CN1791629A - 复合材料的制备方法 - Google Patents

复合材料的制备方法 Download PDF

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CN1791629A
CN1791629A CNA2004800132607A CN200480013260A CN1791629A CN 1791629 A CN1791629 A CN 1791629A CN A2004800132607 A CNA2004800132607 A CN A2004800132607A CN 200480013260 A CN200480013260 A CN 200480013260A CN 1791629 A CN1791629 A CN 1791629A
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base material
vapor deposition
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沙哈比·雅罗米
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Abstract

本发明涉及制备复合材料的方法，所述复合材料包括基材和该基材上的层，所述方法包括气相沉积步骤，其中在低于1000Pa的压力下，将包含三嗪化合物的化合物沉积在该基材上，从而形成该层，在气相沉积步骤期间，基材的温度介于－15℃与+125℃之间。本发明还涉及通过本文公开的方法得到的复合材料。

Description

复合材料的制备方法
本发明涉及制备复合材料的方法，所述复合材料包括基材和该基材上的层，所述方法包括气相沉积步骤，其中在低于1000Pa的压力下，将包含三嗪化合物的化合物沉积在该基材上，从而形成该层。
从WO 99/66097可以得知这样的方法。在WO 99/66097中，含三嗪的层主要作为阻隔层来减少例如基材的氧透过率(OTR)。WO 99/66097提到了各种适合的三嗪化合物，例如蜜胺。
该已知方法的缺点是阻隔性质并不总是足够的。
本发明的目的是减少上述缺点。
本发明的目的通过使气相沉积步骤期间的基材温度在-15℃与+125℃之间而达到。
本发明的优点是获得具有改良性质(特别是阻隔性质)的复合材料。令人惊讶的是，选择较高的基材温度可得到具有改良阻隔性质的复合材料，而在工业上基材温度通常为-20℃或更低。
根据本发明的方法制备的复合材料包括基材。基材是作为层的载体的材料；它是层施加于其上的物体。基材基本上可以由均相材料组成，或者其本身可以是非均相或复合材料。基材可以包括各种层。基材可以是基本上平坦的，或者具有复杂的三维形状。合适的基材的例子是柔性包装材料(例如膜)、工具(tools)，刚性包装材料(例如瓶子)或者预成形包装盒。优选地，基材包括聚合材料、纸、硬纸板、金属、金属化合物、金属氧化物、陶瓷或者其组合。聚合化合物的例子是热塑性化合物和热固性化合物。热塑性化合物的例子是聚乙烯(PE)、聚丙烯(PP)和聚对苯二甲酸乙二醇酯(PET)。这些热塑性化合物通常以膜的形式使用，可以原样使用或者经定向后使用；这样的定向可以是双轴的，例如双轴定向聚丙烯膜(BOPP)。优选地，基材本身是包括含铝、氧化铝、铝和氧化铝、或者氧化硅的气相沉积层的复合材料，因而根据本发明的层是施加于含铝层或者含硅层之上的。
根据本发明的复合材料包括基材上的层。通过气相沉积步骤将该层施于基材上。气相沉积本身是已知的。如所公知的，气相沉积步骤通常在减压(即低于大气压力)下进行。在根据本发明的方法中，压力低于1000Pa。在气相沉积步骤中，化合物沉积在基材上，从而形成层。根据本发明，所述化合物包括三嗪化合物。原则上，可以选择任何三嗪化合物；优选地，三嗪化合物包括蜜胺(melamine)、蜜白胺(melam)、蜜勒胺(melem)、蜜隆(melon)、被可聚合基团官能化的蜜胺、蜜胺盐或者其混合物。更优选地，三嗪化合物包括蜜胺；最优选地，三嗪化合物基本上由蜜胺组成。
在气相沉积步骤中所形成的层的厚度取决于其预期用途，因此可以在宽的范围内变化。优选地，层的厚度小于100μm，更优选小于10μm，甚至更优选小于1μm；最小厚度优选至少2nm，更优选至少10nm。
在气相沉积步骤期间，基材的温度在-15℃与+125℃之间。在这里将基材的温度定义为未被气相沉积的基材部分的温度。例如，如果对控温涂覆滚筒上导引的膜进行气相沉积步骤，则基材的温度是涂覆滚筒被控制的温度，因而是与涂覆滚筒直接接触的膜表面部分的温度。在此情况下，考虑到欲沉积的化合物通常具有远高于125℃的温度，如所公知的，基材被沉积的一侧的温度通常高于未被沉积那一侧的温度。
已发现，与基材温度为-20℃或更低的气相沉积步骤相比，当基材的温度上升至-15℃及以上时，复合材料的阻隔性质有所改善。另一方面，为了维持可接受的沉积速度和确保基材保持完整(即未变形、溶解或者劣化)，基材的温度通常需要保持低于+125℃，或者根据基材的特定性质所需而远低于+125℃，同时保持高于-15℃。优选地，在气相沉积步骤期间，基材的温度为-5℃、0℃或+5℃或者更高；更优选地，所述温度为+10℃、+15℃或+20℃或者更高。已发现，当基材的温度升至更高于-15℃时，阻隔性质有更进一步的提高。如上所示，由于基材稳定性和/或速度经济性的原因，确保气相沉积步骤期间的基材温度保持在+125℃或更低、优选+90℃或更低、更优选+60℃或更低或者+50℃或更低、特别是+40℃或更低、最优选+30℃或更低是有用或者必须的。
确保基材具有所定义的温度的方法是已知的。一个这样的确保基材具有所定义温度的已知方法可以应用于下述情况：基材的至少一个区域、平面或者侧边不会被气相沉积任何层；这样将所述区域、平面或者侧边与冷却表面或者加热表面接触从而使温度达到并且维持在所需水平。作为例子，已知如果基材是膜并且气相沉积步骤作为连续过程或半连续过程进行，从而将层沉积于膜的一侧上，则所述膜可以受控温滚筒(也称之为涂覆滚筒)的导引，其方式使得膜的另一侧(不沉积任何层的一侧)在气相沉积步骤之前和/或期间和/或之后与控温滚筒接触。
根据本发明的气相沉积步骤在1000Pa或更低的压力下进行。已知气相沉积步骤可以在亚大气压下进行，例如在所述1000Pa或者在更低压力例如100Pa或10Pa或者更低。在WO 99/66097的实施例中，压力甚至降至5×10-3Pa与1×10-2Pa之间。令人惊讶地发现，复合材料的性质，例如阻隔性质，可以通过降低气相沉积步骤进行的压力而更进一步地改善，优选降至4×10-3Pa或更低。更优选地，气相沉积步骤在2×10-3Pa或更低或者1×10-3Pa或更低的压力下进行；特别地，气相沉积步骤在5×10-4Pa或更低、或者1×10-4Pa或更低的压力下进行；更特别地，气相沉积步骤在5×10-5Pa或更低、或者1×10-5Pa或更低的压力下进行；最优选地，气相沉积步骤在5×10-6Pa或者甚至1×10-6Pa或更低的压力下进行。目前认为低于1×10-10Pa的压力无法进一步增加以上所提及的好处。
在根据本发明的另一个实施方式中，气相沉积步骤的压力减至4×10-3Pa或更低对所得的复合材料的性质(例如阻隔性质)有如此的影响，以致此方法可以部分地甚至完全地取代在气相沉积步骤期间将基材的温度调整至-15℃与+125℃之间的方法的有益效果。在此实施方式中，因而可以将基材的温度降至-15℃、-20℃、-40℃或者甚至-60℃或更低。
层通常包括含三嗪化合物的晶粒。其中化合物以结晶、非聚合形式存在并且被边界分离的晶粒对本领域的技术人员来说是公知的一般结晶性化合物。如果层基本上是由含三嗪化合物的晶粒组成，则可以实现该层赋予的性质(特别是阻隔性质)的最佳效果。如果该层全部或者几乎全部由含三嗪化合物的晶粒组成，则优选整个层基本上都由三嗪化合物组成。
层中的晶粒具有尺寸，在此定义为晶粒内平行于基材表面(即从顶部观察)的最大尺寸。已发现，在确定重要特性(例如阻隔性质)时，第二层中含三嗪的晶粒的平均尺寸可能与第二层的厚度同样重要，或者甚至更为重要。不受限于任何特定的理论解释，通过仔细调整晶粒间的边界的数量和尺寸而不是沉积层的厚度(这与技术人员的预期相反)，可以达到最佳阻隔性质。据认为，晶粒间的边界在赋予复合材料以阻隔性质方面相对较弱；因此，如果平均晶粒尺寸变得太小，则边界太多从而对阻隔性质有负面影响。另一方面，如果平均晶粒尺寸变得太大，则边界区域本身变得不成比例的大，从而也使阻隔性质受损。平均晶粒尺寸优选至少10nm，更优选至少50nm，甚至更优选至少100nm，最优选至少200nm。平均晶粒尺寸优选至多2000nm，更优选至多1000nm，甚至更优选至多600nm，最优选至多400nm。在本发明上下文中，平均尺寸表示数量平均。在一个优选实施方式中，层基本上由三嗪化合物组成因而晶粒内的三嗪晶体结构并无明显中断。
根据本发明的方法，气相沉积步骤优选以使得含三嗪晶粒的平均尺寸为10nm与2000nm之间的方式进行。已发现，气相沉积晶粒的平均尺寸除其它因素外还取决于晶粒生长于其上的表面上的成核点的数量：成核点数量越多，平均晶粒尺寸则越小。因此可以通过调整气相沉积步骤中影响晶粒生长的成核点数量的工艺条件来改变沉积晶粒的平均尺寸。根据本发明已发现，成核点的数量随着沉积温度的差异(即含三嗪化合物被加热的温度与基材温度的差异)的增大而增加。优选地，所述温度差异介于150℃与370℃之间，而与根据本发明的基材的温度范围有关。同样已发现，如果气相沉积步骤进行的压力升高，则成核点的数量减少。优选地，气相沉积步骤的压力介于10-6Pa与10-2Pa之间。此外，应当注意到基材的性质也影响所形成的成核点数量。因此，本领域的技术人员可以在这里所给出的关于温度差异和压力的教导下，通过实验来确定气相沉积步骤的最佳工艺条件，从而达到在以上所给优选范围内的平均晶粒尺寸。
通过在气相沉积步骤之前或者期间对基材进行进一步的处理，可以有利于进一步增强由根据本发明的方法得到的复合材料的性质。通过在气相沉积步骤期间或者之后对复合材料进行进一步的处理，也可以有利于进一步增强由根据本发明的方法得到的复合材料的性质。这样的进一步的处理的例子是：交联步骤，其中层内的三嗪化合物与自身或者另一种化合物进行反应，该化合物与三嗪化合物被共同施加于层内或者独立地与该层接触；等离子体处理；电晕处理；施加紫外线；施加电子束。这样的进一步的处理有利于增强层的特定目标性质，例如附着力、耐湿性或者耐刮性。进一步的处理可以导致层的晶粒尺寸和/或结构的改变。
优选地，在气相沉积步骤之前或者期间，用等离子体、电晕、紫外线、电子束或者反应性气体对基材进行处理。反应性气体是能与三嗪化合物和/或基材发生反应的气体。所述反应可以立即发生，或者随后发生。所述反应可以不经辅助而发生，或者借助于辅助手段例如温度或辐射处理而发生。反应性气体优选包括水和/或甲醛。在一个优选实施方式中，基材是包括含铝的层的复合材料，从而含三嗪的层被沉积于含铝的层之上，而且反应性气体包含水蒸气。由于水蒸气与铝的化学反应，在含铝的层的表面形成化合物，这增强了含三嗪的层对基材的附着力。
优选地，在气相沉积步骤期间或者之后，用等离子体、电晕、紫外线、电子束或者反应性气体对复合材料进行处理。反应性气体优选包括水和/或甲醛。
在根据本发明的一个实施方式中，第二层被添加于复合材料的含三嗪化合物的气相沉积层(在此实施方式中称之为第一层)之上。第二层可以气相沉积于第一层之上，但是也可以以任何其它已知的方式而施加，例如通过层压。依赖于复合材料的功能和/或所需的性质，第二层可以包含任何化合物。例子是：热塑性或者热固性聚合化合物、与第一层的化合物相同或者不同的三嗪化合物、金属化合物(例如铝)、金属氧化物(例如氧化铝)。第二层本身可以是复合材料。
由于气相沉积技术用于生成第一层，而且考虑到三嗪化合物的特性，已发现第一层可以作为中间层。这里的“中间层”是指可以消除基材表面呈现的任何表面粗糙度的至少一部分的层，从而第二层可以施加于更加光滑的表面(即较低表面粗糙度)；这具有降低损坏第二层的风险的优点。此外，已发现当第一层的平滑化功能为主要功能而且其作为阻隔层的功能并不重要时，气相沉积步骤的基材温度可以处于比上述给出的温度范围更宽的范围内，因此优选-60℃与+125℃之间，更优选-30℃与+50℃之间。
本发明还涉及复合材料，其可通过上述根据本发明的方法而获得。所述复合材料可以用于任何应用中，特别是需要阻隔性质(例如低OTR)的应用，例如对氧敏感的或者易腐败的制品(例如食品)的包装。
下面通过实施例和对比实验来说明本发明。
实施例1
将包含蜜胺的层气相沉积于由双轴定向聚丙烯(BOPP)膜组成的基材之上。气相沉积步骤在10Pa或者约1×10-4大气压的压力下进行。基材的温度是+20℃。由坩锅蒸发蜜胺；坩锅中的蜜胺保持310℃的温度。蜜胺沉积于基材上。以7米每秒的速度沿着坩锅导引基材；这是很高的速度，反映出工业实践的条件。所得到的复合材料具有47cm3/m2.bar.day的氧透过率(OTR)。
对比实验1
以与实施例1相同的方式制备复合材料，但是基材的温度是-20℃而不是+20℃。OTR为120cm3/m2.bar.day，而对没有任何层沉积的基材(BOPP膜)进行测量，OTR为1600cm3/m2.bar.day。
从实施例和对比实验可以容易地看出，与未处理的基材相比，尽管已知方法已经使OTR有利地降低，从而提高阻隔性质，但是根据本发明的方法实现了OTR的进一步降低，即进一步增强了阻隔性质。

Claims (18)

1.制备复合材料的方法，所述复合材料包括基材和该基材上的层，所述方法包括气相沉积步骤，其中在低于1000Pa的压力下，将包含三嗪化合物的化合物沉积在该基材上，从而形成该层，所述方法的特征在于气相沉积步骤期间的基材温度介于-15℃与+125℃之间。
2.根据权利要求1所述的方法，其中在气相沉积步骤期间，基材的温度介于0℃与+50℃之间。
3.根据权利要求1或2-所述的方法，其中气相沉积步骤在低于5×10-3Pa的压力下进行。
4.根据权利要求1-3中任何一项所述的方法，其中三嗪化合物包括蜜胺、蜜白胺、蜜勒胺、蜜隆、被可聚合基团官能化的蜜胺、蜜胺盐或者其混合物。
5.根据权利要求4所述的方法，其中三嗪化合物包括蜜胺。
6.根据权利要求1-5中任何一项所述的方法，其中在气相沉积步骤之前，用等离子体、电晕、紫外线或者电子束对基材进行处理。
7.根据权利要求1-6中任何一项所述的方法，其中在气相沉积步骤之前，用反应性气体对基材进行处理。
8.根据权利要求7所述的方法，其中反应性气体包括水和/或甲醛。
9.根据权利要求8所述的方法，其中基材是包括含铝层的复合材料，因而含三嗪的层被沉积于含铝层之上，并且反应性气体包括水蒸气。
10.根据权利要求1-9中任何一项所述的方法，其中用等离子体、电晕、紫外线或者电子束对所述层进行处理。
11.根据权利要求1-10中任何一项所述的方法，其中用反应性气体对所述层进行处理。
12.根据权利要求11所述的方法，其中反应性气体包括水和/或甲醛。
13.根据权利要求1-12中任何一项所述的方法，其中在气相沉积步骤之后，第二层被添加于已存在的层之上。
14.根据权利要求13所述的方法，其中根据根据权利要求1-11中任何一项所述的层被用作中间层。
15.通过权利要求1-14中任何一项所述的方法所得到的复合材料。
16.根据权利要求15所述的复合材料，其中基材包括聚合膜，特别是双轴定向聚丙烯膜。
17.根据权利要求16所述的复合材料，其中基材包括含铝或氧化铝或氧化硅的气相沉积层，从而使含三嗪化合物的化合物气相沉积在含铝或氧化铝或氧化硅的层上。
18.权利要求15-17中任何一项所述的复合材料在包装特别是食品包装中的用途。
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CN102015289B (zh) * 2007-07-20 2015-07-01 帝斯曼知识产权资产管理有限公司 层压制品、含有基材和涂层的复合层及其制造方法和装置
CN103827179A (zh) * 2011-07-05 2014-05-28 应用材料公司 用于处理柔性基板的方法
CN106893134A (zh) * 2011-07-05 2017-06-27 应用材料公司 用于处理柔性基板的方法

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HK1093078A1 (en) 2007-02-23
US7794786B2 (en) 2010-09-14
US20070207319A1 (en) 2007-09-06
CL2004001060A1 (es) 2005-04-29
US7998527B2 (en) 2011-08-16
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WO2004101662A8 (en) 2005-12-29
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JP2007508161A (ja) 2007-04-05
ATE407168T1 (de) 2008-09-15
BRPI0410337A (pt) 2006-05-30
DE602004016313D1 (de) 2008-10-16
ES2314397T3 (es) 2009-03-16
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BRPI0410337B1 (pt) 2014-11-18
WO2004101662A1 (en) 2004-11-25
KR101130147B1 (ko) 2012-03-28
EP1622970A1 (en) 2006-02-08
CN100478381C (zh) 2009-04-15
RU2005139135A (ru) 2006-04-10
CA2525875C (en) 2012-07-17
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