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CN112143013B - Mlcc陶瓷生片载体用基膜及其制造方法，以及载体膜 - Google Patents

Mlcc陶瓷生片载体用基膜及其制造方法，以及载体膜 Download PDF

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CN112143013B
CN112143013B CN202011063754.3A CN202011063754A CN112143013B CN 112143013 B CN112143013 B CN 112143013B CN 202011063754 A CN202011063754 A CN 202011063754A CN 112143013 B CN112143013 B CN 112143013B
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陈国刚
方隽云
钱荣
王岩
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Zhejiang Jiemei Electronic and Technology Co Ltd
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Abstract

本发明属于薄膜制造技术领域，涉及一种适用于MLCC陶瓷生片载体的基膜及其制造方法，以及载体膜，其中，基膜包括：基材和形成于基材的离型处理面上的涂层，涂层的表面粗糙度Ra为5‑15nm，且Rz小于150nm，涂层由含有颗粒的涂布液固化而成。本发明可以均匀稳定控制表面粗糙度，使得基膜的离型处理面的表面粗糙度Ra为5‑15nm，Rz小于150nm，高平整度表面使得后续的离型层涂性优异，制成的离型膜平整光滑无缺陷，适用于MLCC陶瓷生片载体，特别是1μm以下厚度陶瓷生片的流延成型载体用。

Description

MLCC陶瓷生片载体用基膜及其制造方法，以及载体膜
技术领域
本发明属于薄膜制造技术领域，涉及一种适用于MLCC陶瓷生片载体的基膜及其制造方法，以及带有该基膜的载体膜。
背景技术
MLCC陶瓷生片载体是指用于陶瓷浆料流延成型生片之载体，一般由聚酯薄膜基材（基膜）和其一面上涂的离型层组成。基膜的性能直接影响涂离型层的成型性，继而影响陶瓷生片载体的整体性能。特别是薄膜化陶瓷生片的制造，对载体的要求越来越高，相应的对基膜的要求也越来越严苛。现有技术中，基膜一般为采取A\B\A三层结构的BOPET薄膜。其中，表层A使用包含颗粒的母切片，并且通过控制颗粒的粒径以达到控制基膜的离型涂面(其中一个A层表面)Ra值。
公开号为CN 111267451A的专利提供一种高容量积层陶瓷电容器用剥离薄膜及其制造方法，其基膜为采用3层共挤技术成型的聚酯膜，其中中间层采用回收聚酯树脂，两个表层的聚酯树脂内均加入了SiO2以增加滑性，减少聚酯膜生产时的擦伤、刮伤现象。但在表层的聚酯树脂内添加颗粒，难以避免存在颗粒团聚的问题，造成表层Ra难以均匀稳定控制，存在大粒径的粒子，造成该位置点陶瓷浆料片厚度偏差大，导致Rz值大于10倍的Ra值，甚至产生部分点缺的情况，不利于后续离型层的涂以及陶瓷生片浆料的流延。
公开号为CN111295272A的专利公开了一种陶瓷生片制造用脱模膜，其基膜的一面上通过在线涂方式设置了包含颗粒的易滑涂层，从而实现生片的薄膜化，同时具备防止针孔、部分厚度不均，减少解卷带电。但仍会存在薄膜的离型处理面的表面粗糙度问题，影响后续离型涂层的附着力以及涂性，造成陶瓷生片浆料流延的不均匀性。
发明内容
为解决以上技术问题，首先，本发明提供一种MLCC陶瓷生片载体用基膜，该基膜的离型涂面平整度高，其表面粗糙度Ra为5-15nm，Rz小于150nm，适用于成型1μm以下厚度的陶瓷生片载体用。
技术方案如下：
一种MLCC陶瓷生片载体用基膜，包括：基材和形成于基材的离型处理面上的涂层，涂层的表面粗糙度Ra为5-15nm，且Rz小于150nm，涂层由含有颗粒的涂布液固化而成。
本方案中，颗粒以涂层的方式涂布于基膜表面，既不会带来现有技术中直接将颗粒加入到高分子层中带来的问题，又可以有效控制了基膜离型处理面的表面粗糙度，获得高平整度的基膜，使其完全达到MLCC薄膜化陶瓷生片载体膜的使用要求。
更进一步地，所述涂布液包括主体树脂、固化剂、颗粒和润湿剂，其中，所采用的主体树脂为水性的聚氨酯树脂或者水性丙烯酸树脂，固含量10~60wt%。
进一步地优选，水性丙烯酸树脂，分子量10000-50000，优选15000-30000，在该范围内涂布液稳定性好，不容易破乳析出。
作为优选，所述涂布液采用的固化剂为环氧类固化剂，与主体树脂交联固化反应，增加基膜的硬度，减少弹性形变，当薄膜开卷时压力变小，不易产生静电。
进一步地优选，固化剂添加比例为涂布液总量的0.2~1.2wt%，优选0.25~0.6wt%。
作为优选，涂层中颗粒为SiO2颗粒，粒径为50~200nm。
进一步地优选，颗粒的添加量为涂布液固含量的0.3~4.5wt%。
作为优选，所述涂层所采用的润湿剂选择有机硅类润湿剂或氟系润湿剂，添加量为涂布液的1wt%以内。优选有机硅类润湿剂，相对润湿效果更好，起泡性更低，可保证涂均匀性，如BYK系列润湿剂。
作为优选，所述涂层的厚度（干厚）为50到200nm。
作为优选，基材包括：
A层：成分为聚酯树脂，其外侧面为离型处理面；
B层：位于A层内侧，成分为聚酯树脂；
C层：位于B层内侧，成分为聚酯树脂和500-3000ppm的粒径为1~4μm粒子。
上述技术方案中，A层为不直接添加颗粒，避免了颗粒团聚造成表层Ra难以均匀稳定控制的问题，也解决了颗粒团聚造成陶瓷浆料片厚度偏差大，导致Rz值大于10倍的Ra值，甚至产生部分点缺的技术问题。
但是不添加颗粒，无法增加膜面的爽滑性，为此，本方案中，颗粒以涂层的方式涂于A层表面，既不会带来现有技术中直接将颗粒加入到A层中带来的问题，又可以有效控制了基膜离型处理面的表面粗糙度，获得高平整度的基膜，使其完全达到MLCC薄膜化陶瓷生片载体膜的使用要求。
上述技术方案中，基膜的非离型处理面C层中添加500~3000ppm的粒径为1~4μm粒子，增加基膜的爽滑性，保证后续离型层涂覆和陶瓷生片生产时卷绕的解卷性，不对接触面造成划伤。
作为优选，C层中的粒子为SiO2或者CaCO3颗粒，
作为优选，基膜的总厚度为20~50μm，A、C层分别占总厚度的8~25%，B层占总厚度的50~84%。
作为优选，B层中的聚酯树脂为70~90wt%新的聚酯树脂和30-10wt%回收聚酯树脂，在减轻环境负担的情况下，易于控制基膜的平整性和粗糙度。
本发明还提供上述基膜的制备方法，包括如下步骤：
S-1．铸片：形成A、B、C三层复合结构；
S-2．MD拉伸：在80~100℃的拉伸温度下，纵向拉伸3~4倍；
S-3．在线涂：在A层的离型处理面上进行在线涂，形成涂层；
S-4．TD拉伸：在100~140℃的工艺条件下，完成涂层的烘干和PET膜片的预热，横向拉伸3~4倍；
S-5．热处理：在230℃-240℃的温度下完成涂层的固化和基膜的热定型。
通过上述条件制得基膜，C层Ra为25~50nm，增加爽滑性，防止后续处理过程产生划伤，便于收卷、解卷； A层离型处理面Ra在5-15nm之间，且Rz小于150nm，SiO2颗粒分散均匀性优异。此基膜在A层表面涂离型剂后制得的载体膜可满足5μm以下、特别是1μm以下厚度陶瓷生片的流延成型载体用。
本发明还提供一种用于MLCC陶瓷生片的载体膜，包括上述基膜，在基膜A层的离型处理面上涂离型剂后制得，可满足5μm以下、特别是1μm以下厚度陶瓷生片的流延成型载体用。
本发明具有如下的有益效果：
本发明可以均匀稳定控制表面粗糙度，使得基膜的离型处理面的表面粗糙度Ra为5-15nm，Rz小于150nm，高平整度表面使得后续的离型层涂性优异，制成的离型膜平整光滑无缺陷，适用于MLCC陶瓷生片载体，特别是1μm以下厚度陶瓷生片的流延成型载体用。
具体实施方式
以下是对本发明的较佳实施例进行说明，对本发明的技术方案作进一步的描述，但下述实施例只是本发明中的较佳实施例而非限制本发明。
本发明提供的一种MLCC陶瓷生片载体用基膜，包括：
A层：成分为聚酯树脂，其外侧面为离型处理面；
B层：位于A层内侧，成分为聚酯树脂；
C层：位于B层内侧，成分为聚酯树脂和500-3000ppm的粒径为1~4μm粒子；
涂层：形成于A层的离型处理面上，所述涂层的成分包括主体树脂、固化剂、SiO2颗粒和润湿剂的水性分散液。
各实施例与对比例的各层的组合物组成见下表1；
并对各实施例与对比例所得基膜进行性能检测，结果见表2。
基膜成品良率：
成品卷外观平整性，无凸点、条纹等缺陷为良品，其余为不良品。
离型层成型性：
在制得基膜上进行离型剂涂布，干燥固化后得到载体膜。通过强光下目视判定：
○：离型膜外观均匀，无涂花斑、细划伤
△：有微量涂花斑。
×：涂外观均匀性差，有少量花斑的发生，且膜面有少量划伤。
陶瓷生片成型性：
于载体膜离型层上涂陶瓷浆料，以90℃干燥1分钟后，制得厚度为0.5μm的陶瓷生片。在得到的陶瓷生片的薄膜宽度方向的中央区域，从陶瓷浆料的涂面的相反面照射光，观察光透射而可见的针孔的发生情况，以下述基准进行目视判定。
○：无针孔的发生，厚度不均没有特别问题
△：稍有针孔的发生，稍可见厚度不均。
×：有少量针孔的发生、和厚度不均稍显眼。
表1 各实施例与对比例的各层的组成
Figure DEST_PATH_IMAGE002
表2 各实施例与对比例所得基膜进行性能检测
Figure DEST_PATH_IMAGE004

Claims (9)

1.一种MLCC陶瓷生片载体用基膜，其特征在于，包括：基材和形成于基材的离型处理面上的涂层，涂层的表面粗糙度Ra为5-15nm，且Rz小于150nm，
所述涂层由包括主体树脂、固化剂、颗粒和润湿剂涂布液固化而成；其中，所采用的主体树脂为水性的聚氨酯树脂或者水性丙烯酸树脂，固含量10~60wt%，在含有涂层的离型处理面上涂离型剂制得载体膜。
2.根据权利要求1所述的一种MLCC陶瓷生片载体用基膜，其特征在于，所述涂层所采用的固化剂为环氧类固化剂，添加比例为涂布液总量的0.2~1.2wt%。
3.根据权利要求1所述的一种MLCC陶瓷生片载体用基膜，其特征在于，所述颗粒为SiO2颗粒，粒径为50~200nm。
4.根据权利要求1所述的一种MLCC陶瓷生片载体用基膜，其特征在于，所述颗粒的添加量为涂布液固含量的0.3~4.5wt%。
5.根据权利要求1所述的一种MLCC陶瓷生片载体用基膜，其特征在于，所述涂层的干厚为50到200nm。
6.根据权利要求1所述的一种MLCC陶瓷生片载体用基膜，其特征在于，所述基材包括：
A层：成分为聚酯树脂，其外侧面为离型处理面；
B层：位于A层内侧，成分为聚酯树脂；
C层：位于B层内侧，成分为聚酯树脂和500-3000ppm的粒径为1~4μm粒子。
7.根据权利要求6所述的一种MLCC陶瓷生片载体用基膜，其特征在于，B层中的聚酯树脂为70~90wt%新的聚酯树脂和10-30wt%回收聚酯树脂。
8.如权利要求6所述的一种MLCC陶瓷生片载体用基膜的制备方法，其特征在于，包括如下步骤：
S-1．铸片：形成A、B、C三层复合结构；
S-2．MD拉伸：在80~100℃的拉伸温度下，纵向拉伸3~4倍；
S-3．在线涂布：在A层的离型处理面上进行在线涂布，形成涂层；
S-4．TD拉伸：在100~140℃的工艺条件下，完成涂层的烘干和膜片的预热，横向拉伸3~4倍；
S-5．热处理：在230℃-240℃的温度下完成涂层的固化和基膜的热定型。
9.一种用于MLCC陶瓷生片的载体膜，包含权利要求1所述的MLCC陶瓷生片载体用基膜。
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