TW201615782A - 粘合片，電子部件的製造方法 - Google Patents

粘合片，電子部件的製造方法 Download PDF

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Publication number
TW201615782A
TW201615782A TW104122101A TW104122101A TW201615782A TW 201615782 A TW201615782 A TW 201615782A TW 104122101 A TW104122101 A TW 104122101A TW 104122101 A TW104122101 A TW 104122101A TW 201615782 A TW201615782 A TW 201615782A
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Taiwan
Prior art keywords
mass
adhesive sheet
parts
wafer
acrylate
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TW104122101A
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English (en)
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TWI666294B (zh
Inventor
Tomoya TSUKUI
Gosuke Nakajima
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Denki Kagaku Kogyo Kk
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • H01L21/683—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
    • 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
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/78—Nitrogen
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    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

本發明提供一種粘合片，在切割程序中能夠抑制粘合劑的刮膠，在切割加工中晶片不飛散，易拾取，不易產生膠粘殘餘。 根據本發明，提供一種粘合片，其特徵在於在基材薄膜上層疊粘合劑層而成，所述粘合劑層含有100質量份(甲基)丙烯酸酯共聚物、5~250質量份光聚合性化合物和20~160質量份柔性賦予劑、0.1~30質量份固化劑和0.1~20質量份光聚合引發劑，所述光聚合性化合物重均分子量為40,000~220,000。

Description

粘合片，電子部件的製造方法
本發明涉及用於電子部件製造程序的粘合片，以及採用此粘合片的電子部件的製造方法。
半導體晶片或基板，貼合粘合片後被分配用於元件片的切斷(Dicing)、粘合片的延伸(Expanding)、從粘合片上進行元件片的剝離(拾取)等各程序。用於這些程序的粘合片(切割膠帶)，相對於切割程序中被切斷的元件片(晶片)具有充分的粘合力，但與此同時也希望在拾取程序中粘合力能夠減少至無膠粘殘餘的程度。
作為粘合片，在對於紫外線及/或電子束等活性光線具有透過性的基材薄膜上，塗抹可由紫外線等引起聚合固化反應的粘合劑層。關於此粘合片，於切割程序後用紫外線等照射粘合劑層，使粘合劑層發生聚合固化從而降低其粘合力後，拾取出被切斷的晶片。
作為此類粘合片，在專利文獻1及專利文獻2中，公開了如下內容：在基材薄膜面塗抹一種粘合劑而組成粘合片，該粘合劑含有例如由於活性 光線而可能導致三維網狀化、分子內含有光聚合性不飽和雙鍵的化合物(多功能低聚物)。
【現有技術文獻】 【專利文獻】
【專利文獻1】日本專利特開2006-049509號公報
【專利文獻2】日本專利特開2007-246633號公報
在半導體晶片或基板的切割程序中，稱為高速旋轉割片的薄型砂輪，藉由刮塗粘合片的粘合劑，使粘合劑附著在單片化的晶片側面，有時成為成品率(yield ratio)低下的原因。
因此，本發明以提供以下粘合片為主要目的，該粘合片能夠抑制切割程序中粘合劑的刮膠，切割加工中晶片不飛散，易拾取，不易產生膠粘殘餘。
根據本發明，提供一種粘合片，其特徵在於在基材薄膜上層疊粘合劑層而成，所述粘合劑層含有100質量份(甲基)丙烯酸酯共聚物、5~250 質量份光聚合性化合物、20~160質量份柔性賦予劑和0.1~30質量份固化劑和0.1~20質量份光聚合引發劑，所述光聚合性化合物重均分子量(重量平均分子量，Weight-average Molecular Weight)為40,000~220,000。
優選粘合片特徵為所述光聚合性化合物為聚氨酯丙烯酸酯低聚物。
優選粘合片特徵為所述光聚合性化合物的不飽和雙鍵官能團數為10以上。
優選所述柔性賦予劑為聚酯丙烯酸酯。
優選，提供含有如下程序的電子部件的製造方法。
(a)將上述粘合片粘貼在半導體晶片或基板與環形框架(Ring Frame)上的粘貼程序、(b)將所述半導體晶片或基板進行切割成為半導體晶片或半導體部件的切割程序、(c)將活性光線照射於所述粘合片的光照射程序、(d)為擴大所述半導體晶片或半導體部件之間的間隔，拉伸所述粘合片的擴展程序、(e)從所述粘合片中拾取出半導體晶片或半導體部件的拾取程序
優選所述電子部件的封裝元件為樹脂、陶瓷或金屬。
根據本發明提供一種粘合片，能夠抑製切割程序中粘合劑的刮膠，切割加工中晶片不飛散，易拾取，不易產生膠粘殘餘。
以下，對用於實施本發明的適宜方式進行說明。
另外，以下說明的實施方式，表示本發明的代表性實施方式的其中一例，並非是對本發明範圍的限定性解釋。
本發明的相關粘合片，其特徵在於在基材薄膜上層疊粘合劑層而成，所述粘合劑層含有100質量份(甲基)丙烯酸酯共聚物和5~250質量份光聚合性化合物和20~160質量份柔性賦予劑和0.1~30質量份固化劑和0.1~20質量份光聚合引發劑，所述光聚合性化合物重均分子量為40,000~220,000。
<粘合劑層>
組成粘合劑層的光可固化型粘合劑含有100質量份(甲基)丙烯酸酯共聚物、5~250質量份光聚合性化合物、20~160質量份柔性賦予劑和0.1~30質量份固化劑和0.1~20質量份光聚合引發劑，所述光聚合性化合物重 均分子量為40,000~220,000。
((甲基)丙烯酸酯共聚物)
作為(甲基)丙烯酸酯共聚物，有丙烯酸、甲基丙烯酸以及它們的酯類單體發生聚合而成的聚合物，這類單體與可發生共聚的不飽和單體(例如，乙酸乙烯、苯乙烯、丙烯腈)發生共聚而成的共聚物。本實施方式的粘合片，組成粘合劑層的粘合劑以易於設定粘合力的丙烯酸聚合物為佳，藉由含有固化劑，能夠對粘合力進行更加精密的調整。然後，至少一種組成丙烯酸聚合物的丙烯酸單體，優選單體中含有官能團。優選此含官能團單體在丙烯酸聚合物中混合0.01質量%以上10質量%以下。若此含官能團單體混合比為0.01質量%以上，對於被粘體的粘合力十分強，滲水的發生有被抑制的趨勢，若此含官能團單體混合比為10質量%以下，對於被粘體的粘合力不至於過高，因而膠粘殘留的發生呈可抑制趨勢。
作為此丙烯酸聚合物的主要單體，例如有丁基(甲基)丙烯酸酯、2-丁基(甲基)丙烯酸酯、叔丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、壬基(甲基)丙烯酸酯、癸基(甲基)丙烯酸酯、月桂(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯、肉豆蔻(甲基)丙烯酸酯、十六烷基(甲基)丙烯酸酯、硬脂(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯等(甲基)丙烯酸單體。
作為此丙烯酸單體，特別優選至少其一部分具有含官能團單體。作為此含官能團單體，優選具有羥基、羧基、環氧基、醯胺基、氨基、羥甲基、磺酸基、氨基磺酸基、(亞)磷酸酯基的單體。並且，即使在它們之中，特別以具有這些官能團的乙烯化合物為佳，優選以含有羥基的乙烯化合物。另外，此處所指乙烯化合物，為含有後述丙烯酸酯的物質。
作為具有羥基的含官能團單體，例如有2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯。
作為具有羧基的單體，例如有(甲基)丙烯酸、巴豆酸、馬來酸、衣康酸、富馬酸、丙烯醯胺N-乙醇酸、肉桂酸等。
作為具有環氧基的單體，例如有烯丙基縮水甘油醚、以及(甲基)丙烯酸縮水甘油醚等。
作為具有醯胺基的單體，例如有(甲基)丙烯醯胺等。
作為有氨基的單體，例如有N,N-二甲基氨基乙基(甲基)丙烯酸酯等。
作為有羥甲基的單體，例如有N-羥甲基丙烯醯胺等。
另外，本實施方式的粘合劑層，使上述丙烯酸聚合物以及固化劑發生反應而致粘合劑層發生固化之後，優選組成該丙烯酸聚合物的含有羥基的單體為該丙烯酸聚合物中0.1~10質量%以下。也就是說，根據其他表現，在利用固化劑使粘合劑發生反應的含官能團單體中，含有羧基的含官能團單體優選10質量%以下。
藉由使用含有羧基的含官能團單體，因為對金屬的粘合力增加，所以若與固化劑發生反應後含有羧基的含官能團單體超過10%質量，則對金屬的粘合力增高膠粘殘餘呈發生趨勢，以10質量%以下為佳。因此，作為具有羧基的單體，優選根據與固化劑反應而易於消減，例如優選使用(甲基)丙烯酸、巴豆酸、馬來酸、衣康酸、富馬酸、丙烯醯胺N-乙醇酸以及肉桂酸。
(固化劑)
在本實施方式的粘合片中，用於粘合劑層的粘合劑優選混合固化劑。混合固化劑的情況，相對於100質量份丙烯酸聚合物，固化劑的混合比為0.1質量份以上30質量份以下，優選1質量份以上20質量份以下。
若此固化劑的混合比為0.1質量份以上30質量份以下，則可以抑制膠粘殘餘的發生。
作為混合於光可固化型粘合劑的固化劑，有多官能異氰酸酯固化劑、多官能環氧固化劑、嗪化合物(Azine compound)，三聚氰胺化合物等，優選，以多官能異氰酸酯固化劑、多官能環氧固化劑為佳。藉由使用作為上 述固化劑至少一部分的多官能環氧固化劑或者多官能異氰酸酯固化劑，可以選擇性的使具有羧基的含官能團單體發生反應而消減，可以調節固化後的具有羧基的含官能團單體。
作為多官能異氰酸酯固化劑，例如有芳香族多異氰酸酯固化劑、脂肪族多異氰酸酯固化劑、脂環族多異氰酸酯硬化劑。
芳香族多異氰酸酯沒有特別限定，例如有1,3-亞苯基二異氰酸酯、4,4'-二苯基二異氰酸酯、1,4-亞苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、聯茴香胺二異氰酸酯、4,4'-二苯基醚二異氰酸酯、4,4',4”-三苯基甲烷三異氰酸酯、ω,ω'-二異氰酸酯-1,3-二甲基苯、ω,ω'-二異氰酸酯-1,4-二甲基苯、ω,ω'-二異氰酸酯-1,4-二乙基苯、1,4-四甲基二甲苯二異氰酸酯以及1,3-四甲基氰酸酯等。
脂肪族聚異氰酸酯沒有特別限定，例如有三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-亞丙基二異氰酸酯、2,3-亞丁基二異氰酸酯、1,3-丁二醇二異氰酸酯、十二亞甲基二異氰酸酯以及2,4,4-三甲基二異氰酸酯等。
脂環族聚異氰酸酯沒有特別限定，例如有3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸、1,4-環己烷 二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2，6-二異氰酸酯環己烷、4,4'-亞甲基雙(環己基異氰酸酯)、1,4-雙(異氰酸甲酯基)環己烷以及1,4-雙(異氰酸甲酯基)環己烷。
聚異氰酸酯中，適當使用1,3-亞苯基二異氰酸酯、4,4'-二苯基二異氰酸酯、1,4-亞苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、六亞甲基二異氰酸酯。
多官能環氧固化劑，主要以具有2個以上環氧基團，1個以上叔氮原子的化合物為佳，例如有N‧N-縮水甘油苯胺、N‧N-縮水甲苯胺、間-N‧N-縮水甘油基苯基縮水甘油醚、對-N‧N-縮水甘油基苯基縮水甘油醚、異氰尿酸三縮水甘油酯、N‧N‧N’‧N’-tetraglycidyldiaminodiphenylmethane(TGDDM)、N‧N‧N’‧N’-四縮水甘油-間苯二甲胺、N‧N‧N’‧N’‧N’’-五縮水甘油胺等。
(光聚合性化合物)
作為光聚合性化合物，使用聚氨酯丙烯酸酯低聚物。聚氨酯丙烯酸酯低聚物可藉由如下反應獲得：聚酯型或者聚醚型等多元醇化合物與多價異氰酸酯化合物發生反應得到末端異氰酸酯聚氨酯預聚物，使該末端異氰酸酯聚氨酯預聚物與具有羥基的(甲基)丙烯酸酯發生反應而得。
多價異氰酸酯化合物，例如可使用2,4-甲苯二異氰酸酯、2,6-甲苯二異 氰酸酯、1,3-氰酸酯、1,4-亞二甲苯基二異氰酸酯、二苯基甲烷4,4-二異氰酸酯、三甲基二異氰酸酯、六亞甲基二異氰酸酯、異氰酸酯。另外，具有羥基的(甲基)丙烯酸酯，例如有2-羥乙基(甲基)丙烯酸酯，2-羥丙基(甲基)丙烯酸酯，聚乙二醇(甲基)丙烯酸酯，季戊四醇三丙烯酸酯，縮水甘油二(甲基)丙烯酸酯，二季戊四醇單羥基五丙烯酸酯等。
作為光聚合性化合物，不飽和雙鍵官能團數為10以上15以下的聚氨酯丙烯酸酯低聚物優選紫外線等光照射後的粘合劑的固化良好。
光聚合性化合物的重均分子量為40,000~220,000，優選80,000~120,000。若光聚合性化合物的重均分子量小，則切割時的粘合劑變得易於刮膠，若重均分子量大則不能獲得粘合力，在切割時晶片易於發生飛散。
光聚合性化合物的配合量，相對於100質量份(甲基)丙烯酸酯共聚物，混合量為5~250質量份，優選40~200質量份。若減少光聚合性化合物的混合量，放射線照射後的粘合片剝離性降低，半導體晶片易發生拾取不良。另一方面，若增加光聚合性化合物的混合量，因光照射程序導致粘合力過度降低，在拾取程序中易發生晶片鬆弛，成為產能下降的原因。
(柔軟賦予劑)
為了軟化粘合劑，提高對粗面的粘合力，也可以添加柔軟賦予劑。
作為柔軟賦予劑，使用聚酯丙烯酸酯。如果是具有不飽和雙鍵官能團的聚酯丙烯酸酯的話，藉由紫外線等光照射發生交聯反應，能夠抑制對被粘體的污染。
聚酯丙烯酸酯，使多元醇與多元酸發生反應而得到聚酯多元醇和丙烯酸或者藉由甲基丙烯酸酯化而得。對於多元醇，例如使用乙二醇、聚乙二醇、丙二醇、聚丙二醇、新戊二醇、1,4-丁二醇等。另外，對於多元酸，例如使用琥珀酸、己二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三酸等。
作為聚酯丙烯酸酯，優選不飽和雙鍵官能團數為1以上3以下。若不飽和雙鍵官能團數比這個數量還多，紫外線等光照射後粘合劑會過度固化導致其與基材的密閉性不好。
柔軟賦予劑的混合比，相對於100質量份(甲基)丙烯酸共聚物優選20質量份以上160質量份以下，更加優選40質量份以上140質量份以下。因為若柔軟賦予劑為20質量份以上，則粘合劑可以塑化，所以對粗面的粘合力上升，切割時半導體晶片的保持性得到維持，若為160質量份以下，能夠抑制由於切割時粘合劑的刮膠而導致的對於半導體晶片的膠粘殘餘的發生。
(光聚合引發劑)
光聚合引發劑，可使用苯偶姻、苯偶姻烷基醚類、苯乙酮類、蒽醌類、噻噸酮類、縮酮類、二苯甲酮類或者氧雜蒽酮等。
作為苯偶姻，例如有苯偶姻、苯偶姻甲基醚、苯偶姻***、苯偶姻丙基醚等。作為苯乙酮類，例如有苯偶姻烷基醚類、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。作為蒽醌類，例如有2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌等。作為噻噸酮類，例如有2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮等。作為縮酮類，例如有苯乙酮二甲基縮酮、苄基二甲基縮酮、苄基聯苯基硫醚、一硫化四甲基秋蘭姆、偶氮二異丁腈、二苄基、雙乙醯、β-crawl anthraquinone等。
光聚合引發劑的混合量，相對於100質量份(甲基)丙烯酸酯共聚物，為1質量份以上20質量份以下，優選1質量份以上10質量份以下。若混合量過少，放射線照射後粘合片的剝離性降低，半導體晶片易發生拾取不良。另一方面，若混合量過多，光聚合引發劑從粘合劑表面滲出，成為污染的原因。
光聚合引發劑，也可根據需要將1種或者2種以上現有的公知的光聚合促進劑進行組合一起使用。光聚合促進劑，可以使用苯甲酸類和叔胺等。作為叔胺，例如有三乙胺，四乙基五胺，二甲氨基醚等。
(增粘樹脂)
粘合劑中可以添加增粘樹脂。作為增粘樹脂，是一種萜烯酚醛樹脂，並使其完全或者部分氫化。
萜烯酚醛樹脂，例如可以使1摩爾萜烯化合物和0.1~50摩爾苯酚類發生反應而製造出來。
作為貼烯化合物，例如有月桂烯、別羅勒烯、羅勒烯、α-蒎烯、β-蒎烯、二戊烯、苧烯、α-水芹烯、α-貼品烯、γ-貼品烯、貼品油烯、1,8-案樹腦、1,4-案樹腦、α-貼品醇、β-松油醇、γ-松油醇、莰烯、三環烯、檜烯、對薄荷二烯、卡倫類等。在這些化合物中，本發明特別優選使用α-蒎烯、β-蒎烯、寧烯、月桂烯、別邏勒烯、α-貼品烯。
作為苯酚類，例如有苯酚、甲酚、二甲苯酚、鄰苯二酚、間苯二酚、對苯二酚、雙酚A，但是不限定於這些。
萜烯酚醛樹脂的苯酚類的比例為25~50摩爾%程度，但是不限於這些。
完全或者部分氫化的萜烯酚醛樹脂的羥基值，優選50~250。羥基值不滿50的情況下，其與異氰酸酯類固化劑不能充分反應，從粘合劑表面滲出，成為污染的原因。若比250多則粘度上升，發生與(甲基)丙烯酸酯共聚物等混合不均，拾取特性不安定。
作為氫化的方法，沒有特別限定，例如有鈀、釕、銠等重金屬或者將這些負載在活性炭、活性氧化鋁、矽藻土等載體上的物質作為催化劑使用的方法，氫化率可以藉由溴價檢測、碘價檢測等進行檢測。
完全或部分氫化的萜烯酚醛樹脂的氫化率，優選30摩爾%以上，更優選70摩爾%以上。因為不滿30摩爾%的情況，由於活性光線照射而引起的光聚合性化合物的反應阻礙，導致粘合力不能充分降低，拾取性下降。
完全或部分氫化的萜烯酚醛樹脂的混合比，相對於100質量份(甲基)丙烯酸酯共聚物優選0.5質量份以上100質量份以下，更優選1.0質量份以上50質量份以下。因為若完全或部分氫化的萜烯酚醛樹脂為0.5質量份以上，粘合力不會過低，所以切割時半導體晶片的保持性得到維持，若100質量份以下，可以抑制拾取不良的發生。
(添加劑等)
粘合劑中，例如可以添加軟化劑，防老化劑，填充劑，導電劑，紫外線吸收劑，以及光穩定劑等各種添加劑。
粘合劑層的厚度，優選1μm以上50μm以下，特別優選5μm以上35μm以下。若粘合劑層過厚，粘合力會過高，拾取性降低。另外，若粘合劑層過薄，粘合力會過低，切割時的晶片保持性降低，環形框架和薄片之 間會發生剝離。
(基材薄膜)
作為基材薄膜的材料，例如有聚氯乙烯、聚乙烯對苯二甲酸酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸-丙烯酸酯膜、乙烯-丙烯酸乙酯共聚物、聚乙烯、聚丙烯、丙烯共聚物、乙烯-丙烯酸共聚物以及乙烯-(甲基)丙烯酸共聚物和乙烯-(甲基)丙烯酸-(甲基)丙烯酸酯共聚物等由金屬離子交聯的離子聚合物樹脂等。
基材薄膜可以為這些樹脂的混合物或者共聚物，也可以為這些樹脂組成的薄膜和薄片的層疊體。
基材薄膜的素材優選使用離子聚合物(ionomer)樹脂。離子聚合物樹脂中，利用Na+、K+、Zn2+等金屬離子將具有乙烯單元、甲基丙烯酸單元以及(甲基)丙烯酸烷基酯單元的共聚物進行交聯，若使用獲得的離子聚合物樹脂，切割碎屑抑制效果明顯，適宜使用。
基材薄膜可以為由上述材料組成的單層或者多層薄膜或者薄片，也可以由不同材料組成的薄膜等層疊而成。基材薄膜的厚度為50~200μm，優選70~150μm。
基材薄膜優選實施抗靜電處理。作為抗靜電處理，有將基材薄膜混合抗靜電劑的處理，將基材表面塗抹抗靜電劑的處理，藉由日冕放電的處理。
作為抗靜電劑，例如可以使用季銨鹽單體等。作為季銨鹽單體，例如有二甲基氨基乙基(甲基)異丁烯酯四級氯化物、二乙基氨基乙基(甲基)異丁烯酯四級氯化物、甲基乙基氨基乙基(甲基)異丁烯酯四級氯化物、對-二甲基氨基乙基異丁烯酯四級氯化物(Dimethyl amino ethyl methacrylate quaternary chloride)以及對-二乙基氨基苯乙烯四級氯化物。這其中，優選二甲基氨基乙基(甲基)異丁烯酯四級氯化物(Quaternary chloride)。
潤滑劑以及抗靜電劑的使用方法沒有特別限定，例如可在基材薄膜的一面塗抹粘合劑，在其反面塗抹潤滑劑以及/或者抗靜電劑，也可以將潤滑劑以及/或者抗靜電劑混煉進基材薄膜的樹脂中從而薄片化。
在基材薄膜的一面層疊粘合劑，其他面可以為平均表面粗糙度(Ra)為0.3~1.5μm的壓紋表面。藉由於擴展裝置的機械平臺一側設置壓紋表面(Embossed surface)，可以在切割後的擴展程序輕鬆擴張基材薄膜。
(潤滑劑)
為了提高切割後的擴展性，可以對基材薄膜的非粘合劑接觸面施予潤滑劑，將潤滑劑混煉進基材薄膜。
潤滑劑，若為降低粘合劑與擴展裝置摩擦指數的物質，沒有特別限定，例如有矽樹脂和(變性)矽油等矽化合物、氟樹脂、六方氮化硼、炭黑以 及二硫化鉬等。這些摩擦降低劑可以多個成分混合。因為電子部件的製造在潔淨室進行，優選使用矽樹脂或者氟樹脂。在矽化合物中，特別適宜採用具有矽微單體單元的共聚物，其與抗靜電層的相溶性良好，能夠取得抗靜電性與擴展性的平衡。
按順序說明本發明的相關電子部件的製造方法的具體程序。
(1)粘貼程序
首先，在粘貼程序中，將粘合片粘貼於半導體晶片和環形框架。晶片可以為矽晶片以及氮化鎵晶圓，碳化矽晶片，藍寶石晶片等現有常用的矽晶片。基板也可採用以樹脂將晶片密封的封裝基板，LED封裝基板，陶瓷基板等通用型基板。
(2)切割程序
在切割程序，將矽晶片等切割成為導體晶片或者半導體部件。
(3)光照射程序
在光照程序中，從基材薄膜一側將紫外線等活性光線對光可固化型粘合劑層進行照射。作為紫外線的光源，可使用低壓汞燈，高壓汞燈，超高壓汞燈，金屬鹵化物燈，黑光燈等。另外，也可用電子束替代紫外線，作為電子束的光源也可使用α線，β線，γ線。
藉由光照，粘合劑層發生三維網狀化而固化，粘合劑層的粘合力降低。此時，如上所述，因為即使將本發明的相關粘合片進行加溫，也不會過度密集於晶片，所以藉由紫外線等照射，粘合力得到充分降低。
(4)擴展．拾取程序
在擴展．拾取程序中，會拉伸粘合片藉以擴大半導體晶片或者半導體部件之間的間隔，再利用針狀推桿(needle pin)將晶片或者部件等向上推。在此之後，將晶片或者部件利用真空夾套或空氣鑷子等進行吸附，從粘合片的粘合劑層上剝離而進行拾取。此時，因為藉由紫外線等照射本發明的相關粘合片，其粘合力得到充分降低，所以晶片或者部件與粘合劑層間易於剝離，獲得良好拾取性，也不會發生膠粘殘留等不良現象。
<粘合片的製造>
作為在基材薄膜上形成粘合劑層以作粘合片的方法，例如有在稱為凹版塗布機，缺角塗布機，棒塗布機，刮刀塗布機或輥式塗布機的塗布機上直接塗抹粘合劑的方法，在剝離薄膜上塗抹/乾燥後在基材上粘貼粘合劑的方法。也可利用凸板印刷，凹板印刷，平版印刷，柔性版印刷，膠版印刷或者絲網印刷等將粘合劑印刷在基材薄膜上。
本發明的粘合片，在電子部件的製造程序之切割程序、晶圓背面剪薄程序中，適宜用來貼裝被稱為work的電子部件集合體。
<實施例．比較例>
用以下處方製造了實施例．比較例的相關光可固化型粘合劑以及粘合片。主要的混合配方及各實驗例的結果如表1~表2所示。
光可固化型粘合劑塗抹於聚對苯二甲酸乙二醇酯(polyethylene terephthalate)製的隔膜上，使乾燥後的粘合層厚度為20μm來進行塗裝。將此粘合層層疊在基材上，於40℃成熟7天，得到粘合片。基材薄膜使用如下薄膜：離子聚合物樹脂之乙烯-甲基丙烯酸-丙烯酸烷基酯共聚物的Zn鹽作為主體，MFR值為1.0g/10分鐘(JIS K7210，210℃)，融點86℃，含有Zn2+離子(三井．杜邦聚合化學品公司製，產品編號：HM1855)藉由T型模擠出，製成150μm的膜。
〔光可固化型粘合劑〕 〔(甲基)丙烯酸酯共聚物〕
A-1：60質量%的丙烯酸甲酯、35質量%的2-乙基己酯、4.5質量%的丙烯酸、0.5質量%的2-羥乙基丙烯酸酯的共聚物，重均分子量為20萬，藉由溶液聚合而得。
A-2：54%的丙烯酸乙酯、19%的丙烯酸丁酯、24%的甲氧基丙烯酸乙酯的共聚物，重均分子量為200萬，藉由乳化聚合而得。
〔光聚合性化合物〕
光可固化型化合物為以下物質，使以雙季戊四醇五丙烯酸酯 (Dipentaerythritol pentaacrylate)為主要成分的含有羥基的丙烯酸酯與異佛爾酮二異氰酸酯(Isophorone diisocyanate)的三聚體的異氰酸酯，根據日本專利特開昭61-42529號公報和日本專利特開2012-36253公報等公知的方法進行調整所得，不飽和雙鍵官能團數為15的聚氨酯丙烯酸酯(合成品)。
另外重均分子量為根據凝膠滲透色譜法(GPC)進行聚苯乙烯換算的重均分子量而進行檢測所得值。
具體為，裝置：GPC-8020 SEC系統(Tosoh公司製)
色譜柱：TSK Guard HZ-L+HZM-N 6.0×150mm×3
流量：0.5ml/min
檢測器：RI-8020
濃度：0.2wt/Vol%
註入量：20μL
柱溫：40℃
系統溫度：40℃
溶劑：THF
檢量線：使用標準聚苯乙烯(PL公司製)製作而成，重均分子量(Mw)以聚苯乙烯換算值表示。
結果，
B-1：重均分子量為11,000
B-2：重均分子量為43,000
B-3：重均分子量為79,000
B-4：重均分子量為124,000
B-5：重均分子量為217,000
B-6：重均分子量為338,000
〔柔軟賦予劑〕
X-1：使乙二醇和琥珀酸發生反應所得的聚酯多元醇與丙烯酸進行反應，得到重均分子量為8，000的聚酯丙烯酸酯
X-2：使丙二醇和偏苯三酸發生反應所得的聚酯多元醇與甲基丙烯酸進行反應，得到重均分子量為5000的聚酯丙烯酸酯
〔固化劑〕
C-1：日本聚氨酯工業株式會社製CORONATE L-45E；2,4-甲苯二異氰酸酯(2,4-tolylene diisocyanate)的三羥甲基丙烷加合物。
C-2：日本聚氨酯工業株式會社製CORONATE HL；六亞甲基二氰酸酯(Hexamethylene diisocyanate)的三羥甲基丙烷加合物。
〔光聚合引發劑〕
D-1：BASF公司製IRGACURE184；1-羥基環己基苯基酮(1-Hydroxy cyclohexyl phenyl ketone)。
D-2：BASF公司製IRGACURE651；苄基二甲基(Benzyldimethylketal)。
【表1】
(1)粘合劑的刮膠，晶片保持性以及拾取性評估
將所得粘合片粘貼於長80mm×寬80mm×厚0.6mm的陶瓷(氧化鋁)和環形框架。在此之後，進行切割、拾取各程序。
切割程序的條件如下。
切割裝置：DISCO公司製DAD341
切割刀片：東京精密公司製MD500-35YM030
切割刀片形狀：外徑58mm，刃寬15μm，內徑40mm
切割刀片圈數：30,000rpm
切割刀片寄送速度：20mm/秒
切割大小：5mm角
對於粘合片的切口量：100μm
切削水溫度：25℃
切削水量：1.0升/分鐘
拾取程序的條件如下。
拾取裝置：佳能機械公司製CAP-300II
擴展量(Expanding amount)：5mm
針狀推桿(Needle pin)形狀：250μmR
針狀推桿數：4個
針狀推桿突出的高度：1.5mm
在切割程序及拾取程序中，進行了以下評估。
(1-1)粘合劑的刮膠
粘合劑的刮膠，隨機選擇50個拾取的晶片，用500倍顯微鏡觀察晶片側面，針對晶片側面是否附著粘合劑按照以下標準進行評估。
◎(優)：晶片側面沒有附著粘合劑。
○(良)：晶片側面附著粘合劑不足5%。
×(不可)：晶片側面附著粘合劑為5%以上
(1-2)晶片保持性
晶片保持性，指在切割程序後，根據保持於粘合片的陶瓷晶片的殘餘率，根據以下標準進行評估。
◎(優)：晶片飛濺為5%以下
○(良)：晶片飛濺為5%以上10%以下
×(不可)：晶片飛濺為10%以上
(1-3)拾取性
拾取性，指在拾取程序中，基於陶瓷晶片的拾取成功率，按照以下標準進行評估。
◎(優)：晶片的拾取成功率為95%以上
○(良)：晶片的拾取成功率為80%以上95%以下
×(不可)：晶片的拾取成功率為80%以下
(2)污染性
將粘合片粘貼於矽製鏡面晶圓，0分後用高壓水銀明燈150mJ/cm2照射了紫外線之後，剝離了粘合片。以粒子計數器(Particle Counter)測量了在矽製鏡面晶圓的貼付面上殘留的0.28μm以上的粒子數。
優：粒子數為500個以下
良：粒子數為501個以上2000個以下。
不可：粒子數為2001個以上。
(3)晶片鬆動
在拾取程序中，預定拾取之半導體晶片的相鄰半導體晶片會因推桿(pin)上推衝擊而導致鬆動，而前述晶片鬆動是指基於該鬆動的機率，並且按照以下標準進行評估。
◎(優)：晶片鬆動率為不足1%
○(良)：晶片鬆動率為1%以上~不足3%
×(不可)：晶片鬆動率為3%以上
<考察>
在全部實施例中，對於全部評估專案均得到良好結果。另一方面，在全部的比較例中，至少有一個評估項目沒有得到滿意的結果。在比較例1中，因為光聚合性化合物的重均分子量過小，所以易引起粘合劑的膠粘。在比較例2以及4中，因為光聚合性化合物的混合量過少，所以晶片保持性以及拾取性差。在比較例3以及5中，因為光聚合性化合物的混合量過多，所以易引起晶片鬆動。在比較例5中，晶片上粒子易殘留。在比較例6中，因為光聚合性化合物的重均分子量過大，所以晶片保持性差，並且易引起晶片鬆動。在比較例7中，因為柔軟賦予劑過少，所以晶片保持性差，並且易引起晶片鬆動。在比較例8中，因為柔軟賦予劑過多，所以易引起粘合劑的膠粘，拾取性差，並且晶片上粒子易殘留。在比較例9中，因為 固化劑的混合量過少，所以拾取性差，並且晶片上粒子易殘留。在比較例10中，因為固化劑的混合量過多，所以晶片保持性差。在比較例11中，因為光聚合引發劑的混合量過少，所以拾取性差。
在比較例12中，因為光聚合引發劑的混合量過多，所以晶片保持性差，並且晶片上粒子易殘留。

Claims (6)

  1. 一種粘合片，其特徵在於，所述粘合片由在基材薄膜上層疊粘合劑層而成，所述粘合劑層含有100質量份(甲基)丙烯酸酯共聚物和5~250質量份光聚合性化合物、20~160質量份柔軟賦予劑、0.1~30質量份固化劑和0.1~20質量份光聚合引發劑，所述光聚合性化合物的重量平均分子量為40,000~220,000。
  2. 請求項1中所述的粘合片，其特徵在於，所述光聚合性化合物為聚氨酯丙烯酸酯低聚物。
  3. 請求項1或請求項2中所述的粘合片，其特徵在於，所述光聚合性化合物的不飽和雙鍵官能團數為10以上。
  4. 請求項1~3中的任一項所述的粘合片，其特徵在於，所述柔軟賦予劑為聚酯丙烯酸酯。
  5. 一種電子部件的製造方法，含有以下程序：(a)粘貼程序，將請求項1~4中的任一項所述的粘合片粘貼於半導體晶片或基板與環形框架；(b)切割程序，將所述半導體晶片或基板進行切割成為半導體晶片或半導體部件；(c)光照射程序，對所述粘合片照射活性光線；(d)擴展程序，為擴大所述半導體晶片或半導體部件之間的間隔，拉伸所述粘合片；(e)拾取程序，從所述粘合片拾取(pickup)半導體晶片或半導體部 件。
  6. 請求項5中所述的電子部件的製造方法，其特徵在於，所述電子部件以樹脂、陶瓷或者金屬作為材料進行封裝。
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