TW202405085A - resin composition - Google Patents

resin composition Download PDF

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Publication number
TW202405085A
TW202405085A TW112110850A TW112110850A TW202405085A TW 202405085 A TW202405085 A TW 202405085A TW 112110850 A TW112110850 A TW 112110850A TW 112110850 A TW112110850 A TW 112110850A TW 202405085 A TW202405085 A TW 202405085A
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resin composition
resin
mass
epoxy resin
manufactured
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TW112110850A
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Chinese (zh)
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渡邊真俊
中村洋介
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日商味之素股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

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  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This resin composition comprises an epoxy resin (A) and an inorganic filler (B), wherein the epoxy resin (A) contains a liquid epoxy resin (A-1); the inorganic filler (B) contains a carbon-containing inorganic filler (B-1) having a carbon content of at least 0.2 mass%; the amount of the liquid epoxy resin (A-1) is at least 0.5 mass% with reference to 100 mass% for the nonvolatile component in the resin composition; and the amount of the carbon-containing inorganic filler (B-1) is at least 10 mass% with reference to 100 mass% for the nonvolatile component in the resin composition.

Description

樹脂組成物resin composition

本發明係關於樹脂組成物。又，本發明係關於使用前述樹脂組成物之硬化物、薄片狀層合材料、樹脂薄片、電路基板、半導體晶片封裝及半導體裝置。The present invention relates to a resin composition. Furthermore, the present invention relates to cured products, sheet-like laminated materials, resin sheets, circuit boards, semiconductor chip packages and semiconductor devices using the above-mentioned resin composition.

於電路基板及半導體晶片封裝中一般設置有絕緣層。例如作為電路基板之一種的印刷配線板中設置有作為絕緣層之層間絕緣層。又，例如半導體晶片封裝中設置有作為絕緣層之再配線形成層。此等絕緣層可藉由將樹脂組成物經硬化所得之硬化物而形成(專利文獻1～2)。 又，已知有專利文獻3之技術。 [先前技術文獻] [專利文獻] Insulating layers are generally provided in circuit substrates and semiconductor chip packages. For example, a printed wiring board, which is one type of circuit board, is provided with an interlayer insulating layer as an insulating layer. Furthermore, for example, a semiconductor chip package is provided with a rewiring forming layer as an insulating layer. These insulating layers can be formed from a cured product obtained by curing a resin composition (Patent Documents 1 to 2). Furthermore, the technology of Patent Document 3 is known. [Prior technical literature] [Patent Document]

[專利文獻1] 日本專利第3644761號公報 [專利文獻2] 國際公開第2019/216388號 [專利文獻3] 日本特開2020-37643號公報 [Patent Document 1] Japanese Patent No. 3644761 [Patent Document 2] International Publication No. 2019/216388 [Patent Document 3] Japanese Patent Application Publication No. 2020-37643

[發明所解決的問題][Problem solved by the invention]

近年來電路基板及半導體晶片封裝之大型化、配線之高密度化及通訊之高速化正進行著。由將高密度所形成的微細配線以樹脂組成物進行適當鑲入之觀點來看，對於樹脂組成物要求高流動性。欲達成高流動性，可考慮到降低樹脂組成物之黏度。然而，在降低樹脂組成物之黏度的情況時，將配線以樹脂組成物鑲入時樹脂組成物會流動，而有著硬化該樹脂組成物所得的絕緣層之厚度的穩定性變低之情況產生。例如形成於基板上面的配線藉由樹脂組成物進行鑲入之情況時，配線上部分與配線間之間隙部分會產生樹脂組成物之厚度差，絕緣層之厚度會變得不均勻。特別在大型之電路基板及半導體晶片封裝中，因絕緣層的面積會變大，故使該絕緣層全體的厚度變穩定且均勻的困難性為高。In recent years, circuit boards and semiconductor chip packages have become larger in size, wiring has become more dense, and communications have become faster. From the viewpoint of appropriately embedding the fine wiring formed at high density with the resin composition, the resin composition is required to have high fluidity. To achieve high fluidity, consider reducing the viscosity of the resin composition. However, when the viscosity of the resin composition is lowered, the resin composition may flow when wiring is embedded with the resin composition, and the stability of the thickness of the insulating layer obtained by hardening the resin composition may decrease. For example, when the wiring formed on the substrate is embedded with a resin composition, a thickness difference in the resin composition will occur between the upper part of the wiring and the gap between the wiring, and the thickness of the insulating layer will become uneven. Especially in large-scale circuit boards and semiconductor chip packages, since the area of the insulating layer increases, it is highly difficult to stabilize and make the thickness of the entire insulating layer uniform.

又，藉由如前述之電路基板及半導體晶片封裝的大型化、配線的高密度化及通信的高速化之進行，在近年對於絕緣層的絕緣信賴性之要求水準變高。然而，欲降低樹脂組成物之黏度而採用低黏度之環氧樹脂的情況時，低黏度之環氧樹脂一般含有多量氯，故絕緣信賴性有降低的傾向。In addition, in recent years, as circuit boards and semiconductor chip packages have become larger in size, wiring has become more dense, and communications have become faster, the level of requirements for the insulation reliability of the insulating layer has become higher in recent years. However, when a low-viscosity epoxy resin is used to reduce the viscosity of the resin composition, the low-viscosity epoxy resin generally contains a large amount of chlorine, so the insulation reliability tends to be reduced.

本發明係有鑑於前述課題而創造者，故以提供可得到絕緣信賴性優異的硬化物，且流動性優異的樹脂組成物；前述樹脂組成物之硬化物；含有前述樹脂組成物之薄片狀層合材料及樹脂薄片；含有前述硬化物之電路基板、半導體晶片封裝及半導體裝置者為目的。 [解決課題的手段] The present invention was created in view of the above-mentioned problems, and therefore provides a resin composition that can obtain a cured product with excellent insulation reliability and has excellent fluidity; a cured product of the above-mentioned resin composition; and a sheet-like layer containing the above-mentioned resin composition. Composite materials and resin sheets; circuit substrates, semiconductor chip packages and semiconductor devices containing the aforementioned hardened materials. [Means to solve the problem]

本發明者欲解決前述課題而進行詳細檢討。其結果，本發明者發現組合含有特定範圍之量的(A-1)液狀環氧樹脂之(A)環氧樹脂，及含有特定範圍之量的(B-1)含碳的無機填充材之(B)無機填充材而含有的樹脂組成物可解決前述課題而完成本發明。 即，本發明含有下述者。 The inventors of the present invention conducted detailed examinations in order to solve the aforementioned problems. As a result, the present inventors discovered that (A) epoxy resin containing (A-1) liquid epoxy resin in a specific range is combined with (B-1) a carbon-containing inorganic filler containing an amount in a specific range. The resin composition containing the inorganic filler (B) can solve the above-mentioned problems and complete the present invention. That is, the present invention includes the following.

[1] 一種樹脂組成物，其中含有(A)環氧樹脂及(B)無機填充材，其中(A)環氧樹脂含有(A-1)液狀環氧樹脂，(B)無機填充材含有(B-1)碳含有量0.1質量%以上之含碳的無機填充材，(A-1)液狀環氧樹脂之量相對於樹脂組成物之不揮發成分100質量%而言為0.5質量%以上，(B-1)含碳的無機填充材之量相對於樹脂組成物之不揮發成分100質量%而言為10質量%以上之樹脂組成物。 [2] 如[1]之樹脂組成物，其中進一步含有(C)硬化劑。 [3] 如[1]或[2]所記載的樹脂組成物，其中(B-1)含碳的無機填充材之量相對於(B)無機填充材之全量100質量%而言為20質量%以上。 [4] 如[1]～[3]中任一項所記載的樹脂組成物，其中(B-1)含碳的無機填充材為碳含有量0.2質量%以上之二氧化矽粒子。 [5] 如[1]～[4]中任一項所記載的樹脂組成物，其中(B-1)含碳的無機填充材之碳含有量為5質量%以下。 [6] 如[1]～[5]中任一項所記載的樹脂組成物，其中(A-1)液狀環氧樹脂具有1,000以下之重量平均分子量。 [7] 如[1]～[6]中任一項所記載的樹脂組成物，其中(A-1)液狀環氧樹脂為非芳香族性之環氧樹脂。 [8] 如[1]～[7]中任一項所記載的樹脂組成物，其中(A-1)液狀環氧樹脂具有在25℃為15,000mPa･s以下之黏度。 [9] 如[1]～[8]中任一項所記載的樹脂組成物，其中含有(D)硬化促進劑。 [10] 如[1]～[9]中任一項所記載的樹脂組成物，其中含有(E)熱塑性樹脂。 [11] 如[1]～[10]中任一項所記載的樹脂組成物，其中具有未達4,000poise之最低熔融黏度。 [12] 如[1]～[11]中任一項所記載的樹脂組成物，其中將樹脂組成物在190℃之90分鐘條件下進行熱硬化而得硬化物，於該硬化物在130℃，85%RH之環境下輸入3.3V之電壓100小時之情況時，藉由線/空間為15μm/15μm之梳狀電極(Comb-shaped electrode)所測定的該硬化物之絕緣電阻值為1.0×10 8Ω以上。 [13] 如[1]～[12]中任一項所記載的樹脂組成物，其為絕緣層形成用。 [14] 一種硬化物，其如[1]～[13]中任一項所記載的樹脂組成物的硬化物。 [15] 一種薄片狀層合材料，其中含有如[1]～[13]中任一項所記載的樹脂組成物。 [16] 一種樹脂薄片，其中具備支持體，與形成於該支持體上之樹脂組成物層，樹脂組成物層含有如[1]～[13]中任一項所記載的樹脂組成物。 [17] 一種電路基板，其中含有如[1]～[13]中任一項所記載的樹脂組成物的硬化物。 [18] 一種半導體晶片封裝，其中含有如[1]～[13]中任一項所記載的樹脂組成物的硬化物。 [19] 一種半導體裝置，其中具備如[17]所記載的電路基板。 [20] 一種半導體裝置，其中具備如[18]所記載的半導體晶片封裝。 [發明之效果] [1] A resin composition containing (A) epoxy resin and (B) inorganic filler, wherein (A) epoxy resin contains (A-1) liquid epoxy resin, and (B) inorganic filler contains (B-1) A carbon-containing inorganic filler with a carbon content of 0.1% by mass or more, and the amount of (A-1) liquid epoxy resin is 0.5% by mass relative to 100% by mass of non-volatile components of the resin composition. As mentioned above, (B-1) is a resin composition in which the amount of the carbon-containing inorganic filler is 10% by mass or more based on 100% by mass of the non-volatile components of the resin composition. [2] The resin composition of [1], further containing (C) a hardener. [3] The resin composition according to [1] or [2], wherein the amount of the carbon-containing inorganic filler (B-1) is 20% by mass relative to 100% by mass of the total amount of the (B) inorganic filler. %above. [4] The resin composition according to any one of [1] to [3], wherein (B-1) the carbon-containing inorganic filler is silica particles with a carbon content of 0.2 mass % or more. [5] The resin composition according to any one of [1] to [4], wherein the carbon content of (B-1) the carbon-containing inorganic filler is 5 mass % or less. [6] The resin composition according to any one of [1] to [5], wherein (A-1) the liquid epoxy resin has a weight average molecular weight of 1,000 or less. [7] The resin composition according to any one of [1] to [6], wherein the liquid epoxy resin (A-1) is a non-aromatic epoxy resin. [8] The resin composition according to any one of [1] to [7], wherein (A-1) the liquid epoxy resin has a viscosity of 15,000 mPa･s or less at 25°C. [9] The resin composition according to any one of [1] to [8], which contains (D) a hardening accelerator. [10] The resin composition according to any one of [1] to [9], containing (E) a thermoplastic resin. [11] The resin composition according to any one of [1] to [10], which has a minimum melt viscosity of less than 4,000 poise. [12] The resin composition according to any one of [1] to [11], wherein the resin composition is thermally cured at 190°C for 90 minutes to obtain a cured product, and the cured product is heated at 130°C , when a voltage of 3.3V is input for 100 hours in an environment of 85% RH, the insulation resistance value of the hardened material measured by a Comb-shaped electrode with a line/space of 15μm/15μm is 1.0× 10 8 Ω or more. [13] The resin composition according to any one of [1] to [12], which is used for forming an insulating layer. [14] A cured product of the resin composition according to any one of [1] to [13]. [15] A sheet-like laminated material containing the resin composition according to any one of [1] to [13]. [16] A resin sheet comprising a support and a resin composition layer formed on the support, the resin composition layer containing the resin composition according to any one of [1] to [13]. [17] A circuit board containing a cured product of the resin composition according to any one of [1] to [13]. [18] A semiconductor chip package containing a cured product of the resin composition according to any one of [1] to [13]. [19] A semiconductor device including the circuit board according to [17]. [20] A semiconductor device including the semiconductor chip package described in [18]. [Effects of the invention]

依據本發明可提供可得到絕緣信賴性優異的硬化物，且流動性優異的樹脂組成物；前述樹脂組成物之硬化物；含有前述樹脂組成物的薄片狀層合材料及樹脂薄片；含有前述硬化物的電路基板、半導體晶片封裝及半導體裝置。According to the present invention, it is possible to provide a resin composition that can provide a cured product with excellent insulation reliability and excellent fluidity; a cured product of the above-mentioned resin composition; a sheet-like laminated material and a resin sheet containing the above-mentioned resin composition; and a resin composition containing the above-mentioned cured product. circuit substrates, semiconductor chip packages and semiconductor devices.

[實施發明的型態][Types of carrying out the invention]

以下對於本發明以實施形態及例示物表示而說明。但，本發明並未限定於下述所示實施形態及例示物者，在不逃脫所請範圍及其均等範圍的範圍下可任意變更而實施。The present invention will be described below by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the claimed scope and its equivalent range.

以下說明中，所謂用語「(甲基)丙烯酸」包含丙烯酸、甲基丙烯酸及其組合。又，所謂用語「(甲基)丙烯酸酯」包含丙烯酸酯、甲基丙烯酸酯及其組合。In the following description, the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid and combinations thereof. In addition, the term "(meth)acrylate" includes acrylate, methacrylate, and combinations thereof.

以下說明中，用語「介電率」若無特別說明則表示比電導率。In the following description, the term "dielectric conductivity" means specific conductivity unless otherwise specified.

[樹脂組成物之概要] 有關本發明之一實施形態的樹脂組成物含有(A)環氧樹脂及(B)無機填充材。(A)環氧樹脂含有特定範圍之量的(A-1)液狀環氧樹脂。又，(B)無機填充材含有特定範圍之量的(B-1)含碳的無機填充材。其中，所謂(B-1)含碳的無機填充材表示含有特定範圍之量的碳之無機填充材。 [Outline of Resin Composition] The resin composition according to one embodiment of the present invention contains (A) epoxy resin and (B) inorganic filler. (A) The epoxy resin contains the (A-1) liquid epoxy resin in an amount within a specific range. Moreover, the (B) inorganic filler contains the (B-1) carbon-containing inorganic filler in an amount within a specific range. Here, (B-1) the carbon-containing inorganic filler means an inorganic filler containing an amount of carbon in a specific range.

有關本發明之一實施形態的樹脂組成物可具有優異的流動性。又，依據有關本發明之一實施形態的樹脂組成物可得到絕緣信賴性優異的硬化物。因此，依據有關本發明之一實施形態的樹脂組成物，可改善流動性及絕緣信賴性雙方。且有關本發明之一實施形態的樹脂組成物通常可具有較低的最低熔融黏度。又，依據有關本發明之一實施形態的樹脂組成物，通常可得到優異耐熱性的硬化物。The resin composition according to one embodiment of the present invention can have excellent fluidity. Furthermore, according to the resin composition according to one embodiment of the present invention, a cured product excellent in insulation reliability can be obtained. Therefore, according to the resin composition according to one embodiment of the present invention, both fluidity and insulation reliability can be improved. Furthermore, the resin composition according to one embodiment of the present invention can generally have a lower minimum melt viscosity. Furthermore, according to the resin composition according to one embodiment of the present invention, a cured product having excellent heat resistance can generally be obtained.

本發明者對於藉由有關本發明之一實施形態的樹脂組成物而得到如前述優異效果之構成推測如下述。但，本發明之範圍並未限定於下述說明構成者。The inventors of the present invention speculate as follows on the structure of obtaining the above-mentioned excellent effects by the resin composition according to one embodiment of the present invention. However, the scope of the present invention is not limited to the following description.

有關本發明之一實施形態的樹脂組成物因含有特定範圍之量的(A-1)液狀環氧樹脂，可具有低黏度。因此，可達成優異流動性。然而，一般而言，低黏度的(A-1)液狀環氧樹脂會因該製造方法而有著含有大量氯之傾向。含有如此多量氯之組成物通常絕緣信賴性較差。The resin composition according to one embodiment of the present invention can have low viscosity because it contains the (A-1) liquid epoxy resin in an amount within a specific range. Therefore, excellent fluidity can be achieved. However, generally speaking, low-viscosity (A-1) liquid epoxy resin tends to contain a large amount of chlorine due to this manufacturing method. Compositions containing such large amounts of chlorine generally have poor insulation reliability.

相對於此，有關本發明之一實施形態的樹脂組成物可組合於特定範圍量之(A-1)液狀環氧樹脂中，進一步含有特定範圍量之(B-1)含碳的無機填充材。如此樹脂組成物中，因(B-1)含碳的無機填充材所含的碳可捕捉氯，故可抑制因氯引起的絕緣信賴性降低。因此，可達成流動性及絕緣信賴性雙方的提高。On the other hand, the resin composition according to one embodiment of the present invention can be combined with (A-1) liquid epoxy resin in a specific range, and further contains (B-1) a carbon-containing inorganic filler in a specific range. material. In such a resin composition, since the carbon contained in the carbon-containing inorganic filler (B-1) can capture chlorine, reduction in insulation reliability due to chlorine can be suppressed. Therefore, both fluidity and insulation reliability can be improved.

作為藉由氯抑制絕緣信賴性之降低的其他方法，有可將離子捕集器導入於樹脂組成物之方法。然而，離子捕集器在一般而言與樹脂組成物中之樹脂成分的親和性較為差，故含有該離子捕集器之樹脂組成物在微小水準上的組成均勻性較差。又，離子捕集器在一般而言有著耐熱性較差的傾向。因此，過去含有離子捕集器之樹脂組成物中，作為組成物全體有時黏度變高，有時局部性地產生流動性及耐熱性較差的部分，結果作為樹脂組成物全體而言，其流動性及耐熱性較為差。 相對於此，有關本發明之一實施形態的樹脂組成物中，捕捉氯的碳不會降低無機填充材與樹脂成分之親和性及耐熱性。因此，捕捉氯而提高絕緣信賴性時，亦可同時維持耐熱性而可充分地發揮藉由(A-1)液狀環氧樹脂之流動性的改善效果，故可達成流動性及絕緣信賴性雙方的提高。 As another method of suppressing the decrease in insulation reliability by chlorine, there is a method of introducing an ion trap into a resin composition. However, the ion trap generally has poor affinity with the resin components in the resin composition, so the composition uniformity of the resin composition containing the ion trap is poor at a micro level. In addition, ion traps generally tend to have poor heat resistance. Therefore, in resin compositions containing ion traps in the past, the viscosity of the entire composition may become high, and sometimes parts with poor fluidity and heat resistance may occur locally. As a result, the flow of the resin composition as a whole becomes poor. The performance and heat resistance are relatively poor. On the other hand, in the resin composition according to one embodiment of the present invention, the carbon capturing chlorine does not reduce the affinity and heat resistance between the inorganic filler and the resin component. Therefore, when chlorine is captured to improve insulation reliability, heat resistance can be maintained at the same time and the fluidity improvement effect of (A-1) liquid epoxy resin can be fully exerted, so fluidity and insulation reliability can be achieved. Improvement of both parties.

且，(A-1)液狀環氧樹脂通常為分子量小，而有著環氧當量較小的傾向。因此，含有特定範圍量之(A-1)液狀環氧樹脂的樹脂組成物在進行硬化時，可形成多數環氧基經反應所形成的交聯點。因此，因可緻密地形成交聯結構之網絡，故可得到高耐熱性。故例如可得到具有高玻璃轉移溫度之硬化物。Furthermore, the (A-1) liquid epoxy resin generally has a small molecular weight and tends to have a small epoxy equivalent. Therefore, when the resin composition containing the (A-1) liquid epoxy resin in a specific range is cured, a plurality of crosslinking points formed by the reaction of the epoxy groups can be formed. Therefore, high heat resistance can be achieved because a network of cross-linked structures can be densely formed. Therefore, for example, a hardened product with a high glass transition temperature can be obtained.

又，如前述，與含有離子捕集器之樹脂組成物相異，有關本發明之一實施形態的樹脂組成物可具有高組成之均勻性。因此，該硬化物亦因具有高組成之均勻性，故可抑制成為藉由應力的破壞起點的組成不均勻點之產生。因此，於含有樹脂組成物之硬化物的絕緣層上形成導體層，該絕緣層經加熱而於絕緣層內產生應力之情況時，可抑制藉由該應力之絕緣層的破壞。因此，因可抑制絕緣層之破壞所引起的導體層之剝離，故可得到優異的耐回流焊性。Furthermore, as mentioned above, unlike the resin composition containing an ion trap, the resin composition according to one embodiment of the present invention can have high composition uniformity. Therefore, since the hardened material also has high composition uniformity, it is possible to suppress the occurrence of composition uneven spots that serve as starting points for destruction due to stress. Therefore, when a conductive layer is formed on an insulating layer containing a hardened material of a resin composition, and when the insulating layer is heated and stress is generated in the insulating layer, destruction of the insulating layer due to the stress can be suppressed. Therefore, since peeling of the conductor layer caused by damage to the insulating layer can be suppressed, excellent reflow resistance can be obtained.

[(A)環氧樹脂] 有關本發明之一實施形態的樹脂組成物中含有作為(A)成分之(A)環氧樹脂。(A)環氧樹脂可為具有環氧基之硬化性樹脂。作為(A)環氧樹脂，例如可舉出三羥甲基丙烷型環氧樹脂、新戊二醇型環氧樹脂、雙二甲酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、參酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油基酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、酚芳烷基型環氧樹脂、聯苯基型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯結構的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、螺環含有環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、亞萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂、異氰脲酸酯型環氧樹脂、苯酚鄰苯二甲醯亞胺型環氧樹脂等。(A)環氧樹脂可單獨使用1種類，亦可組合2種類以上而使用。 [(A) Epoxy resin] The resin composition according to one embodiment of the present invention contains (A) epoxy resin as (A) component. (A) The epoxy resin may be a curable resin having an epoxy group. Examples of (A) epoxy resin include trimethylolpropane type epoxy resin, neopentyl glycol type epoxy resin, bisxylenol type epoxy resin, bisphenol A type epoxy resin, and bisphenol type epoxy resin. F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type Varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl Ester epoxy resin, cresol novolak epoxy resin, phenol aralkyl epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure , alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, three Hydroxymethyl epoxy resin, tetraphenylethane epoxy resin, isocyanurate epoxy resin, phenol phthalimide epoxy resin, etc. (A) Epoxy resin can be used individually by 1 type, and can also be used in combination of 2 or more types.

(A)環氧樹脂含有特定範圍量之(A-1)液狀環氧樹脂。(A-1)液狀環氧樹脂在溫度20℃下顯示液狀環氧樹脂。(A-1)液狀環氧樹脂以於1分子中具有2個以上環氧基者為佳。(A) Epoxy resin contains (A-1) liquid epoxy resin in a specific range amount. (A-1) Liquid epoxy resin shows liquid epoxy resin at a temperature of 20°C. (A-1) The liquid epoxy resin preferably has two or more epoxy groups in one molecule.

作為(A-1)液狀環氧樹脂，例如可舉出雙酚A型液狀環氧樹脂、雙酚F型液狀環氧樹脂、雙酚AF型液狀環氧樹脂、萘型液狀環氧樹脂、縮水甘油基酯型液狀環氧樹脂、縮水甘油基胺型液狀環氧樹脂、酚酚醛清漆型液狀環氧樹脂、三羥甲基丙烷型液狀環氧樹脂、新戊二醇型液狀環氧樹脂、具有酯骨架的脂環式液狀環氧樹脂、環己烷型液狀環氧樹脂、環己烷二甲醇型液狀環氧樹脂，及具有丁二烯結構之液狀環氧樹脂。(A-1)液狀環氧樹脂可單獨使用1種類，亦可組合2種類以上而使用。Examples of the (A-1) liquid epoxy resin include bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, bisphenol AF type liquid epoxy resin, and naphthalene type liquid epoxy resin. Epoxy resin, glycidyl ester type liquid epoxy resin, glycidyl amine type liquid epoxy resin, phenolic novolac type liquid epoxy resin, trimethylolpropane type liquid epoxy resin, neopentanol type Glycol-type liquid epoxy resin, alicyclic liquid epoxy resin with ester skeleton, cyclohexane-type liquid epoxy resin, cyclohexanedimethanol-type liquid epoxy resin, and butadiene structure Liquid epoxy resin. (A-1) Liquid epoxy resin can be used individually by 1 type, and can also be used in combination of 2 or more types.

(A-1)液狀環氧樹脂以含有非芳香族性之環氧樹脂者為佳，僅含有非芳香族性之環氧樹脂者為佳。所謂非芳香族性之環氧樹脂表示於該分子中未含有芳香環之環氧樹脂。又，「芳香環」表示於環上π電子系所含的電子數為4p+2個(p為0以上的整數)之依據哈克爾的法則(Hückel’s rule)的環，包含單環式芳香環，及2個以上單環式芳香環經縮合的縮合多環式芳香環。又，於芳香環包含芳香族碳環及芳香族雜環。因此，非芳香族性之環氧樹脂以脂肪族環氧樹脂為佳。非芳香族性之環氧樹脂亦可含有脂環式結構。使用含有非芳香族性之環氧樹脂的(A-1)液狀環氧樹脂之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變的特別良好。(A-1)液狀環氧樹脂之中，作為非芳香族性之環氧樹脂的例子，可舉出三羥甲基丙烷型液狀環氧樹脂、新戊二醇型液狀環氧樹脂、己二醇型液狀環氧樹脂、聚丙二醇型液狀環氧樹脂、具有酯骨架的脂環式液狀環氧樹脂、環己烷型液狀環氧樹脂、環己烷二甲醇型液狀環氧樹脂，及具有丁二烯結構之液狀環氧樹脂。(A-1) The liquid epoxy resin preferably contains non-aromatic epoxy resin, and the liquid epoxy resin preferably contains only non-aromatic epoxy resin. The so-called non-aromatic epoxy resin means an epoxy resin that does not contain an aromatic ring in the molecule. In addition, "aromatic ring" means a ring in which the number of π electrons in the ring is 4p+2 (p is an integer greater than 0) according to Hückel's rule, including monocyclic aromatic rings. , and condensed polycyclic aromatic rings in which two or more monocyclic aromatic rings are condensed. Moreover, the aromatic ring includes an aromatic carbocyclic ring and an aromatic heterocyclic ring. Therefore, the non-aromatic epoxy resin is preferably an aliphatic epoxy resin. Non-aromatic epoxy resins may also contain alicyclic structures. When using (A-1) liquid epoxy resin containing non-aromatic epoxy resin, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can usually be made particularly good. . Among (A-1) liquid epoxy resins, examples of non-aromatic epoxy resins include trimethylolpropane type liquid epoxy resin and neopentyl glycol type liquid epoxy resin. , hexylene glycol type liquid epoxy resin, polypropylene glycol type liquid epoxy resin, alicyclic liquid epoxy resin with ester skeleton, cyclohexane type liquid epoxy resin, cyclohexanedimethanol type liquid epoxy resin, and liquid epoxy resin with butadiene structure.

作為(A-1)液狀環氧樹脂之具體例子，可舉出DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型液狀環氧樹脂)；三菱化學公司製的「828US」、「828EL」、「jER828EL」、「825」、「EPICOAT828EL」(雙酚A型液狀環氧樹脂)；三菱化學公司製的「jER807」、「1750」(雙酚F型液狀環氧樹脂)；三菱化學公司製的「jER152」(酚酚醛清漆型液狀環氧樹脂)；三菱化學公司製的「630」、「630LSD」、「604」(縮水甘油基胺型液狀環氧樹脂)；ADEKA公司製的「ED-523T」(甘露醇液狀環氧樹脂)；ADEKA公司製的「EP-3950L」、「EP-3980S」(縮水甘油基胺型液狀環氧樹脂)；ADEKA公司製的「EP-4088S」(二環戊二烯型液狀環氧樹脂)；日鐵化學&材料公司製的「ZX1059」(雙酚A型液狀環氧樹脂與雙酚F型液狀環氧樹脂之混合品)；Nagase Chemtex公司製的「EX-721」(縮水甘油基酯型液狀環氧樹脂)；Daicel Chemical Industries, Ltd.製的「CELLOXIDE2021P」(具有酯骨架的脂環式液狀環氧樹脂)；Daicel Chemical Industries, Ltd.製的「PB-3600」、日本曹達公司製的「JP-100」、「JP-200」(具有丁二烯結構的液狀環氧樹脂)；日鐵化學&材料製的「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油基環己烷型液狀環氧樹脂)；ADEKA公司製「ED-503」、「ED-503G」(己二醇型液狀環氧樹脂)；ADEKA公司製「ED-505」(三羥甲基丙烷型液狀環氧樹脂)；ADEKA公司製「ED-506」(聚丙二醇型液狀環氧樹脂)；ADEKA公司製「ED-523T」(新戊二醇型液狀環氧樹脂)等。Specific examples of the (A-1) liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type liquid epoxy resin) manufactured by DIC Corporation; "828US" manufactured by Mitsubishi Chemical Corporation ", "828EL", "jER828EL", "825", "EPICOAT828EL" (bisphenol A type liquid epoxy resin); "jER807", "1750" (bisphenol F type liquid epoxy resin) manufactured by Mitsubishi Chemical Corporation Resin); "jER152" (phenolic novolac type liquid epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type liquid epoxy resin) manufactured by Mitsubishi Chemical Corporation ); "ED-523T" (mannitol liquid epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine type liquid epoxy resin) manufactured by ADEKA; ADEKA "EP-4088S" (dicyclopentadiene type liquid epoxy resin) manufactured by the company; "ZX1059" (bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. Mixed product of epoxy resin); "EX-721" (glycidyl ester type liquid epoxy resin) manufactured by Nagase Chemtex Co., Ltd.; "CELLOXIDE2021P" (alicyclic type with ester skeleton) manufactured by Daicel Chemical Industries, Ltd. Liquid epoxy resin); "PB-3600" manufactured by Daicel Chemical Industries, Ltd., "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (liquid epoxy resin with butadiene structure) ; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type liquid epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ED-503" and "ED-503G" manufactured by ADEKA Corporation (hexylene glycol type liquid epoxy resin); ADEKA Co., Ltd.'s "ED-505" (trimethylolpropane type liquid epoxy resin); ADEKA Co., Ltd.'s "ED-506" (polypropylene glycol type liquid epoxy resin) Resin); "ED-523T" (neopentyl glycol type liquid epoxy resin) manufactured by ADEKA, etc.

(A-1)液狀環氧樹脂以具有特定範圍小的重量平均分子量者為佳。(A-1)液狀環氧樹脂之重量平均分子量具體而言，以1000以下為佳，較佳為500以下，更佳為300以下。使用具有該範圍之重量平均分子量的(A-1)液狀環氧樹脂之情況，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。下限值雖無特別限制，例如可為50以上、80以上、100以上等。樹脂之重量平均分子量為藉由凝膠滲透層析法(GPC)法，測定出聚苯乙烯換算之值。(A-1) The liquid epoxy resin preferably has a weight average molecular weight within a specific range. (A-1) The weight average molecular weight of the liquid epoxy resin is specifically preferably 1,000 or less, more preferably 500 or less, and more preferably 300 or less. When the (A-1) liquid epoxy resin having a weight average molecular weight in this range is used, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally be made particularly good. The lower limit value is not particularly limited, but may be, for example, 50 or more, 80 or more, 100 or more, or the like. The weight average molecular weight of the resin is a polystyrene-converted value measured by gel permeation chromatography (GPC).

(A-1)液狀環氧樹脂以具有特定範圍小的黏度者為佳。(A-1)液狀環氧樹脂的前述黏度之範圍，以15,000mPa･s以下為佳，較佳為3,000mPa･s以下，更佳為1,000mPa以下，特佳為500mPa･s以下。使用具有該範圍之黏度的(A-1)液狀環氧樹脂之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。下限值並無特別限制，例如可為5mPa･s以上，10mPa･s以上等。液狀環氧樹脂之黏度為使用E型黏度計，在25℃且20rpm之條件下進行測定。具體的黏度之測定方法可採用後述實施例之＜環氧樹脂之黏度的測定＞所記載的方法。(A-1) The liquid epoxy resin preferably has a viscosity that is small in a specific range. (A-1) The aforementioned viscosity range of the liquid epoxy resin is preferably 15,000 mPa･s or less, more preferably 3,000 mPa･s or less, more preferably 1,000 mPa･s or less, and particularly preferably 500 mPa･s or less. When the (A-1) liquid epoxy resin with a viscosity in this range is used, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally be made particularly good. The lower limit value is not particularly limited, but may be 5 mPa･s or more, 10 mPa･s or more, etc., for example. The viscosity of liquid epoxy resin is measured using an E-type viscometer at 25°C and 20 rpm. A specific method for measuring the viscosity may be the method described in "Measurement of the Viscosity of Epoxy Resin" in the Examples described later.

具有如上述小黏度之(A-1)液狀環氧樹脂一般可含有氯。(A-1)液狀環氧樹脂所含的氯之量相對於(A-1)液狀環氧樹脂100質量%而言，可為0.03質量%以上、0.1質量%以上、0.3質量%以上等。在採用含有如此氯的(A-1)液狀環氧樹脂之情況下，含有特定範圍量之(B-1)含碳的無機填充材的樹脂組成物亦可達成高絕緣性。(A-1)液狀環氧樹脂所含的氯之量的上限以5質量%以下為佳，較佳為3質量%以下，更佳為1質量%以下。(A-1) liquid epoxy resin with a low viscosity as mentioned above may generally contain chlorine. The amount of chlorine contained in the (A-1) liquid epoxy resin may be 0.03 mass% or more, 0.1 mass% or more, or 0.3 mass% or more relative to 100 mass% of the (A-1) liquid epoxy resin. wait. When using (A-1) liquid epoxy resin containing such chlorine, a resin composition containing (B-1) carbon-containing inorganic filler in a specific range can also achieve high insulation properties. (A-1) The upper limit of the amount of chlorine contained in the liquid epoxy resin is preferably 5 mass% or less, more preferably 3 mass% or less, and more preferably 1 mass% or less.

由上述觀點來看，作為特佳(A-1)液狀環氧樹脂之具體例子，可舉出下述式(a-1)所示己二醇型液狀環氧樹脂、下述式(a-2)所示三羥甲基丙烷型液狀環氧樹脂、下述式(a-3)所示聚丙二醇型液狀環氧樹脂、下述式(a-4)所示新戊二醇型液狀環氧樹脂。式(a-3)中，n表示0以上之數。作為己二醇型液狀環氧樹脂之販售品的例子，可舉出ADEKA公司製的「ED-503」(黏度25mPa･s、氯量6.5質量%)、「ED-503G」(黏度15mPa･s、氯量0.3質量%)。作為三羥甲基丙烷型液狀環氧樹脂之販售品的例子，可舉出ADEKA公司製「ED-505」(黏度150mPa･s、氯量8.0質量%)。作為聚丙二醇型液狀環氧樹脂之販售品的例子，可舉出ADEKA公司製「ED-506」(黏度60mPa･s、氯量6.0質量%)。作為新戊二醇型液狀環氧樹脂的販售品之例子，可舉出ADEKA公司製「ED-523T」(黏度15mPa･s、氯量5.0質量%)。From the above viewpoint, specific examples of particularly preferred (A-1) liquid epoxy resins include hexylene glycol type liquid epoxy resin represented by the following formula (a-1), and the following formula (a-1) Trimethylolpropane type liquid epoxy resin represented by a-2), polypropylene glycol type liquid epoxy resin represented by the following formula (a-3), neopentyl glycol represented by the following formula (a-4) Alcohol type liquid epoxy resin. In formula (a-3), n represents a number equal to or greater than 0. Examples of commercial products of hexylene glycol type liquid epoxy resin include "ED-503" (viscosity 25 mPa･s, chlorine content 6.5 mass%) and "ED-503G" (viscosity 15 mPa) manufactured by ADEKA ･s, chlorine content 0.3% by mass). An example of a commercial product of trimethylolpropane type liquid epoxy resin is "ED-505" manufactured by ADEKA (viscosity 150 mPa･s, chlorine content 8.0 mass%). An example of a commercial product of polypropylene glycol type liquid epoxy resin is "ED-506" manufactured by ADEKA (viscosity 60 mPa･s, chlorine content 6.0 mass%). An example of a commercial product of neopentyl glycol type liquid epoxy resin is "ED-523T" manufactured by ADEKA (viscosity 15 mPa･s, chlorine content 5.0 mass%).

(A-1)液狀環氧樹脂的環氧當量之範圍，以50g/eq.～5,000g/eq.為佳，較佳為60g/eq.～3,000g/eq.，更佳為80g/eq.～2,000g/eq.，特佳為110g/eq.～1,000g/eq.。環氧當量表示每環氧基1當量的樹脂之質量。該環氧當量可依據JIS K7236測定。(A-1) The range of the epoxy equivalent of the liquid epoxy resin is preferably 50g/eq.～5,000g/eq., more preferably 60g/eq.～3,000g/eq., and more preferably 80g/eq. eq.～2,000g/eq., the best is 110g/eq.～1,000g/eq. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

有關本發明之一實施形態的樹脂組成物中，含有特定範圍量的(A-1)液狀環氧樹脂。(A-1)液狀環氧樹脂之量的範圍，相對於樹脂組成物中之不揮發成分100質量%而言，通常為0.5質量%以上，以1質量%以上為佳，較佳為2質量%以上，以20質量%以下為佳，較佳為10質量%以下，更佳為5質量%以下。(A-1)液狀環氧樹脂之量為前述範圍的情況時，可提高流動性及絕緣信賴性雙方，且通常可使最低熔融黏度及耐熱性變得良好。The resin composition according to one embodiment of the present invention contains (A-1) liquid epoxy resin in a specific range. (A-1) The range of the amount of liquid epoxy resin is usually 0.5 mass% or more, preferably 1 mass% or more, preferably 2 mass%, based on 100 mass% of non-volatile components in the resin composition. The content is preferably 20 mass% or less, more preferably 10 mass% or less, and more preferably 5 mass% or less. (A-1) When the amount of liquid epoxy resin is within the above range, both fluidity and insulation reliability can be improved, and the minimum melt viscosity and heat resistance can generally be improved.

(A-1)液狀環氧樹脂之量的範圍，相對於樹脂組成物中之樹脂成分100質量%而言，以1質量%以上為佳，以1.5質量%以上為佳，較佳為2質量%以上，特佳為5質量%以上，以40質量%以下為佳，較佳為30質量%以下，更佳為20質量%以下。所謂樹脂組成物之樹脂成分表示樹脂組成物之不揮發成分中，除去(B)無機填充材之成分。(A-1)液狀環氧樹脂之量若為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。(A-1) The range of the amount of liquid epoxy resin is preferably 1 mass % or more, preferably 1.5 mass % or more, and preferably 2 mass %, based on 100 mass % of the resin component in the resin composition. Mass% or more, particularly preferably 5 mass% or more, preferably 40 mass% or less, more preferably 30 mass% or less, more preferably 20 mass% or less. The resin component of the resin composition means the component excluding (B) the inorganic filler among the non-volatile components of the resin composition. (A-1) When the amount of liquid epoxy resin is within the above range, fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally be made particularly good.

(A-1)液狀環氧樹脂以含有大量的在25℃具有前述特定範圍(例如，1,000mPa･s以下)的黏度之液狀環氧樹脂者為佳。25℃中，具有前述特定範圍之黏度的液狀環氧樹脂之量的範圍，相對於(A-1)液狀環氧樹脂之全量100質量%而言，以30質量%以上為佳，較佳為40質量%以上，更佳為50質量%以上，通常為100質量%以下。其中亦以所有(A-1)液狀環氧樹脂為在25℃中之黏度為1,000mPa･s以下的液狀環氧樹脂者為佳。25℃中具有前述特定範圍的黏度之液狀環氧樹脂的量若為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。(A-1) The liquid epoxy resin preferably contains a large amount of liquid epoxy resin having a viscosity in the aforementioned specific range (for example, 1,000 mPa･s or less) at 25°C. At 25°C, the amount of liquid epoxy resin having a viscosity in the specific range mentioned above is preferably 30 mass% or more relative to 100 mass% of the total amount of (A-1) liquid epoxy resin, and preferably Preferably it is 40 mass % or more, more preferably 50 mass % or more, and usually it is 100 mass % or less. Among them, it is preferable that all (A-1) liquid epoxy resins have a viscosity of 1,000 mPa･s or less at 25°C. When the amount of liquid epoxy resin having a viscosity within the specific range specified above at 25°C is within the above range, fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally become particularly good. .

(A)環氧樹脂亦可含有組合於(A-1)液狀環氧樹脂之(A-2)固體狀環氧樹脂。(A-2)固體狀環氧樹脂表示在溫度20℃為固體狀之環氧樹脂。作為(A-2)固體狀環氧樹脂，以於1分子中具有2個以上環氧基之固體狀環氧樹脂為佳，以於1分子中具有3個以上環氧基之固體狀環氧樹脂為較佳。(A) Epoxy resin may contain (A-2) solid epoxy resin combined with (A-1) liquid epoxy resin. (A-2) Solid epoxy resin means an epoxy resin that is solid at a temperature of 20°C. As the solid epoxy resin (A-2), a solid epoxy resin having two or more epoxy groups per molecule is preferred, and a solid epoxy resin having three or more epoxy groups per molecule is preferred. Resin is preferred.

作為(A-2)固體狀環氧樹脂，例如可舉出雙二甲酚型固體狀環氧樹脂、萘型固體狀環氧樹脂、萘型4官能固體狀環氧樹脂、萘酚酚醛清漆型固體狀環氧樹脂、甲酚酚醛清漆型固體狀環氧樹脂、二環戊二烯型固體狀環氧樹脂、參酚型固體狀環氧樹脂、萘酚型固體狀環氧樹脂、聯苯基型固體狀環氧樹脂、亞萘基醚型固體狀環氧樹脂、蒽型固體狀環氧樹脂、雙酚A型固體狀環氧樹脂、雙酚AF型固體狀環氧樹脂、酚芳烷基型固體狀環氧樹脂、四苯基乙烷型固體狀環氧樹脂、苯酚鄰苯二甲醯亞胺型固體狀環氧樹脂。(A-2)固體狀環氧樹脂可單獨使用1種類，亦可組合2種類以上而使用。Examples of (A-2) solid epoxy resins include bisxylenol type solid epoxy resin, naphthalene type solid epoxy resin, naphthalene type tetrafunctional solid epoxy resin, and naphthol novolac type Solid epoxy resin, cresol novolak type solid epoxy resin, dicyclopentadiene type solid epoxy resin, ginseng type solid epoxy resin, naphthol type solid epoxy resin, biphenyl type Type solid epoxy resin, naphthylene ether type solid epoxy resin, anthracene type solid epoxy resin, bisphenol A type solid epoxy resin, bisphenol AF type solid epoxy resin, phenolic aralkyl type Type solid epoxy resin, tetraphenylethane type solid epoxy resin, phenol phthalimide type solid epoxy resin. (A-2) Solid epoxy resin can be used individually by 1 type, and can also be used in combination of 2 or more types.

(A-2)固體狀環氧樹脂由可得到優異耐熱性之硬化物的觀點來看，以含有具有芳香環之固體狀環氧樹脂者為佳，亦可僅含有具有芳香環之固體狀環氧樹脂者。作為含有芳香環之固體狀環氧樹脂，例如可舉出雙二甲酚型固體狀環氧樹脂、萘型固體狀環氧樹脂、萘型4官能固體狀環氧樹脂、萘酚酚醛清漆型固體狀環氧樹脂、甲酚酚醛清漆型固體狀環氧樹脂、參酚型固體狀環氧樹脂、萘酚型固體狀環氧樹脂、聯苯基型固體狀環氧樹脂、亞萘基醚型固體狀環氧樹脂、蒽型固體狀環氧樹脂、雙酚A型固體狀環氧樹脂、雙酚AF型固體狀環氧樹脂、酚芳烷基型固體狀環氧樹脂、四苯基乙烷型固體狀環氧樹脂、苯酚鄰苯二甲醯亞胺型固體狀環氧樹脂。(A-2) Solid epoxy resin From the viewpoint of obtaining a cured product with excellent heat resistance, it is preferable to contain a solid epoxy resin having an aromatic ring. It may also contain only a solid ring having an aromatic ring. Oxygen resin. Examples of the solid epoxy resin containing an aromatic ring include bisxylenol type solid epoxy resin, naphthalene type solid epoxy resin, naphthalene type tetrafunctional solid epoxy resin, and naphthol novolac type solid epoxy resin. epoxy resin, cresol novolak type solid epoxy resin, phenol type solid epoxy resin, naphthol type solid epoxy resin, biphenyl type solid epoxy resin, naphthylene ether type solid epoxy resin, anthracene solid epoxy resin, bisphenol A solid epoxy resin, bisphenol AF solid epoxy resin, phenol aralkyl solid epoxy resin, tetraphenylethane type Solid epoxy resin, phenol phthalimide type solid epoxy resin.

作為(A-2)固體狀環氧樹脂之具體例子，可舉出DIC公司製的「HP4032H」(萘型固體狀環氧樹脂)；DIC公司製的「HP-4700」、「HP-4710」(萘型4官能固體狀環氧樹脂)；DIC公司製的「N-690」(甲酚酚醛清漆型固體狀環氧樹脂)；DIC公司製的「N-695」(甲酚酚醛清漆型固體狀環氧樹脂)；DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」、「HP-7200L」(二環戊二烯型固體狀環氧樹脂)；DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(亞萘基醚型固體狀環氧樹脂)；日本化藥公司製的「EPPN-502H」(參酚型固體狀環氧樹脂)；日本化藥公司製的「NC7000L」(萘酚酚醛清漆型固體狀環氧樹脂)；日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3000FH」、「NC3100」(聯苯基型固體狀環氧樹脂)；日鐵化學&材料公司製的「ESN475V」(萘酚型固體狀環氧樹脂)、「ESN4100V」(萘型固體狀環氧樹脂)；日鐵化學&材料公司製的「ESN485」(萘酚型固體狀環氧樹脂)；日鐵化學&材料公司製的「ESN375」(二羥基萘型固體狀環氧樹脂)；三菱化學公司製的「YX4000H」、「YX4000」、「YX4000HK」、「YL7890」(雙二甲酚型固體狀環氧樹脂)；三菱化學公司製的「YL6121」(聯苯基型固體狀環氧樹脂)；三菱化學公司製的「YX8800」(蒽型固體狀環氧樹脂)；三菱化學公司製的「YX7700」(酚芳烷基型固體狀環氧樹脂)；大阪氣體化學公司製的「PG-100」、「CG-500」；三菱化學公司製的「YL7760」(雙酚AF型固體狀環氧樹脂)；三菱化學公司製的「YL7800」(芴型固體狀環氧樹脂)；三菱化學公司製的「jER1010」(雙酚A型固體狀環氧樹脂)；三菱化學公司製的「jER1031S」(四苯基乙烷型固體狀環氧樹脂)；日本化藥公司製的「WHR991S」(苯酚鄰苯二甲醯亞胺型固體狀環氧樹脂)等。Specific examples of the (A-2) solid epoxy resin include "HP4032H" (naphthalene type solid epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" manufactured by DIC (Naphthalene type tetrafunctional solid epoxy resin); "N-690" (cresol novolac type solid epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type solid epoxy resin) manufactured by DIC Corporation type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type solid epoxy resin) manufactured by DIC Corporation; manufactured by DIC Corporation "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type solid epoxy resin); Nippon Kayaku "EPPN-502H" (ginseng phenol type solid epoxy resin) manufactured by the company; "NC7000L" (naphthol novolac type solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H" manufactured by Nippon Kayaku Co., Ltd. , "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type solid epoxy resin); "ESN475V" (naphthol type solid epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd., "ESN4100V" (naphthalene-type solid epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ESN485" (naphthol-type solid epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene type solid epoxy resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (bisxylenol type solid epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" manufactured by Mitsubishi Chemical Corporation ( Biphenyl type solid epoxy resin); Mitsubishi Chemical Corporation's "YX8800" (anthracene type solid epoxy resin); Mitsubishi Chemical Corporation's "YX7700" (phenol aralkyl type solid epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type solid epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type solid epoxy resin) manufactured by Mitsubishi Chemical Corporation type epoxy resin); "jER1010" (bisphenol A type solid epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenyl ethane type solid epoxy resin) manufactured by Mitsubishi Chemical Corporation; Japanized "WHR991S" (phenol phthalimide type solid epoxy resin) manufactured by a pharmaceutical company, etc.

(A-2)固體狀環氧樹脂之重量平均分子量(Mw)，以100～5,000為佳，較佳為250～3,000，更佳為400～1,500。(A-2) The weight average molecular weight (Mw) of the solid epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and more preferably 400 to 1,500.

(A-2)固體狀環氧樹脂的環氧當量之範圍可與(A-1)液狀環氧樹脂之環氧當量的範圍相同。The range of the epoxy equivalent of the solid epoxy resin (A-2) may be the same as the range of the epoxy equivalent of the liquid epoxy resin (A-1).

作為(A)環氧樹脂，組合(A-1)液狀環氧樹脂與(A-2)固體狀環氧樹脂而使用之情況時，此等質量比((A-1)液狀環氧樹脂：(A-2)固體狀環氧樹脂)以50：1～1：50為佳，較佳為30：1～1：30，特佳為10：1～1：10。When (A) epoxy resin is used in combination with (A-1) liquid epoxy resin and (A-2) solid epoxy resin, the mass ratio of ((A-1) liquid epoxy resin The resin (A-2) solid epoxy resin) is preferably 50:1 to 1:50, more preferably 30:1 to 1:30, and particularly preferably 10:1 to 1:10.

含有(A-1)液狀環氧樹脂及(A-2)固體狀環氧樹脂之(A)環氧樹脂中，以含有於1分子中具有2個以上環氧基之環氧樹脂者為佳。相對於(A)環氧樹脂之全量100質量%而言，於1分子中具有2個以上環氧基之(A)環氧樹脂的量之範圍以50質量%以上為佳，較佳為60質量%以上，特佳為70質量%以上，通常為100質量%以下。The (A) epoxy resin containing (A-1) liquid epoxy resin and (A-2) solid epoxy resin is an epoxy resin containing two or more epoxy groups per molecule. good. The amount of the (A) epoxy resin having two or more epoxy groups in one molecule is preferably in the range of 50 mass% or more, preferably 60 mass%, based on 100 mass% of the total amount of the (A) epoxy resin. Mass % or more, preferably 70 mass % or more, and usually 100 mass % or less.

樹脂組成物中之(A)環氧樹脂的量相對於樹脂組成物中之不揮發成分100質量%而言，以5質量%以上為佳，較佳為10質量%以上，更佳為15質量%以上，以50質量%以下為佳，較佳為40質量%以下，更佳為30質量%以下。(A)環氧樹脂之量在前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。The amount of (A) epoxy resin in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, and more preferably 15 mass% with respect to 100 mass% of the non-volatile components in the resin composition. % or more, preferably 50 mass% or less, more preferably 40 mass% or less, more preferably 30 mass% or less. (A) When the amount of epoxy resin is within the above range, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally become particularly good.

樹脂組成物中之(A)環氧樹脂的量，相對於樹脂組成物中之樹脂成分100質量%而言，以10質量%以上為佳，較佳為30質量%以上，更佳為50質量%以上，以90質量%以下為佳，較佳為80質量%以下，更佳為70質量%以下。(A)環氧樹脂之量在前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。The amount of (A) epoxy resin in the resin composition is preferably 10 mass% or more, preferably 30 mass% or more, and more preferably 50 mass%, based on 100 mass% of the resin component in the resin composition. % or more, preferably 90 mass% or less, more preferably 80 mass% or less, more preferably 70 mass% or less. (A) When the amount of epoxy resin is within the above range, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally become particularly good.

[(B)無機填充材] 有關本發明之一實施形態的樹脂組成物含有作為(B)成分之(B)無機填充材。(B)無機填充材通常以粒子狀態下而含於樹脂組成物中。 [(B) Inorganic filler] The resin composition according to one embodiment of the present invention contains the (B) inorganic filler as the (B) component. (B) The inorganic filler is usually contained in the resin composition in a particle state.

(B)無機填充材可為無機化合物之粒子。作為含於(B)無機填充材的材料，例如可舉出二氧化矽、氧化鋁、玻璃、堇青石、矽酸化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、勃姆石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、酸化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯及磷酸鎢酸鋯等。此等中亦以二氧化矽、氧化鋁為佳，以二氧化矽為特佳。作為二氧化矽，例如可舉出無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又，作為二氧化矽以球形二氧化矽為佳。(B)無機填充材可單獨使用1種類，亦可組合2種以上而使用。(B) The inorganic filler may be particles of inorganic compounds. Examples of materials contained in (B) the inorganic filler include silica, alumina, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite. , boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanate Magnesium, bismuth titanate, titanium oxide, zirconium acidate, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon dioxide and alumina are also preferred, and silicon dioxide is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferred as the silica. (B) Inorganic filler can be used individually by 1 type, and can also be used in combination of 2 or more types.

(B)無機填充材含有特定範圍之量的(B-1)含碳的無機填充材。所謂(B-1)含碳的無機填充材表示含有特定範圍之量的碳之無機填充材。因此，(B-1)可為含有特定範圍之量的碳之無機化合物的粒子。(B-1)含碳的無機填充材之碳含有量的範圍，通常為0.1質量%以上，以0.2質量%以上為佳，更佳為0.3質量%以上，特佳為0.4質量%以上，以5質量%以下為佳，較佳為3質量%以下，更佳為1質量%以下。於(B-1)含碳的無機填充材之碳含有量中，未含有表面處理劑所含有的碳原子之量。因此，例如藉由含有碳原子的表面處理劑施予表面處理的(B-1)含碳的無機填充材之「碳含有量」中未含有前述表面處理劑之碳原子的量。(B) The inorganic filler contains the carbon-containing inorganic filler (B-1) in a specific range. (B-1) The carbon-containing inorganic filler means an inorganic filler containing an amount of carbon in a specific range. Therefore, (B-1) may be particles of an inorganic compound containing an amount of carbon in a specific range. (B-1) The carbon content range of the carbon-containing inorganic filler is usually 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.3 mass% or more, particularly preferably 0.4 mass% or more, and The content is preferably 5 mass% or less, more preferably 3 mass% or less, and more preferably 1 mass% or less. The carbon content of the carbon-containing inorganic filler (B-1) does not include the amount of carbon atoms contained in the surface treatment agent. Therefore, for example, the "carbon content" of the carbon-containing inorganic filler (B-1) surface-treated with a surface treatment agent containing carbon atoms does not include the amount of carbon atoms of the surface treatment agent.

無機填充材之碳含有量可藉由螢光X線分析法及固體NMR法而測定。對於螢光X線分析法，例如可參照九州大學中央分析中心「Center News」vol.40 No. 1,2021(2021年7月5日發行)。但，如前述，於(B-1)含碳的無機填充材之碳含有量中未含有表面處理劑所含有的碳原子之量。因此，(B-1)含碳的無機填充材之碳含有量在表面處理之前進行測定者為佳。對於經表面處理的無機填充材，例如進行強酸及強鹼等化學處理，與無機填充材粒子之最外層同時溶解於表面處理劑後進行測定，可測定碳原子之量。The carbon content of the inorganic filler can be measured by fluorescence X-ray analysis and solid-state NMR. For the fluorescence X-ray analysis method, for example, Kyushu University Central Analysis Center "Center News" vol. 40 No. 1, 2021 (issued on July 5, 2021). However, as mentioned above, the carbon content of the carbon-containing inorganic filler (B-1) does not include the amount of carbon atoms contained in the surface treatment agent. Therefore, it is preferable that the carbon content of (B-1) the carbon-containing inorganic filler be measured before surface treatment. For surface-treated inorganic fillers, chemical treatments such as strong acid and strong alkali are carried out, and the outermost layer of the inorganic filler particles is dissolved in the surface treatment agent at the same time and measured, and the amount of carbon atoms can be measured.

(B-1)含碳的無機填充材通常為將上述無機化合物作為主成分而含有的粒子。因此，(B-1)含碳的無機填充材可含有組合於碳之上述無機化合物。前述無機化合物之中亦由顯著發揮本發明之效果的觀點來看，以二氧化矽為佳。因此，作為(B-1)含碳的無機填充材，以含有特定範圍之量的碳之二氧化矽粒子為佳。該二氧化矽粒子所含有的二氧化矽之量以60質量%以上為佳，較佳為70質量%以上，更佳為80質量%以上，特佳為90質量%以上。二氧化矽之量可藉由螢光X線分析法測定。(B-1) The carbon-containing inorganic filler is usually particles containing the above-mentioned inorganic compound as a main component. Therefore, (B-1) the carbon-containing inorganic filler may contain the above-mentioned inorganic compound combined with carbon. Among the above-mentioned inorganic compounds, silica is preferred from the viewpoint of significantly exhibiting the effects of the present invention. Therefore, as the carbon-containing inorganic filler (B-1), silica particles containing an amount of carbon in a specific range are preferred. The amount of silica contained in the silica particles is preferably 60 mass% or more, more preferably 70 mass% or more, more preferably 80 mass% or more, and particularly preferably 90 mass% or more. The amount of silicon dioxide can be determined by fluorescence X-ray analysis.

上述(B-1)含碳的無機填充材之製造方法並無特別限制。由省能量、省成本及保護環境之觀點來看，(B-1)含碳的無機填充材由植物原料所製造者為佳。例如馬尾科及水稻科之植物具有可由土地中吸收及累積矽成分之性質。因此，藉由燃燒此等植物時，作為燃燒灰可製造二氧化矽(專利第6389349號公報)。以下有時將自如此植物原料製造的二氧化矽稱為「生物質二氧化矽」。生物質二氧化矽通常因含有碳，故可作為(B-1)含碳的無機填充材使用。又，(B-1)含碳的無機填充材亦可使用販售品。作為(B-1)含碳的無機填充材的販售品之例子，可舉出由水稻殻所製造之生物質二氧化矽的M.I.T公司製的「ethical silica」。The manufacturing method of the above-mentioned (B-1) carbon-containing inorganic filler is not particularly limited. From the viewpoint of energy saving, cost saving and environmental protection, (B-1) the carbon-containing inorganic filler material is preferably made of plant raw materials. For example, plants of the Horsetail and Oryzae families have the property of absorbing and accumulating silicon components from the soil. Therefore, when these plants are burned, silica can be produced as combustion ash (Patent No. 6389349). Hereinafter, silica produced from such plant raw materials is sometimes referred to as "biomass silica". Biomass silica usually contains carbon, so it can be used as (B-1) carbon-containing inorganic filler. In addition, (B-1) a commercial product can also be used as the carbon-containing inorganic filler. Examples of commercially available carbon-containing inorganic fillers (B-1) include "ethical silica" produced by M.I.T., which is biomass silica produced from rice husks.

(B-1)含碳的無機填充材可單獨使用1種類，亦可組合2種類以上而使用。(B-1) The carbon-containing inorganic filler may be used alone or in combination of two or more types.

(B-1)含碳的無機填充材之平均粒徑由顯著得到本發明之所望效果之觀點來看，以0.01μm以上為佳，較佳為0.1μm以上，更佳為0.5μm以上，以10μm以下為佳，較佳為8μm以下，更佳為5μm以下。(B-1) The average particle diameter of the carbon-containing inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of significantly obtaining the desired effects of the present invention. It is preferably 10 μm or less, more preferably 8 μm or less, and more preferably 5 μm or less.

(B-1)含碳的無機填充材等之無機填充材的平均粒徑可依據米氏(Mie)散射理論而藉由雷射衍射･散射法進行測定。具體而言，藉由雷射衍射散射式粒徑分布測定裝置，無機填充材之粒徑分布依據體積基準而作成，可將該中位直徑作為平均粒徑而測定。測定試樣使用於樣品瓶中秤取無機填充材100mg及甲基乙基酮10g，以超音波進行10分鐘分散者。將測定試樣使用雷射衍射式粒徑分布測定裝置，將使用光源波長設定為藍色及紅色，以流動池方式測定無機填充材之體積基準的粒徑分布，自所得的粒徑分布算出作為中位直徑之平均粒徑。作為雷射衍射式粒徑分布測定裝置，例如可舉出堀場製作所公司製「LA-960」等。(B-1) The average particle size of inorganic fillers such as carbon-containing inorganic fillers can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, using a laser diffraction scattering particle size distribution measuring device, the particle size distribution of the inorganic filler is prepared based on the volume basis, and the median diameter can be measured as the average particle size. For the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed in a sample bottle and dispersed using ultrasonic waves for 10 minutes. A laser diffraction type particle size distribution measuring device is used for the measurement sample, and the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured using a flow cell method. From the obtained particle size distribution, calculated as Median diameter is the average particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(B-1)含碳的無機填充材之比表面積由顯著得到本發明之所望效果的觀點來看，以0.1m 2/g以上為佳，較佳為0.5m 2/g以上，更佳為1m 2/g以上，特佳為3m 2/g以上，以100m 2/g以下為佳，較佳為70m 2/g以下，更佳為50m 2/g以下，特佳為40m 2/g以下。無機填充材之比表面積依據BET法，使用比表面積測定裝置(Mountech公司製Macsorb HM-1210)，於試料表面吸附氮氣，使用BET多點法算出比表面積而可測定。 (B-1) The specific surface area of the carbon-containing inorganic filler is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, and more preferably 0.5 m 2 /g or more, from the viewpoint of significantly achieving the desired effects of the present invention. 1m 2 /g or more, preferably 3m 2 /g or more, preferably 100m 2 /g or less, preferably 70m 2 /g or less, more preferably 50m 2 /g or less, particularly preferably 40m 2 /g or less . The specific surface area of the inorganic filler material can be measured based on the BET method by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.), adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multi-point method.

(B-1)含碳的無機填充材由提高耐濕性及分散性之觀點來看，以表面處理劑進行處理者為佳。作為表面處理劑，例如可舉出含有氟之矽烷偶合劑、胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸鹽系偶合劑等。表面處理劑可單獨使用1種類，亦可任意組合2種類以上而使用。(B-1) The carbon-containing inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane, and organosilazane. compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

作為表面處理劑之販售品，例如可舉出信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethyl Oxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-" manufactured by Shin-Etsu Chemical Industries, Ltd. 4803" (long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc.

藉由表面處理劑之表面處理的程度，由(B-1)含碳的無機填充材之分散性提高的觀點來看，控制在特定範圍者為佳。具體而言，(B-1)含碳的無機填充材100質量%以藉由0.2質量%～5質量%之表面處理劑進行表面處理者為佳，以藉由0.2質量%～3質量%之表面處理劑進行表面處理者為較佳，以藉由0.3質量%～2質量%之表面處理劑進行表面處理者為更佳。From the viewpoint of improving the dispersibility of the (B-1) carbon-containing inorganic filler, the degree of surface treatment by the surface treatment agent is preferably controlled within a specific range. Specifically, 100% by mass of the carbon-containing inorganic filler (B-1) is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and preferably 0.2% to 3% by mass of a surface treatment agent. It is preferable to perform surface treatment with a surface treatment agent, and it is more preferable to perform surface treatment with a surface treatment agent of 0.3 mass % to 2 mass %.

有關本發明之一實施形態的樹脂組成物含有特定範圍量的(B-1)含碳的無機填充材。(B-1)含碳的無機填充材量之範圍相對於樹脂組成物中之不揮發成分100質量%而言，通常為10質量%以上，以15質量%以上為佳，較佳為20質量%以上，以90質量%以下為佳，較佳為85質量%以下，更佳為80質量%以下。(B-1)含碳的無機填充材之量若為前述範圍的情況時，可提高流動性及絕緣信賴性雙方，且通常可使最低熔融黏度及耐熱性變得良好。The resin composition according to one embodiment of the present invention contains (B-1) a carbon-containing inorganic filler in a specific range. (B-1) The range of the amount of the carbon-containing inorganic filler relative to 100 mass% of the non-volatile components in the resin composition is usually 10 mass% or more, preferably 15 mass% or more, and more preferably 20 mass% % or more, preferably 90 mass% or less, more preferably 85 mass% or less, more preferably 80 mass% or less. (B-1) When the amount of the carbon-containing inorganic filler is within the above range, both fluidity and insulation reliability can be improved, and the minimum melt viscosity and heat resistance can generally be improved.

(B-1)含碳的無機填充材量之範圍相對於(B)無機填充材之全量100質量%而言，以20質量%以上為佳，較佳為25質量%，更佳為30質量%以上，通常為100質量%以下。(B-1)含碳的無機填充材之量為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。(B-1) The range of the amount of the carbon-containing inorganic filler relative to 100% by mass of the total amount of the inorganic filler (B) is preferably 20 mass% or more, more preferably 25 mass%, and more preferably 30 mass% % or more, usually 100 mass% or less. (B-1) When the amount of the carbon-containing inorganic filler is within the above range, fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally be made particularly good.

(B-1)含碳的無機填充材與(A)環氧樹脂之質量比((B-1)含碳的無機填充材/(A)環氧樹脂)的範圍以0.5以上為佳，較佳為1以上，更佳為1.2以上，特佳為1.5以上，以10以下為佳，較佳為8以下，更佳為6以下。質量比((B-1)含碳的無機填充材/(A)環氧樹脂)在前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。The mass ratio of (B-1) carbon-containing inorganic filler to (A) epoxy resin ((B-1) carbon-containing inorganic filler/(A) epoxy resin) is preferably in the range of 0.5 or more, preferably Preferably it is 1 or more, more preferably 1.2 or more, particularly preferably 1.5 or more, preferably 10 or less, preferably 8 or less, more preferably 6 or less. When the mass ratio ((B-1) carbon-containing inorganic filler/(A) epoxy resin) is within the aforementioned range, fluidity and insulation reliability can be effectively improved, and the lowest melt viscosity and heat resistance can usually be achieved. Become particularly good.

(B-1)含碳的無機填充材與(A-1)液狀環氧樹脂之質量比((B-1)含碳的無機填充材/(A-1)液狀環氧樹脂)的範圍以1以上為佳，較佳為5以上，更佳為10以上，以200以下為佳，較佳為150以下，更佳為100以下。質量比((B-1)含碳的無機填充材/(A-1)液狀環氧樹脂)為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。The mass ratio of (B-1) carbon-containing inorganic filler to (A-1) liquid epoxy resin ((B-1) carbon-containing inorganic filler/(A-1) liquid epoxy resin) The range is preferably 1 or more, preferably 5 or more, more preferably 10 or more, preferably 200 or less, preferably 150 or less, and more preferably 100 or less. When the mass ratio ((B-1) carbon-containing inorganic filler/(A-1) liquid epoxy resin) is within the above range, fluidity and insulation reliability can be effectively improved, and the lowest melting point can usually be achieved. The viscosity and heat resistance become particularly good.

(B-1)含碳的無機填充材與「在25℃中之黏度為1,000mPa･s以下之液狀環氧樹脂」之質量比((B-1)含碳的無機填充材/「在25℃中之黏度為1,000mPa･s以下的液狀環氧樹脂」)之範圍，以1以上為佳，較佳為5以上，更佳為10以上，特佳為20以上，以200以下為佳，較佳為150以下，更佳為100以下，特佳為70以下。質量比((B-1)含碳的無機填充材/「在25℃中之黏度為1,000mPa･s以下之液狀環氧樹脂」)為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。(B-1) Mass ratio of carbon-containing inorganic filler to "liquid epoxy resin with a viscosity of 1,000 mPa･s or less at 25°C" ((B-1) Carbon-containing inorganic filler/"in "Liquid epoxy resin with a viscosity of 1,000 mPa･s or less at 25°C") range is preferably 1 or more, more preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more, and 200 or less. Good, preferably below 150, more preferably below 100, particularly preferably below 70. When the mass ratio ((B-1) carbon-containing inorganic filler / "liquid epoxy resin with a viscosity of 1,000 mPa･s or less at 25°C") is within the above range, the fluidity and Insulation reliability, and usually makes the lowest melt viscosity and heat resistance particularly good.

有關本發明之一實施形態的樹脂組成物亦可含有組合於(B-1)含碳的無機填充材之(B-2)任意的無機填充材。(B-2)任意之無機填充材表示(B-1)含碳的無機填充材以外的無機填充材，因此其表示碳含有量之範圍未在上述範圍的無機填充材。The resin composition according to one embodiment of the present invention may contain any inorganic filler (B-2) combined with the carbon-containing inorganic filler (B-1). (B-2) Any inorganic filler means an inorganic filler other than the carbon-containing inorganic filler (B-1), and therefore means an inorganic filler whose carbon content is not within the above range.

(B-2)任意之無機填充材可為上述無機化合物之粒子。無機化合物之中亦以二氧化矽、氧化鋁為佳，以二氧化矽為特佳。作為二氧化矽，例如可舉出無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又，作為二氧化矽以球形二氧化矽為佳。(B-2)任意之無機填充材可單獨使用1種類，亦可組合2種以上而使用。(B-2) The optional inorganic filler may be particles of the above-mentioned inorganic compound. Among the inorganic compounds, silica and alumina are also preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferred as the silica. (B-2) Arbitrary inorganic fillers can be used individually by one type or in combination of two or more types.

作為(B-2)任意之無機填充材的販售品，例如可舉出日鐵化學&材料公司製的「SP60-05」、「SP507-05」；Admatechs公司製的「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」、「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；Denka Company製的「UFP-30」、「DAW-03」、「FB-105FD」；Tokuyama公司製的「SilfirNSS-3N」、「SilfirNSS-4N」、「SilfirNSS-5N」；太平洋水泥公司製「MG-005」等。(B-2) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; and "YC100C" and "YA050C" manufactured by Admatechs. ", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; "UFP-30", "DAW-03" made by Denka Company, "FB-105FD"; "SilfirNSS-3N", "SilfirNSS-4N", "SilfirNSS-5N" made by Tokuyama Co., Ltd.; "MG-005" made by Pacific Cement Co., Ltd., etc.

(B-2)任意之無機填充材的平均粒徑由顯著得到本發明之所望效果的觀點來看，以0.01μm以上為佳，較佳為0.05μm以上，更佳為0.1μm以上，特佳為0.2μm以上，以10μm以下為佳，較佳為5μm以下，更佳為3μm以下。(B-2) The average particle diameter of any inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably from the viewpoint of significantly achieving the desired effects of the present invention. It is 0.2 μm or more, preferably 10 μm or less, more preferably 5 μm or less, more preferably 3 μm or less.

(B-2)任意之無機填充材的比表面積由顯著得到本發明之所望效果的觀點來看，以0.1m 2/g以上為佳，較佳為0.5m 2/g以上，更佳為1m 2/g以上，特佳為3m 2/g以上，以100m 2/g以下為佳，較佳為70m 2/g以下，更佳為50m 2/g以下，特佳為40m 2/g以下。 (B-2) The specific surface area of any inorganic filler is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, and more preferably 1 m 2 from the viewpoint of significantly achieving the desired effects of the present invention. 2 /g or more, particularly preferably 3m 2 /g or more, preferably 100m 2 /g or less, more preferably 70m 2 /g or less, more preferably 50m 2 /g or less, particularly preferably 40m 2 /g or less.

(B-2)任意之無機填充材由提高耐濕性及分散性之觀點來看，以藉由表面處理劑進行處理者為佳。作為(B-2)任意之無機填充材的表面處理劑之例子，可舉出與(B-1)含碳的無機填充材之表面處理劑的相同例子。表面處理劑可單獨使用1種類，亦可任意組合2種類以上而使用。又，藉由(B-2)任意之無機填充材的表面處理劑進行表面處理之程度範圍可與藉由(B-1)含碳的無機填充材的表面處理劑進行表面處理之程度範圍相同。(B-2) Any inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent for the arbitrary inorganic filler (B-2) include the same examples as the surface treatment agent for the carbon-containing inorganic filler (B-1). One type of surface treatment agent may be used alone, or two or more types may be used in any combination. In addition, the extent of surface treatment by the surface treatment agent of (B-2) any inorganic filler can be the same as the extent of surface treatment by the surface treatment agent of (B-1) the carbon-containing inorganic filler. .

樹脂組成物中之(B)無機填充材的量，相對於樹脂組成物之不揮發成分100質量%而言，以10質量%以上為佳，較佳為20質量%以上，更佳為40質量%以上，特佳為50質量%以上，以90質量%以下為佳，較佳為85質量%以下，特佳為80質量%以下。(B)無機填充材之量為前述範圍之情況時，可有效地提高流動性及絕緣信賴性，且通常可使最低熔融黏度及耐熱性變得特別良好。The amount of (B) inorganic filler in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, and more preferably 40 mass%, based on 100 mass% of the non-volatile components of the resin composition. % or more, particularly preferably 50 mass % or more, preferably 90 mass % or less, more preferably 85 mass % or less, particularly preferably 80 mass % or less. (B) When the amount of the inorganic filler is within the above range, the fluidity and insulation reliability can be effectively improved, and the minimum melt viscosity and heat resistance can generally be made particularly good.

[(C)硬化劑] 有關本發明之一實施形態的樹脂組成物亦可進一步含有組合於(A)～(B)成分之作為任意成分的(C)硬化劑。作為(C)成分之(C)硬化劑若無特別說明則未含有相當於上述(A)～(B)成分者。(C)硬化劑可具有與(A)環氧樹脂進行反應而使樹脂組成物硬化的功能。(C)硬化劑可單獨使用1種類，亦可組合2種類以上而使用。 [(C) Hardener] The resin composition according to one embodiment of the present invention may further contain a curing agent (C) as an optional component combined with the components (A) to (B). Unless otherwise specified, the (C) curing agent as the component (C) does not contain components equivalent to the above-mentioned components (A) to (B). (C) The hardener may react with (A) epoxy resin to harden the resin composition. (C) One type of hardening agent may be used alone, or two or more types may be used in combination.

作為較佳(C)硬化劑，例如可舉出活性酯系硬化劑、氰酸酯系硬化劑、酚系硬化劑、碳二亞胺系硬化劑、酸酐系硬化劑、胺系硬化劑、苯並噁嗪系硬化劑、硫醇系硬化劑等。Preferable (C) curing agents include, for example, active ester curing agents, cyanate ester curing agents, phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, and benzene curing agents. Oxazine-based hardeners, thiol-based hardeners, etc.

作為活性酯系硬化劑，一般使用酚酯類、硫代酚酯類、N-羥基胺酯類、雜環羥基化合物的酯類等之1分子中具有2個以上的反應活性高之酯基的化合物為佳。該活性酯系硬化劑係以藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而得者為佳。特別由提高耐熱性之觀點來看，以由羧酸化合物與羥基化合物而得之活性酯系硬化劑為佳，以由羧酸化合物與酚化合物及/或萘酚化合物而得之活性酯系硬化劑為較佳。作為羧酸化合物，例如可舉出安息香酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯四酸等。作為酚化合物或萘酚化合物，例如可舉出氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞嗪、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三醇、二環戊二烯型二酚化合物、酚酚醛清漆等。其中所謂「二環戊二烯型二酚化合物」表示於二環戊二烯1分子中縮合酚2分子而得之二酚化合物。As active ester hardeners, those having two or more highly reactive ester groups in one molecule such as phenolic esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds are generally used. Compounds are better. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based hardener obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is preferred. agent is better. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, and toluene. Sylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phlorotriol, dicyclopentadienyl diphenol Compounds, phenolic novolaks, etc. The "dicyclopentadiene-type diphenol compound" here refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

具體而言，作為活性酯系硬化劑，以二環戊二烯型活性酯系硬化劑、含有萘結構的萘型活性酯系硬化劑、含有酚酚醛清漆的乙醯化物之活性酯系硬化劑、含有酚酚醛清漆的苯甲醯基化物之活性酯系硬化劑為佳，其中亦以選自二環戊二烯型活性酯系硬化劑，及萘型活性酯系硬化劑的至少1種者為較佳。作為二環戊二烯型活性酯系硬化劑，以含有二環戊二烯型二酚結構的活性酯系硬化劑為佳。Specifically, as the active ester-based hardener, a dicyclopentadiene-type active ester-based hardener, a naphthalene-type active ester-based hardener containing a naphthalene structure, and an active ester-based hardener containing an acetate of phenolic novolac are used. , an active ester hardener containing a benzyl compound of phenolic novolak is preferred, and at least one selected from the group consisting of dicyclopentadiene-type active ester hardeners and naphthalene-type active ester hardeners is preferred. For better. As the dicyclopentadiene-type active ester-based hardener, an active ester-based hardener containing a dicyclopentadiene-type diphenol structure is preferred.

作為活性酯系硬化劑之販售品，例如作為含有二環戊二烯型二酚結構之活性酯系硬化劑，可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「EXB-8000L」、「EXB-8000L-65M」、「EXB-8000L-65TM」、「HPC-8000L-65TM」、「HPC-8000」、「HPC-8000-65T」、「HPC-8000H」、「HPC-8000H-65TM」(DIC公司製)；作為含有萘結構的活性酯系硬化劑，可舉出「HP-B-8151-62T」、「EXB-8100L-65T」、「EXB-8150-60T」、「EXB-8150-62T」、「EXB-9416-70BK」、「HPC-8150-60T」、「HPC-8150-62T」、「EXB9416-70BK」、「EXB-8」(DIC公司製)；作為含有磷的活性酯系硬化劑，可舉出「EXB9401」(DIC公司製)；作為酚酚醛清漆之乙醯化物的活性酯系硬化劑，可舉出「DC808」(三菱化學公司製)；作為酚酚醛清漆之苯甲醯基化物的活性酯系硬化劑，可舉出「YLH1026」、「YLH1030」、「YLH1048」(三菱化學公司製)；作為含有苯乙烯基及萘結構之活性酯系硬化劑，可舉出「PC1300-02-65MA」(air water公司製)等。Examples of commercially available active ester hardeners containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "EXB-8000L" , "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H- 65TM" (manufactured by DIC Corporation); examples of active ester-based hardeners containing a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", and "EXB -8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB9416-70BK", "EXB-8" (manufactured by DIC Corporation); as containing phosphorus Examples of active ester-based hardeners include "EXB9401" (manufactured by DIC Corporation); examples of active ester-based hardeners for the acetate of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of phenolic novolacs Examples of active ester hardeners of benzoyl compounds of varnishes include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); as active ester hardeners containing a styrene group and a naphthalene structure, Examples include "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.).

作為氰酸酯系硬化劑，可使用於1分子內中具有1個以上，較佳為具有2個以上氰酸酯基之化合物。作為氰酸酯系硬化劑，例如可舉出雙酚A二氰酸酯、聚酚氰酸酯(寡(3-亞甲基-1,5-伸苯基氰酸酯))、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫代醚、及雙(4-氰酸酯苯基)醚等2官能氰酸酯系硬化劑、由酚酚醛清漆及甲酚酚醛清漆等所衍生的多官能氰酸酯系硬化劑、此等氰酸酯系硬化劑的一部分經三嗪化的預聚物等。作為氰酸酯系硬化劑之具體例子，可舉出Lonza Japan公司製的「PT30」及「PT60」(皆為酚酚醛清漆型多官能氰酸酯系硬化劑)、「BA230」、「BA230S75」(雙酚A二氰酸酯之一部分或全部經三嗪化而成為三聚物之預聚物)等。As the cyanate ester hardener, a compound having one or more, preferably two or more cyanate ester groups per molecule can be used. Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4 '-Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1 , 3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl) Bifunctional cyanate ester hardeners such as ethers, polyfunctional cyanate ester hardeners derived from phenol novolaks, cresol novolacs, etc., and prepolymers in which part of these cyanate ester hardeners are triazinized Things etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" manufactured by Lonza Japan (both are phenolic novolac-type polyfunctional cyanate ester-based hardeners), "BA230", and "BA230S75" (A prepolymer in which part or all of bisphenol A dicyanate is triazinized to become a terpolymer), etc.

作為酚系硬化劑，可使用於苯環、萘環等芳香環的1分子中鍵結1個以上羥基，較佳為具有2個以上的化合物。由耐熱性及耐水性之觀點來看，以具有酚醛清漆結構之酚系硬化劑為佳。又，由密著性之觀點來看，以含氮酚系硬化劑為佳，以含有三嗪骨架之酚系硬化劑為較佳。其中亦由高度滿足耐熱性、耐水性及密著性之觀點來看，以含有三嗪骨架之酚酚醛清漆系硬化劑為佳。作為酚系硬化劑之具體例子，例如可舉出明和化成公司製的「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製的「NHN」、「CBN」、「GPH」、日鐵化學&材料公司製的「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製的「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」、「TD-2090-60M」等。As the phenolic hardener, a compound having one or more hydroxyl groups bonded to one molecule of an aromatic ring such as a benzene ring or a naphthalene ring, preferably two or more, can be used. From the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolak structure is preferred. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is preferred. Among them, a phenolic novolak-based hardener containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN" manufactured by Nippon Steel Chemical & Materials Co., Ltd. -375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" made by DIC Corporation, "TD-2090-60M" etc.

作為碳二亞胺系硬化劑，可使用於1分子內中具有1個以上，較佳為具有2個以上的碳二亞胺基之化合物。作為碳二亞胺系硬化劑之具體例子，可舉出四亞甲基-雙(t-丁基碳二亞胺)、環己烷雙(亞甲基-t-丁基碳二亞胺)等的脂肪族雙碳二亞胺；伸苯基-雙(二甲苯基碳二亞胺)等的芳香族雙碳二亞胺等的雙碳二亞胺；聚六亞甲基碳二亞胺、聚三甲基六亞甲基碳二亞胺、聚環伸己碳二亞胺、聚(亞甲基雙環伸己碳二亞胺)、聚(異佛爾酮碳二亞胺)等的脂肪族聚碳二亞胺；聚(伸苯基碳二亞胺)、聚(亞萘基碳二亞胺)、聚(伸甲苯碳二亞胺)、聚(甲基二異丙基伸苯基碳二亞胺)、聚(三乙基伸苯基碳二亞胺)、聚(二乙基伸苯基碳二亞胺)、聚(三異丙基伸苯基碳二亞胺)、聚(二異丙基伸苯基碳二亞胺)、聚(亞二甲苯碳二亞胺)、聚(四甲基亞二甲苯碳二亞胺)、聚(亞甲基二伸苯基碳二亞胺)、聚[亞甲基雙(甲基伸苯基)碳二亞胺]等的芳香族聚碳二亞胺等的聚碳二亞胺。作為碳二亞胺系硬化劑之販售品，例如可舉出日清紡化學公司製的「碳輝石V-02B」、「碳輝石V-03」、「碳輝石V-04K」、「碳輝石V-07」及「碳輝石V-09」；line chemie公司製的「Stabaxol P」、「Stabaxol P400」、「High Cazir510」等。As the carbodiimide hardener, a compound having one or more, preferably two or more carbodiimide groups per molecule can be used. Specific examples of carbodiimide-based hardeners include tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide). aliphatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide) and other aromatic biscarbodiimides; polyhexamethylenecarbodiimide , polytrimethylhexamethylenecarbodiimide, polycyclohexamethylenecarbodiimide, poly(methylenebicyclohexamethylenecarbodiimide), poly(isophoronecarbodiimide), etc. Aliphatic polycarbodiimide; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide) Carbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylenecarbodiimide) propylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), Polycarbodiimides such as poly[methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides. Examples of commercially available carbodiimide-based hardeners include "carbopyrite V-02B", "carbopyroxene V-03", "carbopyroxene V-04K" and "carbopyroxene V" manufactured by Nisshinbo Chemical Co., Ltd. -07" and "Carbonite V-09"; "Stabaxol P", "Stabaxol P400", "High Cazir510" manufactured by line chemie, etc.

作為酸酐系硬化劑，可使用於1分子內中具有1個以上，較佳為具有2個以上酸酐基之化合物。作為酸酐系硬化劑之具體例子，可舉出鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三酸酐、苯四酸酐、二苯甲酮四羧酸二酐、聯苯基四羧酸二酐、萘四羧酸二酐、氧代二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘酚[1,2-C]呋喃-1,3-二酮、乙二醇雙(脫水偏苯三酸酯)、苯乙烯與馬來酸經共聚合之苯乙烯･馬來酸樹脂等之聚合物型的酸酐等。作為酸酐系硬化劑之販售品，例如可舉出新日本理化公司製的「HNA-100」、「MH-700」、「MTA-15」、「DDSA」、「OSA」；三菱化學公司製的「YH-306」、「YH-307」；日立化成公司製的「HN-2200」、「HN-5500」；clay valley公司製「EF-30」、「EF-40」「EF-60」、「EF-80」等。As the acid anhydride-based hardener, a compound having one or more, preferably two or more acid anhydride groups per molecule can be used. Specific examples of acid anhydride-based hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic anhydride Carboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-dioxo-3-furyl)-naphthol[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate) , polymer-type acid anhydrides such as styrene and maleic acid copolymerized by styrene and maleic acid resin. Examples of commercially available acid anhydride hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Nippon Rika Co., Ltd.; Mitsubishi Chemical Corporation's "YH-306", "YH-307"; "HN-2200", "HN-5500" made by Hitachi Chemical Co., Ltd.; "EF-30", "EF-40" and "EF-60" made by Clay Valley Co., Ltd. , "EF-80", etc.

作為胺系硬化劑，可使用於1分子內中具有1個以上，較佳為具有2個以上的胺基之化合物。作為胺系硬化劑，例如可舉出脂肪族胺類、聚醚胺類、脂環式胺類、芳香族胺類等，其中亦以芳香族胺類為佳。胺系硬化劑以第1級胺或第2級胺為佳，以第1級胺為較佳。作為胺系硬化劑之具體例子，可舉出4,4’-亞甲基雙(2,6-二甲基苯胺)、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、m-苯二胺、m-亞二甲苯二胺、二乙基甲苯二胺、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基聯苯基、2,2’-二甲基-4,4’-二胺基聯苯基、3,3’-二羥基聯苯胺、2,2-雙(3-胺基-4-羥基苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷二胺、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯基、雙(4-(4-胺基苯氧基)苯基)碸、雙(4-(3-胺基苯氧基)苯基)碸等。作為胺系硬化劑之販售品，例如可舉出Seika公司製「SEIKACURE-S」；日本化藥公司製的「KAYABOND C-200S」、「KAYABOND C-100」、「KayahardA-A」、「KayahardA-B」、「KayahardA-S」；三菱化學公司製的「EpicureW」；住友精化公司製「DTDA」等。As the amine-based hardener, a compound having one or more, preferably two or more amine groups in one molecule can be used. Examples of amine-based hardeners include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are also preferred. The amine-based hardener is preferably a first-level amine or a second-level amine, and the first-level amine is more preferred. Specific examples of the amine-based hardener include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, and 4,4'- Diaminodiphenylenediamine, 3,3'-diaminodiphenylenediamine, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diamine Diphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3 '-Dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-amino) Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminobenzene) Oxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Examples of commercially available amine-based hardeners include "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", and "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd. "KayahardA-B", "KayahardA-S"; "EpicureW" manufactured by Mitsubishi Chemical Corporation; "DTDA" manufactured by Sumitomo Seiko Chemicals, etc.

作為苯並噁嗪系硬化劑之具體例子，可舉出JFE化學公司製的「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製的「HFB2006M」；四國化成工業公司製的「P-d」、「F-a」等。Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; " P-d", "F-a", etc.

作為硫醇系硬化劑，例如可舉出三羥甲基丙烷參(3-巰基丙酸酯)、季戊四醇肆(3-巰基丁酸酯)、參(3-巰基丙基)異氰脲酸酯等。Examples of thiol-based hardeners include trimethylolpropane (3-mercaptopropionate), pentaerythritol (3-mercaptobutyrate), and ginseng (3-mercaptopropyl) isocyanurate. wait.

(C)硬化劑之活性基當量，以50g/eq.～3000g/eq.為佳，較佳為100g/eq.～1000g/eq.，更佳為100g/eq.～500g/eq.，特佳為100g/eq.～350g/eq.。活性基當量表示每活性基1當量的樹脂質量。(C) The active radical equivalent of the hardener is preferably 50g/eq.~3000g/eq., preferably 100g/eq.~1000g/eq., more preferably 100g/eq.~500g/eq., especially The optimal range is 100g/eq.～350g/eq. The active group equivalent represents the resin mass per active group equivalent.

將(A)環氧樹脂的環氧基數作為1之情況時，(C)硬化劑之活性基數，以0.01以上為佳，較佳為0.1以上，更佳為0.2以上，以10以下為佳，較佳為5以下，更佳為1以下。所謂「(A)環氧樹脂之環氧基數」表示，將存在於樹脂組成物中之(A)環氧樹脂的不揮發成分之質量除以環氧當量而算出的所有值合計之值。又，將所謂「(C)硬化劑之活性基數」表示樹脂組成物中所存在的(C)硬化劑之不揮發成分的質量除以活性基當量而算出的所有值合計之值。When the epoxy group number of (A) the epoxy resin is 1, the active group number of the (C) hardener is preferably 0.01 or more, more preferably 0.1 or more, more preferably 0.2 or more, and preferably 10 or less. It is preferably 5 or less, more preferably 1 or less. The "epoxy group number of (A) epoxy resin" means the total value calculated by dividing the mass of the non-volatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of active groups of (C) curing agent" means the total value calculated by dividing the mass of non-volatile components of (C) curing agent present in the resin composition by the active group equivalent.

樹脂組成物中之(C)硬化劑的量，相對於樹脂組成物之不揮發成分100質量%而言可為0質量%，亦可為比0質量%大，以1質量%以上為佳，較佳為2質量%以上，更佳為5質量%以上，以40質量%以下為佳，較佳為30質量%以下，更佳為20質量%以下。The amount of (C) hardener in the resin composition may be 0% by mass relative to 100% by mass of the non-volatile components of the resin composition, or may be greater than 0% by mass, preferably 1% by mass or more. It is preferably 2 mass% or more, more preferably 5 mass% or more, preferably 40 mass% or less, preferably 30 mass% or less, and more preferably 20 mass% or less.

樹脂組成物中之(C)硬化劑的量相對於樹脂組成物之樹脂成分100質量%而言，可為0質量%，亦可為比0質量%大，以5質量%以上為佳，較佳為10質量%以上，更佳為20質量%以上，以70質量%以下為佳，較佳為60質量%以下，更佳為50質量%以下。The amount of (C) hardener in the resin composition may be 0% by mass relative to 100% by mass of the resin component of the resin composition, or may be greater than 0% by mass, preferably 5% by mass or more, preferably Preferably it is 10 mass % or more, more preferably 20 mass % or more, 70 mass % or less is preferred, 60 mass % or less is more preferred, and 50 mass % or less is more preferred.

[(D)硬化促進劑] 有關本發明之一實施形態的樹脂組成物中可進一步含有作為任意成分之(D)硬化促進劑。作為(D)成分之(D)硬化促進劑若無另外說明，未含有相當於上述(A)～(C)成分者。(D)硬化促進劑具有作為促進(A)環氧樹脂之硬化的硬化觸媒之功能。 [(D) Hardening accelerator] The resin composition according to one embodiment of the present invention may further contain (D) a hardening accelerator as an optional component. Unless otherwise stated, the (D) hardening accelerator as the component (D) does not contain components equivalent to the above-mentioned components (A) to (C). (D) The hardening accelerator functions as a hardening catalyst that accelerates hardening of (A) epoxy resin.

作為(D)硬化促進劑，例如可舉出磷系硬化促進劑、脲系硬化促進劑、胍系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑、胺系硬化促進劑等。其中亦以咪唑系硬化促進劑為佳。(D)硬化促進劑可單獨使用1種類，亦可組合2種類以上而使用。Examples of the (D) hardening accelerator include phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, and amine-based hardening accelerators. Among them, imidazole-based hardening accelerators are preferred. (D) The hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

作為磷系硬化促進劑，例如可舉出四丁基鏻溴化物、四丁基鏻氯化物、四丁基鏻乙酸酯、四丁基鏻癸酸酯、四丁基鏻月桂酸酯、雙(四丁基鏻)均苯四酸酯、四丁基鏻氫六氫鄰苯二甲酸酯、四丁基鏻2,6-雙[(2-羥基-5-甲基苯基)甲基]-4-甲基苯酚、二-tert-丁基二甲基鏻四苯基硼酸鹽等的脂肪族鏻鹽；甲基三苯基鏻溴化物、乙基三苯基鏻溴化物、丙基三苯基鏻溴化物、丁基三苯基鏻溴化物、苯甲基三苯基鏻氯化物、四苯基鏻溴化物、p-甲苯基三苯基鏻四-p-甲苯基硼酸鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四p-甲苯基硼酸鹽、三苯基乙基鏻四苯基硼酸鹽、參(3-甲基苯基)乙基鏻四苯基硼酸鹽、參(2-甲氧基苯基)乙基鏻四苯基硼酸鹽、(4-甲基苯基)三苯基鏻硫代氰酸酯、四苯基鏻硫代氰酸酯、丁基三苯基鏻硫代氰酸酯等的芳香族鏻鹽；三苯基膦･三苯基硼烷等的芳香族膦･硼烷複合體；三苯基膦･p-苯醌加成反應物等的芳香族膦･醌加成反應物；三丁基膦、三-tert-丁基膦、三辛基膦、二-tert-丁基(2-丁烯基)膦、二-tert-丁基(3-甲基-2-丁烯基)膦、三環己基膦等的脂肪族膦；二丁基苯基膦、二-tert-丁基苯基膦、甲基二苯基膦、乙基二苯基膦、丁基二苯基膦、二苯基環己基膦、三苯基膦、三-鄰甲苯基膦、三-m-甲苯基膦、三-p-甲苯基膦、參(4-乙基苯基)膦、參(4-丙基苯基)膦、參(4-異丙基苯基)膦、參(4-丁基苯基)膦、參(4-tert-丁基苯基)膦、參(2,4-二甲基苯基)膦、參(2,5-二甲基苯基)膦、參(2,6-二甲基苯基)膦、參(3,5-二甲基苯基)膦、參(2,4,6-三甲基苯基)膦、參(2,6-二甲基-4-乙氧基苯基)膦、參(2-甲氧基苯基)膦、參(4-甲氧基苯基)膦、參(4-乙氧基苯基)膦、參(4-tert-丁氧基苯基)膦、二苯基-2-吡啶基膦、1,2-雙(二苯基膦)乙烷、1,3-雙(二苯基膦)丙烷、1,4-雙(二苯基膦)丁烷、1,2-雙(二苯基膦)乙炔、2,2’-雙(二苯基膦)二苯基醚等的芳香族膦等。Examples of the phosphorus-based hardening accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and (Tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenol, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyl Triphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, Tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triphenylethylphosphonium tetraphenylborate, ginseng(3-methylphenyl)ethylphosphonium tetraphenylborate Salt, (2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl Aromatic phosphonium salts such as triphenylphosphonium thiocyanate; aromatic phosphine and borane complexes such as triphenylphosphine and triphenylborane; triphenylphosphine and p-benzoquinone addition reaction Aromatic phosphine･quinone addition reactants of substances; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert- Aliphatic phosphines such as butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, etc.; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, Ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, ginseng (4-ethylphenyl)phosphine, ginseng (4-propylphenyl)phosphine, ginseng (4-isopropylphenyl)phosphine, ginseng (4-butylphenyl)phosphine, ginseng (4-tert- Butylphenyl)phosphine, ginseng (2,4-dimethylphenyl)phosphine, ginseng (2,5-dimethylphenyl)phosphine, ginseng (2,6-dimethylphenyl)phosphine, ginseng (3,5-dimethylphenyl)phosphine, ginseng (2,4,6-trimethylphenyl)phosphine, ginseng (2,6-dimethyl-4-ethoxyphenyl)phosphine, ginseng (2-methoxyphenyl)phosphine, ginseng (4-methoxyphenyl)phosphine, ginseng (4-ethoxyphenyl)phosphine, ginseng (4-tert-butoxyphenyl)phosphine, di Phenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, Aromatic phosphines such as 1,2-bis(diphenylphosphine)acetylene and 2,2'-bis(diphenylphosphine)diphenyl ether.

作為脲系硬化促進劑，例如可舉出1,1-二甲基脲；1,1,3-三甲基脲、3-乙基-1,1-二甲基脲、3-環己基-1,1-二甲基脲、3-環辛基-1,1-二甲基脲等的脂肪族二甲基脲；3-苯基-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-(3,4-二氯苯基)-1,1-二甲基脲、3-(3-氯-4-甲基苯基)-1,1-二甲基脲、3-(2-甲基苯基)-1,1-二甲基脲、3-(4-甲基苯基)-1,1-二甲基脲、3-(3,4-二甲基苯基)-1,1-二甲基脲、3-(4-異丙基苯基)-1,1-二甲基脲、3-(4-甲氧基苯基)-1,1-二甲基脲、3-(4-硝基苯基)-1,1-二甲基脲、3-[4-(4-甲氧基苯氧基)苯基]-1,1-二甲基脲、3-[4-(4-氯苯氧基)苯基]-1,1-二甲基脲、3-[3-(三氟甲基)苯基]-1,1-二甲基脲、N,N-(1,4-伸苯基)雙(N’,N’-二甲基脲)、N,N-(4-甲基-1,3-伸苯基)雙(N’,N’-二甲基脲)[甲苯雙二甲基脲]等的芳香族二甲基脲等。Examples of urea-based hardening accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl- Aliphatic dimethylureas such as 1,1-dimethylurea and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4 -Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl) )-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea , 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- Methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy) )phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl )phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl Aromatic dimethylureas such as -1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

作為胍系硬化促進劑，例如可舉出二氰二胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜聯環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜聯環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(鄰甲苯基)雙胍等。Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dicyanodiamine. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl -1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecane Biguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

作為咪唑系硬化促進劑，例如可舉出2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、1-苯甲基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯並[1,2-a]苯並咪唑、1-十二烷基-2-甲基-3-苯甲基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等的咪唑化合物及咪唑化合物與環氧樹脂之加成物。作為咪唑系硬化促進劑之販售品，例如可舉出四國化成工業公司製的「1B2PZ」、「2E4MZ」、「2MZA-PW」、「2MZ-OK」、「2MA-OK」、「2MA-OK-PW」、「2PHZ」、「2PHZ-PW」、「Cl1Z」、「Cl1Z-CN」、「Cl1Z-CNS」、「C11Z-A」；三菱化學公司製的「P200-H50」等。Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-phenylmethyl-2-methyl Imidazole, 1-phenylmethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl -2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-phenylmethylimidazolium chloride, 2 -Imidazole compounds such as methyl imidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins. Examples of commercially available imidazole hardening accelerators include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA" manufactured by Shikoku Chemical Industry Co., Ltd. -OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

作為金屬系硬化促進劑，例如可舉出鈷、銅、鋅、鐵、鎳、錳、錫等的金屬的有機金屬錯體或有機金屬鹽。作為有機金屬錯體之具體例子，可舉出鈷(II)乙醯丙酮、鈷(III)乙醯丙酮等的有機鈷錯體、銅(II)乙醯丙酮等的有機銅錯體、鋅(II)乙醯丙酮等的有機鋅錯體、鐵(III)乙醯丙酮等的有機鐵錯體、鎳(II)乙醯丙酮等的有機鎳錯體、錳(II)乙醯丙酮等的有機錳錯體等。作為有機金屬鹽，例如可舉出辛基酸鋅、辛基酸錫、環烷烴酸鋅、環烷烴酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetyl acetone and cobalt (III) acetyl acetone, organic copper complexes such as copper (II) acetyl acetone, and zinc ( II) Organic zinc complexes such as acetyl acetone, organic iron complexes such as iron (III) acetyl acetone, organic nickel complexes such as nickel (II) acetyl acetone, etc., organic complexes such as manganese (II) acetyl acetone, etc. Manganese complex, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

作為胺系硬化促進劑，例如可舉出三乙基胺、三丁基胺等的三烷基胺、4-二甲基胺基吡啶、苯甲基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一碳烯等。作為胺系硬化促進劑，可使用販售品，例如可舉出Ajinomoto Fine Techno Co., Ltd.製的「MY-25」等。Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -Shen(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. As the amine-based hardening accelerator, commercially available products can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.

樹脂組成物中之(D)硬化促進劑的量，相對於樹脂組成物之不揮發成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.02質量%以上，更佳為0.03質量%以上，以2質量%以下為佳，較佳為1質量%以下，更佳為0.5質量%以下。The amount of (D) hardening accelerator in the resin composition may be 0% by mass relative to 100% by mass of non-volatile components of the resin composition, or may be greater than 0% by mass, preferably 0.01% by mass or more. It is preferably 0.02 mass% or more, more preferably 0.03 mass% or more, preferably 2 mass% or less, preferably 1 mass% or less, and more preferably 0.5 mass% or less.

樹脂組成物中之(D)硬化促進劑的量，相對於樹脂組成物之樹脂成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.05質量%以上，更佳為0.1質量%以上，以5質量%以下為佳，較佳為2質量%以下，更佳為1質量%以下。The amount of (D) hardening accelerator in the resin composition may be 0% by mass relative to 100% by mass of the resin component of the resin composition, or may be greater than 0% by mass, preferably 0.01% by mass or more, preferably 0.01% by mass or more. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

[(E)熱塑性樹脂] 有關本發明之一實施形態的樹脂組成物中可進一步含有作為任意成分之(E)熱塑性樹脂。作為(E)成分的(E)熱塑性樹脂中，若無特別說明，未含相當於上述(A)～(D)成分者。 [(E)Thermoplastic resin] The resin composition according to one embodiment of the present invention may further contain (E) a thermoplastic resin as an optional component. The (E) thermoplastic resin as the component (E) does not contain components corresponding to the above-mentioned components (A) to (D) unless otherwise specified.

作為(E)熱塑性樹脂，例如可舉出苯氧基樹脂、聚醯亞胺樹脂、聚乙烯縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚伸苯基醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等。(E)熱塑性樹脂可單獨使用1種類，或亦可組合2種類以上而使用。Examples of (E) thermoplastic resin include phenoxy resin, polyamide imine resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamide imine resin, and polyether imide resin. Amine resin, polyester resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. (E) One type of thermoplastic resin may be used alone, or two or more types may be used in combination.

作為苯氧基樹脂，例如可舉出具有選自由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯基骨架、芴骨架、二環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架及三甲基環己烷骨架所成群的1種類以上骨架之苯氧基樹脂。苯氧基樹脂之末端可為酚性羥基、環氧基等中任一種官能基。作為苯氧基樹脂之具體例子，可舉出三菱化學公司製的「1256」及「4250」(皆為含有雙酚A骨架之苯氧基樹脂)；三菱化學公司製的「YX8100」(含有雙酚S骨架的苯氧基樹脂)；三菱化學公司製的「YX6954」(含有雙酚苯乙酮骨架的苯氧基樹脂)；日鐵化學&材料公司製的「FX280」及「FX293」；三菱化學公司製的「YL7500BH30」、「YX6954BH30」、「YX7553」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」、「YL7482」及「YL7891BH30」等。Examples of the phenoxy resin include those having a structure selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and a dicyclopentane skeleton. Phenoxy resin with one or more skeletons consisting of diene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. The terminal of the phenoxy resin can be any functional group such as phenolic hydroxyl group or epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing a bisphenol A skeleton) Phenoxy resin with phenol S skeleton); "YX6954" made by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" made by Nippon Steel Chemical & Materials Co., Ltd.; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Chemical Company.

作為聚醯亞胺樹脂之具體例子，可舉出信越化學工業公司製「SLK-6100」、新日本理化公司製的「RIKACOATSN20」及「RIKACOATPN20」等。Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "RIKACOATSN20" and "RIKACOATPN20" manufactured by Shin-Nippon Rika Co., Ltd., and the like.

作為聚乙烯縮醛樹脂，例如可舉出聚乙烯甲醛樹脂、聚乙烯縮丁醛樹脂，以聚乙烯縮丁醛樹脂為佳。作為聚乙烯縮醛樹脂之具體例子，可舉出電化學工業公司製的「電化縮丁醛4000-2」、「電化縮丁醛5000-A」、「電化縮丁醛6000-C」、「電化縮丁醛6000-EP」；積水化學工業公司製的S-LECBH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列等。Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of the polyvinyl acetal resin include "Electrobutyral 4000-2", "Electrobutyral 5000-A", "Electrobutyral 6000-C" and "Electrobutyral 6000-C" manufactured by Denka Kogyo Co., Ltd. Electrochemical butyral 6000-EP"; S-LECBH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

作為聚烯烴樹脂，例如可舉出低密度聚乙烯、超低密度聚乙烯、高密度聚乙烯、伸乙基-乙酸乙烯基共聚物、伸乙基-丙烯酸乙基共聚物、伸乙基-丙烯酸甲基共聚物等的伸乙基系共聚合樹脂；聚丙烯、伸乙基-伸丙基嵌段共聚物等的聚烯烴系聚合物等。Examples of the polyolefin resin include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylidene-vinyl acetate copolymer, ethylidene-ethyl acrylate copolymer, and ethylidene-acrylate copolymer. Ethylene-based copolymer resins such as methyl copolymers; polyolefin-based polymers such as polypropylene and ethylidene-propylene block copolymers.

作為聚丁二烯樹脂，例如可舉出含有氫化聚丁二烯骨架的樹脂、含有羥基的聚丁二烯樹脂、含有酚性羥基的聚丁二烯樹脂、含有羧基的聚丁二烯樹脂、含有酸酐基的聚丁二烯樹脂、含有環氧基的聚丁二烯樹脂、含有異氰酸酯基的聚丁二烯樹脂、含有胺基甲酸酯基的聚丁二烯樹脂、聚伸苯基醚-聚丁二烯樹脂等。Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, a carboxyl group-containing polybutadiene resin, Anhydride group-containing polybutadiene resin, epoxy group-containing polybutadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether -Polybutadiene resin, etc.

作為聚醯胺醯亞胺樹脂之具體例子，可舉出東洋紡公司製的「VylomaxHR11NN」及「VylomaxHR16NN」。作為聚醯胺醯亞胺樹脂之具體例子，又可舉出日立化成公司製的「KS9100」、「KS9300」(聚矽氧烷骨架含有聚醯胺醯亞胺)等的變性聚醯胺醯亞胺。Specific examples of the polyamideimide resin include "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide imine resin include modified polyamide imine resins such as "KS9100" and "KS9300" (polysiloxane skeleton containing polyamide imine) manufactured by Hitachi Chemical Co., Ltd. amine.

作為聚醚碸樹脂之具體例子，可舉出住友化學公司製的「PES5003P」等。Specific examples of the polyether resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

作為聚碸樹脂之具體例子，可舉出Solvay Advanced Polymers公司製的聚碸「P1700」、「P3500」等。Specific examples of polystyrene resins include polystyrene "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

作為聚伸苯基醚樹脂之具體例子，可舉出SABIC製「NORYL SA90」等。作為聚醚醯亞胺樹脂之具體例子，可舉出GE公司製的「Ultem」等。Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE Corporation.

作為聚碳酸酯樹脂，例如可舉出含有羥基的碳酸酯樹脂、含有酚性羥基的碳酸酯樹脂、含有羧基的碳酸酯樹脂、含有酸酐基的碳酸酯樹脂、含有異氰酸酯基的碳酸酯樹脂、含有胺基甲酸酯基的碳酸酯樹脂等。作為聚碳酸酯樹脂之具體例子，可舉出三菱瓦斯化學公司製的「FPC0220」、旭化成化學公司製的「T6002」、「T6001」(聚碳酸酯二醇)、Kuraray公司製的「C-1090」、「C-2090」、「C-3090」(聚碳酸酯二醇)等。作為聚醚醚酮樹脂之具體例子，可舉出住友化學公司製的「SumiployK」等。Examples of the polycarbonate resin include hydroxyl group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxyl group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, Urethane-based carbonate resin, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090" manufactured by Kuraray Corporation. ”, “C-2090”, “C-3090” (polycarbonate diol), etc. Specific examples of the polyetheretherketone resin include "SumiployK" manufactured by Sumitomo Chemical Co., Ltd. and the like.

作為聚酯樹脂，例如可舉出聚乙烯對苯二甲酸酯樹脂、聚乙烯萘二甲酸酯樹脂、聚丁烯對苯二甲酸酯樹脂、聚丁烯萘二甲酸酯樹脂、聚三亞甲基對苯二甲酸酯樹脂、聚三亞甲基萘二甲酸酯樹脂、聚環己烷二甲基對苯二甲酸酯樹脂等。Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, and polyethylene naphthalate resin. Trimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, etc.

(E)熱塑性樹脂之重量平均分子量(Mw)，以比5,000大為佳，較佳為8,000以上，更佳為10,000以上，特佳為20,000以上，以100,000以下為佳，較佳為70,000以下，更佳為60,000以下，特佳為50,000以下。重量平均分子量可藉由凝膠滲透層析法(GPC)算出聚苯乙烯換算之值而測定。(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, The best price is less than 60,000, and the best price is less than 50,000. The weight average molecular weight can be measured by calculating the polystyrene converted value by gel permeation chromatography (GPC).

樹脂組成物中之(E)熱塑性樹脂的量，相對於樹脂組成物之不揮發成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.05質量%以上，更佳為0.1質量%以上，以20質量%以下為佳，較佳為10質量%以下，更佳為5質量%以下。The amount of (E) thermoplastic resin in the resin composition may be 0% by mass relative to 100% by mass of non-volatile components of the resin composition, or may be greater than 0% by mass, preferably 0.01% by mass or more, preferably 0.01% by mass or more. Preferably it is 0.05 mass% or more, more preferably 0.1 mass% or more, preferably 20 mass% or less, preferably 10 mass% or less, more preferably 5 mass% or less.

樹脂組成物中之(E)熱塑性樹脂的量，相對於樹脂組成物之樹脂成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.1質量%以上，更佳為1質量%以上，以20質量%以下為佳，較佳為10質量%以下，更佳為5質量%以下。The amount of (E) thermoplastic resin in the resin composition may be 0% by mass relative to 100% by mass of the resin component of the resin composition, or may be greater than 0% by mass, preferably 0.01% by mass or more, and more preferably It is 0.1 mass % or more, more preferably 1 mass % or more, 20 mass % or less is preferred, 10 mass % or less is preferred, and 5 mass % or less is more preferred.

[(F)自由基聚合性化合物] 有關本發明之一實施形態的樹脂組成物中可進一步含有作為任意成分之(F)自由基聚合性化合物。作為(F)成分之(F)自由基聚合性化合物中，若無特別說明，未含有相當於上述(A)～(E)成分者。(F)自由基聚合性化合物可單獨使用1種類，亦可組合2種類以上而使用。 [(F) Radically polymerizable compound] The resin composition according to one embodiment of the present invention may further contain (F) a radically polymerizable compound as an optional component. Unless otherwise specified, the radically polymerizable compound (F) as the component (F) does not contain components corresponding to the above-mentioned components (A) to (E). (F) A radical polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(F)自由基聚合性化合物可含有乙烯性不飽和鍵。藉此，(F)自由基聚合性化合物可具有含有乙烯性不飽和鍵之自由基聚合性基。作為自由基聚合性基，例如可舉出乙烯基、烯丙基、1-丙烯基、3-環己烯基、3-環戊烯基、2-乙烯基苯基、3-乙烯基苯基、4-乙烯基苯基等的不飽和烴基；丙烯醯基、甲基丙烯醯基、馬來醯亞胺基(2,5-二氫-2,5-二氧代-1H-吡咯-1-基)等的α,β-不飽和羰基等。(F)自由基聚合性化合物以具有2個以上的自由基聚合性基者為佳。(F) The radically polymerizable compound may contain an ethylenically unsaturated bond. Thereby, (F) the radically polymerizable compound may have a radically polymerizable group containing an ethylenically unsaturated bond. Examples of radically polymerizable groups include vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, and 3-vinylphenyl. , 4-vinylphenyl and other unsaturated hydrocarbon groups; acrylyl, methacrylyl, maleimino (2,5-dihydro-2,5-dioxo-1H-pyrrole-1 - group) and other α, β-unsaturated carbonyl groups, etc. (F) The radically polymerizable compound preferably has two or more radically polymerizable groups.

作為(F)自由基聚合性化合物，例如可舉出(甲基)丙烯酸系自由基聚合性化合物、苯乙烯系自由基聚合性化合物、烯丙基系自由基聚合性化合物、馬來醯亞胺系自由基聚合性化合物等。Examples of (F) radical polymerizable compounds include (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, and maleimide. It is a free radical polymerizable compound, etc.

(甲基)丙烯酸系自由基聚合性化合物，例如為具有1個以上，較佳為具有2個以上丙烯醯基及/或甲基丙烯醯基之化合物。作為(甲基)丙烯酸系自由基聚合性化合物，例如可舉出環己烷-1,4-二甲醇二(甲基)丙烯酸酯、環己烷-1,3-二甲醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,8-辛烷二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等之低分子量(分子量未達1000)之脂肪族(甲基)丙烯酸酯化合物；二噁烷甘醇二(甲基)丙烯酸酯、3,6-二噁-1,8-辛烷二醇二(甲基)丙烯酸酯、3,6,9-三噁十一烷-1,11-二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]芴、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯等之低分子量(分子量未達1000)之含有醚的(甲基)丙烯酸酯化合物；參(3-羥基丙基)異氰脲酸酯三(甲基)丙烯酸酯、參(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、乙氧基化異氰脲酸三(甲基)丙烯酸酯等之低分子量(分子量未達1000)的含有異氰脲酸酯之(甲基)丙烯酸酯化合物；(甲基)丙烯酸變性聚伸苯基醚樹脂等之高分子量(分子量1000以上)的丙烯酸酯化合物等。作為(甲基)丙烯酸系自由基聚合性化合物之販售品，例如可舉出新中村化學工業公司製的「A-DOG」(二噁烷甘醇二丙烯酸酯)、共榮社化學公司製的「DCP-A」(三環癸烷二甲醇二丙烯酸酯)、「DCP」(三環癸烷二甲醇二甲基丙烯酸酯)、日本化藥股份有限公司的「KAYARAD R-684」(三環癸烷二甲醇二丙烯酸酯)、「KAYARAD R-604」(二噁烷甘醇二丙烯酸酯)、SABICinnovative plastics公司製的「SA9000」、「SA9000-111」(甲基丙烯酸變性聚伸苯基醚)等。The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more acryl groups and/or methacryl groups. Examples of the (meth)acrylic radical-polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate and cyclohexane-1,3-dimethanol di(meth)acrylate. Acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Alcohol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate Methacrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Aliphatic (meth)acrylate compounds with low molecular weight (molecular weight less than 1000); dioxane glycol di(meth)acrylate, 3,6-diox-1,8-octanediol di (Meth)acrylate, 3,6,9-trioxundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as di(meth)acrylate; (3-hydroxypropyl)isocyanurate tri(meth)acrylate , ginseng (2-hydroxyethyl) isocyanurate tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate and other low molecular weight (molecular weight less than 1000) containing isoforms (meth)acrylate compounds of cyanurate; high molecular weight (molecular weight 1000 or more) acrylate compounds of (meth)acrylic modified polyphenylene ether resin, etc. Examples of commercially available (meth)acrylic radical polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and Kyoeisha Chemical Co., Ltd. "DCP-A" (tricyclodecane dimethanol dimethacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), Nippon Kayaku Co., Ltd.'s "KAYARAD R-684" (tricyclodecane dimethanol dimethacrylate) cyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate), "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene) manufactured by SABICinnovative Plastics Ether) etc.

苯乙烯系自由基聚合性化合物，例如為於芳香族碳原子上直接鍵結有1個以上，較佳為2個以上乙烯基之化合物。作為苯乙烯系自由基聚合性化合物，例如可舉出二乙烯基苯、2,4-二乙烯基甲苯、2,6-二乙烯基萘、1,4-二乙烯基萘、4,4’-二乙烯基聯苯基、1,2-雙(4-乙烯基苯基)乙烷、2,2-雙(4-乙烯基苯基)丙烷、雙(4-乙烯基苯基)醚等之低分子量(分子量未達1000)的苯乙烯系化合物；乙烯基苯甲基變性聚伸苯基醚樹脂、苯乙烯-二乙烯基苯共聚物等之高分子量(分子量1000以上)的苯乙烯系化合物等。作為苯乙烯系自由基聚合性化合物之販售品，例如可舉出日鐵化學&材料公司製的「ODV-XET(X03)」、「ODV-XET(X04)」、「ODV-XET(X05)」(苯乙烯-二乙烯基苯共聚物)、三菱瓦斯化學公司製的「OPE-2St 1200」、「OPE-2St 2200」(乙烯基苯甲基變性聚伸苯基醚樹脂)。The styrenic radical polymerizable compound is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrenic radical polymerizable compound include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4' -Divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc. Styrene compounds with low molecular weight (molecular weight less than 1000); styrene compounds with high molecular weight (molecular weight above 1000) such as vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Compounds etc. Examples of commercially available styrenic radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" manufactured by Nippon Steel Chemical & Materials Co., Ltd. )" (styrene-divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

烯丙基系自由基聚合性化合物，例如為具有1個以上，較佳為2個以上的烯丙基之化合物。作為烯丙基系自由基聚合性化合物，例如可舉出聯苯甲酸二烯丙基、偏苯三酸三烯丙基、鄰苯二甲酸二烯丙基、間苯二甲酸二烯丙基、對苯二甲酸二烯丙基、2,6-萘二羧酸二烯丙基、2,3-萘羧酸二烯丙基等之芳香族羧酸烯丙基酯化合物；1,3,5-三烯丙基異氰脲酸酯、1,3-二烯丙基-5-縮水甘油基異氰脲酸酯等之異氰脲酸烯丙基酯化合物；2,2-雙[3-烯丙基-4-(縮水甘油基氧基)苯基]丙烷等之環氧含有芳香族烯丙基化合物；雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯並噁嗪-3-基)苯基]甲烷等之苯並噁嗪含有芳香族烯丙基化合物；1,3,5-三烯丙基醚苯等之含有醚的芳香族烯丙基化合物；二烯丙基二苯基矽烷等之烯丙基矽烷化合物等。作為烯丙基系自由基聚合性化合物之販售品，例如可舉出日本化成公司製的「TAIC」(1,3,5-三烯丙基異氰脲酸酯)、NISSHOKU TECHNO FINE CHEMICAL CO., LTD.製的「DAD」(聯苯甲酸二烯丙基)、和光純藥工業公司製的「TRIAM-705」(偏苯三酸三烯丙基)、日本蒸餾工業公司製的商品名「DAND」(2,3-萘羧酸二烯丙基)、四國化成工業公司製「ALP-d」(雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯並噁嗪-3-基)苯基]甲烷)、日本化藥公司製的「RE-810NM」(2,2-雙[3-烯丙基-4-(縮水甘油基氧基)苯基]丙烷)、四國化成公司製的「DA-MGIC」(1,3-二烯丙基-5-縮水甘油基異氰脲酸酯)等。The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more, allyl groups. Examples of the allyl radical polymerizable compound include diallyl biphenylcarboxylate, triallyl trimellitate, diallyl phthalate, and diallyl isophthalate. Aromatic carboxylic acid allyl ester compounds such as diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and diallyl 2,3-naphthalenecarboxylate; 1,3,5 -Allyl isocyanurate compounds such as triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[3- Epoxy containing aromatic allyl compounds such as allyl-4-(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1 , 3-Benzoxazin-3-yl)phenyl]methane and other benzoxazines containing aromatic allyl compounds; 1,3,5-triallyl ether benzene and other ether-containing aromatic alkenes Propyl compounds; allyl silane compounds such as diallyl diphenyl silane, etc. Examples of commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd. and NISSHOKU TECHNO FINE CHEMICAL CO. "DAD" (diallyl diphenylcarbamate) manufactured by ., LTD., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., and brand names manufactured by Nippon Distillation Industry Co., Ltd. "DAND" (diallyl 2,3-naphthalenecarboxylate), "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1) manufactured by Shikoku Chemical Industry Co., Ltd. ,3-benzoxazin-3-yl)phenyl]methane), "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)) manufactured by Nippon Kayaku Co., Ltd. ) phenyl]propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemicals Co., Ltd., etc.

馬來醯亞胺系自由基聚合性化合物，例如為具有1個以上，較佳為具有2個以上馬來醯亞胺基之化合物。馬來醯亞胺系自由基聚合性化合物可為具有脂肪族胺骨架之脂肪族馬來醯亞胺化合物，亦可含有芳香族胺骨架之芳香族馬來醯亞胺化合物。作為馬來醯亞胺系自由基聚合性化合物之販售品，例如可舉出信越化學工業公司製的「SLK-2600」、Digikner Molecules, Inc.製的「BMI-1500」、「BMI-1700」、「BMI-3000J」、「BMI-689」、「BMI-2500」(含有二聚物二胺結構之馬來醯亞胺化合物)、Digikner Molecules, Inc.製的「BMI-6100」(芳香族馬來醯亞胺化合物)、日本化藥公司製的「MIR-5000-60T」、「MIR-3000-70MT」(聯苯基芳烷基型馬來醯亞胺化合物)、K･I化成公司製的「BMI-70」、「BMI-80」、大和化成工業公司製「BMI-2300」、「BMI-TMH」等。又作為馬來醯亞胺系自由基聚合性化合物，亦可使用揭示於發明協會公開技報公技號碼2020-500211號之馬來醯亞胺樹脂(含有茚滿環骨架的馬來醯亞胺化合物)。The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimine radical polymerizable compound may be an aliphatic maleimine compound having an aliphatic amine skeleton, or an aromatic maleimine compound containing an aromatic amine skeleton. Examples of commercially available maleimide radical polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "BMI-1500" and "BMI-1700" manufactured by Digikner Molecules, Inc. ", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure), "BMI-6100" (aromatic) manufactured by Digikner Molecules, Inc. family maleimide compound), "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., K･I Chemicals "BMI-70" and "BMI-80" made by the company, "BMI-2300" and "BMI-TMH" made by Yamato Chemical Industry Co., Ltd., etc. As the maleimide-based radical polymerizable compound, the maleimide resin disclosed in the Technical Publication No. 2020-500211 of the Invention Association (maleimide containing an indan ring skeleton) can also be used. compound).

(F)自由基聚合性化合物的乙烯性不飽和鍵當量以20g/eq.～3,000g/eq.為佳，較佳為50g/eq.～2,500g/eq.，更佳為70g/eq.～2,000g/eq.，特佳為90g/eq.～1,500g/eq.。乙烯性不飽和鍵當量表示每乙烯性不飽和鍵1當量之自由基聚合性化合物的質量。(F) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20 g/eq. to 3,000 g/eq., more preferably 50 g/eq. to 2,500 g/eq., more preferably 70 g/eq. ~2,000g/eq., the best is 90g/eq.~1,500g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per 1 equivalent of the ethylenically unsaturated bond.

(F)自由基聚合性化合物之重量平均分子量(Mw)以40,000以下為佳，較佳為10,000以下，更佳為5,000以下，特佳為3,000以下。下限雖非特別限定者，例如可為150以上等。重量平均分子量可藉由凝膠滲透層析法(GPC)法測定出聚苯乙烯換算之值。(F) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be 150 or more, for example. The weight average molecular weight can be measured in polystyrene conversion by gel permeation chromatography (GPC).

樹脂組成物中之(F)自由基聚合性化合物的量，相對於樹脂組成物中之不揮發成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.1質量%以上，更佳為0.5質量%以上，以10質量%以下為佳，較佳為5質量%以下，更佳為3質量%以下。The amount of (F) radically polymerizable compound in the resin composition may be 0% by mass relative to 100% by mass of non-volatile components in the resin composition, or may be greater than 0% by mass, 0.01% by mass or more. Preferably, it is 0.1 mass % or more, more preferably 0.5 mass % or more, 10 mass % or less is preferred, 5 mass % or less is preferred, and 3 mass % or less is more preferred.

樹脂組成物中之(F)自由基聚合性化合物的量，相對於樹脂組成物中之樹脂成分100質量%而言，可為0質量%，亦可比0質量%大，以0.01質量%以上為佳，較佳為0.1質量%以上，更佳為1質量%以上，以20質量%以下為佳，較佳為10質量%以下，更佳為5質量%以下。The amount of (F) radically polymerizable compound in the resin composition may be 0% by mass relative to 100% by mass of the resin component in the resin composition, or may be greater than 0% by mass, preferably 0.01% by mass or more. Preferably, it is 0.1 mass% or more, more preferably 1 mass% or more, 20 mass% or less is preferred, 10 mass% or less is preferred, and 5 mass% or less is more preferred.

[(G)任意之添加劑] 有關本發明之一實施形態的樹脂組成物可進一步含有作為任意成分之(G)任意之添加劑。作為(G)任意之添加劑，例如可舉出橡膠粒子等的有機填充材；有機銅化合物、有機鋅化合物、有機鈷化合物等的有機金屬化合物；酞菁藍、酞菁綠、碘綠、重氮黃等的著色劑；氫醌、鄰苯二酚、鄰苯三酚、吩噻嗪等的聚合禁止劑；矽氧系塗平劑、丙烯酸聚合物系塗平劑等的塗平劑；膨潤土、蒙脫石等的增黏劑；矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等的消泡劑；苯並三唑系紫外線吸收劑等的紫外線吸收劑；脲矽烷等的接著性向上劑；三唑系密著性賦予劑、四唑系密著性賦予劑、三嗪系密著性賦予劑等的密著性賦予劑；受阻酚系抗氧化劑等的抗氧化劑；芪衍生物等的螢光增白劑；氟系界面活性劑、矽氧系界面活性劑等的界面活性劑；磷系難燃劑(例如磷酸酯化合物、磷腈化合物、膦酸化合物、紅磷)、氮系難燃劑(例如硫酸三聚氰胺)、鹵素系難燃劑等的難燃劑；磷酸酯系分散劑、聚氧化烯系分散劑、乙炔系分散劑、矽氧系分散劑、負離子性分散劑、陽離子性分散劑等的分散劑；硼酸鹽系穩定劑、鈦酸鹽系穩定劑、鋁酸鹽系穩定劑、鋯酸鹽系穩定劑、異氰酸酯系穩定劑、羧酸系穩定劑、羧酸酐系穩定劑等的穩定劑。(G)任意之添加劑可單獨使用1種類，亦可組合2種以上而使用。 [(G) Optional additives] The resin composition according to one embodiment of the present invention may further contain (G) any additive as an optional component. Examples of optional additives (G) include organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, and diazo Yellow and other colorants; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; smoothing agents for silicone-based leveling agents, acrylic polymer-based leveling agents, etc.; bentonite, Tackifiers such as montmorillonite; defoamer such as silicone defoamer, acrylic defoamer, fluorine defoamer, vinyl resin defoamer, etc.; benzotriazole ultraviolet absorber, etc. UV absorbers; adhesion improving agents such as ureasilane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents, etc.; hindered phenols Antioxidants such as antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazenes) Compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, etc.; phosphate ester dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, Dispersants such as silicone-based dispersants, anionic dispersants, and cationic dispersants; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers stabilizers, carboxylic acid-based stabilizers, carboxylic acid anhydride-based stabilizers, etc. (G) Any additive may be used alone or in combination of two or more types.

[(H)溶劑] 有關本發明之一實施形態的樹脂組成物亦可進一步含有組合於上述(A)～(G)成分的不揮發成分之作為任意揮發性成分的(H)溶劑。作為(H)溶劑，通常使用有機溶劑。作為有機溶劑，例如可舉出丙酮、甲基乙基酮、甲基異丁基酮、環己酮等的酮系溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸異戊酯、丙酸甲酯、丙酸乙酯、γ-丁內酯等的酯系溶劑；四氫吡喃、四氫呋喃、1,4-二噁烷、二乙基醚、二異丙基醚、二丁基醚、二苯基醚、苯甲醚等的醚系溶劑；甲醇、乙醇、丙醇、丁醇、乙二醇等的醇系溶劑；乙酸2-乙氧基乙酯、丙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙基二甘醇乙酸酯、γ-丁內酯、甲氧基丙酸甲基等的醚酯系溶劑；乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲基等的酯醇系溶劑；2-甲氧基丙醇、2-甲氧基乙醇、2-乙氧基乙醇、丙二醇單甲基醚、二乙二醇單丁基醚(丁基卡必醇)等的醚醇系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯酮等的醯胺系溶劑；二甲基亞碸等的亞碸系溶劑；乙腈、丙腈等的腈系溶劑；己烷、環戊烷、環己烷、甲基環己烷等的脂肪族烴系溶劑；苯、甲苯、二甲苯、乙基苯、三甲基苯等的芳香族烴系溶劑等。(H)溶劑可單獨使用1種類，亦可組合2種類以上而使用。 [(H)solvent] The resin composition according to one embodiment of the present invention may further contain (H) solvent as an optional volatile component that is combined with the non-volatile components of the above-mentioned (A) to (G) components. As the (H) solvent, an organic solvent is usually used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and acetic acid. Ester solvents such as isopentyl ester, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether , dibutyl ether, diphenyl ether, anisole, etc. ether solvents; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol mono Ether ester solvents such as methyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc.; methyl lactate Ester alcohol solvents such as ester, ethyl lactate, 2-hydroxyisobutyric acid methyl, etc.; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, Ether alcohol solvents such as ethylene glycol monobutyl ether (butylcarbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- Amide solvents such as pyrrolidone; styrene solvents such as dimethyl styrene; nitrile solvents such as acetonitrile and propionitrile; fats such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Aromatic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (H) The solvent may be used individually by 1 type, or in combination of 2 or more types.

(H)溶劑之量雖非特別限定者，相對於樹脂組成物之全成分100質量%而言，例如可為60質量%以下、40質量%以下、30質量%以下、20質量%以下、15質量%以下、10質量%以下等，亦可為0質量%。Although the amount of (H) solvent is not particularly limited, it may be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, based on 100 mass% of the total components of the resin composition. Mass% or less, 10 mass% or less, etc., may also be 0 mass%.

[樹脂組成物之製造方法] 有關本發明之一實施形態的樹脂組成物，例如可藉由混合上述成分而製造。上述成分可同時混和一部分或全部，亦可依序混合。在混合各成分之過程中，亦可將溫度適宜地設定，藉此可暫時性或自始至終進行加熱及/或冷卻。又，混合各成分之過程中亦可進行攪拌或振盪。 [Production method of resin composition] The resin composition according to one embodiment of the present invention can be produced by mixing the above-mentioned components, for example. Some or all of the above ingredients can be mixed at the same time, or they can be mixed sequentially. During the mixing of the ingredients, the temperature can also be set appropriately, whereby heating and/or cooling can be performed temporarily or throughout. In addition, stirring or shaking may be performed during the mixing of each component.

[樹脂組成物之特性] 有關本發明之一實施形態的樹脂組成物可具有高流動性。樹脂組成物之流動性可藉由波動而評估。所謂波動表示形成樹脂組成物之層的情況時，該層的表面高度之最大值與最小值之差。一般而言，該波動越小，表示樹脂組成物之流動性越高。 [Characteristics of resin composition] The resin composition according to one embodiment of the present invention can have high fluidity. The fluidity of the resin composition can be evaluated by fluctuations. The fluctuation refers to the difference between the maximum value and the minimum value of the surface height of the layer when the layer of the resin composition is formed. Generally speaking, the smaller the fluctuation, the higher the fluidity of the resin composition.

其中一例子，於某平面上會形成梳齒狀圖型之導體層。所謂前述導體層的「圖型」表示自導體層的厚度方向所見到的形狀。此時，導體層形成為厚度35μm，L/S=160μm/160μm者。L/S表示導體層之線L(配線寬)與空間S(間隔寬)之比(線/空間)。於形成有該導體層之平面上，藉由樹脂組成物形成層。此後，將樹脂組成物層進行熱硬化而形成絕緣層。測定該絕緣層之表面(與導體層之反側表面)的高度，最高高度與最低高度的差作為波動而測定。通常導體層上部分中之絕緣層表面變得最高，導體層上部分以外的部分中之絕緣層的表面變得最低。如此該例子而測定波動之情況時，有關本發明之一實施形態的樹脂組成物之波動，以3.0μm以下為佳，較佳為2.0μm以下。波動之具體測定方法可採用如後述實施例之＜試驗例3：波動之測定＞所說明的方法。In one example, a comb-shaped pattern of conductor layers is formed on a certain plane. The “pattern” of the conductor layer refers to the shape seen from the thickness direction of the conductor layer. At this time, the conductor layer was formed to have a thickness of 35 μm and L/S=160 μm/160 μm. L/S represents the ratio (line/space) of the line L (wiring width) of the conductor layer to the space S (space width). A layer is formed of a resin composition on the plane on which the conductor layer is formed. Thereafter, the resin composition layer is thermally cured to form an insulating layer. The height of the surface of the insulating layer (the surface opposite to the conductive layer) is measured, and the difference between the highest height and the lowest height is measured as a ripple. Generally, the surface of the insulating layer in the upper portion of the conductor layer becomes the highest, and the surface of the insulating layer in the portion other than the upper portion of the conductor layer becomes the lowest. When the fluctuation is measured in this example, the fluctuation of the resin composition according to one embodiment of the present invention is preferably 3.0 μm or less, and more preferably 2.0 μm or less. A specific method for measuring the fluctuation can be as described in <Test Example 3: Measurement of Fluctuation> in the Examples described later.

有關本發明之一實施形態的樹脂組成物，通常可具有低的最低熔融黏度。例如藉由後述實施例的＜試驗例2：樹脂組成物之最低熔融黏度的測定＞所說明的方法而測定最低熔融黏度之情況時，有關本發明之一實施形態的樹脂組成物的最低熔融黏度，以未達4,000poise為佳，較佳為3,500poise以下，更佳為2,900poise以下。下限由可圓滑地進行較厚絕緣層的形成之觀點來看，例如可為500poise以上，700poise以上等。The resin composition according to one embodiment of the present invention can generally have a low minimum melt viscosity. For example, when the minimum melt viscosity is measured by the method described in <Test Example 2: Measurement of the minimum melt viscosity of the resin composition> in the examples described below, the minimum melt viscosity of the resin composition according to one embodiment of the present invention is , preferably less than 4,000 poise, more preferably less than 3,500 poise, more preferably less than 2,900 poise. From the viewpoint of enabling smooth formation of a thicker insulating layer, the lower limit may be, for example, 500 poise or more, 700 poise or more, or the like.

藉由硬化有關本發明之一實施形態的樹脂組成物而可得到硬化物。前述硬化時，通常對樹脂組成物施予加熱。藉此，通常含於樹脂組成物的成分中，(H)溶劑等的揮發性成分藉由硬化時的熱會揮發，但作為(A)～(G)成分的不揮發成分不會因藉由硬化時的熱而揮發。因此，樹脂組成物之硬化物可包含樹脂組成物之不揮發成分或該反應生成物。A cured product can be obtained by curing the resin composition according to one embodiment of the present invention. During the aforementioned hardening, the resin composition is usually heated. Therefore, among the components generally contained in the resin composition, volatile components such as (H) solvents are evaporated by the heat during curing, but non-volatile components as (A) to (G) components are not evaporated by Volatilizes due to heat during hardening. Therefore, the cured product of the resin composition may contain the non-volatile component of the resin composition or the reaction product.

依據有關本發明之一實施形態的樹脂組成物可得到絕緣信賴性高的硬化物。硬化物之絕緣信賴性可在高溫高濕度環境下藉由進行輸入電壓的耐久性試驗後之硬化物的絕緣電阻值而評估。其中一例子中，將有關本發明之一實施形態的樹脂組成物在190℃且90分鐘的條件下使熱硬化而得到硬化物，對該硬化物在130℃且85%RH之環境下進行輸入3.3V之電壓100小時的耐久性試驗。進行如此耐久性試驗的情況時，線/空間藉由15μm/15μm之梳狀電極所測定的該硬化物之絕緣電阻值，以1.0×10 8Ω以上為佳，較佳為1.0×10 9Ω以上。上限越大越佳，例如可為1.0×10 14Ω以下。絕緣信賴性之具體的評估方法，可採用在後述實施例之＜試驗例4：絕緣信賴性之評估＞所說明的方法。 According to the resin composition according to one embodiment of the present invention, a cured product with high insulation reliability can be obtained. The insulation reliability of the hardened material can be evaluated by measuring the insulation resistance value of the hardened material after a durability test of the input voltage in a high-temperature and high-humidity environment. In one example, a resin composition according to an embodiment of the present invention is thermally cured under conditions of 190°C and 90 minutes to obtain a cured product, and the cured product is imported in an environment of 130°C and 85% RH. Durability test for 100 hours at 3.3V voltage. When conducting such a durability test, the insulation resistance value of the hardened material measured by a 15 μm/15 μm comb-shaped electrode in line/space is preferably 1.0×10 8 Ω or more, and more preferably 1.0×10 9 Ω above. The larger the upper limit, the better. For example, it may be 1.0×10 14 Ω or less. The specific evaluation method of insulation reliability can be based on the method described in <Test Example 4: Evaluation of Insulation Reliability> of the Examples described later.

依據有關本發明之一實施形態的樹脂組成物，通常可得到優異耐熱性之硬化物。硬化物之耐熱性，例如可藉由玻璃轉移溫度表示。其中一例子，將有關本發明之一實施形態的樹脂組成物在190℃且90分鐘之硬化條件下進行熱硬化所得的硬化物之玻璃轉移溫度，以130℃以上為佳，較佳為140℃以上，更佳為150℃以上。玻璃轉移溫度之上限越高越佳，例如可為200℃以下、190℃以下、180℃以下等。玻璃轉移溫度藉由在負載1g且昇溫速度5℃/分鐘的測定條件下經拉伸載荷法進行熱機械分析而測定。玻璃轉移溫度之具體的測定方法，可採用後述實施例的＜試驗例1：硬化物之玻璃轉移溫度及線熱膨脹係數的測定＞所說明的方法。According to the resin composition according to one embodiment of the present invention, a cured product having excellent heat resistance can generally be obtained. The heat resistance of the hardened material can be expressed by the glass transition temperature, for example. As an example, the glass transition temperature of the cured product obtained by thermally hardening the resin composition according to an embodiment of the present invention under the curing conditions of 190°C and 90 minutes is preferably 130°C or higher, and more preferably 140°C. or above, more preferably 150°C or above. The higher the upper limit of the glass transition temperature, the better. For example, it may be 200°C or lower, 190°C or lower, 180°C or lower, etc. The glass transition temperature is measured by thermomechanical analysis using a tensile load method under the measurement conditions of a load of 1 g and a temperature rise rate of 5° C./min. As a specific method for measuring the glass transition temperature, the method described in <Test Example 1: Measurement of Glass Transition Temperature and Linear Thermal Expansion Coefficient of Hardened Materials> in the Examples described later can be used.

依據有關本發明之一實施形態的樹脂組成物，通常可得到耐回流焊性優異的硬化物。耐回流焊性可藉由硬化樹脂組成物所形成的絕緣層上形成導體層，進行含有加熱之耐回流焊試驗而可評估。其中一例子，將有關本發明之一實施形態的樹脂組成物藉由130℃及30分鐘之加熱，以及170℃及30分鐘之加熱經熱硬化所形成的絕緣層上經鍍敷而形成導體層，得到100mm×50mm之2個試樣。然後，將此等試樣進行通過重現吸收峰溫度260℃之焊接回流溫度的回流焊裝置10次的耐回流焊試驗(回流焊溫度輪廓依據IPC/JEDEC J-STD-020C)。此時，產生膨脹等異常部位的數目，以4個以下為佳，更佳為0個。耐回流焊性之具體評估方法可採用後述實施例之＜試驗例5：耐回流焊性之評估＞所說明的方法。According to the resin composition according to one embodiment of the present invention, a cured product excellent in reflow resistance can generally be obtained. Reflow resistance can be evaluated by forming a conductor layer on an insulating layer made of a hardened resin composition and performing a reflow resistance test involving heating. In one example, the resin composition according to an embodiment of the present invention is heated at 130° C. for 30 minutes, and then heated at 170° C. for 30 minutes. The insulating layer is thermally hardened and plated to form a conductor layer. , two samples of 100mm×50mm were obtained. Then, these samples were subjected to a reflow soldering resistance test through a reflow soldering device that reproduced the soldering reflow temperature of the absorption peak temperature of 260°C for 10 times (the reflow soldering temperature profile is based on IPC/JEDEC J-STD-020C). At this time, the number of abnormal parts such as swelling is preferably 4 or less, and more preferably 0. The specific evaluation method of the reflow resistance can be based on the method described in <Test Example 5: Evaluation of the Reflow Resistance> in the Examples described later.

依據有關本發明之一實施形態的樹脂組成物，通常可得到線熱膨脹係數小的硬化物。其中一例子，將有關本發明之一實施形態的樹脂組成物在190℃且90分鐘之硬化條件下進行熱硬化所得的硬化物自25℃至150℃的範圍中之平均線熱膨脹係數，以30ppm以下為佳，較佳為25ppm以下，更佳為23ppm以下。線熱膨脹係數可藉由在負載1g且昇溫速度5℃/分鐘的測定條件經拉伸載荷法進行熱機械分析而可測定。線熱膨脹係數之具體測定方法可採用後述實施例的＜試驗例1：硬化物之玻璃轉移溫度及線熱膨脹係數的測定＞所說明的方法。According to the resin composition according to one embodiment of the present invention, a cured product with a small linear thermal expansion coefficient can generally be obtained. In one example, the average linear thermal expansion coefficient in the range from 25°C to 150°C of the cured product obtained by thermally curing the resin composition according to an embodiment of the present invention under the curing conditions of 190°C and 90 minutes is 30 ppm. The following is preferable, more preferably 25 ppm or less, more preferably 23 ppm or less. The linear thermal expansion coefficient can be measured by thermomechanical analysis using the tensile load method under the measurement conditions of a load of 1 g and a temperature rise rate of 5°C/min. The specific method for measuring the coefficient of linear thermal expansion can be the method described in <Test Example 1: Measurement of Glass Transition Temperature and Coefficient of Linear Thermal Expansion of Hardened Materials> in the Examples described later.

有關本發明之一實施形態的樹脂組成物之硬化物通常可具有優異介電特性。例如硬化物的比電導率以5.0以下為佳，較佳為4.0以下，更佳為3.5以下。比電導率的下限雖無特別限制，例如可為1.5以上、2.0以上等。又，例如硬化物的介電損耗正切以0.0200以下為佳，較佳為0.0100以下，更佳為0.0050以下，特佳為0.0030以下。介電損耗正切之下限並無特別限定，例如可為0.0005以上。硬化物之比電導率及介電損耗正切可使用將樹脂組成物在190℃且90分鐘之硬化條件下進行熱硬化所得的硬化物，藉由空洞共振攝動法以測定頻率5.8GHz且測定溫度23℃之條件進行測定。作為測定裝置，例如可使用安捷倫科技公司製「HP8362B」。The cured product of the resin composition according to one embodiment of the present invention generally has excellent dielectric properties. For example, the specific conductivity of the hardened material is preferably 5.0 or less, more preferably 4.0 or less, and more preferably 3.5 or less. The lower limit of the specific conductivity is not particularly limited, but may be, for example, 1.5 or more, 2.0 or more, or the like. For example, the dielectric loss tangent of the hardened material is preferably 0.0200 or less, more preferably 0.0100 or less, more preferably 0.0050 or less, and particularly preferably 0.0030 or less. The lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0005 or more, for example. The specific conductivity and dielectric loss tangent of the cured product can be obtained by thermally curing the resin composition under the curing conditions of 190°C and 90 minutes. The frequency is 5.8 GHz and the temperature is measured by the cavity resonance perturbation method. Measured at 23°C. As a measuring device, for example, "HP8362B" manufactured by Agilent Technologies Co., Ltd. can be used.

[樹脂組成物之用途] 有關本發明之一實施形態的樹脂組成物可作為絕緣用途之樹脂組成物使用，特別可作為使用於形成絕緣層的樹脂組成物(絕緣層形成用之樹脂組成物)使用為佳。例如有關本實施形態的樹脂組成物可作為使用於形成半導體晶片封裝之絕緣層的樹脂組成物(半導體晶片封裝之絕緣層用的樹脂組成物)，及使用於形成電路基板(含有印刷配線板)之絕緣層的樹脂組成物(電路基板之絕緣層用的樹脂組成物)使用為佳。特別為樹脂組成物可使用於形成設置於導體層與導體層之間的層間絕緣層為佳。 [Use of resin composition] The resin composition according to one embodiment of the present invention can be used as a resin composition for insulating purposes, and is particularly preferably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer). For example, the resin composition according to this embodiment can be used as a resin composition used to form an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), or can be used to form a circuit board (including a printed wiring board). It is preferred to use a resin composition for the insulating layer (resin composition for the insulating layer of the circuit board). In particular, it is preferable that the resin composition can be used to form an interlayer insulating layer provided between conductor layers.

作為半導體晶片封裝，例如可舉出FC-CSP、MIS-BGA封裝、ETS-BGA封裝、Fan-out型WLP(Wafer Level Package)、Fan-in型WLP、Fan-out型PLP(Panel Level Package)、Fan-in型PLP。Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, and Fan-out type PLP (Panel Level Package) , Fan-in type PLP.

又，前述樹脂組成物亦可作為底層填料材使用，例如可作為將半導體晶片連接於基板後使用的MUF (Molding Under Filling)之材料使用。In addition, the aforementioned resin composition can also be used as an underfill material, for example, it can be used as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

前述樹脂組成物進一步可使用於樹脂薄片、預浸料等的薄片狀層合材料、焊接阻劑、模具黏接材、半導體密封材料、填洞樹脂、鑲入零件的樹脂等樹脂組成物之廣泛用途。The aforementioned resin composition can further be used in a wide range of resin compositions such as sheet-like laminate materials such as resin sheets and prepregs, soldering resists, mold adhesive materials, semiconductor sealing materials, hole-filling resins, and resins for inserting parts. use.

[薄片狀層合材料] 樹脂組成物可在塗漆狀態下使用於塗布上，但在工業上，以在含有該樹脂組成物的薄片狀層合材料之形態下使用為佳。 [Sheet-like laminate] The resin composition can be used for coating in a painted state, but industrially, it is preferably used in the form of a sheet-like laminated material containing the resin composition.

作為薄片狀層合材料，以下所示樹脂薄片、預浸料為佳。As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

其中一實施形態中，樹脂薄片具備支持體與形成於該支持體上之樹脂組成物層。樹脂組成物層係由上述樹脂組成物所形成。因此，樹脂組成物層通常含有樹脂組成物，以僅含有樹脂組成物為佳。In one embodiment, the resin sheet includes a support and a resin composition layer formed on the support. The resin composition layer is formed from the above-mentioned resin composition. Therefore, the resin composition layer usually contains the resin composition, and preferably contains only the resin composition.

樹脂組成物層之厚度由薄型化之觀點，及即使因樹脂組成物變薄亦可提高絕緣性優異的硬化物之觀點來看，以50μm以下為佳，較佳為40μm以下。樹脂組成物層的厚度之下限雖無特別限定，可為5μm以上、10μm以上等。The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less, from the viewpoint of thinning and the improvement of a cured product with excellent insulation properties even if the resin composition is thinned. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, or the like.

作為支持體，例如可舉出由塑質材料所成的薄膜、金屬箔、脫模紙，以由塑質材料所成的薄膜、金屬箔為佳。Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

作為支持體使用由塑質材料所成的薄膜之情況時，作為塑質材料，例如可舉出聚乙烯對苯二甲酸酯(以下有時簡稱為「PET」)、聚乙烯萘二甲酸酯(以下有時簡稱為「PEN」)等的聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等的丙烯酸、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中亦以聚乙烯對苯二甲酸酯、聚乙烯萘二甲酸酯為佳，以簡易的聚乙烯對苯二甲酸酯為特佳。When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Polyesters such as ester (hereinafter sometimes abbreviated as "PEN"), polycarbonates (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triethylene Acetocellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and simple polyethylene terephthalate is particularly preferred.

作為支持體使用金屬箔之情況時，作為金屬箔，例如可舉出銅箔、鋁箔等，以銅箔為佳。作為銅箔，可使用由銅之單金屬所成的箔，亦可使用由銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所成的箔。When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper can be used, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

支持體的與樹脂組成物層接合的面亦可施予消光處理、電暈處理、帶電防止處理。The surface of the support that is bonded to the resin composition layer may also be subjected to matting treatment, corona treatment, or antistatic treatment.

作為支持體，亦可使用於與樹脂組成物層接合的面上具有脫模層之附有脫模層的支持體。作為使用於附有脫模層的支持體之脫模層的脫模劑，例如可舉出選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及矽氧樹脂所成群的1種以上脫模劑。附有脫模層的支持體可使用販售品，例如可舉出作為具有將醇酸樹脂系脫模劑作為主成分之脫模層的PET薄膜之Lintec公司製的「SK-1」、「AL-5」、「AL-7」、Toray公司製的「lumirrorT60」、帝人公司製的「Purex」、Unitika Ltd.製的「Unipeel」等。As the support, a release layer-attached support having a release layer on the surface bonded to the resin composition layer can also be used. Examples of the release agent used for the release layer of the support with the release layer include one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The above release agent. A commercially available support with a release layer can be used, and examples thereof include "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin release agent as a main component. AL-5", "AL-7", "lumirrorT60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Ltd., etc.

支持體之厚度雖無特別限定，以5μm～75μm之範圍為佳，以10μm～60μm之範圍為較佳。且，使用附有脫模層的支持體之情況時，將附有脫模層之支持體全體厚度設定在上述範圍者為佳。Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable to set the entire thickness of the support with a release layer within the above range.

其中一實施形態，樹脂薄片可進一步配合所需含有任意層。作為此等任意層，例如可舉出於未與樹脂組成物層之支持體接合的面(即，與支持體的反側面)設置的依據支持體的保護薄膜等。保護薄膜之厚度雖非特別限定者，例如1μm～40μm。藉由層合保護薄膜，可抑制樹脂組成物層之表面的垃圾附著及傷痕。In one embodiment, the resin sheet can further contain any layer as required. Examples of such arbitrary layers include a protective film based on the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but may be, for example, 1 μm to 40 μm. By laminating a protective film, garbage adhesion and scratches on the surface of the resin composition layer can be suppressed.

樹脂薄片，例如藉由直接使用液狀(塗漆狀)之樹脂組成物，或於溶劑中溶解樹脂組成物而調製成液狀(塗漆狀)的樹脂組成物，將此使用模具塗布等的塗布裝置而塗布於支持體上，進一步乾燥後形成樹脂組成物層而可製造。The resin sheet is prepared by directly using a liquid (paint-like) resin composition, or by dissolving the resin composition in a solvent to prepare a liquid (paint-like) resin composition, and applying the resin composition using a mold, etc. The coating device is used to apply the resin composition on the support, and after further drying, a resin composition layer is formed and the resin composition layer can be manufactured.

作為溶劑，可舉出與作為樹脂組成物之成分而說明的(H)溶劑之相同者。溶劑可單獨使用1種類，亦可組合2種類以上而使用。Examples of the solvent include the same solvent (H) described as a component of the resin composition. One type of solvent may be used alone, or two or more types may be used in combination.

乾燥可藉由加熱、吹熱風等乾燥方法而實施。乾燥條件雖無特別限定，但樹脂組成物層中之溶劑的含有量通常為10質量%以下，較佳為乾燥至5質量%以下。雖依據樹脂組成物中之溶劑的沸點而相異，但例如使用含有30質量%～60質量%之溶劑的樹脂組成物之情況時，藉由在50℃～150℃下進行3分鐘～10分鐘乾燥時，可形成樹脂組成物層。Drying can be implemented by drying methods such as heating and blowing hot air. Although the drying conditions are not particularly limited, the solvent content in the resin composition layer is usually 10 mass% or less, and preferably is dried to 5 mass% or less. Although it differs depending on the boiling point of the solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of the solvent, by performing the process at 50°C to 150°C for 3 minutes to 10 minutes When drying, a resin composition layer can be formed.

樹脂薄片可捲成輥狀而保存。樹脂薄片具有保護薄膜之情況時，通常經由剝離保護薄膜而成為可使用。The resin sheet can be rolled into a roll shape and stored. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

其中一實施形態，預浸料係由於薄片狀纖維基材含浸上述樹脂組成物而形成。In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition.

使用於預浸料的薄片狀纖維基材，例如可使用作為玻璃布、芳醯基不織布、液晶聚合物不織布等的預浸料用基材而常用者。由薄型化之觀點來看，薄片狀纖維基材之厚度以50μm以下為佳，較佳為40μm以下，更佳為30μm以下，特佳為20μm以下。薄片狀纖維基材之厚度的下限並無特別限定，通常為10μm以上。The sheet-like fiber base material used for prepregs can be, for example, those commonly used as base materials for prepregs such as glass cloth, aryl-based nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but is usually 10 μm or more.

預浸料可藉由熱熔法、溶劑法等的方法而製造。Prepregs can be manufactured by methods such as hot melt method and solvent method.

預浸料之厚度可為與上述樹脂薄片中之樹脂組成物層的相同範圍。The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

薄片狀層合材料例如可適用於欲形成半導體晶片封裝之製造中之絕緣層(半導體晶片封裝之絕緣用樹脂薄片)上。作為可適用之半導體晶片封裝，例如可舉出Fan-out型WLP、Fan-in型WLP、Fan-out型PLP、Fan-in型PLP等。又，薄片狀層合材料例如可使用於欲形成電路基板之絕緣層(電路基板之絕緣層用樹脂薄片)上。薄片狀層合材料進一步可使用於將半導體晶片連接於基板後而使用的MUF之材料。薄片狀層合材料使用於形成層間絕緣層而較佳。The sheet-like laminated material can be applied to, for example, an insulating layer (insulating resin sheet of a semiconductor chip package) to be formed during manufacturing of a semiconductor chip package. Examples of applicable semiconductor chip packages include Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, and the like. Moreover, the sheet-like laminated material can be used, for example, on the insulating layer to be formed of a circuit board (resin sheet for the insulating layer of the circuit board). The sheet-like laminate material can further be used as a material for MUF used after connecting a semiconductor chip to a substrate. The sheet-like laminated material is preferably used for forming an interlayer insulating layer.

[電路基板] 有關本發明之一實施形態的電路基板含有樹脂組成物之硬化物。通常電路基板具備以樹脂組成物之硬化物所形成的絕緣層。絕緣層含有上述樹脂組成物的硬化物，較佳為僅含有上述樹脂組成物之硬化物。該電路基板例如可藉由含有下述步驟(I)及步驟(II)的製造方法而製造。 (I)於內層基板上形成樹脂組成物層的步驟。 (II)使樹脂組成物層進行硬化而形成絕緣層的步驟。 [Circuit board] A circuit board according to an embodiment of the present invention contains a cured product of a resin composition. Generally, the circuit board has an insulating layer formed of a hardened product of a resin composition. The insulating layer contains a cured product of the above-mentioned resin composition, and preferably contains only a cured product of the above-mentioned resin composition. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (I) and (II). (I) The step of forming a resin composition layer on the inner substrate. (II) The step of hardening the resin composition layer to form an insulating layer.

所謂在步驟(I)使用的「內層基板」為成為電路基板之基材的構件，例如可舉出玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等。又，該基板的該單面或雙面上可具有導體層，該導體層亦可經圖型加工。於基板的單面或雙面上形成導體層(迴路)之內層基板有時稱為「內層電路基板」。又，製造電路基板時，進一步必須形成絕緣層及/或導體層的中間製造物亦含於前述「內層基板」中。電路基板為零件內置迴路板之情況時，亦可使用內置零件之內層基板。The "inner layer substrate" used in step (I) is a member that serves as the base material of the circuit substrate. Examples thereof include glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermal substrate, etc. Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may also be patterned. The inner substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner circuit substrate". In addition, when manufacturing a circuit substrate, intermediate products that further require the formation of an insulating layer and/or a conductor layer are also included in the aforementioned "inner layer substrate". When the circuit board is a circuit board with built-in components, an inner substrate with built-in components can also be used.

將具備有內層基板之導體層進行圖型加工之情況時，由活用優異裂紋耐性的優點之觀點來看，該導體層之最小線/空間比較小為佳。所謂「線」表示導體層之配線寬，所謂「空間」表示配線間之間隔寬。最小線/空間比之範圍以100/100μm以下(即，間距為200μm以下)為佳，較佳為50/50μm以下，更佳為30/30μm以下，更佳為20/20μm以下，更佳為10/10μm以下。下限例如可為0.5/0.5μm以上。間距在導體層全體可為均勻，亦可為不均勻。導體層之最小間距例如可為100μm以下、60μm以下、40μm以下、36μm以下或30μm以下。When patterning a conductor layer having an inner substrate, it is preferable that the minimum line/space ratio of the conductor layer is small in order to take advantage of the excellent crack resistance. The so-called "line" refers to the wiring width of the conductor layer, and the so-called "space" refers to the spacing width between wirings. The range of the minimum line/space ratio is preferably 100/100 μm or less (ie, the pitch is 200 μm or less), preferably 50/50 μm or less, more preferably 30/30 μm or less, more preferably 20/20 μm or less, more preferably Below 10/10μm. The lower limit may be, for example, 0.5/0.5 μm or more. The spacing may be uniform or uneven throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 100 μm or less, 60 μm or less, 40 μm or less, 36 μm or less, or 30 μm or less.

對內層基板上之樹脂組成物層的形成，例如可藉由層合內層基板與樹脂薄片而進行。內層基板與樹脂薄片之層合，例如可藉由自支持體側將樹脂薄片加熱壓著於內層基板而進行。作為將樹脂薄片加熱壓著於內層基板的構件(以下亦稱為「加熱壓著構件」)，例如可舉出經加熱的金屬板(SUS鏡板等)或金屬輥(SUS輥等)。且，並非將加熱壓著構件直接擠壓於樹脂薄片，其為樹脂薄片充分地追隨於內層基板之表面凹凸，隔著耐熱橡膠等彈性材而擠壓者為佳。The resin composition layer on the inner substrate can be formed, for example, by laminating the inner substrate and a resin sheet. The inner layer substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of a member that heat-presses the resin sheet to the inner substrate (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.). Moreover, it is preferable that the resin sheet fully follows the surface irregularities of the inner substrate and is pressed through an elastic material such as heat-resistant rubber, rather than directly pressing the heated pressing member against the resin sheet.

內層基板與樹脂薄片之層合可藉由真空層合法而實施。真空層合法中，加熱壓著溫度以60℃～160℃為佳，較佳為80℃～140℃之範圍，加熱壓著壓力以0.098 MPa～1.77MPa為佳，較佳為0.29MPa～1.47MPa之範圍，加熱壓著時間以20秒～400秒為佳，較佳為30秒～300秒之範圍。層合較佳在壓力26.7hPa以下之減壓條件下而實施。The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, preferably 80°C to 140°C, and the heating and pressing pressure is preferably 0.098 MPa to 1.77MPa, and preferably 0.29MPa to 1.47MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

層合可藉由販售之真空層合體而進行。作為販售之真空層合體，例如可舉出名機製作所公司製的真空加壓式層合體、Nikko Materials公司製的真空施放器、分批式真空加壓層合體等。Lamination can be performed by commercially available vacuum laminates. Examples of commercially available vacuum laminates include vacuum pressurized laminates manufactured by Minki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials, and batch-type vacuum pressurized laminates.

於層合後，常壓下(大氣壓下)例如亦可藉由將加熱壓著構件自支持體側擠壓，進行經層合的樹脂薄片之平滑化處理。平滑化處理之擠壓條件可與上述層合的加熱壓著條件相同。平滑化處理可藉由販售之層合體而進行。且層合與平滑化處理可使用上述販售的真空層合體而連續進行。After lamination, the laminated resin sheets can be smoothed under normal pressure (atmospheric pressure), for example, by pressing a heated pressing member from the support side. The extrusion conditions of the smoothing treatment can be the same as the heat pressing conditions of the above-mentioned lamination. Smoothing can be done with commercially available laminates. Furthermore, lamination and smoothing processing can be performed continuously using the vacuum laminate sold above.

支持體可在步驟(I)與步驟(II)之間除去，亦可在步驟(II)之後除去。The support may be removed between step (I) and step (II), or may be removed after step (II).

步驟(II)中，使樹脂組成物層硬化，形成由樹脂組成物之硬化物所成的絕緣層。樹脂組成物層之硬化通常藉由熱硬化進行。樹脂組成物層之具體硬化條件亦依據樹脂組成物之種類而相異。其中一例子，硬化溫度以120℃～240℃為佳，較佳為150℃～220℃，更佳為170℃～210℃。硬化時間以5分鐘～120分鐘為佳，較佳為10分鐘～100分鐘，更佳為15分鐘～100分鐘。In step (II), the resin composition layer is hardened to form an insulating layer made of a hardened product of the resin composition. The resin composition layer is usually hardened by thermal hardening. The specific hardening conditions of the resin composition layer also vary depending on the type of resin composition. In one example, the hardening temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more preferably 170°C to 210°C. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, more preferably 15 minutes to 100 minutes.

電路基板之製造方法中於樹脂組成物層之熱硬化前，含有將樹脂組成物層在比硬化溫度低的溫度下進行預備加熱者為佳。例如先使樹脂組成物層進行熱硬化，通常為50℃～150℃，以60℃～140℃為佳，較佳為70℃～130℃之溫度，亦可將樹脂組成物層通常進行5分鐘以上，以5分鐘～150分鐘為佳，較佳為15分鐘～120分鐘，更佳為15分鐘～100分鐘之預備加熱。The method for manufacturing a circuit board preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before thermally curing the resin composition layer. For example, the resin composition layer is first thermally hardened, usually at a temperature of 50°C to 150°C, preferably 60°C to 140°C, and preferably at a temperature of 70°C to 130°C. The resin composition layer can also be heated for 5 minutes, usually The above is preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes for preliminary heating.

製造電路基板時，可進一步實施(III)於絕緣層開孔的步驟、(IV)使絕緣層進行粗化處理之步驟、(V)形成導體層之步驟。此等步驟(III)至步驟(V)可使用於電路基板之製造上，可依據斯業者的公知各種方法而實施。且，將支持體在步驟(II)之後除去的情況時，該支持體之除去可在步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間，或步驟(IV)與步驟(V)之間而實施。又，視必要可重複實施步驟(I)～步驟(V)之絕緣層及導體層的形成，製造出具有多層印刷配線板等的多層結構之電路基板。When manufacturing the circuit substrate, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to step (V) can be used in the manufacture of circuit substrates and can be implemented according to various methods known in the industry. And, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or between step (IV). IV) and step (V). If necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) can be repeated to produce a circuit board having a multilayer structure such as a multilayer printed wiring board.

其他實施形態中，電路基板可使用上述預浸料而製造。製造方法基本上可與使用樹脂薄片之情況相同。In other embodiments, the circuit board can be manufactured using the above prepreg. The manufacturing method can be basically the same as when using a resin sheet.

步驟(III)為於絕緣層開孔的步驟，藉此對絕緣層可形成貫通孔、通孔等孔。步驟(III)可配合使用於絕緣層之形成的樹脂組成物之組成等，例如使用鑽頭、雷射、電漿等而實施。孔之尺寸及形狀可配合電路基板之設計而適宜地決定。Step (III) is the step of opening holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. Step (III) can be implemented by using a drill, laser, plasma, etc. in conjunction with the composition of the resin composition used to form the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the circuit substrate.

步驟(IV)為使絕緣層進行粗化處理的步驟。通常該步驟(IV)中亦進行污跡之除去。因此，前述粗化處理有時稱為「除污跡處理」。粗化處理之程序、條件並無特別限定，可採用形成電路基板之絕緣層時通常使用的公知程序、條件。例如依藉由膨潤液之膨潤處理、藉由氧化劑之粗化處理、藉由中和液之中和處理的順序實施而使絕緣層進行粗化處理。Step (IV) is a step of roughening the insulating layer. Usually, stain removal is also performed in this step (IV). Therefore, the aforementioned roughening treatment is sometimes called "stain removal treatment". The procedures and conditions of the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming an insulating layer of a circuit substrate can be adopted. For example, the insulating layer is roughened in the order of swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid.

作為使用於粗化處理之膨潤液，例如可舉出鹼溶液、界面活性劑溶液等，較佳為鹼溶液。作為該鹼溶液，氫氧化鈉溶液、氫氧化鉀溶液為較佳。作為可購得之膨潤液，例如可舉出Atotech Japan Co., Ltd.製的「Swelling Dip Securigant P」、「Swelling Dip SecurigantSBU」等。藉由膨潤液之膨潤處理，例如可藉由於30℃～90℃之膨潤液中浸漬絕緣層1分鐘～20分鐘而進行。由可抑制絕緣層之樹脂的膨潤至適度水準的觀點來看，以於40℃～80℃之膨潤液浸漬絕緣層5分鐘～15分鐘者為佳。Examples of the swelling liquid used in the roughening treatment include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferred. As the alkali solution, sodium hydroxide solution and potassium hydroxide solution are preferred. Examples of commercially available swelling liquids include "Swelling Dip Securigant P" and "Swelling Dip Securigant SBU" manufactured by Atotech Japan Co., Ltd.. The swelling treatment by the swelling liquid can be performed, for example, by immersing the insulating layer in a swelling liquid of 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is better to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 to 15 minutes.

作為使用於粗化處理的氧化劑，例如可舉出於氫氧化鈉之水溶液溶解過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液。藉由鹼性過錳酸溶液等的氧化劑的粗化處理在60℃～100℃進行加熱的氧化劑溶液中浸漬絕緣層10分鐘～30分鐘者為佳。又，鹼性過錳酸溶液中之過錳酸鹽的濃度以5質量%～10質量%為佳。作為可購得之氧化劑，例如可舉出Atotech Japan Co., Ltd.製的「Concentrate Compact CP」、「Dosing Solution Security P」等的鹼性過錳酸溶液。Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. It is preferable to immerse the insulating layer in an oxidizing agent solution heated at 60° C. to 100° C. for 10 to 30 minutes in the roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

作為使用於粗化處理的中和液，以酸性之水溶液為佳，作為販售品，例如可舉出Atotech Japan Co., Ltd.製的「Reduction Solution Securigant P」。可藉由中和液之處理可藉由將藉由氧化劑進行粗化處理的處理面浸漬在30℃～80℃之中和液中5分鐘～30分鐘而進行。由作業性等觀點來看，將藉由氧化劑進行粗化處理之對象物浸漬在40℃～70℃之中和液中5分鐘～20分鐘的方法為佳。As a neutralizing liquid used for roughening treatment, an acidic aqueous solution is preferable. As a commercial product, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. is mentioned, for example. Treatment with a neutralizing liquid can be performed by immersing the treated surface roughened by an oxidizing agent in a neutralizing liquid at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., the method of immersing the object to be roughened by an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferred.

步驟(V)為形成導體層之步驟，於絕緣層上形成導體層。使用於導體層之導體材料並無特別限定。在較佳實施形態中，導體層含有選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成群的1種以上金屬。導體層可為單金屬層亦可為合金層，作為合金層，例如可舉出由選自由上述群的2種以上金屬之合金(例如鎳･鉻合金、銅･鎳合金及銅･鈦合金)所形成的層。其中亦由導體層形成之泛用性、成本、製圖之容易性等觀點來看，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅的單金屬層，或鎳･鉻合金、銅･鎳合金、銅･鈦合金之合金層為佳，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅之單金屬層，或鎳･鉻合金之合金層為較佳，以銅之單金屬層為更佳。Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include an alloy of two or more metals selected from the above group (for example, nickel･chromium alloy, copper･nickel alloy and copper･titanium alloy) the layer formed. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy is also considered from the viewpoint of versatility, cost, and ease of patterning of the conductor layer. , copper･nickel alloy, copper･titanium alloy alloy layer is preferred, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or alloy layer of nickel･chromium alloy is preferred , a single metal layer of copper is better.

導體層可為單層結構，亦可為由相異種類之金屬或者合金所成的單金屬層或合金層經2層以上層合的複層結構。導體層為複層結構之情況時，銜接於絕緣層之層以鉻、鋅或者鈦之單金屬層，或鎳･鉻合金之合金層者為佳。The conductor layer may be a single-layer structure, or may be a multi-layer structure in which a single metal layer or two or more alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

導體層之厚度雖取決於所望電路基板之設計，一般為3μm～35μm，以5μm～30μm為佳。Although the thickness of the conductor layer depends on the design of the desired circuit substrate, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

其中一實施形態，導體層可經鍍敷而形成。例如藉由半添加法、全添加法等過去公知技術而對絕緣層表面進行鍍敷，可形成具有所望配線圖型之導體層。由製造之簡便性的觀點來看，以半添加法為佳。以下表示導體層藉由半添加法而形成的例子。In one embodiment, the conductor layer may be formed by plating. For example, by plating the surface of the insulating layer using conventionally known techniques such as a semi-additive method and a fully additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of ease of production, the semi-additive method is preferred. The following shows an example in which the conductor layer is formed by the semi-additive method.

首先，於絕緣層表面上，藉由無電解鍍敷而形成鍍敷種層。其次於所形成的鍍敷種層上，對應所望配線圖型，形成露出鍍敷種層的一部份的光罩圖型。於露出之鍍敷種層上，藉由電解鍍敷形成金屬層後，除去光罩圖型。其後，將不要的鍍敷種層藉由蝕刻等除去，可形成具有所望配線圖型之導體層。First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern exposing a part of the plating seed layer is formed corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the photomask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching, etc. to form a conductor layer having a desired wiring pattern.

其他實施形態中，導體層可使用金屬箔而形成。使用金屬箔而形成導體層的情況時，步驟(V)在步驟(I)與步驟(II)之間實施者為佳。例如在步驟(I)之後除去支持體，於露出的樹脂組成物層之表面上層合金屬箔。樹脂組成物層與金屬箔之層合可藉由真空層合法而實施。層合之條件可與在步驟(I)所說明之條件相同。其次，實施步驟(II)而形成絕緣層。其後，利用絕緣層上之金屬箔，藉由消減方法、修飾半添加法等過去公知技術，可形成具有所望配線圖型之導體層。In other embodiments, the conductor layer may be formed using metal foil. When forming the conductor layer using metal foil, it is preferable that step (V) is performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The resin composition layer and the metal foil can be laminated by a vacuum lamination method. The conditions for lamination can be the same as those described in step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer with a desired wiring pattern can be formed by using known techniques such as subtractive methods and modified semi-additive methods.

金屬箔例如可藉由電解法、壓延法等公知方法而製造。作為金屬箔之販售品，例如可舉出JX日鑛日石金屬公司製的HLP箔、JXUT-III箔、三井金屬鑛山公司製的3EC-III箔、TP-III箔等。The metal foil can be produced by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Metal Mining Co., Ltd., and the like.

[半導體晶片封裝] 有關本發明之一實施形態的半導體晶片封裝含有樹脂組成物之硬化物。通常半導體晶片封裝含有以樹脂組成物之硬化物所形成的絕緣層。絕緣層含有上述樹脂組成物之硬化物，較佳為僅含有上述樹脂組成物之硬化物。作為該半導體晶片封裝，例如可舉出下述者。 [Semiconductor chip packaging] A semiconductor chip package according to an embodiment of the present invention contains a cured product of a resin composition. Generally, a semiconductor chip package includes an insulating layer formed of a hardened material of a resin composition. The insulating layer contains a cured product of the above-mentioned resin composition, and preferably contains only a cured product of the above-mentioned resin composition. Examples of the semiconductor chip package include the following.

有關第一例的半導體晶片封裝含有上述電路基板與載持於該電路基板之半導體晶片。該半導體晶片封裝可藉由於電路基板接合半導體晶片而製造。The semiconductor chip package of the first example includes the above-mentioned circuit substrate and a semiconductor chip carried on the circuit substrate. The semiconductor chip package can be manufactured by bonding semiconductor chips to a circuit substrate.

電路基板與半導體晶片之接合條件可採用半導體晶片之端子電極與電路基板之迴路配線可經導體接續的任意條件。例如可採用半導體晶片之倒裝晶片實裝中所使用的條件。又，例如於半導體晶片與電路基板之間亦可藉由絕緣性接著劑而接合。The bonding conditions between the circuit board and the semiconductor chip can be any conditions in which the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be connected through conductors. For example, conditions used in flip-chip mounting of semiconductor wafers can be adopted. Furthermore, for example, the semiconductor chip and the circuit board may be joined by an insulating adhesive.

作為接合方法之例子，可舉出將半導體晶片壓著於電路基板之方法。作為壓著條件，壓著溫度通常為120℃～240℃之範圍(以130℃～200℃之範圍為佳，較佳為140℃～180℃之範圍)，壓著時間通常為1秒～60秒之範圍(以5秒～30秒之範圍為佳)。An example of the bonding method is a method of pressing a semiconductor wafer onto a circuit board. As the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, and more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 The range of seconds (the range of 5 seconds to 30 seconds is preferred).

又，作為接合方法之其他例子，可舉出將半導體晶片於電路基板經回流焊而接合之方法。回流焊條件亦可設定在120℃～300℃之範圍。Another example of the bonding method is a method of bonding the semiconductor chip to the circuit board through reflow soldering. Reflow soldering conditions can also be set in the range of 120°C to 300°C.

將半導體晶片接合於電路基板後，亦可將半導體晶片以模具底層填料材進行填充。作為該模具底層填料材，亦可使用上述樹脂組成物。After the semiconductor wafer is bonded to the circuit substrate, the semiconductor wafer can also be filled with mold underfill material. As the mold underfill material, the above-mentioned resin composition can also be used.

有關第二例之半導體晶片封裝含有半導體晶片與以樹脂組成物之硬化物所形成的絕緣層。作為有關第二例之半導體晶片封裝，例如可舉出Fan-out型WLP、Fan-out型PLP等。The semiconductor chip package of the second example includes a semiconductor chip and an insulating layer formed of a hardened material of a resin composition. Examples of the semiconductor chip package related to the second example include Fan-out type WLP, Fan-out type PLP, and the like.

圖1表示作為有關本發明之一實施形態的半導體晶片封裝之一例子的Fan-out型WLP之模式截面圖。作為Fan-out型WLP之半導體晶片封裝100，例如圖1所示，其中具備半導體晶片110；包覆半導體晶片110之周圍而形成的密封層120；設置在與半導體晶片110之密封層120的反側面之作為絕緣層之再配線形成層130；作為導體層之再配線層140；阻焊層150；及顛簸160。FIG. 1 shows a schematic cross-sectional view of a Fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention. The semiconductor chip package 100 of the Fan-out type WLP is, for example, as shown in FIG. On the side, there is a rewiring formation layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and bumps 160.

如此半導體晶片封裝之製造方法含有以下步驟。 (i)於基材層合暫時固定薄膜之步驟、 (ii)將半導體晶片暫時固定於暫時固定薄膜上之步驟、 (iii)於半導體晶片上形成密封層之步驟、 (iv)將基材及暫時固定薄膜自半導體晶片進行剝離之步驟、 (v)於剝離半導體晶片之基材及暫時固定薄膜之面上形成再配線形成層之步驟、 (vi)於再配線形成層上形成作為導體層之再配線層的步驟，以及 (vii)於再配線層上形成阻焊層之步驟。 又前述半導體晶片封裝之製造方法亦可含有 (viii)將複數之半導體晶片封裝切割成各個半導體晶片封裝而使其個片化之步驟。 The manufacturing method of such a semiconductor chip package includes the following steps. (i) The step of laminating and temporarily fixing the film on the base material, (ii) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (iii) The step of forming a sealing layer on the semiconductor wafer, (iv) The step of peeling the base material and the temporary fixing film from the semiconductor wafer, (v) The step of forming a rewiring formation layer on the surface of the peeled semiconductor wafer base material and temporary fixing film, (vi) the step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (vii) The step of forming a solder resist layer on the rewiring layer. In addition, the manufacturing method of the aforementioned semiconductor chip package may also include (viii) The step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to individualize them.

(步驟(i)) 步驟(i)為於基材層合暫時固定薄膜之步驟。基材與暫時固定薄膜之層合條件，與電路基板的製造方法中之內層基板與樹脂薄片之層合條件相同。 (step (i)) Step (i) is a step of laminating a temporarily fixed film on the substrate. The lamination conditions of the base material and the temporary fixing film are the same as the lamination conditions of the inner substrate and the resin sheet in the manufacturing method of the circuit board.

作為基材，例如可舉出矽晶圓；玻璃晶圓；玻璃基板；銅、鈦、不銹鋼、冷間壓延鋼板(SPCC)等的金屬基板；FR-4基板等的於玻璃纖維浸漬環氧樹脂等之經熱硬化處理的基板；由BT樹脂等的雙馬來醯亞胺三嗪樹脂所成的基板等。Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); and glass fiber-impregnated epoxy resin-impregnated FR-4 substrates. Such as substrates that have been thermally cured; substrates made of bismaleimidetriazine resin such as BT resin, etc.

暫時固定薄膜可使用可自半導體晶片剝離，且可使半導體晶片進行暫時固定的任意材料。作為販售品，可舉出日東電工公司製「Riva Alpha」等。Any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer can be used as the temporary fixing film. Examples of commercial products include "Riva Alpha" manufactured by Nitto Denko Co., Ltd.

(步驟(ii)) 步驟(ii)為將半導體晶片暫時固定於暫時固定薄膜上之步驟。半導體晶片之暫時固定，例如可使用倒裝晶片鍵合機、模具鍵合機等裝置而進行。半導體晶片之配置的佈局及配置數可配合暫時固定薄膜之形狀、尺寸、作為目的之半導體晶片封裝的生產數等而適當地設定。例如亦可在複數行且複數列之矩陣狀下整列半導體晶片而進行暫時固定。 (step (ii)) Step (ii) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. Semiconductor wafers can be temporarily fixed using devices such as flip-chip bonding machines and mold bonding machines, for example. The layout and number of arrangements of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixing film, the intended production number of semiconductor wafer packages, and the like. For example, the semiconductor wafers may be arranged in a matrix with a plurality of rows and a plurality of columns and temporarily fixed.

(步驟(iii)) 步驟(iii)為於半導體晶片上形成密封層之步驟。密封層例如可藉由感光性樹脂組成物或熱硬化性樹脂組成物而形成。將該密封層可藉由上述有關實施形態之樹脂組成物的硬化物而形成。密封層通常可藉由含有於半導體晶片上形成樹脂組成物層之步驟，與使該樹脂組成物層經硬化而形成密封層之步驟的方法而形成。 (step (iii)) Step (iii) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer can be formed of, for example, a photosensitive resin composition or a thermosetting resin composition. The sealing layer can be formed from a cured product of the resin composition of the above-described embodiment. The sealing layer can generally be formed by a method including the steps of forming a resin composition layer on the semiconductor wafer, and the steps of hardening the resin composition layer to form the sealing layer.

(步驟(iv)) 步驟(iv)為將基材及暫時固定薄膜自半導體晶片進行剝離之步驟。剝離方法採用配合暫時固定薄膜之材質的適當方法者為佳。作為剝離方法，例如可舉出將暫時固定薄膜經加熱、發泡或膨脹而剝離之方法。又，作為剝離方法，例如可舉出通過基材對暫時固定薄膜照射紫外線，降低暫時固定薄膜之黏著力的剝離方法。 (step (iv)) Step (iv) is a step of peeling off the base material and the temporary fixing film from the semiconductor wafer. The peeling method is preferably an appropriate method that matches the material of the temporarily fixed film. Examples of the peeling method include a method of peeling off the temporarily fixed film by heating, foaming or expanding it. As a peeling method, for example, the temporarily fixed film is irradiated with ultraviolet rays through the base material to reduce the adhesive force of the temporarily fixed film.

如前述將基材及暫時固定薄膜自半導體晶片進行剝離時，露出密封層面。半導體晶片封裝之製造方法亦可含有研磨該露出的密封層面之步驟。藉由研磨可提高密封層之表面的平滑性。When the base material and the temporary fixing film are peeled off from the semiconductor wafer as mentioned above, the sealing layer is exposed. The manufacturing method of the semiconductor chip package may also include the step of grinding the exposed sealing layer. The surface smoothness of the sealing layer can be improved by grinding.

(步驟(v)) 步驟(v)為於剝離半導體晶片之基材及暫時固定薄膜的面上，形成作為絕緣層之再配線形成層的步驟。通常該再配線形成層形成於半導體晶片及密封層上。再配線形成層可藉由上述有關實施形態之樹脂組成物的硬化物而形成。再配線形成層通常可藉由含有，於半導體晶片上形成樹脂組成物層之步驟，與使該樹脂組成物層硬化而形成再配線形成層之步驟的方法而形成。對半導體晶片上之樹脂組成物層的形成，例如取代內層基板而使用半導體晶片以外，可藉由與在前述電路基板之製造方法所說明的對內層基板上的樹脂組成物層之形成方法的相同方法。 (step (v)) Step (v) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporarily fixed film are peeled off. Typically, the rewiring formation layer is formed on the semiconductor wafer and the sealing layer. The rewiring formation layer can be formed by a cured product of the resin composition of the above-described embodiment. The rewiring formation layer can generally be formed by a method including a step of forming a resin composition layer on a semiconductor wafer, and a step of hardening the resin composition layer to form the rewiring formation layer. The resin composition layer on the semiconductor wafer can be formed by, for example, using the semiconductor wafer instead of the inner substrate. The method for forming the resin composition layer on the inner substrate described in the above-mentioned manufacturing method of the circuit substrate can be used. the same method.

於半導體晶片上形成樹脂組成物層後，使該樹脂組成物層進行硬化，得到作為含有樹脂組成物之硬化物的絕緣層之再配線形成層。樹脂組成物層之硬化條件亦可採用與電路基板之製造方法中的樹脂組成物層之硬化條件的相同條件。使樹脂組成物層進行熱硬化之情況時，於該熱硬化之前，對於樹脂組成物層，亦可施予在比硬化溫度低的溫度下進行加熱之預備加熱處理。該預備加熱處理之處理條件，亦可採用與電路基板之製造方法中的預備加熱處理之相同條件。通常形成再配線形成層後，欲接續半導體晶片與再配線層而於再配線形成層形成孔。After the resin composition layer is formed on the semiconductor wafer, the resin composition layer is cured to obtain a rewiring formation layer that is an insulating layer containing a cured product of the resin composition. The curing conditions of the resin composition layer may also be the same as the curing conditions of the resin composition layer in the manufacturing method of the circuit board. When the resin composition layer is thermally cured, the resin composition layer may be subjected to a preparatory heat treatment of heating at a temperature lower than the curing temperature before the thermal curing. The processing conditions of this preliminary heat treatment can also be the same as those of the preliminary heat treatment in the manufacturing method of a circuit board. Usually, after the rewiring formation layer is formed, holes are formed in the rewiring formation layer in order to connect the semiconductor wafer and the rewiring layer.

(步驟(vi)) 步驟(vi)為於再配線形成層上形成作為導體層之再配線層的步驟。於再配線形成層上形成再配線層之方法可與電路基板之製造方法中對於絕緣層上之導體層的形成方法之相同。又，亦可重複進行步驟(v)及步驟(vi)，交互累積(積聚)再配線層及再配線形成層。 (step (vi)) Step (vi) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer may be the same as the method of forming the conductor layer on the insulating layer in the manufacturing method of the circuit substrate. In addition, steps (v) and (vi) can also be repeated to alternately accumulate (accumulate) the rewiring layer and the rewiring formation layer.

(步驟(vii)) 步驟(vii)為於再配線層上形成阻焊層之步驟。阻焊層之材料可使用具有絕緣性之任意材料。其中亦由半導體晶片封裝之製造的容易度之觀點來看，以感光性樹脂組成物及熱硬化性樹脂組成物為佳。阻焊層亦可藉由上述有關實施形態之樹脂組成物的硬化物而形成。 (step (vii)) Step (vii) is a step of forming a solder resist layer on the rewiring layer. The solder resist layer can be made of any insulating material. Among them, photosensitive resin compositions and thermosetting resin compositions are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. The solder resist layer may also be formed by a cured product of the resin composition of the above-described embodiment.

又，在步驟(vii)中，視必要亦可進行形成顛簸之凸塊加工。凸塊加工可藉由焊球、焊接鍍敷等方法而進行。又，凸塊加工中之貫通孔的形成亦可進行與步驟(v)之相同步驟。Furthermore, in step (vii), bump processing may be performed to form bumps if necessary. Bump processing can be performed by solder ball, solder plating and other methods. In addition, the formation of the through-hole in the bump processing can also be carried out in the same step as step (v).

(步驟(viii)) 半導體晶片封裝之製造方法除步驟(i)～(vii)以外亦可含有步驟(viii)。步驟(viii)係將複數半導體晶片封裝切割成各個半導體晶片封裝而使其個片化之步驟。將半導體晶片封裝切割成各個半導體晶片封裝之方法並無特別限定。 (step (viii)) The manufacturing method of semiconductor chip packaging may also include step (viii) in addition to steps (i) to (vii). Step (viii) is a step of cutting the plurality of semiconductor wafer packages into individual semiconductor wafer packages to individualize them. The method of cutting the semiconductor wafer package into individual semiconductor wafer packages is not particularly limited.

[半導體裝置] 半導體裝置具備上述電路基板或半導體晶片封裝。作為半導體裝置，例如可舉出提供於電器製品(例如電腦、手機、智慧型手機、平板電腦類型裝置、可安裝的裝置、數位照相機、醫療機器及電視等)及交通工具(例如機車、汽車、電車、船舶及飛機等)等各種半導體裝置。 [實施例] [Semiconductor device] The semiconductor device includes the above-mentioned circuit board or semiconductor chip package. Examples of semiconductor devices include those provided in electrical products (such as computers, mobile phones, smartphones, tablet type devices, mountable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (such as motorcycles, automobiles, etc.) trains, ships, airplanes, etc.) and other semiconductor devices. [Example]

以下表示實施例而對本發明進行具體說明。但，本發明並非限定於以下實施例者。以下說明中，表示量之「份」及「%」若無另外說明時，各表示「質量份」及「質量%」。特別無特定溫度及壓力之情況的溫度條件及壓力條件時其表示室溫(25℃)及大氣壓(1atm)。以下說明中之「L/S」若無其他說明時，其表示導體圖型之線(配線寬)/空間(間隔寬)比。The present invention will be described in detail below using examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively, unless otherwise stated. In particular, when there are no specific temperature and pressure conditions, the temperature conditions and pressure conditions represent room temperature (25°C) and atmospheric pressure (1atm). Unless otherwise specified, "L/S" in the following description represents the line (wiring width)/space (space width) ratio of the conductor pattern.

＜實施例1＞ 於聯苯基型固體狀環氧樹脂(日本化藥公司製「NC3000L」，環氧當量約269g/eq.)25份、萘型固體狀環氧樹脂(日本化藥公司製「ESN475V」，環氧當量約332g/eq.)15份、三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq，150mPa･s)5份中加入甲基乙基酮(MEK)70份，一邊攪拌一邊使其加熱溶解，得到溶液。將該溶液冷卻至室溫，調製出環氧樹脂之溶解組成物。 <Example 1> 25 parts of biphenyl-type solid epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight is about 269g/eq.), and 25 parts of naphthalene-type solid epoxy resin ("ESN475V" manufactured by Nippon Kayaku Co., Ltd., environmentally friendly Add methyl groups to 15 parts of oxygen equivalent (approximately 332g/eq.) trimethylolpropane type liquid epoxy resin ("ED-505" manufactured by ADEKA, approximately 150g/eq. epoxy, 150mPa･s) 70 parts of ethyl ketone (MEK) was heated and dissolved with stirring to obtain a solution. The solution was cooled to room temperature to prepare a dissolved composition of the epoxy resin.

於該溶解組成物中，混合含有三嗪骨架之酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)5份、活性酯化合物(DIC公司製「HPC-8000-65T」，活性酯基當量約223g/eq.，不揮發成分率65%之甲苯溶液)26份、苯氧基樹脂(三菱化學公司製「YX7553BH30」，不揮發分30質量%之MEK與環己酮之1：1溶液)8份、以矽烷偶合劑(信越化學工業公司製「KBM-573」)經表面處理的生物質二氧化矽(M.I.T公司製「ethical silica」，平均粒徑3.7μm，碳含有量0.6質量%)180份、胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)，不揮發成分5質量%之MEK溶液)4份，以高速轉動混合機均勻地分散後調製出樹脂塗漆。In this dissolved composition, a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, with an active group equivalent of approximately 151 g/eq. and a non-volatile content of 50% 2-methoxy was mixed) Propanol solution) 5 parts, active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active ester group equivalent weight is about 223g/eq., toluene solution with non-volatile content rate 65%), 26 parts phenoxy resin ( "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 8 parts of a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass, surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Material: 180 parts of silicon dioxide ("ethical silica" manufactured by M.I.T., average particle diameter: 3.7 μm, carbon content: 0.6% by mass), amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), non-volatile components 5 mass% MEK solution) 4 parts, disperse it evenly with a high-speed rotating mixer to prepare a resin paint.

作為支持體，準備施予脫模處理之聚乙烯對苯二甲酸酯薄膜(Lintec公司製「AL5」，厚度38μm)。於該支持體之脫模面(施予脫模處理之面)上，均勻地塗布樹脂塗漆至樹脂組成物層之厚度成為40μm，在80℃～120℃(平均100℃)進行5分鐘乾燥後製造出具備支持體及樹脂組成物層之樹脂薄片。As a support, a release-treated polyethylene terephthalate film ("AL5" manufactured by Lintec, thickness 38 μm) was prepared. On the release surface of the support (the surface to be subjected to release treatment), apply resin paint evenly until the thickness of the resin composition layer becomes 40 μm, and dry for 5 minutes at 80°C to 120°C (average 100°C) Finally, a resin sheet with a support and a resin composition layer is produced.

＜實施例2＞ 實施例1中，將含有三嗪骨架之酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)的量自5份變更為12份。又，將活性酯化合物(DIC公司製「HPC-8000-65T」，活性酯基當量約223g/eq.，不揮發成分率65%之甲苯溶液)26份變更為萘酚型硬化劑(日鐵化學&材料公司製「SN-485」，羥基當量約205g/eq.)12份。以上事項以外藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 <Example 2> In Example 1, a phenol-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, an active group equivalent of about 151 g/eq., and a non-volatile component rate of 50% 2-methoxypropanol was used solution) was changed from 5 parts to 12 parts. In addition, 26 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active ester group equivalent weight of about 223g/eq. and a non-volatile content rate of 65%) was changed to a naphthol type hardener (Nippon Steel Co., Ltd. "SN-485" manufactured by Chemical & Materials Co., Ltd., hydroxyl equivalent weight is about 205g/eq.) 12 parts. Except for the above matters, a resin paint and a resin sheet were produced by the same method as Example 1.

＜實施例3＞ 實施例1中，將碳二亞胺系硬化劑(日清紡化學公司製「V-03」，活性基當量約216g/eq.，不揮發成分率50%之甲苯溶液)5份追加於樹脂組成物以外，藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 <Example 3> In Example 1, 5 parts of a carbodiimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution with an active group equivalent of about 216 g/eq. and a non-volatile content rate of 50%) was added to the resin composition. Except for this, a resin paint and a resin sheet were produced in the same manner as in Example 1.

＜實施例4＞ 實施例1中，未使用含有三嗪骨架之酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)5份。又，將活性酯化合物(DIC公司製「HPC-8000-65T」，活性酯基當量約223g/eq.，不揮發成分率65%之甲苯溶液)的量自26份變更為20份。進一步將雙酚A二氰酸酯之預聚物(Lonza Japan公司製「BA230S75」，氰酸酯當量約232g/eq.，不揮發分75質量%之MEK溶液)15份、鈷(III)乙醯丙酮(東京化成公司製)之1質量%的MEK溶液1份追加於樹脂組成物。又，將以矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的生物質二氧化矽(M.I.T公司製「ethical silica」，平均粒徑3.7μm，碳含有量0.6質量%)之量自180份變更為150份。以上事項以外藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 <Example 4> In Example 1, the phenolic hardener containing a triazine skeleton (2-methoxypropyl, manufactured by DIC Corporation "LA-3018-50P" with an active group equivalent of about 151 g/eq. and a non-volatile content rate of 50% was not used. alcohol solution) 5 parts. Furthermore, the amount of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active ester group equivalent weight of approximately 223 g/eq. and a non-volatile content rate of 65%) was changed from 26 parts to 20 parts. Further, 15 parts of bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan, cyanate equivalent of approximately 232 g/eq., MEK solution of 75 mass% non-volatile matter), cobalt (III) ethyl One part of a 1 mass % MEK solution in acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the resin composition. Also, biomass silica ("ethical silica" manufactured by M.I.T., average particle diameter 3.7 μm, carbon content 0.6 mass%) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) The quantity has been changed from 180 servings to 150 servings. Except for the above matters, a resin paint and a resin sheet were produced by the same method as Example 1.

＜實施例5＞ 實施例1中，將三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq.，150mPa･s)5份變更為新戊二醇型液狀環氧樹脂(ADEKA公司製「ED-523T」，環氧當量約140g/eq.，15mPa･s)5份。又，將藉由矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的生物質二氧化矽(M.I.T公司製「ethical silica」，平均粒徑3.7μm，碳含有量0.6質量%)之量自180份變更為60份。進一步將乙烯基苯甲基變性聚伸苯基醚(三菱瓦斯化學公司製「OPE-2St 2200」，不揮發成分率65%之甲苯溶液)5份，及藉由矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製「SO-C2」，平均粒徑0.5μm，碳含有量0%，生物質比率0%)120份追加於樹脂組成物。以上事項以外藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 <Example 5> In Example 1, 5 parts of trimethylolpropane type liquid epoxy resin ("ED-505" manufactured by ADEKA Co., Ltd., epoxy equivalent weight is about 150g/eq., 150mPa･s) was changed to neopentyl glycol type liquid. 5 parts of epoxy resin ("ED-523T" manufactured by ADEKA Co., Ltd., epoxy equivalent weight is about 140g/eq., 15mPa･s). In addition, biomass silica ("ethical silica" manufactured by M.I.T.) was surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), with an average particle diameter of 3.7 μm and a carbon content of 0.6% by mass. ) is changed from 180 servings to 60 servings. Further, 5 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content rate of 65%) was mixed with a silane coupling agent (Shin-Etsu Chemical Industry Co., Ltd. 120 parts of spherical silica (manufactured by Admatechs Co., Ltd. "SO-C2", average particle diameter 0.5 μm, carbon content 0%, biomass ratio 0%) that was surface-treated was added to the resin composition . Except for the above matters, a resin paint and a resin sheet were produced by the same method as Example 1.

＜實施例6＞ 於聯苯基型環氧樹脂(日本化藥公司製「NC3000L」，環氧當量約269g/eq.)10份、雙酚型液狀環氧樹脂(日鐵化學&材料公司製「ZX1059」，雙酚A型與雙酚F型之1：1混合品，環氧當量約169g/eq.，2600mPa･s)5份、亞萘基醚型固體狀環氧樹脂(DIC公司製「HP-6000」，環氧當量約250g/eq.)20份、二環戊二烯型固體狀環氧樹脂(DIC公司製「HP7200HH」，環氧當量約283g/eq.)5份及三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq.，150mPa･s)5份中加入甲基乙基酮70份，一邊攪拌一邊進行加熱溶解，得到溶液。將該溶液冷卻至室溫，調製出環氧樹脂之溶解組成物。 <Example 6> 10 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Chemical & Materials Co., Ltd., epoxy equivalent weight is about 269g/eq.) and bisphenol-type liquid epoxy resin ("ZX1059" manufactured by Nippon Chemical & Materials Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent weight is about 169g/eq., 2600mPa･s) 5 parts, naphthylene ether type solid epoxy resin (DIC Co., Ltd. "HP-6000" ", 20 parts of epoxy equivalent (epoxy equivalent: approximately 250g/eq.), 5 parts of dicyclopentadiene-type solid epoxy resin ("HP7200HH" manufactured by DIC Corporation, epoxy equivalent: approximately 283g/eq.), and trimethylolpropane Add 70 parts of methyl ethyl ketone to 5 parts of type liquid epoxy resin ("ED-505" manufactured by ADEKA Corporation, epoxy equivalent weight is about 150g/eq., 150mPa･s), and heat and dissolve it while stirring to obtain a solution . The solution was cooled to room temperature to prepare a dissolved composition of the epoxy resin.

於該溶解組成物中混合含有三嗪骨架之酚系硬化劑(DIC公司製「LA-3018-50P」，活性基當量約151g/eq.，不揮發成分率50%之2-甲氧基丙醇溶液)5份、活性酯化合物(DIC公司製「EXB9416-70BK」，活性酯基當量約330g/eq.，不揮發成分率70%之甲基異丁基酮溶液)24份、聯苯基芳烷基酚醛清漆型馬來醯亞胺(日本化藥公司製「MIR-3000-70MT」，不揮發成分率70%之MEK/甲苯混合溶液)3份、苯氧基樹脂(三菱化學公司製「YX7553BH30」，不揮發分30質量%之MEK與環己酮之1：1溶液)8份、藉由矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的生物質二氧化矽(M.I.T公司製「ethical silica」，平均粒徑3.7μm，碳含有量0.6質量%)180份，及咪唑系硬化促進劑(四國化成公司製「1B2PZ」，1-苯甲基-2-苯基咪唑，不揮發成分10質量%之MEK溶液)4份，以高速轉動混合機均勻地分散後調製出樹脂塗漆。A phenol-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation) was mixed into the dissolved composition. The active group equivalent was approximately 151 g/eq. and 2-methoxypropane with a non-volatile content rate of 50%. Alcohol solution) 5 parts, active ester compound ("EXB9416-70BK" manufactured by DIC Corporation, methyl isobutyl ketone solution with active ester group equivalent weight about 330g/eq., non-volatile content rate 70%), 24 parts biphenyl group 3 parts of aralkyl novolak-type maleimide ("MIR-3000-70MT" manufactured by Nippon Chemical Company, MEK/toluene mixed solution with a non-volatile content rate of 70%), phenoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX7553BH30", 8 parts of a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass, biomass dioxide surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 180 parts of silicon ("ethical silica" manufactured by M.I.T., average particle diameter 3.7 μm, carbon content 0.6 mass%), and imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd., 1-benzyl-2- Phenyl imidazole, 10 mass% non-volatile content (MEK solution), 4 parts, dispersed evenly with a high-speed rotating mixer to prepare a resin paint.

作為支持體，準備施予脫模處理的聚乙烯對苯二甲酸酯薄膜(Lintec公司製「AL5」，厚度38μm)。於該支持體之脫模面(施予脫模處理之面)上，均勻地塗布樹脂塗漆至樹脂組成物層之厚度成為40μm，在80℃～120℃(平均100℃)進行5分鐘乾燥，製造出具備支持體及樹脂組成物層之樹脂薄片。As a support, a release-treated polyethylene terephthalate film ("AL5" manufactured by Lintec, thickness 38 μm) was prepared. On the release surface of the support (the surface to be subjected to release treatment), apply resin paint evenly until the thickness of the resin composition layer becomes 40 μm, and dry for 5 minutes at 80°C to 120°C (average 100°C) , to produce a resin sheet with a support and a resin composition layer.

＜實施例7＞ 實施例1中，將三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq.，150mPa･s)5份變更為雙酚A型液狀環氧樹脂(三菱化學公司製「828EL」，環氧當量約180g/eq.，13,000mPa･s)5份以外，藉由與實施例1之同樣方法，製造出樹脂塗漆及樹脂薄片。 <Example 7> In Example 1, 5 parts of trimethylolpropane type liquid epoxy resin ("ED-505" manufactured by ADEKA Co., Ltd., epoxy equivalent weight is about 150g/eq., 150mPa･s) was changed to bisphenol A type liquid Resin paint and resin sheets were produced in the same manner as in Example 1 except that 5 parts of epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight is approximately 180 g/eq., 13,000 mPa･s).

＜實施例8＞ 實施例1中，將三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq.，150mPa･s)之量自5份變更為2份。又，將雙二甲酚型固體狀環氧樹脂(環氧當量190g/eq.，三菱化學公司製「YX4000HK」)追加3份於樹脂組成物。以上事項以外藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 <Example 8> In Example 1, the amount of trimethylolpropane-type liquid epoxy resin ("ED-505" manufactured by ADEKA, epoxy equivalent weight is approximately 150 g/eq., 150 mPa･s) was changed from 5 parts to 2 parts. Furthermore, 3 parts of bisxylenol type solid epoxy resin (epoxy equivalent: 190 g/eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation) was added to the resin composition. Except for the above matters, a resin paint and a resin sheet were produced by the same method as Example 1.

＜比較例1＞ 實施例1中，未使用三羥甲基丙烷型液狀環氧樹脂(ADEKA公司製「ED-505」，環氧當量約150g/eq.，150mPa･s)5份。又，將萘型固體狀環氧樹脂(日本化藥公司製「ESN475V」，環氧當量約332g/eq.)之量自15份變更為20份。以上事項以外藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 ＜Comparative example 1＞ In Example 1, 5 parts of trimethylolpropane type liquid epoxy resin ("ED-505" manufactured by ADEKA Co., Ltd., epoxy equivalent weight is approximately 150 g/eq., 150 mPa･s) was not used. Furthermore, the amount of naphthalene-type solid epoxy resin ("ESN475V" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 332 g/eq.) was changed from 15 parts to 20 parts. Except for the above matters, a resin paint and a resin sheet were produced by the same method as Example 1.

＜比較例2＞ 實施例1中，將藉由矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的生物質二氧化矽(M.I.T公司製「ethical silica」，平均粒徑3.7μm，碳含有量0.6質量%)180份變更為藉由矽烷偶合劑(信越化學工業公司製「KBM-573」)進行表面處理的球形二氧化矽(Admatechs公司製「SO-C2」，平均粒徑0.5μm，生物質比率0%)180份以外，藉由與實施例1之相同方法，製造出樹脂塗漆及樹脂薄片。 ＜Comparative example 2＞ In Example 1, biomass silica ("ethical silica" manufactured by M.I.T.) was surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), with an average particle diameter of 3.7 μm and a carbon content of 0.6% by mass), 180 parts were changed to spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), with an average particle diameter of 0.5 μm, and A resin paint and a resin sheet were produced in the same manner as in Example 1 except that the content was 180 parts (substance ratio: 0%).

＜比較例3＞ 比較例2中，將離子補足劑(東亞合成公司製，「IXEPLAS-A3」，水滑石與磷酸鋯之混合物)5份追加於樹脂組成物以外，藉由與比較例2之相同方法，製造出樹脂塗漆及樹脂薄片。 ＜Comparative Example 3＞ In Comparative Example 2, 5 parts of an ion supplementing agent (manufactured by Toagosei Co., Ltd., "IXEPLAS-A3", a mixture of hydrotalcite and zirconium phosphate) was added to the resin composition, and the same method as Comparative Example 2 was used to produce Resin paint and resin flakes.

＜比較例4＞ 比較例2中，將聯苯基型固體狀環氧樹脂(日本化藥公司製「NC3000L」，環氧當量約269g/eq.)之量自25份變更為20份。又，將黑色顏料分散體(日本色素公司製，「NV-7-201」，含有碳黑之液狀雙酚F型環氧樹脂，碳黑量25%)5份追加於樹脂組成物。以上事項以外藉由與比較例2之相同方法，製造出樹脂塗漆及樹脂薄片。 ＜Comparative Example 4＞ In Comparative Example 2, the amount of biphenyl-type solid epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269 g/eq.) was changed from 25 parts to 20 parts. Furthermore, 5 parts of black pigment dispersion (manufactured by Nippon Pigment Co., Ltd., "NV-7-201", liquid bisphenol F-type epoxy resin containing carbon black, carbon black content: 25%) was added to the resin composition. Except for the above matters, a resin paint and a resin sheet were produced by the same method as Comparative Example 2.

＜環氧樹脂之黏度的測定＞ 液狀之環氧樹脂的黏度為使用E型黏度計(使用東機產業製「RE-25U」，1° 34’×R24的錐形轉子)，在25℃且20rpm之條件下測定。 <Measurement of viscosity of epoxy resin> The viscosity of the liquid epoxy resin was measured using an E-type viscometer (using "RE-25U" manufactured by Toki Sangyo, 1° 34'×R24 conical rotor) at 25°C and 20 rpm.

＜試驗例1：硬化物之玻璃轉移溫度及線熱膨脹係數之測定＞ (1)評估用硬化物之製作： 準備具有施予脫模處理的處理面與未施予脫模處理的未處理面之PET薄膜(Lintec公司製「501010」，厚度50μm，240mm平方)。於該PET薄膜之未處理面上重疊玻璃布基材環氧樹脂兩面貼銅層合板(panasonic公司製「R5715ES」，厚度0.7mm，255mm平方)，將四邊以聚醯亞胺接著膠帶(寬10mm)固定。 <Test Example 1: Measurement of glass transition temperature and linear thermal expansion coefficient of hardened material> (1) Preparation of hardened materials for evaluation: A PET film ("501010" manufactured by Lintec, thickness 50 μm, 240 mm square) having a treated surface to which release treatment was applied and an untreated surface to which release treatment was not applied was prepared. On the untreated side of the PET film, lay a glass cloth-based epoxy resin double-sided copper laminate ("R5715ES" manufactured by Panasonic, thickness 0.7mm, 255mm square), and adhere the four sides with polyimide tape (width 10mm) )fixed.

將藉由實施例及比較例所製造之樹脂塗漆，於前述PET薄膜之處理面上，藉由模具塗布至乾燥後之樹脂組成物層厚度成為40μm，藉由80℃～120℃(平均100℃)進行10分鐘乾燥後得到樹脂薄片。其次，投入於190℃之烤箱後，在90分鐘之硬化條件下，使樹脂組成物層熱硬化。熱硬化後，剝離聚醯亞胺接著膠帶，取出玻璃布基材環氧樹脂兩面貼銅層合板，進一步剝離PET薄膜，得到薄片狀之硬化物。將所得的硬化物稱為「評估用硬化物」。The resin paint produced in the Examples and Comparative Examples was applied on the treated surface of the aforementioned PET film through a mold until the thickness of the resin composition layer after drying became 40 μm. °C) and dried for 10 minutes to obtain a resin sheet. Next, after putting it into an oven at 190°C, the resin composition layer is thermally hardened under hardening conditions for 90 minutes. After thermal hardening, peel off the polyimide adhesive tape, take out the glass cloth base epoxy resin double-sided copper laminate, and further peel off the PET film to obtain a thin sheet-like hardened product. The obtained hardened material is called "hardened material for evaluation."

(2)玻璃轉移溫度及線熱膨脹係數之測定： 切斷評估用硬化物，得到寬約5mm，長約15mm之試驗片。對於該試驗片，使用熱機械分析裝置(Rigaku公司製「Thermo Plus TMA8310」)，誒由拉伸載荷法進行熱機械分析。詳細為將試驗片安裝於前述熱機械分析裝置後，在負載1g且昇溫速度5℃/分鐘的測定條件下，連續進行2回的測定。然後，第2次測定中，算出玻璃轉移溫度Tg (℃)與自25℃至150℃之範圍中的平均線熱膨脹係數CTE (ppm/℃)。 (2) Determination of glass transition temperature and linear thermal expansion coefficient: The hardened material for evaluation was cut to obtain a test piece with a width of approximately 5 mm and a length of approximately 15 mm. For this test piece, thermomechanical analysis was performed by the tensile load method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). In detail, after the test piece was mounted on the thermomechanical analysis device, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature rise rate of 5° C./min. Then, in the second measurement, the glass transition temperature Tg (°C) and the average linear thermal expansion coefficient CTE (ppm/°C) in the range from 25°C to 150°C were calculated.

＜試驗例2：樹脂組成物之最低熔融黏度的測定＞ 將以實施例及比較例所製造的樹脂薄片之樹脂組成物層中所含的樹脂組成物之熔融黏度，使用動態黏彈性測定裝置(You B M公司製「Rheosol-G3000」)進行測定。該測定為對於自樹脂組成物層所採取的1g試料，使用直徑18mm之平板進行。測定條件為在開始溫度自60℃至200℃，昇溫速度5℃/分鐘，測定溫度間隔2.5℃，且振動1Hz/deg。自所得的熔融黏度之測定值求得最低熔融黏度。 <Test Example 2: Measurement of the minimum melt viscosity of the resin composition> The melt viscosity of the resin composition contained in the resin composition layer of the resin sheets produced in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by You B M Co., Ltd.). This measurement was performed using a flat plate with a diameter of 18 mm for 1 g of a sample taken from the resin composition layer. The measurement conditions are starting temperature from 60°C to 200°C, temperature rise rate 5°C/min, measurement temperature interval 2.5°C, and vibration 1Hz/deg. The minimum melt viscosity was determined from the obtained measured melt viscosity value.

＜試驗例3：波動之測定＞ 將以實施例及比較例所製造的樹脂薄片，使用分批式真空加壓層合體(名機公司製「MVLP-500」)，層合於以梳齒狀之圖型所形成的導體層(厚度35μm，L/S=160μm/ 160μm)上。層合為藉由30秒減壓下將氣壓設定為13hPa以下後，藉由30秒，100℃之壓力0.74MPa的擠壓而進行。於層合後剝離作為支持體之PET薄膜，在100℃下30分鐘之硬化條件下，進一步在180℃下30分鐘的硬化條件下，使樹脂組成物硬化，形成絕緣層。 <Test Example 3: Measurement of Fluctuation> The resin sheets produced in Examples and Comparative Examples were laminated on a conductor layer ( Thickness: 35μm, L/S=160μm/160μm). Lamination was performed by setting the air pressure to 13hPa or less under reduced pressure for 30 seconds, and then pressing at a pressure of 0.74MPa at 100°C for 30 seconds. After lamination, the PET film as the support was peeled off, and the resin composition was hardened under hardening conditions of 100°C for 30 minutes and further at 180°C for 30 minutes to form an insulating layer.

將絕緣層之導體層上部分的表面高度與絕緣層之該部分以外的部分之表面高度之差作為絕緣層之波動Rt而求得。絕緣層之波動Rt為使用非接觸型表面粗度計(VICO INSTRUMENTS製「WYKO NT3300」)，藉由VSI模式，10倍鏡片，將測定範圍設定在1.2mm×0.91mm，測定作為最大peak-to-valley(峰谷)之值。波動Rt若為2.0μm以下之情況時評估為「○」，波動Rt若為2.0μm～3.0μm之情況時評估為「△」，波動Rt若為比3.0μm大之情況時評估為「×」。The difference between the surface height of the portion above the conductor layer of the insulating layer and the surface height of the portion of the insulating layer other than that portion is obtained as the ripple Rt of the insulating layer. The fluctuation Rt of the insulation layer is measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by VICO INSTRUMENTS) in VSI mode with a 10x lens, setting the measurement range to 1.2mm × 0.91mm, and measuring it as the maximum peak-to -valley (peak and valley) value. If the fluctuation Rt is less than 2.0 μm, it will be evaluated as "○". If the fluctuation Rt is between 2.0 μm and 3.0 μm, it will be evaluated as "△". If the fluctuation Rt is larger than 3.0 μm, it will be evaluated as "×" .

＜試驗例4：絕緣信賴性之評估＞ 準備於表面藉由銅迴路形成梳狀電極(L/S=15μm/ 15μm)之聚醯亞胺薄膜。將以實施例及比較例所製造之樹脂薄片，使用分批式真空加壓層合體(名機公司製「MVLP-500」)進行層合，使於聚醯亞胺薄膜將樹脂薄片之樹脂組成物層接觸銅迴路表面。層合為藉由進行30秒減壓使氣壓設定在13hPa以下後，藉由30秒且100℃之壓力0.74MPa的擠壓而進行。使作為支持體的PET薄膜進行剝離後，在190℃且90分鐘的條件下使樹脂組成物層進行熱硬化，得到絕緣信賴性評估用之試料層合體。 <Test Example 4: Evaluation of Insulation Reliability> Prepare a polyimide film with a comb-shaped electrode (L/S=15μm/15μm) formed on the surface by a copper circuit. The resin sheets produced in the Examples and Comparative Examples were laminated using a batch-type vacuum pressure laminate ("MVLP-500" manufactured by Meiji Co., Ltd.), so that the resin composition of the resin sheet was incorporated into the polyimide film. The physical layer contacts the copper circuit surface. Lamination was performed by depressurizing for 30 seconds so that the air pressure was set to 13 hPa or less, and then pressing at a pressure of 0.74 MPa at 100° C. for 30 seconds. After peeling off the PET film as the support, the resin composition layer was thermally cured at 190° C. for 90 minutes to obtain a sample laminate for insulation reliability evaluation.

將該試料層合體放於高度加速壽命試驗裝置(楠本化成公司製「PM422」)，在130℃且85%RH之條件下，於輸入3.3V之電壓的狀態下經過100小時。其後測定試料層合體之絕緣電阻值。絕緣電阻值為1.0×10 9Ω以上之情況時評估為「○」，將1.0×10 8Ω以上且未達1.0×10 9Ω之情況時評估為「△」，將未達1.0×10 8Ω之情況時評估為「×」。 This sample laminate was placed in a highly accelerated life test device ("PM422" manufactured by Kusumoto Chemical Co., Ltd.), and 100 hours passed under the conditions of 130°C and 85% RH with a voltage of 3.3V input. Thereafter, the insulation resistance value of the sample laminate was measured. When the insulation resistance value is 1.0×10 9 Ω or more, it is evaluated as “○”. When it is 1.0×10 8 Ω or more and less than 1.0×10 9 Ω, it is evaluated as “△”. When it is less than 1.0×10 8 In the case of Ω, it is evaluated as "×".

＜試驗例5：耐回流焊性之評估＞ (1)基底處理內層基板之製作： 準備於表面具有銅箔之玻璃布基材環氧樹脂兩面貼銅層合板(銅箔之厚度18μm，基板之厚度0.8mm，panasonic公司製「R1515A」)。將該內層基板之表面的銅箔，使用微蝕刻劑(MEC Co., Ltd.製之「CZ8101」)，以銅蝕刻量1μm進行蝕刻並進行粗化處理。其後在190℃進行30分鐘乾燥，製作成基底處理內層基板。 <Test Example 5: Evaluation of reflow resistance> (1) Preparation of inner substrate for base treatment: A glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil on the surface was prepared (copper foil thickness: 18 μm, substrate thickness: 0.8 mm, "R1515A" manufactured by Panasonic Corporation). The copper foil on the surface of the inner layer substrate was etched with a copper etching amount of 1 μm using a microetchant ("CZ8101" manufactured by MEC Co., Ltd.) and roughened. Thereafter, it was dried at 190° C. for 30 minutes to prepare a base-treated inner layer substrate.

(2)樹脂薄片之層合及硬化： 將以實施例及比較例所製造之樹脂薄片，使用分批式真空加壓層合體(Nikko Materials公司製2階段積聚層合體「CVP700」)層合基底處理內層基板之兩面，使樹脂組成物層接合前述基底處理內層基板。該層合為，進行30秒減壓使氣壓設定13hPa以下後，藉由溫度100℃且壓力0.74MPa之30秒壓著而實施。其次，將經層合的樹脂薄片在大氣壓下，進行100℃且壓力0.5MPa之60秒的熱壓使其平滑化。進一步將此投入於130℃之烤箱而進行30分鐘加熱，其次移至170℃之烤箱進行30分鐘加熱後使樹脂組成物層進行熱硬化，得到具有支持體/絕緣層/基底處理內層基板/絕緣層/支持體之層構成的中間基板。 (2)Lamination and hardening of resin sheets: The resin sheets produced in Examples and Comparative Examples were laminated using a batch-type vacuum pressure laminate (2-stage accumulation laminate "CVP700" manufactured by Nikko Materials Co., Ltd.), and both sides of the inner substrate were laminated to obtain a resin composition. The layers are bonded to the aforementioned base-processed inner substrate. This lamination was performed by depressurizing for 30 seconds to set the air pressure to 13 hPa or less, and then pressing for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa. Next, the laminated resin sheet was smoothed by hot pressing at 100° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. This was further put into an oven at 130°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes, and then the resin composition layer was thermally hardened to obtain a substrate having a support/insulating layer/base-treated inner layer/ An intermediate substrate composed of an insulating layer/support layer.

(3)藉由鍍敷之導體形成： 自中間基板剝離支持體。其後將中間基板於膨潤液(Atotech Japan Co., Ltd.製的Swelling Dip SecurigantP)在60℃浸漬10分鐘。其次，將中間基板於粗化液(Atotech Japan Co., Ltd.製的Concentrate CompactP；含有KMnO 460g/L、NaOH 40g/L之水溶液)在80℃浸漬20分鐘。進一步將中間基板於中和液(Atotech Japan Co., Ltd.製的Reduction Solution Securigant P)在40℃下浸漬5分鐘。 (3) Formed by plated conductors: The support is peeled off from the intermediate substrate. Thereafter, the intermediate substrate was immersed in a swelling solution (Swelling Dip Securigant P manufactured by Atotech Japan Co., Ltd.) at 60° C. for 10 minutes. Next, the intermediate substrate was immersed in a roughening liquid (Concentrate CompactP manufactured by Atotech Japan Co., Ltd.; an aqueous solution containing 60 g/L KMnO 4 and 40 g/L NaOH) at 80° C. for 20 minutes. Furthermore, the intermediate substrate was immersed in a neutralizing solution (Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd.) at 40° C. for 5 minutes.

繼續，將中間基板於含有PdCl 2的無電鍍用溶液在40℃浸漬5分鐘，其次於無電解銅鍍敷液在25℃浸漬20分鐘。在150℃進行30分鐘加熱而進行退火處理後，於中間基板進一步進行硫酸銅電鍍，形成30μm厚度之導體層。其次，將退火處理在190℃進行60分鐘，得到耐回流焊性評估用基板。 Next, the intermediate substrate was immersed in an electroless plating solution containing PdCl 2 at 40° C. for 5 minutes, and then in an electroless copper plating solution at 25° C. for 20 minutes. After heating and annealing at 150°C for 30 minutes, copper sulfate electroplating was further performed on the intermediate substrate to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 190° C. for 60 minutes to obtain a substrate for reflow resistance evaluation.

(4)耐回流焊性之評估： 將耐回流焊性評估用基板切斷成100mm×50mm之小片，通過重現吸收峰溫度260℃之焊接回流溫度的回流焊裝置(Nippon Antom Co., Ltd.製「HAS-6116」)10次(回流焊溫度輪廓依據IPC/JEDEC J-STD-020C)。評估對2個小片進行，經目視觀察後若為5個以上的膨脹等異常者判斷為「×」，若為1～4個異常者判斷為「△」，所有小片皆為無異常者評估為「○」。 (4) Evaluation of reflow resistance: The substrate for reflow resistance evaluation was cut into small pieces of 100 mm × 50 mm, and passed through a reflow device ("HAS-6116" manufactured by Nippon Antom Co., Ltd.) that reproduces the soldering reflow temperature of 260°C with an absorption peak temperature 10 times. (Reflow temperature profile according to IPC/JEDEC J-STD-020C). The evaluation is carried out on 2 small pieces. After visual observation, if there are more than 5 abnormalities such as swelling, it will be judged as "×", if there are 1 to 4 abnormalities, it will be judged as "△", and if all small pieces have no abnormalities, the evaluation will be "×" 「○」.

[結果] 將上述實施例及比較例之結果表示下述表。 [result] The results of the above-mentioned Examples and Comparative Examples are shown in the following table.

100:半導體晶片封裝 110:半導體晶片 120:密封層 130:再配線形成層 140:再配線層 150:阻焊層 160:顛簸 100:Semiconductor chip packaging 110:Semiconductor wafer 120:Sealing layer 130:Rewiring formation layer 140:Rewiring layer 150: Solder mask 160: bumpy

[圖1]圖1表示作為有關本發明之一實施形態的半導體晶片封裝之一例的將Fan-out型WLP以模式方式表示的截面圖。[Fig. 1] Fig. 1 is a schematic cross-sectional view showing a Fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

100:半導體晶片封裝 100:Semiconductor chip packaging

110:半導體晶片 110:Semiconductor wafer

120:密封層 120:Sealing layer

130:再配線形成層 130:Rewiring formation layer

140:再配線層 140:Rewiring layer

150:阻焊層 150: Solder mask

160:顛簸 160: bumpy

Claims (20)

一種樹脂組成物，其為含有(A)環氧樹脂及(B)無機填充材之樹脂組成物，其中含有 (A)環氧樹脂含有(A-1)液狀環氧樹脂， (B)無機填充材含有(B-1)碳含有量0.1質量%以上之含碳的無機填充材， (A-1)液狀環氧樹脂之量相對於樹脂組成物之不揮發成分100質量%而言為0.5質量%以上， (B-1)含碳的無機填充材之量相對於樹脂組成物之不揮發成分100質量%而言為10質量%以上。 A resin composition containing (A) epoxy resin and (B) inorganic filler, which contains (A) Epoxy resin contains (A-1) liquid epoxy resin, (B) The inorganic filler contains (B-1) a carbon-containing inorganic filler with a carbon content of 0.1% by mass or more, (A-1) The amount of liquid epoxy resin is 0.5% by mass or more based on 100% by mass of non-volatile components of the resin composition, (B-1) The amount of the carbon-containing inorganic filler is 10% by mass or more based on 100% by mass of the non-volatile components of the resin composition. 如請求項1之樹脂組成物，其中進一步含有(C)硬化劑。The resin composition of claim 1 further contains (C) a hardener. 如請求項1之樹脂組成物，其中(B-1)含碳的無機填充材之量相對於(B)無機填充材之全量100質量%而言為20質量%以上。The resin composition of claim 1, wherein the amount of (B-1) carbon-containing inorganic filler is 20 mass % or more relative to 100 mass % of the total amount of (B) inorganic filler. 如請求項1之樹脂組成物，其中(B-1)含碳的無機填充材為碳含有量0.2質量%以上之二氧化矽粒子。The resin composition of claim 1, wherein (B-1) the carbon-containing inorganic filler is silica particles with a carbon content of 0.2 mass% or more. 如請求項1之樹脂組成物，其中(B-1)含碳的無機填充材之碳含有量為5質量%以下。The resin composition of claim 1, wherein (B-1) the carbon-containing inorganic filler has a carbon content of 5 mass% or less. 如請求項1之樹脂組成物，其中(A-1)液狀環氧樹脂具有1,000以下之重量平均分子量。The resin composition of claim 1, wherein (A-1) the liquid epoxy resin has a weight average molecular weight of less than 1,000. 如請求項1之樹脂組成物，其中(A-1)液狀環氧樹脂為非芳香族性之環氧樹脂。The resin composition of claim 1, wherein (A-1) the liquid epoxy resin is a non-aromatic epoxy resin. 如請求項1之樹脂組成物，其中(A-1)液狀環氧樹脂具有在25℃為15,000mPa･s以下之黏度。The resin composition of claim 1, wherein (A-1) the liquid epoxy resin has a viscosity of 15,000 mPa･s or less at 25°C. 如請求項1之樹脂組成物，其中含有(D)硬化促進劑。The resin composition of claim 1, which contains (D) a hardening accelerator. 如請求項1之樹脂組成物，其中含有(E)熱塑性樹脂。The resin composition of claim 1, which contains (E) thermoplastic resin. 如請求項1之樹脂組成物，其中具有未滿4,000poise之最低熔融黏度。Such as the resin composition of claim 1, which has a minimum melt viscosity of less than 4,000 poise. 如請求項1之樹脂組成物，其中將樹脂組成物在190℃之90分鐘條件下進行熱硬化而得硬化物，於該硬化物在130℃，85%RH之環境下輸入3.3V之電壓100小時之情況時，藉由線/空間為15μm/15μm之梳狀電極所測定的該硬化物之絕緣電阻值為1.0×10 8Ω以上。 The resin composition of Claim 1, wherein the resin composition is thermally cured at 190°C for 90 minutes to obtain a cured product, and a voltage of 3.3V is input to the cured product in an environment of 130°C and 85% RH. When the resistance is small, the insulation resistance value of the hardened material measured by a comb-shaped electrode with a line/space of 15 μm/15 μm is 1.0×10 8 Ω or more. 如請求項1之樹脂組成物，其為絕緣層形成用。The resin composition of claim 1 is used for forming an insulating layer. 一種硬化物，其如請求項1～13中任一項之樹脂組成物的硬化物。A cured product of the resin composition according to any one of claims 1 to 13. 一種薄片狀層合材料，其中含有如請求項1～13中任一項之樹脂組成物。A sheet-like laminated material containing the resin composition according to any one of claims 1 to 13. 一種樹脂薄片，其中具備支持體，與形成於該支持體上之樹脂組成物層，樹脂組成物層含有如請求項1～13中任一項之樹脂組成物。A resin sheet comprising a support and a resin composition layer formed on the support, the resin composition layer containing the resin composition according to any one of claims 1 to 13. 一種電路基板，其中含有如請求項1～13中任一項之樹脂組成物的硬化物。A circuit board containing a cured product of the resin composition according to any one of claims 1 to 13. 一種半導體晶片封裝，其中含有如請求項1～13中任一項之樹脂組成物的硬化物。A semiconductor chip package containing a cured product of the resin composition according to any one of claims 1 to 13. 一種半導體裝置，其中具備如請求項17之電路基板。A semiconductor device including the circuit substrate according to claim 17. 一種半導體裝置，其中具備如請求項18之半導體晶片封裝。A semiconductor device including the semiconductor chip package of claim 18.
TW112110850A 2022-04-18 2023-03-23 resin composition TW202405085A (en)

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