JP2002158276A - Adhesive sheet for sticking wafer and semiconductor device - Google Patents

Adhesive sheet for sticking wafer and semiconductor device

Info

Publication number
JP2002158276A
JP2002158276A JP2000353569A JP2000353569A JP2002158276A JP 2002158276 A JP2002158276 A JP 2002158276A JP 2000353569 A JP2000353569 A JP 2000353569A JP 2000353569 A JP2000353569 A JP 2000353569A JP 2002158276 A JP2002158276 A JP 2002158276A
Authority
JP
Japan
Prior art keywords
sensitive adhesive
pressure
adhesive layer
radiation
adhesive sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2000353569A
Other languages
Japanese (ja)
Inventor
Katsuhide Aichi
且英 愛知
Yuji Hasegawa
雄二 長谷川
Minoru Sugiura
実 杉浦
Takashi Masuko
崇 増子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Denko Materials Co Ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2000353569A priority Critical patent/JP2002158276A/en
Publication of JP2002158276A publication Critical patent/JP2002158276A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To keep enough chip space in expanding process after wafer dicing in a adhesive sheet having a wafer fixing function and a die adhesion function, and to realize high anti-reflow-crack for a semiconductor device that uses the adhesive sheet. SOLUTION: This adhesive sheet is provided with a radiation hardening adhesive layer 3, which consists of adhesive and radiation polymerization oligomer, and an adhesive layer for die adhesion 4 on a base element 2 in this order. In this adhesive sheet, the elastic modulus after radiation hardening of the radiation hardening adhesive layer is from 0.1 to 10 MPa, the coefficient of water absorption of the adhesive layer for die adhesion is 1.5 volume % or less, and elastic modulus at 250 deg.C is 10 MPa or less.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はウエハ貼着用粘着シ
ートおよび半導体装置に関し、さらに詳しくは、半導体
ウエハを小片に切断分離する工程とリードフレームにダ
イボンディングする工程に用いられるウエハ貼着用粘着
シート、およびその粘着シートを使用してなる半導体装
置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet for attaching a wafer and a semiconductor device, and more particularly to an adhesive sheet for attaching a wafer used in a step of cutting and separating a semiconductor wafer into small pieces and a step of die bonding to a lead frame. And a semiconductor device using the adhesive sheet.

【０００２】[0002]

【従来の技術】シリコン、ガリウムヒ素などの半導体ウ
エハは大径の状態で製造され、このウエハは小片のダイ
（以下、チップという）に切断分離（ダイシング）され
た後に次の工程であるマウント工程に移されている。こ
の際、半導体ウエハは予め粘着シートに貼着された状態
でダイシング、洗浄、乾燥、エキスパンディング、ピッ
クアップの各工程が加えられた後、次工程のボンディン
グ工程に移送される。2. Description of the Related Art Semiconductor wafers of silicon, gallium arsenide and the like are manufactured in a large diameter state, and this wafer is cut and separated (diced) into small pieces of dies (hereinafter, referred to as chips), and then a mounting step as a next step. Has been moved to. At this time, the semiconductor wafer is subjected to dicing, cleaning, drying, expanding, and pickup steps in a state where the semiconductor wafer is attached to the adhesive sheet in advance, and then transferred to the next bonding step.

【０００３】このような半導体ウエハのダイシング工程
からピックアップ工程に至る工程で用いられる粘着シー
トとしては、ダイシング工程から乾燥工程までは半導体
素子のチップ（以下、チップという）に対して充分な接
着力を有しており、ピックアップ時にはチップに粘着剤
が付着しない程度の接着力を有しているものが望まれて
いる。[0003] Such an adhesive sheet used in a process from a dicing process to a pick-up process of a semiconductor wafer has a sufficient adhesive force to a chip of a semiconductor element (hereinafter referred to as a chip) from a dicing process to a drying process. It is desired that the chip has an adhesive force such that the adhesive does not adhere to the chip during pickup.

【０００４】ピックアップされたチップは、ダイボンデ
ィング工程において、エポキシ接着剤などのダイ接着用
接着剤を介してリードフレームに接着され、半導体装置
が製造されている。しかしながら、チップが非常に小さ
な場合には、適量の接着剤を塗布することが困難であ
り、チップから接着剤がはみ出したり、あるいはチップ
が大きい場合には、接着剤量が不足するなど、充分な接
着力を有するように接着を行うことができないなどとい
う問題点があった。またこのようなダイ接着用接着剤の
塗布作業は煩雑でもあり、プロセスを簡略化するために
も改善が要求されている。[0004] In a die bonding step, the picked-up chip is bonded to a lead frame via a die bonding adhesive such as an epoxy bonding agent to manufacture a semiconductor device. However, if the chip is very small, it is difficult to apply an appropriate amount of adhesive, and if the adhesive protrudes from the chip, or if the chip is large, the amount of adhesive is insufficient. There has been a problem that bonding cannot be performed so as to have adhesive strength. In addition, such an operation of applying the die-bonding adhesive is complicated, and improvement is required to simplify the process.

【０００５】このような問題点を解決するために、ウエ
ハ固定機能とダイ接着機能とを同時に兼ね備えたウエハ
貼着用粘着シートが種々提案されている（たとえば、特
開平２−３２１８１号公報、特開平３−２６８３４５号
公報、特公平３−３４８５３号公報等参照）。In order to solve such problems, various types of pressure-sensitive adhesive sheets for attaching wafers having both a wafer fixing function and a die bonding function have been proposed (for example, Japanese Patent Application Laid-Open Nos. 2-32181 and 2-31181). JP-A-3-268345, JP-B-3-34853, etc.).

【０００６】特開平２−３２１８１号公報には、（メ
タ）アクリル酸エステル共重合体、エポキシ樹脂、光重
合性低分子化合物、熱活性型潜在性エポキシ樹脂硬化剤
および光重合開始剤よりなる組成物から形成される接着
剤層と、基材とからなる粘接着テープが開示されてい
る。この接着剤層は、ウエハダイシング時には、ウエハ
を固定する機能を有し、ダイシング終了後、エネルギー
線を照射すると硬化し、基材との間の接着力が低下す
る。したがって、チップのピックアップを行うと、接着
剤層は、チップとともに剥離する。接着剤層を伴った半
導体素子をリードフレームに載置し、加熱すると、接着
剤層が接着力を発現し、半導体素子とリードフレームと
の接着が完了する。JP-A-2-32181 discloses a composition comprising a (meth) acrylate copolymer, an epoxy resin, a photopolymerizable low-molecular compound, a heat-active latent epoxy resin curing agent and a photopolymerization initiator. An adhesive tape comprising an adhesive layer formed of a product and a substrate is disclosed. This adhesive layer has a function of fixing the wafer at the time of wafer dicing, and after the dicing is completed, is hardened when irradiated with energy rays, and the adhesive strength between the substrate and the base material is reduced. Therefore, when the chip is picked up, the adhesive layer peels off together with the chip. When the semiconductor element with the adhesive layer is placed on a lead frame and heated, the adhesive layer develops an adhesive force, and the bonding between the semiconductor element and the lead frame is completed.

【０００７】特公平３−３４８５３号公報には、剥離層
が実質的に存在しない表面を有する重合体支持フィルム
と、導電性接着剤とからなるダイシング用フィルムが教
示されている。この導電性接着剤は、上記の接着剤層と
略同等の機能を有する。[0007] Japanese Patent Publication No. 3-34853 teaches a dicing film comprising a polymer support film having a surface substantially free of a release layer and a conductive adhesive. This conductive adhesive has substantially the same function as the above-mentioned adhesive layer.

【０００８】また特開平３−２６８３４５号公報には、
支持基材上に設けられた加熱発泡粘着層の上に、ダイ接
着用の接着剤層が設けられており、加熱により該接着剤
層と加熱発泡粘着層とが剥離可能となる、半導体ウエハ
の分断時の支持機能を兼ね備えたダイ接着用シートが教
示されている。Japanese Patent Application Laid-Open No. 3-268345 discloses that
An adhesive layer for die bonding is provided on the heat-foamable pressure-sensitive adhesive layer provided on the supporting substrate, and the adhesive layer and the heat-foamable pressure-sensitive adhesive layer can be peeled off by heating. A die bonding sheet having a supporting function at the time of cutting is taught.

【０００９】上記公報類に開示されているウエハ貼着用
粘着シートは、いわゆるダイレクトダイボンディングを
可能にし、ダイ接着用接着剤の塗布工程を省略できるよ
うになる。[0009] The pressure-sensitive adhesive sheet for attaching a wafer disclosed in the above publications enables so-called direct die bonding, so that the step of applying a die bonding adhesive can be omitted.

【００１０】本発明者らは、このようなダイレクトダイ
ボンディングを可能にするようなウエハ貼着用粘着シー
トの１種として、基材面上に、放射線硬化型粘着剤層
と、ダイ接着用接着剤層とがこの順に形成されてなるウ
エハ貼着用粘着シートについての改良研究を行ってい
る。The present inventors have proposed a kind of pressure-sensitive adhesive sheet for attaching a wafer which enables such direct die bonding, a radiation-curable pressure-sensitive adhesive layer and a die bonding adhesive on a substrate surface. We are studying improvements on pressure-sensitive adhesive sheets for attaching wafers in which layers are formed in this order.

【００１１】放射線硬化型粘着剤としては従来より、光
照射によって三次元網状化しうる、分子内に光重合性炭
素−炭素二重結合を少なくとも２個以上有する低分子量
放射線硬化性化合物からなる粘着剤が提案されている。
粘着剤の硬化は、その粘着剤中に含まれる放射線硬化性
化合物を放射線照射によって硬化させ粘着剤に三次元網
状化構造を与えて、その流動性を著しく低下させる原理
に基づく。As the radiation-curable pressure-sensitive adhesive, a pressure-sensitive adhesive composed of a low-molecular-weight radiation-curable compound having at least two or more photopolymerizable carbon-carbon double bonds in a molecule, which can be formed into a three-dimensional network by light irradiation, has been used. Has been proposed.
The curing of the pressure-sensitive adhesive is based on the principle that a radiation-curable compound contained in the pressure-sensitive adhesive is cured by irradiation with radiation to give a three-dimensional network structure to the pressure-sensitive adhesive, thereby significantly reducing its fluidity.

【００１２】[0012]

【発明が解決しようとする課題】上記した、基材面上
に、放射線硬化型粘着剤層と、ダイ接着用接着剤層とが
この順に形成されてなるウエハ貼着用粘着シートについ
て、特にエキスパンディング工程およびピックアップ工
程において次のような問題点があった。The above-mentioned pressure-sensitive adhesive sheet for attaching a wafer, in which a radiation-curable pressure-sensitive adhesive layer and a die-bonding pressure-sensitive adhesive layer are formed in this order on a substrate surface, is particularly expanded. There are the following problems in the process and the pickup process.

【００１３】エキスパンディング工程は、ダイシングさ
れた半導体素子（チップ）の間隔を広げ、チップのピッ
クアップを容易にする工程である。上記のウエハ貼着用
粘着シートを用いると、粘着剤層の硬化が相当進行し、
粘着剤層がかなり硬くなる（１０〜１００ＭＰａ）。こ
のためシートの伸び率（拡張率）が小さくなるため、所
望のチップ間隔を得るのが困難であった。すなわち、隣
接するチップとチップとの間隔が充分に得られず、ピッ
クアップ工程における認識不良の原因となり、誤動作を
起こすことがあった。また上記のような問題点があるた
め、用いられる基材についても限定される場合があっ
た。The expanding step is a step of widening the interval between diced semiconductor elements (chips) and facilitating chip pickup. When the above-mentioned pressure-sensitive adhesive sheet for wafer attachment is used, the curing of the pressure-sensitive adhesive layer considerably proceeds,
The pressure-sensitive adhesive layer becomes considerably hard (10 to 100 MPa). For this reason, the elongation rate (expansion rate) of the sheet becomes small, so that it was difficult to obtain a desired chip interval. That is, a sufficient distance between adjacent chips cannot be obtained, which may cause a recognition failure in the pickup process and cause a malfunction. In addition, due to the above-mentioned problems, the substrate used may be limited.

【００１４】一方、これまでそれほど注目されなかった
ダイ接着用接着剤について、半導体パッケージの実装方
法が、従来のピン挿入型に代わり、高密度実装に適した
表面実装型が主流になってきたことによる耐熱性の向上
が課題となっている。この表面実装型パッケージは、リ
ードをプリント基板等に直接はんだ付けするために、赤
外線リフローやベーパーフエーズリフロー、はんだディ
ップなどにより、パッケージ全体を加熱して実装され
る。この際、パッケージ全体が２１０〜２６０℃の高温
にさらされるため、パッケージ内部に水分が存在する
と、水分の爆発的な気化により、パッケージクラック
（以下リフロークラックという）が発生する。このリフ
ロークラックは、半導体パッケージの信頼性を著しく低
下させるため、深刻な問題・技術課題となっている。ダ
イ接着用接着剤に起因するリフロークラックの発生メカ
ニズムは、次の通りである。半導体パッケージは、保管
されている間に（１）ダイ接着用接着剤が吸湿し、
（２）この水分がリフローはんだ付けの実装時に、加熱
によって水蒸気化し、（３）この蒸気圧によってダイ接
着用接着剤の破壊やはく離が起こり、（４）リフローク
ラックが発生する。封止材の耐リフロークラック性が向
上してきている中で、ダイ接着用接着剤に起因するリフ
ロークラックは、特に薄型パッケージにおいて、重大な
問題となっており、耐リフロークラック性の改良が強く
要求されている。ダイ接着用接着剤層については、例え
ば特開第２０００−１０４０４０号において、ウエハの
反りや接着剤層中のボイドを低減することにより耐リフ
ロー性の良好なフィルム状接着剤の物性の条件が提案さ
れている。しかし、半導体の実装技術の進歩に対応する
ため、常に改良、改善が要求されつづける必要がある。On the other hand, as for the die bonding adhesive, which has not received much attention until now, the method of mounting a semiconductor package has been replaced by the conventional pin insertion type, and the surface mounting type suitable for high density mounting has become mainstream. Therefore, the improvement of heat resistance due to this has been an issue. This surface mount type package is mounted by heating the entire package by infrared reflow, vapor phase reflow, solder dip, or the like in order to directly solder the leads to a printed circuit board or the like. At this time, since the entire package is exposed to a high temperature of 210 to 260 ° C., if moisture exists inside the package, explosive vaporization of the moisture causes a package crack (hereinafter referred to as a reflow crack). The reflow crack significantly reduces the reliability of the semiconductor package, and is a serious problem and technical problem. The mechanism of occurrence of reflow cracks caused by the die bonding adhesive is as follows. While the semiconductor package is stored, (1) the die bonding adhesive absorbs moisture,
(2) This moisture is vaporized by heating during the reflow soldering, (3) the adhesive for die bonding is broken or peeled off by the vapor pressure, and (4) a reflow crack occurs. As the reflow crack resistance of the encapsulant has been improved, reflow cracks caused by die bonding adhesives have become a serious problem, especially in thin packages, and there is a strong demand for improved reflow crack resistance. Have been. Regarding the adhesive layer for die bonding, for example, Japanese Patent Application Laid-Open No. 2000-104040 proposes conditions for physical properties of a film-like adhesive having good reflow resistance by reducing wafer warpage and voids in the adhesive layer. Have been. However, in order to keep up with the progress of semiconductor mounting technology, it is necessary to keep improving and improving.

【００１５】本発明は、上記のような従来技術に鑑みて
なされたものであって、ウエハ固定機能とダイ接着機能
とを同時に兼ね備えたウエハ貼着用粘着シートにおい
て、粘着剤層に起因するエキスパンディング工程および
ピックアップ工程における上記問題点を解決するのと同
時に、高い耐リフロークラック性を実現する事を目的と
している。また本発明は、上記問題点を解決することに
より、基材の材料マージンを広げることを目的としてい
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been developed in an adhesive sheet for attaching a wafer, which has both a wafer fixing function and a die attaching function, due to an adhesive layer. It is an object of the present invention to solve the above-mentioned problems in the process and the pickup process and to realize high reflow crack resistance. Another object of the present invention is to increase the material margin of the base material by solving the above problems.

【００１６】[0016]

【課題を解決するための手段】本発明に係るウエハ貼着
用粘着シートは、基材面上に、少なくとも粘着剤と放射
線重合性オリゴマーとからなる放射線硬化型粘着剤層
と、ダイ接着用接着剤層とがこの順に形成されてなり、
該放射線硬化型粘着剤層の放射線硬化後における弾性率
が０．１〜１０ＭＰａであり、かつダイ接着用接着剤層
の接着剤層の吸水率が１．５体積％以下であり、２５０
℃における弾性率が１０ＭＰａ以下であることを特徴と
する。The pressure-sensitive adhesive sheet for attaching a wafer according to the present invention comprises a radiation-curable pressure-sensitive adhesive layer comprising at least a pressure-sensitive adhesive and a radiation-polymerizable oligomer on a substrate surface, and a die-bonding adhesive. Layers are formed in this order,
The radiation-curable pressure-sensitive adhesive layer has an elastic modulus after radiation curing of 0.1 to 10 MPa, and the water absorption of the adhesive layer of the die-bonding adhesive layer is 1.5% by volume or less;
The elastic modulus at 10 ° C. is 10 MPa or less.

【００１７】本発明に係るウエハ貼着用粘着シートにお
いては、前記放射線硬化型粘着剤層中において、該放射
線重合性オリゴマーが、１〜３０μｍの分散粒径を有
し、かつ均一に分散されてなることが好ましい。In the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention, the radiation-polymerizable oligomer has a dispersed particle size of 1 to 30 μm and is uniformly dispersed in the radiation-curable pressure-sensitive adhesive layer. Is preferred.

【００１８】[0018]

【発明の実施の形態】本発明に係るウエハ貼着用粘着シ
ート(以下、粘着シートという)１は、その断面図が図１
に示されるように、基材２と、この上に形成された放射
線硬化型粘着剤層３と、放射線硬化型粘着剤層３上に形
成されたダイ接着用接着剤層４とから構成されている。
使用前にはこのダイ接着用接着剤層４を保護するため、
図２に示すようにダイ接着用接着剤層４の上面に剥離性
シート５を仮粘着しておくことが好ましい。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A pressure-sensitive adhesive sheet for sticking a wafer (hereinafter referred to as a pressure-sensitive adhesive sheet) 1 according to the present invention is shown in FIG.
As shown in the figure, the radiation-curable pressure-sensitive adhesive layer 3 formed on the substrate 2, and the die-bonding adhesive layer 4 formed on the radiation-curable pressure-sensitive adhesive layer 3 I have.
Before use, to protect the die bonding adhesive layer 4,
As shown in FIG. 2, it is preferable that the releasable sheet 5 be temporarily adhered to the upper surface of the die bonding adhesive layer 4.

【００１９】本発明に係る粘着シートの形状は、テープ
状、ラベル状などあらゆる形状をとりうる。以下、本発
明で用いられる基材２、放射線硬化型粘着剤層３および
ダイ接着用接着剤層４について順次説明する。The shape of the pressure-sensitive adhesive sheet according to the present invention can take any shape such as a tape shape and a label shape. Hereinafter, the substrate 2, the radiation-curable pressure-sensitive adhesive layer 3, and the die-bonding adhesive layer 4 used in the present invention will be sequentially described.

【００２０】基材２としては、長さ方向および幅方向に
延伸性を有する合成樹脂フィルムを基材として用いるこ
とが好ましい。このような基材２としては、具体的に
は、ポリエチレンフィルム、ポリプロピレンフィルム、
ポリブテンフィルム、ポリ塩化ビニルフィルム、ポリエ
チレンテレフタレートフィルム、ポリブチレンテレフタ
レートフィルム、ポリブタジエンフィルム、ポリウレタ
ンフィルム、ポリメチルペンテンフィルム、エチレン酢
ビフィルム、アイオノマーおよびエチレン・（メタ）ア
クリル酸共重合体フィルム等ならびにこれらの架橋フィ
ルムが用いられる。またこれらの積層フィルムであって
もよい。基材２の膜厚は、通常は１０〜３００μｍ程度
であり、好ましくは５０〜２００μｍ程度である。As the substrate 2, a synthetic resin film having stretchability in the length direction and the width direction is preferably used. As such a substrate 2, specifically, a polyethylene film, a polypropylene film,
Polybutene film, polyvinyl chloride film, polyethylene terephthalate film, polybutylene terephthalate film, polybutadiene film, polyurethane film, polymethylpentene film, ethylene vinyl acetate film, ionomer, ethylene / (meth) acrylic acid copolymer film and the like and cross-linking thereof A film is used. Also, these laminated films may be used. The film thickness of the base material 2 is usually about 10 to 300 μm, preferably about 50 to 200 μm.

【００２１】本発明の粘着シートでは、後述するよう
に、その使用に当たり、電子線（ＥＢ）や紫外線（Ｕ
Ｖ）などの放射線照射が行なわれるが、ＥＢ照射の場合
には、該基材２は透明である必要はないが、ＵＶ照射を
して用いる場合には、透明である必要がある。In the pressure-sensitive adhesive sheet of the present invention, as will be described later, the electron beam (EB) or the ultraviolet (U)
The substrate 2 is not required to be transparent in the case of EB irradiation, but needs to be transparent in the case of UV irradiation.

【００２２】放射線硬化型粘着剤層３は、少なくとも粘
着剤と放射線重合性オリゴマーとから形成されている。
放射線硬化型粘着剤層３の放射線硬化後における弾性率
は、０．１〜１０ＭＰａであり、好ましくは０．５〜５
ＭＰａである。The radiation-curable pressure-sensitive adhesive layer 3 is formed from at least a pressure-sensitive adhesive and a radiation-polymerizable oligomer.
The elastic modulus of the radiation-curable pressure-sensitive adhesive layer 3 after radiation curing is 0.1 to 10 MPa, preferably 0.5 to 5 MPa.
MPa.

【００２３】本発明に係るウエハ貼着用粘着シートにお
いては、放射線硬化後の放射線硬化型粘着剤３層が上記
のように特定の弾性率を有する。したがって、放射線照
射を行うと、放射線硬化型粘着剤層３の粘着力はチップ
のピックアップを行える程度に粘着力が低下し、また充
分なエキスパンディングを行える程度の弾性率が維持さ
れる。この結果、所望のチップ間距離が容易に得られる
ようになる。In the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention, the three layers of the radiation-curable pressure-sensitive adhesive after radiation curing have the specific elastic modulus as described above. Therefore, when the radiation is applied, the adhesive strength of the radiation-curable adhesive layer 3 is reduced to such an extent that a chip can be picked up, and the elastic modulus enough to perform sufficient expanding is maintained. As a result, a desired distance between chips can be easily obtained.

【００２４】このような放射線硬化型粘着剤層３の膜厚
は、通常は、３〜５０μｍ程度であり、好ましくは５〜
３０μｍ程度である。また放射線硬化型粘着剤層３中に
おいて、放射線重合性オリゴマーは、好ましくは１〜３
０μｍ、特に好ましくは１〜１０μｍの分散粒径を有
し、放射線硬化型粘着剤層３中に均一に分散している。
ここで、分散粒径は、放射線硬化型粘着剤層３を、６０
０倍の顕微鏡で観察して、顕微鏡内のスケールにて実測
することで決定される値である。また、均一分散とは、
隣接する粒子間の距離が、０．１〜１０μｍである状態
をいう。分散粒径が３０μｍを超える場合、放射線硬化
性粘着剤層３は、実質上、相分離しており、放射線硬化
前の粘着性も、放射線硬化後のピックアップ性も実現で
きない。また分散粒径が全て０．１μｍ以下の場合は、
放射線硬化性粘着剤層３は、実質上、完全相溶系であ
り、放射線硬化後の弾性率が上昇し、エキスパンディン
グおよびピックアップ性に劣ってしまう。このような構
造は、「海島構造」と呼ばれ、放射線を照射すると重合
硬化する部分（島部）と、重合にあずからない部分（海
部）とが均一に分散にしている状態である。したがっ
て、放射線照射を行うと、重合硬化した部分においては
粘着力、弾性率ともに大幅に低下するが、重合硬化にあ
ずからない部分においては粘着力、弾性率ともに維持さ
れる。この結果、全体としては、チップ（ダイ接着用接
着剤を伴う）のピックアップを行える程度に粘着力が低
下し、また充分なエキスパンディングを行える程度の弾
性率が維持される。The thickness of the radiation-curable pressure-sensitive adhesive layer 3 is usually about 3 to 50 μm, preferably 5 to 50 μm.
It is about 30 μm. In the radiation-curable pressure-sensitive adhesive layer 3, the radiation-polymerizable oligomer is preferably 1 to 3.
It has a dispersed particle size of 0 μm, particularly preferably 1 to 10 μm, and is uniformly dispersed in the radiation-curable pressure-sensitive adhesive layer 3.
Here, the dispersion particle size is such that the radiation-curable pressure-sensitive adhesive layer 3
It is a value determined by observing with a microscope of 0 magnification and actually measuring on a scale in the microscope. Also, what is uniform dispersion?
It refers to a state in which the distance between adjacent particles is 0.1 to 10 μm. When the dispersed particle size exceeds 30 μm, the radiation-curable pressure-sensitive adhesive layer 3 is substantially phase-separated, and cannot realize the tackiness before the radiation curing and the pickup property after the radiation curing. When all the dispersed particle diameters are 0.1 μm or less,
The radiation-curable pressure-sensitive adhesive layer 3 is substantially a completely compatible system, has an increased elastic modulus after radiation curing, and is inferior in expandability and pickup properties. Such a structure is called a “sea-island structure”, in which a portion that is polymerized and cured by irradiation (island portion) and a portion that does not participate in polymerization (sea portion) are uniformly dispersed. Therefore, when irradiation is performed, both the adhesive strength and the elastic modulus are significantly reduced in the polymerized and cured portion, but both the adhesive strength and the elastic modulus are maintained in the portion that does not participate in the polymerization and curing. As a result, as a whole, the adhesive force is reduced to such an extent that the chip (with the adhesive for die bonding) can be picked up, and the elastic modulus enough to perform sufficient expanding is maintained.

【００２５】ここで、弾性率は以下の手法により決定さ
れる値である。すなわち、粘着剤層３を構成する放射線
硬化型粘着剤を８０Ｗ／cmの高圧水銀灯下に置き、１秒
間放射線を照射する。これを円柱状に貼り合わせ、底面
φ８mm、高さ５mmとし、これを粘弾性測定に供した。放
射線硬化後の試料の貯蔵弾性率は、レオメトリックス
（製）ＲＤＳ−IIを用いて剪断法により測定された。測
定条件は、２３℃、５００rad/秒である。Here, the elastic modulus is a value determined by the following method. That is, the radiation-curable pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 3 is placed under a high-pressure mercury lamp of 80 W / cm and irradiated with radiation for one second. This was adhered in a cylindrical shape to make the bottom surface φ8 mm and the height 5 mm, and this was subjected to viscoelasticity measurement. The storage modulus of the sample after radiation curing was measured by a shearing method using Rheometrics (manufactured by RDS-II). The measurement conditions are 23 ° C. and 500 rad / sec.

【００２６】放射線硬化型粘着剤層３を構成する粘着剤
としてはアクリル系粘着剤が好ましく、具体的には、
（メタ）アクリル酸エステルあるいはその誘導体を主た
る構成単量体単位とする（メタ）アクリル酸エステル共
重合体、あるいはこれら共重合体の混合物が用いられ
る。The pressure-sensitive adhesive constituting the radiation-curable pressure-sensitive adhesive layer 3 is preferably an acrylic pressure-sensitive adhesive.
A (meth) acrylate copolymer containing (meth) acrylate or a derivative thereof as a main constituent monomer unit, or a mixture of these copolymers is used.

【００２７】特に、（メタ）アクリル酸エステル共重合
体としては、アルキル基の炭素数が１〜１４である（メ
タ）アクリル酸アルキルエステルから選択される少なく
とも１種以上の（メタ）アクリル酸アルキルエステルモ
ノマーと、（メタ）アクリル酸グリシジル、（メタ）ア
クリル酸ジメチルアミノエチル、（メタ）アクリル酸ジ
エチルアミノエチル、（メタ）アクリル酸2-ヒドロキシ
エチル、酢酸ビニル、スチレン、塩化ビニルから選択さ
れる少なくとも１種の酸基を有しない極性モノマーと、
アクリル酸、メタクリル酸、マレイン酸から選択される
少なくとも１種の酸基を有するコモノマーとの共重合体
が用いられる。Particularly, as the (meth) acrylate copolymer, at least one or more alkyl (meth) acrylates selected from alkyl (meth) acrylates having 1 to 14 carbon atoms in the alkyl group are used. An ester monomer and at least one selected from glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, styrene, and vinyl chloride A polar monomer having no one acid group;
A copolymer with a comonomer having at least one acid group selected from acrylic acid, methacrylic acid, and maleic acid is used.

【００２８】このような（メタ）アクリル酸エステル共
重合体中では、（メタ）アクリル酸アルキルエステルモ
ノマーと、酸基を有しない極性モノマーと、酸基を有す
るコモノマーとの比は、通常３５〜９９／１〜６０／０
〜５であり、特に好ましくは７０〜９５／５〜３０／０
である。In such a (meth) acrylic acid ester copolymer, the ratio of the (meth) acrylic acid alkyl ester monomer, the polar monomer having no acid group, and the comonomer having the acid group is usually 35 to 35. 99/1 to 60/0
To 5, particularly preferably 70 to 95/5 to 30/0.
It is.

【００２９】コモノマーとして、酸基を有しない極性モ
ノマーが６０重量％を超えて共重合されると、放射線硬
化型粘着剤層３は、完全相溶系となり、放射線硬化後に
おける弾性率が１０ＭＰａを超えてしまい、充分なエキ
スパンド性、ピックアップ性が得られなくなり、一方、
１重量％未満で共重合されると、放射線硬化型粘着剤層
３は不均一な分散系となり、良好な粘着物性が得られな
くなる。When a polar monomer having no acid group as a comonomer is copolymerized in an amount exceeding 60% by weight, the radiation-curable pressure-sensitive adhesive layer 3 becomes a completely compatible system and has an elastic modulus after radiation curing of more than 10 MPa. And expandability and pick-up properties cannot be obtained.
If the copolymerization is performed at less than 1% by weight, the radiation-curable pressure-sensitive adhesive layer 3 becomes a non-uniform dispersion system, and good pressure-sensitive adhesive properties cannot be obtained.

【００３０】（メタ）アクリル酸エステル共重合体中に
おける、（メタ）アクリル酸アルキルエステルモノマー
と（酸基を有しない極性モノマー＋酸基を有するコモノ
マー）との重量比は、通常９９／１〜６０／４０であ
り、特に好ましくは９５／５〜８０／２０である。な
お、酸基を有するコモノマーとして（メタ）アクリル酸
が共重合される場合には、（メタ）アクリル酸の共重合
量は、５重量％以下であることが好ましい。酸基を有す
るコモノマーとして（メタ）アクリル酸が５重量％を超
えて共重合されると、放射線硬化型粘着剤層３は、完全
相溶系となり充分なエキスパンド性、ピックアップ性が
得られなくなる場合がある。In the (meth) acrylic acid ester copolymer, the weight ratio of the (meth) acrylic acid alkyl ester monomer to the (polar monomer having no acid group + comonomer having an acid group) is usually 99/1 to 1/99. 60/40, particularly preferably 95/5 to 80/20. When (meth) acrylic acid is copolymerized as a comonomer having an acid group, the copolymerization amount of (meth) acrylic acid is preferably 5% by weight or less. When (meth) acrylic acid is copolymerized in excess of 5% by weight as a comonomer having an acid group, the radiation-curable pressure-sensitive adhesive layer 3 becomes a completely compatible system and may not have sufficient expandability and pickup properties. is there.

【００３１】またこれらのモノマーを共重合して得られ
る（メタ）アクリル酸エステル共重合体の重量平均分子
量は、２．０×１０5〜１０．０×１０5であり、好まし
くは、４．０×１０5〜８．０×１０5である。The weight average molecular weight of the (meth) acrylate copolymer obtained by copolymerizing these monomers is from 2.0 × 10 5 to 10.0 × 10 5 , and preferably 4. It is 0 × 10 5 to 8.0 × 10 5 .

【００３２】放射線硬化型粘着剤層３を構成する放射線
重合性オリゴマーとしては、分子量が３０００〜３００
００程度、好ましくは５０００〜１００００程度であ
り、分子内に炭素−炭素二重結合を少なくとも１個以上
有する化合物が用いられる。具体的には、ウレタンアク
リレート系オリゴマー、エポキシ変性ウレタンアクリレ
ートオリゴマーあるいはエポキシアクリレートオリゴマ
ー等が用いられる。The radiation-polymerizable oligomer constituting the radiation-curable pressure-sensitive adhesive layer 3 has a molecular weight of 3,000 to 300.
It is about 00, preferably about 5,000 to 10,000, and a compound having at least one carbon-carbon double bond in the molecule is used. Specifically, a urethane acrylate oligomer, an epoxy-modified urethane acrylate oligomer or an epoxy acrylate oligomer is used.

【００３３】ウレタンアクリレート系オリゴマーは、ポ
リエステル型またはポリエーテル型などのポリオール化
合物と、多価イソシアネート化合物たとえば２，４−ト
リレンジイソシアネート、２，６−トリレンジイソシア
ネート、１，３−キシリレンジイソシアネート、１，４
−キシリレンジイソシアネート、ジフェニルメタン４，
４−ジイソシアネートなどを反応させて得られる末端イ
ソシアネートウレタンプレポリマーに、ヒドロキシル基
を有するアクリレートあるいはメタクリレートたとえば
２−ヒドロキシエチルアクリレートまたは２−ヒドロキ
シエチルメタクリレート、２−ヒドロキシプロピルアク
リレート、２−ヒドロキシプロピルメタクリレート、ポ
リエチレングリコールアクリレート、ポリエチレングリ
コールメタクリレートなどを反応させて得られる。この
ウレタンアクリレート系オリゴマーは、炭素−炭素二重
結合を少なくとも１個以上有する放射線重合性化合物で
ある。The urethane acrylate oligomer includes a polyol compound such as a polyester type or a polyether type and a polyvalent isocyanate compound such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4
-Xylylene diisocyanate, diphenylmethane 4,
Acrylate or methacrylate having a hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene is added to a terminal isocyanate urethane prepolymer obtained by reacting 4-diisocyanate or the like. It is obtained by reacting glycol acrylate, polyethylene glycol methacrylate and the like. This urethane acrylate oligomer is a radiation polymerizable compound having at least one carbon-carbon double bond.

【００３４】このようなウレタンアクリレート系オリゴ
マーとして、特に分子量が３０００〜３００００、好ま
しくは３０００〜１００００、さらに好ましくは４００
０〜８０００であるものが好ましい。The urethane acrylate oligomer has a molecular weight of 3,000 to 30,000, preferably 3,000 to 10,000, more preferably 400 to 10,000.
What is 0-8000 is preferable.

【００３５】本発明における放射線硬化型粘着剤中の粘
着剤と放射線重合性オリゴマーの配合比は、粘着剤１０
０重量部に対して放射線重合性オリゴマーは２０〜２０
０重量部、特には５０〜１５０重量部の範囲の量で用い
られることが好ましい。この場合には、放射線硬化型粘
着剤層３とダイ接着用接着剤層４との間に大きな初期接
着力が得られ、しかも放射線照射後には接着力は大きく
低下し、容易に半導体素子とダイ接着用接着剤層４とを
該粘着シートからピックアップすることができる。また
ある程度の弾性率が維持されるため、エキスパンディン
グ工程において、所望のチップ間隔を得ることが容易に
なり、かつチップのズレ等も発生せず、ピックアップを
安定して行えるようになる。The compounding ratio of the pressure-sensitive adhesive to the radiation-polymerizable oligomer in the radiation-curable pressure-sensitive adhesive in the present invention is 10
20 to 20 parts by weight of radiation polymerizable oligomer
It is preferably used in an amount of 0 parts by weight, in particular 50 to 150 parts by weight. In this case, a large initial adhesive force is obtained between the radiation-curable pressure-sensitive adhesive layer 3 and the die-adhesive adhesive layer 4, and the adhesive force is significantly reduced after the irradiation, so that the semiconductor element and the die can be easily bonded. The bonding adhesive layer 4 can be picked up from the pressure-sensitive adhesive sheet. In addition, since a certain degree of elasticity is maintained, it is easy to obtain a desired chip interval in the expanding step, and the chip can be stably picked up without any chip displacement.

【００３６】粘着剤層３を構成する放射線硬化型粘着剤
は、上記粘着剤と放射線重合性オリゴマーとを、所定重
量部混合後、攪拌することにより得られる。また必要に
応じては、放射線硬化型粘着剤層３中に、反応性希釈剤
を添加してもよい。反応性希釈剤としては、分子量が１
００〜３０００程度、好ましくは１００〜１５００程度
であり、分子内に炭素−炭素二重結合を少なくとも１個
以上有する重合性化合物が用いられる。具体的には、ト
リメチロールプロパントリアクリレート、テトラメチロ
ールメタンテトラアクリレート、ペンタエリスリトール
トリアクリレート、ペンタエリスリトールテトラアクリ
レート、ジペンタエリスリトールモノヒドロキシペンタ
アクリレート、ジペンタエリスリトールヘキサアクリレ
ートあるいは１，４−ブチレングリコールジアクリレー
ト、１，６−ヘキサンジオールジアクリレート、ポリエ
チレングリコールジアクリレート、市販のオリゴエステ
ルアクリレートなどが用いられる。反応性希釈剤は、粘
着剤１００重量部に対して０〜５０重量部、特には０〜
３０重量部の範囲の量で用いられることが好ましい。The radiation-curable pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 3 is obtained by mixing the above-mentioned pressure-sensitive adhesive and a radiation-polymerizable oligomer in a predetermined amount by weight and stirring the mixture. If necessary, a reactive diluent may be added to the radiation-curable pressure-sensitive adhesive layer 3. Reactive diluents have a molecular weight of 1
A polymerizable compound having a molecular weight of about 00 to 3000, preferably about 100 to 1500, and having at least one carbon-carbon double bond in the molecule is used. Specifically, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate and the like are used. The reactive diluent is used in an amount of 0 to 50 parts by weight, especially 0 to 100 parts by weight of the adhesive.
Preferably, it is used in an amount in the range of 30 parts by weight.

【００３７】さらに上記の放射線硬化型粘着剤層３中
に、光反応開始剤を混入することにより、光照射による
重合硬化時間ならびに光線照射量を少なくなることがで
きる。このような光反応開始剤としては、具体的には、
ベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾ
インメチルエーテル、ベンゾインエチルエーテル、ベン
ゾインイソプロピルエーテル、ベンジルジフェニルサル
ファイド、テトラメチルチウラムモノサルファイド、ア
ゾビスイソブチロニトリル、ジベンジル、ジアセチル、
β−クロールアンスラキノンなどが挙げられる。光反応
開始剤は、粘着剤１００重量部に対して０．１〜１０重
量部、特には０．５〜５重量部の範囲の量で用いられる
ことが好ましい。Furthermore, by mixing a photo-reaction initiator into the radiation-curable pressure-sensitive adhesive layer 3, the polymerization curing time and the amount of light irradiation by light irradiation can be reduced. As such a photoreaction initiator, specifically,
Benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl,
β-chloranthraquinone and the like. The photoreaction initiator is preferably used in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the adhesive.

【００３８】また必要に応じては、放射線硬化型粘着剤
層３中に、放射線照射により着色する化合物を含有させ
ることもできる。このような放射線照射により、着色す
る化合物を粘着剤層３に含ませることによって、粘着シ
ートに放射線が照射された後には該シートは着色され、
したがって光センサーによって半導体素子を検出する際
に検出精度が高まり、半導体素子のピックアップ時に誤
動作が生ずることがない。また粘着シートに放射線が照
射されたか否かが目視により直ちに判明するという効果
が得られる。If necessary, the radiation-curable pressure-sensitive adhesive layer 3 may contain a compound which is colored by irradiation. By including a compound to be colored in the pressure-sensitive adhesive layer 3 by such radiation irradiation, after the pressure-sensitive adhesive sheet is irradiated with radiation, the sheet is colored,
Therefore, the detection accuracy is improved when the semiconductor element is detected by the optical sensor, and a malfunction does not occur when the semiconductor element is picked up. In addition, an effect is obtained that it is immediately possible to visually determine whether or not radiation has been applied to the adhesive sheet.

【００３９】放射線照射により着色する化合物は、放射
線の照射前には無色または淡色であるが、放射線の照射
により有色となる化合物であって、この化合物の好まし
い具体例としてはロイコ染料が挙げられる。ロイコ染料
としては、慣用のトリフェニルメタン系、フルオラン
系、フェノチアジン系、オーラミン系、スピロピラン系
のものが好ましく用いられる。具体的には３−［Ｎ−
（ｐ−トリルアミノ）］−７−アニリノフルオラン、３
−［Ｎ−（ｐ−トリル）−Ｎ−メチルアミノ］−７−ア
ニリノフルオラン、３−［Ｎ−（ｐ−トリル）−Ｎ−エ
チルアミノ］−７−アニリノフルオラン、３−ジエチル
アミノ−６−メチル−７−アニリノフルオラン、クリス
タルバイオレットラクトン、４，４’，４”−トリスジ
メチルアミノトリフェニルメタノール、４，４’，４”
−トリスジメチルアミノトリフェニルメタンなどが挙げ
られる。The compound that is colored by irradiation with radiation is a compound that is colorless or pale before irradiation with radiation, but is a compound that becomes colored by irradiation with radiation. A preferred specific example of this compound is a leuco dye. As the leuco dye, commonly used triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based and spiropyran-based dyes are preferably used. Specifically, 3- [N-
(P-tolylamino)]-7-anilinofluoran, 3
-[N- (p-tolyl) -N-methylamino] -7-anilinofluoran, 3- [N- (p-tolyl) -N-ethylamino] -7-anilinofluoran, 3-diethylamino -6-methyl-7-anilinofluoran, crystal violet lactone, 4,4 ', 4 "-trisdimethylaminotriphenylmethanol, 4,4', 4"
-Trisdimethylaminotriphenylmethane and the like.

【００４０】これらロイコ染料とともに好ましく用いら
れる顕色剤としては、従来から用いられているフェノー
ルホルマリン樹脂の初期重合体、芳香族カルボン酸誘導
体、活性白土などの電子受容体が挙げられ、さらに、色
調を変化させる場合は種々公知の発色剤を組合せて用い
ることもできる。Examples of the developer preferably used together with these leuco dyes include conventionally used electron acceptors such as phenol formalin resin initial polymers, aromatic carboxylic acid derivatives, and activated clay. In the case where is changed, various known color formers can be used in combination.

【００４１】このような放射線照射によって着色する化
合物は、一旦有機溶媒などに溶解された後に接着剤層中
に含ませてもよく、また微粉末状にして粘着剤層中に含
ませてもよい。この化合物は、粘着剤層中に０．０１〜
１０重量％、好ましくは０．５〜５重量％の量で用いら
れることが望ましい。該化合物が１０重量％を超えた量
で用いられると、粘着シートに照射される放射線がこの
化合物に吸収されすぎてしまうため、粘着剤層の硬化が
不十分となることがあり、一方該化合物が０．０１重量
％未満の量で用いられると放射線照射時に粘着シートが
充分に着色しないことがあり、半導体素子のピックアッ
プ時に誤動作が生じやすくなることがある。Such a compound which is colored by irradiation with radiation may be once dissolved in an organic solvent or the like and then included in the adhesive layer, or may be finely powdered and included in the pressure-sensitive adhesive layer. . This compound is present in the pressure-sensitive adhesive layer in an amount of 0.01 to
It is desirable to use it in an amount of 10% by weight, preferably 0.5 to 5% by weight. When the compound is used in an amount exceeding 10% by weight, the radiation applied to the pressure-sensitive adhesive sheet is excessively absorbed by the compound, and thus the curing of the pressure-sensitive adhesive layer may be insufficient. When used in an amount of less than 0.01% by weight, the pressure-sensitive adhesive sheet may not be sufficiently colored at the time of irradiation with radiation, and a malfunction may easily occur when the semiconductor element is picked up.

【００４２】また、上記の放射線硬化型粘着剤層３中に
エキスパンディング剤を添加することもできる。エキス
パンディング剤を添加することにより、放射線硬化型粘
着剤層３の重合硬化後のエキスパンドがさらに容易にな
る。エキスパンディング剤としては、具体的には以下の
ような化合物が用いられる。Further, an expanding agent can be added to the radiation-curable pressure-sensitive adhesive layer 3. The addition of the expanding agent further facilitates the expansion of the radiation-curable pressure-sensitive adhesive layer 3 after polymerization and curing. The following compounds are specifically used as the expanding agent.

【００４３】（ａ）高級脂肪酸またはこれらの誘導体 ステアリン酸、ラウリン酸、リシノール酸、ナフテン
酸、２−エチルヘキソイル酸、オレイン酸、リノール
酸、ミリスチン酸、パルミチン酸、イソステアリン酸、
ヒドロキシステアリン酸、ベヘン酸などの、上記の酸の
エステル類。上記の酸の金属塩たとえばＬｉ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ｃｄ、Ｚｎ、Ｐｂ、Ｓｎ、Ｋ、Ｎａ塩
あるいは上記金属を２種以上含む複合金属塩など。(A) Higher fatty acids or derivatives thereof stearic acid, lauric acid, ricinoleic acid, naphthenic acid, 2-ethylhexoylic acid, oleic acid, linoleic acid, myristic acid, palmitic acid, isostearic acid,
Esters of the above acids, such as hydroxystearic acid and behenic acid. Metal salts of the above acids such as Li, Mg, C
a, Sr, Ba, Cd, Zn, Pb, Sn, K, Na salts or composite metal salts containing two or more of the above metals.

【００４４】（ｂ）Ｓｉあるいはシロキサン構造を有す
る化合物。 シリコーンオイルなど。 （ｃ）フッ素を含む化合物。 （ｄ）エポキシ化合物。 エポキシステアリン酸メチル、エポキシステアリン酸ブ
チル、エポキシ化アマニ油脂肪酸ブチル、エポキシ化テ
トラヒドロナフタレート、ビスフェノールＡジグリシジ
ルエーテル、エポキシ化ブタジエン。(B) Compounds having a Si or siloxane structure. Silicone oil and the like. (C) a compound containing fluorine. (D) an epoxy compound. Methyl epoxy stearate, butyl epoxy stearate, butyl epoxidized linseed oil fatty acid, epoxidized tetrahydronaphthalate, bisphenol A diglycidyl ether, epoxidized butadiene.

【００４５】（ｅ）ポリオール化合物またはこれらの誘
導体。 グリセリン、ジグリセリン、ソルビトール、マンニトー
ル、キシリトール、ペンタエリスリトール、ジペンタエ
リスリトール、トリメチロールプロパン、ポリエチレン
グリコール、ポリビニルアルコールなど。 上記化合物の含窒素または含硫黄あるいは金属錯体。(E) Polyol compounds or derivatives thereof. Glycerin, diglycerin, sorbitol, mannitol, xylitol, pentaerythritol, dipentaerythritol, trimethylolpropane, polyethylene glycol, polyvinyl alcohol and the like. A nitrogen-containing or sulfur-containing or metal complex of the above compound.

【００４６】（ｆ）β−ジケト化合物またはこれらの誘
導体。 アセト酢酸エステル、デヒドロ酢酸、アセチルアセト
ン、ベンゾイルアセトン、トリフルオロアセチルアセト
ン、ステアロイルベンゾイルメタン、ジベンジルメタ
ン。上記化合物の金属錯体。(F) β-diketo compounds or derivatives thereof. Acetoacetate, dehydroacetic acid, acetylacetone, benzoylacetone, trifluoroacetylacetone, stearoylbenzoylmethane, dibenzylmethane. Metal complexes of the above compounds.

【００４７】（ｇ）ホスファイト類 トリフェニルホスフィン、ジフェニル亜ホスフィン、酸
フェニル、水添ビスフェノールＡホスファイトポリマ
ー、(G) Phosphites Triphenylphosphine, diphenylphosphine, phenyl acid, hydrogenated bisphenol A phosphite polymer,

【００４８】[0048]

【化１】 （式中、ＲはＣnＨ2n+1である。）Embedded image ( Where R is C n H 2n + 1 )

【００４９】[0049]

【化２】 （式中、ＲはＣnＨ2n+1である。）Embedded image ( Where R is C n H 2n + 1 )

【００５０】エキスパンディング剤は、粘着剤層３中に
０〜１０重量％、特には０〜５重量％の範囲の量で用い
られることが好ましい。The expanding agent is preferably used in the pressure-sensitive adhesive layer 3 in an amount of 0 to 10% by weight, particularly preferably 0 to 5% by weight.

【００５１】さらに上記の放射線硬化型粘着剤層３中に
帯電防止剤を添加することもできる。帯電防止剤を添加
することにより、エキパンド時あるいはピックアップ時
に発生する静電気を抑制できるため、チップの信頼性が
向上する。帯電防止剤としては、具体的には、アニオン
性、カチオン性、非イオン性、ないし両イオン性の一般
に公知の活性剤、カーボンブラック、銀、ニッケル、ア
ンチモンドープスズ酸化物、スズドープインジウム酸化
物などの粉体等が用いられる。帯電防止剤は、粘着剤層
３中に０〜５０重量％、特には０〜３０重量部の範囲の
量で用いられることが好ましい。Further, an antistatic agent can be added to the radiation-curable pressure-sensitive adhesive layer 3. By adding an antistatic agent, static electricity generated at the time of expansion or at the time of pickup can be suppressed, so that the reliability of the chip is improved. As the antistatic agent, specifically, anionic, cationic, nonionic, or zwitterionic generally known activator, carbon black, silver, nickel, antimony-doped tin oxide, tin-doped indium oxide And the like. The antistatic agent is preferably used in the adhesive layer 3 in an amount of 0 to 50% by weight, particularly 0 to 30% by weight.

【００５２】また上記の粘着剤中に、イソシアナート系
硬化剤を混合することにより、初期の接着力を任意の値
に設定することができる。このような硬化剤としては、
具体的には多価イソシアネート化合物、たとえば２，４
−トリレンジイソシアネート、２，６−トリレンジイソ
シアネート、１，３−キシリレンジイソシアネート、
１，４−キシレンジイソシアネート、ジフェニルメタン
−４，４’−ジイソシアネート、ジフェニルメタン−
２，４’−ジイソシアネート、３−メチルジフェニルメ
タンジイソシアネート、ヘキサメチレンジイソシアネー
ト、イソホロンジイソシアネート、ジシクロヘキシルメ
タン−４，４’−ジイソシアネート、ジシクロヘキシル
メタン−２，４’−ジイソシアネート、リジンイソシア
ネートなどが用いられる。硬化剤は、粘着剤１００重量
部に対して０〜５０重量部、特には０〜２０重量部の範
囲の量で用いられることが好ましい。By mixing an isocyanate-based curing agent in the above-mentioned pressure-sensitive adhesive, the initial adhesive strength can be set to an arbitrary value. As such a curing agent,
Specifically, a polyvalent isocyanate compound such as 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-
2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, lysine isocyanate and the like are used. The curing agent is preferably used in an amount of 0 to 50 parts by weight, particularly 0 to 20 parts by weight based on 100 parts by weight of the adhesive.

【００５３】さらに本発明では、基材中に砥粒が分散さ
れていてもよい。この砥粒は、粒径が０．５〜１００μ
ｍ、好ましくは１〜５０μｍであって、モース硬度は６
〜１０、好ましくは７〜１０である。具体的には、グリ
ーンカーボランダム、人造コランダム、オプティカルエ
メリー、ホワイトアランダム、炭化ホウ素、酸化クロム
(III)、酸化セリウム、ダイヤモンドパウダーなどが用
いられる。このような砥粒は無色あるいは白色であるこ
とが好ましい。このような砥粒は、基材２中に０．５〜
７０重量％、好ましくは５〜５０重量％の量で存在して
いる。このような砥粒は、切断ブレードをウエハのみな
らず基材２にまでも切り込むような深さで用いる場合
に、特に好ましく用いられる。Further, in the present invention, abrasive grains may be dispersed in the base material. This abrasive has a particle size of 0.5 to 100 μm.
m, preferably 1 to 50 μm, and a Mohs hardness of 6
-10, preferably 7-10. Specifically, green carborundum, artificial corundum, optical emery, white alundum, boron carbide, chromium oxide
(III), cerium oxide, diamond powder and the like are used. Such abrasive grains are preferably colorless or white. Such abrasive grains are contained in the base material 2 in an amount of 0.5 to
It is present in an amount of 70% by weight, preferably 5 to 50% by weight. Such abrasive grains are particularly preferably used when the cutting blade is used at such a depth as to cut not only into the wafer but also into the substrate 2.

【００５４】上記のような砥粒を基材中に含ませること
によって、切断ブレードが基材中に切り込んできて、切
断ブレードに粘着剤が付着しても砥粒の研磨効果によ
り、目づまりを簡単に除去することができる。By including the abrasive grains in the base material as described above, the cutting blade cuts into the base material, and even if the adhesive is adhered to the cutting blade, the clogging is easily performed by the polishing effect of the abrasive grains. Can be removed.

【００５５】本発明に係るウエハ貼着用粘着シートは、
上記の基材２、放射線硬化型粘着剤層３およびダイ接着
用接着剤層４からなる。接着剤層４を構成するダイ接着
用接着剤としては次の（１）および（２）の物性をみた
し、好ましくは次の（３）〜（６）の物性を１つ以上み
たす樹脂組成が用いられる。（１）250℃における弾性
率が10MPa以下（２）吸水率が1.0vol％以下（３）残存
揮発分が3.0wt％以下（４）飽和吸湿率が1.5vol％以下
（５）半導体素子を支持部材に接着した段階でダイ接着
用接着剤層中と、ダイ接着用接着剤層及び支持部材の界
面とに存在するボイドの体積率が10％以下（６）ダイ接
着用接着剤層を介して、半導体素子を支持部材に接着し
た段階でのピール強度が０．５ｋｇｆ／５×５ｍｍチッ
プ以上。The pressure-sensitive adhesive sheet for attaching a wafer according to the present invention comprises:
It is composed of the above-mentioned base material 2, radiation-curable pressure-sensitive adhesive layer 3, and die-bonding adhesive layer 4. The adhesive for die bonding constituting the adhesive layer 4 has the following physical properties (1) and (2), and preferably has a resin composition that satisfies at least one of the physical properties (3) to (6) below. Used. (1) Elastic modulus at 250 ° C of 10 MPa or less (2) Water absorption of 1.0 vol% or less (3) Residual volatile content of 3.0 wt% or less (4) Saturated moisture absorption of 1.5 vol% or less (5) Supporting semiconductor element At the stage of bonding to the member, the volume ratio of voids existing in the die bonding adhesive layer and the interface between the die bonding adhesive layer and the support member is 10% or less. (6) Through the die bonding adhesive layer The peel strength at the stage when the semiconductor element is bonded to the support member is 0.5 kgf / 5 × 5 mm chip or more.

【００５６】250℃における弾性率が10MPa以下のダイ接
着用接着剤を使用してダイボンディングを行えば、十分
なピール強度（例えば、ダイボンド条件：温度150〜250
℃、時間0.1秒以上２秒未満、圧力0.1〜4gf/mm2の条件
で0.5Kgf/5×5mmチップ以上の強度）を得ることができ
る。また、ダイ接着用接着剤の吸水率が1.0vol％以下で
あれば、ダイボンディング後、リフロー等で半導体装置
が高温に曝されても、ダイ接着用接着剤中の水分による
クラック発生を大幅に抑制することができる。If die bonding is performed using a die bonding adhesive having an elastic modulus at 250 ° C. of 10 MPa or less, sufficient peel strength (for example, die bonding conditions: temperature 150 to 250)
Under the conditions of a temperature of 0.1 ° C., a time of 0.1 second or more and less than 2 seconds, and a pressure of 0.1 to 4 gf / mm 2 , a strength of 0.5 kgf / 5 × 5 mm chip or more can be obtained. In addition, if the water absorption of the die-bonding adhesive is 1.0 vol% or less, even if the semiconductor device is exposed to a high temperature by reflow or the like after die bonding, cracks due to moisture in the die-bonding adhesive are significantly reduced. Can be suppressed.

【００５７】本発明では、ダイ接着用接着剤層は上記
（１）および（２）に加えて、（３）〜（６）の物性・
特性の二以上を兼ね備えることができる。兼ね備えるこ
とが好ましい物性・特性としては、例えば （Ａ）緩和吸湿率が1.0vol％以下かつ残存揮発分が3.0w
t％以下のダイ接着用接着剤層、（Ｂ）飽和吸湿率が1.0
vol％以下かつ半導体素子を支持部材に接着した段階で
のピール強度が0.5kgf/5×5mmチップ以上のダイ接着用
接着剤層、（Ｃ）残存揮発分が3.0wt％以下、かつ、半
導体素子を支持部材に接着した段階でのピール強度が0.
5kgf/5×5mmチップ以上のダイ接着用接着剤層、（Ｄ）
飽和吸湿率が1.0vol％以下、残存揮発分が3.0wt％以下
かつ半導体素子を支持部材に接着した段階でのピール強
度が0.5kgf/5×5mmチップ以上のダイ接着用接着剤層で
ある。In the present invention, in addition to the above (1) and (2), the adhesive layer for die bonding has physical properties (3) to (6).
It can have two or more of the characteristics. Physical properties and characteristics that are preferably provided include, for example, (A) a relaxed moisture absorption of 1.0 vol% or less and a residual volatile matter of 3.0 w
Adhesive layer for die bonding of less than t%, (B) saturated moisture absorption of 1.0
A die bonding adhesive layer having a peel strength of 0.5 kgf / 5 × 5 mm chip or more when the semiconductor element is adhered to the supporting member at a stage of vol% or less, and (C) a residual volatile content of 3.0 wt% or less, and the semiconductor element The peel strength at the stage where the
5kgf / 5 × 5mm chip or more die bonding adhesive layer, (D)
A die bonding adhesive layer having a saturated moisture absorption of 1.0 vol% or less, a residual volatile content of 3.0 wt% or less, and a peel strength of 0.5 kgf / 5 × 5 mm chip or more when the semiconductor element is bonded to the support member.

【００５８】本発明では、ダイ接着用接着剤層の上記
（３）〜（６）の物性・特性は使用目的に応じ、任意の
組み合わせをとることができる。また、上記の物性・特
性を任意組み合わせたダイ接着用接着剤層を、半導体素
子を支持部材に接着した段階で半導体素子の大きさから
はみ出さないようなフィルム状ダイ接着用接着剤層とし
て使用することが好ましい。In the present invention, the physical properties and characteristics (3) to (6) of the adhesive layer for die bonding can be arbitrarily combined according to the purpose of use. In addition, a die bonding adhesive layer having any combination of the above physical properties and characteristics is used as a film die bonding adhesive layer that does not protrude from the size of the semiconductor element when the semiconductor element is bonded to the support member. Is preferred.

【００５９】ダイ接着用接着剤層４を構成する樹脂組成
として、具体的には、エチレン・酢酸ビニル共重合体、
エチレン・アクリル酸エステル共重合体、ポリアミド、
ポリエチレン、ポリスルホン等の熱可塑性樹脂、エポキ
シ樹脂、ポリイミド樹脂、シリコーン樹脂、フェノール
樹脂等の熱硬化性樹脂、あるいは、アクリル樹脂、ゴム
系ポリマー、フッ素ゴム系ポリマー、フッ素樹脂等の接
着剤が用いられる。またこれらの２種以上の混合物であ
ってもよい。Specific examples of the resin composition constituting the adhesive layer 4 for die bonding include an ethylene / vinyl acetate copolymer,
Ethylene acrylate copolymer, polyamide,
Thermoplastic resins such as polyethylene and polysulfone, epoxy resins, polyimide resins, silicone resins, thermosetting resins such as phenolic resins, or adhesives such as acrylic resins, rubber polymers, fluororubber polymers, and fluororesins are used. . Also, a mixture of two or more of these may be used.

【００６０】本発明におけるダイ接着用接着剤の有機材
料として、ポリイミド樹脂が好ましい。ポリイミド樹脂
の原料として用いられるテトラカルボン酸二無水物とし
ては、1,2−（エチレン）ビス（トリメリテート無水
物）、1,3−（トリメチレン）ビス（トリメリテート無
水物）、1,4−（テトラメチレン）ビス（トリメリテー
ト無水物）、1,5−（ペンタメチレン）ビス（トリメリ
テート無水物）、1,6−（ヘキサメチレン）ビス（トリ
メリテート無水物）、1,7−（ヘプタメチレン）ビス
（トリメリテート無水物）、1,8−（オクタメチレン）
ビス（トリメリテート無水物）、1,9−（ノナメチレ
ン）ビス（トリメリテート無水物）、1,10−（デカメチ
レン）ビス（トリメリテート無水物）、1,12−（ドデカ
メチレン）ビス（トリメリテート無水物）、1,16−（ヘ
キサデカメチレン）ビス（トリメリテート無水物）、1,
18−（オクタデカメチレン）ビス（トリメリテート無水
物）、ピロメリット酸二無水物、3,3′,4,4′−ジフェ
ニルテトラカルボン酸二無水物、2,2′,3,3′−ジフェ
ニルテトラカルボン酸二無水物、2,2−ビス（3,4−ジカ
ルボキシフェニル）プロパン二無水物、2,2−ビス（2,3
−ジカルボキシフェニル）プロパン二無水物、1,1−ビ
ス（2,3−ジカルボキシフェニル）エタン二無水物、1,1
−ビス（3,4−ジカルボキシフェニル）エタン二無水
物、ビス（2,3−ジカルボキシフェニル）メタン二無水
物、ビス（3,4−ジカルボキシフェニル）メタン二無水
物、ビス（3,4−ジカルボキシフェニル）スルホン二無
水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、
ビス（3,4−ジカルボキシフェニル）エーテル二無水
物、ベンゼン−1,2,3,4−テトラカルボン酸二無水物、
3,4,3′,4′−ベンゾフェノンテトラカルボン酸二無水
物、2,3,2′,3−ベンゾフェノンテトラカルボン酸二無
水物、2,3,3′,4′−ベンゾフェノンテトラカルボン酸
二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無
水物、2,3,6,7−ナフタレンテトラカルボン酸二無水
物、1,2,4,5−ナフタレンテトラカルボン酸二無水物、
1,4,5,8−ナフタレンテトラカルボン酸二無水物、2,6−
ジクロロナフタレン−1,4,5,8−テトラカルボン酸二無
水物、2,7−ジクロロナフタレン−1,4,5,8−テトラカル
ボン酸二無水物、2,3,6,7−テトラクロロナフタレン−
1,4,5,8−テトラカルボン酸二無水物、フエナンスレン
−1,8,9,10−テトラカルボン酸二無水物、ピラジン−2,
3,5,6−テトラカルボン酸二無水物、チオフエン−2,3,
4,5−テトラカルボン酸二無水物、2,3,3′,4′−ビフェ
ニルテトラカルボン酸二無水物、3,4,3′,4′−ビフェ
ニルテトラカルボン酸二無水物、2,3,2′,3′−ビフェ
ニルテトラカルボン酸二無水物、ビス（3,4−ジカルボ
キシフェニル）ジメチルシラン二無水物、ビス（3,4−
ジカルボキシフェニル）メチルフェニルシラン二無水
物、ビス（3,4−ジカルボキシフェニル）ジフェニルシ
ラン二無水物、1,4−ビス（3,4−ジカルボキシフェニル
ジメチルシリル）ベンゼン二無水物、1,3−ビス（3,4−
ジカルボキシフェニル）−1,1,3,3−テトラメチルジシ
クロヘキサン二無水物、ｐ−フェニレンビス（トリメリ
テート無水物）、エチレンテトラカルボン酸二無水物、
1,2,3,4−ブタンテトラカルボン酸二無水物、デカヒド
ロナフタレン−1,4,5,8−テトラカルボン酸二無水物、
4,8−ジメチル−1,2,3,5,6,7−ヘキサヒドロナフタレン
−1,2,5,6−テトラカルボン酸二無水物、シクロペンタ
ン−1,2,3,4−テトラカルボン酸二無水物、ピロリジン
−2,3,4,5−テトラカルボン酸二無水物、1,2,3,4−シク
ロブタンテトラカルボン酸二無水物、ビス（エキソ−ビ
シクロ〔2,2,1〕ヘプタン−2,3−ジカルボン酸二無水
物）スルホン、ビシクロ−（2,2,2）−オクト−７−エ
ン−2,3,5,6−テトラカルボン酸二無水物、2,2−ビス
（3,4−ジカルボキシフェニル）ヘキサフルオロプロパ
ン二無水物、2,2−ビス〔４−（3,4−ジカルボキシフェ
ニル）フェニル〕ヘキサフルオロプロパン二無水物、4,
4′−ビス（3,4−ジカルボキシフェノキシ）ジフェニル
スルフィド二無水物、1,4−ビス（２−ヒドロキシヘキ
サフルオロイソプロピル）ベンゼンビス（トリメリット
酸無水物）。1,3−ビス（２−ヒドロキシヘキサフルオ
ロイソプロピル）ベンゼンビス（トリメリット酸無水
物）、５−（2,5−ジオキソテトラヒドロフリル）−３
−メチル−３−シクロヘキセン−1,2−ジカルボン酸二
無水物、テトラヒドロフラン−2,3,4,5−テトラカルボ
ン酸二無水物等があり、２種類以上を混合して用いても
よい。As the organic material of the die bonding adhesive in the present invention, a polyimide resin is preferable. Examples of the tetracarboxylic dianhydride used as a raw material of the polyimide resin include 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramer Methylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate) Anhydride), 1,8- (octamethylene)
Bis (trimellitate anhydride), 1,9- (nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride),
18- (octadecamethylene) bis (trimellitate anhydride), pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyl Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3
-Dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1
-Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride,
3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride ,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-
Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloro Naphthalene
1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,
3,5,6-tetracarboxylic dianhydride, thiophene-2,3,
4,5-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3 2,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-
Dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 3-bis (3,4-
Dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitate anhydride), ethylenetetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic Acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] Heptane-2,3-dicarboxylic dianhydride) sulfone, bicyclo- (2,2,2) -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride,
4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride). 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, and the like, and two or more kinds thereof may be used as a mixture.

【００６１】またポリイミド樹脂の原料として用いられ
るジアミンとしては、ｏ−フェニレンジアミン、ｍ−フ
ェニレンジアミン、ｐ−フェニレンジアミン、3,3′−
ジアミノジフェニルエーテル、3,4′−ジアミノジフェ
ニルエーテル、4,4′−ジアミノジフェニルエーテル、
3,3′−ジアミノジフェニルメタン、3,4′−ジアミノジ
フェニルメタン、4,4′−ジアミノジフェニルメタン、
ビス（４−アミノ−3,5−ジメチルフェニル）メタン、
ビス（４−アミノ−3,5−ジイソプロピルフェニル）メ
タン、3,3′−ジアミノジフェニルジフルオロメタン、
3,4′−ジアミノジフェニルジフルオロメタン、4,4′−
ジアミノジフェニルジフルオロメタン、3,3′−ジアミ
ノジフェニルスルホン、3,4′−ジアミノジフェニルス
ルホン、4,4′−ジアミノジフェニルスルホン、3,3′−
ジアミノジフェニルスルフイド、3,4′−ジアミノジフ
ェニルスルフィド、4,4′−ジアミノジフェニルスルフ
イド、3,3′−ジアミノジフェニルケトン、3,4′−ジア
ミノジフェニルケトン、4,4′−ジアミノジフェニルケ
トン、2,2−ビス（３−アミノフェニル）プロパン、2,
2′−（3,4′−ジアミノジフェニル）プロパン、2,2−
ビス（４−アミノフェニル）プロパン、2,2−ビス（３
−アミノフェニル）ヘキサフルオロプロパン、2,2−
（3,4′−ジアミノジフェニル）ヘキサフルオロプロパ
ン、2,2−ビス（４−アミノフェニル）ヘキサフルオロ
プロパン、1,3−ビス（３−アミノフェノキシ）ベンゼ
ン、1,4−ビス（３−アミノフェノキシ）ベンゼン、1,4
−ビス（４−アミノフェノキシ）ベンゼン、3,3′−
（1,4−フェニレンビス（１−メチルエチリデン））ビ
スアニリン、3,4′−（1,4−フェニレンビス（１−メチ
ルエチリデン））ビスアニリン、4,4′−（1,4−フェニ
レンビス（１−メチルエチリデン））ビスアニリン、2,
2−ビス（４−（３−アミノフェノキシ）フェニル）プ
ロパン、2,2−ビス（４−（４−アミノフェノキシ）フ
ェニル）プロパン、2,2−ビス（４−３−アミノフェノ
キシ）フェニル）ヘキサフルオロプロパン、2,2−ビス
（４−（４−アミノフエノキシ）フエニル）ヘキサフル
オロプロパン、ビス（４−（３−アミノフェノキシ）フ
ェニル）スルフイド、ビス（４−（４−アミノフェノキ
シ）フェニル）スルフイド、ビス（４−（３−アミノフ
ェノキシ）フェニル）スルホン、ビス（４−（４−アミ
ノフェノキシ）フェニル）スルホン等の芳香族ジアミン
や、1,2−ジアミノエタン、1,3−ジアミノプロパン、1,
4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジ
アミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミ
ノオクタン、1,9−ジアミノノナン、1,10−ジアミノデ
カン、1,11−ジアミノウンデカン、1,12−ジアミノドデ
カン等の脂肪族ジアミン等があり、２種類以上を混合し
て用いてもよい。As the diamine used as a raw material of the polyimide resin, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
Bis (4-amino-3,5-dimethylphenyl) methane,
Bis (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane,
3,4'-diaminodiphenyldifluoromethane, 4,4'-
Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diamino Diphenyl ketone, 2,2-bis (3-aminophenyl) propane,
2 '-(3,4'-diaminodiphenyl) propane, 2,2-
Bis (4-aminophenyl) propane, 2,2-bis (3
-Aminophenyl) hexafluoropropane, 2,2-
(3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-amino Phenoxy) benzene, 1,4
-Bis (4-aminophenoxy) benzene, 3,3'-
(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,4-phenylenebis ( 1-methylethylidene)) bisaniline, 2,
2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4-3-aminophenoxy) phenyl) hexa Fluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, Aromatic diamines such as bis (4- (3-aminophenoxy) phenyl) sulfone and bis (4- (4-aminophenoxy) phenyl) sulfone, 1,2-diaminoethane, 1,3-diaminopropane,
4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11- There are aliphatic diamines such as diaminoundecane and 1,12-diaminododecane, and two or more kinds thereof may be used as a mixture.

【００６２】テトラカルボン酸二無水物とジアミンを公
知の方法で縮合反応させてポリイミドを得ることができ
る。すなわち、有機溶媒中で、テトラカルボン酸二無水
物とジアミンを等モル又はほぼ等モル用い（各成分の添
加順序は任意）、反応温度80℃以下、好ましくは０〜50
℃で反応させる。反応が進行するにつれ反応液の粘度が
徐々に上昇し、ポリイミドの前駆体であるポリアミド酸
が生成する。A polyimide can be obtained by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction by a known method. That is, in an organic solvent, tetracarboxylic dianhydride and diamine are used in an equimolar or almost equimolar manner (the order of addition of each component is arbitrary), and the reaction temperature is 80 ° C or lower, preferably 0 to 50 ° C.
React at ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a precursor of polyimide, is generated.

【００６３】ポリイミドは、上記反応物（ポリアミド
酸）を脱水閉環させて得ることができる。脱水閉環は12
0℃〜250℃で熱処理する方法や化学的方法を用いて行な
うことができる。本発明におけるダイ接着用接着剤の有
機材料として、ポリイミドの他、グリシジルエーテル
型、グリシジルアミン型、グリシジルエステル型、脂環
型のエポキシ樹脂が使用できる。The polyimide can be obtained by subjecting the above reaction product (polyamic acid) to dehydration and ring closure. Dehydration ring closure is 12
The heat treatment can be performed at 0 ° C. to 250 ° C. or a chemical method. As the organic material of the adhesive for die bonding in the present invention, glycidyl ether type, glycidylamine type, glycidyl ester type, and alicyclic epoxy resin can be used in addition to polyimide.

【００６４】本発明の半導体装置の製造においては、ダ
イボンド（接着）の条件は、温度100〜350℃、時間0.1
〜20秒、圧力0.1〜30gf/mm2が好ましく、温度150〜250
℃、時間0.1秒以上２秒未満、圧力0.1〜4gf/mm2がより
好ましく、温度150〜250℃、時間0.1秒以上1.5秒以下、
圧力0.3〜2gf/mm2が最も好ましい。In the manufacture of the semiconductor device of the present invention, the conditions for die bonding (adhesion) are as follows:
20 seconds, preferably pressure 0.1~30gf / mm 2, a temperature of 150 to 250
° C, time 0.1 second or more and less than 2 seconds, pressure 0.1-4 gf / mm 2 is more preferable, temperature 150-250 ° C, time 0.1 second or more and 1.5 seconds or less,
A pressure of 0.3-2 gf / mm 2 is most preferred.

【００６５】ダイ接着用接着剤層４の膜厚は、通常は３
〜１００μｍ程度であり、好ましくは１０〜６０μｍ程
度である。さらに、ダイ接着用接着剤層４には、導電性
の付与を目的として、金、銀、銅、ニッケル、アルミニ
ウム、ステンレス、カーボン、またはセラミック、ある
いはニッケル、アルミニウム等を銀で被覆したもののよ
うな導電性フィラーを添加してもよく、また熱伝導性の
付与を目的として、金、銀、銅、ニッケル、アルミニウ
ム、ステンレス、シリコン、ゲルマニウム等の金属材料
やそれらの合金等の熱伝導性物質を配合してもよい。ま
た接着剤層の硬化収縮を抑制し、密着性、硬度などの特
性を向上させる目的で、硫酸バリウム、チタン酸バリウ
ム、酸化ケイ素紛、微粉状酸化ケイ素、無定形シリカ、
結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレ
ー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニ
ウム、水酸化アルミニウム、マイカ等の公知慣用の無機
フィラーを用いる事もできる。これらの添加剤は単独で
又は２種以上配合することができ、ダイ接着用接着剤１
００重量部に対して、１０〜４００重量部程度の割合で
配合されていてもよい。The thickness of the die bonding adhesive layer 4 is usually 3
１００100 μm, preferably about 10-60 μm. Further, the die bonding adhesive layer 4 may be made of gold, silver, copper, nickel, aluminum, stainless steel, carbon, or ceramic, or nickel, aluminum or the like coated with silver for the purpose of imparting conductivity. A conductive filler may be added, and for the purpose of providing thermal conductivity, a heat conductive substance such as a metal material such as gold, silver, copper, nickel, aluminum, stainless steel, silicon, or germanium, or an alloy thereof is used. You may mix. In addition, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, for the purpose of suppressing curing shrinkage of the adhesive layer and improving properties such as adhesion and hardness.
Known and commonly used inorganic fillers such as crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica can also be used. These additives can be used alone or in combination of two or more.
It may be blended at about 10 to 400 parts by weight with respect to 00 parts by weight.

【００６６】以上、説明したような構成のウエハ貼着用
粘着シートに放射線を照射すると、放射線照射後には粘
着材層の粘着力は大きく低下し、容易に半導体素子のチ
ップを該粘着シートからピックアップすることができ
る。またある程度の弾性率が維持されるため、エキスパ
ンディング工程において、所望のチップ間隔を得ること
が容易になり、かつチップのズレ等も発生せず、ピック
アップを安定して行えるようになる。When radiation is applied to the pressure-sensitive adhesive sheet for attaching a wafer having the above-described structure, the adhesive force of the pressure-sensitive adhesive layer is significantly reduced after the irradiation, and the chip of the semiconductor element is easily picked up from the pressure-sensitive adhesive sheet. be able to. In addition, since a certain degree of elasticity is maintained, it is easy to obtain a desired chip interval in the expanding step, and the chip can be stably picked up without any chip displacement.

【００６７】本発明に係るウエハ貼着用粘着シートに
は、その使用前には前記ダイ接着用接着剤層４を保護す
るため、図２に示すようにダイ接着用接着剤層４の上面
に剥離性シート５を仮粘着しておくことが好ましい。こ
の剥離性シート５としては、従来公知のものが特に限定
されることなく用いられる。Before using the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention, the adhesive layer 4 for die bonding is protected on the upper surface of the adhesive layer 4 for die bonding as shown in FIG. It is preferable that the conductive sheet 5 is temporarily adhered. As the releasable sheet 5, a conventionally known sheet is used without any particular limitation.

【００６８】以下本発明に係る粘着シートの使用方法に
ついて説明する。本発明に係る粘着シート１の上面に剥
離性シート５が設けられている場合には、該シート５を
除去し、次いで粘着シート１のダイ接着用接着剤層４を
上向きにして載置し、図３に示すようにして、このダイ
接着用接着剤層４の上面にダイシング加工すべき半導体
ウエハＡを貼着する。この貼着状態でウエハＡに図４の
ようにダイシング、洗浄、乾燥の諸工程が加えられる。
この際、ダイ接着用接着剤層４により半導体ウエハは粘
着シートに充分に接着保持されているので、上記各工程
の間に半導体ウエハが脱落することはない。この時点に
おける放射線硬化型粘着剤層３とダイ接着用接着剤層４
との接着力は、１〜１０００ｇ／25mm程度であり、好ま
しくは１〜５００ｇ／25mm程度である。他方、ダイ接着
用接着剤４と半導体ウエハとの接着力は、５０〜２００
０ｇ／25mm程度であり、好ましくは１００〜１０００ｇ
／25mm程度であるので、半導体ウエハとウエハ貼着用粘
着シート１とは一体化しており、上記の諸工程中に、半
導体ウエハが脱落することはない。Hereinafter, a method for using the pressure-sensitive adhesive sheet according to the present invention will be described. When the peelable sheet 5 is provided on the upper surface of the pressure-sensitive adhesive sheet 1 according to the present invention, the sheet 5 is removed, and then the pressure-sensitive adhesive sheet 1 is placed with the die bonding adhesive layer 4 facing upward, As shown in FIG. 3, a semiconductor wafer A to be diced is attached to the upper surface of the die bonding adhesive layer 4. In this bonded state, various steps of dicing, cleaning and drying are added to the wafer A as shown in FIG.
At this time, the semiconductor wafer is sufficiently adhered and held on the pressure-sensitive adhesive sheet by the die bonding adhesive layer 4, so that the semiconductor wafer does not fall off during each of the above steps. At this time, the radiation-curable pressure-sensitive adhesive layer 3 and the die-bonding adhesive layer 4
Is about 1-1000 g / 25 mm, preferably about 1-500 g / 25 mm. On the other hand, the adhesive strength between the die bonding adhesive 4 and the semiconductor wafer is 50 to 200.
0 g / 25 mm, preferably 100 to 1000 g
/ 25 mm, the semiconductor wafer and the pressure-sensitive adhesive sheet 1 for attaching a wafer are integrated, and the semiconductor wafer does not fall off during the above-mentioned various steps.

【００６９】次に、図５に示すように、紫外線（ＵＶ）
あるいは電子線（ＥＢ）などの放射線Ｂを粘着シート１
の放射線硬化型粘着剤層３に照射し、放射線硬化型粘着
剤層３中に含まれる放射線重合性オリゴマーを重合硬化
せしめる。放射線照射量は、２０〜５００mW／cm2 程度
であり、照射時間は０．１〜１５０秒程度である。この
時点における放射線硬化型粘着剤層３とダイ接着用接着
剤層４との接着力は、１〜５００ｇ／25mm程度であり、
好ましくは１〜１００ｇ／25mm程度である。他方、ダイ
接着用接着剤４と、半導体ウエハまたは半導体ウエハが
ダイシングされた半導体チップＡ1、Ａ2、Ａ3、Ａ4（図
６参照）との接着力は、５０〜４０００ｇ／25mm程度で
あり、好ましくは１００〜３０００ｇ／25mm程度であ
る。この結果、放射線硬化型粘着剤層３とダイ接着用接
着剤層４との間の粘着力は、チップをピックアップでき
る程度に減少し、かつ放射線硬化型粘着剤層３自体があ
る程度の弾性率を維持するため、図６に示すエキスパン
ドにより容易に所望のチップ間隔が得られる。Next, as shown in FIG.
Alternatively, the radiation sheet B such as an electron beam (EB) is applied to the adhesive sheet 1.
To the radiation-curable pressure-sensitive adhesive layer 3 to polymerize and cure the radiation-polymerizable oligomer contained in the radiation-curable pressure-sensitive adhesive layer 3. The radiation dose is about 20 to 500 mW / cm 2 , and the irradiation time is about 0.1 to 150 seconds. At this time, the adhesive strength between the radiation-curable pressure-sensitive adhesive layer 3 and the die-bonding adhesive layer 4 is about 1 to 500 g / 25 mm,
Preferably it is about 1 to 100 g / 25 mm. On the other hand, the adhesive strength between the die bonding adhesive 4 and the semiconductor wafer or the semiconductor chips A1, A2, A3, and A4 (see FIG. 6) diced from the semiconductor wafer is about 50 to 4000 g / 25 mm, and is preferably. It is about 100 to 3000 g / 25 mm. As a result, the adhesive force between the radiation-curable pressure-sensitive adhesive layer 3 and the die-bonding adhesive layer 4 is reduced to such an extent that a chip can be picked up, and the radiation-curable pressure-sensitive adhesive layer 3 itself has a certain elastic modulus. To maintain, the desired chip spacing is easily obtained by the expansion shown in FIG.

【００７０】粘着シート１への放射線照射は、基材２の
放射線硬化型粘着剤層３が設けられていない面から行な
う。したがって前述のように、放射線としてＵＶを用い
る場合には基材２は光透過性であることが必要である
が、放射線としてＥＢを用いる場合には基材２は必ずし
も光透過性である必要はない。The radiation to the pressure-sensitive adhesive sheet 1 is performed from the surface of the substrate 2 on which the radiation-curable pressure-sensitive adhesive layer 3 is not provided. Therefore, as described above, when UV is used as the radiation, the substrate 2 needs to be light-transmitting, but when EB is used as the radiation, the substrate 2 does not necessarily need to be light-transmitting. Absent.

【００７１】エキスパンディング工程の後、図７に示す
ように、基材２の下面から突き上げ針扞６によりピック
アップすべき半導体チップＡ1、Ａ2、Ａ3、Ａ4を突き上
げ、このチップＡ1、Ａ2、Ａ3、Ａ4をたとえば吸引コレ
ット７によりピックアップする。チップＡ1とダイ接着
用接着剤層４との間の粘着力は、ダイ接着用接着剤層４
と放射線硬化型粘着剤層３との間の粘着力よりも大きい
ため、チップＡ1のピックアップを行うと、ダイ接着用
接着剤層４はチップＡ1の下面に付着した状態で剥離す
る（図８参照）。次いで、チップをダイ接着用接着剤４
を介してリードフレーム８に載置し加熱する。加熱温度
は、通常１００〜３００℃、好ましくは１５０〜２５０
℃程度であり、加熱時間は、０．５〜１２０分間、好ま
しくは１〜３０分間程度である。加熱によりダイ接着用
接着剤は再び接着力を発現し、チップとリードフレーム
との接着が完了する（図９参照）。After the expanding step, as shown in FIG. 7, the semiconductor chips A1, A2, A3, and A4 to be picked up by the push-up needle rod 6 are pushed up from the lower surface of the base material 2, and these chips A1, A2, A3, A4 is picked up by the suction collet 7, for example. The adhesive force between the chip A1 and the die bonding adhesive layer 4 is determined by the die bonding adhesive layer 4
When the chip A1 is picked up, the die bonding adhesive layer 4 is peeled off while being attached to the lower surface of the chip A1 because the adhesive strength between the die A1 and the radiation-curable pressure-sensitive adhesive layer 3 is larger than that of the chip A1 (see FIG. 8). ). Next, the chip is bonded to the die bonding adhesive 4.
And is placed on the lead frame 8 and heated. The heating temperature is usually 100 to 300 ° C, preferably 150 to 250 ° C.
C., and the heating time is about 0.5 to 120 minutes, preferably about 1 to 30 minutes. By heating, the die bonding adhesive develops adhesive strength again, and the bonding between the chip and the lead frame is completed (see FIG. 9).

【００７２】このようにして半導体チップＡ1、Ａ2、Ａ
3、Ａ4のピックアップを行なうと、充分なチップ間隔が
得られているので簡単にチップをピックアップすること
ができ、しかも放射線硬化型粘着剤の粘着力は充分に低
下しているので、放射線硬化型粘着剤による汚染のない
良好な品質のチップが得られる。また、ダイ接着用接着
剤を塗布する工程が省略されるため、プロセス上も極め
て有利である。Thus, the semiconductor chips A1, A2, A
3. When picking up A4, the chips can be easily picked up because a sufficient chip spacing is obtained, and the adhesive strength of the radiation-curable pressure-sensitive adhesive is sufficiently reduced. Good quality chips without contamination by the adhesive can be obtained. Further, since the step of applying the die bonding adhesive is omitted, the process is very advantageous.

【００７３】図１０には上記の放射線照射方法の変形例
を示すが、この場合には、突き上げ針扞６の内部を中空
とし、その中空部に放射線発生源９を設けて放射線照射
とピックアップとを同時に行えるようにしており、この
ようにすると装置を簡単化できると同時にピックアップ
操作時間を短縮することができる。FIG. 10 shows a modified example of the above-described radiation irradiation method. In this case, the inside of the push-up needle rod 6 is made hollow, and a radiation source 9 is provided in the hollow part to perform radiation irradiation and pickup. Can be performed at the same time, so that the apparatus can be simplified and the pickup operation time can be shortened.

【００７４】[0074]

【実施例】以下、本発明を実施例により説明するが、本
発明はこれら実施例に限定されるものではない。また以
下の実施例において用いられるポリイミドＡ〜ポリイミ
ドＦは、いずれも以下のような等モルの酸無水物とジア
ミンとを溶媒中で混合し加熱することにより重合させて
得られる。 ポリイミドＡ：1,2−（エチレン）ビス（トリメリテー
ト無水物）とビス（４−アミノ−3,5−ジメチルフェニ
ル）メタンとから合成した。 ポリイミドＢ：1,2−（エチレン）ビス（トリメリテー
ト無水物）と4,4′−ジアミノジフェニルエーテルとか
ら合成した。 ポリイミドＣ：1,2−（エチレン）ビス（トリメリテー
ト無水物）とビス（４−アミノ−3,5−ジイソプロピル
フェニル）メタンとから合成した。 ポリイミドＤは、1,2−（エチレン）ビス（トリメリテ
ート無水物）と2,2−ビス［４−（４−アミノフェノキ
シ）フェニル］プロパンとから合成した。 ポリイミドＥ：1,2−（エチレン）ビス（トリメリテー
ト無水物）および1,10−（デカメチレン）ビス（トリメ
リテート無水物）の等モル混合物と2,2−ビス［４−
（４−アミノフェノキシ）フェニル］プロパンとから合
成した。 ポリイミドＦ：1,10−（デカメチレン）ビス（トリメリ
テート無水物）と2,2−ビス［４−（４−アミノフェノ
キシ）フェニル］プロパンとから合成した。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Further, polyimides A to F used in the following examples are obtained by mixing equimolar acid anhydrides and diamines in a solvent in the following manner and heating them to polymerize them. Polyimide A: synthesized from 1,2- (ethylene) bis (trimellitate anhydride) and bis (4-amino-3,5-dimethylphenyl) methane. Polyimide B: synthesized from 1,2- (ethylene) bis (trimellitate anhydride) and 4,4'-diaminodiphenyl ether. Polyimide C: Synthesized from 1,2- (ethylene) bis (trimellitate anhydride) and bis (4-amino-3,5-diisopropylphenyl) methane. Polyimide D was synthesized from 1,2- (ethylene) bis (trimellitate anhydride) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane. Polyimide E: equimolar mixture of 1,2- (ethylene) bis (trimellitate anhydride) and 1,10- (decamethylene) bis (trimellitate anhydride) and 2,2-bis [4-
(4-aminophenoxy) phenyl] propane. Polyimide F: synthesized from 1,10- (decamethylene) bis (trimellitate anhydride) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane.

【００７５】（実施例１） 「放射線硬化型粘着剤の調製」アクリル系粘着剤（アク
リル系共重合体 ブチルアクリレート：２−ヒドロキシ
エチルメタアクリレート：メタアクリル酸ジメチルアミ
ノエステル＝８５：１０：５）１００重量部と、分子量
約７０００のウレタンアクリレート系オリゴマー１１０
重量部と、硬化剤（芳香族イソシアナート系）５重量部
と、ＵＶ硬化開始剤（ベンゾフェノン系）４重量部を混
合して放射線硬化型粘着剤を調製した。(Example 1) "Preparation of radiation-curable pressure-sensitive adhesive" Acrylic pressure-sensitive adhesive (acrylic copolymer butyl acrylate: 2-hydroxyethyl methacrylate: dimethylamino methacrylate = 85: 10: 5) 100 parts by weight and a urethane acrylate oligomer 110 having a molecular weight of about 7,000
A radiation-curable pressure-sensitive adhesive was prepared by mixing 5 parts by weight of a curing agent (aromatic isocyanate-based) and 4 parts by weight of a UV curing initiator (benzophenone-based).

【００７６】「粘着剤シートの作製」厚さ８０μｍのエチ
レン・メタクリル酸共重合体フィルム上に、上記の放射
線硬化型粘着剤を厚さ１０μｍとなるように塗布して粘
着剤シートを得た。この放射線硬化型粘着剤シートを用
いて、「貯蔵弾性率」を評価した。結果を表１に示す。[Preparation of Pressure-Sensitive Adhesive Sheet] The radiation-curable pressure-sensitive adhesive was applied to a thickness of 10 μm on an ethylene / methacrylic acid copolymer film having a thickness of 80 μm to obtain a pressure-sensitive adhesive sheet. Using this radiation-curable pressure-sensitive adhesive sheet, the "storage modulus" was evaluated. Table 1 shows the results.

【００７７】「ウエハ貼着用粘着シートの作製」作製し
た粘着剤シート上に、厚さ３０μｍとなるように製造し
たダイ接着用接着剤（ポリイミド樹脂をベースとするフ
ィルム状ダイボンディング剤）層をラミネートしてウエ
ハ貼着用粘着シートを作製した。得られたウエハ貼着用
粘着シートを用いて、「分散粒径」、「整列性（エキス
パンド時）」および「整列性（ピックアップ時）」の評
価を行った。結果を表１に示す。[Preparation of pressure-sensitive adhesive sheet to be attached to wafer] A pressure-sensitive adhesive layer (a film-type die bonding agent based on a polyimide resin) manufactured to have a thickness of 30 μm is laminated on the prepared pressure-sensitive adhesive sheet. Thus, an adhesive sheet for attaching a wafer was prepared. Using the obtained pressure-sensitive adhesive sheet for attaching a wafer, "dispersion particle size", "alignment (at the time of expansion)" and "alignment (at the time of pickup)" were evaluated. Table 1 shows the results.

【００７８】（比較例１）実施例１において、アクリル
系粘着剤として、ブチルアクリレート・アクリル酸共重
合体（ブチルアクリレート：アクリル酸（モル比）＝９
０：１０）を用い、分子量約２０００のウレタンアクリ
レート系オリゴマーを用いた以外は、実施例１と同様の
操作を行った。結果を表１に併記する。Comparative Example 1 In Example 1, a butyl acrylate / acrylic acid copolymer (butyl acrylate: acrylic acid (molar ratio) = 9) was used as an acrylic pressure-sensitive adhesive.
0:10), and the same operation as in Example 1 was performed except that a urethane acrylate oligomer having a molecular weight of about 2,000 was used. The results are also shown in Table 1.

【００７９】[0079]

【表１】 [Table 1]

【００８０】なお、表１の実施例１および比較例１にお
いて、「貯蔵弾性率」、「分散粒径」、「整列性（エキ
スパンド時）」および「整列性（ピックアップ時）」は
次のようにして評価した。 貯蔵弾性率 実施例１および比較例１によって得られる放射線硬化型
粘着剤を８０Ｗ／cmの高圧水銀灯下に置き、１秒間放射
線を照射する。これを円柱状に貼り合わせ、底面φ８m
m、高さ５mmとし、これを粘弾性測定に供した。放射線
硬化後の試料の貯蔵弾性率は、レオメトリックス（製）
ＲＤＳ−IIを用いて剪断法により測定された。測定条件
は、２３℃、５００rad/秒である。 分散粒径 実施例１および比較例１によって得られる粘着剤シート
の粘着剤層を８０Ｗ／cmの高圧水銀灯下に置き、１秒間
放射線を照射し、硬化後の粘着剤層表面を６００倍の顕
微鏡で観察して、顕微鏡内のスケールにて硬化部分の粒
径を実測することで「分散粒径」を決定した。 整列性（エキスパンド時） 実施例１および比較例１によって得られる粘着剤シート
にシリコンウエハを貼付した後、１０mm×１０mmにダイ
シングし、その後、粘着剤層に紫外線を空冷式高圧水銀
灯（８０Ｗ／cm、照射距離１０cm）により照射した。次
にエキスパンディング治具（ヒューグル社製 ＨＳ−１
０１０）にて１０mmエキスパンドし、ピックアップ力、
チップ間隔を測定し、同時にチップの配列を目視により
判定した。 整列性（ピックアップ時） 上記の操作の後、ダイボンダー装置（新川社製 ＰＡ−
１０）によるピックアップ試験を行った。ピックアップ
を試みたチップ１００個の内、幾つをピックアップでき
たかで評価した。In Example 1 and Comparative Example 1 in Table 1, "storage modulus", "dispersion particle size", "alignment (at the time of expansion)" and "alignment (at the time of pickup)" are as follows. Was evaluated. Storage elastic modulus The radiation-curable pressure-sensitive adhesive obtained in Example 1 and Comparative Example 1 is placed under a high-pressure mercury lamp of 80 W / cm and irradiated with radiation for 1 second. This is laminated in a columnar shape, bottom surface φ8m
m and a height of 5 mm, which were subjected to viscoelasticity measurement. The storage modulus of the sample after radiation curing is determined by Rheometrics
It was measured by a shear method using RDS-II. The measurement conditions are 23 ° C. and 500 rad / sec. Dispersion Particle Size The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Example 1 and Comparative Example 1 was placed under a high-pressure mercury lamp of 80 W / cm, irradiated with radiation for 1 second, and the surface of the pressure-sensitive adhesive layer after curing was microscope with a magnification of 600 times. And the “dispersed particle size” was determined by actually measuring the particle size of the cured portion on a scale in a microscope. Alignment property (at the time of expansion) A silicon wafer was attached to the pressure-sensitive adhesive sheet obtained in Example 1 and Comparative Example 1, and then diced to 10 mm × 10 mm. , Irradiation distance 10 cm). Next, an expanding jig (HS-1 manufactured by Hugle)
010) to expand by 10mm,
The chip interval was measured, and at the same time, the arrangement of the chips was visually determined. Alignment (at the time of pickup) After the above operation, a die bonder (PA-
A pickup test according to 10) was performed. An evaluation was made based on how many of the 100 chips that had been picked up were picked up.

【００８１】（実施例２、比較例２）表２に示すポリイ
ミド１００ｇ及びエポキシ樹脂１０ｇに、有機溶媒２８
０ｇを加えて溶解させる。ここに、銀粉を所定量加え
て、良く撹拌し、均一に分散させ、塗工用ワニスとし
た。この塗工ワニスをキャリアフィルム（ＯＰＰフィル
ム：二軸延伸ポリプロピレン）上に塗工し、熱風循環式
乾燥機の中で加熱して、溶媒を揮発乾燥させ、表２に示
す組成、吸水率のフィルム状ダイ接着用接着剤を製造し
た。このダイ接着用接着剤を、実施例１で作製した粘着
剤シートにラミネートして、ウエハ貼着用粘着シートを
作製した。厚み３００μｍ、＃２０００研摩のシリコン
ウエハの裏面に上記で作製したウエハ貼着用粘着シート
を貼付し、上記整列性評価時と同様の条件で紫外線照射
後、８ｍｍ×１０ｍｍにダイシングし、ダイ接着用接着
剤層とともにチップをピックアップした。得られたダイ
接着用接着剤層付シリコンチップを、リードフレームの
タブ上に温度３００℃、圧力１２．５ｇｆ／ｍｍ２、時
間５秒で加熱してシリコンチップをマウントし、次いで
ワイヤボンディングを行い、さらに封止材（日立化成工
業株式会社製、商品名ＣＥＬ−９０００）でモールドし
て半導体装置を製造した。半導体装置はＱＦＰ（Ｑｕａ
ｄ Ｆｌａｔ Ｐａｃｋａｇｅ）パッケージで１４×２
０×１．４ｍｍとし、またチップサイズは８×１０ｍ
ｍ、リードフレームは４２アロイリードフレームを使用
した。封止後の半導体装置を８５℃、８５％ＲＨの恒温
恒湿器中で１６８時間処理した後、ＩＲリフロー炉で２
４０℃、１０秒加熱した。その後、半導体装置をポリエ
ステル樹脂で注型し、ダイヤモンドカッターで切断した
断面を顕微鏡で観察して、次式によりリフロークラック
発生率（％）を測定し、耐リフロークラック性を評価し
た。 （リフロークラックの発生数／試験数）×100 ＝リフロークラック発生率（％） 評価結果を表２に併記する。(Example 2, Comparative Example 2) 100 g of polyimide and 10 g of epoxy resin shown in Table 2 were added to an organic solvent 28
Add 0 g and dissolve. Here, a predetermined amount of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. This coating varnish is coated on a carrier film (OPP film: biaxially oriented polypropylene) and heated in a hot air circulation type drier to evaporate and dry the solvent, and a film having the composition and water absorption shown in Table 2 An adhesive for bonding a die was manufactured. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer. The above-prepared pressure-sensitive adhesive sheet for attaching a wafer is attached to the back of a silicon wafer having a thickness of 300 μm and # 2000 polished, irradiated with ultraviolet light under the same conditions as in the evaluation of the alignment property, and then diced to 8 mm × 10 mm, and then bonded for die bonding. The chip was picked up with the agent layer. The obtained silicon chip with an adhesive layer for die bonding is heated on a tab of a lead frame at a temperature of 300 ° C., a pressure of 12.5 gf / mm 2 and a time of 5 seconds to mount the silicon chip, and then wire bonding is performed. Then, a semiconductor device was manufactured by molding with a sealing material (CEL-9000, manufactured by Hitachi Chemical Co., Ltd.). The semiconductor device is a QFP (Qua)
14 x 2 in d Flat Package)
0x1.4mm and chip size is 8x10m
m, a 42 alloy lead frame was used as a lead frame. After the sealed semiconductor device is treated in a thermo-hygrostat at 85 ° C. and 85% RH for 168 hours, the semiconductor device is subjected to IR reflow furnace for 2 hours.
Heated at 40 ° C. for 10 seconds. Thereafter, the semiconductor device was cast with a polyester resin, and a cross section cut with a diamond cutter was observed with a microscope, and a reflow crack generation rate (%) was measured by the following formula to evaluate reflow crack resistance. (Number of occurrences of reflow cracks / number of tests) × 100 = reflow crack occurrence rate (%) The evaluation results are also shown in Table 2.

【００８２】比較のために、予めダイシングしたシリコ
ンチップを、ウエハ貼着用粘着シートの代わりに日立化
成工業株式会社製銀ペースト（商品名エピナール）を８
ｍｇ、リードフレームのタブ上に塗付し、シリコンチッ
プを載せ、スクラブを掛けて充分に塗れ広がらせ、150
℃×1時間の条件で硬化した以外は実施例２と同様にマ
ウントして半導体装置を作製し、耐リフロークラック性
を評価した。評価結果を表２に併記する。また、実施例
３〜５においても上記ペーストを比較例２として使用し
た。For comparison, a silicon chip (Epinal (trade name), manufactured by Hitachi Chemical Co., Ltd.) was used instead of the dicing silicon chip in advance, instead of the adhesive sheet for attaching the wafer.
mg, spread on the tab of the lead frame, put the silicon chip, apply a scrub, spread enough, 150
A semiconductor device was fabricated by mounting in the same manner as in Example 2 except that the composition was cured under the conditions of ° C. × 1 hour, and the reflow crack resistance was evaluated. Table 2 also shows the evaluation results. In Examples 3 to 5, the above paste was used as Comparative Example 2.

【００８３】[0083]

【表２】 [Table 2]

【００８４】なお、吸水率測定方法は、つぎの通りであ
る。５０×５０ｍｍの大きさに180℃×1時間の条件で硬
化したダイ接着用接着剤をサンプルとし、サンプルを真
空乾燥機中で、１２０℃、３時間乾燥させ、デシケータ
中で放冷後、乾燥重量を測定しＭ１とした。サンプルを
蒸留水に室温で２４時間浸せきしてから取り出し、サン
プル表面をろ紙でふきとり、すばやく秤量してＭ２とし
た。 ［（Ｍ２−Ｍ１）／（Ｍ１/ｄ）］×１００＝吸水率
（ｖｏｌ％） として、吸水率を算出した。ｄは接着剤層の密度であ
る。The method of measuring the water absorption is as follows. A die-bonding adhesive cured to a size of 50 x 50 mm at 180 ° C for 1 hour was used as a sample, and the sample was dried in a vacuum dryer at 120 ° C for 3 hours, allowed to cool in a desiccator, and dried. The weight was measured and designated as M1. The sample was immersed in distilled water at room temperature for 24 hours and then taken out. The sample surface was wiped with filter paper and weighed quickly to obtain M2. Water absorption was calculated as [(M2−M1) / (M1 / d)] × 100 = water absorption (vol%). d is the density of the adhesive layer.

【００８５】（実施例３）表３に示すポリイミド１００
ｇ及びエポキシ樹脂１０ｇに、有機溶媒２８０ｇを加え
て溶解させた。ここに、銀粉を所定量加えて、良く撹拌
し、均一に分散させ、塗工用ワニスとした。この塗工ワ
ニスから、実施例２と同様にして、表３に示す組成、飽
和吸湿率のフィルム状ダイ接着用接着剤を製造した。こ
のダイ接着用接着剤を、実施例１で作製した粘着剤シー
トにラミネートして、ウエハ貼着用粘着シートを作製し
た。上記で作製したウエハ貼着用粘着シートを使用し
て、実施例２と同様にダイシングし、ダイ接着用接着剤
層付シリコンチップをピックアップした。得られたダイ
接着用接着剤層付シリコンチップを、リードフレームの
タブ上に、Ｎｏ．１〜６および比較例では、温度３００
℃、圧力１２．５ｇｆ／ｍｍ２、時間５秒で、Ｎｏ．７
〜１０では、温度２３０℃、圧力０．６ｇｆ／ｍｍ２、
時間１秒でマウントした。次いで、実施例２と同様に行
って同パッケージの半導体装置を製造した。封止後の半
導体装置を実施例２と同様にして、耐リフロークラック
性を評価した。評価結果を表３に併記する。Example 3 Polyimide 100 shown in Table 3
g and 10 g of the epoxy resin were dissolved by adding 280 g of an organic solvent. Here, a predetermined amount of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. From this coating varnish, in the same manner as in Example 2, an adhesive for bonding a film die having the composition and saturated moisture absorption shown in Table 3 was produced. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer. Dicing was performed in the same manner as in Example 2 using the pressure-sensitive adhesive sheet for attaching a wafer prepared above, and a silicon chip with an adhesive layer for die bonding was picked up. The obtained silicon chip with an adhesive layer for die bonding is placed on a tab of a lead frame with a No. In Examples 1 to 6 and Comparative Example, the temperature was 300
C., a pressure of 12.5 gf / mm 2 and a time of 5 seconds. 7
At -10, the temperature is 230 ° C., the pressure is 0.6 gf / mm 2 ,
Mounted in 1 second. Next, a semiconductor device having the same package was manufactured in the same manner as in Example 2. The semiconductor device after sealing was evaluated in the same manner as in Example 2 for reflow crack resistance. Table 3 also shows the evaluation results.

【００８６】[0086]

【表３】 [Table 3]

【００８７】飽和吸湿率測定方法は、つぎの通りであ
る。180℃×1時間の条件で硬化したダイ接着用接着剤を
直径１００ｍｍの円形フィルム状に切断し、これをサン
プルとした。サンプルを真空乾燥機中で、１２０℃、３
時間乾燥させ、デシケータ中で放冷後、乾燥重量を測定
しＭ１とした。サンプルを８５℃、８５％ＲＨの恒温恒
湿槽中で吸湿してから取り出し、すばやく秤量して秤量
値が一定になったとき、その重量をＭ２とした。 ［（Ｍ２−Ｍ１）／（Ｍ１/ｄ）］×１００＝飽和吸湿
率（vol％） として、飽和吸湿率を算出した。なお、ｄは接着剤層の
密度である。The method for measuring the saturated moisture absorption is as follows. The die-bonding adhesive cured at 180 ° C. for 1 hour was cut into a circular film having a diameter of 100 mm, and this was used as a sample. The sample is placed in a vacuum dryer at 120 ° C, 3
After drying for a period of time and cooling in a desiccator, the dry weight was measured and defined as M1. The sample was taken out after absorbing moisture in a thermo-hygrostat at 85 ° C. and 85% RH, and was weighed quickly. When the weighed value became constant, the weight was defined as M2. The saturated moisture absorption was calculated as [(M2−M1) / (M1 / d)] × 100 = saturated moisture absorption (vol%). Note that d is the density of the adhesive layer.

【００８８】（実施例４）ポリイミドＦ１００ｇ及びエ
ポキシ樹脂１０ｇに、溶媒としてジメチルアセトアミド
１４０ｇ、シクロヘキサノン１４０ｇを加えて溶解させ
た。ここに、銀粉７４ｇを加えて、良く撹拌し、均一に
分散させ、塗工用ワニスとした。この塗工ワニスから、
実施例２と同様にして、表４に示す組成、残存揮発分の
フィルム状ダイ接着用接着剤を製造した。このダイ接着
用接着剤を、実施例１で作製した粘着剤シートにラミネ
ートして、ウエハ貼着用粘着シートを作製した。上記で
作製したウエハ貼着用粘着シートを使用して、実施例２
と同様にダイシングし、ダイ接着用接着剤層付シリコン
チップをピックアップした。得られたダイ接着用接着剤
層付シリコンチップを、リードフレームのタブ上に、温
度２３０℃、圧力０．６ｇｆ／ｍｍ２、時間１秒でシリ
コンチップをマウントした。ついで、実施例２と同様に
行って同パッケージの半導体装置を製造した。封止後の
半導体装置について実施例２と同様に耐リフロークラッ
ク性を評価した。評価結果を表４に併記する。Example 4 140 g of dimethylacetamide and 140 g of cyclohexanone as solvents were dissolved in 100 g of polyimide F and 10 g of epoxy resin. Here, 74 g of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. From this coating varnish,
In the same manner as in Example 2, the composition shown in Table 4 and the adhesive for film-like die bonding of the remaining volatile components were produced. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer. Example 2 Using the wafer-adhered pressure-sensitive adhesive sheet prepared above,
Then, a silicon chip with an adhesive layer for die bonding was picked up. The obtained silicon chip with an adhesive layer for die bonding was mounted on a tab of a lead frame at a temperature of 230 ° C., a pressure of 0.6 gf / mm 2 and a time of 1 second. Next, a semiconductor device having the same package was manufactured in the same manner as in Example 2. The semiconductor device after sealing was evaluated for reflow crack resistance in the same manner as in Example 2. The evaluation results are also shown in Table 4.

【００８９】[0089]

【表４】 [Table 4]

【００９０】残存揮発分測定方法は、つぎの通りであ
る。５０×５０ｍｍの大きさに切断した180℃×1時間の
条件で硬化したダイ接着用接着剤をサンプルとし、サン
プルの重量を測定しＭ１とし、サンプルを熱風循環恒温
槽中で２００℃、２時間加熱後、秤量としてＭ２とし、 ［（Ｍ２−Ｍ１）/Ｍ１］×１００＝残存揮発分（ｗｔ
％） として、残存揮発分を算出した。The method for measuring the remaining volatile components is as follows. A die bonding adhesive cured under the conditions of 180 ° C. × 1 hour cut into a size of 50 × 50 mm was used as a sample, and the weight of the sample was measured to be M1. The sample was heated at 200 ° C. for 2 hours in a hot-air circulating thermostat. After heating, the weight was set to M2, and [(M2-M1) / M1] × 100 = remaining volatile matter (wt
%), And the residual volatile matter was calculated.

【００９１】（実施例５）ポリイミドＤ１００ｇ及びエ
ポキシ樹脂１０ｇに、溶媒としてジメチルアセトアミド
１４０ｇ、シクロヘキサノン１４０ｇを加えて溶解させ
た。ここに、銀粉７４ｇを加えて、良く撹拌し、均一に
分散させ、塗工用ワニスとした。この塗工ワニスから、
実施例２と同様にして表５に示す組成、ボイド体積率を
有するフィルム状ダイ接着用接着剤を製造した。このダ
イ接着用接着剤を、実施例１で作製した粘着剤シートに
ラミネートして、ウエハ貼着用粘着シートを作製した。
なお、ここで、ボイド体積率とは、半導体素子を支持部
材に接着した段階で、ダイ接着用接着剤層内部と、前記
ダイ接着用接着剤層及び支持部材の界面とに存在するボ
イドの体積率である。上記で作製したウエハ貼着用粘着
シートを使用して、実施例２と同様にしてダイシング
し、ダイ接着用接着剤と共にチップをピックアップし
た。得られた接着剤層付シリコンチップを、実施例２と
同様にリードフレームのタブ上にマウントし、同パッケ
ージの半導体装置を製造した。封止後の半導体装置を実
施例２と同様に耐リフロークラック性を評価した。評価
結果を表５に併記する。Example 5 To 100 g of polyimide D and 10 g of epoxy resin, 140 g of dimethylacetamide and 140 g of cyclohexanone were added and dissolved as solvents. Here, 74 g of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. From this coating varnish,
In the same manner as in Example 2, an adhesive for bonding a film die having the composition and the void volume ratio shown in Table 5 was produced. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer.
Here, the void volume ratio is the volume of voids existing inside the die bonding adhesive layer and at the interface between the die bonding adhesive layer and the support member when the semiconductor element is bonded to the support member. Rate. Using the above-prepared pressure-sensitive adhesive sheet for attaching a wafer, dicing was performed in the same manner as in Example 2, and a chip was picked up together with a die bonding adhesive. The obtained silicon chip with an adhesive layer was mounted on a tab of a lead frame in the same manner as in Example 2 to manufacture a semiconductor device of the same package. The semiconductor device after sealing was evaluated for reflow crack resistance in the same manner as in Example 2. Table 5 also shows the evaluation results.

【００９２】[0092]

【表５】 [Table 5]

【００９３】ボイド体積率測定方法は、つぎの通りであ
る。リードフレームとシリコンチップとをダイ接着用接
着剤層で実施例２と同じ条件で接着してサンプルを作製
し、軟Ｘ線装置を用いて、サンプル上面から観察した画
像を写真撮影した。写真のボイドの面積率を画像解析装
置によって測定し、上面から透視したボイドの面積率＝
ボイドの体積率（％）とした。The method for measuring the void volume ratio is as follows. A sample was prepared by bonding the lead frame and the silicon chip with the die bonding adhesive layer under the same conditions as in Example 2, and an image observed from the top surface of the sample was photographed using a soft X-ray apparatus. The area ratio of voids in the photograph was measured by an image analyzer, and the area ratio of voids seen through from the top surface =
The void volume ratio (%) was used.

【００９４】（実施例６）表６に示すポリイミドＤ１０
０ｇ及びエポキシ樹脂１０ｇに、有機溶媒２８０gを加
えて溶解させた。ここに、銀粉を所定量加えて、良く撹
拌し、均一に分散させ、塗工用ワニスとした。この塗工
ワニスから、実施例２と同様にして表６に示す組成、ピ
ール強度を有するフィルム状ダイ接着用接着剤を製造し
た。このダイ接着用接着剤を、実施例１で作製した粘着
剤シートにラミネートして、ウエハ貼着用粘着シートを
作製した。ここで、ピール強度は、半導体素子を支持部
材にダイ接着用接着剤層を介して接着した段階でのダイ
接着用接着剤層のピール強度である。上記で作製したウ
エハ貼着用粘着シートを使用して、実施例２と同様にダ
イシングし、ダイ接着用接着剤層付シリコンチップをピ
ックアップした。得られたダイ接着用接着剤層付シリコ
ンチップを、リードフレームのタブ上に、Ｎｏ．１〜５
については温度３００℃、圧力１２．５ｇｆ／ｍｍ２、
時間５秒で、Ｎｏ．６〜１０については温度２３０℃、
圧力０．６ｇｆ／ｍｍ２、時間１秒でマウントした。次
いで、実施例２と同様に行って同パッケージの半導体装
置を製造した。封止後の半導体装置を実施例２と同様に
耐リフロークラック性を評価した。評価結果を表６に併
記する。Example 6 Polyimide D10 shown in Table 6
To 0 g and 10 g of the epoxy resin, 280 g of an organic solvent was added and dissolved. Here, a predetermined amount of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. From this coating varnish, a film-like die bonding adhesive having the composition and peel strength shown in Table 6 was produced in the same manner as in Example 2. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer. Here, the peel strength is the peel strength of the adhesive layer for die bonding at the stage when the semiconductor element is bonded to the support member via the adhesive layer for die bonding. Dicing was performed in the same manner as in Example 2 using the pressure-sensitive adhesive sheet for attaching a wafer prepared above, and a silicon chip with an adhesive layer for die bonding was picked up. The obtained silicon chip with an adhesive layer for die bonding is placed on a tab of a lead frame with a No. 1-5
About 300 ° C., pressure 12.5 gf / mm 2 ,
With a time of 5 seconds, No. 230 ° C for 6-10,
The mounting was performed at a pressure of 0.6 gf / mm 2 and a time of 1 second. Next, a semiconductor device having the same package was manufactured in the same manner as in Example 2. The semiconductor device after sealing was evaluated for reflow crack resistance in the same manner as in Example 2. The evaluation results are also shown in Table 6.

【００９５】[0095]

【表６】 [Table 6]

【００９６】（ピール強度測定方法）厚み３００μｍ、
＃２０００研摩のシリコンウエハの裏面に実施例６で作
製したウエハ貼着用粘接着シートを貼付し、紫外線照射
後、５ｍｍ×５ｍｍにダイシングし、ダイ接着用接着剤
層とともにピックアップし、得られた接着剤層付シリコ
ンチップを、リードフレームのタブ表面等の半導体素子
を支持する支持部材に接着したものを、２４０℃の熱盤
上に、２０秒間保持し、図１１に示すように、プッシュ
プルゲージを用いて、試験速度０．５ｍｍ/分でピール
強度を測定した。図１１においては、Ａ１はチップ、４
はダイ接着用接着剤層、８はリードフレーム、２４はプ
ッシュプルゲージ、２５は熱盤である。尚、この場合に
は２４０℃、２０秒間に保持して測定したが、半導体装
置の使用目的によって半導体装置を実装する温度が異な
る場合は、その半導体装置実装温度で保持して測定し
た。(Method of Measuring Peel Strength) Thickness 300 μm,
The wafer-adhesive adhesive sheet prepared in Example 6 was attached to the back surface of a # 2000-polished silicon wafer, irradiated with ultraviolet light, diced to 5 mm × 5 mm, and picked up together with the die-bonding adhesive layer. A silicon chip with an adhesive layer adhered to a support member for supporting a semiconductor element such as a tab surface of a lead frame is held on a hot plate at 240 ° C. for 20 seconds, and as shown in FIG. The peel strength was measured at a test speed of 0.5 mm / min using a gauge. In FIG. 11, A1 is a chip, 4
Denotes an adhesive layer for bonding a die, 8 denotes a lead frame, 24 denotes a push-pull gauge, and 25 denotes a hot plate. In this case, the measurement was performed while the temperature was maintained at 240 ° C. for 20 seconds. However, when the temperature at which the semiconductor device was mounted was different depending on the purpose of use of the semiconductor device, the measurement was performed while maintaining the semiconductor device mounting temperature.

【００９７】（実施例７）ポリイミドＦ１００ｇ及びエ
ポキシ樹脂１０ｇに、有機溶媒２８０gを加えて溶解さ
せた。ここに、銀粉を所定量加えて、良く撹拌し、均一
に分散させ、塗工用ワニスとした。この塗工ワニスか
ら、実施例２と同様にして表７のような２５０℃での弾
性率を示すフィルム状ダイ接着用接着剤を製造した。こ
のダイ接着用接着剤を、実施例１で作製した粘着剤シー
トにラミネートして、ウエハ貼着用粘着シートを作製し
た。上記で作製したウエハ貼着用粘着シートを使用し
て、実施例２と同様にしてダイシングし、ダイ接着用接
着剤と共にチップをピックアップした。得られた接着剤
層付シリコンチップを、表７に示すダイボンディング条
件でマウントした。このピール強度を表７に併記する。(Example 7) 280 g of an organic solvent was added to and dissolved in 100 g of polyimide F and 10 g of epoxy resin. Here, a predetermined amount of silver powder was added, stirred well, and uniformly dispersed to obtain a coating varnish. In the same manner as in Example 2, an adhesive for bonding a film die having an elastic modulus at 250 ° C. as shown in Table 7 was produced from this coating varnish. The adhesive for die bonding was laminated on the pressure-sensitive adhesive sheet prepared in Example 1 to prepare a pressure-sensitive adhesive sheet for attaching a wafer. Using the above-prepared pressure-sensitive adhesive sheet for attaching a wafer, dicing was performed in the same manner as in Example 2, and a chip was picked up together with a die bonding adhesive. The obtained silicon chip with an adhesive layer was mounted under die bonding conditions shown in Table 7. The peel strength is also shown in Table 7.

【００９８】[0098]

【表７】 [Table 7]

【００９９】（フィルム弾性率測定法）フィルム状に18
0℃×1時間の条件で硬化したダイ接着用接着剤を、
（株）東洋精製製作所社製レオログラフソリッドＳ型を
用いて、昇温速度５℃／ｍｉｎ、周波数１０Ｈｚで、動
的粘弾性を測定し、２５０℃における貯蔵弾性率Ｅ´を
弾性率とした。 （ピール強度測定法）実施例６と同じである。(Measurement method of film elastic modulus)
The die bonding adhesive cured under the condition of 0 ° C × 1 hour,
The dynamic viscoelasticity was measured at a heating rate of 5 ° C./min and a frequency of 10 Hz using a rheograph solid S type manufactured by Toyo Seisakusho Co., Ltd., and the storage elastic modulus E ′ at 250 ° C. was defined as the elastic modulus. did. (Peel strength measurement method) The same as in Example 6.

【０１００】[0100]

【発明の効果】以上説明してきたように、本発明に係る
ウエハ貼着用粘着シートによれば、放射線照射後には、
放射線硬化型粘着剤層の粘着力が大きく低下し、容易に
半導体素子とダイ接着用接着剤とを該粘着シートからピ
ックアップすることができる。またある程度の弾性率が
維持されるため、エキスパンディング工程において、所
望のチップ間隔を得ることが容易になり、かつチップの
ズレ等も発生せず、ピックアップを安定して行えるよう
になる。しかもチップをリードフレームに接着する際
に、ダイ接着用接着剤をチップ裏面に塗布する工程を省
略できるため、プロセス上も極めて有利である。さらに
そのダイ接着剤層の物性値を所定の値に設定することに
より、実装したパッケージの信頼性、特に耐リフロー性
が向上する。As described above, according to the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention, after irradiation,
The adhesive strength of the radiation-curable pressure-sensitive adhesive layer is greatly reduced, and the semiconductor element and the die bonding adhesive can be easily picked up from the pressure-sensitive adhesive sheet. In addition, since a certain degree of elasticity is maintained, it is easy to obtain a desired chip interval in the expanding step, and the chip can be stably picked up without any chip displacement. In addition, when the chip is bonded to the lead frame, the step of applying the die bonding adhesive to the back surface of the chip can be omitted, which is extremely advantageous in terms of the process. Further, by setting the physical property value of the die adhesive layer to a predetermined value, the reliability of the mounted package, particularly the reflow resistance, is improved.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明に係るウエハ貼着用粘着シートの一例の
断面図である。FIG. 1 is a cross-sectional view of an example of an adhesive sheet for attaching a wafer according to the present invention.

【図２】本発明に係るウエハ貼着用粘着シートの別の例
の断面図である。FIG. 2 is a cross-sectional view of another example of the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention.

【図３】本発明に係るウエハ貼着用粘着シートにウエハ
を貼着した状態を示す。FIG. 3 shows a state in which a wafer is attached to the adhesive sheet for attaching a wafer according to the present invention.

【図４】本発明に係るウエハ貼着用粘着シートを半導体
ウエハのダイシング工程に用いた場合の説明図である。FIG. 4 is an explanatory view when the pressure-sensitive adhesive sheet for attaching a wafer according to the present invention is used in a dicing process of a semiconductor wafer.

【図５】図４に示す工程の後、ウエハ貼着用粘着シート
に、裏面から放射線を照射した状態を示す。FIG. 5 shows a state where the pressure-sensitive adhesive sheet to be attached to the wafer is irradiated with radiation from the back surface after the step shown in FIG. 4;

【図６】図５に示す工程の後、ウエハ貼着用粘着シート
をエキスパンドした状態を示す。FIG. 6 shows a state where the pressure-sensitive adhesive sheet for attaching a wafer is expanded after the step shown in FIG. 5;

【図７】図６に示す工程の後、チップをピックアップす
る工程を示す。FIG. 7 shows a step of picking up a chip after the step shown in FIG. 6;

【図８】ピックアップされたチップとダイ接着用接着剤
を示す。FIG. 8 shows a picked-up chip and a die bonding adhesive.

【図９】チップをリードフレームにボンディングした状
態を示す。FIG. 9 shows a state where the chip is bonded to a lead frame.

【図１０】図５に示した放射線照射方法の一変形例を示
す。FIG. 10 shows a modification of the radiation irradiation method shown in FIG.

【図１１】プッシュプルゲージを用いてピール強度を測
定する方法を説明する正面図である。FIG. 11 is a front view illustrating a method of measuring the peel strength using a push-pull gauge.

【符号の説明】[Explanation of symbols]

１…ウエハ貼着用粘着シート ２…基材 ３…放射線硬化型粘着剤層 ４…ダイ接着用接着剤層 ５…剥離性シート ６…突き上げ針扞 ７…吸引コレット ８…リードフレーム ９…放射線発生源 ２４…プッシュプルゲージ ２５…熱盤 Ａ…ウエハ Ａ1、Ａ2、Ａ3、Ａ4…チップ Ｂ…放射線 DESCRIPTION OF SYMBOLS 1 ... Adhesive sheet for wafer attachment 2 ... Substrate 3 ... Radiation-curable adhesive layer 4 ... Adhesive layer for die bonding 5 ... Releasable sheet 6 ... Push-up needle rod 7 ... Suction collet 8 ... Lead frame 9 ... Radiation source 24: Push-pull gauge 25: Hot plate A: Wafer A1, A2, A3, A4: Chip B: Radiation

───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉浦 実 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 (72)発明者 増子 崇 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 Ｆターム(参考） 4J004 AA02 AA06 AA09 AA10 AA11 AA12 AA13 AA14 AB06 CA04 CA05 CA06 EA06 FA05 5F031 CA02 HA02 5F047 BA33 BA34 BA35 BA36 BA37 BA38 BA39 BA40 BB19  ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Minoru Sugiura 48 Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. On-site F term (reference) 4J004 AA02 AA06 AA09 AA10 AA11 AA12 AA13 AA14 AB06 CA04 CA05 CA06 EA06 FA05 5F031 CA02 HA02 5F047 BA33 BA34 BA35 BA36 BA37 BA38 BA39 BA40 BB19

Claims (8)

【特許請求の範囲】[Claims] 【請求項１】 基材面上に、少なくとも粘着剤と放射線
重合性オリゴマーとからなる放射線硬化型粘着剤層と、
ダイ接着用接着剤層とがこの順に形成されてなるウエハ
貼着用粘着シートにおいて、該放射線硬化型粘着剤層の
放射線硬化後における弾性率が０．１〜１０ＭＰａであ
り、かつダイ接着用接着剤層の吸水率が１．５体積％以
下であり、２５０℃における弾性率が１０ＭＰａ以下で
あることを特徴とするウエハ貼着用粘着シート。1. A radiation-curable pressure-sensitive adhesive layer comprising at least a pressure-sensitive adhesive and a radiation-polymerizable oligomer on a substrate surface,
In a pressure-sensitive adhesive sheet for bonding a wafer, in which a die-bonding adhesive layer is formed in this order, the radiation-curable pressure-sensitive adhesive layer has an elastic modulus after radiation curing of 0.1 to 10 MPa, and the die-bonding adhesive. A pressure-sensitive adhesive sheet for attaching a wafer, wherein the layer has a water absorption of 1.5% by volume or less and an elastic modulus at 250 ° C. of 10 MPa or less. 【請求項２】 前記放射線硬化型粘着剤層中において、
該放射線重合性オリゴマーが、１〜３０μｍの分散粒径
を有し、かつ均一に分散されてなる請求項１に記載のウ
エハ貼着用粘着シート。2. In the radiation-curable pressure-sensitive adhesive layer,
The pressure-sensitive adhesive sheet according to claim 1, wherein the radiation-polymerizable oligomer has a dispersed particle size of 1 to 30 µm and is uniformly dispersed. 【請求項３】 上記ダイ接着用接着剤層の残存揮発分が
３．０重量％以下である請求項１または２に記載のウエ
ハ貼着用粘着シート。3. The pressure-sensitive adhesive sheet according to claim 1, wherein the adhesive layer for die bonding has a residual volatile content of 3.0% by weight or less. 【請求項４】 上記ダイ接着用接着剤層は、半導体素子
と該支持部材とを接着した段階でのピール強度が０．５
ｋｇｆ/５ｍｍ×５ｍｍチップ以上である請求項１〜３
のいずれかに記載のウエハ貼着用粘着シート。4. The die bonding adhesive layer has a peel strength of 0.5 at the stage when the semiconductor element and the supporting member are bonded.
4 kgf / 5 mm × 5 mm chip or more.
The pressure-sensitive adhesive sheet for attaching a wafer according to any one of the above. 【請求項５】 上記ダイ接着用接着剤層の飽和吸湿率が
１．０体積％以下である請求項１〜４のいずれかに記載
のウエハ貼着用粘着シート。5. The pressure-sensitive adhesive sheet according to claim 1, wherein the adhesive layer for die bonding has a saturated moisture absorption of 1.0% by volume or less. 【請求項６】 上記ダイ接着用接着剤層で上記半導体素
子を上記支持部材に接着した段階で、上記接着剤層内部
と、上記接着剤層及び上記支持部材の界面とに存在する
ボイドが、ボイド体積率１０％以下である請求項１〜５
のいずれかに記載のウエハ貼着用粘着シート。6. At the stage where the semiconductor element is bonded to the support member with the die bonding adhesive layer, voids present inside the adhesive layer and at the interface between the adhesive layer and the support member are: The void volume ratio is 10% or less.
The pressure-sensitive adhesive sheet for attaching a wafer according to any one of the above. 【請求項７】 上記基材層が、エネルギー線透過型であ
る請求項１〜６のいずれかに記載のウエハ貼着用粘着シ
ート。7. The pressure-sensitive adhesive sheet for attaching a wafer according to claim 1, wherein the base material layer is of an energy ray transmission type. 【請求項８】 少なくとも半導体素子と支持部材とを含
む半導体装置であって、請求項１〜７のいずれかに記載
のウエハ貼着用粘着シートのダイ接着用接着剤層を介し
て、半導体素子が支持部材に接着されていることを特徴
とする半導体装置。8. A semiconductor device comprising at least a semiconductor element and a support member, wherein the semiconductor element is formed via the die-bonding adhesive layer of the pressure-sensitive adhesive sheet for attaching a wafer according to claim 1. A semiconductor device, which is bonded to a support member.
JP2000353569A 2000-11-20 2000-11-20 Adhesive sheet for sticking wafer and semiconductor device Pending JP2002158276A (en)

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Publication Number Publication Date
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