CN105051573B - 用于光伏阵列的抗反射膜 - Google Patents
用于光伏阵列的抗反射膜 Download PDFInfo
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- CN105051573B CN105051573B CN201480016844.3A CN201480016844A CN105051573B CN 105051573 B CN105051573 B CN 105051573B CN 201480016844 A CN201480016844 A CN 201480016844A CN 105051573 B CN105051573 B CN 105051573B
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Abstract
本发明提供一种含有聚合物粒子的膜,所述聚合物粒子具有0.75μm到15μm的平均粒径以及从所述粒子的中心到表面连续变化的折射率。所述粒子被包埋在包含聚烯烃的连续聚合物相中。从400nm到800nm测量的所述聚合物粒子与所述连续聚合物相之间的平均折射率差异不超过0.02。
Description
本发明涉及一种特别适用于构建光伏模块的抗反射膜。
有多种方法可使可见光从光伏阵列的反射浪费减到最小,包括将一种低介电常数层施加到所述阵列的表面上。举例来说,为此目的,美国专利第7,604,866号揭示了一种包含二氧化硅粒子的膜。然而,这种方法及其它方法不能使膜-玻璃界面处的表面反射减到最少。
本发明解决的问题是提供一种特别适用于构建光伏模块的抗反射膜。
发明内容
本发明提供一种膜,其包含聚合物粒子,所述聚合物粒子具有:(a)0.75μm到15μm的平均粒径;及(b)从所述粒子的中心到表面连续变化的折射率;以及包含聚烯烃的连续聚合物相;其中从400nm到800nm测量的所述聚合物粒子与所述连续聚合物相之间的平均折射率差异不超过少0.02。
具体实施方式
除非另外规定,否则百分比是重量百分比(wt%)并且温度以℃为单位。除非另外规定,否则折射率(RI)值是以钠D线测定,其中在20℃下,λ=589.29nm。聚合物粒子包含有机聚合物,优选加成聚合物,并且优选实质上呈球形。平均粒径D50定义为用粒度分析仪,优选库尔特计数器(Coulter counter)测量的粒度分布的中值。Tg值是使用福克斯等式(Foxequation)由均聚物Tg值计算;参见《美国物理学会公报》(Bulletin of the AmericanPhysical Society)1,3,第123页(1956)。组成在整个粒子中变化的聚合物粒子的Tg是所述粒子中不同组合物的Tg值的重量平均值。多阶段聚合物中每一阶段的单体重量百分比是基于在所述阶段中添加到聚合混合物中的单体的总重量来计算。如本文所用,术语“(甲基)丙烯酸”是指丙烯酸或甲基丙烯酸,并且“(甲基)丙烯酸酯”是指丙烯酸酯或甲基丙烯酸酯。术语“(甲基)丙烯酰胺”是指丙烯酰胺(AM)或甲基丙烯酰胺(MAM)。“丙烯酸系单体”包括丙烯酸(AA)、甲基丙烯酸(MAA)、AA和MAA的酯、衣康酸(IA)、丁烯酸(CA)、丙烯酰胺(AM)、甲基丙烯酰胺(MAM),以及AM和MAM的衍生物,例如烷基(甲基)丙烯酰胺。AA和MAA的酯包括但不限于,烷基酯、羟烷基酯、磷酸烷基酯以及磺基烷基酯,例如甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯(EMA)、甲基丙烯酸丁酯(BMA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、甲基丙烯酸羟丙酯(HPMA)、丙烯酸羟丁酯(HBA)、丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、丙烯酸2-乙基己酯(EHA)、甲基丙烯酸环己酯(CHMA)、丙烯酸苯甲酯(BzA)以及甲基丙烯酸磷酸烷酯(例如PEM)。“苯乙烯系单体”包括苯乙烯、α-甲基苯乙烯;2-烷基苯乙烯、3-烷基苯乙烯或4-烷基苯乙烯,包括甲基苯乙烯和乙基苯乙烯;优选苯乙烯。
术语“乙烯基单体”是指含有连接到杂原子(如氮或氧)上的碳-碳双键的单体。乙烯基单体的实例包括但不限于,乙酸乙烯酯、乙烯基甲酰胺、乙烯基乙酰胺、乙烯基吡咯烷酮、乙烯基己内酰胺,以及长链烷酸乙烯酯,如新癸酸乙烯酯和硬脂酸乙烯酯。术语“聚烯烃”是指烯烃的聚合物或共聚物,所述烯烃优选是具有两个到十个碳原子,优选地两个到八个碳原子,优选地两个到四个碳原子的那些烯烃,优选是丙烯或乙烯。优选地,连续聚合物相包含至少75wt%,优选地至少85wt%,优选地至少95wt%,优选地至少98wt%的聚烯烃。优选的聚烯烃包括烯烃的共聚物,尤其是乙烯与其它烯烃,优选具有三个到八个碳原子的那些烯烃的共聚物;所述其它烯烃优选是以0-90wt%,优选地2wt%-50wt%,优选地3wt%-40wt%的总量存在。优选地,聚烯烃的重量平均分子量是50,000到500,000,优选是70,000到300,000。优选地,聚烯烃的玻璃化转变温度低于25℃,优选低于10℃。优选地,聚烯烃的熔融温度不超过200℃,优选不超过190℃,优选不超过180℃;优选所述熔融温度是至少100℃。
优选地,聚合物粒子的平均粒径是至少1μm,优选是至少1.5μm,优选是至少2μm,优选是至少2.5μm,优选是至少3μm,优选是至少3.5μm;优选地,这些粒子的平均粒径不超过12μm,优选不超过10μm,优选不超过8μm,优选不超过6μm,优选不超过5.5μm。优选地,聚合物粒子的粒度分布指示单一模式;优选地,所述粒度分布在半高处的宽度是0.1μm到3μm,优选是0.2μm到1.5μm。所述膜可以含有具有不同平均直径的粒子,条件是具有每一种平均直径的粒子的粒度分布如上文刚刚所描述。粒度分布是使用粒度分析仪来测定。
本文中所陈述的折射率差异是绝对值。优选地,从800nm到2500nm测量的聚合物粒子与连续聚合物相之间的折射率差异(即,差异的绝对值)是至少0.04,优选是至少0.06,优选是至少0.08,优选是至少0.1。优选地,从800nm到2500nm测量的聚合物粒子与连续聚合物相之间的折射率差异不超过0.2,优选地不超过0.17,优选地不超过0.15。优选地,从400nm到800nm测量的聚合物粒子与连续聚合物相之间的折射率差异不超过0.015,优选地不超过0.01,优选地不超过0.005,优选地不超过0.003。优选地,聚合物粒子的折射率是1.43到1.55,优选是1.45到1.53,优选是1.46到1.52,优选是1.47到1.51。优选地,连续聚合物相的折射率是1.4到1.6,优选是1.45到1.55,优选是1.47到1.53,优选是1.48到1.52。优选地,在红外区(即,800nm-2500nm)中,聚合物粒子的折射率大于连续聚合物相的折射率。出于计算折射率差异的目的,GRIN粒子的折射率是粒子表面处的折射率。
膜中的聚合物粒子是具有径向折射率梯度的粒子(“GRIN”粒子,参见例如US20090097123)。优选地,GRIN粒子在中心处的折射率高于在表面处的折射率。优选地,GRIN粒子在中心处的折射率是1.51到1.63,优选是1.52到1.60,优选是1.53到1.59,优选是1.54到1.59;并且在表面处的折射率是1.45到1.53,优选是1.46到1.52,优选是1.47到1.51。在另一个优选实施例中,GRIN粒子在中心处的折射率低于在表面处的折射率。GRIN粒子的核心可以来源于用于产生所述GRIN粒子的聚合物种子(polymer seed)。优选地,GRIN粒子的核心是所述粒子的不超过95wt%,优选地不超过80wt%,优选地不超过60wt%,优选地不超过40wt%,优选地不超过20wt%。
优选地,以完整膜的重量计,连续聚合物相包含0.5wt%到15wt%;优选至少1wt%,优选至少1.5wt%,优选至少2wt%,优选至少3wt%,优选至少5wt%;优选地不超过12wt%,优选地不超过10wt%,优选地不超过9wt%的聚合物粒子。就存在连接聚合物所有部分的不间断路径的意义上说,连续聚合物相是连续的。
优选地,聚合物粒子包含至少60%,优选地至少65%,优选地至少70%,优选地至少75%,优选地至少80%的丙烯酸系单体的聚合残基。优选地,聚合物粒子包含至少70%,优选地至少80%,优选地至少90%,优选地至少95%,优选地至少97%的丙烯酸系单体与苯乙烯系单体的聚合残基。优选地,聚合物粒子还包含0到5%的酸单体(例如AA、MAA、IA、CA)的聚合残基,优选地包含0.5%到4%的AA和/或MAA,并且也可以含有少量的乙烯基单体残基。
交联剂是具有两个或更多个烯系不饱和基团的单体,或偶联剂(例如硅烷)或离子交联剂(例如金属氧化物)。具有两个或更多个烯系不饱和基团的交联剂可以包括例如二乙烯基芳香族化合物;二(甲基)丙烯酸酯、三(甲基)丙烯酸酯和四(甲基)丙烯酸酯;二烯丙基、三烯丙基和四烯丙基醚或酯化合物;以及(甲基)丙烯酸烯丙酯。此类单体的优选实例包括二乙烯基苯(DVB)、三羟甲基丙烷二烯丙基醚、四烯丙基季戊四醇、三烯丙基季戊四醇、二烯丙基季戊四醇、邻苯二甲酸二烯丙酯、顺丁烯二酸二烯丙酯、氰脲酸三烯丙酯、双酚A二烯丙基醚、烯丙基蔗糖、亚甲基双丙烯酰胺、三羟甲基丙烷三丙烯酸酯、甲基丙烯酸烯丙酯(ALMA)、乙二醇二甲基丙烯酸酯(EGDMA)、己-1,6-二醇二丙烯酸酯(HDDA)以及丁二醇二甲基丙烯酸酯(BGDMA)。优选地,聚合物粒子中聚合交联剂残基的量不超过8%,优选地不超过6%,优选地不超过5%;优选是至少0.1%,优选是至少0.5%,优选是至少1%,优选是至少2%。优选地,如果存在交联剂,那么其分子量是100到250,优选是110到230,优选是110到200,优选是115到160。优选地,交联剂是双官能性或三官能性的,即,其分别是二烯系不饱和或三烯系不饱和的,优选是双官能性的。
优选地,本发明的包含聚合物粒子的膜是通过挤出聚烯烃与聚合物粒子的混合物来制造。优选地,用于所述膜的衬底是玻璃、木材、皮革或光学透明的塑料,例如聚(邻苯二甲酸乙二酯);优选玻璃或光学透明的塑料,优选玻璃。优选地,用于此应用的塑料和玻璃的折射率在最小1.4(对于聚偏二氟乙烯)到1.8(对于掺杂有氧化铊(T120)的玻璃)间变化。膜样品还可以涂布粘着剂层,以达到多层结构中膜与膜层合及改进与衬底的接触的目的。
可以使用具有不同官能度和分子量的水性或溶剂基丙烯酸聚合物及树脂来粘附多层。优选地,粘着剂是由胶态聚合物分散于水和或溶剂中以得到高固体含量(30-50%w/w)的溶液或悬浮液来制备。优选地,在施加粘着剂之前,衬底通过暴露于放电进行处理,以达到降低表面能及增进粘着的目的。优选地,涂布粘着剂的衬底在干燥烘箱中在80℃到170℃范围内的温度梯度下干燥10到15分钟。
优选地,粘着剂组合物是由低玻璃化转变丙烯酸聚合物(优选Tg低于25℃)与呈直径范围处最小0.85μm到最大30μm的略微交联的球体形式的丙烯酸聚合物的混合物制备。优选地,呈球体形式的丙烯酸聚合物是交联的;优选地,聚合交联剂残基的量总的来说在4%与20%之间。优选地,第一聚合反应阶段包括以下一种或多种单体:乙二醇二丙烯酸酯、丙二醇二丙烯酸酯及丁二醇二丙烯酸酯。优选地,第二阶段包括在4%与20%之间的以下一种或多种交联剂部分:二乙二醇双(烯丙基碳酸酯)、甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、丙二醇二甲基丙烯酸酯及丁二醇二甲基丙烯酸酯。
粘着剂组合物被设计用于施加到粗糙和光滑表面,所述表面填充有限制表面构形的完全覆盖度的较大突出部分。粘着剂溶剂来源的溶液或水性分散液可以通过多种方式施加到衬底上。优选地,如果衬底较硬并且填充有呈高纵横比粒子形式的表面不规则性,那么用凹板式涂布机将粘着剂涂布到所述表面上。或者,可以用多种粘合剂调配粘着剂珠粒组合物以产生可以施加(例如通过喷雾或辊涂、喷射或印刷)到适当衬底上的水性或溶剂基涂料组合物。分散粒子的最高效的几何布置是在衬底上具有球体单层,在所述布置中,粒子处于面心立方或六方密堆积布置。
当粘着剂珠粒组合物是以水性分散液形式施加时,优选粘合剂包括如氨基硅烷、环氧化物、环氧基硅烷、烷基硅烷、脂肪酸或硅油等涂布剂。优选氨基硅烷是氨基乙基氨基丙基三甲氧基硅烷和丙烯酸纤维素溶液。其它适合的水性粘合剂包括选自丙烯酸、乙烯基的(共)聚合物(如乙酸乙烯酯或乙酸乙烯酯-乙烯)、聚氨基甲酸酯、硅氧烷、天然橡胶、合成橡胶聚合物(如苯乙烯-丁二烯(SBR)嵌段共聚物)、蛋白质聚合物、纤维素聚合物及其混合物和组合,例如丙烯酸氨基甲酸酯。
当所述珠粒组合物具有溶剂稳定性时,所述粘着剂组合物可以通过溶剂浇注来施加。用于溶剂浇注的溶剂包括甲基乙基酮、甲基异丁基酮、乙酸乙酯、乙酸丁酯、甲苯、异丙醇、乙醇及二甲苯和甲苯。
粘着剂组合物还可以包括以下各物中的任一种或全部:防腐剂、抗氧化剂、氢化木松香的甘油酯、玉米淀粉或马铃薯淀粉、乙二醇、丙二醇、丁二醇、戊二醇、己二醇、丙二醇、丙三醇、2,3-丁二醇、1,3-丁二醇、二乙二醇、三乙二醇、聚乙二醇、亚乙基脲、脲、山梨醇及甘露醇。还可以将增粘树脂(如松香和萜烯酚)添加到共混物组合物中。
或者,粘着剂可以基于α聚烯烃与乙烯的共聚物。优选用氢化烃增粘剂增粘的配制物。粘着剂配制物可以硅烷以改进与玻璃表面的粘着性。在一些实施例中,所述膜可以呈多层结构,由此可以剥离掉一个层,从而呈现一个新的表面。在这个实施例中,优选每一层的厚度小于100μm,厚度优选小于50μm并且总层数大于2,优选大于3,优选大于5,优选大于7。在具有多层配置的实施例中,优选粘着剂层存在于所述膜之间。优选从400nm到800nm测量的膜与粘着剂之间的平均折射率差异不超过0.02,优选不超过0.01,优选不超过0.005。优选粘着剂层的干燥厚度小于50μm,优选干燥厚度小于20μm。
优选地,所述膜的总厚度(无论其是否由多个层组成)是10μm到2mm,优选是15μm到2mm,优选是20μm到1.5mm。
优选地,聚合物粒子是在水性介质中通过已知的乳液聚合技术,接着喷雾干燥所得聚合物胶乳来制备。喷雾干燥典型地产生平均直径是1μm到15μm的聚合物粒子的凝集块。优选地,通过熔融混合工艺,在挤出机中,优选地在190℃到250℃、优选地195℃到240℃、优选地200℃到230℃的挤出温度下将这些凝集块直接(不减小尺寸)分散到包含聚烯烃的聚合物中以产生膜。
实例
通过喷雾干燥将GRIN粒子从水性介质分离。
比较实例1
通过熔融挤出工艺,由纯聚合物树脂的团粒制备板。在雷士挤出机(Leistritzextruder)中,在200℃到225℃范围内的机筒温度下对聚丙烯树脂(亨斯曼雷耶(HuntsmanReyen),RI=1.49,Tg-10℃,Tm 173℃)进行熔融加工。熔融混合之后进行粒化,在真空烘箱中在60℃下干燥,并且在221℃与236℃之间的温度下进行注塑模制。由注塑模制得到的测试板具有以下尺寸:66.9mm×66.9mm×1.5mm。通过ASTM D 10003-00(有关透明塑料的浊度和光透射率的标准测试方法)和ASTM E 313-00(有关由仪器测量的颜色坐标计算黄度和白度指数的标准操作)来评估这些板。数据提供于下表I中。
实例2-4
通过熔融挤出工艺,由GRIN粒子与聚合物树脂的混合物来制备板。将通过以下概述的聚合方法制备并且组成是聚((丙烯酸苯甲酯/ALMA=76/4)//MMA/EA=16/4)的GRIN粒子(RI=1.56-1.49并且粒度直径等于0.75μm)与聚丙烯树脂(亨斯曼雷耶,RI=1.49)干式共混,随后在雷士挤出机中于200℃到225℃范围内的机筒温度下进行熔融混合。熔融混合使用了一种特殊的过滤网组合布置,即80/120/300/120/80筛目,以产生GRIN粒子的最终分散体。熔融混合之后进行粒化,在真空烘箱中在60℃下干燥,并且在221℃与236℃之间的温度下进行注塑模制。由注塑模制得到的测试板具有以下尺寸:66.9mm×66.9mm×1.5mm。通过ASTM D 10003-00(有关透明塑料的浊度和光透射率的标准测试方法)和ASTM E 313-00(有关由仪器测量的颜色坐标计算黄度和白度指数的标准操作)来评估这些板。数据提供于下表I中。
实例5-7
通过熔融挤出工艺,由GRIN粒子与聚合物树脂的混合物来制备板。将通过以下概述的聚合方法制备并且组成是聚((丙烯酸苯甲酯/ALMA=76/4)//苯乙烯=20)的GRIN粒子(RI=1.56-1.59并且粒度直径等于0.80μm)与聚丙烯树脂(亨斯曼雷耶,RI=1.49)干式共混,随后在雷士挤出机中于200℃到225℃范围内的机筒温度下进行熔融混合。熔融混合使用了一种特殊的过滤网组合布置,即80/120/300/120/80筛目,以产生GRIN粒子的最终分散体。熔融混合之后进行粒化,在真空烘箱中在60℃下干燥,并且在221℃与236℃之间的温度下进行注塑模制。由注塑模制得到的测试板具有以下尺寸:66.9mm×66.9mm×1.5mm。通过ASTM D 10003-00(有关透明塑料的浊度和光透射率的标准测试方法)和ASTM E 313-00(有关由仪器测量的颜色坐标计算黄度和白度指数的标准操作)来评估这些板。数据提供于下表II中。
实例8(预种子聚合物)
本实例说明了用于在水性分散液中制造较大种子粒子的直径是0.25μm的交联聚合物预种子(pre-seed)的制备。用去离子水制备以下混合物A-C:
混合物 | 组分 | 重量份 |
A1 | 水 | 180 |
碳酸钠 | 0.40 | |
B1 | 丙烯酸正丁酯 | 98.0 |
丙烯酸烯丙酯 | 1.75 | |
1,4-丁二醇二丙烯酸酯 | 0.25 | |
22.5%十二烷基苯磺酸钠水溶液 | 2.22 | |
水 | 40.8 | |
C1 | 过硫酸钠 | 0.06 |
水 | 11.9 |
向配备有搅拌棒和冷凝器并且用氮气覆盖的反应器中装入混合物A1,并且加热到83℃。向反应器内容物中添加10%经乳化的混合物B1和25%的混合物C1。将温度维持在83℃并且搅拌混合物60分钟,之后在搅拌下经120分钟时间向反应器中添加剩余的混合物B1和混合物C1。在83℃下继续搅拌90分钟,之后将反应器内容物冷却到室温。如通过布鲁克海文仪器公司(Brookhaven Instruments)的粒度分析仪BI-90所测量,所得粒子预种子的粒度是0.25μm。
实例9(聚合物种子)
在本实例中,使用丙烯酸正丁酯、苯乙烯以及1-己硫醇使实例8的乳液中的预种子粒子生长到0.56μm直径。用去离子水制备以下混合物A2-G2:
混合物 | 组分 | 重量份 |
A2 | 碳酸钠 | 0.08 |
9.76%十二烷基苯磺酸钠水溶液 | 0.01 | |
水 | 156.00 | |
B2 | 30.10%来自实例8的水性乳液 | 29.80 |
C2 | 丙烯酸正丁酯 | 81.80 |
苯乙烯 | 18.20 | |
9.76%十二烷基苯磺酸钠水溶液 | 4.53 | |
水 | 57.50 | |
D2 | 1-己硫醇 | 18.80 |
9.76%十二烷基苯磺酸钠水溶液 | 0.58 | |
水 | 15.00 | |
E2 | 过硫酸钠 | 0.11 |
水 | 47.40 | |
F2 | 叔丁基过氧化氢70% | 0.30 |
水 | 15.00 | |
G2 | 甲醛次硫酸氢钠 | 0.20 |
水 | 6.67 |
向实例8的反应器中添加混合物A2,并且在搅拌下加热到88℃。用氮气置换反应器中的空气。当反应器温度稳定在88℃时,向反应器中装入混合物B2。随后在搅拌下,经300分钟时间向反应器中添加经乳化的混合物C2和D2以及混合物E2。在88℃下继续搅拌90分钟。将反应器内容物冷却到65℃。添加混合物F2和G2,并且在搅拌下将反应器内容物在65℃维持1小时,之后将反应器内容物冷却到室温。如通过布鲁克海文仪器公司的粒度分析仪BI-90所测量,所得乳液粒子的直径是0.56μm。
实例10(GRIN球组合物)
在本实例中,在阶段I中使用丙烯酸正丁酯和甲基丙烯酸烯丙酯,随后进行阶段II的甲基丙烯酸甲酯与丙烯酸乙酯的共聚合,使实例9的乳液中的粒子扩张以产生5μm直径的发散透镜。用去离子水制备以下混合物A3-G3:
向实例8的反应器中添加A3,在搅拌下将其加热到90℃。用氮气置换反应器中的空气。当反应器温度稳定在90℃时,向反应器中装入混合物B3。用均质机将混合物C3乳化并且将其装入反应器中。在60℃下搅拌反应器1小时。用均质机将混合物D3乳化并且将其装入反应器中。在60℃下搅动1小时之后,将反应器逐步加热到65℃-70℃,同时发生放热聚合。在达到峰值温度之后,继续搅动,同时将反应器在30分钟内冷却到73℃。装入一半的混合物F3。然后,经2小时的时间向反应器中单独地添加混合物E3、F3的其余部分以及G3。将温度维持在73℃-75℃之间并且继续搅拌1小时,接着将反应器冷却到室温。如通过库尔特公司(Coulter Corporation)的Multisizer IIE粒度分析仪所测量,所得乳液粒子的直径是5μm。
实例11(普通球组合物)
在本实例中,使用甲基丙烯酸甲酯和甲基丙烯酸烯丙酯使实例9的乳液中的粒子扩张以产生5μm直径的会聚透镜。用去离子水制备以下混合物A3-C3:
向实例1的反应器中添加A3,在搅拌下将其加热到60℃。用氮气置换反应器中的空气。当反应器温度稳定在60℃时,将混合物B3装入反应器中。用均质机将混合物C3乳化并且将其装入反应器中。在60℃下搅拌反应器1小时。用均质机将混合物D3乳化并且将其装入反应器中。在60℃下搅动1小时之后,将反应器逐步加热到80℃,同时发生放热聚合。在达到峰值温度之后,继续在88℃下搅动,直到聚合反应显示>92%转化。聚合反应之后,使反应器在30分钟内冷却到73℃。将温度维持在73℃-75℃之间并且继续搅拌1小时,接着将反应器冷却到室温。如通过库尔特公司的Multisizer IIE粒度分析仪所测量,所得乳液粒子的直径是5μm。
通过干涉显微镜检法,借助于蔡司杰纳沃干涉显微镜(Zeiss JenavalInterference microscope)(250-CF系列JENA)分析由上文所描述的聚合反应方案获得的5微米球。由干涉条纹,如上准确地确定并描绘折射率随每一球体的半径的变化。已经使用如上文所描述的蔡司杰纳沃因特非科干涉显微镜(Zeiss Jenaval InterphakoInterference Microscope),用众所周知的实验技术分析了使用本文中所描述的相同种子粒子膨胀/聚合反应方法制造的平均粒度是2μm的粒子,由此测定从粒子的中心到表面的折射率。本领域的普通技术人员将预期通过相同的种子粒子膨胀/聚合反应方法制造的较小粒子展现相同的折射率特性逐步变化,并且将认识到,平均直径是0.3μm到1.9μm的给定粒子所展现的折射率分布可以基于通过相同方法制造并且具有相同组成的5μm粒子所展现的折射率分布间接确定。
表I:聚丙烯(PP)与GRIN粒子的共混物的光学特性
实例 | 组成(PP∶GRIN) | L | a | b | 浊度 | Tt | YI | 亮度 |
1 | 100∶00 | 96.4 | 0.22 | 2.17 | 62.3 | 93.59 | 4.17 | 90.69 |
2 | 99.5∶0.50 | 96.72 | 0.04 | 2.98 | 74.48 | 93.54 | 5.53 | 89.59 |
3 | 99∶1.00 | 95.25 | -0.14 | 5.01 | 81.67 | 90.72 | 9.29 | 84.19 |
4 | 98.5∶1.50 | 93.54 | -0.06 | 5.86 | 84.00 | 87.50 | 11.14 | 79.98 |
表II:聚丙烯与GRIN粒子的共混物的光学特性
实例 | 组成(PP∶GRIN) | L | a | b | 浊度 | Tt | YI | 亮度 |
5 | 99.5∶0.50 | 96.34 | 0.11 | 3.86 | 81.94 | 92.81 | 7.24 | 87.71 |
6 | 99∶1.00 | 93.26 | 0.14 | 5.64 | 85.26 | 86.98 | 10.91 | 79.77 |
7 | 98.5∶1.50 | 90.67 | 0.20 | 6.27 | 86.05 | 82.22 | 12.51 | 74.42 |
Tt是可见光的透射率%(根据ASTM D 10003-00测量)。
YI是黄度指数(根据ASTM E 313-00测量)
浊度是根据ASTM D 10003-00测量。
Claims (9)
1.一种膜,其包含0.5wt%到15wt%的聚合物粒子,所述聚合物粒子具有:(a)至少70wt%的丙烯酸系单体的聚合残基;(b)0.75μm到15μm的平均粒径;及(c)从所述粒子的中心到表面连续变化的折射率;以及包含至少85wt%的聚烯烃的连续聚合物相,所述聚烯烃是具有两个到八个碳原子的烯烃的聚合物或共聚物;其中从400nm到800nm测量的所述聚合物粒子与所述连续聚合物相之间的平均折射率差异不超过0.02。
2.如权利要求1所述的膜,其中所述平均粒径是1.5μm到10μm。
3.如权利要求2所述的膜,其中所述聚合物粒子的折射率是1.45到1.53。
4.如权利要求3所述的膜,其中在所述聚合物粒子的中心处的折射率是1.52到1.60并且在所述表面处的折射率是1.46到1.52。
5.如权利要求4所述的膜,其中所述连续聚合物相包含1wt%到12wt%的所述聚合物粒子。
6.如权利要求5所述的膜,其中所述平均粒径是2μm到8μm。
7.如权利要求6所述的膜,其中所述聚合物粒子包含至少80wt%的丙烯酸单体与苯乙烯单体的聚合残基。
8.如权利要求7所述的膜,其中所述连续聚合物相包含1到9wt%的聚合物粒子。
9.如权利要求8所述的膜,其中所述连续聚合物相包含至少95wt%的聚丙烯。
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