CN107190521B - 一种低气味pvc人造革及其制备方法 - Google Patents
一种低气味pvc人造革及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉55‑65份、增塑剂30‑40份、发泡剂5‑8份、安定剂1‑3份、颜料0‑6份、助剂0‑3份；所述增塑剂包括环氧大豆油和领苯类增塑剂，所述环氧大豆油和领苯类增塑剂的重量比为2.5‑5:1；所述发泡剂为物理发泡剂；所述安定剂为钙锌复合稳定剂；所述油漆层是由水性聚氨酯树脂制备而成的。本发明还公开了该低气味PVC人造革的制备方法。本发明的低气味PVC人造革，经PV3900 C3气味等级检测，其气味等级为3.5级，满足国内外汽车厂商的要求。
Description
技术领域
本发明涉及汽车内饰材料领域，具体涉及一种低气味PVC人造革及其制备方法。
背景技术
随着现代化程度的迅速提高，人们对车辆的依赖也日益明显。除了家庭和工作场所，车辆成为人类主要滞留的场所之一。在2014年的《中国人群暴露手册》(成人卷)中查阅到普通的驾乘人员在所有的交通工具中暴露时间最长的是小轿车，全国的平均暴露时间是40分钟每天，其中北京、天津、广东等地驾乘人员的平均暴露时间高达60分钟每天。因此车内环境近年来备受关注，国家也制定了相应法规GB/T27630(2011)，其中规定了八项对人体伤害较大的有机挥发物限制，分别是苯、甲苯、乙苯、二甲苯、苯乙烯、甲醛、乙醛、丙烯醛，此法规将于2017成为强制法规。而作为汽内环境有机挥发及气味主要贡献来源的PVC内饰材料制造商来说将面临巨大挑战。因此，如何制备远低于国家标准和行业标准的低气味低散发PVC人造革，已成为行业内的研发焦点。。
PVC人造革生产涉及主要原材料有增塑剂、PVC粉、发泡剂和基布。其中增塑剂，不可避免会有游离醇产生，而游离醇含量是影响气味的主要来源之一；此外，大部分PVC生产厂商使用的是化学类发泡剂，此为发泡剂在高温发泡后会有强刺激性气体氨气残留。基于以上原因，普通PVC人造革根据气味测试方法PV3900 C3气味等级将≥4级(有明显气味，且让人感觉不适)，无法满足中国大部分中高端汽车用户的要求，例如，大众，宝马和奔驰等汽车供应商。此外，普通PVC人造革使用的基布和油漆原材料分别存在残留乙醛和甲苯，这使得成品PVC人造革很难通过欧美中高端汽车用户的PVC人造革散发测试。
发明内容
本发明的目的在于克服现有技术存在的以上问题，提供一种低气味PVC人造革，其能降低PVC人造革气味，提升了产品的健康安全性和舒适性。
本发明的另一目的在于提供一种上述PVC人造革的制备方法。
为实现上述技术目的，达到上述技术效果，本发明通过以下技术方案实现：
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉55-65份、增塑剂30-40份、发泡剂5-8份、安定剂1-3份、颜料0-6份、助剂0-3份；
所述增塑剂包括环氧大豆油和领苯类增塑剂，所述环氧大豆油和领苯类增塑剂的重量比为2.5-5:1；所述发泡剂为物理发泡剂；所述安定剂为钙锌复合稳定剂；所述油漆层是由水性聚氨酯树脂制备而成的。
环氧大豆油是用大豆油经过氧化处理后制得的一种化工产品，与PVC树脂相容性好，挥发性低、迁移性小，具有优良的热稳定性和光稳定性，且无毒性，是国际认可的用于食品包装材料的绿色增塑剂。环氧大豆油能吸收PVC树脂在受热分解时放出的HCl，另一方面又能改善PVC制品的光稳定性和热稳定性。而环氧大豆油和领苯类增塑剂的复配作为增塑剂对于降低气味更加有效果，主要原因是环氧大豆油能与聚酯类增塑剂发生协同作用，减少增塑剂的用量，从而减少了气味的主要来源。
本发明优选的方案为，所述环氧大豆油和领苯类增塑剂的质量比为3:1。
本发明优选的方案为，所述助剂包括阻燃剂、光稳定性和抗氧剂；所述阻燃剂为无机阻燃剂；所述光稳定剂为受组胺类光稳定剂；所述抗氧剂为受阻酚类抗氧剂或芳香胺类抗氧剂。
本发明优选的方案为，所述PVC皮层还包括0.5-2份的气味吸收剂，所述气味吸收剂为比表面积大于500m2/g的分子筛，所述分子筛的粒径为60-100μm。
分子筛具有很大的比表面积，对于极性分子和不饱和分子均表现出强烈的吸附能力。作为PVC皮层的原料时，与PVC分子之间具有良好的分散性，且能吸附PVC受热时产生的氯化氢分子，以及增塑剂中的醛类物质，从而达到降低气味和VOC散发的目的。
本发明优选的方案为，所述分子筛为活性炭分子筛或沸石分子筛。
本发明优选的方案为，所述PVC皮层是由如下的组分制备而成的：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份、气味吸收剂2份。
本发明还公开了上述低气味PVC人造革的制备方法，包括如下的步骤：
1)制备PVC浆料：按配方的配比将PVC皮层的原料混合、搅拌30-60min，接着抽真空5-10min，然后在抽真空的条件下继续搅拌5-10min，得到PVC浆料；
2)制备PVC皮层：将步骤1)制备的PVC浆料涂在离型纸上、烘干；接着继续涂上一层PVC浆料、烘干；然后涂上胶水，并复合上一层基布、烘干；最后撕去离型纸，即得PVC皮层；
3)制备油漆层：向步骤2)制备的PVC皮层上涂上一层底漆、烘干；再涂上一层面漆、烘干；
4)压花：使用压花设备在油漆层上压制花纹，即得本发明所述的低气味PVC人造革。
本发明优选的方案为，在步骤2)所述烘干的温度为180-240℃，所述烘干的时间为2-8min；在步骤3)中，所述烘干的温度为100-120℃，所述烘干的时间为5-10min。通过选择适当的干燥温度和时间，能使得气味分子和有机物充分散发。
本发明优选的方案为，所述基布选用含天然绵成分更多的基布，此外增加基布水洗工艺，进一步去除合成纤维中残留的油，降低了基布的气味。
本发明优选的方案为，在制备油漆层和压花的过程中，降低涂油漆和压花的速度，有利于延长产品生产过程中气味和有机挥发物的散发时间，从而达到进一步降气味和降散发性能的效果。
本发明的有益效果是:
本发明的低气味PVC人造革，经PV3900 C3气味等级检测，其气味等级低于3.5级，满足国内外汽车厂商的要求；本发明所用的塑化剂、安定剂、发泡剂等配料均不含有对人体有害的物质，绿色环保，且使用水性聚氨酯作为油漆层的原料，大大降低了VOC的散发量，使车内空气安全健康；本发明生产工艺简单，不易造成二次污染，有利于环境保护。
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详细说明如后。本发明的具体实施方式由以下实施例详细给出。
具体实施方式
下面将结合本发明实施例，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。
实施例1
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份、气味吸收剂2份。
本实施例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为3:1；发泡剂为物理发泡剂，如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份；气味吸收剂为活性炭分子筛。
上述低气味人造革的制备方法如下：
本发明还公开了上述低气味PVC人造革的制备方法，包括如下的步骤：
1)制备PVC浆料：按配方的配比将PVC皮层的原料混合、搅拌30-60min，接着抽真空5-10min，然后在抽真空的条件下继续搅拌5-10min，得到PVC浆料；
2)制备PVC皮层：将步骤1)制备的PVC浆料涂在离型纸上、烘干；接着继续涂上一层PVC浆料、烘干；然后涂上胶水，并复合上一层基布、烘干；最后撕去离型纸，即得PVC皮层；
3)制备油漆层：向步骤2)制备的PVC皮层上涂上一层底漆、烘干；再涂上一层面漆、烘干；
4)压花：使用压花设备在油漆层上压制花纹，即得本发明所述的低气味PVC人造革。
在步骤2)所述烘干的温度为180-240℃，所述烘干的时间为2-8min；在步骤3)中，所述烘干的温度为100-120℃，所述烘干的时间为5-10min。
实施例2
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉55份、增塑剂30份、发泡剂5份、安定剂1份、助剂1份、气味吸收剂0.5份。
本实施例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为2.5:1；发泡剂为物理发泡剂，如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化镁0.5份、受组胺类光稳定剂0.5份；气味吸收剂为沸石炭分子筛。
制备方法同实施例1。
实施例3
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉65份、增塑剂40份、发泡剂8份、安定剂3份、颜料6份、助剂3份、气味吸收剂2份。
本实施例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为5:1；发泡剂为物理发泡剂，如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化镁2份、受组酚类抗氧剂1份；气味吸收剂为沸石炭分子筛。
制备方法同实施例1。
实施例4
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉62份、增塑剂38份、发泡剂6份、安定剂2份、颜料4份、助剂2份、气味吸收剂1.5份。
本实施例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为4:1；发泡剂为物理发泡剂，如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化镁1份、受组酚类抗氧剂0.5份；气味吸收剂为沸石炭分子筛。
制备方法同实施例1。
实施例5
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份。
本实施例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为3:1；发泡剂为物理发泡剂，如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份。
制备方法同实施例1。
对比例1
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份。
本对比例中，增塑剂为领苯类增塑剂；发泡剂为化学发泡剂，偶氮二甲酰胺；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份。
制备方法同实施例1。
对比例2
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份。
本对比例中，增塑剂为环氧大豆油；发泡剂为化学发泡剂，如偶氮二甲酰胺；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份。
制备方法同实施例1。
对比例3
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份。
本对比例中，增塑剂为环氧大豆油和领苯类增塑剂的混合物，两者的重量比为3:1；发泡剂为化学发泡剂，如偶氮二甲酰胺；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份。
制备方法同实施例1。
对比例4
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份，气味吸收剂3份。
本对比例中，增塑剂为领苯类增塑剂；发泡剂为化学发泡剂，如偶氮二甲酰胺；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份，气味吸收剂为沸石炭分子筛。
制备方法同实施例1。
对比例5
一种低气味PVC人造革，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的组分：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份。
本对比例中，增塑剂为领苯类增塑剂；发泡剂为物理发泡剂，如如氟代烃类；安定剂为钙锌复合稳定剂；助剂为氢氧化铝1份、受组胺类光稳定剂1份、受阻酚类抗氧剂1份。
制备方法同实施例1。
性能检测
取实施例1-5及对比例1-5制备得到的PVC人造革，按照德国大众公司的标准PV3900-2000进行检测，所得结果如表1所示。材料的气味特性根据标准规定分为：1级，无气味；2级，有气味，但无干扰性气味；3级，有明显气味，但无干扰性气味；4级，有干扰性气味；5级，有强烈的干扰性气味；6级，有不能忍受的气味。
取实施例1-5及对比例1-5制备得到的PVC人造革，然后按照TS-BD-003规定的方法，测定内饰材料的VOC含量，所得结果如表2所示：
表1 实施例及对比例的气味等级测试
| 气味等级 | 气味等级 | ||
| 实施例1 | 2 | 对比例1 | 6 |
| 实施例2 | 3 | 对比例2 | 4.5 |
| 实施例3 | 3 | 对比例3 | 4 |
| 实施例4 | 2.5 | 对比例4 | 4.5 |
| 实施例5 | 3.5 | 对比例5 | 5 |
从表1中可以看出，本发明PVC的配料对于人造革气味的影响。比较对比例1-3可知，增塑剂对于降低PVC人造革的气味等级有着重要的影响。具体说来，与使用领苯类增塑剂作为增塑剂相比，使用环氧大豆油作为增塑剂，能在一定程度上降低PVC人造革的气味等级，主要原因是一方面环氧大豆油能吸收PVC树脂在分解时放出的HCl，另一方面又能改善PVC制品的光稳定性和热稳定性。而环氧大豆油和领苯类增塑剂的复配作为增塑剂对于降低气味更加有效果，主要原因是环氧大豆油能与聚酯类增塑剂发生协同作用，减少增塑剂的用量，从而减少了气味的主要来源。比较对比例1、对比例4-5，可以看出，使用物理发泡剂和在配方中添加气味吸收剂均对于降低气味等级有一定的效果。主要原因是物理发泡剂在发泡过程中直接逸出，不产生任何刺激性气味气体，气味吸收剂具有很高的比表面积，其分散在PVC基体中，能吸附PVC基体中散发出的异味气体。
比较实施例1-5及对比例1-5，可以看出，本发明的PVC人造革的气味等级明显低于对比例，且所有的实施例中气味等级均低于3.5，满足国内外汽车厂商的要求。
表2 实施例及对比例的VOC散发浓度结果
由表2公开的结果可知，本发明实施例的PVC人造革的VOC散发量明显低于对照组，也明显低于GB T 27630-2011中关于VOC含量的规定。
以上结果表明，本发明的低气味PVC人造革，具有低气味和低VOC散发量的特征，符合国标的规定，满足国内外汽车厂商的要求，是一种绿色环保的汽车内饰材料。
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 (6)
1.一种低气味PVC人造革，其特征在于，自下而上依次包括基布层、PVC皮层和油漆层；所述PVC皮层包括按照重量份计的如下组分：PVC粉55-65份、增塑剂35-40份、发泡剂5-8份、安定剂1-3份、颜料0-6份、助剂0-3份、气味吸收剂0.5-2份；
所述增塑剂包括环氧大豆油和邻苯类增塑剂，所述环氧大豆油和邻苯类增塑剂的重量比为2.5-5:1；所述发泡剂为物理发泡剂；所述安定剂为钙锌复合稳定剂；所述油漆层是由水性聚氨酯树脂制备而成的；
所述助剂包括阻燃剂、光稳定剂 和抗氧剂；所述阻燃剂为无机阻燃剂；所述光稳定剂为受阻胺类光稳定剂；所述抗氧剂为受阻酚类抗氧剂或芳香胺类抗氧剂。
2.如权利要求1所述的低气味PVC人造革，其特征在于，所述环氧大豆油和邻苯类增塑剂的重量比为3:1。
3.如权利要求1所述的低气味PVC人造革，其特征在于，所述气味吸收剂为比表面积大于500m2/g的分子筛，所述分子筛的粒径为60-100μm。
4.如权利要求3所述的低气味PVC人造革，其特征在于，所述分子筛为活性炭分子筛或沸石分子筛。
5.如权利要求1所述的低气味PVC人造革，其特征在于，所述PVC皮层是由如下的组分制备而成的：PVC粉60份、增塑剂35份、发泡剂6份、安定剂2份、颜料3份、助剂3份、气味吸收剂2份。
6.一种如权利要求1-5任一项所述的低气味PVC人造革的制备方法，其特征在于，包括如下的步骤：
1)制备PVC浆料：按配方的配比将PVC皮层的原料混合、搅拌30-60min，接着抽真空5-10min，然后在抽真空的条件下继续搅拌5-10min，得到PVC浆料；
2)制备PVC皮层：将步骤1)制备的PVC浆料涂在离型纸上、烘干；接着继续涂上一层PVC浆料、烘干；然后涂上胶水，并复合上一层基布再烘干；最后撕去离型纸，即得PVC皮层；
3)制备油漆层：向步骤2)制备的PVC皮层上涂上一层底漆、烘干；再涂上一层面漆、烘干；
4)压花：使用压花设备在油漆层上压制花纹，即得所述的低气味PVC人造革。
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| CN107747233A (zh) * | 2017-10-27 | 2018-03-02 | 佛山威明塑胶有限公司 | 一种低气味的pvc人造革及其制备方法 |
| CN107938371A (zh) * | 2017-11-15 | 2018-04-20 | 佛山市高明区生产力促进中心 | 一种pvc人造革及其制备方法 |
| CN108252113A (zh) * | 2017-11-27 | 2018-07-06 | 安徽博朗凯德车用皮革科技有限公司 | 一种耐磨车用pvc皮革基材及其制造工艺 |
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| CN110607702A (zh) * | 2018-06-15 | 2019-12-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | 聚氯乙烯发泡组合物及由其制备的人造革 |
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| CN114149644B (zh) * | 2021-11-15 | 2023-02-03 | 昆山阿基里斯新材料科技有限公司 | 环保合成皮革及其制备方法 |
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