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TW201332766A - 光伏打模組用之具有改良顏料分散性的背膜 - Google Patents

光伏打模組用之具有改良顏料分散性的背膜 Download PDF

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TW201332766A
TW201332766A TW101137466A TW101137466A TW201332766A TW 201332766 A TW201332766 A TW 201332766A TW 101137466 A TW101137466 A TW 101137466A TW 101137466 A TW101137466 A TW 101137466A TW 201332766 A TW201332766 A TW 201332766A
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Andreas Pawlik
Martin Wielpuetz
Michael Beyer
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Evonik Industries Ag
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Abstract

一種包含下列層之膜:a)模製組成物第一外層,其包含I.至少35重量%之聚醯胺含量,及II. 1至65重量%之光反射填料含量,及c)模製組成物第二外層,其具有I.至少35重量%之聚醯胺含量,及II. 1至65重量%之填料含量,其中百分比分別以整體模製組成物為基準計,選自聚醚酯醯胺和聚醚醯胺之聚醯胺彈性體被用作為根據a)的該層之模製組成物中及/或根據c)的該層之模製組成物中的聚醯胺組份,使得根據a)的該層之模製組成物及/或根據c)的該層之模製組成物含有1至25重量%之聚醯胺彈性體。此等膜被用作為光伏打模組的背蓋件,以根據a)的該層結合至已埋入密封層中的太陽能電池。

Description

光伏打模組用之具有改良顏料分散性的背膜
本發明關於作為含聚醯胺之太陽能模組用之具有改良顏料及填料分散性的背膜之多層膜
也常被稱為光伏打模組的太陽能模組適用於自日光發電且由包含太陽能電池系統作為核心層之層合板所組成。此核心層係由封裝材料包封,該封裝材料充當為免於機械和風化(weathering)相關影響的防護。
活性太陽能電池在此係介於前蓋件與背蓋件之間。前蓋件為透明且通常由玻璃所組成;其係利用常由乙烯-乙酸乙烯酯共聚物所組成的黏著性促進層結合至包含太陽能電池之層。背蓋件保證電遮蔽且充當為免於風化影響(諸如UV光)的防護及水氣阻障層。
由氟聚合物膜及聚酯所組成的膜複合物目前用作為背蓋件的標準物。在外側之氟聚合物膜保證抗風化性、聚酯膜機械穩定性及所欲電絕緣性質。在內部之另外的氟聚合物膜適用於附著至太陽能電池系統的密封層。然而,此等氟聚合物膜對用作為太陽能電池本身的包埋材料之密封層僅具有低黏著性。另外,氟聚合物膜僅貢獻低微程度的電絕緣性,其導致必須使用比較厚的聚酯膜。
WO 2008138022因此提出以耐綸-12(PA12)膜替換在此等複合物中之兩個氟聚合物膜。在其發展中,WO 2011066595提出面向太陽能電池之熱塑性層包含光反射填料,諸如二氧化鈦,而遠離太陽能電池之熱塑性層包含第二填料,諸如玻璃纖維、矽灰石或雲母,其造成此層較高的導熱性。例證之熱塑物係出自於聚醯胺、聚酯或聚醯胺與聚烯烴之摻合物的群組。明確述及的是PA11、PA12和PA1010,及其與聚烯烴之摻合物。
在此等光伏打模組中,光反射填料的分布有特別的重要性。因此,太陽能電池的反射程度及由此的發電量係隨著分散性增加而增加。另外,分布的優勢同時影響背膜的表面品質。此在背蓋件的通常以純聚醯胺為底質之層中格外重要,該層面向實際太陽能電池且可於外部看見,且因為層厚度薄之故,使顏料黏聚物在此變得特別明顯。
因此本發明的目的係在光伏打模組之背膜的兩個外層中達成改良之顏料及填料分散性
驚訝地發現此目的可藉由使用聚醚酯醯胺或聚醚醯胺類型之聚醯胺彈性體而達成。
本發明因此提供包含下列層之膜:a)模製組成物第一外層,其包含I.至少35重量%,較佳為至少40重量%,更佳為至少45重量%,尤其佳為至少50重量%,而最佳為至少55重量%之聚醯胺含量,及II. 1至65重量%,較佳為2至60重量%,更佳為 3至55重量%,尤其佳為4至50重量%,而最佳為5至45重量%之光反射填料含量,b)隨意地熱塑性模製組成物中間層,及c)模製組成物第二外層,其具有I.至少35重量%,較佳為至少40重量%,更佳為至少45重量%,尤其佳為至少50重量%,而最佳為至少55重量%之聚醯胺含量,及II. 1至65重量%,較佳為2至60重量%,更佳為3至55重量%,尤其佳為4至50重量%,而最佳為5至45重量%之填料含量,其中百分比分別以整體模製組成物為基準計,且其中膜複合物係藉由使用選自聚醚酯醯胺和聚醚醯胺之聚醯胺彈性體作為根據a)的層之模製組成物中及/或根據c)的層之模製組成物中的聚醯胺組份而改質,使得根據a)的層之模製組成物及/或根據c)該層之模製組成物含有1至25重量%,較佳為2至20重量%,而更佳為4至20重量%之聚醯胺彈性體。
在此例子中,根據a)、b)及c)的該等層係直接接著另一者。根據a)的層及根據c)的層二者另外較佳地包含聚醯胺彈性體。在一些例子中,在根據a)與b)的該等層之間及/或在根據b)與c)的該等層之間的層黏著性可藉由插入黏著性促進層而改良。
聚醯胺可為部分結晶性聚醯胺,例如PA6、PA66、PA610、PA612、PA10、PA810、PA106、PA1010、 PA11、PA1011、PA1012、PA1210、PA1212、PA814、PA1014、PA618、PA512、PA613、PA813、PA914、PA1015、PA11、PA12或稱為聚酞醯胺(PPA)之半芳族聚醯胺(聚醯胺之命名係對應於國際標準,前面的數字(等)表示起始二胺的碳原子數目及最後的數字(等)表示二羧酸的碳原子數目。若只提到1個數字,此意指起始材料為α,ω-胺基羧酸或自其衍生之內醯胺;其餘者參考H.Domininghaus,Die Kunststoffe und ihre Eigenschaften [The polymers and their properties],pages 272 ff.,VDI-Verlag,1976)。適合的PPA為例如PA66/6T、PA6/6T、PA6T/MPMDT(MPMD代表2-甲基五亞甲基二胺)、PA9T、PA10T、PA11T、PA12T、PA14T和該等類型與脂族二胺及脂族二羧酸或與ω-胺基羧酸或內醯胺之共聚縮合物。部分結晶性聚醯胺具有超過25焦耳/公克之熔合焓,其係在第二加熱步驟中根據ISO 11357之DSC方法及熔融峰積分所測量。
聚醯胺亦可為半結晶性聚醯胺。半結晶性聚醯胺具有4至25焦耳/公克之熔合焓,其係在第二加熱步驟中根據ISO 11357之DSC方法及熔融峰積分所測量。適合的半結晶性聚醯胺之實例為:- 1,10-癸二酸或1,12-十二烷二酸及4,4'-二胺基二環己基甲烷(PA PACM10和PA PACM12)之聚醯胺,來自具有35至65%之反,反異構物含量的4,4-二胺基二環己基甲烷; - 以前述部分結晶性聚醯胺為底質的共聚物;及- 前述部分結晶性聚醯胺與可相容之非晶形聚醯胺的摻合物。聚醯胺亦可為非晶形聚醯胺。非晶形聚醯胺具有低於4焦耳/公克之熔合焓,其係在第二加熱步驟中根據ISO 11357之DSC方法及熔融峰積分所測量。
非晶形聚醯胺之實例為:- 對苯二甲酸及/或間苯二甲酸及2,2,4-與2,4,4-三甲基六亞甲基二胺的異構物混合物之聚醯胺,- 間苯二甲酸及1,6-六亞甲基二胺之聚醯胺,- 對苯二甲酸/間苯二甲酸與1,6-六亞甲基二胺之混合物的共聚醯胺,隨意地在與4,4'-二胺基二環己基甲烷之混合物中,- 對苯二甲酸及/或間苯二甲酸、3,3'-二甲基-4,4'-二胺基二環己基甲烷及月桂內醯胺或己內醯胺之共聚醯胺,- 1,12-十二烷二酸或癸二酸、3,3'-二甲基-4,4'-二胺基二環己基甲烷及隨意的月桂內醯胺或己內醯胺之(共)聚醯胺,- 間苯二甲酸、4,4'-二胺基二環己基甲烷及月桂內醯胺或己內醯胺之共聚醯胺,- 1,12-十二烷二酸及4,4'-二胺基二環己基甲烷(在低的反,反異構物含量之例子中)之聚醯胺,- 對苯二甲酸及/或間苯二甲酸及經烷基取代之雙 (4-胺基環己基)甲烷同系物之(共)聚醯胺,隨意地在與六亞甲基二胺之混合物中,- 隨意地與另外的二胺一起的雙(4-胺基-3-甲基-5-乙基環己基)甲烷及隨意地與另外的二羧酸一起的間苯二甲酸之共聚醯胺,- 間-伸二甲苯二胺與另外的二胺(例如,六亞甲基二胺)之混合物及隨意地與另外的二羧酸(例如,對苯二甲酸及/或2,6-萘二羧酸)一起的間苯二甲酸之共聚醯胺,- 雙(4-胺基環己基)甲烷與雙(4-胺基-3-甲基環己基)甲烷之混合物及具有8至14個碳原子的脂族二羧酸之共聚醯胺,及- 包含1,14-十四烷二酸與芳族、芳基脂族或環脂族二胺的混合物之聚醯胺或共聚醯胺。
該等實例可藉由添加另外的組份(例如,己內醯胺、月桂內醯胺或二胺/二羧酸組合)或藉由以其他組份部分或完全替換起始組份而達到非常重大程度的改變。
聚醚酯醯胺係例如從DE-A-25 23 991和DE-A-27 12 987已知;該等含有聚醚二醇作為共單體。聚醚醯胺係例如從DE-A-30 06 961已知;該等含有聚醚二胺作為共單體。
在聚醚二醇或聚醚二胺中,聚醚單元可以例如1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇或1,3-丁二醇為底質。聚醚單元亦可具有混合型結構,例如具有源自二 醇之單元的無規或嵌段式分布。聚醚二醇或聚醚二胺之重量平均莫耳質量為200至5000公克/莫耳,而較佳為400至3000公克/莫耳;其在聚醚酯醯胺或聚醚醯胺中的比率較佳為4至60重量%,而更佳為10至50重量%。適合的聚醚二胺係藉由對應之聚醚二醇以還原胺化作用或偶合在丙烯腈上及接著氫化而獲得。其在市場上可自例如Huntsman Corp.以JEFFAMINE® D或ED類型或ELASTAMINE®類型之形式或自BASF SE以聚醚胺D系列之形式取得。若使用支鏈聚醚醯胺,則亦有可能使用較少量的聚醚三胺,例如JEFFAMINE® T類型。優先選擇使用在鏈中以每個醚氧原子計含有平均至少2.3個碳原子的聚醚二胺或聚醚三胺。根據本發明,由於水解穩定性較佳,優先選擇為聚醚醯胺。
根據a)的層之模製組成物可含有前述聚醯胺中之一或其二或多者之混合物。另外,可以模製組成物之整體聚合物含量為基準計有至多40重量%之其他熱塑物的存在,例如衝擊修飾橡膠。依照先前技藝,任何存在的橡膠較佳地含有官能基,以其獲得與聚醯胺基質的相容性。另外,可有習用於聚醯胺之助劑和添加劑的存在,尤其為光及/或熱穩定劑。光反射填料可為具有反射能力大於根據a)的層之熱塑性組份的反射能力之任何填料;其尤其為二氧化鈦(WO 2011066595)。
根據b)的層之模製組成物可含有例如聚醯胺、聚烯烴及/或聚酯作為熱塑物。另外,可有習知的助劑和添加 劑的存在,尤其為光及/或熱穩定劑、光反射填料(例如,二氧化鈦)和強化填料(例如,玻璃纖維、矽灰石或雲母)。
關於根據c)的層之模製組成物,可應用與根據a)的層之模製組成物相同者,而關於填料,亦可應用與根據b)的層之模製組成物相同者。另外,根據c)的層之模製組成物可著色及/或包含消光劑。
在三層具體例中,各個膜層通常具有下列厚度:.根據a)和c)的層:15至100微米,而較佳為25至50微米;.根據b)的層:100至500微米,而較佳為150至400微米。
在兩層具體例中,層厚度通常如下:.根據a)的層:15至100微米,而較佳為25至50微米;.根據c)的層:100至500微米,而較佳為150至400微米。
在根據a)與b)的該等層之間或在b)與c)的該等層之間存在的任何黏著性促進層通常為3至40微米,而較佳為5至25微米厚度。
依照本發明所使用之多層膜可以所有的先前技藝方法製造,例如共擠壓或層合。
本發明亦提供根據申請專利範圍之膜作為光伏打模組的背蓋件之用途。出於此目的,根據a)的層係藉由例如 層合或黏著而結合至太陽能電池已埋入其中的密封層。由於聚醯胺或聚醯胺彈性體在根據a)的層中之比率,層合給予密封層好的黏著性。所使用之密封層可為根據先前技藝常使用之任何材料。
本發明進一步提供光伏打模組,其包含根據申請專利範圍之多層膜作為背蓋件,以根據a)的層結合至太陽能電池已埋入其中的密封層。
本發明係以下文之實例方式例證。下列的模製組成物係出於此目的而製造;〝份〞通常為重量份:
用於外層之混練物1:
將79.25份VESTAMID® L1901 nf(PA12)、0.5份IRGANOX® 1098(位阻酚抗氧化劑)、0.2份TINUVIN® 312(UV吸收劑)與20份二氧化鈦Sachtleben R 420在220℃之機筒溫度藉助雙軸擠壓機(Coperion Werner & Pfleiderer ZSK 25 WLE,36 L/D)而混合。將擠壓物藉助水浴而冷卻且切碎;接著將丸粒在強加空氣的烘箱中以80℃經12小時乾燥。
用於外層之混練物2:
將71.75份VESTAMID® L1901 nf、7.5份聚醚酯醯胺(從63.796重量%之月桂內醯胺、6.645重量%之十二烷 二酸、29.492重量%之PTHF 1000及0.067重量%之50%次磷酸製得)、0.5份IRGANOX® 1098、0.2份TINUVIN® 312與20份二氧化鈦Sachtleben R 420在220℃之機筒溫度藉助雙軸擠壓機(Coperion Werner & Pfleiderer ZSK 25 WLE,36 L/D)而混合。將擠壓物藉助水浴而冷卻且切碎;接著將丸粒在強加空氣的烘箱中以80℃經12小時乾燥。
用於外層之混練物3:
將64.25份VESTAMID® L1901 nf、15份與混練物2中相同的聚醚酯醯胺、0.5份IRGANOX® 1098、0.2份TINUVIN® 312與20份二氧化鈦Sachtleben R 420在220℃之機筒溫度藉助雙軸擠壓機(Coperion Werner & Pfleiderer ZSK 25 WLE,36 L/D)而混合。將擠壓物藉助水浴而冷卻且切碎;接著將丸粒在強加空氣的烘箱中以80℃經12小時乾燥。
用於中間層之混練物4:
將50.6份VESTAMID® L1901、26份MOPLEN HP552L(均聚丙烯,擠壓型)、20份TEC 110高嶺土、3份KRATON® FG1901(經順丁烯二酸酐改質之苯乙烯-乙烯/丁烯嵌段共聚物)與0.4份IRGANOX® 1098在200℃之機筒溫度藉助雙軸擠壓機(Coperion Werner & Pfleiderer ZSK 25 WLE,36 L/D)而混合。將擠壓物藉助 水浴而冷卻且切碎;接著將丸粒在強加空氣的烘箱中以80℃經12小時乾燥。
三層膜之擠壓:
使用來自Collin之多層膜系統(300毫米狹縫模具,0-6毫米間距,用於3-層膜或5-層膜之共擠壓進料塊)在約230℃之加工溫度製造3-層膜。中間層設定為250微米,而每個外層設定為50微米。將結果顯示於表1中。
改良之顏料分散性表現在依照本發明的反射性改善。

Claims (12)

  1. 一種包含下列層之膜,a)模製組成物第一外層,其包含I.至少35重量%之聚醯胺含量,及II. 1至65重量%之光反射填料含量,及c)模製組成物第二外層,其具有I.至少35重量%之聚醯胺含量,及II. 1至65重量%之填料含量,其中百分比分別以整體模製組成物為基準計,該膜的特徵在於選自聚醚酯醯胺和聚醚醯胺之聚醯胺彈性體被用作為根據a)的該層之模製組成物中及/或根據c)的該層之模製組成物中的聚醯胺組份,使得根據a)的該層之模製組成物及/或根據c)的該層之模製組成物含有1至25重量%之聚醯胺彈性體。
  2. 根據申請專利範圍第1項之膜,其中根據a)的該層之模製組成物及/或根據c)的該層之模製組成物含有2至20重量%之聚醯胺彈性體。
  3. 根據申請專利範圍第1項之膜,其中該聚醯胺彈性體為聚醚醯胺。
  4. 根據申請專利範圍第1至3項中任一項之膜,其中下列層係存在於根據a)與c)的該等層之間:b)熱塑性模製組成物的中間層。
  5. 根據申請專利範圍第4項之膜,其中黏著性促進層係存在於根據a)與b)的該等層之間及/或根據b)與c) 的該層之間。
  6. 根據申請專利範圍第1至3項中任一項之膜,其中根據a)及c)的該等層係呈直接連續。
  7. 根據申請專利範圍第4項之膜,其中- 根據a)和c)的該等層具有15至100微米之厚度,及- 根據b)的該層具有100至500微米之厚度。
  8. 根據申請專利範圍第5項之膜,其中該黏著性促進層或該等黏著性促進層各自具有3至40微米之厚度。
  9. 根據申請專利範圍第6項之膜,其中- 根據a)的該層具有15至100微米之厚度,及- 根據c)的該層具有100至500微米之厚度。
  10. 根據申請專利範圍第1至3項中任一項之膜,其中該光反射填料為二氧化鈦。
  11. 一種根據前述申請專利範圍中任一項之膜的用途,其係作為光伏打模組之背蓋件,以根據a)的該層結合至太陽能電池已埋入其中的密封層。
  12. 一種光伏打模組,其包含根據申請專利範圍1至10中任一項之膜作為背蓋件,以根據a)的層結合至太陽能電池已埋入其中的密封層。
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US20130092227A1 (en) 2013-04-18
EP2581225A1 (de) 2013-04-17
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KR20130040722A (ko) 2013-04-24
DE102011084520A1 (de) 2013-04-18
CN103072354A (zh) 2013-05-01
JP2013086511A (ja) 2013-05-13
TWI558562B (zh) 2016-11-21
JP6180096B2 (ja) 2017-08-16
KR101998412B1 (ko) 2019-07-09
EP2581225B1 (de) 2016-09-14
ES2606373T3 (es) 2017-03-23

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