CN101248115A - 双轴拉伸透气性薄膜及其制造方法和用途 - Google Patents
双轴拉伸透气性薄膜及其制造方法和用途 Download PDFInfo
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Abstract
本发明涉及包括聚合物混合物的双轴拉伸透气性薄膜,该聚合物混合物包括基于聚合物混合物总重量的/-至少50%的至少一种聚醚嵌段共聚物;和-0.5-少于50%的至少一种聚酯。本发明也涉及制造所述薄膜的方法和用途。本发明还涉及含有至少一种聚醚嵌段共聚物的双轴拉伸透气性薄膜的制备方法。
Description
技术领域
本发明涉及双轴拉伸透气性薄膜。本发明也涉及制造所述薄膜的方法和这种薄膜的用途。
背景技术
包含聚酯和聚醚嵌段共聚物的薄膜被描述在现有技术中,诸如WO 01/85451中所述。WO 01/84451中公开了用于制造卡片的混合物,该混合物包含无定形共聚聚酯和热塑性聚酯弹性体如Hytrel,其量为大于20重量%并小于50重量%的热塑性聚酯弹性体。
在US 6 436 531中,各聚合物的存在量为基于共混物总重量的约20-约80重量%,更优选在至少40重量%。一种组合物,其包含基于共混物总重量40重量%的聚对苯二甲酸乙二酯(PET)和60重量%的Hytrel。然而,US 6 436 531中的薄膜不是双轴拉伸的。
双轴拉伸薄膜在本领域是公知的。US 5 846 642公开了包含与基于弹性体的聚酯如Hytrel或Arnitel以81∶19-98∶2的比率混合的聚酯与另一种聚酯层压的聚酯薄膜。此流延聚酯薄膜可以同时或逐次进行双轴拉伸。
JP 2002003707公开了在不破坏阻气性能的条件下,除线性可撕裂性能外具有抗冲击性的双轴取向的聚酯薄膜。该薄膜是通过将聚醚-酯弹性体以5-30重量%的比例分散在PET中得到的,其特征在于弹性体含21-60重量%的聚丁二醇(PTMG)。
US 5 912 060公开了热塑性聚酯树脂比如PET和聚酯嵌段共聚物作为聚醚酯嵌段共聚物的混合物,其各自的量为50-95重量%和50-5重量%。得到的薄膜可以双轴拉伸。此参考文献的聚酯嵌段聚合物可以是聚醚;单独公开为含20%聚醚的共混物。在该浓度下,最终的薄膜是非透气性的。
US 6 458 437公开了由聚酯组合物制备的热缩聚酯薄膜,该组合物含有所述聚酯组合物50-95重量%的聚酯和所述组合物3-50重量%的聚酯弹性体。构成所用聚酯的二羧酸组分可以包括对苯二甲酸,构成所用聚酯的二醇组分可以包括乙二醇。聚酯弹性体指由软链段和硬链段构成的聚酯嵌段共聚物,其中软段可以是聚醚酯链段,即聚酯弹性体可以是聚醚嵌段共聚物。这些薄膜可以双轴拉伸。
EP 644 226公开了由具有包含连续相和分散相的海岛结构的两种或更多种热塑性树脂制成的易撕裂薄膜。该薄膜可以双轴拉伸。其中,提及了聚对苯二甲酸乙二酯和聚酯弹性体如Hytrel。不同相的比例为使得连续相/分散相等于约35-98/2-65重量%,优选约50-95/5-50重量%。可以在热塑性树脂混合时添加相容剂,以便使分散粒子更细。然而,此相容剂的量相对于100重量份的包括连续相和分散相的热塑性树脂总重量为不应超过30重量份,否则海岛结构将消失。
透气性薄膜在本领域是公知的。US 2002/0076554公开了聚醚嵌段共聚物制备固有的透气性薄膜,比如Pebax和Hytrel。此专利申请也公开了双轴拉伸的薄膜将变成透气性薄膜。在此专利申请中,通过在薄膜聚合物配制品中采用填料,将填料/基体聚合物配制品挤出到薄膜中,然后充分拉伸薄膜以造成粒子附近的空洞,使薄膜变成为透气性的,由此赋予双轴拉伸薄膜以透气性。
US 6 582 810也公开了上述基于挤出的填料/基体聚合物配制品、拉伸以赋予其透气性的透气性且弹性的薄膜。在此专利中,可构成约35-95重量%的透气性薄膜的基体聚合物配制品可以是聚酰胺聚醚嵌段共聚物,并且填料粒子可以是聚对苯二甲酸乙二酯。多嵌段弹性共聚物如Pebax聚醚嵌段酰胺、Hytrel聚酯可用作弹性纤维以提供弹性。根据US 6 582 810,当期望薄膜具有优良透气性和中等强度时,所述透气性薄膜可包含约30-55重量%的基体聚合物、及45-70重量%的微粒填料。
US 2002/098353公开了聚合物的各种共混物。该文件的实施例21-24公开了含50%或60%的聚醚聚合物如Hytrel和聚酯的共混物。但薄膜仅是流延的而非拉伸的。此文件中薄膜用于耐高温胶带的制造。其中未提及薄膜的透气性,也未提及需要该性能的任何最终用途。
用于同时在纵向和横向两方向上拉伸塑料薄膜的方法也是本领域中公知的。实际上,US 3 890 421公开了上述方法;其内容在此引入作为参考。
虽然某些上述本领域公知的薄膜可以是透气的或是双轴拉伸的,但是它们都不是双轴拉伸的透气性薄膜。因其具有特别的气体选择性和液体渗透性,透气性薄膜被用于许多应用中。寻找双轴拉伸薄膜是因为双轴拉伸改进了塑料薄膜的某些性质,如耐久性、弹性,并减小了薄膜厚度。当尝试逐次双轴拉伸本领域公知的透气性薄膜时,面临的问题是薄膜破裂或收缩。因此需要可以双轴拉伸的透气性薄膜,即能够制备所述薄膜的组合物以及制造所述薄膜的方法,以便改进透气性薄膜的机械性能和热性能。
发明内容
本发明涉及:
1)一种包含聚合物混合物的双轴拉伸的透气性薄膜,该聚合物混合物包含基于聚合物混合物总重量:
-至少50%的至少一种聚醚嵌段共聚物;和
-0.5-少于50%的至少一种聚酯。
2)一种制备本发明薄膜的方法,其包括以下步骤:
(1)形成作为流延薄膜的聚合物混合物,和
(2)同时或逐次双轴拉伸步骤(1)的流延薄膜,优选逐次拉伸PET或PET共聚物含量为15-50%的薄膜。
3)一种制备包含至少一种聚醚嵌段共聚物的双轴拉伸透气性薄膜的方法,该方法包括以下步骤:
(1)形成流延薄膜,和
(2)同时双轴拉伸步骤(1)的流延薄膜,其中该拉伸包括以下步骤:
(i)用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分;
(ii)在用所述夹具抓紧薄膜后,沿所述滑座间邻近中心线延长等距离的轨道向下游推进所述滑座,同时保持所述夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中所述滑座的推进受相对于相邻上游滑座的各下游滑座加速的影响。
4)本发明薄膜用于制备包装薄膜、防护服、衣服、隔膜生产的用途。
5)本发明薄膜进一步与至少一种选自以下组中的支撑物结合:塑料、纤维无纺织物、纺织织物、弹力织物、纸、聚烯烃和聚酯,及其制造方法。
附图说明
图1所示为以温度为函数的薄膜收缩率(实施例9);
图2所示为以薄膜伸长率为函数的应力变化(实施例9)。
具体实施方式
本发明中所用的聚醚嵌段共聚物包括高熔点结晶聚合物链段(硬段)和低熔点软质聚合物结晶聚合物链段(软段)。
本发明所用聚醚嵌段共聚物为任意具有透气性能的聚醚嵌段共聚物。这里采用的具有透气性能的聚醚嵌段共聚物指(根据ASTM D570方法)浸入水中24小时后聚合物在23℃增重最少1.5%。换言之,聚合物是亲水的。
本发明的聚醚嵌段共聚物可以是,例如聚醚酯、聚醚氨酯、聚醚酯氨酯、聚醚酰胺、聚醚酯酰胺、或其混合物。优选的聚醚为聚醚酯。
聚醚酰胺包括例如键合到具有酸末端的聚酯序列的含端羟基的聚醚序列。这种结构也可以包括二醇(例如1,4-丁二醇)。
聚醚氨酯包括例如通过氨基甲酸酯部分键合到二异氰酸酯的含端羟基的聚醚序列。
聚醚酯为热塑性共聚物,一方面其是由聚酯序列通过二羧酸衍生物(如对苯二甲酸酯)和二醇(如丁二醇)的反应产生,另一方面是由聚醚序列如聚亚烷基(醚)二醇或多元醇(软段)制得。
硬段优选包括聚对苯二甲酸丁二酯(PBT),软段包括多元醇长链组分。优选硬段分子量为3000-9000、优选5000-7000g/mol。优选多元醇长链组分包括聚乙二醇(PEG)、聚丙二醇(PPG)或聚亚丙基醚二醇(PPEG)、聚1,4-丁二醇(PTMG或PTHF)聚四亚甲基醚乙二醇、及其组合。优选的多元醇长链组分分子量为200-4000g/mol,优选1000-3000g/mol。
这种聚醚酯的实例有可商购自DuPont的Hytrel、可商购自AkzoChimie的Arnitel、可商购自GE的Lomod和可商购自Toyobo的Perprene。
聚醚酯氨酯相应于聚醚氨酯,其中聚醚序列和异氰酸酯(氨基甲酸酯)由酯键分开。
聚醚酯酰胺为带有反应性端基的聚酰胺嵌段与带有反应性端基的聚醚嵌段共缩聚的产物,其中,例如带有二羧基链端基的聚酰胺嵌段和聚醚二醇嵌段。这类聚酰胺嵌段的数均分子量一般为500-10000,优选为600-5000。聚醚酯酰胺的聚酰胺嵌段优选由聚酰胺6、6.6、6.12、11、12或12.12(PA-6、PA-6.6、PA-6.12、PA-11、PA-12、PA-12.12)构成,或由其单体缩聚得到的共聚酰胺组成。
聚醚的数均分子量一般在200-6000,并优选600-3000。聚醚嵌段优选由均聚或共聚的聚丁二醇(PTMG)、聚丙二醇(PPG)或聚乙二醇(PEG)组成。聚醚酯酰胺优选由5-85重量%的聚醚和95-15重量%的聚酰胺构成,更优选由20-85重量%的聚醚和80-15重量%的聚酰胺构成。
优选这些聚醚酯酰胺为聚醚嵌段聚酰胺,其中聚醚嵌段含均聚或共聚的PEG,并且优选其中聚酰胺嵌段是由均聚或共聚的PA-12、PA-11、PA-12.12得到的那些,例如共聚PA-6.12。
本发明适合的聚醚酯酰胺的实例为Pebax,其可商购自Arkema。
本发明所用聚酯为其主要部分包含任何芳族重复酯单元的任何聚酯。本发明中术语聚酯指由芳香二羧酸如对苯二甲酸、2,6-萘二甲酸、间苯二甲酸、邻苯二甲酸、4,4′-联苯二甲酸和脂肪族二醇如通常是乙二醇或1,4-丁二醇的缩聚得到的聚合物。
除均聚物外,这类聚合物也可以是含有第三组分或若干组分的共聚物。在这种情况下,所述二羧酸组分也可以是例如己二酸、癸二酸、十二烷二羧酸和1,4-环己二甲酸;可以采用含氧羧酸,如对羟苯甲酸或5-磺基间苯二甲酸钠。二醇可以是例如乙二醇、二甘醇、三甘醇、丙二醇(1,2和1,3两种)、丁二醇、新戊二醇、1,4-环己烷二甲醇、聚乙二醇和聚丁二醇。
这种聚酯的实例有聚萘二甲酸乙二酯(PEN)、聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸乙二酯(PET),后者为优选的聚酯。
混合物也可能任选地含另一种不同于聚酯的聚合物。本发明所用聚酯的特性粘度可以在例如0.45-0.7间变化,该粘度在30℃的苯酚四氯乙烷中测定。MW可以在技术人员可理解的较宽界限中变化。
本发明的聚醚嵌段共聚物和聚酯的混合物是均质混合物,即混合物的任一组分相对于另一种组分来说都不是填料粒子。因此本发明的薄膜显示出非常精细的海岛结构,其中较少的组分通常具有小于300nm的尺寸,优选100-200nm或更小。本发明的双轴拉伸透气性薄膜包含混合物,该混合物包括基于聚合物混合物总重量至少50重量%的聚醚嵌段共聚物和1-少于50重量%的至少一种聚酯。
优选聚合物混合物包括至少1重量%的至少一种聚酯。更优选聚合物混合物包括50-95重量%的聚醚嵌段共聚物和5-50重量%的至少一种聚酯。优选聚合物混合物包括至少50重量%、优选60-95重量%的聚醚嵌段共聚物和小于50重量%、优选至少1重量%、优选5-少于40重量%的聚对苯二甲酸乙二酯,其中聚醚嵌段共聚物含有聚对苯二甲酸丁二酯(PBT)的硬段和分子量为200-4000g/mol、优选1000-3000g/mol的含有聚乙二醇和/或聚丙二醇和/或聚亚丙基醚二醇的软段。
优选本发明的双轴拉伸透气性薄膜厚度为0.5-15微米,优选2-6微米。
本发明的薄膜具有良好的机械性能。优选地,所述薄膜的拉伸强度耐久性为至少30N/mm2,拉伸强度根据ASTM D 882-80测定(100%/min,在室温下)。
本发明薄膜提供了良好的热性能。优选在至多60℃、优选至多70℃、更优选至多80℃下薄膜的收缩率为小于5%、优选小于2.5%、更优选小于1.5%,收缩率通过在可商购的热机械分析仪(例如Mettler Toledo TMA 40)、在恒定空载并伴以10℃/min的加热速率条件下测定薄膜样品尺寸来确定。
如前所述,本发明拉伸薄膜是透气性的。在一个实施方案中,根据标准ISO 15496用15微米厚的薄膜在23℃下测定的湿气传输速率(MVTR)为至少250g/m2/天、优选至少500g/m2/天。
本发明薄膜未显示相分离;本发明薄膜中的聚合物分散良好。
所述薄膜可以含有无机填料粒子以改进薄膜的加工和缠绕。优选聚酯含有无机填料粒子。优选聚酯含有量为1000-60000ppm的粒子。所述无机填料粒子可以非限制性的是碳酸钙、粘土、氧化硅、沸石、硅氧烷珠粒(官能化的聚二甲基硅氧烷)、磷酸二钙(DPC)、磷酸三钙(TPC)、中空微珠(cenosphere)、空心微珠(zeeosphere)、滑石、二氧化钛、硫酸钡和钛酸钡。填料粒子尺寸分布可以是单峰、双峰和三峰的。对于单峰、双峰和三峰分布而言,优选平均粒径为0.1-10微米。
本发明双拉伸透气性薄膜可以与另一种薄膜或材料或支撑物结合(例如层压的、经由粘合剂或非粘合剂粘合的、共挤出的、(热)压延的,等)。优选将薄膜层压在另一种薄膜或材料或支撑物上,例如塑料、纤维无纺织物、纤维织物、纺织织物、弹力织物、纸、聚烯烃和聚酯等。
本发明薄膜与已知薄膜相比具有减小的厚度,显示出良好的机械性能比如拉应力耐受性和弹性、热稳定性,并且是透气性的。因此所述薄膜在许多应用中都非常有用,比如衣服(apparel)、过滤、包装。
本发明的薄膜尤其可以用于防护服(protective apparel)如医用大褂或化学防护服的制作上,以及用于户外或休闲服装的制作。通过制造膜,比如制造反渗透膜、纳滤膜、渗透蒸发膜、超滤膜、气体分离膜,这类薄膜也可以用于过滤。此外,本发明薄膜可以用作包装材料,尤其是需要鲜切果蔬包装材料,其中需要在O2和CO2间有适当的选择性。
本发明双轴透气性薄膜可以通过双轴拉伸、更优选通过同时双轴拉伸透气性薄膜得到。
这种双轴拉伸的方法描述于例如US 3 890 421中,其内容在此引入作为参考。
本发明制备薄膜的方法包括流延本发明聚醚嵌段共聚物和聚酯的聚合物混合物的步骤。
聚醚嵌段共聚物和聚酯的聚合物混合物可以在挤出机中掺混和熔化。挤出机可以是单螺杆挤出机,但优选双螺杆挤出机。在挤出机中进行分散和均化后,使聚合物共混物经由熔融泵穿过由管道***和过滤单元组成的熔化***,停留时间为5-30分钟。
优选通过在狭缝模头***中形成聚合物、在骤冷箱上冷却薄膜得到流延薄膜。
流延聚合物混合物随后进行优选同时的双轴拉伸。
该同时的双轴拉伸可以通过包括以下步骤的方法进行:用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分;在用夹抓紧薄膜后,沿滑座间邻近中心线延长等距离的轨道向下游推进滑座,同时保持夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中该滑座的推进受相对于相邻上游滑座各下游滑座加速的影响。
根据本发明的另一个实施方案,该方法优选适用于包含至少一种聚醚嵌段共聚物的双轴拉伸透气性薄膜的制备,即包含这种聚合物、不一定含有聚酯的任何薄膜。
优选滑座各自连接直线电动机的活动元件。在这种情况下,滑座的推进受各活动元件与之接合的直线电动机固定元件的励磁场绕组的影响,并且该方法进一步包括以下步骤:用比相邻上游场绕组逐渐增大的能量励磁下游场绕组,以使相对于相邻上游夹具的各下游夹具加速,因此在推进方向的纵向和横向上拉伸薄膜。
此优选方法应适用于本发明薄膜、即包括聚醚嵌段共聚物和聚酯的聚合物混合物的制备,或是包括至少一种聚醚嵌段共聚物的双轴拉伸透气性薄膜的制备。
进行拉伸的温度可以是120-190℃。
也可参考下列专利:US-P-3890421、US-P-4675582、US-P-4853602、US-P-4825111、US-P-5429785、US-P-5885501、US-P-5051225和US-P-5072493,以及可从Brückner商购的LISIM拉伸法,其在此引入作为参考。
以上公开的与含聚酯的薄膜有关的聚醚的实施方案也可应用于包含至少一种聚醚的任何薄膜。
根据本发明优选的实施方案,对于任何上述方法,拉伸比为2-5倍,优选3-4.5倍。
优选所述方法进一步包括尺寸松弛处理双轴拉伸薄膜的步骤。
优选地,所述尺寸松弛处理的进行是通过在用夹具抓紧薄膜后,沿滑座间邻近中心线延长等距离的轨道向下游推进滑座,同时保持夹具对沿与中心线的范围呈正交的第二线排列,其中该滑座的推进受相对于相邻上游滑座的各下游滑座减速的影响,滑座推进的所述步骤任选地进一步包括朝中心线延长等距离横向移动滑座、其间滑座向下游推进的步骤。
优选地,在由松弛处理后的方法得到的薄膜具有稳定的尺寸,这意味着在所述处理后薄膜不再显示回缩。
同时拉伸之后,所述方法也可以包括热处理薄膜的步骤。
根据本发明的一个实施方案,所述方法进一步包括将双轴拉伸薄膜(包括任选具有聚酯的聚醚)与选自以下组中的至少一种支撑物结合的步骤:塑料、纤维、无纺织物、纺织织物、弹力织物、纸、聚烯烃和聚酯。
优选地,所述方法进一步包括将薄膜层压在支撑物上的步骤。更优选地,层压步骤经由热熔方法进行。
优选地,所述方法包括经由热熔方法将薄膜层压在无纺织物或织物、更好为弹力织物上的步骤。
本发明薄膜与任何塑料的结合也可以通过共挤出进行,尤其当支撑物属于聚酯类型时。
下列实施例用作说明本发明,而不应视作限制。实施例也包括被视为本发明最优方式的。
实施例
实施例1
将聚对苯二甲酸乙二酯(PET)和含55重量%的PBT和45重量%的摩尔组成为64%的环氧丙烷和36%的环氧乙烷的聚亚烷基二醇的聚醚嵌段共聚物加入双螺杆挤出机中,其各自量为基于聚合物混合物总重量的5重量%和95重量%。聚醚嵌段共聚物的吸水率基于ASTM D570法、24小时后、23℃下对于此聚合物是2.5%。
整体加热到250-285℃。
通过在狭缝模头***中形成聚合物并且在骤冷箱上的冷却薄膜得到流延薄膜。
在实验室双轴薄膜拉伸机(可商购自Brueckner(Karo IV)或T.M Long或Inventure Laboratory Inc.。在此技术中,薄膜用同时或逐次在轴向和横向上移动的夹子夹紧)中,使流延薄膜成为双轴拉伸薄膜。
拉伸以拉伸比3.5×3.5进行。
在实验室拉伸机中同时拉伸后,使薄膜松弛,也就是指通过室温下在相应两个方向上移动,轴向和横向上的尺寸变化为5-10%,优选5-7.5%。
得到的双轴拉伸薄膜厚10-15微米。
实施例2
将聚对苯二甲酸乙二酯(PET)和与实施例1相同的聚醚嵌段共聚物引入单螺杆挤出机,各自量为基于聚合物混合物总重量35重量%和65重量%。
拉伸和松弛条件与实施例1相似,除了拉伸比为3.0×3.0。
得到的双轴拉伸薄膜厚25-30微米。
实施例3
将聚对苯二甲酸乙二酯(PET)和实施例1所用的相同聚醚嵌段共聚物引入双螺杆挤出机,各自量为基于聚合物混合物总重量50重量%和50重量%。
拉伸条件与实施例1的相似,但这次没有松弛。
得到的双轴拉伸薄膜厚15-20微米。
实施例4
采用由46重量%的PBT和55重量%的摩尔组成为29%环氧乙烷和71%环氧丙烷的聚亚烷基二醇的聚醚嵌段共聚物。基于ASTM D570法的吸水率在24小时后、23℃下对于此聚合物是30%。将基于10重量%的具有1000g/mol分子量的共聚聚酯PEG和2重量%的5-磺基间苯二甲酸钠的共聚聚酯在双螺杆挤出机中与95重量%的上述聚醚嵌段共聚物混合。
挤出以及拉伸条件与实施例1相似,除了拉伸比为3.0×3.0,松弛为7.5-12.5%,优选7.5-10%。
得到的双轴拉伸薄膜厚15-20微米。
实施例5
采用与实施例4相同的操作条件,除了聚合物混合物包含聚酯。
得到的双轴拉伸薄膜厚15-20微米。
实施例6
采用与实施例4相同的操作条件,除了聚合物混合物含基于17重量%的间苯二甲酸酯的聚酯共聚物。
得到的双轴拉伸薄膜厚15-20微米。
实施例7
采用与实施例6相同的操作条件,除了拉伸比为3.5×3.5。
得到的双轴拉伸薄膜厚15-20微米。
实施例8
将与实施例6相同的聚合物混合物引入双螺杆挤出机。
拉伸比为3.5×3.5,并且松弛为7.5-12.5%,优选7.5-10%。
得到的双轴拉伸薄膜厚10-15微米。
实施例9
采用与实施例8相同的操作条件,除了拉伸比为4.0×4.0,松弛为10-15%,优选10-12.5%。
得到的双轴拉伸薄膜厚10-15微米。
图1和图2所示分别为以温度为函数的薄膜收缩率和以薄膜伸长为函数的应力变化。
实施例10
采用与实施例8相同的操作条件,除了松弛在40-50%、优选45-50%的范围在温度为100-170℃下进行。
得到的双轴拉伸薄膜厚10-15微米。
实施例11
采用与实施例8相同的操作条件,除了松弛在约25%、温度为40-80℃下进行。
得到的双轴拉伸薄膜厚10-15微米。
实施例12
采用与实施例6相同的操作条件,除了聚合物混合物包含15重量%的聚酯和85%的聚醚嵌段共聚物。
得到的双轴拉伸薄膜厚15-20微米。
实施例13
采用与实施例12相同的操作条件,除了拉伸比为3.5×3.5。
得到的双轴拉伸薄膜厚15-20微米。
实施例14
采用与实施例7相同的操作条件,除了将流延薄膜逐次拉伸,其中MD拉伸以比TD上高6倍的拉伸速度进行。拉伸比MD相对TD方向为3.3-3.5倍。以优选用于高PET含量的逐次拉伸法没有得到良好拉伸的薄膜。
对于除实施例14外的所有上述实施例,薄膜的透气性采用标准ISO15496在23℃测定。也给出了厚度。薄膜的拉伸强度经ASTM D882-80在100%/min下测定。薄膜的收缩率通过在可商购的热机械分析仪中、在恒定空载伴以10℃/min的加热速率条件下以测定薄膜样品尺寸的方法确定。负值表示薄膜的收缩,而正值意味着薄膜的膨胀。热性能(即在MD和TD方向上的平均收缩率)在60、80、100和120℃下进行确定。结果在下表中给出。
实施例 | 厚度(μm) | MVTR(g/m2/h) | MD拉伸强度(N/mm2) | MD伸长率(%) | TD拉伸强度(N/mm2) | TD伸长率(%) | 平均MD/TD收缩率(%) | |||
60℃ | 80℃ | 100℃ | 120℃ | |||||||
1 | 10 | 2700 | 73 | 120 | 85 | 200 | -0.1 | -2.5 | -6.5 | 11.7- |
2 | 27.5 | 613 | 80 | 147 | 131 | 119 | 0.3 | -1.7 | -8.0 | -16.0 |
3 | 20 | 247 | 130 | 90 | 112 | 100 | 0.1 | -0.8 | -4.3 | -9.8 |
4 | 17 | 12160 | 36 | 137 | 29 | 74 | 0.3 | -1.0 | -3.7 | -8.4 |
5 | 18 | 11026 | 41 | 205 | 50 | 288 | 0.3 | -1.3 | -4.3 | -9.6 |
6 | 18 | 6877 | 41 | 256 | 36 | 232 | 0.4 | -2.1 | -5.0 | -10.1 |
7 | 16 | 8822 | 69 | 274 | 42 | 248 | -0.1 | -2.3 | -5.3 | -10.5 |
8 | 18 | 10778 | 50 | 275 | 51 | 267 | 0.2 | -1.0 | -2.7 | -5.4 |
9 | 13 | 13627 | 46 | 168 | 46 | 198 | 0.2 | -1.2 | -3.1 | -6.2 |
10 | 17 | 9971 | 44 | 217 | 36 | 192 | 0.0 | -0.9 | -2.1 | -3.9 |
11 | 14.5 | 11799 | 36 | 131 | 47 | 199 | 0.6 | -0.1 | -2.2 | -5.4 |
12 | 20 | 513 | 59 | 203 | 50 | 184 | 0.4 | -4.3 | -7.1 | -10.7 |
13 | 12 | 1644 | 47 | 251 | 47 | 226 | -0.3 | -4.7 | -7.5 | -10.7 |
Claims (32)
1.一种包含聚合物混合物的双轴拉伸透气性薄膜,以聚合物混合物总重量计所述聚合物混合物包含:
-至少50%的至少一种聚醚嵌段共聚物;和
-0.5-少于50%的至少一种聚酯。
2.权利要求1的薄膜,其中所述聚合物混合物包含:
-至少一种量为所述混合物的50-95重量%的聚醚嵌段共聚物;和
-至少一种量为所述混合物的0.5-50重量%的聚酯。
3.权利要求1或2的薄膜,其中所述聚醚嵌段共聚物选自以下组中:聚醚酯、聚醚氨酯、聚醚酯氨酯、聚醚酰胺、聚醚酯酰胺、及它们的混合物。
4.权利要求3的薄膜,其中所述聚醚嵌段共聚物为聚醚酯。
5.权利要求1-4之一的薄膜,其中所述聚醚嵌段共聚物包括含有聚对苯二甲酸丁二酯(PBT)的硬段,和分子量为200-4000g/mol、含有聚乙二醇和/或聚丙二醇和/或聚亚丙基醚二醇的软段。
6.权利要求1-5之一的薄膜,其中所述聚酯为聚对苯二甲酸乙二酯(PET)或聚酯共聚物。
7.权利要求1-6之一的薄膜,其中所述薄膜的厚度为0.5-20微米,优选2-6微米。
8.权利要求1-7之一的薄膜,其中相对于厚度为15微米的薄膜,所述薄膜的最小湿气传输速率为至少300g/m2/天,优选5000-15000g/m2/天。
9.权利要求1-8之一的薄膜,其中所述薄膜的拉伸强度为至少35N/mm2,优选50-160N/mm2。
10.权利要求1-9之一的薄膜,其中在至多60℃的温度下所述薄膜的收缩值为小于或等于1%,和/或其中在至多80℃的温度下所述薄膜的收缩值为小于或等于5%,优选2.5-4%。
11.权利要求1-10之一的薄膜,其中所述薄膜包含优选量为500-60000份/百万份(ppm)的无机填料粒子。
12.权利要求1-11之一的薄膜,其进一步与至少一种选自以下组中的支撑物结合:塑料、纤维无纺织物、纺织织物、弹力织物、纸、聚烯烃和聚酯。
13.权利要求1-12之一的薄膜用于制备包装薄膜、防护服、衣服、膜的用途。
14.一种用于制备权利要求1-12之一的薄膜的方法,其包括以下步骤:
(1)形成作为流延薄膜的聚合物混合物,和
(2)同时或逐次双轴拉伸步骤(1)的流延薄膜,优选逐次拉伸PET或PET共聚物含量为15-50%的薄膜。
15.权利要求14的方法,其中所述同时双轴拉伸包括以下步骤:
(i)用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分;
(ii)在用所述夹具抓紧薄膜后,沿所述滑座间邻近中心线延长等距离的轨道向下游推进所述滑座,同时保持所述夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中所述滑座的推进受相对于相邻上游滑座的各下游滑座加速的影响。
16.权利要求15的方法,其中所述同时双轴拉伸包括以下步骤:
(i)用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分,其中所述滑座各自连接直线电动机的活动元件;
(ii)在用所述夹具抓紧薄膜后,沿所述滑座间邻近中心线延长等距离的轨道向下游推进所述滑座,同时保持所述夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中所述滑座的推进受各活动元件与之接合的直线电动机固定元件的励磁场绕组的影响;和
(iii)用比相邻上游场绕组逐渐增大的能量励磁下游场绕组,以使相对于相邻上游夹具的各下游夹具加速,因此在推进方向的纵向和横向上拉伸薄膜。
17.一种用于制备包含至少一种聚醚嵌段共聚物的双轴拉伸透气性薄膜的方法,该方法包括以下步骤:
(1)形成流延薄膜,和
(2)同时双轴拉伸步骤(1)的流延薄膜,其中所述拉伸包括以下步骤:
(i)用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分;
(ii)在用所述夹具抓紧薄膜后,沿所述滑座间邻近中心线延长等距离的轨道向下游推进所述滑座,同时保持所述夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中所述滑座的推进受相对于相邻上游滑座的各下游滑座加速的影响。
18.权利要求17的方法,其中所述拉伸包括以下步骤:
(i)用滑座上安装的相反的夹具对沿流延薄膜的相反边缘连续地抓紧流延薄膜的连续部分,其中所述滑座各自连接直线电动机的活动元件;
(ii)在用所述夹具抓紧薄膜后,沿所述滑座间邻近中心线延长等距离的轨道向下游推进所述滑座,同时保持所述夹具对沿与中心线的范围呈正交的第二线排列,所述滑座的推进步骤进一步包括从中心线延长等距离横向移开滑座、其间滑座向下游推进的步骤,其中所述滑座的推进受各活动元件与之接合的直线电动机固定元件的励磁场绕组的影响;和
(iii)用比相邻上游场绕组逐渐增大的能量励磁下游场绕组,以使相对于相邻上游夹具的各下游夹具加速,因此在推进方向的纵向和横向上拉伸薄膜。
19.权利要求17或18的方法,其中所述聚醚嵌段共聚物选自以下组中:聚醚酯、聚醚氨酯、聚醚酯氨酯、聚醚酰胺、聚醚酯酰胺、及它们的混合物。
20.权利要求19的方法,其中所述聚醚嵌段共聚物为聚醚酯。
21.权利要求17-20之一的方法,其中相对于厚度为15微米的薄膜,所述薄膜的湿气传输速率为至少300g/m2/天,优选5000-17000g/m2/天。
22.权利要求14-21之一的方法,其中拉伸比为2-5倍,优选3-4.5倍。
23.权利要求14-22之一的方法,其中所述流延薄膜在狭缝模头上形成,并在骤冷箱上冷却。
24.权利要求14-23之一的方法,其进一步包括对在步骤(2)得到的双轴拉伸薄膜进行尺寸松弛处理的步骤。
25.权利要求24的方法,其包括以下步骤:
(iv)在用夹具抓紧薄膜后,沿滑座间邻近中心线延长等距离的轨道向下游推进滑座,同时保持夹具对沿与中心线的范围呈正交的第二线排列,其中所述滑座的推进受相对于相邻上游滑座的各下游滑座减速的影响,滑座推进的所述步骤任选地进一步包括朝中心线延长等距离横向移动滑座、其间滑座向下游推进的步骤。
26.权利要求14-25之一的方法,其进一步包括拉伸后热处理所述薄膜的步骤。
27.一种用于制备与至少一种支撑物结合的权利要求12的薄膜的方法,其包括将所述双轴拉伸薄膜与选自以下组中的一种支撑物结合的步骤:塑料、纤维、无纺织物、纺织织物、弹力织物、纸、聚烯烃和聚酯。
28.权利要求27的方法,其中所述薄膜被层压在所述支撑物上。
29.权利要求28的方法,其中所述薄膜经由热熔方法进行层压。
30.权利要求17-26之一的方法,其进一步包括将双轴拉伸薄膜与选自以下组中的一种支撑物结合的步骤:塑料、纤维、无纺织物、纺织织物、弹力织物、纸、聚烯烃和聚酯。
31.权利要求30的方法,其中所述薄膜被层压在所述支撑物上。
32.权利要求31的方法,其中所述薄膜经由热熔方法进行层压。
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US (1) | US8592028B2 (zh) |
EP (2) | EP1757651A1 (zh) |
JP (1) | JP5189487B2 (zh) |
KR (4) | KR101491453B1 (zh) |
CN (1) | CN101248115B (zh) |
WO (1) | WO2007022990A1 (zh) |
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-
2005
- 2005-08-25 EP EP20050291786 patent/EP1757651A1/en not_active Withdrawn
-
2006
- 2006-08-25 JP JP2008527398A patent/JP5189487B2/ja active Active
- 2006-08-25 EP EP06777065.1A patent/EP1917295B1/en active Active
- 2006-08-25 US US11/990,963 patent/US8592028B2/en active Active
- 2006-08-25 WO PCT/EP2006/008350 patent/WO2007022990A1/en active Application Filing
- 2006-08-25 KR KR1020137028703A patent/KR101491453B1/ko active IP Right Grant
- 2006-08-25 KR KR1020147033728A patent/KR101601650B1/ko active IP Right Grant
- 2006-08-25 CN CN200680030811XA patent/CN101248115B/zh active Active
- 2006-08-25 KR KR1020147033731A patent/KR101577206B1/ko active IP Right Grant
- 2006-08-25 KR KR1020087003767A patent/KR20080038345A/ko active Application Filing
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CN103100313A (zh) * | 2011-11-15 | 2013-05-15 | 中国科学院大连化学物理研究所 | 一种peba与peg或peo的共混膜及其制备和应用 |
CN103437162A (zh) * | 2013-08-27 | 2013-12-11 | 杭州艾吉克膜科技有限公司 | 一种干膜亲水药剂 |
CN103437162B (zh) * | 2013-08-27 | 2015-12-23 | 苏州艾吉克膜科技有限公司 | 一种干膜亲水药剂 |
CN105926168A (zh) * | 2016-05-12 | 2016-09-07 | 武汉纺织大学 | 一种双向拉伸的聚苯硫醚纤维多孔膜的制备方法 |
CN108724869A (zh) * | 2017-04-20 | 2018-11-02 | 佛山金万达科技股份有限公司 | 一种透汽阻隔型功能薄膜层合物 |
CN108724869B (zh) * | 2017-04-20 | 2021-08-20 | 佛山金万达科技股份有限公司 | 一种透汽阻隔型功能薄膜层合物 |
TWI735323B (zh) * | 2020-08-31 | 2021-08-01 | 南亞塑膠工業股份有限公司 | 改性熱塑性聚酯彈性體及透溼防水膜 |
US11802202B2 (en) | 2020-08-31 | 2023-10-31 | Nan Ya Plastics Corporation | Modified thermoplastic polyester elastomer |
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Also Published As
Publication number | Publication date |
---|---|
US20090117362A1 (en) | 2009-05-07 |
EP1757651A1 (en) | 2007-02-28 |
KR20130124596A (ko) | 2013-11-14 |
US8592028B2 (en) | 2013-11-26 |
KR101601650B1 (ko) | 2016-03-09 |
JP5189487B2 (ja) | 2013-04-24 |
KR20080038345A (ko) | 2008-05-06 |
JP2009506147A (ja) | 2009-02-12 |
KR101491453B1 (ko) | 2015-02-10 |
WO2007022990A1 (en) | 2007-03-01 |
KR101577206B1 (ko) | 2015-12-15 |
KR20150002892A (ko) | 2015-01-07 |
EP1917295B1 (en) | 2016-12-21 |
KR20150002893A (ko) | 2015-01-07 |
EP1917295A1 (en) | 2008-05-07 |
CN101248115B (zh) | 2011-05-25 |
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