CN110920172A - 一种聚酯覆铁膜以及覆膜金属板 - Google Patents

一种聚酯覆铁膜以及覆膜金属板 Download PDF

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CN110920172A
CN110920172A CN201811090656.1A CN201811090656A CN110920172A CN 110920172 A CN110920172 A CN 110920172A CN 201811090656 A CN201811090656 A CN 201811090656A CN 110920172 A CN110920172 A CN 110920172A
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copolyester
polyester film
film
blended polyester
homopolyester
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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 CN201811090656.1A priority Critical patent/CN110920172A/zh
Priority to ES19863378T priority patent/ES2955213T3/es
Priority to US17/277,170 priority patent/US20210371644A1/en
Priority to EP19863378.6A priority patent/EP3854584B1/en
Priority to PCT/CN2019/106467 priority patent/WO2020057553A1/zh
Publication of CN110920172A publication Critical patent/CN110920172A/zh
Priority to PH12021550586A priority patent/PH12021550586A1/en
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Abstract

本发明公开一种共混聚酯薄膜，包括共聚聚酯和均聚聚酯，由上、中、下三层构成，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，共聚聚酯包括通过原位聚合加入质量份数为800‑2000ppm的SiO2。共聚聚酯中的二元醇成份包括乙二醇、1,4‑环己烷二甲醇、1,4‑丁二醇。共聚聚酯和均聚聚酯的份数比分别为8:2、7:3、以及5:5。共聚聚酯的熔点在200‑240℃之间。本发明的共混聚酯薄膜具有优良加工性能、优良耐酸、碱等耐化学性，优良均匀性。由共混聚酯薄膜制备的覆膜金属板可以同时满足复杂成型加工和高耐蚀性的食品饮料包装用金属容器的性能需求。

Description

一种聚酯覆铁膜以及覆膜金属板
技术领域
本发明涉及金属包装用覆膜金属板领域，更具体地指一种聚酯覆铁膜以及覆膜金属板。
背景技术
近年来，聚对苯二甲酸乙二醇酯(聚酯)工业发展十分迅速，国内外已有一大批著名的生产聚酯材料及聚酯设备的公司，1987年聚酯的世界产量已跃居工程塑料的第五位，薄膜是聚酯材料应用领域中的一个重要分支，广泛应用于食品、饮料的包装领域。近年来，由于金属覆膜技术的兴起，将覆铁膜与金属板通过热熔覆合的方式相结合，克服了传统金属罐内侧必须经过涂装加工所导致的有害物质——双酚A类(Bis-phenol A)的析出问题，而这一问题已受到全球范围的高度重视。随着金属板覆膜技术的逐步推广，覆铁膜替代涂料以提升灌装的食品安全性已得到广泛认可。
现有技术中，改性聚酯薄膜用于金属包装用覆膜金属板基本可以满足各种成型要求，然而及满足成型要求又满足耐酸、碱性等耐化学性的功能性覆铁膜还存在较大的技术优化空间。
发明内容
本发明的目的是提供一种具有优良加工性能的、优良耐酸、碱等耐化学性的，优良均匀性的，采用聚酯覆铁膜制备的覆膜金属板。
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，提供一种共混聚酯薄膜，所述共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚聚酯包括通过原位聚合加入质量份数为800-2000ppm的SiO2。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯中的二元醇成份包括乙二醇、1,4-环己烷二甲醇、1,4-丁二醇。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯和所述均聚聚酯的份数比分别为8:2、7:3、以及5:5。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯的熔点在200-240℃之间。
根据本发明的一个方面的共混聚酯薄膜中，所述共混聚酯薄膜采用双向拉伸方法在250-270℃的制造温度下制备而成。
在上述方案中，在共聚聚酯中通过原位加入质量份数为800-2000ppm的SiO2，不仅达到开口剂的基板需求，同时有利于明显提升薄膜的综合性能。
根据本发明的另一个方面，提供一种覆膜金属板，其包括金属基板和覆盖在所述金属基板表面上的如上所述的共混聚酯薄膜。
根据本发明的另一个方面的覆膜金属板中，所述金属基板材料选自镀铬钢板、镀锡钢板、低锡钢板、镀锌钢板、冷轧钢板、以及不锈钢板中的一种。
根据本发明的另一个方面的覆膜金属板中，所述共混聚酯薄膜采用热熔覆合的方式在压力2～10Kg、温度180～260℃下直接热覆合到金属基板表面上。
根据本发明的另一个方面的覆膜金属板中，所述金属基板厚0.10～0.50mm。
根据本发明的再一个方面，提供一种应用于食品饮料包装用的金属容器，其由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：
本发明通过采用将共混聚酯薄膜通过热覆合的方式覆合到金属板，使得由所述共混聚酯薄膜制备的覆膜金属板可以同时满足复杂成型加工和高耐蚀性的食品饮料包装用金属容器的性能需求。由于所述聚酯覆铁膜的共聚聚酯中采用原位聚合方式加入了800-2000ppm的SiO2，没有使用普通的含硅聚酯切片，不存在高温聚酯树脂(熔点大于245℃)的介入，不仅达到了传统SiO2开口剂的基本需求，同时可明显提升薄膜的综合性能。
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。
根据本发明的共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚聚酯包括通过原位聚合加入质量份数为800-2000ppm的SiO2。
根据本发明的共混聚酯薄膜中，所述共聚聚酯中的二元醇成份包括乙二醇、1,4-环己烷二甲醇、1,4-丁二醇。
根据本发明的共混聚酯薄膜中，所述共聚聚酯和所述均聚聚酯的份数比分别为8:2、7:3、以及5:5。
根据本发明的共混聚酯薄膜中，所述共聚聚酯的熔点在200-240℃之间。
根据本发明的共混聚酯薄膜中，所述共混聚酯薄膜采用双向拉伸方法在250-270℃的制造温度下制备而成。
实施例1
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括7份共聚聚酯，3份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为200℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1300ppm的SiO2。
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。
实施例2
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括5份共聚聚酯，5份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为230℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有2000ppm的SiO2。
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。
实施例3
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括8份共聚聚酯，2份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为240℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有800ppm的SiO2。
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。
实施例4
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用流延法制造，制造温度250-270℃，所述聚酯覆铁膜包括8份共聚聚酯，2份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为220℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1500ppm的SiO2。
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。
实施例5
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用流延法制造，制造温度250-270℃，所述聚酯覆铁膜包括5份共聚聚酯，5份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为200℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1800ppm的SiO2。
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。
实施例6
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括7份共聚聚酯，3份均聚聚酯，所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇、1,4-丁二醇的混合物，且熔点为230℃，所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1300ppm的SiO2。
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。
上述六个实施例中通过共聚聚酯和均聚聚酯共混后制膜，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覆铁膜。且采用该聚酯覆铁膜制备的覆膜金属板有优良的耐冲压成型性和延伸性，以及优良的耐酸、碱性等耐化学性能。并且通过在共聚聚酯中通过原位合成加入SiO2，因没有在聚酯覆铁膜中使用普通的含硅聚酯切片，不存在高温聚酯树脂(熔点大于245℃)的介入，可以明显提升覆膜金属板综合性能的均匀性。同时，SiO2的加入有利于聚酯覆铁膜收放卷。
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。
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)

1.一种共混聚酯薄膜，其特征在于：所述共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚聚酯包括通过原位聚合加入质量份数为800-2000ppm的SiO2。
2.如权利要求1所述的共混聚酯薄膜，其特征在于：所述共聚聚酯中的二元醇成份包括乙二醇、1,4-环己烷二甲醇、1,4-丁二醇。
3.如权利要求1或2所述的共混聚酯薄膜，其特征在于：所述共聚聚酯和所述均聚聚酯的份数比分别为8:2、7:3、以及5:5。
4.如权利要求1或2所述的共混聚酯薄膜，其特征在于：所述共聚聚酯的熔点在200-240℃之间。
5.如权利要求1或2所述的共混聚酯薄膜，其特征在于：所述共混聚酯薄膜采用双向拉伸方法在250-270℃的制造温度下制备而成。
6.一种覆膜金属板，其特征在于：包括金属基板和所述金属基板表面上覆盖的如权利要求2-5中任一项所述的共混聚酯薄膜。
7.如权利要求6所述的覆膜金属板，其特征在于：所述金属基板材料选自镀铬钢板、镀锡钢板、低锡钢板、镀锌钢板、冷轧钢板、以及不锈钢板中的一种。
8.如权利要求6所述的覆膜金属板，其特征在于：所述共混聚酯薄膜采用热熔覆合的方式在压力2～10Kg、温度180～260℃下直接热覆合到金属基板表面上。
9.如权利要求6所述的覆膜金属板，其特征在于：所述金属基板厚0.10～0.50mm。
10.一种应用于食品饮料包装用的金属容器，其特征在于，所述金属容器由如权利要求6-9之一所述的覆膜金属板制成。
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