CN114525700A - 防水热敏纸 - Google Patents

防水热敏纸 Download PDF

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CN114525700A
CN114525700A CN202210180270.XA CN202210180270A CN114525700A CN 114525700 A CN114525700 A CN 114525700A CN 202210180270 A CN202210180270 A CN 202210180270A CN 114525700 A CN114525700 A CN 114525700A
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钱泉
俞海波
唐喜万
盛伟
吴昊
汪蒙蒙
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Ricoh Thermal Media Wuxi Co Ltd
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Abstract

本发明属于热敏纸技术领域,具体涉及防水热敏纸。本发明在底涂层即热敏层的底部涂布含有AKD(烷基烯酮二聚体)和PVA的抗水增强材料与原纸层中本身即存在AKD紧密结合,不仅提高纸的表面强度的同时增加热敏涂层和纸的结合力,使用聚乙烯醇优良成膜性使材料整体具备有塑料膜的特性,利用其与纤维素的粘结力增加层间结合力。此外,水性有机硅清漆作为保护层来提高热敏材料的抗水性能和柔韧性。本发明提高纸质热敏材料的强度,抗水性,改变材料柔韧性,实现膜类热敏材料的功能,并提高热敏材料的耐热性,耐化学药品的特性,增强在低温,高温,或需要消毒等特殊使用场景的耐腐蚀性,以提高综合使用特性和保存性。

Description

防水热敏纸
技术领域
本发明属于热敏纸技术领域,具体涉及防水热敏纸。
背景技术
热敏纸又被称为热敏传真纸、热敏记录纸、热敏复印纸,是一种加工纸,其制造原理就是在原纸上涂布一层热敏涂料,热敏涂料在受热条件下起显色反应。目前热敏纸在生产生活中使用日益广泛,如终端POS,银行柜台,票证,门票,标签、物流面单等等。纸质热敏材料受纸的特性的限制,遇水或受外力导致材料破损或基材和热敏层剥落的几率很高,特别是在湿度高的环境完全无法使用,因此有部分热敏纸以塑料膜添加至纸中,以增强其防水性能,但是塑料膜不够环保,对热敏纸的生产产生限制。此外,热敏纸中的热敏涂布的纸质基材易于吸收水分,且纸浆纤维之间结合力弱,纸表面粗糙,和热敏涂布层结合力差,亦造成热敏涂布层防水性能弱。
发明内容
针对上述现有技术的不足,本发明提供了防水热敏纸,目的是为了解决没有添加塑料材质的纸质热敏纸,遇水或受外力导致材料破损或基材和热敏层剥落的几率很高,特别是在湿度高的环境完全无法使用,以及纸中的热敏涂布的纸质基材易于吸收水分,且纸浆纤维之间结合力弱,纸表面粗糙,和热敏涂布层结合力差,亦造成热敏涂布层防水性能弱的技术问题。
本发明提供的防水热敏纸,具体技术方案如下:
防水热敏纸,由下至上依次包括原纸层、底涂层、发色层和第二保护层,在所述原纸层和所述底涂层之间设有抗水增强材料,所述抗水增强材料包括15%固形分、所述固形分包括45%烷基烯酮二聚体和55%聚乙烯醇,所述第二保护层包括水性有机硅清漆。
在某些实施方式中,所述抗水增强材料按照80kg/T纸浆的比例涂布于所述底涂层底部,所述纸浆为制备原纸层的纸浆。
在某些实施方式中,所述第二保护层还包括水性上光油,所述水性上光油与所述水性有机硅清漆的混合比例为1:(0.5-5)。
在某些实施方式中,所述第二保护层通过涂布的方式设置在所述发色层上,工艺参数如下:涂布温度:20-25℃;涂布量:2.5-5.3g/m2;干燥方式:烘箱,干燥温度:35-50℃
在某些实施方式中,还包括第一保护层,所述第一保护层设于所述发色层与所述第二保护层之间,所述第一保护层为有机硅树脂颗粒。
在某些实施方式中,所述底涂层包括煅烧高岭土、颜料分散剂、胶粘剂及保水剂。
进一步,所述底涂层还添加有5-20%的聚乙烯醇。
在某些实施方式中,所述发色层包括无色染料、显色剂、增感剂、沉淀碳酸钙、无机颜料分散剂、低聚合度聚乙烯醇和助剂。
本发明具有以下有益效果:本发明提供的防水热敏纸,在底涂层的底部涂布含有AKD(烷基烯酮二聚体)和PVA的抗水增强材料,由于原纸层中本身即存在AKD作为施胶剂,抗水增强材料渗透进入原纸纤维,相同原料紧密结合,使用AKD在提高纸的表面强度的同时增加热敏涂层和纸的结合力,使用聚乙烯醇优良成膜性使材料整体具备有塑料膜的特性,利用其与纤维素的粘结力增加层间结合力。此外,水性有机硅清漆作为保护层来提高热敏材料的抗水性能和柔韧性,因该涂层具有隔绝作用,同时提高热敏材料的耐热,耐化学品的特性。本发明提高纸质热敏材料的强度,抗水性,改变材料柔韧性,实现膜类热敏材料的功能,并提高热敏材料的耐热性,耐化学药品的特性,增强在低温,高温,或需要消毒等特殊使用场景的耐腐蚀性,以提高综合使用特性和保存性。
附图说明
图1是本发明提供的防水热敏纸层级结构示意图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图1,对本发明进一步详细说明。
本发明提供的防水热敏纸,具体技术方案如下:
防水热敏纸,由下至上依次包括原纸层、底涂层、发色层和第二保护层,原纸层包含AKD,在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,其中固形分中45%AKD和55%聚乙烯醇,第二保护层包括水性有机硅清漆。AKD:烷基烯酮二聚体(外文名alkylketene dimmer)性状:蜡状固体;熔点51~52℃,其物化性质:一种不饱和内酯,产品是不溶于水的蜡状固体,熔点为51~52℃左右。用于造纸施胶剂的AKD必须制成乳液,其产品的颗粒粒径约为0.5~2μm,乳液呈白色,且极易水解,所以一般贮存期较短,仅3~6个月。由于合成和乳化技术的发展,AKD乳液的固含量可达40%或更高,其水解和迁移倾向被大大限制。有机硅清漆是以有机硅聚合物或有机硅改性聚合物为主要成膜物质的涂料,具有优良的耐热耐寒、电绝缘、耐电晕、耐辐射、耐潮湿和憎水、耐候、耐沾污及耐化学腐蚀等特性
具体的,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部。其中的纸浆为制备原纸层的纸浆。
具体的,第二保护层还包括水性上光油,水性上光油与水性有机硅清漆的混合比例为1:(0.5-5)。
具体的,第二保护层通过涂布的方式设置在发色层上,工艺参数如下:涂布温度:20-25℃;涂布量:2.5-5.3g/m2;干燥方式:烘箱,干燥温度:35-50℃。
具体的,还包括第一保护层,第一保护层设于发色层与第二保护层之间,第一保护层为有机硅树脂颗粒。
保护层是在热敏显色层(发光层)上形成的层,保护层包含树脂、交联剂,并且如果需要的话,还可以包含填料和其它物质。
树脂根据期望的目的没有任何限制地进行适当选择,条件是它是包含活性羰基(一个或多个)的聚乙烯醇。包含活性羰基(一个或多个)的聚乙烯醇根据期望的目的没有任何限制地进行适当选择,和其实例包括双丙酮改性的聚乙烯醇。包含活性羰基(一个或多个)的聚乙烯醇可以通过常规的方法产生,如在其中每个包含活性羰基(一个或多个)的乙烯单体和脂肪酸乙烯酯进行共聚合的方法。包含活性基团(一个或多个)的乙烯单体根据期望的目的没有任何限制地进行适当选择。其实例包括:包含酯键的基团的单体、和包含丙酮基的单体。在它们当中,包含双丙酮基的乙烯基单体为优选的,并且具体地,双丙酮丙烯酰胺和甲基双丙酮丙烯酰胺(methadiacetoneacrylamide)为优选的。为了获得前述双丙酮改性的聚乙烯醇,使用双丙酮丙烯酰胺、甲基双丙酮丙烯酰胺等。脂肪酸乙烯酯根据预期目的没有限制地进行适当选择。其实例包括甲酸乙烯酯、乙酸乙烯酯和丙酸乙烯酯。在它们当中,乙酸乙烯酯为优选的。双丙酮改性的聚乙烯醇可以与乙烯单体共聚合。能够共聚合这种双丙酮改性聚乙烯醇的乙烯单体根据预期目的没有任何限制地进行适当选择。其实例包括丙烯酸酯、丁二烯、乙烯、丙烯、丙烯酸、甲基丙烯酸、马来酸、马来酸酐和衣康酸。双丙酮改性聚乙烯醇中包含的双丙酮基团的量根据预期目的没有任何限制地进行适当限制,但是一般为相对于聚合物总量的约0.5摩尔%至约20摩尔%,和优选为2摩尔%至10摩尔%,以改善生成的热敏记录材料的耐水性。当其量小于2摩尔%时,其耐水性对于实际的应用是不够的。当其量大于10摩尔%时,其耐水性没有进一步地改善,但是生产成本增加。双丙酮改性的聚乙烯醇的聚合度根据预期目的没有任何限制地进行适当选择,但是优选为300至3,000,更优选为500至2200。双丙酮改性的聚乙烯醇的皂化度优选为80%或更高。
交联剂根据预期目的没有任何限制地进行适当选择,条件是它包含酰肼化合物。酰肼化合物根据预期目的没有任何限制地进行适当选择,其实例包括二酰肼(dihydrazide)化合物如脂肪二酰肼和邻苯二甲酸二酰肼。而且,以上提到的一种或多种交联剂可以与本领域已知的一种或多种交联剂组合地使用。
填料根据预期目的没有任何限制地进行适当选择。它们实例包括:无机粉末如氢氧化铝、碳酸钙、二氧化硅、氧化锌、氧化钛、氢氧化锌、硫酸钡、粘土、滑石、表面处理的钙、和表面处理的硅石;和有机粉末如有机硅树脂颗粒、脲-福尔马林树脂、聚乙烯-甲基丙烯酸共聚物和聚苯乙烯树脂。在它们当中,氢氧化铝和碳酸钙是优选的,因为当热敏记录材料用于长时间打印的时候,它们提供对热敏打印头具有良好耐磨性的热敏记录材料。
具体的,按重量份计,底涂层是由煅烧高岭土85~95份,颜料分散剂0.5~1份,胶粘剂7~10份和保水剂0.5~2份搅拌混合,形成固含量为40%~50%的底涂层涂布液。将上述底涂层涂布液进行涂布形成底涂层。此外底涂层中还添加有5-20%的聚乙烯醇。与原纸层中含有的PVA结合得更紧密,更能产生结合力和耐水性。
具体的,发色层制备方法如下:首先将无色染料85~90份和低聚合度聚乙烯醇10~15份混合获得无色染料混合液,显色剂85~90份和低聚合度聚乙烯醇10~15份混合获得显色剂染料混合液,增感剂(1,2-二苯氧基乙烷)85~90份和低聚合度聚乙烯醇10~15份获得增感剂混合液,沉淀碳酸钙99~100份和无机颜料分散剂0.5~1份混合获得分散剂混合液。其次,将上述20~25份无色染料混合液、40~45份显色剂染料混合液、10~20份增感剂混合液、5~10份分散剂混合液和1~5份助剂混合获得发色层涂布液。最后将发色层涂布液涂布于底涂层上,形成发色层。此外,上述均按照重量份计。
实施例1
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层和第二保护层,在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,固形分为45%AKD和55%聚乙烯醇,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部,第二保护层包括水性有机硅清漆。
实施例2
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层、第一保护层和第二保护层,在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,固形分为45%AKD和55%聚乙烯醇,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部,第一保护层为有机硅树脂颗粒,第二保护层包括水性有机硅清漆。
实施例3
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层和第二保护层,在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,固形分为45%AKD和55%聚乙烯醇,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部,底涂层中添加有聚乙烯醇,第二保护层包括水性有机硅清漆。
实施例4
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层、第一保护层和第二保护层,在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,固形分为45%AKD和55%聚乙烯醇,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部,底涂层中添加有聚乙烯醇,第一保护层为有机硅树脂颗粒,第二保护层包括水性有机硅清漆。
对比例1
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层。在原纸层和底涂层之间设有抗水增强材料,抗水增强材料包括15%固形分,固形分为45%AKD和55%聚乙烯醇,抗水增强材料按照80kg/T纸浆的比例涂布于底涂层底部。
对比例2
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层和第二保护层。原纸层为常规原纸,第二保护层包括水性有机硅清漆。
对比例3
本实施例提供的防水热敏纸,由下至上依次包括原纸层、底涂层、发光层。原纸层为常规原纸,第二保护层包括水性有机硅清漆。
对实施例1-4及对比例1-3的热敏纸性能进行测试,其中耐水摩擦用RTM评价的方法,打印适配性在是RTM中实施的zebra的粘附评价。如表1所示,本发明提供的热敏纸性能良好,其中实施例4的热敏纸耐水摩擦性能及打印适配性是最佳的,本发明提供的热敏纸能够保证良好的耐水摩擦和打印适配性。
表1 实施例1-4及对比例1-3的热敏纸性能测试结果
实施例1 实施例2 实施例3 实施例4 对比例1 对比例2 对比例3
耐水摩擦 × × ××
打印适配性
*在耐水摩擦性能中,表中符号含义如下:
◎:即使摩擦超过100次,层会剥离,纸张不会破裂。
○:摩擦50次~99次时,层会剥离,纸张会破裂。
×:摩擦25次~49次,层会剥离,纸张会破裂。
××:摩擦25次以下发生层剥离,纸张破裂。
*在打印适配性中,表中符号含义如下:
◎:打印长度不缩短,并且不发生打印跳格
○:打印跳格虽然发生,但打印长度不缩短
×:发生打印跳格,同时打印长度缩短。
上述仅本发明较佳可行实施例,并非是对本发明的限制,本发明也并不限于上述举例,本技术领域的技术人员,在本发明的实质范围内,所作出的变化、改型、添加或替换,也应属于本发明的保护范围。

Claims (8)

1.防水热敏纸,其特征在于,由下至上依次包括原纸层、底涂层、发色层和第二保护层,在所述原纸层和所述底涂层之间设有抗水增强材料,所述抗水增强材料包括15%固形分、所述固形分包括45%烷基烯酮二聚体和55%聚乙烯醇,所述第二保护层包括水性有机硅清漆。
2.根据权利要求1所述的防水热敏纸,其特征在于,所述抗水增强材料按照80kg/T纸浆的比例涂布于所述底涂层底部,所述纸浆为制备原纸层的纸浆。
3.根据权利要求1所述的防水热敏纸,其特征在于,所述第二保护层还包括水性上光油,所述水性上光油与所述水性有机硅清漆的混合比例为1:(0.5-5)。
4.根据权利要求1所述的防水热敏纸,其特征在于,所述第二保护层通过涂布的方式设置在所述发色层上,工艺参数如下:涂布温度:20-25℃;涂布量:2.5-5.3g/m2;干燥方式:烘箱,干燥温度:35-50℃。
5.根据权利要求1所述的防水热敏纸,其特征在于,还包括第一保护层,所述第一保护层设于所述发色层与所述第二保护层之间,所述第一保护层为有机硅树脂颗粒。
6.根据权利要求1所述的防水热敏纸,其特征在于,所述底涂层包括煅烧高岭土、颜料分散剂、胶粘剂及保水剂。
7.根据权利要求6所述的防水热敏纸,其特征在于,所述底涂层还添加有5-20%的聚乙烯醇。
8.根据权利要求1所述的防水热敏纸,其特征在于,所述发色层包括无色染料、显色剂、增感剂、沉淀碳酸钙、无机颜料分散剂、低聚合度聚乙烯醇和助剂。
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