CN103415556B - 耐水解性聚酯膜 - Google Patents
耐水解性聚酯膜 Download PDFInfo
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- CN103415556B CN103415556B CN201280011977.2A CN201280011977A CN103415556B CN 103415556 B CN103415556 B CN 103415556B CN 201280011977 A CN201280011977 A CN 201280011977A CN 103415556 B CN103415556 B CN 103415556B
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- polyester
- film
- hydrolysis stabilizer
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- polyester films
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Abstract
一种包含聚酯和至少一种选自支链单羧酸的缩水甘油酯中的水解稳定剂的双轴取向聚酯膜,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述膜中,以及其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过所述水解稳定剂与所述聚酯的端基反应获得所述反应产物。
Description
技术领域
本发明涉及聚酯膜,尤其是聚对苯二甲酸乙二酯(PET)膜,其表现出改善的耐水解性,并涉及其生产方法。
背景技术
聚酯膜优越的机械性能、尺寸稳定性和光学性能是众所周知的。然而,聚酯膜易受水解降解,而导致这种聚合物的本征粘度降低,并因此导致所述膜的一种或多种上述所需的性能,尤其是机械性能劣化。较差的耐水解性在膜用于潮湿条件下和/或升高的温度下和/或在外部应用,如光伏(PV)电池中时尤其问题重重。
为了提高聚酯膜的耐水解性,已知将水解稳定剂并入到膜中。例如,在US-5885709和EP-0838500等中提出了在聚酯组合物中添加碳二亚胺作为封端剂,但这样的添加剂具有排放有害气体副产物的倾向。US-2003/021914-A1报道了使用聚合的碳二亚胺作为水解稳定剂降低气体产生的倾向。US-2002/0065346-A1教导了选自酚类化合物、噁唑啉和/或单体或聚合的碳二亚胺的水解稳定剂可选地与有机亚磷酸酯/盐组合。GB-1048068教导了使用有机羧酸的铜盐作为水解稳定剂。US-3657191和US-3869427教导了通过与碳酸亚乙酯或单官能缩水甘油醚反应的聚酯端基的改性。通过使用含端部环氧基团的化合物稳定的耐水解聚酯也公开于EP-0292251-A中。在EP-1209200中报道了缩水甘油酯和缩水甘油醚的组合在促使缩水甘油基和羧基之间的反应的催化剂存在下提高聚酯的耐水解性,但是该公开内容只涉及结晶远快于PET的聚对苯二甲酸丁二醇酯(PBT)以及其在生产注塑成型材料中的应用。US-6498212公开了聚酯,其中水解稳定性通过使用选自环氧乙烯-丙烯酸乙酯共聚物、环氧苯乙烯-丁二烯-苯乙烯嵌段共聚物和氨基聚乙烯共聚物中的聚合物封端剂而提高。在聚酯组合物中使用环氧化脂肪酸烷基酯(如环氧化硬脂酸2-乙基-己基酯)和/或环氧化脂肪酸甘油酯(如环氧化大豆油或环氧化亚麻籽油)作为水解稳定剂公开于CA-2514589-A、US-4540729、US-5589126、US-7229697、US-7241507、US-2005/0137299-Al、US-2007/0238816-A1和US-2007/0237972-A1中。其它改善聚对苯二甲酸乙二酯(PET)膜的水解稳定性的方法包括同步控制参数,如本征粘度、二乙二醇含量和结晶度,如在EP-0738749-A中公开的。控制本征粘度和结晶度,结合抗氧化剂的存在,报道于EP-0620245-A中,因为改善高温(180℃)老化特性,而不损害用作电动马达和电容内绝缘材料的聚酯膜的平面内分层性质。US-4115350和US-4130541教导,聚酯与单羧酸、酰胺和硫代酸的环氧化烷基酯的反应产物会改善纤维和由其制成的绳(软线,cord)的热稳定性。US-3372143教导,聚酯与环氧化烷氧基醚或芳氧基醚的反应产物提高由其制得的纤维的可着色性。
与将水解稳定剂并入聚酯膜相关的问题之一是尽管提高添加剂浓度能够改进耐水解性,但这样做是以聚酯膜熔点的降低和聚酯膜机械性能的劣化为代价的。机械性能降低的后果之一是成膜聚酯的可加工性变差,而膜网的破裂会发生于制作和后续加工期间。
基于环氧化脂肪酸,尤其是环氧化脂肪酸甘油酯的水解稳定剂用于现有技术的聚酯膜中的另一个问题在于这种添加剂在膜制作和加工期间具有发生分解而产生丙烯醛这种剧毒、易燃、恶臭物质的倾向。
使用已知的水解稳定剂,尤其是基于某些环氧化脂肪酸甘油酯和多官能缩水甘油基化合物的那些水解稳定剂的其它问题是,当这种添加剂按照改善耐水解性的有效量并入所述膜中时会降低膜质量和可加工性能。具体而言,这种添加剂会导致聚酯膜中剖面缺陷和不可接受水平的分模线,即,横跨膜网的厚度和/或光透射的均一性较差,而挤出物因为膜网破裂可能变成不能够于膜线(film-line)上处理。认为这样的问题至少部分可归咎于交联和凝胶形成,这会干扰其制作期间膜所经历的拉伸过程。对于使用多官能缩水甘油基化合物作为PET的水解稳定剂的进一步问题是,其较高的聚酯链延伸速率会提高熔体粘度,这进而又降低给定温度下的挤出量,而这是经济上不划算的。虽然粘度理论上可以通过升高熔体温度而降低,但这将导致聚合物和水解稳定剂的降解速率加快并导致凝胶形成。凝胶形成在其它聚酯产品如注塑成型PBT产品的生产中并不太成问题,部分是因为这些产品相比于聚酯膜厚度要大得多。
发明内容
本发明的目的是提供可替换的耐水解聚酯膜,尤其是其中耐水解性改善,尤其是其中膜可以在不产生有毒副产物的情况下进行制作和使用,尤其是在保持或改善膜制作的方便性、效率和经济性的同时而不会增加膜破裂,尤其是其中分模线和剖面缺陷水平得以降低,尤其不会损害膜的机械和/或光学性质。
根据本发明,提供了一种包含聚酯(优选聚对苯二甲酸乙二酯)和至少一种选自支链单羧酸的缩水甘油酯中的水解稳定剂的双轴取向聚酯膜,其中单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于膜中,以及其中聚酯膜进一步包含选自由第I族和第II族金属阳离子组成的组中的金属阳离子。
在本发明中,在催化该反应的第I族或第II族金属阳离子存在下,通过水解稳定剂与聚酯的端基的反应获得所述反应产物。
根据本发明进一步的方面,提供了一种包含聚酯(优选聚对苯二甲酸乙二酯)和至少一种选自支链单羧酸的缩水甘油酯的水解稳定剂的双轴取向聚酯膜,其中单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于膜中,以及其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过水解稳定剂与聚酯的端基的反应获得所述反应产物。
本发明中所用的水解稳定剂通过与聚酯的羧基端基和/或羟基端基反应而起到聚酯的端基封端剂的作用,并且认为主要反应是与羧基端基的反应。羧基端基已经证实主要进行包括聚对苯二甲酸乙二酯的聚酯的水解降解。水解稳定剂的缩水甘油基在升高的温度下快速与聚酯的端基发生反应,而重要的是,在改性聚酯生产期间或随后的生产和聚酯膜的使用期间,与此一起进行有毒副产物的零消除。水解稳定剂易于充分并入到聚酯中。
金属阳离子按照足以催化水解稳定剂和至少一些所述聚酯的端基之间的反应的催化活性量存在。
在优选的实施方式中,金属阳离子存在于膜中,和/或存在于反应混合物中的量,在水解稳定剂与聚酯的端基反应期间,相对于生成的聚酯量,为按重量计至少40ppm,优选至少45ppm,优选至少65ppm,优选至少80ppm,且优选至少100ppm。优选地,相对于聚酯的量,金属阳离子的量按重量计不超过约1000ppm,优选不超过约500ppm,优选不超过约275ppm,通常不超过约200ppm,在一个实施方式中不超过约150ppm。优选地,相对于聚酯的量,金属阳离子的量按重量计在45ppm-500ppm,更优选65ppm-275ppm,更优选100ppm-200ppm的范围内。
在可替换的实施方式中,金属阳离子存在于膜,和/或存在于反应混合物中的量,在水解稳定剂与聚酯的端基反应期间,相对于生成的聚酯量,为按重量计至少10ppm,优选至少15ppm,优选至少35ppm,优选至少50ppm,优选至少70ppm。在该实施方式中,相对于聚酯的量,金属阳离子的量通常不超过按重量计约1000ppm,不超过约500ppm,优选不超过约250ppm,通常不超过约150ppm,在一个实施方式中不超过约100ppm。在该实施方式中,相对于聚酯的量,金属阳离子的量按重量计优选在15ppm-500ppm,更优选35ppm-250ppm,更优选70ppm-150ppm的范围内。
正如本文中所用,术语“第I族”和“第II族”具有其常规化学意义并且是指周期表中相应的族。在优选的实施方式中,金属阳离子是第I族金属阳离子,优选钠或钾,优选钠。
认为催化效果是由于阳离子,因此,催化剂相应的阴离子可以是任何合适的带负电荷的分子或原子。在一个实施方式中,阴离子选自氢氧根、聚丙烯酸根、碳酸氢根、羧酸根、氯离子、乙酸根、甲酸根和硝酸根。在优选的实施方式中,阴离子选自氢氧根或聚丙烯酸根。适宜的聚丙烯酸根是具有分子量约1,000至约10,000的那些。
聚酯膜是自保持膜(自持膜,self-supportingfilm)或自保持薄片(自持薄片),其是指不存在支持基材(supportingbase)时能够独立存在的膜或薄片。
所述聚酯膜的聚酯优选聚对苯二甲酸乙二酯或聚萘二甲酸乙二酯,更优选聚对苯二甲酸乙二酯,但其也可以包含相对少量的一种或多种衍生于其它二羧酸和/或二醇的残余物。其它二羧酸包括间苯二甲酸,邻苯二甲酸,1,4-萘二甲酸、2,5-萘二甲酸、2,6-萘二甲酸或2,7-萘二甲酸,4,4′-联苯二甲酸,六氢对苯二甲酸,1,10-癸二甲酸和通式为CnH2n(COOH)2的脂族二羧酸,其中n为2-8,如琥珀酸、戊二酸、癸二酸、己二酸、壬二酸、辛二酸或庚二酸。其它二醇包括脂族和脂环族二醇,如1,4-环己烷二甲醇。优选聚酯膜只包含一种二羧酸,即对苯二甲酸。优选聚酯只包含一种二醇,即乙二醇。聚酯树脂是膜的主要组分,占膜总重量的按重量计至少50%,优选至少65%,优选至少80%,优选至少90%,优选至少95%。
膜由其制成的聚酯的本征粘度优选至少约0.65,优选至少约0.70,优选至少约0.75,优选至少约0.80。
聚酯的形成按照已知的缩合或酯交换方式,一般在可达约295℃的温度下方便实施。在优选的实施方式中,使用本领域公知的常规技术,例如使用诸如氮流化床或使用旋转真空干燥机的真空流化床的流化床,固态聚合可以用于将本征粘度提高至所需的值。
相对于膜的总重量,水解稳定剂优选以在约0.1%至约5%,更优选约0.1%至约2.5%,更优选约0.1%至约2.0%,更优选约0.3%至约1.75%,更优选约0.3%至约1.5%的范围内的量存在。
水解稳定剂由其衍生的支链单羧酸具有5-50个碳原子,优选5-25个碳原子,优选5-15个碳原子,优选8-12个碳原子,优选9-11个碳原子,在一个实施方式中,具有10个碳原子。单羧酸优选是饱和的,即,分子中的碳-碳键是单键。支链单羧酸优选其中邻近羧基的碳原子(以下简称为“α-碳”原子)是叔碳原子,即,它经由三个碳-碳单键连接至3个除了羧基碳原子以外的碳原子,而所述3个碳原子中的每一个可以是亚烷基或烷基的部分。单羧酸优选合成材料,即,它是通过根据常规方法包含至少一个合成步骤的有机合成方法制备的(请参阅例如WO-01/56966-A1),而不是可能需要从天然物质中分离出来的天然产生的材料(如脂肪酸)。
本发明中所用的水解稳定剂可以通过表氯醇与所需的支链单羧酸的已知反应而制成。该反应可以使用常规酸或碱催化剂,如碱金属羧酸盐和季铵卤化物,通常在升高的温度(通常是50-120℃范围内的温度)下进行。
在一个实施方式中,聚酯膜中使用单一水解稳定剂,而在优选的实施方式中,可以使用本文中定义的水解稳定剂的混合物,在这种情况下水解稳定剂的总浓度处于上述范围之内。由于以上所给出的原因,优选根据本发明在不存在其它水解稳定剂的情况下(即,不存在不是支链单羧酸的缩水甘油酯的水解稳定剂),在一个实施方式中不存在缩水甘油醚化合物,尤其是二缩水甘油醚化合物或聚缩水甘油醚化合物的情况下使用本文中所述的缩水甘油酯。在一个实施方式中,本文中所述的聚酯膜基本上由聚对苯二甲酸乙二酯和至少一种选自支链单羧酸的缩水甘油酯中的水解稳定剂构成。在本发明的一个实施方式中,本发明中所用的水解稳定剂基本上由至少一种支链单羧酸的缩水甘油酯构成。
在一个实施方式中,水解稳定剂具有下式(I):
其中:
R1和R2独立地选自烷基,优选R1和R2中至少一个(在一个实施方式中仅一个)选自甲基;
R3选自氢和烷基,优选烷基;以及
其中在烷基R1、R2和R3中碳原子总数为3-48,优选3-23,优选3-13,优选6-10,优选7-9,在一个实施方式中为8。
在一个实施方式中,使用水解稳定剂的混合物,每一种根据式(I)独立选择,在一个实施方式中使混合物的每种组分中的烷基R1、R2和R3的碳原子总数相同。
在优选的实施方式中,R1选自甲基,R2和R3独立地选自烷基,其中在烷基R2和R3中的碳原子总数为2-47,优选2-22,优选2-12,优选5-9,优选6-8,在一个实施方式中为7。在一个实施方式中,使用这些优选的水解稳定剂的混合物,优选使混合物的每种组分中烷基R1、R2和R3中的碳原子总数相同。
如本文中所用的,术语“烷基”优选是指式[-CnH2n+1]的未取代直链无环烃基。
水解稳定剂,例如以上式(I)的化合物,可以表现出手性,在这种情况下水解稳定剂可以作为对映体或对映体的混合物存在。
在一个实施方式中,根据ASTMD445测定,水解稳定剂在20℃下优选具有小于100mPa.s,优选小于50mPa.s,优选小于25mPa.s的粘度。
本发明中所用的水解稳定剂与聚酯在升高的温度,通常约160℃-300℃下发生反应,且以快速的反应时间进行,通常在290℃下远小于1s。
水解稳定剂可以在制膜过程期间的各个阶段引入,即:
1、通过在由其单体生产聚酯期间加入添加剂,这一般将会在聚合过程结束时进行。在挤出成为丸粒之前立即进行。在一个实施方式中,改性聚酯随后可以进一步通过固态聚合进行处理以将IV提高至所需值。
2、通过将聚酯片熔融,并将熔体与添加剂混合而使添加剂与聚酯片离线反应,随后将改性聚酯再挤出并粒化成片。
3、通过将添加剂(通常其中添加剂是液体)在将聚合物引入到制膜过程中所用的挤出机中之前或期间加入到聚合物片中(例如,通过将添加剂加入到挤出机料斗中的聚合物中),然后挤出该混合物,使添加剂和聚酯在挤出机(通常是双螺杆挤出机)中一起反应。
4、通过将添加剂(通常其中添加剂是液体)注入到挤出过程所产生的熔体聚合物(即,一旦聚合物在挤出机,通常是双螺杆挤出机中处于熔体状态,通常在聚合物已通过任何液化区之后)中,但在将聚合物浇铸成膜之前。
5、通过在由其单体生产聚酯期间加入添加剂,这优选在聚合过程结束,直接挤出成膜之前进行。直接挤出过程本文中称为“耦合(coupled)聚合膜生产”或“强耦合(紧密耦合,嵌合耦合,close-coupled)聚合膜生产”,其中造粒的中间步骤被省略,这是特别有利的。强耦合过程可以采用聚合反应器和成膜模具之间的静态或动态混合设置进行操作,其中所述混合在加入水解稳定剂之后进行。静态和动态混合***在本领域中是常规的。在静态混合设置中,固定组件的设置在熔体流(melt-stream)流过混合机时连续掺混物料。合适的动态混合***包括挤出机或其它阿基米德螺旋***。在本发明优选的实施方式中,紧密耦合过程采用静态混合设置操作,本发明人出乎意料地观察到,达到本发明益处的充分混合仅采用静态混合设置就可以获得。出乎意料的是,适用于该***的强耦合过程能够免除动态混合而不损害最终的膜性能。在强耦合过程中,可以,并且优选避免影响固态聚合步骤。强耦合过程降低存在于聚合物中的水量,从而避免对膜形成前的干燥步骤的需求,并且还降低存在于聚合物基质中可以与水解稳定剂发生反应的水量。降低的水含量使得能够避免干涉固态聚合步骤,并使得聚酯膜能够耐受更高的羧基端基含量而不会损失水解稳定性。因此,在该实施方式中,羧基端基的含量通常在约15×l0-6至约50×l0-6毫当量/g(meq/g),通常约20×10-6至约40×l0-6毫当量/g的范围内,而典型的SSP过程将羧基端基含量降低至小于约15×l0-6meq/g,通常约10×10-6meq/g。羧基含量通过在聚合物溶解于热苄醇(苯甲醇)中之后用氢氧化钠滴定进行测定。
在一个实施方式中,水解稳定剂通过以上途径(2)、(3)和(4)中的一种,优选通过途径(4)引入。在一个实施方式中,母料通过相对于最终膜中所需量加入过量的水解稳定剂进行生产,这对于以上工艺途径(2)特别有用。在进一步优选的实施方式中,水解稳定剂通过途径(5)引入。
在本发明中,金属阳离子可以在加入水解稳定剂之前或同时加入到聚酯或其单体中。可替换地,金属阳离子可以在将水解稳定剂加入到聚酯或其单体中之前或同时加入到所述水解稳定剂中。优选金属阳离子加入到聚酯或单体中,优选在向其中加入水解稳定剂之前。在优选的实施方式中,金属阳离子在制备聚酯的聚合反应开始时加入。
本发明人出乎意料地观察到,使用工艺途径(4)改善了产品性能,尤其是通过该途径制作的膜证实相对于采用具有以上途径(2)的母料技术生产的膜改善了水解稳定性。认为在挤出工艺过程中向聚酯中相对较晚地加入水解稳定剂使得由制膜期间热降解所致的羧基端基的增加最小化。此外,途径(4)相对于母料途径的优点,例如,在于它使得能够更充分地利用回收膜(即,制膜过程的废膜,例如,由展幅阶段之后为了提供均匀宽度的膜而通常进行的“切边”所产生)。回收聚酯通常比原始聚酯片具有较低的本征粘度,较高浓度的羧基端基,而相对较晚加入水解稳定剂使得原始聚酯和回收聚酯都产生稳定作用。使用更高水平的回收聚酯同时提供改善的水解稳定性是本发明的独特优点。
在改善的水解稳定性方面,使用工艺途径(5)也观察到出乎意料的改善的产品性能。
在一个实施方式中,膜可以另外具有UV吸收剂。UV吸收剂具有远高于聚酯的消光系数,使得大部分入射UV光被UV吸收剂吸收而不是由聚酯吸收。UV-吸收剂一般以热耗散所吸收的能量,从而避免聚合物链的降解,提高聚酯对UV光的稳定性。通常,UV吸收剂是有机UV吸收剂,合适的实例包括公开于Kirk-Othmer的《EncyclopaediaofChemicalTechnology》,第三版,JohnWiley&Sons,第23卷,第615页至第627页中的那些。UV吸收剂的具体实例包括二苯甲酮、苯并***(US-4684679、US-4812498和US-4681905)、苯并噁嗪酮(US-4446262、US-5251064和US-5264539)、和三嗪(US-3244708、US-3843371、US-4619956、US-5288778和WO94/05645)。UV吸收剂可以根据本文所描述的方法中的一种并入到膜中。在一个实施方式中,UV吸收剂可以化学并入到聚酯链中。EP-A-0006686、EP-A-0031202、EP-A-0031203和EP-A-0076582,例如,描述了将二苯甲酮引入聚酯中。关于UV-吸收剂的上述文献的具体教导并入本文中作为参考。在特别优选的实施方式中,本发明中改善的UV稳定性通过三嗪,更优选羟苯基三嗪,特别是式(II)的羟苯基三嗪化合物提供:
其中R是氢、C1-C18烷基、由卤素或C1-C12烷氧基取代的C2-C6烷基,或者是苄基,R1是氢或甲基。优选R为C1-C12烷基或苄基,更优选C3-C6烷基,尤其是己基。R1优选是氢。特别优选的UV-吸收剂是2-(4,6-联苯基-l,3,5-三嗪-2-基)-5-(己基)氧基-苯酚,这可以从Ciba-Additives作为TinuvinTM商购获得。
UV-吸收剂的用量,相对于膜的总重量,优选在按重量计0.1%-10%,更优选0.2%-7%,更优选0.6%-4%,尤其是0.8%-2%,尤其是0.9%-1.2%的范围内。
膜优选还包含抗氧化剂。各种抗氧化剂都可以使用,如通过捕获自由基或分解过氧化物起作用的抗氧化剂。合适的自由基捕获抗氧化剂包括受阻酚,仲芳胺和受阻胺,如TinuvinTM770(Ciba-Geigy)。适合的分解过氧化物的抗氧化剂包括三价磷化合物,如亚膦酸酯,亚磷酸酯(例如,磷酸三苯酯和三烷基亚磷酸酯)和硫代增效剂(例如,硫代二丙酸的酯,如硫代二丙酸二月桂酯)。受阻酚抗氧化剂是优选的。尤其优选的受阻酚是四-(亚甲基-3-(4′-羟基-3′,5′-二-叔丁基苯基丙酸酯)甲烷,其为市售的IrganoxTM1010(Ciba-Geigy)。其它合适的市售受阻酚包括IrganoxTM1035、1076、1098和1330(Ciba-Geigy),SantanoxTMR(Monsanto),CyanoxTM抗氧化剂(AmericanCyanamid)和GoodriteTM抗氧化剂(BFGoodrich)。存在于聚酯膜中的抗氧化剂优选在聚酯的50ppm-5000ppm的范围内,更优选在300ppm-1500ppm的范围内,尤其是在400ppm-1200ppm的范围内,特别是在450ppm-600ppm的范围内。可以使用多于一种抗氧化剂的混合物,在这种情况下,其总浓度优选在上述范围内。将抗氧化剂并入到聚酯中可以通过常规技术,优选通过与聚酯由其衍生的单体反应物混合,尤其是在直接酯化或酯交换反应结束时,缩聚之前进行。
膜可以进一步包含聚酯膜制作中常规采用的任何其它添加剂。因此,诸如交联剂、染料、填料、颜料、空隙剂、润滑剂、自由基清除剂、热稳定剂、阻燃剂和抑制剂、抗粘连剂、表面活性剂、滑动助剂,光泽改良剂、助降解剂、粘度调节剂和分散稳定剂的试剂都可以适当并入。这种组分可以按照常规方式引入到聚合物中。例如,通过与该成膜聚合物由其衍生的单体反应物混合,或者这些组分可以与聚合物通过滚筒或干混或通过在挤出机中混炼(复合)而进行混合,然后通过冷却,通常粉碎成颗粒或碎片。母料技术也可以采用。
具体而言,膜可以包含颗粒填料,其可以改善制作期间的处理和可卷绕性,并且可以用于调节光学性质。颗粒填料,例如,可以是颗粒无机填料(例如,金属或类金属氧化物,如氧化铝、二氧化钛、滑石和二氧化硅(尤其是沉淀的或硅藻土和硅胶),煅烧的瓷粘土和碱金属盐,如钙和钡的碳酸盐和硫酸盐)。任何现有的无机填料应进行精细化,其体积分布中值粒径(等效球体直径相当于所有颗粒体积的50%,在与颗粒直径的体积%相关的累积分布曲线上读取—通常被称为“D(v,0.5)”值)优选在0.01-5μm,更优选0.05-1.5μm,尤其是0.15-1.2μm的范围内。优选按体积计至少90%,更优选至少95%的无机填料颗粒在体积分布中值粒径±0.8μm,尤其是±0.5μm的范围内。填料颗粒的粒径可以通过电子显微镜、库尔特计数器、沉降分析和静态或动态光散射进行测定。基于激光衍射的技术是优选的。中值粒径可以通过绘制表示低于所选择粒径的颗粒体积的百分比的累积分布曲线和测定第50百分位(percentile)而确定。
聚酯膜的形成可以通过本领域众所周知的常规挤出技术进行。在一般情况下,工艺过程包括以下步骤:在约280至约300℃范围内的温度下挤出熔体聚合物层,冷激(骤冷,quenching)挤出物并使经冷激的挤出物取向。取向可以通过任何本领域已知用于生产取向膜的方法,例如管式或平板膜法进行。双轴取向通过在膜平面内的两个相互垂直的方向上拉伸膜以达到机械和物理性能的良好组合而进行。在管式方法中,同时双轴取向可以通过挤出热塑性聚酯管,随后冷激,再加热,然后通过内部气体压力膨胀以诱导横向取向,并按照将会诱导纵向取向的速率拉制而进行。在优选的平板膜方法中,成膜聚酯挤出通过狭缝模,并在冷浇铸转鼓上冷激以确保聚酯被冷激至无定形状态。随后取向通过在高于聚酯的玻璃化转变温度的温度下在至少一个方向上拉伸经冷激的挤出物进行。连续取向可以通过首先在一个方向,通常是纵向方向上,即,通过膜拉伸机的正向方向,然后在横向方向上拉伸平坦冷激的挤出物。挤出物的正向拉伸在旋转辊的组或在两对夹辊之间很方便地进行,横向拉伸随后在展幅装置中进行。通常进行拉伸以使取向膜的尺寸为其在拉伸方向或每一个拉伸方向上的原始尺寸的2-5倍,更优选2.5-4.5倍。通常,拉伸在高于聚酯的Tg的温度,优选高于Tg约15℃的温度下进行。如果仅在一个方向上需要取向,则可以使用较大的拉伸比(例如,可达约8倍)。在机器方向和横向等量拉伸是没有必要的,但是如果需要平衡的性能,则这是优选的。
拉伸膜可以,优选通过在高于聚酯的玻璃化转变温度而低于其熔化温度的温度下,在尺寸支持下热固化进行尺寸稳定,以诱导聚酯的所需结晶。在热固化期间,少量的尺寸松弛可以在横向方向(TD)上通过已知为“前束(toe-in)”的方法和步骤进行。前束可以包括2%-4%级别的尺寸收缩,但在工艺过程或机器方向(MD)上类似的尺寸松弛很难实现,因为需要低线张力,并且膜控制和卷绕变得问题重重。实际的热固温度和时间将根据膜的组成及其所需的最终热收缩而变化,但不应选择以使之显著劣化膜的韧性如耐撕裂性的热固温度和时间。在这些限制中,热固温度为约180-245℃通常是可取的。在一个实施方式中,热固温度在约200至约225℃的范围内,这会提供意想不到的水解稳定性改善。经过热固化之后,膜通常快速冷激以产生聚酯的所需结晶。
在一个实施方式中,膜可以通过使用在线松弛阶段进一步稳定。可替换地,松弛处理可以离线进行。在此另外的步骤中,膜在低于热固阶段温度的温度下加热,并施加大大降低的MD和TD张力。膜经受的张力是低张力,通常小于5kg/m膜宽度,优选小于3.5kg/m膜宽度,更优选在1至约2.5kg/m膜宽度的范围内,通常在1.5-2kg/m膜宽度的范围内。对于控制膜速度的松弛工艺,膜速度的降低(因此应变松弛)通常在0-2.5%,优选0.5-2.0%的范围内。在热稳定化步骤期间膜的横向尺寸没有增加。用于热稳定化步骤的温度可以根据最终膜的所需性质的组合而变化,较高的温度会提供较好的,即,较低的残余收缩性能。135-250℃的温度一般是合乎需要的,优选150-230℃,更优选170-200℃。加热的持续时间将取决于所用的温度,但通常在10-40s的范围内,优选20-30s的持续时间。这种热稳定化工艺可以通过多种方法,包括平面和垂直结构和作为独立工艺步骤的“离线”方法或作为制膜工艺延续的“在线”方法。由此处理的膜将表现出比不存在这样的后热固松弛的情况下产生更小的热收缩。
聚酯膜的厚度优选在约5至约500μm的范围内,更优选不超过约250μm,通常为约37μm-150μm。
在一个实施方式中,膜不透明,这种膜尤其适用于作为PV-电池中的底板。不透明膜优选表现出至少0.4,优选至少0.5,优选至少0.6,优选至少0.7,优选至少1.0,且优选至少1.5的透光密度(TOD),在一个实施方式中优选至少2.0,优选至少3.0,优选至少4.0的透光密度。不透明膜可以按需着色,在本发明的一个实施方式中,本发明的膜是白色的、灰色的或黑色的。任何合适的遮光剂和/或增白剂都可以使用,这在本领域是已知的。
在进一步的实施方式中,膜是白色的,其可以通过向其中并入有效量的增白剂的影响。合适的增白剂包括颗粒无机填料,如本文以上涉及的那些,不相容的树脂填料,或者两种或更多种这种填料的混合物。优选增白剂是颗粒无机填料,优选二氧化钛和/或硫酸钡,在优选的实施方式中填料仅为硫酸钡。并入膜中的无机填料的量通常基于该层中聚酯的重量在按重量计5%-30%,优选按重量计10%-25%的范围内。白色膜优选表现出的白色指数,按照本文的描述测定,在约80至约120单位的范围内。白色膜通常表现出的TOD在0.4-1.75的范围内,优选至少0.5,优选至少0.6,优选至少0.7。
在可替换的实施方式中,膜是灰色或黑色的,通常表现出的TOD为至少2.0,更通常为至少3.0,更通常为至少4.0,这可以通过向其中并入有效量的遮光剂,如碳黑或金属填料如铝粉而达到,这在本领域是已知的。碳黑是优选的遮光剂。通常,这种膜含有基于聚酯重量的按重量计约0.3%至约10%,优选0.5%-7%,尤其是1%-5%,尤其是2%-4%的遮光剂。遮光剂合适地具有0.01-1.5μm,尤其是0.02-0.05μm的平均粒径。这种不透明膜可以可选地含有增白剂。
在优选的实施方式中,聚酯膜是半透明或光学透明的。如本文中的定义,光学透明膜具有的散射可见光%(浊度(haze))不超过30%,优选不超过15%,优选不超过10%,优选不超过6%,更优选不超过3.5%,尤其是不超过1.5%,和/或光的总透射率(TLT)在可见光区(400-700nm)为至少80%,优选至少85%,更优选至少约90%,优选的光学透明膜同时都表现出这些浊度和TLT标准。半透明膜可以具有至少50%,优选至少60%,优选至少70%的TLT。在该实施方式中,在膜中的任何填料主要目的都是为了改善膜的处理,通常只按照少量,一般不超过聚酯的按重量计约0.5%,优选低于按重量计约0.3%的量存在,而且通常选自二氧化硅和滑石,优选二氧化硅。二氧化钛也可以应用于该实施方式中,例如以根据需要调节膜的半透明度,并也通常只按照少量,一般不超过聚酯的按重量计约1.0%,更通常不超过按重量计约0.5%,优选不超过按重量计约0.3%的量存在。在该实施方式中,膜的可卷绕性(即,当膜卷绕成辊时不存在阻塞或粘着)得以改善,没有不可接受的浊度或其它光学性能的降低。
聚酯膜的本征粘度优选为至少0.65,优选至少0.7,在一个实施方式中在约0.65至约0.75的范围内。使用具有相对较高的本征粘度的聚酯膜提供改善的水解稳定性。
在一个实施方式中,聚酯膜的聚酯在(A)℃的温度下表现出吸热高温峰和在(B)℃的温度下表现出吸热低温峰,两峰都通过差示扫描量热法(DSC)进行测定,其中(A-B)的值在15℃-50℃的范围内,优选15℃-45℃的范围内,更优选15℃-40℃的范围内,在一个实施方式中在20℃-40℃的范围内,这一特性可以按照本文的公开通过控制所用的具体聚酯的热固温度而获得。本文所公开的范围内表现出(A-B)值的优势在于获得水解稳定性出乎意料的改善。
聚酯膜优选表现出低收缩率,在150℃下在30min内优选小于3%,优选小于2%,优选小于1.5%,优选小于1.0%,尤其是在膜,尤其是双轴取向膜的机器方向(纵向尺寸)上,优选这种低收缩率值同时表现在膜的两种尺寸(即,纵向和横向尺寸)上。
除了表现出改善的耐水解性之外,本发明的聚酯膜相对于现有技术的膜,尤其是包括含有环氧化脂肪酸甘油酯的水解稳定剂的那些,还表现出膜均匀性和质量的出乎意料的改善。具体而言,本发明的膜表现出几乎没有剖面缺陷和/或分模线;改善的厚度均匀性和通过膜网的透光率;以及改善的可加工性,在膜网中没有缺陷或破损。
在一个实施方式中,如上所述的膜可以具有一个或多个设置于其一个或两个表面上的附加层,以形成复合结构,例如,以提供另外的机械强度或电绝缘性。这种复合结构的形成可通过共挤出来进行,通过各成膜层同时共挤出通过多孔模具的独立孔,此后汇聚仍处于熔融状态的层,或者优选地,通过其中各聚合物的熔体流首先汇集于引导至模具歧管的通道中,随后在流线流的条件下从模具孔口一起挤出而不相互混合以由此产生多层膜,这种多层膜可以按照本文此前的描述进行取向和热固。其它形成多层膜的方法包括两个或多个预成形层的层压,和成膜层在基础层一个或两个表面上的涂覆。涂覆可以使用任何合适的涂覆技术进行,包括凹版辊涂法、逆辊涂布、浸涂、珠涂、挤出涂布、熔融涂层或静电喷涂法。任何涂覆步骤优选避免使用有机溶剂,优选“在线”进行,即,其中,涂覆步骤发生于制膜期间和任何采用的拉伸操作之前、期间或之间。
任何附加层优先选自衍生于本文以上所述的二羧酸和二醇的聚酯,而优先选自PET或基于PET的聚酯。任何附加层可以包含任何以上提及的添加剂,尤其是一种或多种独立选自水解稳定剂、UV-吸收剂、抗氧化剂和颗粒有机填料的添加剂,其中在任何附加层中的添加剂可以与本文以上所述的本发明的膜中的任何这种添加剂相同或不同,其中所述添加剂,特别是水解稳定剂可以与以上描述的那些相同或不同。附加层具有的厚度优选在约50至约500μm的范围内,更优选不超过约250μm,通常为约100-250μm,优选为约100-150μm。
在本发明的一个实施方式中,本文以上所述的膜在其第一表面上设置有一个附加聚合物层,优选在所述膜的第二表面上无任何另外的层。在该实施方式中,本发明的膜优选是不透明膜或白色膜,而附加聚合物层优选透明,浊度不超过约30%,通常不超过约20%,在一个实施方式中不超过约15%。根据本发明的该实施方式的膜尤其适用于用作PV电池中的底板。
本发明的膜适合用于任何其中水解稳定性苛刻的环境中,例如在潮湿条件下和升高的温度下,以及适用于外部应用中,在此方面尤其感兴趣的是光伏(PV)电池。PV电池是多层组件,通常包括前基板、电极层、光伏活性层和底板。染料敏化的PV电池尤其感兴趣,其中活性光吸收层包含受吸收入射光激发的染料。本发明的膜尤其适用于用作PV电池的前基板或底板,或作为其上存在的一个层,尤其是底板。
根据本发明进一步的方面,提供了包含前基板、电极层、光伏活性层和底板的光伏电池,其中前基板和/或底板包含本发明的膜,尤其是其中至少底板包含本发明的膜。
根据本发明进一步的方面,提供了包含前基板(其可以是柔性聚合物前基板或玻璃前基板)、电极层、光伏活性层和底板的光伏电池,通常其中电极层和光伏活性层封装于本领域已知的合适密封剂(如乙烯醋酸乙烯酯(EVA)树脂基质)中,其中底板包含本发明的膜,优选其中所述膜是不透明或白色膜,优选其中所述膜在其第一表面上设置有附加聚合物层,优选在所述膜的第二表面上没有任何另外的层,其中所述附加聚合物层优选是透明的,具有的浊度不超过约30%,通常不超过约20%,在一个实施方式中不超过约15%。在这种PV电池中,本发明的膜处于多层组件的最外层且通常暴露于环境,所述附加聚合物层,例如,使用合适的粘合剂如EVA,层压于光伏活性层。
根据本发明进一步的方面,提供了一种用于制作本文中定义的包含聚酯(优选聚对苯二甲酸乙二酯)的双轴取向聚酯膜的方法,其中所述方法包括:
(i)挤出熔体聚酯(优选聚对苯二甲酸乙二酯)和选自支链单羧酸的缩水甘油酯中的水解稳定剂的层,优选其中所述挤出温度在约280至约300℃的范围内(更优选在约285至约290℃的范围内),其中单羧酸具有5-50个碳原子,其中水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于挤出物中,其中聚酯进一步包含选自由第I族和第II族金属阳离子组成的组中的金属阳离子和/或其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过水解稳定剂与聚酯的端基反应获得反应产物;
(ii)冷激挤出物;
(iii)在两个相互垂直的方向上拉伸经冷激的挤出物;以及
(iv)优选在通过在约200至约225℃范围的温度下热固化进行稳定的温度范围内的温度下热固化所述膜。
根据本发明进一步的方面,提供了一种改善双轴取向聚酯膜的耐水解性的方法,所述方法包括将聚酯(优选聚对苯二甲酸乙二酯)与至少一种选自支链单羧酸的缩水甘油酯的水解稳定剂发生反应的步骤,其中单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于膜中,其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过水解稳定剂与聚酯的端基反应获得所述反应产物。所述方法进一步包括以下步骤:按照本文的描述制作所述双轴取向的聚酯膜,具体而言包括本文以上涉及的挤出、冷激、拉伸和热固步骤(i)-(iv)的步骤。
根据本发明进一步的方面,提供了选自由第I族和第II族金属阳离子组成的组中的金属阳离子的用途,尤其是其中所述用途是所述金属阳离子作为催化剂的用途,其目的是改善包含至少一种选自支链单羧酸的缩水甘油酯中的水解稳定剂的双轴取向聚酯膜(优选聚对苯二甲酸乙二酯)的耐水解性,其中单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于膜中,其中在第I族或第II族金属阳离子存在下,通过水解稳定剂与聚酯的端基反应获得所述反应产物。
根据本发明进一步的方面,提供了选自由第I族和第II族金属阳离子组成的组中的金属阳离子的用途,尤其是其中所述用途是所述金属阳离子作为催化剂的用途,结合使用选自支链单羧酸的缩水甘油酯中的水解稳定剂,目的是改善双轴取向聚酯膜(优选聚对苯二甲酸乙二酯)的耐水解性,其中单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于膜中,其中在第I族或第II族金属阳离子存在下,通过水解稳定剂与聚酯的端基反应获得所述反应产物。
根据本发明进一步的方面,提供了本文中定义的膜或复合结构作为光伏电池中的底板的用途。
性质测定
以下分析用于表征本文中所述的膜:
(i)透明度通过使用M57D球面浊度计(DiffusionSystems)根据标准测试方法ASTMD103测定通过膜的整个厚度的总透光率(TLT)和浊度(%散射的透射可见光)进行评价。
(ii)透光密度(TOD)使用Macbeth密度仪TR927(获自DentandWoodsLtd,Basingstoke,UK)按照透过模式测定。
(ⅲ)白度指数(whitenessindex)使用ColorgardSystem2000,Model/45(PacificScientific制造)和ASTMD313的原理进行测定。
(iv)本征粘度(以dL/g为单位)根据ASTMD5225-98(2003)通过溶液粘度测定法在ViscotekTMY-501C相对粘度计(参见,例如,Hitchcock,Hammons&YauinAmericanLaboratory(August1994)“Thedual-capillarymethodformodern-dayviscometry”)上通过使用按重量计0.5%聚酯在邻氯苯酚中的溶液在25℃下和使用计算本征粘度的Billmeyer单点方法测定:
η=0.25ηred+0.75(lnηrel)/c
其中:
η=本征粘度(以dL/g计),
ηrel=相对粘度,
c=浓度(以g/dL计),以及
ηred=降低的粘度(以dL/g计),其等于(nrel-1)/c(也表示为ηsp/c,其中ηsp是比粘度)。
(v)膜的耐水解性通过在高压釜测试中加速老化进行评价。膜的样品切成10mm宽的条带,并放置于121℃和1.2巴的压力下操作的高压釜中。随后在不同时间间隔下测定与聚合物老化有关的属性。具体而言,聚酯的拉伸强度(脆性)作为聚合物的断裂伸长率(ETB)进行测定。并未老化的膜通常表现出100%以内的ETB值。在一般情况下,膜在其最终使用直至其ETB值减少到小于10%的时间点内仍是有用的。本发明优选的膜在本文中所述的加速老化测试中,在121℃和1.2巴的压力下至少56h,优选至少60h,优选至少64h,优选至少68h,优选至少72h,优选至少76h,优选至少84h,优选至少88h和更优选至少92h之后表现出的ETB为至少10%。
(vi)断裂伸长率根据测试方法ASTMD882进行测定。使用直边和校准的样品切割器(10mm+\-0.5mm),沿着机器方向切下5个膜条带(100mm长)。每个样品采用Instron型号3111材料试验机,使用具有橡胶颚面(jawface)的气动操作夹进行测试。控制温度(23℃)和相对湿度(50%)。十字头速度(分离速率)为25mm·min-1。应变速率为50%。这通过夹具之间的初始距离(样品长度)除以分离速率进行计算。设备记录每一样品断裂时的伸长率。断裂伸长率定义为:
(断裂时的伸长量/L0)×100
其中L0是夹具之间的试样的原始长度。
(vii)根据ISO4892-2测试聚酯膜的耐候性。
(viii)热收缩率对于尺寸200mm×10mm的膜样品进行评价,在相对于膜的机器方向和横向的特定方向切割样品并对视觉测量结果进行标记。样品的较长尺寸(即,200mm尺寸)对应于膜收缩率测试的方向,即,对机器方向上的收缩率进行评价,测试样品的200mm尺寸沿着膜的机器方向取向。在将样品加热到150℃的预定温度(通过放置于该温度下的加热烘箱中),并保持30min的时间间隔,将其冷却至室温,并重新手动测量其尺寸。热收缩率经过计算,表示为原始长度的百分比。
(ix)使用PerkinElmerDSC7仪获得差示扫描量热(DSC)扫描。重5mg的聚酯膜样品封装到标准PerkinElmer铝质DSC坩埚中。将膜和坩埚压平以确保所述膜部分压在一起,以最小化加热期间取向松弛的影响。将试样放置于仪器的样品固定器上,并以80℃/min从30℃加热至300℃以记录相关的扫描线。使用干燥的惰性吹扫气体(氮)。DSC仪的温度和热流轴线针对实验条件,即,针对升温速率和气体流速进行完全校准。采集峰温度的值,即,吸热高温峰(A)和吸热低温峰(B),作为从每个吸热熔化过程开始至每个吸热熔化过程结束所绘制的基线之上的最大位移。峰温测量采用PerkinElmer软件内的标准分析方法获得。测量的精度和准确度为±2℃。样品曲线图如图1所示。
本发明参照图1进行示出,这是对于根据本发明的聚酯膜获得的典型DSC扫描(热流-温度)。图1中标记的峰(A)是具有250℃的值的吸热高温峰,标记(B)的峰是具有220℃的值的吸热低温峰,因此值(A-B)为(250-220)=30℃。
本发明通过下列实施例进一步地示出。这些实施例并非旨在限制如上文所述的本发明。可以做出细节改变而不脱离本发明范围。
具体实施方式
实施例
对照1;比较例1和2;实施例1-12
第一系列的聚酯膜通过将CarduraTME10P(HexionSpecialtyChemicals,Ohio,US;密度0.97g/cm3)作为水解稳定剂,以预先确定的流速(0、800或960mL/h)直接计量加入膜线(film-line)双螺杆挤出机中的PET熔体流中,即,在聚酯处于熔融状态之后,正如下表1中所示,以提供具有不同含量的水解稳定剂的最终膜。PET的流速为93.3kg/h。PET含有用量为0、250、500或1000ppm(按重量计,相对于产生的最终聚合物的重量)的DispexG40(Ciba/BASF;丙烯酸共聚物的钠盐;作为40%固体含量的含水分散体供给),这在聚合过程开始时连同对苯二甲酸和乙二醇一起加入。PET聚合物还含有含量为聚酯的按重量计0.3wt%的TiO2,以及含量为聚酯的按重量计0.3wt%的SiO2。PET聚合物片具有的本征粘度为0.79。
将该混合物在285℃下熔体挤出,浇铸到冷却的旋转鼓上,并在86℃的温度下在挤出方向上拉伸至其原始尺寸的约2.9倍。冷却的拉伸膜随后传递到110℃温度下的拉幅炉(stenteroven)中,在其中膜被干燥并在侧向方向拉伸至其原始尺寸的约3.4倍。双轴拉伸膜在220℃或232℃的温度下热固。所得到的膜的最终厚度为50μm。膜半透明,TLT为76%,浊度为66%。膜的耐水解性通过在加速老化之前和之后测定其断裂伸长率进行评价,正如本文中的定义。最终膜中水解稳定剂的量可以通过1HNMR(D2-1,1,2,2-四氯乙烷作为溶剂;在80℃下的GSX-Δ400仪)进行测定。
表1中的结果表明,水解稳定剂提高聚酯膜的耐水解性,甚至在没有通过Dispex添加剂提供的钠离子存在下也是如此(这在比较例1和2与对照1进行比较时是显而易见的),但也表明,在加入通过Dispex添加剂提供的钠离子之后观察到耐水解性甚至更大的改善(例如,当实施例1-3相比于比较例1时,这是显而易见的)。
在根据上述本发明的所有实施例中,膜的均匀性和膜的质量都是优异的,分模线或剖面缺陷水平非常低;在膜模具周围没有检测到异味;所有膜证实具有良好的可加工性。
比较例3和4;实施例13-20
除了PET聚合物含有500ppm在聚合过程开始时加入的IrganoxTM1010(Ciba-Geigy)而不含TiO2或SiO2之外,采用上述方法制备第二系列的聚酯膜,所述膜是光学透明的。PET含有用量为500ppm(按重量计,相对于产生的最终聚合物的重量)的在聚合过程开始时加入的DispexG40。膜的耐水解性按照之前进行测定,结果示出于表2中。这些数据表明对于本发明的无填料的膜也表现出水稳定剂和金属阳离子组合出乎意料的效果。该第二系列的膜一般表现出的耐水解性优于第一系列的膜,本发明人将这种差异归咎于第二系列中填料的缺乏,因为填料颗粒能够充当导致较大易脆性的额外结晶的成核剂。
比较例5;实施例21
在这些实施例中,聚合和制膜过程经由按照如本文以上所述的强耦合设置的静态混合器连接。PET聚合物通过对苯二甲酸二甲酯(DMT)和乙二醇发生酯交换和在真空下根据标准技术聚合而制备。Dispex添加剂在聚合阶段之前以500ppm的量注入到单体流中。Cardura添加剂在聚合反应器之后以在最终聚合物中提供0.5wt%的量注入到聚合物流中。除了最终膜厚度为125μm而结晶器温度为228℃之外,另外一般地根据以上所述的方法制作膜。结果示出于表3中。
Claims (61)
1.一种包含聚酯和至少一种水解稳定剂的双轴取向聚酯膜,所述至少一种水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述膜中,以及其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过所述水解稳定剂与所述聚酯的端基的反应获得所述反应产物。
2.一种包含聚酯和至少一种水解稳定剂的双轴取向聚酯膜,所述至少一种水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述膜中,以及其中所述聚酯膜进一步包含选自由第I族金属阳离子组成的组中的金属阳离子。
3.根据权利要求1所述的聚酯膜,其中所述金属阳离子选自由第I族金属阳离子组成的组中。
4.根据权利要求1、2或3所述的聚酯膜,其中所述金属阳离子是钠阳离子。
5.根据权利要求1-3中任一项所述的聚酯膜,其中在所述水解稳定剂与所述聚酯的端基反应期间存在于所述膜中,和/或存在于反应混合物中的所述金属阳离子的量,相对于聚酯的量,为按重量计至少45ppm。
6.根据权利要求1-3中任一项所述的聚酯膜,其中在所述聚酯膜中的所述聚酯的本征粘度为至少0.65。
7.根据权利要求1-3中任一项所述的聚酯膜,其中所述水解稳定剂相对于层的总重量以0.1%-2.0%范围内的量存在。
8.根据权利要求1-3中任一项所述的聚酯膜,其中在所述聚酯膜中的所述水解稳定剂由至少一种支链单羧酸的缩水甘油酯组成。
9.根据权利要求1-3中任一项所述的聚酯膜,其中所述支链单羧酸具有5-15个碳原子,和/或其中所述支链单羧酸是饱和的,和/或所述支链单羧酸是合成材料。
10.根据权利要求1-3中任一项所述的聚酯膜,其中所述水解稳定剂通过表氯醇与所述支链单羧酸反应而制备。
11.根据权利要求1-3中任一项所述的聚酯膜,其中所述水解稳定剂具有式(I):
其中:
R1和R2独立地选自烷基,R1和R2中至少一个选自甲基;
R3选自氢和烷基;以及
其中在所述烷基R1、R2和R3中的碳原子总数为3-48。
12.根据权利要求11所述的聚酯膜,其中R1选自甲基,R2和R3独立地选自烷基,其中所述烷基R2和R3中的碳原子总数为7。
13.根据权利要求1-3中任一项所述的聚酯膜,其中所述水解稳定剂通过在将熔体聚合物浇铸成膜之前将添加剂注入所述聚合物中而与所述聚酯发生反应。
14.根据权利要求1-3中任一项所述的聚酯膜,其中所述聚酯膜进一步包含UV吸收剂。
15.根据权利要求14所述的聚酯膜,其中UV-吸收剂的量相对于层的总重量在按重量计0.1%至10%的范围内。
16.根据权利要求1-3中任一项所述的聚酯膜,其通过在200℃至225℃范围内的温度下热固化而稳定。
17.根据权利要求1-3中任一项所述的聚酯膜,其中所述聚酯膜的所述聚酯在A℃的温度下表现出吸热高温峰而在B℃的温度下表现出吸热低温峰,两峰都通过差示扫描量热法DSC进行测定,其中A-B的值在15℃至50℃的范围内。
18.根据权利要求1-3中任一项所述的聚酯膜,当在121℃和1.2巴的压力下老化至少56h之后,根据ASTMD882进行测定,其表现出至少10%的断裂伸长率。
19.根据权利要求1-3中任一项所述的聚酯膜,其表现出不超过30%的浊度和/或至少50%的TLT。
20.根据权利要求1-3中任一项所述的聚酯膜,其选自由白色膜、黑色膜、和不透明膜组成的组中。
21.根据权利要求1-3中任一项所述的聚酯膜,进一步包含抗氧化剂。
22.根据权利要求1-3中任一项所述的聚酯膜,在其第一表面上设置有附加聚合物层,其中所述附加聚合物层是可选地包含一种或多种独立选自水解稳定剂、UV-吸收剂、抗氧化剂、和颗粒无机填料中的添加剂的聚酯层。
23.根据权利要求1-3中任一项所述的聚酯膜,其中所述聚酯是聚对苯二甲酸乙二酯。
24.根据权利要求1-3中任一项所述的聚酯膜,所述聚酯膜具有设置于其一个或两个表面上的一个或多个附加层,以形成复合结构。
25.根据权利要求24所述的聚酯膜,其中所述一个或多个附加层选自PET或基于PET的聚酯。
26.根据权利要求24所述的聚酯膜,其中所述一个或多个附加层包含至少一种水解稳定剂。
27.根据权利要求26所述的聚酯膜,其中所述一个或多个附加层选自PET或基于PET的聚酯,以及其中所述一个或多个附加层的所述水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述一个或多个附加层中。
28.根据权利要求27所述的聚酯膜,其中所述一个或多个附加层中的所述水解稳定剂是如在权利要求9-12中任一项所限定的。
29.根据权利要求22所述的聚酯膜,其中所述膜是通过各成膜层的共挤出形成的。
30.根据权利要求5所述的聚酯膜,其中所述金属阳离子的量为按重量计至少65ppm。
31.根据权利要求5所述的聚酯膜,其中所述金属阳离子的量为按重量计不超过500ppm。
32.根据权利要求5所述的聚酯膜,其中所述金属阳离子的量为按重量计不超过200ppm。
33.根据权利要求6所述的聚酯膜,其中在所述聚酯膜中的所述聚酯的本征粘度为至少0.7。
34.根据权利要求6所述的聚酯膜,其中在所述聚酯膜中的所述聚酯的本征粘度为至少0.75。
35.根据权利要求6所述的聚酯膜,其中在所述聚酯膜中的所述聚酯的本征粘度为至少0.8。
36.根据权利要求11所述的聚酯膜,其中R1和R2中仅一个选自甲基。
37.根据权利要求11所述的聚酯膜,其中R3选自烷基。
38.根据权利要求11所述的聚酯膜,其中在所述烷基R1、R2和R3中的碳原子总数选自3-13。
39.根据权利要求14所述的聚酯膜,其中所述UV吸收剂是有机UV-吸收剂。
40.根据权利要求14所述的聚酯膜,其中所述UV吸收剂选自二苯甲酮、苯并***、苯并噁嗪酮和三嗪。
41.根据权利要求14所述的聚酯膜,其中所述UV吸收剂选自三嗪。
42.根据权利要求18所述的聚酯膜,其中在121℃和1.2巴的压力下老化至少60h。
43.根据权利要求18所述的聚酯膜,其中在121℃和1.2巴的压力下老化至少64h。
44.根据权利要求18所述的聚酯膜,其中在121℃和1.2巴的压力下老化至少68h。
45.根据权利要求18所述的聚酯膜,其中在121℃和1.2巴的压力下老化至少84h。
46.根据权利要求18所述的聚酯膜,其中在121℃和1.2巴的压力下老化至少92h。
47.根据权利要求22所述的聚酯膜,其中第二层表现出不超过30%的浊度。
48.根据权利要求1-47中任一项所述的聚酯膜作为光伏电池中的层的用途,所述光伏电池包括前基板、电极层、光伏活性层、和底板。
49.根据权利要求48所述的用途,其中所述底板包括所述聚酯膜。
50.一种包含前基板、电极层、光伏活性层、和底板的光伏电池,其中所述前基板和/或所述底板包括根据权利要求1-47中任一项所限定的膜。
51.根据权利要求50所述的光伏电池,其中所述电极层和光伏活性层封装于合适的密封剂中,以及其中所述底板包括根据权利要求1-47中任一项所限定的膜。
52.根据权利要求51所述的光伏电池,其中所述膜是不透明膜或白色膜,其中所述膜在其第一表面上设置有附加聚合物层,其中所述附加层表现出不超过30%的浊度,以及其中所述膜在多层组件的最外层。
53.一种用于制作根据权利要求1所述的双轴取向聚酯膜的方法,其中所述方法包括:
(i)挤出熔体聚酯和至少一种水解稳定剂的层,所述至少一种水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于挤出物中,以及其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过所述水解稳定剂与所述聚酯的端基反应获得所述反应产物;
(ii)冷激所述挤出物;
(iii)在两个相互垂直的方向上拉伸经冷激的所述挤出物;以及
(iv)热固化所述膜。
54.根据权利要求53所述的方法,其中所述双轴取向聚酯膜是如权利要求3-47中任一项所限定的。
55.根据权利要求53或权利要求54所述的方法,其中所述方法进一步包括通过表氯醇与所述支链单羧酸反应而制备所述水解稳定剂的步骤。
56.根据权利要求53或54所述的方法,其中所述水解稳定剂通过在挤出所述层之前将添加剂注入熔体聚合物中而与所述聚酯发生反应。
57.根据权利要求53或54所述的方法,其中所述膜具有设置于其一个或两个表面上的一个或多个附加层,以形成复合结构,以及其中所述方法包括各成膜层的共挤出。
58.根据权利要求53所述的方法,其中在200℃至225℃范围内的温度下通过热固化而热固化所述膜。
59.一种改善双轴取向聚酯膜的耐水解性的方法,所述方法包括将所述聚酯与至少一种水解稳定剂反应的步骤,所述至少一种水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述膜中,其中在选自由第I族和第II族金属阳离子组成的组中的金属阳离子存在下,通过所述水解稳定剂与所述聚酯的端基的反应获得所述反应产物。
60.选自由第I族和第II族金属阳离子组成的组中的金属阳离子用于改善包含至少一种水解稳定剂的双轴取向聚酯膜的耐水解性的用途,所述至少一种水解稳定剂选自支链单羧酸的缩水甘油酯而不存在缩水甘油醚化合物,其中所述单羧酸具有5-50个碳原子,其中所述水解稳定剂以其与至少一些所述聚酯的端基的反应产物的形式存在于所述膜中,以及其中在所述第I族或第II族金属阳离子存在下,通过所述水解稳定剂与所述聚酯的端基的反应获得所述反应产物。
61.根据权利要求59所述的方法或根据权利要求60所述的用途,其中所述双轴取向聚酯膜是如权利要求1-47中任一项所限定的。
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2011
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2012
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- 2012-03-07 TW TW101107745A patent/TWI572646B/zh active
- 2012-03-07 CN CN201280011977.2A patent/CN103415556B/zh active Active
- 2012-03-07 EP EP12710528.6A patent/EP2683761B1/en active Active
- 2012-03-07 BR BR112013022881-4A patent/BR112013022881B1/pt active IP Right Grant
- 2012-03-07 PL PL12710528T patent/PL2683761T3/pl unknown
- 2012-03-07 JP JP2013557165A patent/JP6005075B2/ja active Active
- 2012-03-07 KR KR1020137025933A patent/KR102007754B1/ko active IP Right Grant
- 2012-03-07 US US14/003,676 patent/US9333692B2/en active Active
- 2012-03-07 ES ES12710528T patent/ES2570170T3/es active Active
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2015
- 2015-02-05 US US14/614,518 patent/US20150151474A1/en not_active Abandoned
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CN1354199A (zh) * | 2000-11-22 | 2002-06-19 | 东丽株式会社 | 聚酯组合物及连接器 |
CN101890830A (zh) * | 2009-05-18 | 2010-11-24 | 三菱聚酯薄膜有限公司 | 具有改进的粘合性能的共挤出的双轴取向的聚酯膜,用于太阳能模件的背面层压体,和太阳能模件 |
Also Published As
Publication number | Publication date |
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US9333692B2 (en) | 2016-05-10 |
BR112013022881B1 (pt) | 2020-12-15 |
US20140053901A1 (en) | 2014-02-27 |
US20150151474A1 (en) | 2015-06-04 |
KR20140011479A (ko) | 2014-01-28 |
JP2014513162A (ja) | 2014-05-29 |
PL2683761T3 (pl) | 2016-08-31 |
TW201245296A (en) | 2012-11-16 |
EP2683761B1 (en) | 2016-03-02 |
GB2488787A (en) | 2012-09-12 |
WO2012120260A1 (en) | 2012-09-13 |
EP2683761A1 (en) | 2014-01-15 |
KR102007754B1 (ko) | 2019-08-06 |
CN103415556A (zh) | 2013-11-27 |
ES2570170T3 (es) | 2016-05-17 |
TWI572646B (zh) | 2017-03-01 |
GB201103855D0 (en) | 2011-04-20 |
JP6005075B2 (ja) | 2016-10-12 |
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