CN101134878B - 切割管芯键合膜 - Google Patents

切割管芯键合膜 Download PDF

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CN101134878B
CN101134878B CN2007101477770A CN200710147777A CN101134878B CN 101134878 B CN101134878 B CN 101134878B CN 2007101477770 A CN2007101477770 A CN 2007101477770A CN 200710147777 A CN200710147777 A CN 200710147777A CN 101134878 B CN101134878 B CN 101134878B
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layer
thermosetting resin
tackiness agent
dicing
film
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CN101134878A (zh
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H·陈
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Abstract

切割管芯键合粘合膜，布置于半导体硅片和切割支承胶带之间，其包括与切割胶带接触的层-1粘合剂，和与硅半导体晶片接触的层-2粘合剂，其中层-2与硅片的粘着力高于层-1与切割胶带的粘着力至少0.1N/cm。

Description

切割管芯键合膜
本申请是于2004年4月1日提出的、现已放弃的美国序列号10/815,420的部分继续申请。
技术领域
本发明涉及多层粘合膜，其包括热塑性橡胶和热固性树脂的组合物，具体用作半导体封装中的切割管芯键合膜(dicing die bondingfilm)。
背景技术
一种将半导体管芯结合到衬底上的方法使用布置于管芯和衬底间的膜形式的管芯键合粘合剂。粘合膜在半导体硅片被锯成单独的芯片或管芯前被应用于该半导体硅片上。为了在切割过程中保护并支撑硅片，使粘合膜与称为切割胶带的胶带接触。应用于这种构造的粘合膜被称为“切割管芯键合”膜。因此，晶片、粘合膜和切割胶带装配被构建于晶片切割前。
粘合膜和切割胶带在晶片上的应用，在一种构建方法中实现，该方法是通过首先将粘合膜应用于晶片上，然后将切割胶带应用于粘合膜上。在第二种构建方法中，粘合膜首先被应用于切割胶带上，然后膜和胶带的组合体被应用于晶片上。
晶片被切割后，将贴有粘合剂的单独管芯从切割胶带上移走，并置于衬底上用于进一步加工处理。为了使管芯加上粘合剂的移除发生，粘合剂对晶片应比对切割胶带具有更高的粘着力。目前可用的切割管芯键合膜由单层粘合剂组成。为了实现贴有粘合剂的管芯从切割胶带上的剥离，粘合剂与硅管芯间的粘着力和粘合剂与切割胶带间的粘着力之间必须存在足够差异。这在目前的一种方法中，通过使用能被UV照射部分地或完全地固化的粘合剂而实现。粘合剂硬化，粘性降低，容易从切割胶带上移去。
将切割管芯键合膜在范围为室温到50℃和70,000到700,000Pa压力的条件下层压到半导体晶片上。高于50℃的层压温度——这是获得硅与目前可应用的材料之间的足够粘着通常所必需的，由于热应力引起晶片的显著变形。高温也能引起粘合剂与切割胶带粘结过强，导致当其被拾取用于后续装配步骤时，被拉离硅管芯。但是，当使用低于50℃温度时，结果通常是不能充分粘连到硅管芯上，导致当管芯被拾取时，粘合膜留在切割胶带上。
通过提供一种多层膜，本发明是上述问题的解决方案，该多层膜在层压温度下对硅片和切割胶带提供不同的粘着水平，所述层压温度不会引起晶片变形或阻碍管芯和粘合剂从切割胶带上剥离。
附图说明
图1表示本发明切割管芯键合膜与现有技术的单层管芯附着膜(die attach film)的比较。图2表示本发明切割管芯键合膜与现有技术的单层管芯附着膜当层压到晶片上时的比较。图3描述了利用本发明的不需UV固化的切割管芯键合膜与利用现有技术的需要UV固化的单层管芯附着膜的过程比较。
发明内容
本发明是应用于半导体硅片的切割管芯键合粘合膜，其中粘合膜被置于半导体硅片和切割支承胶带之间。粘合膜包括(a)层-1粘合剂，将与切割胶带接触，和(b)层-2粘合剂，将与硅半导体晶片接触，其中层2与硅片的粘着力高于层1与切割胶带的粘着力至少0.1N/cm。应用此粘着力差异消除对UV照射以固化接触切割胶带的粘合剂的需求，并使其被剥离。适合的切割胶带是聚烯烃和聚氯乙烯膜，如来自Lintec公司以商标AdwillG-64出售的那些，或来自Nitto Denko以商标Elepholder V-8-T出售的那些。其它商业可获得的及适合的切割胶带是那些由聚酯或聚酰亚胺构成的切割胶带。
在一种实施方式中，层1粘合剂对切割胶带具有的特征剥离强度在0.05到0.5N/cm以下的范围内，层2粘合剂对硅片具有的特征剥离强度为0.5N/cm或更高，条件是在两种粘着力数值间存在至少0.1N/cm的差异。多层膜使得对切割管芯键合过程中所遇材料的粘着专用化。
在另一种实施方式中，本发明是切割支承胶带、包括层-1粘合剂和层-2粘合剂的粘合膜以及半导体晶片的装配，其中层-1粘合剂紧邻切割支承胶带，层-2粘合剂紧邻半导体晶片；其特征在于层2对硅片的粘着力高于层1对切割胶带的粘着力至少0.1N/cm。在进一步的实施方式中，层1粘合剂对切割胶带具有的特征剥离强度在0.05到0.5N/cm以下的范围内，而层2粘合剂对硅片具有的特征剥离强度为0.5N/cm或更高，条件是在两个粘着力数值间存在至少0.1N/cm的差异。
具体实施方式
层-1可以是任何粘合剂组合物，其对切割胶带具有的特征剥离强度在0.05到0.5N/cm以下的范围内，且可被层压到层-2上。层-2可以是任何粘合剂组合物，其对硅晶片具有0.5N/cm或更高的特征剥离强度，并可被层压到层-1上。在一些情况下，超出上述范围是可能的，条件是总是存在至少0.1N/cm的剥离强度差值。尽管任何符合上述剥离强度和层压标准的粘合剂可以被使用，但层-1和层-2的适当的配方将包括(a)热塑性橡胶，(b)热固性树脂，(c)硬化剂，(d)促进剂，和(e)填料，其中层1的热固性树脂将具有60℃以上的软化点，层2的热固性树脂将具有60℃以下的软化点。在本说明书中，材料的软化点被定义为其熔点(Tm)或玻璃化转变温度(Tg)。此实施方式的典型重量百分比范围是30-85wt％热塑性橡胶、15-70wt％热固性树脂、0.05-40wt％硬化剂、0.01-10wt％促进剂和1-55wt％填料。
在层-1的进一步的实施方式中，热固性树脂将是固体环氧树脂，其软化点为60℃以上，且具有100到1000的环氧当量(weight per epoxyequivalent，WPE)。适合的固体环氧树脂包括双酚A、双酚F、线型酚醛树脂或甲酚-线型酚醛(cresol novolac)，这些可从Shell Chemicals以及Dainippon Ink and Chemicals，Inc商业获得。
在层-2的进一步的实施方式中，热固性树脂将是环氧树脂，如，双酚A环氧树脂、双酚F环氧树脂、线型酚醛环氧树脂(phenol novolacepoxy)或甲酚-线型酚醛环氧树脂(cresol novolac epoxy)，并具有100到1000的环氧当量(WPE)，和60℃以下的软化点。这些环氧树脂可从可从Shell Chemicals以及Dainippon Ink and Chemicals，Inc商业获得。
在层-2的进一步的实施方式中，热固性树脂的组合物可被使用，在此种情况下，总热固性树脂的至少20％应具有60℃以下的软化点。除环氧树脂的组合物之外，其它适于层-2的热固性树脂包括马来酰亚胺、丙烯酸酯、乙烯基醚和聚丁二烯，其分子中具有至少一个双键。
适合的马来酰亚胺树脂包括那些具有一般结构
Figure G071E7777020070904D000041
的树脂，其中n为1到3，X1为脂族基或芳基。示例性X1实体包括聚丁二烯、聚碳酸酯、聚氨酯、聚醚、聚酯、简单烃类和含官能团的简单烃类，所含官能团如羰基、羧基、酰胺、氨基甲酸酯、脲或醚。这些类型的树脂是商业可得的，并可从，例如，National Starch and ChemicalCompany和Dainippon Ink and Chemical，Inc获得。在一种实施方式中，马来酰亚胺树脂选自：
Figure G071E7777020070904D000042
其中C36表示36个碳原子的直链或支链(含或不含环状部分)；
Figure G071E7777020070904D000043
Figure G071E7777020070904D000044
Figure G071E7777020070904D000045
适合的丙烯酸酯树脂包括那些具有一般结构
Figure G071E7777020070904D000051
的树脂，其中n为1到6，R1为-H或-CH3，X2为芳基或脂族基。示例性X2实体包括聚丁二烯、聚碳酸酯、聚氨酯、聚醚、聚酯、简单烃类和含官能团的简单烃类，所含官能团如羰基、羧基、酰胺、氨基甲酸酯、脲或醚。商业可得的材料包括(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸-正十二烷基酯、(甲基)丙烯酸-烷基酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸-正十八酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸-2-苯氧基乙酯、(甲基)丙烯酸异冰片酯、1，4-丁二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸(1，6己二醇)酯、1，9-壬二醇二(甲基)丙烯酸酯、(甲基)丙烯酸全氟辛基乙酯(perfluorooctylethyl(meth)acrylate，)、1，10癸二醇二(甲基)丙烯酸酯(1，10 decandiol di(meth)acrylate)、(甲基)丙烯酸壬基酚聚丙氧酯(nonylphenol polypropoxylate(meth)acrylate)和聚戊氧基化物丙烯酸四氢糠酯(polypentoxylate tetrahydrofurfuryl acrylate)，可从Kyoeisha Chemical Co.，LTD获得；聚丁二烯聚氨酯二甲基丙烯酸酯(polybutadiene urethane dimethacrylate)(CN302，NTX6513)和聚丁二烯二甲基丙烯酸酯(CN301，NTX6039，PRO6270)，可从SartomerCompany，Inc获得；聚碳酸酯聚氨酯二丙烯酸酯(polycarbonate urethanediacrylate)(ArtResin UN9200A)，可从Negami Chemical Industries Co.，LTD获得；丙烯酸化的脂族氨基甲酸乙酯低聚物(acrylated aliphaticurethane oligomers)(Ebecryl 230，264，265，270，284，4830，4833，4834，4835，4866，4881，4883，8402，8800-20R，8803，8804)，可从RadcureSpecialities，Inc获得；聚酯丙烯酸酯低聚物(polyester acrylate oligomers)(Ebecryl 657，770，810，830，1657，1810，1830)，可从RadcureSpecialities，Inc获得；和环氧丙烯酸酯树脂(epoxy acrylate resins)(CN104，111，112，115，116，117，118，119，120，124，136)，可从Sartomer Company，Inc获得。在一种实施方式中，丙烯酸酯树脂选自丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、具有丙烯酸酯官能度的聚丁二烯和具有甲基丙烯酸酯官能度的聚丁二烯。
适合的乙烯基醚树脂包括那些具有一般结构的树脂，其中n为1到6，X3为芳基或脂族基。示例性的X3实体包括聚丁二烯、聚碳酸酯、聚氨酯、聚醚、聚酯、简单烃类和含官能团的简单烃类，所含官能团如羰基、羧基、酰胺、氨基甲酸酯、脲或醚。商业可得的树脂包括环己烷二甲醇二乙烯基醚(cyclohenanedimethanoldivinylether)、十二烷基乙烯基醚、环己基乙烯基醚、2-乙基己基乙烯基醚、双丙甘醇二乙烯基醚(dipropyleneglycol divinylether)、己二醇二乙烯醚(hexanediol divinylether)、十八烷基乙烯基醚和丁二醇二乙烯醚(butandiol divinylether)，可从International Speciality Products(ISP)获得；Vectomer 4010、4020、4030、4040、4051、4210、4220、4230、4060、5015，可从Sigma-Aldrich，Inc获得。
适合的聚丁二烯树脂包括聚丁二烯、环氧化聚丁二烯、顺丁烯二酸聚丁二烯(maleic poly(butadienes))、丙烯酸化聚丁二烯(acrylatedpoly(butadienes))、丁二烯-苯乙烯共聚物和丁二烯-丙烯腈共聚物。商业可获得材料包括丁二烯均聚物(Ricon130，131，134，142，150，152，153，154，156，157，P30D)，可从Sartomer Company，Inc获得；丁二烯和苯乙烯的无规共聚物(Ricon 100，181，184)，可从Sartomer Company Inc获得；顺丁烯二酸化聚丁二烯(Ricon 130MA8，130MA13，130MA20，131MA5，131MA10，131MA17，131MA20，156MA17)，可从SartomerCompany，Inc获得；丙烯酸化聚丁二烯(CN302，NTX6513，CN301，NTX6039，PRO6270，Ricacryl 3100，Ricacryl 3500)，可从Sartomer Inc获得；环氧化聚丁二烯(Polybd 600，605)，可从Sartomer Company.Inc.获得；及Epolead PB3600，可从Daicel Chemical Industries，Ltd获得；以及丙烯腈和丁二烯的共聚物(Hycar CTBN系列，ATBN系列，VTBN系列and ETBN系列)，可从Hanse Chemical获得。
对于层-1或者层-2，热塑性橡胶将以30-85wt％的含量存在；适合的热塑性橡胶包括以羧基封端的丁腈(butadiene-nitrile)(CTBN)/环氧加合物和丁腈橡胶(NBR)。CTBN环氧加合物由约20-80wt％CTBN和约20-80wt％双酚A二环氧甘油醚：双酚A环氧树脂(DGEBA)组成。CTBN将具有范围为约100到1000的分子量，而DGEBA将具有范围为约500到5000的当量(或每环氧重量，g/环氧)。最终加合物将具有约500到5000g/环氧的当量和150℃时5000到100,000cP的熔体粘度。多种CTBN材料可从Noveon Inc获得，多种双酚A环氧树脂材料可从Dainippon Ink and Chemicals，Inc.以及Shell Chemicals获得。NBR由范围在20-25wt％的丙烯腈和范围在50-80wt％的丁二烯组成，并具有从-40℃到+20℃的玻璃化转化温度(Tg)和100,000到1,000,000的分子量(Mw)。这种类型的NBR橡胶可从Zeon Corporation商业获得。
层-1或层-2的硬化剂将以0.5到40wt％的含量存在；适合的硬化剂包括酚醛塑料、芳族二胺、双氰胺和聚酰胺。适合的酚醛塑料具有90到110的OH值和60到110℃的软化点，可从Schenectadyinternational，Inc商业获得。适合的芳族二胺是伯二胺(primarydiamines)，包括二氨基二苯砜和二氨基二苯甲烷，可从Sigma-AldrichCo商业获得。适合的双氰胺可从SKW Chemicals，Inc获得。适合的聚酰胺可从Air Products and Chemicals，Inc商业获得。
层-1或层-2的促进剂将以0.01到10wt％的含量存在；合适的促进剂包括咪唑或叔胺。适合的咪唑可从Air Products and Chemicals，Inc商业获得。合适的叔胺可从Sigma-Aldrich Co商业获得。
层-1或层-2的填料具有0.1到10μm的粒子大小，并将以1到80wt％的含量存在。根据最终应用，填充剂可以是导电或导热的或非传导的。适合的传导性填料的例子包括银、铜、金、钯、铂、镍、铝和炭黑。非传导性填料包括氧化铝、氢氧化铝、硅土、蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙子、玻璃、硫酸钡和卤化乙烯聚合物，如四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。
也可添加其它填料，如助粘剂，使用技术领域中已知的类型和量。
此膜构建将在切割管芯键合膜的商业上可接受的范围内进行，其对切割胶带具有的特征剥离强度在0.05到0.5N/cm以下的范围内，而对晶片的特征剥离强度为0.5N/cm或更高。在商业上可接受的条件下，即25℃到50℃温度和70,000到700,000Pa压力，该膜能够被层压到半导体晶片上。
实施例
在下列实施例中，制备了四个切割管芯键合膜，并比较其粘着于硅片后的性能。实施例1和2为本发明的两层膜，实施例3和4为对比的单层膜。实施例5展示了性能结果和测试方法。
实施例1.膜A
通过将下列重量份(pbw)的成分混合于足量的丁酮中而形成糊状物，制备层1(用于粘着至切割胶带)：60pbw环氧改性的CTBN(Mn：15015，Tg：-17℃)；29pbw甲酚-线型酚醛环氧树脂(环氧当量：220，软化点：90℃)；7pbw 3，3′二氨基二苯砜，1pbw 2-苯基4-甲基咪唑，3pbw硅土填料(平均大小：0.5μm)糊状物被涂在50μm厚的防粘涂布聚酯膜(release-coated polyesterfilm)上，并在90℃干燥5分钟而形成膜A，10μm厚的层1。
通过将下列重量份(pbw)的成分混合于足量丁酮中而形成糊状物，制备用于粘着至硅片的层2：60pbw环氧改性的CTBN(Mn：15015，Tg：-17℃)，30pbw双酚F环氧树脂(环氧当量：290，软化点：4℃，粘性：50℃时，35,000mPaS)，6pbw 3，3′二氨基二苯砜，1pbw 2-苯基4-甲基咪唑，3pbw硅土填料(平均大小：0.5μm)此糊状物被涂于50μm厚的防粘涂布聚酯膜上，并在90℃干燥5分钟而形成膜A，15μm厚的层2。
利用覆膜机(roll laminator)，在80℃和0.21MPa下，将两层相互层压，并将层压膜切割成直径为220mm的圆形。将层1的剥离衬垫剥去，并将切割胶带(AdwillG-64，从Lintec Corporation商业获得)在室温和0.21MPa的压力下层压到层1的表面上。
实施例2.膜B
通过将下列重量份(pbw)的成分混合于足量的丁酮中而形成糊状物，制备层1(用于粘着至切割胶带)：60pbw环氧改性的CTBN(Mn：15015，Tg：-17℃)；29pbw甲酚-线型酚醛环氧树脂(环氧当量：220，软化点：90℃)；7pbw 3，3′二氨基二苯砜，1pbw 2-苯基4-甲基咪唑，3pbw硅土填料(平均大小：0.5μm)此糊状物被涂于50μm厚的防粘涂布聚酯膜上，并在90℃干燥5分钟而形成13μm厚的层1。
通过将下列重量份(pbw)的成分混合于足量的丁酮中而形成糊状物，制备用于粘着至硅片的层2：25pbw羧化丙烯腈丁二烯共聚物橡胶(carboxylatedacrylonitrile butadiene copolymer rubber)(Mw：350,000，丙烯腈含量：27wt％，Tg：-20℃)，15pbw乙烯基封端的丁腈橡胶(丙烯腈含量：21.5％，Tg：-45℃)，20pbw 4，4′-双马来酰亚胺-二苯基-甲烷(4，4`-bismaleimido-diphenyl-methane)，25pbw三环癸烷-二甲醇和3-异丙烯基-二甲基苄基异氰酸酯的加合物，5pbw过氧化二枯基10pbw硅土填料(平均大小：0.5μm)此糊状物被涂于50μm厚的防粘涂布聚酯膜上，并在90℃干燥5分钟而形成12μm厚的层2。
利用覆膜机，在80℃和0.21MPa下，将两层相互层压，并将层压膜切割成直径为220mm的圆形。将层1的剥离衬垫剥去，并将切割胶带(Adwill
Figure G071E7777020070904D000092
G-64)在室温和0.21MPa的压力下层压到层1的表面上。
对比实施例3.膜C
通过将下列重量份(pbw)的成分混合于丁酮中而形成糊状物，制备膜C；60pbw环氧改性的CTBN(Mn：15015，Tg：-17℃)；29pbw甲酚-线型酚醛环氧树脂(环氧当量：220，软化点：90℃)；7pbw 3，3′二氨基二苯砜，1pbw 2-苯基4-甲基咪唑，3pbw硅土填料(平均大小：0.5μm)此糊状物被涂于50μm厚的防粘涂布聚酯膜上，并在90℃干燥5分钟而形成25μm厚的膜C。将该膜的剥离衬垫剥去，并将切割胶带(Adwill
Figure G071E7777020070904D000101
G-64)在室温和0.21MPa的压力下层压到其表面上。
对比实施例4.膜D
通过将下列重量份(pbw)的成分混合于丁酮中而形成糊状物，制备膜D；25pbw羧化丙烯腈丁二烯共聚物橡胶(Mw：350,000，丙烯腈含量：27wt％，Tg：-20℃)，15pbw乙烯基封端的丁腈橡胶(丙烯腈含量：21.5％，Tg：-45℃)，20pbw 4，4′-双马来酰亚胺-二苯基-甲烷，25pbw三环癸烷-二甲醇和3-异丙烯基-二甲基苄基异氰酸酯的加合物，5pbw过氧化二枯基，10pbw硅土填料(平均大小：0.5μm)此糊状物被涂于50μm厚的防粘涂布聚酯膜上，并在90℃干燥5分钟而形成25μm厚的膜D。将该膜的剥离衬垫剥去，并将切割胶带(Adwill
Figure G071E7777020070904D000102
G-64)在室温和0.21MPa的压力下层压到起表面上。
实施例5.性能及测试方法
在多个温度下，将膜A到D的每一个和商业可得的单层粘合带(膜H)层压到硅片上，并测定90°剥离强度。此测试的结果表示在表1中。
Figure G071E7777020070904D000111
结果表明，在所有测试的层压温度下，对于良好切割和管芯拾取性能而言，多层膜A和B都提供了可接受的剥离强度，对切割胶带的剥离强度在0.05到0.5N/cm以下之间，对硅片在0.5到10N/cm之间。对比膜C在所有层压温度下，对切割胶带具有在可接受范围内的剥离强度；但是，其对硅片的粘着力在低于50℃的商业要求的层压温度下，是不可接受的。对比膜D在所有层压温度下，对硅片具有在可接受范围内的剥离强度；但是，在所有测试条件下，其对切割胶带的粘着力都过高。对比的商业膜H对切割胶带具有良好的粘着，但在50℃以下的温度下，其对硅片的粘着不足。
通过首先从切割胶带移除剥离衬垫，以及从待测试的膜移除剥离衬垫，制备样本，用于对切割胶带剥离强度的测试。两个膜随后在室温和0.21MPa压力下被层压到一起，并切割成10mm宽的条。将剥离衬垫从膜的剩余的、暴露面移除，并随后在适当的测试温度下将层压结构(切割胶带加膜)层压到载波片上，切割胶带在上，膜贴着玻璃。剥离用手起动。
通过在待测试的指定温度下，首先从待测试的膜移除剥离衬垫，并将其层压到硅片上，制备样本，用于对硅片剥离强度的测试。然后，对管芯附着膜具有20N/cm以上剥离强度的压敏粘合剂(PSA)在室温和0.21MPa压力下被用于膜上。然后，切割10mm宽的膜加PSA部分(同时粘附至晶片)，并用手起动样本的剥离。
使用Imada SV-52N剥离测试仪，在室温下测试90度下的剥离强度，剥离速度为50mm/min。结果被汇总并求平均值。

Claims (9)

1.切割管芯键合膜在结合半导体硅片至切割支承胶带的方法中的应用，所述切割管芯键合膜包括：
层-1粘合剂，将与所述切割支承胶带接触，和
层-2粘合剂，将与所述半导体硅片接触，
其中所述层-2对硅片的粘着力高于所述层-1对切割胶带的粘着力至少0.1N/cm，
其中所述应用包括在不使所述膜暴露于紫外线照射的情况下使所述膜从所述切割支承胶带上剥离。
2.权利要求1所述的应用，其中所述层-1粘合剂对切割胶带具有的特征剥离强度在0.05到0.5N/cm以下的范围内，所述层-2粘合剂对半导体硅片具有的特征剥离强度为0.5N/cm或更高。
3.权利要求1所述的应用，其中所述层-1粘合剂包括(a)热塑性橡胶、(b)软化点为60℃以上的热固性树脂、(c)硬化剂、(d)促进剂和(e)填料；其中所述层-2粘合剂包括(a)热塑性橡胶、(b)热固性树脂，其中所述热固性树脂的至少20％具有60℃以下的软化点、(c)硬化剂、(d)促进剂和(e)填料。
4.权利要求3所述的应用，其中所述层-1粘合剂包括(a)30-85wt％热塑性橡胶，(b)15-70wt％热固性树脂，其具有60℃以上的软化点，(c)0.05-40wt％硬化剂，(d)0.01-10wt％促进剂，和(e)1-55wt％填料，所述层-2粘合剂包括(a)30-85wt％热塑性橡胶，(b)15-70wt％热固性树脂，其中所述热固性树脂的至少20％具有60℃以下的软化点，(c)0.05-40wt％硬化剂，(d)0.01-10wt％促进剂，和(e)1-55wt％填料。
5.权利要求3所述的应用，其中层-1中的所述热固性树脂是固体环氧树脂，其具有60℃以上的软化点和100到1000的环氧当量。
6.权利要求3所述的应用，其中层-2中的所述热固性树脂是环氧树脂，其具有60℃以下的软化点和100到1000的环氧当量。
7.权利要求3所述的应用，其中层-2中的所述热固性树脂是热固性树脂的混合物，且全部层-2热固性树脂的至少20％具有60℃以下的软化点。
8.权利要求3所述的应用，其中所述热塑性橡胶是羧基封端的丁腈/环氧加合物和丁腈橡胶。
9.权利要求8所述的应用，其中所述羧基封端的丁腈/环氧加合物由20-80wt％羧基封端的丁腈和20-80wt％的双酚A二环氧甘油醚组成。
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