CN105745236A - 粘合剂、带粘合剂背衬的构件以及用于构件之间连接的方法 - Google Patents
粘合剂、带粘合剂背衬的构件以及用于构件之间连接的方法 Download PDFInfo
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Abstract
本发明提供了一种用于在构件之间接合的方法,该方法包括:通过向第一构件表面施加包含不具有辐射可聚合官能团的热固性树脂、硬化剂、具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物、具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物、以及热膨胀胶囊的液体组合物来形成粘合剂层;通过照射辐射到所述粘合剂层上来半固化粘合剂层;在半固化粘合剂层上方设置第二构件,从而与第一构件表面相对;以及通过加热以膨胀和固化所述半固化粘合剂层来接合第一构件和第二构件。
Description
技术领域
本发明涉及用于构件之间连接的方法,并涉及用于该方法的粘合剂以及带粘合剂背衬的构件。
背景技术
众所周知,可使用含有诸如环氧树脂的热固性树脂的粘合剂以用于接合无法通过机械紧固或焊接接合的构件。当提前向待接合的构件表面提供粘合剂层时,考虑到处理、贮存稳定性、对于工作环境的影响等时,通常会使用膜型或片型粘合剂(参见日本未经审查的专利申请公布H08-165459A以及未经审查的专利申请公布H09-095600A)。
此外,在日本未经审查的专利申请公布2007-106963A中,尝试使用混合热膨胀胶囊的片状粘合剂来接合具有粗糙度等的构件。
发明内容
但是已发现,膜型或片型粘合剂需要用于根据待粘合部分的形状定制粘合剂的处理步骤以及用于使用压力将该粘合剂转移至粘附表面的步骤(在某些情况下会同时进行加热),但是对于形状存在限制,并在处理期间可发生材料的损失。
另一方面,需要可通过根据构件之间的间隙来调整粘合剂结合部的厚度并且可确保足够的粘合力的粘合剂。
因此,本发明的目标之一是使用带粘合剂背衬的构件提供构件之间的接合方法,该带粘合剂背衬的构件可展示构件之间的出色的粘合性能,并且可用于填充构件之间的间隙。
在本发明的一个方面,提供了用于在构件之间接合的方法。该方法包括:通过向第一构件表面施加包含不具有辐射可聚合官能团的热固性树脂、硬化剂、具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物、具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物、以及热膨胀胶囊的液体组合物来形成粘合剂层;通过照射辐射到粘合剂层来半固化粘合剂层;在半固化粘合剂层上方设置第二构件,从而与第一构件表面相对;以及通过加热以膨胀和固化半固化粘合剂层来接合第一构件和第二构件。
在本发明的另一方面,提供了用于填充间隙的粘合剂。该粘合剂包含液体组合物,该液体组合物包含:不具有辐射可聚合官能团的热固性树脂;硬化剂;具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物;具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物;以及热膨胀胶囊。
在本发明的另外的方面,提供了带粘合剂背衬的构件,该构件包括通过上述粘合剂形成的层。
根据本发明,可提供构件之间的接合方法,该方法使用带粘合剂背衬的构件,该带粘合剂背衬的构件可展示构件之间的出色的粘合性能,并且/或者可用于填充构件之间的间隙。
通过构件之间的接合方法,可提前在构件表面上形成粘合剂层,并且可大量提供展示出色粘合性能的带粘合剂背衬的构件。此外,在粘合剂层中加入热膨胀胶囊可允许在加热之前在两个构件之间存在间隙,从而加热期间两个构件由于粘合剂层的膨胀而以高可靠性粘合。
附图说明
图1为剖视图,其示意性地示出根据本发明实施方案的构件之间的接合方法。
图2为透视图,其示意性地示出根据本发明实施方案的带粘合剂背衬的构件的一个实施方案。
图3为透视图,其示意性地示出根据本发明实施方案的带粘合剂背衬的构件的一个实施方案。
图4为透视图,其示意性地示出根据本发明实施方案的带粘合剂背衬的构件的一个实施方案。
图5为透视图,其示意性地示出根据本发明实施方案的带粘合剂背衬的构件的一个实施方案。
本发明的示例性实施方案
在下文参照附图详细描述了本发明的实施方案,但是本发明不限于下面的实施方案。在下面的描述中,将相同附图标号分配给了相同或相似的部分,而省去了多余的描述。
本发明实施方案的构件之间的接合方法包括:通过向第一构件表面施加液体组合物来形成粘合剂层的步骤、以辐射照射粘合剂层以半固化粘合剂层的步骤、在半固化粘合剂层上方设置第二构件以与第一个构件表面相对的步骤、以及通过加热使半固化粘合剂层膨胀并固化来接合第一构件和第二构件的步骤。在此所述的“粘合剂层上方”是指粘合剂层的一面不接触第一构件。
(液体组合物)
根据本发明实施方案的液体组合物包含:(a)不具有辐射可聚合官能团的热固性树脂;(b)硬化剂;(c)具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物;(d)具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物;以及(e)热膨胀胶囊。
(a)组分:热固性树脂
(a)组分不具有具体限制并且可为不具有辐射可聚合官能团的任何热固性树脂,并且它们的示例包括环氧树脂和氰酸酯树脂。
环氧树脂的形式在室温下可为固态、半固态或液态,并且环氧树脂可与不同类型的环氧树脂结合使用。环氧树脂的示例包括双酚型环氧树脂(诸如双酚A型环氧树脂、双酚F型环氧树脂等等),通过氢化双酚型环氧树脂、脂族环氧树脂、卤化环氧树脂以及酚醛型环氧树脂的芳环获得的氢化环氧树脂。可使用酚醛型环氧树脂之外的具有多官能环氧树脂或侧链中有多环芳族基团的环氧树脂来提升耐热性。多官能环氧树脂的示例包括对氨基苯酚三缩水甘油醚和其他缩水甘油胺型环氧树脂、三羟基苯基甲烷三缩水甘油醚以及乙二醛苯酚酚醛四缩水甘油醚;并且侧链中含有多环芳族基团的环氧树脂的示例包括芴系环氧树脂。可独立使用单个类型的环氧树脂或可混合使用两个或更多个类型。
对于氰酸酯树脂,二氰酸酯化合物为优选的,并且示例包括双(4-氰酸苯酯)甲烷、双(3-甲烷-4-氰酸苯酯)甲烷、双(3-乙基-4-氰酸苯酯)甲烷、双(3′5-二甲基-4-氰酸苯酯)甲烷、1′1-双(4-氰酸苯酯)乙烷以及2′2-双(4-氰酸苯酯)丙烷以及由这些物质衍生的预聚物。
当考虑到施加液体组合物时的粘度以及半固化粘合剂层表面厚度之间的平衡,作为液体组合物总质量的标准(a)组分的含量优选地介于10质量%至90质量%之间,更优选地介于25质量%至85质量%之间。
(b)组分:硬化剂
可根据用作(a)组分的热固性树脂的类型来选择(b)组分。
对于(b)组分,当将环氧树脂用作(a)组分时,硬化剂不受具体限制,只要可以通过热来硬化环氧树脂即可,但是可使用在近室温下为惰性并且通过热活化的潜伏性硬化剂。潜伏性硬化剂的示例包括双氰胺及其衍生物、酰肼化合物、三氟化硼-胺络合物以及胺化合物的反应产物(尿素衍生物)和异氰酸酯化合物或尿素化合物。硬化加速剂也可与环氧树脂的硬化剂结合用作(b)组分。硬化加速剂的示例包括咪唑化合物、胺化合物和环氧化合物的反应产物(胺-环氧加合物)、尿素衍生物等等。
从增强耐热性的角度出发,优选的是选择环氧树脂和硬化剂的组合,使得环氧化合物的玻璃化转变温(Tg)为100℃或以上,并且更为优选的是进行选择以达到150℃或以上。
当将氰酸酯树脂用作(a)组分时,有机金属盐、有机金属盐化合物或其他硬化催化剂可作为(b)组分的示例提供。铁、铜、锌、钴、锰、镍、锡等等可作为金属的示例提供,这些金属组成有机金属盐或有机金属络合物。有机金属盐的示例包括环烷酸铁、环烷酸铜、环烷酸锌、环烷酸钴、环烷酸镍、环烷酸锰等等。有机金属络合物的示例包括乙酰丙酮铜等等。
当环氧树脂用作(a)组分并且当考虑到室温下的固化速率以及贮存稳定性时,(b)组分的含量相对于100份质量的(a)组分优选地为0.1至80份质量,更为优选地为1至50份质量。当将氰酸酯树脂用作(a)组分时,含量优选地为0。相对于100份(a)组分质量为0.01到10份质量,更为优选地为0.01到1份质量。
(c)组分:第一可聚合化合物
(c)组分不受具体限制,只要它是具有至少一个或多个辐射可聚合官能团和可热固化官能团中的每一种的可聚合化合物即可。将(c)组分包括在内增强了和(a)组分或(b)组分的相容性并提升了所形成的粘合剂层的粘合力。
辐射可聚合官能团是具有可聚合不饱和键的基团,该可聚合不饱和键在受到紫外线、电子束、可见光或其他辐射照射时会发生反应,并且其示例包括丙烯酰基、甲基丙烯酰基、乙烯基等等。
可热固化的官能团是可以和(a)组分或(b)组分反应的基团,其示例包括羧基、缩水甘油基、羟基、氨基等等。
具有羧基和丙烯酰基或甲基丙烯酰基的化合物的示例包括丙烯酸、甲基丙烯酸、丙烯酰氧基乙基邻苯二甲酸盐、甲基丙烯酰氧基乙基邻苯二甲酸盐、丙烯酰氧基乙基琥珀酸盐、甲基丙烯酰氧基乙基琥珀酸盐、ω-羧基-聚己内酯单丙烯酸盐、邻苯二甲酸单羟基乙基丙烯酸盐、丙烯酸二聚物等等。
具有缩水甘油基和丙烯酰基或甲基丙烯酰基的化合物的示例包括丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、N-[4-(2,3-环氧丙氧基)-3,5-二甲基苄基]丙烯酰胺等等。
具有羟基和丙烯酰基或甲基丙烯酰基的化合物的示例包括2-羟乙基丙烯酸酯、2-羟乙基甲基丙烯酸酯、2-羟丙基丙烯酸酯、2-羟丙基甲基丙烯酸酯等等。
(d)组分:第二可聚合化合物
(d)组分不受具体限制,只要它是具有至少一个辐射可聚合官能团并且不具有可热固化官能团的可聚合化合物即可。可独立使用单个类型的(d)组分或可混合使用两个或更多个类型。
(d)组分的示例为均聚物的玻璃化转变温度小于0℃的单烯键式不饱和单体(下文称为“低Tg单体”),以及均聚物的玻璃化转变温度大于0℃的单烯键式不饱和单体(下文称为“高Tg单体”)。
对于低Tg单体,具有带2至20个碳原子的烷基的非叔烷基醇与丙烯酸或甲基丙烯酸的酯为优选的,并且具有带4至12个碳原子的烷基的非叔烷基醇与丙烯酸或甲基丙烯酸的酯为更优选的。该类型低Tg单体的示例包括丙烯酸正丁酯、丙烯酸己酯、丙烯酸2-乙基己酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸十二烷基酯、丙烯酸月桂酯、丙烯酸十八烷基酯或它们的混合物。
高Tg单体的示例包括丙烯酸异冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸环己酯、丙烯酸二环戊酯、甲基丙烯酸二环戊烯酯、丙烯酰基吗啉、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-乙烯基哌啶、N,N-二甲基丙烯酰胺、丙烯腈等等。
当由液体组合物形成的粘合剂层受到辐射照射时,(d)组分可与(c)组分形成共聚物。由此将粘合剂层硬化。从增强耐热性的角度出发,优选的是选择可聚合化合物作为(d)组分,从而由(c)组分和(d)组分构成的共聚物的固化产物的Tg为100℃或更高。可根据Fox公式(TGFox,Bull.Am.Phys.Soc.,1,123(1956)(TGFox,《美国物理学会通报》,第1卷,第123页,1956年))计算共聚物的Tg。
(c)组分和(d)组分在液体组合物中的含量比率按质量比率((c)组分:(d)组分)计优选地为90∶10至1∶99,并且更优选地为60∶40至2∶98。
以上范围是为了更易于体现和(a)组分的相容性、热膨胀期间的流动性以及固化(硬化)后的粘合性之间的平衡。
(e)组分:热膨胀胶囊
热膨胀微胶囊可用作(e)组分,其中作为膨胀剂的低沸点化合物由热塑性树脂包裹。在受热时热膨胀微胶囊因为构成壳的热塑性树脂软化而膨胀,而包裹在其中的膨胀剂气化,由此升高蒸汽压力而使壳膨胀。
由偏二氯乙烯、丙烯腈、苯乙烯、丙烯酸酯、甲基丙烯酸酯等等合成的共聚物可用作热塑性树脂。低沸点烃可有利地用作低沸点化合物,并且示例包括异戊烷、正戊烷、异丁烷等等。
市售产品,诸如日本Fillite株式会社(JapanFilliteCo.,Ltd.)制造的Expancel(注册商标)、松本油脂制药株式会社(MatsumotoYushi-SeiyakuCo.,Ltd.)制造的Matsumoto微球体(注册商标)、日本吴羽株式会社(Kureha,Inc.)制造的微球体等等,可用作热膨胀胶囊。
(e)组分在液体组合物中的含量优选地为0.1至50质量%,更优选地为0.3至30质量%。当(e)组分的含量为0.1质量%或更高时,轻松地得到足够膨胀,并且当为50质量%或更低时,轻松地确保硬化后的粘合强度。当考虑到确保硬化后的强粘合强度时,优选的是混合(e)组分使加热时厚度方向上的膨胀率为五倍或更小,并且更优选的是进行混合使其膨胀率为三倍或更小。
除了上述组分之外,根据本发明实施方案的液体组合物也可根据需要包含其他组分,诸如光聚合引发剂、热聚合引发剂、交联剂、链转移剂、抗氧化剂、有机或无机填料、硅烷偶联剂等等。
(f)组分:光聚合引发剂
从通过放射照射促进(c)组分和(d)组分之间的反应的角度出发,根据本发明实施方案的液体组合物还可包含光聚合引发剂。
存在两类光聚合引发剂:裂解型和夺氢型。裂解型光聚合引发剂的示例包括苯并乙醚、二乙氧基苯乙酮、2,2-二甲氧基-1,2-二苯基-1-乙酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环己基苯基酮、2-羟基-1--2-甲基-1-丙酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-1-丙酮、2-苄基-2-二甲氨基-1-(4-吗啉基苯基)-丁酮-1,2-二甲氨基-2-(4-甲苄基)1-(4-吗啉-4-基-苯基)-1-丁酮、双(2,4,6-三甲基苯甲酰)-氧化苯磷、2,4,6-三甲基苯甲酰-联苯-氧化膦等等。夺氢型光聚合引发剂的示例包括苯甲酮、2,4-二乙基噻吨酮等等。
从通过加热半固化粘合剂层来促进硬化的角度出发,根据本发明实施方案的液体组合物还可包含热聚合引发剂。热聚合引发剂的示例包括偶氮化合物,诸如偶氮二异丁腈等等,以及有机过氧化物,诸如过氧化苯甲酰等等。
任何可以和(c)组分以及(d)组分反应并且不会抑制(a)组分硬化的化合物都可用作交联剂。交联剂的示例包括二乙烯醚、多官能丙烯酸酯、多官能甲基丙烯酸酯、多官能异氰酸酯化合物、嵌段型多官能异氰酸酯化合物等等。多官能丙烯酸酯的示例包括1,6-己烷二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、1,2-乙二醇二丙烯酸酯等等。
链转移剂的示例包括四溴化碳、巯基化合物等等。巯基化合物的示例包括乙硫醇、丁硫醇、十二硫醇、巯基乙醇(硫代乙二醇)、3-巯基-丙醇、二羟丙硫醇(巯基甘油)、巯基醋酸(巯基乙酸)、2-巯基丙酸(硫代乳酸)、3-巯基丙酸、α-巯基异丁酸、巯基丙酸甲酯、巯基丙酸乙酯等等。
可根据如下目标向液体组合物添加有机或无机填料:诸如增加数量、减轻重量、赋予阻燃性、赋予热传导性、改变流量控制、着色等等。有机或无机填料的示例包括碳酸钙、云母、滑石、中空玻璃微珠、氢氧化铝、氢氧化镁、二氧化硅、核-壳橡胶、热解法二氧化硅、有机颜料、无机颜料等等。
硅烷偶联剂的示例包括具有官能团(诸如氨基、环氧基以及巯基等)的烷氧基硅烷。
此外,诸如苯氧基树脂和聚乙烯缩丁醛树脂的聚合物组分,以及诸如二甲基硅氧烷、二苯基硅氧烷等等的有机聚硅氧烷可另外混合在液体组合物中。
可通过向液体组合物添加溶剂来调整粘度,但是对于液体组合物优选地使用无溶剂体系,因为它无需干燥步骤即可去除溶剂,并且可在不考虑施加后膜减少的情况下调整粘合剂层的膜厚度。采用无溶剂的液体组合物,200μm或更厚的厚膜包衣是可行的。
根据本发明实施方案制备液体组合物的方法不受具体限制,但是(例如)可根据以下所述进行制备。
首先,组分(a)、(b)和(c)在搅拌设备中混合以制备均匀的预混合物。接下来,向预混合物添加(b)化合物和(e)化合物,并且这些化合物均匀分散以获得目标液体组合物。此外,当(f)组合物也混入时,可将其添加至预混合物。将化合物(b)、(e)和(f)添加至预混合物可在室温下或接近室温时进行。
接近室温(例如25℃)的液体组合物的粘度优选地为0.001至1000Pa·s,并且更优选地为1至1000Pa·s。
根据本发明实施方案的液体组合物可用作粘合剂。包括液体组合物的该粘合剂可按原样施加至粘附体。
根据本发明实施方案的粘合剂的特征在于它可用于填充间隙,并且包括液体组合物,该液体组合物包含:不具有辐射可聚合官能团的热固性树脂、硬化剂、具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物、具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物、以及热膨胀胶囊。从增强耐热性的角度出发,热固性树脂可为环氧树脂或氰酸酯树脂。
由于根据本发明实施方案的粘合剂可直接施加至粘附体而不用经过形成膜的步骤,并且因为方法经过简化并且粘合剂在室温下为液体,因此易于调整厚度以匹配间隙。此外,根据本发明实施方案的粘合剂可施加至设置为具有预定间隙的构件之间。
根据本发明实施方案的带粘合剂背衬的构件的特征在于具有通过上述粘合剂形成的层。带粘合剂背衬的构件具有半固化粘合剂层,其中粘合剂施加至为粘附体的第一构件,形成粘合剂层,并随后通过辐射照射粘合剂层。该类带粘合剂背衬的构件可通过加热半固化粘合剂层膨胀和固化而与第二构件接合。
(构件之间的接合方法)
图1为剖视图,其示意性地示出根据本发明实施方案的构件之间的接合方法。
(第一步)
首先,如图1的(a)中所示,将液体组合物施加至为粘附体的第一构件2,在形成粘合剂层1之后,用辐射照射粘合剂层1来制备带粘合剂背衬的半固化构件。
第一构件2未受具体限制,并且可使用各种金属、耐热树脂(诸如聚苯硫醚)、永磁体等等。第一构件2可具有平坦形状或可具有各种形状,诸如斜面、台阶、表面粗糙度等等。根据本发明实施方案的液体组合物可按细线施加,即使对于具有三维形状的构件也可如此。
图2至图5为透视图,其示意性地示出根据本发明实施方案的带粘合剂背衬的构件的一个实施方案。例如,如图2中所述,可形成粘合剂层1,该粘合剂层的厚度已改变以匹配与具有凹陷部分的第一构件2之间的高差。此外,如图3中所示,由于可在平坦的第一构件2上形成外覆层,粘合剂层1具有阶梯形状。此外,如图4中所示,可在平坦的第一构件2上形成具有复杂二维形状的粘合剂层1。
可将用于液体垫圈等应用中的手动或自动分配器用于向第一构件2施加。分配器可为接触式或非接触式的。使用分配器可实现细化施加,诸如线状施加、点状施加等等。当使用分配器时,如图5所述,可在第一构件2上形成粘合剂层1。
当将紫外光用作辐射光束时,则可将高压水银蒸气灯、金属卤素灯、LED等等用作光源,并且照射强度可为约300mWcm2,并且紫外光可在低氧气氛中进行照射。
在此,“半固化”是指表面的大部分没有粘着性,并且即使在外部接触,半固化粘合剂层1中也不存在流动性或变形。
在25℃和1Hz的条件下,半固化粘合剂层的剪切储能模量优选地为100kPa或更高,更优选地为200kPa或更高,并且最优选地为300kPa或更高。剪切储能模量为100kPa或更高的半固化粘合剂层抑制诸如灰尘的外来碎屑粘附至粘合剂层表面,并在设置在第二构件上时有助于减小摩擦力。半固化粘合剂层1的剪切储能模量的上限未受具体限制,但是可为约10,000kPa。
(第二步)
接下来如图1的(b)中所示,为单独粘附体的第二构件4设置在半固化粘合剂层1的上方,之后对半固化粘合剂层1进行加热。
第二构件4的材料未受具体限制,并且可和第一构件的材料相同,或者可为不同的材料。
(第三步)
在加热后,如图1的(c)中所示,半固化粘合剂层1通过热膨胀以形成固化接合层10,并且第一构件2和第二构件4通过填充第一构件2和第二构件4之间的间隙接合。当考虑到确保硬化后的强粘合强度时,优选的是在加热半固化粘合剂层1后厚度方向上的膨胀率为五倍或更小,更优选地为三倍或更小。
加热温度通常介于100℃至180℃,并且优选地介于130℃至170℃。
此外,根据粘附体的形状,通过再次向上述第二步骤中固化的粘合剂层上施加液体组合物来半固化粘合剂层并用辐射照射它的步骤可重复。如果粘附体之间的间隙较宽,则提供具有表面高差的粘附体是有效的。接合层10可不仅用于在构件之间进行固定,也可用作密封层或减震层。
如上所述,根据本发明实施方案的构件之间的接合方法可应用于通过填充各种粘附体之间的间隙进行接合,并且也有利于接合不同材料,诸如金属和塑料、金属和陶瓷等等。
根据本发明实施方案的构件之间的接合方法可应用于附连用在运输设备、工业设备、电气和电子设备、建筑构件等等中的金属、玻璃、陶瓷、耐热树脂加工部件等等。更具体地讲,它们的接合方法可应用于:固定机动车车身相关的部件,附连汽车和工业设备中马达内的磁体、绝缘构件、线圈等;附连自行车、家具和建筑应用中的构件;附连电子组件;固定运动设备组件;结合汽车和电子设备中的减震功能进行固定。
实施例
使用实施例在下文提供了本发明的详细描述,但是本发明并不据此受限。
(实施例1至5以及比较例1)
相应地混合表1中示出的每种组分的混合量(质量份)来制备液体组合物。请注意,表1中所示的组分如下。
(a)组分:热固性树脂
YDPN-638(酚-酚醛型环氧树脂,由新日铁住金化学有限公司(NipponSteel&SumikinChemicalCo.,Ltd.)制造)
TACTIX742(环氧树脂,由亨兹曼公司(Huntsman)制造
BT-2160RX(氰酸酯树脂,由三菱瓦斯化学株式会社(MitsubishiGasChemicalCo.,Ltd.)制造)
(b)组分:硬化剂
CG1200G(双氰胺,由空气产品公司(AirProducts)制造)
2P4MHZ-PW(咪唑衍生物,由四国化成工业有限公司(ShikokuChemicalsCo.,Ltd.)制造)
2MA-OK-PW(咪唑衍生物,由四国化成工业有限公司(ShikokuChemicalsCo.,Ltd.)制造)
环烷酸锌(由和光纯化学工业有限公司(WakoPureChemicalIndustries,Ltd.)制造)
(c)组分:第一可聚合化合物
GMA(甲基丙烯酸缩水甘油酯,由三菱人造丝有限公司(MitsubishiRayonCo.,Ltd.)制造)
(d)组分:第二可聚合化合物
FA5I3M(二环戊基甲基丙烯酸酯,由日立化学有限公司(HitachiChemicalCo.,Ltd.)制造)
(e)组分:热膨胀胶囊
FN100SS(由松本油脂制药株式会社(MatsumotoYushi-SeiyakuCo.,Ltd.)制造)
FN100M(由松本油脂制药株式会社(MatsumotoYushi-SeiyakuCo.,Ltd.)制造)
(f)组分:光聚合引发剂
Irgacure819(由巴斯夫公司(BASF)制造)
Irgacure184(由巴斯夫公司(BASF)制造)
(g)组分:核-壳聚合物颗粒
AC3355(由AikaeIndustry有限公司(AikaeIndustryCo.,Ltd.)制造)
(h)组分:碳酸钙粉末
WhitonSBred(由白石钙有限公司(ShiraishiCalciumCo.,Ltd.)制造)
(i)组分:抗氧化剂
Irganox1010(由巴斯夫公司(BASF)制造)
(j)组分:细二氧化硅
RX200(由日本微粉硅胶株式会社(NipponAerosilCo.,Ltd.)制造)
TS720(由卡博特有限公司(CabotCo.,Ltd.)制造)
[表1]
制备的液体组合物以厚度0.2mm至10mm施加至测得的尺寸为25×50×2mm(厚度)的PPS树脂板(由东曹株式会社(TosohCo.,Ltd)制造)的末端部分,并通过高压水银蒸气灯(优志旺公司(Ushio,Inc.)制造的SpotcureSP-II,UVA_600mW/cm2)受照射15秒,形成半固化粘合剂层。
(半固化粘合剂层的粘着性)
半固化粘合剂层的粘着性使用下面的过程测量。
首先,半固化粘合剂层在上述照射条件下形成0.5mm的厚度,并且将四层的该半固化粘合剂层堆叠以制备厚度为约2mm的试件。接下来,用直径25mm的平行板保持试件,并使用Rheometrics公司(RheometricsCorporation)制造的RDA-II测量测试温度为25℃并且测试频率为1Hz时的剪切储能模量。对于储存弹性模量超出1000kPa的测试材料,通过将测试材料倒圆来制备圆柱形试件,从而该圆柱形试件具有约8mm的直径、约10mm的高度,并且该试件由直径为7.9mm的平行板保持。测量在相同的条件下进行。结果示于表2中。
(硬化后的粘合性能)
通过经由金属丝间隔件在半固化粘合剂层上方设置测得的尺寸为25×100mm、厚度为1.6mm的冷轧铜板(通过夹具压力保持)来制备试件,从而形成宽度为25mm、长度为10mm的粘合剂表面区域。使用感应加热设备(由Aronicus制造的HotShot2)以16.7℃/min的平均升温速率将试件从25℃加热至150℃,接下来将该试件置于150℃的烘箱中达20分钟以硬化(固化)粘合剂层,从而制备评估试件。改变间隔件的厚度以提供达到半固化粘合剂层厚度1.5倍至9倍的间隙。例如,表2中的“1.5倍”意味着间隔件的厚度为半固化粘合剂层厚度的1.5倍。
在环境温度、大气压以及5mm/min的移动速度下使用张力检验器(RTC1325A,由Orientec有限公司(Orientec,Inc.)制造)测量处于张力下的评估试件的剪切粘结强度。
在实施例1至5中,半固化粘合剂层受热而暂时流化,同时开始膨胀以填充通过金属丝间隔件确定的间隙,然后在该状态下硬化。同时在比较例1中,由于没有发生膨胀,因此间隙没有被填充,并且当在加热后去除夹具时,PPS和铜板易于分离。在表2中提供了结果。在表2中,“可以”表示间隙被完全填充,而“不好”则表示间隙没有被填充。
[表2]
Claims (6)
1.一种用于在构件之间接合的方法,包括:通过向第一构件表面施加包含不具有辐射可聚合官能团的热固性树脂、硬化剂、具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物、具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物、以及热膨胀胶囊的液体组合物来形成粘合剂层的步骤;通过照射辐射到所述粘合剂层来半固化所述粘合剂层的步骤;在所述半固化粘合剂层上方设置第二构件,从而与所述第一构件表面相对的步骤;以及通过加热以膨胀和固化所述半固化粘合剂层来接合所述第一构件和所述第二构件的步骤。
2.根据权利要求1所述的方法,其中所述半固化粘合剂层的剪切储能模量在25℃和1Hz下不小于100kPa。
3.根据权利要求1或2所述的方法,其中所述热固性树脂为环氧树脂或氰酸酯树脂。
4.一种用于填充间隙的粘合剂,包含液体组合物,所述液体组合物包含:不具有辐射可聚合官能团的热固性树脂、硬化剂、具有辐射可聚合官能团以及可热固化官能团的第一可聚合化合物、具有辐射可聚合官能团并且不具有可热固化官能团的第二可聚合化合物、以及热膨胀胶囊。
5.根据权利要求4所述的粘合剂,其中所述热固性树脂为环氧树脂或氰酸酯树脂。
6.一种带粘合剂背衬的构件,包括由根据权利要求4或5所述的粘合剂形成的层。
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- 2014-11-20 WO PCT/US2014/066556 patent/WO2015077419A1/en active Application Filing
- 2014-11-20 BR BR112016011647A patent/BR112016011647A2/pt not_active Application Discontinuation
- 2014-11-20 EP EP14809227.3A patent/EP3071611B1/en active Active
- 2014-11-20 CN CN201480063272.4A patent/CN105745236B/zh not_active Expired - Fee Related
- 2014-11-20 US US15/037,690 patent/US20160298008A1/en not_active Abandoned
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CN108977111A (zh) * | 2017-06-02 | 2018-12-11 | Dic株式会社 | 粘接胶带、物品以及物品的制造方法 |
CN113993965A (zh) * | 2019-04-25 | 2022-01-28 | 3M创新有限公司 | 用于结构粘合剂应用的增粘剂 |
CN111253877A (zh) * | 2020-03-20 | 2020-06-09 | 安徽富印新材料有限公司 | 一种具有抗污功能的丙烯酸泡棉胶带 |
TWI755089B (zh) * | 2020-10-07 | 2022-02-11 | 鉅昕鋼鐵股份有限公司 | 可回收的焊接用背襯 |
Also Published As
Publication number | Publication date |
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BR112016011647A2 (pt) | 2017-08-08 |
CN105745236B (zh) | 2020-07-31 |
JP2015101607A (ja) | 2015-06-04 |
US20160298008A1 (en) | 2016-10-13 |
WO2015077419A1 (en) | 2015-05-28 |
KR20160088349A (ko) | 2016-07-25 |
JP6433651B2 (ja) | 2018-12-05 |
EP3071611A1 (en) | 2016-09-28 |
EP3071611B1 (en) | 2021-03-31 |
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