CN107177242A - 耐醇的热塑性聚烯烃汽车内饰材料及其制备方法 - Google Patents

耐醇的热塑性聚烯烃汽车内饰材料及其制备方法 Download PDF

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CN107177242A
CN107177242A CN201710373383.0A CN201710373383A CN107177242A CN 107177242 A CN107177242 A CN 107177242A CN 201710373383 A CN201710373383 A CN 201710373383A CN 107177242 A CN107177242 A CN 107177242A
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tpo
automotive interior
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sealing wax
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CN107177242B (zh
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吴飞飞
陈红梅
滕大勇
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Benecke Changshun Automotive Interior Materials (zhangjiagang) Co Ltd
Benecke Changshun Auto Trim Zhangjiagang Co Ltd
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Abstract

本发明提供一种耐醇的热塑性聚烯烃汽车内饰材料及其制备方法,本发明的TPO汽车内饰材料依次包括TPO层和水漆层,所述水漆层涂饰在所述TPO层上,所述水漆层具有三层结构,所述三层结构依次为胶水层、底漆层和面漆层,本发明的TPO汽车内饰材料具有水漆层与TPO层之间的机械力学性能良好、粘结性强、不掉浆、不裂浆、耐磨,兼具优良的耐醇性,胶水层、底漆层和面漆层更是赋予本发明TPO汽车内饰材料类似真皮的舒适度和手感,且采用的是水性表面修饰材料,本发明TPO汽车内饰材料更为安全环保。

Description

耐醇的热塑性聚烯烃汽车内饰材料及其制备方法
技术领域
本发明涉及汽车内饰材料的技术领域,具体地是一种耐醇的热塑性聚烯烃汽车内饰材料及其制备方法。
背景技术
目前以汽车内饰材料应用广泛,汽车内饰材料除了对美观方面的要求,更多的是对性能上的要求,例如汽车内饰材料的耐醇性问题,目前能够满足耐醇性要求的产品类别主要包括PVC汽车内饰材料和TPO(热塑性聚烯烃) 汽车内饰材料,PVC汽车内饰材料与TPO汽车内饰材料相比,PVC汽车内饰材料无法满足轻质的特点,但目前针对TPO汽车内饰材料仍存在技术空白,而用在PVC汽车内饰材料的水性表面处理剂(即水漆层材料)大多数无法直接用在TPO汽车内饰材料表面上,因为TPO层表面张力极低,即使经过电晕处理,也无法保证基材与一般水性表面处理剂的粘结力,具有水漆层剥落的风险,进一步导致最终汽车内饰材料产品不耐高温、机械力学性差、易破裂等问题;在TPO汽车内饰材料上使用溶剂型表面处理剂不安全、危害性较大,存在VOC和气味问题。
另一方面在汽车内饰材料表面处理过程中常使用属于生殖毒性的物质——N-甲基吡咯烷酮和N-乙基吡咯烷酮,危害人体健康,现有TPO汽车内饰材料,多数以水性表面处理剂进行表面处理,存在VOC和气味问题,因此,迫切需要阻燃性能好、可自行熄灭、机械强度高、安全可靠、稳定性强的汽车内饰材料。
发明内容
针对以上问题,本发明提供一种耐醇的热塑性聚烯烃汽车内饰材料,其具有水漆层与TPO层之间的机械力学性能良好、粘结性强、不掉浆、不裂浆、耐磨,采用本发明配方的TPO汽车内饰材料兼具优良的耐醇性,胶水层、底漆层和面漆层更是赋予本发明TPO汽车内饰材料类似真皮的舒适度和手感,且采用的是水性表面修饰材料,本发明TPO汽车内饰材料更为安全环保。
本发明所采取的技术方案是:其依次包括TPO层和水漆层,所述水漆层涂饰在所述TPO层上,所述水漆层具有三层结构,所述三层结构依次为胶水层、底漆层和面漆层,其中,所述TPO层由以下质量份的成分组成:TPO粒子40-70份、聚双酚酸苯基磷酸酯1-2份、稳定剂0.5-1份、聚乙烯蜡0.1-0.3 份、十二烷基磺酸钠0.01-0.5份。
作为优选,所述TPO层由以下质量份的成分组成:TPO粒子40-60份、聚双酚酸苯基磷酸酯1-1.5份、稳定剂0.5-0.8份、聚乙烯蜡0.1-0.25份,因为 TPO层含有十二烷基磺酸钠,确保TPO层和水漆层之间的粘结性,使得汽车内饰材料的机械性能更强。
钛酸酯优选单烷氧基磷酸酯钛酸酯偶联剂Tl-411-A,因为阴离子型表面活性剂和两性表面活性剂之间的复配会产生显著的增效作用,本发明选用十二烷基磺酸钠与钛酸酯之间的协同作用,一方面提高表面活性剂的性能、进一步增强TPO层与胶水层粘结的稳定性,无需在TPO层的配方中另加其他稳定剂,另一方面因为钛酸酯偶联剂Tl-411-A钛酸酯本身含有磺酸基和磷酸酯基等多种活性基团赋予TPO层体系一定的粘结性,TPO粒子与具有表面活性较强的十二烷基磺酸钠、钛酸酯共同起到协同作用,钛酸酯偶联剂中所含有的磺酸基和磷酸酯基等多种活性基团,与聚双酚酸苯基磷酸酯相互作用,使粘结性更强,满足了产品不掉浆、不裂浆、粘层牢固、耐磨的质量要求。
作为优选,所述胶水层由以下质量份的成分组成:磷酸酯基环氧树脂改性的水性聚氨酯20-50份、2-甲基四氢呋喃25-35份、钛酸酯1-2.5份、聚乙烯亚胺0.5-1份,磷酸酯基环氧树脂改性的水性聚氨酯使本发明TPO汽车内饰材料产品的耐醇性更优,钛酸酯与具有磷酸酯基的磷酸酯基环氧树脂改性的水性聚氨酯相互交联,使胶水层与TPO层之间具有较强的粘结性,再者,聚乙烯亚胺可以同时吸附水漆层、TPO层中释放的偏酸性醛类物质,使本发明的TPO汽车内饰材料产品的安全性更高。
作为优选,所述底漆层由以下质量份的成分组成:TPO粒子25-40份;苯并噁嗪树脂8-12份;聚双酚酸苯基磷酸酯1-1.5份,苯并噁嗪树脂的界面性能,使汽车内饰材料的拉伸强度和弯曲强度分别提高了52.74%和102.82%,使制备的TPO汽车内饰材料在力学性能方面达到了增强和增韧的双重效果,同时胶水层表面的钛酸酯与底漆层表面的苯并噁嗪树脂、聚双酚酸苯基磷酸酯之间相互作用,粘结性更强,而且还增加了TPO汽车内饰材料整体的阻燃特性;环氧树脂纳米复合材料本身的耐磨强度和韧性强、耐低温力学性能强、粘结性能强,不仅满足了汽车内饰材料产品轻质的特性,而且与TPO粒子的相容性较好,进一步增强水漆层的机械稳定性能。
作为优选,所述面漆层由以下质量份的成分组成:氢化苯基甲烷二异氰酸酯20-50份;苯并噁嗪树脂5-15份;2-甲基四氢呋喃25-35份;手感剂1-3 份;聚双酚酸苯基磷酸酯1-2份,本发明水漆体系中不含有行业内常用的N- 甲基吡咯烷酮和N-乙基吡咯烷酮强极性溶剂(N-甲基吡咯烷酮和N-乙基吡咯烷酮都已经被欧盟法规列为属于生殖毒性的物质),而是采用了2-甲基四氢呋喃作为溶解TPO的溶剂;又因为聚双酚酸苯基磷酸酯是以生物质资源双酚酸为原料制备的阻燃剂,使得最终的汽车内饰材料产品更安全、更环保;再者,氢化苯基甲烷二异氰酸酯赋予了本发明TPO汽车内饰材料更优越的耐醇性能。
所述手感剂由以下质量份的成分组成:石蜡10份、脂肪酸5份、微晶蜡 2份、失水山梨醇单油酸酯聚氧乙烯醚1.8份、聚丙烯酸钠1份、乳化硅油0.4 份,使水漆层整体更加温暖柔软的丝绸手感,更接近于真皮之手感效果。
采用以上配方后,本发明耐醇的热塑性聚烯烃汽车内饰材料与现有技术相比具有以下优点:
首先,本发明配方中TPO材料的使用,满足了汽车内饰材料质轻的要求,采用的是水性表面修饰材料,用水性表面修饰材料作为水漆层的原料,使本发明TPO汽车内饰材料更为环保、安全系数高;
其次,本发明配方的TPO汽车内饰材料层与层之间的粘结性较强,每层之间化合物和聚合物之间可以建立起分子间或离子间作用力,使层与层之间的协同粘结性更强,更进一步地保证了产品不掉浆、不裂浆、粘层牢固、耐磨的质量要求;
再者,本发明胶水层、底漆层和面漆层所形成的水漆层稳定性更强、更环保。配方中不含有行业内常用的N-甲基吡咯烷酮和N-乙基吡咯烷酮强极性溶剂(N-甲基吡咯烷酮和N-乙基吡咯烷酮都已经被欧盟法规列为属于生殖毒性的物质);聚双酚酸苯基磷酸酯中因为芳基磷酸酯的存在,可以适度改变 TPO的表面张力;再者,聚双酚酸苯基磷酸酯是以生物质资源双酚酸为原料制备的原材料,使最终汽车内饰材料产品更安全、更环保;
而且,采用本发明配方的TPO汽车内饰材料中磷酸酯基环氧树脂改性的水性聚氨酯和氢化苯基甲烷二异氰酸酯赋予本发明产品优良的耐醇性;本发明TPO汽车内饰材料可广泛运用于汽车内饰件等。
本发明的另一目的是提供一种耐醇的热塑性聚烯烃汽车内饰材料的制备方法,该制备方法包括以下步骤:
(1)将TPO层的组分材料充分均匀混合,经混炼、塑炼,然后挤出,电晕处理,得半成品;
(2)将水漆层中胶水层、底漆层和面漆层的材料分别充分搅拌混匀,并对步骤(1)制得的半成品进行表面处理,冷却,得汽车内饰材料成品。
其中,所述步骤(1)中的混炼温度120-140℃,混炼时间2-5min;所述步骤(1)中塑炼的温度100-110℃,塑炼时间9-12min;所述步骤(1)中挤出机挤出得到的0.3-1mm的薄膜材料;所述步骤(1)中电晕处理为在5-10kV 条件下处理5-10s。
所述步骤(2)中的表面处理具体是指依次进行以下步骤:①涂饰所述胶水层的厚度10-15μm的水漆,100-120℃固化烘干;②涂饰所述底漆层的厚度 10-20μm的水漆,90-100℃固化烘干;③涂饰所述面漆层的厚度10-15μm的水漆,80-100℃固化烘干。可以采用滚涂或喷涂等方式进行表面修饰。
利用本发明耐醇的热塑性聚烯烃汽车内饰材料的制备方法与现有技术相比具有以下优点:(1)TPO层预先采用电晕处理,以降低表面张力,确保层与层之间的粘结性;(2)表面处理采用一种创新的处理方式,分三层结构,可以根据产品特性,以提供不同的性能要求;(3)本发明的耐醇的热塑性聚烯烃汽车内饰材料的制备方法简单,结合材料本身特点,操作温度比现有技术的温度要求低,避免了因温度过高引发火灾等问题,也更节约能源,生产成本更低。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。本发明的具体实施方式由以下实施例及其附图详细给出。
附图说明
为了更清楚地说明本发明实施例技术中的技术方案,下面将对实施例技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例。
图1是本发明耐醇的热塑性聚烯烃汽车内饰材料的结构示意图;
图2是本发明对比例4耐乙醇的Crock Meter测试;
图3是本发明对比例5耐乙醇的Crock Meter测试。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
下面结合附图和具体实施方式对本发明作进一步说明。
如图1为本发明耐醇的热塑性聚烯烃汽车内饰材料的结构示意图,本发明汽车内饰材料具有四层机构,依次为TPO层、水漆层,其中水漆层具有三层结构,依次为胶水层、底漆层和面漆层。
实施例1
手感剂由以下成分组成:石蜡10g、脂肪酸5g、微晶蜡2g、失水山梨醇单油酸酯聚氧乙烯醚1.8g、聚丙烯酸钠1g、乳化硅油0.4g,称好后,充分混匀。
按照下表1中实施例1的重量份称取TPO层组分,并充分混合均匀,将准确称量的TPO层组分在高速分散混合机内充分混合均匀,保持搅拌温度115℃,再转移至温度130℃的混炼机内混炼,混炼时间4min;将混炼好的混合材料,传输至温度为100℃的炼胶机上进行塑炼,塑炼时间10min,然后挤出机挤出得到的0.3-1mm的薄膜材料。
按照表2、表3、表4中实施例1的重量份分别称量胶水层、底漆层和面漆层组分,充分混匀,备用。
将薄膜材料在7kV条件下进行电晕处理5s,送入压花机内加热,并涂覆的水漆层:涂覆条件依次为:①涂饰胶水层:厚度10μm的水漆,100℃固化烘干;②涂饰底漆层:厚度15μm的水漆,95℃固化烘干;③涂饰面漆层:厚度15μm的水漆,90℃固化烘干,经冷却定型即可得到本发明的汽车内饰材料。
实施例2
手感剂配方同实施例1,按照下表1中实施例2的重量份称取TPO层组分,并充分混合均匀,将准确称量的TPO层组分在高速分散混合机内充分混合均匀,保持搅拌温度115℃,再转移至温度120℃的混炼机内混炼,混炼时间5min;将混炼好的混合材料,传输至温度为110℃的炼胶机上进行塑炼,塑炼时间12min,然后挤出机挤出得到的0.3-1mm的薄膜材料。
按照表2、表3、表4中实施例2的重量份分别称量胶水层、底漆层和面漆层组分,充分混匀,备用。
将薄膜材料在5kV条件下进行电晕处理10s,送入压花机内加热,并涂覆的水漆层:涂覆条件依次为:①涂饰胶水层:厚度15μm的水漆,120℃固化烘干;②涂饰底漆层:厚度20μm的水漆,100℃固化烘干;③涂饰面漆层:厚度15μm的水漆,100℃固化烘干,经冷却定型即可得到本发明的汽车内饰材料。
实施例3
手感剂配方同实施例1,按照下表1中实施例3的重量份称取TPO层组分,并充分混合均匀,将准确称量的TPO层组分在高速分散混合机内充分混合均匀,保持搅拌温度115℃,再转移至温度140℃的混炼机内混炼,混炼时间2min;将混炼好的混合材料,传输至温度为110℃的炼胶机上进行塑炼,塑炼时间9min,然后挤出机挤出得到的0.3-1mm的薄膜材料。
按照表2、表3、表4中实施例3的重量份分别称量胶水层、底漆层和面漆层组分,充分混匀,备用。
将薄膜材料在10kV条件下进行电晕处理5s,送入压花机内加热,并涂覆的水漆层:涂覆条件依次为:①涂饰胶水层:厚度10μm的水漆,100℃固化烘干;②涂饰底漆层:厚度15μm的水漆,90℃固化烘干;③涂饰面漆层:厚度10μm的水漆,80℃固化烘干,经冷却定型即可得到本发明的汽车内饰材料。
实施例4
按照下表1、表2、表3、表4中实施例4的重量份分别称取TPO层、胶水层、底漆层和面漆层组分,并充分混合均匀,其他同实施例1。
对比例1
按照下表1、表2、表3、表4中对比例1的重量份分别称取TPO层、胶水层、底漆层和面漆层组分,并充分混合均匀,其他同实施例1。
对比例2
按照下表1、表2、表3、表4中对比例2的重量份分别称取TPO层、胶水层、底漆层和面漆层组分,并充分混合均匀,其他同实施例1。
对比例3
按照下表1、表2、表3、表4中对比例3的重量份分别称取TPO层、胶水层、底漆层和面漆层组分,并充分混合均匀,其他同实施例1。
对比例4
选取同样大小且经过表面修饰的常规PVC汽车内饰材料产品,用于表面修饰的水漆层为溶剂型表面修饰材料。
对比例5
在TPO层上不涂覆水漆层,其他同实施例4。
对比例6
在TPO层上不涂覆面漆层,其他同实施例4。
表1各实施例中TPO层组份含量(单位:kg)
表2各实施例中胶水层组份含量(单位:kg)
表3各实施例中底漆层组份含量(单位:kg)
TPO 苯并噁嗪树脂 聚双酚酸苯基磷酸酯
实施例1 25 5 1.0
实施例2 37 8 1.2
实施例3 40 12 1.5
实施例4 40 15 1.2
对比例1 25 13 1.5
对比例2 37 0 0
对比例3 26 20 1.2
表4各实施例中水漆层组份含量(单位:kg)
结果验证实验
验证例1:力学性能测试
按照ASTM D1415方法测定所制备的汽车内饰材料硬度,采用GB 2917.1-2002标准刚果红法测定汽车内饰材料的热稳定性能;按照GB/T 17928-1999标准测定汽车内饰材料的撕裂强度,上述结果见表5。按照GB 21550-2008标准测定汽车内饰材料中有害物质限量,尤其是挥发性物质的含量小于4.11g/m3、氯乙烯单体含量小于0.8mg/kg,均明显低于国家标准,结果表明实施例1-4中制备的汽车内饰材料是一种环境友好型汽车内饰材料。
表5力学性能测试验证试验结果
邵氏硬度/HA 热稳定性/min 撕裂强度/N
实施例1 65 10 41
实施例2 74 14 49
实施例3 80 12 57
实施例4 86 18 63
对比例1 59 8 22
对比例2 53 7 17
对比例3 62 15 40
明显看出,实施例1-4中的力学机械性、热稳定性等参数整体效果是优于对比例1-3的,尽管对比例3中的整体效果与本实施例中的效果相对接近,但是因为并没有使用手感剂,考虑到实际生产中消费者对最终产品质感的需求,增加了手感剂的配方,而且通过实验室检测,选用本发明配方的手感剂使汽车内饰材料附着力更强、并赋予产品耐湿擦以及温暖柔软的丝绸质感。
验证例2:耐醇性测试
使用水性表面修饰材料作为水漆层的原料,对实施例4和对比例4-6进行耐乙醇、异丙醇的Drop Test和Crock Meter测试,乙醇的Crock Meter测试(如图2和图3)、异丙醇的Crock Meter测试、异丙醇的Drop Test测试结果见表 6,实验表明,本发明的TPO汽车内饰材料具有与使用溶剂型表面修饰材料作为水漆层的原料PVC产品的效果,但是传统PVC汽车内饰材料不能满足轻质、无公害的绿色环保需求。
表6耐醇性测试验证试验结果
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (7)

1.一种耐醇的热塑性聚烯烃汽车内饰材料,其依次包括TPO层和水漆层,所述水漆层涂饰在所述TPO层上,其特征在于:所述水漆层具有三层结构,所述三层结构依次为胶水层、底漆层和面漆层,其中,所述TPO层由以下质量份的成分组成:TPO粒子40-70份、聚双酚酸苯基磷酸酯1-2份、稳定剂0.5-1份、聚乙烯蜡0.1-0.3份、十二烷基磺酸钠0.01-0.5份。
2.根据权利要求1所述的耐醇的热塑性聚烯烃汽车内饰材料,其特征在于:所述胶水层由以下质量份的成分组成:磷酸酯基环氧树脂改性的水性聚氨酯20-50份、2-甲基四氢呋喃25-35份、钛酸酯1-2.5份、聚乙烯亚胺0.5-1份。
3.根据权利要求1所述的耐醇的热塑性聚烯烃汽车内饰材料,其特征在于:所述面漆层由以下质量份的成分组成:氢化苯基甲烷二异氰酸酯20-50份;苯并噁嗪树脂5-15份;2-甲基四氢呋喃25-35份;手感剂1-3份;聚双酚酸苯基磷酸酯1-2份。
4.根据权利要求4所述的耐醇的热塑性聚烯烃汽车内饰材料,其特征在于:所述手感剂由以下质量份的成分组成:石蜡10份、脂肪酸5份、微晶蜡2份、失水山梨醇单油酸酯聚氧乙烯醚1.8份、聚丙烯酸钠1份、乳化硅油0.4份。
5.一种耐醇的热塑性聚烯烃汽车内饰材料的制备方法,其特征在于:该制备方法包括以下步骤:
(1)将TPO层的组分材料充分均匀混合,经混炼、塑炼,然后挤出机挤出薄膜材料,电晕处理,得半成品;
(2)将水漆层中胶水层、底漆层和面漆层的材料分别充分搅拌混匀,并对步骤(1)制得的半成品进行表面处理,冷却,得汽车内饰材料成品。
6.根据权利要求5所述的耐醇的热塑性聚烯烃汽车内饰材料的制备方法,其特征在于:所述步骤(1)中的混炼温度120-140℃,混炼时间2-5min;所述步骤(1)中塑炼的温度100-110℃,塑炼时间9-12min;所述步骤(1)中的挤出机挤出得到的0.3-1mm的薄膜材料;所述步骤(1)中电晕处理为在5-10kV条件下处理5-10s。
7.根据权利要求5所述的耐醇的热塑性聚烯烃汽车内饰材料的制备方法,其特征在于:所述步骤(2)中的表面处理具体是指依次进行以下步骤:①涂饰所述胶水层的厚度10-15μm的水漆,100-120℃固化烘干;②涂饰所述底漆层的厚度10-20μm的水漆,90-100℃固化烘干;③涂饰所述面漆层的厚度10-15μm的水漆,80-100℃固化烘干。
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