CN107073847B - 表面可改性注塑成型体及其制造方法 - Google Patents

表面可改性注塑成型体及其制造方法 Download PDF

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CN107073847B
CN107073847B CN201580048197.9A CN201580048197A CN107073847B CN 107073847 B CN107073847 B CN 107073847B CN 201580048197 A CN201580048197 A CN 201580048197A CN 107073847 B CN107073847 B CN 107073847B
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molded article
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CN107073847A (zh
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沃尔夫冈·费舍尔
伯恩哈德·胡贝尔
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Lisa Draexlmaier GmbH
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Abstract

本发明涉及一种表面可改性注塑成型体(1)，包含热塑性聚合物基体(2)并且至少部分地包含第二聚合物材料(3)，其中聚合物基体(2)与第二聚合物材料(3)具有不同的重均分子量和极性，并且第二聚合物材料(3)适合作为粘合剂。本发明还涉及一种用于其制造的方法。

Description

表面可改性注塑成型体及其制造方法
技术领域
本发明涉及一种表面可改性注塑成型体，其包含热塑性聚合物基体并且至少部分地包含第二聚合物材料，并且涉及一种相应的用于其制造的方法，以及用途。
汽车工程中的合成材料如今占重量的15至20百分比之间，该份额持续增长。此处涉及的部分通常是外部和内部构件，该外部和内部构件通过将各种表面装饰物粘附在注塑成型的构件上而具有相应的光学、触觉和功能特性。对质量、经济性和资源的有效利用的日益增长的需求，以及全球竞争压力，都要求涂覆工艺越来越经济、可持续和灵活。
注塑成型体形式的塑料件特别地用于诸如仪表板、门板或中控台这样的汽车内饰应用。它们经常设置有皮革或箔的表面装饰物，以给予它们更优雅的外观。这些装饰物通过分散或热熔粘合剂的方式固定并且结合在成型体上。
这通常需要用于预处理成型体的表面的步骤，以确保在限定的处理窗口期内获得合适的表面张力。通常，通过利用火焰或等离子体处理或气相氟化来活化表面，从而优化粘合性能。
然而，该方法的一个缺点在于，在制造过程中需要至少一个额外的步骤。并且，需要通常复杂并且昂贵的额外的设备。尤其是，利用酸和溶剂处理表面具有严重的环境影响。
背景技术
这已经引起了减少由塑料制成的附着体中的胶合步骤的数量的发展趋势，例如通过将胶合功能集成到注塑成型工艺中。
聚丙烯或强化聚丙烯是有成本效益的，并且是经常用于注塑成型部件的塑料。在大多数情况下，由于聚丙烯的非极性性质，不能够在没有预处理的情况下进一步处理或精加工注塑成型部件。预处理是必要的，特别是在胶合和涂漆的情况下，否则粘合剂和油漆将不会充分地粘结至表面。
在所谓的“按需加工处理”中，在紧接着注塑成型之后的工艺步骤中，将胶或粘合剂层施加到注塑成型部件。
例如，DE 103 49 177 A1公开了一种用于精加工预先成型的板件的工艺，其包括以下步骤：
(a)将基于反应性聚氨酯的固体粘合剂型的热熔(Hot Melt)100％层利用刮板或辊施加于用于被覆目的的层压制件、箔或膜的两个表面中的一个表面，所述层压制件、箔或膜特别是由聚合物材料或天然材料或工业织物制成的；
(b)将用于被覆的层压制件、箔或膜放置在待精加工的面板的相应表面上；
(c)预热用于被覆的层压制件、箔或膜；
(d)通过热压，使待精加工的面板被用于被覆的层压制件、箔或膜覆盖。
特别地，在金属-塑料复合材料领域中找到了可比的方法。
EP 2 374 593 A1公开了一种用于改性非极性聚合物的成型体的表面的注塑成型方法、适合于该目的的多层箔以及具有改性表面的成型聚合物部件。该方法涉及背面注塑成型多层箔，该多层箔至少具有第一非极性层和具有至少一种与第一层不同的表面性质的第二层。将箔背面注塑成型是本身已知的技术，其中，首先将箔放置在注塑成型工具的腔体内，或者在注塑模具上展开。将箔压入腔体内，然后按照腔体的形状成型。然后将聚合物注入腔体内，随之箔的面向聚合物的一侧与聚合物粘结。由此得到被覆有箔的成型部件。现如今，特别地在装饰箔中应用背面注塑成型，如在称为“模内装饰”(in-mold-decoration，IMD)的技术中。
然而，根据EP 2 374 593 A1，多层箔具有至少一个非极性层以及至少一个第二层，该第二层具有至少一种与第一层不同的表面性质，该多层箔以如下方式置入注塑成型工具的腔体内：第一非极性层面向腔体的内部，同时第二层靠置在腔体的内壁上。然后将非极性聚合物注入模具的内部。在模具中，被注入的聚合物与多层箔的第一非极性层彼此接触，并且随后结合在一起。
EP 2 664 643 A1示出了成型的材料，其中，复合材料具有包含热塑性粘结剂的强化纤维。
US 2005/163998 A1中已知用于涂覆强化纤维的仅具有一种聚合物组分的化合物。
WO 2008/064950 A1示出了要被附着于金属或塑料基质的成型部件，其完全由热熔粘合剂构成。
此处，多层箔的第二层具有至少一种与第一非极性层不同的表面性质。
发明内容
因此，本发明的目的是提供一种注塑成型体或者成型塑料体，其具有能够容易地改性的粘着和润湿性能，即在满足粘附的质量要求的同时减少了用于成型体的粘附的工艺步骤数量以及必要工具的成本。
本发明的另一目的是提供一种相应的方法，其中，在注塑成型期间或者之后，功能性地提高成型部件的表面的粘着和润湿性能，而不需额外的工作或费用。
根据本发明，通过具有本发明的特征的注塑成型体以及本发明的方法，实现上述目的。
本发明的基本思想在于，表面可改性注塑成型体包含热塑性聚合物基体并且至少部分地包含第二聚合物材料。聚合物基体和第二聚合物材料具有不同的重均分子量和极性，并且第二聚合物材料适合作为粘合剂。
换言之，第二聚合物材料已经作为可粘结组分被并入注塑成型体中的热塑性聚合物基体内。在成品中，在冷却状态下，可粘结组分至少部分地形成了诸如表面层这样的分离层。为进一步的处理或粘合而加热期望的成型体区域。这种性质的活性表面由此表现为好像已经施加了粘合剂。这一方面体现为表面的粘性，并且另一方面体现为表面张力的增加，因为极性组分迁移到表面。
鉴于现有技术，对于本领域技术人员意想不到和不可预见的是，本发明的目的可以通过本发明的注塑成型体及其制造方法来实现。本发明的特别的优点在于，通过注塑成型体和上述提出的方法，完全消除了单独地激活基质以及从外部施加粘合剂的步骤。
当表面可改性注塑成型体经受热量时，随着第二聚合物材料富集在注塑成型体的表面上，热塑性聚合物和第二聚合物材料至少部分地进入相分离(phase separation)。这意味着在注塑成型过程之前或期间，热塑性聚合物基体和增粘的第二聚合物组分初始作为大程度的均匀混合物存在于注塑成型材料中。在热影响之下，例如通过加热或辐射以及随后的冷却，表面可改性注塑成型体得以变化。由于第二聚合物组分的低平均分子量和密度，以及其相对于基体材料较高的极性，其在被加热时在聚合物基体内相对自由地移动。在冷却时，实现能够用作粘合功能的热力学控制的相分离。
这不仅节省了用于粘合剂施加和/或激活的设备的投资成本，而且还消除了与激活设备相关以及与施加粘合剂相关的操作成本。
热塑性聚合物基体优选地选自由丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丙烯腈(SAN)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、或其混合物所组成的组。它们可以被纤维强化。
第二聚合物材料优选为官能化热塑性聚烯烃弹性体(POE)、烯烃嵌段共聚物(OBC)、或其混合物。
此处，第二聚合物材料优选地是能够熔融并且再固化的。
所述第二聚合物材料还优选地以5-40质量％，优选地以10-30质量％，并且特别优选地以10-25质量％的比例包含在表面可改性注塑成型体中。
第二聚合物材料优选地具有11,000至37,000g/mol的平均分子量。
表面可改性注塑成型体，即第一和/或第二聚合物优选地具有能够通过微波处理偶联的添加剂。
能够微波处理的添加剂优选地包含碳纤维、碳纳米管、石墨烯等。这使得成型体在必要时能够仅通过微波处理而被加热。
本发明的用于制造表面改性成型体的方法包括以下步骤：
a)提供热塑性聚合物基体和第二聚合物材料，其中聚合物基体与第二聚合物材料具有不同的重均分子量和极性，并且第二聚合物材料适合作为粘合剂；
b)在注塑成型工具中熔融、注塑成型并且冷却材料，其中在熔融时，随着第二聚合物材料富集在注塑成型体的表面上，热塑性聚合物和第二聚合物材料至少部分地进入相分离；
c)从注塑成型工具中移除成型体；
d)加热或者熔融并且再固化注塑成型体，其中，第二聚合物材料用作将注塑成型体粘结至另一构件的粘合剂。
注塑成型体优选地在梯度控制下被加热或者熔融并且冷却，使得第二聚合物材料在注塑成型体的预定的表面或表面区域上选择性地、受控制地富集。由此，可以想到只有成型体的选定表面区域被加热并粘附至另一构件。
注塑成型体优选地以如下方式在梯度控制下被加热、熔融和/或冷却：在注塑成型体的可见表面上发生第二聚合物材料的选择性富集，并且该可见区域然后被粘结或粘附至平面装饰部。由此，可以通过加热以及随后将加热的表面可改性注塑成型体粘附至适当的装饰部来有利地提供成型体，其中，能够消除施加粘合剂的方法步骤。粘合剂已经是成型体的内在部分，并且能够利用简单的加热而选择性地释放。
实施例：
下面的实例意在说明本发明而非限制本发明。
实例以表格形式示出了多种官能化聚烯烃弹性体(POE)、烯烃嵌段共聚物(OBC)、或其混合物，作为根据本发明的第二聚合物材料。
近来投放市场的一些产品实例包括“InfuseTM”(陶氏化学公司(Dow ChemicalCompany))烯烃嵌段共聚物(OBC)和“AffinityTM”GA(陶氏化学公司)聚烯烃弹性体(POE，TPO)，它们代表了用于注塑成型部件的热熔粘合剂技术的起点。
与传统的聚烯烃相比，两种聚合物通常具有非常低的平均分子量和密度，而具有高极性。其它特殊的物理化学性质已在其他地方讨论过。
“InfuseTM”(陶氏化学公司)烯烃嵌段共聚物(OBC)是乙烯和α-烯烃共聚物，由交替的半结晶和弹性体嵌段或链段组成，其以多嵌段结构呈随机分布，并有助于它们的热熔-粘合功能。
下表示出了“AffinityTM”GA(陶氏化学公司)聚烯烃弹性体(POE，TPO)的不同性质的实例。
表1官能化聚烯烃弹性体“AffinityTM GA 1000R”
表2适合的粘合剂“AffinityTM GA”聚烯烃弹性体的物理性质
实例的原材料：
a)聚丙烯(PP)的聚合物基体
b)“Infuse 9817”：乙烯与辛烯的共聚物，熔点120℃，弯曲模量23MPa，密度0.877g/m3，接枝前熔融指数15g/10min且接枝后熔融指数4g/10min
c)“AffinityTM GA”聚烯烃弹性体
实施例1：
在注塑成型机中，在熔融状态下，将Infuse 9817以10-30质量％的比例与PP混合，并以平面成型体的形式施加。
然后加热，粘附成型体并且对成型体进行工业粘合强度试验：
a)根据DIN，粘结在一起的两个成型体具有>7000N的拉伸强度。
b)根据DIN，与平面装饰部件(PVC，PUR，发泡的)粘结的成型体在加热至大约180℃之后具有>10-50N的拉伸强度。
测得的拉伸强度在量级上对应于通过施加传统粘合剂实现的拉伸强度。
实施例2：
此外，用于测量表面张力的分析方法也用于表征表面和粘合剂分布：
a)作为参考材料，纯PP的成型体表面在加热后，根据DIN具有28mN/m的表面张力。
b)根据本发明的PP+TPO/OBC成型体表面在加热后，根据DIN具有32-34mN/m的表面张力。
由表面的明显的粘性所标志的表面张力的显着增加证明了极性TPO/OBC聚合物组分在表面中的富集。
附图说明
下面参考附图详细说明注塑成型体和/或其制造以及用途的各个实施例。
在附图中：
图1示出根据本发明的表面可改性注塑成型体的示意性图示，其具有热塑性聚合物基质和至少部分的第二聚合物材料；
图2示出在经受热量的同时，表面可改性注塑成型体的结构变化和/或相分离的示意性图示；以及
图3示出加热后的表面可改性注塑成型体与装饰部的粘附的示意性图示。
在注塑成型期间注塑成型体1的一般性结构由热塑性聚合物基体2产生，示为较大的缠结的球。基体可以由各自为纤维强化或者未强化的丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丙烯腈(SAN)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、或其混合物构成。
一体化到该基体中的是产品“InfuseTM”(陶氏化学公司)烯烃嵌段共聚物(OBC)，和/或“AffinityTM”GA(陶氏化学公司)聚烯烃弹性体(POE)，其形成了成型体的增粘组分，并且示为较小的缠结的球。它们特别地以低平均分子量和相对高的极性区别于基体材料。
在注塑成型工艺之前或期间，热塑性聚合物基体2和增粘烯烃嵌段共聚物(OBC)和/或聚烯烃弹性体(POE)初始作为大程度地均匀混合物存在于注塑成型颗粒中，并且随后作为均匀的随机混合物存在于注塑材料中。
图2示出例如通过加热或辐射而经受热影响，并且随后冷却的表面可改性注塑成型体1中的结构的改变。由于烯烃嵌段共聚物(OBC)和聚烯烃弹性体的低平均分子量和密度，以及它们相对于基体材料的较高的极性，在被加热时，它们在聚合物基体2中相对自由地移动。在冷却期间发生了热力学控制的相分离，其中烯烃嵌段共聚物(OBC)和/或聚烯烃弹性体优选地积聚在较冷的工具部分和/或注塑成型体1的一个表面或多个表面上。
图3示出如何使用烯烃嵌段共聚物(OBC)和/或聚烯烃弹性体(POE)的热熔粘合官能化的示意性图示。烯烃嵌段共聚物(OBC)和/或聚烯烃弹性体(POE)现在已经积聚在成型体表面上，加热表面可改性注塑成型体1然后粘附至适当的装饰部。加热可以仅通过微波处理进行，优选地利用能够通过微波处理偶联的一体化的添加剂支持加热。不需要单独地施加粘合剂。装饰部特别地是弹性的平面覆盖元素，例如皮革或人造皮革。

Claims (13)

1.一种表面可改性注塑成型体(1)，包含热塑性聚合物基体(2)并且至少部分地包含第二聚合物材料(3)，其中所述聚合物基体(2)与所述第二聚合物材料(3)具有不同的重均分子量和极性，与所述热塑性聚合物基体(2)相比，所述第二聚合物材料(3)的重均分子量较低且极性较高，并且所述第二聚合物材料(3)适合作为粘合剂，其特征在于，
在暴露于热量的情况下，所述热塑性聚合物基体(2)和所述第二聚合物材料(3)至少部分地进入相分离，其中所述第二聚合物材料(3)积聚在所述注塑成型体(1)的表面上并且表面张力增加。
2.根据权利要求1所述的表面可改性注塑成型体(1)，其中所述热塑性聚合物基体(2)选自纤维强化或者未强化的丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丙烯腈(SAN)、聚苯乙烯(PS)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、或其混合物所组成的组。
3.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中所述第二聚合物材料(3)是官能化热塑性聚烯烃弹性体(POE)、烯烃嵌段共聚物(OBC)、或其混合物。
4.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中所述第二聚合物材料(3)是能够熔融并且再固化的。
5.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中以5-40质量％包含所述第二聚合物材料。
6.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中以10-30质量％包含所述第二聚合物材料。
7.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中以10-25质量％包含所述第二聚合物材料。
8.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中所述第二聚合物材料具有11,000至37,000g/mol的平均分子量。
9.根据权利要求1或2所述的表面可改性注塑成型体(1)，其中所述热塑性聚合物基体(2)和/或所述第二聚合物材料(3)具有能够通过微波处理偶联的添加剂。
10.根据权利要求9所述的表面可改性注塑成型体(1)，其中能够微波处理的所述添加剂包含碳纤维、碳纳米管或石墨烯。
11.一种用于制造表面改性成型体的方法，包括以下步骤：
a)提供一种混合物，该混合物包含至少一种热塑性聚合物基体(2)和第二聚合物材料(3)，其中所述聚合物基体(2)与所述第二聚合物材料(3)具有不同的重均分子量和极性，与所述热塑性聚合物基体(2)相比，所述第二聚合物材料(3)的重均分子量较低且极性较高，并且所述第二聚合物材料(3)适合作为粘合剂；
b)在注塑成型工具中注塑成型所述混合物，其中所述热塑性聚合物基体(2)和所述第二聚合物材料(3)呈随机分布；
c)从所述注塑成型工具中移除注塑成型体；
d)熔融并且再固化所述注塑成型体(1)，其中所述热塑性聚合物基体(2)和所述第二聚合物材料(3)至少部分地进入相分离，其中所述第二聚合物材料(3)积聚在所述注塑成型体(1)的表面上；以及
e)将所述注塑成型体(1)粘附到另一构件，其中所述第二聚合物材料用作将所述注塑成型体(1)粘结至其它构件的粘合剂。
12.根据权利要求11所述的方法，其中以如下方式在梯度控制下将所述注塑成型体(1)至少部分地加热和/或熔融并且冷却：在所述注塑成型体(1)的预定的表面或表面区域上发生所述第二聚合物材料(3)的选择性积聚。
13.根据权利要求11所述的方法，其中以如下方式在梯度控制下将所述注塑成型体(1)至少部分地加热和/或熔融并且冷却：在所述注塑成型体(1)的可见表面上发生所述第二聚合物材料(3)的选择性积聚，该可见表面随后被粘附至平面装饰部(4)。
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CN107073847A (zh) 2017-08-18
US11001018B2 (en) 2021-05-11

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