CN110684226A - 一种印刷用pvc复合膜材料 - Google Patents

一种印刷用pvc复合膜材料 Download PDF

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CN110684226A
CN110684226A CN201910969845.4A CN201910969845A CN110684226A CN 110684226 A CN110684226 A CN 110684226A CN 201910969845 A CN201910969845 A CN 201910969845A CN 110684226 A CN110684226 A CN 110684226A
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printing
parts
layer
pvc
composite film
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任明淑
盖树人
彭春宁
苏腾龙
李梦倩
王大庆
柳青
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Lucky Film Co Ltd
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Abstract

一种印刷用PVC复合膜材料，所述复合膜材料包括PVC基材层、依次设置在基材层之上的隔离层和承印层；所述隔离层的涂料按照重量份数计由如下原料制成：水溶性树脂10‑50，硅溶胶10‑50，水10‑50，乙醇5‑20，消泡剂1‑10，表面活性剂0.1‑10。本发明用PVC复合膜材料替代纸张印刷，价格低廉，在生产、使用过程中，不产生荷叶边现象，防水性能好，具备优异的阻挡、隔热、粘结力强的特性，适合于HP indigo印刷。

Description

一种印刷用PVC复合膜材料
技术领域
本发明涉及薄膜技术领域，特别是一种复合薄膜材料。
背景技术
随着印刷技术的发展，数字印刷技术以其印刷速度快、影像质量高、个性化容易、印刷过程无污染等优点而得到越来越广泛的应用。印刷所用基材种类繁多，最常用印刷介质为纸张。但在实际应用过程中，在高温高湿下纸张四周吸水膨胀，产生荷叶边现象，这对印刷过程都会带来无穷的烦恼，不但输纸困难，印刷时极易出现折皱、套印不准和皱纹等问题，有严重荷叶边的纸张则不能进行印刷。
PVC是世界上用量最大的塑料产品之一，价格便宜，经久耐用，而且强度大，防穿孔、抗撕裂、耐磨、耐折叠性好，100％防水。由于PVC同时具有塑料和纸张的特性，因此在很多方面有广泛的用途，特别适用于HP indigo印刷，如高质量的照片输出、广告宣传、婚纱摄影、灯箱片制作等，不会产生荷叶边弊病，且防水性能好。但PVC材料在使用过程中存在很大的缺陷：使用一个氯原子取代聚乙烯中的一个氢原子制得的高分子材料PVC本身的硬度是比较大的，为了提高PVC膜作为印刷基材的性能，在PVC合成过程中需要添加大量的增塑剂；然而，该增塑剂在长时间放置过程中容易从PVC膜中析出，引起PVC膜表面能下降，造成图像印刷不完全并污染印刷部件。同时，PVC膜因其材料本身具有的特性(热稳定性较低)，在印刷的加热加压过程中，很容易发生变形；变形弯曲的PVC膜在印刷过程中与印版接触不紧密，造成印刷性能缺失，产生大量不符合要求的产品。
如何解决PVC膜在数字印刷使用过程中的增塑剂迁移及热变形问题，保证印刷质量、减少印刷品的报废量成为急待解决的问题。
发明内容
本发明的发明目的是针对上述PVC膜在使用过程中存在的问题，提供一种印刷用PVC复合膜材料，以解决PVC膜中的增塑剂迁移造成的印刷性能缺失和对印刷部件的污染问题，同时，还能阻隔印刷加热时的热能传递，防止PVC膜变形，从而保证印刷过程的顺利进行。
为解决上述技术问题，本发明提供如下技术方案：
一种印刷用PVC复合膜材料，所述复合膜材料包括PVC基材层、依次设置在基材层之上的隔离层和承印层,所述PVC基材层中含有增塑剂；
所述隔离层的涂料按照重量份数计由如下原料制成：
水溶性树脂10-50重量份，其中固含量为20％，
硅溶胶10-50重量份，
水10-50重量份，
乙醇5-20重量份，
消泡剂1-10重量份，
表面活性剂0.1-10重量份。
所述承印层的涂料按照重量份数计由如下原料制成；
水分散性树脂乳液10-50重量份，其中固含量为20％
抗静电剂1-10重量份
乙醇10-50重量份
消泡剂1-20重量份
表面活性剂1-10重量份。
上述印刷用PVC复合膜材料，所述隔离层中水溶性树脂与增塑剂的溶度参数差≥5(J./cm3)0.5，优选≥10(J./cm3)0.5所述J/cm3为单位体积内聚能密度。
上述印刷用PVC复合膜材料，所述隔离层的厚度为0.1-100μm。
上述印刷用PVC复合膜材料，所述水溶性树脂为聚乙烯吡咯烷酮、聚乙烯醇、羟乙基纤维素、水溶性淀粉中的一种或几种，优选聚乙烯醇。
上述印刷用PVC复合膜材料，所述硅溶胶胶体粒子平均粒径＜100nm，优选胶体粒子平均粒径＜30nm。
上述印刷用PVC复合膜材料，所述承印层的厚度为0.1-10μm
上述印刷用PVC复合膜材料，所述水分散性树脂乳液为丙烯酸乳液、聚氨酯乳液、苯丙乳液、乙烯共聚物乳液、丙烯酸共聚物乳液等物质中的一种或几种组成。
上述印刷用PVC复合膜材料，所述PVC基材层厚度为50-500μm。
本发明选择隔离层中水溶性树脂的溶度参数与PVC基材中增塑剂的溶度参数差≥5。溶度参数是表征聚合物-溶剂相互作用的参数。溶度参数可以作为衡量两种材料是否共容的一个较好的指标。当两种材料的溶度参数相近时，它们可以互相共混且具有良好的共容性。两种材料的溶度参数相差越大，这两种物质越不能共混共容。发明人经试验反复验证，隔离层中水溶性树脂的溶度参数与增塑剂的溶度参数差≥5(J./cm3)0.5时，隔离层中的水溶性树脂与PVC中的增塑剂不能共混共容，表面能测量正常，印刷图像转印完全，无图像缺失。若隔离层中水溶性树脂的溶度参数与增塑剂的溶度参数差＜5(J./cm3)0.5，则出现表面能下降，印刷时图像缺失并粘附在橡皮布上。经分析发现，当隔离层中水溶性树脂的溶度参数与增塑剂的溶度参数差≥5(J./cm3)0.5时，隔离层中的水溶性树脂与PVC中的增塑剂不能共混共容，此时隔离层产生屏障效应，可有效阻止增塑剂渗透到隔离层并继续迁移到承印层的表面引起表面能下降而造成的印刷性能缺失问题。二者的溶度参数差越大，隔离层的屏蔽效果越好，优选≥10(J./cm3)0.5。若隔离层中水溶性树脂的溶度参数与增塑剂的溶度参数差＜5(J./cm3)0.5，PVC基材中的增塑剂选用邻苯二田酸酯类。渗透到隔离层中后与隔离层中的树脂共混，并继续向承印层迁移，致使隔离层作用减弱或失效。PVC中增塑剂的溶度参数为18.0(J./cm3)0.5.符合本发明的隔离层中的水溶性树脂。PVC塑料配方主要由聚氯乙烯和添加剂组成，其中添加剂按功能又分为增塑剂、热稳定剂、润滑剂、加工改性剂、抗氧剂、紫外光吸收剂、发泡剂等。在聚氯乙烯树脂中加入适量的增塑剂，可制成多种硬质、软质和透明制品。其中增塑剂含量越高，PVC材质越软，软质PVC增塑剂含量为30-70％。为提高PVC膜作为印刷基材的性能，需用增塑剂改善PVC的硬度。有聚乙烯吡咯烷酮、聚乙烯醇、羟乙基纤维素、水溶性淀粉，优选溶度参数为29.1(J./cm3)0.5的聚乙烯醇。
硅溶胶为纳米级的二氧化硅颗粒在水中或溶剂中的分散液。其外观为乳白色或青白色，半透明状，胶体粒子粒径越小透明度越好。本发明中所选硅溶胶中胶体粒子平均粒径小于100nm，不会影响承印层的光泽度。若硅溶胶的胶体粒子平均粒径大于100nm，则会降低承印层的光泽度。优选胶体粒子平均粒径小于30nm。
硅溶胶中的无机离子熔点高，导热性差，加热时不容易产生形变，可保障隔离层为一定厚度，从而有效阻隔印刷加热时的热能传递，防止PVC基材层变形，降低因PVC基材层变形而造成印刷性能缺失和产生的废片率；本发明中硅溶胶的用量为10-50重量份，若硅溶胶用量小于10重量份，则起不到阻隔热量传递的作用；若硅溶胶用量大于50重量份，则会在隔离层中形成空隙，破坏隔离层的致密性，增塑剂会沿空隙迁移至承印层，影响印刷性能。
硅溶胶还具有较好的粘结性，将硅溶胶与水溶性树脂匹配使用，可有效改善膜层的脆性，干燥后即形成柔韧的膜结构，增强了与PVC基材层的粘附力。
因此，隔离层选用一定的水溶性树脂和硅溶胶匹配使用，具备优异的阻挡、隔热、粘结力强的特性。
本发明的有益效果如下：
(1)用PVC复合膜材料替代纸张印刷，价格低廉，在生产、使用过程中，不产生荷叶边现象，防水性能好。
(2)在承印层和PVC基材之间加涂一层隔离层，隔离层中水溶性树脂的溶度参数与增塑剂的溶度参数差需≥5(J./cm3)0.5，优选≥10(J./cm3)0.5.。此条件下，隔离层中的水溶性树脂与PVC中的增塑剂不能共混共容，从而使隔离层产生屏障效应，阻止增塑剂渗透到隔离层并继续迁移到承印层的表面而引起表面能下降，造成印刷过程中印刷性能缺失和印刷部件的污染问题，保障印刷工作的顺利进行。
(3)隔离层中含有硅溶胶，硅溶胶中的无机离子熔点高，导热性差，加热时不容易产生形变，可支撑隔离层为一定厚度，从而有效阻隔印刷加热时的热能传递，防止PVC基材层变形，降低因PVC基材层变形而导致的印刷性能缺失和产生的废片率。
(4)硅溶胶还具有较好的粘结性，将硅溶胶与水溶性树脂匹配使用，可有效改善膜层的脆性，干燥后即形成柔韧的膜结构，增强了与PVC基材层的粘附力。
总之，本发明隔离层选用与增塑剂溶度参数差≥5的水溶性树脂和硅溶胶匹配使用，具备优异的阻挡、隔热、粘结力强的特性。
附图说明
图1为本发明结构示意图。
图中各标号分别表示为：1、承印层，2、隔离层，3、基材层。
具体实施方式
以下结合几个实施例对本发明作进一步详述。
实施例1
(1)将30g去离子水、30g聚乙烯醇、20g水性淀粉加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入10g硅溶胶、10g乙醇、1g消泡剂、10g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为250μm的PVC基材层上，涂布量为100g/m2。70℃烘箱中干燥3分钟，干燥后涂层厚度为50μm。
(2)将30g聚氨酯乳液、1g抗静电剂、10g乙醇、5g消泡剂、5g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为,4.5g/m2.。在70℃干燥条件下干燥3分钟，干燥后涂层厚度为5μm。
实施例2
(1)将50g去离子水、30g羟乙基纤维素树脂加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入50g硅溶胶、5g乙醇、5g消泡剂、5g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为50μm的PVC基材层上，涂布量为300g/m2.，70℃烘箱中干燥3分钟，干燥后涂层厚度为100μm。
(2)将10g丙烯酸乳液、10g抗静电剂、30g乙醇、1g消泡剂、10g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为3g/m2.。在70℃干燥条件下干燥3分钟，干燥后涂层厚度为0.1μm。
实施例3
(1)将10g去离子水、10g聚乙烯醇加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入30g硅溶胶、20g乙醇、10g消泡剂、0.1g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为500μm的PVC基材层上，涂布量为,1g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为0.1μm。
(2)将35g苯丙乳液、15g乙烯共聚物乳液、5g抗静电剂、50g乙醇、20g消泡剂、10g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为110g/m,2.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为10μm。
实施例4
(1)将30g去离子水、10g聚乙烯吡咯烷酮、10g水溶性淀粉加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入20g硅溶胶、10g乙醇、3g消泡剂、2g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为200μm的PVC基材层上，涂布量为,5g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为1.5μm。
(2)将25g丙烯酸共聚物乳液、5g抗静电剂、20g乙醇、8g消泡剂、1g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为20g/m,2.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为2μm。
实施例5
(1)将30g去离子水、20g聚乙烯醇加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入20g硅溶胶、10g乙醇、3g消泡剂、2g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为200μm的PVC基材层上，涂布量为,5g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为1.5μm。
(2)将25g丙烯酸共聚物乳液、5g抗静电剂、20g乙醇、8g消泡剂、1g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为20g/m,2.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为2μm。
对比咧1(无隔离层)
将30g聚氨酯乳液、1g抗静电剂、10g乙醇、5g消泡剂、5g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒直接涂布于未有隔离层的PVC基材层上，涂布量为,4.5g/m2.。在70℃干燥条件下干燥3分钟，干燥后涂层厚度为5μm。
对比咧2(硅溶胶含量少，易引起pvc膜印刷变形)
(1)将30g去离子水、10g聚乙烯吡咯烷酮、10g水溶性淀粉加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入5g硅溶胶、10g乙醇、3g消泡剂、2g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为200μm的PVC基材层上，涂布量为,10g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为3μm。
(2)将25g丙烯酸共聚物乳液、5g抗静电剂、20g乙醇、8g消泡剂、1g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为20g/m,2.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为2μm。
对比咧3(硅溶胶含量过高，导致pvc膜印刷后形成空隙)
(1)将30g去离子水、10g聚乙烯吡咯烷酮、10g水溶性淀粉加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入80g硅溶胶、10g乙醇、3g消泡剂、2g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为200μm的PVC基材层上，涂布量为10g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为3μm。
(2)将25g丙烯酸共聚物乳液、5g抗静电剂、20g乙醇、8g消泡剂、1g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于上述已涂布隔离层的PVC上，涂布量为20g/m,2.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为2μm。
对比例4(溶度参数差＜5)
(1)将10g去离子水、10g聚氧乙烯【溶度参数20(J./cm3)0.5】、加入容器中，在80℃下搅拌加热至完全溶解，冷却至30℃下，加入30g硅溶胶、20g乙醇、10g消泡剂、0.1g表面活性剂搅拌均匀，制备隔离层涂布液。将上述涂布液使用涂布棒涂布于厚度为500μm的PVC基材层上，涂布量为15g/m2.，在70℃烘箱中干燥3分钟，干燥后涂层厚度为0.3μm。
(2)将25g丙烯酸共聚物乳液、5g抗静电剂、20g乙醇、8g消泡剂、3g表面活性剂加入容器中搅拌均匀，制备承印层涂布液。将上述涂布液使用涂布棒涂布于之前已涂布隔离层的PVC上，涂布量为20g/m2,.。70℃干燥条件下干燥3分钟，干燥后涂层厚度为2μm。
将上述9个示例中涂好的PVC复合膜材料样片做以下测试：
a)表面能测试
使用达因笔在承印层表面画一道墨水线，如果所画的线能在2秒内保持均匀不收缩，则承印层的表面能大于或等于达因笔的号数，如果所画的线在2秒内发生了收缩，则承印层的表面能小于达因笔的号数。
b)涂层牢度测试
采用百格法(GB/T9286-88)测试涂层牢度。
c)PVC膜材料变形测试
目测印刷后的PVC复合膜材料是否平整，有无弯曲。
d)图像印刷牢度测试
使用HP indigo12000印刷机、指定印刷测试图案印刷前面9个示例中涂好的PVC复合膜材料，目测印刷图像是否转印完全，有无缺失，并用下列方法测试图像牢度。
将印刷好的带有青(100％C)、品(100％M)、黄(100％Y)、黑(100％K)图像的PVC复合膜材料，放在平坦的台面上，用3M胶带的一端分别粘贴青(100％C)、品(100％M)、黄(100％Y)、黑(100％K)的色块处，粘贴长度至少超过色块20mm，胶带的另一端不粘贴，然后用直尺将胶带刮平保证接触良好，以接近90℃撕拉方向将胶带揭下，反射密度计测试粘揭前后的反射密度数据，粘揭后密度/粘揭前密度的数据≥90％即为合格。
各项测试数据如下：
Figure BDA0002231696770000071
Figure BDA0002231696770000081
Figure BDA0002231696770000082
由表中可以看出：
涂布隔离层后承印层的表面能不会下降，PVC复合膜印刷后无变形，indigo印刷后图像转印完全，无缺失，牢度高。

Claims (9)

1.一种印刷用PVC复合膜材料，其特征在于，所述复合膜材料包括PVC基材层(3)、依次设置在基材层之上的隔离层(2)和承印层(1)；
所述隔离层(2)的涂料按照重量份数计由如下原料制成：
水溶性树脂10-50重量份
硅溶胶10-50重量份
水10-50重量份
乙醇5-20重量份
消泡剂1-10重量份
表面活性剂0.1-10重量份。
2.根据权利要求1所述的印刷用PVC复合膜材料，其特征在于，所述承印层的涂料按照重量份数计由如下原料制成；
水分散性树脂乳液10-50重量份，
抗静电剂1-10重量份，
乙醇10-50重量份，
消泡剂1-20重量份，
表面活性剂1-10重量份。
3.根据权利要求1或2所述的印刷用PVC复合膜材料，其特征在于，所述隔离层中水溶性树脂与增塑剂的溶度参数差≥5(J./cm3)0.5，优选≥10(J/cm3)0.5。
4.根据权利要求3所述的印刷用PVC复合膜材料，其特征在于，所述隔离层的厚度为0.1-100μm。
5.根据权利要求4所述的印刷用PVC复合膜材料，其特征在于，所述水溶性树脂为聚乙烯吡咯烷酮、聚乙烯醇、羟乙基纤维素、水溶性淀粉中的一种或其混合物，优选聚乙烯醇。
6.根据权利要求5所述的印刷用PVC复合膜材料，其特征在于，所述硅溶胶胶体粒子平均粒径＜100nm，优选胶体粒子平均粒径＜30nm。
7.根据权利要求6所述的印刷用PVC复合膜材料，其特征在于，所述承印层的厚度为0.1-10μm。
8.根据权利要求7所述的印刷用PVC复合膜材料，其特征在于，所述水分散性树脂乳液为丙烯酸乳液、聚氨酯乳液、苯丙乳液、乙烯共聚物乳液、丙烯酸共聚物乳液等物质中的一种或几种组成。
9.根据权利要求8所述的印刷用PVC复合膜材料，其特征在于，所述PVC基材层厚度为50-500μm。
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