CN105714574A - 一种发泡热塑性聚氨酯人造革及其制备方法 - Google Patents

一种发泡热塑性聚氨酯人造革及其制备方法 Download PDF

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CN105714574A
CN105714574A CN201610127756.1A CN201610127756A CN105714574A CN 105714574 A CN105714574 A CN 105714574A CN 201610127756 A CN201610127756 A CN 201610127756A CN 105714574 A CN105714574 A CN 105714574A
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thermoplastic polyurethane
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CN105714574B (zh
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王光阜
张生
王娜
王仁鸿
宋红玮
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Miracll New Material Co Ltd
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Abstract

本发明涉及一种发泡热塑性聚氨酯人造革及其制备方法，所述发泡热塑性聚氨酯人造革由面层，发泡层和底层依次按照从上而下的顺序复合而得，其中,面层由热塑性聚氨酯颗粒A采用压延工艺制备，发泡层由热塑性聚氨酯颗粒B、润滑剂和色母粒通过超临界二氧化碳发泡与挤出流延相结合的方式得到，底层通过将纤维布浸渍在水性PU树脂中烘干得到。采用本技术方案所制备的发泡热塑性聚氨酯人造革产品具有闭孔率高，闭孔率≥90％，良好的耐磨性，弹性，手感，生产过程环保，产品质量稳定，适合工业化连续生产。

Description

一种发泡热塑性聚氨酯人造革及其制备方法
技术领域
本发明涉及一种发泡热塑性聚氨酯人造革及其制备方法,属于人造革材料领域。
背景技术
目前市场上常用的人造革材料是PU合成革和PVC合成革。但是上述合成革材料在生产以及使用过程中会有氯化物，硫化物，异氰酸酯等有害物质排放，危害使用者的健康，同时会造成严重的环境污染问题。
热塑性聚氨酯弹性体材料(TPU)具有较宽泛的硬度范围，优异的耐磨性、机械强度、耐水、耐油、耐化学腐蚀、耐霉菌，对环境友好，可回收利用等优点。基于上述优点，采用TPU生产人造革具有广泛的应用前景。
专利101021046A公开了一种热塑性聚氨酯人造革的配方及其制法，该方法采用了热塑性聚氨酯弹性体树脂作为主料，取代传统的人造革主料PU或PVC合成皮，使得制作的人造革具有环保无毒，可降解的特性。但是该方法在生产过程中使用化学发泡剂，生产过程中不环保，生产的产品质量难以控制稳定。
发明内容
本发明所要解决的技术问题是提供一种发泡热塑性聚氨酯人造革及其制备方法,本方法借助超临界二氧化碳发泡与挤出流延相结合的生产工艺，所制备的发泡热塑性聚氨酯人造革产品具有闭孔率高(闭孔率≥90％)，良好的耐磨性，弹性，手感，生产过程环保，产品质量稳定，适合工业化连续生产。
本发明解决上述技术问题的技术方案如下：一种发泡热塑性聚氨酯人造革的制备方法，包括：
1)将100重量份的热塑性聚氨酯颗粒A投入挤出机中，采用压延工艺制备面层；
2)将纤维布浸渍在固含量为10-40％的水性PU树脂中10-30分钟，取出后在80-100℃下烘干1-5小时后，制得底层，
其中，上述步骤1)和步骤2)工序不分先后顺序；
3)将100重量份热塑性聚氨酯颗粒B，0-5重量份润滑剂，0-10重量份色母粒混合均匀后投入第一挤出机中，控制第一挤出机的螺杆温度，得到TPU聚合物熔体，并在第一挤出机的末端注入超临界流体，TPU聚合物熔体和超临界流体混合1-60秒后，经熔体泵加入到第二挤出机中，控制第二挤出机的螺杆温度，使超临界流体与TPU聚合物熔体混合均匀，形成均相体系，均相体系通过第二挤出机模头流延制备发泡层；
4)将面层、发泡层和底层输送至贴合机，在130-200℃下依次按面层、发泡层和底层的顺序从上而下进行复合，经压花后得到发泡热塑性聚氨酯人造革。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，在1)中，所述挤出机的螺杆温度为120-180℃，优选125-175℃，特别优选130-170℃
进一步，所述热塑性聚氨酯颗粒A和热塑性聚氨酯颗粒B的邵氏硬度分别为50A-85D，优选邵氏硬度为55A-85D，特别优选邵氏硬度为60A-95A，基于ASTM-D2240测得；熔体流动速率分别不高于100g/10min,优选熔体流动速率不高于90g/10min,特别优选熔体流动速率不高于80g/10min,其根据ASTM-1238在200℃施加5kg的重量测得，其中，热塑性聚氨酯颗粒A和热塑性聚氨酯颗粒B的邵氏硬度，熔体流动速率相同或不同。
进一步，在3)中，所述润滑剂为PE蜡、芥酸酰胺、油酸酰胺、硬脂酸酰胺、蒙旦蜡中的一种或几种的混合物，优选为PE蜡。
进一步，在3)中，所述第一挤出机的螺杆温度为150-200℃。
进一步，在3)中，所述超临界流体为超临界二氧化碳，其加入量为热塑性聚氨酯颗粒B重量的1-30％，优选5-25％，特别优选10-20％。
进一步，在3)中，所述第二挤出机的螺杆温度为150-180℃，第二挤出机的模头温度为130-150℃，模头压力为1-10Mpa，模头处的压力降速率为1-3MPa/s。
本发明还提供一种上述的制备方法制备的发泡热塑性聚氨酯人造革。
本发明使用超临界二氧化碳作为发泡剂，由于超临界二氧化碳具有非常大的扩散系数和良好的流动性，使得超临界二氧化碳可以很容易的与TPU聚合物熔体形成均相体系，且超临界二氧化碳在TPU聚合物熔体中分布均匀，使得最终发泡热塑性聚氨酯人造革发泡层的泡孔尺寸均匀，闭孔率高，具有良好的弹性。避免了常用的化学发泡剂(如AC发泡剂)由于活性过高，发气量大导致泡孔尺寸不均匀，气泡合并、破裂等问题。
本发明采用超临界二氧化碳发泡与挤出流延相结合的工艺，通过控制第二挤出机螺杆温度使TPU聚合物熔体强度增加，避免了由于TPU聚合物熔体强度过低导致超临界二氧化碳“逃逸”形成的破孔等问题，所制备的发泡热塑性聚氨酯人造革的密度为0.1-0.5g/cm3，同时密度可控。另外，超临界二氧化碳与TPU聚合物熔体在流经模头时，通过控制模头处的压力降速率与温度，使体系迅速达到热力学不稳定状态，促进气泡成核，从而有利于形成均匀的泡孔结构，同时泡孔具有高的闭孔率。另外需要指出的是，超临界二氧化碳与TPU聚合物熔体在流经模头时，由于模头处温度降低，使得发泡层表面具有“自结皮”的结构，采用本技术方案所制备的产品具有更加优异的耐磨性能。
与现有技术相比，本发明具有如下的优点和有益效果：
1.使用超临界二氧化碳作为发泡剂来代替常用的化学发泡剂，利用超临界二氧化碳的特性，使得最终发泡热塑性聚氨酯人造革发泡层的泡孔尺寸均匀，并且生产过程中环保。
2.采用超临界二氧化碳发泡与挤出流延相结合的工艺，通过控制模头处的压力降速率与温度，所制备的产品具有高的闭孔率，更加优异的耐磨性能，回弹性与手感,产品的密度为0.1-0.5g/cm3,同时密度可控。
3.与传统人造革制备工艺相比，本技术方案生产过程环保，产品质量稳定，适合工业化连续生产。
附图说明
图1为实施例1制备的发泡热塑性聚氨酯人造革的外观图；
图2为实施例1制备的发泡热塑性聚氨酯人造革横截面的扫描电镜图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
(1)将100重量份热塑性聚氨酯颗粒A在100℃干燥4小时后投入挤出机中，挤出机螺杆温度在120-150℃，采用压延工艺制备面层；
其中，热塑性聚氨酯颗粒A邵氏硬度为50A，熔体流动速率为20g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(2)将纤维布经固含量为10％的水性PU树脂浸渍10分钟后，在100℃温度下烘干1小时后，制得底层，
其中，上述步骤(1)和步骤(2)工序不分先后顺序；
(3)采用高混机将100重量份热塑性聚氨酯颗粒B，1重量份PE蜡，1重量份色母粒混合均匀后加入到第一挤出机中，控制第一挤出机螺杆温度为150-165-180-175℃，得到TPU聚合物熔体，并在第一挤出机的末端注入1重量份的超临界二氧化碳；在第一挤出机中混合60秒后将TPU聚合物熔体和超临界二氧化碳经熔体泵加入到第二挤出机中，控制第二挤出机的螺杆温度为170-165-160-155℃，使超临界流体与TPU聚合物熔体混合均匀，形成均相体系；将第二挤出机模头温度设定为150℃，模头处的压力为1Mpa，模头处压力降速率为1MPa/s，将超临界二氧化碳与TPU聚合物熔体均相体系通过第二挤出机模头流延制备发泡层，其中，热塑性聚氨酯颗粒B邵氏硬度为50A，熔体流动速率为20g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(4)将上述制备的面层、发泡层和底层输送至贴合机，在130℃下复合10分钟，将复合好的制品经压花后，得到发泡热塑性聚氨酯人造革。
本实施例所制备的发泡热塑性聚氨酯人造革以及截面泡孔情况如图1与图2所示。从图1可以看出所制备的发泡热性聚氨酯人造革表面光滑，无明显的缺陷。从图2可以看出，截面泡孔尺寸为40-45um，尺寸均匀，闭孔率为93％。后续实施例中所制备的发泡热塑性聚氨酯人造革外观与截面泡孔情况与实施例1类似，不再一一提供。本实施例所制备的发泡热塑性聚氨酯人造革的性能情况参见表1所示。
实施例2
(1)将100重量份热塑性聚氨酯颗粒A投入挤出机中，挤出机螺杆温度为130-160℃，采用流延工艺制备面层；
其中，热塑性聚氨酯颗粒A邵氏硬度为60A，熔体流动速率为30g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(2)将纤维布经固含量为20％的水性PU树脂浸渍20分钟后，在100℃温度下烘干2小时后制得底层，
其中，上述步骤(1)和步骤(2)工序不分先后顺序；
(3)采用高混机将100重量份热塑性聚氨酯颗粒B，2重量份芥酸酰胺，5重量份色母粒混合均匀后加入到第一挤出机中，控制第一挤出机螺杆温度为160-175-190-185℃，得到TPU聚合物熔体，并在第一挤出机的末端注入10重量份的超临界二氧化碳；在第一挤出机中混合30秒后将TPU聚合物熔体和超临界二氧化碳经熔体泵加入第二挤出机中，控制第二挤出机螺杆温度为180-175-170-165℃，使超临界流体与TPU聚合物熔体混合均匀，形成均相体系；将第二挤出机模头温度设定为160℃，模头处的压力为5Mpa，模头处压力降速率为2MPa/s，将超临界二氧化碳与TPU聚合物熔体均相体系通过第二挤出机模头流延制备发泡层B，其中热塑性聚氨酯颗粒B邵氏硬度为70A，熔体流动速率为30g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(4)将上述制备的面层,发泡层，底层输送至贴合机，在140℃下复合20分钟，将复合好的制品经压花后得到发泡热塑性聚氨酯人造革。
实施例3
(1)将100重量份热塑性聚氨酯颗粒A投入挤出机中，挤出机螺杆温度在140-180℃，采用压延工艺制备面层；
其中，热塑性聚氨酯颗粒A邵氏硬度为80A，熔体流动速率为40g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(2)将纤维布经固含量为40％的水性PU树脂浸渍30分钟后，在100℃温度下烘干3小时后制得底层，
其中，上述步骤(1)和步骤(2)工序不分先后顺序；
(3)采用高混机将100重量份热塑性聚氨酯颗粒B，5重量份硬脂酸酰胺，10重量份色母粒混合均匀后加入到第一挤出机中，控制第一挤出机螺杆温度为170-185-200-195℃，得到TPU聚合物熔体，并在第一挤出机的末端注入30重量份的超临界二氧化碳；在第一挤出机中混合1秒后将TPU聚合物熔体和超临界二氧化碳经熔体泵加入第二挤出机中，控制第二挤出机螺杆温度为190-185-175-170℃，使超临界流体与TPU聚合物熔体混合均匀，形成均相体系；将第二挤出机模头温度设定为165℃，模头处的压力为10Mpa，模头处压力降速率为3MPa/s，将超临界二氧化碳与TPU聚合物熔体均相体系通过第二挤出机模头流延制备发泡层，
其中，热塑性聚氨酯颗粒B邵氏硬度为90A，熔体流动速率为30g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(4)将上述制备的面层、发泡层和底层输送至贴合机，在150℃下复合30分钟，将复合好的制品经压花后得到发泡热塑性聚氨酯人造革。
对比例1
(1)将100重量份热塑性聚氨酯颗粒A在100℃干燥4小时后投入挤出机中，挤出机螺杆温度在120-150℃，采用压延工艺制备面层；
其中，热塑性聚氨酯颗粒A的邵氏硬度为50A，熔体流动速率为20g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(2)将纤维布经固含量为10％的水性PU树脂浸渍10分钟后，在100℃温度下烘干1小时后制得底层，
其中，上述步骤(1)和步骤(2)工序不分先后顺序；
(3)采用高混机将100重量份热塑性聚氨酯颗粒B，1重量份PE蜡，1重量份色母粒混合均匀后加入到第一挤出机中，控制第一挤出机螺杆温度为150-165-180-175℃，得到TPU聚合物熔体，并在第一挤出机的末端加入1重量份的AC发泡剂；将初步混合的TPU聚合物熔体和AC发泡剂经熔体泵加入第二挤出机中，控制第二挤出机螺杆温度为170-165-160-155℃，使AC发泡剂与TPU聚合物熔体混合均匀，形成均相体系；将第二挤出机模头温度设定为150℃，将AC发泡剂与TPU聚合物熔体均相体系通过第二挤出机模头流延制备发泡层B，其中，热塑性聚氨酯颗粒B邵氏硬度为50A，熔体流动速率为20g/10min,其根据ASTM-1238在200℃施加5kg的重量测得；
(4)将上述制备的面层、发泡层和底层输送至贴合机，在130℃下复合10分钟，将复合好的制品经压花后得到发泡热塑性聚氨酯人造革。
表1
性能 标准 单位 实施例1 实施例2 实施例3 对比例1
密度 ASTM-D792 g/cm3 0.2 0.15 0.3 0.6
泡孔尺寸 — um 40-45 35-40 45-50 100-200
闭孔率 — ％ 93％ 92％ 95％ 75％
回弹性 ISO 8307 ％ 55 56 58 45％
耐磨性 DIN 53516 Mm3 100 120 115 180
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种发泡热塑性聚氨酯人造革的制备方法，其特征在于，包括：
1)将100重量份的热塑性聚氨酯颗粒A投入挤出机中，采用压延工艺制备面层；
2)将纤维布浸渍在固含量为10-40％的水性PU树脂中10-30分钟，取出后在80-100℃下烘干1-5小时后，制得底层，
其中，上述步骤1)和步骤2)工序不分先后顺序；
3)将100重量份热塑性聚氨酯颗粒B，0-5重量份润滑剂，0-10重量份色母粒混合均匀后投入第一挤出机中，控制第一挤出机的螺杆温度，得到TPU聚合物熔体，并在第一挤出机的末端注入超临界流体，TPU聚合物熔体和超临界流体混合1-60秒后，经熔体泵加入到第二挤出机中，控制第二挤出机的螺杆温度，使超临界流体与TPU聚合物熔体混合均匀，形成均相体系，均相体系通过第二挤出机模头流延制备发泡层；
4)将面层、发泡层和底层输送至贴合机，在130-200℃下依次按面层、发泡层和底层的顺序从上而下进行复合，经压花后得到发泡热塑性聚氨酯人造革。
2.根据权利要求1所述的制备方法，其特征在于，在1)中，所述挤出机的螺杆温度为120-180℃。
3.根据权利要求1所述的制备方法，其特征在于，所述热塑性聚氨酯颗粒A和热塑性聚氨酯颗粒B的邵氏硬度分别为50A-85D，基于ASTM-D2240测得；熔体流动速率分别不高于100g/10min,其根据ASTM-1238在200℃施加5kg的重量测得，其中，热塑性聚氨酯颗粒A和热塑性聚氨酯颗粒B的邵氏硬度，熔体流动速率相同或不同。
4.根据权利要求1所述的制备方法，其特征在于，在3)中，所述润滑剂为PE蜡、芥酸酰胺、油酸酰胺、硬脂酸酰胺、蒙旦蜡中的一种或几种的混合物。
5.根据权利要求4所述的制备方法，其特征在于，所述润滑剂为PE蜡。
6.根据权利要求1所述的制备方法，其特征在于，在3)中，所述第一挤出机的螺杆温度为150-200℃。
7.根据权利要求1所述的制备方法，其特征在于，在3)中，所述超临界流体为超临界二氧化碳，其加入量为热塑性聚氨酯颗粒B重量的1-30％。
8.根据权利要求1所述的制备方法，其特征在于，在3)中，所述第二挤出机的螺杆温度为150-180℃，第二挤出机的模头温度为130-150℃，模头压力为1-10Mpa，模头处的压力降速率为1-3MPa/s。
9.一种如权利要求1-8任一所述的制备方法制备的发泡热塑性聚氨酯人造革。
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Publication number Priority date Publication date Assignee Title
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CN106739319A (zh) * 2016-11-15 2017-05-31 浙江环龙新材料科技有限公司 一种热塑性聚氨酯发泡革的制备方法
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101021046A (zh) * 2006-05-31 2007-08-22 叶志成 一种热塑性聚氨酯人造革的配方及其制法
CN104611942A (zh) * 2015-02-10 2015-05-13 浙江佳阳塑胶新材料有限公司 一种tpu物理发泡合成革及其生产工艺和应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101021046A (zh) * 2006-05-31 2007-08-22 叶志成 一种热塑性聚氨酯人造革的配方及其制法
CN104611942A (zh) * 2015-02-10 2015-05-13 浙江佳阳塑胶新材料有限公司 一种tpu物理发泡合成革及其生产工艺和应用

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CN113510990A (zh) * 2020-09-29 2021-10-19 东莞市元普塑胶科技有限公司 超临界氮气发泡技术生产制备仿真皮人造革
CN112342797A (zh) * 2020-11-27 2021-02-09 苏州瑞高新材料有限公司 一种水性聚氨酯/tpu合成革
CN112342797B (zh) * 2020-11-27 2022-11-08 苏州瑞高新材料有限公司 一种水性聚氨酯/tpu合成革
CN113561400A (zh) * 2021-07-28 2021-10-29 南通海嘉智能科技有限公司 一种tpu颗粒发泡工艺
WO2024031688A1 (zh) * 2022-08-08 2024-02-15 广东汇齐新材料有限公司 可回收环保型热塑性tpu发泡人造皮革及其制备工艺
KR102678832B1 (ko) * 2024-03-11 2024-06-27 삼부정밀화학 주식회사 Tpu 분말을 함유하는 폴리우레탄 폼 조성물 및 이를 이용한 신발 갑피용 폴리우레탄 폼 시트의 제조방법
CN118359916A (zh) * 2024-05-20 2024-07-19 广东中鼎科技发展有限公司 一种基于鞋材边角料回收的tpu发泡材料及其制备工艺

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