CN106488963A - 粘合片、电子部件的制造方法 - Google Patents

粘合片、电子部件的制造方法 Download PDF

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Publication number
CN106488963A
CN106488963A CN201580037940.0A CN201580037940A CN106488963A CN 106488963 A CN106488963 A CN 106488963A CN 201580037940 A CN201580037940 A CN 201580037940A CN 106488963 A CN106488963 A CN 106488963A
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bonding sheet
mass parts
methyl
agent
photopolymerizable compound
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CN201580037940.0A
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CN106488963B (zh
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津久井友也
中岛刚介
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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Abstract

提供了在切割工序中可以抑制粘合剂的刮起，在切割加工中芯片不飞散，容易拾取，不易产生残胶的粘合片。根据本发明，提供一种在基材膜上层叠粘合剂层而成的粘合片，其特征在于，构成所述粘合剂层的成分为(甲基)丙烯酸酯共聚物100质量份、光聚合性化合物5～250质量份、柔性赋予剂20～160质量份、固化剂0.1～30质量份和光聚合引发剂0.1～20质量份，所述光聚合性化合物的重均分子量为40000～220000。

Description

粘合片、电子部件的制造方法
技术领域
本发明涉及一种在电子部件的制造工序中使用的粘合片，以及使用该粘合片的电子部件的制造方法。
背景技术
半导体晶圆或基板，在贴合于粘合片后，被分配到切割成元件小片(切割)、延伸粘合片(延展)、从粘合片上剥离元件小片(拾取)等各个工序中。理想的是在这些工序中所使用的粘合片(切割胶带)既具有在切割工序中对被切断的元件小片(芯片)具有足够的粘合力，同时又可以在拾取工序中粘合力减少至粘合剂不会残留的程度。
作为粘合片，在对紫外线和/或电子束等活性光线具有透光性的基材膜上涂布通过紫外线等进行聚合固化反应的粘合剂层。该粘合片可用于在切割工序后对其粘合剂层照射紫外线等，使粘合剂层聚合固化降低粘合力后，从而拾取被切断芯片的方法中。
作为这种粘合片，在专利文献1和2中已经公开了：在基材膜面涂布含有例如可以通过活性光线三维网状化的，在分子内具有光聚合性不饱和双键的化合物(多官能性低聚物)而成的粘合剂的粘合片。
现有技术文献
专利文献
专利文献1：日本特开2006-049509号公报
专利文献2：日本特开2007-246633号公报
发明内容
发明要解决的问题
在半导体晶圆或基板的切割工序中，有时候被称为高速旋转刀片的薄型砂轮刮起粘合片的粘合剂，使粘合剂粘附在已单片化的芯片的侧面上，从而成为成品率下降的主要原因。
因此，本发明的目的在于提供一种可以在切割工序中抑制粘合剂的刮起，在切割加工中芯片不飞散，容易拾取，从而不易产生残胶的粘合片。
用于解决问题的方案
根据本发明，提供了一种通过在基材膜上层叠粘合剂层而成的粘合片，其特征在于，所述粘合剂层含有(甲基)丙烯酸酯共聚物100质量份、光聚合性化合物5～250质量份、柔性赋予剂20～160质量份、固化剂0.1～30质量份和光聚合引发剂0.1～20质量份，所述光聚合性化合物的重均分子量为40000～220000。
优选粘合片的特征在于，所述光聚合性化合物是聚氨酯丙烯酸酯低聚物。
优选粘合片的特征在于，所述光聚合性化合物的不饱和双键官能团数为10以上。
优选所述柔性赋予剂为聚酯丙烯酸酯。
优选提供一种电子部件的制造方法，其包含以下工序：
(a)将上述粘合片粘贴在半导体晶圆或基板和环状框上的贴附工序，
(b)将所述半导体晶圆或基板切割成半导体芯片或半导体部件的切割工序，
(c)向所述粘合片照射活性光线的光照射工序，
(d)为扩展所述半导体芯片或半导体部件相互之间的间隔而拉伸所述粘合片的延展工序，
(e)从所述粘合片上摘取半导体芯片或半导体部件的拾取工序。
优选所述电子部件是以树脂、陶瓷或金属为材料的封装体。
发明的效果
根据本发明，提供了一种在切割工序中可以抑制粘合剂的刮起，在切割加工中芯片不飞散，能够容易拾取，不易产生残胶的粘合片。
具体实施方式
以下说明本发明的优选实施方式。应予说明，以下说明的实施方式为本发明具有代表性的实施方式的一个例子，本发明的范围不会因此而被过窄地解释。
本发明的粘合片是一种在基材膜上层叠粘合剂层而成的粘合片，其特征在于，
所述粘合剂层含有(甲基)丙烯酸酯共聚物100质量份、光聚合性化合物5～250质量份、柔性赋予剂20～160质量份、固化剂0.1～30质量份以及光聚合引发剂0.1～20质量份，所述光聚合性化合物的重均分子量为40000～220000。
<粘合剂层>
构成粘合剂层的光固化型粘合剂含有(甲基)丙烯酸酯共聚物100质量份、光聚合性化合物5～250质量份、柔性赋予剂20～160质量份、固化剂0.1～30质量份以及光聚合引发剂0.1～20质量份，光聚合性化合物的重均分子量为40000～220000。
((甲基)丙烯酸酯共聚物)
作为(甲基)丙烯酸酯共聚物，有丙烯酸、异丁烯酸以及使这些酯单体聚合而得的聚合物，使这些单体与可发生共聚的不饱和单体(例如醋酸乙烯酯，苯乙烯，丙烯腈)发生共聚而得的共聚物。本实施方式的粘合片，构成粘合剂层的粘合剂为容易设计其粘合力的丙烯酸共聚物较好，通过含有固化剂，可以更精确地调整粘合力。并且，优选构成丙烯酸共聚物的丙烯酸单体的至少一个包括含官能团单体。优选此含官能团单体在丙烯酸共聚物中混合0.01质量％以上10质量％以下而聚合。当此含官能团单体的混合比在0.01质量％以上时，对被粘合体的粘合力足够强，有抑制渗水的发生的趋势，当此含官能团单体的混合比为10质量％以下时，由于对被粘合体的粘合力不会变得过高，有可以抑制残胶的发生的倾向。
作为丙烯酸聚合体主要的单体，可以列举如(甲基)丙烯酸丁酯、2-(甲基)丙烯酸丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸十八酰酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄酯等。
作为这种丙烯酸单体，特别优选在至少一部分具有含有官能团的单体。作为这种含有官能团的单体，优选具有羟基、羧基、环氧基、酰胺基、氨基、羟甲基、磺酸基、氨基磺酸基、(亚)磷酸酯基的单体。并且，其中特别是具有这些官能团的乙烯基化合物较好，优选具有羟基的乙烯基化合物。应予说明，在这里所述的乙烯基化合物包括后面叙述的丙烯酸。
作为具有羟基的含官能团单体，有例如(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、以及(甲基)丙烯酸2-羟基丁酯。
作为具有羧基的单体，可以列举例如(甲基)丙烯酸、巴豆酸、马来酸、衣康酸、富马酸、丙烯酰胺N-乙醇酸、以及桂皮酸等。
作为具有环氧基的单体，可以列举例如烯丙基缩水甘油醚、以及(甲基)丙烯酸缩水甘油醚等。
作为具有酰胺基的单体，可以列举例如(甲基)丙烯酰胺等。
作为具有氨基的单体，可以列举例如N，N-二甲氨基乙基(甲基)丙烯酸等。
作为具有羟甲基的单体，可以列举例如N-(羟甲基)丙烯酰胺等。
应予说明，本实施方式的粘合剂层在使上述丙烯酸共聚物和固化剂反应而固化粘合剂层后，构成这种丙烯酸共聚物的包含羧基单体优选在丙烯酸共聚物中的含量为0.1～10质量％以下。即，使粘合剂以固化剂进行反应的含官能团单体中，优选含羧基含官能团单体为10质量％以下。通过使用具有羧基的含官能团单体，由于增加对金属的粘合力，与固化剂反应后的具有羧基的含官能团单体如果超过10质量％，则有对金属的粘合力高而产生残胶的倾向，因此优选10质量％以下。从而，作为具有羧基的单体，优选通过与固化剂反应而容易减少的，例如优选使用(甲基)丙烯酸、巴豆酸、马来酸、衣康酸、富马酸、丙烯酰胺N-乙醇酸、以及桂皮酸。
(固化剂)
在本实施方式的粘合片中，用于粘合剂层的粘合剂优选混合固化剂。在混合固化剂时，相对于丙烯酸共聚物100质量份，固化剂的混合比为0.1质量份以上30质量份以下，优选为1质量份以上20质量份以下。这是由于当固化剂的混合比在0.1质量份以上30质量份以下时，可以抑制残胶的发生。
作为混合在光固化型粘合剂中的固化剂，有多官能异氰酸固化剂、多官能环氧固化剂、氮丙啶化合物、三聚氰胺化合物等，其中优选多官能异氰酸固化剂、多官能环氧固化剂。作为上述固化剂中的至少一部分，通过使用多官能环氧固化剂或多官能异氰酸固化剂，可以选择性地使具有羧基的含官能团单体产生反应并消除，从而能够调节固化后的具有羧基的含官能团单体量。
作为多官能异氰酸固化剂，有例如芳香族聚异氰酸固化剂、脂肪族聚异氰酸固化剂、脂环族聚异氰酸固化剂。
对芳香族聚异氰酸酯不做特别限定，可以列举如1，3-苯二异氰酸酯、4，4'-二苯基甲烷二异氰酸酯、1，4-苯二基二异氰酸酯、4，4'-二苯基甲烷基二异氰酸酯、2，4-甲苯基二异氰酸酯、2，6-甲苯基二异氰酸酯、4，4'-甲苯胺二异氰酸酯、2，4，6-异氰酸酯甲苯、1，3，5-三异氰酸酯苯、联茴香胺异氰酸酯、4，4'-二苯基醚二异氰酸酯、4，4'，4”-三苯基甲烷三异氰酸酯、ω，ω'-二异氰酸酯1，3-二甲基苯、ω，ω'-二异氰酸酯1，4-二甲基苯、ω，ω'-二异氰酸酯1，4-二乙基苯、1，4-四甲基亚二甲苯基二异氰酸酯以及1，3-四甲基亚二甲苯基二异氰酸酯等。
对脂肪族聚异氰酸酯不做特别限定，可以列举如三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、1，2-亚丙基二异氰酸酯、2，3-亚丁基二异氰酸酯、1，3-亚丁基二异氰酸酯、十二亚甲基二异氰酸酯以及2，4，4-三甲基六亚甲基二异氰酸酯等。
对脂环族聚异氰酸酯不做特别限定，例如有3-异氰酸酯甲基-3，5，5-三甲基环己基异氰酸酯、1，3-环戊烷二异氰酸酯、1，3-环己烷二异氰酸酯、1，4-环己烷二异氰酸酯、甲基-2，4-环己烷二异氰酸酯、甲基-2，6-环己烷二异氰酸酯、4，4'-亚甲基双(环己基异氰酸酯)、1，4-双(异氰酸酯甲基)环己烷以及1，4-双(异氰酸酯甲基)环己烷。
在聚异氰酸酯中，优选使用1，3-苯二基二异氰酸酯、4，4'-二苯基甲烷二异氰酸酯、1，4-苯二基二异氰酸酯、4，4'-二苯基甲烷基二异氰酸酯、2，4-甲苯基二异氰酸酯、2，6-甲苯基二异氰酸酯、4，4'-甲苯胺二异氰酸酯、六亚甲基二异氰酸酯。
多官能团环氧树脂固化剂，以含有2个以上环氧树脂基和一个以上第3级氮原的化合物为主，可以列举如N·N-二环丙氧基苯胺、N·N-缩水甘油基甲苯胺、m-N·N-三缩水甘油基间氨基苯酚、p-N·N-三缩水甘油基间氨基苯酚、异氰尿酸三缩水甘油酯、N·N·N'·N'-四缩水甘油基二氨基二苯基甲烷、N·N·N'·N'-四缩水甘油基-m-间苯二甲胺、N·N·N'·N'·N″-五缩水二乙烯三胺等。
(光聚合性化合物)
作为光聚合性化合物可以使用聚氨酯丙烯酸酯低聚物。聚氨酯丙烯酸酯低聚物可以通过将由聚酯型或聚醚型等多元醇化合物与多价异氰酸化合物反应制得的末端异氰酸酯基氨基甲酸酯预聚物，与具有羟基的(甲基)丙烯酸相反应而制得。
作为多价异氰酸酯化合物，可以使用如2，4-甲苯基二异氰酸酯、2，6-甲苯基二异氰酸酯、1，3-苯二甲基二异氰酸酯、1，4-苯二甲基二异氰酸酯、4，4-二苯基甲烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯等。另外，含有羟基官能团的(甲基)丙烯酸酯，可以使用如(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸聚乙二醇酯、丙烯酸三季戊四醇酯、(甲基)丙烯酸缩水甘油酯、聚二季戊四醇五丙烯酸酯等。
作为光聚合性化合物，优选使用不饱和双键官能团数为10以上15以下的聚氨酯丙烯酸酯低聚物，由于其具有在紫外线等光照射后粘合剂固化性良好的优点。
光聚合性化合物的重均分子量为40000～220000，优选80000～120000。若光聚合性化合物的重均分子量小，则在切割时易造成对粘合剂刮起过多，而若重均分子量大则粘合力不足时，在切割时容易发生芯片飞散。
光聚合性化合物的混合量，相对于(甲基)丙烯酸酯共聚物100质量份为5～250质量份，优选为40～200质量份。若光聚合性化合物的混合量少，则放射线照射后粘合片的剥离性下降，容易发生半导体芯片拾取不良。另一方面，若光聚合性化合物的混合量多，则因光照射工序而造成粘合力降低过度，在拾取工序中会发生芯片松动(loosen)，成为生产性下降的主要原因。
(柔性赋予剂)
将粘合剂进行软化，以提高对粗糙面的粘合力，也可以添加柔性赋予剂。
作为柔性赋予剂，可以使用聚酯丙烯酸酯。如具有不饱和双键官能团的聚酯丙烯酸酯，可以通过由紫外线等的光照射而发生交联反应，来抑制对被粘合体的污染。
聚酯丙烯酸酯是通过多元醇与多元酸反应制得的聚酯多元醇和丙烯酸或甲基丙烯酸进行酯化反应制得。多元醇可以使用如乙二醇、聚乙二醇、丙二醇、聚丙二醇、新戊二醇、1，4-丁二醇等。多元酸可用如琥珀酸、己二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸等。
作为聚酯丙烯酸酯，优选不饱和双键官能团数为1以上3以下。不饱和双键官能团数如果超过这个范围，在紫外线等光照射后粘合剂固化过度，从而造成与基材的密合性不良。
柔性赋予剂的混合比为优选相对于(甲基)丙烯酸酯共聚物100质量份为20质量份以上160质量份以下，更优选40质量份以上140质量份以下。若柔性赋予剂为20质量份以上，则由于能够可塑化粘合剂，对于粗糙面的粘合力强度增强，可以在切割时维持半导体芯片的保持性，而若在160质量份以下，则可以抑制因切割时粘合剂被刮起而导致的对半导体芯片产生的残胶。
(光聚合引发剂)
作为光聚合引发剂，可以使用如安息香、安息香酸烷基醚类、苯乙酮类、蒽醌类、噻吨酮类、缩醛类、二苯甲酮类或氧杂蒽酮类等。
作为安息香，有例如安息香、安息香甲基醚、安息香乙醚、安息香丙醚等。
作为苯乙酮类，例如有如安息香烷基醚类、苯乙酮、2，2-二甲氧基-2-苯乙酮、2，2―二乙氧基-2-苯乙酮、1，1-二氯苯乙酮等。
作为蒽醌类，有如2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌等。
作为噻吨酮类，例如有2，4-二甲基噻吨酮、2，4-二异丙基噻吨酮、2-氯噻吨酮、2，4-二异丙基噻吨酮等。
作为缩酮类，例如有苯乙酮二甲基缩酮、安息香二甲醚、苄基苯基硫醚、一硫化四甲基秋兰姆、偶氮二异丁腈、联苄、二乙酰、β-氯蒽醌等。
光聚合引发剂的混合量相对于(甲基)丙烯酸酯共聚物100质量份为0.1质量份以上20质量份以下，优选1质量份以上10质量份以下。若混合量过少，则放射线照射后的粘合片的剥离性降低，容易发生半导体芯片的拾取不良。另一方面，若混合量过多，则光聚合引发剂溢出至粘合剂表面，成为污染的原因。
在光聚合引发剂中，根据需要也可以将一种或两种以上已公开的光聚合促进剂进行组合而并用。在光聚合促进剂中，可以使用苯甲酸系、叔胺等。作为叔胺，可以列举如三乙胺、四乙基五胺、二甲氨基醚等。
(增粘树脂)
在粘合剂中，可以添加增粘树脂。作为增粘树脂，是将萜烯酚树脂完全或部分氢化的萜烯酚树脂。
萜烯酚树脂，例如，可通过1摩尔的萜烯化合物与0.1～50摩尔的酚类反应而制造。
作为萜烯化合物，可以列举如月桂烯、别罗勒烯、罗勒烯、α-蒎烯、β-蒎烯、二烯萜、柠檬烯、α-水芹烯、α-萜品烯、γ-萜品烯、萜品油烯、1，8-桉树脑、1，4-桉树脑、α-萜品醇、β-萜品醇、γ-萜品醇、莰烯、三环烯、香桧烯、对薄荷二烯类、蒈烯类等。在这些化合物中，特别优选使用α-蒎烯、β-蒎烯、柠檬烯、月桂烯、别罗勒烯、α-萜品烯。
作为苯酚类可以列举如苯酚、甲酚、二甲苯酚、邻苯二酚、间苯二酚、对苯二酚、双酚A等，不限定于此。
萜烯酚树脂的酚类的比率为25～50摩尔％左右，但不限于此。
完全或部分氢化的萜烯酚树脂的羟值优选为50～250。羟值低于50时，与异氰酸系固化剂的反应不充分，溢出至粘合剂表面，成为污染的原因，如果高于250则粘度增强，发生与(甲基)丙烯酸酯共聚物等的混合不均，从而造成拾取特性不稳定。
作为氢化方法，没有特别限定，可以列举如使用钯、钌、铑等贵金属或将这些负载于活性炭、活性氧化铝、硅藻土等而得到的产品作为催化剂来进行氢化的方法，氢化率可以通过溴值测定、碘值测定等来测定。
完全或部分氢化的萜烯酚树脂的氢化率优选为30摩尔％以上，更优选为70摩尔％以上。当低于30摩尔％时，由活性光线的照射所引发的光聚合性化合物的反应障碍导致粘合力没有充分减低，导致拾取性下降。
完全或部分氢化的萜烯酚树脂的混合比，优选相对于(甲基)丙烯酸酯共聚物100质量份为0.5质量份以上100质量份以下，更优选为1.0质量份以上50质量份以下。若完全或部分氢化的萜烯酚树脂为0.5质量份以上，则由于粘合力并不太低，因此在切割时能够维持半导体芯片的保持性，若为100质量份以下，则可抑制拾取不良的发生。
(添加剂等)
粘合剂中可以添加如软化剂、抗老化剂、填充剂、导电剂、紫外线吸收剂以及光稳定剂等各种添加剂。
粘合剂层的厚度，优选为1μm以上50μm以下，特别优选为5μm以上35μm以下。粘合剂层如果过厚则粘合力变得过高，导致拾取性下降。并且，粘合剂层如果过薄则粘合力变得过低，造成切割时芯片保持性下降，在环状框与片材之间有发生剥离的现象。
(基材膜)
作为基材膜材料，可以列举如聚氯乙烯、聚对苯二甲酸、乙烯-醋酸乙烯酯共聚物、乙烯丙烯酸-丙烯酸酯膜、乙烯丙烯酸乙酯共聚物、聚乙烯、聚亚丙基、亚丙基系共聚物、乙烯丙烯酸共聚物、和乙烯(甲基)丙烯酸共聚物、乙烯(甲基)丙烯酸-(甲基)丙烯酸酯共聚物等通过金属离子交叉链接的离聚物树脂等。基材膜可以是这些树脂混合物或共聚物，也可以是由这些树脂构成的膜或片的叠层体。
基材膜的材料优选使用离子键共聚物树脂。离子键共聚物树脂中，如果使用具有乙烯单元、甲基丙烯酸单元，以及(甲基)丙烯酸烷基酯单元的共聚物经Na+，K+，Zn2+等金属离子进行交联而得的离子键共聚物树脂，则刨花的抑制效果显著，优选使用。
基材膜，可以是由上述材料构成的单层或多层的膜或片，也可以通过层叠由不同材料构成的膜而得到。基材膜的厚度为50～200μm，优选为70～150μm。
对基材膜优选实施防静电处理。作为防静电处理，有在基材膜上混合防静电剂的处理、在基材膜表面上涂布防静电剂的处理、利用电晕放电的处理。
作为防静电剂，可使用例如季铵盐单体等。作为季铵盐单体，可以列举如二甲基氨基乙基(甲基)丙烯酸酯季盐化物、二乙基氨基乙基(甲基)丙烯酸酯季盐化物、甲基乙基氨基乙基(甲基)丙烯酸酯季盐化物、对二甲基氨基苯乙烯季盐化物和对二乙基氨基苯乙烯季盐化物。其中，优选为二甲基氨基乙基甲基丙烯酸酯季盐化物。
对滑动剂以及防静电剂的使用方法不做特别限定，例如可以在基材膜的一侧上涂布粘合剂，在其反面涂布滑动剂以及/或防静电剂，也可以将滑动剂以及/或防静电剂与基材膜的树脂混炼后成片。
在基材膜的一侧层叠粘合剂，可以使另一面为平均表面粗糙度(Ra)为0.3～1.5μm的压纹表面。通过在延展装置的机床工作台面设置压纹表面，可以在切割后的延展工序中使基材膜易于延展。
(滑动剂)
为了提高切割后的延展性，可以在基材膜上的粘合剂非接触面上施以滑动剂，也可以将滑动剂混炼于基材膜。
滑动剂只要是能使粘合片与延展装置的摩擦系数降低的物质，就不做特别限定，可以列举如硅酮树脂、(变性)硅酮油等的硅酮化合物，含氟树脂、六方氮化硼、炭黑以及二硫化钼等。这样的减摩剂可以是由几种不同的成分混合而成。由于电子部件的制造是在无尘室中进行的，优选使用硅酮化合物或含氟树脂。硅酮化合物中特别是具有硅酮大分子单体单元的共聚物对防静电层的兼容性良好，为了能够平衡防静电性与延展性，优选使用。
以下依次说明本发明的电子部件制造方法的具体工序。
(1)贴附工序
首先，在贴附工序中，将粘合片贴附于半导体晶圆或基板与环状框上。晶圆可以是硅晶圆及氮化镓晶圆、碳化硅晶圆、蓝宝石晶圆等目前广泛使用的晶圆。基板可为以树脂密封了芯片的封装基板、LED封装基板、陶瓷基板等广泛使用的基板。
(2)切割工序
在切割工序中，将硅晶圆等切割而形成半导体芯片或半导体部件。
(3)光照射工序
在光照射工序中，从基材膜侧对光固化型粘合剂层照射紫外线等活性光线。作为紫外线的光源，可以使用低压汞灯、高压汞灯、超高压汞灯、金属卤化物灯。另外，还可以使用电子束代替紫外线，作为电子束的光源可以使用α射线、β射线、γ射线。
通过光照射，粘合剂层三维网状化而固化，导致粘合剂层的粘合力降低。此时，如上所述，即使将本发明的粘合片加温也不会过度地粘合于晶圆等，因此通过紫外线等的照射能够使粘合力充分地降低。
(4)延展·拾取工序
在延展·拾取工序中，为了扩大半导体芯片或半导体部件相互之间的间隔而将粘合片拉伸，用针销等顶起芯片或元件。然后，用真空筒夹或空气镊子等吸附芯片或元件，从粘合片的粘合剂层剥离而拾取。此时，由于本发明的粘合片，通过照射紫外线等可以使粘合力充分地降低，故芯片或部件与粘合剂层之间的剥离变得容易，得到良好的拾取性，也不会发生残胶等不良的情况。
<粘合片的制造>
作为在基材膜上形成粘合剂层而作为粘合片，有例如通过使用凹印涂布机、逗点涂布机、棒涂布机、刮刀涂布机或辊涂布机之类的涂布机在基材膜上直接涂布粘合剂的方法，在剥离膜上涂布粘合剂/干燥后贴合在基材膜上的方法。也可以通过凸版印刷、凹版印刷、平版印刷、柔性印刷、胶版印刷或丝网印刷等，将粘合剂印刷在基材膜上。
本发明的粘合片在电子部件制造工序的切割工序、背面研磨工序中，适合用于粘合被称作是工件的电子部件集合体。
<实施例·比较例>
实施例·比较例的光固化型粘合剂以及粘合片使用如下配方制得。主要成分和各实验例的结果如表1～表2所示。
光固化型粘着剂涂布在聚对苯二甲酸乙二酯制的隔离膜上，进行涂工使干燥后粘着剂层的厚度为20μm。将此粘合剂层叠层于基材膜上，40℃下熟化7天，得到粘合片。基材膜上使用作为离聚物树脂的苯乙烯-甲基丙烯酸-甲基丙烯酸烷基酯共聚物的Zn盐作为主体，MFR值1.0g/10分(JISK7210、210℃)，熔点86℃，含有Zn2+离子(三井杜邦聚合化学公司制造，产品编号：HM1855)，通过T型模挤压为150μm的成膜物。
[光固化型粘合剂]
〔(甲基)丙烯酸酯共聚物〕
A-1：丙烯酸甲酯60质量％、丙烯酸2-乙基己酯35质量％、丙烯酸4.5质量％、丙烯酸2-羟乙基酯0.5质量％的共聚物，重均分子量为20万，通过溶液聚合而得。
A-2：丙烯酸乙酯54％、丙烯酸丁酯19％、丙烯酸2-甲氧基乙酯24％の共聚物、重均分子量为200万，通过乳液聚合而得。
〔光聚合性化合物〕
将以异佛尔酮二异氰酸酯的三聚体的异氰酸酯中双季戊四醇无丙烯酸酯为主要成分的羟基含有丙烯酸酯通过日本专利公开昭61-42529号公报和日本专利公开2012-36253公报等公知的方法来调整，为不饱和双键官能团数为15の聚氨酯丙烯酸酯(合成品)。应予说明，重均分子量是通过凝胶渗透色谱法(GPC)，作为聚苯乙烯換算的重均分子量来测定的值。具体为：
装置：GPC-8020SEC系统(东曹株式会社制)
柱：TSKGuardHZ-L+HZM-N6.0×150mm×3
流量：0.5ml/min
检测器：RI-8020
浓度：0.2wt/Vol％
进样量：20μL
柱温度：40℃
系统温度：40℃
溶剂：THF
校准线：使用标准聚苯乙烯(PL株式会社制)来制作，重均分子量(Mw)以聚苯乙烯对应值来表示。
结果为，
B-1：重均分子量11000
B-2：重均分子量43000
B-3：重均分子量79000
B-4：重均分子量124000
B-5：重均分子量217000
B-6：重均分子量338000。
〔柔性赋予剂〕
X-1：将乙二醇和丁二酸反应得到的聚酯多元醇与丙烯酸反应得到重均分子量为8000的聚酯丙烯酸酯。
X-2：将丙二醇和偏苯三酸反应得到的聚酯多元醇与异丁烯酸反应得到重均分子量为5000的聚酯丙烯酸酯。
〔固化剂〕
C-1：日本聚氨酯工业株式会社制CORONATE L-45E；2,4-二异氰酸酯的三羟甲基丙烷加成物。
C-2：日本聚氨酯工业株式会社制CORONATE L；六亚甲基二异氰酸酯的三羟甲基丙烷加成物。
〔光聚合引发剂〕
D-1：BASF日本株式会社制IRGACURE184；1-羟环己基苯酮。
D-2：BASF日本株式会社制IRGACURE651；苯甲基二甲基缩铜。
[表1]
[表2]
(1)粘合剂的刮起，芯片保持性以及拾取性评价
用制得的粘合片将长80mm×宽80mm×厚0.6mm的陶瓷(氧化铝)与环状框贴合。然后，进行切割、拾取各工序。
切割工序的条件如下。
切割装置：DISCO株式会社制DAD341
切割刀片：东京精密公司制MD500-35YM030
切割刀片形状：外径58mm、刃宽15μm、内径40mm
切割刀片转数：30，000rpm
切割刀片进给速度：20mm/秒
切割尺寸：5mm角
粘合片切入量：100μm
切割水温度：25℃
切割水量：1.0升/分
拾取工序的条件如下。
拾取装置：佳能机械株式会社制CAP-300II
延展量：5mm
针销形状：250μmR
针销数：4根
针销突起高度：1.5mm
对切割工序和拾取工序进行了如下评价。
(1-1)粘合剂的刮起
粘合剂的刮起，根据随机选择50个被拾取的芯片，使用500倍的显微镜对芯片的侧面进行观察，关于芯片侧面有无附着粘合剂，按以下的基准进行了评价。
◎(优)：在芯片侧面粘合剂没有附着
○(良)：在芯片侧面粘合剂的附着低于5％
×(不可)：在芯片侧面粘合剂的附着为5％以上
(1-2)芯片保持性
芯片保持性，根据切割工序后陶瓷芯片保持于粘合片上的陶瓷芯片的残留率，按以下的基准进行了评价。
◎(优)：芯片飞散低于5％
○(良)：芯片飞散为5％以上且低于10％
×(不可)：芯片飞散为10％以上
(1-3)拾取性
拾取性，根据拾取工序中可拾取陶瓷芯片的比例，按以下的基准进行了评价。
◎(优)：芯片的拾取成功率为95％以上
○(良)：芯片的拾取成功率为80％以上且低于95％
×(不可)：芯片的拾取成功率低于80％
(2)污染性
将粘合片贴附于硅制镜面晶圆上，20分钟后使用高圧汞灯以150mJ/cm2对紫外线照射后，将粘合片剥离。使用颗粒计数器测定硅制镜面晶圆贴附面上残留的0.28μm以上的粒子数。
优：粒子数为500个以下
良：粒子数为501个以上2000个以下。
不可：粒子数为2001个以上。
(3)芯片松动(loosen)
芯片松动，基于在拾取工序中与欲拾取半导体芯片相邻的半导体芯片因受到针销突起的冲击而造成的松动比率，按照以下的基准进行了评价。
◎(优)：芯片松动低于1％
○(良)：芯片松动为1％以上且低于3％
×(不可)：芯片松动为3％以上
<考察>
在全部实施例中，对全部评价项目均得到了良的结果。另一方面，在全部比较例中，没有任何一个评价项目得到令人满意的结果。比较例1中，由于光聚合性化合物的重均分子量过小，所以容易发生粘合剂的刮起。比较例2以及4中，由于光聚合性化合物的混合量过小，芯片保持性以及拾取性差。比较例3以及5中，由于光聚合性化合物的混合量过多，芯片松动容易发生。比较例5中，晶圆上容易残留粒子。比较例6中，由于光聚合性化合物的重均分子量过大，芯片保持性差，且容易引起芯片松动。比较例7中，由于柔性赋予剂过少，芯片保持性差，且容易引起芯片松动。比较例8中，由于柔性赋予剂过多，容易引起粘合剂的刮起，拾取性差，且在晶圆上容易残留粒子。比较例9中，由于固化剂的混合量过少，拾取性差，且在晶圆上容易残留粒子。比较例10中，由于固化剂的混合量过多，芯片保持性差。比较例11中，由于光聚合引发剂的混合量过少，拾取性差。比较例12中，由于光聚合引发剂的混合量过多，芯片保持性差，且在晶圆上容易残留粒子。

Claims (6)

1.一种粘合片，该粘合片为在基材膜上层叠粘合剂层而成的粘合片，其特征在于：
所述粘合剂层含有(甲基)丙烯酸酯共聚物100质量份、光聚合性化合物5～250质量份、柔性赋予剂20～160质量份、固化剂0.1～30质量份以及光聚合引发剂0.1～20质量份，
所述光聚合性化合物的重均分子量为40000～220000。
2.根据权利要求1所述的粘合片，其特征在于，所述光聚合性化合物为聚氨酯丙烯酸酯低聚物。
3.根据权利要求1或2所述的粘合片，其特征在于，所述光聚合性化合物的不饱和双键官能团数为10以上。
4.根据权利要求1-3中任一项所述的粘合片，其特征在于，所述柔性赋予剂为聚酯丙烯酸酯。
5.一种电子部件的制造方法，其特征在于，具有如下工序：
(a)将权利要求1-4中任一项所述的粘合片贴附于半导体晶圆或基板和环状框上的贴附工序，
(b)将所述半导体晶圆或基板切割成为半导体芯片或半导体部件的切割工序，
(c)向所述粘合片照射活性光线的光照射工序，
(d)为扩展所述半导体芯片或半导体部件相互之间的间隔而拉伸所述粘合片的延展工序，
(e)从所述粘合片拾取半导体芯片或半导体部件的拾取工序。
6.根据权利要求5所述的电子部件的制造方法，其特征在于，所述电子部件是以树脂、陶瓷或金属为材料的封装体。
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