CN107501703A - 一种环保eva鞋中底 - Google Patents

一种环保eva鞋中底 Download PDF

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CN107501703A
CN107501703A CN201710714875.1A CN201710714875A CN107501703A CN 107501703 A CN107501703 A CN 107501703A CN 201710714875 A CN201710714875 A CN 201710714875A CN 107501703 A CN107501703 A CN 107501703A
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eva
midsole
sebs
parts
poe
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张振秀
孙琰
张昕
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Fujian Xingxun New Material Technology Co ltd
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Qingdao University of Science and Technology
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Abstract

本发明提供一种环保EVA发泡珠粒及鞋中底的制作方法，以EVA颗粒、或EVA和POE共混物颗粒、或EVA和SEBS共混物颗粒、或者EVA、POE、SEBS三者的共混物颗粒为原料，采用辐照交联技术与间歇式超临界氮气发泡技术，制备得到高弹发泡珠粒，之后通过蒸汽热压成型，制得发泡中底，与现有传统的化学发泡鞋底相比，超临界氮气发泡的交联弹性体发泡材料泡孔结构更完整，饱满，弹性更佳且无有害残留物。

Description

一种环保EVA鞋中底
技术领域
本发明涉及一种环保EVA发泡珠粒及鞋中底的制作方法。
背景技术
近年来，随着人们对身体健康的关注，越来越多的人们开始热衷于各种体育运动，高性能的运动鞋也就成为紧俏产品。目前市场上的EVA发泡鞋底基本都采用化学发泡法，通过加入过氧化物交联剂和发泡剂偶氮二甲酰胺(AC)，在高温下硫化发泡得到成品。着此种鞋底中，交联剂和化学发泡剂在制备过程中都会有部分有毒物质的残留，人们对残留物、气味的关注度也逐渐提高，因此新型环保的鞋材需求非常迫切。
现在市场上阿迪达斯的BOOST鞋非常火爆，不仅是因为TPU所带来的高性能，而且它采用的是超临界发泡工艺制备的，但是相对于EVA，TPU的价格昂贵，而降低成本，在达到环保的同时保证鞋材的性能就显得尤为关键。对于含有EVA的超临界发泡材料也有相关的专利。在专利2016101509713中EVA的共混物是以过氧化物为交联剂，之后再采用间歇式降压法发泡工艺，得到超临界的EVA发泡材料，在专利201510014608.4中仅公开了一种环保发泡材料的成型方法，虽然提及超临界发泡EVA材料，但是并没有公开其超临界发泡材料的具体制备步骤和工艺参数。王波等人研究了γ射线辐照改性对于LDPE/EVA共混物结构和性能的影响，但其共混物中LDPE占主要份数，且使用的是超临界二氧化碳为物理发泡剂。
发明内容
本发明的目的在于提供一种完全环保的高性能的发泡中底，采用辐射交联技术与间歇式超临界氮气发泡技术，制备得到高弹发泡珠粒，之后通过蒸汽热压成型，制得发泡中底，与现有传统的化学发泡鞋底相比，超临界氮气发泡的交联弹性体发泡材料泡孔结构更完整，饱满，弹性更佳且无有害残留物。
为实现上述目的，一种EVA发泡珠粒及鞋中底的制作方法，其中，主要原料包括乙烯-醋酸乙烯酯(EVA)、或EVA与聚烯烃弹性体POE的共混物、或EVA与聚苯乙烯—丁二烯—苯乙烯三嵌段共聚物(SEBS)的共混物、或EVA、POE、SEBS三者的共混物，敏化剂0-2份，碳酸钙0.1-20份，抗氧剂1010 0.5-2份，抗菌剂ZnO 0.1-2份，钛白粉0.1-10份，染料0.1-2份，其特征在于，制备步骤如下：
(1)将原料依次放入密炼机中于110-140℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；
(2)将上述颗粒放入电子束辐射器中对其进行辐照交联，辐照量为30-90kGy；
(3)将辐照交联的颗粒放入反应釜中，通入氮气，密封饱和2-12h，之后泄压，将颗粒卸出，放入烘箱/烘道中进行发泡，得到EVA发泡珠粒；
(4)将发泡珠粒放入模具中进行蒸汽热压成型，得到发泡鞋中底。
其中，EVA和POE的共混物中EVA含量为60％-95％，POE含量为5％-40％；EVA和SEBS的共混物中EVA含量为60％-95％，SEBS含量为5％-40％；EVA、POE和SEBS的共混物中，EVA含量为60％-90％，SEBS含量为5％-20％，POE含量为5％-20％。
其中，所述敏化剂为TAIC或TMPTMA中的任一种。
其中，制备步骤(3)中反应釜的温度为30-90℃，通入氮气后釜内压力为15-60Mpa，烘箱/烘道发泡时温度为70-140℃。
其中，发泡珠粒在蒸汽压成型过程中，蒸汽压力为0.5-4Mpa，时间为20-100s。
本发明的有益效果为：通过辐射交联-超临界氮气发泡技术可以制备得到真正意义上的环保鞋底材料，采用间歇式超临界升温法可以大大提高其产率，且密度低于目前市面上的发泡鞋底，具有良好的回弹性及较低的压缩永久变形。
附图说明
图1本发明制备方法中，实施例1的扫描电镜图；
图2本发明制备方法中，实施例1的照片。
具体实施方式：
下面结合实施例对本发明做进一步说明：
对比例1
配方：乙烯-醋酸乙烯酯(EVA)60份，苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)40份，DCP 0.7份，AC3000H 2.8份，ZnO 0.8份，
制备步骤：调整开炼机的辊轮温度为90℃，辊距0.5mm，加入主要树脂原料打料，包辊后放大辊距再依次加入填料、AC(发泡剂)、ZnO，打散后在加入DCP(交联剂)，打均匀，在将料束薄3次，出片并按模具形状进行裁片，装模热压发泡170℃，800s，冷却定型，在室温下放置24h，裁样，进行性能测试。
基本性能：密度为0.23g/cm3，回弹为48，压缩永久变形为率为32％。
实施例1
配方：EVA 100份、碳酸钙3份，抗氧剂1010 0.5份，抗菌剂ZnO 1份，钛白粉6份。
制备步骤：将原料依次放入密炼机中于120℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；将上述颗粒放入电子束辐射器中对其进行辐照交联，辐照量为80kGy；将辐照交联的颗粒放入反应釜中釜中温度为55℃，通入氮气后使釜内压力达到30Mpa，密封饱和16h，之后泄压，将颗粒卸出，放入110℃烘箱中发泡10min，得到发泡珠粒；之后将发泡珠粒放入模具中进行蒸汽热压成型，蒸汽压力为1.2MPa，得到发泡鞋中底。
基本性能：密度为0.16g/cm3，回弹为55，硬度48，压缩永久变形率为45％，拉伸强度为1.6MPa，扯断伸长率为270％，耐黄变级别4级。
实施例2
配方：EVA70份、POE 30份，TMPTMA 1份，碳酸钙5份，抗氧剂1010 1份，抗菌剂ZnO 1份。
制备步骤：将原料依次放入密炼机中于115℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；将上述颗粒放入电子束辐射器中对其进行辐照交联，辐照量为50kGy；将辐照交联的颗粒放入反应釜中釜中温度为30℃，通入氮气后使釜内压力达到35Mpa，密封饱和8h，之后泄压，将颗粒卸出，放入120℃烘箱中发泡12min，得到发泡珠粒；之后将发泡珠粒放入模具中进行蒸汽热压成型，蒸汽压力为1.2MPa，得到发泡鞋中底。
基本性能：密度为0.18g/cm3，回弹为58，硬度45，压缩永久变形率为40％，拉伸强度为1.3MPa，扯断伸长率为201％，耐黄变级别4级。
实施例3
EVA85份，SEBS 15份，TMPTMA 0.2份，碳酸钙5份，抗氧剂1010 1份，抗菌剂ZnO1份。
制备步骤：将原料依次放入密炼机中于115℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；将上述颗粒放入电子束辐射中对其进行辐照交联，辐照量为60kGy；将辐照交联的颗粒放入反应釜中釜中温度为70℃，通入氮气后使釜内压力达到30Mpa，密封饱和8h，之后泄压，将颗粒卸出，放入120℃烘箱中发泡，得到发泡珠粒；之后将发泡珠粒放入模具中进行蒸汽热压成型，蒸汽压力为1.2MPa，得到发泡鞋中底。
基本性能：密度为0.165g/cm3，回弹为62，硬度42，压缩永久变形率为39％，拉伸强度为1.2MPa，扯断伸长率为175％，耐黄变级别4级。
实施例3
EVA60份，POE30份，SEBS 10份，TMPTMA 0.1份，碳酸钙3份，抗氧剂1010 1份。制备步骤：将原料依次放入密炼机中于115℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；将上述颗粒放入电子束辐射中对其进行辐照交联，辐照量为65kGy；将辐照交联的颗粒放入反应釜中釜中温度为70℃，通入氮气后使釜内压力达到30Mpa，密封饱和8h，之后泄压，将颗粒卸出，放入120℃烘箱中发泡，得到发泡珠粒；之后将发泡珠粒放入模具中进行蒸汽热压成型，蒸汽压力为1.2MPa，得到发泡鞋中底。
基本性能：密度为0.17g/cm3，回弹为65，硬度41，压缩永久变形率为40％，拉伸强度为1.0MPa，扯断伸长率为215％，耐黄变级别4级。

Claims (5)

1.一种环保EVA发泡珠粒及鞋中底的制作方法，其主要原料包括乙烯-醋酸乙烯酯(EVA)、或EVA与聚烯烃弹性体POE的共混物、或EVA与聚苯乙烯—丁二烯—苯乙烯三嵌段共聚物(SEBS)的共混物、或EVA、POE、SEBS三者的共混物，敏化剂0-2份，碳酸钙0.1-20份，抗氧剂1010 0.5-2份，抗菌剂ZnO 0.1-2份，钛白粉0.1-10份，染料0.1-2份。其特征在于，制备步骤如下：
(1)将原料依次放入密炼机中于110-140℃下混炼，待混炼均匀后，排出，将胶片加入挤出机中，挤出造粒，烘干；
(2)将上述颗粒放入电子束辐射器中对其进行辐照交联，辐照量为30-90kGy；
(3)将辐照交联的颗粒放入反应釜中，通入氮气，密封饱和2-12h，之后泄压，将颗粒卸出，放入烘箱或烘道中进行发泡，得到EVA发泡珠粒；
(4)将EVA发泡珠粒放入模具中进行蒸汽热压成型，得到发泡鞋中底。
2.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法，其特征在于EVA和POE的共混物中EVA含量为60％-95％，POE含量为5％-40％；EVA和SEBS的共混物中EVA含量为60％-95％，SEBS含量为5％-40％；EVA、POE和SEBS的共混物中，EVA含量为60％-90％，SEBS含量为5％-20％，POE含量为5％-20％。
3.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法，其特征在于敏化剂为三烯丙基异氰脲酸酯(TAIC)或三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)中的任一种。
4.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法，其特征在于制备步骤(3)中反应釜的温度为30-90℃，通入氮气后釜内压力为15～60Mpa，烘箱/烘道发泡时温度为70～140℃，发泡时间为2-20min。
5.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法，其特征在于发泡珠粒在蒸汽压成型过程中，蒸汽压力为0.5-4Mpa，时间为20-100s。
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CN108102338A (zh) * 2018-01-26 2018-06-01 青岛科技大学 一种发泡鞋中底
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