CN105949984B - 通用型聚酯薄膜用在线涂布液及其制作方法 - Google Patents

通用型聚酯薄膜用在线涂布液及其制作方法 Download PDF

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CN105949984B
CN105949984B CN201610349903.XA CN201610349903A CN105949984B CN 105949984 B CN105949984 B CN 105949984B CN 201610349903 A CN201610349903 A CN 201610349903A CN 105949984 B CN105949984 B CN 105949984B
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朱斌
秦志凤
刘全
姬康元
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JIANGSU YUXING FILM TECHNOLOGY CO LTD
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Abstract

本发明涉及一种通用型聚酯薄膜用在线涂布液，按质量百分比，包括15～30％水溶性的主体树脂、3～5％的固化剂、0.01～0.1％的附着力促进剂、0.01～0.1％的润湿剂、0.1～1％的纳米助剂以及余量的去离子水或纯水，主体树脂为封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂的比例在1:1:1的混合物，附着力促进剂为硅烷偶联剂，纳米助剂为无机纳米氧化物分散在水相介质中形成的分散液。本发明能有效的提高聚酯薄膜与功能化涂层的粘结力，通过在线涂布后得到的聚酯薄膜，粘结力高且通用，可同时满足印刷、喷绘、复合、镀铝、IMD、扩散、增亮、硬化对聚酯薄膜附着力的要求。

Description

通用型聚酯薄膜用在线涂布液及其制作方法
技术领域
本发明涉及一种通用型聚酯薄膜用在线涂布液及其制作方法，属于聚酯薄膜在线涂布技术领域。
背景技术
聚酯薄膜表面结晶度高，表面能低，导致涂层分子难以渗透入膜内，也使其不易与涂层形成良好的界面粘接，即使通过常规电晕处理，仍然无法满足后道涂层对高附着力的要求。为了赋予薄膜某些特定的功能，满足市场需求，在线涂布技术孕育而生。通过在聚酯薄膜生产过程中，将涂布液涂覆在薄膜表面，干燥后得到的底涂可以提高薄膜对后续涂层的粘结力，扩大了聚酯薄膜的应用领域，实现了其功能化。
在线涂布技术的关键在于在线涂布液，目前在线涂布液各不相同，针对领域也比较单一。由于后道涂层的制造水平和产品种类繁多，而且为了实现功能化，涂层中常常会引入功能性填料、助剂，严重降低了粘结力，丰富多样的功能化涂层以及苛刻环境要求对于聚酯薄膜粘结力提出了的严峻挑战。目前聚酯薄膜往往存在很多这样的问题：粘结力力可以满足印刷却无法满足扩散、增亮；可以满足增亮、硬化却无法满足复合、镀铝；可以满足IMD中个别油墨却无法满足大众油墨；无法直接满足后道涂层，需要后道涂层配方上多次调整等。CN102757739A公开的《通用型预涂膜》，预涂膜包括依次结合在一起的基材、中间层、热熔胶层和增粘层，基材为双向拉伸塑料薄膜，中间层为聚乙烯亚胺，增粘层为具有热敏性或压敏性的水性胶粘剂，因此预涂膜的通用只是针对于提高印刷油墨类的粘结力，而对于其他应用领域未涉及。而CN103740251A公开的《一种光学聚酯薄膜用高附着力水性涂布液》，该水性涂布液包括了2～15wt％树脂、0.01～5wt％纳米级细微粒子、0.001～0.05wt％润湿剂以及pH调节剂和余量为去离子水，该在线涂布液的粘结力针对光学薄膜领域的扩散、增亮、硬化等，但对于其他领域也未涉及。因此现有的在线涂布液可以满足针对领域的附着力要求，但是很难做到通用。
发明内容
本发明的目的是提供一种能有效的提高聚酯薄膜与功能化涂层的粘结力，适用性广的通用型聚酯薄膜用在线涂布液及其制作方法。
本发明为达到上述目的的技术方案是：一种通用型聚酯薄膜用在线涂布液，其特征在于：按质量百分比，包括15～30％水溶性的主体树脂、3～5％的固化剂、0.01～0.1％的附着力促进剂、0.01～0.1％的润湿剂、0.1～1％的纳米助剂以及余量的去离子水或纯水，其中，所述水溶性的主体树脂为封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂的混合物，所述的混合比例为1:1:1，附着力促进剂为硅烷偶联剂，纳米助剂为无机纳米氧化物分散在水相介质中形成的分散液。
其中：所述封闭型异氰酸酯树脂的分子量在20000～30000，NCO含量为5～10％，树脂固含量为28～30％。
所述聚酯树脂的分子量在10000～20000，羟值为5～10mgKOH/g，树脂固含量为28～30％。
所述丙烯酸树脂的分子量在15000～25000，羟值为10～15mgKOH/g，树脂固含量为28～30％。
所述固化剂为三聚氰胺树脂或聚异氰酸酯树脂的一种或两种混合物。
所述的润湿剂为BYK347、BYK348或BYK349中的一种或任意两种以上的混合物。
所述的附着力促进剂为硅烷偶联剂KH550或KH560的其中一种或两种混合物。
所述的纳米助剂为纳米SiO2、TiO2、ZnO或Al2O3分散液的一种或任意两种以上的混合物，且纳米助剂的粒径在50～200nm。
本发明通用型聚酯薄膜用在线涂布液的制备方法，其特征在于采用以下步骤：
⑴、先将封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂分别用1/5～1/4的去离子水或纯水稀释后，再混合搅拌25～35min混合均匀，制得水溶性的主体树脂；
⑵、在对主体树脂搅拌过程中分别缓慢加入润湿剂、附着力促进剂和纳米助剂，继续搅拌25～35min混合均匀；
⑶、向混合液内缓慢加入固化剂，最后加入剩余去离子水或纯水后继续搅拌0.5～1.5h即得到通用型聚酯薄膜用在线涂布液。
本发明水溶性的主体树脂采用封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂，并将封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂按1:1:1比例的共混，通过主体树脂中的-NCO、-OH及-COOH基团的交联反应，使制得在线涂布液能适应后道涂层的种类繁多；同时加入高官能度三聚氰胺树脂或聚异氰酸酯树脂作为固化剂，使其形成三维高交联密度结构，使得涂层的粘结力大幅提升，获得高耐水性、耐溶剂性、耐热性等特性。本发明在线涂布液采用硅烷偶联剂作为附着力促进剂，利用其水解特性，产生烷氧基与PET基材表面结合，另一端活性基团与主体树脂结合，作为架桥作用使得涂层更加致密，进一步提高粘结力，特别是耐湿热等苛刻环境下的粘结力。本发明通过纳米助剂改善涂层的耐溶剂性及耐水性，并能大幅提升后道涂层的附着力。本发明通过润湿剂能极大的降低了在线涂布液的表面张力，使其可以在PET表面形成良好的铺张，烘干后涂层连续致密，而具有较好的附着力。用本发明的涂布液在线涂布后得到的聚酯薄膜，粘结力高且通用，能同时满足印刷、喷绘、复合、镀铝、IMD、扩散、增亮、硬化对聚酯薄膜附着力的要求，能有效的提高聚酯薄膜与功能化涂层的粘结力，当涂覆有本发明的在线涂布液的聚酯薄膜，能对后道功能化涂层的通用性高，不需要后道涂层配方过多的调整来满足附着力要求。
具体实施方式
本发明的通用型聚酯薄膜用在线涂布液，按质量百分比，包括15～30％水溶性的主体树脂、3～5％的固化剂、0.01～0.1％的附着力促进剂、0.01～0.1％的润湿剂、0.1～1％的纳米助剂以及余量的去离子水或纯水，其中，水溶性的主体树脂为封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂的混合物，混合比例为1:1:1，该混合比例按质量份数，附着力促进剂为硅烷偶联剂，纳米助剂为无机纳米氧化物分散在水相介质中形成的分散液。
本发明封闭型异氰酸酯树脂的分子量约20000～30000，NCO含量为5～10％，树脂固含量为28～30％，该封闭型异氰酸酯树脂为水溶性聚氨酯树脂，结构中含有封闭型异氰酸酯官能团，在常温下液态，能与水任意比例互溶。本发明聚酯树脂的分子量在10000～20000，羟值为5～10mgKOH/g，树脂固含量为28～30％，该聚酯树脂为水溶性聚酯树脂，结构中含有羧基官能团，上述在常温下液态，能与水任意比例互溶。本发明丙烯酸树脂的分子量在15000～25000，羟值为10～15mgKOH/g，树脂固含量为28～30％，丙烯酸树脂为水溶性丙烯酸树脂，结构中含有羟甲基、羧基官能团，在常温下液态，能与水任意比例互溶，本发明的在线涂布液涂在聚酯薄膜经热处理后，通过主体树脂中-NCO、-OH、-COOH基团的交联反应，形成较多的强极性基团，与后道涂层形成较强的化学吸引力，同时丙烯酸树脂引入双键，可针对后道Uv固化提高粘接力，使得在线涂布液能适应后道涂层的种类繁多。发明的固化剂采用三聚氰胺树脂或/和聚异氰酸酯树脂，使其形成三维高交联密度结构，而大幅提升涂层的粘结力，获得高耐水性、耐溶剂性、耐热性等性能。本发明的附着力促进剂为硅烷偶联剂，附着力促进剂为硅烷偶联剂KH550或KH560的其中一种或两种混合物，利用其水解特性，产生烷氧基与PET基材表面结合，另一端活性基团与主体树脂结合，作为架桥作用使得涂层更加致密，进一步提高粘结力，特别是耐湿热等苛刻环境下的粘结力。本发明的纳米助剂为纳米SiO2、TiO2、ZnO、Al2O3的一种或两种以上的混合物，且纳米助剂的粒径在50～200nm，通过纳米助剂改善涂层的耐溶剂性及耐水性，且在涂层表面形成凹凸粗糙度可以大幅提升后道涂层的附着力。本发明的润湿剂为BYK347、BYK348或BYK349中的一种或任意两种以上的混合物，极大的降低了在线涂布液的表面张力，使其可以在PET表面形成良好的铺张，烘干后涂层连续致密，附着力佳。
本发明的通用型聚酯薄膜用在线涂布液的具体组分及质量百分比见表1。
表1
本发明通用型聚酯薄膜用在线涂布液的制备方法，采用以下步骤：
⑴、先将封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂分别用1/5～1/4的去离子水或纯水稀释后，具体添加量见表1所示，再混合搅拌25～35min制得水溶性的主体树脂。
⑵、在对主体树脂搅拌过程中分别缓慢加入润湿剂、附着力促进剂和纳米助剂，继续搅拌25～35min混合均匀，制得混合液。
⑶、向混合液内缓慢加入固化剂，最后加入剩余去离子水或纯水后继续搅拌0.5～1.5h即得到通用型聚酯薄膜用在线涂布液。
刮涂施工，在聚酯薄膜纵向拉伸之后，横向拉伸之前，用涂布机模头将配制好在线涂布液喷涂在经过3.0～3.5倍纵向拉伸后的聚酯薄膜的膜面上，可喷在一面或两面，再通过线棒精确计量进行刮涂，将涂布液均匀涂覆在膜面上，将涂布后的聚酯薄膜在90-130℃的温度下进行横拉预热后，再经100-150℃温度、3-5倍的横向拉伸倍率下进行横向拉伸，聚酯薄膜经190-240℃的条件下进行烘干固化和热定型处理，最后经30-110℃冷却后牵引收卷，经过拉伸烘干固化后可以得到80～200nm的涂层。
采用表2中的组份按质量百分比作为对比例制得涂布液。
表2
将本发明制得的各实施例涂布液涂布在聚酯薄膜以及将各对比文例中的涂布液涂布在聚酯薄膜后，用百格法GB/T 9286-1998测试后道印刷、喷绘、IMD、扩散、增亮、硬化用油墨的附着力；用剥离强度试验法GB/T 2790-1995测试在复合中，与Eva膜的剥离强度或与PU胶的剥离强度；用胶带法QY/HNDP31-2001测试真空镀铝铝层的附着力，聚酯薄膜的性能测试结果见表3。
表3
从表3可以看出，采用本发明的通用型聚酯薄膜用在线涂布液，通过在线涂布后得到的聚酯薄膜，粘结力高且通用，可同时满足印刷、喷绘、复合、镀铝、IMD、扩散、增亮、硬化对聚酯薄膜附着力的要求，能有效的提高聚酯薄膜与功能化涂层的粘结力。

Claims (8)

1.一种通用型聚酯薄膜用在线涂布液，其特征在于：按质量百分比，包括15～～30％水溶性的主体树脂、3～5％的固化剂、0.01～0.1％的附着力促进剂、0.01～0.1％的润湿剂、0.1～1％的纳米助剂以及余量的去离子水或纯水，其中，所述水溶性的主体树脂为封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂的混合物，按质量比，所述的混合比例为1:1:1，附着力促进剂为硅烷偶联剂，纳米助剂为无机纳米氧化物分散在水相介质中形成的分散液，所述固化剂为三聚氰胺树脂或聚异氰酸酯树脂的一种或两种混合物。
2.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述封闭型异氰酸酯树脂的分子量在20000～30000，NCO含量为5～10％，树脂固含量为28～30％。
3.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述聚酯树脂的分子量在10000～20000，羟值为5～10mgKOH/g，树脂固含量为28～30％。
4.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述丙烯酸树脂的分子量在15000～25000，羟值为10～15mgKOH/g，树脂固含量为28～30％。
5.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述的润湿剂为BYK347、BYK348或BYK349中的一种或任意两种以上的混合物。
6.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述的附着力促进剂为硅烷偶联剂KH550或KH560的其中一种或两种混合物。
7.根据权利要求1所述的通用型聚酯薄膜用在线涂布液，其特征在于：所述的纳米助剂为纳米SiO2、TiO2、ZnO或Al2O3分散液的一种或任意两种以上的混合物，且纳米助剂的粒径在50～200nm。
8.根据权利要求1所述的通用型聚酯薄膜用在线涂布液的制备方法，其特征在于采用以下步骤：
⑴、先将封闭型异氰酸酯树脂、聚酯树脂和丙烯酸树脂分别用1/5～1/4的去离子水或纯水稀释后，再混合搅拌25～35min制得水溶性的主体树脂；
⑵、在对主体树脂搅拌过程中分别缓慢加入润湿剂、附着力促进剂和纳米助剂，继续搅拌25～35min混合均匀；
⑶、向混合液内缓慢加入固化剂，最后加入剩余去离子水或纯水后继续搅拌0.5～1.5h即得到通用型聚酯薄膜用在线涂布液。
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