more preferably 9 〇 mol% or more. More preferably, it is 95% or more. Further? The polycarbonate-based resin which is a main constituent of the first layer is a 2,2-bis(4-hydroxyphenyl)-propyl compound which is a dihydroxydiaryl compound from the viewpoint of further improving heat resistance and moist heat resistance. A polycarbonate resin which is generally referred to as A) as a main component is more preferable. In the laminated sheet of the present invention, the molecular weight of the polycarbonate resin is preferably a number average molecular weight (Mn) of 10 Å or more and 50,000 or less. More preferably, it is 12,000 or more and 40,000 or less, and more preferably ι5〇〇〇 or more and 3 or less. In the laminated sheet of the present invention, the glass transition temperature Tg of the polycarbonate resin is high in resistance to moist heat or heat, and in the case of using the solar battery back sheet, the power generation battery pack and the sealing material are used. The viewpoint of the form retention of the sealing step of the laminate sheet in the step of closing is preferred.
Tg之測定係依照JIS K7 122(1 987),以升溫速度20 °C /min,將樹脂自25°C升溫至300°C (IstRUN),在該狀 態下保持5分鐘。接著’予以驟冷成為2 5 °C以下,再次 自室溫以20°C /min之升溫速度,進行升溫至300。〇,所 付之2ndRUN之示差掃描熱量測定圖表,於玻璃轉移之 階梯狀之變化部分’以;US K7 121 (1987)之「9.3玻璃轉 移溫度之求法(1)中間點玻璃轉移溫度Tmg」記載之方法 求得。 201244940 玻璃轉移溫度Tg,較佳為125。(:以上,更佳為130 °C以上,再佳為135。(:以上,特佳為14〇<t以上。 又,本發明之積層片之為P2層之主要構成成分的丙 烯酸系樹脂,係指藉由將具有丙烯醯基、曱基丙烯醯基 [以下,丙烯醯基與甲基丙烯醯基一併稱為(甲基)丙烯醯 基。對於(曱基)丙烯酸、(甲基)丙烯酸酯等亦為相同表現] 之化合物予以聚合而可得之聚合物。 在本發明之積層片,以使用於丙烯酸系樹脂之具有 (甲基)丙稀醯基之化合物之例而言,作為單官能化合 物,可例舉(甲基)丙烯酸甲酯、(曱基)丙烯酸乙酯、(甲 基)丙烯酸丁酯、(曱基)丙烯酸己酯、(甲基)丙烯酸月桂 酯、(甲基)丙烯酸硬脂醯酯、(曱基)丙烯酸異莰酯等之(甲 基)丙烯酸烷酯類;(曱基)丙烯酸2-羥乙酯、聚乙二醇單 (甲基)丙烯酸酯、(甲基)丙烯酸羥丙酯、聚丙二醇單(甲 基)丙烯酸酯、(甲基)丙烯酸2-羥丁酯、丙烯酸4_羥丁酯、 曱基α-(羥曱基)丙烯酸酯、乙基α_(羥曱基)丙烯酸酯、 正丁基α-(羥曱基)丙烯酸酯、參(2-羥基)異三聚氰酸酯二 丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、2_(甲基) 丙烯醯氧乙基-2 -羥乙基酜酸甘油單曱基丙烯酸酯等之 具有輕基之丙烯酸g旨類;2-(曱基)丙稀醯氧乙基-琥王白 酸、2-(曱基)丙烯醯氧乙基-酞酸、2-(曱基)丙烯醯氧乙基 六氫酞酸等具有羧酸基之丙烯酸酯;(曱基)丙烯酸苯 酯、苯基赛璐蘇(曱基)丙烯酸酯、壬基苯氧基聚乙二醇(甲 基)丙烯酸酯等之烷基末端聚伸烷二醇單(曱基)丙烯酸酯 類;Ν,Ν-二甲基胺基丙基(曱基)丙烯醯胺、丙烯醯基味 201244940 。林、N-異丙基(甲基)丙烯醯胺等之(甲基)丙烯醯胺類,其 他1分子中具有1個(甲基)丙烯醯基的化合物等為例, 不過並非限定於該等。又,該等可單獨使用,依照需要 使用複數種亦無妨。 又’在本發明之丙烯酸系樹脂,除了上述具有(曱基) 丙烯酿基之化合物,亦可使用二官能以上之化合物。作 為其例’可例舉參(2_羥基)異三聚氰酸酯二丙烯酸酯、3· 丙稀酿氧甘油單曱基丙烯酸酯、二甲基丙烯酸甘油酯、 1,6-己二醇二(甲基)丙烯酸酯、聚丙二醇二(曱基)丙烯酸 酉旨、經三甲基乙酸新戊二醇二(曱基)丙烯酸酯、2,2 ’ - 雙(4-(甲基)丙烯醯氧聚乙烯氧苯基)丙烷、2,2,-雙 (4-(甲基)丙烯醯基氧聚丙烯氧苯基)丙烷、二環戊烷二 (甲基)丙烯酸酯、苯基環氧丙醚丙烯酸酯甲伸苯二異氰 酸醋、己二酸二乙烯酯等,其他1分子中具有2個(甲基) 丙烯醯基之化合物;新戊四醇三(曱基)丙烯酸酯三羥甲 基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(曱基)丙烯酸 酯 '參[(曱基)丙烯醯基氧乙基]異氰酸酯,其他1分子中 具有3個(曱基)丙烯醯基之化合物;新戍四醇四(曱基)丙 烯酸酯、甘油二(甲基)丙烯酸酯六亞甲基二異氰酸酯, 其他1分子中具有4個(曱基)丙烯醯基之化合物;五官能 化合物係二新戊四醇單羥五(曱基)丙烯酸酯、其他1分子 中具有5個(甲基)丙烯醢基之化合物;六官能化合物係二 新戊四醇六(甲基)丙烯酸酯、其他1分子中具有6個(曱基) 丙烯醯基之化合物等。 -12- 201244940 之丙嫌_ /在本發月之積層片,為P2層之主要構成成分 =稀酸系樹脂,由抗熱性或擠壓性之觀點,以作為具 ,..τ基甲基丙烯酸酯為主要 成分者較佳。此外,在眇餅句 ^ ^ ^ t s的主要成分,係指使用於 丙席s夂系樹脂之全部且有( 〇0^^0/ 丨,、有(甲基)丙烯醯基之化合物中為 8 〇莫耳/〇以上、再佳為9 〇莫 . 具耳。以上、更佳為95莫耳❶/0以 上° 本發明之積層片中,為爲+ + m ^ m , ” 之主要構成成分的丙烯 &糸树月曰,由成形性或積層性之觀點 點,在溫度25(TC、剪斷过厗1ΠΛ 田成巾性4之 上3 1〇_… 中炫融黏度5000泊以 上3 1 0 〇 〇泊以下較佳。更佳 ^ , 又猛為5000'泊以上20000泊以下。 在本电明之積層片之Ρ2層含右 极係#· i曰认田 有無機微粒。該無機微 “糸依其目的用以賦予必要的功能於薄犋 適當使用之微粒而言,可例示 X月了 初忐&咿β胁缺/ 系外線吸收能之無機微 粒或與1破酸S曰糸樹脂之折 性之微粒、顏料等之物,藉=粒’具有導電 反射性、白色性等的光學特性、紫外線性或光 粒係…已投影的換算等匕卜微 circus conversion diame 之直徑(叩㈤咖 • )斤致初級粒徑(primarv partlcle diameter)為 5nm 以上 '(primary 說明,在本發明中,粒徑俜沪 ’X,只要無特別 粒之意。 卡刀級粒@ ’微粒係初級微 進一步就微粒予以詳細說 而丄 γ你丨與如, 在本發明以無機微粒 而,,可例舉例如金、銀、銅、鉑 鈷、鐵、鋅、在了、鐯、鉻 、釩、鐵、 錄1呂錫、#、&、Μ、 201244940 ^ 鑭4之金屬;氧化鋅、氧化鈦、氧化 絶氧化銻、氧化錫、自·錫氧化物氧化釔、氧化鑭、 氧化鍅:氧化鋁、氧化矽等之金屬氧化物;氟化鋰、氟 化鎂t化鋁、冰晶石等之金屬氟化物;_酸鈣等之金 屬雄酸鹽;碳酸艇I 。β . ^ » 等之奴酸鹽;硫酸鎖專之硫酸鹽;滑 石及高嶺土等。 在本發明’鑑於在屋外使用頻度高’具有紫外線吸 收能m例如在無機微粒使用氧化鈦、氧化辞、氧 化鈽等之金屬氧化物之情形,可靈活運用微粒所致抗紫 外線、歷經長期門雜4* 、 ' 十 、 d門,准持機械強度,而顯著發揮本發明之 果進V ,由可提供高反射特性之觀點,使用氧 鈦作為無機微粒較佳,以你—此[& ^ 钗佳,以使抗紫外線性更高之觀點,以 使用金紅石型氧化鈦更佳。 使用於本發明之精屏 ^ ^ ^ ^ 積層片之無機微粒之已投影的換算 專h Η所致體積平均粒徑 平又佳為1 Onm以上3 μηι以下, 特佳為15nm以上2μιη以下。 在本發明之積層κ 2層之無機微粒含有率Wa2為 1質:!: %以上2 0質詈。w 丁 ^ 、 曰 下。更佳為3質量%以上1 §質 董%以下,進一步較佳A % 孕又佳為4為量0/〇以上12質量%以下。 在無機微粒含有率Wa ? I t α 羊Μ小於1質量%之情形’則無法充 二"、效果’尤其是在具有紫外線吸收能之微粒之情 =則性並不充分,會有長期使用時機械強度 -溥 於破裂之情形。又,無機微粒含有率Wa2 在超過20質量。/〇之愔拟,&士 之清形會有積層片變脆,薄片之機械 寺性降低之情形。在本發明 + ¾ 槓層片,藉由使p2層之無 -14- .201244940 機微粒含有率Wa2為1皙旦。, π干dZ荷1質里%以上20質量。/。以下,則可 維持薄片之機械特性’同時顯現微粒之添加效果。 在本發月之積層片,在層含有無機微粒較佳。藉 由在Ρ1 &含有無機微粒,而可更加提高微粒之添加效 果在此所說的無機微粒,係指可使用與上述Ρ2層所含 的無機微粒相同之物。此時,P1之無機微粒含有率Wal, 較佳為0.1質量%以上15質量%以下。更佳為i質量。/〇 以上10質量%以下’再佳為3質量%以上8質量%以下。 P1層之無機微粒含量Wal超過丨5質量%時,則有抗濕 熱性降低之可能性。 ‘' 又,在本發明之積層片,在P1層含有無機微粒之情 形,p 1層之無機微粒含量Wal與P2層之無機微粒含有 率Wa2之比Wal/Wa2,以〇以上〇 8以下為佳。更佳為 0以上0.7以下,進一步較佳為〇以上〇 5以下。 超過0.8時,則Wal變得過大,會有抗濕熱性降低之情 形。在本發明之積層片,藉由使P1層之無機微粒含有^ Wal與P2層之無機微粒含有率Wa2之比Wal/Wa2為〇 以上0.8以下,則不致降低抗濕熱性,可將使之含有微 粒所致效果顯現最大限。 在本發明之積層片,較佳為P 1層與P2層之微粒含 有率之平均Wave為3質量%以上。在此,p 1層與P2層 之微粒含有率之平均Wave係指根據下述式(1)所得之 值。 無機微粒含有率之平均 Wave = (Wal χτί + Wa2 T2)/(T1 + T2)…(1) Χ 201244940 其中,T1為P1層之層厚度(^),丁2為p2層之層 厚度(μηι)。 a P1層與P2層之微粒含有率之平均Wave,更佳為$ f量。/。以>上,再佳為10質量%以上。在本發明之積層^ , 藉由使薄膜全體之無機微粒率Wave設在3質量%以上 則使之含有無機微粒作為P1層與P2層之全體°所致效 果’例如可使抗紫外線性更高,又使用氧化鈦等作為無 機微粒之情形,可提高積層片之光反射特性。 … 在本發明之積層片,由使P2層之機械特性更高的觀 點,較佳為含有彈性成分。該情形之彈性成分之含量 Wb2,較佳為在P2層中添加5質量%以上5〇質量%以下。 更佳為10質量%以上40質量%以下,再佳為12質量%以1 30質量。/。以下,特佳為15質量%以上25質量%以下。以彈 性成分之例而言,除了丙烯酸酯系化合物、聚矽氧 酸系化合物等之具有彈性之微粒成分之外,亦可適 用聚醋系樹脂、聚烯烴系樹脂、聚醯胺系樹脂、聚:亞 胺系樹脂、聚醚系樹脂、聚醋醯胺系樹脂、聚醚酿 脂、丙烯㈣樹脂、聚胺基甲_旨系樹脂、聚碳酸酿 樹脂、聚氯化乙烯系樹脂等之熱塑性樹脂。 曰” 又’在本發明之積層片之ρι層、以層,在不損及 本’明效果之範圍内,亦可調配其他添加劑(可例舉例如 抗熱穩定劑、紫外線吸收劑、抗氣候穩定劑、有機之順 滑劑(一—)、顔料、染料、填充劑、 核劑等。其中’本發明所謂無機微粒並無意涵在此所說 的添加劑)。例如’選擇紫外線吸收劑作為添加劑之情 201244940 形,則可更加提高本發日月㈣片之抗紫外線性。以例如 聚碳酸s旨系樹脂、或與丙稀酸系樹脂互溶的有機系紫外 線吸收劑之例而言,可例舉水揚酸系、二苯酮系、苯并 二唑系、二啩系、氰丙烯酸酯系等之紫外線吸收劑及受 阻胺系等之紫外線吸收劑等。具體言之,可例舉例如水 揚酸系之水楊酸對-三級丁基笨8旨、水揚酸對辛基苯酿、 二苯嗣系之2,4·二趣二苯酮、2-經基_4-甲氧基二苯酮、 2-羥基-4-甲氧基-5-磺酸美-贫 尹' 馱基―本酮、2,2,,4,4’-四羥二苯 酮、雙(2 -甲氧基-4-麵其 ς u 基_5-卞基苯基)曱烷、苯并***系 之2-(2,-經基-5,-▼基苯基)苯并三〇坐、2_(2,_經基_5 基苯基)苯并***、2 2,_ ώ甲雙[4-(1,1,3,3-四曱基丁 基)-6-即苯并三。坐_2_基)紛]、三听系之2_(4,6_二苯基 一_ :)5[(己基)氧]-酚、氰丙烯酸酯系之乙基 -2 -氰- 3,3’-二苯基丙稀酸炉、. 邱吸^)、跫阻胺系之雙(2,2,6,6_四 甲基如底。定基)癸二酸,、璩站酸二甲酿· ^經乙 基)-4-羥基四甲基哌啶縮聚物。 其他可例舉2_(4,6_二笨基-1,3,5-三基)-5-[(己 基)氧]-酚、雙(辛基笨基 基-3,5,-—級τ其)爪化鎳、及2,4-二-三級丁基苯 ,一一級丁基十,笨甲酸酿等。 本發明之積層片係句八 上述要件的P1層▲ P2 3 積層結構,其含有滿足 表層側設置P2層的構成二:過較佳為在其至少單側之 最外層為P2層之構成、較佳是積層片之至少一 P1 ^ . , m 。進一步較佳為,另一最外層為 層错由成為本構成 置η層於與封閉材料^成-種積層#,其係藉由設 一他構成構件之密接之面側,並 201244940 使P2層成為與率Μ 勹〇在接之面為相反側之層,而可以 賦予對積層片之抗、县埶性、 3 4級 一 ,.、、,、、、 及使之含有微粒所致柱从坦 南效果,且(在與其他構件之貼合時)具有更高密接性 本發明之積層片之總厚度較佳 ’。 以下,進-步較佳為2。,以上45〜以下,最佳上: 以上400μηι以下。 佳為30μηι φ ^ , 將本發明之積層片使用於太陽 電池背板用途之情形,因應背板所要 上述範圍内適宜調整厚产。 又電壓,在 •序度。本發明之積層g 1 Ομιη之情形,薄片 予度小於 會有降低使之含有微或Ρ2層變得過薄, 。,更厚之情形,例如使用作為太 ::二 形’會有太陽能電池電池組之全體厚度變得過厚 在本發明之積声片,腺pija ^ P2層之層厚度設為曰Τ2Γ η θ之層厚度設為Tl(㈣, 足下述式⑴。‘"、㈣時,兩者之比Τ1/Τ2有必要滿 (Wa2+ 18)/9.5^ T1/T2(I) 更佳為Ti/T2為3以上,再佳為*以上。此外,pi 曰及/或P2層為複數層之情形以其合 層之層厚度為:π、Ρ2^ °又,使P1 TUP2之層厚度丁2 ” Μ1層之層厚度 則舍右a η 比m若無法滿足上述式⑴, 有涛片之機械特性降低,易於破裂之情形。又,在 將本發明之積層# ρ 過大之情形。在:i::::片之構成時’會有捲曲變得 性。此外,就用等可適用的機械特 之上限,雖無特別限定,不過例如 201244940 以共擠壓法進行製膜時,劍眩盔 ^ ^為良好’由抗紫外線性或 光子特性成為良好的觀點,較佳為丁1/72為3〇以下更 佳為20以下,特佳為15以下。 在本發明之積層片,Ρ2層之層厚度Τ2較隹為Η㈣ 以上。更佳為5,以上,再佳為7μιη以上,特佳為1〇叫 層之層厚度Τ2Μ3·5μιη時,則無機微粒添 加所致特性提高效果傾向於降低。在本發明之積層片, 藉由將”層之層厚度Τ2設為3.5μιη以上,則可‘現微 粒之添加效果。此外,Ρ2層之層厚纟Τ2之上限,並益 特別限制’以使Τ1/Τ2設在滿足上述式⑴式之範圍,則 薄片士之機械特性成為良好’且將積層片設為非對稱之構 成日寸’以可抑制捲曲變大的觀點較佳。 又,本發明之積層片’係根據ASTM D882 97(參照 1 999年版ASTM標準年鑑)而測定的斷裂伸長率為 以上較佳。更佳為5G%以上、再佳為Μ%以上。藉由設 在此種範圍’可將積層片適當使用於太陽能電㈣板用 等。 又,本發明之積層片,在溫度125t、濕度i〇〇%rh 之環境下,、經48 +時處理後之伸長保持率(ei()ngati()n 咖Won)為20%以上較佳。更佳& 3〇%以上、再佳為4〇% 以上、特佳為5G%以上。在此所說伸長保持率係指根據 astm-D882_97(參照1 999年㈤伽標準年鑑)所測定 之物’其中將處理前之積層片之斷裂伸長率設為別、該 處理後之斷裂伸長率設為E時’係根據下述⑺式所求得 之值。 -19- 201244940 伸長保持率(%)= (Ε/ΕΟ)χ1〇〇…(2)式 此外在測定時,將試料切出成測定片之形狀後,實 施處理’測定處理後之試樣。藉由設在此種範圍,可使 積層片之抗濕熱性更進一步良好,可製成使用本發明之 積層片的太陽能電池之抗濕熱性成為良好之物。 又本發明之積層片係在溫度6 0 °C、5 0 % R Η之環境 下,以強度100mW/cm2之金屬鹵素燈(波長範圍:295至 4 50nm、波峰波長:365nm),經48小時照射處理後之伸 長保持率為2 5 %以上為較佳。更佳為3 5以上、再佳為 3 7 以上特佳為4 0 %以上。此外,在本發明之積層片 照射金屬鹵素燈之情形,係使本發明之積層片之ρ2層側 暴露。又,在測定時,將試料切出成為測定片之形狀後, 實施處理’測定處理後之試樣。藉由設定此種範圍',則 可使薄片之抗紫外線性成為良好。 本發明之積層片係在溫度125。〇、濕度1〇〇%RH之 環境下,經48小時處理後之伸長保持率為2〇%以上,且 在溫度60°C、50%RH之環境下,在強度1〇〇mW/cm2之 金屬il素燈(波長範圍:295至45〇nm、波峰波長: 3 65nm)’經48小時照射處理後之伸長保持率為25%以上 為較佳。可使該範圍並存之積層片,相對於包含先前之 聚碳酸S旨系、樹脂的帛# ,0可成為抗濕熱性與抗紫外線 性優異之物,故例如可適用作為太陽能電池背板,使用 時亦可歷經長期間維持機械強度。 又,本發明之積層片可與其他薄膜等積層。在該其 他4膜之例,有用以提高機械強度之聚酯層、抗靜電層' -20- 201244940 與其他材料之密接層 抗 紫外線層、用以赋二進一步提高抗紫外線性· 賦予難燃性之難燃層、用以提高批衝擊 性或抗摩擦性之硬涂 * a選 更土布層等,可因應用途而任意地泛 擇。/、具體例,可侦與· ^ υ舉·在將本發明之積層片使用作為 太%此電池背板之,声 .U. 牙极之if形,為了進一步提高與其他薄片材 料 '或埋入發電元件 ^ ^m) 〕封閉材料(例如伸乙基乙酸乙婦- 之密接性之易拯罢_ s k ., 约锲者層、抗紫外線層、難燃層,除此之外 可形成導電層箄,甘a,4 α备 ^ 其係使為絶緣性指標的部分放電現象 之發生的電壓提高。 接者,例舉本發明之積層#之製造方法為例加以說 明0 在本發明之積層片,為Ρ1層之主要構成成分的聚碳 酸酯系樹脂’係將二羥二芳基化合物與光氣、或二苯基 碳酸醋等之碳酸自旨以周知之方法反應而得。又,亦可適 當使用出光興產股份有限公司製‘‘ TARFL〇N„ 、帝人化 成股伤有限公司製“ Panlite” 、三菱工程塑膠股份有限 公司製 Novarex” 、住友Dow股份有限公司製 “Calibre等市售之聚碳酸酯系樹脂。 又’為P2層之主要構成成分之丙烯酸系樹脂係藉由 將具有丙烯醯基、曱基丙烯醯基[以下,丙烯醯基與甲基 丙烯醯基一併稱為(甲基)丙烯醯基。就(曱基)丙歸酸、(甲 基)丙烯酸醋等亦作同樣之表現]之化合物予以聚合而可 得。又,橡膠等之改善柔軟性的成分,可在聚合時添加, 亦可在聚合後予以複合化之方法,任一方法可適告使 用。又,亦可適當使用住友化學股份有限公司製 -2 1- 201244940The measurement of Tg was carried out in accordance with JIS K7 122 (1 987) at a temperature increase rate of 20 ° C /min, and the temperature of the resin was raised from 25 ° C to 300 ° C (IstRUN), and held in this state for 5 minutes. Then, it was quenched to 25 ° C or lower, and the temperature was raised again to 300 at room temperature at a temperature increase rate of 20 ° C /min. 〇, the 2ndRUN differential scanning calorimetry chart, the change in the step shape of the glass transition is described in US K7 121 (1987) "9.3 Glass transition temperature method (1) Intermediate point glass transition temperature Tmg" The method is obtained. 201244940 Glass transition temperature Tg, preferably 125. (The above is more preferably 130 ° C or more, and still more preferably 135. (: Above, particularly preferably 14 〇 < t or more. Further, the laminated sheet of the present invention is an acrylic resin which is a main component of the P2 layer. By propylene group, fluorenyl fluorenyl group [hereinafter, propylene fluorenyl group and methacryl fluorenyl group are collectively referred to as (meth) acryl fluorenyl group. For (mercapto) acrylic acid, (methyl a polymer obtained by polymerizing a compound having the same performance as an acrylate or the like. In the laminate of the present invention, as an example of a compound having a (meth) propyl group based on an acrylic resin, The monofunctional compound may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate or lauryl (meth)acrylate. (meth)acrylic acid alkyl esters such as stearyl acrylate, isodecyl acrylate, etc.; 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Hydroxypropyl (meth) acrylate, polypropylene glycol mono (meth) propylene Acid ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl acrylate, decyl α-(hydroxydecyl) acrylate, ethyl α-(hydroxyindenyl) acrylate, n-butyl α-( Hydroxymercapto) acrylate, bis(2-hydroxy)isocyanate diacrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(methyl) propylene oxirane 2-2-hydroxyethyl phthalic acid monoglyceryl acrylate, etc. An acrylate having a carboxylic acid group such as a methoxyethyl-capric acid or a 2-(indenyl) propylene oxyethyl hexahydrophthalic acid; a phenyl (meth) acrylate or a phenyl cyanoacrylate Alkyl-terminated polyalkylene glycol mono(mercapto) acrylates such as esters, nonylphenoxy polyethylene glycol (meth) acrylates, etc.; hydrazine, hydrazine-dimethylaminopropyl (fluorenyl) ) acrylamide, acryl oxime 201294440. (meth) acrylamide such as forest, N-isopropyl (meth) acrylamide, etc., one (meth) acryl oxime in one molecule For example, However, these may be used singly, and it is also possible to use a plurality of kinds as needed. Further, the acrylic resin of the present invention may be used in addition to the above compound having a (fluorenyl) acryl-based group. A compound having a functional group or more. As an example thereof, exemplified by (2-hydroxyl)isomeric cyanurate diacrylate, propylene oxyglycerol monodecyl acrylate, glyceryl dimethacrylate, 1, 6-Hexanediol di(meth)acrylate, polypropylene glycol bis(indenyl)acrylic acid, trimethylacetate neopentyl glycol bis(indenyl)acrylate, 2,2 '-bis (4- (Meth) propylene oxime ethoxy phenyl) propane, 2,2,-bis(4-(methyl) propylene fluorenyl oxypropyl oxy) propylene, dicyclopentane bis (meth) acrylate Ester, phenyl epoxidized ether acrylate methyl benzene diisocyanate vinegar, divinyl adipate, etc., other compounds having two (meth) acrylonitrile groups in one molecule; neopentaerythritol three ( Mercapto) acrylate trimethylolpropane tri(meth) acrylate, trimethylolethane tris(曱Acetate 'shen [(indenyl) acryloyloxyethyl] isocyanate, other compounds having 3 (fluorenyl) acrylonitrile groups in one molecule; neodecyl alcohol tetrakis(meth) acrylate, glycerol (meth) acrylate hexamethylene diisocyanate, another compound having 4 (fluorenyl) acrylonitrile groups in one molecule; pentafunctional compound pentaerythritol monohydroxy penta(meth) acrylate, other a compound having five (meth) acrylonitrile groups in one molecule; a hexafunctional compound is dipentaerythritol hexa(meth) acrylate, and a compound having six (fluorenyl) acryl fluorenyl groups in one molecule; . -12- 201244940 A suspected _ / laminated film in this month, is the main component of the P2 layer = dilute acid resin, from the viewpoint of heat resistance or extrusion, as a .. τ methyl group Acrylate is preferred as the main component. In addition, the main component of the 眇 句 ^ ^ ^ ^ ts refers to all of the compounds used in the 夂 夂 夂 resin and has ( 〇 0 ^ ^ 0 / 丨, in the compound with (meth) acryl oxime 8 〇 耳 〇 〇 、 、 、 、 、 、 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具 具. The propylene & eucalyptus sapphire of the composition, from the point of view of formability or buildup, at a temperature of 25 (TC, cut off 厗 1 ΠΛ 成 成 性 4 4 3 3 3 3 3 3 3 3 3 3 3 3 3 1 0 The following is better. It is better, and it is more than 5000' poise and more than 20,000 poise. In the layer of the electric layer, the second layer contains the right pole system. For the purpose of imparting the necessary functions to the microparticles to be used properly, it is possible to exemplify the inorganic particles of X 了 忐 amp 胁 胁 / / / / 系 系 / / / 系 或 或 或 或 或Resin-like particles, pigments, etc., which have optical properties such as conductive reflectivity and whiteness, ultraviolet light or light granules...projected The conversion is equal to the diameter of the microcircus conversion diame (叩(五)咖•) The primary particle size (primarv partlcle diameter) is 5nm or more' (primary description, in the present invention, the particle size of the Shanghai 'X, as long as there is no special The meaning of the granules. The knives of the granules of the granules are as follows: Iron, zinc, in, bismuth, chromium, vanadium, iron, recorded 1 Lu Xi, #, &, Μ, 201244940 ^ 镧 4 metal; zinc oxide, titanium oxide, oxidized ruthenium oxide, tin oxide, from Tin oxide cerium oxide, cerium oxide, cerium oxide: metal oxides such as aluminum oxide and cerium oxide; metal fluorides such as lithium fluoride, magnesium fluoride, aluminum oxide, cryolite, etc.; Salt; carbonated boat I. β. ^ » sulphate; sulfate-specific sulfate; talc, kaolin, etc. In the present invention 'in view of the high frequency of use outside the house' has ultraviolet absorption energy m, for example, oxidation in inorganic particles Titanium, oxidized, yttrium oxide, etc. In the case of the compound, it is possible to flexibly use the ultraviolet rays caused by the particles, the long-term gates 4*, the 'ten, d gates, and the mechanical strength, and the effect of the present invention is significantly improved, from the viewpoint of providing high reflection characteristics. It is preferable to use oxytitanium as the inorganic fine particles, and it is preferable to use rutile-type titanium oxide from the viewpoint that the ultraviolet ray resistance is higher. The fine screen used in the present invention ^ ^ ^ ^ The projected average conversion of the inorganic particles of the laminated sheets is preferably 1 Onm or more and 3 μηι or less, and particularly preferably 15 nm or more and 2 μηη or less. In the laminated layer κ 2 layer of the present invention, the inorganic fine particle content rate Wa2 is 1 mass: !: % or more. w Ding ^, 曰 下. More preferably, it is 3% by mass or more and 1 § is less than or equal to 20% by mass, and further preferably A% is preferably 4% by weight or more than 12% by mass or less. In the case where the inorganic microparticle content rate Wa? I t α is less than 1% by mass, the 'unable to charge', the effect 'especially in the case of particles having ultraviolet absorption energy is not sufficient, and there is a long-term use. Mechanical strength - in the case of cracking. Further, the inorganic fine particle content rate Wa2 is more than 20% by mass. / 〇 〇 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the +3⁄4 bar layer of the present invention, by making the p2 layer free of -14-201244940, the particle content rate Wa2 is 1 day. , π dry dZ load 1 quality more than 20%. /. In the following, the mechanical properties of the sheet can be maintained while the effect of adding particles is exhibited. In the laminate of this month, it is preferred to contain inorganic particles in the layer. By adding inorganic fine particles to Ρ1 &, it is possible to further increase the effect of adding fine particles. The inorganic fine particles as used herein mean the same as the inorganic fine particles contained in the above two layers. In this case, the inorganic fine particle content rate of P1 is preferably from 0.1% by mass to 15% by mass. Better for i quality. /〇 The above 10% by mass or less is more preferably 3% by mass or more and 8% by mass or less. When the inorganic fine particle content Wal of the P1 layer exceeds 5% by mass, there is a possibility that the moist heat resistance is lowered. Further, in the laminated sheet of the present invention, when the inorganic fine particles are contained in the P1 layer, the ratio of the inorganic fine particle content Wal of the p 1 layer to the inorganic fine particle content ratio Wa2 of the P2 layer is Wal/Wa2, and 〇8 or less is 〇8 or less. good. More preferably, it is 0 or more and 0.7 or less, and further preferably 〇 or more and 5 or less. When it exceeds 0.8, Wal becomes too large, and there is a case where the resistance to moist heat is lowered. In the laminated sheet of the present invention, when the ratio of the inorganic fine particle content Wa2 of the P1 layer to the inorganic fine particle content Wa2 of the P2 layer, Wal/Wa2, is 0.8 or more, the moisture resistance is not lowered, and it can be contained. The effect caused by the particles appears to be the maximum. In the laminated sheet of the present invention, it is preferable that the average wavelength of the fine particles of the P 1 layer and the P 2 layer is 3% by mass or more. Here, the average Wave of the particle content ratio of the p 1 layer and the P 2 layer means a value obtained by the following formula (1). The average particle content of the inorganic particles is Wave = (Wal χτί + Wa2 T2) / (T1 + T2) (1) Χ 201244940 where T1 is the layer thickness of the P1 layer (^), and D2 is the layer thickness of the p2 layer (μηι ). a The average Wave content of the P1 layer and the P2 layer is more preferably the amount of $f. /. It is preferably 10% by mass or more in terms of >. In the laminate of the present invention, when the inorganic fine particle ratio Wave of the entire film is set to 3% by mass or more, the inorganic fine particles are contained as the entire effect of the P1 layer and the P2 layer, and the ultraviolet ray resistance can be made higher, for example. In the case where titanium oxide or the like is used as the inorganic fine particles, the light reflection characteristics of the laminated sheet can be improved. In the laminated sheet of the present invention, it is preferable to contain an elastic component from the viewpoint of making the mechanical properties of the P2 layer higher. In this case, the content Wb2 of the elastic component is preferably 5% by mass or more and 5% by mass or less based on the P2 layer. More preferably, it is 10 mass% or more and 40 mass% or less, and further preferably 12 mass% and 1 mass. /. Hereinafter, it is particularly preferably 15% by mass or more and 25% by mass or less. In the case of the elastic component, in addition to the elastic particulate component such as an acrylate compound or a polyoxyacid compound, a polyester resin, a polyolefin resin, a polyamide resin, or a poly Thermoplastics such as an imide resin, a polyether resin, a polyacetamide resin, a polyether butter, a propylene (tetra) resin, a polyamine-based resin, a polycarbonate resin, and a polyvinyl chloride resin. Resin. Further, in the layer of the layered sheet of the present invention, the layer may be blended with other additives in the range which does not impair the effect of the present invention (for example, heat stabilizer, ultraviolet absorber, and weather resistance) Stabilizer, organic smoothing agent (I-), pigments, dyes, fillers, nucleating agents, etc., wherein 'the so-called inorganic fine particles of the present invention are not meant to be referred to herein.) For example, 'selecting ultraviolet absorbers as additives In the case of the 201244940 shape, the UV resistance of the film of the present day (fourth) can be further improved. For example, for example, a polycarbonate-based resin or an organic ultraviolet absorber which is miscible with an acrylic resin, Examples thereof include ultraviolet absorbers such as oxalic acid, benzophenone, benzodiazole, diterpene, and cyanoacrylate, and ultraviolet absorbers such as hindered amines. Specifically, for example, water yang can be exemplified. Acidic salicylic acid p-tertiary butyl stupid, salicylic acid p-octylbenzene, diphenyl fluorene 2,4 di benzophenone, 2-pyridyl 4-methoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid, mei-poor ' 驮 ― ketone, 2, 2 , 4,4'-tetrahydroxybenzophenone, bis(2-methoxy-4-facet-4-yl-5-nonylphenyl) decane, benzotriazole 2-(2,- Benzyl-5,-▼-phenylphenyl)benzotriazine, 2_(2,_transyl-5-phenyl)benzotriazole, 2 2, _ ώ 双 [4-(1,1, 3,3-tetradecylbutyl)-6-, benzotriene. Sit. _2_base), and 3) (4,6-diphenyl- _:)5[(hexyl)oxy ]-Phenol, cyanoacrylate type ethyl-2-cyanide-3,3'-diphenyl propylene acid furnace, . Qiu suction ^), bismuth amine series double (2,2,6,6_ Tetramethyl as a base, a fixed base, azelaic acid, a succinic acid, and an ethyl 4-hydroxytetramethylpiperidine polycondensate. Other examples are 2_(4,6_diphenyl) -1,3,5-triyl)-5-[(hexyl)oxy]-phenol, bis(octylphenyl)-3,5,--stage τ which is clawed nickel, and 2,4-di - a tertiary butyl benzene, a primary butyl ketone, a benzic acid saponin, etc. The laminated sheet of the present invention is a P1 layer ▲ P2 3 laminated structure of the above requirements, which contains a composition 2 which satisfies the P2 layer on the surface side: Preferably, the outermost layer on at least one side thereof is a P2 layer, preferably at least one P1 ^ of the laminated sheet. Further, it is preferable that the other outermost layer is a stacking layer which is formed by the η layer and the layered layer of the sealing material, which is formed by a side surface of the member, and 201244940 The P2 layer is formed as a layer on the opposite side to the surface of the layer, and the layer can be imparted with resistance to the laminated sheet, the grade of the layer, the level of 34, the film, the film, and the like. The column has a higher effect from the tanzan effect and (in the case of bonding with other members) the total thickness of the laminated sheet of the present invention is better. Hereinafter, the step is preferably 2. , above 45~ below, the best on: above 400μηι. Preferably, the laminated sheet of the present invention is used in the use of a solar cell back sheet, and the thick sheet is suitably adjusted in the above range in accordance with the back sheet. And the voltage, in the order. In the case of the laminate g 1 Ομιη of the present invention, the degree of sheeting is less than that which is lowered to make the layer containing micro or ruthenium too thin. In the case of a thicker case, for example, the use of as a ": dimorph" will cause the entire thickness of the solar cell battery pack to become too thick. In the sounding sheet of the present invention, the layer thickness of the gland pija ^ P2 layer is set to 曰Τ2 Γ η θ The layer thickness is set to Tl ((4), and the following formula (1). '", (4), the ratio of the two Τ 1 / Τ 2 is necessary to be full (Wa2+ 18) / 9.5 ^ T1/T2 (I) better Ti / T2 It is 3 or more, and more preferably * or more. In addition, when the pi 曰 and/or P2 layer is a plurality of layers, the layer thickness of the layer is π, Ρ 2 ^ °, and the layer thickness of P1 TUP2 is 2 Μ Μ 1 If the layer thickness of the layer is rounded off, the right a η ratio m does not satisfy the above formula (1), and the mechanical properties of the tile are lowered, which is liable to be broken. Further, in the case where the laminate # ρ of the present invention is excessively large, at: i:: In the case of the composition of the sheet, the curling property is changed. In addition, the upper limit of the applicable mechanical limit is not particularly limited, but for example, 201244940, when the film is formed by the co-extrusion method, the sword glare helmet ^ ^ From the viewpoint of good ultraviolet light resistance or photon characteristics, it is preferably from 1/72 to 3 Torr, more preferably 20 or less, and particularly preferably 15 or less. In the laminated sheet of the present invention, the layer thickness Τ2 of the Ρ2 layer is more than Η(4) or more, more preferably 5 or more, and more preferably 7 μmη or more, particularly preferably 1 〇 层 layer layer thickness Τ2Μ3·5μιη, then inorganic particles In the laminated sheet of the present invention, by adding the layer thickness Τ2 of the layer to 3.5 μm or more, the effect of adding the particles can be increased. Further, the layer thickness of the layer 2 is 2 The upper limit, and the special limit 'is such that Τ1/Τ2 is set in the range satisfying the above formula (1), the mechanical properties of the thin layer become good 'and the laminated sheet is made asymmetric, and the curl can be suppressed. Further, the laminated sheet of the present invention is preferably an elongation at break as measured according to ASTM D882 97 (refer to the ASTM Standard Yearbook of the 1999 edition), more preferably 5 G% or more, and more preferably Μ. % or more. By providing such a range, the laminated sheet can be suitably used for a solar electric (four) plate, etc. Further, the laminated sheet of the present invention is in an environment of a temperature of 125t and a humidity of i〇〇%rh, and 48. +Elongation retention rate after treatment (ei()ngati() n 咖 Won) is preferably 20% or more. More preferably & 3 % or more, more preferably 4% by weight or more, and particularly preferably 5 % by weight or more. Here, the elongation retention ratio is based on astm-D882_97 (refer to In the case of the 999 (5) gamma standard yearbook, the elongation at break of the laminated sheet before the treatment is set to be different, and the elongation at break after the treatment is set to E, which is obtained according to the following formula (7). -19- 201244940 Elongation retention ratio (%) = (Ε/ΕΟ)χ1〇〇 (2) In addition, during the measurement, the sample is cut into the shape of the measurement piece, and then the test is performed. kind. By setting it in such a range, the moisture resistance of the laminated sheet can be further improved, and the heat resistance of the solar cell using the laminated sheet of the present invention can be improved. Further, the laminated sheet of the present invention is subjected to a metal halide lamp having a strength of 100 mW/cm 2 (wavelength range: 295 to 450 nm, peak wavelength: 365 nm) at a temperature of 60 ° C and 50% R Η for 48 hours. The elongation retention after the irradiation treatment is preferably 25% or more. More preferably, it is 3 5 or more, and more preferably 3 7 or more is particularly preferably 40% or more. Further, in the case where the laminated sheet of the present invention is irradiated with the metal halide lamp, the ρ2 layer side of the laminated sheet of the present invention is exposed. Further, at the time of measurement, the sample was cut out into the shape of the measurement piece, and then the sample after the measurement measurement process was carried out. By setting such a range ', the ultraviolet resistance of the sheet can be made good. The laminate of the present invention is at a temperature of 125. In the environment of 〇 and humidity of 1〇〇%RH, the elongation retention after 48 hours of treatment is 2% or more, and in the environment of temperature 60°C and 50% RH, the strength is 1〇〇mW/cm2. The metal il lamp (wavelength range: 295 to 45 〇 nm, peak wavelength: 3 65 nm) is preferably 25% or more after the irradiation treatment for 48 hours. The laminate sheet which can coexist in the range can be used as a solar battery back sheet, and can be used as a solar battery back sheet, because it can be excellent in moisture resistance and ultraviolet resistance with respect to 帛#,0 containing the conventional polycarbonate. It is also possible to maintain mechanical strength over a long period of time. Further, the laminated sheet of the present invention can be laminated with other films and the like. In the case of the other four films, the polyester layer for improving the mechanical strength, the antistatic layer of the antistatic layer '-20-201244940 and other materials, and the ultraviolet layer for the adhesion of the other materials are used to further improve the ultraviolet resistance and impart flame retardancy. The flame retardant layer, the hard coating for improving the impact resistance or the rubbing resistance, and the like, can be arbitrarily selected according to the application. /, specific examples, detectable and ^ ^ υ · 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Into the power generation component ^ ^ m) 〕 sealing material (such as the extension of ethyl acetate - the adhesion of the easy to save _ sk., about the layer, anti-UV layer, flame retardant layer, in addition to forming conductive The layer 箄, 甘 a, 4 备 ^ 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The polycarbonate resin which is a main constituent component of the first layer is obtained by reacting a dihydroxydiaryl compound with phosgene or carbonic acid such as diphenyl carbonate or the like by a known method. "TARFL〇N" manufactured by Idemitsu Kosan Co., Ltd., "Panlite" manufactured by Teijin Chemicals Co., Ltd., "Novarex" manufactured by Mitsubishi Engineering Plastics Co., Ltd., and "Calibre" manufactured by Sumitomo Dow Co., Ltd. are commercially available. Polycarbonate resin. Also' The acrylic resin which is a main component of the P2 layer is obtained by having an acrylonitrile group or a mercapto propylene group [hereinafter, the acryl fluorenyl group and the methacryl fluorenyl group are collectively referred to as a (meth) acrylonitrile group. A compound obtained by polymerizing a thiol acid or a (meth)acrylic acid vinegar or the like can be obtained by polymerization. Further, a component which improves flexibility such as rubber can be added during polymerization or after polymerization. Any method can be used as a method of compounding. Also, it can be used as appropriate. Sumitomo Chemical Co., Ltd.-2 1- 201244940
Sunupex 、Kuraray股份有限公司製“p㈣pd”、三 菱Rayon股份有限公司塑“ a ,, 抖日t 1 Acrypet等市售之丙烯酸系 樹脂。 +在本發明之積層片’以積層ρι層及p2層之方法而 5 ’例如可使用:4"1層用原料與P2層用原料各自投 二臺擠壓機’予以熔融,在自卡口冷卻的鑄製鼓輪 。進U壓,加工成薄片狀之方法(共擠壓法);在以 單膜製作的薄片’投人被覆層原料於擠壓機,進行炼融 擠堡,自卡q —、息4氣两, & 邊擠堡—邊層合之方法(熔融層合法); 各自個別的製作各薄膜,以經加熱的輥群等予以熱壓合 (th㈣。咖叫——㈣)之方法(熱層合法);經由接 者劑貼合之方法(接著法);其他,將;容解於溶劑之物予 以塗布·摩乞燥之方法(塗布法)、&纪合該等之方法等。 :等中’以製造步驟短’且層間之接著性良好之觀點, 為共擠壓法。以下’詳述共擠壓法之製法。 情形在:A P1 ^之聚碳酸酯系樹脂中添加無機微粒之 、二方法,係預先將聚碳酸酯系樹脂與無機微粒, 用通氣式二軸捏合擠壓機或串列(tandem)型擠壓機, 乜σ之方法為較佳。在此,在使之含有無機微 ’因承受熱過程,使不少聚碳酸g旨系樹脂劣化。因 匕旦由k濕熱性之觀點’較佳是相較於ρι層所含無機微 二=,製作無機微粒添加量多的高濃度母粒使其與聚 :S:知糸樹脂混合並稀釋’製成規定的ρι層之無機微粒 含有率。 -22- 201244940 ,時’高濃度母粒之濃度較佳為2〇質量%以上8〇 貝量下,再佳為25質量%以上70質眚 為30皙旦《ν 貝量°/〇以下、更佳 馬 ϋ資里/〇以上60質量%以下、特佳A “ ι^曰 60皙旦0/,、, 幵佳為40質量%以上 之㈣。^下。在不足2〇質量。/。之情形,添加於P1屏 之母料之夏變多,結果在ρι層中劣化曰 夕吾鐵夕 J峨石及酸酯糸樹脂 夕,會有抗濕熱性降低之情形。又,超過 旦 料化變得困難,在將母料現合於聚碳酸: 糸树月曰之情形,會有均勻地混合變得困難之情形。 ,又,在構成Ρ2層之丙烯酸系樹脂添加無i微粒之情 形:该方法較佳是預先將丙烯酸系樹脂及無機微粒,使 I通氣式二軸捏合擠壓機或串列型擠壓機,進行熔融捏 合之方法。在此,在使之含有無機微粒時因承受熱過程, 故使不少丙烯酸系樹脂劣化。因此’ “2層之機械強度 之觀耗之’較佳是製作相較於p 2層所含無機微粒量之 無機微粒添加量多的高濃度母粒,使其與丙烯酸系樹脂 混合並予稀釋,製成規定的P2層之無機微粒含有率者。 此日卞,咼濃度母粒之濃度較佳為2 〇質量%以上8 〇 質量/。以下,更佳為2 5質量%以上7 〇質量。/。以下、再佳 為30質量%以上6〇質量%以下、特佳為4〇質量%以上 60質量%以下。在不足2〇質量%之情形,添加於p2層 之母料之量變多,其結果在P2層中劣化的丙烯酸系樹脂 之里變夕’會有使P2層之機械強度降低之情形。又超過 80質量%之情形,母料化變得困難,或在將母料混合於 丙烯酸系樹脂之情形,以均勻地混合之物變得困難之情 形。 -23- 201244940 接者,在將本發明之積層片以共擠壓法製作 形,首先,將混合了含有取 / 凊 粒的母粒之P1層用έ且成物v糸樹脂原料、無機微 層用組成物予以乾燥後,在氮氣流下 減壓下,供給於加熱至24〇t以上3〇〇<>c以下 佳 25rc以·"靴以下的擠壓機並予炫融。又,將混人: 含有丙稀酸系樹脂原料、無機微粒之母粒的p2層用: 物各自乾燥後’在氮氣流下或者減壓下,供給於加' 幫…7〇t以下,更佳為⑽以上25吖以; !他播壓機並予以炼融。接著,使用多歧管模或進料套 官或靜態混合器、複合裝置(Pinol)等,將P1層與”屛 合流、積層,自模進行共播壓。 將藉由則述方法自模排出的積層片,在缚塑鼓輪等 之冷卻體上進行擠壓、冷卻固化,而可獲得本發明:積 層片。此時由所得薄片之平面性之觀點,以第1段之冷 卻時冷卻體溫度設為飢以上丙稀酸系樹脂之玻璃轉: 溫度-HTC以下較佳。又,此時,係使用金屬線狀、帶狀、 針狀或者77狀等之電㉟,以#電力冑接_塑鼓輪κ 冷卻體為佳。 以4方法所得之本發明之積層片在不損及本發明效 果之範圍,可依照需要增加熱處理等之加工處理。此外, 以熱處理溫度之上限而言,由薄片之平面性等而言,較 佳是丙烯酸系樹脂之玻璃轉移溫度“〇c>c以下、更佳為玻 璃轉移溫度以了、再佳為玻璃轉移溫度_3〇t以 下。又,熱處理時間為5秒以上3〇分以下。藉由熱處理 而可提高本發明積層片之熱尺寸穩定性。 -24- 201244940 之密接 方法而 樹脂作 不同之 以共擠 單膜製 壓,自 自個別 之方法 他,將 ,及組 又,為了提高前述方法所得 性,亦可實施電晕處理、電聚處理。積層片 月之積層片’以與其他薄膜積層之 =,可使用例如:在穡声夕々 為主要構成材料之情形:將不二材料係將熱塑性 擠壓機,予以炫融,自卡!:同之材料各自投入 :,:加工成為薄片狀之方法(共擠壓法 以 作的薄片投入被覆層眉枓於检广 ,, 盾原於擠壓機,進行熔融擠 :二邊擠壓一邊層合之方法(溶融層合法);各 製作各薄膜,错由所加熱地輥群等予以熱壓合 (熱層合法);經由接著劑貼合之方法(接著法广豆 洛解於溶劑之物予以塗布•乾燥之方法(塗布法 合該等之方法等。 本發明之積層片可藉由前述方法來 '製造。所得之種 層片相較於先前之聚碳酸酷系樹脂薄#,抗 紫外線性、光學特性(光反射性 & & & υ于订|王(尤汉射性、白色性等)優異。此筹 積層片,除了太陽能電池用背板以外,以液晶顯示器用 反射板、汽車用材料、建築材料為始,在重視抗濕熱性 對於紫外線之耐性、光反射性般之用途,可適當使用。 尤其是藉由使用此等積層片,則可提供具有高耐久性纪 太陽能電池背板及使用其之太陽能電池。 本發明之太陽忐電池,其特徵為使用本發明之積層 片作為月板。藉由使用本發明之積層片,則相較於先前 之太陽能電池’可提高耐久性及變薄。其構成之例如第 1圖所示。在將連接擷取電力的引線(在第1圖未示出) -25- 201244940 的發電元件以EVA系樹脂等之透明的封閉劑層 物上,將玻璃等之透明基板4及本發明之積;片二 成作為太陽能電池用背板丨,但並 〇萬 1民疋於此,可#用 於任意之構成。此外’在第1圖雖係表示在本發明= 層片早體之例’不過因應其他被視為必要的 亦可使用本發明之積層片與其他薄膜之複人薄片特性, 背二二=之太陽能電池,上述太陽能電池用 奇板1,係δ又置於封閉發電元件的封閉劑層2之 =此較佳是配置使本發明積層片之ρ2層位 愈封 閉劑層2為相反側(第1圖之6)的位置。藉;摄 成,而可提高對於自地面反射 成為该構 A - y a L e 糸卜線專的耐性’可成 為向耐久之太陽能電池’並使厚度變薄。 之積層片為非對稱之構成中,在 00 在本發明 之情形,以可-封閉材二二t早側表面包含P1層 了閉材枓之密接性f古认站B … 層孫邮要士或, 更间的觀點較佳是P】 層係配置成為位於封閉材料層2側之位置。 發電元件3係將太陽光之 者,可將結晶石夕系、多έ士… 里良換成電氣能量 坊4 夕、,Ό日日石夕系、微結晶矽系、非曰开, 夕系、銅銦硒化物系、化合物半導俨系、“' 依目的之任音亓杜 Α糸色素增感系等, 1思疋件’因應所期望 數個予以串聯1 M 電i或者電〜,將複 甲%P次並聯地連接而使用。 具有透光性之诱明A 4 表層位置,故除了高透;率之外係位於太陽能電池之最 ‘I高抗污染性、高機械強度特性高抗氣候 明之太陽能電池,I f之透明材料。在本發 述特性,則可使用=材H透明基板4若可滿足上 〜材質以其例而言,可例舉玻璃、 -26- 201244940 四敦化乙稀-乙烯共聚物(ETFE)、聚氟化乙烯樹脂 (PVF)、聚氟化亞乙烯樹脂(pVDF)、聚四氟化乙烯樹脂 (TFE)、四就化乙烯-六氟化丙烯共聚物(FEp)、聚三氟化 氣化乙烯樹脂(CTFE)、聚氟化亞乙烯樹脂等之氟系樹 脂、烯烴系樹脂、丙烯酸系樹脂、及該等之混合物等為 佳。在玻璃之情形,以使用經強化之物更佳。又,在使 用樹脂製的透光基材之情形,由機械強度之觀點觀之, 將上述樹脂進行一軸或二軸延伸之物亦可適當使用。 又,在該等基材,為了賦予與為發電元件之封閉材 料的EVA系樹脂等之接著性,故較佳是在表面實施電暈 處理、電漿處理、臭氧處理、易接著處理。 用以封閉發電元件之封閉材料2,其目的係以樹脂 被覆叙電元件表面之凹凸並予固定,自外部環境保護發 電兀件,並予電性絶緣,除此之外,因係接著於具有透 光性的基材或背板與發電元件,故可使用具有高透明 性、尚抗氣候性、高接著性、高抗熱性的材料。以其例 而言,較佳可使用乙烯-乙酸乙烯酯共聚物(EVA)、乙烯_ 丙烯酸曱酯共聚物(EMA)、乙烯·丙烯酸乙酯共聚物(eea) 樹脂、乙烯-曱基丙烯酸共聚物(EMAA)、多離子聚合物 樹月曰、聚乙烯丁縮醛樹脂、及該等混合物等。 如上述,藉由將使用於本發明之積層片的太陽能電 池背板組裝於太陽能電池系統,相較於先前之太陽能電 池,而可製成高耐久及/或薄型之太陽能電池系統。本發 明之太陽能電池,太陽光發電系統、小型電子零件之電 源等,不限於屋外用途、屋内用途,而可適當使用於各 種用途》 -27- 201244940 [特性之評價方法] A. 層厚度ΤΙ、T2、積層比T1/T2 以下述(A1)至(A 4)之順序求得。此外,測定係 10處場所而測定,以其平均值,設定P1層之層 ΤΙ(μιη)、P2 之層厚度 Τ2(μιη)、積層比 T1/T2。 (Α1)使用薄片切片機(micortome),使積層片剖 在厚度方向毁壞’而相對於積層片面方向垂直地切 (A2)接著將切斷的剖面’使用電子顯微鏡觀察 得擴大500倍而觀察的影像。此外,觀察場所係隨 決定’不過係使影像之上下方向與積層片之厚度方 平行、而使影像之左右方向與積層片之面方向呈平 此外’在厚度方向全體無法容納於1幅影像中之情 則準備一影像,在厚度方向挪動觀察位置觀察,並 匹配複數幅影像,而可確認厚度全體。 (A 3)求得在該(A 2)所得影像中p 1層之層厚度 層P2之層厚度T2。 (A4)T1除以T2,計算積層比T1/T2。 B. 無機微粒含有率Wal、Wa2,Wave 自積層片切削P 1層、P2層之各層,就該等以 方法求得無機微粒含有率Wa 1、Wa 2。 測定已切削之物之質量wa(g)。接著,溶解於二 烷t,在已離心分離的不溶成分中’分餾無機微粒 所得之無機微粒以二氣曱烷洗淨、離心分離。此外 複進行洗淨作業,至即使在離心分離後之洗淨液添 醇亦不再白濁為止。求得所得之無機微粒之 wa’(g) ’自下述式(3)測定無機微粒含有率 改變 厚度 面不 斷。 ,獲 意地 向呈 行。 形, 藉由 T1、 下述 氯甲 。將 ,重 加乙 質量 -28- .201244940 無機微粒含有率(質i%)=(wa’/wa)xl〇〇".(3) 又’P1層與P2層之無機微粒含有率wave係以下述 式(1)求得。 無機微粒含有率之平均 Wave = (Wa 1 X T 1 + Wa2 X T2)/(T1 + T2)... (1) 其中’ ΤΙ為ρΐ層之層厚度(μπι),Τ2為Ρ2層之層 厚度(πι)。 C ·薄片機械特性 根據ASTM-D882(參照ASTM標準年鑑,1 999年 版)’測定將試樣切出1 cmx20cm之大小,以夾盤間5cm、 拉伸速度300mm/min拉伸時之斷裂伸長率。此外,試樣 數為n=5,又,就積層片之縱方向、橫方向之各方向進 行測定後’作為該等平均值求得。Sunupex, Kuraray Co., Ltd. "p (four) pd", Mitsubishi Rayon Co., Ltd. plastic "a,, shaken t 1 Acrypet and other commercially available acrylic resin. + In the laminated sheet of the present invention, the laminated layer of p1 layer and p2 layer For the method 5', for example, 4"1 layer raw material and P2 layer raw material are respectively cast into two extruders to be melted, and the casting drum cooled from the bayonet is pressed into a sheet shape. Method (co-extrusion method); in a thin film made of a single film, the coated material is poured into an extruder, and the smelting and squeezing is carried out, and the self-carding, the gas, the gas, the gas, the gas, the gas, the gas Combined method (melting layer method); each individual film is produced, and is heat-compressed by a heated roller group or the like (th (four). Coffee--(4)) method (thermal layering); bonding via a carrier The method (subsequent method); the other method of coating the solvent in the solvent, the method of drying (coating method), the method of combining the methods, etc. The viewpoint of good adhesion between layers is the co-extrusion method. The method of the method. In the case where the inorganic fine particles are added to the polycarbonate resin of A P1 ^, the polycarbonate resin and the inorganic fine particles are previously subjected to a vented two-axis kneading extruder or a tandem ( Tandem) type extruder, 乜σ method is preferred. Here, it is made to contain inorganic micro-because of the thermal process, so that many polycarbonates are degraded. Because of the k-heating property 'It is preferable to prepare a high-concentration masterbatch with a large amount of inorganic fine particles added to the inorganic fine particles contained in the ρ layer, and mix and dilute it with the poly:S: 糸 糸 resin to make the inorganic particles of the prescribed ρ layer -22- 201244940, when the concentration of the high-concentration masterbatch is preferably 2〇% by mass or more and 8 lbs, and then more than 25% by mass. 70 眚 is 30 皙 《 ν 量 ° / 〇The following, the best horses in the capital / 〇 above 60% by mass, the best A " ι ^ 曰 60 皙 0 0 /,,, 幵 good is 40% by mass or more (four). ^Under. In less than 2 〇 quality. /. In the case where the amount of the masterbatch added to the P1 screen is increased, the deterioration of the ρ 吾 铁 铁 铁 峨 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及Further, in the case where the master batch is difficult to be formed, it is difficult to uniformly mix the master batch in the case of the polycarbonate: eucalyptus. Further, in the case where the acrylic resin constituting the ruthenium layer 2 is added with no io particles, the method preferably uses an acrylic resin and inorganic fine particles in advance, and a ventilated two-axis kneading extruder or a tandem type extruder. A method of performing melt kneading. Here, when the inorganic fine particles are contained, they are subjected to a heat process, so that many acrylic resins are deteriorated. Therefore, it is preferable to produce a high-concentration masterbatch having a larger amount of inorganic fine particles than the inorganic fine particles contained in the p 2 layer, and to mix and dilute it with the acrylic resin. The content of the inorganic fine particles in the predetermined P2 layer is set. The concentration of the cerium concentration masterbatch is preferably 2 〇 mass% or more and 8 〇 mass /. or less, more preferably 2 5 mass % or more and 7 〇 mass. The following is more preferably 30% by mass or more and 6% by mass or less, and particularly preferably 4% by mass or more and 60% by mass or less. In the case of less than 2% by mass, the amount of the master batch added to the p2 layer is increased. As a result, in the case of the deteriorated acrylic resin in the P2 layer, there is a case where the mechanical strength of the P2 layer is lowered. In the case of more than 80% by mass, the masterbatch becomes difficult, or the master batch is mixed. In the case of an acrylic resin, it is difficult to uniformly mix the objects. -23- 201244940 Next, in the case where the laminated sheets of the present invention are formed by a co-extrusion method, first, the mixture is mixed and contained. P1 layer of the masterbatch of the granules After drying the composition of the inorganic microlayer, it is supplied to a press machine which is heated to 24 〇t or more and 3 〇〇<>c or less to the following 25 liters under the pressure of nitrogen gas. In addition, it will be mixed: The p2 layer containing the acrylic resin raw material and the inorganic fine particle masterbatch is used: After the materials are dried, they are supplied under the nitrogen flow or under reduced pressure, and are added to the '7 〇t or less. More preferably (10) or more and 25 吖; ! He smelts the machine and smelts it. Then, using the multi-manifold die or feed sleeve or static mixer, composite device (Pinol), etc., the P1 layer and the 屛 流, layering, self-casting and co-casting. The laminated sheet discharged from the mold by the method described above is pressed, cooled and solidified on a cooling body such as a binding drum, whereby the present invention can be obtained: a laminated sheet. At this time, from the viewpoint of the planarity of the obtained sheet, the temperature of the cooling body at the time of cooling in the first stage is set to be a glass transition of the acrylic resin of a hungry or higher: temperature - HTC or less is preferable. Further, in this case, it is preferable to use a wire 35 such as a metal wire, a belt, a needle, or a 77, and it is preferable to use a power splicing_plastic drum κ heat sink. The laminated sheet of the present invention obtained by the method 4 can be subjected to a processing such as heat treatment as needed without impairing the effects of the present invention. Further, in terms of the upper limit of the heat treatment temperature, the glass transition temperature of the acrylic resin is preferably 〇c>c or less, more preferably the glass transition temperature, and more preferably the glass transition. The temperature is not more than 3 〇t. Further, the heat treatment time is 5 seconds or more and 3 minutes or less. The heat dimensional stability of the laminated sheet of the present invention can be improved by heat treatment. The bonding method of -24-201244940 and the resin are different. Extrusion of single-film pressure, from individual methods, hesitation, and group, in order to improve the performance of the above method, corona treatment, electropolymerization treatment can also be carried out. Layered sheets of laminated sheets are laminated with other films. =, for example, in the case where the 穑 々 々 is the main constituent material: the thermoplastic material extruder will be fused, self-carding!: The same materials are put into each other::: processed into flaky Method (The co-extrusion method is used to put the sheet into the coating layer for inspection, and the shield is used in the extruder to perform melt extrusion: a method of laminating on one side of the extrusion (melting layer method); each film is produced ,wrong The heated roll group or the like is subjected to thermocompression bonding (thermal lamination); a method of bonding by means of an adhesive (the method of coating and drying the method in which the method is applied to the solvent) (the method of coating the method, etc.). The laminated sheet of the present invention can be 'manufactured by the aforementioned method. The obtained layer sheet is thinner than the previous polycarbonate thin resin, UV resistance, optical characteristics (light reflectivity &&&& It is excellent for the anti-moisture heat of the liquid crystal display, including the reflector for the liquid crystal display, the automotive materials, and the building materials. For the purpose of ultraviolet resistance and light reflectivity, it can be suitably used. In particular, by using such a laminated sheet, a solar cell having a high durability and a solar cell using the same can be provided. It is characterized in that the laminated sheet of the present invention is used as a moon plate. By using the laminated sheet of the present invention, durability and thinning can be improved as compared with the prior solar battery. As shown in the figure, a transparent substrate 4 such as glass is placed on a transparent sealing layer of an EVA-based resin such as a lead wire for connecting power drawn (not shown in Fig. 1) -25-201244940 The product of the present invention; the film is used as a back sheet for a solar cell, but it can be used for any configuration. In addition, in the first figure, it is shown in the present invention. The example of the body 'but the other is considered necessary, can also use the laminated sheet of the present invention and the characteristics of the composite sheet of the other film, the back solar cell, the solar cell with the odd plate 1, the δ is placed again The sealant layer 2 of the closed power generating element is preferably disposed such that the ρ2 layer of the laminated sheet of the present invention is at the opposite side (6 of Fig. 1). By taking it, it is possible to improve the resistance to the reflection of the structure from the ground to the structure A - y a L e , which can become a durable solar cell and thin the thickness. In the case of the present invention, in the case of the present invention, the front side surface of the closable material and the second side of the second layer includes the P1 layer, and the closeness of the closed material f 古 f 古 古 ... ... ... ... ... ... 孙 孙 孙 孙Or, the more preferable viewpoint is that the layer system is disposed at a position on the side of the sealing material layer 2. The power generation component 3 is a person who uses sunlight, and can replace the crystal gems and the many gentlemen... Liliang is replaced by the electric energy workshop 4 eve, the Ό日日石夕, the microcrystalline 矽 system, the non-opening, the eve , copper indium selenide system, compound semi-conducting lanthanide system, "' according to the purpose of the 亓 亓 亓 Α糸 Α糸 Α糸 Α糸 Α糸 等 , , ' ' ' ' ' ' ' ' ' ' ' ' 因 , , , , , , , , , , , , , The composite parts are connected in parallel and used in parallel. The light-transmissive shape of the A 4 surface layer is the highest in the solar cell, and the high mechanical strength is high. Anti-climate solar cell, transparent material of I f. In the present invention, the material can be used for the transparent substrate 4, if it can satisfy the above-mentioned material, for example, glass, -26-201244940 Ethylene-ethylene copolymer (ETFE), polyvinyl fluoride resin (PVF), polyvinylidene fluoride resin (pVDF), polytetrafluoroethylene resin (TFE), tetra-ethylene-hexafluoropropylene copolymer Fluorine resin or olefin such as (FEp), polyfluorinated vaporized ethylene resin (CTFE), or polyvinylidene fluoride resin A hydrocarbon resin, an acrylic resin, a mixture thereof, etc. are preferable. In the case of glass, it is more preferable to use a reinforced material. Further, in the case of using a light-transmitting substrate made of a resin, from the viewpoint of mechanical strength It is to be noted that the above-mentioned resin may be suitably used for one-axis or two-axis extension. Further, in order to impart adhesion to an EVA-based resin or the like which is a sealing material for a power-generating element, it is preferable to provide such a substrate. The surface is subjected to corona treatment, plasma treatment, ozone treatment, and easy subsequent treatment. The sealing material 2 for enclosing the power generation element is designed to cover the surface of the electric component by resin and fix it, and the external environmental protection power generation element And electrical insulation, in addition to the light-transmitting substrate or backing plate and power generation components, it can be used with high transparency, weather resistance, high adhesion, high heat resistance For example, ethylene-vinyl acetate copolymer (EVA), ethylene methacrylate copolymer (EMA), ethylene ethyl acrylate copolymer (eea) resin, ethylene-ruthenium may be preferably used. base An olefinic acid copolymer (EMAA), a polyionic polymer tree, a polyvinyl butyral resin, and the like, etc. As described above, the solar cell back sheet used in the laminated sheet of the present invention is assembled to solar energy. The battery system can be made into a highly durable and/or thin solar cell system compared to the prior solar cell. The solar cell of the present invention, the solar power generation system, the power source of small electronic parts, and the like are not limited to outdoor use, indoors. For use, it can be suitably used in various applications. -27- 201244940 [Evaluation method of characteristics] A. Layer thickness ΤΙ, T2, and laminate ratio T1/T2 are obtained in the following order (A1) to (A 4). The measurement was performed at 10 locations, and the layer ΤΙ (μιη) of the P1 layer, the layer thickness P2 (μιη) of P2, and the layering ratio T1/T2 were set as the average value. (Α1) Using a microtome, the laminated sheet was cut in the thickness direction and cut perpendicularly to the direction of the laminated sheet surface (A2), and then the cut cross section was observed by an electron microscope to be enlarged by 500 times. image. In addition, the observation site is determined by the fact that the upper and lower directions of the image are parallel to the thickness of the laminated sheet, and the left and right direction of the image is flat with the direction of the laminated sheet. In the thickness direction, the entire image cannot be accommodated in one image. In the case, an image is prepared, and the observation position is observed in the thickness direction, and a plurality of images are matched, and the thickness is confirmed. (A 3) The layer thickness T2 of the layer thickness layer P2 of the p 1 layer in the image obtained in (A 2) was obtained. (A4) T1 is divided by T2, and the layering ratio T1/T2 is calculated. B. Inorganic fine particle content rate Wal, Wa2, Wave Each layer of the P1 layer and the P2 layer was cut from the laminated sheet, and the inorganic fine particle contents Wa1 and Wa2 were determined by the method. The mass wa (g) of the cut material was measured. Next, the inorganic fine particles obtained by fractionating the inorganic fine particles in the insoluble components which have been centrifuged are dissolved in dioxane t, washed with dioxane, and centrifuged. Further, the washing operation is repeated until the alcohol is no longer turbid even after the centrifugation. The wa'(g) ' of the obtained inorganic fine particles was determined from the following formula (3). The inorganic fine particle content was changed and the thickness was not changed. , and intend to present it. Shape, by T1, the following chlorine. Will, add B quality -28-.201244940 Inorganic particle content rate (mass i%) = (wa'/wa)xl〇〇". (3) And 'P1 layer and P2 layer inorganic particle content rate wave system It is obtained by the following formula (1). The average particle content of the inorganic particles is Wave = (Wa 1 XT 1 + Wa2 X T2) / (T1 + T2)... (1) where 'ΤΙ is the layer thickness of the ΐ layer (μπι), and Τ2 is the layer thickness of the layer 2 (πι). C ·Mechanical properties of the sheet According to ASTM-D882 (refer to ASTM Standard Yearbook, 1 999 edition)', the specimen was cut out to a size of 1 cm x 20 cm, and the elongation at break was stretched at a distance of 5 cm between the chucks and a tensile speed of 300 mm/min. . Further, the number of samples was n = 5, and the measurement was performed as the average value in the respective directions of the longitudinal direction and the lateral direction of the laminated sheet.
就所得之斷裂伸長率,以下述方式判定 斷裂伸長率為80%以上之情形:s 斷裂伸長率為60%以上小於8〇%之情形:A 斷裂伸長率為40%以上小於6〇%之情形:B 斷裂伸長率為30°/°以上小於40%之情形:c 斷裂伸長率為2〇%以上小於3〇%之情形:D 斷裂伸長率為小於2〇%之情形:E &主〇為良好,其中 D.抗濕熱試驗後之斷裂伸長率% 1料刀出成測定片之形狀(lcmx20cm)後,以平α 製作所股份有限公λ 丄 a司製壓力鍋,在溫度12 5 ΐ、相對 度l〇〇%RH之你π 條件下進行48小時處理,其後根據上对 '29- 201244940 •項測疋斷裂伸長率。此外,測定為η = 5,又,就各積 a片之縱方向、橫方向之各方向進行測定後,將其平均 值作為斷裂伸長率E1。 斷裂伸長率為4 0 %以上之情形:S 斷'裂伸長率為3 0 %以上小於4 0 %之情形:a 斷裂伸長率為2 0 %以上小於3 0 %之情形:b 斷裂伸長率為15q/()以上小於2〇%之情形:C 斷裂伸長率為1 〇 %以上小於1 5 %之情形:〇 斷裂伸長率為小於1 〇 %之情形:E S至D為良好,其中以§最優異。 E•耐光性試驗後之伸長保持率 _將°式料切出成測定片之形狀(1 c m X 2 0 c m)後,以岩崎 電氣月又份有限公司製Esuper UV試驗機SUV-W131,在 溫度60。(:、相對濕度5〇%RH、強度1〇〇mW/cm2(光源: 金屬_素燈、波長範圍:295至45〇nm、波峰波長:365nm) Ί条件下照射4 8小時’其後依照上述c ·項測定斷裂伸 長率此外,測定為η = 5,又,就薄膜之縱方向、橫方 向之各方向進行測定後,將其平均值設為斷裂伸長率 Ε2。又,就進行處理前之薄膜,亦依照上述c·項測定斷 裂伸長率Ε0,使用如此所得之斷裂伸長率Ε0、Ε2,根 據次之式(4),計算伸長保持率。 伸長保持率(%)= (Ε2/Ε0)χ100…(4) 就所得之伸長保持率,以下述方式判定。 伸長保持率為50%以上之情形:S 伸長保持率為4 0 %以上小於5 0 %之情形:a -30- 201244940With respect to the obtained elongation at break, the case where the elongation at break was 80% or more was determined in the following manner: the case where the elongation at break of s was 60% or more and less than 8% by weight: the elongation at break of A was 40% or more and less than 6% by weight. :B Case where the elongation at break is 30°/° or more and less than 40%: c. Elongation at break of 2〇% or more and less than 3〇%: Case where elongation at break of D is less than 2〇%: E & main 〇 It is good, in which D. The elongation at break after the damp heat test is 1%. After the shape of the test piece is formed (lcmx20cm), the pressure cooker of the company is made of flat α, at a temperature of 12 5 ΐ, relative Degree l〇〇%RH is treated for 48 hours under π conditions, and then the elongation at break is measured according to the upper pair of '29-201244940. Further, the measurement was η = 5, and after the measurement was performed in each of the longitudinal direction and the transverse direction of each of the sheets, the average value was defined as the elongation at break E1. The case where the elongation at break is more than 40%: the case where the elongation at break of S is more than 30% and less than 40%: a. The elongation at break is more than 20% and less than 30%: b elongation at break 15q/() or more and less than 2〇%: C elongation at break is 1% or more and less than 15%: the elongation at break of 〇 is less than 1%%: ES to D is good, of which § is the most Excellent. E•Elongation retention rate after the light resistance test _ After the ° material was cut into the shape of the measurement piece (1 cm X 2 0 cm), the Esuper UV tester SUV-W131 manufactured by Iwasaki Electric Co., Ltd. was used. Temperature 60. (:, relative humidity 5〇%RH, intensity 1〇〇mW/cm2 (light source: metal _ lamp, wavelength range: 295 to 45 〇 nm, peak wavelength: 365 nm) 照射 conditions for 4 8 hours' thereafter In addition, the breaking elongation of the above c. is measured as η = 5, and after measuring in the longitudinal direction and the transverse direction of the film, the average value is taken as the breaking elongation Ε 2. Further, before the treatment The film was also measured for elongation at break Ε0 according to the above item c. Using the elongation at break Ε0, Ε2 thus obtained, the elongation retention ratio was calculated according to the following formula (4). Elongation retention ratio (%) = (Ε2/Ε0 Χ100 (4) The elongation retention ratio obtained is determined in the following manner: The elongation retention ratio is 50% or more: S elongation retention is 40% or more and less than 50%: a -30- 201244940
伸長保持率為30%以上小於40%之情形:b 伸長保持率為20%以上小於30%之情形:c 伸長保持率為10%以上小於2〇%之情形:D 伸長保持率為小於1 〇 %之情形:E S至D為良好,其中以s最優異。此外,在積層片 為非對稱之構成之情形,則自本發明之積層片之p2層側 照射紫外線。 F·相對反射率 ^使用分光光度計U-341〇(日立製作所股份有限公司 製)’測定波長56〇nm之反射率作為相對反射率。試樣數 ::=5,測定各自之相對反射率,並計算其平均值。測 定單元係使用Φ60ιηιη之積分球(型號13〇_〇632),安裝 1〇°傾斜間隔件。X,在標準白色板係使用氧化紹(型號 210-0740)。此外,在積層片為非對稱之構成之情形车 自積層片之Ρ 2層側進行測定。 y ’、 就所得之反射率以下述方式進行判定。 相對反射率為94%以上之情形:s 相對反射率為92%以上小於94%之情形:a 相對反射率為89%以上小於92。/()之情形:β 相對反射率為85%以上小於89%之情形:c 相對反射率為小於8 5 %之情形:d S至C為良好’其中以s最優異。 G.色調(b值) 根據JIS-Z-8722(1 994年版),使用分光式色差 本電色工業製SE-2000、光源鹵素燈12V4A hS_=c 後分光方式)’根據反射法,測定薄片之色調(b值)。 201244940 Η ·紫外線照射後之色調變化Ab 將薄片以岩崎電氣股份有限公司製Esuper紫外線試 驗機S-W131 ’在溫度6〇t、相對濕度5〇%、強度 100mW/cm (光源.金屬鹵素燈、波長範圍:295至 450nm、波峰波長:365nm)之條件下 ’將照射48小時後 之b值與試驗前後之b值’依照上述g項測定,將其差 作為紫外線照射後之色調變化。 就所得之色調變化(△",係以下述方式進行判定。 色調變化Ab為1以下之情形:$ 色調變化△!)大於1、1 5以下之情形:A 色調變化Ab大於1.5、2以下之情形:B 色調變化Ab大於2、3以下之情形:c 色調變化ΔΙ)大於3、5以下之情形:D 色調變化Ab大於5之情形:e S至D為良好,其中以s最優異。 此外,積層片為非對稱之構成之情形,係自本發明 之積層片之P2層側照射紫外線。 密接性 根據JIS K 68 54(1994年版),測定與EVA薄片之接 著力。測定試驗片係在厚度〇 · 3mm之半強化玻璃上,重 疊Sanvic股份有限公司製500μιη厚之EVA薄片、及已 進行電暈處理之實施例、比較例之積層片,使用市隹破 螭貼合機(laminator) ’在真空吸引後,於n5t加熱條件 下,使用以29.4N/cm2負荷,經15分鐘壓製處理之物 接著強度試驗之試驗片之寬設為l〇mm,並準備2片t式驗 -32- 201244940 片,就各甙驗片,改轡 —枯—τ 文%所進仃3處之測定’將所得測 疋值之平均值作為 m作為接者強度值。接荖強声Α 100N/50nm以上者,則划“ 值 者強度為 ^ 者則N斷為實用上無問題的等級。 所付之剝離強度以下述方式判定 剝離強度為65N/1Gmm以上之情形:s 形When the elongation retention ratio is 30% or more and less than 40%: b. The elongation retention ratio is 20% or more and less than 30%: c elongation retention ratio is 10% or more and less than 2% by weight: D elongation retention ratio is less than 1 〇 % case: ES to D is good, with s being the best. Further, in the case where the laminated sheet is asymmetric, ultraviolet rays are irradiated from the side of the p2 layer of the laminated sheet of the present invention. F·relative reflectance ^ The reflectance at a wavelength of 56 〇 nm was measured using a spectrophotometer U-341 (manufactured by Hitachi, Ltd.) as a relative reflectance. The number of samples: ::= 5, the relative reflectance of each was measured, and the average value was calculated. The measuring unit uses a Φ60ιηιη integrating sphere (model 13〇_〇632) to mount a 1°° tilting spacer. X, in the standard white plate system using Oxidation (model 210-0740). Further, in the case where the laminated sheet is asymmetric, the measurement is performed on the side of the second layer of the laminated sheet. y ', the reflectance obtained is determined in the following manner. The case where the relative reflectance is 94% or more: the case where the relative reflectance of s is 92% or more and less than 94%: a relative reflectance is 89% or more and less than 92. Case of /(): a case where the relative reflectance of β is 85% or more and less than 89%: the case where the relative reflectance of c is less than 85 %: d S to C is good, wherein s is the most excellent. G. Hue (b value) According to JIS-Z-8722 (1 994 edition), using Separation type color difference industrial color SE-2000, light source halogen lamp 12V4A hS_=c post-split mode) 'Measurement sheet according to reflection method Hue (b value). 201244940 Η ·Color change after UV irradiation Ab The sheet is made of Iso UV tester S-W131 from Iwasaki Electric Co., Ltd. at a temperature of 6〇t, a relative humidity of 5〇%, and a strength of 100mW/cm (light source, metal halide lamp, In the wavelength range: 295 to 450 nm, peak wavelength: 365 nm), the b value after 48 hours of irradiation and the b value before and after the test were measured in accordance with the above g term, and the difference was changed as the color tone after ultraviolet irradiation. The obtained color tone change (Δ" is determined in the following manner. When the color tone change Ab is 1 or less: $color change Δ!) is larger than 1, 15 or less: A color change Ab is larger than 1.5 or less Case: B case where the hue change Ab is larger than 2, 3 or less: c hue change ΔΙ) is larger than 3, 5 or less: D case where the hue change Ab is greater than 5: e S to D is good, and s is the most excellent. Further, in the case where the laminated sheet is asymmetric, the ultraviolet rays are irradiated from the side of the P2 layer of the laminated sheet of the present invention. Adhesion The adhesion to the EVA sheet was measured in accordance with JIS K 68 54 (1994 edition). The test piece was laminated on a semi-reinforced glass having a thickness of 〇·3 mm, and a 500 μm thick EVA sheet manufactured by Sanvic Co., Ltd., and a laminated sheet of Examples and Comparative Examples which were subjected to corona treatment were used, and the laminate was laminated. Machine (laminator) After the vacuum suction, under the heating condition of n5t, using the load of 29.4 N/cm2, the object treated by pressing for 15 minutes, the width of the test piece after the strength test is set to l〇mm, and 2 pieces of t are prepared. Test -32- 201244940 pieces, for each test piece, change 枯 枯 枯 τ 文 文 % % τ τ 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定In the case of a strong sound Α 100N/50nm or more, the value of the value of the value is ^, and the N is a practically problem-free grade. The peel strength to be applied is determined by the following method: the peel strength is 65 N/1 Gmm or more: s shape
剝離強度為55N/1〇mm以上小於6谓⑺mm之情 A 以上小於 55N/1 0mm之情 以上小於 4 5 N /1 0 m m之情 以上小於 35N/10mm之情 形The peeling strength is 55N/1〇mm or more and less than 6 (7)mm. A is less than 55N/1 0mm. The above is less than 4 5 N /1 0 m m. The above is less than 35N/10mm.
剝離強度為45N/l〇mm B 形Peel strength is 45N/l〇mm B shape
剝離強度為35N/10mm CPeel strength is 35N/10mm C
剝離強度為25N/10mm 形:D 剝離強度為小於25N/l〇mm之情形:e S至D為良好’其中以§最優異。 [實施例] 以下茲就本發明例舉實施例加以說明,不過本發明 未必是限定於該等者。 (原料) •聚碳酸酯系樹脂(PC(1)) 使用出光興產股份有限公司製“ tarflon,, A2200。此外,該聚碳酸酯系樹脂,係將作為二羥二芳基 化合物之2,2 -雙(4 -羥苯基)丙烧(通稱雙酚a)作為主要成 分之聚碳酸酯系樹脂,在溫度300。〇、負荷1 2kg之 為 1 2cm3/1 Omin。 -33- 201244940 •聚碳酸酯系樹脂(PC(2)) 使用出光興產股份有限公司製“ Tarfi〇n” A2600。 此外’該聚碳酸酯系樹脂,係將作為二羥二芳基化合物 之2,2 -雙(4 -經苯基)丙烧(通稱雙紛a)作為主要成分之聚 碳酸酯系樹脂,在溫度300X:、負荷1.2kg之MVR為 6cm3/1 Omin 〇 .丙烯酸系樹脂(丙烯酸(1)) 使用 Kuraray 股份有限公司製 “ parapet,, HRL100 0-L。此外,該丙烯酸系樹脂係將作為具有(甲基) 丙烯醯基之化合物之曱基甲基丙烯酸酯作為主要成分之 丙烯酸樹脂,係不含彈性成分之丙烯酸系樹脂。 •丙烯酸系樹脂(丙烯酸(2)) 使用住友化學股份有限公司製“ Sumipex,, ΗY50Y。此外,該丙烯酸系樹脂係將作為具有(甲基)丙 烯醯基之化合物之曱基曱基丙烯酸酯作為主要成分之丙 烯酸樹脂,係含有彈性成分30重量%之丙烯酸樹脂。 (參考例1) 將50質量份PC(1)與50質量份之平均粒徑21〇nm 之金紅石变氧化欽微粒’在已通氣的260。〇二軸捏合擠 壓機内予以熔融捏合,並予熔融擠壓,排出成為股線狀。 以溫度25°C之水冷卻後,即刻切割,並製作氧化鈦微粒 濃度50質量%之母料(ΜB 1)。 (參考例2) 除了使用PC(2)作為聚碳酸酯系樹脂以外,其他以與 參考例1相同之方法,製作氧化鈦微粒濃度5〇質量%之 母料(MB2)。 -34- 201244940 (參考例3) 將50質量份丙烯酸(2)與5〇質量份之平均粒秤 21〇nm之金紅石型氡化鈦微粒,在已通氣的22〇。〇之: 軸捏合擠壓機内進行熔融捏合,並予熔融擠壓排出成為 股線狀。以溫度25°C之水冷卻後,即刻切割並製作氧化 鈦被粒濃度50質量%之母料(mb3)。 (參考例4) 除了使用50質量份之平均粒徑29〇nm之氧化鋅微 粒以外,其他以與參考例3相同之方法,獲得氧化鋅微 粒50質量%之母料(mb4)。 (實施例1) 使用主擠壓機與副擠壓機,在主擠壓機(單軸擠壓機 )中,將PC(1)與參考例i所得之氧化鈦母料(MB1),予 以混合以使氧化鈦含有率成為表丨所示P1層之組成之物 ,在110°c之溫度經6小時熱風乾燥後,供給之,並以 280 °C之溫度熔融擠壓後,進行以8〇μπι截止過濾器 (cut-off filter)之過遽。一方面,在副擠壓機’係將二浠 酸(1)與丙烯酸(2)、參考例3所得之氧化鈦母料(mb3), 予以混合以使氧化鈦含有率、橡膠成分含量成為表丨所 示P2層之組成,在110Τ:之溫度進行6小時熱風 ,供給之,並予熔融擠壓。接著在自主擠壓機所供給之 ’予以合流以 Τ模卡口内, P 1層單側’將自副擠壓機所供給的p 2層 使厚度比率成為P1層·:Ρ2層=2: 1,白 進行熔融二層積層共擠壓,製成積層片,在保持於表面 溫度7〇°C的鼓輪上,以靜電外加法予以密接冷卻固化, 其後冷卻至室溫為止,獲得厚度3〇〇μιη之積層片。 -35- 201244940 就所得之積層片’求得声 1所示,又評價薄;^特性的二、積層比,結 表2所示,可知為薄片機械^性12所示。其 層片。又,光反射性、密'、2抗紫外線性優 (實施例2至1 5) 抗濕熱性亦為良 除了將P1層、5>2居夕{丄 ”層之厚度之比改為二:外改::二之組成’ 獲得厚度30〇μίη之積層片。評俨^巧,、貫靶例1 結果如表1、2所示。可知° :传之積層片之 又片」又’光反射性、密接性、抗濕敎 艮好。又’就實施例5至 、…、 Μ Η 1〇、12,相較於實施例 存片機械特性、抗紫外妗 .^ 仉I外線性、光反射性、密接性 熱性之特性均衡性良好。 (實施例1 6) 除了使m Ρ2層之組成成為表i之 主擠壓機所供給之p!層兩側,將自副擠壓機所 、2層,以厚度比率設為P2層:P 1層:P2層=i : 並予合流以外,其他與實施例1相同,獲得厚度 之積層片。評價所得積層片之特性結果如表i 可知薄片機械特性、抗紫外線性、光反射性、抗 句優異的積層片。但是,相較於其他實施例,結 接性低。 ' ° (實施例1 7) 除了將P1層、P2層之組成改為表i之組成 更Pi層、P2層之層厚度之比成為表i以外其 果如表 結果如 異的積 好。 P1層、 相同, 特性, 外線性 性亦為 [至4, 、抗濕 ,且在 供給之 8:1, 3 ΟΟμπι 所示。 濕熱性 果是密 ,並變 他與實 -36- 201244940 施例1同樣地獲得厚度300μηι之積層片。評價所得積厚 片之特性’結果如表1、2所示。可知為薄片機械特性曰、 抗紫外線性均優異的積層片。又,光反射性、密接性、 抗濕熱性亦良好。 ' (實施例18) 除了將Ρ2層之微粒改為氧化辞微粒,Ρ1 I、Ρ2層 之組成改為表1之組成,且PI f、Ρ2層之層厚度之比 變更為表1以外,其他與實施例i同樣地獲得厚度m 之積層片。評價所得積層片之特性,結果如表卜2所示。 可知為薄片機械特性、抗紫外線性優異的積層片。又, 光反射性、密接性、抗濕熱性亦良好。 (比較例1至6) 除了將P1層 其他與實施例丨同樣之方法 片。評價所得積層片之特性, 層之組成成為表1之組成以外 獲得厚度 結果如表1 3ΟΟμηι之積層 在比較例1、4、 化。又在比較例2至 (比較例7) 、2所示。 、6 ’結果是各薄片之機械特性劣 5結果是抗紫外線性劣化。 一町"八叹刀·<-衝脂改為P C糸核 脂’且Ρ1層、Ρ2層之细士妗达士 、、且成改為表1之組成以外,其相 與實施例1同樣之方法,婼 獲付;度300μιη之積層X。言气 價所得積層片之特性,έ士果如矣 ”。果如表1、2所示。相較於實摊 例,結果是抗紫外線性劣化。 -3 7- 201244940 [產業上可利用性] 本發明之積層片,可提供一種積層片,其相較 前之聚碳酸酯系樹脂薄片,對於紫外線之耐性優異 具有適用於太陽能電池背板的機械特性。此等積層 薄片,除了太陽能電池用背板之外,以液晶顯示器 射板、汽車用材料、建築材料為始,在重視相對於 線之耐性、光反射性之用途可適當使用。尤其是藉 用此等聚碳酸酯系樹脂薄片,則可提供具有高耐久 太陽能電池用背板及使用其之太陽能電池。 於先 ,亦 樹脂 用反 紫外 由使 性的 -38- 201244940 表1-1 原料 P1層 P2層 樹脂 母料 樹脂⑴ 樹脂(2) 母料 種類 質量% 種類 質量% 種類 質量% 種類 質量% 種類 質量% 實施例1 PC⑴ 90 MB1 10 丙烯酸(1) 32.3 丙烯酸(2) 65.7 MB3 2 實施例2 PC⑴ 90 MB1. 10 丙烯酸(1) 32.3 丙烯酸(2) 65.7 MB3 2 實施例3 PC⑴ 90 MB1 10 丙烯酸(1) 13.3 丙烯酸(2) 46.7 MB3 40 實施例4 PC⑴ 90 MB1 10 丙烯酸(1) 13.3 丙烯酸(2) 46.7 MB3 40 實施例5 PC(1) 90 MB1 10 丙烯酸(1) 30.3 丙烯酸(2) 63.7 MB3 6 實施例6 PC⑴ 90 MB1 10 丙烯酸(1) 30.3 丙烯酸(2) 63.7 MB3 6 實施例7 PC⑴ 90 MB1 10 丙烯酸(1) 21.3 丙烯酸(2) 54.7 MB3 24 實施例8 PC⑴ 90 MB1 10 丙烯酸(1) 21.3 丙烯酸(2) 54.7 MB3 24 實施例9 PC⑴ 90 MB1 10 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例10 PC⑴ 90 MB1 10 丙烯酸(1) 56.7 丙烯酸(2) 23.3 MB3 20 實施例11 PC⑴ 90 MB1 10 丙烯酸(1) 73.3 丙烯酸(2) 6.7 MB3 20 實施例12 PC⑴ 90 MB1 10 丙烯酸(1) 6.7 丙烯酸(2) 73.3 MB3 20 實施例13 PC(1) 80 MB1 20 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例14 PC⑴ 94 MB1 6 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例15 PC⑴ 98 MB1 2 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例16 PC⑴ 90 MB1 10 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例17 PC(2) 90 MB2 10 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB3 20 實施例18 PC(1) 90 MB1 10 丙烯酸(1) 23.3 丙烯酸(2) 56.7 MB4 20 比較例1 PC⑴ 90 MB1 10 丙烯酸(1) 32.3 丙烯酸(2) 65.7 MB3 2 比較例2 PC⑴ 90 MB1 10 丙烯酸(1) 32.8 丙烯酸(2) 66.2 MB3 1 比較例3 PC⑴ 90 MB1 10 丙烯酸(1) 32.8 丙烯酸(2) 66.2 MB3 1 比較例4 PC⑴ 90 MB1 10 丙烯酸(1) 8.3 丙烯酸(2) 41.7 MB3 50 比較例5 PC⑴ 90 MB1 10 丙烯酸(1) 8.3 丙烯酸(2) 41.7 MB3 50 比較例6 PC⑴ 90 MB1 10 丙烯酸(1) 13.3 丙烯酸(2) 46.7 MB3 40 比較例7 PC⑴ 90 MB1 10 PC 80 - 0 MB1 20 -39- 201244940 表卜2 積層片構成 層構成 積層比 T1/T2 無機微粒量 Wal 無機微粒量 Wa2 彈性成分 Wb2 WalAVa2 (Wa+18)/9.5 平均微粒含量 - 質量% 質量% 質量% - 質量% 實施例1 P1/P2 2 5 1 20 5 2 3.67 實施例2 P1/P2 30 5 1 20 5 2 4.87 實施例3 P1/P2 30 5 20 20 0.25 4 5.48 實施例4 P1/P2 4 5 20 20 0.25 4 8 實施例5 P1/P2 4 5 3 20 1.67 2.21 4.6 實施例6 P1/P2 15 5 3 20 1.67 2.21 4.88 實施例7 P1/P2 15 5 12 20 0.42 3.16 5.44 實施例8 P1/P2 4 5 12 20 0.42 3.16 6.4 實施例9 P1/P2 8 5 10 20 0.5 2.95 5.56 實施例10 P1/P2 8 5 10 10 0.5 2.95 5.56 實施例11 P1/P2 8 5 10 5 0.5 2.95 5.56 實施例12 P1/P2 8 5 10 25 0.5 2.95 5.56 實施例13 P1/P2 8 10 10 20 1 2.95 10 實施例14 P1/P2 8 3 10 20 0.3 2.95 3.78 實施例15 P1/P2 8 1 10 20 0.1 2.95 2 實施例16 P2/P1/P2 4 5 10 20 0.5 2.95 6.00 實施例17 P1/P2 8 5 10 20 0.5 2.95 5.56 實施例18 P1/P2 8 5 10 20 0.5 2.95 5.56 比較例1 P1/P2 1.5 5 1 20 5 2 3.4 比較例2 P1/P2 2 5 0.5 20 10 1.95 3.5 比較例3 P1/P2 30 5 0.5 20 10 1.95 4.85 比較例4 P1/P2 30 5 25 20 0.2 4.53 5.65 比較例5 P1/P2 4 5 25 20 0.2 4.53 9 比較例6 P1/P2 3 5 20 20 0.25 4 8.75 比較例7 P1/P2 8 5 10 0 0.5 2.95 5.56 -40- 201244940 表2The peel strength was 25 N/10 mm shape: the case where the D peel strength was less than 25 N/l 〇 mm: e S to D was good', and § was the most excellent. [Examples] Hereinafter, the examples of the invention are described, but the invention is not necessarily limited thereto. (Materials) • Polycarbonate-based resin (PC (1)) tarflon, A2200, manufactured by Idemitsu Kosan Co., Ltd., and the polycarbonate resin, which is a dihydroxydiaryl compound, A polycarbonate resin containing 2 - bis(4-hydroxyphenyl)propane (commonly known as bisphenol a) as a main component at a temperature of 300 Torr, and a load of 12 kg is 12 cm 3 /1 Omin. -33 - 201244940 • Polycarbonate-based resin (PC(2)) "Tarfi〇n" A2600 manufactured by Idemitsu Kosan Co., Ltd.. In addition, the polycarbonate resin is a 2,2-double which is a dihydroxydiaryl compound. (4 - phenyl) propylene (commonly known as bis) a polycarbonate resin as a main component, at a temperature of 300X: a load of 1.2kg, MVR is 6cm3 / 1 Omin 丙烯酸. Acrylic resin (acrylic acid (1) ) "Parapet, HRL100 0-L, manufactured by Kuraray Co., Ltd.". In addition, the acrylic resin is an acrylic resin containing, as a main component, a mercapto methacrylate having a (meth)acrylonyl group as a main component, and is an acrylic resin containing no elastic component. • Acrylic resin (acrylic acid (2)) is manufactured by Sumitomo Chemical Co., Ltd. "Sumipex, ΗY50Y. In addition, this acrylic resin is used as a mercapto methacrylate having a compound having a (meth) acrylonitrile group. The acrylic resin which is a main component is an acrylic resin containing 30% by weight of an elastic component. (Reference Example 1) 50 parts by mass of PC(1) and 50 parts by mass of rutile oxidized oxidized particles having an average particle diameter of 21 〇 nm The ventilated 260. 〇 two-axis kneading extruder is melt-kneaded and melt-extruded, and discharged into a strand shape. After cooling at a temperature of 25 ° C, it is immediately cut, and the titanium oxide particle concentration is 50% by mass. (Master B 1) (Reference Example 2) A masterbatch of a titanium oxide fine particle concentration of 5% by mass was produced in the same manner as in Reference Example 1 except that PC (2) was used as the polycarbonate resin. MB2) -34- 201244940 (Reference Example 3) 50 parts by mass of acrylic acid (2) and 5 parts by mass of an average particle size of 21 〇 nm of rutile-type titanium telluride fine particles, which were ventilated at 22 〇. : Melting in the shaft kneading extruder After kneading, it was melt-extruded and discharged into a strand shape. After cooling with water at a temperature of 25 ° C, the master batch (mb3) having a titanium oxide particle concentration of 50% by mass was immediately cut and formed (Reference Example 4). A masterbatch (mb4) of 50% by mass of zinc oxide fine particles was obtained in the same manner as in Reference Example 3 except for the zinc oxide fine particles having an average particle diameter of 29 Å. (Example 1) Using a main extruder and In the secondary extruder, in the main extruder (single-axis extruder), the PC (1) and the titanium oxide masterbatch (MB1) obtained in Reference Example i are mixed to make the titanium oxide content rate The composition of the composition of the P1 layer was dried by hot air at a temperature of 110 ° C for 6 hours, and was melt-extruded at a temperature of 280 ° C, and then subjected to a cut-off filter of 8 μm. On the one hand, in the secondary extruder, the dibasic acid (1) and the acrylic acid (2), the titanium oxide masterbatch (mb3) obtained in Reference Example 3 are mixed to make the titanium oxide content, rubber The composition content is the composition of the P2 layer shown in Table ,, and the hot air is supplied at a temperature of 110 Τ for 6 hours, supplied, and melted. Then, the pressure is supplied to the self-extruding machine, and the thickness of the p 2 layer supplied from the sub-extruder is made into the P1 layer: Ρ 2 layers = 2 : 1. The white layer is co-extruded by molten two layers to form a laminated sheet, which is cooled and solidified by electrostatic external application on a drum maintained at a surface temperature of 7 ° C, and then cooled to room temperature to obtain -35- 201244940 The laminated sheet obtained is obtained as shown in the sound 1 and evaluated as thin; the second characteristic of the characteristic, the layering ratio, as shown in Table 2, is known as the mechanical properties of the sheet. 12 is shown. Its layer. Further, the light reflectivity, the dense ', and the 2 ultraviolet resistance are excellent (Examples 2 to 15). The moist heat resistance is also good except that the ratio of the thickness of the P1 layer, the 5>2 layer is changed to two: External modification:: the composition of the two 'obtained a layer of thickness 30 〇μίη. Review 巧 ^ Qiao, the results of the target example 1 as shown in Table 1, 2. It can be seen that: the film of the layer of the film "and the light" Reflective, adhesive, and moisture resistant. Further, in the examples 5 to 3, ..., Μ Η 1 〇, 12, the mechanical characteristics of the film, the ultraviolet ray resistance, the light linearity, the light reflectivity, and the heat of adhesion were excellent in balance. (Example 1 6) In addition to making the composition of the m Ρ 2 layer into both sides of the p! layer supplied from the main extruder of Table i, the two layers from the sub-extruder were set to the P2 layer by the thickness ratio: P One layer: P2 layer = i: and the same as in the first embodiment, the laminate of the thickness was obtained in the same manner as in the first embodiment. As a result of evaluating the characteristics of the obtained laminated sheet, a laminated sheet excellent in sheet mechanical properties, ultraviolet resistance, light reflectivity, and anti-sentence was obtained. However, compared to other embodiments, the connectivity is low. '° (Example 1 7) In addition to changing the composition of the P1 layer and the P2 layer to the composition of the table i, the ratio of the layer thicknesses of the Pi layer and the P2 layer is the same as that of the table i. The P1 layer, the same, the characteristics, and the external linearity are also [to 4, moisture resistant, and are shown in the supply of 8:1, 3 ΟΟμπι. The moist heat of the fruit was dense, and it was obtained in the same manner as in Example 1 of the Japanese Patent Application Laid-Open No.-36-201244940. The characteristics of the obtained thick sheet were evaluated. The results are shown in Tables 1 and 2. It is known that the laminated sheet is excellent in sheet mechanical properties and ultraviolet resistance. Moreover, light reflectivity, adhesion, and moist heat resistance are also good. (Example 18) In addition to changing the particles of the Ρ2 layer to the oxidized particles, the composition of the Ρ1 I and Ρ2 layers was changed to the composition of Table 1, and the ratio of the layer thicknesses of the PI f and Ρ 2 layers was changed to other than Table 1. A laminate of thickness m was obtained in the same manner as in Example i. The characteristics of the obtained laminated sheets were evaluated, and the results are shown in Table 2. It is known that it is a laminated sheet excellent in sheet mechanical properties and ultraviolet ray resistance. Moreover, light reflectivity, adhesiveness, and moist heat resistance are also good. (Comparative Examples 1 to 6) The same method as in the Example 将 except the P1 layer was used. The characteristics of the obtained laminated sheets were evaluated, and the composition of the layers was made up of the composition of Table 1. The results were as shown in Table 1 3 ΟΟ μηι in Comparative Examples 1, 4, and Chemicals. Further, it is shown in Comparative Example 2 to (Comparative Examples 7) and 2. The result of 6' is that the mechanical properties of each sheet are inferior. 5 As a result, the ultraviolet resistance is deteriorated. Ichikawa "Eight slasher<-milk is changed to PC糸 nucleolipid' and Ρ1 layer, Ρ2 layer of 士士达达士, and the composition is changed to Table 1, the phase and the embodiment 1 In the same way, the seizure is paid; the layer X of 300 μιηη. The characteristics of the laminated sheets obtained by the price of the gas are as follows: the results are shown in Tables 1 and 2. Compared with the actual examples, the results are UV-resistant deterioration. -3 7- 201244940 [Industrial Applicability] The laminated sheet of the present invention can provide a laminated sheet which is excellent in ultraviolet resistance and has mechanical properties suitable for a solar battery back sheet as compared with the conventional polycarbonate resin sheet. These laminated sheets are used for solar cells. In addition to the back sheet, it is suitable for applications such as liquid crystal display panels, automotive materials, and building materials, and it is suitable for use in resistance to light and light reflectivity. In particular, by using such polycarbonate resin sheets, It can provide a backsheet with high durability solar cells and a solar cell using the same. First, the resin is also used for anti-UV by -38- 201244940 Table 1-1 Raw material P1 layer P2 resin masterbatch resin (1) Resin ( 2) Masterbatch type mass% Species mass% Species mass% Species mass% Species mass% Example 1 PC(1) 90 MB1 10 Acrylic acid (1) 32.3 Acrylic acid (2) 65.7 MB3 2 Example 2 PC(1) 90 MB1. 10 Acrylic (1) 32.3 Acrylic (2) 65.7 MB3 2 Example 3 PC(1) 90 MB1 10 Acrylic (1) 13.3 Acrylic (2) 46.7 MB3 40 Example 4 PC(1) 90 MB1 10 Acrylic (1) 13.3 Acrylic ( 2) 46.7 MB3 40 Example 5 PC(1) 90 MB1 10 Acrylic (1) 30.3 Acrylic (2) 63.7 MB3 6 Example 6 PC(1) 90 MB1 10 Acrylic (1) 30.3 Acrylic (2) 63.7 MB3 6 Example 7 PC(1) 90 MB1 10 Acrylic (1) 21.3 Acrylic (2) 54.7 MB3 24 Example 8 PC(1) 90 MB1 10 Acrylic (1) 21.3 Acrylic (2) 54.7 MB3 24 Example 9 PC(1) 90 MB1 10 Acrylic (1) 23.3 Acrylic (2) 56.7 MB3 20 Example 10 PC(1) 90 MB1 10 Acrylic (1) 56.7 Acrylic acid (2) 23.3 MB3 20 Example 11 PC(1) 90 MB1 10 Acrylic acid (1) 73.3 Acrylic acid (2) 6.7 MB3 20 Example 12 PC(1) 90 MB1 10 Acrylic ( 1) 6.7 Acrylic acid (2) 73.3 MB3 20 Example 13 PC(1) 80 MB1 20 Acrylic acid (1) 23.3 Acrylic acid (2) 56.7 MB3 20 Example 14 PC(1) 94 MB1 6 Acrylic acid (1) 23.3 Acrylic acid (2) 56.7 MB3 20 Example 15 PC(1) 98 MB1 2 Acrylic acid (1) 23.3 Acrylic acid (2) 56.7 MB3 20 Example 16 PC(1) 90 MB1 10 Acrylic (1) 23.3 Acrylic (2) 56.7 MB3 20 Example 17 PC(2) 90 MB2 10 Acrylic (1) 23.3 Acrylic (2) 56.7 MB3 20 Example 18 PC(1) 90 MB1 10 Acrylic (1 23.3 Acrylic acid (2) 56.7 MB4 20 Comparative Example 1 PC(1) 90 MB1 10 Acrylic acid (1) 32.3 Acrylic acid (2) 65.7 MB3 2 Comparative Example 2 PC(1) 90 MB1 10 Acrylic acid (1) 32.8 Acrylic acid (2) 66.2 MB3 1 Comparative Example 3 PC(1) 90 MB1 10 Acrylic (1) 32.8 Acrylic (2) 66.2 MB3 1 Comparative Example 4 PC(1) 90 MB1 10 Acrylic (1) 8.3 Acrylic (2) 41.7 MB3 50 Comparative Example 5 PC(1) 90 MB1 10 Acrylic (1) 8.3 Acrylic (2 41.7 MB3 50 Comparative Example 6 PC(1) 90 MB1 10 Acrylic (1) 13.3 Acrylic (2) 46.7 MB3 40 Comparative Example 7 PC(1) 90 MB1 10 PC 80 - 0 MB1 20 -39- 201244940 Table 2 Layer of laminated sheets constitutes laminate ratio T1/T2 inorganic fine particle amount Wal inorganic fine particle amount Wa2 elastic component Wb2 WalAVa2 (Wa+18) / 9.5 average particle content - mass % mass % mass % - mass % Example 1 P1/P2 2 5 1 20 5 2 3.67 Example 2 P1/P2 30 5 1 20 5 2 4.87 Example 3 P1/P2 30 5 20 20 0.25 4 5.48 Example 4 P1 /P2 4 5 20 20 0.25 4 8 Example 5 P1/P2 4 5 3 20 1.67 2.21 4.6 Example 6 P1/P2 15 5 3 20 1.67 2.21 4.88 Example 7 P1/P2 15 5 12 20 0.42 3.16 5.44 Example 8 P1/P2 4 5 12 20 0.42 3.16 6.4 Example 9 P1/P2 8 5 10 20 0.5 2.95 5.56 Example 10 P1/P2 8 5 10 10 0.5 2.95 5.56 Example 11 P1/P2 8 5 10 5 0.5 2.95 5.56 Example 12 P1/P2 8 5 10 25 0.5 2.95 5.56 Example 13 P1/P2 8 10 10 20 1 2.95 10 Example 14 P1/P2 8 3 10 20 0.3 2.95 3.78 Example 15 P1/P2 8 1 10 20 0.1 2.95 2 Example 16 P2/P1/P2 4 5 10 20 0.5 2.95 6.00 Example 17 P1/P2 8 5 10 20 0.5 2.95 5.56 Example 18 P1/P2 8 5 10 20 0.5 2.95 5.56 Comparative Example 1 P1/P2 1.5 5 1 20 5 2 3.4 Comparative Example 2 P1/P2 2 5 0.5 20 10 1.95 3.5 Comparative Example 3 P1/P2 30 5 0.5 20 10 1.95 4.85 Comparative Example 4 P1/P2 30 5 25 20 0.2 4.53 5.65 Comparative Example 5 P1/ P2 4 5 25 20 0.2 4.53 9 Comparative Example 6 P1/P2 3 5 20 20 0.25 4 8.75 Comparative Example 7 P1/P2 8 5 10 0 0.5 2.95 5.56 -40- 201244940 Table 2
機械特性 抗紫外線性 光學特性 密接性 抗濕熱性 薄片強度 紫外線照射後的色調 變化△ b 耐光性試驗後的 伸長保持率 相對反射率 剝離強度 抗濕熱試驗後的 伸長 實施例1 D C C B A A 實施例2 S D D B A A 實施例3 S S S A A A 實施例4 D S S S A A 實施例5 B S S B A A 實施例6 A S S B A A 實施例7 A S S A A A 實施例8 B S S A A A 實施例9 A S S A A A 實施例10 A S S A A A 實施例11 C S S A A A 實施例12 A S S A A A 實施例13 B S S S B C 實施例14 A S A B S S 實施例15 A S C C S s 實施例16 A S S A E A 實施例17 S S S A B A 實施例18 A S S B A A 比較例1 E D D C A A 比較例2 D E D C A A 比較例3 A E D C A A 比較例4 E S S A A A 比較例5 E S S S A A 比較例6 E S S S A A 比較例7 S E S A A A 【圖式簡單說明】 第1圖係使用本發明之聚碳酸酯系樹脂薄片的太陽 圖 面 剖 性 式 模明 5說 例號 一,符 之件 成U 構天 池要 電主 能t 1 太陽能電池用背板 2 封閉劑層 3 發電元件 4 透明基板 5 太陽能電池背板之封閉劑層2側之面 太陽能電池背板之與封閉劑層2相反側之面 -4 1- 6Mechanical properties, UV resistance, optical properties, adhesion, moisture resistance, sheet strength, color change after ultraviolet irradiation, Δ b, elongation retention after light resistance test, reflectance, peel strength, elongation after damp heat test, Example 1 DCCBAA, Example 2, SDDBAA implementation Example 3 SSSAAA Embodiment 4 DSSSAA Embodiment 5 BSSBAA Embodiment 6 ASSBAA Embodiment 7 ASSAAA Embodiment 8 BSSAAA Embodiment 9 ASSAAA Embodiment 10 ASSAAA Embodiment 11 CSSAAA Embodiment 12 ASSAAA Embodiment 13 BSSSBC Embodiment 14 ASABSS Embodiment 15 ASCCS s Example 16 ASSAEA Example 17 SSSABA Example 18 ASSBAA Comparative Example 1 EDDCAA Comparative Example 2 DEDCAA Comparative Example 3 AEDCAA Comparative Example 4 ESSAAA Comparative Example 5 ESSSAA Comparative Example 6 ESSSAA Comparative Example 7 SESAAA [Simplified Schematic] No. 1 The figure is a solar-surface cross-sectional formula of the polycarbonate resin sheet of the present invention, which is exemplified by the example No. 1, and the member of the U-shaped Tianchi is required to have a main energy. 1 Back panel for solar cell 2 Sealant layer 3 Power generating element 4 Transparent substrate 5 Side of the sealant layer 2 of the solar cell back sheet Surface of the solar cell back sheet opposite to the sealant layer 2 -4 1- 6
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TW101110959A TW201244940A (en) | 2011-03-30 | 2012-03-29 | Laminated sheet and solar cell using the same |
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JP (1) | JPWO2012133368A1 (en) |
TW (1) | TW201244940A (en) |
WO (1) | WO2012133368A1 (en) |
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ES2662924T3 (en) * | 2013-10-11 | 2018-04-10 | Mgc Filsheet Co., Ltd. | Scratch resistant polycarbonate resin laminate material |
JP6680036B2 (en) * | 2015-03-31 | 2020-04-15 | 三菱ケミカル株式会社 | Laminate |
KR102589053B1 (en) * | 2022-12-27 | 2023-10-13 | (주)동신폴리켐 | Canopy type polycarbonate solar module |
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JPH05339400A (en) * | 1992-06-15 | 1993-12-21 | Sekisui Chem Co Ltd | Polycarbonate molding |
JPH06198823A (en) * | 1992-12-28 | 1994-07-19 | Dainippon Plastics Co Ltd | Corrugated board for barn |
JP4360510B2 (en) * | 2000-09-01 | 2009-11-11 | 日本化薬株式会社 | Film having cured film of radiation curable resin composition |
JP3681169B2 (en) * | 2002-01-21 | 2005-08-10 | 有限会社 原田塗装工業所 | Method for forming a hard coat layer on a polycarbonate resin substrate surface |
JP2003291277A (en) * | 2002-03-29 | 2003-10-14 | Nissan Motor Co Ltd | Resin laminated body |
JP4080967B2 (en) * | 2003-07-18 | 2008-04-23 | 出光興産株式会社 | Light reflecting sheet and molded product thereof |
JP2006324556A (en) * | 2005-05-20 | 2006-11-30 | Toppan Printing Co Ltd | Solar cell back sheet and solar cell module using the same |
JP5396951B2 (en) * | 2009-03-18 | 2014-01-22 | 三菱化学株式会社 | Active energy ray-curable composition and laminate |
-
2012
- 2012-03-27 JP JP2013507584A patent/JPWO2012133368A1/en active Pending
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