CN103619585A - 多层聚氯乙烯/氟化聚合物结构用于保护太阳能板背面的用途 - Google Patents
多层聚氯乙烯/氟化聚合物结构用于保护太阳能板背面的用途 Download PDFInfo
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Abstract
本发明涉及将氟化聚合物和PVC组合的多层结构作为用在光伏太阳能板背面处的保护的新用途,所述结构具有改善的在户外环境中的耐久性,同时保持与背板有关的其它性质,即良好的电绝缘、在体积和尺寸方面的热稳定性以及良好的对封装材料的粘附。本发明涉及多层结构作为在太阳能板的背面处的保护的用途,所述结构包括至少一个氟化聚合物层和一个PVC层。
Description
本发明大体上涉及多层膜的领域,并且尤其是涉及基于氟化聚合物和PVC的多层结构(多层结构体)。本发明还涉及用于制造这样的结构的各种方法(尤其是通过共挤出或通过涂覆),且涉及它们在太阳能板的背面保护中的用途。
太阳能板或组件由于由此获得的能量的可再生和无污染的性质而正在引起越来越多的兴趣。太阳能组件包括由光电子部件(通常基于晶体硅)组成的光伏电池的集合,其当暴露于光时产生电压。光伏电池置于透明的覆盖材料和在背面处的保护材料之间,所述透明的覆盖材料是由玻璃或塑料制成的片,所述保护材料经常是塑料膜。
位于光伏太阳能板的背面处的保护膜(称为背板)暴露于包括如水、氧和/或UV辐射一样的多种多样的因素的环境。因此背板的第一功能是对太阳能板提供良好的电绝缘、降低的水蒸气透过、保护不受UV辐射和氧阻挡性质。由于光电池通常封装在基于乙烯/醋酸乙烯酯(EVA)共聚物的封装剂或热塑性封装剂中,该背板的另一功能在于:当这些不同的材料层压在一起时提供良好的对EVA或对热塑性封装剂材料的粘附。而且,该保护膜在体积和尺寸方面必须是热稳定的,以防止在电池装配期间的热膨胀且尤其是收缩。
以钢或铝板(片,sheet)形式的金属制成的背板是已知的。新近,已经以聚合物材料如PET或(基于聚氟乙烯的材料)制造背板。背板通常由被两个由氟化聚合物制成的外层保护的聚酯层组成。最普遍的多层是使用通过溶剂路线沉积的聚氨酯粘合剂装配的:氟化聚合物/粘合剂/双轴取向PET/粘合剂/氟化聚合物。双轴取向PET是具有75到350微米厚度的板,而作为对UV辐射的阻挡物(PET的保护)的氟化膜具有10到40微米的厚度。现在市场上存在用于背板的新型膜,其使用单一的氟化层(例如:EVA/PET/氟化聚合物)或不使用氟化层(背板100%PET,由聚酰胺12制成的背板(由Isovolta出售)或基于聚酰胺和聚烯烃的背板())。
PET膜具有尺寸上稳定的优点,且具有优异的电绝缘特性。然而,这些膜对在暴露于环境因素如UV辐射和湿气后的分解是敏感的。结果是,使用PET未使得可获得具有良好的耐气候性性质的背板。
已经尝试用另外的聚合物代替PET层,所述另外的聚合物当与氟化聚合物层组合使用时赋予更大的耐湿气性和耐辐射性,换句话说其展现出改善的耐气候性。这样的聚合物以PVC为代表,PVC是便宜的热塑性材料,其可容易地挤出,且其与PET相比展现出更好的耐水解性和更好的对UV辐射的稳定性。
本发明计划提供将氟化聚合物和PVC组合的多层结构作为光伏太阳能板的背面保护的新用途,其展现出改善的耐气候性,同时保持背板的其它性质,即良好的电绝缘、在体积或尺寸上的热稳定性和良好的对封装剂材料的粘附。
为此,本发明的主题是包括至少一个氟化聚合物层和一个PVC层的多层结构在太阳能板的背面保护中的用途。
根据第一可选实施方式,所述多层结构由两层组成,即包括氟化聚合物的外层和PVC内层。
“外层”理解为是指与外部介质接触的层;“内层”理解为是指与光伏电池的封装剂材料接触的层。
根据第二可选实施方式,所述多层结构由三层组成,即氟化聚合物外层、PVC中间层和氟化聚合物内层。
而且,在这些可选形式的每一个中,可在氟化聚合物层和PVC层之间使用丙烯酸类、氟化或聚氨酯型的粘合剂。
在这些可选形式的每一个中,所述氟化聚合物层可由氟化聚合物的单一膜或若干(数个)膜组成。同样,所述PVC层可由PVC的单一膜或若干膜组成。
这些结构可通过共挤出、通过涂覆或通过用粘合剂的层压来制造。
现在对本发明进行详细描述。
本发明涉及包括至少一个氟化聚合物层和一个PVC层的多层结构在太阳能板的背面保护中的用途,其中各氟化聚合物层包括VDF均聚物或VDF和能与VDF共聚的氟化共聚单体的共聚物。
氟化聚合物是VDF均聚物或VDF和能与VDF共聚的氟化共聚单体的共聚物。因此,各氟化聚合物层由基于VDF的聚合物构成。
有利地,能与VDF共聚的氟化共聚单体选自例如:氟乙烯;三氟乙烯(VF3);三氟氯乙烯(CTFE);1,2-二氟乙烯;四氟乙烯(TFE);六氟丙烯(HFP);全氟(烷基乙烯基)醚如全氟(甲基乙烯基)醚(PMVE)、全氟(乙基乙烯基)醚(PEVE)和全氟(丙基乙烯基)醚(PPVE);全氟(1,3-间二氧杂环戊烯);全氟(2,2-二甲基-1,3-间二氧杂环戊烯)(PDD);和它们的混合物。
优选地,氟化共聚单体选自三氟氯乙烯(CTFE)、六氟丙烯(HFP)、三氟乙烯(VF3)、四氟乙烯(TFE)和它们的混合物。共聚单体有利地为HFP,因为它与VDF良好地共聚且使得可引入良好的热机械性质。优选地,共聚物仅包括VDF和HFP。
优选地,氟化聚合物是VDF均聚物(PVDF)或包括至少50重量%的VDF、有利地至少75重量%的VDF和优选地至少90重量%的VDF的VDF的共聚物如VDF-HFP。更特别地,可提及例如以下VDF均聚物或包括超过75%的VDF和余量的HFP的VDF的共聚物:由Arkema出售的710、720、740、Kynar2850或Kynar3120。
有利地,VDF均聚物或共聚物具有范围100Pa.s到3000Pa.s的粘度,该粘度在230℃下在100s-1的剪切梯度下使用毛细管流变仪测量。这是因为这种类型的聚合物良好地适于挤出。优选地,聚合物具有范围500Pa.s到2900Pa.s的粘度,该粘度在230℃下在100s-1的剪切梯度下使用毛细管流变仪测量。
在一个实施方式中,氟化聚合物包括以额外的聚合物形式的至少一种添加剂,其可为甲基丙烯酸甲酯(MMA)的均聚物或共聚物,任选地添加有无机颗粒。
除了存在额外的MMA聚合物之外,氟化聚合物层还可包括由无机和/或有机颗粒形成的一种或多种填料。
关于MMA聚合物,有利地可使用甲基丙烯酸甲酯(MMA)的均聚物和包括至少50重量%的MMA和能与MMA共聚的至少一种其它单体的共聚物。
可提及以下作为能与MMA共聚的共聚单体的实例:(甲基)丙烯酸烷基酯、丙烯腈、丁二烯、苯乙烯或异戊二烯。(甲基)丙烯酸烷基酯的实例在Kirk-Othmer,Encyclopedia of Chemical Technology,第4版(1991),第1卷,第292-293页和第16卷,第475-478页中描述。
有利地,MMA聚合物(均聚物或共聚物)包括0到20重量%和优选地5到15重量%的(甲基)丙烯酸C1-C8烷基酯,其优选为丙烯酸甲酯和/或丙烯酸乙酯。MMA聚合物(均聚物或共聚物)可被官能化,也就是说它包括酸、酰基氯、醇或酸酐官能团。这些官能团可通过接枝或通过共聚引入。有利地,官能度尤其是通过丙烯酸共聚单体引入的酸官能团。还可使用包括两个相邻的丙烯酸官能团的单体,所述两个相邻的丙烯酸官能团可脱水以形成酸酐。官能度的比例可为MMA聚合物的0到15重量%,优选地0到10重量%。
MMA聚合物可有利地包括至少一种冲击改性添加剂。存在商品级的“抗冲击”MMA聚合物,其包括以多层颗粒形式的丙烯酸类冲击改性添加剂。于是冲击改性添加剂存在于如市售的MMA聚合物中(也就是说,在制造过程期间引入MMA树脂中),但是其也可在膜的制造期间添加。冲击改性添加剂的比例对于每70到100份MMA聚合物在从0到30份变化,总共形成100份。
由多层颗粒(也公知地称为核-壳颗粒)组成的所述类型的冲击改性添加剂包括至少一个弹性体(或软)层(即由具有小于-5℃的玻璃化转变温度(Tg)的聚合物形成的层)和至少一个刚性(或硬)层(即由具有大于25℃的Tg的聚合物形成)。颗粒的尺寸通常小于1μm,且有利地在50和300nm之间。以核-壳型的多层颗粒形式的冲击改性添加剂的实例在以下文献中找到:EP1061100A1、US2004/0030046A1、FR-A-2446296或US2005/0124761A1。优选具有至少80重量%的软弹性体相的核-壳型颗粒。
MMA聚合物的MVI(熔体体积指数)可在2和25cm3/10分钟之间,其在230℃下在3.8kg的负荷下测量。
在氟化聚合物层中MMA聚合物的含量在1和55重量%之间,有利地在2和40重量%之间,优选在3和25重量%之间。
关于无机颗粒,可使用金属氧化物例如二氧化钛(TiO2)、氧化锌或硫化锌、二氧化硅、石英、氧化铝、碳酸盐如碳酸钙、滑石、云母、白云石(CaCO3·MgCO3)、蒙脱土(铝硅酸盐)、BaSO4、ZrSiO4、Fe3O4和它们的混合物。
这些颗粒具有使组合物在UV/可见光区中不透明的功能。从该观点来看,尤其优选TiO2填料。矿物填料例如TiO2型的矿物填料作为遮光剂以具有不透明的膜,主要通过UV辐射以及可见光的散射/反射。
还可添加颜色为(pigmented)黑色的颗粒。它们是碳黑或碳纳米管,其在低于其渗透阈值的含量下使用。
这些颗粒具有通常在0.05和20微米之间、有利地在0.1μm和10μm之间、优选在0.2μm和5μm之间的以平均直径表示的尺寸。在氟化聚合物层中无机颗粒的含量在0.1和30重量%之间,有利地在5和28重量%之间,优选在10和27重量%之间且更优选在15和25重量%之间。
根据本发明,氟化聚合物层的组合物(成分)可通过使得可获得参与该氟化聚合物层的组合物的聚合物和任选的添加剂和/或填料的均匀混合物的任何方法来制备。
在这些方法中,尤其可提及熔体挤出、压制(compacting)或辊捏合(rollkneading)。
更特别地,根据本发明的组合物通过使所有聚合物以及任选的添加剂和纤维熔体共混而制备,且然后通过在本领域技术人员已知的设备如双螺杆挤出机、共捏合机或混合机上配混而转化,例如以粒料的形式。该组合物可与另外的材料共挤出或以膜的形式挤出。
氟化聚合物层的厚度从10到150微米,优选从15到40微米变化,包括界限。
PVC层由刚性、半刚性或增塑的PVC构成。PVC可为任何氯乙烯聚合物或共聚物:氯乙烯均聚物,任选地氯化(CPVC);和由氯乙烯与一种或多种不饱和烯属共聚单体产生的共聚物,任选地交联。所述不饱和烯属共聚单体选自:偏氯乙烯,偏氟乙烯,羧酸乙烯酯如醋酸乙烯酯、丙酸乙烯酯或丁酸乙烯酯,丙烯酸和甲基丙烯酸,源自丙烯酸和甲基丙烯酸的腈、酰胺和烷基酯、尤其是丙烯腈、丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯或丙烯酸-2-乙基己基酯,乙烯基芳衍生物如苯乙烯,或烯烃如乙烯、丙烯或1-丁烯。
填料,尤其是无机填料,也可添加到PVC中以改善组合物的热机械强度。以非限制的方式,给出二氧化硅、氧化铝或碳酸钙或碳纳米管或玻璃纤维作为实例。
优选的PVC是氯乙烯均聚物和共聚物。有利地,后者具有约65W/m2K的传热系数U。
PVC、CPVC或PVC/CPVC层以重量计可包括:
-50到82重量%的一种或多种PVC和/或CPVC树脂。PVC树脂的系数U可在50和100W/m2K之间。这样的树脂通过悬浮、本体、乳液或微悬浮聚合法获得。通过本体PVC树脂的氯化过程获得的CPVC树脂的系数U可在60和70W/m2K之间;
-0.1到30%的选自稳定剂、加工助剂、润滑剂或阻燃剂的添加剂。尤其是,在通常用于基于乙烯基树脂的组合物中的添加剂中,可提及有机羧酸金属盐、有机磷酸、沸石、水滑石、环氧化的化合物、β-二酮、多元醇、含磷、含硫或酚类抗氧化剂、紫外线吸收剂例如二苯甲酮、苯并三唑和草酰替苯胺衍生物、氰基丙烯酸酯、受阻胺光稳定剂(HALS)、高氯酸盐、和其它基于金属的无机化合物、润滑剂例如有机蜡、脂肪醇、脂肪酸、酯、金属盐、填料例如白垩或滑石、和颜料如二氧化钛;
-0到11%的乳浊(不透明)填料,如二氧化钛、氧化锌或硫化锌;
-0到20%的一种或多种增塑剂;
-0到20%的基于丙烯腈或丙烯酸酯的热塑性化合物;
-0到20%的玻璃纤维。
用于PVC、CPVC或PVC/CPVC层的增塑剂选自壬二酸酯、偏苯三酸酯、癸二酸酯、己二酸酯、酞酸酯、柠檬酸酯、苯甲酸酯、树脂酸酯、戊二酸酯、富马酸酯、马来酸酯、油酸酯、棕榈酸酯、醋酸酯、环氧化的大豆油和它们的混合物。
为了增强PVC的热机械强度,一种或多种纺织或无纺基材可与后者组合使用。这些基材可由玻璃纤维、碳纤维、聚合物纤维(如聚酯、聚酰胺等)或天然纤维(亚麻、大麻等)构成。在这种情况中,PVC层由PVC-基材组合形成。
用于PVC、CPVC或PVC/CPVC层的热塑性化合物优选为基于丙烯腈或丙烯酸酯的热塑性化合物。其可得自选自苯乙烯/丙烯腈、丙烯腈/苯乙烯/丙烯酸酯或乙烯/丙烯酸甲酯共聚物的化合物。
PVC、CPVC或PVC/CPVC层使得可确保良好地保持热机械强度直到太阳能板的层压温度(120-150℃,5-30分钟)以及良好的抗UV老化性。
为了获得该PVC、CPVC或PVC/CPVC层而使用的转化方法优选为在100℃和180℃、实际上甚至220℃之间的温度范围中的挤出。由此获得的PVC、CPVC或PVC/CPVC层的厚度从150到450微米、优选地从200到300微米变化,包括界限。PVC组合物的实例列于以下表1中:
组分 | 重量% |
Lacovyl GB1040(PVC树脂) | 71.1 |
Micromya(CaCO3填料) | 7.9 |
Kane ACE B382(冲击改性剂) | 2.1 |
Plastistrength770(加工助剂) | 0.7 |
内润滑剂 | 1.1 |
外润滑剂 | 0.3 |
Ca/Zn(热稳定剂) | 3.9 |
Kronos2220(TiO2) | 2.6 |
玻璃纤维(增强填料) | 10.3 |
总共 | 100 |
表1
在由多层结构构成的背板中使用PVC引入许多优点:
-可与包括PET的结构比较的竞争价格;
-比PET好的耐水解性;
-与PET相比改善的对UV辐射的稳定性;
-优异的燃烧(火,fire)性质(根据UL94标准的V0)。这在集成在建筑中的太阳能板(BIPV)的情况中是优点;
-对于PV规格来说令人满意的电性质;
-以单阶段制造背板。
将氟化聚合物与PVC组合的多层结构的使用使得可获得具有以下主要特性的用于光伏组件的背板:
-良好的水阻挡性质(对于200微米,<1g/m2/24h);
-优异的电性质(通过部分放电试验确定的高的最大工作电压、高的绝缘强度(介电强度));
-低的收缩(在150℃下小于3%);
-直到太阳能板的层压温度(120℃-150℃)的良好的热机械性质;
-良好的燃烧性质;
-对在85和150℃之间的温度的恰当的蠕变强度;
-对封装剂膜(EVA、聚烯烃等)的粘附;
-容易添加有色颜料/UV阻挡物。
为了模拟在层压阶段期间背板遭遇的极端应力,应用以下方案。
对具有300μm厚度的组合物样品进行以下试验。所述样品由不同作用的(加工的,worked)起始材料的混合物以如下表中限定的比例在两辊混合机中在205℃下5分钟而制备。该材料然后在185℃下在200巴的压力下压缩240秒。
该试验由收缩的测量构成。测量以前,样品必须在环境温度中放置至少2小时。在140×140mm的板上,在距离边缘20mm处,在纵向和横向上绘制基准。标记由此获得的方形的中央。标记并测量在方形的中心处获得的纵向和横向距离(分别L0和T0)。将样品置于合适尺寸的木制板上,且然后将整个集合引入处于规定温度的炉中给定的时间。一旦该时间过去,从炉中取出样品并且在与用于试验之前样品整理(调节,conditioning)的相同条件下放置至少30分钟。然后再测量纵向和横向距离(分别为L和T)。
然后可根据下式(参见标准NF EN ISO11501)计算收缩:
·纵向收缩ΔL=(L0-L)*100/L0
·横向收缩ΔT=(T0-T)*100/T0。
根据本发明的PVC、CPVC或PVC/CPVC层使得可获得在0.85和2.7%之间的收缩值,如以下表2中所示的:
表2
以下所示的说明本发明的多层结构的实施例不是穷举的。它们都可用作保护太阳能板的背面(SiC、薄层等)的背板。
在这些实施例中,以下产品用作氟化聚合物:
-Kynar740:具有169℃的熔点(M.p.)和1700MPa的弹性模量的偏氟乙烯均聚物;
-Kynar Flex3120-50,具有165℃的熔点和690MPa的弹性模量。
所述M.p.值通过DSC或差示扫描量热法测量。弹性模量根据标准ISO527测量。
用于以下组合物中的PMMA是PMMA Altuglas BS550(甲基丙烯酸甲酯和丙烯酸乙酯的共聚物-MFR17-20g/10分钟(230℃;3.8kg))。
Elastollan C85是基于聚酯的聚氨酯。
1.通过共挤出获得的结构的实施例
多层膜通过在Amut商标(牌,brand)的挤出生产线上压延(CAST)而制造。该生产线由三个挤出机构成:
-Kraus Maffei商标的具有60mm直径的圆锥形双螺杆挤塑机,其专门用于PVC挤出,
-Samafor商标的具有45mm直径的单螺杆挤出机,用于PVDF或粘合剂的挤出,
-Dr Collin商标的具有30mm直径的单螺杆挤出机,用于PVDF外层的挤出,
该生产线还装备有500mm的Verbugren多支管(multimanifold)模头。多支管系统使得可制造具有具有可变的厚度分布(例如:30/30/350微米)的三层膜或板(层1/层2/层3)。工艺参数如下所示地设置:
-T°挤出层1和2:240℃
-T°挤出层3:180℃
-模头的T°:200℃
-生产线速度为3m/分钟。
通过共挤出获得根据本发明的结构的以下实施例:
1.1-CPVC或PVC/PMMA V082550%-Kynar Flex3120-5050%/Kynar740(350/10/30微米)
内层通过在制造时在机器的底部干混而制造。
1.2-CPVC或PVC/PMMA V082550%-Kynar Flex3120-5050%/Kynar74060%-PMMA24%-TiO216%
内层通过在制造时在机器的底部干混而制造。包括TiO2的PVDF外层通过在共捏合机中在不超过240℃的温度下配混而制造。在第一步中,在双螺杆挤出机上制备PMMA/TiO2母料;该母料随后在共捏合机中或在双螺杆挤出机中与PVDF共混。
1.3-CPVC或PVC/Kynar74040%-PMMA44%-TiO216%/Kynar740
包括TiO2的内层通过如对于实施例1.2描述的配混而制造。
1.4-CPVC或PVC/PMMA35%-Kynar74035%-改性剂S2001(Mitsubishi Rayon)30%/Kynar74060%-PMMA24%-TiO216%
包括改性剂S2001的内层通过在双螺杆挤出机中配混而制备。包括TiO2的外层通过如以上对于1.2所述的配混而制造。
1.5-CPVC或PVC/PMMA50%-PVDF50%/PVDF73.3%-PMMA4.7%-ZnO15%-TiO27%
包括TiO2和ZnO的外层通过配混而制造。将TiO2引入PVDF中使得必须在双螺杆挤出机上预先制备PMMA/TiO2母料;该母料随后在共捏合机中或在双螺杆挤出机中与PVDF共混。
1.6-CPVC或PVC/PVDF60%-PMMA24%-TiO216%
包括TiO2的外层通过如对于1.2所述的配混而制造。
1.7-CPVC或PVC/PVDF60%-PMMA16%-ZnO24%
包括ZnO的外层通过在双螺杆挤出机中配混而制造。
1.8-CPVC或PVC/Elastollan C85/Kynar74060%-PMMA24%-TiO216%
包括TiO2的外层通过如对于1.2所述的配混而制造。
1.9-CPVC或PVC/Elastollan C85/Kynar74073.3%-PMMA4.7%-ZnO15%-TiO27%
将TiO2引入PVDF中需要在双螺杆挤出机上预先制备PMMA/TiO2母料;该母料随后在共捏合机中或在双螺杆挤出机中与PVDF共混。
1.10-Kynar74060%-PMMA24%-TiO216%/CPVC或PVC/ElastollanC85/Kynar74060%-PMMA24%-TiO216%
包括TiO2的外层通过如对于1.2所述的配混而制造。
1.11-PVDF73.3%-PMMA4.7%-ZnO15%-TiO27%/CPVC或PVC/PMMA50%-PVDF50%/PVDF73.3%-PMMA4.7%-ZnO15%-TiO27%
包括TiO2和ZnO的外层通过配混而制造。将TiO2引入PVDF中需要在双螺杆挤出机上预先制备PMMA/TiO2母料;该母料随后在共捏合机中或在双螺杆挤出机中与PVDF共混。
2.通过挤出涂覆获得的结构的实施例
通过挤出涂覆制造的结构是在Dr Collin商标的挤出生产线上制造的。该生产线由三个挤出机构成,所述挤出机装备有标准聚烯烃螺杆轮廓(profile)、可变共挤出区块(block)和250mm衣架式(coathanger)模头。共挤出区块允许制造具有可变的厚度分布的(如:30/250微米)的1到5层的膜。付出(paying-out)装置系统使得可解开各种支撑体,包括PVDF膜。工艺参数如下所示地设置:
-T°挤出层1:200℃
-T°挤出层2:180℃
-T°共挤出箱和模头:200℃。
生产线速度为2m/分钟。
通过挤出涂覆或挤出层压制造的结构的实施例:
2.1–CPVC或PVC/Elastollan C85(基于聚酯的TPU)(30/250微米):共挤出且然后涂覆到具有30微米厚度的多层Kynar膜(PVDF/Kynar74040%-PMMA44%-TiO216%/PVDF5/20/5微米)上的膜。
2.2–CPVC或PVC/Elastollan C85(基于聚酯的TPU)(30/250微米):共挤出且然后涂覆到具有18μm厚度的单层膜(Kynar74073.3%-PMMA4.7%-ZnO15%-TiO27%)上的膜。
2.3–CPVC或PVC/Elastollan C85(基于聚酯的TPU)(30/250微米):共挤出且然后层压在具有30微米厚度的两个多层薄膜(PVDF/Kynar74040%-PMMA44%-TiO216%/PVDF5/20/5微米)之间的膜。
2.4–CPVC或PVC/Elastollan C85(基于聚酯的TPU)(30/250微米):共挤出且然后层压在具有18μm厚度的两个单层膜(Kynar74073.3%-PMMA4.7%-ZnO15%-TiO27%)之间的膜。
Kynar膜通过吹膜技术在装备有薄煎饼型模头的Dr Collin商标的5层管状生产线上预先制造。
3.通过层压(粘合剂)获得的结构的实施例
所述多层结构还可根据以下方案通过基于溶剂的粘合剂以两阶段装配:
i)膜的挤出
-根据本领域技术人员已知的技术,通过平膜挤出制造的具有250微米厚度的CPVC膜;
-Kynar膜1:具有30微米厚度的多层膜(PVDF/Kynar74060%-PMMA24%-TiO216%/PVDF5/20/5微米);
-Kynar膜2:具有18μm厚度的单层膜(Kynar74073.3%-PMMA4.7%-ZnO15%-TiO27%)。
膜1和2通过吹膜技术在装备有薄煎饼型模头的Dr Collin商标的5层管状生产线上预先制造。
ii)粘合剂的施加
以如下方式制造目标结构(PVC膜(350微米)/粘合剂/PVDF膜(膜1或2)):
·使用刮棒涂布机对PVC板施加具有30微米厚度的粘合剂层(未干燥)。所使用的粘合剂的配方如下:(供应商Bostick):HBTS ESP877(100份)+Biscodur1621固化剂(9份)。涂有粘合剂的PVC板随后在环境温度下放置1分钟,然后在50℃下放置5分钟。
·随后用手将Kynar膜层压到涂有粘合剂层的PVC板上;
·随后在80℃、5分钟、3巴下将该结构压缩。
在试验或使用之前,随后将所述结构在60℃的炉中放置3天,目的是使粘合剂充分交联。
通过层压获得以下结构:
3.1–CPVC或PVC/二组分的基于PU酯溶剂的粘合剂/Kynar膜1;
3.2–CPVC或PVC/二组分的基于PU酯溶剂的粘合剂/Kynar膜2;
3.3–Kynar膜1/二组分的基于PU酯溶剂的粘合剂/CPVC或PVC/二组分的基于PU酯溶剂的粘合剂/Kynar膜1;
3.4–Kynar膜2/二组分的基于PU酯溶剂的粘合剂/CPVC或PVC/二组分的基于PU酯溶剂的粘合剂/Kynar膜2。
4.多层PVC板的制造的实施例
使用压延生产线通过两个PVC板在玻璃织物上热的热层压制造PVC/玻璃纤维织物/PVC(150μm/50μm/150μm)多层结构。将PVC板在恒温控制的辊上预热,且然后在压延机上热层压。压延机的温度、夹紧力、和生产线速度作为使用的PVC配方和玻璃织物的函数而调节。
缩写:
PV-光伏
PVC–包括聚氯乙烯和其衍生物、尤其是氯化衍生物如CPVC的通称
CPVC–氯化聚氯乙烯
背板–光伏板的背面
PVDF–聚偏氟乙烯
PET–聚对苯二甲酸乙二醇酯
MMA–甲基丙烯酸甲酯
M.p.–熔点
MVI–熔体体积指数
MFR–熔体流动速率,用g/分钟表示
Claims (15)
1.包括至少一个氟化聚合物层和一个PVC层的多层结构用于太阳能板的背面保护的用途,其中所述氟化聚合物是VDF均聚物或VDF和能与VDF共聚的氟化共聚单体的共聚物。
2.权利要求1的用途,其中能与VDF共聚的氟化共聚单体选自氟乙烯、三氟乙烯、三氟氯乙烯、1,2-二氟乙烯、四氟乙烯、六氟丙烯、全氟(烷基乙烯基)醚如全氟(甲基乙烯基)醚、全氟(乙基乙烯基)醚和全氟(丙基乙烯基)醚、全氟(1,3-间二氧杂环戊烯)、全氟(2,2-二甲基-1,3-间二氧杂环戊烯)、和它们的混合物。
3.权利要求1的用途,其中所述共聚物是包括至少50重量%的VDF、有利地至少75重量%的VDF和优选至少90重量%的VDF的VDF-HFP共聚物。
4.权利要求1到3任一项的用途,其中所述氟化聚合物另外包括至少一种甲基丙烯酸甲酯的均聚物或共聚物。
5.权利要求4的用途,其中所述氟化聚合物另外包括选自二氧化钛、氧化锌或硫化锌、二氧化硅、石英、氧化铝、碳酸钙、滑石、云母、白云石、蒙脱土、BaSO4、ZrSiO4、Fe3O4、和它们的混合物的无机颗粒。
6.权利要求1到5任一项的用途,其中PVC是选自如下的聚合物:氯乙烯均聚物,其任选地氯化;以及由氯乙烯和一种或多种不饱和烯属共聚单体共聚产生的共聚物,其任选地交联。
7.权利要求6的用途,其中所述不饱和烯属共聚单体选自:偏氯乙烯、偏氟乙烯、醋酸乙烯酯、丙酸乙烯酯和丁酸乙烯酯、丙烯酸和甲基丙烯酸、腈、丙烯腈、丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸2-乙基己酯、苯乙烯、乙烯、丙烯和1-丁烯。
8.权利要求1到7任一项的用途,其中所述多层结构由两层组成,即包括氟化聚合物的外层和PVC内层。
9.权利要求1到7任一项的用途,其中所述多层结构由三层组成,即氟化聚合物外层、PVC中间层和氟化聚合物内层。
10.权利要求1到9任一项的用途,其中丙烯酸类、氟化或聚氨酯型的粘合剂置于所述氟化聚合物层和所述PVC层之间。
11.权利要求1到10任一项的用途,其中所述氟化聚合物层由氟化聚合物的单一膜或若干膜组成。
12.权利要求1到11任一项的用途,其中所述PVC层由PVC的单一膜或若干膜组成。
13.权利要求1到12任一项的用途,其中所述多层结构通过共挤出制造。
14.权利要求1到12任一项的用途,其中所述多层结构通过挤出涂覆制造。
15.权利要求1到12任一项的用途,其中所述多层结构通过层压制造。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR1153585A FR2974535A1 (fr) | 2011-04-27 | 2011-04-27 | Utilisations d'une structure multicouche pvc/polymere fluore pour la protection arriere des panneaux solaires |
FR1153585 | 2011-04-27 | ||
PCT/FR2012/050944 WO2012146880A1 (fr) | 2011-04-27 | 2012-04-27 | Utilisation d'une structure multicouche pvc/polymere fluore pour la protection arriere des panneaux solaires |
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CN103619585A true CN103619585A (zh) | 2014-03-05 |
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CN201280031550.9A Pending CN103619585A (zh) | 2011-04-27 | 2012-04-27 | 多层聚氯乙烯/氟化聚合物结构用于保护太阳能板背面的用途 |
Country Status (5)
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US (1) | US20140044976A1 (zh) |
EP (1) | EP2701906A1 (zh) |
CN (1) | CN103619585A (zh) |
FR (1) | FR2974535A1 (zh) |
WO (1) | WO2012146880A1 (zh) |
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CN112863336A (zh) * | 2021-01-11 | 2021-05-28 | 武汉华星光电半导体显示技术有限公司 | 显示模组及显示装置 |
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CN109733011A (zh) * | 2013-03-14 | 2019-05-10 | 施内勒公司 | 用于运输的具有改善的阻燃特性的柔软触感层压材料 |
JP6611642B2 (ja) * | 2016-03-04 | 2019-11-27 | ダイヤプラスフィルム株式会社 | ポリ塩化ビニル系樹脂組成物および反射フィルム |
US11731405B2 (en) * | 2017-11-16 | 2023-08-22 | Argotec, LLC | Polyvinylidene fluoride-acrylate and thermoplastic polyurethane multilayer protective film |
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2012
- 2012-04-27 EP EP12725066.0A patent/EP2701906A1/fr not_active Withdrawn
- 2012-04-27 CN CN201280031550.9A patent/CN103619585A/zh active Pending
- 2012-04-27 US US14/113,034 patent/US20140044976A1/en not_active Abandoned
- 2012-04-27 WO PCT/FR2012/050944 patent/WO2012146880A1/fr active Application Filing
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CN1239603C (zh) * | 2002-07-17 | 2006-02-01 | 阿托菲纳公司 | 可与pvdf共挤出的组合物 |
US20080124556A1 (en) * | 2003-04-11 | 2008-05-29 | Kernander Carl P | Bright white protective laminates |
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FR2974535A1 (fr) | 2012-11-02 |
US20140044976A1 (en) | 2014-02-13 |
EP2701906A1 (fr) | 2014-03-05 |
WO2012146880A1 (fr) | 2012-11-01 |
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