TWI766069B - resin sheet - Google Patents

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TWI766069B
TWI766069B TW107124231A TW107124231A TWI766069B TW I766069 B TWI766069 B TW I766069B TW 107124231 A TW107124231 A TW 107124231A TW 107124231 A TW107124231 A TW 107124231A TW I766069 B TWI766069 B TW I766069B
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resin composition
resin
composition layer
resin sheet
mass
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TW201918509A (en
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渡邉康貴
根津裕介
杉野貴志
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日商琳得科股份有限公司
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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
    • 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
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J2463/00—Presence of epoxy resin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

本發明是一種樹脂薄片，是在半導體裝置的製造方法，用於密封電子零件的樹脂薄片，上述樹脂薄片，具備硬化性的樹脂組成物層，上述樹脂組成物層，由含有著色材料的樹脂組成物形成，上述著色材料，包含構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料、及絕緣性的金屬化合物的至少一方，上述樹脂組成物層硬化而成的硬化層，在波長1500～1000nm的光線穿透率在40%以下，波長800～400nm的光線穿透率在10%以下。根據該樹脂薄片，在所得半導體裝置，可達成電子零件優良的隱蔽性的同時，亦可抑制因來自外部電磁波的錯誤動作，使樹脂組成物層硬化而成的硬化層具有優良的絕緣性。The present invention is a resin sheet, a resin sheet for sealing electronic parts in a method of manufacturing a semiconductor device, the resin sheet, and a resin composition layer having curability, and the resin composition layer is composed of a resin containing a coloring material The above-mentioned coloring material includes at least one of a carbon-based material in which the ratio of carbon atoms constituting an aliphatic hydrocarbon group to all carbon atoms exceeds 3% by mass, and an insulating metal compound, and a hardened layer formed by hardening the above-mentioned resin composition layer , The transmittance of light with wavelengths of 1500 to 1000 nm is below 40%, and the transmittance of light with wavelengths of 800 to 400 nm is below 10%. According to this resin sheet, the obtained semiconductor device can achieve excellent concealability of electronic components, and can suppress malfunction due to external electromagnetic waves, and the cured layer formed by curing the resin composition layer has excellent insulating properties.

Description

樹脂薄片resin sheet

本發明是關於在半導體裝置的製造方法使用於密封電子零件的樹脂薄片。The present invention relates to a resin sheet used for sealing electronic parts in a method of manufacturing a semiconductor device.

先前在半導體裝置的製造方法，使用具有硬化性的樹脂組成物層的樹脂薄片，進行密封半導體晶片等的電子零件。例如，對設於基板上的電子零件，積層該樹脂薄片的樹脂組成物層之後，使該樹脂組成物層硬化形成硬化層，進行電子零件的密封。Conventionally, in the manufacturing method of a semiconductor device, electronic components, such as a semiconductor wafer, are encapsulated using a resin sheet having a curable resin composition layer. For example, after laminating the resin composition layer of the resin sheet on an electronic component provided on a substrate, the resin composition layer is cured to form a cured layer, and the electronic component is sealed.

例如，在專利文獻1，揭示如上所述的樹脂薄片的一例。在專利文獻1，由得到良好的雷射標記性的觀點，揭示可在樹脂組成物層含有顏料（專利文獻1的段落0055及0056），特別是在實施例，製造含有碳黑作為顏料的樹脂薄片（專利文獻1的表1）。 ［先前技術文獻］ ［專利文獻］For example, Patent Document 1 discloses an example of the above-mentioned resin sheet. In Patent Document 1, from the viewpoint of obtaining good laser marking properties, it is disclosed that a pigment can be contained in the resin composition layer (paragraphs 0055 and 0056 of Patent Document 1), and particularly in Examples, resins containing carbon black as a pigment are produced Sheet (Table 1 of Patent Document 1). [PRIOR ART DOCUMENTS] [PATENT DOCUMENTS]

專利文獻1︰日本特開2016-000784號公報Patent Document 1: Japanese Patent Application Laid-Open No. 2016-000784

［發明所欲解決的課題］[Problems to be solved by the invention]

但由於碳黑是導電性，故使用專利文獻1所揭示的樹脂薄片所形成的硬化層，無法具有充分絕緣性，在使用該樹脂薄片所形成的半導體裝置，可能發生短路所造成的錯誤動作，或發生絕緣破壞。However, since carbon black is conductive, the hardened layer formed using the resin sheet disclosed in Patent Document 1 cannot have sufficient insulating properties, and a semiconductor device formed using the resin sheet may malfunction due to a short circuit. or insulation damage occurs.

另一方面，使用不含碳黑的樹脂薄片製造半導體裝置時，難以良好地隱蔽密封的電子零件，而有損及所得半導體裝置外觀之虞。On the other hand, when a semiconductor device is produced using a resin sheet that does not contain carbon black, it is difficult to conceal the sealed electronic parts well, and the appearance of the obtained semiconductor device may be impaired.

此外，半導體裝置，有時因來自外部的電磁場而發生錯誤動作，而要求抑制如此的問題。In addition, a semiconductor device may malfunction due to an external electromagnetic field, and it is required to suppress such a problem.

本發明有鑑於如此的實際情況所完成，以提供可在所得到的半導體裝置達成電子零件優良的隱蔽性的同時，亦可抑制來自外部電磁波的錯誤動作，此外，使樹脂組成物層硬化而成的硬化層可成為具有優良絕緣性的樹脂薄片為目標。 ［用於解決課題的手段］The present invention has been made in view of such a situation, to provide a semiconductor device that can achieve excellent concealment of electronic components, and also to suppress malfunction from external electromagnetic waves, and further, to provide a resin composition layer cured by curing a resin composition layer. The hardened layer can be targeted as a resin sheet with excellent insulating properties. [Means for solving problems]

為達成上述目標，第1，本發明提供一種樹脂薄片，其特徵在於：其是在半導體裝置的製造方法，用於密封電子零件的樹脂薄片，上述樹脂薄片，具備硬化性的樹脂組成物層，上述樹脂組成物層，是由含有著色材料的樹脂組成物形成，上述著色材料，包含構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料、及絕緣性的金屬化合物的至少一方，使上述樹脂組成物層硬化而成的硬化層，在波長1500～1000nm的光線穿透率在40%以下，波長800～400nm的光線穿透率在10%以下（發明1）。In order to achieve the above object, firstly, the present invention provides a resin sheet, which is a resin sheet for sealing electronic parts in a manufacturing method of a semiconductor device, the resin sheet, and a resin composition layer having curability, The resin composition layer is formed of a resin composition containing a coloring material, and the coloring material contains a carbon-based material in which the ratio of carbon atoms constituting the aliphatic hydrocarbon group to all carbon atoms exceeds 3% by mass, and an insulating metal compound. At least one of the cured layers obtained by curing the resin composition layer has a light transmittance of 40% or less at a wavelength of 1500 to 1000 nm, and a light transmittance of 10% or less at a wavelength of 800 to 400 nm (Invention 1).

在關於上述發明（發明1）的樹脂薄片，藉由樹脂組成物層由含有上述著色材料的樹脂組成物所形成的同時，將該硬化該樹脂組成物層硬化而成的硬化層顯示上述光線穿透率，在所製造的半導體裝置，可達成電子零件優良的隱蔽性的同時，亦可抑制於來自外部電磁波的錯誤動作。再者，上述著色材料，由於具有良好的絕緣性，將含有該著色材料的樹脂組成物所成的樹脂組成物層硬化而成的硬化層亦具有良好的絕緣性，在使用上述樹脂薄片所製造的半導體裝置，可抑制因短路所造成的錯誤動作及發生絕緣破壞。With regard to the resin sheet of the above invention (Invention 1), the resin composition layer is formed of the resin composition containing the above-mentioned coloring material, and the cured layer obtained by curing the resin composition layer exhibits the above-mentioned light penetration. Transmittance, the manufactured semiconductor device can achieve excellent concealment of electronic components, and at the same time can suppress malfunction from external electromagnetic waves. Furthermore, since the above-mentioned coloring material has good insulating properties, a cured layer formed by hardening a resin composition layer formed of a resin composition containing the coloring material also has good insulating properties, and is produced by using the above-mentioned resin sheet. The semiconductor device can suppress malfunction and insulation breakdown caused by short circuit.

在上述發明（發明1），其中上述樹脂組成物中的上述著色材料的含量，以0.5質量%以上，5質量%以下為佳（發明2）。In the above invention (Invention 1), the content of the coloring material in the resin composition is preferably 0.5 mass % or more and 5 mass % or less (Invention 2).

在上述發明（發明1、2），其中上述著色材料以黑色為佳（發明3）。In the above inventions (Inventions 1 and 2), the coloring material is preferably black (Invention 3).

在上述發明（發明1～3），其中上述碳系材料的平均粒徑以0.1μm以上，10μm以下為佳（發明4）。In the above inventions (Inventions 1 to 3), the average particle diameter of the carbon-based material is preferably 0.1 μm or more and 10 μm or less (Invention 4).

在上述發明（發明1～3），其中上述金屬化合物的平均粒徑以10nm以上，500nm以下為佳（發明5）。In the above inventions (Inventions 1 to 3), the average particle diameter of the metal compound is preferably 10 nm or more and 500 nm or less (Invention 5).

在上述發明（發明1～5），其中上述金屬化合物是第4族元素的金屬的氮化物（發明6）。In the above inventions (Inventions 1 to 5), the metal compound is a nitride of a metal of a Group 4 element (Invention 6).

在上述發明（發明1～6），其中上述樹脂組成物，含有熱硬化性樹脂為佳（發明7）。In the above inventions (Inventions 1 to 6), the resin composition preferably contains a thermosetting resin (Invention 7).

在上述發明（發明1～7），其中上述樹脂組成物，含有熱塑性樹脂為佳（發明8）。In the above inventions (Inventions 1 to 7), the resin composition preferably contains a thermoplastic resin (Invention 8).

在上述發明（發明1～8），其中上述樹脂組成物，含有二氧化矽填充劑為佳（發明9）。In the above inventions (Inventions 1 to 8), the resin composition preferably contains a silica filler (Invention 9).

在上述發明（發明9），其中上述樹脂組成物中的上述二氧化矽填充劑的含量，以65質量%以上，95質量%以下為佳（發明10）。 ［發明的效果］In the above invention (Invention 9), the content of the silica filler in the resin composition is preferably 65% by mass or more and 95% by mass or less (Invention 10). [Effect of invention]

本發明的樹脂薄片，可在所得到的半導體裝置，達成電子零件優良的隱蔽性的同時，亦可抑制來自外部電磁波的錯誤動作，此外，使樹脂組成物層硬化而成的硬化層具有優良的絕緣性。The resin sheet of the present invention can achieve excellent concealability of electronic components in the obtained semiconductor device, and can suppress malfunction from external electromagnetic waves. In addition, the cured layer formed by curing the resin composition layer has excellent Insulation.

以下，說明關於本發明的實施形態。 1. 樹脂組成物層 關於本實施形態的樹脂薄片，具備硬化性樹脂組成物層。在此，所謂樹脂組成物層具有硬化性，是指樹脂組成物層可藉由加熱等而硬化。即，樹脂組成物層在構成樹脂薄片的狀態為未硬化。樹脂組成物層，可為熱硬化性，或活性能量線硬化性亦佳，惟以熱硬化性為佳。藉由具有熱硬化性，即使是難以對積層的樹脂組成物層照射能量線時，亦可良好地硬化該樹脂組成物層。Hereinafter, embodiments of the present invention will be described. 1. Resin composition layer The resin sheet of the present embodiment includes a curable resin composition layer. Here, that the resin composition layer has curability means that the resin composition layer can be cured by heating or the like. That is, the resin composition layer is not hardened in a state of constituting a resin sheet. The resin composition layer may be thermosetting or active energy ray hardening, but thermosetting is more preferable. By having thermosetting properties, even when it is difficult to irradiate the laminated resin composition layer with energy rays, the resin composition layer can be cured favorably.

在關於本實施形態的樹脂薄片，樹脂組成物層由含有著色材料的樹脂組成物形成。然後，該著色材料，包含構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料、及絕緣性的金屬化合物的至少一方。再者，在關於本實施形態的樹脂薄片，在使樹脂組成物層硬化而成的硬化層，在波長1500～1000nm的光線穿透率在40%以下，在波長800～400nm的光線穿透率在10%以下。In the resin sheet of the present embodiment, the resin composition layer is formed of a resin composition containing a coloring material. Then, the coloring material contains at least one of a carbon-based material in which the ratio of carbon atoms constituting the aliphatic hydrocarbon group to all carbon atoms exceeds 3 mass %, and an insulating metal compound. Furthermore, in the resin sheet of the present embodiment, in the cured layer formed by curing the resin composition layer, the light transmittance at a wavelength of 1500 to 1000 nm is 40% or less, and the light transmittance at a wavelength of 800 to 400 nm is 40% or less. below 10%.

藉由樹脂組成物層由含有上述著色材料的樹脂組成物形成的同時，使該樹脂組成物層硬化而成的硬化層顯示上述光線穿透率，藉此硬化層可良好地遮斷可見光，而可達成電子零件優良的隱蔽性。此外，由於硬化層亦可良好地遮斷誘發半導體裝置的錯誤動作的電磁波的穿透，故所製造的半導體裝置，可抑制來自外部的該電磁波所引起的錯誤動作。When the resin composition layer is formed of the resin composition containing the above-mentioned coloring material, the hardened layer formed by hardening the resin composition layer exhibits the above-mentioned light transmittance, whereby the hardened layer can block visible light well, and Excellent concealment of electronic parts can be achieved. In addition, since the hardened layer can also well block the penetration of electromagnetic waves that induce malfunctions of the semiconductor device, the manufactured semiconductor device can suppress malfunctions caused by the electromagnetic waves from the outside.

再者，由於上述的著色材料具有良好的絕緣性，故將含有該著色材料的樹脂組成物層硬化而成的硬化層亦成為具有良好的絕緣性之物。因此，使用上述樹脂薄片所製造的半導體裝置，可抑制短路所造成的錯誤動作及發生絕緣破壞。Furthermore, since the above-mentioned coloring material has good insulating properties, the cured layer obtained by curing the resin composition layer containing the coloring material also has good insulating properties. Therefore, in the semiconductor device manufactured using the above-mentioned resin sheet, malfunction due to short circuit and occurrence of insulation breakdown can be suppressed.

此外，藉由樹脂組成物層由含有上述著色材料的樹脂組成物形成，對使該樹脂組成物層硬化而成的硬化層進行雷射印刷時，該硬化層的表面成為容易吸收雷射的能量。藉此，可良好地進行打印，而達成優良的雷射標記性。In addition, since the resin composition layer is formed of the resin composition containing the above-mentioned coloring material, when the cured layer obtained by curing the resin composition layer is subjected to laser printing, the surface of the cured layer can easily absorb the energy of the laser beam . Thereby, printing can be performed well, and excellent laser marking properties can be achieved.

再者，在本實施形態的樹脂組成物，與上述著色材料一起，以含有熱硬化性樹脂、熱塑性樹脂及二氧化矽填充劑為佳，進一步含有硬化觸媒為佳。Furthermore, the resin composition of the present embodiment preferably contains a thermosetting resin, a thermoplastic resin, and a silica filler together with the above-mentioned coloring material, and further preferably contains a curing catalyst.

（1）著色材料 本實施形態的著色材料，包含構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料、及絕緣性的金屬化合物的至少一方。藉由使本實施形態的樹脂組成物層，由含有如此的著色材料的樹脂組成物所形成，可達成如上所述的優良的隱蔽性、遮斷誘發錯誤動作的電磁波的效果、優良的絕緣性比、及優良的雷射標記性。再者，由容易達成該等效果的觀點，上述碳系材料，以碳系顏料為佳。(1) Coloring Material The coloring material of the present embodiment contains at least one of a carbon-based material in which the ratio of carbon atoms constituting an aliphatic hydrocarbon group to all carbon atoms exceeds 3 mass %, and an insulating metal compound. By forming the resin composition layer of the present embodiment with a resin composition containing such a coloring material, the above-mentioned excellent concealability, the effect of blocking electromagnetic waves that induce malfunction, and excellent insulating properties can be achieved. ratio, and excellent laser marking. Furthermore, the carbon-based material is preferably a carbon-based pigment from the viewpoint of easily achieving these effects.

上述著色材料，以黑色為佳。藉此，使樹脂組成物層硬化而成的硬化層變成黑色，使硬化層容易滿足上述光線穿透率的同時，可製造具有所期望的外觀的半導體裝置。此外，藉由使硬化層為黑色，對該硬化層的表面雷射印刷時，可使列印的文字與其周圍的對比變得更明確，而雷射標記性變得更優良。The above-mentioned coloring material is preferably black. Thereby, the cured layer obtained by curing the resin composition layer is made black, and the cured layer can easily satisfy the above-mentioned light transmittance, and a semiconductor device having a desired appearance can be manufactured. In addition, by making the hardened layer black, when the surface of the hardened layer is laser-printed, the contrast between the printed character and its surroundings can be made clearer, and the laser marking property can be improved.

構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料之例，碳填充劑、焦炭、木炭、鑽石等，該等之中，由容易達成關於本實施形態的樹脂薄片的上述效果的觀點，以碳填充劑為佳。所謂碳填充劑，雖主要是具有碳原子的共軛系連接的構造，但具有該碳原子的共軛被脂肪烴基適度遮斷的構造的非晶質碳物質。碳填充劑，主要是藉由碳原子的共軛系，吸收既定波長的電磁波。因此，藉由使用碳填充劑作為著色材料，可得如上所述的優良隱蔽性、有效地遮斷誘發錯誤動作的電磁波及優良的雷射標記性的效果。再者，碳填充劑，碳原子的共軛被脂肪烴基遮斷，電子不容易在碳骨架上非局部化，而成為絕緣性優良。因此，藉由使用碳填充劑作為著色材料，使用關於本實施形態的樹脂薄片所形成的硬化層容易達成優良的絕緣性。Examples of carbon-based materials in which the ratio of carbon atoms constituting the aliphatic hydrocarbon group to all carbon atoms exceeds 3% by mass are carbon fillers, coke, charcoal, diamond, and the like. From the viewpoint of the above-mentioned effects, a carbon filler is preferable. The carbon filler is mainly an amorphous carbon material having a structure in which a conjugated system of carbon atoms is connected, but a structure in which the conjugation of the carbon atom is appropriately interrupted by an aliphatic hydrocarbon group. Carbon fillers absorb electromagnetic waves of a predetermined wavelength mainly through the conjugated system of carbon atoms. Therefore, by using the carbon filler as the coloring material, the above-mentioned effects of excellent concealability, effective blocking of electromagnetic waves that induce erroneous operations, and excellent laser marking properties can be obtained. Furthermore, in the carbon filler, the conjugation of carbon atoms is blocked by an aliphatic hydrocarbon group, and electrons are not easily delocalized on the carbon skeleton, so that they have excellent insulating properties. Therefore, by using a carbon filler as a coloring material, the hardened layer formed using the resin sheet according to the present embodiment can easily achieve excellent insulating properties.

再者，碳黑，是主要具有碳原子共軛的構造的結晶性物質。碳黑，雖有在其表面具有脂肪烴基的情形，但構成脂肪烴基的碳原子對全部碳原子的比例在3質量%以下。因此，通常，碳黑並不符合本實施形態的碳系材料。碳黑，構成脂肪烴基的碳原子對全部碳原子的比例在3質量%以下，由於具有碳原子充分連接的構造，故電子可在碳骨架上活躍地發生移動，顯示優良的導電性。因此，在具備含有碳黑的樹脂組成物層的先前的樹脂薄片，使該樹脂組成物層硬化而成的硬化層不具有絕緣性。因此，使用如此的先前的樹脂所製造的半導體裝置，有因短路而造成的錯誤動作，或發生絕緣破壞之虞。Furthermore, carbon black is a crystalline substance mainly having a structure in which carbon atoms are conjugated. Carbon black may have an aliphatic hydrocarbon group on its surface, but the ratio of carbon atoms constituting the aliphatic hydrocarbon group to all carbon atoms is 3 mass % or less. Therefore, carbon black is generally not suitable for the carbon-based material of the present embodiment. Carbon black has a carbon atom constituting an aliphatic hydrocarbon group in a ratio of 3 mass % or less to all carbon atoms, and has a structure in which carbon atoms are sufficiently connected, so that electrons can actively move on the carbon skeleton and exhibit excellent electrical conductivity. Therefore, in the conventional resin sheet including the resin composition layer containing carbon black, the cured layer obtained by curing the resin composition layer does not have insulating properties. Therefore, the semiconductor device manufactured using such a conventional resin may malfunction due to a short circuit, or may cause insulation breakdown.

碳系材料的平均粒徑，以10μm以下為佳，以5μm以下特別佳，進一步以3μm以下為佳。碳系材料的平均粒徑在10μm以下，則碳系材料的表面積會變得充分大，而可有效地吸收既定波長的電磁波。藉此可得如上所述的優良的隱蔽性、遮斷誘發錯誤動作的電磁波及優良的雷射標記性的效果。再者，碳系材料的平均粒徑的下限值，並無特別限定，例如，以0.1μm以上為佳，以0.5μm以上特別佳。再者，在本說明書的碳系材料的平均粒徑，以動態光散射法所測定之值，例如使用粒度分佈測定裝置（日機裝公司製，產品名「Nanotrac Wave-UT151」）測定。The average particle diameter of the carbon-based material is preferably 10 μm or less, particularly preferably 5 μm or less, and more preferably 3 μm or less. When the average particle diameter of the carbon-based material is 10 μm or less, the surface area of the carbon-based material becomes sufficiently large, and electromagnetic waves of a predetermined wavelength can be effectively absorbed. Thereby, the above-mentioned effects of excellent concealability, shielding of electromagnetic waves that induce erroneous operations, and excellent laser marking properties can be obtained. In addition, the lower limit value of the average particle diameter of the carbon-based material is not particularly limited, but, for example, it is preferably 0.1 μm or more, and particularly preferably 0.5 μm or more. In addition, the average particle diameter of the carbon-based material in this specification is measured by a dynamic light scattering method, for example, using a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name "Nanotrac Wave-UT151").

絕緣性的金屬化合物，只要是具有絕緣性的同時，亦可吸收既定的波長的電磁波，使關於本實施形態的樹脂薄片可達成如上所述的優良的隱蔽性及遮斷誘發錯誤動作的電磁波的效果，則並無限定。再者，二氧化矽(silica)是從金屬化合物去除。該絕緣性的金屬化合物之例，可列舉第4族元素金屬的氮化物、鐵及其他的第4週期過渡金屬的複合氧化物等。該等之中，由絕緣性優良的同時，亦可良好地吸收既定波長的電磁波的觀點，以4族元素金屬的氮化物為佳。As long as the insulating metal compound has insulating properties, it can also absorb electromagnetic waves of a predetermined wavelength, so that the resin sheet of this embodiment can achieve the above-mentioned excellent concealment and blocking of electromagnetic waves that induce malfunctions. The effect is not limited. Furthermore, silica is removed from the metal compound. Examples of the insulating metal compound include nitrides of metals of Group 4 elements, composite oxides of iron and other transition metals of the fourth period, and the like. Among these, from the viewpoint of being excellent in insulating properties and absorbing electromagnetic waves of a predetermined wavelength well, nitrides of metals of group 4 elements are preferable.

第4族元素金屬的氮化物，可舉鈦、鋯、鉿等的氮化物。特別是如上所述，由容易得到吸收既定波長的電磁波的效果的觀點，4族元素金屬的氮化物，以鈦的氮化物為佳，此外，由同樣的觀點，以第4族元素的金屬的氮化物、以第4族元素的金屬的氮化氧化物為佳。第4族元素的金屬氮化物之例，可舉氮氧化鈦、氮化鈦、氮氧化鋯、氮化鋯、氮氧化鉿、氮化鉿等，該等之中，由容易得到如上所述的吸收既定波長的電磁波的效果的觀點，使用氮氧化鈦為佳。The nitride of the group 4 element metal includes nitrides of titanium, zirconium, hafnium, and the like. In particular, as described above, from the viewpoint of easily obtaining the effect of absorbing electromagnetic waves of a predetermined wavelength, the nitride of the metal of the Group 4 element is preferably the nitride of titanium, and from the same viewpoint, the nitride of the metal of the Group 4 element is preferred. Nitrides and nitride oxides of metals of Group 4 elements are preferred. Examples of metal nitrides of Group 4 elements include titanium oxynitride, titanium nitride, zirconium oxynitride, zirconium nitride, hafnium oxynitride, hafnium nitride, and the like. Among these, the above-mentioned ones are easily obtained. From the viewpoint of the effect of absorbing electromagnetic waves of a predetermined wavelength, titanium oxynitride is preferably used.

在本實施形態的金屬化合物的絕緣性，只要本實施形態的硬化層顯示所期望的絕緣性，並無特別限定，該金屬化合物的體積電阻率，以1Ω‧cm以上為佳，以2Ω‧cm以上特別佳，進一步以2.5Ω‧cm以上為佳。藉由該體積電阻率在1Ω‧cm以上，本實施形態的硬化層可容易達成良好的絕緣性，所製造的半導體裝置具有更優良的性能。The insulating properties of the metal compound of the present embodiment are not particularly limited as long as the cured layer of the present embodiment exhibits desired insulating properties. The volume resistivity of the metal compound is preferably 1 Ω·cm or more, and 2 Ω·cm or more. The above is particularly preferable, and more preferably 2.5Ω·cm or more. When the volume resistivity is 1 Ω·cm or more, the cured layer of the present embodiment can easily achieve good insulating properties, and the manufactured semiconductor device has better performance.

金屬化合物的平均粒徑，以500nm以下為佳，以300nm以下特別佳，進一步以150nm以下為佳。金屬化合物的平均粒徑在500nm以下，則金屬化合物的表面積變得充分大，可有效吸收既定波長的電磁波。藉此，可有效地得到如上所述的優良的隱蔽性、遮斷誘發錯誤動作的電磁波及優良的雷射標記性的效果。再者，金屬化合物的平均粒徑的下限值，並無特別限定，例如以10nm以上為佳，以20nm以上更佳。再者，在本說明書的金屬化合物的平均粒徑，以動態光散射法所測定之值，例如使用粒度分佈測定裝置（日機裝公司製，產品名「Nanotrac Wave-UT151」）測定。The average particle diameter of the metal compound is preferably 500 nm or less, particularly preferably 300 nm or less, and more preferably 150 nm or less. When the average particle diameter of the metal compound is 500 nm or less, the surface area of the metal compound becomes sufficiently large and can effectively absorb electromagnetic waves of a predetermined wavelength. This makes it possible to effectively obtain the above-described effects of excellent concealability, shielding of electromagnetic waves that induce erroneous operations, and excellent laser marking properties. In addition, the lower limit value of the average particle diameter of a metal compound is not specifically limited, For example, 10 nm or more is preferable, and 20 nm or more is more preferable. In addition, the average particle diameter of the metal compound in this specification is the value measured by the dynamic light scattering method, for example, is measured using the particle size distribution analyzer (Nikiso Co., Ltd., product name "Nanotrac Wave-UT151").

以上所說明的著色材料，可以單獨使用1種，亦可以組合2種以上使用。The coloring materials described above may be used alone or in combination of two or more.

在樹脂組成物中的著色材料的含量，以0.5質量%以上為佳，以1.0質量%以上更佳。此外，該含量以5質量%以下為佳，以3質量%以下更佳。藉由使該含量在0.5質量%以上，可有效地得到如上所述的優良的隱蔽性、遮斷誘發錯誤動作的電磁波及優良的雷射標記性的效果。此外，藉由使該含量在5質量%以下，變得容易確保其他成分在在樹脂組成物的含量，容易形成具有所期望性質的樹脂組成物層。The content of the coloring material in the resin composition is preferably 0.5 mass % or more, more preferably 1.0 mass % or more. Moreover, this content is preferably 5 mass % or less, more preferably 3 mass % or less. By setting the content to 0.5 mass % or more, the above-mentioned effects of excellent concealability, electromagnetic wave blocking that induces malfunction, and excellent laser marking properties can be effectively obtained. Moreover, by making this content 5 mass % or less, it becomes easy to ensure the content of other components in a resin composition, and it becomes easy to form a resin composition layer which has desired properties.

（2）熱硬化性樹脂 在關於本實施形態的樹脂薄片，樹脂組成物含有熱硬化性樹脂為佳。藉此，可使該樹脂組成物所形成的樹脂組成物層良好地硬化，可將電子零件牢固的密封。熱硬化性樹脂，只要是可使樹脂組成物層硬化，並無特別限定，可使用例如，密封材通常含有的樹脂。具體可舉環氧樹脂、酚樹脂、三聚氰胺樹脂、尿素樹脂、聚酯樹脂、胺甲酸乙脂樹脂、丙烯酸樹脂、聚醯亞胺樹脂、苯並㗁樹脂、苯氧基樹脂、酸酐化合物、胺系化合物、萘酚系樹脂、活性酯系樹脂、苯並㗁系樹脂、氰酸酯系樹脂等，該等可以1種單獨或組合2種以上使用。該等之中使用環氧樹脂、酚樹脂，或該等的混合物。(2) Thermosetting resin In the resin sheet of the present embodiment, it is preferable that the resin composition contains a thermosetting resin. Thereby, the resin composition layer which consists of this resin composition can be hardened favorably, and an electronic component can be sealed firmly. The thermosetting resin is not particularly limited as long as it can harden the resin composition layer, and for example, a resin generally contained in a sealing material can be used. Specific examples include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, benzos resins, phenoxy resins, acid anhydride compounds, amines A type compound, a naphthol type resin, an active ester type resin, a benzodiazepine type resin, a cyanate ester type resin, etc., may be used alone or in combination of two or more types. Among these, epoxy resins, phenol resins, or mixtures of these are used.

環氧樹脂一般具有受到加熱會三維網狀化，形成堅固的硬化物的性質。如此的環氧樹脂，可使用習知的各種環氧樹脂，具體可舉雙酚A、雙酚F、間苯二酚、苯酚酚醛、甲酚酚醛等的酚類的縮水甘油醚；丁二醇、聚乙二醇、聚丙二醇等的醇類的縮水甘油醚；鄰苯二甲酸、間苯二甲酸、四氫化鄰苯二甲酸等的羧酸的縮水甘油醚；將鍵結在苯胺異三聚氰酸酯的氮原子的活性氫以縮水甘油基取代的縮水甘油型或烷基縮水甘油型的環氧樹脂；乙烯基環己烷二環氧化合物、3,4-環氧基環己基甲基-3,4-二環己酸酯、2-(3,4-環氧基)環己基-5,5-螺(3,4-環氧基)環己烷-間二噁烷等，將在分子內的碳-碳雙鍵鍵結，例如藉由氧化導入環氧基的所謂脂環型環氧化合物。其他，亦可使用具有，聯苯骨架、三苯基甲烷骨架、二環己二烯骨架、萘骨架等的環氧樹脂。該等環氧樹脂，可以1種單獨或組合2種以上使用。上述環氧樹脂之中，使用具有雙酚A的縮水甘油醚（雙酚A型環氧樹脂）、具有聯苯骨架的環氧樹脂（聯苯型環氧樹脂）、具有萘骨架的環氧樹脂（萘型環氧樹脂）或該等的組合為佳。Epoxy resins generally have the property of being three-dimensionally networked when heated to form a solid hardened product. As such epoxy resins, various conventional epoxy resins can be used, and specific examples include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolac, cresol novolac, and the like; butanediol; , glycidyl ethers of alcohols such as polyethylene glycol, polypropylene glycol, etc.; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; Glycidyl-type or alkyl-glycidyl-type epoxy resins in which the active hydrogen of the nitrogen atom of the cyanate ester is substituted with a glycidyl group; vinylcyclohexane diepoxide compound, 3,4-epoxycyclohexylmethyl group -3,4-dicyclohexanoate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. The carbon-carbon double bond in the molecule is, for example, a so-called alicyclic epoxy compound in which an epoxy group is introduced by oxidation. In addition, the epoxy resin which has a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, etc. can also be used. These epoxy resins can be used alone or in combination of two or more. Among the above epoxy resins, glycidyl ethers having bisphenol A (bisphenol A type epoxy resins), epoxy resins having biphenyl skeletons (biphenyl type epoxy resins), and epoxy resins having naphthalene skeletons are used (Naphthalene type epoxy resin) or a combination of these is preferred.

酚樹脂，可舉例如，雙酚A、四甲基雙酚A、二烯丙基雙酚A、雙苯酚、雙酚F、二烯丙基雙酚F、三苯甲烷型酚、四酚、酚醛型酚、甲酚酚醛樹脂、具有聯苯芳烷基骨架的酚（聯苯型酚）等，該等之中，使用聯苯型酚為佳。該等酚樹脂，可以1種單獨或組合2種以上使用。再者，使用環氧樹脂作為硬化性樹脂時，與環氧樹脂的反應性等的觀點，並用酚樹脂為佳。Phenol resins include, for example, bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, bisphenol, bisphenol F, diallyl bisphenol F, triphenylmethane-type phenol, tetraphenol, A novolac-type phenol, a cresol novolak resin, a phenol having a biphenyl aralkyl skeleton (biphenyl-type phenol), etc., among these, a biphenyl-type phenol is preferably used. These phenol resins may be used alone or in combination of two or more. Furthermore, when an epoxy resin is used as the curable resin, it is preferable to use a phenol resin in combination from the viewpoint of reactivity with the epoxy resin.

熱硬化性樹脂在樹脂組成物中的含量，以10質量%以上為佳，以15質量%以上特別佳，進一步以20質量%以上為佳。此外，該含量，以60質量%以下為佳，以50質量%以下特別佳，進一步以40質量%以下為佳。藉由使該含量，在10質量%以上，可使樹脂組成物層的硬化更充分，可更堅固地密封電子零件。此外，藉由使該含量在60質量%以下，可更加抑制樹脂組成物層在非預期階段的硬化，使儲存穩定性更優良。The content of the thermosetting resin in the resin composition is preferably 10% by mass or more, particularly preferably 15% by mass or more, and more preferably 20% by mass or more. In addition, the content is preferably 60 mass % or less, particularly preferably 50 mass % or less, and more preferably 40 mass % or less. By making this content 10 mass % or more, hardening of a resin composition layer can be made more sufficient, and an electronic component can be sealed more firmly. Moreover, by making this content 60 mass % or less, hardening of a resin composition layer in an unexpected stage can be suppressed more, and storage stability can be made more excellent.

（3）熱塑性樹脂 關於本實施形態的樹脂薄片，樹脂組成物進一步含有熱塑性樹脂為佳。藉此，容易將樹脂組成物層形成為薄片狀。熱塑性樹脂之例，可舉苯氧基系樹脂、聚乙烯醇縮醛樹脂、烯烴系樹脂、聚酯系樹脂、聚胺甲酸乙酯系樹脂、聚酯胺甲酸乙酯系樹脂、醯胺系樹脂、苯乙烯系樹脂、矽烷系樹脂、橡膠系樹脂等，該等可以1種單獨或組合2種以上使用。(3) Thermoplastic resin The resin sheet of the present embodiment preferably further contains a thermoplastic resin in the resin composition. Thereby, the resin composition layer can be easily formed into a sheet shape. Examples of thermoplastic resins include phenoxy-based resins, polyvinyl acetal resins, olefin-based resins, polyester-based resins, polyurethane-based resins, polyester urethane-based resins, and amide-based resins , styrene-based resin, silane-based resin, rubber-based resin, etc., these can be used alone or in combination of two or more.

上述苯氧基系樹脂，雖並無特別限定，可例示例如，雙酚A型、雙酚F型、雙酚A/雙酚F共聚合型、雙酚S型、雙酚苯乙酮型、酚醛型、茀型、二環戊二烯型、降莰烯型、萘型、蒽型、金剛烷型、萜烯型、三甲基環己烷型、二苯酚型、聯苯型等，該等之中，使用雙酚A型苯氧基樹脂為佳。Although the above-mentioned phenoxy-based resin is not particularly limited, for example, bisphenol A type, bisphenol F type, bisphenol A/bisphenol F copolymer type, bisphenol S type, bisphenol acetophenone type, Phenolic type, fentanyl type, dicyclopentadiene type, norbornene type, naphthalene type, anthracene type, adamantane type, terpene type, trimethylcyclohexane type, diphenol type, biphenyl type, etc. Among them, it is preferable to use a bisphenol A type phenoxy resin.

在樹脂組成物中的熱塑性樹脂的含量，以1質量%以上為佳，以3質量%以上特別佳，進一步以5質量%以上為佳。此外，該含量，以30質量%以下為佳，以20質量%以下，進一步以10質量%以下為佳。藉由使該含量在上述範圍，可更容易將樹脂組成物層形成為板片狀。The content of the thermoplastic resin in the resin composition is preferably 1 mass % or more, particularly preferably 3 mass % or more, and more preferably 5 mass % or more. Moreover, this content is preferably 30 mass % or less, 20 mass % or less, and more preferably 10 mass % or less. By making this content into the said range, it becomes easier to form a resin composition layer into a sheet shape.

（4）二氧化矽填充劑 關於本實施形態的樹脂薄片，樹脂組成物進一步含有二氧化矽填充劑為佳。藉此，使樹脂組成物層硬化而成的硬化層，可有效地發揮優良的機械強度。(4) Silica filler In the resin sheet of the present embodiment, it is preferable that the resin composition further contains a silica filler. Thereby, the cured layer formed by curing the resin composition layer can effectively exhibit excellent mechanical strength.

二氧化矽填充劑的形狀，可為粒狀、針狀、板狀、不定型等的任一，惟該等之中，以球狀為佳。The shape of the silica filler can be any of granular, needle-like, plate-like, and indeterminate shapes, but among them, spherical shape is preferred.

上述二氧化矽填充劑的平均粒徑，以0.01μm以上為佳，以0.1μm以上特別佳，進一步以0.3μm以上為佳。此外，上述二氧化矽填充劑的平均粒徑，以3.0μm以下為佳，以1.0μm以下特別佳。藉由使二氧化矽填充劑的平均粒徑在上述範圍，可使樹脂組成物層硬化而成的硬化層，可有效地發揮優良的機械強度。再者，在本說明書的二氧化矽填充劑的平均粒徑，以動態光散射法所測定之值，例如使用粒度分佈測定裝置（日機裝公司製，產品名「Nanotrac Wave-UT151」）測定。The average particle size of the silica filler is preferably 0.01 μm or more, particularly preferably 0.1 μm or more, and more preferably 0.3 μm or more. In addition, the average particle size of the silica filler is preferably 3.0 μm or less, particularly preferably 1.0 μm or less. By setting the average particle diameter of the silica filler within the above-mentioned range, the cured layer formed by curing the resin composition layer can effectively exhibit excellent mechanical strength. Furthermore, the average particle size of the silica filler in this specification is a value measured by a dynamic light scattering method, for example, using a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name "Nanotrac Wave-UT151"). .

此外，上述二氧化矽填充劑的最大粒徑，以0.05μm以上為佳，以0.5μm以上特別佳。此外，該最大粒徑，以5μm以下為佳，以3μm以下特別佳。藉由使二氧化矽填充劑的最大粒徑在上述範圍，容易在硬化層中填充二氧化矽填充劑，使硬化層具有更優良的機械強度。再者，在本說明書的二氧化矽填充劑的最大粒徑，是使用動態光散射法測定之值，例如可使用粒度分佈測定裝置（日機裝公司製，產品名「Nanotrac Wave-UT151」）測定。In addition, the maximum particle size of the silica filler is preferably 0.05 μm or more, particularly preferably 0.5 μm or more. In addition, the maximum particle diameter is preferably 5 μm or less, and particularly preferably 3 μm or less. By setting the maximum particle size of the silica filler within the above range, it is easy to fill the silica filler in the hardened layer, so that the hardened layer has better mechanical strength. In addition, the maximum particle size of the silica filler in this specification is the value measured by the dynamic light scattering method. For example, a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name "Nanotrac Wave-UT151") can be used. Determination.

關於本實施形態的樹脂薄片，二氧化矽填充劑以表面處理劑進行表面處理為佳。藉此，可改善二氧化矽填充劑在樹脂組成物中的分散性及填充性。特別是該表面處理劑的最小披覆面積，以未滿550m2 /g為佳，以520m2 /g以下特別佳，進一步以450m2 /g以下為佳，此外，表面處理劑的最小披覆面積，以100m2 /g以上為佳，以200m2 /g以上特別佳，進一步以300m2 /g以上為佳。藉由使表面處理劑的最小披覆面積在上述範圍，可使二氧化矽填充劑在樹脂組成物中的分散性及填充性更優良。Regarding the resin sheet of the present embodiment, it is preferable that the silica filler is surface-treated with a surface-treating agent. Thereby, the dispersibility and filling property of the silica filler in the resin composition can be improved. In particular, the minimum coating area of the surface treatment agent is preferably less than 550 m 2 /g, particularly preferably 520 m 2 /g or less, and more preferably 450 m 2 /g or less. In addition, the minimum coating area of the surface treatment agent is The area is preferably 100 m 2 /g or more, particularly preferably 200 m 2 /g or more, and more preferably 300 m 2 /g or more. By making the minimum coating area of the surface treatment agent within the above range, the dispersibility and filling property of the silica filler in the resin composition can be improved.

上述表面處理劑之例，可舉環氧基矽烷及乙烯基矽烷。該等之中，使用環氧基矽烷為佳。環氧基矽烷的具體例，可舉例如3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、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矽烷、2-(3,4-環氧環己基）乙基三甲氧基矽烷等。該等之中，使用3-環氧丙氧基丙基三甲氧基矽烷為佳。Examples of the above-mentioned surface treatment agent include epoxysilane and vinylsilane. Among these, epoxysilane is preferably used. Specific examples of epoxysilanes include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl Dimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Among these, 3-glycidoxypropyltrimethoxysilane is preferably used.

上述乙烯基矽烷的具體例，可舉例如，乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三氯矽烷、乙烯基三(2-甲氧基乙氧基）矽烷等。該等之中，使用乙烯基三甲氧基矽烷為佳。Specific examples of the above vinylsilane include vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(2-methoxysilane) ethoxy) silane, etc. Among these, vinyltrimethoxysilane is preferably used.

將二氧化矽填充劑以表面處理劑進行表面處理的方法，並無特別限定，能夠以一般的方法進行。例如，使用混合機，將未處理的二氧化矽填充劑在常溫攪拌，對此噴霧表面處理劑之後，進一步藉由攪拌既定時間進行表面處理。噴霧後的攪拌時間，例如以5分鐘以上，15分鐘以下為佳。再者，為使表面處理劑充分固定在二氧化矽填充劑，亦可在上述操作之後，將二氧化矽填充劑從混合機取出放置1天以上，此外，亦可進行輕微的加熱處理。此外，為均勻地進行表面處理，亦可在噴霧表面處理劑之後，進一步添加有機溶劑，進行上述攪拌。混合機，可使用習知的混合機，例如，V形混合器、螺帶式混合器、雙錐混合機等的混合器、亨舍爾攪拌機、混凝土攪拌機等的攪拌機、球磨機等，該等之中，使用攪拌機為佳。The method of surface-treating the silica filler with the surface-treating agent is not particularly limited, and it can be performed by a general method. For example, using a mixer, the untreated silica filler is stirred at normal temperature, and after spraying the surface treatment agent, the surface treatment is further performed by stirring for a predetermined time. The stirring time after spraying is preferably 5 minutes or more and 15 minutes or less, for example. Furthermore, in order to fully fix the surface treatment agent on the silica filler, the silica filler may be taken out from the mixer and left for more than one day after the above operation, and a slight heat treatment may also be performed. In addition, in order to uniformly perform surface treatment, after spraying the surface treatment agent, an organic solvent may be further added and the above-mentioned stirring may be performed. As the mixer, known mixers can be used, for example, mixers such as V-shaped mixers, ribbon mixers, double-cone mixers, etc., Henschel mixers, concrete mixers and other mixers, ball mills, etc., etc. , it is better to use a blender.

在樹脂組成物中的二氧化矽填充劑的含量，以65質量%以上為佳，以70質量%以上特別佳，進一步以72質量%以上為佳。此外，該含量以95質量%以下為佳，以90質量%以下特別佳，進一步以80質量%以下為佳。藉由使二氧化矽填充劑的含量在65質量%以上，能夠使樹脂組成物層硬化而成的硬化層具有更良好的機械強度。此外，藉由使二氧化矽填充劑的含量在95質量%以下，可使樹脂組成物層容易硬化，可使用樹脂薄片製造品質更佳的半導體裝置。The content of the silica filler in the resin composition is preferably 65% by mass or more, particularly preferably 70% by mass or more, and more preferably 72% by mass or more. Further, the content is preferably 95% by mass or less, particularly preferably 90% by mass or less, and more preferably 80% by mass or less. By making content of a silica filler 65 mass % or more, the hardened layer which hardened the resin composition layer can have more favorable mechanical strength. In addition, by setting the content of the silica filler to 95% by mass or less, the resin composition layer can be easily cured, and a semiconductor device of better quality can be produced using the resin sheet.

（5）硬化觸媒 關於本實施形態的樹脂薄片，樹脂組成物進一步含有硬化觸媒為佳。藉此可有效地進行熱硬化性樹脂的硬化反應，可更良好地硬化樹脂組成物層。硬化觸媒之例，可舉咪唑系硬化觸媒、胺系硬化觸媒、磷系硬化觸媒等。(5) Hardening Catalyst Regarding the resin sheet of the present embodiment, it is preferable that the resin composition further contains a hardening catalyst. Thereby, the hardening reaction of the thermosetting resin can be efficiently performed, and the resin composition layer can be hardened more favorably. Examples of the curing catalyst include imidazole-based curing catalysts, amine-based curing catalysts, phosphorus-based curing catalysts, and the like.

咪唑系硬化觸媒的具體例，可舉2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-苯基咪唑、2-苯基4-甲基咪唑、1-苄基-2-苯基咪唑、1,2-二甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二(羥基甲基)咪唑等，由反應性的觀點，使用2-乙基-4-甲基咪唑為佳。Specific examples of imidazole-based curing catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, etc., from the viewpoint of reactivity, 2-ethyl-4-methylimidazole was used Kilimidazole is preferred.

胺系硬化觸媒的具體例，可舉2,4-二胺基-6-(2'-甲基咪唑基-(1'))乙基-s-三嗪等的三嗪化合物、1,8-二氮雜二環[5,4,0]十一烯-7（DBU）、三伸乙二胺、苄基二甲基胺、三乙醇胺等的三級胺化合物。其中，以2,4-二胺基-6-(2'-甲基咪唑基-(1'）)乙基-s-三嗪為佳。Specific examples of the amine-based curing catalyst include triazine compounds such as 2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine, 1, Tertiary amine compounds such as 8-diazabicyclo[5,4,0]undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine, etc. Among them, 2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine is preferred.

此外，磷系硬化觸媒的具體例，可舉三苯膦、三丁膦、三(對甲基苯基)膦、三(壬基苯基)膦等。In addition, specific examples of the phosphorus-based curing catalyst include triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, tris(nonylphenyl)phosphine, and the like.

上述硬化觸媒，可以1種單獨使用，亦可並用2種以上。The said hardening catalyst may be used individually by 1 type, and may use 2 or more types together.

硬化觸媒在樹脂組成物中的含量，以0.01質量%以上為佳，以0.05質量%以上特別佳，進一步以0.1質量%以上為佳。此外，該含量以2.0質量%以下為佳，以1.5質量%以下特別佳，進一步以1.0質量以下為佳。藉由使該含量在上述範圍，可使樹脂組成物層更良好地硬化。The content of the curing catalyst in the resin composition is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. In addition, the content is preferably 2.0 mass % or less, particularly preferably 1.5 mass % or less, and more preferably 1.0 mass % or less. By making this content into the said range, a resin composition layer can be hardened more favorably.

（6）其他的成分 本實施形態的樹脂組成物，可進一步含有可塑劑、穩定劑、黏著賦予劑、偶合劑、帶電防止劑、抗氧化劑等。(6) Other components The resin composition of the present embodiment may further contain a plasticizer, a stabilizer, an adhesion imparting agent, a coupling agent, an antistatic agent, an antioxidant, and the like.

（7）樹脂組成物層的物性等 本實施形態的樹脂薄片，使樹脂組成物層硬化而成的硬化層，在波長1500～1000nm的光線穿透率在40%以下，以30%以下為佳，以20%以下特別佳。在波長1500～1000nm的光線穿透率超過40%，則該波長區域的光穿透硬化層，而到達存在於所製造的半導體裝置內的電子零件，而成為發生電子零件的錯誤動作的原因。特別是在波長1500～1000nm的光，由於屬於用於紅外線照相機及紅外線通信等的近紅外光的光，是在製造半導體裝置所使用的環境常用的光，上述光線穿透率超過40%時，無法充分抑制上述的錯誤動作。雖關於波長1500～1000nm的光線穿透率的下限值，並無特別限定，惟例如以1%以上為佳，以2%以上特別佳。再者，在本說明書，所謂「波長1500～1000nm的光線穿透率在40%以下」表示在波長1500～1000nm的全範圍，光線穿透率在40%以下的意思，別的類似的表示亦相同。上述波長1500～1000nm的光線穿透率的測定方法，如後述試驗例所述。(7) Physical properties, etc. of the resin composition layer In the resin sheet of the present embodiment, the cured layer formed by curing the resin composition layer has a light transmittance of 40% or less at wavelengths of 1500 to 1000 nm, preferably 30% or less. , 20% or less is particularly good. When the transmittance of light with a wavelength of 1500 to 1000 nm exceeds 40%, the light in this wavelength region penetrates the hardened layer and reaches the electronic components present in the manufactured semiconductor device, causing malfunction of the electronic components. In particular, light with a wavelength of 1500 to 1000 nm belongs to the near-infrared light used for infrared cameras, infrared communication, etc., and is commonly used in the environment used for manufacturing semiconductor devices. When the above-mentioned light transmittance exceeds 40%, The above-mentioned erroneous operation cannot be sufficiently suppressed. The lower limit value of the light transmittance with a wavelength of 1500 to 1000 nm is not particularly limited, but, for example, it is preferably 1% or more, and particularly preferably 2% or more. Furthermore, in this specification, the so-called "light transmittance with a wavelength of 1500 to 1000 nm is less than 40%" means that the light transmittance is less than 40% in the entire wavelength range of 1500 to 1000 nm, and other similar expressions are also used. same. The measurement method of the light transmittance at the wavelength of 1500 to 1000 nm is as described in the later-described test example.

在本實施形態的樹脂薄片，在硬化樹脂組成物層而成的硬化層，在波長800～400nm的光線穿透率，在10%以下，以5%以下為佳，以1%以下特佳。波長800～400nm的光是可見光，波長800～400nm的光線穿透率超過10%，則在製造的半導體裝置，可視認被密封的電子零件，而損及半導體裝置的外觀。關於波長800～400nm的光線穿透率的下限值，並無特別限定，惟例如以0.01%以上為佳，以0.1%以上特別佳。再者，在本說明書，所謂「波長800～400nm的光線穿透率在10%以下」的表現，指光線穿透率在波長800～400nm的全範圍均在10%以下，別的類似的表現亦相同。上述波長800～400nm的光線穿透率的測定方法，如後述試驗例所述。In the resin sheet of the present embodiment, the cured layer formed of the cured resin composition layer has a light transmittance at a wavelength of 800 to 400 nm of 10% or less, preferably 5% or less, and particularly preferably 1% or less. Light with a wavelength of 800 to 400 nm is visible light, and the transmittance of light with a wavelength of 800 to 400 nm exceeds 10%. In the manufactured semiconductor device, sealed electronic parts can be recognized, and the appearance of the semiconductor device is impaired. The lower limit value of the light transmittance with a wavelength of 800 to 400 nm is not particularly limited, but, for example, it is preferably 0.01% or more, and particularly preferably 0.1% or more. Furthermore, in this specification, the so-called "light transmittance with a wavelength of 800-400 nm is less than 10%" means that the light transmittance is less than 10% in the entire range of wavelength 800-400 nm, and other similar manifestations. The same is true. The measurement method of the light transmittance at the wavelength of 800 to 400 nm is as described in the later-described test example.

在本實施形態的樹脂組成物層的厚度，以20μm以上為佳，以50μm以上特別佳，進一步以100μm以上為佳。另一方面，樹脂組成物層的厚度，在1000μm以下，以500μm以下為佳，以300μm以下特別佳。藉由使樹脂組成物層的厚度在20μm以上，可使對電子零件的包埋性優良。此外，樹脂組成物層的厚度在1000μm以下，使用本實施形態的樹脂薄片容易使製造的半導體裝置小型化‧薄膜化。The thickness of the resin composition layer of the present embodiment is preferably 20 μm or more, particularly preferably 50 μm or more, and more preferably 100 μm or more. On the other hand, the thickness of the resin composition layer is 1000 μm or less, preferably 500 μm or less, and particularly preferably 300 μm or less. By setting the thickness of the resin composition layer to be 20 μm or more, the embedding property for electronic components can be excellent. In addition, the thickness of the resin composition layer is 1000 μm or less, and the use of the resin sheet of the present embodiment makes it easy to miniaturize and reduce the thickness of the semiconductor device to be manufactured.

2. 剝離薄片 關於本實施形態的樹脂薄片，亦可在樹脂組成物層的至少一方的面積層剝離薄片。剝離薄片的構成為任意，可舉例如聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯等的聚酯薄膜、聚丙烯、聚乙烯等的聚烯烴薄膜等的塑膠薄膜。在該等的剝離面（與樹脂薄片的樹脂組成物層接觸的面），施以剝離處理為佳。用於剝離處理的剝離劑，可舉例如聚矽氧系、氟系、長鏈烷基系等的剝離劑。2. Release sheet The resin sheet of the present embodiment may be a release sheet in at least one area layer of the resin composition layer. The structure of the release sheet is optional, and examples thereof include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polypropylene, polyethylene, and the like. plastic films such as polyolefin films. It is preferable to apply a peeling treatment to these peeling surfaces (surfaces that are in contact with the resin composition layer of the resin sheet). As the release agent used for the release treatment, for example, release agents such as polysiloxane-based, fluorine-based, and long-chain alkyl-based release agents can be exemplified.

關於剝離板片的厚度，並無特別限制，通常為20μm以上，250μm以下。The thickness of the peeling sheet is not particularly limited, but is usually 20 μm or more and 250 μm or less.

3. 樹脂薄片的製造方法 關於本實施形態的樹脂薄片，並無特別限定，例如調製含有上述樹脂組成物的塗層液，藉由塗佈該塗層液形成樹脂組成物層而製造樹脂薄片，或者亦可藉由將上述的樹脂組成物擠出成形，形成樹脂組成物層而製造樹脂薄片。3. Manufacturing method of resin sheet The resin sheet of the present embodiment is not particularly limited. For example, a coating liquid containing the above-mentioned resin composition is prepared, and a resin composition layer is formed by applying the coating liquid to manufacture a resin sheet. Alternatively, a resin sheet may be produced by extruding the above-mentioned resin composition to form a resin composition layer.

藉由塗佈上述塗層液形成樹脂組成物層的方法，可例如，調製含有樹脂組成物、及根據所期望進一步含有溶劑或分散劑的塗層液，在剝離薄片的剝離面上，以模具塗佈機、淋幕塗佈機、噴霧塗佈機、狹縫塗佈機、刮刀塗佈機等塗佈該塗層液形成塗膜，藉由將該塗膜乾燥而製造樹脂薄片。The method of forming a resin composition layer by applying the coating liquid described above can, for example, prepare a coating liquid containing a resin composition and, if desired, a solvent or a dispersing agent, and apply a mold to the peeling surface of the peeling sheet. A coater, a curtain coater, a spray coater, a slit coater, a knife coater, etc. apply the coating liquid to form a coating film, and dry the coating film to produce a resin sheet.

塗層液，只要可以進行塗佈，其性狀，並無特別限定，有含有用於形成樹脂層的成分作為溶質之情形，亦有含有作為分散質之情形。上述溶劑之例，可舉環己酮、甲苯、乙酸乙酯、甲乙酮、丙酮、二甲苯等的有機溶劑等。剝離薄片可作為工程材料剝離，亦可用於保護樹脂組成物層到使用之前。The properties of the coating liquid are not particularly limited as long as it can be applied, and the component for forming the resin layer may be contained as a solute or may be contained as a dispersoid. Examples of the solvent include organic solvents such as cyclohexanone, toluene, ethyl acetate, methyl ethyl ketone, acetone, and xylene. The release sheet can be peeled off as an engineering material and can also be used to protect the resin composition layer until use.

此外，在樹脂組成物層的兩面分別積層剝離薄片的積層體的製造方法，可在一剝離薄片的剝離面上塗佈塗層液形成塗膜，將此乾燥、形成由樹脂組成物層與一剝離薄片所形成的積層體，在該積層體的樹脂組成物層側的與一剝離片的相反側的面黏貼其他剝離薄片的剝離面，得到具有一剝離薄片/樹脂組成物層/其他剝離薄片所構成的樹脂薄片。此時，剝離薄片的至少一方可作為工程材料剝離，亦可用於保護樹脂組成物層到使用之前。In addition, the method for producing a laminate in which release sheets are laminated on both sides of the resin composition layer, can be obtained by applying a coating liquid on the release side of a release sheet to form a coating film, drying this to form a layer consisting of the resin composition layer and a layer. A layered product formed from a release sheet, and a release surface of another release sheet is adhered to the surface of the layered product on the side of the resin composition layer on the opposite side of a release sheet to obtain a release sheet having a release sheet/resin composition layer/another release sheet Formed resin sheet. In this case, at least one of the peeling sheets can be peeled off as a construction material, and can also be used to protect the resin composition layer until use.

4. 樹脂薄片的使用方法 關於本實施形態的樹脂薄片是在半導體裝置的製造方法，用於電子零件的密封。可例如，對設於基板上、或黏著薄片等的假固定材上的電子零件，積層樹脂薄片的樹脂組成物層之後，使樹脂組成物層硬化形成硬化層，而進行電子零件的密封。4. How to use the resin sheet The resin sheet according to the present embodiment is used in the manufacturing method of a semiconductor device, and is used for sealing electronic parts. For example, after laminating a resin composition layer of a resin sheet on an electronic component provided on a substrate or a dummy fixing material such as an adhesive sheet, the resin composition layer is cured to form a hardened layer to seal the electronic component.

在關於本實施形態的樹脂薄片，藉由樹脂組成物層由含有上述著色材料的樹脂組成物形成的同時，使該樹脂組成物層硬化而成硬化層顯示上述光線穿透率，在所製造的半導體裝置，可達成電子零件優良的隱蔽性的同時，亦可抑制來自外部電磁波的錯誤動作。再者，藉由樹脂組成物層由含有上述著色材料的樹脂組成物所形成，硬化層具有良好的絕緣性。因此，藉由使用關於本實施形態的樹脂薄片，具有優良的外觀的同時，亦可製造抑制錯誤動作或發生絕緣破壞的品質優良的半導體裝置。In the resin sheet of the present embodiment, the resin composition layer is formed of the resin composition containing the above-mentioned coloring material, and the resin composition layer is hardened so that the hardened layer exhibits the above-mentioned light transmittance. The semiconductor device can achieve excellent concealment of electronic components and at the same time suppress malfunctions from external electromagnetic waves. Furthermore, since the resin composition layer is formed of the resin composition containing the above-mentioned coloring material, the cured layer has good insulating properties. Therefore, by using the resin sheet according to the present embodiment, it is possible to manufacture a high-quality semiconductor device that suppresses malfunction and insulation breakdown while having an excellent appearance.

上述硬化，藉由加熱樹脂組成物層進行為佳。此時，加熱溫度，以100℃以上為佳，以120℃以上特別佳。此外，該溫度，以240℃以下為佳，以200℃以下特別佳。此外，上述加熱時間，以15分鐘以上為佳，以20分鐘以上特別佳。此外，該時間，以300分鐘以下為佳，以100分鐘以下特別佳。The above-mentioned curing is preferably performed by heating the resin composition layer. At this time, the heating temperature is preferably 100°C or higher, particularly preferably 120°C or higher. In addition, the temperature is preferably 240°C or lower, particularly preferably 200°C or lower. In addition, the above-mentioned heating time is preferably at least 15 minutes, and particularly preferably at least 20 minutes. In addition, this time is preferably 300 minutes or less, and particularly preferably 100 minutes or less.

此外，樹脂組成物層以上述加熱的硬化，以複數次的加熱處理分階段進行為佳。此時的加熱，分成2次以上進行為佳，特別是進行以溫度T1使之熱硬化的第1加熱處理，及以較溫度T1高的溫度T2使之熱硬化的第2加熱處理的2階段加熱處理為佳。此時，在第1加熱處理，溫度T1，以100℃以上，130℃以下為佳，加熱處理的時間，以15分鐘以上，60分鐘以下為佳。此外，在第2加熱處理，溫度T2，以150℃以上，220℃以下為佳，加熱處理的時間，以30分鐘以上，120分鐘以下為佳。In addition, it is preferable that the resin composition layer is hardened by the above-mentioned heating, and is preferably carried out in stages by a plurality of heat treatments. The heating at this time is preferably carried out in two or more times, and in particular, two stages of a first heat treatment for thermosetting at a temperature T1 and a second heat treatment for thermosetting at a temperature T2 higher than the temperature T1 are carried out in two stages. Heat treatment is preferred. In this case, in the first heat treatment, the temperature T1 is preferably 100° C. or more and 130° C. or less, and the heat treatment time is preferably 15 minutes or more and 60 minutes or less. In addition, in the second heat treatment, the temperature T2 is preferably 150° C. or higher and 220° C. or lower, and the heat treatment time is preferably 30 minutes or more and 120 minutes or less.

關於本實施形態的樹脂薄片，僅在樹脂組成物層的單面具有剝離薄片時，該剝離薄片，在將樹脂組成物層積層於電子零件之後，可在將樹脂組成物層硬化前從樹脂組成物層剝離，或亦可使樹脂組成物層硬化之後，從形成的硬化層剝離。關於本實施形態的樹脂薄片，在樹脂組成物層的兩面具有剝離薄片時，將一剝離薄片剝離，使露出的樹脂組成物層的露出面積層於電子零件，而其他剝離薄片，則可在樹脂組成物層的硬化前後的任一時點剝離。Regarding the resin sheet of the present embodiment, only when the resin composition layer has a release sheet on one side of the resin composition layer, the release sheet can be formed from the resin composition before the resin composition layer is cured after laminating the resin composition on the electronic component. The material layer may be peeled off, or the resin composition layer may be hardened and then peeled off from the formed hardened layer. Regarding the resin sheet of the present embodiment, when there are release sheets on both sides of the resin composition layer, one release sheet is peeled off so that the exposed area of the exposed resin composition layer is layered on the electronic component, and the other release sheets can be used on the resin composition layer. The composition layer peeled off at any point before and after hardening of the composition layer.

上述電子零件之例，只要是一般成為密封對象的電子零件，並無特別限定，可舉例如，半導體晶片等。此外，製造的半導體裝置，可舉零件內藏基板、半導體封裝等，以零件內藏基板為佳。An example of the above-mentioned electronic component is not particularly limited as long as it is an electronic component that is generally an object of sealing, and examples thereof include semiconductor wafers and the like. In addition, the manufactured semiconductor device includes a component-embedded substrate, a semiconductor package, and the like, and a component-embedded substrate is preferable.

以上說明的實施形態，是為容易理解本發明所記載，並非用於限定本發明的記載。因此，揭示於上述實施形態的各要素，包含屬於本發明的技術上範圍的所有設計變更或均等物。 ［實施例］The embodiments described above are described to facilitate understanding of the present invention and are not intended to limit the present invention. Therefore, each element disclosed in the above-described embodiment includes all design changes and equivalents that belong to the technical scope of the present invention. [Example]

以下藉由表示實施例及試驗例等更詳細地說明本發明，惟本發明不應限定於下述試驗例等。Hereinafter, the present invention will be described in more detail by showing examples, test examples, and the like, but the present invention should not be limited to the following test examples and the like.

［實施例1～2及比較例1～3］ 將表1所示構成成分混合，以環己酮稀釋，得到固體成分濃度為58質量%的樹脂組成物的塗層液。將該塗層液，塗佈在一面經聚矽氧系剝離處理的剝離薄膜（LINTEC公司製，產品名「SP-PET382150」）的剝離面上，將所得塗膜以烘箱以100℃乾燥1分鐘，得到厚度25μm的樹脂組成物層與剝離薄膜所形成的樹脂薄片。[Examples 1 to 2 and Comparative Examples 1 to 3] The constituent components shown in Table 1 were mixed and diluted with cyclohexanone to obtain a coating liquid of a resin composition having a solid content concentration of 58% by mass. This coating liquid was applied to the peeling surface of a release film (manufactured by LINTEC, product name "SP-PET382150") which had undergone a polysiloxane-based release treatment on one side, and the resulting coating film was dried in an oven at 100°C for 1 minute. , a resin sheet formed of a resin composition layer with a thickness of 25 μm and a release film was obtained.

再者，以目視確認製造的樹脂薄片的樹脂組成物層的顏色，實施例1～2及比較例1的樹脂組成物層為黑色，比較例2～3的樹脂組成物層為灰色。In addition, visually confirming the color of the resin composition layer of the manufactured resin sheet, the resin composition layer of Examples 1-2 and Comparative Example 1 was black, and the resin composition layer of Comparative Examples 2-3 was gray.

在此，表1所示構成成分的細節如下所示。 ［熱硬化性樹脂］ BisA型環氧樹脂︰雙酚A型環氧樹脂（三菱化學公司製，產品名「jER828」） 聯苯型環氧樹脂：聯苯型環氧樹脂（日本化藥公司製，產品名「NC-3000-L」） 萘型環氧樹脂︰萘型環氧樹脂（DIC公司製，產品名「HP-6000」） 聯苯型酚︰聯苯型酚（明和化成公司製，產品名「MEHC-7851-H」） ［熱塑性樹脂］ BisA型苯氧基樹脂︰雙酚A型苯氧基樹脂（三菱化學公司製，產品名「jER1256」） ［硬化觸媒］ 咪唑系熱硬化觸媒︰2-乙基-4-甲基咪唑（四國化成公司製，產品名「2E4MZ」） ［二氧化矽填充劑］ 經環氧基矽烷處理二氧化矽填充劑︰二氧化矽（將ADOMATEX公司製，產品名「SO-C2」，平均粒徑︰0.5μm，最大粒徑︰2μm，形狀︰球狀），以3-環氧丙氧基丙基三甲氧基矽烷（信越化學公司製，產品名「KBM-403」，最小披覆面積︰330m2 /g）表面處理之物 ［著色材料］ 碳填充劑︰碳填充劑（Cosmo石油公司製，產品名「CCF-R01L」，形狀︰不定形，平均粒徑︰1μm，脂肪烴基的碳原子對全部碳原子的比例︰5%） 氮氧化鈦︰氮氧化鈦（三菱材料公司製，產品名「13M」，形狀︰六面晶，平均粒徑︰97nm，體積電阻率︰2.5Ω‧cm） 碳黑︰碳黑（三菱化學公司製，產品名「#3030B」，形狀︰球狀，平均粒徑︰60nm，脂肪烴基的碳原子對全部碳原子的比例︰＜1.0%） 鐵錳複合氧化物︰鐵錳複合氧化物（東罐材料技術公司製，產品名「42-313A」，形狀︰不定形，平均粒徑︰1.3μm） 鐵鎳複合氧化物︰鐵鎳複合氧化物（東罐材料技術公司製，產品名「42-714A」，形狀︰不定形，平均粒徑︰1.7μm）Here, the details of the constituent components shown in Table 1 are as follows. [Thermosetting resin] BisA type epoxy resin: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828") Biphenyl type epoxy resin: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. , product name "NC-3000-L") Naphthalene-type epoxy resin: Naphthalene-type epoxy resin (manufactured by DIC Corporation, product name "HP-6000") Biphenyl-type phenol: Biphenyl-type phenol (manufactured by Meiwa Chemical Co., Ltd., Product name "MEHC-7851-H") [Thermoplastic resin] BisA-type phenoxy resin: Bisphenol A-type phenoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1256") [Curing catalyst] Imidazole-based thermosetting Catalyst: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Co., Ltd., product name "2E4MZ") [Silicon dioxide filler] Epoxysilane treated Silica ADOMATEX Corporation, product name "SO-C2", average particle size: 0.5μm, maximum particle size: 2μm, shape: spherical), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. , product name "KBM-403", minimum coating area: 330m 2 /g) Surface-treated thing [coloring material] Carbon filler: carbon filler (manufactured by Cosmo Oil Co., Ltd., product name "CCF-R01L", shape: Unshaped, average particle size: 1 μm, ratio of carbon atoms of aliphatic hydrocarbon groups to all carbon atoms: 5%) Titanium oxynitride: Titanium oxynitride (manufactured by Mitsubishi Materials Corporation, product name "13M", shape: hexahedron, average Particle size: 97nm, Volume resistivity: 2.5Ω·cm) Carbon black: Carbon black (manufactured by Mitsubishi Chemical Corporation, product name "#3030B", shape: spherical, average particle size: 60nm, all carbon atoms of aliphatic hydrocarbon groups Proportion of carbon atoms: <1.0%) Iron-manganese composite oxide: Iron-manganese composite oxide (manufactured by Tokan Material Technology Co., Ltd., product name "42-313A", shape: amorphous, average particle size: 1.3μm) iron-nickel Composite oxide: Iron-nickel composite oxide (manufactured by Tokan Material Technology Co., Ltd., product name "42-714A", shape: amorphous, average particle size: 1.7 μm)

［試驗例1］（光線穿透率的評估） 從實施例及比較例所製作的樹脂薄片剝離剝離薄膜，以100℃加熱30分鐘，進一步以180℃加熱60分鐘使樹脂組成物層硬化，形成厚度25μm的硬化層。[Test Example 1] (Evaluation of Light Transmittance) The release film was peeled off from the resin sheets prepared in Examples and Comparative Examples, heated at 100° C. for 30 minutes, and further heated at 180° C. for 60 minutes to harden the resin composition layer to form Hardened layer with a thickness of 25 μm.

對該硬化層，使用分光光度計（SHIMADZU公司製，產品名「UV-VIS-NIR SPECTROPHOTOMETER UV-3600」）測定穿透率。測定是使用附屬的大形試料室MPC-3100，不使用內建的積分球進行測定。The transmittance of this hardened layer was measured using a spectrophotometer (manufactured by SHIMADZU, product name "UV-VIS-NIR SPECTROPHOTOMETER UV-3600"). The measurement was performed using the attached large sample cell MPC-3100 without the built-in integrating sphere.

從上述測定結果，取出波長在400～800nm的範圍的光線穿透率（%），根據以下的基準評估可見光區域（波長400～800nm）的光線穿透率。將結果示於表1。 ○：在波長400～800nm的全範圍光線穿透率在10%以下。 ×：在波長400～800nm的至少一部分波長，光線穿透率超過10%。From the above measurement results, the light transmittance (%) in the wavelength range of 400 to 800 nm was extracted, and the light transmittance in the visible light region (wavelength 400 to 800 nm) was evaluated according to the following criteria. The results are shown in Table 1. ○: The light transmittance in the entire range of wavelength 400 to 800 nm is 10% or less. ×: The light transmittance exceeds 10% at at least a part of the wavelengths of 400 to 800 nm.

再者，從上述測定結果，取出波長在1000～1500nm的範圍的光線穿透率（%），根據以下的基準評估近紅外光區域（波長1000～1500nm）的光線穿透率。將結果示於表1。 ○：在波長1000～1500nm的全範圍光線穿透率在40%以下。 ×：在波長1000～1500nm的至少一部分波長，光線穿透率超過40%。In addition, the light transmittance (%) of the wavelength range of 1000-1500nm was extracted from the said measurement result, and the light transmittance of the near-infrared light region (wavelength 1000-1500nm) was evaluated based on the following reference|standard. The results are shown in Table 1. ○: The light transmittance in the entire range of wavelength 1000 to 1500 nm is 40% or less. ×: The light transmittance exceeds 40% at at least a part of the wavelengths of 1000 to 1500 nm.

再者，使用在近紅外光區域（波長1000～1500nm）的光線穿透率為「○」的樹脂薄片所製造的半導體裝置，由於近紅外光區域的光可藉由硬化層良好地遮斷，故可良好地抑制起因於該光的半導體裝置的錯誤動作。Furthermore, semiconductor devices manufactured using a resin sheet with a light transmittance of "○" in the near-infrared region (wavelength of 1000 to 1500 nm) can be well blocked by the hardened layer in the near-infrared region. Therefore, malfunction of the semiconductor device due to the light can be suppressed favorably.

［試驗例2］（絕緣性的評估） 將實施例及比較例所調製的塗層液、塗佈在一面經聚矽氧剝離處理的剝離薄膜（LINTEC公司製，產品名「SP-PET382150」）的剝離面上，將所得塗膜以烘箱以100℃乾燥1分鐘，得到2片厚度25μm的樹脂組成物層與剝離薄膜所形成的樹脂薄片。將所得2片樹脂薄片的樹脂組成物層，以熱層壓機（Roye1 Sovereign公司製，產品名「RSL-382S」，層壓溫度︰120℃）黏合，作成厚度50μm的單一樹脂組成物層。將該單一樹脂組成物層，以100℃加熱30分鐘，進一步以180℃加熱60分鐘使之硬化，形成厚度50μm的硬化層。[Test Example 2] (Evaluation of Insulation Properties) The coating liquids prepared in Examples and Comparative Examples were coated on one side of a release film (manufactured by LINTEC, product name "SP-PET382150") subjected to polysiloxane release treatment. The obtained coating film was dried at 100° C. for 1 minute in an oven to obtain a resin sheet composed of two resin composition layers with a thickness of 25 μm and a release film. The resin composition layers of the obtained two resin sheets were bonded together with a thermal laminator (manufactured by Roye1 Sovereign, product name "RSL-382S", lamination temperature: 120°C) to prepare a single resin composition layer with a thickness of 50 μm. The single resin composition layer was heated at 100° C. for 30 minutes, and further heated at 180° C. for 60 minutes to be cured to form a cured layer having a thickness of 50 μm.

接著，使用絕緣電阻試驗機（菊花水電子工業社製，產品名「TOS9201」），對所得到的硬化層的一面與另一面之間，施加10秒5.0kV的電壓，確認有無發生絕緣破壞，根據以下的基準評估絕緣性。將結果示於表1。 ○：沒有發生絕緣破壞 ×︰發生絕緣破壞。Next, using an insulation resistance tester (manufactured by Kikuhasui Electronics Co., Ltd., product name "TOS9201"), a voltage of 5.0 kV was applied between one side and the other side of the obtained hardened layer for 10 seconds, and it was confirmed whether or not insulation failure occurred. Insulation was evaluated according to the following criteria. The results are shown in Table 1. ○: Dielectric breakdown did not occur ×: Dielectric breakdown occurred.

［試驗例3］（以雷射印刷的文字深度的測定） 將實施例及比較例所製作的樹脂薄片，以100℃加熱60分鐘，進一步以180℃加熱60分鐘使樹脂組成物層硬化，形成厚度25μm的硬化層。[Test Example 3] (Measurement of Character Depth by Laser Printing) The resin sheets produced in Examples and Comparative Examples were heated at 100° C. for 60 minutes, and further heated at 180° C. for 60 minutes to harden the resin composition layer to form Hardened layer with a thickness of 25 μm.

接著，使用雷射刻印機（EO TECHNICS公司製，產品名「CSM300」），從如上述所得硬化層的一面側，使用波長532nm的雷射光，以4.2mW的輸出照射，在該面雷射印刷。然後，使用雷射顯微鏡（KEYENCE公司製，產品名「VK-9710」），測定構成印刷文字的溝的深度（μm）。將結果示於表1。再者，關於無法藉由雷射印刷適當的印刷，而無法測定上述深度之例，則記「無法測定」。Next, using a laser marker (manufactured by EO TECHNICS, product name "CSM300"), from one surface side of the cured layer obtained as described above, laser light having a wavelength of 532 nm was irradiated with an output of 4.2 mW, and laser printing was performed on the surface. . Then, using a laser microscope (manufactured by KEYENCE Corporation, product name "VK-9710"), the depth (μm) of the grooves constituting the printed characters was measured. The results are shown in Table 1. In addition, regarding an example in which the above-mentioned depth cannot be measured because it cannot be properly printed by laser printing, it will be described as "unmeasured".

［試驗例4］（隱蔽性的評估） 將實施例及比較例所製作的樹脂薄片的樹脂組成物層側的面，在矽晶圓（直徑150mm，厚度100μm）的2000號研磨面，使用真空層壓裝置，以溫度90℃，壓力0.2MPa，及時間30秒的條件黏貼。之後，將剝離薄膜從樹脂薄片剝離，以100℃加熱30分鐘，進一步以180℃加熱60分鐘使樹脂組成物層硬化，形成硬化層。接著，隔著該硬化層，以目視確認研磨面，根據以下基準，評估所形成的硬化層的隱蔽性。將結果示於表1。 ○：不能確認研磨痕。 ×︰可確認研磨痕。[Test Example 4] (Evaluation of Concealment) The surface on the resin composition layer side of the resin sheets produced in the Examples and Comparative Examples was polished on a No. 2000 surface of a silicon wafer (diameter 150 mm, thickness 100 μm) using a vacuum. The lamination device was pasted under the conditions of a temperature of 90° C., a pressure of 0.2 MPa, and a time of 30 seconds. Then, the release film was peeled off from the resin sheet, heated at 100° C. for 30 minutes, and further heated at 180° C. for 60 minutes to harden the resin composition layer to form a hardened layer. Next, the polished surface was visually confirmed through the hardened layer, and the concealability of the formed hardened layer was evaluated according to the following criteria. The results are shown in Table 1. ○: Grinding marks cannot be confirmed. ×: Grinding marks can be confirmed.

[表1]

Figure 107124231-A0304-0001
[Table 1]
Figure 107124231-A0304-0001

如上根據實施例所得樹脂薄片，可形成具有優良的絕緣性的硬化層。再者，根據實施例所得樹脂薄片，對硬化層以雷射印刷印刷時，構成印刷的文字的溝具有充分的深度，可藉此印刷視認性優良的文字。 [產業上的可利性]As described above, according to the resin sheet obtained in the examples, a hardened layer having excellent insulating properties can be formed. Furthermore, according to the resin sheet obtained in the Example, when the cured layer is printed by laser printing, the grooves constituting the printed characters have a sufficient depth, whereby characters with excellent visibility can be printed. [Industrial Profitability]

關於本發明的樹脂薄片，可良好地利用在零件內藏基板的半導體裝置的製造。The resin sheet of the present invention can be suitably used for the manufacture of a semiconductor device in which a substrate is built into a component.

無。none.

無。none.

Claims (8)

一種樹脂薄片，其特徵在於：其係在半導體裝置的製造方法，用於密封電子零件的樹脂薄片，上述樹脂薄片，具備硬化性的樹脂組成物層，上述樹脂組成物層，係由含有著色材料的樹脂組成物所形成，上述著色材料，包含構成脂肪烴基的碳原子對全部碳原子的比例超過3質量%的碳系材料，使上述樹脂組成物層硬化而成的硬化層，在波長1500~1000nm的光線穿透率在40%以下，波長800~400nm的光線穿透率在10%以下。 A resin sheet, which is used in a method of manufacturing a semiconductor device, a resin sheet for sealing electronic parts, the resin sheet, and a resin composition layer having curability, and the resin composition layer is composed of a coloring material containing The above-mentioned coloring material contains a carbon-based material in which the ratio of carbon atoms constituting the aliphatic hydrocarbon group to all carbon atoms exceeds 3 mass %, and the hardened layer formed by hardening the above-mentioned resin composition layer has a wavelength of 1500~ The light transmittance of 1000nm is below 40%, and the light transmittance of wavelength 800~400nm is below 10%. 如申請專利範圍第1項之樹脂薄片，其中上述樹脂組成物中的上述著色材料的含量在0.5質量%以上，5質量%以下。 The resin sheet of claim 1, wherein the content of the coloring material in the resin composition is 0.5 mass % or more and 5 mass % or less. 如申請專利範圍第1項之樹脂薄片，其中上述著色材料為黑色。 The resin sheet of claim 1, wherein the coloring material is black. 如申請專利範圍第1項之樹脂薄片，其中上述碳系材料的平均粒徑在0.1μm以上，10μm以下。 The resin sheet of claim 1, wherein the average particle size of the carbon-based material is 0.1 μm or more and 10 μm or less. 如申請專利範圍第1項之樹脂薄片，其中上述樹脂組成物，含有熱硬化性樹脂。 The resin sheet of claim 1, wherein the resin composition contains a thermosetting resin. 如申請專利範圍第1項之樹脂薄片，其中上述樹脂組成物，含有熱塑性樹脂。 The resin sheet according to claim 1, wherein the above-mentioned resin composition contains a thermoplastic resin. 如申請專利範圍第1項之樹脂薄片，其中上述樹脂組成物，含有二氧化矽填充劑。 According to the resin sheet of claim 1, the above-mentioned resin composition contains a silica filler. 如申請專利範圍第7項之樹脂薄片，其中上述樹脂組成物中的上述二氧化矽填充劑的含量在65質量%以上，95質量%以下。 The resin sheet according to claim 7, wherein the content of the above-mentioned silica filler in the above-mentioned resin composition is 65% by mass or more and 95% by mass or less.
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