CN104827735B - 共挤薄膜以及用于制备共挤薄膜的方法 - Google Patents

共挤薄膜以及用于制备共挤薄膜的方法 Download PDF

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CN104827735B
CN104827735B CN201410858532.9A CN201410858532A CN104827735B CN 104827735 B CN104827735 B CN 104827735B CN 201410858532 A CN201410858532 A CN 201410858532A CN 104827735 B CN104827735 B CN 104827735B
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outer layer
coextruded film
stretching
less
tpe
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CN104827735A (zh
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H·索尔曼
H·贝德
M·皮里克
M·格罗斯曼
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Mondi Gronau GmbH
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Mondi Consumer Packaging Technologies GmbH
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
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  • Laminated Bodies (AREA)
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Abstract

本发明涉及带有热塑性弹性体核心层(1)以及分别由弹性小于热塑性弹性体的聚合物形成的两个外层(2)的共挤薄膜，其中所述外层(2)各自的层厚小于15μm，而且具有通过发泡形成的空穴(3)。根据本发明，所述发泡外层(2)的密度小于0.800g/cm3，其中所述外层每立方毫米(mm3)体积具有500个以上的空穴(3)。本发明的主题还有用于制备共挤薄膜的方法，其中为发泡外层(2)，在35和75巴之间的压力下向挤出机添加发泡剂。

Description

共挤薄膜以及用于制备共挤薄膜的方法
描述
本发明涉及一种带有热塑性弹性体核心层以及分别由聚合物形成的第一外层和第二外层的共挤薄膜，所述聚合物的弹性小于热塑性弹性体，其中所述外层各自的层厚小于15μm，并具有通过发泡形成的空穴。
该共挤薄膜被尤其设计为弹性材料用于一次性卫生产品，并例如用作弹性束带或作为尿布的弹性端接件。尽管在这样的应用上对拉伸特性和回弹力提出高要求，但该材料在相应于一次性用品的件数背景下必须尽可能成本低廉。
在此要注意，针对上述应用往往提供多层叠层材料，其中共挤薄膜在一侧或在两侧与其它层，尤其是覆盖层的非织造物结合。
由EP 0 500 590 B1已知一种带有弹性核心层和非弹性外层的薄膜。该外层相对僵硬，并例如由聚烯烃，尤其是聚乙烯或聚丙烯、聚对苯二甲酸乙二醇酯或聚丙烯酸酯组成。该外层具有微孔结构，它通过把层材料拉伸超出该外层的弹性极限而产生。该微结构由小褶皱组成，其在牵拉后该薄膜的弹性复位时形成，其中褶皱取向依赖于拉伸方向。该薄膜可以单轴向或双轴向拉伸。该微结构感觉上是粗糙的、柔软的表面结构。
由EP 1 316 418 A1已知一种共挤薄膜，其具有热塑性弹性体构成的核心层和弹性较小的材料构成的外层。该外层由带有脆性硬化分子连接的热塑性塑料组成，其在施加拉伸力时只少许拉伸，而在超过预先给定的断裂强度下会无过渡地撕裂。所述脆性的硬化分子连接通过称为激活的垂直于挤出方向的单轴向拉伸不可逆转地开裂。以此使该共挤薄膜可以在垂直于挤出方向上弹性拉伸。该外层可以由通过后处理脆化的聚烯烃，一种由聚烯烃和聚苯乙烯组成的混合物，或由聚烯烃、聚苯乙烯和乙烯醋酸乙烯酯组成的混合物构成。在挤出方向，亦称机器方向上，脆性硬化分子连接保持不变并使该材料硬化。在机器方向上所述层复合物不具有弹性。
由EP 2 471 652 A1已知一种带有文端所描述的特征的共挤薄膜。该共挤薄膜在覆盖层中具有通过发泡和后续拉伸所形成的孔。通过共挤薄膜的牵拉，亦称激活，使该共挤薄膜获得弹性特征，而同时获得织构化的覆盖层。覆盖层中的孔改善了该共挤薄膜的弹性特征，它在其激活之后很大程度上是能可逆拉伸的。通过所述孔还得到垫子状不均匀的表面。
本发明的任务在于，提供一种共挤薄膜，其表征为在首次拉伸时特别小的拉伸力和良好、均匀的机械特性。
从这种类型的共挤薄膜出发，根据本发明的任务如下解决，所述发泡的外层具有小于0.800g/cm3密度，并且每1立方毫米(mm3)体积具有500个以上，尤其是1000个以上的空穴。
因此，根据本发明，应该提供一种带有非常多小空穴的特别均匀的结构。在此本发明基于这样的认识，即正是所述发泡外层的结构对该共挤薄膜的首次拉伸具有特殊意义。根据本发明，所述外层在首次拉伸(即激活)之前测量时，也至少发泡得使密度小于0.800g/cm3，优选小于0.700g/cm3。
因此，从外层的常规聚合物材料出发，例如尤其是聚烯烃，表现出至少15％，优选至少25％的密度减小。
同时该空穴相对较小并在外层中均匀分布。这将导致在施加拉力时该带有空穴而且在它们之间安排的聚合物材料桥(Stegen)的材料，类似于网络仅仅由于其结构在一定程度上是可拉伸的。因此，在首次拉伸刚开始时只需要相对微小的力。
在拉伸的刚开始，外层以及其空穴在一定程度上被拉长，该外层的聚合物随后塑性延伸或者还局部开裂。在塑性拉伸的情况下还有这样的优点，使得在此通过小空穴的均匀分布使外层各个比较薄的聚合物带被拉长。
最后还表现出这样的优点，由于空穴特别是小胞室式的均匀结构，该外层的开裂通过特别宽的拉伸范围进行，因此当空穴开裂时，外层在那里局部首先获得一定的可移动性，因此直接邻接的空穴通常明显稍后才开裂。这种情况还导致，在首次拉伸刚开始时，达到按照现有技术未知的材料柔软特性。
鉴于拉伸特性，在本发明的范围内表现出更多优点。首先也称作激活的首次拉伸可较容易和更好受控地进行。视应用情况而定，还可能完全不用首次拉伸。虽然，使用者在首次拉伸时发现明显增大的阻力，然而该共挤薄膜单独或在具有贴上的非织造层的层复合物中是不太硬的，以致使用者认为没有激活的共挤薄膜是可拉伸的，并相应地操作。
此外，在本发明的范围内还可以进一步改善外层的手感。产生一种特别柔软的令人愉快的表面。借此还可以考虑，视应用情况而定，出于成本原因在共挤薄膜的至少一侧放弃通常设置的非织造材料的贴覆，以便提供一种带有织物特征的非常柔软的、保护皮肤的结构。额外地，该特别均匀的结构还导致所述外层在用其它层贴覆时可以特别容易地粘结。
所述空穴不仅可以作为封闭的胞室，也可以作为敞开的胞室结构或以混合形式存在。
在敞开胞室结构中相邻的空穴部分地彼此贯通。这时，基本上凸面的细胞形的空间称作空穴。
根据本发明一个优选实施方案，所述外层每1mm3体积具有2500个以上，特别优选10000个以上的空穴。在该共挤薄膜的俯视图上看，所述空穴还可部分地彼此重叠地排列。
为了在本发明的范围内可以产生特别小的且均匀分布的空穴，对于所述共挤薄膜的外层的制造使用特殊的方法。在此必须做到是，紧接在熔融液态塑料离开共挤喷嘴之后，冲击式地同时产生非常多的、小的空穴，其中所述共挤薄膜还必须在小空穴能够自己融合之前凝固。为了做到这一点，可以设计一种制造方法，其中向第一挤出机提供核心层用的热塑性弹性体的塑料熔体，向第二挤出机提供至少一个外层用的热塑性基质的塑料熔体，其中在第二挤出机中以35和75巴之间的压力向该热塑性基质添加液态和/或气态发泡剂，且其中所述发泡剂通过从共挤喷嘴挤出后的压力下降膨胀，并在相应的外层中导致空穴的均匀分布。
通过发泡剂的高压使其在热塑性基质中分散，而且还在一定程度上溶于聚合物熔体。
作为发泡剂尤其可以考虑二氧化碳和氮气，其中所述发泡剂特别优选在蒸汽-液体-平衡中作为超临界液体引入挤出机。通过在超临界状态下提供发泡剂，其基本上表现为不可压缩，并仍然可以比较好地溶于聚合物熔体。通过挤出喷嘴后的压力下降，所述发泡剂冲击式地膨胀，并形成特别均匀的和微细的空穴分布。
为了支持尽可能多的小空穴的形成，可以向热塑性基质添加呈颗粒形式的填料作为核化剂。就核化剂而言，优选无机固体颗粒诸如滑石粉，其作为粉末提供。单个均匀地分布在所述热塑性基质中的颗粒使得从喷嘴缝喷出后局部形成空穴变得容易。
根据本发明，两个外层都有均匀分布的小空穴。因此，从上述方法出发，出自第二挤出机的所述热塑性基质在共挤喷嘴之前分开，以便形成这两个外层。作为替代方案，还可以设置第三挤出机，这时其中这两个外层由分开导入的热塑性基质形成。在这样一个实施方式的范围内还有这样的可能性，即针对两个外层使用不同的材料。
与文端使尽量降低制造成本成为可能的想法相反，在本发明的范围内使用比较耗费的并因此高成本的共挤薄膜制造方法。但在此背景下，本发明基于这样的认识，正是通过在外层中特别选定的特别微细的空穴分布和结构，可以实现机械特性的显著的预料不到的改善。
外层的层厚优选介于0.5和10μm之间，而核心层例如具有介于15和150μm之间的厚度。
原则上，在本发明的范围内，在这两个外层和核心层之间还可以安排其它中间层。然而，本发明优选涉及只由这两个外层和核心层组成的三层共挤薄膜。相应地挤出薄膜的总厚度一般在约20和180μm之间。
所述外层作为热塑性基质优选具有聚烯烃。特别适合的是坚韧可拉伸的聚乙烯和聚丙烯混合物。
作为热塑性弹性体尤其可以考虑具有弹性特性的苯乙烯嵌段共聚物、热塑性聚氨酯和聚烯烃嵌段共聚物。对于苯乙烯嵌段共聚物尤其可以列举苯乙烯-异戊二烯-苯乙烯-嵌段共聚物(SIS)、苯乙烯-丁二烯-苯乙烯-共聚物(SBS)、苯乙烯-乙烯丁烯-苯乙烯-共聚物(SEBS)、苯乙烯-异戊二烯-丁二烯-共聚物(SIBS)和苯乙烯-乙烯丙烯苯乙烯-共聚物(SEPS)，它们也可以以混合物使用。
所述共挤薄膜特别有利的特性直接通过拉伸和尤其是首次拉伸(激活)产生。首先，所述共挤薄膜从制造之后的未拉伸的状态出发在生产方向上和/或在横向上可拉伸至少100％，特别优选至少200％。
拉伸特性的检验例如可以这样进行，使得所述共挤薄膜在首次拉伸时伸长150％并借此激活。不可逆拉伸比例，即在未拉伸的薄膜和一次拉伸的薄膜之间的长度变化优选小于20％，特别优选小于10％。
根据本发明，该共挤薄膜的特征正在于，用于首次拉伸所必要的力比较微小。显然，首次拉伸时的拉伸力高于后续拉伸。然而，根据本发明的优选实施方式设定，在生产方向上和/或在横向上，确定的首次拉伸150％(激活)与随后的第二次拉伸的直至100％拉伸时所消耗的拉伸功的比率小于2∶1。
特别容易的可拉伸性不仅反映在拉伸功(即该行程上拉伸力的积分)上，而且反映在拉伸力本身上。根据本发明的共挤薄膜还相应地满足这样的前提，使得在生产方向上和/或在横向上，确定的首次拉伸150％(激活)与随后的第二次拉伸在100％拉伸时测定的拉伸力的比率小于3∶2。
在本发明的范围内制备的共挤薄膜还可以毫无困难地卷起来。尽管核心层材料一般具有高粘性，并因此有结块的倾向，根据本发明的共挤薄膜在较长储存期之后还可以从卷材展开并加工。所述发泡的外层不仅在激活状态下，而且在未激活的状态下用作隔离垫片，其中通过激活达到表面积的额外增大。
所描述的核心层和外层用的材料的加工温度一般介于150℃和230℃之间。
按照一个实施例，总厚度为56μm的三层共挤薄膜通过浇注薄膜挤出形成。结构对称时，这两个外层都具有8μm的层厚，其中与非发泡的致密层相比体积增大33％。所述外层由聚乙烯和聚丙烯的混合物形成，并含有滑石粉作为核化剂。对此，核心层以40μm层厚由苯乙烯嵌段共聚物形成。具有外层发泡的共挤出按照Trexel Inc.开发的“MuCell方法”进行。所述共挤薄膜的特征在于特别低的首次拉伸力和良好的机械特性。该共挤薄膜的表面表现出均匀且柔软。
现将参照附图阐述本发明。附图中：
图1是根据本发明的共挤薄膜的示意图；而
图2显示共挤薄膜在生产方向(机器方向)上拉伸的拉伸曲线图。
图1显示带有热塑性弹性体核心层1以及分别由弹性小于热塑性弹性体的聚合物形成的外层2的共挤薄膜。在所示的实施例中，外层2的层厚与核心层厚度的比率介于1∶3和1∶10，尤其1∶5之间。在对称的层构造下，外层2可以具有8μm的厚度，而核心层1的厚度为40μm。
在图1还可以看出，两个外层2具有通过发泡形成的空穴3。
根据本发明，优选由聚烯烃，尤其是PE和PP的混合物形成的外层，如此程度地发泡，使得密度小于0.800g/cm3，尤其小于0.700g/cm3。另外还可以看出，空穴3小而均匀地分布在外层2中。例如，外层2每1mm3体积具有500个以上的空穴3，优选有1000个以上的空穴3，特别优选5000个以上的空穴3。
为了易于形成特别小而分布均匀的空穴3，外层2的热塑性基质包含颗粒形式的填料作为核化剂，其中尤其考虑滑石粉作为核化剂。
核心层1由苯乙烯嵌段共聚物作为热塑性弹性体组成。
通过空穴3微细的分布，在该实施例中，总共仅8μm厚度的外层2是特别容易拉伸的。首次拉伸时外层2可以首先在一定程度上拉长，直至空穴3之间的聚合物材料塑性变形，而最后各个区域可能开裂。这样的开裂在首次拉伸时就在相对较大的行程范围产生。
由此出发，图2示例性显示力-拉伸曲线图。以％记录拉伸力与共挤薄膜伸长的关系。曲线A显示该共挤薄膜生产之后首次拉伸时的拉伸力进程，其中首次拉伸亦称激活。首次拉伸时，共挤薄膜从其原长度起拉伸到150％，其中曲线C显示共挤薄膜在其复位或拉伸回缩时的拉伸力进程。
曲线B显示由此出发激活之后第二次拉伸的拉伸力进程。
首次拉伸(曲线A)所必要的力比随后的拉伸(曲线B)时的大。然而，根据本发明的共挤薄膜相比已知的实施方式，该差别相对微小。例如可以看出曲线A的变化进程，刚好在拉伸开始时，可能有相对轻微的变形。而在现有技术已知的共挤薄膜的情况下观察到陡得多的线性的拉伸力变化进程，根据本发明的共挤薄膜可以相对较容易激活。例如，在生产方向上和/或在横向上，测定的首次拉伸150％(曲线A)与随后的第二次拉伸的直至100％拉伸时所消耗的拉伸功的比率小于2∶1。因此，基于图2，对比曲线A和B下直至数值100％所包围的面积。
另外还可以看出，在生产方向上和/或在横向上测定的首次拉伸150％与随后的第二次拉伸在100％拉伸时测定的拉伸力比率小于3∶2。这在可以在图2中作为FA，100和FB，100读出相应的相对值。

Claims (12)

1.带有热塑性弹性体核心层(1)以及第一外层(2)和第二外层(2)的共挤薄膜，外层分别由弹性小于热塑性弹性体的聚合物形成，其中所述外层(2)各自的层厚小于15μm，而且具有通过发泡形成的空穴(3)，其特征在于，所述发泡外层(2)的密度小于0.800g/cm3，且该外层(2)每1立方毫米(mm3)体积具有500个以上的空穴。
2.根据权利要求1的共挤薄膜，其特征在于，所述外层(2)每1mm3体积具有1000个以上的空穴。
3.根据权利要求1或2的共挤薄膜，其特征在于，所述外层(2)的密度小于0.7g/cm3。
4.根据权利要求1或2的共挤薄膜，其特征在于，所述外层(2)的层厚在0.5和10μm之间。
5.根据权利要求1或2的共挤薄膜，其特征在于，所述核心层(1)的厚度在15和150μm之间。
6.根据权利要求1或2的共挤薄膜，其特征在于，所述热塑性弹性体选自下组：苯乙烯嵌段共聚物、热塑性聚氨酯和聚烯烃嵌段共聚物。
7.根据权利要求1或2的共挤薄膜，其特征在于，所述外层(2)作为热塑性基质具有聚烯烃，尤其是聚乙烯和聚丙烯的混合物。
8.根据权利要求1或2的共挤薄膜，其特征在于，所述外层(2)包含呈颗粒形式的填料作为核化剂。
9.根据权利要求1或2的共挤薄膜，其特征在于，在生产方向上和/或在横向上，确定的首次拉伸150％与随后的第二次拉伸的直至100％拉伸时所消耗的拉伸功的比率小于2:1。
10.根据权利要求1或2的共挤薄膜，其特征在于，在生产方向上和/或在横向上，确定的首次拉伸150％与随后的第二次拉伸在100％拉伸时测定的拉伸力比率小于3:2。
11.用于制备根据权利要求1至10之一的共挤薄膜的方法，
其中向第一挤出机提供用于核心层(1)的热塑性弹性体的塑料熔体，
其中向第二挤出机提供用于外层(2)的至少一个的热塑性基质的塑料熔体，
其中在第二挤出机中以35和75巴之间的压力向热塑性基质添加液态和/或气态发泡剂，和
其中所述发泡剂离开共挤喷嘴之后通过压力下降而膨胀，并在相应的外层中造成空穴(3)的均匀分布。
12.根据权利要求11的方法，其中针对至少一个外层(2)向热塑性基质添加呈颗粒形式的核化剂。
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US10414134B2 (en) 2019-09-17
CN104827735A (zh) 2015-08-12
PL2886326T3 (pl) 2017-12-29
US20150174871A1 (en) 2015-06-25
ES2641753T3 (es) 2017-11-13
JP2015120349A (ja) 2015-07-02

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