CN104691074B - 天然纤维高分子复合物及汽车内饰材料用环保轻量基材 - Google Patents

天然纤维高分子复合物及汽车内饰材料用环保轻量基材 Download PDF

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CN104691074B
CN104691074B CN201410710332.9A CN201410710332A CN104691074B CN 104691074 B CN104691074 B CN 104691074B CN 201410710332 A CN201410710332 A CN 201410710332A CN 104691074 B CN104691074 B CN 104691074B
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mentioned
base material
automotive interior
preparation
natural fiber
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CN201410710332.9A
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CN104691074A (zh
Inventor
金基成
池相圭
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Han Il E HWA Co Ltd
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Han Il E HWA Co Ltd
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Priority claimed from KR1020130150824A external-priority patent/KR101543597B1/ko
Priority claimed from KR1020140103366A external-priority patent/KR101619977B1/ko
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Abstract

本发明涉及汽车内饰材料用环保轻量基材，其特征在于，为了完善包含有在高温多湿环境下表现不稳定的天然材料的三明治结构的汽车内饰材料用基材的性能，添加水分硬化型异氰酸酯或环氧树脂，完善因天然纤维的水分浸透所致的物性低下，由此改善天然纤维加强层的耐湿性和强度，并利用热覆膜在热塑性发泡片芯材层连续地制备基材。利用本发明来制备的基材属于环保材料，不仅能够通过减轻重量来实现轻量化，而且具有优秀的耐湿性和强度，能够应用于包括汽车内饰材料领域的铁道、飞机及建筑用内饰材料等各种工业领域。

Description

天然纤维高分子复合物及汽车内饰材料用环保轻量基材
技术领域
本发明涉及天然纤维高分子复合物及汽车用环保轻量基材。
背景技术
汽车内饰用基材作为与乘客直接接触的汽车部件，很多部件通过组装来保持形态并发挥着保护乘客免受外部环境影响的作用，因此，要求在各种温度及湿度的外部环境中保持尺寸稳定性和物性。并且，近年来由于环境污染和全球变暖等问题，还要求使用环保材料和以轻量化来提高耗能。
通常，汽车内饰材料用基材主要采用三明治结构，在该结构中，用于赋予形态稳定性的加强层层叠于用于赋予吸隔音性的芯材层的一面或两面，以往主要使用热硬化性酚醛树脂浸渍于玻璃纤维毡子的加强层与利用聚氨酯发泡片的芯材层。
但是，用于加强层的玻璃纤维毡子在制造时会产生粉尘，这种粉尘不仅对作业人员的身体有害，而且在自然环境下几乎无法降解，使得具有所产生的废弃物造成环境污染的问题，作为粘结剂使用的酚醛树脂在自然环境下也几乎无法降解，并且难以回收再利用，因此不具有环保性。不仅如此，由于这些材料的密度高，当应用于汽车部件时，导致重量增加，耗能下降。并且，用于芯材层的聚氨酯发泡片不溶于热，当层叠加强层时，需要实施涂敷粘合剂或者使用热熔胶膜的补充工序，使得具有不仅工序复杂，而且也会导致费用增加的问题。
近年来，为了解决上述问题，将天然纤维作为加强层使用并将热塑性发泡片作为芯材层使用，从而在常温下使用时，在基材的轻量化和环保化部分表现出优秀性，但由于天然纤维在水分环境下不稳定的缺点，在高温多湿的环境下，基材会出现错位或悬垂现象，进而造成形态不稳定的问题。
为了解决这种存在问题，一直以来持续进行了诸多预处理方法相关研究，该研究采用如电子束照射、等离子照射、碱性处理及硅烷处理等各种物理化学方法，试图提高天然纤维的水分抵抗性，但预处理所需工序设置费用昂贵，而且还需要额外加工时间，在产业应用层面存在局限性。
发明内容
如上所述，本发明是为了解决现有包含天然纤维并采用三明治结构的汽车内饰材料用基材所表现出的在高温多湿环境中的悬垂现象和物性低下的问题，本发明的目的在于提供一种具有优秀的轻量性的汽车内饰材料用基材的制备方法，其通过使用异氰酸酯来改善天然纤维加强层的耐湿性和强度，并以此来改善基材的悬垂问题及物性低下问题。
本发明的目的在于提供一种采用环保材料，而且还具有优秀的耐湿性和轻量性的汽车内饰材料用基材的制备方法，其通过向由天然纤维和合成纤维构成的毡子涂敷异氰酸酯来制造耐湿性得到改善的薄膜加强层，并连续地向热塑性发泡片进行热覆膜。
为了实现上述技术问题，本发明提供耐湿性得到强化的汽车内饰材料用环保轻量基材的制备方法，其特征在于，包括：第一步骤，以天然纤维和合成纤维制备毡子；第二步骤，向上述毡子涂敷液状异氰酸酯之后，利用热轧辊来实施半硬化反应，由此制备薄片；第三步骤，通过向上述薄片涂敷热塑性高分子粉末之后，经过热烤炉，形成热塑性高分子粉末层及完成硬化反应，通过轧辊来制备薄膜加强层；第四步骤，通过热覆膜工序向由热塑性发泡片构成的芯材层的一面或两面连续地层叠所制备的上述薄膜加强层，由此制备基材。
并且，本发明提供耐湿性得到强化的汽车内饰材料用环保轻量基材的制备方法，其特征在于，包括：第一步骤，通过梳理来混合天然纤维和合成纤维，借助铺网和针刺工序制备毡子；第二步骤，向上述毡子涂敷或浸渍异氰酸酯或环氧树脂，通过150℃至250℃的热轧辊，以半硬化状态成型之后，通过进行施压来制备成薄片；第三步骤，向上述薄片涂敷10g/m2至100g/m2的热塑性粉末，并经过150℃至250℃的热烤炉之后，以热辊进行施压来准备薄膜加强层；以及第四步骤，通过热覆膜工序连续地向热塑性发泡片层叠所制备的上述薄膜加强层，由此制备基材。
优选地，上述热塑性发泡片为聚丙烯、聚乙烯或聚酯，发泡倍率为5倍至40倍，厚度为2mm至10mm。
优选地，上述异氰酸酯为二苯甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)。
优选地，涂敷或浸渍于上述天然纤维薄膜加强层的异氰酸酯的重量为5g/m2至100g/m2。
优选地，包含在上述薄膜加强层的环氧树脂或异氰酸酯以喷洒工序或浸渍辊子的方式进行添加。
优选地，上述薄膜加强层的厚度为0.5mm至2mm，重量为120g/m2至700g/m2。
优选地，在本发明中，用于上述薄膜加强层的合成纤维采用选自长度为30mm至100mm的聚丙烯纤维、皮芯型低熔点聚酯纤维、聚酯纤维、聚乙烯纤维、丙烯酸纤维或生物降解性纤维中的一种以上。
优选地，用于上述薄膜加强层的合成纤维的含量为30重量％至70重量％。
优选地，用于上述薄膜加强层的天然纤维选自长度为30mm至100mm的洋麻、黄麻、亚麻、***、竹子或剑麻中的一种以上。
优选地，用于上述薄膜加强层的天然纤维的含量为30重量％至70重量％。
优选地，上述热塑性粉末使用选自低密度聚乙烯、高密度聚乙烯或聚丙烯中的一种或一种以上。
优选地，本发明的耐湿性优秀的环保轻量基材的重量为300g/m2至1500g/m2。
而且，本发明还提供耐湿性得到强化的汽车内饰材料用环保轻量基材，其特征在于，上述汽车内饰材料用环保轻量基材是借助上述制备方法中的一种方法制备，并且其以在热塑性发泡片构成的芯材层的一面或两面进行薄膜加强层的热覆膜而形成的，上述薄膜加强层是通过向天然纤维和合成纤维毡子层表面涂敷或浸渍液状异氰酸酯之后，通过进行热轧辊来实现半硬化，接着向上述薄膜加强层涂敷热塑性粉末之后，经过热烤炉，来完成热塑性粉末层的形成及异氰酸酯或环氧树脂的硬化反应。
本发明还提供耐湿性得到强化的汽车内饰材料用环保轻量基材，其特征在于，耐湿弯曲强度超过1.0kgf/5cm，耐湿悬垂量L为2.0以下。
(其中，耐湿弯曲强度(kgf/5cm)的测量标准为，针对“50mm x150mm x厚度”及“660g/m2”重量的试片，以5mm/min的试验速度、100mm的跨距(span width)，并在50℃、95RH％湿度条件下放置24小时之后，在23℃、95RH％的条件下实施1小时稳定化之后，依据ASTMD790进行测量；
耐湿悬垂量L的测量标准为，针对“50mm x 200mm x厚度”及“660g/m2”重量的试片，固定末端部分70mm，在相反侧部分放置40mmx 60mm的34.2g的锤，测量从底面到试片下方的初始高度L1和在50℃、95RH％湿度条件下放置7小时后重新测量的后期高度L2，通过L＝L1-L2计算得出。)
如上所述，本发明的汽车内饰材料用环保轻量基材将以往的用于汽车产业领域的玻璃纤维替换成天然纤维，使得具有采用对人体无害的环保材料的优点，而且放弃使用为了粘结发泡片和加强层而使用的粘合剂或热熔胶膜，而采用热覆膜工序，从而具有使工序变得简单，价格低廉，向工作人员营造对人体无害的作业环境的优点。并且，通过采用价格低廉和工序简单的方法，将异氰酸酯(或环氧树脂)适用于天然纤维加强层，可一定程度上改善现有的包含天然纤维的三明治结构的汽车内饰材料用基材所具有的在高温多湿环境中的悬垂现象、错位现象及物性低下的问题，因此，不仅适用于汽车内饰材料，还具有可应用于火车内饰材料、飞机内饰材料及建筑内饰材料等各种产业领域的优点。
并且，本发明的制备方法，在制备这种轻量基材时，仅向现有的生产工序补充简单的工序，从而使追加设备等相关费用的负担降至最小，使得具有能够以低成本完成制备的效果。
附图说明
图1为表示异氰酸酯应用前后的天然纤维高分子复合物的拉伸强度的差异的图表。
图2为表示异氰酸酯应用前后的天然纤维高分子复合物的耐湿时间下的表面形态的图片。
图3为表示异氰酸酯应用前后的随耐湿时间的天然纤维高分子复合物的拉伸强度的变化的图表。
图4为表示根据本发明的一实施例的汽车内饰材料用环保轻量基材的构成图。
附图标记的说明
10：薄膜加强层 20：芯材层
30：汽车内饰材料用环保轻量基材
具体实施方式
以下记载内容是为了详细说明本发明的适用效果，且仅仅是对本发明的例示，并非用于限制本发明的范围。
首先，对天然纤维高分子复合物进行说明。
<材料>
1.异氰酸酯：4,4'-methylenediphenyl diisocyanate(㈱PIUSYS)
2.天然纤维：洋麻(kenaf)(平均直径70μm，长度60～80mm)
3.热塑性高分子：聚丙烯(㈱韩国FIBER，直径6D，长度51mm),聚酯纤维(熊津化学㈱，直径6D，长度51mm)
<实施例1：天然纤维/高分子复合物的制备>
根据本发明的天然纤维/高分子复合物的制备依照以下工序顺序，并按照表1所示的混合物的比例实施。成型条件为热压温度200℃、热压时间60秒、冷压温度23℃、冷压时间60秒钟。
工序顺序
i)经过天然纤维和热塑性高分子纤维的混合、开松、梳理、铺网及针刺工序来制备天然纤维/高分子毡子。ii)向上述毡子喷涂或者沾在滚子上，添加1至30phr的异氰酸酯之后，通过热轧辊将异氰酸酯以半硬化状态成型。iii)在其上涂敷热塑性高分子粉末之后，再次通过热轧辊完成异氰酸酯的硬化，形成热塑性高分子粉末层，从而制备天然纤维/高分子复合物。
【表1】
<实施例2：测量拉伸强度>
针对在实施例1中制备的天然纤维/高分子复合物，图1示出了根据异氰酸酯的含量的拉伸强度。如图1所示，相比于未添加异氰酸酯的情况，所测出的拉伸强度较高，在添加5％异氰酸酯的情况下，拉伸强度约为23％，在添加10％异氰酸酯的情况下，拉伸强度约为38％。
<实施例3:评估耐湿性>
针对在实施例1中制备的天然纤维高分子复合物，借助不同耐湿时间下的形态和拉伸强度的变化，来实施对异氰酸酯层适用前后的耐湿性的评估。图2表示异氰酸酯添加前后根据耐湿时间的天然纤维高分子复合物的表面形态。如图2所示，相比于涂敷异氰酸酯之前，涂敷异氰酸酯之后表面随着耐湿时间的经过而被损伤的现象显著减少。
图3表示适用异氰酸酯层前后根据耐湿时间的天然纤维高分子复合物的拉伸强度的变化。在未适用异氰酸酯层的情况下，在50℃、相对湿度为95％的条件下经过15天，最大拉伸强度减少约25％；而在添加异氰酸酯的情况下，拉伸强度减少约8％。
综合以上结果，通过添加异氰酸酯，可以有效提高天然纤维高分子复合物的拉伸强度和耐湿性。
以下，将对以如上所述的方法制备的天然纤维高分子复合物作为薄膜加强层使用的汽车内饰材料用环保轻量基材的制备方法进行说明。
汽车内饰材料用环保轻量基材包括芯材层发泡片和薄膜加强层。根据以往的采用天然纤维的汽车内饰材料用基材，由于天然纤维不耐水分的特性，在高温多湿的环境下，会发生悬垂及错位等现象，被指出在形态稳定性方面存在问题。
因此，在本发明中，将在发泡片上作为薄膜加强层而适用异氰酸酯的天然纤维薄片，经过热覆膜工序，连续地层叠，可提高耐湿性及弯曲强度。
根据本发明的汽车内饰材料用环保轻量基材的制备依照以下工序顺序进行。
ⅰ)天然纤维和合成纤维按照4：6的重量比并通过混合工序、梳理工序、铺网工序、针刺工序来制备天然纤维毡子。
ⅱ)经过喷洒工序向上述毡子涂敷/浸渍异氰酸酯之后，通过热轧辊来使异氰酸酯以半硬化状态成型。
ⅲ)在其上涂敷高密度聚乙烯粉末，经过热烤炉后完成高密度聚乙烯粉末层的形成及异氰酸酯的硬化反应，使用轧辊施压并制备薄膜加强层10。
ⅳ)在作为芯材层20的聚丙烯发泡片上，通过热覆膜来将薄膜加强层10连续地向两面进行层叠，由此制备汽车内饰材料用环保轻量基材30。
表2示出了相比于以往的试片的，根据本发明所制备的试片的常温、耐湿弯曲强度及耐湿悬垂量。通过表2的比较，在相同的重量条件下，分别添加12g/m2、24g/m2的异氰酸酯时，弯曲强度状态分别为60％、85％，耐湿弯曲强度分别增加约90％、110％，耐湿悬垂量也分别减少50％、80％，耐湿性和机械特性显著得到改善。
相比于以往的高重量基材，即便重量下降了约20％，但在添加12g/m2异氰酸酯的情况下表现出优秀的耐湿性，在添加24g/m2的情况下，弯曲强度和耐湿性得到显著改善，由此可知，根据本发明可实现环保基材的轻量化。
弯曲强度的测量依据ASTM D790并以50mm x 150mm x厚度大小的试片、5mm/min的试验速度、100mm的跨距(span width)实施，关于耐湿弯曲强度条件，在50℃、95RH％湿度条件下放置24小时之后，在23℃、95RH％的条件下实施1小时稳定化，并按照上述条件进行试验。
关于耐湿悬垂量，针对50mm x 200mm x厚度的试片，固定末端部分70mm之后，在相反侧部分放置40mm x 60mm的34.2g的锤，测量从底面到试片下方的初始高度L1和在50℃、95RH％湿度条件下放置7小时后重新测量的高度L2，并将赋予湿度前后的高度的变化量作为耐湿悬垂量L进行计算。
耐湿悬垂量L＝初始高度L1-后期高度L2
【表2】

Claims (14)

1.一种天然纤维高分子复合物的制备方法，其中，包括：
制备由天然纤维和热塑性高分子纤维的混合物构成的毡子的步骤；
向上述毡子表面喷雾或涂敷液状异氰酸酯的步骤；以及
通过对上述喷雾有液状异氰酸酯的毡子进行热压来实施硬化，由此制成薄片形态的硬化步骤，
其中，在上述硬化步骤中，通过上述热压来实施薄片化，使得上述异氰酸酯呈半硬化状态之后，向上述毡子的表面涂敷热塑性高分子粉末之后，借助冷压来完成异氰酸酯的硬化。
2.根据权利要求1所述的天然纤维高分子复合物的制备方法，其中，上述天然纤维为纤维素类纤维。
3.根据权利要求1所述的天然纤维高分子复合物的制备方法，其中，上述异氰酸酯为二苯甲烷二异氰酸酯或甲苯二异氰酸酯。
4.一种汽车内饰材料用环保轻量基材的制备方法，其中，包括：
第一步骤，以天然纤维和合成纤维制备毡子；
第二步骤，向上述毡子涂敷异氰酸酯之后，利用热轧辊来成型，使得上述异氰酸酯呈半硬化状态，由此制备薄片；
第三步骤，向上述薄片涂敷热塑性粉末之后进行加热，从而在上述薄片的表面形成热塑性粉末层，由此完成上述异氰酸酯硬化反应，并通过向上述薄片施压来制备薄膜加强层；以及
第四步骤，通过热覆膜工序向由热塑性发泡片构成的芯材层的一面或两面连续地层叠上述所制备的薄膜加强层。
5.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，上述热塑性发泡片为聚丙烯、聚乙烯或聚酯，发泡倍率为5倍至40倍，厚度为2mm至10mm。
6.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，上述异氰酸酯为二苯甲烷二异氰酸酯或甲苯二异氰酸酯。
7.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，包含在上述薄膜加强层的异氰酸酯的重量为5g/m2至100g/m2。
8.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，上述薄膜加强层的厚度为0.5mm至2mm，重量为120g/m2至700g/m2。
9.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，用于上述薄膜加强层的合成纤维采用选自长度为30mm至100mm的聚丙烯纤维、皮芯型低熔点聚酯纤维、聚酯纤维、聚乙烯纤维、丙烯酸纤维或生物降解性纤维中的一种或一种以上。
10.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，用于上述薄膜加强层的合成纤维的含量为30重量％至70重量％。
11.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，用于上述薄膜加强层的天然纤维选自长度为30mm至100mm的洋麻、黄麻、亚麻、***、竹子或剑麻中的一种以上。
12.根据权利要求4所述的汽车内饰材料用环保轻量基材的制备方法，其中，上述热塑性粉末使用选自低密度聚乙烯、高密度聚乙烯或聚丙烯中的一种或一种以上。
13.一种汽车内饰材料用环保轻量基材，其中，通过权利要求4所述的制备方法来制备。
14.根据权利要求13所述的汽车内饰材料用环保轻量基材，其中，基于如下基准的耐湿弯曲强度超过1.0kgf/5cm，耐湿悬垂量L为2.0mm以下，
其中，耐湿弯曲强度kgf/5cm的测量标准为，针对“50mm x 150mm x厚度”及“660g/㎡”重量的试片，以5mm/min的试验速度、100mm的跨距，并在50℃、95RH％湿度条件下放置24小时之后，在23℃、95RH％的条件下实施1小时稳定化之后，依据ASTM D790进行测量；
耐湿悬垂量L的测量标准为，针对“50mm x 200mm x厚度”及“660g/㎡”重量的试片，固定末端部分70mm，在相反侧部分放置40mm x 60mm的34.2g的锤，测量从底面到试片下方的初始高度L1和在50℃、95RH％湿度条件下放置7小时后重新测量的后期高度L2，通过L＝L1-L2计算得出。
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