TW201940635A - Thermosetting resin composition, film-form adhesive, adhesive sheet, and method for producing semiconductor device - Google Patents

Thermosetting resin composition, film-form adhesive, adhesive sheet, and method for producing semiconductor device Download PDF

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TW201940635A
TW201940635A TW108103139A TW108103139A TW201940635A TW 201940635 A TW201940635 A TW 201940635A TW 108103139 A TW108103139 A TW 108103139A TW 108103139 A TW108103139 A TW 108103139A TW 201940635 A TW201940635 A TW 201940635A
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Taiwan
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film
adhesive
resin composition
thermosetting resin
component
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TW108103139A
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Chinese (zh)
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TWI785196B (en
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舛野大輔
中村祐樹
橋本慎太郎
菊地健太
山崎智陽
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日商日立化成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
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    • C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J7/00—Adhesives in the form of films or foils
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    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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  • Physics & Mathematics (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Wire Bonding (AREA)

Abstract

Disclosed is a thermosetting resin composition comprising: an epoxy resin; a hardening agent; a first elastomer having a weight-average molecular weight of 200,000 to 1,300,000, and having at least one type of functional group selected from the group consisting of a carboxy group and a hydroxy group; and a second elastomer having a weight-average molecular weight of 200,000 to 1,300,000 and having neither a carboxy group or a hydroxy group. The total content of the first elastomer and the second elastomer is less than 40% by mass with respect to the total quantity of the thermosetting resin composition.

Description

熱硬化性樹脂組成物、膜狀接著劑、接著片及半導體裝置的製造方法Thermosetting resin composition, film-shaped adhesive, adhesive sheet, and method for manufacturing semiconductor device

本發明是有關於一種熱硬化性樹脂組成物、膜狀接著劑、接著片及半導體裝置的製造方法。The present invention relates to a method for producing a thermosetting resin composition, a film-like adhesive, an adhesive sheet, and a semiconductor device.

先前，於半導體晶片與用以搭載半導體晶片的支撐構件的接合中，主要使用銀糊。但是，隨著近年來半導體晶片的小型化·積體化，對於所使用的支撐構件亦開始要求小型化、細密化。另一方面，於使用銀糊的情況下，有時會出現起因於糊的露出或半導體晶片的斜度的於打線接合（wire bonding）時產生的不良、膜厚控制困難、產生空隙等問題。Previously, silver paste was mainly used for bonding a semiconductor wafer to a supporting member for mounting the semiconductor wafer. However, in recent years, with the miniaturization and integration of semiconductor wafers, there has also been a demand for miniaturization and miniaturization of the supporting members used. On the other hand, when a silver paste is used, problems such as defects in wire bonding caused by exposure of the paste or the inclination of the semiconductor wafer, difficulty in controlling film thickness, and generation of voids may occur.

因此，近年來一直使用用以接合半導體晶片與支撐構件的膜狀接著劑（例如參照專利文獻1）。於使用包括切割帶（dicing tape）及積層於切割帶上的膜狀接著劑的接著片的情況下，藉由於半導體晶圓的背面貼附膜狀接著劑，並藉由切割來使半導體晶圓單片化，而可獲得帶有膜狀接著劑的半導體晶片。所獲得的帶有膜狀接著劑的半導體晶片可經由膜狀接著劑而貼附於支撐構件，並藉由熱壓接而接合。
[現有技術文獻]
[專利文獻]Therefore, in recent years, a film-shaped adhesive for joining a semiconductor wafer and a support member has been used (for example, refer to Patent Document 1). When a bonding sheet including a dicing tape and a film-shaped adhesive layered on the dicing tape is used, the semiconductor wafer is attached by the film-shaped adhesive on the back surface of the semiconductor wafer, and the semiconductor wafer is diced. By singulating, a semiconductor wafer with a film-like adhesive can be obtained. The obtained semiconductor wafer with a film-shaped adhesive can be attached to a support member via the film-shaped adhesive, and can be bonded by thermocompression bonding.
[Prior Art Literature]
[Patent Literature]

專利文獻1：日本專利特開2007-053240號公報Patent Document 1: Japanese Patent Laid-Open No. 2007-053240

[發明所欲解決之課題]
然而，隨著半導體晶片的尺寸變小，而於加壓時施加至每單位面積的力變大，因而於高溫加壓處理（例如加壓固化等）中，有時會產生膜狀接著劑自半導體晶片露出的被稱為滲出（bleed）的現象。[Problems to be Solved by the Invention]
However, as the size of a semiconductor wafer becomes smaller, the force applied to a unit area during pressing becomes larger. Therefore, in a high-temperature pressure treatment (such as pressure curing), a film-like adhesive may be generated. A phenomenon in which a semiconductor wafer is exposed is called bleed.

另外，於將膜狀接著劑用作作為導線埋入型膜狀接著劑的導線上膜（Film Over Wire，FOW）或作為半導體晶片埋入型膜狀接著劑的晶片上膜（Film Over Die，FOD）的情況下，就提升埋入性的觀點而言，於熱壓接時要求流動性高。因此，有滲出的發生頻率及量進一步增大的傾向。視情況而有時會滲出至半導體晶片上表面，由此而有導致電氣不良或打線接合不良之虞。In addition, a film-over-adhesive film (Film Over Wire, FOW) is used as a wire-embedded film-shaped adhesive, or a wafer-over film (Film Over Die, In the case of FOD), from the viewpoint of improving the embedding property, high fluidity is required at the time of thermocompression bonding. Therefore, the frequency and amount of exudation tend to increase. It may bleed to the upper surface of a semiconductor wafer depending on circumstances, and there exists a possibility of causing electrical failure or a wire bonding failure.

本發明是鑒於此種情況而成，主要目的在於提供一種於熱壓接時具有良好的埋入性，並且能夠抑制高溫加壓處理時的滲出量的增加的熱硬化性樹脂組成物。This invention is made in view of such a situation, The main objective is to provide the thermosetting resin composition which has favorable embedding property at the time of thermocompression bonding, and can suppress the increase of the exudation amount at the time of a high-temperature pressurization process.

[解決課題之手段]
本發明的一方面提供一種熱硬化性樹脂組成物，其含有：環氧樹脂；硬化劑；第一彈性體，重量平均分子量為20萬～130萬，具有選自由羧基及羥基所組成的群組中的至少一種官能基；以及第二彈性體，重量平均分子量為20萬～130萬，不具有羧基及羥基；且以熱硬化性樹脂組成物總量為基準，第一彈性體及第二彈性體的合計含量為40質量%以下。根據此種熱硬化性樹脂組成物，於熱壓接時具有良好的埋入性，並且能夠抑制高溫加壓處理時的滲出量的增加。[Means for solving problems]
One aspect of the present invention provides a thermosetting resin composition comprising: an epoxy resin; a hardener; a first elastomer having a weight average molecular weight of 200,000 to 1.3 million, and having a group selected from the group consisting of a carboxyl group and a hydroxyl group; At least one of the functional groups; and a second elastomer having a weight average molecular weight of 200,000 to 1.3 million, and having no carboxyl group and hydroxyl group; and based on the total amount of the thermosetting resin composition, the first elastomer and the second elastic body The total body content is 40% by mass or less. According to such a thermosetting resin composition, it has a good embedding property at the time of thermocompression bonding, and it is possible to suppress an increase in the amount of bleeding during a high-temperature pressure treatment.

硬化劑可包含酚樹脂。The hardener may include a phenol resin.

第一彈性體可為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。另外，第二彈性體可為不具有羧基及羥基的丙烯酸樹脂。The first elastomer may be an acrylic resin having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group. The second elastomer may be an acrylic resin having no carboxyl group and hydroxyl group.

環氧樹脂可包含25℃下為液體的環氧樹脂。The epoxy resin may include an epoxy resin that is liquid at 25 ° C.

熱硬化性樹脂組成物可更含有無機填料。另外，熱硬化性樹脂組成物可更含有硬化促進劑。The thermosetting resin composition may further contain an inorganic filler. The thermosetting resin composition may further contain a hardening accelerator.

熱硬化性樹脂組成物可於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上，並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中，用來壓接第二半導體元件並且埋入第一導線的至少一部分。The thermosetting resin composition can be used in a semiconductor device in which a first semiconductor element is connected to a substrate by wire bonding via a first wire, and a second semiconductor element is pressure-bonded to the first semiconductor element. The second semiconductor element is crimped and at least a part of the first wire is buried.

進而，本發明可有關於一種含有環氧樹脂、硬化劑、具有選自由羧基及羥基所組成的群組中的至少一種官能基的第一彈性體、以及不具有羧基及羥基的第二彈性體的熱硬化性樹脂組成物的作為接著劑的應用或用來製造接著劑的應用，其中所述熱硬化性樹脂組成物於將第一半導體元件經由第一導線而以打線接合的方式連接於基板上，並且於第一半導體元件上壓接第二半導體元件而成的半導體裝置中，用來壓接第二半導體元件並且埋入第一導線的至少一部分。Furthermore, the present invention may relate to a first elastomer containing an epoxy resin, a hardener, at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, and a second elastomer having no carboxyl group and hydroxyl group. The use of a thermosetting resin composition as an adhesive or an application for manufacturing an adhesive, wherein the thermosetting resin composition is used for connecting a first semiconductor element to a substrate by wire bonding via a first wire; In the semiconductor device formed by crimping the second semiconductor element on the first semiconductor element, the second semiconductor element is crimped and at least a part of the first wire is buried.

另一方面中，本發明提供一種膜狀接著劑，其是將所述熱硬化性樹脂組成物形成為膜狀而成。In another aspect, the present invention provides a film-like adhesive obtained by forming the thermosetting resin composition into a film.

又一方面中，本發明提供一種接著片，其包括基材及設置於基材上的所述膜狀接著劑。In another aspect, the present invention provides an adhesive sheet including a substrate and the film-shaped adhesive provided on the substrate.

基材可為切割帶。再者，本說明書中，有時將基材為切割帶的接著片稱為「切割黏晶一體型接著片」。The substrate may be a dicing tape. In addition, in this specification, the adhesive sheet whose base material is a dicing tape may be called a "cutting sticky crystal integrated type adhesive sheet."

接著片可更包括積層於膜狀接著劑的與基材為相反側的面上的保護膜。The adhesive sheet may further include a protective film laminated on a surface of the film-shaped adhesive on the side opposite to the substrate.

進而又一方面中，本發明提供一種半導體裝置的製造方法，其包括：打線接合步驟，於基板上經由第一導線而電性連接第一半導體元件；層壓步驟，於第二半導體元件的單面貼附所述膜狀接著劑；以及黏晶（die bond）步驟，經由膜狀接著劑而壓接貼附有膜狀接著劑的第二半導體元件，藉此將第一導線的至少一部分埋入膜狀接著劑中。In yet another aspect, the present invention provides a method for manufacturing a semiconductor device, including: a wire bonding step, electrically connecting a first semiconductor element on a substrate via a first wire; a laminating step, Surface-bonding the film-shaped adhesive; and a die bond step, in which at least a portion of the first lead is buried by crimping the second semiconductor element to which the film-shaped adhesive is attached via the film-shaped adhesive. Into film adhesive.

再者，半導體裝置可為藉由將第一半導體晶片經由第一導線而以打線接合的方式連接於半導體基板上，並且於第一半導體晶片上，經由接著膜而壓接第二半導體晶片，從而將第一導線的至少一部分埋入接著膜中而成的導線埋入型的半導體裝置；亦可為將第一導線及第一半導體晶片埋入接著膜中而成的晶片埋入型的半導體裝置。Furthermore, the semiconductor device may be connected to the semiconductor substrate by wire bonding via the first wire through the first semiconductor wafer, and the second semiconductor wafer may be crimped onto the first semiconductor wafer via an adhesive film, thereby A lead-embedded semiconductor device in which at least a portion of the first lead is buried in the adhesive film; or a wafer-embedded semiconductor device in which the first lead and the first semiconductor wafer are embedded in the adhesive film. .

[發明的效果]
根據本發明，可提供一種於熱壓接時具有良好的埋入性，並且能夠抑制高溫加壓處理時的滲出量的增加的熱硬化性樹脂組成物。因此，將該熱硬化性樹脂組成物形成為膜狀而成的膜狀接著劑可有效用作作為半導體晶片埋入型膜狀接著劑的晶片上膜（Film Over Die，FOD）或作為導線埋入型膜狀接著劑的導線上膜（Film Over Wire，FOW）。另外，根據本發明，可提供使用此種膜狀接著劑的接著片及半導體裝置的製造方法。[Effect of the invention]
According to the present invention, it is possible to provide a thermosetting resin composition which has a good embedding property at the time of thermocompression bonding and is capable of suppressing an increase in the amount of bleeding during a high-temperature pressure treatment. Therefore, the film-shaped adhesive formed by forming the thermosetting resin composition into a film shape can be effectively used as a film over die (FOD) as a semiconductor wafer-embedded film-shaped adhesive, or as a conductor buried. Film Over Wire (FOW) of a film-type adhesive. Moreover, according to this invention, the adhesive sheet using such a film adhesive and the manufacturing method of a semiconductor device can be provided.

以下，適當參照圖式來對本發明的實施形態進行說明。但，本發明並不限定於以下的實施形態。Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings. However, the present invention is not limited to the following embodiments.

本說明書中，(甲基)丙烯酸是指丙烯酸或與其對應的甲基丙烯酸。關於(甲基)丙烯醯基等其他的類似表述亦同樣。In this specification, (meth) acrylic acid means acrylic acid or a corresponding methacrylic acid. The same applies to other similar expressions such as (meth) acrylfluorenyl.

[熱硬化性樹脂組成物]
本實施形態的熱硬化性樹脂組成物含有：（A）環氧樹脂、（B）硬化劑、（C）具有選自由羧基及羥基所組成的群組中的至少一種官能基的第一彈性體、以及（D）不具有羧基及羥基的第二彈性體。熱硬化性樹脂組成物經過半硬化（B階段）狀態且於硬化處理後可成完全硬化物（C階段）狀態。[Thermosetting resin composition]
The thermosetting resin composition of this embodiment contains (A) an epoxy resin, (B) a hardener, and (C) a first elastomer having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group. And (D) a second elastomer having no carboxyl group and hydroxyl group. The thermosetting resin composition is in a semi-hardened (B-stage) state and can be completely hardened (C-stage) after hardening.

＜（A）成分：環氧樹脂＞
（A）成分只要為分子內具有環氧基者則可並無特別限制地使用。作為（A）成分，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、含二環戊二烯骨架的環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含茀骨架的環氧樹脂、三苯酚苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、苯基芳烷基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、多官能苯酚類、蒽等多環芳香族類的二縮水甘油醚化合物等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就流動性的觀點而言，（A）成分較佳為150℃熔融黏度為1.0 Pa·s以下者。另外，（A）成分亦可包含環氧樹脂於25℃下為液體的環氧樹脂。＜ (A) component: epoxy resin ＞
The component (A) can be used without particular limitation as long as it has an epoxy group in the molecule. Examples of the component (A) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. Bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, epoxy resin containing dicyclopentadiene skeleton, styrenic epoxy resin, epoxy resin containing triazine skeleton, Epoxy skeleton-containing epoxy resin, triphenolphenol methane epoxy resin, biphenyl epoxy resin, xylyl epoxy resin, phenylaralkyl epoxy resin, biphenylaralkyl epoxy Resins, naphthalene-type epoxy resins, polyfunctional phenols, polycyclic aromatic diglycidyl ether compounds such as anthracene, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of fluidity, the component (A) is preferably one having a melt viscosity at 150 ° C. of 1.0 Pa · s or less. In addition, the component (A) may include an epoxy resin whose epoxy resin is liquid at 25 ° C.

（A）成分的環氧當量並無特別限制，可為90 g/eq～300 g/eq、110 g/eq～290 g/eq、或110 g/eq～290 g/eq。若（A）成分的環氧當量為此種範圍，則有可維持膜狀接著劑的整體強度（bulk intensity）並且確保流動性的傾向。The epoxy equivalent of the component (A) is not particularly limited, and may be 90 g / eq to 300 g / eq, 110 g / eq to 290 g / eq, or 110 g / eq to 290 g / eq. When the epoxy equivalent of a component (A) exists in this range, there exists a tendency for the bulk intensity | strength of a film-form adhesive to be maintained and fluidity to be ensured.

作為（A）成分的市售品，例如可列舉迪愛生（DIC）股份有限公司製造的HP-7200系列、新日鐵住金化學股份有限公司製造的YDCN系列、日本化藥股份有限公司製造的NC-3000、NC-7000系列等。Examples of the commercially available product of the component (A) include the HP-7200 series manufactured by DIC Corporation, the YDCN series manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the NC manufactured by Nippon Kayaku Co., Ltd. -3000, NC-7000 series, etc.

（B）成分並無特別限制，可使用作為環氧樹脂的硬化劑而通常所使用者。作為（B）成分，例如可列舉：酚樹脂、酯化合物、芳香族胺、脂肪族胺、酸酐等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就反應性及經時穩定性的觀點而言，（B）成分可包含酚樹脂。(B) A component is not specifically limited, It can be used normally as a hardener of an epoxy resin. Examples of the component (B) include a phenol resin, an ester compound, an aromatic amine, an aliphatic amine, and an acid anhydride. These may be used alone or in combination of two or more. Among these, from the viewpoint of reactivity and stability with time, the (B) component may include a phenol resin.

酚樹脂只要為分子內具有酚性羥基者則可並無特別限制地使用。作為酚樹脂，例如可列舉：使苯酚、甲酚、間苯二酚（resorcin）、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂、聯苯芳烷基型酚樹脂、苯基芳烷基型酚樹脂等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就耐熱性的觀點而言，酚樹脂較佳為於85℃、85%RH的恆溫恆濕槽中48小時的條件下，吸水率為2質量%以下，且利用熱重量分析儀（thermogravimetric analyzer，TGA）測定出的350℃下的加熱質量減少率（升溫速度：5℃/min，環境：氮）小於5質量%者。The phenol resin is not particularly limited as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenol resin include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or α- Novolac-type phenol resins obtained by the condensation or co-condensation of naphthols such as naphthol, β-naphthol, and dihydroxynaphthalene with formaldehyde compounds such as formaldehyde under acidic catalysts; Allylated bisphenol F, allylated naphthalene glycol, phenol novolac, phenols such as phenol and / or naphthol and dimethoxy-p-xylene or bis (methoxymethyl) biphenyl Synthetic phenol aralkyl resin, naphthol aralkyl resin, biphenylaralkyl phenol resin, phenylaralkyl phenol resin, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, the phenol resin is preferably used in a constant temperature and humidity bath at 85 ° C. and 85% RH for 48 hours, with a water absorption of 2% by mass or less, and a thermogravimetric analyzer is used. (Thermogravimetric analyzer (TGA)) The heating mass reduction rate (heating rate: 5 ° C / min, environment: nitrogen) measured at 350 ° C is less than 5% by mass.

作為酚樹脂的市售品，例如可列舉：芬萊特（Phenolite）KA系列、TD系列（DIC股份有限公司製造）；米萊斯（Mirex）XLC系列、XL系列（三井化學股份有限公司製造）；HE系列（空氣水（AIR WATER）股份有限公司製造）等。Examples of commercially available phenol resins include: Phenolite KA series, TD series (manufactured by DIC Corporation); Mirex XLC series, XL series (manufactured by Mitsui Chemicals Co., Ltd.); HE series (made by AIR WATER), etc.

酚樹脂的羥基當量並無特別限制，可為80 g/eq～250 g/eq、90 g/eq～200 g/eq、或100 g/eq～180 g/eq。若酚樹脂的羥基當量為此種範圍，則有可保持膜狀接著劑的流動性並且更高地維持接著力的傾向。The hydroxyl equivalent of the phenol resin is not particularly limited, and may be 80 g / eq to 250 g / eq, 90 g / eq to 200 g / eq, or 100 g / eq to 180 g / eq. When the hydroxyl equivalent of the phenol resin is in such a range, the fluidity of the film-like adhesive tends to be maintained and the adhesive force tends to be higher.

就硬化性的觀點而言，（A）成分的環氧當量與（B）成分的羥基當量的比（環氧樹脂的環氧當量/酚樹脂的羥基當量）可為0.30/0.70～0.70/0.30、0.35/0.65～0.65/0.35、0.40/0.60～0.60/0.40、或0.45/0.55～0.55/0.45。若該當量比為0.30/0.70以上，則有可獲得更充分的硬化性的傾向。若該當量比為0.70/0.30以下，則可防止黏度變得過高，可獲得更充分的流動性。From the viewpoint of hardenability, the ratio of the epoxy equivalent of the (A) component to the hydroxyl equivalent of the (B) component (epoxy equivalent of the epoxy resin / hydroxy equivalent of the phenol resin) may be 0.30 / 0.70 to 0.70 / 0.30 , 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45. If this equivalent ratio is 0.30 / 0.70 or more, there exists a tendency for sufficient hardenability to be obtained. When the equivalent ratio is 0.70 / 0.30 or less, it is possible to prevent the viscosity from becoming too high and obtain more sufficient fluidity.

以熱硬化性樹脂組成物總量為基準，（A）成分及（B）成分的合計含量可為10質量%～80質量%。（A）成分及（B）成分的合計含量可為20質量%以上、25質量%以上、或30質量%以上，且可為70質量%以下、60質量%以下、或50質量%以下。若以熱硬化性樹脂組成物總量為基準，（A）成分及（B）成分的合計含量為10質量%以上，則有可獲得充分的接著力的傾向。若以熱硬化性樹脂組成物總量為基準，（A）成分及（B）成分的合計含量為80質量%以下，則有可防止黏度變得過低，可進一步抑制滲出量的傾向。Based on the total amount of the thermosetting resin composition, the total content of (A) component and (B) component may be 10% by mass to 80% by mass. The total content of (A) component and (B) component may be 20% by mass or more, 25% by mass or more, or 30% by mass or more, and may be 70% by mass or less, 60% by mass or less, or 50% by mass or less. When the total content of the (A) component and the (B) component is 10% by mass or more based on the total amount of the thermosetting resin composition, a sufficient adhesive force tends to be obtained. When the total content of the (A) component and the (B) component is 80% by mass or less based on the total amount of the thermosetting resin composition, the viscosity may be prevented from becoming too low, and the amount of bleeding may be further suppressed.

＜（C）第一彈性體＞
（C）成分為重量平均分子量為20萬～130萬，且具有選自由羧基及羥基所組成的群組中的至少一種官能基的彈性體。（C）成分可為具有羧基的彈性體。藉由熱硬化性樹脂組成物含有（C）成分，而於熱壓接時進行交聯反應，熱硬化性樹脂組成物增黏，從而能夠抑制高溫加壓處理時的滲出量的增加。（C）成分較佳為構成彈性體的聚合物的玻璃轉移溫度（Tg）為50℃以下者。＜ （C） First Elastomer ＞
The component (C) is an elastomer having a weight average molecular weight of 200,000 to 1.3 million, and having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group. The component (C) may be an elastomer having a carboxyl group. When the thermosetting resin composition contains the component (C), a cross-linking reaction is performed at the time of thermocompression bonding, and the thermosetting resin composition is thickened, thereby suppressing an increase in the amount of bleeding during high-temperature pressure treatment. The component (C) is preferably one having a glass transition temperature (Tg) of the polymer constituting the elastomer of 50 ° C or lower.

（C）成分只要為具有選自由羧基及羥基所組成的群組中的至少一種官能基者則並無特別限制，例如可列舉為丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、矽酮樹脂、丁二烯樹脂、丙烯腈樹脂及該些的改質體等，且具有選自由羧基及羥基所組成的群組中的至少一種官能基者。(C) The component is not particularly limited as long as it has at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, and examples thereof include acrylic resin, polyester resin, polyamide resin, and polyimide. A resin, a silicone resin, a butadiene resin, an acrylonitrile resin, and these modified bodies, and the like, and having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group.

就對溶劑的溶解性、流動性的觀點而言，（C）成分可為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。此處，所謂丙烯酸樹脂，是指包含源自(甲基)丙烯酸酯的結構單元的聚合物。丙烯酸樹脂較佳為包含源自具有醇性或酚性羥基、或者羧基的(甲基)丙烯酸酯的結構單元作為結構單元的聚合物。另外，丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。From the viewpoint of solubility and fluidity of the solvent, the component (C) may be an acrylic resin having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group. Here, the acrylic resin refers to a polymer including a structural unit derived from a (meth) acrylate. The acrylic resin is preferably a polymer containing, as a structural unit, a structural unit derived from a (meth) acrylate having an alcoholic or phenolic hydroxyl group or a carboxyl group. The acrylic resin may be an acrylic rubber such as a copolymer of (meth) acrylate and acrylonitrile.

（C）成分的玻璃轉移溫度（Tg）可為-50℃～50℃或-30℃～30℃。若丙烯酸樹脂的Tg為-50℃以上，則有可防止熱硬化性樹脂組成物的柔軟性變得過高的傾向。藉此，於晶圓切割時容易將膜狀接著劑切斷，能夠防止毛刺的產生。若丙烯酸樹脂的Tg為50℃以下，則有可抑制熱硬化性樹脂組成物的柔軟性下降的傾向。藉此，當將膜狀接著劑貼附於晶圓時，有容易將空隙充分埋入的傾向。另外，能夠防止由晶圓的密接性的下降所導致的切割時的碎化（chipping）。此處，玻璃轉移溫度（Tg）是使用示差掃描熱量計（Differential Scanning Calorimeter，DSC）（例如理學股份有限公司製造的「Thermo Plus 2」）所測定出的值。The glass transition temperature (Tg) of the component (C) may be -50 ° C to 50 ° C or -30 ° C to 30 ° C. When the Tg of the acrylic resin is -50 ° C or higher, the flexibility of the thermosetting resin composition tends to be prevented from becoming too high. This makes it easy to cut the film-like adhesive during wafer dicing, and prevents the occurrence of burrs. When the Tg of the acrylic resin is 50 ° C. or lower, the softness of the thermosetting resin composition tends to be suppressed from decreasing. Thereby, when a film-shaped adhesive is attached to a wafer, it tends to be easy to fully embed a space | gap. In addition, chipping at the time of dicing caused by a decrease in the adhesiveness of the wafer can be prevented. Here, the glass transition temperature (Tg) is a value measured using a differential scanning calorimeter (DSC) (for example, "Thermo Plus 2" manufactured by Rigaku Corporation).

（C）成分的重量平均分子量（Mw）為20萬～130萬。（C）成分的Mw可為30萬以上、40萬以上、或45萬以上，且可為110萬以下、100萬以下、或95萬以下。若丙烯酸樹脂的Mw為此種範圍，則可適當地控制膜形成性、膜狀時的強度、可撓性、黏性等，並且回流性優異，可提升埋入性。此處，Mw是指藉由凝膠滲透層析法（Gel Permeation Chromatography，GPC）進行測定，並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。(C) The weight average molecular weight (Mw) of a component is 200,000-1.3 million. The Mw of the component (C) may be 300,000 or more, 400,000 or more, or 450,000 or more, and may be 1.1 or less, 1 or less, or 950,000 or less. When the Mw of the acrylic resin is within such a range, the film forming properties, strength, flexibility, and tackiness at the time of the film shape can be appropriately controlled, and the reflow properties can be excellent, and the embedding properties can be improved. Here, Mw is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

就硬化性的觀點而言，具有羧基的（C）成分的酸價可為1 mgKOH/g～60 mgKOH/g、3 mgKOH/g～50 mgKOH/g、或5 mgKOH/g～40 mgKOH/g。若酸價為此種範圍，則有可防止清漆中的凝膠化及B階段狀態的流動性的下降的傾向。From the viewpoint of hardenability, the acid value of the component (C) having a carboxyl group may be 1 mgKOH / g to 60 mgKOH / g, 3 mgKOH / g to 50 mgKOH / g, or 5 mgKOH / g to 40 mgKOH / g . When the acid value is within this range, there is a tendency that gelation in the varnish and a decrease in fluidity in the B-stage state tend to be prevented.

就硬化性的觀點而言，具有羥基的（C）成分的羥基價可為1 mgKOH/g～60 mgKOH/g、3 mgKOH/g～50 mgKOH/g、或5 mgKOH/g～40 mgKOH/g。若羥基價為此種範圍，則有可防止清漆中的凝膠化及B階段狀態的流動性的下降的傾向。From the viewpoint of hardenability, the hydroxyl value of the component (C) having a hydroxyl group may be 1 mgKOH / g to 60 mgKOH / g, 3 mgKOH / g to 50 mgKOH / g, or 5 mgKOH / g to 40 mgKOH / g . When the hydroxyl value is within this range, there is a tendency that gelation in the varnish and a decrease in the fluidity in the B-stage state tend to be prevented.

作為（C）成分的市售品，例如可列舉：SG-70L、SG-708-6、WS-023 EK30、SG-280 EK23（均為長瀨化成（Nagase ChemteX）股份有限公司製造）。Examples of the commercially available component (C) include SG-70L, SG-708-6, WS-023 EK30, and SG-280 EK23 (all manufactured by Nagase ChemteX Co., Ltd.).

＜（D）第二彈性體＞
（D）成分為重量平均分子量為20萬～130萬，且不具有羧基及羥基的彈性體。（D）成分可為具有羧基及羥基以外的官能基（例如縮水甘油基等）的彈性體。藉由熱硬化性樹脂組成物含有（D）成分，經時穩定性可變良好。（D）成分較佳為構成彈性體的聚合物的玻璃轉移溫度（Tg）為50℃以下者。＜ （D） Second Elastomer ＞
The component (D) is an elastomer having a weight average molecular weight of 200,000 to 1.3 million and having no carboxyl group and hydroxyl group. The component (D) may be an elastomer having a functional group (for example, a glycidyl group) other than a carboxyl group and a hydroxyl group. When the thermosetting resin composition contains the (D) component, the stability over time can be improved. The component (D) is preferably one having a glass transition temperature (Tg) of a polymer constituting the elastomer of 50 ° C or lower.

（D）成分只要為不具有羧基及羥基者則並無特別限制，例如可列舉為丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、矽酮樹脂、丁二烯樹脂、丙烯腈樹脂及該些的改質體等，且不具有羧基及羥基者。(D) The component is not particularly limited as long as it does not have a carboxyl group and a hydroxyl group, and examples thereof include acrylic resin, polyester resin, polyamide resin, polyimide resin, silicone resin, butadiene resin, and acrylic Nitrile resins and those modified products, etc., which do not have a carboxyl group or a hydroxyl group.

就對溶劑的溶解性、流動性的觀點而言，（D）成分可為不具有羧基及羥基的丙烯酸樹脂。丙烯酸樹脂的含義與上文相同。丙烯酸樹脂較佳為包含具有縮水甘油基等環氧基的官能性單體（(甲基)丙烯酸酯等）的聚合物。另外，丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。From the viewpoint of solubility and fluidity of the solvent, the component (D) may be an acrylic resin having no carboxyl group and hydroxyl group. The meaning of acrylic resin is the same as above. The acrylic resin is preferably a polymer containing a functional monomer (such as (meth) acrylate) having an epoxy group such as a glycidyl group. The acrylic resin may be an acrylic rubber such as a copolymer of (meth) acrylate and acrylonitrile.

（D）成分的玻璃轉移溫度（Tg）可為-50℃～50℃或-30℃～30℃。若丙烯酸樹脂的Tg為-50℃以上，則有可防止熱硬化性樹脂組成物的柔軟性變得過高的傾向。藉此，於晶圓切割時容易將膜狀接著劑切斷，能夠防止毛刺的產生。若丙烯酸樹脂的Tg為50℃以下，則有可抑制熱硬化性樹脂組成物的柔軟性下降的傾向。藉此，當將膜狀接著劑貼附於晶圓時，有容易將空隙充分埋入的傾向。另外，能夠防止由晶圓的密接性的下降所導致的切割時的碎化。此處，玻璃轉移溫度（Tg）是使用DSC（示差掃描熱量計）（例如理學股份有限公司製造的「Thermo Plus 2」）所測定出的值。The glass transition temperature (Tg) of the component (D) may be -50 ° C to 50 ° C or -30 ° C to 30 ° C. When the Tg of the acrylic resin is -50 ° C or higher, the flexibility of the thermosetting resin composition tends to be prevented from becoming too high. This makes it easy to cut the film-like adhesive during wafer dicing, and prevents the occurrence of burrs. When the Tg of the acrylic resin is 50 ° C. or lower, the softness of the thermosetting resin composition tends to be suppressed from decreasing. Thereby, when a film-shaped adhesive is attached to a wafer, it tends to be easy to fully embed a space | gap. In addition, it is possible to prevent chipping at the time of dicing due to a decrease in the adhesiveness of the wafer. Here, the glass transition temperature (Tg) is a value measured using a DSC (differential scanning calorimeter) (for example, "Thermo Plus 2" manufactured by Rigaku Corporation).

（D）成分的重量平均分子量（Mw）為20萬～130萬。（C）成分的Mw可為30萬以上、40萬以上、50萬以上、或60萬以上，且可為120萬以下、110萬以下、100萬以下、95萬以下、或90萬以下。若丙烯酸樹脂的Mw為此種範圍，則可適當地控制膜形成性、膜狀時的強度、可撓性、黏性等，並且回流性優異，可提升埋入性。此處，Mw是指藉由凝膠滲透層析法（GPC）進行測定，並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。The weight average molecular weight (Mw) of the component (D) is 200,000 to 1.3 million. The Mw of the component (C) may be 300,000 or more, 400,000, 500,000 or more, or 600,000 or more, and may be 1.2 million or less, 1.1 million or less, 1 million or less, 950,000 or less, or 900,000 or less. When the Mw of the acrylic resin is within such a range, the film forming properties, strength, flexibility, and tackiness at the time of the film shape can be appropriately controlled, and the reflow properties can be excellent, and the embedding properties can be improved. Here, Mw is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

作為（D）成分的市售品，例如可列舉：SG-P3、SG-80H、HTR-860P-3CSP（均為長瀨化成（Nagase ChemteX）股份有限公司製造）。Examples of commercially available products of the component (D) include SG-P3, SG-80H, and HTR-860P-3CSP (all manufactured by Nagase ChemteX Co., Ltd.).

以熱硬化性樹脂組成物總量為基準，（C）成分及（D）成分的合計含量為40質量%以下。（C）成分及（D）成分的合計含量可為35質量%以下、30質量%以下、或28質量%以下。若以熱硬化性樹脂組成物總量為基準，（C）成分及（D）成分的合計含量為40質量%以下，則有埋入性更優異的傾向。（C）成分及（D）成分的合計含量可為1質量%以上、5質量%以上、10質量%以上、或15質量%以上。Based on the total amount of the thermosetting resin composition, the total content of the components (C) and (D) is 40% by mass or less. The total content of the components (C) and (D) may be 35% by mass or less, 30% by mass or less, or 28% by mass or less. When the total content of the (C) component and (D) component is 40% by mass or less based on the total amount of the thermosetting resin composition, the embedding property tends to be more excellent. The total content of the components (C) and (D) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more.

（C）成分相對於熱硬化性樹脂組成物中的（C）成分及（D）成分的總量而言的質量比（（C）成分的含量/（C）成分及（D）成分的含量的總量）可為0.01～0.50。質量比可為0.02以上、0.03以上、或0.05以上，且可為0.30以下、0.20以下、或0.10以下。若（C）成分相對於（C）成分及（D）成分而言的質量比為0.01以上，則有可進一步抑制高溫加壓處理時的滲出量的增加的傾向。若（C）成分相對於（C）成分及（D）成分而言的質量比為0.50以下，則有可維持更良好的埋入性的傾向。Mass ratio of (C) component with respect to the total amount of (C) component and (D) component in a thermosetting resin composition (content of (C) component / content of (C) component and (D) component (Total amount) may be 0.01 to 0.50. The mass ratio may be 0.02 or more, 0.03 or more, or 0.05 or more, and may be 0.30 or less, 0.20 or less, or 0.10 or less. When the mass ratio of (C) component with respect to (C) component and (D) component is 0.01 or more, there exists a tendency for the increase of the exudation amount at the time of a high-temperature pressure process to be suppressed more. When the mass ratio of (C) component with respect to (C) component and (D) component is 0.50 or less, there exists a tendency for the more favorable embedding property to be maintained.

＜（E）成分：無機填料＞
本實施形態的熱硬化性樹脂組成物可更含有（E）無機填料。作為無機填料，例如可列舉：氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶性二氧化矽、非晶性二氧化矽等。該些可單獨使用一種或者將兩種以上組合使用。就所獲得的膜狀接著劑的導熱性進一步提升的觀點而言，無機填料可包含氧化鋁、氮化鋁、氮化硼、結晶性二氧化矽或非晶性二氧化矽。另外，就調整熱硬化性樹脂組成物的熔融黏度的觀點及對熱硬化性樹脂組成物賦予觸變性的觀點而言，無機填料可包含氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、結晶性二氧化矽或非晶性二氧化矽。＜ (E) component: inorganic filler ＞
The thermosetting resin composition of this embodiment may further contain (E) an inorganic filler. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and nitride. Boron, crystalline silicon dioxide, amorphous silicon dioxide, etc. These may be used alone or in combination of two or more. From the viewpoint of further improving the thermal conductivity of the obtained film-shaped adhesive, the inorganic filler may include alumina, aluminum nitride, boron nitride, crystalline silicon dioxide, or amorphous silicon dioxide. In addition, from the viewpoint of adjusting the melt viscosity of the thermosetting resin composition and the viewpoint of imparting thixotropy to the thermosetting resin composition, the inorganic filler may include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and silicon. Calcium acid, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silicon dioxide or amorphous silicon dioxide.

就接著性進一步提升的觀點而言，（E）成分的平均粒徑可為0.005 μm～0.5 μm或0.05 μm～0.3 μm。此處，平均粒徑是指藉由根據布厄特（Brunauer-Emmett-Teller，BET）比表面積進行換算而求出的值。From the viewpoint of further improvement in adhesion, the average particle diameter of the (E) component may be 0.005 μm to 0.5 μm or 0.05 μm to 0.3 μm. Here, the average particle diameter refers to a value obtained by conversion from a specific surface area of Brunauer-Emmett-Teller (BET).

就其表面與溶劑、其他成分等的相容性、接著強度的觀點而言，（E）成分可藉由表面處理劑進行表面處理。作為表面處理劑，例如可列舉矽烷偶合劑等。作為矽烷偶合劑的官能基，例如可列舉：乙烯基、(甲基)丙烯醯基、環氧基、巰基、胺基、二胺基、烷氧基、乙氧基等。From the viewpoint of compatibility of the surface with a solvent, other components, and the like, and adhesive strength, the (E) component can be surface-treated with a surface-treating agent. Examples of the surface treatment agent include a silane coupling agent and the like. Examples of the functional group of the silane coupling agent include a vinyl group, a (meth) acrylfluorenyl group, an epoxy group, a mercapto group, an amine group, a diamine group, an alkoxy group, and an ethoxy group.

相對於（A）成分、（B）成分、（C）成分及（D）成分的總量100質量份而言，（E）成分的含量可為10質量份～90質量份或10質量份～50質量份。若相對於（A）成分、（B）成分、（C）成分及（D）成分的總量100質量份而言，（E）成分的含量為10質量份以上，則有硬化前的接著層的切割性提升，硬化後的接著層的接著力提升的傾向。若相對於（A）成分、（B）成分、（C）成分及（D）成分的總量100質量份而言，（E）成分的含量為90質量份以下，則可抑制流動性的下降，能夠防止硬化後的膜狀接著劑的彈性係數變得過高。The content of the component (E) may be 10 parts by mass to 90 parts by mass or 10 parts by mass relative to 100 parts by mass of the total amount of the components (A), (B), (C), and (D). 50 parts by mass. When the content of the (E) component is 10 parts by mass or more with respect to 100 parts by mass of the total amount of the components (A), (B), (C), and (D), there is an adhesive layer before curing. The cutting ability is improved, and the adhesive force of the adhesive layer after curing is increased. When the content of the (E) component is 90 parts by mass or less with respect to 100 parts by mass of the total amount of the (A) component, (B) component, (C) component, and (D) component, a decrease in flowability can be suppressed. It is possible to prevent the elastic modulus of the film-like adhesive after curing from becoming too high.

＜（F）成分：硬化促進劑＞
本實施形態的熱硬化性樹脂組成物可更含有（F）硬化促進劑。硬化促進劑並無特別限定，可使用通常所使用者。作為（F）成分，例如可列舉：咪唑類及其衍生物、有機磷系化合物、二級胺類、三級胺類、四級銨鹽等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就反應性的觀點而言，（F）成分可為咪唑類及其衍生物。＜ (F) component: hardening accelerator ＞
The thermosetting resin composition of this embodiment may further contain (F) a hardening accelerator. The hardening accelerator is not particularly limited and can be used by ordinary users. Examples of the component (F) include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among these, from the viewpoint of reactivity, the component (F) may be imidazoles and derivatives thereof.

作為咪唑類，例如可列舉：2-甲基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑等。該些可單獨使用一種或者將兩種以上組合使用。Examples of the imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole Wait. These may be used alone or in combination of two or more.

相對於（A）成分、（B）成分、（C）成分及（D）成分的總量100質量份而言，（F）成分的含量可為0.04質量份～3質量份或0.04質量份～0.2質量份。若（F）成分的含量為此種範圍，則有可兼具硬化性及可靠性的傾向。The content of the component (F) may be 0.04 parts by mass to 3 parts by mass or 0.04 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C), and (D). 0.2 parts by mass. When the content of the (F) component is within such a range, there is a tendency that both the hardenability and the reliability can be achieved.

＜其他成分＞
本實施形態的熱硬化性樹脂組成物可更含有抗氧化劑、矽烷偶合劑、流變控制劑等作為其他成分。相對於（A）成分、（B）成分、（C）成分及（D）成分的總量100質量份而言，該些成分的含量可為0.02質量份～3質量份。＜ Other ingredients ＞
The thermosetting resin composition of this embodiment may further contain an antioxidant, a silane coupling agent, a rheology control agent, and the like as other components. The content of these components may be 0.02 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C), and (D).

本實施形態的接著劑組成物可作為經溶劑稀釋的接著劑清漆來使用。溶劑只要為可溶解（E）成分以外的成分者則並無特別限制。作為溶劑，例如可列舉：甲苯、二甲苯、均三甲苯、異丙苯（cumene）、對異丙基甲苯等芳香族烴；己烷、庚烷等脂肪族烴；甲基環己烷等環狀烷烴；四氫呋喃、1,4-二噁烷等環狀醚；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、4-羥基-4-甲基-2-戊酮等酮；乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯等酯；碳酸伸乙酯、碳酸伸丙酯等碳酸酯；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺等。該些可單獨使用一種或者將兩種以上組合使用。該些中，就溶解性及沸點的觀點而言，溶劑可為甲苯、二甲苯、甲基乙基酮、甲基異丁基酮、或環己烷。The adhesive composition of this embodiment can be used as an adhesive varnish diluted with a solvent. The solvent is not particularly limited as long as it is a component other than the soluble (E) component. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-isopropyl toluene; aliphatic hydrocarbons such as hexane and heptane; and rings such as methylcyclohexane. Alkane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc. Ketones; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone; carbonates such as ethyl carbonate and propyl carbonate; N, N-dimethyl Formamide such as formamidine, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility and boiling point, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexane.

以接著劑清漆的總質量為基準，接著劑清漆中的固體成分濃度可為10質量%～80質量%。Based on the total mass of the adhesive varnish, the solid content concentration in the adhesive varnish may be 10% by mass to 80% by mass.

接著劑清漆可藉由將（A）成分、（B）成分、（C）成分、（D）成分及溶劑、以及視需要的（E）成分、（F）成分及其他成分加以混合、混煉而進行製備。混合及混煉可將通常的攪拌機、擂潰機、三輥磨機（three-rod roll mill）、球磨機（ball mill）、珠磨機（bead mill）等分散機適當組合而進行。於含有（E）成分的情況下，藉由在預先混合（E）成分與低分子量成分後調配高分子量成分，而可縮短進行混合的時間。另外，於製備接著劑清漆後，可藉由真空脫氣等將清漆中的氣泡去除。The adhesive varnish can be mixed and kneaded by mixing (A) component, (B) component, (C) component, (D) component and solvent, and optionally (E) component, (F) component and other components. Instead, preparation is performed. Mixing and kneading can be performed by appropriately combining a dispersing machine such as a general mixer, a masher, a three-rod roll mill, a ball mill, and a bead mill. When the component (E) is contained, by mixing the component (E) and the low-molecular-weight component in advance, the high-molecular-weight component is blended, thereby reducing the mixing time. In addition, after preparing the adhesive varnish, the air bubbles in the varnish can be removed by vacuum degassing or the like.

[膜狀接著劑]
圖1為表示一實施形態的膜狀接著劑的示意剖面圖。膜狀接著劑10為將以上所述的接著劑組成物形成為膜狀而成者。膜狀接著劑10可為半硬化（B階段）狀態。此種膜狀接著劑10可藉由將接著劑組成物塗佈於支撐膜而形成。於使用接著劑清漆的情況下，可將接著劑清漆塗佈於支撐膜，並進行加熱乾燥而將溶劑去除，藉此而形成膜狀接著劑10。[Film adhesive]
FIG. 1 is a schematic cross-sectional view showing a film-shaped adhesive according to an embodiment. The film-like adhesive 10 is obtained by forming the above-mentioned adhesive composition into a film. The film-like adhesive 10 may be in a semi-hardened (B-stage) state. Such a film-like adhesive 10 can be formed by applying an adhesive composition to a support film. When an adhesive varnish is used, the adhesive varnish may be applied to a support film, and the solvent may be removed by heating and drying to form a film-like adhesive 10.

支撐膜並無特別限制，例如可列舉：聚四氟乙烯、聚乙烯、聚丙烯、聚甲基戊烯、聚對苯二甲酸乙二酯、聚醯亞胺等的膜。支撐膜的厚度例如可為60 μm～200 μm或70 μm～170 μm。The supporting film is not particularly limited, and examples thereof include films such as polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, and polyimide. The thickness of the support film may be, for example, 60 μm to 200 μm or 70 μm to 170 μm.

作為將接著劑清漆塗佈於支撐膜的方法，可使用公知的方法，例如可列舉：刮塗法、輥塗法、噴塗法、凹版塗佈法、棒塗法、簾塗法等。加熱乾燥的條件只要為所使用的溶劑充分揮發的條件則無特別限制，例如可為50℃～200℃下0.1分鐘～90分鐘。As a method of applying an adhesive varnish to a support film, a known method can be used, and examples thereof include a blade coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. The conditions for heating and drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 0.1 to 90 minutes at 50 ° C to 200 ° C.

膜狀接著劑的厚度可根據用途而適當調整。就將半導體晶片、導線、基板的配線電路等凹凸等充分埋入的觀點而言，膜狀接著劑的厚度可為20 μm～200 μm、30 μm～200 μm、或40 μm～150 μm。The thickness of the film-shaped adhesive can be appropriately adjusted according to the application. The thickness of the film-shaped adhesive may be 20 μm to 200 μm, 30 μm to 200 μm, or 40 μm to 150 μm from the viewpoint of sufficiently embedding unevenness such as a semiconductor wafer, a lead wire, and a wiring circuit of a substrate.

[接著片]
圖2為表示一實施形態的接著片的示意剖面圖。接著片100包括基材20及設置於基材上的以上所述的膜狀接著劑10。[Next film]
Fig. 2 is a schematic cross-sectional view showing a bonding sheet according to an embodiment. The adhesive sheet 100 includes a substrate 20 and the above-mentioned film-shaped adhesive 10 provided on the substrate.

基材20並無特別限制，可為基材膜。基材膜可為與所述支撐膜相同者。The substrate 20 is not particularly limited, and may be a substrate film. The base film may be the same as the support film.

基材20可為切割帶。此種接著片可用作切割黏晶一體型接著片。該情況下，由於對半導體晶圓的層壓步驟為一次，因此可有效率地作業。The substrate 20 may be a dicing tape. Such a bonding sheet can be used as a cutting-bond-integrated bonding sheet. In this case, since the lamination step of the semiconductor wafer is performed once, it is possible to operate efficiently.

作為切割帶，例如可列舉：聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚醯亞胺膜等塑膠膜等。另外，切割帶視需要可進行底塗塗佈、UV處理、電暈放電處理、研磨處理、蝕刻處理等表面處理。切割帶較佳為具有黏著性者。此種切割帶可為對所述塑膠膜賦予黏著性者，亦可為於所述塑膠膜的單面設置有黏著劑層者。Examples of the dicing tape include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. In addition, the dicing tape may be subjected to surface treatments such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment as necessary. The dicing tape is preferably one having adhesiveness. Such a cutting tape may be one that imparts adhesiveness to the plastic film, or one that is provided with an adhesive layer on one side of the plastic film.

接著片100可與形成以上所述的膜狀接著劑的方法同樣地，藉由將接著劑組成物塗佈於基材膜而形成。將接著劑組成物塗佈於基材20的方法可與將以上所述的接著劑組成物塗佈於支撐膜的方法相同。The adhesive sheet 100 can be formed by applying an adhesive composition to a base film in the same manner as the method for forming the film-like adhesive described above. The method of applying the adhesive composition to the substrate 20 may be the same as the method of applying the adhesive composition described above to the support film.

接著片100可使用預先製作的膜狀接著劑來形成。該情況下，接著片100可藉由使用輥層壓機、真空層壓機等於規定條件（例如室溫（20℃）或加熱狀態）下進行層壓而形成。接著片100可連續地製造，就效率佳而言，較佳為於加熱狀態下使用輥層壓機來形成。The adhesive sheet 100 can be formed using a previously prepared film-like adhesive. In this case, the adhesive sheet 100 can be formed by laminating under a predetermined condition (for example, room temperature (20 ° C.) or a heated state) using a roll laminator or a vacuum laminator. The next sheet 100 can be continuously manufactured, and is preferably formed using a roll laminator in a heated state in terms of good efficiency.

就半導體晶片、導線、基板的配線電路等凹凸等的埋入性的觀點而言，膜狀接著劑10的厚度可為20 μm～200 μm、30 μm～200 μm、或40 μm～150 μm。若膜狀接著劑10的厚度為20 μm以上，則有可獲得更充分的接著力的傾向，若膜狀接著劑10的厚度為200 μm以下，則經濟且能夠響應半導體裝置的小型化的要求。The thickness of the film-like adhesive 10 may be from 20 μm to 200 μm, from 30 μm to 200 μm, or from 40 μm to 150 μm from the viewpoint of embeddedness of unevenness such as semiconductor wafers, leads, and wiring circuits of substrates. When the thickness of the film-shaped adhesive 10 is 20 μm or more, a sufficient adhesive force tends to be obtained. When the thickness of the film-shaped adhesive 10 is 200 μm or less, it is economical and can respond to the request for miniaturization of a semiconductor device. .

圖3為表示另一實施形態的接著片的示意剖面圖。接著片110更包括積層於膜狀接著劑10的與基材20為相反側的面上的保護膜30。保護膜30可為與以上所述的支撐膜相同者。保護膜的厚度例如可為15 μm～200 μm或70 μm～170 μm。Fig. 3 is a schematic cross-sectional view showing a bonding sheet according to another embodiment. The adhesive sheet 110 further includes a protective film 30 laminated on the surface of the film-shaped adhesive 10 on the side opposite to the substrate 20. The protective film 30 may be the same as the support film described above. The thickness of the protective film may be, for example, 15 μm to 200 μm or 70 μm to 170 μm.

[半導體裝置]
圖4為表示一實施形態的半導體裝置的示意剖面圖。半導體裝置200是藉由將第一階段的第一半導體元件Wa經由第一導線88而以打線接合的方式連接於基板14，並且於第一半導體元件Wa上，經由膜狀接著劑10而壓接第二半導體元件Waa，從而將第一導線88的至少一部分埋入膜狀接著劑10中而成的半導體裝置。半導體裝置可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置，亦可為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置。另外，半導體裝置200中，進而經由第二導線98而將基板14與第二半導體元件Waa電性連接，並且藉由密封材42而將第二半導體元件Waa密封。[Semiconductor device]
FIG. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment. The semiconductor device 200 is connected to the substrate 14 by wire bonding the first semiconductor element Wa in the first stage via the first wire 88, and is crimped onto the first semiconductor element Wa via the film-shaped adhesive 10. The second semiconductor element Waa is a semiconductor device in which at least a portion of the first wire 88 is buried in the film-shaped adhesive 10. The semiconductor device may be a lead-embedded semiconductor device in which at least a portion of the first lead 88 is embedded, or a semiconductor device in which the first lead 88 and the first semiconductor element Wa are embedded. In addition, in the semiconductor device 200, the substrate 14 and the second semiconductor element Waa are further electrically connected via a second wire 98, and the second semiconductor element Waa is sealed by a sealing material 42.

第一半導體元件Wa的厚度可為10 μm～170 μm，第二半導體元件Waa的厚度可為20 μm～400 μm。埋入至膜狀接著劑10內部的第一半導體元件Wa為用以驅動半導體裝置200的控制器晶片。The thickness of the first semiconductor element Wa may be 10 μm to 170 μm, and the thickness of the second semiconductor element Waa may be 20 μm to 400 μm. The first semiconductor element Wa embedded in the film-shaped adhesive 10 is a controller wafer for driving the semiconductor device 200.

基板14包括電路圖案84、94分別於表面各形成有兩處的有機基板90。第一半導體元件Wa經由接著劑41而壓接於電路圖案94上。第二半導體元件Waa以覆蓋未壓接有第一半導體元件Wa的電路圖案94、第一半導體元件Wa、及電路圖案84的一部分的方式經由膜狀接著劑10而壓接於基板14。於由基板14上的電路圖案84、94所引起的凹凸的階差中埋入有膜狀接著劑10。並且，利用樹脂製的密封材42而將第二半導體元件Waa、電路圖案84及第二導線98密封。The substrate 14 includes two organic patterns 90 formed on the surface of the circuit patterns 84 and 94, respectively. The first semiconductor element Wa is crimped onto the circuit pattern 94 via an adhesive 41. The second semiconductor element Waa is crimped to the substrate 14 via a film-like adhesive 10 so as to cover a part of the circuit pattern 94, the first semiconductor element Wa, and the circuit pattern 84 of the first semiconductor element Wa, which is not crimped. A film-like adhesive 10 is embedded in a step of unevenness caused by the circuit patterns 84 and 94 on the substrate 14. The second semiconductor element Waa, the circuit pattern 84, and the second lead 98 are sealed with a resin sealing material 42.

[半導體裝置的製造方法]
本實施形態的半導體裝置的製造方法包括：於基板上經由第一導線而電性連接第一半導體元件的第一打線接合步驟；於第二半導體元件的單面貼附以上所述的膜狀接著劑的層壓步驟；以及經由膜狀接著劑來壓接貼附有膜狀接著劑的第二半導體元件，藉此將第一導線的至少一部分埋入膜狀接著劑中的黏晶步驟。[Manufacturing method of semiconductor device]
The method for manufacturing a semiconductor device according to this embodiment includes a first wire bonding step of electrically connecting a first semiconductor element to a substrate via a first wire; and attaching the above-mentioned film-like adhesive to one side of the second semiconductor element. A laminating step of the adhesive; and a die bonding step in which at least a part of the first lead is buried in the film-shaped adhesive by crimping the second semiconductor element to which the film-shaped adhesive is attached via the film-shaped adhesive.

圖5～圖9為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。本實施形態的半導體裝置200為將第一導線88及第一半導體元件Wa埋入而成的半導體裝置，可藉由以下程序而製造。首先，如圖5所示，於基板14上的電路圖案94上壓接具有接著劑41的第一半導體元件Wa，且經由第一導線88而將基板14上的電路圖案84與第一半導體元件Wa電性接合連接（第一打線接合步驟）。5 to 9 are schematic cross-sectional views showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment. The semiconductor device 200 of this embodiment is a semiconductor device in which a first lead wire 88 and a first semiconductor element Wa are embedded, and can be manufactured by the following procedure. First, as shown in FIG. 5, a first semiconductor element Wa having an adhesive 41 is crimped onto a circuit pattern 94 on the substrate 14, and the circuit pattern 84 on the substrate 14 and the first semiconductor element are bonded via a first wire 88. Wa electrical bonding connection (first wire bonding step).

其次，於半導體晶圓（例如厚度為100 μm、尺寸為8吋）的單面上層壓接著片100，並剝去基材20，藉此而於半導體晶圓的單面貼附膜狀接著劑10（例如厚度為110 μm）。並且，於將切割帶貼合於膜狀接著劑10後，切割為規定的大小（例如7.5 mm見方），藉此而如圖6所示，獲得貼附有膜狀接著劑10的第二半導體元件Waa（層壓步驟）。Next, the adhesive sheet 100 is laminated on one side of a semiconductor wafer (for example, a thickness of 100 μm and a size of 8 inches), and the substrate 20 is peeled off, thereby attaching a film-shaped adhesive on one side of the semiconductor wafer. 10 (for example, 110 μm thick). Then, after the dicing tape is bonded to the film-shaped adhesive 10, it is cut to a predetermined size (for example, 7.5 mm square), thereby obtaining a second semiconductor to which the film-shaped adhesive 10 is attached as shown in FIG. 6. Element Waa (lamination step).

層壓步驟的溫度條件可為50℃～100℃或60℃～80℃。若層壓步驟的溫度為50℃以上，則可獲得與半導體晶圓的良好的密接性。若層壓步驟的溫度為100℃以下，則可抑制膜狀接著劑10於層壓步驟中過度流動，因而可防止引起厚度的變化等。The temperature conditions of the lamination step may be 50 ° C to 100 ° C or 60 ° C to 80 ° C. When the temperature of the lamination step is 50 ° C. or higher, good adhesion to the semiconductor wafer can be obtained. When the temperature in the laminating step is 100 ° C. or lower, excessive flow of the film-like adhesive 10 in the laminating step can be suppressed, and a change in thickness or the like can be prevented.

作為切割方法，例如可列舉：使用旋轉刀刃的刀片切割、藉由雷射而將膜狀接著劑或晶圓與膜狀接著劑的兩者切斷的方法等。Examples of the dicing method include a dicing using a rotary blade, a method of cutting both a film-shaped adhesive or a wafer and a film-shaped adhesive by laser, and the like.

並且，將貼附有膜狀接著劑10的第二半導體元件Waa壓接於經由第一導線88而接合連接有第一半導體元件Wa的基板14。具體而言，如圖7所示，以藉由膜狀接著劑10來覆蓋第一導線88及第一半導體元件Wa的方式載置貼附有膜狀接著劑10的第二半導體元件Waa，繼而，如圖8所示，藉由使第二半導體元件Waa壓接於基板14而將第二半導體元件Waa固定於基板14（黏晶步驟）。黏晶步驟較佳為將膜狀接著劑10於80℃～180℃、0.01 MPa～0.50 MPa的條件下壓接0.5秒～3.0秒。於黏晶步驟之後，將膜狀接著劑10於60℃～175℃、0.3 MPa～0.7 MPa的條件下加壓及加熱5分鐘以上。Then, the second semiconductor element Waa to which the film-shaped adhesive 10 is attached is pressure-bonded to the substrate 14 to which the first semiconductor element Wa is bonded and connected via the first wire 88. Specifically, as shown in FIG. 7, the second semiconductor element Waa to which the film-shaped adhesive 10 is attached is placed so that the first lead 88 and the first semiconductor element Wa are covered with the film-shaped adhesive 10, and then As shown in FIG. 8, the second semiconductor element Waa is fixed to the substrate 14 by crimping the second semiconductor element Waa to the substrate 14 (the die bonding step). The die-bonding step is preferably performed by pressure-bonding the film-shaped adhesive 10 at 80 ° C. to 180 ° C. and 0.01 MPa to 0.50 MPa for 0.5 seconds to 3.0 seconds. After the sticking step, the film-like adhesive 10 is pressurized and heated under conditions of 60 ° C. to 175 ° C. and 0.3 MPa to 0.7 MPa for more than 5 minutes.

繼而，如圖9所示，於將基板14與第二半導體元件Waa經由第二導線98而電性連接後（第二打線接合步驟），利用密封材42將電路圖案84、第二導線98及第二半導體元件Waa密封。藉由經過此種步驟而可製造半導體裝置200。Then, as shown in FIG. 9, after the substrate 14 and the second semiconductor element Waa are electrically connected via the second wire 98 (second wire bonding step), the circuit pattern 84, the second wire 98, and The second semiconductor element Waa is sealed. The semiconductor device 200 can be manufactured by going through such steps.

作為其他實施形態，半導體裝置亦可為將第一導線88的至少一部分埋入而成的導線埋入型的半導體裝置。
[實施例]As another embodiment, the semiconductor device may be a lead-embedded semiconductor device in which at least a portion of the first lead 88 is embedded.
[Example]

以下，列舉實施例來對本發明進行更具體的說明。但本發明並不限定於該些實施例。Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

（實施例1～實施例7及比較例1～比較例3）
＜接著劑片的製作＞
將以下所示的各成分以表1所示的調配比例（質量份）混合，並使用環己酮作為溶媒來製備固體成分為40質量%的熱硬化性樹脂組成物的清漆。其次，利用100目的過濾器對所獲得的清漆進行過濾，並進行真空脫泡。將真空脫泡後的清漆塗佈於作為基材膜的厚度38 μm的已實施脫模處理的聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）膜上。以90℃下5分鐘、繼而140℃下5分鐘的兩階段對所塗佈的清漆進行加熱乾燥。如此而獲得於基材膜上具有處於半硬化（B階段）狀態的厚度110 μm的膜狀接著劑的接著片。(Examples 1 to 7 and Comparative Examples 1 to 3)
＜ Production of adhesive sheet ＞
Each component shown below was mixed in the formulation ratio (mass part) shown in Table 1, and the varnish of the thermosetting resin composition with a solid content of 40 mass% was prepared using cyclohexanone as a solvent. Next, the obtained varnish was filtered with a 100-mesh filter and vacuum-defoamed. The vacuum-defoamed varnish was applied to a polyethylene terephthalate (PET) film having a thickness of 38 μm, which had been subjected to a release treatment, as a base film. The applied varnish was heat-dried in two stages of 5 minutes at 90 ° C and 5 minutes at 140 ° C. In this way, an adhesive sheet having a film-like adhesive having a thickness of 110 μm in a semi-hardened (B-stage) state on a substrate film was obtained.

再者，表1中的各成分如下所述。In addition, each component in Table 1 is as follows.

（A）環氧樹脂
A-1：含二環戊二烯骨架的環氧樹脂，DIC股份有限公司製造，商品名：HP-7200L，環氧當量：242 g/eq～252 g/eq
A-2：甲酚酚醛清漆型環氧樹脂，新日鐵住金化學股份有限公司製造，商品名：YDCN-700-10，環氧當量：209 g/eq
A-3：雙酚F型環氧樹脂（25℃下為液體），DIC股份有限公司製造，商品名：EXA-830CRP，環氧當量：159 g/eq
（B）硬化劑
B-1：聯苯芳烷基型酚樹脂，空氣水股份有限公司製造，商品名：HE-200C-10，羥基當量：205 g/eq
B-2：苯基芳烷基型酚樹脂，空氣水股份有限公司製造，商品名：HE100C-30，羥基當量：175 g/eq
（C）第一彈性體（具有選自由羧基及羥基所組成的群組中的至少一種官能基的彈性體）
C-1：丙烯酸橡膠，長瀨化成股份有限公司製造，商品名：WS-023 EK30，重量平均分子量：50萬，酸價：20 mgKOH/g，Tg：-10℃
C-2：丙烯酸橡膠，長瀨化成股份有限公司製造，商品名：SG-708-6，重量平均分子量：70萬，酸價：9 mgKOH/g，Tg：4℃
C-3：丙烯酸橡膠，長瀨化成股份有限公司製造，商品名：SG-280 EK23，重量平均分子量：90萬，酸價：30 mgKOH/g，Tg：-29℃
（D）第二彈性體（不具有羧基及羥基的彈性體）
D-1：丙烯酸橡膠，長瀨化成股份有限公司製造，商品名：HTR-860P-3CSP，重量平均分子量：80萬，含縮水甘油基的單體比率：3%，Tg：-7℃
D-2：丙烯酸橡膠，長瀨化成股份有限公司製造，商品名：HTR-860P-30B-CHN，重量平均分子量：23萬，含縮水甘油基的單體比率：8%，Tg：-7℃
D-3：丙烯酸橡膠，長瀨化成股份有限公司製造，HTR-860P-3CSP改良品（商品名：HTR-860P-3CSP，長瀨化成股份有限公司製造的丙烯酸橡膠中，除去源自丙烯腈的結構單元者），重量平均分子量：60萬，Tg：12℃
（E）無機填料
E-1：二氧化矽填料分散液，熔融二氧化矽，雅都瑪（Admatechs）股份有限公司製造，商品名：SC2050-HLG，平均粒徑：0.50 μm
（F）硬化促進劑
F-1：1-氰基乙基-2-苯基咪唑，四國化成工業股份有限公司製造，商品名：固唑（Curezol）2PZ-CN(A) Epoxy resin
A-1: Dicyclopentadiene skeleton-containing epoxy resin, manufactured by DIC Corporation, trade name: HP-7200L, epoxy equivalent: 242 g / eq to 252 g / eq
A-2: Cresol novolac epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name: YDCN-700-10, epoxy equivalent: 209 g / eq
A-3: Bisphenol F-type epoxy resin (liquid at 25 ° C), manufactured by DIC Corporation, trade name: EXA-830CRP, epoxy equivalent: 159 g / eq
(B) Hardener
B-1: Biphenylaralkyl phenol resin, manufactured by Air Water Co., Ltd., trade name: HE-200C-10, hydroxyl equivalent: 205 g / eq
B-2: Phenylaralkyl-type phenol resin, manufactured by Air Water Co., Ltd., trade name: HE100C-30, hydroxyl equivalent: 175 g / eq
(C) The first elastomer (an elastomer having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group)
C-1: Acrylic rubber, manufactured by Nagase Chemical Co., Ltd., trade name: WS-023 EK30, weight average molecular weight: 500,000, acid value: 20 mgKOH / g, Tg: -10 ° C
C-2: Acrylic rubber, manufactured by Nagase Chemical Co., Ltd., trade name: SG-708-6, weight average molecular weight: 700,000, acid value: 9 mgKOH / g, Tg: 4 ° C
C-3: Acrylic rubber, manufactured by Nagase Chemical Co., Ltd., trade name: SG-280 EK23, weight average molecular weight: 900,000, acid value: 30 mgKOH / g, Tg: -29 ° C
(D) The second elastomer (an elastomer having no carboxyl group and hydroxyl group)
D-1: Acrylic rubber, manufactured by Nagase Kasei Co., Ltd., trade name: HTR-860P-3CSP, weight average molecular weight: 800,000, glycidyl group-containing monomer ratio: 3%, Tg: -7 ° C
D-2: Acrylic rubber, manufactured by Nagase Chemical Co., Ltd., trade name: HTR-860P-30B-CHN, weight average molecular weight: 230,000, glycidyl group-containing monomer ratio: 8%, Tg: -7 ° C
D-3: Acrylic rubber, manufactured by Nagase Kasei Co., Ltd., an improved product of HTR-860P-3CSP (brand name: HTR-860P-3CSP, Nagase Kasei Co., Ltd., acrylic acid rubber is removed from acrylic rubber Structural unit), weight average molecular weight: 600,000, Tg: 12 ° C
(E) Inorganic filler
E-1: Silicon dioxide filler dispersion, fused silica, manufactured by Admatechs Co., Ltd., trade name: SC2050-HLG, average particle size: 0.50 μm
(F) Hardening accelerator
F-1: 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Curezol 2PZ-CN

＜各種物性的評價＞
對所獲得的實施例1～實施例7及比較例1～比較例3的接著片進行埋入性及滲出量的評價。＜ Evaluation of various physical properties ＞
The obtained adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated for embedding property and exudation amount.

[埋入性評價]
製作以下評價樣品來對接著片的埋入性進行評價。對於以上所獲得的膜狀接著劑（厚度110 μm），剝去基材膜並貼附於切割帶，獲得切割黏晶一體型接著片。其次，將厚度100 μm的半導體晶圓（8吋）加熱至70℃而貼附於接著劑側。其後，將該半導體晶圓切割為7.5 mm見方，藉此而獲得半導體晶片A。其次，準備切割黏晶一體型接著片（日立化成股份有限公司，商品名：HR9004-10）（厚度10 μm），加熱至70℃而貼附於厚度50 μm的半導體晶圓（8吋）。其後，將該半導體晶圓切割為4.5 mm見方，藉此而獲得帶有黏晶膜的半導體晶片B。繼而，準備塗佈有阻焊劑（太陽日酸股份有限公司，商品名：AUS308）的總厚度為260 μm的評價用基板，以帶有黏晶膜的半導體晶片B的黏晶膜與評價用基板的阻焊劑接觸的方式，於120℃、0.20 MPa、2秒的條件下進行壓接。其後，以半導體晶片A的膜狀接著劑與半導體晶片B的半導體晶圓接觸的方式，於120℃、0.20 MPa、1.5秒的條件下進行壓接，獲得評價樣品。此時，以先前所壓接的半導體晶片B處於半導體晶片A的中央的方式進行位置對準。對以所述方式獲得的評價樣品，利用超音波數位圖像診斷裝置（因賽特（Insight）股份有限公司製造，探針：75 MHz）來觀測空隙的觀測的有無，於觀測到空隙的情況下算出每單位面積的空隙的面積的比例，並將該些分析結果作為埋入性進行評價。評價基準如下所述。將結果示於表1中。
A：未觀察到空隙。
B：雖觀測到空隙，但其比例小於5面積%。
C：觀察到空隙，且其比例為5面積%以上。[Embedded evaluation]
The following evaluation samples were prepared to evaluate the embedding property of the adhesive sheet. With respect to the film-shaped adhesive (thickness: 110 μm) obtained above, the substrate film was peeled off and attached to a dicing tape to obtain a cut-and-stick crystal-integrated adhesive sheet. Next, a semiconductor wafer (8 inches) with a thickness of 100 μm was heated to 70 ° C. and attached to the adhesive side. Thereafter, the semiconductor wafer was cut into 7.5 mm squares, thereby obtaining a semiconductor wafer A. Next, a die-bonding integrated wafer (Hitachi Kasei Co., Ltd., trade name: HR9004-10) (thickness 10 μm) was prepared, and it was heated to 70 ° C. and attached to a semiconductor wafer (8 inches) with a thickness of 50 μm. Thereafter, the semiconductor wafer was cut into a 4.5 mm square, thereby obtaining a semiconductor wafer B with a die attach film. Next, an evaluation substrate having a total thickness of 260 μm coated with a solder resist (Sun Solar Acid Co., Ltd., trade name: AUS308) was prepared, and a die-bond film of the semiconductor wafer B with a die-bond film and a substrate for evaluation were prepared. The method of contacting the solder resist is crimping at 120 ° C, 0.20 MPa, and 2 seconds. Thereafter, the film-shaped adhesive of the semiconductor wafer A was brought into contact with the semiconductor wafer of the semiconductor wafer B, and pressure-bonded under conditions of 120 ° C., 0.20 MPa, and 1.5 seconds to obtain an evaluation sample. At this time, the alignment is performed so that the previously pressed semiconductor wafer B is located at the center of the semiconductor wafer A. For the evaluation samples obtained in the above-mentioned manner, the presence or absence of void observation was observed using an ultrasonic digital image diagnostic apparatus (produced by Insight Co., Ltd., probe: 75 MHz). The ratio of the area of the voids per unit area was calculated below, and these analysis results were evaluated as embedding properties. The evaluation criteria are as follows. The results are shown in Table 1.
A: No void was observed.
B: Although voids are observed, the proportion is less than 5 area%.
C: A void is observed, and its ratio is 5 area% or more.

[滲出量評價]
僅對所述埋入性評價中評價為「A」或「B」者進行滲出量評價。藉由與所述埋入性評價中所製作的評價樣品相同的程序來製作評價樣品。將半導體晶片A的膜狀接著劑與半導體晶片B的半導體晶圓，於120℃、0.20 MPa、1.5秒的條件下壓接。繼而，使用加壓烘箱，於140℃、0.7 MPa、30分鐘的條件下進行高溫加壓處理（加壓固化），於加壓固化前後，利用顯微鏡來觀察評價樣品，自評價樣品的四邊的中心，分別測定膜狀接著劑的滲出量（露出量）。將加壓固化前的滲出量設為L1，將加壓固化後的滲出量設為L2，並基於下式來算出滲出量增加率。將結果示於表1中。

滲出量增加率（%）=（L2-L1）/L1×100[Exudation Evaluation]
Exudation amount evaluation was performed only for those evaluated as "A" or "B" in the embedded evaluation. An evaluation sample was prepared by the same procedure as the evaluation sample prepared in the embedment evaluation. The film-like adhesive of the semiconductor wafer A and the semiconductor wafer of the semiconductor wafer B were pressure-bonded under conditions of 120 ° C., 0.20 MPa, and 1.5 seconds. Next, a pressure oven was used to perform a high-temperature pressure treatment (pressure curing) under the conditions of 140 ° C, 0.7 MPa, and 30 minutes. Before and after the pressure curing, the evaluation samples were observed with a microscope, and the centers of the four sides of the evaluation samples were measured. The amount of exudation (exposure) of the film-shaped adhesive was measured. The exudation amount before the pressure curing was set to L1, the exudation amount after the pressure curing was set to L2, and the increase rate of the exudation amount was calculated based on the following formula. The results are shown in Table 1.

Increase rate of exudation (%) = (L2-L1) / L1 × 100

[表1]

[Table 1]

如表1所示，與僅含有第一彈性體或第二彈性體的任一者的比較例1～比較例3相比，含有第一彈性體及第二彈性體的實施例1～實施例7的埋入性優異，高溫加壓處理時的滲出量增加率亦低。根據該些結果而確認到：本發明的熱硬化性樹脂組成物於熱壓接時具有良好的埋入性，並且能夠抑制高溫加壓處理時的滲出量的增加。
[產業上之可利用性]As shown in Table 1, compared with Comparative Examples 1 to 3 containing only either the first elastic body or the second elastic body, Examples 1 to 2 containing the first elastic body and the second elastic body were compared. 7 is excellent in embedding property, and the increase rate of exudation amount during high-temperature pressure treatment is also low. From these results, it was confirmed that the thermosetting resin composition of the present invention has good embedding properties during thermocompression bonding, and can suppress an increase in the amount of bleeding during high-temperature pressure treatment.
[Industrial availability]

如以上結果所示，本發明的熱硬化性樹脂組成物於熱壓接時具有良好的埋入性，並且可抑制高溫加壓處理時的滲出量的增加，因此將熱硬化性樹脂組成物形成為膜狀而成的膜狀接著劑可有效用作作為晶片埋入型膜狀接著劑的晶片上膜（Film Over Die，FOD）或作為導線埋入型膜狀接著劑的導線上膜（Film Over Wire，FOW）。As shown in the above results, the thermosetting resin composition of the present invention has good embedding properties during thermocompression bonding, and can suppress an increase in the amount of bleeding during high-temperature pressure treatment. Therefore, the thermosetting resin composition is formed. The film-like adhesive formed into a film can be effectively used as a film over die (FOD) as a wafer-embedded film adhesive or a wire-on film (Film) as a wire-embedded film adhesive. Over Wire, FOW).

10‧‧‧膜狀接著劑10‧‧‧ film adhesive

14‧‧‧基板 14‧‧‧ substrate

20‧‧‧基材 20‧‧‧ substrate

30‧‧‧保護膜 30‧‧‧ protective film

41‧‧‧接著劑 41‧‧‧ Adhesive

42‧‧‧密封材 42‧‧‧sealing material

84、94‧‧‧電路圖案 84, 94‧‧‧ circuit pattern

88‧‧‧第一導線 88‧‧‧first lead

90‧‧‧有機基板 90‧‧‧ organic substrate

98‧‧‧第二導線 98‧‧‧Second Lead

100、110‧‧‧接著片 100, 110‧‧‧ followed

200‧‧‧半導體裝置 200‧‧‧ semiconductor device

Wa‧‧‧第一半導體元件 Wa‧‧‧First Semiconductor Element

Waa‧‧‧第二半導體元件 Waa‧‧‧Second Semiconductor Element

圖1為表示一實施形態的膜狀接著劑的示意剖面圖。FIG. 1 is a schematic cross-sectional view showing a film-shaped adhesive according to an embodiment.

圖2為表示一實施形態的接著片的示意剖面圖。 Fig. 2 is a schematic cross-sectional view showing a bonding sheet according to an embodiment.

圖3為表示另一實施形態的接著片的示意剖面圖。 Fig. 3 is a schematic cross-sectional view showing a bonding sheet according to another embodiment.

圖4為表示一實施形態的半導體裝置的示意剖面圖。 FIG. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment.

圖5為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 5 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

圖6為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 FIG. 6 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

圖7為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 7 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

圖8為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 8 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

圖9為表示一實施形態的半導體裝置的製造方法的一系列步驟的示意剖面圖。 9 is a schematic cross-sectional view showing a series of steps in a method of manufacturing a semiconductor device according to an embodiment.

Claims (12)

一種熱硬化性樹脂組成物，其含有： 環氧樹脂； 硬化劑； 第一彈性體，重量平均分子量為20萬～130萬，具有選自由羧基及羥基所組成的群組中的至少一種官能基；以及 第二彈性體，重量平均分子量為20萬～130萬，不具有羧基及羥基；且 以熱硬化性樹脂組成物總量為基準，所述第一彈性體及所述第二彈性體的合計含量為40質量%以下。A thermosetting resin composition containing: Epoxy resin hardener; A first elastomer having a weight average molecular weight of 200,000 to 1.3 million and having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group; and The second elastomer has a weight average molecular weight of 200,000 to 1.3 million, and does not have a carboxyl group and a hydroxyl group; and Based on the total amount of the thermosetting resin composition, the total content of the first elastomer and the second elastomer is 40% by mass or less. 如申請專利範圍第1項所述的熱硬化性樹脂組成物，其中所述硬化劑包含酚樹脂。The thermosetting resin composition according to item 1 of the scope of patent application, wherein the hardener comprises a phenol resin. 如申請專利範圍第1項或第2項所述的熱硬化性樹脂組成物，其中所述第一彈性體為具有選自由羧基及羥基所組成的群組中的至少一種官能基的丙烯酸樹脂。The thermosetting resin composition according to claim 1 or claim 2, wherein the first elastomer is an acrylic resin having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group. 如申請專利範圍第1項至第3項中任一項所述的熱硬化性樹脂組成物，其中所述第二彈性體為不具有羧基及羥基的丙烯酸樹脂。The thermosetting resin composition according to any one of claims 1 to 3, wherein the second elastomer is an acrylic resin having no carboxyl group and hydroxyl group. 如申請專利範圍第1項至第4項中任一項所述的熱硬化性樹脂組成物，其中所述環氧樹脂包含25℃下為液體的環氧樹脂。The thermosetting resin composition according to any one of claims 1 to 4, wherein the epoxy resin includes an epoxy resin that is liquid at 25 ° C. 如申請專利範圍第1項至第5項中任一項所述的熱硬化性樹脂組成物，其更含有無機填料。The thermosetting resin composition according to any one of claims 1 to 5 of the scope of patent application, which further contains an inorganic filler. 如申請專利範圍第1項至第6項中任一項所述的熱硬化性樹脂組成物，其更含有硬化促進劑。The thermosetting resin composition according to any one of claims 1 to 6 of the scope of patent application, further comprising a hardening accelerator. 一種膜狀接著劑，其是將如申請專利範圍第1項至第7項中任一項所述的熱硬化性樹脂組成物形成為膜狀而成。A film-shaped adhesive formed by forming the thermosetting resin composition according to any one of claims 1 to 7 in a patent application into a film. 一種接著片，其包括： 基材；以及 設置於所述基材上的如申請專利範圍第8項所述的膜狀接著劑。An adhesive film comprising: Substrate; and The film-shaped adhesive as described in item 8 of the scope of patent application, which is provided on the substrate. 如申請專利範圍第9項所述的接著片，其中所述基材為切割帶。The adhesive sheet according to item 9 of the patent application scope, wherein the substrate is a dicing tape. 如申請專利範圍第9項或第10項所述的接著片，其更包括積層於所述膜狀接著劑的與所述基材為相反側的面上的保護膜。The adhesive sheet according to claim 9 or claim 10, further comprising a protective film laminated on the surface of the film-shaped adhesive on the side opposite to the substrate. 一種半導體裝置的製造方法，其包括： 打線接合步驟，於基板上經由第一導線而電性連接第一半導體元件； 層壓步驟，於第二半導體元件的單面貼附如申請專利範圍第8項所述的膜狀接著劑；以及 黏晶步驟，經由所述膜狀接著劑而壓接貼附有所述膜狀接著劑的第二半導體元件，藉此將所述第一導線的至少一部分埋入所述膜狀接著劑中。A method for manufacturing a semiconductor device includes: A wire bonding step, electrically connecting the first semiconductor element on the substrate via the first wire; A laminating step, attaching a film-shaped adhesive as described in item 8 of the patent application scope on one side of the second semiconductor element; and In the die bonding step, the second semiconductor element to which the film-shaped adhesive is attached is pressure-bonded via the film-shaped adhesive, thereby burying at least a part of the first lead wire in the film-shaped adhesive.
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