CN103459539A - 改进的结构粘合剂 - Google Patents
改进的结构粘合剂 Download PDFInfo
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- CN103459539A CN103459539A CN2012800161233A CN201280016123A CN103459539A CN 103459539 A CN103459539 A CN 103459539A CN 2012800161233 A CN2012800161233 A CN 2012800161233A CN 201280016123 A CN201280016123 A CN 201280016123A CN 103459539 A CN103459539 A CN 103459539A
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Abstract
一种可热硬化的结构粘合剂材料,一旦固化,则其断裂伸长率为至少10%和玻璃化转变温度(Tg)大于或等于80℃,且可在机动车中用作结构粘合剂,以减少尤其事故期间粘结体的变形,该粘合剂在环境温度下触摸起来干燥,且可在比热硬化发生时低的温度下熔融加工。该粘合剂可用于要求高断裂应变,大于80℃的玻璃化转变温度,高刚度和高强度组合的应用中。这一组合在航空和机动车工业中是尤其感兴趣的。
Description
本发明涉及粘合剂材料,和特别地涉及增韧材料,和特别地涉及拥有高的断裂应力的增韧粘合剂材料,有时称为结构粘合剂。特别地,本发明涉及可热硬化、可交联的粘合剂材料,它将产生具有在感兴趣的宽温度范围内得以维持所需机械性能的粘合剂。例如,在热和冷的气候中使用机动车,和在机动车中使用的任何粘合剂应当在机动车制造者规定的温度范围(这是预期的操作温度范围)内维持其粘合性能。因此,期望在固化之后,粘合剂具有高的Tg,这是因为在比Tg高的温度下,聚合物材料变为橡胶状和因此具有降低的刚硬度(即,具有低的弹性模量)。结构粘合剂的一种所需的性能是高的断裂伸长率,以便当发生变形时延迟断裂。另外,高的断裂应变材料常常,但不总是更加抗冲击。在优选的实施方案中,在热硬化之前,粘合剂在环境温度下触摸起来干燥,且可在中间温度下通过诸如熔融涂布、挤出或注塑之类的技术加工且没有发生聚合物体系的显著交联。
环氧树脂广泛地用于粘合剂中,这是因为它们具有典型地通过加热固化(交联)生产结实、回弹性粘结体的能力。由环氧树脂,例如双酚A或双酚F基环氧树脂形成的粘合剂可具有充足高的Tg,然而,一般地,具有高Tg的粘合剂不具有高的断裂伸长率。粘合剂的配制者选择各成分,以便获得所需性能的组合。尝试通过在粘合剂配方内包括橡胶状材料或其他聚合物来增加断裂伸长率。然而,添加这些成分会降低固化粘合剂的Tg且常常削弱粘合剂和常常减少粘合剂的粘合耐久性或抗水解性,其中聚酰胺-环氧杂化物是一个实例。因此,事先增加生产率导致Tg,弹性模量和常常强度非所需的降低。本发明克服了这一问题。
本发明提供具有所需Tg和高断裂伸长率的组合的可热硬化的结构粘合剂。
在优选的实施方案中,粘合剂是固体且在室温下触摸起来干燥,并可通过在低于其固化时的温度下加热来加工,结果尤其可通过熔融涂布,挤出或注塑来加工该粘合剂,且在成形工艺过程中,在没有固化的情况下,可在冷却时再硬化。
本发明的目的尤其在于可在机动车和航空工业中使用的粘合剂,通过硬化基底(组件)之间的粘结,并在没有赋予非所需的脆度的情况下,增加该粘结体的刚度,该粘合剂可增加其中使用粘合剂的区域的强度。可使用粘合剂,提供结构粘合性能,尤其它们可在机动车中用作折边法兰粘合剂,并且也可提供抗碎性,其中期望变形时较大的抗断裂伸长率。为了在机动车工业中使用,粘合剂一旦固化,则需要在可预期车辆将遭受来自于环境暴露的合适的温度范围内,例如-40℃至80℃下保持其机械性能,但在一些情况下,可经历较高的温度,这是车辆生成的热导致的。
结构粘合剂是已知的,例如在PCT公布WO2008/157129中描述的那些。然而,不可能获得具有对于某些应用来说性能的最佳组合的材料。粘合剂的配制者和使用者关心的环氧基结构粘合剂的性能是断裂伸长率,玻璃化转变温度,刚度和强度,这取决于应用,同样可具有其他重要的性能,例如断裂韧度,抗剥离性。一般地,期望每一种性能尽可能高。然而,迄今为止,不可能获得多种性能的最佳组合。可以实现高玻璃化转变温度,高刚度和高强度的组合。此外,可实现高伸长率和高强度的组合,但代价是高玻璃化转变温度和典型地高的刚度。
WO2008/157129涉及一种粘合剂配方,它包括环氧树脂,冲击改性剂和/或增韧剂和固化剂。该粘合剂在环境温度下是粘性的。在优选的实施方案中,粘合剂含有热塑性聚醚,例如苯氧基树脂。设计该配方,产生具有高的楔形冲击强度的粘合剂,且特征在于一种或更多种下述特征的组合:使用具有0.8mm厚EG-60Adherends的ISO-11343Impact Wedge Peel,在小于-30℃的温度下,粘合剂材料的冲击强度大于15N/mm,优选大于20N/mm。WO2008/157129因此不涉及提供具有80℃以上的高Tg,和高断裂伸长率(高于10%)的组合的粘合剂。
类似地,WO2009/124709涉及增加粘合剂对环境暴露的楔形冲击强度和回弹性。另外,WO2009/124709不涉及增加环氧基粘合剂体系的断裂伸长率。此外,它不涉及在环境温度下触摸起来干燥且可在低于其活化温度的温度下加工的可热活化的粘合剂。对于一些应用来说,尤其对于其中基底材料在可能经历高水平的塑性变形的位置内的那些应用中,由这些结合物生产的固化粘合剂非所需地脆。
典型地将结构粘合剂以液体或糊剂形式施加到待粘结的区域中,所述液体或糊剂会导致储存问题且涉及在储存和运输过程中,糊剂或液体可吸收赃物和污染物。此外,要求泵和液体容器以供施加。因此,期望提供一种粘合剂组合物,它为固体,且在环境温度下触摸起来干燥,并通过加热,可造粒,和加工以及输送到待粘结的区域,以提供在低于它将热硬化(固化)时的温度下,可润湿它施加到其上的表面的材料。因此,尽管在优选的实施方案材料中,本发明的粘合剂可以是液体或糊剂,但在环境温度下,它们是固体且触摸起来干燥,并可通过熔融涂布,挤出或注塑施加,且可在冷却时再硬化,并且可随后活化,产生结构粘合剂的性能。
粘合剂的伸长率表明它在应力下变形的能力,伸长率越大,则在没有断裂的情况下,变形能力越大。高伸长率的优势的一个实例是当在其上使用粘合剂的一种或多种基底经历塑性变形,例如在机动车碰撞中对金属组件可能发生的塑性变形时,使用具有高伸长率的粘合剂(与所需的粘结强度结合)可导致各区域保持稳定。当所使用的材料厚度增加时,高水平的伸长率尤其重要。当在折边中使用粘合剂时,可实现高伸长率的其他优势,因为被损坏的组件(例如门)可在修补回到其起始形状的过程中弯曲且没有使粘合剂断裂,从而维持腐蚀防护。
因此,本发明提供可热硬化的结构粘合剂材料,一旦固化,则它除了具有高的弹性模量外,还具有高的断裂伸长率和大于或大于80℃的玻璃化转变温度(Tg)。
在本申请中,tgδ被视为(Tg)且由动态机械分析试验(DMA)获得。通过试验ASTM D638Type1,测量粘合剂的拉伸性能,其中包括伸长率。使用平行板流变仪,测量粘度。
固化粘合剂的断裂伸长率为至少10%,优选至少15%,和更优选至少20%,且可以是最多50%。固化粘合剂的玻璃化转变温度为80℃以上,和优选90℃以上。该粘合剂也可具有优选至少100MPa的高的弹性模量,这通过刚度表明,且通过搭接剪切证明的强度优选至少7MPa,更优选至少10MPa。然而,可实现的搭接剪切值部分取决于在固化工艺过程中,材料是否膨胀或发泡。若材料发泡,则与该材料不发泡时相比,可预期较低水平的搭接剪切强度。
该粘合剂组合物可以是液体或糊剂,尽管它优选是固体且在环境温度(例如20℃)下触摸起来不发粘。未固化的粘合剂在低于其活化温度下可加工,结果它可以以熔体形式提供,例如通过挤出到其中它被使用的位置或者它被注塑形成粘合剂的组件。该组件可以完全是粘合剂或者可包括与粘合剂一起重叠注塑的载体。或者,可在所需的位置处熔融涂布粘合剂。可加工性所要求的粘度是本领域已知的那些,且取决于待使用的加工技术和加工温度。滑爽剂可包括在粘合剂配方内,以便辅助加工。滑爽剂的实例包括油酰胺和二十二烷酰胺。然而,使用滑爽剂可降低固化粘合剂的Tg,结果所使用的用量应当最小化,且优选使用小于1wt%的滑爽剂。
在进一步的实施方案中,本发明提供可热硬化的环氧基粘合剂组合物,它能产生Tg等于或大于80℃和断裂伸长率为至少10%的固化粘合剂。
我们已发现,若合适的热塑性改性剂,例如热塑性环氧树脂与增韧剂一起包括在粘合剂配方内,则可采用环氧基粘合剂,实现这一所需的性能组合。热塑性改性剂优选是当环氧树脂固化时,与环氧树脂相容的产品,以提供所要求的强度和Tg,且热塑性组分有助于提供所要求的伸长率。合适的热塑性改性剂的实例包括苯氧基树脂和聚醚胺。
尽管存在热塑性环氧树脂可增加伸长率,但其增加可能不足以使配制的材料在可以被本发明提出的所有应用中能起作用。因此,根据平衡所要求的性能,其他添加剂可包括在本发明的配方内的。可通过在配方内掺入其他添加剂,例如,尤其有用的核/壳材料,进一步增加伸长率。其他优选的添加剂包括羟基封端的聚氨酯聚合物,聚乙烯基聚合物,尤其聚乙烯缩丁醛或聚酰胺,尤其低熔点聚酰胺。添加剂的选择和添加剂的优选组合取决于所要求的粘合剂的性能,然而,我们已发现,含羟基封端的聚氨酯预聚物的添加剂的结合物可得到约20%的伸长率,尤其当与核/壳材料和CTBN改性的环氧材料一起使用时。类似地,含聚乙烯基聚合物,尤其聚乙烯缩丁醛的添加剂的结合物可得到15%-25%的伸长率。和当与羟基封端的聚氨酯预聚物一起使用时,可得到高至50%的伸长率和有时更高。
该组合物优选在环境温度(20℃)下触摸起来干燥,且优选可在比可能存在的固化剂和发泡剂的活化温度低的温度下造粒和模塑。该组合物因此优选熔点为80℃至120℃,更优选80℃至110℃,且热硬化或固化温度为130℃-210℃,优选130℃-150℃。
在粘合剂配方内各组分的优选浓度取决于粘合剂材料打算的应用。本发明的粘合剂材料可施加到各种制造制品上以供粘附(例如结构粘附)一种,两种或更多种组件(例如膜)的第一表面到一种,两种或更多种组件的第二表面上。这一粘合可提供结构完整性和/或粘合制品中的组件,且也可提供制品中的组件密封,阻尼,增强或类似性能。这些制造制品的实例没有限制地包括家庭或工业用具,家具,储存容器,建筑物,结构体或类似物。在优选的实施方案中,将粘合剂材料施加到机动车车辆的组件,例如车身或框架组件(例如,车架轨道)上。在本发明中,可在粘合剂粘附到表面上的预活化的状态下,施加粘合剂材料到组件或制品之一的一个或更多个表面上,同时维持可热硬化,从而作为熔体施加时,它将粘附到表面上且没有固化。可随后活化该材料,以便固化或硬化,和任选地膨胀和/或发泡。一旦施加,则粘合剂材料典型地润湿该材料接触的表面,结果粘合到这些表面上。
在一个实施方案中,粘合剂可以是可发泡的,在此情况下,它将含有物理和/或化学发泡剂。在这一实施方案中,该材料的体积将膨胀到比未膨胀状态下其体积大(例如,大至少5%,大至少20%或者甚至可能地大至少50%)。在其中期望给料(input)时减少变形的区域内使用粘合剂的情况下,优选至少对于结构粘合剂来说,体积膨胀相对低,以便膨胀体积小于400%,更典型地小于300%,甚至更典型地小于200%,相对于起始未膨胀的体积。
本文的百分数是指重量百分数,除非另有说明。
现更加详细地描述本发明中使用的材料。
环氧树脂
本文使用环氧树脂是指含有至少一个环氧官能团的任何常规的环氧材料。环氧树脂可以是双官能,三官能,多官能的,或其组合或者别的情况。而且,可使用术语环氧树脂,表示一种环氧树脂或者环氧树脂的组合。聚合物-基材料可以是具有通过开环反应可聚合的一个或更多个烷环的含环氧基的材料。在优选的实施方案中,本发明的粘合剂材料包括约2%-70wt%环氧树脂,更优选约7%-50wt%环氧树脂,和甚至更优选约15%-40wt%环氧树脂,和甚至可能地约15%-约25wt%环氧树脂。
环氧可以是脂族,脂环族或芳族的。环氧可以以固体形式(例如,以粒料,大块,小片或类似物形式)或者液体(例如环氧树脂)或者这两种形式供应。若树脂在23℃的温度下为固体,则本文所使用的树脂被视为固体树脂,和若它在23℃下为液体,则被视为液体树脂。存在环氧树脂会增加粘合剂的粘合性,流动性能,或这两种性能。一种例举的环氧树脂可以是苯酚树脂,它可以是可溶能熔酚醛树脂型或其他类型的树脂。例如,可使用双酚A树脂,双酚F树脂,其结合物或类似物。而且,可使用数种不同环氧树脂的各种混合物。合适的环氧树脂的实例以商品名DER<(R)>(例如DER331,DER661,DER662)销售,其商购于Dow Chemical Company,Midland,Michigan。
可使用的液体环氧树脂典型地在23℃的温度下的粘度为至少5000,更典型地至少8000和甚至可能地至少11,000cps,但典型地小于30,000,典型地小于22,000和甚至可能地小于15,000cps,但较高和较低的数值也可以是可能的,除非另有说明。液体环氧树脂的环氧当量典型地为至少80,更典型地至少150和甚至可能地至少185g/eq,但典型地小于300,更典型地小于220和甚至可能地小于195g/eq,但较高和较低的数值也是可能的,除非另有说明。优选的液体树脂包括二缩水甘油基醚(它可以是芳族苯酚基(双酚A或F))且以商品名DER331商购于Dow Chemical Company,和以EPON828和EPON863商购于Hexion Specialty Chemicals而销售。
在优选的实施方案中,所使用的环氧树脂使得配制的粘合剂在环境温度下触摸起来干燥。
热塑性改性剂
热塑性改性剂典型地为含侧挂羟基部分的聚醚。尤其所需的热塑性聚醚是苯氧基树脂。本文所使用的苯氧基树脂是具有沿着聚合物主链的醚键和侧挂的羟基的聚羟基醚。有用的苯氧基树脂是苯酚基双官能环氧树脂和双官能苯酚的反应产物(例如,双酚A环氧树脂与双酚A的反应产物)。也可由双酚(例如双酚A)和表氯醇直接合成类似的材料。环氧端基可以开环生成α二醇端基。苯氧基树脂的重均分子量为至少约5,000,更典型地至少约25,000,和仍然更典型地至少约50,000,但小于约100,000,更典型地小于约75,000,和仍然更典型地小于约60,000。有用的苯氧基树脂的实例包括获自Inchem Corp的PAPHENPhenoxy Resin PKHH和PKHJ。优选苯氧基树脂具有宽的分子量分布。
其他热塑性改性剂包括在它们主链内的芳族醚/胺重复单元,例如聚醚胺,聚(氨基醚),单乙醇胺和二缩水甘油基醚的共聚物,它们的结合物或类似物。热塑性聚醚的实例公开于美国专利5,275,853;5,464,924和5,962,093中。
热塑性改性剂,例如聚醚优选占粘合剂材料的3%-约40wt%,和甚至更优选约10%-30%,更优选10%-约15%。
固化剂
固化剂通过交联聚合物,环氧树脂和该粘合剂材料内的其他成分,辅助粘合剂材料固化。在粘合剂材料内存在的固化剂或固化剂促进剂的用量范围为约0.001wt%-约9wt%,和更典型地约0.2-约6wt%,和甚至更典型地约2wt%-约6wt%。固化剂材料可选自脂族或芳族胺,或它们各自的加合物,酰胺基胺,聚酰胺,脂环族胺,酸酐,聚羧酸聚酯,异氰酸酯,苯酚-基树脂(例如,苯酚或甲酚可溶能熔酚醛树脂,共聚物,例如苯酚萜烯的那些,聚乙烯苯酚或双酚A甲醛共聚物,双羟基苯基烷烃或类似物),二酰肼,磺酰胺,二氨基二苯基砜,酸酐,硫醇,咪唑,脲,叔胺,BF3络合物或其混合物。尤其优选的固化剂包括改性和未改性的多胺或聚酰胺,例如三亚乙基四胺,二亚乙基三胺,四亚乙基五胺,氰基胍,双氰胺和类似物。
也可提供用于固化剂的促进剂(例如,改性或未改性的脲,例如亚甲基二苯基双脲,咪唑,封闭的胺或其结合物)用以制备粘合剂材料。
粘合剂配制剂可含有其他添加剂,例如增韧剂,冲击改性剂,聚合物或共聚物填料和其他伸长促进添加剂。
伸长促进添加剂和增韧剂
在本发明的粘合剂内存在不具有环氧反应性的某些聚合物可导致固化粘合剂的增加的断裂伸长率和/或增加固化粘合剂的挠性。尽管相关机理目前没有充分地了解,但认为该聚合物在环氧反应性组分的固化过程中,经历相分离,从而在固化粘合剂内部提供更加挠性的区域。或者,添加剂可充当增塑剂,所述增塑剂与环氧树脂相容,但在交联的环氧分子之间形成区域,这些区域有助于材料变形的能力且没有断裂。它们可用于增加总的聚合物基体的塑性,通过例如橡胶改性的环氧树脂的相分离和使用核/壳聚合物,这反过来使得添加其他类的增韧剂更加有效。我们已发现,羟基封端的聚氨酯聚合物尤其有用,应当避免异氰酸酯封端,因为它可产生简单组分的材料,这些简单组分的材料因异氰酸酯官能度与或者大气或者材料内部的湿气反应导致具有有限的货架稳定性。
或者,已发现,在特别的聚乙烯缩丁醛内的聚乙烯酯,例如获自Solutia的Butvar树脂,尤其获自Kuraray的Butvar90和Mowital树脂是有用的。
使用术语增韧剂可涉及单一的增韧剂或者多种不同的增韧剂结合物。尽管可使用其他增韧剂,但优选的增韧剂包括胺改性,环氧改性的聚合物或者这二者。这些聚合物可包括热塑性材料,热固性材料或可热固化的材料,弹性体或其结合物或类似物。可采用芳族或非-芳族环氧改性这些聚合物,和/或采用双酚-F型,双酚-A型或其结合物或其他类型的环氧改性这些聚合物。优选的增韧剂的实例是以商品名EPS-350和EPS-80商购于Akzo Nobel而销售的环氧化聚硫化物。
获自Huntsman的增韧剂DY965CH是尤其有用的。另一优选的增韧剂的实例是以商品名HYPOX DA323商购于CVC SpecialtyChemicals而销售的环氧-二聚体酸弹性体。其他优选的增韧剂的实例是以商品名GME-3210和GME-3220商购于GNS Technologies而的聚氨酯改性的环氧树脂。在没有束缚于理论的情况下,认为当包括聚氨酯改性的环氧增韧剂时;粘合剂材料可基本上维持低温下的冲击强度(例如,抗冲击性),同时最小化Tg的下降(例如与其他增韧剂相比)。优选的增韧剂的再进一步的实例是胺或环氧封端的聚醚,例如商购于Huntsman的JEFFAMINE D-2000,和商购于Dow Chemical Company的DER<(R)>732。基于腰果的坚果壳液体的增韧剂,例如环氧化液体Cardolite NC-514和Cardolite Lite2513HP也是有用的增韧剂。本文讨论的所有单独的增韧剂可在本发明的粘合剂材料中独立地或者彼此结合使用,除非另有说明。
低熔点的热塑性聚酰胺,例如获自Du Pont的Elvamide树脂是尤其有用的。优选在范围为110℃-175℃,尤其115℃-160℃的温度下熔融的聚酰胺树脂。羟基封端的聚氨酯预聚物,例如获自Lubrizol的Estane产品和获自Merquinson的Pearlbond产品也是有用的。
典型地,增韧剂为粘合剂材料的至少2%,更典型地至少3%和甚至可能地至少5wt%,但典型地小于粘合剂材料的50%,更典型地小于35%和甚至可能地小于20wt%,尽管较高和较低的数值也可以是可能的,除非另有说明。还认为特别地,在其中用环氧组分改性增韧剂的实施方案中,增韧剂的用量可以较高。
冲击改性剂
本发明的粘合剂材料包括至少一种冲击改性剂,有时称为增韧剂,通过在粘合剂体系内分配能量,它有助于粘合剂所需的机械性能,例如搭接剪切和T剥离强度。通常优选冲击改性剂为粘合剂材料的至少4%,更典型地为10%,和甚至更典型地至少20wt%,和还优选冲击改性剂为粘合剂的小于70%,更典型地小于40%,甚至更典型地小于30wt%。
术语“冲击改性剂”可包括一种冲击改性剂或数种冲击改性剂。冲击改性剂可包括热塑性材料,热固性材料或可热固化的材料,弹性体,其结合物或类似物。在优选的实施方案中,冲击改性剂包括弹性体(其中包括含弹性体的材料),核/壳聚合物(它可包括弹性体),或其结合物。
在优选的实施方案中,使用至少两种冲击改性剂,且冲击改性剂包括显著部分的核/壳冲击改性剂。当它包括核/壳聚合物时,优选冲击改性剂由至少60%,更典型地至少80%和甚至可能地至少97%核/壳聚合物组成。本文所使用的术语核/壳冲击改性剂表示其中显著部分(例如以重量计,大于30%,50%,70%或更大)的冲击改性剂由基本上完全被第二聚合物材料(即第二或壳材料)包围的第一聚合物材料(即,第一或核材料)组成。本文所使用的第一和第二聚合物材料可由组合或者一起反应(例如按序聚合)的一种,两种,三种或更多种聚合物组成,或者可以是独立的一部分或者相同的核/壳体系。
核/壳冲击改性剂中的第一和第二聚合物材料可包括弹性体,聚合物,热塑性材料,共聚物,其他组分,其结合物或类似物。在优选的实施方案中,核/壳冲击改性剂中的第一聚合物材料,第二聚合物材料或这二者包括一种或更多种热塑性材料或者基本上由其组成(例如,以重量计,至少70%,80%,90%或更大)。例举的热塑性材料没有限制地包括聚苯乙烯类,聚丙烯腈类,聚丙烯酸酯类,聚乙酸酯类,聚酰胺,和聚烯烃。
通过乳液聚合,接着凝结或喷雾干燥,形成优选的核/壳冲击改性剂。在一些应用中,已发现,对于促进对在其上具有杂质,例如灰尘、油(例如金属冲压油)或类似物的表面的粘合来说,凝结等级的核/壳冲击改性剂是尤其所需的。这种冲击改性剂可降低粘合剂故障的可能性(这与内聚破坏相反)。
可用作冲击改性剂的有用的核-壳接枝共聚物的实例是其中含硬段的化合物,例如苯乙烯,丙烯腈或甲基丙烯酸酯接枝到由含软或弹性段的化合物,例如丁二烯或丙烯酸丁酯的聚合物制成的核上的那些。美国专利3,985,703描述了有用的核-壳聚合物,其中的核聚合物由丙烯酸丁酯制成,但可基于丙烯酸的乙酯,异丁酯,2-乙基己酯或其他烷酯或其混合物。核聚合物也可包括含有其他可共聚的化合物,例如丙烯,乙酸乙烯酯,甲基丙烯酸甲酯,丁二烯,异戊二烯或类似物。核聚合物材料也可包括具有大致等反应性的两个或更多个非共轭双键的交联单体,例如乙二醇二丙烯酸酯,丁二醇二甲基丙烯酸酯和类似物。核聚合物也可包括具有不相同反应性的两个或更多个非共轭双键的接枝连接的单体,例如马来酸二烯丙酯和甲基丙烯酸烯丙酯。
可由甲基丙烯酸甲酯和任选地其他甲基丙烯酸烷酯,例如甲基丙烯酸的乙酯和丁酯或其混合物,聚合壳部分。最多40wt%或更多的壳单体可以是苯乙烯,乙酸乙烯酯,氯乙烯和类似物。可用于本发明实施方案的额外的核-壳接枝共聚物公开于美国专利3,984,497;4,096,202;4,034,013;3,944,631;4,306,040;4,495,324;4,304,709;和4,536,436中。核-壳接枝共聚物的实例包括,但不限于,"MBS"(甲基丙烯酸酯-丁二烯-苯乙烯)聚合物,它由在聚丁二烯或聚丁二烯共聚物橡胶存在下,聚合甲基丙烯酸甲酯而制造。MBS接枝共聚物树脂通常具有苯乙烯-丁二烯橡胶核,和丙烯酸类聚合物或共聚物的壳。其他有用的核-壳接枝共聚物的实例包括ABS(丙烯腈-丁二烯-苯乙烯),MABS(甲基丙烯酸酯-丙烯腈-丁二烯-苯乙烯),ASA(丙烯酸酯-苯乙烯-丙烯腈),所有丙烯酸类,SA EPDM(在乙烯-丙烯二烯烃单体的弹性体主链上接枝的苯乙烯-丙烯腈),MAS(甲基丙烯酸类-丙烯酸类橡胶-苯乙烯),和类似物及其混合物。
一种优选的冲击改性剂是核/壳聚合物,其中包括聚甲基丙烯酸甲酯(PMMA)或丙烯腈聚合物或共聚物的壳,和丁二烯或苯乙烯丁二烯聚合物材料的核。有用的冲击改性剂的实例包括,但不限于,获自Rohm&Haas Co的以商品名PARALOID销售的那些。优选的PARALOID等级是EXL-2691A或EXL-2650A。其他优选的材料是获自Arkema的CLEARSTRENGTH E-950和Biostrength150。
其他优选的核/壳冲击改性剂包括具有相对软的丙烯酸酯核(例如聚丙烯酸丁酯或其他低Tg的丙烯酸酯)和硬的丙烯酸酯壳(例如,PMMA)的那些。优选的材料以商品名DURASTRENGTH D-440获自Arkema,和以商品名EXL-2300和2314获自Rohm and Haas而销售。
在本发明的一个方面中,可期望冲击改性剂的一部分或全部在粘合剂材料内形成离散的辅助相。在这一实施方案中,以重量计,至少30%,更典型地至少60%和甚至可能地至少90%或全部的冲击改性剂具有相对低的Tg,和优选在固化之前,之中或之后,在粘合剂材料内形成离散的辅助相。优选地,相对低的Tg为低于20℃,更典型地低于50℃和低于70℃。对于任何核/壳聚合物来说,核,壳,或这二者可具有相对低的Tg。然而,在优选的实施方案中,核可具有相对低的Tg,而壳可具有较高的Tg,和潜在地与粘合剂材料的其余部分相容(即,不是辅助相部分的那部分粘合剂)。
进一步有用的聚合物添加剂包括粒状物(例如粉碎或研磨)弹性体或橡胶或其加合物(例如羧基封端的丁二烯丙烯腈橡胶/环氧加合物)。这种改性剂可用于增加伸长率,然而,它们倾向于降低Tg到某一程度,这取决于在该材料内所使用的弹性体的百分数和类型。所需的这类冲击改性剂的实例包括获自CVC专用化学品的HYPOX RK8-4或者获自Huntsman Chemical的Araldite LT1522ES。也可使用液体橡胶改性的环氧树脂。尤其优选羧化的固体环氧加合物,固体高分子量的腈类橡胶。也可期望包括另一腈类橡胶,例如氢化丁二烯-腈类橡胶作为全部冲击改性剂的一部分。这些可与核/壳聚合物协同地相互作用,以增加伸长率,但应当以低的用量使用,以保持所需的Tg为大于或等于80℃。
在优选的实施方案中,本发明的粘合剂材料包括约5%-70wt%加合物,优选10-50wt%,更优选15-30wt%。
发泡剂
若粘合剂组合物是可发泡的,则它将含有一种或更多种发泡剂,所述发泡剂典型地产生惰性气体,所述惰性气体将粘合剂转化成开孔和/或闭孔的泡孔结构。膨胀可有助于改进粘合剂,密封能力,声音阻尼,减少密度,或各因素的组合。可使用的发泡剂和发泡剂促进剂的用量可宽泛地变化,这取决于所需的泡孔结构的类型,粘合剂材料所需量的发泡,该材料的熔体粘度,和所需的发泡速率。在可活化的材料内,发泡剂和发泡剂促进剂的例举用量范围是约0.001wt%-2%。
可使用的化学发泡剂包括一种或更多种含氮的基团,例如酰胺,胺和类似物。合适的发泡剂的实例包括二亚硝基五亚甲基四胺,偶氮二甲酰胺,二亚硝基-五亚甲基四胺,4,4'氧-双-(苯磺酰肼),三肼基三嗪和N,N'-二甲基-Ν,Ν'-二亚硝基-对苯二甲酰胺。
可另外或替代地使用物理发泡剂。作为一个实例,可使用当暴露于热下时软化并膨胀的溶剂填充的聚合物壳。典型实例以商品名Expancel由Akzo Nobel销售。
也可在粘合剂中提供用于化学发泡剂的促进剂,增加发泡剂形成惰性气体时的速度。一种优选的发泡剂促进剂是金属盐,例如氧化物,例如氧化锌。其他优选的促进剂包括有机碱,例如脲和有机酸,例如己二酸或苯甲酸。苯磺酸锌也可以是所需的促进剂。
聚合物或共聚物
粘合剂材料可包括一种或更多种额外的聚合物(例如,共聚物),它们典型地,但不一定是共聚物或三元共聚物,所述聚合物可包括各种不同的聚合物,例如热塑性材料,弹性体,热固性材料,可热固化的材料,其结合物或类似物。例如,且没有限制地,可以合适地掺入到粘合剂材料内的聚合物包括卤化聚合物,聚碳酸酯,聚酮,和氨基甲酸酯的聚合物,聚酯,硅烷,砜,烯丙基,烯烃,苯乙烯类,丙烯酸酯类,甲基丙烯酸酯类,环氧化物,硅酮,酚类,橡胶,聚苯醚,对苯二甲酸酯,乙酸酯(例如EVA),丙烯酸酯类,甲基丙烯酸酯类(例如,乙烯丙烯酸甲酯聚合物)或其混合物。其他潜在的聚合物可以是或者可没有限制地包括聚烯烃(例如聚乙烯,聚丙烯),聚苯乙烯,聚丙烯酸酯,聚(环氧乙烷),聚(乙烯亚胺),聚酯,聚氨酯,聚硅氧烷,聚醚,聚膦嗪,聚酰胺,聚酰亚胺,聚异丁烯,聚丙烯腈,聚(氯乙烯),聚(甲基丙烯酸甲酯),聚(乙酸乙烯酯),聚(偏氯乙烯),聚四氟乙烯,聚异戊二烯,聚丙烯酰胺,聚丙烯酸,聚甲基丙烯酸酯。尽管不要求,但可期望粘合剂材料包括一种或更多种乙烯聚合物或共聚物,例如乙烯丙烯酸酯,乙烯乙酸酯或类似物。乙烯甲基丙烯酸酯和乙烯乙酸乙烯酯是两种优选的乙烯共聚物。
优选地,当使用时,一种或更多种额外的聚合物占粘合剂材料的约0.1%-约50%,更优选约1%-约20%,和甚至更优选约5%-约15wt%。
当在配方内使用时,这些成分的主要目的是在未固化状态下提供更多的热塑性-状特性。这可能包括在未固化状态下更多未固化的挠性,较低的粘性,固化之前降低的冷流动,当使用典型的聚合物加工设备时,改进的加工性。在固化工艺过程中,这些材料可充当粘度改性剂,以改性流挂和流动行为。
填料和其他组分与添加剂
本发明的粘合剂材料也可包括一种或更多种填料,其中包括,但不限于,粒状物质(例如,粉末),珠粒,微球或类似物。使用填料可赋予粘合剂诸如强度,尺寸稳定性和抗冲击性之类的性能,然而,它们可降低伸长性能。添加填料也可减少配方成本,并产生在固化之前具有较低粘性的产品。
可使用的填料的实例包括氧化硅,硅藻土,玻璃,粘土(例如,包括纳米粘土),滑石,颜料,着色剂,玻璃珠或泡,碳纤维或陶瓷纤维,和尼龙或聚酰胺纤维(例如,Kevlar)。合适的填料的实例没有限制地包括硅灰石,滑石,蛭石,页硅酸盐,锌蒙脱石,皂石,绿脱石,蒙脱石或其混合物。适合于粘合剂材料的粘土可以煅烧或者未煅烧。可用作填料的粘土可包括选自高岭石,伊利石,绿泥石,蒙皂石或海泡石组中的粘土,它们可以被煅烧。粘土也可包括微量的其他成分,例如碳酸盐,长石,云母和石英。
在一个优选的实施方案中,一种或更多种矿物或石头类型的填料,例如碳酸钙,碳酸钠或类似物可用作填料。在另一优选的实施方案中,硅酸盐矿物,例如云母可用作填料。
当使用时,在粘合剂材料内的填料量范围可以是以重量计,2%到大于30%或更大,但更典型地约8-25wt%,然而,低于20%的用量是优选的,以便保持粘合剂所需的伸长率。根据一些实施方案,粘合剂材料可包括约0%-约3wt%,和更优选略小于1wt%粘土或类似填料。粉化(例如约0.01-约50,和更优选约1-25微米的平均粒径)的矿物类型的填料可占约5%-40wt%,更优选约10%-约25wt%。
其他添加剂,试剂或性能改性剂也可视需要包括在粘合剂材料内,其中包括,但不限于,抗UV剂,阻燃剂,热稳定剂,着色剂,加工助剂,润滑剂,增强剂/填料(例如短切或连续的玻璃、陶瓷、芳族聚酰胺或碳纤维,粒状物或类似物)。
对于一些实施方案来说,粘合促进剂可以是所需的。尽管可使用许多粘合促进剂,但已发现,胺或环氧官能的分子,例如胺或环氧官能的硅烷是尤其所需的。一种例举的粘合促进剂是以商品名Z-6040商购于Dow Corning而销售的环氧丙氧丙基三甲氧基硅烷。可包括增粘剂,例如脂族,芳族或脂族/芳族石油树脂,也可以是天然的松香酯增粘剂。
本发明的优选的结构粘合剂组合物包括:
i.10%-50%环氧树脂;
ii.10%-30%热塑性改性剂;
iii.2%-10%固化剂;
iv.2%-50%增韧剂;
v.5%-40%冲击改性剂;
vi.0%-25%填料。
冲击改性剂可以是冲击改性剂的混合物。
任选地含有发泡剂,以提供可发泡的配方。
百分数以重量计,且基于所存在的成分(i)-(vii)的总量。
粘合剂材料的形成与应用
粘合剂可以是液体,糊剂或固体。在优选的实施方案中,以在环境温度下为固体,触摸起来不发粘,且具有基本上均匀组成的材料形式,形成粘合剂材料。可使用各种混合技术,获得这种材料。
根据一个实施方案,可通过加热通常比较容易软化或者液化的一种或更多种组分,例如,聚合物基材料,诱导这些组分变为可混合状态,从而形成粘合剂材料。之后,其余组分可与软化组分混合。
在优选的实施方案中,单独地,以它们的混合物或结合物形式提供这些材料到挤出机中。然后挤出机混合这些材料,形成粘合剂材料。或者,可充分地混合粘合剂材料并成形,然后喂入到挤出机中以供分配。
重要的是,在混合过程中,各组分的温度保持低于活化温度,所述活化温度将引起粘合剂材料热硬化(固化)和发泡,若存在发泡剂的话。值得注意的是,当粘合剂材料含有发泡剂时,粘合剂材料的温度应当保持低于将活化发泡剂、固化剂或二者的温度。主要的是,可在比发生固化和任选地发泡时低的温度下,施加该材料到待粘结的表面上。在其中期望维持粘合剂材料在较低温度下的情况中,可期望使用压力或压力与热的组合,维持各组分在半固体或粘弹性状态下,以混合粘合剂材料的各组分。可设计各种机器,例如挤出机或者其他机器,施加热量,压力或这二者到材料上。
在形成粘合剂材料之后,典型地施加该材料到表面或基底上。优选地,在比发生固化和发泡时低的温度下以熔体形式施加粘合剂。可对该材料造粒以供在挤出和注塑(它们是优选的施加方法)中使用。然而,可能的情形是,可形成粘合剂材料,和随后将它与所需的基底接触简单地放置。当基底和所形成的含粘合剂材料的材料暴露于热量下时,发生粘合与活化。在施加之后,可冷却该材料,在基底上提供触摸起来干燥的可热硬化的粘合剂层。然后可能地在运输之后,可将基底与待粘结的其他组件一起组装,然后通过加热活化粘合剂,产生粘合性能并形成粘结。在其中粘合剂材料包括发泡剂的情况下,材料的活化可包括至少一定程度的发泡或起泡。这种发泡或起泡可辅助粘合剂材料润湿基底并与基底形成紧密粘结。然而,或者应当意识到,可活化粘合剂材料,在没有发泡或起泡的情况下,软化和/或流动,且仍然可基本上润湿基底,形成紧密粘结。
取决于打算的应用,可按照许多不同的方式和在不同的时间下,施加粘合剂材料,并活化。因此,以下讨论粘合剂材料的例举用途,以阐述粘合剂材料的优选的施加和活化方法。特别地,粘合剂材料可尤其用于增强,密封和粘合,声音阻挡或类似用途。粘合剂材料的潜在用途的实例公开于美国专利7,125,461和美国专利申请11/757,499中。该粘合剂也可用作折边粘合剂,正如WO03/022953;欧洲专利申请2231348和英国专利申请1201943.6中所述。
作为另一实例,可在待粘结在一起的表面之间挤压粘合剂材料,和随后活化。还应当意识到待粘结的表面可以是单一组件或元件或者两个或更多个组件或元件的一部分,它们通过粘合剂材料和任选的额外的连接件彼此连接。
在一个实施方案中,待粘结的表面是机动车车辆的组件的一部分。在这一实施方案中,典型地,在机动车涂布干燥操作所使用的高温条件下(例如,在电泳涂漆或机动车刷漆操作常见的温度下,典型地120℃-250℃的温度),活化粘合剂材料。结构粘合剂应用的实例公开于美国专利申请10/234,902;10/386,287;60/451,811中。
在一些应用中,尤其在机动车工业中,粘合剂的进一步的要求是,粘合剂将粘附到携带冲压油的金属表面上。另外,优选粘合剂流动,以覆盖整个金属表面,和对金属表面的粘合性大于在粘合剂内部的内粘合(例如在金属上的内聚破坏)。这通过分离粘结的金属表面并测定携带粘合剂的表面区域的百分数来评估。
在另一实施方案中,以预成形的部件形式施加粘合剂材料;可例如通过模塑或挤出和/或切割,成型粘合剂材料,形成基本上预定尺寸的粘合剂材料部件。
将粘合剂材料形成为预成形的部件可提供优点。它可避免对庞大且昂贵的泵送和分配设备的需求。在其中可泵送的粘合剂难以施加的位置上,尤其在难以到达的位置上,它可提供粘合剂材料的容易施加。可预施加粘合剂材料部件到组件表面,例如金属冲压件上,以便粘合剂材料被供应到装置操作PIA(part-in-assembly)中(例如,粘合剂材料被施加到装置上,当粘合剂材料已经施加到其上的组件被组装到装置中时)。在例如电泳涂漆和/或磷酸化操作中,粘合剂材料也可显示出所需的抗"冲脱(wash off)”。这些预成形的部分粘合剂尤其可用作折边粘合剂,和在碰撞过程中,在机动车中在易于变形的区域内用作粘合剂,在所述变形下,高的伸长率可减少对修理和保持腐蚀防护的需求。
通过下述实施例阐述本发明。
在实施例中使用下述材料。
使用加热的σ刀片式混合器混合各成分(如下所述,单位wt%)。
实施例 | 1 | 2 | 3 | 4 | 5 | 6 |
Araldite GT7071 | 8.60 | 5.43 | 5.26 | 5.45 | 5.9 | |
DER331 | 5.00 | |||||
Hypox RF1341 | 12.00 | |||||
Araldite GY282 | 4.30 | 5.43 | 5.26 | 7.9 | 6.7 | |
Araldite LT1522ES | 14.50 | 18.47 | 17.87 | 13.00 | 19 | 16.65 |
Phenoxy MB(Inchem) | 21.89 | 25 | ||||
Phenoxy MB Kukdo | 24.19 | 24.49 | 20.82 | |||
SP-TMEP | 35.95 |
Butvar B-90 | 4.26 | |||||
Mowital LP B16H | 4.86 | 4.71 | 4.76 | 4.05 | ||
Paraloid EXL2650A | 11.75 | 13.4 | 12.99 | 17.00 | 13.15 | 11.18 |
DY965CH | 7.70 | 9.8 | 9.5 | 9.00 | 7.35 | 5 |
Cardolite Lite2513HP | 2.60 | 3.26 | 3.16 | 3.25 | 2.75 | |
Armoslip CPV | 2.60 | 0.3 | 3.16 | |||
Armoslip B | 0.6 | |||||
Lotryl35BA320 | 5.15 | 5 | 5.15 | 4.38 | ||
Calibrite OG | 14.45 | 15 | ||||
Garmite1958 | 0.40 | 0.6 | 0.6 | 0.6 | 0.5 | |
颜料 | 0.1 | 0.1 | 0.1 | 0.1 | ||
Omicure U52 | 0.50 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Dyhard100S | 5.70 | 7.1 | 7.1 | 6.8 | 7.1 | 6.04 |
Cellcom AC7000DB | 0.75 | 0.6 | 0.5 | 0.75 | 0.6 | 0.43 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
冷却混合物,提供在环境温度下触摸起来干燥的固体材料。
实施例1-4是对比例,和实施例5与6是本发明。
产品在90℃下的粘度为:
实施例 | 1 | 2 | 3 | 4 | 5 | 6 |
0,1s-1(kPa.s) | 9.21 | 10.6 | 10.6 | 14.9 | 19.2 | 21.2 |
10s-1(kPa.s) | 2.12 | 2.53 | 2.03 | 2.98 | 3.28 | 3.52 |
1000s-1(kPa.s) | 0.043 | 0.042 | 0.0048 | 0.019 |
密度和膨胀程度如下所述。
实施例 | 1 | 2 | 3 | 4 | 5 | 6 |
密度g/cm | 1.16 | 1.05 | 1.08 | 1.03 | 1.1 | 1.18 |
膨胀(25×25×1mm) | 107 | 100 | 65 | 72 | 81 | 79 |
使用试验方法ASTM D638Type1,测量粘合剂的强度性能,并如下所述:
实施例 | 1 | 2 | 3 | 4 | 5 | 6 |
拉伸模量(MPa) | 296 | 178 | 119 | 215 | 162 | 204 |
最大应力(MPa) | 4.06 | 3.35 | 4.67 | 4.2 | 6.58 | 7.01 |
伸长率(%) | 8.55 | 7.06 | 53.7 | 13.49 | 21.74 | 15.26 |
Tg(℃)DMA | 84.7 | 86.9 | 77.85 | 87.9 | 88.5 | 91.9 |
在覆盖有冲压油的金属样片上涂布该材料。通过在烘箱内经20分钟加热金属到185℃,进行该材料的粘结、膨胀和固化测试。
金属样片的搭接剪切和断裂为
实施例 | 1 | 2 | 3 | 4 | 5 | 6 |
最大应力,搭接剪切(MPa) | 6.23 | 7.23 | 8.22 | 11.52 | 9.96 | 9.35 |
断裂(%内聚破坏) | 100% | 97% | 98% | 100% | 100% | 100% |
实施例7
以与实施例1-6所使用的相同方式,制备下述粘合剂配方,用量以wt%计算。
Phenoxy MB | 22.3 |
Butvar B90 | 10.4 |
Araldite LT1522E5 | 21.4 |
Biostrength150 | 8.9 |
Cardolite NC514 | 8.3 |
Kane Ace MX267 | 9.5 |
Elvamide8061 | 10.4 |
填料 | 2.4 |
Amicure CG1200 | 4.5 |
氧化锌 | 0.2 |
Cellcom AC7000DB | 1.1 |
Omicure U52 | 0.5 |
与实施例1-6中一样,固化粘合剂并发泡。当使用试验方法ASTMD638Type1测量时,25x25x1mm模制品的膨胀为120%和粘合剂的强度性能如下所述:
模量(MPa) | 220 |
最大应力(MPa) | 5.5 |
伸长率(%) | 17.7 |
Tg(℃)DMA | 89 |
膨胀(25x25x1mm) | 120% |
Claims (35)
1.一种可热硬化的结构粘合剂材料,一旦固化,则其断裂伸长率为至少10%且玻璃化转变温度(Tg)大于或等于80℃。
2.权利要求1的粘合剂,其中固化粘合剂的断裂伸长率为至少15%,优选至少20%。
3.权利要求1或2的粘合剂,其中固化粘合剂的刚度为至少100MPa和搭接剪切为至少7MPa。
4.前述任何一项权利要求的粘合剂,它包括在环境温度下触摸起来不发粘的固体。
5.前述任何一项权利要求的粘合剂,它在比硬化温度低的高温下可加工。
6.前述任何一项权利要求的粘合剂,它包括环氧树脂,热塑性改性剂,增韧剂,冲击改性剂和固化剂。
7.权利要求6的粘合剂,其中热塑性改性剂包括热塑性环氧树脂。
8.权利要求7的粘合剂,其中热塑性环氧树脂是苯氧基树脂。
9.权利要求6-8任何一项的粘合剂,其中冲击改性剂包括核/壳材料。
10.权利要求6-9任何一项的粘合剂,其中冲击改性剂包括羧基封端的丁二烯橡胶的环氧加合物。
11.权利要求6-10任何一项的粘合剂,其中增韧剂包括羟基封端的聚氨酯聚合物。
12.权利要求6-11任何一项的粘合剂,其中增韧剂包括聚乙烯基聚合物。
13.权利要求6-12任何一项的粘合剂,其中增韧剂包括聚酰胺。
14.权利要求6-13任何一项的粘合剂,其中热塑性改性剂是聚醚。
15.权利要求14的粘合剂,其中聚醚是苯氧基树脂。
16.权利要求6-15任何一项的粘合剂,其中增韧剂包括聚合物,所述聚合物是胺改性的环氧树脂。
17.权利要求6-16任何一项的粘合剂,其中增韧剂是环氧化聚硫化物。
18.前述任何一项权利要求的粘合剂,它含有发泡剂。
19.权利要求18的粘合剂,其中发泡剂在比粘合剂能熔融加工时的温度高的温度下加热活化。
20.前述任何一项权利要求的粘合剂,它包括一种或更多种填料。
21.前述任何一项权利要求的粘合剂,它的固化温度为120℃-250℃。
22.前述任何一项权利要求的粘合剂,它在范围为80℃-120℃的温度下能熔融加工。
23.前述任何一项权利要求的粘合剂,它包括7-50wt%的环氧树脂。
24.前述任何一项权利要求的粘合剂,它包括3-40wt%的热塑性改性剂。
25.前述任何一项权利要求的粘合剂,它包括2-50wt%的增韧剂。
26.前述任何一项权利要求的粘合剂,它包括4-70wt%的冲击改性剂。
27.前述任何一项权利要求的粘合剂,它包括0.2-6wt%的固化剂。
28.前述任何一项权利要求的粘合剂,它包括0.01-2wt%的发泡剂。
29.前述任何一项权利要求的粘合剂,它含有用量不大于1wt%的滑爽剂。
30.前述任何一项权利要求的粘合剂,它含有用量不大于20wt%的填料。
31.一种结构粘合剂组合物,它包括:
i.10%-50%环氧树脂;
ii.10%-30%热塑性改性剂;
iii.2%-10%固化剂;
iv.2%-50%增韧剂;
v.5%-40%冲击改性剂;
vi.0%-25%填料;
任选地含有发泡剂。
32.前述任何一项权利要求的结构粘合剂用于粘结机动车组件的用途。
33.权利要求32的用途,作为折边法兰生产中的粘合剂。
34.权利要求32的用途,用于提供在冲击下具有改进的变形的粘合剂粘结。
35.权利要求32-34任何一项的用途,其中在机动车的电泳涂漆或刷漆操作过程中,在机动车的组件上挤出粘合剂,并活化,以将各组件粘结在一起。
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CN112585190A (zh) * | 2018-08-06 | 2021-03-30 | 泽菲罗斯有限公司 | 具有更高断裂伸长率的高弹性模量泡沫结构材料 |
CN114127151A (zh) * | 2019-04-03 | 2022-03-01 | 汉高股份有限及两合公司 | 基于改性环氧树脂的双组分(2k)组合物 |
CN111287034A (zh) * | 2020-03-03 | 2020-06-16 | 中国船舶重工集团公司第七一一研究所 | 有轨电车钢轨的防护装置 |
CN112831303A (zh) * | 2021-02-20 | 2021-05-25 | 上海清津光电子科技有限公司 | 一种可去除胶水及其制备方法 |
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BR112013020896A2 (pt) | 2016-09-27 |
CN103459539B (zh) | 2016-11-16 |
EP2675860B1 (en) | 2020-02-12 |
EP2675860A1 (en) | 2013-12-25 |
WO2012110230A1 (en) | 2012-08-23 |
KR20140012667A (ko) | 2014-02-03 |
US9394468B2 (en) | 2016-07-19 |
US20140113983A1 (en) | 2014-04-24 |
GB201102672D0 (en) | 2011-03-30 |
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