CN103842458B - 经时变化小的水性粘结剂组合物 - Google Patents
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Abstract
本发明涉及几乎没有随着经时变化的粘结物理性质的下降的水性粘结剂组合物。本发明的水性粘结剂组合物,其技术特征在于,包含具有羟基的单体,在聚合后不形成螯合物,具有几乎没有随着凝胶含量的增大的粘结物理性质的减少的优点。
Description
技术领域
本发明涉及水性粘结剂组合物,更详细地涉及几乎没有随着粘结剂的凝胶含量的增大的粘结物理性质的减少的水性粘结剂组合物。
背景技术
目前,通用于粘结带或标签等的粘结剂大部分为溶剂型,因而排放挥发性有机物质(VOCs,volatile organic compounds)。因此,最近根据环境制约的强化,而进行从溶剂型到水性粘结剂的技术改良。
在韩国登录专利公报第10-0177541号等文献中公开了与水性粘结剂组合物相关的技术。通常,就通过乳化聚合制成的以往的水性粘结剂而言,为了赋予高的剥离力及凝聚力,将丙烯酸用作官能团单体(functional monomer)。若在水性粘结剂组合物中使用丙烯酸,则可以与粘附物的种类无关地赋予高的粘结特性。但是,这种丙烯酸与包含于为了乳化聚合而使用的引发剂、乳化剂,中和剂、增粘剂的离子杂质进行反应,并在聚合后形成螯合物。这种螯合物增大凝胶含量,由此将增加粘结剂本身的硬度,并减少粘结物理性质。
如上所述,为了防止通过丙烯酸和离子杂质来形成螯合物,也会实施低离子类乳化聚合。但是,由于聚合稳定性的下降及凝聚物的发生等理由,利用最小限度的非离子类化学物质的乳化聚合存在生产率下降的问题。并且,存在最终制成的粘结涂敷层发生缺陷的问题。
因此,当前,为了解决这种问题,需要开发不受当进行乳化聚合时所使用的离子杂质的影响的水性粘结剂组合物。
发明内容
技术问题
本发明用于解决如上所述的问题,其目的在于,提供水性粘结剂组合物,上述水性粘结剂组合物抑制通过丙烯酸和离子杂质来形成螯合物,由此将如剥离力等下降的经时变化最小化。
解决问题的手段
用于达成上述目的的本发明的实施例的水性粘结剂组合物,其特征在于,包含具有羟基的单体,在聚合后不形成螯合物。
发明的效果
由于本发明的水性粘结剂组合物包含具有羟基的单体,且不使用丙烯酸系列的物质,因而在聚合后不形成螯合物。由此,利用本发明的水性粘结剂组合物的粘结片具有几乎没有随着凝胶含量的增大的粘结物理性质的减少的优点。
附图说明
图1为表示本发明的一实施例的粘结片的结构的剖视图。
具体实施方式
参照附图详细说明的实施例会让本发明的优点和特征以及实现这些优点和特征的方法更加明确。但是,本发明不局限于以下所公开的实施例,能够以互不相同的各种方式实施,本实施例只用于使本发明的公开内容更加完整,有助于本发明所属技术领域的普通技术人员完整地理解本发明的范畴,本发明仅由发明要求保护范围定义。在说明书全文中,相同的附图标记表示相同的结构要素。
以下,参照附图,对本发明的水性粘结剂组合物进行详细的说明。
图1示出本发明的一实施例的粘结片。首先,对本发明的水性粘结剂组合物进行说明。
水性粘结剂组合物
本发明的水性粘结剂组合物,其特征在于,包含具有羟基的单体,在聚合后不形成螯合物。
本发明的水性粘结剂组合物,其技术特征在于,不将丙烯酸用作聚合单体,而使用具有羟基的单体,来在乳化聚合后不形成螯合物。
因此,本发明的水性粘结剂组合物能够将螯合物引起的粘结物理性质下降导致的问题最小化。
本发明的包含在水性粘结剂组合物的具有羟基的单体不与在水性粘结剂聚合后所生成的离子杂质形成螯合物,只要是将羟基用作官能团的单体,那么就不受特别的限制地使用。例如,可使用包含选自由丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯及丙烯酸羟丁酯构成的组中的一种以上的物质。
并且,本发明的水性粘结剂组合物还可以包含软单体及硬单体。
可为了赋予本发明的水性粘结剂组合物的初期粘结性而使用上述软单体。上述软单体可使用包含选自由丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-羟乙酯、丙烯酸异丁酯、丙烯酸-2-乙基丁酯、丙烯酸己酯、丙烯酸庚酯、甲基丙烯酸月桂酯、丙烯酸戊酯及丙烯酸-2-乙基己酯构成的组中的一种以上的物质。
可为了本发明的水性粘结剂组合物的凝聚性及粘结性而使用上述硬单体。上述硬单体可使用包含选自由丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、丙烯酸丁酯及甲基丙烯酸-2-乙基己酯构成的组中的一种以上的物质。
并且,本发明的水性粘结剂组合物还可以包含引发剂、乳化剂及增粘剂。
使用上述引发剂是为了引发本发明的水性粘结剂的聚合,这并不受特别的限制。例如,上述引发剂可使用包含选自由过硫酸钾(KPS,Potasium Persulfate)、过硫酸铵(APS,Ammonium Persulfate)、过硫酸钠(SPS,Sodium Persulfate)、偶氮二异丁腈(AIBN,Azoisobutylonitrile)及过氧化二苯甲酰(BPO,Benzoil Peroxide)构成的组中的一种以上的物质。
上述乳化剂只要是用于乳化聚合的公知的乳化剂,那么就不受特别的限制。例如,除了作为阴离子表面活性剂的十二烷基硫酸钠(Sodium Dodecyl Sulfate)、十二烷基苯磺酸钠(Sodium dodecyl benzenesulfonate)和作为非离子表面活性剂的壬基酚聚氧乙烯醚(Polyoxyethylene nonylphenyl ether)之外,可将作为反应性非离子表面活性剂的2-POE-3-烷氧基-1-丙基烯丙基醚(2-POE-3-alkoxy-1-propyl allyl ether)和公知的反应性阴离子表面活性剂等中的一种以上进行混合来使用。
上述增粘剂作为向形成水性粘结剂组合物的反应物赋予粘性的成分,可使用公知的增粘剂,例如,可使用非离子性聚氨酯类增粘剂。
作为非离子性聚氨酯类增粘剂的商业性的例,可提出UH-420(艾迪科(ADEKA)公司制造)。
利用水性粘结剂组合物的粘结片
如图1所示,本发明的粘结片100包括含有水性粘结剂组合物的涂敷层1和离型膜2。
就上述粘结片100而言,通过将本发明的水性粘结剂组合物涂敷于离型膜2的单面或双面,来形成涂敷层1。具体地,可在上述离型膜2的表面涂敷水性粘结剂组合物并进行干燥,来制作形成有涂敷层1的粘结片100。
上述涂敷层1由本发明的水性粘结剂组合物形成,对此的说明如前述。
另一方面,上述涂敷层1可形成于离型膜2的上部。只要上述离型膜2为当对本发明的包含水性粘结剂组合物的涂敷层1进行剥离时,以不残留粘结物的方式容易进行剥离,就不受限制。
例如,作为上述离型膜2,可使用涂敷有硅离型剂的聚对苯二甲酸乙二醇酯。
以下,通过实施例及比较例,对本发明进行更详细的说明,但是本发明不局限于以下的实施例。
实施例
实施例1
在具有温度计、搅拌器、滴液漏斗、氮导入管及回流冷凝器的1L容量的玻璃反应器,以所有反应物100重量份为基准,预先将约18重量份的超纯水和约0.10重量份的过硫酸铵装入反应器,并将内部温度保持为80℃。
在单独的容器中,以所有单体100重量份为基准,放入丙烯酸丁酯(BA)55重量份、丙烯酸甲酯(MA)25重量份、丙烯酸-2-羟乙酯(HEA)20重量份和正十二烷硫醇(n-DDM)0.12重量份、二甲基丙烯酸乙二醇酯(EGDMA)0.3重量份,并以所有反应物100重量份为基准,放入超纯水约28重量份、过硫酸铵约0.5重量份、作为增粘剂放入适量的UH-420(日本艾迪科(ADEKA)公司),作为乳化剂放入将作为阴离子性乳化剂的十二烷基硫酸钠(SDS)和日本艾迪科公司的作为非离子性乳化剂的ER-10以7:3混合而成的混合物0.5重量份后,进行聚合来制备了预乳液。
使用滴液漏斗来将规定量的上述预乳液添加到上述反应器,并将搅拌速度保持规定的同时,以相同的速度滴液了约3个小时。
滴液结束后,进行2个小时的时效处理,再投入作为规定量的氧化还原催化剂的叔丁基过氧化氢及雕白粉(Rongalite/sodium formaldehyde sulfoxylate),并进行了1个小时的反应。反应结束后,降低温度并冷却至室温。此后,用28%浓度的氨水溶液进行中和,来将pH调整为7~8之间。
由此,制备了实施例1的水性粘结剂组合物。
比较例1
在上述实施例1中,以所有单体100重量份为基准,使用了丙烯酸丁酯(BA)55重量份、丙烯酸甲酯(MA)35重量份、丙烯酸(AA)10重量份,作为乳化剂使用了将作为阴离子性乳化剂的十二烷基硫酸钠(SDS)和作为非离子性乳化剂的ER-10以6:4混合而成的混合物,且未使用增粘剂,除此之外,以与上述实施例1相同的方法制备了比较例1的水性粘结剂组合物。
比较例2
在上述比较例1中,作为乳化剂使用了将作为阴离子性乳化剂的十二烷基硫酸钠(SDS)和作为非离子性乳化剂的ER-10以2:8混合而成的混合物,除此之外,以与上述实施例1相同的方法制备了比较例2的水性粘结剂组合物。
评价
1.测定剥离力
将通过上述实施例及比较例聚合的水性粘结剂组合物以30μm的厚度涂敷于聚对苯二甲酸乙二醇酯(PET)离型膜上。将制成的上述粘结片附着于SUS,经过30分钟后,以300mm/分钟的速度测定了剥离力。
并且,将准备的上述样品放置在50℃温度的烘箱3天,再同样地
将上述样品附着于SUS,并以300mm/分钟的速度测定了剥离力。
2.测定凝胶含量
为了观察粘结剂本身的凝胶含量的增大,将实施例及比较例的水性
粘结剂组合物涂敷于PET基材膜上之后,只分离上述粘结剂涂敷层来测
定了凝胶含量。并且,也测定了在50℃温度的烘箱中放置3天的粘结剂
涂敷层的凝胶含量。
3.测定离子含量
采集各自的水性粘结剂树脂并进行干燥后,用ICP测定了实施例及
比较例的离子含量。
本试验例为测定实施例及比较例的初期剥离力及凝胶含量,并测定
在50℃温度的烘箱中放置3天后的剥离力及凝胶含量,来观察水性粘结
剂的经时变化与否的。
将对实施例及比较例的剥离力、凝胶含量及离子含量的试验结果表
示在以下的表1中。
表1
察看上述表1的结果,可知在使用丙烯酸的比较例1及比较例2中,即使水性粘结剂内的离子含量低,也因在高温放置后粘结片本身的凝胶含量的增大而使剥离力下降。
但是,可知,在不使用丙烯酸的实施例1及实施例2中,在高温放置后也没有发生粘结片本身的凝胶含量的增大,并且没有发生由此引起的剥离力的下降。.
即,由于本发明的水性粘结剂组合物包含具有羟基的单体来替代丙烯酸,从而在聚合后不形成螯合物,因此具有如剥离力下降等经时变化小的优点。
以上,以本发明的实施例为中心进行了说明,但这只是用于例示的,只要是本发明所属技术领域的普通技术人员就能够理解可从中进行各种变形及均等的其他实施例。因此,本发明的真正的技术保护范围应根据所附的发明要求保护范围来判断。
Claims (7)
1.一种水性粘结剂组合物,其特征在于,包含具有羟基的单体,在聚合后不形成螯合物;
上述水性粘结剂组合物还包含软单体及硬单体;
上述软单体包含选自由丙烯酸丁酯、丙烯酸乙酯、丙烯酸异丁酯、丙烯酸-2-乙基丁酯、丙烯酸己酯、丙烯酸庚酯、甲基丙烯酸月桂酯、丙烯酸戊酯及丙烯酸-2-乙基己酯构成的组中的一种以上的物质;
上述硬单体包含选自由丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯及甲基丙烯酸-2-乙基己酯构成的组中的一种以上的物质;
所述水性粘结剂组合物不将丙烯酸用作聚合单体;
以所有单体100重量份为基准,所述具有羟基的单体的量为20重量份。
2.根据权利要求1所述的水性粘结剂组合物,其特征在于,上述具有羟基的单体包含选自由丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯及丙烯酸羟丁酯构成的组中的一种以上的物质。
3.根据权利要求1所述的水性粘结剂组合物,其特征在于,上述水性粘结剂组合物还包含引发剂、乳化剂及增粘剂。
4.根据权利要求3所述的水性粘结剂组合物,其特征在于,上述引发剂包含选自由过硫酸钾、过硫酸铵、过硫酸钠、偶氮二异丁腈及过氧化二苯甲酰构成的组中的一种以上的物质。
5.根据权利要求3所述的水性粘结剂组合物,其特征在于,上述乳化剂包含选自由阴离子表面活性剂及非离子表面活性剂构成的组中的一种以上的物质。
6.根据权利要求3所述的水性粘结剂组合物,其特征在于,上述增粘剂为非离子性聚氨酯类增粘剂。
7.一种粘结片,其特征在于,包括粘结剂层,上述粘结剂层是利用权利要求1至6中任一项所述的水性粘结剂组合物形成的。
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