CN103687920B - 用在电子器件上的两部分双固化粘合剂 - Google Patents

用在电子器件上的两部分双固化粘合剂 Download PDF

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Publication number
CN103687920B
CN103687920B CN201280036192.0A CN201280036192A CN103687920B CN 103687920 B CN103687920 B CN 103687920B CN 201280036192 A CN201280036192 A CN 201280036192A CN 103687920 B CN103687920 B CN 103687920B
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substrate
adhesive composition
isocyanate
light emitting
emitting diode
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CN201280036192.0A
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CN103687920A (zh
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A·M·乔治尼
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HB Fuller Licensing and Financing Inc
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HB Fuller Licensing and Financing Inc
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Abstract

本发明涉及一种两部分双固化粘合剂组合物，所述两部分双固化粘合剂组合物包含含有可辐射聚合的多异氰酸酯预聚物的第一部分(A)和含有多元醇的第二部分(B)。本发明所公开的粘合剂可用在具有电子元件的基底上以制备电子组件。

Description

用在电子器件上的两部分双固化粘合剂
本申请要求于2012年7月22日提交的并入本文中的美国临时申请No.61/510,820的权益。
发明内容
在一些方面，本发明涉及制备电子组件的方法，该电子组件包括第一基底、第二基底和至少一个位于两个基底之间的电子元件。该方法包括向第一基底的至少一部分施加两部分双固化粘合剂组合物。然后，使第二基底的至少一部分与第一基底上的粘合剂接触。第一和第二基底的至少一者在施加粘合剂组合物前包括至少一个电子元件。粘合剂组合物包含可辐射聚合的多异氰酸酯预聚物（A部分）和多元醇（B部分）。
在一个实施例中，可辐射聚合的多异氰酸酯预聚物是可辐射聚合的化合物和脂族多异氰酸酯预聚物的反应产物。
在一些方面，本发明涉及包括第一基底、第二基底、至少一个位于两个基底之间的电子元件和粘合剂的电子组件，其中第一基底的至少一部分通过粘合剂粘结到第二基底的至少一部分。粘合剂包含可辐射聚合的多异氰酸酯预聚物（A部分）和多元醇（B部分）的双固化反应产物。
附图说明
图1显示了位于两个基底之间的电子元件的剖视图。
图2显示了位于两个基底之间的电子元件的剖视图，其中粘合剂围绕组件的边缘。
图3显示了位于两个基底之间的电子元件的剖视图，其中粘合剂遍及整个组件。
术语表
关于本发明，这些术语具有下述含义：
“(甲基)丙烯酸酯”是指丙烯酸酯、甲基丙烯酸酯和它们的混合物。
“双固化”是指组合物通过两种不同的机理固化，例如对可辐射固化的官能团的辐射以及异氰酸酯官能团与羟基之间的化学反应。
“可辐射聚合的化合物”是指在其分子中包含活性氢和可辐射聚合的官能团的化合物。
“可辐射聚合的组分”是指在其分子中包含可辐射聚合的官能团但不含活性氢的化合物。
“脂族多异氰酸酯预聚物”是指作为脂族异氰酸酯和多元醇的反应产物的多异氰酸酯预聚物。
具体实施方式
粘合剂组合物
该粘合剂组合物是包含第一部分（A部分）和第二部分（B部分）的两部分双固化粘合剂组合物，第一部分包含可辐射聚合的多异氰酸酯预聚物和任选的非可辐射聚合的多异氰酸酯单体或异氰酸酯封端的预聚物；第二部分包含多元醇和/或胺。粘合剂组合物还可以包含光引发剂，该光引发剂可以存在于A部分或B部分或它们的组合中。或者，可独立于A部分和B部分向组合物提供光引发剂。优选地将A部分和B部分合并以实现约1:1至约2:1、或约1.2:1至约1.6:1、或约1.4:1的异氰酸酯(NCO)与羟基(OH)化学计量比（即NCO:OH）。就胺而言，异氰酸酯(NCO)与胺中的活性氢的化学计量比与异氰酸酯(NCO)与羟基(OH)的化学计量比相似。A部分和B部分的合并量优选地使得在固化前按组合物的重量计组合物包含约5重量%、或约30重量%、或约50重量%、或约60重量%至不超过约80重量%、或不超过约70重量%的可辐射聚合的多异氰酸酯预聚物；最多约50重量%、或从约5重量%、或约10重量%至不超过约50重量%、或不超过约40重量%、或不超过约30重量%的多异氰酸酯单体或异氰酸酯封端的预聚物；从约20重量%或约30重量%至不超过约90重量%或不超过约70重量%的多元醇；以及最多约5重量%、或从0.2重量%、或0.5重量%至约5重量%、或至约1重量%的光引发剂。
将粘合剂组合物的A部分和B部分在施加粘合剂前立即混合物在一起。当合并A部分和B部分时，粘合剂组合物在65℉至170℉的温度下的粘度优选地为约250厘泊至约5000厘泊。双固化粘合剂组合物的两个部分然后随着时间的推移彼此反应，从而形成交联。该反应的发生速率影响双固化组合物的适用期，即可以施加粘合剂组合物并用于其预期目的所处的时期。优选地，双固化粘合剂组合物表现出至少30分钟或甚至至少45分钟的适用期。如上指出，粘合剂组合物随着时间的推移通过预聚物（A部分）的异氰酸酯基团与多元醇（B部分）的羟基的反应而继续固化。
由于粘合剂通过暴露于辐射以及异氰酸酯基团与羟基之间的化学反应而固化，因此将该粘合剂称为“双固化”粘合剂。粘合剂组合物在暴露于辐射时优选地表现出适于允许对层合物进行处理和后续加工的搭接剪切强度。优选地，粘合剂组合物在暴露于紫外辐射后表现出至少10克/平方英寸(g/in2)、或至少25g/in2、或至少50g/in2、或至少约60g/in2的搭接剪切。固化的粘合剂组合物还优选地表现出至少25克/直线英寸的剥离强度，或甚至对与其粘结到的基底表现出破坏性粘结。
当与电子组件一起使用时，粘合剂优选地表现出某些特性。例如，粘合剂优选地能够在低温下在低成本基底上加工。它优选地能够用于自动化卷对卷制造工艺。它优选地表现出无需B阶段的快速附连。组合物优选地具有长开放时间或长凝固时间。组合物优选地表现出对低能材料比如塑料的良好的初始强度和最终粘结强度。它还优选地为柔性的。它优选地表现出良好的湿气和氧气阻隔性能。它优选地为光学透明的并且当暴露于紫外辐射或较高的温度时不会黄化。它优选地表现出低渗气和空隙。并且它优选地通过消耗密封组件内部的残余湿气而起到干燥剂或除湿剂的作用。
A部分
两部分双固化粘合剂组合物的第一部分（A部分）包含可辐射聚合的多异氰酸酯预聚物和任选的非可辐射聚合的多异氰酸酯单体或异氰酸酯封端的预聚物。在一些实施例中，可辐射聚合的多异氰酸酯预聚物具有(甲基)丙烯酸酯官能团。按A部分的重量计，A部分优选地包含约40重量%、或约50重量%、或约60重量%至不超过约90重量%、或不超过约80重量%的可辐射聚合的多异氰酸酯预聚物，以及最多约60重量%、或从约10重量%、或15重量%、或20重量%、或30重量%、或40重量%至不超过60重量%、或不超过50重量%的多异氰酸酯单体或异氰酸酯封端的预聚物。
可辐射聚合的多异氰酸酯预聚物可辐射聚合的多异氰酸酯预聚物包含可辐射固化的官能团和异氰酸酯官能团。这些官能团在预聚物上位于侧边、末端或它们的组合。优选地，官能团在预聚物上位于末端，即预聚物由官能团封端。可辐射聚合的多异氰酸酯预聚物优选地包含约5重量%、或约10重量%至不超过约20重量%的异氰酸酯官能团，和一定量的足以提供在暴露于辐射时表现出适于后续加工的初始搭接剪切强度的粘合剂组合物的可辐射聚合的官能团。
在A部分中可辐射聚合的官能团与异氰酸酯基团的当量比优选地为约0.1:1至约5:1、或约0.5:1至约4:1、或约0.6:1至约3:1、或约1:1。可辐射聚合的多异氰酸酯预聚物的平均官能度优选地为约1.8、或约2至不超过8、或不超过约4；并且可辐射聚合的多异氰酸酯预聚物的数均分子量优选地为约200至约100,000g/mol、或约400至约50,000g/mol、或约600至约10,000g/mol。
可辐射聚合的多异氰酸酯预聚物优选地通过使包含活性氢和可辐射聚合的官能团的可辐射聚合的化合物与多异氰酸酯预聚物优选地在存在过量异氰酸酯的情况下反应而制备。优选地，可辐射聚合的化合物与多异氰酸酯预聚物的反应量使得多异氰酸酯预聚物上约10%至约80%、或约20%至约70%、或约30%至约60%的异氰酸酯基团被包含活性氢和可辐射聚合的官能团的可辐射聚合的化合物替代。
术语“活性氢”是指羟基、胺或巯基官能团上的活性氢。
可辐射聚合的官能团的例子包括丙烯酸酯、甲基丙烯酸酯、烯基（例如乙烯基、烯丙基和己烯基）、乙烯基醚、乙烯基酯、乙烯基酰胺、马来酸酯、富马酸酯和苯乙烯官能团以及它们的组合。
包含活性氢和可辐射聚合的官能团的合适的可辐射聚合的化合物包括（例如）丙烯酸和甲基丙烯酸羟烷基酯类（例如丙烯酸-2-羟乙酯(HEA)、甲基丙烯酸-2-羟乙酯(HEMA)、丙烯酸-2-羟丙酯、丙烯酸-3-羟丙酯(HPA)和甲基丙烯酸-2-羟丙酯、甲基丙烯酸-3-羟丙酯、丙烯酸-1,3-二羟基丙酯、丙烯酸-2,3-二羟基丙酯和甲基丙烯酸-1,3-二羟基丙酯、甲基丙烯酸-2,3-二羟基丙酯、2-羟乙基丙烯酰胺和甲基丙烯酰胺、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸-4-羟丁酯、(甲基)丙烯酸2-羟基-3-苯氧基丙酯、单(甲基)丙烯酸-1,4-丁二醇酯、2-羟基烷基(甲基)丙烯酰基磷酸酯类、(甲基)丙烯酸-4-羟基环己酯、单(甲基)丙烯酸-1,6-己二醇酯、单(甲基)丙烯酸新戊二醇酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基乙烷二(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、N-烷基-N-羟乙基丙烯酰胺类和甲基丙烯酰胺类、羟乙基丙烯酸β-羧乙酯、丙烯酸羟己酯和甲基丙烯酸羟辛酯以及它们的混合物。
可用的丙烯酸羟乙酯类和丙烯酸羟丙酯类可从密歇根州米德兰陶氏化学公司(DowChemical,MidlandMich.)和日本大阪市大阪有机化学工业株式会社(OsakaOrganicChemicalIndustryLtd.,Osaka,Japan)商购获得。可用的丙烯酸羟丁酯类可从大阪有机化学工业株式会社(OsakaOrganicChemicalIndustryLtd.)商购获得。可用的羟基聚酯丙烯酸酯类可以商品名TONEMONOMERM-100从陶氏化学公司(DowChemicalCompany)以及以VISCOAT2308从大阪有机化学工业株式会社(OsakaOrganicChemicalIndustryLtd.)商购获得。可用的羟基聚醚丙烯酸酯类可以商品名ARCOLR-2731从宾夕法尼亚州匹兹堡拜耳化学公司(BayerChemicals,Pittsburgh,Pa.)商购获得。
多异氰酸酯预聚物是多异氰酸酯和多元醇的反应产物。多异氰酸酯和多元醇在反应混合物中的量使得异氰酸酯(NCO)与羟基(OH)的比率为约2:1。所得的多异氰酸酯预聚物不含羟基并且具有从约500g/mol、或约1000g/mol至不超过13,000g/mol、或不超过6000g/mol、或不超过4000g/mol的数均分子量。
可用于制备多异氰酸酯预聚物的多异氰酸酯类具有至少两个异氰酸酯基团并包括（例如）脂族、环脂族、芳脂族、芳烷基、烷芳基和芳族异氰酸酯类以及它们的混合物；和二异氰酸酯类、三异氰酸酯类、四异氰酸酯类以及它们的混合物。
优选的多异氰酸酯预聚物包括作为脂族多异氰酸酯和多元醇的反应产物的那些。
可用的脂族多异氰酸酯类包括（例如）1,3-环戊烷二异氰酸酯、1,4-环己烷二异氰酸酯、1,3-环己烷二异氰酸酯、氢化MDI（即二环己基甲烷二异氰酸酯，H12-MDI）、2,4-环己烷二异氰酸甲酯、2,6-环己烷二异氰酸甲酯、1,4-双(异氰酸根合甲基)环己烷、1,3-双(异氰酸根合甲基)环己烷。
可用的芳族多异氰酸酯类包括（例如）二苯甲烷二异氰酸酯化合物(MDI)（包括其异构体）、碳二亚胺改性的MDI、二苯甲烷4,4'-二异氰酸酯、二苯甲烷2,2'-二异氰酸酯、二苯甲烷2,4'-二异氰酸酯、低聚亚甲基异氰酸酯类、甲苯二异氰酸酯(TDI)（包括其异构体）、萘二异氰酸酯的异构体、三苯甲烷三异氰酸酯的异构体以及它们的混合物。
其他合适的二异氰酸酯类包括（例如）4,4'-二苯基二异氰酸酯、4,4'-甲苯胺二异氰酸酯、联甲氧基苯胺二异氰酸酯(dianisidinediisocyanate)、4,4'-二苯醚二异氰酸酯、1,3-苯二亚甲基二异氰酸酯（包括1,3-二异氰酸根合邻二甲苯、1,3-二异氰酸根合对二甲苯和1,3-二异氰酸根合间二甲苯）、1,4-苯二亚甲基二异氰酸酯、ω,ω'-二异氰酸根合-1,4-二乙基苯、四甲基苯二亚甲基二异氰酸酯的异构体、二烷基二苯基甲烷二异氰酸酯类、四烷基二苯基甲烷二异氰酸酯类、4,4'-二苄基二异氰酸酯、1,3-亚苯基二异氰酸酯、1,4-亚苯基二异氰酸酯以及它们的混合物。
另外的合适的二异氰酸酯类的例子包括1,2-二异氰酸根合乙烷、1,3-二异氰酸根合丙烷、1,2-二异氰酸根合丙烷、1,4-二异氰酸根合丁烷、1,5-二异氰酸根合戊烷、1,6-二异氰酸根合己烷、双(3-异氰酸根合丙基)醚、双(3-异氰酸根合丙基)硫醚、1,7-二异氰酸根合庚烷、1,5-二异氰酸根合-2,2-二甲基戊烷、1,6-二异氰酸酯-3-甲氧基己烷、1,8-二异氰酸根合辛烷、1,5-二异氰酸根合-2,2,4-三甲基戊烷、1,9-二异氰酸根合壬烷、1,4-丁二醇的1,10-二异氰酸根合丙醚、1,11-二异氰酸根合十一烷、1,12-二异氰酸根合十二烷、双(异氰酸根合己基)硫醚、2,4-二异氰酸根合-1-氯苯、2,4-二异氰酸根合-1-硝基苯、2,5-二异氰酸根合-1-硝基苯、间亚苯基二异氰酸酯、1-甲氧基-2,4-亚苯基二异氰酸酯、1-甲氧基-2,4-亚苯基二异氰酸酯、3,3'-二甲基-4,4'-二苯基甲烷二异氰酸酯、1-甲基-2,4-二异氰酸根合环己烷、1,6-二异氰酸根合-2,2,4-三甲基己烷、1,6-二异氰酸根合-2,4,4-三甲基己烷、1-异氰酸根合甲基-3-异氰酸根合-1,5,5-三甲基环己烷(IPDI)、氯化和溴化的二异氰酸酯类、含磷的二异氰酸酯类、4,4'-二异氰酸根合苯基全氟乙烷、四甲氧基丁烷-1,4-二异氰酸酯、双异氰酸根合乙基邻苯二甲酸酯；包含反应性卤素原子的多异氰酸酯类（例如1-氯甲基苯基-2,4-二异氰酸酯、1-溴乙基苯基-2,6-二异氰酸酯和3,3-双氯甲基醚-4,4'-二苯基二异氰酸酯）；含硫的多异氰酸酯类；二聚脂肪酸二异氰酸酯类以及它们的组合。合适的三异氰酸酯类的例子包括4,4',4''-三苯基甲烷三异氰酸酯和2,4,6-甲苯三异氰酸酯。四异氰酸酯类的一个例子是4,4'-二甲基-2,2'-5,5'-二苯基甲烷四异氰酸酯。另一种合适的异氰酸酯是聚亚甲基聚亚苯基多异氰酸酯。
其他可用的异氰酸酯类在例如并入本文中的美国专利No.6,387,449、6,355,317、6,221,978、4,820,368、4,808,255、4,775,719和4,352,858中有所公开。
尤其优选的二异氰酸酯类为脂族异氰酸酯或脂族异氰酸酯类的共混物，因为它们提供优异的紫外稳定性（不黄化）和水解稳定性。
可用的市售脂族异氰酸酯类包括（例如）均得自宾夕法尼亚州匹兹堡拜耳公司(Bayer,Pittsburg,PA)的DESMODURW、DESMODURI和DESMODURN3600以及得自新泽西州帕西潘尼赢创德固赛公司(EvonikDegussa,Parsippany,NJ)的VESTANATIPDI和VESTANATH12MDI。市售的芳族异氰酸酯类包括（例如）以商品名MONDURML得自宾夕法尼亚州匹兹堡拜耳化学公司(BayerChemicals,Pittsburgh,Pa.)、以ISONATE50OP和ISONATE125M得自密歇根州米德兰陶氏化学公司(DowChemicalCompany,MidlandMich.)和以LUPRANATEMI得自德国巴斯夫公司(BASF,Germany)的芳族异氰酸酯类。
用于形成多异氰酸酯预聚物的多元醇具有至少两个羟基(OH)和约250g/mol、或约500g/mol或约1000g/mol至不超过12000g/mol、或不超过4000g/mol、或不超过2000g/mol的数均分子量。此类多元醇类包括聚酯多元醇类、聚醚多元醇类、聚碳酸酯类和聚缩醛类。
聚酯多元醇类可通过酸和/或酸酐与至少一种醇的缩聚而制备，例如多羧酸或酸酐和多元醇的缩聚。适用于制备聚酯多元醇类的多羧酸类包括（例如）脂族、环脂族、芳脂族、芳族和杂环多羧酸类和酸酐类。此类多羧酸类和酸酐类的例子包括琥珀酸、己二酸、辛二酸、壬二酸、癸二酸、环己二酸、戊二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、四氯邻苯二甲酸酐、内次甲基四氢邻苯二甲酸酐、戊二酸酐、马来酸、马来酸酐、富马酸、二聚脂肪酸类、三聚脂肪酸、偏苯三酸、偏苯三酸酐以及它们的组合。
可用于制备聚酯多元醇类的多元醇类包括脂族多元醇类（例如新戊二醇、乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、1,6-己二醇、己烯二醇类、己炔二醇类、1,7-庚二醇、庚烯二醇类、庚炔二醇类、1,8-辛二醇、辛烯二醇类和辛炔二醇类）、环己烷二甲醇、甘油、三羟甲基丙烷、季戊四醇、山梨醇和葡萄糖以及它们的混合物。可用的聚醚多元醇类包括多元醇类和聚环氧烷类的反应产物。可用于制备聚醚多元醇类的多元醇类包括乙二醇、丙二醇、丁二醇类、己二醇类、丙三醇类、三羟甲基乙烷、三羟甲基丙烷和季戊四醇以及它们的混合物。可用于制备聚醚多元醇类的环氧烷类包括环氧乙烷、环氧丙烷和丁烯类氧化物以及它们的混合物。
多异氰酸酯单体和异氰酸酯封端的预聚物。A部分还可以包含不能辐射聚合、用以提供过量异氰酸酯官能度的另外的多异氰酸酯单体或异氰酸酯封端的预聚物。也就是说，这些任选的成分在其分子中不具有可辐射聚合的官能团。过量的异氰酸酯官能度优选地以下述量存在于粘合剂组合物中，该量足以得到当根据本文所述的剥离粘附力测试方法进行测试时表现出破坏性剥离的粘合剂组合物。合适的多异氰酸酯单体包括上文所示的多异氰酸酯类和通过上文所示并且并入本文中的异氰酸酯单体和多元醇类形成的异氰酸酯封端的预聚物。优选地，多异氰酸酯单体为脂族异氰酸酯；并且异氰酸酯封端的预聚物为脂族异氰酸酯和多元醇的反应产物。
B部分
两部分双固化粘合剂组合物的第二部分（B部分）包含多元醇和任选的光引发剂。按B部分的重量计，B部分优选地包含约70重量%至约100重量%、或约80重量%至约100重量%、或约90重量%至约100重量%的多元醇和0重量%至约10重量%、或约0.2重量%至约5重量%、或约0.5重量%至约1重量%的光引发剂。
多元醇。B部分的合适多元醇类包括用于制备上述多异氰酸酯预聚物的那些，例如二醇类、三醇类以及它们的混合物。优选的多元醇类包括聚酯多元醇类、聚醚多元醇类、聚烯烃二醇类、聚二烯嵌段多元醇类以及它们的组合。优选的多元醇类的官能度为约1.5、或约2、或约3至不超过4.0、或不超过3.5。优选的多元醇类的Tg小于10℃，或甚至小于0℃，数均分子量为约500g/mol至约12000g/mol、或约750g/mol至约2000g/mol。
可用的多元醇类别包括（例如）聚酯多元醇类，包括（例如）内酯多元醇类及其环氧烷加合物，以及二聚酸基聚酯多元醇类；特制多元醇类，包括（例如）聚丁二烯多元醇类、氢化聚丁二烯多元醇类、聚碳酸酯多元醇类、双酚A的羟基烷基衍生物（例如双(2-羟乙基)双酚A）；聚醚多元醇类，包括（例如）聚硫醚多元醇类和氟化聚醚多元醇类；丙烯酸多元醇类、多酚的环氧烷加合物、聚四亚甲基二醇类、官能化甘油酯类（例如蓖麻油）和多羟基硫化聚合物。
可用的聚酯多元醇类由多羧酸类、其酸酐类、其酯类或其卤化物以及化学计量过量的多元醇的反应产物制备。合适的多羧酸类包括二羧酸类和三羧酸类，包括（例如）芳族二羧酸类及其酸酐类和酯类（例如对苯二甲酸、间苯二甲酸、对苯二甲酸二甲酯、对苯二甲酸二乙酯、邻苯二甲酸、邻苯二甲酸酐、甲基六氢邻苯二甲酸、甲基六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸、甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸、六氢邻苯二甲酸酐和四氢邻苯二甲酸）、脂族二羧酸类及其酸酐类（例如马来酸、马来酸酐、琥珀酸、琥珀酸酐、戊二酸、戊二酸酐、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、氯菌酸、1,2,4-丁烷-三羧酸、十二烷二羧酸、十八烷二羧酸、二聚酸、二聚脂肪酸类、三聚脂肪酸类和富马酸），以及脂环族二羧酸类（例如1,3-环己烷二羧酸和1,4-环己烷二羧酸）。
可衍生出聚酯多元醇类的合适多元醇类的例子包括脂族多元醇类，例如乙二醇类、丙烷二醇类（例如1,2-丙二醇和1,3-丙二醇）、丁二醇类（例如1,3-丁二醇、1,4-丁二醇和1,7-丁二醇）、1,3-丁烯二醇、1,4-丁烯二醇、1,4-丁炔二醇、戊二醇类（例如1,5-戊二醇）、戊烯二醇类、戊炔二醇类、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、新戊二醇、二甘醇、三甘醇、四甘醇、聚乙二醇类、丙二醇、聚丙二醇类（例如双丙甘醇和三丙二醇）、新戊二醇、1,4-环己烷二甲醇、1,4-环己二醇、二聚二醇类、双酚A、双酚F、氢化双酚A、氢化双酚F、甘油、1,4-丁二醇、聚四亚甲基二醇、3-甲基-1,5-戊二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、三羟甲基丙烷、季戊四醇、山梨醇、葡萄糖以及它们的组合。
可用的聚酯多元醇类的例子包括聚二醇己二酸酯类、聚对苯二甲酸乙二醇酯多元醇类、聚己内酯多元醇类和聚己内酯三醇类。
合适的市售多元醇类包括（例如）以商品名DESMOPHEN系列（包括例如DESMOPHENXF-7395-200、DESMOPHENS-1011-P-210、DESMOPHENS-1011-110和DESMOPHENS-1011-55）得自宾夕法尼亚州匹兹堡拜耳化学公司(BayerChemicals,Pittsburgh,Pa.)的聚酯多元醇类；以商品名PRIPLAST系列（包括例如PRIPLAST3187、3190、3196和3197）得自特拉华州纽卡斯尔有利凯玛公司(UNIQEMA,NewCastle,Del.)的二聚酸基聚酯多元醇类；以商品名POLYBDR-20LM、R-45HT和R-45M得自宾夕法尼亚州艾克斯顿克雷威利公司(CrayValley,Exton,Pa.)的聚丁二烯多元醇类，以及以商品名POLYTAIL得自日本三菱化学株式会社(MitsubishiChemicalCorp.,Japan)的氢化聚丁二烯多元醇类。
合适的聚醚多元醇类包括从环状氧化物例如环氧乙烷、环氧丙烷、环氧丁烷和四氢呋喃的聚合反应得到的产物，或者一种或多种此类氧化物与具有至少两个活性氢的多官能引发剂例如水、多元醇类（如乙二醇、丙二醇、二甘醇、环己烷二甲醇、甘油、三羟甲基丙烷、季戊四醇和双酚A）、乙二胺、丙二胺、三乙醇胺和1,2-丙烷二硫醇进行加成反应得到的产物。尤其有用的聚醚多元醇类包括（例如）聚氧丙烯二醇类和三醇类、通过将环氧乙烷和环氧丙烷同时或依次加到合适的引发剂中获得的聚(氧化乙烯-氧化丙烯)二醇类和三醇类，以及通过四氢呋喃的聚合反应获得的聚四亚甲基醚二醇类。
光引发剂
粘合剂组合物还可以包含光引发剂。光引发剂可存在于组合物的任何部分中，包括（例如）A部分、B部分以及它们的组合。优选的光引发剂能够在暴露于合适波长和强度的辐射时促进烯键式不饱和部分的自由基聚合，交联，或兼而有之。光引发剂可单独使用，或与合适的供体化合物或合适的共引发剂结合使用。光引发剂及其量优选为实现与所固化组合物的厚度相应的均一反应转化率，以及足够高程度的总体转化率，以便实现所需的初始处理强度（即，搭接剪切强度）。
可用的光引发剂包括（例如）“α裂解型”光引发剂，包括（例如）苯偶姻、苯偶姻缩醛类（例如苄基二甲基缩酮）、苯偶姻醚类（例如苯偶姻乙醚、苯偶姻异丙醚和苯偶姻异丁醚）、羟基烷基苯基酮类（例如1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基丙-1-酮和1-(4-异丙基苯基)-2-羟基-2-甲基丙-1-酮）、苯甲酰基环己醇、二烷氧基苯乙酮衍生物（例如2,2-二乙氧基苯乙酮）、酰基膦氧化物（例如双(2,4,6-三甲基苯甲酰基)苯基膦氧化物、双(2,6-二甲氧基苯甲酰基)-(2,4,4-三甲基戊基)膦氧化物和2,4,4-三甲基苯甲酰基二苯基膦氧化物）、甲基硫代苯基吗啉代酮类（例如2-甲基-1,4(甲硫基)和苯基-2-吗啉代-1-丙酮）以及吗啉代苯基氨基酮类；基于苯甲酮类、噻吨酮类、苄基类、樟脑醌类和香豆素酮类的包含光引发剂和共引发剂的夺氢型光引发剂；以及它们的组合。优选的光引发剂包括酰基膦氧化物，包括（例如）双(2,4,6-三甲基苯甲酰基)苯基膦氧化物、双(2,6-二甲氧基苯甲酰基)-(2,4,4-三甲基戊基)膦氧化物和2,4,4-三甲基苯甲酰基二苯基膦氧化物。
其他合适的光引发剂包括（例如）有机过氧化物、偶氮化合物、醌类、亚硝基化合物、酰基卤化物、腙类(hydrazones)、巯基化合物、吡喃鎓化合物、三丙烯酰基咪唑类、双咪唑类、氯烷基三嗪类、苯偶姻醚类、苯偶酰缩酮类、噻吨酮类和苯乙酮衍生物以及它们的混合物。
可用的市售光引发剂可按以下商品名获得：IRGACURE369吗啉代苯基氨基酮、IRGACURE819双(2,4,6-三甲基苯甲酰基)苯基膦氧化物、IRGACURECGI403双(2,6-二甲氧基苯甲酰基)-(2,4,4-三甲基戊基)膦氧化物、IRGACURE651苄基二甲基缩酮、IRGACURE1841-羟基环己基苯基酮和IRGACURE29594-(2-羟基乙氧基)苯基-(2-羟基-2-甲基丙基)酮、DAROCUR11732-羟基-2-甲基-1-苯基-丙-1-酮（它也被称为羟甲基苯基丙酮）、DAROCUR42652-羟基-2-甲基-1-苯基丙-1-酮和2,4,6-三甲基苯甲酰二苯基氧化膦的50:50共混物以及CGI1700双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基膦和2-羟基-2-甲基-1-苯基丙-1-酮的25:75共混物，它们均可得自巴斯夫公司(BASF)。
光引发剂优选地以足以提供所需的光聚合速率的量存在。该量将部分地取决于光源、待暴露于辐射能的层的厚度以及光引发剂在相应波长下的消光系数。通常，光引发剂按组合物的重量计将以最高约5重量%、或从约0.01重量%、或约0.1重量%、或约0.2重量%至不超过约5重量%的量存在。
任选的可辐射聚合的组分
粘合剂组合物可任选地在A部分或B部分中包含与上述A部分中的可辐射聚合的多异氰酸酯预聚物不同的另外的可辐射聚合的组分。该任选的可辐射聚合的组分包含至少两个可通过紫外或电子束辐射而聚合的可辐射聚合的官能团。然而，该任选的可辐射聚合的组分不含活性氢，因此也与上述可辐射聚合的化合物不同。该任选的可辐射聚合的组分可包含任何水平的可辐射聚合的官能度，包括单、双、三、四和更高的官能度。具有多个可辐射聚合的官能团的任选的可辐射聚合的组分的合适例子包括(甲基)丙烯酸酯类，包括（例如）由丙烯酸和/或甲基丙烯酸和脂族醇类、芳族多元醇类、脂族多元醇类、环脂族多元醇类以及它们的组合制备的丙烯酸和甲基丙烯酸的酯类，聚醚醇类的(甲基)丙烯酸酯类，氨基甲酸酯(甲基)丙烯酸酯低聚物、环氧(甲基)丙烯酸酯低聚物以及它们的组合。
脂族醇类的可用丙烯酸酯类包括（例如）(甲基)丙烯酸异冰片酯、(甲基)丙烯酸-2-乙氧基乙氧基乙酯以及它们的组合。脂族二醇类的可用丙烯酸酯类包括（例如）二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸-1,6-己二醇酯、三羟甲基丙烷三(甲基)丙烯酸酯、四(甲基)丙烯酸酯季戊四醇酯以及山梨糖醇和其他糖醇类的(甲基)丙烯酸酯类。这些脂族和环脂族二醇类的(甲基)丙烯酸酯类可用脂族酯或用环氧烷改性。通过脂族酯改性的丙烯酸酯类包括（例如）新戊二醇羟基新戊酸酯二(甲基)丙烯酸酯、己内酯改性的新戊二醇羟基新戊酸酯二(甲基)丙烯酸酯类以及它们的组合。环氧烷改性的丙烯酸酯化合物包括（例如）环氧乙烷改性的新戊二醇二(甲基)丙烯酸酯类、环氧丙烷改性的新戊二醇二(甲基)丙烯酸酯类、环氧乙烷改性的1,6-己二醇二(甲基)丙烯酸酯类或环氧丙烷改性的1,6-己二醇二(甲基)丙烯酸酯类以及它们的组合。
合适的衍生自聚醚多元醇类的丙烯酸酯单体包括（例如）新戊二醇改性的三羟甲基丙烷二(甲基)丙烯酸酯类、聚乙二醇二(甲基)丙烯酸酯类、丙二醇二(甲基)丙烯酸酯类等。三官能或更高级的多官能丙烯酸酯单体包括（例如）三羟甲基丙烷三(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸二季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、己内酯改性的六(甲基)丙烯酸二季戊四醇酯、四(甲基)丙烯酸季戊四醇酯、三[(甲基)丙烯酰氧乙基]异氰脲酸酯、己内酯改性的三[(甲基)丙烯酰氧乙基]异氰脲酸酯类或三羟甲基丙烷四(甲基)丙烯酸酯以及它们的组合。
合适的多官能(甲基)丙烯酸酯单体包括（例如）三丙二醇二丙烯酸酯、新戊二醇丙氧基二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯和季戊四醇三丙烯酸酯以及它们的组合。
其他添加剂
粘合剂组合物还可以包含其他添加剂，包括（例如）抗氧化剂、增塑剂、增粘剂、粘附促进剂、非反应性树脂、紫外线稳定剂、催化剂、流变改性剂、杀生物剂、缓蚀剂、脱水剂、有机溶剂、着色剂（例如颜料和染料）、填充剂、表面活性剂、阻燃剂、蜡以及它们的混合物。这些添加剂可存在于A部分或B部分或两者的组合中。这些添加剂当存在时优选为具有有限的紫外吸收，以使透过材料并用于光引发剂分子引发光聚合过程的光量最大化。
粘合剂可任选地包含增塑剂。合适的增塑剂包括（例如）邻苯二甲酸酯类、苯甲酸酯类、磺酰胺类和它们的混合物，以及环氧化大豆油。邻苯二甲酸二辛酯和邻苯二甲酸二异癸酯的可用来源包括以商品名JAYFLEXDOP和JAYFLEXDIDP得自埃克森化工(ExxonChemical)的那些。可用的二苯甲酸酯类可以商品名BENZOFLEX9-88、BENZOFLEX50和BENZOFLEX400得自伊士曼化学公司(EastmanChemicalCo.)。大豆油可商购获得，例如以商品名FLEXOLEPO得自陶氏化学公司(DowChemical)。
增塑剂当存在时优选地以约0.25重量%至约10重量%、不超过约5重量%、不超过约3重量%或甚至约0.5重量%至2重量%存在。
粘合剂可任选地包含填充剂。合适的填充剂包括（例如）热解法二氧化硅、沉淀二氧化硅、滑石、碳酸钙、炭黑、硅酸铝、粘土、沸石、陶瓷、云母、二氧化钛以及它们的组合。当存在时，组合物优选地包含至少0.5重量%、约1重量%至约50重量%、或甚至约5重量%至约10重量%的量的填充剂。对于最典型的应用，将不使用填充剂以保持透明性。
粘合剂可以任选地包含热塑性聚合物，包括（例如）乙烯醋酸乙烯酯、乙烯-丙烯酸、甲基丙烯酸乙烯酯和乙烯-丙烯酸正丁酯共聚物、聚乙烯醇、羟乙基纤维素、羟丙基纤维素、聚乙烯基甲基醚、聚环氧乙烷、聚乙烯基吡咯烷酮、聚乙基噁唑啉类、淀粉、纤维素酯以及它们的组合。
制备和使用方法
本发明所公开的粘合剂可用于整个电子制造工艺。在一些实施例中，粘合剂用于将电子组件的多个层粘结在一起。示例性多层组件在图1中示出。图1显示了一般组件10。组件10包括第一基底12和第二基底14。组件10包括至少一个位于基底12与基底14之间的电子元件20。应当理解，组件10可如图1所示包括不止一个电子元件20。
组件10可任选地包括位于电子元件20与基底12和14之间的导电层16和18。导电层可以是导电涂层、导电油墨或导电粘合剂。导电层可以沿着基底为连续的或不连续的。示例性导电层为氧化铟锡(ITO)。电子元件20置于第一基底12与第二基底14之间的方式可使得与导电层16和18直接或间接电导通。直接导通可以是紧密接触，而间接导通可借助导电材料或介质。可能理想的是，电子元件的一侧对应于阳极侧，而另一侧对应于阴极侧。
粘合剂可用于如图2所示通过将粘合剂24施加到组件的边缘或如图3所示通过用粘合剂24淹没组件而将组件10的层粘结或密封在一起。
本发明所公开的粘合剂组合物可用于制造电子组件。当与电子器件一起使用时，粘合剂组合物可起到导电粘合剂、半导电粘合剂、绝缘粘合剂或密封剂的作用。组件可包括多个电子元件。示例性电子元件包括发光二极管(LED)、有机LED、高亮度LED、射频识别(RFID)标签、电致变色显示器、电泳显示器、电池、传感器、太阳能电池以及光伏电池。
使用粘合剂将基底粘附在一起或密封两个基底之间的电子元件可提供比如使元件免受诸如湿气、紫外辐射、氧气等影响的有益效果。它还可以避免从组件中的材料逸出气体。它还允许电子在两个基底之间移动。
粘合剂组合物包含在将粘合剂组合物施加到基底之前不久合并到一起的(A)部分和(B)部分。(A)部分和(B)部分优选地不在将混合物施加到基底之前较长的时间合并（或混合在一起），因为(A)部分和(B)部分在合并后不久就会开始固化。
在一些实施例中，本发明所公开的粘合剂可用于将多个电子元件层合在两个柔性基底之间。具体地讲，粘合剂可用于将至少两个基底层合在一起，该基底中的至少一个在其上具有至少一个电子元件。示例性层合工艺包括卷对卷制造工艺。粘合剂可按多种方式施加到基底上。例如，粘合剂可按液态施加。可以使用任何合适的涂布工艺施加粘合剂，这些工艺包括（例如）气刀、拖刀、喷涂、喷射、刷涂、浸渍、刮墨刀、辊涂、凹版涂布、照相凹版涂布、轮转凹版涂布、线性挤出机、手喷枪、挤出机熔珠以及它们的组合。粘合剂还可按预定的图案被印刷上。粘合剂还可以施加到隔离衬片上，其中将粘合剂/衬片复合材料粘附到基底上。
粘合剂组合物优选地在室温下为液体。可用的涂布温度在65℉至170℉的范围内。粘合剂的涂层厚度可根据层合物的所需性质而差异巨大，例如从约1密耳至约80密耳。涂布到第一基底上后，将第一基底与第二基底接触。第二基底可具有相对于第一基底的材料相同或不同的材料，但对紫外辐射足够透明。两个基底的至少一者在施加粘合剂前在其上具有至少一个电子元件。粘结过程可重复多次，使得可能产生由不止两个粘结的层组成的制品。
在一个实施例中，制备电子组件的方法包括用两部分双固化粘合剂组合物涂布第一基底，将涂布的粘合剂组合物暴露于辐射，然后使第一基底上的涂布粘合剂组合物与第二基底接触。两个基底的至少一者在施加粘合剂前在其上具有至少一个电子元件。在另一个实施例中，制备电子组件的方法包括用两部分双固化粘合剂组合物涂布第一基底，使第二基底与第一基底上的涂布粘合剂接触，然后将电子元件位于两个基底之间的层合的两个基底暴露于辐射。两个基底的至少一者在施加粘合剂前在其上具有至少一个电子元件。
将粘合剂组合物暴露于辐射可在将涂布的粘合剂与第二基底接触之前和/或之后进行。粘合剂组合物可直接暴露于辐射或通过对紫外辐射足够透明的基底中的至少一个而暴露于辐射。将粘合剂组合物暴露于辐射引发存在于组合物中的辐射固化性官能团的自由基聚合，这将为层合物赋予初始粘合剂特性，例如搭接剪切强度。涉及存在于组合物中的异氰酸酯基团和羟基的相对缓慢的反应也随着时间的推移而发生，并提供粘合剂组合物及由其构造的层合物的最终性能特性。
组合物可使用例如电子束、紫外线（即，约200nm至约400nm范围内的辐射）、可见光（具有约400nm至约800nm范围内的波长的辐射）以及它们的组合而辐射固化。可用的辐射源包括例如超高压汞灯、高压汞灯、中压汞灯、金属卤化物灯、微波供电灯、氙灯、激光束源（包括例如准分子激光和氩离子激光）以及它们的组合。
在一些实施例中，本发明所公开的粘合剂可用于密封电子元件以提供进一步的防护。在此类应用中，粘合剂可只施加到基底的边缘，或可施加到基底的整个表面，从而包封电子元件。粘合剂可使用上述工艺中的任一种而施加。
在一些实施例中，本发明所公开的粘合剂可用于将电子元件粘结到一起而作为制造工艺的一部分。这一应用与层合工艺的相似之处在于将两个基底粘结到一起。但是，此工艺可用于刚性和柔性基底。
基底
粘合剂组合物可用于多种刚性或柔性基底。示例性基底包括柔性薄膜，诸如金属箔（铝箔），由聚合物制备的聚合物薄膜和金属化聚合物薄膜，这些聚合物包括（例如）聚烯烃类（例如聚丙烯、聚乙烯、低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、聚丙烯和定向聚丙烯；聚烯烃类和其他共聚单体的共聚物）、金属化聚烯烃类（例如金属化聚丙烯）、金属化聚醚对苯二甲酸酯、乙烯-乙酸乙烯酯、乙烯-甲基丙烯酸离聚物、乙烯-乙烯基醇、聚酯类（例如聚对苯二甲酸乙二醇酯）、聚碳酸酯类、聚酰胺类（例如尼龙-6和尼龙-6,6）、聚氯乙烯、聚偏二氯乙烯、聚乳酸、纤维素、聚苯乙烯、玻璃纸以及纸张。薄膜的厚度可以变化，但是柔性薄膜的厚度通常小于约0.5毫米，例如从约10微米至约150微米，更通常的是从约8微米至约100微米。基底的表面可使用任何合适的方法包括（例如）电晕处理、化学处理和火焰处理进行表面处理，从而提高粘附力。
其他合适的基底包括（例如）织造网、非织造网、纸张、纸板和多孔柔性片材（例如聚乙烯泡沫、聚氨酯泡沫、海绵和泡沫橡胶）。织造和非织造网可包含纤维，纤维包括（例如）棉花、聚酯、聚烯烃、聚酰胺和聚酰亚胺纤维。其他基底可包括玻璃、透明塑料（诸如聚烯烃类、聚醚砜类、聚碳酸酯类、聚酯、聚丙烯酸酯类）和聚合物薄膜。
以上说明书、例子和数据描述了本发明。可在不脱离本发明的精神和范围的情况下产生另外的实施例。除非另外指明，否则实例中所述的所有份数、比率、百分比和量均按重量计。
实例
测试方法
搭接剪切强度
搭接剪切强度根据ASTMD3163测定，其中将试件构造成在具有1英寸×1英寸基底重叠的、层合到10密耳厚的聚对苯二甲酸乙二醇酯(PET)第二基底上的10密耳厚的聚对苯二甲酸乙二醇酯(PET)第一基底上具有5密耳粘合剂涂层。
测定最大负荷，并将结果以g/in2为单位记录为搭接剪切强度。记录三个样品的平均值。
湿气透过率(MVTR)
湿气透过率(MVTR)根据题为“StandardTestMethodforWaterVaporTransmissionRateThroughPlasticFilmandSheetingusingaModulatedInfraredSensor”（使用调制红外线传感器的水蒸气透过塑料薄膜和片材的穿透率的标准测试方法）的ASTMF1249-90。在约37℃(100℉)和90%相对湿度下对具有指定厚度的薄膜形式的粘合剂样品进行该测试。
剥离粘附力测试方法
T剥离强度根据题为“StandardTestMethodforPeelResistanceofAdhesives”（粘合剂抗剥离性的标准测试方法）的ASTMD1876-01测定，其中将试件构造成在具有1英寸×1英寸基底重叠的、层合到10密耳厚的聚对苯二甲酸乙二醇酯(PET)第二基底上的10密耳厚的聚对苯二甲酸乙二醇酯(PET)第一基底上具有5密耳粘合剂涂层。
剥离速度为12英寸每分钟。结果以克每直线英寸记录。记录三个样品的平均值。
%NCO
存在于粘合剂组合物中的异氰酸酯百分比(%NCO)通过首先将预聚物溶于甲苯，使预定体积的预聚物/甲苯溶液与预定体积的二丁基胺溶液反应而测定。胺与异氰酸酯基团反应。然后将过量的胺用预定的氯化氢溶液进行滴定。再将氯化氢溶液的体积用于计算存在于组合物中的%NCO。
粘度
粘合剂组合物的粘度在25℃下使用具有6号转子的BrookfieldThermosel粘度计测定。
实例1
A部分如表1所示通过向反应器中加入DESMOPHENS-1011-210聚酯多元醇（宾夕法尼亚州匹兹堡拜耳公司(BayerCorporation,Pittsburg,Pa.)）然后加热到130℉而制备。在此工艺过程中自始至终使用氮气净化。然后将LUPRANATEMI单体2,4'-二苯基甲烷二异氰酸酯(MDI)（密歇根州怀恩多特巴斯夫公司(BASFCorporation,Syandotte,Mich.)）以足以实现2/1(NCO/OH)至2.5/1(NCO/OH)的化学计量NCO/OH比的量加入反应器。对混合物进行搅拌，将温度升至160℉至170℉。反应在一至两个小时内完成。定期检查%NCO，以确定反应是否完成，即是否得到目标%NCO。然后停止搅拌，将丙烯酸-2-羟乙酯(HEA)（密歇根州米德兰陶氏化学公司(DowChemicalCompany,Midland,Mich.)）加入反应器，将温度维持在160℉至170℉下进行反应。第二反应在1至2小时内完成。检查%NCO以确定反应是否完成。然后停止搅拌，将另外的LUPRANATEMI单体MDI加入反应器。然后重新开始搅拌并持续搅拌直到混合物均匀。
B部分通过合并97.45%羟值为约200的DESMOPHENXF-7395-200聚酯多元醇、0.05%的铋/锌盐（催化剂）和2.5%的DAROCUR1173光引发剂而制备。
在涂布之前立即将A部分与B部分混合，以提供1.4:1.0的NCO:OH化学计量比。
层合物1根据本文所述的搭接剪切强度和剥离粘附力测试方法通过将粘合剂组合物涂布到第一PET基底上然后将涂布的第一基底与第二基底层合而制备。之后，将层合物以100英尺每分钟的传输速度暴露于功率为300瓦的中压汞灯的辐射。
层合物2通过将粘合剂组合物涂布到第一PET基底上然后将第一基底上的涂布粘合剂以100英尺每分钟的传输速度暴露于功率为300瓦的中压汞灯的辐射而制备。之后，将具有部分固化的粘合剂组合物的第一基底与第二PET基底层合。
对层合物1和2根据本文所述的搭接剪切强度测试方法和剥离强度测试方法进行了测试，结果在下表2中示出。
实例2
除了以下方面，根据与实例1相同的工序制备了如表1所示的A部分、B部分、粘合剂组合物、层合物1和层合物2：在A部分中使用DESMODURN3600六亚甲基二异氰酸酯的单体均聚物代替LUPRANATEMI单体2,4'-二苯基甲烷二异氰酸酯(MDI)。
对层合物1和2根据本文所述的搭接剪切强度测试方法和剥离强度测试方法进行了测试，结果在下表2中示出。
实例3
除了以下方面，根据与实例1相同的工序制备了如表1所示的A部分、B部分、粘合剂组合物、层合物1和层合物2：在A部分中使用DESMODURW单体二环己甲烷二异氰酸酯代替LUPRANATEMI单体2,4'-二苯基甲烷二异氰酸酯(MDI)。
对层合物1和2根据本文所述的搭接剪切强度测试方法和剥离强度测试方法进行了测试，结果在下表2中示出。
表1实例1-3的A部分预聚物
实例1 实例2 实例3
DESMOPHEN S-1011-210 25.40 23.75
DESMOPHEN S-1011-55 10.24
LUPRANATE MI 35.50
DESMODUR N3600 43.71
DESMODUR W 36.71
2-HEA 8.60 8.83 8.13
第2次加入的异氰酸酯量
LUPRANATE MI 30.50
DESMODUR N3600 37.22
DESMODUR W 31.41
100.00% 100.00% 100.00%
最终%NCO 15.00% 15.50% 14.90%
表2
*n/t：未测试。

Claims (34)

1.一种制备电子组件的方法，包括：
将两部分双固化粘合剂组合物施加到第一基底的至少一部分上，所述粘合剂组合物包含含有可辐射聚合的多异氰酸酯预聚物的(A)部分和含有多元醇的(B)部分，其中将A部分和B部分合并以实现1:1至2:1的NCO基团与OH基团的化学计量比即NCO:OH；以及
使所述第一基底上的所述粘合剂与第二基底的至少一部分接触，所述第一和第二基底的至少一者在施加所述粘合剂组合物前包括至少一个电子元件。
2.根据权利要求1所述的方法，其中NCO基团与CO基团的化学计量比为1.2:1至1.6:1。
3.根据权利要求2所述的方法，其中NCO基团与CO基团的化学计量比为1.4:1。
4.根据权利要求1所述的方法，其中所述(A)部分还含有不能辐射聚合的异氰酸酯单体或异氰酸酯封端的预聚物。
5.根据权利要求1所述的方法，其中(A)部分或(B)部分还包含选自丙烯酸酯单体、丙烯酸酯聚合物以及它们的组合的可辐射聚合的组分。
6.根据权利要求1所述的方法，其中(A)部分或(B)部分还包含选自丙烯酸酯单体、丙烯酸酯低聚物以及它们的组合的可辐射聚合的组分。
7.根据权利要求1所述的方法，其中所述可辐射聚合的多异氰酸酯预聚物包含选自丙烯酸酯、烯基、苯乙烯以及它们的组合和衍生物的辐射官能团。
8.根据权利要求1所述的方法，其中所述可辐射聚合的多异氰酸酯预聚物包含可辐射聚合的化合物和脂族多异氰酸酯预聚物的反应产物。
9.根据权利要求1所述的方法，还包括在使所述第一基底上的所述粘合剂与所述第二基底接触之前或之后将所述粘合剂组合物暴露于辐射。
10.根据权利要求4所述的方法，其中所述异氰酸酯封端的预聚物为脂族异氰酸酯和多元醇的反应产物。
11.根据权利要求4所述的方法，其中所述异氰酸酯单体为脂族异氰酸酯。
12.根据权利要求1所述的方法，其中所述第一和第二基底具有相同或不同的材料并独立地选自聚乙烯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯以及它们的混合物。
13.根据权利要求1所述的方法，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、电池以及传感器。
14.根据权利要求13所述的方法，其中所述发光二极管是高亮度发光二极管。
15.根据权利要求13所述的方法，其中所述发光二极管是有机发光二极管。
16.根据权利要求1所述的方法，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、传感器以及太阳能电池。
17.根据权利要求1所述的方法，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、传感器以及光伏电池。
18.根据权利要求1所述的方法，其中所述粘合剂组合物还包含光引发剂。
19.一种电子组件，包括：
第一基底；
第二基底；
至少一个位于所述第一与第二基底之间的电子元件；以及
包含含有可辐射聚合的多异氰酸酯预聚物的(A)部分和含有多元醇的(B)部分的双固化反应产物的粘合剂组合物，其中将A部分和B部分合并以实现1:1至2:1的NCO基团与OH基团的化学计量比即NCO:OH，
所述第一基底的至少一部分通过所述粘合剂组合物粘结到所述第二基底的至少一部分。
20.根据权利要求19所述的组件，其中NCO基团与CO基团的化学计量比为1.2:1至1.6:1。
21.根据权利要求19所述的组件，其中NCO基团与CO基团的化学计量比为1.4:1。
22.根据权利要求19所述的组件，其中所述粘合剂组合物的(A)部分还包含异氰酸酯封端的预聚物或异氰酸酯单体。
23.根据权利要求19所述的组件，其中所述可辐射聚合的多异氰酸酯预聚物的所述辐射官能团选自丙烯酸酯、烯基、苯乙烯以及它们的混合物和衍生物。
24.根据权利要求19所述的组件，其中(A)部分或(B)部分还包含选自丙烯酸酯单体、丙烯酸酯聚合物以及它们的混合物的可辐射聚合的组分。
25.根据权利要求19所述的组件，其中(A)部分或(B)部分还包含选自丙烯酸酯单体、丙烯酸酯低聚物以及它们的混合物的可辐射聚合的组分。
26.根据权利要求19所述的组件，其中所述第一或第二基底具有相同或不同的材料并独立地选自聚乙烯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯以及它们的混合物。
27.根据权利要求19所述的组件，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、电池以及传感器。
28.根据权利要求27所述的组件，其中所述发光二极管是高亮度发光二极管。
29.根据权利要求27所述的组件，其中所述发光二极管是有机发光二极管。
30.根据权利要求19所述的组件，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、传感器以及太阳能电池。
31.根据权利要求19所述的方法，其中所述电子元件选自发光二极管、射频识别标签、电致变色显示器、电泳显示器、传感器以及光伏电池。
32.根据权利要求19所述的组件，其中所述异氰酸酯封端的预聚物为脂族异氰酸酯和多元醇的反应产物。
33.根据权利要求19所述的组件，其中所述粘合剂还包含光引发剂。
34.根据权利要求19所述的组件，其中所述粘合剂还包含选自以下的添加剂：抗氧化剂、增塑剂、增粘剂、粘附促进剂、非反应性树脂、紫外线稳定剂、催化剂、流变改性剂、杀生物剂、缓蚀剂、脱水剂、有机溶剂、着色剂、填充剂、表面活性剂、阻燃剂、蜡以及它们的组合。
CN201280036192.0A 2011-07-22 2012-07-19 用在电子器件上的两部分双固化粘合剂 Expired - Fee Related CN103687920B (zh)

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