CN1466483A - 制造微孔膜的挤出方法和设备 - Google Patents
制造微孔膜的挤出方法和设备 Download PDFInfo
- Publication number
- CN1466483A CN1466483A CNA018162088A CN01816208A CN1466483A CN 1466483 A CN1466483 A CN 1466483A CN A018162088 A CNA018162088 A CN A018162088A CN 01816208 A CN01816208 A CN 01816208A CN 1466483 A CN1466483 A CN 1466483A
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Images
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- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/9165—Electrostatic pinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
Abstract
一种制造微孔膜的方法和设备。本方法使用铸造表面(14)和凝聚表面(18)。凝聚表面(18)与铸造表面(18)相隔,形成一个夹缝。形成夹缝的两个表面之间的距离较小,优选小于3厘米。能够通过热致相分离形成微孔膜的一种材料铸造到铸造表面(14)上,优选是通过常规挤出方法进行的。所述材料包含至少一种蒸发组分,该组分通常在形成微孔膜时闪蒸掉,并凝聚在凝聚表面(14)上。
Description
本申请要求2000年9月24提交的美国临时专利申请60/235222(其全部内容参考结合于此)的优先权。本发明一般涉及挤出材料用的方法和设备,更具体涉及把片材(例如薄膜)挤出到一个氛围中的挤出方法和设备,该氛围能让挤出材料中的蒸发组分在其中凝聚并收集。
发明背景
微孔膜可用热致相分离(TIPS)方法进行制备。所述方法通常包括把材料挤出到铸造表面上。例如,铸造的膜可以是微孔膜的前体,它是至少一种可结晶聚合物(如聚乙烯)和可互溶稀释剂化合物(如矿物油)的熔体溶液从高温(例如:400°F)的模头挤出到低温(例如150°F)铸造辊上形成的。当挤出到铸造表面上以后进行冷却时,就发生均匀溶液的相分离,形成聚合物和化合物的两相膜。该可互溶化合物(如矿物油)可在随后的过程中(如溶剂抽提方法等)除去。得到的膜也可在随后的过程中进行拉幅操作,而发生变化,在膜中形成互相连通的微孔网络。本发明的微孔材料可用在其微孔结构有用的各种用途。微孔制品可以是自撑因而可独立使用的膜,也可以是将本发明微孔层固定在基材上的结构体,如根据用途由聚合物、机织材料、非织造材料、箔或泡沫材料、或者它们的组合制成的结构体。例如,它们可用在不同的用途中,如胶体的超滤、扩散膜、面油去除物、漫射光反射镜或电化学电池中的隔膜。此外,它们也可层压到各种基材上,这些层压制品可用来形成,如雨衣或其它外衣或者露营装备(如帐篷和睡袋)等制品。本发明的微孔板膜可层压到机织布或非织造布(如非织造稀布)上。这种稀布可用来制造一次性的保护性外衣上,所述保护性外衣可用在旅馆或电子洁净室或其它地方,如存在腐蚀性化学溢出物问题的地方。
微孔膜材料还可用作过滤材料,用来净化抗生素、啤酒、油、细菌培养基液体,也可用于空气分析中的样品收集并收集微生物样本。它们也可用于制造外科敷料、绷带和其它医学用途。本领域中的技术人员会认识到本发明得到的微孔材料的许多其它用途。例如,可参见共同转让的美国专利4726989和4539256,其全部内容参考结合于此。
在这种方法中,已发现所得的微孔膜的质量会通过一些机理而降低。首先,挤出在铸造辊上的薄膜的均匀淬冷是用来形成无缺陷膜制品。如果静电固定线(pinning wire)受到污染或破坏,那么对于薄膜生成的供料会不均匀,从而造成缺陷,如称为“螺纹(worm)”的沿薄膜料上的线条。
在薄膜铸造领域中,通常认为可提供带静电的静电荷固定线利用电荷来把挤出材料固定在铸造表面上。在一种方法中,该静电固定线连续往返在薄膜宽度上移动,提供新鲜的静电固定线表面,从而在挤出材料上形成无缺陷的表面。但是,在制造微孔膜的情况,稀释剂相(如矿物油)即使在室温下蒸发低,但在挤出的高温下仍有足够大的挥发性,会闪蒸或蒸发掉一部分。这种低蒸发溶剂(通常是矿物油等)的闪蒸以非常快的速度和数量凝聚在静电固定线上,足以形成“螺纹”缺陷。
其次,微孔膜的外观会受到常用薄膜挤出头所处氛围的负面影响。在这些模头中的空气流或者是不受控的室内型空气,或者更糟的是,甚至更高速空气的流(如来自排风管和压力通风系统),这些空气流产生不均匀的通风或部分地捕获闪蒸的低蒸发稀释剂。这种空气流和导致的不均匀传热可在最终薄膜上形成大区域的外观缺陷,这些外观缺陷类似于干燥涂层上观察到的“木材纹理”或“斑纹”图像。这是相分离的不均匀条件或发生在挤出膜上淬冷过程的结果。另外,不均匀条件通常会在微孔特性方面产生不好的改变。
最后,对于连续运行的微孔薄膜铸造过程,一个不好的结果是,低温低挥发性溶剂(如矿物油)从薄膜中闪蒸出来后会重新凝聚,并在过程中污染邻近的设备。来自低挥发性蒸发组分的凝结物也会污染最终微孔膜产品。而且,有些油/溶剂不可避免地会释放到空气和氛围中。
发明概述
在本发明中,在热致相分离过程中,微孔膜铸造的缺点是通过将薄膜铸造到铸造辊时提供一个受控氛围来克服。受控的氛围可减少缺陷,提高对设备的控制和导致缺陷的过程条件的控制。可用毛细凝聚表面技术来产生此受控的氛围。结合使用毛细凝聚表面技术和热致相分离技术就可提供一种形成微孔膜的改进方法。
本发明是一种制备微孔膜的方法。这种方法利用了铸造表面和凝聚表面。凝聚表面与铸造表面分隔形成一层夹缝。形成夹缝的两个表面的距离较小,优选小于3厘米。优选使用常规的挤出方法在铸造表面上铸造一种材料。这种材料能通过热致相分离形成微孔膜。
在本发明中,当材料铸造在铸造表面上时,铸造表面是移动的。铸造表面在相对凝聚表面的方向上移动,使材料通过夹缝移动。这种材料包含至少一种蒸发组分,该蒸发组分通常在形成微孔膜时闪蒸掉,并凝聚在凝聚表面上。凝聚表面的温度可加控制,调节材料中至少一种蒸发组分的凝聚速率。
本方法适合于形成微孔膜,该微孔膜没有常规方法中蒸发组分凝聚时形成的缺陷。在一个优选的实施方式中,本方法适合形成微孔自撑膜或本发明微孔膜固定在基材上的结构体,如根据用途由聚合物、机织材料、非织造材料、箔或泡沫材料、或者它们的组合的材料构成的结构体。例如,它们可用在不同的用途中,如胶体的超滤、扩散膜、面油去除物、漫射光反射镜或电化学电池中的隔膜。此外,它们可层压到各种基材上,这些层压制品可形成,如雨衣或其它外衣或露营设备如帐篷和睡袋等制品。本发明的微孔膜可层压到机织布或非织造布(如非织造稀布)。这种稀布可用来制造一次性的保护性外衣上,所述保护性外衣可用在旅馆或电子洁净室或其它地方,如存在腐蚀性化学溢出物问题的地方。
微孔膜材料还可用作过滤材料用来净化抗生素、啤酒、油、细菌培养基液体,也可用于空气分析中的样品收集并收集微生物样本。它们也可用于制造外科敷料、绷带和其它医学用途。本领域中的技术人员可根据本发明得到微孔材料的许多其它用途。
本发明也包括通过热致相分离制造微孔膜用的设备。这种装置包括适合于接受铸造材料的铸造表面。所述材料能够通过热致相分离形成微孔膜。通常,所述材料包含至少一种在形成所述微孔膜时蒸发的材料。一个凝聚表面与铸造表面分隔,在铸造表面和凝聚表面之间形成一层夹缝。铸造表面可相对于凝聚表面移动,使铸造材料通过夹缝移动。凝聚表面的温度要保持在能将至少一种蒸发组分的至少一部分凝聚在凝聚表面上。
为了本发明的目的,在本申请中使用的下述术语,定义如下:
“微孔”指产品或材料的特征是具有许多可结晶热塑性聚合物的间隔的、无规分布的、形状不均匀的、各向等大的颗粒;
“蒸发组分”指在薄膜形成步骤中作为主相(稀释剂)的成分或者组分或者在铸造温度下挥发的另一种组分。
其它特定和优点将根据下述实例的说明和权利要求书进行详细描述。
附图简述
参照附图,根据下列详细描述,本领域的技术人员易发现上述和本发明的其它优点:
图1是本发明的示意图;
图2是图1沿着基线2-2的本发明另一个示意图;
图3是本发明一个可用实施方式的组装图。
发明详述
如图1和2所示,本发明设备是一种利用热致相分离过程10的设备,它包括具有铸造表面14的铸造辊12。有个凝聚板16紧挨铸造表面14放置,在铸造表面14和凝聚表面18之间形成间距H的一层夹缝。使用挤出机模头26把铸造材料28铸造到铸造表面14上。该材料是能够通过热致相分离过程形成微孔膜的组合物。在铸造到铸造表面14上后,该材料相分离成聚合物微孔膜和在聚合物结晶温度不能与聚合物互溶的液体。一部分液体通常在接近聚合物结晶温度的温度蒸发。然后凝聚表面可凝聚至少一部分蒸发组分V。凝聚表面上可以有一些毛细凹槽20,其作用是帮助把凝聚液体输送到凝聚表面的外缘22。边缘板24可用来从凝聚板16的外缘22除去凝聚材料。所述设备10可以包括一根带电荷的线29,帮助把铸造材料28固定在铸造表面14上。
铸造表面通常是任何常用基材,适合接受能够通过热致相分离形成微孔膜的材料。常用基材包括辊、带或轮。铸造表面优选相对于凝聚表面移动,用以通过夹缝输送铸造材料。优选控制铸造表面的温度,以便帮助形成微孔材料。本领域的技术人员可认识到,对于特定材料的加工的最终用途来说,铸造表面的表面特征是很重要的。铸造表面的其它例子是聚合物膜和非织造基材。
本发明紧挨铸造表面使用至少一个凝聚表面。凝聚表面与铸造在铸造表面上的材料的外露表面相邻。凝聚表面提供了凝聚的驱动力,使溶剂蒸气穿过夹缝进行传递。当材料通过两个表面之间的夹缝进行传递时,就发生了蒸发组分的凝聚和回收。本发明结合了热致相分离技术和夹缝干燥技术。夹缝干燥系统如美国专利6047151、4980697、5813133、5694701、5581905和6134808(其全部内容参考结合于此)所述。凝聚表面和铸造膜表面之间的夹缝距离优选小于3厘米。在一个优选的实施方式中,这个夹缝小于0.3厘米,以更好地控制空气流和蒸发组分的收集。
本发明的凝聚表面上可以有一些横向开口凹槽或通道(以下称为“毛细表面”),它们用毛细力来防止凝聚液体返回到铸造材料的外露表面上。毛细力也把凝聚液体横向输送到表面的边缘。毛细力或毛细压力是表面张力作用在弯曲的弯月面上的结果。它由已知Young-Laplace方程这个毛细管作用基本方程决定。Young-Laplace方程是: 其中Δpc是界面两侧的压力,σ是表面张力,R1和R2是在界面的主曲率半径。毛细管作用详细描述在Adamson,A.W.“表面物理化学,第四版”,John Wiley & SonsInc.(1982)。
毛细表面的具体类型定义为满足Concus-Finn不等式:α+θs<90°的几何比表面,其中α是任何夹角的内角的一半,θs是气体/液体/固体静止接触角。静止接触角由液体对气体中给定表面材料用的表面张力决定。毛细表面更详细的描述在Lopez de Ramos,A.L.,“Capillary Enhanced Diffusion of Co2 in PorousMedia,”博士论文,University of Tulsa(1993)。
通过毛细力,凝聚在表面18上的液体被吸引到凹槽中,然后横向流到边缘板24(如图1-3所示)。当液体到达凹槽20的末端时,它与边缘板24和凝聚表面18之间的角相交。液体的弯月面形成了一个低压区域,该低压区域能够把液体从毛细表面牵引到至少一个边缘板24上。液体重力克服了弯月面处的毛细力,因此以膜状或水滴的形式沿着边缘板的表面向下流。从边缘板24上即可收集凝聚液体进行分析、循环、处理等。凝聚液体在板上的流动又使蒸发物质连续凝聚到凝聚板的表面上,致使凝聚液体不会滴回到铸造材料的外露表面上。
凝聚表面上的凹槽可以是三角形、矩形、圆形或其它更复杂的形状。要设计凹槽的材料、几何形状和尺寸以完成所需的物质流,该物质流取决于凝结液的分离速率和物理性质,主要是表面张力、粘度和密度。示意图中表示的是矩形和三角形凹槽。
尽管其它类型的材料可用作毛细凝聚表面,例如多孔介质,但是横向的凹槽提供了高的液体传递速率,消除了对于板长度的要求,因为免除了沿着材料上的去除。
在一个优选的实例中,凝聚板可做成多个区。多区是指有不止一块板排列在铸造表面周围。每个板区可以有对于控制过程中的任何参数来说独立的设置,这些参数例如夹缝间距、凝聚板温度和其它。这就可控制不同的过程操作参数来得到更大的产率以及更好的产品质量。
本发明的另一个可用的实施方式是在凝聚板的尾端使用一个蒸气收集装置。该装置紧挨材料的表面放置,以便收集没有凝聚在凝聚板上的蒸气。通常,通过材料层在相邻于材料表面的气相部分中运动来运送蒸气。适合上述目的的蒸气收集系统详细描述在与本申请同时提交的美国专利申请____(代理人案卷号56021US002)中,其全部内容完全参考结合于此。
微孔膜中的具体组分是可结晶聚合物、稀释剂和成核剂。合适的可结晶聚合物、成核剂和稀释剂的例子包括在前述美国专利4726989中提到的物质。其它成核剂包括:γ-喹吖啶酮、醌茜磺酸铝盐、二氢喹吖啶二酮(dihydroquimiacridin-dione)和喹吖啶四酮、三酚双三嗪(triphenenolditriazine)、双组分引发剂如碳酸钙和有机酸或者硬脂酸钙和庚二酸、硅酸钙、周期表第二主族金属的二羧酸盐、Δ-喹吖啶酮、己二酸或软木酸的二酰胺、软木酸或庚二酸的钙盐、不同类型的溶靛素和苯氨基化合物(carbantine)有机颜料、喹吖啶酮、N’,N’-二环己基-2,6-萘二酰胺(dicarboxamind)、和蒽醌(antraquinon)红和双偶氮黄色颜料。优选的成核剂包括γ-喹吖啶酮、软木酸钙盐、庚二酸钙盐和多元酸的钙、锌和钡盐。
另外,在微孔膜材料中可使用其它组分,包括表面活性剂、表面活化剂、抗静电剂、紫外吸收剂、抗氧化剂、有机或无机着色剂、稳定剂、阻燃剂、芳香剂、增塑剂、杀菌剂、防水剂和防污剂化合物。
在操作时,毛细凝聚表面的温度应设定为低于挤出模头的温度。毛细凝聚表面的温度也应设定为低于微孔膜中溶剂/油的沸点或发烟点温度。毛细表面温度优选设定为高于周围氛围空气中水的露点,以防止水在装置上不好的“发汗”现象。本领域的技术人员能根据一定的氛围和所制的材料来设定系统。
得到的微孔产品的特征为具有许多可结晶热塑性聚合物的间隔的、无规分布的、非均匀形状的、各向等大的颗粒。这种聚合物颗粒被稀释剂材料包围,而相互隔离,形成通过纤丝互连的微孔网络。通过上述铸造方法来控制微孔的形状和尺寸。得到的膜可以进行单轴或双轴拉伸,以控制孔隙尺寸。另外,可以除去稀释剂,来控制孔隙结构。
凝聚板可构造成能提供放置静电固定线的夹缝或间隔。毛细凝聚表面装置的表面也可以用一种电绝缘材料做成或覆盖,以防止不宜有的起弧现象或对静电固定过程的干扰。另外,可在静电固定线附近吹以小容量的空气或其他气体流,以保持该处氛围对于低蒸发油或溶剂来说几乎是不饱和的。如图1和3所示。这种空气流动必须均匀并加控制,使得从不均匀空气流向铸造膜表面上的不均匀热传递造成的在TIPS材料中产生不良的微孔分布昼避免。小于1米/秒(200fpm)的空气流是需要的,优选是小于0.15米/秒的更小空气流。空气流应尽可能地均匀并是层流。
试看图3,本发明的设备30通常包括铸造表面32、凝聚板34和36以及吹气装置38。材料42通过凝聚板34和36的下面。蒸发材料凝聚在凝聚板44上,并如上述通过毛细表面46进行输送。使用静电固定线48来把材料固定在铸造表面32上。吹气装置38引导空气流F穿过静电固定线48,防止蒸发材料凝聚在静电固定线48上。可以装上一个流动分布介质40来提供均匀的空气流。
提供这种小空气流的一种方法是使用多孔介质。该多孔板可由许多种材料制成,如烧结金属、烧结塑料或烧结陶瓷、纸或合成过滤介质、筛网、冲孔板或它们的组合,产生对于空气层流来说必需的均匀阻力。如果静电固定线用的吹气位于毛细表面之间,那么电绝缘涂层可用来屏蔽凝聚板的两端以及用来涂覆或建造汇流管,因为金属导电接地表面会不利地消耗由静电固定线发出的带电离子,结果减少其效率。这可通过涂覆聚合物或陶瓷、电绝缘薄板或用电绝缘材料制造来达到这一点。气体可以是任何不与铸造材料或设备发生不当反应的气流,也不应包含颗粒和可凝聚的污染物。这种气体可以是空气、氮气、二氧化碳、氦气、其它惰性气体等。
与挤出模头相邻的凝聚表面上优选有个与模头的密封,以防止气体和载有溶剂/油的蒸气逃逸。因为热模头本身会产生自然对流的烟囱效应而促使这种逃逸。所述密封可以使模头表面上的夹缝精确紧密地配合于模头或者是使用适当的耐温度和耐油的密封材料(如金属箔、W.L.Gore and Associates生产的TeflonTM、扩展的TeflonTM衬垫材料、陶瓷和陶瓷纤维板或绳子等)。冷的凝聚板与模头不应直接接触,因为这会使模头冷却和凝聚板加热。因此,需要使用具有低导热性的材料来进行密封。另外,在这个位置可安装其它真空收集槽。
实施例
实施例1
本实施例显示受控铸造方法对于制造TIPS微孔膜的作用。
对于样品1A,将包含(1)45份可结晶聚合物(聚丙烯DS 5D45,熔体流动指数为0.6-0.8,购自Union Carbide Corp.,Danbury,Connecticut),(2)55份稀释剂(名称为White Mineral Oil#31的矿物油,购自Chevron Products Company,San Francisco,California)和(3)以可结晶聚合物为100份计的包含0.2份成核剂(购自Milliken Chemical的Millad 3988的二亚苄基山梨糖醇(dibenzylidinesorbitol))的熔体混合物,加入到25毫米共轴旋转的双螺杆挤出机(购自Berstorff,Charlotte,NC的ZE 25A型)中,形成熔体组合物。稀释剂是通过进料口加入到挤出机中的熔体混合物是预先熔融混合97.5份载体聚合物(聚丙烯DS5D45,熔体流动指数为0.6-0.8,购自Union Carbide Corp.,Danbury,Connecticut)和2.5份成核剂形成的母料。所有组分的总进料速度是6.8千克/小时。挤出机1-3区的温度分别保持在约204℃、271℃和271℃。挤出机4-9区的温度分别保持在227℃。螺杆转速是150rpm。
将此熔体组合物通过过滤器,再泵送通过保持在227℃的381毫米薄膜模头,送到93℃的成形铸造轮上,所述铸造轮的转速近似4.3mpm。这样就形成了厚度约114微米微孔的膜。
具体是薄膜离开薄膜模头后,但在重结晶之前,通过一毛细凝聚表面结构体(位于离开铸造轮表面约3厘米的地方)的下面。毛细凝聚表面结构体直接靠着薄膜模头,防止蒸发的矿物油从此位置逸出。毛细凝聚表面结构体由两块板组成,其间隔为8厘米供安置静电固定装置之用。在本实施例中不使用静电固定线,因此使用透明聚酯膜的50微米膜盖住这两块毛细凝聚表面板之间的间隔,使矿物油不致在这个位置逸出。
用循环水冷却毛细凝聚表面结构体。毛细凝聚表面板的温度为10℃。
如同样品1A制备样品1B,不同的是毛细凝聚表面板的温度上升到34℃。
如同样品1A制备样品1C,不同的是毛细凝聚表面板的温度上升到57℃。
如同样品1A制备比较例1(C1),不同的是在铸造微孔膜时不使用毛细凝聚表面板。即铸造轮上方的空间是没有装置的。
与样品C1相比,样品1A-1C显示出较少的矿物油蒸发。当存在毛细凝聚表面板时,铸造轮区域周围的空气流量减少。这使得矿物油的蒸发朝着铸造轮旋转的方向,并收集在毛细凝聚表面板上。由于总的通过量低和相应的少量矿物油蒸发,在毛细凝聚表面结构体上最接近薄膜模头的前两个凹槽中填充着矿物油,而其它凹槽大多没有矿物油凝聚物。
提高毛细凝聚表面板温度之后,矿物油的蒸发降低。这对应于当温度上升时有更多的矿物油凝聚在板上。
当存在毛细凝聚表面板时,显示薄膜淬冷的“霜线”进一步移动到铸造轮上片材的下面(到5点钟位置),而比较例1,该“霜线”靠近模头(在1点钟位置)。在样品1A-1C中形成的微孔膜按当前标准是可接受的。
实施例2
本实施例显示了毛细凝聚表面结构体凝聚其它微孔膜添加剂的能力。
如同实施例1a一样制备样品2A,不同的是使用不同的熔体组合物和进料速率。铸造轮速度和所得膜的厚度也与实施例1A不同。对于样品2A,将包含(1)63份可结晶聚合物(聚丙烯DS 5D45,熔体流动指数为0.6-0.8,购自Union CarbideCorp.,Danbury,Connecticut),(2)35份稀释剂(名称为White Mineral Oil#31的矿物油,购自Chevron Products Company,San Francisco,California),(3)0.02份成核剂(购自Clariant,Minneapolis,MN的Hostaperm E3B Red永久颜料的γ-喹吖啶酮)和(4)2.0份熔体添加剂(购自Ruger Chemical Company,Irvington,New Jersey的Span-20)(以可结晶聚合物为100份计)的熔混合物加入到25毫米共轴旋转的双螺杆挤出机(购自Berstorff,Charlotte,NC的ZE 25A型)中,形成熔体组合物。稀释剂是通过进样口加入到挤出机中。熔体混合物是预先熔融混合96份载体聚合物(聚丙烯,熔体流动指数2.5,购自Fina Oil & Chemical,Dallas,Texas的Fina 3374)和4.0份成核剂形成的母料。所有组分的总进料速度是4.5千克/小时。对样品2A,铸造轮速度为2.3rpm,结果得到微孔膜的厚度为178微米。毛细凝聚表面结构体的温度保持在10℃。
如同样品1A制备样品2B,不同的是毛细凝聚表面板的温度上升到36℃。
如同样品1A制备样品2C,不同的是毛细凝聚表面板的温度上升到56℃。
如同样品2A制备比较例2,不同的是在铸造微孔膜时不使用毛细凝聚表面板。即铸造轮上方的空间没有装置。
加入Span-20通常会在铸造区域周围增加大约75-100%的蒸发组分。实施例1所见的情况,如提高毛细凝聚表面结构体温度导致了更多挥发组分的凝聚,也见于实施例2。如同实施例1,挤出机的总通过量限帛了挥发组分的回收量。因此,很难定量测定回收的Span-20的量和矿物油的量。但是,在毛细凝聚表面板的出口,似乎并未增加烟尘的量。这可使人相信,凝聚板可有效地凝聚额外的挥发物质。
根据对本发明普通原理的上述描述和前述详细说明,本领域的技术人员容易对本发明作出各种改进。因此,本发明的范围只限于下述权利要求书及其等价内容。
Claims (30)
1.一种挤出方法,它包括:
(a)提供一个铸造表面和一个冷凝表面,所述凝聚表面与所述铸造表面有一定间隔,在所述铸造表面和所述凝聚表面之间形成夹缝;
(b)将一种材料挤出到所述铸造表面上,所述材料能够通过热致相分离形成微孔膜,在形成所述微孔膜的过程中,所述材料具有至少一种蒸发组分;
(c)在相对于所述凝聚表面的方向上移动所述铸造表面,以便所述材料移动通过所述夹缝;
(d)保持所述凝聚表面的温度,使得在所述凝聚表面上凝聚至少一部分所述至少一种蒸发组分。
2.如权利要求1所述的方法,它还包括调节所述夹缝,控制所述至少一种蒸发组分凝聚速率的步骤。
3.如权利要求1所述的方法,其特征在于所述材料是在高于所述铸造表面温度的温度挤出到所述铸造表面上的。
4.如权利要求1所述的方法,其特征在于所述铸造表面由一个辊、带或轮所提供,因此移动所述铸造表面包括使所述辊、带或轮运动。
5.如权利要求1所述的方法,其特征在于调节所述夹缝或所述凝聚表面的温度,用以改变所述至少一种蒸发组分的凝聚速率。
6.如权利要求1所述的方法,其特征在于所述材料包含热塑性聚合物、稀释剂和成核剂。
7.如权利要求1所述的方法,它还包括当所述凝聚物保持液态时,从所述凝聚表面除去凝聚物的步骤。
8.如权利要求1所述的方法,其特征在于所述凝聚表面包括毛细表面。
9.如权利要求1所述的方法,其特征在于相对于所述铸造表面的运动,所述凝聚表面具有一个尾端,并相邻于所述尾端装有一个排出口,所述方法还包括捕获通过所述排出口离开所述夹缝的废气。
10.如权利要求1所述的方法,它还包括在挤出所述材料后,将所述材料静电固定到所述铸造表面上的步骤。
11.如权利要求10所述的方法,其特征在于所述静电固定是用带电荷的导线完成的。
12.如权利要求11所述的方法,其特征在于所述凝聚表面包括通过一个槽子分隔的两部分凝聚表面,从而将所述材料外露在所述带电荷的导线形成的电场中。
13.如权利要求12所述的方法,它还包括使气体流过带电荷的导线,用以减少在带电线附近所述蒸发组分浓度的步骤。
14.如权利要求1所述的方法,其特征在于所述将材料挤出到铸造表面上的步骤还包括在铸造表面上形成一层膜。
15.如权利要求1所述的方法,它还包括控制铸造表面的温度、材料的温度、或结合控制这两者的温度,用来调节所述蒸发组分的蒸发速率的步骤。
16.一种铸造方法,它包括:
(a)提供一个铸造表面和一个冷凝表面,所述凝聚表面与所述铸造表面有一定间隔,在所述铸造表面和所述凝聚表面之间形成夹缝;
(b)将一种材料挤出到所述铸造表面上,所述材料能够通过热致相分离形成微孔膜,在形成所述微孔膜的过程中,所述材料具有至少一种蒸发组分;
(c)沿相对于所述凝聚表面的方向移动所述铸造表面,以便使所述材料移动通过所述夹缝;
(d)保持所述凝聚表面的温度,在所述凝聚表面上凝聚至少一部分所述至少一种蒸发组分。
17.如权利要求16所述的方法,其特征在于所述铸造是通过挤出完成的。
18.一种形成微孔膜的设备,它包括:
(a)适合接受铸造材料的铸造表面,所述材料能够通过用热致相分离形成微孔膜,在形成所述微孔膜的过程中,所述材料至少具有一种蒸发组分;
(b)与所述铸造表面隔开的凝聚表面,从而在所述铸造表面和所述凝聚表面之间形成夹缝,所述铸造表面能够沿相对于凝聚表面的方向移动,从而使所述材料移动通过所述夹缝,所述凝聚表面保持的温度使得在所述凝聚表面上凝聚至少一部分所述至少一种蒸发组分。
19.如权利要求18所述的设备,其特征在于所述铸造表面由辊、带或轮提供,移动所述铸造表面包括使所述辊、带子或轮运动。
20.如权利要求18所述的设备,其特征在于所述夹缝是可调节的。
21.如权利要求18所述的设备,其特征在于在高于所述铸造表面温度的温度将所述材料挤出到所述铸造表面上。
22.如权利要求18所述的设备,其特征在于调节所述夹缝或所述凝聚表面温度,用以改变所述至少一种蒸发组分的蒸发速率。
23.如权利要求18所述的设备,其特征在于所述材料包含热塑性聚合物、稀释剂和成核剂。
24.如权利要求18所述的设备,它还包括在所述凝聚物保持液态时,从所述凝聚表面上除去凝聚物的机构。
25.如权利要求24所述的设备,其特征在于所述凝聚表面包括毛细表面。
26.如权利要求18所述的设备,其特征在于相对于所述铸造表面的运动,所述凝聚表面具有一个尾端,且相邻所述尾端装有一个排出口。
27.如权利要求18所述的设备,它还包括将所述材料固定到所述铸造表面上的静电固定线。
28.如权利要求27所述的设备,其特征在于所述凝聚表面包括通过一个槽分隔的两部分凝聚表面,从而将所述材料外露在所述静电固定线形成的电场中。
29.如权利要求28所述的设备,它还包括使气体流过带电荷的线,用以减少在静电固定线附近的所述蒸发组分的设备。
30.一种防止静电固定线污染的方法,它包括使气体流过静电固定线,用以减少在静电固定线附近所述蒸发组分的浓度。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005014522A (ja) * | 2003-06-27 | 2005-01-20 | Toshiba Mach Co Ltd | フィルム・シート成形装置 |
JP2006083292A (ja) | 2004-09-16 | 2006-03-30 | Fuji Photo Film Co Ltd | 微細多孔性膜の安定製造方法および核酸分離精製方法におけるその使用 |
WO2008019532A1 (fr) * | 2006-08-11 | 2008-02-21 | Golden Energy Fuel Cell Co., Ltd. | Procédé de coulage en solution |
US20080233297A1 (en) * | 2007-03-23 | 2008-09-25 | Xerox Corporation | Methods of forming a photoreceptor device having a self-assembled patterned binder layer |
US7842214B2 (en) * | 2007-03-28 | 2010-11-30 | 3M Innovative Properties Company | Process for forming microporous membranes |
US20090074976A1 (en) * | 2007-09-14 | 2009-03-19 | Freking Anthony J | Method of reducing mottle and streak defects in coatings |
JP5162660B2 (ja) * | 2007-10-01 | 2013-03-13 | 東レバッテリーセパレータフィルム株式会社 | 押出成型品をプロセス凝縮液から保護する器具及び方法 |
WO2009120647A1 (en) * | 2008-03-26 | 2009-10-01 | 3M Innovative Properties Company | Methods of slide coating two or more fluids |
US20110027493A1 (en) * | 2008-03-26 | 2011-02-03 | Yapel Robert A | Methods of slide coating fluids containing multi unit polymeric precursors |
US20110014391A1 (en) * | 2008-03-26 | 2011-01-20 | Yapel Robert A | Methods of slide coating two or more fluids |
US8361611B2 (en) | 2009-03-20 | 2013-01-29 | Whiteoptics Llc | Diffusively light reflective paint composition, method for making paint composition, and diffusively light reflective articles |
FR2954595B1 (fr) | 2009-12-21 | 2012-03-30 | Bollore | Film de separateur, son procede de fabrication, supercondensateur, batterie et condensateur munis du fim |
US8460591B2 (en) * | 2010-03-23 | 2013-06-11 | GM Global Technology Operations LLC | Porous membranes and methods of making the same |
JP2013531236A (ja) * | 2010-06-07 | 2013-08-01 | スリーエム イノベイティブ プロパティズ カンパニー | 濾過方法及びデバイス |
RU2550157C2 (ru) * | 2010-12-23 | 2015-05-10 | Призмиан С.П.А. | Непрерывный способ для изготовления силового кабеля высокого напряжения |
US9248414B2 (en) | 2012-03-30 | 2016-02-02 | Pall Corporation | Large pore polymeric membrane |
CN105283161B (zh) * | 2013-06-13 | 2019-10-15 | 3M创新有限公司 | 个人卫生制品及其容器 |
JP6047264B1 (ja) * | 2015-02-04 | 2016-12-21 | 東レバッテリーセパレータフィルム株式会社 | 微多孔ポリオレフィン樹脂シートの製造装置および製造方法 |
DE102019119505A1 (de) * | 2019-07-18 | 2021-01-21 | Brückner Maschinenbau GmbH & Co. KG | Verfahren und Vorrichtung zur Herstellung eines Schmelze- und/oder Kunststofffilms |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2282009A (en) * | 1939-12-09 | 1942-05-05 | Eastman Kodak Co | Manufacture of vinyl resin film and sheeting |
GB1409786A (en) | 1972-05-12 | 1975-10-15 | Ici Ltd | Quenching of polymeric film |
DE3065278D1 (en) * | 1979-08-01 | 1983-11-17 | Ici Plc | Apparatus and process for extruding and quenching a thermoplastics film |
US4539256A (en) | 1982-09-09 | 1985-09-03 | Minnesota Mining And Manufacturing Co. | Microporous sheet material, method of making and articles made therewith |
SE458065B (sv) | 1986-10-16 | 1989-02-20 | Tore Eklund | Parabolantennfaeste som aer roerligt foer instaellning saavael foer utstraeckning i lodplanet som foer vinkel instaellning i lodplanet |
US4726989A (en) * | 1986-12-11 | 1988-02-23 | Minnesota Mining And Manufacturing | Microporous materials incorporating a nucleating agent and methods for making same |
US4999927A (en) * | 1988-05-13 | 1991-03-19 | Hoechst Aktiengesellschaft | Process and device for drying a liquid layer applied to a moving carrier material |
JPH06285953A (ja) * | 1993-04-05 | 1994-10-11 | Mitsubishi Heavy Ind Ltd | フィルム等の成形装置 |
US5581905A (en) | 1995-09-18 | 1996-12-10 | Minnesota Mining And Manufacturing Company | Coated substrate drying system |
US5694701A (en) | 1996-09-04 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Coated substrate drying system |
KR100449962B1 (ko) * | 1995-09-18 | 2005-01-15 | 미네소타 마이닝 앤드 매뉴팩춰링 캄파니 | 피복기재의건조장치 |
US5928582A (en) | 1996-03-19 | 1999-07-27 | Xenon Research, Inc. | Microporous membranes, method of manufacture |
US5813133A (en) * | 1996-09-04 | 1998-09-29 | Minnesota Mining And Manufacturing Company | Coated substrate drying system with magnetic particle orientation |
US5906862A (en) * | 1997-04-02 | 1999-05-25 | Minnesota Mining And Manufacturing Company | Apparatus and method for drying a coating on a substrate |
JPH1177802A (ja) * | 1997-09-09 | 1999-03-23 | Japan Steel Works Ltd:The | シート成形方法及び装置 |
US6047151A (en) | 1998-05-06 | 2000-04-04 | Imation Corp. | Drying system and method for an electrophotographic imaging system |
US6134808A (en) | 1998-05-18 | 2000-10-24 | Minnesota Mining And Manufacturing Company | Gap drying with insulation layer between substrate and heated platen |
CA2423125A1 (en) * | 2000-09-21 | 2002-03-28 | 3M Innovative Properties Company | Vapor collection method and apparatus |
JP4699660B2 (ja) | 2001-09-27 | 2011-06-15 | 富士フイルム株式会社 | 塗布膜の乾燥方法および装置 |
JP4631242B2 (ja) | 2001-09-27 | 2011-02-16 | 富士フイルム株式会社 | 塗布膜の乾燥方法および装置 |
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2001
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- 2001-09-21 AT AT01973751T patent/ATE380108T1/de not_active IP Right Cessation
- 2001-09-21 US US09/961,025 patent/US6790404B2/en not_active Expired - Lifetime
- 2001-09-21 DE DE60131758T patent/DE60131758T2/de not_active Expired - Lifetime
- 2001-09-21 KR KR1020037004174A patent/KR100770812B1/ko not_active IP Right Cessation
- 2001-09-21 WO PCT/US2001/042246 patent/WO2002024432A2/en active IP Right Grant
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- 2001-09-21 AU AU2001293302A patent/AU2001293302A1/en not_active Abandoned
- 2001-09-21 JP JP2002528480A patent/JP4745594B2/ja not_active Expired - Fee Related
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101410234B (zh) * | 2006-03-28 | 2012-08-08 | 富士胶片株式会社 | 聚合物膜的制备设备和制备方法 |
CN101583474B (zh) * | 2007-01-26 | 2012-08-29 | 佳能株式会社 | 生产在表面上具有凹形部的固形物的方法 |
CN114585490A (zh) * | 2019-08-14 | 2022-06-03 | 康宁股份有限公司 | 通过照射来减少湿挤出物上的表面油纹的系统和方法 |
CN114585490B (zh) * | 2019-08-14 | 2023-04-28 | 康宁股份有限公司 | 通过照射来减少湿挤出物上的表面油纹的系统和方法 |
CN112691558A (zh) * | 2020-12-02 | 2021-04-23 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | 膜材料的制备方法及系统 |
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CA2422261A1 (en) | 2002-03-28 |
US20050003033A1 (en) | 2005-01-06 |
BR0114028A (pt) | 2003-07-22 |
JP2004508979A (ja) | 2004-03-25 |
KR20040010529A (ko) | 2004-01-31 |
WO2002024432A2 (en) | 2002-03-28 |
EP1320452B1 (en) | 2007-12-05 |
KR100770812B1 (ko) | 2007-10-26 |
MXPA03002502A (es) | 2004-05-05 |
WO2002024432A3 (en) | 2002-06-13 |
US6790404B2 (en) | 2004-09-14 |
AU2001293302A1 (en) | 2002-04-02 |
ATE380108T1 (de) | 2007-12-15 |
EP1320452A2 (en) | 2003-06-25 |
JP4745594B2 (ja) | 2011-08-10 |
US20020135087A1 (en) | 2002-09-26 |
DE60131758D1 (de) | 2008-01-17 |
US6994533B2 (en) | 2006-02-07 |
CN100464826C (zh) | 2009-03-04 |
DE60131758T2 (de) | 2008-11-06 |
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