CN104619782B - 热塑性树脂复合组合物、热塑性树脂复合材料及其制备方法 - Google Patents

热塑性树脂复合组合物、热塑性树脂复合材料及其制备方法 Download PDF

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CN104619782B
CN104619782B CN201280075504.9A CN201280075504A CN104619782B CN 104619782 B CN104619782 B CN 104619782B CN 201280075504 A CN201280075504 A CN 201280075504A CN 104619782 B CN104619782 B CN 104619782B
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thermoplastic resin
wood chip
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CN104619782A (zh
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金成珉
吴爱利
郑在烈
金熙俊
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Abstract

本发明提供一种包含玻璃纤维、柱状的木片以及热塑性树脂的热塑性树脂复合组合物。

Description

热塑性树脂复合组合物、热塑性树脂复合材料及其制备方法
技术领域
本发明涉及一种热塑性树脂复合组合物、热塑性树脂复合材料及其制备方法。
背景技术
复合材料是通过结合两种以上的材料而形成的材料，它具有被称为增强相(reinforcing phase)的纤维、板、粒子形态的材料被埋于被称为基质相(matrix phase)的树脂形态的材料的结构。基质相应提供增强材料的侧面支撑力，传递载荷，承受外部的冲击，而增强材料则应具有高强度及高刚性的特性。
由于大部分热塑性塑料树脂缺乏耐热性并具有结晶性(cristallinity)，因而存在冲击强度差、成型时的收缩率高的缺点。为了改善上述缺点，目前已经开发了引入聚合物合金(alloy)或将无机物的玻璃纤维作为增强材料来投入的技术。
目前已有以利用木材的粉末对包含玻璃纤维的聚丙烯树脂的物理性质进行改良为目的的树脂组合物，但木粉仅仅起到填充材料的作用，而不是增强材料的作用，因此，无法期待能够增强复合材料的刚性，而且如果木粉含量变高，就会降低加工性，因而存在不适合注射及挤压成型的缺点。
发明内容
本发明要解决的技术问题
根据本发明的一实例，提供一种物理刚性(modulus)和冲击吸收性优秀，并且能够将弯曲等的变形最小化的热塑性树脂复合组合物。
根据本发明的再一实例，提供一种对上述热塑性树脂复合组合物进行成型而制备的热塑性树脂复合材料。
根据本发明的另一实例，提供一种上述热塑性树脂复合材料的制备方法。
技术方案
根据本发明的一实例，提供一种包含玻璃纤维、柱状的木片(wood materialchips)以及热塑性树脂的热塑性树脂复合组合物。
上述柱状可具有至少一个平坦面。
上述柱状可包含针状。
上述木片的上述柱状的高度与宽度之比可以是约1:10至约1:40。
上述柱状的平均宽度可以是约6mm至约40mm。
上述玻璃纤维的平均直径可以是约15μm至约17μm。
上述热塑性树脂可包含选自由聚丙烯、聚乙烯、聚酰胺及它们的组合组成的组中的一种。
上述热塑性树脂复合组合物可包含100重量份的上述热塑性树脂、约25重量份至约80重量份的上述玻璃纤维及约大于0重量份至约80重量份的上述木片。
根据本发明的再一实例，提供一种在热塑性树脂基质分散有玻璃纤维及柱状的木片的热塑性树脂复合材料。
根据本发明的另一实例，提供一种热塑性树脂复合材料的制备方法，其包括以下步骤：混合热塑性树脂及柱状的木片的步骤；将玻璃纤维混合于上述热塑性树脂及上述木片的混合物的步骤；对上述热塑性树脂、上述木片及玻璃纤维的混合物进行压缩成型的步骤；以及对由上述中间层、上述至少一个表面层及上述至少一个热塑性树脂层层叠而成的层叠体进行压缩成型来制备层叠体的步骤。
使用第一挤压机来混合热塑性树脂及柱状的木片，使用第二挤压机来将玻璃纤维混合于上述热塑性树脂及上述木片的混合物。
在上述第一挤压机及上述第二挤压机中，可在约190℃至约230℃的温度下进行混合。
热塑性树脂复合材料可通过长纤维增强热塑性塑料的直接加工(LFT-D，LongFiber Thermoplastic-Direct)工艺制备。
有益效果
对上述热塑性树脂复合组合物进行成型而制备的复合材料，其物理刚性(modulus)和冲击吸收性优秀，且能够将弯曲等的变形最小化。
附图说明
图1是表示根据本发明的一实例的热塑性树脂复合材料的制备步骤的制备方法的示意图。
图2是根据实施例1及比较例1来制备的热塑性树脂复合材料的照片。
具体实施方式
以下，将对本发明的实例进行详细说明。下述实例只是作为示例而提出的，本发明并不受限于此，本发明仅由所附的发明要求保护范围来定义。
根据本发明的一实例，提供一种包含玻璃纤维、柱状的木片以及热塑性树脂的热塑性树脂复合组合物。
上述热塑性树脂复合组合物通过在热塑性树脂中混合加强材料，提高物理刚性与冲击吸收性，能够将在产品成型时成问题的弯曲等的变形最小化，并且，在价格方面，通过使用低廉的木片，能够节省其制备成本。
上述热塑性树脂复合组合物通过包含柱状的木片，在由上述热塑性树脂复合组合物成型而制备的复合材料中，通过上述木片的排列，提高排列方向刚性，并且提高上述复合材料的整体冲击吸收性，与仅用玻璃纤维对热塑性树脂进行加强时相比，能够改善热塑性树脂的收缩异方性，从而能够将上述复合材料的弯曲最小化。
上述木片的柱状可包含具有规定高度的所有杆状。例如，上述柱状可具有至少一个平坦面。上述平坦面的形状可包含三角形、四角形等多角形，且平坦面的形状不受限制。
并且，上述柱状可包含针状。上述针状意味着以一面为基准，另一面的宽度逐渐变窄的针模样的形状，可包含所有具有规定高度的针状。
上述木片的柱状的高度与宽度之比具体地可以是约1:10至约1:40，具体地可以是约1:12至约1:16。通过使用具有上述形状比的木片，能够容易地实现通过包含如上所述的木片所能够得到的优点。
上述“柱状的高度”是指一面的垂直长度；上述“柱状的宽度”是指横跨柱状的横向的宽度。
例如，上述柱状的平均宽度可以是约6mm至约40mm。例如，上述柱状的平均高度可以是约1mm至约2mm。
上述木片可以无限制地使用任意一种工业用木材，例如，能够使用松树等木材，不仅能够使用木材的芯材，还能够使用对接近于除芯材之外的剩余表面的部分进行破碎而取得的木片。
具有上述柱状的木片不仅起到填充材料作用，而且与玻璃纤维一同在材料内起到增强材料的作用，来增大热塑性树脂复合组合物的刚性。例如，上述木片的密度可以是1.1g/cm3。
相对于100重量份的上述热塑性树脂，可包含约大于0重量份至约80重量份的上述木片，具体地可包含约20重量份至约50重量份。上述热塑性树脂复合组合物通过包含上述含量比的木片，能够容易地实现通过包含如上所述的木片所能够得到的优点。
上述玻璃纤维不受特别限制，能够无限制地使用公知的物质。例如，为了防止与组合物内的其他成分的分离现象，能够使用涂层有用于提升表面粘合力的硅烷偶联剂的玻璃纤维。再例如，上述玻璃纤维能够使用无碱玻璃纤维连续纤维类型。
具体地，上述玻璃纤维主要采用平均直径为约15μm至约17μm的流动类型。上述玻璃纤维在制备过程中，在挤压机内通过螺旋桨时其长度被切短，因此，不限制于特定长度的玻璃纤维。
相对于100重量份的上述热塑性树脂，可包含约25重量份至约80重量份的上述玻璃纤维，具体地可包含约20重量份至约40重量份。上述热塑性树脂复合组合物通过包含上述含量比的玻璃纤维，能够使强度及收缩异方性的改善效果都变得优秀，同时在价格方面也能够进行适当调整。
上述热塑性树脂不受特别限制，能够无限制地使用公知的可成型为膜或片的热塑性树脂。上述热塑性树脂的具体例子可包含选自包括聚丙烯、聚乙烯、聚酰胺及它们的组合的组中的一种。根据一实例，上述热塑性树脂能够使用均聚聚丙烯、共聚聚丙烯树脂或它们的组合，例如，上述热塑性树脂可以是流动指数(g/10分钟)为约40至约800的树脂。
根据所要实现的物理性质，上述热塑性复合树脂组合物可还包含选自由热稳定剂、偶联剂等以及它们的组合组成的组中的添加剂。相对于100重量份的上述热塑性树脂，可包含约1重量份至约5重量份的上述添加剂。
根据本发明的再一实例，提供一种在热塑性树脂基质上分散有玻璃纤维及柱状的木片的热塑性树脂复合材料。
上述热塑性树脂复合材料能够通过对上述热塑性树脂复合组合物进行成型而制备。对上述热塑性树脂复合组合物进行成型的具体方法将记载于后述内容中。根据后述的方法制备的上述热塑性树脂复合材料，在上述热塑性树脂基质上均匀地分散有上述玻璃纤维和上述木片。
上述热塑性树脂、上述玻璃纤维、上述柱状的木片相关内容如上所述。
上述热塑性树脂复合材料的拉伸性及弯曲刚性、耐冲击性优秀，收缩异方性问题得到改善，将有效改善产品成型时弯曲等的变形问题。并且，上述热塑性树脂复合材料使用价格相对低廉的木片，从而能够降低制备成本，具体地，能够作为汽车轻量化材料，能够有效地应用于车底护板或座椅靠背等。
根据本发明的另一实例，提供一种热塑性树脂复合材料的制备方法，包括以下步骤：混合热塑性树脂及柱状的木片的步骤；将玻璃纤维混合于上述热塑性树脂及上述木片的混合物的步骤；对上述热塑性树脂、上述木片及玻璃纤维的混合物进行压缩成型的步骤；以及对由上述中间层、上述至少一个表面层及上述至少一个热塑性树脂层层叠而成的层叠体进行压缩成型来制备层叠体的步骤。
根据上述制备方法，能够制备上述热塑性树脂复合材料。
图1是表示根据本发明的一实例的热塑性树脂复合材料的制备步骤的制备方法的示意图。
根据图1，准备两台挤压机，即第一挤压机及第二挤压机，利用上述两台挤压机，例如，首先，混合以粒料形态制备的热塑性树脂和上述柱状的木片，投入于第一挤压机，接着，将玻璃纤维投入于第二挤压机后，对通过上述步骤取得的热塑性树脂、玻璃纤维及木片的混合物进行压缩成型，来制备上述热塑性树脂复合材料。
在上述第一挤压机及上述第二挤压机中，气缸筒的温度能够根据热塑性树脂的类型进行适当调整，具体地，可以在约190℃至约230℃的温度下完成挤压捏合。
如上所述，首先，通过将热塑性树脂和木片一同混合投入于第一挤压机，提高木片对于热塑性树脂的浸渍性，从而能够提高加工性。在混合上述柱状的木片的情况下，存在由于加工性下降因而不适合注射及挤压成型的忧虑，但通过采用上述制备方法，消除了这种忧虑，并且，由于木片具有如上所述的柱状，因而在与玻璃纤维一同排列时，能够得到向着所排列的方向能够增大物理性质的效果。
在一实例中，上述热塑性树脂复合材料的制备方法可通过长纤维增强热塑性塑料的直接加工工艺执行。
以下将记载本发明的实施例及比较例。但下述实施例仅仅是本发明的一实施例，本发明并不限定于下述实施例。
实施例及比较例
<实施例1>
按照长纤维增强热塑性塑料的直接加工工艺，首先将通过对聚丙烯树脂进行成型而制备的粒料100重量份及木片(wood chip，柱状的平均宽度为15mm，柱状的高度与宽度之比为1:4)33.3重量份混合投入于第一挤压机，接着，在第二挤压机中投入用硅烷类偶联剂涂敷的玻璃纤维(SE4121_聚丙烯上浆(Polypropylene Sizing)，欧文斯科宁(OCV)制造)33.3重量份，来取得长纤维增强热塑性塑料束(Strand)。如上所述，上述长纤维增强热塑性塑料束通过投入材料并在220℃的第一挤压机气缸筒及220℃的第二挤压机的气缸筒分别挤压捏合而取得，接着，在63℃成型模中对上述长纤维增强热塑性塑料束进行50秒钟左右的挤压成型，制备出热塑性树脂复合材料。
<实施例2>
除上述木片的投入量为23.08重量份、玻璃纤维的投入量为30.77重量份之外，采用与上述实施例1相同的方法，制备出热塑性树脂复合材料。
<实施例3>
除上述木片的投入量为14.28重量份、玻璃纤维的投入量为28.57重量份之外，采用与上述实施例1相同的方法，制备出热塑性树脂复合材料。
<比较例1>
除不使用上述木片而使用热塑性树脂100重量份及玻璃纤维25重量份之外，采用与上述实施例1相同的方法，制备出热塑性树脂复合材料。
<比较例2>
除以平均直径为2mm的木粉替代上述木片之外，采用与上述实施例1相同的方法，制备出热塑性树脂复合材料。
评价
对于在实施例1～实施例3及比较例1～比较例2中制备的热塑性树脂复合材料，采用下列方法测定了物理性质。
[弯曲刚性]
为了测定由于含有木片而提升的刚性，依据ASTM D790，沿着增强材料的排列方向，制备出长度为5英寸、宽度为1/2英寸的试片，测定弯曲刚性并将结果显示于下述表1。
[拉伸刚性]
为了测定由于含有木片而提升的刚性，依据ASTM D638，沿着增强材料的排列方向，制备了狗骨头形状的试片，测定拉伸刚性并将结果显示于下表1。
[冲击强度]
为了测定由于含有木片而提升的冲击强度性，依据ISO180/1A，在常温下测定缺口冲击强度，并将结果显示于下述表1。
[收缩异方性的改善]
在上述实施例及比较例中，制备热塑性树脂复合材料时，将从约220℃的第二挤压机气缸筒取得的上述长纤维增强热塑性塑料束放入约63℃的挤压机的成型模时，随着冷却将发生收缩。图2是通过压缩成型而制备的实施例1及比较例1的热塑性树脂复合材料的照片，从照片中可以确认，实施例1的热塑性树脂复合材料与比较例1的热塑性树脂复合材料相比，收缩异方性得到了改善。
表1

Claims (10)

1.一种热塑性树脂复合组合物，其特征在于，包括玻璃纤维、柱状的木片以及热塑性树脂；
所述柱状具有至少一个平坦面；
所述木片的所述柱状的高度与宽度之比为1:10至1:40；
所述柱状的平均宽度为6mm至40mm；
包括100重量份的所述热塑性树脂、25重量份至80重量份的所述玻璃纤维及大于0重量份至80重量份的所述木片。
2.根据权利要求1所述的热塑性树脂复合组合物，其特征在于，所述玻璃纤维的平均直径为15μm至17μm。
3.根据权利要求1所述的热塑性树脂复合组合物，其特征在于，所述热塑性树脂包含选自由聚丙烯、聚乙烯、聚酰胺及它们的组合组成的组中的一种。
4.一种热塑性树脂复合材料，其特征在于，在热塑性树脂基质分散有玻璃纤维及柱状的木片；
所述柱状具有至少一个平坦面；
所述木片的所述柱状的高度与宽度之比为1:10至1:40；
所述柱状的平均宽度为6mm至40mm；
包括100重量份的所述热塑性树脂基质、25重量份至80重量份的所述玻璃纤维及大于0重量份至80重量份的所述木片。
5.根据权利要求4所述的热塑性树脂复合材料，其特征在于，所述玻璃纤维的平均直径为15μm至17μm。
6.根据权利要求4所述的热塑性树脂复合材料，其特征在于，所述热塑性树脂包含选自由聚丙烯、聚乙烯、聚酰胺及它们的组合组成的组中的一种。
7.一种热塑性树脂复合材料的制备方法，其特征在于，包括以下步骤：
混合热塑性树脂及柱状的木片的步骤；
将玻璃纤维混合于所述热塑性树脂及所述木片的混合物的步骤；
对所述热塑性树脂、所述木片及玻璃纤维的混合物进行压缩成型的步骤；以及
对由所述中间层、所述至少一个表面层及所述至少一个热塑性树脂层层叠而成的层叠体进行压缩成型来制备层叠体的步骤；
所述柱状具有至少一个平坦面；
所述木片的所述柱状的高度与宽度之比为1:10至1:40；
所述柱状的平均宽度为6mm至40mm；
包括100重量份的所述热塑性树脂、25重量份至80重量份的所述玻璃纤维及大于0重量份至80重量份的所述木片。
8.根据权利要求7所述的热塑性树脂复合材料的制备方法，其特征在于，使用第一挤压机来混合热塑性树脂及柱状的木片，使用第二挤压机来将玻璃纤维混合于所述热塑性树脂及所述木片的混合物。
9.根据权利要求7所述的热塑性树脂复合材料的制备方法，其特征在于，在所述第一挤压机及所述第二挤压机中，在190℃至230℃的温度下进行混合。
10.根据权利要求7所述的热塑性树脂复合材料的制备方法，其特征在于，通过长纤维增强热塑性塑料的直接加工工艺执行。
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