CN110920168B - 一种双层聚酯薄膜及覆膜金属板 - Google Patents

一种双层聚酯薄膜及覆膜金属板 Download PDF

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Publication number
CN110920168B
CN110920168B CN201811090600.6A CN201811090600A CN110920168B CN 110920168 B CN110920168 B CN 110920168B CN 201811090600 A CN201811090600 A CN 201811090600A CN 110920168 B CN110920168 B CN 110920168B
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China
Prior art keywords
copolyester
film
layer
polyester film
mass
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CN201811090600.6A
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CN110920168A (zh
Inventor
谢龙
陈红星
戴竞舸
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to CN201811090600.6A priority Critical patent/CN110920168B/zh
Priority to EP19862314.2A priority patent/EP3854582A4/en
Priority to US17/278,052 priority patent/US20210379868A1/en
Priority to PCT/CN2019/106483 priority patent/WO2020057557A1/zh
Publication of CN110920168A publication Critical patent/CN110920168A/zh
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Publication of CN110920168B publication Critical patent/CN110920168B/zh
Priority to PH12021550588A priority patent/PH12021550588A1/en
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Abstract

本发明公开一种双层聚酯薄膜，为上下两层结构，上下两层中的每一层包括共聚聚酯和其它树脂，为所述共聚聚酯与所述其它树脂的均匀混合物，共聚聚酯包括通过原位聚合加入质量份数为1200ppm的SiO2。共聚聚酯为间苯二甲酸、1/4‑环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯。本发明能制备出厚度较薄的聚酯薄膜。聚酯薄膜与金属板热粘合性优、耐深冲加工和复杂变形加工性优、耐腐蚀性优等诸多优点，可广泛用于金属包装行业。

Description

一种双层聚酯薄膜及覆膜金属板
技术领域
本发明涉及金属包装用覆膜金属板领域，具体地涉及一种双层聚酯薄膜及覆膜金属板。
背景技术
在金属制罐行业，传统做法是通过将金属板表面进行涂装处理后再进行制罐加工成型，其中，涂装处理所采用的溶剂型涂料含有双酚A类的非食品安全物质，且涂装过程由于大量溶剂挥发导致环保问题和大量能耗。近年来，行业内一直致力于寻找合格的新材料以克服上述难题。
覆膜铁是将柔性聚酯薄膜与金属板通过热熔方式直接粘合在一起，可以满足下游用户的制罐成型加工、差异化的印刷需求、多种内容物的灌装以及耐酸碱盐等高温杀菌方式、长时间的货架保存期。
随着环保政策趋严和人们对食品安全的关注度提升，覆膜铁作为一种环保高性能新材料在制罐行业的关注度也越来越高，近年来已经有一部分企业的覆膜铁产品进入市场应用。为满足不同用途的差异化需求，需要对聚酯薄膜的原料和膜层结构进行优化设计，以达到下游各工序的不同要求。
公开号为CN1839036的专利申请公开了一种覆膜金属板及其使用的拉拔罐，该专利以双层膜薄膜与金属薄板覆合，容易在制罐成型过程中产生分层、脱落等缺陷，其采用的乙烯基离聚物作为中间粘接层，在灌装高温杀菌时性能不良。
公开号为CN102432984 A的专利申请公开了一种流延聚酯薄膜及其使用的金属板合金属罐，该专利采用单层聚酯薄膜与金属薄板覆合，因阻隔抗性的能力不足，容易导致所制备的金属罐在灌装时耐酸碱盐高温杀菌时性能不良。
公告号为CN 106142782 B的专利公开了一种用于覆铁热封聚酯薄膜及其制备方法，该专利特点在于以三层结构的聚酯薄膜与金属薄板覆合，因该薄膜的性能受限于其高结晶的下表层而导致加工成型性能不足，不适合用于深冲和复杂变形方式用途。
公开好为CN102463725 A的专利申请公开了一种聚酯薄膜及其制备方法，该专利的聚酯薄膜为三层(ABA)结构用在电子标签领域，其特点在于两个表层为相同树脂，很难同时满足与金属板粘合、与模具接触满足成型加工、与罐内内容物接触等多种性能需求，容易导致性能兼顾困难而顾此失彼，不适合用于制罐行业。
现有技术中，满足覆膜金属板深冲加工需求的单层薄膜在灌装耐酸碱盐高温杀菌性能欠缺，满足灌装耐酸碱盐高温杀菌需求多层薄膜又不能达到深冲加工需求；传统的双层薄膜在深加工成型时容易导致薄膜的层间剥离。传统的薄膜中采用含硅切片母粒方式加入开口剂，导致薄膜中的树脂种类过于多样化，不适合用于深冲加工。
发明内容
本发明的目的是提供一种双层聚酯薄膜以及覆膜金属板，可满足深冲和复杂变形要求的食品饮料包装用金属容器的性能需求。
为了实现上述目的，本发明采用以下技术方案。
根据本发明的一个方面，提供一种双层聚酯薄膜，所述双层聚酯薄膜分为上下两层，所述上下两层中的每一层包括共聚聚酯和其它树脂，为所述共聚聚酯与所述其它树脂的均匀混合物，所述共聚聚酯包括通过原位聚合加入质量份数为1200ppm的SiO2。
根据本发明的一个方面的双层聚酯薄膜中，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，
根据本发明的一个方面的双层聚酯薄膜中，所述其它树脂选自均聚聚酯树脂、含钛白粉母粒聚酯树脂、以及均聚聚酯树脂和金色聚酯母粒树脂的混合物中的一种。
根据本发明的一个方面的双层聚酯薄膜中，双层结构的聚酯薄膜采用共挤和双向拉伸法在250-280℃的温度下制成。
根据本发明的一个方面的双层聚酯薄膜中，上层薄膜中其它树脂的比例不大于40％，下层薄膜中其它树脂的比例不大于10％
根据本发明的一个方面的双层聚酯薄膜中，上层薄膜中其它树脂的比例不大于30％
较佳地，上层薄膜中其它树脂的比例不大于30％
根据本发明一个方面的应用于中高端食品饮料包装的双层聚酯薄膜的制备方法中，上层厚度为8-25μm，下层厚度为3-6μm。
较佳地，下层厚度为4-5μm。
根据本发明一个方面的应用于中高端食品饮料包装的双层聚酯薄膜的制备方法中，所述共聚聚酯的熔点在200-240℃之间。
较佳地，所述共聚聚酯的熔点在210-230℃之间。
根据本发明的另一个方面，提供一种覆膜金属板，包括金属基板和覆盖在金属基板表面上的如上所述的双层聚酯薄膜。
根据本发明的另一个方面的覆膜金属板中，所述双层聚酯薄膜在压力2～10Kg、温度180～260℃下热贴合在所述金属基板表面上。
根据本发明的另一个方面的覆膜金属板中，金属基板厚0.10～0.50mm，金属基板选自镀铬钢板、镀锡钢板、低锡钢板、镀锌钢板、冷轧钢板、或不锈钢板。
根据本发明的再一个方面，提供一种应用于中高端食品饮料包装用金属容器，所述金属容器采用如上所述的覆膜金属板制成。
与现有技术相比，本发明具有如下有益效果：本发明的双层聚酯薄膜与金属板有优异的热粘合性能，其特殊之处更在于可用于深冲加工和多种复杂变形加工方式而不会发生薄膜内分层的现象，而且本发明的双层聚酯薄膜赋予了比单层膜更优异的耐腐蚀性。
聚合物中通过原位聚合加入SiO2，从整体上均匀地改善聚酯薄膜的结晶性能；并且通过改善传统以母粒形式加入SiO2的方式，避免了高熔点树脂加入薄膜中。上述两点使聚酯薄膜的综合性能得到明显提升，包含本发明薄膜的覆膜铁的耐复杂加工性、覆膜铁的耐腐蚀性能等得到显著提高。
具体实施方式
以下在具体实施方式中通过对非限制性实施例所作的详细描述，本发明的目的、特征、和优点将变得更清楚明显，其内容足以使本领域技术人员了解和实施本发明。
实施例1
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为230℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比、熔点为230℃共聚聚酯和30％质量百分比、熔点262℃的均聚聚酯；下层薄膜90％质量百分比、熔点为230℃的共聚聚酯和10％质量百分比、熔点262℃的均聚聚酯树脂。所述共聚聚酯中含有1200ppm的SiO2。
覆膜金属板的制备：将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
根据本发明的双层聚酯薄膜包括上下两层结构，上下两层中的每一层包括共聚聚酯和其它树脂，为共聚聚酯与所述其它树脂的均匀混合物，共聚聚酯包括通过原位聚合加入质量份数为1200ppm的SiO2。
根据本发明的双层聚酯薄膜中，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，
根据本发明的双层聚酯薄膜中，所述其它树脂选自均聚聚酯树脂、含钛白粉母粒聚酯树脂、以及均聚聚酯树脂和金色聚酯母粒树脂的混合物中的一种。
采用双向拉伸法以及共挤法由共聚聚酯和其它树脂的均匀混合物形成上下两层的双层结构的聚酯薄膜。
采用共挤双向拉伸法在250-280℃的温度下制备双层结构的聚酯薄膜。
在双层结构的聚酯薄膜中，上层厚度为8-25μm，下层厚度为3-6μm。
实施例2
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃。
所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为230℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比、熔点为230℃的共聚聚酯和30％质量百分比、熔点为260℃的含钛白粉母粒聚酯树脂，所述含钛白粉母粒聚酯树脂中TiO2含量为质量百分比60％；下层薄膜95％质量百分比、熔点为230℃的共聚聚酯和5％质量百分比、熔点262℃的均聚聚酯。所述共聚聚酯中含有1200ppm的SiO2。
实施例3
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃。
所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为230℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比、熔点为230℃的共聚聚酯和30％质量百分比的其它树脂，其中所述其它树脂包括1/3质量百分比的熔点为262℃的均聚聚酯和2/3质量百分比的熔点为262℃的金色聚酯母粒树脂；下层薄膜98％质量百分比、熔点为230℃的共聚聚酯和2％质量百分比、熔点262℃的均聚聚酯树脂。所述共聚聚酯中含有1200ppm的SiO2。
实施例4
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为230℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为90％质量百分比熔点为230℃共聚聚酯和10％质量百分比的262℃的均聚聚酯；下层薄膜100％质量百分比熔点为230℃共聚聚酯。所述共聚聚酯中含有1200ppm的SiO2。
实施例5
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为230℃。所述聚酯薄膜采用上中下三层共挤法制造，上中下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，所述的三层结构中上中两层的树脂完全相同，其中上中两层薄膜中为90％质量百分比熔点为230℃共聚聚酯和10％质量百分比的262℃的均聚聚酯，其实质为一层结构；下层薄膜100％质量百分比熔点为230℃共聚聚酯。所述共聚聚酯中含有1200ppm的SiO2。
实施例6
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为200℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比熔点为200℃共聚聚酯和30％质量百分比的262℃的均聚聚酯；下层薄膜90％质量百分比熔点为200℃共聚聚酯和10％质量百分比的262℃的均聚聚酯树脂。所述共聚聚酯中含有1200ppm的SiO2。
实施例7
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为240℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比熔点为240℃共聚聚酯和30％质量百分比的262℃的均聚聚酯；下层薄膜90％质量百分比熔点为240℃共聚聚酯和10％质量百分比的262℃的均聚聚酯树脂。所述共聚聚酯中含有1200ppm的SiO2。
实施例8
一种聚酯薄膜的生产方法，所述聚酯薄膜采用双向拉伸方法制造，制造温度250-280℃，所述聚酯薄膜包括共聚聚酯和其它树脂，所述共聚聚酯为间苯二甲酸、1/4-环己烷二甲醇、新戊二醇进行共聚改性的PET聚酯，且熔点为210℃。所述聚酯薄膜采用共挤法制造，薄膜包括上下两层，上下两层均为均匀混合的所述共聚聚酯与所述其它树脂的混合物，其中上层薄膜中为70％质量百分比、熔点为210℃的共聚聚酯和30％质量百分比的262℃的均聚聚酯；下层薄膜90％质量百分比、熔点为210℃的共聚聚酯和10％质量百分比的262℃的均聚聚酯树脂。所述共聚聚酯中含有1200ppm的SiO2。
在上述八个实施例中，通过共聚聚酯和其它树脂共混后制备成上下两层结构的薄膜，在流延法制膜和双向拉伸法制膜的成型性都良好，能制备出厚度较薄的聚酯薄膜。所述聚酯薄膜与金属板热粘合性优、耐深冲加工和复杂变形加工性优、耐腐蚀性优等诸多优点，可广泛用于金属包装行业。
通过在共聚聚酯中通过原位合成加入SiO2，因没有在聚酯薄膜中使用普通的含硅聚酯切片，避免了多种聚酯树脂(熔点大于245℃)的介入，不仅达到了开口剂的基本需求，同时有利于明显提升薄膜的综合性能。
最后，需要指出的是，虽然本发明已参照当前的具体实施例来描述，但是本技术领域中的普通技术人员应当认识到，以上的实施例仅是用来说明本发明，而并非用作为对本发明的限定，在不脱离本发明构思的前提下还可以作出各种等效的变化或替换，因此，只要在本发明的实质精神范围内对上述实施例的变化、变型都将落在本发明的权利要求书范围内。

Claims (10)

1.一种双层聚酯薄膜，其特征在于：所述双层聚酯薄膜分为上下两层，所述上下两层中的每一层包括共聚聚酯和均聚聚酯，所述共聚聚酯与所述均聚聚酯均匀混合，所述共聚聚酯包括通过原位聚合加入质量份数为1200ppm的SiO2，
所述共聚聚酯为间苯二甲酸、1,4-环己烷二甲醇和新戊二醇进行共聚改性的PET聚酯；
其中，上层薄膜中共聚聚酯的质量百分比为70%，均聚聚酯的质量百分比为30%；
下层薄膜中共聚聚酯的质量百分比为90%，均聚聚酯的质量百分比为10%，或者下层薄膜中共聚聚酯的质量百分比为95%，均聚聚酯的质量百分比为5%，或者下层薄膜中共聚聚酯的质量百分比为98%，均聚聚酯的质量百分比为2%。
2.如权利要求1所述的双层聚酯薄膜，其特征在于：所述均聚聚酯还含有钛白粉母粒和/或金色聚酯母粒。
3.如权利要求1所述的双层聚酯薄膜，其特征在于：上层薄膜厚度为8-25µm，下层薄膜厚度为3-6µm。
4.如权利要求3所述的双层聚酯薄膜，其特征在于：下层薄膜厚度为4-5µm。
5.如权利要求1所述的双层聚酯薄膜，其特征在于：所述共聚聚酯的熔点在200-240℃之间。
6.如权利要求5所述的双层聚酯薄膜，其特征在于：所述共聚聚酯的熔点在210-230℃之间。
7.一种覆膜金属板，其特征在于：包括金属基板和覆盖在所述金属基板表面上的如权利要求1-6中任一项所述的双层聚酯薄膜。
8.如权利要求7所述的覆膜金属板，其特征在于：所述金属基板厚0.10~0.50mm，所述金属基板选自镀铬钢板、镀锡钢板、镀锌钢板、冷轧钢板、或不锈钢板。
9.如权利要求7所述的覆膜金属板，其特征在于：采用热熔覆合的方式将双层聚酯薄膜直接覆合到加热的金属基板表面上。
10.一种食品饮料包装用金属容器，其特征在于，所述金属容器采用如权利要求7-9之一所述的覆膜金属板制成。
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