CN103003062A - 具有改进的阻隔作用和耐刮擦性能的透明的耐候性阻隔膜 - Google Patents
具有改进的阻隔作用和耐刮擦性能的透明的耐候性阻隔膜 Download PDFInfo
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Abstract
本发明涉及通过层合、挤出层合(粘合剂、熔体或热熔体层合)或挤出涂覆制备透明的耐候性阻隔膜。所述膜也可以含有耐刮擦涂层。为此,将两个或更多个透明膜复合体彼此接合,所述透明膜复合体各自由两个外部聚烯烃层或聚酯层构成,所述聚烯烃层或聚酯层各自经无机涂覆并采用所述无机层在内部彼此粘接。所述复合体与耐候性透明膜(例如PMMA或PMMA-聚烯烃共挤出物或PMMA-聚酯共挤出物)层合。所述无机氧化物层具有高光学透明性以及同时具有好的对水蒸气和氧气的阻隔作用的性能,而所述PMMA层带来气候稳定性。
Description
技术领域
本发明涉及通过层合、挤出层合(粘合剂、熔体或热熔体层合)或挤出涂覆制备透明的耐候性阻隔膜。为此,将两个或更多个透明膜复合体与耐候性透明膜(例如PMMA或PMMA-聚烯烃共挤出物或PMMA-聚酯共挤出物)层合,所述透明膜复合体各自由两个外部聚烯烃层或聚酯层构成,所述聚烯烃层或聚酯层各自经无机涂覆并采用所述无机层在内部彼此粘接。所述无机氧化物层具有高光学透明性以及同时具有好的对水蒸气和氧气的阻隔作用的性能,而所述PMMA层带来气候稳定性。所述膜此外包含提高耐刮擦性的涂层。
背景技术
基于聚甲基丙烯酸酯的耐候性、透明且抗冲击性膜由申请人以品名销售。专利DE3842796A1描述了基于丙烯酸酯的透明抗冲击性模塑组合物的制备,由它制备的膜和模制品,以及制备模塑组合物的方法。这些膜具有的优点是,它们在暴露于热和湿气中的情况下不变色和/或变脆。另外,它们避免当暴露于冲击或弯曲应力下时的所谓的应力发白。这些膜是透明的并甚至在暴露于热和湿气下,在气候作用下以及在暴露于下冲击或弯曲应力下时仍保持这样。
所述模塑组合物的加工以获得所述透明、抗冲击性膜理想地如下进行:经由宽缝模头挤出熔体并在辊床上平整。这种膜的特征是持久透明性、对热和冷的不敏感性、耐候性、低泛黄和变脆并在弯折或折叠时表现出低应力发白,并因此它们适合例如作为帆布车篷、汽车遮盖物或帆船中的窗体。此类膜具有小于1mm,例如0.02mm-0.5mm的厚度。一种重要的应用领域是在刚性、尺寸稳定的基础型体,例如金属片、厚纸板、刨花板、塑料片材等上形成厚度例如0.02mm-0.5mm的薄表面层。为了制备此种覆层,存在各种可利用的方法。例如,可以将所述膜挤出成模塑组合物,平整并层合到基材上。经由挤出涂覆技术,可以将挤出的线料施加于基材的表面上并利用辊子平整。如果热塑性塑料用作基材本身,则可以将这两种组合物共挤出而形成由本发明透明模塑组合物形成的表面层。
然而,PMMA膜对水蒸气和氧气的阻隔性能仅是不足够的,然而此种性能对用于医疗应用、包装工业中的应用,但尤其是在户外领域中使用的电气应用中是必要的。
对于改进阻隔性能的目的,将透明的无机层施加于聚合物膜上。硅的氧化物层和铝的氧化物层已经尤其变得成熟。这些无机氧化物层(SiOx或AlOx)通过真空镀覆方法施加(以化学方式,JP-A-10025357、JP-A-07074378;热或电子束蒸发、溅镀,EP1018166B1、JP2000-307136A、WO2005-029601A2)。EP1018166B1中公开了SiOx层的UV吸收可能受到SiOx层中硅与氧的比例影响。为了保护下方的层免受UV辐射,这是重要的。然而,缺点是改变硅与氧的比例也改变阻隔性能。这样,透明性和阻隔作用不能彼此独立地改变。
这些无机氧化物层主要地施加到聚酯和聚烯烃上,因为这些材料经受住蒸发工艺期间的温度应力。另外,无机氧化物层对聚酯和聚烯烃充分地粘附,其中所述聚烯烃在涂覆之前经历电晕处理。然而,因为这些材料对气候作用不稳定,所以它们经常与卤化膜层合,例如WO94/29106中所述那样。然而,卤化膜出于环境保护原因是成问题的。
如由U.Moosheimer,Galvanotechnik90,第9期,1999,第2526-2531页公开的那样,用无机氧化物层涂覆PMMA不改进对水蒸气和氧气的阻隔作用,因为PMMA是无定形的。然而,与聚酯和聚烯烃不同,PMMA是气候稳定的。
在DE102009000450.5中,申请人使用在无机层和粘合促进剂之间造成良好粘附的涂料。如本领域技术人员已知的那样,有机和无机层之间的粘附比在这一方面相同种类的层之间更难以达到。
AlcanPackaging公司尤其于2008年6月25日在巴塞尔的“有机发光体(Organische Lichtemitters)”会议中介绍了由不同的用硅的氧化物涂覆的PET膜构成的多层层合体,该PET膜又彼此由粘合剂层接合。然而,对于在户外领域中的太阳能应用,这些层合体太敏感且寿命短,因为它们在UV辐射下迅速地分解。
发明内容
问题
本发明要解决的问题是提供具有宽的可使用性并甚至在极端气候条件下仍长寿命的挠性光生伏打体系。
本发明基于的目的因此是提供制备这种挠性光生伏打体系的阻隔膜,该阻隔膜是气候稳定和高度透明的(在>300nm的波长范围内>80%),其中确保高的对水蒸气和氧气的阻隔性能。
另外,将达到大于1000V的局部放电电压。
解决方案
所述问题由新的多层膜层合体解决,该膜层合体具有由含有PMMA层的至少三层的第一层合体作为载体层合体与含有多个无机氧化物层的多层第二层合体作为阻隔层合体形成的组合。载体层合体和阻隔层合体又由粘合剂层彼此接合。
所述问题尤其通过包括阻隔层合体和对气候尤其稳定的载体层合体的膜层合体解决。所述性能由多层膜达到,其中各个层通过真空蒸气涂覆、层合、挤出层合(粘合剂、熔体或热熔体层合)或挤出涂覆彼此组合。为此,可以使用常用的方法,例如S.E.M.Selke,J.D.Cul ter,R.J.Hernandez,"Plas tics Packaging",第二版,Hanser-Verlag,ISBN1-56990-372-7第226和227页所述的那些。
在这种构造中,载体层合体位于膜层合体的外侧。相应地,一般在基材上粘接的阻隔层合体位于载体层合体和基材之间。载体层合体和阻隔层合体彼此通过粘合剂层(下文中称作粘合剂4)接合。
第一层合体(下面称作载体层合体)由包含0.1-5.0wt%,优选0.5-3.0wt%,更优选2.0-3.0wt%UV稳定剂的外部的PMMA保护层,和由透明聚酯或聚烯烃,优选PET或聚丙烯构成的第二载体膜组成。所述保护层和载体膜又通过粘合剂层(下文中:粘合剂1),优选通过热熔体,更优选通过包含丙烯酸酯-乙烯共聚物的热熔体彼此接合。
所述PMMA保护层满足气候稳定性的性能,载体层导致层合体的稳定性。因为PMMA的直接无机涂层根据现有技术是不可能的,所以此外载体层要确保与任选地在表面上带有无机层的阻隔层合体的长久和牢固的接合。该PMMA层又保护聚酯或聚烯烃载体膜免受气候老化影响。
任选地,又涂覆PMMA保护层。所述涂层用来减小表面刮痕和/或改进耐磨性和/或作为抗污涂层,耐刮擦涂层是尤其重要的。
另外,防护UV辐射的功能不再如现有技术中那样由无机氧化物层承担,而是改为由PMMA层承担。因此,氧化物层仅仅可以根据光学和阻隔指标优化。
阻隔层合体又由至少三个涂有无机阻隔层的聚合物膜,例如聚酯膜或聚烯烃膜,优选聚酯膜,更优选PET膜组成。无机阻隔层优选是硅的氧化物层,下面称作SiOx层。无机氧化物层履行阻隔性能,特别是对于空气氧和水蒸气的阻隔性能。所述至少三个SiOx-涂覆的膜又通过粘合剂,优选双组分聚氨酯粘合剂彼此接合。这样形成载体层合体。当将两个氧化物层彼此接合时,粘合剂层涉及粘合剂2,当将膜中的两个彼此接合时,粘合剂层涉及粘合剂3,或当将氧化物层与聚合物膜接合时,粘合剂层涉及粘合剂2a。
为了更容易地理解,下面描述基于优选的SiOx-涂覆的PET膜的体系。然而,应当说明的是,由此仅描述一个优选的实施方案,并且SiOx层应当理解为是其它无机氧化物层的代表,PET薄是其它聚酯或聚烯烃膜的代表。
载体层合体由至少三个且不超过八个,优选四个或六个SiOx-涂覆的PET膜组成。这些又通过粘合剂层彼此接合。层的顺序可以改变。在一个实施方案中,PET膜位于表面上,即随后与载体层合体接合的那面上,并因此,例如,在光生伏打器件的应用领域,在朝向日光的那面上。在它上面随后有SiOx层,在该SiOx层上面随后又有粘合剂层2a,在该粘合剂层2a上面随后又是PET膜、第二SiOx层和第二粘合剂层2a。所有进一步的膜(高达总共八个)在这个示例性的实施方案中沿相同方向层合。
在一个优选实施方案中,无机和有机层之间的粘附经常发生的问题如下规避:将两个无机涂覆的膜彼此粘接,其中无机面向内且有机膜面向外。其然后可以容易地与其它有机聚合物,如载体层合体的底侧,或第二双重层合体接合。因此,对于阻隔层合体得到一种尤其优选的具有以下顺序的构造:
PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET。
任选地,并因此同样尤其优选地,其是由这些个体膜中的六个构成的膜体系。这样产生以下顺序:
PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET。
用粘合剂2实现的无机层之间的粘附可以例如使用聚氨酯基双组分粘合剂(2K-PU粘合剂)实现,所述粘合剂在无机层上被优化。
PET膜,或聚醚或聚烯烃膜同样可以利用2K-PU粘合剂,熔体粘合剂(例如,基于EVA或丙烯酸酯-乙烯),或挤出层合而彼此接合。在后一种情况下,免除粘合剂3层。另选,也可以双面用SiOx涂覆PET膜。这些膜又与单面涂覆的PET膜层合。在这种情况下,例如,对于具有四个SiOx层的体系,所得的构造如下:
PET-SiOx-粘合剂2-SiOx-PET-SiOx-粘合剂2-SiOx-PET。
2个无机涂覆(配备有阻隔层)的载体层的复合体具有的优点是这两个无机层受这两个外部载体层保护。因此,当与保护膜层合时,阻隔层不受损害。另外,用于制备该复合体的粘合剂可以对于无机层而优化。
发明详述
本发明的优点:
本发明的阻隔膜
●是尤其气候稳定的。
●是无卤的。
●对水蒸气和氧气具有高阻隔作用(<0.01g/(m d))。
●独立于SiOx层的组成而保护位于下方的层以防UV辐射。
●可以廉价地制备,因为对于无机真空蒸气涂覆的不连续方法可以使用薄的膜。
●可以容易地制备,因为无机层仅与无机层彼此接合,且有机层仅与有机层彼此接合。
本发明膜层合体的另一个特征是它具有至少1000V的局部放电电压和在大于300nm范围内大于80%的透明度。
载体层合体
载体层合体由载体膜、保护层、任选的耐刮擦涂层和任选的粘合剂层1组成。载体层合体通过粘合剂层4与阻隔层合体接合。
保护层
作为保护层,并因此作为第一层合体的最外层,使用优选由聚甲基丙烯酸甲酯(PMMA)或抗冲击性PMMA(im-PMMA)构成的膜。另选,除PMMA膜之外,还可以使用PVDF/PMMA双层膜或由PVDF/PMMA共混物构成的膜作为保护层,如DE102009000450中已经描述的那些。PMMA保护层具有10-200μm,优选20-150μm,更优选30-100μm的厚度。
抗冲改性的聚(甲基)丙烯酸酯塑料由20wt%-80wt%,优选30wt%-70wt%的聚(甲基)丙烯酸酯基体和80wt%-20wt%,优选70wt%-30wt%的弹性体颗粒组成,所述弹性体颗粒的平均颗粒直径是10-150nm(例如用超离心法测量)。
抗冲改性的聚(甲基)丙烯酸酯塑料(im-PMMA)由基体聚合物部分(由至少80wt%甲基丙烯酸甲酯的单元以及任选的0wt%-20wt%可与甲基丙烯酸甲酯共聚的单体的单元聚合)和在该基体中分布的基于交联的聚(甲基)丙烯酸酯的抗冲改性剂部分组成。
所述基体聚合物更尤其是由80wt%-100wt%,优选90wt%-99.5wt%的自由基聚合的甲基丙烯酸甲酯单元和任选的0wt%-20wt%,优选0.5wt%-10wt%其它可自由基聚合的共聚单体,例如(甲基)丙烯酸C1-C4烷基酯,更尤其是丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯组成。基体的平均分子量Mw(重均)优选在90000g/mol-200000g/mol,更尤其是100000g/mol-150000g/mol的范围内(利用凝胶渗透色谱法参照聚甲基丙烯酸甲酯作为校准标准物测定Mw)。分子量Mw可以例如通过凝胶渗透色谱法或通过光散射方法测定(参见,例如H.F.Mark等人的Encyclopedia of Polymer Science and Engineering,第二版,第10卷,第1页及后续页,J.Wiley,1989)。
优选由90wt%-99.5wt%的甲基丙烯酸甲酯和0.5wt%-10wt%的丙烯酸甲酯形成的共聚物。维卡软化温度VST(ISO306-B50)可以位于至少90℃,优选95-112℃的范围内。
聚甲基丙烯酸酯基体优选包含抗冲改性剂,其可以是例如具有两或三壳构造的弹性体颗粒。
聚甲基丙烯酸酯塑料的抗冲改性剂是公知的。抗冲改性的聚甲基丙烯酸酯模塑组合物的制备和构成例如描述在EP-A0113924、EP-A0522351、EP-A0465049和EP-A0683028中。
在聚甲基丙烯酸酯基体中存在1wt%-30wt%,优选2wt%-20wt%,更优选3wt%-15wt%,更尤其是5wt%-12wt%的抗冲改性剂。抗冲改性剂是按本身已知的方式通过成珠聚合或通过乳液聚合获得的。
在最简单的情况下,其涉及可利用成珠聚合获得的并具有10-150nm,优选20-100nm,更尤其是30-90nm的平均颗粒尺寸的交联颗粒。这些一般由至少40wt%,优选50wt%-70wt%的甲基丙烯酸甲酯,20wt%-40wt%,优选25wt%-35wt%的丙烯酸丁酯和0.1wt%-2wt%,优选0.5wt%-1wt%的交联单体,例如多官能(甲基)丙烯酸酯例如甲基丙烯酸烯丙酯,和任选的其它单体例如0wt%-10wt%,优选0.5wt%-5wt%的甲基丙烯酸C1-C4烷基酯,例如丙烯酸乙酯或甲基丙烯酸丁酯,优选丙烯酸甲酯,或其它可乙烯基聚合的单体例如苯乙烯组成。
优选的抗冲改性剂是可以具有双层或三层核-壳型构造并通过乳液聚合而获得的聚合物颗粒(参见,例如,EP-A0113924、EP-A0522351、EP-A0465049和EP-A0683028)。然而,对于本发明目的,这些乳液聚合物的适合的颗粒尺寸必须在10-150nm,优选20-120nm,更优选50-100nm的范围内。
具有一个核和两个壳的三层或三相构造可以如下完成:最内部的(硬)壳可以例如基本上由甲基丙烯酸甲酯,低比例的共聚单体例如丙烯酸乙酯,和交联剂部分,例如甲基丙烯酸烯丙酯组成。中间的(软)壳可以例如由丙烯酸丁酯和任选的苯乙烯构造,而最外面的(硬)壳通常基本上与基体聚合物相对应,这引起与基体的相容性和对其的良好连接。抗冲改性剂中的聚丙烯酸丁酯比例对抗冲击性作用是关健的并优选在20wt%-40wt%,更优选25wt%-35wt%的范围内。
可以在挤出机中将抗冲改性剂和基体聚合物以熔体混合而获得抗冲改性的聚甲基丙烯酸酯模塑组合物。一般,首先将排出的材料切粒。其可以利用挤出或注塑而进一步加工成模制品,例如片材或注塑部件。
优选地,特别是对于膜的制备,不过并不限于此,使用原理上从EP0528196A1获知的体系,该体系包含由以下物质组成的两相抗冲改性的聚合物:
a1)10wt%-95wt%的具有大于70℃的玻璃化转变温度Tg的由以下物质构成的连贯硬相,
a11)80wt%-100wt%(基于a1)甲基丙烯酸甲酯,和
a12)0wt%-20wt%一种或多种其它烯属不饱和可自由基聚合
的单体,和
a2)90wt%-5wt%的分布在硬相内并具有小于-10℃的玻璃化转变温度Tg的由以下物质构成的韧性相,
a21)50wt%-99.5wt%的丙烯酸C1-C10烷基酯(基于a2)
a22)0.5wt%-5wt%含两个或更多个烯属不饱和可自由基聚合的基团的交联单体,和
a23)任选地,其它烯属不饱和可自由基聚合的单体,
其中所述硬相a1)的至少15wt%与所述韧性相a2)以共价键连接。
所述两相抗冲改性剂可以通过在水中的二阶段乳液聚合制备,例如DE-A3842796中所述那样。在第一阶段中,制备韧性相a2),其由至少50%,优选大于80%的丙烯酸低级烷基酯构成,从而得到这种相的小于-10℃的玻璃化转变温度Tg。所使用的交联单体a22)是二醇的(甲基)丙烯酸系酯,例如乙二醇二甲基丙烯酸酯或1,4-丁二醇二甲基丙烯酸酯,具有两个乙烯基或烯丙基的芳族化合物,例如二乙烯基苯,或其它具有两个烯属不饱和可自由基聚合的基团的交联剂,例如甲基丙烯酸烯丙酯,作为接枝交联剂。
作为具有三个或更多个不饱和、可自由基聚合的基团,例如烯丙基或(甲基)丙烯酰基的交联剂可提及例如,氰脲酸三烯丙酯,三羟甲基丙烷三丙烯酸酯和三甲基丙烯酸酯,和季戊四醇四丙烯酸酯和四甲基丙烯酸酯。在这方面的其它实例给出在US4,513,118中。
在a23)下提及的烯属不饱和可自由基聚合单体可以是例如,丙烯酸和/或甲基丙烯酸,以及它们的含1-20个碳原子的烷基酯,其中烷基可以是直链、支链或环状的。另外,a23)可以包含可与(甲基)丙烯酸烷基酯a21)共聚合的其它可自由基聚合的脂族共聚单体。然而,意于排除显著比例的芳族共聚单体,例如苯乙烯、α-甲基苯乙烯或乙烯基甲苯,因为它们导致模塑组合物A的不希望的性能,尤其是在经历气候作用时。
当在第一阶段制备韧性相时,必须精确注意调节颗粒尺寸和它的不均一性。在这方面,韧性相的颗粒尺寸主要取决于乳化剂的浓度。颗粒尺寸可以有利地通过使用种子胶乳控制。基于水相,使用0.15wt%-1.0wt%的乳化剂浓度获得平均(重均)颗粒尺寸低于130nm,优选低于70nm且颗粒尺寸的多分散度U80低于0.5(U80是由对通过超离心测定的颗粒尺寸分布进行积分评价而测定的。适用的是U80=[(r90-r10)/r50]-1,其中r10、r50、r90=平均积分颗粒半径,对于该颗粒半径适用的是,10、50、90%的颗粒半径低于该值且90%、50%和10%的颗粒半径高于该值),优选低于0.2的颗粒。这特别适合于阴离子乳化剂,例如尤其优选的烷氧基化和硫酸化的链烷烃。所使用的聚合引发剂是例如,0.01wt%-0.5wt%的过氧二硫酸碱金属盐或过氧二硫酸铵,基于水相,并且在20-100℃温度下引发聚合反应。优选在20-80℃的温度下使用氧化还原体系,例如0.01wt%-0.05wt%有机氢过氧化物和0.05wt%-0.15wt%羟甲基亚磺酸钠组成的组合。
至少以15wt%与韧性相a2)共价连接的硬相a1)具有至少70℃的玻璃化转变温度并且可以仅仅由甲基丙烯酸甲酯构成。至多20wt%的一种或多种其它烯属不饱和可自由基聚合的单体可以作为共聚单体a12)存在于硬相中,其中(甲基)丙烯酸烷基酯,优选含1-4个碳原子的丙烯酸烷基酯,按满足玻璃化转变温度不低于上述玻璃化转变温度的用量使用。
硬相a1)的聚合在第二阶段中同样在乳液中,在使用常规助剂,例如也用于韧性相a2)的聚合的那些的情况下进行。
在一个优选实施方案中,硬相按0.1wt%-10wt%,优选0.5wt%-5wt%的量包含低分子量UV吸收剂和/或共聚合的UV吸收剂,基于A,作为硬相中的共聚单体组分a12)的成分。尤其描述在US4576870中的可聚合UV吸收剂的实例可提及2-(2’-羟苯基)-5-甲基丙烯酰氨基苯并三唑或2-羟基-4-甲基丙烯酰氧基二苯甲酮。低分子量UV吸收剂可以是,例如,2-羟基二苯甲酮或2-羟苯基苯并三唑或水杨酸苯酯的衍生物。一般而言,低分子量UV吸收剂具有小于2×103(g/mol)的分子量。尤其优选的是在加工温度下具有低挥发性且与聚合物A的硬相a1)具有均匀混容性的UV吸收剂。
还可以使用聚甲基丙烯酸酯和聚烯烃或聚酯的共挤出物。聚丙烯和PMMA的共挤出物是优选的。另外,还可以的是氟化的、卤化的层,例如PVDF与PMMA的共挤出物或PVDF和PMMA的共混物,然而在此会丢失不存在卤素的优点。
保护层具有20μm-500μm的厚度;厚度优选是50μm-400μm,非常优选200μm-300μm。
光稳定剂
根据本发明,可将光稳定剂添加到载体层中。
所谓的光稳定剂是指UV吸收剂、UV稳定剂和自由基清除剂。
任选存在的UV保护剂是例如,二苯甲酮的衍生物,其取代基例如羟基和/或烷氧基通常位于2和/或4位。它们包括2-羟基-4-正辛氧基二苯甲酮,2,4-二羟基二苯甲酮,2,2'-二羟基-4-甲氧基二苯甲酮,2,2',4,4'-四羟基二苯甲酮,2,2'-二羟基-4,4'-二甲氧基二苯甲酮、2-羟基-4-甲氧基二苯甲酮。另外非常适合作为UV防护添加剂的是取代的苯并三唑,对此特别包括2-(2-羟基-5-甲基苯基)苯并三唑、2-[2-羟基-3,5-二(α,α-二甲基苄基)苯基]苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)苯并三唑、2-(2-羟基-3,5-丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-3,5-二叔戊基苯基)苯并三唑、2-(2-羟基-5-叔丁基苯基)苯并三唑、2-(2-羟基-3-仲丁基-5-叔丁基苯基)苯并三唑和2-(2-羟基-5-叔辛基苯基)苯并三唑,苯酚,2,2'-亚甲基双[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)]。
除所述苯并三唑之外还可以使用2-(2’-羟苯基)-1,3,5-三嗪类别的UV吸收剂,例如苯酚,2-(4,6-二苯基-1,2,5-三嗪-2-基)-5-(己氧基)。
另外,可以使用的UV稳定剂是2-氰基-3,3-二苯基丙烯酸乙酯、2-乙氧基-2′-乙基-N,N’-草酰二苯胺、2-乙氧基-5-叔丁基-2′-乙基-N,N’-草酰二苯胺和取代的苯甲酸苯基酯。
光稳定剂和/或UV保护剂可以作为低分子量化合物(如上所指出)存在于待稳定化的聚甲基丙烯酸烷基酯组合物中。然而,基体聚合物分子中的UV吸收性基团也可通过与可聚合UV-吸收化合物,例如二苯甲酮衍生物或苯并三唑衍生物的丙烯酸系-、甲基丙烯酸系-或烯丙基衍生物共聚而被共价地键合。
UV保护剂的比例一般是0.01wt%-10wt%,特别是0.01wt%-5wt%,更尤其是0.02wt%-2wt%,基于(甲基)丙烯酸酯共聚物,其中其也可以是化学不同的UV保护剂的混合物。
作为自由基清除剂/UV稳定剂的实例在此可提及空间位阻胺,它们以品名HALS(受阻胺光稳定剂)已知。它们可在涂料和塑料中,尤其在聚烯烃塑料中用于抑制老化过程(Kunststoffe,74(1984)10,第620-623页;Farbe+Lack,96年度,9/1990,第689-693页)。HALS化合物的稳定化作用由它们中所含有的四甲基哌啶基团担负。这类化合物既可在哌啶氮上未被取代,又可在其上被烷基或酰基取代。空间位阻的胺在UV范围内不吸收。它们清除所形成的自由基,这是UV吸收剂又不可能做到的。具有稳定化作用的也可以作为混合物采用的HALS化合物的实例如下:
癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3-8-三氮杂螺[4.5]癸烷-2,5-二酮、琥珀酸双(2,2,6,6-四甲基-4-哌啶基)酯、聚(N-β-羟乙基-2,2,6,6-四甲基-4-羟基-哌啶-琥珀酸酯)或癸二酸双(N-甲基-2,2,6,6-四甲基-4-哌啶基)酯。
自由基清除剂/UV稳定剂按0.01wt%-15wt%,特别是0.02wt%-10wt%,更尤其是0.02wt%-5wt%的量用于本发明的聚合物混合物,基于(甲基)丙烯酸酯共聚物。
UV吸收剂优选在PMMA层中,但是其也可以存在于聚烯烃层或聚酯层中。
此外,保护层具有足够的层厚度以确保1000V的局部放电电压。例如,在PMMA的情况下,这自250μm的厚度起给出。局部放电电压是指放电发生时的电压,其部分地桥接绝缘材料(参见DIN EN60664-1)。
耐刮擦涂层
术语“耐刮擦涂层”与本发明相关地理解为是为了减小表面刮痕和/或改进耐磨性施加的涂层的统称。为了在例如光生伏打体系中使用所述膜层合体,高耐磨性尤其非常重要。
耐刮擦涂层的另一个重要的性能在最宽的意义上是该层不会不利地改变膜复合体的光学性能。作为耐刮擦涂层,可以使用聚硅氧烷,例如得自SDC Techologies Inc.公司的CRYSTALCOATTM MP-100,都得自Momentive Performance Materials公司的AS400-SHP401或UVHC3000K。这些涂料配方通过例如辊涂、刀涂或流涂施加到膜复合体或覆盖膜的表面上。
作为考虑的其它涂覆技术的实例可提及PVD(物理蒸气沉积;物理气相沉积)以及CVD等离子体(化学蒸气沉积;化学气相沉积)。
载体膜
作为载体膜或同义的载体层,使用由优选聚酯(PET、PET-G、PEN)或聚烯烃(PE、PP)形成的膜。载体膜的选择由以下强制必要的性能决定:该膜必须是高度透明、挠性和抗热变形的。作为具有这种性能分布的膜已经证明尤其合适是聚酯膜,特别是共挤出的双轴取向聚对苯二甲酸乙二醇酯(PET)膜。
载体层具有10-500μm的厚度,厚度优选在100-400μm,非常优选150-300μm之间。
载体层在>300nm,优选350-2000nm,更优选380-800nm的波长范围中具有大于80%,优选大于85%,更优选大于90%的透明度。
粘合剂层1
取决于材料组合,通过膜共挤出或通过层合,例如通过挤出层合而制备PMMA保护层和载体膜。在此,粘合剂的选择由待彼此粘接的基材和对于粘合剂层的透明度的高要求得出。对于PMMA和PET的组合,优选熔体粘合剂。此种熔体粘合剂的实例是乙烯-乙酸乙烯酯热熔体(EVA热熔体)或丙烯酸酯-乙烯热熔体。丙烯酸酯-乙烯热熔体是优选的。粘合剂层1一般具有10-100μm,优选20-80μm,更优选40-70μm的厚度。
阻隔层合体
如前已述,阻隔层合体的特征在于由配备有无机阻隔层的聚合物膜构成的不同阻隔膜的序列。
聚合物膜
所使用的聚合物膜是优选由聚烯烃(PE,PP)或聚酯(PET、PET-G、PEN)构成的膜。也可以使用由其它聚合物构成的膜(例如,聚酰胺或聚乳酸)。所述载体层具有1-100μm的厚度,厚度优选是5-50μm,非常优选10-30μm。
聚合物膜的透明度在>300nm,优选350-2000nm,更优选380-800nm的波长范围中大于80%,优选大于85%,更优选大于90%。
阻隔层
将阻隔层施加于载体层上并且阻隔层优选由无机氧化物,例如SiOx或AlOx构成。然而,也可以使用其它无机材料(例如SiN、SiNxOy、ZrO、TiO2、ZnO、FexOy、透明有机金属化合物)。对于精确的层构造,参见实施例。作为SiOx层优选使用具有1:1-1:2,更优选1:1.3-1:1.7的硅与氧的比例的层。层厚度是5-300nm,优选10-100nm,更优选20-80nm。
在AlOx的情况下,x是0.5-1.5,优选1-1.5,非常优选1.2-1.5的范围(其中x=1.5Al2O3)。层厚度是5-300nm,优选10-100nm,更优选20-80nm。
无机氧化物可以利用物理真空沉积(电子束或热过程)、磁控管溅射或化学真空沉积施加。这可以反应性地(在供应氧气的情况下)或非反应性地进行。火焰、等离子或电晕预处理同样是可能的。
粘合剂层2
采用粘合剂层2实现的无机层之间的粘附优选用聚氨酯基双组分粘合剂(2K-PU粘合剂)达到,所述粘合剂对于无机层而优化。粘合剂2的层厚度是0.1-10μm,优选0.5-5μm,更优选0.5-1μm。
另外,粘合剂层2任选地包含改进对SiOx的粘附的组分,例如含硅氧烷基的丙烯酸酯或甲基丙烯酸酯,例如甲基丙烯酰氧基丙基三甲氧基硅烷。含硅氧烷基的丙烯酸酯或甲基丙烯酸酯在粘合剂层中的存在量可以是0wt%-48wt%。粘合剂层含有0.1%-10wt%,优选0.5%-5wt%,更优选1%-3wt%的引发剂,例如184或651。作为调节剂,粘合剂层还可以含有0wt%-10wt%,优选0.1wt%-10wt%,更优选0.5wt%-5wt%的硫化合物。一个变型是,主组分的一部分用0wt%-30wt%的预聚物替换。粘合剂组分任选地包含0wt%-40wt%对于粘合剂而言常用的添加剂。
还可以使用基于环氧树脂的UV/Vis-固化体系,例如DELOKATIOBOND LP655、LP VE19781或LP VE19663,它们还改进阻隔作用。
粘合剂层2a
使用粘合剂2a,将无机氧化物层另选地直接与聚合物膜,优选PET或聚烯烃膜接合。取决于材料组合,粘合剂2a可以对应于粘合剂2或粘合剂3。
粘合剂层3
PET膜,或聚酯或聚烯烃膜,可以利用2K-PU粘合剂,熔体粘合剂(例如,基于EVA或丙烯酸酯-乙烯),或挤出层合彼此接合。在后一种情况下,免除粘合剂3层。另选,也可以双面用SiOx涂覆PET膜。另选,还可以采用在粘合剂4部分中描述的体系。
粘合剂层3具有1-100μm,优选2-50μm,更优选5-20μm的厚度。
粘合剂层4
粘合剂层4位于载体层合体和阻隔层之间。它允许实现这两者之间的粘附。粘合剂层具有1-100μm,优选2-50μm,更优选5-20μm的厚度。粘合剂层4在组成和厚度方面也可以等同于粘合剂层3。
粘合剂层4可以由熔体粘合剂形成。其可以由聚酰胺、聚烯烃、热塑性弹性体(聚酯、聚氨酯或共聚酰胺弹性体)或由共聚物构成。优选使用乙烯-乙酸乙烯酯共聚物或乙烯-丙烯酸酯共聚物或乙烯-甲基丙烯酸酯共聚物。粘合剂层可以利用辊涂方法在层合中施加或利用喷嘴在挤出层合中或在挤出涂覆中施加。
粘合剂层5
可以利用由粘合剂5构成的粘合剂层使膜层合体粘接到基材上,该粘合剂层施加于底侧,即阻隔层合体的背离载体层合体的那侧。基材可以是,例如,半导体例如硅。粘合剂在这种情况下可以是热熔体,例如乙烯-乙酸乙烯酯EVA。该热熔体层一般具有50-500μm的厚度。
应用
这种阻隔膜可以用于包装工业、显示技术、有机光生伏打器件、薄层光生伏打器件、结晶硅模块和用于有机LED。
具体实施方式
实施例
用阻隔层(例如SiOx)涂覆聚合物膜(例如PET)。通过辊涂方法,利用粘合剂层2,以让SiOx层彼此面对的方式使它与第二SiOx-涂覆的聚合物膜接合。利用压敏粘合剂通过层合使所得的阻隔复合体与第二阻隔复合体接合。将通过PMMA、热熔体和PP的共挤出制备的载体层合体施加于所得的膜复合体上。作为用于层合的粘合剂层4,可以例如,使用聚氨酯基粘合促进剂。这可以通过辊涂方法(辊涂或吻涂)涂布。
实施例1
保护层:PVDF(层厚度:10μm)和im-PMMA(层厚度:50μm)的共挤出物
粘合剂层1:Admer AT1955(层厚度:50μm)
载体膜:PE Dowlex2108G(层厚度:180μm)
粘合剂层4:得自Henke l的双组分体系Liofol LA2692-21和硬化剂UR7395-22
包括阻隔层的聚合物膜:Alcan Cerami s(层厚度12μm)
粘合剂层2:DELO KATIOBOND LP655(层厚度:1μm)
将由聚合物膜、阻隔层和粘合剂层2构成的阻隔复合体与第二阻隔复合体层合。
粘合剂层3:等同于粘合剂层4
构造:参见图1
实施例2
耐刮擦涂层:CRYSTALCOATTM MP-100(层厚度:10μm)
保护层:im-PMMA(层厚度:50μm)
粘合剂层1:Bynel22E780(层厚度:40μm)
载体膜:PP Clyrell RC124H(层厚度:200μm)
粘合剂层4:62%Laromer UA9048V、31%己二醇二丙烯酸酯、2%甲基丙烯酸羟乙酯、3%I rgacure184、2%丙烯酸丁酯(层厚度:10μm)
聚合物膜:双轴拉伸的PET(Hos taphan RNK层厚度12μm)
阻隔层:SiO1.5
粘合剂层2:60%Laromer UA9048V、30%己二醇二丙烯酸酯、2%甲基丙烯酸羟乙酯、3%Irgacure184、2%丙烯酸丁酯、4%甲基丙烯酰氧基丙基三甲氧基硅烷(层厚度:1μm)
粘合剂层3:等同于粘合剂层4
粘合剂层5:得自Et imex的EVA Vis tasolar486.00(层厚度:200μm)
构造:参见图2
实施例3
耐刮擦涂层:UVHC3000K(层厚度:15μm)
保护层:im-PMMA(层厚度:70μm)
粘合剂层1:Bynel22E780(层厚度:30μm)
载体膜:得自Eastman的PET Tritan FX100(层厚度:180μm)
粘合剂层4:得自Henkel的双组分体系Liofol LA2692-21和硬化剂UR7395-22
聚合物膜:双轴拉伸的PET(Hos taphan RNK,层厚度12μm)
阻隔层:Al2O3
粘合剂层2:DELO KATIOBOND LP VE19663(层厚度:0.8μm)
首先将由聚合物膜、阻隔层和粘合剂层2构成的阻隔复合体与第二阻隔复合体层合,然后与第三阻隔复合体层合。
粘合剂层3:等同于粘合剂层4
阻隔性能的测量
根据ASTM F-1249在23℃/85%相对湿度下测量膜体系的水蒸气透过率。
根据DIN61730-1和IEC60664-1或DIN EN60664-1测量局部放电电压。
对比实施例:
根据现有技术(EP1018166B1)的膜,例如具有50μm的层厚度的SiOx涂覆的ETFE具有0.7g/(m d)的水蒸气透过率。
具有4个阻隔复合体的本发明膜具有小于0.01g/(m d)的水蒸气透过率(参见实施例3)。
实施例中的%数据总是表示wt%。
附图标记列表
A 载体层合体
B 阻隔层合体的总和
(1) 耐刮擦涂层
(2) 保护层
(3) 载体膜
(4) 聚合物膜
(5) 阻隔层
(6) 重复的阻隔层合体
(a1) 粘合剂层1
(a2) 粘合剂层2
(a3) 粘合剂层3
(a4) 粘合剂层4
(a5) 粘合剂层5
权利要求书(按照条约第19条的修改)
1.膜层合体,其特征在于所述膜层合体至少由以下组成:
a)从外到内至少由PMMA保护层、粘合剂层粘合剂1和载体膜组成的气候稳定性载体层合体,
b)至少一个粘合剂层粘合剂4和
c)包括至少三个改进对水蒸气和氧气的阻隔作用的无机氧化物层的阻隔层合体。
2.根据权利要求1的膜层合体,其特征在于所述粘合剂层粘合剂1是乙烯-丙烯酸酯热熔体并且所述载体膜是聚酯膜或聚烯烃膜。
3.根据权利要求1或2中至少一项的膜层合体,其特征在于所述载体膜具有100-400μm的厚度,所述粘合剂层粘合剂1具有20-80μm的厚度,所述PMMA层具有50-400μm的厚度。
4.根据权利要求1-3中至少一项的膜层合体,其特征在于所述PMMA层具有耐刮擦涂层。
5.根据权利要求1的膜层合体,其特征在于所述阻隔层合体至少由至少三个聚合物膜、至少三个无机氧化物层和由粘合剂2和/或粘合剂3构成的至少两个粘合剂层组成。
6.根据权利要求5的膜层合体,其特征在于所述聚合物膜是具有5-50μm的厚度的聚酯膜或聚烯烃膜。
7.根据权利要求1-6中至少一项的膜层合体,其特征在于所述无机氧化物层是具有1.3-1.7的x值的SiOx层,和所述氧化物层各自具有10-100nm的厚度。
8.根据权利要求1-6中至少一项的膜层合体,其特征在于所述无机氧化物层是具有1.2-1.5的x值的AlOx层,和所述氧化物层各自具有10-100nm的厚度。
9.根据权利要求1-8中至少一项的膜层合体,其特征在于所述阻隔层合体具有的构造为:PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET、PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET或PET-SiOx-粘合剂2-SiOx-PET-SiOx-粘合剂2-SiOx-PET。
10.根据权利要求1-9中至少一项的膜层合体,其特征在于所述膜层合体从外到内具有的构造为:载体层合体、粘合剂层粘合剂4和阻隔层合体,和粘合剂层粘合剂5被涂布在所述阻隔层合体的底侧上。
11.根据权利要求1的膜层合体,其特征在于它具有至少1000V的局部放电电压和在大于300nm范围内大于80%的透明度。
12.制备根据权利要求1的膜层合体的方法,其特征在于
a)利用真空蒸气涂覆或溅镀无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少两个另外的无机涂覆的膜接合,并利用层合、挤出层合或挤出涂覆将所得的阻隔层合体与根据权利要求2的耐候性载体膜组合,或
b)利用真空蒸气涂覆或溅镀双面无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少一个另外的无机涂覆的膜接合,并利用层合、挤出层合或挤出涂覆将所得的阻隔层合体与根据权利要求2的耐候性载体膜组合,或
c)利用真空蒸气涂覆或溅镀双面无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少一个另外的双面无机涂覆的膜接合,并利用挤出涂覆将所得的膜复合体与根据权利要求2的耐候性载体膜组合,和
d)在a)-c)中所述的物理真空蒸气涂覆中,利用电子束使硅的氧化物或铝的氧化物蒸发,或
e)在a)-c)中所述的物理真空蒸气涂覆中,利用热使硅的氧化物或铝的氧化物蒸发。
13.根据权利要求1的膜层合体用于包装工业、显示技术中和用于有机LED的用途。
14.根据权利要求1的阻隔膜用于有机光生伏打器件、薄层光生伏打器件和结晶硅模块中的用途。
Claims (15)
1.膜层合体,其特征在于所述膜层合体至少由以下组成:
a)包括至少一个PMMA层的至少三层的气候稳定性载体层合体,
b)至少一个粘合剂层粘合剂4和
c)包括至少三个改进对水蒸气和氧气的阻隔作用的无机氧化物层的阻隔层合体。
2.根据权利要求1的膜层合体,其特征在于所述载体层合体从外到内至少由PMMA保护层、粘合剂层粘合剂1和载体膜组成。
3.根据权利要求2的膜层合体,其特征在于所述粘合剂层粘合剂1是乙烯-丙烯酸酯热熔体并且所述载体膜是聚酯膜或聚烯烃膜。
4.根据权利要求2或3中至少一项的膜层合体,其特征在于所述载体膜具有100-400μm的厚度,所述粘合剂层粘合剂1具有20-80μm的厚度,所述PMMA层具有50-400μm的厚度。
5.根据权利要求1-4中至少一项的膜层合体,其特征在于所述PMMA层具有耐刮擦涂层。
6.根据权利要求1的膜层合体,其特征在于所述阻隔层合体至少由至少三个聚合物膜、至少三个无机氧化物层和由粘合剂2和/或粘合剂3构成的至少两个粘合剂层组成。
7.根据权利要求6的膜层合体,其特征在于所述聚合物膜是具有5-50μm的厚度的聚酯膜或聚烯烃膜。
8.根据权利要求1-7中至少一项的膜层合体,其特征在于所述无机氧化物层是具有1.3-1.7的x值的SiOx层,和所述氧化物层各自具有10-100nm的厚度。
9.根据权利要求1-7中至少一项的膜层合体,其特征在于所述无机氧化物层是具有1.2-1.5的x值的AlOx层,和所述氧化物层各自具有10-100nm的厚度。
10.根据权利要求1-8中至少一项的膜层合体,其特征在于所述阻隔层合体具有的构造为:PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET、PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET-粘合剂3-PET-SiOx-粘合剂2-SiOx-PET或PET-SiOx-粘合剂2-SiOx-PET-SiOx-粘合剂2-SiOx-PET。
11.根据权利要求1-10中至少一项的膜层合体,其特征在于所述膜层合体从外到内具有的构造为:载体层合体、粘合剂层粘合剂4和阻隔层合体,和粘合剂层粘合剂5被涂布在所述阻隔层合体的底侧上。
12.根据权利要求1的膜层合体,其特征在于它具有至少1000V的局部放电电压和在大于300nm范围内大于80%的透明度。
13.制备膜层合体的方法,其特征在于
a)利用真空蒸气涂覆或溅镀无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少两个另外的无机涂覆的膜接合,并利用层合、挤出层合或挤出涂覆将所得的阻隔层合体与根据权利要求2的耐候性载体膜组合,或
b)利用真空蒸气涂覆或溅镀双面无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少一个另外的无机涂覆的膜接合,并利用层合、挤出层合或挤出涂覆将所得的阻隔层合体与根据权利要求2的耐候性载体膜组合,或
c)利用真空蒸气涂覆或溅镀双面无机地涂覆聚合物膜,并利用粘合剂层将这种膜与至少一个另外的双面无机涂覆的膜接合,并利用挤出涂覆将所得的膜复合体与根据权利要求2的耐候性载体膜组合,和
d)在a)-c)中所述的物理真空蒸气涂覆中,利用电子束使硅的氧化物或铝的氧化物蒸发,或
e)在a)-c)中所述的物理真空蒸气涂覆中,利用热使硅的氧化物或铝的氧化物蒸发。
14.根据权利要求1的膜层合体用于包装工业、显示技术中和用于有机LED的用途。
15.根据权利要求1的阻隔膜用于有机光生伏打器件、薄层光生伏打器件和结晶硅模块中的用途。
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DE102010038288.4 | 2010-07-22 | ||
DE201010038288 DE102010038288A1 (de) | 2010-07-22 | 2010-07-22 | Transparente, witterungsbeständige Barrierefolie mit verbesserter Barrierewirkung und Kratzfesteigenschaften |
PCT/EP2011/058889 WO2012010361A1 (de) | 2010-07-22 | 2011-05-31 | Transparente, witterungsbeständige barrierefolie mit verbesserter barrierewirkung und kratzfesteigenschaften |
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US (1) | US20130059139A1 (zh) |
EP (1) | EP2595803A1 (zh) |
JP (1) | JP2013539418A (zh) |
KR (1) | KR20130132756A (zh) |
CN (1) | CN103003062A (zh) |
AU (1) | AU2011281877A1 (zh) |
DE (1) | DE102010038288A1 (zh) |
SG (1) | SG187180A1 (zh) |
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DE102013217285A1 (de) * | 2013-08-29 | 2015-03-05 | Robert Bosch Gmbh | Mehrlagige Kunststofffolie |
WO2017126609A1 (ja) * | 2016-01-20 | 2017-07-27 | 凸版印刷株式会社 | 発光体保護フィルム及びその製造方法、並びに波長変換シート及び発光ユニット |
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US20130059139A1 (en) | 2013-03-07 |
KR20130132756A (ko) | 2013-12-05 |
AU2011281877A1 (en) | 2013-03-14 |
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JP2013539418A (ja) | 2013-10-24 |
TW201219225A (en) | 2012-05-16 |
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DE102010038288A1 (de) | 2012-01-26 |
WO2012010361A1 (de) | 2012-01-26 |
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