CN105500840A - 刚性轻质的复合片材及其制造方法 - Google Patents

刚性轻质的复合片材及其制造方法 Download PDF

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Publication number
CN105500840A
CN105500840A CN201610024543.6A CN201610024543A CN105500840A CN 105500840 A CN105500840 A CN 105500840A CN 201610024543 A CN201610024543 A CN 201610024543A CN 105500840 A CN105500840 A CN 105500840A
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China
Prior art keywords
composite sheet
sandwich layer
fiber
weight
sheet material
Prior art date
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Pending
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CN201610024543.6A
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English (en)
Inventor
德克·A·努德格拉夫
鲁道夫·纳斯
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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Publication of CN105500840A publication Critical patent/CN105500840A/zh
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Abstract

本发明涉及一种刚性轻质的复合片材及其制造方法。本发明公开了包括A类表面抛光的刚性轻质的复合材料，以及制造这些复合体的方法和包括这些复合体的制品。纤维补强的HPPC复合片材包括玻璃层压层和金属层。金属层被覆HPPC复合体中的单向的玻璃纤维，同时玻璃层压层向复合体提供抗机械刺穿性，同时提供具有A类表面抛光性质的复合片材，其仍然是轻质的。

Description

刚性轻质的复合片材及其制造方法
本申请为申请日为2009年6月3日，申请号为200980120956.2，发明名称为“具有A类表面抛光的轻质高刚度复合体”的发明专利申请的分案申请。
技术领域
本发明涉及聚合物复合材料，特别涉及具有A类表面抛光的轻质、高刚度复合片材，以及用于制造这些复合片材和包括这些复合片材的制品的方法。
背景技术
高性能热塑性复合(HPPC)片材由于HPPC材料的特性在很多机动车应用中的用途日益增加。这些片材比常规复合片材有所改进，常规复合片材一般包括在热固性的环氧或聚酯材料基质(matrix)中的玻璃纤维或碳纤维。
反之，HPPC材料使用热塑性基质而不是热固性基质，使用连续的玻璃纤维作为硬化材料。这些材料与标准复合片材相比并不凹陷(sag)，一般提供与铝金属片相同的刚度。
然而，HPPC片材一般不提供在它们表面上的非常良好的美观性，这限制它们在片材的美观性与它们的功能同样重要的很多应用如车体面板中的用途。获得HPPC片材A类表面的一种解决方案是用热塑性箔被覆HPPC片材。然而，在这些实施方案中，HPPC中的单向玻璃纤维在高光泽度应用中是可见的。这由玻璃基质和其间的热塑性材料之间的不同热膨胀引起。喷漆该部分仍然不能补救这些问题。
另一解决方案是将HPPC片材如AzdelSuperLight(SL)与薄(0.1-0.3mm)铝箔进行组合。在这些实施方案中，外表面具有与玻璃基质类似的热膨胀，因此这些产品能提供A类抛光。这些复合片材的缺点在于这些薄箔容易被锋利物体刺穿，使得它们不适用于很可能发生刺穿的很多应用中。此外，耐冲击性很可能降低。
因此，提供具有比现有技术复合片材更好的表面抛光而不具有与现有技术方案相关的一个或多个问题的刚性轻质复合片材会是有益的。提供制造具有比现有技术复合片材更好的表面抛光的刚性轻质复合片材的方法也会是有益的。
发明内容
本发明通过提供以下方案解决与现有技术相关的问题，提供包括A类表面抛光的刚性轻质复合片材以及制造这些复合片材和包括这些复合片材的制品的方法。本发明包括纤维补强的HPPC复合片材，其包括玻璃层压层(glasslaminatelayer)和金属层，以提供A类表面品质和充分的机械刺穿强度从而满足大多数结构要求。金属层被覆HPPC复合体中的单向玻璃纤维，同时玻璃层压层向复合体提供抗机械刺穿性。整个组件仍然是轻质的。
因此，一方面，本发明提供刚性轻质复合片材，其包括：芯层，其具有第一面和第二面，并包含热塑性材料和至少一种纤维；与芯层第一面附着的金属层；以及与芯层第二面附着的玻璃层压层；其中该复合片材具有A类表面抛光。
另一方面，本发明提供制造刚性轻质复合片材的方法，该方法包括以下步骤：提供具有第一面和第二面并包含热塑性材料和至少一种纤维的芯层；将金属层附着至芯层的第一面；以及将玻璃层压层层压至芯层第二面；其中该复合片材具有A类表面抛光。
具体实施方式
以下述描述和仅是说明性的实施例来更具体地描述本发明，其中很多改进或变体对本领域技术人员而言是显而易见的。说明书和权利要求书中所用的单数形式"一个(a)"、"一种(an)"和"该(the)"可以包括复数指示物，除非上下文中另有明确说明。此外，在说明书和权利要求书中所用的术语"包含"可以包括"由……组成"和"基本上由……组成"的实施方案。此外，文中公开的所有范围都包括端点，并且是可独立组合的。整个说明书中的术语“一个实施方案”、“另一实施方案”、“实施方案”、“一方面”、“另一方案”等意思是指所述与实施方案相关的具体要素(例如性质、结构、和/或特性)被包括于本文所述的至少一个实施方案/方面中，并可以存在或可以不存在于其它实施方案/方面中。此外，应理解所述要素可以以任何适当的方式在各种实施方案/方面中组合。
文中所用的近似语言可以用以修饰任何定量表述，该定量表述可以改变而不引起与其相关的基本功能的变化。因此，由术语如“约”和“基本上”修饰的值有时可以不限于规定的精确值。至少在一些情况下，近似语言可以相应于用于测量值的仪器的精度。
本发明提供包括A类表面抛光的刚性轻质复合材料，以及制造这些复合体和包括这些复合体的制品的方法。HPPC片材是纤维补强的HPPC复合片材，其包括至少一层玻璃层压层和金属层，玻璃层压层用于提供刚度和/或充分的机械刺穿强度，从而满足大多数结构要求；金属层用于提供A类表面品质抛光。整个组件仍然是轻质的。
HPPC片材包括至少三层，各自设计为向复合片材提供不同特性。在第一方面中，HPPC片材包括芯层。该芯层包括热塑性树脂和至少一种纤维。纤维向芯层提供刚度和/或冲击强度，由此向HPPC片材提供刚度/或冲击强度。HPPC片材在芯层一面上还包括玻璃层压层。玻璃层压层设计为向HPPC片材提供抗刺穿性。HPPC片材在芯层第二面上还包括金属层。该金属层被覆芯层中的纤维，并有助于向HPPC片材提供A类表面抛光。在供选择的实施方案中，HPPC片材包括位于金属片层和芯层之间的第二玻璃层压层。第二玻璃层压层还向HPPC片材提供另外的刚度，以及向HPPC片材提供另外的抗刺穿性。
因此，一方面，本发明提供HPPC片材，其包括包含热塑性树脂的芯层。在一种实施方案中，适当的热塑性树脂包括但不限于聚乙烯、聚丙烯、聚苯乙烯、丙烯腈-苯乙烯共聚物(acrylonitrylstyrene)、聚丁二烯(butadiene)、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚四氯丁烯(polybutyleneterachlorate)和聚氯乙烯(这些材料增塑的和未增塑的)，以及这些材料彼此的共混物或这些材料与其它聚合物材料的共混物。其它适当的热塑性树脂包括但不限于聚亚芳基醚、聚碳酸酯、聚酯碳酸酯、热塑性聚酯、聚醚酰亚胺、丙烯腈-丙烯酸丁酯-苯乙烯共聚物、无定形尼龙、聚亚芳基醚酮、聚苯硫醚、聚芳砜、聚醚砜、液晶聚合物、聚(1,4-亚苯基)化合物、耐高温聚碳酸酯、耐高温尼龙、和硅酮，以及这些材料彼此之间或与其它聚合物材料的合金和共混物。可以预料在本发明中能使用任何这样的热塑性树脂，其能通过加热充分软化从而使得熔融和/或成型，而没有化学分解或热分解。
除了有机聚合物基础树脂以外，本发明的复合材料还包括至少一种纤维，其设计为有助于向芯层提供强度，并由此向复合片材提供强度。适用于本发明的纤维包括玻璃纤维、碳纤维、石墨纤维、合成的有机纤维、特别是高模量有机纤维如对-和间-芳族聚酰胺纤维、尼龙纤维、聚酯纤维、或适用作纤维的上述任何热塑性树脂、天然纤维如大麻、剑麻、黄麻、亚麻、椰丝维、洋麻和纤维素纤维、矿物纤维如玄武岩、矿物棉(例如岩棉或渣棉)、硅灰石、矾土、和硅石等、或其混合物，金属纤维、金属化天然和/或合成纤维、陶瓷纤维、或其混合物。在一种实施方案中，芯层中的纤维含量可以为芯层重量的15％至85％，在供选择的实施方案中，为芯层重量的45％至60％。
在一种实施方案中，芯层中的纤维短于7毫米，不过这些较短纤维可能未向芯层提供充分的支撑，这有赖于HPPC片材的预计用途。在另一实施方案中，芯层中的纤维可以长于200毫米，不过这些较长纤维可能需要另外的加工时间以形成芯层，进而形成HPPC片材。因此，在本发明的有益实施方案中，在芯层中使用的纤维具有7至200毫米的长度，在供选择的实施方案中，具有10至75毫米的长度。除了它们的长度以外，在一种实施方案中，芯层中的纤维具有7至25微米的平均直径，在供选择的实施方案中，具有10至20微米的平均直径。
在一种实施方案中，芯层包含材料，其可得自Azdel,Inc。在该实施方案中，芯层是低密度玻璃毡(glassmat)热塑性复合物(GMT)。有利地，GMT的面密度为400克/平方米GMT(g/m2)至4000g/m2，不过面密度可以低于400g/m2或大于4000g/m2，这有赖于具体应用需要。有利地，密度上限应低于4000g/m2。
芯层一般使用以下材料制备：短切玻璃纤维、热塑性树脂和热塑性聚合物膜，以及用玻璃纤维或热塑性树脂纤维如聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、PC/PBT共混物、或PC/PET共混物制成的编织物或无纺布。一般而言，PP、PBT、PET、以及PC/PET和PC/PBT共混物是热塑性树脂。为了生产低密度GMT，将材料和其它添加剂计量至在装备有叶轮(impeller)的顶部开口混合槽中容纳的分散泡沫中。泡沫有助于分散玻璃纤维和热塑性树脂粘合剂。玻璃和热塑性树脂的分散混合物经由分配歧管被泵入至位于造纸机网部(wiresection)上方的网前箱(head-box)。然后随着分散的混合物使用真空通过移动的金属丝网，泡沫而不是玻璃纤维或热塑性树脂被去除，连续地产生均一的纤维性湿网(wetweb)。湿网通过干燥器以降低湿气含量并熔融热塑性树脂。当热网离开干燥器时，通过使玻璃纤维、热塑性树脂和热塑性聚合物膜的网通过成组热辊的辊隙，热塑性膜可以层压至网(web)中。无纺布和/或纺织品层还可以与热塑性膜一起或代替热塑性膜附着至网的一面或两面，从而提高处理玻璃纤维补强毡的容易性。芯层然后可以通过张力辊，并连续切割(裁切)至选定的尺寸，用于之后形成最终产品制品。
除了芯层以外，本发明的HPPC片材还包括玻璃层压层，其设计为向片材提供刚度和抗刺穿性。玻璃层压层包括多根通过热塑性树脂粘合在一起的基本上单向的补强玻璃纤维。术语"单向的"意思是指纤维基本上彼此平行排列，使得纤维的纵轴基本上平行。此处所用的"基本上平行"是指以下纤维，它们之间具有角度，其中该角度平均不偏离超过10度。此外，玻璃层压层基本上不含有纤维转换接头(cross-over)，其中转换接头纤维与排列纤维的纵轴形成的角度等于或大于30度。在那些包括两层以上玻璃层压层的HPPC片材实施方案中，相邻的玻璃层压层包括补强玻璃纤维，所述补强玻璃纤维在各玻璃层压层中是单向的，但在玻璃层压层中排列的玻璃纤维可以以与相邻玻璃层压层中排列的玻璃纤维成某一角度设置。该角度可以在0度至90度范围内。
在一种实施方案中，玻璃层压层是预浸渍体结构，其通过在排列的玻璃纤维上或在排列的纤维周围浸渍树脂形成。可以利用形成预浸渍体结构的各种方法，非限制性地包括溶液加工、浆液加工、用熔融聚合物直接浸渍纤维束、纤维共混(co-mingling)、以及热塑性粉末烧结为纤维束等。该技术一般是本领域中已知的。
在玻璃层压层中使用的热塑性树脂可以选自上述适用于芯层的热塑性树脂。芯层中的热塑性树脂可以与玻璃层压层中的热塑性树脂相同或不同。在使用多层玻璃层压层的那些实施方案中，在一层玻璃层压层中的热塑性树脂还可以与任何其它玻璃层压层中的热塑性树脂相同或不同。
尽管玻璃层压层描述成采用玻璃纤维，不过应当理解，在供选择的实施方案中和根据HPPC片材的预计用途，可以使用替换性纤维代替玻璃纤维，或者除了玻璃纤维以外使用替换性纤维。这些替换性纤维可以选自前述适用于芯层的纤维。
玻璃层压层可以在芯层的制造工艺期间附着至芯层，或者玻璃层压层可以在形成使用HPPC片材的制品之前附着。非限制性地，在制品形成工艺前，玻璃层压层可以通过以下附着至芯层：将玻璃层压层层压至芯层，玻璃层压层声波焊接至芯层，或将玻璃层压层简单敷设越过芯层。还可以使用本领域中已知的其它适当技术。
除了芯层和玻璃层压层以外，本发明的HPPC片材还包括金属层，其设计为向HPPC片材提供A类表面抛光。在一种实施方案中，金属层是具有0.01至0.5mm厚度的薄金属层。在另一实施方案中，金属层具有0.1至0.4mm的厚度。在再一实施方案中，金属层具有0.2至0.3mm的厚度。
金属层可以选自任何能向HPPC片材提供A类表面抛光的金属。范例性金属包括但不限于铝、铜、钢、或其组合。
使用任何能结合金属层至热塑性层的方法，可以将金属层结合至芯层，或者在供选择的实施方案中结合至玻璃层压层。在一种实施方案中，使用粘合剂将金属层结合至芯层或玻璃层压层。范例性粘合剂包括但不限于热塑性粘合剂，包括压敏粘合剂和热熔融粘合剂，如聚酰胺、改性聚烯烃、氨基甲酸酯(urethane)和聚烯烃。可以使用用粘合剂层预制的金属层，并在部分形成工艺中结合至HPPC结构。
在供选择的实施方案中，金属层可以包括一个或多个另外的处理步骤，有赖于抛光基质的潜在用途。例如，在一种实施方案中，金属层可以包括腐蚀处理，其在接合金属层之前应用。在供选择的实施方案中，金属层可以包括涂施于金属外面的底漆层，以使得金属层能随后被上漆。在再一实施方案中，金属层可以包括所有上述处理，如腐蚀保护处理、粘合剂和/或底漆。在供选择的实施方案中，可以使用金属层适用的其它处理。
如上所讨论，本发明的复合材料可以用于各种应用，其中刚性轻质材料用于美观性应用中，使得可以利用A类表面抛光的优点。该应用的实例包括但不限于建筑基础结构、飞行器、火车和海军舰艇侧壁面板、天花板、货物衬垫(cargoliner)、办公室隔墙、升降机井衬里、吊顶板材(ceilingtiles)、用于照明器具的嵌入式外壳(housing)，以及一般用蜂窝夹层结构、热塑性片、和FRP制成的其它该应用。
根据本发明的复合片材可以使用本领域中已知的方法成型为各种制品，包括压力成型、热成型、热压印(thermalstamping)、真空成型、压缩成型、和施压成型(autoclaving)。
该成文说明书使用实施例来公开包括最佳方式的本发明，以及使得本领域技术人员能实施并使用本发明。本发明的专利保护范围通过权利要求来限定，其可以包括本领域技术人员想到的其它实例。如果其它实例具有并未不同于权利要求书文字语言的结构要素，或者它们包括与权利要求书文字语言无实质性差异的等价结构要素，则该其它实例在本发明的范围内。文中引用的所有文献明确地引入本文作为参考。

Claims (10)

1.刚性轻质的复合片材，其包括：
芯层，其具有第一面和第二面，并包含热塑性材料和至少一种纤维；
金属层，其附着至所述芯层的第一面；和
玻璃层压层，其附着至所述芯层的第二面；
其中该复合片材具有A类表面抛光。
2.根据权利要求1所述的复合片材，其中所述芯层包括选自以下的热塑性树脂：聚乙烯，聚丙烯，聚苯乙烯，丙烯腈-苯乙烯共聚物，聚丁二烯，聚对苯二甲酸乙二醇酯，聚对苯二甲酸丁二醇酯，聚四氯丁烯，聚氯乙烯，聚苯醚、聚碳酸酯，聚酯碳酸酯，热塑性聚酯，聚醚酰亚胺，丙烯腈-丙烯酸丁酯-苯乙烯共聚物，无定形尼龙，聚亚芳基醚酮，聚苯硫醚，聚芳砜，聚醚砜，聚(1,4-亚苯基)化合物，硅酮，或包括前述树脂中至少一种的组合。
3.根据权利要求1或2所述的复合片材，其中所述芯层包括至少一种选自以下的纤维：金属纤维，金属化无机纤维，金属化合成纤维，玻璃纤维，石墨纤维，碳纤维，陶瓷纤维，芳族聚酰胺纤维，或包括前述纤维中至少一种的组合。
4.根据前述权利要求中任一项所述的复合片材，其中所述芯层包含20重量％至80重量％的至少一种纤维和20重量％至80重量％的热塑性树脂。
5.根据权利要求4所述的复合片材，其中所述芯层包含35重量％至55重量％的至少一种纤维和45重量％至65重量％的热塑性树脂。
6.根据前述权利要求中任一项所述的复合片材，其中所述金属层包括铝金属层。
7.根据权利要求6所述的复合片材，其中所述铝金属层的厚度为0.1至0.4mm。
8.根据权利要求7所述的复合片材，其中所述铝金属层的一面预先涂布有粘合剂。
9.根据权利要求8所述的复合片材，其中所述铝金属层已用腐蚀保护处理进行预处理，且该铝金属层已涂布有底漆用于随后在相对于粘合剂的另一面上进行上漆操作。
10.制造刚性轻质复合片材的方法，该方法包括：
提供芯层，其具有第一面和第二面，并包含热塑性材料和至少一种纤维；
将金属层附着至所述芯层的第一面；和
将玻璃层压层层压至所述芯层的第二面；
其中该复合片材具有A类表面抛光。
CN201610024543.6A 2008-06-03 2009-06-03 刚性轻质的复合片材及其制造方法 Pending CN105500840A (zh)

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