CN111619186A - 一种发泡双向拉伸热敏薄膜 - Google Patents

一种发泡双向拉伸热敏薄膜 Download PDF

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CN111619186A
CN111619186A CN202010499340.9A CN202010499340A CN111619186A CN 111619186 A CN111619186 A CN 111619186A CN 202010499340 A CN202010499340 A CN 202010499340A CN 111619186 A CN111619186 A CN 111619186A
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biaxially oriented
foamed
sensitive film
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CN111619186B (zh
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钱昇阳
姜烨
朱小峰
徐波
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Wuxi He Shuo Feng New Material Co ltd
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Abstract

本发明涉及一种发泡双向拉伸热敏薄膜，主要用于不干胶标签面材。本发明提供一种发泡双向拉伸热敏薄膜，薄膜包括多层结构，其中包括至少一层白色层，以及一层除白色之外其他颜色的颜色层，白色层为发泡层，颜色层为非发泡层，白色层位于颜色层之上，受热之前发色密度为A，当薄膜受热后白色层熔化收缩从而显现出颜色层，实现热敏功能，受热后发色密度为B，满足(B‑A)≥0.5，发色密度测量能级为20能级。本发明的双向拉伸热敏薄膜，其具备良好的发色性能，相对完善的打印感度，完美的耐候性能，可以接近永久的保存打印信息。

Description

一种发泡双向拉伸热敏薄膜
技术领域
本发明涉及一种发泡双向拉伸热敏薄膜，主要用于不干胶标签面材。具体涉 及五层共挤双向拉伸热敏薄膜的配方及其制备方法，属热敏薄膜技术领域。
背景技术
信息多样化和需求扩大推动了信息记录领域中各种记录材料的研究和开发， 并且各种材料已经投入实际应用。在它们之中，使用热敏记录材料是有利的，原 因在于：(1)它允许利用加热法而容易地记录图像，(2)相应的装置可以具有简单 机构并且可以容易地被减少尺寸；和(3)易于操纵且成本便宜。
因此，热敏记录材料广泛用于各个领域，包括数据处理(台式计算器、计算 机等的输出)、用于医疗测量的记录器、低速或高速传真、自动售票机(火车票、 入场券等)、热复印、用于POS系统的标签、标签等。
传统热敏记录材料在纸载体上具有包含成色剂的层，所述成色剂通过热产生 显色反应。然而，考虑到尺寸稳定性、机械强度、和水不溶性——它们是记录纸 需要的性质，合成纸或合成树脂薄膜被用作载体。目前热敏标签薄膜主要采用隐 色染料遇热发色的原理生产，由于使用隐色燃料在温度作用下与显色剂混合后发 色，发色反应属于氧化还原反应，因此受限于长期的保存条件，在各类环境下易 发生逆向反应从而导致未显色部分显色，显色部分褪色等不良现象，最终导致材 料保存信息丢失。为了保持信息能够长久保存，不得不对材料进行各种耐候性能 提升，加之配方技术及涂布复杂，成本较高。
其实在隐色燃料出现之前，还有两类热敏材料分别为金属氧化物显色以及熔 融透明显色。金属氧化物由于重金属超标已经基本不再发展，熔融透明型是一类 一直在发展但进展缓慢的技术。难度在于工艺复杂以及熔融层施工技术难度过 大。传统的热敏纸大多使用纸张作为基材，熔融透明型热敏一般选用有色纸张作 为基材，在有色底纸上涂覆一层不透明的蜡作为遮盖层，当蜡受热后即发生融化 从而变得透明，从而显现信息。这种热敏纸不存在记录保存等问题，其保存时间 完全取决于色纸的保存能力，因此耐候性能相当优异。但是其也存在先天不足， 由于表层的蜡强度有限，受到机械尖针剐蹭后即会出现露底现象，从而导致材料 抗刮性能较差。此外较高的显色温度往往导致打印机记录针损伤，影响了其广泛 性的应用。
在现有技术中，上述显色工艺存在工艺复杂，成本较高的缺陷，也没有直接 利用聚丙烯薄膜制备热敏薄膜的先例。
发明内容
本发明解决的技术问题为提供一种发泡双向拉伸热敏薄膜，其使用双向拉伸 工艺生产，可以较大批量低成本的生产，可以在热敏打印机的打印下可以显现颜 色，达到一般热敏纸的热敏显色效果。
本发明另一目的是提供一种发泡双向拉伸热敏薄膜的制备方法。
本发明的上述目的是通过如下的技术手段来实现的：
一种发泡双向拉伸热敏薄膜，薄膜包括多层结构，其中包括至少一层白色层， 以及一层除白色之外其他颜色的颜色层，白色层为发泡层，颜色层为非发泡层， 白色层位于颜色层之上，受热之前发色密度为A，当薄膜受热后白色层熔化收缩 从而显现出颜色层，实现热敏功能，受热后发色密度为B，满足(B-A)≥0.5，发 色密度测量能级为20能级。
进一步的，发泡层发泡密度≤0.4g/cm3，优选发泡密度≤0.3g/cm3。
进一步的，受热之前发色密度A≤0.5，受热后发色密度B≥1.0。
进一步的，发泡层的发泡剂为含苯环的聚酯结构，优选聚对苯二甲酸丁二醇 酯PBT，并且不包括其他发泡剂。
进一步的，薄膜为五层结构，从上至下分别为上表层、上次表层、芯层、下 次表层和下表层，上次表层为白色发泡层，下次表层为颜色层，芯层为透明层。
进一步的，颜色层为黑色层、红色层、黄色层或蓝色层。
进一步的，各层厚度中，上表层和下表层厚度为1-5um，上次表层和下次表 层厚度为5-15um，芯层厚度为20-60um。
进一步的，上次表层组成为80-90％的共聚聚丙烯和10-20％的PBT组成，其 中共聚聚丙烯为丙烯和乙烯以及降冰片烯共聚物，PBT重均分子量为5万-20万， 分子量分布为1.5-2，如金发PF020。
进一步的，芯层组成为三元共聚聚丙烯，熔融指数在3-4g/10min，共聚聚 丙烯为丙烯、乙烯、丁烯共聚物。优选使用牌号FS5612，EP560，3C30F，TF1007。
进一步的，上表层组成为消光聚丙烯母料，优选PE和PP的共混改性母料， 如金发科技M973。优选50-70％的PP和50-30％的PE。
进一步的，下表层包括PP的均聚物或共聚物，包括均聚聚丙烯，二元共聚 聚丙烯(如金山石化F800，中国石化RP210M)，三元共聚聚丙烯(如C30F,FS5612)， 进一步选择下表层为共聚聚丙烯混合白色母料和二氧化硅母料。
进一步的，所述的发泡双向拉伸热敏薄膜的制备方法，包括如下步骤：(1) 按要求准备各层原料；(2)采用五台挤出机挤出后经流延，纵向拉伸，横向拉 伸牵引收卷后分切得到所述发泡双向拉伸热敏薄膜，其中发泡过程是伴随着纵向 拉伸和横向拉伸的。
进一步的：消光料经挤出机熔融后作为上表层挤出，挤出温度220度，上次 表层挤出温度220度，芯层挤出温度240度，下次表层挤出温度250度，下表层 挤出温度220度。熔体分别经过滤器过滤后在五层使用衣架式模头汇合形成流延 体，模头温度250度。熔体经铸片机急冷辊冷却成片后进入水槽冷却，急冷辊温 度30度，水槽温度35度。经过冷却后的材料经过风刀和压辊除水后进入纵向拉 伸机构。厚片经过纵拉辊筒预热后经过拉伸辊拉伸，其中预温度120-130度，拉 伸温度110度，拉伸比4.8-5.2倍。经过定型后进入横向拉伸机构，定型温度 145度。横向拉伸机构采用链夹拉伸的方式按照轨道对材料进行连续拉伸，其中 预热温度145-160度，拉伸温度120-140度，定型温度130-150度，拉伸比 7.5-8.0，材料经过冷却后进入牵引段对双面进行电晕处理后收卷。电晕功率上 表面60KW，下表面120KW，收卷幅宽7.0-7.5米，随后使用分切机切成需求宽度
进一步的：消光料经挤出机熔融后作为上表层挤出，挤出温度220度，上次 表层采用均共聚聚丙烯混合PBT，比例为85：15，挤出温度220度，芯层采用三 元共聚聚聚丙烯，挤出温度230度，下次表层采用黑色母料混合共聚聚丙烯挤出， 黑色母料有效成分为炭黑，含量为50％，比例为1:9，挤出温度230度，下表层 采用共聚聚丙烯混合白色母料和二氧化硅母料，比例为75:20:5，白色母料有效 成分是二氧化钛，有效含量为60％，二氧化硅有效含量20％，挤出温度220度。
进一步的，所述的发泡双向拉伸热敏薄膜的用途，用于不干胶面签材料，实 现无碳带热敏打印。
本发明的热敏功能是通过如下原理实现的：发泡材料由于高发泡作用产生出 对光线强烈的折射和散射作用从而出现较高遮盖性能。当这一层位于带有颜色的 聚丙烯层上方时，因此材料呈现出白色或灰白色或特定颜色。当发泡材料经过热 敏打印机时，热敏打印机发色触点接触材料表面，材料表面受热后融化转为透明 色，底色被显现从而表现出热敏特性。
本发明的技术效果：可以得到双向拉伸热敏薄膜，其具备良好的发色性能， 相对完善的打印感度，完美的耐候性能，可以接近永久的保存打印信息。材料由 于不存在热敏隐色染料的反应发色原理，因此不存在褪色问题。打印信息可以长 久的被保留。由于采用均匀的底色方案，可以适合超高精度打印等特殊应用。由 于采用的是原膜直接发色原理，其对于各种溶剂具备几乎完美的耐性。是一种低 成本的高性能热敏薄膜。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明双向拉伸热敏薄膜的一种结构的结构示意图。
图2是双向拉伸热敏薄膜的生产工艺流程图。
具体实施方式
实施例中所采用的测定标准为GB T 28210-2011热敏纸标准
实施例中采用的各原料来源如下：
共聚聚丙烯A：丙烯和乙烯以及降冰片烯共聚物，其中丙烯占比55％，乙烯 占比30％，降冰片烯占比15％，比例为摩尔比
PBT重均分子量为10万，分子量分布为1.6
共聚聚丙烯B:金山石化F800
消光聚丙烯：金发科技M973
共聚聚丙烯：中国石油TF1007
白色母料：金发科技WT602
CaCO3：市售
NaHCO3：市售
实施例1
制备方法如下：按要求准备各层原料；消光料经挤出机熔融后作为上表层挤 出，挤出温度220度，上次表层挤出温度220度，芯层挤出温度240度，下次表 层挤出温度250度，下表层挤出温度220度。熔体分别经过滤器过滤后在五层使 用衣架式模头汇合形成流延体，模头温度250度。熔体经铸片机急冷辊冷却成片 后进入水槽冷却，急冷辊温度30度，水槽温度35度。经过冷却后的材料经过风 刀和压辊除水后进入纵向拉伸机构。厚片经过纵拉辊筒预热后经过拉伸辊拉伸， 其中预温度120-130度，拉伸温度110度，拉伸比4.8-5.2倍。经过定型后进入 横向拉伸机构，定型温度145度。横向拉伸机构采用链夹拉伸的方式按照轨道对 材料进行连续拉伸，其中预热温度175-180度，拉伸温度150-155度，定型温度 160-170度，拉伸比7.5-8.0，材料经过冷却后进入牵引段对双面进行电晕处理 后收卷。电晕功率上表面60KW，下表面120KW，收卷幅宽7.0-7.5米，随后使用 分切机切成需求宽度。
采用的各层原料如下：
上表层 消光聚丙烯 2um
上次表层 85％共聚聚丙烯A+15％PBT 10um
芯层 共聚聚丙烯 39um
下次表层 共聚聚丙烯+10％黑色母料 7um
下表层 75％共聚聚丙烯B+20％白色母料+5％二氧化硅 2um
实施例2-10采用相同的制备方法，差别在于上次表层的组成不同，详细组 成以及表征情况如下，其中：理论发泡密度＝((总厚度)*材料密度-(除上次 表层外各层厚度*各层相应的密度之和))/(上次表层厚度)
Figure BDA0002524195780000051
Figure BDA0002524195780000061
Figure BDA0002524195780000071
由上述实施例可以获知：在实施例1-3中的实施了不同发泡剂的比较，采用 PBT和碳酸钙都可以对上次表层进行有效发泡，但采用NaHCO3时发泡效果较差， 材料密度和发泡层理论密度较高，白度较低，实施例1和实施例2中获得的背景 色密度相似，但进行发色密度测试时，采用PBT发泡的实施例1中明显更优，发 色密度在10-25能级上都取得了更好的效果。实施例1、以及4-6实施了不同种 类的上次表层聚丙烯材料的比较，说明采用丙烯-乙烯-降冰片烯作为上次表层材 料比乙丙共聚、三元乙丙共聚以及均聚聚丙烯在发色密度以及背景色密度差值上 表现更优。实施例1，7-8实施了不同含量PBT的上次表层，综合来看15％的效 果好于10％和20％的技术方案。

Claims (13)

1.一种发泡双向拉伸热敏薄膜，其特征在于：薄膜包括多层结构，其中包括至少一层白色层，以及一层除白色之外其他颜色的颜色层，白色层为发泡层，颜色层为非发泡层，白色层位于颜色层之上，受热之前发色密度为A，当薄膜受热后白色层熔化收缩从而显现出颜色层，实现热敏功能，受热后发色密度为B，满足(B-A)≥0.5，发色密度测量能级为20能级。
2.根据权利要求1所述的发泡双向拉伸热敏薄膜，发泡层发泡密度≤0.4g/cm3，优选发泡密度≤0.3g/cm3。
3.根据权利要求1所述的发泡双向拉伸热敏薄膜，受热之前发色密度A≤0.5，受热后发色密度B≥1.0。
4.根据权利要求1所述的发泡双向拉伸热敏薄膜，发泡剂为含苯环的聚酯结构，优选聚对苯二甲酸丁二醇酯PBT，并且不包括其他发泡剂。
5.根据权利要求1-4之一所述的发泡双向拉伸热敏薄膜，薄膜为五层结构，从上至下分别为上表层、上次表层、芯层、下次表层和下表层，上次表层为白色发泡层，下次表层为颜色层，芯层为透明层。
6.根据权利要求1-4之一所述的发泡双向拉伸热敏薄膜，颜色层为黑色层、红色层、黄色层或蓝色层。
7.根据权利要求1-4之一所述的发泡双向拉伸热敏薄膜，各层厚度中，上表层和下表层厚度为1-5um，上次表层和下次表层厚度为5-15um，芯层厚度为20-60um。
8.根据权利要求1-4之一所述的发泡双向拉伸热敏薄膜，上次表层组成为80-90％的共聚聚丙烯和10-20％的PBT组成，其中共聚聚丙烯为丙烯和乙烯以及降冰片烯共聚物，PBT重均分子量为5万-20万，分子量分布为1.5-2。
9.根据权利要求1-3之一所述的发泡双向拉伸热敏薄膜，芯层组成为共聚聚丙烯，熔融指数在3-4g/10min，共聚聚丙烯为丙烯、乙烯、丁烯三元共聚物。
10.根据权利要求1-3之一所述的发泡双向拉伸热敏薄膜，上表层组成为消光聚丙烯母料，优选PE和PP的共混改性母料。
11.根据权利要求1-3之一所述的发泡双向拉伸热敏薄膜，下表层包括PP的均聚物或共聚物，包括均聚聚丙烯，二元共聚聚丙烯，三元共聚聚丙烯，进一步优选下表层为共聚聚丙烯混合白色母料和二氧化硅母料。
12.根据权利要求1-11之一所述的发泡双向拉伸热敏薄膜的制备方法，包括如下步骤：(1)按要求准备各层原料；(2)采用五台挤出机挤出后经流延，纵向拉伸，横向拉伸牵引收卷后分切得到所述发泡双向拉伸热敏薄膜，其中发泡过程是伴随着纵向拉伸和横向拉伸的。
13.根据权利要求1-11之一所述的发泡双向拉伸热敏薄膜的用途，用于不干胶面签材料，实现无碳带热敏打印。
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