CN114990937A - 一种高耐酒精热敏纸及其制备方法 - Google Patents
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Abstract
本发明涉及热敏纸技术领域,公开了一种高耐酒精热敏纸及其制备方法,自下而上包括纸基层、底涂层、发色层、保护层;发色层的组分包括:第一填料、显色剂、胶黏剂、染料、增感剂、安定剂;保护层的组分包括:第二填料、树脂、聚乙烯蜡乳液、胶黏剂。本发明减少了增感剂的使用,能够在保证热敏纸发色感度的同时提高其耐酒精性。
Description
技术领域
本发明涉及热敏纸技术领域,尤其涉及一种高耐酒精热敏纸及其制备方法。
背景技术
现常用的热敏纸如热敏传真纸,发色温度范围一般为65~75℃,发色后遇水会迅速褪色,不耐酒精、油脂、发腊等,磨擦及接触后易变花变脏,无法达到抗水及耐其他溶剂的要求指标,不能满足特种热敏纸的指标要求;而热敏纸在国内常被广泛应用在彩票实体投注站等领域,这种特殊热敏纸必须保持在一定温、湿度环境下底色不发色,显色部分良好可识别读取,还必须具备一定的耐水、食用油、25%体积比酒精、耐刮擦、耐光、耐高温等性能。
然而,由于电商的迅速崛起,热敏纸在物流标签上的使用被迅速推广,快速替代了拥有手写繁琐、字迹潦草不清楚等缺点的无碳复写纸,改善了热转印碳带耗材替换成本高、高度打印不可实现等缺点,这种快速应用使得物流热敏纸的行业使用标准沿用了国家推荐的使用标准,为了实现热敏纸的高速打印,热敏纸的国家标准中规定了平滑度、灵敏度发色等,导致价格较高的增感剂被广泛使用,其在提高热敏纸发色感度的同时又会导致降低底色的耐高温性和耐酒精性。
发明内容
为了能够在保证热敏纸发色感度的同时提高其耐酒精性,本发明的技术方案提供了一种高耐酒精热敏纸及其制备方法。技术方案如下:
本发明提供了一种高耐酒精热敏纸,自下而上包括纸基层、底涂层、发色层、保护层;发色层的组分按重量份数计包括:第一填料60~100份、显色剂60~100份、胶黏剂25~45份、染料25~40份、增感剂5~10份、安定剂20~40份。
优选的,显色剂采用4,4′-磺酰基双[2-(2-丙烯基)]苯酚、2,4二苯砜基苯酚、4-羟基二苯砜异丙基醚、3-(3-甲苯基脲基)苯基4-甲基苯磺酸酯、4,4′-(1-苯乙基)双酚中的一种或几种。
优选的,安定剂采用1,1,3-三(2-甲基-4-羟基-5-叔丁苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-环己基苯基)丁烷、1,2,3,4-丁四羧酸四(1,2,2,6,6-五甲基-4-哌啶基)酯中的一种或几种。
优选的,保护层的组分按重量份数计包括:第二填料80~100份、树脂50~70份、聚乙烯蜡乳液8~15份、胶黏剂20~40份。
优选的,树脂采用氟改性聚氨酯树脂、环氧树脂、聚酯树脂、聚酯改性丙烯酸树脂中的一种或几种。
优选的,底涂层的组分包括第三填料,第三填料设为高中空率的球状材料。
本发明还提供了一种高耐酒精热敏纸的制备方法,其特征在于,包括以下步骤:
S1:将底涂层的涂布液涂覆于纸基层上,烘干即得底涂层;
S2:按重量份数计将60~100份第一填料、60~100份显色剂、25~45份胶黏剂、25~40份染料、5~10份增感剂、20~40份安定剂混合并搅拌均匀,得到发色层的涂布液;
S3:将分散均匀的发色层的涂布液涂覆于底涂层上,烘干即得发色层;
S4:按重量份数计将80~100份第二填料、50~70份树脂、8~15份聚乙烯蜡乳液、20~40份胶黏剂混合并搅拌均匀,得到保护层的涂布液;S5:将分散均匀的保护层的涂布液涂覆于发色层上,烘干即得保护层;S6:通过热压工艺与纸基层、底涂层、发色层、保护层复合在一起。
与现有技术相比,本发明的优点在于:
1)本发明的保护层中加入了憎水性化合物聚乙烯蜡乳液,不但可以增加成膜的滑感,还可以增强保护层的疏水性、耐酒精性;
2)本发明的保护层中所使用的树脂都是耐酒精性比较高的树脂,可以进一步提高热敏纸的耐酒精程度;
3)本发明底涂层中所使用的第三填料为高中空率材料,可以增强热量的隔绝,提升热敏纸的耐热性以及灵敏度,从而作为辅助减少增感剂的用量;
4)本发明采用显色剂以一定的比例搭配安定剂、增感剂,减少了增感剂的用量,降低了成本的同时仍旧可以达到GB/T的要求;并且安定剂的使用还可以提高发色基团的稳定性,使得发色基团即使在潮湿的环境中也能保持稳定,变相提高了热敏纸的耐酒精性。
具体实施方式
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开,下文中对特定例子的部件和设置进行描述。当然,它们仅仅为示例,并且目的不在于限制本发明。此外,本发明可以在不同例子中重复参考数字和/或参考字母,这种重复是为了简化和清楚的目的,其本身不指示所讨论各种实施方式和/或设置之间的关系。
本发明的一实施例,一种高耐酒精热敏纸,自下而上包括纸基层、底涂层、发色层、保护层;其中,底涂层的组分主要包括第三填料、胶黏剂,该第三填料采用高中空率的球状材料或者可以增加底层平滑度的片状材料,不但可以保证感热均一性、增强热量的隔绝,从而提升热敏纸的耐热性以及灵敏度,还可以进而作为辅助减少增感剂的用量,降低成本,提高热敏纸的耐酒精性;胶黏剂采用苯乙烯丙烯酸树脂、聚乙烯醇、丙烯酸树脂中的一种或几种。
本实施例中,发色层的组分按重量份数计包括:第一填料60~100份、显色剂60~100份、胶黏剂25~45份、染料25~40份、增感剂5~10份、安定剂20~40份;其中,第一填料采用氢氧化铝、轻质碳酸钙、瓷土、二氧化硅、高岭土中的一种或几种;显色剂采用4,4′-磺酰基双[2-(2-丙烯基)]苯酚、2,4二苯砜基苯酚、4-羟基二苯砜异丙基醚、3-(3-甲苯基脲基)苯基4-甲基苯磺酸酯、4,4′-(1-苯乙基)双酚中的一种或几种;胶黏剂采用丁苯胶乳乳液、聚乙烯醇、丙烯酸胶乳、淀粉乳液中的一种或几种;染料采用2-苯胺基-3-甲基-6-(N-乙基-N-对甲苯基氨基)荧烷、2-苯胺基-3-甲基-6-二丁基氨基荧烷、2-(2-4-二甲苯胺基)-3-甲基-6-二乙氨基荧烷中的一种;增感剂采用二(4-氯苄基)草酸酯、1,2-双(3-甲基苯氧基)乙烷、双二甲苯基乙烷、1,2-二苯氧基乙烷中的一种或几种;安定剂采用1,1,3-三(2-甲基-4-羟基-5-叔丁苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-环己基苯基)丁烷、1,2,3,4-丁四羧酸四(1,2,2,6,6-五甲基-4-哌啶基)酯中的一种或几种;通过将显色剂与安定剂、增感剂搭配使用,一定程度上减少了增感剂的用量,降低了成本的同时仍旧可以达到热敏纸的GB/T要求;同时,安定剂的使用还可以提高发色基团的稳定性,抑制该发色基团在潮湿环境中的逆反应程度,使得发色基团在潮湿环境中稳定性能大大提高,变相提高了热敏纸的耐酒精性。
本实施例中,保护层的组分按重量份数计包括:第二填料80~100份、树脂50~70份、聚乙烯蜡乳液8~15份、胶黏剂20~40份;其中,第二填料采用云母、氧化钙、高岭土、粘土、碳酸钙中的一种或几种;树脂采用氟改性聚氨酯树脂、环氧树脂、聚酯树脂、聚酯改性丙烯酸树脂中的一种或几种,这些树脂都是耐酒精性比较高的树脂,可以进一步提高热敏纸的耐酒精程度,比如氟元素的引入可以使得涂层的表面能显著降低,具有良好的拉伸强度和耐水性,可以显著提升聚氨酯树脂耐水、耐油性、耐酒精、耐化学品等性能,环氧树脂的复配也可以使得在成膜的过程中形成三维交联结构,产生不可逆的共价交联,显着提高涂层的拉伸强度和耐水性、耐酒精、耐化学品等性能;憎水性聚乙烯蜡乳液的添加不但可以通过增滑作用以改善薄膜的抗回粘性,增加膜的手感,使成膜更好,还可以增强保护层的疏水性和耐酒精性,当然,除了聚乙烯蜡乳液之外,还可以选用憎水性的蜡粉或其他蜡乳液;胶黏剂采用脲醛树脂、聚乙酸乙烯酯乳液、橡胶乳液、水性阳离子型聚氨酯、丙烯酸酯乳液中的一种或几种。
本实施例中,一种高耐酒精热敏纸的制备方法,包括以下步骤:
S1:将底涂层的涂布液涂覆于纸基层上,烘干即得底涂层;
S2:按重量份数计将60~100份第一填料、60~100份显色剂、25~45份胶黏剂、25~40份染料、5~10份增感剂、20~40份安定剂混合并搅拌均匀,得到发色层的涂布液;
S3:将分散均匀的发色层的涂布液涂覆于底涂层上,烘干即得发色层;
S4:按重量份数计将80~100份第二填料、50~70份树脂、8~15份聚乙烯蜡乳液、20~40份胶黏剂混合并搅拌均匀,得到保护层的涂布液;
S5:将分散均匀的保护层的涂布液涂覆于发色层上,烘干即得保护层;
S6:通过热压工艺与纸基层、底涂层、发色层、保护层复合在一起。
实施例1
发色层的组分按重量份数计包括:第一填料60份、显色剂60份、胶黏剂25份、染料25份、增感剂5份、安定剂20份。
保护层的组分按重量份数计包括:第二填料80份、树脂50份、聚乙烯蜡乳液8份、胶黏剂20份。
高耐酒精热敏纸的制备方法包括以下步骤:
将底涂层的涂布液涂覆于纸基层上,烘干即得底涂层;按重量份数计将60份第一填料、60份显色剂、25份胶黏剂、25份染料、5份增感剂、20份安定剂混合并搅拌均匀,得到发色层的涂布液,将该涂布液涂覆于底涂层上,烘干即得发色层;再按重量份数计将80份第二填料、50份树脂、8份聚乙烯蜡乳液、20份胶黏剂混合并搅拌均匀,得到保护层的涂布液,将该涂布液涂覆于发色层上,烘干即得保护层;最终通过热压工艺与纸基层、底涂层、发色层、保护层复合在一起。
实施例2
发色层的组分按重量份数计包括:第一填料100份、显色剂100份、胶黏剂45份、染料40份、增感剂10份、安定剂40份。
保护层的组分按重量份数计包括:第二填料100份、树脂70份、聚乙烯蜡乳液15份、胶黏剂40份。
高耐酒精热敏纸的制备方法包括以下步骤:
将底涂层的涂布液涂覆于纸基层上,烘干即得底涂层;按重量份数计将100份第一填料、100份显色剂、45份胶黏剂、40份染料、10份增感剂、40份安定剂混合并搅拌均匀,得到发色层的涂布液,将该涂布液涂覆于底涂层上,烘干即得发色层;再按重量份数计将100份第二填料、70份树脂、15份聚乙烯蜡乳液、40份胶黏剂混合并搅拌均匀,得到保护层的涂布液,将该涂布液涂覆于发色层上,烘干即得保护层;最终通过热压工艺与纸基层、底涂层、发色层、保护层复合在一起。
实施例3
发色层的组分按重量份数计包括:第一填料80份、显色剂80份、胶黏剂35份、染料33份、增感剂7份、安定剂30份。
保护层的组分按重量份数计包括:第二填料90份、树脂60份、聚乙烯蜡乳液10份、胶黏剂30份。
高耐酒精热敏纸的制备方法包括以下步骤:
将底涂层的涂布液涂覆于纸基层上,烘干即得底涂层;按重量份数计将80份第一填料、80份显色剂、35份胶黏剂、33份染料、7份增感剂、30份安定剂混合并搅拌均匀,得到发色层的涂布液,将该涂布液涂覆于底涂层上,烘干即得发色层;再按重量份数计将90份第二填料、60份树脂、10份聚乙烯蜡乳液、30份胶黏剂混合并搅拌均匀,得到保护层的涂布液,将该涂布液涂覆于发色层上,烘干即得保护层;最终通过热压工艺与纸基层、底涂层、发色层、保护层复合在一起。
表1实施例和对比例的对比性能测试
如表1所示,根据《GB/T 28210-2011热敏纸-静态发色性能的测定》、《GB/T 28210-2011热敏纸-动态发色性能的测定》、《GB/T28210-2011热敏纸-图像防护性能的测定》进行性能测试,对比了上述实施例和对比例热敏纸的静态光密度与动态显色灵敏度、耐热性及防乙醇性能数据,其中,防乙醇性能试验的过程为:将实施例1~3和对比例的试样分别放在平板玻璃上,发色面朝上,再将圈液器置于饱和发色的试样上,吸取1.0mL乙醇滴入圈液器重,室温条件下放置3h后,移开试样上的圈液器,用滤纸轻轻吸取试样表面上残留的乙醇,用吹风机冷风吹干后测定其光密度值并计算图像保留率,其中,图像保留率=防乙醇试验3h后的静态饱和发色光密度/防乙醇试验前的静态饱和发色光密度。
由表1的数据可以看出,相比于对比例的试样,实施例1~3的试样在酒精防护性能上具备优异的稳定性,打印文字后的热敏纸在浸泡酒精3h后也具备优异的可辨识性和高保留率,说明本发明公开实施例具备高耐酒精性能;并且,与对比例比较,本发明实施例的静态饱和发色光密度有所提升的同时动态显色灵敏度有所下降,说明本发明中的热量传递受到了抑制,底涂层与保护层起到了隔热作用,提高了热敏纸的打印精细性,并且完全符合热敏纸的GB/T要求。
本领域技术人员在考虑说明书及实践这里的发明后,将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化,这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的,本发明的真正范围和精神由权利要求指出。
应当理解的是,本发明并不局限于上面已经描述的内容,并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。
Claims (7)
1.一种高耐酒精热敏纸,其特征在于,自下而上包括纸基层、底涂层、发色层、保护层;所述发色层的组分按重量份数计包括:第一填料60~100份、显色剂60~100份、胶黏剂25~45份、染料25~40份、增感剂5~10份、安定剂20~40份。
2.根据权利要求1所述的一种高耐酒精热敏纸,其特征在于,所述显色剂采用4,4′-磺酰基双[2-(2-丙烯基)]苯酚、2,4二苯砜基苯酚、4-羟基二苯砜异丙基醚、3-(3-甲苯基脲基)苯基4-甲基苯磺酸酯、4,4′-(1-苯乙基)双酚中的一种或几种。
3.根据权利要求1所述的一种高耐酒精热敏纸,其特征在于,所述安定剂采用1,1,3-三(2-甲基-4-羟基-5-叔丁苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-环己基苯基)丁烷、1,2,3,4-丁四羧酸四(1,2,2,6,6-五甲基-4-哌啶基)酯中的一种或几种。
4.根据权利要求1所述的一种高耐酒精热敏纸的制备方法,其特征在于,所述保护层的组分按重量份数计包括:第二填料80~100份、树脂50~70份、聚乙烯蜡乳液8~15份、胶黏剂20~40份。
5.根据权利要求4所述的一种高耐酒精热敏纸,其特征在于,所述树脂采用氟改性聚氨酯树脂、环氧树脂、聚酯树脂、聚酯改性丙烯酸树脂中的一种或几种。
6.根据权利要求1所述的一种高耐酒精热敏纸,其特征在于,所述底涂层的组分包括第三填料,所述第三填料设为高中空率的球状材料。
7.根据权利要求1所述的一种高耐酒精热敏纸的制备方法,其特征在于,包括以下步骤:
S1:将所述底涂层的涂布液涂覆于所述纸基层上,烘干即得所述底涂层;
S2:按重量份数计将60~100份第一填料、60~100份显色剂、25~45份胶黏剂、25~40份染料、5~10份增感剂、20~40份安定剂混合并搅拌均匀,得到所述发色层的涂布液;
S3:将分散均匀的所述发色层的涂布液涂覆于所述底涂层上,烘干即得所述发色层;
S4:按重量份数计将80~100份第二填料、50~70份树脂、8~15份聚乙烯蜡乳液、20~40份胶黏剂混合并搅拌均匀,得到所述保护层的涂布液;
S5:将分散均匀的所述保护层的涂布液涂覆于所述发色层上,烘干即得所述保护层;
S6:通过热压工艺与所述纸基层、所述底涂层、所述发色层、所述保护层复合在一起。
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