CN1394228A - 筒装单组分密封胶分散体 - Google Patents
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Abstract
本发明涉及一种基于乙烯基聚合物分散体的单组分密封胶,湿状态下基本不含挥发性有机化合物VOC,干状态下具有自粘性。本发明密封胶特别适合聚烯烃材料的接合。
Description
本发明涉及一种基于乙烯基聚合物分散体的单组分密封胶(sealant),该密封胶在湿状态下基本不含挥发性有机化合物,干状态下具有自粘性。本发明还涉及该密封胶的制备和用途,以及涂有该密封胶的材料。
材料的接合一般分为粘接和封接(sealing)。从金属加工业到建筑业,各行各业都会用到封接。密封胶的作用是调节部件之间的移动和密封接口。接口必须密封,以防止固体、液体或气体渗入不该去的地方。另一方面,对于胶粘剂而言,其主要作用在于形成某种粘合,这样,胶粘剂的粘合性和粘合强度就变得很重要。用于材料接合的粘接组合物和封接组合物可根据其稠度分为固体、弹性体或塑性体。随着拉伸剪切强度的降低,组合物的拉伸通过其最大值,同时,组合物由固体区经弹性区转变为塑性区。组合物的稠度决定它是胶粘剂(固体至弹性体)还是密封胶(弹性体至塑性体)。因此,胶粘剂的拉伸强度必须足以形成结构性粘合连接。另一方面,作为密封胶的组合物一般具有弹性体特征,即具有一定的膨胀能力(expansion capacity)以适应膨胀和收缩,从而避免裂纹或裂缝导致的渗漏。已知密封胶能够在施加后固化,因而不会残留污染物粘在表面。
在建筑业中,为了封接聚乙烯膜等聚烯烃材料,目前使用的是基于溶剂因而含有挥发性有机化合物的密封胶。出于环保考虑,也是因为其强烈的异味,此类密封胶正遭到越来越多的抵制,最近的开发方向是无溶剂密封胶。
因此,本发明的目的在于提供一种能够有效封接聚烯烃材料但挥发性有机化合物含量尽可能低的密封胶。
为了实现这一目的,本发明提供了一种单组分密封胶,它基本上不含挥发性有机化合物,基于乙烯基聚合物分散体,而且在干状态下具有自粘性。
因此,本发明提供了一种基于乙烯基聚合物分散体的单组分密封胶,它在湿状态下基本不含挥发性有机化合物,干状态下具有自粘性。本发明还提供制备本发明密封胶的方法,以及用它来连接和/或封接材料尤其是聚烯烃材料的用途。本发明还提供了涂有本发明密封胶的材料。各从属权利要求和以下叙述描述了本发明的优选实施方式。
本发明的密封胶在干状态下具有自粘性。密封胶表面的粘性可按照“压敏胶粘剂的试验方法”第6版,压敏胶带协会,Itasca III,用滚球法进行测定,滚球路径短于30cm,短于20cm更好。本发明的密封胶在干燥后具有自粘性;换言之,可在任何时候,即使在干燥后,实现粘接,并可保持这种自粘性。
合适的乙烯基聚合物包括各种至少单体之一选自“压敏技术手册”第二版,Donatas Satas,1989,Van Nostrand Reinhold,0-442-28026-2的第444-450页所述的聚合物。出于多种考虑,尤其是抗老化稳定性,尤其适合的是至少基于丙烯酸酯和/或甲基丙烯酸酯单体的乙烯基聚合物。这些丙烯酸酯和/或聚甲基丙烯酸酯类聚合物如果还包含其他单体,则最好是乙烯基单体,例如乙酸乙烯酯,乙烯基醚,卤乙烯或乙烯基芳族化合物,例如苯乙烯或乙烯基苯,或脂族单体,例如乙烯,丁二烯或丙烯。尤其适合的是酯基团含有约1-15个碳原子的聚丙烯酸酯和/或聚甲基丙烯酸酯。最好的是采用含丙烯酸2-乙基己酯和/或丙烯酸丁酯的聚丙烯酸酯。适用于本发明的聚乙烯基化合物可通过本领域所熟知的分散聚合法来制备。因此,市售聚丙烯酸酯分散体一般约含30-60wt%水和40-70wt%聚丙烯酸酯及合适的添加剂。
湿状态下的密封胶包含分散在水性介质中的乙烯基聚合物。本发明优选的密封胶,以湿状态下密封胶重量为100%计,约含15-90wt%乙烯基聚合物,以25-80wt%为佳,30-50wt%更好,约含5-50wt%水性介质,以5-40wt%为佳,15-30wt%更好,其余则为添加剂。水性介质包含水和适当的水溶性添加剂。这些添加剂的作用包括提高密封胶的抗冻性。根据加入量(本领域技术人员不难确定),冻点可降低至-20℃。所述添加剂最好是水溶性无机盐,例如氯化钠,氯化钾,氯化钙或硫酸钠,或是水溶性溶剂,例如甲醇,乙醇,丙醇或丙酮;或是水溶性高沸点和/或增塑性化合物,例如乙二醇或丙二醇。所述水溶性添加剂可以单用,也可以联用。
本发明密封胶可包含的添加剂选自无机填料;有机填料,尤其是增塑剂,增粘剂,低聚填料,聚合物填料和流变改性剂,例如增稠剂或触变剂;交联剂;增粘剂;稳定剂;消泡剂;表面活性剂;干燥剂;挥发性有机化合物(VOC);和前述水溶性添加剂。这些添加剂可以单用,也可以联用。它们的含量为:按100重量份湿状态下的密封胶计算,约为0-80重量份有机和/或无机填料;0-60重量份增塑剂;0-80重量份增粘剂;0-80重量份低聚物和/或聚合物填料;0-20重量份流变改性剂;0-15重量份交联剂;0-10重量份增粘剂;0-15重量份稳定剂;0-10重量份消泡剂;0-10重量份表面活性剂;0-20重量份干燥剂;0-10重量份挥发性有机化合物(VOC)(以0-5重量份为佳,0-3重量份更好)。以上各添加剂都是本领域已知的,就各自单独而言没有什么特别限制。优选的无机填料是沉淀或天然硫酸钡,二氧化钛,沉淀或天然碳酸钙(即白垩),沉淀或天然高岭土,滑石,氢氧化镁或氢氧化铝(后者可调节耐火级数(fire class),氧化锌,锆盐,玻璃珠或各种中空微珠。优选的有机填料是例如:烃类或松香类树脂,松浆树脂(tall resin),相脂树脂,萜烯,低聚物,例如丁烯,例如丙烯酸酯或其他分子量较低的含乙烯基分子,氨基甲酸酯或其他分子量较低的酯,聚酯类聚合物增塑剂,例如Benzoflex。合适的有机填料还包括聚合物填料,例如聚丙烯酸酯,聚苯乙烯,聚酯,聚酰胺,聚氨酯,聚氯乙烯,聚烯烃,聚乙酸乙烯酯,聚异戊二烯或聚异丁烯,及它们的嵌段共聚物的抗冲改性剂,聚合纤维或聚合物粉末。根据DIN 55945,增塑剂是一种低蒸汽压的液态或固态惰性有机物。由于溶解能力和溶胀能力,它们能降低乙烯基聚合物的硬度,改变它们的粘合力。合适的增塑剂是邻苯二甲酸酯,己二酸酯,柠檬酸酯,磷酸酯,偏苯三酸或磺酸。增粘剂优选松香类或烃类树脂。交联剂优选金属盐,例如乙酸锌,乙酸镁或锆盐;氮丙啶,乙醛酸盐或三甘醇二乙烯基醚。流变改性剂优选聚氨酯增稠剂,丙烯酸酯增稠剂,纤维素增稠剂,聚乙烯醇增稠剂,硅酸盐,乙烯基醚/马来酸酐或聚环氧乙烷。增粘剂优选pH添加剂(例如丙烯酸);硅烷,氮丙啶或含氟试剂。用于抗高温的稳定剂优选位阻酚,例如Irganox 110,Antioxidant 330或Cyanox 2246,用于抗UV的稳定剂优选位阻酚和/或位阻胺,例如Irganox 1076或1010,Tinuvin P,Tinuvin 326或770,或Antioxidant330,或改性二氧化钛。消泡剂优选含硅氧烷类,聚环氧乙烷类或含液态烷烃类。表面活性剂优选润湿剂,例如阴离子或阳离子型润湿剂或F-或Si-类润湿剂,尤其好的是“涂料添加剂手册”第152和516页所述那些润湿剂,Leonard J.Calbo,1987,Marcel Dekker Inc.,0-8247-7561-9。合适的干燥剂包括锆衍生物。用于本发明的挥发性有机化合物(VOC)是20℃蒸汽压至少为0.1mbar,1013.25mbar下沸点不超过240℃的化合物。它们又可分为沸点150℃以下的溶剂和沸点在150-240℃之间的高沸溶剂,可参见“挥发性有机化合物的鼓励性税收条例”(OVOC814.018),瑞士环保法(LPE 1997)第一部分第一条(定义)。按100重量份湿状态密封胶计算,挥发性有机化合物的用量以0-3重量份为宜,以0.1-0.5重量份为佳。然而,如前文所述,也可以使用更多的VOC。特别适合作为VOC的溶剂是乙醇,丙醇或乙酸乙酯。适合作为VOC的高沸溶剂是二醇类,例如乙二醇或丙二醇。此外,本发明的密封胶还可包含例如抗菌剂(防腐剂)或颜料等常规添加剂,参见“涂料添加剂手册”第195-197页所述那些添加剂,Leonard J.Calbo,1987,MarcelDekker Inc.,0-8247-7561-9。
稳定剂特别用于丙烯酸酯类乙烯基聚合物与脂族单体(例如乙酸乙烯酯或丁二烯)或芳族单体(例如苯乙烯或乙烯基苯)联用时。此外,在使用非氢化增粘剂时,最好加入稳定剂以获取理想的抗老化稳定性。增粘剂,低聚物填料及其他有机填料的作用是提高密封胶的自粘性,内聚力和防水性。本领域技术人员可通过选择合适的填料和交联剂获得最适合的内聚力。在建筑业中,所述内聚力应在70℃仍能满足要求。因此,熟练技术人员可通过适当选择乙烯基聚合物的链长,以及填料和交联剂的种类和用量对最适内聚力进行微调。由于内聚力的优化常与粘合力相冲突,因此必须选择合适的内聚力使之不高于粘合力要求所允许的值。
按100重量份湿状态密封胶计,添加剂的量一般约为0-80重量份,以10-70重量份为宜,30-60重量份最好。前述用于提高抗冻性的水溶性添加剂的含量以0-30重量份为宜,0-15重量份更好,同时,其他添加剂的含量则约为0-70重量份,以20-50重量份为佳。
用心轴(spindle)6,10rpm,按照Brookfield A型测定,湿状态密封胶的ISO 2555粘度以23℃时至少50Pa·s为宜。较好的是,用心轴7,10rpm,按照Brookfield A型测定,23℃的粘度至少约为200Pa·s,至少约350Pa·s更好。粘度的上限是:只要还能对密封胶进行操作。合适的粘度可由本领域技术人员用前述流变改性剂和/或其他添加剂,通过常规试验来确定。也可以加入流变改性剂来改善密封胶的操作性。借助于例如增稠剂或触变剂等流变改性剂,可获得一种易于通过筒体(cartridge)或塑料袋挤出和操作的半固流态(firm fluid)密封胶。同时,这些改性剂提高了瞬时强度,使得密封胶能够承受例如聚烯烃材料的重量。用表面活性剂润湿待封接材料。由于此类表面活性剂会产生泡沫,所以需混入消泡剂。用增稠剂提高粘度则可避免待封接材料对密封胶的排斥作用。
根据本发明,干状态的密封胶至少包括一相,本发明中又称之为粘合基质(binding matrix)。这一相包含乙烯基聚合物和所有可溶于其中的添加剂。该粘合基质的玻璃转化温度Tg低于约10℃,以介于-80℃至10℃之间为宜,尤其好的是-80℃至-40℃之间,该玻璃转化温度Tg可如下用DSC法(差示扫描量热法)测定。先将30mg样品以-10℃/min的速度冷却至-120℃,然后以10℃/min的速度升温至40℃。升温期间,Cp曲线(Cp代表热容)出现一个跃升,其中点即玻璃转化温度Tg。这一中点可以通过对曲线的微分来测定。增塑剂、低聚物填料和/或增粘剂的使用也使得采用玻璃转化温度高于10℃的乙烯基聚合物尤其是聚丙烯酸酯成为可能,因为这些添加剂可将粘合基质的玻璃转化温度降至要求的水平。通常,相数决定于密封胶的组成。除粘合基质之外,密封胶还宜至少另含一相,尤其是另含两相。这些其他相包含水和不溶于粘合基质的添加剂。
根据本发明,干状态指在70℃按照300g干重/m2将密封胶涂到Si纸上1小时后的状态。本发明所述“湿状态”则指密封胶制得后和保存时(例如于塑料袋或筒中)的状态。
在5-50℃按照DIN EN(欧洲标准)1939在聚烯烃材料上测定,本发明密封胶干状态下的剥离粘合力至少约为5N/25mm,以5-50N/25mm为佳。本发明密封胶不仅在聚烯烃材料上,而且在例如纸张、非织造材料、聚酰胺或聚酯等其他材料上也具有这样的剥离粘合力,但在表面张力非常低的诸如硅化或氟化表面上则没有这样的剥离粘合力。该剥离粘合力是一种可重复剥离粘合力。这样的剥离粘合力可通过调节乙烯基聚合物的极性而获得,本领域技术人员不难通过常规试验做到。如果乙烯基聚合物的极性过高,则对聚烯烃材料的亲和力过低;相反,如果乙烯基聚合物的极性过低,其中的双键太少,不足以与聚烯烃材料之间发生足够的范德华力相互作用。此时,必须将密封胶配制成与聚乙烯材料的粘合力高于其自身的内聚力(内部强度)。乙烯基聚合物尤其是聚丙烯酸酯的极性可通过对单体的选择加以调节。短酯基(例如甲酯或乙酯)丙烯酸酯单体极性高,长酯基丙烯酸酯(例如丙烯酸十八烷酯)极性低。聚丙烯酸酯的极性还可以用乙烯基类化合物来调节,例如用乙酸乙烯酯,乙烯基醚,卤化烯或乙烯基芳族化合物,例如苯乙烯。加入二乙烯基或三乙烯基共聚单体可以调节聚合物的内聚力、分子量和剪切模量。
按后文方法测定,干状态密封胶的动态剪切模量G′在25℃时最好介于5×105Pa至5×103Pa,尤其是,-10℃以下,最好-25℃以下时低于5×105Pa,高于60℃,最好高于80℃时则高于5×103Pa。本发明所述的剪切模量G′是一个弹性模量(或储能模量),用800微米厚的样品,在流变仪/板/板系统上,1Hz频率,0.2%延伸率,5℃/min升温速度测得。
本发明对于密封胶的制备方法没有限制。前述组分宜在5-100℃之间的温度下混和,可用各种适合的混合设备,例如静态或动态混合机。较好的是采用可对速度进行程序调节的混合机,这样就可以规定生产的顺序。较好的是采用高转速混合机,确切转速取决于密封胶的组成。如果采用了高粘度添加剂,可在混合前进行加热,以便操作。混合在真空下进行,最好在约200-80mbar下进行。然后,将形成的膏体装入筒中或塑料袋中,这样,至少可保存1年。
使用时,用压力枪将密封胶从简或塑料袋中压出。然后,密封胶因水分蒸发而干燥。干状态下,按100wt%干密封胶计,密封胶约含0-20wt%水,特别好的是0-10wt%。
可在约1-60℃之间的温度对密封胶进行操作。优选的操作温度约为5-50℃。如果需采用更低的温度,可加入前述水溶性添加剂来提高抗冻性。干状态下,本发明密封胶可在-20-80℃之间的温度发挥其功能。
所述密封胶是用于封接和/或接合材料,尤其是接合材料。由于所述密封胶可与除硅化和氟化表面之外的所有材料(例如聚烯烃,纸张,非织造材料,聚酰胺和聚酯)粘合,只要有此类材料尤其是聚烯烃材料有待封接,就可采用所述密封胶,尤其是在没有外露表面时。然而,所述密封胶还可用于污垢的留存并无破坏性的场合。所述密封胶尤其适用于建筑行业,例如用于柱脚条(pedestal strips),型材(profile),尤其是含聚烯烃的型材,还适用于工业应用。建筑业中的一种特殊应用是用作房顶,用于将聚烯烃材料与例如木材、灰泥、混凝土、石灰石或砖块等漆后或无漆墙面等固体材料接合。合适的聚烯烃材料例如薄膜,织物,注塑件,纤维和缆线。
因此,优选的本发明密封胶具有以下特征和优点:- 基本上不含VOC,即基本上不含溶剂和高沸溶剂,因此,异味少;- 干状态下在聚烯烃材料上的剥离粘合力在5℃和23℃时都至少5N/25mm(根据DIN EN 1939);- -20至80℃下,干状态下具有自粘性;- 抗老化,即使老化,剥离粘合力也不会降至5N/25mm(根据DIN EN 1939)以下;- 粘合基质的玻璃转化温度低于10℃;- 可用筒和压力枪进行操作。
因此,本发明提供了一种基本上不含VOC,并具有良好粘合力,尤其是在聚烯烃材料上粘合力的密封胶。
以下用实施例来说明本发明,它们代表了本发明的优选实施方式。
实施例
60重量份聚丙烯酸酯分散体,其玻璃转化温度Tg=-40℃,与PO材料的剥离粘合力至少为15N/25mm,固体含量65wt%,水含量35%,固体中99.5wt%为聚丙烯酸酯其余为乳化剂,在室温下(23℃)和100mbar,将其与6重量份水溶性添加剂即硫酸钠,以及以下其他添加剂混合:9重量份树脂,7重量份聚酰胺纤维,13重量份聚异丁烯,1重量份聚氨酯增稠剂,2重量份聚乙烯醇增稠剂,0.3重量份抗UV稳定剂,0.2重量份抗菌剂和0.5重量份表面活性剂。湿状态下,所得膏体的23℃粘度约为370Pa·s(根据Brookfield,A型,心轴7,10rpm)。干状态下,所得组合物的剪切模量G′为-25℃时5×105Pa至100℃的5×103Pa,23℃与聚烯烃材料的剥离粘合力为20N/25mm。干密封胶具有自粘性,表面粘性测定为:滚球路径长7cm。所述粘合基质的玻璃转化温度约为-30℃。所有测定均按前文所述方法进行。
Claims (16)
1.一种基于乙烯基聚合物分散体的单组分密封胶,其湿状态下基本不含挥发性有机化合物VOC,干状态下具有自粘性。
2.根据权利要求1所述的密封胶,5-50℃之间,干状态下与聚烯烃材料的剥离粘合力至少为5N/25mm。
3.根据权利要求1或2所述的密封胶,干状态下的剪切模量G′为:25℃时5×105Pa至5×103Pa,-10℃以下时低于5×105Pa,60℃以上时高于5×103Pa。
4.根据权利要求1至3中任一项所述的密封胶,干状态下至少含一相,其玻璃转化温度Tg低于10℃。
5.根据前述权利要求中任一项所述的密封胶,按100重量份密封胶计,湿状态用0-80重量份添加剂改性,所述添加剂中挥发性有机化合物VOC少于3重量份。
6.根据前述权利要求中任一项所述的密封胶,湿状态下23℃的粘度至少为50Pa·s。
7.根据前述权利要求中任一项所述的密封胶,所述乙烯基聚合物包含基于至少一种丙烯酸酯和/或甲基丙烯酸酯单体的聚合物。
8.根据前述权利要求中任一项所述的密封胶,湿状态下,乙烯基聚合物占密封胶总重的约15-90wt%。
9.根据前述权利要求中任一项所述的密封胶,湿状态下,乙烯基聚合物占密封胶总重的约25-80wt%。
10.根据权利要求5至9中任一项所述的密封胶,所述添加剂包括至少一种以下化合物,它们选自:水溶性化合物,无机填料,有机填料,交联剂,增粘剂,稳定剂,消泡剂,表面活性剂,干燥剂和挥发性有机化合物VOC。
11.根据权利要求10所述的密封胶,所述水溶性化合物中至少其一选自:氯化钠,氯化钾,氯化钙,硫酸钠,甲醇,乙醇,丙醇,丙酮,乙二醇和丙二醇。
12.根据前述权利要求中任一项所述的密封胶,它装在筒或塑料袋中。
13.根据权利要求1至12中任一项所述密封胶的用途,即用于材料的封接和/或接合。
14.根据权利要求13所述的用途,至少所述材料之一是聚烯烃材料。
15.涂有权利要求1至12中任一项所述密封胶的材料。
16.一种制备前述权利要求中任一项所述密封胶的方法,包括在真空下混合所述密封胶的各组分。
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DE20022732U1 (de) | 2000-01-12 | 2002-05-16 | Silu Verwaltung Ag | Einkomponentige Dichtmasse auf Basis einer Dispersion von Vinylpolymeren |
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-
2000
- 2000-01-12 DE DE20022732U patent/DE20022732U1/de not_active Expired - Lifetime
- 2000-01-12 DE DE10000940A patent/DE10000940B4/de not_active Revoked
- 2000-01-12 DE DE20023056U patent/DE20023056U1/de not_active Expired - Lifetime
- 2000-01-12 DE DE20023341U patent/DE20023341U1/de not_active Expired - Lifetime
- 2000-01-12 DE DE20023180U patent/DE20023180U1/de not_active Expired - Lifetime
- 2000-01-12 DE DE20023181U patent/DE20023181U1/de not_active Expired - Lifetime
- 2000-01-12 DE DE20023340U patent/DE20023340U1/de not_active Expired - Lifetime
-
2001
- 2001-01-10 DK DK02023786T patent/DK1288273T3/da active
- 2001-01-10 DK DK01900414T patent/DK1173525T3/da active
- 2001-01-10 EP EP02023786A patent/EP1288273B1/de not_active Revoked
- 2001-01-10 DE DE50102751T patent/DE50102751D1/de not_active Expired - Lifetime
- 2001-01-10 AU AU25145/01A patent/AU2514501A/en not_active Abandoned
- 2001-01-10 EP EP04014375A patent/EP1477542A1/de not_active Withdrawn
- 2001-01-10 WO PCT/EP2001/000235 patent/WO2001051582A1/de not_active Application Discontinuation
- 2001-01-10 CN CN01803544A patent/CN1394228A/zh active Pending
- 2001-01-10 EP EP01900414A patent/EP1173525B1/de not_active Revoked
- 2001-01-10 AT AT02023786T patent/ATE270317T1/de active
- 2001-01-10 CZ CZ2002-2415A patent/CZ304438B6/cs not_active IP Right Cessation
- 2001-01-10 HU HU0204031A patent/HU226902B1/hu not_active IP Right Cessation
- 2001-01-10 DE DE20122638U patent/DE20122638U1/de not_active Ceased
- 2001-01-10 CA CA002396949A patent/CA2396949A1/en not_active Abandoned
- 2001-01-10 AT AT01900414T patent/ATE236967T1/de not_active IP Right Cessation
- 2001-01-10 CH CH01027/02A patent/CH693232A5/de not_active IP Right Cessation
- 2001-01-10 DE DE50100156T patent/DE50100156D1/de not_active Revoked
- 2001-01-10 JP JP2001551157A patent/JP2003519715A/ja active Pending
- 2001-01-10 PL PL01362786A patent/PL362786A1/xx not_active Application Discontinuation
-
2002
- 2002-07-11 NO NO20023347A patent/NO20023347D0/no not_active Application Discontinuation
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