CN113748180B - 粘合胶带 - Google Patents

粘合胶带 Download PDF

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Publication number
CN113748180B
CN113748180B CN202080032230.XA CN202080032230A CN113748180B CN 113748180 B CN113748180 B CN 113748180B CN 202080032230 A CN202080032230 A CN 202080032230A CN 113748180 B CN113748180 B CN 113748180B
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Prior art keywords
acrylic resin
adhesive tape
resin
meth
acrylate
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CN113748180A (zh
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阿部宪明
佐藤信之
吉原裕美
太刀川透
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Arisawa Mfg Co Ltd
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Arisawa Mfg Co Ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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Abstract

本发明涉及粘合胶带，其具有包含酸值为30～100mgKOH/g的第1丙烯酸树脂、和酸值为0～10mgKOH/g的第2丙烯酸树脂的粘合层，前述粘合胶带中，前述第1丙烯酸树脂与前述第2丙烯酸树脂的比例为第1丙烯酸树脂：第2丙烯酸树脂＝85：15～65：35，前述第1丙烯酸树脂与第2丙烯酸树脂具有半互穿聚合物网络结构。

Description

粘合胶带
技术领域
本发明涉及主要用于半导体器件的制造的粘合胶带。
背景技术
在LSI的安装技术中，CSP(Chip Size/Scale Package，芯片尺寸封装)技术受到关注，其中，关于由QFN(Quad Flat Non-leaded package，四侧无引脚扁平封装)代表的将引线端子引入至封装内部的形态的封装，在小型化和高集成的方面是有利的。作为这样的QFN的制造方法，采用了下述方法：将多个QFN用半导体芯片排列在引线框的封装图案区域的芯片焊盘上，在模具的模腔内用密封树脂一并密封之后，切分成独立的QFN结构物，由此提高引线框每单位面积的生产率。
在如上所述的将多个半导体芯片一并密封的QFN的制造方法中，树脂密封时由注塑模具所夹的区域仅为已扩展至比封装图案区域更靠外侧位置的树脂密封区域的更外侧的区域。因此，容易发生如下问题：密封树脂漏出至引线框背面，因由模制树脂产生的毛刺而导致连接不良，QFN的端子等被树脂被覆。因此认为，在QFN的制造方法中，在引线框的背面侧贴附耐热性的粘合胶带、通过利用了该粘合胶带的自粘力(遮蔽)的密封效果来防止树脂密封时的向引线框背面侧的树脂泄漏是有效的。
在这样的制造方法中，采用了下述方法：在引线框上搭载半导体芯片后，或者在实施引线接合后开始进行粘合胶带的贴合的方法；在最初的阶段将粘合胶带贴合于引线框的背面(外部焊盘(outerpad)面)，其后，经由半导体芯片的搭载工序、引线接合工序，进行基于密封树脂的密封工序的方法。此时，提出了可以使用具有粘合剂层的耐热性粘合胶带、在防止树脂泄漏的同时实施引线接合等一系列工序的制造方法(参见专利文献1)。
另外，在专利文献2中，公开了在粘合剂成分中添加脱模剂成分而得到的耐热性粘合胶带，并报道了由此能够适宜地防止密封工序中的树脂泄漏，而且由于粘合剂层中包含脱模剂，因此能够容易地进行密封工序后的剥离，可抑制由剥离应力导致的经注塑的树脂的剥离、破损。
现有技术文献
专利文献
专利文献1：日本特开2002-184801号公报
专利文献2：日本特开2010-157752号公报
发明内容
发明所要解决的课题
在QFN中使用的引线框为PPF(pre-plated leadframe，预镀引线框)的情况下，不能进行将粘合胶带剥离后的物理研磨。即，在PPF的情况下不能进行机械清洗，因此存在如下问题：由于目视无法辨别的纳米水平的粉浆残留，引起焊料不附着等特性恶化、由变色导致的成品率恶化。
就这一点而言，在使用有机硅树脂作为粘合胶带的粘合层的情况下，存在容易受到热分解、在密封工序后产生由硅氧烷气体造成的污染这样的问题。另外，在使用丙烯酸树脂作为粘合层的情况下，虽然能够通过充分进行交联反应来防止污染，但为了抑制由模制树脂产生的毛刺所需要的密封工序中的密合力降低。
另外，专利文献2中公开的粘合胶带虽然密合性良好，但另一方面，从同时实现密合性和对粉浆残留的防止这样的观点考虑，尚不能说是充分的。
本发明是鉴于上述情况而作出的，其目的在于提供同时实现了密合性和耐污染性的粘合胶带，其防止密封工序中的模制树脂毛刺，并且不发生胶带剥离工序中的粉浆残留。
用于解决课题的手段
本申请的发明人为了解决上述课题而进行了深入研究，结果发现，以特定比例包含具有特定范围的酸值的至少2种丙烯酸树脂、并且具有半互穿聚合物网络结构的粘合胶带能够解决上述课题，从而完成了本发明。
即，本发明如下所述。
[1]
粘合胶带，其具有包含酸值为30～100mgKOH/g的第1丙烯酸树脂、和酸值为0～10mgKOH/g的第2丙烯酸树脂的粘合层，前述粘合胶带中，
前述第1丙烯酸树脂与前述第2丙烯酸树脂的比例为第1丙烯酸树脂：第2丙烯酸树脂＝85：15～65：35，
前述第1丙烯酸树脂与第2丙烯酸树脂具有半互穿聚合物网络结构。
[2]
如上述[1]所述的粘合胶带，其中，前述第1丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下，前述第2丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下。
[3]
如上述[1]或[2]所述的粘合胶带，其中，前述第1丙烯酸树脂的重均分子量(Mw)为40～100万，前述第2丙烯酸树脂的重均分子量(Mw)为40～80万。
[4]
如上述[1]～[3]中任一项所述的粘合胶带，其中，前述粘合层还含有固化剂，前述粘合胶带是利用前述固化剂使前述第1丙烯酸树脂固化而得到的。
[5]
如上述[4]所述的粘合胶带，其中，前述固化剂为环氧树脂。
[6]
如上述[4]或[5]所述的粘合胶带，其中，前述固化剂的含量相对于前述第1丙烯酸树脂而言为0.4～0.6当量。
[7]
如上述[1]～[6]中任一项所述的粘合胶带，其中，前述粘合层还含有固化催化剂。
[8]
如上述[1]～[7]中任一项所述的粘合胶带，其用于半导体器件的制造。
发明的效果
根据本发明，能够提供同时实现了密合性和耐污染性的粘合胶带，其防止密封工序中的模制树脂毛刺，并且不发生胶带剥离工序中的粉浆残留。
附图说明
[图1]为示出使用本发明的粘合胶带的半导体器件的制造方法的一个例子的工序图。
具体实施方式
以下，对本发明的具体实施方式(以下，简称为“本实施方式”。)进行详细说明。以下的本实施方式是用于对本发明进行说明的示例，并非旨在将本发明限定于以下内容。本发明可以在其主旨的范围内适当地进行变形而实施。需要说明的是，本说明书中，只要没有特别说明，则“(甲基)丙烯酸”是指“丙烯酸”及/或“甲基丙烯酸”，同样地，“(甲基)丙烯酰基”是指“丙烯酰基”及/或“甲基丙烯酰基”，“(甲基)丙烯酸酯”是指“丙烯酸酯”及/或“甲基丙烯酸酯”，所谓“固化”，不仅包括完全固化，而且也包括半固化。
本实施方式的粘合胶带具有包含酸值为30～100mgKOH/g的第1丙烯酸树脂、和酸值为0～10mgKOH/g以下的第2丙烯酸树脂的粘合层，前述粘合胶带中，前述第1丙烯酸树脂与前述第2丙烯酸树脂的比例为第1丙烯酸树脂：第2丙烯酸树脂＝85：15～65：35，前述第1丙烯酸树脂与第2丙烯酸树脂具有半互穿聚合物网络结构。
本实施方式的粘合胶带的粘合层中包含的第1丙烯酸树脂与第2丙烯酸树脂具有半互穿聚合物网络结构。此处，所谓“互穿聚合物网络”，是具有不同种类的交联聚合物网络彼此相互侵入而成的网络结构的混合物，作为简称，也称为IPN(InterpenetratingPolymer Network)。本实施方式的半互穿聚合物网络结构(半IPN)是指下述结构：一种成分为直链状(或大致直链状)，另一种成分为交联聚合物网络状，直链状的丙烯酸树脂的一部分或全部侵入至交联聚合物网络状的另一种丙烯酸树脂之间。
本实施方式的粘合胶带通过具有上述结构，从而在第1丙烯酸树脂的交联聚合物网络结构内保持有第2丙烯酸树脂，因此，能够防止由第2丙烯酸树脂的漏出导致的粉浆残留。另外，由于第2丙烯酸树脂未交联或者交联密度低，所以能够提高高温时的密合力，因此，能够抑制由密封树脂的漏出导致的树脂毛刺。
[丙烯酸树脂]
作为本实施方式的粘合胶带中包含的丙烯酸树脂，可举出例如包含(甲基)丙烯酸酯和不饱和羧酸作为结构单元的共聚物，优选为包含(甲基)丙烯酸酯和不饱和羧酸作为结构单元、并且在侧链具有羧基和(甲基)丙烯酰基的共聚物。
作为具有不饱和羧酸的单体，可举出例如(甲基)丙烯酸、巴豆酸、马来酸、衣康酸等。在丙烯酸树脂为包含(甲基)丙烯酸酯和(甲基)丙烯酸作为结构单元的共聚物的情况下，可以使用2种以上的(甲基)丙烯酸酯，作为(甲基)丙烯酸，可以使用甲基丙烯酸和丙烯酸这2种。
作为上述的丙烯酸树脂，具有羧基及乙烯性不饱和键即可，例如可举出至少包含下述物质中的任一者作为单体的丙烯酸树脂等：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十四烷基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸异硬脂基酯等(甲基)丙烯酸烷基酯；(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-3-羟基丙酯等(甲基)丙烯酸羟基烷基酯；丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-甲基甲基丙烯酰胺等丙烯酰胺类；单甲基氨基乙基、单乙基氨基乙基、单甲基氨基丙基、单乙基氨基丙基等的丙烯酸单烷基氨基酯。
这些之中，从在相对于被粘物的贴附性、初始的追随性等方面更优异这样的观点考虑，优选为包含(甲基)丙烯酸正丁酯及/或(甲基)丙烯酸-2-乙基己酯的丙烯酸树脂。需要说明的是，只要在不损害本实施方式的效果的范围内，则也可以进一步包含羟基、氨基、酰胺基等官能团。
丙烯酸树脂可以还含有除上述的(甲基)丙烯酸酯、不饱和羧酸以外的结构单元。
本实施方式中的粘合片材的粘合层包含酸值高的第1丙烯酸树脂、和酸值低的第2丙烯酸树脂。酸值高的第1丙烯酸树脂通过利用固化剂进行交联而形成交联密度大的聚合物网络结构。另一方面，酸值低的第2丙烯酸树脂即使在利用固化剂进行了交联的情况下，交联密度也低，呈直链状或大致直链状。
第1丙烯酸树脂的酸值为30～100mgKOH/g，优选为45～80mgKOH/g。在第1丙烯酸树脂的酸值低于30mgKOH/g的情况下，交联密度不充分，发生由低分子量成分的漏出导致的污染的风险变高。另一方面，若酸值大于100mgKOH/g，则未反应的酸性官能团与密封树脂进行反应，在加工后重剥离化的风险变高。
第2丙烯酸树脂的酸值为0～10mgKOH/g，优选为0～5mgKOH/g。第2丙烯酸树脂的酸值特别优选为0mgKOH/g，但只要在发挥本申请发明的效果的范围内，则第2丙烯酸树脂的酸值也可以大于0mgKOH/g，在该情况下，第2丙烯酸树脂可以与后述的固化剂反应。作为第2丙烯酸树脂的酸值的上限，若大于10mgKOH/g，则高温时的与引线框(外部焊盘面)的密合力降低，产生树脂毛刺的风险变高。
酸值可以按照后述的实施例中记载的方法来测定。
关于丙烯酸树脂的重均分子量(Mw)，没有特别限定，但优选第1丙烯酸树脂的重均分子量(Mw)、与第2丙烯酸树脂的重均分子量(Mw)之差为0～40万。第1及第2丙烯酸树脂的重均分子量之差在上述范围内的情况下，两者的相容性提高，有本申请发明所发挥的效果变得更显著的倾向。
从密合力的观点考虑，第1丙烯酸树脂的重均分子量优选为40～100万，更优选为60～90万。
从耐污染性的观点考虑，第2丙烯酸树脂的重均分子量优选为40～80万。
关于丙烯酸树脂的分子量分布，优选第1丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下，第2丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下。第1及第2丙烯酸树脂的分子量分布在上述范围内的情况下，在第1丙烯酸树脂的聚合物网络结构的内部充分且稳定地保持有第2丙烯酸树脂，有本申请发明所发挥的效果变得更显著的倾向。
本实施方式的粘合胶带的粘合层中包含的第1丙烯酸树脂与第2丙烯酸树脂的比例为第1丙烯酸树脂：第2丙烯酸树脂＝85：15～65：35，更优选为80：20～70：30。若粘合层中包含的第1丙烯酸树脂的比例过高，则由于高温时的密合性不充分而产生由密封工序中的模制树脂形成的毛刺的风险增高。另一方面，若粘合层中包含的第2丙烯酸树脂的比例过高，则发生胶带剥离工序中的粉浆残留，半导体器件被污染的风险增高。
[丙烯酸树脂的制造方法]
丙烯酸树脂的制造方法没有特别限定，可以使用以往已知的方法等。例如，在酸值高的第1丙烯酸树脂的制造中可以采用游离基聚合，在酸值低的第2丙烯酸树脂的制造中可以采用活性自由基聚合。
[固化剂]
对于本实施方式中的粘合胶带而言，粘合层可以还含有固化剂，前述粘合胶带是利用前述固化剂使第1丙烯酸树脂固化而得到的。第2丙烯酸树脂可以利用固化剂进行固化，也可以不进行固化，但从密合性的观点考虑，优选不进行固化。作为固化剂，可举出例如环氧树脂、异氰酸酯树脂等。这些之中，从耐热性等的观点考虑，优选为环氧树脂。作为环氧树脂，从反应性的观点考虑，优选环氧当量为90～300g/eq。
作为环氧树脂，可举出例如双酚A型环氧树脂、双酚F型环氧树脂、Novolac型环氧树脂、胺型环氧树脂等，其中，从耐热性的观点考虑，优选为Novolac型环氧树脂、胺型环氧树脂。此外，从与第1丙烯酸树脂的相容性的观点考虑，优选为Novolac型环氧树脂，进一步优选Novolac型环氧树脂的重复单元n为2～10，更优选为2～5。
作为异氰酸酯树脂，从反应性的观点考虑，优选为多官能团异氰酸酯。例如，可举出乙二异氰酸酯、丁二异氰酸酯、六亚甲基二异氰酸酯、亚环戊基二异氰酸酯、亚环己基二异氰酸酯、异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二甲撑二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯等。
粘合胶带的粘合层中包含的固化剂的含量没有特别限定，但优选相对于第1丙烯酸树脂而言为0.4～0.6当量。若固化剂的含量为0.4当量以上，则第1丙烯酸树脂的交联充分进行，有耐污染性进一步提高的倾向。另一方面，在固化剂的含量为0.6当量以下的情况下，有密合性进一步提高的倾向。
[固化催化剂]
本实施方式的粘合胶带的粘合层中可以还包含固化催化剂。作为固化催化剂，优选使用活性温度为120℃以下的固化催化剂。作为固化催化剂，可举出例如过氧化苯甲酰、甲基乙基酮过氧化物、过氧化-2-乙基己酸叔丁酯、氢过氧化枯烯、过氧化环己酮、过氧化二异丙苯等有机过氧化物；2-甲基咪唑、N-苄基-2-甲基咪唑等咪唑系引发剂；2,2’-偶氮双(2-甲基丁腈)、2,2’-偶氮双异丁腈等偶氮系引发剂、三氟化硼单乙胺等路易斯酸配合物、多胺、三聚氰胺树脂等。上述之中，从由催化剂残渣导致的污染的观点考虑，优选为2-甲基咪唑、2-十一烷基咪唑等咪唑系引发剂。
相对于丙烯酸树脂100质量份而言的固化催化剂的含量优选为0.01～3质量份。若固化催化剂的含量为3质量份以下，则有被粘物污染的风险变低的倾向，若为0.01质量份以上，则有能够充分引发聚合的倾向。相对于丙烯酸树脂100质量份而言的固化催化剂的含量更优选为0.05～2质量份，进一步优选为0.05～1质量份。
本实施方式的粘合胶带中包含的粘合层可以除了含有上述物质以外还含有其他添加剂等。作为这样的其他添加剂，可举出脱模剂、紫外线吸收剂、赋粘剂、软化剂、填充剂、抗老化剂、颜料、染料、硅烷偶联剂等各种添加剂。
[粘合胶带]
本实施方式的粘合胶带是具有包含上述的特定丙烯酸树脂的粘合层的粘合胶带。此处，粘合胶带可以由粘合层和基材层构成。
例如，可以通过将构成本实施方式的粘合层的树脂组合物涂布在基材(有时也称为基底膜等。)等上并使其形成粘合层等方式来制成粘合胶带。
本实施方式的粘合胶带的粘合层的厚度优选为3～40μm，更优选为3～20μm。若粘合层的厚度为3μm以上，则有在密封工序中得到充分的密封性的倾向。另一方面，若厚度为40μm以下，则有下述倾向：即使在模具的紧固压力的作用下，粘合层也不会被破坏，能够稳定地制造粘合胶带。
另一方面，基材层的厚度没有特别限定，但从防止折断、开裂的观点考虑，优选为5μm以上，从操作性的观点考虑，更优选为10～100μm。
作为构成基材层的材料，没有特别限定，可举出例如聚对苯二甲酸乙二醇酯(PET)系基材、聚酰亚胺(PI)系基材、聚酰胺(PA)系基材、聚萘二甲酸乙二醇酯(PEN)系基材、聚苯硫醚(PPS)系基材等。这些之中，从耐热性等的观点考虑，优选为聚酰亚胺系基材。另外，也可以对基材实施电晕处理、等离子体处理等这样的表面改性处理。由此，基材的经时性的物性变化的防止、各种表面改性等成为可能。
对于本实施方式的粘合胶带而言，可以在使用前利用脱模膜(分离膜)等对粘合层进行保护。通过预先贴合这样的脱模膜，能够维持粘合层的粘合力等。作为脱模膜，没有特别限定，也可以适当地使用已知的膜。作为脱模膜，可举出例如实施了有机硅系脱模处理、氟系脱模处理的聚对苯二甲酸乙二醇酯膜、聚丙烯膜、聚乙烯膜、脱模纸等。
作为本实施方式的粘合胶带的制造方法，可举出例如下述方法等：准备使构成粘合层的树脂组合物溶解于有机溶剂而成的溶液，将该溶液涂布在基材上，使其干燥等，由此在基材上形成粘合层。
作为有机溶剂，可举出例如甲醇、乙醇等醇类；乙二醇、丙二醇等二醇类；乙二醇单甲基醚、乙二醇单乙基醚等二醇单烷基醚类；乙二醇二甲基醚、乙二醇二乙基醚等二醇二烷基醚；乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酰乙酸甲酯、乙酰乙酸甲酯等烷基酯类；丙酮、甲基乙基酮、甲基异丁基酮、环己酮等酮类；苯、甲苯、二甲苯、乙基苯等芳香族烃类；己烷、环己烷、辛烷等脂肪族烃类；二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类；四氢呋喃、二氧杂环己烷等环状醚类等。
关于涂布方法，没有特别限定，也可以采用已知的方法。例如，可以使用模涂机、逗号涂布机、凹版涂布机等。
[半导体器件的制造方法]
本实施方式的粘合胶带是为了在对电子部件或半导体部件进行树脂密封时遮蔽端子部而粘贴使用的粘合胶带。
图1为使用本实施方式的粘合胶带的半导体器件的制造方法的一个例子的工序图。本实施方式的半导体器件的制造方法如图1所示，至少包括半导体芯片3的搭载工序、和基于密封树脂5的密封工序。本实施方式的半导体器件的制造方法可以还包括将已被密封的结构物切断的切割工序。
搭载工序如图1(a)～(d)所示，是在使粘合胶带1贴合于引线框背面侧(图的下侧)而得到的金属制引线框2的芯片焊盘上接合半导体芯片3的工序。
所谓引线框2，是以例如铜等金属作为原材料而刻有QFN的端子图案的框架，也有时在其电气接点部分用银、镍、钯、金等原材料进行了被覆(镀覆)。引线框2的厚度通常为100～300μm。需要说明的是，局部通过蚀刻等进行了减薄加工的部分不在此限。引线框2优选以容易通过后面的切断工序进行切分的方式整齐地排列有各个QFN的配置图案。
粘合胶带1至少粘贴于比封装图案区域更靠外侧的位置，优选粘贴于包含进行树脂密封的树脂密封区域的外侧的整周的区域。引线框2通常在端边附近具有用于进行树脂密封时的定位的、引导销用孔，优选粘贴于不将其堵塞的区域。另外，树脂密封区域在引线框2的长边方向上配置有多个，因此，优选以跨过这多个区域的方式连续地粘贴粘合胶带1。
在如上所述的引线框2上搭载半导体芯片3、即作为半导体集成电路部分的硅晶片·芯片。为了在引线框2上固定该半导体芯片3，设置有被称为芯片焊盘的固定区域，向该芯片焊盘的接合(固定)的方法使用导电性糊剂，或者可使用粘接胶带、粘接剂等各种方法。在使用导电性糊剂、热固性的粘接剂等进行芯片接合的情况下，通常于150～200℃左右的温度进行30分钟～90分钟左右的加热固化。对于搭载有半导体芯片的引线框，为了将芯片粘结材料等的污垢除去、提高线连接性、模具/框架间的粘接性，可以实施图1(c)所示那样的等离子体处理。
通常，在其之后进行引线接合工序，即，利用接合线(bonding wire)将前述引线框的端子部前端与前述半导体芯片上的电极焊盘进行电连接。引线接合工序如图1(d)所示，是利用接合线4将引线框2的端子部(内部引线)的前端与半导体芯片3上的电极焊盘进行电连接的工序。作为接合线4，可使用例如金线或铝线等。通常在已加热至120～250℃的状态下，通过基于超声波的振动能和基于外加加压的压接能的并用来接线。此时，通过对粘贴于引线框2的粘合胶带1的面进行真空抽吸，从而能够可靠地固定于加热模块(heat block)。需要说明的是，上文中示出了对半导体芯片进行面朝上(face-up)式安装从而进行接线工序的情况，但在对半导体芯片进行面朝下(face-down)式安装的情况下，可适当地实施回流焊工序。
密封工序如图1(e)所示，是利用密封树脂5对半导体芯片侧进行单面密封的工序。密封工序是为了对搭载于引线框2上的半导体芯片3、接合线4进行保护而实施的，特别地，使用以环氧系的树脂为首的密封树脂在模具中进行成型是代表性的。此时，通常使用具有多个模腔的由上模具和下模具形成的模具，利用多个密封树脂5同时实施密封工序。具体而言，例如树脂密封时的加热温度为170～180℃，于该温度进行数分钟的固化后，进一步进行数小时的模后固化(post-mold cure)。在密封工序之后，如图1(f)所示，将贴合于引线框2的粘合胶带剥离。需要说明的是，粘合胶带1优选在模后固化之前剥离。
切割工序如图1(g)所示，是将已被密封的结构物切断成独立的半导体器件10的工序。通常可举出使用切割机等的旋切刀对密封树脂5的切断部进行切割的切割工序。
需要说明的是，本实施方式的粘合胶带可以如上所述地在半导体芯片的搭载工序之前与引线框贴合，也可以在半导体芯片的搭载工序后(引线接合后)、且在密封工序前与引线框贴合。
实施例
通过以下的实施例及比较例来更详细地说明本发明，但本发明不受以下实施例的任何限定。
各评价方法及测定方法如下所述。
＜酸值＞
利用氢氧化钾溶液进行滴定，由此测定酸值。具体而言，按照以下的计算式算出酸值。
酸值(mgKOH/g)＝{(5.61×a×F)/S}/(不挥发成分浓度/100)
其中，S：试样的采集量(g)，a：0.1N醇性氢氧化钾溶液的消耗量(ml)，F：0.1N醇性氢氧化钾溶液的滴定度
＜重均分子量及分子量分布＞
使用凝胶渗透色谱(Gel Permeation Chromoatography：GPC)来测定。
＜半IPN的确认＞
根据下述情况确认了粘合层具有半IPN结构：在粘合层的截面中对形态进行观察，将海岛的面积比与聚合物的混合比进行比较时，与较少的聚合物的比率相比，岛的比率更小。
更具体而言，针对粘合胶带的粘合剂层，使用切片机(microtome)法沿厚度方向制作薄膜片。针对所制作的薄膜片，利用电子显微镜(Hitachi High-TechnologiesCorporation制的S-4800)拍摄5000倍的照片。基于该照片中拍摄到的海岛结构，算出下述式的X。
X＝α(面积比例)/β(添加比例)
α＝岛(第2丙烯酸树脂)的面积相对于海岛结构的总面积(第1丙烯酸树脂与第2丙烯酸树脂的合计面积)的比例。
β＝第2丙烯酸树脂的添加量(重量份)相对于第1丙烯酸树脂与第2丙烯酸树脂的合计添加量(重量份)的比例。
X为0.9～1.0：×(未形成半IPN结构)
X低于0.9：○(形成了半IPN结构)
＜污染性的评价＞
在实施了NiPdAu镀覆的金属板上将粘合胶带进行辊式层压(30℃，0.4MPa，1m/min)，然后，在175℃的干燥机中加热6小时。加热后将粘合胶带剥离，利用ESCA(ThermoFisher Scientific Inc.制的K-Alpha)对胶带剥离面进行分析。由得到的碳原子的原子数浓度(C)、和层压前的粘合胶带的碳原子的原子数浓度(D)，基于下述求出Y的值，对其污染性进行评价。
Y＝100-[C/D×100](％)
Y为10％以下：〇
Y大于10％且为20％以下：△
Y大于20％：×
＜热剥离力的测定＞
在轧制铜箔(厚度为35μm)的光泽面侧将粘合胶带进行辊式层压(30℃，0.4MPa，1m/min)，然后，制成25mm宽的试验片。将所制作的试验片的轧制铜箔面与不锈钢板用双面胶带贴合，利用带有恒温槽的测定装置[岛津制作所公司制，Autograph AGS-500]，在150℃的气氛下放置3分钟后，在相同气氛下，测定将粘合胶带沿180°方向以200mm/min的速度剥离时的剥离力。
75mN/25mm以上：〇
50mN/25mm以上且低于75mN/25mm：△
低于50mN/25mm：×
＜压制后剥离力的测定＞
将粘合胶带贴合于轧制铜箔(厚度为35μm)的光泽面侧，在180℃、3.0MPa、60分钟的条件下进行加热加压，然后，制成25mm宽的试验片。将所制作的试验片的轧制铜箔面与不锈钢板用双面胶带贴合，利用测定装置(同上)，测定将粘合胶带沿180°方向以200mm/min的速度剥离时的剥离力。
[合成例1：乙基-2-甲基-2-正丁基碲-丙酸酯]
使金属碲[Aldrich公司制，制品名“Tellurium(-40mesh)”]6.38g(50mmol)悬浮在四氢呋喃(THF)50mL中，于室温向其中缓缓滴加正丁基锂[Aldrich公司制，1.6mol/L己烷溶液]34.4mL(55mmol)。对该反应溶液进行搅拌直至金属碲完全消失。于室温向该反应溶液中加入2-溴异丁酸乙酯10.7g(55mmol)，搅拌2小时。反应结束后，在减压条件下将溶剂浓缩，继续进行减压蒸馏，得到作为黄色油状物的乙基-2-甲基-2-正丁基碲-丙酸酯8.98g(收率为59.5％)。
[合成例2：聚合物A]
在用氩进行了置换的手套箱内，于60℃使合成例1中制造的乙基-2-甲基-2-正丁基碲-丙酸酯68μL(0.28mmol)、丙烯酸丁酯130.8g(1.02mol)、丙烯酸11.4g(158mmol)及2,2’-偶氮双(异丁腈)[AIBN；Aldrich公司制]4.6mg(0.03mmol)反应20小时。反应结束后，将反应器从手套箱取出，溶解于乙酸乙酯500mL中之后，将该聚合物溶液通入用活性氧化铝[和光纯药工业公司制]制成的柱中。以聚合物溶液的粘度成为7,000mPa·s(25℃)的方式添加乙酸乙酯，得到聚合物A的溶液。得到的聚合物A溶液的固态成分为23.0质量％。
聚合物A的由凝胶渗透色谱(GPC)求出的重均分子量为64.4万，分子量分布(MW/MN)＝1.78。另外，聚合物A的酸值为60mgKOH/g。
[合成例3：聚合物B]
以丙烯酸丁酯：丙烯酸2-羟基乙酯＝80：20的比例使其反应，除此以外，通过与合成例2同样的方法得到聚合物B的溶液。聚合物B的重均分子量为59.7万，分子量分布(MW/MN)＝1.82。另外，聚合物B的酸值为0mgKOH/g。
[合成例4：聚合物C]
向反应容器中加入乙酸乙酯100g、丙烯酸丁酯100.0g(780mmol)、丙烯酸8.7g(121mmol)及2,2’-偶氮双(异丁腈)0.33g(2.0mmol)，于70℃进行搅拌。从反应开始60分钟后每隔30分钟取出反应溶液的一部分，用去离子水使反应停止，利用甲基乙基酮进行萃取，利用凝胶渗透色谱(GPC)对萃取溶液进行分析。根据GPC分析，在反应物的分子量成为50万以上的阶段将反应容器冷却，使反应停止。利用去离子水对得到的混合物进行水洗，进行干燥，由此得到聚合物C的溶液。
聚合物C的由GCP求出的重均分子量为81.4万，分子量分布(MW/MN)＝4.77。另外，聚合物C的酸值为61mgKOH/g。
[合成例5：聚合物D]
以丙烯酸丁酯：丙烯酸＝98：2的比例使其反应，除此以外，通过与合成例2同样的方法得到聚合物D的溶液。聚合物D的重均分子量为60.3万，分子量分布(MW/MN)＝1.96。另外，聚合物D的酸值为16mgKOH/g。
[合成例6：聚合物E]
以丙烯酸丁酯：丙烯酸＝98：2的比例使其反应，除此以外，通过与合成例6同样的方法得到聚合物E的溶液。聚合物E的重均分子量为62.1万，分子量分布(MW/MN)＝4.78。另外，聚合物E的酸值为17mgKOH/g。
[合成例7：聚合物F]
使41μL(0.17mmol)的乙基-2-甲基-2-正丁基碲-丙酸酯进行反应，除此以外，通过与合成例2同样的方法得到聚合物F的溶液。聚合物F的重均分子量为96.6万，分子量分布(MW/MN)＝1.79。另外，聚合物F的酸值为62mgKOH/g。
[实施例1]
于室温对聚合物A溶液29.3g(23.0％)、聚合物B溶液11.3g(20.0％)、Novolac型环氧树脂[DIC株式会社制，Epiclon N730A]0.66g(0.5当量)、咪唑催化剂[四国化成工业株式会社制，CUREZOL C11Z]、及甲基乙基酮19g进行搅拌，得到组合物1。将组合物1以干燥后的厚度成为7μm的方式涂布于聚酰亚胺膜(厚度为25μm)，于150℃干燥5分钟，得到粘合胶带。通过层压而将实施了脱模处理的脱模膜的脱模面贴合于粘合胶带的粘合层，于105℃加热24小时，得到带有脱模膜的粘合胶带。
使用得到的粘合胶带进行各物性的评价。将评价结果示于表1(只要没有特别标明，则表中的含量的单位表示“质量份”。)。
[实施例2]～[实施例6]
将形成粘合层的组合物中包含的各成分的种类及含量替换为表1～3所示的种类及含量，除此以外，通过与实施例1同样的方法制造粘合胶带，进行各物性的评价。
[比较例1]～[比较例13]
将形成粘合层的组合物中包含的各成分的种类及含量替换为表1～3所示的种类及含量，除此以外，通过与实施例1同样的方法制造粘合胶带，进行各物性的评价。
[表1]
Figure BDA0003327088420000171
[表2]
Figure BDA0003327088420000181
[表3]
Figure BDA0003327088420000182
如表1～3所示，可知实施例1～6的粘合胶带同时实现了密合性和耐污染性，能够同时达成密封工序中的模制树脂毛刺的防止、和胶带剥离工序中的粉浆残留的抑制。
本申请基于在2019年12月27日向日本专利局提出申请的日本专利申请(特愿2019-238895)，其内容通过引用并入本申请中。
产业上的可利用性
本发明的粘合胶带具有作为在半导体器件的制造中使用的粘合胶带的产业上的可利用性。

Claims (5)

1.粘合胶带，其具有包含酸值为30～100mgKOH/g的第1丙烯酸树脂、和酸值为0～10mgKOH/g的第2丙烯酸树脂的粘合层，所述粘合胶带中，
所述第1丙烯酸树脂与所述第2丙烯酸树脂的比例为第1丙烯酸树脂：第2丙烯酸树脂＝85：15～65：35，
所述第1丙烯酸树脂与第2丙烯酸树脂具有半互穿聚合物网络结构，
所述粘合层还含有固化剂，所述粘合胶带是利用所述固化剂使所述第1丙烯酸树脂固化而得到的，
所述固化剂为环氧树脂，
所述粘合胶带用于半导体器件的制造。
2.如权利要求1所述的粘合胶带，其中，所述第1丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下，所述第2丙烯酸树脂的分子量分布(Mw/Mn)为2.0以下。
3.如权利要求1或2所述的粘合胶带，其中，所述第1丙烯酸树脂的重均分子量(Mw)为40～100万，所述第2丙烯酸树脂的重均分子量(Mw)为40～80万。
4.如权利要求1或2所述的粘合胶带，其中，所述固化剂的含量相对于所述第1丙烯酸树脂而言为0.4～0.6当量。
5.如权利要求1或2所述的粘合胶带，其中，所述粘合层还含有固化催化剂。
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