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CN104711772A - 一种复合热熔胶网膜及其制备工艺 - Google Patents

一种复合热熔胶网膜及其制备工艺 Download PDF

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CN104711772A
CN104711772A CN201510106668.9A CN201510106668A CN104711772A CN 104711772 A CN104711772 A CN 104711772A CN 201510106668 A CN201510106668 A CN 201510106668A CN 104711772 A CN104711772 A CN 104711772A
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melt adhesive
hot
nethike embrane
composite
hot melt
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CN104711772B (zh
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李哲龙
朱万育
马星全
曾作祥
张勇健
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Kunshan Tianyang New Material Co ltd
Tianyang New Material Shanghai Technology Co ltd
East China University of Science and Technology
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Shanghai Tianyang Holt Melt Adhesive Materials Co Ltd
Kunshan Tianyang Hot Melt Adhesives Co Ltd
East China University of Science and Technology
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Priority to CN201510106668.9A priority Critical patent/CN104711772B/zh
Publication of CN104711772A publication Critical patent/CN104711772A/zh
Priority to DE112015005639.4T priority patent/DE112015005639T5/de
Priority to CH00792/17A priority patent/CH712138B1/de
Priority to PCT/CN2015/097640 priority patent/WO2016095823A1/zh
Priority to US15/537,305 priority patent/US10472547B2/en
Priority to KR1020177020144A priority patent/KR101937389B1/ko
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Abstract

本发明公开了一种复合热熔胶网膜及其制备工艺，特别是一种用于粘接金属与非极性材料用复合热熔胶网膜及其制备工艺，由于采用了特定的配方，使得极性的聚酰胺热熔胶和含有增容剂的非极性的聚烯烃有效熔融，根据本发明所制得的复合热熔胶网膜，其粘接强度大，粘接持久稳定，特别适用于不锈钢、铝、铜等金属材料与聚乙烯、聚丙烯等非极性聚合物的粘接复合。同时，本发明所提出的制备工艺，从原料预处理到最后制成热熔胶网膜产品，均在一套生产流程中完成，可以大大减少生产故障，生产效率高，成本低。

Description

一种复合热熔胶网膜及其制备工艺
技术领域
本发明涉及一种复合热熔胶网膜及其制备工艺，特别是涉及一种用于粘接金属与非极性材料用的复合热熔胶网膜及其制备工艺，通过本发明所制得复合热熔胶网膜，特别适用于不锈钢、铝、铜等金属材料与聚乙烯、聚丙烯等非极性聚合物的粘接复合。
背景技术
热熔胶网膜是一种耐腐蚀、耐老化、热稳定性好并具有良好的抗拉、抗顶破以及良好的透水性能的材料，因此广泛应用于服装、汽车、电子等行业。
CN 101240148 B提供了一种热熔胶网膜的制备方法，包括热熔胶原料的熔融，加入结晶成核剂，挤压，纺丝，气流牵伸，摆丝成网等工序，该专利特别涉及利用共聚酰胺热熔胶为原料制备热熔胶网膜。CN 101967733 B 提供了一种热熔胶网膜的制备方法，通过控制热熔胶的熔融温度，喷丝速度，红外温度等，制备出孔径均匀，克重稳定的热熔胶网膜，该专利尤其涉及利用聚酯热熔胶为原料制备热熔胶网膜的方法。CN 103059792 B提供了一种用以粘接极性聚合物和金属材料的聚酯弹性体热熔胶及其制备方法。CN1699491A亦公开了一种热熔胶膜的制备方法，尤其适用于书画装裱用的双面热熔胶膜。
随着工业化的发展，随着工业化的进展，越来越多的领域要求把极性材料与非极性材料粘接在一起，既可以降低成本，又可以扩大材料的应用领域。而目前常规的热熔胶相关产品，如网膜或胶膜基本上都是针对于粘接极性材料，对非极性材料的粘接性很差。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种复合热熔胶网膜及其制备工艺，通过本发明所制得复合热熔胶网膜，其粘接强度大，粘接持久稳定，特别适用于不锈钢、铝、铜等金属材料与聚乙烯、聚丙烯等非极性聚合物的粘接复合。
本发明所采用的技术方案如下:
一种复合热熔胶网膜，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，该聚酰胺热熔胶网膜所用聚酰胺热熔胶的DSC终熔点为116-130℃，熔体流动速率为30-50g/10min/160℃；该聚烯烃热熔胶网膜所用聚烯烃热熔胶的成分按质量百分比计，包括：增容剂8 -15%，聚乙烯50-70%，其他聚烯烃3-10%，引发剂0.2-0.8%，硅烷偶联剂0.7-1.3%，增黏剂8-20%，无机填料1.0-10%，抗氧化剂0.4-0.8%；
上述增容剂选自马来酸酐接枝高密度聚乙烯、马来酸酐接枝低密度聚乙烯、马来酸酐接枝聚丙烯、马来酸酐接枝线性低密度聚乙烯中的一种，所述马来酸酐接枝率为0.8-1.2%；
上述聚乙烯选自高密度聚乙烯、低密度聚乙烯和线性低密度聚乙烯中的一种，其熔体流动速率为0.9-7g/10min/190℃；
上述其他聚烯烃选自乙烯-辛烯共聚物、聚丙烯、聚苯乙烯中的一种，其熔体流动速率为1.6-14g/10min/190℃；
上述引发剂选自过氧化苯甲酰、过氧化二叔丁基和偶氮二异丁腈中的一种；
上述硅烷偶联剂选自乙烯基三甲氧基硅烷和γ-氨基丙基三甲氧基硅烷中的一种；
上述增黏剂选自松香145、萜烯树脂和氢化碳五树脂中的一种；
上述无机填料选自滑石粉、高岭土和纳米碳酸钙中的一种；
上述抗氧化剂选自抗氧化剂1010、抗氧化剂BHT和抗氧化剂264中的一种。
一种复合热熔胶网膜的制备工艺，选取上述复合热熔胶所用的聚酰胺热熔胶及聚烯烃热熔胶作为原料，进行下述步骤处理：
（1）分别将聚酰胺热熔胶、聚烯烃热熔胶熔融后泵入到两个独立的第一喷丝板和第二喷丝板内；
（2）上述聚酰胺热熔胶经第一喷丝板在第一气流的牵引下以第一预设速度喷丝到传送带上，然后经过第一红外加热区加热，形成第一层网膜；
（3）上述聚烯烃热熔胶经第二喷丝板在第二气流的牵引下以第二预设速度喷丝丝到传送带上，并趁热与第一层网膜复合，然后经过第二红外加热区加热，形成双层复合网膜；
（4）上述双层复合网膜经冷却、结晶固化、收卷，形成热熔胶网膜产品；
上述第一喷丝板的温度小于上述第二喷丝板的温度，上述第一喷丝板的温度为170-210℃，第二喷丝板的温度范围为180-230℃；
上述第一预设速度大于第二预设速度，第一预设速度为15-30m/min，第二预设速度为10-25m/min；
上述第一气流速度大于第二气流速度，第一气流及第二气流的速度范围为30-120m/min；
上述第一红外加热区的温度高于所述第二红外加热区的温度，第一红外加热区温度为90-120℃，第二红外加热区温度为60-90℃；
上述传送带的速度为12-20m/min，第一喷丝板与第二喷丝板之间的距离为0.7-1.3m。
本发明的有效果：本发明所提出的复合热熔胶网膜及其制备工艺，由于采用了特定的配方，使得极性的聚酰胺热熔胶和含有增容剂的非极性的聚烯烃有效熔融，根据本发明所制得的复合热熔胶网膜，其粘接强度大，粘接持久稳定，特别适用于不锈钢、铝、铜等金属材料与聚乙烯、聚丙烯等非极性聚合物的粘接复合。同时，本发明所提出的制备工艺，从原料预处理到最后制成热熔胶网膜产品，均在一套生产流程中完成，可以大大减少生产故障，生产效率高，成本低。
附图说明
图1为本发明所提制备工艺流程图。
具体实施方式
实施例1
一种复合热熔胶网膜，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，所用聚酰胺热熔胶的DSC终熔点122℃，熔体流动速率为30g/10min/160℃；所用聚烯烃热熔胶的组分及其质量百分比为：
马来酸酐接枝高密度聚乙烯（接枝率1%）                  8%；
高密度聚乙烯（熔体流动速率0.9g/10min/190℃）         50%；
乙烯-辛烯共聚物（融体流动速率1.6g/10min/190℃）     10%；
过氧化苯甲酰                                                        0.2%；
乙烯基三甲氧基硅烷                                                1%；
松香145                                                                20%；
滑石粉                                                                  10%；
抗氧剂1010                                                            0.8%。
一种复合热熔胶网膜的制备工艺，分别将上述聚酰胺和聚烯烃热熔胶熔融后泵入到相互独立的第一喷丝板和第二喷丝板；两喷丝板之间间距0.7m，传送带（钢丝带）工作，调整其传送速度为12m/min；开启第一喷丝板，调整其内温为170℃，喷丝速度为20m/min，气流（压缩空气）速度为120m/min，聚酰胺热熔胶从第一喷丝板并在气流牵引下喷丝到传送带形成网状膜；该网状膜经过温度为100℃的第一红外加热区加热，形成第一层网膜；开启第二喷丝板，调整其内温度为180℃，喷丝速度为12m/min，气流速度（压缩空气）为85m/min，聚烯烃热熔胶从第二喷丝板并在气流牵引下喷丝到传送带，并与第一层网膜趁热复合，随后经过温度为60℃的第二红外加热区加热形成双层网膜；然后经冷却、结晶固化，收卷形成最终用于粘接金属与非极性材料用的复合热熔胶网膜产品。
根据实施例配方及制备工艺所得产品标记为A。
实施例2
一种复合热熔胶网膜，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，所用聚酰胺热熔胶的DSC终熔点116℃，熔体流动速率为50g/10min/160℃；所用聚烯烃热熔胶的组分及其质量百分比为：
马来酸酐接枝低密度聚乙烯（接枝率1.2%）                15%；
线性低密度聚乙烯（熔体流动速率2g/10min/190℃）      60%；
乙烯-辛烯共聚物（融体流动速率3g/10min/190℃）        5%；
过氧化二叔丁基                                                      0.4%；
γ-氨基丙基三甲氧基硅烷                                         1.3%；
氢化碳五树脂                                                         10%；
纳米碳酸钙                                                            7.7%；
抗氧剂1010                                                            0.6%。
一种复合热熔胶网膜的制备工艺，分别将上述聚酰胺和聚烯烃热熔胶熔融后泵入到相互独立的第一喷丝板和第二喷丝板；两喷丝板之间间距0.7m，传送带（钢丝带）工作，调整其传送速度为12m/min；开启第一喷丝板，调整其内温为170℃，喷丝速度为20m/min，气流（压缩空气）速度为120m/min，聚酰胺热熔胶从第一喷丝板并在气流牵引下喷丝到传送带形成网状膜；该网状膜经过温度为100℃的第一红外加热区加热，形成第一层网膜；开启第二喷丝板，调整其内温度为180℃，喷丝速度为12m/min，气流速度（压缩空气）为85m/min，聚烯烃热熔胶从第二喷丝板并在气流牵引下喷丝到传送带，并与第一层网膜趁热复合，随后经过温度为60℃的第二红外加热区加热形成双层网膜；然后经冷却、结晶固化，收卷形成最终用于粘接金属与非极性材料用的复合热熔胶网膜产品。
根据实施例配方及制备工艺所得产品标记为B。
实施例3
一种复合热熔胶网膜，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，所用聚酰胺热熔胶的DSC终熔点130℃，熔体流动速率为45g/10min/160℃；所用聚烯烃热熔胶的组分及其质量百分比为：
马来酸酐接枝线性低密度聚乙烯（接枝率1%）           10%；
低密度聚乙烯（熔体流动速率7g/10min/190℃）           65%；
聚苯乙烯（融体流动速率10g/10min/190℃）               3%；
偶氮二异丁腈                                                        0.8%；
γ-氨基丙基三甲氧基硅烷                                        0.7%；
萜烯树脂                                                              15%；
高岭土                                                                5%；
抗氧剂BHT                                                         0.5%。
一种复合热熔胶网膜的制备工艺，分别将上述聚酰胺和聚烯烃热熔胶熔融后泵入到相互独立的第一喷丝板和第二喷丝板；两喷丝板之间间距1.1m，传送带（钢丝带）工作，调整其传送速度为17m/min；开启第一喷丝板，调整其内温为190℃，喷丝速度为23m/min，气流（压缩空气）速度为115m/min，聚酰胺热熔胶从第一喷丝板并在气流牵引下喷丝到传送带形成网状膜；该网状膜经过温度为120℃的第一红外加热区加热，形成第一层网膜；开启第二喷丝板，调整其内温度为210℃，喷丝速度为16m/min，气流速度（压缩空气）为90m/min，聚烯烃热熔胶从第二喷丝板并在气流牵引下喷丝到传送带，并与第一层网膜趁热复合，随后经过温度为80℃的第二红外加热区加热形成双层网膜；然后经冷却、结晶固化，收卷形成最终用于粘接金属与非极性材料用的复合热熔胶网膜产品。
根据实施例配方及制备工艺所得产品标记为C。
实施例4
一种复合热熔胶网膜，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，所用聚酰胺热熔胶的DSC终熔点124℃，熔体流动速率为35g/10min/160℃；所用聚烯烃热熔胶的组分及其质量百分比为：
马来酸酐接枝的聚丙烯（接枝率1.2%）                     13%；
低密度聚乙烯（熔体流动速率4g/10min/190℃）          70%；
聚丙烯（融体流动速率14g/10min/190℃）                  6%；
过氧化苯甲酰                                                       0.7%；
乙烯基三甲氧基硅烷                                              0.9%；
萜烯树脂                                                             8%；
纳米碳酸钙                                                          1%；
抗氧剂264                                                          0.4%。
一种复合热熔胶网膜的制备工艺，分别将上述聚酰胺和聚烯烃热熔胶熔融后泵入到相互独立的第一喷丝板和第二喷丝板；两喷丝板之间间距1.3m，传送带（钢丝带）工作，调整其传送速度为20m/min；开启第一喷丝板，调整其内温为200℃，喷丝速度为26m/min，气流（压缩空气）速度为100m/min，聚酰胺热熔胶从第一喷丝板并在气流牵引下喷丝到传送带形成网状膜；该网状膜经过温度为110℃的第一红外加热区加热，形成第一层网膜；开启第二喷丝板，调整其内温度为230℃，喷丝速度为18m/min，气流速度（压缩空气）为80m/min，聚烯烃热熔胶从第二喷丝板并在气流牵引下喷丝到传送带，并与第一层网膜趁热复合，随后经过温度为90℃的第二红外加热区加热形成双层网膜；然后经冷却、结晶固化，收卷形成最终用于粘接金属与非极性材料用的复合热熔胶网膜产品。
根据实施例配方及制备工艺所得产品标记为D。
性能测试
考察上述实施例得到的热熔胶网膜在160℃、0.30MPa、热压120s粘接PE/铝、PP/铝、PE/不锈钢、PP/不锈钢的180°剥离强度，具体测试结果见下表1：
表1热熔胶网膜对不同基材的粘接强度。
从上表中，可明显看出：根据本发明所制得的复合热熔胶网膜，其粘接强度大，粘接持久稳定，特别适用于不锈钢、铝、铜等金属材料与聚乙烯、聚丙烯等非极性聚合物的粘接复合。且本发明所提出的制备工艺，从原料预处理到最后制成热熔胶网膜产品，均在一套生产流程中完成，可以大大减少生产故障，生产效率高，成本低。

Claims (13)

1.一种复合热熔胶网膜，其特征在于，由聚酰胺热熔胶网膜及聚烯烃热熔胶网膜复合而成，其中，所述聚酰胺热熔胶网膜所用的聚酰胺热熔胶的DSC终熔点为116-130℃，熔体流动速率为30-50g/10min/160℃；所述聚烯烃热熔胶网膜所用的聚烯烃热熔胶的成分按质量百分比计，包括：增容剂8 -15%，聚乙烯50-70%，其他聚烯烃3-10%，引发剂0.2-0.8%，硅烷偶联剂0.7-1.3%，增黏剂8-20%，无机填料1.0-10%，抗氧化剂0.4-0.8%。
2.如权利要求1所述的复合热熔胶网膜，其特征在于，所述增容剂选自马来酸酐接枝高密度聚乙烯、马来酸酐接枝低密度聚乙烯、马来酸酐接枝聚丙烯、马来酸酐接枝线性低密度聚乙烯中的一种，且马来酸酐接枝率为0.8-1.2%。
3.如权利要求1所述的复合热熔胶网膜，其特征在于，所述聚乙烯选自高密度聚乙烯、低密度聚乙烯和线性低密度聚乙烯中的一种，其熔体流动速率为0.9-7g/10min/190℃。
4.如权利要求1所述的复合热熔胶网膜，其特征在于，所述其他聚烯烃选自乙烯-辛烯共聚物、聚丙烯、聚苯乙烯中的一种，其熔体流动速率为1.6-14g/10min/190℃。
5.如权利要求1所述的复合热熔胶网膜，其特征在于，所述引发剂选自过氧化苯甲酰、过氧化二叔丁基和偶氮二异丁腈中的一种。
6.如权利要求1所述的复合热熔胶网膜，其特征在于，所述无机填料选自滑石粉、高岭土和纳米碳酸钙中的一种。
7.一种复合热熔胶网膜的制备工艺，其特征在于，将权利要求1~6任一项所述的复合热熔胶网膜所用的聚酰胺热熔胶及聚烯烃热熔胶作为原料，进行下述步骤处理：
（1）分别将聚酰胺热熔胶、聚烯烃热熔胶熔融后泵入到两个独立的第一喷丝板和第二喷丝板内；
（2）所述聚酰胺热熔胶经第一喷丝板在第一气流的牵引下以第一预设速度喷丝到传送带上，然后经过第一红外加热区加热，形成第一层网膜；
（3）所述聚烯烃热熔胶经第二喷丝板在第二气流的牵引下以第二预设速度喷丝丝到传送带上，并趁热与第一层网膜复合，然后经过第二红外加热区加热，形成双层复合网膜；
（4）所述双层复合网膜经冷却、结晶固化、收卷，形成热熔胶网膜产品。
8.如权利要求7所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一喷丝板的温度小于所述第二喷丝板的温度，所述第一预设速度大于所述第二预设速度，所述第一气流速度大于所述第二气流速度，所述第一红外加热区的温度高于所述第二红外加热去的温度。
9.如权利要求8所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一喷丝板的温度为170-210℃，所述第二喷丝板的温度范围为180-230℃。
10.如权利要求8所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一预设速度为15-30m/min，所述第二预设速度为10-25m/min。
11.如权利要求8所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一气流及第二气流的速度范围为30-120m/min。
12.如权利要求8所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一红外加热区温度为90-120℃，第所述二红外加热区温度为60-90℃。
13.如权利要求7所述的复合热熔胶网膜的制备工艺，其特征在于，所述第一喷丝板及所述第二喷丝板之间的距离为0.7-1.3m，所述传送带的传送速度为12-20m/min。
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CN110699013A (zh) * 2019-11-04 2020-01-17 巢进化学(上海)有限公司 一种用于粘结金属与塑料的热熔胶及其制备方法
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