JP5910630B2 - Adhesive composition, film adhesive, adhesive sheet and semiconductor device - Google Patents

Adhesive composition, film adhesive, adhesive sheet and semiconductor device Download PDF

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Publication number
JP5910630B2
JP5910630B2 JP2013516253A JP2013516253A JP5910630B2 JP 5910630 B2 JP5910630 B2 JP 5910630B2 JP 2013516253 A JP2013516253 A JP 2013516253A JP 2013516253 A JP2013516253 A JP 2013516253A JP 5910630 B2 JP5910630 B2 JP 5910630B2
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Japan
Prior art keywords
adhesive
film
resin
adhesive composition
semiconductor element
Prior art date
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Expired - Fee Related
Application number
JP2013516253A
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Japanese (ja)
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JPWO2012160916A1 (en
Inventor
増子　崇
崇 増子
悟史 黒澤
悟史 黒澤
伊澤　弘行
弘行 伊澤
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Showa Denko Materials Co Ltd
Original Assignee
Hitachi Chemical Co Ltd
Showa Denko Materials Co Ltd
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Publication of JPWO2012160916A1 publication Critical patent/JPWO2012160916A1/en
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Publication of JP5910630B2 publication Critical patent/JP5910630B2/en
Expired - Fee Related legal-status Critical Current
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
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    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3142—Sealing arrangements between parts, e.g. adhesion promotors
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Description

本発明は、接着剤組成物、フィルム状接着剤、接着シート及びこれを用いた半導体装置に関する。   The present invention relates to an adhesive composition, a film adhesive, an adhesive sheet, and a semiconductor device using the same.

従来、半導体素子をリードフレーム等の半導体素子搭載用支持部材に接着するためのダイボンディング層を形成するダイボンディング用接着剤としては、銀ペーストが主に使用されていた。しかし、銀ペーストの場合、近年の半導体素子の大型化、半導体パッケージの小型化及び高性能化に伴って、ぬれ広がり性によるダイボンディング後のダイボンディング層のはみ出し、半導体素子の傾きに起因するワイヤボンディング時の不具合の発生、ダイボンディング層の膜厚精度の不足、及びダイボンディング層におけるボイド等の問題が生じやすくなる。そのために、半導体パッケージの小型化及び高性能化のための支持部材の小型化及び細密化の要求を満足することが困難となっていた。そこで、近年、支持部材の小型化及び細密化に対して有利な、フィルム状接着剤がダイボンディング用の接着剤として広く用いられている（例えば、特許文献１、特許文献２参照。）。このフィルム状接着剤は、例えば、個片貼付け方式（ｐｉｅｃｅ ｌａｍｉｎａｔｉｏｎ ｐｒｏｃｅｓｓ）及びウェハ裏面貼付方式（ｗａｆｅｒ ｂａｃｋ−ｓｉｄｅ ｌａｍｉｎａｔｉｏｎ ｐｒｏｃｅｓｓ）の半導体パッケージ（半導体装置）の製造方法において使用される。   Conventionally, silver paste has been mainly used as a die bonding adhesive for forming a die bonding layer for bonding a semiconductor element to a semiconductor element mounting support member such as a lead frame. However, in the case of silver paste, with the recent increase in size of semiconductor elements, downsizing and high performance of semiconductor packages, the die bonding layer protrudes after die bonding due to wetting and spreadability, and the wires due to the inclination of the semiconductor elements Problems such as occurrence of defects during bonding, insufficient film thickness accuracy of the die bonding layer, and voids in the die bonding layer are likely to occur. For this reason, it has been difficult to satisfy the demands for miniaturization and densification of support members for miniaturization and high performance of semiconductor packages. Therefore, in recent years, film adhesives that are advantageous for miniaturization and densification of support members have been widely used as adhesives for die bonding (see, for example, Patent Document 1 and Patent Document 2). This film adhesive is used in, for example, a method for manufacturing a semiconductor package (semiconductor device) of a piece laminating process and a wafer back-side laminating process.

個片貼付け方式においては、リール状のフィルム状接着剤をカッティング又はパンチングによって個片に切り出して支持部材に接着した後、支持部材上のフィルム状接着剤を介して、ダイシングによって個片化された半導体素子を支持部材に接着（ダイボンディング）する。その後、ワイヤボンド工程、封止工程等を経て半導体装置が製造される（例えば、特許文献３参照。）。しかし、この個片貼付け方式の場合、フィルム状接着剤を切り出して支持部材に接着するための専用の組立装置が必要となるために、銀ペーストを使用する場合に比べて製造コストが高くなるという問題があった。   In the piece pasting method, a reel-like film adhesive was cut into pieces by cutting or punching and bonded to a support member, and then separated into pieces by dicing through the film adhesive on the support member. The semiconductor element is bonded to the support member (die bonding). Thereafter, a semiconductor device is manufactured through a wire bonding process, a sealing process, and the like (see, for example, Patent Document 3). However, in the case of this piece pasting method, a dedicated assembly device for cutting out the film adhesive and bonding it to the support member is required, so that the manufacturing cost is higher than when silver paste is used. There was a problem.

一方、ウェハ裏面貼付け方式においては、半導体ウェハの裏面にフィルム状接着剤を貼り付け、貼り付けられたフィルム状接着剤の上にダイシングテープを貼り付けた後、半導体ウェハをダイシングによって個片化することによりフィルム状接着剤付きの半導体素子を得、これをピックアップして支持部材に接着（ダイボンディング）する。その後、ワイヤボンド工程、封止工程等を経て半導体装置が製造される。このウェハ裏面貼付け方式の場合、フィルム状接着剤を切り出して支持部材に接着するための専用の組立装置を必要とせず、従来の銀ペースト用の組立装置をそのまま用いるか、又はこれに熱盤（ｈｅａｔｉｎｇ ｐｌａｔｅｎ）を付加する等の部分的な改造を施した装置を用いて行うことができる。そのため、フィルム状接着剤を用いた組立方法の中では、製造コストが比較的安く抑えられる方法として注目されている（例えば、特許文献４参照。）。   On the other hand, in the wafer back surface pasting method, a film adhesive is pasted on the back surface of a semiconductor wafer, a dicing tape is pasted on the pasted film adhesive, and then the semiconductor wafer is diced by dicing. Thus, a semiconductor element with a film adhesive is obtained, and this is picked up and bonded (die bonding) to the support member. Thereafter, a semiconductor device is manufactured through a wire bonding process, a sealing process, and the like. In the case of this wafer back surface pasting method, a dedicated assembly device for cutting out the film adhesive and bonding it to the support member is not required, and a conventional silver paste assembly device is used as it is, or a heating plate ( It is possible to use a device that has been partially modified such as adding a heating platen. Therefore, in the assembly method using a film adhesive, it attracts attention as a method in which the manufacturing cost can be kept relatively low (for example, see Patent Document 4).

ダイボンディングフィルムを用いた半導体装置には、信頼性、すなわち、耐熱性、耐湿性、耐リフロー性等が求められる。耐リフロー性を確保するためには、２６０℃前後のリフロー加熱温度において、ダイボンディング層の剥離又は破壊を抑制できる高い接着強度を有することが求められる。   A semiconductor device using a die bonding film is required to have reliability, that is, heat resistance, moisture resistance, reflow resistance, and the like. In order to ensure reflow resistance, it is required to have a high adhesive strength that can suppress the peeling or breakage of the die bonding layer at a reflow heating temperature of around 260 ° C.

これまで、耐熱性樹脂組成物として、特定の酸成分と特定のアミン成分とからなり、有機溶剤に可溶なガラス転移温度が３５０℃以下のポリイミド樹脂１００重量部と、（Ｂ）１分子中に少なくとも２個以上のエポキシ基を有するエポキシ化合物５〜１００重量部と、（Ｃ）該エポキシ化合物と反応可能な活性水素基を有する化合物０．１〜２０重量部とを主たる成分として含有する樹脂組成物が開示されている（特許文献５）。   Up to now, as a heat-resistant resin composition, 100 parts by weight of a polyimide resin consisting of a specific acid component and a specific amine component and having a glass transition temperature of 350 ° C. or less soluble in an organic solvent, and (B) in one molecule A resin containing 5 to 100 parts by weight of an epoxy compound having at least two epoxy groups and (C) 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound A composition is disclosed (Patent Document 5).

特開平０３−１９２１７８号公報Japanese Patent Laid-Open No. 03-192178 特開平０４−２３４４７２号公報Japanese Patent Laid-Open No. 04-234472 特開平０９−０１７８１０号公報JP 09-017810 A 特開平０４−１９６２４６号公報Japanese Patent Laid-Open No. 04-196246 特許第３０１４５７８号Patent No. 3014578

ところで、最近になって、多機能化を目的として支持部材に複数の半導体素子が積層された、いわゆる３Ｄパッケージの半導体装置が急増している。そして、このような３Ｄパッケージの半導体装置においても、半導体装置全体の厚さを薄くすることが求められるため、半導体ウェハの更なる極薄化が進行している。これに伴い、ウェハ裏面へダイボンディングフィルムを貼付けた時のウェハ反りが顕在化してきている。そこで、これを防止するために、１５０℃よりも低温でウェハ裏面への貼り付けが可能なダイボンディングフィルムが求められている。   By the way, recently, there has been a rapid increase in so-called 3D package semiconductor devices in which a plurality of semiconductor elements are stacked on a support member for the purpose of multifunctionalization. Even in such a semiconductor device of a 3D package, since it is required to reduce the thickness of the entire semiconductor device, further ultrathinning of the semiconductor wafer is progressing. Along with this, wafer warpage when a die bonding film is attached to the back surface of the wafer has become apparent. Therefore, in order to prevent this, there is a demand for a die bonding film that can be attached to the back surface of the wafer at a temperature lower than 150 ° C.

また、組立プロセスの簡略化を目的に、フィルム状接着剤の一方の面に、ダイシングシートを貼り合せた接着シート、すなわちダイシングシートとダイボンディングフィルムとを一体化させたフィルム（以下、「一体型フィルム」という。）とすることによって、ウェハ裏面への貼り合せプロセスの簡略化を図った手法が提案されている。このような一体型フィルムの形態にするためには、ダイシングテープの軟化温度が１５０℃以下であり、ウェハ裏面への貼り合せ時の熱応力によるウェハ反りの抑制のため、１５０℃よりも低温で貼り付けが可能であることが求められる。このように、低温ラミネート性を含むプロセス特性と、耐リフロー性を含む半導体装置の信頼性を高度に両立できるダイボンディングフィルムに対する要求が強くなってきている。   For the purpose of simplifying the assembly process, an adhesive sheet in which a dicing sheet is bonded to one surface of a film adhesive, that is, a film in which a dicing sheet and a die bonding film are integrated (hereinafter referred to as “integrated type”). A method for simplifying the bonding process on the back surface of the wafer has been proposed. In order to make such an integrated film form, the softening temperature of the dicing tape is 150 ° C. or lower, and in order to suppress the wafer warp due to thermal stress at the time of bonding to the wafer back surface, the temperature is lower than 150 ° C. It is required that pasting is possible. As described above, there is an increasing demand for a die bonding film that can achieve a high degree of compatibility between process characteristics including low-temperature laminating properties and reliability of semiconductor devices including reflow resistance.

一方、例えば支持部材が表面に配線を有する有機基板である場合のように、接着面に配線段差等の段差が存在する場合、上述した特性に加えて、この段差に対する十分な充填性（埋め込み性）を確保することが、半導体装置の耐湿信頼性及び配線間の絶縁信頼性を確保する上で重要である。この埋め込み性が確保されなかった場合、未充填による空隙が原因で、耐湿信頼性及び耐リフロー性の低下が懸念される。このような半導体装置の最下段である半導体素子及び配線段差付き有機基板との接着に用いられるダイボンディングフィルムにおいては、半導体装置の組立工程において、発泡することなく、またボイドが発生することなく、基板表面の配線段差への埋め込み性を確保できる熱時流動性（ｈｏｔ ｆｌｕｉｄｉｔｙ）を有することが望まれる。   On the other hand, when there is a step such as a wiring step on the adhesive surface, for example, when the support member is an organic substrate having a wiring on the surface, in addition to the above-described characteristics, sufficient filling property (embedding property) It is important to ensure the moisture resistance reliability of the semiconductor device and the insulation reliability between the wirings. If this embedding property is not ensured, there is a concern that the moisture resistance reliability and the reflow resistance may be deteriorated due to voids due to unfilling. In the die bonding film used for bonding with the semiconductor element at the bottom of such a semiconductor device and an organic substrate with a wiring step, in the assembly process of the semiconductor device, without foaming and without generating voids, It is desired to have hot fluidity that can ensure embedding in the wiring step on the substrate surface.

しかしながら、上述した段差への埋め込みを可能にする熱時流動性の確保と、低温貼付性及び耐リフロー性を含めた高温時の耐熱性とを両立できる材料（接着剤組成物）、及びその設計はまだ十分ではない。   However, a material (adhesive composition) capable of achieving both high temperature fluidity that enables embedding in the above-described step and high temperature heat resistance including low temperature sticking property and reflow resistance, and its design Is not enough.

本発明は、上述した従来技術の問題に鑑み、成膜性、低温貼付性及び熱時流動性に優れ、かつ、ピール強度等の半導体装置の信頼性を満足することができる接着剤組性物、並びにこれを用いたフィルム状接着剤、接着シート及び半導体装置を提供することを目的とする。   In view of the above-described problems of the prior art, the present invention is an adhesive assembly that is excellent in film formability, low-temperature stickability, and fluidity during heat, and can satisfy the reliability of a semiconductor device such as peel strength. And a film-like adhesive, an adhesive sheet and a semiconductor device using the same.

本発明は、ポリウレタン樹脂と熱硬化性成分とを含み、Ｂステージでの１２０℃におけるフロー量が５００μｍ以上であり、かつＣステージでの１２０℃におけるフロー量が５００μｍ未満であり、上記Ｂステージでの１２０℃におけるフロー量を（Ａ）、上記Ｃステージでの１２０℃におけるフロー量を（Ｂ）としたとき、（Ａ）−（Ｂ）の値が１００μｍ以上である接着剤組成物を提供する。   The present invention includes a polyurethane resin and a thermosetting component, and the flow amount at 120 ° C. at the B stage is 500 μm or more, and the flow amount at 120 ° C. at the C stage is less than 500 μm. When the flow amount at 120 ° C. is (A) and the flow amount at 120 ° C. in the C stage is (B), an adhesive composition having a value of (A)-(B) of 100 μm or more is provided. .

上記接着剤組成物は、成膜性、低温貼付性及び熱時流動性に優れ、かつ、ピール強度等の半導体装置の信頼性を満足することができる。   The adhesive composition is excellent in film formability, low-temperature sticking property, and hot fluidity, and can satisfy the reliability of the semiconductor device such as peel strength.

本明細書中、「Ｂステージ」とは、後述する接着剤層形成用ワニスを厚さ６０μｍの二軸延伸ポリプロピレン（ＯＰＰ）基材上に厚さ４０±５μｍのフィルム状の接着剤層を形成するように塗工した後、オーブン中で、８０℃で３０分、続いて１２０℃で３０分の条件で加熱した後の状態をいい、「Ｃステージ」とはオーブン中で更に１８０℃で５時間の条件で加熱硬化した後の状態をいう。   In this specification, “B stage” means that a film-like adhesive layer having a thickness of 40 ± 5 μm is formed on a biaxially stretched polypropylene (OPP) base material having a thickness of 60 μm using a later-described adhesive layer forming varnish. After coating, the state after heating in an oven at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes is referred to as “C stage”. The state after heat-curing under time conditions.

また、本明細書中、「フロー量」とは、厚さが６０μｍのＯＰＰ基材上に厚さ４０±５μｍのフィルム状の接着剤層が形成された接着シートを、１０ｍｍ×１０ｍｍサイズに切断し、この接着シートを２枚のスライドグラス（松浪硝子工業株式会社製、７６ｍｍ×２６ｍｍ×１．０〜１．２ｍｍ厚）の間に挟んだサンプルを用意し、このサンプルに１２０℃の熱盤上で１００ｋｇｆ／ｃｍ２の荷重をかけ、１５秒間加熱圧着した後の上記ＯＰＰ基材の四辺からの接着剤のはみ出し量をそれぞれ光学顕微鏡で計測して得られた値から算術平均により求めた平均値をいう。In addition, in this specification, “flow amount” means that an adhesive sheet in which a film-like adhesive layer having a thickness of 40 ± 5 μm is formed on an OPP substrate having a thickness of 60 μm is cut into a size of 10 mm × 10 mm. A sample is prepared by sandwiching this adhesive sheet between two slide glasses (Matsunami Glass Industrial Co., Ltd., 76 mm × 26 mm × 1.0 to 1.2 mm thickness). The average obtained by arithmetic average from the values obtained by measuring the amount of protrusion of the adhesive from the four sides of the OPP substrate after applying a load of 100 kgf / cm 2 above and thermocompression bonding for 15 seconds, respectively, with an optical microscope. Value.

上記熱硬化性成分はエポキシ樹脂又はビスマレイミド樹脂を含むことが好ましい。また、上記接着剤組成物は更にフィラーを含有することが好ましい。   The thermosetting component preferably contains an epoxy resin or a bismaleimide resin. Moreover, it is preferable that the said adhesive composition contains a filler further.

上記接着剤組成物は、半導体素子同士、又は半導体素子と半導体素子搭載用支持部材との接着用であることが好ましく、半導体素子搭載用支持部材は、半導体素子を搭載する面に配線段差を有する有機基板であることが好ましい。   The adhesive composition is preferably for bonding between semiconductor elements or between a semiconductor element and a semiconductor element mounting support member, and the semiconductor element mounting support member has a wiring step on a surface on which the semiconductor element is mounted. An organic substrate is preferred.

本発明はまた、上記接着剤組成物をフィルム状に形成してなるフィルム状接着剤を提供する。かかるフィルム状接着剤は、上記接着剤組成物を用いているため、低温貼付性、熱時流動性に優れ、ピール強度等の半導体装置の信頼性を満足することができる。   The present invention also provides a film adhesive formed by forming the adhesive composition into a film. Since such a film-like adhesive uses the above-mentioned adhesive composition, it is excellent in low-temperature sticking property and hot fluidity, and can satisfy the reliability of the semiconductor device such as peel strength.

本発明は更に、支持基材と、該支持基材の主面上に形成された上記フィルム状接着剤とを備える接着シートを提供する。かかる接着シートは、上記接着剤組成物を用いているため、低温貼付性及び熱時流動性に優れ、かつピール強度等の半導体装置の信頼性を満足することができる。   The present invention further provides an adhesive sheet comprising a support substrate and the film adhesive formed on the main surface of the support substrate. Since such an adhesive sheet uses the above-mentioned adhesive composition, it is excellent in low-temperature sticking property and hot fluidity and can satisfy the reliability of the semiconductor device such as peel strength.

上記支持基材はダイシングシートであることが好ましく、ダイシングシートは、基材フィルム及び該基材フィルム上に設けられた粘着材層を有することが好ましい。   The support substrate is preferably a dicing sheet, and the dicing sheet preferably has a substrate film and an adhesive layer provided on the substrate film.

本発明はまた、半導体素子と半導体素子搭載用支持部材とが上記接着剤組成物の硬化物により接着された構造、又は隣接する半導体素子同士が上記接着剤組成物の硬化物により接着された構造を備える半導体装置を提供する。かかる半導体装置は、上記接着剤組成物を用いているため、ピール強度等の信頼性が高いものとなる。   The present invention also provides a structure in which a semiconductor element and a semiconductor element mounting support member are bonded by a cured product of the adhesive composition, or a structure in which adjacent semiconductor elements are bonded by a cured product of the adhesive composition. A semiconductor device is provided. Since such a semiconductor device uses the above-described adhesive composition, it has high reliability such as peel strength.

本発明は、ポリウレタン樹脂と熱硬化性成分とを含み、Ｂステージでの１２０℃におけるフロー量が５００μｍ以上であり、かつＣステージでの１２０℃におけるフロー量が５００μｍ未満であり、Ｂステージでの１２０℃におけるフロー量を（Ａ）、前記Ｃステージでの１２０℃におけるフロー量を（Ｂ）としたとき、（Ａ）−（Ｂ）の値が１００μｍ以上である組成物の接着剤としての応用、及び当該組成物の接着剤の製造のための応用ということもできる。   The present invention includes a polyurethane resin and a thermosetting component, and the flow amount at 120 ° C. at the B stage is 500 μm or more, and the flow amount at 120 ° C. at the C stage is less than 500 μm. Application as an adhesive of a composition having a value of (A)-(B) of 100 μm or more, where (A) is the flow amount at 120 ° C. and (B) is the flow amount at 120 ° C. in the C stage. And the application of the composition for the production of an adhesive.

本発明によれば、成膜性、低温貼付性及び熱時流動性に優れ、かつ、ピール強度等の半導体装置の信頼性を満足することができる接着剤組性物、並びにこれを用いたフィルム状接着剤を提供することができる。このような接着剤組成物及びフィルム状接着剤は、極薄ウェハ及び複数の半導体素子を積層した半導体装置に対応できるウェハ裏面貼付け方式の半導体素子の固定用に好適に用いることができる。   ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which is excellent in film forming property, low-temperature sticking property, and fluidity at the time of heat, and can satisfy the reliability of a semiconductor device such as peel strength, and a film using the same An adhesive can be provided. Such an adhesive composition and a film-like adhesive can be suitably used for fixing a semiconductor element of a wafer back surface attachment type that can be applied to an ultra-thin wafer and a semiconductor device in which a plurality of semiconductor elements are laminated.

ウェハ裏面にフィルム状接着剤を貼り付ける際に、通常、フィルム状接着剤が溶融する温度まで加熱するが、本発明のフィルム状接着剤を使用すれば、極薄ウェハの保護テープ又は貼り合わせるダイシングテープの軟化温度よりも低い温度でウェハ裏面に貼り付けることが可能となる。これにより、熱応力も低減され、大径化及び薄化するウェハの反り等の問題を解決できる。   When a film adhesive is affixed to the back side of the wafer, it is usually heated to a temperature at which the film adhesive melts. If the film adhesive of the present invention is used, a protective tape for ultra-thin wafer or dicing to be bonded is used. It becomes possible to affix on the wafer back surface at a temperature lower than the softening temperature of the tape. Thereby, thermal stress is also reduced, and problems such as warping of the wafer that is increased in diameter and thinned can be solved.

また、本発明のフィルム状接着剤によれば、ダイボンド時の熱と圧力によって、基板表面の配線段差への良好な埋め込みを可能にする熱時流動性を確保でき、複数の半導体素子を積層した半導体装置の製造工程に好適に対応できる。   In addition, according to the film adhesive of the present invention, the heat and pressure at the time of die bonding can ensure the fluidity at the time of heating that enables good embedding in the wiring step on the substrate surface, and a plurality of semiconductor elements are laminated. It can respond suitably to the manufacturing process of a semiconductor device.

また、本発明のフィルム状接着剤によれば、高温時の高い接着強度を確保できるため、硬化後の耐熱性を向上できる。さらに半導体装置の製造工程を簡略化できる。さらに、低温での貼り付けが可能であるため、応力緩和特性に優れており、ウェハの反り等の熱応力を低減しつつ、ダイシング時のチップ飛び（ｃｈｉｐ ｓｃａｔｔｅｒｉｎｇ）を抑えることができる。   Moreover, according to the film adhesive of this invention, since the high adhesive strength at the time of high temperature can be ensured, the heat resistance after hardening can be improved. Furthermore, the manufacturing process of the semiconductor device can be simplified. Furthermore, since it can be attached at a low temperature, it has excellent stress relaxation characteristics, and it is possible to suppress chip scattering during dicing while reducing thermal stress such as wafer warpage.

また、本発明のフィルム状接着剤によれば、ダイシング時の良好な切断性及びダイシング後の良好なピックアップ性を確保できるため、半導体装置の製造時の作業性を向上できる。   Moreover, according to the film-like adhesive of the present invention, it is possible to ensure good cutting performance at the time of dicing and good pick-up performance after dicing, so that workability at the time of manufacturing the semiconductor device can be improved.

また、本発明によれば、成膜性に優れ、かつ低コストの接着剤組成物を提供できる。また、本発明によれば、上述のフィルム状接着剤とダイシングシートを貼りあわせた接着シートを提供することができる。   Further, according to the present invention, it is possible to provide an adhesive composition having excellent film forming properties and low cost. Moreover, according to this invention, the adhesive sheet which bonded the above-mentioned film adhesive and the dicing sheet can be provided.

本発明の接着シートによれば、ダイシング工程までの貼付工程を簡略化し、パッケージの組立熱履歴に対しても安定した特性を確保できる材料を提供することが可能である。また、本発明によれば、ダイシングシートとダイボンディングフィルムの両機能を併せ持った粘接着剤層と基材とからなる接着シートを提供することができる。   According to the adhesive sheet of the present invention, it is possible to provide a material that can simplify the pasting process up to the dicing process and secure stable characteristics against the assembly heat history of the package. Moreover, according to this invention, the adhesive sheet which consists of an adhesive layer and a base material which have both functions of the dicing sheet and the die-bonding film can be provided.

本発明の実施形態に係る接着シートの一例を示す模式断面図である。It is a schematic cross section which shows an example of the adhesive sheet which concerns on embodiment of this invention. 本発明の実施形態に係る接着シートの一例を示す模式断面図である。It is a schematic cross section which shows an example of the adhesive sheet which concerns on embodiment of this invention. 本発明の実施形態に係る接着シートの一例を示す模式断面図である。It is a schematic cross section which shows an example of the adhesive sheet which concerns on embodiment of this invention. 本発明の実施形態に係る接着シートの一例を示す模式断面図である。It is a schematic cross section which shows an example of the adhesive sheet which concerns on embodiment of this invention. 本発明の実施形態に係る接着シートの一例を示す模式断面図である。It is a schematic cross section which shows an example of the adhesive sheet which concerns on embodiment of this invention. 本発明の実施形態に係る半導体装置の一例を示す模式断面図である。1 is a schematic cross-sectional view showing an example of a semiconductor device according to an embodiment of the present invention. 本発明の実施形態に係る半導体装置の一例を示す模式断面図である。1 is a schematic cross-sectional view showing an example of a semiconductor device according to an embodiment of the present invention. 接着力評価装置を示す模式部分断面図である。It is a model fragmentary sectional view which shows an adhesive force evaluation apparatus.

以下、必要に応じて図面を参照しつつ、本発明の好適な実施形態について詳細に説明する。図面中、同一又は相当部分には同一符号を付し、重複する説明は適宜省略する。上下左右等の位置関係は、特に断らない限り、図面に示す位置関係に基づくものとする。図面の寸法比率は図示の比率に限られるものではない。   Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and repeated description will be omitted as appropriate. The positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. The dimensional ratios in the drawings are not limited to the illustrated ratios.

図１に示す接着シート１００は、後述する接着剤組成物をフィルム状に成形した接着剤層１のみからなるものである。接着剤層１の厚みは、１〜１００μｍ程度であることが好ましい。接着シート１００を保存及び搬送する際には、幅１〜２０ｍｍ程度のテープ状又は、幅１０〜５０ｃｍ程度のシート状とし、巻き芯に巻きつけた状態とすることが好ましい。これにより、接着シート１００の保管及び搬送が容易となる。接着シート１００は、接着剤層１を複数重ねて貼り合せた積層体であってもよい。   The adhesive sheet 100 shown in FIG. 1 consists only of the adhesive layer 1 which shape | molded the adhesive composition mentioned later into a film form. The thickness of the adhesive layer 1 is preferably about 1 to 100 μm. When the adhesive sheet 100 is stored and transported, it is preferable that the adhesive sheet 100 has a tape shape with a width of about 1 to 20 mm or a sheet shape with a width of about 10 to 50 cm and is wound around a winding core. Thereby, storage and conveyance of the adhesive sheet 100 are facilitated. The adhesive sheet 100 may be a laminate in which a plurality of adhesive layers 1 are stacked and bonded together.

図２に示す接着シート１１０は、支持基材（基材フィルム２）と、基材フィルム２の両主面上に積層されたフィルム状の接着剤層１とを備える。また、基材フィルム２の片面上のみにフィルム状の接着剤層１が設けられていてもよい。基材フィルム２としては、接着剤層１を形成する際の加熱に耐えることができるものであれば特に限定されず、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエーテルナフタレートフィルム、メチルペンテンフィルム等を好適に用いることができる。基材フィルム２はこれらのフィルムを２種以上組み合わせた多層フィルムであってもよい。また、基材フィルム２の表面はシリコーン系、シリカ系等の離型剤で処理されていてもよい。   The adhesive sheet 110 shown in FIG. 2 includes a supporting base material (base material film 2) and a film-like adhesive layer 1 laminated on both main surfaces of the base material film 2. Further, the film-like adhesive layer 1 may be provided only on one surface of the base film 2. The base film 2 is not particularly limited as long as it can withstand the heating when the adhesive layer 1 is formed. For example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film Polyether naphthalate film, methyl pentene film and the like can be suitably used. The base film 2 may be a multilayer film in which two or more of these films are combined. The surface of the base film 2 may be treated with a release agent such as silicone or silica.

図３に示す接着シート１２０は、基材フィルム２と、基材フィルム２の一方の主面上に積層されたフィルム状の接着剤層１と、接着剤層１の基材フィルム２とは反対側の面上に積層された保護フィルム（保護テープ）３とを備える。保護フィルム３は、接着剤層１の損傷及び汚染を防ぐために、接着剤層１の基材フィルム２とは反対側の面を覆うように設けられている。この場合、接着シート１２０は、保護フィルム３を剥離してからダイボンディングに用いられる。   The adhesive sheet 120 shown in FIG. 3 is opposite to the base film 2, the film-like adhesive layer 1 laminated on one main surface of the base film 2, and the base film 2 of the adhesive layer 1 And a protective film (protective tape) 3 laminated on the side surface. The protective film 3 is provided so as to cover the surface of the adhesive layer 1 opposite to the base film 2 in order to prevent damage and contamination of the adhesive layer 1. In this case, the adhesive sheet 120 is used for die bonding after the protective film 3 is peeled off.

フィルム状の接着剤層１は、本発明の接着剤組成物をフィルム状に形成することにより得られる。以下、本発明の接着剤組成物について説明する。   The film-like adhesive layer 1 is obtained by forming the adhesive composition of the present invention into a film shape. Hereinafter, the adhesive composition of the present invention will be described.

本発明の接着剤組成物は、ポリウレタン樹脂及び熱硬化性成分を少なくとも含有する。   The adhesive composition of the present invention contains at least a polyurethane resin and a thermosetting component.

ポリウレタン樹脂としては、主鎖中にウレタン（カルバミド酸エステル）結合を持つ重合体であれば特に限定されないが、重量平均分子量が５０００〜５０００００、熱流動温度が２００℃以下の重合体であることが、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等の有機溶剤への溶解性、薄膜形成性、熱時流動性等の点で好ましい。中でも、下記式（Ｉ）で表されるポリウレタン樹脂が、有機溶剤への溶解性及び薄膜形成性に加えて、高接着性等を付与できる点で好ましく用いられる。   The polyurethane resin is not particularly limited as long as it is a polymer having a urethane (carbamic acid ester) bond in the main chain, but it may be a polymer having a weight average molecular weight of 5,000 to 500,000 and a heat flow temperature of 200 ° C. or less. , N-methyl-2-pyrrolidone (NMP) and the like in organic solvents, thin film formability, hot fluidity and the like. Among these, a polyurethane resin represented by the following formula (I) is preferably used in that it can impart high adhesiveness in addition to solubility in an organic solvent and thin film formability.

Figure 0005910630
式（Ｉ）中、ｎは１〜１００の整数を示し、好ましくは５〜１００であり、より好ましくは１０〜１００である。式（Ｉ）中、ｍは１〜１００の整数を示し、好ましくは２〜１００であり、より好ましくは５〜５０である。一般式（Ｉ）中、＊は結合手を示す。
Figure 0005910630
 In formula (I), n shows the integer of 1-100, Preferably it is 5-100, More preferably, it is 10-100. In formula (I), m shows the integer of 1-100, Preferably it is 2-100, More preferably, it is 5-50. In general formula (I), * indicates a bond.

上記ポリウレタン樹脂の具体例としては、ＤＩＣ Ｂａｙｅｒ Ｐｏｌｙｍｅｒ（ディーアイシー バイエル ポリマー）（株）製ＰＡＮＤＥＸシリーズ、Ｄｅｓｍｏｐａｎシリーズ、Ｔｅｘｉｎシリーズ等が挙げられる。   Specific examples of the polyurethane resin include PANDEX series, Desmopan series, and Texin series manufactured by DIC Bayer Polymer (DCI Bayer Polymer).

接着剤組成物のウェハ裏面への貼り付け可能温度は、ウェハの保護テープ及びダイシングテープの軟化温度以下であることが好ましく、また半導体ウェハの反りを抑えるという観点からも、上記貼り付け温度は、２０〜１００℃が好ましく、２０〜８０℃がより好ましく、２０〜６０℃がさらにより好ましい。   The temperature at which the adhesive composition can be applied to the back surface of the wafer is preferably equal to or lower than the softening temperature of the protective tape and dicing tape of the wafer, and also from the viewpoint of suppressing warpage of the semiconductor wafer, 20-100 degreeC is preferable, 20-80 degreeC is more preferable, and 20-60 degreeC is still more preferable.

これらの範囲の温度での貼り付けを可能にするためには、接着剤組成物のＴｇが１００℃以下であることが好ましく、そのためには、熱流動温度が２００℃以下のポリウレタン樹脂を選択することが望ましい。   In order to enable application at a temperature in these ranges, the adhesive composition preferably has a Tg of 100 ° C. or lower, and for this purpose, a polyurethane resin having a heat flow temperature of 200 ° C. or lower is selected. It is desirable.

ポリウレタン樹脂の熱流動温度が２００℃以下であると、ウェハ裏面への貼り付け温度を１００℃以下にできる接着剤設計がより容易となる傾向にある。ポリウレタン樹脂の熱流動温度の下限値は特に制限はないが、０℃以上とすることができる。０℃以上であると、Ｂステージ状態でのフィルム表面の粘着力が適度な強さになる傾向にあり、取り扱い性がより向上する他、本接着剤組成物付き半導体ウェハをダイシングした後のダイシングテープからのピックアップ性がより向上する傾向がある。   When the heat flow temperature of the polyurethane resin is 200 ° C. or lower, it is likely that the adhesive design capable of setting the temperature of attachment to the back surface of the wafer to 100 ° C. or lower becomes easier. The lower limit value of the heat flow temperature of the polyurethane resin is not particularly limited, but can be 0 ° C. or higher. When the temperature is 0 ° C. or higher, the adhesive force on the film surface in the B-stage state tends to be moderately strong, and handling properties are further improved, and dicing after dicing the semiconductor wafer with the adhesive composition There is a tendency that the pickup property from the tape is further improved.

熱流動温度が上記範囲内のポリウレタン樹脂を選択することにより、ウェハ裏面への貼り付け温度を低く抑えることができるだけでなく、低温でのダイボンドも確保することができ、半導体素子の反りの増大を抑制できる。   By selecting a polyurethane resin having a heat flow temperature within the above range, not only can the temperature of bonding to the backside of the wafer be kept low, but also die bonding at a low temperature can be secured, increasing the warpage of the semiconductor element. Can be suppressed.

なお、本明細書において、重量平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ；例えば株式会社島津製作所製、商品名：Ｃ−Ｒ４Ａ）により、下記測定条件で測定して得られる標準ポリスチレン換算値である。
溶媒：ジメチルホルムアミド（ＤＭＦ）＋臭化リチウム（ＬｉＢｒ）（０．０３ｍｏｌ（対ＤＭＦ１Ｌ）＋りん酸（０．０６ｍｏｌ（対ＤＭＦ１Ｌ））
カラム：Ｇ６０００ＨＸＬ＋Ｇ４０００ＨＸＬ＋Ｇ２０００ＨＸＬ（東ソー株式会社製）試料濃度：１０ｍｇ／５ｍＬ
注入量：０．５ｍＬ
圧力：１００ｋｇｆ／ｃｍ２
流量：１．００ｍＬ／分
測定温度：２５℃。
また、上記熱流動温度とは、フィルム化した試料を使用して、レオメトリックス製粘弾性アナライザーＲＳＡ−２を用いて、フィルムサイズ３５ｍｍ×１０ｍｍ×４０μｍ厚、昇温速度５℃／分、周波数１Ｈｚ、測定温度−１５０〜３００℃の条件で測定し、貯蔵弾性率が０．１ＭＰａ以下となる温度である。In the present specification, the weight average molecular weight is a standard polystyrene conversion value obtained by measurement under the following measurement conditions by gel permeation chromatography (GPC; manufactured by Shimadzu Corporation, trade name: C-R4A). It is.
Solvent: dimethylformamide (DMF) + lithium bromide (LiBr) (0.03 mol (vs DMF1L) + phosphoric acid (0.06 mol (vs DMF1L))
Column: G6000HXL + G4000HXL + G2000HXL (manufactured by Tosoh Corporation) Sample concentration: 10 mg / 5 mL
Injection volume: 0.5 mL
Pressure: 100 kgf / cm 2
Flow rate: 1.00 mL / min Measurement temperature: 25 ° C.
The heat flow temperature refers to a film sample, a rheometric viscoelasticity analyzer RSA-2, a film size of 35 mm × 10 mm × 40 μm thickness, a heating rate of 5 ° C./min, and a frequency of 1 Hz. The measurement temperature is a temperature at which the storage elastic modulus is 0.1 MPa or less, measured under the condition of -150 to 300 ° C.

ポリウレタン樹脂の含有量は、接着剤組成物全量に対して、５〜９５質量％であることが好ましく、１０〜９０質量％であることがより好ましく、２０〜８０質量％であることが更に好ましい。   The content of the polyurethane resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 20 to 80% by mass with respect to the total amount of the adhesive composition. .

熱硬化性成分は、熱により架橋反応を起こす反応性化合物からなる成分であれば特に制限はなく、例えば、エポキシ樹脂、シアネートエステル樹脂、ビスマレイミド樹脂、ビスアリルナジイミド樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、アルキド樹脂、アクリル樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、シリコーン樹脂、レゾルシノールホルムアルデヒド樹脂、キシレン樹脂、フラン樹脂、ケトン樹脂、トリアリルシアヌレート樹脂、ポリイソシアネート樹脂、トリス（２−ヒドロキシエチル）イソシアヌラートを含有する樹脂、トリアリルトリメリタートを含有する樹脂、シクロペンタジエンから合成された熱硬化性樹脂、芳香族ジシアナミドの三量化による熱硬化性樹脂等の他、多官能のアクリレート及び／又はメタクリレート化合物、ビニル基あるいはスチリル基を含む化合物、及びそれらの重合体等が挙げられる。中でも、高温での優れた接着力をもたせることができる点で、エポキシ樹脂が好ましく、高温での高い弾性率を付与できる点で、ビスマレイミド樹脂が好ましい。なお、これら熱硬化性成分は単独で又は２種類以上を組み合わせて用いることができる。   The thermosetting component is not particularly limited as long as it is a component composed of a reactive compound that causes a crosslinking reaction by heat. For example, epoxy resin, cyanate ester resin, bismaleimide resin, bisallyl nadiimide resin, phenol resin, urea resin , Melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, tris (2-hydroxy Ethyl) isocyanurate-containing resin, triallyl trimellitate-containing resin, thermosetting resin synthesized from cyclopentadiene, thermosetting resin by trimerization of aromatic dicyanamide, and other polyfunctional acrylates as well as/ The methacrylate compound, a compound containing a vinyl group or a styryl group, and a polymer or the like thereof. Among them, an epoxy resin is preferable in that it can have an excellent adhesive force at a high temperature, and a bismaleimide resin is preferable in that a high elastic modulus can be imparted at a high temperature. In addition, these thermosetting components can be used individually or in combination of 2 or more types.

熱硬化性成分の含有量は、ポリウレタン樹脂１００質量部に対して、５〜３００質量部が好ましく、１０〜２００質量部がより好ましく、２０〜１５０質量部がさらに好ましい。上記含有量が３００質量部を超えると、加熱時のアウトガスが多くなる他、フィルム形成性（靭性）が損なわれる傾向があり、上記含有量が５質量部未満であると、Ｂステージでの熱時流動性付与及びＣステージでの耐熱性並びに高温接着性を有効に付与できなくなる可能性が高くなる。   The content of the thermosetting component is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the polyurethane resin. If the content exceeds 300 parts by mass, outgassing during heating tends to increase, and film formability (toughness) tends to be impaired. If the content is less than 5 parts by mass, heat at the B stage There is a high possibility that the fluidity at the time, the heat resistance at the C stage and the high-temperature adhesiveness cannot be effectively imparted.

上記熱硬化性成分の硬化のために、硬化剤、触媒、過酸化物を使用することができ、必要に応じて硬化剤と硬化促進剤又は触媒と助触媒を併用することができる。上記硬化剤及び硬化促進剤、過酸化物の添加量並びに添加の有無については、後述する望ましい熱時流動性及び硬化後の耐熱性を確保できる範囲で判断、調整する。   In order to cure the thermosetting component, a curing agent, a catalyst, and a peroxide can be used, and a curing agent and a curing accelerator or a catalyst and a cocatalyst can be used in combination as necessary. About the addition amount of the said hardening | curing agent, a hardening accelerator, and a peroxide, and the presence or absence of addition, it judges and adjusts in the range which can ensure the desired thermal fluidity mentioned later and the heat resistance after hardening.

好ましい熱硬化性成分の一つであるエポキシ樹脂としては、分子内に少なくとも２個のエポキシ基を含むものがより好ましく、硬化性及び硬化物特性の点からフェノールのグリシジルエーテル型のエポキシ樹脂が極めて好ましい。   As the epoxy resin which is one of the preferred thermosetting components, those containing at least two epoxy groups in the molecule are more preferable, and phenol glycidyl ether type epoxy resins are extremely preferable in terms of curability and cured product characteristics. preferable.

このような樹脂としては、例えば、ビスフェノールＡ型、ＡＤ型、Ｓ型又はＦ型のグリシジルエーテル、水添加ビスフェノールＡ型のグリシジルエーテル、エチレンオキシド付加体ビスフェノールＡ型のグリシジルエーテル、プロピレンオキシド付加体ビスフェノールＡ型のグリシジルエーテル、フェノールノボラック樹脂のグリシジルエーテル、クレゾールノボラック樹脂のグリシジルエーテル、ビスフェノールＡノボラック樹脂のグリシジルエーテル、ナフタレン樹脂のグリシジルエーテル、３官能型（又は４官能型）のグリシジルエーテル、ジシクロペンタジエンフェノール樹脂のグリシジルエーテル、ジアリルビスフェノールＡジグリシジルエーテル、アリル化ビスフェノールＡとエピクロルヒドリンの重縮合物、ダイマー酸のグリシジルエステル、３官能型（又は４官能型）のグリシジルアミン、ナフタレン樹脂のグリシジルアミン等が挙げられる。これらは単独で又は２種類以上を組み合わせて使用することができる。   Examples of such resins include bisphenol A type, AD type, S type or F type glycidyl ether, water added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, propylene oxide adduct bisphenol A. Type glycidyl ether, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolak resin, glycidyl ether of naphthalene resin, trifunctional (or tetrafunctional type) glycidyl ether, dicyclopentadienephenol Resin glycidyl ether, diallyl bisphenol A diglycidyl ether, polycondensate of allylated bisphenol A and epichlorohydrin, dimer acid glyceride Succinimidyl ester, 3 glycidylamine functional type (or tetrafunctional), and glycidyl amines of naphthalene resins. These can be used alone or in combination of two or more.

また、これらのエポキシ樹脂には不純物イオンである、アルカリ金属イオン、アルカリ土類金属イオン及びハロゲンイオン（特に塩素イオン）、並びに不純物イオンを発生する加水分解性塩素等を３００ｐｐｍ以下に低減した高純度品を用いることがエレクトロマイグレーション防止及び金属導体回路の腐食防止のために好ましい。   In addition, these epoxy resins have a high purity in which impurity ions, alkali metal ions, alkaline earth metal ions and halogen ions (especially chlorine ions), and hydrolyzable chlorine that generates impurity ions are reduced to 300 ppm or less. It is preferable to use a product for preventing electromigration and preventing corrosion of a metal conductor circuit.

上記エポキシ樹脂を使用する場合は、必要に応じて硬化剤を使用することもできる。上記硬化剤としては、例えば、フェノール系化合物、脂肪族アミン、脂環族アミン、芳香族ポリアミン、ポリアミド、脂肪族酸無水物、脂環族酸無水物、芳香族酸無水物、ジシアンジアミド、有機酸ジヒドラジド、三フッ化ホウ素アミン錯体、イミダゾール類、第３級アミン等が挙げられ、中でもフェノール系化合物が好ましく、分子中に少なくとも２個のフェノール性水酸基を有するフェノール系化合物がより好ましい。   When using the said epoxy resin, a hardening | curing agent can also be used as needed. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acids. Examples thereof include dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. Among them, phenolic compounds are preferable, and phenolic compounds having at least two phenolic hydroxyl groups in the molecule are more preferable.

硬化剤としては、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ｔ−ブチルフェノールノボラック樹脂、ジシクロペンタジエンクレゾールノボラック樹脂、ジシクロペンタジエンフェノールノボラック樹脂、キシリレン変性フェノールノボラック樹脂、ナフトール系化合物、トリスフェノール系化合物、テトラキスフェノールノボラック樹脂、ビスフェノールＡノボラック樹脂、ポリ−ｐ−ビニルフェノール樹脂、フェノールアラルキル樹脂等が挙げられる。   Examples of the curing agent include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol novolak resin, dicyclopentadiene phenol novolak resin, xylylene-modified phenol novolak resin, naphthol compound, trisphenol compound, tetrakis Phenol novolac resin, bisphenol A novolak resin, poly-p-vinylphenol resin, phenol aralkyl resin and the like can be mentioned.

これらの中で、数平均分子量が４００〜１５００の範囲内のものが好ましい。これにより、半導体装置を組立てて加熱する際に、半導体素子、装置等の汚染の原因となるアウトガスを有効に低減できる。なお、硬化物の耐熱性を確保するためにも、これらのフェノール系化合物の配合量は、エポキシ樹脂のエポキシ当量と、フェノール系化合物のＯＨ当量の当量比が、０．９５：１．０５〜１．０５：０．９５となることが好ましい。   Among these, those having a number average molecular weight in the range of 400 to 1500 are preferable. Thereby, when the semiconductor device is assembled and heated, outgas that causes contamination of the semiconductor element, the device, and the like can be effectively reduced. In order to secure the heat resistance of the cured product, the compounding amount of these phenolic compounds is such that the equivalent ratio of the epoxy equivalent of the epoxy resin and the OH equivalent of the phenolic compound is 0.95: 1.05. It is preferably 1.05: 0.95.

また、必要に応じて、硬化促進剤を使用することもできる。硬化促進剤としては、熱硬化性樹脂を硬化させるものであれば特に制限はなく、例えば、イミダゾール類、ジシアンジアミド誘導体、ジカルボン酸ジヒドラジド、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、２−エチル−４−メチルイミダゾール−テトラフェニルボレート、１，８−ジアザビシクロ［５．４．０］ウンデセン−７−テトラフェニルボレート等が挙げられる。   Moreover, a hardening accelerator can also be used as needed. The curing accelerator is not particularly limited as long as it cures a thermosetting resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like.

好ましい熱硬化性成分の一つであるビスマレイミド樹脂としては、分子内にマレイミド基を２個以上含むことが好ましく、下記一般式（ＩＩＩ）で表されるビスマレイミド化合物、及び下記一般式（ＩＶ）で表されるノボラック型マレイミド化合物から選ばれる少なくとも１種であることがより好ましい。   The bismaleimide resin that is one of the preferred thermosetting components preferably contains two or more maleimide groups in the molecule. The bismaleimide compound represented by the following general formula (III) and the following general formula (IV) It is more preferable that it is at least 1 sort (s) chosen from the novolak-type maleimide compound represented by this.

Figure 0005910630
一般式（ＩＩＩ）中、Ｒは、芳香族環又は直鎖、分岐鎖又は環状脂肪族炭化水素基を含む２価の有機基を示す。Ｒは、ベンゼン残基、トルエン残基、キシレン残基、ナフタレン残基若しくは直鎖、分岐鎖若しくは環状飽和炭化水素基、又はこれらの組み合わせから構成される２価の基であることが好ましい。
Figure 0005910630
 In general formula (III), R represents a divalent organic group containing an aromatic ring or a linear, branched or cyclic aliphatic hydrocarbon group. R is preferably a divalent group composed of a benzene residue, a toluene residue, a xylene residue, a naphthalene residue, a linear, branched or cyclic saturated hydrocarbon group, or a combination thereof.

Figure 0005910630
一般式（ＩＶ）中、ｒは０〜２０の整数を示す。
Figure 0005910630
 In general formula (IV), r shows the integer of 0-20.

接着剤組成物のＣステージでの耐熱性及び高温接着力をより高度に付与できる点で、ビスマレイミド樹脂は、Ｒが下記式（ｖ）、（ｖｉ）若しくは（ｖｉｉ）で表される２価の基である一般式（ＩＩＩ）で表されるビスマレイミド化合物、又は一般式（ＩＶ）で表されるノボラック型マレイミド化合物であることが好ましい。

Figure 0005910630
Figure 0005910630
Figure 0005910630
 なお、これらのビスマレイミド樹脂は、それぞれ、１種を単独で又は２種以上を組み合わせて使用することができる。The bismaleimide resin is divalent in which R is represented by the following formula (v), (vi), or (vii) in that the heat resistance and high-temperature adhesive strength at the C stage of the adhesive composition can be imparted to a higher degree. It is preferable that it is a bismaleimide compound represented by the general formula (III) which is a group, or a novolac maleimide compound represented by the general formula (IV).
Figure 0005910630
Figure 0005910630
Figure 0005910630
 In addition, these bismaleimide resins can be used individually by 1 type or in combination of 2 or more types, respectively.

ビスマレイミド樹脂の加熱による硬化を促進するために、必要に応じて有機過酸化物が接着剤組成物に含有されていてもよい。接着シート作製時の硬化抑制、及びＢステージでの保存安定性の点から、１分間半減期温度が１２０℃以上の有機過酸化物を使用することが好ましい。接着剤組成物に含まれる有機過酸化物の含有量は、保存安定性、低アウトガス性、硬化性の観点から、マレイミド化合物の量を基準として０．０１〜１０質量％であることが好ましい。   In order to accelerate curing of the bismaleimide resin by heating, an organic peroxide may be contained in the adhesive composition as necessary. It is preferable to use an organic peroxide having a one-minute half-life temperature of 120 ° C. or higher from the viewpoint of suppressing the curing during the preparation of the adhesive sheet and storage stability at the B stage. The content of the organic peroxide contained in the adhesive composition is preferably 0.01 to 10% by mass based on the amount of the maleimide compound from the viewpoints of storage stability, low outgassing properties, and curability.

接着剤組成物は、更にフィラーを含有することが好ましい。フィラーとしては、例えば、銀粉、金粉、銅粉、ニッケル粉等の金属フィラー、アルミナ、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、結晶性シリカ、非晶性シリカ、窒化ホウ素、チタニア、ガラス、酸化鉄、セラミック等の無機フィラー、カーボン、ゴム系フィラー等の有機フィラー等が挙げられ、種類・形状等にかかわらず特に制限なく使用することができる。   It is preferable that the adhesive composition further contains a filler. Examples of the filler include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Inorganic fillers such as aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramics, and organic fillers such as carbon and rubber fillers are included. Regardless, it can be used without any particular restrictions.

フィラーは所望する機能に応じて使い分けることができる。例えば、金属フィラーは、接着剤組成物に導電性、熱伝導性、チキソ性等を付与する目的で添加され、非金属無機フィラーは、接着剤層に熱伝導性、低熱膨張性、低吸湿性等を付与する目的で添加され、有機フィラーは接着剤層に靭性等を付与する目的で添加される。これら金属フィラー、無機フィラー又は有機フィラーは、単独で又は２種類以上を組み合わせて使用することができる。   The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the adhesive composition, and the nonmetallic inorganic filler is thermally conductive, low thermal expansion, low hygroscopicity to the adhesive layer. The organic filler is added for the purpose of imparting toughness to the adhesive layer. These metal fillers, inorganic fillers or organic fillers can be used alone or in combination of two or more.

上記した中でも、半導体装置用接着材料に求められる、導電性、熱伝導性、低吸湿特性、絶縁性等を付与できる点で、金属フィラー、無機フィラー又は絶縁性のフィラーが好ましく、無機フィラー又は絶縁性フィラーの中では、樹脂ワニスに対する分散性が良好でかつ、熱時の高い接着力を付与できる点で窒化ホウ素フィラー又はシリカフィラーがより好ましい。   Among the above, metal fillers, inorganic fillers or insulating fillers are preferred, and inorganic fillers or insulating fillers are preferred in that they can provide the electrical conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, etc. required for adhesive materials for semiconductor devices. Among the fillers, a boron nitride filler or a silica filler is more preferable in that the dispersibility with respect to the resin varnish is good and a high adhesive force during heating can be imparted.

フィラーの使用量は、接着剤層に付与する特性又は機能に応じて決められるが、樹脂成分とフィラーの合計に対して１０〜４０体積％、好ましくは１０〜３０体積％、より好ましくは１０〜２０体積％である。フィラーを適度に増量させることにより、フィルム表面低粘着化及び高弾性率化が図れ、ダイシング性（ダイサー刃による切断性）、ピックアップ性（ダイシングテープとの易はく離性）、ワイヤボンディング性（超音波効率）、熱時の接着強度を有効に向上できる。   Although the usage-amount of a filler is determined according to the characteristic or function provided to an adhesive bond layer, it is 10 to 40 volume% with respect to the sum total of a resin component and a filler, Preferably it is 10 to 30 volume%, More preferably, it is 10 to 10 volume%. 20% by volume. By appropriately increasing the amount of filler, the film surface can be reduced in adhesion and elastic modulus, dicing (cutting with a dicer blade), pick-up (easy peeling from dicing tape), wire bonding (ultrasonic) Efficiency) and can effectively improve the adhesive strength during heating.

フィラーを必要以上に増量させると、低温貼付性、被着体との界面接着性及び熱時流動性が損なわれ、耐リフロー性を含む信頼性の低下を招く傾向にあるため、フィラーの使用量は上記の範囲内に収めることが好ましい。求められる特性のバランスをとるべく、最適フィラー含量を決定する。フィラーを用いた場合の混合・混練は、通常の攪拌機、らいかい機、三本ロール、ボールミル等の分散機を適宜、組み合わせて行うことができる。   If the filler is increased more than necessary, the low-temperature sticking property, interfacial adhesion to the adherend and hot fluidity tend to be impaired, leading to a decrease in reliability including reflow resistance. Is preferably within the above range. The optimal filler content is determined to balance the required properties. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

接着剤組成物には、異種材料間の界面結合を良くするために、各種カップリング剤を添加することもできる。カップリング剤としては、例えば、シラン系、チタン系、アルミニウム系等が挙げられ、中でも効果が高い点で、シラン系カップリング剤が好ましい。上記カップリング剤の使用量は、カップリング剤の効果、硬化後の耐熱性及びコストの面から、ポリウレタン樹脂１００質量部に対して、０．０１〜２０質量部とするのが好ましい。   Various coupling agents can be added to the adhesive composition in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective. The amount of the coupling agent used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the polyurethane resin from the viewpoint of the effect of the coupling agent, heat resistance after curing, and cost.

接着剤組成物には、イオン性不純物を吸着して、吸湿時の絶縁信頼性を良くするために、更にイオン捕捉剤を添加することもできる。このようなイオン捕捉剤としては、特に制限はなく、例えば、トリアジンチオール化合物、及びビスフェノール系還元剤等の銅がイオン化して溶け出すのを防止するため銅害防止剤として知られる化合物、並びに、ジルコニウム系及びアンチモンビスマス系マグネシウムアルミニウム化合物等の無機イオン吸着剤等が挙げられる。上記イオン捕捉剤の使用量は、イオン補足剤の添加による効果、硬化後の耐熱性、コスト等の点から、ポリウレタン樹脂１００質量部に対して、０．０１〜１０質量部が好ましい。   An ion scavenger can be further added to the adhesive composition in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited, for example, a triazine thiol compound, a compound known as a copper damage inhibitor to prevent copper from being ionized and dissolved, such as a bisphenol reducing agent, and the like, Examples thereof include inorganic ion adsorbents such as zirconium-based and antimony bismuth-based magnesium aluminum compounds. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyurethane resin from the viewpoints of the effect of adding the ion scavenger, heat resistance after curing, cost, and the like.

また、接着剤組成物には、適宜、軟化剤、老化防止剤、着色剤、難燃剤、テルペン系樹脂等の粘着付与剤、熱可塑系高分子成分を添加してもよい。接着性向上及び硬化時の応力緩和性を付与するため用いられる熱可塑系高分子成分としては、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリビニルブチラール樹脂、キシレン樹脂、フェノキシ樹脂、尿素樹脂、アクリルゴム等が挙げられる。これら高分子成分は、重量平均分子量が５０００〜１００００００のものが好ましい。   In addition, a softener, an anti-aging agent, a colorant, a flame retardant, a tackifier such as a terpene resin, and a thermoplastic polymer component may be appropriately added to the adhesive composition. Examples of thermoplastic polymer components used to improve adhesion and provide stress relaxation during curing include polyester resin, polyamide resin, polyimide resin, polyvinyl butyral resin, xylene resin, phenoxy resin, urea resin, acrylic rubber, etc. Is mentioned. These polymer components preferably have a weight average molecular weight of 5,000 to 1,000,000.

接着剤組成物の熱時流動性を調整するために、必要に応じて反応性可塑剤を添加してもよい。このような可塑剤としては、液状であれば特に制限はないが、エポキシ基含有無溶剤型液状アクリルポリマー（例えば、東亜合成（株）製：ＵＧ−４０１０）等が好ましく用いられる。   In order to adjust the hot fluidity of the adhesive composition, a reactive plasticizer may be added as necessary. Such a plasticizer is not particularly limited as long as it is liquid, but an epoxy group-containing solventless liquid acrylic polymer (for example, UG-4010 manufactured by Toa Gosei Co., Ltd.) is preferably used.

上記エポキシ基含有無溶剤型液状アクリルポリマーの含有量は、Ｂステージでの良好な熱時流動性、低アウトガス性とＣステージでの耐熱性の点から、ポリウレタン樹脂１００質量部に対して、１〜３００質量部であることが好ましく、５〜２００質量部であることがより好ましく、１０〜１００質量部であることがさらに好ましい。この含有量が１質量部未満であると、上記特性を両立する効果が小さくなる傾向があり、３００質量部を超えると、加熱時のアウトガスが多くなり、成膜性及び取り扱い性が徐々に低下する傾向にある。   The content of the epoxy group-containing solventless liquid acrylic polymer is 1 with respect to 100 parts by mass of the polyurethane resin from the viewpoint of good thermal fluidity at the B stage, low outgassing property, and heat resistance at the C stage. It is preferable that it is -300 mass parts, It is more preferable that it is 5-200 mass parts, It is further more preferable that it is 10-100 mass parts. If the content is less than 1 part by mass, the effect of achieving the above characteristics tends to be small. If the content exceeds 300 parts by mass, outgassing during heating increases, and the film formability and handleability gradually decrease. Tend to.

本発明の接着剤組成物は、Ｂステージでの１２０℃におけるフロー量を（Ａ）、Ｃステージでのフロー量を（Ｂ）としたとき、（Ａ）−（Ｂ）が１００μｍ以上であり、２００μｍ以上であるとより好ましく、５００μｍ以上であるとさらに好ましい。（Ａ）−（Ｂ）が１００μｍ未満であると、Ｂステージでの熱流動による熱圧着性とＣステージでの熱流動抑制による高温接着性を両立が困難となる傾向にあり、半導体素子固定用フィルム状接着剤としての機能を備えることが困難になる。   In the adhesive composition of the present invention, when the flow amount at 120 ° C. at the B stage is (A) and the flow amount at the C stage is (B), (A)-(B) is 100 μm or more, More preferably, it is 200 μm or more, and further preferably 500 μm or more. If (A)-(B) is less than 100 μm, it tends to be difficult to achieve both thermocompression bonding due to thermal fluidization at the B stage and high-temperature adhesiveness due to thermal fluidity suppression at the C stage. It becomes difficult to provide a function as a film adhesive.

本発明の接着剤組成物のＢステージの１２０℃におけるフロー量は５００μｍ以上であり、１０００μｍ以上であるとより好ましく、２０００μｍ以上であるとさらに好ましい。また、接着剤組成物のＣステージの１２０℃におけるフロー量は５００μｍ未満であり、３００μｍ未満であるとより好ましく、１００μｍ未満であるとさらにより好ましい。   The flow amount at 120 ° C. of the B stage of the adhesive composition of the present invention is 500 μm or more, more preferably 1000 μm or more, and further preferably 2000 μm or more. Further, the flow amount at 120 ° C. of the C-stage of the adhesive composition is less than 500 μm, more preferably less than 300 μm, and even more preferably less than 100 μm.

これにより、表面に配線等が形成されている有機基板のような表面凹凸を有する支持部材に、半導体素子を８０〜２００℃の温度で１ＭＰａ以下の圧力で圧着したときに、上記支持部材表面凹凸による段差に対する十分な埋め込み性を確保できる。   As a result, when the semiconductor element is pressure-bonded to a support member having surface unevenness such as an organic substrate having wirings formed on the surface at a pressure of 1 MPa or less at a temperature of 80 to 200 ° C., the surface unevenness of the support member Sufficient embedding with respect to the level difference due to can be ensured.

上記Ｂステージの１２０℃におけるフロー量が５００μｍ未満であると、上述した熱流動による熱圧着性を確保できる温度が１２０℃を超える可能性が高くなり、熱応力による反りの発生等熱ひずみに影響を与える可能性が高くなる他、基板上の凹凸に対する埋め込み性が低下する。   When the flow amount at 120 ° C. of the B stage is less than 500 μm, there is a high possibility that the temperature at which the thermocompression bonding due to the above-described heat flow can be ensured exceeds 120 ° C., which affects the thermal strain such as the occurrence of warpage due to thermal stress The embedding property with respect to the unevenness on the substrate is reduced.

上記Ｂステージの１２０℃におけるフロー量の上限は特に限定されないが、例えば５０００μｍ以下とすることができる。５０００μｍを超えると、８０〜１５０℃での加熱圧着時の熱流動が大きくなりすぎて、支持部材界面に残存する空気の巻き込み又は発泡等により、フィルム状接着剤内部にボイドが残存し易くなる傾向がある。   The upper limit of the flow amount at 120 ° C. of the B stage is not particularly limited, but can be, for example, 5000 μm or less. When it exceeds 5000 μm, the heat flow at the time of thermocompression bonding at 80 to 150 ° C. becomes too large, and voids tend to remain inside the film adhesive due to entrainment or foaming of air remaining at the support member interface. There is.

また、上記Ｃステージでの１２０℃におけるフロー量が５００μｍを超えると、上述した高温接着性の確保が困難になり、はんだリフロー時の熱流動による発泡等、耐リフロー性の確保が困難になる。上記Ｃステージでの１２０℃におけるフロー量の下限は特に限定されないが、例えば０μｍ以上とすることができる。   On the other hand, if the flow amount at 120 ° C. in the C stage exceeds 500 μm, it becomes difficult to ensure the above-mentioned high-temperature adhesion, and it becomes difficult to ensure reflow resistance such as foaming due to thermal flow during solder reflow. The lower limit of the flow amount at 120 ° C. in the C stage is not particularly limited, but may be, for example, 0 μm or more.

フィルム状接着剤は、上述の成分を有機溶媒中で混合、混練してワニス（接着剤層形成用ワニス）を調製した後、基材フィルム上に上記ワニスの層を形成させ、加熱乾燥した後に基材を除去することで得ることができる。   The film-like adhesive is prepared by mixing and kneading the above components in an organic solvent to prepare a varnish (adhesive layer forming varnish), and then forming the varnish layer on a base film and drying by heating. It can be obtained by removing the substrate.

上記の混合、混練は、通常の攪拌機、らいかい機、三本ロール、ボールミル等の分散機を適宜、組み合わせて行うことができる。上記の加熱乾燥の条件は、使用した溶媒が充分に揮散する条件であれば特に制限はないが、通常５０〜２００℃で、０．１〜９０分間加熱して行う。   The above mixing and kneading can be carried out by appropriately combining dispersers such as ordinary stirrers, crackers, three rolls, and ball mills. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently volatilized, but the heating is usually performed at 50 to 200 ° C. for 0.1 to 90 minutes.

上記接着剤層の製造の際に用いる有機溶媒、即ちワニス溶剤は、材料を均一に溶解、混練又は分散できるものであれば制限はなく、例えば、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ―メチル−２−ピロリドン、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、トルエン、ベンゼン、キシレン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、エチルセロソルブ、エチルセロソルブアセテート、ブチルセロソルブ、ジオキサン、シクロヘキサノン、酢酸エチル等が挙げられる。   The organic solvent used in the production of the adhesive layer, that is, the varnish solvent is not limited as long as the material can be uniformly dissolved, kneaded, or dispersed. For example, dimethylformamide, dimethylacetamide, N-methyl-2- Examples include pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate.

フィルム状接着剤の製造時に使用する基材フィルムは、上記の加熱乾燥の条件に耐えるものであれば特に制限するものではなく、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエーテルナフタレートフィルム、メチルペンテンフィルム等が挙げられる。これらの基材としてのフィルムは２種以上組み合わせて多層フィルムとしてもよく、表面がシリコーン系、シリカ系等の離型剤等で処理されたものであってもよい。   The base film used in the production of the film adhesive is not particularly limited as long as it can withstand the above-mentioned heat drying conditions. For example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyether Examples include imide films, polyether naphthalate films, and methylpentene films. Two or more kinds of these base films may be combined to form a multilayer film, or the surface may be treated with a release agent such as a silicone or silica.

図４に示す接着シート１３０は、支持基材（基材フィルム７）及び支持基材の一方の主面上に積層された粘着剤層６を有するダイシングシート５と、ダイシングシート５の粘着剤層６上に積層されたフィルム状の接着剤層１とを備える。基材フィルム７は、上述の基材フィルム２と同様のものを使用することができるが、引張テンションを加えたときの伸び（通称、エキスパンド）を確保できるフィルムであることが好ましく、材質がポリオレフィンのフィルムが好ましく用いられる。また、接着シート１３０における接着剤層１は、これを貼り付ける半導体ウェハの形状に近い形状に予め形成されていることが好ましい。   The adhesive sheet 130 shown in FIG. 4 includes a dicing sheet 5 having a pressure-sensitive adhesive layer 6 laminated on one main surface of a support base material (base film 7) and the support base material, and a pressure-sensitive adhesive layer of the dicing sheet 5. 6 and a film-like adhesive layer 1 laminated on top of each other. The base film 7 can be the same as the base film 2 described above, but is preferably a film that can ensure elongation (commonly known as an expand) when a tensile tension is applied, and the material is polyolefin. These films are preferably used. Moreover, it is preferable that the adhesive layer 1 in the adhesive sheet 130 is formed in advance in a shape close to the shape of the semiconductor wafer to which the adhesive layer 1 is attached.

上記接着シート１３０は、ダイシングフィルムとしての機能を果たす粘着剤層６と、粘着剤層６上に積層されたダイボンディング用接着剤としての接着剤層１とを備えていることにより、ダイシング工程においてはダイシングフィルムとして、ダイボンディング工程においてはダイボンディングフィルムとして機能することができる。例えば、半導体ウェハの裏面にフィルム状の接着剤層１の側が半導体ウェハと密着するように接着シート１３０が貼り付けられた状態でダイシングした後、フィルム状の接着剤層１が付いた半導体素子をダイシングシート５からピックアップして、これをそのままダイボンディング工程に用いることができる。   In the dicing process, the adhesive sheet 130 includes the pressure-sensitive adhesive layer 6 that functions as a dicing film, and the adhesive layer 1 as an adhesive for die bonding laminated on the pressure-sensitive adhesive layer 6. Can function as a dicing film and in the die bonding step as a die bonding film. For example, after dicing in a state where the adhesive sheet 130 is attached so that the film-like adhesive layer 1 side is in close contact with the semiconductor wafer on the back surface of the semiconductor wafer, the semiconductor element with the film-like adhesive layer 1 is attached. It can be picked up from the dicing sheet 5 and used as it is in the die bonding step.

粘着剤層６は、感圧型又は放射線硬化型の粘着剤のいずれで形成されていてもよく、ダイシング時には半導体素子が飛散しない十分な粘着力を有し、その後の半導体素子のピックアップ工程においては半導体素子を傷つけない程度の低い粘着力を有するものであれば特に制限することなく従来公知のものを使用することができる。中でも、粘着剤層６は、放射線硬化型の粘着剤で形成されていることが好ましい。放射線硬化型の粘着剤は、ダイシングの際には高粘着力で、ダイシング後のピックアップの際にはピックアップ前の放射線照射によって低粘着力となるといったように、粘着力の制御が容易である。   The pressure-sensitive adhesive layer 6 may be formed of either a pressure-sensitive or radiation-curable pressure-sensitive adhesive, and has a sufficient adhesive force that prevents the semiconductor element from scattering during dicing. Any conventionally known material can be used without particular limitation as long as it has a low adhesive strength that does not damage the element. Especially, it is preferable that the adhesive layer 6 is formed with the radiation curing type adhesive. The radiation curable pressure-sensitive adhesive has a high adhesive strength when dicing, and has a low adhesive strength when picked up after dicing and has a low adhesive strength due to radiation irradiation before picking up.

粘着剤層６が放射線硬化型の粘着剤で形成されている場合、半導体ウェハの裏面に接着剤層１が密着するように接着シート１３０を貼り付けた場合に、半導体ウェハに対するフィルム状接着剤の２５℃での９０°ピール剥離力をＣとし、露光量５００ｍＪ／ｃｍ２の条件でＵＶ照射した後の粘着剤層のフィルム状接着剤に対する２５℃での９０°ピール剥離力をＤとしたときに、（Ｃ−Ｄ）の値が１Ｎ／ｍ以上であることが好ましい。この（Ｃ−Ｄ）の値は５Ｎ／ｍ以上がより好ましく、１０Ｎ／ｍ以上がさらに好ましい。（Ｃ−Ｄ）の値が１Ｎ／ｍ未満であると、ピックアップ時に半導体素子を傷つけたり、ピックアップ時に半導体ウェハとフィルム状接着剤との界面において先に剥離を生じてしまい、正常にピックアップできなくなったりする傾向にある。When the pressure-sensitive adhesive layer 6 is formed of a radiation curable pressure-sensitive adhesive, when the adhesive sheet 130 is attached so that the adhesive layer 1 is in close contact with the back surface of the semiconductor wafer, the film-like adhesive for the semiconductor wafer When 90 ° peel peel strength at 25 ° C. is C, and 90 ° peel peel strength at 25 ° C. is 25 ° C. with respect to the film adhesive of the pressure-sensitive adhesive layer after UV irradiation under the condition of exposure amount 500 mJ / cm 2 In addition, the value of (C−D) is preferably 1 N / m or more. The value of (CD) is more preferably 5 N / m or more, and further preferably 10 N / m or more. If the value of (C−D) is less than 1 N / m, the semiconductor element may be damaged at the time of pick-up, or peeling may occur first at the interface between the semiconductor wafer and the film adhesive at the time of pick-up, making it impossible to pick up normally. It tends to be.

なお、本実施形態に係る接着シートは、図５に示す接着シート１４０のように、接着シート１３０におけるダイシングシート５に代えて基材フィルム７のみからなるダイシングシート５を設けた接着シート１４０であってもよい。この態様の場合には、フィルム状の接着剤層１が予めウェハに近い形状に形成されている（プリカット（ｐｒｅｃｕｔ））ことが好ましい。   Note that the adhesive sheet according to the present embodiment is an adhesive sheet 140 provided with a dicing sheet 5 made of only the base film 7 instead of the dicing sheet 5 in the adhesive sheet 130, as in the adhesive sheet 140 shown in FIG. May be. In the case of this aspect, it is preferable that the film-like adhesive layer 1 is formed in advance in a shape close to the wafer (precut).

接着シート１３０及び１４０は、半導体装置製造工程を簡略化する目的で、接着剤層１とダイシングシート又は引張テンションを加えたときの伸び（通称、エキスパンド）を確保できる基材フィルム７とを少なくとも備える一体型の接着シートである。即ち、ダイシングシートとダイボンディングフィルムの両者に要求される特性を兼ね備える接着シートである。そのため、上述の一体型の接着シートは、半導体ウェハの裏面に一体型接着シートのフィルム状接着剤を加熱しながらウェハ裏面にラミネートし、ダイシングした後、フィルム状接着剤付き半導体素子としてピックアップして使用することができる。   For the purpose of simplifying the semiconductor device manufacturing process, the adhesive sheets 130 and 140 include at least the adhesive layer 1 and a base film 7 that can ensure elongation (commonly referred to as expanded) when a dicing sheet or tensile tension is applied. It is an integrated adhesive sheet. That is, it is an adhesive sheet having characteristics required for both a dicing sheet and a die bonding film. Therefore, the above-mentioned integrated adhesive sheet is laminated on the back surface of the wafer while heating the film adhesive of the integrated adhesive sheet on the back surface of the semiconductor wafer, diced, and then picked up as a semiconductor element with a film adhesive. Can be used.

本発明の接着剤組成物及びフィルム状接着剤は、ＩＣ、ＬＳＩ等の半導体素子と、４２アロイリードフレーム、銅リードフレーム等のリードフレーム；ポリイミド樹脂、エポキシ樹脂等のプラスチックフィルム；ガラス不織布等基材にポリイミド樹脂、エポキシ樹脂等のプラスチックを含浸、硬化させたもの；アルミナ等のセラミックス等の半導体搭載用支持部材等の被着体とを貼り合せるためのダイボンディング用接着材料として用いることができる。   The adhesive composition and the film-like adhesive of the present invention include semiconductor elements such as IC and LSI, lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resins and epoxy resins; A material obtained by impregnating and curing a plastic such as polyimide resin or epoxy resin on a material; can be used as an adhesive material for die bonding for bonding an adherend such as a ceramic mounting support member such as ceramics such as alumina. .

上記した中でも、表面に有機レジスト層を具備してなる有機基板、表面に配線を有する有機基板等の、表面に凹凸を有する有機基板と半導体素子とを接着するためのダイボンディング用接着材料として好適に用いられる。また、複数の半導体素子を積み重ねた構造のＳｔａｃｋｅｄ−ＰＫＧにおいて、半導体素子と半導体素子とを接着するための接着材料としても好適に用いられる。   Among the above, it is suitable as an adhesive material for die bonding for bonding an organic substrate having an uneven surface to a semiconductor element, such as an organic substrate having an organic resist layer on the surface and an organic substrate having wiring on the surface. Used for. Further, in the Stacked-PKG having a structure in which a plurality of semiconductor elements are stacked, it is also suitably used as an adhesive material for bonding the semiconductor elements to the semiconductor elements.

上記フィルム状接着剤の用途のうち、このフィルム状接着剤を備える半導体装置について図面を用いて具体的に説明する。ただし、上述のフィルム状接着剤の用途は、以下に説明する実施形態に係る半導体装置に限定されるものではない。   Among the uses of the film adhesive, a semiconductor device provided with the film adhesive will be specifically described with reference to the drawings. However, the use of the above-mentioned film adhesive is not limited to the semiconductor device according to the embodiment described below.

図６に示す半導体装置２００は、半導体素子９が、上記フィルム状接着剤によって形成されたダイボンディング層（硬化した接着剤層）８を介して半導体素子搭載用支持部材１０に接着され、半導体素子９の接続端子（図示せず）がワイヤ１１を介して外部接続端子（図示せず）と電気的に接続され、更に、封止材１２によって封止された構成を有している。   In a semiconductor device 200 shown in FIG. 6, a semiconductor element 9 is bonded to a semiconductor element mounting support member 10 via a die bonding layer (cured adhesive layer) 8 formed by the film adhesive. 9 connection terminals (not shown) are electrically connected to external connection terminals (not shown) via wires 11, and are further sealed with a sealing material 12.

図７に示す半導体装置２１０は、一段目の半導体素子９ａが上記フィルム状接着剤によって形成されたダイボンディング層（硬化した接着剤層）８、を介して半導体素子搭載用支持部材１０に接着され、半導体素子９ａの上に半導体素子９ｂが上記フィルム状接着剤によって形成されたダイボンディング層（硬化した接着剤層）８を介して接着され、全体が封止材１２によって封止された構成を有している。半導体素子９ａ及び半導体素子９ｂの接続端子（図示せず）は、それぞれワイヤ１１を介して外部接続端子（図示せず）と電気的に接続されている。   In the semiconductor device 210 shown in FIG. 7, the first-stage semiconductor element 9a is bonded to the semiconductor element mounting support member 10 via the die bonding layer (cured adhesive layer) 8 formed of the film adhesive. The semiconductor element 9b is bonded onto the semiconductor element 9a via the die bonding layer (cured adhesive layer) 8 formed of the film adhesive, and the whole is sealed with the sealing material 12. Have. The connection terminals (not shown) of the semiconductor elements 9a and 9b are electrically connected to external connection terminals (not shown) via wires 11, respectively.

図６及び図７に示す半導体装置（半導体パッケージ）は、本実施形態に係るフィルム状接着剤を用いたダイボンディング工程と、これに続くワイヤボンディング工程、封止材による封止工程等の工程と、を備える製造方法により製造することができる。ダイボンディング工程においては、フィルム状接着剤が積層された半導体素子を、支持部材との間にフィルム状接着剤が挟まれるように支持部材の上に載せた状態で、全体を加熱及び加圧することにより、半導体素子が支持部材に接着される。ダイボンディング工程における加熱の条件は、通常、２０〜２５０℃で０．１〜３００秒間である。   The semiconductor device (semiconductor package) shown in FIGS. 6 and 7 includes a die bonding process using the film adhesive according to the present embodiment, a subsequent wire bonding process, a sealing process using a sealing material, and the like. , Can be manufactured by a manufacturing method. In the die bonding step, the semiconductor element laminated with the film adhesive is heated and pressurized in a state where the semiconductor element is placed on the support member so that the film adhesive is sandwiched between the semiconductor element and the support member. Thus, the semiconductor element is bonded to the support member. The heating conditions in the die bonding step are usually 20 to 250 ° C. and 0.1 to 300 seconds.

以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to these.

〔実施例１〜３、比較例１〜６〕
下記材料を用い、表１に示す組成（質量部）で混合し、実施例１〜３及び比較例１〜６の接着剤層形成用ワニスをそれぞれ調製した。[Examples 1 to 3, Comparative Examples 1 to 6]
Using the following materials, the compositions (parts by mass) shown in Table 1 were mixed to prepare adhesive layer forming varnishes of Examples 1 to 3 and Comparative Examples 1 to 6, respectively.

〔材料〕
ＰＵ：ＤＩＣ Ｂａｙｅｒ Ｐｏｌｙｍｅｒ（ディーアイシー バイエル ポリマー）、ポリウレタン樹脂Ｔ−８１７５（Ｔｇ：−２３℃，重量平均分子量：８１０００）
ＺＸ−１３９５：東都化成、ビスフェノールＦ型フェノキシ樹脂（Ｔｇ：６８℃、重量平均分子量：８８０００）〔material〕
PU: DIC Bayer Polymer (DIB Bayer Polymer), polyurethane resin T-8175 (Tg: -23 ° C, weight average molecular weight: 81000)
ZX-1395: Toto Kasei, bisphenol F type phenoxy resin (Tg: 68 ° C., weight average molecular weight: 88000)

ＥＳＣＮ−１９５：住友化学、クレゾールノボラック型エポキシ樹脂（エポキシ当量２００）
ＨＰ−８５０Ｎ：日立化成、フェノールノボラック樹脂（ＯＨ当量：１０６）
ＴＰＰＫ：東京化成、テトラフェニルホスホニウムテトラフェニルボラート
２Ｐ４ＭＨＺ：四国化成株式会社製、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール
ＢＭＩ−１０００：東京化成株式会社製、４，４’−ビスマレイミドジフェニルメタン
パークミルＤ：日本油脂株式会社製、ジクミルパーオキサイド
ＵＧ−４０１０：東亜合成株式会社製、エポキシ基含有無溶剤型液状アクリルポリマー（ＡＲＵＦＯＮ，Ｔｇ：−５７℃，重量平均分子量：２９００）
ＨＰ−Ｐ１：水島合金鉄、窒化ホウ素フィラー
ＮＭＰ：関東化学、Ｎ−メチル−２−ピロリドンESCN-195: Sumitomo Chemical, cresol novolac type epoxy resin (epoxy equivalent 200)
HP-850N: Hitachi Chemical, phenol novolac resin (OH equivalent: 106)
TPPK: Tokyo Kasei, tetraphenylphosphonium tetraphenylborate 2P4MHZ: Shikoku Kasei Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole BMI-1000: Tokyo Kasei Co., Ltd., 4,4'-bismaleimide Diphenylmethane Park Mill D: manufactured by Nippon Oil & Fats Co., Ltd., Dicumyl Peroxide UG-4010: manufactured by Toa Gosei Co., Ltd., epoxy group-containing solvent-free liquid acrylic polymer (ARUFON, Tg: −57 ° C., weight average molecular weight: 2900)
HP-P1: Mizushima alloy iron, boron nitride filler NMP: Kanto Chemical, N-methyl-2-pyrrolidone

ＰＩ−１：下記の方法により製造されたポリイミド樹脂
温度計、攪拌機、冷却管、及び窒素流入管を装着した３００ｍＬフラスコ中に、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（信越化学工業株式会社製、商品名：ＬＰ−７１００）１５．５３ｇ、ポリオキシプロピレンジアミン（ＢＡＳＦ株式会社製、商品名：Ｄ４００、分子量：４５０）２８．１３ｇ、及びＮＭＰ１００．０ｇを仕込んで攪拌して、反応液を調製した。ポリオキシプロピレンジアミンが溶解した後、フラスコを氷浴中で冷却しながら、予め無水酢酸からの再結晶により精製した４，４’−オキシジフタル酸二無水物３２．３０ｇを反応液に少量ずつ添加した。常温（２５℃）で８時間反応させた後、キシレン６７．０ｇを加え、窒素ガスを吹き込みながら１８０℃で加熱することにより、水と共にキシレンを共沸除去した。その反応液を大量の水中に注ぎ、沈澱した樹脂を濾過により採取し、乾燥してポリイミド樹脂（ＰＩ−１）を得た。得られたポリイミド樹脂（ＰＩ−１）の分子量をＧＰＣにて測定したところ、ポリスチレン換算で、数平均分子量Ｍｎ＝２１２００、重量平均分子量Ｍｗ＝４３４００であった。ポリイミド樹脂（ＰＩ−１）のＴｇは４５℃であった。PI-1: Polyimide resin produced by the following method 1,3-bis (3-aminopropyl) tetramethyldisiloxane (Shin-Etsu) in a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet pipe Chemical Industry Co., Ltd., trade name: LP-7100) 15.53 g, polyoxypropylene diamine (BASF Corporation, trade name: D400, molecular weight: 450) 28.13 g, and NMP 100.0 g were charged and stirred. A reaction solution was prepared. After the polyoxypropylenediamine was dissolved, 32.30 g of 4,4′-oxydiphthalic dianhydride purified in advance by recrystallization from acetic anhydride was added to the reaction solution little by little while the flask was cooled in an ice bath. . After reacting at room temperature (25 ° C.) for 8 hours, 67.0 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water. The reaction solution was poured into a large amount of water, and the precipitated resin was collected by filtration and dried to obtain a polyimide resin (PI-1). When the molecular weight of the obtained polyimide resin (PI-1) was measured by GPC, it was number average molecular weight Mn = 21200 and weight average molecular weight Mw = 43400 in terms of polystyrene. Tg of the polyimide resin (PI-1) was 45 ° C.

ＰＩ−２：下記の方法により製造されたポリイミド樹脂
温度計、攪拌機、冷却管、及び窒素流入管を装着した３００ｍＬフラスコ中に、２，２−ビス（４−アミノフェノキシフェニル）プロパン１３．６８ｇ、４，９−ジオキサドデカン−１，１２−ジアミン６．８０ｇ、及びＮＭＰ１６５．８ｇを仕込んで攪拌して、反応液を調製した。４，９−ジオキサドデカン−１，１２−ジアミンが溶解した後、フラスコを氷浴中で冷却しながら、予め無水酢酸からの再結晶により精製したデカメチレンビストリメリテート二無水物３４．８０ｇを反応液に少量ずつ添加した。常温（２５℃）で８時間反応させた後、キシレン１１０．５ｇを加え、窒素ガスを吹き込みながら１８０℃で加熱することにより、水と共にキシレンを共沸除去した。その反応液を大量の水中に注ぎ、沈澱した樹脂を濾過により採取し、乾燥してポリイミド樹脂（ＰＩ−３）を得た。得られたポリイミド樹脂（ＰＩ−２）の分子量をＧＰＣにて測定したところ、ポリスチレン換算で、数平均分子量Ｍｎ＝２８９００、重量平均分子量Ｍｗ＝８８６００であった。ポリイミド樹脂（ＰＩ−２）のＴｇは６７℃であった。PI-2: Polyimide resin produced by the following method In a 300 mL flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet pipe, 13.68 g of 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-Dioxadodecane-1,12-diamine 6.80 g and NMP 165.8 g were charged and stirred to prepare a reaction solution. After 4,9-dioxadodecane-1,12-diamine was dissolved, 34.80 g of decamethylene bistrimellitate dianhydride previously purified by recrystallization from acetic anhydride was cooled while the flask was cooled in an ice bath. To the reaction solution was added little by little. After reacting at room temperature (25 ° C.) for 8 hours, 110.5 g of xylene was added, and heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water. The reaction solution was poured into a large amount of water, and the precipitated resin was collected by filtration and dried to obtain a polyimide resin (PI-3). When the molecular weight of the obtained polyimide resin (PI-2) was measured by GPC, it was number average molecular weight Mn = 28900 and weight average molecular weight Mw = 88600 in terms of polystyrene. The Tg of the polyimide resin (PI-2) was 67 ° C.

実施例１〜３及び比較例１〜６の接着剤組成物の特性評価を以下に記載の方法に従って行った。
〔成膜性の評価〕
接着シートの作製
実施例１〜３及び比較例１〜６の接着剤層形成用ワニスを、乾燥後の膜厚が４０μｍ±５μｍとなるように、それぞれ支持フィルム上に塗布した。支持フィルムとして二軸延伸ポリプロピレン（ＯＰＰ）フィルム（厚さ６０μｍ）を用いた。塗布された接着剤層形成用ワニスをオーブン中にて８０℃で３０分間、続いて、１２０℃で３０分間加熱することにより乾燥して、支持フィルム及び該支持フィルム上に形成されたフィルム状の接着剤層を有する接着シートを得た。The characteristic evaluation of the adhesive composition of Examples 1-3 and Comparative Examples 1-6 was performed according to the method as described below.
[Evaluation of film formability]
Production of Adhesive Sheets The adhesive layer forming varnishes of Examples 1 to 3 and Comparative Examples 1 to 6 were each applied on a support film so that the film thickness after drying was 40 μm ± 5 μm. A biaxially stretched polypropylene (OPP) film (thickness 60 μm) was used as the support film. The applied varnish for forming an adhesive layer is dried by heating in an oven at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes to form a support film and a film-like film formed on the support film. An adhesive sheet having an adhesive layer was obtained.

成膜性の評価
上記条件で得られた接着シートについて、以下の基準により成膜性を評価した。下記基準で成膜性の評価がＡであるとき、薄膜形成性が優れることを意味する。
Ａ：フィルム状の接着剤層が支持基材上でハジキ（ｃｉｓｓｉｎｇ）がなく塗工可能であり、得られた接着シートから支持基材をはく離可能
Ｃ：支持基材上でフィルム状の接着剤層のハジキがある（得られたフィルム面積が７０％以下に縮小）Evaluation of film formability The film formability of the adhesive sheet obtained under the above conditions was evaluated according to the following criteria. When the film forming property evaluation is A based on the following criteria, it means that the thin film forming property is excellent.
A: A film-like adhesive layer can be applied without cissing on a supporting substrate, and the supporting substrate can be peeled off from the obtained adhesive sheet. C: A film-like adhesive on the supporting substrate. There is repelling of the layer (the obtained film area is reduced to 70% or less)

〔低温貼付性の評価〕
接着シートの作製
実施例１〜３及び比較例１〜６の接着剤層形成用ワニスを４０μｍの厚さに、それぞれ基材（剥離剤処理ＰＥＴ）上に塗布し、オーブン中で、８０℃で３０分、続いて１２０℃で３０分加熱し、基材及び該基材上に形成されたフィルム状の接着剤層を有する接着シートを得た。[Evaluation of low temperature adhesiveness]
Production of Adhesive Sheet The varnish for forming an adhesive layer of Examples 1 to 3 and Comparative Examples 1 to 6 was applied to a substrate (peeling agent-treated PET) to a thickness of 40 μm, and in an oven at 80 ° C. It was heated for 30 minutes and then at 120 ° C. for 30 minutes to obtain an adhesive sheet having a base material and a film-like adhesive layer formed on the base material.

低温貼付性の評価
得られた各接着シートから、幅１０ｍｍ、長さ４０ｍｍの試験片を切り出した。この試験片を、支持台上に載せたシリコンウェハ（６インチ径、厚さ４００μｍ）の裏面（支持台と反対側の面）に、接着剤層がシリコンウェハ側になる向きで積層した。積層は、ロール（温度１００℃、線圧４ｋｇｆ／ｃｍ、送り速度０．５ｍ／分）で加圧する方法により行った。Evaluation of low-temperature sticking property A test piece having a width of 10 mm and a length of 40 mm was cut out from each of the obtained adhesive sheets. This test piece was laminated on the back surface (surface opposite to the support table) of the silicon wafer (6 inch diameter, thickness 400 μm) placed on the support table so that the adhesive layer was on the silicon wafer side. Lamination was performed by a method of pressurizing with a roll (temperature 100 ° C., linear pressure 4 kgf / cm, feed rate 0.5 m / min).

このようにして準備したサンプルについて、レオメータ（株式会社東洋精機製作所製、「ストログラフＥ−Ｓ」（商品名））を用いて常温で９０°ピール試験を行って、接着剤層−シリコンウェハ間のピール強度を測定した。測定結果から、以下の基準により低温貼付性を評価した。下記基準でピール強度の評価がＡであるとき、低温貼付性が優れることを意味する。
Ａ：ピール強度が２Ｎ／ｃｍ以上
Ｃ：ピール強度が２Ｎ／ｃｍ未満The sample prepared in this manner is subjected to a 90 ° peel test at room temperature using a rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd., “Strograph ES” (trade name)), and between the adhesive layer and the silicon wafer. The peel strength was measured. From the measurement results, the low temperature sticking property was evaluated according to the following criteria. When the evaluation of peel strength is A based on the following criteria, it means that the low temperature sticking property is excellent.
A: Peel strength is 2 N / cm or more C: Peel strength is less than 2 N / cm

〔フロー量〕
成膜性の評価と同様の方法により得られた、厚さ６０μｍのＯＰＰ基材上に４０μｍ厚にフィルム状の接着剤層を形成させた接着シートを、１０ｍｍ×１０ｍｍサイズに切断して試験片とした。この試験片を、２枚のスライドグラス（松浪硝子工業株式会社製、７６ｍｍ×２６ｍｍ×１．０〜１．２ｍｍ厚）の間に挟み、１２０℃の熱盤上で全体に１００ｋｇｆ／ｃｍ２の荷重を加えながら１５秒間加熱圧着した。加熱圧着後の上記ＯＰＰ基材の四辺からのフィルム状接着剤のはみ出し量をそれぞれ光学顕微鏡で計測し、それらの平均値をフロー量とした。Ｂステージ状態の接着シート及びＣステージ状態の接着シートについて、このフロー量を測定した。なお、Ｂステージとは、接着剤層形成用ワニスをＯＰＰ基材上に塗工後、オーブン中にて８０℃で３０分間、続いて１２０℃で３０分間の条件で加熱した後の状態のことであり、Ｃステージとはオーブン中で更に１８０℃で５時間の条件で加熱硬化した後の状態のことである。また、フィルムの厚さは±５μｍの誤差で調整した。Ｂステージでのフロー量が多く、Ｃステージでのフロー量が少ない程、熱時流動性に優れることを意味する。[Flow amount]
A test piece obtained by cutting a 10 mm × 10 mm size adhesive sheet obtained by forming a film-like adhesive layer to a thickness of 40 μm on an OPP base material having a thickness of 60 μm, obtained by the same method as the evaluation of film formability It was. The test piece was sandwiched between two slide glasses (manufactured by Matsunami Glass Industry Co., Ltd., 76 mm × 26 mm × 1.0-1.2 mm thickness), and 100 kgf / cm 2 overall on a 120 ° C. hot platen. The pressure bonding was performed for 15 seconds while applying a load. The amount of protrusion of the film adhesive from the four sides of the OPP substrate after thermocompression bonding was measured with an optical microscope, and the average value thereof was taken as the flow amount. This flow amount was measured for the adhesive sheet in the B stage state and the adhesive sheet in the C stage state. The B stage refers to the state after the adhesive layer forming varnish is coated on the OPP substrate and then heated in an oven at 80 ° C. for 30 minutes and then at 120 ° C. for 30 minutes. The C stage is a state after being further cured by heating in an oven at 180 ° C. for 5 hours. The film thickness was adjusted with an error of ± 5 μm. The larger the amount of flow in the B stage and the smaller the amount of flow in the C stage, the better the thermal fluidity.

〔ピール強度〕
成膜性の評価と同様の方法により得られた各接着シートの接着剤層（５ｍｍ×５ｍｍ×４０μｍ厚）を、４２アロイリードフレームと、突起部を有するシリコンチップ（５ｍｍ×５ｍｍ×４００μｍ厚）との間に介在させ、その状態で加熱圧着した。加熱温度は実施例１〜３、比較例１、３、５及び６では１５０℃、比較例２及び４では２００℃に設定した。加圧は荷重：１ｋｇｆ／ｃｈｉｐ、時間：５秒間の条件で行った。加熱圧着後、オーブン中で１８０℃で５時間加熱して接着剤層を硬化させて、ピール強度測定用のサンプルとしての積層体を得た。[Peel strength]
The adhesive layer (5 mm × 5 mm × 40 μm thickness) of each adhesive sheet obtained by the same method as the evaluation of film formability was used, and a silicon chip (5 mm × 5 mm × 400 μm thickness) having 42 alloy lead frames and protrusions. Between them and heat-pressed in that state. The heating temperature was set to 150 ° C. in Examples 1 to 3 and Comparative Examples 1, 3, 5 and 6, and 200 ° C. in Comparative Examples 2 and 4. The pressurization was performed under the conditions of load: 1 kgf / chip, time: 5 seconds. After thermocompression bonding, the adhesive layer was cured by heating at 180 ° C. for 5 hours in an oven to obtain a laminate as a sample for peel strength measurement.

図８に示す接着力評価装置を用いて２６０℃ピール強度を測定した。図８に示す接着力評価装置３００は、熱盤３６とプッシュプルゲージ３１とを有する。プッシュプルゲージ３１に取り付けられたロッドの先端に、取手３２が支点３３の周りで角度可変に設けられている。   The 260 ° C. peel strength was measured using the adhesive strength evaluation apparatus shown in FIG. The adhesive force evaluation apparatus 300 shown in FIG. 8 has a hot platen 36 and a push-pull gauge 31. A handle 32 is provided at a tip end of a rod attached to the push-pull gauge 31 so as to have a variable angle around a fulcrum 33.

２６０℃に加熱された熱盤３６上に、シリコンウェハ９と４２アロイリードフレーム３５とが硬化した接着剤層１を介して接着された積層体を、４２アロイリードフレーム３５が熱盤３６側になる向きで載置し、サンプルを２０秒間加熱した。次いで、シリコンウェハ９の突起部に取手３２を引っ掛けた状態で、取手３２を０．５ｍｍ／秒でサンプルの主面に平行な向きで移動させ、そのときのシリコンウェハ９の剥離応力をプッシュプルゲージ３１で測定した。測定された剥離応力を２６０℃ピール強度とした。   A laminated body in which the silicon wafer 9 and the 42 alloy lead frame 35 are bonded to each other via the cured adhesive layer 1 is heated on the heating platen heated to 260 ° C., and the 42 alloy lead frame 35 is placed on the heating platen 36 side. And the sample was heated for 20 seconds. Next, with the handle 32 hooked on the protrusion of the silicon wafer 9, the handle 32 is moved at a rate of 0.5 mm / second in a direction parallel to the main surface of the sample, and the peeling stress of the silicon wafer 9 at that time is push-pull. Measurement was performed with a gauge 31. The measured peel stress was defined as 260 ° C. peel strength.

実施例１〜３及び比較例１〜６の特性評価結果を表１にまとめて示す。

Figure 0005910630
Table 1 summarizes the results of characteristic evaluation of Examples 1 to 3 and Comparative Examples 1 to 6.
Figure 0005910630

表１に示されるように、実施例の接着剤組成物を用いたものは、比較例と比較して、薄膜形成性、低温貼付性、熱時流動性に優れ、２６０℃ピール強度が十分に高いことが明らかである。   As shown in Table 1, those using the adhesive compositions of the examples are excellent in thin film forming properties, low-temperature sticking properties, and hot fluidity as compared with the comparative examples, and have a sufficient 260 ° C. peel strength. Clearly high.

１…接着剤層、２…基材フィルム、３…保護フィルム、５…ダイシングシート、６…粘着剤層、７…基材フィルム、８…ダイボンディング層（硬化した接着剤層）、９，９ａ，９ｂ…半導体素子（シリコンチップ、シリコンウェハ等）、１０…半導体素子搭載用支持部材、１１…ワイヤ、１２…封止材、１３…端子、３１…プッシュプルゲージ、３２…取手、３３…支点、３５…４２アロイリードフレーム、３６…熱盤、１００、１１０、１２０、１３０、１４０…接着シート、２００、２１０…半導体装置、３００…接着力評価装置。   DESCRIPTION OF SYMBOLS 1 ... Adhesive layer, 2 ... Base film, 3 ... Protective film, 5 ... Dicing sheet, 6 ... Adhesive layer, 7 ... Base film, 8 ... Die bonding layer (hardened adhesive layer), 9, 9a , 9b ... Semiconductor element (silicon chip, silicon wafer, etc.), 10 ... Semiconductor element mounting support member, 11 ... Wire, 12 ... Sealing material, 13 ... Terminal, 31 ... Push-pull gauge, 32 ... Handle, 33 ... Support point 35 ... 42 alloy lead frame, 36 ... hot plate, 100, 110, 120, 130, 140 ... adhesive sheet, 200, 210 ... semiconductor device, 300 ... adhesive strength evaluation device.

Claims (11)

下記式（Ｉ）で表されるポリウレタン樹脂と熱硬化性成分とを含み、
Ｂステージでの１２０℃におけるフロー量が５００μｍ以上であり、かつＣステージでの１２０℃におけるフロー量が５００μｍ未満であり、
前記Ｂステージでの１２０℃におけるフロー量を（Ａ）、前記Ｃステージでの１２０℃におけるフロー量を（Ｂ）としたとき、（Ａ）−（Ｂ）の値が１００μｍ以上である接着剤組成物。
Figure 0005910630
［式中、ｎは１〜１００の整数を示し、ｍは１〜１００の整数を示し、＊は結合手を示す。］ A polyurethane resin represented by the following formula (I) and a thermosetting component;
The flow amount at 120 ° C. at the B stage is 500 μm or more, and the flow amount at 120 ° C. at the C stage is less than 500 μm,
The adhesive composition in which the value of (A)-(B) is 100 μm or more, where (A) is the flow amount at 120 ° C. in the B stage and (B) is the flow amount at 120 ° C. in the C stage. object.
Figure 0005910630
[Wherein n represents an integer of 1 to 100, m represents an integer of 1 to 100, and * represents a bond. ] 前記熱硬化性成分がエポキシ樹脂を含む、請求項１に記載の接着剤組成物。   The adhesive composition according to claim 1, wherein the thermosetting component includes an epoxy resin. 前記熱硬化性成分がビスマレイミド樹脂を含む、請求項１に記載の接着剤組成物。   The adhesive composition according to claim 1, wherein the thermosetting component includes a bismaleimide resin. 更にフィラーを含有する、請求項１〜３のいずれか一項に記載の接着剤組成物。   Furthermore, the adhesive composition as described in any one of Claims 1-3 containing a filler. 半導体素子同士、又は半導体素子と半導体素子搭載用支持部材との接着用である、請求項１〜４のいずれか一項に記載の接着剤組成物。   The adhesive composition according to any one of claims 1 to 4, which is for bonding between semiconductor elements or between a semiconductor element and a semiconductor element mounting support member. 前記半導体素子搭載用支持部材が、前記半導体素子を搭載する面に配線段差を有する有機基板である、請求項５に記載の接着剤組成物。   The adhesive composition according to claim 5, wherein the semiconductor element mounting support member is an organic substrate having a wiring step on a surface on which the semiconductor element is mounted. 請求項１〜４のいずれか一項に記載の接着剤組成物をフィルム状に形成してなるフィルム状接着剤。   The film adhesive formed by forming the adhesive composition as described in any one of Claims 1-4 in a film form. 支持基材と、該支持基材の主面上に形成された請求項７に記載のフィルム状接着剤と、を備える接着シート。   An adhesive sheet provided with a support base material and the film adhesive of Claim 7 formed on the main surface of this support base material. 前記支持基材がダイシングシートである、請求項８に記載の接着シート。   The adhesive sheet according to claim 8, wherein the support substrate is a dicing sheet. 前記ダイシングシートが、基材フィルム及び該基材フィルム上に設けられた粘着剤層を有する、請求項９に記載の接着シート。   The adhesive sheet according to claim 9, wherein the dicing sheet has a base film and a pressure-sensitive adhesive layer provided on the base film. 半導体素子と半導体素子搭載用支持部材とが請求項１〜４のいずれか一項に記載の接着剤組成物の硬化物により接続された構造、又は隣接する半導体素子同士が請求項１〜４のいずれか一項に記載の接着剤組成物の硬化物により接続された構造を備える半導体装置。
The structure where the semiconductor element and the supporting member for mounting the semiconductor element are connected by the cured product of the adhesive composition according to any one of claims 1 to 4, or the adjacent semiconductor elements are those of claims 1 to 4. A semiconductor device provided with the structure connected by the hardened | cured material of the adhesive composition as described in any one.
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