CN104507979B - 包含含有侧接可自由基聚合的季铵取代基的聚(异丁烯)共聚物的粘合剂 - Google Patents
包含含有侧接可自由基聚合的季铵取代基的聚(异丁烯)共聚物的粘合剂 Download PDFInfo
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- CN104507979B CN104507979B CN201380017561.6A CN201380017561A CN104507979B CN 104507979 B CN104507979 B CN 104507979B CN 201380017561 A CN201380017561 A CN 201380017561A CN 104507979 B CN104507979 B CN 104507979B
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明描述了包含异丁烯重复单元与烯烃重复单元的共聚物的粘合剂组合物。所述烯烃重复单元的至少一部分键合至包含可自由基聚合的取代基的季铵盐的侧接氮原子。所述粘合剂任选地包含诸如增粘剂、非官能化的聚异丁烯聚合物、增塑剂及它们的组合的其它组分。
Description
背景技术
聚异丁烯(PIB)被认为是用于低表面能(LSE)粘结应用的值得注意的材料,因为它在烯烃基热塑性塑料上具有优异的粘附特性。(参见例如WO 2011/062852和WO 2011/062851)
发明内容
本发明描述了包含异丁烯重复单元与烯烃重复单元的共聚物的粘合剂组合物。烯烃重复单元的至少一部分键合至包含可自由基聚合的取代基的季铵盐的侧接氮原子。粘合剂任选地包含诸如增粘剂、非官能化的聚异丁烯聚合物、增塑剂及它们的组合的其它组分。
在一个实施例中,共聚物具有通式:
其中a为至少20,b和c的总和为至少1,并且Z为包含可自由基聚合的取代基的季铵盐基团。
具体实施方式
本文所述的发明涉及由异丁烯共聚物制备的粘合剂和密封剂,以及由其制备的条带制品。在有利的实施例中,粘合剂为压敏粘合剂。
粘合剂组合物包含异丁烯重复单元与烯烃重复单元的共聚物,其中烯烃重复单元的至少一部分键合至包含可自由基聚合的取代基的季铵基团的侧接氮原子。在一些实施例中,共聚物本身可用作粘合剂。在其它实施例中,粘合剂包含与增粘剂组合的此类异丁烯共聚物、非官能化的异丁烯聚合物(即,共聚物或均聚物)或它们的组合。
异丁烯共聚物包含烯烃重复单元。如本文所用,“烯烃”是指具有不饱和基团的直链或支化的二价烃,例如异戊二烯、丁烯、戊烯、己烯、辛烯,等等。在典型实施例中,共聚物的烯烃重复单元通常包含异戊二烯、丁烯或它们的组合。在一些实施例中,共聚物包含异丁烯重复单元与异戊二烯重复单元的共聚物,其中异戊二烯重复单元的一部分键合至包含可自由基聚合的取代基的季铵基团的侧接氮原子。
如本文所用,“可自由基聚合的”基团或取代基是指在暴露于合适的自由基源时参与交联反应的烯键式不饱和部分。可自由基聚合的基团包括例如(甲基)丙烯酰基,诸如(甲基)丙烯酸酯和(甲基)丙烯酰胺;以及乙烯基(例如芳环的乙烯基)。可自由基聚合的基团使用二价连接基团诸如(例如支链或直链)亚烷基键合至季铵基团的氮原子。亚烷基连接基团通常具有至少2个碳原子并且不超过18或12个碳原子,诸如,例如乙烯基、丙烯基、丁烯基、新戊烯基、己烯基和辛烯基。
在一些实施例中,异丁烯重复单元和诸如衍生自异戊二烯或丁二烯的烯烃重复单元为共聚物的唯一重复单元。然而,共聚物可任选地包含低浓度的其它重复单元,诸如包含对甲基苯乙烯的重复单元,前提条件是其它重复单元不减损粘合剂的剥离和剪切特性。对甲基苯乙烯单体单元还可以通过对甲基苯乙烯本身的内聚力和硬度赋予共聚物耐热性和强度。然而,本文所述的粘合剂组合物在不存在包含对甲基苯乙烯重复单元的共聚物的情况下表现出良好的粘附力以及高剪切值(10,000分钟+室温下)。
异丁烯重复单元与烯烃重复单元的共聚物通常包含较低浓度的烯烃(例如异戊二烯)重复单元,该重复单元键合至包含可自由基聚合的取代基的季铵基团的氮原子。浓度大于共聚物的0重量%并通常为共聚物的至少1、2、3、4或5重量%。键合至季胺基团的氮原子的烯烃(例如异戊二烯)重复单元的浓度通常不大于20重量%并且在一些实施例中不大于15、14、13、12或10重量%。由于可自由基聚合的取代基的分子量通常为包含可自由基聚合的取代基的季铵基团的分子量的约一半,可自由基聚合的基团的浓度通常为异丁烯共聚物的至少0.5、1、1.5或2重量%并且通常不大于10或7.5或7.0或6.5或6或5重量%。低浓度的可自由基聚合的基团易于经由交联来增加剪切强度,而不会在(例如热熔融)处理期间过早形成凝胶。
衍生自键合至季胺基团的氮原子的异戊二烯的重复单元可由下式表示:
其中Z为包含可自由基聚合的取代基的季铵基团。
如以下反应方案中所述,通常通过对可商购获得的卤化PIB(包括具有叔胺的卤化聚(异丁烯-共-异戊二烯))进行亲核置换,从而形成其中卤素(如溴)被置换为带负电的抗衡离子的季铵盐,由此制备共聚物。
用于此类亲核置换的合适叔胺包括例如丙烯酸3-(二甲氨基)新戊酯、甲基丙烯酸2-(二甲氨基)乙酯、N-[3-(二甲氨基)丙基]丙烯酰胺和乙烯基吡啶。
当共聚物包含衍生自异戊二烯的重复单元时,反应方案可如下描述:
其中X2为卤素,优选地为溴;
Z为具有式–+(NR2R3R4)(X2)-或
(X2)-的季胺,
R2包含可自由基聚合的基团;
R3和R4中的每一个独立地为C1-C18烷基;
a为至少20;并且
b和c的总和为至少1。
将认识到具有下标“a”的单体单元为聚合的异丁烯单体单元。另外,下标“b”和“c”经选择使得共聚物包含1至20重量%的相应单体单元,如此前所述。
在一些实施例中,与溴化共聚物反应的叔胺具有式NR2R3R4;而季铵盐基团Z具有通式(NR2R3R4)+(X2)-。
如此形成的叔胺和季铵盐的取代基中的至少两个(例如R3和R4)通常独立地为C1-C18烷基。烷基可为环状的(合在一起形成环的R3和R4)、直链的或支化的。在一些实施例中,R3和R4独立地为C1-C4,诸如甲基。
叔胺可由下式表示:
其中R3和R4为烷基,如此前所述
X为–O-或–NR6-,
x为0或1;
R5为亚烷基,并且
R6为氢或C1-C4烷基。
在其它实施例中,诸如当将乙烯基吡啶用作叔胺时,氮原子为芳环结构的一部分。五价氮环化合物也被认为是季铵化合物。
尽管可采用催化剂或烷基化剂,但此类反应可仅通过升高温度(如约100℃)来引发。
可替代地,包含含有可自由基聚合的取代基的侧接季铵盐的异丁烯共聚物可通过如下方式形成:使卤化的(通常是溴化的)异丁烯共聚物与具有亲核体(如羟烷基)的胺反应,该亲核体随后可与亲电体(诸如丙烯酰氯)反应,从而将羟基转化成可自由基聚合的基团。此类反应物如下描述:
在一些实施例中,用于形成包含侧接可自由基聚合的基团的异丁烯的原料为可商购获得的溴化共聚物,诸如可以商品名“Lanxess Bromobutyl 2030”得自朗盛公司(Lanxess)的溴化共聚物(溴含量为约1.5至2.0重量%且分子量(Mw)为约500,000克/摩尔)。在其它实施例中,可通过与N-溴代琥珀酰亚胺(NBS)或溴原子反应,随后与包含可自由基聚合的取代基的叔胺化合物反应,由此卤化非官能化的异丁烯共聚物。另外,非官能化的均聚物和共聚物可与包含侧接季铵盐基团的聚异丁烯共聚物共混。因此,非官能化的异丁烯共聚物可用作原料。非官能化的聚异丁烯共聚物和均聚物还可用作粘合剂组合物的任选但附加的组分。聚异丁烯均聚物由于在聚合物中缺乏卤化所需的不饱和基团而不可用作原料。此类不饱和基团由烯烃共聚单体重复单元来提供。
通常通过在诸如氯化铝、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存在下,单独地聚合异丁烯或通过聚合异丁烯与其他烯键式不饱和单体(诸如异戊二烯、丁二烯或它们的组合)来制备聚异丁烯材料。共聚物通常为无规共聚物。然而,或者可采用嵌段共聚物。
在一些实施例中,包含侧接可自由基聚合的季铵基团的异丁烯共聚物的重均分子量(Mw)为至少25,000克/摩尔、至少50,000克/摩尔、至少100,000克/摩尔或至少150,000克/摩尔。在一些实施例中,重均分子量通常不大于4,000,000克/摩尔,或3.000,000克/摩尔,或2,000,000克/摩尔,或1,000,000克/摩尔或500,000克/摩尔。
非官能化的异丁烯共聚物通常为具有聚异丁烯主链的合成橡胶。在一些实施例中,异丁烯的异丁烯共聚物为其中异丁烯与另一种单体共聚的合成橡胶。合成橡胶包括丁基橡胶,该丁基橡胶是大部分异丁烯与少量烯烃(诸如异戊二烯)的共聚物,例如,可以商品名VISTANEX(埃克森化学公司(Exxon Chemical Co.))和JSR BUTYL(日本丁基聚合物有限公司(Japan Butyl Co.,Ltd.))获得的丁基橡胶。合成橡胶还包括大部分异丁烯与正丁烯或丁二烯的共聚物。在一些实施例中,可使用异丁烯均聚物和丁基橡胶的混合物,即第一聚异丁烯包含异丁烯的均聚物,而第二聚异丁烯包含丁基橡胶;或第一聚异丁烯包含丁基橡胶,而第二聚异丁烯包含异丁烯的均聚物。
在一些实施例中,粘合剂还包含非官能化的异丁烯均聚物以及异丁烯重复单元与烯烃重复单元的共聚物,其中烯烃重复单元的一部分键合至包含可自由基聚合的取代基的季铵盐的侧接氮原子。
均聚物可(例如)以商品名OPPANOL(例如,OPPANOL B10、B15、B30、B50、B80、B100、B150和B200)从新泽西州弗洛勒姆帕克的巴斯夫公司(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35,000至4,000,000克/摩尔的范围内。其它示例性的均聚物可以宽泛的分子量范围从俄罗斯圣彼得堡的联合化工产品公司(UnitedChemical Products(UCP),St.Petersburg,Russia)商购获得。例如,以商品名SDG从UCP商购获得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从UCP商购获得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从UCP商购获得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经由自由基聚合形成共价键的反应性双键。
当采用时,压敏粘合剂组合物中的非官能化的异丁烯共聚物或均聚物的浓度通常为至少5重量%,或10重量%、15重量%。非官能化的异丁烯共聚物或均聚物的浓度通常不大于50重量%,或45重量%,或40重量%,或35重量%。
在其它实施例中,粘合剂包含至少一种增粘剂。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,在趋向于产生热的应用中,通常选择软化点为至少75℃的增粘剂。这样的软化点在粘合剂组合物经受诸如来自电子设备或电子部件的热时可帮助使增粘剂与粘合剂组合物的余下部分的分离最小化。通常选择软化温度为至少80℃、至少85℃、至少90℃或至少95℃。然而,在不产生热的应用中,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,例如氢化脂环族树脂、氢化芳香族树脂或者它们的组合。合适的增粘剂为可商购获得的并包括例如,以商品名“ARKON”(例如,“ARKON P”或“ARKON M”)从日本大阪的荒川化学工业有限公司(Arakawa ChemicalIndustries Co.,Ltd.(Osaka,Japan))获得的那些;以商品名ESCOREZ(例如ESCOREZ 1315、1310LC、1304、5300、5320、5340、5380、5400、5415、5600、5615、5637和5690)从德克萨斯州休斯敦的埃克森美孚公司(Exxon Mobil Corporation,Houston,TX)获得的那些;和以商品名REGALREZ(例如REGALREZ 1085、1094、1126、1139、3102和6108)从田纳西州金斯波特的伊士曼化工公司(Eastman Chemical,Kingsport,TN)获得的那些。
增粘剂的浓度可根据预期的粘合剂组合物而变化。在一些实施例中,增粘剂的量为至少5重量%、10重量%或15重量%。增粘剂的最大量通常为不大于45重量%,或40重量%,或35重量%,或30重量%,或25重量%的增粘树脂。
增塑剂也可以用于粘合剂配方中,以提供润湿作用和/或粘度控制。这些增塑剂在本领域中是熟知的,并且可以包括烃油;液态或柔软的增粘剂,包括液态烃类树脂、液态聚萜烯、液态聚(异丁烯)诸如GlissopalTM等;蜡;以及油的混合物。本发明的压敏粘合剂中的增塑剂的含量为粘合剂组合物的1、2、3、4或5重量%,并且通常不大于30或25或20或15或10重量%。
本领域的技术人员还将会知道,可以将其它添加剂(诸如填料、抗氧化剂、稳定剂和着色剂)与粘合剂共混,以获得有益的特性。
侧接季铵基团的可自由基聚合的基团可按照本领域中已知的方式固化。在一些有利的实施例中,可自由基聚合的基团是辐射固化的(诸如通过光固化)。在此类实施例中,光引发剂通常被加入粘合剂组合物。
光交联剂优选地为发色团-取代的氯代-甲基-s-三嗪交联剂。在一个实施例中,交联剂如U.S.4,330,590(Vesley)中所述,并具有下式:
其中R10、R12、R13和R14独立地为氢、烷基或烷氧基;并且R10、R12、R13和R14基团中的1-3个为氢。优选地,烷基和烷氧基具有不超过12个碳原子,并且常常不超过4个碳原子。优选地,R12和R13均为烷氧基,因为这往往提供更短的反应时间。相邻的烷氧基取代基可以互连以形成环。光敏s-三嗪组分可以通过在HCl气体和路易斯酸(诸如AlCl3、AlBr3等)的存在下使芳基腈与三氯乙腈共三聚而制得,如在Bull.Chem.Soc.Japan(日本化学学会公报),第42卷,第2924页(1969)中所述。
在另一个实施例中,交联剂如U.S.4,329,384(Vesley)中所述,并具有下式:
其中R15和R16独立地为氢、烷基或烷氧基。通过这种图示,它意指R15和R16可以在稠环的任一者上。优选地,光敏s-三嗪组分的任何烷基或烷氧基具有不超过12个碳原子,并且不超过2个烷基和烷氧基具有超过6个碳原子。在某些实施例中,它们具有不超过4个碳原子,并且烷基常常为甲基或乙基,并且烷氧基常常为甲氧基或乙氧基。相邻的烷氧基取代基可以互连以形成环。光敏s-三嗪组分可以通过在HCl气体和路易斯酸(诸如AlCl3、AlBr3等)的存在下使多核腈与三氯乙腈共三聚而制得,如在Bull.Chem.Soc.Jap.(日本化学学会公报),第42卷,第2924-2930页(1969)中所述。
合适的氯化三嗪交联剂的例子包括但不限于如U.S.4,330,590(Vesley)中所述的2,4-双(三氯甲基)-6-(4-甲氧基)苯基)-s-三嗪、2,4-双(三氯甲基)-6-(3,4-二甲氧基)苯基)-s-三嗪、2,4-双(三氯甲基)-6-(3,4,5-三甲氧基)苯基)-s-三嗪、2,4-双(三氯甲基)-6-(2,4-二甲氧基)苯基)-s-三嗪、2,4-双(三氯甲基)-6-(3-甲氧基)苯基)-s-三嗪,以及如U.S.4,329,384(Vesley)中所述的2,4-双(三氯甲基)-6-萘次甲基-s-三嗪和2,4-双(三氯甲基)-6-(4-甲氧基)萘次甲基-s-三嗪。
氯化三嗪交联剂优选为光交联剂。更优选地,三嗪交联剂为发色团取代的氯-甲基-s-三嗪交联剂,其可根据Wakabayashi等人的Bull.Chem.Soc.Jap.(日本化学学会公报),第42卷,第2924-2930页(1969)而制备。
可以使用在入射到选择用于组合物的特定光敏交联剂上时产生自由基的足够能量(即波长范围)的光化辐射源来固化粘合剂组合物,该粘合剂组合物包含具有侧接季胺基团的异丁烯共聚物,该侧接季胺基团包含烯键式不饱和可自由基聚合的基团。上文所公开的用于光敏交联剂的优选波长范围为400至250nm。使本发明的粘合剂膜交联所需的该优选波长范围内的辐射能为100至1500毫焦耳/平方厘米,更优选地为200至800毫焦耳/平方厘米。光固化方法的细节在U.S.4,181,752(Martens等人)和4,329,384(Vesley等人)中公开。
在一些实施例中,粘合剂组合物以溶剂溶液或分散体的形式施用,在暴露于光化辐射(诸如UV)时溶剂蒸发,且粘合剂组合物发生交联。此类溶剂型组合物的交联可以在涂覆和除去溶剂之前进行,但优选地在涂覆和除去溶剂之后进行。合适的溶剂,诸如烷烃、乙酸乙酯、甲苯和四氢呋喃与共聚物组分的可自由基聚合的基团不反应。
在其它实施例中,诸如热熔性粘合剂组合物,粘合剂以无溶剂形式根据熔体施用。热熔融涂覆PSA组合物消除了溶剂处理的需要。为了热熔融处理粘合剂组合物,所述组合物通常在涂覆工艺之前或在涂覆工艺期间不交联;然而,为了实现剪切粘附,交联通常是优选的。在热熔融涂覆过程中,这通常通过暴露于高能辐射(例如电子束或高强度紫外线辐射)完成。通常,当使用高强度紫外线辐射时,将诸如二苯甲酮的光敏交联物质加入组合物。一般来讲,与溶液涂覆组合物相比,热熔性粘合剂组合物需要聚(异丁烯)共聚物具有更窄的分子量范围。太低的话,交联聚合物的内聚强度会不足。太高的话,组合物不能进行挤出涂覆。通常,非官能化的聚(异丁烯)共聚物的分子量为50,000至5,000,000克/摩尔。在一些实施例中,非官能化的聚(异丁烯)共聚物的分子量不大于1,000,000克/摩尔,或500,000克/摩尔,或400,000克/摩尔,或300,00克/摩尔,或200,000克/摩尔或100,000克/摩尔。
在一些实施例中,提供了在熔融状态下施用至基材的热熔性粘合剂组合物。此类热熔性粘合剂组合物是基本上不含溶剂的。热熔性粘合剂是通用的,并广泛用于工业应用,诸如装订、硬纸箱、塑料件和木制品等等。热熔体通常为100%固体粘合剂,其中施用温度从约150至约180℃发生变化。
在有利的实施例中,(例如固化)粘合剂为压敏粘合剂。根据压敏条带协会,已知压敏粘合剂(PSA)具有包括以下的特性:(1)有力而持久的粘着力;(2)用不超过指压的压力即可粘附;(3)具有足够固定到粘合体上的能力;以及(4)足够的内聚强度以便使其从粘合体干净地移除。已发现作为PSA充分发挥作用的材料包括经设计和配制以表现出所需粘弹性的聚合物,所述粘弹性实现所期望的粘着力、剥离粘附力与剪切保持力的平衡。PSA的特征在于通常在室温(例如20℃)是发粘的。PSA不包括仅具有粘性或仅能够附着到某表面的组合物。
通常使用设计用来逐个地测量粘着力、粘附力(剥离强度)和内聚力(剪切保持力)的测试方法来评估这些要求,如A.V.Pocius在由俄亥俄州辛辛那提汉瑟加德纳出版社(Hanser Gardner Publication,Cincinnati,OH)于2002年出版的Adhesion andAdhesives Technology:An Introduction(粘附和粘合剂技术:概论)(第2版)中所指明的那样。这些量度合在一起构成了经常用来表征PSA的特性的平衡。
例如,如果弹性体的玻璃化转变温度(Tg)或模量过高,并高于粘性的Dahlquist标准(在室温和1Hz的振动频率下3×106达因/cm2的储能模量),则所述材料将不是粘性,且本身不可用作PSA材料。通常在这种情况中,低分子量高Tg树脂聚合物(增粘剂)或低分子量低Tg聚合物(增塑剂)常用于将Tg和模量调节至最佳PSA范围内。
本发明的粘合剂可使用常规涂覆技术涂覆在多种柔性和非柔性背衬材料上以制成粘合剂涂覆的材料。柔性基材在本文中定义为通常用作条带背衬或可具有任何其它弹性材料的任何材料。例子包括(但不限于)塑料薄膜,诸如聚丙烯、聚乙烯、聚氯乙烯、聚酯(聚对苯二甲酸乙二醇酯)、聚碳酸酯、聚甲基(甲基)丙烯酸酯(PMMA)、醋酸纤维素、三乙酸纤维素和乙基纤维素。可使用泡沫背衬。非柔性基材的实例包括(但不限于)金属、金属化聚合物膜、氧化铟锡涂覆的玻璃和聚酯、PMMA板、聚碳酸酯板、玻璃或陶瓷片材。粘合剂涂覆的片材可采用常规已知能够与粘合剂组合物一起使用的任何制品形式,诸如标签、条带、指示牌、封面、标记标志、显示组件、触摸面板等等。还可想到具有微复制型表面的柔性背衬材料。
采用改进的适用于具体基材的常规的涂覆技术,将上述组合物涂覆在基材上。例如,可通过以下方法诸如辊涂、流涂、浸涂、旋涂、喷涂、刮涂和压模涂覆将这些组合物施用至多种固体基材。这些各种涂覆方法使得组合物以可变的厚度被置于基材上,从而使得这些组合物得到更广泛的应用。涂层的厚度可以有差别,但是可设想2至500微米(干燥厚度),优选约25至250微米的涂层厚度。
本发明的粘合剂可特别用于形成对低表面能(LSE)基材的强粘结。本文所用的低表面能基材为表面能小于约45达因/厘米,更典型地小于约40达因/厘米,且最典型地小于约35达因/厘米的那些。此类材料中包括烯烃基热塑性塑料(聚丙烯、聚乙烯、高密度聚乙烯或HDPE、乙烯-丙烯-二烯单体橡胶(EPDM))以及聚苯乙烯和聚(甲基丙烯酸甲酯)(PMMA)。此类材料通常用于汽车、涂料、电器及电子产品市场。其它基材也可由于在基材的表面上有残余物(诸如油状残余物)或薄膜(诸如涂料)而具有低表面能特性。然而,即使本发明的粘合剂良好地粘结至低表面能表面,本发明也不限于粘结至低表面能基材,因为已发现,本发明的粘合剂也可良好地粘结至较高表面能的基材,诸如,例如其它塑料、陶瓷、玻璃和金属。本文所述的粘合剂组合物由于具有低气味和生理惰性而还适于医用粘合剂领域。
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热塑性弹性体的90度剥离为至少5盎司/英寸(5N/dm)。对于遮蔽条带,对玻璃、不锈钢、HDPE、PP或TPE的90度剥离通常为15-20盎司/英寸(16-22N/dm)。在一些有利的实施例中,粘合剂表现出对高表面能基材和低表面能基材二者的良好粘附力。在一些实施例中,对玻璃、不锈钢、EPDM或PP的90度剥离独立地为至少25、30、35、40、45或50盎司/英寸。在至少一些实施例中,室温(23℃)下的剪切为至少300分钟、500分钟或800分钟。在一些有利的实施例中,室温(23℃)或70℃下的剪切为至少2,000分钟、4,000分钟、8,000分钟或10,000分钟。
取决于基材待用于的特定应用而选择基材(PSA粘结至所述基材)。例如,可将粘合剂施用至片材产品(例如装饰性图形和反射性产品)、标签纸(label stock)和条带背衬。另外,可将粘合剂直接施用至基材(诸如汽车面板或玻璃窗)上,使得另一基材或物体可被附接到所述面板或窗。
粘合剂也可以压敏粘合剂转移条带的形式提供,其中粘合剂的至少一层设置于剥离衬垫上以用于在以后施用至持久基材。粘合剂也可作为单一涂覆或双涂覆的条带提供,其中粘合剂设置于持久背衬上。背衬可由塑料(例如聚丙烯(包括双轴向取向的聚丙烯)、乙烯树脂、聚乙烯、聚酯(诸如聚对苯二甲酸乙二醇酯))、非织造物(例如纸、布、非织造稀松布)、金属箔、泡沫(例如聚丙烯酸类、聚乙烯、聚氨酯、氯丁橡胶)等制成。泡沫可购自多个供应商,诸如3M公司(3M Co.)、Voltek公司(Voltek)、积水株式会社(Sekisui)和其它。泡沫可成型为共挤出的片材,所述片材在泡沫的一侧或两侧上具有粘合剂,或者粘合剂可被层合至所述片材。当粘合剂被层合至泡沫时,可能有利的是处理表面以改善粘合剂对泡沫或对任何其它类型的背衬的粘附力。这种处理通常基于粘合剂的材料的性质和泡沫或背衬的性质来进行选择,并包括底漆和表面改性(例如电晕处理、表面磨损)。另外的条带构造包括描述于U.S.5,602,221(Bennett等人)的那些,所述专利以引用方式并入本文。
对于单侧条带,与设置粘合剂之处相对的背衬表面的侧面通常涂覆有合适的剥离材料。剥离材料是已知的,并包括诸如例如有机硅、聚乙烯、聚氨基甲酸酯、聚丙烯酸类等的材料。对于双涂覆条带,另一粘合剂层设置于与本发明的粘合剂设置之处相对的背衬表面上。另一粘合剂层可不同于本发明的粘合剂,例如,常规丙烯酸类PSA,或者其可为具有相同或不同配方的与本发明相同的粘合剂。双涂覆的条带通常承载在剥离衬垫上。
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。
实例
如实例中所用,pph是指每百份聚合物的份数。一百份聚合物包括季胺改性的聚异丁烯聚合物和任何非官能化的聚异丁烯(例如MWPIB)的总量。
测试方法:
90°角剥离粘合强度测试。
使用ASTM国际标准D3330方法F中所述的工序,用IMASS SP-200滑动/剥离测试仪(得自马萨诸塞州阿科德艾玛氏有限公司(IMASS,Inc.,Accord MA))以305mm/min(12英寸/分钟)的剥离速率以90°角测量剥离粘合强度。使用被表1中所示的对应溶剂润湿的纸巾通过用力手压的方式将面板擦拭8至10次,从而准备好测试面板。再用被溶剂润湿的干净纸巾将该工序重复两次。使清洁的面板干燥。将粘合带切割成测量尺寸为1.27cm×20cm(1/2英寸×8英寸)的条带,然后用2.0kg(4.5磅)的橡胶辊将条带滚到清洁后的面板上,共滚两次。测试之前将制备的样品在23℃/50%RH下保存24小时。针对每个实例测试两个样品,平均值用N/dm表示。注意失效模式,并记为COH-内聚(即条带和测试表面上均有粘合剂裂缝留下的残余物),ADH-粘合(即粘合剂从测试表面上干净地剥离),以及MIX–粘合剂从一些区域干净地剥离并附着到其它区域的表面。
表1–剥离粘合测试面板材料
材料 | 溶剂 |
HDPE:高密度聚乙烯 | 异丙醇 |
PP:聚丙烯 | 异丙醇 |
基于EPDM和聚丙烯的热塑性弹性体(TPE) | 异丙醇 |
SS:不锈钢 | 庚烷 |
材料 | 溶剂 |
玻璃:钠钙玻璃 | 庚烷 |
静态剪切强度
如ASTM国际标准D3654工序A中所述在23℃/50%RH(相对湿度)下用1000g负荷评价静态剪切强度。用剥离粘合测试中所述的清洁面板和粘附条带的方法将测量为1.27cm×15.24cm(1/2英寸_×6英寸)的条带测试样品附着到1.5英寸_×2英寸的不锈钢(SS)面板。条带与面板重叠的部分为1.27cm×2.5cm,将条带本身在粘合剂侧折叠,然后再折叠。将钩子挂在第二折叠部分中,并通过将条带网装固定在钩子上进行固定。将砝码附接到钩子,然后将面板悬挂在23℃/50%RH的室中。记录以分钟计的失效时间。如果10,000分钟后没有观察到失效,则停止测试并记录10,000分钟的值。还记录剥离粘合测试中所述的失效模式。
实例所用的材料
·BPIB–异丁烯与溴化异戊二烯的共聚物(Lanxess Bromobutyl2030,俄亥俄州阿克伦的朗盛公司(Lanxess Corporation;Akron,OH))
·LPIB–低分子量(1K g/mol)液体聚异丁烯(Glissopal 1000,增塑剂,新泽西州弗伦翰公园的巴斯夫公司(BASF;Florham Park,NJ))
·增粘剂–脂环烃基增粘剂(ESCOREZ 5340增粘剂,德克萨斯州贝敦埃克森美孚公司(ExxonMobil Corporation;Baytown,TX))MWPIB–非官能化的中等分子量(80K g/mol)聚异丁烯(OPPANOL B15聚合物,新泽西州弗伦翰公园的巴斯夫公司)3SAB–涂底漆的聚酯膜(南卡罗来纳州格里尔的三菱公司(Mitsubishi,Greer,SC))
·交联剂(2,4-双-三氯甲基-6(3,4-二甲氧基-苯基)-S-三嗪),其可根据Wakabayashi等人的Bull.Chem.Soc.Jap.日本化学学会公报),第42卷,第2924-2930页(1969)中所述来制备)。
·溶剂包括异丙醇、庚烷和丙酮(密苏里州圣路易斯的西格玛-奥德里奇公司(Sigma Aldrich,St.Louis,MO))
·甲苯–99.5%,(新泽西州吉布斯敦的EMD公司(EMD,Gibbstown,NJ))
叔胺
·甲基丙烯酸2-(二甲氨基)乙酯(俄勒冈州波特兰的TCI美国公司(TCI America,Portland,OR))
·N-[3-(二甲氨基)丙基]丙烯酰胺(俄勒冈州波特兰的TCI美国公司)
·丙烯酸3-(二甲氨基)丙酯(俄勒冈州波特兰的TCI美国公司)
·丙烯酸3-二甲氨基新戊酯(宾夕法尼亚州沃林顿的聚合科学公司(Polysciences,Warrington,PA))
丙烯酸3-(二甲氨基)丙酯接枝PIB(聚合物1)的制备
向配备有回流冷凝器、温度计和氮气入口的三颈圆底烧瓶中放置LanxessBromobutyl 2030共聚物(20.0g)、丙烯酸3-(二甲氨基)丙酯(1.0g)和甲苯(80.0g)。在室温下在氮气气氛下用磁力搅拌棒搅拌烧瓶的内容物。待所有组分完全溶解后,将烧瓶加热至105℃。5小时后,将反应冷却至室温。将溶液倾注到丙酮中,以使改性的聚合物凝结。用新鲜的丙酮将分离的聚合物洗涤三次以除去反应溶剂和未反应的反应物。然后过滤聚合物,并在真空烘箱中于50℃下干燥12小时,然后冷却至室温。
丙烯酸3-二甲氨基新戊酯接枝PIB(聚合物2)的制备
聚合物2按照聚合物1中的工序来合成,不同的是使用丙烯酸2,3-二甲氨基新戊酯代替丙烯酸3-(二甲氨基)丙酯。
甲基丙烯酸2-(二甲氨基)乙酯接枝PIB(聚合物3)的制备
聚合物3按照聚合物1中的工序来合成,不同的是使用甲基丙烯酸3,2-(二甲氨基)乙酯代替丙烯酸3-(二甲氨基)丙酯。
N-[3-(二甲氨基)丙基]丙烯酰胺接枝PIB(聚合物4)的制备
聚合物4按照聚合物1中的工序来合成,不同的是使用N-[3-(二甲氨基)丙基]丙烯酰胺代替丙烯酸3-(二甲氨基)丙酯。
实例1-2和对照组合物C1-C2
通过在包含400份甲苯的100mL广口瓶以表2中示出的量将改性聚合物(聚合物1),或C1的溴化异丁烯(BPIB)与C1的共聚物,以及任选的非官能化的中等分子量聚异丁烯(MWPIB)、增粘剂(ESCOREZ5340增粘剂)和交联剂(2,4-双-三氯甲基-6(3,4-二甲氧基-苯基)-S-三嗪)混合来制备粘合剂组合物。将广口瓶在滚磨机上混合过夜。
表2–粘合剂组合物
将所得组合物刮涂到6英寸×25英寸的聚酯膜背衬条带的涂底漆侧上至约15密耳的湿厚。在设定为70℃的烘箱中将涂覆的膜干燥20分钟,以提供具有2密耳粘合剂涂层厚度的条带。使用UV处理器(马里兰州盖瑟斯堡辐深紫外系统有限公司(Fusion UV System,Inc.,Gaithersburg,MD)),通过用UV光(400mJ/cm2,UVB)照射而使涂覆的条带固化。
将条带在23℃、50%RH下调节24小时,然后测试90°剥离粘附力和室温剪切强度(RT剪切力)。测试结果示于表3中。
表3–粘合剂特性
实例3–8
粘合剂组合物和条带按照实例1-2中所述进行制备,不同的是改性PIB为聚合物2、3和4。粘附性组合物示出于表5中。室温和90°剥离粘附力测试结果示出于表6中。
表5–粘合剂组合物
表6–具有聚合物2-4的条带的粘附特性
热熔性(无溶剂)粘合剂组合物和条带按照实例9–10中所述进行制备。通过以表7中示出的量将溴化异丁烯(BPIB)的共聚物、非官能化的中等分子量聚异丁烯(MWPIB)、甲基丙烯酸2-(二甲氨基)乙酯、交联剂(2,4-双-三氯甲基-6(3,4-二甲氧基-苯基)-S-三嗪)、低分子量液体聚异丁烯(LPIB)和增粘剂(ESCOREZ 5340增粘剂)混合来制备组合物。
混合在希拉本德混合器(新泽西州南哈肯萨克的C.W.希拉本德仪器公司(C.W. Instruments,Inc South Hackensack,NJ))中于100℃下进行。典型的混合时间为5-10分钟。
表7–粘合剂组合物
然后,在170℃下将所制备的粘合剂组合物热压到6英寸×25英寸的聚酯膜背衬条带的涂底漆侧上至约5密耳的厚度。使用UV处理器(马里兰州盖瑟斯堡辐深紫外系统有限公司(Fusion UV System,Inc.,Gaithersburg,MD)),通过用UV光(400mJ/cm2,UVB)照射而使涂覆的条带固化。测试结果示出于表8中。
表8–条带粘合特性
Claims (15)
1.一种粘合剂组合物,其包含异丁烯重复单元与烯烃重复单元的共聚物和任选地增粘剂,其中所述烯烃重复单元衍生自异戊二烯、丁二烯、或它们的组合,其中所述烯烃重复单元的至少一部分键合至包含可自由基聚合的取代基的季铵盐基团的侧接氮原子,其中所述共聚物具有式
其中a为至少20,b和c的总和为至少1,并且Z为包含可自由基聚合的取代基的季铵盐基团。
2.根据权利要求1所述的粘合剂组合物,其包含大于0重量%但小于20重量%的键合至所述季铵盐基团的氮原子的烯烃重复单元。
3.根据权利要求1所述的粘合剂组合物,其中所述季铵盐基团具有式:
—+(NR2R3R4)(X2)-或(X2)-,
其中R2包含可自由基聚合的基团,并且R3和R4中的每一个独立地为C1-C18烷基;且
X2为卤素。
4.根据权利要求3所述的粘合剂组合物,其中所述可自由基聚合的基团为(甲基)丙烯酸酯或(甲基)丙烯酰胺基团。
5.根据权利要求1所述的粘合剂组合物,其中所述共聚物的重均分子量为50,000至5,000,000克/摩尔。
6.根据权利要求5所述的粘合剂组合物,其中所述共聚物的重均分子量不大于1,000,000克/摩尔。
7.根据权利要求1所述的粘合剂组合物,其还包含光交联剂。
8.根据权利要求7所述的粘合剂组合物,其中所述光交联剂选自醛、酮、醌和发色团取代的卤代甲基均三嗪光交联剂,所述酮包括噻吨酮。
9.根据权利要求1所述的粘合剂组合物,其还包含5至50重量%的增粘剂。
10.根据权利要求1所述的粘合剂组合物,其还包含5至50重量%的非官能化的聚异丁烯聚合物。
11.根据权利要求10所述的粘合剂组合物,其中所述非官能化的聚异丁烯聚合物的重均分子量不大于100,000克/摩尔。
12.根据权利要求1所述的粘合剂组合物,其还包含增塑剂。
13.根据权利要求1所述的粘合剂组合物,其中所述粘合剂为热熔性粘合剂。
14.一种交联的根据权利要求1所述的粘合剂组合物。
15.一种粘合剂制品,其在背衬上包含根据权利要求1至14中任一项所述的粘合剂组合物。
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KR102102636B1 (ko) * | 2015-11-05 | 2020-04-22 | 주식회사 엘지화학 | 광학용 점착제 조성물, 광학용 점착제 조성물의 제조방법 및 광학용 점착 필름 |
US11702525B2 (en) | 2018-12-04 | 2023-07-18 | Exxonmobil Chemical Patents Inc. | Cationomeric polyolefin compositions and methods for production and use thereof |
WO2020117495A1 (en) * | 2018-12-04 | 2020-06-11 | Exxonmobil Chemical Patents Inc. | Cationomeric polyolefin compositions and methods for production and use thereof |
US20220220347A1 (en) * | 2019-06-18 | 2022-07-14 | Avery Dennison Corporation | Butyl rubber based pressure sensitive adhesives |
JP2021172812A (ja) * | 2020-04-21 | 2021-11-01 | Jsr株式会社 | 熱可塑性エラストマー組成物及び成形体 |
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