CN102414023A - 透明的耐候性阻隔膜、通过层合、挤出层合或挤出涂覆的制备 - Google Patents
透明的耐候性阻隔膜、通过层合、挤出层合或挤出涂覆的制备 Download PDFInfo
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- CN102414023A CN102414023A CN201080018105XA CN201080018105A CN102414023A CN 102414023 A CN102414023 A CN 102414023A CN 201080018105X A CN201080018105X A CN 201080018105XA CN 201080018105 A CN201080018105 A CN 201080018105A CN 102414023 A CN102414023 A CN 102414023A
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Abstract
本发明涉及阻隔膜,其中阻隔复合材料(5)借助层合或挤出涂覆与气候老化稳定性的保护层(1)结合,所述阻隔复合材料由两个载体膜(3)构成,所述载体膜各含有无机阻隔层(4)(SiOx或AlOx),其中使用粘合促进剂作为粘合剂层(2)。
Description
技术领域
本发明涉及通过层合、挤出层合(粘合剂层合、熔体层合或热熔体层合)或挤出涂覆制备透明的耐候性阻隔膜。为此,将透明膜复合材料与耐候性透明膜(例如PMMA或PMMA-聚烯烃共挤出物或PMMA-聚酯共挤出物)层合,所述透明膜复合材料由两个外部聚烯烃或聚酯层构成,这两个层各自配备有无机涂层并且与该无机层在内部彼此粘结。该无机氧化物层具有高的透明的对水蒸气和氧气的阻隔性能,而PMMA层带来气候老化稳定性。
背景技术
耐候性的透明且抗冲击性的基于聚甲基丙烯酸酯的膜由本申请人以品名销售。专利DE 38 42 796 A1描述了透明的抗冲击性丙烯酸酯基模塑料的制备,由其制备的膜和模制品和所述模塑料的制备方法。这些膜具有的优点是它们在热和湿气的作用下不变色和/或变脆。另外,它们避免在冲击作用或弯曲应力下所谓的白色裂纹。这些膜是透明的并甚至在热和湿气作用下,在气候作用下和在冲击或弯曲应力下保持这样。
所述模塑料的加工以获得所述透明的抗冲击性膜的过程理想地通过经由宽缝模头挤出熔体并在辊磨机上平整来进行。此种膜表现出永久透明性、对热和冷不敏感性、耐候性、轻微泛黄和变脆并在弯折或折叠时表现出轻微白色裂纹并因此适合作为例如帆布棚、汽车顶板或帆船中的窗体。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、纸板、刨花板、塑料片材等上形成厚度例如为0.02-0.5mm的薄表面层。各种方法可用于制备此类覆盖物。例如,可以挤出所述膜而获得模塑料,平整并与基底层合。利用挤出涂覆技术,可以将挤出的线料施加于基底的表面上并利用辊子平整。如果热塑性塑料用作基底本身,则存在由该发明的透明模塑料形成表面层的情况下所述两种材料的共挤出的可能性。
然而,PMMA膜仅提供对水蒸气和氧气不足够的阻隔性能,而这对用于医疗应用、包装工业中的应用,而且特别是在户外使用中的电气应用中是必要的。
为了改进阻隔性能,将透明的无机层施加于聚合物膜上。特别地,硅氧化物和铝氧化物层已经变得成熟。这种无机氧化物层(SiOx或AlOx)是通过真空涂覆方法施加的(以化学方式,JP-A-10025357、JP-A-07074378;热或电子束蒸发、溅射,EP 1 018 166 B1、JP2000-307136A、WO 2005-029601 A2)。EP 1018166 B1中描述了SiOx层的UV吸收可能受SiOx层的硅与氧之比影响。这对保护位于其下方的层免受UV辐射是重要的。然而,缺点是,随硅与氧的比例的改变,阻隔性能也改变。这样,透明性和阻隔性可能不彼此独立地改变。
无机氧化物层有时候主要施加到聚酯和聚烯烃上,因为这些材料经得起在蒸发过程期间的热应力。此外,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老化不稳定,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。
如从U.Moosheimer,Galvanotechnik 90 No.9,1999,第2526-2531页获知的那样,用无机氧化物层涂覆PMMA不改进对水蒸气和氧气的阻隔性能,因为PMMA是无定形的。然而,与聚酯和聚烯烃相反,PMMA是气候老化稳定的。
在DE 102009000450.5中,申请人使用导致无机层和粘合促进剂之间良好粘附的涂料。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两个相同类型的层之间的粘附更难以达到。
发明内容
目的的提出
本发明所基于的目的是提供气候老化稳定性的且高度透明的(在>300nm的波长范围中>80%)的阻隔膜,其中确保对水蒸气和氧气的高阻隔性能。PMMA满足气候老化稳定性性能,而无机氧化物层满足阻隔性能。
本发明首先具有的目的是将作为载体层的PMMA与无机氧化物层结合。
其次,保护以免受UV辐射的功能将不再由无机氧化物层承担,由此这可以仅仅根据光学标准加以优化,而不是PMMA层的那些。第三,大于1000V的局部放电电压将通过这种材料组合达到。
第四,PMMA层具有保护位于下方的聚烯烃或聚酯层免受气候老化影响的功能。
解决方案
本发明的目的通过对气候老化稳定的阻隔膜达到。所述性能由多层膜达到,其中各个层通过真空气相沉积、层合、挤出层合(粘合剂层合、熔体层合或热熔体层合)或挤出涂覆而彼此结合。为此可以使用常用的方法,例如,S.E.M.Selke,J.D.Culter,R.J.Hernandez,“Plastics Packaging”,第二版,Hanser-Verlag,ISBN 1-56990-372-7,第226和227页所述那样。
因为PMMA的直接无机涂覆根据现有技术是不可能的,所以通过气相沉积为聚酯或聚烯烃膜提供无机层。PMMA层保护聚酯或聚烯烃膜免受气候老化影响。
无机和有机层之间的粘附问题通过将两个经无机涂覆的膜彼此通过粘合剂粘结而规避,其中所述膜具有的无机侧面向内,膜的有机侧面朝外。这然后可以容易地与其它有机聚合物接合。
无机层之间的粘附可以例如采用对于无机层优化的聚氨酯基粘合剂达到。
含有所述两个无机层的膜复合材料可以利用热熔粘合剂与PMMA、抗冲PMMA或包括PMMA或抗冲PMMA和聚烯烃或聚酯的膜复合材料通过挤出层合彼此接合。
所述PMMA层还含有保护聚酯或聚烯烃膜免受UV辐射的UV吸收剂。然而,UV吸收剂还可以存在于聚烯烃或聚酯层中。还可以使用PMMA和聚烯烃的共挤出物代替PMMA层,这具有成本优点,因为聚烯烃比PMMA更经济。
本发明的优点:
●根据本发明的阻隔膜是对气候老化稳定性的。
●根据本发明的阻隔膜是无卤的。
●根据本发明的阻隔膜具有对水蒸气和氧气高的阻隔作用(<0.05g/(m2d))。
●根据本发明的阻隔膜独立于SiOx层的组成地保护位于下方的层免受UV辐射。
●根据本发明的阻隔膜可以经济地制备,因为薄的膜可以用于不连续的无机真空气相沉积的方法。
●根据本发明的阻隔膜可以容易地制备,因为仅必须无机层与无机层彼此接合和有机层与有机层彼此接合。
保护层
优选包含聚甲基丙烯酸甲酯(PMMA)或抗冲PMMA(sz-PMMA)的膜用作保护层。
抗冲改性的聚(甲基)丙烯酸酯塑料
抗冲改性的聚(甲基)丙烯酸酯塑料由20重量%-80重量%,优选30重量%-70重量%聚(甲基)丙烯酸酯基体和80重量%-20重量%,优选70重量%-30重量%弹性体颗粒组成,所述弹性体颗粒的平均颗粒直径是10-150nm(例如使用超离心法测量)。
优选地,所述聚(甲基)丙烯酸酯基体中分布的弹性体颗粒具有包含软弹性体相和与其键合的硬相的核。
抗冲改性的聚(甲基)丙烯酸酯塑料(szPMMA)由一定比例的基体聚合物(由至少80重量%甲基丙烯酸甲酯单元以及非必要的0重量%-20重量%可与甲基丙烯酸甲酯共聚的单体的单元聚合获得)和在该基体中分布的一定比例的抗冲改性剂构成,该抗冲改性剂基于交联的聚(甲基)丙烯酸酯。
所述基体聚合物尤其是由80重量%-100重量%,优选90重量%-99.5重量%经自由基聚合的甲基丙烯酸甲酯单元,和任选的0重量%-20重量%,优选0.5重量%-10重量%能够自由基聚合的其它共聚单体,例如(甲基)丙烯酸C1-C4-烷基酯,尤其是丙烯酸甲酯,丙烯酸乙酯或丙烯酸丁酯构成。优选地,基体的平均分子量Mw(重均)在90000g/mol-200000g/mol,尤其是100000g/mol-150000g/mol的范围内(利用凝胶渗透色谱参照聚甲基丙烯酸甲酯作为校准标准物测定Mw)。例如,分子量Mw的测定可以通过凝胶渗透色谱或通过光散射方法进行(参见例如H.F.Mark等人,Encyclopedia of PolymerScience and Engineering,第2版,第10卷,第1页及后续页,J.Wiley,1989)。
优选由90重量%-99.5重量%甲基丙烯酸甲酯和0.5重量%-10重量%丙烯酸甲酯形成的共聚物。维卡软化温度VET(ISO 306-B50)可以在至少90℃,优选95-112℃的范围内。
抗冲改性剂
聚甲基丙烯酸酯基体含有抗冲改性剂,该抗冲改性剂可以是例如,由两个或三个壳构成的抗冲改性剂。
用于聚甲基丙烯酸酯塑料的抗冲改性剂是充分熟知的。抗冲改性的聚甲基丙烯酸酯模塑料的制备和构成例如,描述在EP-A 0 113 924、EP-A 0 522 351、EP-A 0 465 049和EP-A 0 683 028中。
抗冲改性剂
聚甲基丙烯酸酯基体中含有1重量%-30重量%,优选2重量%-20重量%,尤其优选3重量%-15重量%,尤其是5重量%-12重量%抗冲改性剂,该抗冲改性剂是由交联的聚合物颗粒构成的弹性体相。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,所述颗粒是可利用成珠聚合获得的交联颗粒,它们的平均颗粒尺寸是10nm-150nm,优选20nm-100nm,尤其是30nm-90nm。它们一般由如下物质构成:至少40重量%,优选50重量%-70重量%甲基丙烯酸甲酯,20重量%-40重量%,优选25重量%-35重量%丙烯酸丁酯,和0.1重量%-2重量%,优选0.5重量%-1重量%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0重量%-10重量%,优选0.5重量%-5重量%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。
优选的抗冲改性剂是可以具有两或三层核-壳型结构并通过乳液聚合而获得的聚合物颗粒(参见例如,EP-A 0 113 924、EP-A 0 522 351、EP-A 0 465 049和EP-A 0 683 028)。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10nm-150nm,优选20nm-120nm,尤其优选50nm-100nm的范围内。
具有一个核和两个壳的三层或三相结构可以如下完成。最内(硬)壳可以例如主要由甲基丙烯酸甲酯,低比例的共聚单体,如丙烯酸乙酯,和一定比例的交联剂,如甲基丙烯酸烯丙酯构成。中间的(软)壳可以例如由丙烯酸丁酯和任选的苯乙烯构成,而最外面的(硬)壳基本上大多数与基体聚合物相应,从而导致对基体的相容性和良好接合。聚丙烯酸丁酯在抗冲改性剂中的比例对于抗冲效果是决定性的并优选为20重量%-40重量%,尤其优选25重量%-35重量%。
抗冲改性的聚甲基丙烯酸酯模塑料
可以在挤出机中将抗冲改性剂和基体聚合物在熔体中混合而获得抗冲改性的聚甲基丙烯酸酯模塑料。一般首先将排出的材料切割成粒料。这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。
根据EP 0 528 196 A1的两相抗冲改性剂
尤其是对于膜制备而言,不过并不限于此,优选使用原理上从EP0 528 196 A1获知的体系,该体系是两相抗冲改性的聚合物,其包含:
a1)10重量%-95重量%内聚的、玻璃化转变温度Tmg大于70℃的硬相,其由以下物质构成:
a11)80重量%-100重量%(基于a1)甲基丙烯酸甲酯,和
a12)0重量%-20重量%一种或多种其它能够自由基聚合的烯属不饱和单体,和
a2)90重量%-5重量%分布在硬相中的、玻璃化转变温度Tmg低于-10℃的韧性相,其由以下物质构成:
a21)50重量%-99.5重量%丙烯酸C1-C10烷基酯(基于a2),
a22)0.5重量%-5重量%含两个或更多个能够自由基聚合的烯属不饱和基团的交联单体,和
a23)任选的其它能够自由基聚合的烯属不饱和单体,
其中所述硬相a1)的至少15重量%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而产生,例如,DE-A 38 42 796中所述那样。在第一阶段中,产生韧性相a2),其包含至少50重量%,优选大于80重量%丙烯酸低级烷基酯,从而得到低于-10℃的该相的玻璃化转变温度Tmg。所使用的交联单体a22)是二醇的(甲基)丙烯酸酯,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,带有两个乙烯基或烯丙基的芳族化合物,例如二乙烯基苯,或带有两个烯属不饱和的、能够自由基聚合的基团的其它交联剂,例如甲基丙烯酸烯丙酯,作为接枝交联剂。
可以作为实例提及的带有三个或更多个不饱和的、能够自由基聚合的基团,如烯丙基或(甲基)丙烯酰基的交联剂是氰脲酸三烯丙酯,三羟甲基丙烷三丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯以及季戊四醇四丙烯酸酯和季戊四醇四甲基丙烯酸酯。US 4,513,118中给出了在这方面的其它实例。
在a23)部分中提及的能够自由基聚合的烯属不饱和单体可以例如是丙烯酸或甲基丙烯酸或它们的含1-20个碳原子的烷基酯,只要还没有提到,这里的烷基可以是直链、支链或环状的。另外,a23)可以包含能够自由基聚合并可与丙烯酸烷基酯a21)共聚的其它脂族共聚单体。然而,意于排除相当大比例的芳族共聚单体,如苯乙烯,α-甲基苯乙烯或乙烯基甲苯,因为它们(特别是在气候作用下)导致模塑料A的不希望的性能。
当在第一阶段中产生韧性相时,必须精确注意调节颗粒尺寸及其多分散性。韧性相的颗粒尺寸在此基本上取决于乳化剂的浓度。有利地,可以通过利用种子胶乳控制颗粒尺寸。基于水相,使用0.15-1.0重量%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性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考虑而测定的。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、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盐化的链烷烃。所使用的聚合引发剂是例如,0.01重量%-0.5重量%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至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,由0.01重量%-0.05重量%有机氢过氧化物和0.05-0.15重量%羟甲基亚磺酸钠组成的组合。
至少以15重量%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只由甲基丙烯酸甲酯构成。至多20重量%一种或多种能够自由基聚合的其它烯属不饱和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的用量满足,上述玻璃化转变温度不会达不到。
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。
在一个优选的实施方案中,硬相含有0.1重量%-10重量%,优选0.5重量%-5重量%的量的低分子量和/或经聚合的UV吸收剂,基于作为硬相中的共聚单体组分a 12)的成分的A。对于可聚合UV吸收剂,尤其如US 4 576 870中描述的那样,可以举例提及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。在加工温度下具有低挥发性并与聚合物A的硬相a1)具有均匀混容性的UV吸收剂是尤其优选的。
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,氟化的卤化层也是可能的,例如,PVDF与PMMA的共挤出物或PVDF和PMMA的共混物,但是在此不含卤素的优点将不存在。
保护层具有20μm-500μm的厚度,厚度优选是50μm-400μm,非常尤其优选200μm-300μm。
光稳定剂
根据本发明,可以将光稳定剂添加到载体层中。光稳定剂应理解为是指UV吸收剂、UV稳定剂和自由基清除剂。
任选存在的UV稳定剂是,例如,二苯甲酮的衍生物,其取代基,如羟基和/或烷氧基,多数存在于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。此外,取代的苯并三唑非常适合作为添加的UV稳定剂,其特别包括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、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)]。
除了苯并三唑之外,还可以使用2-(2’-羟苯基)-1,3,5-三嗪,例如酚、2-(4,6-二苯基-1,2,5-三嗪-2-基(xy))-5-(己氧基)类别的UV吸收剂。
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-草酰苯胺、2-乙氧基-5-叔丁基-2′-乙基-草酰苯胺和取代的苯甲酸苯基酯。
光稳定剂或UV稳定剂可以作为低分子量化合物,如上给出的那些,存在于待稳定化的聚甲基丙烯酸酯材料中。然而,UV-吸收性基团也可在与可聚合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酰基衍生物、甲基丙烯酰基衍生物或烯丙基衍生物的共聚后共价地键合于基体聚合物分子内。UV稳定剂(它们也可以是化学上不同的UV稳定剂的混合物)的比例一般是0.01-10重量%,特别是0.01-5重量%,尤其是0.02-2重量%,基于(甲基)丙烯酸酯共聚物。
作为自由基清除剂/UV稳定剂的实例,这里可以提及空间位阻胺,其已知称作HALS(Hindered Amine Light Stabilizer(受阻胺光稳定剂))。它们可在涂料和塑料中,特别是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)。存在于HALS化合物中的四甲基哌啶基团担负起所述化合物的稳定化作用。这类化合物可在哌啶氮上未被取代,也可在其上被烷基或酰基取代。所述空间位阻胺在UV范围内不吸收。它们捕获形成的自由基,UV吸收剂则不能发挥这种作用。起稳定化作用的并且也可以以混合物形式使用的HALS化合物的实例是:
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-羟基乙基-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。
用于根据本发明的聚合物混合物中的自由基清除剂/UV稳定剂的量是0.01-15重量%,特别是0.02-10重量%,尤其是0.02-5重量%,基于(甲基)丙烯酸酯共聚物。
UV吸收剂优选存在于PMMA层中,但是也可以存在于聚烯烃或聚酯层中。
保护层还具有足够的层厚度以确保1000V的局部放电电压。例如,在PMMA情况下,这是自250μm起,这取决于厚度。局部放电电压应理解为是指放电发生时的电压,其部分地桥接绝缘部分(参见DIN EN60664-1)。
载体层
优选由聚烯烃(PE、PP)或聚酯(PET、PET-G、PEN)构成的膜用作载体层。还可以使用由其它聚合物(例如聚酰胺或聚乳酸)构成的膜。载体层具有1μm-100μm的厚度;厚度优选是5μm-50μm,非常尤其优选10μm-30μm。
载体层在>300nm,优选350-2000nm,尤其优选380-800nm的波长范围中具有大于80%,优选大于85%,尤其优选大于90%的透明度。
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,还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)。对于精确的层结构,参见实施例。所使用的SiOx层优选是具有1∶1-1∶2,尤其优选1∶1.3-1∶1.7的硅与氧之比的层。层厚度是5nm-300nm,优选10nm-100nm,尤其优选20nm-80nm。
在AlOx情况下对于x适用的是,0.5-1.5;优选1-1.5,非常尤其优选1.2-1.5的范围(其中x=1.5 Al2O3)。层厚度是5nm-300nm,优选10nm-100nm,尤其优选20nm-80nm。
无机氧化物可以利用物理真空沉积(电子束或热过程)、磁控溅射或化学真空沉积施加。这可以反应性(供应氧气)或非反应性地进行。火焰预处理、等离子预处理或电晕预处理也是可能的。
阻隔复合材料-由2个具有无机涂层的载体层构成
包括2个具有无机涂层(=配备有阻隔层的载体层)的复合材料具有的优点是所述两个无机层被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,用于制备复合材料的粘合剂可以对于无机层而优化。“粘合剂层”部分中描述的配方可以用作粘合剂。聚氨酯基双组分粘合剂在此是优选的。
粘合剂层
粘合剂层存在于保护层和阻隔层之间。它允许这两个层之间的粘附。粘合剂层具有1μm-100μm,优选2μm-50μm,尤其优选2μm-20μm的厚度。粘合剂层可以由随后固化的涂料配方形成。这优选通过UV辐射进行,但是也可以热的方式进行。所述粘合剂层含有1重量%-80重量%多官能甲基丙烯酸酯或丙烯酸酯或其混合物作为主组分。优选使用多官能丙烯酸酯,例如己二醇二甲基丙烯酸酯。为了提高挠性,可以添加单官能丙烯酸酯或甲基丙烯酸酯,例如甲基丙烯酸羟乙酯或甲基丙烯酸月桂酯。另外,粘合剂层任选地含有改进对SiOx粘附的组分,例如含硅氧烷基团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可以按0重量%-48重量%的量存在于粘合剂层中。粘合剂层含有0.1重量%-10重量%,优选0.5重量%-5重量%,尤其优选1重量%-3重量%引发剂,例如184或651。粘合剂层可以还含有0重量%-10重量%,优选0.1重量%-10重量%,尤其优选0.5重量%-5%硫化合物作为调节剂。一个变型是,用0重量%-30重量%预聚物替代一部分主组分。粘合剂组分任选地含有0重量%-40重量%对于粘合剂常用的添加剂。然而,粘合剂层也可以由热熔粘合剂形成。这可以由聚酰胺、聚烯烃、热塑性弹性体(聚酯、聚氨酯或共聚酰胺弹性体)或共聚物构成。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是优选的。粘合剂层可以利用辊涂方法以层合涂布或利用喷嘴以挤出层合或以挤出涂覆涂布。
预聚物应理解为是指通过将单体仅部分聚合而形成的单体-聚合物混合物(参见例如DE10349544A1)。
应用
这种阻隔膜可以用于包装工业、显示技术、有机光致电压技术、薄膜光致电压技术、结晶硅模块和用于有机LED。
具体实施方式
实施例
图1示出了具有保护层-粘合剂层-阻隔复合材料(层合)的实施例
用阻隔层4(例如SiOx)涂覆载体层3(例如PET)。将它与第二SiOx-涂覆的载体层通过辊涂方法利用粘合剂层2’接合。通过层合将保护层1(例如PMMA)施加在这种阻隔复合材料上。例如,丙烯酸酯或甲基丙烯酸酯基粘合促进剂可以用作粘合剂层2用于这种层合。这可以通过辊涂方法(辊涂或吻涂)施加。保护层1的特征在于它含有UV吸收剂。
方法:
1.真空涂覆(PVD、CVD)载体层4
2.通过利用辊涂方法将两个经涂覆载体层粘结而制备阻隔复合材料,借此产生粘合剂层2’
3.利用层合(辊涂方法)借助于是粘合剂层2的粘合促进剂将保护层1施加到阻隔复合材料5上
4.通过UV辐射固化粘合剂层2
图2示出了具有保护层-阻隔复合材料(挤出涂覆)的实施例
用阻隔层4(例如SiOx)涂覆载体层3(例如PET)。将它与第二SiOx-涂覆的载体层通过辊涂方法利用粘合剂层2’接合。通过挤出涂覆将呈熔体状态的保护层1(例如PMMA-PP共挤出物)施加在这种阻隔复合材料上。任选地,所述保护层在阻隔层上的粘附可以通过粘合剂层2,例如丙烯酸酯或甲基丙烯酸酯基粘合促进剂,或热熔粘合剂(例如基于乙烯-丙烯酸酯共聚物)而改进。
保护层1的特征在于它含有UV吸收剂并且它由两个或三个层(PMMA和PP或PMMA、粘合促进剂或热熔粘合剂和PP)构成。
方法:
1.真空涂覆(PVD、CVD)载体层4
2.通过利用辊涂方法将两个经涂覆载体层粘结而制备阻隔复合材料,借此产生粘合剂层2’
3.利用多层挤出涂覆,可能地借助于热熔粘合剂(其是粘合剂层2),将保护层1施加到阻隔复合材料5上。
图3示出了具有保护层-阻隔复合材料-载体层(挤出层合)的实施例
用阻隔层4(例如SiOx)涂覆载体层3(例如PET)。将它与第二SiOx-涂覆的载体层通过辊涂方法利用粘合剂层2’接合。通过挤出层合将保护层1(例如PMMA膜或PMMA和聚烯烃的共挤出物)施加在这种阻隔复合材料5上。例如,热熔粘合剂(例如基于乙烯-丙烯酸酯共聚物)可以用作粘合剂层2用于这种层合。利用模头在阻隔复合材料5和保护层1之间挤出呈熔体状态的这种热熔粘合剂。保护层1的特征在于它含有UV吸收剂。
方法:
1.真空涂覆(PVD、CVD)载体层4
2.通过利用辊涂方法将两个经涂覆载体层粘结而制备阻隔复合材料,借此产生粘合剂层2’
3.在保护层1和阻隔复合材料之间挤出层合呈熔体状态的粘合剂层2
根据本发明的膜的阻隔性能的测量
根据ASTM F-1249在23℃/85%相对湿度下进行膜体系的水蒸气透过率的测量。
根据DIN 61730-1和IEC 60664-1或DIN EN 60664-1进行局部放电电压的测量。
实施例
对比实施例:
根据现有技术(EP 1 018 166 B1)的膜,例如具有50μm的层厚度的SiOx涂覆的ETFE,具有0.7g/(m2d)的水蒸气透过率。
根据本发明的具有50μm的阻隔复合材料5的层厚度的膜具有0.01-0.05g/(m2d)的水蒸气透过率(参见实施例1)。
实施例1
粘合剂层2:62% Laromer UA 9048 V、31%己二醇二甲基丙烯酸酯、2%甲基丙烯酸羟乙酯、3% Irgacure 651、2%3-甲基丙烯酰氧基丙基三甲氧基硅烷
阻隔复合材料5由以下层构成:
载体层3:PET Mitsubishi Hostaphan RN12,层厚度:12μm。
阻隔层4:利用电子束真空蒸发施加的SiO1.5,层厚度:40nm。
粘合剂层2’:双组分体系Liofol LA 2692-21和得自Henkel的固化剂UR 7395-22
实施例2
粘合剂层2:62% Laromer UA 9048 V、31%己二醇二丙烯酸酯、2%甲基丙烯酸羟乙酯、3% Irgacure 184、2%丙烯酸丁酯
阻隔复合材料5由以下层构成:
载体层3:PEN,层厚度:20μm
阻隔层4:Al2O3,层厚度40nm,利用磁控溅射施加。
粘合剂层2’:60% Laromer UA 9048 V、30%己二醇二丙烯酸酯、2%甲基丙烯酸羟乙酯、3% Irgacure 184、2%丙烯酸丁酯、4%甲基丙烯酰氧基丙基三甲氧基硅烷
实施例3
粘合剂层2:62% Ebecryl 244、31%己二醇二丙烯酸酯、2%甲基丙烯酸羟乙酯、3% Irgacure 651、2% Glymo
阻隔复合材料5由以下层构成:
载体层3:PET,层厚度23μm。
阻隔层4:SiO1.7,层厚度80nm,利用磁控溅射施加。
粘合剂层2’:70%己二醇二丙烯酸酯、17%季戊四醇四丙烯酸酯、5%甲基丙烯酸甲酯、2%Irgacure 184、2%甲基丙烯酸羟乙酯、2%甲基丙烯酰氧基丙基三甲氧基硅烷
实施例4
保护层1:抗冲PMMA(例如Plex 8943F)的共挤出物,层厚度40μm,含有1.5%UV吸收剂360和聚乙烯(例如Dowlex SC 2108G),层厚度200μm。粘合促进剂:Dupont Bynel 22 E 780(乙烯-丙烯酸酯共聚物)。
粘合剂层2:Dupont Bynel 22 E 780
阻隔复合材料5由以下层构成:
载体层3:PET Mitsubishi Hostaphan RN75,层厚度75μm
阻隔层4:SiO1.7,层厚度80nm,利用电子束真空蒸发施加。
粘合剂层2’:双组分体系Liofol LA 2692-21和得自Henkel的固化剂UR 7395-22
实施例中的%数据总是重量%。
参考标记列表
1保护层
2粘合剂层
2’阻隔复合材料5的粘合剂层
3载体层
4阻隔层
5阻隔复合材料
Claims (9)
1.阻隔膜,其由气候老化稳定性的保护层和阻隔复合材料构成,其中所述保护层对气候老化是稳定性的并且所述阻隔复合材料含有改进对水蒸气和氧气的阻隔作用的两个无机氧化物层。
2.根据权利要求1的阻隔膜,其特征在于它是无卤的。
3.根据权利要求1的阻隔膜,其特征在于它具有至少1000V的局部放电电压。
4.根据权利要求1的阻隔膜,其特征在于它在大于300nm的范围内具有大于80%的透明度。
5.根据权利要求1的阻隔膜,其特征在于在所述阻隔复合材料和所述保护层之间存在由具有以下组成的粘合促进剂形成的粘合剂层:
a)1重量%-80重量%单或多官能丙烯酸酯或甲基丙烯酸酯
b)0重量%-30重量%预聚物
c)0重量%-48重量%含硅氧烷基团的丙烯酸酯或甲基丙烯酸酯
d)0.1重量%-10重量%至少一种引发剂
e)0重量%-10重量%至少一种调节剂
f)0重量%-40重量%常用的添加剂。
6.根据权利要求1的阻隔膜,其特征在于所述无机阻隔层和所述保护层之间存在由热熔粘合剂形成的粘合剂层。
7.制备阻隔膜的方法,其特征在于
a)利用真空蒸发或溅射为载体膜(聚烯烃、聚酯)提供无机涂层并利用粘合剂层将这种膜与具有无机涂层的另一个膜接合,并利用层合将这样产生的膜复合材料与气候老化稳定性的塑料膜(PMMA,PMMA和聚烯烃的共挤出物)结合,或
b)利用真空蒸发或溅射为载体膜(聚烯烃、聚酯)提供无机涂层并利用粘合剂层将这种膜与具有无机涂层的另一个膜接合,并利用挤出层合将这样产生的膜复合材料与气候老化稳定性的塑料膜(PMMA,PMMA和聚烯烃的共挤出物)结合,或
c)利用真空蒸发或溅射为载体膜(聚烯烃、聚酯)提供无机涂层并利用粘合剂层将这种膜与具有无机涂层的另一个膜接合,并利用挤出涂覆将这样产生的膜复合材料与气候老化稳定性的塑料膜(PMMA,PMMA和聚烯烃的共挤出物)结合,和
d)在7a)-c)中所提及的物理真空蒸发中利用电子束使SiO蒸发,或
e)在7a)-c)中所提及的物理真空蒸发中使SiO热蒸发。
8.根据权利要求1的阻隔膜在包装工业、显示技术中和用于有机LED的用途。
9.根据权利要求1的阻隔膜在有机光致电压技术、薄膜光致电压技术和结晶硅模块中的用途。
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- 2009-05-19 DE DE200910003225 patent/DE102009003225A1/de not_active Withdrawn
-
2010
- 2010-04-28 CN CN201080018105XA patent/CN102414023A/zh active Pending
- 2010-04-28 WO PCT/EP2010/055660 patent/WO2010133427A1/de active Application Filing
- 2010-04-28 MA MA34356A patent/MA33483B1/fr unknown
- 2010-04-28 SG SG2011067675A patent/SG174882A1/en unknown
- 2010-04-28 KR KR1020117027535A patent/KR20120014161A/ko not_active Application Discontinuation
- 2010-04-28 MX MX2011012180A patent/MX2011012180A/es active IP Right Grant
- 2010-04-28 EP EP10716337A patent/EP2432638A1/de not_active Withdrawn
- 2010-04-28 BR BRPI1013032A patent/BRPI1013032A2/pt not_active IP Right Cessation
- 2010-04-28 US US13/259,155 patent/US20120021236A1/en not_active Abandoned
- 2010-04-28 AU AU2010251358A patent/AU2010251358A1/en not_active Abandoned
- 2010-04-28 JP JP2012511221A patent/JP2012527361A/ja active Pending
- 2010-04-28 CA CA2762599A patent/CA2762599A1/en not_active Abandoned
- 2010-05-14 TW TW99115476A patent/TW201119853A/zh unknown
-
2011
- 2011-09-09 TN TN2011000462A patent/TN2011000462A1/fr unknown
- 2011-09-11 IL IL215070A patent/IL215070A0/en unknown
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108198869A (zh) * | 2017-12-06 | 2018-06-22 | 中国乐凯集团有限公司 | 一种柔性太阳能电池用封装膜 |
CN113748016A (zh) * | 2019-03-27 | 2021-12-03 | 阿贝尔服务 | 用于形成挠性容器的层压材料和包括所述层压材料的挠性管裙 |
CN113748016B (zh) * | 2019-03-27 | 2023-06-02 | 阿贝尔服务 | 用于形成挠性容器的层压材料和包括所述层压材料的挠性管裙 |
CN110497671A (zh) * | 2019-08-06 | 2019-11-26 | 安徽天润医用新材料有限公司 | 一种高阻隔复合层医用输液袋及其生产方法 |
CN110497671B (zh) * | 2019-08-06 | 2021-05-11 | 安徽天润医用新材料有限公司 | 一种高阻隔复合层医用输液袋及其生产方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201119853A (en) | 2011-06-16 |
DE102009003225A1 (de) | 2010-11-25 |
CA2762599A1 (en) | 2010-11-25 |
SG174882A1 (en) | 2011-11-28 |
US20120021236A1 (en) | 2012-01-26 |
EP2432638A1 (de) | 2012-03-28 |
TN2011000462A1 (en) | 2013-03-27 |
IL215070A0 (en) | 2011-11-30 |
AU2010251358A1 (en) | 2011-10-13 |
KR20120014161A (ko) | 2012-02-16 |
MA33483B1 (fr) | 2012-08-01 |
WO2010133427A1 (de) | 2010-11-25 |
BRPI1013032A2 (pt) | 2019-09-24 |
JP2012527361A (ja) | 2012-11-08 |
MX2011012180A (es) | 2011-12-08 |
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