CN1404518A - 预混物和由预混物制备粘合剂和腻子的方法 - Google Patents
预混物和由预混物制备粘合剂和腻子的方法 Download PDFInfo
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Abstract
本发明提供了可用于粘合剂和腻子的流体预混物组。还提供了使用该预混物组提供粘合剂系列和腻子系列的方法。进一步提供了基于该粘合剂和腻子系列的各种粘合剂和腻子。除了由延迟产品差异提供的其它益处,制造商、销售商、或使用者可使用该方法在制造、销售或使用场所调节该粘合剂或腻子以适应处理和最终使用条件。
Description
相关申请的交叉参考
本申请要求美国临时申请60/183,655(申请日:2000年2月18日)60/183,656(申请日:2000年2月18日)和60/247639(申请日:2000年11月10日)的优先权。
本发明的背景
本发明的领域
本发明涉及成套粘结剂预混物、由该成套预混物制备粘合剂和腻子的方法,并涉及由该成套预混物制备各种粘合剂和腻子的方法。
在待审U.S.专利申请系列Nos.60/183,655;60/183,656;和60/247,639中;我们描述了预油漆和由这些采用延迟产品差异的预油漆制造油漆的方法。在这些申请中描述的成套预混成分或原料的使用可延伸至粘合剂的制备。
粘合剂配制包括以合适比例选择和混合合适的粘合剂成分以得到具有特定处理和使用性能,以及所需最终干粘合剂膜性能的粘合剂。许多粘合剂的主要成分是粘结剂,可有可无的增粘剂,和流体介质(如果配方不是净存在的),该流体介质是水(如果粘合剂是水基粘合剂),或溶剂(如果粘合剂是溶剂基粘合剂)。普通的可有可无的成分包括消泡剂,凝结剂,增塑剂,增稠剂,流变改性剂,溶剂,干燥剂,抗结皮剂,表面活性剂,杀霉剂,杀虫剂,交联剂,白色不透明化颜料,增量剂颜料,着色剂,和分散剂。在流体粘合剂配制并施用到表面上之后,粘合剂通过在施加或不施加热或辐射的情况下蒸发水和/或溶剂而干燥,且粘结剂形成其中包含颜料和增量剂颗粒(如果有的话)的膜。
配制粘合剂是复杂的-它不是简单地以不同比率混合一些成分。相反,它包括,根据所需粘合剂的种类选择和混合不同比率的不同成分。这要求制造商在制造过程中根据正在制备的特定粘合剂种类储存许多不同的成分并改变成分。
另外,它要求供应链,尤其是粘合剂零售商的有关人员传送大量的粘合剂以提供各种粘合剂,如各种剥离水平,粘度水平,粘附水平,可去除性水平和可再定位水平。
根据所需成分的数目,配制粘合剂不如配制建筑油漆复杂。但与通常在施用建筑油漆时所经历的条件相比,粘合剂的处理和使用施用可涉及较宽范围的条件。例如,粘合剂根据所用的处理设备(例如,挤塑,凹版和Mayer棒型涂布器,辊和模头涂布,和类似物)而以不同的剪切速率施用,并在宽温度范围内(例如,从低温或全温施用中的低于0℃至某些包装场合中的大于40℃)使用。
因此,最好使用有限数目的成分在大规模工业设备或在较小规模的、施用点、销售点、或使用点场所制备粘合剂,以制备出所有的这些不同的粘合剂,这样使制备各种粘合剂所需的成分的数目和种类最小化。因此,有利地具有一种使得制造商、销售商、或使用者在制造、销售或施用时调节该粘合剂以适应处理和使用条件的体系。
本发明的综述
本发明提供了成套流体预混物粘结剂,一种或多种粘合剂系列,和一定范围的粘合剂。本文所用的″流体″是指任何流动的材料,包括液体,可流动的粉末,和粘稠的,无定形固体。本文所用的预混物是″相互相容的″,如果混合这些预混物而形成的粘合剂没有胶体不稳定性如絮凝的迹象。优选,由这些预混物形成的粘合剂在该粘合剂经过325目筛时具有每升粘合剂低于5克的残余物,如凝胶和砂石,更优选低于1克残余物/升。优选,预混物在经过325目筛时具有每升预混物低于5克的残余物,如凝胶和砂石,更优选低于1克残余物/升预混物。如果预混物和所包括的用以增强特定粘合剂性能的可有可无的添加剂完全相容,即,它们可以任何比率共混而不导致胶体不稳定性,因此它们可以落在所需配制空间内的任何组合共混以在最终粘合剂中获得所需的性能分布。但足够的是,预混物和可有可无的添加剂可以所需比率共混而不导致,以在各种粘合剂中获得所需的性能分布。本文所用的″粘合剂″在广义上使用,包括所有种类的粘合剂,包括净的,水基,和溶剂基粘合剂,包括压敏粘合剂和非压敏粘合剂。可通过本发明方法制成的压敏粘合剂(″PSAs″)包括任何常规PSAs包括,但不限于,热熔体粘合剂,溶剂-基橡胶粘合剂,苯乙烯丁二烯橡胶乳液粘合剂,和丙烯酸粘合剂。这些PSAs用于许多场合,例如用于胶带和标签场合。″粘合剂″的这种定义意味着包括通常称作密封剂,连接水泥,石膏,糊,陶瓷瓦粘合剂,腻子,和类似建筑粘合剂的产品。
本文所用的″粘合剂系列″包括至少两种不同的粘合剂,它们所提供的性能在至少一个可观察的性能,如对某些基材的粘附性,粘度,可去除性,和可再定位性上基本上相互不同。粘合剂制造商和零售商提供各种粘合剂,其范围包括至少两个粘合剂系列。本文所用的″其范围包括至少两个粘合剂系列″是指,定义第一粘合剂系列的可观察性能的具体选择水平与定义第二粘合剂系列等的可观察性能的具体选择水平相结合以定义各种粘合剂中的粘合剂。例如,制备包括5种粘合剂的一定范围的粘合剂可能需要制备包括两个剥离水平,两个粘度水平,两个粘附水平,两个可去除性水平,两个可再定位性水平,和优选其所有组合的粘合剂。因此,可能需要32种不同的粘合剂配方(2x2x2x2x2)。但也包括一定范围的粘合剂,其中因商业原因或因稳定性原因而省略了确定数目的粘合剂系列或预混物,包括最高达总数的10-60%。
足以配制至少一种粘合剂系列的一组不同的,但相互相容的,流体粘合剂粘结剂预混物包括(a)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,粘性低于约300克,和剪切大于约50小时的聚合物粘结剂;(b)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂,和(c)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,粘性大于约500克,和剪切低于约10小时的聚合物粘结剂。优选,预混物的数目是3-15。
本发明也提供了一种粘合剂组合物,包括以上所述的成套预混物,和可有可无的至少一种选自增粘剂,增稠剂,和交联剂的其它成分。
视需要,至少一种预混物进一步包含至少一种可有可无的添加剂,选自增粘剂,增塑剂,增稠剂和交联剂。
也提供了一种配制至少一种粘合剂系列的方法,该方法包含以下步骤:(a)选择一组不同的,但相互相容的,流体粘合剂粘结剂预混物,包含:
(i)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,Polyken粘性低于约300克和剪切大于约50小时的聚合物粘结剂;(ii)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,Polyken粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂;和(iii)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,Polyken粘性大于约500克,和剪切低于约10小时的聚合物粘结剂;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成粘合剂系列。优选,预混物的数目是3-15。
进一步提供可一种提供一定范围的粘合剂的方法,其范围包括至少两个粘合剂系列,该方法包含以下步骤:
(a)选择一组不同的,但相互相容的,流体粘合剂粘结剂预混物,该组包括(i)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,Polyken粘性低于约300克,和剪切大于约50小时的聚合物粘结剂,(ii)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,Polyken粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂,(iii)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,Polyken粘性大于约500克,和剪切低于约10小时的聚合物粘结剂具有;和(iv)至少一种其它的不同预混物,选自(i),(ii),或(iii);和
(b)将预定量的每种预混物分配到容器或涂布器中以形成粘合剂系列。优选,预混物的数目是4-15。
本文的方法可进一步包括提供至少一种增粘剂,至少一种增稠剂,至少一种交联剂,或其组合的步骤。将预定量的增粘剂,增稠剂和/或交联剂分配到容器或涂布器中。
也提供一不同组的足以形成至少一种不同粘合剂系列的预混物,该组包括至少两种不同的,但相互相容的,流体粘合剂粘结剂预混物,选自(a)至少一种预混物,包含至少一种在固化时形成Tg约-70℃-约0℃的聚合物粘结剂的可固化的预聚物;(b)至少一种流体预混物,包含至少一种在固化时形成Tg约-10℃-约70℃的聚合物粘结剂的可固化的预聚物;(c)至少一种预混物,包含至少一种Tg约0℃-约30℃的聚合物粘结剂;(d)至少一种预混物,包含至少一种Tg约-15℃-约15℃的聚合物粘结剂;和(e)至少一种预混物,包含至少一种Tg约-70℃-约0℃的聚合物粘结剂。
也提供一种提供至少一种粘合剂系列的方法,该方法包括以下(a)提供一组不同的,但相互相容的,流体粘合剂粘结剂预混物,包含至少两种选自以下的预混物:(i)至少一种预混物,包含至少一种在固化时形成Tg约-70℃-约0℃的聚合物粘结剂的可固化的预聚物;(ii)至少一种预混物,包含至少一种在固化时形成Tg约-10℃-约70℃的聚合物粘结剂的可固化的预聚物;(iii)至少一种预混物,包含至少一种Tg约0℃-约30℃的聚合物粘结剂;(iv)至少一种预混物,包含至少一种Tg约-15℃-约15℃的聚合物粘结剂;和(v)至少一种预混物,包含至少一种Tg约-70℃-约0℃的聚合物粘结剂;和(b)将预定量的每种预混物分配到容器或涂布器中以形成所述一种粘合剂系列。
进一步提供一种提供一定范围的粘合剂的方法,其范围包括至少两个粘合剂系列,该方法包括以下步骤:(a)提供一组不同的,但相互相容的,流体粘合剂粘结剂预混物,包含至少两种选自以下的预混物:(i)至少一种预混物,包含至少一种在固化时形成Tg约-70℃-约0℃的聚合物粘结剂的可固化的预聚物;(ii)至少一种预混物,包含至少一种在固化时形成Tg约-10℃-约70℃的聚合物粘结剂的可固化的预聚物;(iii)至少一种预混物,包含至少一种Tg约0℃-约30℃的聚合物粘结剂;(iv)至少一种预混物,包含至少一种Tg约-15℃-约15℃的聚合物粘结剂;和(v)至少一种预混物,包含至少一种Tg约-70℃-约0℃的聚合物粘结剂;和(b)将预定量的每种预混物分配到容器或涂布器中以形成所述一种粘合剂系列。
本文的方法还可包括,加入能增强粘合剂的施用或最终性能的材料,如增粘剂,增塑剂,增稠剂,交联剂,及其混合物。
腻子与粘合剂和密封剂的类似之处在于它们基于软聚合物。许多腻子另外与油漆的类似之处在于它们可填充以颜料和增量剂。腻子以其较高的固体含量和较高的粘度及其用以填充和密封裂缝、连接处、和类似物的用途而区别。
如果需要一种粘合剂系列,即,如果要改变一个主要性能(例如,剥离,粘度,粘附,可去除性,或可再定位性),那么完整的粘合剂系列可由以上描述的预混物(i),(ii),和(iii)中的一种或另外由以上描述的(a)-(e)中的至少两种而得到。
如果需要包括两个粘合剂系列的一定范围的粘合剂,即,如果要改变两种主要性能(例如,选自剥离,粘度,粘附,可去除性,和可再定位性的两种性能),那么该范围的粘合剂可由至少一种预混物(i)-(iii)和至少一种其它的但不同的选自预混物(i)-(iii)的预混物,或另外由至少两种以上描述的预混物(a)-(e)和至少一种其它的选自上述预混物(a)-(e)的不同预混物而得到,这取决于所要改变的主要性能。
如果需要包括三种粘合剂系列的一定范围的粘合剂,即,如果要改变三种主要性能(例如,选自剥离,粘度,粘附,可去除性,和可再定位性的三种性能),那么该范围的粘合剂可由至少一种预混物(i),预混物(ii),和预混物(iii)和至少两种其它的选自(i),(ii),或(iii)的不同预混物,或另外由至少一种预混物(a)-(e)和至少两种其它的选自(a)-(e)的不同的预混物而得到,这取决于所要改变的主要性能。
如果需要包括四种粘合剂系列的一定范围的粘合剂,即,如果要改变四种主要性能(例如,选自剥离,粘度,粘附,可去除性,和可再定位性的四种性能),那么该范围的粘合剂可由至少一种预混物(i),预混物(ii),和预混物(iii)和至少三种其它的选自(i)-(iii)的不同预混物而得到,这取决于所要改变的主要性能。
该技术可根据所需的许多其它的主要性能而继续改变。
″选自(i),(ii),和(iii)的其它的预混物″是指一种不同于相应的粘合剂预混物(i),(ii),和(iii),但以其它方式满足有关预混物(i),(ii),和(iii)的限制的粘合剂粘结剂预混物。″选自(a),(b),(c),(d),和(e)的其它的预混物″在本文中是指一种不同于相应的粘合剂预混物(a),(b),(c),(d),或(e),但以其它方式满足有关预混物(a),(b),(c),(d),或(e)的限制的粘合剂粘结剂预混物。
分别在以上实施方案中,选择预混物以覆盖宽的配方空间,这样所需最终粘合剂性能落在这些预混物极端时所定义的共混空间内。在许多情况下,这些预混物本身不是实际的粘合剂,但通过将这些预混物推向这些极端,人们可以将用于粘合剂体系的共混空间最大化。如果预混物,添加剂,和着色剂都是完全相容的,它们可以所需比率共混,得到所需粘合剂系列和各种粘合剂而不会导致胶体不稳定性。
该技术与用于混合组分设计的统计实验设计和分析的设计原理类似;但人们是设计混合物空间的边界以使该粘合剂体系的适应性最大化,而不是设计一种混合物空间以在其内探究响应表面。成功的关键是各成分和预混物在该混合物空间内具有相互相容性。
粘合剂性能可通过许多方式预期。一种途径是使用标准的混合物组分实验设计统计工具开发该共混空间的响应表面模型。这些简单的统计模型可随后通过一个线性优化程序,通过大量格坐标检索,或通过图解分析工具而使用。另一途径是简单地使用经验方法来确定那种共混物为特定粘合剂系列所需并随后将这些简单地经验处方加入粘合剂制造机器软件。
该技术的一个扩展是使粘合剂机器自动预测试某些这样性能(如,粘度,与某些基材的粘附性,剥离,粘性,剪切)并在由预混物配制粘合剂的过程中进行较小的调整。植入粘合剂机器中的反馈回路可提供对颜色,粘附性,剥离强度,粘性,剪切强度,和粘度目标的精确匹配。
优选的是,用于本文的所有流体预混物具有相同或类似的粘度以帮助混合。最终粘合剂配方中的粘度波动预期因为事先平衡该预混物中的各成分而下降。
这些预混物配制使得粘合剂制造的适应性最大化。不是购买单个的粘合剂成分,粘合剂制造商,甚至在销售点和使用点的购买者(家庭装修商店、建筑产品公司、和承包商)可购买制备所需范围粘合剂所需的成套预混物。这些成套预混物包含至少一种预混物(i),(ii)和(iii)和可能的其它的预混物,这取决于所需的配制适应性。视需要,将以上预混物与包括至少一种着色剂如着色颜料或染料的其它的预混物进行混合。
本发明的组和方可用于腻子。
在生产具有所需成套性能的腻子时,粘结剂选择是一个主要因素。本领域熟练技术人员容易看出,粘结剂特征如固体含量,单体选择,分子量,Tg,模量和许多其它的因素影响腻子的性能。本领域熟练技术人员还定性地认识到如何控制这些特征以得到所需腻子性能。这些性能包括拉伸强度对伸长性/柔韧性,粘附,表面粘性,沟开裂,透明度,发黄,收缩,和成本之间的平衡。尽管粘结剂特征和性能之间的定量关系难以得到,但本领域熟练技术人员容易选择适用于粘结剂预混物的粘结剂以得到所需腻子性能。
在腻子实施方案中,该组包括(a)至少一种腻子粘结剂预混物,包含至少一种Tg低于约0℃的聚合物粘结剂;(b)至少一种粘结剂预混物,包含至少一种Tg低于约25℃的聚合物粘结剂;和(c)视需要,至少一种增量剂预混物,包含至少一种增量剂;其中预混物的固体含量至少为约50%重量。
也提供一种形成至少一种腻子系列的方法,该方法包含以下步骤:
(a)提供一组足以形成至少一种腻子系列的不同的,但相互相容的,流体腻子粘结剂预混物,该组包括(i)至少一种腻子粘结剂预混物,包含至少一种Tg低于约0℃的聚合物粘结剂;(ii)至少一种粘结剂预混物,包含至少一种Tg低于约25℃的聚合物粘结剂;和(iii)视需要,至少一种增量剂预混物,包含至少一种增量剂;其中预混物的固体含量至少为约50%重量;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成至少一种腻子系列。
增量剂预混物可进一步包含至少一种不透明化颜料。另外,该组腻子预混物可进一步包含至少一种流动的相互相容的预混物,其中包含至少一种不透明化颜料。
本文的方法可进一步包括在粘合剂或腻子粘结剂预混物分配到容器中之前、过程中或之后将它们进行混合的步骤。该方法还可包括在这些预混物分配到容器中之前或过程中将它们进行混合的步骤。该方法还可包括,在将这些预混物分配到容器中之前、过程中或之后或在将它们分配到涂布器中之前或过程中,调节它们的粘度的步骤。本文的方法可在制造设备、分配器、销售点、或使用点连续实施。另外,该方法可通过计算机控制。″其它的预混物[“a”,“b”,或“c”]是指一种不同于相应的腻子粘结剂预混物(a)和(b)和腻子增量剂预混物(c),但以其它方式满足与腻子预混物(a),(b)和(c)有关的限制的腻子预混物。
尽管例举了压敏粘合剂和腻子,但本方法不限于仅制备压敏粘合剂或腻子本身,而是也可扩展用于制备任何水基或溶剂基粘合剂,密封剂,腻子或相关建筑产品。其中可以使用由本发明方法之处的粘合剂和相关产品的工业和市场部门包括用于建筑,初始木材粘结,家具,地面运输-OEM,汽车后市场,航天空间,电气/电子器件,包装,装订,纺织品,鞋类,压敏磨料,摩擦材料,铸造厂,消费者,气溶胶,医疗,牙科,各种产品组件,和类似物的粘合剂。
本发明的详细描述
本文的预混物分别包含具有特定性能的聚合物粘结剂。聚合物粘结剂是形成粘合剂的基本膜的聚合物或预聚物。粘结剂粘结颜料(如果存在)和/或增量剂并提供所需的粘合剂流动性。选择用于预混物的粘结剂取决于该配制粘合剂的最终用途。
合适的聚合物粘结剂包括水基和溶剂基天然和合成聚合物,包括(但不限于),均聚物,共聚物或三元聚合物如丙烯酸和/或甲基丙烯酸聚合物,聚乙酸乙烯酯,聚乙烯基醇,苯乙烯-丙烯酸共聚物,苯乙烯-丁二烯共聚物,乙酸乙烯酯-丙烯酸共聚物,乙烯-乙酸乙烯酯共聚物,乙酸乙烯酯-versatic酸乙烯酯共聚物,乙酸乙烯酯-马来酸乙烯基酯共聚物,乙酸乙烯酯-氯乙烯-丙烯酸三元聚合物,乙烯-乙酸乙烯酯-丙烯酸三元聚合物,聚氨酯,聚乙烯基缩丁醛,结构丙烯酸聚合物,厌氧的氰基丙烯酸酯聚合物,聚氯乙烯,聚偏二氯乙烯,聚乙烯,乙烯-乙酸乙烯酯共聚物,聚丙烯,乙烯/丙烯酸共聚物,乙烯/丙烯酸甲基酯共聚物,辐射的聚乙烯,聚酰胺,聚酯,环氧,苯酚,氨基,呋喃,聚酰亚胺,天然橡胶,苯乙烯共聚物和三元聚合物,非嵌段苯乙烯系嵌段共聚物,氯丁橡胶,腈橡胶,丁烯,聚丁烯,乙烯-丙烯-二烯橡胶,橡胶硅氧烷,动物胶,酪蛋白,淀粉和小麦粉,糊精,纤维素,沥青,松香,木质素,硅酸盐,苯乙烯-丁二烯橡胶,苯乙烯-丁二烯,丙烯腈-丁二烯-苯乙烯,卤代二烯,和类似物。聚合物或预聚物可视需要包含最高约10%重量的官能单体,例如,但不限于,羧酸,磷酸盐,硫酸盐,磺酸盐,和酰胺单体和其组合,非官能单体,及其混合物。聚合物粘结剂优选为水基胶乳聚合物。
对于预混物,视需要包括少量,即,基于预混物的总重低于约20%重量的常规粘合剂添加剂如增粘剂,增塑剂,交联剂,增稠剂,酸,碱,消泡剂,凝结剂,助溶剂,分散树脂,杀霉剂,杀虫剂,抗冻剂;不透明化颜料,增量剂颜料,着色剂,玻璃和聚合物珠和类似物。这些添加剂必须与用于配制粘合剂系列的一种或多种预混物中的其它的粘合剂成分相容。这些可有可无的成分可单独加入或加入预混物中。在实施例中,增粘剂,交联剂,和/或增稠剂作为单独成分被包括,而不是加入预混物中。
粘性,剥离强度,和耐剪切性是填充相互排斥的性能,它们在调节适用于特定场合的粘合剂组合物时非常重要。粘性一般度量在快应变速率和低应力数值下的粘稠流动。剥离强度度量在中应变速率和中至高应力数值下的耐流动性、以及粘合剂的内聚强度。耐剪切性度量在中应力数值下的耐流动性。
可以加入聚合物添加剂,如增粘剂和增塑剂以改进粘合剂的性能包括,例如,成品粘合剂的粘弹性。所选的特定聚合物添加剂可例如根据所涉及的粘合剂和所寻求的改进而变化。
一般来说,为了增强粘合剂的性能特性,增粘剂应该针对它所加入的粘合剂而具有一定范围的性能。例如,增粘剂一般应该具有低于粘合剂聚合物的分子量。另外,增粘剂一般应该具有高于粘合剂聚合物的玻璃转变温度(Tg)。增粘剂的软化温度一般应该高于粘合剂聚合物,且增粘剂一般应该具有与粘合剂聚合物的最低相容性。
合适的增粘剂包括分散的和固体等级的增粘剂如松香酯,松香酸,和烃树脂,包括脂族和芳族树脂,和类似物。
增塑剂可例如加入粘合剂组合物以增加其可使用性、柔韧性和/或膨胀性。它们的分子小于存在于粘合剂体系中的聚合物粘结剂分子。
根据所涉及的粘合剂体系,增塑剂的加入可降低总体系的熔体粘度,弹性模量,和玻璃转变温度(Tg)。增塑剂也可加入聚合物配方,通过促进聚合物分子和增塑剂之间而不是聚合物分子本身之间的成键而增加柔韧性。增塑剂分子隔离粘结剂的较大聚合物链并降低它们之间的吸引力,因此用作润滑剂。此时,增塑剂也可增加所得粘合剂组合物的比体积并改变折射指数。增塑剂的加入也可增加粘合剂组合物的粘度。
合适的交联剂包括多价金属如锌,镁,铝,钙,铁,锆,和类似物。
合适的不透明化颜料包括二氧化钛(TiO2)或二氧化钛和辅助遮盖颜料如空隙化胶乳聚合物颗粒,氧化锌,氧化铅,合成聚合物颜料,及其混合物的组合。金红石和锐钛矿级二氧化钛适用于本文。
金红石二氧化钛是优选的。其中二氧化钛的表面可用各种有机和/或无机表面处理剂,如,硅石,矾土,和氧化锆的氧化物进行处理。热解法钛氧化物也可用于本文。
可用于本文的空隙化胶乳颗粒的颗粒尺寸直径为约100nm-约2,500nm且空隙分数为约10%-约75%。
优选,空隙化胶乳颗粒的颗粒尺寸为约500nm-约1,100nm。空隙化胶乳颗粒具有至少一个空隙不可具有多个空隙,非球形空隙,相互连接的空隙,具有连接到可能外部的通道的空隙,和描述为起疱的和海绵状的结构。优选,它们可具有单个空隙。空隙化胶乳颗粒的玻璃转变温度(Tg)至少为约20℃,优选至少约50℃。
玻璃转变温度越高,颗粒越硬且它越不易塌陷。如果空隙化胶乳颗粒塌陷,它们不能用于遮盖。空隙化胶乳颗粒可通过本领域已知的常规聚合反应工艺,如描述于US-A3,784,391,US-A-4,798,691,US-A-4,908,271,US-A-4,972,000,US-A-5,041,464,US-A-5,157,084,US-A-5,216,044和US-6,020,435,以及日本专利申请60/223,873,61/62510,61/66710,61/86941,62/127336,62/156387,01/185311,和02/140272的那些工艺而制成。优选,空隙化胶乳颗粒根据US-A-4,427,836,US-A-4,469,825,US-A-4,594,363,US-A4,880,842,US-A-5,494,971和US-A-6,020,435而制成。
适用于本文的增量剂颜料包括硫酸钡(约1-约15微米),BlancFixe(约0.5-约5微米),碳酸钙(约0.05-约35微米),硅石(约0.001-约14微米),硅酸镁(约0.5-约15微米),硅酸铝(约0.2-约5微米),云母,膨润土,硅铝酸镁,热解法矾土,胶态硅镁土,合成无定形硅铝酸钠,硅铝酸钠钾,和类似物。
增稠剂是一个总称,包括任何加入粘合剂中以改变其流变分布的材料。优选的增稠剂是缔合增稠剂。适用于本文的增稠剂包括聚乙烯醇(PVA),本领域称作HASE乳液的憎水改性的,碱溶性乳液,本领域称作ASE乳液的碱溶性或碱可膨胀的乳液,本领域称作HEUR增稠剂的憎水改性的氧化乙烯-氨基甲酸乙酯聚合物,和纤维素增稠剂如羟基甲基纤维素(HMC),羟基乙基纤维素(HEC),憎水改性的羟基乙基纤维素(HMHEC),羧基甲基纤维素钠(SCMC),羧基甲基2-羟基乙基纤维素钠,2-羟基丙基甲基纤维素,2-羟基乙基甲基纤维素,2-羟基丁基甲基纤维素,2-羟基乙基乙基纤维素,2-羟基丙基纤维素,和类似物。也可用作增稠剂的是热解法硅石,硅镁土粘土和其它种类的粘土,钛酸盐螯合剂,和类似物。
适用于本文的分散剂包括非离子,阴离子,和阳离子分散剂如2-氨基2-甲基1-丙醇(AMP),二甲基氨基乙醇(DMAE),三聚磷酸钾(KTPP),三聚磷酸钠(TSPP),柠檬酸酸和其它的羧酸,和类似物。阴离子聚合物如基于多羧酸的均聚物和共聚物,包括已憎水改性的或亲水改性的那些,如,用各种单体如苯乙烯,丙烯酸酯或甲基丙烯酸酯,二异丁烯,和其它的亲水或憎水共聚单体改性的聚丙烯酸或聚甲基丙烯酸或马来酸酐也适用作分散剂,还包括前述分散剂的盐,及其混合物。
合适的消泡剂包括炔二醇,硅氧烷-基和矿物油基消泡剂,和类似物。
合适的凝结剂,增塑剂,和其它的可有可无的溶剂包括乙二醇,丙二醇,己二醇,2,2,4-三甲基-1,3-戊烷二醇单异丁酸酯(TEXANOLTM),二醇醚,矿物精,甲基卡必醇,丁基卡必醇,邻苯二甲酸酯,己二酸酯,和类似物。
合适的杀霉剂和杀虫剂包括氧化锌,异噻唑啉酮,***,和类似物。
合适的表面活性剂包括阳离子,阴离子,和非离子表面活性剂。
为了将制备一定范围的粘合剂所需的粘合剂成分的数目减至最低,需要考虑该范围粘合剂所需的主要性能的极端并配制能够以各种组合共混的粘合剂预混物,在极端值和之间点时所需的主要性能。特定性能也可通过包括能增强所需性能的粘合剂添加剂而提高。
本文公开的所有范围是包括性的,且所列范围的最小值和最大值是可合并的。粘性按照PSTC标准粘性试验在速率12英寸/分钟下测量。剥离按照PSTC标准剥离试验在Polyken测试仪上测量。剪切在温度55-80°F下,在静态剪切下,针对一个在1平方英寸上叠放有1kg重物的测试样品进行测量。
所有的以上测量使用涂布厚度0.9-1.1mils进行。
玻璃转变温度(“Tg”)通过示差扫描量热法以速率20℃/分钟进行。
实施例
实施例1-粘合剂粘结剂预混物的制备
预混物1通过将100克丙烯酸压敏聚合物(N-619,得自Rohm和HaasCompany,Philadelphia,PA)与0.5克标准市售非离子或阴离子润湿剂,1.0克乙氧基化苯酚机械稳定剂,和0.5克标准消泡剂进行混合而制成。pH用氨调节至8.0以上。
预混物2通过将100克丙烯酸压敏聚合物(N-580,得自Rohm和HaasCompany,Philadelphia,PA)与0.5克标准市售非离子或阴离子润湿剂,1.0克乙氧基化苯酚机械稳定剂,和0.5克标准消泡剂进行混合而制成。pH用氨调节至8.0以上。
预混物3通过将100克丙烯酸压敏聚合物(N-1031,得自Rohm和HaasCompany,Philadelphia,PA)与0.5克标准市售非离子或阴离子润湿剂,1.0克乙氧基化苯酚机械稳定剂,和0.5克标准消泡剂进行混合而制成。pH用氨调节至8.0以上。
实施例2-粘合剂的制备
粘结剂1,2,和3可以各种比率与各种量的分散的增粘剂和交联剂一起合并,生产出具有适用于压敏场合如胶带和标签场合压敏粘合剂(PSAs)的特性的粘合剂。具有低粘度的粘合剂可通过凹版和Mayer棒-型涂布器施用。具有较高粘度的粘合剂适用于辊和模头涂布器。
增稠剂是HASE增稠剂(Acrysol TT-615,得自Rohm和HaasCompany,Philadelphia,PA)。增粘剂是一种分散的松香酯,松香酸,或烃。交联剂是多价金属型。
该粘合剂预混物的配方示于下表。成分量以克计。
Adhesive Type | ||||||||||||
成分 | 聚烯烃粘附** | 聚烯烃粘附 | 通用低剥离 | 通用低剥离 | 通用高剥离** | 通用高剥离 | 可再定位 | 可再定位 | 可去除低剥离 | 可去除低剥离 | 可去除高剥离 | 可去除高剥离 |
预混物1 | 50-60 | 50-60 | - | - | 70-80 | 70-80 | 20-30 | 20-30 | - | - | 10 to 20 | 10 to 20 |
预混物2 | - | - | 40-50 | 40-50 | - | - | 70-80 | 70-80 | 10 to 20 | 10 to 20 | - | - |
预混物3 | 50 to 60 | 5 to 20 | 40-50 | 40-50 | - | - | - | - | 80 to 90 | 80 to 90 | 80-90 | 80-90 |
增稠剂 | - | 1 to 1.5 | - | 1 to 1.5 | - | 1 to 1.5 | 1 to 1.5 | 1 to 1.5 | - | 1 to 1.5 | - | 1 to 1.5 |
增粘剂 | 20-30** | 20-30 | 50 to 10 | 5 to 10 | 20-30*** | 20-30 | 1 to 1.5 | 1 to 1.5 | - | - | - | - |
交联剂 | - | - | - | - | - | - | 1 to 2 | 1 to 2 | 1 to 2 | 1 to 20 | 1 to 2 | 1 to 2 |
评价 | 与聚烯烃表面的粘附性,**范围导致中至高粘附 | 较高粘度涂布器 | 对于标签场合,结果可从低至中粘附 | 较高粘度涂布器 | 高粘附/表面依赖性***范围导致中至高粘附 | 较高粘度涂布器 | 具有导致永久粘附的短期可去除性的标签PSA | 较高粘度涂布器 | 在不同表面的各种可去除性 | 较高粘度涂布器 | 高粘附和在不同表面的各种可去除性 | 较高粘度涂布器 |
实施例3-腻子预混物的制备
以下预混物用于配制一系列腻子。
第一粘结剂预混物包含一种Tg为-50℃的软丙烯酸粘结剂(Rhople1950,得自Rohm和Haas Company,Philadelphia,PA)。该粘结剂的固体含量是约62-65%该软丙烯酸粘结剂与本领域熟练技术人员熟知的腻子添加剂,如二醇,表面活性剂,防腐剂,杀霉剂,消泡剂,和可有可无的添加剂,如,粘附用硅烷一起配制。
第二粘结剂预混物包含聚合物粘结剂,它是Tg为-9℃且固体含量为约55%的成本较低的乙烯基或乙烯基/丙烯酸粘结剂(Rovace 86,得自Rohm和Haas Company,Philadelphia,PA)。将它配制成较低成本的预混物,其中使用增塑剂以进一步降低Tg和例如用于以上丙烯酸粘结剂的其它的腻子添加剂。
增量剂预混物通过将钙碳酸盐和二氧化钛在水与选择用以产生稳定预混物的分散剂和增稠剂一起研磨而制成。该预混物应该在尽可能高的固体含量下制备以降低引入腻子的水的量。所得腻子在用于填充间隙时收缩较少。因此,固体颜料和/或填料可用于进一步增加腻子的固体含量。该腻子要求混合或研磨技术能够驾驭其高粘度。
包含固体级羟基乙基纤维素(Natrosol 250MXR,Hercules,Inc.,Wilmington,DE)的添加剂预混物制备用作增稠剂。
实施例4-腻子的制备
腻子通过将一种或这两种粘结剂预混物与增量剂预混物进行共混而制成。随后加入添加剂预混物并将所得混合物在Sigma磨机或Hockmeyer混合器(Hockmeyer设备公司,Elizabeth City,NC)上研磨或混合。视需要,该磨机或混合器可包含一个填充腻子管的加料螺杆,因此产生用于生产腻子的连续工艺。采用本发明的方法,腻子的这种连续生产可根据需要提供系列腻子。
上述四种预混物通过将它们以不同比例合并而用于生产系列腻子。例如,利用第一粘结剂预混物、增量剂预混物、和添加剂预混物,可生产出高质量腻子。几种等级的腻子可使用不同的量增量剂预混物而提供。第二粘结剂预混物可以类似方式用于生产几种较低质量/较低成本的腻子。腻子质量和性能上的其它变化可通过使用第一和第二粘结剂预混物的组合以及增量剂预混物,和添加剂预混物(即,增稠剂)而实现。排除增量剂预混物,得到透明腻子。使用一种或这两种粘结剂预混物得到一定品质范围的透明腻子。
该实施例可以有许多变化。填料和颜料可以单独预混物的形式提供且它们的比率和含量可加以控制,这样可改变性能如粘附和表面粘性.具有较少或没有二氧化钛的腻子可用其它颜色染色或着色。可以使用需要用碱中和的增稠剂,包括,例如,憎水改性的,碱可膨胀的乳液如AcrysolTM TT-615(得自Rohm和Haas Company,Philadelphia,PA)。如果使用这种增稠剂,碱如铵或氢氧化钠可在混合或研磨腻子的过程中加入。可以使用增稠剂的混合物。许多其它的腻子添加剂,如热解法硅石,闪锈抑制剂,锌配合物,位阻胺光稳定剂和类似物可用于各种预混物。
Claims (36)
1.一组不同的,但相互相容的,流体粘合剂粘结剂预混物,该组包括:
(i)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,粘性低于约300克,和剪切大于约50小时的聚合物粘结剂;
(ii)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂,和
(iii)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,粘性大于约500克,和剪切低于约10小时的聚合物粘结剂。
2.一种粘合剂,包含根据权利要求1的预混物组和至少一种选自增粘剂,增塑剂,增稠剂,交联剂,及其混合物的添加剂。
3.根据权利要求1的预混物组,其中预混物的数目是3-15。
4.根据权利要求1的预混物组,其中至少一种预混物进一步包含至少一种选自增粘剂,增塑剂,增稠剂,和交联剂的添加剂。
5.一种形成至少一种粘合剂系列的方法,该方法包含以下步骤:(a)提供一组不同的,但相互相容的,流体粘合剂粘结剂预混物,该组包含:
(ii)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,Polyken粘性低于约300克和剪切大于约50小时的聚合物粘结剂;
(iii)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,Polyken粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂;和
(iv)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,Polyken粘性大于约500克,和剪切低于约10小时的聚合物粘结剂;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成粘合剂系列。
6.一种形成一定范围的粘合剂的方法,该范围包括至少两种粘合剂系列,该方法包含以下步骤:
(a)提供一组不同的,但相互相容的,流体粘合剂粘结剂预混物,该组包含:
(ii)至少一种预混物,包含至少一种剥离低于约20盎司/英寸,Polyken粘性低于约300克和剪切大于约50小时的聚合物粘结剂;
(iii)至少一种预混物,包含至少一种剥离低于约20-约50盎司/英寸,Polyken粘性约300-约500克,和剪切约5-约50小时的聚合物粘结剂;和
(iv)至少一种预混物,包含至少一种剥离大于约50盎司/英寸,Polyken粘性大于约500克,和剪切低于约10小时的聚合物粘结剂;和
(v)至少一种其它的选自预混物(i)-(iii)的不同粘结剂预混物;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成粘合剂系列。
7.根据权利要求5或权利要求6的方法,还包括提供至少一种选自增粘剂,增塑剂,增稠剂,和交联剂的添加剂的步骤。
8.根据权利要求7的方法,还包括经历预定量的添加剂分配到容器或涂布器中的步骤。
9.根据权利要求5或权利要求6的方法,其中至少一种预混物进一步包含至少一种选自增粘剂,增塑剂,增稠剂,和交联剂的添加剂。
10.根据权利要求5或权利要求6的方法,其中预混物的数目是4-15。
11.一组不同的足以形成至少一种不同粘合剂系列的预混物,该组包括至少两个选自以下的预混物:
(a)至少一种预混物,包含至少一种在固化时形成Tg约-70℃-约0℃的聚合物粘结剂的可固化的预聚物;
(b)至少一种流体预混物,包含至少一种在固化时形成Tg约-10℃-约70℃的聚合物粘结剂的可固化的预聚物;
(c)至少一种预混物,包含至少一种Tg约0℃-约30℃的聚合物粘结剂;
(d)至少一种预混物,包含至少一种Tg约-15℃-约15℃的聚合物粘结剂;和
(e)至少一种预混物,包含至少一种Tg约-70℃-约0℃的聚合物粘结剂。
12.一种形成至少一种粘合剂系列的方法,该方法包括:(a)提供根据权利要求11的粘结剂预混物组;和(b)将预定量的每种预混物分配到容器或涂布器中以形成粘合剂系列。
13.一种提供一定范围的粘合剂的方法,其范围包括至少两个粘合剂系列,该方法包括以下步骤:
(a)提供一组不同的,但相互相容的,流体粘合剂粘结剂预混物,包含至少两种选自以下的预混物:
(i)至少一种预混物,包含至少一种在固化时形成Tg约-70℃一约0℃的聚合物粘结剂的可固化的预聚物;
(ii)至少一种预混物,包含至少一种在固化时形成Tg约-10℃-约70℃的聚合物粘结剂的可固化的预聚物;
(iii)至少一种预混物,包含至少一种Tg约0℃-约30℃的聚合物粘结剂;
(iv)至少一种预混物,包含至少一种Tg约-15℃-约15℃的聚合物粘结剂;和
(v)至少一种预混物,包含至少一种Tg约-70℃-约0℃的聚合物粘结剂;和
(vi)至少一种其它的选自预混物(i),(ii),(iii),(iv),和(v)的不同预混物;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成所述粘合剂系列。
14.根据权利要求5,6,12或13的方法,进一步包括在将预混物分配到容器中之前、过程中或之后混合这些预混物的步骤。
15.根据权利要求5,6,12或13的方法,进一步包括在将预混物分配到涂布器中之前或过程中混合这些预混物的步骤。
16.根据权利要求5,6,12或13的方法,进一步包括在将预混物分配到容器中之前、过程中或之后调节这些预混物的粘度的步骤。
17.根据权利要求5,6,12或13的方法,进一步包括在将预混物分配到涂布器中之前或过程中调节这些预混物的粘度的步骤。
18.根据权利要求5,6,12或13的方法,其中该方法在一个制造设备上进行。
19.根据权利要求5,6,12或13的方法,其中该方法在销售点进行。
20.根据权利要求5,6,12或13的方法,其中该方法在使用点进行。
21.根据权利要求5,6,12或13的方法,其中该方法通过计算机控制。
22.根据权利要求5,6,12或13的方法,进一步包括提供至少一种选自增粘剂和增塑剂的添加剂的步骤。
23.一组足以形成至少一种腻子系列的不同的,但相互相容的,流体预混物,该组包括:
(i)至少一种腻子粘结剂预混物,包含至少一种Tg低于约0℃的聚合物粘结剂;
(ii)至少一种粘结剂预混物,包含至少一种Tg低于约25℃的聚合物粘结剂;和
(iii)视需要,至少一种增量剂预混物,包含至少一种增量剂。
24.根据权利要求23的预混物组,该组进一步包含至少一种其它的流体粘结剂预混物或流体增量剂预混物。
25.根据权利要求24的预混物组,其中流体增量剂预混物进一步包含至少一种不透明化颜料。
26.根据权利要求23的预混物组,进一步包括至少一种包含至少一种不透明化颜料的流体不透明化预混物。
27.一种形成至少一种腻子系列的方法,该方法包括:
(a)提供根据权利要求23,24,25或26的预混物组;和
(b)将预定量的每种预混物分配到容器或涂布器中以形成腻子系列。
28.根据权利要求27的方法,其中该方法是连续的。
29.根据权利要求27的方法,进一步包括在将预混物分配到容器中之前、过程中或之后混合这些预混物的步骤。
30.根据权利要求27的方法,进一步包括在将预混物分配到涂布器中之前或过程中混合这些预混物的步骤。
31.根据权利要求27的方法,进一步包括在将预混物分配到容器中之前、过程中或之后调节这些预混物的粘度的步骤。
32.根据权利要求27的方法,进一步包括在将预混物分配到涂布器中之前或过程中调节这些预混物的粘度的步骤。
33.根据权利要求27的方法,其中该方法在一个制造设备上进行。
34.根据权利要求27的方法,其中该方法在销售点进行。
35.根据权利要求27的方法,其中该方法在使用点进行。
36.根据权利要求27的方法,其中该方法通过计算机控制。
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CN01805208A Pending CN1416455A (zh) | 2000-02-18 | 2001-02-16 | 预油漆和由预油漆制备路标漆的方法 |
CNB018052037A Expired - Lifetime CN1208407C (zh) | 2000-02-18 | 2001-02-16 | 含有不透明颜料的稳定混合物 |
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CNB018052037A Expired - Lifetime CN1208407C (zh) | 2000-02-18 | 2001-02-16 | 含有不透明颜料的稳定混合物 |
CNB018052096A Expired - Fee Related CN1188478C (zh) | 2000-02-18 | 2001-02-16 | 预油漆和从预油漆制备油漆的方法 |
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-
2001
- 2001-02-14 MX MXPA01001665 patent/MXPA01001665A/es unknown
- 2001-02-16 TW TW090103659A patent/TWI283698B/zh not_active IP Right Cessation
- 2001-02-16 EP EP01914399A patent/EP1268683A2/en not_active Withdrawn
- 2001-02-16 AU AU39790/01A patent/AU783738B2/en not_active Ceased
- 2001-02-16 CN CN01805205A patent/CN1404518A/zh active Pending
- 2001-02-16 CN CN01805208A patent/CN1416455A/zh active Pending
- 2001-02-16 EP EP01916111A patent/EP1257605A2/en not_active Withdrawn
- 2001-02-16 JP JP2001560299A patent/JP2003523440A/ja not_active Withdrawn
- 2001-02-16 PL PL01366299A patent/PL366299A1/xx not_active Application Discontinuation
- 2001-02-16 BR BR0108470-4A patent/BR0108470A/pt not_active Application Discontinuation
- 2001-02-16 AT AT01910953T patent/ATE299921T1/de not_active IP Right Cessation
- 2001-02-16 US US09/785,152 patent/US6531537B2/en not_active Expired - Fee Related
- 2001-02-16 CN CNB018052037A patent/CN1208407C/zh not_active Expired - Lifetime
- 2001-02-16 AU AU2001238426A patent/AU2001238426A1/en not_active Abandoned
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- 2001-02-16 DE DE60112060T patent/DE60112060T2/de not_active Expired - Lifetime
- 2001-02-16 KR KR20027010663A patent/KR100754939B1/ko not_active IP Right Cessation
- 2001-02-16 BR BR0108474-7A patent/BR0108474A/pt not_active Application Discontinuation
- 2001-02-16 MX MXPA02007926 patent/MX235121B/es active IP Right Grant
- 2001-02-16 JP JP2001560303A patent/JP2004500461A/ja active Pending
- 2001-02-16 AU AU43173/01A patent/AU4317301A/en not_active Withdrawn
- 2001-02-16 US US09/785,147 patent/US20020016405A1/en not_active Abandoned
- 2001-02-16 KR KR1020027010654A patent/KR20030032919A/ko not_active Application Discontinuation
- 2001-02-16 CN CNB018052096A patent/CN1188478C/zh not_active Expired - Fee Related
- 2001-02-16 BR BR0108468-2A patent/BR0108468A/pt not_active Application Discontinuation
- 2001-02-16 JP JP2001560305A patent/JP2003523442A/ja active Pending
- 2001-02-16 EP EP01912830A patent/EP1265970A2/en not_active Withdrawn
- 2001-02-16 WO PCT/US2001/005307 patent/WO2001060925A2/en active IP Right Grant
- 2001-02-16 BR BR0108475-5A patent/BR0108475A/pt not_active Application Discontinuation
- 2001-02-16 TW TW090103658A patent/TW583292B/zh not_active IP Right Cessation
- 2001-02-16 KR KR1020027010664A patent/KR20030076924A/ko not_active Application Discontinuation
- 2001-02-16 WO PCT/US2001/005205 patent/WO2001060931A2/en active IP Right Grant
- 2001-02-16 KR KR1020027010659A patent/KR100810949B1/ko not_active IP Right Cessation
- 2001-02-16 WO PCT/US2001/005308 patent/WO2001060936A2/en not_active Application Discontinuation
- 2001-02-16 PL PL01365175A patent/PL365175A1/xx unknown
- 2001-02-16 WO PCT/US2001/005101 patent/WO2001060929A2/en not_active Application Discontinuation
- 2001-02-16 PL PL01357302A patent/PL357302A1/xx unknown
- 2001-02-16 US US09/785,376 patent/US6919400B2/en not_active Expired - Lifetime
- 2001-02-16 JP JP2001560308A patent/JP2003523443A/ja active Pending
- 2001-02-16 AU AU41572/01A patent/AU4157201A/en not_active Abandoned
- 2001-02-16 US US09/785,389 patent/US6613832B2/en not_active Expired - Fee Related
- 2001-02-16 WO PCT/US2001/005110 patent/WO2001060930A2/en active Application Filing
- 2001-02-16 AR ARP010100727A patent/AR029800A1/es not_active Application Discontinuation
- 2001-02-16 EP EP01910953A patent/EP1268689B1/en not_active Revoked
- 2001-02-16 MX MXPA02007924 patent/MX248298B/es active IP Right Grant
- 2001-02-16 AU AU38509/01A patent/AU781472B2/en not_active Expired
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101974262A (zh) * | 2010-11-16 | 2011-02-16 | 天津市叁零叁化工建材有限公司 | 一种具有柔韧性的中性耐水腻子膏及其制备方法 |
CN101974262B (zh) * | 2010-11-16 | 2012-07-11 | 天津市万畅建材有限公司 | 一种具有柔韧性的中性耐水腻子膏及其制备方法 |
CN106433524A (zh) * | 2016-08-30 | 2017-02-22 | 泰兴联创绝缘材料有限公司 | 一种丙烯酸乳液共混剥离力连续可调压敏胶配方、制备方法 |
CN106433524B (zh) * | 2016-08-30 | 2018-07-06 | 泰兴联创绝缘材料有限公司 | 一种丙烯酸乳液共混剥离力连续可调压敏胶配方、制备方法 |
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