CN113912326B - 一种无卤改性高填充可回收塑胶板材及其成型方法 - Google Patents

一种无卤改性高填充可回收塑胶板材及其成型方法 Download PDF

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CN113912326B
CN113912326B CN202111274751.9A CN202111274751A CN113912326B CN 113912326 B CN113912326 B CN 113912326B CN 202111274751 A CN202111274751 A CN 202111274751A CN 113912326 B CN113912326 B CN 113912326B
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halogen
recyclable plastic
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CN113912326A (zh
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戴会斌
董利杰
李鑫
章忠飞
王涛
李猛飞
曹江川
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Zhejiang Jingtong New Material Group Co ltd
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Priority to PCT/CN2021/130406 priority patent/WO2023070754A1/zh
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Abstract

本申请公开了一种无卤改性高填充可回收塑胶板材，包括基材层以及自下而上依次设置于所述基材层上表面的印刷层和保护层；其中，以质量百分比计，所述基材层的原料包括20‑25％PEAT树脂、70‑75％石粉、0.5‑0.8％扩链剂、1‑2％白油、3‑6％PE以及0.4‑0.8％硬脂酸。本发明提供的塑胶板材，采用热压的方法成型，不需要胶水粘合，整体性好，制成的板材表面张力大，表面容易加工，且基材层与印刷层、保护层相容性好，可整体进行回收使用。

Description

一种无卤改性高填充可回收塑胶板材及其成型方法
技术领域
本发明涉及塑胶地板技术领域，尤其涉及一种无卤改性高填充可回收塑胶板材及其成型方法。
背景技术
目前，市面上塑胶地板较为通用的是以pvc为主要塑胶原料的地板，尽管其产品在使用的时候比较环保，但是在加工以及加热时候，会分解释放氯化氢、二噁英等有毒气体。随着人们环保概念的深入，市场对无卤产品的呼声越来越高。常规的无卤塑胶原物料都存在的自身缺陷，如pe，虽然可以填充很多石粉，但是自己膨胀率大；pp材料成型的板材表面张力较小，后续表面加工比较困难；pet材料的熔点高，材料本身较脆，无法大量填充石粉。
发明内容
本发明针对上述问题，提出了一种无卤改性高填充的可回收塑胶板材，采用热压的方法成型，不需要胶水粘合，整体性好，制成的板材表面张力大，表面容易加工，且基材层与印刷层、保护层相容性好，可整体进行回收使用。
本发明采取的技术方案如下：本发明提供一种无卤改性高填充可回收塑胶板材，包括基材层以及自下而上依次设置于所述基材层上的印刷层和保护层。
其中，以质量百分比计，所述基材层的原料包括20-25％PEAT树脂、70-75％石粉、0.5-0.8％扩链剂、1-2％白油、3-6％PE以及0.4-0.8％硬脂酸。
具体地，PEAT树脂为聚对苯二甲酸乙二醇酯-co-聚己二酸乙二醇酯，通过PTA(精对苯二甲酸)、己二酸、乙二醇、磷酸及其酯衍生物、二甘醇以及催化剂酯化反应缩聚而成。
PEAT树脂的性能参数如下：
特性黏度：0.85～0.9dL/g；
端羧基：6～13mmol/kg；
二甘醇：1～1.5％；
熔点：195～205℃。
PEAT树脂可以起到粘合作用。石粉作为填充剂，增加产品的稳定性。扩链剂可以增加链的长度，加工不易分解。白油可以润滑增加塑化，便于挤出。此外，硬脂酸也具有润滑作用。其中，扩链剂与白油、硬脂酸一同使用，可使产品在挤出翟工的时候更容易成型，不易断料。
印刷层为petg(聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯)白膜印刷膜或数码印刷膜。保护层可以为petg透明片或无卤树脂(uv、pur)。保护层的表面设有纹路，纹路可以通过钢板钢辊压制或者数码打印。但不限于此，保护层表面也可以是平面结构。
基材可以单层或多层结构，且基材底部可以设置平衡层和/或静音垫。平衡层为petg透明片。
可选地，以质量百分比计，所述PEAT树脂由65-70％PTA、13-20％己二酸、13-20％乙二醇、0.0012-0.0025％磷酸及其酯衍生物、1-1.5％二甘醇以及0.02-0.03％催化剂酯化反应而成。
可选地，以质量百分比计，所述PEAT树脂由55-60％PTA、13-20％己二酸、13-20％乙二醇、0.0012-0.0025％磷酸及其酯衍生物、1-1.5％二甘醇、0.02-0.03％催化剂以及10-15％回收PET酯化反应而成。
PET为聚对苯二甲酸乙二醇酯。回收PET来自于回收的饮料瓶片。采用PET回料更加环保，且不会影响制成的塑胶板材整体性能。
可选地，所述催化剂为锑系催化剂，具体可以为乙二醇锑。由于乙二醇锑结构具有与乙二醇结构相似的基团，根据相似相容的原理，乙二醇锑在乙二醇中的溶解度大，分散性好，而且锑含量高，活性好，有利于促进酯化反应。
可选地，所述扩链剂为含环氧官能团的共聚物。扩链剂中含有的活性环氧基团可与PEAT树脂链端的羧基反应，而且环氧基团的开环温度低，扩链效率高。具体可以为2-甲基-2-丙烯酸环氧乙烷基甲基酯，与经酯化反应缩聚而成的PEAT树脂均具有酯基团，不会带入新杂质。
可选地，所述PE为HDPE(高密度聚乙烯)。HDPE的熔点高，适合高温加工，硬度、拉伸强度和蠕变性均优于低密度的聚乙烯。
HDPE的性能参数如下：
分子量：大于25万；
密度：0.940～0.976g/cm3；
结晶度：80％～90％；
软化点：125～135℃。
本发明还提供一种无卤改性高填充可回收塑胶板材的成型方法，具体包括如下步骤：
(1)将PEAT树脂、石粉、扩链剂、白油、PE和硬脂酸进行高速搅拌，直至搅拌温度达到100℃，停止搅拌；
(2)通过挤出机采用多段式挤出温度挤出成型，并经钢辊压合成片形成基材层；
(3)在基材层表面通过数码打印、辊压或者粘附带图案的膜层形成印刷层；
(4)在保护层粘附或涂布于印刷层上，并对保护层进行压纹形成塑胶板材。
所述多段式挤出温度包括从高到低顺次设置的五段挤出温度，所述多段式挤出温度的温度范围为185-210℃，每段挤出温度的持续时间为13-17s。由于前期的石粉含量更多，在三段前必须更好塑化，所以需加温。而且，在第三段温度和第四段温度之间进行抽真空处理，真空度为0.8mpa，将加工产生或携带的气体进行抽走，使板材内部没有泡，为了保证在三段温度前充分塑化，需要较高的温度进行加工，以免未塑化还是粉状被抽真空抽走。塑化后温度需要降低，因为高温的时候物料较软，这样的料无法很好的挤出成型，所以将温度降低。
其中，基材层表面通过数码打印形成印刷层时，可以在印刷层表面涂布uv(如uv光油等)进行图案保护。
上述方法制得的塑胶板材的测试数据如下表1所示。
表1塑胶板材的测试内容及结果
测试内容 检测标准 结果
尺寸稳定性 ISO23999 0.08％
翘曲 ISO23999 0.2mm
残余凹陷 ISO24343-1 0.01mm
耐磨 EN13329 AC4
针刮 ISO1518-1 2700g
马丁代尔 EN16094 A1B1
轮椅测试25000r ISO4918 Pass
邻苯检测 EN14372 ND
重金属 ASTMF963 Pass
甲醛 EN717-1 ND
本发明的有益效果是：本发明制成的塑胶板材整体无卤素元素；基材层中的石粉填充量≥70％，制成的塑胶板材的热稳定性80℃收缩≤0.08％，膨胀≤0.15％；基材层的表面可直接贴合petg膜，或者直接采用数码打印无须胶水；PEAT树脂可使用部分pet回料进行取代，减少碳排放。除此之外，板材各部分的材料均可相容，报废的板材可进行直接破碎再加工。
具体实施方式
下面通过具体实施例，对本发明进行详细、完整的描述。
实施例1
将16份PEAT树脂、50份石粉、0.5份扩链剂、0.8份白油、0.4份硬脂酸、3份PE(按质量分数计)进行高速搅拌，待搅拌温度达到100℃停止搅拌，通过喂料机进行喂料，通过双螺杆挤出机进行挤出，设置五段挤出温度分别为210℃、200℃、195℃、190℃、185℃，平均每段挤出温度时间为15s，且在第三段挤出温度和第四段挤出温度之间进行抽真空，真空度为0.8mpa，模具两端温度设置210℃，中间设置200℃，挤出，通过两钢辊压合成片，两钢辊温度均为140℃，同时表面通过胶辊贴合petg印刷层和petg透明片(贴合面0.01mm的压纹)，再用两钢辊进行压合，上钢辊温度150℃，有压纹，下钢辊温度140℃。复合好的片材冷却到50℃进行裁切分片。
实施例2
将16份PEAT树脂、55份石粉、0.5份扩链剂、0.8份白油、0.4份硬脂酸、3份PE(按质量分数计)进行高速搅拌，待搅拌温度达到100℃停止搅拌，通过喂料机进行喂料，通过双螺杆挤出机进行挤出，设置五段挤出温度分别为210℃、205℃、200℃、190℃、185℃，平均每段挤出温度的持续时间为15s，且在第三段挤出温度和第四段挤出温度之间进行抽真空，真空度为0.8mpa，模具两端温度设置210℃，中间设置200℃，挤出，通过两钢辊压合成片，获得基材层。基材层表面通过数码打印形成印刷层，印刷层表面通过涂布uv进行图案保护，通过数码3D打印设置纹路。
实施例3
将16份PEAT树脂、55份石粉、0.5份扩链剂、0.8份白油、0.4份硬脂酸、3份PE(按质量分数计)进行高速搅拌，待搅拌温度达到100℃停止搅拌，通过喂料机进行喂料，通过双螺杆挤出机进行挤出，设置五段挤出温度分别为210℃、205℃、200℃、190℃、185℃，平均每段挤出温度时间为15s，且在第三段挤出温度和第四段挤出温度之间进行抽真空，真空度为0.8mpa，模具两端温度设置210℃，中间设置200℃，挤出，通过两钢辊压合成片，将petg印刷层置于基材表面，petg透明片分别置于印刷层表面形成保护层和基材底部形成平衡层，上下设置钢板，通过压机压合。压机热压温度130℃，压机压力设置三段4、5、6mpa，每段时间分别为6分钟、8分钟、8分钟，冷机温度设置35℃，压力设置三段8、9、10mpa，每段时间为6分钟、10分钟、10分钟，获得塑胶板材。
以上所述仅为本发明的优选实施例，并非因此即限制本发明的专利保护范围，凡是运用本发明说明书内容所作的等效结构变换，直接或间接运用在其他相关的技术领域，均同理包括在本发明的保护范围内。

Claims (10)

1.一种无卤改性高填充可回收塑胶板材，其特征在于，包括基材层以及自下而上依次设置于所述基材层上表面的印刷层和保护层；
其中，以质量百分比计，所述基材层的原料包括20-25％PEAT树脂、70-75％石粉、0.5-0.8％扩链剂、1-2％白油、3-6％PE以及0.4-0.8％硬脂酸。
2.根据权利要求1所述的无卤改性高填充可回收塑胶板材，其特征在于，以质量百分比计，所述PEAT树脂由65-70％PTA、13-20％己二酸、13-20％乙二醇、0.0012-0.0025％磷酸及其酯衍生物、1-1.5％二甘醇以及0.02-0.03％催化剂酯化反应而成。
3.根据权利要求1所述的无卤改性高填充可回收塑胶板材，其特征在于，以质量百分比计，所述PEAT树脂由55-60％PTA、13-20％己二酸、13-20％乙二醇、0.0012-0.0025％磷酸及其酯衍生物、1-1.5％二甘醇、0.02-0.03％催化剂以及10-15％回收PET酯化反应而成。
4.根据权利要求2或3所述的无卤改性高填充可回收塑胶板材，其特征在于，所述催化剂为乙二醇锑。
5.根据权利要求1所述的无卤改性高填充可回收塑胶板材，其特征在于，所述扩链剂为2-甲基-2-丙烯酸环氧乙烷基甲基酯。
6.根据权利要求1所述的无卤改性高填充可回收塑胶板材，其特征在于，所述PE为HDPE。
7.根据权利要求1所述的无卤改性高填充可回收塑胶板材，其特征在于，所述基材层的下表面设有平衡层；所述保护层和所述平衡层均为petg透明片。
8.一种权利要求1-7任意一项所述的无卤改性高填充可回收塑胶板材的成型方法，其特征在于，具体包括如下步骤：
(1)将PEAT树脂、石粉、扩链剂、白油、PE和硬脂酸进行高速搅拌，直至搅拌温度达到100℃，停止搅拌；
(2)通过挤出机采用多段式挤出温度挤出成型，并经钢辊压合成片形成基材层；
(3)在基材层表面通过数码打印、辊压或者粘附带图案的膜层形成印刷层；
(4)在保护层粘附或涂布于印刷层上，并对保护层进行压纹形成塑胶板材。
9.根据权利要求8所述的成型方法，其特征在于，所述多段式挤出温度包括从高到低顺次设置的五段挤出温度，所述多段式挤出温度的温度范围为185-210℃，每段挤出温度的持续时间为13-17s。
10.根据权利要求9所述的成型方法，其特征在于，第三段挤出温度和第四段挤出温度之间进行抽真空处理，真空度为0.8mpa。
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