TWI431791B - Multi - layer films for solar cell substrates - Google Patents
Multi - layer films for solar cell substrates Download PDFInfo
- Publication number
- TWI431791B TWI431791B TW097119214A TW97119214A TWI431791B TW I431791 B TWI431791 B TW I431791B TW 097119214 A TW097119214 A TW 097119214A TW 97119214 A TW97119214 A TW 97119214A TW I431791 B TWI431791 B TW I431791B
- Authority
- TW
- Taiwan
- Prior art keywords
- multilayer film
- layer
- solar cell
- scattering layer
- support layer
- Prior art date
Links
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Classifications
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Description
本發明係有關太陽電池基材用多層薄膜。
太陽電池中,一般有:以玻璃為基材之剛硬型、與以塑膠薄膜為基材之可撓型。剛硬型相較於可撓型,其太陽電池之能量轉換效率雖高,惟其機器之薄型化,輕量化卻受限,且受撞擊時亦可能導致太陽電池模組受損。因此,可撓型之太陽電池之有用性倍受矚目,具有各種構造之可撓型太陽電池(被揭示如:特開平1-198081號、特開平2-260577號、特公平6-5782號、特開平6-350117號),例如:作為用於手錶、手機、手提電腦等移動體通訊機器之電源(主要為補助電源)。
如上述之可撓型太陽電池係於發電層(半導體層)使用非晶質矽或微結晶矽,使發電層厚度作成數十μm以下、特別作成數μm以下之薄膜型者為其主流。薄膜太陽電池中,以為提昇光電轉換效率,於發電層之層內增加光吸收量者為其課題,於基材表面上形成中心線平均表面粗度Ra為100nm左右的凹凸之導電層,使光擴散,藉由增加發電層層內之光的光路長(亦即「關閉光之效果(light trapping effect)」),嘗試解決該課題。
惟,為使金屬、金屬氧化物所成之導電層形成具有凹凸形狀,一般必須以400℃以上的高溫進行處理,因此不
適用於以塑膠薄膜為基材之可撓型太陽電池。對於此,提出有使用含有填充劑之樹脂組成物,於支撐層上形成凹凸,其上藉由形成導電層後,實現具有凹凸之導電層的技術(特開平4-196364號及特開平1-119074號)。惟,藉由此等方法,為得到足夠凹凸效果時,務必提高填充劑濃度,將出現損及基材強度之缺點。另外,於專利第3749015號中記載,於支撐層表面塗佈紫外線硬化性樹脂,於塑模擠壓後硬化,形成凹凸,其上形成導電層之技術。惟,此方法其步驟煩雜,成本提昇之主因外,更使形成凹凸層時所使用之樹脂溶液之殘留溶媒於導電層形成時出現脫氣而受影響後,導致形成凹凸層之形狀未能順利反映於導電層之問題存在。於特公平7-50794號記載有利用上述脫氣體之凹凸形成之技術,惟,其不易定量控制樹脂中之殘留溶媒及脫氣體量,對於凹凸形狀之調節極為不易。
更且,於上述任一技術中,均於賦予凹凸之導電層上配置發電層,因此,必須採取其各發電層完全追隨凹凸,而不會出現短路之電池結構,太陽電池之薄膜化受限,且發電層設計自由度低,提昇光電轉換效率亦受限。
本發明之目的係為解決該先前技術之課題,提供一種在維持發電層形成時層設計自由度為廣範圍的同時,顯示可得到高度光關閉效果之高度光擴散效果之太陽電池基材
用多層薄膜。
亦即,本發明之該課題係藉由由支撐層與散射層所成之太陽電池基材用多層薄膜,該支撐層係由熱塑性結晶性樹脂所成,該散射層係由熱塑性結晶性樹脂及具有與該熱塑性結晶性樹脂之折射率不同之折射率的粒子所成,該散射層中粒子之含有率以散射層之體積為基準下,為0.05~20體積%,而散射層中之粒子折射率與散射層之熱塑性結晶性樹脂之折射率之差的絕對值為0.01~1.00,該多層薄膜之兩面中心線平均表面粗度Ra分別為50nm以下,該多層薄膜之總光線透過率Tt為80%以上,且濁度率為8%以上之太陽電池基材用多層薄膜所達成。
另外,該濁度率係指擴散成份佔薄膜之總光線透過率之比例。
[發明實施之最佳形態]
以下,詳細說明本發明。
(支撐層)
本發明之太陽電池基材用多層薄膜之支撐層係由熱塑性結晶性樹脂所成。熱塑性結晶性樹脂為可熔融擠壓成型,耐熱性良好,故適於太陽電池之製造。作為此熱塑性
結晶性樹脂者,可使用如:聚醚醚酮、聚苯撐硫化物、聚醯胺、聚酯等。其中由其步驟,最後製品之耐久性觀點視之,出現低吸水率,且具較高之氣體隔離性的聚酯為較佳。作為聚酯例者可列舉如:以對苯二甲酸乙二醇酯成份為主要重覆單位之聚酯、乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯。支撐層所使用之對苯二甲酸乙二醇酯成份為主要重覆單位之聚酯中,對苯二甲酸乙二醇酯成份之含有比例,對於聚酯中總重覆單位而言,為80~100莫耳%者宜,更佳者為90~100莫耳%。作為此時之共聚成份者如:間苯二甲酸、2,6-萘二羧酸等例。用於支撐層之乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯中乙烯-2,6-萘二羧酸酯成份之含有比例,對於聚酯中總重覆單位而言,為80~100莫耳%者宜,更佳者為90~100莫耳%。作為此時之共聚成份者,如:對苯二甲酸、間苯二甲酸等例。
此等熱塑性結晶性樹脂中,又以乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯較可得到高度尺寸安定性較為理想。
(散射層)
本發明之太陽電池基材用多層薄膜之散射層係由熱塑性結晶性樹脂及具有與該熱塑性結晶性樹脂之折射率不同之折射率的粒子所構成。
作為此熱塑性結晶性樹脂者,考量於太陽電池所加工
之步驟,以耐熱性高之樹脂者宜,可使用如:聚醚醚酮、聚苯撐硫化物、聚醯胺、聚酯。其中由步驟,最後製品之耐久性之觀點視之,又以聚酯出現低吸水率,具有較高之氣體隔離性為較理想者。作為此聚酯例者如:以對苯二甲酸乙二醇酯成份為主要重覆單位之聚酯,以乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯例者。用於散射層之以對苯二甲酸乙二醇酯成份為主要重覆單位之聚酯中對苯二甲酸乙二醇酯成份之含有比例,對於聚酯中之總重覆單位而言,為65~100莫耳%者宜,較佳者為70~100莫耳%,更佳者為80~100莫耳%,特別以90~100莫耳%最為理想。作為此時之共聚成份者,如:間苯二甲酸、2,6-萘二羧酸為例。用於散射層之乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯中乙烯-2,6-萘二羧酸酯成份之含有比例對於聚酯中之總重單位而言,為65~100莫耳%者宜,較佳者為70~100莫耳%,更佳者為80~100莫耳%,特別以90~100莫耳%最為理想。作為此時之共聚成份者,如:對苯二甲酸、間苯二甲酸等例。
此等熱塑性結晶性樹脂中,由得到高度尺寸穩定性面觀之,又以乙烯-2,6-萘二羧酸酯成份為主要重覆單位之聚酯者較佳。
散射層之熱塑性結晶性樹脂與支撐層之熱塑性結晶性樹脂可為相同,亦可為相異者。支撐層由聚乙烯-2,6-萘二羧酸酯所成,散射層由粒子及聚乙烯-2,6-萘二羧酸酯所成之多層薄膜由其高溫雰圍下之熱收縮率,如:200℃、10
分鐘處理後之熱收縮率被抑制降低之觀點視之,為特別理想。
作為散射層中之粒子形狀者,如:球狀、立方體狀、四足(tetrapod)狀、板狀、棒狀等例。粒子之平均粒徑為0.05~10μm者宜,更佳者為0.1~8μm、特別以0.2~6μm最為理想。當粒子之平均粒徑未達0.05μm時,則將未能充份使光散射,反之,超出10μm則不易有效維持光線透過率故不佳。此粒子之平均粒徑係利用(股份)島津製作所製,CP-50型、Centrifugal Particle Size Annalyzer測定後由得到離心沈降曲線為基準所算出之各粒徑粒子與其存量之合計曲線讀取相當於50重量%之粒徑之值。該平均粒徑其粒子為球狀以外之形狀時,作成相當於球徑所讀取之值。
粒子之折射率為1.20~2.50。本發明藉由散射層之熱塑性結晶性樹脂與粒子之折射率差,得到光散射效果。其中,熱塑性結晶性樹脂之折射率係指,以該熱塑性結晶性樹脂作為薄膜時之面內之折射率之平均值,如:使熱塑性結晶性樹脂之薄膜藉由熔融擠壓進行製造時為薄膜面內製膜方向之折射率nMD與面內之製膜方向所垂直方向的折射率nTD之平均值。又,多層薄膜為延伸薄膜時,熱塑性結晶性樹脂之折射率係指延伸薄膜狀態下之折射率。
散射層之熱塑性結晶性樹脂之折射率與粒子之折射率之差愈大,愈容易得到光散射效果,但當折射率差太大時,恐降低光線透過率。為了兼具光散射效果與光線透過
性,該散射層中粒子之折射率與熱塑性結晶性樹脂之折射率之差的絕對值為0.01~1.00者宜,更佳者為0.05~0.90,特別以0.10~0.50最為理想。
使用聚乙烯-2,6-萘二羧酸酯作為散射層之熱塑性結晶性樹脂時,其折射率若為1.75,則為了兼具有良好的光散射效果與光線透過性,粒子折射率為1.10~1.70之範圍或1.80~2.20之範圍者宜。作為該粒子者,如:無機粒子、有機粒子、矽酮樹脂粒子、有機鹽粒子可被列舉。作為構成無機粒子之材料者,如:二氧化矽、碳酸鈣、氧化鋁、二氧化鈦、沸石、陶土黏土及此等複合體以及硫酸鋇等例。作為該複合體者,如:複合氧化物、芯穀型之複合體等例。作為有機粒子者,以交聯高分子粒子者宜,具體例如:交聯聚苯乙烯粒子、蜜胺樹脂粒子可被列舉。作為構成有機鹽粒子之材料者,如:包含金屬原子之包攝化合物及錯化物等例,作為該金屬原子者,如:銀、銅、鐵等例。此時,散射層之粒子含有比例為0.05~20體積%者宜,更佳者為0.1~15體積%。其中體積%係指,由散射層中粒子重量%單位之含有比例利用粒子之真密度及樹脂之非晶狀態之密度,計算所求出之值。粒子之含有比例若未達0.05體積%則,無法使光充分散射,反之超出20體積%則構成該樹脂之層變脆,將無法得到實用的機械強度,而不理想。其中所使用之粒子可為1種粒子、或二種、三種以上之粒子均可。上述任意情況均可併用不同平均粒徑粒子。
使用聚苯撐硫化物為散射層之熱塑性結晶性樹脂時,其折射率若為1.77,則為了兼具良好的光散射效果與光線透過性,粒子折射率為1.12~1.72之範圍,或1.82~2.52之範圍者宜。作為此時之粒子者,如:無機粒子、有機粒子、有機鹽粒子、氟樹脂粒子可被列舉。其中,針對分別構成無機粒子、有機粒子、有機鹽粒子之材料,其散射層之熱塑性結晶性樹脂與上述相同,作成適用於聚乙烯-2,6-萘二羧酸酯時之無機粒子、有機粒子及有機鹽粒子。此時,散射層之粒子含有比例為0.01~20體積%者宜,更佳者為0.1~15體積%。
使用聚醯胺為散射層之熱塑性結晶性樹脂時,該聚醯胺若為折射率1.54之尼龍,則為了兼具良好的光散射效果與光線透過性,粒子之折射率為1.09~1.49之範圍或1.59~2.21之範圍者宜。作為該粒子者,如:無機粒子、有機粒子、有機鹽粒子、氟樹脂粒子可被列舉。其中,針對分別構成無機粒子、有機粒子及有機鹽粒子之材料,其散射層之熱塑性結晶性樹脂與上述相同,作成適用於聚乙烯-2,6-萘二羧酸酯時之無機粒子、有機粒子及有機鹽粒子。此時,散射層中粒子之含有比例為0.01~20體積%者宜,更佳者為0.1~18體積%。
(添加劑)
支撐層及散射層之熱塑性結晶性樹脂中,單面或雙面,均可添加添加劑。其中作為可添加之添加劑者,可列
舉如:紫外線吸收劑、抗氧化劑、熱穩定化劑、易滑劑(如:蠟)、難燃劑、靜電防止劑等。
該紫外線吸收劑係為進一步提昇多層薄膜之耐候性,添加於熱塑性結晶性樹脂者宜。作為該紫外線吸收劑者,為少量有效之吸光係數大的化合物者宜,如:2,2’-p-苯撐雙(3,1-苯並噁嗪-4-酮)、2,2’-(4,4’-二苯撐)雙(3,1-苯並噁嗪-4-酮)或2,2’-(2,6-萘)雙(3,1-苯並噁嗪-4-酮)者宜。摻合紫外線吸收劑時,其摻合量以多層薄膜之重量為基準下,例如為0.01~10重量%。
(太陽電池基材用多層薄膜之構成)
本發明之太陽電池基材用多層薄膜係如上述由支撐層與散射層所成。多層薄膜亦可由一層支撐層與一層散射層所成之雙層薄膜,支撐層及散射層中之單面或雙面亦可為雙層以上之多層薄膜。作成三層以上之多層構成時,至少使支撐層配置於單面之最外層者宜。特別為支撐層/散射層之雙層構造、或支撐層/散射層/支撐層之三層構造最為理想。
本發明太陽電池基材用多層薄膜之厚度為15~250μm者宜、更佳者為50~200μm,特別以60~125μm最為理想。當厚度未達15μm時,則作為太陽電池支撐體之基材之僵硬性變小而無法支撐太陽電池,因而不理想,反之,超出250μm則太陽電池模件之厚度變太厚,失去可撓性而不理想。
為提高多層薄膜之總光線透過率,使含於支撐層之粒子比例,於上述範圍內,儘可能減少,同時擴大支撐層厚度與散射層厚度之比率(支撐層之厚度/散射層之厚度)即可。為提昇光擴散效果,務必使散射層亦達某程度之厚度。多層薄膜為支撐層/散射層之雙層構造時之厚度比率為0.1~30者宜、較佳者為1~30、更佳者為3~20,特別以5~25最佳。多層薄膜之支撐層及散射層中之單面或雙面為雙層以上時之支撐層厚度之合計與散射層厚度之合計之比率(支撐層厚度合計/散射層厚度合計)為1~30者宜、更佳者為1.5~20、特別佳者為2~15。
(中心平均表面粗度)
本發明太陽電池基材用多層薄膜,其兩面之中心線平均表面粗度Ra分別為50nm以下。又,理想之多層薄膜之至少單面之中心線平均表面粗度Ra為30nm以下。
多層薄膜為支撐層/散射層之雙層構造時,該多層薄膜之支撐層側表面之中心線平均表面粗度Ra為30nm以下,散射層側之中心線平均表面粗度Ra為50nm以下者宜。多層薄膜為支撐層/散射層/支撐層之三層構造時,該多層薄膜之兩側表面之中心線平均表面粗度Ra分別為30nm以下者宜。
上述任意情況下,其多層薄膜之兩面中心線平均表面粗度Ra分別為30nm以下者宜,更佳者為10nm以下。多層薄膜表面之中心線平均表面粗度Ra若超出50nm,則為
了抑制短路等情況,其發電層之厚度、形狀等均受限,用於提昇發電層之光電轉換效率之層設計自由度降低,而不理想。
(光學特性)
本發明之太陽電池基材用多層薄膜其總光線透過率Tt為80%以上,較佳者為80~100%。擴散成份佔多層薄膜之總光線透過率Tt之比例之濁度率為8%以上,較佳者為8~100%、更佳者為15~100%。
光線光線透過率Tt未達80%時,則入射於太陽電池之入射光量將降低,無法得到高度發電效率。當濁度率未達8%則光擴散變少,無法充份得到光關閉效果。
該光學特性係以熱塑性結晶性樹脂構成支撐層,使散射層由熱塑性結晶性樹脂及具有與該熱塑性結晶性樹脂折射率不同之折射率之粒子所構成,該散射層中之粒子含有率以散射層之體積為基準下為0.05~20體積%,且使散射層中之粒子折射率與散射層之熱塑性結晶樹脂之折射率之差的絕對值作成0.01~1.00,則可達成。
(熱收縮率)
本發明太陽電池基材用多層薄膜由太陽電池製造步驟之加熱步驟的抑制尺寸變化之觀點視之,以200℃下處理10分鐘時之熱收縮率為1%以下者宜,更佳者為0.8%以下,特別佳者為0.6%以下。該熱收縮率係藉由作為支撐
層者,使如:乙烯-2,6-萘二羧酸成份為主要重覆單位之聚酯,更佳者為乙烯-2,6-萘二羧酸酯成份對於聚酯中之總重覆單位而言,使用含有90~100莫耳%之聚酯後,可達成。
(多層薄膜之製造方法)
本發明之太陽電池基材用多層薄膜分別使構成支撐層之熱塑性結晶性樹脂與構成散射層之熱塑性結晶性樹脂以及由粒子所成之組成物進行熔融,將此等藉由共同擠壓法進行熔融擠壓後延伸製造為宜。另外,若以溶液法製造薄膜時,為了對於太陽電池進行加工,於後步驟,於薄膜上設置導電層之步驟,或形成光發電層之步驟,會產生源於殘留溶媒之氣體,妨礙減壓步驟,或有雜質殘留之情況,因而不理想。
使薄膜多層化之方法,可使用例如將由各別之擠壓器所擠出之樹脂藉由分流器合流,以塑模擠出之方法,使由分別之擠壓器所擠出之樹脂利用複式接頭塑模(multi-manifold die)於塑模內,在擠壓前合流進行擠出之方法等。
於散射層中以高濃度添加粒子時,為充份得到實用之機械強度,藉由雙軸延伸製造多層薄膜者宜。
以下,詳述使用聚酯為熱塑性結晶性樹脂時之多層薄膜之製造方法。此例係藉由共同擠壓,得到未延伸多層薄膜,之後,逐次藉由雙軸延伸法取得雙軸延伸多層薄膜。
由構成支撐層之熱塑性結晶性樹脂、與構成散射層之
熱塑性結晶性樹脂,及粒子所成之組成物,於必要時,常壓下,加熱或減壓下經由乾燥去除水份後,以該業界常用之熔融擠壓溫度,亦即熔點(以下,以「Tm」示之)以上,於(Tm+50℃)以下之溫度下各自之擠壓器下進行熔融,利用給料裝置成雙層構成之多層化後,由塑模之縫隙進行擠出後,冷卻至各層之樹脂中玻璃轉移溫度(以下,以「Tg」示之)之最低樹脂之Tg以下進行冷卻之旋轉冷卻滾筒上,經由急冷固化後,取得非晶質之薄片。所取得之薄片其各層之樹脂中,Tg為最高樹脂之Tg以上,(Tg+50℃)以下之範圍,以2.5~4.5倍之延伸倍率往縱方向進行延伸,接著各層之樹脂中Tg為最高樹脂之Tg以上,(Tg+50℃)以下之範圍,以2.5~4.5倍之延伸倍率往橫方向進行延伸。縱延伸與橫延伸同時進行之同時雙軸延伸亦因容易得到縱橫之機械特性的平衡點,而為理想。
往縱橫延伸之薄膜,其各層樹脂中結晶化溫度(以下以「Tc」示之)為最低之樹脂之Tc以上,其各層之樹脂中Tm為最高樹脂之(Tm-20℃)以下之溫度範圍下進行熱固定。之後,為使熱收縮率更低之目的下,縱方向及橫方向中之單方向或雙方向以弛緩率0.5~15%之範圍下,進行熱弛緩處理者宜。熱弛緩處理於薄膜製造時,進行之方法之外,亦可於卷曲後於另一步驟進行熱處理。卷曲後之熱處理方法可使用如:特開平1-275031號公報所示之使薄膜於懸垂狀態下進行弛緩熱處理之方法。
(太陽電池)
本發明太陽電池基材用多層薄膜可適用於各種太陽電池之基材。特別是用於可撓型之薄膜太陽電池之基材時,可以最大限發揮本發明之有利效果,極為理想。
本發明太陽電池基材用多層薄膜其兩面的中心線平均表面粗度Ra分別為50nm以下時,極為平滑,因此,發電層之設計自由度變大,提昇了太陽電池之薄膜化及光電轉換效率。
多層薄膜之各面中心線平均表面粗度Ra各自不同時,就使發電層之設計自由度更大的觀點而言,較佳為使發電層配置於中心線平均表面粗度Ra小之面之側。如:多層薄膜為支撐層/散射層之雙層構造時,使發電層配置於支撐層側之面者宜。
(實施例)
以下,藉由實施例進行本發明進一步之說明。
另外,各特別值係以下方法所測定。
(1)因有黏度
藉由鄰氯苯酚溶媒於35℃下測定求得溶液之黏度。
(2)各層厚度
將薄膜樣品切取三角形,固定於包埋膠囊後,以環氧樹脂進行包埋。將包埋之樣品以切薄片機(Reichert公司
製、品名「ULTRACUT-S」)往縱方向使平行之截面作成50nm厚之薄膜切片後,利用透過型電子顥微鏡,以加速電壓100kV進行觀察及照相,由相片測出各層厚度。
(3)熱收縮率
設定200℃溫度之烤箱中,於無拉伸狀態下使薄膜保持10分鐘,分別測定熱處理之標點間距離L0、與熱處理後之標點問距離L,將其尺寸變化率作成熱收縮率S(%),藉由下式算出。
S=((L0-L)/L0)×100
另外,評點間距離係將隔著約300mm之間隔而標識之2個評點間之距離測定至0.1mm的單位來求得。
(4)粒子之平均粒徑
以使用(股份)島津製作所製,CP-50型Centrifugal Particle Size Annalyzer進行測定所得之離心沈降曲線為基準下,由所算出之各粒徑之粒子及其存在量之合計曲線,讀取相當於50重量%之粒徑。
(5)中心線平均表面粗度(Ra)
使用非接觸式3維粗度計((股份)小坂研究所製、型號「ET30HK」),以波長780nm之半導體雷射、波束徑
1.6μm之光觸針,於測定長度(LX)1mm,採樣間距2μm、截止點(cut-off)0.25nm、縱方向擴大倍率5,000倍、橫方向擴大倍率200倍、掃描線數100根(故,Y方向之測定長度LY=0.2mm)之條件下,測定薄膜表面之突起外觀,使其粗度曲面以Z=F(X、Y)代表時,求取下式得到之值(Ra、單位nm)為薄膜之中心線表面粗度(Ra)。
(6)多層薄膜之總光線透過率(Tt)
總光線透過率Tt(%)係依JIS規格,K6714進行測定。
(7)濁度率(擴散成份佔多層薄膜之總光線透過率之比例)
依JIS規格K6714,使用日本電色工業(股份)製之濁度計「NDH-2000」,測定多層薄膜之濁度率。另外,多層薄膜表面之中心線平均表面粗度Ra於表裏不同時,其多層薄膜之中心線表面粗度(Ra)係針對粗面之表面進行測定。
多層薄膜之濁度率愈高,作為太陽電池基材用多層薄膜之光的散射效率愈高。
(8)折射率
熱塑性結晶性樹脂之折射率係針對熔融擠壓呈薄膜狀成形之熱塑性結晶性樹脂薄膜,利用Metrlcon公司製之「稜晶玻璃」於波長633nm所測定之全方位折射率中,薄膜面內製膜方向之折射率nMD與往面內製膜方向垂直之方向之折射率nTD之平均值。
[實施例1]
將作為支撐層之熱塑性結晶性樹脂之聚乙烯-2,6-萘二羧酸酯(非晶密度1.33、固有黏度:0.65)與,作為散射層之組成物,平均粒徑0.3μm之球狀二氧化矽(日本觸媒(股份)製、「C-Hoster-KEP-30」、真密度2.0、折射率1.43(覽表值)為含有0.1體積%之聚乙烯-2,6-萘二羧酸酯(非晶密度1.33、固有黏度:0.65、折射率1.76),分別於170℃下進行乾燥6小時後,供入各自之擠壓器。
將此等分別於305℃之溫度下,進行熔融後,利用給料裝置,作成支撐層/散射層/支撐層之三層構成進行合流,由縫隙狀塑模擠出,使表面溫度維持於50℃之旋轉冷卻滾筒上,進行急冷固化,得到未延伸薄膜。
接著,往縱方向於140℃,延伸3.1倍後,往橫方向於145℃,進行延伸3.3倍,更於245℃下進行熱固定處理5秒後往寬方向收縮2%後,得到厚度50μm之三層構成之太陽電池基材用多層薄膜。所得到多層薄膜之支撐層之厚度為10μm,散射層之厚度為30μm、散射層之表面中
心線平均表面粗度Ra為1.2nm、薄膜之總光線透過率Tt為84%、濁度率(擴散成份佔薄膜之總光線透過率之比例)為8.3%。此多層薄膜之熱收縮率為0.5%。
[實施例2~3]
分別使支撐層及散射層之厚度及散射層中粒子之含有比例如表1及表2所載進行變更之外,與實施例1同法製造太陽電池基材用多層薄膜。所得到多層薄膜之特性示於表3。所有多層薄膜之光擴散效率均高,中心線平均表面粗度Ra為30nm以下,熱收縮率為0.6%。
[實施例4]
於支撐層中,使作為紫外線吸收劑之2,6-萘雙(1,3-苯並噁嗪-4-酮)對於100重量份支撐層之樹脂進行添加2重量份之外,與實施例1同法製造太陽電池基材用多層薄膜。所得到多層薄膜之特性示於表3。所有的多層薄膜其光擴散效率均高,中心線平均表面粗度Ra為30nm以下,熱收縮率為0.6%。
[實施例5]
將層構成作成支撐層/散射層之雙層構成之外,與實施例1同法製造太陽電池基材用多層薄膜。所得到之多層薄膜之特性示於表3。所有的多層薄膜之光擴散效率均高,中心線平均表面粗度Ra為30nm以下,熱收縮率為
0.5%。
[實施例6~8]
將散射層所含之粒子種類及含有比例以及散射層之厚度如表1進行變更之外,與實施例1同法製造太陽電池基材用多層薄膜。得到多層薄膜之特性示於表2。所有多層薄膜之光擴散效率均高,中心線平均表面粗度Ra為30nm以下,熱收縮率為0.6%。
[實施例9~11]
將用於散射層之熱塑性結晶性樹脂種類如表1進行變更之外,與實施例6同法製造太陽電池基材用多層薄膜之。得到多層薄膜之特性示於表2。所有多層薄膜之光擴散率均高,中心線平均表面粗度Ra為30nm以下,熱收縮率其實施例9之多層薄膜為0.7%、實施例10及11之多層薄膜為1.0%。
[比較例1]
作為散射層之組成物中無添加粒子之外,與實施例1同法製造薄膜。此薄膜之特性示於表2。得到光擴散效率低之薄膜。
[比較例2]
作為散射層之組成物中無添加粒子之外,與實施例9
同法製造薄膜。此薄膜之特性示於表2。得到光擴散效率低之薄膜。
另外,上述表中,粒子及熱塑性結晶性樹脂之略稱分別如下。
粒子
二氧化矽:日本觸媒(股)製,品號「C-Hoster-KEP-30」
蜜胺樹脂1:日本觸媒(股份)製、品號「eposter-M30」
蜜胺樹脂2:日本觸媒(股份)製、品號「eposter-M05」
蜜胺樹脂3:日本觸媒(股份)製、品號「eposter-S12」
熱塑性結晶性樹脂
PEN:聚乙烯-2,6-萘二羧酸酯
8MTA共聚PEN:共聚8莫耳%對苯二甲酸酯成份之聚乙烯-2,6-萘二羧酸酯/聚對苯二甲酸乙二醇酯共聚物
18.5MTA共聚PEN:共聚18.5莫耳對苯二甲酸酯成份之聚乙烯-2,6-萘二羧酸酯/聚對苯二甲酸乙二醇酯共聚物
30MTA共聚PEN:共聚30莫耳%對苯二甲酸酯成份之聚乙烯-2,6-萘二羧酸酯/聚對苯二甲酸乙二醇酯共聚物
實施例5之雙層構造薄膜中,以支撐層側之面作為表面。
本發明提供一種在大幅維持發電層層設計之幅度的同時,顯示得到高度光關閉效果之高度光擴散效果太陽電池基材用多層薄膜。
Claims (9)
- 一種太陽電池基材用多層薄膜,其係由支撐層與散射層所成之太陽電池基材用多層薄膜,其特徵為該支撐層係由熱塑性結晶性樹脂所成,該散射層係由熱塑性結晶性樹脂及具有與該熱塑性結晶性樹脂之折射率不同之折射率的粒子所成,該散射層中之粒子含有率以散射層之體積為基準下,為0.05~20體積%,而散射層中之粒子折射率與散射層之熱塑性結晶性樹脂之折射率之差的絕對值為0.01~1.00,該多層薄膜之兩面中心線平均表面粗度Ra分別為50nm以下,該多層薄膜之總光線透過率Tt為80%以上,且濁度率為8%以上,該多層薄膜中之支撐層及散射層,係藉由共同擠壓法進行熔融擠壓而層合者。
- 如申請專利範圍第1項之太陽電池基材用多層薄膜,其中支撐層及散射層之熱塑性結晶性樹脂為熱塑性聚酯。
- 如申請專利範圍第2項之太陽電池基材用多層薄膜,其中支撐層及散射層之熱塑性聚酯係以乙烯-2,6-萘二羧酸酯成份作為主要重覆單位之聚酯。
- 如申請專利範圍第3項之太陽電池基材用多層薄膜,其中粒子為二氧化矽粒子或蜜胺樹脂粒子。
- 如申請專利範圍第1項之太陽電池基材用多層薄膜,其中多層薄膜之至少單面之中心線平均表面粗度Ra為30nm以下。
- 如申請專利範圍第1項至第5項中任一項之太陽 電池基材用多層薄膜,其中多層薄膜為支撐層/散射層之雙層構造,該多層薄膜之支撐層側表面之中心線平均表面粗度Ra為30nm以下,散射層側之中心線平均表面粗度Ra為50nm以下。
- 如申請專利範圍第1項至第5項中任一項之太陽電池基材用多層薄膜,其中多層薄膜為支撐層/散射層/支撐層之三層構造,該多層薄膜之兩側表面之中心線平均表面粗度Ra分別為30nm以下。
- 如申請專利範圍第1項至第5項中任一項之太陽電池基材用多層薄膜,其特徵為可撓型之薄膜太陽電池之基材用者。
- 一種如申請專利範圍第1項之太陽電池基材用多層薄膜之製造方法,其特徵為,係經過將該多層薄膜中之支撐層及散射層,藉由共同擠壓法進行熔融擠壓以層合的步驟。
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KR (1) | KR101364790B1 (zh) |
CN (1) | CN101681940B (zh) |
AU (1) | AU2008255673B2 (zh) |
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JP2010278180A (ja) * | 2009-05-28 | 2010-12-09 | Sumitomo Bakelite Co Ltd | 太陽電池用基板 |
FR2955207B1 (fr) | 2010-01-08 | 2012-02-10 | Saint Gobain Technical Fabrics | Dispositif collecteur de rayonnement |
FR2958081B1 (fr) * | 2010-03-23 | 2012-04-27 | Polyrise | Dispositifs photovoltaiques comportant une couche anti-reflet a base d'objets disperses presentant des domaines d'indices de refraction distincts |
TW201219210A (en) * | 2010-11-08 | 2012-05-16 | Eternal Chemical Co Ltd | Film used for solar cell module and module thereof |
US20140124030A1 (en) * | 2011-06-30 | 2014-05-08 | Kaneka Corporation | Thin film solar cell and method for manufacturing same |
CN103311332A (zh) * | 2012-03-12 | 2013-09-18 | 杜邦太阳能有限公司 | 太阳能模组及其制造方法 |
EP2970692B1 (en) * | 2013-03-13 | 2017-04-19 | SABIC Global Technologies B.V. | Thermo-responsive assembly and methods for making and using the same |
WO2014164010A1 (en) * | 2013-03-13 | 2014-10-09 | Sabic Innovative Plastics Ip B.V. | Polyetherimides with improved melt stability and reduced corrosivity |
CN104448512A (zh) * | 2013-09-17 | 2015-03-25 | 国新科技股份有限公司 | 太阳光电池模组用封装膜组合物 |
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JPH02181975A (ja) * | 1989-01-07 | 1990-07-16 | Nitto Denko Corp | フィルム太陽電池 |
JP2774136B2 (ja) | 1989-03-31 | 1998-07-09 | 帝人株式会社 | 非晶質シリコン太陽電池の製造方法 |
JPH0750794B2 (ja) | 1990-06-28 | 1995-05-31 | 三洋電機株式会社 | 光電変換素子の製造方法 |
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KR20100014795A (ko) | 2010-02-11 |
CN101681940B (zh) | 2011-05-04 |
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TW200926428A (en) | 2009-06-16 |
JP5156739B2 (ja) | 2013-03-06 |
US20100167012A1 (en) | 2010-07-01 |
EP2161759B1 (en) | 2015-03-11 |
AU2008255673B2 (en) | 2013-08-29 |
WO2008146896A1 (ja) | 2008-12-04 |
EP2161759A1 (en) | 2010-03-10 |
NZ581526A (en) | 2011-03-31 |
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AU2008255673A1 (en) | 2008-12-04 |
CN101681940A (zh) | 2010-03-24 |
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