CN105008111A - 制造聚合物多层膜的方法 - Google Patents

制造聚合物多层膜的方法 Download PDF

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CN105008111A
CN105008111A CN201480014579.5A CN201480014579A CN105008111A CN 105008111 A CN105008111 A CN 105008111A CN 201480014579 A CN201480014579 A CN 201480014579A CN 105008111 A CN105008111 A CN 105008111A
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microns
multilayer film
opening
polymer
layer
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大卫·F·斯拉玛
加思·V·安蒂拉
史蒂文·J·弗拉纳根
布伦特·R·汉森
托马斯·P·汉斯申
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3M Innovative Properties Co
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Abstract

本发明提供一种制造至少两种不同的、单独的聚合物膜的方法。本文所述的聚合物多层膜的实施例可例如用于过滤或吸声。

Description

制造聚合物多层膜的方法
相关申请交叉引用
本申请要求2013年3月12日提交的美国临时专利申请61/777535的权益，其公开内容以引用方式全文并入本文。
背景技术
穿孔膜通常用于个人卫生领域，该个人卫生领域提供流体输送膜，以使得流体能够从靠近皮肤的区域移除并且进入吸收区域中。其它常见应用在食品包装工业以及最近的吸声中。用于这些应用的穿孔膜通常小于100微米(0.004英寸)厚(更通常小于50微米(0.002英寸)厚)，并且由例如烯烃、聚丙烯6或聚乙烯制成。
用于生产穿孔膜的典型加工方法包括：将膜真空吸入穿孔板或辊，使用加压流体来形成并刺穿膜，使用冷针或热针、或激光进行针刺以使膜中的孔熔化。然而，这些工艺往往具有诸如膜的孔尺寸、孔密度和/或膜厚度等加工局限性。
真空形成或加压流体形成穿孔膜因可用来使膜变形并刺穿膜的力而往往局限于相对薄的膜(即，小于100微米厚的膜)。另外，用于这种类型的形成工艺的材料往往局限于烯烃基聚合物。这种类型的工艺的另一个特性是在膜中形成突起，在该突起中膜被拉伸直至形成穿孔。此突起在流体控制方面可为优点，在该流体控制中，突起可充当定向流控制特征结构。然而，突起也可在需要低压降的应用中成为缺点。突起形成细长的孔，从而增加表面积并且增加流体曳力。
针刺工艺还广泛用于相对薄的膜，但有时看到最多至约254微米(0.010英寸)的膜厚度。关于此工艺的局限性往往包括膜中的每单位面积穿孔直径孔、和突起。
激光穿孔工艺可提供相对小的孔(即，小于50微米)，可穿透各种厚度，可形成与膜表面在同一平面的穿孔(即，没有例如与针刺工艺相关联的突起)。激光穿孔工艺的局限性包括适用于该工艺的材料类型、以及加工速度和成本。激光穿孔工艺往往最适合由聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、或其它较高玻璃化转变温度材料来加工膜。激光例如在穿透烯烃基材料方面通常不是很有效。
发明内容
在一个方面，本公开描述了一种制造至少两种不同的、单独的聚合物膜的方法，所述方法包括：
将至少两个(在一些实施例中，至少三个、四个、五个或更多个)聚合物层挤出到辊隙中，以提供聚合物多层膜，其中所述辊隙包括具有结构化表面的第一辊，所述结构化表面赋予穿过所述聚合物多层膜的第一主平坦(即，所述压痕除外的相对平坦平面主表面)表面的压痕；
使具有所述压痕的所述第一主平坦表面从冷却辊上经过，同时向所述聚合物多层膜的大体相背对的第二主表面施加热源，其中从所述热源施加热量导致形成开口阵列，所述开口阵列在所述聚合物多层膜的第一主表面和第二主表面之间延伸；以及
将具有所述开口阵列的所述聚合物多层膜的至少第一层和第二层分开，以提供至少两种不同的、单独的聚合物膜。
本文所述的聚合物多层膜的实施例可例如用于过滤和吸声。
附图说明
图1、图1A、图1B和图1C是用于制造示例性聚合物膜的示例性方法的示意图。
图2、图2A、图2B、图2C和图2D是用于制造示例性聚合物膜的另一个示例性方法的示意图。
具体实施方式
参见图1，示出了用于制造至少两种不同的、单独的聚合物膜140,141的示意性方法的示意图。将至少两个聚合物层120,121挤出到辊隙135中，以提供聚合物多层膜110。辊隙135包括具有结构化表面137的第一辊136，该结构化表面赋予穿过聚合物多层膜110的第一主平坦表面111的压痕113。使具有压痕113的第一主平坦表面111从冷却辊138上经过，同时向聚合物多层膜110的大体相背对的第二主表面112施加热源139。从热源139施加热量导致形成开口阵列123，该开口阵列在聚合物多层膜110的第一主表面111与第二主表面112之间延伸。聚合物多层膜110的至少第一层120和第二层121具有开口阵列123，以提供至少两种不同的、单独的聚合物膜140,141。
在查看包括工作实例的当前公开内容之后，用于制造本文所述的多层膜的合适的挤出设备(包括用于制造设备的部件的材料)对于本领域的技术人员而言应该是显而易见的。例如，辊(例如，134,136,138,234,236,238)可由诸如钢的金属制成。在一些实施例中，接触一种或多种聚合物材料的辊表面为镀铬的、镀镍的、镀铜的或铝的。可例如使用常规技术诸如水冷来冷却辊。可例如通过气压缸来提供夹力。
示例性挤出速度包括3至15米/分钟。(在一些实施例中，介于15至50米/分钟、50至100米/分钟或更多的范围内)。示例性挤出温度介于200℃至230℃的范围内(在一些实施例中，介于230℃至260℃、260至300℃或更大的范围内)。
多层聚合物膜通常包括聚烯烃、聚乙烯和聚丙烯。
用于制造聚合物多层膜的示例性聚合物材料包括聚酰胺6、聚酰胺66、聚对苯二甲酸乙二醇酯(PET)、共聚多酯(PETg)、醋酸丁酸纤维素(CAB)、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二酯(PEN)、聚烯烃、聚乙烯和聚苯乙烯(PS)、乙烯-乙烯醇(EVOH)、聚碳酸酯(PC)和聚丙烯。合适的聚丙烯材料包括均聚聚丙烯和改性聚丙烯诸如嵌段共聚物、耐冲击共聚物和无规共聚物。
任选地，包含本文所述制品的聚合物材料中的任一种可包含添加剂，诸如无机填料、颜料、增滑剂和阻燃剂。
在本文所述的聚合物多层膜的一些实施例中，具有大于125微米、150微米、200微米、250微米、500微米、750微米、1000微米、1500微米、2000微米、或者甚至至少2500微米的厚度；在一些实施例中，介于125微米至1500微米、或者甚至125微米至2500微米的范围内。
开口可呈多种形状中的任一种，包括圆形和卵形。
在本文所述的聚合物多层膜的一些实施例中，具有至少30个开口/cm2(在一些实施例中，至少100个开口/cm2、200个开口/cm2、250个开口/cm2、300个开口/cm2、400个开口/cm2、500个开口/cm2、600个开口/cm2、700个开口/cm2、750个开口/cm2、800个开口/cm2、900个开口/cm2、1000个开口/cm2、2000个开口/cm2、3000个开口/cm2、或者甚至至少4000个开口/cm2；在一些实施例中，介于30个开口/cm2至200个开口/cm2、200个开口/cm2至500个开口/cm2、或者甚至500个开口/cm2至4000个开口/cm2的范围内)。
本文所述的聚合物多层膜的实施例可例如用于过滤和吸声。
示例性实施例
1.一种制造至少两种不同的、单独的聚合物膜的方法，所述方法包括：
将至少两个聚合物层挤出到辊隙中，以提供聚合物多层膜，其中所述辊隙包括具有结构化表面的第一辊，所述结构化表面赋予穿过所述聚合物多层膜的第一主平坦表面的压痕；以及
使具有所述压痕的所述第一主平坦表面从冷却辊上面经过，同时向所述聚合物多层膜的大体相背对的第二主表面施加热源，其中从所述热源施加热量导致形成开口阵列，所述开口阵列在所述聚合物多层膜的第一主表面和第二主表面之间延伸；
将具有所述开口阵列的所述聚合物多层膜的至少第一层和第二层分开，以提供至少两种不同的、单独的聚合物膜。
2.根据示例性实施例1所述的方法，其中所述第一层具有不大于125微米(在一些实施例中，不大于100微米、75微米、或者甚至不大于50微米；在一些实施例中，介于25微米至125微米、25微米至100微米、或者甚至25微米至75微米的范围)的厚度。
3.根据示例性实施例1或2所述的方法，其中所述第二层具有不大于125微米(在一些实施例中，不大于100微米、75微米、或者甚至不大于50微米；在一些实施例中，介于25微米至125微米、25微米至100微米、或者甚至25微米至75微米的范围)的厚度。
4.根据前述示例性实施例中任一项所述的方法，具有至少30个开口/cm2(在一些实施例中，至少100个开口/cm2、200个开口/cm2、250个开口/cm2、300个开口/cm2、400个开口/cm2、500个开口/cm2、600个开口/cm2、700个开口/cm2、750个开口/cm2、800个开口/cm2、900个开口/cm2、1000个开口/cm2、2000个开口/cm2、3000个开口/cm2、或者甚至至少4000个开口/cm2；在一些实施例中，介于30个开口/cm2至200个开口/cm2、200个开口/cm2至500个开口/cm2、或者甚至500个开口/cm2至4000个开口/cm2的范围)。
本发明的优点和实施例通过下面的实例进一步加以说明，但这些实例中所引用的特定材料及其量、以及其它条件和细节不应被视为过度限制本发明。除非另外指明，否则所有份数和百分比均按重量计。
实例1
使用下面的过程来制备穿孔多层聚合物膜。通过下述方式来制备由层A、层B和层C组成的三层聚合物膜(ABC)：使用三个挤出机来馈送25cm宽的3层多歧管模头(以商品名“CLOEREN”得自德克萨斯州奥兰治的Cloeren有限公司(Cloeren Inc.,Orange TX))。挤出工艺垂直向下进行到由工具辊236和光滑的钢支承辊234组成的辊隙中。挤出工艺被构造成使得层A接触工具辊236并且层C接触支承辊234，如图2示意性地示出。向用于层A的聚合物提供6.35cm的单螺杆挤出机。向用于层B的聚合物提供6.35cm的单螺杆挤出机。向用于层C的聚合物提供3.2cm的单螺杆挤出机。三个挤出机的加热区温度示于下面的表1中。
表1
挤出机的每分钟转数列于下面的表2中。
表2
使用低密度聚乙烯树脂(55熔体流动速率；以商品名“DOW 959S”得自密歇根州米德兰的陶氏化学公司(Dow Chemical Company,Midland,MI))挤出层A211和层C213。用于层A211和层C213的基重分别为81g/m2和52g/m2。使用聚丙烯/聚乙烯耐冲击共聚物(35熔体流动速率；以商品名“DOW C700 35N”得自陶氏化学公司(Dow ChemicalCompany))挤出层B212。层B212的基重为64g/m2。
包括辊隙的两个辊为具有标称30.5cm的直径和40.6cm的面宽度的水冷辊234,236。通过气压缸来提供夹力。光滑的钢支承辊234的温度设定点为21℃。工具辊236具有切入辊的表面的凸形柱特征结构237。凸形柱特征结构为镀铬的。工具表面上的凸形特征结构(限定为柱)237为具有方形基部的平坦方顶椎体。柱的顶部为94平方微米，并且基部为500平方微米。柱总高度为914微米。柱的中心至中心间距在径向方向和交叉辊方向两者上为820微米。工具辊236具有38℃的温度设定点。工具辊236和支承辊234为直接驱动的。两个压料辊之间的夹力为531牛顿每线性厘米。挤出物带离线速度为3.0m/min。
用于三个层的聚合物从模头230直接挤出到工具辊236与支承辊234之间的辊隙235中。工具辊236上的凸形特征结构237在挤出物中形成压痕214。聚合物薄层215保留在工具辊236与支承辊234之间。通常此层215小于20微米厚。挤出物保留在工具辊236上达180包辊度，以使挤出物冷却并固化成多层聚合物膜。然后将多层膜卷绕成辊形式。
然后按下述方式将包含压痕的多层聚合物膜转换成穿孔膜。使用一种火焰穿孔系统来熔化并移除薄层215，该火焰穿孔系统描述于美国专利7,037,100(Strobel等人)中，其公开内容以引用方式并入本文，并且利用来自美国专利7,635,264(Strobel等人)的燃烧器设计，其公开内容以引用方式并入本文。
对用于此试验的设备和工艺条件的具体修改如下：
冷却辊238为不具有蚀刻或雕刻图案的光滑表面辊。
燃烧器231为如美国专利7,635,264(Strobel等人)所述的30.5厘米(12英寸)的六端口燃烧器、防啸叫设计，其公开内容以引用方式并入本文，并且得自纽约州新罗谢尔的Flynn Burner公司(FlynnBurner Corporation,New Rochelle,NY)。
退绕张力：178牛顿总张力
卷绕机张力：178牛顿总张力
燃烧器231BTU的5118BTU/cm/小时
1％过量氧气
燃烧器231与膜表面之间的间隙：12mm
线速度：30米/分钟
冷却辊238的冷却水设定点：15.5℃。
多层聚合物膜通过图2A示意性地示出的设备在上述条件下进行加工。幅材取向成使得具有薄聚合物层215的膜210的侧面最接近燃烧器231并且与冷却辊238相对。冷却辊238冷却膜的主体，从而使膜的大部分保持在聚合物的软化点之下。来自燃烧器火焰239的热量使留下的薄聚合物层215熔化，从而在膜中形成穿孔216。层A、层B和层C彼此分开并且各自卷绕成单独的辊。
在不脱离本发明的范围和实质的情况下，本公开的可预知的变型和更改对本领域的技术人员而言将是显而易见的。本发明不应受限于本申请中出于说明目的所示出的实施例。

Claims (4)

1.一种制造至少两种不同的、单独的聚合物膜的方法，所述方法包括：
将至少两个聚合物层挤出到辊隙中，以提供聚合物多层膜，其中所述辊隙包括具有结构化表面的第一辊，所述结构化表面赋予穿过所述聚合物多层膜的第一主平坦表面的压痕；以及
使具有所述压痕的所述第一主平坦表面从冷却辊上经过，同时向所述聚合物多层膜的大体相背对的第二主表面施加热源，其中从所述热源施加热量导致形成开口阵列，所述开口阵列在所述聚合物多层膜的第一主表面和第二主表面之间延伸；
将具有所述开口阵列的所述聚合物多层膜的至少第一层和第二层分开，以提供至少两种不同的、单独的聚合物膜。
2.根据权利要求1所述的方法，其中所述第一层具有不大于125微米的厚度。
3.根据权利要求1或2所述的方法，其中所述第二层具有不大于125微米的厚度。
4.根据前述权利要求中任一项所述的方法，具有至少30个开口/cm2。
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