CN113306393A - 氨基甲酸酯和石墨烯内部饰板 - Google Patents

氨基甲酸酯和石墨烯内部饰板 Download PDF

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CN113306393A
CN113306393A CN202110208397.3A CN202110208397A CN113306393A CN 113306393 A CN113306393 A CN 113306393A CN 202110208397 A CN202110208397 A CN 202110208397A CN 113306393 A CN113306393 A CN 113306393A
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skin
graphene
panel
urethane
tpu
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M·M·雷迪
G·J·法拉尔
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Cpk Interior Decoration Materials Co ltd
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Abstract

提供了一种氨基甲酸酯和石墨烯内部饰板。在另一方面，该内部饰板可以是机动车辆仪表板、气囊盖、门饰板、中央控制台、膝垫、座椅机构盖、柱盖等。另一方面包括注入有石墨烯的热塑性聚氨酯化合物，并且更具体地包括TPU‑石墨烯组合物或混合物，该组合物或混合物可以被研磨、模制、然后用于车辆内部应用。

Description

氨基甲酸酯和石墨烯内部饰板
技术领域
本披露内容总体上涉及一种内部饰板，并且更具体地涉及一种氨基甲酸酯和石墨烯内部饰板。
背景技术
传统上，机动车辆仪表板蒙皮由多种多样的聚合材料制成，包括聚氯乙烯(“PVC”)、热塑性聚氨酯(“TPU”)、热塑性聚烯烃(“TPO”)以及热塑性弹性体(“TPE”)。这些蒙皮可以通过比如凝塑旋转模制和热成型等方法制成。在以下专利中披露了示例：由Farrar发明的题为“Polyvinylchloride for Seamless Airbag Doors[用于无缝气囊门的聚氯乙烯]”美国专利公开号2017/0240736，以及于2009年7月14日授予Tansey的题为“PVC Alloyfor Use in Air Bag Doors[用于气囊门的PVC合金]”的美国专利号7,560,515，这两个专利均通过引用并入本文。
在过去，TPU用于被组装到仪表板上的单独气囊门。最近，于1998年10月20日授予Humphrey等人的题为“Light Stable Aliphatic Thermoplastic Urethane Elastomersand Method of Making Same[光稳定性脂族热塑性氨基甲酸酯弹性体及其制作方法]”的美国专利号5,824,738讨论了通过凝塑模制形成的光稳定性脂族热塑性聚氨酯的传统用途。这项专利通过引用并入本文。然而，传统的TPU会在通过用刀等刻划蒙皮而有意地形成气囊盖门撕裂缝的地方不期望地“自我抚平”或重接。此外，据信脂族TPU和PVC共混物/合金当在内部装饰部件的寿命期间暴露于高热时展现出其原来的物理特性降低并且随着时间的流逝趋于变脆。
韩国专利号2014-0005684披露了一种热塑性聚氨酯膜，包含按重量计30-40％的石墨烯粉末。石墨烯的这种非常高的浓度不期望地导致TPU变得坚硬和刚性。因此，缺乏柔性使得难以将膜从模具中移除，并且最终产品缺乏车辆乘员想要的柔软感和冲击吸收，并且不包含所需的弯曲特性以允许令人满意的气囊展开。
发明内容
根据本发明，提供了一种氨基甲酸酯和石墨烯内部饰板。在另一方面，该内部饰板可以是机动车辆仪表板、气囊盖、门饰板、中央控制台、膝垫、座椅机构盖、柱盖等。另一方面包括注入有石墨烯的热塑性聚氨酯化合物，并且更具体地包括TPU-石墨烯组合物或混合物，该组合物或混合物可以被研磨、模制、然后用于车辆内部应用。还披露了一种制造氨基甲酸酯和石墨烯内部饰板的方法。
本发明的设备和方法优于传统的装置。例如，本发明的注入有石墨烯的热塑性聚氨酯产生了增强的热性能以及改善的电磁干扰(“EMI”)屏蔽特性。此外，本发明的方法采用研磨工艺，其与比如PVC和TPU等传统的低温可展开级塑料相比会在凝塑或旋转模制期间使得最终产品具有优异的流动性和粘度。本发明的设备和方法采用有利浓度的石墨烯，其保持了最终板的柔性和柔软性，但仍实现了组装到饰板上或位于其后方的比如电子控制器、传感器等电子部件的预期电磁干扰屏蔽。根据以下结合附图的描述以及权利要求，可以确定其他特征和优点。
附图说明
图1是示出本发明的内部饰板的立体图；
图2是沿图1的线2-2截取的截面视图，示出了本发明的内部饰板；
图3是示出了制造本发明的内部饰板的方法的示意图；以及
图4和图5是示出了用于制造本发明的内部饰板的方法步骤的示意流程图。
具体实施方式
在图1和图2中示出了用于轮式机动陆地车辆的内部饰板。内部饰板优选地是仪表板11，但是可以可替代地包括中央控制台13、单独气囊盖、门饰板、中央控制台、膝垫、座椅机构盖、柱盖等。仪表板11包括外蒙皮15、中间柔韧性泡沫层17以及内部刚性基底19。
蒙皮15的一段用作一体式气囊门21，在其后方是包括滑槽25的气囊组件23。当膨胀的气囊使蒙皮15中的撕裂缝31破裂时，气囊门21围绕与大致水平伸长的基底边缘27相邻的上下弯曲线铰接或枢转。蒙皮15的“无缝”或隐藏样式是优选的，由此使得撕裂缝31位于其背面表面上并且对于车辆乘员或使用者而言是不可见的。撕裂缝31优选地具有H形，尽管可以采用比如U形和X形等其他构型。
可以使用龙门架驱动式激光器或铰接式机器人驱动式刀来形成撕裂缝31，该刀在蒙皮15形成之后沿着其背面表面水平滑动。在刻划之后，余留的撕裂缝31材料是在0.3-0.66mm之间，平均为0.50mm。尽管可用较薄的撕裂缝，但如果小于0.457mm，则刻划线将会通透到零件的表面。因此，刻划的深度大于一半但小于全部蒙皮厚度。蒙皮上的刻划线当在120℃下暴露了1000小时的时候没有展现出任何抚平或重接。换句话说，注入有石墨烯的TPU无法自我抚平，并且有助于以部分地隔断和分开的壁的方式保持刻划线。
当将最终板安装在车辆中时，混合式TPU和石墨烯组合物的组合导致良好的高温和低温性能。在120℃下加热老化500小时之后，本文所用组合物的拉伸强度、伸长率和撕裂强度的变化不应超过±30％。更具体地，优选实施例的偏差预期不超过±15％。此外，物理特性也可以在-30℃下执行以作为寒冷气候气囊展开的指标。在-30℃下未老化的物理特性预期与室温特性一致，伸长率值大于300％，这是这种材料在这个温度下在气囊展开期间不应破碎的指标。
整个蒙皮15由混杂的注入有石墨烯的热塑性聚氨酯干共混物制成，并且可以可选地包括一对相容剂，比如马来酸酐和乙烯乙酸乙烯酯(“EVA”)。优选的未处理的石墨烯纳米颗粒41为6-10层的机械剥离的石墨烯粉末的形式，并且平均薄片尺寸为约40μm的。石墨烯粉末有助于实现蒙皮15和最终形成的仪表板(蒙皮形成了仪表板的一部分)的EMI屏蔽、机械特性增强、散热、静电放电、抗静电性、抗UV性以及气障功能。而且，TPU基质中的石墨烯层控制了耐热性的程度，其中，剥离越大，耐热性、导电性和EMI屏蔽越大。
优选的TPU脂族化合物的体积密度为500-700kg/m3。优选的悬浮级树脂是由脂环族异氰酸酯与聚醚多元醇的反应制得的来自Covestro的Texin 3042。此外，可能的相容剂可以包括马来酸酐接枝的TPU和/或马来酸酐接枝的聚丙烯/聚乙烯(比如来自Westlake的Epolene E-43/C-19)、丙烯马来酸酐共聚物(比如Honeywell的
Figure BDA0002950280040000041
597P)以及乙烯乙酸乙烯酯共聚物(比如来自Honeywell的
Figure BDA0002950280040000042
400A)。马来酸酐/乙基乙酸共乙烯酯优选为总共混配方的按重量计1-8％，更优选为2-5％，并且有助于所需的机械特性。
在凝塑模制之后(也称为滚塑模制或滚铸)，气囊区域21中的蒙皮15的典型的平均材料厚度为近似1.10mm，但是可以低至0.70mm。通过非限制性示例，正态容差优选为0.9-1.1mm。在复合时，材料的玻璃化转变值为负30℃至负65℃。
现在参照图3和图4，将石墨烯41和热塑性聚氨酯43的组合物进送到双螺杆挤出机45中，然后在其中熔融共混，接着进行研磨以获得凝塑级粉末。还可以添加可选的添加剂47，比如光和UV稳定剂、相容剂、着色颜料等。这种配方形成高性能凝塑TPU，非常适合用于机动车辆内部的无缝气囊应用。
可以使用以下工艺来形成蒙皮15。挤出热分布为180-220℃。将预定量的TPU、着色颜料和稳定剂添加剂包进给到挤出机45中，然后添加石墨烯。挤出工艺有助于将石墨烯层分散和混合到TPU基质中。然后将浆料共混物泵出挤出机喷嘴以在水下制粒。然后将由此获得的干燥粒料51送至研磨机53以获得凝塑级粉末55。研磨机可以进行低温研磨、水下研磨、粉碎、湿/干磨等。
如图3、图4和图5所见，将由镍基金属制成的多部件式浆料模具61预热至180℃至250℃。将粉末55放置在模具61内部的密闭粉末箱中。当粉末55在箱中熔化时，机器使模具61旋转。当粉末液化时，箱自动松开并在模具内打开，由此在模具保持加热和旋转的同时使液态TPU-石墨烯混合物分散以完全覆盖模具内表面。混合物随后在模具61内固化，并且模具冷却至约50℃。此后，打开模具，并且可以将柔性蒙皮脱模或从中移除。
如先前所讨论的，刀或激光器在蒙皮的背面表面上部分地切开撕裂缝。随后，将已刻划的蒙皮放置在另一个第二模具腔体中，并且将预先注塑模制的刚性聚合物基底插入第二模具腔体中，它们之间具有局部间隙。关闭这个第二模具，并且在第二模具内的蒙皮与基底之间的间隙中注射开孔软质泡沫。这种工艺可以称为“现场发泡”或低压注塑模制工艺。然后使泡沫固化，并且从第二模具中移除完成的内部饰板。而且，可以刺出孔，并且此后可以将比如托架、夹子、紧固件、装饰性贴花、HVAC出口等附加部件组装到内部饰板上以形成饰板子组件或模块。
在一个示例中，蒙皮材料具有按重量计80-95％的TPU树脂、按重量计1-20％的石墨烯以及按重量计1-5％的酸酐相容剂。在一个示例中，未处理的石墨烯粉末最多可具有10层。
在气囊展开时，在-30℃和2分钟延迟下，气囊展开不会引起蒙皮碎裂。在120℃下加热老化之后，蒙皮材料的伸长率变化不超过+30％。而且，在120℃下加热老化之后，蒙皮材料的拉伸强度变化不超过+30％。此外，在120℃下加热老化之后，撕裂缝处的撕裂强度变化不超过30％。
通过可以用于评估材料在正常大气条件下的流动能力的简单测试来确定静止角(“AOR”)。粉末可分为几种流动性类别，但是对于一般用途：低于30°角表示材料将具有优异的流动特性；低于40°产生一般的流动特性；以及大于45表示较差的材料流动特性。柔性蒙皮材料的流动能力可以归因于许多因素，包括：其摩擦系数；其密度；颗粒的尺寸、形状/孔隙度；以及所使用的树脂和增塑剂体系的含量和类型。作为示例，具有良好的耐寒性能的用于仪表板应用的高增塑PVC具有较大的静止角(超过45°)，这会导致材料流动性较差、废料增加以及针对给定零件设计所允许的几何自由度降低。相反，本文描述的使用石墨烯的本发明的材料具有优异的流动特性，从而导致废料较少、设计自由度增加以及晶粒结构改善。本发明的TPU-石墨烯材料的静止角的值是26-34°。
电磁干扰是破坏性电磁能量经由辐射或传导路径或两者而从一个电子装置传输到另一个电子装置的过程。在机动车辆电子系统中，EMI会对内部集成电路的性能、以及紧邻的其他电子部件的性能产生不利影响。本发明的石墨烯纳米颗粒是导电填料，理想地适合于屏蔽EMI并且有效解决或减少问题。本发明的注入有石墨烯的TPU表现出适度的高导电性(在1S.m-1左右)。此外，所获得的对于本发明的注入有石墨烯的TPU材料的EMI屏蔽效能为5-10dB。
当采用水下研磨时，可以形成具有以下尺寸分布的球形颗粒：
筛网 开口(μm) 保留度％
35US 500 0-10
45US 355 0-30
60US 250 0-20
80US 180 30-80
100US 150 10-30
120US 125 0-10
PAN 0 0-10
为了说明和描述的目的，已经提供了实施例的前述描述。例如，撕裂缝和/或气囊门可以具有不同的形状或位置，尽管可能无法实现某些优点。此外，基底可以可选地包括一体模制的凸缘或偏置斜壁。虽然披露了中间泡沫层，然而其对于某些饰板来说是可以省略的，尽管没有观察到某些本发明的优点。本发明的内部饰板可以可替代地用于其他运输工具，包括飞机、水运工具和轨道车。特定实施例的各个元件或特征通常不限于此特定实施例，而是在适用的情况下是可互换的，并且即使未具体示出或描述也可以在选定的实施例中使用，并且所有从属权利要求都可以是任何组合的多项从属权利要求。这样的变化不应被认为是背离本披露内容，并且所有这样的修改旨在被包含在本披露内容的范围和精神内。

Claims (23)

1.一种车辆内部饰板，包括外蒙皮，所述外蒙皮包括按重量计80-97％的氨基甲酸酯以及按重量计1-20％的石墨烯。
2.如权利要求1所述的板，进一步包括按重量计2-4％的以下至少一种：相容剂和稳定剂。
3.如权利要求1所述的板，其中，所述石墨烯至少在熔化之前包括6-10层，并且被剥离到所述氨基甲酸酯中，所述氨基甲酸酯是热塑性聚氨酯基质。
4.如权利要求1所述的板，其中，所述石墨烯包括混杂在整个所述氨基甲酸酯中的粉状纳米颗粒。
5.如权利要求1所述的板，进一步包括刚性聚合物基底以及位于所述蒙皮的一部分与所述基底之间的软质开孔泡沫。
6.如权利要求1所述的板，其中，除了在易碎的撕裂缝处以外，所述蒙皮在气囊门处保持完整，并且在-30℃下气囊展开不会引起蒙皮碎裂。
7.如权利要求1所述的板，其中：
在120℃下加热老化500小时之后，所述蒙皮的伸长率变化不超过30％；
在120℃下加热老化500小时之后，所述蒙皮的拉伸强度变化不超过30％；以及
在120℃下加热老化500小时之后，所述蒙皮中撕裂缝处的撕裂强度变化不超过30％。
8.如权利要求1所述的板，进一步包括以下至少一种：光和UV稳定剂，所述光和UV稳定剂在所述蒙皮的旋转浇铸或凝塑模制之前与所述氨基甲酸酯和所述石墨烯混合。
9.如权利要求1所述的板，进一步包括以下至少一种相容剂：马来酸酐和乙基乙酸乙烯酯，在所述蒙皮的旋转浇铸或凝塑模制之前与所述氨基甲酸酯和所述石墨烯混合。
10.如权利要求1所述的板，其中，静止角的值为26-34°。
11.如权利要求1所述的板，其中，所述蒙皮的EMI屏蔽效能为5-10dB。
12.如权利要求1所述的板，其中，气囊撕裂缝在所述蒙皮的背面表面保持部分隔断，并且在初始刻划所述撕裂缝之后在所述撕裂缝处不会出现所述蒙皮的自我抚平。
13.如权利要求1所述的板，其中，所述车辆内部饰板是冲击吸收板，其中所述蒙皮是柔软的，并且所述板能附接到以下之一：(a)轮式机动陆地车辆，(b)轨道车，(c)飞机，以及(d)水运工具。
14.一种车辆内部饰板，包括：
柔性EMI屏蔽外蒙皮，包括热塑性聚氨酯以及按重量计1-20％的石墨烯；
比所述蒙皮更具刚性的内部聚合物基底；以及
柔性泡沫，所述柔性泡沫位于所述蒙皮的各段与所述基底之间并将所述各段附接到所述基底。
15.一种仪表板，包括：
外蒙皮，该外蒙皮包括氨基甲酸酯和石墨烯；
内部基底，该内部基底比所述蒙皮更具刚性；
柔性泡沫，该柔性泡沫位于所述蒙皮的各段与所述基底之间并且将所述各段附接到所述基底；以及
易碎的气囊撕裂缝，所述撕裂缝部分地隔断了所述蒙皮的背面表面；
所述仪表板是轮式机动陆地车辆仪表板。
16.一种制造方法，包括：
(a)将TPU与石墨烯混合；
(b)将所述TPU和石墨烯混合物熔融挤出；
(c)将稳定剂和相容剂中的至少一种添加到TPU中：
(d)形成所述注入有石墨烯的TPU混合物的粒料；
(e)研磨所述粒料；
(f)将经研磨的粒料放置到模具中；以及
(g)使所述模具旋转以形成具有EMI屏蔽特性的车板的柔性蒙皮。
17.如权利要求16所述的方法，进一步包括在180-220℃下剥离所述TPU中的所述石墨烯的各层。
18.如权利要求16所述的方法，进一步包括:
对基底进行注塑模制；以及
在所述蒙皮的各部分与所述基底之间注射柔韧的泡沫。
19.如权利要求16所述的方法，进一步包括:
在所述蒙皮的背面表面中刻划撕裂缝；
在所述蒙皮中使用按重量计80-97％的所述TPU；
在所述蒙皮中使用按重量计1-20％的所述石墨烯；以及
在所述蒙皮中使用按重量计2-4％的相容剂和/或稳定剂。
20.如权利要求16所述的方法，其中，所述石墨烯包括6-10层呈未处理形式的纳米颗粒。
21.如权利要求16所述的方法，其中，在-30℃下没有由于气囊展开的蒙皮碎裂。
22.如权利要求16所述的方法，其中，在120℃下加热老化500小时之后，所述蒙皮的伸长率变化不超过30％。
23.如权利要求16所述的方法，其中，所述蒙皮的EMI屏蔽效能是5-10dB。
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