CN114889291A - 一种铝塑膜及其制备方法 - Google Patents

一种铝塑膜及其制备方法 Download PDF

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CN114889291A
CN114889291A CN202210315245.8A CN202210315245A CN114889291A CN 114889291 A CN114889291 A CN 114889291A CN 202210315245 A CN202210315245 A CN 202210315245A CN 114889291 A CN114889291 A CN 114889291A
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film
polyurethane prepolymer
aluminum
preparing
bopa
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CN114889291B (zh
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关秋
井光辉
戴平翔
樊天倩
戴晓兵
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Jiangxi Shengwei Material Co ltd
Zhuhai Smoothway Electronic Materials Co Ltd
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Jiangxi Shengwei Material Co ltd
Zhuhai Smoothway Electronic Materials Co Ltd
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Abstract

本发明公开了一种铝塑膜及其制备方法，包括步骤：(1)聚氨酯预聚体的制备：将脂肪酸改性的芳香族共聚酯二元醇与异氰酸酯反应制得聚氨酯预聚体；(2)封闭聚氨酯预聚体的制备：将所述聚氨酯预聚体与封闭剂反应制得封闭聚氨酯预聚体；(3)热熔胶膜的制备：将所述封闭聚氨酯预聚体、热塑性聚氨酯弹性体复配成为胶黏剂，再将所述胶黏剂涂布离型膜上，干燥形成PU膜，将所述PU膜与BOPA膜复合得到PU/BOPA复合膜；(4)制备铝塑膜：将所述PU/BOPA复合膜与铝箔复合得到铝塑膜。本发明公开的铝塑膜的制备方法，固化后比较柔韧，能够提供良好的可冷冲深性能，使用过程不需要施胶和烘箱设备，没有污染，储存稳定。

Description

一种铝塑膜及其制备方法
技术领域
本发明涉及铝塑膜技术领域，更具体地涉及一种铝塑膜及其制备方法。
背景技术
铝塑膜是软包装电池的重要材料，比其他包装材料具有独特优势。例如同等容量的三元电池，采用铝塑膜的电池的重量比钢壳、铝壳包装电池分别轻40％，20％。这意味着同等重量的电池，铝塑膜电池拥有更高的能量密度。特别是在便携的消费电子产品和运动的车辆动力电池领域，铝塑膜拥有的如电池轻量化、高能量密度、尺寸灵活、低内阻等独特优点，得到了广泛应用。在铝塑膜制造业，普遍采用干法复合工艺，即采用溶剂型胶粘剂涂布在铝箔上，再于烘道内干燥，再与膜材复合的工艺。复合的膜材因功能的不同分为抗电解液及耐腐蚀的CPP层与高冲深阻隔水汽的BOPA层，保护性的PET层等。
干法复合工艺的优势是低成本，技术路线成熟，高强度等，但是其缺点如溶剂VOC排放、VOC治理、VOC排放的无效能耗和工人的健康保证逐渐引起社会的关注。随着国家强制性法规《胶粘剂挥发性有机化合物限量GB33372-2020》对胶粘剂VOC提出了限量的要求。溶剂挥发中带走的热量和溶剂治理中损耗电能，这些都是无效的碳排放。热熔胶膜在热复合具有广泛的应用，例如制鞋鞋垫的复合，防护服或者冲锋衣接缝的热封，汽车座椅多层材料复合等，然而这些热熔胶膜在铝塑膜的复合上还存在各种不足。
发明内容
为了克服现有技术的缺陷，本发明的目的是提供一种铝塑膜的制备方法，通过该方法制备的铝塑膜，具有良好的可冷冲深性能和较高的高温剥离强度，且相较现有工艺更为环保。
为了实现上述目的，本发明公开了一种铝塑膜的制备方法，包括步骤：
(1)聚氨酯预聚体的制备：
将脂肪酸改性的芳香族共聚酯二元醇与异氰酸酯反应制得聚氨酯预聚体；
(2)封闭聚氨酯预聚体的制备：
将聚氨酯预聚体与封闭剂反应制得封闭聚氨酯预聚体；
(3)热熔胶膜的制备：
将封闭聚氨酯预聚体、热塑性聚氨酯弹性体复配成为胶黏剂，再将胶黏剂涂布基材上，干燥形成PU膜，将PU膜与BOPA膜复合得到PU/BOPA复合膜；
(4)制备铝塑膜：
将PU/BOPA复合膜与铝箔复合得到铝塑膜。
与现有技术相比，本发明的铝塑膜的制备方法，在聚氨酯预聚体的制备材料中采用脂肪酸改性的芳香族共聚酯二元醇，固化后比较柔韧，能够提供良好的可冷冲深性能。
相应地，本发明还提供一种铝塑膜，采用上述制备方法制得。
具体实施方式
为详细说明本发明的技术内容、构造特征、所实现目的及效果，以下结合实施方式进行详予说明。
本发明提供一种铝塑膜的制备方法，包括步骤：
(1)聚氨酯预聚体的制备：
将脂肪酸改性的芳香族共聚酯二元醇与异氰酸酯反应制得聚氨酯预聚体；
(2)封闭聚氨酯预聚体的制备：
将聚氨酯预聚体与封闭剂反应制得封闭聚氨酯预聚体；
(3)热熔胶膜的制备：
将封闭聚氨酯预聚体、热塑性聚氨酯弹性体复配成为胶黏剂，再将胶黏剂涂布基材上，干燥形成PU膜，将PU膜与BOPA膜复合得到PU/BOPA复合膜；
(4)制备铝塑膜：
将PU/BOPA复合膜与铝箔复合得到铝塑膜。
需要说明的是，可以通过制备原料来实现芳香族聚酯二元醇的脂肪酸改性，本实施例中，脂肪酸改性的芳香族共聚酯二元醇的制备原料含癸二酸，癸二酸的加入赋予芳香族聚酯二元醇进行脂肪酸改性，从而使其固化后比较柔韧，能够提供良好的可冷冲深性能。进一步，芳香族共聚酯二元醇为不结晶的脂肪酸改性的芳香族共聚酯二元醇，由于不结晶的脂肪酸改性的芳香族共聚酯二元醇固化后较坚硬，可提供良好的高温剥离强度。进一步，可以通过制备原料来实现不结晶，本实施例中采用间苯二甲酸以实现脂肪酸改性的芳香族共聚酯二元醇不结晶，而采用对苯二甲酸会使得脂肪酸改性的芳香族共聚酯二元醇结晶，因此，优选采用间苯二甲酸制备脂肪酸改性的芳香族共聚酯二元醇。更具体地，脂肪酸改性的芳香族共聚酯二元醇的制备原料包括间苯二甲酸、癸二酸、新戊二醇和乙二醇。优选地，间苯二甲酸、癸二酸、新戊二醇和乙二醇的用量比为25:25:40:10。
在一个优选地的技术方案中，提供一种脂肪酸改性的芳香族共聚酯二元醇的制备方法，步骤包括：向反应釜中加入间苯二甲酸、癸二酸、新戊二醇、乙二醇、抗氧剂，升温真空脱水，加入钛酸四异丙基酯催化剂，进行反应，控制羟值为20-24，然后降温制得脂肪酸改性的芳香族共聚酯二元醇。进一步，脂肪酸改性的芳香族共聚酯二元醇为小分子量，该分子量为500-2000，需要理解的是该分子量为重均分子量，如分子量为500、1000、1500、2000，本发明采用小分子量脂肪酸改性的芳香族共聚酯二元醇，具有较小的粘度，有利于封闭聚氨酯预聚体的形成及解封，尤其是可实现低温解封，比如后期PU/BOPA复合膜与铝箔的复合温度为80-120℃，该温度可为但不限于80℃、90℃、100℃、110℃、120℃。
在一个优选地的技术方案中，提供一种封闭聚氨酯预聚体的制备方法，包括步骤：将脂肪酸改性的芳香族共聚酯二元醇、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、丁二醇、催化剂和碳酸二甲酯进行溶液聚合，得到聚氨酯预聚体，再将封闭剂滴加在所述聚氨酯预聚体中，搅拌反应，得到封闭聚氨酯预聚体。进一步，聚合温度为90-92℃。在一个优选的实施例中，封闭剂选自腰果酚，其分子量较大，不会挥发，热解封后腰果酚一部分与尼龙(BOPA)产生氢键，增加胶粘剂的附着力，另一部分残留在胶粘剂中使胶膜变软，起到增塑剂作用，且由于腰果酚的使用，可实现低温解封，提高解封效率。
在一个优选地的技术方案中，本发明还提供一种热熔胶膜的制备方法，包括步骤：将封闭聚氨酯预聚体、热塑性聚氨酯弹性体(TPU)、抗氧剂、钛白粉、气相二氧化硅、溶剂、流平剂复配成为胶黏剂，再将胶黏剂涂布在离型纸，干燥形成PU膜，然后将PU膜与BOPA膜复合，去除离型纸，得到PU/BOPA复合膜。进一步，热塑性聚氨酯弹性体(TPU)采用聚己内酯聚氨酯弹性体TPU，能够在较低温度活化，提供较高的剥离强度，尤其是可提供良好的高温剥离强度。当热解封后，在粘结界面的异氰酸酯与基材快速反应，在胶黏剂内部的异氰酸酯能与端羟基聚己内酯聚氨酯交联形成热固性胶膜，实现较高的剥离强度，达到粘结的可靠性。
值得说明的是，将所述PU/BOPA复合膜与铝箔复合得到铝塑膜，PU/BOPA复合膜的PU膜侧与铝箔复合。更为优选地，铝箔表面先采用钝化剂进行预处理。热熔胶膜复合过程，通过加热使热熔胶中异氰酸酯封闭剂解封，异氰酸酯与铝箔表面的钝化剂和BOPA膜中的尼龙快速反应，使粘结的过程不可逆，确保粘结的可靠性，其中腰果酚的酚基团与尼龙通过氢键结合进一步提高粘合强度。进一步，铝箔的另一侧可设有CPP膜。
下面通过几个具体的优选实施例来进一步阐述本发明的铝塑膜的制备方法，但并不因此而限定本发明的保护范围。
本发明实施例中所使用的原料如下：
腰果酚NX-2026，卡德莱化工(珠海)有限公司
催化剂BICAT 8118，领先化学,
碳酸二甲酯，济南创世化工有限公司
聚己内酯聚氨酯弹性体TPU，路博润
钛白粉，杜邦R902+
气相二氧化硅，德山QS102
其中，实施例中所用原料未列出的，均属于市售。
实施例1
一种铝塑膜的制备方法，包括步骤：
(1)脂肪酸改性的芳香族共聚酯二元醇的制备：
向反应釜中加入间苯二甲酸、癸二酸、新戊二醇、乙二醇和抗氧剂168，升温到120℃真空脱水，通入氮气，升温至180℃真空脱水，保温2小时后继续升温，并逐步加大氮气量强化脱水，再升温至225±5℃恒温，恒温1小时后加入催化剂钛酸四异丙基酯，再过30分钟后降低氮气流量并逐步开始抽真空，进行酯交换，从抽真空开始计时4小时后每2小时取一次样品分析，至最终酸值＜2mgKOH/g，羟值为56mgKOH/g，恢复常压，开始降温，降温至120℃，即可制得脂肪酸改性的芳香族共聚酯二元醇，分子量为2000。
其中，脂肪酸改性的芳香族共聚酯二元醇的制备过程中各材料的用量配比见表1。
表1脂肪酸改性的芳香族共聚酯二元醇的制备过程中各材料的用量配比
Figure BDA0003568879060000051
Figure BDA0003568879060000061
(2)封闭聚氨酯预聚体的制备：
将脂肪酸改性的芳香族共聚酯二元醇、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯三聚体(HDI三聚体)、乙二醇、催化剂和碳酸二甲酯进行溶液聚合，反应温度为90度，检测NCO含量为0.5％，然后滴加腰果酚封闭剂，90度搅拌1h，检测NCO含量低于为0.02％，冷却到室温终止反应，获得封闭聚氨酯预聚体，
其中，封闭聚氨酯预聚体的制备过程中各材料的用量配比见表2。
表2封闭聚氨酯预聚体的制备过程中各材料的用量配比
物料 重量比
芳香族共聚酯二元醇 38.53
MDI 7.60
HDI三聚体 0.03
乙二醇 0.27
催化剂 0.002
碳酸二甲酯 50
封闭剂腰果酚 3.47
总计 100.00
(3)热熔胶膜的制备：
将封闭聚氨酯预聚体、热塑性聚氨酯弹性体TPU、抗氧剂168、钛白粉、气相二氧化硅、乙酸乙酯、丁酮、流平剂BYK333、消泡剂BYK-A 530复配成为胶黏剂，再将胶黏剂涂布在单硅离型纸，三段烘箱干燥，干燥形成PU膜，然后将PU膜与BOPA膜复合，BOPA的厚度为15um，去除离型纸，复合后得到热固PU/BOPA膜，厚度为25um。
其中，热熔胶膜的制备过程中各材料的用量配比见表3。
表3热熔胶膜的制备过程中各材料的用量配比
物料 重量比
50％封闭聚氨酯预聚体 72.1
聚己内酯聚氨酯弹性体TPU 5.0
抗氧剂168 0.46
钛白粉 2.74
气相二氧化硅 0.1
流平剂BYK333 0.1
消泡剂BYK-A 530 0.1
丁酮 9.7
乙酸乙酯 9.7
总计 100
(4)制备铝塑膜：
将所述PU/BOPA复合膜与铝箔复合得到铝塑膜，工艺为：温度120℃，车速10m/s，压力0.4mPa。
实施例2
该实施例与实施例1中铝塑膜的制备方法基本相同，不同在于：封闭聚氨酯预聚体的制备方法中，实施例1采用腰果酚作为封闭剂，而实施例2采用对氯苯酚作为封闭剂，其余相同，在此不进行具体阐述。
实施例3
该实施例中铝塑膜的制备方法与实施例1基本相同，不同在于：对于脂肪酸改性的芳香族共聚酯二元醇的制备方法中，实施例3采用对苯二甲酸，而实施例1采用间苯二甲酸，其余相同，在此不进行具体阐述。
实施例4
该实施例中铝塑膜的制备方法与实施例1基本相同，不同在于：对于热熔胶膜的制备方法中，实施例4采用热塑性聚己二酸丁二醇型聚氨酯弹性体，而实施例1采用的热塑性聚氨酯弹性体为聚己内酯型聚氨酯弹性体TPU，其余相同，在此不进行具体阐述。
设置对比例1，采用市售干法复合聚氨酯胶粘剂，涂布量5.0g/平方米，复合烘道温度：50℃～60℃、60℃～70℃、70℃～80℃；熟化条件70℃*7天；
将实施例1-4得到的铝塑膜进行剥离强度、单坑冲深深度和小坑冲深深度测试，测试结果见表4。
其中，剥离强度的测试方法为：GB/T 8808-1988软质复合塑料材料剥离试验方法，测试速度100mm/min，单位N/15m；
单坑冷冲深的测试方法为：冲头形状为60mm*100mm，R角＝1.0mm，间隙0.3mm，深度6.0mm；40个；
湿热老化的测试方法为：温度85度&湿度85％R.H.&7天，查看是否存在白线分层，气泡分层，面分层，褶皱等。
表4试验结果
Figure BDA0003568879060000081
由表1中实施例1与实施例2的比较可知，剥离强度和冲深方面具有同等的效果，但是在湿热条件下，采用苯酚封闭的实施例2出现50％的线分层，可能的原因是苯酚极性方面比腰果酚强，对尼龙的解离破坏严重。
实施例1与实施例3的比较可知，实施例3在剥离强度上具有优势，然而其冲深破损达到50％，湿热老化后有100％白线分层，可能的原因是使用对苯二甲酸的封闭聚氨酯不够柔软。
实施例1与实施例4的比较可知，实施例4在剥离强度上具有优势，然而其冲深破损达到12.5％，湿热老化后有5％线分层，可能的原因是聚己二酸丁二醇型不够柔软而且耐高温性不够。
实施例1与对比例1达到了同样的效果，然而对比例1在使用过程需要烘箱挥发溶剂，并且立刻复合，否则会失效；而实施例1不需要烘箱，可以作为一种热固PU/BOPA复合膜稳定储存。
以上所揭露的仅为本发明的优选实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明申请专利范围所作的等同变化，仍属本发明所涵盖的范围。

Claims (10)

1.一种铝塑膜的制备方法，其特征在于，包括步骤：
(1)聚氨酯预聚体的制备：
将脂肪酸改性的芳香族共聚酯二元醇与异氰酸酯反应制得聚氨酯预聚体；
(2)封闭聚氨酯预聚体的制备：
将聚氨酯预聚体与封闭剂反应制得封闭聚氨酯预聚体；
(3)热熔胶膜的制备：
将封闭聚氨酯预聚体、热塑性聚氨酯弹性体复配成为胶黏剂，再将胶黏剂涂布离型膜上，干燥形成PU膜，将PU膜与BOPA膜复合得到PU/BOPA复合膜；
(4)制备铝塑膜：
将PU/BOPA复合膜与铝箔复合得到铝塑膜。
2.如权利要求1所述的铝塑膜的制备方法，其特征在于，芳香族共聚酯二元醇为不结晶的脂肪酸改性的芳香族共聚酯二元醇。
3.如权利要求2所述的铝塑膜的制备方法，其特征在于，脂肪酸改性的芳香族共聚酯二元醇的制备原料包括间苯二甲酸、癸二酸、新戊二醇和乙二醇。
4.如权利要求3所述的铝塑膜的制备方法，其特征在于，脂肪酸改性的芳香族共聚酯二元醇的制备方法如下：
向反应釜中加入间苯二甲酸、癸二酸、新戊二醇、乙二醇、抗氧剂，升温真空脱水，加入钛酸四异丙基酯催化剂，进行反应，控制羟值为56-280mgKOH/g，酸值＜2mgKOH/g然后降温制得脂肪酸改性的芳香族共聚酯二元醇。
5.如权利要求1所述的铝塑膜的制备方法，其特征在于，脂肪酸改性的芳香族共聚酯二元醇为小分子量，该分子量为400-2000。
6.如权利要求1所述的铝塑膜的制备方法，其特征在于，封闭剂选自腰果酚。
7.如权利要求1所述的铝塑膜的制备方法，其特征在于，封闭聚氨酯预聚体的制备方法如下：
将脂肪酸改性的芳香族共聚酯二元醇、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、丁二醇、催化剂和碳酸二甲酯进行溶液聚合，得到聚氨酯预聚体，
再将封闭剂滴加在聚氨酯预聚体中，搅拌反应，得到封闭聚氨酯预聚体。
8.如权利要求1所述的铝塑膜的制备方法，其特征在于，热熔胶膜的制备方法如下：
将封闭聚氨酯预聚体、热塑性聚氨酯弹性体、抗氧剂、钛白粉、气相二氧化硅、溶剂、流平剂复配成为胶黏剂，再将胶黏剂涂布在离型纸，干燥形成PU膜，然后将PU膜与BOPA膜复合，去除离型膜，得到PU/BOPA复合膜。
9.如权利要求1所述的铝塑膜的制备方法，其特征在于，PU/BOPA复合膜与铝箔的复合温度为80-120℃。
10.一种铝塑膜，其特征在于，采用如权利要求1-9任一项的制备方法制得。
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CN113736411A (zh) * 2021-08-25 2021-12-03 广东巨圣新材料科技有限公司 一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法

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CN115260969A (zh) * 2022-08-30 2022-11-01 江西省盛纬材料有限公司 一种铝塑膜用热熔复合胶黏剂及其制备方法和应用
CN115260969B (zh) * 2022-08-30 2024-04-05 江西省盛纬材料有限公司 一种铝塑膜用热熔复合胶黏剂及其制备方法和应用

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