CN102666714B - 包含合成橡胶和与丙烯酸类聚合物结合的官能化合成橡胶的共混物的压敏粘合剂 - Google Patents
包含合成橡胶和与丙烯酸类聚合物结合的官能化合成橡胶的共混物的压敏粘合剂 Download PDFInfo
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- CN102666714B CN102666714B CN201080052309.5A CN201080052309A CN102666714B CN 102666714 B CN102666714 B CN 102666714B CN 201080052309 A CN201080052309 A CN 201080052309A CN 102666714 B CN102666714 B CN 102666714B
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Abstract
本发明描述了一种压敏粘合剂组合物,其包含未官能化(如聚异丁烯)合成橡胶和具有与丙烯酸类聚合物结合的官能化聚异丁烯聚合物的丙烯酸类聚合物。在一些实施例中,所述官能化聚异丁烯聚合物具有第一官能团,其与存在于丙烯酸类聚合物主链中的第二官能团氢键结合。在其他实施例中,官能化聚异丁烯聚合物与丙烯酸类聚合物主链共价结合。还描述了粘合剂制品如胶带、粘结性粘合的方法以及制备压敏粘合剂的方法。
Description
背景技术
压敏粘合剂(PSA)是一类重要的材料。
近年来,汽车、器具和电子器件市场中对塑料、硫化橡胶和热塑性硫化橡胶(“TPV”)的使用显著增加。一般来讲,这些材料将硫化橡胶的有利特性与热塑性材料的易加工性结合在一起。然而,粘合到这些和其他低表面能基底上通常需要在与压敏粘合剂(“PSA”)粘合之前对基底表面涂底漆。涂底漆工艺昂贵而又费力,还可能存在环境污染问题。
因此,行业内要找到其可表现出对多种基底(如低表面能基底)具有良好粘附力的优点的新型压敏粘合剂。
发明内容
在一个实施例中,描述了一种压敏粘合剂组合物,其包含未官能化(如聚异丁烯)合成橡胶和具有与丙烯酸类聚合物结合的官能化聚异丁烯聚合物的丙烯酸类聚合物。在一些实施例中,官能化聚异丁烯聚合物具有第一官能团,其与存在于丙烯酸类聚合物主链中的第二官能团氢键结合。在其他实施例中,官能化聚异丁烯聚合物与丙烯酸类聚合物主链共价结合。
在另一个实施例中,描述了压敏粘合剂涂覆制品,例如胶带。该制品包括基底和本文所述的涂覆在基底的至少一个表面上的压敏粘合剂。
在另一个实施例中,描述了一种粘合方法,其包括:提供基底;将本文所述的压敏粘合剂涂覆在基底表面上;以及使压敏粘合剂与另一基底接触。
在另一个实施例中,描述了一种制备压敏粘合剂的方法。该方法包括将未官能化合成橡胶和具有与丙烯酸类聚合物结合的官能化聚异丁烯聚合物的丙烯酸类聚合物共混。
在这些实施例中的每一个中,官能化聚异丁烯通常为较低分子量的液态聚合物,其数均分子量小于10,000克/摩尔。未官能化(如PIB)合成橡胶通常为较高分子量的聚合物,其重均分子量的范围为约75,000克/摩尔至4,000,000克/摩尔。
附图说明
图1为总计50重量%的未官能化聚异丁烯与50重量%的丙烯酸类聚合物的共混物的显微(10X)图像。
图2为总计50重量%的官能化和未官能化聚异丁烯与50重量%的丙烯酸类聚合物的共混物的显微(10X)图像。
图3为总计75重量%的官能化和未官能化聚异丁烯与25重量%的丙烯酸类聚合物的共混物的显微(20X)图像。
图4为总计50重量%的官能化和未官能化聚异丁烯与50重量%的丙烯酸类聚合物的共混物的显微(20X)图像。
图5为总计25重量%的官能化和未官能化聚异丁烯与75重量%的丙烯酸类聚合物的共混物的显微(20X)图像。
具体实施方式
如本领域中所用,术语“压敏粘合剂”是指具有如下性质的粘合剂组合物:(1)有力且持久的粘着性,(2)不超过指压进行粘合,(3)足够的固定在粘附体上的能力,和(4)足够的内聚强度以从粘附体干净地移除。
本文所述的压敏粘合剂组合物包含至少一种具有第一官能团的聚异丁烯,也称为“官能化聚异丁烯”。官能化聚异丁烯的官能团通常为可与丙烯酸类聚合物主链(如侧羧酸基团)氢键结合或共价结合的(如末端)基团或附接至丙烯酸类聚合物(如主链)的官能团。
在一些实施例中,官能化聚异丁烯为异丁烯的官能化均聚物。在其他实施例中,官能化聚异丁烯为共聚物,该共聚物包含异丁烯重复单元和少量的衍生自另一单体(例如苯乙烯、异戊二烯、丁烯或丁二烯)的单元。这些共聚物通常由单体混合物制备,所述单体混合物包含基于单体混合物中的单体重量计至少70重量%的、至少75重量%的、至少80重量%的、至少85重量%的、至少90重量%的、或至少95重量%的异丁烯。通常,至少70重量%的、至少75重量%的、至少80重量%的、至少85重量%的或至少90重量%的聚异丁烯共聚物由异丁烯重复单元形成。示例性的共聚物包括与异戊二烯共聚的异丁烯。
官能化聚异丁烯通常为数均(Mn)分子量为较低至中等的液态聚合物。Mn通常为至少500克/摩尔、750克/摩尔或约1,000克/摩尔。在一些实施例中,官能化聚异丁烯的Mn不大于25,000克/摩尔,或10,000克/摩尔,或5,000克/摩尔。
根据差示扫描量热法(DSC)测定,官能化聚异丁烯的玻璃化转变温度通常不大于约-30℃或更低,不大于约-50℃,或不大于约-70℃。
官能化PIB的官能团可为与丙烯酸类聚合物主链(如侧羧酸基团)形成氢键或共价键的任何官能团或附接至丙烯酸类聚合物(如主链)的官能团。
在一些实施例中,第一官能团和第二官能团形成氢键。在此实施例中,聚异丁烯的官能团与丙烯酸类聚合物之间的主键为氢键。因此,在此实施例中,此类官能团不形成共价键。氢键为存在于极性化合物的吸引力或桥键,在该极性化合物中,一个分子或官能团的氢原子被吸引至另一分子或官能团的未共享电子。氢原子为一个极性分子或官能团的正电端(又称为氢键供体)并与另一分子或官能团(又称为氢键受体)的负电端形成键。具有非极性共价键的官能团不形成氢键。
常见的氢键供体包括羧酸、膦酸、磷酸酯、磺酸、亚磺酸、一元醇和酚。
常见的氢键受体包括含氮基团(例如胺、酰胺基、亚胺、酰亚胺、腈和脲)以及芳族氮基官能团(例如吡啶、咪唑等)。其他氢键受体包括羧化物基团(羧酸、羧酸酯)、膦酸酯、亚砜、砜和氨基甲酸酯。
在一个实施例中,丙烯酸类聚合物具有羧酸官能团,并且官能化PIB具有与丙烯酸类聚合物的羧酸基团氢键结合的官能(如末端)基团。在此实施例中,官能化PIB的官能团不为丙烯酸酯、甲基丙烯酸酯,或经由自由基聚合与(甲基)丙烯酸酯基团共价结合的官能团。此方法是优选的,因为其可利用具有含氮端基(例如胺或酰亚胺)的市售的官能化PIB。
各种官能化PIB材料可商购获得。例如,数均分子量(Mn)为约1,000克/摩尔且摩尔质量分布(Mw/Mn=1.6)的聚异丁烯胺可以商品名“PIBA03”从BASF Corporation(Florham Park,NJ)商购获得。另外,聚异丁烯琥珀酰亚胺可以商品名“PIBSI”从BASF商购获得。具有约1,000克/摩尔的(Mn)酸酐封端的聚异丁烯可以商品名“Glissopal SA”从BASF商购获得。
市售的官能化PIB材料适于形成氢键,其中羧酸基团为质子供体(即H键供体)并且含氮基团(即胺或酰亚胺)质子受体(即H键受体)。
然而,应理解官能团可颠倒。例如,官能化PIB可具有(如末端)羧酸基团,前提条件是丙烯酸类聚合物的羧酸基团经预先反应以将这些基团转化成之后又与PIB的羧酸基团形成氢键的官能团。
例如,聚异丁烯胺(如PIBA03)可与酸酐(例如琥珀酸酐或戊二酸酐)反应得到羧酸官能化PIB材料。羧酸官能化PIB还可这样制备:通过酸酐封端的聚异丁烯(如Glissopal SA)与醇(例如1-辛醇)反应,得到以酯基和羧酸封端的PIB链。
可通过至少一种氨基共聚单体与(甲基)丙烯酸烷基酯单体共聚来制备胺官能化丙烯酸类聚合物。合适的氨基共聚单体为烯属不饱和可聚合化合物,其包含至少一个伯氨基或仲氨基,例如氨基丙烯酸甲酯,如甲基丙烯酸叔丁氨基乙酯或间-异丙烯基-α,α-二甲基苄胺。还可通过酸聚合物与氮丙啶(如吖丙啶)反应或其他已知用于向聚合物添加胺官能团的技术获得氨基。
已知各种氨基共聚单体,包括例如N,N-二甲基氨丙基甲基丙烯酰胺(DMAPMAm);N,N-二乙氨基丙基甲基丙烯酰胺(DEAPMAm);丙烯酸N,N-二甲氨基乙酯(DMAEA);丙烯酸N,N-二乙氨基乙酯(DEAEA);丙烯酸N,N-二甲氨基丙酯(DMAPA);丙烯酸N,N-二乙氨基丙酯(DEAPA);甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA);甲基丙烯酸N,N-二乙氨基乙酯(DEAEMA);N,N-二甲氨基乙基丙烯酰胺(DMAEAm);N,N-二甲氨基乙基甲基丙烯酰胺(DMAEMAm);N,N-二乙氨基乙基丙烯酰胺(DEAEAm);N,N-二乙氨基乙基甲基丙烯酰胺(DEAEMAm);N,N-二甲氨基乙基乙烯基醚(DMAEVE);N,N-二乙氨基乙基乙烯基醚(DEAEVE);以及它们的混合物。其他可用的碱性单体包括乙烯基吡啶、乙烯基咪唑、叔氨基官能化苯乙烯(例如4-(N,N-二甲氨基)-苯乙烯(DMAS)、4-(N,N-二乙氨基)-苯乙烯(DEAS))以及它们的混合物。
其他官能化聚异丁烯可通过本领域中已知的各种方法制备。例如,还可通过使酸酐封端的聚异丁烯(如Glissopal SA)与氨基醇或二醇反应,或通过使聚异丁烯胺(如PIBA03)与2-氯乙醇或环氧化物反应来合成羟基官能化PIB。可通过使氨基或含羟基吡啶化合物与聚异丁烯(如琥珀酸)酸酐(如SA)反应来合成吡啶官能化PIB基材料。或者,聚异丁烯胺(如PIBA03)可与3-(氯甲基)吡啶反应得到吡啶基取代的PIB衍生物。可通过使聚异丁烯胺(如PIBA03)与异氰酸酯亲电体反应得到氨基甲酸酯官能化PIB。
或者,官能化PIB的第一官能团与丙烯酸类聚合物的第二官能团形成共价键。在此实施例中,官能化PIB的第一官能团可为与丙烯酸类聚合物主链形成共价键的任何官能团。或者,官能化PIB的第一官能团为可与典型的(甲基)丙烯酸烷基酯单体共聚的可聚合(甲基)丙烯酸酯官能团。
许多常见的官能团可用于在PIB材料与丙烯酸类聚合物之间形成共价键。例如,胺或醇官能化PIB材料可与包含活性酯型官能团的(甲基)丙烯酸酯聚合物反应。此类活性酯包括酸酐、N-羟基琥珀酰亚胺酯基、五氟苯基酯和酸性氯化物。例如,可通过将N-羟基琥珀酰亚胺丙烯酸酯用作丙烯酸酯单体来制备包含N-羟基琥珀酰亚胺酯官能团的丙烯酸酯聚合物。或者,可通过本领域的技术人员已知的一般方法将(甲基)丙烯酸酯聚合物中的羧酸残基转化成活性酯。制备共价结合PIB丙烯酸酯材料的另一途径为使胺或醇官能化PIB材料与包含吖内酯环的(甲基)丙烯酸酯聚合物反应。可通过将2-乙烯基-4,4-二甲基-5-噁唑酮用作共聚单体来制备具有吖内酯环的(甲基)丙烯酸酯聚合物。合适的胺官能化PIB材料为PIBA03。
制备共价结合PIB(甲基)丙烯酸酯材料的另一策略为使胺或羟基官能化PIB材料与异氰酸酯官能化(甲基)丙烯酸酯聚合物反应。通过将甲基丙烯酸2-异氰酸基乙酯用作共聚单体来制备此类(甲基)丙烯酸酯聚合物。
还可将第一反应官能团和第二反应官能团颠倒。例如,胺或羟基官能化(甲基)丙烯酸酯聚合物可与由活性酯官能化的PIB聚合物反应。可通过将胺官能化(甲基)丙烯酸酯单体(见上文)用作共聚单体来制备胺官能化(甲基)丙烯酸酯聚合物。例如,可通过将丙烯酸2-羟乙酯或甲基丙烯酸2-羟乙酯在(甲基)丙烯酸酯聚合物的制备中用作共聚单体来制备醇官能化(甲基)丙烯酸酯聚合物。适于胺或醇官能化(甲基)丙烯酸酯聚合物的反应搭配物为酸酐官能化PIB材料,例如SA。
甲基丙烯酸酯和丙烯酸酯官能化PIB可按本领域中已知的方式合成。参见例如WO2008/066914、美国专利No.5,171,760和“Sytheses andCharacterization of Polyisobutylene Macromonomer with Methacrylate,Acrylate,Glycidyl Ether,or Vinyl Ether End-Functionality”,(Macromolecules 2009,42,3958-3964)(具有甲基丙烯酸酯、丙烯酸酯、缩水甘油醚或乙烯基醚末端官能团的大分子单体的合成和表征,《大分子》2009年,42,3958-3964页))。另外,US5665823和US60554549描述了具有硅烷醇端基的PIB基材料,其可用于制备在PIB链与丙烯酸酯官能团之间具有硅氧烷键的丙烯酸酯官能化PIB聚合物。
官能化PIB材料内的官能团的存在和浓度可通过核磁共振来确定。通常,官能化PIB材料包含至少3摩尔%官能团。官能团的浓度通常不大于10摩尔%。
压敏粘合剂组合物中官能化PIB材料的量可根据粘合剂组合物的所需最终用途而变化。通常,然而,官能化PIB材料的浓度为至少2重量%、或5重量%或10重量%,以提高与低表面能基底(如由聚烯烃制备的那些)的粘附力。官能化PIB材料的浓度通常不大于40重量%。特别是当压敏粘合剂组合物还旨在与高表面能基底一起使用时,官能化PIB材料的浓度通常为5重量%至30重量%(当使用具有较低分子量的(如Mn小于10,000克/摩尔)的官能化PIB材料时)。
参照图1-2,推测官能化PIB材料使较高分子量的PIB材料与丙烯酸类聚合物材料相容。官能化PIB材料与未官能化(如PIB)合成橡胶材料的重量比可在约1∶1至约1∶3的范围内。
本文所述的压敏粘合剂组合物还包含至少一种丙烯酸类聚合物。丙烯酸类聚合物通常包含至少一种(甲基)丙烯酸烷基酯与至少一种共聚单体的反应产物,最通常为羧酸,其提供沿丙烯酸类聚合物主链的官能团。在一些实施例中,粘合剂组合物的丙烯酸类共聚物包含至少约70重量%、在一些实施例中至少约80重量%、至少约90重量%、至少约95重量%或甚至约98重量%的至少一种(甲基)丙烯酸烷基酯。
在一些实施例中,(甲基)丙烯酸烷基酯包含4至20个碳原子,例如4至8个碳原子。示例性(甲基)丙烯酸烷基酯包括丙烯酸异辛酯(IOA)、2-丙烯酸辛酯(2-OA)、丙烯酸2-乙基己酯(2-EHA)、丙烯酸丁酯(BA)、丙烯酸异冰片酯(IBA)以及它们的组合。在一些实施例中,用于PSA中的丙烯酸类共聚物包含此类(甲基)丙烯酸烷基酯如丙烯酸异辛酯和丙烯酸异冰片酯中的至少两种。
在一些实施例中,丙烯酸类粘合剂组合物包含不大于10份的共聚单体,例如羧酸。因此,在一些实施例中,共聚单体提供了补充PIB官能度的官能团,共聚单体的浓度通常为至少0.5、1、2、3、4或5重量%。示例性共聚单体包括羧酸,例如丙烯酸或甲基丙烯酸。在一些实施例中,共聚单体(如(甲基)丙烯酸)5重量%至10重量%或15重量%的浓度提供了提高的内聚强度,如剪切力值所表明。
压敏粘合剂组合物中丙烯酸类聚合物的量可根据粘合剂组合物的所需最终用途而变化。通常,然而,丙烯酸类聚合物的浓度为至少20重量%或25重量%。丙烯酸类聚合物的浓度范围高达75重量%或80重量%。特别是当预期将压敏粘合剂组合物与低表面能基底和高表面能基底两者一起使用时,丙烯酸类聚合物的浓度范围通常为30重量%至70重量%、35重量%至65重量%或40重量%至60重量%。参照图3-5,由于丙烯酸类聚合物与总的PIB聚合物(即官能化PIB和未官能化PIB两者的总量)的重量比接近1∶1,因此共混物可具有双连续相形态(即半互穿网络)。
在一些实施例中,(甲基)丙烯酸烷基酯单体和官能化共聚单体预聚成丙烯酸类聚合物,然后与官能化PIB混合。
在其他实施例中,(甲基)丙烯酸烷基酯单体和官能化共聚单体与官能化PIB混合,然后将这些单体聚合。(甲基)丙烯酸烷基酯单体和官能化PIB可通过使用热引发剂或光引发剂聚合。热引发剂通常为过氧化物、氢过氧化物或偶氮化合物。或者,通过用α裂解型光引发剂(包括但不限于安息香或安息香烷基醚),使用紫外线辐射来聚合(甲基)丙烯酸烷基酯单体。任一制备方法形成包含官能化PIB和丙烯酸类聚合物的共混物的组合物,其中官能化PIB与沿丙烯酸类聚合物主链的官能团氢键结合或共价结合。
对于其中(甲基)丙烯酸烷基酯单体和官能化共聚单体预聚成丙烯酸类聚合物,然后与官能化PIB混合的实施例而言,官能化PIB与丙烯酸类聚合物的反应产物可如下表示,其中Z表示互补官能团之间的氢键或共价键:
在一些实施例中,粘合剂可仅包含在不存在交联剂或其他任选组分的情况下与丙烯酸类聚合物和未官能化(如PIB)合成橡胶氢键结合或共价结合的官能化PIB。
在其他实施例中,本发明的粘合剂可以通过交联提高它们的机械性能。在许多实施例中,优选化学交联来提高压敏粘合剂的内聚强度(如静态剪切力所示)。例如,粘合剂可包含化学交联剂,其适于使丙烯酸类聚合物的(如羧酸)官能团彼此交联或使丙烯酸类聚合物的官能团与官能化PIB的官能团交联。合适的交联剂是本领域已知的,例如氮丙啶或双氮丙啶交联剂。一种合适的双氮丙啶交联剂根据2009年3月9日提交的美国临时申请No.61/158,485(Peiwang Zhu等人,AZIRIDINE CROSSLINKING AGENTS FOR ACRYLIC ADHESIVES(用于丙烯酸类粘合剂的氮丙啶交联剂))的描述进行制备。
当压敏粘合剂(如前体))另外包含化学交联剂时,官能化PIB与丙烯酸类聚合物的反应产物可按如下表示:
当存在时,压敏粘合剂组合物中化学交联剂的浓度为通常至少0.025重量%且不大于2重量%。
粘合剂另外包含至少一种未官能化(如PIB)合成橡胶材料。未官能化(如PIB)合成橡胶材料通常具有显著高于官能化(如PIB)合成橡胶材料的分子量。在一些实施例中,未官能化(如PIB)合成橡胶材料的重均分子量(Mw)为至少75,000克/摩尔、至少100,000克/摩尔、至少250,000克/摩尔、至少500,000克/摩尔或甚至至少1,000,000克/摩尔。重均分子量通常不大于4,000,000克/摩尔。
未官能化(如PIB)合成橡胶材料可为均聚物、共聚物或其混合物。共聚物可为无规共聚物或嵌段共聚物。嵌段共聚物可在聚合物材料的主链、侧链或主链和侧链两者中含有聚异丁烯部分。通常通过单独的聚合异丁烯或通过聚合异丁烯外加烯键式不饱和单体,在存在诸如氯化铝、三氯化硼(四氯化钛作为助催化剂)或三氟化硼的路易斯酸催化剂的情况下制备聚异丁烯材料。
未官能化聚异丁烯材料可从若干制造商商购获得。均聚物可(例如)以商品名OPPANOL(例如,OPPANOL B10、B15、B30、B50、B100、B150和B200)从BASF Corp.(Florham Park,NJ)商购获得。这些聚合物的重均分子量(Mw)通常在约40,000至4,000,000克/摩尔的范围内。其他实例性的均聚物可以宽泛的分子量范围商购自UnitedChemical Products(UCP)(St.Petersburg,Russia)。例如,以商品名SDG商购自UCP的均聚物的粘均分子量(Mv)在约35,000至65,000克/摩尔的范围内。以商品名EFROLEN商购自UCP的均聚物的粘均分子量(Mv)在约480,000至约4,000,000克/摩尔的范围内。以商品名JHY商购自UCP的均聚物的粘均分子量在约3000克/摩尔至约55,000克/摩尔的范围内。这些均聚物通常不具有反应性双键。应意识到未官能化(如PIB)合成橡胶可具有极小浓度的反应性双键或其聚合残基的其他官能团。此类反应性双键或其他官能团的浓度通常小于5摩尔%、4摩尔%、3摩尔%或2摩尔%。此类烯属不饱和基团通常为非极性的,因此不是形成氢键的合适官能团。此类烯属不饱和基团也通常不是经由自由基聚合形成共价键的合适官能团。
压敏粘合剂组合物中的未官能化(如PIB)合成橡胶材料的浓度通常为至少5重量%、10重量%或15重量%且不大于40重量%或50重量%。在一些实施例中,未官能化(如PIB)合成橡胶的浓度范围基于分子量为约500,000克/摩尔的未官能化(如PIB)合成橡胶计。
在一些实施例中,粘合剂包含与丙烯酸类聚合物氢键结合或共价结合的官能化(如PIB)合成橡胶、交联剂以及高分子量未官能化(如PIB)合成橡胶和低分子量未官能化(如PIB)合成橡胶。低分子量(如PIB)合成橡胶材料在室温下为液体,并且可与多种弹性体材料一起充当增塑剂。一般来讲,此类聚异丁烯材料的数均分子量不大于10,000克/摩尔,如不大于5,000克/摩尔,或甚至不大于2,000克/摩尔。数均分子量通常为至少约500克/摩尔或1000克/摩尔。重均分子量与数均分子量的比率通常在约1.6至2.0的范围内。
示例性的低分子量聚异丁烯均聚物可以商品名GLISSOPAL(例如,GLISSOPAL 1000、1300和2300)从BASF Corp.(Florham Park,NJ)商购获得。这些聚异丁烯材料通常具有末端双键并被视为反应性聚异丁烯材料。
当存在时,压敏粘合剂组合物中的未官能化低分子量聚异丁烯(如PIB)材料的浓度通常为至少5重量%、10重量%或20重量%且不大于30重量%。
在一些实施例中,粘合剂可包含与丙烯酸类聚合物氢键结合的官能化(如PIB)合成橡胶、交联剂、未官能化高分子量(如PIB)合成橡胶材料,不存在任何增粘剂或增塑剂。在其它实施例中,粘合剂包含至少一种增粘剂、增塑剂或其混合物。
增粘剂可具有任何合适的软化温度或软化点。软化温度通常小于200℃、小于180℃、小于160℃、小于150℃、小于125℃或小于120℃。然而,在趋于发热的应用中,通常选择软化点为至少75℃的增粘剂。当粘合剂组合物经受例如来自电子器件或元件的热量时,此类软化点有助于将增粘剂与粘合剂组合物其余部分的分离降至最低。软化温度通常选择为至少80℃、至少85℃、至少90℃或至少95℃。然而,在不发热的应用中,增粘剂可具有小于75℃的软化点。
示例性增粘剂包括烃类树脂和氢化烃类树脂,如氢化环脂族树脂、氢化芳香族树脂或者它们的组合。合适的增粘剂可以商购获得,包括(例如)以商品名ARKON(如ARKON P或ARKON M)得自ArakawaChemical Industries Co.,Ltd.(Osaka,Japan)的那些;以商品名ESCOREZ(如ESCOREZ 1315、1310LC、1304、5300、5320、5340、5380、5400、5415、5600、5615、5637和5690)得自Exxon Mobil Corporation(Houston,TX)的那些;以及以商品名REGALREZ(如REGALREZ 1085、1094、1126、1139、3102和6108)得自Eastman Chemical(Kingsport,TN)的那些。
增粘剂的浓度可根据预期粘合剂组合物而变化。在一些实施例中,增粘剂的量为至少10重量%或20重量%。增粘剂的最大量通常为不大于40重量%、50重量%或60重量%。
其他任选的添加剂可包括(例如)引发剂、紫外吸收剂(例如苯并三唑、噁唑酸酰胺、二苯甲酮或它们的衍生物)、紫外稳定剂(例如受阻胺或其衍生物、咪唑或其衍生物、磷基稳定剂和硫酯基稳定剂)、抗氧化剂(例如受阻酚化合物、磷酸酯或它们的衍生物)。示例性的抗氧化剂包括得自Ciba Specialty Chemicals Incorporated(Tarrytown,NY)的那些。
本发明的粘合剂可以与基底结合以形成多种典型的粘合剂制品,如单面和双面涂布胶带以及层合粘合剂。一般来讲,层合粘合剂可以包括自由的粘合剂膜或嵌入载体(如织造或非织造稀松布)中的粘合剂膜。可以通过将粘合剂施加(如涂布、浇铸或挤出)到隔离衬片上,然后干燥和/或固化粘合剂来形成此类产品。
也可以将本发明的粘合剂施加到基底的一面或两面上,以形成单面或双面涂布胶带。可以使用任何已知的基底,包括具有纸材、聚合物膜和金属(如金属箔)中的一者或多者的单层和多层基底。在一些实施例中,基底的一个或多个层可以是泡沫。在一些实施例中,单或双粘合剂层可以直接粘合到基底上。在一些实施例中,单或双粘合剂层可以间接粘合到基底上。例如,在一些实施例中,可以将一个或多个中间层(如底漆层)置于基底与粘合剂层之间。
粘合剂可用于粘合多种金属和聚合物材料。金属的表面能通常为至少约500达因/厘米。例如,据报道不锈钢的表面能为约700-1100达因/厘米。无机氧化物通常具有低于金属的表面能。例如,据报道玻璃的表面能为约250-500达因/厘米。粘合剂特别可用于粘合多种聚合物材料。诸如塑料的聚合物材料的表面能通常小于100达因/厘米、75达因/厘米或50达因/厘米。例如,据报道聚酯的表面能为43达因/厘米;聚碳酸酯的表面能为42达因/厘米;聚氯乙烯的表面能为39达因/厘米;以及丙烯酸类树脂的表面能为38达因/厘米。具有甚至更低表面能的材料的表面能小于37达因/厘米。这些包括例如据报道表面能为31达因/厘米的聚醋酸乙烯酯、聚苯乙烯、乙缩醛、乙烯-醋酸乙烯酯和聚乙烯。
根据预期的最终用途,压敏粘合剂可表现出各种剥离和剪切特性。
在一些实施例中,对于可临时移除的或低温PSA,对玻璃、不锈钢、高密度聚乙烯(HDPE)、聚丙烯(PP)或EPDM的90度剥离为至少5盎司/英寸(5N/dm)。对于遮蔽胶带,对玻璃、不锈钢、HDPE、PP或EPDM的90度剥离通常为15-20盎司/英寸(16-22N/dm)。在其它实施例中,对玻璃、不锈钢、HDPE或PP的90度剥离为至少50、60、70、80或90盎司/英寸(55、66、77、88或99N/dm)。在至少一些实施例中,室温(23℃)时的剪切为至少300分钟、500分钟或800分钟。在一些有利的实施例中,粘合剂表现出对高表面能基底和低表面能基底的良好粘附力。在此类实施例中,对玻璃或不锈钢的90度剥离为至少50、60、70、80或90盎司/英寸(55、66、77、88或99N/dm),以及对PP的90度剥离为至少30、40、50,或60盎司/英寸。另外,对EPDM的90度剥离通常为至少30、40,或50盎司/英寸;而对HDPP的90度剥离为至少30、40,或50盎司/英寸。在一些有利的实施例中,室温(23℃)或70℃时的剪切为至少2,000分钟;4,000分钟;8,000分钟;或10,000分钟。
以下非限制性实例进一步描述本发明的示例性粘合剂和粘合剂制品,以及制备此类粘合剂和粘合剂制品的示例性方法。所有百分比均按重量计,除非另外指明。
测试方法:
90°角剥离粘附强度测试。如ASTM国际标准D3330中的方法F所述,用1.3cm×20cm(1/2英寸×8英寸)试件和IMASS SP-200滑动/剥离试验机(得自IMASS,Inc.,Accord,MA)以305mm/min(12英寸/分钟)的剥离速率进行90°角剥离粘附强度评价。通过用2.0kg(4.5磅)的橡胶辊在胶带上滚动4次将样品粘附到测试面板上。测试面板包括:
将测试面板用1∶1异丙醇/水混合物清洗并在使用之前充分干燥。除非另外指明,否则都在测试面板上在受控环境的室内达到15分钟的放置时间后进行剥离测试。基于2个试样,从面板上移除胶带所需的平均剥离粘附力以盎司测量,并以盎司/英寸表示。
23℃/50%相对湿度下的静态剪切强度:如ASTM国际标准D3654中的工序A所述,用1.3cm×2.5cm(1/2英寸×1英寸)试件和1000g负载进行静态剪切强度的评价。测试面板为不锈钢(“SS”)。失效时间以分钟记录。如果10,000分钟后没有观察到失效,停止测试并记录>10,000分钟的数值。
70℃下的静态剪切强度:如ASTM国际标准D3654中的工序A所述,用1.3cm×2.5cm(1/2英寸×1英寸)试件和500g负载进行静态剪切强度的评价。测试面板为不锈钢(“SS”)。失效时间以分钟记录。如果10,000分钟后没有观察到失效,停止测试并记录>10,000分钟的数值。
材料
一般工序。所有反应均原样使用商业试剂在圆底烧瓶或玻璃广口瓶/小瓶中进行。
另外包含未官能化PIB粘合剂组合物根据以下工序制备:将PIBA03添加到玻璃小瓶中。然后,添加丙烯酸异辛酯/丙烯酸共聚物溶液(如35%重量%乙酸乙酯溶液中的94∶6丙烯酸异辛酯∶丙烯酸或90∶10丙烯酸异辛酯∶丙烯酸),然后添加未官能化PIB(在15重量%的甲苯溶液中)与增粘剂(如E1310)。添加额外的甲苯使得总固体浓度等于35重量%。各制剂中每种组分的浓度在表中示出。通过摇振直至使溶液变为半透明并且组分均匀分散来充分混合组分。在即将涂覆之前,添加双氮丙啶交联剂(甲苯中15重量%溶液),并将制剂再摇振并且混合均匀。使用9密耳间隙在有机硅隔离衬垫(SilphanS36 M74A)上进行手动牵拉涂布。将膜在70℃的烘箱中干燥30分钟。然后,使粘合剂膜冷却至室温。粘合剂膜为0.0019"厚。在内聚力和粘附力强度测试期间,将2密耳(0.0020")厚阳极化铝层合在PSA胶带上作为粘合剂背衬。
参照图1-2,经由显微镜法(10X)检验对照例B和实例1的组合物的形态。参照图2,包含与丙烯酸类聚合物结合的官能化PIB(如PIBA03)的实例1的粘合剂与图1中缺乏官能化PIB的对照例B的粘合剂相比表现出更均匀分散的相域。尽管无意于受理论的束缚,但据推测相域的分散均匀度与粘附性质紧密相关。例如,对照例B表现出对低表面能基底(例如PP和EPDM)的较低剥离粘附力。将此类结果与对照例A(纯丙烯酸类-PSA)进行比较。然而,实例1和2表现出更均匀的相和较小的相域。因此,可得出结论,官能化PIB的存在使未官能化高分子量(如PIB)合成橡胶与丙烯酸类聚合物的不溶混相相容。所得粘合剂组合物表现出对低能表面基底的提高的剥离粘附力。
参照图3-5,经由显微镜法(20X)检验实例3-5的组合物的形态。在图3中,具有75重量%的(45重量%的未官能化和30重量%的官能化)PIB的共混物表现出连续PIB域,如图3中较亮区域以及丙烯酸类共聚物域的暗色融合区域所示。在图4中,在具有50重量%PIB的共混物中,形态转变为双连续相(即半互穿网络)。如图5所示,在具有25重量%PIB的共混物中,PIB域变成嵌入连续丙烯酸类共聚物相中的小滴。
a.用1000g负载在大约30℃的室温下在不锈钢上用0.5"×1.0"的带获得剪切数据
b.和10重量%的F85
PIB丙烯酸酯大分子单体。向4盎司琥珀色瓶配备具有大约1/8"洞口的塑料盖。添加SA(60.0g)和磁力搅拌棒。然后,添加丙烯酸2-羟乙基酯(6.00mL,6.07g,52.2mmol)和4-(二甲基氨基)吡啶(0.0520g,0.426mmol)。将反应物用塑料盖封盖,并将一件管透过洞口螺入,并且推入反应混合物底部。使空气通过管并在整个反应过程中鼓泡通过反应混合物。在搅拌情况下将反应物置于被加热到100℃的油浴中。3天后,将反应物从油浴中移出并冷却至室温。得到呈浅黄色极粘滞液体的丙烯酸酯产物。
使用PIB大分子单体制备丙烯酸类共聚物的一般工序。将PIB大分子单体(1.00g)添加到4盎斯具有包绕螺纹的琥珀色瓶中。添加己烷(8.50mL,5.60g),并将混合物超声处理40分钟以溶解大分子单体。然后,添加丙烯酸异辛酯(2.00g)、丙烯酸(0.150g)和67(0.010g),并将混合物混合直至均匀。将反应物用氮气鼓泡7分钟,然后用衬里的塑料盖快速密封。将反应物进一步用胶带和绝缘带密封。将反应物置于65℃的水浴/摇动器中并且缓缓搅动。24小时后,将反应物从水浴中移出并冷却至室温。然后在搅拌的同时将反应混合物添加到甲醇(100mL)中,以使聚合物产物沉淀。倾析出混浊的甲醇溶液,并将粘稠的浅黄色物质用甲醇洗涤(3×5mL)。将沉淀产物转移到具有己烷的20mL玻璃小瓶中,然后真空干燥,得到呈透明、浅黄色橡胶状固体的聚合物产物(2.31g,73.1%)。
然后使用丙烯酸酯PIB共聚物按照与前述相同的方式制备粘合剂组合物。
Claims (19)
1.一种压敏粘合剂组合物,其包含:
未官能化合成橡胶;和
丙烯酸类聚合物,其中所述丙烯酸类聚合物为至少一种(甲基)丙烯酸烷基酯和至少一种羧酸的共聚物,所述共聚物具有与所述丙烯酸类聚合物的侧羧酸基团氢键结合或共价结合的官能化聚异丁烯聚合物。
2.根据权利要求1所述的压敏粘合剂组合物,其中所述官能化聚异丁烯聚合物具有第一官能团,其与存在于所述丙烯酸类聚合物主链中的第二官能团氢键结合。
3.根据权利要求2所述的压敏粘合剂组合物,其中所述第一或第二官能团为氢键受体,和另一官能团为氢键供体。
4.根据权利要求1所述的压敏粘合剂组合物,其中所述官能化聚异丁烯聚合物与所述丙烯酸类聚合物主链共价结合。
5.根据权利要求4所述的压敏粘合剂组合物,其中与所述丙烯酸类聚合物主链共价结合的所述官能化聚异丁烯聚合物通过使(甲基)丙烯酸酯-官能化PIB与(甲基)丙烯酸烷基酯单体聚合来制备。
6.根据权利要求1所述的压敏粘合剂组合物,其中所述未官能化合成橡胶包含聚异丁烯。
7.根据权利要求1-6任一项所述的压敏粘合剂组合物,其中所述官能化聚异丁烯聚合物的数均分子量小于10,000克/摩尔。
8.根据权利要求1-6任一项所述的压敏粘合剂组合物,其中所述未官能化合成橡胶的重均分子量的范围为75,000克/摩尔至4,000,000克/摩尔。
9.根据权利要求1所述的压敏粘合剂组合物,其中所述(甲基)丙烯酸烷基酯为(甲基)丙烯酸C4至C20烷基酯。
10.根据权利要求1所述的压敏粘合剂组合物,其中所述(甲基)丙烯酸烷基酯为(甲基)丙烯酸C4至C8烷基酯。
11.根据权利要求2或3所述的压敏粘合剂组合物,其中所述粘合剂组合物另外包含共价交联所述第一官能团和第二官能团的化学交联剂。
12.根据权利要求11所述的压敏粘合剂组合物,其中所述交联剂选自氮丙啶交联剂。
13.根据权利要求1-6任一项所述的压敏粘合剂组合物,其中所述组合物包含数均分子量小于10,000克/摩尔的未官能化聚异丁烯。
14.根据权利要求1-6任一项所述的压敏粘合剂组合物,其还包含增粘树脂、增塑剂或其混合物。
15.一种制品,其包括:
基底;和
涂覆在所述基底的至少一个表面上的权利要求1-14任一项所述的压敏粘合剂组合物。
16.根据权利要求15所述的制品,其中所述制品为胶带。
17.一种粘合方法,该方法包括:
提供基底;
将权利要求1-14中任一项所述的压敏粘合剂组合物涂覆在所述基底的表面上;和
使所述压敏粘合剂组合物与另一基底接触。
18.根据权利要求17所述的方法,其中至少一种基底的表面能小于37达因/厘米。
19.一种制备压敏粘合剂的方法,该方法包括共混:
未官能化合成橡胶;和
丙烯酸类聚合物,其中所述丙烯酸类聚合物为至少一种(甲基)丙烯酸烷基酯和至少一种羧酸的共聚物,所述共聚物具有与所述丙烯酸类聚合物的侧羧酸基团氢键结合或共价结合的官能化聚异丁烯聚合物。
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WO2011062852A1 (en) | 2009-11-19 | 2011-05-26 | 3M Innovative Properties Company | Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer |
JP5094832B2 (ja) * | 2009-12-25 | 2012-12-12 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
WO2012067741A1 (en) | 2010-11-16 | 2012-05-24 | 3M Innovative Properties Company | Uv curable anhydride-modified poly(isobutylene) |
US8663407B2 (en) | 2010-11-17 | 2014-03-04 | 3M Innovative Properties Company | Isobutylene (Co)polymeric adhesive composition |
US8629209B2 (en) | 2010-12-02 | 2014-01-14 | 3M Innovative Properties Company | Moisture curable isobutylene adhesive copolymers |
US9562180B2 (en) | 2012-03-29 | 2017-02-07 | 3M Innovative Properties Company | Adhesives comprising poly(isobutylene) copolymers comprising pendent free-radically polymerizable quaternary ammonium substituent |
CN104254552B (zh) * | 2012-04-27 | 2018-12-11 | 汉高知识产权控股有限责任公司 | 具有反应性官能团的接枝遥爪聚异丁烯、其制备方法和包含其的可固化组合物 |
KR20150008873A (ko) * | 2012-05-02 | 2015-01-23 | 헨켈 유에스 아이피 엘엘씨 | 경화성 캡슐화제 및 그의 용도 |
US9422464B2 (en) | 2012-05-11 | 2016-08-23 | 3M Innovative Properties Company | Adhesives comprising reaction product of halogenated poly(isobutylene) copolymers and polyamines |
US8697789B2 (en) | 2012-06-05 | 2014-04-15 | 3M Innovative Properties Company | Adhesives comprising poly(isobutylene) polymers and unreacted alkyl amine |
EP2885363B1 (en) * | 2012-08-14 | 2018-02-07 | 3M Innovative Properties Company | Adhesives comprising grafted isobutylene copolymer |
US20160032162A1 (en) | 2013-04-18 | 2016-02-04 | 3M Innovative Properties Company | Buried clay/nanosilica static dissipative coatings |
WO2015009129A1 (ko) * | 2013-07-19 | 2015-01-22 | 주식회사 엘지화학 | 봉지 조성물 |
EP2832780B1 (en) | 2013-08-01 | 2019-09-25 | 3M Innovative Properties Company | Rubber-Based Pressure Sensitive Adhesive Foam |
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DE102013215296A1 (de) | 2013-08-02 | 2015-02-05 | Tesa Se | Haftklebemasse |
DE102013224774A1 (de) * | 2013-12-03 | 2015-06-03 | Tesa Se | Mehrschichtiges Produkt |
US9757898B2 (en) | 2014-08-18 | 2017-09-12 | Lord Corporation | Method for low temperature bonding of elastomers |
CN104479599B (zh) * | 2014-12-31 | 2019-11-15 | 3M创新有限公司 | 多基材适应性拉伸移除型粘合剂制品、粘合剂组合物及组件 |
US20190284451A1 (en) * | 2016-05-16 | 2019-09-19 | 3M Innovative Properties Company | Self-priming adhesive |
DE102016224684A1 (de) * | 2016-12-12 | 2018-06-14 | Tesa Se | Verfahren zur Herstellung einer Klebverbindung zwischen einer Klebmasseschicht und einer LSE-Substratoberfläche |
DE102017200471A1 (de) * | 2017-01-12 | 2018-07-12 | Tesa Se | Verfahren zur Verklebung von Profilen auf Substratoberflächen |
JP7069117B2 (ja) | 2017-03-16 | 2022-05-17 | 株式会社カネカ | ビニル系櫛型共重合体 |
CN110678513A (zh) * | 2017-06-14 | 2020-01-10 | 汉高知识产权控股有限责任公司 | 具有超低湿气渗透性的层压膜粘合剂 |
US20190054527A1 (en) * | 2017-08-18 | 2019-02-21 | General Electric Company | Thermoplastic binders for use in binder jetting additive manufacturing |
MX2020006022A (es) | 2017-12-14 | 2020-08-17 | Avery Dennison Corp | Adhesivo sensible a la presion con amplio intervalo de temperaturas y frecuencias de amortiguacion. |
US20220298676A1 (en) * | 2019-08-21 | 2022-09-22 | 3M Innovative Properties Company | Core-sheath filaments including polyisobutylene compositions and methods of printing the same |
CN110791223B (zh) * | 2019-11-14 | 2021-07-02 | 中国农业科学院麻类研究所 | 小分子粘合剂及其制备方法 |
CN114891447B (zh) * | 2022-05-18 | 2024-02-20 | 江苏翎慧材料科技有限公司 | 一种丙烯酸酯/聚异丁烯橡胶杂化压敏胶组合物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0519278A2 (en) * | 1991-06-19 | 1992-12-23 | Nitto Denko Corporation | Automobile paint film-protective sheet |
CN1125956A (zh) * | 1993-05-11 | 1996-07-03 | 埃克森化学专利公司 | 含异丁烯与对甲基苯乙烯的卤化共聚物和羧基改性弹性体的相容共混物 |
CN101370889A (zh) * | 2006-01-24 | 2009-02-18 | 3M创新有限公司 | 粘合剂封装组合物膜以及有机电致发光器件 |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6346280A (ja) * | 1986-04-17 | 1988-02-27 | Idemitsu Petrochem Co Ltd | 接着剤 |
US5656286A (en) | 1988-03-04 | 1997-08-12 | Noven Pharmaceuticals, Inc. | Solubility parameter based drug delivery system and method for altering drug saturation concentration |
US5171760A (en) | 1988-08-05 | 1992-12-15 | Edison Polymer Innovation Corp. | UV curable polymer formulation |
US6630238B2 (en) | 1995-02-16 | 2003-10-07 | 3M Innovative Properties Company | Blended pressure-sensitive adhesives |
US6632522B1 (en) | 1995-02-16 | 2003-10-14 | 3M Innovative Properties Company | Blended pressure-sensitive adhesives |
US6063838A (en) | 1995-02-16 | 2000-05-16 | 3M Innovative Properties Company | Blended pressure-sensitive adhesives |
US5665823A (en) | 1996-08-30 | 1997-09-09 | Dow Corning Corporation | Polyisobutylene polymers having acrylic functionality |
JPH10158618A (ja) * | 1996-11-27 | 1998-06-16 | Nippon Synthetic Chem Ind Co Ltd:The | 感圧性接着剤組成物 |
JP3604117B2 (ja) * | 1997-03-06 | 2004-12-22 | 株式会社クラレ | 熱可塑性重合体組成物 |
JPH10298522A (ja) * | 1997-04-30 | 1998-11-10 | Kuraray Co Ltd | 接着剤組成物 |
US6054549A (en) | 1998-11-25 | 2000-04-25 | Dow Corning Asia, Ltd. | Alkenyl ether functional polyisobutylenes and methods for the preparation thereof |
US6497949B1 (en) | 2000-08-11 | 2002-12-24 | 3M Innovative Properties Company | Adhesive blends comprising hydrophilic and hydrophobic pressure sensitive adhesives |
US6642298B2 (en) | 2001-03-16 | 2003-11-04 | National Starch And Chemical Investment Holding Corporation | Rubber-acrylic adhesive formulation |
TW593614B (en) | 2001-03-16 | 2004-06-21 | Nat Starch Chem Invest | Rubber-acrylic adhesive formulation |
DE10208039A1 (de) | 2002-02-26 | 2003-09-04 | Basf Ag | Haftklebstoffe, enthaltend Polyethylen |
US6893718B2 (en) | 2002-05-20 | 2005-05-17 | 3M Innovative Properties Company | Pressure sensitive adhesive composition, articles made therewith and method of use |
JP4557305B2 (ja) | 2003-06-19 | 2010-10-06 | 日東電工株式会社 | ゴム系粘着剤組成物とその粘着シート |
JP5596250B2 (ja) | 2005-03-02 | 2014-09-24 | スリーエム イノベイティブ プロパティズ カンパニー | 湿気反応性組成物及び有機el素子 |
EP1862520A1 (de) | 2006-06-01 | 2007-12-05 | Basf Aktiengesellschaft | Folienetiketten |
US20070281151A1 (en) | 2006-06-01 | 2007-12-06 | Basf Aktiengesellschaft | Film-backed labels |
KR101519831B1 (ko) | 2006-11-30 | 2015-05-13 | 더 유니버시티 오브 아크론 | 폴리이소부틸렌 및 그 제조방법 |
US7932316B2 (en) * | 2006-12-30 | 2011-04-26 | Bridgestone Corporation | Processable rubber composition |
JP4437502B2 (ja) | 2007-04-03 | 2010-03-24 | 日東電工株式会社 | 塗膜保護用シート |
CN102076803B (zh) | 2008-06-02 | 2014-11-12 | 3M创新有限公司 | 粘合剂封装组合物以及用其制备的电子器件 |
JP5890177B2 (ja) | 2008-06-02 | 2016-03-22 | スリーエム イノベイティブ プロパティズ カンパニー | 接着剤封入組成物及びそれを用いて作製される電子デバイス |
ATE545688T1 (de) | 2008-07-02 | 2012-03-15 | 3M Innovative Properties Co | Oberflächenenergiearmer klebstoff |
JP2010163566A (ja) | 2009-01-16 | 2010-07-29 | Three M Innovative Properties Co | エポキシ樹脂組成物 |
EP2406338B1 (en) | 2009-03-09 | 2012-11-28 | 3M Innovative Properties Company | Aziridine crosslinking agents for acrylic adhesives |
WO2010141248A1 (en) | 2009-06-04 | 2010-12-09 | 3M Innovative Properties Company | Stretch releasable pressure-sensitive adhesives |
TW201111463A (en) | 2009-08-04 | 2011-04-01 | 3M Innovative Properties Co | Non-halogentaed polyisobutylene-thermoplastic elastomer blend pressure sensitive adhesives |
WO2011062852A1 (en) | 2009-11-19 | 2011-05-26 | 3M Innovative Properties Company | Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer |
JP2014503640A (ja) | 2010-12-13 | 2014-02-13 | スリーエム イノベイティブ プロパティズ カンパニー | 低表面エネルギー基材用感圧接着剤 |
-
2010
- 2010-11-15 EP EP10779654.2A patent/EP2501759B1/en not_active Not-in-force
- 2010-11-15 CN CN201080052309.5A patent/CN102666714B/zh not_active Expired - Fee Related
- 2010-11-15 WO PCT/US2010/056646 patent/WO2011062851A1/en active Application Filing
- 2010-11-15 KR KR1020127015693A patent/KR20120089343A/ko active IP Right Grant
- 2010-11-15 JP JP2012539955A patent/JP5695657B2/ja not_active Expired - Fee Related
- 2010-11-15 US US13/499,921 patent/US8530578B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0519278A2 (en) * | 1991-06-19 | 1992-12-23 | Nitto Denko Corporation | Automobile paint film-protective sheet |
CN1125956A (zh) * | 1993-05-11 | 1996-07-03 | 埃克森化学专利公司 | 含异丁烯与对甲基苯乙烯的卤化共聚物和羧基改性弹性体的相容共混物 |
CN101370889A (zh) * | 2006-01-24 | 2009-02-18 | 3M创新有限公司 | 粘合剂封装组合物膜以及有机电致发光器件 |
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US8530578B2 (en) | 2013-09-10 |
EP2501759B1 (en) | 2013-07-17 |
JP5695657B2 (ja) | 2015-04-08 |
CN102666714A (zh) | 2012-09-12 |
KR20120089343A (ko) | 2012-08-09 |
JP2013511593A (ja) | 2013-04-04 |
WO2011062851A1 (en) | 2011-05-26 |
EP2501759A1 (en) | 2012-09-26 |
US20120216953A1 (en) | 2012-08-30 |
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