CN102399402A - 基于聚乙烯醇缩醛的对uv辐射具有选择透过性的含增塑剂的膜 - Google Patents
基于聚乙烯醇缩醛的对uv辐射具有选择透过性的含增塑剂的膜 Download PDFInfo
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- CN102399402A CN102399402A CN2011102482109A CN201110248210A CN102399402A CN 102399402 A CN102399402 A CN 102399402A CN 2011102482109 A CN2011102482109 A CN 2011102482109A CN 201110248210 A CN201110248210 A CN 201110248210A CN 102399402 A CN102399402 A CN 102399402A
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- polyvinyl acetal
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Abstract
Description
技术领域
本发明涉及基于聚乙烯醇缩醛的对UV辐射具有选择透过性(Durchl?ssigkeit)且具有低泛黄趋势(Vergilbungsneigung)的含增塑剂的膜,以及采用其制得的玻璃层压体。
背景技术
市场上常见的用于复合玻璃的类型的含增塑剂的聚乙烯醇缩丁醛膜(PVB膜)多年来配备有UV吸收剂,由此使得UV辐射(与可见光相反)不能透过复合玻璃。这样,可以以简单方式确保在复合玻璃之后的人或物体几乎彻底地受到保护以免受有害UV辐射。除了提供保护以免于切割损伤,这是与单块玻璃相比的重要优点,因为单块玻璃对UV辐射是基本透明的。
对于PVB膜作为包封材料在光电模块(Photovoltaikmodule)中的应用,使用甚至提高量的UV吸收剂,这是因为认为由于太阳能模块的强日光暴露可能会导致发生PVB膜的泛黄。
2-羟基苯基苯并三唑衍生物(其可以各种取代模式获得,例如以商品名Tinuvin P、Tinuvin 328、Tinuvin 327、Tinuvin 326)已证实特别适合和广泛地作为UV吸收剂。PVB膜中苯并三唑型UV吸收剂以它们的优异长期稳定性、良好溶解性和在整个UV范围(UV-B和UV-A)内的高吸收性能著称。但是,依据取代模式,在可见光谱范围内、即400nm下也发生或多或少强烈的吸收,由此这些UV吸收剂可能导致PVB膜的一定黄变,取决于用量和取代基分布。
如果对于复合安全玻璃的绝大多数可能应用需要对于UV辐射的尽可能彻底的保护、即大于99%的吸收,那么存在其中期望对于UV辐射的高透过性的特定应用:
-在用于种植蔬菜或切花的温室中,需要尽可能高的能量输入和最小的UV辐射。此外,还基于UV对比指引用于授粉(蜜蜂、大黄蜂)的昆虫。
-在除了可见光之外还能使用部分UV光谱用于产生光伏电流且其中将PVB膜在面向日光那侧上置于其前面的光电模块中,如果使用传统苯并三唑型UV吸收剂时PVB膜对UV辐射几乎完全不透明,能量效率变得更低。
-在无需UV保护情况下的室内领域中的应用中,容许提高的UV透过,以使无色部件显示更自然的颜色,特别是与低铁玻璃组合时,这是因为UV-稳定化的PVB膜具有低的复合材料黄度值。
-作为UV-可透过的复合玻璃,用于借助UV-A-固化粘合剂组装,例如在家具玻璃领域中。
-作为鸟类保护用窗玻璃(Vogelschutzveglasung)的部件(即用于保护鸟类),其中与PVB膜层合的玻璃板应是部分UV-透过的,以实现鸟类可以感知的对比。
发明目的
本发明目的是制备具有低泛黄趋势、对UV-A辐射(325nm-400nm)和可见光高透过率、以及同时对UV-B辐射(280nm-325nm)低透过性的PVB膜。
聚乙烯醇缩丁醛是由饱和单元构成的共聚物,即其含有烯属或芳族键,但是通常存在缺陷,且由此在280-400nm的波长范围(UV-A+UV-B)内并不存在显著的吸收。此外,主要将非芳族增塑剂用于增塑PVB,且相同论断适用于这些增塑剂相对于UV吸收。这点导致用于生产膜的由PVB和增塑剂组成的混合物相对高的固有UV稳定性。
PVB可能含有损害其UV稳定性的缺陷和/或杂质,取决于原材料聚乙烯醇和/或丁醛的质量以及合成和后处理中的方法进程。此外,膜配制剂中添加的添加剂如颜料或酚类抗氧化剂可能是UV敏感性的,由此PVB膜经常含有UV吸收剂。
简单省略UV吸收剂存在的缺陷是,大量的高能UV-B辐射(280-350nm)由此被容许通过,但是这点对于温室而言可能是不期望的,取决于栽培植物类型,且在光电模块的情形下可能导致材料损伤,同时对于无色窗玻璃并不产生进一步的黄度值降低。
此外,酚类抗氧化剂本身可能在UV、特别是UV-B辐射的影响下发生变黄,使得由此膜的黄度值随时间推移而增加且在太阳光光谱的可见光范围内的透射率降低。商业上最重要的酚类抗氧化剂具有子结构丙酸(2,5-二叔丁基-4-羟基苯基)酯,其下尤其包括Irganox 1010、Irganox 1076和Irganox 1035型的产品,在用于玻璃层压体中的PVB膜时在UV和/或温度的影响下导致泛黄。
完全没有UV吸收剂的PVB膜由此仅在保持一些边界条件时是成功的,因此其可靠地满足了对于各种应用的长期稳定性的各种高要求。此外,采用其制备的窗玻璃和/或采用其制造的光电模块还存在的缺陷是,特别有害的UV-B辐射能不受阻碍地透过窗玻璃和/或进入PV模块。
令人吃惊地发现,含有增塑剂的聚乙烯醇缩醛膜可以这样来制备,使得其具有低泛黄趋势以及对UV-A辐射和可见光的高透过率,同时对UV-B辐射具有低透过性。这样,在用于温室窗玻璃时,可以改进它们的直接辐射透射率TE(依据EN 410),且在用于光电模块时可以改进它们的光电电流效率。在用于其中将PVB膜在面向日光的那侧之上位于电池前面的光电模块时,如果该电池在波长范围325-380nm内具有灵敏性,可以显著地提高它们的光电电流效率。在使用UV-A-可透过的PVB膜特别是在用于无色窗玻璃时,可以降低黄色色调,因为该膜在380-450nm的波长范围内是完全透明的。对于UV-A辐射的透明性也容许将含有PVB膜的复合玻璃用UV-A-固化粘合剂组装,其中复合玻璃可以毫无问题地用固化该粘合剂所需的UV-A光辐照。此外,由于对于UV-A辐射的透明性,可以容易地产生在UV范围内鸟类可感知的对比,例如用额外地覆盖UV-A范围的另一UV吸收剂部分地印刷该膜。
发明内容
由此本发明的主题是含有至少一种聚乙烯醇缩醛和至少一种增塑剂的含增塑剂的膜,其特征在于添加0.001-1重量%的至少一种依据式1的草酰替苯胺型化合物作为UV吸收剂,
其中R1,R2=具有1-10个碳原子的烃基。
优选地,作为依据式1的草酰替苯胺化合物,本发明膜含有2-乙基-2’-乙氧基-草酰替苯胺,CAS no. 23949-66-8作为UV吸收剂。其可例如从BASF(CIBA)以“Tinuvin 312”,从SONGWON以“Songsorb 3120”或者从CLARIANT以“Sanduvor VSU”商购获得。
通过改变取代基,当然也容易产生其它类似结构,其可以相应地在本发明的范围之内使用。
本发明膜优选地含有用量为0.01-0.75重量%、优选0.05-0.50重量%且最优选0.075-0.35重量%的草酰替苯胺型UV吸收剂。
本发明膜在0.76mm厚度下依据EN 410在380nm下在2×2mm低铁浮法玻璃之间进行测量时具有大于50%、优选大于70%、更优选大于80%且特别优选大于85%的透射率。同时,这种层压体在325nm下的透射率小于50%,优选小于30%且特别优选小于20%。
直接辐射透射率TE相比于配备有常规使用的苯并三唑型UV吸收剂(Tinuvin 328)的膜,从大约82.5%增加到大于84%,这在例如温室窗玻璃中是有利的。
对于PVB膜物料的热稳定化以防止特别是在挤出过程期间的链降解,需要酚类抗氧化剂,这与UV吸收剂的存在无关。
在使用草酰替苯胺型UV吸收剂时,更高份额的UV-A辐射可能由于特定酚类抗氧化剂而导致膜泛黄,因此此时优选使用不含有丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的那些。能够仅以少量使用具有丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的抗氧化剂,即优选在该膜中不超过400ppm,优选不超过200ppm,优选不超过100ppm且最优选不超过50ppm。
但是,与此不同,在该膜可以存在用量为0.005-0.5重量%的不含丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的适宜抗氧化剂。不含丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的适宜抗氧化剂是例如Lowinox 44B25型或Irganox 129型的双环酚类抗氧化剂,Songsorb 2908型(CAS: 67845-93-6)、BHT (CAS: 128-37-0)、对-辛基苯酚的单环酚类抗氧化剂,多环抗氧化剂如Topanol CA (CAS: 1843-03-4)或Wingstay L (31851-03-3)。同样还可以考虑含有一个或多个硫原子但不含丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的酚类抗氧化剂。
除了草酰替苯胺型UV吸收剂之外,本发明膜特别优选地含有一种或多种依据式(2)、(3)或(4)的具有丙酸(3-叔丁基-4-羟基-5-甲基苯基)酯子结构的酚类抗氧化剂。
适宜的式(2)稳定剂包括例如式(3)的那些
(3)
其中n=1-10,和式4的那些。
依据式(2)、(3)或(4)的适宜稳定剂是CAS登记号36443-68-2的那些,其可例如以IRGANOX 245从CIBA公司,以Lowinox GP45从CHEMTURA公司或以Songnox 2450从SONGWON公司获得,以及CAS登记号90498-90-1的那些,其可以名称Sumilizer GA 80从SUMITOMO公司获得。
本发明混合物或膜优选地含有0.005-0.5重量%、特别优选0.01-0.25重量%、特别是0.02-0.1重量%且最优选0.03-0.08重量%的具有依据式(2)、(3)或(4)的丙酸(3-叔丁基-4-羟基-5-甲基苯基)酯子结构的酚类抗氧化剂。
除了使用依据式(2)、(3)或(4)的具有丙酸(3-叔丁基-4-羟基-5-甲基苯基)酯子结构的酚类抗氧化剂之外,该热塑性混合物/膜可以具有采用本身由于其它性能如高挥发性而不那么适用的其它光稳定的酚类抗氧化剂的基本稳定化。在本发明范围之内,还包括在PVB膜的挤出和加工条件下具有提高的挥发性的抗氧化剂,这一点通常适用于分子量小于300g/mol的酚类抗氧化剂。本发明热塑性混合物和/或膜优选地含有用量为0.001-0.25重量%的分子量小于300g/mol的酚类抗氧化剂(相对于该膜混合物)。特别适宜的分子量小于300g/mol的酚类抗氧化剂有例如BHT (CAS登记号:128-37-0)或4-叔丁基苯酚(CAS登记号:140-66-9)。
前述分子量小于300g/mol的酚类抗氧化剂可以以所述用量单独地或者与另一酚类抗氧化剂组合使用。
除了使用草酰替苯胺UV吸收剂之外,本发明混合物设定为低碱滴定度(Alkalititer),例如在中和聚乙烯醇缩醛时,可以产生本发明膜的改进本征颜色和光热稳定性。
碱滴定度,如实施例中所示,通过用盐酸中和本发明混合物和/或膜来测量,且优选为2-70、特别是3-50且最优选5-30。
碱滴定度可以通过在聚乙烯醇的缩醛化制备期间或之后聚乙烯醇的相应中和,或者通过向本发明混合物添加金属盐来调节。在将本发明膜用于复合玻璃层压体时,金属盐通常还起到防粘剂的作用。
本发明膜可以含有碱土金属离子、锌离子、铝离子和/或碱金属离子作为防粘剂。它们在该混合物/膜中以单价或多价无机酸或者单价或多价有机酸的盐形式存在。抗衡离子实例包括例如有机羧酸盐,例如甲酸盐、乙酸盐、三氟乙酸盐、丙酸盐、丁酸盐、苯甲酸盐、2-乙基己酸盐等,但是优选使用优选具有小于10个碳原子、优选小于8个、优选小于6个、优选小于4个和特别优选小于3个碳原子的羧酸。无机抗衡离子的实例包括盐酸盐、硝酸盐、硫酸盐、磷酸盐。其它抗衡离子可以包括归类为表面活性剂如磺酸盐或磷酸盐表面活性剂的阴离子。
本发明膜优选地含有大于5ppm、优选大于10ppm、优选大于15ppm、优选大于20ppm、优选大于25ppm的选自碱土金属(Be、Mg、Ca、Sr、Ba、Ra)、锌和铝的离子。为了避免不需要的浑浊,另一方面应当含不超过250ppm的前述多价金属。
同时,应调节含增塑剂的基于聚乙烯醇缩醛的膜中的碱金属离子含量(Li、Na、K、Rb、Cs、Fr)尽可能低。该膜优选地含有小于150ppm、优选小于100ppm、优选小于75ppm、优选小于50ppm、优选小于25ppm、优选小于10ppm且特别优选小于5ppm的碱金属离子。
依据本发明使用的聚乙烯醇缩醛可以聚乙烯醇PVA与醛如丁醛的缩醛化产物获得。本发明膜可以含有一种或多种聚乙烯醇缩醛,它们在分子量、缩醛化程度、残余醇含量或缩醛基碳原子数方面可以不同。
此外,本发明膜的前述有益光学性能可以通过对用于制备该聚乙烯醇缩醛的聚乙烯醇(PVA)的选择来改进。如果在PVA层面上作为缺陷在聚合物链中存在不饱和单元,在由此制得的聚乙烯醇缩醛中也必然存在缺陷,使得其UV辐射吸收增加且其光稳定性恶化。不饱和单元可以以孤立的双键或者与另一双键共轭或与羰基键共轭的双键形式存在。这些不饱和单元可以通过UV光谱在PVA中检测到。
非常大含量的缺陷导致所用的PVA在H2O中的4重量%溶液中测量时在280nm下几乎1的消光度。由此优选使用在280nm下在4重量%水溶液中消光度小于0.5、优选小于0.3、特别是0.2和尤其是0.1的聚乙烯醇来制备依据本发明所用的聚乙烯醇缩醛。
除了使用对于UV-A辐射几乎透明的草酰替苯胺型UV吸收剂和使用不容易泛黄的酚类抗氧化剂和/或使用具有特别低缺陷含量的聚乙烯醇缩醛和/或调节碱滴定度之外,依据本发明制备的膜可以配备有一种或多种非芳族光稳定剂、特别是采用HALS型的空间位阻胺和/或空间位阻型氨基醚(非HALS)来制备。
本发明膜优选地含有0.005-1重量%、特别优选0.01-0.5重量%、特别是0.03-0.3重量%和最优选0.05-0.25重量%的HAS、HALS或非HALS型空间位阻胺作为光稳定剂。
特别适宜的空间位阻胺包括通式(5)、(6)和/或(7)的那些,
(5) (6) (7)
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11 = 例如H、C1–C20 烷基、羟基烷基、烷氧基烷基、酰基氧基烷基,各自未被取代或者被醛、酮或环氧基团取代,
R12 = 简单键(glatte Verbindung),C1–C20烷基、羟基烷基、烷氧基烷基、酰基氧基烷基,各自未被取代或者被醛、酮或环氧基团取代,
n = 2-4
m = 1–10。
这类化合物例如通过产品Tinuvin 123 (NOR-HALS)、Tinuvin 144、Tinuvin 622、Tinuvin 770以及其二-N-甲基化衍生物从BASF (Ciba Specialities)商购获得。例如,Songwon International公司的Songlight 2920,Asahi Denka Co.公司的ADK Stab LA-57、LA-52或LA-62以及BASF SE的UVINUL 4050 H是特别适宜的。
为了制备聚乙烯醇缩醛,将聚乙烯醇溶解于水中并用醛例如丁醛、甲醛或丙醛在添加酸催化剂情况下进行缩醛化。将沉淀的聚乙烯醇缩醛分离、洗涤至中性、任选地悬浮在碱性含水介质中,随后再次洗涤至中性并干燥。
用于缩醛化的酸必须在反应之后再次中和。特别地,可以通过省略通常用于催化剂中和的氢氧化钠或氢氧化钾和/或碳酸盐,或者通过彻底洗涤在缩醛化中获得的聚乙烯醇缩醛,可以在聚乙烯醇缩醛的合成中实现低碱金属离子含量。作为碱NaOH或KOH的替代,也可以例如通过吹入二氧化碳或环氧乙烷来中和来自缩醛化步骤的催化剂酸。
聚乙烯醇缩醛的聚乙烯醇含量可以通过缩醛化中醛的用量来调节。
也能够采用具有2-10个碳原子(例如戊醛)的其它醛或多种醛来进行缩醛化。
基于含增塑剂的聚乙烯醇缩醛的膜优选地含有未交联的聚乙烯醇缩丁醛(PVB),其通过聚乙烯醇与丁醛的缩醛化获得。
同样能够使用交联的聚乙烯醇缩醛、特别是交联的聚乙烯醇缩丁醛(PVB)。适宜的交联的聚乙烯醇缩丁醛描述于例如EP 1527107 B1和WO 2004/063231 A1 (含羧基的聚乙烯醇缩醛的热自交联),EP 1606325 A1 (采用多元醛交联的聚乙烯醇缩醛)以及WO 03/020776 A1 (采用乙醛酸交联的聚乙烯醇缩醛)。这些专利申请的公开内容被全部引入作为参考。
在本发明的范围之内,也可以使用水解的乙酸乙烯酯/乙烯共聚物的三元共聚物作为聚乙烯醇。通常将这些化合物水解超过98mol%,且含有1-10重量%基于乙烯的单元(例如Kuraray Europe GmbH的“Exceval”型)。
在本发明的范围之内,还可以使用水解的乙酸乙烯酯和至少一种其它烯属不饱和单体的共聚物作为聚乙烯醇。
在本发明的范围之内,聚乙烯醇可以以纯物质形式或者以不同聚合度或水解度的聚乙烯醇混合物使用。
除了缩醛单元之外,聚乙烯醇缩醛还含有产生自乙酸乙烯酯和乙烯醇的单元。依据本发明使用的聚乙烯醇缩醛优选地具有小于22重量%、20重量%或18重量%,小于16重量%或15重量%且特别地小于14重量%的聚乙烯醇含量。聚乙烯醇含量应不低于12重量%。
依据本发明使用的聚乙烯醇缩醛的聚乙酸乙烯酯含量优选地小于5重量%,小于3重量%或小于1重量%,特别优选小于0.75重量%,最特别优选小于0.5重量%且尤其是小于0.25重量%。
缩醛化程度可以由聚乙烯醇含量和残留乙酸酯含量来计算确定。
该膜优选地具有总的增塑剂含量,即该膜中所有增塑剂的含量范围为5-45重量%、12-36重量%、14-32重量%、16-30重量%、特别地20-28重量%。本发明膜和/或由此粘合的层压体/模块可以含有一种或多种增塑剂。
选自下列的一种或多种化合物非常适合作为用于本发明膜的增塑剂:癸二酸二-2-乙基己酯(DOS)、己二酸二-2-乙基己酯(DOA)、己二酸二己酯(DHA)、癸二酸二丁酯(DBS)、三乙二醇双-正庚酸酯(3G7)、四乙二醇双-正庚酸酯(4G7)、三乙二醇双-2-乙基己酸酯(3GO和/或3G8)、四乙二醇双-正-2-乙基己酸酯(4GO和/或4G8)、己二酸二-2-丁氧基乙酯(DBEA)、己二酸二-2-丁氧基乙氧基乙酯(DBEEA)、癸二酸二-2-丁氧基乙酯(DBES)、邻苯二甲酸二-2-乙基己酯(DOP)、邻苯二甲酸二异壬酯(DINP)、三乙二醇双异壬酸酯、三乙二醇-双-2-丙基己酸酯、三(2-乙基己基)磷酸酯(TOF)、1,2-环己烷二羧酸二异壬基酯(DINCH)、己二酸二异壬酯(DINA)和二丙二醇苯甲酸酯。
最特别适用于本发明膜的增塑剂是其极性(由式100×O/(C+H)表示)小于或等于9.4的增塑剂,其中O、C和H表示各个分子中氧原子、碳原子和氢原子的数目。下表显示了可以依据本发明使用的增塑剂以及依据式100×O/(C+H)的极性值。
对于在光电模块的应用,本发明膜在23℃下85%环境湿度下,优选地具有至少1E+11 ohm*cm、优选至少5E+11 ohm*cm、优选1E+12 ohm*cm、优选5E+12 ohm*cm、优选 1E+13 ohm*cm、优选5E+13 ohm*cm、优选1E+14 ohm*cm的电阻率。
此外,本发明混合物或膜可以额外地含有其它添加剂,例如抗静电剂、填料、IR-吸收纳米颗粒和/或发色团、染料、表面活性物质、漂白剂、稳定剂、酸/碱缓冲剂、螯合剂、含环氧基团的化合物、颜料和粘合调节剂。
特别地,还包括与选择性IR-辐射-反射或吸收颗粒的组合。
此外,本发明的主题是本发明膜用于制备光电模块、玻璃层压体、温室覆盖物、在家具领域、鸟类保护用窗玻璃中的用途,特别地用于
·温室窗玻璃,具有对UV-A辐射提高的能量透射率和透过性,
·作为光电模块的包封膜,具有通过利用太阳光谱的UV-A部分提高的光电电流产率,
·作为层压膜,特别地用于中性颜色的建筑窗玻璃,
·作为UV-可透过的复合玻璃,用于例如在家具玻璃领域中用UV-A-固化粘合剂组装,
·作为鸟类保护用窗玻璃的一部分,其中与PVB膜层合的玻璃板是部分UV-透过性的,以实现UV对比。
本发明具有对UV-A辐射高透明性的膜与传统几乎UV-不透明的膜在一个组件中的组合也是可考虑的和有意义的。例如,对于嵌入两层膜之间的太阳能电池的PV模块应用情形,面向光线的那侧上的前置膜可以具有如上所述对UV-A辐射的高透明性,由此提高能量效率,但是在后侧上的膜可以通常方式对UV-B和UV-A辐射不透明,使得在这侧之后的材料例如可以聚合物背板或粘附上的接线盒免受UV损伤,或者在集成到建筑物内部建筑外壳上的玻璃/玻璃模块的情形下提供保护以免受UV辐射影响。
为了实现颜色中性,在使用多个膜层时,例如3 × 0.76 mm,仅一个膜层可以用配备有传统UV吸收剂,但是其它两个用依据本发明使用的草酰替苯胺吸收剂来制备。这样在足够的UV吸收情况下,可以使PVB膜对窗玻璃的黄色色调的贡献保持最小。
本发明膜在厚度为0.76mm下优选地具有小于1、优选小于0.7、特别优选小于0.5且尤其是小于0.3的黄度值db,以及小于5、优选小于2.5、特别优选小于2且尤其是小于1.5的Δb*值。
为了实现在温室覆盖物的情形下最大的能量透射率,同时实现针对UV-B辐射的保护,将本发明膜特别地与低铁玻璃组合。基于用于层压的单个玻璃,其可以具有1-5mm、优选1.5-4mm、且最优选2-3mm的厚度。
附图说明
图1阐述了对比实施例1(无UV稳定剂,在UV-B范围内不足的吸收)、对比实施例3(在UV-A范围内过低的透射率)和实施例3(在UV-B范围内的高吸收和对UV-A辐射的高透明性)的膜的不同透射率。
具体实施方式
试验和测量方法
在两块2mm厚的Optiwhite?型(低铁含量的玻璃,来自Pilkington公司)玻璃之间的复合玻璃中测试膜的辐射稳定性。依据EN 12543,使尺寸15×15cm的层压体在辐射室内暴露20周的时间。但是,与EN 12543的条件偏离的是,设定更高的样品温度,也即恒定80℃,因为这样更接近地对应于在不利条件下应用时实际发生的组合的辐射和温度负荷。
通过辐射过的层压体相对于在黑暗中储存的原始层压体的b*值(CIELab)的对比测量,b*值的相对增加可以用作具有各种类型稳定剂和/或各个稳定剂组合的PVB膜的辐射稳定性的量度。b*值在从制造商Hunterlab获得的“ColorQuest XE”颜色测量仪中在CIELab体系中以透射率(10°/D65)测量。Δb*值以辐射样品的b*值与原始样品的b*值之间的差值获得。
为了区分出挤出膜的本征颜色,在Hunterlab 2°/C中在ColorQuest XE上测量具有两块2mm厚Optiwhite玻璃板连同0.76mm厚膜的复合玻璃(未另外通过辐射负载)。在该方法中,通过测量相同玻璃批次中的两块玻璃将玻璃的本征颜色平均作为零样品(Nullprobe),并在数量上测量中间层对黄色着色的贡献作为黄度值db。
聚乙烯醇缩醛的聚乙烯醇和聚乙烯醇乙酸酯含量依据ASTM D 1396-92测量。通过原子吸收光谱(AAS)分析金属离子含量。采用Karl Fischer法测量膜的水含量和/或湿度含量。
为了测量缩醛化中所用聚乙烯醇的UV吸收值,在UV/VIS分光光度计例如Perkin-Elmer Lambda 950中以4%水溶液在1cm层厚下在280nm波长下进行测量该值。该测量值基于PVA的干燥固体含量。
在2×2mm Optiwhite之间层压的样品膜的辐射技术性能(光透射率TL,直接透射率TE,UV透射率,在给定波长下的透射率,各自以%计表示)依据DIN EN 410在UV/VIS分光光度计Perkin-Elmer Lambda 950上测量。
实施例
采用如下表中所示组成的混合物和厚度制备膜,并将其在2块2mm厚白玻璃(Optiwhite)之间加工成层压体并进行测试。
对比实施例1(无UV稳定剂)显示在UV-B范围内极高的透射率。对比实施例3显示在UV-A范围内过低的透射率。对比实施例2显示在UV-B和UV-A范围内足够低或高的能量透射率,但是在辐射试验中由于存在酚类抗氧化剂Irganox 1076而趋于泛黄。
依据实施例1-9的本发明膜显示对UV-A辐射的高透明性,且由此非常适用于在该波长范围内需要尽可能高的辐射组分的所有应用。
同时,在UV-B范围内的吸收值是高的(即透射率低),使得存在对在该波长范围内高能辐射的足够材料保护和/或足够材料稳定化。这点在辐射试验中由于低的泛黄而言是显然的。
图1阐述了对比实施例1(无UV稳定剂,在UV-B范围内不足的吸收)、对比实施例3(在UV-A范围内过低的透射率)和实施例3(在UV-B范围内的高吸收和对UV-A辐射的高透明性)的膜的不同透射率。
表中使用了下列缩写:
3G8 三乙二醇-双-2-乙基己酸酯
DBEA 己二酸二-2-丁氧基乙酯(任选地以重量混合比与3G8混和)
DINCH 1,2-环己烷二羧酸二异壬基酯
PVB 具有特定PVA含量的聚乙烯醇缩丁醛
S 2450 Songnox 2450
I 1076 Irganox 1076
L 44B25 Lowinox 44B25
S GA-80 Sumilizer GA-80
TE 直接辐射透射率TE (300-2500 nm),以%计
TL 光透射率TL (380-780 nm),以%计
UV UV-透射率TUV (280-380 nm),以%计
Db* 基于EN 12543在20周辐射测试之后的Δb*值
Tinuvin 328 Tinuvin 328 (苯并三唑型UV吸收剂)
Tinuvin 312 Tinuvin 312 (草酰替苯胺型UV吸收剂)
层压体试验 在2×2mm Optiwhite玻璃之间的层压体中进行的层压体试验值
黄度值 db 黄度值 db Colorquest XE
ng 未测试
(A) 以重量%计的值,基于PVB
(B) 以ppm计的值,基于PVB
(C) 以重量%计的值,基于该膜。
表1
对比实施例1 | 对比实施例2 | 对比实施例3 | |
膜厚,mm | 0.76 | 0.76 | 0.76 |
PVB的PVOH含量(a) | 19.8 | 20.1 | 19.8 |
PVB中抗氧化剂含量(b) | 800 | 800 | 800 |
抗氧化剂类型 | S 2450 | I 1076 | S 2450 |
PVB(c) | 72.5 | 72.5 | 72.5 |
3G8/DBEA 10:1(c) | 27.5 | 27.5 | 27.5 |
DINCH(c) | - | - | - |
MgAc2 * 4 H2O (c) | 0.015 | 0.015 | 0.015 |
Songlight 2920 (HALS) (c) | |||
Tinuvin 328(c) | 0.15 | ||
Tinuvin 312(c) | 0.15 | ||
层压体试验 | |||
黄度值db | 0.25 | 0.29 | 0.40 |
TE% | 86.5 | 84.8 | 82.6 |
TL% | 90.1 | 90.2 | 89.6 |
UV% | 64.2 | 28.9 | 0.1 |
325 nm下透射率, % | 38.4 | 0.1 | 0 |
380 nm下透射率, % | 84.2 | 79.2 | 2.7 |
Db* | 3.4 | 8.8 | 0.4 |
表2
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | |
膜厚,mm | 0.38 | 0.38 | 0.76 | 0.38 | 0.76 | 0.76 | 0.76 | 0.76 | 0.76 |
PVB的PVOH含量(a) | 19.8 | 19.8 | 19.8 | 19.8 | 20 | 19.9 | 20 | 15.2 | 19.9 |
抗氧化剂含量(b) | 800 | 800 | 800 | 800 | 800 | 1100 | 800 | 800 | 1100 |
抗氧化剂类型 | S 2450 | S 2450 | S 2450 | S 2450 | L44B25 | BHT | S GA-80 | S 2450 | BHT |
PVB (c) | 72.5 | 72.5 | 72.5 | 72.5 | 72.5 | 72.5 | 72.5 | 74 | 72.5 |
3G8/DBEA 10:1 (c) | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 | - | 27.5 |
DINCH(c) | - | - | - | - | - | - | - | 26 | - |
MgAc2 * 4 H2O (c) | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 | 0.015 |
Songlight2920 (HALS) (c) | 0.10 | ||||||||
Tinuvin 328(c) | |||||||||
Tinuvin 312(c) | 0.05 | 0.10 | 0.15 | 0.20 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
层压体试验 | |||||||||
黄度值db | 0.10 | 0.10 | 0.23 | 0.10 | 0.20 | 0.23 | 0.21 | 0.16 | 0.20 |
TE% | 87.1 | 86.7 | 85.2 | 86.4 | 85.3 | 85.2 | 85.4 | 85.3 | 85.1 |
TL% | 91.0 | 90.9 | 90.5 | 90.9 | 90.4 | 90.3 | 90.5 | 90.8 | 90.2 |
UV% | 56.6 | 48.9 | 32.5 | 40.4 | 31.7 | 33.6 | 34.5 | 33.0 | 34.2 |
325nm下透射率% | 15.8 | 5.3 | 0.1 | 0.6 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
380nm下透射率% | 87.9 | 87.6 | 83.8 | 87.3 | 83.2 | 83.8 | 83.6 | 83.4 | 83.4 |
Db* | ng | ng | 1.2 | ng | 4.3 | 0.9 | 1.1 | 0.8 | 0.4 |
Claims (13)
2.权利要求1的膜,特征在于,使用CAS登记号23949-66-8的UV吸收剂作为式1的UV吸收剂。
3.权利要求1或2的膜,特征在于,该膜具有2-70的碱滴定度。
5.权利要求1-4中任一项的膜,特征在于,该膜额外地含有用量为0.005-0.5重量%的分子量小于300g/mol的酚类抗氧化剂。
6.权利要求1-5中任一项的膜,特征在于,该膜额外地含有0.001-1重量%的HAS/HALS/非-HALS型非芳族光稳定剂。
7.权利要求1-6中任一项的膜,特征在于,该膜具有小于3的Δb*值。
8.权利要求1-7中任一项的膜,特征在于,该膜具有小于1的本征颜色的黄度值db。
9.权利要求1-8中任一项的膜,特征在于,该聚乙烯醇缩醛通过聚乙烯醇的缩醛化来制备,其在4重量%水溶液中在280nm下具有小于0.5的消光度。
10.权利要求1-9中任一项的膜,特征在于,该膜含有超过5ppm的选自碱土金属、锌和铝的金属离子,以及小于150ppm的碱金属离子。
11.权利要求1-10中任一项的膜,特征在于,该膜额外地含有用量为0.005-0.5重量%的酚类抗氧化剂,该酚类抗氧化剂不含丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构。
12.权利要求1-11中任一项的膜,特征在于,该膜额外地含有不超过400ppm的具有丙酸(2,5-二叔丁基-4-羟基苯基)酯子结构的酚类抗氧化剂。
13.依据权利要求1-12中任一项的膜用于制备光电模块、温室覆盖物、家具领域中的玻璃层压体、无色窗玻璃、鸟类保护用窗玻璃的用途。
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