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TW202328266A - resin composition - Google Patents

resin composition Download PDF

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Publication number
TW202328266A
TW202328266A TW111131992A TW111131992A TW202328266A TW 202328266 A TW202328266 A TW 202328266A TW 111131992 A TW111131992 A TW 111131992A TW 111131992 A TW111131992 A TW 111131992A TW 202328266 A TW202328266 A TW 202328266A
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TW
Taiwan
Prior art keywords
substituent
resin composition
mass
group
aryl
Prior art date
Application number
TW111131992A
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Chinese (zh)
Inventor
川合賢司
長岡二朗
Original Assignee
日商味之素股份有限公司
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Publication of TW202328266A publication Critical patent/TW202328266A/en

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    • 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
    • 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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • 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
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

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

Abstract

The present invention addresses the problem of providing a resin composition from which a cured product having excellent crack resistance can be obtained. The present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester curing agent, and (C) an inorganic filler, wherein: the content of component (C) is at least 60 mass% when a non-volatile component in the resin composition is 100 mass%; and component (B) includes (B1) an active ester curing agent having a structure represented by formula (B1-1). Each symbol is as defined in the attached specification.

Description

樹脂組成物resin composition

本發明係關於含有環氧樹脂之樹脂組成物。進一步而言，係關於使用該樹脂組成物所得到之樹脂薄片、印刷配線板，及半導體裝置。The present invention relates to resin composition containing epoxy resin. Furthermore, it is related with the resin sheet obtained by using this resin composition, a printed wiring board, and a semiconductor device.

作為印刷配線板之製造技術，已知有以將絕緣層與導體層交互重疊之增層方式所進行的製造方法。於以增層方式所進行的製造方法中，一般而言，絕緣層係使樹脂組成物硬化而形成。近年來，絕緣層之介電正切等之介電特性的進一步提高係受到需求。As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up method which alternately overlaps an insulating layer and a conductor layer is known. In the manufacturing method performed by the build-up method, generally speaking, the insulating layer is formed by hardening the resin composition. In recent years, further improvement in dielectric properties such as the dielectric tangent of the insulating layer has been demanded.

至今為止，已知藉由使用高填充無機填充材而得之環氧樹脂組成物，或摻合活性酯化合物以取代一般的酚系硬化劑的環氧樹脂組成物，作為用以形成絕緣層之樹脂組成物，而可將絕緣層之介電正切抑制在更低水準(專利文獻1)。再者，至今為止，已知有各種活性酯系硬化劑(專利文獻2及3)。 [先前技術文獻] [專利文獻] Hitherto, epoxy resin compositions obtained by using highly filled inorganic fillers or epoxy resin compositions incorporating active ester compounds instead of general phenolic hardeners are known as methods for forming insulating layers. The resin composition can suppress the dielectric tangent of the insulating layer to a lower level (Patent Document 1). Furthermore, various active ester curing agents have been known so far (Patent Documents 2 and 3). [Prior Art Literature] [Patent Document]

[專利文獻1]日本特開2020-23714號公報 [專利文獻2]日本專利第6862701號公報 [專利文獻3]日本特開2021-14545號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2020-23714 [Patent Document 2] Japanese Patent No. 6862701 [Patent Document 3] Japanese Patent Laid-Open No. 2021-14545

[發明所欲解決之課題][Problem to be Solved by the Invention]

但是，於高填充無機填充材而得的環氧樹脂組成物中使用活性酯化合物時，雖可將介電正切抑制得更低，但除膠渣處理後有容易產生龜裂之傾向。However, when active ester compounds are used in epoxy resin compositions highly filled with inorganic fillers, although the dielectric tangent can be suppressed even lower, cracks tend to easily occur after desmearing treatment.

本發明之課題，為提供可得到龜裂耐性優良的硬化物之樹脂組成物。 [用以解決課題之手段] The object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in crack resistance. [Means to solve the problem]

為了達成本發明之課題，本發明者等人深入探討的結果，意外地發現於(C)無機填充材之含量為60質量%以上的含有(B)活性酯系硬化劑之環氧樹脂組成物中，藉由使用於末端苯氧基羰基部位之對位導入大體積之基的活性酯系硬化劑作為(B)活性酯系硬化劑，可得到龜裂耐性優良的硬化物，而完成本發明。In order to achieve the subject of the present invention, as a result of intensive research by the present inventors, it was unexpectedly found that an epoxy resin composition containing (B) an active ester-based hardener in an amount of (C) an inorganic filler of 60% by mass or more Among them, by using an active ester-based hardener for introducing a bulky group into the para-position of the terminal phenoxycarbonyl moiety as (B) active ester-based hardener, a hardened product with excellent crack resistance can be obtained, and the present invention has been completed .

亦即本發明包含以下內容。 [1]一種樹脂組成物，其係含有(A)環氧樹脂、(B)活性酯系硬化劑及(C)無機填充材之樹脂組成物，其中 以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為60質量%以上， (B)成分，包含(B1)具有式(B1-1)： That is, the present invention includes the following contents. [1] A resin composition comprising (A) an epoxy resin, (B) an active ester-based hardener, and (C) an inorganic filler, wherein When the non-volatile components in the resin composition are 100% by mass, the content of component (C) is 60% by mass or more, (B) a component comprising (B1) having the formula (B1-1):

[式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； a表示0、1或2； *表示鍵結部位。] 表示之結構的活性酯系硬化劑(以下有時稱「(B1)末端立體障礙型活性酯系硬化劑」)。 [2] 如上述[1]之樹脂組成物，其中(B1)成分，包含除了式(B1-1)表示之結構以外，進一步具有式(B1-2b)： [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have a substituent; R 1c represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 each independently represent a substituent; a represents 0, 1 or 2; * represents a bonding site. ] Active ester-based hardener with the structure shown (hereinafter sometimes referred to as "(B1) terminal steric barrier-type active ester-based hardener"). [2] The resin composition according to the above [1], wherein component (B1) includes, in addition to the structure represented by formula (B1-1), further has formula (B1-2b):

[式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； R 3係分別獨立地表示氫原子或甲基； 環X 1表示可具有取代基之芳香族碳環； a表示0、1或2； *表示鍵結部位] 表示之結構的活性酯系硬化劑。 [3] 如上述[1]或[2]之樹脂組成物，其中(B1)成分包含式(B1c)： [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have a substituent; R 1c represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 each independently represent a substituent; R 3 independently represents a hydrogen atom or a methyl group; Ring X 1 represents an aromatic carbocyclic ring that may have a substituent; a represents 0, 1 or 2; * represents the bonding site] The active ester hardener of the structure represented . [3] The resin composition according to the above [1] or [2], wherein the component (B1) contains the formula (B1c):

[式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； R 3係分別獨立地表示氫原子或甲基； 環X 1及環Y 1係分別獨立地表示可具有取代基之芳香族碳環； a係分別獨立地表示0、1或2； b表示0，或1以上之整數] 表示之樹脂。 [4] 如上述[1]~[3]中任一項之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(B1)成分之含量為3質量%~20質量%。 [5] 如上述[1]~[4]中任一項之樹脂組成物，其中(B)成分進一步包含(B2)具有式(B2-1)： [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have substituents; R 1c each independently represent an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 are each independently Represents a substituent; R 3 each independently represents a hydrogen atom or a methyl group; Ring X 1 and ring Y 1 each independently represent an aromatic carbocyclic ring that may have a substituent; a represents independently 0, 1 or 2 ; b represents 0, or an integer greater than 1] represents the resin. [4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (B1) is 3% by mass to 20% by mass when the non-volatile components in the resin composition are 100% by mass %. [5] The resin composition according to any one of the above [1] to [4], wherein component (B) further includes (B2) having the formula (B2-1):

[式中， R 4、R 5及R 6，係(1)R 4表示氫原子、鹵素原子、甲基或R 41-A-，且R 5及R 6係分別獨立地表示氫原子或取代基，或(2)R 4及R 5一起鍵結，而形成可具有取代基之芳香族碳環，且R 6表示氫原子或取代基，或(3)R 5及R 6一起鍵結，而形成可具有取代基之芳香族碳環，且R 4表示氫原子、鹵素原子、甲基或R 41-A-； R 7及R 8係分別獨立地表示氫原子或取代基； R 41表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； A表示-CH 2-、-CH(CH 3)-、-CO-，或-O-； *表示鍵結部位] 表示之結構的活性酯系硬化劑。 [6] 如上述[1]~[5]中任一項之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(A)成分之含量為1質量%~20質量%。 [7] 如上述[1]~[6]中任一項之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(B)成分之含量為12質量%以上。 [8] 如上述[1]~[7]中任一項之樹脂組成物，其中(C)成分為二氧化矽。 [9] 如上述[1]~[8]中任一項之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為70質量%以上。 [10] 如上述[1]~[9]中任一項之樹脂組成物，其進一步含有(D)硬化促進劑。 [11] 如上述[1]~[10]中任一項之樹脂組成物，其進一步含有選自由酚系硬化劑及碳二亞胺系硬化劑所成之群的硬化劑。 [12] 如上述[1]~[11]中任一項之樹脂組成物，其中以5.8GHz、23℃進行測定時，樹脂組成物之硬化物之介電正切(Df)為0.003以下。 [13] 如上述[1]~[12]中任一項之樹脂組成物，其中樹脂組成物之硬化物之玻璃轉移溫度(Tg)為140℃以上。 [14] 如上述[1]~[13]中任一項之樹脂組成物，其係用以形成導體層之絕緣層形成用。 [15] 如上述[1]~[13]中任一項之樹脂組成物，其係印刷配線板之絕緣層形成用。 [16] 一種如上述[1]~[15]中任一項之樹脂組成物之硬化物。 [17] 一種薄片狀層合材料，其含有如上述[1]~[15]中任一項之樹脂組成物。 [18] 一種樹脂薄片，其具有支撐體，與設置於該支撐體上的由如上述[1]~[15]中任一項之樹脂組成物所形成的樹脂組成物層。 [19] 一種印刷配線板，其具備由如上述[1]~[15]中任一項之樹脂組成物之硬化物所構成的絕緣層。 [20] 一種半導體裝置，其包含如上述[19]之印刷配線板。 [發明之效果] [In the formula, R 4 , R 5 and R 6 are (1) R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-, and R 5 and R 6 represent independently a hydrogen atom or a substitution group, or (2) R 4 and R 5 are bonded together to form an aromatic carbocyclic ring that may have a substituent, and R 6 represents a hydrogen atom or a substituent, or (3) R 5 and R 6 are bonded together, And form an aromatic carbocyclic ring that may have a substituent, and R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-; R 7 and R 8 represent a hydrogen atom or a substituent independently; R 41 represents An alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-; * Indicates the bonding site] is an active ester-based hardener with a structure indicated. [6] The resin composition according to any one of the above [1] to [5], wherein the content of component (A) is 1% by mass to 20% by mass when the non-volatile components in the resin composition are 100% by mass %. [7] The resin composition according to any one of [1] to [6] above, wherein the content of the component (B) is 12% by mass or more based on 100% by mass of non-volatile components in the resin composition. [8] The resin composition according to any one of the above [1] to [7], wherein the component (C) is silica. [9] The resin composition according to any one of [1] to [8] above, wherein the content of component (C) is 70% by mass or more based on 100% by mass of non-volatile components in the resin composition. [10] The resin composition according to any one of the above [1] to [9], further comprising (D) a hardening accelerator. [11] The resin composition according to any one of [1] to [10] above, further comprising a curing agent selected from the group consisting of a phenol-based curing agent and a carbodiimide-based curing agent. [12] The resin composition according to any one of [1] to [11] above, wherein the cured product of the resin composition has a dielectric tangent (Df) of 0.003 or less when measured at 5.8 GHz and 23°C. [13] The resin composition according to any one of the above [1] to [12], wherein the glass transition temperature (Tg) of the cured product of the resin composition is 140°C or higher. [14] The resin composition according to any one of the above [1] to [13], which is used for forming an insulating layer for forming a conductor layer. [15] The resin composition according to any one of the above [1] to [13], which is used for forming an insulating layer of a printed wiring board. [16] A cured product of the resin composition according to any one of the above [1] to [15]. [17] A sheet-like laminate comprising the resin composition according to any one of the above-mentioned [1] to [15]. [18] A resin sheet comprising a support, and a resin composition layer formed of the resin composition according to any one of the above [1] to [15] provided on the support. [19] A printed wiring board including an insulating layer made of a hardened resin composition according to any one of [1] to [15] above. [20] A semiconductor device comprising the printed wiring board according to the above [19]. [Effect of Invention]

依照本發明之樹脂組成物，可得到龜裂耐性優良的硬化物。According to the resin composition of the present invention, a cured product having excellent crack resistance can be obtained.

以下，基於其適合的實施形態詳細說明本發明。惟，本發明不限定於下述實施形態及例示物，在不脫離本發明之申請專利範圍及其均等範圍的範圍內可任意變更來實施。Hereinafter, the present invention will be described in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and illustrations, and can be implemented with arbitrary modifications within a range that does not depart from the scope of claims and equivalents of the present invention.

＜樹脂組成物＞ 本發明之樹脂組成物，含有(A)環氧樹脂、(B)活性酯系硬化劑，及(C)無機填充材，以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為60質量%以上，(B)成分包含(B1)末端立體障礙型活性酯系硬化劑。依照如此之樹脂組成物，可得到龜裂耐性優良的硬化物。 ＜Resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) active ester-based hardener, and (C) inorganic filler. When the non-volatile components in the resin composition are 100% by mass, (C) The content of the component is 60% by mass or more, and the component (B) contains (B1) a terminal steric barrier type active ester-based hardener. According to such a resin composition, a cured product having excellent crack resistance can be obtained.

本發明之樹脂組成物，於(A)環氧樹脂、(B)活性酯系硬化劑及(C)無機填充材以外，亦可進一步含有任意成分。任意成分例如可列舉(D)硬化促進劑、(E)其他添加劑及(F)有機溶劑。The resin composition of the present invention may further contain optional components other than (A) epoxy resin, (B) active ester hardener and (C) inorganic filler. Examples of optional components include (D) curing accelerators, (E) other additives, and (F) organic solvents.

以下詳細說明樹脂組成物中所含有的各成分。Each component contained in the resin composition will be described in detail below.

＜(A)環氧樹脂＞ 本發明之樹脂組成物含有(A)環氧樹脂。(A)環氧樹脂係指具有環氧基之硬化性樹脂。 ＜(A) Epoxy resin＞ The resin composition of this invention contains (A) epoxy resin. (A) Epoxy resin refers to a curable resin having an epoxy group.

(A)環氧樹脂，例如可列舉聯二甲酚型環氧樹脂、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、三酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、酚芳烷基型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯結構之環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環之環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂、異三聚氰酸酯型環氧樹脂、酚苄甲內醯胺(phenolphthalimidine)型環氧樹脂等。(A)環氧樹脂，可1種單獨使用、亦可組合2種以上使用。(A) epoxy resin, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin , dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac 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 type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin , biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexyl Alkane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate Type epoxy resin, phenolphthalimidine type epoxy resin, etc. (A) Epoxy resins may be used alone or in combination of two or more.

樹脂組成物，較佳含有1分子中具有2個以上之環氧基的環氧樹脂，作為(A)環氧樹脂。相對於(A)環氧樹脂之不揮發成分100質量%而言，1分子中具有2個以上之環氧基的環氧樹脂之比例較佳為50質量%以上、更佳為60質量%以上、特佳為70質量%以上。The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50% by mass, more preferably at least 60% by mass, relative to 100% by mass of the non-volatile components of the epoxy resin (A) , especially preferably more than 70% by mass.

環氧樹脂中，係有於溫度20℃為液狀之環氧樹脂(以下有時稱「液狀環氧樹脂」)，與於溫度20℃為固體狀之環氧樹脂(以下有時稱「固體狀環氧樹脂」)。本發明之樹脂組成物，作為環氧樹脂，可僅含有液狀環氧樹脂，或可僅含有固體狀環氧樹脂，或亦可組合含有液狀環氧樹脂與固體狀環氧樹脂，較佳為組合含有液狀環氧樹脂與固體狀環氧樹脂。Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins"). solid epoxy resin"). The resin composition of the present invention, as an epoxy resin, may only contain liquid epoxy resin, or may only contain solid epoxy resin, or may also contain liquid epoxy resin and solid epoxy resin in combination, preferably It contains liquid epoxy resin and solid epoxy resin in combination.

液狀環氧樹脂，較佳為1分子中具有2個以上之環氧基的液狀環氧樹脂。The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

液狀環氧樹脂，較佳為甘草醇型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、酚酚醛清漆型環氧樹脂、具有酯骨架之脂環式環氧樹脂、環己烷二甲醇型環氧樹脂、環狀脂肪族縮水甘油醚，及具有丁二烯結構之環氧樹脂；更佳為甘草醇型環氧樹脂、環狀脂肪族縮水甘油醚、雙酚A型環氧樹脂，及雙酚F型環氧樹脂。Liquid epoxy resin, preferably glycyrrhizin type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type Epoxy resins, glycidylamine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol type epoxy resins, cycloaliphatic glycidyl ethers, and Epoxy resins having a butadiene structure; more preferably glycyrrhizin type epoxy resins, cyclic aliphatic glycidyl ethers, bisphenol A type epoxy resins, and bisphenol F type epoxy resins.

液狀環氧樹脂之具體例子，可列舉Nagase ChemteX公司製之「EX-992L」、三菱化學公司製之「YX7400」、DIC公司製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製之「828US」、「828EL」、「jER828EL」、「825」、「Epikote 828EL」(雙酚A型環氧樹脂)；三菱化學公司製之「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製之「jER152」(酚酚醛清漆型環氧樹脂)；三菱化學公司製之「630」、「630LSD」、「604」(縮水甘油胺型環氧樹脂)；ADEKA公司製之「ED-523T」(甘草醇型環氧樹脂)；ADEKA公司製之「EP-3950L」、「EP-3980S」(縮水甘油胺型環氧樹脂)；ADEKA公司製之「EP-4088S」(二環戊二烯型環氧樹脂)；NIPPON STEEL Chemical & Material公司製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)；Nagase ChemteX公司製之「EX-721」(縮水甘油酯型環氧樹脂)；Nagase ChemteX公司製之「EX-991L」(含有伸烷氧基骨架及丁二烯骨架之環氧樹脂)；Daicel公司製之「Celloxide 2021P」(具有酯骨架之脂環式環氧樹脂)；Daicel公司製之「PB-3600」、日本曹達公司製之「JP-100」、「JP-200」(具有丁二烯結構之環氧樹脂)；NIPPON STEEL Chemical & Material公司製之「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油基環己烷型環氧樹脂)；大阪瓦斯化學公司製之「EG-280」(含有茀結構之環氧樹脂)；Nagase ChemteX公司製「EX-201」(環狀脂肪族縮水甘油醚)等。Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Co., Ltd., "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032" manufactured by DIC Corporation, "HP4032D", and "HP4032SS" (naphthalene ring epoxy resin); Mitsubishi Chemical Corporation's "828US", "828EL", "jER828EL", "825", "Epikote 828EL" (bisphenol A epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750 "(bisphenol F type epoxy resin); "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" and "604" (glycidylamine type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "ED-523T" (licyrrhizol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; ADEKA Corporation "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) ; "EX-721" manufactured by Nagase ChemteX (glycidyl ester type epoxy resin); "EX-991L" manufactured by Nagase ChemteX (epoxy resin containing an alkene oxide skeleton and a butadiene skeleton); Daicel "Celloxide 2021P" manufactured by the company (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation; "JP-100" and "JP-200" manufactured by Nippon Soda Corporation (with epoxy resin with ene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "EG -280" (epoxy resin containing a fennel structure); "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Co., Ltd., etc.

固體狀環氧樹脂，較佳為1分子中具有3個以上之環氧基的固體狀環氧樹脂、更佳為1分子中具有3個以上之環氧基的芳香族系之固體狀環氧樹脂。Solid epoxy resin, preferably solid epoxy resin having 3 or more epoxy groups in 1 molecule, more preferably aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule resin.

固體狀環氧樹脂，較佳為聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、萘酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、酚芳烷基型環氧樹脂、四苯基乙烷型環氧樹脂、酚苄甲內醯胺型環氧樹脂。Solid epoxy resin, preferably bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4 functional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type Epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol benzyl lactam type epoxy resin.

固體狀環氧樹脂之具體例子，可列舉DIC公司製之「HP4032H」(萘型環氧樹脂)；DIC公司製之「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製之「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製之「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製之「HP-7200」、「HP-7200HH」、「HP-7200H」、「HP-7200L」(二環戊二烯型環氧樹脂)；DIC公司製之「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)；日本化藥公司製之「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製之「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製之「NC3000H」、「NC3000」、「NC3000L」、「NC3000FH」、「NC3100」(聯苯型環氧樹脂)；NIPPON STEEL Chemical & Material公司製之「ESN475V」、「ESN4100V」(萘型環氧樹脂)；NIPPON STEEL Chemical & Material公司製之「ESN485」(萘酚型環氧樹脂)；NIPPON STEEL Chemical & Material公司製之「ESN375」(二羥基萘型環氧樹脂)；三菱化學公司製之「YX4000H」、「YX4000」、「YX4000HK」、「YL7890」(聯二甲酚型環氧樹脂)；三菱化學公司製之「YL6121」(聯苯型環氧樹脂)；三菱化學公司製之「YX8800」(蒽型環氧樹脂)；三菱化學公司製之「YX7700」(酚芳烷基型環氧樹脂)；大阪瓦斯化學公司製之「PG-100」、「CG-500」；三菱化學公司製之「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製之「YL7800」(茀型環氧樹脂)；三菱化學公司製之「jER1010」(雙酚A型環氧樹脂)；三菱化學公司製之「jER1031S」(四苯基乙烷型環氧樹脂)；日本化藥公司製之「WHR991S」(酚苄甲內醯胺型環氧樹脂)等。此等可1種單獨使用、亦可組合2種以上使用。Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation. ; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200" manufactured by DIC Corporation , "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA -7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Chemical "NC7000L" (naphthol novolak type epoxy resin) manufactured by a pharmaceutical company; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin ); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by NIPPON STEEL Chemical &Material; "ESN485" (naphthol-type epoxy resin) manufactured by NIPPON STEEL Chemical &Material; NIPPON STEEL Chemical & Material "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by the company; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka "PG-100" and "CG-500" manufactured by Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ; "jER1010" (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol A) manufactured by Nippon Kayaku Corporation benzyl lactamide type epoxy resin), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

組合使用固體狀環氧樹脂與液狀環氧樹脂作為(A)環氧樹脂時，該等之質量比(固體狀環氧樹脂：液狀環氧樹脂)，較佳為10：1~1：50、更佳為5：1~1：20、特佳為2：1~1：10。When using solid epoxy resin and liquid epoxy resin in combination as (A) epoxy resin, the mass ratio (solid epoxy resin: liquid epoxy resin) is preferably 10:1~1: 50. The best is 5:1~1:20, and the best is 2:1~1:10.

(A)環氧樹脂之環氧當量，較佳為50g/eq.~5,000g/eq.、更佳為60g/eq.~2,000g/eq.、又更佳為70g/eq.~1,000g/eq.、又再更佳為80g/eq.~500g/eq.。環氧當量為相對於環氧基1當量而言之樹脂質量。該環氧當量，可遵照JIS K7236測定。(A) The epoxy equivalent of epoxy resin is preferably 50g/eq.~5,000g/eq., more preferably 60g/eq.~2,000g/eq., and more preferably 70g/eq.~1,000g /eq., and more preferably 80g/eq.~500g/eq. Epoxy equivalent is the mass of resin relative to 1 equivalent of epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

(A)環氧樹脂之重量平均分子量(Mw)，較佳為100~5,000、更佳為250~3,000、又更佳為400~1,500。樹脂之重量平均分子量，可藉由凝膠滲透層析(GPC)法，作為以聚苯乙烯換算之值來測定。(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5,000, more preferably 250-3,000, and more preferably 400-1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

樹脂組成物中之(A)環氧樹脂之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為30質量%以下、更佳為25質量%以下、又更佳為20質量%以下、又再更佳為15質量%以下、特佳為12質量%以下。樹脂組成物中之(A)環氧樹脂之含量之下限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為0.01質量%以上、更佳為0.1質量%以上、又更佳為1質量%以上、又再更佳為5質量%以上、特佳為10質量%以上。The content of (A) epoxy resin in the resin composition is not particularly limited, and when the non-volatile components in the resin composition are 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably Preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less, Most preferably, it is 12 mass % or less. The lower limit of the content of (A) epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, it is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, More preferably, it is at least 1% by mass, still more preferably at least 5% by mass, and most preferably at least 10% by mass.

＜(B)活性酯系硬化劑＞ 本發明之樹脂組成物含有(B)活性酯系硬化劑。(B)活性酯系硬化劑，可具有作為與(A)環氧樹脂反應而硬化的環氧樹脂硬化劑之功能。(B)活性酯系硬化劑，可1種單獨使用、亦可以任意比率組合使用2種以上。 ＜(B) Active ester hardener＞ The resin composition of the present invention contains (B) an active ester-based hardener. (B) The active ester-based hardener can function as an epoxy resin hardener that reacts with (A) epoxy resin and hardens. (B) The active ester-based curing agent may be used alone or in combination of two or more at any ratio.

作為(B)活性酯系硬化劑，一般而言較佳使用酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之1分子中具有2個以上之反應活性高的酯基之化合物。(B)活性酯系硬化劑，較佳為藉由羧酸化合物及/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所得到者。特別就耐熱性提高之觀點，較佳為由羧酸化合物與羥基化合物所得到的活性酯化合物、更佳為由羧酸化合物與酚系化合物所得到的活性酯化合物。羧酸化合物，例如可列舉苯甲酸、乙酸、琥珀酸、馬來酸、依康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。酚系化合物，例如可列舉氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酸式酚酞、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、兒茶酚、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、均苯三酚、苯三醇、二環戊二烯型二酚化合物、酚酚醛清漆等。As (B) active ester-based hardener, it is generally preferable to use phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactions in one molecule. Ester-based compound with high activity. (B) The active ester-based hardener is preferably obtained through the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenolic compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Phenolic compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated 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, pyroglucinol, pyroglucinol, dicyclopentadiene type diphenol compound, phenolic novolac wait.

(B)活性酯系硬化劑之活性酯基當量(作為硬化劑之反應基當量)，較佳為50g/eq.~500g/eq.、更佳為50g/eq.~400g/eq.、又更佳為100g/eq.~300g/eq.。活性酯基當量，為相對於可與環氧樹脂反應之酯基1當量而言，活性酯系硬化劑之質量。(B) The active ester group equivalent of the active ester hardener (as the reactive group equivalent of the hardener), preferably 50g/eq.~500g/eq., more preferably 50g/eq.~400g/eq., and More preferably 100g/eq.~300g/eq. Active ester group equivalent is the mass of active ester hardener relative to 1 equivalent of ester group that can react with epoxy resin.

樹脂組成物中之(B)活性酯系硬化劑之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為0.1質量%以上、更佳為1質量%以上、又更佳為5質量%以上、又更佳為10質量%以上、又再更佳為12質量%以上、又再更佳為14質量%以上、特佳為15質量%以上。樹脂組成物中之(B)活性酯系硬化劑之含量之上限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為50質量%以下、更佳為40質量%以下、又更佳為30質量%以下、又再更佳為25質量%以下、特佳為20質量%以下。The content of (B) active ester-based hardener in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably at least 0.1% by mass, more preferably at least 1% by mass, More preferably, it is at least 5% by mass, more preferably at least 10% by mass, still more preferably at least 12% by mass, still more preferably at least 14% by mass, and most preferably at least 15% by mass. The upper limit of the content of (B) active ester-based hardener in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass At most, more preferably at most 30% by mass, even more preferably at most 25% by mass, most preferably at most 20% by mass.

＜(B1)末端立體障礙型活性酯系硬化劑＞ (B)活性酯系硬化劑，包含(B1)具有式(B1-1)： ＜(B1) Terminal steric barrier type active ester hardener＞ (B) Active ester-based hardeners comprising (B1) having the formula (B1-1):

[式中，R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環；R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基；R 2係分別獨立地表示取代基；a表示0、1或2；*表示鍵結部位] 表示之結構的活性酯系硬化劑。 [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have a substituent; R 1c represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 each independently represent a substituent; a stands for 0, 1 or 2; * stands for the bonding site] is an active ester-based hardener with the structure represented.

R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環。 R 1a and R 1b independently represent an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together to form a substituent Based on non-aromatic carbocycle.

烷(基)意指直鏈、分支鏈及/或環狀之1價之脂肪族飽和烴基。烷(基)只要無特別指定，較佳為碳數1~14之烷(基)、更佳為碳數1~10之烷(基)、又更佳為碳數1~6之烷(基)。烷(基)，例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、sec-丁基、tert-丁基、戊基、異戊基、sec-戊基、新戊基、tert-戊基、己基、異己基、庚基、異庚基、辛基、異辛基、tert-辛基、環戊基、環己基等。Alkyl (group) means a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) with 1 to 14 carbons, more preferably an alkyl (group) with 1 to 10 carbons, and more preferably an alkyl (group) with 1 to 6 carbons. ). Alkyl (group), for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, Neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, etc.

烯(基)意指具有至少1個碳-碳雙鍵之直鏈、分支鏈及/或環狀之1價之脂肪族不飽和烴基。烯(基)只要無特別指定，較佳為碳數2~14之烯基、更佳為碳數2~10之烯基、又更佳為碳數2~6之烯基。烯(基)，例如可列舉乙烯基、丙烯基(烯丙基、1-丙烯基、異丙烯基)、丁烯基(1-丁烯基、巴豆基、甲基烯丙基(metallyl)、異巴豆基等)、戊烯基(1-戊烯基等)、己烯基(1-己烯基等)、庚烯基(1-庚烯基等)、辛烯基(1-辛烯基等)、環戊烯基(2-環戊烯基等)、環己烯基(3-環己烯基等)等。Alkenyl (yl) means a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl (group) is preferably an alkenyl group having 2 to 14 carbons, more preferably an alkenyl group having 2 to 10 carbons, and still more preferably an alkenyl group having 2 to 6 carbons, unless otherwise specified. Alkenyl, for example, vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methallyl, isocrotyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octene group, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl, etc.) and the like.

芳(基)，意指去除芳香族碳環之1個氫原子而成的1價之芳香族烴基。芳(基)只要無特別指定，較佳為碳數6~14之芳(基)、更佳為碳數6~10之芳(基)。芳(基)，例如可列舉苯基、1-萘基、2-萘基等。Aryl (group) refers to a monovalent aromatic hydrocarbon group obtained by removing one hydrogen atom from an aromatic carbocyclic ring. Unless otherwise specified, the aryl (group) is preferably an aryl (group) with 6 to 14 carbon atoms, more preferably an aryl (group) with 6 to 10 carbon atoms. Aryl(yl) includes, for example, phenyl, 1-naphthyl, 2-naphthyl and the like.

非芳香族碳環，意指環全體中具有芳香族性之芳香族碳環以外之環。非芳香族碳環，僅以碳原子作為環構成原子。非芳香族碳環，可為僅由單鍵所構成的飽和碳環，或具有雙鍵及三鍵中至少任一者的不飽和碳環。非芳香族碳環，較佳為碳數4~20之非芳香族碳環、更佳為碳數5~12之非芳香族碳環。非芳香族碳環之適合的具體例子，例如可列舉環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、環十一烷環、環十二烷環等之單環系之飽和碳環；雙環[2.2.1]庚烷環(降莰烷環)、雙環[4.4.0]癸烷環(十氫萘環)、雙環[5.3.0]癸烷環、雙環[4.3.0]壬烷環(八氫茚環)、雙環[3.2.1]辛烷環、雙環[5.4.0]十一烷環、雙環[3.3.0]辛烷環、雙環[3.3.1]壬烷環等之二環系之飽和碳環；三環[5.2.1.0 2,6]癸烷環(四氫二環戊二烯環)、三環[3.3.1.1 3,7]癸烷環(金剛烷環)、三環[6.2.1.0 2,7]十一烷環等之三環系之飽和碳環；四環[6.2.1.1 3,6.0 2,7]十二烷環等之四環系之飽和碳環；五環[9.2.1.1 4,7.0 2,1.0 3,8]十五烷環、五環[6.5.1.1 3,6.0 2,7.0 9,13]十五烷環(四氫三環戊二烯環)等之五環系之飽和碳環等。又，非芳香族碳環，亦可於可縮合的位置與1或2個以上之芳香族碳環縮合。與芳香族碳環縮合的非芳香族碳環，例如可列舉茚烷環、茚環、四氫萘環、1,2-二氫萘環、1,4-二氫萘環、茀環、9,10-二氫蒽環、9,10-二氫菲環等。 The non-aromatic carbocyclic ring refers to a ring other than an aromatic carbocyclic ring having aromaticity among all rings. A non-aromatic carbocyclic ring, which uses only carbon atoms as ring constituent atoms. The non-aromatic carbocycle may be a saturated carbocycle composed only of single bonds, or an unsaturated carbocycle having at least any one of double bonds and triple bonds. The non-aromatic carbocycle is preferably a non-aromatic carbocycle with 4-20 carbons, more preferably a non-aromatic carbocycle with 5-12 carbons. Suitable specific examples of non-aromatic carbocyclic rings include, for example, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, cyclononane rings, cyclodecane rings, cyclodecane rings, Monocyclic saturated carbocycles such as undecane ring and cyclododecane ring; bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring ), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (octahydroindene ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo [3.3.0] octane ring, bicyclo [3.3.1] nonane ring and other saturated carbocycles of the bicyclic ring system; tricyclic [5.2.1.0 2,6 ] decane ring (tetrahydrodicyclopentadiene ring ), tricyclic [3.3.1.1 3,7 ] decane ring (adamantane ring), tricyclic [6.2.1.0 2,7 ] undecane ring and other saturated carbocyclic rings of the tricyclic system; tetracyclic [6.2. 1.1 3,6 .0 2,7 ] saturated carbocyclic rings of tetracyclic rings such as dodecane ring; pentacyclic [9.2.1.1 4,7 .0 2,1 .0 3,8 ] pentadecane ring, Cyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]pentadecane ring (tetrahydrotricyclopentadiene ring) and other pentacyclic saturated carbocycles. Also, a non-aromatic carbocycle may be condensed with one or two or more aromatic carbocycles at a condensable position. Non-aromatic carbocycles condensed with aromatic carbocycles include, for example, indane rings, indene rings, tetrahydronaphthalene rings, 1,2-dihydronaphthalene rings, 1,4-dihydronaphthalene rings, fennel rings, 9 , 10-dihydroanthracene, 9,10-dihydrophenanthrene, etc.

芳香族碳環，意指環上之π電子系中所含有的電子數為4p+2個(p為自然數)之遵守休克爾法則(Hückel's Rule)之烴環。芳香族碳環，僅以碳原子作為環構成原子。芳香族碳環，於一實施形態中，較佳為6~14員之芳香族碳環、更佳為6~10員之芳香族碳環。芳香族碳環之適合的具體例子，可列舉苯環、萘環、蒽環、菲環等，更佳為苯環或萘環、特佳為苯環。Aromatic carbocycle refers to a hydrocarbon ring that obeys Hückel's Rule and the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). Aromatic carbocyclic rings have only carbon atoms as ring constituent atoms. In one embodiment, the aromatic carbocycle is preferably an aromatic carbocycle with 6 to 14 members, more preferably an aromatic carbocycle with 6 to 10 members. Specific examples of suitable aromatic carbocycles include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc., more preferably benzene ring or naphthalene ring, particularly preferably benzene ring.

R 1a及R 1b表示之烷基及烯基中之「取代基」並不特別限定，例如可列舉鹵素原子、芳基、烷基-芳基(經烷基取代之芳基)、烯基-芳基(經烯基取代之芳基)、芳基-芳基(經芳基取代之芳基)、烷基-氧基、烯基-氧基、芳基-氧基、烷基-羰基、烯基-羰基、芳基-羰基、烷基-氧基-羰基、烯基-氧基-羰基、芳基-氧基-羰基、烷基-羰基-氧基、烯基-羰基-氧基、芳基-羰基-氧基等。R 1a及R 1b表示之芳基中之「取代基」並不特別限定，例如可列舉鹵素原子、烷基、烯基、芳基、芳基-烷基(經芳基取代之烷基)、烷基-芳基-烷基(經經烷基取代之芳基取代之烷基)、烯基-芳基-烷基(經經烯基取代之芳基取代之烷基)、芳基-芳基-烷基(經經芳基取代之芳基取代之烷基)、烷基-芳基、烯基-芳基、芳基-芳基、烷基-氧基、烯基-氧基、芳基-氧基、烷基-羰基、烯基-羰基、芳基-羰基、烷基-氧基-羰基、烯基-氧基-羰基、芳基-氧基-羰基、烷基-羰基-氧基、烯基-羰基-氧基、芳基-羰基-氧基等。R 1a及R 1b所形成的非芳香族碳環中之「取代基」並不特別限定，例如可列舉鹵素原子、烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基、烷基-氧基、烯基-氧基、芳基-氧基、烷基-羰基、烯基-羰基、芳基-羰基、烷基-氧基-羰基、烯基-氧基-羰基、芳基-氧基-羰基、烷基-羰基-氧基、烯基-羰基-氧基、芳基-羰基-氧基、側氧基(=O)等。 The "substituent" in the alkyl and alkenyl groups represented by R 1a and R 1b is not particularly limited, for example, halogen atoms, aryl groups, alkyl-aryl groups (aryl groups substituted by alkyl groups), alkenyl- Aryl (alkenyl substituted aryl), aryl-aryl (aryl substituted aryl), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, Aryl-carbonyl-oxyl, etc. The "substituent" in the aryl group represented by R 1a and R 1b is not particularly limited, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted by an aryl group), Alkyl-aryl-alkyl (alkyl substituted with aryl substituted with alkyl), alkenyl-aryl-alkyl (alkyl substituted with aryl substituted with alkenyl), aryl-aryl Alkyl-alkyl (alkyl substituted by aryl substituted aryl), alkyl-aryl, alkenyl-aryl, aryl-aryl, alkyl-oxy, alkenyl-oxy, aryl Base-oxyl, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy radical, alkenyl-carbonyl-oxyl, aryl-carbonyl-oxyl, etc. The "substituent" in the non-aromatic carbocyclic ring formed by R 1a and R 1b is not particularly limited, and examples include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, and alkyl-aryl groups -Alkyl, alkenyl-aryl-alkyl, aryl-aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl, alkyl-oxy, alkenyl-oxy radical, aryl-oxyl, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl- Carbonyl-oxy, alkenyl-carbonyl-oxy, aryl-carbonyl-oxy, pendant oxy (=O), and the like.

鹵素原子係指氟原子、氯原子、溴原子，或碘原子，較佳為氯原子。The halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.

R 1a及R 1b，分別獨立地，於一實施形態中，較佳為可具有取代基之烷基，或可具有取代基之芳基；更佳為可具有取代基之烷基；又更佳為烷基；又再更佳為R 1a為甲基且R 1b為烷基；又進一步更佳為R 1a為甲基且R 1b為碳數2以上之烷基；特佳為R 1a為甲基且R 1b為乙基。 R 1a and R 1b are each independently, in one embodiment, preferably an alkyl group that may have a substituent, or an aryl group that may have a substituent; more preferably an alkyl group that may have a substituent; still more preferably It is an alkyl group; it is more preferable that R 1a is a methyl group and R 1b is an alkyl group; it is even more preferable that R 1a is a methyl group and R 1b is an alkyl group with more than 2 carbon atoms; it is especially preferable that R 1a is a methyl group and R 1b is ethyl.

R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基。 R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

R 1c表示之烷基及烯基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之烷基及烯基中之「取代基」所例示的相同者。R 1c表示之芳基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the alkyl and alkenyl represented by R 1c is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the alkyl and alkenyl represented by R 1a and R 1b . The "substituent" in the aryl group represented by R 1c is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b .

R 1c，於一實施形態中，較佳為可具有取代基之烷基，或可具有取代基之芳基；更佳為可具有取代基之烷基；又更佳為烷基；特佳為甲基。 R 1c , in one embodiment, is preferably an alkyl group that may have a substituent, or an aryl group that may have a substituent; more preferably an alkyl group that may have a substituent; still more preferably an alkyl group; particularly preferably methyl.

以R 1c、R 1c及R 1c與該等所鍵結之碳原子所形成之基，亦即(R1)： The group formed by R 1c , R 1c and R 1c and the carbon atoms to which they are bonded, that is (R1):

[式中，各記號係如上述] 表示之1價之基之具體例子，可列舉tert-丁基、tert-戊基(tert-戊基)、1-甲基環丁基、1,1-二甲基丁基、1-乙基-1-甲基丙基、1-甲基環戊基、1-乙基環丁基、1,1-二甲基戊基、1,1,2-三甲基丁基、1-乙基-1-甲基丁基等之3級烷基；1,1-二甲基-2-丙烯基等之1位經烯基取代之2級烷基；α-異丙苯基等之1位經芳基取代之2級烷基等。 [In the formula, the symbols are as above] Specific examples of the monovalent group represented include tert-butyl, tert-pentyl (tert-pentyl), 1-methylcyclobutyl, 1,1-dimethylbutyl, 1-ethyl -1-methylpropyl, 1-methylcyclopentyl, 1-ethylcyclobutyl, 1,1-dimethylpentyl, 1,1,2-trimethylbutyl, 1-ethyl - 3rd grade alkyl such as 1-methylbutyl; 2nd grade alkyl such as 1,1-dimethyl-2-propenyl substituted by alkenyl; 1st position of α-cumyl phenyl etc. Secondary alkyl substituted by aryl, etc.

R 2係分別獨立地表示取代基。 R 2 systems each independently represent a substituent.

R 2表示之「取代基」並不特別限定，例如，除了式(R1)表示之1價之基以外，可列舉鹵素原子、烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基、烷基-氧基、烯基-氧基、芳基-氧基、烷基-羰基、烯基-羰基、芳基-羰基、烷基-氧基-羰基、烯基-氧基-羰基、芳基-氧基-羰基、烷基-羰基-氧基、烯基-羰基-氧基、芳基-羰基-氧基等。 The "substituent" represented by R2 is not particularly limited. For example, in addition to the monovalent group represented by formula (R1), halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, and alkyl groups can be mentioned. -aryl-alkyl, alkenyl-aryl-alkyl, aryl-aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl, alkyl-oxyl, alkenyl Base-oxyl, aryl-oxyl, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, Alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, aryl-carbonyl-oxy, and the like.

R 2，分別獨立地，於一實施形態中，較佳為烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基，或芳基-芳基。 R 2 , each independently, in one embodiment, preferably alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl Base-aryl-alkyl, alkyl-aryl, alkenyl-aryl, or aryl-aryl.

a表示0、1或2。a，於一實施形態中，較佳為0或1；更佳為0。a means 0, 1 or 2. a, in one embodiment, is preferably 0 or 1; more preferably 0.

(B1)成分，較佳為包含除了式(B1-1)表示之結構以外，進一步具有式(B1-2a)：The component (B1) preferably includes the structure represented by the formula (B1-1), and further has the formula (B1-2a):

[式中，R 1係分別獨立地表示取代基；R 3係分別獨立地表示氫原子或甲基；環X 1表示可具有取代基之芳香族碳環；e係分別獨立地表示0、1、2、3或4；*表示鍵結部位] 表示之結構的活性酯系硬化劑。 [In the formula, R 1 represents a substituent independently; R 3 represents a hydrogen atom or a methyl group independently; Ring X 1 represents an aromatic carbocyclic ring that may have a substituent; e represents 0, 1 independently , 2, 3 or 4; * indicates the bonding site] The active ester hardener of the structure indicated.

R 1表示之「取代基」並不特別限定，可列舉與作為R 2表示之「取代基」所例示的相同者。 The "substituent" represented by R 1 is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" represented by R 2 .

R 1係分別獨立地表示取代基。R 1，分別獨立地，於一實施形態中，較佳為烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基，或式(R1)表示之1價之基；更佳為式(R1)表示之1價之基。 R 1 systems each independently represent a substituent. R 1 , each independently, in one embodiment, preferably alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl Base-aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl, or a monovalent group represented by formula (R1); more preferably a monovalent group represented by formula (R1) base.

R 3係分別獨立地表示氫原子或甲基。R 3，分別獨立地，於一實施形態中，較佳為氫原子。 R 3 systems each independently represent a hydrogen atom or a methyl group. R 3 , each independently, is preferably a hydrogen atom in one embodiment.

環X 1表示可具有取代基之芳香族碳環。 Ring X1 represents an aromatic carbocyclic ring which may have a substituent.

環X 1表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring X 1 is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b .

環X 1，於一實施形態中，較佳為可具有取代基之苯環，或可具有取代基之萘環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代的苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代的萘環；又更佳為(1)可經烷基取代之苯環，或(2)可經烷基取代之萘環；又再更佳為可經烷基取代之苯環；特佳為(無取代之)苯環。 Ring X 1 , in one embodiment, is preferably a benzene ring that may have substituents, or a naphthalene ring that may have substituents; Alkyl, and a phenyl ring substituted by a group selected from alkyl-aryl, or (2) may be substituted by a group selected from alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl Naphthalene ring; more preferably (1) benzene ring which may be substituted by alkyl, or (2) naphthalene ring which may be substituted by alkyl; still more preferably benzene ring which may be substituted by alkyl; especially preferably (Unsubstituted) benzene ring.

e係分別獨立地表示0、1、2、3或4。e，分別獨立地，於一實施形態中，較佳為0、1、2或3；更佳為0、1或2；又更佳為0或1；特佳為0。e means 0, 1, 2, 3 or 4 each independently. e, each independently, in one embodiment, preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; still more preferably 0 or 1; particularly preferably 0.

(B1)成分更佳為包含除了式(B1-1)表示之結構以外，進一步具有式(B1-2b)：The component (B1) is more preferably comprised of the structure represented by the formula (B1-1), and further has the formula (B1-2b):

[式中，各記號係如上述] 表示之結構的活性酯系硬化劑。 [In the formula, the symbols are as above] Active ester hardener with the structure shown.

於適合的實施形態中，(B1)成分包含式(B1a)：In a suitable embodiment, (B1) component comprises formula (B1a):

[式中，環X係分別獨立地表示可具有取代基之芳香族碳環，或可具有取代基之非芳香族碳環；環Y 1及環Z 1係分別獨立地表示可具有取代基之芳香族碳環；X a係分別獨立地表示單鍵、-C(R a) 2-、-O-、-CO-、-S-、-SO-、-SO 2-、-CONH-，或-NHCO-；R a係分別獨立地表示氫原子、可具有取代基之烷基，或可具有取代基之芳基，或者2個R a一起鍵結，而形成可具有取代基之非芳香族碳環；b表示0，或1以上之整數；c係分別獨立地表示0、1、2或3；d係分別獨立地表示0或1；其他記號係如上述] 表示之樹脂。b單位及c單位，分別就每個結構單位而言可為相同、亦可為相異。 [In the formula, the ring X is an aromatic carbocycle that may have a substituent independently, or a non-aromatic carbocycle that may have a substituent; the ring Y1 and the ring Z1 are each independently a carbocyclic ring that may have a substituent. Aromatic carbocycle; X a series independently represent a single bond, -C(R a ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; R a each independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, or two R a are bonded together to form a non-aromatic group that may have a substituent Carbocycle; b represents 0, or an integer greater than 1; c represents 0, 1, 2 or 3 independently; d represents 0 or 1 independently; other symbols are resins represented by ]. The unit b and the unit c may be the same or different for each structural unit.

環X係分別獨立地表示可具有取代基之芳香族碳環，或可具有取代基之非芳香族碳環。Ring X each independently represents an aromatic carbocycle which may have a substituent, or a non-aromatic carbocycle which may have a substituent.

環X表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。環X所形成的非芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b所形成的非芳香族碳環中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring X is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b . The "substituent" in the non-aromatic carbocycle formed by ring X is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the non-aromatic carbocycle formed by R 1a and R 1b .

環X，於一實施形態中，較佳為可具有取代基之芳香族碳環；更佳為可具有取代基之苯環，或可具有取代基之萘環；又更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之萘環；又再更佳為可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環；又再更佳為可經烷基取代之苯環；特佳為(無取代之)苯環。Ring X, in one embodiment, is preferably an aromatic carbocyclic ring that may have a substituent; more preferably a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent; and more preferably (1) may A benzene ring substituted by a group selected from alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl, or (2) may be substituted by an alkyl, alkenyl, aryl, aryl-alk group, and a naphthalene ring substituted by a group selected from an alkyl-aryl group; more preferably, it may be substituted by a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and a group selected from an alkyl-aryl group A benzene ring; still more preferably a benzene ring which may be substituted by an alkyl group; especially preferably an (unsubstituted) benzene ring.

環Y 1係分別獨立地表示可具有取代基之芳香族碳環。 Ring Y 1 each independently represents an aromatic carbocyclic ring which may have a substituent.

環Y 1表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring Y 1 is not particularly limited, and examples thereof include the same ones exemplified as the "substituent" in the aryl group represented by R 1a and R 1b .

環Y 1，分別獨立地，於一實施形態中，較佳為可具有取代基之苯環，或可具有取代基之萘環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之萘環；又更佳為(1)可經烷基取代之苯環，或(2)可經烷基取代之萘環；又再更佳為可經烷基取代之苯環；特佳為(無取代之)苯環。 Ring Y 1 , each independently, in one embodiment, is preferably a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent; , aryl-alkyl, and alkyl-aryl substituted phenyl rings, or (2) can be substituted through alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl A naphthalene ring substituted by a selected group; more preferably (1) a benzene ring which may be substituted by an alkyl group, or (2) a naphthalene ring which may be substituted by an alkyl group; still more preferably a benzene ring which may be substituted by an alkyl group ; Especially preferably (unsubstituted) benzene ring.

環Z 1係分別獨立地表示可具有取代基之芳香族碳環。 The rings Z 1 each independently represent an aromatic carbocyclic ring which may have a substituent.

環Z 1表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 2表示之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocyclic ring represented by ring Z1 is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" represented by R2 .

環Z 1，分別獨立地，於一實施形態中，較佳為可具有取代基之苯環，或可具有取代基之萘環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基，及式(R1)表示之1價之基中選出之基取代之苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基，及式(R1)表示之1價之基中選出之基取代之萘環；又更佳為可經由烷基、烯基、芳基、芳基-烷基、烷基-芳基-烷基、烯基-芳基-烷基、芳基-芳基-烷基、烷基-芳基、烯基-芳基、芳基-芳基，及式(R1)表示之1價之基中選出之基取代之苯環；又再更佳為可經式(R1)表示之1價之基取代之苯環；特佳為經式(R1)表示之1價之基取代之苯環。 Ring Z 1 , each independently, in one embodiment, is preferably a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent; , aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl-aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl group, and a benzene ring substituted by a group selected from the monovalent group represented by formula (R1), or (2) can be substituted by alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl-alkane group, alkenyl-aryl-alkyl group, aryl-aryl-alkyl group, alkyl-aryl group, alkenyl-aryl group, aryl-aryl group, and the monovalent group represented by formula (R1) A naphthalene ring substituted with a selected group; and more preferably through alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl- Aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl, and a substituted benzene ring selected from monovalent groups represented by formula (R1); A benzene ring substituted with a monovalent group represented by formula (R1); particularly preferably a benzene ring substituted with a monovalent group represented by formula (R1).

X a係分別獨立地表示單鍵、-C(R a) 2-、-O-、-CO-、-S-、-SO-、-SO 2-、-CONH-，或-NHCO-。X a，分別獨立地，於一實施形態中，較佳為單鍵、-C(R a) 2-，或-O-；更佳為-C(R a) 2-；特佳為-C(R 3)(CH 3)-。 X a each independently represent a single bond, -C(R a ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-. X a , each independently, in one embodiment, is preferably a single bond, -C(R a ) 2 -, or -O-; more preferably -C(R a ) 2 -; particularly preferably -C (R 3 )(CH 3 )-.

R a係分別獨立地表示氫原子、可具有取代基之烷基，或可具有取代基之芳基，或者2個R a一起鍵結，而形成可具有取代基之非芳香族碳環。 R a each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or two R a are bonded together to form a non-aromatic carbocyclic ring which may have a substituent.

R a表示之烷基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之烷基，及烯基中之「取代基」所例示的相同者。R a表示之芳基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。R a所形成的非芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b所形成的非芳香族碳環中之「取代基」所例示的相同者。 The "substituent" in the alkyl group represented by R a is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the alkyl group represented by R 1a and R 1b , and the alkenyl group. The "substituent" in the aryl group represented by R a is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b . The "substituent" in the non-aromatic carbocycle formed by R a is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the non-aromatic carbocycle formed by R 1a and R 1b .

R a，分別獨立地，於一實施形態中，較佳為氫原子，或可具有取代基之烷基；較佳為氫原子，或可具有取代基之烷基；更佳為氫原子或烷基；特佳為氫原子或甲基。 R a , each independently, in one embodiment, preferably a hydrogen atom, or an alkyl group that may have a substituent; preferably a hydrogen atom, or an alkyl group that may have a substituent; more preferably a hydrogen atom or an alkyl group group; particularly preferably a hydrogen atom or a methyl group.

b表示0，或1以上之整數。b，於一實施形態中，較佳為0，或1~100之整數；更佳為0，或1~10之整數；特佳為0，或1~5之整數。b represents 0, or an integer of 1 or more. b, in one embodiment, preferably 0, or an integer of 1-100; more preferably 0, or an integer of 1-10; particularly preferably 0, or an integer of 1-5.

c係分別獨立地表示0、1、2或3。c，分別獨立地，於一實施形態中，較佳為0、1或2；更佳為0或1；特佳為1。c represents 0, 1, 2 or 3 each independently. c, each independently, in one embodiment, preferably 0, 1 or 2; more preferably 0 or 1; particularly preferably 1.

d係分別獨立地表示0或1。d，分別獨立地，於一實施形態中，較佳為1。The d systems each independently represent 0 or 1. d, each independently, preferably 1 in one embodiment.

於更適合的實施形態中，(B1)成分，包含式(B1b)：In a more suitable embodiment, the component (B1) includes formula (B1b):

[式中，各記號係如上述] 表示之樹脂。 [In the formula, the symbols are as above] Indicates the resin.

於又更適合的實施形態中，(B1)成分，包含式(B1c)：In another more suitable embodiment, the component (B1) includes the formula (B1c):

[式中，各記號係如上述] 表示之樹脂。 [In the formula, the symbols are as above] Indicates the resin.

式(B1-2a)、(B1-2b)、(B1b)及(B1c)中之式(X)：Formula (X) in formula (B1-2a), (B1-2b), (B1b) and (B1c):

[式中，其他記號係如上述] 表示之部分結構之例子，可列舉式(X-1)~(X-12)： [In the formula, other symbols are as above] Examples of partial structures represented by formulas (X-1)~(X-12):

[式中，R x係分別獨立地表示烷基、烯基、芳基、芳基-烷基，或烷基-芳基；x係分別獨立地表示0、1或2；其他記號係如上述] 等表示之結構，其中尤佳為式(X-1)~(X-3)表示之結構，於一實施形態中，特佳為式(X-2)表示之結構。R x，分別獨立地，於一實施形態中，較佳為烷基。x，分別獨立地，於一實施形態中，較佳為0或1；更佳為0。 [wherein, R x systems represent independently alkyl, alkenyl, aryl, aryl-alkyl, or alkyl-aryl; x represent independently 0, 1 or 2; other symbols are as above ] and the like, particularly preferably the structures represented by the formulas (X-1) to (X-3), and in one embodiment, particularly preferably the structures represented by the formula (X-2). R x , each independently, are preferably an alkyl group in one embodiment. x, each independently, in one embodiment, preferably 0 or 1; more preferably 0.

式(B1a)、(B1b)及(B1c)中之式(Y)：Formula (Y) in formula (B1a), (B1b) and (B1c):

[式中，其他記號係如上述] 表示之部分結構之例子，可列舉式(Y-1)~(Y-12)： [In the formula, other symbols are as above] An example of the partial structure represented by the formula (Y-1)~(Y-12):

[式中，R y係分別獨立地表示烷基、烯基、芳基、芳基-烷基，或烷基-芳基；y係分別獨立地表示0、1或2；其他記號係如上述] 等表示之結構，其中尤佳為式(Y-2)表示之結構。R y，分別獨立地，於一實施形態中，較佳為烷基。y，分別獨立地，於一實施形態中，較佳為0或1；更佳為0。 [wherein, R y systems independently represent alkyl, alkenyl, aryl, aryl-alkyl, or alkyl-aryl; y systems independently represent 0, 1 or 2; other symbols are as above ] etc., especially the structure represented by formula (Y-2). R y , each independently, is preferably an alkyl group in one embodiment. y, each independently, are preferably 0 or 1 in one embodiment; more preferably 0.

(B1)成分，除了式(B1a)、(B1b)或(B1c)表示之樹脂以外，可能再含有合成時所產生的反應中間體之樹脂(例如單末端或兩末端為羥基及/或羧基)、源自原料雜質之樹脂等。Component (B1), in addition to the resin represented by formula (B1a), (B1b) or (B1c), may further contain resins of reaction intermediates generated during synthesis (such as hydroxyl and/or carboxyl at one or both ends) , Resin derived from raw material impurities, etc.

(B1)成分可使用市售品、亦可使用公知方法或根據其之方法合成。(B1) The component can use a commercial item, and can also synthesize|combine using a well-known method or the method based on it.

樹脂組成物中之(B1)成分之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為50質量%以下、更佳為30質量%以下、又更佳為20質量%以下，就更提高硬化物之玻璃轉移溫度之觀點，又再更佳為15質量%以下、特佳為10質量%以下。樹脂組成物中之(B1)成分之含量之下限不特別限定，就更顯著得到本發明之所期望之效果之觀點，以樹脂組成物中之不揮發成分為100質量%時，較佳為0.1質量%以上、更佳為1質量%以上、又更佳為3質量%以上、又再更佳為5質量%以上、特佳為7質量%以上。The content of the component (B1) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less, from the viewpoint of further increasing the glass transition temperature of the cured product, it is still more preferably 15% by mass or less, and most preferably 10% by mass or less. The lower limit of the content of the component (B1) in the resin composition is not particularly limited. From the viewpoint of obtaining the desired effect of the present invention more significantly, when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.1 % by mass or more, more preferably at least 1 mass %, more preferably at least 3 mass %, still more preferably at least 5 mass %, particularly preferably at least 7 mass %.

(B)活性酯系硬化劑中之(B1)成分之含量，以(B)活性酯系硬化劑為100質量%時，亦可為100質量%，就更提高硬化物之玻璃轉移溫度之觀點，較佳為95質量%以下、更佳為90質量%以下、又更佳為80質量%以下、又再更佳為70質量%以下、特佳為60質量%以下。(B)活性酯系硬化劑中之(B1)成分之含量之下限不特別限定，就更顯著得到本發明之所期望之效果之觀點，以(B)活性酯系硬化劑為100質量%時，較佳為1質量%以上、更佳為10質量%以上、又更佳為20質量%以上、又再更佳為30質量%以上、特佳為40質量%以上。(B) The content of the component (B1) in the active ester-based hardener may be 100% by mass when the (B) active ester-based hardener is 100% by mass. From the viewpoint of further increasing the glass transition temperature of the hardened product , preferably at most 95% by mass, more preferably at most 90% by mass, more preferably at most 80% by mass, still more preferably at most 70% by mass, most preferably at most 60% by mass. (B) The lower limit of the content of the component (B1) in the active ester-based hardener is not particularly limited. From the viewpoint of obtaining the desired effect of the present invention more significantly, when the (B) active ester-based hardener is 100% by mass , preferably at least 1% by mass, more preferably at least 10% by mass, more preferably at least 20% by mass, still more preferably at least 30% by mass, and most preferably at least 40% by mass.

相對於樹脂組成物中之(A)環氧樹脂而言，(B1)成分之質量比((B1)成分/(A)成分)不特別限定，較佳為0.05以上、更佳為0.1以上、又更佳為0.5以上。相對於樹脂組成物中之(A)環氧樹脂而言，(B1)成分之質量比((B1)成分/(A)成分)之上限不特別限定，較佳為10以下、更佳為5以下，就更提高硬化物之玻璃轉移溫度之觀點，又更佳為1以下。The mass ratio of (B1) component ((B1) component/(A) component) with respect to (A) epoxy resin in a resin composition is not specifically limited, Preferably it is 0.05 or more, More preferably, it is 0.1 or more, Still more preferably, it is 0.5 or more. The upper limit of the mass ratio of (B1) component ((B1) component/(A) component) to the (A) epoxy resin in the resin composition is not particularly limited, but is preferably 10 or less, more preferably 5 Below, from the viewpoint of further increasing the glass transition temperature of the cured product, it is more preferably 1 or less.

＜(B2)其他活性酯系硬化劑＞ (B)活性酯系硬化劑，亦可進一步包含(B1)成分以外之活性酯系硬化劑(以下有時稱「(B2)其他活性酯系硬化劑」)。 ＜(B2) Other active ester hardeners＞ (B) The active ester-based hardener may further contain active ester-based hardeners other than the component (B1) (hereinafter sometimes referred to as "(B2) other active ester-based hardeners").

(B)活性酯系硬化劑，較佳包含具有式(B2-1)：(B) Active ester-based hardeners, preferably comprising formula (B2-1):

[式中，R 4、R 5及R 6，係(1)R 4表示氫原子、鹵素原子、甲基或R 41-A-，且R 5及R 6係分別獨立地表示氫原子或取代基，或(2)R 4及R 5一起鍵結，而形成可具有取代基之芳香族碳環，且R 6表示氫原子或取代基，或(3)R 5及R 6一起鍵結，而形成可具有取代基之芳香族碳環，且R 4表示氫原子、鹵素原子、甲基或R 41-A-；R 7及R 8係分別獨立地表示氫原子或取代基；R 41表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基；A表示-CH 2-、-CH(CH 3)-、-CO-，或-O-；*表示鍵結部位] 表示之結構的活性酯系硬化劑，作為(B2)其他活性酯系硬化劑。 [In the formula, R 4 , R 5 and R 6 are (1) R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-, and R 5 and R 6 represent independently a hydrogen atom or a substitution group, or (2) R 4 and R 5 are bonded together to form an aromatic carbocyclic ring that may have a substituent, and R 6 represents a hydrogen atom or a substituent, or (3) R 5 and R 6 are bonded together, And form an aromatic carbocyclic ring that may have a substituent, and R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-; R 7 and R 8 represent a hydrogen atom or a substituent independently; R 41 represents An alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-;* Indicates the bonding site] The active ester-based hardener with the structure shown is (B2) other active ester-based hardeners.

R 4不形成芳香族碳環時，係表示氫原子、鹵素原子、甲基，或R 41-A-。R 4不形成芳香族碳環時，於一實施形態中，較佳為氫原子、甲基，或R 41-A-；更佳為氫原子，或R 41-A-。 When R 4 does not form an aromatic carbocycle, it represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-. When R 4 does not form an aromatic carbocycle, in one embodiment, it is preferably a hydrogen atom, a methyl group, or R 41 -A-; more preferably a hydrogen atom, or R 41 -A-.

A表示-CH 2-、-CH(CH 3)-、-CO-，或-O-。A，於一實施形態中，較佳為-CH 2-，或-CH(CH 3)-；更佳為-CH(CH 3)-。 A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-. A, in one embodiment, is preferably -CH 2 -, or -CH(CH 3 )-; more preferably -CH(CH 3 )-.

R 41表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基。 R 41 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

R 41表示之烷基，及烯基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之烷基，及烯基中之「取代基」所例示的相同者。R 41表示之芳基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the alkyl group represented by R 41 and the alkenyl group is not particularly limited, and the same ones as exemplified as the "substituent group" in the alkyl group and alkenyl group represented by R 1a and R 1b are exemplified. The "substituent" in the aryl group represented by R 41 is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b .

R 41，於一實施形態中，較佳為可具有取代基之芳基；更佳為芳基；特佳為苯基。 In one embodiment, R 41 is preferably an aryl group which may have a substituent; more preferably an aryl group; and particularly preferably a phenyl group.

R 5及R 6不形成芳香族碳環時，係分別獨立地表示氫原子或取代基。 When R 5 and R 6 do not form an aromatic carbocycle, they each independently represent a hydrogen atom or a substituent.

R 5及R 6表示之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" represented by R 5 and R 6 is not particularly limited, and the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b are exemplified.

R 5及R 6不形成芳香族碳環時，分別獨立地，於一實施形態中，較佳為氫原子、烷基、烯基、芳基、芳基-烷基，或烷基-芳基；更佳為氫原子、烷基、芳基，或芳基-烷基。 When R and R do not form an aromatic carbocycle, each independently, in one embodiment, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group ; more preferably a hydrogen atom, an alkyl group, an aryl group, or an aryl-alkyl group.

R 4、R 5及R 6形成芳香族碳環時，R 4及R 5或R 5及R 6係一起鍵結，而形成可具有取代基之芳香族碳環。 When R 4 , R 5 and R 6 form an aromatic carbocycle, R 4 and R 5 or R 5 and R 6 are bonded together to form an aromatic carbocycle which may have a substituent.

R 4、R 5及R 6所形成的芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle formed by R 4 , R 5 and R 6 is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b .

R 4、R 5及R 6形成芳香族碳環時，於一實施形態中，R 4及R 5或R 5及R 6一起鍵結，較佳為形成可具有取代基之苯環；更佳為形成可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環；又更佳為形成(無取代之)苯環。 When R 4 , R 5 and R 6 form an aromatic carbocyclic ring, in one embodiment, R 4 and R 5 or R 5 and R 6 are bonded together, preferably forming a benzene ring that may have a substituent; more preferably To form a benzene ring which may be substituted by a group selected from alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl; more preferably to form an (unsubstituted) benzene ring.

R 7及R 8係分別獨立地表示氫原子或取代基。 R 7 and R 8 are each independently representing a hydrogen atom or a substituent.

R 7及R 8表示之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" represented by R 7 and R 8 is not particularly limited, and the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b are exemplified.

R 7及R 8，分別獨立地，於一實施形態中，較佳為氫原子、烷基、烯基、芳基、芳基-烷基，或烷基-芳基；更佳為氫原子、烷基、芳基，或芳基-烷基。 R 7 and R 8 are independently, in one embodiment, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; more preferably a hydrogen atom, Alkyl, aryl, or aryl-alkyl.

第一實施形態中，較佳為R 4、R 5、R 7及R 8為氫原子，且R 6為烷基，或芳基；更佳為R 4、R 5、R 7及R 8為氫原子，且R 6為甲基，或苯基。 In the first embodiment, preferably R 4 , R 5 , R 7 and R 8 are hydrogen atoms, and R 6 is an alkyl group or aryl group; more preferably R 4 , R 5 , R 7 and R 8 are hydrogen atom, and R 6 is a methyl group, or a phenyl group.

第二實施形態中，較佳為R 4為氫原子，或R 41-A-，A為-CH 2-，或-CH(CH 3)-，R 41為芳基，且R 5、R 6、R 7及R 8為氫原子，或芳基-烷基(特佳為R 4為R 41-A-且/或R 5、R 6、R 7及R 8中至少1個為芳基-烷基)；更佳為R 4為氫原子，或R 41-A-，A為-CH(CH 3)-，R 41為苯基，且R 5、R 6、R 7及R 8為氫原子，或α-甲基苄基(特佳為R 4為R 41-A-且/或R 5、R 6、R 7及R 8中至少1個為α-甲基苄基)。 In the second embodiment, preferably R 4 is a hydrogen atom, or R 41 -A-, A is -CH 2 -, or -CH(CH 3 )-, R 41 is an aryl group, and R 5 , R 6 , R 7 and R 8 are hydrogen atoms, or aryl-alkyl (preferably R 4 is R 41 -A- and/or at least one of R 5 , R 6 , R 7 and R 8 is aryl- alkyl); more preferably R 4 is a hydrogen atom, or R 41 -A-, A is -CH(CH 3 )-, R 41 is phenyl, and R 5 , R 6 , R 7 and R 8 are hydrogen atom, or α-methylbenzyl (especially preferably R 4 is R 41 -A- and/or at least one of R 5 , R 6 , R 7 and R 8 is α-methylbenzyl).

第三實施形態中，較佳為R 4及R 5一起鍵結而形成苯環，且R 6、R 7及R 8為氫原子，或者R 5及R 6一起鍵結而形成苯環，且R 4、R 7及R 8為氫原子。 In the third embodiment, preferably R 4 and R 5 are bonded together to form a benzene ring, and R 6 , R 7 and R 8 are hydrogen atoms, or R 5 and R 6 are bonded together to form a benzene ring, and R 4 , R 7 and R 8 are hydrogen atoms.

於適合的實施形態中，(B2)成分包含式(B2a)：In a suitable embodiment, (B2) component comprises formula (B2a):

[式中，環X’係分別獨立地表示可具有取代基之芳香族碳環，或可具有取代基之非芳香族碳環；環Y 2及環Z 2係分別獨立地表示可具有取代基之芳香族碳環；X b係分別獨立地表示單鍵、-C(R b) 2-、-O-、-CO-、-S-、-SO-、-SO 2-、-CONH-，或-NHCO-；R b係分別獨立地表示氫原子、可具有取代基之烷基，或可具有取代基之芳基，或者2個R b一起鍵結，而形成可具有取代基之非芳香族碳環；b’表示0，或1以上之整數；c’係分別獨立地表示0、1、2或3；d’係分別獨立地表示0或1；其他記號係如上述] 表示之樹脂。b’單位及c’單位，分別就每個結構單位而言可為相同、亦可為相異。 [In the formula, the ring X' represents an aromatic carbocycle that may have a substituent, or a non-aromatic carbocycle that may have a substituent; the ring Y 2 and the ring Z 2 independently represent a carbocyclic ring that may have a substituent Aromatic carbocyclic ring; X b represents independently a single bond, -C(R b ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, Or -NHCO-; R b are each independently a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, or two R b are bonded together to form a non-aromatic group that may have a substituent group carbocyclic ring; b'represents 0, or an integer greater than 1; c'represents 0, 1, 2 or 3 independently; d'represents 0 or 1 independently; other symbols are resins represented as above] . The b' unit and the c' unit may be the same or different for each structural unit.

環X’係分別獨立地表示可具有取代基之芳香族碳環，或可具有取代基之非芳香族碳環。Ring X' each independently represents an aromatic carbocyclic ring which may have a substituent, or a non-aromatic carbocyclic ring which may have a substituent.

環X’表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。環X’表示之非芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b所形成的非芳香族碳環中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring X' is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b . The "substituent" in the non-aromatic carbocycle represented by ring X' is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the non-aromatic carbocycle formed by R 1a and R 1b .

環X’，分別獨立地，於一實施形態中，較佳為可具有取代基之苯環、可具有取代基之萘環，或可具有取代基之碳數5~12之非芳香族碳環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環、(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之萘環，或(3)可經由烷基、烯基、芳基、芳基-烷基、烷基-芳基，及側氧基中選出之基取代之碳數5~12之非芳香族碳環(特佳為四氫二環戊二烯環)。Ring X', each independently, in one embodiment, is preferably a benzene ring that may have a substituent, a naphthalene ring that may have a substituent, or a non-aromatic carbocyclic ring with 5 to 12 carbon atoms that may have a substituent more preferably (1) a benzene ring that can be substituted by a group selected from alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl, (2) can be substituted by an alkyl, alkenyl, Aryl, aryl-alkyl, and alkyl-aryl substituted naphthalene rings, or (3) can be selected via alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl , and a non-aromatic carbocycle with 5 to 12 carbons substituted by a group selected from the side oxygen group (tetrahydrodicyclopentadiene ring is particularly preferred).

環Y 2係分別獨立地表示可具有取代基之芳香族碳環。 Ring Y 2 each independently represent an aromatic carbocyclic ring which may have a substituent.

環Y 2表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring Y 2 is not particularly limited, and examples thereof include the same ones as exemplified as "substituents" in the aryl group represented by R 1a and R 1b .

環Y 2，分別獨立地，於一實施形態中，較佳為可具有取代基之苯環，或可具有取代基之萘環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之萘環。 Ring Y 2 , each independently, in one embodiment, is preferably a benzene ring that may have substituents, or a naphthalene ring that may have substituents; , aryl-alkyl, and alkyl-aryl substituted phenyl rings, or (2) can be substituted through alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl The selected group substituted naphthalene ring.

環Z 2係分別獨立地表示可具有取代基之芳香族碳環。 Ring Z 2 each independently represents an aromatic carbocyclic ring which may have a substituent.

環Z 2表示之芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。 The "substituent" in the aromatic carbocycle represented by ring Z 2 is not particularly limited, and the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b are exemplified.

環Z 2，分別獨立地，於一實施形態中，較佳為可具有取代基之苯環，或可具有取代基之萘環；更佳為(1)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之苯環，或(2)可經由烷基、烯基、芳基、芳基-烷基，及烷基-芳基中選出之基取代之萘環。 Ring Z 2 , each independently, in one embodiment, is preferably a benzene ring that may have a substituent, or a naphthalene ring that may have a substituent; , aryl-alkyl, and alkyl-aryl substituted phenyl rings, or (2) can be substituted through alkyl, alkenyl, aryl, aryl-alkyl, and alkyl-aryl The selected group substituted naphthalene ring.

X b係分別獨立地表示單鍵、-C(R b) 2-、-O-、-CO-、-S-、-SO-、-SO 2-、-CONH-，或-NHCO-。X b，分別獨立地，於一實施形態中，較佳為單鍵、-C(R b) 2-，或-O-；更佳為單鍵，或-O-。 X b each independently represent a single bond, -C(R b ) 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-. X b , each independently, in one embodiment, is preferably a single bond, -C(R b ) 2 -, or -O-; more preferably a single bond, or -O-.

R b係分別獨立地表示氫原子、可具有取代基之烷基，或可具有取代基之芳基，或者2個R b一起鍵結，而形成可具有取代基之非芳香族碳環。R b表示之烷基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之烷基，及烯基中之「取代基」所例示的相同者。R b表示之芳基中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b表示之芳基中之「取代基」所例示的相同者。R b所形成的非芳香族碳環中之「取代基」並不特別限定，可列舉與作為R 1a及R 1b所形成的非芳香族碳環中之「取代基」所例示的相同者。 R b each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, or two R b are bonded together to form an optionally substituted non-aromatic carbocyclic ring. The "substituent" in the alkyl group represented by R b is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the alkyl group represented by R 1a and R 1b , and the alkenyl group. The "substituent" in the aryl group represented by R b is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the aryl group represented by R 1a and R 1b . The "substituent" in the non-aromatic carbocycle formed by R b is not particularly limited, and examples thereof include the same ones as exemplified as the "substituent" in the non-aromatic carbocycle formed by R 1a and R 1b .

R b，分別獨立地，於一實施形態中，較佳為氫原子，或可具有取代基之烷基；更佳為氫原子，或烷基；特佳為氫原子，或甲基。 R b , each independently, in one embodiment, is preferably a hydrogen atom or an alkyl group which may have a substituent; more preferably a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom or a methyl group.

b’表示0，或1以上之整數。b’，於一實施形態中，較佳為0，或1~100之整數；更佳為0，或1~10之整數；特佳為0，或1~5之整數。b' represents 0, or an integer of 1 or more. b', in one embodiment, is preferably 0, or an integer of 1-100; more preferably 0, or an integer of 1-10; particularly preferably 0, or an integer of 1-5.

c’係分別獨立地表示0、1、2或3。c’，分別獨立地，於一實施形態中，較佳為0、1或2；更佳為0或1。c' represents 0, 1, 2 or 3 each independently. c', each independently, in one embodiment, is preferably 0, 1 or 2; more preferably 0 or 1.

d’係分別獨立地表示0或1。d' represents 0 or 1 each independently.

式(B2a)中之式(Y’)：Formula (Y') in formula (B2a):

[式中，其他記號係如上述] 表示之部分結構之例子，可列舉式(Y-1)~(Y-12)等表示之結構。 [In the formula, other symbols are as above] Examples of the partial structures represented include structures represented by formulas (Y-1) to (Y-12).

(B2)成分，除了式(B2a)表示之樹脂以外，可能再含有合成時所產生之反應中間體之樹脂(例如單末端或兩末端為羥基及/或羧基)、源自原料雜質之樹脂等。(B2) Components, in addition to the resin represented by formula (B2a), may contain resins of reaction intermediates generated during synthesis (such as hydroxyl and/or carboxyl at one or both ends), resins derived from raw material impurities, etc. .

(B2)成分可使用市售品、亦可使用公知方法或根據其之方法合成。(B2)成分之市售品，就包含二環戊二烯型二酚結構之活性酯化合物而言，可列舉「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」、「HPC-8000L-65TM」、「HPC-8000H」、「HPC-8000H-65TM」(DIC公司製)；就包含萘結構之活性酯化合物而言，可列舉「HP-B-8151-62T」、「EXB-8100L-65T」、「EXB-9416-70BK」、「EXB-8」、「HPC-8150-62T」(DIC公司製)；就含有磷之活性酯化合物而言，可列舉「EXB9401」(DIC公司製)；就酚酚醛清漆之乙醯化物之活性酯化合物而言，可列舉「DC808」(三菱化學公司製)；就酚酚醛清漆之苯甲醯化物之活性酯化合物而言，可列舉「YLH1026」、「YLH1030」、「YLH1048」(三菱化學公司製)；就包含苯乙烯基及萘結構之活性酯化合物而言，可列舉「PC1300-02-65MA」(AIR WATER公司製)等。(B2) A commercial item can be used for a component, and it can also synthesize|combine using a well-known method or the method based on it. Commercially available products of the component (B2) include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", " "HPC-8000L-65TM", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); examples of active ester compounds containing a naphthalene structure include "HP-B-8151-62T", " EXB-8100L-65T”, “EXB-9416-70BK”, “EXB-8”, “HPC-8150-62T” (manufactured by DIC Corporation); examples of phosphorus-containing active ester compounds include “EXB9401” ( DIC Corporation); as the active ester compound of acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "PC1300-02-65MA" (manufactured by Air Water Corporation) etc. are mentioned as an active ester compound containing a styryl group and a naphthalene structure.

樹脂組成物中之(B2)成分之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為40質量%以下、更佳為20質量%以下、又更佳為15質量%以下、又再更佳為10質量%以下、特佳為8質量%以下。樹脂組成物中之(B2)成分之含量之下限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，例如為0質量%以上、0.1質量%以上，就更提高硬化物之玻璃轉移溫度之觀點，較佳為1質量%以上、更佳為3質量%以上、特佳為5質量%以上。The content of the component (B2) in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, and more preferably 20% by mass or less. 15% by mass or less, more preferably 10% by mass or less, and most preferably 8% by mass or less. The lower limit of the content of the (B2) component in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, for example, it is 0% by mass or more, 0.1% by mass or more, and the content of the hardened product is further improved. From the viewpoint of the glass transition temperature, it is preferably at least 1% by mass, more preferably at least 3% by mass, and particularly preferably at least 5% by mass.

相對於樹脂組成物中之(A)環氧樹脂而言，(B2)成分之質量比((B2)成分/(A)成分)不特別限定，較佳為10以下、更佳為5以下、又更佳為1以下。相對於樹脂組成物中之(A)環氧樹脂而言，(B2)成分之質量比((B2)成分/(A)成分)之下限，例如為0以上，就更提高硬化物之玻璃轉移溫度之觀點，較佳為0.1以上、更佳為0.5以上。The mass ratio of (B2) component ((B2) component/(A) component) with respect to (A) epoxy resin in a resin composition is not specifically limited, Preferably it is 10 or less, More preferably, it is 5 or less, More preferably, it is 1 or less. With respect to the (A) epoxy resin in the resin composition, the lower limit of the mass ratio of (B2) component ((B2) component/(A) component), for example, is 0 or more, and the glass transition of the cured product will be improved. From the viewpoint of temperature, it is preferably at least 0.1, more preferably at least 0.5.

＜(B’)其他硬化劑＞ 本發明之樹脂組成物，亦可進一步含有(B)成分以外之(B’)硬化劑作為任意成分。(B’)其他硬化劑，可1種單獨使用、亦可任意組合2種以上使用。(B’)其他硬化劑，係與(B)活性酯系硬化劑同樣地，可具有作為與(A)環氧樹脂反應而使其硬化的環氧樹脂硬化劑之功能。 ＜(B’)Other hardeners＞ The resin composition of the present invention may further contain (B') curing agent other than the component (B) as an optional component. (B') Other curing agents may be used alone or in any combination of two or more. The (B') other curing agent, like the (B) active ester curing agent, can function as an epoxy resin curing agent that reacts with (A) epoxy resin to harden it.

(B’)其他硬化劑並不特別限定，例如可列舉酚系硬化劑、碳二亞胺系硬化劑、酸酐系硬化劑、胺系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑，及硫醇系硬化劑。其中尤佳為選自由酚系硬化劑及碳二亞胺系硬化劑所成之群的硬化劑。(B') Other curing agents are not particularly limited, and examples thereof include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate-based hardener, and mercaptan hardener. Among them, a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents is particularly preferable.

作為酚系硬化劑，就耐熱性及耐水性之觀點，較佳為具有酚醛清漆結構之酚系硬化劑。又，就對被黏著體之密合性之觀點，較佳為含氮酚系硬化劑、更佳為含有三嗪骨架之酚系硬化劑。其中就高度滿足耐熱性、耐水性，及密合性之觀點，尤佳為含有三嗪骨架之酚酚醛清漆樹脂。酚系硬化劑之具體例子，例如可列舉明和化成公司製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製之「NHN」、「CBN」、「GPH」、NIPPON STEEL Chemical & Material公司製之「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製之「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」、「KA-1160」等。The phenolic curing agent is preferably a phenolic curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesiveness to an adherend, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a phenol novolac resin containing a triazine skeleton is particularly preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness. Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd. ", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by NIPPON STEEL Chemical & Material Co., Ltd. ", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "KA -1160", etc.

作為碳二亞胺系硬化劑，可列舉1分子中具有1個以上、較佳為2個以上的碳二亞胺結構之硬化劑，例如可列舉四亞甲基-雙(t-丁基碳二亞胺)、環己烷雙(亞甲基-t-丁基碳二亞胺)等之脂肪族雙碳二亞胺；伸苯基-雙(二甲苯基碳二亞胺)等之芳香族雙碳二亞胺等之雙碳二亞胺；聚六亞甲基碳二亞胺、聚三甲基六亞甲基碳二亞胺、聚環伸己基碳二亞胺、聚(亞甲基雙環伸己基碳二亞胺)、聚(異佛酮碳二亞胺)等之脂肪族聚碳二亞胺；聚(伸苯碳二亞胺)、聚(伸萘碳二亞胺)、聚(伸甲苯碳二亞胺)、聚(甲基二異丙基伸苯碳二亞胺)、聚(三乙基伸苯碳二亞胺)、聚(二乙基伸苯碳二亞胺)、聚(三異丙基伸苯碳二亞胺)、聚(二異丙基伸苯碳二亞胺)、聚(伸二甲苯碳二亞胺)、聚(四甲基伸二甲苯碳二亞胺)、聚(亞甲基二伸苯碳二亞胺)、聚[亞甲基雙(甲基伸苯基)碳二亞胺]等之芳香族聚碳二亞胺等之聚碳二亞胺。Examples of carbodiimide-based curing agents include those having one or more, preferably two or more, carbodiimide structures in one molecule, for example, tetramethylene-bis(t-butyl carbon Diimide), aliphatic biscarbodiimide such as cyclohexanebis(methylene-t-butylcarbodiimide); aromatic bis(xylylcarbodiimide) such as phenylene-bis(xylylcarbodiimide) Biscarbodiimides such as biscarbodiimides; polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(methylene aliphatic polycarbodiimides such as dicyclohexylcarbodiimide), poly(isophoronecarbodiimide), etc.; Poly(toluenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly( Polycarbodiimide such as aromatic polycarbodiimide such as methylene diphenylene carbodiimide), poly[methylene bis(methyl phenylene carbodiimide], etc.

碳二亞胺系硬化劑之市售品，例如可列舉日清紡化學公司製之「Carbodilite V-02B」、「Carbodilite V-03」、「Carbodilite V-04K」、「Carbodilite V-07」及「Carbodilite V-09」；Rhein Chemie公司製之「Stabaxol P」、「Stabaxol P400」、「Hycasyl 510」等。Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-07" manufactured by Nisshinbo Chemical Co., Ltd. V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein Chemie, etc.

作為酸酐系硬化劑，可列舉1分子中具有1個以上的酸酐基之硬化劑，較佳為1分子中具有2個以上的酸酐基之硬化劑。酸酐系硬化劑之具體例子，可列舉鄰苯二甲酸酐、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、甲基降莰烯二酸酐、氫化甲基降莰烯二酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二側氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二甲酸酐、偏苯三甲酸酐、苯均四酸酐、二苯甲酮四甲酸二酐、聯苯四甲酸二酐、萘四甲酸二酐、氧基二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四甲酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇雙(偏苯三甲酸酐)、苯乙烯與馬來酸共聚合而得的苯乙烯/馬來酸樹脂等之聚合物型之酸酐等。酸酐系硬化劑之市售品，可列舉新日本理化公司製之「HNA-100」、「MH-700」、「MTA-15」、「DDSA」、「OSA」、三菱化學公司製之「YH-306」、「YH-307」、日立化成公司製之「HN-2200」、「HN-5500」、Cray Valley公司製「EF-30」、「EF-40」「EF-60」、「EF-80」等。Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, preferably those having two or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Anhydride, Methylnorbornene dianhydride, Hydrogenated Methylnorbornene dianhydride, Trialkyltetrahydrophthalic anhydride, Dodecenylsuccinic 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 anhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexa Hydrogen-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ), polymer-type anhydrides of styrene/maleic acid resins obtained by copolymerization of styrene and maleic acid, etc. Commercially available acid anhydride hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shinnihon Chemical Co., Ltd., and "YH" manufactured by Mitsubishi Chemical Corporation. -306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., "EF-30", "EF-40", "EF-60", "EF -80", etc.

作為胺系硬化劑，可列舉1分子中具有1個以上、較佳為2個以上的胺基之硬化劑，例如可列舉脂肪族胺類、聚醚胺類、脂環式胺類、芳香族胺類等，其中，就發揮本發明之所期望之效果的觀點，尤佳為芳香族胺類。胺系硬化劑較佳為1級胺或2級胺、更佳為1級胺。胺系硬化劑之具體例子，可列舉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-苯二甲胺、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、2,2’-二甲基-4,4’-二胺基聯苯、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、雙(4-(4-胺基苯氧基)苯基)碸、雙(4-(3-胺基苯氧基)苯基)碸等。胺系硬化劑亦可使用市售品，例如可列舉SEIKA公司製「SEIKACURE-S」、日本化藥公司製之「KAYABOND C-200S」、「KAYABOND C-100」、「KAYAHARD A-A」、「KAYAHARD A-B」、「KAYAHARD A-S」、三菱化學公司製之「Epicure W」等。Examples of the amine-based curing agent include those having one or more, preferably two or more, amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic Among the amines, aromatic amines are particularly preferred from the viewpoint of exerting the desired effects of the present invention. The amine hardener is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine hardeners include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diamine phenylenediamine, 3,3'-diaminodiphenylene, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenyl Aniline, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenoxy)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl , bis(4-(4-aminophenoxy)phenyl)pyridine, bis(4-(3-aminophenoxy)phenyl)pyridine, etc. Commercially available amine hardeners can also be used, for example, "SEIKACURE-S" manufactured by SEIKA Corporation, "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

苯并噁嗪系硬化劑之具體例子，可列舉JFE化學公司製之「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製之「HFB2006M」；四國化成工業公司製之「P-d」、「F-a」等。Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa High Polymer Co., Ltd.; "P-d" manufactured by Shikoku Chemical Industry Co., Ltd. , "F-a", etc.

氰酸酯系硬化劑，例如可列舉雙酚A二氰酸酯、多酚氰酸酯(寡聚(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)硫醚，及雙(4-氰酸酯苯基)醚等之2官能氰酸酯樹脂、由酚酚醛清漆及甲酚酚醛清漆等所衍生的多官能氰酸酯樹脂、此等氰酸酯樹脂一部分經三嗪化之預聚物等。氰酸酯系硬化劑之具體例子，可列舉Lonza Japan公司製之「PT30」及「PT60」(均為酚酚醛清漆型多官能氰酸酯樹脂)、「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體之預聚物)等。Cyanate-based hardeners, such as 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-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether, etc. Bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolaks and cresol novolacs, and prepolymers in which a part of these cyanate resins has been triazinated, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resins), "BA230" and "BA230S75" (bisphenol A Part or all of the dicyanate is triazinated to become a trimer prepolymer), etc.

硫醇系硬化劑，例如可列舉三羥甲基丙烷參(3-巰基丙酸酯)、季戊四醇肆(3-巰基丁酸酯)、參(3-巰基丙基)異三聚氰酸酯等。Thiol-based hardeners, for example, trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol tetramethylene (3-mercaptobutyrate), ginseng (3-mercaptopropyl) isocyanurate, etc. .

(B’)其他硬化劑之反應基當量，較佳為50g/eq.~3000g/eq.、更佳為100g/eq.~1000g/eq.、又更佳為100g/eq.~500g/eq.、特佳為100g/eq.~300g/eq.。反應基當量，為反應基每1當量之硬化劑之質量。反應基意指與環氧樹脂反應之基，若是酚系硬化劑，為酚性羥基，若是碳二亞胺系硬化劑，則為碳二亞胺基，依硬化劑之種類而異。(B') The reactive group equivalent weight of other curing agents is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., and more preferably 100g/eq.~500g/eq ., the best is 100g/eq.~300g/eq. Reactive group equivalent is the mass of reactive group per 1 equivalent of hardener. The reactive group refers to the group that reacts with the epoxy resin. If it is a phenolic hardener, it is a phenolic hydroxyl group. If it is a carbodiimide hardener, it is a carbodiimide group. It depends on the type of hardener.

樹脂組成物中之(B’)其他硬化劑之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為15質量%以下、更佳為10質量%以下、又更佳為5質量%以下、特佳為3質量%以下。樹脂組成物中之(B’)其他硬化劑之含量之下限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，例如可為0質量%以上、0.01質量%以上、0.1質量%以上、1質量%以上、1.5質量%以上等。The content of (B') other hardeners in the resin composition is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, and More preferably, it is at most 5 mass %, and most preferably it is at most 3 mass %. The lower limit of the content of (B') other hardeners in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, for example, it can be 0% by mass or more, 0.01% by mass or more, or 0.1% by mass % or more, 1 mass % or more, 1.5 mass % or more, etc.

樹脂組成物中之(B)活性酯系硬化劑之含量，當以樹脂組成物中之(B)活性酯系硬化劑與(B’)其他硬化劑之合計為100質量%時，較佳為10質量%以上、更佳為30質量%以上、又更佳為40質量%以上、特佳為50質量%以上。The content of (B) active ester-based hardener in the resin composition is preferably 10 mass % or more, more preferably 30 mass % or more, still more preferably 40 mass % or more, especially preferably 50 mass % or more.

樹脂組成物中之(A)環氧樹脂中之環氧基之總莫耳當量數，與(B)活性酯系硬化劑及(B’)其他硬化劑中之硬化劑反應基之總莫耳當量數之比(硬化劑反應基/環氧基)，較佳為0.2~2之範圍、更佳為0.5~1.8之範圍、又更佳為1~1.5之範圍。「(A)環氧樹脂中之環氧基之總莫耳當量數」，表示樹脂組成物中所存在的(A)環氧樹脂之質量除以環氧當量所得之值的合計。又，「(B)活性酯系硬化劑及(B’)其他硬化劑中之硬化劑反應基之總莫耳當量數」，表示樹脂組成物中所存在的(B)活性酯系硬化劑之質量除以活性酯基當量之值，及(B’)其他硬化劑之質量除以反應基當量所得之值的合計。The total molar equivalents of (A) epoxy groups in the epoxy resin in the resin composition, and the total molar equivalents of (B) active ester hardeners and (B') hardener reactive groups in other hardeners The ratio of equivalents (hardener reactive group/epoxy group) is preferably in the range of 0.2-2, more preferably in the range of 0.5-1.8, and more preferably in the range of 1-1.5. "The total number of molar equivalents of epoxy groups in (A) epoxy resin" means the sum of the values obtained by dividing the mass of (A) epoxy resin present in the resin composition by the epoxy equivalent. Also, "the total molar equivalents of the reactive groups of the (B) active ester-based hardener and (B') other hardeners" indicates the amount of (B) active ester-based hardener present in the resin composition. The sum of the value obtained by dividing the mass by the active ester group equivalent, and (B') the mass of other hardeners divided by the reactive group equivalent.

＜(C)無機填充材＞ 本發明之樹脂組成物含有(C)無機填充材。(C)無機填充材，係以粒子之狀態含於樹脂組成物中。 ＜(C) Inorganic filler＞ The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.

作為(C)無機填充材之材料，係使用無機化合物。(C)無機填充材之材料，例如可列舉二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁石、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、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯，及磷酸鎢酸鋯等。此等之中尤以二氧化矽特別適合。二氧化矽，例如可列舉無定形二氧化矽、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，二氧化矽較佳為球形二氧化矽。(C)無機填充材可1種單獨使用、亦可依任意比率組合2種以上來使用。As a material of (C) the inorganic filler, an inorganic compound is used. (C) Materials for inorganic fillers, such as silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore , aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. Silica includes, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Also, silica is preferably spherical silica. (C) The inorganic fillers may be used alone or in combination of two or more of them in arbitrary ratios.

(C)無機填充材之市售品，例如可列舉NIPPON STEEL Chemical & Material公司製之「SP60-05」、「SP507-05」；Admatechs公司製之「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」；Denka公司製之「UFP-30」；Tokuyama公司製之「Silfil NSS-3N」、「Silfil NSS-4N」、「Silfil NSS-5N」；Admatechs公司製之「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；Denka公司製之「DAW-03」、「FB-105FD」；日揮觸媒化成公司製之「BA-S」等。(C) Commercially available inorganic fillers, for example, "SP60-05" and "SP507-05" manufactured by NIPPON STEEL Chemical &Material; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatechs ", "YA010C"; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ" and " SO-C4", "SO-C2", "SO-C1"; "DAW-03" and "FB-105FD" manufactured by Denka Corporation; "BA-S" manufactured by Nikki Catalyst Chemicals Co., Ltd., etc.

(C)無機填充材之平均粒徑不特別限定，較佳為10μm以下、更佳為5μm以下、又更佳為4μm以下、又再更佳為3μm以下、特佳為2.7μm以下。(C)無機填充材之平均粒徑之下限不特別限定，較佳為0.01μm以上、更佳為0.05μm以上、又更佳為0.1μm以上、特佳為0.2μm以上。(C)無機填充材之平均粒徑，可藉由基於米氏(Mie)散射理論之雷射繞射/散射法來測定。具體而言，可藉由以雷射繞射散射式粒徑分布測定裝置，由體積基準製成無機填充材之粒徑分布，並以其中位直徑為平均粒徑來測定。測定樣品可使用將無機填充材100mg、甲基乙基酮10g量取至小玻璃瓶，經超音波分散10分鐘者。將測定樣品使用雷射繞射式粒徑分布測定裝置，將使用光源波長設為藍色及紅色，以流通槽方式測定無機填充材之體積基準之粒徑分布，由所得之粒徑分布，作為中位直徑而算出平均粒徑。雷射繞射式粒徑分布測定裝置，例如可列舉堀場製作所公司製「LA-960」等。(C) The average particle size of the inorganic filler is not particularly limited, but is preferably not more than 10 μm, more preferably not more than 5 μm, more preferably not more than 4 μm, still more preferably not more than 3 μm, and most preferably not more than 2.7 μm. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, still more preferably at least 0.1 μm, and most preferably at least 0.2 μm. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone are measured into a small glass bottle and dispersed by ultrasonic waves for 10 minutes. Use a laser diffraction particle size distribution measuring device for the measurement sample, set the wavelength of the light source to blue and red, and measure the volume-based particle size distribution of the inorganic filler in a flow cell, and use the obtained particle size distribution as Calculate the average particle size from the median diameter. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. and the like are mentioned.

(C)無機填充材之比表面積不特別限定，較佳為0.1m 2/g以上、更佳為0.5m 2/g以上、又更佳為1m 2/g以上、特佳為3m 2/g以上。(C)無機填充材之比表面積之上限不特別限定，較佳為100m 2/g以下、更佳為70m 2/g以下、又更佳為50m 2/g以下、特佳為40m 2/g以下。無機填充材之比表面積，可藉由遵照BET法，使用比表面積測定裝置(Mountech公司製Macsorb HM-1210)，使氮氣吸附於試樣表面，使用BET多點法算出比表面積而得到。 (C) The specific surface area of the inorganic filler is not particularly limited, but is preferably at least 0.1m 2 /g, more preferably at least 0.5m 2 /g, still more preferably at least 1m 2 /g, most preferably at least 3m 2 /g above. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably at most 100m 2 /g, more preferably at most 70m 2 /g, still more preferably at most 50m 2 /g, most preferably at most 40m 2 /g the following. The specific surface area of the inorganic filler can be obtained by calculating the specific surface area using the BET multipoint method by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method.

(C)無機填充材，可為空孔率0體積%之非中空無機填充材(較佳為非中空二氧化矽)、亦可為空孔率超過0體積%之中空無機填充材(較佳為中空二氧化矽)，亦可包含兩者。就將介電率抑制在更低的觀點，(C)無機填充材較佳僅包含中空無機填充材(較佳為中空二氧化矽)，或包含非中空無機填充材(較佳為非中空二氧化矽)與中空無機填充材(較佳為中空二氧化矽)兩者。中空無機填充材之空孔率較佳為70體積%以下、更佳為50體積%以下、特佳為30體積%以下。(C)無機填充材之空孔率之下限，例如可為超過0體積%、1體積%以上、5體積%以上、10體積%以上等。無機填充材之空孔率P(體積%)，係定義為相對於以粒子之外表面為基準的粒子全體之體積而言，於粒子內部存在有1個或2個以上的空孔之合計體積的體積基準比例(空孔之合計體積/粒子之體積)，例如，係使用無機填充材之實際的密度之測定值D M(g/cm 3)，及形成無機填充材之材料的物質密度之理論值D T(g/cm 3)，藉由下述式(1)算出。 (C) The inorganic filler can be a non-hollow inorganic filler with a porosity of 0% by volume (preferably non-hollow silica), or a hollow inorganic filler with a porosity of more than 0% by volume (preferably is hollow silica), may also contain both. From the viewpoint of keeping the dielectric constant lower, the (C) inorganic filler preferably only includes a hollow inorganic filler (preferably hollow silica), or contains a non-hollow inorganic filler (preferably a non-hollow silica). silicon oxide) and hollow inorganic filler (preferably hollow silicon dioxide). The porosity of the hollow inorganic filler is preferably 70% by volume or less, more preferably 50% by volume or less, most preferably 30% by volume or less. (C) The lower limit of the porosity of the inorganic filler may be, for example, more than 0 volume %, more than 1 volume %, more than 5 volume %, or more than 10 volume %. The porosity P (volume %) of the inorganic filler is defined as the total volume of one or more pores inside the particle relative to the volume of the entire particle based on the outer surface of the particle The volume reference ratio (total volume of voids/volume of particles), for example, is the measured value D M (g/cm 3 ) of the actual density of the inorganic filler used, and the ratio of the material density of the material forming the inorganic filler The theoretical value D T (g/cm 3 ) was calculated by the following formula (1).

無機填充材之實際的密度，例如可使用真密度測定裝置來測定。真密度測定裝置，例如可列舉QUANTACHROME公司製之ULTRAPYCNOMETER1000等。測定氣體，例如係使用氮。The actual density of the inorganic filler can be measured, for example, using a true density measuring device. As a true density measuring device, for example, ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME CORPORATION, etc. are mentioned. As the gas to be measured, for example, nitrogen is used.

(C)無機填充材，就提高耐濕性及分散性之觀點，較佳為經表面處理劑處理。表面處理劑，例如可列舉含有氟之矽烷偶合劑、胺基矽烷系偶合劑、環氧基矽烷系偶合劑、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、鈦酸酯系偶合劑等。又，表面處理劑，可1種單獨使用、亦可任意組合2種以上使用。(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Surface treatment agents, for example, silane coupling agents containing fluorine, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds , Titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

表面處理劑之市售品，例如可列舉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」(長鏈環氧基型矽烷偶合劑)、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。Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethylsilane). oxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxy silane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

以表面處理劑進行表面處理之程度，就提高無機填充材之分散性的觀點，較佳控制在特定之範圍。具體而言，無機填充材100質量%，較佳經0.2質量%~5質量%之表面處理劑表面處理、更佳經0.2質量%~3質量%表面處理、又更佳經0.3質量%~2質量%表面處理。The degree of surface treatment with a surface treatment agent is preferably controlled within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably treated with a surface treatment agent at 0.2% to 5% by mass, more preferably treated at 0.2% to 3% by mass, and more preferably treated at 0.3% to 2% by mass. Mass % surface treatment.

以表面處理劑進行表面處理之程度，可藉由無機填充材之每單位表面積的碳量來評估。無機填充材之每單位表面積的碳量，就提高無機填充材之分散性的觀點，較佳為0.02mg/m 2以上、更佳為0.1mg/m 2以上、又更佳為0.2mg/m 2以上。另一方面，就防止樹脂組成物之熔融黏度或於薄片形態之熔融黏度的上昇之觀點，較佳為1.0mg/m 2以下、更佳為0.8mg/m 2以下、又更佳為0.5mg/m 2以下。 The degree of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler 2 or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the sheet form from rising, it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and more preferably 0.5 mg / m2 or less.

(C)無機填充材之每單位表面積的碳量，可於將表面處理後之無機填充材以溶劑(例如甲基乙基酮(MEK))進行洗淨處理後來測定。具體而言，係將作為溶劑之足夠量的MEK添加至經表面處理劑表面處理之無機填充材，於25℃進行5分鐘超音波洗淨。去除上清液，將固體成分乾燥後，可使用碳分析計測定無機填充材之每單位表面積的碳量。碳分析計可使用堀場製作所公司製「EMIA-320V」等。(C) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd., etc. can be used.

樹脂組成物中之(C)無機填充材之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳可為90質量%以下、更佳可為85質量%以下、又更佳可為80質量%以下、特佳可為75質量%以下。樹脂組成物中之(C)無機填充材之含量之下限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，例如較佳為5質量%以上，或10質量%以上、更佳為20質量%以上，或30質量%以上、又更佳為40質量%以上，或50質量%以上、又再更佳為55質量%以上，或60質量%以上、特佳為65質量%以上，或70質量%以上。The content of the (C) inorganic filler in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably not more than 90% by mass, more preferably not more than 85% by mass, More preferably, it is at most 80% by mass, and particularly preferably at most 75% by mass. The lower limit of the content of (C) inorganic filler in the resin composition is not particularly limited. When the non-volatile components in the resin composition are 100% by mass, for example, it is preferably 5% by mass or more, or 10% by mass or more, and more Preferably at least 20% by mass, or at least 30% by mass, more preferably at least 40% by mass, or at least 50% by mass, still more preferably at least 55% by mass, or at least 60% by mass, especially preferably at least 65% by mass or more, or more than 70% by mass.

＜(D)硬化促進劑＞ 本發明之樹脂組成物，亦可含有(D)硬化促進劑作為任意成分。(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 of the present invention may contain (D) a hardening accelerator as an optional component. (D) A hardening accelerator has a function as a hardening catalyst which accelerates hardening of (A) epoxy resin.

(D)硬化促進劑，例如可列舉磷系硬化促進劑、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。(D)硬化促進劑，較佳包含咪唑系硬化促進劑。(D)硬化促進劑，可1種單獨使用、亦可組合2種以上使用。(D) Hardening accelerators include, for example, 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. (D) The hardening accelerator preferably includes an imidazole-based hardening accelerator. (D) The curing accelerator may be used alone or in combination of two or more.

磷系硬化促進劑，例如可列舉四丁基鏻溴化物、四丁基鏻氯化物、四丁基鏻乙酸鹽、四丁基鏻癸酸鹽、四丁基鏻月桂酸鹽、雙(四丁基鏻)苯均四酸鹽、四丁基鏻氫六氫鄰苯二甲酸鹽、四丁基鏻2,6-雙[(2-羥基-5-甲基苯基)甲基]-4-甲基酚鹽、二-tert-丁基二甲基鏻四苯基硼酸鹽等之脂肪族鏻鹽；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、苄基三苯基鏻氯化物、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)三苯基鏻硫代氰酸鹽、四苯基鏻硫代氰酸鹽、丁基三苯基鏻硫代氰酸鹽等之芳香族鏻鹽；三苯基膦/三苯基硼烷等之芳香族膦/硼烷複合體；三苯基膦/p-苯醌加成反應物等之芳香族膦/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、三環己基膦等之脂肪族膦；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-o-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(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,2-雙(二苯基膦基)乙炔、2,2’-雙(二苯基膦基)二苯基醚等之芳香族膦等。Phosphorus-based hardening accelerators, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium phosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4 - Aliphatic phosphonium salts of methylphenate, di-tert-butyldimethylphosphonium tetraphenylborate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenyl Phosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolyl borate, tetraphenyl Phosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenyl borate, reference (3-methylphenyl) ethylphosphonium tetraphenyl borate, reference (2-Methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenyl Aromatic phosphonium salts such as phosphonium thiocyanates; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone addition reactants, etc. Aromatic phosphine/quinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl( Aliphatic phosphines such as 3-methyl-2-butenyl)phosphine and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyl diphenylphosphine Phenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, ginseng (4 -Ethylphenyl) phosphine, reference (4-propylphenyl) phosphine, reference (4-isopropylphenyl) phosphine, reference (4-butylphenyl) phosphine, reference (4-tert-butyl Phenyl) 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, diphenyl -2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane , 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether and other aromatic phosphines.

脲系硬化促進劑，例如可列舉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-1,1-二甲基脲等之脂肪族二甲基脲；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]等之芳香族二甲基脲等。Urea-based hardening accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1, Aliphatic dimethylurea such as 1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea, etc.; 3-phenyl-1,1-dimethylurea, 3-(4-chloro Phenyl)-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-methoxy phenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)benzene base]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)benzene base]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1 , 3-phenylene) bis (N', N'-dimethylurea) [toluene bisdimethylurea] and other aromatic dimethylureas.

胍系硬化促進劑，例如可列舉二氰二胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[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-(o-甲苯基)雙胍等。Guanidine hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl guanidine, 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-octadecylbiguanide, 1,1-Dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

咪唑系硬化促進劑，例如可列舉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-苄基-2-甲基咪唑、1-苄基-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甲酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸鹽、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-三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、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-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂之加合體。Imidazole-based hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-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-phenyl imidazolium 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'-methylimidazole Base-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotriazine Polycyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzyl imidazolium chloride, 2-methyl Imidazole compounds such as imidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

咪唑系硬化促進劑，亦可使用市售品，例如可列舉四國化成工業公司製之「1B2PZ」、「2MZA-PW」、「2PHZ-PW」、「C11Z-A」、三菱化學公司製之「P200-H50」等。As the imidazole-based hardening accelerator, commercially available products can also be used, for example, "1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Mitsubishi Chemical Corporation, etc. "P200-H50" etc.

金屬系硬化促進劑，例如可列舉鈷、銅、鋅、鐵、鎳、錳、錫等之金屬之有機金屬錯合物或有機金屬鹽。有機金屬錯合物之具體例子，可列舉乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等之有機鈷錯合物、乙醯丙酮銅(II)等之有機銅錯合物、乙醯丙酮鋅(II)等之有機鋅錯合物、乙醯丙酮鐵(III)等之有機鐵錯合物、乙醯丙酮鎳(II)等之有機鎳錯合物、乙醯丙酮錳(II)等之有機錳錯合物等。有機金屬鹽，例如可列舉辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, etc. Organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, manganese (II) acetylacetonate ) and other organomanganese complexes. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

胺系硬化促進劑，例如可列舉三乙基胺、三丁基胺等之三烷基胺；4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一烯等。Amine-based hardening accelerators, for example, trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-ginseng ( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

胺系硬化促進劑，亦可使用市售品，例如可列舉味之素Fine-Techno公司製之「MY-25」等。As the amine-based hardening accelerator, a commercially available product can also be used, for example, "MY-25" by Ajinomoto Fine-Techno Co., Ltd., etc. are mentioned.

樹脂組成物中之(D)硬化促進劑之含量不特別限定，以樹脂組成物中之不揮發成分為100質量%時，較佳為15質量%以下、更佳為10質量%以下、又更佳為5質量%以下、特佳為2質量%以下。樹脂組成物中之(D)硬化促進劑之含量之下限不特別限定，以樹脂組成物中之不揮發成分為100質量%時，例如可為0質量%以上、0.001質量%以上、0.01質量%以上等。The content of the (D) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably at most 15% by mass, more preferably at most 10% by mass, and even more preferably Preferably, it is 5 mass % or less, and especially preferably, it is 2 mass % or less. The lower limit of the content of the (D) hardening accelerator in the resin composition is not particularly limited, and when the non-volatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.001% by mass or more, or 0.01% by mass above and so on.

＜(E)其他添加劑＞ 本發明之樹脂組成物，亦可進一步含有任意之添加劑。如此之添加劑，例如可列舉具有乙烯基苯基、丙烯醯基、甲基丙烯醯基、馬來醯亞胺基(2,5-二氫-2,5-二側氧基-1H-吡咯-1-基)等之自由基聚合性化合物；過氧化物系自由基聚合起始劑、偶氮系自由基聚合起始劑等之自由基聚合起始劑；環氧基丙烯酸酯樹脂、胺基甲酸酯丙烯酸酯樹脂、胺基甲酸酯樹脂、氰酸酯樹脂、苯并噁嗪樹脂、不飽和聚酯樹脂、酚樹脂、三聚氰胺樹脂、聚矽氧樹脂等之環氧樹脂以外之熱硬化性樹脂；苯氧基樹脂、聚乙烯基縮醛樹脂、聚烯烴樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等之熱可塑性樹脂；過氧化物系自由基聚合起始劑、偶氮系自由基聚合起始劑等之自由基聚合起始劑；橡膠粒子等之有機填充材；有機銅化合物、有機鋅化合物、有機鈷化合物等之有機金屬化合物；酞花青藍、酞花青綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑等之著色劑；氫醌、兒茶酚、五倍子酚、酚噻嗪等之聚合禁止劑；聚矽氧系調平劑、丙烯酸聚合物系調平劑等之調平劑；Benton(膨潤土)、蒙脫土等之增黏劑；聚矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等之消泡劑；苯并三唑系紫外線吸收劑等之紫外線吸收劑；脲矽烷等之接著性提高劑；三唑系密合性賦予劑、四唑系密合性賦予劑、三嗪系密合性賦予劑等之密合性賦予劑；受阻酚系抗氧化劑等之抗氧化劑；二苯乙烯衍生物等之螢光增白劑；氟系界面活性劑、聚矽氧系界面活性劑等之界面活性劑；磷系難燃劑(例如磷酸酯化合物、膦氮烯化合物、次磷酸化合物、紅磷)、氮系難燃劑(例如硫酸三聚氰胺)、鹵素系難燃劑、無機系難燃劑(例如三氧化銻)等之難燃劑；磷酸酯系分散劑、聚氧化烯系分散劑、乙炔系分散劑、聚矽氧系分散劑、陰離子性分散劑、陽離子性分散劑等之分散劑；硼酸酯系安定劑、鈦酸酯系安定劑、鋁酸酯系安定劑、鋯酸酯系安定劑、異氰酸酯系安定劑、羧酸系安定劑、羧酸酐系安定劑等之安定劑等。(E)其他添加劑，可1種單獨使用、亦可以任意比率組合使用2種以上。(E)其他添加劑之含量為所屬技術領域中具有通常知識者可適當設定。 ＜(E)Other additives＞ The resin composition of the present invention may further contain arbitrary additives. Such additives include, for example, vinylphenyl, acryl, methacryl, maleimide (2,5-dihydro-2,5-diendoxy-1H-pyrrole- 1-radical) and other radical polymerizable compounds; free radical polymerization initiators such as peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc.; epoxy-based acrylate resins, amine-based Formate acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, polysiloxane resins and other thermosetting epoxy resins Resin; phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyresin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Plastic resins; free radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organic fillers such as rubber particles; organic copper compounds, organic zinc compounds, organic cobalt Organometallic compounds such as compounds; coloring agents of phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; hydroquinone, catechol, gallol, phenothiazine, etc. Polymerization inhibitors; Silicone-based leveling agents, acrylic polymer-based leveling agents, etc.; Benton (bentonite), montmorillonite, etc. Defoamers, fluorine-based defoamers, vinyl resin-based defoamers, etc.; benzotriazole-based UV absorbers, etc.; UV absorbers, such as urea-silane; Adhesion-imparting agents such as tetrazole-based adhesion-imparting agents and triazine-based adhesion-imparting agents; antioxidants such as hindered phenolic antioxidants; fluorescence enhancers such as stilbene derivatives Whitening agents; Surfactants such as fluorine-based surfactants, polysiloxane-based surfactants, etc.; phosphorus-based flame retardants (such as phosphate compounds, phosphazene compounds, hypophosphorous compounds, red phosphorus), nitrogen-based flame retardants flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants (such as antimony trioxide), etc.; phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, polysilicon Oxygen-based dispersants, anionic dispersants, cationic dispersants, etc.; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers, etc. (E) For other additives, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. (E) The content of other additives can be appropriately set by those who have common knowledge in the technical field.

＜(F)有機溶劑＞ 本發明之樹脂組成物，有時進一步含有任意之有機溶劑。作為(F)有機溶劑，可適當使用公知者，其種類並不特別限定。(F)有機溶劑，例如可列舉丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮系溶劑；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-丁內酯等之酯系溶劑；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、苯甲醚等之醚系溶劑；甲醇、乙醇、丙醇、丁醇、乙二醇等之醇系溶劑；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、甲氧基丙酸甲酯等之醚酯系溶劑；乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲酯等之酯醇系溶劑；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)等之醚醇系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等之醯胺系溶劑；二甲基亞碸等之亞碸系溶劑；乙腈、丙腈等之腈系溶劑；己烷、環戊烷、環己烷、甲基環己烷等之脂肪族烴系溶劑；苯、甲苯、二甲苯、乙基苯、三甲基苯等之芳香族烴系溶劑等。(F)有機溶劑，可1種單獨使用、亦可以任意比率組合使用2種以上。 ＜(F) Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent. As (F) organic solvent, a well-known thing can be used suitably, and the kind is not specifically limited. (F) Organic solvents, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, Esters solvents such as isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl Ether-based solvents such as ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol Ether ester solvents such as monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc.; lactic acid Ester alcohol solvents such as methyl ester, ethyl lactate, and methyl 2-hydroxyisobutyrate; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, Ether alcohol solvents such as diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2 -Amide-based solvents such as pyrrolidone, etc.; ethylene-based solvents such as dimethyloxide; nitrile-based solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (F) Organic solvents may be used alone or in combination of two or more in arbitrary ratios.

乾燥前之塗漆狀的樹脂組成物中之(F)有機溶劑之含量不特別限定，以樹脂組成物中之全部成分為100質量%時，例如為40質量%以下、30質量%以下、較佳為20質量%以下、更佳為10質量%以下、又更佳為8質量%以下、特佳為6質量%以下。樹脂薄片中形成乾燥後之樹脂組成物層的樹脂組成物中之(F)有機溶劑之含量不特別限定，以樹脂組成物中之全部成分為100質量%時，較佳為5質量%以下、更佳為3質量%以下、又更佳為2質量%以下、特佳為1質量%以下。The content of (F) organic solvent in the paint-like resin composition before drying is not particularly limited, and when the total components in the resin composition are 100% by mass, for example, it is 40% by mass or less, 30% by mass or less, relatively Preferably, it is 20 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 8 mass % or less, Most preferably, it is 6 mass % or less. The content of the (F) organic solvent in the resin composition forming the dried resin composition layer in the resin sheet is not particularly limited, but it is preferably 5% by mass or less when the total components in the resin composition are 100% by mass. More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less, Most preferably, it is 1 mass % or less.

＜樹脂組成物之製造方法＞ 本發明之樹脂組成物，例如，可藉由於任意之調製容器，以任意順序及/或同時添加一部分或全部的(A)環氧樹脂、(B)活性酯系硬化劑、(C)無機填充材、依需要之(D)硬化促進劑、依需要之(E)其他添加劑，及依需要之(F)有機溶劑，並予以混合而製造。又，於添加各成分予以混合的過程中，可適當設定溫度，亦可一時地或始終進行加熱及/或冷卻。又，於添加並混合的過程中或於其後，亦可將樹脂組成物例如使用混合器等之攪拌裝置或振盪裝置進行攪拌或振盪，使其均勻分散。又，在攪拌或振盪的同時，亦可於真空下等之低壓條件下進行脫泡。 ＜Manufacturing method of resin composition＞ The resin composition of the present invention, for example, can add part or all of (A) epoxy resin, (B) active ester hardener, (C) inorganic filler in any order and/or at the same time by using any preparation container Materials, (D) hardening accelerator as needed, (E) other additives as needed, and (F) organic solvent as needed, and mixed to manufacture. Moreover, in the process of adding and mixing each component, temperature may be set suitably, and heating and/or cooling may be performed temporarily or always. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring device such as a mixer or an oscillating device to uniformly disperse it. Moreover, you may defoam under low pressure conditions, such as a vacuum, with stirring or shaking.

＜樹脂組成物之特性＞ 本發明之樹脂組成物，含有(A)環氧樹脂、(B)活性酯系硬化劑，及(C)無機填充材，且以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為60質量%以上，(B)成分包含(B1)末端立體障礙型活性酯系硬化劑。依照如此之樹脂組成物，可得到龜裂耐性優良的硬化物。 ＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) active ester hardener, and (C) inorganic filler, and when the non-volatile components in the resin composition are 100% by mass, (C The content of the component ) is 60% by mass or more, and the component (B) contains (B1) a terminal steric barrier type active ester-based hardener. According to such a resin composition, a cured product having excellent crack resistance can be obtained.

本發明之樹脂組成物之硬化物，可具有可抑制除膠渣處理(粗化處理)後之龜裂產生的特徵。因此，於一實施形態中，如下述試驗例3般製作電路基板及進行除膠渣處理後，觀察100個電路基板之銅墊(copper pad)部時，龜裂較佳可為10個以下(10%以下)。The cured product of the resin composition of the present invention can have the feature of suppressing the generation of cracks after the desmearing treatment (roughening treatment). Therefore, in one embodiment, after making the circuit board as in the following test example 3 and carrying out desmearing treatment, when observing the copper pad (copper pad) portion of 100 circuit boards, the number of cracks is preferably less than 10 ( 10% or less).

於一實施形態中，本發明之樹脂組成物之硬化物，可具有將介電正切(Df)抑制在低水準的特徵。因此，於一實施形態中，如下述試驗例1般於5.8GHz、23℃進行測定時之樹脂組成物之硬化物的介電正切(Df)，較佳可為0.010以下、更佳可為0.008以下、又更佳可為0.007以下、又再更佳可為0.005以下，或0.003以下、特佳可為0.0025以下，或0.002以下。In one embodiment, the cured product of the resin composition of the present invention can have a feature of suppressing the dielectric tangent (Df) to a low level. Therefore, in one embodiment, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23°C as in Test Example 1 below is preferably 0.010 or less, more preferably 0.008 or less, more preferably less than 0.007, still more preferably less than 0.005, or less than 0.003, most preferably less than 0.0025, or less than 0.002.

於一實施形態中，本發明之樹脂組成物之硬化物，可具有玻璃轉移點(Tg)高的特徵。因此，於一實施形態中，如下述試驗例2般進行測定時之玻璃轉移溫度(Tg)，較佳可為100℃以上、更佳可為120℃以上、又更佳可為130℃以上、又再更佳可為140℃以上、特佳可為150℃以上。In one embodiment, the cured product of the resin composition of the present invention may have a high glass transition point (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in Test Example 2 below is preferably 100°C or higher, more preferably 120°C or higher, still more preferably 130°C or higher, Still more preferably, it may be above 140°C, and most preferably, it may be above 150°C.

＜樹脂組成物之用途＞ 本發明之樹脂組成物，可適合使用作為絕緣用途之樹脂組成物，特別是用以形成絕緣層之樹脂組成物。具體而言，可適合使用作為用以形成於絕緣層上所形成之導體層(包含再配線層)的用以形成該絕緣層之樹脂組成物(用以形成導體層之絕緣層形成用樹脂組成物)。又，於後述之印刷配線板中，可適合使用作為用以形成印刷配線板之絕緣層的樹脂組成物(印刷配線板之絕緣層形成用樹脂組成物)。又，本發明之樹脂組成物可廣範圍地使用於樹脂薄片、預浸物等之薄片狀層合材料、阻焊劑、底部填充材、晶粒接合材、半導體密封材、填孔樹脂、零件埋入樹脂等以樹脂組成物為必要之用途。 ＜Applications of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, especially a resin composition for forming an insulating layer. Specifically, a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) as a conductive layer (including a redistribution layer) formed on an insulating layer can be suitably used things). Moreover, in the printed wiring board mentioned later, the resin composition (resin composition for insulating layer formation of a printed wiring board) as a resin composition for forming the insulating layer of a printed wiring board can be used suitably. In addition, the resin composition of the present invention can be used in a wide range of sheet-like laminates such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, parts embedding materials, etc. Injection into resin, etc., where the resin composition is necessary.

又，例如，經過以下之(1)~(6)步驟來製造半導體晶片封裝時，本發明之樹脂組成物，亦可適合使用作為當作用以形成再配線層的絕緣層之再配線形成層用之樹脂組成物(再配線形成層形成用之樹脂組成物)，及用以密封半導體晶片之樹脂組成物(半導體晶片密封用之樹脂組成物)。製造半導體晶片封裝時，亦可於密封層上進一步形成再配線層。 (1)於基材上層合暫時固定膜之步驟、 (2)將半導體晶片暫時固定於暫時固定膜上之步驟、 (3)於半導體晶片上形成密封層之步驟、 (4)將基材及暫時固定膜從半導體晶片剝離之步驟、 (5)於半導體晶片之經剝離基材及暫時固定膜之面上，形成當作絕緣層之再配線形成層之步驟，及 (6)於再配線形成層上，形成當作導體層之再配線層之步驟。 Also, for example, when a semiconductor chip package is produced through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a rewiring formation layer as an insulating layer for forming a rewiring layer Resin composition (resin composition for rewiring formation layer formation), and resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). When manufacturing a semiconductor chip package, a redistribution layer can also be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring formation layer serving as an insulating layer on the surface of the semiconductor wafer on which the base material and the temporary fixing film have been peeled off, and (6) A step of forming a rewiring layer serving as a conductor layer on the rewiring forming layer.

又，本發明之樹脂組成物，可產生零件埋入性良好的絕緣層，故亦可適合使用於印刷配線板為零件內藏電路板的情況。In addition, the resin composition of the present invention can form an insulating layer with good parts embedding properties, so it can also be suitably used when the printed wiring board is a circuit board with built-in parts.

＜薄片狀層合材料＞ 本發明之樹脂組成物，雖亦可以塗漆狀態進行塗佈來使用，但工業上一般而言，以含有該樹脂組成物之薄片狀層合材料的形態來用較為適宜。 ＜Flake laminated materials＞ Although the resin composition of the present invention can also be used by coating in a painted state, industrially, it is generally suitable to use it in the form of a sheet-like laminate containing the resin composition.

作為薄片狀層合材料，較佳為以下所示之樹脂薄片、預浸物。As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

於一實施形態中，樹脂薄片，包含支撐體，與設置於該支撐體上的樹脂組成物層而成，樹脂組成物層係由本發明之樹脂組成物所形成。In one embodiment, the resin sheet includes a support body and a resin composition layer disposed on the support body, and the resin composition layer is formed of the resin composition of the present invention.

樹脂組成物層之厚度，就印刷配線板之薄型化，及即使該樹脂組成物之硬化物為薄膜亦可提供絕緣性優良的硬化物之觀點，較佳為50μm以下、更佳為40μm以下。樹脂組成物層之厚度之下限不特別限定，通常可為5μm以上、10μm以上等。The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and generally, it may be 5 μm or more, 10 μm or more, and the like.

支撐體，例如可列舉由塑膠材料所構成之薄膜、金屬箔、離型紙，較佳為由塑膠材料所構成之薄膜、金屬箔。Examples of the support include films, metal foils, and release paper made of plastic materials, preferably films and metal foils made of plastic materials.

使用由塑膠材料所構成之薄膜作為支撐體時，塑膠材料，例如可列舉聚對苯二甲酸乙二酯(以下有時略稱為「PET」)、聚萘二甲酸乙二酯(以下有時略稱為「PEN」)等之聚酯、聚碳酸酯(以下有時略稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等之丙烯酸樹脂、環狀聚烯烴、三乙醯基纖維素(TAC)、聚醚硫醚(PES)、聚醚酮、聚醯亞胺等。其中尤佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯；特佳為價格便宜的聚對苯二甲酸乙二酯。When using a film made of plastic materials as a support, the plastic materials include, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes Polyesters such as "PEN" for short), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic resins such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl Cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Especially preferred are polyethylene terephthalate and polyethylene naphthalate; particularly preferred is polyethylene terephthalate which is cheap.

使用金屬箔作為支撐體時，金屬箔，例如可列舉銅箔、鋁箔等，較佳為銅箔。作為銅箔，可使用由銅之單金屬所構成的箔，亦可使用由銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所構成的箔。When metal foil is used as a support body, metal foil, for example, copper foil, aluminum foil, etc. are mentioned, Preferably it is copper foil. As the copper foil, a foil composed of a single metal of copper, or a foil composed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

支撐體在與樹脂組成物層接合之面上亦可實施消光處理、電暈處理、抗靜電處理。Matting treatment, corona treatment, and antistatic treatment may also be performed on the surface of the support that is bonded to the resin composition layer.

又，作為支撐體，亦可使用在與樹脂組成物層接合之面上具有離型層之附離型層之支撐體。附離型層之支撐體的離型層所使用之離型劑，例如可列舉選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂，及聚矽氧樹脂所成之群的1種以上之離型劑。附離型層之支撐體亦可使用市售品，例如可列舉具有以醇酸樹脂系離型劑為主成分之離型層的PET薄膜即琳得科公司製之「SK-1」、「AL-5」、「AL-7」、東麗公司製之「Lumirror T60」、帝人公司製之「Purex」、Unitika公司製之「Unipeel」等。Moreover, as a support body, the support body with a release layer which has a release layer on the surface bonded to a resin composition layer can also be used. The release agent used for the release layer of the support with release layer includes, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins The above release agent. The support body with the release layer can also be a commercially available product, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, that is, "SK-1" manufactured by Lintec Corporation, "SK-1", " AL-5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Corporation, etc.

支撐體之厚度不特別限定，較佳為5μm~75μm之範圍、更佳為10μm~60μm之範圍。再者，使用附離型層之支撐體時，較佳為附離型層之支撐體全體之厚度為上述範圍。The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer as a whole falls within the said range.

於一實施形態中，樹脂薄片亦可進一步依需要包含任意之層。該任意之層，例如可列舉設置於樹脂組成物層之未與支撐體接合之面(亦即與支撐體相反側之面)上的同等於支撐體的保護膜等。保護膜之厚度不特別限定，例如為1μm~40μm。藉由層合保護膜，可抑制灰塵等對樹脂組成物層表面之附著或者是傷痕。In one embodiment, the resin sheet may further include an arbitrary layer as needed. The optional layer includes, for example, a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, for example, it is 1 μm˜40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer or scratches.

樹脂薄片，例如可藉由將液狀(塗漆狀)之樹脂組成物直接，或調製將樹脂組成物溶解於有機溶劑而得之液狀(塗漆狀)之樹脂組成物，並將其使用模塗佈器等塗佈於支撐體上，進一步進行乾燥而形成樹脂組成物層來製造。Resin flakes, for example, can be used by directly dissolving a liquid (painted) resin composition or preparing a liquid (painted) resin composition obtained by dissolving a resin composition in an organic solvent. Manufactured by coating on a support with a die coater or the like, and drying to form a resin composition layer.

作為有機溶劑，可列舉與作為樹脂組成物之成分所說明的有機溶劑相同者。有機溶劑可單獨使用1種，亦可組合2種以上使用。Examples of the organic solvent include the same ones as those described as the components of the resin composition. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

乾燥可藉由加熱、吹熱風等之公知方法實施。乾燥條件不特別限定，但係乾燥至使樹脂組成物層中之有機溶劑之含量成為10質量%以下、較佳成為5質量%以下。雖亦依樹脂組成物中之有機溶劑之沸點而異，例如使用含有30質量%~60質量%之有機溶劑的樹脂組成物時，可藉由於50℃~150℃進行3分鐘~10分鐘乾燥，來形成樹脂組成物層。Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but are dried until the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it also depends on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of organic solvent, it can be dried at 50°C to 150°C for 3 minutes to 10 minutes, to form a resin composition layer.

樹脂薄片可捲成滾筒狀來保存。樹脂薄片具有保護膜時，可藉由剝離保護膜來使用。Resin sheets can be rolled into rolls for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

於一實施形態中，預浸物係使本發明之樹脂組成物含浸於薄片狀纖維基材而形成。In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet-shaped fiber base material.

預浸物所用之薄片狀纖維基材不特別限定，可使用玻璃布、聚芳醯胺不織布、液晶聚合物不織布等之作為預浸物用基材而常用者。就印刷配線板之薄型化之觀點，薄片狀纖維基材之厚度，較佳為50μm以下、更佳為40μm以下、又更佳為30μm以下、特佳為20μm以下。薄片狀纖維基材之厚度之下限不特別限定。通常為10μm以上。The sheet-like fiber substrate used for the prepreg is not particularly limited, and glass cloth, polyaramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc., which are commonly used as prepreg substrates, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber base is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the flake-like fibrous substrate is not particularly limited. Usually 10 μm or more.

預浸物可藉由熱熔法、溶劑法等之公知方法製造。The prepreg can be produced by known methods such as a hot melt method and a solvent method.

預浸物之厚度，可為與上述樹脂薄片中之樹脂組成物層相同之範圍。The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

本發明之薄片狀層合材料，可適合使用於形成印刷配線板之絕緣層(印刷配線板之絕緣層用)，可更適合使用於形成印刷配線板之層間絕緣層(印刷配線板之層間絕緣層用)。The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (interlayer insulation of a printed wiring board). layer).

＜印刷配線板＞ 本發明之印刷配線板，包含由使本發明之樹脂組成物硬化所得的硬化物所構成之絕緣層。 ＜Printed Wiring Board＞ The printed wiring board of the present invention includes an insulating layer composed of a cured product obtained by curing the resin composition of the present invention.

印刷配線板，例如可使用上述樹脂薄片，藉由包含下述(I)及(II)之步驟的方法來製造。 (I)於內層基板上，將樹脂薄片以樹脂薄片之樹脂組成物層與內層基板接合的方式層合之步驟 (II)將樹脂組成物層硬化(例如熱硬化)而形成絕緣層之步驟 A printed wiring board can be manufactured by the method including the following (I) and (II) process using the said resin sheet, for example. (I) The step of laminating the resin sheet on the inner substrate in such a way that the resin composition layer of the resin sheet is bonded to the inner substrate (II) Step of hardening (for example, thermosetting) the resin composition layer to form an insulating layer

步驟(I)所用之「內層基板」，係指作為印刷配線板之基板的構件，例如可列舉玻璃環氧樹脂基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。又，該基板，可於其單面或兩面具有導體層，該導體層亦可經圖型加工。於基板之單面或兩面上形成有導體層(電路)的內層基板，有時稱為「內層電路基板」。又，製造印刷配線板時，會進一步形成絕緣層及/或導體層的中間製造物亦包含於本發明所稱的「內層基板」中。印刷配線板為零件內藏電路板時，亦可使用內藏有零件之內層基板。The "inner layer substrate" used in step (I) refers to a member as a substrate of a printed wiring board, for example, a glass epoxy resin substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermal Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may also be patterned. An inner layer substrate with a conductive layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". In addition, an intermediate product in which an insulating layer and/or a conductor layer is further formed in the manufacture of a printed wiring board is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner substrate with built-in parts can also be used.

內層基板與樹脂薄片之層合，例如可藉由自支撐體側將樹脂薄片加熱壓接於內層基板來進行。將樹脂薄片加熱壓接於內層基板之構件(以下亦稱「加熱壓接構件」)，例如可列舉經加熱之金屬板(SUS鏡板等)或金屬輥(SUS輥)等。再者，較佳為以樹脂薄片充分追附於內層基板之表面凹凸的方式，透過耐熱橡膠等之彈性材進行按壓(press)，而非將加熱壓接構件直接按壓於樹脂薄片。The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by heat-compression bonding the resin sheet to the inner layer substrate from the side of the support. A member for thermocompression-bonding a resin sheet to an inner layer substrate (hereinafter also referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Furthermore, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently adheres to the surface irregularities of the inner substrate, rather than directly pressing the thermocompression bonding member on the resin sheet.

內層基板與樹脂薄片之層合，可藉由真空疊合法實施。真空疊合法中，加熱壓接溫度較佳為60℃~160℃、更佳為80℃~140℃之範圍，加熱壓接壓力較佳為0.098MPa~1.77MPa、更佳為0.29MPa~1.47MPa之範圍，加熱壓接時間較佳為20秒~400秒、更佳為30秒~300秒之範圍。層合較佳可於壓力26.7hPa以下之減壓條件下實施。The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C~160°C, more preferably 80°C~140°C, and the heating and crimping pressure is preferably 0.098MPa~1.77MPa, more preferably 0.29MPa~1.47MPa The range of the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can preferably be carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

層合可藉由市售之真空疊合機來進行。市售之真空疊合機，例如可列舉名機製作所公司製之真空加壓式疊合機、Nikko-Materials公司製之真空塗抹器、批式真空加壓疊合機等。Lamination can be performed with a commercially available vacuum lamination machine. Commercially available vacuum lamination machines include, for example, a vacuum pressure lamination machine manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko-Materials, and a batch vacuum pressure lamination machine.

層合之後，亦可於常壓下(大氣壓下)，例如藉由將加熱壓接構件從支撐體側進行按壓，來進行經層合之樹脂薄片之平滑化處理。平滑化處理之按壓條件，可設為與上述層合之加熱壓接條件相同之條件。平滑化處理可藉由市售之疊合機進行。再者，層合與平滑化處理，亦可使用上述之市售之真空疊合機連續地進行。After lamination, smoothing of the laminated resin sheet can also be performed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the above-mentioned thermocompression bonding conditions for lamination. The smoothing treatment can be performed by a commercially available laminating machine. Furthermore, the lamination and smoothing treatment can also be carried out continuously using the above-mentioned commercially available vacuum lamination machine.

支撐體可於步驟(I)與步驟(II)之間去除、亦可於步驟(II)之後去除。The support can be removed between step (I) and step (II), and can also be removed after step (II).

步驟(II)中，係使樹脂組成物層硬化(例如熱硬化)，而形成由樹脂組成物之硬化物所構成的絕緣層。樹脂組成物層之硬化條件不特別限定，可使用形成印刷配線板之絕緣層時通常採用的條件。In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a printed wiring board can be used.

例如，樹脂組成物層之熱硬化條件，雖亦依樹脂組成物之種類等而異，於一實施形態中，硬化溫度較佳為120℃~240℃、更佳為150℃~220℃、又更佳為170℃~210℃。硬化時間較佳可為5分鐘~120分鐘、更佳可為10分鐘~100分鐘、又更佳可為15分鐘~100分鐘。For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and More preferably, it is 170°C~210°C. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 100 minutes.

使樹脂組成物層熱硬化之前，亦可將樹脂組成物層於較硬化溫度更低的溫度下進行預備加熱。例如，在使樹脂組成物層熱硬化之前，亦可於50℃~120℃、較佳為60℃~115℃、更佳為70℃~110℃之溫度下，將樹脂組成物層進行預備加熱5分鐘以上、較佳為5分鐘~150分鐘、更佳為15分鐘~120分鐘、又更佳為15分鐘~100分鐘。Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the resin composition layer can also be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C More than 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes.

於製造印刷配線板時，亦可進一步實施(III)對絕緣層開孔之步驟、(IV)將絕緣層進行粗化處理之步驟、(V)形成導體層之步驟。此等之步驟(III)至步驟(V)，可遵照印刷配線板之製造所用的所屬技術領域中具有通常知識者公知之各種方法實施。再者，於步驟(II)之後去除支撐體時，該支撐體之去除，可於步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間，或步驟(IV)與步驟(V)之間實施。又，亦可依需要，重複實施步驟(II)~步驟(V)之絕緣層及導體層之形成，來形成多層配線板。When manufacturing a printed wiring board, (III) the step of opening holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further implemented. These steps (III) to (V) can be implemented in accordance with various methods known to those skilled in the art for the production of printed wiring boards. Furthermore, when removing the support after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or step (IV ) and step (V) between implementation. In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated as required to form a multilayer wiring board.

其他實施形態中，本發明之印刷配線板，可使用上述之預浸物製造。製造方法基本上係與使用樹脂薄片的情況相同。In other embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

步驟(III)為對絕緣層開孔之步驟，藉此可於絕緣層形成通孔(via hole)、穿通孔(through hole)等之孔洞。步驟(III)可因應絕緣層之形成所使用的樹脂組成物之組成等，例如使用鑽頭、雷射、電漿等來實施。孔洞之尺寸或形狀，可因應印刷配線板之設計來適當決定。Step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be implemented according to the composition of the resin composition used for forming the insulating layer, for example, by using a drill, laser, plasma, etc. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

步驟(IV)為將絕緣層進行粗化處理之步驟。通常，於該步驟(IV)中，亦進行膠渣之去除。粗化處理之流程、條件不特別限定，可採用形成印刷配線板之絕緣層時通常使用的公知流程、條件。例如，可依序實施以膨潤液所進行之膨潤處理、以氧化劑所進行之粗化處理、以中和液所進行之中和處理，而將絕緣層進行粗化處理。Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the removal of scum is also carried out. The flow and conditions of the roughening treatment are not particularly limited, and generally known flow and conditions used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing swelling treatment with swelling liquid, roughening treatment with oxidizing agent, and neutralization treatment with neutralizing solution.

粗化處理所用之膨潤液不特別限定，可列舉鹼溶液、界面活性劑溶液等，較佳為鹼溶液，該鹼溶液更佳為氫氧化鈉溶液、氫氧化鉀溶液。市售之膨潤液，例如可列舉Atotech Japan公司製之「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。以膨潤液所進行之膨潤處理不特別限定，例如可藉由於30℃~90℃之膨潤液中將絕緣層浸漬1分鐘~20分鐘來進行。就將絕緣層之樹脂之膨潤抑制在適度的等級之觀點，較佳於40℃~80℃之膨潤液中將絕緣層浸漬5分鐘~15分鐘。The swelling solution used in the roughening treatment is not particularly limited, and examples include alkali solution, surfactant solution, etc., preferably alkali solution, more preferably sodium hydroxide solution, potassium hydroxide solution. As a commercially available swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment with the swelling liquid is not particularly limited, for example, it can be carried out by immersing the insulating layer in the swelling liquid at 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 preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

粗化處理所用之氧化劑不特別限定，例如可列舉於氫氧化鈉之水溶液中溶解有過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液。以鹼性過錳酸溶液等之氧化劑所進行的粗化處理，較佳於加熱至60℃~100℃之氧化劑溶液中將絕緣層浸漬10分鐘~30分鐘來進行。又，鹼性過錳酸溶液中之過錳酸鹽之濃度較佳為5質量%~10質量%。市售之氧化劑，例如可列舉Atotech Japan公司製之「Concentrate Compact CP」、「Dosing Solution Securiganth P」等之鹼性過錳酸溶液。The oxidizing agent used in the roughening treatment is not particularly limited, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Also, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

又，粗化處理所用之中和液，較佳為酸性之水溶液，市售品例如可列舉Atotech Japan公司製之「Reduction Solution Securiganth P」。In addition, the neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., for example.

以中和液所進行之處理，可藉由將經氧化劑粗化處理之處理面於30℃~80℃之中和液中浸漬5分鐘~30分鐘來進行。就作業性等之觀點，較佳為將經氧化劑粗化處理之對象物，於40℃~70℃之中和液中浸漬5分鐘~20分鐘之方法。The treatment with the neutralizing solution can be carried out by immersing the surface roughened by the oxidant in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability, etc., a method of immersing the object roughened by an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

於一實施形態中，粗化處理後之絕緣層表面之算術平均粗糙度(Ra)不特別限定，較佳為500nm以下、更佳為400nm以下、又更佳為300nm以下。下限不特別限定，例如可為1nm以上、2nm以上等。又，粗化處理後之絕緣層表面之均方根粗糙度(Rq)，較佳為500nm以下、更佳為400nm以下、又更佳為300nm以下。下限不特別限定，例如可為1nm以上、2nm以上等。絕緣層表面之算術平均粗糙度(Ra)及均方根粗糙度(Rq)，可使用非接觸型表面粗糙度計測定。In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, but is preferably less than 500 nm, more preferably less than 400 nm, and more preferably less than 300 nm. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, and the like. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, and the like. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured with a non-contact surface roughness meter.

步驟(V)為形成導體層之步驟，係於絕緣層上形成導體層。導體層所使用之導體材料不特別限定。於適合的實施形態中，導體層包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成之群的1種以上之金屬。導體層可為單金屬層亦可為合金層，合金層例如可列舉由選自上述群的2種以上之金屬的合金(例如鎳/鉻合金、銅/鎳合金及銅/鈦合金)所形成之層。其中就導體層形成之通用性、成本、圖型化之容易性等之觀點，尤佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層，或鎳/鉻合金、銅/鎳合金、銅/鈦合金之合金層；更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層，或鎳/鉻合金之合金層；又更佳為銅之單金屬層。Step (V) is a step of forming a conductive layer, which is to form a conductive layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductive layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (such as nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy). layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium is particularly preferred from the viewpoint of the versatility, cost, and ease of patterning of the conductor layer formation. alloy, copper/nickel alloy, copper/titanium alloy alloy layer; more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel/chromium alloy alloy layer; and More preferably a single metal layer of copper.

導體層可為單層結構、亦可為由不同種類之金屬或合金所構成的單金屬層或合金層層合2層以上而得的複層結構。導體層為複層結構時，與絕緣層鄰接之層，較佳為鉻、鋅或鈦之單金屬層，或鎳/鉻合金之合金層。The conductor layer may have a single-layer structure, or may have a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer adjacent 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，雖依所期望之印刷配線板之設計而異，一般而言為3μm~35μm、較佳為5μm~30μm。Although the thickness of the conductor layer varies according to the desired design of the printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

於一實施形態中，導體層可藉由鍍敷而形成。例如，可藉由半加成法、全加成法等之以往公知之技術對絕緣層之表面鍍敷，而形成具有所期望之配線圖型的導體層，就製造之簡便性之觀點，較佳為藉由半加成法來形成。以下，敘明以半加成法形成導體層的例子。In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by conventionally known techniques such as semi-additive method and full-additive method to form a conductor layer with a desired wiring pattern. Preferably formed by a semi-additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be described.

首先，於絕緣層之表面，藉由無電解鍍敷形成鍍敷種子層。接著，於所形成之鍍敷種子層上，對應於所期望之配線圖型，形成使鍍敷種子層之一部分露出的遮罩圖型。於所露出之鍍敷種子層上，藉由電解鍍敷而形成金屬層後，去除遮罩圖型。之後，將不要的鍍敷種子層藉由蝕刻等而去除，可形成具有所期望之配線圖型的導體層。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 is formed to expose a part of the plating seed layer corresponding to the desired wiring pattern. On the exposed plating seed layer, after forming a metal layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like 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。使用金屬箔形成導體層時，步驟(V)適合於步驟(I)與步驟(II)之間實施。例如，於步驟(I)之後，將支撐體去除，於所露出之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，可藉由真空疊合法實施。層合之條件，可設為與針對步驟(I)所說明的條件相同。接著，實施步驟(II)而形成絕緣層。之後，利用絕緣層上之金屬箔，藉由減成法、改良半加成法等之以往公知之技術，可形成具有所期望之配線圖型的導體層。In other embodiments, the conductive layer can be formed using metal foil. When metal foil is used to form the conductor layer, step (V) is suitably implemented between step (I) and step (II). For example, after the step (I), the support body is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The conditions for lamination can be set to be the same as those described for the step (I). Next, step (II) is implemented to form an insulating layer. Afterwards, using the metal foil on the insulating layer, a conductive layer having a desired wiring pattern can be formed by conventionally known techniques such as subtractive method and modified semi-additive method.

金屬箔例如可藉由電解法、壓延法等之公知方法製造。金屬箔之市售品，例如可列舉JX日鑛日石金屬公司製之HLP箔、JXUT-III箔、三井金屬鑛山公司製之3EC-III箔、TP-III箔等。Metal foil can be manufactured by known methods, such as an electrolysis method and a rolling method, for example. As a commercial item of metal foil, the HLP foil by JX Nippon Oil & Metals Co., Ltd., JXUT-III foil, the 3EC-III foil by Mitsui Metal Mining Co., Ltd., TP-III foil, etc. are mentioned, for example.

＜半導體裝置＞ 本發明之半導體裝置，包含本發明之印刷配線板。本發明之半導體裝置，可使用本發明之印刷配線板來製造。 ＜Semiconductor Devices＞ The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

作為半導體裝置，可列舉供電氣製品(例如、電腦、行動電話、數位相機及電視等)及交通工具(例如機車、汽車、電車、船舶及航空機等)等使用的各種半導體裝置。 [實施例] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trains, ships, and aircraft). [Example]

以下藉由實施例以具體說明本發明。本發明不限定於此等之實施例。再者，以下，表示量的「份」及「%」，只要無另外指明，分別意指「質量份」及「質量%」。無特別指定溫度時之溫度條件，係為室溫(23℃)，無特別指定壓力時之壓力條件，係為大氣壓(1atm)。The following examples illustrate the present invention in detail. The present invention is not limited to these examples. In addition, hereinafter, "parts" and "%" indicating the amount mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition when no special temperature is specified is room temperature (23°C), and the pressure condition when no special pressure is specified is atmospheric pressure (1atm).

＜合成例1：活性酯A(末端立體障礙型酯系硬化劑)之製造＞ 於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入p-tert-戊基酚492質量份、甲苯200質量份、二乙烯基苯(NIPPON STEEL Chemical & Material股份有限公司製「DVB-810」二乙烯基苯純度81%、含有乙基苯乙烯19%)130質量份、p-甲苯磺酸一水合物1質量份。一邊攪拌燒瓶之內容物一邊昇溫至120℃，於120℃攪拌1小時進行反應。反應結束後，添加49%氫氧化鈉水溶液1質量份進行中和後，添加甲苯400質量份，以水200質量份洗淨3次。於加熱減壓條件下將甲苯等餾去，得到包含未反應之p-tert-戊基酚與含有酚性羥基之樹脂(A-1)之混合物(1)601質量份。 <Synthesis example 1: Production of active ester A (terminal steric barrier type ester hardener)> In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, feed 492 parts by mass of p-tert-amylphenol, 200 parts by mass of toluene, divinylbenzene (NIPPON STEEL Chemical & Material shares "DVB-810" produced by Co., Ltd. has a divinylbenzene purity of 81%, contains 130 parts by mass of ethylstyrene (19%), and 1 part by mass of p-toluenesulfonic acid monohydrate. The temperature was raised to 120° C. while stirring the contents of the flask, and the reaction was carried out by stirring at 120° C. for 1 hour. After completion of the reaction, 1 part by mass of a 49% sodium hydroxide aqueous solution was added for neutralization, and then 400 parts by mass of toluene was added, followed by washing three times with 200 parts by mass of water. Toluene and the like were distilled off under heat and reduced pressure to obtain 601 parts by mass of a mixture (1) containing unreacted p-tert-amylphenol and a phenolic hydroxyl group-containing resin (A-1).

於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入間苯二甲酸氯化物152質量份與甲苯1000質量份，一邊將系統內減壓、氮取代，同時使其溶解。接著，給入先前所得之混合物(1)297質量份，一邊將系統內減壓、氮取代，同時使其溶解。添加四丁基銨溴化物0.4g，一邊實施氮氣沖洗，一邊將反應系統內控制於60℃以下，花費3小時滴下20%氫氧化鈉水溶液300質量份。滴下結束後，繼續攪拌1小時進行反應。反應結束後，將反應混合物靜置，進行分液，去除水層。對剩下的有機層添加水，攪拌混合約15分鐘後，將混合物靜置，進行分液，去除水層。重複該操作至水層之pH成為7後，於加熱減壓條件下將甲苯等餾去，得到活性酯A 409質量份。所得之活性酯A之活性酯當量為271。將該活性酯A以甲苯調製不揮發成分70質量%之溶液，用於實施例之樹脂組成物之調製。Put 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. dissolve. Next, 297 parts by mass of the previously obtained mixture (1) was introduced, and the system was depressurized and replaced with nitrogen, and dissolved. 0.4 g of tetrabutylammonium bromide was added, nitrogen flushing was performed, and the inside of the reaction system was controlled to 60° C. or lower, and 300 parts by mass of a 20% sodium hydroxide aqueous solution was dropped over 3 hours. After completion of the dropping, stirring was continued for 1 hour to perform a reaction. After the reaction was completed, the reaction mixture was left to stand for liquid separation, and the water layer was removed. Water was added to the remaining organic layer, and after stirring and mixing for about 15 minutes, the mixture was left still for liquid separation, and the water layer was removed. After repeating this operation until the pH of the water layer became 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain 409 parts by mass of active ester A. The active ester equivalent weight of the obtained active ester A was 271. This active ester A was prepared with toluene to prepare a solution of 70% by mass of non-volatile components, and used it for the preparation of the resin composition of the example.

(活性酯A之凝膠滲透層析(GPC)) 活性酯A之GPC圖係如圖1所示。 測定條件如下述。 測定裝置：東曹股份有限公司製「HLC-8420GPC」 管柱：東曹股份有限公司製保護管柱「HXL-L」+東曹股份有限公司製「TSK-GEL SuperHZ2000」+東曹股份有限公司製「TSK-GEL SuperHZ2000」+東曹股份有限公司製「TSK-GEL SuperHZ3000」+東曹股份有限公司製「TSK-GEL SuperHZ4000」 檢測器：RI(示差折射計) 數據處理：東曹股份有限公司製「GPC WorkStation EcoSEC-WorkStation」 管柱溫度：40℃ 展開溶劑：四氫呋喃 流速：0.35ml/分鐘 標準：根據前述「GPC WorkStation EcoSEC-WorkStation」之測定手冊，使用分子量已知之下述單分散聚苯乙烯。 試樣與測定：以樹脂固體成分換算成為0.2質量%的方式以四氫呋喃溶液進行稀釋，之後以微濾器過濾，對所得之樣品10μl進行測定。 (Gel Permeation Chromatography (GPC) of Active Ester A) The GPC chart of active ester A is shown in Figure 1. The measurement conditions are as follows. Measuring device: "HLC-8420GPC" manufactured by Tosoh Co., Ltd. String: Protective string "HXL-L" made by Tosoh Co., Ltd. + "TSK-GEL SuperHZ2000" made by Tosoh Co., Ltd. + "TSK-GEL SuperHZ2000" made by Tosoh Co., Ltd. + made by Tosoh Co., Ltd. "TSK-GEL SuperHZ3000" + Tosoh Co., Ltd. "TSK-GEL SuperHZ4000" Detector: RI (Differential Refractometer) Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35ml/min Standard: According to the measurement manual of the aforementioned "GPC WorkStation EcoSEC-WorkStation", the following monodisperse polystyrene with known molecular weight was used. Sample and measurement: After diluting with a tetrahydrofuran solution so that the resin solid content becomes 0.2% by mass, it was filtered with a microfilter, and 10 μl of the obtained sample was measured.

(活性酯A之紅外分光分析(IR)) 活性酯A之IR圖係如圖2所示。 測定條件如下述。 測定裝置：日本分光股份有限公司製 FT/IR-4600 測定方法：KBr薄片法、透過測定 試樣與測定：以樹脂固體成分換算成為10質量%的方式以四氫呋喃溶液進行稀釋，調製樣品。將該樣品0.1ml對KBr板滴下，以烘箱100℃將THF與H 2O乾燥10分鐘後，進行透過測定。 (Infrared spectroscopic analysis (IR) of active ester A) The IR chart of active ester A is shown in FIG. 2 . The measurement conditions are as follows. Measuring device: FT/IR-4600 manufactured by JASCO Co., Ltd. Measuring method: KBr sheet method, transmission measurement Sample and measurement: Prepare a sample by diluting it with a tetrahydrofuran solution so that the resin solid content becomes 10% by mass. 0.1 ml of this sample was dropped on a KBr plate, and after drying THF and H 2 O in an oven at 100° C. for 10 minutes, the permeation measurement was performed.

＜合成例2：活性酯B(末端鄰甲酚型酯系硬化劑)之合成＞ 於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入2,7-二羥基萘320g(2.0莫耳)、苄基醇184g(1.7莫耳)、對甲苯磺酸･1水合物5.0g，於室溫下，一邊吹入氮一邊攪拌。之後，昇溫至150℃，一邊將所生成之水餾去至系統外一邊攪拌4小時。反應結束後，添加甲基異丁基酮900g、20%氫氧化鈉水溶液5.4g進行中和後，藉由分液去除水層，以水280g進行3次水洗，將甲基異丁基酮於減壓下去除，得到苄基改質萘化合物(A-1)460g。所得之苄基改質萘化合物(A-1)為黑色固體，羥基當量為180克/當量。 <Synthesis example 2: Synthesis of active ester B (terminal o-cresol type ester hardener)> In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, feed 2,7-dihydroxynaphthalene 320g (2.0 moles), benzyl alcohol 184g (1.7 moles), p-toluenesulfonate Acid ･monohydrate 5.0 g was stirred while blowing nitrogen at room temperature. Then, it heated up to 150 degreeC, and stirred for 4 hours, distilling the produced|generated water out of a system. After the reaction was completed, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added for neutralization, the water layer was removed by liquid separation, and water was washed three times with 280 g of water, and the methyl isobutyl ketone was It was removed under reduced pressure to obtain 460 g of a benzyl-modified naphthalene compound (A-1). The obtained benzyl-modified naphthalene compound (A-1) was a black solid with a hydroxyl equivalent weight of 180 g/equivalent.

於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入間苯二甲酸氯化物203.0g(酸氯化物基之莫耳數：2.0莫耳)與甲苯1400g，將系統內減壓、氮取代，使其溶解。接著，給入鄰甲酚72.4g(0.67莫耳)、苄基改質萘化合物(A-1)240g(酚性羥基之莫耳數：1.33莫耳)，將系統內減壓、氮取代，使其溶解。之後，使四丁基銨溴化物0.70g溶解，一邊實施氮氣沖洗，一邊將系統內控制於60℃以下，花費3小時滴下20%氫氧化鈉水溶液400g。接著於該條件下持續攪拌1.0小時。反應結束後，靜置分液，去除水層。進一步於溶解有反應物之甲苯層中投入水，攪拌混合15分鐘，靜置分液，去除水層。重複該操作，至水層之pH成為7。之後，藉由傾析器脫水去除水分，得到不揮發成分61.5質量%之甲苯溶液狀態之活性酯B。所得之活性酯B之活性酯當量為206g/eq.。In the flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, put 203.0 g of isophthalic acid chloride (the number of moles of the acid chloride base: 2.0 moles) and 1400 g of toluene, and the system Under reduced pressure and nitrogen substitution, it was dissolved. Next, 72.4 g (0.67 mol) of o-cresol and 240 g of benzyl-modified naphthalene compound (A-1) (the mole number of phenolic hydroxyl group: 1.33 mol) were introduced, and the system was decompressed and replaced by nitrogen. Let it dissolve. Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the liquid was separated by standing, and the water layer was removed. Water was further added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Afterwards, water was removed by dehydration with a decanter to obtain active ester B in a toluene solution state with a non-volatile content of 61.5% by mass. The active ester equivalent of the active ester B obtained is 206g/eq.

＜合成例3：活性酯C(末端鄰苯基酚型酯系硬化劑)之合成＞ 於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入間苯二甲酸氯化物203.0g(酸氯化物基之莫耳數：2.0莫耳)與甲苯1400g，將系統內減壓、氮取代，使其溶解。接著，給入鄰苯基酚113.9g(0.67莫耳)、苄基改質萘化合物(A-1)240g(酚性羥基之莫耳數：1.33莫耳)，將系統內減壓、氮取代，使其溶解。之後，使四丁基銨溴化物0.70g溶解，一邊實施氮氣沖洗，一邊將系統內控制於60℃以下，花費3小時滴下20%氫氧化鈉水溶液400g。接著於該條件下持續攪拌1.0小時。反應結束後，靜置分液，去除水層。進一步於溶解有反應物之甲苯層中投入水，攪拌混合15分鐘，靜置分液，去除水層。重複該操作，至水層之pH成為7。之後，藉由傾析器脫水去除水分，得到不揮發成分65質量%之甲苯溶液狀態之活性酯C。所得之活性酯C之活性酯當量為238g/eq.。 <Synthesis example 3: Synthesis of active ester C (terminated ortho-phenylphenol type ester hardener)> In the flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, put 203.0 g of isophthalic acid chloride (the number of moles of the acid chloride base: 2.0 moles) and 1400 g of toluene, and the system Under reduced pressure and nitrogen substitution, it was dissolved. Next, 113.9 g (0.67 moles) of o-phenylphenol and 240 g (the number of moles of phenolic hydroxyl groups: 1.33 moles) of benzyl-modified naphthalene compound (A-1) were introduced, and the system was decompressed and nitrogen replaced , to dissolve it. Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the liquid was separated by standing, and the water layer was removed. Water was further added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Afterwards, water was removed by dehydration with a decanter to obtain active ester C in a toluene solution state with 65% by mass of non-volatile components. The active ester equivalent of the active ester C obtained is 238g/eq.

＜合成例4：活性酯D(末端苯乙烯化酚型酯系硬化劑)之合成＞ 於安裝有溫度計、滴液漏斗、冷卻管、分餾管、攪拌器之燒瓶中，給入間苯二甲酸氯化物203.0g(酸氯化物基之莫耳數：2.0莫耳)與甲苯1400g，將系統內減壓、氮取代，使其溶解。接著，給入苯乙烯化酚(酚之苯乙烯加成反應物、三光公司製「SP」)132.7g(0.67莫耳)、苄基改質萘化合物(A-1)240g(酚性羥基之莫耳數：1.33莫耳)，將系統內減壓、氮取代，使其溶解。之後，使四丁基銨溴化物0.70g溶解，一邊實施氮氣沖洗，一邊將系統內控制於60℃以下，花費3小時滴下20%氫氧化鈉水溶液400g。接著於該條件下持續攪拌1.0小時。反應結束後，靜置分液，去除水層。進一步於溶解有反應物之甲苯層中投入水，攪拌混合15分鐘，靜置分液，去除水層。重複該操作，至水層之pH成為7。之後，藉由傾析器脫水去除水分，得到不揮發成分65質量%之甲苯溶液狀態之活性酯D。所得之活性酯D之活性酯當量為259g/eq.。 <Synthesis Example 4: Synthesis of Active Ester D (Terminal Styrenated Phenol Type Ester Hardener)> In the flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, put 203.0 g of isophthalic acid chloride (the number of moles of the acid chloride base: 2.0 moles) and 1400 g of toluene, and the system Under reduced pressure and nitrogen substitution, it was dissolved. Next, 132.7 g (0.67 moles) of styrenated phenol (a styrene addition reaction product of phenol, “SP” produced by Sanko Co., Ltd.), 240 g (A-1) of a benzyl-modified naphthalene compound (a phenolic hydroxyl group) Number of moles: 1.33 moles), the system was decompressed and replaced with nitrogen to dissolve it. Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the inside of the system was controlled at 60° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the liquid was separated by standing, and the water layer was removed. Water was further added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Afterwards, water was removed by dehydration with a decanter to obtain active ester D in a toluene solution state with 65% by mass of non-volatile components. The active ester equivalent of the active ester D obtained is 259g/eq.

＜實施例1＞ 將環氧樹脂「ESN475V」(NIPPON STEEL Chemical & Material公司製、環氧當量：約330g/eq.)6份，與環氧樹脂「HP-4032-SS」(DIC公司製、環氧當量：約144g/eq.)4份，溶解於甲基乙基酮(MEK)10份，得到環氧樹脂溶液。 <Example 1> 6 parts of epoxy resin "ESN475V" (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., epoxy equivalent: about 330 g/eq.) and epoxy resin "HP-4032-SS" (manufactured by DIC Corporation, epoxy equivalent: about 330 g/eq.) 144g/eq.) 4 parts, dissolved in 10 parts of methyl ethyl ketone (MEK), to obtain an epoxy resin solution.

對所得之環氧樹脂溶液，添加合成例1所得之活性酯A(末端立體障礙型酯系硬化劑、不揮發成分70質量%之甲苯溶液)11份、末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」、活性酯當量229、不揮發成分61.5質量%之甲苯溶液)11份、經胺系烷氧基矽烷化合物(信越化學工業公司製「KBM573」)表面處理之球形二氧化矽(Admatechs公司製「SO-C2」、平均粒徑0.77μm)65份、咪唑系硬化促進劑(四國化成公司製「1B2PZ」)0.2份，以高速旋轉混合器均勻分散，調製塗漆狀之樹脂組成物。To the epoxy resin solution obtained, 11 parts of the active ester A obtained in Synthesis Example 1 (terminal steric hindrance type ester hardener, toluene solution with 70% by mass of non-volatile content), 11 parts of the terminal naphthol type active ester hardener ( "HPC-8150-62T" manufactured by DIC Corporation, 11 parts of toluene solution with an active ester equivalent of 229 and a non-volatile content of 61.5% by mass) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 65 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.77 μm), 0.2 parts of imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.), uniformly dispersed with a high-speed rotary mixer, and prepared Painted resin composition.

＜實施例2＞ 使用末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8000-65T」、活性酯當量223、不揮發成分65質量%之甲苯溶液)11份，以取代末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)11份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 <Example 2> Use 11 parts of terminal naphthol-type active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223, non-volatile content 65% by mass toluene solution) to replace the terminal naphthol-type active ester-based hardener A paint-like resin composition was prepared in the same manner as in Example 1 except for 11 parts of the agent ("HPC-8150-62T" manufactured by DIC Corporation).

＜實施例3＞ 將球形二氧化矽(Admatechs公司製「SO-C2」)之使用量由65份變更為70份，將咪唑系硬化促進劑(四國化成公司製「1B2PZ」)之使用量由0.2份變更為0.02份，進一步地，添加酚系硬化劑(DIC公司製「LA-3018-50P」、酚當量151、不揮發成分50質量%之1-甲氧基-2丙醇溶液)2份，及碳二亞胺系硬化劑(日清紡化學公司製「V-03」、不揮發成分50質量%之甲苯溶液)1份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 <Example 3> The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) was changed from 65 parts to 70 parts, and the amount of imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.) was changed from 0.2 parts to 0.02 parts, and further, 2 parts of phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, 1-methoxy-2 propanol solution with a phenol equivalent of 151 and a non-volatile content of 50% by mass) were added, and carbon A paint-like resin composition was prepared in the same manner as in Example 1 except for 1 part of a diimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with 50% by mass of non-volatile content).

＜實施例4＞ 將球形二氧化矽(Admatechs公司製「SO-C2」)之使用量由65份變更為70份，將咪唑系硬化促進劑(四國化成公司製「1B2PZ」)之使用量由0.2份變更為0.02份，進一步地，添加酚系硬化劑(DIC公司製「LA-3018-50P」、酚當量151、不揮發成分50質量%之1-甲氧基-2丙醇溶液)2份，及碳二亞胺系硬化劑(日清紡化學公司製「V-03」、不揮發成分50質量%之甲苯溶液)1份，除此以外係與實施例2同樣地調製塗漆狀之樹脂組成物。 <Example 4> The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) was changed from 65 parts to 70 parts, and the amount of imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd.) was changed from 0.2 parts to 0.02 parts, and further, 2 parts of phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, 1-methoxy-2 propanol solution with a phenol equivalent of 151 and a non-volatile content of 50% by mass) were added, and carbon A paint-like resin composition was prepared in the same manner as in Example 2 except for 1 part of a diimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with 50% by mass of non-volatile content).

＜實施例5＞ 將球形二氧化矽(Admatechs公司製「SO-C2」)之使用量由70份變更為35份，進一步地，添加經胺系烷氧基矽烷化合物(信越化學工業公司製「KBM573」)表面處理之中空二氧化矽(日揮觸媒化成公司製「BA-S」、平均粒徑2.6μm、空孔率25體積%)35份，除此以外係與實施例3同樣地調製塗漆狀之樹脂組成物。 <Example 5> The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) was changed from 70 parts to 35 parts, and an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added for surface treatment. 35 parts of hollow silica ("BA-S" manufactured by Nikki Catalyst Chemicals Co., Ltd., average particle size 2.6 μm, porosity 25% by volume) was prepared in the same manner as in Example 3, except that a paint-like resin was prepared. Composition.

＜實施例6＞ 不使用末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)，且將合成例1所得之活性酯A(末端立體障礙型酯系硬化劑)之使用量由11份變更為22份，除此以外係與實施例5同樣地調製塗漆狀之樹脂組成物。 <Example 6> No terminal naphthol-type active ester-based hardener ("HPC-8150-62T" manufactured by DIC Corporation) was used, and the amount of active ester A (terminal steric barrier-type ester-based hardener) obtained in Synthesis Example 1 was changed from 11 parts Except having changed it into 22 parts, it prepared the resin composition of the paint shape similarly to Example 5.

＜實施例7＞ 使用合成例2所得之活性酯B(末端鄰甲酚型活性酯系硬化劑、不揮發成分65質量%之甲苯溶液)11份，以取代末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)11份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 <Example 7> Use 11 parts of the active ester B obtained in Synthesis Example 2 (terminal o-cresol type active ester hardener, toluene solution with 65% by mass of non-volatile content) to replace the terminal naphthol type active ester hardener (manufactured by DIC Corporation " HPC-8150-62T") was 11 parts, and the paint-like resin composition was prepared similarly to Example 1 except this.

＜實施例8＞ 使用合成例3所得之活性酯C(末端鄰苯基酚型活性酯系硬化劑、不揮發成分65質量%之甲苯溶液)11份，以取代末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)11份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 <Example 8> Use 11 parts of the active ester C obtained in Synthesis Example 3 (terminal o-phenylphenol type active ester hardener, toluene solution with 65% by mass of non-volatile content) to replace the terminal naphthol type active ester hardener (manufactured by DIC Corporation) "HPC-8150-62T") was 11 parts, and it prepared the resin composition of the paint form similarly to Example 1 except this.

＜實施例9＞ 使用合成例4所得之活性酯D(末端苯乙烯化酚型活性酯系硬化劑、不揮發成分65質量%之甲苯溶液)11份，以取代末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)11份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 <Example 9> Use 11 parts of the active ester D obtained in Synthesis Example 4 (terminal styrenated phenol type active ester hardener, toluene solution with 65 mass % of non-volatile content) to replace the terminal naphthol type active ester hardener (manufactured by DIC Corporation) "HPC-8150-62T") was 11 parts, and it prepared the resin composition of the paint form similarly to Example 1 except this.

＜比較例1＞ 不使用合成例1所得之活性酯A(末端立體障礙型酯系硬化劑)，且將末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)之使用量由11份變更為22份，除此以外係與實施例1同樣地調製塗漆狀之樹脂組成物。 ＜Comparative example 1＞ The active ester A obtained in Synthesis Example 1 (terminal steric barrier type ester hardener) was not used, and the usage amount of the terminal naphthol type active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation) was changed from 11 parts Except having changed it into 22 parts, it prepared the resin composition of the paint shape similarly to Example 1.

＜比較例2＞ 不使用合成例1所得之活性酯A(末端立體障礙型酯系硬化劑)，且將末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8000-65T」)之使用量由11份變更為22份，除此以外係與實施例2同樣地調製塗漆狀之樹脂組成物。 ＜Comparative example 2＞ The active ester A (terminal steric hindrance type ester hardener) obtained in Synthesis Example 1 was not used, and the usage amount of the terminal naphthol type active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation) was changed from 11 parts Except having changed it into 22 parts, it prepared the resin composition of the paint shape similarly to Example 2.

＜比較例3＞ 不使用合成例1所得之活性酯A(末端立體障礙型酯系硬化劑)，且將末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8150-62T」)之使用量由11份變更為22份，除此以外係與實施例3同樣地調製塗漆狀之樹脂組成物。 ＜Comparative example 3＞ The active ester A obtained in Synthesis Example 1 (terminal steric barrier type ester hardener) was not used, and the usage amount of the terminal naphthol type active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation) was changed from 11 parts Except having changed it into 22 parts, it prepared the resin composition of the paint shape similarly to Example 3.

＜比較例4＞ 不使用合成例1所得之活性酯A(末端立體障礙型酯系硬化劑)，且將末端萘酚型活性酯系硬化劑(DIC公司製「HPC-8000-65T」)之使用量由11份變更為22份，除此以外係與實施例4同樣地調製塗漆狀之樹脂組成物。 ＜Comparative example 4＞ The active ester A (terminal steric hindrance type ester hardener) obtained in Synthesis Example 1 was not used, and the usage amount of the terminal naphthol type active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation) was changed from 11 parts Except having changed it into 22 parts, it prepared the resin composition of the paint form similarly to Example 4.

＜製作例1：樹脂組成物層之厚度為40μm之樹脂薄片＞ 作為支撐體，係準備具備離型層之聚對苯二甲酸乙二酯薄膜(琳得科公司製「AL5」、厚度38μm)。於該支撐體之離型層上，將實施例及比較例所得之樹脂組成物，以乾燥後之樹脂組成物層之厚度成為40μm的方式進行均勻塗佈。之後，使樹脂組成物於80℃~100℃(平均90℃)乾燥4分鐘，得到包含支撐體及樹脂組成物層之樹脂薄片。 <Production example 1: Resin sheet with a resin composition layer thickness of 40 μm> As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) equipped with a release layer was prepared. On the release layer of the support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying became 40 μm. Afterwards, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet comprising a support body and a resin composition layer.

＜製作例2：樹脂組成物層之厚度為25μm之樹脂薄片＞ 與製作例1同樣地將實施例及比較例所得之樹脂組成物以乾燥後之樹脂組成物層之厚度成為25μm的方式進行均勻塗佈，於70℃~80℃(平均75℃)乾燥2.5分鐘，得到包含支撐體及樹脂組成物層之樹脂薄片。 <Production example 2: Resin sheet with a resin composition layer thickness of 25 μm> In the same manner as Production Example 1, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the dried resin composition layer became 25 μm, and dried at 70°C to 80°C (75°C on average) for 2.5 minutes , to obtain a resin sheet comprising a support body and a resin composition layer.

＜試驗例1：介電正切(Df)･介電率(Dk)之測定＞ 將製作例1所製作的厚度40μm之樹脂薄片於190℃加熱90分鐘，使樹脂組成物層熱硬化。之後，將支撐體剝離，得到樹脂組成物之硬化物。將該硬化物切斷為寬2mm、長80mm之試驗片。針對該試驗片，使用安捷倫科技公司製「HP8362B」，藉由共振腔微擾法，以測定頻率5.8GHz、測定溫度23℃測定介電正切(Df)、介電率(Dk)。針對3片試驗片進行測定，將其平均值示於下述表1。 <Test example 1: Measurement of dielectric tangent (Df) and dielectric constant (Dk)> The resin sheet with a thickness of 40 μm produced in Production Example 1 was heated at 190° C. for 90 minutes to thermoset the resin composition layer. Thereafter, the support body was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. For this test piece, the dielectric tangent (Df) and the dielectric constant (Dk) were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the resonant cavity perturbation method using “HP8362B” manufactured by Agilent Technologies. The measurement was performed on three test pieces, and the average values are shown in Table 1 below.

＜試驗例2：玻璃轉移溫度(Tg)之測定＞ 將試驗例1所製作的硬化物切出長20mm、寬6mm，作為評估樣品。針對各評估樣品，使用Rigaku公司製TMA裝置，由25℃至250℃以5℃/分鐘之昇溫速度測定玻璃轉移溫度(Tg)。針對同一試驗片進行2次測定，紀錄第2次之值。 <Test Example 2: Measurement of Glass Transition Temperature (Tg)> The cured product produced in Test Example 1 was cut out to have a length of 20 mm and a width of 6 mm, and it was used as an evaluation sample. For each evaluation sample, the glass transition temperature (Tg) was measured from 25° C. to 250° C. at a heating rate of 5° C./min using a TMA apparatus manufactured by Rigaku Corporation. Carry out 2 measurements on the same test piece, and record the second value.

＜試驗例3：除膠渣處理後之龜裂耐性之評估＞ 將製作例2所製作的厚度25μm之樹脂薄片，以成為殘銅率60%的方式，於以400μm間隔將直徑350μm之圓形之銅墊(銅厚35μm)形成為格子狀之芯材(日立化成工業公司製「E705GR」、厚度400μm)之兩面，使用批式真空加壓疊合機(Nikko-Materials公司製2階段增層疊合機「CVP700」)，以樹脂組成物層與前述內層基板接合的方式，疊合於內層基板之兩面。該疊合係藉由減壓30秒使氣壓成為13hPa以下後，於溫度100℃、壓力0.74MPa壓接30秒來實施。將之投入130℃之烘箱中，加熱30分鐘，接著移至170℃之烘箱，加熱30分鐘。進一步剝離支持層，將所得之電路基板於60℃浸漬於膨潤液Atotech Japan(股)之Swelling Dip Securiganth P中10分鐘。接著於80℃浸漬於粗化液Atotech Japan(股)之Concentrate Compact P(KMnO 4：60g/L、NaOH：40g/L之水溶液)中30分鐘。最後於40℃浸漬於中和液Atotech Japan(股)之Reduction Solution Securiganth P中5分鐘。觀察100個的粗化處理後之電路基板之銅墊部，確認有無樹脂組成物層之龜裂。龜裂若為10個以下視為「〇」、多於10個則視為「×」。 <Test Example 3: Evaluation of Cracking Resistance after Desmear Treatment> The resin sheet with a thickness of 25 μm produced in Production Example 2 was placed in a circular shape with a diameter of 350 μm at intervals of 400 μm so that the remaining copper ratio was 60%. The copper pads (copper thickness 35 μm) are formed on both sides of a grid-shaped core material ("E705GR" manufactured by Hitachi Chemical Industry Co., Ltd., thickness 400 μm), using a batch vacuum pressure lamination machine (manufactured by Nikko-Materials Co., Ltd. 2-stage build-up lamination) Lamination machine "CVP700") is laminated on both sides of the inner substrate in such a way that the resin composition layer is bonded to the aforementioned inner substrate. This lamination was carried out by pressure-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds after depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less. Put it into an oven at 130°C and heat it for 30 minutes, then move it to an oven at 170°C and heat it for 30 minutes. The supporting layer was further peeled off, and the obtained circuit board was immersed in a swelling solution of Atotech Japan Co., Ltd. Swelling Dip Securiganth P at 60° C. for 10 minutes. Next, it was immersed in the roughening solution Concentrate Compact P (KMnO 4 : 60 g/L, NaOH: 40 g/L aqueous solution) of Atotech Japan Co., Ltd. for 30 minutes at 80°C. Finally, immerse in Reduction Solution Securiganth P of Atotech Japan Co., Ltd., a neutralizing solution, at 40°C for 5 minutes. The copper pads of 100 roughened circuit boards were observed to confirm the presence or absence of cracks in the resin composition layer. When there were less than 10 cracks, it was regarded as "o", and when more than 10, it was regarded as "x".

各實施例及比較例之樹脂組成物中所含有的原料之使用量、試驗例之測定結果及評估結果歸納於下述表1。The usage-amount of the raw material contained in the resin composition of each Example and a comparative example, the measurement result and evaluation result of a test example are summarized in Table 1 below.

由上述表1所示之結果，得知使用含有(B1)末端立體障礙型活性酯系硬化劑之樹脂組成物時，相較於不含(B1)末端立體障礙型活性酯系硬化劑者而言，可得到龜裂耐性優良的硬化物。又，得知使用除了(B1)末端立體障礙型活性酯系硬化劑以外進一步含有(B2)其他活性酯系硬化劑之樹脂組成物時，可得到玻璃轉移溫度優良的硬化物。又，就使用中空二氧化矽作為(C)成分之實施例5、6而言，介電率較實施例3、4更為減低，為更佳之一態樣。From the results shown in Table 1 above, it can be seen that when the resin composition containing (B1) terminal steric barrier type active ester hardener is used, compared with the resin composition without (B1) terminal steric barrier type active ester hardener In other words, a hardened product with excellent crack resistance can be obtained. In addition, it was found that when a resin composition containing (B2) other active ester curing agent is used in addition to (B1) terminal steric barrier type active ester curing agent, a cured product having an excellent glass transition temperature can be obtained. Also, for Examples 5 and 6, which use hollow silica as the component (C), the dielectric constant is lower than that of Examples 3 and 4, which is a better aspect.

本案係以對日本國特許廳申請的日本特願2021-138354(申請日2021年8月26日)為基礎，其內容全部包含於本說明書中。This case is based on Japanese Patent Application No. 2021-138354 (filing date: August 26, 2021) filed with the Japan Patent Office, and its contents are fully included in this specification.

[圖1]圖1表示合成例1之活性酯A(末端立體障礙型酯系硬化劑)之GPC圖。 [圖2]圖2表示合成例1之活性酯A(末端立體障礙型酯系硬化劑)之IR圖。 [FIG. 1] FIG. 1 shows the GPC chart of active ester A (terminal steric hindrance type ester-based hardener) of Synthesis Example 1. [FIG. [ Fig. 2] Fig. 2 shows the IR chart of active ester A (terminal steric hindrance type ester-based hardener) of Synthesis Example 1.

Claims (20)

一種樹脂組成物，其係含有(A)環氧樹脂、(B)活性酯系硬化劑及(C)無機填充材之樹脂組成物，其中 以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為60質量%以上， (B)成分，包含(B1)具有式(B1-1)： [式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； a表示0、1或2； *表示鍵結部位] 表示之結構的活性酯系硬化劑。 A resin composition, which is a resin composition containing (A) epoxy resin, (B) active ester hardener and (C) inorganic filler, wherein when the non-volatile components in the resin composition are 100% by mass , (C) component content is more than 60% by mass, (B) component, including (B1) has the formula (B1-1): [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have a substituent; R 1c represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 each independently represent a substituent; a stands for 0, 1 or 2; * stands for the bonding site] is an active ester hardener with the structure represented. 如請求項1之樹脂組成物，其中(B1)成分，包含除了式(B1-1)表示之結構以外，進一步具有式(B1-2b)： [式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； R 3係分別獨立地表示氫原子或甲基； 環X 1表示可具有取代基之芳香族碳環； a表示0、1或2； *表示鍵結部位] 表示之結構的活性酯系硬化劑。 The resin composition as claimed in item 1, wherein component (B1) includes, in addition to the structure represented by formula (B1-1), further has formula (B1-2b): [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have a substituent; R 1c represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 each independently represent a substituent; R 3 independently represents a hydrogen atom or a methyl group; Ring X 1 represents an aromatic carbocyclic ring that may have a substituent; a represents 0, 1 or 2; * represents the bonding site] The active ester hardener of the structure represented . 如請求項1之樹脂組成物，其中(B1)成分包含式(B1c)： [式中， R 1a及R 1b係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基，或者R 1a及R 1b一起鍵結，而形成可具有取代基之非芳香族碳環； R 1c係分別獨立地表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； R 2係分別獨立地表示取代基； R 3係分別獨立地表示氫原子或甲基； 環X 1及環Y 1係分別獨立地表示可具有取代基之芳香族碳環； a係分別獨立地表示0、1或2； b表示0，或1以上之整數] 表示之樹脂。 The resin composition as claimed in item 1, wherein the component (B1) comprises the formula (B1c): [wherein, R 1a and R 1b represent independently an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, or R 1a and R 1b are bonded together, and Form a non-aromatic carbocyclic ring that may have substituents; R 1c each independently represent an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R 2 are each independently Represents a substituent; R 3 each independently represents a hydrogen atom or a methyl group; Ring X 1 and ring Y 1 each independently represent an aromatic carbocyclic ring that may have a substituent; a represents independently 0, 1 or 2 ; b represents 0, or an integer greater than 1] represents the resin. 如請求項1之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(B1)成分之含量為3質量%~20質量%。Such as the resin composition of claim 1, wherein when the non-volatile components in the resin composition are 100% by mass, the content of the component (B1) is 3% by mass to 20% by mass. 如請求項1之樹脂組成物，其中(B)成分進一步包含(B2)具有式(B2-1)： [式中， R 4、R 5及R 6，係(1)R 4表示氫原子、鹵素原子、甲基或R 41-A-，且R 5及R 6係分別獨立地表示氫原子或取代基，或(2)R 4及R 5一起鍵結，而形成可具有取代基之芳香族碳環，且R 6表示氫原子或取代基，或(3)R 5及R 6一起鍵結，而形成可具有取代基之芳香族碳環，且R 4表示氫原子、鹵素原子、甲基或R 41-A-； R 7及R 8係分別獨立地表示氫原子或取代基； R 41表示可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之芳基； A表示-CH 2-、-CH(CH 3)-、-CO-，或-O-； *表示鍵結部位] 表示之結構的活性酯系硬化劑。 The resin composition as claimed in item 1, wherein (B) component further comprises (B2) having the formula (B2-1): [In the formula, R 4 , R 5 and R 6 are (1) R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-, and R 5 and R 6 represent independently a hydrogen atom or a substitution group, or (2) R 4 and R 5 are bonded together to form an aromatic carbocyclic ring that may have a substituent, and R 6 represents a hydrogen atom or a substituent, or (3) R 5 and R 6 are bonded together, And form an aromatic carbocyclic ring that may have a substituent, and R 4 represents a hydrogen atom, a halogen atom, a methyl group or R 41 -A-; R 7 and R 8 represent a hydrogen atom or a substituent independently; R 41 represents An alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; A represents -CH 2 -, -CH(CH 3 )-, -CO-, or -O-; * Indicates the bonding site] is an active ester-based hardener with a structure indicated. 如請求項1之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(A)成分之含量為1質量%~20質量%。Such as the resin composition of claim 1, wherein when the non-volatile components in the resin composition are 100% by mass, the content of component (A) is 1% by mass to 20% by mass. 如請求項1之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(B)成分之含量為12質量%以上。The resin composition according to Claim 1, wherein when the non-volatile components in the resin composition are 100% by mass, the content of component (B) is 12% by mass or more. 如請求項1之樹脂組成物，其中(C)成分為二氧化矽。The resin composition as claimed in claim 1, wherein component (C) is silicon dioxide. 如請求項1之樹脂組成物，其中以樹脂組成物中之不揮發成分為100質量%時，(C)成分之含量為70質量%以上。The resin composition according to claim 1, wherein when the non-volatile components in the resin composition are 100% by mass, the content of component (C) is 70% by mass or more. 如請求項1之樹脂組成物，其進一步含有(D)硬化促進劑。The resin composition according to claim 1, further comprising (D) a hardening accelerator. 如請求項1之樹脂組成物，其進一步含有選自由酚系硬化劑及碳二亞胺系硬化劑所成之群的硬化劑。The resin composition according to claim 1, further comprising a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents. 如請求項1之樹脂組成物，其中以5.8GHz、23℃進行測定時，樹脂組成物之硬化物之介電正切(Df)為0.003以下。The resin composition according to claim 1, wherein when measured at 5.8GHz and 23°C, the dielectric tangent (Df) of the cured product of the resin composition is 0.003 or less. 如請求項1之樹脂組成物，其中樹脂組成物之硬化物之玻璃轉移溫度(Tg)為140℃以上。The resin composition according to claim 1, wherein the glass transition temperature (Tg) of the cured product of the resin composition is above 140°C. 如請求項1之樹脂組成物，其係用以形成導體層之絕緣層形成用。The resin composition as claimed in claim 1 is used for forming an insulating layer for forming a conductor layer. 如請求項1之樹脂組成物，其係印刷配線板之絕緣層形成用。The resin composition according to claim 1 is used for forming an insulating layer of a printed wiring board. 一種如請求項1~15中任一項之樹脂組成物之硬化物。A cured product of the resin composition according to any one of claims 1-15. 一種薄片狀層合材料，其含有如請求項1~15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 1-15. 一種樹脂薄片，其具有支撐體，與設置於該支撐體上的由如請求項1~15中任一項之樹脂組成物所形成的樹脂組成物層。A resin sheet, which has a support body, and a resin composition layer formed of the resin composition according to any one of claims 1 to 15 arranged on the support body. 一種印刷配線板，其具備由如請求項1~15中任一項之樹脂組成物之硬化物所構成的絕緣層。A printed wiring board comprising an insulating layer made of a hardened resin composition according to any one of claims 1 to 15. 一種半導體裝置，其包含如請求項19之印刷配線板。A semiconductor device comprising the printed wiring board according to claim 19.
TW111131992A 2021-08-26 2022-08-25 resin composition TW202328266A (en)

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