CN115141584B - Tpu汽车保护膜用丙烯酸酯压敏胶及其制备方法和使用方法 - Google Patents
Tpu汽车保护膜用丙烯酸酯压敏胶及其制备方法和使用方法 Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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Abstract
本发明属于C09J151/00粘合剂技术领域,更具体的涉及一种TPU汽车保护膜用丙烯酸酯压敏胶及其制备方法和使用方法。一种TPU汽车保护膜用丙烯酸酯压敏胶,制备原料按重量份计,包括:软单体10‑13份,硬单体15‑20份,功能单体0.1‑3份,溶剂70份,引发剂0.01‑0.05份,助剂0.05‑1份。通过研究软硬单体配比,调整分子量及分子量分布,进一步通过研究胶粘剂的粘弹性及润湿性的分析,制备出与TPU基础结合力强的胶粘剂,其与TPU基材撕扯开的剥离强度;经本发明制备的压敏胶具有高初粘、高剥离、高内聚的优点。通过高玻璃化温度加宽分子量分布加高分子量最大峰值,并且通过协同交联作用,使制备得到的胶粘剂剥离强度达到2000gf/25mm以上,持粘性能达到150℃高温下24h无位移。
Description
技术领域
本发明属于C09J151/00粘合剂技术领域,更具体的涉及一种TPU汽车保护膜用丙烯酸酯压敏胶及其制备方法和使用方法。
背景技术
汽车漆面保护膜也叫做隐形车衣,是通过高分子聚合材料贴附于汽车车漆表面,达到保护原漆、装饰车身的目的,并可随时轻易揭除的保护膜,其按基材分类,主要分为PVC、TPH或TPU薄膜的漆面保护膜,具备更加便于施工,柔韧性、耐久性、抗化学腐蚀性等诸多优点。可有效保证施工过程中面对曲折车身表面时可进行准确、无缝隙、无气泡贴复。不会对车漆造成损害,相反,会充分保护车辆的原漆。
目前TPU材质的汽车漆面保护膜,具有高张力、拉力,优良的耐老化性能、抗腐蚀等特点长期占领汽车漆面保护膜的高端产品市场,具有长远的发展潜力,但TPU材料表面能低,使用常规胶粘剂较难实现良好的粘基力,从而引起漆面保护膜掉胶脱胶等问题,严重者会破坏车漆表面,大大影响使用效果。同时汽车流线型结构复杂多样,市场常规胶粘剂粘接性一般,较难满足剥离强度适中,粘附性好且不损坏车漆,边角抗起翘能力好,可重复撕贴。最后,作为一款外贴膜,压敏胶对耐老化及耐黄变要求极其苛刻,这也是本胶粘剂主要解决的问题之一。
申请号为201110410123.9的中国发明专利公开了一种窗膜用丙烯酸酯压敏胶粘剂,公开专利中提出了通过丙烯酸酯单体、功能单体、可聚合表面活性单体、引发剂和溶剂制备得到一种静电较小、易于贴膜、贴覆面平整、透明效果好、附着力强的丙烯酸酯胶粘剂,但是经过太阳长时间照射可能导致其出现黄变现象,影响车外观的美感。
发明内容
为了解决上述技术问题,本发明的第一方面提供了一种TPU汽车保护膜用丙烯酸酯压敏胶,制备原料按重量份计,包括:软单体10-13份,硬单体15-20份,功能单体0.1-3份,溶剂70份,引发剂0.01-0.05份,助剂0.05-1份。
在一些优选的实施方式中,所述的软单体选自丙烯酸酯丁酯、丙烯酸异辛酯、丙烯酸乙酯中的至少一种。
在一些优选的实施方式中,所述的软单体为丙烯酸丁酯。
在一些优选的实施方式中,所述的硬单体选自丙烯酸甲酯、甲基丙烯酸甲酯中的至少一种。
进一步优选的,所述的硬单体为丙烯酸甲酯。
在一些优选的实施方式中,所述的功能单体选自丙烯酸、β-丙烯酰氧基丙酸、丙烯酸羟乙酯、甲基丙烯酸羟乙酯中的至少一种。
进一步优选的,所述的功能单体为丙烯酸。
在一些优选的实施方式中,所述的溶剂选自乙酸乙酯、甲苯、庚烷、丙酮、异丙醇、乙酸丁酯中的至少一种。
为了进一步提升丙烯酸酯压敏胶制备过程中制备原料之间的混合效果,进一步优选的,所述的溶剂为乙酸乙酯和甲苯的混合溶液。
在一些优选的实施方式中,所述的乙酸乙酯和甲苯的重量比为(1-10):3。
进一步优选的,所述的乙酸乙酯和甲苯的重量比为4:3。
在一些优选的实施方式中,所述的引发剂选自偶氮二异丁腈、过氧化二月桂酰、过氧化2-乙基己酸叔戊酯中的至少一种。
进一步优选的,所述的引发剂为偶氮二异丁腈。
在一些优选的实施方式中,所述的助剂包括紫外吸收剂、抗氧剂、稳定剂、流平剂、消泡剂、硅烷偶联剂中的至少一种。
在一些优选的实施方式中,所述的助剂为紫外吸收剂和/或抗氧剂。
在一些优选的实施方式中,所述的紫外吸收剂为501紫外吸收剂和/或284紫外吸收剂。
在一些优选的实施方式中,所述的抗氧剂为抗氧剂1010和/或抗氧剂1024。
在实验过程中申请人经过大量创造性实验探究发现,在本体系中通过偶氮二异丁的加入,可以快速产生自由基,引发硬单体、软单体和功能单体之间的相互作用,保证了使用过程中引发剂的完全分解,避免了在本体系中与单体发生副反应而导致的压敏胶性能的下降;另外,在经过申请人大量创造性实验探究发现,在本体系中通过紫外吸收剂的加入,其与本体系中硬单体、软单体和功能单体之间的相互作用,可以在体系中形成的网络结构之间形成一层保护屏障,在对260-400nm范围内的紫外波长吸收之外,还会避免碳碳双键的断裂,降低太阳光在压敏胶表面长时间对表面的破坏,提升了其耐黄变的效果;
另外,在实验过程中申请人发现,在本体系中加入抗氧剂也可以改善耐黄变的效果,同时,还可以提升其与TPU基材的结合力,申请人推测可能是因为:抗氧剂中存在的活性基团可以在体系中与基材的活性基团之间形成强氢键相互作用,保证其与基材之间高的结合力的同时还能提升压敏胶在使用过程中的稳定性,避免黄变的出现。
本发明的第二方面提供了一种TPU汽车保护膜用丙烯酸酯压敏胶的制备方法,包括以下步骤:
1)按照比例将软单体、硬单体、功能单体、溶剂、引发剂混合均匀后,将其均分为两部分;
2)将其中一部分加入反应瓶加热使其回流反应,反应维持70-85℃,保温30-90分钟;
3)然后将另外一部分入步骤2)中,滴加的时间为90-180分钟,滴加结束后,70-75℃保温3-5小时,然后降温,降温后加入助剂并搅拌均匀,即得。
本发明的第三方面提供了一种TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,在压敏胶中加入固化剂和溶剂并搅拌均匀,用涂布机在TPU薄膜上进行涂布。
在一些优选的实施方式中,所述的固化剂的用量为压敏胶重量的0.5-5wt%。
在一些优选的实施方式中,所述的固化剂选自异氰酸酯类固化剂、氮丙啶类固化剂、金属盐类固化剂中的至少一种。
有益效果:与现有技术相比,本发明具有以下优点:
1、通过研究软硬单体配比,调整分子量及分子量分布,进一步通过研究胶粘剂的粘弹性及润湿性的分析,制备出与TPU基础结合力强的胶粘剂,其与TPU基材撕扯开的剥离强度;
2、胶粘剂耐黄变性能优异,可以达到QUV试验2500h,△b<0.8(测试标准依据为ASTMG154);
3、经本发明制备的压敏胶具有高初粘、高剥离、高内聚的优点。通过高玻璃化温度加宽分子量分布加高分子量最大峰值,并且通过协同交联作用,使制备得到的胶粘剂剥离强度达到2000gf/25mm以上,持粘性能达到150℃高温下24h无位移。
具体实施方式
实施例
实施例1-6和对比例1-3
实施例1-6和对比例1-3的配方组成见下表1。
其中:所述的溶剂为乙酸乙酯和甲苯,其重量比为4:3;
所述的引发剂为偶氮二异丁腈;
所述的助剂为紫外吸收剂,所述的紫外吸收剂为501UV吸收剂,购于德国巴斯夫;
另外:制备原料以重量份计,具体如下:
表1:
一种TPU汽车保护膜用丙烯酸酯压敏胶的制备方法,包括以下步骤:
1)按照比例将软单体、硬单体、功能单体、溶剂、引发剂混合均匀后,将其均分为两部分;
2)将其中一部分加入反应瓶加热使其回流反应,反应维持78℃,保温60分钟;
3)然后将另外一部分入步骤2)中,滴加的时间为120分钟,滴加结束后,73℃保温4小时,然后降温,降温后加入助剂并搅拌均匀,即得。
一种TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,在压敏胶中加入固化剂和溶剂并搅拌均匀,用涂布机在TPU薄膜上进行涂布。
所述的固化剂为六亚甲基二异氰酸酯;
所述的溶剂为乙酸乙酯;
所述的固化剂的用量为压敏胶重量的2wt%,所述的溶剂的重量与胶粘剂的重量比为1:1;
性能测试
将实施例1-6和对比例1-3制备得到的压敏胶进行性能测试:
压敏胶主要性能指标如下:
1.玻璃化转变温度测试、分子量及其分布测试、180°剥离强度的测定、持粘性能测试、初粘性能测试:
与TPU结合力测试:用醋酸乙酯将压敏胶稀释至20%固含量,加入计量的交联剂搅拌均匀,制得涂布液;用涂布器均匀地涂布于25μmPET离型膜,在120±5℃下干燥3min后,转涂至150μmTPU膜,制得胶带,干胶厚度25μm,将样品放置24h后,进行与TPU结合性能测试,按GB/T 2792-1998(机拉测试)、手撕或手搓进行测定,出现不掉胶与原样品一致记为合格,用★★★★★表示,★越少代表测试结果越差。
玻璃化转变温度(Tg)测试:通过示差扫描热量分析进行测试,是在N2的保护下进行的,温度范围为-80~100℃,升温速率为10℃/min。
分子量及分子量分布测试:将制备得到的膜在适量的THF中浸泡一定的时间待其溶解,保证样品在3~4mg之间。
初粘测试:测试方法按照GB/T 2794-2013。
剥离强度测试:测试方法参照PSTC-101。
耐高温持粘性能测定:150℃参照PSTC-107方法测定。
持粘性能:用醋酸乙酯将压敏胶稀释至20%固含量,加入计量的交联剂搅拌均匀,制得涂布液;用涂布器均匀地涂布于25μmPET离型膜,在120±5℃下干燥3min后,转涂至150μmTPU膜,制得胶带,干胶厚度25μm,将压敏胶贴在宽度约200mm,长度约300mm的重1kg的试件上,150℃,4小时后测量位移,并记录。
将实验结果记录于下表2。
表2:
实施例7-13和对比例4-6的配方组成见下表3。
所述的软单体为丙烯酸丁酯;
所述的硬单体为丙烯酸甲酯;
所述的功能单体为丙烯酸;
所述的溶剂为乙酸乙酯和甲苯,其重量比为4:3;
表3:
一种TPU汽车保护膜用丙烯酸酯压敏胶的制备方法,包括以下步骤:
1)按照比例将软单体、硬单体、功能单体、溶剂、引发剂混合均匀后,将其均分为两部分;
2)将其中一部分加入反应瓶加热使其回流反应,反应维持78℃,保温60分钟;
3)然后将另外一部分入步骤2)中,滴加的时间为120分钟,滴加结束后,73℃保温4小时,然后降温,降温后加入助剂并搅拌均匀,即得。
一种TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,在压敏胶中加入固化剂和溶剂并搅拌均匀,用涂布机在TPU薄膜上进行涂布。
所述的固化剂为六亚甲基二异氰酸酯;
所述的溶剂为乙酸乙酯;
所述的固化剂的用量为压敏胶重量的2wt%,所述的溶剂的重量与胶粘剂的重量比为1:1;
性能测试
将实施例7-13和对比例4-6制备得到的压敏胶用于耐黄变性能测试,用醋酸乙酯将压敏胶稀释至20%固含量,加入计量的交联剂搅拌均匀,制得涂布液;用涂布器均匀地涂布于25μmPET离型膜,在120±5℃下干燥3min后,转涂至150μmTPU膜,制得胶带,干胶厚度25μm,将150μmTPU样品膜贴于玻璃板(0.35cm)上,在QUV老化试验箱中进行测试(UV(60℃)加热8h,冷凝(50℃)4h)2500h,放置结束后,测试黄变值(ASTMG154)并将黄变值的测试结果记录于下表4。
表4:
实验 | 耐黄变△b |
实施例7 | 0.71 |
实施例8 | 0.59 |
实施例9 | 0.57 |
实施例10 | 0.62 |
实施例11 | 0.67 |
实施例12 | 0.68 |
实施例13 | 0.74 |
对比例4 | 0.98 |
对比例5 | 0.84 |
对比例6 | 0.91 |
Claims (7)
1.一种TPU汽车保护膜用丙烯酸酯压敏胶,其特征在于,制备原料按重量份计,包括:软单体12.8份,硬单体17.6份,功能单体1.6份,溶剂70份,引发剂0.01-0.05份,助剂0.05-1份;
所述的软单体为丙烯酸丁酯;所述的硬单体为丙烯酸甲酯;所述的功能单体为丙烯酸;
所述的TPU汽车保护膜用丙烯酸酯压敏胶的制备方法,包括以下步骤:
1)按照比例将软单体、硬单体、功能单体、溶剂、引发剂混合均匀后,将其均分为两部分;
2)将其中一部分加入反应瓶加热使其回流反应,反应维持70-85℃,保温30-90分钟;
3)然后将另外一部分入步骤2)中,滴加的时间为90-180分钟,滴加结束后,70-75℃保温3-5小时,然后降温,降温后加入助剂并搅拌均匀,即得。
2.根据权利要求1所述的TPU汽车保护膜用丙烯酸酯压敏胶,其特征在于,所述的溶剂选自乙酸乙酯、甲苯、庚烷、丙酮、异丙醇、乙酸丁酯中的至少一种。
3.根据权利要求1所述的TPU汽车保护膜用丙烯酸酯压敏胶,其特征在于,所述的引发剂选自偶氮二异丁腈、过氧化二月桂酰、过氧化2-乙基己酸叔戊酯中的至少一种。
4.根据权利要求1所述的TPU汽车保护膜用丙烯酸酯压敏胶,其特征在于,所述的助剂包括紫外吸收剂、抗氧剂、稳定剂、流平剂、消泡剂、硅烷偶联剂中的至少一种。
5.一种根据权利要求1-4任一项所述的TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,其特征在于,在压敏胶中加入固化剂和溶剂并搅拌均匀,用涂布机在TPU薄膜上进行涂布。
6.根据权利要求5所述的TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,其特征在于,所述的固化剂的用量为压敏胶重量的0.5-5wt%。
7.根据权利要求6所述的TPU汽车保护膜用丙烯酸酯压敏胶的使用方法,其特征在于,所述的固化剂选自异氰酸酯类固化剂、氮丙啶类固化剂、金属盐类固化剂中的至少一种。
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