TW201939680A - Adhesive sheet for encapsulation having excellent adhesion to a substrate - Google Patents

Adhesive sheet for encapsulation having excellent adhesion to a substrate Download PDF

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TW201939680A
TW201939680A TW108107390A TW108107390A TW201939680A TW 201939680 A TW201939680 A TW 201939680A TW 108107390 A TW108107390 A TW 108107390A TW 108107390 A TW108107390 A TW 108107390A TW 201939680 A TW201939680 A TW 201939680A
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sheet
semiconductor element
packaging
mass
adhesive sheet
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TW108107390A
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Chinese (zh)
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TWI806980B (en
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土生剛志
清水祐作
飯野智
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日商日東電工股份有限公司
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    • 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
    • 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
    • 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
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2463/00—Presence of epoxy resin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

An adhesive sheet for encapsulation having excellent adhesion to a substrate is provided. The adhesive sheet for encapsulation is used for encapsulating an electronic component on a substrate and bonding the same to the substrate. The adhesive sheet for encapsulation comprises an adhesive composition. With respect to the adhesive sheet for encapsulation before heating, the amount of outgas generated when the adhesive sheet for encapsulation is heated at 150 DEG C for 30 minutes is 500 ppm or more.

Description

封裝用接著薄片Packaging adhesive sheet

本發明係有關於一種封裝用接著薄片。The present invention relates to a bonding sheet for packaging.

以往，已知有藉由封裝用樹脂薄片，將構裝於基板之電子元件(電子裝置)進行封裝，而製造電子裝置者。Conventionally, it has been known to manufacture an electronic device by packaging an electronic component (electronic device) mounted on a substrate with a resin sheet for packaging.

例如，有人提出一種電子裝置封裝體之製造方法，其係將電子裝置封裝用樹脂薄片層合於電子裝置上，接著使電子裝置封裝用樹脂薄片硬化而形成封裝體(例如參照日本特開2017-98353號公報)。For example, someone has proposed a method for manufacturing an electronic device package, which comprises laminating a resin sheet for electronic device packaging on an electronic device, and then hardening the resin sheet for electronic device packaging to form a package (for example, refer to Japanese Patent Application Laid-Open No. 2017- 98353).

然而，電子裝置封裝用薄片係將半導體晶片進行封裝，同時接著於由半導體晶片露出之基板的表面而固定。藉此，可製造可靠性優良的電子裝置封裝體。因此，電子裝置封裝用薄片係要求對基板之良好的接著性。However, the electronic device packaging sheet is a semiconductor wafer that is packaged and then fixed to the surface of the substrate exposed from the semiconductor wafer. Thereby, an electronic device package having excellent reliability can be manufactured. Therefore, the sheet for packaging electronic devices is required to have good adhesion to a substrate.

本發明係提供一種對基板之接著性優良的封裝用接著薄片。The present invention provides a packaging adhesive sheet having excellent adhesiveness to a substrate.

本發明(1)係包含一種封裝用接著薄片，其係將構裝於基板上之電子元件進行封裝，同時接著於前述基板之封裝用接著薄片，其中，含有接著組成物，相對於加熱前之前述封裝用接著薄片而言，前述封裝用接著薄片於150℃下加熱30分鐘時之排氣的發生量為500ppm以上。The present invention (1) includes a bonding sheet for packaging, which is used for packaging electronic components mounted on a substrate, and is then bonded to the aforementioned bonding sheet for packaging. The bonding sheet contains a bonding composition, which is larger than that before heating. With respect to the sealing adhesive sheet, the amount of outgassed when the sealing adhesive sheet is heated at 150 ° C. for 30 minutes is 500 ppm or more.

本發明(2)係包含如(1)之封裝用接著薄片，其中，前述接著組成物含有熱硬化性成分、無機填充劑及偶合劑。(2) The present invention includes the adhesive sheet for packaging according to (1), wherein the adhesive composition contains a thermosetting component, an inorganic filler, and a coupling agent.

本發明(3)係包含如(2)之封裝用接著薄片，其中，相對於前述熱硬化性成分及前述無機填充劑的總量100質量份而言，前述偶合劑之摻合份數為1質量份以上。The present invention (3) is a sealing sheet according to (2), wherein the blending amount of the coupling agent is 1 with respect to 100 parts by mass of the total amount of the thermosetting component and the inorganic filler. More than mass parts.

本發明(4)係包含如(2)或(3)之封裝用接著薄片，其中，前述偶合劑為含有環氧基之矽烷偶合劑。(4) The present invention includes an adhesive sheet for packaging according to (2) or (3), wherein the coupling agent is a silane coupling agent containing an epoxy group.

本發明(5)係包含如(1)～(4)中任一項之封裝用接著薄片，其係含有殘留溶媒，其中，前述殘留溶媒之於封裝用接著薄片中的比例為5ppm以上。(5) The present invention includes the adhesive sheet for encapsulation according to any one of (1) to (4), which contains a residual solvent, wherein the proportion of the residual solvent in the adhesive sheet for encapsulation is 5 ppm or more.

由於本發明之封裝用接著薄片含有接著組成物，因此對基板之接著性優良。Since the adhesive sheet for packaging of the present invention contains an adhesive composition, it has excellent adhesion to a substrate.

又，由於本發明之封裝用接著薄片於150℃下加熱30分鐘時之排氣的發生量為上述下限以上，因此，可藉由所述足量之排氣而提升封裝用接著薄片之硬化物的硬化接著薄片對基板之接著性。In addition, since the amount of exhaust gas generated when the encapsulating adhesive sheet of the present invention is heated at 150 ° C. for 30 minutes is equal to or more than the above lower limit, the hardened product of the encapsulating adhesive sheet can be improved by the sufficient amount of exhaust gas. Adhesion of the hardened adhesive sheet to the substrate.

因此，此封裝用接著薄片其可靠性優良。Therefore, this bonding sheet for packaging has excellent reliability.

茲參照圖1～圖2B來說明本發明之封裝用接著薄片之一實施形態的半導體元件封裝用接著薄片。1 to 2B, a semiconductor device package adhesive sheet according to an embodiment of the package adhesive sheet according to the present invention will be described.

此半導體元件封裝用接著薄片1係將作為構裝於基板2之電子元件之一例的半導體元件3(參照圖2A)進行封裝，同時接著於基板2的封裝用接著薄片。This bonding sheet 1 for packaging semiconductor elements is a packaging sheet for packaging a semiconductor element 3 (see FIG. 2A) as an example of an electronic component mounted on a substrate 2, and a bonding sheet for packaging on a substrate 2.

又，半導體元件封裝用接著薄片1係用來製造後述之半導體元件封裝體集合體4(參照圖2B)的零件，非為半導體元件封裝體4本身，半導體元件封裝用接著薄片1不包含半導體元件3及構裝半導體元件3之基板2，具體而言，係以單獨零件流通，為產業上可利用之裝置。The bonding sheet 1 for semiconductor element packaging is a component used to manufacture the semiconductor element package assembly 4 (see FIG. 2B) described later, and is not the semiconductor element package 4 itself. The bonding sheet 1 for semiconductor element packaging does not include semiconductor elements. 3 and the substrate 2 on which the semiconductor element 3 is mounted, specifically, are circulated as separate parts and are industrially available devices.

此外，半導體元件封裝用接著薄片1非為封裝半導體元件3後的硬化接著薄片10(參照圖2B)(後述)，亦即，其為封裝半導體元件3前的薄片。The bonding sheet 1 for semiconductor element packaging is not a hardened bonding sheet 10 (see FIG. 2B) (described later) after packaging the semiconductor element 3, that is, a sheet before packaging the semiconductor element 3.

如圖1所示，半導體元件封裝用接著薄片1係具有朝與厚度方向正交之方向(面方向)延伸的略平板形狀(薄膜狀)。又，半導體元件封裝用薄片1係具備作為位於厚度方向其中一側之一方的面之一例的接著面5，及作為與接著面5於厚度方向相對向之另一面之一例的第1相向面6。接著面5及第1相向面6均具有平坦面，且彼此平行。As shown in FIG. 1, the adhesive sheet 1 for a semiconductor element package has a substantially flat plate shape (thin film shape) extending in a direction (plane direction) orthogonal to the thickness direction. The semiconductor device package sheet 1 includes a bonding surface 5 as an example of a surface located on one side of the thickness direction, and a first facing surface 6 as an example of the other surface facing the bonding surface 5 in the thickness direction. . Both the subsequent surface 5 and the first facing surface 6 have flat surfaces and are parallel to each other.

接著面5係位於半導體元件封裝用接著薄片1之厚度方向另一側的面(下表面)，如圖2B所示，當半導體元件封裝用接著薄片1封裝半導體元件3時，係接觸半導體元件3及基板2而接著的接觸面(厚度方向另一面)。The bonding surface 5 is a surface (lower surface) located on the other side in the thickness direction of the bonding sheet 1 for semiconductor element packaging. As shown in FIG. The contact surface (the other surface in the thickness direction) that is next to the substrate 2.

另一方面，第1相向面6係半導體元件封裝用接著薄片1封裝半導體元件3時，未與半導體元件3接觸，而與基板2之被接著面8(後述)於厚度方向隔著間隔相向配置的非接觸面(厚度方向其中一面)(上表面)。On the other hand, when the first opposing surface 6 is a semiconductor element packaging adhesive sheet 1 for packaging the semiconductor element 3, the semiconductor element 3 is not in contact with the semiconductor element 3 but is opposed to the bonding surface 8 (described later) of the substrate 2 at intervals in the thickness direction. Non-contact surface (one surface in the thickness direction) (upper surface).

半導體元件封裝用薄片1係含有接著組成物。具體而言，半導體元件封裝用接著薄片1之材料為接著組成物(封裝性接著組成物)。接著組成物係含有例如熱硬化性成分、無機填充劑及偶合劑。The semiconductor device package sheet 1 contains an adhesive composition. Specifically, the material of the adhesive sheet 1 for semiconductor element packaging is an adhesive composition (encapsulating adhesive composition). The composition system contains, for example, a thermosetting component, an inorganic filler, and a coupling agent.

熱硬化性成分係在半導體元件封裝用接著薄片1(封裝組成物)中，使無機填充劑彼此結合的黏著劑成分，可藉由熱硬化而提升接著組成物的硬度，由此使接著組成物展現接著力。較佳可舉出環氧系熱硬化性成分(後述)。The thermosetting component is an adhesive component that binds inorganic fillers to the bonding sheet 1 (encapsulating composition) for semiconductor device packaging, and can increase the hardness of the bonding composition by heat curing, thereby making the bonding composition Show cohesion. Preferred examples include epoxy-based thermosetting components (described later).

熱硬化性成分係包含例如主劑(封裝樹脂)、硬化劑及硬化促進劑。The thermosetting component system includes, for example, a main agent (encapsulating resin), a curing agent, and a curing accelerator.

作為主劑，可舉出例如環氧樹脂、酚樹脂、三聚氰胺樹脂、乙烯酯樹脂、氰基酯樹脂、馬來醯亞胺樹脂、聚矽氧樹脂等。作為主劑，基於耐熱性等觀點，較佳可舉出環氧樹脂。主劑若為環氧樹脂，則熱硬化性成分係構成後述之硬化劑(環氧系硬化劑)及硬化促進劑(環氧系硬化促進劑)，以及環氧系熱硬化性成分。Examples of the main agent include epoxy resin, phenol resin, melamine resin, vinyl ester resin, cyanoester resin, maleimide resin, and polysiloxane resin. As the main agent, from the viewpoint of heat resistance and the like, an epoxy resin is preferably mentioned. If the main agent is an epoxy resin, the thermosetting component is a hardener (epoxy-based hardener) and a hardening accelerator (epoxy-based hardening accelerator) described later, and an epoxy-based thermosetting component.

又，主劑為將半導體元件封裝用薄片1加熱而將半導體元件3進行封裝時，發生源自主劑之氣體(主劑(較佳為環氧樹脂)之氣化物)的氣體發生成分。The main agent is a gas generating component that generates a gas derived from the main agent (evaporation of the main agent (preferably an epoxy resin)) when the semiconductor element 3 is packaged by heating the semiconductor element packaging sheet 1.

作為環氧樹脂，可舉出例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、改質雙酚A型環氧樹脂、改質雙酚F型環氧樹脂、聯苯型環氧樹脂等2官能環氧樹脂，例如酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、參羥基苯基甲烷型環氧樹脂、四羥苯基乙烷型環氧樹脂、二環戊二烯型環氧樹脂等3官能以上之多官能環氧樹脂等。此等環氧樹脂可單獨使用或併用2種以上。Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, modified bisphenol A epoxy resin, modified bisphenol F epoxy resin, and biphenyl epoxy resin. Bifunctional epoxy resins such as resins, such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, p-hydroxyphenylmethane-type epoxy resin, tetrahydroxyphenylethane-type epoxy resin, dicyclopentyl Difunctional epoxy resins such as diene epoxy resins and more. These epoxy resins can be used alone or in combination of two or more.

較佳可舉出單獨使用2官能環氧樹脂，具體而言，可舉出單獨使用雙酚F型環氧樹脂。Preferably, a bifunctional epoxy resin is used alone, and specifically, a bisphenol F-type epoxy resin is used specifically.

環氧樹脂的環氧當量例如為10g/eq.以上，較佳為100g/eq.以上；又，例如為300g/eq.以下，較佳為250 g/eq.以下。The epoxy equivalent of the epoxy resin is, for example, 10 g / eq. Or more, preferably 100 g / eq. Or more; and, for example, 300 g / eq. Or less, and preferably 250 g / eq. Or less.

主劑(較佳為環氧樹脂)的軟化點例如為50℃以上，較佳為70℃以上；又，例如為110℃以下，較佳為90℃以下。The softening point of the main agent (preferably epoxy resin) is, for example, 50 ° C or higher, preferably 70 ° C or higher; and, for example, 110 ° C or lower, preferably 90 ° C or lower.

主劑(較佳為環氧樹脂)的比例，在接著組成物中，例如為1質量%以上，較佳為2質量%以上；又，例如為30質量%以下，較佳為10質量%以下。此外，主劑(較佳為環氧樹脂)的比例，在熱硬化性成分中，例如為50質量%以上，較佳為60質量%以上；又，例如為90質量%以下，較佳為10質量%以下。The proportion of the main agent (preferably epoxy resin) in the adhesive composition is, for example, 1% by mass or more, preferably 2% by mass or more; and, for example, 30% by mass or less, and preferably 10% by mass or less. . The proportion of the main component (preferably epoxy resin) in the thermosetting component is, for example, 50% by mass or more, preferably 60% by mass or more; and, for example, 90% by mass or less, preferably 10 Mass% or less.

主劑(較佳為環氧樹脂)的比例若為上述下限以上，則可釋放出足量之源自主劑之氣體，而發生所要量的排氣。If the proportion of the main agent (preferably epoxy resin) is above the lower limit described above, a sufficient amount of gas derived from the main agent can be released, and the required amount of exhaust can occur.

硬化劑係藉由加熱而使上述主劑硬化的成分(較佳為環氧樹脂硬化劑)。作為硬化劑，可舉出例如酚酚醛清漆樹脂等酚樹脂。The hardener is a component (preferably an epoxy resin hardener) that hardens the main agent by heating. Examples of the hardener include a phenol resin such as a phenol novolac resin.

硬化劑的比例，若主劑為環氧樹脂、硬化劑為酚樹脂，係以相對於環氧樹脂中的環氧基1當量，酚樹脂中之羥基的合計例如為0.7當量以上，較佳為0.9當量以上，例如為1.5當量以下，較佳為1.2當量以下的方式來調整。具體而言，相對於主劑100質量份，硬化劑的摻合份數例如為30質量份以上，較佳為50質量份以上；又，例如為75質量份以下，較佳為60質量份以下。The proportion of the hardener, if the main agent is an epoxy resin and the hardener is a phenol resin, is 1 equivalent to the epoxy group in the epoxy resin, and the total number of hydroxyl groups in the phenol resin is, for example, 0.7 equivalent or more, preferably It is adjusted to 0.9 or more, for example, 1.5 or less, and preferably 1.2 or less. Specifically, the blending amount of the hardener is, for example, 30 parts by mass or more, and preferably 50 parts by mass or more, based on 100 parts by mass of the main agent; for example, 75 parts by mass or less, and preferably 60 parts by mass or less. .

硬化促進劑為藉由加熱而促進主劑之硬化的觸媒(熱硬化觸媒)(較佳為環氧樹脂硬化促進劑)，可舉出例如有機磷系化合物；例如2-苯基-4-甲基-5-羥基甲基咪唑(2P4MHZ)等咪唑化合物等。較佳可舉出咪唑化合物。相對於主劑100質量份，硬化促進劑的摻合份數例如為0.05質量份以上；又，例如為5質量份以下。The hardening accelerator is a catalyst (thermosetting catalyst) (preferably an epoxy resin hardening accelerator) that accelerates hardening of the main agent by heating, and examples thereof include organic phosphorus compounds; for example, 2-phenyl-4 -Imidazole compounds such as methyl-5-hydroxymethylimidazole (2P4MHZ) and the like. Preferably, an imidazole compound is mentioned. The blending number of the hardening accelerator is, for example, 0.05 parts by mass or more, and, for example, 5 parts by mass or less with respect to 100 parts by mass of the main agent.

無機填充劑係用來提升半導體元件封裝用接著薄片1之強度，且對半導體元件封裝用薄片1賦予優良的韌性的無機粒子。作為無機填充劑之材料，可舉出例如石英玻璃、滑石、二氧化矽、氧化鋁、氮化鋁、氮化矽、氮化硼等無機化合物。此等可單獨使用或併用2種以上。較佳可舉出二氧化矽。The inorganic filler is an inorganic particle used to improve the strength of the bonding sheet 1 for semiconductor device packaging, and to impart excellent toughness to the sheet 1 for semiconductor device packaging. Examples of the material of the inorganic filler include inorganic compounds such as quartz glass, talc, silicon dioxide, aluminum oxide, aluminum nitride, silicon nitride, and boron nitride. These can be used alone or in combination of two or more. Preferable examples include silicon dioxide.

無機填充劑的形狀不特別限定，可舉出例如略球狀、略板狀、略針狀、不定形狀等。較佳可舉出略球狀。The shape of the inorganic filler is not particularly limited, and examples thereof include a slightly spherical shape, a slightly plate shape, a slightly needle shape, and an irregular shape. Preferably, a slightly spherical shape is mentioned.

無機填充劑之最大長度的平均值(若為略球狀則為平均粒徑)M例如為50μm以下，較佳為20μm以下，更佳為10μm以下；又，例如為0.1μm以上，較佳為0.5μm以上。此外，平均粒徑M係基於例如藉由雷射散射法中之粒度分布測定法所求得的粒度分布，以D50值(累積50%中值徑)求得。The average value of the maximum length of the inorganic filler (if it is slightly spherical, the average particle diameter) M is, for example, 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less; and, for example, 0.1 μm or more, preferably 0.5 μm or more. The average particle diameter M is obtained based on, for example, a particle size distribution obtained by a particle size distribution measurement method in a laser scattering method, and is obtained as a D50 value (50% cumulative median diameter).

又，無機填充劑可包含第1填充劑，與具有小於第1填充劑之最大長度的平均值M1之最大長度的平均值M2的第2填充劑。The inorganic filler may include a first filler and a second filler having an average value M2 of a maximum length that is smaller than an average value M1 of the maximum length of the first filler.

第1填充劑之最大長度的平均值(若為略球狀則為平均粒徑)M1例如為1μm以上，較佳為3μm以上；又，例如為50μm以下，較佳為30μm以下。The average value of the maximum length of the first filler (if it is slightly spherical, the average particle diameter) M1 is, for example, 1 μm or more, preferably 3 μm or more; and, for example, 50 μm or less, and preferably 30 μm or less.

第2填充劑之最大長度的平均值(若為略球狀則為平均粒徑)M2例如為未滿1μm，較佳為0.8μm以下；又，例如為0.01μm以上，較佳為0.1μm以上。The average value of the maximum length of the second filler (if it is slightly spherical, the average particle diameter) M2 is, for example, less than 1 μm, preferably 0.8 μm or less; and, for example, 0.01 μm or more, preferably 0.1 μm or more .

第1填充劑之最大長度的平均值相對於第2填充劑之最大長度的平均值的比(M1/M2)例如為2以上，較佳為5以上；又，例如為50以下，較佳為20以下。The ratio (M1 / M2) of the average value of the maximum length of the first filler to the average value of the maximum length of the second filler is, for example, 2 or more, preferably 5 or more; and, for example, 50 or less, preferably 20 or less.

第1填充劑及第2填充劑之材料可均為相同或相異。較佳的是第1填充劑及第2填充劑之材料皆相同，具體而言為二氧化矽。The materials of the first filler and the second filler may be the same or different. It is preferable that the materials of the first filler and the second filler are the same, specifically, silicon dioxide.

再者，無機填充劑其表面亦可部分或全部以矽烷偶合劑等進行表面處理。較佳可舉出併用未經表面處理之第1填充劑與經表面處理之第2填充劑。In addition, the surface of the inorganic filler may be partially or completely surface-treated with a silane coupling agent or the like. Preferably, the first filler without surface treatment and the second filler with surface treatment are used in combination.

無機填充劑(若併用第1填充劑及第2填充劑則為彼等的總量)的比例，在半導體元件封裝用接著薄片1 (接著組成物)中，例如為50質量%以上，較佳為超過50質量%，更佳為55質量%以上，再更佳為60質量%以上；又，例如為95質量%以下，例如為90質量%以下，較佳為85質量%以下，更佳為75質量%以下，再更佳為70質量%以下，尤佳為未滿70質量%。The proportion of the inorganic filler (the total amount of the first filler and the second filler if they are used in combination) is, for example, 50% by mass or more in the adhesive sheet 1 (adhesive composition) for semiconductor device encapsulation. It is more than 50% by mass, more preferably 55% by mass or more, still more preferably 60% by mass or more; and, for example, 95% by mass or less, for example, 90% by mass or less, more preferably 85% by mass or less, more preferably 75 mass% or less, still more preferably 70 mass% or less, and even more preferably less than 70 mass%.

無機填充劑的比例若高於上述之下限，則可確保半導體元件封裝用接著薄片1的韌性。When the ratio of the inorganic filler is higher than the lower limit described above, the toughness of the adhesive sheet 1 for semiconductor device packaging can be secured.

另一方面，無機填充劑的比例若低於上述之上限，則可抑制半導體元件封裝用接著薄片1脆化，而確實地封裝半導體元件3。On the other hand, if the ratio of the inorganic filler is lower than the above-mentioned upper limit, the semiconductor device 3 can be reliably packaged while suppressing embrittlement of the bonding sheet 1 for semiconductor device packaging.

當無機填充劑包含上述第1填充劑與第2填充劑時，第1填充劑的比例，在接著組成物中例如為40質量%以上，較佳為超過50質量%；又，例如為80質量%以下，較佳為70質量%以下。When the inorganic filler includes the first filler and the second filler, the proportion of the first filler in the adhesive composition is, for example, 40% by mass or more, preferably more than 50% by mass; and, for example, 80% by mass. % Or less, preferably 70% by mass or less.

當無機填充劑包含上述第1填充劑與第2填充劑時，相對於第1填充劑100質量份而言，第2填充劑的摻合份數例如為30質量份以上，較佳為45質量份以上，更佳為50質量份以上，再更佳為超過50質量份；又，例如為未滿100質量份，較佳為80質量份以下，更佳為70質量份以下，再更佳為60質量份以下。When the inorganic filler includes the first filler and the second filler, the blending amount of the second filler is, for example, 30 parts by mass or more, and preferably 45 parts by mass, relative to 100 parts by mass of the first filler. More than 50 parts by mass, more preferably more than 50 parts by mass; and, for example, less than 100 parts by mass, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less.

第2填充劑的摻合份數若高於上述下限或者低於上述上限，則可藉由第2填充劑有效地填充第1填充劑間之較大的間隙，而獲得韌性優良的半導體元件封裝用薄片1，甚而硬化接著薄片10。If the blending amount of the second filler is higher than the lower limit or lower than the upper limit, the large gap between the first fillers can be effectively filled by the second filler, and a semiconductor device package having excellent toughness can be obtained. With sheet 1, the sheet 10 is even hardened.

偶合劑係用來使熱硬化性成分(尤為主劑及硬化劑)與無機填充劑(較佳為二氧化矽)(的表面)偶合(形成化學鍵)，而形成具韌性之硬化接著薄片10的反應性成分。又，偶合劑亦為將半導體元件封裝用薄片1加熱而將半導體元件3進行封裝時，發生源自偶合劑之氣體(偶合劑氣化之氣體及藉由偶合劑之水解反應(後述)而生成的生成物(R’4-n Si-OHn )(化學式的細節茲參照下式(1))之氣體)，與源自殘留溶媒之氣體(於後述，較佳為烷氧基與空氣中的水分進行水解反應而生成之源自醇(ROH)等溶媒的溶媒氣體)的氣體發生成分。此外，上述之源自偶合劑之氣體與源自殘留溶媒之氣體係與上述之源自主劑之氣體(環氧樹脂之氣化物)共同構成(含於)排氣。The coupling agent is used to couple (form a chemical bond) the thermosetting component (especially the main agent and the hardener) with the inorganic filler (preferably silicon dioxide) (to form a chemical bond) to form a tough, hardened adhesive sheet 10 Of reactive ingredients. In addition, the coupling agent is also generated when the semiconductor element 3 is packaged by heating the semiconductor element packaging sheet 1, and a gas derived from the coupling agent (a gas vaporized by the coupling agent and a hydrolysis reaction (described later) by the coupling agent) are generated. Product (R ' 4-n Si-OH n ) (for details of the chemical formula, refer to the gas of the following formula (1)), and the gas derived from the residual solvent (to be described later, preferably alkoxy and air A gas generating component derived from a solvent gas such as alcohol (ROH) generated by a hydrolysis reaction of water. In addition, the above-mentioned gas derived from the coupling agent and the gas system derived from the residual solvent and the above-mentioned gas derived from the autonomous agent (evaporation of epoxy resin) constitute (include) the exhaust gas.

偶合劑係於1分子中具有可與主劑反應之第1反應性基，及可與無機填充劑反應之第2反應性基此至少2種反應性基。作為第1反應性基，可舉出例如環氧基、乙烯基、(甲基)丙烯醯基、胺基、異氰酸酯基、巰基等。第1反應性基可單獨使用或併用。作為第1反應性基，較佳可舉出環氧基。作為第2反應性基，可舉出烷氧基等。The coupling agent has at least two types of reactive groups in one molecule, including a first reactive group capable of reacting with the main agent and a second reactive group capable of reacting with the inorganic filler. Examples of the first reactive group include an epoxy group, a vinyl group, a (meth) acrylfluorenyl group, an amine group, an isocyanate group, and a mercapto group. The first reactive groups can be used alone or in combination. The first reactive group is preferably an epoxy group. Examples of the second reactive group include an alkoxy group.

具體而言，偶合劑例如為矽烷偶合劑。Specifically, the coupling agent is, for example, a silane coupling agent.

矽烷偶合劑係例如以下述式(1)表示。The silane coupling agent is represented by the following formula (1), for example.

R’4-n Si-ORn (1)
式(1)中，R表示甲基、乙基等碳數1以上2以下之烷基。R’表示具有第1反應性基(較佳為後述之環氧基)之基。n例如表示1以上且3以下之整數，較佳為1或2之整數。R ' 4-n Si-OR n (1)
In formula (1), R represents an alkyl group having 1 to 2 carbon atoms, such as a methyl group and an ethyl group. R 'represents a group having a first reactive group (preferably an epoxy group described later). n represents, for example, an integer of 1 or more and 3 or less, and is preferably an integer of 1 or 2.

具體而言，就矽烷偶合劑而言，可舉出例如具有環氧基、乙烯基、(甲基)丙烯醯基、胺基、異氰酸酯基、巰基等作為上述第1反應性基的矽烷偶合劑。具體而言，作為矽烷偶合劑，可舉出例如含有環氧基之矽烷偶合劑、含有乙烯基之矽烷偶合劑、含有(甲基)丙烯醯基之矽烷偶合劑、含有胺基之矽烷偶合劑、含有異氰酸酯基之矽烷偶合劑、含有巰基之矽烷偶合劑等。Specific examples of the silane coupling agent include a silane coupling agent having an epoxy group, a vinyl group, a (meth) acrylfluorenyl group, an amine group, an isocyanate group, and a mercapto group as the first reactive group. . Specific examples of the silane coupling agent include a silane coupling agent containing an epoxy group, a silane coupling agent containing a vinyl group, a silane coupling agent containing a (meth) acrylfluorenyl group, and a silane coupling agent containing an amine group. , Silane coupling agent containing isocyanate group, Silane coupling agent containing mercapto group, etc.

作為含有環氧基之矽烷偶合劑，可舉出例如3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷等3-環氧丙氧基二烷基二烷氧基矽烷；例如3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等3-環氧丙氧基烷基三烷氧基矽烷。Examples of the epoxy-containing silane coupling agent include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Glycidoxydialkyldialkoxysilane; such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Alkylalkyltrialkoxysilane.

作為含有乙烯基之矽烷偶合劑，可舉出例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等。Examples of the vinyl-containing silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, and the like.

作為含有(甲基)丙烯醯基之矽烷偶合劑，可舉出例如3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等含有甲基丙烯醯基之矽烷偶合劑、例如、3-丙烯醯氧丙基三甲氧基矽烷等含有丙烯醯基之矽烷偶合劑等。Examples of the (meth) acrylfluorenyl-containing silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3 -Methacrylic acid silane-containing silane coupling agents, such as methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, for example, 3-propenyloxypropane Acrylic acid-based silane coupling agents such as trimethoxysilane and the like.

作為含有胺基之矽烷偶合劑，可舉出例如N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺基丙基三甲氧基矽烷等。Examples of the amine-containing silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-di Methyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.

作為含有異氰酸酯基之矽烷偶合劑，可舉出例如3-異氰酸酯丙基三乙氧基矽烷等。Examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane.

作為含有巰基之矽烷偶合劑，可舉出例如3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。Examples of the mercapto-containing silane coupling agent include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

作為偶合劑，較佳可舉出含有環氧基之矽烷偶合劑，更佳可舉出3-環氧丙氧基烷基三烷氧基矽烷。The coupling agent is preferably a silane coupling agent containing an epoxy group, and more preferably a 3-glycidoxyalkyltrialkoxysilane.

偶合劑的比例，在接著組成物中例如為0.2質量%以上，較佳為0.5質量%以上，更佳為1.0質量%以上；又，例如為10質量%以下，較佳為5質量%以下。又，相對於熱硬化性成分及無機填充劑的總量100質量份，偶合劑的摻合份數例如為0.2質量份以上，較佳為0.5質量份以上，更佳為1質量份以上；又，例如為10質量份以下，較佳為5質量份以下。The ratio of the coupling agent in the adhesive composition is, for example, 0.2% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more; and, for example, 10% by mass or less, and preferably 5% by mass or less. The blending amount of the coupling agent is, for example, 0.2 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of the thermosetting component and the inorganic filler. It is, for example, 10 parts by mass or less, and preferably 5 parts by mass or less.

偶合劑的比例及/或摻合份數若為上述下限以上，可使熱硬化性成分與無機填充劑確實地偶合，同時釋放出足量之源自偶合劑之氣體及源自殘留溶媒之氣體，而能夠發生所要量的排氣。If the ratio of the coupling agent and / or the blending amount is above the lower limit, the thermosetting component can be reliably coupled with the inorganic filler, and at the same time, a sufficient amount of the gas derived from the coupling agent and the gas derived from the residual solvent can be released. And the required amount of exhaust can occur.

另一方面，偶合劑的比例及/或摻合份數若為上述上限以下，較無半導體元件封裝用接著薄片1製造後向表面(接著面5及第1相向面6)析出(滲出)之虞，而能夠製作穩定的清漆(後述)。On the other hand, if the ratio of the coupling agent and / or the blending amount is below the upper limit described above, it will be less than the surface (adhesion surface 5 and the first facing surface 6) of the semiconductor element packaging adhesive sheet 1 (exudation) after the production of the adhesive sheet 1. It is possible to produce a stable varnish (described later).

此外，亦可對接著組成物以適宜的比例添加熱塑性樹脂、顏料等添加劑。In addition, additives such as a thermoplastic resin and a pigment may be added to the adhesive composition at an appropriate ratio.

熱塑性樹脂為提升加熱時的硬化接著薄片10之柔軟性的成分。The thermoplastic resin is a component that enhances the flexibility of the hardened adhesive sheet 10 during heating.

作為熱塑性樹脂，可舉出例如天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、聚醯胺樹脂(6-尼龍或6,6-尼龍等)、苯氧基樹脂、丙烯酸樹脂、飽和聚酯樹脂(PET等)、聚醯胺醯亞胺樹脂、氟樹脂、苯乙烯-異丁烯-苯乙烯嵌段共聚物等。此等熱塑性樹脂可單獨使用或併用2種以上。Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and polybutylene Diene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin (6-nylon or 6,6-nylon, etc.), phenoxy resin, acrylic resin, saturated polyester resin (PET, etc.), Polyamidoamine imine resin, fluororesin, styrene-isobutylene-styrene block copolymer, etc. These thermoplastic resins can be used alone or in combination of two or more.

作為熱塑性樹脂，較佳的是，基於提升與主劑(較佳為環氧樹脂)之分散性的觀點，可舉出丙烯酸樹脂。The thermoplastic resin is preferably an acrylic resin from the viewpoint of improving dispersibility with a base agent (preferably an epoxy resin).

作為丙烯酸樹脂，可舉出例如將包含具有直鏈或分支之烷基之(甲基)丙烯酸烷基酯，與其他單體(共聚合性單體)的單體成分聚合而成之含有羧基的(甲基)丙烯酸酯共聚物(較佳為含有羧基的丙烯酸酯共聚物)等。Examples of the acrylic resin include a carboxyl group-containing one obtained by polymerizing an alkyl (meth) acrylate containing a linear or branched alkyl group with a monomer component of another monomer (copolymerizable monomer). A (meth) acrylate copolymer (preferably a carboxyl group-containing acrylate copolymer) and the like.

作為烷基，可舉出例如甲基、乙基、丙基、異丙基、正丁基、三級丁基、異丁基、戊基、己基等碳數1~6之烷基。Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, tertiary butyl, isobutyl, pentyl, and hexyl.

作為其他單體，可舉出例如丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、巴豆酸等含有羧基的單體。Examples of other monomers include monomers containing a carboxyl group such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, iconic acid, maleic acid, fumaric acid, and crotonic acid.

熱塑性樹脂的重量平均分子量例如為10萬以上，較佳為30萬以上；又，例如為100萬以下，較佳為80萬以下。此外，重量平均分子量係根據凝膠滲透層析法(GPC)，基於標準聚苯乙烯換算值來測量。The weight average molecular weight of the thermoplastic resin is, for example, 100,000 or more, preferably 300,000 or more; and, for example, 1 million or less, and preferably 800,000 or less. In addition, the weight average molecular weight is measured based on a standard polystyrene conversion value by gel permeation chromatography (GPC).

熱塑性樹脂的比例(固體成分比例)係以不妨礙接著組成物之熱硬化的方式來調整，具體而言，相對於接著組成物，例如為1質量%以上，較佳為2質量%以上，更佳為3.5質量%以上；又，例如為10質量%以下，較佳為5質量%以下，更佳為5質量%以下。The ratio of the thermoplastic resin (solid content ratio) is adjusted so as not to hinder the thermal curing of the bonding composition. Specifically, it is, for example, 1% by mass or more, preferably 2% by mass or more, with respect to the bonding composition. It is preferably 3.5 mass% or more; for example, it is 10 mass% or less, preferably 5 mass% or less, and more preferably 5 mass% or less.

此外，熱塑性樹脂亦能以適當溶媒稀釋而調製。In addition, the thermoplastic resin can be prepared by dilution with a suitable solvent.

作為顏料，可舉出例如碳黑等黑色顏料。顏料的平均粒徑例如為0.001μm以上，且例如為1μm以下。相對於接著組成物，顏料的比例例如為0.1質量%以上，且例如為2質量%以下。Examples of the pigment include black pigments such as carbon black. The average particle diameter of the pigment is, for example, 0.001 μm or more, and for example, 1 μm or less. The ratio of the pigment to the adhesive composition is, for example, 0.1% by mass or more, and, for example, 2% by mass or less.

要調製接著組成物，係摻合熱硬化性成分、無機填充劑、偶合劑與視需求而定之添加劑，並將該等混合。較佳為摻合上述之各成分與溶媒，將該等混合，而調製清漆。To prepare an adhesive composition, a thermosetting component, an inorganic filler, a coupling agent, and additives as required are blended, and these are mixed. It is preferable that the above-mentioned components and a solvent are blended, and these are mixed to prepare a varnish.

作為溶媒，不特別限定，可舉出例如甲基乙基酮等酮；例如甲苯等芳香族系溶媒；例如乙酸乙酯等酯；例如甲醇、乙醇等醇等。較佳可舉出酮。The solvent is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone; aromatic solvents such as toluene; esters such as ethyl acetate; alcohols such as methanol and ethanol; and the like. Preferably, a ketone is mentioned.

又，溶媒較佳為低分子量，具體而言，其分子量例如為300以下，較佳為200以下，更佳為100以下；又，例如為20以上，較佳為50以上。溶媒的分子量若為上述上限以下且下限以上，可充分發生構成排氣的一部分的源自殘留溶媒之氣體(源自溶媒之氣體)，而發生所要量的排氣。The solvent preferably has a low molecular weight. Specifically, the molecular weight is, for example, 300 or less, preferably 200 or less, and more preferably 100 or less; and, for example, 20 or more, and preferably 50 or more. If the molecular weight of the solvent is equal to or less than the upper limit and greater than the lower limit, a gas derived from the residual solvent (gas derived from the solvent) constituting a part of the exhaust gas can be sufficiently generated, and a desired amount of exhaust gas can be generated.

溶媒的摻合份數係適宜設定，相對於上述之成分的總量(熱硬化性成分、無機填充劑、矽烷偶合劑及添加劑的總量)(所謂的固體成分的總量)100質量份，例如為5質量份以上，較佳為25質量份以上，更佳為75質量份以上；又，例如為1000質量份以下，較佳為500質量份以下。溶媒的摻合份數若為上述下限以上，可充分發生構成排氣的一部分的源自殘留溶媒之氣體(源自溶媒之氣體)，而發生所要量的排氣。溶媒的摻合份數若為上述上限以下，則可藉由塗佈及乾燥等簡易地製造較厚的半導體元件封裝用薄片1。The blending amount of the solvent is appropriately set, and 100 parts by mass with respect to the total amount of the aforementioned components (the total amount of the thermosetting component, the inorganic filler, the silane coupling agent, and the additive) (the total amount of the so-called solid content) For example, it is 5 parts by mass or more, preferably 25 parts by mass or more, more preferably 75 parts by mass or more; and, for example, 1,000 parts by mass or less, and preferably 500 parts by mass or less. If the blending amount of the solvent is at least the above lower limit, a gas derived from the residual solvent (gas derived from the solvent) constituting a part of the exhaust gas can be sufficiently generated, and a desired amount of exhaust gas can be generated. If the blending amount of the solvent is equal to or less than the above upper limit, a thicker semiconductor element packaging sheet 1 can be easily manufactured by coating, drying, or the like.

其次，說明半導體元件封裝用接著薄片1之製造方法。Next, a method for manufacturing the adhesive sheet 1 for semiconductor element packaging will be described.

要製造半導體元件封裝用接著薄片1，例如，首先係調製上述之清漆。其次，如圖1所示，將清漆塗佈於第1剝離薄片15並加以乾燥。乾燥條件係不使熱硬化性成分硬化(具體而言為未完全硬化)，另外可去除溶媒之大部分(非全部的量之溶媒)的條件，具體而言，加熱溫度例如為40℃以上，較佳為70℃以上；又，130℃以下，較佳為120℃以下；又，加熱時間例如為10秒以上，較佳為1分以上；又，例如為15分以下，較佳為10分以下。To manufacture the adhesive sheet 1 for semiconductor device packaging, for example, the above-mentioned varnish is first prepared. Next, as shown in FIG. 1, the varnish is applied to the first release sheet 15 and dried. Drying conditions are conditions in which the thermosetting component is not hardened (specifically, incomplete hardening), and most of the solvent (not all of the solvent) can be removed. Specifically, the heating temperature is, for example, 40 ° C or higher. It is preferably 70 ° C or higher; 130 ° C or lower, preferably 120 ° C or lower; and the heating time is, for example, 10 seconds or longer, preferably 1 minute or longer; and, for example, 15 minutes or lower, preferably 10 minutes or longer the following.

藉此，在被第1剝離薄片15所支撐的狀態下製造半導體元件封裝用接著薄片1。其後，將第2剝離薄片16配置於相對於半導體元件封裝用接著薄片1與第1剝離薄片15相反之一側。換言之，係以由第1剝離薄片15及第2剝離薄片16於厚度方向包夾之狀態製造半導體元件封裝用接著薄片1。半導體元件封裝用接著薄片1的接著面5及第1相向面6各者係各自接觸第1剝離薄片15及第2剝離薄片16。Thereby, the adhesive sheet 1 for semiconductor element packages is manufactured in the state supported by the 1st release sheet 15. After that, the second release sheet 16 is disposed on the side opposite to the first release sheet 15 with respect to the semiconductor device package adhesive sheet 1. In other words, the adhesive sheet 1 for a semiconductor element package is manufactured in a state where the first release sheet 15 and the second release sheet 16 are sandwiched in the thickness direction. Each of the adhesive surface 5 and the first facing surface 6 of the adhesive sheet 1 for semiconductor element packaging is in contact with the first release sheet 15 and the second release sheet 16, respectively.

第1剝離薄片15及第2剝離薄片16各者係具有可撓性，且具有朝面方向延伸的薄片形狀。作為第1剝離薄片15及第2剝離薄片16之材料，可舉出例如聚對苯二甲酸乙二酯、聚醯亞胺等樹脂，例如不鏽鋼等金屬等，較佳可舉出樹脂。又，第1剝離薄片15及第2剝離薄片16的表面(接觸半導體元件封裝用接著薄片1的接觸面)亦可實施剝離處理。第1剝離薄片15及第2剝離薄片16各者的厚度例如為1μm以上，較佳為10μm以上；又，例如為1000μm以下，較佳為500μm以下。Each of the first release sheet 15 and the second release sheet 16 is flexible and has a sheet shape extending in a planar direction. Examples of the material of the first release sheet 15 and the second release sheet 16 include resins such as polyethylene terephthalate and polyimide, and metals such as stainless steel, and resins are preferred. In addition, the surfaces of the first release sheet 15 and the second release sheet 16 (contact surfaces that contact the bonding sheet 1 for a semiconductor element package) may be subjected to a peeling treatment. The thickness of each of the first release sheet 15 and the second release sheet 16 is, for example, 1 μm or more, preferably 10 μm or more; and, for example, 1000 μm or less, and preferably 500 μm or less.

另外，也可不調製清漆，而是藉由混練擠出而由接著組成物(實質上不含溶媒之組成物)製造半導體元件封裝用接著薄片1。第1剝離薄片15及第2剝離薄片16係配置於擠出後之半導體元件封裝用接著薄片1。In addition, instead of preparing a varnish, the adhesive sheet 1 for semiconductor element packaging may be produced from an adhesive composition (a composition substantially free of a solvent) by kneading and extrusion. The first release sheet 15 and the second release sheet 16 are arranged on an extruded adhesive sheet 1 for a semiconductor element package.

較佳為調製清漆，並將其藉由塗佈形成半導體元件封裝用薄片1。若由清漆形成半導體元件封裝用薄片1，則可發生所要量的排氣(尤為源於溶媒的源自殘留溶媒之氣體)。It is preferable to prepare a varnish and apply the varnish to form the semiconductor device package sheet 1. When the sheet 1 for encapsulating a semiconductor element is formed of a varnish, a desired amount of exhaust gas (especially a gas derived from a residual solvent originating from a solvent) can be generated.

半導體元件封裝用接著薄片1中的熱硬化性成分例如為B階段(非完全硬化之半硬化)。B階段係熱硬化性成分處於呈液狀之A階段與完全硬化之C階段之間的狀態，係僅些微進行硬化及凝膠化，且壓縮彈性模數小於C階段之彈性模數的狀態。The thermosetting component in the bonding sheet 1 for semiconductor element packaging is, for example, B-stage (semi-hardened half-hardened). The B-stage is a state where the thermosetting component is in a liquid state between the A-stage and the fully-hardened C-stage. It is a state in which the compressive elastic modulus is less than that of the C-stage when it is hardened and gelled slightly.

藉此，以接著面5及第1相向面6各者由第1剝離薄片15及第2剝離薄片16支撐(保護)之狀態製造半導體元件封裝用接著薄片1。Thereby, each of the adhesive surface 5 and the first facing surface 6 is supported (protected) by the first release sheet 15 and the second release sheet 16 to produce a semiconductor device package adhesive sheet 1.

此半導體元件封裝用薄片1中，較佳為容許溶媒的殘留。換言之，半導體元件封裝用薄片1係含有殘留溶媒。以往，殘留溶媒為半導體元件封裝用薄片1中不佳之成分，而於一實施形態中，許容殘留溶媒反而較佳。In this semiconductor device package sheet 1, it is preferable to allow a solvent to remain. In other words, the semiconductor device package sheet 1 contains a residual solvent. In the past, the residual solvent was an unfavorable component in the semiconductor device packaging sheet 1, but in one embodiment, it is better to allow a residual solvent.

殘留溶媒係包含例如清漆調製時追加摻合之溶媒，及偶合劑與空氣中的水分進行水解反應而生成的醇(甲醇、乙醇等的ROH(參照下式(2))等。The residual solvent system includes, for example, a solvent that is additionally blended during the preparation of the varnish, and an alcohol (ROH (such as methanol, ethanol, etc.) (refer to the following formula (2))) generated by the hydrolysis reaction of the coupling agent with moisture in the air.

此外，偶合劑的水解反應係以下述式(2)表示。The hydrolysis reaction of the coupling agent is represented by the following formula (2).

R’4-n Si-ORn +nH2 O→R’4-n Si-OHn +nROH (2)
式(2)中，R、R’及n係與上述式(1)所例示者相同。R ' 4-n Si-OR n + nH 2 O → R' 4-n Si-OH n + nROH (2)
In formula (2), R, R 'and n are the same as those exemplified in the above formula (1).

殘留溶媒之於半導體元件封裝用接著薄片1中的比例，以質量基準計例如為5ppm以上，較佳為10ppm以上，更佳為20ppm以上，再更佳為30ppm以上；又，例如為500ppm以下，較佳為200ppm以下。The proportion of the residual solvent in the adhesive sheet 1 for semiconductor element packaging is, for example, 5 ppm or more, preferably 10 ppm or more, more preferably 20 ppm or more, and even more preferably 30 ppm or more on a mass basis; and, for example, 500 ppm or less, It is preferably 200 ppm or less.

殘留溶媒的比例若為上述下限以上，則可發生以下所說明之所要量的排氣，而提升接著面5對基板2之接著性。If the ratio of the residual solvent is greater than or equal to the above-mentioned lower limit, the required amount of exhaust gas can be generated as described below, and the adhesion of the bonding surface 5 to the substrate 2 can be improved.

殘留溶媒的比例係基於GC-MS的甲基乙基酮換算來測定，其細節係於後述實施例中說明。The ratio of the residual solvent is measured based on GC-MS methyl ethyl ketone conversion, and details thereof will be described in Examples described later.

而且，相對於加熱前的半導體元件封裝用接著薄片1，此半導體元件封裝用薄片1於150℃下加熱30分鐘時之排氣的發生量，以質量基準計為500ppm以上，較佳為750ppm，更佳為1,000ppm以上，再更佳為1,250ppm以上，再佳為1,300ppm以上，再佳為1,400ppm以上，再佳為1,500ppm以上；又，例如為10,000ppm以下，較佳為5,000ppm以下。In addition, the amount of exhaust gas generated when the semiconductor device package bonding sheet 1 before heating is heated at 150 ° C. for 30 minutes is 500 ppm or more, preferably 750 ppm, on a mass basis. More preferably, it is 1,000 ppm or more, even more preferably 1,250 ppm or more, even more preferably 1,300 ppm or more, even more preferably 1,400 ppm or more, even more preferably 1,500 ppm or more; and, for example, 10,000 ppm or less, and preferably 5,000 ppm or less .

上述加熱條件(於150℃下加熱30分鐘)係用來使半導體元件封裝用薄片1完全硬化而獲得硬化接著薄片10的條件之一例，具體而言，亦為用來獲得接著(接觸)於基板2之硬化接著薄片10的條件之一例。The above heating conditions (heating at 150 ° C. for 30 minutes) are examples of conditions for completely curing the semiconductor device package sheet 1 to obtain a cured adhesive sheet 10. Specifically, the heating conditions are also used to obtain (contact) the substrate. 2 is an example of the conditions for curing and bonding the sheet 10.

傳統上，排氣係於由半導體元件封裝用薄片1獲得硬化接著薄片10時發生，屬不佳之成分；而於此一實施形態中，反而需要發生大量排氣。Traditionally, exhaust gas is generated when the semiconductor device package sheet 1 is hardened and then the sheet 10 is a bad component. However, in this embodiment, a large amount of exhaust gas needs to be generated instead.

排氣係於上述之加熱條件(具體而言為用以獲得硬化接著薄片10之加熱條件)中由半導體元件封裝用薄片1(詳言之為由半導體元件封裝用薄片1轉移至硬化接著薄片10的途中之薄片或者硬化接著薄片10)所發生之低分子量(例如為300以下，較佳為200以下；又，例如為20以上，較佳為50以上的低分子量)的有機氣體。The exhaust gas is transferred from the semiconductor device packaging sheet 1 (specifically, the semiconductor device packaging sheet 1 to the hardened bonding sheet 10) under the heating conditions described above (specifically, the heating conditions for obtaining the cured bonding sheet 10). Organic gas having a low molecular weight (for example, 300 or less, preferably 200 or less; and, for example, 20 or more, and preferably 50 or more) occurring on the way of the sheet or the hardened adhesive sheet 10).

具體而言，排氣係包含例如上述之源自主劑之氣體、源自偶合劑之氣體、源自殘留溶媒之氣體(源於殘留溶媒之溶媒氣體)等。Specifically, the exhaust system includes, for example, the gas derived from the above-mentioned autonomous agent, the gas derived from the coupling agent, the gas derived from the residual solvent (the solvent gas derived from the residual solvent), and the like.

排氣係以驅氣及集氣氣相層析儀測定，其詳細的條件係於後述之實施例詳細敘述。Exhaust gas is measured by a purging and gas-collecting gas chromatograph, and detailed conditions thereof are described in detail in Examples described later.

半導體元件封裝用接著薄片1的厚度不特別限定，例如為100μm以上；又，例如為2000μm以下。The thickness of the semiconductor device package adhesive sheet 1 is not particularly limited, and is, for example, 100 μm or more; and, for example, 2000 μm or less.

其次，茲說明使用此半導體元件封裝用接著薄片1來封裝半導體元件3，而製造半導體元件封裝體4的方法。Next, a method of manufacturing a semiconductor element package 4 by using this semiconductor element package bonding sheet 1 to package a semiconductor element 3 will be described.

製造半導體元件封裝體4之方法係具備：準備半導體元件3之步驟(參照圖2A)；準備半導體元件封裝用接著薄片1之步驟(參照圖1及圖2A)；及藉由半導體元件封裝用接著薄片1封裝半導體元件3，而得到半導體元件封裝體4之步驟(參照圖2B)。The method for manufacturing the semiconductor element package 4 includes: a step of preparing a semiconductor element 3 (see FIG. 2A); a step of preparing a wafer 1 for a semiconductor element package (see FIGS. 1 and 2A); The step of packaging the semiconductor element 3 with the sheet 1 to obtain a semiconductor element package 4 (see FIG. 2B).

於此方法中，係如圖2A所示，首先，準備半導體元件3。In this method, as shown in FIG. 2A, first, a semiconductor element 3 is prepared.

作為半導體元件3，不特別限定，可舉出各種半導體元件。又，半導體元件3係例如具有朝面方向延伸的略平板形狀。半導體元件3之厚度方向的一方之面(下表面)上，於面方向隔著間隔設有配置的多個端子(未圖示)。The semiconductor element 3 is not particularly limited, and various semiconductor elements can be mentioned. The semiconductor element 3 has, for example, a substantially flat plate shape extending in a planar direction. On one surface (lower surface) of the semiconductor element 3 in the thickness direction, a plurality of terminals (not shown) are arranged at intervals in the surface direction.

半導體元件3係構裝於基板2的被接著面8(上表面)(後述)。具體而言，半導體元件3係經由上述端子，例如對基板2進行覆晶安裝。The semiconductor element 3 is mounted on an adhered surface 8 (upper surface) of the substrate 2 (described later). Specifically, the semiconductor element 3 is, for example, a flip-chip mounting of the substrate 2 through the terminals.

基板2係具有朝面方向延伸的略平坦形狀之構裝基板。又，基板2係具有構裝半導體元件3的被接著面8(上表面)；及與被接著面8於厚度方向隔著間隔地配置的第2相向面9。The substrate 2 is a structural substrate having a substantially flat shape extending in a planar direction. The substrate 2 includes a bonding surface 8 (upper surface) on which the semiconductor element 3 is mounted, and a second facing surface 9 disposed at intervals from the bonding surface 8 in the thickness direction.

被接著面8係接觸硬化接著薄片10之接著面5而接著的面，具有沿著面方向之平面。又，被接著面8係構裝半導體元件3的構裝面，具有包圍多個半導體元件3的大小。換言之，基板2的被接著面8係具有俯視下與半導體元件3重疊的重疊區域11，及未與半導體元件3重疊而由基板2露出，而直接接著於硬化接著薄片10的被接著區域(露出區域)12。被接著面8係於重疊區域11具備對應半導體元件3之端子(未圖示)的基板端子(未圖示)。此外，圖2A及圖2B中，雖未圖示，重疊區域11係與半導體元件3的下表面於厚度方向隔著微小間隙地配置。The adhered surface 8 is a surface that is contact-cured and adhered to the adhesive surface 5 of the sheet 10 and has a plane along the planar direction. The bonding surface 8 is a mounting surface on which the semiconductor element 3 is mounted, and has a size that surrounds the plurality of semiconductor elements 3. In other words, the bonded surface 8 of the substrate 2 has an overlapping region 11 overlapping the semiconductor element 3 in a plan view, and is exposed from the substrate 2 without overlapping the semiconductor element 3, and directly adheres to the bonded region 10 of the hardened adhesive sheet 10 (exposed Zone) 12. The bonding surface 8 is a substrate terminal (not shown) provided with a terminal (not shown) corresponding to the semiconductor element 3 in the overlap region 11. In addition, although not shown in FIGS. 2A and 2B, the overlapping region 11 is arranged with a small gap in the thickness direction from the lower surface of the semiconductor element 3.

第2相向面9係平行於被接著面8，具有沿著面方向之平面。The second facing surface 9 is parallel to the adhered surface 8 and has a plane along the plane direction.

就此方法，係另外如圖1及圖2A所示，準備半導體元件封裝用接著薄片1。具體而言，係如圖1之箭號及假想線所示，將第1剝離薄片15從半導體元件封裝用接著薄片1的接著面5剝離。In this method, as shown in FIGS. 1 and 2A, a bonding sheet 1 for packaging a semiconductor device is prepared. Specifically, as shown by an arrow and an imaginary line in FIG. 1, the first peeling sheet 15 is peeled from the bonding surface 5 of the bonding sheet 1 for a semiconductor element package.

如圖2A之箭號及圖2B所示，其後，將半導體元件封裝用接著薄片1，以其接著面5接觸半導體元件3之厚度方向另一面(上表面)的方式配置於半導體元件3上。As shown by the arrow of FIG. 2A and FIG. 2B, the semiconductor element packaging adhesive sheet 1 is then placed on the semiconductor element 3 so that its adhesive surface 5 contacts the other surface (upper surface) of the semiconductor element 3 in the thickness direction. .

如圖2B所示，接著，藉由半導體元件封裝用接著薄片1封裝半導體元件3。As shown in FIG. 2B, the semiconductor element 3 is then packaged by a semiconductor element packaging adhesive sheet 1.

例如，使用具備下板及上板的平板壓機(未圖示)，將半導體元件封裝用接著薄片1加熱及加壓，而以半導體元件封裝用接著薄片1封裝半導體元件3。For example, a flat plate press (not shown) including a lower plate and an upper plate is used to heat and press the bonding sheet 1 for semiconductor element packaging, and to package the semiconductor element 3 with the bonding sheet 1 for semiconductor element packaging.

又，藉由上述之加熱，半導體元件封裝用接著薄片1即熱硬化。具體而言，暫時軟化後，半導體元件封裝用接著薄片1之接著組成物便完全硬化(進行C-階段化)。Furthermore, by the above-mentioned heating, the bonding sheet 1 for semiconductor element packaging is thermally cured. Specifically, after temporarily softening, the bonding composition of the bonding sheet 1 for semiconductor element packaging is completely hardened (C-staged).

加熱條件係使接著組成物完全硬化之條件。具體而言，加熱溫度例如為85℃以上，較佳為100℃以上；又，例如為125℃以下，較佳為110℃以下。加熱時間例如為10分鐘以上，較佳為30分鐘以上；又，例如為300分鐘以下，較佳為180分鐘以下。壓力不特別限定，例如為0.1MPa以上，較佳為0.5MPa以上；又，例如為10MPa以下，較佳為5MPa以下。The heating conditions are conditions for completely curing the adhesive composition. Specifically, the heating temperature is, for example, 85 ° C or higher, preferably 100 ° C or higher; and, for example, 125 ° C or lower, preferably 110 ° C or lower. The heating time is, for example, 10 minutes or more, preferably 30 minutes or more; and, for example, 300 minutes or less, and preferably 180 minutes or less. The pressure is not particularly limited, and is, for example, 0.1 MPa or more, preferably 0.5 MPa or more; and, for example, 10 MPa or less, and preferably 5 MPa or less.

半導體元件封裝用接著薄片1經暫時軟化，即會埋覆半導體元件3。換言之，半導體元件3便由半導體元件封裝用接著薄片1包埋。When the bonding sheet 1 for semiconductor element packaging is temporarily softened, the semiconductor element 3 is buried. In other words, the semiconductor element 3 is embedded in the semiconductor element packaging adhesive sheet 1.

半導體元件封裝用接著薄片1的接著面5被覆半導體元件3的上表面及周側面，同時觸及被接著面8的被接著區域12。The bonding surface 5 of the bonding sheet 1 for semiconductor element packaging covers the upper surface and the peripheral side surface of the semiconductor element 3, and simultaneously touches the bonding region 12 of the bonding surface 8.

藉此，半導體元件3即藉由半導體元件封裝用接著薄片1而封裝。又，基板2的被接著區域12被半導體元件封裝用接著薄片1接觸(密接)。Thereby, the semiconductor element 3 is packaged by the semiconductor element packaging adhesive sheet 1. In addition, the adhered region 12 of the substrate 2 is contacted (closely adhered) by the semiconductor device package adhesive sheet 1.

此外，將半導體元件3進行封裝且接觸基板2的被接著區域12之半導體元件封裝用接著薄片1係既已藉由加熱而呈熱硬化(完全硬化)(C階段)狀態。因此，半導體元件封裝用接著薄片1便成為硬化接著薄片10。硬化接著薄片10為半導體元件封裝用接著薄片1之硬化物。In addition, the semiconductor element packaging adhesive sheet 1 for packaging the semiconductor element 3 and contacting the adhered region 12 of the substrate 2 has been thermally cured (completely cured) (C stage) by heating. Therefore, the adhesive sheet 1 for semiconductor element packaging becomes a cured adhesive sheet 10. The cured adhesive sheet 10 is a cured product of the adhesive sheet 1 for semiconductor element packaging.

透過上述之半導體元件封裝用接著薄片1的接著組成物完全硬化，硬化接著薄片10即顯現對基板2及半導體元件3之接著力。The adhesive composition of the adhesive sheet 1 for semiconductor element packaging described above is completely cured, and the adhesive force to the substrate 2 and the semiconductor element 3 is developed by curing the adhesive sheet 10.

如圖2B之箭號所示，其後，將第2剝離薄片16從硬化接著薄片10的第1相向面6剝離。換言之，使第1相向面6露出。As shown by an arrow in FIG. 2B, thereafter, the second release sheet 16 is peeled from the first facing surface 6 of the cured adhesive sheet 10. In other words, the first facing surface 6 is exposed.

藉此，可獲得具備基板2、半導體元件3及硬化接著薄片10的半導體元件封裝體4(硬化接著構造體20)。As a result, a semiconductor element package 4 (cured adhesive structure 20) including the substrate 2, the semiconductor element 3, and the cured adhesive sheet 10 can be obtained.

而且，由於此半導體元件封裝用薄片1含有接著組成物，因此對基板2之接著性優良。Moreover, since this semiconductor device package sheet 1 contains an adhesive composition, it has excellent adhesion to the substrate 2.

又，由於此半導體封裝用接著薄片1於150℃下加熱30分鐘時之排氣的發生量為上述下限以上，因此，可藉由所述足量之排氣而提升半導體元件封裝用接著薄片1之硬化物的硬化接著薄片10對基板之接著性。In addition, since the amount of exhaust gas generated when the adhesive sheet 1 for semiconductor packaging is heated at 150 ° C. for 30 minutes is equal to or more than the above lower limit, the adhesive sheet 1 for semiconductor element packaging can be improved by the sufficient amount of exhaust gas. Adhesiveness of the cured product of the cured sheet 10 to the substrate.

由此推測其主因在於，排氣，具體而言為包含源自主劑之氣體、源自偶合劑之氣體、源自殘留溶媒之氣體的排氣，尤為自主劑之氣體及源自偶合劑之氣體對基板2之構裝面8的露出區域12進行表面處理(於露出區域12彼此反應)，由此提升構裝面8與接著面5的接著力。It is speculated that the main reason is that the exhaust gas, specifically, the gas containing the source agent, the gas derived from the coupling agent, the gas derived from the residual solvent, especially the gas from the autonomous agent and the gas derived from the coupling agent Surface treatment is performed on the exposed regions 12 of the mounting surface 8 of the substrate 2 (reaction with each other in the exposed regions 12), thereby increasing the bonding force between the mounting surface 8 and the bonding surface 5.

＜變形例＞
就以下變形例，對於與上述一實施形態相同的構件及步驟，係附加相同的參照符號，並省略其詳細的說明。此外，就各變形例，除非特別明記，否則可發揮與一實施形態同樣的作用效果。而且，一實施形態及變形例可適宜組合。＜ Modifications ＞
In the following modifications, the same components and steps as those of the above-mentioned embodiment are denoted by the same reference numerals, and detailed descriptions thereof are omitted. In addition, each modification can exhibit the same functions and effects as those of the first embodiment unless it is specifically noted. Moreover, an embodiment and a modification can be combined suitably.

雖未圖示，惟亦可藉由半導體元件封裝用接著薄片1來封裝多個半導體元件3。此時，係將封裝有多個半導體元件3的硬化接著薄片10以切割機等進行切斷加工。Although not shown, a plurality of semiconductor elements 3 may be packaged by a semiconductor element packaging adhesive sheet 1. At this time, the cured adhesive sheet 10 in which the plurality of semiconductor elements 3 are packaged is cut with a cutter or the like.

此外，於一實施形態中，作為封裝用接著薄片之一例係舉出半導體元件封裝接著用薄片1來封裝作為電子元件之一例的半導體元件3，但不限定於此，例如，雖未圖示，惟亦可為供封裝其他電子元件的電子元件封裝用接著薄片。此時，可藉由電子元件封裝用接著薄片來封裝電子元件，而得到電子元件封裝體。

實施例In addition, in one embodiment, as an example of the bonding sheet for packaging, a semiconductor element package is used and then a semiconductor element 3 as an example of an electronic element is packaged with the sheet 1, but it is not limited to this. For example, although not shown, However, it may also be a bonding sheet for packaging electronic components for packaging other electronic components. At this time, an electronic element package can be obtained by packaging the electronic element with an adhesive sheet for electronic element packaging.

Examples

以下示出實施例及比較例，對本發明更具體地加以說明。此外，本發明不受實施例及比較例任何限定。此外，以下記載中所使用之摻合比例(比例)、物性值、參數等具體之數值可替換為上述之「實施方式」中所記載，且對應於彼等之摻合比例(比例)、物性值、參數等該記載之上限(以「以下」、「未滿」所定義之數值)或下限(以「以上」、「超過」所定義之數值)。Examples and comparative examples are shown below to describe the present invention more specifically. In addition, this invention is not limited at all by an Example and a comparative example. In addition, specific numerical values such as the blending ratio (ratio), physical property values, and parameters used in the following description may be replaced with those described in the above-mentioned "Embodiment" and correspond to their blending ratios (ratio) and physical properties. The upper limit (values defined by "below" and "underfilled") or the lower limit (values defined by "above" and "exceeded") of the records such as values and parameters.

以下示出實施例及比較例中所使用之各成分、薄片等。The components, flakes, and the like used in the examples and comparative examples are shown below.

環氧樹脂：新日鐵化學公司製YSLV-80XY (熱硬化性成分)(雙酚F型環氧樹脂(2官能環氧樹脂)、環氧當量200g/eq.軟化點80℃)
硬化劑：群榮化學公司製LVR-8210DL(熱硬化性成分)(酚醛清漆型酚樹脂、環氧樹脂硬化劑、羥基當量：104g/eq.、軟化點：60℃)
硬化促進劑：四國化成工業公司製2PHZ-PW(熱硬化性成分)(2-苯基-4,5-二羥基甲基咪唑)、環氧樹脂硬化促進劑
第1填充劑：Denka公司製FB-8SM(球狀熔融二氧化矽粉末(無機填充劑)、平均粒徑15μm)
第2填充劑：將Admatechs公司製SC220G-SMJ(平均粒徑0.5μm)以3-甲基丙烯醯氧丙基三甲氧基矽烷(信越化學公司製之製品名：KBM-503)進行表面處理之無機填充劑。相對於100質量份的SC220G-SMJ以1質量份的矽烷偶合劑進行表面處理之無機填充劑。Epoxy resin: YSLV-80XY (thermosetting component) manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F-type epoxy resin (bifunctional epoxy resin), epoxy equivalent 200g / eq. Softening point 80 ° C)
Hardener: LVR-8210DL (thermosetting component) manufactured by Qunrong Chemical Co., Ltd. (Novolac phenol resin, epoxy resin hardener, hydroxyl equivalent: 104g / eq., Softening point: 60 ° C)
Hardening accelerator: 2PHZ-PW (thermosetting component) (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd., epoxy resin hardening accelerator, first filler: manufactured by Denka Corporation FB-8SM (spherical fused silica powder (inorganic filler), average particle size 15 μm)
Second filler: SC220G-SMJ (average particle size: 0.5 μm) manufactured by Admatechs Co., Ltd. was surface-treated with 3-methacryloxypropyltrimethoxysilane (product name: Shin-Etsu Chemical Co., Ltd. KBM-503) Inorganic filler. An inorganic filler that is surface-treated with 1 part by mass of a silane coupling agent with respect to 100 parts by mass of SC220G-SMJ.

矽烷偶合劑：信越化學公司製KBM-403(含有環氧基之偶合劑)(3-環氧丙氧基丙基三甲氧基矽烷)
熱塑性樹脂：根上工業公司製HME-2006M，含有羧基的丙烯酸酯共聚物，重量平均分子量：60萬、固含量濃度20質量%之甲基乙基酮溶液
顏料：三菱化學公司製＃20(碳黑)
溶媒：甲基乙基酮Silane coupling agent: KBM-403 (coupling agent containing epoxy group) (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
Thermoplastic resin: HME-2006M manufactured by Genjo Industrial Co., a carboxyl group-containing acrylate copolymer, weight average molecular weight: 600,000, methyl ethyl ketone solution with a solid content concentration of 20% by mass, pigment: Mitsubishi Chemical Corporation # 20 (carbon black )
Vehicle: methyl ethyl ketone

實施例1～4及比較例1～2
依循表1所記載之摻合配方，將各成分溶解及分散於甲基乙基酮，而得到清漆。Examples 1 to 4 and Comparative Examples 1 to 2
Each component was dissolved and dispersed in methyl ethyl ketone according to the blending formula described in Table 1 to obtain a varnish.

將清漆塗佈於第1剝離薄片15的表面後，以110℃加以乾燥5分鐘。藉此，製成厚度260μm的半導體元件封裝用接著薄片1。其後，在半導體元件封裝用接著薄片1的第1相向面6配置第2剝離薄片16。The varnish was applied to the surface of the first release sheet 15 and then dried at 110 ° C. for 5 minutes. Thereby, a bonding sheet 1 for a semiconductor element package having a thickness of 260 μm was produced. Thereafter, a second release sheet 16 is disposed on the first facing surface 6 of the bonding sheet 1 for a semiconductor element package.

藉此，分別在接著面5及第1相向面6配置第1剝離薄片15及第2剝離薄片16各者，而得到處於B階段的半導體元件封裝用薄片1。Thereby, each of the first release sheet 15 and the second release sheet 16 is disposed on the adhesive surface 5 and the first facing surface 6, respectively, to obtain a semiconductor element packaging sheet 1 in a B stage.

[物性]
針對半導體元件封裝用薄片1，測定下述項目。將其結果記載於表1。[Physical properties]
For the semiconductor device package sheet 1, the following items were measured. The results are shown in Table 1.

(排氣的測定)
採取具有2mm見方大小的半導體元件封裝用薄片1作為試樣，將此試樣裝入管瓶中，秤量試樣的質量。接著，將試樣於150℃下加熱30分鐘。將於此期間由試樣所發生的排氣捕集至經冷卻的捕集管中，將其加熱，藉由連接於質譜儀的氣相層析儀(GC-MS)，根據以甲基乙基酮為標準物質的檢量線，算出捕集之全部排氣的質量。接著，以算出之排氣的質量除以裝入之半導體元件封裝用薄片1的質量所得的值作為排氣量(單位：ppm)而得(動態頂空注入分析法)。(Measurement of exhaust gas)
The semiconductor device packaging sheet 1 having a size of 2 mm square was taken as a sample, and this sample was placed in a vial, and the mass of the sample was measured. Next, the sample was heated at 150 ° C for 30 minutes. The exhaust gas generated from the sample during this period is trapped in a cooled trap tube, and it is heated. The gas chromatograph (GC-MS) connected to the mass spectrometer is based on methyl ethyl acetate. The ketone is a calibration curve of a standard substance, and the mass of the entire exhaust gas collected is calculated. Next, the value obtained by dividing the calculated mass of the exhaust gas by the mass of the semiconductor device package sheet 1 is set as the exhaust gas volume (unit: ppm) (dynamic headspace injection analysis method).

作為排氣濃縮裝置，係使用GL Sciences製MSTD-258M。As the exhaust gas concentrating device, MSTD-258M manufactured by GL Sciences was used.

作為排氣的捕集條件，係以腔室驅氣氣體流量為N2 氣體340mL/min、捕集時間30分鐘來實施。The trap conditions for the exhaust gas were carried out with a chamber purge gas flow rate of 340 mL / min of N 2 gas and a trap time of 30 minutes.

作為分析方法，係使用分析裝置之GC-MS；作為分析條件，管柱係使用J&W毛細管柱DB-5MS，管柱溫度取40℃保持3分鐘後，至220℃前係以升溫速度9℃/分進行升溫20分鐘，進而以升溫速度10℃/分，以8分鐘升溫至300℃，於300℃下保持3分鐘。As the analysis method, GC-MS was used as the analytical device. As the analysis conditions, J & W capillary column DB-5MS was used for the column. After the column temperature was maintained at 40 ° C for 3 minutes, the temperature was increased to 9 ° C / 220 ° C The temperature was raised for 20 minutes, and then the temperature was increased to 10 ° C./minute, and the temperature was increased to 300 ° C. in 8 minutes, and the temperature was maintained at 300 ° C. for 3 minutes.

注入口的溫度係設為250℃。The inlet temperature was set at 250 ° C.

載流氣體係使用He，流速為1.5mL/min，分流比取1：10。The carrier gas system uses He, the flow rate is 1.5 mL / min, and the split ratio is 1:10.

MS分析(質量分析)係使用分析裝置(Agilent公司製HP6890/5973-GC/MS)，根據電子離子化法來實施。MS analysis (mass analysis) was performed using an analysis device (HP6890 / 5973-GC / MS manufactured by Agilent Corporation) according to an electron ionization method.

檢測器的溫度係取230℃。The temperature of the detector was 230 ° C.

(殘留溶媒的測定)
根據基於GC-MS的甲基乙基酮換算之測定，測定半導體元件封裝用薄片1的殘留溶媒。(Determination of residual solvent)
The residual solvent of the semiconductor device package sheet 1 was measured by a GC-MS-based methyl ethyl ketone conversion measurement.

[硬化接著薄片的評定]
依循下述評定硬化接著薄片10的接著性(接著強度的測定)。[Evaluation of Hardened Adhesive Sheet]
The adhesiveness of the hardened adhesive sheet 10 (measurement of adhesive strength) was evaluated in accordance with the following evaluation.

如圖3A(剖面圖)及圖3B(俯視圖)所示，準備由長50mm、寬10mm、厚200μm之氧化鋁基板所構成的基板2。此外，基板2非為構裝半導體元件3，而是用來測定接著強度的測試基板。As shown in FIGS. 3A (cross-sectional view) and FIG. 3B (top view), a substrate 2 made of an alumina substrate having a length of 50 mm, a width of 10 mm, and a thickness of 200 μm is prepared. The substrate 2 is not a semiconductor device 3 but a test substrate for measuring the adhesion strength.

如圖3A之假想線及箭號所示，接著準備具有2mm見方大小的半導體元件封裝用薄片1，將半導體元件封裝用薄片1之接著面5貼附於基板2的表面。其次，於150℃下加熱30分鐘。藉此，將半導體元件封裝用薄片1接著固定於基板2。由此，製成具有半導體元件封裝用薄片1及基板2的硬化接著構造體20。As shown by an imaginary line and an arrow in FIG. 3A, a semiconductor element packaging sheet 1 having a size of 2 mm square is prepared next, and the bonding surface 5 of the semiconductor element packaging sheet 1 is attached to the surface of the substrate 2. Next, it heated at 150 degreeC for 30 minutes. Thereby, the semiconductor device package sheet 1 is subsequently fixed to the substrate 2. As a result, a cured bonding structure 20 having the semiconductor device package sheet 1 and the substrate 2 is produced.

其後，使用萬能型黏結強度試驗機(Nordson Advanced Technology公司製Dage4000)來測定硬化接著構造體20之半導體元件封裝用薄片1及基板2的剝離強度。如圖3A及圖3B所示，萬能型黏結強度試驗機係具備可沿縱向移動的量器30。量器30係於縱向其中一側具有可對硬化接著薄片10按壓的按壓面31(縱向的一方之面)。Then, the peeling strength of the semiconductor device package sheet 1 and the substrate 2 which were cured and adhered to the structure 20 was measured using a universal-type adhesive strength tester (Dage4000 manufactured by Nordson Advanced Technology). As shown in FIGS. 3A and 3B, the universal adhesive strength tester is provided with a measuring device 30 that can move in the longitudinal direction. The measuring device 30 has a pressing surface 31 (one surface in the vertical direction) that can press the hardened adhesive sheet 10 on one side in the vertical direction.

剝離強度的測定係將量器30，於硬化接著薄片10的縱向其中一側與基板2的表面隔著50μm的間隔(間隙)地配置。接著，一邊將量器30朝向硬化接著薄片10，朝縱向另一側移動，一邊將量器30的按壓面31抵接硬化接著薄片10的側面(下端部除外的部分)，接著將量器30朝向縱向另一側推壓(加壓)。The measurement of the peeling strength was performed by placing the measuring device 30 at a distance (gap) of 50 μm from the surface of the substrate 2 on one side in the longitudinal direction of the cured adhesive sheet 10. Next, while moving the measuring device 30 toward the hardening and bonding sheet 10 and moving the other side in the longitudinal direction, the pressing surface 31 of the measuring device 30 is brought into contact with the side surface of the hardening and bonding sheet 10 (except the lower end portion), and then Push (pressurize) towards the other side in the longitudinal direction.

然後，獲得硬化接著薄片10由基板2剝離時的強度(剪切強度)作為接著強度。Then, the strength (shear strength) when the cured adhesive sheet 10 was peeled from the substrate 2 was obtained as the adhesive strength.

同時，硬化接著薄片10由基板2剝離時，就破壞模式，係將硬化接著薄片10與基板2發生界面剝離者評為「○」；於硬化接著薄片10僅發生些微內聚破壞時評為「△」；於硬化接著薄片10發生內聚破壞時評為「×」。At the same time, when the hardened adhesive sheet 10 is peeled from the substrate 2, the failure mode is determined. The person who peeled the interface between the hardened adhesive sheet 10 and the substrate 2 is rated as "○". ";" When the cohesive failure of the hardened adhesive sheet 10 occurred.

表1中，若未特別記述時，數值為摻合份數。In Table 1, unless otherwise stated, the numerical value is the number of blending parts.

此外，上述說明係作為本發明所例示之實施形態提供，其僅為例示，不應限定性地解釋。由該技術領域之本業者所明瞭的本發明之變形例係包含於後述申請專利範圍。In addition, the above description is provided as an exemplary embodiment of the present invention, which is merely an example and should not be interpreted in a limited manner. Modifications of the present invention which are known to those skilled in the art are included in the scope of patent application to be described later.

1‧‧‧半導體元件封裝用接著薄片1‧‧‧ Adhesive sheet for semiconductor element packaging

2‧‧‧基板 2‧‧‧ substrate

3‧‧‧半導體元件 3‧‧‧Semiconductor element

4‧‧‧半導體元件封裝體 4‧‧‧Semiconductor element package

5‧‧‧接著面 5‧‧‧ continue

6‧‧‧第1相向面 6‧‧‧ the first facing

8‧‧‧被接著面 8‧‧‧ was followed

9‧‧‧第2相向面 9‧‧‧ 2nd facing

10‧‧‧硬化接著薄片 10‧‧‧ Hardened and flakes

11‧‧‧重疊區域 11‧‧‧ overlapping area

12‧‧‧被接著區域 12‧‧‧ followed area

15‧‧‧第1剝離薄片 15‧‧‧The first peeling sheet

16‧‧‧第2剝離薄片 16‧‧‧ 2nd release sheet

20‧‧‧硬化接著構造體 20‧‧‧ Hardened and bonded structure

30‧‧‧量器 30‧‧‧ Measuring device

31‧‧‧按壓面 31‧‧‧Pressing surface

圖1表示本發明之封裝用接著薄片之一實施形態的半導體元件封裝用接著薄片的剖面圖。FIG. 1 is a cross-sectional view of a bonding sheet for packaging a semiconductor device, which is an embodiment of a bonding sheet for packaging according to the present invention.

圖2A～圖2B表示使用圖1所示半導體元件封裝用接著薄片，將半導體元件進行封裝，同時接著於基板，而製造半導體元件封裝體之方法的步驟圖；圖2A表示分別準備半導體元件與半導體元件封裝用接著薄片之步驟；圖2B表示藉由半導體元件封裝用接著薄片將半導體元件進行封裝，同時接著於基板之步驟。 FIG. 2A to FIG. 2B show steps of a method for manufacturing a semiconductor element package by using the semiconductor element packaging bonding sheet shown in FIG. 1 to package a semiconductor element and then bonding it to a substrate; The step of bonding a wafer for element packaging; FIG. 2B shows the step of packaging a semiconductor element by a bonding wafer for a semiconductor element packaging, and then the step of bonding to a substrate.

圖3A～圖3B為實施例中之接著強度測定的示意圖；圖3A表示剖面圖，圖3B表示俯視圖。 FIG. 3A to FIG. 3B are schematic diagrams of adhesion strength measurement in the embodiment; FIG. 3A shows a cross-sectional view, and FIG. 3B shows a top view.

Claims (5)

一種封裝用接著薄片，其係將構裝於基板上之電子元件進行封裝，同時接著於前述基板之封裝用接著薄片，其特徵為： 含有接著組成物， 相對於加熱前之前述封裝用接著薄片而言，前述封裝用接著薄片於150℃下加熱30分鐘時之排氣的發生量為500ppm以上。An encapsulating adhesive sheet is used for encapsulating an electronic component constructed on a substrate, and at the same time adhering an encapsulating adhesive sheet to the aforementioned substrate, which is characterized in that: Contains an adhesive composition, The generation amount of the exhaust gas when the sealing adhesive sheet for packaging was heated at 150 ° C. for 30 minutes with respect to the sealing adhesive sheet before heating was 500 ppm or more. 如請求項1之封裝用接著薄片，其中，前述接著組成物含有熱硬化性成分、無機填充劑及偶合劑。The adhesive sheet for packaging according to claim 1, wherein the adhesive composition contains a thermosetting component, an inorganic filler, and a coupling agent. 如請求項2之封裝用接著薄片，其中，相對於前述熱硬化性成分及前述無機填充劑的總量100質量份而言，前述偶合劑之摻合份數為1質量份以上。The sealing sheet for encapsulation according to claim 2, wherein the blending amount of the coupling agent is 1 part by mass or more based on 100 parts by mass of the total amount of the thermosetting component and the inorganic filler. 如請求項2之封裝用接著薄片，其中，前述偶合劑為含有環氧基之矽烷偶合劑。The sealing sheet according to claim 2, wherein the coupling agent is a silane coupling agent containing an epoxy group. 如請求項1之封裝用接著薄片，其係含有殘留溶媒，其中，前述殘留溶媒之於封裝用接著薄片中的比例為5ppm以上。For example, the sealing sheet for packaging according to claim 1 contains a residual solvent, wherein the proportion of the residual solvent in the sealing sheet for packaging is 5 ppm or more.
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