CN110776835B - 一种硬质光滑基材表面用标示膜 - Google Patents

一种硬质光滑基材表面用标示膜 Download PDF

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CN110776835B
CN110776835B CN201911086687.4A CN201911086687A CN110776835B CN 110776835 B CN110776835 B CN 110776835B CN 201911086687 A CN201911086687 A CN 201911086687A CN 110776835 B CN110776835 B CN 110776835B
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李金洞
杜小冬
邓丽霞
张乃凡
牛杏梅
王利红
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Jiaozuo Zhuoli Film Material Co ltd
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Abstract

本发明针对现有技术中存在热转印碳带难以应用到金属等基材表面的局限，提供一种硬质光滑基材表面用标示膜，通过以下方法制成：由热转印碳带将标示信息热转印至TPU薄膜表面，然后加热加压使TPU薄膜熔融并与金属的表面相粘接，冷却后即得标示膜；所述热转印碳带包括带基，所述带基的两侧分别涂布有背涂层和热转印层，所述热转印层从带基一侧表面自内向外依次由保护层和粘接层构成。该标示膜能够达到使用所需的粘接强度，耐腐蚀性能好，且避免了化学蚀刻引起的损伤。

Description

一种硬质光滑基材表面用标示膜
技术领域
本发明属于热转印材料技术领域，具体涉及一种硬质光滑基材表面用标示膜及其加工工艺。
背景技术
近年来，随着热转印技术的发展，采用碳带热转印的方式来取代传统印刷方式越来越广泛，但是金属等材料表面的印刷受制于碳带的转印方式限制，要么采用碳带打印到标签后通过粘贴的方式，要么采用化学蚀刻的方式进行。前者粘接强度和耐受酒精、日晒、酸碱腐蚀等复杂条件性能差，后者会对玻璃、陶瓷等造成损坏，经济型不好。
发明内容
本发明针对现有技术中存在热转印碳带难以应用到金属等基材表面的局限，提供一种硬质光滑基材表面用标示膜，该标示膜能够达到使用所需的粘接强度，不仅耐腐蚀性能好，而且避免了化学蚀刻引起的损伤。
本发明采用如下技术方案：
一种硬质光滑基材表面用标示膜，通过以下方法制成：由热转印碳带将标示信息热转印至TPU薄膜表面，然后加热加压使TPU薄膜熔融并与硬质光滑基材的表面相粘接，冷却后即得标示膜；所述热转印碳带包括带基，所述带基的两侧分别涂布有背涂层和热转印层，所述热转印层从带基一侧表面自内向外依次由保护层和粘接层构成；
其中，所述硬质光滑基材包括玻璃、金属、陶瓷等。
优选地，所述热转印碳带为耐高温树脂基碳带。
优选地，所述保护层由以下重量百分比的原料制成：聚四氟乙烯蜡25％-35％、聚酰亚胺树脂0～5％、余量为有机硅橡胶，所述有机硅橡胶的硬度在70A以上，断裂伸长率在700％以上。
有机硅橡胶的硬度在70A以上，断裂伸长率在700％以上，能够保证在加热TPU薄膜时，印迹能够不因为TPU高温受热变形而改变，保证印迹的保证完整性，同时提供足够的牢度。
优选地，所述粘接层由以下重量配比的原料制成：蜡、间苯二酚甲醛树脂、亚甲基供体和炭黑的质量比为3-6：80-87：2-3：8-13，其中，所述间苯二酚甲醛树脂的软化点在95-100℃，其中游离的甲醛和游离苯酚的含量低于5ppm。根据产品使用条件，软化点在95-100℃的间苯二酚甲醛树脂既能够保证打印温度，又能够在加热反应后保持足够的粘接力。
优选地，所述亚甲基供体选自甲醛，多聚甲醛，六亚甲基四胺，六甲氧基甲基密胺以及2-N-2-甲基-1-丙醇中的一种或多种。
优选地，所述背涂层厚度为0.1～0.2μm，所述保护层厚度为0.8-1.2μm，所述粘接层厚度0.8-1.5μm。
优选地，所述TPU薄膜厚度为2-4μm，熔点为180℃以上，断裂伸长率大于600％，防水指数大于1500mmH2O。
优选地，所述耐高温树脂基碳带的制备过程包括以下步骤：
a、在带基一侧表面涂布背涂层浆料，烘干后得到所述背涂层；
b、按重量配比将有机硅橡胶、聚四氟乙烯蜡和聚酰亚胺树脂溶于有机溶剂中，在100℃-110℃下涂布在带基另一侧表面，烘干后得到所述保护层；
c、按重量配比将蜡、间苯二酚甲醛树脂和亚甲基供体溶于有机溶剂中，再按重量配比加入炭黑进行研磨后涂布，涂布在步骤b所得的保护层表面，烘干得到所述粘接层；至此，制备得到所述耐高温树脂基碳带。
本发明的有益效果如下：
本发明通过使用热敏打印机将耐高温树脂基碳带打印至TPU薄膜材料上，通过加热加压该TPU薄膜使其熔融粘接至陶瓷、金属、玻璃等基材的表面，冷却后能够达到足够的粘接强度，且耐溶剂、酸碱腐蚀性强，同时避免了化学蚀刻对材料表面的损伤。
其中，本发明中的保护层选用了有特殊性能要求的有机硅橡胶，该有机硅橡胶能够保证在加热TPU薄膜时，印迹能够不因为TPU高温受热变形而改变，保证印迹的保证完整性，同时提供足够的牢度，此外本发明的保护层还通过利用有机硅树脂的耐高温、耐溶剂等方面的优势，辅助聚四氟乙烯蜡和聚酰亚胺树脂通过印刷形成一个能够在热转印后保护印迹的涂层，同时也能避免TPU在高温转印过程中过度变形。
本发明的粘接层主要是利用间苯二酚甲醛树脂和亚甲基供体在高温作用下形成一个热固性树脂，能够在加热TPU材料时产生足够的粘接力，且能够抵抗溶剂、汗液等侵蚀。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚，下面结合具体实施例对本发明的技术方案作出进一步的说明。
以下实施例优选采用以下原料：
带基厚度4.5μm，选用日本东丽的BOPET膜；
有机硅橡胶采用美国迈图TSE221系列产品(TSE221-3U～6U)，其干燥后的硬度可达到70A(邵氏硬度)以上；断裂伸长率700％-900％；
聚四氟乙烯蜡的熔点在300～320℃之间，采用美国三叶公司SST系列产品；
粘接层的蜡主要用聚乙烯微粉蜡，原始粒径为2μm，熔点为130℃，优选美国honeywell公司的cμmist C3；
所采用的TPU薄膜具体为：薄膜厚度：10mm；材料熔点：140-150℃；材料的断裂伸长率大于600％-800％，购自东莞百骏新材料有限公司；
实施例1
一种硬质光滑基材表面用标示膜，通过以下方法制成：采用热敏打印机，通过脉冲加热的方式加热热转印碳带，从而将标示信息热转印至TPU薄膜表面，然后加热加压(温度140-150℃、压力1.3MPa-1.5MPa、加热时间5-8s)使TPU薄膜表面熔融并与金属的表面相粘接，冷却后即得标示膜；所述热转印碳带包括带基，所述带基的两侧分别涂布有背涂层和热转印层，所述热转印层从带基一侧表面自内向外依次由保护层和粘接层构成；
本实施例中，所述热转印碳带为耐高温树脂基碳带，其采用如下配比的原料制备而成：
Figure BDA0002265620840000031
制备方法具体如下：
a)背涂层：将背涂材料主剂改性有机硅材料120g、溶剂甲苯45g加热60度用甲苯溶解完全后冷却至室温，加入助剂异氰酸酯1g搅拌均匀，制备成背涂层材料涂布在带基的一侧，烘干温度为80℃，背涂层厚度0.2μm；
b)以重量计，将有机硅橡胶60g、聚四氟乙烯蜡35g、聚酰亚胺树脂5g，用65mL甲苯和5mL DMF的混合溶剂加热至100℃溶解，并在此温度下涂布在带基一侧，涂布密度为4g/m2，在80～85℃下烘干形成厚度0.9μm的保护层；
c)以重量计，聚乙烯蜡6g：间苯二酚甲醛树脂80g：六次甲基四胺1.5g：六甲氧基甲基蜜胺1g，用甲苯和丁酮将上述树脂和蜡溶解，加入炭黑11.5g进行研磨后涂布，涂布在保护层表面，涂布密度5g/m2，在80～100℃下烘干形成厚度1.2μm的粘接层。
实施例2
本实施例与实施例1的不同之处在于所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000041
涂布时，背涂层厚度0.2μm，保护层厚度1.0μm，粘接层厚度1.3μm。
实施例3
本实施例与实施例1的不同之处在于所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000042
Figure BDA0002265620840000051
涂布时，背涂层厚度0.2μm，保护层厚度1μm，粘接层厚度1.4μm。
实施例4
本实施例与实施例1的不同之处在于所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000052
涂布时，背涂层厚度0.2μm，保护层厚度0.9μm，粘接层厚度1.3μm；
实施例5
本实施例与实施例1的不同之处在于所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000053
Figure BDA0002265620840000061
涂布时，背涂层厚度0.2μm，保护层厚度1.2μm，粘接层厚度1.2μm。
实施例6
本实施例与实施例1的不同之处在于：(1)标示膜粘贴于玻璃表面；(2)所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000062
涂布时，背涂层厚度0.2μm，保护层厚度1.0μm，粘接层厚度1.3μm。
实施例7
本实施例与实施例1的不同之处在于：(1)标示膜粘贴于陶瓷表面；(2)所述热转印碳带为耐高温树脂基碳带的原料配比不同以及涂布厚度不同，本实施例中所述热转印碳带为耐高温树脂基碳带采用如下配比的原料制备而成：
Figure BDA0002265620840000071
涂布时，背涂层厚度0.2μm，保护层厚度1.1μm，粘接层厚度1.5μm。
现对实施例1至7的标示膜的粘接强度和耐腐蚀性进行检测：
1、剥离强度
检测设备：拉力试验机，检测方法：GB/T 2792-1998；经检测，实施例1至7的标示膜与基材表面的剥离强度分别为12.7N/cm、17.5N/cm、14.3N/cm、15.8N/cm、14.6N/cm、15.2N/cm，16.3N/cm均大于10N/cm，能够满足使用要求。
2、耐乙醇性能
检测设备：磨耗试验机；负荷500g，500次以上无变化。
3、耐低温性能；
-40℃低温存放24H，粘结效果无变化
4、耐酸碱性能
检测设备：磨耗试验机酸性碱性实验介质(酸性：PH值为2-3的稀盐酸、碱性：PH值为11-12碳酸氢钠水溶液)，负荷500g 500次以上无变化
5、耐水性能
打印过的TPU材料使用(60±3)℃的水温进行洗涤，2h为1周期，连续洗涤4周期，结果印迹无变化、无变淡脱色等情况。
最后所应说明的是：上述实施例仅用于说明而非限制本发明的技术方案，任何对本发明进行的等同替换及不脱离本发明精神和范围的修改或局部替换，其均应涵盖在本发明权利要求保护的范围之内。

Claims (5)

1.一种硬质光滑基材表面用标示膜，其特征在于，通过以下方法制成：由热转印碳带将标示信息热转印至TPU薄膜表面，然后加热加压使TPU薄膜熔融并与硬质光滑基材的表面相粘接，冷却后即得标示膜；所述热转印碳带包括带基，所述带基的两侧分别涂布有背涂层和热转印层，所述热转印层从带基一侧表面自内向外依次由保护层和粘接层构成；
所述保护层由以下重量百分比的原料制成：聚四氟乙烯蜡 25%-35%、聚酰亚胺树脂 0~5%、余量为有机硅橡胶，所述有机硅橡胶的硬度在70A以上，断裂伸长率在700%以上；
所述粘接层由以下重量配比的原料制成：蜡、间苯二酚甲醛树脂、亚甲基供体和炭黑的质量比为3-6：80-87：2-3：8-13，其中，所述间苯二酚甲醛树脂的软化点在95-100℃；
所述热转印碳带为耐高温树脂基碳带；
热转印碳带通过如下步骤制备得到：
a、在带基一侧表面涂布背涂层浆料，烘干后得到所述背涂层；
b、按重量配比将有机硅橡胶、聚四氟乙烯蜡和聚酰亚胺树脂溶于有机溶剂中，在100℃-110℃下涂布在带基另一侧表面，烘干后得到所述保护层；
c、按重量配比将蜡、间苯二酚甲醛树脂和亚甲基供体溶于有机溶剂中，再按重量配比加入炭黑进行研磨后涂布，涂布在步骤b所得的保护层表面，烘干得到所述粘接层；至此，制备得到所述热转印碳带。
2.根据权利要求1所述的硬质光滑基材表面用标示膜，其特征在于，所述亚甲基供体选自甲醛，多聚甲醛，六亚甲基四胺，六甲氧基甲基密胺的一种或多种。
3.根据权利要求1所述的硬质光滑基材表面用标示膜，其特征在于：所述TPU薄膜厚度为2-4μm，熔点为180℃以上，断裂伸长率大于600%，防水指数大于1500mmH2O。
4.根据权利要求1所述的硬质光滑基材表面用标示膜，其特征在于，所述硬质光滑基材包括玻璃、金属、陶瓷。
5.根据权利要求1或2所述的硬质光滑基材表面用标示膜，其特征在于：所述背涂层厚度为0.1~0.2μm，所述保护层厚度为0.8-1.2μm，所述粘接层厚度0.8-1.5μm。
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