CN114645488A - 一种纸基可回收复合材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层或所述纸基层外侧从内向外还可以依次设置包括阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂12‑15份，纳米二氧化硅涂料6‑12份，柔顺剂1‑2份，稳定剂1‑2份，消泡剂1‑2份，纯化水68‑79份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3‑4份、环氧树脂12‑13份、聚四氟乙烯1‑2份、碳酸钙0.5‑1.5份。本发明阻隔性能强，水蒸气透过率、氧气透过率低，热封性能好，拉伸强度大，易于回收，各方面综合性能优越。
Description
技术领域
本发明涉及复合片材领域，具体涉及一种纸基可回收复合材料及其制备方法。
背景技术
纸张作为绿色环保的包装材料已被广泛应用于消费品领域。由于纸张的阻隔性不佳，通常需复合铝箔或塑料薄膜来实现包装的功能如阻隔及热封等特性，但铝箔及塑料等不易于降解和回收利用，不符合建立环境友好型社会的要求。故以纸基为主体的包装复合材料如何被下游厂商回收处理成为了当今社会的一大难题。
因此研究一款阻隔性能强，热封性能好，综合性能优越的纸基可回收复合材料是本领域技术人员亟待解决的技术问题。
发明内容
本发明为克服现有技术中的缺陷，提供一种纸基可回收复合材料，其阻隔性能强，水蒸气透过率、氧气透过率低，热封性能好，拉伸强度大，易于回收，各方面综合性能优越。
为实现上述目的，本发明的技术方案是提供一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂12-15份，纳米二氧化硅涂料6-12份，柔顺剂1-2份，稳定剂1-2份，消泡剂1-2份，纯化水68-79份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3-4份、环氧树脂12-13份、聚四氟乙烯1-2份、碳酸钙0.5-1.5份。
所述的纸基层采用超高压长纤木浆原纸，具有良好的阻氧及阻油性。胶粘剂层采用水性聚氨酯或聚丙烯酸酯粘合剂，绿色环保，热封层采用生物基聚乳酸材料、丙烯酸乳液，可实现生物降解。
进一步的所述纸基层外侧从内向外依次包括阻隔涂层、胶粘剂层、热封层。可采用单层纸张，通过两次串联涂布分别增加阻隔性能和热封性能。
进一步的所述柔顺剂为双聚乙烯聚二甲基硅氧烷、双十八烷基二甲基氯化铵、聚二甲基硅氧烷二季胺盐中的一种或几种。柔软剂是一类能改变材料的静、动摩擦系数的化学物质。当改变静摩擦系数时，手感触摸有平滑感，易于在材料上移动；当改变动摩擦系数时，阻隔涂层各组分之间的微细结构易于相互移动，也就是材料易于变形，增加对纸基层的亲和力，从而增加复合材料的热封性能及阻隔性能。
进一步的所述稳定剂为硬脂酸镁、二辛基琥珀酸磺酸钠、2-甲基丙烯酸环氧乙烷基甲酯中的一种或几种。能增加溶液、胶体、固体、混合物的稳定性能的化学物质都叫稳定剂，稳定剂的施加可以增强阻隔涂层各组分的相容性，增加其协同作用，促进复合材料功能的实现。
进一步的所述消泡剂为二甲基硅油、氰脲酰氯三聚氰胺、聚氧丙烯甘油醚中的一种或几种。消泡剂能降低水、溶液、悬浮液等的表面张力，防止泡沫形成，或使原有泡沫减少或消灭的物质。消泡剂的使用能够使阻隔涂层各组分均匀分布，保持体系性状稳定，增加阻隔涂层的阻隔性能。
进一步的所述纳米二氧化硅涂料粒径为7-40nm。纳米二氧化硅是一种无机化工材料，俗称白炭黑。由于是超细纳米级，尺寸范围在1-100nm，因此具有许多独特的性质。纳米二氧化硅的尺寸选择是一个关键因素，将纳米二氧化硅颗粒充分、均匀地分散到树脂材料中，可全面改善树脂基材料性能，增加了产品的密封性和阻隔性能，同时能够增加材料的力学性能。
进一步的所述胶粘剂层胶粘剂为水性聚氨酯或聚丙烯酸酯中的一种或两种。根据应用的领域不同，复合胶或压敏型胶粘剂更利于层间材料的分离及下游的回收处理工艺，可作为优选采用。
进一步的所述热封层采用聚乳酸乳液、丙烯酸乳液中的一种或两种。
本发明还提供一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用胶粘剂层通过干式复合将各层层压在一起形成复合材料。以超高压纸基作为涂布基材，并处以在线电晕、等离子处理或火焰处理对纸基层进行改性处理，从而提高纸基层的表面张力，增加纸基层的拉伸强度及阻隔性能。
本发明的优点和有益效果在于：采用该纸基复合材料具有良好的阻隔性能，可有效阻隔水汽、氧气等气体的渗透，提高包装内容物的保质期，同时具有良好的热封性能，既满足包装密封的需求，又完全符合可回收处理的要求。纸张阻隔性能提升，OTR/WVTR均可满足≤1.0的指标。复合材料通过配方以及生产工艺的改进，材料拉伸强度≥25MPa。阻隔涂层可用于制备组成两层及多层复合薄膜。胶粘剂层采用水性聚氨酯或聚丙烯酸酯类复合胶或压敏胶，工艺适应性得到提升。采用生物基材料，可实现生物降解，复合材料符合绿色环保要求。本发明成本优势明显，各方面综合性能优越，产业化能力强、质量稳定可控，具有较强的应用前景。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
实施例1
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂12份，纳米二氧化硅涂料6份，所述纳米二氧化硅涂料粒径为7nm，柔顺剂双聚乙烯聚二甲基硅氧烷1份，稳定剂硬脂酸镁1份，消泡剂二甲基硅油1份，纯化水68份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3份、环氧树脂12份、聚四氟乙烯1份、碳酸钙0.5份。所述胶粘剂层胶粘剂为水性聚氨酯，所述热封层采用聚乳酸乳液wt％：丙烯酸乳液wt％＝1:1的混合乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过在线电晕改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用水性聚氨酯胶粘剂层通过干式复合将各层层压在一起形成复合材料。
实施例2
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述纸基层外侧从内向外依次包括阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂15份，纳米二氧化硅涂料12份，所述纳米二氧化硅涂料粒径为40nm，柔顺剂双十八烷基二甲基氯化铵2份，稳定剂二辛基琥珀酸磺酸钠2份，消泡剂氰脲酰氯三聚氰胺2份，纯化水79份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷4份、环氧树脂13份、聚四氟乙烯2份、碳酸钙1.5份。所述胶粘剂层胶粘剂为聚丙烯酸酯中，所述热封层采用丙烯酸乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过等离子处理改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用聚丙烯酸酯胶粘剂层通过干式复合将各层层压在一起形成复合材料。
实施例3
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂14份，纳米二氧化硅涂料10份，所述纳米二氧化硅涂料粒径为20nm，柔顺剂聚二甲基硅氧烷二季胺2份，2-甲基丙烯酸环氧乙烷基甲酯稳定剂1.5份，消泡剂聚氧丙烯甘油醚2份，纯化水75份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷4份、环氧树脂12份、聚四氟乙烯2份、碳酸钙1份。所述胶粘剂为水性聚氨酯wt％：聚丙烯酸酯wt％＝2:1构成的胶粘剂层，所述热封层采用聚乳酸乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过火焰处理改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用水性聚氨酯wt％：聚丙烯酸酯wt％＝2:1构成的胶粘剂层通过干式复合将各层层压在一起形成复合材料。
实施例4
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂13份，纳米二氧化硅涂料8份，所述纳米二氧化硅涂料粒径为30nm，双聚乙烯聚二甲基硅氧烷wt％：双十八烷基二甲基氯化铵wt％＝5:1的柔顺剂1.5份，稳定剂二辛基琥珀酸磺酸钠1份，消泡剂二甲基硅油1份，纯化水70份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3份、环氧树脂12份、聚四氟乙烯2份、碳酸钙0.5份。所述胶粘剂层胶粘剂为水性聚氨酯，所述热封层采用丙烯酸乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过在线电晕改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用水性聚氨酯胶粘剂层通过干式复合将各层层压在一起形成复合材料。
实施例5
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂12份，纳米二氧化硅涂料12份，所述纳米二氧化硅涂料粒径为15nm，柔顺剂聚二甲基硅氧烷二季胺盐2份，二辛基琥珀酸磺酸钠wt％：2-甲基丙烯酸环氧乙烷基甲酯wt％＝1:3的稳定剂2份，消泡剂氰脲酰氯三聚氰胺1份，纯化水79份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3份、环氧树脂13份、聚四氟乙烯2份、碳酸钙1.5份。所述胶粘剂层胶粘剂为聚丙烯酸酯，所述热封层采用聚乳酸乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过等离子处理改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用聚丙烯酸酯胶粘剂层通过干式复合将各层层压在一起形成复合材料。
实施例6
一种纸基可回收复合材料，所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述纸基层外侧从内向外依次包括阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂14份，纳米二氧化硅涂料11份，柔顺剂双十八烷基二甲基氯化铵1份，稳定剂硬脂酸镁2份，二甲基硅油wt％：氰脲酰氯三聚氰胺wt％＝1:1的消泡剂1份，纯化水68份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3份、环氧树脂12份、聚四氟乙烯1份、碳酸钙0.5份。所述胶粘剂层胶粘剂为聚丙烯酸酯，所述热封层采用聚乳酸乳液。
所述一种纸基可回收复合材料的制备方法，所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过火焰处理改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用聚丙烯酸酯胶粘剂层通过干式复合将各层层压在一起形成复合材料。
对比例
对比例以实施例1为基础，区别在于，对比例1中未加入纳米二氧化硅涂料，对比例2中未加入柔顺剂，对比例3中未加入稳定剂。考察水蒸气透过率(WVTR)，氧气透过率(OTR)。
1.实施例1-6的发明与对比例实验结果
| 测试项目 | WVTR | OTR | 热封性能 | 拉伸强度(MPa) |
| 实施例1 | 0.85 | 0.95 | 完整 | 25.3 |
| 实施例2 | 0.89 | 0.92 | 完整 | 26.1 |
| 实施例3 | 0.86 | 0.89 | 完整 | 25.6 |
| 实施例4 | 0.91 | 0.84 | 完整 | 25.0 |
| 实施例5 | 0.88 | 0.85 | 完整 | 27.2 |
| 实施例6 | 0.92 | 0.94 | 完整 | 26.3 |
| 对比例1 | 1.62 | 1.55 | 完整 | 22.4 |
| 对比例2 | 1.15 | 1.09 | 开层 | 21.1 |
| 对比例3 | 1.05 | 1.03 | 开层 | 24.6 |
通过考察实施例1-6，水蒸气透过率(WVTR)，氧气透过率(OTR)均小于1.0。实施例显示纸基复合材料具有较好的阻隔性能，水蒸气透过率、氧气透过率低。对比例1中未加入纳米二氧化硅涂料，其WVTR、OTR值上升明显，对比例2中未加入柔顺剂，对比例3中未加入稳定剂其WVTR、OTR值均有上升，均在1.0以上，可见纳米二氧化硅涂料、柔顺剂、稳定剂均能显著影响其水蒸气透过率和氧气透过率。发明热封性能良好，复合材料膜层在使用过程中能够保持完整，而对比例2、对比例3均出现了开层现象。可见柔顺剂和稳定剂的使用能够明显改善材料的热封性能。实施例1-6拉伸强度≥25MPa，对比例的拉伸强度均有不同程度的下降，而对比例2的拉伸强度下降尤为明显，可见对阻隔涂层的材料进行改性，可以极大的提高复合材料的拉伸强度。
综上所述本发明采用的纸基复合材料具有良好的阻隔性能，可有效阻隔水汽、氧气等气体的渗透，提高包装内容物的保质期，同时具有良好的热封性能，既满足包装密封的需求，又完全符合可回收处理的要求。纸张阻隔性能提升，OTR/WVTR均可满足≤1.0的指标。复合材料通过配方以及生产工艺的改进，材料拉伸强度≥25MPa。阻隔涂层可用于制备组成两层及多层复合薄膜。胶粘剂层采用水性聚氨酯或聚丙烯酸酯类复合胶或压敏胶，工艺适应性得到提升。采用生物基材料，可实现生物降解，复合材料符合绿色环保要求。本发明成本优势明显，各方面综合性能优越，产业化能力强、质量稳定可控，具有较强的应用前景。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种纸基可回收复合材料，其特征在于：所述复合材料从外向内依次包括纸基层、阻隔涂层、胶粘剂层、热封层；所述阻隔涂层成分包括改性丙烯酸树脂12-15份，纳米二氧化硅涂料6-12份，柔顺剂1-2份，稳定剂1-2份，消泡剂1-2份，纯化水68-79份；所述改性丙烯酸树脂包括甲基三乙氧基硅烷3-4份、环氧树脂12-13份、聚四氟乙烯1-2份、碳酸钙0.5-1.5份。
2.根据权利要求1所述的一种纸基可回收复合材料，其特征在于：所述纸基层外侧从内向外依次包括阻隔涂层、胶粘剂层、热封层。
3.根据权利要求1或2所述的一种纸基可回收复合材料，其特征在于：所述柔顺剂为双聚乙烯聚二甲基硅氧烷、双十八烷基二甲基氯化铵、聚二甲基硅氧烷二季胺盐中的一种或几种。
4.根据权利要求3所述的一种纸基可回收复合材料，其特征在于：所述稳定剂为硬脂酸镁、二辛基琥珀酸磺酸钠、2-甲基丙烯酸环氧乙烷基甲酯中的一种或几种。
5.根据权利要求4所述的一种纸基可回收复合材料，其特征在于：所述消泡剂为二甲基硅油、氰脲酰氯三聚氰胺、聚氧丙烯甘油醚中的一种或几种。
6.根据权利要求5所述的一种纸基可回收复合材料，其特征在于：所述纳米二氧化硅涂料粒径为7-40nm。
7.根据权利要求6所述的一种纸基可回收复合材料，其特征在于：所述胶粘剂层胶粘剂为水性聚氨酯或聚丙烯酸酯中的一种或两种。
8.根据权利要求7所述的一种纸基可回收复合材料，其特征在于：所述热封层采用聚乳酸乳液、丙烯酸乳液中的一种或两种。
9.根据权利要求1-8中任一项所述的一种纸基可回收复合材料的制备方法，其特征在于：所述阻隔涂层通过网纹辊涂布转移的方式将阻隔涂层均匀的涂布在经过改性处理的纸基层上，经过涂布机的干燥处理形成均一致密的阻隔涂层，最后收卷制成阻隔纸基材料；采用胶粘剂层通过干式复合将各层层压在一起形成复合材料。
10.根据权利要求9所述的一种纸基可回收复合材料的制备方法，其特征在于：所述纸基层改性处理的操作为在线电晕、等离子处理或火焰处理。
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| CN105802366A (zh) * | 2016-04-08 | 2016-07-27 | 北京凯瑞捷成新材料科技有限公司 | 涂料组合物及其制备的水性聚四氟乙烯雨刷涂料 |
| CN109971267A (zh) * | 2017-12-28 | 2019-07-05 | 常德金德新材料科技股份有限公司 | 一种高阻隔性涂料及其制备方法 |
| CN113416459A (zh) * | 2021-06-11 | 2021-09-21 | 安徽强邦新材料股份有限公司 | 一种印刷版保护涂层及其制备方法 |
| CN113619242A (zh) * | 2021-08-09 | 2021-11-09 | 江苏利特尔绿色包装股份有限公司 | 一种可生物降解高阻隔纸塑包装复合膜及其制备方法 |
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